± 0 4 8 Miles

2007 RMP Status and TrendsMonitoring

10 ng/g dryweight

TDCPP

TCPP

Sum PBDEs

Sum PCBs

1. Stapleton et al. 2009. Environ. Sci. Technol. 43:7490–7495.

2. US EPA, Furniture Flame Retardancy Partnership: Environmental Pro-files of Chemical Flame Retardant Alternatives for Low Density Poly-urethane Foam. In EPA 742-R-05-002A. 2005.

3. World Health Organization. Flame Retardants: Tris (chloropropyl) phosphate and tris (2 chloroethyl) phosphate; Geneva, 1998; Environ-mental Health Criteria 209.

4. Babich, M. A. CPSC Staff Preliminary Risk Assessment of Flame Retar-dant (FR) Chemicals in Upholstered Furniture Foam; USCPSC: Bethesda, MD, 2006; www.cpsc.gov/library/foia/foia07/brief/ufurn2.pdf.

5. Klosterhaus, S. et al. 2009. Poster presentation at the BFR Workshop, Ottawa, Ontario.

6. Marklund, A. et al. 2005. Environ. Sci. Technol., 39:7423-7429.

7. Bester, K. 2005. J . Environ. Monit., 7:509–513.

8. Martinez-Carballo, E. et al. 2007. Sci Tot Environ 388:290–299.

9. Draft European Union Risk Assessment. 2007. R426_0703_ENV. http://ecb.jrc.ec.europa.eu/documents/ExistingChemicals/RISK_ASSESSMENT/DRAFT/R426_0703_env.pdf

10. Stachel, B. et al. 2005. J Environ Sci Health, A40:265–287.

11. Garcia-Lopez, M. et al. 2009. J of Chromatogr A, 1216:6986–6993.

12. Kawagoshi, Y. et al. 1999. J Mater Cycles Waste Manag, 1:53–61.

13. US EPA Inventory Update Rule (http://www.epa.gov/iur/).

14. Gold, M.D. et al. 1978. Science 200, 785–787.

15. State of California Proposition 65 (http://www.oehha.org/prop65.html)

Acknowledgments

We thank Karin North, City of Palo Alto, for providing biosolids samples.

Contact information

Susan Klosterhaus: susan@sfei.org

References

Location Year TDCPP TCPP TPP Reference San Francisco Bay Area 2008 700 - 105,000 300 - 4,300 500 - 2,600 This study Sweden 2003 3 - 260 60 - 1,900 50 - 320 6 Germany 2002 - 1,000 - 21,000 - 7

Location Year TDCPP TCPP TPP Reference San Francisco Bay 2007 1 - 19 <1 - 16 <1 - 20 This study Austria 2005 <1 <1 - 1,300 <1 - 160 8 Germany, Czech Republic 2001,2002 <1 - 44 6 - 300 NA 9,10 Rivers Danube, Neckar, Rhine NA Max 1,300 NA NA 9 Spain NA <1 <5 - 30 <4 - 6 11 Japan (waste disposal site) 1991-1997 <MDL - 700 2 - 1,200 <MDL - 130 12

Table 1. Organophosphate Flame Retardants in Biosolids/Sewage Sludge (ng/g dry weight)

Table 2. Organophosphate Flame Retardants in Aquatic Sediments (ng/g dry weight)

Values were blank corrected. Due to high concentrations in one laboratory blank sample, these values should be considered estimates. The samples are in the process of being re-analyzed.

NA – not analyzed or available

Materials and MethodsSample Collection• Biosolid grab samples were collected in February 2008 from

two WWTPs that discharge effluent to San Francisco Bay (n=3 samples at one time point per WWTP).

• Surface sediment samples were collected in August 2007 via Ponar grab from 10 sites spatially distributed throughout San Francisco Bay.

Chemical Analysis• Subsamples of biosolids (0.3 g) and sediments (5-50 g) extracted

using pressurized fluid extraction (3X with 50:50 dichloromethane (DCM)/hexane; 100°C and at 1500 psi). Quantification standard 13C-CDE 141 added prior to extraction.

• Extracts purified using 4 g of 6% deactivated alumina; eluted with 50 mL of 50:50 hexane:DCM.

• Extracts blown to dryness under a N2 stream; biosolid extracts were reconstituted in DCM for GPC clean-up.

• Biosolids extracts were purified using a GPC column (EnvirogelTM GPC Cleanup 90x300 mm column, DCM mobile phase, flow rate of 5 mL/min). The first 60 mL of eluate were discarded, and the following 40 mL were collected.

• Extracts were solvent-switched to hexane.

• Analyzed using GC/MS (EI); 0.25 mm (I.D.) x 15 m fused silica capillary column coated with 5% phenyl methylpolysiloxane (0.25 μm film thickness).

• PTV injection; inlet temperature 80 °C for 0.3 min and then a 600 °C/min ramp to 300 °C.

• GC oven temperature program: hold at 80 °C for 2 min, ramp of 20 °C /min to 250 °C, ramp of 1.5°C/min to 260 °C, ramp of 25 °C/min to 300 °C, 12 min hold.

• Transfer line and ion source temperature: 300 °C and 200°C respectively.

