Evaluation of Unknown Organic Contaminants in the San Francisco Estuary
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Transcript of 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:
Terrestrialhigher plant detritus (erosion, runoff)plant waxes and pollen (atmospheric)
Aquaticphytoplanktonzooplankton
Anthropogenic Sources:
Agricultural runoffVehicular engines (lube oil, exhaust residues)POTW effluents (direct input)
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Major natural compound groups in samples.
Compound Group Plant SourceI. Homologous Series
n-Alkanes epicuticular waxesn-Alkenes alteration productsn-Alkanals epicuticular waxesn-Alkanoic acids internal lipid substancesn-Alkanols epicuticular waxesn-Alkanones epicuticular waxes
II. Molecular BiomarkersMonoterpenoids (C10) essential oilsSesquiterpenoids (C15) essential oilsDiterpenoids (C20) gymnosperm resin, waxSteroids internal lipid substancesIsoprenoids internal lipid substancesWax esters epicuticular waxes
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Major anthropogenic compound groups in samples.
Compound Group Use
Alkylbenzenes surfactants in detergentsNitro and polycyclic fragrances in cosmetics,
musks personal care productsPAHs combustion productsPBDEs flame retardants Pesticides pest controlPhenols antioxidants, preservativesPhthalates plasticizers
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O
Br Br
Br Br
Br Br
O
Br
Br
Br
Br
BrO
Br Br
Br Br
Contaminants of Concern
TetraBDE PentaBDE
HexaBDE
Sources: textiles, household and industrial productsUse: reduces flame capacity of materialsMax level: ppt (ng/L) Sacramento River waterConcern: endocrine system disruption, bioaccumulation
P
O
O
O
O
Triphenylphosphate
Flame Retardants
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Sources: household and industrial productsUse: lowers surface tension of waterMax level: ppt (ng/L) Sacramento River water Concern: endocrine system disruption, bioaccumulation
Nonylphenol
H(OCH2CH2)nOOH
Anaerobic metabolism
p-Nonylphenol ethoxylates(n= 1-15)
Surfactants
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OO
O
OOO
O
O
O
OOO
Sources: household and industrial products Use: adds flexibility to polymersMax level: ppb (g/L) Dumbarton Bridge water
Concern: endocrine system disruption, bioaccumulation
Di-n-butylphthalate Butylbenzyl phthalate
Bis(2-ethylhexyl)-phthalate
Plasticizers
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O
O2N NO2
Musk ambrette
O2N NO2
NO2
Musk xylene
O
O2N NO2
Musk ketone
O
Galaxolide
O
Versalide
NH2
O2N NO2
4-Amino musk xylene(metabolic product)
O
Tonalide
Sources: cosmetics and personal care productsUse: fragrancesMax level: ppb (g/L) San Pablo Bay waterConcern: bioaccumulation, toxicity
Nitro and Polycyclic Musks
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OH
Butylated hydroxy toluene (BHT)
OH
O
Butylated hydroxy anisole (BHA)
Sources: preservatives in foods and cosmeticsUses: prevents free radical oxidationMax level: ppb (g/L) Sacramento River waterConcern: Unknown effects
Antioxidants and Related Products
O
O
2,6-Di-t-butyl-p-benzoquinone
O
OH
2,6-Di-t-butyl-4-hydroxy-4-methyl-2,5-cyclohexadienone
O
4-Methylene-2,6-di-t-butyl-2,5-cyclohexadien-1-one
OH
NO2
2,6-Di-t-butyl-4-nitrophenol
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OH OH
OH
OH
2,4,6-Tris(1-methyl-1-phenylethyl)-phenol
2,4-Bis(dimethyl)benzyl-6-tert-butyl-phenol
2,4-Bis(dimethyl)benzyl-phenol
2,6-Bis(1,1-dimethyl)-4-(1-methyl-1-phenylethyl)-phenol
Antioxidants and Related Products (continued)
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OH
Cl
Chloroxylenol
O
ClCl
Cl OH
Triclosan
O
Cl Cl
OCl
CH3
Methoxytriclosan
Sources: consumer and personal care productsUse: preservatives and disinfectantsMax level: ppq (pg/L) waste water final effluent Concern: toxicity
Antiseptics
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F
FF
N
NO2
O2N
Benfluralin
F
FF
N
NO2
O2N
Trifluralin
O
NN
O
Cl
Cl
O
Oxadiazon
O
NCl
Cl
Propyzamide
Sources: urban and agricultural runoffUses: pest controlMax level: ppt (ng/L) San Pablo Bay waterConcern: toxicity
Cl
Cl
Cl
Cl
O
O
O
O
Dacthal
Herbicides
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NO
Diethyltoluamide(insecticide)
Cl
Cl
Cl
Cl
Cl
NO2
Quintozene(fungicide)
Sources: urban and agricultural runoffUses: pest controlMax level: ppt (ng/L) San Pablo Bay waterConcern: toxicity
Pesticides
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OH
Cl
Chlorophene(bactericide)
Source: household, hospital, and veterinary disinfectants Uses: antibacterial agentsMax level: ppq (pg/L) waste water final effluentConcern: toxicity
O
O
Iridomyrmecin(bactericide)
Disinfectants
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Sources: engine exhaust residues, seepage, oil spillsUse: fuel, lubricating oilsMax level: ppt (µg/kg) South Bay sedimentsConcern: toxicity from UCM and PAH
R
R = C2H5 - C8H17
R
R = H, C2H5, C3H7 - C8H17
R
R = H, CH3, C2H5
Extended tricyclic terpanes
Hopanes Steranes
Petroleum Products
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O
O
CH3O
Octylmethoxy cinnamate(UV blocker in sunscreens)
O
Benzophenone(fixative in soaps)
Other Common Contaminants
Retene(conifer wood burning)
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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
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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