GEORGIA DEPARTMENT OF NATURAL RESOURCES ENVIRONMENTAL PROTECTION DIVISION Air Protection Branch Ambient Monitoring Program 2012 Ambient Air Surveillance Report This document is published annually by the Ambient Monitoring Program, in the Air Protection Branch of the Georgia Department of Natural Resources, Environmental Protection Division. Date of Initial Publication November 1, 2013 DISCLAIMER: Any reference to specific brand names is not an endorsement of that brand by Georgia Environmental Protection Division. TABLE OF CONTENTS TABLE OF CONTENTS ........................................................................................................................i LIST OF FIGURES.............................................................................................................................. iii LIST OF TABLES .................................................................................................................................v EXECUTIVE SUMMARY.....................................................................................................................vi GLOSSARY ...................................................................................................................................... viii INTRODUCTION................................................................................................................................. 1 CHEMICAL MONITORING ACTIVITIES ............................................................................................. 2 CARBON MONOXIDE (CO)......................................................................................... 8 OXIDES OF NITROGEN (NO, NO2, NOx and NOy) .................................................... 13 SULFUR DIOXIDE (SO2) ........................................................................................... 19 OZONE (O3)............................................................................................................... 24 LEAD (Pb).................................................................................................................. 37 PARTICULATE MATTER ........................................................................................... 42 PM10 ........................................................................................................................... 43 PMCoarse ...................................................................................................................... 49 PM2.5 .......................................................................................................................... 51 PM2.5 SPECIATION .................................................................................................... 63 PHOTOCHEMICAL ASSESSMENT MONITORING STATIONS (PAMS) .......................................... 69 CARBONYL COMPOUNDS ....................................................................................... 74 AIR TOXICS MONITORING .............................................................................................................. 83 METALS..................................................................................................................... 85 HEXAVALENT CHROMIUM (Cr6) .............................................................................. 90 VOLATILE ORGANIC COMPOUNDS (TO-14/15)...................................................... 92 SEMI-VOLATILE ORGANIC COMPOUNDS .............................................................. 96 METEOROLOGICAL REPORT ........................................................................................................100 STATE CLIMATOLOGY AND METEOROLOGICAL SUMMARY OF 2012................100 SUMMARY OF METEOROLOGICAL MEASUREMENTS FOR 2012........................107 OZONE AND PM2.5 FORECASTING AND DATA ANALYSIS ....................................109 PM2.5 CASE STUDY ANALYSES ..............................................................................113 QUALITY ASSURANCE...................................................................................................................118 QUALITY CONTROL AND QUALITY ASSESSMENT ...............................................119 GASEOUS POLLUTANTS ........................................................................................120 PARTICULATE MATTER ..........................................................................................123 AIR TOXICS..............................................................................................................128 NATTS ......................................................................................................................128 PHOTOCHEMICAL ASSESSMENT MONITORING ..................................................132 METEOROLOGY ......................................................................................................136 QUALITY CONTROL REPORTS ..............................................................................137 STANDARDS LABORATORY ...................................................................................137 LABORATORY AND FIELD STANDARD OPERATING PROCEDURE.....................137 SITING EVALUATIONS ............................................................................................137 RISK ASSESSMENT .......................................................................................................................139 INTRODUCTION .......................................................................................................139 RESULTS AND INTERPRETATION .........................................................................139 SUMMARY AND DISCUSSION ................................................................................149 OUTREACH AND EDUCATION.......................................................................................................155 MEDIA OUTREACH..................................................................................................160 OTHER OUTREACH OPPORTUNITIES ...................................................................160 Appendix A: Additional Criteria Pollutant Data ..................................................................................162 Carbon Monoxide (CO) .............................................................................................162 Nitrogen Dioxide (NO2)..............................................................................................162 Nitric Oxide (NO).......................................................................................................162 Oxides of Nitrogen (NOx) ..........................................................................................163 Reactive Oxides of Nitrogen (NOy) ...........................................................................163 i Sulfur Dioxide (SO2) ..................................................................................................164 Ozone (O3) ................................................................................................................165 Lead (Pb) ..................................................................................................................167 Fine Particulate Matter (PM2.5) ..................................................................................168 Appendix B: Additional PM2.5 Particle Speciation Data .....................................................................174 Appendix C: Additional PAMS Data..................................................................................................179 PAMS Continuous Hydrocarbon Data (June-August 2012) .......................................179 PAMS 2012 24-hour Canister Hydrocarbons.............................................................183 Appendix D: Additional Toxics Data..................................................................................................187 2012 Volatile Organic Compounds ............................................................................192 2012 Carbonyl Compounds, 3-hour (June-August)....................................................198 2012 Carbonyl Compounds, 24-hour.........................................................................199 Appendix E: Monitoring Network Survey ..........................................................................................200 Appendix F: Siting Criteria ................................................................................................................205 Appendix G: Instrument and Sensor Control Limits ..........................................................................207 References .......................................................................................................................................208 ii LIST OF FIGURES Figure 1: Georgia Air Monitoring Site Map ........................................................................................... 7 Figure 2: Common Sources of Carbon Monoxide (CO) in Georgia in 2008.......................................... 8 Figure 3: Carbon Monoxide (CO) Emission in Georgia in 2008 Spatial View .................................... 8 Figure 4: Carbon Monoxide Site Monitoring Map............................................................................... 10 Figure 5: Carbon Monoxide First Maximum, Compared to 1-Hour Standard...................................... 12 Figure 6: Carbon Monoxide First Maximum, Compared to 8-Hour Standard...................................... 12 Figure 7: Typical Diurnal Pattern of Nitrogen Dioxide ........................................................................ 13 Figure 8: Common Sources of Nitrogen Oxides in Georgia in 2008................................................... 14 Figure 9: Nitrogen Oxides Emission in Georgia in 2008 Spatial View ............................................. 15 Figure 10: Oxides of Nitrogen Monitoring Site Map ........................................................................... 17 Figure 11: Nitrogen Dioxide Annual Averages Compared to Standard, 2000-2012............................ 18 Figure 12: Nitrogen Dioxide 1-Hour Design Values, 2000-2012......................................................... 18 Figure 13: Common Sources of Sulfur Dioxide (SO2) in Georgia in 2008 .......................................... 19 Figure 14: Sulfur Dioxide Emission in Georgia in 2008 Spatial View............................................... 19 Figure 15: SO2 99th% of 1-Hour Maximum Daily Averages, 2000-2012 ............................................. 20 Figure 16: SO2 1-Hour Design Values, 2000-2012 ............................................................................ 20 Figure 17: Statewide SO2 1-Hour Design Value Averages, Maximums, and Minimums, 1998-2012.. 21 Figure 18: Sulfur Dioxide Monitoring Site Map................................................................................... 23 Figure 19: Typical Urban 1-Hour Ozone Diurnal Pattern.................................................................... 24 Figure 20: Ozone Formation Process ................................................................................................ 24 Figure 21: Common Sources of Volatile Organic Compounds (VOCs) in Georgia in 2008 ................ 25 Figure 22: Volatile Organic Compounds (VOCs) Emission in Georgia in 2008 Spatial View ........... 25 Figure 23: Ozone Monitoring Site Map .............................................................................................. 28 Figure 24: Georgia's 8-Hour Ozone Nonattainment Area Map for 1997 Standard ............................. 30 Figure 25: Georgia's 8-Hour Ozone Nonattainment Area Map for 2008 Standard ............................. 31 Figure 26: Atlanta-Sandy Springs-Marietta MSA Ozone- Number of Violation Days per Year ........... 32 Figure 27: Ozone Design Values, 2000-2012 .................................................................................... 33 Figure 28: Atlanta-Sandy Springs-Marietta MSA Ozone Exceedance Map........................................ 35 Figure 29: Ozone Concentrations in ppm, 2010 (Fourth Highest Daily Maximum 8-Hour Concentrations)........................................................................................................................... 36 Figure 30: Common Sources of Lead in Georgia in 2008 .................................................................. 37 Figure 31: Lead Emission in Georgia in 2008 Spatial View............................................................. 37 Figure 32: Lead Monitoring Site Map ................................................................................................. 39 Figure 33: Three-Month Rolling Averages of Lead, 2010-2012.......................................................... 41 Figure 34: Lead Concentrations in g/m3, 2010 (Maximum 3-month Averages) ................................ 41 Figure 35: Analogy of Particulate Matter Size to Human Hair ............................................................ 42 Figure 36: PM10 Monitoring Site Map ................................................................................................. 44 Figure 37: Second Highest 24-Hour PM10 Concentration................................................................... 46 Figure 38: Statewide PM10 Concentrations (2nd Highest 24-Hour)...................................................... 47 Figure 39: PM10 Annual Arithmetic Mean Chart ................................................................................. 48 Figure 40: PM10 Second Maximum 24-Hour Concentrations (g/m3), 2010 ....................................... 49 Figure 41: PMcoarse Daily Averages, 2011-2012 ................................................................................. 50 Figure 42: Common Sources of Particulate Matter 2.5 in 2008 .......................................................... 51 Figure 43: Particulate Matter 2.5 Emission in Georgia in 2008 Spatial View ................................... 52 Figure 44: PM2.5 Federal Reference Method Monitoring Site Map...................................................... 54 Figure 45: PM2.5 Continuous and Speciation Monitoring Site Map ..................................................... 55 Figure 46: PM2.5 Three-Year 24-Hour Averages, By Site ................................................................... 57 Figure 47: PM2.5 Three-Year Annual Averages, By Site..................................................................... 59 Figure 48: Georgia's PM2.5 Nonattainment Area Map ........................................................................ 61 Figure 49: PM2.5 Annual and 24-Hour Concentrations across the United States, 2010 ...................... 62 Figure 50: PM2.5 Speciation, by Species, 2003-2012 ......................................................................... 64 Figure 51: PM2.5 Speciation, by Site, 2003-2012................................................................................ 66 Figure 52: 2012 Annual Averages of PM2.5 Composition Data in Georgia.......................................... 68 Figure 53: PAMS Monitoring Site Map............................................................................................... 70 iii Figure 54: Average Yearly Profile of Isoprene, 2003-2012 ................................................................ 71 Figure 55: Toluene Average Annual Occurrence, 2003-2012 ............................................................ 72 Figure 56: Toluene & Isoprene, Typical Urban Daily Profile............................................................... 73 Figure 57: Carbonyls Monitoring Site Map ......................................................................................... 75 Figure 58: Average South DeKalb 3-Hour Carbonyls, June-August, 2005-2012................................ 76 Figure 59: Average 24-Hour Carbonyl Concentrations and Number of Detects, by Site, 2005-2012.. 77 Figure 60: Average 24-Hour Carbonyl Concentrations vs. Number of Detects, by Species, 2005-2012 ................................................................................................................................................... 78 Figure 61: Daily Traffic versus Select Carbonyls at South DeKalb, 2012........................................... 79 Figure 62: Regression Analysis of Daily Traffic and Select Carbonyls at South DeKalb, 2012........... 80 Figure 63: Acrolein Concentrations and Percent Detections, 2007- 2012 .......................................... 81 Figure 64: Metals Monitoring Site Map .............................................................................................. 87 Figure 65: Percentage of Metals Detections by Site, 2005-2012 ....................................................... 88 Figure 66: Average Concentration and Percentage Detections of Metals, by Species, 2005-2012 .... 89 Figure 67: Average Concentration Comparison of Zinc, by Site, 2005-2012...................................... 90 Figure 68: Hexavalent Chromium at South DeKalb ........................................................................... 91 Figure 69: Total Volatile Organic Compounds Percent Detected per Site, 2005-2012 ....................... 92 Figure 70: Average Concentration and Percent Detection of Common Volatile Organic Compounds (TO-15), 20052012 ................................................................................................................... 93 Figure 71: Total Volatile Organic Compound Loading all Species, by Site, 2005-2012...................... 94 Figure 72: VOC and SVOC Monitoring Site Map ............................................................................... 95 Figure 73: Semi-Volatile Organic Compounds Percentage of Detections Per Site, 2009-2012 .......... 96 Figure 74: Total Average Concentration and Percentage Detections of Semi-Volatile Organic Compounds by Compound, 2005-2012....................................................................................... 97 Figure 75: Rainfall from Tropical Storm Beryl ...................................................................................101 Figure 76: Rainfall from Tropical Storm Debby .................................................................................102 Figure 77: Drought Impacts from Tropical Storm Debby ...................................................................103 Figure 78: Highest Recorded Temperatures for the Month of June ..................................................104 Figure 79: Post-tropical Cyclone Sandy Tracking Northeastward .....................................................105 Figure 80: Drought Conditions across the State with Rainfall Departures and Streamflows ..............107 Figure 81: Meteorological Site Map ..................................................................................................108 Figure 82: Ozone Predictions and Observations for the Atlanta-Sandy Springs-Marietta MSA During the 2012 Ozone Season ............................................................................................................110 Figure 83 a: PM2.5 Predictions and Observations for the Atlanta-Sandy Springs-Marietta MSA During 2012...........................................................................................................................................111 Figure 83 b: PM2.5 Predictions and Observations for the Atlanta-Sandy Springs-Marietta MSA During 2012...........................................................................................................................................112 Figure 84: Time Series of Hourly PM2.5.............................................................................................113 Figure 85: 12Z Rawinsonde from Peachtree City, GA ......................................................................114 Figure 86: GASP Aerosol Optical Imagery........................................................................................114 Figure 87: Surface Wind Direction ....................................................................................................115 Figure 88: Objective Surface Analysis ..............................................................................................116 Figure 89: Wind Shift and Corresponding PM2.5 Increase .................................................................117 Figure 90: Formulas for Calculating Risk and Hazard Quotient ........................................................144 Figure 91: Aggregate Cancer Risk and Hazard Index by Site for 2007-2012 ....................................147 Figure 92: Estimated Tract-Level Cancer Risk from the 2005 National Air Toxics Assessment ........153 Figure 93: Estimated Tract-Level Total Respiratory Hazard Index from the 2005 National Air Toxics Assessment ...............................................................................................................................154 Figure 94: The AQI...........................................................................................................................156 Figure 95: Number of Days with an AQI Value Above 100 ...............................................................158 Figure 96: 2012 AQI Values, Atlanta-Sandy Springs-Marietta MSA..................................................159 Figure 97: Sample AIRNOW Ozone Concentration Map ..................................................................161 iv LIST OF TABLES Table 1: National Ambient Air Quality Standards Summary ................................................................. 3 Table 2: 2012 Georgia Air Monitoring Network .................................................................................... 6 Table 3: Common Oxides of Nitrogen Species and Terms ................................................................ 14 Table 4: Audits Performed for Each Air Monitoring Program in 2012 ................................................119 Table 5: NO Data Quality Assessment .............................................................................................121 Table 6: NO2 Data Quality Assessment ............................................................................................121 Table 7: NOX Data Quality Assessment............................................................................................121 Table 8: CO Data Quality Assessment .............................................................................................122 Table 9: SO2 Data Quality Assessment ............................................................................................122 Table 10: O3 Data Quality Assessment.............................................................................................123 Table 11: PM2.5 Data Quality Assessment for FRM Samplers ...........................................................125 Table 12: PM2.5 Data Quality Assessment for Semi-Continuous Samplers........................................126 Table 13: PM10 Data Quality Assessment of 24-Hour Integrated and Semi-Continuous Samplers ...126 Table 14: Summary of Unexposed Filter Mass Replicates................................................................127 Table 15: Summary of Exposed Filter Mass Replicates....................................................................127 Table 16: Current List of NATTS Sites with AQS Site Codes............................................................130 Table 17: Measurement Quality Objectives for the NATTS Program ................................................131 Table 18: MQO Data Sources for the Georgia NAATS Program.......................................................131 Table 19: 23 Selected HAPs and Their AQS Parameter Codes........................................................132 Table 20: Percent Completeness of Georgia's 2012 AQS Data, Selected Compounds ....................132 Table 21: PAMS Speciated VOCs Yearly Data Quality Assessment for South DeKalb .....................133 Table 22: PAMS Speciated VOCs Yearly Data Quality Assessment for Conyers .............................134 Table 23: PAMS Speciated VOCs Yearly Data Quality Assessment for Yorkville .............................135 Table 24: PAMS Speciated VOCs Yearly Data Quality Assessment for Ambient Monitoring Program Summary ...................................................................................................................................136 Table 25: Meteorological Measurements Accuracy Results..............................................................137 Table 26: Compounds Monitored and Screening Values Used in Initial Assessment........................141 Table 27: Summary of Chemicals Analyzed in 2012.........................................................................142 Table 28: Site-Specific Detection Frequency and Mean Chemical Concentration, 2012 ...................143 Table 29: Cancer Risk and Hazard Quotient by Location and Chemical, 2012 .................................145 Table 30: Aggregate Cancer Risk and Hazard Indices for Each Site, Excluding Carbonyls, 2012 ....146 Table 31: Summary Data for Select VOCs at PAMS Sites, 2012 ......................................................148 Table 32: Summary Observations, Cancer Risk, and Hazard Quotient for Carbonyls, 2012.............149 Table 33: AQI Summary Data, 2012.................................................................................................157 v EXECUTIVE SUMMARY The Ambient Monitoring Program of the Air Protection Branch of the Environmental Protection Division (EPD) has monitored air quality in the State of Georgia for more than thirty years. During that time, the list of monitored compounds has grown to more than 200 pollutants and EPD has expanded the types of samplers used at monitoring sites across the state. This monitoring is performed to protect public health and environmental quality. The resulting data is used for a broad range of regulatory and research purposes, as well as to inform the public. This report is the summary of the monitoring data from 2012, and is an assessment of the data in conjunction with previous years' findings. The Chemical Monitoring Activities, Photochemical Assessment Monitoring (PAMS), and Air Toxics Monitoring sections provide an in-depth discussion of the chemicals that are monitored and maps identify individual monitoring sites. These sections also contain discussions on general health effects, measurement techniques, and attainment designations for the criteria pollutants that are monitored. Additionally, these sections discuss trends and common sources for the monitored pollutants. Six pollutants fall within the criteria pollutant list. These pollutants are carbon monoxide, sulfur dioxide, lead, ozone, nitrogen dioxide, and particulate matter (now regulated in two size categories). The ambient concentrations of these pollutants must meet a regulatory standard, which is health-based. Concentrations above the standard are considered unhealthy for sensitive groups. Another set of compounds called air toxics are monitored throughout the state in the Air Toxics Network. The sources of these emitted compounds include vehicle emissions, stationary source emissions, and natural sources. These air toxic compounds do not have ambient air regulatory standards. However, a review of the monitoring results is screened for theoretical lifetime cancer risk and potential non-cancer health effects on a yearly basis. This analysis is presented in the Risk Assessment section of this report. Estimates of theoretical cancer risk posed by these compounds are primarily driven by a small number of chemicals in the metals, volatile organic compounds, and carbonyls groups of the air toxics. The estimates of theoretical lifetime cancer risk related to air toxic pollutants in the areas monitored across the state ranged from 1 in 10,000 to 1 in 1,000,000. The potential risk of non-cancer health effects from air toxic pollutants is estimated differently, and most chemicals fell well below the hazard quotient of 1. The Ambient Monitoring Program also operates an extensive network of meteorological stations. The Meteorological Report section discusses Georgia's climatology, based on the meteorological data captured at PAMS sites and statewide sites. The meteorological sites provide, at a minimum, wind speed and wind direction data. Some stations are very sophisticated and provide information on barometric pressure, relative humidity, solar radiation, temperature, and precipitation. A discussion of the Georgia ozone and PM2.5 forecasting effort is also included in this section. The Quality Assurance section shows the Ambient Monitoring Program's undertaking to produce quality data. The data has to be collected and measured in a certain manner to meet requirements that are set forth by the EPA. The requirements for each monitored pollutant are provided, including field and laboratory techniques, as well as the results of quality assurance audits. The Outreach and Education section provides information concerning the efforts of the Clean Air Campaign to change the commuting habits of residents of Atlanta. The voluntary program partners with the public and private sector to reduce vehicle congestion and aid in reducing vehicle emissions. This section includes a description of educational and news media outreach activities, and explains how the Air Quality Index (AQI) is used to offer the public an easy to use indicator of air quality. The appendices of this document contain summary tables for the pollutants measured during 2012. Included in the summary tables is information about the location of air pollutant detections, the number of samples collected, as well as average and maximum concentrations. vi Copies of this and previous annual reports are available in Adobe Acrobat format via the Ambient Monitoring Program website at http://www.air.dnr.state.ga.us/amp/. A limited number of print copies are available and may be requested at 404-363-7006. Real time air monitoring information for the criteria pollutants may be found at the above website by selecting the pollutant of concern. In addition, the website also provides links to the Clean Air Campaign and the air quality forecast. vii Aerosols AM APB AQCR Anthropogenic ARITH MEAN AQS By-product BAM CAA CFR CO CV DNR EPA EPD FRM GEO MEAN HAP HI HQ IUR LOD g/m3 m/s MDL Mean MSA NAAQS NAMS NATTS NMHC NO2 NOx NOy NUM OBS NWS ODC O3 PAH PAMS Pb PM2.5 PM10 ppb ppbC ppm Precursor PUF QTR Rawinsonde RfC Screening Value GLOSSARY A gaseous suspension of fine solid or liquid particles Annual Mean Air Protection Branch Air Quality Control Region Resulting from human activity Arithmetic Mean Air Quality System Something produced in making something else; secondary result Beta Attenuation Monitor Clean Air Act Code of Federal Regulations Carbon Monoxide Coefficient of Variation Department of Natural Resources (state agency) Environmental Protection Agency (federal agency) Environmental Protection Division (state agency) Federal Reference Method- the official measurement technique for a given pollutant Geometric Mean Hazardous Air Pollutant Hazard Index Hazard Quotient Inhalation Unit Risk Limit of Detection Micrograms per cubic meter Meters per second Method Detection Limit Average Metropolitan Statistical Area, as defined by the U.S. Census Bureau National Ambient Air Quality Standard National Ambient Monitoring Site National Air Toxics Trends Station Non-Methane Hydrocarbons Nitrogen Dioxide Oxides of Nitrogen Reactive oxides of Nitrogen Number of Observations National Weather Service Ozone depleting Chemicals Ozone Polycyclic Aromatic Hydrocarbons Photochemical Assessment Monitoring Station Lead Particles with an aerodynamic diameter of 2.5 microns or less Particles with an aerodynamic diameter of 10 microns or less Parts per billion Parts per billion Carbon Parts per million A substance from which another substance is formed Polyurethane Foam Calendar Quarter A source of meteorological data for the upper atmosphere Reference Concentration Initial level of air toxic compounds used in risk assessment viii SLAMS SO2 SPMS TEOM TNMOC TRS TSP UV VOC w/m2 State and Local Air Monitoring Site Sulfur Dioxide Special Purpose Monitoring Site Tapered Element Oscillating Microbalance Total Non-Methane Organic Compounds Total Reduced Sulfur Total Suspended Particulates Ultraviolet Volatile Organic Compound Watts per square meter ix 2012 Georgia Ambient Air Surveillance Report Section: Introduction INTRODUCTION This report summarizes the air quality data collected by the State of Georgia during calendar year 2012. The Air Protection Branch is a subdivision of the state's Department of Natural Resources (DNR), Environmental Protection Division (EPD). The United States Environmental Protection Agency (EPA) regulates air quality standards nationwide through authority granted by Congress in the Clean Air Act. Few people realize, though, that the air quality monitoring that is required by the Act is performed almost entirely by state and local governments. The Ambient Monitoring Program conducts monitoring in Georgia, both to satisfy Clean Air Act monitoring requirements and to exceed them in cases where additional monitoring proves beneficial to the citizens and industries of the state. Monitoring is performed to facilitate the protection of public health, as well as to protect our natural environment. The data is collected and quality assured using equipment and techniques specified by EPA. Once the data is ready, it is submitted to EPA's national air quality database (AQS), where it is available to a broad community of data users. Despite the technical nature of the information collected, every effort has been made to make the data relevant and useful to those who do not routinely study air quality data. To provide additional information for those who have interest in more detailed technical information, extensive appendices are included. Further information about air quality in Georgia and nationwide is available from EPA. 1 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities CHEMICAL MONITORING ACTIVITIES This section contains a summary of the National Ambient Air Quality Standards (NAAQS) and the monitoring techniques used to measure ambient air quality for comparison with these standards. The Clean Air Act (CAA) requires the EPA Administrator to identify pollutants that may endanger public health or welfare. The Administrator is required to issue air quality criteria that reflect current scientific knowledge, useful in indicating the type and extent of identifiable effects on public health or welfare that may be expected from the presence of such pollutants in ambient air. Under the CAA, the EPA Administrator establishes National Ambient Air Quality Standards (NAAQS) for each pollutant for which air quality criteria have been issued. The EPA is to set standards where "the attainment and maintenance are requisite to protect public health" with "an adequate margin of safety." In 1971, the EPA established standards for five "criteria" pollutants as required by the Clean Air Act. The standards and pollutants have changed over time to keep up with improvements in scientific knowledge and now consist of six pollutants. These pollutants are carbon monoxide, sulfur dioxide, lead, ozone, nitrogen dioxide, and particulate matter (now regulated in two size categories). For the most current list of standards, please refer to EPA's website (http://www.epa.gov/air/criteria.html). The following table displays 2012 criteria pollutants and standards. 2 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Pollutant Primary/ Averaging [final rule cite] Secondary Time Level Form Carbon Monoxide [76 FR 54294, Aug primary 31, 2011] 8-hour 1-hour 9 ppm Not to be exceeded more than once 35 ppm per year Lead primary [73 FR 66964, Nov and 12, 2008] secondary Rolling 3 month average 0.15 g/m3 (1) Not to be exceeded Nitrogen Dioxide [75 FR 6474, Feb primary 1-hour 9, 2010] [61 FR 52852, Oct 8, 1996] primary and secondary Annual Ozone [73 FR 16436, Mar 27, 2008] primary and secondary 8-hour Particle Pollution [71 FR PM2.5 primary and Annual secondary 24-hour 61144, Oct 17, 2006] PM10 primary and secondary 24-hour Sulfur Dioxide [75 FR 35520, Jun primary 1-hour 22, 2010] [38 14, FR 25678, 1973] Sept secondary 3-hour 100 ppb 98th percentile, averaged over 3 years 53 ppb (2) Annual Mean 0.075 ppm (3) Annual fourth-highest daily maximum 8-hr concentration, averaged over 3 years 15 g/m3 annual mean, averaged over 3 years 35 g/m3 98th percentile, averaged over 3 years 150 Not to be exceeded more than once g/m3 per year on average over 3 years 99th percentile of 1-hour daily 75 ppb (4) maximum concentrations, averaged over 3 years 0.5 ppm Not to be exceeded more than once per year (1) Final rule signed October 15, 2008. The 1978 lead standard (1.5 g/m3 as a quarterly average) remains in effect until one year after an area is designated for the 2008 standard, except that in areas designated nonattainment for the 1978, the 1978 standard remains in ef fect until implementation plans to attain or maintain the 2008 standard are approved. (2) The official level of the annual NO2 standard is 0.053 ppm, equal to 53 ppb, which is shown here for the purpose of clear er comparison to the 1hour standard. (3) Final rule signed March 12, 2008. The 1997 ozone standard (0.08 ppm, annual fourth-highest daily maximum 8-hour concentration, averaged over 3 years) and related implementation rules remain in place. In 1997, EPA revoked the 1-hour ozone standard (0.12 ppm, not to be exceeded more than once per year) in all areas, although some areas have continued obligations under that standard ("anti-backsliding"). The 1-hour ozone standard is attained when the expected number of days per calendar year with maximum hourly average concentrations above 0.12 ppm is less than or equal to 1. (4) Final rule signed June 2, 2010. The 1971 annual and 24-hour SO2 standards were revoked in that same rulemaking. However, these standards remain in effect until one year after an area is designated for the 2010 standard, except in areas designated nonattainment f or the 1971 standards, where the 1971 standards remain in effect until implementation plans to attain or maintain the 2010 standard are approved. (Source: http://www.epa.gov/air/criteria.html) Table 1: National Ambient Air Quality Standards Summary As shown in Table 1, there are two categories for ambient air quality standards, primary and secondary. Primary standards are intended to protect the most sensitive individuals in a population. These "sensitive" individuals include children, the elderly, and people with chronic illnesses. The secondary standards are designed to protect public welfare or the quality of life. This includes visibility protection, limiting economic damage, damage to wildlife, the climate, or man-made material. The varied averaging times are to address the health impacts of each pollutant. Short-term averages are to protect against acute effects. Long-term averages are to protect against chronic effects. The Georgia ambient air monitoring network provides information on the measured concentrations of criteria and non-criteria pollutants at pre-selected locations. The 2012 Georgia Air Sampling Network consisted of 52 sites in 31 counties across the state. Table 2, on pages 5 and 6, is a list of sites in the monitoring network along with details of pollutants monitored and their locations. Monitoring occurs year-round, although some pollutants have various required monitoring periods. Ozone, with the 3 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities exception of the South DeKalb and CASTNET sites, is sampled from March through October, and the continuous (hourly) Photochemical Assessment Monitoring Stations (PAMS) volatile organic compounds are sampled from June through August. Figure 1, following Table 2, is a spatial display of the air monitoring locations in the state. Please note that not all pollutants are monitored at all sites. Maps of the monitoring locations for individual pollutants are provided in each pollutant's respective section in this report. For more details regarding the ambient air monitoring network, refer to Georgia EPD's Ambient Air Monitoring Plan found on EPD's website at http://www.air.dnr.state.ga.us/amp/. The number of monitoring sites and their respective locations can vary from year to year. This variation depends on the availability of long-term space allocation, regulatory needs, and other factors such as the sufficiency of resources. Once a site is established, the most common goal for its use is to monitor for long-term trends. All official monitoring performed in support of the National Ambient Air Quality Standards (NAAQS) must use U.S. EPA-defined reference methods described in 40 CFR Part 53, Appendix A, or equivalent methods designated in accordance with Part 53 of that chapter. All data collected in the network undergoes an extensive quality assurance review and is then submitted to the Air Quality System (AQS) database that is maintained by the EPA. In general, the basic monitoring objectives that govern the selection of sites are: 1) to measure the highest observable concentration; 2) to determine representative concentrations in areas of high population density; 3) to determine the impact of significant sources or source categories on ambient pollution levels; 4) to determine the general background concentration levels; and 5) to determine the concentration of a number of compounds which contribute to the formation of ground level ozone. Data collected from continuous monitors in Georgia's monitoring network are presented on EPD's website at http://www.air.dnr.state.ga.us/amp/. The data is updated hourly at 15 minutes past the hour. Specific annual summary data for 2012 are available in Appendix A. 4 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities SITE ID COMMON NAME / CITY Rome MSA 131150003 Coosa Elementary, Rome Brunswick MSA 131270004 Arco Pump Station, Brunswick 131270006 Risley Middle, Brunswick Valdosta MSA 131850003 Mason Elem., Valdosta Warner Robins MSA 131530001 Air Force Base, Warner Robins Dalton MSA 132130003 Fort Mountain, Chatsworth Albany MSA 130950007 Turner Elem., Albany Gainesville MSA 131390003 Boys & Girls Club, Gainesville Athens-Clark County MSA 130590002 College Station Rd., Athens Macon MSA 130210007 Allied Chemical, Macon 130210012 GA Forestry Comm., Dry Branch Columbus Georgia- Alabama MSA 132150001 132150008 Health Dept., Columbus Airport, Columbus 132150009 UPS, Columbus 132150010 Fort Benning, Columbus 132150011 Cusseta Elem., Columbus 132151003 Crime Lab, Columbus Savannah MSA 130510014 Shuman Middle, Savannah 130510017 Market Street, Savannah 130510021 E. President St., Savannah 130510091 Mercer Middle, Savannah 130511002 L & A, Savannah Augusta Georgia-South Carolina MSA 130730001 Riverside Park, Evans 132450005 Med. College GA, Augusta 132450091 Bungalow Rd., Augusta COUNTY Floyd Glynn Glynn Lowndes Houston Murray Dougherty Hall Clarke Bibb Bibb Muscogee Muscogee Muscogee Muscogee Muscogee Muscogee Chatham Chatham Chatham Chatham Chatham Columbia Richmond Richmond PM2.5 PM2.5 PM2.5 PM10 Acid PAMS Carb- O3 CO FRM Cont. Spec. NO NOx NO2 NOy SO2 TRS Pb PM10 Cont. Rain VOC VOC SVOC onyls S S X S S S S S S M S S S S S S S S S S S S S X S X S S S S S NR NR S S S S S X S S S S S S S S S S S S S S X S S S S NR NR NR Met Aeth. Cr6 Metals NR NR NR NR NR NR NR NR NR NR 5 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities PM2.5 PM2.5 PM2.5 PM10 Acid PAMS Carb- SITE ID COMMON NAME / CITY COUNTY O3 CO FRM Cont. Spec. NO NOx NO2 NOy SO2 TRS Pb PM10 Cont. Rain VOC VOC SVOC onyls Met Aeth. Cr6 Metals Atlanta-Sandy Springs-Marietta MSA 130150003 Cartersville Lead, Cartersville Bartow S 130630091 Georgia DOT, Forest Park Clayton S 130670003 National Guard, Kennesaw Cobb S S 130670004 Macland Aquatic, Powder Sp Cobb S 130770002 Univ. of West GA, Newnan Coweta S S NR 130850001 GA Forestry, Dawsonville Dawson S NR NR NR NR NR 130890002 South DeKalb, Decatur DeKalb S/P/C S/P/C S/C S/C T/C S/P S/P S/P S/P/C C C P N N P/N P N N N 130890003 DMRC, Decatur DeKalb S 130892001 Police Dept., Doraville DeKalb S S 130893001 Idlewood Rd., Tucker DeKalb NR 130970004 W. Strickland St., Douglasville Douglas S NR 131130001 Georgia DOT, Fayetteville Fayette S NR 131210032 E. Rivers School, Atlanta Fulton S S 131210039 Fire Station #8, Atlanta Fulton S 131210048 Georgia Tech, Atlanta Fulton S NR 131210055 Confederate Ave., Atlanta Fulton S S S NR 131210099 Roswell Road, Atlanta Fulton S 131350002 Gwinnett Tech, Lawrenceville Gwinnett S S S 131510002 County Extension, McDonough Henry S S 132230003 King Farm, Yorkville Paulding S/P S/P S S S/P S/P S/P P NR NR P NR 132319991 EPA CASTNET Pike A 132470001 Monastery, Conyers Rockdale S/P S/P S/P S/P P P Chattanooga Tennessee-Georgia MSA 132950002 Maple Street, Rossville W alker S S X Not In An MSA 130550001 Fish Hatchery, Summerville Chattooga S S 130690002 General Coffee SP, Douglas Coffee X NR NR NR 132611001 Union High School, Leslie Sumter S 133030001 Health Dept., Sandersville Washington S S 133190001 Police Dept., Gordon Wilkinson S Monitoring Types: S=SLAMS; P=PAMS; C=NCore; M=SPM; X=Supplemental Speciation; T=STN; N=NATTS; NR=Non-Regulatory; G=General Information; A=CASTNET Samplers in red are not operational Table 2: 2012 Georgia Air Monitoring Network 6 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities All Georgia Sites MSAs Shown as Solid Colors Figure 1: Georgia Air Monitoring Site Map 7 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report CARBON MONOXIDE (CO) Section: Chemical Monitoring Activities GENERAL INFORMATION Carbon monoxide (CO) is an odorless, colorless, and poisonous gas that is a by-product of incomplete burning. In most large metropolitan areas, the primary source of CO pollution is engendered from automobile exhaust. The CO emissions from automobiles are responsible for approximately 60% of CO emissions nationwide. Other contributors of CO are fires, industrial processes, cigarettes, and other sources of incomplete burning in the indoor environment. Figure 2 and Figure 3 give a visual representation of the CO emissions in Georgia. These figures are taken from EPA's latest available records on air emission sources, based on 2008 data. (From EPA's Air Emissions Sources) Figure 2: Common Sources of Carbon Monoxide (CO) in Georgia in 2008 (From EPA's Air Emissions Sources) Figure 3: Carbon Monoxide (CO) Emission in Georgia in 2008 Spatial View 8 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities In colder months, a few factors come together that can cause concentrations of ambient CO to be found at higher levels than the rest of the year. During the winter months, cooler temperatures prevent complete combustion of fuels, causing an increase in CO emissions. This can especially affect fuel combustion in gas-powered automobiles, as friction is increased during cold engine operation. At the same time, winter is subjected to more frequent atmospheric inversion layers. In standard conditions, the troposphere contains temperatures that decrease with increasing altitude. An inversion layer can occur when a layer of warmer air traps cooler air near the surface, disrupting the descending temperature gradient of the troposphere and preventing the usual mixing that would occur in normal conditions. During this time, the increased CO emissions can be trapped by the cap that is formed by the inversion layer, locking in CO emissions near the earth's surface. The Clean Air Act (CAA) requires that Metropolitan Statistical Areas (MSAs) with a population greater than 500,000, as determined by the last census (2010), to have at least two CO State and Local Air Monitoring Stations (SLAMS). In Georgia, only the Atlanta-Sandy Springs-Marietta MSA meets the population requirement. Currently, Georgia's CO sites are located at Roswell Road, Yorkville, and South DeKalb (Figure 4, on the next page). The Roswell Road site was established to monitor for CO at a microscale level. The purpose of microscale measurements is to measure peak concentrations in major urban traffic areas. A microscale site monitors an air mass that covers a distance of several meters to about 100 meters. In addition, high sensitivity CO monitors are located at the Yorkville and South DeKalb sites. The purpose of these CO monitors is to aid in the detection of combustion and smoke plumes from power plants. Furthermore, the South DeKalb site is required to monitor CO as part of the National Core (NCore) Multi-pollutant Monitoring Network. 