Recommendations for the advancement of oil-in-water media and source oil characterization in aquatic toxicity test studies.

During toxicity testing, chemical analyses of oil and exposure media samples are needed to allow comparison of results between different tests as well as to assist with identification of the drivers and mechanisms for the toxic effects observed. However, to maximize the ability to compare results between different laboratories and biota, it has long been recognized that guidelines for standard protocols were needed. In 2005, the Chemical Response to Oil Spills: Ecological Effects Research Forum (CROSERF) protocol was developed with existing common analytical methods that described a standard method for reproducible preparation of exposure media as well as recommended specific analytical methods and analyte lists for comparative toxicity testing. At the time, the primary purpose for the data collected was to inform oil spill response and contingency planning. Since then, with improvements in both analytical equipment and methods, the use of toxicity data has expanded to include their integration into fate and effect models that aim to extend the applicability of lab-based study results to make predictions for field system-level impacts. This paper focuses on providing a summary of current chemical analyses for characterization of oil and exposure media used during aquatic toxicity testing and makes recommendations for the minimum analyses needed to allow for interpretation and modeling purposes.

Recommendations for advancing test protocols examining the photo-induced toxicity of petroleum and polycyclic aromatic compounds.

Photo-induced toxicity of petroleum products and polycyclic aromatic compounds (PACs) is the enhanced toxicity caused by their interaction with ultraviolet radiation and occurs by two distinct mechanisms: photosensitization and photomodification. Laboratory approaches for designing, conducting, and reporting of photo-induced toxicity studies are reviewed and recommended to enhance the original Chemical Response to Oil Spills: Ecological Research Forum (CROSERF) protocols which did not address photo-induced toxicity. Guidance is provided on conducting photo-induced toxicity tests, including test species, endpoints, experimental design and dosing, light sources, irradiance measurement, chemical characterization, and data reporting. Because of distinct mechanisms, aspects of photosensitization (change in compound energy state) and photomodification (change in compound structure) are addressed separately, and practical applications in laboratory and field studies and advances in predictive modeling are discussed. One goal for developing standardized testing protocols is to support lab-to-field extrapolations, which in the case of petroleum substances often requires a modeling framework to account for differential physicochemical properties of the constituents. Recommendations are provided to promote greater standardization of laboratory studies on photo-induced toxicity, thus facilitating comparisons across studies and generating data needed to improve models used in oil spill science.

Toxicity of oil spill response agents and crude oils to five aquatic test species.

The majority of aquatic toxicity data for petroleum products has been limited to a few intensively studied crude oils and Corexit chemical dispersants, and acute toxicity testing in two standard estuarine test species: mysids (Americamysis bahia) and inland silversides (Menidia beryllina). This study compared the toxicity of two chemical dispersants commonly stock piled for spill response (Corexit EC9500A®, Finasol®OSR 52), three less studied agents (Accell Clean®DWD dispersant; CytoSol® surface washing agent; Gelco200® solidifier), and three crude oils differing in hydrocarbon composition (Dorado, Endicott, Alaska North Slope). Consistent with listings on the U.S. National Contingency Plan Product Schedule, general rank order toxicity was greatest for dispersants and lowest for the solidifier. The results indicate that freshwater species can have similar sensitivity as the conventionally tested mysids and silversides, and that the sea urchin (Arbacia punctulata) appears to be a reasonable addition to increase taxa diversity in standardized oil agent testing.

Relative sensitivity of Arctic species to physically and chemically dispersed oil determined from three hydrocarbon measures of aquatic toxicity.

The risks to Arctic species from oil releases is a global concern, but their sensitivity to chemically dispersed oil has not been assessed using a curated and standardized dataset from spiked declining tests. Species sensitivity to dispersed oil was determined by their position within species sensitivity distributions (SSDs) using three measures of hydrocarbon toxicity: total petroleum hydrocarbons (TPH), polycyclic aromatic hydrocarbon (PAHs), and naphthalenes. Comparisons of SSDs with Arctic/sub-Arctic versus non-Arctic species, and across SSDs of compositionally similar oils, showed that Arctic and non-Arctic species have comparable sensitivities even with the variability introduced by combining data across studies and oils. Regardless of hydrocarbon measure, hazard concentrations across SSDs were protective of sensitive Arctic species. While the sensitivities of Arctic species to oil exposures resemble those of commonly tested species, PAH-based toxicity data are needed for a greater species diversity including sensitive Arctic species.

Development and practical application of petroleum and dispersant interspecies correlation models for aquatic species.

Assessing the acute toxicity of oil has generally relied on existing toxicological data for a relatively few standard test species, which has limited the ability to estimate the impacts of spilled oil on aquatic communities. Interspecies correlation estimation (ICE) models were developed for petroleum and dispersant products to facilitate the prediction of toxicity values to a broader range of species and to better understand taxonomic differences in species sensitivity. ICE models are log linear regressions that can be used to estimate toxicity to a diversity of taxa based on the known toxicity value for a surrogate tested species. ICE models have only previously been developed for nonpetroleum chemicals. Petroleum and dispersant ICE models were statistically significant for 93 and 16 unique surrogate-predicted species pairs, respectively. These models had adjusted coefficient of determinations (adj-R(2)), square errors (MSE) and positive slope ranging from 0.29 to 0.99, 0.0002 to 0.311, and 0.187 to 2.665, respectively. Based on model cross-validation, predicted toxicity values for most ICE models (>90%) were within 5-fold of the measured values, with no influence of taxonomic relatedness on prediction accuracy. A comparison between hazard concentrations (HC) derived from empirical and ICE-based species sensitivity distributions (SSDs) showed that HC values were within the same order of magnitude of each other. These results show that ICE-based SSDs provide a statistically valid approach to estimating toxicity to a range of petroleum and dispersant products with applicability to oil spill assessment.

