2007 ambient air surveillance report [Nov. 1, 2008]

GEORGIA DEPARTMENT OF NATURAL RESOURCES
ENVIRONMENTAL PROTECTION DIVISION
Air Protection Branch Ambient Monitoring Program
2007 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, 2008

TABLE OF CONTENTS
LIST OF FIGURES................................................................................................................................ iii LIST OF TABLES ................................................................................................................................... v EXECUTIVE SUMMARY....................................................................................................................... vi GLOSSARY..........................................................................................................................................viii INTRODUCTION.................................................................................................................................... 1 CHEMICAL MONITORING ACTIVITIES................................................................................................2
CARBON MONOXIDE (CO) ...........................................................................................7 OXIDES OF NITROGEN (NO, NO2, NOx and NOy)......................................................10 SULFUR DIOXIDE (SO2)..............................................................................................13 OZONE (O3)..................................................................................................................15 LEAD (Pb).....................................................................................................................24 PARTICULATE MATTER .............................................................................................26 PM10 ..............................................................................................................................27 PM2.5 .............................................................................................................................32 PM2.5 SPECIATION ......................................................................................................39 ACID PRECIPITATION.................................................................................................47 PHOTOCHEMICAL ASSESSMENT MONITORING STATIONS (PAMS)............................................52 CARBONYL COMPOUNDS .........................................................................................57 AIR TOXICS MONITORING................................................................................................................. 63 METALS .......................................................................................................................65 HEXAVALENT CHROMIUM (Cr6) ................................................................................72 VOLATILE ORGANIC COMPOUNDS (TO-14/15)........................................................73 SEMI-VOLATILE ORGANIC COMPOUNDS ................................................................78 METEOROLOGICAL REPORT............................................................................................................ 82 STATE CLIMATOLOGY AND METEOROLOGICAL SUMMARY OF 2007.................. 82 SUMMARY OF METEOROLOGICAL MEASUREMENTS (2007) ................................84 OZONE AND PM2.5 FORECASTING AND DATA ANALYSIS ...................................... 87 SELECT METEOROLOGICAL AND AIR QUALITY STUDIES FOR 2007 ...................91 QUALITY ASSURANCE....................................................................................................................... 94 QUALITY CONTROL AND QUALITY ASSESSMENT ................................................. 95 GASEOUS POLLUTANTS ...........................................................................................96 PARTICULATE MATTER .............................................................................................99 AIR TOXICS ...............................................................................................................104 NATTS ........................................................................................................................109 PHOTOCHEMICAL ASSESSMENT MONITORING................................................... 112 METEOROLOGY ........................................................................................................ 116 QUALITY CONTROL REPORTS ...............................................................................117 STANDARDS LABORATORY ....................................................................................117 LABORATORY AND FIELD STANDARD OPERATING PROCEDURE..................... 117 SITING EVALUATIONS..............................................................................................118 RISK ASSESSMENT ......................................................................................................................... 119 INTRODUCTION ........................................................................................................119 RESULTS AND INTERPRETATION ..........................................................................119 SUMMARY AND DISCUSSION .................................................................................130 OUTREACH AND EDUCATION ........................................................................................................135 MEDIA OUTREACH ...................................................................................................138 OTHER OUTREACH OPPORTUNITIES....................................................................138 Appendix A: Additional Criteria Pollutant Data ................................................................................... 141 Carbon Monoxide (CO)...............................................................................................141 Nitrogen Dioxide (NO2) ...............................................................................................141 Nitric Oxide (NO) ........................................................................................................141 Oxides of Nitrogen (NOx) ...........................................................................................142 Reactive Oxides of Nitrogen (NOy) ............................................................................142 Sulfur Dioxide (SO2)....................................................................................................143
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Ozone (O3)..................................................................................................................144 Lead (Pb) ....................................................................................................................146 Fine Particulate Matter (PM2.5)....................................................................................147 Appendix B: Additional PM2.5 Particle Speciation Data...............................................151 Appendix C: Additional Meteorological Data ...................................................................................... 156 Appendix D: Additional PAMS Data ................................................................................................... 176 PAMS Continuous Hydrocarbon Data (June-August 2007)........................................ 176 PAMS 2007 24-hour Canister Hydrocarbons .............................................................180 Appendix E: Additional Toxics Data ................................................................................................... 184 2007 Metals ................................................................................................................184 2007 Semi-Volatile Compounds .................................................................................188 2007 Volatile Organic Compounds .............................................................................194 2007 Carbonyl Compounds, 24-hour..........................................................................209 2007 Carbonyl Compounds, 3-hour (June-August) ...................................................210 Appendix F: Monitoring Network Survey ............................................................................................ 211 Appendix G: Siting Criteria ................................................................................................................. 216 Appendix H: Instrument and Sensor Control Limits ...........................................................................218 References ......................................................................................................................................... 219
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LIST OF FIGURES
Figure 1: Georgia Air Monitoring Site Map ............................................................................................. 6 Figure 2: Common Sources of Carbon Monoxide (CO) .........................................................................7 Figure 3: Carbon Monoxide Site Monitoring Map................................................................................... 8 Figure 4: Oxides of Nitrogen Monitoring Site Map ...............................................................................12 Figure 5: Sulfur Dioxide Monitoring Site Map....................................................................................... 14 Figure 6: Typical Urban 1-Hour Ozone Diurnal Pattern .......................................................................15 Figure 7: Demonstration of Ozone Formation ...................................................................................... 15 Figure 8: Ozone Formation Process .................................................................................................... 16 Figure 9: Ozone Monitoring Site Map................................................................................................... 18 Figure 10: Georgia's 8-Hour Ozone Nonattainment Area Map ............................................................20 Figure 11: Metro Atlanta Ozone- Number of Violation Days per Year .................................................21 Figure 12: Metro Atlanta Ozone Exceedance Map ..............................................................................22 Figure 13: Ozone Concentrations in ppm, 2006 (Fourth Highest Daily Maximum 8-Hour
Concentrations) ............................................................................................................................. 23 Figure 14: Lead Monitoring Site Map ................................................................................................... 25 Figure 15: Analogy of Particulate Matter Size to Human Hair..............................................................26 Figure 16: PM10 Monitoring Site Map ...................................................................................................28 Figure 17: PM10 Annual Arithmetic Mean Chart ...................................................................................30 Figure 18: PM10 24-Hour Design Values ..............................................................................................31 Figure 19: PM2.5 Federal Reference Method Monitoring Site Map .......................................................34 Figure 20: PM2.5 Monitoring Site Map, Continuous and Speciation Monitors.......................................35 Figure 21: Georgia's PM2.5 Nonattainment Area Map ..........................................................................37 Figure 22: PM2.5 Annual and 24-Hour Concentrations across the United States, 2006 ....................... 38 Figure 23: 2003 PM2.5 Speciation.........................................................................................................39 Figure 24: 2004 PM2.5 Speciation.........................................................................................................40 Figure 25: 2005 PM2.5 Speciation.........................................................................................................40 Figure 26: 2006 PM2.5 Speciation.........................................................................................................41 Figure 27: 2007 PM2.5 Speciation.........................................................................................................41 Figure 28: PM2.5 Speciation, Trends in Ammonium Concentrations ....................................................43 Figure 29: PM2.5 Speciation, Trends in Elemental Carbon Concentrations..........................................43 Figure 30: PM2.5 Speciation, Trends in Organic Carbon Concentrations.............................................. 44 Figure 31: PM2.5 Speciation, Trends in Sulfate Concentrations ...........................................................44 Figure 32: PM2.5 Speciation, Trends in Nitrate Concentrations ............................................................45 Figure 33: PM2.5 Speciation, Trends in Crustal Matter Concentrations ................................................45 Figure 34: Process of Acid Rain Deposition......................................................................................... 47 Figure 35: Acid Rain Monitoring Site Map............................................................................................ 48 Figure 36: Acid Rain Trends, Statewide............................................................................................... 49 Figure 37: Acid Rain Trends, by Location ............................................................................................ 49 Figure 38: Comparison of DNR and NADP Annual Acid Rain Averages ............................................. 50 Figure 39: Three-year Average Precipitation of Sulfate Concentrations (SO42-) in 1989-1991 and
2004-2006...................................................................................................................................... 51 Figure 40: PAMS Monitoring Site Map ................................................................................................. 53 Figure 41: Isoprene Yearly Profile, 2003-2007..................................................................................... 54 Figure 42: Toluene Yearly Profile, 2003-2007...................................................................................... 55 Figure 43: Toluene & Isoprene, Typical Urban Daily Profile ................................................................56 Figure 44: Carbonyls Monitoring Site Map ........................................................................................... 58 Figure 45: Average South DeKalb 3-Hour Carbonyls, June-August, 2005-2007 ................................. 59 Figure 46: Average 24-Hour Carbonyls Concentration and Number of Detects, by Site, 2005-2007 .. 60 Figure 47: Average 24-Hour Carbonyls Concentration vs. Number of Detects, by Species, 2005-2007
....................................................................................................................................................... 61 Figure 48: Acrolein Concentrations and Number of Detections, 2007 ................................................. 62 Figure 49: Metals Monitoring Site Map................................................................................................. 67 Figure 50: Total Detections of Metals, by Site, 2005-2007 ..................................................................68 Figure 51: Average Concentration and Total Detections of Metals, by Species, 2005-2007 ............... 69
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Figure 52: Average Comparison of Zinc, by Site, 2005-2007 ..............................................................70 Figure 53: Zinc at Utoy Creek, 2005-2007 ........................................................................................... 71 Figure 54: Hexavalent Chromium at South DeKalb .............................................................................72 Figure 55: Total Volatile Organic Compounds Detected per Site, 2005-2007 .....................................73 Figure 56: Number of Volatile Organic Compounds (TO-14/15) Detected, Select Compounds, 2005
2007............................................................................................................................................... 74 Figure 57: Total Volatile Organic Compound Loading all Species, by Site, 2005-2007 ....................... 75 Figure 58: Volatile Organic Compounds, Seasonal Effects, 2005-2007 ..............................................76 Figure 59: VOC and SVOC Monitoring Site Map .................................................................................77 Figure 60: Total Semi-Volatile Organic Compounds Detections Per Site, 2005-2007 ......................... 78 Figure 61: Number of Semi-Volatile Organic Compound Detections, by Compound, 2005-2007 ....... 79 Figure 62: Semi-Volatile Organic Compounds at South DeKalb, 2007................................................80 Figure 63: Meteorological Site Map...................................................................................................... 86 Figure 64: Forecasted and Observed 8-hr Ozone for Metro Atlanta for May-Sept. 2007 ....................88 Figure 65: Forecasted and Observed PM2.5 for Metro Atlanta for January June 2007...................... 89 Figure 66: Forecasted and Observed PM2.5 for Metro Atlanta for July December 2007 .................... 90 Figure 67: Comparison of the Maximum Ozone and Particle Pollution Concentration Days Between
2006 and 2007............................................................................................................................... 91 Table 28: PAMS Speciated VOCs Yearly Data Quality Assessment for Conyers ............................. 114 Figure 68: Formulas For Calculating Risk and Hazard Quotient........................................................124 Figure 69: Aggregate Cancer Risk and Hazard Index by Site for 2005-2006 .................................... 128 Figure 70: Aggregate Cancer Risk and Hazard Index by Site for 2007 .............................................128 Figure 71: Estimated County-Level Cancer Risk From the 1999 National Air Toxics Assessment
(NATA99)..................................................................................................................................... 134 Figure 72: The AQI............................................................................................................................. 136 Figure 73: Sample AIRNOW Ozone Concentration Map ...................................................................139
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LIST OF TABLES
Table 1: Georgia Ambient Air Standards Summary ...............................................................................3 Table 2: 2007 Georgia Air Monitoring Network ...................................................................................... 5 Table 3: Common Oxides of Nitrogen Species and Terms ..................................................................10 Table 4: Comparison of Monthly Rainfall Amounts for 2007 and the 30 Year Average for Select Cities
in Georgia ...................................................................................................................................... 83 Table 5: Temperature and Rainfall Statistics for Select Georgia Cities in 2007................................... 84 Table 6: Meteorological Parameters Measured, 2007 .........................................................................85 Table 7: Audits Performed for Each Air Monitoring Program in 2007 ..................................................95 Table 8: NO Data Quality Assessment................................................................................................. 97 Table 9: NO2 Data Quality Assessment................................................................................................97 Table 10: NOX Data Quality Assessment .............................................................................................98 Table 11: CO Data Quality Assessment............................................................................................... 98 Table 12: SO2 Data Quality Assessment..............................................................................................98 Table 13: O3 Data Quality Assessment ................................................................................................99 Table 14: PM2.5 Data Quality Assessment for FRM Samplers............................................................ 101 Table 15: PM2.5 Data Quality Assessment for Semi-Continuous Samplers........................................ 102 Table 16: PM10 Data Quality Assessment of 24-Hour Integrated Samplers....................................... 103 Table 17: Summary of Unexposed Filter Mass Replicates ................................................................104 Table 18: Summary of Exposed Filter Mass Replicates.....................................................................104 Table 19: Metals Data Quality Assessment for Utoy Creek ...............................................................106 Table 20: Semi-VOCs Data Quality Assessment for Utoy Creek.......................................................107 Table 21: VOCs Data Quality Assessment for Utoy Creek ................................................................108 Table 22: NATTS Sites with EPA Region Numbers and AQS Site Codes.........................................110 Table 23: Measurement Quality Objectives for the NATTS Program................................................. 110 Table 24: MQO Data Sources for the Georgia NAATS Program .......................................................111 Table 25: 23 Selected HAPs and Their AQS Parameter Codes ........................................................112 Table 26: Percent Completeness of Georgia's 2006 AQS Data, Selected Compounds .................... 112 Table 27: PAMS Speciated VOCs Yearly Data Quality Assessment for South DeKalb..................... 113 Table 28: PAMS Speciated VOCs Yearly Data Quality Assessment for Conyers ............................. 114 Table 29: PAMS Speciated VOCs Yearly Data Quality Assessment for Yorkville ............................. 115 Table 30: PAMS Speciated VOCs Yearly Data Quality Assessment for Ambient Monitoring Program
..................................................................................................................................................... 116 Table 31: Meteorological Measurements Accuracy Results ..............................................................117 Table 32: Compounds Monitored and Screening Values Used in Initial Assessment........................ 121 Table 33: Summary of Chemicals Analyzed in 2007..........................................................................122 Table 34: Site-Specific Detection Frequency and Mean Chemical Concentration, 2007 ................... 123 Table 35: Cancer Risk and Hazard Quotient by Location and Chemical, 2007 ................................. 125 Table 36: Aggregate Cancer Risk and Hazard Indices for Each Site, Excluding Carbonyls, 2007.... 127 Table 37: Summary Data for Select VOCs at PAMS Sites, 2007 ......................................................129 Table 38: Summary Observations, Cancer Risk, and Hazard Quotient for Carbonyls, 2007............. 130 Table 39: AQI Summary Data, 2007 .................................................................................................. 137 Table 40: AIRNOW Participation Evaluation Results .........................................................................140
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. The list of compounds monitored has grown over the thirty years to more than 200 pollutants using several types of samplers at sites statewide. 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 2007, 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 with maps identifying individual monitoring sites. These sections also contain discussions on health effects, measurement techniques, and attainment designations for the chemicals that are monitored. Additionally, these sections discuss trends and common sources for the monitored pollutants.
Six (6) 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. The regulatory standard is health-based. Concentrations above the standard are considered unhealthy for sensitive groups. After several years of favorable weather patterns, though, Georgia's 2005 and 2006 data show an uptick in ozone concentrations. It is possible that, given the long-term trend toward improving air quality in the state, that this change is a result of natural variation in weather patterns. At the same time, this recent data is less favorable to Georgia's regulatory status with respect to the national standards. Also, in December 2006 the national limit on 24-hour averaged concentrations of fine particulate matter was reduced. No exceedances of the stricter 24-hour standard occurred before the end of the year, but several sites recorded design values that violate the annual standard.
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, the compounds monitored in the Air Toxics Network are analyzed annually for theoretical lifetime cancer risk and potential non-cancer health effects. 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 2 in 100,000 to 1 in 1,000,000. The potential risk of non-cancer health effects from air toxic pollutants is estimated differently, and most chemicals were well below the `acceptable' 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 the PAMS sites and the sites located statewide. 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 effort in producing 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 is provided, including field and laboratory techniques, as well as results of the 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
vi