9 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 4: Carbon Monoxide Site Monitoring Map 10 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities HEALTH IMPACTS Once CO is inhaled, it enters the blood stream, where it binds chemically to hemoglobin. Hemoglobin is the component of blood that is responsible for carrying oxygen to the cells. When CO binds to hemoglobin, it reduces the ability of hemoglobin to do its job, and in turn reduces the amount of oxygen delivered throughout the body. The percentage of hemoglobin affected by CO depends on the amount of air inhaled, the concentration of CO in air, and the length of exposure. Negative health effects of CO include weakening the contractions of the heart that reduces blood flow to various parts of the body. In a healthy person, this effect significantly reduces the ability to perform physical activities. In persons with chronic heart disease, this effect can threaten the overall quality of life, because their systems may be unable to compensate for the decrease in oxygen. CO pollution is also likely to cause such individuals to experience chest pain during activity. Adverse effects have also been observed in individuals with heart conditions who are exposed to CO pollution in heavy freeway traffic for one or more hours. In addition, fetuses, young infants, pregnant women, elderly people, and individuals with anemia or emphysema are likely to be more susceptible to the effects of CO. For these individuals, the effects are more pronounced when exposure takes place at high altitude locations, where oxygen concentration is lower. CO can also affect mental functions, visual acuity, and the alertness of healthy individuals, even at relatively low concentrations. MEASUREMENT TECHNIQUES CO is monitored using an EPA-approved reference or equivalent method. The analyzers are selfcontained and capable of measuring ambient CO on a continuous, real-time basis using the nondispersive infrared analysis and gas filter correlation methods. CO is monitored using specialized analyzers based on the principle that CO absorbs infrared radiation. The sample is drawn through the sample bulkhead and the optical bench. Radiation from an infrared source is chopped and then passed through a gas filter alternating between CO and N2. The radiation then passes through a narrow bandpass interference filter and enters the optical bench where absorption by the sample gas occurs. The infrared radiation then exits the optical bench and falls on an infrared detector. The N2 side of the filter wheel produces a measure beam which can be absorbed by CO in the cell. The chopped detector signal is modulated by the alternation between the two gas filters with amplitude related to the concentration of CO in the sample cell. Thus, the gas filter correlation system responds specifically to CO. The CO concentration is then displayed on the front panel display and sent to the analog or digital output. The sampler is equipped with a microprocessor that enables digital measurement of CO, automatic compensation for changes in temperature and pressure, and internal diagnostics. ATTAINMENT DESIGNATION Data collected from the continuous monitors are used to determine compliance with the Clean Air Act (CAA) 8-hour and 1-hour standard for CO. The 8-hour standard requires that, for 8-hour averages, no concentration greater than 9 ppm may be observed more than once per year. For 1-hour averages, no concentration greater than 35 ppm may be observed more than once a year [76 FR 54294, August 31, 2011]. The next two graphs (Figure 5 and Figure 6) show how Georgia's CO compares to the two standards. The first graph shows a comparison to the 1-hour standard of 35 parts per million (ppm), and the second graph shows a comparison to the 8-hour standard of 9 ppm. Georgia's CO values have dropped considerably since 1995 and are well below the standards. If the data shows that these criteria are met, then the area is considered to be in attainment of the standard. All of Georgia is in attainment of both the 8-hour and 1-hour standards for carbon monoxide. For additional summary data on carbon monoxide, see Appendix A. 11 Georgia Department of Natural Resources Environmental Protection Division Concentration (ppm) 2012 Georgia Ambient Air Surveillance Report 35 30 25 20 15 10 5 0 Section: Chemical Monitoring Activities 35 ppm standard South DeKalb Roswell Rd Yorkville Figure 5: Carbon Monoxide First Maximum, Compared to 1-Hour Standard Concentration (ppm) 9 8 7 9 ppm standard 6 5 4 3 2 1 0 South DeKalb Roswell Rd Yorkville Figure 6: Carbon Monoxide First Maximum, Compared to 8-Hour Standard 12 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities OXIDES OF NITROGEN (NO, NO2, NOx and NOy) GENERAL INFORMATION Oxides of nitrogen (see Table 3 on the following page) exist in various forms in the atmosphere. The most common is nitric oxide (NO), but other forms such as nitrogen dioxide (NO2), nitric acid (HNO3) and dinitrogen pentoxide (N2O5) are also present. The bulk of these compounds in the atmosphere are produced from high temperature combustion and lightning. Nitrogen is a very stable molecule and is essentially inert unless subjected to extreme conditions. The oxides of nitrogen are less stable, however, and are key participants in atmospheric chemistry, converting back and forth between numerous states under different conditions. Many of these reactions involve the conversion of oxygen atoms between their atomic (O2) and ozone (O3) forms. As such, oxides of nitrogen are studied as precursors of (and alternately by-products of) ozone formation. With the many forms of oxides of nitrogen in the atmosphere, they are sometimes referred to using the generic terms NOx or NOy. Nitric acid (HNO3) is the most oxidized form of nitrogen in the atmosphere. This species is water-soluble and is removed from the atmosphere in the form of acidic raindrops. NO is changed to NO2 in very rapid atmospheric reactions. During daylight hours, ultraviolet (UV) radiation from the sun breaks apart NO2 into NO and free oxygen (O). The free oxygen atom (O) will attach itself to molecular oxygen (O2) creating an ozone (O3) molecule. This is the origin of the majority of ground level ozone. With the UV radiation breaking apart the NO2 and N2O5, daytime levels are low. Then the concentrations rise rapidly overnight with the lack of UV radiation. When the sun rises again in the morning, the compounds are converted back to NO and ozone. The following graph, Figure 7, is a representation of this typical diurnal pattern of NO2. Refer to the ozone section and Figure 19 for a comparison of each diurnal pattern. Concentration (ppm) 0.025 0.02 0.015 0.01 0.005 0 Hour Figure 7: Typical Diurnal Pattern of Nitrogen Dioxide 13 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities ABBREVIATION NO NO2 HNO3 PAN NOx NOy FULL NAME CREATION PROCESSES ELIMINATION PROCESSES Nitrous Oxide Nitrogen Dioxide Nitric Acid Result of ozone photochemistry High-temperature combustion High-temperature combustion Reaction of NO and ozone NO2 + H2O Reacts with ozone to form NO2 and oxygen Reacts with oxygen in strong sun to form ozone plus NO "Washes out" in rain "Washes out" in rain Peroxyacetyl Nitrate Oxidation of hydrocarbons in sunlight Slow devolution to NO2 Name for NO + NO2 Name for all atmospheric oxides of nitrogen- mostly NO, NO2, HNO3, N2O5, and PAN Table 3: Common Oxides of Nitrogen Species and Terms Nitrogen dioxide (NO2) is one of the important oxides of nitrogen. It is a light brown gas, and can be an important component of urban haze, depending upon local sources. Nitrogen oxides usually enter the air as the result of high-temperature combustion processes, such as those occurring in automobiles and industries (Figure 8). Home heaters, gas stoves, and non-road equipment also produce substantial amounts of NO2. NO2 is formed from the oxidation of nitric oxide (NO), which has a pungent odor at high concentrations and a bleach smell at lower concentrations. NO2 is a precursor to ozone formation and can be oxidized to form nitric acid (HNO3), one of the compounds that contribute to acid rain. Nitrate particles and NO2 can block the transmission of light, reducing visibility. Figure 9, on the next page, shows a spatial view of the varying concentrations of nitrogen oxides by county in Georgia during 2008. The following figures are taken from the latest emissions report from EPA, based on 2008 data. (From EPA's Air Emissions Sources) Figure 8: Common Sources of Nitrogen Oxides in Georgia in 2008 14 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities (From EPA's Air Emissions Sources) Figure 9: Nitrogen Oxides Emission in Georgia in 2008 Spatial View Efforts are being taken to reduce the emissions of harmful nitrogen oxides. School bus retrofitting, truck stop electrification, and locomotive conversions are three alternative methods that are being used as to reduce emissions. School bus retrofitting focuses on older school buses that are being fitted with an emission control device to reduce emitted NOx. A specific type of retrofit known as selective catalytic reduction (SCR) reduces output by converting nitrogen oxides to molecular nitrogen and oxygen-rich exhaust streams. SCR systems are enhanced by using a low sulfur fuel. The amount of sulfur in diesel was recently reduced by 97 percent, creating low sulfur fuel. As sulfur tends to hamper exhaust-control devices, the introduction of low sulfur fuel has allowed retrofitting to be an effective means of reducing emissions. Truck stop electrification (TRE) reduces idling by diesel powered commercial trucks. Truck drivers are typically required to rest 8 hours for every 10 hours of travel time. During this resting period, diesel engines are idled as a means to power their air conditioning and heating systems. TRE eliminates this diesel dependence by providing an electrical system that charges battery-powered appliances including air conditioning, heating, and other electronic devices. In addition, cool or warm air is pumped into the trucks via a hose hookup at the truck stops as another method of cutting down on idling and emissions. All of this reduces oxides of nitrogen that would be produced by unnecessary idling. Locomotive conversions reduce emissions by replacing old single diesel engines used by switch locomotives with smaller, more efficient modular diesel engines. Switch locomotives, or switchers, assemble and disassemble trains at rail yards. When they are not in action, they idle on the rails until another train comes along. The new engines, known as "genset" and eventually Tier 4 engines, utilize two or more smaller engines that can combine to equal the strength of the older engines to pull the maximum load. They can function individually, or with less horsepower, to handle less demanding loads, while cutting down on the fuel needed to perform the task. These lower-emitting off-road diesel engines also feature an automatic engine start/stop technology to reduce idling when not in use. 15 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities HEALTH IMPACTS Exposure to high levels of NO2 for short durations (less than three hours) can lead to respiratory problems. Asthma sufferers, in particular, are sensitive to NO2. This sensitivity was expressed in a study that examined changes in airway responsiveness of exercising asthmatics during exposure to relatively low levels of NO2. Other studies also indicate a relationship between indoor NO2 exposures and increased respiratory illness rates in young children, but definitive results are still lacking. In addition, many animal analyses suggest that NO2 impairs respiratory defense mechanisms and increases susceptibility to infection. Several other observations also show that chronic exposure to relatively low NO2 pollution levels may cause structural changes in the lungs of animals. These studies suggest that chronic exposure to NO2 could lead to adverse health effects in humans, but specific levels and durations likely to cause such effects have not yet been determined. MEASUREMENT TECHNIQUES Oxides of nitrogen, particularly NO2, are monitored using specialized analyzers that continuously measure the concentration of oxides of nitrogen in ambient air using the ozone-phase chemiluminescent method. Nitric oxide (NO) and ozone (O3) react to produce a characteristic luminescence with an intensity, linearly proportional to the NO concentration. Infrared light emission results when electronically excited NO2 molecules decay to lower energy states. NO2 must first be converted to NO before it can be measured using the chemiluminescent reaction. NO2 is converted to NO by a molybdenum NO2-to-NO converter, heated to about 325oC. The ambient air sample is drawn into the sample bulkhead. The sample flows through a particulate filter, a capillary, then to the mode solenoid valve. The solenoid valve routes the sample either straight to the reaction chamber (NO mode) or through the NO2-to-NO converter and then to the reaction chamber (NOx mode). Dry air enters the dry air bulkhead through a flow sensor, and then through a silent discharge ozonator. The ozonator generates the necessary ozone concentration needed for the chemiluminescent reaction. The ozone reacts with the NO in the ambient air to produce electronically excited NO2 molecules. A photomultiplier tube housed in a thermoelectric cooler detects the NO2 luminescence. The NO and NO2 concentrations calculated in the NO and NOx modes are stored in memory, and the difference between the concentrations are used to calculate the NO2 concentration. The sampler outputs NO, NO2, and NOx concentrations on the front panel display and the analog or digital outputs. There are two major instrument designs. While they are closely related, they do not monitor the same species. NOx analyzers measure NO, NO2, and NOx. NOy analyzers measure NO and NOy, but cannot measure NO2. The NOy analyzers are also specialized for measuring trace-level concentrations; as such, they cannot measure higher concentrations. Because of these tradeoffs, it is necessary to operate a network of both instrument types to get a complete picture of local conditions. Of the oxides of nitrogen, only NO2 is regulated under the NAAQS. Therefore, only the NOx type analyzers produce data directly relevant to the standard. NO2 monitoring is required in urban areas with populations greater than 1,000,000. The Atlanta-Sandy Springs-Marietta MSA is the only urban area in Georgia that meets that population requirement. In 2012, the Atlanta-Sandy Springs-Marietta MSA had three NO2 sites collecting data. They are located at the South DeKalb, Conyers, and Yorkville sites. In addition, as of January 1, 2014, GA EPD will be conducting near-road NO2 monitoring. The complete oxides of nitrogen monitoring network, including NOx and NOy monitor locations, can be found in Figure 10. 16 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 10: Oxides of Nitrogen Monitoring Site Map ATTAINMENT DESIGNATION Data collected from continuous monitors are used to determine compliance with the NAAQS primary and secondary annual standards for NO2. These standards require that a site's annual average 17 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities concentration not exceed 0.053 ppm or 53 ppb. In the following figure, Georgia's annual average NO2 concentrations are shown from 2000 to 2012. Annual average concentrations are well below the standard of 53 parts per billion (ppb). In order to protect public health against adverse effects associated with short-term NO2 exposure, on January 22, 2010, EPA strengthened the NO2 standard to include a 1-hour form [Federal Register, Vol. 75, No. 26, page 6474, dated February 9, 2010]. This form of the standard is a three-year average of the 98th% of the annual daily maximum 1-hour averages. The level for this standard is 100 parts per billion. For this standard, EPA is interested in monitoring near-road concentrations and the effects of traffic emissions. By January 1, 2014, GA EPD will have established one of a limited number of sites, launched nationwide. To show how past and current NO2 data would compare to this new standard, Figure 12 below, displays the three-year averages of ambient data, as available from 2000 to 2012. The 1-hour design values are well below the 100 ppb standard, and have consistently dropped since the 2000-2002 values. The Atlanta-Sandy Springs-Marietta MSA is in attainment of both the annual and the 1-hour NO2 standard. For additional summary data on this topic, see Appendix A. 50 53 ppb standard 40 Annual Average (ppb) 30 20 10 0 South DeKalb Yorkville Conyers Figure 11: Nitrogen Dioxide Annual Averages Compared to Standard, 2000-2012 Three-Year Average 98% Daily Maximum 1-Hour Averages (ppb) 100 90 80 100 ppb standard 70 60 50 40 30 20 10 0 South DeKalb Yorkville Figure 12: Nitrogen Dioxide 1-Hour Design Values, 2000-2012 Conyers 18 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities SULFUR DIOXIDE (SO2) GENERAL INFORMATION Sulfur dioxide (SO2) is a colorless reactive gas that is formed by burning sulfur-containing material, such as coal, or by processing sulfur-containing ores. Most SO2 emissions in Georgia come from electric generation (Figure 13). SO2 is odorless at low concentrations, but pungent at very high concentrations. It can be oxidized in the atmosphere into sulfuric acid. When locomotives, large ships, and non-road equipment burn sulfur-bearing fuel, or when ores that contain sulfur are processed, the sulfur is oxidized to form SO2. SO2 then can react with other pollutants to form aerosols. In liquid form, SO2 may be found in clouds, fog, rain, aerosol particles, and in surface liquid films on these particles. Both SO2 and NO2 are precursors to the formation of acid rain that lead to acidic deposition. SO2 is also a precursor for sulfate particles. Major sources of SO2 are fossil fuel-burning power plants and industrial boilers. Figure 13, below, shows common SO2 sources and Figure 14, below, shows SO2 emissions by county in Georgia. These figures are based on 2008 data and are taken from the latest emissions report from EPA. (From EPA's Air Emissions Sources) Figure 13: Common Sources of Sulfur Dioxide (SO2) in Georgia in 2008 (From EPA's Air Emissions Sources) Figure 14: Sulfur Dioxide Emission in Georgia in 2008 Spatial View 19 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities On June 2, 2010, the SO2 primary National Ambient Air Quality Standard was strengthened. In order to protect public health from high short-term concentrations, 1-hour SO2 concentrations are now compared to this standard. Three-year averages of the 99th% of annual daily maximum 1-hour averages are compared to the level of 75 ppb. The next three graphs (Figure 15, Figure 16 and Figure 17) show how Georgia's SO2 data compares to the 1-hour standard. Figure 15 displays all the 99th% of the maximum values for the 1-hour averages from 2000 to 2012. Figure 16 shows the three-year averages as the past and current air quality would relate to the newer standard. The highest 2012 SO2 three-year averages of the 1-hour, 99th% of the daily maximum were found at the Rome-Coosa and Savannah-E. President sites, with 74 ppb. Concentration (ppb) 140 2000 120 2001 100 2002 2003 80 2004 60 2005 2006 40 2007 20 2008 0 2009 2010 2011 2012 *Rotational sampler for at least part of operation Figure 15: SO2 99th% of 1-Hour Maximum Daily Averages, 2000-2012 120 98-00 99-01 100 00-02 75 ppb standard 01-03 80 02-04 03-05 60 04-06 40 05-07 06-08 20 07-09 08-10 0 09-11 10-12 Three-Year Averages of 99th% Daily Max 1-Hour Averages (ppb) Figure 16: SO2 1-Hour Design Values, 2000-2012 *Sampler started in 2010 20 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 17 displays an overall statewide average, maximum, and minimum three-year averages compared to the SO2 1-hour, 99th percentile daily maximum (75 ppb). The statewide averages have decreased 47% between 2000 and 2012 as shown in Figure 17. The average of the SO2 three-year averages peaked at 82 ppb for the 2005-2007 average and has decreased to 37 ppb in the current 2010-2012 average. 120 Maximum 100 3 year averages of 99th% daily max 1-hour averages (ppb) 80 EPA Standard 60 Average 40 Minimum 20 0 Figure 17: Statewide SO2 1-Hour Design Value Averages, Maximums, and Minimums, 19982012 HEALTH IMPACTS Exposure to SO2 can cause impairment of respiratory function, aggravation of existing respiratory disease (especially bronchitis), and a decrease in the ability of the lungs to clear foreign particles. It can also increase mortality, especially if elevated levels of particulate matter (PM) are present. Individuals with hyperactive airways, cardiovascular disease, and asthma are most sensitive to the effects of SO2. In addition, elderly people and children are also likely to be sensitive to this air pollutant. The effects of short-term peak exposures to SO2 have been evaluated in controlled human exposure studies. These studies show that SO2 generally increases airway resistance in the lungs, and can cause significant constriction of air passages in sensitive asthmatics. These impacts have been observed in subjects engaged in moderate to heavy exercise while exposed to relatively high peak concentrations. These changes in lung function are accompanied by perceptible symptoms such as wheezing, shortness of breath, and coughing in these sensitive groups. The presence of particle pollution appears to aggravate the impact of SO2 pollution. Several studies of chronic effects have found that people living in areas with high particulate matter and SO2 levels have a higher incidence of respiratory illnesses and symptoms than people living in areas without such a combination of pollutants. MEASUREMENT TECHNIQUES Sulfur dioxide is measured in the ambient air using EPA-approved equivalent method instruments as defined in 40 CFR Part 53, Appendix A. Georgia's sulfur dioxide network consists of continuous instruments using a pulsed ultraviolet (UV) fluorescence technique. This monitoring technique is 21 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities based on measuring the emitted fluorescence of SO2 produced by its absorption of UV radiation. Pulsating UV light is focused through a narrow bandpass filter allowing only light wavelengths of 1,900 to 2,300 angstrom units (A_) to pass into the fluorescence chamber. SO2 absorbs light in this region without any quenching by air or most other molecules found in polluted air. The SO2 molecules are excited by UV light and emit a characteristic decay radiation. A second filter allows only this decay radiation to reach a photomultiplier tube. Electronic signal processing transforms the light energy impinging on the photomultiplier tube into a voltage which is directly proportional to the concentration of SO2 in the sample stream being analyzed. The sampler outputs the SO2 concentration to the front panel display and to an analog or digital output. Data gained from the continuous monitors are used to determine compliance with the NAAQS for SO2. ATTAINMENT DESIGNATION To determine if an SO2 monitor is in attainment, the 1-hour daily maximum values, and 3-hour averages are evaluated. The data collected has to be at least 75 percent complete in each calendar quarter. A 24-hour block average is considered valid if at least 75 percent of the hourly averages for that 24-hour period are available [61 FR 25579, May 22, 1996]. To be considered in attainment of the secondary standard, an SO2 site must have no more than one 3-hour average exceeding 0.5 ppm (500 ppb) [38 FR 25678, September 14, 1973]. In addition, for the newer 1-hour primary standard, the three-year averages of the 99th% of annual daily maximum 1-hour averages should be less than 75 ppb [Federal Register, Vol. 75, No. 119, page 35520, dated June 22, 2010], as shown above. For 2012, the State of Georgia is in attainment of the sulfur dioxide standards. For additional summary data on this topic, see Appendix A. Figure 18 shows the locations of the Georgia SO2 monitoring stations for 2012. 22 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 18: Sulfur Dioxide Monitoring Site Map 23 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities OZONE (O3) GENERAL INFORMATION Ground level ozone formation occurs through a complex series of photochemical reactions that take place in the presence of strong sunlight. Since the reactions must take place in the presence of sunlight, ozone concentrations have a strong diurnal pattern (occurring daily and in daylight hours). Figure 19 shows this typical diurnal pattern of ozone concentration throughout the day. 0.1 0.08 Concentration (ppm) 0.06 0.04 0.02 0 Hour Figure 19: Typical Urban 1-Hour Ozone Diurnal Pattern For these photochemical reactions to take place, certain components, or precursors, must be available. The precursors1 to ozone are oxides of nitrogen (NOx) and photochemically reactive volatile organic compounds (VOCs) (Figure 20). Common sources of NOx include combustion processes from vehicles and industrial processes. Examples of the reactive VOCs that contribute to ozone formation are: hydrocarbons found in automobile exhaust (benzene, propane, toluene); vapors from cleaning solvents (toluene); and biogenic emissions from plants (isoprene). (Courtesy of Jamie Smith) Figure 20: Ozone Formation Process 1 For a more complete discussion on ozone precursors, please see the NO2 section and the PAMS section of this report. 24 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Sources of VOCs in Georgia are shown in Figure 21, below, followed by a spatial view of VOC emissions across the state in Figure 22. In Georgia, biogenic emissions may be most common source, but they are not part of the emission inventory. These figures are taken from the latest emissions report from EPA, based on 2008 data. Ozone is a colorless gas; however, when mixed with particles and other pollutants, such as NO2, the atmospheric reaction forms a brownish, pungent mixture. This type of pollution first gained attention in the 1940's in Los Angeles as photochemical "smog". Since then, smog has been observed frequently in many other cities. (From EPA's Air Emissions Sources) Figure 21: Common Sources of Volatile Organic Compounds (VOCs) in Georgia in 2008 (From EPA's Air Emissions Sources) Figure 22: Volatile Organic Compounds (VOCs) Emission in Georgia in 2008 Spatial View 25 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities As indicated above, ozone is formed when its precursors come together in the presence of strong sunlight. The reaction only occurs when both precursors are present, and the reaction itself consumes the precursors as it produces ozone. The amount of ozone produced, assuming sufficient sunlight, is controlled by what is known as the "limiting reactant." This limiting reactant can be thought of in terms of household baking. One can only bake cookies until any one of the ingredients is gone. If the flour is gone, it does not matter how much milk and sugar there is; no more cookies can be made without more flour. In the same way, ozone production can only occur until the process has consumed all of any one of the required ingredients. As it turns out, natural background hydrocarbon levels are quite low in Los Angeles. Therefore, in that area, hydrocarbons are typically the reactant that limits how much ozone can be produced. The control measures that proved effective in reducing smog in the Los Angeles area involved reducing hydrocarbon emissions. These control measures and the science behind them have become relatively advanced because the Los Angeles ozone problem was so severe and developed so long ago. However, many of the fundamental lessons learned about smog formation in Los Angeles over many years of research have proven to not apply in the same way in Georgia. At the start of air quality control implementation in Georgia, the assumption was that Georgia was also hydrocarbon limited. However, the initial control measures seemed ineffective in actually reducing ozone levels. In time, researchers discovered that vegetation naturally emits large quantities of hydrocarbons. The solution to ozone control in Georgia, then, would have to focus on a different limiting reactant. Since there will always be strong sunshine in the summer, and there will always be oxygen, the only effective way left to control ozone production is to reduce emissions of oxides of nitrogen. Various strategies have been put into place to control hydrocarbons and oxides of nitrogen. With respect to reducing emissions from automobile engines, for example, the addition of relatively simple and inexpensive catalytic converters to existing engine design was a great leap forward in reducing hydrocarbon emissions, and has been used with great success since the early 1970's. In Atlanta, while catalytic converters and many other VOC controls have been put into place, control measures have also been implemented for the reduction of oxides of nitrogen, including selective catalytic reduction (SCR) on power plant generators. A final difference between ozone and the other pollutants is that ozone is sometimes good. While ground level ozone is considered a hazardous pollutant, the ozone in the upper atmosphere, approximately 10-22 miles above the earth's surface, protects life on earth from the sun's harmful ultraviolet (UV) rays. This ozone is gradually being depleted due to man-made products called ozone depleting chemicals, including chlorofluorocarbons (CFC), which when released naturally, migrate to the upper atmosphere. In the upper atmosphere, CFCs break down due to the intensity of the sun's UV rays, releasing chlorine and bromine atoms. These atoms react with the ozone and destroy it. Scientists say that one chlorine atom can destroy as many as 100,000 "good" ozone molecules. The destruction of this ozone may lead to more harmful ultraviolet rays reaching the earth's surface, causing increased skin cancer rates. This reduction in the protection provided by ozone in the upper atmosphere is usually referred to as the "ozone hole" and is most pronounced in polar regions. With the exception of the South DeKalb site, ozone in Georgia, unlike other pollutants previously discussed, is only monitored during the "summer" months (March through October), according to EPA's 40 Code of Federal Regulations Part 58 monitoring requirements. The South DeKalb site began year-round monitoring as of November 2009. Many urban areas experience high levels of ground level ozone during the summer months. High ozone levels can also be seen in rural and mountainous areas. This is often caused by ozone and/or its precursors being transported by wind for many hundreds of miles. As part of the Clean Air Status and Trends Network (CASTNET), EPA established a monitoring site in Georgia in 1988. The CASTNET site is part of a national air quality monitoring network put in place to 26 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities assess long-term trends in atmospheric deposition and ecological effects of air pollutants. The CASTNET site is one of 85 regional sites across rural areas of the United States and Canada measuring nitrogen, sulfur, and ozone concentrations, and deposition of sulfur and nitrogen. Like the South DeKalb ozone monitor, the CASTNET ozone monitor also collects data year-round. As of 2011, the CASTNET ozone monitor met the Code of Federal Regulations (40 CFR), and met quality assurance and completeness criteria. Therefore, as of 2011, data collected by this monitor can be used for comparison to the NAAQS. In 2012, the GA Environmental Protection Division monitored ground level ozone at 20 sites throughout the state, and the EPA collected data at the CASTNET site. The following figure shows the locations of all the ozone monitoring stations, including the Fayetteville station, which has been temporarily discontinued. 27 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 23: Ozone Monitoring Site Map 28 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities HEALTH IMPACTS Ozone and other photochemical oxidants such as peroxyacetyl nitrate (PAN) and aldehydes are associated with adverse health effects in humans. Peroxyacetyl nitrate and aldehydes cause irritation that is characteristic of photochemical pollution. Ozone has a greater impact on the respiratory system, where it irritates the mucous membranes of the nose, throat, and airways. Ninety percent of the ozone inhaled into the lungs is never exhaled. Symptoms associated with exposure include cough, chest pain, and throat irritation. Ozone can also increase susceptibility to respiratory infections. In addition, ozone impairs normal functioning of the lungs and reduces the ability to perform physical exercise. Recent studies also suggest that even at lower ozone concentrations some healthy individuals engaged in moderate exercise for six to eight hours may experience symptoms. All of these effects are more severe in individuals with sensitive respiratory systems, and studies show that moderate levels may impair the ability of individuals with asthma or respiratory disease to engage in normal daily activities. The potential chronic effects of repeated exposure to ozone are of even greater concern. Laboratory studies show that people exposed over a six to eight hour period to relatively low ozone levels develop lung inflammation. Animal studies suggest that if exposures are repeated over a long period (e.g. months, years, lifetime), inflammation of this type may lead to permanent scarring of lung tissue, loss of lung function, and reduced lung elasticity. MEASUREMENT TECHNIQUES Georgia's ozone analyzers continuously measure the concentration of ozone in ambient air using the ultraviolet (UV) photometric method and are EPA-approved for regulatory air monitoring programs. The degree to which the UV light is absorbed is directly related to the ozone concentration. The ambient air is drawn into the sample bulkhead and is split into two gas streams. One gas stream flows through an ozone scrubber to become the reference gas. The reference gas then flows to the reference solenoid valve. The sample gas flows directly to the sample solenoid valve. The solenoid valves alternate the reference and sample gas streams between the two cells every 10 seconds. When cell A contains reference gas, cell B contains sample gas and vice versa. The UV light intensities of each cell are measured by detectors A and B. When the solenoid valves switch the reference and sample gas streams to opposite cells, the light intensities are ignored for several seconds to allow the cells to be flushed. The sampler calculates the ozone concentration for each cell and outputs the average concentration to both the front panel display and the analog or digital output. Data gained from the continuous monitors are used to determine compliance with the NAAQS for ozone. ATTAINMENT DESIGNATION Ozone monitoring has been in place in the Atlanta area since 1980. The 1980 network consisted of two monitors located in DeKalb and Rockdale Counties. Currently the Atlanta-Sandy Springs-Marietta MSA ozone network includes ten monitors located in ten counties. In July 1997 the U.S. EPA issued an 8-hour ozone standard intended to eventually replace the older 1-hour standard. This 8-hour standard is attained when the average of the fourth highest concentration measured is equal to or below 0.08 ppm (up to 0.085 ppm with third digit truncated, or cut off) averaged over three years (see Table 1; 62 FR 38894, July 18, 1997). Areas that EPA designated attainment with the 1-hour standard were immediately exempt from that standard, and thereafter are subject to the 8-hour standard. In the summer of 2005, the metro Atlanta area was designated attainment with the 1-hour standard. As of the printing of this report, only the 8-hour ozone standard is applicable in Georgia. Data shows that the Atlanta area will be in attainment with the 1997 8-hour standard of 0.085 ppm, but has not been officially redesignated as attainment. For attainment designations to be official, the maintenance state implementation plan (SIP) needs to be submitted by GA EPD and approved by EPA. GA EPD has submitted the maintenance SIP and is awaiting approval. The current Atlanta ozone nonattainment area compared to the 1997 standard consists of Barrow, Cherokee, Clayton, Cobb, Coweta, DeKalb, Douglas, Fayette, Forsyth, Fulton, Gwinnett, 29 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Henry, Paulding, Rockdale, Bartow, Carroll, Hall, Newton, Spalding, and Walton Counties. All other metropolitan statistical areas in Georgia are currently in attainment of this standard. Catoosa County is part of the Chattanooga Early Action Compact area. Figure 24 shows the boundaries of this nonattainment area. Figure 24: Georgia's 8-Hour Ozone Nonattainment Area Map for 1997 Standard On March 27, 2008 the ozone primary standard level was lowered to 0.075 ppm for the 8-hour averaging time, fourth maximum value, averaged over three years (Federal Register, Vol. 73, No. 60, page 16436). With the implementation of the 2008 ground-level ozone standard, the boundary of the Atlanta nonattainment area is defined as a 15-county area. The 15-county area includes Bartow, Cherokee, Clayton, Cobb, Coweta, DeKalb, Douglas, Fayette, Forsyth, Fulton, Gwinnett, Henry, Newton, Paulding, and Rockdale Counties. A map of this area is shown in the following figure on the next page. Because the Atlanta area was defined with a `marginal' designation compared to the 2008 ground-level ozone standard, a SIP is not required. 30 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 25: Georgia's 8-Hour Ozone Nonattainment Area Map for 2008 Standard A number of activities to aid in controlling the precursors to ozone formation have been implemented. A new State Implementation Plan (SIP) will be developed to assist in ozone reduction. As new areas are declared in nonattainment, these control measures may be expanded to include them. One activity could include a vehicle inspection program. However, as the vehicle fleet gets younger, this is not as beneficial. Other activities include installing controls on stationary emission sources, and the establishment of a voluntary mobile emissions reduction program. An example of such a program in the Atlanta-Sandy Springs-Marietta MSA is called The Clean Air Campaign (CAC). Activities of The Clean Air Campaign include distributing daily ozone forecasts (as well as PM2.5 forecasts produced by EPD and Georgia Tech) during the ozone season to enable citizens in the sensitive group category, as well as industries, to alter activities on days that are forecasted to be conducive to ozone formation. This is also done for the Macon and Columbus metropolitan areas. In addition to the daily forecasts, citizens have access to forecast and monitoring data on an as needed basis by either calling 1-800-427-9605 or by accessing the Georgia DNR/EPD Ambient Air Monitoring website at 31 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities http://www.air.dnr.state.ga.us/amp/index.php. For a more detailed discussion concerning the CAC, see the section in this report titled "Outreach and Education". Figure 26 shows how past air quality would relate to the current 0.075 ppm 8-hour ozone standard (red line), and how current air quality relates to the old 0.085 ppm 8-hour ozone standard (blue line). This chart was produced by comparing measurement data against both ambient standards. This demonstrates the relative strictness of each standard and shows how the Atlanta-Sandy SpringsMarietta MSA's air quality has changed over time. Despite a great deal of fluctuation, over the course of the past twenty-seven years, there has been a gradual reduction in the number of days exceeding either ozone standard. A trendline, produced by regression analysis, was created for both the 8-hour standards. Trendlines for both standards show that the number of days that exceed the ozone standard has fallen by approximately one day each year over this time period. Even with the new, lower 8-hour ozone standard, the data shows a decrease in the number of days with ozone exceedances for the Atlanta-Sandy Springs-Marietta MSA. In 2012, the Atlanta-Sandy SpringsMarietta MSA area had a total of 17 days that violated the current (0.075 ppm) 8-hour standard. Exceedance Days 100 90 80 70 60 50 40 30 20 10 0 0.085 ppm 0.075 ppm Linear (0.085 ppm) Linear (0.075 ppm) Figure 26: Atlanta-Sandy Springs-Marietta MSA Ozone- Number of Violation Days per Year 32 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities In the following graph, the three-year ozone design values are shown for all twenty of GA EPD's ozone sites across the state. Seven sites (all within the Atlanta-Sandy Springs-Marietta MSA) have 2010-2012 three-year ozone design values (shown in light blue) above the standard. Leslie Conyers Augusta CASTNET* Yorkville Columbus Fort Mountain McDonough Gwinnett Tech 0.075 ppm standard 10-12 09-11 08-10 07-09 06-08 05-07 04-06 03-05 02-04 01-03 00-02 Albany Site Confederate Ave Douglasville South DeKalb Dawsonville Newnan Evans Kennesaw Athens Summerville Savannah Macon 0 0.02 0.04 0.06 0.08 0.1 0.12 Concentration (ppm) *Incomplete; 2011-2012 Figure 27: Ozone Design Values, 2000-2012 33 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 28, on the next page, maps each Atlanta-Sandy Springs-Marietta MSA ozone monitor that exceeded the 8-hour ozone standard in 2012, and also indicates the monthly breakdown of the exceedances. Since the 8-hour increment is calculated as a running 8-hour timeframe, there are a number of averages each day. Figure 28 shows the number of days that each monitor had 8-hour averages above the 0.075 ppm standard. The Confederate Avenue site shows the highest number of days with 8-hour ozone averages above 0.075 ppm, with a total of 10 days for the 2012 ozone season. Nine of the total eleven ozone sites collecting data in the Atlanta-Sandy Springs-Marietta MSA had exceedance days in 2012. For additional ozone summary data, see Appendix A. 34 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 28: Atlanta-Sandy Springs-Marietta MSA Ozone Exceedance Map 35 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities The following map was taken from the EPA document "Our Nation's Air- Status and Trends through 2010". It shows the fourth maximum reading for the 8-hour ozone readings across the United States. Georgia's fourth maximum ozone readings in 2010 were in the 0.060-0.075 ppm (light blue) and 0.076-0.095 ppm (yellow) ranges. (From EPA's "Our Nation's Air Quality-Status and Trends through 2010") Figure 29: Ozone Concentrations in ppm, 2010 (Fourth Highest Daily Maximum 8-Hour Concentrations) 36 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities LEAD (Pb) GENERAL INFORMATION In the past, the Clean Air Act required extensive lead monitoring in order to detect the high levels of airborne lead that resulted from the use of leaded gasoline. With the phase-out of leaded gasoline, lead concentrations had decreased to nearly detection level by the late 1980s. Since then, the concentrations have hovered just above detection level. Based on data from EPA's Air Emission Sources for 2008, Georgia's primary source of lead emissions comes from mobile sources (Figure 30). Other sources of lead emissions include industrial processes (metals processing, iron and steel production), combustion of solid waste, and lead-acid battery manufacturing. Figure 31, below, shows a spatial view of Georgia's lead emissions, also from EPA's Air Emission Sources, based on 2008 data. (From EPA's Air Emissions Sources) Figure 30: Common Sources of Lead in Georgia in 2008 (From EPA's Air Emissions Sources) Figure 31: Lead Emission in Georgia in 2008 Spatial View 37 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities At the beginning of 2009, there were two dedicated lead monitors remaining in Georgia for comparison to the NAAQS lead standard. One was in the Atlanta-Sandy Springs-Marietta MSA for monitoring long-term trends in ambient lead levels, and the other was located in the Columbus GA-AL MSA for industrial source monitoring (given the historical issues with lead pollution in the area). At the end of 2008, EPA strengthened the standard and monitoring requirements. In addition to lowering the standard, further monitors were to be placed in areas with demonstrated lead emissions of 1.0 or more tons per year and in urban areas with a population in excess of 500,000 (Federal Register, Vol. 73, No. 219, dated November 12, 2008). In response to this rule change, in December of 2009, GA EPD added a lead monitoring site in the Cartersville area in order to observe an additional pollutant source. Since this time (December 14, 2010), EPA has lowered the source-oriented lead emission levels to 0.5 tons per year (tpy), and changed the population based requirement to include the `NCore network' (40CFR58, Docket #EPA-HQ-OAR-2006-0735). To monitor industrial facilities that emit greater than 0.5 tpy, GA EPD reopened two lead monitors in the Columbus GA-AL MSA in 2012 to determine proper siting in this area. The current criteria lead monitoring network is indicated in Figure 32. For summary data on criteria lead monitoring, see Appendix A. In addition to the criteria network sites, lead is also being monitored at sites throughout the state as a trace metal in the Georgia Air Toxics Monitoring Network, the National Air Toxics Trends Station (NATTS), and with PM2.5 speciation samplers. In the Air Toxics Network, samples are taken from total suspended particles in the ambient air. The NATTS sampler is a PM10 sampler and collects particles up to 10 microns in size. With the PM2.5 speciation samplers, particles are collected up to 2.5 microns in size. For additional summary data concerning lead collected as an Air Toxics trace metal, see Appendix D. 38 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 32: Lead Monitoring Site Map 39 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities HEALTH IMPACTS Exposure to lead occurs mainly through inhalation and ingestion of lead in food, water, soil, or dust. Lead particles can re-enter the environment through re-entrainment of dust from vehicle traffic, construction activities, and agricultural activities. It accumulates in the blood, bones, and soft tissues. Lead can adversely affect the kidneys, liver, nervous system, and other organs. Excessive exposure to lead may cause neurological impairments, such as seizures, mental retardation, and behavioral disorders. Even at low doses, lead exposure is associated with damage to the nervous systems of fetuses and young children, resulting in learning deficits and lowered IQ. Recent studies also show that lead may be a factor in high blood pressure and subsequent heart disease. Lead can also be deposited on the leaves of plants, presenting a hazard to grazing animals. Lead deposition in soil puts children at particular risk exposure since they commonly put hands, toys, and other items in their mouths, which may come in contact with lead-containing dust and dirt. MEASUREMENT TECHNIQUES Since lead is a particulate, the measurement for ambient air lead concentrations is performed using a manual method, unlike measurements for the gaseous pollutants discussed earlier (ozone, SO2, NO2 and CO). Samples are collected on 8" x 10" pre-weighed fiberglass filters with a high-volume total suspended particulate (TSP) sampler for 24 hours, collecting particles with diameters of 100 microns or less. High volumes of ambient air in the flow range of 40-60 cubic feet per minute are sampled at a constant rate during the sampling period. This produces a uniform distribution of particles deposited on the sample filter downstream of the sampler inlet. Samples collected with the TSP high volume sampler can be used to determine the average ambient TSP concentration over a sampling period followed by subsequent analysis to determine the identity and quantity of inorganic metals present in the TSP. The filter sample is shipped to a laboratory for analysis using inductively coupled plasma mass spectroscopy (commonly known as ICP-MS). Data gained from the criteria lead samplers are used to determine compliance with the National Ambient Air Quality Standards for lead. In addition to the criteria lead network sites, lead is monitored as a trace metal in the Georgia Air Toxics Monitoring Network, the National Air Toxics Trends Station (NATTS), and with the PM2.5 speciation samplers. Air Toxics Network, samples are obtained with a High-Volume sampler collecting total suspended particles in the ambient air. NATTS lead is sampled using a PM10 sampler, and particles are sampled up to 10 microns in size. PM2.5 speciation samplers collect particles up to 2.5 microns in size. All three of these sampling techniques also collect 24-hour samples on pre-weighed filters, ship samples to a laboratory for analysis, and are analyzed with ICP-MS. ATTAINMENT DESIGNATION Compliance with the national primary and secondary ambient air quality standards for lead and its compounds is determined based on the assumption that all lead is elemental lead. In order to comply with both the primary and secondary standards, the concentration of lead in the air must have an arithmetic mean no higher than 0.15 micrograms per cubic meter averaged on a rolling 3-month basis (Federal Register, Vol. 73, No. 219, dated November 12, 2008). On October 15, 2008 this standard was changed from the original standard of 1.5 g/m3 averaged per calendar quarter that had been