Emerging Contaminants & Aquatic Impacts in

San Francisco Bay

Rebecca Sutton, Ph.D. San Francisco Estuary Institute

January 11th, 2017

Goal: Collect data, communicate information about water quality to support management decisions

Stakeholders

Govern-ment

Scientists

Industry

Innovative Partnership Celebrating our 25th year!

Nonylphenol & Nonylphenol Ethoxylates: Environmental Detections

SF Bay 2009-2010 Klosterhaus et al. 2013

4-NP: ND - 73 ng/L Water

Sediment

Effluent

4-NP: 22-86 ng/g dw 4-NP1EO: 4-40 ng/g dw

4-NP2EO: ND-19 ng/g dw

4-NP: 41 ng/L

4-NP: 506-1690 ng/L 4-NP1EO: 1220-1760 ng/L 4-NP2EO: 1690-2610 ng/L

Puget Sound 2013-2014 Meador et al. 2016

DATA GAP: Other Members of NPE Family

• Sensitive species: Barnacle Balanus amphritite Reduced larval settlement: 60 ng/L NP

Billinghurst et al. 1998

• Synergistic impacts: Estrogenicity (in vivo) – APs/APEs and pesticides (bifenthrin, diuron)

Schlenk et al. 2012

Nonylphenol & Nonylphenol Ethoxylates: Additional Hazard Traits

Moderate Concern for San Francisco Bay

• Toilet paper – Diehl et al. 2012

• PVC water pipes – Cheng et al. 2016

• Polyethylene (food-grade) – Hamlin et al. 2015

• Plastic (as aquatic contaminant) – Hirai et al. 2011: Plastic from North Pacific Central

Gyre contains NP (6-1000 ng/g ww), likely additive

– Gassel et al. 2013: Plastic-mediated exposure to NP linked to fish from this Gyre

Nonylphenol & Nonylphenol Ethoxylates: Consumer Product Sources

Detergent Cleaning surfactant Coatings Paints Resins Sealants Adhesives Caulk Printing ribbon component Food additive Food contact adhesives and coatings Pesticide ingredient Agriculture use for animals Fuel additive Plastic and polymer additive

Hardener Lubricant Colorant or ink component Emulsifier Epoxy catalyst Rheology modifier Wetting agent Catalyst Processing aid Defoamer Antioxidant Corrosion inhibitor Paint stripper Paint primer …

EPA Proposes Significant New Use Rule October 1, 2014

Nonylphenol & Nonylphenol Ethoxylates: Consumer Product Sources

Up to 40 ng/g dw

Kerrigan et al. 2015

Lower South Bay: 68 ± 26 ng/L Sacramento River: 17 ± 9 ng/L

Water

Sediment

Triclosan: Recent Environmental Detections in SF Bay

Effluent JUL 2011: 313 ± 72 ng/L JAN 2012: 58 ± 4 ng/L

Hensley et al. 2015 Palo Alto Regional Water

Quality Control Plant n = 4 each

RMP unpublished data, 2008 Kerrigan et al. 2015

0 1 2 3 4

00 - 02

02 - 04

04 - 06

06 - 08

08 - 10

14 - 16

18 - 20

24 - 26

28 - 30

32 - 34

36 - 38

40 - 42

44 - 46

Sediment Concentration TCS (ng/g)

Core

Inte

rval

(cm

)

South Bay Sediment Core

0 5 10 15 20

00 - 04

04 - 08

08 - 10

12 - 14

16 - 18

20 - 22

24 - 26

28 - 30

32 - 34

38 - 40

42 - 44

48 - 52

Sediment Concentration TCS (ng/g)

Core

Inte

rval

(cm

)

Central Bay Sediment Core 2007

1992

1950

2009

1994

1971

1950

produced in the 1960’s

produced in the 1960’s

Kerrigan et al. 2015

Triclosan

Triclosan: Key Data Gaps

Methyl Triclosan

Identified in SF Bay mussels via non-targeted analysis

Special Study 2017: Triclosan and Methyl Triclosan in Small Fish

• Chlorinated phosphates

• Triphenyl phosphate – Plastic component – Persistence and ecotoxicity – Levels in SF Bay near PNEC – Additional monitoring in 2017

Other Chemicals of Concern: Phosphate Flame Retardants

• Bisphenols – 2017 ✓ • Brominated azo dyes • Poly- and perfluorinated substances • Quaternary ammonium compounds • Synthetic musk fragrance ingredients

• Non-targeted analysis ✓

Future Monitoring Priorities

References Billinghurst Z, Clare AS, Fileman T, McEvoy J, Readman J, Depledge MH. 1998. Inhibition of barnacle settlement by the environmental oestrogen 4-nonylphenol and the natural oestrogen 17β oestradiol. Mar Poll Bull 36:833-839. Cheng Y-C, Chen H-W, Chen W-L, Chen C-Y, Wang G-S. 2016. Occurrence of nonylphenol and bisphenol A in household water pipes made of different materials. Environ Mon Assess 188:562. Diehl J, Johnson SE, Xia K, West A, Tomanek L. 2012. The distribution of 4-nonylphenol in marine organisms of North American Pacific Coast estuaries. Chemosphere 87:490-497. Gassel M, Harwani S, Park JS, Jahn A. 2013. Detection of nonylphenol and persistent organic pollutants in fish from the North Pacific Central Gyre. Mar Pollut Bull 73:231-242. Hamlin HJ, Marciano K, Downs CA. 2015. Migration of nonylphenol from food-grade plastic is toxic to the coral reef fish species Pseudochromis fridmani. Chemosphere 139:223-228. Hensley RN, Kerrigan JF, Pang H, Erickson PR, Grandbois M, McNeill K, et al. 2015. Triclosan, chlorinated triclosan derivatives, and hydroxylated polybrominated diphenyl ethers (OH-BDEs) in wastewater effluents. Environ Sci Wat Res Technol 1:316. Hirai H, Takada H, Ogata Y, Yamashita R, Mizukawa K, Saha M, et al. 2011. Organic micropollutants in marine plastics debris from the open ocean and remote and urban beaches. Mar Pollut Bull 62:1683-1692. Kerrigan JF, Engstrom DR, Yee D, Sueper C, Erickson PR, Grandbois M, et al. 2015. Quantification of hydroxylated polybrominated diphenyl ethers (OH-BDEs), triclosan, and related compounds in freshwater and coastal systems. PLoS One 10:e0138805. Klosterhaus SL, Grace R, Hamilton MC, Yee D. 2013. Method validation and reconnaissance of pharmaceuticals, personal care products, and alkylphenols in surface waters, sediments, and mussels in an urban estuary. Environ Int 54:92-99. Meador JP, Yeh A, Young G, Gallagher EP. 2016. Contaminants of emerging concern in a large temperate estuary. Environ Pollut 213:254-267. Schlenk D, Lavado R, Loyo-Rosales JE, Jones W, Maryoung L, Riar N, et al. 2012. Reconstitution studies of pesticides and surfactants exploring the cause of estrogenic activity observed in surface waters of the San Francisco Bay Delta. Environ Sci Technol 46:9106-9111.