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 2007. Included in the summary tables is information on where air toxic compounds were detected, the number of samples collected, and average and maximum concentrations. Copies of this and previous annual reports are available in Adobe Acrobat format via the Ambient Monitoring Internet website at http://www.georgiaair.org/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 smog forecast.
vii

Aerosols AM APB AQCR Anthropogenic ARITH MEAN By-product BAM CAA
CFA 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 ppbC ppm Precursor PUF QTR Rawinsonde RfC Screening Value SLAMS SO2

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 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 US 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 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 State and Local Air Monitoring Site Sulfur Dioxide
viii

SPMS TEOM TNMOC TRS TSP UV VOC w/m2

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

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2007 Georgia Ambient Air Surveillance Report

Section: Introduction

INTRODUCTION

This report summarizes the air quality data collected by the State of Georgia during calendar year 2007. 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, 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

2007 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 reasonably be anticipated to endanger public health or welfare. The Act also requires the Administrator to issue air quality criteria that reflect the latest scientific knowledge useful in indicating the kind and extent of all identifiable effects on public health or welfare that may be expected from the presence of such pollutant in ambient air. Under the CCA, the EPA Administrator establishes 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 includes seven pollutants. The current list is summarized in Table 1.

As shown in Table 1, there are primary and secondary ambient air quality standards. Primary standards are designed to protect the most sensitive individuals in a population. These sensitive individuals include children, the elderly, and those with chronic illnesses. The secondary standards are designed to protect public welfare or quality of life. This includes visibility protection, limiting economic damage, damage to wildlife, the climate or man-made material.

The various averaging times are to address the health impacts of the pollutants. Short-term averages, such as the limit for 8-hour ozone averages, are to protect against acute effects. Long term averaging, such as the annual limit for fine particles, is to protect against chronic effects.

The Georgia ambient air monitoring network provides information on the measured concentrations of criteria and non-criteria pollutants at selected locations. The 2007 Georgia Air Sampling Network collects data at 62 locations in 36 counties. Monitoring takes place year-round, with the exception of ozone, which is sampled from March through October, and the continuous Photochemical Assessment Monitoring Stations (PAMS) volatile organic compounds that sample from June through August. For a list of all the sites in the monitoring network, detailing what pollutants are monitored at which sites, see Table 2. That information is followed by Figure 1, which is an overview map of all the air monitoring locations in the state. Not all pollutants are monitored at all sites. Maps of the monitoring locations for individual pollutants are provided in each pollutant's respective section.

The number and location of the individual sites varies from year to year, depending on: availability of long-term space allocation, regulatory needs, etc. 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 the data collected in the networks undergoes extensive quality assurance review and is then submitted to the Air Quality System (AQS) database maintained by 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 from EPD's continuous monitors are published on EPD's web site at http://www.georgiaair.org/amp. The data is updated hourly. Specific annual summary data for 2007 may be found in Appendix A of this document.

2 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Compound
Sulfur Dioxide
Particulate Matter (PM2.5)
Particulate Matter (PM10)
Carbon Monoxide Ozone
Nitrogen Dioxide Lead

Primary Standard

Secondary Standard

Units

Time Interval



0.5

3 Hour

0.14



24 Hour

0.03



ppm

Annual Mean

Same as

15.0

Primary

Annual Arithmetic Mean (3 years)

98th percentile: 35.0
2nd Maximum: 150

Same as Primary
Same as Primary

micrograms per cubic meter
micrograms per cubic meter

24 Hour 24 Hour

2nd Maximum:

35.0



1 Hour

2nd Maximum: 9.0



ppm

8 Hour Average

4th Maximum: 0.085

Same as Primary

ppm

8 Hour Average

Same as

0.053

Primary

ppm

Annual Mean

Same as micrograms per Calendar Quarter

1.5

Primary cubic meter

Average

Table 1: Georgia Ambient Air Standards Summary

3 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

SITE ID

COMMON NAME

PM2.5 PM2.5 PM2.5

PM10 Acid PAMS

Carb- Meteoro- Aethal-

COUNTY O3 CO FRM Cont. Spec. NO NOx NO2 NOy SO2 TRS Pb PM10 Cont. Rain VOC VOC SVOC onyls logy ometer Cr6 Metals

Rome MSA

131150003

Coosa Elementary

Floyd

S

131150004

Co. Health Dept.

Floyd

NR NR

NR

131150005

Coosa High

Floyd

S

X

S

Brunswick MSA

131270004

Arco Pump Station

Glynn

S

131270006

Risley Middle

Glynn S

S

S M

NR

131273001

Brunswick College

Glynn

NR NR NR

NR

Valdosta MSA

131850003

Mason Elem. Lowndes

S

NR NR

NR

Warner Robins MSA

131530001

Robins Air Base Houston

S

NR NR

NR

Dalton MSA

132130003

Fort Mountain

Murray S

NR

Albany MSA

130950007

Turner Elem. Dougherty

S

S

Gainesville MSA

131390003

Fair St. Elementary

Hall

S

NR NR

NR

Athens-Clark County MSA

130590002

College Station Rd.

