A baseline assessment of contamination in the Sacramento deep water ship channel.

The Sacramento Deep Water Ship Channel (SDWSC) in the San Francisco Estuary, which is an active commercial port, is critical habitat for pelagic fish species including delta smelt (Hypomesus transpacificus), longfin smelt (Spirinchus thaleichthys), and Sacramento perch (Archoplites interruptus). Pelagic organism decline has been attributed to covarying factors such as manipulation of habitat, introduction of invasive species, decrease in food production, and contaminant exposure. Quantification of bioavailable toxicant loads in the SDWSC is limited despite previous surveys that have detected elevated contaminant concentrations in the sediments. Therefore, the focus of the present study was to characterize the bioavailability of the contaminants in the SDWSC from six sites along the channel. At each site, organochlorine pesticides (OCPs), pyrethroid insecticides, polyaromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were quantified in sediment, zooplankton, and suspended solids. In addition, Tenax extraction was used to measure the bioaccessible fraction of sediment-associated contaminants freely dissolved in the water. Bioaccessible contaminants in the sediment provided an uptake route for these stressors into invertebrates and fish with bioaccessible OCPs being found at all sites, particularly 4,4'-dichlorodiphenyldichloroethylene (DDE). Bifenthrin was the only pyrethroid detected in the chosen matrices and it was found at concentrations below levels of concern. Bioaccessible PAHs were found at all sites, with highest detections for phenanthrene and pyrene. No PCBs were detected in sediments, but were detected in both suspended solids and zooplankton. Contaminant concentrations overall were significantly higher in suspended solids, followed by zooplankton and sediments. The highest sediment concentrations of DDE, fluoranthene, pyrene, and dibenzo[a,h]anthracene exceeded sediment quality benchmarks indicating potential risk to sediment-dwelling species. Finally, elevated contaminant levels were found in both suspended solids and zooplankton, suggesting additional risk to pelagic species in the SDWSC.

The Roles of Diet and Habitat Use in Pesticide Bioaccumulation by Juvenile Chinook Salmon: Insights from Stable Isotopes and Fatty Acid Biomarkers.

Stable isotopes (SI) and fatty acid (FA) biomarkers can provide insights regarding trophic pathways and habitats associated with contaminant bioaccumulation. We assessed relationships between SI and FA biomarkers and published data on concentrations of two pesticides [dichlorodiphenyltrichloroethane and degradation products (DDX) and bifenthrin] in juvenile Chinook Salmon (Oncorhynchus tshawytscha) from the Sacramento River and Yolo Bypass floodplain in Northern California near Sacramento. We also conducted SI and FA analyses of zooplankton and macroinvertebrates to determine whether particular trophic pathways and habitats were associated with elevated pesticide concentrations in fish. Relationships between DDX and both sulfur (δ34S) and carbon (δ13C) SI ratios in salmon indicated that diet is a major exposure route for DDX, particularly for individuals with a benthic detrital energy base. Greater use of a benthic detrital energy base likely accounted for the higher frequency of salmon with DDX concentrations > 60 ng/g dw in the Yolo Bypass compared to the Sacramento River. Chironomid larvae and zooplankton were implicated as prey items likely responsible for trophic transfer of DDX to salmon. Sulfur SI ratios enabled identification of hatchery-origin fish that had likely spent insufficient time in the wild to substantially bioaccumulate DDX. Bifenthrin concentration was unrelated to SI or FA biomarkers in salmon, potentially due to aqueous uptake, biotransformation and elimination of the pesticide, or indistinct biomarker compositions among invertebrates with low and high bifenthrin concentrations. One FA [docosahexaenoic acid (DHA)] and DDX were negatively correlated in salmon, potentially due to a greater uptake of DDX from invertebrates with low DHA or effects of DDX on FA metabolism. Trophic biomarkers may be useful indicators of DDX accumulation and effects in juvenile Chinook Salmon in the Sacramento River Delta.

Using an internal body residue approach to assess acute pesticide toxicity in juvenile Chinook salmon (Oncorhynchus tshawytscha).

The use of internal body residues has the potential to improve toxicological assessments of hydrophobic pesticides. The acute toxicity of three classes of pesticides were assessed in juvenile Chinook salmon using internal body residues. Chinook salmon were exposed to two current-use pesticides bifenthrin and fipronil, and 4,4'- dichlorodiphenyldichloroethylene (DDE), which is a degradation product of the legacy pesticide dichlorodiphenyltrichloroethane (DDT). After 96-h of aqueous exposure to each pesticide, the pesticide content in whole-body Chinook salmon homogenates was measured using gas chromatography/mass spectrometry with methane negative chemical ionization. The wet-weight (ww) normalized lethal residue at 50% mortality (LR50) was lowest for bifenthrin (0.654 nmol/g ww), followed by fipronil (7.17 nmol/g ww) and the sum of fipronil and its sulfone, sulfide, and desulfinyl degradation products (8.72 nmol/g ww). No lethality was observed for DDE, even at the highest body residue (>116 nmol/g ww). LR50 estimates were also normalized to dry weight and lipid content and compared to field-caught fish to assess risk. The use of a risk quotient approach indicated that bifenthrin imparts the highest risk of acute toxicity in juvenile Chinook salmon among the three pesticides tested. In comparison to external dose metrics, the use of internal body residues has the potential to improve risk assessment by providing a more direct link between pesticide concentration at the receptor site and toxicological effects.