• Quantitative/qualitative ions monitored (m/z): 381/383 for TDCPP; 277/201 for TCPP; 326/325 for TPP.

All sample measurements were blank corrected by subtracting the average level measured in the laboratory blanks.

Results and DiscussionOrganophosphate Flame Retardants in Biosolids

• TDCPP, TCPP, and TPP were detected in biosolids from both Bay Area WWTPs.

• Compared to concentrations in biosolids from Europe, concentrations of TDCPP and TPP from SF Bay were higher and concentrations of TCPP were within range or lower.

• Detection of TDCPP, TCPP, and TPP in biosolids suggests these compounds are migrat-ing from consumer products and likely entering aquatic environments via municipal wastewater effluent.

• Very limited data are available for these compounds in biosolids.

Organophosphate Flame Retardants in Sediments

• TDCPP was detected in all samples and TCPP and TPP were detected in most samples of SF Bay sediment.

• Compared to concentrations in biosolids from Europe, concentrations of TDCPP, TCPP, and TPP in SF Bay were within range or lower.

• Limited data are available for these compounds in sediments.

• TDCPP and TCPP concentrations were highest in Central and South Bays, areas most influenced by industrial activities and urbanization. The Lower South Bay is a depositional environment and compared to other areas of San Francisco Bay, often contains the highest concentrations of chemical contaminants due to high population density and relatively less dilution (Figure 2).

• TDCPP and TCPP concentrations in Bay sediments were comparable to concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) (Figure 2).

Conclusions • TDCPP, TCPP, and TPP were detected in Bay sediments and biosolids

collected from WWTPs that discharge effluent to San Francisco Bay.

• Continued exposures of TDCPP and TCPP to wildlife in the Bay are expected due to their environmental persistence (9) and current high volume production and use in new products (10-50 million lbs were produced/imported in US in 2006; automobile and furniture foam is a primary application; 13).

• Lack of ecotoxicity information is a concern, particularly because the effects of long-term exposure to low ppb concentrations are largely unknown. However the following toxicity information is available:

• TDCPP was phased out of use in children’s sleepwear in the late 1970s after a study suggested it is a weak mutagen (14); the World Health Organization (WHO) and US Consumer Product Safety Commission have identified it as a probable human carcinogen (3,4); the US EPA considers TDCPP a moderate cancer hazard and a moderate hazard for reproductive and developmental effects (2).

• TCPP is structurally similar to tris(chloroethyl)phosphate (TCEP), which has been identified as a carcinogen by the WHO (3) and the state of California (15).

BackgroundWorldwide restrictions on the use of polybrominated diphenyl ethers (PBDEs) have led to the use of alternative flame retardant chemicals to meet consumer product flammability standards. Organophosphate (OP) compounds have been used as flame retardants for decades and they have been suggested as potential alternatives to the use of PentaBDE in polyurethane foam (1-4).

Our recent work has indicated:

• Triphenyl phosphate (TPP) is a major component (17% by weight) of Firemaster 550, the PentaBDE replacement product used in the highest volume to meet the California furniture flammability standard (5);

• Tris(1,3-dichloro-2-propyl)phosphate (TDCPP) and tris(1-chloro-2-propyl) phosphate (TCPP) are common additives to polyurethane foam used in furniture purchased since the phaseout of PBDEs in 2003/2004, with concentrations as high as 5% by weight (1);

• TPP, TDCPP, and TCPP are common components of house dust and TDCPP concentrations were similar or higher than PBDEs in the same samples (1).

Though the San Francisco Bay Area and California are known hotspots for PBDEs, concentrations of the OP chemicals used to replace PBDEs have not yet been analyzed in environmental samples from California.

Study ObjectivesDetermine the concentrations of TDCPP, TCPP, and TPP (Figure 1) in:

1) Biosolids from two Bay Area wastewater treatment plants (WWTPs) — this information will be used to determine the potential for these chemi-cals to enter aquatic environments via municipal wastewater effluent.

2) Sediments collected from San Francisco Bay — this information will be used to determine if management actions are needed to reduce expo-sure to San Francisco Bay wildlife.

O

O

Cl

Cl

OPO

Cl

TCPPTris (1-chloro-2-propyl) phosphate

CAS 13674-84-5

Cl

O OP

O

O

Cl

Cl

Cl

Cl

Cl

TDCPPTris (1, 3-dichloro-2-propyl) phosphate

CAS 13674-87-8

TPPTriphenyl phosphate

CAS 115-86-6

O

O

OO P

Structures of the

Organophosphate Compounds Analyzed in This Study

Figure 1 >

< Figure 2

Organophosphate Flame Retardants in San Francisco Bay

Sediments (ng/g dry weight)

REGIONAL MONITORING PROGRAM FOR WATER QUALITY IN THE SAN FRANCISCO ESTUARY

ORGANOPHOSPHATE FLAME RETARDANTS IN SAN FRANCISCO BAY BIOSOLIDS AND SEDIMENTS SUSAN KLOSTERHAUS1, ELIZABETH F. DAVIS2, AND HEATHER M. STAPLETON2

1) San Francisco Estuary Institute, Oakland, CA, USA 2) Duke University, Nicholas School of the Environment, Durham, NC, USA