Phototoxicity Assessments of Field Sites in Barataria Bay, Louisiana, USA, and Heavily Weathered Macondo Crude Oil: 4 Years after the Deepwater Horizon Oil Spill.

The Deepwater Horizon oil spill resulted in the release of large amounts of crude oil into waters of the Gulf of Mexico (USA). A significant portion of the oil reached coastal waters and shorelines where aquatic organisms reside. Four years after the spill, oil remains in small quantities along the coast. Given the high volume of oil coupled with the high ultraviolet light intensities of the Gulf of Mexico, continued polycyclic aromatic hydrocarbon phototoxicity may be occurring in the Gulf region. The objective of the present study was to determine the potential for phototoxicity at 5 field sites (oiled, remediated, and unoiled) in Barataria Bay (LA, USA) to caged mysid shrimp and sheepshead minnows and to evaluate the phototoxic potential of field-collected oil water accommodated fractions (WAFs). Water chemistries were similar between field-collected oil WAFs and ambient waters, excluding the most oiled field site. Field bioassays indicated no phototoxic risk of heavily weathered crude oil under the highly turbid conditions present during the study. Laboratory WAFs of field-collected oil resulted in phototoxicity to mysid shrimp, suggesting a potential for phototoxicity of heavily weathered crude oil remaining in the Gulf of Mexico. Environ Toxicol Chem 2019;38:1811-1819. © 2019 SETAC.

Photo-enhanced toxicity of undispersed and dispersed weathered Macondo crude oil to Pacific (Crassostrea gigas) and eastern oyster (Crassostrea virginica) larvae.

During the Deepwater Horizon oil spill rapid natural weathering of Macondo crude oil occurred during the transport of oil to coastal areas. In response to the DWH incident, dispersant was applied to Macondo crude oil to reduce the movement of oil to coastal regions. This study aimed to assess the narcotic and phototoxicity of water-accommodated fractions (WAFs) of weathered Macondo crude oil, and chemically-enhanced WAFs of Corexit 9500 to Pacific (Crassostrea gigas) and eastern (Crassostrea virginica) oyster larvae. Phototoxic effects were observed for larval Pacific oysters exposed to combinations of oil and dispersant, but not for oil alone. Phototoxic effects were observed for larval eastern oysters exposed to oil alone and combinations of oil and dispersant. Corexit 9500 did not exhibit phototoxicity but resulted in significant narcotic toxicity for Pacific oysters. Oyster larvae may have experienced reduced survival and/or abnormal development if reproduction coincided with exposures to oil or dispersant.

Predicting phototoxicity of alkylated PAHs, mixtures of PAHs, and water accommodated fractions (WAF) of neat and weathered petroleum with the phototoxic target lipid model.

The toxicity of petroleum can increase considerably after exposure to solar radiation, during which certain components in the mixture, including polycyclic aromatic hydrocarbons (PAHs), absorb light in ultraviolet and visible portions of the solar radiation spectrum. A phototoxic target lipid model (PTLM), previously developed to predict the phototoxicity of single PAHs, is validated for 4 species (Americamysis bahia, Rhepoxynius abronius, Daphnia magna, and Pimephales promelas) exposed to 12 compounds that are components of petroleum, including alkylated PAHs and dibenzothiophene. The PTLM is also used to predict the phototoxicity of binary and ternary mixtures of 3 PAHs, pyrene, anthracene, and fluoranthene, to A. bahia and Menidia beryllina. Finally, it is used to predict the toxicity of water accommodated fractions of neat and naturally weathered Macondo crude oil samples from the Deepwater Horizon oil spill sites. The Gulf of Mexico species, including A. bahia, M. beryllina, Cyprinodon variegatus, and Fundulus grandis were exposed to the oil samples under natural and simulated solar radiation. The results support the applicability of the PTLM for predicting the phototoxicity of petroleum. Environ Toxicol Chem 2018;37:2165-2174. © 2018 SETAC.

Phototoxic potential of undispersed and dispersed fresh and weathered Macondo crude oils to Gulf of Mexico Marine Organisms.

