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THE NATIONAL DIOXIN AIR MONITORING NETWORKMEASUREMENTS OF CDDs, CDFs AND COPLANAR

PCBs AT 18 RURAL, 8 NATIONAL PARKS, AND 2 SUBURBAN AREAS OF THE UNITED STATES: RESULTS

FOR THE YEAR 2000

David H. CleverlyNational Center for Environmental Assessment

Office of Research and DevelopmentU. S. Environmental Protection Agency

Washington, DC 20460

DIOXIN 2002: 22st International Symposium on Halogenated Organics and POPs, Barcelona, SpainAugust 12– 16, 2002

The views presented in this paper are those of the authors and may not represent the the US

Environmental Protection Agency

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NDAMN was established in 1998 to measure atmospheric levels of CDDs, CDFs and cp-PCBs in rural and agricultural areas, and to:

Establish background levels Determine temporal and geographical variability Investigate long-range transport and transboundary

movement Verify/calibrate air transport models

Objectives of the National Dioxin Air Monitoring Network (NDAMN)

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Measured Analytes

CDD Congener CDF Congener Coplanar PCB(IUPAC #)

2378-TCDD12378-PeCDD123478-HxCDD123678-HxCDD123789-HxCDD1234678-HpCDD12346789-OCDD

2378-TCDF12378-PeCDF23478-PeCDF123478-HxCDF123678-HxCDF123789-HxCDF234678-HxCDF1234678-HpCDF1234789-HpCDF12346789-OCDF

(77) 3,3',4,4'-TCB(126)3,3',4,4',5-PeCB(169)3,3',4,4',5,5'-HxCB(105)2,3,3',4,4'-PeCB(118)2,3',4,4',5-PeCB(156)2,3,3',4,4',5-HxCB(167)2,3,3',4,4'5-HxCB

.

Total TetraCDDTotal PentaCDDTotal HexaCDDTotal HeptaCDD

Total PCDD

Total TetraCDFTotal PentaCDFTotal HexaCDFTotal HeptaCDF

Total PCDF

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1. Penn Nursery, PA 11. Bennington, VT 21. North Platte, NE

2. Penn Nursery, PA (duplicate) 12. Jasper, NY 22. Goodwell, OK3. Clinton Crops, NC 13. Beltsville, MD 23. Big Bend, TX4. Everglades NP, FL 14. Caldwell, OH 24. Grand Canyon, AZ

5. Lake Dubay, WI 15. Oxford, OH 25. Theodore Roosevelt N.P., ND6. Monmouth, IL 16. Dixon Springs, IL 26. Craters Moon, ID

7. McNay, IA 17. Quincy, FL 27. Chiricahua, AZ8. Lake Scott, KS 18. Bay St. Louis, MS 28. [TBD]

9. Bixby, OK 19. Padre Island, TX 29. Hyslop Farm, OR10. Arkadelphia, AR 20. Fond Du Lac, MN 30. Ozette Lake, WA

31. Fort Cronkhite, CA

1. Penn Nursery, PA 11. Bennington, VT 21. North Platte, NE

2. Penn Nursery, PA (duplicate) 12. Jasper, NY 22. Goodwell, OK3. Clinton Crops, NC 13. Beltsville, MD 23. Big Bend, TX4. Everglades NP, FL 14. Caldwell, OH 24. Grand Canyon, AZ

5. Lake Dubay, WI 15. Oxford, OH 25. Theodore Roosevelt N.P., ND6. Monmouth, IL 16. Dixon Springs, IL 26. Craters Moon, ID

7. McNay, IA 17. Quincy, FL 27. Chiricahua, AZ8. Lake Scott, KS 18. Bay St. Louis, MS 28. [TBD]

9. Bixby, OK 19. Padre Island, TX 29. Hyslop Farm, OR10. Arkadelphia, AR 20. Fond Du Lac, MN 30. Ozette Lake, WA

31. Fort Cronkhite, CA

National Parks4,19,23,24,25,26,27,30

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HI-VOL Dioxin PUF Sampler

Magnehelic Gauge(0 – 100”)

Sampling Head

Venturi

VoltageVariatorBlower

Motor7-dayTimer

Exhaust Hose

Aluminum Housing

Airflow

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Sampling Frame

Sampling Period: 24 hrs/d; 5 d/wk 28 days

All stations operate simultaneously with 4 sampling periods/year

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Detection Limits (fg/m3)

In order to meet these detection limits, it is necessary to sample 6000 – 8000 m3 of air

TCDD/CDF 0.07 PCB77 3PeCDD/CDF 0.2 PCB118 70HxCDD 0.4 PCB105 40HxCDF 0.2 PCB126 0.3HpCDD/CDF 0.4 PCB156 10OCDD 3 PCB157 3OCDF 0.6 PCB169 0.1

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Moment number Approximate sampling dates Season assignment

