Evaluation of Unknown Organic Contaminants in the San Francisco Estuary

1. Evaluation of Unknown Organic Contaminants in the San Francisco Estuary Daniel R. Oros and Nicole David San Francisco Estuary Institute Robert Risebrough Bodega Bay Institute

2. Question asked by RMP investigators in 2000: • What are ALL the unknown peaks in the GC-MS chromatograms? • Significance • first attempt at “surveillance monitoring” • makes system more “proactive” in identifying potential problem contaminants in the SF Estuary

3. Objectives • identify ALL the unknowns in the GC-MS chromatograms • estimate levels and determine distributions • link contaminants to known/suspected adverse impacts • target potential problem contaminants for monitoring

4. Methods Samples (archived GC-MS full scan data): • SF Estuary water (93/94, along Estuary spine) • SF Estuary sediment (93, along Estuary spine) • Sacramento and San Joaquin river water (93/94) • POTW waste water final effluent (98) Chemical Analysis: • sample solvent extraction and concentration • fractionation (3 each of increasing polarity) • gas chromatography-mass spectrometry (GC-MS)

5. Results Natural Sources: • Terrestrial • higher plant detritus (erosion, runoff) • plant waxes and pollen (atmospheric) • Aquatic • phytoplankton • zooplankton Anthropogenic Sources: • Agricultural runoff • Vehicular engines (lube oil, exhaust residues) • POTW effluents (direct input)

6. Major natural compound groups in samples. Compound GroupPlant Source I. Homologous Series n-Alkanes epicuticular waxes n-Alkenes alteration products n-Alkanals epicuticular waxes n-Alkanoic acids internal lipid substances n-Alkanols epicuticular waxes n-Alkanones epicuticular waxes II. Molecular Biomarkers Monoterpenoids (C10) essential oils Sesquiterpenoids (C15) essential oils Diterpenoids (C20) gymnosperm resin, wax Steroids internal lipid substances Isoprenoids internal lipid substances Wax esters epicuticular waxes

7. Major anthropogenic compound groups in samples. Compound GroupUse Alkylbenzenes surfactants in detergents Nitro and polycyclic fragrances in cosmetics, musks personal care products PAHs combustion products PBDEs flame retardants Pesticides pest control Phenols antioxidants, preservatives Phthalates plasticizers

11. Contaminants of Concern Flame Retardants TetraBDE PentaBDE Triphenylphosphate HexaBDE Sources: textiles, household and industrial products Use: reduces flame capacity of materials Max level: ppt (ng/L) Sacramento River water Concern: endocrine system disruption, bioaccumulation

12. Surfactants p-Nonylphenol ethoxylates (n= 1-15) Nonylphenol Sources: household and industrial products Use: lowers surface tension of water Max level: ppt (ng/L) Sacramento River water Concern: endocrine system disruption, bioaccumulation

13. Plasticizers Di-n-butylphthalate Butylbenzyl phthalate Bis(2-ethylhexyl)- phthalate Sources: household and industrial products Use: adds flexibility to polymers Max level: ppb (g/L) Dumbarton Bridge water Concern: endocrine system disruption, bioaccumulation

14. Nitro and Polycyclic Musks Musk ambrette Musk ketone Musk xylene 4-Amino musk xylene (metabolic product) Galaxolide Tonalide Versalide Sources: cosmetics and personal care products Use: fragrances Max level: ppb (g/L) San Pablo Bay water Concern: bioaccumulation, toxicity

15. Antioxidants and Related Products Butylated hydroxy toluene (BHT) Butylated hydroxy anisole (BHA) 4-Methylene-2,6-di-t-butyl-2,5-cyclohexadien-1-one 2,6-Di-t-butyl-4-hydroxy-4-methyl-2,5-cyclohexadienone 2,6-Di-t-butyl-p- benzoquinone 2,6-Di-t-butyl-4- nitrophenol Sources: preservatives in foods and cosmetics Uses: prevents free radical oxidation Max level: ppb (g/L) Sacramento River water Concern: Unknown effects

16. Antioxidants and Related Products (continued)

17. Antiseptics Triclosan Methoxytriclosan Chloroxylenol Sources: consumer and personal care products Use: preservatives and disinfectants Max level: ppq (pg/L) waste water final effluent Concern: toxicity

18. Herbicides Benfluralin Trifluralin Oxadiazon Propyzamide Dacthal Sources: urban and agricultural runoff Uses: pest control Max level: ppt (ng/L) San Pablo Bay water Concern: toxicity

19. Pesticides Quintozene (fungicide) Diethyltoluamide (insecticide) Sources: urban and agricultural runoff Uses: pest control Max level: ppt (ng/L) San Pablo Bay water Concern: toxicity

20. Disinfectants Chlorophene (bactericide) Iridomyrmecin (bactericide) Source: household, hospital, and veterinary disinfectants Uses: antibacterial agents Max level: ppq (pg/L) waste water final effluent Concern: toxicity

21. Petroleum Products Extended tricyclic terpanes Hopanes Steranes Sources: engine exhaust residues, seepage, oil spills Use: fuel, lubricating oils Max level: ppt (µg/kg) South Bay sediments Concern: toxicity from UCM and PAH

22. Other Common Contaminants Octylmethoxy cinnamate (UV blocker in sunscreens) Benzophenone (fixative in soaps) Retene (conifer wood burning)

23. Conclusions • most unknown peaks were identified (>90%) • levels ranged from pg/L (ppq) to g/L (ppb) • contaminants did not exceed lowest LC50 toxicity thresholds for most sensitive aquatic species

24. contaminants of concern were identified based on ability to bioaccumulate, induce toxicity, and persist • contaminants recommended for 2002 RMP monitoring: Nitro and polycyclic musks (tissue only) Nonylphenol (water, sediment, tissue) PBDEs (water, sediment, tissue) Phthalates (water, sediment, tissue) Triphenylphosphate (water, sediment, tissue)

25. Future Work • analyze recent RMP tissue, sediment, and water samples for new contaminants

26. Acknowledgements Dr. Wayne Sovocool, U.S. EPA Environmental Chemistry Branch, National Exposure Research Laboratory, Las Vegas, NV