Crude oils contain a mixture of hydrocarbons, including phototoxic polycyclic aromatic hydrocarbons (PAHs) that have the ability to absorb ultraviolet (UV) light. Absorption of UV light by PAHs can substantially increase their toxicity to marine organisms. The objective of the present study was to examine the potential for phototoxicity of fresh and naturally weathered Macondo crude oils alone and in combination with the dispersant Corexit 9500 to mysid shrimp (Americamysis bahia), inland silverside (Menidia beryllina), sheepshead minnow (Cyprinodon variegatus), and Gulf killifish (Fundulus grandis). Acute toxicity tests were conducted using combinations of natural or artificial sunlight and low-energy water-accommodated fractions (WAFs) of fresh and weathered Macondo crude oils collected from the Gulf of Mexico. Studies were also conducted to compare the phototoxicity resulting from natural and artificial sunlight. Fresh Macondo crude oil was more phototoxic than weathered crude oils, both in the presence and in the absence of UV light. Differences in toxicity between fresh and weathered crude oils were likely attributed to lighter-ringed PAHs in fresh crude oils. Phototoxic PAHs were relatively resistant to weathering compared with lighter-ringed PAHs. The addition of Corexit 9500 to crude oil increased toxicity compared with tests with crude oil alone, by increasing phototoxic PAH concentrations in WAFs. Macondo crude oils had the potential to be phototoxic to Gulf of Mexico marine organisms if specific light conditions and PAH concentrations were present during the Deepwater Horizon oil spill. Environ Toxicol Chem 2017;36:2640-2650. © 2017 SETAC.

Evaluation of the phototoxicity of unsubstituted and alkylated polycyclic aromatic hydrocarbons to mysid shrimp (Americamysis bahia): Validation of predictive models.

Crude oils are composed of an assortment of hydrocarbons, some of which are polycyclic aromatic hydrocarbons (PAHs). Polycyclic aromatic hydrocarbons are of particular interest due to their narcotic and potential phototoxic effects. Several studies have examined the phototoxicity of individual PAHs and fresh and weathered crude oils, and several models have been developed to predict PAH toxicity. Fingerprint analyses of oils have shown that PAHs in crude oils are predominantly alkylated. However, current models for estimating PAH phototoxicity assume toxic equivalence between unsubstituted (i.e., parent) and alkyl-substituted compounds. This approach may be incorrect if substantial differences in toxic potency exist between unsubstituted and substituted PAHs. The objective of the present study was to examine the narcotic and photo-enhanced toxicity of commercially available unsubstituted and alkylated PAHs to mysid shrimp (Americamysis bahia). Data were used to validate predictive models of phototoxicity based on the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap approach and to develop relative effect potencies. Results demonstrated that photo-enhanced toxicity increased with increasing methylation and that phototoxic PAH potencies vary significantly among unsubstituted compounds. Overall, predictive models based on the HOMO-LUMO gap were relatively accurate in predicting phototoxicity for unsubstituted PAHs but are limited to qualitative assessments. Environ Toxicol Chem 2017;36:2043-2049. © 2017 SETAC.

Photo-enhanced toxicity of two weathered Macondo crude oils to early life stages of the eastern oyster (Crassostrea virginica).

Polycyclic aromatic hydrocarbons (PAHs) have been reported to absorb ultraviolet (UV) light, resulting in enhanced toxicity. Early developmental stages of bivalves may be particularly susceptible to photo-enhanced toxicity during oil spills. In the current study, toxicity tests were conducted with sperm and three larval ages of the eastern oyster (Crassostrea virginica) to evaluate the photo-enhanced toxicity of low-energy water-accommodated fractions (WAFs) of two weathered Macondo crude oils collected from the Deepwater Horizon incident. Larvae exposed to oil WAFs under UV-filtered light demonstrated consistently higher survival and normal development than larvae exposed to WAFs under UV light. The phototoxicity of weathered Macondo oil increased as a function of increasing UV light intensity and dose. Early developing oyster larvae were the most sensitive to photo-enhanced toxicity, whereas later shelled prodissoconch larvae were insensitive. Comparisons between two weathered crude oils demonstrated that toxicity was dependent on phototoxic PAH concentration and UV light intensity.

Chronic effects of non-weathered and weathered crude oil and dispersant associated with the Deepwater Horizon incident on development of larvae of the eastern oyster, Crassostrea virginica.

