Mace G. Barron

Comparative toxicity of eight oil dispersants, Louisiana sweet crude oil (LSC), and chemically dispersed LSC to two aquatic test species

The present study describes the acute toxicity of eight commercial oil dispersants, South Louisiana sweet crude oil (LSC), and chemically dispersed LSC. The approach used consistent test methodologies within a single laboratory in assessing the relative acute toxicity of the eight dispersants, including Corexit 9500A, the predominant dispersant applied during the DeepWater Horizon spill in the Gulf of Mexico. Static acute toxicity tests were performed using two Gulf of Mexico estuarine test species, the mysid shrimp (Americamysis bahia) and the inland silversides (Menidia beryllina). Dispersant-only test solutions were prepared with high-energy mixing, whereas water-accommodated fractions of LSC and chemically dispersed LSC were prepared with moderate energy followed by settling and testing of the aqueous phase. The median lethal concentration (LC50) values for the dispersant-only tests were calculated using nominal concentrations, whereas tests conducted with LSC alone and dispersed LSC were based on measured total petroleum hydrocarbon (TPH) concentrations. For all eight dispersants in both test species, the dispersants alone were less toxic (LC50s: 2.9 to >5,600 µl/L) than the dispersant-LSC mixtures (0.4-13 mg TPH/L). Louisiana sweet crude oil alone had generally similar toxicity to A. bahia (LC50: 2.7 mg TPH/L) and M. beryllina (LC50: 3.5 mg TPH/L) as the dispersant-LSC mixtures. The results of the present study indicate that Corexit 9500A had generally similar toxicity to other available dispersants when tested alone but was generally less toxic as a mixture with LSC.

Critical evaluation of CROSERF test methods for oil dispersant toxicity testing under subarctic conditions

The aquatic organisms toxicity testing protocols developed by the chemical response to oil spills: Ecological Research Forum (CROSERF) were evaluated for applicability to assessing chemical dispersant toxicity under subarctic conditions. CROSERF participants developed aquatic toxicity testing protocols with the foremost objective of standardizing test methods and reducing inter-laboratory variability. A number of refinements are recommended to adapt the CROSERF protocols for testing with subarctic species under conditions of expected longer oil persistence. Recommended refinements of the CROSERF protocols include testing fresh and moderately weathered oil under conditions of moderate mixing energy, preparing toxicity test solutions using variable dilutions rather than variable loading, performing tests with subarctic species using static exposures in open chambers, increasing the duration of tests from 4 to 7 days, quantifying approximately 40 PAHs and their alkyl homologs, assessing the potential for photoenhanced toxicity, and incorporating a bioaccumulation endpoint by measuring tissue concentrations of PAHs. Refinements in the preparation of oil dosing solutions, exposure and light regimes, and analytical chemistry should increase the utility of the test results for interpreting the toxicity of chemically dispersed oil and making risk management decisions regarding dispersant use under subarctic conditions.

Determinants of variability in acute to chronic toxicity ratios for aquatic invertebrates and fish

Variability in acute to chronic ratios (ACRs; median lethal or effect concentration divided by chronic value) has been of continuing interest in aquatic toxicology because of the reliance on ACRs to estimate chronic toxicity for chemicals and species with known acute toxicity data but with limited or no information for chronic toxicity. To investigate the variability and significant differences in ACRs, an extensive data set was compiled of 456 same-species pairs of acute and maximum acceptable toxicant concentrations for metals, narcotics, pesticides, and other organic chemicals. The overall median value for 456 aquatic invertebrate and fish ACRs analyzed in the present study was 8.3, with a 16,000-fold range in values (1.1-18,550) and a 32-fold range in 10th and 90th percentile values (2.5-79.5). Median ACRs for taxa, ambient habitat media, chronic test end point, and chemical mode of action (MOA)/class categories generally were similar but, in some cases, extremely variable (ranges of 1 to >10,000). No significant differences (p <or= 0.05) were found in median ACRs between taxa, although invertebrate ACRs generally were more variable than fish ACRs. Freshwater organisms had median ACRs significantly greater than those of saltwater species and also were more variable. No significant differences were found in median ACRs among chemical MOA/class data sets; however, ACR variance differed significantly among MOAs. Although few significant differences occurred among median ACRs for different groups, those categories that were highly variable are at an increased risk of underestimated chronic toxicity when mean or median ACRs are used.

