Air Toxics Analysis—Particularly Metals17th International Emission Inventory Conference

Portland, ORJune 2-5, 2008

Karen Hagelstein, Ph.D., CIHTIMES LimitedSheridan, WY USAaircaredoc@aol.com

John Heinze, Ph.D.Environmental Health Research Foundation, Chantilly, VA USAjheinze@ehrf.info

Particulate Metal Emissions Sources Industry InventoriesMetal Industry AssessmentsWorker ExposuresHealth Hazard RankingsBiomonitoringRecommendations

Air Pollution Sources—Including Particulates

AREA/NATURAL = 25%

MAJOR INDUSTRIAL/POINT = 25%(10 to 25 HAPs tons/year)

ALL MOBILE = 50% AIR POLLUTION

Urban Air Is Improving

www.epd.gov.hk

020406080

100120140160180

1990 1994 1999 2004

Perc

ent C

hang

e

Total Electricity ParticulatesSulfur Dioxides Nitrogen Oxides

Particulates

Electricity

Particulate Standards Differ

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35

Chongqing, PRC

Tainjin, China

Calcutta, India

Cairo, Egypt

Dehli, India

mg/m3

Particulate Matter Sulfur Dioxide Nitrogen Dioxide

*EPA PM10 = 0.15 mg/m3

**WHO PM10 = 0.03 mg/m3

WORKER EXPOSURE LIMITS (ACGIH and OSHA):Respirable Particulates = 3.0 to 5.0 mg/m3

Total Inhalable Particulates = 10 to 15 mg/m3

** *

Controlling Particulate Metals-Additive

• Cyclone/Scrubber• Fabric Filters• Electrostatic

Precipitation• Wet Flue Gas

Desulfurization

>90%

47-99%

Particulate Matter/SO2/NOX

Selective Catalytic Reduction + ESP:CS + Wet FGDSelective Catalytic Reduction + Spray Dryer + FF

56-74%89%

Particulate Matter/SO2

ESP:CS + Wet Flue-Gas Desulfurization (FGD)FF + Wet FGD

2-63%27-48%87-93%

Particulate MatterElectrostatic Precipitator: Cold-Side (ESP:CS)Electrostatic Precipitator: Hot-SideFabric Filter (FF)

% MERCURYCapture

Dependent on Coal TypeAir Pollution Controls

EPA TRI Total Metal ReleasesIndustry Trends

0

10

20

30

40

50

60Pe

rcen

t of T

otal

Met

al R

elea

ses

ElectricUtitlities

PrimaryMetals

RCRA MetalMining

2002 2003 2004 2005

Industry Airborne Metal Releases

0

5

10

15

20

25

30

35

40

Perc

ent o

f Tot

al M

etal

Rel

ease

s

ElectricUtitlities

PrimaryMetals

RCRA MetalMining

2003 2004

0

20

40

60

80

100

Perc

ent

HAZARDOUS AIR POLLUTANT REDUCTIONS PROJECTED

Total Air Toxics (12,000+tons/year)Metal Emissions (40 tons/year)Particulates (3,000+tons/year)

Projected Reductions Not Verified:Secondary Aluminum Plants (Primary Metals) USEPA 40 CFR Part 63, 2000

EPA TRI IndustryTotal Mercury & Selenium Releases

0

100

200

300

400

500

600

Tons

/Yea

r

Mercury2003

Mercury2004

Mercury2005

Selenium2003

Selenium2004

Selenium2005

Electric Utilities Primary Metals RCRA Landfills

2005 EPA TRI Total Metal Emissions

(Million Pounds)

TOTAL (18 Metals)

Selenium

Mercury

Lead

Cadmium

Arsenic

METALS

2,310

3.47

4.40

470

3.33

185

ALL Industries

38417% Total

1.25

0.15

8.27

No Data

6.45

Electric Utilities

47020% Total

0.43

0.03

34.0

1.14

5.25

Primary Metals

1687.3% Total

1.13

0.44

19.7

1.56

1.77

RCRA

1,16050% Total

0.46

3.67

394

0.52

172

Metal Mining

Summary: EPA TRI 2005 Metal Emissions

TOTAL METALS (18 Metals)Metals Industry > Electric Utilities ReleasesDecreasing Total Emissions from 2000 to 2005Majority (77%) Total Metal Releases OffsiteAIRBORNE METALSOnsite Total Metals Released to Air ~7%Majority (>70%) Are Point SourcesMetals Industry Is Largest Source (35%)Selenium>Mercury Emissions

CASE STUDY 2003—Environmental Samples at Three Aluminum Facilities

• Process MaterialsAluminum Melt, Alloy, & Dross

• Solid WastesBaghouse Dust Salt Cake

• Air QualityStack EmissionsWorkplace--Area & Personal Samples

Worker Monitoring—Particulate Metals Worst Case Exposures• Respirable Particulates• Pumps/Cassettes/Filter

Metals—ICAP-AES, XRD• Real Time Particulate

Infrared Sensors• Colorimetric Detector

Tubes for Gases (AsH3)• Area/Breathing Zones

Hazardous Metal Wastes

Ranking Solid Wastes: EPA TCLP ValuesMercury = 0.2 mg/LSelenium = 1.0 mg/LCadmium = 1.0 mg/LLead = 5.0 mg/LChromium = 5.0 mg/LArsenic = 5.0 mg/L