in place since October 5, 1978 (43 FR 46258). This new lead standard became effective on January 12, 2009 and was implemented by January 1, 2010. Then on December 14, 2010, EPA revised the requirements for measuring lead in the ambient air. The emission threshold for placing lead monitors near industrial facilities was lowered from 1.0 tons per year (tpy) to 0.5 tpy. In addition, EPA is requiring that lead monitors be placed at the NCore sites. The new lead monitors were required to be operational by December 27, 2011 [40CFR58, Docket No. EPA-HQ-OAR-2006-0735, 12/14/10]. GA EPD meets the requirement of monitoring lead at the South DeKalb NCore site, with the sampler located at the nearby DMRC site. To accommodate the changes to monitor industries with lead emissions greater than 0.5 tpy, GA EPD reopened two monitors in the Columbus GA-AL MSA in 2012 to determine proper location of this source-oriented monitor. In addition, GA EPD had previously established a source-oriented lead monitor in the Cartersville area. 40 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities The following graph shows how Georgia's lead data compares to the rolling three-month average standard for 2010 through 2012. The last of the three months used for each average is indicated on the graph. The two monitors that were reopened in the Columbus GA-AL MSA have shown higher readings compared to the other monitors in the Columbus GA-AL MSA or the Atlanta-Sandy SpringsMarietta MSA. As more lead data is collected, it will be observed to see if this trend continues. For additional summary data on this topic, see Appendix A. 0.25 Concentration (g/m3) 0.20 0.15 g/m3 standard 0.15 0.10 0.05 0.00 Cartersville Atlanta Columbus-Cusseta Columbus-UPS Columbus- Ft Benning Figure 33: Three-Month Rolling Averages of Lead, 2010-2012 The following map was taken from EPA's document "Our Nation's Air Quality-Status and Trends through 2010" showing the maximum three-month lead averages across the United States. Georgia's three-month maximum lead averages in 2010 were in the lowest range, 0.00-0.07 ppm (dark blue). (From EPA's "Our Nation's Air Quality-Status and Trends through 2010") Figure 34: Lead Concentrations in g/m3, 2010 (Maximum 3-month Averages) 41 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities PARTICULATE MATTER GENERAL INFORMATION Particulate matter is a broad range of material that consists of solid particles, fine liquid droplets, or condensed liquids absorbed onto solid particles. Airborne particulates are not a single pollutant as discussed for the other criteria pollutants, but rather a mixture of many different air pollutants. Primary sources that emit particles include combustion, incineration, construction, mining, metals smelting, metal processing, and grinding. Other sources include motor vehicle exhaust, road dust, wind blown soil, forest fires, open burning of vegetation for land clearing or waste removal, ocean spray, and volcanic activity. There are two ways (primary and secondary) that particulate matter is formed. Primary particulate is emitted directly from a source, like a vehicle's tailpipe or a factory's smokestack. However, a great deal of particulate matter is not directly emitted from such sources. In fact, the vast majority of primary air pollution is in the form of gases. Those gaseous air pollutants readily react in the atmosphere with oxygen and with each other. While many of those reactions produce other gases, they frequently produce particles. Particles formed through this process are known as secondary particulate matter. Examples of secondary particulates include: Atmospheric sulfate particles, formed from the oxidation of gaseous SO2. Atmospheric nitrate particles, such as ammonium nitrate, formed from a complex series of reactions that transform gaseous NOx. Atmospheric calcium nitrate or sodium nitrate particulates formed from a series of atmospheric reactions involving gaseous nitric acid (HNO3) reacting with sodium chloride/calcium carbonate. Since diesel combustion and vehicle exhaust are sources of particulate matter, efforts are being made to reduce these emissions by retrofitting diesel engines and making alternative diesel fuels available. Retrofitting is defined as the addition of an emission control device designed to remove emissions from an exhaust engine. Currently, school buses and diesel powered commercial trucks are being retrofitted for emission reduction. One method is a particulate trap, which essentially filters exhaust from the engine. In some cases, as the particulate accumulates in the filter, the particulate is oxidized or burned off in order to regenerate the filter and reuse it. Regeneration is achieved by various techniques that reduce the temperature necessary to oxidize accumulated particulate matter. Disposable filters are also used when the particulate matter cannot be cleaned by oxidation. For information about Georgia EPD's program, go to http://www.georgiaair.org/retrofit/index.htm. In addition to retrofitting, alternative diesel fuels are available that emit less particulate matter, as well as other pollutants. Ultra-low sulfur diesel fuel is one fuel that emits less sulfur and particulate matter. Biodiesel fuel emits less particulate matter, carbon monoxide, hydrocarbons, and air toxics. Also, emulsified diesel emits less nitrogen oxides and particulate matter. Particulate pollution may be categorized by size since there are different health impacts associated with the different sizes. The Georgia Ambient Air Monitoring Program currently monitors for three sizes of particles: PM10 (up to 10 microns in diameter), PM2.5 (up to 2.5 microns in diameter) and PMcoarse (PM10 minus PM2.5). All of these particles are very small in size. For example, Figure 35 shows how approximately ten PM10 Figure 35: Analogy of Particulate Matter Size to Human Hair 42 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities particles can fit on a cross section of a human hair, and approximately thirty PM2.5 particles would fit on a cross section of a hair. Maps of each of the particulate matter networks (PM10, PMcoarse, PM2.5 federal reference method, PM2.5 continuous, and PM2.5 speciation) are included in the following subsections that discuss particulate matter. PM10 Particulate matter (PM) less than or equal to 10 microns in diameter is defined as PM10. These particles can be solid matter or liquid droplets from smoke, dust, fly ash, or condensing vapors that can be suspended in the air for long periods of time. PM10 represents part of a broad class of chemically diverse particles that range in size from molecular clusters of 0.005 microns in diameter to coarse particles of 10 microns in diameter (for comparison, an average human hair is 70-100 microns in diameter, as shown in the previous figure). PM results from all types of combustion. The carbonbased particles that result from incomplete burning of diesel fuel in buses, trucks, and cars are examples of major sources of PM10. Another important combustion source is the burning of wood in stoves and fireplaces in residential settings. Also of concern are the sulfate and nitrate particles that are formed as a by-product of SO2 and NO2 emissions, primarily from fossil fuel-burning power plants and vehicular exhausts. For a map of the PM10 network, refer to Figure 36 on the next page. HEALTH IMPACTS The U.S. national ambient air quality standard was originally based on particles up to 25-45 microns in size, termed "total suspended particles" (TSP). In 1987, EPA replaced TSP with an indicator that includes only those particles smaller than 10 microns, termed PM10. These smaller particles cause adverse health effects because of their ability to penetrate deeply into the lungs. The observed human health effects of PM include breathing and respiratory problems, aggravation of existing respiratory and cardiovascular disease, alterations in the body's defense system against inhaled materials and organisms, and damage to lung tissue. Groups that appear to be most sensitive to the effects of PM include individuals with chronic lung or cardiovascular disease, individuals with influenza, asthmatics, elderly people, and children. 43 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 36: PM10 Monitoring Site Map 44 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities MEASUREMENT TECHNIQUES The Georgia PM10 monitoring network consists of two types of EPA-approved reference or equivalent monitors. Both types of monitors are used to determine attainment with the PM10 standard. The first type of monitor is an integrated low-volume sampler that collects samples for a 24-hour period. Ambient air is sampled through an impaction inlet device that only allows particles with 10 microns or less in diameter to reach the filter media. The flow rate is controlled by an electronic mass-flow controller, which uses a flow sensor installed below the filter holder to monitor the mass flow rate and control the speed of the motor accordingly. Filters are weighed in a laboratory before and after the sampling period. The change in the filter weight corresponds to the mass of PM10 particles collected. That mass, divided by the total volume of air sampled, corresponds to the mass concentration of the particles in the air. The second type of PM10 monitor that Georgia EPD operates is a continuous monitor. The continuous monitor measures and records hourly particulate mass concentrations in ambient air. The monitor consists of three basic components; the central unit, the sampling pump and the sampling inlet hardware. In order to sample particles that are 10 microns or less, the inlet is designed to cut out particles larger than 10 microns in size. The monitor uses beta ray attenuation to calculate collected particle mass concentrations in units of micrograms per cubic meter (g/m3). A 14C element (60 Ci +/- 15 C) emits a constant source of low-energy electrons, also known as beta particles. The beta rays are attenuated as they collide with particles collected on a filter tape. The decrease in signal detected by the scintillation counter is inversely proportional to the mass loading on the filter tape. The pump turns on at the beginning of the hour and runs for 50 minutes. During the last 10 minutes of the hour, the pump turns off while the tape transport operates, final mass reading is collected, and selftests are performed. PM10 concentrations are displayed on the front panel and sent to the analog or digital output. ATTAINMENT DESIGNATION The primary and secondary standards for PM10 are the same. In order for an area to be considered in compliance with the PM10 standard, the 24-hour concentration of 150 micrograms per cubic meter should not be exceeded more than once per year on average over three years [52 FR 24663, July 1, 1987, as amended at 62 FR 38711, July 18, 1997; 65 FR 80779, Dec. 22, 2000]. Figure 37, on the next page, shows how Georgia compares to the 24-hour standard for PM10, which remains set at 150 g/m3. The standard allows one exceedance per year, averaged over a 3-year period; therefore, this chart shows the second highest 24-hour average for each site. Although there is variation from year to year at any given site, the statewide 24-hour average is relatively stable, with a gradual decrease over ten years. The concentrations of PM10 in 2007 were above normal due to excessive smoke from the Sweat Farm/Big Turnaround/Bugaboo Fire in the Okefenokee Swamp. Due to this wildfire, Georgia EPD requested from the U.S. EPA that two PM10 data points from the Albany site be flagged as an exceptional event, and not be used in regulatory calculations. The U.S. EPA has approved this request. However, since the public was exposed to these levels of PM10 concentrations, they are included in Figure 37, Figure 38, and Figure 39, on the following pages. In Figure 37, the 2007 data (shown in teal), the second highest 24-hour value of 187 g/m3 for the Albany site is one of the two exceptional event data points that were taken out of the dataset for regulatory calculations. The other data point was Albany's highest value of 189 g/m3. In 2008 (shown in dark blue), almost all of the sites show a marked decline in the second highest 24-hour concentration of PM10, with many sites' concentrations below the level of the 2006 concentrations (shown in light green). With the 2012 data (shown in brown), all of the sites continue to show a decrease in 24-hour PM10 concentrations. For the past four years, all of the second highest 24-hour PM10 concentrations have remained below 60 g/m3, well below the 150 g/m3 limit. For additional PM10 summary data, see Appendix A. 45 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Statewide (avg) Section: Chemical Monitoring Activities Sandersville Augusta Columbus Brunswick Georgia Tech 150 g/m3 limit E Rivers Site Rome Albany Doraville South DeKalb Summerville Savannah Macon 0 2003 30 60 90 120 150 180 Second Highest 24-Hour PM10 Concentration (g/m3)+ 2004 2005 2006 2007 2008 2009 2010 2011 2012 + Includes all data for 2007 that was excluded for exceptional events * Sites consolidated, data combined for Rome-Coosa Elem and Coosa High in 2009 Figure 37: Second Highest 24-Hour PM10 Concentration 46 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities In Figure 38 below, the PM10 statewide concentrations are explored further. The statewide annual average, maximum, and minimum of the second highest 24-hour concentrations are shown. The statewide annual averages have consistently remained around 40-50 g/m3 and then dropped to around 35 g/m3 in 2012. The statewide average of the 24-hour PM10 concentrations decreased 30% between 1996 and 2012. While the minimum concentrations have remained low, with values ranging from about 20-40 g/m3, the maximum concentrations have fluctuated over the years. The 2007 wildfire in the Okefenokee Swamp is reflected in the peak second maximum value of 187 g/m3 for PM10 in a 24-hour period. 200 180 EPA Standard, 150 g/m3 160 Concentration (g/m) 140 120 Maximum 100 80 Average 60 40 Minimum 20 0 Figure 38: Statewide PM10 Concentrations (2nd Highest 24-Hour) 47 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 39 shows the annual PM10 averages in Georgia from 2003 through 2012. On an annual basis, PM10 levels in Georgia are relatively low. However, there was an increase in the annual averages of PM10 for 2007 that was a product of the Sweat Farm/Big Turnaround/Bugaboo Fire in the Okefenokee Swamp. In 2008, there was a noticeable reduction in annual average concentrations of PM10 across the state. This trend has continued through 2012, with annual average concentrations of PM10 ranging from 13-21 g/m3. 40.0 Average Concentration (g/m) 35.0 30.0 25.0 20.0 15.0 10.0 Macon Albany Columbus Savannah Rome* Augusta Summerville E.Rivers School Sandersville South DeKalb Georgia Tech Doraville Brunswick + Includes exceptional event data for 2007 *Rome data consolidated for 131150003 and 131150005 in 2009 Figure 39: PM10 Annual Arithmetic Mean Chart 48 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 40 shows a map that was taken from the EPA document "Our Nation's Air-Status and Trends through 2010". It shows PM10 second maximum 24-hour concentrations across the United States for 2010. This gives a comparison of Georgia's PM10 data, related to the rest of the country. For Georgia, the second maximum 24-hour concentrations were in the lowest range of 2-54 g/m3 (dark blue). (From EPA's "Our Nation's Air Quality-Status and Trends through 2010") Figure 40: PM10 Second Maximum 24-Hour Concentrations (g/m3), 2010 PMCoarse PMcoarse, or PM10-2.5, is described as particulate matter (PM) less than 10 microns in diameter and greater than 2.5 microns in diameter. The composition of PMcoarse is predominantly crustal matter (from construction, demolition, mining, agricultural activities, sea spray, dust) and organic materials (from resuspension of biological material from soil surfaces and roads). However, composition and sources can vary greatly by region. Regional relative humidity can affect the level of water present within the particles and affect how much dissolved gases or reactive species enter the lungs. The amount of water within the PMcoarse material can also affect size and particle deposition characteristics. As part of the NCore requirements, the South DeKalb site began PMcoarse sampling as of January 1, 2011. Figure 41, below, displays daily PMcoarse averages across the state from 2011 through 2012. During the two year span, PMcoarse daily average concentrations have been found primarily in the 5-15 g/m range, and fell by about 2.5 g/m (shown by the black trend line) over that timeframe. The peak PMcoarse daily average concentration for both 2011 and 2012 was found in April. As more data continues to be collected, it will be observed for possible trends or seasonal variations. 49 Georgia Department of Natural Resources Environmental Protection Division Concentration (g/m3) 2012 Georgia Ambient Air Surveillance Report 25 20 15 10 5 0 Section: Chemical Monitoring Activities Figure 41: PMcoarse Daily Averages, 2011-2012 HEALTH IMPACTS At this point, there is a limited amount of available data on health effects of PMcoarse material. Studies have shown that short-term exposure to high levels of ambient PMcoarse is associated with decreased lung function, increased hospital admissions for respiratory systems and heart disease, and possible premature death. Efforts are being made to collect more information on sources, characteristics and toxicity levels of PMcoarse that will help with understanding potential health effects. MEASUREMENT TECHNIQUES Georgia EPD measures PMcoarse with two beta attenuation particle monitors networked together. Both units are identical except for the inlet size. The PM10 unit has an inlet that only allows particles of 10 microns or smaller in size, while the PM2.5 unit has a Very Sharp Cut Cyclone (VSCC) inlet allowing only particles of 2.5 microns in size or smaller. At the beginning of each hourly measurement cycle, beta rays containing 14C are emitted across clean filter tape, and then measured with a photomultiplier tube with a scintillator. Next, air is sampled through the clean spot on the filter tape. The particulate matter is collected on the tape, and the beta rays are measured across the dirty spot. The difference between the clean and dirty spots determines the concentration. A PMcoarse board and synchronization cable connects the two samplers. Each hour, the PM10 sampler measures the PM10 concentration, collects the PM2.5 concentration from the PM2.5 sampler, and calculates the PM10-2.5 concentration. ATTAINMENT DESIGNATION Currently, there is no attainment standard for PMcoarse. PMcoarse measurements are performed to support the regulatory, analytical, and public health purposes of the program. While it is understood that these PMcoarse particles are harmful, the severity and type of health outcomes, rural versus urban area sources, and composition are not well understood. By collecting data about current concentrations, researchers can later compare Georgia EPD's data with health data to better understand the health effects. For a map of that includes the location of Georgia EPD's PMcoarse monitor, refer to Figure 36 in the previous section. 50 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities PM2.5 The U.S. EPA defines 2.5 particulate matter as solid particles and liquid droplets present in the air that are less than or equal to 2.5 microns in diameter. These particles and droplets are invisible to the naked eye. However, collectively, they may appear as a fog-like haze or clouds and are often referred to as "fine" particles. Fine particles are produced by various sources, including fires, industrial combustion, residential combustion, and vehicle exhaust (Figure 42 and Figure 43, on the next page). However, fine particles are also formed when combustion gases are chemically transformed. Fine particles can soil and accelerate the deterioration of man-made materials. In addition, fine particles impair visibility and are an important contributor to haze, particularly in humid conditions. The visibility effect is roughly doubled at 85% relative humidity as compared to humidity under 60% (U.S. EPA, 2004a). Based on data from EPA's Air Emission Sources for 2008, Georgia's primary source of PM2.5 emissions is fires, with over 68,000 tons attributed to this emission source. This information is displayed in Figure 42. Figure 43, on the next page, shows a spatial view of Georgia's PM2.5 emissions, also from EPA's Air Emission Sources, based on 2008 data. Considerable effort is being undertaken to analyze the chemical composition of fine particles (PM2.5) so that pollution control efforts can be focused in areas which create the greatest hazard reductions. Therefore, Georgia currently monitors fifty-three (53) particle species, which include gold, sulfate, lead, arsenic, and silicon. This speciation data is discussed further in the PM2.5 Speciation section. (From EPA's Air Emissions Sources) Figure 42: Common Sources of Particulate Matter 2.5 in 2008 51 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities (From EPA's Air Emissions Sources) Figure 43: Particulate Matter 2.5 Emission in Georgia in 2008 Spatial View HEALTH IMPACTS Fine particles can penetrate into the sensitive regions of the respiratory tract, which make them a health concern. Recently published community health studies indicate that significant respiratory and cardiovascular-related problems are associated with exposure to fine particle levels below the existing particulate matter standards. In addition, fine particles are likely to cause the most serious health effects, which include premature death, hospital admissions from respiratory causes, and increased respiratory problems. Long-term exposure to particulate matter may increase the rate of respiratory and cardiovascular illnesses and reduce the life span of an individual. Some data also suggests that fine particles can pass through lung tissues and enter the bloodstream. Therefore, children, the elderly, and individuals with cardiovascular disease or lung diseases such as emphysema and asthma are especially vulnerable. MEASUREMENT TECHNIQUES PM2.5 mass concentrations are measured with two types of methods. These two techniques consist of an integrated method and a continuous method. At sites where mass PM2.5 samples are taken on an integrated basis, the samples are measured using very similar techniques utilized for measuring PM10. The official reference method requires that samples are collected on Teflon filters with a PM2.5 sampler for 24 hours. A specialized particle size sorting device is used to filter the air, collecting only particles 2.5 microns in size and smaller. The filters are weighed in a laboratory before and after the sampling period. The change in the filter weight corresponds to the mass weight of PM2.5 particles collected. That mass weight, divided by the total volume of air sampled, corresponds to the mass concentration of the particles in the air for that 24-hour period. The reference method filters are used for attainment determinations. However, due to the delay in collecting each filter, shipping it to the laboratory, and weighing, weeks may pass before the results are known. Although this method is very accurate, it is not useful for real-time determinations of PM2.5 concentrations in ambient air. At sites where the continuous method is utilized, Georgia EPD uses two types of instruments. One type GA EPD uses is the beta attenuation method. The continuous monitor measures and records hourly particulate mass concentrations in ambient air. The monitor consists of three basic components; the central unit, the sampling pump and the sampling inlet hardware. In order to sample particles that are 2.5 microns or less, the inlet is designed to cut out particles larger than 2.5 microns 52 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities in size. The monitor uses beta ray attenuation to calculate collected particle mass concentrations in units of micrograms per cubic meter (g/m3). A 14C element (60 Ci +/- 15 C) emits a constant source of low-energy electrons, also known as beta particles. The beta rays are attenuated as they collide with particles collected on a filter tape. The decrease in signal detected by the scintillation counter is inversely proportional to the mass loading on the filter tape. The pump turns on at the beginning of the hour and runs for 50 minutes. During the last 10 minutes of the hour, the pump turns off while the tape transport operates, final mass readings are collected, and self-tests are performed. PM2.5 concentrations are displayed on the front panel and sent to the analog or digital output. The sampling method for the BAM type of continuous PM2.5 monitor was approved as Federal Equivalent Method (FEM) in Notices of the Federal Register/Vol.73, No.49 dated March 12, 2008 when used with a "Very Sharp Cut Cyclone". When GA EPD begins operating the continuous BAM as an FEM with a "Very Sharp Cut Cyclone", these samplers will be used for making attainment decisions relative to the NAAQS. As of January 1, 2011, Georgia EPD began running a BAM as an FEM sampler at the South DeKalb site (associated with the PMcoarse unit described above), and this sampler can be used for attainment designations. At the other locations where Georgia EPD samples PM2.5 on a continuous basis, the tapered element oscillating microbalance (TEOM) method is used. These monitors use an inline PM2.5 cyclone for particle size selection and an inline Sample Equilibration System (SES), which uses a diffusion drying technique to minimize water vapor interference with the particle mass measurement. The instrument oscillates the sample filter on a microbalance continuously while particles are collected from ambient air. By measuring the change in the oscillation frequency, the change in filter mass can be determined. PM2.5 concentrations are displayed on the front panel and sent to the analog or digital output. As configured in the Georgia ambient air monitoring network, these analyzers (TEOM) are not approved as reference or equivalent method, and the data collected from these samplers cannot be used for making attainment decisions relative to the NAAQS. Both types of PM2.5 continuous samplers are used to support the development of air quality models and forecasts, including the Air Quality Index (AQI), and provide the public with information about pollutant concentrations in real time. Continuous PM2.5 data is reported every hour, at fifteen minutes after the end of each hour, on Georgia's Ambient Air Monitoring web page located at http://www.air.dnr.state.ga.us/amp/index.php. The immediate availability of this data allows the public to make informed decisions regarding their outdoor activities. Figure 44 shows the location of Georgia's PM2.5 FRM monitors and Figure 45, on the following page, shows the location of PM2.5 continuous and speciation monitors. 53 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 44: PM2.5 Federal Reference Method Monitoring Site Map 54 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 45: PM2.5 Continuous and Speciation Monitoring Site Map 55 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities ATTAINMENT DESIGNATION In order for an area to be in attainment of the national primary and secondary annual ambient air PM2.5 standard, the area must have an annual arithmetic mean concentration less than or equal to 15.0 micrograms per cubic meter [62 FR 38711, July 18, 1997]. In addition, the 24-hour primary and secondary standard requires that the three year average of the 98th percentile of the 24-hour concentration be less than or equal to 35 micrograms per cubic meter [71 FR 61144, October 17, 2006]. All sample analyses used for determining compliance with the standards must use a reference method based on information present in 40 CFR Appendix L or an equivalent method as designated in accordance with Part 53. As can be seen in Figure 46 on the following page, the three-year averages of 98th percentile of PM2.5 24-hour data are compared to the 24-hour standard of 35 g/m3. For the 2003-2006 data, there were no exceptional events to consider. The 2007 data was affected by the Sweat Farm/Big Turnaround/Bugaboo Fire in the Okefenokee Swamp. To show the complete data set that was collected, the 2007 data includes the exceptional event data that was taken out for regulatory purposes. Therefore, in Figure 46 the three-year average calculations including the 2007 data (20052007, 2006-2008, and 2007-2009) are not a regulatory comparison to the 24-hour standard. The 98th percentile of 24-hour average concentrations have consistently decreased from the 2004-2006 to the 2010-2012 averages for almost all the sites. A recent trend in the past two three-year averages (20092011, 2010-2012) shows a slight increase in the values at the Savannah-Mercer, Savannah-Market Street and Valdosta sites. A wildfire took place in the Okefenokee Swamp (Honey Prairie Fire) in the summer of 2011. GA EPD believes that the PM2.5 concentrations in the Savannah MSA, and the Valdosta MSA (to a lesser extent) were influenced by this wildfire. The impact of the Honey Prairie Fire on PM2.5 concentrations, and a request that the affected data not be used for regulatory purposes will be submitted to the U.S. EPA in a separate exceptional event report. All of the 2010-2012 98th percentile of 24-hour averages (shown in purple) are well below the standard of 35 g/m3. 56 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Gordon Sandersville Rossville Augusta Bungalow Rd. Augusta Med. Col. Yorkville Columbus Cussetta Rd. Columbus Airport** Columbus H.D. Valdosta Warner Robins Gainesville Gwinnett 35 g/m3 limit Site Brunswick Atl. F.S. # 8* Atl. E. Rivers Sch. Rome*** Albany Doraville South DeKalb Powder Springs Kennesaw Forest Park Athens College Station Rd.** Sav. Mercer Sav. Market St. Macon Forestry Macon Allied Chem. 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 98th Percentile Concentration (g/m3)+ 04-06 05-07 06-08 07-09 08-10 09-11 10-12 + Includes all data from 2007 that was excluded for exceptional events * Site was shut down from 9/06 to 12/08; averages not complete 3 years ** Sites established in 2005 *** Sites consolidated in 2009, data combined for Rome-Coosa Elem and Rome-Coosa High Figure 46: PM2.5 Three-Year 24-Hour Averages, By Site 57 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 47, on the next page, also shows a non-regulatory comparison of three-year averages of annual PM2.5 data to the annual standard of 15.0 g/m3. This graph also includes the PM2.5 exceptional event data for 2007 to show the complete data set that was collected. Therefore, in Figure 47 the 2005-2007, 2006-2008 and 2007-2009 annual averages are not a regulatory comparison to the standard. There is an overall continual decreasing trend in the annual PM2.5 data since the 2004-2006 design value year. For the 2010-2012 design values (shown in purple), the lowest was 9.0 g/m3 at the Brunswick site and the highest was 13.1 g/m3 at the Macon-Allied. For additional PM2.5 summary data, see Appendix A. 58 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Gordon Sandersville Rossville Augusta Bungalow Rd. Augusta Medical Col. Yorkville Columbus Cusseta Rd. Columbus Airport Columbus Health Dept. Valdosta Warner Robins 15.0 g/m3 limit Site Gainesville Gwinnett Brunswick Atlanta Fire Station # 8** Atlanta E. Rivers School Rome*** Albany Doraville South DeKalb Powder Springs Kennesaw Forest Park Athens College Station Rd.* Savannah Mercer Savannah Market St. Macon Forestry Macon Allied Chem. 0 2 4 6 8 10 12 14 16 18 Concentration (g/m3)+ 04-06 05-07 06-08 07-09 08-10 09-11 10-12 + Includes all data for 2007 that was excluded for exceptional events * Site established 2005; 04-06 and 05-07 averages incomplete ** Site was shut down 9/06 to 12/08; averages do not include three full years until 09-11 *** Sites consolidated in 2009, data combined for Rome-Coosa Elem and Rome-Coosa High Figure 47: PM2.5 Three-Year Annual Averages, By Site 59 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities The PM2.5 annual standard attainment and nonattainment designations require three years of monitoring data. Therefore, Georgia's initial attainment status was not determined until late 2004. Based on the three years of data (2001-2003), EPA officially declared several areas of Georgia in nonattainment of the annual standard. Nonattainment areas included Walker and Catoosa counties, which are a part of the metro Chattanooga nonattainment area. All of Bibb County and portions of Monroe County were included in the Macon nonattainment area. Floyd County itself was declared a nonattainment area. Finally, the metro Atlanta nonattainment area was also declared. This includes Barrow, Bartow, Carroll, Cherokee, Clayton, Cobb, Coweta, DeKalb, Douglas, Fayette, Forsyth, Fulton, Gwinnett, Hall, Henry, Newton, Paulding, Rockdale, Spalding, and Walton Counties, along with portions of Heard and Putnam Counties. Figure 48, on the next page, illustrates the boundaries of Georgia's four PM2.5 annual standard nonattainment areas. Currently, based on 2007-2009 data, all of Georgia is meeting the PM2.5 annual standard, but has not been officially designated as in attainment. For attainment designations to be official, the maintenance state implementation plan (SIP) needs to be submitted and approved by EPA. GA EPD has submitted the maintenance SIP to EPA and is awaiting approval. For the PM2.5 24-hour standard, the entire State of Georgia is classified as in attainment. The 24-hour standard is also based on three years of monitoring data, and this attainment status is based on the 2005-2007 data. 60 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Figure 48: Georgia's PM2.5 Nonattainment Area Map Figure 49, on the next page, shows maps that were taken from the EPA document "Our Nation's Air Status and Trends through 2010". The first map shows PM2.5 annual average concentrations across the United States for 2010, and the second map shows the 24-hour average concentrations. This gives a comparison of Georgia's PM2.5 data, related to the rest of the country. It appears that for Georgia, the annual average concentrations were in the 3.1-12.0 g/m3 (dark blue) and 12.1-15.0 g/m3 (light blue) ranges. The 24-hour average concentrations were in the 16-35 g/m3 (light blue) range across the state. 61 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Annual Concentrations Section: Chemical Monitoring Activities Daily Concentrations (From EPA's "Our Nation's Air- Status and Trends through 2010") Figure 49: PM2.5 Annual and 24-Hour Concentrations across the United States, 2010 62 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities PM2.5 SPECIATION As required by the national PM2.5 speciation program (40 CFR 58), EPD monitors the mass concentration of fine particulate matter (in micrograms per cubic meter of air) along with the chemical composition of those particles. Attempts to control the concentration of fine particulate matter are considered a national priority, and are reliant upon listings in the National Ambient Air Quality Standards. Therefore, regulations intended to reduce levels of fine particulate matter are now being implemented on a widespread basis. The desired reduction of fine particulate matter concentrations is expected to produce benefits in human health and assist in the improvement of visibility by reducing the presence of haze. It is known that particulate matter has varying health effects depending on their size and chemical composition. The particles that compose fine particulate matter are not uniform. While they are all smaller than 2.5 microns in diameter, size does vary. Some fine particles are emitted into the air directly from engine exhaust, fossil fuel combustion, unpaved roads, and the tilling of fields; others are formed in the atmosphere through reactions between gaseous pollutants. Each individual particle, regardless of its source, has a distinct chemical composition. The overall composition of all particles that make up the fine particulate matter in a given volume of air may also vary, depending on local sources and a variety of other factors. Within the make-up of the particulate matter, some chemicals are more toxic than others. There has been some disagreement on whether the quantity or toxicity of fine particulate matter is most responsible for health concerns. This reinforces the need to monitor and analyze both the species of particulate matter and weight of the species. Georgia currently monitors fifty-three species, which include gold, sulfate, lead, arsenic, and silicon. However, there are only approximately six chemicals that are detected frequently. Of these, sulfate and organic carbon are detected in the highest concentrations, with magnitudes of up to five to nine times greater than the other major species. Figure 50 illustrates the average concentrations of these six chemicals from 2003 to 2012. The chemical elements typical of the Earth's crust are grouped together as "crustal". All of the sites are shown for one bar, showing how each site makes up the total of each of the major constituents of the speciation data. Note that the Rossville site began collecting data in 2005; therefore, the blue bars are not included in the 2003 and 2004 data. With the exception of the 2007 data, which was affected by the Okefenokee Swamp wildfire, there seems to be a general downward trend in the data. Below the figures is a listing of the most significant chemical constituents of fine particulate matter. Refer to Figure 45 for a map of Georgia's PM2.5 Speciation monitors. 63 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Other Crustal Nitrate Species Sulfate 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 0 5 10 15 20 25 30 35 40 45 50 55 Concentration (ug/m3) Organic Carbon Elemental Carbon Ammonium Ion Macon Athens Douglas South DeKalb Rome* Columbus Augusta Rossville** * Rome consolidated 2009 **Rossvile started 2005 Figure 50: PM2.5 Speciation, by Species, 2003-2012 64 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities PREDOMINANT SPECIES FOUND IN PM2.5 Ammonium Ion: commonly released by fertilizer production, livestock production, coke production, and some large refrigeration systems. Ironically, it can be emitted by NOx control systems installed on large fossil fuel combustion systems, which use ammonia or urea as a reactant. Sulfate products: formed during the oxidation of SO2 in the atmosphere. SO2 is primarily produced by coal burning boilers. Nitrate products: formed through a complex series of reactions that convert NOx to nitrates. Vehicle emissions and fossil fuel burning produce NOx. Crustal products: components that are the result from the weathering of Earth's crust. They may include ocean salt and volcanic discharges. Crustal products include aluminum, calcium, iron, titanium, and silicon. These components are released by metals production, and can be resuspended in the atmosphere by mechanisms that stir up fine dust, such as mining, agricultural processes, and vehicle traffic. Elemental carbon: carbon in the form of soot. Sources of elemental carbon include diesel engine emissions, wood-burning fireplaces, and forest fires. Organic carbon: consist of hundreds of organic compounds that contain more than 20 carbon atoms. These particles may be released directly, but are also formed through a series of chemical reactions in the air, mostly as a result of the burning of fossil fuels and wood. Data on the composition of fine particulate matter is a useful input to scientific models of air quality. Ultimately, it helps scientists and regulators track the progress and effectiveness of newly implemented pollution controls. The data also improves scientific understanding of the relationship between particle composition, visibility impairment, and adverse human health effects. Figure 51 presents a different view of the above PM2.5 speciation data to facilitate visualization of trends. Each site is shown with all species making up the composition of each bar. Each year is shown separately. 65 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities Rossville** Augusta Columbus Rome* Species 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 0 2 4 6 8 10 12 14 16 18 South DeKalb Douglas Athens Macon Concentration (ug/m3) Ammonium Ion Elemental Carbon Organic Carbon Sulfate Nitrate Crustal Other *Rome consolidated 2009 **Rossville started 2005 Figure 51: PM2.5 Speciation, by Site, 2003-2012 66 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Chemical Monitoring Activities To look at the data by site, there is a general trend downward of the PM2.5 speciated parameters, except in 2007 when the data was affected by the Sweat Farm/Big Turnaround/Bugaboo Fire in the Okefenokee Swamp, as discussed in the PM10 and PM2.5 sections. The rural background site, General Coffee, continues to show the smallest total average concentration. In 2012, the General Coffee site showed an overall concentration of approximately 5.8 g/m3. The remaining sites had overall concentrations of 7 to 8.5 g/m3. Ammonium ion concentrations (shown in pink) are relatively even statewide, with concentrations lowest at the General Coffee site. The concentrations ranged from 0.24 g/m3 at the General Coffee site to 0.57 g/m3 at the Athens site in 2012. Ammonium ion is the third largest single contributor to the total speciation make up. The Rome area has the highest elemental carbon concentration, 0.84 g/m3 shown in burgundy. Cities with less heavy vehicle traffic generally have lower concentrations. The General Coffee site has the lowest elemental carbon concentration, with 0.20 g/m3 in 2012. Organic carbon concentrations (shown in green) are relatively consistent throughout the state, usually consisting of about 3-4 g/m3 of the total speciation concentration. The General Coffee site collected a slightly lower concentration of 2.5 g/m3. Organic carbon concentrations are much higher than typical ammonium ion or elemental carbon concentrations, having one of the largest contributions to the total PM2.5 mass concentrations. Sulfate (shown in dark blue) is also found in higher concentrations, with concentrations around 1.5-2.0 g/m3 in 2012. Concentrations are relatively consistent statewide, though somewhat lower in rural areas, and their relatively large observed mass means that they are also a major contributor to overall PM2.5 mass concentrations. Nitrate concentrations (shown in purple) are relatively small (0.21-0.61 g/m3 in 2012), usually contributing the fourth or fifth largest single component of the total five major constituents. Atmospheric forms of nitrate can be formed from the conversion of NOx. Other forms of nitrate can be found in fertilizers, animal and human organic waste, medications, and used in welding. Crustal matter concentrations (shown in gray) are generally one of the lowest speciation concentrations (0.19-0.49 g/m3 in 2012) and consistent in most areas. Rome and Macon have in some years recorded unexpectedly high crustal matter concentrations. This may be attributed to local industry, or possibly a sign of poor dust control at agricultural, construction, or mining operations in those areas. The section labeled `Other' (shown in orange) is a make-up of all the rest of the compounds not included in the five major contributors or crustal make-up. This is a total of the remaining 43 compounds in the speciation sample. Concentrations ranged from 0.93 to 1.1 g/m3 in 2012. For PM2.5 speciation summary data, see Appendix B. To show the distribution of Georgia's 2012 PM2.5 annual speciation averages collected across the state, the following map was produced. The regional similarities and differences of the PM2.5 species composition become apparent from this analysis. All across the state, organic carbon (pink) and sulfate (peach) show the greatest contribution of the all the PM2.5 species collected. The Rome and Atlanta sites have more contribution of elemental carbon, while the Macon site collects more of the crustal species. Ammonium ion (green) and nitrate (light green) also show relatively more contribution at the Athens site, compared to the other sites. 67 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Rossville Section: Chemical Monitoring Activities Rome Atlanta Athens Columbus Macon Augusta Douglas Figure 52: 2012 Annual Averages of PM2.5 Composition Data in Georgia MEASUREMENT TECHNIQUES Particle speciation measurements require the use of a wide variety of sampling and analytical techniques, but all generally use filter media to collect the particles to be analyzed. Laboratory techniques currently in use are gravimetric (microweighing); X-ray fluorescence and particle-induced X-ray emission for trace elements; ion chromatography for anions and selected cations; controlled combustion for carbon; and gas chromatography/mass spectroscopy (GC/MS) for semi-volatile organic particles. ATTAINMENT DESIGNATION Particle speciation measurements are performed to support the regulatory, analytical, and public health purposes of the program. Currently, there are no ambient air quality standards regarding the speciation of particles. 68 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations PHOTOCHEMICAL ASSESSMENT MONITORING STATIONS (PAMS) GENERAL INFORMATION Ozone is the most prevalent photochemical oxidant and an important contributor to photochemical pollutants. The understanding of the chemical processes in ozone formation and the specific understanding of the atmospheric mixture in nonattainment areas nationwide are essential. To better understand the chemical processes and develop a strategy for solving those problems, EPA revised the ambient air quality surveillance regulations. In February 1993, Title 40, Part 58 of the Code of Federal Regulations (40 CFR Part 58) was developed to include provisions for enhanced monitoring of ozone, oxides of nitrogen, volatile organic compounds (VOCs), selected carbonyl compounds, and the monitoring of meteorological parameters. These parameters would be monitored at Photochemical Assessment Monitoring Stations (PAMS). Stated in Title 40, Part 58 of the Code of Federal Regulation (40 CFR Part 58), the increased monitoring of ozone and its precursor concentrations allows for the characterization of precursor emissions within the area, transport of ozone and its precursors, and the photochemical processes leading to nonattainment. By expanding on the study of ozone formation, PAMS monitoring sites better serve as a means to study trends and spatial and diurnal variability. As described in the Technical Assistance Document (TAD), PAMS monitoring was to be implemented in cities that were classified as serious, severe, or extreme for ozone nonattainment. The classifications were based on the number of exceedances of the ozone standard, and the severity of those exceedances. Nineteen areas nationwide were required to implement a PAMS network. In the Atlanta metropolitan area, a network of four sites was established beginning in 1993. The monitoring sites were selected depending on the pollutants monitored in relation to the prevailing winds in the area. The Yorkville site serves as a Type 1 site. It is a rural background site, upwind of the city, which aids in determining the role of transport of pollutants into the Atlanta area. The South DeKalb and Tucker sites were the primary and secondary wind directions for an urban core-type site, serving as Type 2 sites. These sites are expected to measure the highest precursor concentrations of NOx and VOCs in the Atlanta area. The Conyers site is the downwind site where titration of the precursors has occurred and the ozone concentrations should be at their highest. The Conyers site serves as a Type 3 site. Until the end of 2006, this was the setup of the PAMS network. At the end of 2006, the Tucker site was shut down. From that point, South DeKalb has served as the urban core-type site. When the PAMS network was originally designed, there was a plan for a Type 4 site, which samples the air once it has returned to background levels far downwind from the metropolitan area. However, when the network was instituted, this type of site was not used. The PAMS network as it was set up for the 2012 monitoring year can be seen in Figure 53, on the next page. 69 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations Figure 53: PAMS Monitoring Site Map 70 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations Of the fifty-six PAMS compounds monitored, the same volatile organic compounds (VOCs) consistently show the highest average concentrations at all three sites. These compounds include isoprene, m/p xylene, toluene, propane, ethane, isopentane, n-butane and n-pentane. Propane, ethane, isopentane, n-butane, and n-pentane have a limited reactivity for ozone formation, and therefore are the most prevalent of the volatile organic compounds measured. However, when the characterization of the top compounds is based upon contributions to ozone formation potential, the list is slightly different. Isoprene, the tracer for VOCs emissions from vegetation, is by far the largest contributor to ozone formation at every site. Isoprene is a 5 carbon organic compound naturally released in large quantities by conifer trees. These trees are very abundant in the Southeastern United States, contributing a significant portion to the overall carbon loading of the atmosphere in this region. Isoprene's chemical structure makes it a highly reactive substance with a short atmospheric lifetime and large ozone forming potential. Figure 54, below, shows the seasonal occurrence of isoprene from 2003 to 2012. This figure represents a combination of the 6-day, 24-hour data shown as monthly averages over the ten years from the three PAMS sites, and concentrations are given in parts per billion Carbon (ppbC). Evidence of isoprene's natural origin is shown in this figure, where the ambient concentration is essentially nonexistent from November to May. 12.0 Average Annual Concentration (ppbC) 10.0 8.0 6.0 4.0 2.0 0.0 J F M A M J J A S O N D Month South DeKalb Yorkville Figure 54: Average Yearly Profile of Isoprene, 2003-2012 Conyers 71 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations The anthropogenic compounds detected at all sites with the highest ozone formation potential were toluene, m/p xylene, propylene, ethylene, and isopentane. The sources for these five compounds are varied. All five compounds are emitted by mobile sources, with ethylene being an important tracer for vehicle emissions. Toluene (generally the most abundant species in urban air), m/p xylene, and isopentane are also emitted by solvent use and refinery activities. Toluene reaches the air from a variety of sources such as combustion of fossil fuels and evaporative emissions. This hydrocarbon is in motor vehicle fuel and is also used as a common solvent in many products such as paint. It has a substituted benzene ring possessing modest atmospheric reactivity. Figure 55 below, compares the seasonal occurrence of toluene with monthly averaged data from 2003 through 2012. Again, this figure is a combination of the 6-day, 24-hour data from the three PAMS sites, and concentrations are given in parts per billion Carbon (ppbC). Annual Average Concentration (ppbC) 8.00 7.00 6.00 5.00 4.00 3.00 2.00 1.00 0.00 J F M A M J J A S O N D Month South DeKalb Yorkville Figure 55: Toluene Average Annual Occurrence, 2003-2012 Conyers As shown in Figure 55, above, the atmospheric levels of toluene are relatively constant throughout the year, suggesting a steady level of emissions year-round. Over the past ten years, an occasional spike in concentration has occurred without evidence of a pattern. Overall, the PAMS site that is situated in the urban area (South DeKalb) has slightly higher levels of toluene, while the sites located on the outskirts of the Atlanta metropolitan area (Yorkville and Conyers) show lower levels of toluene. 