Clarke S

S

S

X

Macon MSA

130210007

Allied Chemical

Bibb

S

X

S

130210012

Forestry

Bibb S

S

S

S

NR NR

NR

NR

130210013

Lake Tobesofkee

Bibb S

S

NR

Columbus Georgia- Alabama MSA

132150001

Health Dept. Muscogee

S

132150008

Airport Muscogee S

S

S

S

132150011

Cusseta Elementary Muscogee

S

X

S S

132151003

Crime Lab Muscogee S

NR

132155000

Columbus State Muscogee

NR NR

NR

Savannah MSA

130510014

Shuman Middle School Chatham

S

130510017

Market St. Chatham

S

130510021

E. President St. Chatham S

S

NR NR NR NR

NR

130510091

Mercer Middle Chatham

S

130511002 W. Lathrop & Augusta Ave. Chatham

S

S

NR

Augusta Georgia-South Carolina MSA

130730001

Riverside Park Columbia S

S

NR

131890001

Fish Hatchery McDuffie

G

132450005

Med. College GA Richmond

S

132450091

Bungalow Rd. Richmond S

S

S

X

S

NR

132450092

Clara Jenkins School Richmond

NR NR

NR

4 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

SITE ID

COMMON NAME

PM2.5 PM2.5 PM2.5

PM10 Acid PAMS

Carb- Meteoro- Aethal-

COUNTY O3 CO FRM Cont. Spec. NO NOx NO2 NOy SO2 TRS Pb PM10 Cont. Rain VOC VOC SVOC onyls logy ometer Cr6 Metals

Atlanta MSA 130630091 130670003

Georgia DOT

Clayton

S

National Guard

Cobb S

S

130670004 Macland Aquatic Center

Cobb

S

130770002

Univ. of West GA

Coweta S

S

NR

130850001

GA Forestry Dawson S

G

NR NR NR NR

NR

130890002

South DeKalb

DeKalb S/P S/P S

S

T S/P S/P S/P S/P

P

N N

P/N

P

N

N

N

130890003

DMRC

DeKalb

S

130892001 130893001

Police Dept.

DeKalb

S

Tucker

DeKalb

S NR

130970003

Beulah Pump Station Douglas

S

130970004

W. Strickland St. Douglas S

131130001

Georgia DOT

Fayette S

NR

131210001

County Health Dept

Fulton

S

131210020

Utoy Creek

Fulton

NR NR

NR

NR

131210032

E. Rivers School

Fulton

S

S

131210048

Georgia Tech

Fulton

S

SS S

S

S

131210055

Confederate Ave.

Fulton S

S

S

131210099

Roswell Road

Fulton

S

131350002

Gwinnett Tech Gwinnett S

S

S

131510002

County Extension

Henry S

S

132230003

Yorkville Paulding S/P S/P S

S

S/P S/P S/P

P NR NR

P

NR

132470001

Monastery Rockdale S/P

S/P S/P S/P

P

P

132550002 UGA Exp. Station-Griffin Spalding

S

132970001

Fish Hatchery

Walton

S

Chattanooga Tennessee-Georgia MSA

132950002

Co. Health Dept.

Walker

S

S

X

Not In An MSA

130090001

Baldwin Co. Airport Baldwin

S/M

NR NR

NR

130550001

Fish Hatchery Chattooga S

130690002 General Coffee State Park

Coffee

X

NR NR

NR

132611001

Union High

Sumter S

132810001

Lake Burton

Towns

G

133030001

Co. Health Dept. Washington

S

S

133190001

Police Dept. Wilkinson

S

Monitoring Types: S=SLAMS; P=PAMS; M=SPM; X=Supplemental Speciation; T=STN; N=NATTS; NR=Non-Regulatory; G=General Information

Table 2: 2007 Georgia Air Monitoring Network

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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, poisonous gas that is a by-product of the incomplete burning of fuels. The primary source of CO pollution in most large urban areas, including Metro Atlanta, is the vehicle, which contributes approximately 60% of CO emissions nationwide. Other sources include fires, industrial processes, cigarettes, and other sources of incomplete burning in the indoor environment (Figure 2). Higher concentrations of ambient CO may be present during the colder months of the year. In cool weather, weather patterns called inversion layers occur more frequently. These inversions trap pollutants near the surface.

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 length of exposure. At the levels usually found in ambient air, CO primarily affects people with cardiovascular disease.

The Clean Air Act (CAA) requires that Metropolitan Statistical Areas (MSAs) with a population greater than 500,000, as determined by the last census (2000), have at least two CO State and Local Air Monitoring Stations (SLAMS). In Georgia, only the Atlanta MSA meets the population requirement. Currently, the SLAMS site is located at Roswell Road (Figure 3). 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 substitution for a second SLAMS monitor, high sensitivity CO monitors have been installed at the Yorkville and South DeKalb sites. The purpose of these monitors is to detect very small concentrations of CO in order to gain a more complete understanding of the background levels of CO and its role in atmospheric chemistry.

Figure 2: Common Sources of Carbon Monoxide (CO)
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Figure 3: Carbon Monoxide Site Monitoring Map
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HEALTH IMPACTS Health effects of CO include weakening the contractions of the heart, which reduces blood flow to various parts of the body, decreasing the oxygen available to the body. In a healthy person, this effect significantly reduces the ability to perform physical activities. In persons with chronic heart disease, these effects 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 function, visual acuity, and the alertness of healthy individuals, even at relatively low concentrations.

MEASUREMENT TECHNIQUES CO is monitored using specialized analyzers made for that specific purpose. The analyzers continuously measure the concentration of CO in ambient air using the non-dispersive infrared analysis and gas filter correlation methods.

ATTAINMENT DESIGNATION Data collected from the continuous monitors is used to determine compliance with the Clean Air Act (CAA) 8-hour and 1-hour standard for CO. This 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. 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 this topic, see Appendix A.

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OXIDES OF NITROGEN (NO, NO2, NOx and NOy)

GENERAL INFORMATION Oxides of Nitrogen (see Table 3) 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 more intensely than their direct health impacts would imply; they are precursors of (and alternately by-products of) ozone formation. The many forms of oxides of nitrogen in the atmosphere are the reason that they are sometimes referred to using the generic terms NOx or NOy.
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 will attach itself to molecular oxygen (O2) creating an ozone (O3) molecule. This is the origin of all ground level ozone. Daytime levels of NO2 and N2O5 are low but their concentration rises rapidly in overnight. When the sun rises again in the morning, they are converted back to NO and ozone. 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.

Abbreviation NO
NO2
HNO3 PAN
NOx NOy

Full Name

Creation Processes

Elimination Processes

Nitrous Oxide

Result of ozone

Reacts with ozone to

photochemistry High-temperature

form NO2 and oxygen

combustion

Nitrogen Dioxide

High-temperature

Reacts with oxygen in

combustion

strong sun to form

Reaction of NO and

ozone plus NO

ozone

"Washes out" in rain

Nitric Acid

NO2 + H2O

"Washes out" in rain

Peroxyacetyl Nitrate Oxidation of hydrocarbons in

Slow devolution to NO2

sunlight

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 power plants. Home heaters and gas stoves 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. NO2 and sulfur dioxide (SO2) can react with other substances in the atmosphere to form acidic

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products that can be deposited in rain, fog, snow, or as particle pollution. Nitrate particles and NO2 can block the transmission of light, reducing visibility.

HEALTH IMPACTS Respiratory problems develop when individuals are exposed to high levels of NO2 for short durations (less than three hours). Asthmatics are especially sensitive to NO2. Changes in airway responsiveness have been observed in some studies of exercising asthmatics exposed to relatively low levels of NO2. Studies also indicate a relationship between indoor NO2 exposures and increased respiratory illness rates in young children, but definitive results are still lacking. Many animal studies suggest that NO2 impairs respiratory defense mechanisms and increases susceptibility to infection.

Several studies 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, and in particular NO2, are monitored using specialized analyzers made for that specific purpose. The analyzers continuously measure the concentration of oxides of nitrogen in ambient air using the ozone-phase chemiluminescent method. 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. As such 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. Atlanta is the only urban area in Georgia that meets that population requirement. Atlanta metro area has four NO2 sites. They are located at the South DeKalb, Georgia Tech, Conyers, and Yorkville sites. The complete oxides of nitrogen monitoring network, including NOx and NOy monitor locations, can be found in Figure 4.

ATTAINMENT DESIGNATION Data collected from the continuous monitors is used to determine compliance with the NAAQS primary and secondary annual standards for NO2. This standard requires that a site's annual average concentration exceed 0.053 ppm no more than an average of once a year over a three-year period. The Atlanta MSA is in attainment of the NO2 standard. For additional summary data on this topic, see Appendix A.

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Figure 4: Oxides of Nitrogen Monitoring Site Map
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SULFUR DIOXIDE (SO2)

GENERAL INFORMATION Sulfur dioxide (SO2) is a colorless reactive gas that is formed by burning of sulfur-containing material, such as coal, or by processing sulfur-containing ores. It is odorless at low concentrations, but pungent at very high concentrations. It can be oxidized in the atmosphere into sulfuric acid. When
sulfur-bearing fuel is burned or ores that contain sulfur are processed, the sulfur is oxidized to form SO2, which 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 and lead to acidic deposition. SO2 can also be a precursor for sulfate particles. Major sources of SO2 are fossil fuel-burning power plants and industrial boilers.

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 lead to increased mortality, especially if elevated levels of particulate matter (PM) are present. Groups that appear most sensitive to the effects of SO2 are asthmatics, people with hyperactive airways, and individuals with chronic obstructive lung or cardiovascular disease. Elderly people and children are also likely to be sensitive to SO2.

Effects of short-term peak exposures 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 PM and SO2 levels have a higher incidence of respiratory illnesses and symptoms than people living in areas without such a combination of pollutants. Figure 5 shows the locations of the Georgia SO2 monitoring stations for 2007.

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 network consists of instruments using a pulsed UV fluorescence technique. In Brunswick, a variation of this instrument is configured to monitor for total reduced sulfur (TRS), which monitors for other sulfur-bearing compounds such as hydrogen sulfide.

ATTAINMENT DESIGNATION To determine if an SO2 monitor is in attainment, an annual average, a 24-hour average, and a 3-hour average are evaluated. The data 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, an SO2 site must have an annual mean less than 0.03 parts per million (ppm), no more than one 24-hour average exceeding 0.14 ppm, and no more than one 3-hour average exceeding 0.50 ppm. All of Georgia is in attainment of the sulfur dioxide standard. For additional summary data on this topic, see Appendix A.

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Figure 5: Sulfur Dioxide Monitoring Site Map
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OZONE (O3)

Section: Chemical Monitoring Activities

GENERAL INFORMATION Ground level ozone, unlike the other gaseous air pollutants previously discussed, is not a primary pollutant. This means that ozone is not directly emitted by any sources, mobile or stationary. Ozone forms through a complex series of chemical reactions, which take place in the presence of strong sunlight (photochemical reactions). For these reactions to take place, certain ingredients (precursors) must be available. Since the reactions must take place in the presence of strong sunlight, ozone concentrations have a strong diurnal pattern (Figure 6).

