Evaluation of Unknown Organic Contaminants in the San Francisco Estuary

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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
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• 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

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• 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

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• 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)

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• 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)

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Major natural compound groups in
samples. Compound Group Plant 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
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• Major anthropogenic compound groups in samples.
• Compound Group Use
• 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

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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
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Surfactants
Nonylphenol
p-Nonylphenol ethoxylates (n 1-15)
Sources household and industrial products Use
lowers surface tension of water Max level ppt
(ng/L) Sacramento River water Concern endocrine
system disruption, bioaccumulation
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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
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Nitro and Polycyclic Musks
Musk ambrette
Musk xylene
Musk ketone
4-Amino musk xylene (metabolic product)
Galaxolide
Versalide
Tonalide
Sources cosmetics and personal care
products Use fragrances Max level ppb (?g/L)
San Pablo Bay water Concern bioaccumulation,
toxicity
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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-p- benzoquinone
2,6-Di-t-butyl-4-hydroxy-4-methyl-2,5-cyclohexadie
none
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
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Antioxidants and Related Products (continued)
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Antiseptics
Chloroxylenol
Triclosan
Methoxytriclosan
Sources consumer and personal care products Use
preservatives and disinfectants Max level ppq
(pg/L) waste water final effluent Concern
toxicity
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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
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Pesticides
Diethyltoluamide (insecticide)
Quintozene (fungicide)
Sources urban and agricultural runoff Uses pest
control Max level ppt (ng/L) San Pablo Bay
water Concern toxicity
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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
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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
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Other Common Contaminants
Octylmethoxy cinnamate (UV blocker in sunscreens)
Benzophenone (fixative in soaps)
Retene (conifer wood burning)
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• Conclusions
• most unknown peaks were identified (gt90)
• levels ranged from pg/L (ppq) to ?g/L (ppb)
• contaminants did not exceed lowest LC50 toxicity
  thresholds for most sensitive aquatic species

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• 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)

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

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