72 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations In the following graph, Figure 56, the daily profiles of toluene and isoprene are plotted. This graph uses data gathered in the summer, and shows a constant background of toluene emissions with higher levels resulting from morning and evening rush hour traffic. The graph shows the typical diurnal, or daily, profile for a typical urban area. During morning hours, when the nocturnal inversion has not yet broken, emissions become trapped within the boundary layer, resulting in a temporary increase in atmospheric concentration. Nighttime toluene levels are constant from midnight to 5:00 am. From 6:00 am to 7:00 am, increased vehicular activity releasing emissions into an atmosphere with limited dispersing ability produces an increase in the ambient concentration. This behavior is typical of area source anthropogenic emissions with modest to long atmospheric lifetimes. Isoprene, on the other hand, exhibits very different behavior. At night, emission levels are at zero as photosynthesis ceases. At sunrise (about 6:00 am) concentrations begin to rise and continue to do so throughout the daylight hours. The vertical flux, or mass input per unit area, in the atmosphere of this substance is massive, being only slightly influenced by the enhanced mid-morning mixing. This effect can be seen at 9:00 am when a slight drop in concentration occurs followed by a quick resumption in rise. Concentration (ppbC) 12.0 10.0 8.0 6.0 4.0 2.0 0.0 Time of Day Toluene Isoprene Figure 56: Toluene & Isoprene, Typical Urban Daily Profile 73 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report CARBONYL COMPOUNDS Section: Photochemical Assessment Monitoring Stations Carbonyl compounds define a large group of substances, which include acetaldehyde, acrolein, and formaldehyde. These compounds can act as precursors to ozone formation. Some of the sources of carbonyl compounds include vehicle exhaust and the combustion of wood. Depending on the amount inhaled, exposure to these compounds can cause irritation to the eyes, ears, nose, and throat, dizziness, and damage to the lungs. Each of the seven carbonyl compounds that Georgia EPD monitors is discussed further in the following paragraphs. The South DeKalb site is part of both the PAMS network and the National Air Toxics Trends Stations (NATTS) network, and collects samples every six days throughout the year, and every three hours throughout the summer. For a map of locations monitoring carbonyl compounds, see Figure 57, on the next page. Acrolein is primarily used as an intermediate in the manufacture of acrylic acid. It can be formed from the breakdown of certain organic pollutants in outdoor air, from forest fires and wildfires, as well as from vehicle exhaust. It is also found in cigarette smoke. Acetaldehyde is mainly used as an intermediate in the production of other chemicals. Acetaldehyde is formed as a product of incomplete wood combustion (in fireplaces and woodstoves, forest fires, and wildfires), pulp and paper production, stationary internal combustion engines and turbines, vehicle exhaust, and wastewater processing. Formaldehyde is used mainly to produce resins used in particleboard products and as an intermediate in the production of other chemicals. The major sources of emissions to the air are forest fires and wildfires, marshes, stationary internal combustion engines and turbines, pulp and paper plants, petroleum refineries, power plants, manufacturing facilities, incinerators, cigarette smoke, and vehicle exhaust. Acetone is used industrially as a reactant with phenol to produce bisphenol A, which is an important component of polymers. It is used in nail polish removers, superglue removers, and as a drying agent. It is also used to dissolve plastic. Acetone is highly volatile and evaporates quickly. Inhalation of acetone can lead to liver damage. Benzaldehyde is the simplest form of the aromatic aldehydes. It has an almond scent and is used in the food industry. It is also used as an industrial solvent, and is used in making pharmaceuticals, plastic additives, and aniline dyes. Liquid phase oxidation or chlorination of toluene can form benzaldehyde. In addition, benzaldehyde can be formed from a reaction between benzene and carbon monoxide. The combustion of gasoline, diesel fuel, wood burning, and incinerators emit benzaldehyde into the atmosphere. Butyraldehyde is used in the manufacture of synthetic resins, solvents, and plasticizers. It is emitted into the air by combustion of gasoline, diesel fuel, and wood. Propionaldehyde is a highly volatile compound that is produced or used in making propionic acid, plastics, rubber chemicals, alkyd resins, and is also used as a disinfectant and preservative. It is released into the atmosphere by combustion of gasoline, diesel fuel, wood, and polyethylene. 74 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations Figure 57: Carbonyls Monitoring Site Map 75 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations As part of the PAMS network, the South DeKalb site collects 3-hour samples of carbonyls during the summer months (June, July, and August). Samples are collected at hours 6:00, 9:00, 12:00, and 15:00, every three days. The average concentrations (shown in micrograms per cubic meter) of all the 3-hour samples of carbonyls collected during those months for 2005 through 2012 have been combined for a given hour and are shown in Figure 58. There are a few notable observations when evaluating the data from 2005 through 2012. The early morning ambient concentrations are generally lower for all constituents. Overall, most of the concentrations appear to peak at the 12:00 hour. There appears to be a cyclic trend, particularly for the compounds with higher concentrations, formaldehyde and acetone. Acetaldehyde, acetone, and formaldehyde continue to be the biggest contributors, and for the past two years the other three compounds (benzaldehyde, propionaldehyde, and butyraldehyde) have had no detections. 16 14 12 10 8 6 4 2 0 2005 2006 2007 2008 2009 2010 2011 2012 Figure 58: Average South DeKalb 3-Hour Carbonyls, June-August, 2005-2012 76 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations The next two graphs address 24-hour samples of carbonyls data. Due to the differences in sampling method, analysis method, and the sites collecting acrolein data, acrolein is discussed separately in later paragraphs. In Figure 59, below, the average concentration of the other six carbonyls is compared with the total number of detections at each of the sampling sites. Detections are shown as a percentage of the overall samples taken since the South DeKalb site collects data every six days with the PAMS and NATTS networks, while the Savannah and Dawsonville sites collect data every twelve days with the Air Toxics Network (discussed in next section). A detection of any given pollutant is counted as any number that is above half the limit of detection. To compare the data collected from 2005 to 2012, there are some notable changes. The Savannah site had a dramatic increase in concentration in 2010, but levels have dropped back down the past two years. The Dawsonville site had a visible increase in concentration in 2007 and 2010, but levels are also back down the past two years. The South DeKalb site has consistently had overall higher average concentrations, and the last two years has seen an uptick in total average concentrations. In 2012, percent detections ranged from 37% at the Savannah site, to 46% at the South DeKalb site. As stated earlier, carbonyls are emitted into the air by combustion of gasoline and wood, and have industrial uses. 35.0 100.0 Total Average Concentration (ug/m3) Percent Detections 30.0 75.0 25.0 20.0 50.0 15.0 10.0 25.0 5.0 0.0 0.0 Concentration Name of Site Detects 2005 2006 2007 2008 2009 2010 2011 2012 2005 2006 2007 2008 2009 2010 2011 2012 Figure 59: Average 24-Hour Carbonyl Concentrations and Number of Detects, by Site, 20052012 77 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations Figure 60, below, shows six of the seven species in the analyte group according to their statewide annual abundance, based on percentage of detections and average concentration. A graph of the seventh carbonyl, acrolein, is shown separately, as it is collected with the canister method and involves all the Air Toxics sites (discussed below). A gradient is evident from this graph below, with formaldehyde and acetone as the most abundant carbonyls. For the most part, it appears that the number of detections track the average concentration. With the higher average concentration, there are higher percent detections. Acetaldehyde does not follow this pattern, however, having a higher percentage of detections compared to lower concentrations. Generally, all the compounds had an increase in total average concentrations in 2010, mainly attributed to the Savannah site, as seen in the above graph. Since then, all average concentrations except formaldeyhde have dropped back down the past two years. Overall, percent detections decreased in 2012, and this contributes to the decrease in average concentrations. The proportion of each compound remained the same throughout all eight years of data, with the biggest contributors (formaldehyde, acetone, and acetaldehyde) continuing through the years. 30.0 100.0 25.0 75.0 20.0 15.0 50.0 10.0 25.0 5.0 0.0 0.0 Total Average Concentration (g/m3) Percentage of Detections Name of Carbonyl Species Concentration Detects 2005 2006 2007 2008 2009 2010 2011 2012 2005 2006 2007 2008 2009 2010 2011 2012 Figure 60: Average 24-Hour Carbonyl Concentrations vs. Number of Detects, by Species, 20052012 78 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations Since vehicle exhaust is a contributor to carbonyl concentrations, an analysis was done on daily traffic versus these compounds. Vehicle traffic volume data was obtained from the Georgia Department of Transportation's I-285 traffic counter site (089-3341) in closest proximity to the Georgia EPD air monitoring site at South DeKalb. Twenty-four hour carbonyl data was compared with total daily traffic volume for the year 2012 (Figure 61). Acetaldehyde and formaldehyde are shown in the graph below, as the other compounds had very little or no concentrations shown on the graph. Daily Traffic (Number of Vehicles) Concentration (g/m3) 180000 170000 70 160000 60 150000 50 140000 130000 40 120000 30 110000 20 100000 90000 10 80000 0 Number of Vehicles Acetaldehyde Formaldehyde Figure 61: Daily Traffic versus Select Carbonyls at South DeKalb, 2012 79 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations Although the featured carbonyl parameters are associated with vehicle exhaust, regression analysis of individual parameters versus the daily number of vehicles delivered no apparent correlation at the South DeKalb site (Figure 62 below). Formaldehyde vs. Traffic, 2012 80 Concentration (g/m) 70 60 y = 0.0001x R = -0.011 50 40 30 20 10 0 90000 100000 110000 120000 130000 140000 Number of Vehicles 150000 160000 170000 180000 Acetaldehyde vs. Traffic, 2012 12 Concentration (g/m) 10 y = 2E-05x 8 R = 0.0036 6 4 2 0 90000 100000 110000 120000 130000 140000 150000 Number of Vehicles 160000 170000 180000 Figure 62: Regression Analysis of Daily Traffic and Select Carbonyls at South DeKalb, 2012 Due to EPA research to improve acrolein sampling and analysis, a new method was developed by EPA and implemented in Georgia in July of 2007. The sampling method uses the volatile organic compounds (VOCs) canister collection method, and the analysis method uses gas chromatograph and mass spectroscopy (GC/MS). This change occurred due to EPA's findings during the new School Air Toxics Monitoring Initiative. For more information on this study, please see EPA's website, http://www.epa.gov/ttnamti1/airtoxschool.html. Georgia EPD began using the new method for the National Air Toxics Trends Station (NATTS) at the South DeKalb site and other Air Toxics sites (discussed in the next section). In previous years, acrolein was sampled, along with the six other carbonyls, with a dinitrophenylhydrazine (DNPH) cartridge method and analyzed with high performance liquid chromatography (HPLC) at select sites across the state. The DNPH sampling and HPLC analysis method were used on the data that is displayed in the three previous carbonyls graphs. Since acrolein is no longer collected with DNPH and analyzed with HPLC, it is not shown in the previous carbonyls graphs. Before the new methods were used, in 2005, there were a total of four detections above detection limit, in 2006 there were zero detections, and in 2007 there was one 80 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations detection above the detection limit in Georgia. With the canister collection, GC/MS analysis method, and the addition of Air Toxics sites, the number of acrolein detections above detection limit drastically increased the second half of 2007. All sites demonstrated more than 80% detection, and some had 100% detection (shown in orange in Figure 63, below) after July 2007. From 2007 to 2009, the average concentrations remained relatively stable. However, in 2010, there was a drastic increase in average concentrations. Every site had at least twice the 2009 concentration. The Savannah site had the highest increase from 0.34 g/m3 in 2009 to 4.25 g/m3 in 2010. This was followed by an equally dramatic decrease in concentration for 2011, with concentration levels reduced by half or more. For most sites, this downward trend continued with the 2012 data, with average concentrations returning to levels consistent with those prior to 2010. Acrolein may enter the environment as a result of combustion of trees and other plants, tobacco, gasoline, and oil. Additionally, it can be used as a pesticide for algae, weeds, bacteria, and mollusks (ATSDR, 2007c). The potential for acrolein to cause health effects is not well understood. At very low concentrations, it is an upper respiratory irritant. At very high concentrations it may produce more serious damage to the lining of the upper respiratory tract and lungs (ATSDR, 2007c; U.S. EPA, 2003). Average Concentration (g/m3) Percent Detections 4.5 100.00% 4 3.5 80.00% 3 60.00% 2.5 2 40.00% 1.5 1 20.00% 0.5 0 0.00% 2007 2008 Concentration 2009 2010 2011 Site 2012 2007 2008 Detects 2009 2010 Figure 63: Acrolein Concentrations and Percent Detections, 2007- 2012 2011 2012 MEASUREMENT TECHNIQUES A number of methods are used to conduct the PAMS hydrocarbon portion of the analyses. Throughout the year, 24-hour integrated volatile organic compounds samples are taken every sixth day at the PAMS sites (Conyers, South DeKalb, and Yorkville) and analyzed in the GA EPD laboratory for 56 hydrocarbon compounds. A SUMMA polished canister is evacuated to a nearperfect vacuum and attached to a sampler with a pump controlled by a timer. The canister is filled to greater than 10 psig. Then, the canister is analyzed using a gas chromatograph with mass spectroscopy detection (GC/MS). Additionally, during June, July, and August, hydrocarbon samples are analyzed hourly at the PAMS sites (Conyers, South DeKalb, and Yorkville) using a gas chromatography unit with a Flame Ionization Detector (FID). The gas chromatograph produces analyses of the ambient air for the same 56 hydrocarbons. 81 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Photochemical Assessment Monitoring Stations The carbonyls are sampled with two types of methods. One method includes an absorbent cartridge filled with dinitrophenylhydrazine (DNPH) coated silica that is attached to a pump to allow approximately 180 L of air to be sampled. The cartridge is analyzed using High Performance Liquid Chromatography. Twenty-four hour integrated samples are collected throughout the year, every 12 days at the Air Toxics sites (Dawsonville and Savannah) and every 6 days at the NATTS site (South DeKalb). Also, during June, July, and August, four integrated three-hour carbonyl samples are taken every third day at the NATTS site (South DeKalb). All analyses are conducted at the GA EPD laboratory. Another collection method is the canister sampler that is used for sampling volatile organic compounds (described above); acrolein is analyzed using this method. Specific annual summaries for the 2012 PAMS data may be found in Appendix C. ATTAINMENT DESIGNATION There are no specific ambient air standards for the hydrocarbon and aldehyde species measured. PAMS measurements are performed to support the regulatory, analytical, and public health purposes of the ambient air monitoring program. By performing these measurements, GA EPD can better understand the characterization of precursor emissions within the area, transport of ozone and its precursors, and the photochemical processes leading to nonattainment. In addition, by studying local atmospheric chemistry, it improves the ability to control the formation of secondary pollutants like ozone and particulate matter. By making such data available, scientists can study air quality and how it relates to human health. This data can serve to guide policymakers toward making decisions that protect public health. 82 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report AIR TOXICS MONITORING Section: Air Toxics Monitoring GENERAL INFORMATION Air toxic pollutants, or hazardous air pollutants (HAPs), are a group of air pollutants that have a wide variety of sources. Air toxic compounds are released from mobile sources (such as vehicles), stationary industrial sources, small area sources, indoor sources (such as cleaning materials), and other environmental sources (such as volcanoes and wildfires). The lifetime, transportation, and make-up of these pollutants are affected by both weather (rain and wind) and landscape (mountains and valleys). They can be transported far away from the original source, or be caught in rain and brought down to waterways or land. In addition, some HAPs that are no longer used, but were commonly used in the past, can still be found in the environment today. All of these air toxic pollutants can potentially have negative health and environmental effects. Negative effects on human health range from headaches, nausea, and dizziness to cancer, birth defects, problems breathing, and other serious illnesses. These effects can vary depending on frequency of exposure, length of exposure time, health of the person that is exposed, along with the toxicity of the compound. People can be exposed to HAPs by breathing contaminated air, consuming food or water contaminated by air pollutants, or touching contaminated water or soil. These air pollutants also affect the environment. Wildlife experiences symptoms similar to those in humans. Pollutants accumulate in the food chain. Many air pollutants can also be absorbed into waterways and have toxic effects on aquatic wildlife. Some of the substances tend to have only one critical effect, while others may have several. Some of the effects may occur after a short exposure and others appear after long-term exposure, or many years after being exposed. Exposure is not only through direct inhalation of the pollutant, but also through the consumption of organisms (such as fish) that have absorbed the pollutant. In order for GA EPD to expand the understanding of the quality of Georgia's air regarding ambient concentrations of hazardous air pollutants, GA EPD began state-sponsored monitoring activities. HAPs monitoring efforts were undertaken to provide a more complete picture of the state's air quality. In 1994, GA EPD conducted an intensive air quality study in Savannah (GADNR, 1996a). Following the study, in 1996, GA EPD conducted an additional study in Glynn County as part of a multimedia event with EPA (GADNR, 1996b). These studies provided detailed pictures of the air quality in local communities, but were not long-term studies and could not provide information on seasonal variation or trends. A reassessment of the air toxic monitoring program occurred, and in 1996 GA EPD embarked on establishing a statewide hazardous air pollutant-monitoring network. The network was not designed to monitor any one particular industry, but to provide information concerning trends, seasonal variations, and rural versus urban ambient concentrations of air toxics. In order to evaluate the rural air quality, two background sites were proposed: one in North Georgia and one in South Georgia. The majority of the other sites were located in areas with documented emissions to the atmosphere of HAPs exceeding one million (1,000,000) pounds per year as indicated by the 1991 Toxic Release Inventory (GADNR, 1993). After six years, the 2002 Air Toxics Network (ATN) consisted of fourteen sites statewide, including a collocated (where two sets of monitors sample side by side) site at Utoy Creek, which monitored for a common set of toxic compounds. From the list of 187 HAPs compounds identified by EPA, toxic compounds included metals, volatile organic compounds, and semi-volatile organic compounds. In addition, three of the ATN sites (Brunswick, Dawsonville, and Savannah) monitored carbonyl compounds (discussed in the previous section). In 2003, a National Air Toxics Trends site was added to the network at the South DeKalb site, bringing the total to fifteen air toxics sites. The National Air Toxics Trends Station (NATTS) network was established in 2003 and is intended for long-term operation for the purpose of discerning national trends. The NATTS Network consists of 27 sites nationwide, 20 urban and 7 rural. The South DeKalb 83 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring site monitors the same compounds as other air toxics sites, as well as hexavalent chromium, black carbon, and carbonyls (already being monitored with PAMS network). With the inception of the NATTS network, there was an effort to standardize detection limits for all air toxic monitoring and evaluate air toxics data at a level that would reflect potential cancer risk. Therefore, in 2004, the laboratory methodology was changed for the Air Toxics Network compounds, which lowered detection and reporting limits. This enabled analysis of a broader range of data. Instead of only seeing the higher numbers that were detected and using those numbers for average concentrations, now both sides of the spectrum show a truer average for each chemical. Also, including the lower concentrations for each chemical allows for a better understanding of what levels can cause chronic health problems and potential cancer risk. Seeing only the higher levels of concentration (spikes) only yields data useful for identifying acute health effects. However, with the lower concentration levels included in the data, there can be further assessment of potential chronic health effects and potential cancer risk. In addition, all possible effects of the analyzed chemicals can be viewed, with lower limits included in the data. In 2008, nine of the 15 Air Toxics samplers were discontinued due to budgetary constraints and lack of available personnel. The remaining six sites in the Air Toxics Network are reflected in the following subsections and included in the following maps of the current network. The following section discusses air toxic compounds, possible sources, monitoring techniques, 2012 findings, and a comparison of 2012 data to previous years. 84 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report METALS Section: Air Toxics Monitoring The metals subcategory includes antimony, arsenic, beryllium, cadmium, chromium, cobalt, lead, manganese, nickel, selenium, and zinc. Antimony is used as a hardener in lead for storage batteries, in matches, as an alloy in internal combustion engines, and in linotype printing machines. Antimony compounds are used in making materials flame-retardant, and in making glass, ceramic enamels, and paints. Forms of the antimony metal are also used in medicines, and can be found in gasoline and diesel exhaust. Arsenic occurs naturally at trace levels in soil and water. Most people are not exposed to arsenic through air pollution, but it can be found in food. The arsenic found in air comes mainly from the burning of coal or fuel oil, from metal smelters or iron foundries, and from the burning of waste. Beryllium is a lightweight and rigid metal and used in watch springs, computer equipment, and is used in the production of beryllium-copper as an alloying agent. This strong alloy is used to conduct heat and electricity in spot welding, electrical contacts, and high-speed aircrafts. Until 1949, beryllium was used in fluorescent lighting until it was determined to have caused berylliosis, a disease that primarily affects the respiratory system and skin. Beryllium in ambient air is mainly a result of the burning of coal or fuel oil. Cadmium emissions, like beryllium and arsenic, occur mainly from the burning of fossil fuels such as coal or oil. The incineration of municipal waste and the operation of zinc, lead, or copper smelters also release cadmium in the air. For nonsmokers, food is generally the largest source of cadmium exposure. Chromium sources include the combustion of coal and oil, electroplating, vehicle exhaust, iron and steel plants, and metal smelters. The emissions from these sources are a combination of elemental chromium and compounds including chromium ions. The most toxic form is hexavalent chromium. Cobalt is used as a pigment (blue and green coloring agent), as a drying agent for paints, inks and varnishes, and as a catalyst for the petroleum and chemical industries. It is used as an alloy for parts in turbine aircraft engines, corrosion-resistant alloys, magnets, battery electrodes, and steel-belted tires. Cobalt also has a medicinal use as a radioactive metal in radiotherapy. It is also found in gasoline and diesel exhaust. Cobalt is actually necessary to many forms of life, when ingested through the digestive tract, in small amounts, as a micronutrient. It is a central component of vitamin B-12. As with most micronutrients, however, human activity can cause it to accumulate in unnatural locations or in unnatural concentrations. In those cases, it may be harmful and is considered a pollutant. Lead is used in the manufacturing of batteries. The largest source of lead in the atmosphere used to be from the combustion of leaded gasoline. With the elimination of lead from gasoline, lead levels in the air have decreased considerably. Other sources of lead emissions include combustion of solid waste, coal, oils, emissions from iron and steel production, and lead smelters. Exposure to lead can also occur from food and soil. Children are at particular risk to lead exposure, because they commonly put hands, toys, and other items in their mouths that may come in contact with lead-containing dust and dirt. Lead-based paints were commonly used for many years. Flaking paint, paint chips, and weathered paint powder may be a major source of lead exposure, particularly for children. Manganese is a naturally occurring substance found in many types of rock and soil. It is ubiquitous in the environment and found in low levels in water, air, soil, and food. Manganese can also be released into the air by combustion of coal, oil, wood, and the operation of iron and steel production plants. 85 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring Nickel is found in the air as a result of oil and coal combustion, residential heating, nickel metal refining, lead smelting, sewage sludge incineration, manufacturing facilities, mobile sources, and other sources. Selenium is a by-product of mining and smelting sulfide ores, such as silver, copper, and pyrite. It is found in soils, and can also be released by burning coal. Selenium has photovoltaic and photoconductive properties and is therefore used in photocells and solar panels. It is used as a pigment (red coloring agent) in enamels and glass, and also as a toner in photographs and in photocopying. Selenium is found in gasoline and diesel exhaust. It is also a micronutrient, needed at very low levels for the health of all living creatures. However, it is normally absorbed through the digestive tract, and not desirable in the air. Zinc is found in gasoline and diesel exhaust. It is used to prevent corrosion of galvanized steel. It is also used in diecasting, and as part of battery containers. Zinc has been used as the primary metal for producing the U.S. penny since 1982. Zinc compounds are used to make white pigment, sunscreen, deodorant, calamine lotions, and pigments for glow in the dark items. It is also used in the rubber industry. Like selenium, zinc is also a micronutrient that is needed for the health of living beings when consumed through the digestive system. When found in the air, though, it may be considered a pollutant. For a map of the current metals monitoring locations, see Figure 64 on the next page. 86 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring Figure 64: Metals Monitoring Site Map 87 Georgia Department of Natural Resources Environmental Protection Division Percentage Detections 2012 Georgia Ambient Air Surveillance Report 100 90 80 70 60 50 40 30 20 10 0 Section: Air Toxics Monitoring 2005 2006 2007 Site 2008 2009 2010 Figure 65: Percentage of Metals Detections by Site, 2005-2012 2011 *From PM10 Fraction 2012 Figure 65 shows the percentage of metal species detected above the detection limit at each site for the years 2005 through 2012. Following EPA's guidance, a detection of any given pollutant is counted as any number that is above half the limit of detection. It is important to note that the South DeKalb metals sampler is designed to take the sample from the smaller PM10 fraction of the air as part of the NATTS network, while the other samplers in the Air Toxics Network collect samples from all the total suspended particles. Lower limits of detection (LOD) were introduced in September of 2004; therefore to be consistent, the data represented in these figures starts with the 2005 data. There have been only eight full years of data collected at the lower limits, therefore true trends may not be discernible at this time. In Figure 65, the distribution of metals at various locations across the state can be clearly examined, as well as any changes to pollutant levels in the past eight years. The distribution across these six sites is relatively similar. For all sites, the percent detections remain around 75% to 90% of the total samples collected. Variability across sampling locations is modest, considering the vast geographic distribution of the sites, and climatological and anthropogenic influences from local urban development. 88 Georgia Department of Natural Resources Environmental Protection Division Average Concentration (g/m3) Percent Detections 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring Figure 66 shows the network's percentage of detections above detection limit and total average concentrations by metallic species at all Air Toxics sites during 2005 through 2012. The detection of any given pollutant is counted as any number that is above half the limit of detection. One point of interest when looking at data is to track the percentage of detections along with the concentration. When examining this aspect, it appears that most metals had several detections, almost consistently up to 100%. Therefore, each metal detection contributes little concentration to the overall total concentration. This does not seem to be the case for zinc. While its detection frequency was almost the same as the other metals, zinc had the highest average concentration for all eight years. This would indicate that for each zinc detection, there was a higher concentration of that metal. Some metals including zinc, nickel, antimony, lead, chromium, and cadmium have been associated with emissions from tires and brake linings. The use of vehicles on Georgia's roads could be a reason for higher levels associated with some of these metals. With the concentrations of zinc being much higher than the other metals, zinc is explored further in Figure 67 (on the following page), which examines the concentrations of zinc by site. 0.16 100.0 0.14 90.0 80.0 0.12 70.0 0.1 60.0 0.08 50.0 0.06 40.0 30.0 0.04 20.0 0.02 10.0 0 0.0 2005 2006 2007 Concentration 2008 2009 2010 2011 Name of Metal 2012 2005 2006 2007 Detects 2008 2009 2010 2011 2012 Figure 66: Average Concentration and Percentage Detections of Metals, by Species, 2005-2012 89 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring Figure 67, below, investigates the total average concentrations of zinc, divided by site, more closely for 2005 through 2012. It is important to note that zinc does not have a health based screening value (see Risk Assessment section for more details) that is considered harmful to humans. In addition, zinc is not one of the 189 hazardous air pollutants; however, it is reported here for completeness. With a few exceptions, most sites have had a consistent level of zinc throughout the eight years of data. As noted earlier, the South DeKalb metals sampler is designed to take the sample from the smaller PM10 fraction of particles in the air, while the other samplers collect samples from all the total suspended particles. The lower levels at the South DeKalb site, in comparison, could be due to the larger particles (larger than PM10 size) being restricted by the sampler, indicating that some of the zinc sample could be lost in the larger, restricted fraction of particles. An obvious change over the eight years of data is the Macon site's 2009 average zinc concentration, which more than doubled from the 2008 average concentration. This data was investigated further; however, results were inconclusive as to the cause of the Macon site's higher values in 2009. The changes in zinc levels at the Macon site could be due to changes in local industry. Zinc can be released into the environment from mining, metal processing, steel production, burning coal, and burning certain wastes. In 2010 (shown in pink), the average zinc concentration for the Macon site decreased by about half again, resulting in a level near that of 2008. With the remaining 2010 zinc data, the Savannah site's average zinc concentration had a small increase, while the other four sites' average concentrations remained about the same as 2009 levels. In 2012, the General Coffee, South DeKalb and Savannah sites had a noticeable decrease from the average zinc concentrations in 2011. The additional air toxics sites continued to show zinc concentrations around the same level as seen in previous years. 0.060 Average Concentration (g/m3) 0.050 0.040 0.030 0.020 0.010 0.000 Site 2005 2006 2007 2008 2009 2010 2011 2012 Figure 67: Average Concentration Comparison of Zinc, by Site, 2005-2012 *From PM10 Fraction HEXAVALENT CHROMIUM (Cr6) Hexavalent chromium (chromium in its +6 oxidation state) in the environment is almost always related to human activity. Hexavalent chromium can be released into the atmosphere through the production of stainless steel, chrome plating, coating processes, and painting. It is also found in vehicle engines. The presence of chromium compounds is common at hazardous waste sites. From locations such as these, exposure of populations residing or working nearby can occur through inhalation of air containing particulates or mists of chromium compounds. These particles can also find their way into drinking water if soluble forms of chromium leach into groundwater. Human exposure can also occur 90 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring through skin contact with soil at hazardous waste sites. Hexavalent chromium is absorbed most readily through the lungs or digestive tract. Other forms of the metal, such as chromium in the +3 oxidation state, occur naturally in the environment and are not as efficient at entering the body. In general, hexavalent chromium compounds are more toxic than other chromium compounds. The toxicity of hexavalent chromium is in part due to the generation of free radicals formed when biological systems reduce hexavalent chromium to the +3 oxidation state. Effects in humans exposed occupationally to high levels of chromium or its compounds, primarily hexavalent chromium, by inhalation may include nasal septum ulceration and perforation, and other irritating respiratory effects. Cardiovascular effects, gastrointestinal and hematological effects, liver and kidney effects, and increased risks of death from lung cancer may also result from such exposure. In addition to the respiratory effects, exposure to chromium compounds can be associated with allergic responses (e.g., asthma and dermatitis) in sensitized individuals. Hexavalent chromium dioxide is a tetravalent chromium compound with limited industrial application. It is used to make magnetic tape, as a catalyst in chemical reactions, and in ceramics. Because of its limited industrial uses, the potential for human exposure is less for chromium dioxide than for the more industrially important hexavalent chromium and chromium +3 compounds. This is the eighth year hexavalent chromium has been monitored at the South DeKalb site, as part of the NATTS network. The data for 2005 through 2012 is presented in Figure 68. The sampler did not operate the last quarter of 2007 through part of May 2008; therefore, a gap in the data is shown. Observed concentrations range over an order of magnitude, from 0.01 to 0.3 ng/m3 (nanograms per cubic meter). To observe the lower data points, the maximum concentration shown on the graph is 0.10 ng/m3. The observed concentrations are represented with the points, the black line represents a moving average across the data set, and the yellow line represents the overall linear trend in the dataset. It appears that from 2005 through 2007 the hexavalent chromium concentrations were sporadic and included some higher values. Then from 2008 through 2012, the concentrations seem more consistent and lower. The highest data point of 0.3 ng/m3 was observed in 2006, while the highest data points from 2008 through 2012 were 0.09 ng/m3. As the data set continues to grow, possible seasonal variation in concentration or other trends may be observed. 0.10 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0.00 Moving Average Date Linear (Concentration) *sampler did not operate from 9/15/07 until 5/12/08 Figure 68: Hexavalent Chromium at South DeKalb Concentration (ng/m3) 91 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring VOLATILE ORGANIC COMPOUNDS (TO-14/15) Volatile organic compounds (VOCs) make up a group of chemicals from various industrial, stationary, and mobile sources. VOCs reach the atmosphere by way of evaporative emissions as well as incomplete combustion processes. Chlorinated compounds are very stable in the atmosphere, with lifetimes of several years. Dichlorodifluoromethane, a chlorinated compound, was the refrigerant of choice for automotive cooling. This material has not been manufactured since the mid-1990s (cars now use R-134a), yet dichlorodifluoromethane remains prevalent in the environment. Chloromethane is a volatile industrial solvent. Toluene is a major component of paints, solvents and is also present in gasoline. Benzene is found in vehicle emissions, evaporation from gasoline service stations, emissions from the burning of coal and oil, and in industrial solvents. Carbon tetrachloride and the Freons are generally used as refrigerants, industrial solvents, and as fire suppressants (though generally known as Halon in that application). The atmospheric reactivity of aromatic compounds is relatively high, with lifetimes in the weeks to months range. Figure 69 shows the statewide detection distribution of air toxic (TO-15) type volatile organic compounds (VOCs) from 2005 to 2012 across the state's Air Toxics Network. The detection of any given pollutant is counted as any number that is above half the limit of detection. The South DeKalb site has samples collected every six days; therefore, all of the site's detections are shown as a percentage of samples taken. The distribution is relatively even across the state, although the sites are located in different geographic regions, and have different local influences. The percentage of detections has remained relatively low throughout the eight years shown here. Out of all the VOCs samples taken, the percent detections have consistently been about 8% to 15%. 18.0 16.0 14.0 12.0 10.0 8.0 6.0 4.0 2.0 0.0 Percent Detections 2005 2006 2007 Site 2008 2009 2010 2011 2012 Figure 69: Total Volatile Organic Compounds Percent Detected per Site, 2005-2012 92 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring Figure 70, below, compares the relationship between the concentrations observed and percent detections above detection limit, showing the top ten compounds of the VOCs group that were detected for 2005 through 2012. Although there are 42 species in this analyte group, only a relatively smaller subset is typically detected with any regularity. The percentage of detections was derived using any detection that was above half of the method detection limit. To obtain the average concentration for compounds with a minimum of one detection, the half method detection limit for that compound was substituted for any number lower than that compound's half method detection limit. Chloromethane and trichlorofluoromethane consistently had the same pattern of the highest detection rates, but the total average concentrations were frequently the second and third highest over the eight years. This would indicate that the concentrations of chloromethane and trichlorofluoromethane are relatively average per each consistent detection. Conversely, dichlorodifluoromethane had one of the highest levels of concentration and one of the highest detection rates consistently for the eight years of data. This would indicate that for each detection, the dichlorodifluoromethane concentration had a consistently higher weight. From the 2009 to 2010 data, there was a noticeable increase in benzene and cyclohexane (shown in dark purple). The higher benzene levels seem to be attributed to samples collected at both the Macon and Dawsonville sites, while the higher cyclohexane appears to have been collected at the Macon site. In 2011 (shown in brown), both benzene and cyclohexane concentrations dropped back down below levels seen in 2009. Carbon tetrachloride had a slight increase in concentration, while the other frequently detected compounds remained relatively stable in 2011. The 2012 average concentrations of VOCs remain consistent and in proportion with previous years. 16 100.0 14 90.0 80.0 12 70.0 10 60.0 8 50.0 6 40.0 30.0 4 20.0 2 10.0 0 0.0 Total Average Concentration (g/m3) Percent Detections Name of Compound Concentration Detects 2005 2006 2007 2008 2009 2010 2011 2012 2005 2006 2007 2008 2009 2010 2011 2012 Figure 70: Average Concentration and Percent Detection of Common Volatile Organic Compounds (TO-15), 20052012 93 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring Figure 71 shows the total volatile organic compound concentration, or loading, at each site for 2005 through 2012. This "total loading" measurement is produced by adding all the detected concentrations of all VOCs, even those below half of the detection limit as discussed earlier. It is intended as a surrogate measure showing general trends in overall VOC concentrations. When considering Figure 71, it is important to note that the South DeKalb site could appear elevated since this site has a larger number of scheduled samplings than the rest of the sites in the network. Samples are collected on a 6-day schedule at the South DeKalb site, as part of the NATTS network. It is important to note that the Macon site was shut down for most of 2008 (shown in maroon) due to damage to the site, causing that value to appear much lower than the other Air Toxics sites. Data trends show there seems to be some fluctuation of VOC concentrations at most sites, and a slight decrease in 2008. Then in 2009, there was a slight increase in total VOC concentrations. In 2010, all of the sites showed an increase in total VOC concentrations, except the General Coffee site. The Dawsonville and Macon sites had a significant increase in total concentrations in 2010. For the Macon site, these higher concentrations seem to be attributed primarily to cyclohexane, dichloromethane, and benzene samples. While at the Dawsonville site, the higher concentrations seem to be attributed primarily to the benzene samples. Then in 2011, the Macon and Dawsonville sites had a dramatic decrease, to levels below those of 2009, while the other sites' total concentrations remained relatively stable or had a slight increase. For 2012, total VOCs concentrations were within the ranges reported in the previous seven years. Concentration (ppb) 240 220 200 180 160 140 120 100 80 60 40 20 0 Site 2005 2006 2007 2008 2009 2010 2011 2012 Figure 71: Total Volatile Organic Compound Loading all Species, by Site, 2005-2012 For a map of VOC and SVOC monitoring locations, see Figure 72 on the next page. 94 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring Figure 72: VOC and SVOC Monitoring Site Map 95 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report SEMI-VOLATILE ORGANIC COMPOUNDS Section: Air Toxics Monitoring Polycyclic aromatic hydrocarbons (PAHs), also called semi-volatile organic compounds (SVOCs) are chemical compounds that consist of fused, six-carbon aromatic rings. They are formed by incomplete combustion of carbon-containing fuels such as wood, coal, diesel fuel, fat or tobacco. Over 100 different chemicals are comprised within this designation. Many of them are known or suspected carcinogens. Some environmental facts about this class of compounds are listed below. PAHs enter the air mostly as releases from volcanoes, forest fires, burning coal, and automobile exhaust. PAHs can occur in air attached to dust particles. Some PAH particles can readily evaporate into the air from soil or surface waters. PAHs can break down by reacting with sunlight and other chemicals in the air over a period of days to weeks. PAHs can enter water through discharges from industrial and wastewater treatment plants. Most PAHs do not dissolve easily in water. They stick to solid particles and settle to the bottoms of lakes or rivers. Microorganisms can break down PAHs in the soil or water after a period of weeks to months. In soils, PAHs are most likely to stick tightly to particles. Certain PAHs can seep through soil to contaminate groundwater. PAH content of plants and animals may be much higher than the PAH content of the soil or water in which they live. For a map of SVOC monitoring locations, see Figure 72, on the previous page. 