The present study examined the effects of chronic exposure of eastern oyster (Crassostrea virginica) larvae to the water-accommodated fractions of fresh and weathered oils collected from the Deepwater Horizon incident, with and without additions of the dispersant Corexit 9500A, as well as to solutions of Corexit alone. Both shell growth of larvae exposed to test materials for a period of 10 d and larval settlement after 28 d of exposure were the most sensitive endpoints, with the 10-d growth endpoint being less variable among replicates. Growth and settlement endpoints were more sensitive than larval survival and normal development after 10 d and 28 d. Acute-to-chronic ratios calculated in the present study suggest that acute toxicities of oils and dispersant for oysters are not predictive of chronic effect levels for growth and settlement; therefore, chronic bioassays are necessary to assess these sublethal effects, in addition to standard 48-h acute toxicity tests. Comparison of 10% effective concentration (EC10) values for chronic 10-d growth and 28-d settlement endpoints with concentrations of total polycyclic aromatic hydrocarbons and dipropylene glycol n-butyl ether (a marker for Corexit) in seawater samples, collected during and after the Deepwater Horizon incident, indicated it was unlikely that elevated concentrations of water-soluble fractions of oil and dispersant in the nearshore environment had significant adverse effects on the growth and settlement of eastern oyster larvae. Environ Toxicol Chem 2016;35:2029-2040. © 2016 SETAC.

Acute effects of non-weathered and weathered crude oil and dispersant associated with the Deepwater Horizon incident on the development of marine bivalve and echinoderm larvae.

Acute toxicity tests (48-96-h duration) were conducted with larvae of 2 echinoderm species (Strongylocentrotus purpuratus and Dendraster excentricus) and 4 bivalve mollusk species (Crassostrea virginica, Crassostrea gigas, Mytilus galloprovincialis, and Mercenaria mercenaria). Developing larvae were exposed to water-accommodated fractions (WAFs) and chemically enhanced water-accommodated fractions (CEWAFs) of fresh and weathered oils collected from the Gulf of Mexico during the Deepwater Horizon incident. The WAFs (oils alone), CEWAFs (oils plus Corexit 9500A dispersant), and WAFs of Corexit alone were prepared using low-energy mixing. The WAFs of weathered oils had no effect on survival and development of echinoderm and bivalve larvae, whereas WAFs of fresh oils showed adverse effects on larval development. Similar toxicities were observed for weathered oil CEWAFs and WAFs prepared with Corexit alone for oyster (C. gigas and C. virginica) larvae, which were the most sensitive of the tested invertebrate species to Corexit. Mean 10% effective concentration values for total polycyclic aromatic hydrocarbons and dipropylene glycol n-butyl ether (a marker for Corexit) in the present study were higher than all concentrations reported in nearshore field samples collected during and after the Deepwater Horizon incident. The results suggest that water-soluble fractions of weathered oils and Corexit dispersant associated with the Deepwater Horizon incident had limited, if any, acute impacts on nearshore larvae of eastern oysters and clams, as well as other organisms with similar sensitivities to those of test species in the present study; however, exposure to sediments and long-term effects were not evaluated. Environ Toxicol Chem 2016;35:2016-2028. © 2016 SETAC.

Quantifying the concentration of crude oil microdroplets in oil-water preparations.

Dissolved constituents of crude oil, particularly polycyclic aromatic hydrocarbons (PAHs), can contribute substantially to the toxicity of aquatic organisms. Measured aqueous concentrations of high-molecular weight PAHs (e.g., chrysenes, benzo[a]pyrene) as well as long-chain aliphatic hydrocarbons can exceed the theoretical solubility of these sparingly soluble compounds. This is attributed to the presence of a "microdroplet" or colloidal oil phase. It is important to be able to quantify the dissolved fraction of these compounds in oil-in-water preparations that are commonly used in toxicity assays because the interpretation of test results often assumes that the compounds are dissolved. A method is presented to determine the microdroplet contribution in crude oil-in-water preparations using a comparison of predicted and measured aqueous concentrations. Measured concentrations are reproduced in the model by including both microdroplets and dissolved constituents of petroleum hydrocarbons. Microdroplets were found in all oil-water preparation data sets analyzed. Estimated microdroplet oil concentrations typically ranged from 10 to 700 µg oil/L water. The fraction of dissolved individual petroleum hydrocarbons ranges from 1.0 for highly soluble compounds (e.g., benzene, toluene, ethylbenzene, and xylene) to far less than 0.1 for sparingly soluble compounds (e.g., chrysenes) depending on the microdroplet oil concentration. The presence of these microdroplets complicates the interpretation of toxicity test data because they may exert an additional toxic effect due to a change in the exposure profile. The implications of the droplet model on toxicity are also discussed in terms of both dissolved hydrocarbons and microdroplets.

Predicting the toxicity of neat and weathered crude oil: toxic potential and the toxicity of saturated mixtures.

