California Ambient Dioxin Air Monitoring Program

(CADAMP)

Kathy GillAir Resources Board

Monitoring and Laboratory Division California Environmental Protection Agency

April 19, 2005

Background• Program initiated in 2000 - funding for two years of

ambient monitoring

• Sampling began in December 2001 with 10 sites.

• Sampling conducted by BAAQMD, SCAQMD and ARB staff

• Monitoring for dioxins/furans, dioxin-like PCBs, and PBDEs (flame retardants)

• Data will be used to help understand dioxin levels in ambient air and prioritize risk management strategies

U.S. EPA Site Locations

• U.S. EPA established a national dioxin air monitoring network (NDAMN) to estimate rural ambient air concentrations of dioxins/furans and PCBs throughout the U.S. Operated from 1998 through 2002 with up to 30 sites.

• CADAMP design similar to NDAMN (1/28 days vs. 1/3 months)

• NDAMN sites in California located in: - Bay Area (Fort Cronkhite, San Francisco) - Central Valley (Rancho Seco Park)

Bay Area Sites

2

5

3

4

1

FortCronkhite(NDAMN)

SanFrancisco(NDAMN)

9

8

67

9

86

7

1

2

43

5

Sacramento* Rancho Seco

1- San Jose2- Livermore3- Oakland4- Crockett5- Richmond6- Reseda7- Boyle Heights8- Rubidoux9- Wilmington

* NDAMN sites

CADAMP SITES

South Coast Sites

Sampling • Based on U.S. EPA Method TO-9A

– PS-1 type high volume sampler– normally used for 24-hour samples

• Each sample– 1 PUF/XAD/PUF sandwich in glass cartridge– 4 Quartz Fiber Filters (QFF)

• CADAMP extended sampling periods of 28 days – Four sub-periods (5-6 days on, 1-2 days off)– QFF changed each week to prevent overloading and

maintain flow rate– PUF/XAD/PUF remains in place for all 28 days

Sampling Head

Chart Recorder

Timer and Flow Controller

Magnehelic Gauge

Benefits of Long Duration/Large Volume

SamplingCollecting 6000 - 8000 L of air

• Provides low detection limits (~0.2 fg/m3 for 2,3,7,8-TCDD)

• Minimizes the non-detects

• Provides comprehensive temporal coverage (representativeness)

• Minimizes number of samples collected

• Reduces lab costs

Analysis

• U.S. EPA Established Procedures– Method TO-9A/1613A for 17 dioxins/furans– Method 1668A for 14 PCBs – Draft Method 1614 for 44 PBDEs– Single sample; extract split 3 ways

• Dioxin/Furans• PCBs and PBDEs• Archive portion

O

O Cl

Cl

Cl

Cl

2,3,7,8 -TCDD

Cl

O Cl

Cl

Cl

2,3,7,8-TCDFCl

Cl

Cl

Cl

3,3’,4,4’-TeCB

O

Br

Br

Br

Br

Br

2,2’,4,4’,6-Pentabromodiphenyl Ether

Valid Results

Extensive field and laboratory validation criteria applied to data

• 2002– 101 valid samples (84% completeness)– 21 valid field blanks (88% completeness)

• 2003– 145 valid samples (93% completeness)– 25 valid field blanks (96% completeness)

Toxicity Equivalence Factors (TEFs)

• Concentrations for dioxins expressed as toxicity equivalence (TEQ)– TEFs are numerical factors that express toxicity of

each dioxin, furan or PCB relative to the toxicity of 2,3,7,8-TCDD

• 1997 WHO TEFs– Adopted by California in 2003 - replaced the I-TEFs– Used in NDAMN, making data comparisons

between the two networks possible

Concentration Results

• Lab results– reported as picograms/sample

• (pg = 10-12)

• Calculate air concentration – femtograms/cubic meter

• (fg = 10-15)

• Convert to Toxicity Equivalence – fg TEQ/cubic meter

2002/2003 QC

• Collocated Samples

• Average Field Blank Concentrations• 0.48 fg TEQ/m3 for D/F• 0.04 fg TEQ/m3 for PCBs

# Valid Pairs

D/F Relative Percent

Difference (RPD)

PCB Relative Percent

Difference (RPD)