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0 Percentage Detections Site 2009 2010 2011 2012 Figure 73: Semi-Volatile Organic Compounds Percentage of Detections Per Site, 2009-2012 Figure 73 displays the percentage of detections (according to site) from the fourth quarter of 2009 through 2012 for all semi-volatile organic compounds combined in the Air Toxics Network, as well as the South DeKalb (NATTS) site. Prior to the fourth quarter of 2009, the semi-VOCs data collected within the Air Toxics Network was analyzed by the GA EPD laboratory with a gas chromatograph with Electron Capture Detector, while the semi-VOCs data collected within the NATTS network were analyzed with a gas chromatograph by an EPA contract laboratory. Then, in the fourth quarter of 2009, the GA EPD laboratory began analyzing the Air Toxics Network data with a gas chromatograph, the same method used to analyze data from the South DeKalb site. This caused an increase in detection rate for the five sites in the Air Toxics Network. Traditionally, there were only a few compounds that would have any detections, and most compounds would have no detections. Since 96 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring the change in laboratory analysis method, the detection rates have ranged from about 6% to 35%, for the five sites in the Air Toxics Network. Even though the same laboratory analysis method is used for this analysis, the South DeKalb data has historically shown a significantly higher percentage of detections, ranging from about 35% to 88% detection rate. As of July 2012, the GA EPD laboratory began analyzing the semi-VOCs collected at the South DeKalb site as well. Detections were counted as any number that was above half of the method detection limit. As data is collected in the future, the relationship between these sites will continue to be tracked. In addition, the data will be observed for possible continuing increase in detections with the gas chromatograph laboratory analysis method. Figure 74, below, shows the percentage of detections compared to the total average concentration for the seventeen semi-volatile organic compounds that all six sites have in common from fourth quarter 2009 through 2012. The percentage detections were derived using any detection that was above half of the method detection limit. To obtain the average concentration for compounds with at least one detection, the half method detection limit for that compound was substituted for any number lower than that compound's half method detection limit. As discussed above, until 2009, the percentage of detections and average concentrations were very low. Before the laboratory analysis method change for the Air Toxics Network data, the percent detections were below 10% and the average concentrations were below 0.01 g/m3. With the laboratory analysis change in the last quarter of 2009, there were significant increases in detections and concentrations for some compounds. Since the analysis method is the same, the following graph combines the Air Toxics Network data and the NATTS data. The largest semi-VOC contributor in both total average concentration and percent detections is naphthalene. The concentrations of naphthalene range from about 0.09 g/m3 to 0.21 g/m3, and percent detections are around 92 to 99%. These concentrations are approximately four to nine-fold higher than the next highest concentrations of around 0.015 to 0.033 g/m3 for phenanthrene. Phenanthrene's total detections have been in the 80% to 95% range, indicating that there were several small concentrations detected, as compared to having higher concentrations for each detection of naphthalene. Over half of the compounds continue to have low average concentrations and percent detections below 50%. Polycyclic aromatic hydrocarbons such as these are found in the air from the burning of coal, oil, gas, and garbage, and are found in dyes, cigarette smoke, coal tar, plastics, and pesticides. They have been found to bother the skin and mucous membranes and have even been linked to cancer. 0.22 100.0 0.2 90.0 0.18 80.0 0.16 70.0 0.14 60.0 0.12 50.0 0.1 0.08 40.0 0.06 30.0 0.04 20.0 0.02 10.0 0 0.0 Total Average Concentration (g/m3) Percentage Detections Name of Compound 2009 Concentration 2010 2011 2012 2009 Detects 2010 2011 2012 Figure 74: Total Average Concentration and Percentage Detections of Semi-Volatile Organic Compounds by Compound, 2005-2012 97 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring MONITORING TECHNIQUES In 2012 air toxics samples were collected from a total of six sites, including a NATTS site, and two background (rural) sites. The compounds sampled at the ATN sites are shown in Appendix D. The list was derived from the 189 compounds EPA has designated as Hazardous Air Pollutants (HAPS). Many of the HAPS do not have standardized ambient air sampling and analytical methods. In order to collect the compounds of interest for the Georgia network, three types of samplers are used at all locations: the HIVOL, PUF, and canister. In addition, carbonyls were monitored at two of the ATN sites, as well as one NATTS/PAMS site, in 2012. This equipment samples for metals, semi-volatile organic compounds, and volatile organic compounds once every twelve days following a pre-established schedule that corresponds to a nationwide sampling schedule. The South DeKalb site collects samples every six days, as part of the National Air Toxics Trends (NATTS) network. On the run day, the sampler runs midnight to midnight and takes a 24-hour integrated sample. The HIVOL sampler used for sampling metals is a timed sampler. The sampler is calibrated to collect 1300 to 2000 liters of air per minute. Particulate material is trapped on an 8.5" x 11" quartz fiber filter. The particulates include dust, pollen, diesel fuel by-products, particulate metal, etc. The filters are preweighed at a remote laboratory prior to use and weighed again after sampling. The filters are subjected to a chemical digestion process and are analyzed on an inductively coupled plasma spectrometer. The PUF (polyurethane foam) sampler used for sampling semi-volatile organic compounds is a timed sampler. The sampler is calibrated to collect 198 to 242 liters (L) of air per minute. A multi-layer cartridge is prepared which collects both the particulate fraction and the volatile fraction of this group of compounds. The plug, filter and absorbent are extracted at a remote laboratory and analyzed using a gas chromatograph. The canister sampler used for sampling volatile organic compounds is a timed sampler. A SUMMA polished canister is evacuated to a near-perfect vacuum and attached to a sampler with a pump controlled by a timer. The canister is filled to greater than 10 psig. The canister is analyzed using a gas chromatograph with mass spectroscopy detection (GC/MS). The carbonyls are sampled with two types of methods. One type is an absorbent cartridge filled with dinitrophenylhydrazine (DNPH) coated silica that is attached to a pump to allow approximately 180 L of air to be sampled. The cartridge is analyzed using High Performance Liquid Chromatography (HPLC). A 24-hour integrated carbonyl sample is taken every six days throughout the year. The other method used for collecting carbonyls is the cansiter sampler that is used for sampling volatile organic compounds. Acrolein is a carbonyl compound that is collected using the canister method, described above, and analyzed with the GC/MS method. As part of the National Air Toxics Trends network, the above listed compounds, as well as hexavalent chromium and black carbon are monitored at the South DeKalb site. In addition, metals are monitored on a PM10 sampler at the South DeKalb site. The hexavalent chromium sampler used for sampling Cr+6 is a timed sampler. Samples are collected at a flow rate of 15 liters of air per minute using a 37 mm diameter substrate of bicarbonate impregnated cellulose. The filter is controlled by an auto cover which remains closed until sampling, and fully exposes the filter when the sampler is running. The sample is analyzed using the modified California Air Resources Board (CARB) SOP 039. The filters are extracted in deionized water via sonication, which is analzyed by ion chromatography. Cr+6 is separated through a column, forming a 98 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Air Toxics Monitoring complex with diphenylcarbohydrazide. Dianex Peaknet chromatography software is used to determine the peak analysis. The aethalometer is a continuous sampler used for sampling black and organic carbon. Operating at 60 watts / 110V AC, the aethalometer uses quartz tape to perform an optical analysis to determine the concentration of carbon particles passing through an air stream. The analysis is conducted using spectrophotometry, measuring the wavelength of the light energy absorbed and plotting the results on the site computer. The PM10 sampler used for sampling toxic metal particles less than or equal to 10 microns in diameter is a timed sampler. Collecting 1020 to 1240 liters of air per minute, the sampler uses a 8.5" x 11" quartz glass fiber filter to trap particulate matter. The sample is analyzed using inductively coupled plasma mass spectrometry (ICP-MS). In ICP-MS, an argon gas is used to atomize and ionize the elements in a sample. The resulting ions are used to identify the isotopes of the elements and a mass spectrum is used to identify the element proportional to a specific peak formed from an isotope. ATTAINMENT DESIGNATION Currently, there are no attainment standards for the air toxics compounds, with the exception of lead, which has its designation as a criteria pollutant. Air toxics measurements are performed to support the regulatory, analytical, and public health purposes of the program. While it is understood that these compounds are toxic, it is not well understood what airborne concentrations of each compound may be harmful. By collecting data about their current concentrations, researchers can later compare GA EPD's data with health data to determine what levels of each compound may be safe. 99 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report METEOROLOGICAL REPORT STATE CLIMATOLOGY AND METEOROLOGICAL SUMMARY OF 2012 The climate of north and central Georgia, which includes the metropolitan areas of Atlanta, Columbus and Macon, involves summers of warm, humid weather, and variable temperatures during the winter months. The climate across northern Georgia is largely a function of terrain. Average amounts of rainfall reach between 45-50 inches, with September and October averaging as the driest months and the wettest being March. According to the National Weather Service office in Peachtree City, Georgia, 2012 was a year of warmer than average temperatures and below average precipitation. The month of January was characterized by above normal temperatures and precipitation totals varying from north to south across the state. Several cities averaged temperatures several degrees above normal, including Atlanta (+5.8), Athens (+3.6), Columbus (+4.7), Macon (+3.6) and Brunswick (+4.1). Precipitation ranged from slightly above average in the north, to well below average in the south. The sharp contrast between northern drought-free areas and southern Exceptional drought areas intensified in January, according to the U.S. Drought Monitor. By the end of the month, over 50% of Georgia remained in D3 (Extreme) drought conditions, while approximately 16% were in D4 (Exceptional). There was a sharp drought gradient across the state, with south Georgia experiencing the worst conditions and areas of northwest Georgia not within a drought at all. Central to north Georgia ranged from abnormally dry to severe drought. A National Weather Service Assessment Team determined that an EF0 tornado occurred in northern Dooly County on January 21st. EF-1 tornadoes touched down in Macon County and in south central Coweta County on the 21st as well. There were also reports of golf-ball sized hail and straight-line wind damage. Flash flooding was observed with this event, as well, near and west of downtown Atlanta. February saw a continuation of above average temperatures with several records set across the state. St. Simons Island reached a high temperature of 84 on the 24th, breaking the old record of 82 set in 1962. Athens tied a record high of 79 on the 23rd, which is the 7th highest maximum temperature recorded there since 1893. Augusta reached 82 on the 23rd, breaking a previous record of 81. Precipitation remained well below normal for areas of the state. A few active weeks in early to mid- February brought some improvement to the area as several pulses of moisture crossed the state. March proved to be a very memorable month with a severe weather event, elevated pollen counts, and record-setting temperatures. The month began with an intense, spring-like storm system that moved across the southeast producing widespread severe weather. A supercell thunderstorm produced two tornadoes in Georgia during this event, including an EF-3 in Paulding and Harrison Counties and an EF-1 in Cobb County. The La Nina pattern of warm temperatures seen throughout the winter, continued into March with near summer-like temperatures occurring before the official start of spring. March 2012 recorded the warmest average temperature on record at several official climate sites, including Atlanta, Athens, and Columbus. Several cities also set new March records for consecutive days at or above 80 degrees. The unusually high temperatures in the southeast during March could be partly attributed to a persistent blocking high-pressure system in the Atlantic Ocean. This blocking pattern during March kept the polar jet stream bulged well to the north. The mild winter also played a role in setting new record high pollen counts in March. The previous record for AtlantaSandy Springs-Marietta MSA, set in 1999, of 6,103 particles per cubic meter was broken on March 19th with a total of 8,164 particles per cubic meter. The pollen count reached even higher on the 20th at 9,369 particles per cubic meter. The overall pattern of above normal temperatures and below normal precipitation persisted state-wide throughout the month of April. Despite a cold snap on April 12th, leading to numerous at or below freezing low temperatures across the north, numerous cities still set new high temperature records during April. This includes Atlanta (87 on 3rd), Columbus (90 on 29th and 94 on 30th), Brunswick (89 on 2nd), and Macon (92 on 29th and 93 on 30th). Observed rainfall for the month reflected larger 100 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report amounts in the far northeast corner of the state, with smaller amounts recorded in areas that could benefit the most from it. May provided welcome rainfall in southern and eastern parts of the state from Tropical Storm Beryl, while other areas still remained below normal. Areas of coastal Georgia received well over 5 inches of rain in a short period of time as the storm system moved northeast along the coast on the 29th and 30th (Figure 75). The preseason tropical activity had little effect, however, on other rainfall deficits across the state, as the storm system did not move far enough inland to provide long-term drought relief. Climate stations such as Macon, Atlanta, and Athens reflected slightly below normal rainfall during May (-0.61, -0.26, -0.33, respectively). Figure 75: Rainfall from Tropical Storm Beryl June was characterized by abundant rainfall from Tropical Storm Debby across south Georgia and Florida, as well as record-breaking heat across much of the U.S. Debby engulfed Florida with flooding rains beginning June 23rd and continued the deluge into parts of extreme southern and southeast Georgia through the 27th. The National Weather Service (NWS) climate station at St. Simons Island recorded 5.99 inches of rainfall during the period of the 23rd-27th, with a record daily maximum amount set on the 26th. The record daily rainfall of 2.9 inches on the 26th broke the old record of 2.77 inches set in 1963. CoCoRaHS rainfall reports topped 10 inches in many areas, with readings such as 12.96 inches in Kingsland and 10.05 inches at Kings Bay. The heaviest rainfall totals for the 7-day period of 21st through 27th were confined to extreme southern and southeast Georgia, similar to Tropical Storm Beryl (Figure 76). 101 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Figure 76: Rainfall from Tropical Storm Debby Rainfall totals decreased further north, as drier air filtered in from a strong high pressure system in the wake of Debby. Alma, Georgia only reported 1.49 inches of rainfall for the event. Although Tropical Storm Debby provided drought relief across Florida and southeast Georgia (as registered by the 102 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Drought Monitor), it did not reach the heart of the drought-stricken areas in southwestern and central Georgia, including the central Savannah River valley (Figure 77). Figure 77: Drought Impacts from Tropical Storm Debby The official start of summer was followed by a remarkable heat wave event, from June 29 through July 1, as a strong upper level ridge dominated across the southeast. Numerous temperature records were set, not only in Georgia, but across the U.S as well. During the three-day period, many locations reported temperatures well above 100F. Several high temperature records were tied or broken during this event. Columbus and Atlanta set new all-time record highs of 106 F on the 30th, while Athens set a new record of 109F on the 29th. Macon tied a record of 108F, which was last observed in 1980. Figure 78 below details the highest recorded temperatures for the month of June, most of which occurred during the extreme heat event. These record high temperatures, along with dry, highly stable atmospheric conditions provided stagnant conditions for north Georgia at the end June, which allowed for very poor air quality to occur as well. The Atlanta-Sandy Springs-Marietta MSA recorded a rare Code Purple at the Environmental Protection Division (EPD)'s McDonough, GA site on the 29th, which is considered Very Unhealthy under EPA's Air Quality Standards for ozone. The concentration reached an 8-hr average of 122 parts per billion by volume (ppbv). The last Code Purple the AtlantaSandy Springs-Marietta MSA experienced was on Aug 15th, 2007. The GA EPD site at Conyers, GA reached 109 ppbv on the 29th, which is a high Code Red ("Unhealthy"). 103 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Figure 78: Highest Recorded Temperatures for the Month of June The month of July was characterized by a typical summertime pattern of scattered afternoon and evening thunderstorms due to daytime heating. A Bermuda High Pressure system in the Atlantic Ocean extended across the region, slightly suppressing convection and allowing rainfall totals to remain below normal for the month. A persistent upper level trough pattern over the eastern U.S. 104 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report brought beneficial rainfall to many areas of the state during the month of August. Augusta recorded its fifth wettest month of all time and the second wettest August on record, with rainfall totals of 12.28 inches recorded at Bush Field. Augusta also set a new maximum daily rainfall record on the 11th of 4.68 inches as thunderstorms passed through. Southern areas of the state received additional rainfall from the outer bands of Hurricane Isaac during the latter part of the month. The track of Isaac remained west of the state, but contributed significant precipitation to some areas of Georgia. A persistent trough of low pressure over the northeast continued to be the dominant synoptic feature through much of September. Temperatures remained near normal across most of the state. Periods of moderate rainfall allowed portions of the extreme northwest and all of the southwest to receive over two inches of above normal rainfall for the month. Areas within the core of the drought saw brief periods of beneficial rainfall, allowing the spatial coverage of the severe to exceptional drought to decrease in parts of the north and central Georgia. As is typical, the month of October was relatively quiet across the state with temperatures averaging near normal throughout the month. Dry conditions continued across much of the drought-stricken region. Below normal rainfall of over two inches was recorded across many areas of the state. Both Alma and Macon recorded rainfall deficits over 2.5 inches for the entire month. Among first order climate sites and select cooperative observing stations, the average precipitation departure was -9.61 inches, with Plains, GA having its driest year-to-date. The month of October ended on a significant note as former hurricane turned post-tropical cyclone Sandy tracked northeast up the Atlantic coast (Figure 79). The storm moved parallel to the South Carolina coast on the 27th and 28th, with winds increasing across coastal Georgia the 29th as the pressure gradient tightened. This produced breezy conditions across the state from the 29th through the 31st, which prompted the issuance of wind advisories for portions of north Georgia. Peak gusts of over 40 mph were also recorded at several NWS sites during the period. Figure 79: Post-tropical Cyclone Sandy Tracking Northeastward 105 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Temperatures stayed below the record-setting warmth of November 2011 for Atlanta and Athens. The drought continued to expand across already-stricken areas of Georgia due to a lack of sufficient rainfall during the month. The four major climate sites in northern and central Georgia received an inch and a half to nearly three inches below normal precipitation for the month. White County reported a mean year-to-date rainfall deficit of 12 inches, receiving 80.3% of its normal year-to-date totals. A brief period of rainfall brought minor relief to some areas, with Atlanta setting a record daily maximum rainfall of 1.25 inches on November 6th. This broke the old record of 1.10 inches set in 1995. November 30th marked a rather quiet close to a busy Atlantic hurricane season. The 2012 season produced 19 named storms, of which 10 became hurricanes and one became a major hurricane. The number of named storms topped the average of 12, while the number of hurricanes also surpassed the average of 6. Although NOAA has classified the season as above-normal, due to the combined number, intensity, and duration of all the tropical storms and hurricanes, it is still not considered an exceptional season. December was a mild month with temperatures averaging above normal for much of the state, as the neutral El Nino Southern Oscillation (ENSO) pattern continued in the Pacific. Atlanta set a record high temperature of 74F on December 3rd, which tied the old record set in 1982. The 90-day rainfall departure for the state at this time (Figure 80) shows some improvement in of north and central Georgia, while drier than average conditions prevailed over the extreme southeast and parts of the southwest. St. Simons Island was nearly an inch below the monthly normal of 2.64 inches as drought conditions persisted and intensified across the region. 106 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Figure 80: Drought Conditions across the State with Rainfall Departures and Streamflows SUMMARY OF METEOROLOGICAL MEASUREMENTS FOR 2012 A complete suite of meteorological instrumentation is used to characterize meteorological conditions around metropolitan Atlanta. The basic surface meteorological parameters were measured at the Photochemical Assessment Monitoring Sites (PAMS). The PAMS sites are Conyers, South DeKalb, Tucker, and Yorkville. South DeKalb is considered an NCore and a NATTS site as well. The Tucker site primarily records meteorological data for possible future modeling or comparative purposes. All PAMS sensors measure hourly-averaged scalar wind speed and vector-averaged wind direction at the 10-meter level, and hourly-averaged surface temperature, relative humidity and barometric pressure at the 2-meter level. Several sites include instruments to record precipitation, global solar radiation and total ultraviolet radiation. The standard deviation of the wind direction is also computed at the South DeKalb (NCore, NATTS site). Upper air meteorological observations (primarily wind speed and direction) are made at Peachtree City using a PA5-LR SODAR system. A map of the GA 107 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report EPD meteorological network, along with which measurements are taken at each location, is shown in Figure 81, below. Figure 81: Meteorological Site Map 108 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report OZONE AND PM2.5 FORECASTING AND DATA ANALYSIS Each day a team of meteorologists from Georgia Department of Natural Resources, Environmental Protection Division (EPD) and Georgia Tech scientists meet at 1:30 EST to issue an air quality forecast for the Atlanta, Macon, and Columbus metropolitan areas. The air quality forecast is then relayed to the Clean Air Campaign and EPA, which disseminate the forecast to important national outlets, such as National Weather Service (NWS), USA Today, and The Weather Channel. The forecasts are determined based upon several meteorological factors, such as the synoptic regime, surface and upper air meteorology, satellite imagery, as well as the ambient concentration of pollutant. Multiple 2D and 3D forecasting models generated by Georgia Tech are utilized in addition to NWS synoptic forecasting models. These synoptic models consist of the North American Model (NAM/WRF), the Global Forecasting System (GFS), the European, and the Canadian models to name a few. During the 2012 ozone season (March through October), Metropolitan Atlanta had 17 ozone violations. Augusta and Athens each experienced 3 ozone violations. Macon had 2 ozone violations, while the north Georgia mountains had no violations. This was considered to be a typical to slightly below average ozone season for the Atlanta-Sandy Springs-Marietta MSA. Monthly time series plots of ozone predictions and observations for the Atlanta-Sandy Springs-Marietta MSA during the 2012 ozone season are shown in Figure 82. The dark squares shown in Figure 82, on the next page, indicate days where an ozone violation occurred, but was not forecasted, or did not occur and was forecasted. Most violations occurred during the months of June and July, with the highest concentration day, a rare Code Purple occurring on June 29th (122 parts per billion by volume, ppbv). This violation occurred at EPD's McDonough monitoring site southeast of the city under light northwest flow conditions during a record-setting heat wave event (June 29th through July 1st). During this violation, the eastern two thirds of the continental United States was dominated by a very strong high-pressure system, placing north Georgia on the eastern flank of the ridge with light downsloping flow from the Appalachians. This provided a highly stable air mass with clear skies and stagnant conditions, leading to the Code Purple ozone violation. As shown in Figure 82, there were only two ozone violations during August and only one in September for the Atlanta-Sandy Springs-Marietta MSA. There were 2 ozone violations in May, 6 in June, and 6 in July. On a day-of-the-week basis, the greatest number of violations occurred from the middle to the end of the week, with the most number of violations (5) occurring on both Thursday and Friday. Some of this could possibly be attributed to the buildup of traffic around the Atlanta-Sandy Springs-Marietta MSA as the weekend approaches. Overall forecasting performance for the team for the 2012 ozone season was 90.2% on an event to a non-event basis (binary error) and 68% on an AQI basis (color category). The team called 17 events, with 10 hits and 7 misses. Of the 17 ozone events, the team had 8 misses. In terms of AQI color code, there were 76 green days, 59 yellow days, 15 orange days, 1 red day, and 1 purple day. 109 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Maximun O3 concentrations (ppbv) 2012 90 80 70 60 50 40 30 20 100 90 80 70 60 50 40 30 20 120 100 O3 observed O3 predicted MAY JUN JUL 80 60 40 20 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 Day of the month 2012 O3 observed O3 predicted 80 60 40 AUG 20 Maximun 8-hrs O3 concentrations (ppbv) 80 60 40 20 SEP 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 Day of the month Figure 82: Ozone Predictions and Observations for the Atlanta-Sandy Springs-Marietta MSA During the 2012 Ozone Season With the continuous PM2.5 samplers used for forecasting (see PM2.5 section for sampler details), there were eight PM2.5 values above the standard in 2012. Three of these higher particle pollution values occurred in the Atlanta-Sandy Springs-Marietta MSA, 2 in the Augusta-Richmond County GA, SC MSA, 2 in south Georgia, and 1 in the Macon MSA. Monthly time series plots of PM2.5 predictions and observation for the Atlanta-Sandy Springs-Marietta MSA during 2012 are shown in Figure 83, on the next two pages. 110 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report PM2.5 (ug/m3) PM2.5 (ug/m3) JANUARY 2012 50 40 Observed Predicted 30 20 10 0 0 5 10 15 20 25 30 FEBRUARY 2012 40 30 20 10 0 0 5 10 15 20 25 30 MARCH 2012 30 20 10 0 0 5 10 15 20 25 30 PM2.5 (ug/m3) APRIL 2012 30 PM2.5 (ug/m3) 20 10 0 0 5 10 15 20 25 30 MAY 2012 30 PM2.5 (ug/m3) 20 10 PM2.5 (ug/m3) 0 0 5 10 15 20 25 30 JUNE 2012 40 Observed 30 Predicted 20 10 0 0 5 10 15 20 25 30 Figure 83 a: PM2.5 Predictions and Observations for the Atlanta-Sandy Springs-Marietta MSA During 2012 111 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report PM2.5 (ug/m3) PM2.5 (ug/m3) JULY 2012 40 Observed 30 Predicted 20 10 0 0 5 10 15 20 25 30 AUGUST 2012 30 20 10 0 0 5 10 15 20 25 30 SEPTEMBER 2012 30 20 10 0 0 5 10 15 20 25 30 PM2.5 (ug/m3) OCTOBER 2012 30 Observed 20 Predicted PM2.5 (ug/m3) 10 0 0 5 10 15 20 25 30 NOVEMBER 2012 30 PM2.5 (ug/m3) 20 10 0 0 5 10 15 20 25 30 DECEMBER 2012 30 PM2.5 (ug/m3) 20 10 0 0 5 10 15 20 25 30 (Data compiled by Dr. Carlos Cardelino of Georgia Tech) Figure 83 b: PM2.5 Predictions and Observations for the Atlanta-Sandy Springs-Marietta MSA During 2012 112 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report PM2.5 CASE STUDY ANALYSES One interesting PM2.5 episode, a possible exceptional event, occurred at the beginning of the year due to New Year's Eve local fireworks. Figure 84 shows the increase in PM2.5 levels occurring between midnight and noon on New Year's Day. This increase could have been further enhanced by prefrontal pooling ahead of an approaching strong wintertime cold front. The 12Z rawinsonde from Peachtree City (Figure 85 on next page) shows strong winds aloft due to an increasing polar jet along with a surge of cold air advection. GASP aerosol optical imagery (Figure 86 on next page) shows some enhancement of aerosol optical depth (AOD) around the Atlanta-Sandy Springs-Marietta MSA, possibly due to smoke from fireworks. However, there is also increasing cloudiness associated with the frontal passage during the pass, which makes it somewhat difficult to separate the cloud optical thickness from the smoke AOD. Figure 84: Time Series of Hourly PM2.5 113 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Figure 85: 12Z Rawinsonde from Peachtree City, GA Figure 86: GASP Aerosol Optical Imagery 114 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report The second PM2.5 episode occurred on April 8th-9th in south Georgia and near the southeast Georgia coast. This particle pollution event was due to the Osceola fire near the Georgia/Florida border. Surface wind direction (Figure 87 below) and objective surface analysis (Figure 88 on next page) show transport of forest fire smoke from the wildfire activity. An increase in particle pollution concentrations occurred at the Valdosta monitoring site on April 8th, under ESE and SE flow, while a lesser increase occurred at the Savannah-L&A monitoring site on April 9th, as the winds shifted more from the WSW. This wind shift and corresponding PM2.5 increase is shown in Figure 89 presented below. This is a good example showing how the fire/smoke plume recirculated across the state as a high pressure ridge built across the area. Figure 87: Surface Wind Direction 115 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Figure 88: Objective Surface Analysis 116 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Meteorological Report Figure 89: Wind Shift and Corresponding PM2.5 Increase 117 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance QUALITY ASSURANCE The purpose of this report is to provide ambient air quality users and the general public, with a summary of the quality of the 2012 ambient air monitoring data in quantifiable terms. It presents an overview of various quality assurance and quality control activities. The tables included in this report provide summary data for ambient air monitoring stations in the statewide network. The Georgia Air Protection Branch mission is to promote and protect public health, welfare, and ecological resources through effective and efficient reduction of air pollutants while recognizing and considering the effects on the economy of the state. The Ambient Air Monitoring Program provides a key element of that mission through collecting and reporting quality information on a large number of pollutants and for a vast air monitoring network. The Ambient Air Monitoring Program, directed by federal law, conducts various monitoring projects in support of the Georgia Department of Natural Resources (GA DNR), Georgia Environmental Protection Division (GA EPD), and the United States Environmental Protection Agency (U.S. EPA). The monitoring projects include gaseous criteria and non-criteria pollutants, particulate matter, air toxics, non-methane hydrocarbons, and meteorological parameters. Data from these monitoring sources provide the means to determine the nature of the pollution problem and assess the effectiveness of the control measures and programs. It is the goal of the Ambient Monitoring Program to provide accurate, relevant, and timely measurements of air pollutants and their precursors associated with the corresponding meteorological data to support Georgia's Air Protection Branch for the protection of environment and public health. The Quality Assurance Unit conducts various quality assurance activities to ensure that data collected comply with procedures and regulations set forth by the U.S. EPA and can be considered good quality data and data for record. What is quality assurance? Quality assurance is an integrated system of management activities that involves planning, implementing, assessing, and assuring data quality through a process, item, or service that meets users needs for quality, completeness, representativeness and usefulness. Known data quality enables users to make judgment about compliance with quality standards, air quality trends and health effects based on sound data with a known level of confidence. The objective of quality assurance is to provide accurate and precise data, minimize data loss due to malfunctions, and to assess the validity of the air monitoring data to provide representative and comparable data of known precision and accuracy. Quality assurance (QA) is composed of two activities: quality control and quality assessment. Quality control (QC) is composed of a set of internal tasks performed routinely at the instrument level that ensures accurate and precise measured ambient air quality data. Quality control tasks address sample collection, handling, analysis, and reporting. Examples include calibrations, routine service checks, chain-of-custody documentation, duplicate analysis, development and maintenance of standard operating procedures, and routine preparation of quality control reports. Quality assessment is a set of external, quantitative tasks that provide certainty that the quality control system is satisfactory and that the stated quantitative programmatic objectives for air quality data are indeed met. Staff independent of those generating data perform these external tasks. Tasks include conducting regular performance audits, on-site system audits, inter-laboratory comparisons, and periodic evaluations of internal quality control data. Performance audits ascertain whether the samplers are operating within the specified limits as stated in the Standard Operating Procedures (SOPs). Table 4, on the next page, illustrates the types of performance audits currently performed by the QA Program in 2012. Field and laboratory performance audits are the most common. System audits are performed on an as needed basis or by request. Whole air sample comparisons are conducted for the toxic air contaminants and non-methane hydrocarbons. 118 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance Air Monitoring Program Gaseous Pollutants Particulate Matter Air Toxic Contaminants Non-Methane Hydrocarbons Meteorology Field Performance Audit X X X X X Laboratory Performance Audit X X X X System Audit X X X X Whole Air Audit X X Table 4: Audits Performed for Each Air Monitoring Program in 2012 QUALITY CONTROL AND QUALITY ASSESSMENT The Quality Assurance Program supports all ambient monitoring programs undertaken by Georgia EPD, which in 2012 includes gaseous pollutants, particulate pollutants, air toxics contaminants, nonmethane hydrocarbons and meteorological sensors run by the Ambient Monitoring Program. In 2012, 52 air monitoring sites operated in Georgia (see Table 2 on pages 5-6 for details). Appendix E of this document provides information about the air monitoring network (i.e., sampling schedules, number of instruments, collection/analysis method, etc.). The air quality monitors collect data in both real-time and on a time integrated basis. The data is used to define the nature, extent, and trends of air quality in the state; to support programs required by state and federal laws; and to track progress in attaining air quality standards. The precision and accuracy necessary depends on how the data will be used. Data that must meet specific requirements (i.e., criteria pollutants) are referred to as controlled data sets. Criteria for the accuracy, precision, completeness, and sensitivity of the measurement in controlled data sets must be met and documented. The process by which one determines the quality of data needed to meet the monitoring objective is sometimes referred to as the Data Quality Objectives Process. Data quality indicators associated with measurement uncertainty include: Precision: A measurement of mutual agreement among individual measurements of the same property usually under prescribed similar conditions, expressed generally in terms of the standard deviation. Bias: The systematic or persistent distortion of a measurement process, which causes errors in one direction. Accuracy: The degree of agreement between an observed value and an accepted reference value. Accuracy includes a combination of random error (imprecision) and systematic error (bias) components that are due to sampling and analytical operations. Completeness: A measure of the amount of valid data obtained from a measurement system compared to the amount that is expected to be obtained under correct, normal conditions. Detectability: The low critical range value of a characteristic that a method specific procedure can reliably discern. Data without formal data quality objectives (i.e., GA EPD's air toxics network) are called descriptive data sets. The data quality measurements are made as accurately as possible in consideration of how the data are being used. Quantified quality assessment results describe the measurement variability in standard terminology, but no effort is made to confine the data set to values within a predetermined quality limit. 119 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance The Georgia Air Sampling Network's (GASN) Quality Assurance Program is outlined in a five-volume Quality Assurance Manual. The volumes, listed below, guide the operation of the quality assurance programs used by the GASN. Volume I: Quality Assurance Plan Volume II: Standard Operating Procedures for Air Quality Monitoring Volume III: Laboratory Standard Operating Procedures Volume IV: Monitoring Methods for the State Ambient Air Quality standards Volume V: Audit Procedures for Air Quality Monitoring Volume I lists the data quality objectives and describes quality control and quality assessment activities used to ensure that the data quality objectives are met. GASEOUS POLLUTANTS Sampling Cone Ambient concentrations of carbon monoxide (CO), nitrogen dioxide (NO2), ozone (O3), and sulfur dioxide (SO2) are continuously monitored by an automated network of stations run by the Georgia Ambient Air Monitoring Program. Exposure to these pollutants may cause adverse health effects such as: respiratory impairment, fatigue, permanent lung damage, and increased susceptibility to infection in the general population. Gaseous criteria and non-criteria pollutant data are a controlled data set and are subject to meeting mandatory regulations. Accuracy: Annually, EPA conducts field through-the-probe (TTP) performance audits for gaseous pollutants to verify the system accuracy of the automated methods and to ensure the integrity of the sampling system. Accuracy is represented as an average percent difference. The average percent difference is the combined differences from the certified value of all the individual audit points. The upper and lower probability limits represent the expected accuracy of 95 percent of all the single analyzer's individual percent differences for all audit test levels at a single site. Bias is the systematic or persistent distortion of a measurement process, which causes errors in one direction. Overall, the responses of the individual analyzers indicate that as a whole, the network is providing accurate data. Ninety-five percent of the gaseous pollutant instruments audited in 2012 were found to be operating within the Georgia Ambient Air Monitoring control limits (15%). The tables below summarize the 2012 performance audit results for each gaseous pollutant. Precision: On a weekly basis, site operators confirm the linear response of the instrument by performing zero, precision and span checks. The zero precision check confirms the instrument's ability to maintain a stable reading. The span precision check confirms the instrument's ability to respond to a known concentration of gas. The degree of variability in each of these weekly measurements is computed as the precision of that instrument's measurements. Annually, the Quality Assurance Unit conducts a precision data analysis as an overall indicator of data quality. The analysis addresses three parameters: precision data submission, precision data validity, and a combination of the two referred to as data usability rates. The precision performance goal for all three parameters is 85%. The submission rate is the number of precision points submitted for a pollutant divided by the expected number of bi-weekly submissions. Data validity is the percent difference of the actual and indicated values of each precision check. These differences should not exceed 15% for gaseous analyzers. Usable data rates are determined by multiplying the data submission and data validity rates that indicate the completeness of verifiable air quality data on the official database. The tables below show the Georgia annual Data Quality Assessment summary for the gaseous pollutants (NO, NO2, NOX, CO, SO2, O3). 120 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance NO Yearly Data Quality Assessment Summary Site Code Site Name Validation of Bias Annual Performance Evaluation Bias No. of Precision Absolute Bias Obs. CV (%) Estimate (%) Avg 95% LPL 95% UPL No. of Avg (%) (%) (%) Obs. (%) Completeness 95% LPL 95% UPL (%) (%) (%) 13-089-0002 Decatur - S. DeKalb 50 3.26 4.47 -3.65 -9.19 1.88 4 0.77 -1.63 3.17 97 13-223-0003 Yorkville - King's Farm 55 4.49 8.09 -7.40 -14.90 0.48 8 -2.60 -13.01 7.82 89 13-247-0001 Conyers - Monastery 48 2.46 4.12 -3.59 -7.77 0.58 8 -9.01 -13.87 -4.15 96 Georgia Ambient Air Monitoring Program 153 3.45 5.66 -4.98 -11.05 1.08 20 -4.49 -11.93 2.96 94 95% LPL: 95% Lower Probability Limit 95% UPL: 95% Upper Probability Limit Table 5: NO Data Quality Assessment NO2 Yearly Data Quality Assessment Summary Site Code Site Name Validation of Bias Annual Performance Evaluation Bias No. of Precision Absolute Bias Obs. CV (%) Estimate (%) Avg 95% LPL 95% UPL No. of Avg (%) (%) (%) Obs. (%) Completeness 95% LPL 95% UPL (%) (%) (%) 13-089-0002 Decatur - S. DeKalb 55 3.60 3.02 -1.09 -7.25 5.07 8 6.89 -2.24 16.01 97 13-223-0003 Yorkville - King's Farm 61 4.35 4.20 2.22 -5.32 9.69 8 1.12 -2.57 4.81 89 13-247-0001 Conyers - Monastery 53 2.87 2.25 0.07 -4.82 4.96 8 -7.24 -17.98 3.51 96 Georgia Ambient Air Monitoring Program 169 3.64 3.20 0.47 -5.87 6.81 24 0.26 -8.16 8.67 94 95% LPL: 95% Lower Probability Limit 95% UPL: 95% Upper Probability Limit Table 6: NO2 Data Quality Assessment NOx Yearly Data Quality Assessment Summary Site Code Site Name Validation of Bias Annual Performance Evaluation Bias No. of Precision Absolute Bias Obs. CV (%) Estimate (%) Avg 95% LPL 95% UPL No. of Avg (%) (%) (%) Obs. (%) Completeness 95% LPL 95% UPL (%) (%) (%) 13-089-0002 Decatur - S. DeKalb 54 2.95 2.45 -0.87 -5.91 4.17 4 1.98 0.34 3.63 97 13-223-0003 Yorkville - King's Farm 49 2.92 3.32 2.31 -2.64 7.27 8 -2.44 -12.69 7.81 89 13-247-0001 Conyers - Monastery 49 2.72 3.83 3.20 -1.40 7.81 8 -11.37 -16.15 -6.59 96 Georgia Ambient Air Monitoring Program 152 2.87 3.18 1.47 -3.41 6.35 20 -5.13 -12.42 2.16 94 95% LPL: 95% Lower Probability Limit 95% UPL: 95% Upper Probability Limit Table 7: NOX Data Quality Assessment 121 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance CO Yearly Data Quality Assessment Summary Site Code Site Name Validation of Bias Annual Performance Evaluation Bias No. of Precision Absolute Bias Obs. CV (%) Estimate (%) Avg 95% LPL 95% UPL No. of Avg (%) (%) (%) Obs. (%) Completeness 95% LPL 95% UPL (%) (%) (%) 13-121-0099 Atlanta - Roswell Rd. 66 2.84 2.38 -0.87 0.00 4.39 12 -4.75 -16.48 6.98 98 13-223-0003 Yorkville - King's Farm 55 3.44 4.39 -4.50 -9.34 2.43 3 -1.90 -4.38 4.38 97 13-089-0002 Decatur-South DeKalb 53 4.05 4.22 3.11 -3.89 9.94 6 -1.22 -16.04 13.60 98 Georgia Ambient Air Monitoring Program 174 3.11 3.29 -2.52 -7.90 2.86 21 -2.99 -13.91 7.94 96.7 95% LPL: 95% Lower Probability Limit 95% UPL: 95% Upper Probability Limit Table 8: CO Data Quality Assessment SO2 Yearly Data Quality Assessment Summary Site Code Site Name Validation of Bias Annual Performance Evaluation Bias No. of Precision Absolute Bias Obs. CV (%) Estimate (%) Avg 95% LPL 95% UPL No. of Avg (%) (%) (%) Obs. (%) Completeness 95% LPL 95% UPL (%) (%) (%) 13-021-0012 Macon - Forestry 54 2.78 3.94 -3.25 -8.00 1.49 8 0.00 -1.90 1.13 97 Savannah - East President 13-051-0021 St. 56 1.96 2.34 -1.79 -5.17 1.55 4 0.36 -1.06 1.78 97 13-051-1002 Savannah - L & A 55 1.64 1.31 -0.41 -3.22 2.40 4 -6.77 -16.79 3.26 99 13-215-0008 Columbus Airport 58 4.96 7.99 -7.08 -15.46 1.60 4 6.38 5.64 7.11 98 13-115-0003 Rome - Coosa Elementary 57 1.08 1.78 -1.51 -3.37 0.35 8 -5.78 -7.64 -3.93 96 13-121-0055 Atlanta - Confederate Ave. 57 3.46 2.90 1.57 -4.37 7.51 4 -8.29 -11.91 -4.67 97 13-127-0006 Brunswick - Risley School 56 2.60 6.98 -6.47 -10.93 -2.00 4 8.07 -3.24 19.37 97 13-089-0002 Atlanta-South DeKalb 58 4.29 3.46 -2.30 -9.63 5.12 8 -8.35 -14.26 -2.44 98 Georgia Ambient Air Monitoring Program 451 2.65 3.91 -2.72 -8.55 3.12 44 -1.07 -5.71 3.56 97.4 95% LPL: 95% Lower Probability Limit 95% UPL: 95% Upper Probability Limit Table 9: SO2 Data Quality Assessment 122 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance O3 Yearly Data Quality Assessment Summary Site Code Site Name No. of Obs. Precision Estimate CV (%) Absolute Bias Estimate (%) Validation of Bias Avg (%) 95% LPL (%) 95% UPL (%) Annual Performance Evaluation Bias No. of Avg Obs. (%) 95% LPL (%) 95% UPL (%) Completeness (%) 13-021-0012 Macon - Forestry 32 1.83 1.43 -0.11 -3.09 2.87 4 4.94 -7.36 17.23 99 13-051-0021 Savannah - East President St. 31 0.98 0.64 0.39 -1.20 1.97 4 -0.75 -12.52 11.02 97 13-055-0001 Summerville - DNR Fish Hatchery 38 1.14 1.66 1.52 -0.49 3.28 4 1.56 -3.28 6.40 99 13-059-0002 Athens - Fire Station 7 36 1.15 1.04 -0.76 -2.66 1.14 4 0.73 0.41 1.05 99 13-067-0003 Kennesaw - Georgia National Guard 35 0.93 1.91 1.69 0.16 3.22 4 6.67 3.04 10.30 99 13-073-0001 Evans - Riverside Park 33 2.78 1.82 0.29 -4.25 4.83 4 0.50 -0.41 1.41 98 13-077-0002 Newnan - University of West Georgia 40 2.35 2.57 -2.08 -5.74 2.09 4 -0.52 -3.33 2.29 99 13-085-0001 Dawsonville - Georgia Forestry 33 1.86 1.23 -0.23 -3.27 2.82 4 0.44 -3.54 4.41 99 13-089-0002 Decatur - South DeKalb 57 1.47 1.17 0.37 -1.94 3.11 4 -0.52 -3.32 2.28 99 13-097-0004 Douglasville - West Strickland Street 36 1.97 4.19 -3.73 -6.98 -0.48 4 3.66 -0.47 7.79 96 13-121-0055 Atlanta - Confederate Ave. 35 1.91 3.03 -2.57 -5.72 0.57 4 0.35 -5.77 6.47 99 13-127-0006 Brunswick - Risley School 39 3.07 3.10 -1.85 -6.96 3.25 4 0.25 -3.41 3.91 96 13-135-0002 Lawrenceville - Gwinnett Tech 35 2.25 1.50 -0.09 -3.79 3.61 4 -1.65 -6.50 3.20 99 13-151-0002 McDonough - County Extension Office 36 1.27 0.92 -0.43 -2.53 1.67 4 -1.95 -7.23 3.33 99 13-213-0003 Chatsworth - Fort Mountain 35 1.49 1.24 -0.61 -3.06 1.83 4 -3.04 -7.66 1.59 99 13-215-0008 Columbus - Airport 35 1.04 0.71 0.47 -1.24 2.17 4 1.48 -1.89 4.84 99 13-223-0003 Yorkville - King's Farm 36 0.97 2.46 -2.23 -3.83 -0.62 4 1.65 -0.13 3.43 99 13-245-0091 Augusta - Bungalow Rd. 36 0.79 2.18 -2.00 -3.30 -0.70 4 14.29 13.03 15.54 95 13-247-0001 Conyers - Monastery 36 1.52 0.90 0.26 -2.28 2.75 4 1.13 -2.51 4.76 98 13-261-1001 Leslie - Union High School 37 3.08 2.68 -1.13 -6.23 3.96 4 -5.56 -7.24 -3.87 97 Georgia Ambient Air Monitoring Program 731 1.70 1.82 -0.64 -3.67 2.39 80 1.18 -3.97 6.34 98.2 95% LPL: 95% Lower Probability Limit 95% UPL: 95% Upper Probability Limit Table 10: O3 Data Quality Assessment PARTICULATE MATTER Particulate matter is a mixture of substances that include elements such as carbon, metals, nitrates, organic compounds and sulfates; complex mixtures such as diesel exhaust and soil. Particles with an aerodynamic diameter of 10 microns or smaller pose an increased health risk because they can deposit deep in the lung and contain substances that are particularly harmful to human health. Respirable particulate matter (PM10) and fine particulate matter (PM2.5) increase the chance of respiratory disease, lung damage, cancer, and premature death. Particulate matter monitoring is conducted using both manual and continuous type samplers. Manual samplers are operated on a six-day sampling schedule for PM10, and a similar, or more frequent schedule, for PM2.5. The Georgia Ambient Monitoring particulate program also includes total suspended particulates (TSP), sulfate, mass and lead monitoring. Particulate matter is a controlled data set, and as such is subject to formal data quality objectives and federal and state regulations. Accuracy (field): The accuracy of particulate samplers is determined by comparing the instrument's flow rate to a certified variable orifice (PM10 and TSP), or a calibrated mass flow meter (TEOM, BAM, and PM2.5 samplers) that is certified against a National Institute of Standards and Technology (NIST) 123 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance traceable flow device or calibrator. Since an accurate measurement of particulate matter is dependent upon flow rate, the Ambient Monitoring Program conducts semi-annual flow rate audits at each site. The average percent difference between the sampler flow rates and the audit flow rates represents the combined differences from the certified value of all the individual audit points for each sampler. The upper and lower probability limits represent the expected flow rate accuracy for 95 percent of all the single analyzer's individual percent differences for all audit test levels at a single site. Overall, the 2012 flow audit results indicate that the flow rates of samplers in the network are almost all within bounds. Approximately ninety-eight percent of the instruments audited in 2012 operated within the Georgia Ambient Monitoring Program's control limits. The 2012 PM2.5 yearly data quality assessment summary of integrated and analyzation using federal reference method, the PM2.5 yearly data quality assessment summary semi-continuous measurements, and the PM10 yearly data quality assessment summary of 24-hour integrated measurements and semi-continuous measurements are shown in the tables below. 