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

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

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

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)

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)

Major natural compound groups in samples. Compound GroupPlant Source I. Homologous Series n-Alkanesepicuticular waxes n-Alkenesalteration products n-Alkanalsepicuticular waxes n-Alkanoic acidsinternal lipid substances n-Alkanolsepicuticular waxes n-Alkanonesepicuticular waxes II. Molecular Biomarkers Monoterpenoids (C 10 )essential oils Sesquiterpenoids (C 15 )essential oils Diterpenoids (C 20 )gymnosperm resin, wax Steroidsinternal lipid substances Isoprenoidsinternal lipid substances Wax estersepicuticular waxes

Major anthropogenic compound groups in samples. Compound GroupUse Alkylbenzenessurfactants in detergents Nitro and polycyclicfragrances in cosmetics, muskspersonal care products PAHscombustion products PBDEsflame retardants Pesticidespest control Phenolsantioxidants, preservatives Phthalatesplasticizers

Contaminants of Concern TetraBDEPentaBDE 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 Triphenylphosphate Flame Retardants

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

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

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

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

Antioxidants and Related Products (continued)

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

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

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

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

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 Extended tricyclic terpanes HopanesSteranes Petroleum Products

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

Conclusions most unknown peaks were identified (>90%) levels ranged from pg/L (ppq) to g/L (ppb) contaminants did not exceed lowest LC 50 toxicity thresholds for most sensitive aquatic species

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)

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

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