Issues and challenges with oil toxicity data and implications for their use in decision making: a quantitative review.

Aquatic toxicity considerations are part of the net environmental benefit analysis and approval decision process on the use of dispersants in the event of an offshore oil spill. Substantial information is available on the acute toxicity of physically and chemically dispersed oil to a diverse subset of aquatic species generated under controlled laboratory conditions. However, most information has been generated following standard laboratory practices, which do not realistically represent oil spill conditions in the field. The goal of the present quantitative review is to evaluate the use of standard toxicity testing data to help inform decisions regarding dispersant use, recognizing some key issues with current practices, specifically, reporting toxicity metrics (nominal vs measured), exposure duration (standard durations vs short-term exposures), and exposure concentrations (constant vs spiked). Analytical chemistry data also were used to demonstrate the role of oil loading on acute toxicity and the influence of dispersants on chemical partitioning. The analyses presented here strongly suggest that decisions should be made, at a minimum, based on measured aqueous exposure concentrations and, ideally, using data from short-term exposure durations under spiked exposure concentrations. Available data sets are used to demonstrate how species sensitivity distribution curves can provide useful insights to the decision-making process on dispersant use. Finally, recommendations are provided, including the adoption of oil spill-appropriate toxicity testing practices.

Effectiveness and potential ecological effects of offshore surface dispersant use during the Deepwater Horizon oil spill: a retrospective analysis of monitoring data.

The Special Monitoring of Applied Response Technologies (SMART) program was used during the Deepwater Horizon oil spill as a strategy to monitor the effectiveness of sea surface dispersant use. Although SMART was implemented during aerial and vessel dispersant applications, this analysis centers on the effort of a special dispersant missions onboard the M/V International Peace, which evaluated the effectiveness of surface dispersant applications by vessel only. Water samples (n = 120) were collected from background sites, and under naturally and chemically dispersed oil slicks, and were analyzed for polycyclic aromatic hydrocarbons (TPAHs), total petroleum hydrocarbons (TPH), and a chemical marker of Corexit (dipropylene glycol n-butyl ether, DPnB). Water chemistry results were analyzed relative to SMART field assessments of dispersant effectiveness ("not effective," "effective," and "very effective"), based on in situ fluorometry. Chemistry data were also used to indirectly determine if the use of dispersants increased the risk of acute effects to water column biota, by comparison to toxicity benchmarks. TPAH and TPH concentrations in background, and naturally and chemically dispersed samples were extremely variable, and differences were not statistically detected across sample types. Ratios of TPAH and TPH between chemically and naturally dispersed samples provided a quantitative measure of dispersant effectiveness over natural oil dispersion alone, and were in reasonable agreement with SMART field assessments of dispersant effectiveness. Samples from "effective" and "very effective" dispersant applications had ratios of TPAH and TPH up to 35 and 64, respectively. In two samples from an "effective" dispersant application, TPHs and TPAHs exceeded acute benchmarks (0.81 mg/L and 8 µg/L, respectively), while none exceeded DPnB's chronic value (1,000 µg/L). Although the primary goal of the SMART program is to provide near real-time effectiveness data to the response, and not to address concerns regarding acute biological effects, the analyses presented here demonstrate that SMART can generate information of value to a larger scientific audience. A series of recommendations for future SMART planning are also provided.

Risk assessment of the National Institute of Standards and Technology petroleum crude oil standard water accommodated fraction: further application of a copepod-based, full life-cycle bioassay.

The U.S. National Institute of Standards and Technology (NIST) petroleum crude oil was used to generate NIST water-accommodated hydrocarbon fractions (WAFs) for standardized assessment of crude oil effects on the copepod Amphiascus tenuiremis. Effects were assessed using a 96-well microplate, full life-cycle test. Briefly, nauplii (age, 24 h) were reared individually to adults (n > or =120 nauplii/treatment) in microplate wells containing 200 microl of treatment solution (seawater control [0%] or 10, 30, 50, or 100% NIST-WAF). Nauplii were monitored through development to adulthood, and mature virgin male:female pairs mated in wells containing original treatments (<30 d). A second bioassay using 0, 10, 30, and 50% WAFs (n > or =60 nauplii/treatment) was conducted to assess the effects of ultraviolet (UV) light on naupliar endpoints (<16 d). In the first experiment, nauplius-to-copepodite survival in exposures to 100% WAF was 27% +/- 6% lower than in controls (92% +/- 1%), but copepodite-to-adult survival was greater than 90% across all treatments. Analysis of development curves showed that nauplii in the 10% WAF developed into copepodites 25% faster, whereas nauplii in the 50 and 100% WAFs developed 17% slower, than controls. Copepodite development into male and female copepods was significantly delayed (2 and 4 d, respectively) in the 100% WAF compared to controls. Although none of the WAF exposures had significant effects on fertilization success or total viable production (p > 0.05), embryo hatching in the 100% WAF was significantly less (70.0% +/- 21.2%) than that in controls (87.0% +/- 19.4%). Results from the UV bioassay showed that relatively short exposures (<14 d) to 30 and 50% WAFs in the presence of UV light caused negative effects on copepod survival and development. Naupliar-stage survival and developmental endpoints were the most sensitive indicators of exposure to the NIST crude oil WAF