124 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance PM2.5 Yearly Data Quality Assessment Summary of Integrated Sampling and Analyzation Using Federal Reference Method Site Code Site Name Collocated (g/m3) One-Point Flow Rate Check (L/min) No. of Obs. Precision Estimate CV (%) No. of Obs. Avg Absolute Signed (%) Bias (%) Bias (%) Semi-Annual Flow Check (L/min) (Bias %) No. of Obs. Avg (%) 95% 95% LPL UPL (%) (%) Completeness (%) 13-021-0007 Macon - Allied Chemical 28 13-021-0012 Macon - Macon SE NA 13-051-0017 Savannah - Market Street (Scott) 20 13-051-0091 Savannah - Mercer Jr. High School NA 13-059-0001 Athens - Fire Station 7 NA 13-063-0091 Forest Park - D.O.T. NA 13-067-0003 Kennesaw - National Guard NA Powder Springs - Macland Aquatic 13-067-0004 Center NA 13-089-2001 Doraville-Health Department NA 13-089-0002 Decatur - South DeKalb 23 13-095-0007 Albany - Turner Elem. School NA 13-115-0005 Rome - Coosa High School NA 13-121-0032 Atlanta - E. Rivers School 268 13-121-0048 Atlanta - Georgia Tech NA 13-127-0006 Brunswick - Risley Middle Sch. NA 13-135-0002 Lawrenceville - Gwinnett Tech NA 13-139-0003 Gainesville - Fair St. Elem. Sch. NA 13-153-0001 Warner Robins Air Base NA 13-185-0003 Valdosta - S. L. Mason School 28 13-215-0001 Columbus - Health Department NA 13-215-0008 Columbus - Airport NA 13-215-0011 Columbus - Cusseta Rd. Sch. NA 13-223-0003 Yorkville - King's Farm NA 13-245-0005 Augusta - Med. Col. Of GA 24 13-245-0091 Augusta - Bungalow Rd. Sch. NA 13-295-0002 Rossville Maple Street NA 13-303-0001 Sandersville - Health Department NA 13-319-0001 Gordon - Police Dept. NA 6.28 NA 5.76 NA NA NA NA NA NA 16.85 NA NA 8.71 NA NA NA NA NA 6.28 NA NA NA NA 6.99 NA NA NA NA 12 -1.02 1.48 11 -0.80 1.24 12 -0.13 1.14 11 1.52 1.95 12 -0.56 1.02 12 -0.18 0.47 14 -0.83 1.51 -1.48 -1.24 +/-1.14 +1.95 -1.02 -0.47 +/-1.51 9 0.11 0.64 12 -1.04 1.54 12 -1.11 1.40 13 0.09 0.43 11 -0.45 0.67 14 -0.02 0.99 12 -0.58 1.71 12 -0.74 1.04 12 -0.30 0.65 11 -1.02 1.48 12 0.44 1.30 12 -1.02 1.48 12 0.35 0.76 12 0.05 0.42 12 0.17 0.73 10 -0.28 0.60 11 0.07 1.05 11 -0.11 0.85 13 -0.45 0.80 11 -6.15 16.01 12 -0.73 1.05 +/-0.64 -1.54 -1.4 +/-0.43 -0.67 +/-0.99 +/-1.71 -1.04 -0.65 -1.48 +/-1.3 -1.48 +/-0.76 +/-0.42 +/-0.73 -0.6 +/-1.05 +/-0.85 +/-0.8 -16.01 -1.05 5 1.28 0.17 2.39 2 1.03 0.52 1.54 2 1.40 -0.14 2.94 2 1.95 -2.63 6.53 2 1.60 -2.01 5.21 2 1.62 0.33 2.90 2 -1.15 -3.67 1.37 2 -0.62 -1.04 -0.21 6 -0.02 -2.13 2.09 2 -0.66 -1.15 -0.16 2 3.03 1.97 4.08 2 -0.06 -1.38 1.27 4 1.47 -0.43 3.37 2 0.69 0.44 0.95 2 -1.27 -1.67 -0.87 2 0.42 -1.25 2.10 2 0.94 -1.17 3.06 2 2.22 -0.91 5.34 5 1.28 0.17 2.39 2 0.64 -1.13 2.40 2 0.30 -0.53 1.14 2 1.80 1.03 2.58 2 -0.65 -0.65 -0.65 4 0.92 -0.12 1.97 2 1.46 1.29 1.63 4 -0.27 NA NA 2 0.97 0.29 1.65 2 1.93 1.84 2.01 86.00 86.00 79.00 78.00 83.00 84.00 85.00 87.00 82.00 77.00 90.00 86.00 85.00 87.00 81.00 61.00 82.00 87.00 87.00 84.00 79.00 85.00 85.00 86.00 86.00 83.00 81.00 83.00 Georgia Ambient Air Monitoring Program 363 44.59 95% LPL: 95% Lower Probability Limit 330 -0.50 1.53 69 0.72 -2.76 1.88 95% UPL: 95% Upper Probability Limit 83.00 Table 11: PM2.5 Data Quality Assessment for FRM Samplers 125 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance PM2.5 Yearly Data Quality Assessment Summary of Semi-Continuous Measurements Site Code Site Name One-Point Flow Rate Check Semi-Annual Flow Check (L/min) (Bias (L/min) %) Completeness No. of Avg Absolute Signed No. of Avg 95% LPL 95% UPL (%) Obs. (%) Bias (%) Bias (%) Obs. (%) (%) (%) 13-021-0012 Macon - Macon SE 12 -0.95 1.27 -1.27 3 -1.27 -3.44 0.89 86 13-051-1002 Savannah - W. Lathrop & Augusta Ave. 11 1.32 1.85 +1.85 2 1.93 0.29 3.57 89 13-059-0002 Athens - Fire Station 7 12 -1.49 1.74 -1.74 2 -1.68 -3.04 -0.31 83 13-077-0002 Newnan - University of West Georgia 12 -0.74 1.05 -1.05 2 -0.06 -0.23 0.11 93 13-089-0002 Decatur - South DeKalb 14 -0.42 0.58 -0.58 2 -0.09 -0.17 -0.01 82 13-121-0055 Atlanta - Confederate Ave. 11 0.55 0.92 +0.92 2 0.03 -0.05 0.11 92 13-135-0002 Lawrenceville - Gwinnett Tech 12 -1.39 1.60 -1.6 3 -1.71 -2.45 -0.96 82 13-151-0002 McDonough - County Extension Office 12 1.64 2.04 +2.04 2 1.52 0.15 2.89 84 13-215-0008 Columbus - Airport 12 -4.23 4.58 -4.58 2 -5.01 -5.01 -5.01 85 13-223-0003 Yorkville - King's Farm 12 0.18 0.56 +/-0.56 2 0.21 -0.71 1.13 83 13-245-0091 Augusta - Bungalow Rd. Sch. 12 -2.72 3.37 -3.37 2 -3.55 -6.25 -0.84 93 Georgia Ambient Air Monitoring Program 132 -0.77 1.77 24 -0.93 -5.09 3.08 87 95% LPL: 95% Lower Probability Limit 95% UPL: 95% Upper Probability Limit Table 12: PM2.5 Data Quality Assessment for Semi-Continuous Samplers PM10 Yearly Data Quality Assessment Summary of 24-Hour Integrated and Semi-Continuous Measurements Site Code Site Name Collocated (g/m3) One-Point Flow Rate Check Semi-Annual Flow Check (L/min) (L/min) Completeness No. of Obs. Precision Estimate CV (%) No. of Obs. Avg (%) Absolute Bias (%) Signed Bias (%) No. of Obs. Avg (%) 95% 95% LPL UPL (%) (%) (%) 13-021-0007 Macon - Allied Chemical 49 7.59 14 2.11 2.83 +2.83 6 -0.24 -2.57 2.10 97 13-051-0014 Savannah - Shuman School NA NA 11 -0.52 1.45 +/-1.45 2 -0.33 -0.58 -0.08 92 13-055-0001 Summerville - DNR Fish Hatchery NA NA 12 0.52 0.80 +0.8 2 0.21 -1.70 2.13 95 13-089-2001 Doraville - Police Department NA NA 12 0.04 0.49 +/-0.49 3 1.51 -0.63 3.64 93 13-095-0007 Albany - Turner Elem. School NA NA 10 -0.35 0.82 +/-0.82 3 1.51 -0.63 3.64 93 13-115-0005 Rome - Coosa High School NA NA 11 -0.86 1.53 -1.53 3 0.34 -8.62 9.29 98 13-121-0032 Atlanta - E. Rivers School 52 18.54 11 -0.60 0.89 -0.89 4 -1.22 -3.53 1.10 95 13-115-0004 Brunswick - Arco Pump Station NA NA 12 0.89 1.74 +/-1.74 2 1.53 1.36 1.70 82 Columbus - Cusseta Rd. Elem. 13-121-0039 School NA NA 12 -0.06 0.76 +/-0.76 3 1.23 -1.67 4.13 98 Augusta - Bungalow Rd. Elem. 13-245-0091 School NA NA 11 -0.17 1.10 +/-1.1 2 2.02 1.49 2.56 95 13-303-0001 Sandersville - Health Department NA NA 11 0.90 2.27 +/-2.27 2 1.15 0.47 1.83 90 13-121-0048 GA Tech NA NA 12 -0.16 1.30 +/-1.3 2 0.36 -0.30 1.02 89 13-089-0002 South DeKalb NA NA 13 -0.92 1.87 -1.87 2 0.36 1.68 2.54 93 Georgia Ambient Air Monitoring Program: 101 26.13 127 0.23 1.36 36 0.46 -2.26 1.92 93 NA: Not Applicable 95% LPL: 95% Lower Probability Limit 95% UPL: 95% Upper Probability Limit Table 13: PM10 Data Quality Assessment of 24-Hour Integrated and Semi-Continuous Samplers Precision (field): Precision data for non-continuous particulate samplers is obtained through collocated sampling whereby two identical samplers are operated side-by-side and the same laboratory conducts filter analyses. Collocated samplers are located at selected sites and are intended to represent overall network precision. Validity of the data is based on the percent difference 126 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance of the mass concentrations of the two samplers. In 2012 collocated PM2.5 samplers were operated at Augusta-Medical College, Atlanta-E. Rivers, Decatur-South DeKalb, Savannah-Market Street and Macon-Allied. Collocated PM10 samplers were operated at Atlanta-E. Rivers and Macon-Allied, and collocated TSP-Lead samplers were operated at Atlanta-DMRC. Particulate samplers (collocated PM10 and TSP) must have mass concentrations greater than or equal to 20 g/m3 to be used in data validity calculations. The difference between the mass concentrations must be no greater than 5 g/m3. If the mass concentrations are greater than 80 g/m3, the difference must be within 7% of each other. TSP (lead) samplers must have both mass concentrations greater than or equal to 0.15 g/m3 to be used in data validity calculations. For collocated PM2.5 samplers, data probability limits validity is based on the sampler's coefficient of variation, which cannot exceed 10%. Both sample masses must also be greater than 6 g/m3. Precision for continuous PM2.5 monitors is based on the comparison of the sampler's/analyzer's indicated and actual flow rates. The differences between the flow rates must be within 15. Accuracy (lab): Annual performance audits for PM10 and PM2.5 mass analysis programs include an on-site check and assessment of the filter weighing balance, relative humidity and temperature sensors, and their documentation. The performance audits conducted in 2012 found that the Ambient Monitoring Program was operating in accordance with U.S. EPA guidelines and that the data were of good quality and should be considered data-for-record. Precision (lab): Laboratories perform various quality control tasks to ensure that quality data are produced. Tasks include duplicate weighing on exposed and unexposed filters, replicate analysis on every tenth filter, and a calibration of the balance before each weighing session. Upon receipt of particulate matter filters from the field, laboratory staff has up to 30 days to analyze the PM10 and PM2.5 samples. Filters are visually inspected for pinholes, loose material, poor workmanship, discoloration, non-uniformity, and irregularities, and are equilibrated in a controlled environment for a minimum of 24 hours prior to the filters being weighed. If room conditions are not within the established U.S. EPA control limits, weighing is done only after the proper environment is reestablished and maintained for 24 hours. In 2012, there were no occurrences in which the Georgia's Ambient Monitoring laboratory balance room was outside of control limits. The analytical precision results indicate that the Ambient Monitoring Program is providing precise particulate matter data. The tables below show the unexposed and exposed filter replicate results for the Air Protection Branch's (APB) laboratory in 2012. QC Checks for Pre-weighed Filters PM10 Total # of sample analyzed 700 Total # of replicates 35 Total % replicated 5% Total # out-of-range 0 Source: Laboratory Section, Quality Control Report Table 14: Summary of Unexposed Filter Mass Replicates QC Checks for Post-weighed Filters PM10 Total # of samples analyzed 602 Total # of replicates 42 Total % replicated 7% Total # out-of-range 0 Source: Laboratory Section, Quality Control Report Table 15: Summary of Exposed Filter Mass Replicates PM2.5 5995 663 11% 0 PM2.5 4761 482 10% 0 127 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance AIR TOXICS In 1996, the Air Protection Branch established an Air Toxics Network in major urban areas of the state to determine the average annual concentrations of air toxics. The program was established to assess the effectiveness of control measures in reducing air toxics exposures. Compounds identified as air toxics vaporize at ambient temperatures, play a critical role in the formation of ozone, and have adverse chronic and acute health effects. Sources of air toxics include motor vehicle exhaust, waste burning, gasoline marketing, industrial and consumer products, pesticides, industrial processes, degreasing operations, pharmaceutical manufacturing, and dry cleaning operations. Under the current air toxic sampling schedule, ambient air is collected in a stainless steel canister, on a quartz filter, and on a multi-layer cartridge every 12 days over a 24-hour sampling period at each of the network stations. Toxic particulate samples are collected and analyzed for air toxic contaminants to support the Georgia Air Toxic Network. By using a low-flow multi-channel sampler capable of sampling onto filters or cartridges, ambient air is collected and analyzed for carbonyls, polycyclic aromatic hydrocarbons (PAH) compounds (also called semi-volatile organic compounds or semi-VOCs), volatile organic compounds (VOCs), and toxic metals. The quality of the air toxic data set is governed by a series of quality assurance activities, including audits. The laboratory and monitoring staff are made aware of any exceedance found during an audit, and every effort is made to ensure that the data collected is as accurate as possible. Flow audits of the toxic metal, VOCs, semi-VOCs and carbonyl samplers are conducted annually at each site to ensure the accuracy of measuring these compounds. Flow rates are a determining factor in calculating concentration and are included as part of the Quality Assurance Program. Although toxics data are a descriptive data set, completeness is issued based on the operating parameters of the sampler. Corrections are made to the samplers if an audit finds the sampler to be outside the Air Toxic Program control limits. Precision (field and lab): As part of the Air Toxic Program laboratory analyses, internal QC techniques such as blanks, control samples, and duplicate samples are applied to ensure the precision of the analytical methods and that the toxics data are within statistical control Stainless steel canisters used to collect ambient air samples are also checked for contamination. Canisters are analyzed for aromatic and halogenated hydrocarbons. One canister per batch of eight is assayed to ensure individual compound measurements fall below the limit of detection. In the event a compound exceeds canister cleanliness criteria, the canister and all other canisters represented in the batch are re-cleaned until compounds meet the cleanliness criteria. In addition, Xontech 910A air samplers are checked for cleanliness. Failed air collection media are re-cleaned and re-tested until they pass Xontech 910A cleanliness criteria. Accuracy (field): The accuracy of air toxic samples is determined by comparing the instrument's flow rate to a certified variable orifice, or a calibrated mass flow meter, that is certified against a National Institute of Standards and Technology (NIST) traceable flow device or calibrator. Since an accurate measurement of air toxics data is dependent upon flow rate, the Ambient Monitoring Program conducts annual flow rate audits at each site. The percent difference between the sampler flow rates and the audit flow rates is computed for each air toxics sampler. NATTS There are currently 189 hazardous air pollutants (HAPs), or air toxics, with emissions regulated under the Clean Air Act (CAA). These compounds have been associated with a wide variety of adverse human health and ecological effects, including cancer, neurological effects, reproductive effects, and developmental effects. According to the Government Performance Results Act (GPRA), the U.S. Environmental Protection Agency (U.S. EPA) is committed to reducing air toxics emissions by 75 percent from 1993 levels in order to significantly reduce Americans' risk of cancer and of other serious 128 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance health effects caused by airborne toxic chemicals. Early efforts toward this end have focused on emissions reductions through the assessment of technical feasibility. However, as new assessment tools are developed, more attention is being placed on the goal of risk reduction associated with exposure to air toxics. To meet the GPRA goals, the National Air Toxics Trends Station (NATTS) network has been established, consisting of 27 stations nationwide, with one in Georgia. Having data of sufficient quality is paramount for a network such as the NATTS. As such, Georgia has closely followed the Quality System (QS) for the NATTS, established by U.S. EPA, two aspects of which are Technical Systems Audits (TSAs) and Instrument Performance Audits (IPAs) of each network station and its affiliated sample analysis laboratory. Another integral part of the QS is the quarterly analysis of performance evaluation (PE) samples. Furthermore, the sampling and analytical techniques selected to collect and quantify the air toxics of concern must demonstrate acceptable analytical and overall sampling precision, as well as suitable overall method detection limits that are compatible with expected ambient air toxics concentrations. There are 27 sites nationwide in the NATTS network. Georgia joined the network with one site established in Decatur at the South DeKalb Monitoring Station. The location of all sites, whether the site is located in an urban or rural area, the unique AQS identification code (site code), and current status for all the sites are given in Table 16, on the next page. The list was taken from the U.S. EPA website, http://www.epa.gov/ttnamti1/natts.html. 129 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance (Source: http://www.epa.gov/ttnamti1/natts.html) Table 16: Current List of NATTS Sites with AQS Site Codes 130 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance Several Measurement Quality Objectives (MQOs) have been established for the NATTS network in order to ensure that only data of the highest quality are collected by the NATTS network, and to meet the NATTS Data Quality Objective (DQO): "to be able to detect a 15 percent difference (trend) between two consecutive 3-year annual mean concentrations within acceptable levels of decision error"2. Initially, the four compounds of primary importance to the NATTS program were benzene, 1,3butadiene, formaldehyde, and PM10 arsenic. The Data Quality Objective MQOs for these four compounds are summarized in Table 17 below. Compound Benzene 1,3-Butadiene Formaldehyde Arsenic Completeness > 85 % > 85 % > 85 % > 85 % Precision (Coefficient of Variation) < 15 % < 15 % < 15 % < 15 % Laboratory Bias < 25 % < 25 % < 25 % < 25 % Method Detection Limit (MDL) 0.044 g/m3 0.020 g/m3 0.014 g/m3 0.046 ng/m3 Table 17: Measurement Quality Objectives for the NATTS Program Other compounds have been added to the list of compounds, including hexavalent chromium, acrolein, and polycyclic aromatic hydrocarbons (PAHs). GA EPD collects data to monitor for these compounds as part of the NATTS program, as well as organic carbon, additional carbonyls, and additional volatile organic compounds. The MQOs require that: (1) sampling occurs every sixth day and is successful 85 percent of the time; (2) precision as measured by the coefficient of variation (CV) be controlled to less than 15 percent; and (3) that laboratory (measurement) bias be less than 25 percent. Data acquired to assess compliance with the above stated MQOs are derived from a variety of sources. These sources are given in Table 18. Criteria Completeness Precision Bias - Laboratory Bias - Field MDL Data Source Air Quality System (AQS) AQS and Proficiency Testing Proficiency Testing Audits of Sampler Flowrates Laboratories MQO Limit < 15 % < 15 % < 25 % < 10 % 0.046 ng/m3 to 0.044 g/m3 Table 18: MQO Data Sources for the Georgia NAATS Program The Air Quality System (AQS) database contains raw data that is used to assess data completeness, and to estimate precision from results of replicate analyses and collocated sampling. In addition, results from the analysis of proficiency testing samples allow one to calculate laboratory precision and bias. Completeness (of NATTS Data): The AQS database was accessed and the raw data records analyzed for 23 compounds having the AQS codes given in Table 19 on the next page. The completeness of the 2012 AQS dataset was assessed for four compounds: benzene, 1,3-butadiene, formaldehyde, and arsenic. The results are shown in Table 20, on the next page. The percent completeness ranged from 85% to 90.6%, with sampling occurring every sixth day. Primary and collocated data are differentiated in AQS by use of parameter occurrence codes (POCs). 2 Quality Assurance Handbook for Air Pollution Measurement System. Volume 1. Principles. EPA-600/R94/038A, January 1994. 131 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance Compound Name Benzene 1,3-Butadiene Carbon Tetrachloride Chloroform 1,2-Dibromoethane 1,2-Dichloropropane 1,2-Dichloroethane Dichloromethane 1,1,2,2-Tetrachloroethane Tetrachloroethylene Trichloroethylene Vinyl Chloride Cis-1,3-Dichloropropene Trans-1,3-Dichloropropene Formaldehyde Acetaldehyde Arsenic Beryllium Cadmium Lead Manganese Mercury Nickel AQS Code 45201 43218 43804 43803 43843 43829 43815 43802 43818 43817 43824 43860 43831 43830 43502 43503 82103 82105 82110 82128 82132 82142 82136 Table 19: 23 Selected HAPs and Their AQS Parameter Codes Site Decatur, GA Completeness of Compound by AQS Number and by Name 45201 43218 43502 benzene 1,3-butadiene formaldehyde 90.6% 90.6% 90% 82103 arsenic 85% Table 20: Percent Completeness of Georgia's 2012 AQS Data, Selected Compounds PHOTOCHEMICAL ASSESSMENT MONITORING In 1996, the Air Protection Branch began a routine seasonal sampling program to gather information about non-methane hydrocarbon (NMHC) species that were precursors to ozone formation in high ozone areas. In 1994, federal regulations required states to establish photochemical assessment monitoring stations (PAMS) as part of their State Implementation Plan (SIP) for monitoring networks in areas designated as serious or higher for ozone. Monitoring is to continue until the ozone standard is reached. The PAMS program is intended to supplement ozone monitoring and add detailed sampling for its precursors. PAMS sites collect data on real-time total NMHC, PAMS speciated VOCs, carbonyls, and various meteorological parameters at ground level and aloft. As this is a descriptive data set, there are currently no mandatory data quality objectives or regulations for the data. However, efforts are made to ensure that accurate data are collected and that the analyzers are operating within PAMS audit standards. Accuracy (field and lab): Laboratory performance audits are conducted annually to assess the laboratory's ability to measure ambient levels of hydrocarbons. Through-the-probe sampler 132 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance performance audits are conducted semi-annually at each monitoring site to assess the integrity of the sampling, analysis, and transport system. The 2012 PAMS speciated VOCs yearly data quality assessment summary for the three PAMS sites on the tables below show that most results were within the PAMS' control limits of 20%. PAMS Speciated VOCs Yearly Data Quality Assessment Summary for Decatur - South DeKalb Site Parameter Code Parameter Name 2-Comp. Std. Weekly Check No. of Obs. Precision Estimate CV (%) Absolute Bias Estimate (%) Validation of Bias Avg (%) 95% LPL (%) 95% UPL (%) Annual Perform, Evaluation Bias No. of Obs. Avg (%) 95% LPL (%) 95% UPL (%) 43202 Ethane+ NA NA NA NA NA NA 3 11.48 6.17 16.80 43204 Propane* 18 21.41 22.58 -18.08 -48.12 16.52 3 11.23 5.99 16.46 43214 Isobutane+ NA NA NA NA NA NA 3 -9.95 -18.77 -1.14 43216 Trans-2-Butene+ NA NA NA NA NA NA 3 -58.17 -61.88 -54.46 43220 N-Pentane+ NA NA NA NA NA NA 3 -24.07 -32.92 -15.23 43285 2-Methylpentane+ NA NA NA NA NA NA 3 -55.85 -62.41 -49.28 43243 Isoprene+ NA NA NA NA NA NA 3 -81.50 -82.83 -80.18 43231 N-Hexane+ NA NA NA NA NA NA 3 -28.22 -49.15 -7.29 45201 Benzene* 18 28.1 47.62 -32.54 -80.98 3.86 3 -10.34 -37.1 16.42 43232 N-Heptane+ NA NA NA NA NA NA 3 -63.50 -67.89 -59.11 45202 Toluene+ NA NA NA NA NA NA 3 -69.13 -75.66 -62.59 45203 Ethylbenzene+ NA NA NA NA NA NA 3 -68.29 -73.79 -62.79 43238 N-Decane+ NA NA NA NA NA NA 3 -40.69 -42.35 -39.02 45225 1,2,3-Trimethylbenzene+ NA NA 95% LPL: 95% Lower Probability Limit PQAO: Primary Quality Assurance Organization * NIST traceable + Only NIST traceable by weight NA NA NA NA 3 -50.82 -53.34 -48.30 95% UPL: 95% Upper Probability Limit Completeness (%) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Table 21: PAMS Speciated VOCs Yearly Data Quality Assessment for South DeKalb 133 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance PAMS Speciated VOCs Yearly Data Quality Assessment Summary for Conyers - Monastery Site Parameter Code Parameter Name 2-Comp. Std. Weekly Check No. of Obs. Precision Estimate CV (%) Absolute Bias Estimate (%) Validation of Bias Avg (%) 95% LPL (%) 95% UPL (%) Annual Perform, Evaluation Bias No. of Obs. Avg (%) 95% LPL (%) 95% UPL (%) 43202 Ethane+ NA NA NA NA NA NA 3 -12.53 -26.60 1.54 43204 Propane* 6 19.48 14.18 -3.23 -24.90 18.44 3 -9.80 -18.78 -0.83 43214 Isobutane+ NA NA NA NA NA NA 3 23.36 20.77 25.96 43216 Trans-2-Butene+ NA NA NA NA NA NA 3 22.83 17.43 28.22 43220 N-Pentane+ NA NA NA NA NA NA 3 25.40 22.29 28.51 43285 2-Methylpentane+ NA NA NA NA NA NA 3 -16.09 -38.33 6.15 43243 Isoprene+ NA NA NA NA NA NA 3 -24.06 -40.98 -7.14 43231 N-Hexane+ NA NA NA NA NA NA 3 -19.00 -27.57 -10.43 45201 Benzene* 6 11.65 10.09 4.54 -8.41 17.5 3 -6.66 -22.99 9.67 43232 N-Heptane+ NA NA NA NA NA NA 3 -18.52 -25.66 -11.38 45202 Toluene+ NA NA NA NA NA NA 3 -21.03 -28.39 -13.67 45203 Ethylbenzene+ NA NA NA NA NA NA 3 -1.85 -7.52 3.81 43238 N-Decane+ NA NA NA NA NA NA 3 24.35 14.72 33.97 45225 1,2,3-Trimethylbenzene+ NA NA 95% LPL: 95% Lower Probability Limit PQAO: Primary Quality Assurance Organization * NIST traceable + Only NIST traceable by weight NA NA NA NA 3 -8.44 -13.02 -3.86 95% UPL: 95% Upper Probability Limit Completeness (%) 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Table 22: PAMS Speciated VOCs Yearly Data Quality Assessment for Conyers 134 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance PAMS Speciated VOCs Yearly Data Quality Assessment Summary for Yorkville King's Farm Site Parameter Code Parameter Name 2-Comp. Std. Weekly Check No. of Obs. Precision Estimate CV (%) Absolute Bias Estimate (%) Validation of Bias Avg (%) 95% LPL (%) 95% UPL (%) Annual Perform, Evaluation Bias No. of Obs. Avg (%) 95% LPL (%) 95% UPL (%) 43202 Ethane+ NA NA NA NA NA NA 3 0.54 -1.29 2.36 43204 Propane* 15 14.65 11.80 -2.29 -24.18 18.64 3 -3.67 -7.25 -0.09 43214 Isobutane+ NA NA NA NA NA NA 3 -6.03 -8.34 -3.72 43216 Trans-2-Butene+ NA NA NA NA NA NA 3 -4.25 -7.55 -0.95 43220 N-Pentane+ NA NA NA NA NA NA 3 -2.91 -8.37 2.55 43285 2-Methylpentane+ NA NA NA NA NA NA 3 -7.85 -9.85 -5.84 43243 Isoprene+ NA NA NA NA NA NA 3 -29.19 -37.16 -21.22 43231 N-Hexane+ NA NA NA NA NA NA 3 31.58 22.91 40.25 45201 Benzene* 15 23.49 26.77 17.64 -16.88 51.8 3 18.77 15.84 21.7 43232 N-Heptane+ NA NA NA NA NA NA 3 29.01 22.54 35.49 45202 Toluene+ NA NA NA NA NA NA 3 16.21 14.13 18.3 45203 Ethylbenzene+ NA NA NA NA NA NA 3 19.21 16.38 22.05 43238 N-Decane+ NA NA NA NA NA NA 3 23.04 15.17 30.9 45225 1,2,3-Trimethylbenzene+ NA NA 95% LPL: 95% Lower Probability Limit PQAO: Primary Quality Assurance Organization * NIST traceable + Only NIST traceable by weight NA NA NA NA 3 25.51 -0.58 51.61 95% UPL: 95% Upper Probability Limit Completeness (%) 84.00 84.00 84.00 84.00 84.00 84.00 84.00 84.00 84.00 84.00 84.00 84.00 84.00 84.00 Table 23: PAMS Speciated VOCs Yearly Data Quality Assessment for Yorkville 135 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance PAMS Speciated VOCs Yearly Data Quality Assessment for GA EPD Ambient Air Monitoring Program Summary Parameter Code Parameter Name 2-Comp. Std. Weekly Check No. of Obs. Precision Estimate CV (%) Absolute Bias Estimate (%) Validation of Bias Avg (%) 95% LPL (%) 95% UPL (%) Annual Perform, Evaluation Bias No. of Obs. Avg (%) 95% LPL (%) 95% UPL (%) 43202 Ethane+ NA NA NA NA NA NA 9 -0.17 -8.92 8.58 43204 Propane* 39 18.51 17.14 -9.72 -36.87 17.42 9 -0.75 -7.09 5.60 43214 Isobutane+ NA NA NA NA NA NA 9 2.46 -3.01 7.93 43216 Trans-2-Butene+ NA NA NA NA NA NA 9 -13.20 -17.43 -8.96 43220 N-Pentane+ NA NA NA NA NA NA 9 -0.53 -6.79 5.74 43285 2-Methylpentane+ NA NA NA NA NA NA 9 -26.59 -40.03 -13.16 43243 Isoprene+ NA NA NA NA NA NA 9 -44.92 -55.74 -34.09 43231 N-Hexane+ NA NA NA NA NA NA 9 -5.21 -19.20 8.77 45201 Benzene* 39 23.80 33.83 -7.54 -44.03 28.95 9 0.59 -17.59 18.77 43232 N-Heptane+ NA NA NA NA NA NA 9 -17.67 -23.78 -11.55 45202 Toluene+ NA NA NA NA NA NA 9 -24.65 -30.46 -18.84 45203 Ethylbenzene+ NA NA NA NA NA NA 9 -16.98 -21.82 -12.13 43238 N-Decane+ NA NA NA NA NA NA 9 2.23 -5.01 9.47 45225 1,2,3-Trimethylbenzene+ NA NA 95% LPL: 95% Lower Probability Limit PQAO: Primary Quality Assurance Organization * NIST traceable + Only NIST traceable by weight NA NA NA NA 9 -11.25 -26.62 4.12 95% UPL: 95% Upper Probability Limit Completeness (%) 93.00 93.00 93.00 93.00 93.00 93.00 93.00 93.00 93.00 93.00 93.00 93.00 93.00 93.00 Table 24: PAMS Speciated VOCs Yearly Data Quality Assessment for Ambient Monitoring Program Summary METEOROLOGY The Ambient Monitoring Program monitors meteorological parameters such as wind speed, wind direction, ambient temperature, relative humidity, barometric pressure, total ultra violet radiation, precipitation and total solar radiation. Real-time meteorological data are generated to characterize meteorological processes such as transport and diffusion, and to make air quality forecasts and burn day decisions. The data are also used for control strategy modeling, case study analysis, and urban airshed modeling. A state/local meteorology subcommittee of the Air Monitoring Technical Advisory Commission (AMTAC) agreed to define the level of acceptability for meteorological data as those used by the U.S. EPA for both the Prevention of Significant Deterioration (PSD) and Photochemical Assessment Monitoring Stations (PAMS) programs. The Quality Assurance Unit audits to those levels. The data variability collected by this element of the monitoring program is generally described as meeting or not meeting the PSD requirements. Station operators are notified if an exceedance is found during an audit, and every effort is made to ensure that the data meets the audit standards. The wind speed, wind direction, ambient temperature and relative humidity data sets are controlled data sets, and subject to meeting PAMS objectives. Since the inception of the meteorological audit program, the data quality has improved significantly. 136 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance Accuracy (field): The accuracy of meteorological sensors is checked by annual performance audits. Table 25 summarizes the 2012 data quality assessment results. The average difference (average degree difference with respect to ambient temperature) represents the combined differences from the certified value of all the individual audit points for each sensor. The upper and lower probability limits represent the expected accuracy of 95 percent of all the single sensor's individual percent differences for all audit test levels at a single site. Meteorological Measurements Yearly Data Quality Assessment Summary for GA EPD Ambient Air Monitoring Program (as a PQAO) Parameter Code Parameter Name Annual Audit (Bias %) No. of Obs. No. of Site Avg (%) 95% LPL (%) 95% UPL (%) 61101 Wind Speed 52 61102 Wind Direction 52 62101 Ambient Temperature 9 64101 Barometric Pressure 6 62201 Relative Humidity 9 95% LPL: 95% Lower Probability Limit PQAO: Primary Quality Assurance Organization 13 0.58 -1.18 2.35 13 0.13 -0.46 0.71 9 -1.48 -6.58 3.62 6 0.16 -0.20 0.53 9 3.55 -12.48 19.57 95% UPL: 95% Upper Probability Limit Completeness (%) 98.5 98.4 94.8 100.0 94.8 Table 25: Meteorological Measurements Accuracy Results QUALITY CONTROL REPORTS Quality Control (QC) reports are summaries of the quality control activities conducted by the laboratory to support accurate and precise measurements. These activities include: blanks, duplicates, controls, spiked samples, limits of detection, calibrations, and audit results. STANDARDS LABORATORY The U.S. EPA Region IV Standards Laboratory yearly performs technical support and certification services for Georgia's ozone primary standard. Flow rate transfer standards and certification of compressed gas cylinders are sent to the manufacturers for re-certification to ensure that all are traceable to standards of the NIST. A calibration establishes a correction factor to adjust or correct the output of an instrument; a certification establishes traceability of a transfer standard to a NISTtraceable standard; and verification establishes comparability of a standard to a NIST-traceable standard of equal rank. LABORATORY AND FIELD STANDARD OPERATING PROCEDURE Standard Operating Procedures (SOPs) are guidance documents for the operation of quality assurance programs used by the Georgia Ambient Monitoring Program. The SOPs are intended for field operators and supervisors; laboratory, data processing and engineering personnel; and program managers responsible for implementing, designing, and coordinating air quality monitoring projects. Each SOP has a specific method that must be followed to produce data-for-record. The SOPs are developed and published to ensure that, regardless of the person performing the operation, the results will be consistent. SITING EVALUATIONS To generate accurate and representative data, ambient monitoring stations should meet specific siting requirements and conditions. It is assumed that the stations meet the siting criteria in place at the time 137 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Quality Assurance initial operation began. The siting requirements of the AMP Quality Assurance Manual Volume II; 40 CFR 58, Appendix E; U.S. EPA's Quality Assurance Handbook Volume IV: U.S. EPA's Prevention of Significant Deterioration (PSD); and U.S. EPA's PAMS guidelines present siting criteria to ensure the collection of accurate and representative data. The siting criterion for each pollutant varies depending on the pollutant's properties, monitoring objective and intended spatial scale. The U.S. EPA's siting criteria are stated as either "must meet" or "should meet". According to 40 CFR 58, Appendix E, the "must meet" requirements are necessary for high quality data. Any exception from the "must meet" requirements must be formally approved through the Appendix E waiver provision. The "should meet" criteria establish a goal for data consistency. Siting criteria are requirements for locating and establishing stations and samplers to meet selected monitoring objectives, and to help ensure that the data from each site are collected uniformly. There are four main monitoring objectives: to determine highest concentrations expected to occur in the area covered by the network; to determine representative concentrations in areas of high population density; to determine the impact on ambient pollution levels of significant sources or source categories; and to determine general background concentration levels. Typical siting designations are: micro, middle, neighborhood, urban, and regional. These designations represent the size of the area surrounding the monitoring site which experiences relatively uniform pollutant concentrations. Typical considerations for each of these site designations are, for example, the terrain, climate, population, existing emission sources, and distances from trees and roadways. The Quality Assurance Unit conducts siting evaluations annually. Physical measurements and observations include probe/sensor height above ground level, distance from trees, type of ground cover, residence time, obstructions to air flow, and distance to local sources. These measurements and observations are taken to determine compliance with 40 CFR Part 58, Appendix E requirements. 138 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment RISK ASSESSMENT INTRODUCTION In 2012, Georgia EPD collected air toxic samples from five Air Toxics Network (ATN) sites (including two rural background sites) and one National Air Toxics Trends Station (NATTS) site. The following risk assessment reflects data collected at these six locations. Compounds sampled at these sites are shown in Table 26, on the next page. The list was derived from the 189 compounds EPA has designated as Hazardous Air Pollutants (HAPS). Many of the HAPS do not have standardized ambient air sampling and analytical methods. In order to collect the compounds of interest for the Georgia network, at least three types of samplers are used at all locations: HIVOL, PUF, and canister. In addition, a carbonyls sampler was located at the Dawsonville, Savannah, and South DeKalb sites in 2012. This equipment samples for metals, semi-volatile organic compounds, volatile organic compounds, and carbonyls once every twelve days following a pre-established schedule that corresponds to a nationwide sampling schedule. On the twelfth day the sampler runs midnight to midnight and takes a 24-hour composite sample. An exception to this sampling schedule is the South DeKalb site, which samples every six days as part of the National Air Toxics Trends Station (NATTS) and Photochemical Assessment Monitoring Stations (PAMS) networks. In addition, during June, July, and August, the South DeKalb site collects four integrated three-hour carbonyls samples every third day as part of the PAMS and NATTS networks. Some of the chemicals monitored in the ATN are also monitored at sites in the PAMS network. While the monitoring schedule and some analysis methods are different at the PAMS sites and ATN sites, several of the compounds from the PAMS sites were also evaluated and compared to concentrations measured at nearby ATN sites for this report. To provide an idea of the size of risks from environmental hazards as risk analysts will describe them, the continuum below presents risk statistics for some familiar events. Risk analysts describe cancer risks numerically in scientific notation, for example 1 x 10[-5] or 1 x 10-5 or 1.00E-05, which means that there is one chance in 100,000 of an event occurring. It is important to note that these risk statistics are population averages, while risk analysts usually estimate risk to the maximum exposed individual. Additionally, it should be noted that these risk values are considered additional risk. That is, risk above and beyond the normal background risk from exposure in everyday life. Putting Risks in Perspective RESULTS AND INTERPRETATION The air toxics data [volatile organic compounds (VOCs), semi-volatile organic compounds, and metals] collected during 2012 from the Air Toxics Network was evaluated to assess the potential for health concerns. The data collected for the group of chemicals known as carbonyls were assessed separately from the other air toxics, with the exception of acrolein, because those chemicals were only monitored at two of the ATN sites and one of the PAMS locations. 139 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment The initial evaluation consisted of a comparison of the monitored results to "health based" screening values. These values were calculated using procedures recommended in EPA's latest guidance on risk assessment for air toxics, `A Preliminary Risk-Based Screening Approach for Air Toxics Monitoring Data Sets' (U.S. EPA, 2006). Briefly, EPA's prioritized chronic dose-response values for both noncancer (reference concentrations, RfC) and cancer (inhalation unit risks, IUR) were used to generate screening air concentrations. To screen for noncancer effects, the reference concentration was used as a starting point. However, to account for possible exposure to multiple contaminants, the screening air concentration was obtained by dividing the RfC by 10. Screening values for the cancer endpoint were determined by calculating air concentrations equivalent to a risk level of one in one million. Most screening values utilized in this assessment are listed in Appendix A of the previously mentioned guidance document (U.S. EPA, 2006) and updated "Table 1. Prioritized Chronic DoseResponse Values for Screening Risk Assessments (5/21/2012)" (U.S. EPA, 2012). These screening values and the chemicals monitored are displayed in Table 26. For a limited number of chemicals, other resources such as toxicity values from the Regional Screening Table (http://www.epa.gov/reg3hwmd/risk/human/rb-concentration_table/index.htm) were used to calculate conservative screening values. These compounds are indicated with an asterisk. When available, both the names derived from the International Union of Chemistry (IUC) and the common names are given. It is important to emphasize that the screening values were calculated in a very conservative manner. Assumptions were made that accounted for the potential for continuous exposure to air toxics for 24 hours per day for 70 years. The conservative screening process was utilized so that the chance of underestimating the potential for health impacts would be minimized, as chemicals were excluded from further quantitative analysis. Because results for many of the chemicals assessed were routinely below detection limits of the analytical methods available, the initial review of the data was based on an assessment of the number of chemicals detected and the frequency with which they were detected. The process included determining how often (if at all) a chemical was detected (present), if it was present above detection limits, and if those concentrations were above screening values of concern. 140 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment Chemical Screen Value Chemical (g/m3) Screen Value (g/m3) Metals Antimony 0.02 Cobalt 0.01 Arsenic 0.00023 Lead 0.15 Beryllium 0.00042 Manganese 0.005 Cadmium 0.00056 Nickel 0.0021 Chromium 0.000083 Selenium 2 Chromium VI 0.000083 Zinc N/A Semi-Volatiles Acenaphthene 0.3 Cyclopenta(cd)pyrene N/A Acenaphthylene 0.3 Dibenzo(a,h)anthracene 0.00083 Anthracene 0.3 Fluoranthene 0.3 Benzo(a)anthracene 0.0091 Fluorene 0.3 Benzo(b)fluoranthene 0.0091 9-Fluorenone N/A Benzo(k)fluoranthene 0.0091 Ideno(1,2,3-c,d)pyrene 0.0091 Benzo(g,h,i)perylene 0.3 Naphthalene 0.029 Benzo(a)pyrene 0.00091 Phenanthrene 0.3 Benzo(e)pyrene 0.3 Perylene N/A Chrysene 0.091 Pyrene 0.3 Coronene N/A Retene N/A Volatile Organic Compounds Benzene 0.13 1,3 and 1,4-Dimethylbenzene (m/p-Xylene) 10 Benzenecarbonal (Benzaldehyde) Benzyl chloride Bromomethane (Methyl bromide) 1,3-Butadiene Butanal (Butyraldehyde) Chlorobenzene (Phenyl chloride) Chloroethane (Ethyl chloride) Chloroethene (Vinyl chloride) Chloromethane (Methyl chloride) Cyclohexane 1,2-Dibromoethane (Ethylene bromide) 1,2-Dichlorobenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene Dichlorodifluoromethane (Freon 12) 1,1-Dichloroethane (Ethylidene chloride) cis-1,2-Dichloroethene 1,1-Dichloroethene (1,1-Dichloroethylene) Dichloromethane (Methylene chloride) 1,2-Dichloropropane (Propylene chloride) cis-1,3-Dichloropropene trans-1,3-Dichloropropene N/A 0.02 0.5 0.03 N/A 100 1000 0.11 9.0 6300* 0.002 0.091 N/A 0.091 100* 0.63 370 210* 100 0.3 N/A N/A Ethanal (Acetaldehyde) Ethylbenzene Ethenylbenzene (Styrene) 1-Ethyl,4-methyl benzene (4-Ethyltoluene) Freon 113 Hexachloro-1,3-Butadiene(Hexachlorobutadiene) n-Hexane Methanal (Formaldehyde) Methylbenzene/Phenylmethane (Toluene) Propanal (Propionaldehyde) 2-Propanone (Acetone) Propenal (Acrolein) 1,1,2,2-Tetrachloroethane Tetrachloroethene (Perchloroethylene) Tetrachlormethane (Carbon tetrachloride) 1,2,4-Trichlorobenzene 1,2,3-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3,5-Trimethylbenzene 1,1,1-Trichloroethane (Methylchloroform) 1,1,2-Trichloroethane Trichloroethene (Trichloroethylene) 0.45 100 100 N/A N/A 0.045 70 0.0769 500 0.8 32000* 0.002 0.017 3.846 0.067 20 5.2* 7.3* N/A 100 0.063 0.244 1,1-Dichloro-1,2,2,2-tetrafluoroethane(Freon114) N/A Trichlorofluoromethane (Freon 11) 1,2-Dimethylbenzene (o-Xylene) 10 Trichloromethane (Chloroform) 730* 9.8 *From Regional Screening Table (http://www.epa.gov/reg3hwmd/risk/human/rb-concentration_table/index.htm) Table 26: Compounds Monitored and Screening Values Used in Initial Assessment 141 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment Table 27 summarizes the total number of chemicals monitored at each site (excluding all carbonyls except acrolein), the number of chemicals detected, and the number of chemicals detected above the health based screening values for 2012. Seventy-one chemicals were monitored at all the Air Toxics sites, except the South DeKalb site, where 77 air toxic chemicals were monitored. In 2012, thirty-three of the 71 sampled compounds were not detected at the sites, and an additional 12 compounds had 2 or fewer sites with detections. The number of chemicals that were detected at concentrations above the screening levels was even less, with a mean value of 5. Of the three categories of chemicals measured at all sites (VOC, semi-VOC, metals), most of the chemicals that were detected above screening values belonged to the metals group. Location County Number of Compounds Monitored Number of Compounds Detected Number Greater than Screening Value Dawsonville Dawson 71* 24 5 General Coffee Coffee 71 19 5 Macon Bibb 71 30 6 Savannah Chatham 71* 29 5 South DeKalb DeKalb 77* 39 5 Yorkville Paulding 71 21 4 * 6 additional carbonyls were monitored at these locations; compounds that exceed the screening value are summarized in Table 32 Table 27: Summary of Chemicals Analyzed in 2012 142 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment Table 28 shows only the chemicals that were detected above screening values at each Air Toxics site in 2012. It also provides detailed information on how often they were detected (frequency), and the overall average (mean) in micrograms per cubic meter. The number of detects were counted as any number that was above half the method detection limit. The average was computed using the sample concentration when it was above half the method detection limit and substituting half the method detection limit if the sample concentration was below this limit. Location Dawsonville General Coffee Macon Savannah South DeKalb Yorkville Chemical Acrolein Arsenic Benzene Carbon Tetrachloride Chromium Acrolein Arsenic Benzene Chromium Nickel Acrolein Arsenic Benzene Chromium Manganese Nickel Acrolein Arsenic Benzene Chromium Nickel Acrolein Arsenic Benzene Chromium Naphthalene Acrolein Arsenic Benzene Chromium Mean (g/m3) 7.89 x 10-1 8.90 x 10-4 7.67 x 10-1 7.89 x 10-1 1.64 x 10-3 4.91 x 10-1 1.16 x 10-3 4.13 x 10-1 1.40 x 10-3 2.24 x 10-3 5.46 x 10-1 7.10 x 10-4 7.29 x 10-1 1.65 x 10-3 7.80 x 10-3 2.26 x 10-3 6.17 x 10-1 8.90 x 10-4 7.94 x 10-1 1.91 x 10-3 2.98 x 10-3 7.65 x 10-1 5.00 x 10-4 5.47 x 10-1 1.16 x 10-3 7.43 x 10-2 4.27 x 10-1 5.00 x 10-4 4.07 x 10-1 1.42 x 10-3 Detection Frequency 29/30 21/29 28/30 1/30 27/29 18/28 27/28 8/30 28/28 28/28 18/26 23/28 21/30 27/28 28/28 28/28 14/25 20/26 14/29 25/26 26/26 52/59 43/55 33/61 55/55 58/58 20/27 18/28 3/30 24/28 Table 28: Site-Specific Detection Frequency and Mean Chemical Concentration, 2012 143 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment Formula For Calculating Risk Using IUR For Carcinogens Risk IUR*Conc Formula For Calculating Hazard Quotient Using RfC For Noncarcinogens HQ Conc RfC Equation Parameters Risk Theoretical lifetime cancer risk (unitless probability) HQ Hazard quotient (unitless ratio) Conc Measured ambient air concentration in g/m3 IUR Inhalation unit risk (1/(g/m3)) RfC Reference concentration (g/m3) Figure 90: Formulas for Calculating Risk and Hazard Quotient Figure 90 shows the formulas used to calculate cancer risk and non-cancer hazard for chemicals that were carried beyond the screening process into the quantitative assessment. On the following page, Table 29 shows the theoretical cancer risk and non-cancer hazard that would result from an individual breathing air containing the detected chemicals at the estimated concentrations daily for seventy years, or a full lifetime. These cancer risk and hazard quotient estimates are likely conservative because they were calculated assuming continuous exposure to outdoor air at breathing rates typical of moderate exertion. Real risk cannot be calculated, but may be substantially lower. Lifetime cancer risks for the limited number of chemicals exceeding screening values (and excluding that from carbonyls) exceeded 1 x 10-6 or one in one million, a value generally deemed as insignificant. However, lifetime cancer risks for these chemicals did not exceed 1 x 10-4 or one in ten thousand. This value is generally taken as a crude upper limit for "allowable" risk in many regulatory contexts. Individual hazard quotients (HQs) are ratios that relate daily exposure concentrations, or dose, to a concentration or an amount thought to be without appreciable risks of causing deleterious non-cancer effects in sensitive individuals as well as the general population. HQ values less than 1.0 indicate the air "dose" is less than the amount required to cause toxic effects other than cancer. In July of 2007, Georgia EPD changed the analysis method for acrolein. The sampling method changed from a dinitrophenylhydrazine (DNPH) cartridge with high performance liquid chromatography (HPLC) analysis to the VOCs canister collection with gas chromatograph with mass spectroscopy (GC/MS) analysis. This change occurred due to EPA's findings during the School Air Toxics Monitoring Initiative. For more information on this study, please see EPA's website, http://www.epa.gov/ttnamti1/airtoxschool.html. With this GC/MS analysis method, there were several more detections of acrolein than have been seen in previous years, with the HPLC cartridge method. These results are shown along with the other hazard quotients for the Air Toxics sites. The HQ numbers for acrolein are significantly higher than for the other air toxic compounds. This may be due to methodological changes. Potential reasons for differences are still being investigated. 