Josh D. Butler

The primary biodegradation of dispersed crude oil in the sea.

Dispersants are important tools for stimulating the biodegradation of large oil spills. They are essentially a bioremediation tool - aiming to stimulate the natural process of aerobic oil biodegradation by dispersing oil into micron-sized droplets that become so dilute in the water column that the natural levels of biologically available nitrogen, phosphorus and oxygen are sufficient for microbial growth. Many studies demonstrate the efficacy of dispersants in getting oil off the water surface. Here we show that biodegradation of dispersed oil is prompt and extensive when oil is present at the ppm levels expected from a successful application of dispersants - more than 80% of the hydrocarbons of lightly weathered Alaska North Slope crude oil were degraded in 60 d at 8 °C in unamended New Jersey (USA) seawater when the oil was present at 2.5 ppm by volume. The apparent halftime of the biodegradation of the hydrocarbons was 13.8 d in the absence of dispersant, and 11 d in the presence of Corexit 9500 - similar to rates extrapolated from the field in the Deepwater Horizon response.

A novel passive dosing system for determining the toxicity of phenanthrene to early life stages of zebrafish.

Reliable experimental early life stage chronic toxicity data for fish are limited and further data are needed for polyaromatic hydrocarbons to establish environmental quality objectives and compare with toxicity model predictions. Efforts are underway to develop a zebrafish embryo toxicity test guideline to reduce, refine and replace the use of vertebrates in animal testing. An adaptation of this method which includes embryo lethal and sub-lethal developmental endpoints after a 5-day exposure as well as larval survival and growth endpoints during a subsequent 25-day test period is described using phenanthrene as a model test substance. To deliver well controlled exposure concentrations, a passive dosing system consisting of silicone coated vials and silicone O-rings was employed. Acute results indicated that edema and spinal curvature were the most sensitive sub-lethal effects observed and in many cases preceded observed mortality. The 30-day LC/EC10 for larval survival and growth was 40 and 67 μg/L respectively. Concentrations shown to cause adverse effects in this study are in the range of previous studies that have investigated the chronic effects of phenanthrene on fish. Further, results indicate that predicted water quality objectives for phenanthrene derived using the target lipid model are protective of early life stage effects on zebrafish. Based on these results the predicted water quality objectives for phenanthrene derived using the target lipid model (10 μg/L) would be protective of early life stage effects on zebrafish.

The Rate of Crude Oil Biodegradation in the Sea

Various groups have studied the rate of oil biodegradation in the sea over many years, but with no consensus on results. This can be attributed to many factors, but we show here that the principal confounding influence is the concentration of oil used in different experiments. Because of dilution, measured concentrations of dispersed oil in the sea are sub-parts-per-million within a day of dispersal, and at such concentrations the rate of biodegradation of detectable oil hydrocarbons has an apparent half-life of 7-14 days. This can be contrasted with the rate of degradation at the higher concentrations found in oil slicks or when stranded on a shoreline; there the apparent half-life varies from many months to many years.

Chronic toxicity of selected polycyclic aromatic hydrocarbons to algae and crustaceans using passive dosing.

Because of the large number of possible aromatic hydrocarbon structures, predictive toxicity models are needed to support substance hazard and risk assessments. Calibration and evaluation of such models requires toxicity data with well-defined exposures. The present study has applied a passive dosing method to generate reliable chronic effects data for 8 polycyclic aromatic hydrocarbons (PAHs) on the green algae Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia. The observed toxicity of these substances on algal growth rate and neonate production were then compared with available literature toxicity data for these species, as well as target lipid model and chemical activity-based model predictions. The use of passive dosing provided well-controlled exposures that yielded more consistent data sets than attained by past literature studies. Results from the present study, which were designed to exclude the complicating influence of ultraviolet light, were found to be well described by both target lipid model and chemical activity effect models. The present study also found that the lack of chronic effects for high molecular weight PAHs was consistent with the limited chemical activity that could be achieved for these compounds in the aqueous test media. Findings from this analysis highlight that variability in past literature toxicity data for PAHs may be complicated by both poorly controlled exposures and photochemical processes that can modulate both exposure and toxicity. Environ Toxicol Chem 2016;35:2948-2957.

A re‐evaluation of PETROTOX for predicting acute and chronic toxicity of petroleum substances

The PETROTOX model was developed to perform aquatic hazard assessment of petroleum substances based on substance composition. The model relies on the hydrocarbon block method, which is widely used for conducting petroleum substance risk assessments providing further justification for evaluating model performance. Previous work described this model and provided a preliminary calibration and validation using acute toxicity data for limited petroleum substance. The objective of the present study was to re-evaluate PETROTOX using expanded data covering both acute and chronic toxicity endpoints on invertebrates, algae, and fish for a wider range of petroleum substances. The results indicated that recalibration of 2 model parameters was required, namely, the algal critical target lipid body burden and the log octanol-water partition coefficient (KOW ) limit, used to account for reduced bioavailability of hydrophobic constituents. Acute predictions from the updated model were compared with observed toxicity data and found to generally be within a factor of 3 for algae and invertebrates but overestimated fish toxicity. Chronic predictions were generally within a factor of 5 of empirical data. Furthermore, PETROTOX predicted acute and chronic hazard classifications that were consistent or conservative in 93 and 84% of comparisons, respectively. The PETROTOX model is considered suitable for the purpose of characterizing petroleum substance hazard in substance classification and risk assessments. Environ Toxicol Chem 2017;36:2245-2252.