Concentration

0.1

0.09

0.08

0.07

0.06

0.05

0.04

0.03

0.02

0.01

0

0:00

2:00

4:00

6:00

8:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00

Hour

Figure 6: Typical Urban 1-Hour Ozone Diurnal Pattern
The precursors1 to ozone formation are oxides of nitrogen (NOx) and reactive organic substances (sometimes referred to as VOCs or hydrocarbons). Examples of such reactive organic substances include hydrocarbons found in automobile exhaust (like benzene and propane), vapors from cleaning solvents (like toluene), and biogenic emissions (like isoprene). Ozone is a colorless gas, but when mixed with particles and other pollutants, such as NO2, forms smog, a brownish, pungent mixture (see Figure 7 and Figure 8). This type of pollution first gained attention in the 1940's as Los Angeles photochemical "smog". Since then, photochemical smog has been observed frequently in many other cities. Figure 7: Demonstration of Ozone Formation
As indicated above, ozone is formed when its precursors come together in the presence of strong sunlight. This 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

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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sunlight, is controlled by what is known as the "limiting reactant." This limiting reactant can be thought of in terms of household baking. You can only bake cookies until you run out of any one of the ingredients you need. If you run out of flour, it doesn't matter how much milk and sugar you have on hand; you can't make any more cookies 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, so 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 there 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. But many of the fundamental lessons learned about smog formation in Los Angeles over many years of research have proven not to apply in the same way in Georgia.

Figure 8: Ozone Formation Process
At the start of air quality control implementation in Georgia, the then-standard 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 trees naturally emit 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.
Air quality science had not, and still has not, had time to fully catch up with this discovery. The control technologies that reduce hydrocarbon emissions are generally not effective on oxides of nitrogen, so a whole new set of control technologies had to be developed. This area has been in some ways unable to take full advantage of the technologies developed for Los Angeles, then, because those technologies were not suited to local conditions. With respect to reducing emissions from automobile engines, for example, the addition of relatively simple and inexpensive catalytic converters to existing engine designs was a great leap forward in reducing hydrocarbon emissions. Catalytic converters have been used with great success since the early 1970s. Thus far, emissions of oxides of nitrogen have proven more difficult to control than hydrocarbon emissions, especially given that the control measures have not had forty years to mature. Research on the topic continues, and new emissions control equipment is always under development. For example, where catalytic converters could be added to existing engine designs to greatly reduce hydrocarbon emissions, solutions for reducing
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emissions of oxides of nitrogen have generally required far more reengineering of the engines themselves. There is no easy "bolt on" solution.

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. Many urban areas experience high levels of ground level ozone during the summer months. We also see high ozone levels in rural and mountainous areas. This is often caused by ozone and/or its precursors being transported by wind for many hundreds of miles.
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 chloroflourocarbons (CFC), which when released naturally migrate to the upper atmosphere. Once in the upper atmosphere, the 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.
The Georgia Environmental Protection Division monitors ground level ozone at 23 sites throughout the state (Figure 9).

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Figure 9: 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 6 to 8 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 Ozone is monitored using specialized commercial instruments made for that specific purpose. The analyzers continuously measure the concentration of ozone in ambient air using the U.V. photometric method and are EPA-approved for regulatory air monitoring programs. Data gained from the continuous monitors is used to determine compliance with the NAAQS 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 metro Atlanta ozone network includes eleven monitors located in ten counties.

In July 1997 the US EPA issued a new 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 (0.085 ppm with the EPA rounding convention) averaged over three years (see Table 1; 62 FR 38894, July 18, 1997). Areas EPA has declared in attainment of 1-hour standard are immediately exempt from that standard, but thereafter are subject to the 8-hour standard. In the summer of 2005, metro Atlanta was declared in attainment of the 1hour standard. As of the printing of this report, then, only the 8-hour ozone standard is applicable in Georgia.

The Atlanta ozone nonattainment area currently consists of Bartow, Cherokee, Clayton, Cobb, Coweta, DeKalb, Douglas, Fayette, Forsyth, Fulton, Gwinnett, Henry, Paulding, Rockdale, Barrow, Carroll, Hall, Newton, Spalding, and Walton Counties. All other MSA's are currently in attainment. Catoosa County is party of the Chattanooga Earl Action Compact area. Figure 10, on the next page, shows the boundaries of these nonattainment areas.

A number of activities to aid in controlling the precursors to ozone formation have been implemented. As new areas are declared in nonattainment, these control measures may be expanded to include them. These activities could include a strict vehicle inspection program, controls on stationary emission sources, and the establishment of a voluntary mobile emissions reduction program. An example of such a program in metro Atlanta 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) 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

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also done for the Macon area. 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 our website at http://www.georgiaair.org/amp. For a more detailed discussion concerning the CAC, see the section titled "Outreach and Education".

Figure 10: Georgia's 8-Hour Ozone Nonattainment Area Map
Figure 11 shows how past air quality would relate to the new standard and how current air quality relates to the old standard. This chart was produced by comparing measurement data against both ambient standards. This demonstrates the relative strictness of each standard and shows how our air quality has changed over time. Despite a great deal of fluctuation, over the course of the past twenty years we have seen a gradual reduction in the number of days exceeding either ozone standard. The trendline, produced by regression analysis, shows that the number of days that exceed the current 8hour ozone standard has fallen by about a half day each year over this time period. The most recent
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years of data show an upturn in the number of exceedance days. This is believed to be a result of natural variation in weather patterns, not a sign of a reversal of the long-term trend.

Exceedance Days

80

70

60

50

40

30

20

10

0

1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 Year

1-Hour

8-Hour

Trendline of 8-Hour

Figure 11: Metro Atlanta Ozone- Number of Violation Days per Year

Figure 12, on the next page, maps each Metro Atlanta ozone monitor that exceeded the 8-hour ozone standard in 2007, and also indicates the monthly breakdown of the exceedances.

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Figure 12: Metro Atlanta Ozone Exceedance Map
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The following map was taken from the EPA document "Latest Findings on National Air Quality: Status and Trends through 2006". It shows the fourth maximum reading for the 8-hour ozone readings across the United States. It is interesting to see the correlation of higher readings with the more populated areas across the United States. One can also see how Georgia's ozone readings compare with other states across the country.

(From EPA's "Latest Findings on National Air Quality: Status and Trends through 2006") Figure 13: Ozone Concentrations in ppm, 2006 (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 decreased to nearly zero by the late 1980s. Since then, the concentrations have hovered just above zero. Today, metals processing is the major source of lead emissions to the atmosphere. Other sources of lead emissions include the combustion of solid waste, coal, oils, emissions from iron and steel production, and the two remaining uses for lead in gasoline (aviation gasoline and racing gasoline).

Based on EPA guidance and the very small amounts of lead pollution remaining in Georgia, the lead monitoring network shrunk in 2005. Two lead monitoring sites in Columbus were closed. There are now two dedicated lead monitors remaining in Georgia for comparison to the NAAQS lead standard. One is in the Atlanta area for monitoring long-term trends in ambient lead levels. The other is in Columbus for industrial source monitoring, given the historical issues with lead pollution in the area.

The current criteria lead monitoring network is as indicated in Figure 14. For more information on criteria lead monitoring, see Appendix A. In addition to the criteria network sites, lead is also being monitored at 15 sites throughout Georgia as a trace metal in the Georgia Air Toxics Monitoring Network. The equipment used at those sites can detect far smaller concentrations. For additional summary data on lead as collected as an Air Toxics trace metal, see Appendix E.

HEALTH IMPACTS Exposure to lead occurs mainly through inhalation and ingestion of lead in food, water, soil, or dust. 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 the leadcontaining dust and dirt.

MEASUREMENT TECHNIQUES Measurement for ambient air lead concentrations is performed using a manual method, unlike measurements for ozone, SO2, NO2 and CO. Samples are collected on 8" x 10" pre-weighed fiberglass filters with a high-volume sampler for 24 hours. 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 lead sampler is used to determine compliance with the National Ambient Air Quality Standards for lead.

ATTAINMENT DESIGNATION The 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 standard, the concentration of lead in the air must have an arithmetic mean no higher than 1.5 micrograms per cubic meter averaged over a calendar quarter. (See Secs. 109, 301(a) Clean Air Act as amended (42 U.S.C. 7409, 7601(a)) [43 FR 46258, Oct. 5, 1978]. All of Georgia is in attainment of the lead standard. For additional summary data on this topic, see Appendix A.

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Figure 14: Lead Monitoring Site Map
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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 that particulate matter is formed. Primary particulate is emitted directly from a source, like a vehicle's tailpipe or a factory's smokestack. But 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. But 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.

Particulate pollution may also be categorized by size since there are different health impacts associated with the different sizes. The Ambient Air Monitoring Program monitors for two sizes of particles: PM10 (up to 10 microns in diameter) and PM2.5 (up to 2.5 microns in diameter). Both of these particles are very small in size. For example, Figure 15 shows how approximately ten (10) PM10 particles can fit on a cross section of a human hair, and approximately thirty (30) PM2.5 particles would fit on a cross section of a hair.

Maps of each of the

particulate

matter

networks (PM10, PM2.5

federal reference method,

PM2.5 continuous, and

PM2.5 speciation) are

included in the following

subsections that discuss

particulate matter.

Figure 15: Analogy of Particulate Matter Size to Human Hair

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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 of particular concern. 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.

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 most of the 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.

For a map of the PM10 network, refer to Figure 16 on the next page.

HEALTH IMPACTS Marked increases in daily mortality have been statistically associated with very high 24-hour concentrations of PM10, with some increased risk of mortality at lower concentrations. Small increases in mortality appear to exist at even lower levels. Risks to sensitive individuals increase with consecutive, multi-day exposures to elevated PM10 concentrations. The research also indicates that aggravation of bronchitis occurs with elevated 24-hour PM10 levels, and small decreases in lung function take place when children are exposed to lower 24-hour peak PM10 levels. Lung function impairment lasts for 2-3 weeks following exposure to PM10.

27 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Figure 16: PM10 Monitoring Site Map
28 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

MEASUREMENT TECHNIQUES The Georgia PM10 monitoring network consists of two types of monitors. The first is an event monitor in which samples are collected for 24 hours on a quartz microfiber filter. A specialized sample-sorting device is used so that the filter collects only particles 10 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 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. Because of the need for manual filter loading and unloading, shipping back to the laboratory, and so forth, there is significant time lag between taking the measurement and obtaining data. The other monitor is fundamentally similar, but has been greatly modernized. It draws particle-laden air through a filter and analyzes how the mass of the filter changes on an hourly or nearly continuous basis. This monitor gives much more information about how PM10 concentrations vary over time, is less labor-intensive, and produces results almost instantly.

ATTAINMENT DESIGNATION The primary and secondary standards for PM10 are the same. In order for an area to be considered in compliance with the standard, the 99th percentile 24-hour concentration is less than or equal to 150 micrograms per cubic meter [62 FR 38711, July 18, 1997]. For example, if 100 PM10 samples were taken over the course of the year and one sample exceeded 150 micrograms per cubic meter (g/m3), then the area would meet the standard. If two or more samples were over 150 micrograms per cubic meter, then the area would not be in attainment of the standard. There was also an annual average standard for PM10 until December 17, 2006. EPA revoked the standard because of a lack of evidence of chronic health effects resulting from long-term exposure to moderate levels of PM10.
The Albany site is currently the only site that is above the standard for PM10. The Georgia EPD believes that this site was affected by the Okefenokee Swamp wildfire that took place in the spring of 2007. For the previous five years, the Albany site's second highest annual PM10 averages ranged from 41 to 51 g/m3, consequently the rise in level to 187 g/m3 was thought to be exceptional (refer to Figure 18 on page 31). Therefore, Georgia EPD has requested from EPA to have the higher readings removed from the data set. If these numbers were removed from the dataset, the Albany site would be below the standard. The other areas of Georgia are currently in attainment of the PM10 standard. For additional summary data on this topic, see Appendix A.