Boyle Heights 15 6.1% 9.5%

Oakland 10 6.9% 7.6%

San Francisco Bay Area Sampling Period TEQ Averages

2002 2003

0

10

20

30

40

50

60

70

12/2

0/01

1/17

/02

2/14

/02

3/14

/02

4/11

/02

5/16

/02

6/6/

02

7/4/

02

8/1/

02

8/29

/02

9/26

/02

10/3

1/02

11/2

1/02

WH

O-9

7 T

EQ

, fg

/m3

12/1

9/02

1/16

/03

2/13

/03

3/13

/03

4/10

/03

5/8/

03

6/5/

03

7/3/

03

7/31

/03

8/28

/03

9/25

/03

10/2

3/03

11/2

0/03

D/Fs PCBs

Includes all valid samples for each sampling period

South Coast Area Sampling Period TEQ Averages

2002 2003

0

10

20

30

40

50

60

70

12/2

0/01

1/17

/02

2/14

/02

3/14

/02

4/11

/02

5/16

/02

6/6/

02

7/4/

02

8/1/

02

8/29

/02

9/26

/02

10/3

1/02

11/2

1/02

WH

O-9

7 T

EQ

, fg

/m3

12/1

9/02

1/16

/03

2/13

/03

3/13

/03

4/10

/03

5/8/

03

6/5/

03

7/3/

03

7/31

/03

8/28

/03

9/25

/03

10/2

3/03

11/2

0/03

D/Fs PCBs

Includes all valid samples for each sampling period

CADAMP Averages

• PCB contribution to Total TEQ was up to 50%

D/F

fg TEQ/m3

PCB

fg TEQ/m3

Site Annual Average 13 - 43 2 - 10

Statewide Average 23 5.6

Comparison of CADAMP Results

• Key Factors to Consider in Comparing Data to Other Studies– TEFs (which scheme used?)– Detection limits (DL)

• factored as DL, 1/2 DL or zero for TEQ calculation

• if elevated (due to volume collected or analytical technique) can impact TEQ

– Blank corrections– Short vs. long duration sampling– CADAMP annual averages vs. few data points– Remote - rural - urban - source impacted?

Average Range

NDAMN Remote 2000 1.2 0.12 - 6.1 NDAMN Remote 2001 1.0 0.05 - 3.6

NDAMN Ft. Cronkhite, CA 2001 2.9 1.3 - 7.2

NDAMN 'Rural' 2000 14 0.67 - 130 NDAMN 'Rural' 2001 13 1.2 - 78

NDAMN, Beltsville, MD 2000 17 8.6 - 24 NDAMN, Beltsville, MD 2001 11 8.1 - 14

Calcasieu Parish, LA 2001 14 2.7 - 92

CADAMP 2002 24 6.1 - 190 CADAMP 2003 23 4.4 - 71

fg TEQ/m3

Dioxin/Furan Comparisons

Average Range

NDAMN Remote 2000 0.3 0 - 2.0 NDAMN Remote 2001 0.2 0.05 - 1.0

NDAMN Ft. Cronkhite, CA 2001 0.4 0.3 - 0.6

NDAMN 'Rural' 2000 0.7 0.07 - 5.9 NDAMN 'Rural' 2001 1.0 0.08 - 12

NDAMN, Beltsville, MD 2000 2.7 1.0 - 7.0 NDAMN, Beltsville, MD 2001 2.4 1.2 - 4.7

Calcasieu Parish, LA 2001 1.4 0.4 - 2.6

CADAMP 2002 5.8 0.5 - 21 CADAMP 2003 6.1 1.0 - 19

PCB Comparisons

fg TEQ/m3

2004/2005 Monitoring

• 2004 continued as 2003 with 10 sites and 2 collocated samplers

• 2005 - Retained one Bay Area site (Livermore) and one South Coast site (Rubidoux)

• Installed sampler in San Joaquin Valley at Fresno in January 2005

• Will add rural San Joaquin Valley site to conduct high population urban vs. rural comparison and obtain rural PBDE data

• Continue for 13 sampling moments

ARB Web Pageswww.arb.ca.gov/aaqm/qmosopas/dioxins/dioxins.htm

• Web pages contain: – Maps and site histories– QAPP, FOP, methods, sampling schedules– Individual congener concentrations and TEQ for both D/F

and PCB at each site– Quarterly and annual averages for each site– Regional and statewide averages

• Downloadable data - Excel format

• 2003 PBDE and all 2004 data expected to be released and on web in near future

ARB Dioxin Web Site

www.arb.ca.gov/aaqm/qmosopas/dioxins/dioxins.htm