Assessing Aromatic-Hydrocarbon Toxicity to Fish Early Life Stages Using Passive-Dosing Methods and Target-Lipid and Chemical-Activity Models

Aromatic hydrocarbons (AH) are known to impair fish early life stages (ELS). However, poorly defined exposures often confound ELS-test interpretation. Passive dosing (PD) overcomes these challenges by delivering consistent, controlled exposures. The objectives of this study were to apply PD to obtain 5 d acute embryo lethality and developmental data and 30 d chronic embryo-larval survival and growth-effects data using zebrafish with different AHs; to analyze study and literature toxicity data using target-lipid (TLM) and chemical-activity (CA) models; and to extend PD to a mixture and test the assumption of AH additivity. PD maintained targeted exposures over a concentration range of 6 orders of magnitude. AH toxicity increased with log Kow up to pyrene (5.2). Pericardial edema was the most sensitive sublethal effect that often preceded embryo mortality, although some AHs did not produce developmental effects at concentrations causing mortality. Cumulative embryo-larval mortality was more sensitive than larval growth, with acute-to-chronic ratios of <10. More-hydrophobic AHs did not exhibit toxicity at aqueous saturation. The relationship and utility of the TLM-CA models for characterizing fish ELS toxicity is discussed. Application of these models indicated that concentration addition provided a conservative basis for predicting ELS effects for the mixture investigated.

Evaluating persistence of petroleum hydrocarbons in aerobic aqueous media.

Evaluating chemical persistence is essential in performing environmental risk assessments with biodegradation data being a key requirement of many national, regional and local regulatory bodies. The results from such assessments will, together with information relating to toxicity and bioaccumulation, determine classification and labeling under global (Global Harmonized System; GHS, Winder et al., 2005) and/or regional (Classification, Labelling and Packaging; CLP, Lahl and Hawxwell, 2006) regulations. The physical and chemical variability found in petroleum hydrocarbons however, present unique challenges in assessing

Investigating the role of dissolved and droplet oil in aquatic toxicity using dispersed and passive dosing systems.

Characterization of the aquatic toxicity of oil is needed to support hazard assessment and inform spill response. Natural processes and mitigation strategies involving dispersant use can result in exposures to both dissolved and droplet oil that are not typically differentiated when oil exposures are characterized in toxicity tests. Thus, the impact of droplets on aquatic toxicity is largely uncharacterized. To improve the understanding of the role of droplets, acute toxicity tests with Daphnia magna and Americamysis bahia were performed with Endicott crude oil in low-energy mixing systems with and without Corexit 9500 dispersant. Exposures were also prepared by placing crude oil in silicone tubing and passively dosing test media to provide dissolved oil exposures without droplets. A framework is described for characterizing dissolved phase exposures using both mechanistic modeling and passive sampling measurements. The approach is then illustrated by application to data from the present study. Expression of toxicity in terms of toxic units calculated from modeled dissolved oil concentrations or passive sampling measurements showed similar dose responses between exposure systems and organisms, despite the gradient in droplet oil. These results indicate that droplets do not appreciably contribute to toxicity for the 2 species investigated and further support hazard evaluation of dispersed oil on the basis of dissolved exposure metrics. Environ Toxicol Chem 2017;36:1020-1028.

Application of the Target Lipid Model and Passive Samplers to Characterize the Toxicity of Bioavailable Organics in Oil Sands Process-Affected Water

Oil sand operations in Alberta, Canada will eventually include returning treated process-affected waters to the environment. Organic constituents in oil sand process-affected water (OSPW) represent complex mixtures of nonionic and ionic (e.g., naphthenic acids) compounds, and compositions can vary spatially and temporally, which has impeded development of water quality benchmarks. To address this challenge, it was hypothesized that solid phase microextraction fibers coated with polydimethylsiloxane (PDMS) could be used as a biomimetic extraction (BE) to measure bioavailable organics in OSPW. Organic constituents of OSPW were assumed to contribute additively to toxicity, and partitioning to PDMS was assumed to be predictive of accumulation in target lipids, which were the presumed site of action. This method was tested using toxicity data for individual model compounds, defined mixtures, and organic mixtures extracted from OSPW. Toxicity was correlated with BE data, which supports the use of this method in hazard assessments of acute lethality to aquatic organisms. A species sensitivity distribution (SSD), based on target lipid model and BE values, was similar to SSDs based on residues in tissues for both nonionic and ionic organics. BE was shown to be an analytical tool that accounts for bioaccumulation of organic compound mixtures from which toxicity can be predicted, with the potential to aid in the development of water quality guidelines.