The toxicity of oils can be understood using the concept of toxic potential, or the toxicity of each individual component of the oil at the water solubility of that component. Using the target lipid model to describe the toxicity and the observed relationship of the solubility of oil components to log (Kow), it is demonstrated that components with lower log (Kow) have greater toxic potential than those with higher log (Kow). Weathering removes the lower-log (Kow) chemicals with greater toxic potential, leaving the higher-log (Kow) chemicals with lower toxic potential. The replacement of more toxically potent compounds with less toxically potent compounds lowers the toxicity of the aqueous phase in equilibrium with the oil. Observations confirm that weathering lowers the toxicity of oil. The idea that weathering increases toxicity is based on the erroneous use of the total petroleum hydrocarbons or the total polycyclic aromatic hydrocarbons (PAHs) concentration as if either were a single chemical that can be used to gauge the toxicity of a mixture, regardless of its makeup. The toxicity of the individual PAHs that comprise the mixture varies. Converting the concentrations to toxic units (TUs) normalizes the differences in toxicity. A concentration of one TU resulting from the PAHs in the mixture implies toxicity regardless of the specific PAHs that are present. However, it is impossible to judge whether 1 microg/L of total PAHs is toxic without knowing the PAHs in the mixture. The use of toxic potential and TUs eliminates this confusion, puts the chemicals on the same footing, and allows an intuitive understanding of the effects of weathering.

Toxicity of weathered Exxon Valdez crude oil to pink salmon embryos.

Research was conducted at the University of Idaho (Moscow, ID, USA) on the toxicity of weathered Exxon Valdez crude oil to embryos of pink salmon from 2001 to 2003 for the purpose of comparing these data with those from the National Oceanic and Atmospheric Administration Fisheries Laboratory at Auke Bay (AK, USA). Mortality reported at Auke Bay for embryos chronically exposed to very low concentrations of aqueous solutions of weathered oil, measured as dissolved polycyclic aromatic hydrocarbons (PAHs), was inconsistent with that in other published research. Using the Auke Bay experimental design, we found that toxicity is not evident in pink salmon embryos until chronic exposure to laboratory weathered and naturally weathered oil concentrations exceeding 1,500 and 2,250 ppm, respectively, representing a total PAH tissue burden in excess of 7,100 ppb. Effluent hydrocarbons also drop well below concentrations sufficient to cause harm over the time frame of a few weeks, regardless of oiling level. Resolution of differences with Auke Bay involved the source of contributing hydrocarbons. The experimental design did not exclude dispersed oil droplets from the aqueous solution; thus, toxicity was not limited to the dissolved hydrocarbon fraction. The implications of the present results are discussed regarding the toxic risk of weathered oil to pink salmon embryos in streams of Prince William Sound (AK, USA).

Hydrocarbon composition and toxicity of sediments following the Exxon Valdez oil spill in Prince William Sound, Alaska, USA.

An 1-year study of the 1989 Exxon Valdez oil spill found that spill residues on the oiled shorelines rapidly lost toxicity through weathering. After 1990, toxicity of sediments remained at only a few heavily oiled, isolated locations in Prince William Sound (AK, USA), as measured by a standard amphipod bioassay using Rhepoxynius abronius. Data from 648 sediment samples taken during the 1990 to 1993 period were statistically analyzed to determine the relationship between the total concentration of 39 parent and methyl-substituted polycyclic aromatic hydrocarbons (defined as total polycyclic aromatic hydrocarbons [TPAH]) and amphipod mortality and the effect of oil weathering on toxicity. A logistic regression model yielded estimates of the lower threshold, LC10 (lethal concentration to 10% of the population), and LC50 (median lethal concentration) values of 2,600, 4,100, and 10,750 ng/g TPAH (dry wt), respectively. Estimates of the threshold and LC50 values in this field study relate well to corresponding sediment quality guideline (SQG) values reported in the literature. For sediment TPAH concentrations >2,600 ng/g, samples with high mortality values (>90%) had relatively high fractions of naphthalenes and those with low mortality (<20%) had relatively high fractions of chrysenes. By 1999, the median sediment TPAH concentration of 117 ng/g for the post-1989 worst-case sites studied were well below the 2,600 ng/g toxicity threshold value, confirming the lack of potential for long-term toxic effects. Analysis of biological community structure parameters for sediment samples taken concurrently found that species richness and Shannon diversity decreased with increasing TPAH above the 2,600 ng/g threshold, demonstrating a correspondence between sediment bioassay results and biological community effects in the field. The low probability of exposure to toxic concentrations of weathered spill residues at the worst-case sites sampled in this study is consistent with the rapid overall recovery of shoreline biota observed in 1990 to 1991.