29 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

40.0

35.0

30.0

Average Concentration (g/m3)

25.0

20.0

15.0

10.0

5.0

0.0 2002

2003

Albany Metro Savannah*

Augusta Rome

* Average includes one site for 2007

2004
Brunswick Rossville

2005 Year
Columbus Sandersville

2006
Macon Summerville

2007 Metro Atlanta

Figure 17: PM10 Annual Arithmetic Mean Chart

Figure 17 shows how the metro areas in Georgia stand relative to the annual average PM10 standard. On an annual basis, PM10 levels in Georgia are relatively low. Most inland areas have similar annual average concentrations, and coastal areas typically have less PM10 than inland areas. Longer-term PM10 data generally suggest a slow decrease in PM10 concentrations overall.

Figure 18 shows how the same areas compare 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 2nd highest 24-hour average for each site or metro area. Although there is a
great deal of variation from year to year at any given site, the statewide average is relatively stable. It
is believed that concentrations of PM10 in 2007 were above normal due to excessive smoke from the Okeefenokee Swamp wildfire.

30 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Statewide (avg)

Sandersville

Rossville

Augusta

Columbus

Brunswick

Site

Rome

Albany

Metro Atlanta

Summerville

Savannah Macon

150 g/m3 limit

0

20

40

60

80

100

120

140

160

180

200

Second Highest 24-Hour PM10 Concentration (g/m3)

2007 2006 2005 2004 2003 2002

Figure 18: PM10 24-Hour Design Values

31 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

PM2.5

Particulate matter including PM2.5 consists of the solid particles and liquid droplets found in the air. Individually, these particles and droplets are invisible to the naked eye. Collectively, however, they can appear as clouds or a fog-like haze.

Particulate matter less than or equal to 2.5 microns in diameter is referred to as "fine" particles. In comparison, a human hair is 70-100 microns in diameter. Fine particles are produced by many different sources, including industrial combustion, residential combustion, and vehicle exhaust, so their composition varies widely. Fine particles can also be formed when combustion gases are chemically transformed into particles. Considerable effort is being undertaken by Georgia to analyze the fine PM2.5 particles for the chemical constituents that make up the particles, so pollution control efforts can be focused in areas that create the greatest reductions. We currently monitor fifty-three (53) particle species, which include gold, sulfate, lead, arsenic, and silicon.

HEALTH IMPACTS Fine particles are of health concern because they can penetrate into the sensitive regions of the respiratory tract and they are linked to the most serious health effects. They can cause persistent coughs, phlegm, wheezing, and physical discomfort.

Several recently published community health studies indicate that significant respiratory and cardiovascular-related problems are associated with exposure to particle levels well below the existing particulate matter standards. These negative effects 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 illness and reduce life span. Some data also suggests that fine particles can pass through lung tissues and into the bloodstream. Children, the elderly, and individuals with cardiovascular disease or lung diseases such as emphysema and asthma are especially vulnerable.

Much new evidence of these health impacts is discussed in EPA's "Air Quality Criteria for Fine Particulate Matter" document. It indicates that fine particles are also thought to enhance the delivery of other pollutants and allergens deep into lung tissue, where their effects are more pronounced. The cancer risk alone of long-term exposure to elevated fine particle concentrations has been estimated to be similar to that of the additional risk to a non-smoker of living with a smoker. Early estimates of the impact of long-term exposure to elevated fine particle concentrations indicate an average life span reduction of one to two years (U.S. EPA, 2004a). Taking this information and that from many other studies into account, EPA strengthened the 24-hour PM2.5 standard effective December 17, 2006.

Fine particles can soil man-made materials, making them look sooty and speeding their deterioration. They also impair visibility and are an important contributor to haze, especially in humid conditions. The visibility effect is roughly doubled at 85% relative humidity as compared to humidities under 60% (U.S. EPA, 2004a).

MEASUREMENT TECHNIQUES Measurement techniques for PM2.5 are very similar to those for PM10. The official reference method requires that samples are collected on Teflon filters with a PM2.5 sampler for 24 hours. A specialized sample-sorting device is used so that the filter collects 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 of PM2.5 particles collected. That mass, divided by the total volume of air sampled, corresponds to the mass concentration of the particles in the air for that 24-hour period. Only these reference method filters may be used for attainment determinations. But because of the delay in picking up each filter, shipping it to the laboratory, and weighing each filter, weeks pass before the results are known. As such this method is very accurate but is useless when trying to decide if it is safe to go jogging or to let children play outside.

32 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

As with PM10, continuous samplers for PM2.5 are also used to report "real time" data to support programs like air quality forecasting and public information efforts like the Air Quality Index (AQI). These instruments produce hourly averaged data that is available almost immediately after the end of each hour. By having information available so quickly, the public can make informed decisions about their levels of physical activity. It is important to note that the EPA does not certify these continuous samplers as being fully equivalent to the reference method when sampling PM2.5. This means that data from these continuous samplers cannot be used for determining if an area is in attainment of the NAAQS; only data from the reference method may be used. However, evaluation of another type of continuous PM2.5 sampler that has federal equivalency method is underway. It is possible that this type of continuous PM2.5 sampler could be used for attainment purposes in the future. Continuous PM2.5 data is reported every hour on the Ambient Air Monitoring web page located at http://www.air.dnr.state.ga.us/amp.

Figure 19 shows the location of Georgia's PM2.5 FRM monitors and Figure 20 shows the location of PM2.5 continuous and speciation monitors.

33 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Figure 19: PM2.5 Federal Reference Method Monitoring Site Map
34 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Figure 20: PM2.5 Monitoring Site Map, Continuous and Speciation Monitors
35 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

ATTAINMENT DESIGNATION For an area to be in attainment of the national primary and secondary annual ambient air PM2.5 standard, it must have an annual arithmetic mean concentration of less than or equal to 15.0 micrograms per cubic meter. In addition, there was a 24-hour primary and secondary standard that requires that the 98th percentile 24-hour concentration be less than or equal to 65 micrograms per cubic meter [62 FR 38711, July 18, 1997]. This 24-hour limit was reduced to a 35-microgram limit effective December 17, 2006. All sample analyses used for determining compliance with the standards must use a reference method based on information in 40 CFR Appendix L or an equivalent method as designated in accordance with Part 53.

Because the PM2.5 standard required three years of monitoring data before attainment or nonattainment could be determined, Georgia's attainment status was not determined until late 2004. As was expected, large portions of the United States were found to be in nonattainment of the standard when EPA made its initial attainment determinations. Based on the three years of data, EPA officially declared several areas of Georgia in nonattainment of the standard. Walker and Catoosa Counties are included in the metro Chattanooga nonattainment area. All of Bibb County and portions of Monroe County have been included in the Macon nonattainment area. Floyd County itself has been declared a nonattainment area. Finally, the metro Atlanta nonattainment area has been 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 21 illustrates the boundaries of Georgia's PM2.5 nonattainment areas.

36 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Figure 21: Georgia's PM2.5 Nonattainment Area Map
The PM2.5 FRM data for 2007 is currently under review. When this data is completely assessed, this
report will be updated.
Figure 22, on the next page, shows maps that were taken from the EPA document "Latest Findings on National Air Quality: Status and Trends through 2006". The first map shows PM2.5 annual average concentrations across the United States for 2006, and the second map shows the 24-hour average concentrations. It appears that for Georgia, the annual average concentrations were in the 0-12 g/m3 range up to the 15.1-18 g/m3 range. The 24-hour average concentrations were primarily in the 16-35 g/m3 range across Georgia.
37 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report Annual Concentrations

Section: Chemical Monitoring Activities

Daily Concentrations

(From EPA's "Latest Findings on National Air Quality: Status and Trends through 2006")
Figure 22: PM2.5 Annual and 24-Hour Concentrations across the United States, 2006
38 Georgia Department of Natural Resources
Environmental Protection Division

2007 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. Refer to Figure 20 for a map of Georgia's PM2.5 Speciation monitors. Attempts to control the concentration of fine particulate matter are now a national priority through 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 particlulate matter has varying health effects depending of 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, their size varies. 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.

Georgia currently monitors fifty-three (53) species, which include gold, sulfate, lead, arsenic, and silicon. However, there are only approximately six (6) chemicals that are detected frequently (the chemical elements typical of the Earth's crust are grouped together as "crustal"). Of these, sulfate and organic carbon are detected in the highest concentrations. Figure 23, Figure 24, Figure 25, Figure 26, and Figure 27 illustrate the average concentrations of these six chemicals from 2003 to 2007. Below the figures is a listing of the most significant chemical constituents of fine particulate matter.

6

5

Concentration (ug/m3)

4

3

2

1

0 Ammonium Ion

Elemental Carbon

Organic Carbon

Sulfate Species

Nitrate

Crustal

Macon Savannah Athens Douglas SDK Rome Columbus Augusta

Figure 23: 2003 PM2.5 Speciation
39 Georgia Department of Natural Resources
Environmental Protection Division

Other

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

6

5

Concentration (ug/m3)

4

3

2

1

0 Ammonium Ion

Elemental Carbon

Organic Carbon

Macon Savannah Athens

Sulfate
Species Douglas SDK

Nitrate

Crustal

Rome Columbus Augusta

Figure 24: 2004 PM2.5 Speciation

Other

6

5

Concentration (ug/m3)

4

3

2

1

0 Ammonium Ion

Elemental Organic Carbon Carbon

Sulfate Species

Nitrate

Crustal

Macon Athens Douglas Atlanta Rome Columbus Augusta Rossville

Other

Figure 25: 2005 PM2.5 Speciation
40 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

7

6

5

Concentration (ug/m3)

4

3

2

1

0 Ammonium Ion

Elemental Organic Carbon Carbon

Sulfate Species

Macon Athens Douglas Atlanta Rome

Nitrate

Crustal

Columbus Augusta Rossville

Figure 26: 2006 PM2.5 Speciation

Other

Concentration (ug/m3)

9

8

7

6

5

4

3

2

1

0 Ammonium Ion

Elemental Carbon

Organic Carbon

Sulfate Species

Nitrate

Crustal

Macon Athens Douglas Atlanta Rome Columbus Augusta Rossville

Figure 27: 2007 PM2.5 Speciation
41 Georgia Department of Natural Resources
Environmental Protection Division

Other

2007 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: are 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 will help scientists and regulators track the progress and effectiveness of newly implemented pollution controls. The data will also improve scientific understanding of the relationship between particle composition, visibility impairment, and adverse human health effects.