INDUSTRIAL EXPERIENCES: USA $$

XU.S. Five States 1993/1998

XAluminum Recycling Facility

XXXGold Mining Heap Leach

XXXXXPhosphate Waste Shale Disposal

XXXXXCopper Mining Wetlands

XXXXOil Refinery Wastewater

XXXXXCoal Fly Ash Disposal

Hazardous Waste Impacts

Mammal Impacts

Bird Impacts

USEPAFish Advisories

Surface Water Impacts

Ground Water Impacts

SELENIUM Contaminant of Concern

Worker Health & Particulate Metals

• OSHA Exceedences (2000-2005):Noise, Dust, Fumes (SIC 33XX)Test Substances = 1-75 (No Selenium Compounds)Maximum Number of Tests ~ 300/Year

• 2007 NIOSH Chromium Exposures ~30% Industries Had:No Exposure Data (i.e. Noise)No Air Monitoring for 3 Years

• 2007 Aluminum Alloy Welding Study:Alloys with Lower Melting & Boiling Points are More Reactive = Higher Particulate Emissions

• Boiler Maintenance Workers: Cr, Cu, Mn, Ni, Pb, Ni Exposures and Increased Autonomic Cardiac Dysfunction

• Battery Assembly Workers: Cadmium Dust Exposures and Increased Kidney Failure, Lung Cancer, Bone Disease

Worker Biological Exposure Indices (BEIs, ACGIH, 2005)Taiwan Steel Worker Overexposures (As, Be, Se)

0 10 20 30 40 50

Selenium

Nickel

Mercury

Lead

Chromium

Copper

Cadmium

Beryllium

Arsenic

ug/g creatinine in urine ug/L urine

Lead ~100 ug/g creatinine in urine

Metal BEIs:Hair/Nails

Health-Based Metal Concentrations

X

21.6

25 ug/g creat. Urine

0.05

1.0

0.20

126

4.0E-5

1.8E-2

70.20

Se

10.6

5.0

1.1

95.0 Dust

Zn

0.050.050.100.0070.002IFC Metal Mining Standards(mg/m3)

36

3.0E-5X

4

4.9E-4

42

8.0E-4X

5 (Cr+6)2.0E-4

13

3.0E-5

56

8.0E-5

17

3.1E-3

EPA Hazardous Air Pollutant RANKTotal = 189 HAPSDetection Limit (mg/m3)High Analytical Confidence

7.3E-23.1E-43.7E-7TetraethylPb

5.51.5E-19.9E-77.5E-74.1E-7EPA Ambient Air Risk-Based Conc. (mg/m3)

32.128.733.332.729.432.939.740.4Total Chemical Hazard Score (1-100 IRCHS)

2 ug/g creat. Urine

35 ug/g creat. Urine

30 ug/100 ml Blood

25 ug/LUrine

50 ug/gcreat.Urine

5 ug/g creat.Urine

2 ug/g creat. Urine

35 ug/LUrine

Biological Exposure IndicesTaiwan Steel Worker Overexposures

X

1.0

60.10

Cu

X

0.002

0.2

60.10

Hg

XXXXEcosystem BioaccumulationLichen Studies (120)

0.0150.10.0050.0040.05EPA Drinking WaterMCL (mg/L)

70.05.05.01.00.0075.0EPA Hazardous Solid WasteTCLP (mg/L)

40.015X

50.05

8 0.50

20.005X

10.002X

30.01X

OSHA PEL RANK(mg/m3)CANCER

NiPdCr CdBeAsMETALS (10)

0

10

20

30

40

50

Tota

l Haz

ard

Valu

e Sc

ore

Metal Compounds

Arsenic Beryllium Cadmium CopperChromium Lead Mercury NickelSelenium Selenium Dioxide Zinc

Total Environmental Hazard Scores Indiana Relative Chemical Hazard Scores (1-100)

Biological Monitoring—Background Urinary MetalsHuman Exposure to Environmental Chemicals (CDC Third Report July, 2005)

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2 4.4 4.6 4.8

Uranium

Tungsten

Thallium

Platinum

Mercury

Lead

Cobalt

Cesium

Cadmium

Beryllium

Barium

Antimony

ug/g creatinine in urine2001-2002 1999-2000

Molybdenum 45.5 (2001-2002)

Metal Biological Benchmarks (1999 to 2005)

• USA blood lead levels have decreased.• All USA women & children monitored have

non toxic & decreasing levels of mercury.• However, global mercury levels increasing.• Cadmium levels are increasing (smokers).• Cesium levels high due to medical testing.• Five Metal Health Hazards Not

Monitored by CDC: As, Cu, Cr, Ni, Se.

Airborne Metals Management

• Major USA Sources--Metals Industry & Electric Utilities

• Recycling Industry Increasing• Selenium Emissions Are Increasing

Component of Coal & Manganese Metals• Particulates & Metal Indicators:

Arsenic, Cadmium, Chromium, Lead, Mercury, Selenium

• Biomonitoring Recommended• Air Pollution Controls Effective But

Emissions & Factors Uncertain

THANK YOU FOR YOUR

TIME