Contaminant exposure and effects in pinnipeds: implications for Steller sea lion declines in Alaska

After nearly 3 decades of decline, the western stock of Steller sea lions (SSL; Eumetopias jubatus) was listed as an endangered species in 1997. While the cause of the decline in the 1970s and 1980s has been attributed to nutritional stress, recent declines are unexplained and may result from other factors including the presence of environmental contaminants. SSL tissues show accumulation of butyltins, mercury, PCBs, DDTs, chlordanes and hexachlorobenzene. SSL habitats and prey are contaminated with additional chemicals including mirex, endrin, dieldrin, hexachlorocyclohexanes, tetrachlorodibenzo-p-dioxin (TCDD) and related compounds, cadmium and lead. In addition, many SSL haulouts and rookeries are located near other hazards including radioactivity, solvents, ordnance and chemical weapon dumps. PCB and DDT concentrations measured in a few SSL during the 1980s were the highest recorded for any Alaskan pinniped. Some contaminant exposures in SSL appear to be elevated in the Gulf of Alaska and Bering Sea compared to southeast Alaska, but there are insufficient data to evaluate geospatial relationships with any certainty. Based on very limited blubber data, current levels of PCBs may not pose a risk to SSL based on comparison to immunotoxicity tissue benchmarks, but SSL may have been at risk from pre-1990 PCB exposures. While exposure to PCBs and DDTs may be declining, SSL are likely exposed to a multitude of other contaminants that have not been monitored. The impacts of these exposures on SSL remain unknown because causal effects have not been established. Field studies with SSL have been limited in scope and have not yet linked contaminant exposures to adverse animal health or population effects. Several biomarkers may prove useful for monitoring exposure and additional research is needed to evaluate their utility in SSL. We conclude that there are insufficient data to reject the hypothesis that contaminants play a role in the continued decline of SSL, and suggest that a coordinated monitoring program be developed which can be related to key biological, ecological and laboratory toxicity data.

Potential for Photoenhanced Toxicity of Spilled Oil in Prince William Sound and Gulf of Alaska Waters

Photoenhanced toxicity is the increase in the toxicity of a chemical in the presence of ultraviolet light (UV) compared to a standard laboratory test conducted with fluorescent lighting (minimal UV). Oil products, weathered oil, and specific polycyclic aromatic compounds present in oil are 2 to greater than 1000 times more toxic in the presence of UV. The photoenhanced toxicity of oil to fish and aquatic invertebrates appears to occur through a process of photosensitization, rather than photomodification of the aqueous phase oil. In photosensitization, the bioaccumulated chemical transfers light energy to other molecules causing toxicity through tissue damage rather than a narcosis mechanism. The available evidence indicates that phototoxic components of oil are specific 3-5 ring polycyclic aromatic hydrocarbons (PAHs) and heterocycles. Determinants of photoenhanced toxicity include the extent of oil bioaccumulation in aquatic organisms and the spectra and intensity of UV exposure. No studies have specifically investigated the photoenhanced toxicity of spilled oil in Alaska waters. Although there are substantial uncertainties, the results of this evaluation indicate there is potential for photoenhanced toxicity of spilled oil in Prince William Sound and the Gulf of Alaska. The potential hazard of photoenhanced toxicity may be greatest for embryo and larval stages of aquatic organisms that are relatively translucent to UV and inhabit the photic zone of the water column and intertidal areas. Photoenhanced toxicity should be considered in oil spill response because the spatial and temporal extent of injury to aquatic organisms may be underestimated if based on standard laboratory bioassays and existing toxicity databases. Additionally, the choice of counter measures and oil removal operations may influence the degree of photoenhanced toxicity.

Protectiveness of species sensitivity distribution hazard concentrations for acute toxicity used in endangered species risk assessment

A primary objective of threatened and endangered species conservation is to ensure that chemical contaminants and other stressors do not adversely affect listed species. Assessments of the ecological risks of chemical exposures to listed species often rely on the use of surrogate species, safety factors, and species sensitivity distributions (SSDs) of chemical toxicity; however, the protectiveness of these approaches can be uncertain. We comprehensively evaluated the protectiveness of SSD first and fifth percentile hazard concentrations (HC1, HC5) relative to the application of safety factors using 68 SSDs generated from 1,482 acute (lethal concentration of 50%, or LC50) toxicity records for 291 species, including 24 endangered species (20 fish, four mussels). The SSD HC5s and HCls were lower than 97 and 99.5% of all endangered species mean acute LC50s, respectively. The HC5s were significantly less than the concentrations derived from applying safety factors of 5 and 10 to rainbow trout (Oncorhynchus mykiss) toxicity data, and the HCls were generally lower than the concentrations derived from a safety factor of 100 applied to rainbow trout toxicity values. Comparison of relative sensitivity (SSD percentiles) of broad taxonomic groups showed that crustaceans were generally the most sensitive taxa and taxa sensitivity was related to chemical mechanism of action. Comparison of relative sensitivity of narrow fish taxonomic groups showed that standard test fish species were generally less sensitive than salmonids and listed fish. We recommend the use of SSDs as a distribution-based risk assessment approach that is generally protective of listed species.

Influence of taxonomic relatedness and chemical mode of action in acute interspecies estimation models for aquatic species.