Monitoring for the chemical speciation of fine particlulate matter began late in 2001, therefore, limited data is available. As the data set becomes more robust, other conclusions may be drawn. However, some general observations can already be made. The concentrations of sulfate and organic carbon are less at the General Coffee site than at the remaining seven (7) sites. This is expected since the sulfate and organic carbon fractions are mainly caused by human activities. The Douglas-General Coffee site is considered a rural background site and will be used in future comparisons between rural and urban areas.

Figure 28, Figure 29, Figure 30, Figure 31, Figure 32, and Figure 33 present a different view of the same data to facilitate visualization of trends. Note that because each chemical component presented appears in varying concentrations, each chart uses a different scale for the mass concentrations.

42 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Concentratin (ug/m3)

2 1.8 1.6 1.4 1.2
1 0.8 0.6 0.4 0.2
0 Macon Savannah Athens

Douglas

Atlanta Site

Rome Columbus Augusta

2003 2004 2005 2006 2007

Rossville

Figure 28: PM2.5 Speciation, Trends in Ammonium Concentrations

1.4

1.2

1

Concentration (ug/m3)

0.8

0.6

0.4

0.2

0 Macon Savannah Athens

Douglas

Atlanta Site

Rome Columbus Augusta Rossville

2003 2004 2005 2006 2007

Figure 29: PM2.5 Speciation, Trends in Elemental Carbon Concentrations

43 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Concentration (ug/m3)

9

8

7

6

5

4

3

2

1

0 Macon Savannah Athens

Douglas

Atlanta

Rome Columbus Augusta Rossville

Site

2003 2004 2005 2006 2007

Figure 30: PM2.5 Speciation, Trends in Organic Carbon Concentrations

6

5

Concentration (ug/m3)

4

3

2

1

0 Macon Savannah Athens

Douglas

Atlanta Site

Rome Columbus Augusta Rossville

2003 2004 2005 2006 2007

Figure 31: PM2.5 Speciation, Trends in Sulfate Concentrations

44 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

1.4

1.2

1

Concentration (ug/m3)

0.8

0.6

0.4

0.2

0 Macon Savannah Athens

Douglas

Atlanta Site

Rome Columbus Augusta Rossville

2003 2004 2005 2006 2007

Figure 32: PM2.5 Speciation, Trends in Nitrate Concentrations

Concentration (g/m3)

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0 Macon Savannah Athens

General Coffee

Atlanta

Rome Columbus Augusta Rossville

Site 2003 2004 2005 2006 2007

Figure 33: PM2.5 Speciation, Trends in Crustal Matter Concentrations

45 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Ammonium Ion concentrations are relatively even statewide, ignoring some unexplained high and low averages observed during 2005.

The Atlanta and Macon areas have the highest elemental carbon concentrations, which is no surprise given their location on major Interstate trucking corridors. Cities with less heavy vehicle traffic have lower concentrations, and the rural site (General Coffee) has the least elemental carbon.

Organic carbon concentrations are also relatively consistent throughout the state, although rural areas like General Coffee are slightly lower. Organic carbon concentrations are much higher than typical ammonium ion or elemental carbon concentrations, which means that organic carbon is a relatively large contributor to the total PM2.5 mass concentrations.

Sulfate concentrations can be described much the same as organic carbon concentrations. They 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 PM2.5mass concentrations.
Nitrate concentrations are relatively small, but are less consistent from site to site. However there is an increase in concentrations at Athens and Rossville. Their concentrations do seem to track somewhat with NOx emission patterns. The high concentrations at the Athens site could be attributed to industry in the area.

Crustal matter concentrations are relatively low and consistent in most areas. Rome and Macon have in some years recorded unexpectedly high crustal matter concentrations. This may be a sign of poor dust control at agricultural, construction, or mining operations in those areas.

For additional PM2.5 speciation data, see Appendix B.

MEASUREMENT TECHNIQUES Particle speciation measurements require the use of a wide variety of 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. There are no ambient air quality standards regarding the speciation of particles.

46 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report
ACID PRECIPITATION

Section: Chemical Monitoring Activities

In 2007, acid precipitation was monitored in four counties. The samples were collected weekly and were weighed and analyzed for acidity, conductivity, and selected compounds. There are no national or state standards for acid precipitation, but it is generally desirable for rain to have a relatively neutral pH. However, in many regions of industrialized nations, rainfall absorbs air emissions that make it acidic, with lower pH numbers. Most of the culprits of this acidification are sulfur and nitrogen compounds, and the result is rain that contains excess acidity from sulfuric acid and nitric acid. The excess acidity in the rain causes damage to buildings and vehicles, and can acidify ponds and small lakes to the point of killing off all life in them. Figure 34 shows a diagram of the acid rain deposition process.

Figure 34: Process of Acid Rain Deposition Georgia's Acid Rain monitoring network is shown in Figure 35, on the following page.
47 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Figure 35: Acid Rain Monitoring Site Map
48 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Figure 36 shows an analysis of statewide average data back to 1982. It indicates a small but significant trend toward pH neutrality. The rate of this increase is a pH gain of 0.007 per year over the period shown.

Average pH

5.9 5.7 5.5 5.3 5.1 4.9 4.7 4.5 4.3 4.1
1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 Monitoring Year

pH of Pristine Rain

Statewide Avg.

Trendline

Figure 36: Acid Rain Trends, Statewide

5.2

5

4.8

pH

4.6

4.4

4.2

4 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Year

Dawsonville

Hiawassee

McDuffie

Summerville

Figure 37: Acid Rain Trends, by Location

49 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Analysis of the same data set for individual areas (Figure 37) shows that through the 1990s Summerville was the most acidic and McDuffie the most neutral. In recent years, the difference between these areas has diminished and all of the sites have rainfall with roughly the same pH.

Figure 38 depicts a comparison between GA DNR acid rain monitoring sites and the National Atmospheric Deposition Program/National Trends Network (NADP) annual average pH readings for 2005 through 2007. As discussed above, Dawsonville, Hiawassee, McDuffie, and Summerville are in the DNR network. The sites that are in the NADP network are in Bellville, Chula, Okefenokee, and Sapelo Island. It appears that the annual averages for the NADP sites are slightly less acidic. These NADP sites are south of the Fall Line. The less acidic rain in the NADP monitoring areas may be related to South Georgia's greater proximity to sea breezes, which carry sodium ions that could affect the pH of rain in those areas.

Average pH Level

5

4.9

4.8

4.7

4.6

4.5

4.4

4.3 Dawsonville (DNR)

Hiawassee (DNR)

McDuffie (DNR) Summerville (DNR)

Bellville (NADP)

Site

Chula

(NADP)

Okefenokee

(NADP) Sapelo

Island

(NADP)

2005 2006 2007

Figure 38: Comparison of DNR and NADP Annual Acid Rain Averages

50 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Chemical Monitoring Activities

Dots show monitoring locations. (Data source: National Atmospheric Deposition Program, http://nadp.sws.uiuc.edu/) From EPA's "Latest Findings on National Air Quality: Status and Trends through 2006"
Figure 39: Three-year Average Precipitation of Sulfate Concentrations (SO42-) in 1989-1991 and 2004-2006
Figure 39 shows the different levels of sulfate found in precipitation across the United States from a period of 1989 to 1991 compared to a period of 2004 to 2006. Sulfate is a contributor to acid rain levels. The levels of sulfate appear to have dropped from the first timeframe to the next timeframe by about 30% in most areas of the East. This reduction is more than likely due to a reduction in SO2 and NOX emissions from industrial power plants.
51 Georgia Department of Natural Resources
Environmental Protection Division

2007 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 smog. The understanding of the chemical processes in ozone formation and the specific understanding of the atmospheric mixture in nonattainment areas nationwide became apparently essential to EPA. 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 monitoring of meteorological parameters. These chemicals would be monitored at Photochemical Assessment Monitoring Stations (PAMS).
According to EPA, 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 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. 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. Until the end of 2006, this was the set up 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. The PAMS network as it was set up for the 2007 monitoring year can be seen in Figure 40.

52 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

Figure 40: PAMS Monitoring Site Map
53 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

An analysis of the PAMS data finds that the top ten volatile organic compounds (VOCs) for all sites contained the following species consistently across the years: isoprene, m/p xylene, toluene, propane, ethane, isopentane or isopentane/cyclopentane, n-butane and n-pentane. Propane, ethane, isopentane, n-butane, and n-pentane have a limited reactivity for ozone formation and therefore were the most prevalent of the volatile organic compounds measured. However, when the characterization of the top ten species is based upon contributions to ozone formation potential, we find that the list is slightly different. Isoprene, the tracer for VOC emissions from vegetation, is by far the largest contributor to ozone formation at every site.

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, the most abundant species in urban air, m/p xylene, and isopentane also are emitted by solvent use and refinery activities.

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. Toluene reaches the air from a variety of sources such as combustion of fossil fuels and evaporative emissions. It has a substituted benzene ring possessing modest atmospheric reactivity. This hydrocarbon is in motor vehicle fuel and is also used as a common solvent in many products such as paint.
35

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0 JanuaryM-0a3rch-0M3 ay-S0J3euplyte-0mN3boevre-m03bJear-n0u3aryM-0a4rch-0M4 ay-S0J4eupltye-0mN4boevre-m04bJear-n0u4aryM-0a5rch-0M5 ay-S0J5eupltye-0mN5boevre-m05bJear-n0u5aryM-0a6rch-0M6 ay-S0J6eupltye-0mN6boevre-m06bJear-n0u6aryM-0a7rch-0M7 ay-S0J7eupltye-0mN7boevre-m07ber-07
Date

South DeKalb

Yorkville

Conyers

Figure 41: Isoprene Yearly Profile, 2003-2007
Figure 41 and Figure 42 compare the seasonal occurrence of these two compounds from 2003 to 2007. They are a combination of the 6-day, 24-hour data from the three PAMS sites, and
54 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

concentrations are given in parts per billion Carbon (ppbC). Evidence of isoprene's natural origin is shown in Figure 41, where the ambient concentration is essentially non-existent from November to May. All three sites exhibit the seasonal cycle, with an occasional spike outside the consistent cycle. The site with the highest concentration of isoprene appears to vary year to year. With the Yorkville and Conyers sites being in a rural area, or semi-rural area, one would expect to see higher levels of isoprene. This has been true for most years. As part of the seasonal cycle, in 2003, Conyers had the highest concentration with 16 ppbC, in 2004 Yorkville had the highest with 17 ppbC, in 2005, South DeKalb had the highest with 18 ppbC, in 2006, Conyers had the highest concentration with 22 ppbC, and in 2007 Yorkville had the highest concentration with 35 ppbC. With the 2007 data, there appears to be a slight upward turn in the highest seasonal levels of isoprene data. However, since there are a limited number of years worth of data at this point, it would be hard to discern a distinguishable trend.