1 June 23, 1998 - July 21, 1998 Summer

2 August 18, 1998 - September 15, 1998 Summer

3 November 24, 1998 - December 22, 1998 Fall

4 January 26, 1999 - February 23, 1999 Winter

5 March 23, 1999 - April 20, 1999 Spring

6 May 18, 1999 - June 15, 1999 Spring

7 July 6, 1999 - August 3, 1999 Summer

8 August 24, 1999 - September 21, 1999 Summer

9 November 9, 1999 - December 7, 1999 Fall

10 January 18, 2000 - February 15, 2000 Winter

11 April 4, 2000 - May 2, 2000 Spring

12 August 22, 2000 - September 19, 2000 Summer

13 November 22, 2000 - December 19, 2000 Fall

Sampling Moments 1998 - 2000

9 Figure displaying frequency of detection, by compound.Figure displaying frequency of detection, by compound.

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Average 2,3,7,8-TCDD Concentrations (fg/m3) for Sampling Moments 10 through 13 by Location, ExcludingInfluential Observations.Average 2,3,7,8-TCDD Concentrations (fg/m3) for Sampling Moments 10 through 13 by Location, ExcludingInfluential Observations.

2,3,7,8-TCDD

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Rural DF TEQ: 14.6 fg/m3Parks DF TEQ: 2.0 fg/m3Rural PCB TEQ: 1.1 fg/m3Parks PCB TEQ: 0.2 fg/m3

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13

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Conclusions

The mean TEQDF–WHO98 and PCB-TEQ air concentration measured at 18 rural areas is 14.6 fg m-3, and 1.1 fg m-3, recpectively.

The mean TEQDF–WHO98 and PCB-TEQ air concentration measured at 8 national parks is 2.0 fg m-3 and 0.2 fg m-3 ,respectively.

There was no change in CDD/CDF and PCB air concentrations from 1999.

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Conclusions

    All 2,3,7,8-substituted CDD/CDF congeners were detected in ambient air at the 18 rural stations.

CDD/CDF compounds were detected in over 70% of the samples.

Excluding PCB 169, PCB compounds were detected in all samples.

In general, these results indicate that NDAMN sampling and analytical procedures are appropriate for generating sufficient data to assess background levels of CDD/CDFs and PCBs in rural areas of the united states.

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Conclusions

The two suburban site (stations 13 and 31) had a mean TEQDF–WHO98 and PCB-TEQ

of 15.5 fg m-3 and 2.0 fg m-, respectively. Thus the suburban sites had similar air concentrations of DF-TEQ as rural areas, but 10-fold higher mean PCB levels as compared to rural areas.

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Conclusions

There was a 28-fold range in TEQDF–

WHO98 annual average air concentrations at

the rural sites: 60 to 2.5 fg m-3 .

PCB-TEQ air concentrations ranged from 0.2 fg m-3 to 9.9 fg m-3, a range of approximately 50.

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Conclusions

The lowest mean annual air concentration of dioxin-like compounds has consistently been observed at the Grand Canyon national park (site 24), with a mean of 0.3 fg m-3 DF-TEQ and 0.1 fg m-3 PCB-TEQ.

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1 2

11 12

13

3

4

17 18

19

23

27

24

31 28

29

30

26

25

21

8

9 22

20

5

7 6

10

16 15

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1. Potters Mill , PA 3. Clinton Crops , Clinton, NC 4. Everglades National Park, FL 5. Lake Dubay , Darcy , WI 6. Monmouth ,IL 7. Mcnay , IA 8. Lake Scott State Park, KS 9. Bixby , OK

10. Arkadelphia , AR 11. Bennington , VT 12. Jasper, NY 13. Beltsvill , MD 14. Caldwell, OH 15. Oxford, OH 16. Dixon Spring, IL 17. Quincy, FL

18. Bay St. Louis, MS 19. Padre Island NP,TX 20. Fond Du Lac, MN 21. North Platte, NE 22. Goodwell , OK 23. Big Bend NP, TX 24. Grand Canyon NP, AZ 25. Theodore Roosevelt NP, ND

26. Craters-of-the-Moon NP, ID 27. Chiricahua National Mom, AZ 28. Rancho Ceco , CA 29. Hyslop Farm, Benton, OR 30. Lake Ozette , Olympic NP, WA 31. Fort Cronkhite NP, CA

NP = National Park

NDAMN Stations in 2000

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SamplerSampler

View of sampler and surrounding areaView of sampler and surrounding area

Grand Canyon National Park, Arizona

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Grand Canyon

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Grand Canyon

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Conclusions

The articulation of “background” concentrations of CDDs, CDFs and PCBs requires prolonged measurements taken annually over the course of several years. Furthermore, “background” should be associated with at least 3 distinct classifications of human habitation: rural, wilderness, and urban/suburban.

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Acknowledgements

EPA: Dwain winters, Joe Ferrario, Chris Byrne, Aubrey Dupuy

Battelle: Karen Riggs, Pamela Hartford, Darrell Joseph, Tony Wisbith