Ecological risks to aquatic organisms are typically assessed using acute toxicity data for relatively few species and with limited understanding of relative species sensitivity. We developed a comprehensive set of interspecies correlation estimation (ICE) models based on acute toxicity data for aquatic organisms and evaluated three key sources of model uncertainty: taxonomic relatedness, chemical mode of action (MOA), and model parameters. Models are least-squares regressions of acute toxicity of surrogate and predicted species. A total of 780 models were derived from acute values for 77 species of aquatic organisms and over 550 chemicals. Cross-validation of models showed that accurate model prediction was greatest for models with surrogate and predicted taxa within the same family (91% of predictions within 5-fold of measured values). Recursive partitioning provided user guidance for selection of robust models using model mean square error and taxonomic relatedness. Models built with a single MOA were more robust than models built using toxicity values with multiple MOAs, and improve predictions among species pairs with large taxonomic distance (e.g., within phylum). These results indicate that between-species toxicity extrapolation can be improved using MOA-based models for less related taxa pairs and for those specific MOAs.

A review of the tissue residue approach for organic and organometallic compounds in aquatic organisms

This paper reviews the tissue residue approach (TRA) for toxicity assessment as it applies to organic chemicals and some organometallic compounds (Sn, Hg, and Pb) in aquatic organisms. Specific emphasis was placed on evaluating key factors that influence interpretation of critical body residue (CBR) toxicity metrics including data quality issues, lipid dynamics, choice of endpoints, processes that alter toxicokinetics and toxicodynamics, phototoxicity, species- and life stage-specific sensitivities, and biotransformation. The vast majority of data available on TRA is derived from laboratory studies of acute lethal responses to organic toxicants exhibiting baseline toxicity. Application of the TRA to various baseline toxicants as well as substances with specific modes of action via receptor-mediated processes, such as chlorinated aromatic hydrocarbons, pesticides, and organometallics is discussed, as is application of TRA concepts in field assessments of tissue residues. In contrast to media-based toxicity relationships, CBR values tend to be less variable and less influenced by factors that control bioavailability and bioaccumulation, and TRA can be used to infer mechanisms of toxic action, evaluate the toxicity of mixtures, and interpret field data on bioaccumulated toxicants. If residue-effects data are not available, body residues can be estimated, as has been done using the target lipid model for baseline toxicants, to derive critical values for risk assessment. One of the primary unresolved issues complicating TRA for organic chemicals is biotransformation. Further work on the influence of biotransformation, a better understanding of contaminant lipid interactions, and an explicit understanding of the time dependency of CBRs and receptor-mediated toxicity are all required to advance this field. Additional residue-effects data on sublethal endpoints, early life stages, and a wider range of legacy and emergent contaminants will be needed to improve the ability to use TRA for organic and organometallic compounds.

Are Exposure and Ecological Risks of PAHs Underestimated at Petroleum Contaminated Sites

Ecological risk assessments conducted under the provisions of the Resource Conservation and Recovery Act (RCRA) and the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) typically rely on either U.S. Environmental Protection (USEPA) priority pollutant or Appendix IX analyte lists. These methods quantify only a limited subset of the polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatics found in oil and oil process wastes. Advances in analytical chemistry and petroleum fingerprinting techniques now show that the alkylated PAHs found in petroleum are more abundant and more persistent than the non-alkylated PAHs quantified by the traditional analytical methods applied in ecological risk assessments. We performed a screening level evaluation using case studies of PAH contamination from petroleum releases in a lake receiving refinery wastes and intertidal sediments exposed to spilled oil to assess the magnitude of underestimation of risks to benthic invertebrates and wildlife. Risks were assessed using a probabilistic approach and demonstrated that traditional analytical chemistry approaches applied at RCRA and CERCLA sites will underestimate exposure and risks of petrogenic PAHs contaminating aquatic systems. This analysis also shows that the numerical correction factor that has been proposed to account for ‘unmeasured’ alkylated PAHs can also result in a substantial underestimation of PAH risks from petroleum releases

Minimizing risks from spilled oil to ecosystem services using influence diagrams: the Deepwater Horizon spill response.

Decision science tools can be used in evaluating response options and making inferences on risks to ecosystem services (ES) from ecological disasters. Influence diagrams (IDs) are probabilistic networks that explicitly represent the decisions related to a problem and their influence on desired or undesired outcomes. To examine how IDs might be useful in probabilistic risk management for spill response efforts, an ID was constructed to display the potential interactions between exposure events and the trade-offs between costs and ES impacts from spilled oil and response decisions in the DWH spill event. Quantitative knowledge was not formally incorporated but an ID platform for doing this was examined. Probabilities were assigned for conditional relationships in the ID and scenarios examining the impact of different response actions on components of spilled oil were investigated in hypothetical scenarios. Given the structure of the ID, potential knowledge gaps included understanding of the movement of oil, the ecological risk of different spill-related stressors to key receptors (e.g., endangered species, fisheries), and the need for stakeholder valuation of the ES benefits that could be impacted by a spill. Framing the Deepwater Horizon problem domain in an ID conceptualized important variables and relationships that could be optimally accounted for in preparing and managing responses in future spills. These features of the developed IDs may assist in better investigating the uncertainty, costs, and the trade-offs if large-scale, deep ocean spills were to occur again.