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JanuaryM-0a3rch-0M3 ay-0SJ3euplyte-0mN3boevre-0m3bJear-n0u3aryM-0a4rch-0M4 ay-0SJ4euplyte-0mN4boevre-0m4bJear-n0u4aryM-0a5rch-0M5 ay-0SJ5euplyte-0mN5boevre-0m5bJear-n0u5aryM-0a6rch-0M6 ay-0SJ6euplyte-0mN6boevre-0m6bJear-n0u6aryM-0a7rch-0M7 ay-0SJ7euplyte-0mN7boevre-0m7ber-07 Date

South DeKalb

Yorkville

Conyers

Figure 42: Toluene Yearly Profile, 2003-2007
The atmospheric levels of toluene are relatively constant throughout the year, suggesting a steady level of emissions year-round (Figure 42). There is an occasional spike in concentration, but no evident high or low pattern for the past five years. 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. Yorkville appears to have an upward swing throughout 2006, but the levels decline in 2007. As data is collected in the future, this site can be examined for a possible trend. The jaggedness of these graphs is an artifact of the sampling frequency.

55 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

The daily profile plots for toluene and isoprene are found in Figure 43. 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 slight drop in concentration occurs followed by a quick resumption in rise.

Concentration (ppbC)

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Toluene

Isoprene

Figure 43: Toluene & Isoprene, Typical Urban Daily Profile

56 Georgia Department of Natural Resources
Environmental Protection Division

2007 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. The majority of carbonyl compounds come from vehicle exhaust or 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 carbonyls 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 samples every six days throughout the year and every three hours throughout the summer. Savannah, Dawsonville, and Brunswick are part of the Air Toxics Network and sample every twelve days. For a map of monitoring locations, see Figure 44.

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; so can 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 the making of 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.

57 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

Figure 44: Carbonyls Monitoring Site Map
58 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

The 2007 average concentration (shown in micrograms per cubic meter) of all 3-hour samples of carbonyls collected during the summer months (June, July, and August) has been combined for a given hour and is shown in Figure 45 for the South DeKalb site. The early morning ambient concentrations are generally lower for all constituents. The concentrations appear to peak at the 12:00 hour for all the carbonyls components except benzaldehyde, which tends to peak at the 15:00 hour. There are a few noticeable changes when comparing the 2005 data through 2007. All of the concentrations seem to gradually increase year to year, except for acrolein. There were no detections of acrolein in 2006 or 2007 with the dinitrophenylhydrazine (DNPH) cartridge method (a different collection method discussed later in this section). This is down from about 1 to 4 detections per hour and an average concentration of about 0.57 g/m3 at each hour in 2005. Acetyladehyde, acetone, and formaldehyde continue to be the biggest contributors, following the same pattern of the averages increasing from the 6:00 to 9:00, and again from the 9:00 to 12:00 hours, then decreasing at the 15:00 hour.

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Formaldehyde Acetone Acetaldehyde Benzaldehyde Propionaldehyde Butyraldehyde
Acrolein

Figure 45: Average South DeKalb 3-Hour Carbonyls, June-August, 2005-2007

59 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

As can be seen in Figure 46, when the average concentration of all carbonyls is compared with the
total number of detections at each of the sampling sites, the carbonyl detections and concentrations
tend to track each other directly. It should be noted that the South DeKalb site collects data every six
days with the PAMS network, while Savannah, Dawsonville, and Brunswick collect data every twelve
days with the Air Toxics Network (discussed in next section). All else being equal, by taking twice as
many samples at those locations, one would normally expect to see twice as many detections. To
compare the data collected from 2005 to 2007, there are some noticeable changes. The Dawsonville site had a visible increase in concentration from 2006 to 2007, almost tripling from 7.7 g/m3 to 21.3 g/m3. The Brunswick site shows a lower average concentration from 2005 to 2006 (18.4 g/m3 to 10.5 g/m3), but remained the same from 2006 to 2007. Overall, the number of detections are
roughly the same from 2005 to 2007.

Total Average Concentration (ug/m3) Total Number of Detections

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S. DeKalb Name of Site

0 Brunswick

Concentration

Detects

2005 2006 2007 2005 2006 2007

Figure 46: Average 24-Hour Carbonyls Concentration and Number of Detects, by Site, 20052007
Figure 47 shows the seven species in the analyte group according to their statewide annual abundance, based on number of detections and average concentration. A gradient is evident from this graph, with formaldehyde as the most abundant carbonyl. For the most part, it appears that the number of detections track the average concentration. Acetaldehyde does not follow this pattern, however, having more detections compared to the concentration. For all the compounds, there appears to be a slight decrease from the 2005 to 2006 data, and then an increase from the 2006 to 2007 data. The proportion of each compound remained about the same throughout all three years of data, with the biggest contributors (formaldehyde, acetone, and acetaldehyde) remaining the same.

60 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

Total Average Concentration (g/m3) Total Number of Detections

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Figure 47: Average 24-Hour Carbonyls Concentration vs. Number of Detects, by Species, 20052007
Due to EPA research to improve acrolein sampling and analysis, a new method was developed using volatile organic compounds (VOCs) canister collection with gas chromatograph and mass spectroscopy (GC/MS). Georgia EPD began using the new method for NATTS and at the 15 air toxics sites (discussed in the next section) in July of 2007. In previous years, acrolein was sampled only with the method of a dinitrophenylhydrazine (DNPH) cartridge with high performance liquid chromatography (HPLC) analysis at five select sites. The DNPH/HPLC method was used on the data that is displayed in the three previous carbonyls graphs. With the canister collection and GC/MS analysis method and additional sampling locations, the number of acrolein detections drastically increased in 2007 (compare Figure 47 and Figure 48 on the next page). The total average concentration for all the sites was 9.656 g/m3, compared to an average concentration of 0.571 g/m3 in 2007 with the DNPH/HPLC method.
In Figure 48, on the next page, the average concentrations for the six month period from July through December ranged from 0.399 g/m3 at the Savannah site to 1.04 g/m3 at the Brunswick site (using half the detection limit for non-detected samples). This is over two times the difference between the lowest level of concentration to the highest level. This shows a variation of acrolein concentrations across the state. The number of detections seems to be mostly consistent across the state. Again, the South DeKalb site had more collection days, being on a 6-day schedule instead of a 12-day schedule like the other sites. When there is a full year of data in 2008, it may be possible to see more clearly how concentrations and detections would differ across the state. Acrolein may enter the environment as a result of combustion of trees and other plants, tobacco, gasoline, and oil. Additionally, it has a number of industrial uses as a chemical intermediate (ATSDR, 2005c). The potential for acrolein to cause health effects is not well understood. At very low concentrations, it is an upper respiratory irritant. At very high concentrations it may produce more serious damage to the lining of the upper respiratory tract and lungs (ATSDR, 2005c; U.S. EPA, 2003).

61 Georgia Department of Natural Resources
Environmental Protection Division

Total Average Concentration (ug/m 3)
Total Number of Detections

2007 Georgia Ambient Air Surveillance Report

Section: Photochemical Assessment Monitoring Stations

1.1

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AugustaBrunsGwiecnkeral Coffee ColumbuDsawsonvilleGainesville

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RomeSavannSaohuth DeKalbU* toy Creek ValdWosatarner Robins Yorkville

Concentration Detects 2007 2007

Figure 48: Acrolein Concentrations and Number of Detections, 2007
MEASUREMENT TECHNIQUES A number of methods are used to conduct the PAMS hydrocarbon portion of the analyses. Throughout the year, 24-hour integrated hydrocarbon samples are taken and analyzed in the EPD laboratory for 56 hydrocarbon compounds. A 24-hour integrated carbonyl sample is taken once every sixth day throughout the year and analyzed. During June, July, and August, four integrated threehour carbonyl samples are taken every third day. All analyses are conducted at the EPD Laboratory.
During June, July, and August, hydrocarbon samples are analyzed hourly on-site using a gas chromatography unit with a Flame Ionization Detector (FID). The gas chromatograph produces analyses of the ambient air for the same 56 hydrocarbons. Specific annual summaries for 2007 may be found in Appendix D.
The carbonyls are sampled with two types of methods. One type is an absorbent cartridge filled with dinitrophenylhydrazine (DNPH) coated silica that is attached to a pump to allow approximately 180 L of air to be sampled. The cartridge is analyzed using High Performance Liquid Chromatography. The other method is the canister sampler that is used for sampling volatile organic compounds. Acrolein is analyzed using this method. A SUMMA polished canister is evacuated to a near-perfect vacuum and attached to a sampler with a pump controlled by a timer. The canister is filled to greater than 10 psig. The canister is analyzed using a gas chromatograph with mass spectroscopy detection (GC/MS).
ATTAINMENT DESIGNATION There are no specific ambient air standards for the hydrocarbon and aldehyde species measured. PAMS measurements are performed to support the regulatory, analytical, and public health purposes of the program. By performing these measurements, we can better serve two major goals. First, by studying local atmospheric chemistry, we improve our ability to control the formation of secondary pollutants like ozone and particulate matter. Second, we are monitoring the concentration of pollutants (aside from the defined criteria air pollutants) expected to be harmful to human health, but are not well enough understood to be regulated. By making such data available, scientists who study human health as it relates to air quality can study how these pollutants may affect our health. When this understanding is further refined, their data can serve to guide policymakers toward making decisions that protect public health.
62 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report
AIR TOXICS MONITORING

Section: Air Toxics Monitoring

GENERAL INFORMATION The citizens of Georgia have demonstrated a long-term interest in the quality of Georgia's air. Since the 1970's, ambient ozone concentrations have been monitored in several communities throughout the state. As the state's population grew, more compounds have been monitored in ambient air as required by the Federal Clean Air Act. In 1993, the EPD began to monitor a number of compounds that have no established ambient air standard. The monitoring has been conducted under two efforts, the first being the previously discussed Photochemical Assessment Monitoring Station (PAMS) project, a federally mandated program for areas in serious, severe, or extreme non-attainment of the ozone standard. The second effort is the EPD-sponsored monitoring activities for ambient concentration of hazardous air pollutants (HAPs). That effort was undertaken since monitoring only criteria pollutants would not provide an adequate understanding of the quality of Georgia's air.
In 1994, the EPD conducted an intensive air quality study in Savannah (GADNR, 1996a). In 1996, the EPD conducted an intensive study in Glynn County as part of a multimedia event with EPA (GADNR, 1996b). These studies provided detailed pictures of the air quality in the communities, but the studies were not long-term studies and could not provide information on seasonal variation or trends. A reassessment of the toxic monitoring program occurred, and in 1996 the EPD embarked on establishing a statewide hazardous air pollutant-monitoring network. The network was not designed to monitor any one particular industry, but to provide information concerning trend, seasonal variation, and rural versus urban ambient concentration of air toxics. In order to evaluate the rural air quality, two background sites were proposed: one in North Georgia and one in South Georgia. The majority of the other sites were located in areas with documented emissions to the atmosphere of HAPs exceeding one million (1,000,000) pounds per year as indicated by the 1991 Toxic Release Inventory (GADNR, 1993).

