2012 ambient air surveillance report [Nov. 1, 2013]

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
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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

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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

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Section: Chemical Monitoring Activities
All Georgia Sites MSAs Shown as Solid Colors

Figure 1: Georgia Air Monitoring Site Map
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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
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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.

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Figure 4: Carbon Monoxide Site Monitoring Map
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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.

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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

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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

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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
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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.
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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.

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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
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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
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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
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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
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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.

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Figure 18: Sulfur Dioxide Monitoring Site Map
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Environmental Protection Division

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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.
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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
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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

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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.

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Figure 23: Ozone Monitoring Site Map
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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,

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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.
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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
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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

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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

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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.

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Figure 28: Atlanta-Sandy Springs-Marietta MSA Ozone Exceedance Map
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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)
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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
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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.

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Figure 32: Lead Monitoring Site Map
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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.

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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)
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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
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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.

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Figure 36: PM10 Monitoring Site Map
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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 Sout