144 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment Location Dawsonville General Coffee Macon Savannah South DeKalb Yorkville Chemical Acrolein Arsenic Benzene Carbon Tetrachloride Chromium Acrolein Arsenic Benzene Chromium Nickel Acrolein Arsenic Benzene Chromium Manganese Nickel Acrolein Arsenic Benzene Chromium Nickel Acrolein Arsenic Benzene Chromium Naphthalene Acrolein Arsenic Benzene Chromium Cancer Risk 4 x 10-6 6 x 10-6 5 x 10-6 2 x 10-5 5 x 10-6 3 x 10-6 2 x 10-5 3 x 10-6 6 x 10-6 2 x 10-5 4 x 10-6 6 x 10-6 2 x 10-5 2 x 10-6 4 x 10-6 1 x 10-5 3 x 10-6 2 x 10-6 3 x 10-6 2 x 10-5 Hazard Quotient 39 0.06 0.03 0.008 0.02 25 0.08 0.01 0.01 0.02 27 0.05 0.02 0.02 0.2 0.03 31 0.06 0.03 0.02 0.03 38 0.03 0.02 0.01 0.02 21 0.03 0.01 0.01 Table 29: Cancer Risk and Hazard Quotient by Location and Chemical, 2012 145 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment Table 30, below, shows total or aggregate theoretical cancer risk and hazard indices (added hazard quotients) for the chemicals (VOCs, semi-VOCS, and metals) carried through the quantitative assessment. For screening purposes such as this, it is generally considered appropriate to treat the potential for effects in an additive manner and to sum cancer risk and hazard quotients, respectively. For example, if cancer risk for two separate chemicals were 1 x 10-4 and 2 x 10-4, then the sum or aggregate cancer risk would equal 3 x 10-4. Likewise, if cancer risk for two separate chemicals were 1 x 10-4 and 1 x 10-5, then total cancer risk for the two would equal 1.1 x 10-4, or rounded to 1 x 10-4. Similarly, if hazard quotients were 0.6 and 0.5 for two different chemicals, it would indicate that each chemical alone is not likely to result in detrimental effects. However, summing the two would yield a hazard index (HI) of 1.1 or rounded to 1. Comparing this value to the threshold value of 1.0, this HI suggests at least the potential for detrimental effects from the combination of the two chemicals. In 2012, the aggregate theoretical cancer risk (excluding carbonyls) for all Air Toxics sites exceeded 1 x 10-6, with risks ranging from 2 x 10-5 to 4 x 10-5. Both the hazard indices (HIs) calculated without the acrolein data and calculated with the acrolein data are shown. The HIs ranged from 0.1 to 0.3 without the acrolein data, and the HIs ranged from 21 to 39 with the acrolein data. Location Dawsonville General Coffee Macon Savannah South DeKalb Yorkville Cancer Risk 4 x 10-5 3 x 10-5 3 x 10-5 3 x 10-5 2 x 10-5 3 x 10-5 Hazard Index without Acrolein 0.1 0.1 0.3 0.1 0.1 0.1 Hazard Index with Acrolein 39 25 27 31 38 21 Table 30: Aggregate Cancer Risk and Hazard Indices for Each Site, Excluding Carbonyls, 2012 146 Georgia Department of Natural Resources Environmental Protection Division Hazard Index Cancer Risk 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment The information from Table 30 is summarized in Figure 91, below, and also shows the previous five years of hazard indices and cancer risk for comparison. With the GC/MS analysis used for the acrolein compound, the hazard indices significantly increased starting with the 2007 data. Before this method change, the highest hazard index generally seen with the Air Toxics data was 0.5. In 2007, the lowest hazard index was 20, at the Savannah site, and the highest was 39, at the Dawsonville site. In 2008 and 2009, the hazard indices were lower overall, with values ranging from 12 at the Macon site to 34 at the South DeKalb site. Then in 2010, there was a dramatic increase at all the sites, with the highest hazard index reading of 213 at the Savannah site. Subsequently, in 2011, the hazard indices decreased drastically, with the lowest value of 18 at the Yorkville site, and the highest value of 66 at the General Coffee site. In 2012, hazard index values remained generally low; the lowest hazard index value was recorded at the General Coffee site (25) and the highest at the Dawsonville site (39). The aggregate theoretical cancer risks have remained relatively consistent though the six years, with values ranging from 2 x 10-5 to 7 x 10-5. 250 8.00E-05 7.00E-05 200 6.00E-05 150 5.00E-05 4.00E-05 100 3.00E-05 2.00E-05 50 1.00E-05 0 0.00E+00 2007 Hazard Index 2008 2009 2010 Site 2011 2012 Cancer Risk 2007 2008 2009 2010 2011 2012 Figure 91: Aggregate Cancer Risk and Hazard Index by Site for 2007-2012 A few of the compounds collected from the PAMS network were evaluated in conjunction with the Air Toxics data. The PAMS network is a federally mandated network required to monitor for ozone precursors in those areas classified as serious, severe, or extreme for ozone nonattainment. Fifty-six chemicals are monitored on six-day intervals at these sites. In Georgia, the PAMS sites are located in Conyers, South DeKalb, and Yorkville. Of the 56 chemicals monitored at these sites, many are ozone precursors, and have not had a screening value developed for determining the toxicity of those compounds. Therefore, for this study, only twelve chemicals were assessed for their potential to have detrimental effects on human health if present in ambient air. Those twelve chemicals were benzene, cyclohexane, ethyl benzene, p-ethyltoluene, n-hexane, 1,2,3-trimethylbenzene, 1,2,4trimethylbenzene, 1,3,5-trimethylbenzene, styrene, toluene, m/p-xylenes, and o-xylene. 147 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment Of those twelve chemicals evaluated from the PAMS network, only benzene and 1,2,4- trimehtylbenzene were found in concentrations above the screening values in 2012. Table 31, below, shows the number of samples collected, first and second highest sample concentrations (1st and 2nd Max), averages (means) in micrograms per cubic meter (g/m3), hazard quotients (HQ) and cancer risk (CR) for chemicals evaluated in the quantitative assessment at each of the three PAMS sites for 2012. Benzene was detected consistently and when evaluated as a potential carcinogen, produced theoretical cancer risks as great as 3 x 10-5 and hazard quotient of 0.1 at the South DeKalb site. The lowest theoretical cancer risk was at the Yorkville site with 1 x 10-5 and hazard quotient of 0.05. 1,2,4- trimethylbenzene was detected above the screening value at all the PAMS sites, and when evaluated as a potential non-cancer hazard, produced a hazard quotient in the range of 1 (Conyers) to 4 (Yorkville). Location Conyers South DeKalb Yorkville Chemical Benzene 1,2,4-Trimethylbenzene Benzene 1,2,4-Trimethylbenzene Benzene 1,2,4-Trimethylbenzene Detection Frequency 50/58 30/58 56/61 44/61 40/51 14/51 1st Max (g/m3) 6.39 98.32 10.22 63.91 3.83 855.41 2nd Max (g/m3) 6.07 93.41 8.31 54.10 3.83 108.16 Mean (g/m3) 2.33 10.27 3.39 13.52 1.41 27.53 HQ 0.08 1 0.1 2 0.05 4 CR 2 x 10-5 3 x 10-5 1 x 10-5 Table 31: Summary Data for Select VOCs at PAMS Sites, 2012 148 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment With the exclusion of acrolein, the carbonyls (acetaldehyde, acetone, benzaldehyde, butyraldehyde, formaldehyde, and propionaldehyde) were measured at only two of the ATN sites (Savannah and Dawsonville) and one PAMS/NATTS site (South DeKalb) in 2012. For that reason, their results are displayed separately from the rest of the data. Detection frequency, average (mean) concentration in micrograms per cubic meter (g/m3), cancer risk, and non-cancer HQs for the carbonyls are shown in Table 32. This table also shows the sum of the cancer risk and hazard quotients, which are the aggregate cancer risk and hazard index (HI), per site. Of the six carbonyls sampled, acetaldehyde and formaldehyde were detected above the screening value in 2012. All the sites monitoring for acetaldehyde and formaldehyde detected these compounds with a relatively high detection frequency. Formaldehyde was detected 78% to 96% of the time, with the Dawsonville site having the lowest detection frequency, and the South DeKalb site having the highest detection frequency. Acetaldehyde was detected 22% to 67% of the time, with the Dawsonville site having the lowest detection rate and the South DeKalb site having the highest. Acetaldehyde had relatively low theoretical cancer risks, ranging from 2 x 10-6 to 5 x 10-6, and relatively low hazard quotients, ranging from 0.09 to 0.3. Formaldehyde had theoretical cancer risks, ranging from 2 x 10-5 to 2 x 10-4, and hazard quotients, ranging from 0.2 to 2. Location Chemical Detection Frequency Mean (g/m3) Cancer Risk Hazard Quotient Dawsonville Savannah South DeKalb Acetaldehyde Formaldehyde SUM Acetaldehyde Formaldehyde SUM Acetaldehyde Formaldehyde SUM 6/27 21/27 9/27 24/27 36/54 52/54 0.81 1.58 1.06 4.57 2.49 15.45 2 x 10-6 2 x 10-5 2 x 10-5 2 x 10-6 6 x 10-5 6 x 10-5 5 x 10-6 2 x 10-4 2 x 10-4 0.09 0.2 0.3 0.1 0.5 0.6 0.3 2 2 Table 32: Summary Observations, Cancer Risk, and Hazard Quotient for Carbonyls, 2012 SUMMARY AND DISCUSSION In 2012, there were 71 air toxics compounds monitored at 6 sites across the state, with the exception of the South DeKalb site that monitored 77 air toxic compounds. Of these compounds monitored, 33 were not detected and 12 compounds were detected at two sites or less. 50% of the compounds detected above the screening value were in the metals category, 38% were in the volatile organic compounds category, and 13% were in the semi-volatile organic compounds category. For the 2012 data, there was an average of 5 compounds per site that were above the screening value. In 2012, out of all of the volatile organic compounds, benzene and carbon tetrachloride were evaluated in the quantitative assessment. (Acrolein is discussed along with the carbonyls, as it was previously detected with the carbonyls). Benzene was found above the screening value at all six Air Toxics sites. Average benzene concentrations at the Air Toxics sites ranged from 0.4 to 0.8 g/m3. These concentrations correspond to the predicted theoretical lifetime cancer risk in the range of 3 x 10-6 to 6 x 10-6. All three PAMS sites detected benzene above the screening value as well. Average concentrations of benzene measured in the PAMS network ranged from 1.4 to 3.4 g/m3. These concentrations correspond to predicted theoretical lifetime cancer risks in the range of 1 x 10-5 to 3 x 10-5 for the PAMS sites. Major sources of benzene to the environment include automobile service stations, exhaust from motor vehicles, and industrial emissions (ATSDR, 1997a). Most data relating effects of long-term exposure to benzene are from studies of workers employed in industries that make or use benzene, where people were exposed to amounts hundreds or thousands of times greater than those reported herein. Under these circumstances of high exposure, benzene can cause problems in the blood, including anemia, excessive bleeding, and harm to the immune system. Exposure to large amounts of benzene for long periods of time may also cause cancer of the blood- 149 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment forming organs, or leukemia (ATSDR, 1997a). The potential for these types of health effects from exposure to low levels of benzene, as reported in this study, are not well understood. Benzene has been determined to be a known carcinogen (U.S. EPA, 2000) and was evaluated as such in this study. Carbon tetrachloride (CCl4) was found above the screening value at the Dawsonville site, with a concentration of 0.8 g/m3. There was one detection out of thirty samples, a detection frequency of 3%. Theoretical lifetime cancer risk for carbon tetrachloride, calculated from the mean concentration, was 5 x 10-6 with a non-cancer hazard quotient of 0.008. In the past, carbon tetrachloride was used to produce refrigeration fluids, as propellants for aerosol cans, as a pesticide, in fire extinguishers, as a spot cleaner, and as a degreasing agent (ATSDR, 2005a). Because of concerns regarding carbon tetrachloride's toxicity, these uses have been stopped or severely restricted. Large exposures to carbon tetrachloride can damage the liver, kidneys, and nervous system. U.S. EPA has classified carbon tetrachloride as a probable human carcinogen (U.S. EPA, 1991a). In 2012, naphthalene was the only compound in the semi-volatile organic group found above the screening value. It was detected at the South DeKalb site with every sample taken, or 100% detection frequency. The theoretical lifetime cancer risk for the South DeKalb site was 3 x 10-6, with a non- cancer hazard quotient of 0.02. Naphthalene is found in moth repellents, petroleum, coal, and is used in making polyvinyl chloride (PVC) plastics. Exposure to large amounts can cause hemolytic anemia (ATSDR, 2005e). Four metals, manganese, arsenic, chromium, and nickel, were evaluated in the quantitative assessment. Manganese was detected above the screening value for one of the six Air Toxics sites. Manganese is a trace element, and small amounts are needed to support good health. However, exposure to very large amounts through inhalation can result in neurological effects (ATSDR, 2000a). Manganese was evaluated as a neurotoxin, but did not contribute significantly in the quantitative assessment with a HQ of 0.2 at the Macon site. This HQ suggests that there is little potential for neurological effects from ambient air concentrations of manganese. Arsenic was found above the screening value at all six Air Toxics sites. Arsenic occurs naturally in soil and rocks, and was used extensively in the past as a pesticide on cotton fields and in orchards (ATSDR, 2005b). However, the majority of arsenic found in the atmosphere comes from the burning of coal and oil, incineration, and smelting operations. Arsenic has been recognized as a human poison since ancient times. Inhalation of large quantities of some forms of arsenic may cause irritation of the throat and upper respiratory tract. Long-term exposure either by inhalation or ingestion may result in a unique pattern of skin changes, and circulatory and peripheral nervous disorders (ATSDR, 2005b). Inhalation of some forms of arsenic may also cause cancer, so arsenic was evaluated as a carcinogen in this assessment. The detection frequency was relatively high, with the lowest, 64%, at the Yorkville site, and highest at the General Coffee site, 96%. Theoretical lifetime cancer risks estimated from the data collected in 2012 ranged from 2 x 10-6 to 5 x 10-6, and the HQs ranged from 0.03 to 0.08. In 2012, total chromium was detected at all six Air Toxics sites and displayed a high detection frequency, ranging from 86% (Yorkville site) to 100% (General Coffee and South DeKalb sites). The theoretical cancer risk ranged from 1 x 10-5 to 2 x 10-5. The site with the lowest theoretical cancer risk was the South DeKalb site at 1 x 10-5, and all other sites shared a risk of 2 x 10-5. Chromium is a naturally occurring element and is common in low amounts in foodstuffs (ATSDR, 2000b). Natural processes such as wind generating dust and even volcanoes may release chromium into the atmosphere. However, many human activities such as coal and oil combustion, electroplating, smelting, and iron and steel production also release it into the atmosphere. The chemistry of chromium is complex. It may occur in different forms or oxidation states in the environment, having very different degrees of toxicity. Chromium+3 is the form that often 150 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment predominates in the natural environment, and is also an essential element required for good nutrition. Hexavalent chromium (chromium+6) is the most toxic form of chromium and is often related to releases from industrial activities (ATSDR, 2000b). Inhaling large amounts of chromium+6 may cause upper respiratory track irritation, and chromium+6 has also been shown to be a carcinogen, causing increases in the risk of lung cancer (ATSDR, 2000b). Studies have shown that in ambient air, even near industrial sites, chromium+6 is usually only a small portion of total chromium, with measured concentrations for chromium+6 accounting for a range of values from 1 to 25% of total chromium (ATSDR, 2000b). As part of the NATTS network, sampling for chromium+6 takes place at the South DeKalb site. When the 2012 concentration of chromium+6 is compared to the total chromium concentration, it shows that the chromium+6 is 0.9% of the total chromium accounted for at the South DeKalb site. However the concentrations of chromium+6 detected were below the screening value and were not evaluated further as a potential cancer risk. The South DeKalb site is located within and representative of an urban area. Since the chromium+6 concentrations were below the screening value for the South DeKalb site, this could indicate that chromium+6 levels are low throughout the network. The other sites that measure for chromium, measure for the total form. Therefore, the measurements used in this study were for the total form, and distinctions cannot be made as to how much of the different states of chromium are present at the other Air Toxics sites. In the interest of conservativeness, chromium was evaluated with the most stringent toxicity index, as chromium+6, even though the chromium metal measured was not in this most toxic form. Data collected on the ratio of chromium+6 to total chromium (ATSDR, 2000b) indicates that this process may appreciably overestimate risk. Further work is needed to better understand chemical forms of chromium in Georgia's air, and determine if chromium is an important contributor to risk. In 2012, nickel was detected above the screening value at three of the six Air Toxics sites, with hazard quotients ranging from 0.02 to 0.03. When detected, nickel had a high detection frequency, occurring in 100% of the collected samples at the three sites. Nickel is a naturally occurring element used in many consumer and industrial products such as stainless steel, alloys, and coins, and is also released in the burning of oil and coal. If large amounts are breathed, nickel can cause damage to the lungs and nasal cavities, and can be carcinogenic (ATSDR, 2005d). Carbonyls were monitored at three sites in Georgia in 2012. Two sites, Dawsonville and Savannah are ATN sites, while the other site, South DeKalb, is in the PAMS/NATTS network. Three carbonyls, formaldehyde, acetaldehyde, and acrolein, were detected above the screening level and included in the quantitative assessment. Formaldehyde, the simplest of the aldehydes, is produced by natural processes, and from the fertilizer, paper, and manufactured wood products industries (ATSDR, 1999). It is also found in vehicle emissions. Formaldehyde is a health concern because of its respiratory irritancy and as a possible carcinogen. It may cause irritation of the eye, nose, throat, and skin, and has the potential under certain exposure scenarios to cause cancers of the nose and throat (ATSDR, 1999). Acetaldehyde, like formaldehyde, is also a concern as an upper respiratory irritant, and because of its potential to cause nasal tumors in animal studies. However, research has shown it to be significantly less potent than formaldehyde. Acetaldehyde, as an intermediate product of plant respiration and a product of incomplete combustion, is ubiquitous in the environment. (U.S. EPA, 1987; U.S. EPA 1991b). Recent studies of acetaldehyde background levels have found average background concentrations at 0.16 g/m3 in remote areas of North America (McCarthy, Hafner, & Montzka, 2006). In 2012, formaldehyde and acetaldehyde were detected at all three locations where carbonyls were assessed. The highest average concentrations of both formaldehyde and acetaldehyde were found at the South DeKalb site, 15.45 g/m3 and 2.49 g/m3 respectively. As shown above, 0.16 g/m3 of the acetaldehyde average concentration could be attributed to the background concentration. When the theoretical cancer risk for formaldehyde was evaluated, the risk ranged from 2 x 10-5 to 2 x 10-4 for 151 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment 2012. The hazard quotients ranged from 0.2 to 2. When acetaldehyde was evaluated for theoretical cancer risk, the risk ranged from 2 x 10-6 to 5 x 10-6. The hazard quotients ranged from 0.09 to 0.3. Due to EPA research to improve acrolein sampling and analysis, GA EPD began collecting acrolein with the other VOCs in a canister and analyzing it using a GC/MS method. This method was started in July of 2007, drastically changing the number of detections that were found across the state. In previous years, acrolein was analyzed along with the carbonyls, at select sites. With the GC/MS and canister method, this allowed acrolein to be sampled at all of the air toxics sites. In 2012, it was detected at all the sites, with the detection frequency ranging from 56% to 97% of samples. Acrolein was evaluated as a potential non-carcinogen, and the hazard quotients ranged from 21 to 39, shown in Table 29, above. The average concentrations ranged from 0.43 g/m3 to 0.79 g/m3 (using half the detection limit for non-detected samples). The highest acrolein average was found at the Dawsonville site. Acrolein may enter the environment as a result of combustion of trees and other plants, tobacco, gasoline, and oil. Additionally, it can be used as a pesticide for algae, weeds, bacteria, and mollusks (ATSDR, 2007c). The potential for acrolein to cause health effects is not well understood. At very low concentrations, it is an upper respiratory irritant. At very high concentrations it may produce more serious damage to the lining of the upper respiratory tract and lungs (ATSDR, 2007c; U.S. EPA, 2003). Of the PAMS compounds assessed, benzene and 1,2,4-trimethylbenzene were the only compounds detected above the screening value, and they were found at all three PAMS sites (Conyers, South DeKalb and Yorkville) in 2012. When evaluated as a theoretical cancer risk, the levels of benzene ranged from 1 x 10-5 at the Yorkville site to 3 x 10-5 at the South DeKalb site. The hazard quotients ranged from 0.05 at the Yorkville site to 0.1 at the South DeKalb site. As stated earlier, major sources of benzene to the environment include automobile service stations, exhaust from motor vehicles, and industrial emissions (ATSDR, 1997a). 1,2,4-Trimethylbenzene occurs naturally in coal tar and petroleum crude oil. It is a component of gasoline, and has other uses in industry as an intermediate in the production of dyes, drugs, and coatings. Exposure to very large amounts of 1,2,4trimethylbenzene may cause skin and respiratory irritancy and nervous system depression, fatigue, headache, and drowsiness. However, risks resulting from exposure to low ambient concentrations of 1,2,4-trimethylbenzene have not been studied extensively (U.S. EPA, 1994a). For this study, 1,2,4trimethylbenzene was evaluated as a non-carcinogen with potential to cause central nervous system and irritant effects (U.S. EPA, 2004b). The 1,2,4-trimethylbenzene hazard quotients ranged from 2 at the Conyers site to 4 at the Yorkville site. In Figure 92 and Figure 93, below, maps are shown of the most recent official National Air Toxics Assessment (NATA) that was based on 2005 air toxics emissions inventory. The estimated total cancer risk levels and estimated total respiratory hazard index are given per tract across the United States. The maps indicate that the estimated tract level total cancer risk and estimated tract level total respiratory hazard index, respectively, are higher in more populated areas and along transportation corridors. 152 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment (http://www.epa.gov/ttn/atw/nata2005/05pdf/sum_results.pdf) Figure 92: Estimated Tract-Level Cancer Risk from the 2005 National Air Toxics Assessment 153 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Risk Assessment (http://www.epa.gov/ttn/atw/nata2005/05pdf/sum_results.pdf) Figure 93: Estimated Tract-Level Total Respiratory Hazard Index from the 2005 National Air Toxics Assessment As stated previously, the estimates of risk presented herein are likely overestimates due to conservative assumptions used in this exercise. Conservative assumptions were used to estimate the potential for possible exposures (high inhalation rates and long term exposure) and toxicity values. In the absence of good exposure information, this practice is warranted to decrease the potential for underestimating risk. The results presented herein suggest that the majority of calculated risk is due to a small number of chemicals. The risk values presented in this report should not be interpreted as indicators of true or "real" risk, but for relative comparisons of a chemical's contribution to aggregate risk, or for comparisons of risk between locations within the monitoring network or in other areas of the country. 154 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Outreach and Education OUTREACH AND EDUCATION Maintaining effective public outreach and education is important to the Ambient Monitoring Program's mission. The Ambient Monitoring Program (AMP) seeks to address the air quality issues that are most vital to the citizens of Georgia by identifying the pollutants that represent the greatest risks, continually monitoring the pollutants, and then communicating the monitoring results directly to the public. The goal is to provide an understanding of the presence of air pollution throughout the state, and to educate the public on the steps they can take to improve air quality and protect health. AMP accomplishes this goal by issuing smog alerts and providing information about the Air Quality Index (AQI), maintaining a partnership with the Clean Air Campaign, and conducting other outreach strategies aimed at keeping the public up to date on air quality issues. What is the Clean Air Campaign? The Clean Air Campaign (CAC) is a not-for-profit organization that works to reduce traffic congestion and improve air quality in the metro Atlanta nonattainment area through a variety of voluntary programs and services, including free employer assistance, incentive programs, public information and children's education. The Clean Air Campaign and its partners offer assistance to more than 1,600 employers to design and implement commute options programs that make business sense; protect public health; offer targeted incentives to commuters and employers; and work with elementary, middle and high schools to protect children from harmful pollution and empower children to take a positive role in reducing traffic and cleaning the air. In addition to addressing commuters' driving habits, CAC utilizes the AQI to relay air quality information to metro Atlanta residents by providing Smog Alert notifications. The Air Quality Index The Air Quality Index (AQI) is a national air standard rating system developed by the U.S. Environmental Protection Agency. The AQI is used statewide to provide the public, on a daily basis, with an analysis of air pollution levels and possible related health risks. Generally, an index scale of 0 to 500 is used to assess the quality of air, and these numbers are synchronized with a corresponding descriptor word such as: Good, Moderate, Unhealthy for Sensitive Groups, Unhealthy, and Very Unhealthy. To protect public health the EPA has set an AQI value of 100 to correspond to the NAAQS for the following pollutants: Ozone (O3), Sulfur Dioxide (SO2), Carbon Monoxide (CO), Particulate Matter 10 (PM10), and Nitrogen Dioxide (NO2). For Particulate Matter 2.5 (PM2.5), the AQI is set up for the range of 15.5 to 40.4 g/m3 to be equivalent to the 51 to 100 AQI value. The AQI for a reporting region equates to the highest rating recorded for any pollutant within that region. Therefore, the larger the AQI value, the greater level of air pollution present, and the greater expectation of potential health concerns. However, this system only addresses air pollution in terms of acute health effects over time periods of 24 hours or less and does not provide an indication of chronic pollution exposure over months or years. Figure 94, on the next page, shows how the recorded concentrations correspond to the AQI values, descriptors and health advisories. 155 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Outreach and Education Maximum Pollutant Concentration PM2.5 PM10 (24hr) (24hr) g/m3 g/m3 SO2 (1hr)* ppm O3 (8hr)^ ppm O3 (1hr) ppm CO (8hr) ppm NO2 (1hr) ppm AQI Value Descriptor EPA Health Advisory 0.0 15.4 0 54 0 0.035 0.000 0.059 None 0.0 4.4 0 0.053 0 to 50 Good (green) Air quality is considered satisfactory, and air pollution poses little or no risk. 15.5 40.4 55 154 0.036 0.060 0.075 0.075 None 4.5 0.054- 51 to 9.4 0.100 100 Moderate (yellow) Air quality is acceptable; however, for some pollutants there may be a moderate health concern for a very small number of people. For example, people who are unusually sensitive to the condition of the air may experience respiratory symptoms. 40.5 65.4 155 254 0.076 0.076 0.125 9.5 0.185 0.095 0.164 12.4 Unhealthy Members of sensitive groups for Sensitive (people with lung or heart Groups disease) are at greater risk from 0.101- 101 to exposure to particle pollution. 0.360 150 Those with lung disease are at (orange) risk from exposure to ozone. The general public is not likely to be affected in this range. 65.5 150.4 255 0.186 0.096 0.165 12.5 0.361- 151 to 354 0.304* 0.115 0.204 15.4 0.64 200 Unhealthy (red) Everyone may begin to experience health effects in this range. Members of sensitive groups may experience more serious health effects. 150.5 355 0.305 0.116 0.205 15.5 0.65 201 to 250.4 424 0.604* 0.374 0.404 30.4 1.24 300 Very Unhealthy (purple) AQI values in this range trigger a health alert. Everyone may experience more serious health effects. When the AQI is in this range because of ozone, most people should restrict their outdoor exertion to morning or late evening hours to avoid high ozone exposures. 250.5 350.4 425 504 0.605 0.804* None^ 0.405 30.5 1.25 0.504 40.4 1.64 301 to 400 350.5 500.4 505 604 0.805 1.004* None^ 0.505 40.5 1.65 0.604 50.4 2.04 401 to 500 AQI values over 300 trigger Hazardous health warnings of emergency conditions. The entire (maroon) population is more likely to be affected. *AQI values of 200 or greater are calculated with 24-hr SO2 concentrations. ^AQI values of 301 or greater are calculated with 1-hr O3 concentrations. Figure 94: The AQI 156 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Outreach and Education Each day the AQI values for Athens, Atlanta, Augusta, Columbus, Macon, North Georgia Mountains, and Savannah are available to the public through GA EPD's website http://www.air.dnr.state.ga.us/amp/. The following table shows a summary of the 2012 AQI values for these sites, as well as all sites that collect criteria data in Georgia. The majority of days had an AQI value in the `Good' (0-50) category for all the sites. Air Quality Index Summary by MSA Number of Days Unhealthy AQI for Sensitive Very Category Good Moderate Groups Unhealthy Unhealthy Hazardous (0-50) (51-100) (101-150)** (151-200)** (201-300)** (>300)** Pollutants Monitored in 2012 Albany MSA 2012 254 104 2 Athens-Clark County MSA 0 0 0 PM10, PM2.5 2012 262 99 4 1 0 0 O3, PM2.5 Atlanta-Sandy Springs-Marietta MSA 2012 114 233 16 2 1 0 O3, NO2, PM2.5 Augusta-Richmond County, GA-SC MSA 2012 238 124 4 Brunswick MSA 0 0 0 O3, PM2.5 2012 360 4 0 Chattanooga, TN-GA MSA 0 0 0 O3, SO2, PM10, PM2.5 2012 194 150 8 Columbus GA-AL MSA 0 0 0 O3, PM2.5 2012 252 113 1 Dalton MSA 0 0 0 O3, PM10, PM2.5 2012 222 22 1 0 0 0 O3 Gainesville MSA 2012 210 118 0 Macon MSA 0 0 0 PM2.5 2012 225 139 2 Rome MSA 0 0 0 O3, SO2, PM2.5 2012 48 315 3 Savannah MSA 0 0 0 SO2, PM2.5 2012 236 122 8 Valdosta MSA 0 0 0 O3, SO2, PM2.5 2012 167 176 2 Warner Robins MSA 0 0 0 PM2.5 2012 217 112 1 0 0 0 **AQI numbers above 100 may not be equivalent to a violation of the standard. (Source: http://www.epa.gov/airquality/airdata/ad_rep_aqi.html) PM2.5 Table 33: AQI Summary Data, 2012 157 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Outreach and Education In the following graph, the number of days that the AQI value was above 100 is plotted for each metropolitan statistical area (MSA) in Georgia where an AQI value is produced. The data was generated starting in 1972 and is shown through 2012. To be consistent, the most current standards were applied throughout the historical dataset. As one would expect, the Atlanta-Sandy SpringsMarietta MSA (shown in red below) has historically had the highest number of days with the AQI above 100. The pattern materializing across the forty year timeframe seems to be cyclic. However, the number of days above 100 for the Atlanta-Sandy Springs-Marietta MSA decreased dramatically from 1999 to 2004 and from 2006 to 2009. The number dropped from 95 days in 1999 to 33 days in 2004 and from 63 days in 2006 to 15 days in 2009. More recently, the Atlanta-Sandy Springs-Marietta MSA's number of days with AQI above 100 decreased from 44 days in 2011 to 19 days in 2012. The remaining MSA sites had eight or fewer days with the AQI above 100 in 2012. Brunswick and Gainesville MSAs did not have any days with the AQI above 100 in 2012. Days Above an AQI Value of 100 100 90 80 70 60 50 40 30 20 10 0 Year Albany Atlanta-Sandy Springs-Marietta Brunswick Columbus GA-AL Gainesville Rome Valdosta Figure 95: Number of Days with an AQI Value Above 100 Athens-Clarke County Augusta-Richmond County GA-SC Chattanooga TN-GA Dalton Macon Savannah Warner Robins 158 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Outreach and Education Figure 96 shown below displays in more detail the 2012 AQI values for the Atlanta-Sandy SpringsMarietta MSA shown over the twelve month period. The majority of the 19 days with an AQI value above 100 occurred in the seasonally warmer months between May and September. This can be expected as ozone, a major driver of an elevated AQI, can be higher in the summer months due to increased sunlight. Higher ozone and PM2.5 concentrations are the primary sources of AQI values in the "Unhealthy for Sensitive Groups" category for the Atlanta-Sandy Springs-Marietta MSA shown below. Air Quality Index Score Very Unhealthy 200 Unhealthy 150 Unhealthy for Sensitive Groups 100 Moderate 50 Good 0 Figure 96: 2012 AQI Values, Atlanta-Sandy Springs-Marietta MSA How does Georgia's Ambient Monitoring Program (AMP) Cooperate with The Clean Air Campaign (CAC)? The Ambient Monitoring Program is responsible for measuring air pollutant levels in metro Atlanta and throughout the state. Equipment at fourteen continuous monitoring stations across metro Atlanta is used for these measurements of particulate matter (PM), sulfur dioxide (SO2), carbon monoxide (CO), nitrogen dioxide (NO2), and ozone (O3). This data is reported hourly on a website which is maintained and updated by the Ambient Monitoring Program. Based on these levels, AMP calculates the Air Quality Index (AQI), which represents overall air quality in a way that is quick and easy for the general public to understand. The Ambient Monitoring Program's website is linked to a website maintained by CAC. The AQI is then displayed on The Clean Air Campaign's website. The CAC also distributes AQI information to people who have signed up to receive daily air quality forecasts via email. When a smog alert is forecasted, an automated fax blast informs all local media as well. Through these connections, thousands of metro Atlanta citizens and businesses keep abreast of current air quality conditions. The Ambient Monitoring Program also encourages the public to access the CAC's website and learn about voluntary measures that are available locally to improve air quality. 159 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Outreach and Education MEDIA OUTREACH The Ambient Monitoring Program continuously contacts citizens as well as the news media through phone calls, website updates and media interviews. At many times throughout the year, the demand for a story puts AMP in the spotlight. The Program Manager and staff of the Ambient Monitoring Program make themselves available to television and newspaper reporters, thus educating the public about the AQI, statewide air monitors, and the Clean Air Campaign. OTHER OUTREACH OPPORTUNITIES Meteorologists Forecasters from the Ambient Monitoring Program issue air quality forecasts on a daily basis. In addition, forecasters answer questions for the news media and calls from the public. For more information regarding the work done by the Ambient Monitoring Program's meteorologists, refer to the Meteorological Section of this report. Elementary and Middle Schools Educating school children and incorporating air quality information into the classroom-learning environment is also an outreach strategy for the Ambient Monitoring Program. AMP staff visit Georgia classrooms to discuss air quality, forecasting, and monitoring. Each program presented by the AMP is designed to supplement grade-specific curricula. Learning opportunities include meteorological lessons and forecasting techniques, among other relevant topics. In many situations, these lessons involve hands-on activities and mini-field trips to the monitoring sites. High School students simulate forecasting conditions and use scientific methods to create their own forecasts. AMP staff also participate in Career Days at both elementary and high schools to promote environmental and meteorological careers. Colleges and Universities The Ambient Monitoring Program works with colleges and universities in several capacities. Utilizing a more technical, advanced approach, AMP has participated in several college-level seminars, providing scientific expertise on the subject of meteorology and forecasting. Through this close contact with university staff, AMP staff have co-authored scientific papers in peer-reviewed scientific journals. AMP staff provide technical data to professors as well as students, thus incorporating realtime data into college courses and projects. Additionally, AMP works with Georgia Institute of Technology in a joint forecasting effort. AMP also hosts an annual Air Quality Seminar and Air Monitoring Station fieldtrip for college interns in the Centers for Disease Control and Prevention's (CDC) Environmental Health Summer Intern Program, thereby reaching top college students from all over the country. Monitoring Data Requests AMP also regularly receives requests for specific, detailed monitoring data from members of the research community and the broader public. Completely fulfilling the needs of these data users often requires not just data, but also providing guidance on how the data can be interpreted and what the limitations of the data set may be. AMP welcomes these opportunities to serve the public and the research community, and to ensure that the data collected is put to its fullest and most advantageous use in protecting the health and welfare of Georgia's citizens and the state's natural environment. EPA AIRNOW Website Georgia supplies ozone and particulate matter data to the U.S. EPA every hour for pollution mapping activities. AIRNOW is a cooperative effort between EPA, states, and local air pollution control agencies to provide near real-time information on ground level ozone and PM2.5 concentrations. EPA uses the data to produce maps that display ozone and PM2.5 contours covering the Midwest, New 160 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Outreach and Education England, Mid-Atlantic, Southeastern, South central and Pacific coastal regions of the country. Colorcoded, animated concentration gradient AQI maps are created that show daily ozone and PM2.5 formation and transport at various spatial scales. The information is available on the EPA's AIRNOW website at: http://www.airnow.gov/. See Figure 97 for a sample map. Figure 97: Sample AIRNOW Ozone Concentration Map The AIRNOW Data Management Center (DMC) regularly evaluates the performance of monitoring agencies that participate in the AIRNOW project based on three criteria: 1. Percent of hourly data files received 2. Average arrival time (earlier in the hour is better) 3. Percent completeness of the data within the submission files There is a three-tier system (top, middle, and lower) set up to evaluate each agency based on these performance criteria. An agency is placed in a tier based on how it performs these three criteria, with respect to all participating agencies. GA EPD Website and Call-In System The Ambient Monitoring Program also provides a public-access website with Georgia-specific current and historical air quality data, often more promptly and with more detail than what is available at the AIRNOW website. AMP's website provides hourly information about current pollutant concentrations from Georgia's continuous and semi-continuous monitoring equipment, and is updated with each hour's data only 15 minutes after the hour ends. The site also offers downloads of bulk data, and electronic copies of archived Annual Reports such as this one, on a self-serve basis to facilitate research projects and satisfy public interest on these topics. Finally, the Ambient Monitoring Program also maintains an automated dial-in system that provides current air quality information for those who may not have ready access to the internet. These resources are listed below. Ambient Monitoring Program Website: http://www.air.dnr.state.ga.us/amp Call-In System: (800) 427-9605 (statewide) (404) 362-4909 (metro Atlanta free calling zone) 161 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix A Appendix A: Additional Criteria Pollutant Data Carbon Monoxide (CO) Units: parts per million Site ID City County 130890002 Atlanta DeKalb 131210099 Atlanta Fulton 132230003 Yorkville Paulding Site Name South DeKalb Roswell Road Yorkville Hours Measured 8573 8567 8277 Max 1 - Hour 1st 2nd 1.613 1.602 Obs. > 35 0 1.8 1.7 0 1.5 0.8 0 Max 8 - Hour 1st 2nd 1.4 1.4 Obs. > 9 0 1.1 1.1 0 0.7 0.6 0 Nitrogen Dioxide (NO2) Units: parts per billion Site ID City County Site Name 130890002 132230003 132470001 Decatur Yorkville Conyers DeKalb Paulding Rockdale South DeKalb Yorkville Monastery Hours Measured 8479 7774 8468 98th% 52.6 15.1 18.3 Max 1-Hour 1st 2nd 70.1 66.7 27.0 21.1 22.8 21.7 Annual Arithmetic Mean 11.54 2.76 4.21 Nitric Oxide (NO) Units: parts per billion Site ID City County Site Name 130890002 132230003 132470001 Decatur Yorkville Conyers DeKalb Paulding Rockdale South DeKalb Yorkville Monastery Hours Measured 8479 7774 8468 Max 1-Hour 1st 2nd 370.9 22.8 52.3 330.4 15.4 50.9 Annual Arithmetic Mean 18.31 1.03 1.56 162 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Oxides of Nitrogen (NOx) Units: parts per billion Site ID City County Site Name 130890002 132230003 132470001 Decatur Yorkville Conyers DeKalb Paulding Rockdale South DeKalb Yorkville Monastery Hours Measured 8479 7774 8468 Section: Appendix A Max 1-Hour 1st 2nd 417.5 43.3 64.6 373.8 36.6 58.3 Annual Arithmetic Mean 29.47 2.74 4.79 Reactive Oxides of Nitrogen (NOy) Units: parts per billion Site ID City County Site Name Hours Measured Max 1-Hour 1st 2nd Annual Arithmetic Mean 130890002 Decatur DeKalb South DeKalb 8506 200.0 200.0 29.39 ** The NOy instrument is specialized for measurement of trace concentrations, so its range is only 0-200 ppb. Actual 1st Max appears to have exceeded the instrument's measurement range. Since all ambient concentrations exceeding the instrument's range are recorded as 200 instead of the actual (higher) value, the reported annual arithmetic mean may be biased slightly downward from the true concentration. 