After six years, by 2002, the Air Toxics Network (ATN) consisted of fourteen (14) sites statewide, including a collocated (where two sets of monitors sample side by side) site at Utoy Creek, monitoring for a common set of toxic compounds. From the list of 188 compounds identified by EPA as being HAPs, the toxic compounds include metals, volatile organic compounds, and semi-volatile organic compounds. In addition, three of the ATN sites (Brunswick, Dawsonville, and Savannah) monitor carbonyl compounds (as seen in the previous section).
In 2003, a National Air Toxics Trends site was added to the network at the South DeKalb site, bringing the total to fifteen (15) air toxics sites. The National Air Toxics Trends Station (NATTS) network was established in 2003 and is intended for long-term operation for the purpose of discerning national trends. The NATTS Network consisted of 23 sites, 18 urban and 7 rural, with two of the urban sites added in 2007. At the South DeKalb site, the same compounds are monitored as at the other air toxics sites, as well as hexavalent chromium, black carbon, and carbonyls.
All of these air toxic pollutants can have negative effects on human health, ranging from causing headaches, nausea, dizziness, cancer, birth defects, problems breathing, and other serious illnesses. These effects can vary depending on frequency, length of time, health of the person that is exposed, along with the toxicity of the compound. These air pollutants also affect the environment. Wildlife experiences symptoms similar to those in humans. Pollutants accumulate in the food chain. Many air pollutants can also be absorbed into waterways and have toxic effects on aquatic wildlife. Some of the substances tend to have only one critical effect, while others may have several. Some of the effects may occur after a short exposure and others appear after long-term exposure or many years after being exposed. Exposure is not only through direct inhalation of the pollutant, but also through the consumption of organisms such as fish that have absorbed the pollutant.

Air toxic compounds are released from many different sources, including mobile sources (such as vehicles), stationary industrial sources, small area sources, indoor sources (such as cleaning

63 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Air Toxics Monitoring

materials), and other environmental sources (such as wildfires). The lifetime, transportation, and make-up of these pollutants are affected by both weather (rain and wind) and landscape (mountains and valleys). They can be transported far away from the original source, or be caught in rain and brought down to waterways or land. The following section discusses air toxic compounds, possible sources, monitoring techniques, findings for 2007 and a comparison of 2007 data to previous years.

In 2004, the Air Toxics Network underwent changes to the detection limits and reporting limits of the chemicals in this network. Lowering the limit of detection helps the data better represent reality. Instead of only seeing the higher numbers that were detected and using those numbers for average concentrations, one is able to see both sides of the spectrum and have a truer average for each chemical. Also, including the lower concentrations for each chemical allows for a better understanding of what levels can cause chronic health problems. Seeing only the higher levels of concentration, or possibly spikes, only yields data useful for identifying acute health effects. However, with the lower concentration levels included in the data, there can be further assessment of potential chronic health effects. With the lower limits included in the data, one is able to see all possible effects of the chemicals analyzed.

64 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report
METALS

Section: Air Toxics Monitoring

The metals subcategory includes antimony, arsenic, beryllium, cadmium, chromium, cobalt, lead, manganese, nickel, selenium, and zinc.

Antimony is used as a hardener in lead for storage batteries, in matches, as an alloy in internal combustion engines, and in linotype printing machines. Antimony compounds are used in making materials flame-retardant, and in making glass, ceramic enamels, and paints. Forms of the antimony metal are also used in medicines, and can be found in gasoline and diesel exhaust.

Arsenic occurs naturally at trace levels in soil and water. Most people are not exposed to arsenic through air pollution, but it can be found in food. The arsenic found in air comes mainly from the burning of coal or fuel oil, from metal smelters or iron foundries, and from the burning of waste.

Beryllium is a lightweight and rigid metal and used in watch springs, computer equipment, and used in the production of beryllium-copper as an alloying agent. This strong alloy is used to conduct heat and electricity, in spot welding, electrical contacts, and high-speed aircraft. Until 1949, beryllium was used in fluorescent lighting, until it was determined to have caused berylliosis, a disease that primarily affects the respiratory system and skin. Beryllium in ambient air is mainly a result of the burning of coal or fuel oil.

Cadmium emissions, like beryllium and arsenic, are mainly from the burning of fossil fuels such as coal or oil. The incineration of municipal waste and the operation of zinc, lead, or copper smelters also release cadmium to the air. For nonsmokers, food is generally the largest source of cadmium exposure.

Chromium sources include the combustion of coal and oil, electroplating, vehicle exhaust, iron and steel plants, and metal smelters. The emissions from these sources are a combination of elemental chromium and compounds including chromium ions. The most toxic form is hexavalent chromium.

Cobalt is used as a pigment (blue and green coloring agent), as a drying agent for paints, inks and varnishes, and as a catalyst for the petroleum and chemical industries. It is used as an alloy for parts in turbine aircraft engines, corrosion-resistant alloys, magnets, battery electrodes, and steel-belted tires. Cobalt also has a medicinal use as a radioactive metal in radiotherapy. It is also found in gasoline and diesel exhaust. Cobalt is actually necessary to many forms of life, when ingested through the digestive tract, in small amounts, as a micronutrient. It is a central component of vitamin B-12. As with most micronutrients, however, human activity can cause it to accumulate in unnatural locations or in unnatural concentrations. In those cases, it may be harmful and is considered a pollutant.

Lead is used in the manufacturing of batteries. The largest source of lead in the atmosphere used to be from the combustion of leaded gasoline. With the elimination of lead from gasoline, lead levels in the air have decreased considerably. Other sources of lead emissions include combustion of solid waste, coal, oils, emissions from iron and steel production, and lead smelters. Exposure to lead can also occur from food and soil. Children are at particular risk to lead exposure, because they commonly put hands, toys, and other items in their mouths that may come in contact with leadcontaining dust and dirt. Lead-based paints were commonly used for many years. Flaking paint, paint chips, and weathered paint powder may be a major source of lead exposure, particularly for children.

Manganese is a naturally occurring substance found in many types of rock and soil; it is ubiquitous in the environment and found in low levels in water, air, soil, and food. Manganese can also be released into the air by combustion of coal, oil, wood, the operation of iron and steel production plants.

65 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Air Toxics Monitoring

Nickel is found in the air as a result of oil and coal combustion, residential heating, nickel metal refining, lead smelting, sewage sludge incineration, manufacturing facilities, mobile sources, and other sources.

Selenium is a by-product of mining and smelting sulfide ores, such as silver, copper, and pyrite. It is found in soils, and can also be released by burning coal. Selenium has photovoltaic and photoconductive properties and is therefore used in photocells and solar panels. It is used as a pigment (red coloring agent) in enamels and glass. It is also used as a toner in photographs and in photocopying. Selenium is also found in gasoline and diesel exhaust. Selenium is a micronutrient, needed at very low levels for the health of all living creatures. It is normally absorbed through the digestive tract, though, and is not desirable in the air.

Zinc is found in gasoline and diesel exhaust. It is used to prevent corrosion of galvanized steel. It is also used in diecasting, and as part of battery containers. Zinc has been used as the primary metal in making the U.S. penny since 1982. Zinc compounds are used in making white pigment, sunscreen, deodorant, calamine lotions, and pigments for glow in the dark items. It is also used in the rubber industry. Like selenium, zinc is also a micronutrient needed for the health of living beings when consumed through the digestive system. When found in the air, though, it may be considered a pollutant.

See Figure 49 for a map of monitoring locations for metals.

66 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Air Toxics Monitoring

Figure 49: Metals Monitoring Site Map
67 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Air Toxics Monitoring

550

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0 Augusta BrunswGicekneral Coffee ColumbusDawsonvilleGainesville*

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Valdostaarner Robins W

Yorkville

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2005 2006 2007

*The South DeKalb sampler runs twice as often as the other sites. Gainesville runs one extra sample a month.

Figure 50: Total Detections of Metals, by Site, 2005-2007
Figure 50 shows the total number of metal species detected at each site for the years 2005 to 2007. Unlike the rest of the network measuring metals, the equipment at South DeKalb collects only the PM10 fraction of the total suspended solids. The South DeKalb site also has data collected every six days, as opposed to every twelve days at the other sites. It should also be noted that that Gainesville site has one extra sampling collection a month. Therefore, it is understandable that these sites have the highest number of detections. Without these sites included in the graph, the distribution across the sites would be relatively similar. Lower limits of detection (LOD) were introduced in September of 2004, therefore to be consistent, the data represented in these figures starts with the 2005 data. There have been only three full years of data collected at the lower limits, therefore true trends may not be discernible at this time. However, there appears to be a downward trend in the number of metals detected across the state. With Figure 50, the distribution of metals at the various locations across the state can be examined as well as any changes in the past three years. The variability across the various sampling locations is modest, considering the vast geographic distribution of the sites, and climatological and anthropogenic influences from nearby urban development.

68 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Air Toxics Monitoring

Figure 51 shows the network's frequency of detection and total average concentration by metallic species at all Air Toxics sites during 2005 through 2007. As seen in the previous graph, the number of detections has shown a slight decrease in 2007. One point of interest when looking at data is to track the number of detections along with the concentration. When examining this aspect, it appears that most metals had several detections. Therefore, each metal detection contributes little concentration to the overall total concentration. This does not seem to be the case for zinc. While its detection frequency was almost the same as the other metals, zinc had the highest average concentration for all three years. This would indicate that for each zinc detection, there was a higher concentration of that metal. Some metals including zinc, nickel, antimony, lead, chromium, and cadmium have been associated with emissions from tires and brake linings. The use of vehicles on Georgia's roads could be a reason for higher levels associated with some of these metals. With the concentrations of zinc being much higher than the other metals, zinc is explored further in Figure 52.

Average Concentration Number of Detections

0.45

500

0.4

450

0.35

400

0.3

350

300 0.25
250 0.2
200

0.15

150

0.1

100

0.05

50

0

0

Antimony

Arsenic

Berrylium

Cadmium Chromium

Cobalt

Lead Manganese

Nickel

Selenium

Zinc

Name of Metal

Concentration

Detects

2005 2006 2007 2005 2006 2007

Figure 51: Average Concentration and Total Detections of Metals, by Species, 2005-2007

69 Georgia Department of Natural Resources
Environmental Protection Division

2007 Georgia Ambient Air Surveillance Report

Section: Air Toxics Monitoring

With Figure 52, the total average concentrations of zinc are investigated more closely, divided by site, for 2005 through 2007. Several sites had a consistent level of zinc through the three years, and a few sites even had a decrease in zinc levels throughout the three years of data. The General Coffee, Columbus, Gainesville, and Valdosta sites, however, had a noticeable increase in zinc levels from 2005 to 2006. With the 2007 data, these four sites showed a slight decrease. Another change to take note of is the increase of zinc at the Brunswick site from 2006 to 2007. There was an increase of over two times the 2006 level of zinc at the Brunswick site. To look at the overall levels of zinc, the Utoy Creek site has consistently had the highest concentration from 2005 to 2007, with levels almost nine times as high as the lowest concentrations, which were at the South DeKalb site. It is surprising to see the South DeKalb site, which is situated in the metro Atlanta area, display such lower concentrations. The Utoy Creek site is situated at the Utoy Creek Wastewater Treatment Facility. Zinc can be used to help keep galvanized steel from corroding, and is possibly used for this reason on the pipes at the wastewater treatment facility. There are industries in the area that discharge their wastewater into the Utoy Creek Wastewater Treatment Facility. Al