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 Group I. Homologous Series n-Alkanes n-Alkenes n-Alkanals n-Alkanoic acids n-Alkanols n-Alkanones II. Molecular Biomarkers Monoterpenoids (C10) Sesquiterpenoids (C15) Diterpenoids (C20) Steroids Isoprenoids Wax esters Plant Source epicuticular waxes alteration products epicuticular waxes internal lipid substances epicuticular waxes epicuticular waxes essential oils essential oils gymnosperm resin, wax internal lipid substances internal lipid substances epicuticular waxes Major anthropogenic compound groups in samples. Compound Group Use Alkylbenzenes Nitro and polycyclic musks PAHs PBDEs Pesticides Phenols Phthalates surfactants in detergents fragrances in cosmetics, personal care products combustion products flame retardants pest control antioxidants, preservatives plasticizers RESPONSE 50 40 30 20 10 20 30 40 n-C26 n-C27 Pentabromo diphenyl ether n-C29 Hexabromo diphenyl ether n-C30 n-C31 n-C23 n-C24 n-C25 n-C21 n-C22 n-C20 1-Methyl-undecylbenzene 1-Ethyl-undecylbenzene 1-Methyl-dodecylbenzene BHT n-C15 1-Methyl-nonylbenzene 1-Ethyl-nonylbenzene 1-Methyl-decylbenzene kCounts 0 50 minutes TIME GC-MS total ion current trace of a 1994 river water sample from Sacramento River, Rio Vista, showing dissolved organic components (F1). Abbreviation: BHT = butylated hydroxy toluene. RESPONSE 125 100 75 50 25 150 20 30 Fluoranthene Pyrene 40 n-C24al Benzo[k]fluoranthene Benzo[a]pyrene n-C29 n-C31 n-C28al Indeno[1,2,3-cd]pyrene Benzo[ghi]perylene n-C30al C1-Pyrenes Cyclopenta[cd]pyrene n-C22al S8 Phenanthrene C1-Phenanthrenes 1,2,3,5-Tetrachloro-4,6-dimethylbenzene Acenaphthene D10 kC ounts 0 UCM 50 60 m inutes TIME GC-MS total ion current traces of a 1993 sediment sample from San Pablo Bay showing organic components (F2). Abbreviations: S8 = elemental sulfur, UCM = unresolved complex mixture. 20 30 40 50 Si Cholesta-3,5-diene Si Si Si 5 Si Si Galaxolide 4-Amino-musk xylene Oxadiazon U U 10 C16 FAME Musk ketone 15 C15 FAME RESPONSE 20 U Benzophenone U 2,6-Di-tert-butyl-pbenzoquinone U kCounts minutes TIME GC-MS total ion current trace of a 1993 water sample from Dumbarton Bridge showing dissolved organic components (F3). Abbreviations: FAME = fatty acid methyl ester, Si = silicone, U = unknown. Contaminants of Concern Flame Retardants Br Br Br Br O O Br Br Br Br Br TetraBDE PentaBDE Br Br O O P O O O Br Br Br HexaBDE Br Triphenylphosphate 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 Surfactants Anaerobic metabolism H(OCH2CH2)nO p-Nonylphenol ethoxylates (n= 1-15) HO 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 Plasticizers O O O O Di-n-butylphthalate O O O Butylbenzyl phthalate O O O O O 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 Nitro and Polycyclic Musks O2N NO2 O2N NO2 NO2 O2N NO2 O2N O O Musk ambrette Musk ketone O NH2 NO2 Musk xylene 4-Amino musk xylene (metabolic product) O O Galaxolide Tonalide Versalide Sources: cosmetics and personal care products Use: fragrances Max level: ppb (g/L) San Pablo Bay water Concern: bioaccumulation, toxicity Antioxidants and Related Products OH OH O O Butylated hydroxy Butylated hydroxy toluene (BHT) anisole (BHA) O OH 2,6-Di-t-butyl-4-hydroxy-4methyl-2,5-cyclohexadienone 4-Methylene-2,6-di-t-butyl2,5-cyclohexadien-1-one O OH O NO2 2,6-Di-t-butyl-pbenzoquinone 2,6-Di-t-butyl-4nitrophenol 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 (continued) OH 2,4,6-Tris(1-methyl-1phenylethyl)-phenol OH 2,4-Bis(dimethyl)benzyl6-tert-butyl-phenol OH 2,6-Bis(1,1-dimethyl)-4-(1-methyl1-phenylethyl)-phenol OH 2,4-Bis(dimethyl)benzylphenol Antiseptics CH3 Cl O Cl O Cl OH OH O Cl Cl Cl Cl Triclosan Methoxytriclosan Chloroxylenol Sources: consumer and personal care products Use: preservatives and disinfectants Max level: ppq (pg/L) waste water final effluent Concern: toxicity Herbicides NO2 Cl NO2 N N N O2N F F Benfluralin F O2N F Cl O N O Cl Cl O O Propyzamide Cl O Oxadiazon Cl Cl O F Trifluralin O Cl N F O Dacthal Sources: urban and agricultural runoff Uses: pest control Max level: ppt (ng/L) San Pablo Bay water Concern: toxicity Pesticides NO2 O Cl Cl Cl Cl N Cl Quintozene (fungicide) Diethyltoluamide (insecticide) Sources: urban and agricultural runoff Uses: pest control Max level: ppt (ng/L) San Pablo Bay water Concern: toxicity Disinfectants OH Cl Chlorophene (bactericide) O O Iridomyrmecin (bactericide) Source: household, hospital, and veterinary disinfectants Uses: antibacterial agents Max level: ppq (pg/L) waste water final effluent Concern: toxicity Petroleum Products R R R = C2H5 - C8H17 Extended tricyclic terpanes R R = H, CH3, C2H5 R = H, C2H5, C3H7 - C8H17 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 Other Common Contaminants O CH3O O O Octylmethoxy cinnamate (UV blocker in sunscreens) Retene (conifer wood burning) Benzophenone (fixative in soaps) 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 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