163 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix A Sulfur Dioxide (SO2) 24-Hour, 3-Hour, 1-Hour Maximum Observations, 99th Percentile 1-hour, and Maximum 5-minute Units: parts per billion Site ID City 130210012 Macon 130510021 Savannah 130511002 Savannah 130890002 Decatur 131150003 Rome 131210055 Atlanta 131270006 Brunswick 132150008 Columbus County Site Name Bibb Chatham Chatham DeKalb Floyd Fulton Glynn Muscogee Georgia Forestry Comm. East President St. W. Lathrop & Augusta Ave. South DeKalb Coosa Elem. School Confederate Ave. Risley Middle School Columbus Airport Hours Measur -ed 8531 8488 8709 8637 8391 8558 8521 8644 Max 24 Hour 1st 2nd 4.0 3.7 29.5 23.5 41.0 35.1 2.5 2.3 29.9 28.7 3.8 3.0 1.7 1.5 2.5 2.4 Max 3 Hour 1st 2nd 24.5 16.0 61.9 55.8 84.3 82.2 9.6 8.9 85.1 82.8 8.9 8.1 6.6 3.8 8.3 7.5 Max 1-Hour 1st 2nd 99th Pctl 1- Hr Maximum 5-Minute Average Annual Arithme -tic Mean 41.3 23.5 20.6 334.3 1.17 96.6 87.3 77.9 229.8 2.31 127.6 111.7 73.8 244.5 2.69 13.6 13.0 11.4 42.0 0.46 160.6 133.5 75.9 326.3 1.62 12.4 11.0 9.5 27.4 1.11 11.2 5.3 3.8 7.8 1.03 18.9 14.0 8.4 29.1 1.11 164 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Ozone (O3) Units: parts per million Site ID City County 130210012 130510021 130550001 130590002 130670003 130730001 130770002 130850001 130890002 130970004 131210055 131270006 131350002 131510002 132130003 132150008 132230003 132319991 132450091 132470001 132611001 Macon Savannah Summerville Athens Kennesaw Evans Newnan Dawsonville Decatur Douglasville Atlanta Brunswick Lawrenceville McDonough Chatsworth Columbus Yorkville Williamson Augusta Conyers Leslie Bibb Chatham Chattooga Clarke Cobb Columbia Coweta Dawson DeKalb Douglas Fulton Glynn Gwinnett Henry Murray Muscogee Paulding Pike Richmond Rockdale Sumter 1-Hour Averages Site Name GA Forestry Comm. E. President Street DNR Fish Hatchery College Station Rd. Georgia National Guard Riverside Park Univ. of West Georgia GA Forestry Comm. South DeKalb W. Strickland St. Confederate Ave. Risley Middle School Gwinnett Tech. County Extension Office Fort Mountain Columbus Airport Yorkville CASTNET Bungalow Road Elementary School Conyers Monastery Leslie Community Center Days Measured 245 241 245 245 244 241 244 242 245 239 244 234 244 245 243 245 244 227 232 242 233 Section: Appendix A 1st Max 0.104 0.086 0.078 0.091 0.102 0.094 0.080 0.074 0.116 0.085 0.114 0.069 0.112 0.146 0.091 0.082 0.087 0.115 0.093 0.103 0.072 2nd Max 0.093 0.082 0.078 0.090 0.089 0.094 0.078 0.072 0.101 0.085 0.101 0.067 0.091 0.106 0.079 0.076 0.084 0.086 0.091 0.101 0.072 165 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix A Ozone (O3) 8-Hour Averages Units: parts per million Site ID City County Site Name Days 1st Measured Max 2nd Max 3rd Max 4th Max 130210012 Macon Bibb GA Forestry Comm. 245 0.084 0.083 0.075 0.072 130510021 Savannah Chatham E. President Street 239 0.068 0.067 0.064 0.063 130550001 Summerville Chattooga DNR Fish Hatchery 245 0.073 0.072 0.067 0.067 130590002 Athens Clarke College Station Road 245 0.085 0.083 0.076 0.071 130670003 Kennesaw Cobb Georgia National Guard 244 0.087 0.076 0.076 0.075 130730001 Evans Columbia Riverside Park 239 0.086 0.084 0.075 0.071 130770002 Newnan Coweta Univ. of West Georgia 242 0.074 0.070 0.064 0.062 130850001 Dawsonville Dawson GA Forestry Comm. 242 0.068 0.067 0.065 0.063 130890002 Decatur DeKalb South DeKalb 244 0.099 0.087 0.086 0.085 130970004 Douglasville Douglas W. Strickland St. 236 0.080 0.078 0.073 0.073 131210055 Atlanta Fulton Confederate Ave. 242 0.101 0.089 0.087 0.087 131270006 Brunswick Glynn Risley Middle School 232 0.059 0.058 0.058 0.057 131350002 Lawrenceville Gwinnett Gwinnett Tech. 243 0.093 0.080 0.080 0.080 131510002 McDonough Henry County Extension Office 245 0.122 0.092 0.089 0.088 132130003 Chatsworth Murray Fort Mountain 242 0.076 0.072 0.070 0.070 132150008 Columbus Muscogee Columbus Airport 245 0.071 0.070 0.068 0.066 132230003 Yorkville Paulding Yorkville 243 0.080 0.075 0.074 0.072 132319991 Williamson Pike CASTNET 224 0.100 0.080 0.078 0.077 132450091 Augusta Richmond Bungalow Road Elementary School 231 0.083 0.079 0.078 0.072 132470001 Conyers Rockdale Conyers Monastery 243 0.097 0.096 0.083 0.081 132611001 Leslie Sumter Community Center 232 0.069 0.067 0.066 0.065 Number of Days > 0.075 2 0 0 3 3 2 0 0 9 2 10 0 6 8 1 0 1 4 3 8 0 4th max used in 3-year average, therefore if number above 0.075 is more than 4 per site, it is shown in bold. 166 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Lead (Pb) Section: Appendix A 3-Month Rolling Averages Using Federal Equivalent Method Site ID City County Units: micrograms per cubic meter 130150003 130890003 Cartersville Atlanta Bartow DeKalb 132150009 Columbus Muscogee 132150010 Columbus Muscogee Site Name Number of Obs. Nov 2011-Jan 2012 Dec 2011-Feb 2012 Jan 2012-Mar 2012 Feb 2012-Apr 2012 Mar 2012-May 2012 Apr 2012-Jun 2012 May 2012-Jul 2012 Jun 2012-Aug 2012 Jul 2012-Sep 2012 Aug 2012-Oct 2012 Sep 2012-Nov 2012 Oct 2012-Dec 2012 # of Values > 0.15 Cartersville 61 0.0133 0.0241 0.0265 0.0228 0.0166 0.0157 0.0135 0.0099 0.0109 0.0156 0.0166 0.0134 0 DMRC 60 0.0027 0.0028 0.0028 0.0031 0.0028 0.0029 0.0021 0.0020 0.0018 0.0020 0.0026 0.0026 0 UPS 56 N/A N/A N/A 0.0465 0.1164 0.1299 0.1429 0.1146 0.1202 0.2300 0.2175 0.1914 3 Fort Benning 61 N/A N/A 0.0455 0.0636 0.0917 0.1457 0.1597 0.1704 0.1600 0.1440 0.1639 0.1045 4 132150011 Columbus Muscogee Cusseta School 58 0.0059 0.0065 0.0068 0.0059 0.0095 0.0112 0.0104 0.0052 0.0129 0.0192 0.0259 0.0177 0 Columbus-UPS site 132150009 re-opened on 2/13/12, Columbus-Fort Benning site 132150010 re-opened 12/27/11. 167 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix A Fine Particulate Matter (PM2.5) 98th% and Annual Arithmetic Mean Integrated Sampling (midnight to midnight) Using Federal Reference Method Units: micrograms per cubic meter Site ID City County 130210007 Macon Bibb 130210012 Macon Bibb 130510017 Savannah Chatham Site Name Allied Chemical GA Forestry Comm. Market St. Days Measured 347 98th Percen- tile 24.5 Values Exceeding Applicable Daily Standard 0 109 18.2 0 104 23.8 1 Annual Arithmetic Mean 11.36 9.02 9.97 130510091 Savannah Chatham Mercer School 95 20.3 130590002 Athens Clarke College Station Rd. 101 16.4 130630091 Forest Park Clayton Georgia DOT 116 20.8 130670003 Kennesaw Cobb GA National Guard 340 18.9 130670004 Powder Springs Cobb Macland Aquatic Center 119 17.5 130890002 Decatur DeKalb South DeKalb 336 19.5 0 9.24 0 9.28 0 10.75 0 10.14 0 9.83 0 9.92 130892001 Doraville DeKalb Police Dept. 332 17.6 130950007 Albany Dougherty Turner Elem. School 244 24.9 131150003 Rome Floyd Coosa Elementary 308 20.3 131210032 Atlanta Fulton E. Rivers School 347 20.2 0 10.06 2 10.64 0 10.59 0 10.18 131210039 Atlanta Fulton Fire Station #8 111 18.2 131270006 Brunswick Glynn Risley Middle School 66 14.5 0 11.03 0 7.49 168 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix A Fine Particulate Matter (PM2.5) (continued) 98th% and Annual Arithmetic Mean Integrated Sampling (midnight to midnight) Using Federal Reference Method Units: micrograms per cubic meter Site ID City County 131350002 131390003 131530001 131850003 Lawrenceville Gainesville Warner Robins Valdosta 132150001 Columbus 132150008 Columbus 132150011 Columbus 132230003 Yorkville Gwinnett Hall Houston Lowndes Muscogee Muscogee Muscogee Paulding Site Name Gwinnett Tech Fair St. Elem. Robins AFB S.L. Mason Elem. Health Dept. Columbus Airport Cusseta Rd. School Yorkville Days Measured 119 98th Percen- tile 20.0 Values Exceeding Applicable Daily Standard 1 Annual Arithmetic Mean 10.27 114 16.6 0 9.30 114 19.4 0 9.51 103 14.4 0 8.57 104 24.0 0 10.83 58 20.4 0 10.21 114 27.5 1 10.40 113 17.1 0 8.81 132450005 Augusta Richmond Medical College 106 22.7 132450091 Augusta Richmond Bungalow Rd. School 109 22.0 132950002 Rossville Walker Health Dept. 104 19.0 133030001 Sandersville Washington Health Dept. 107 20.7 133190001 Gordon Wilkinson Police Dept. 108 22.3 0 10.70 0 10.43 0 10.54 0 9.80 0 10.85 169 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Fine Particulate Matter (PM2.5) Hourly Averages of Semi-Continuous Measurements Section: Appendix A Units: micrograms per cubic meter Site ID City County Site Name 130210012 130511002 130590002 130770002 130890002 Macon Savannah Athens Newnan Decatur Bibb Chatham Clarke Coweta DeKalb GA Forestry Comm. Lathrop & Augusta Avenues College Station Rd. Univ. of West Georgia South DeKalb Hours Measured 8686 8679 8483 8648 7608 1st Max 60.0 2nd Max 57.2 Annual Arithmetic Mean 8.65 136.0 132.9 9.45 57.9 52.0 9.62 90.0 74.9 9.30 172.0 76.0 13.43 130950007 Albany Dougherty Turner Elem 8004 268.0 223.0 9.95 131150003 Rome Floyd 131210055 Atlanta Fulton 131350002 Lawrenceville Gwinnett Coosa Elem Confederate Avenue Gwinnett Tech 8182 8612 8514 108.0 91.0 86.3 57.1 117.4 116.3 19.13 9.79 9.80 131390003 131510002 131530001 131850003 Gainesville McDonough Warner Robins Valdosta Hall Henry Houston Lowndes Gainesville County Extension Office Warner Robins Valdosta 7877 89.0 51.0 10.78 8462 87.4 80.8 9.83 7781 8162 474.0 193.0 200.0 140.0 11.30 12.93 132150008 Columbus Muscogee Columbus Airport 8703 118.0 105.2 9.51 132230003 132450091 Yorkville Augusta Paulding Richmond Yorkville Bungalow Rd. School 8616 8456 181.9 138.7 270.2 234.7 11.84 10.34 132950002 Rossville Walker Health Department 7915 105.0 94.0 11.86 Except for the South DeKalb monitor, these semi-continuous methods for measuring PM2.5 are not approved for use in making attainment determinations. 170 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix A Particulate Matter (PM10) 24-Hour Integrated Measurements Units: micrograms per cubic meter Site ID City County 130210007 Macon Bibb 130510014 Savannah Chatham 130550001 Summerville Chattooga Site Name Allied Chemical Shuman School DNR Fish Hatchery Days Measured 1st Max Number Values >150 Annual Arithmetic Mean 59 46 0 20.6 56 32 0 15.7 58 23 0 13.0 130892001 Doraville DeKalb Police Dept. 57 36 0 16.1 130950007 Albany Dougherty Turner Elementary 57 36 0 17.4 131150003 Rome Floyd Coosa Elem School 60 33 0 19.5 131210032 Atlanta Fulton E. Rivers School 58 30 0 15.2 131270004 Brunswick Glynn Arco Pump Station 50 41 0 16.3 132150011 Columbus Muscogee Cusseta Rd. Elem. School 60 68 0 15.4 132450091 Augusta Richmond Bungalow Rd. Elem. School 58 36 0 15.1 133030001 Sandersville Washington Health Dept. 55 31 0 16.1 171 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix A Particulate Matter (PM10) Hourly Averages of Semi-Continuous Measurements Units: micrograms per cubic meter Site ID City County Site Name 130890002 Decatur DeKalb 131210048 Atlanta Fulton South DeKalb Georgia Tech Hours Measured 8190 7847 1st Max 43 38 Annual Arithmetic Mean 20.3 19.1 172 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix A Coarse Particulate Matter (PM10-2.5) Hourly Averages of Semi-Continuous Measurements Units: micrograms per cubic meter Site ID City County Site Name 130890002 Decatur DeKalb South DeKalb Hours Measured 7860 1st Max 199.0 Annual Arithmetic Mean 8.24 173 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix B Appendix B: Additional PM2.5 Particle Speciation Data Particle Speciation- 2012 Statewide Average Organic Carbon 42% Sulfate 24% Other 14% Elemental Carbon 5% Ammonium Ion 5% Nitrate 6% Crustal 4% 174 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix B Particle Speciation - Macon 2012 Organic Carbon 42% Sulfate 23% Other 14% Elemental Carbon 5% Ammonium Ion 5% Nitrate 5% Crustal 6% Particle Speciation - Athens 2012 Organic Carbon 38% Elemental Carbon 3% Ammonium Ion 7% Sulfate 26% Other 14% Nitrate 8% Crustal 4% 175 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Particle Speciation - Douglas 2012 Section: Appendix B Organic Carbon 43% Sulfate 26% Other 16% Elemental Carbon 4% Ammonium Ion 4% Nitrate 4% Crustal 3% Particle Speciation- Atlanta 2012 Organic Carbon 41% Sulfate 24% Elemental Carbon 9% Ammonium Ion 5% Other 13% Nitrate 5% Crustal 3% 176 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix B Particle Speciation - Rome 2012 Organic Carbon 38% Sulfate 24% Other 13% Elemental Carbon 10% Ammonium Ion 6% Nitrate 5% Crustal 4% Particle Speciation - Columbus 2012 Organic Carbon 45% Sulfate 24% Other 14% Elemental Carbon 4% Ammonium Ion 5% Nitrate 5% Crustal 3% 177 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix B Particle Speciation - Augusta 2012 Organic Carbon 42% Sulfate 24% Other 14% Nitrate 7% Crustal 3% Elemental Carbon 4% Ammonium Ion 6% Particle Speciation - Rossville 2012 Organic Carbon 45% Sulfate 23% Other 12% Nitrate 6% Crustal 4% Elemental Carbon 4% Ammonium Ion 6% 178 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix C Appendix C: Additional PAMS Data PAMS Continuous Hydrocarbon Data (June-August 2012) (concentrations in parts per billion Carbon (ppbC)) Name Site #Samples Avg. 1st Max 2nd Max PAMSHC S. DeKalb Conyers Yorkville 1465 1232 1864 20.43 35.00 22.87 160.2 135.3 204.7 158.8 132.8 183.6 TNMOC S. DeKalb Conyers Yorkville 1465 1232 1864 25.82 43.87 32.00 216.9 182.5 283.0 208.2 176.7 219.0 Ethane S. DeKalb Conyers Yorkville 1462 1229 1752 2.930 1.958 2.743 10.68 9.60 7.78 7.78 8.52 7.14 Ethylene S. DeKalb 1462 1.249 8.90 8.69 Conyers 1229 0.367 3.50 2.67 Yorkville 1752 0.296 2.89 2.26 Propane S. DeKalb Conyers Yorkville 1462 1229 1752 2.850 2.028 2.418 27.50 11.18 50.05 20.36 10.81 15.36 Propylene S. DeKalb 1462 0.845 3.98 3.94 Conyers 1229 0.378 2.04 1.56 Yorkville 1752 0.349 1.94 1.89 Acetylene S. DeKalb 1462 0.370 9.00 3.70 Conyers 1229 0.150 1.50 1.00 Yorkville 1752 0.180 2.80 1.00 n-Butane S. DeKalb 1462 1.183 8.41 7.12 Conyers 1229 1.518 5.50 4.89 Yorkville 1752 0.694 5.31 4.02 Isobutane S. DeKalb 1462 0.468 4.81 4.78 Conyers 1229 0.617 4.34 3.51 Yorkville 1752 0.230 2.96 2.44 trans-2-Butene S. DeKalb 1462 0.023 1.96 1.27 Conyers 1229 0.011 0.54 0.48 Yorkville 1752 0.022 5.10 4.67 cis-2-Butene S. DeKalb 1462 0.020 3.48 1.69 Conyers 1229 0.011 1.14 0.74 Yorkville 1752 0.021 3.45 1.30 n-Pentane S. DeKalb Conyers Yorkville 1462 1229 1752 1.393 1.419 0.541 12.84 14.55 4.84 12.37 13.42 3.28 Isopentane S. DeKalb Conyers Yorkville 1462 1229 1752 1.829 2.190 0.840 16.02 30.40 8.33 15.82 21.70 5.98 1-Pentene S. DeKalb 1462 0.034 0.85 0.54 Conyers 1229 0.031 1.05 0.46 Yorkville 1752 0.009 2.30 0.89 179 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix C PAMS Continuous Hydrocarbon Data (June-August 2012)(continued) Name (concentrations in ppbC) Site #Samples Avg. 1st Max 2nd Max trans-2-Pentene S. DeKalb 1462 0.036 0.68 0.67 Conyers 1229 0.010 2.40 0.42 Yorkville 1752 0.008 2.36 0.94 cis-2-Pentene S. DeKalb 1462 0.017 1.20 0.50 Conyers 1229 0.008 1.09 0.52 Yorkville 1752 0.007 3.09 0.59 3-Methylpentane S. DeKalb 1462 0.140 2.82 2.55 Conyers 1229 0.229 4.72 1.56 Yorkville 1752 0.094 1.96 1.83 n-Hexane S. DeKalb 529 0.582 5.00 4.96 Conyers 1211 0.920 6.42 4.34 Yorkville 1838 0.366 5.64 5.24 n-Heptane S. DeKalb 529 0.223 2.05 2.00 Conyers 1210 0.122 1.57 1.10 Yorkville 1838 0.031 3.10 1.46 n-Octane S. DeKalb 529 0.101 1.01 1.00 Conyers 1210 0.051 1.32 1.13 Yorkville 1838 0.034 5.67 3.92 n-Nonane S. DeKalb 529 0.084 3.19 2.30 Conyers 1211 0.058 1.58 1.54 Yorkville 1838 0.026 3.23 1.35 n-Decane S. DeKalb 529 0.295 4.81 3.10 Conyers 1211 0.233 2.68 2.48 Yorkville 1838 0.103 4.92 3.64 Cyclopentane S. DeKalb 1462 0.249 7.55 7.18 Conyers 1229 0.133 1.66 1.21 Yorkville 1752 0.016 1.89 0.47 Isoprene S. DeKalb 1462 1.744 15.22 14.82 Conyers 1229 10.456 58.54 57.21 Yorkville 1752 8.335 105.18 103.82 2,2-Dimethylbutane S. DeKalb 1462 0.065 4.14 3.36 Conyers 1229 0.121 1.22 1.16 Yorkville 1752 0.008 3.88 0.81 2,4-Dimethylpentane S. DeKalb 293 0.144 1.05 1.03 Conyers 1211 0.062 2.64 1.71 Yorkville 1838 0.027 6.17 0.78 Cyclohexane S. DeKalb 529 0.071 0.92 0.90 Conyers 1211 0.068 1.35 1.18 Yorkville 1838 0.022 6.15 0.84 3-Methylhexane S. DeKalb 529 0.375 4.03 2.69 Conyers 1211 0.217 2.24 2.11 Yorkville 1838 0.103 3.73 1.72 2,2,4-Trimethylpentane S. DeKalb 529 0.535 4.71 4.60 Conyers 1210 0.309 3.37 3.15 Yorkville 1838 0.142 4.11 3.81 180 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix C PAMS Continuous Hydrocarbon Data (June-August 2012)(continued) Name (concentrations in ppbC) Site #Samples Avg. 1st Max 2nd Max 2,3,4-Trimethylpentane S. DeKalb 529 0.178 1.66 1.65 Conyers 1210 0.046 1.22 0.91 Yorkville 1838 0.027 3.56 1.62 3-Methylheptane S. DeKalb 529 0.080 1.03 0.83 Conyers 1210 0.092 1.38 1.16 Yorkville 1838 0.014 3.64 0.93 Methylcyclohexane S. DeKalb 529 0.135 2.08 1.52 Conyers 1210 0.146 1.24 1.00 Yorkville 1838 0.015 4.32 0.61 Methylcyclopentane S. DeKalb 293 0.351 2.05 2.05 Conyers 1211 0.111 1.93 1.87 Yorkville 1838 0.042 3.72 1.11 2-Methylhexane S. DeKalb 529 0.205 2.08 2.03 Conyers 1211 0.052 1.73 1.65 Yorkville 1838 0.055 2.54 1.09 1-Butene S. DeKalb 1462 0.123 2.50 2.43 Conyers 1229 0.217 0.64 0.61 Yorkville 1752 0.013 2.95 0.75 2,3-Dimethylbutane S. DeKalb 1462 0.105 7.43 3.76 Conyers 1229 0.041 1.45 0.80 Yorkville 1752 0.015 1.10 0.42 2-Methylpentane S. DeKalb 1462 0.267 8.02 4.01 Conyers 1229 0.288 4.87 2.04 Yorkville 1752 0.170 4.79 1.39 2,3-Dimethylpentane S. DeKalb 508 0.127 1.34 1.33 Conyers 1211 0.033 1.38 1.06 Yorkville 1838 0.042 8.56 3.07 n-Undecane S. DeKalb 529 0.294 10.35 5.17 Conyers 1211 0.210 3.31 3.02 Yorkville 1838 0.513 17.05 6.35 2-Methylheptane S. DeKalb 529 0.039 0.67 0.62 Conyers 1210 0.024 1.01 0.79 Yorkville 1838 0.019 3.30 1.81 m & p Xylenes S. DeKalb 529 0.773 5.63 5.59 Conyers 1211 0.404 4.06 2.94 Yorkville 1838 0.235 3.96 3.12 Benzene S. DeKalb 529 0.559 10.42 4.28 Conyers 1211 0.276 2.70 2.14 Yorkville 1838 0.139 3.67 2.31 Toluene S. DeKalb 529 1.972 14.89 14.29 Conyers 1210 1.184 6.99 6.63 Yorkville 1838 0.707 8.65 5.92 Ethylbenzene S. DeKalb 529 0.205 1.85 1.79 Conyers 1211 0.116 1.31 1.13 Yorkville 1838 0.046 2.90 2.80 181 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix C PAMS Continuous Hydrocarbon Data (June-August 2012)(continued) Name (concentrations in ppbC) Site #Samples Avg. 1st Max 2nd Max o-Xylene S. DeKalb 529 0.327 2.80 2.67 Conyers 1211 0.178 1.78 1.19 Yorkville 1838 0.065 3.52 1.89 1,3,5-Trimethylbenzene S. DeKalb 477 0.177 9.92 3.96 Conyers 1211 0.081 1.20 1.02 Yorkville 1838 0.037 3.02 1.32 1,2,4-Trimethylbenzene S. DeKalb 529 0.589 4.86 4.65 Conyers 1211 0.471 2.99 2.84 Yorkville 1838 0.511 42.44 11.03 n-Propylbenzene S. DeKalb 529 0.090 3.98 0.96 Conyers 1211 0.073 1.66 1.34 Yorkville 1838 0.065 3.40 2.29 Isopropylbenzene S. DeKalb 529 0.016 0.47 0.47 Conyers 1211 0.033 1.49 1.48 Yorkville 1838 0.118 5.27 1.73 o-Ethyltoluene S. DeKalb 529 0.184 1.63 1.60 Conyers 1211 0.175 2.37 2.34 Yorkville 1838 0.157 3.90 3.38 m-Ethyltoluene S. DeKalb N/A Conyers N/A Yorkville N/A m-Diethylbenzene S. DeKalb 529 0.121 2.32 2.03 Conyers 1211 0.062 2.66 2.64 Yorkville 1838 0.022 4.94 4.32 p-Diethylbenzene S. DeKalb 529 0.460 16.19 3.71 Conyers 1211 0.070 1.78 1.56 Yorkville 1838 0.016 2.83 0.57 Styrene S. DeKalb 529 0.140 2.97 1.78 Conyers 1211 0.238 1.76 1.67 Yorkville 1838 0.045 3.63 1.65 Beta Pinene and 1,2,3- S. DeKalb 529 2.271 11.00 10.98 Trimethylbenzene Conyers 1211 4.410 57.11 53.79 Yorkville 1838 1.955 90.16 74.26 Pinene and p-Ethyltoluene S. DeKalb N/A Conyers N/A Yorkville N/A m and p-Ethyltoluene S. DeKalb 477 1.463 13.05 9.26 Conyers 23 4.036 10.93 10.83 Yorkville 1251 0.849 8.31 7.11 m/p-Ethyltoluene S. DeKalb N/A Conyers 1188 2.665 28.98 28.70 Yorkville 587 2.684 85.47 59.15 N/A indicates not applicable 182 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix C PAMS 2012 24-hour Canister Hydrocarbons (concentrations in parts per billion Carbon (ppbC)) Name Site #Samples #Detects^ Avg.* 1st Max 2nd Max PAMSHC TNMOC Ethane S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 61 50.07 120.0 110.0 58 33.24 82.0 63.0 51 23.37 190.0 46.0 61 125.92 240.0 230.0 58 161.00 640.0 430.0 51 84.57 260.0 190.0 40 3.47 13.0 11.0 39 2.85 9.3 7.9 36 2.82 12.0 6.7 Ethylene Propane Propylene S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 15 0.76 5.4 4.8 58 0.46 2.4 2.1 10 0.25 1.4 1.3 54 5.47 18.0 13.0 53 3.94 9.0 9.0 48 3.74 12.0 9.3 44 0.81 2.8 2.7 32 0.34 1.3 0.9 12 0.14 0.4 0.4 Acetylene n-Butane Isobutane trans-2-Butene cis-2-Butene n-Pentane Isopentane 1-Pentene trans-2-Pentene S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 S. DeKalb 61 Conyers 58 Yorkville 51 49 2.13 13.0 10.0 39 1.50 9.1 8.9 31 0.93 6.4 6.1 56 4.53 14.0 14.0 51 2.00 6.3 5.6 41 1.31 6.9 5.7 46 1.25 4.0 3.9 34 0.55 1.9 1.7 25 0.38 2.3 1.6 2 0.10 0.4 0.4 ND ND 1 0.10 0.3 2 0.17 2.4 2.2 ND 59 2.77 8.5 8.2 54 1.33 5.3 3.5 41 0.60 2.0 1.5 58 4.32 15.0 14.0 55 2.02 7.0 6.4 47 1.02 4.6 3.6 14 0.30 9.2 1.5 5 0.13 0.9 0.6 1 0.10 0.3 21 0.54 3.7 3.5 10 0.34 3.1 2.0 7 0.29 2.9 2.8 183 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix C PAMS 2012 24-hour Canister Hydrocarbons (continued) Name (concentrations in ppbC) Site #Samples #Detects^ Avg.* 1st Max 2nd Max cis-2-Pentene S. DeKalb 61 9 0.37 4.5 3.0 Conyers 58 7 0.53 4.6 4.3 Yorkville 51 15 0.83 4.4 4.1 3-Methylpentane S. DeKalb 61 47 0.64 2.8 2.2 Conyers 58 37 1.24 12.0 11.0 Yorkville 51 9 0.15 0.7 0.5 n-Hexane S. DeKalb 61 50 0.88 2.8 2.4 Conyers 58 39 0.33 1.9 1.3 Yorkville 51 16 0.17 1.7 1.6 n-Heptane S. DeKalb 61 32 0.33 1.1 1.1 Conyers 58 12 0.13 0.5 0.4 Yorkville 51 1 0.09 0.2 n-Octane S. DeKalb 61 20 0.20 1.1 0.9 Conyers 58 3 0.10 0.4 0.3 Yorkville 51 3 0.10 0.4 0.2 n-Nonane S. DeKalb 61 7 0.11 0.3 0.3 Conyers 58 1 0.09 0.3 Yorkville 51 ND n-Decane S. DeKalb 61 8 0.12 0.4 0.3 Conyers 58 3 0.10 0.3 0.2 Yorkville 51 ND Cyclopentane S. DeKalb 61 5 0.11 0.4 0.3 Conyers 58 4 0.17 2.3 1.6 Yorkville 51 1 0.10 0.5 Isoprene S. DeKalb 61 37 3.06 16.0 13.0 Conyers 58 32 3.12 17.0 13.0 Yorkville 51 28 1.83 13.0 7.3 2,2-Dimethylbutane S. DeKalb 61 24 0.21 0.9 0.7 Conyers 58 21 0.56 3.6 2.8 Yorkville 51 ND 2,4-Dimethylpentane S. DeKalb 61 16 0.17 0.7 0.6 Conyers 58 4 0.13 1.1 0.9 Yorkville 51 3 0.13 1.8 0.3 Cyclohexane S. DeKalb 61 11 0.13 0.5 0.4 Conyers 58 ND Yorkville 51 ND 3-Methylhexane S. DeKalb 61 42 0.45 1.5 1.1 Conyers 58 30 0.37 1.8 1.2 Yorkville 51 2 0.10 0.2 0.2 2,2,4-Trimethylpentane S. DeKalb 61 55 1.17 4.1 3.4 Conyers 58 34 0.26 1.3 1.0 Yorkville 51 1 0.01 0.3 2,3,4-Trimethylpentane S. DeKalb 61 28 0.26 1.9 0.8 Conyers 58 5 0.11 0.5 0.3 Yorkville 51 ND 184 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix C PAMS 2012 24-hour Canister Hydrocarbons (continued) Name (concentrations in ppbC) Site #Samples #Detects^ Avg.* 1st Max 2ndMax 3-Methylheptane S. DeKalb 61 2 0.10 0.3 0.2 Conyers 58 1 0.09 0.2 Yorkville 51 ND Methylcyclohexane S. DeKalb 61 12 0.13 0.5 0.5 Conyers 58 1 0.09 0.2 Yorkville 51 ND Methylcyclopentane S. DeKalb 61 37 0.39 1.5 1.1 Conyers 58 7 0.19 3.2 0.8 Yorkville 51 1 0.09 0.2 2-Methylhexane S. DeKalb 61 33 0.33 1.1 0.9 Conyers 58 7 0.80 26.0 12.0 Yorkville 51 2 0.10 0.5 0.2 1-Butene S. DeKalb 61 19 0.20 0.7 0.7 Conyers 58 12 0.14 0.7 0.4 Yorkville 51 1 0.24 7.6 2,3-Dimenthylbutane S. DeKalb 61 29 0.32 2.0 1.4 Conyers 58 15 0.37 3.5 2.5 Yorkville 51 4 0.12 0.8 0.4 2-Methylpentane S. DeKalb 61 49 0.99 3.7 2.8 Conyers 58 40 0.51 3.1 2.0 Yorkville 51 14 0.18 1.8 0.7 2,3-Dimethylpentane S. DeKalb 61 21 0.20 0.9 0.7 Conyers 58 10 0.24 4.6 2.2 Yorkville 51 3 0.11 0.5 0.4 n-Undecane S. DeKalb 61 17 0.18 1.0 0.6 Conyers 58 3 0.10 0.3 0.2 Yorkville 51 ND 2-Methylheptane S. DeKalb 61 2 0.10 0.4 0.2 Conyers 58 3 0.11 0.4 0.3 Yorkville 51 ND m & p Xylenes S. DeKalb 61 57 1.41 4.7 4.0 Conyers 58 44 0.46 2.5 1.7 Yorkville 51 12 0.08 0.7 0.6 Benzene S. DeKalb 61 56 1.06 3.2 2.6 Conyers 58 50 0.73 2.0 1.9 Yorkville 51 40 0.44 1.2 1.2 Toluene S. DeKalb 61 61 3.25 10.0 10.0 Conyers 58 57 1.56 5.0 4.5 Yorkville 51 46 0.61 1.4 1.4 Ethylbenzene S. DeKalb 61 32 0.28 1.1 1.0 Conyers 58 9 0.07 1.6 0.6 Yorkville 51 1 0.01 0.4 o-Xylene S. DeKalb 61 42 0.50 4.3 1.6 Conyers 58 15 0.09 0.8 0.7 Yorkville 51 2 0.02 0.6 0.2 185 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix C PAMS 2012 24-hour Canister Hydrocarbons (continued) Name (concentrations in ppbC) Site #Samples #Detects^ Avg.* 1st Max 2ndMax 1,3,5-Trimethylbenzene S. DeKalb 61 15 0.22 2.5 2.1 Conyers 58 4 0.21 4.9 1.7 Yorkville 51 6 0.19 2.2 1.8 1,2,4-Trimethylbenzene S. DeKalb 61 44 2.75 13.0 11.0 Conyers 58 30 2.09 20.0 19.0 Yorkville 51 14 5.60 174.0 22.0 n-Propylbenzene S. DeKalb 61 1 0.10 0.3 Conyers 58 2 0.10 0.4 0.2 Yorkville 51 ND Isopropylbenzene S. DeKalb 61 ND Conyers 58 ND Yorkville 51 ND o-Ethyltoluene S. DeKalb 61 19 0.24 1.2 1.0 Conyers 58 9 0.17 1.8 0.7 Yorkville 51 4 0.12 0.5 0.5 m-Ethyltoluene S. DeKalb 61 33 0.43 2.7 1.5 Conyers 58 23 0.19 1.6 0.4 Yorkville 51 4 0.16 1.5 1.4 p-Ethyltoluene S. DeKalb 61 34 0.33 1.3 1.1 Conyers 58 37 0.47 3.6 1.6 Yorkville 51 5 0.11 0.5 0.3 m-Diethylbenzene S. DeKalb 61 4 0.10 0.3 0.3 Conyers 58 8 0.31 2.7 1.7 Yorkville 51 2 0.12 0.9 0.9 p-Diethylbenzene S. DeKalb 61 7 0.11 0.3 0.3 Conyers 58 6 0.27 3.8 3.0 Yorkville 51 2 0.10 0.4 0.2 Styrene S. DeKalb 61 47 0.40 1.1 1.0 Conyers 58 51 1.01 3.2 2.3 Yorkville 51 39 0.46 2.0 1.4 1,2,3-Trimethylbenzene S. DeKalb 61 30 0.30 1.2 1.0 Conyers 58 17 0.32 3.4 2.7 Yorkville 51 4 0.14 1.4 0.7 ND indicates no detection ^Detect is counted as any value above half method detection limit. *When a detected concentration is below one half of the method detection limit, then one half of the method detection level is used to calculate the average. 186 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D Name Antimony Arsenic Beryllium Cadmium Chromium Chromium+6*** Cobalt Appendix D: Additional Toxics Data 2012 Metals (concentrations in micrograms per cubic meter (g/m3)) Site #Samples #Detects^ Avg.* Macon 28 28 0.00092 Savannah 26 24 0.00055 General Coffee 28 27 0.00030 Dawsonville 29 26 0.00055 South DeKalb** 55 55 0.00101 Yorkville 28 26 0.00083 Macon 28 Savannah 26 General Coffee 28 Dawsonville 29 South DeKalb** 55 Yorkville 28 23 0.00071 20 0.00089 27 0.00116 21 0.00089 43 0.00050 18 0.00050 Macon 28 Savannah 26 General Coffee 28 Dawsonville 29 South DeKalb** 55 Yorkville 28 ND 1 0.00003 ND 2 0.00003 2 0.00003 ND Macon 28 Savannah 26 General Coffee 28 Dawsonville 29 South DeKalb** 55 Yorkville 28 24 0.00010 25 0.00028 26 0.00011 26 0.00009 52 0.00007 21 0.00012 Macon 28 Savannah 26 General Coffee 28 Dawsonville 29 South DeKalb** 55 Yorkville 28 27 0.00165 25 0.00191 28 0.00140 27 0.00164 55 0.00116 24 0.00142 South DeKalb 54 32 0.00001 Macon 28 Savannah 26 General Coffee 28 Dawsonville 29 South DeKalb** 55 Yorkville 28 19 0.00009 24 0.00009 14 0.00006 11 0.00007 18 0.00006 10 0.00012 1st Max 0.00207 0.00159 0.00113 0.00089 0.00365 0.00328 0.00173 0.00231 0.00333 0.00514 0.00124 0.00136 0.00009 0.00004 0.00006 0.00023 0.00070 0.00034 0.00035 0.00029 0.00086 0.00469 0.00386 0.00216 0.00566 0.0019 0.00283 0.00010 0.00024 0.00026 0.00014 0.00020 0.00010 0.00185 2nd Max 0.00154 0.00140 0.00062 0.00051 0.00319 0.00241 0.00153 0.00223 0.00298 0.00488 0.00120 0.00114 0.00003 0.00006 0.00022 0.00054 0.00026 0.00028 0.00018 0.00081 0.00256 0.00308 0.00207 0.00565 0.00184 0.00276 0.00006 0.00019 0.00015 0.00008 0.00015 0.00010 0.00008 187 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D Name 2012 Metals (continued) (concentrations in g/m3) Site #Samples #Detects^ Avg.* 1st Max 2nd Max Lead Macon 28 28 0.00269 0.01231 0.00765 Savannah 26 26 0.00202 0.00497 0.00379 General Coffee 28 28 0.00139 0.00242 0.00222 Dawsonville 29 28 0.00162 0.00720 0.00360 South DeKalb** 55 55 0.00120 0.00260 0.00250 Yorkville 28 27 0.00203 0.01222 0.00379 Manganese Macon 28 28 0.00780 0.02762 0.01632 Savannah 26 26 0.00422 0.01025 0.00805 General Coffee 28 28 0.00331 0.00801 0.00709 Dawsonville 29 28 0.00380 0.01439 0.01132 South DeKalb** 55 55 0.00254 0.00635 0.00581 Yorkville 28 27 0.00365 0.01987 0.00960 Nickel Macon 28 28 0.00226 0.01502 0.00603 Savannah 26 26 0.00298 0.00723 0.00620 General Coffee 28 28 0.00224 0.00978 0.00472 Dawsonville 29 28 0.00163 0.00616 0.00471 South DeKalb** 55 55 0.00109 0.00360 0.00359 Yorkville 28 27 0.00183 0.01018 0.00406 Selenium Macon 28 26 0.00121 0.02001 0.00113 Savannah 26 24 0.00058 0.00129 0.00125 General Coffee 28 23 0.00117 0.02171 0.00119 Dawsonville 29 22 0.00059 0.00350 0.00272 South DeKalb** 55 44 0.00030 0.00080 0.00078 Yorkville 28 18 0.00063 0.00991 0.00094 Zinc Macon 28 28 0.02189 0.06733 0.06630 Savannah 26 26 0.02776 0.28960 0.03229 General Coffee 28 28 0.01748 0.02831 0.02593 Dawsonville 29 28 0.01448 0.07201 0.04824 South DeKalb** 55 55 0.01155 0.02825 0.02304 Yorkville 28 27 0.02042 0.10554 0.06566 *When a detected concentration is below one half of the method detection limit, then one half of the method detection level is used to calculate the average. ** Selected PM10 Hi-Vol, sample collected every 6 days *** Hexavalent Chromium, sample collected every 6 days ND indicates no detection ^Detect is counted as any value above half method detection limit. 188 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D Name Acenaphthene Acenaphthylene Anthracene Benzo(a)anthracene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene 2012 Semi-Volatile Compounds (concentrations in g/m3) Site #Samples #Detects^ Avg.** Macon 29 25 0.00342 Savannah 23 22 0.00228 General Coffee 30 21 0.00130 Dawsonville 29 8 0.00030 South DeKalb* 58 52 0.00213 Yorkville 28 5 0.00029 Macon 29 2 0.00022 Savannah 23 ND General Coffee 30 ND Dawsonville 29 South DeKalb* 58 ND 12 0.00027 Yorkville 28 ND Macon 29 ND Savannah 23 5 0.00039 General Coffee 30 ND Dawsonville 29 South DeKalb* 58 ND 10 0.00037 Yorkville 28 ND Macon 28 ND Savannah 21 ND General Coffee 28 ND Dawsonville 27 ND South DeKalb* 58 3 0.00016 Yorkville 26 ND Macon 28 ND Savannah 21 ND General Coffee 28 ND Dawsonville 27 ND South DeKalb* 58 8 0.00019 Yorkville 26 ND Macon 28 1 0.00018 Savannah 21 General Coffee 28 1 0.00017 ND Dawsonville 27 ND South DeKalb* 58 2 0.00016 Yorkville 26 ND Macon 29 1 0.00018 Savannah 22 ND General Coffee 30 ND Dawsonville 29 ND South DeKalb* 58 3 0.00016 Yorkville 26 ND 1st Max 0.01367 0.00636 0.00660 0.00116 0.00723 0.00165 0.00144 0.00213 0.00204 0.00675 0.00091 0.00100 0.00101 0.00063 0.00037 0.00097 0.00065 2nd Max 0.00750 0.00454 0.00356 0.00083 0.00610 0.00135 0.00092 0.00149 0.00136 0.00329 0.00021 0.00082 0.00023 0.00034 189 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D Name 2012 Semi-Volatile Compounds (continued) (concentrations in g/m3) Site #Samples #Detects^ Avg.** 1st Max Benzo(e)pyrene Macon 29 ND Savannah 23 ND General Coffee 30 ND Dawsonville 29 ND South DeKalb* 58 3 0.00016 0.00045 Yorkville 28 ND Benzo(g,h,i)perylene Macon 29 1 0.00031 0.00471 Savannah 22 ND General Coffee 30 ND Dawsonville 29 ND South DeKalb* 58 3 0.00016 0.00038 Yorkville 28 ND Chrysene Macon 29 2 0.00018 0.00061 Savannah 23 1 0.00017 0.00069 General Coffee 30 ND Dawsonville 29 ND South DeKalb* 58 7 0.00018 0.00102 Yorkville 28 ND Dibenzo(a,h)anthracene Macon 26 ND Savannah 19 ND General Coffee 27 ND Dawsonville 29 ND South DeKalb* 58 ND Yorkville 25 ND Fluoranthene Macon 29 19 0.00147 0.00668 Savannah 23 20 0.00110 0.00325 General Coffee 30 ND Dawsonville 29 4 0.00019 0.00051 South DeKalb* 58 38 0.00063 0.00246 Yorkville 28 7 0.00022 0.00066 Fluorene Macon 29 22 0.00346 0.01049 Savannah 23 22 0.00333 0.00909 General Coffee 30 12 0.00090 0.00377 Dawsonville 29 11 0.00080 0.00236 South DeKalb* 58 51 0.00295 0.00650 Yorkville 28 9 0.00085 0.00346 Indeno(1,2,3-cd)pyrene Macon 29 ND Savannah 22 ND General Coffee 30 ND Dawsonville 29 ND South DeKalb* 58 3 0.00016 0.00047 Yorkville 28 ND Naphthalene Macon 29 29 0.02754 0.05406 Savannah 23 23 0.01630 0.06120 General Coffee 30 30 0.00911 0.03386 Dawsonville 28 27 0.01176 0.03270 2nd Max 0.00041 0.00037 0.00044 0.00044 0.00628 0.00247 0.00047 0.00199 0.00065 0.00754 0.00670 0.00282 0.00225 0.00547 0.00337 0.00037 0.05355 0.05975 0.01950 0.02185 190 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D Name 2012 Semi-Volatile Compounds (continued) (concentrations in g/m3) Site #Samples #Detects^ Avg.** 1st Max Naphthalene (continued) South DeKalb* 58 58 0.07433 0.18300 Yorkville 28 28 0.01243 0.02829 Phenanthrene Macon 29 29 0.00766 0.02798 Savannah 23 23 0.00579 0.01785 General Coffee 30 23 0.00164 0.00503 Dawsonville 29 27 0.00158 0.00257 South DeKalb* 58 57 0.00400 0.00772 Yorkville 28 27 0.00169 0.00346 Pyrene Macon 29 11 0.00051 0.00345 Savannah 23 11 0.00045 0.00172 General Coffee 30 ND Dawsonville 29 1 0.00015 0.00025 South DeKalb* 58 32 0.00034 0.00170 Yorkville 28 2 0.00015 0.00025 Retene South DeKalb* 29 21 0.00043 0.00245 9-fluorenone South DeKalb* 29 29 0.00079 0.00155 Cyclopenta(cd)pyrene South DeKalb* 29 ND Coronene South DeKalb* 29 ND Perylene South DeKalb* 35 1 0.00015 0.00019 2nd Max 0.18000 0.02391 0.01696 0.01131 0.00367 0.00252 0.00742 0.00324 0.00204 0.00115 0.00079 0.00016 0.00156 0.00121 ND indicates no detection ^Detect is counted as any value above half method detection limit. *Sample collected every 6 days and analyzed at ERG laboratory with gas chromatography. **When a detected concentration is below one half of the method detection limit, then one half of the method detection level is used to calculate the average. 191 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D Name Freon 113 Freon 114 1,3-Butadiene Cyclohexane Chloromethane Dichloromethane Chloroform Carbon tetrachloride 2012 Volatile Organic Compounds (concentrations in g/m3) Site #Samples #Detects^ Avg.** Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Macon 26 1 0.4364 Savannah 25 3 0.5009 General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Macon 26 26 1.3640 Savannah 25 13 1.2161 General Coffee 28 28 1.5063 Dawsonville 30 30 1.2950 South DeKalb* 61 61 1.2298 Yorkville 27 27 1.2201 Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 4 1.1855 Yorkville 27 ND Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 1 0.6965 Yorkville 27 ND Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 1 0.7894 1st Max 0.5854 2.1696 1.7763 9.0879 1.9622 1.6524 1.9002 1.6524 14.2368 5.8601 0.8807 2nd Max 0.5166 1.6730 1.9209 1.9002 1.6110 1.5284 1.5284 13.5423 192 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D 2012 Volatile Organic Compounds (continued) (concentrations in g/m3) Name Site #Samples #Detects^ Avg.** 1st Max Carbon tetrachloride South DeKalb* 61 ND (continued) Yorkville 27 ND Trichlorofluoromethane Macon 26 26 1.3141 1.6297 Savannah 25 25 1.2925 1.6859 General Coffee 28 28 1.2925 1.6859 Dawsonville 30 30 1.2719 1.5735 South DeKalb* 61 61 1.4197 1.9107 Yorkville 27 27 1.2613 1.5735 Chloroethane Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,1-Dichloroethane Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Methyl chloroform Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Ethylene dichloride Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Tetrachloroethylene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,1,2,2-Tetrachloroethane Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 2nd Max 1.6297 1.6297 1.5735 1.5173 1.9107 1.5735 193 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D 2012 Volatile Organic Compounds (continued) (concentrations in g/m3) Name Site #Samples #Detects^ Avg.** 1st Max Bromomethane Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,1,2-Trichloroethane Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Dichlorodifluoromethane Macon 26 26 2.4134 3.0163 Savannah 25 24 2.3369 2.9174 General Coffee 28 28 2.3594 3.0163 Dawsonville 30 30 2.3455 2.8680 South DeKalb* 61 61 2.4829 3.4613 Yorkville 27 27 2.3350 2.8680 Trichloroethylene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,1-Dichloroethylene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,2-Dichloropropane Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND trans-1,3- Macon 26 ND Dichloropropylene Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND cis-1,3-Dichloropropylene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND 2nd Max 2.9669 2.8680 2.9174 2.7196 3.3625 2.8680 194 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D 2012 Volatile Organic Compounds (continued) (concentrations in g/m3) Name Site #Samples #Detects^ Avg.** 1st Max cis-1,3-Dichloropropylene South DeKalb* 61 ND (continued) Yorkville 27 ND cis-1,2-Dichloroethene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Ethylene dibromide Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Hexachlorobutadiene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Vinyl chloride Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND m/p Xylene Macon 26 1 0.5872 1.6940 Savannah 25 1 0.5595 0.9556 General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 5 0.5561 0.8687 Yorkville 27 ND Benzene Macon 26 21 0.7292 1.3735 Savannah 25 14 0.7941 2.2679 General Coffee 28 8 0.4130 0.5750 Dawsonville 30 28 0.7666 1.4374 South DeKalb* 61 33 0.5472 1.3097 Yorkville 27 3 0.4070 0.5430 Toluene Macon 26 5 0.5382 1.2431 Savannah 25 9 0.6087 1.7328 General Coffee 28 Dawsonville 30 ND 2 0.4771 0.6404 South DeKalb* 61 39 0.9386 3.7669 Yorkville 27 ND Ethylbenzene Macon 26 ND Savannah 25 ND 2nd Max 0.7384 1.3416 1.9485 0.4791 1.1819 1.2458 0.4472 0.9040 1.1301 0.4897 3.2772 195 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D 2012 Volatile Organic Compounds (continued) (concentrations in g/m3) Name Site #Samples #Detects^ Avg.** 1st Max Ethylbenzene General Coffee 28 ND (continuted) Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND o- Xylene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,3,5-Trimethylbenzene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,2,4-Trimethylbenzene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Styrene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Benzene,1-ethenyl-4- Macon 26 ND methyl Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Chlorobenzene Macon 26 8 0.6400 1.1053 Savannah 25 11 0.9726 3.2698 General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,2-Dichlorobenzene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 2nd Max 0.9211 2.4408 196 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D 2012 Volatile Organic Compounds (continued) (concentrations in g/m3) Name Site #Samples #Detects^ Avg.** 1st Max 1,3-Dichlorobenzene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,4-Dichlorobenzene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND Benzyl chloride Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 1,2,4-Trichlorobenzene Macon 26 ND Savannah 25 ND General Coffee 28 ND Dawsonville 30 ND South DeKalb* 61 ND Yorkville 27 ND 2nd Max ND indicates no detection ^Detect is counted as any value above half method detection limit. *Sample collected every 6 days **When a detected concentration is below one half of the method detection limit, then one half of the method detection level is used to calculate the average. 197 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D Name 2012 Carbonyl Compounds, 3-hour (June-August) (concentrations in micrograms per cubic meter) Site Time #Samples #Detects^ Avg.* 1st Max 2nd Max Formaldehyde S. DeKalb 0600 31 0900 30 1200 30 1500 31 30 5.5671 32.7778 25.3889 29 6.6917 19.5556 18.7778 28 7.8545 19.2222 16.3889 29 8.1444 21.9444 18.3333 Acetaldehyde S. DeKalb 0600 31 0900 29 1200 30 1500 31 9 1.0435 3.6222 2.9722 20 1.6060 3.7722 3.4056 24 2.0054 4.5389 3.5444 24 1.9604 4.9667 3.7833 Propionaldehyde S. DeKalb 0600 31 ND 0900 30 ND 1200 30 ND 1500 31 ND Butyraldehyde S. DeKalb 0600 31 ND 0900 30 ND 1200 30 ND 1500 31 ND Acetone S. DeKalb 0600 31 0900 30 1200 30 1500 31 30 4.3237 9.3889 9.0556 28 4.3692 10.5556 8.1111 27 5.0687 12.1111 9.6111 28 5.3460 12.3889 11.0556 Benzaldehyde S. DeKalb 0600 31 ND 0900 30 ND 1200 30 ND 1500 31 ND ND indicates no detection ^Detect is counted as any value above half method detection limit. * When a detected concentration is below one half of the method detection limit, then one half of the method detection level is used to calculate the average. 198 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix D Name Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde Acetone Benzaldehyde Acrolein (with canister method) 2012 Carbonyl Compounds, 24-hour (concentrations in micrograms per cubic meter) Site #Samples #Detects^ Avg.** Savannah 27 24 4.5705 Dawsonville 27 21 1.5792 S. DeKalb* 54 52 15.4481 Savannah 27 9 1.0559 Dawsonville 27 6 0.8095 S. DeKalb* 54 36 2.4892 Savannah Dawsonville S. DeKalb* 27 ND 27 ND 54 5 0.5838 Savannah Dawsonville S. DeKalb* 27 ND 27 ND 54 3 0.5857 Savannah 27 22 3.8782 Dawsonville 27 26 2.9974 S. DeKalb* 54 39 4.0270 Savannah Dawsonville S. DeKalb* 27 ND 27 ND 54 1 0.5729 Macon 26 Savannah 25 General Coffee 28 Dawsonville 30 South DeKalb* 59 Yorkville 27 18 0.5463 14 0.6172 18 0.4909 29 0.7889 52 0.7648 20 0.4270 1st Max 9.8750 4.0278 71.7647 3.7938 3.2222 11.1765 2nd Max 9.3529 3.0611 66.7427 2.3765 1.7944 6.8824 1.0000 0.7778 1.1941 10.9412 6.7778 8.7222 0.9706 8.4706 6.3333 8.6471 1.1529 1.3079 2.5239 1.1472 1.3767 2.9828 0.7801 1.2161 2.0880 1.0555 1.3308 1.6291 0.7342 ND indicates no detection ^Detect is counted as any value above half method detection limit. * When a detected concentration is below one half of the method detection limit, then one half of the method detection level is used to calculate the average. 199 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix E Appendix E: Monitoring Network Survey (40 CFR 58, Appendix D) Georgia Gaseous Criteria Pollutant Monitoring as of January 2012 Parameter Measured Sampling Schedule Number of GASN Sites Method Used EPA Reference Method Data Availability Ozone Nitrogen Dioxide Carbon Monoxide Continuous hourly average Sulfur Dioxide 20 3 3 7 Ultraviolet photometry Ultraviolet photometry Ultraviolet photometry Ultraviolet photometry Non-dispersive Infrared photometry Non-dispersive Infrared photometry Ultraviolet fluorescence detector Spectrophotometry (pararosaniline method) U.S. EPA Air Quality System (AQS) (http://www.epa.gov/ttn/airs/airsaqs/) and GA DNR/EPD Ambient Air Monitoring Program (http://www.air.dnr.state.ga.us/amp) 200 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix E Georgia Ambient Air Particulate Matter Monitoring as of January 2012 Parameter Measured PM10 Mass (integrated) Mass (semicontinuous) PM2.5 Mass (integrated) Mass (semicontinuous) Speciated Sampling Schedule Collection Method Sampling Media Every 6 days Mass sequential, single channel Teflon filter 46.2mm, Continuous hourly averages BAM Proprietary filter; filter tape Varies; daily, every day, every third day, or every sixth day FRM sampler Teflon filter 46.2mm Continuous hourly averages TEOM; BAM Proprietary filter; filter tape 1 in 6 days; 1 in 3 days for South DeKalb Speciation air sampling system (SASS) Teflon, nylon & quartz filter 46.2mm Number of Sites 11 Analyzed 2 28 17 8 Number of Collocated 2 0 Sites Analysis Method Method 016 Electronic analytical balance Method 079; TEOM gravimetric at 50 degrees C; Method 122 Beta Attenuation Monitor 5 0 0 Method 055 Electronic analytical balance Method 703 R&P TEOM with SCC at 30 degrees C; Beta Attenuation Monitor Method 055 Electronic analytical balance Method 014 x-ray fluorescence Method 062 filter preparation Method 064 Ion chromatography Method 065 Thermal/optical carbon Data Availability U.S. EPA Air Quality System (AQS) (http://www.epa.gov/ttn/airs/airsaqs/) and GA DNR/EPD Ambient Air Monitoring Program (http://www.air.dnr.state.ga.us/amp) 201 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix E Georgia Organic Air Toxic Contaminant Monitoring as of January 2012 Parameter Volatile Organic Measured Compounds (VOCs) Carbonyls Semi - VOCs Metals Method TO-15 TO-11A TO 13A 10-2.I Sampling Schedule Collection Equipment Sampling Media Number of Sites Analyzed Number of Collocated Sites Every 12 days, 24-hour; 1 in 6 day schedule for South DeKalb AVOCS or ATEC2200 Polished stainless steel canister 6** 1 Every 12 days, 24-hour; 1 in 6 day schedule for South DeKalb ATEC100 and or ATEC2200 DNPH-coated silica cartridges and Polished stainless steel canister 3 1 Every 12 days, 24hour; 1 in 6 day schedule for South DeKalb Every 12 days, 24hour; 1 in 6 day schedule for South DeKalb* PUF sampler High volume TSP Polyurethane Foam filter Quartz micro-fiber filter 8 x 10 inch 6** 6** 1 1 Data Availability U.S. EPA Air Quality System (AQS) (http://www.epa.gov/ttn/airs/airsaqs/) and GA DNR/EPD Ambient Air Monitoring Program (http://www.air.dnr.state.ga.us/amp) * Sampler at this site is a PM10 Hi-Vol ** 5 GA ATN sites, 1 NATTS (South DeKalb) 202 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report PAMS Monitoring as of January 2012 Section: Appendix E Parameter Sampling Schedule Collection Equipment Sampling Media Number of Sites Analysis Method Data Availability 56 PAMS-Speciated VOCs & Total NMHC Continuous 56PAMS Speciated VOCs & Total NMHC 24-hour 1 in 6 day schedule (all year) ATEC 2200 Continuous hourly average (June-August) Perkin-Elmer HC GC Polished stainless steel canister Direct injection Carbonyl Compounds 3-hour sample (June-August); 24-hour, 1 in 6 day (all year) ATEC 8000; PUF Sampler DNPH coated silica gel Cartridge 3 3 1 PAMS GC/FID GC/FID High performance liquid chromatograph/ultraviolet detector U.S. EPA Air Quality System (AQS) (http://www.epa.gov/ttn/airs/airsaqs/) and GA DNR/EPD Ambient Air Monitoring Program (http://www.air.dnr.state.ga.us/amp) 203 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Georgia Meteorological Monitoring as of January 2012 Section: Appendix E Parameter Measured Sampling Schedule Wind Speed (m/s) Wind Direction (degrees) Ambient Temperature (C) Relative Humidity (%) Atmosphere Pressure (mb) Continuous hourly average Solar Radiation (w/m2) Precip (in) Sig. Theta (deg) Total Ultraviolet Radiation Number of Sites 17 17 8 8 6 3 6 1 3 Method Used Propeller or cup anemometer Wind vane potentiometer Aspirated Thermocouple or thermistor Thin film capacitor Pressure transducer Thermopile or Tipping Wind UV pyranometer bucket direction radiometer Data Availability U.S. EPA Air Quality System (AQS) (http://www.epa.gov/ttn/airs/airsaqs/) and GA DNR/EPD Ambient Air Monitoring Program (http://www.air.dnr.state.ga.us/amp) 204 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Appendix F: Siting Criteria (40 CFR 58, Appendix E) Section: Appendix F Instrument PM10, AISI Nephelo- meter Dichot, TEOM, PM2.5 Lead, TSP O3 CO NO2 Height Above Ground Micro Other 2-7m 2-15m 2-7m 2-15m 207m 2-15m 3-15m 3-15m 2.5 3.5m 3-5m 3-15m 3-15m Space Between Samplers 2m 1m 2m 1m Height Above Obstructions 1m 2 times height of obstacle above inlet 1m Distance From Obstacles Distance From Tree Dripline 2 times height or obstacle above inlet 2 times height or obstacles above inlet 2 times height of obstacles above inlet 2 times height of obstacles above inlet Micro: must be no trees between sampler and road Others: must be 10m if trees, 5m above sampler 2 times height of obstacle above inlet Should be 20m, must be 10m if considered an obstruction Should be 20m, must be 10m if considered an obstruction Micro and middle: no trees between sampler and source Neighborhood: should be 20m, must be 10m if considered an obstruction Should be 20m, must be 10m if considered an obstruction Micro: must be no trees between sampler and road Others: must be 10m if trees, 5m above sampler Should be 20m, if individual tree 5m above probe, must be 10m from dripline Distance from Walls, Parapets, etc. 2m 2m 2m 1m 1m 1m Airflow Arc 270 270 270 270, or on side of building 180 270, or on side of building 180 270, or on side of building 180 205 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix F Instrument Height Above Ground Micro Other SO2 3-15m 3-15m H2S 3-15m 3-15m CH4, THC, NMHC, PAMS 3-15m 3-15m Toxics: Gaseous 910, 910A, 929, 920 3-15m 3-15m Temperature and Relative Humidity 1.252m 2.252m Wind Speed and Direction Solar Radiation 10m 1.5m 10m 1.5m Space Between Samplers Height Above Obstructions 1m 1m 1m 2m Distance From Obstacles 2 times height of obstacle above inlet 2 times height of obstacle above inlet 2 times height of obstacle above inlet 2 times height of obstacle above inlet 4 times height of obstacle above sensor 1.5 times height of obstacle above sensor Distance From Tree Dripline Should be 20m, must be 10m if considered an obstruction Should be 20m, must be 10m if considered an obstruction Should be 20m, must be 10m in direction of urban core Distance from Walls, Parapets, etc. 1m 1m 1m 1 tower width from tower side 2 tower widths from tower side, 1 tower width from tower top 4.5m Airflow Arc 270, or on side of building 180 270, or on side of building 180 270, or on side of building 180 206 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: Appendix G Appendix G: Instrument and Sensor Control Limits (from manuals) ARB'S CONTROL AND WARNING LIMITS LIMITS Control 15% 15% 10% Warning 10% 10% 7% 4% (Flow) 5% (Design) 20% None None None INSTRUMENT All gaseous criteria and non-criteria analyzers Total suspended particulate (TSP) samplers PM10 Dichotomous (Dichot), Lead (Pb), Tapered Element Oscillating Microbalalance (TEOM), Toxic Air Contaminant (XonTech920) Samplers, Beta Attenuation Monitors (BAM), and Carbonyl (XonTech9250) Samplers PM2.5 Laboratory audits (Toxics, PAMS, Motor Vehicle Exhaust and Total Metals) ACCEPTANCE CRITERIA FOR METEOROLOGICAL (MET) SENSORS LIMITS SENSOR 1.0 Celsius (0.5C PAMS only) 1mb~ _ 0.75mm Mercury (Hg) 5% RH for <10% or >90% RH 5% Watts/m2 Less than or equal to 5 combined accuracy and orientation error Between 0.5 and 5m/s and less 0.2m/s 5% difference above 5 m/s Less than or equal to 0.5m/s 0.25 m/s between 0.5 and 5 m/s and less than 5% difference above 5 m/s Less than or equal to 0.5 m/s Ambient Temperature Barometric Pressure Relative Humidity Solar Radiation and Total UV Radiation Wind Direction Horizontal Wind Speed Horizontal Wind Speed Starting Threshold Vertical Wind Speed Vertical wind Speed Starting Threshold 207 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report References Section: References http://www.airnow.gov/index.cfm?action=static.aqi. 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U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry, Atlanta, Georgia. 208 Georgia Department of Natural Resources Environmental Protection Division 2012 Georgia Ambient Air Surveillance Report Section: References ATSDR, 2005b. Toxicological Profile for Arsenic, Draft For Public Comment. U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Registry, Atlanta, Georgia. ATSDR, 2005d. ToxFAQS for Nickel. U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Registry, Atlanta, Georgia. ATSDR, 2005e. Toxicological Profile for Naphthalene, 1-Methylnaphthalene, and 2-Methylnaphthalene. U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Registry, Atlanta, Georgia. ATSDR, 2006a. ToxFAQS for 1,1,1-Trichloroethane. 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