Search

Oil spill exposures are highly dynamic and are not comparable to laboratory exposures used in standard toxicity tests. Toxicokinetic-toxicodynamic (TKTD) models allow translation of effects observed in the laboratory to the field. To improve TKTD model calibration, new and previously published data from 148 tests were analyzed to estimate rates characterizing the time course of toxicity for 10 fish and 42 invertebrate species across 37 hydrocarbons. A key parameter in the TKTD model is the first-order rate that incorporates passive elimination, biotransformation, and damage repair processes. The results indicated that temperature (4-26 °C), organism size (0.0001-10 g), and substance log octanol-water partition coefficient (2-6) had limited influence on this parameter, which exhibited a 5th to 95th percentile range of 0.2-2.5 day

Bioaccumulation (B) assessment is challenging because there are various B‐metrics from laboratory and field studies, multiple criteria and thresholds for classifying bioaccumulative (B), very bioaccumulative (vB), and not bioaccumulative (nB) chemicals, as well as inherent variability and uncertainty in the data. These challenges can be met using a weight of evidence (WoE) approach. The Bioaccumulation Assessment Tool (BAT) provides a transparent WoE assessment framework that follows Organisation for Economic Co‐operation and Development (OECD) principles for performing a WoE analysis. The BAT guides an evaluator through the process of data collection, generation, evaluation, and integration of various lines of evidence (LoE) (i.e., B‐metrics) to inform decision‐making. Phenanthrene (PHE) is a naturally occurring chemical for which extensive B and toxicokinetics data are available. A B assessment for PHE using the BAT is described that includes a critical evaluation of 74 measured in vivo LoE for fish and invertebrate species from laboratory and field studies. The number of LoE are reasonably well balanced across taxa (i.e., fish and invertebrates) and the different B‐metrics. Additionally, in silico and in vitro biotransformation rate estimates and corresponding model‐predicted B‐metrics are included as corroborating evidence. Application of the BAT provides a consistent, coherent, and scientifically defensible WoE evaluation to conclude that PHE is not bioaccumulative (nB) because the overwhelming majority of the bioconcentration, bioaccumulation, and biomagnification metrics for both fish and invertebrates are below regulatory thresholds. An analysis of the relevant data using fugacity ratios is also provided, showing that PHE does not biomagnify in aquatic food webs. The critical review identifies recommendations to increase the consistency of B assessments, such as improved standardization of B testing guidelines, data reporting requirements for invertebrate studies, and consideration of temperature and salinity effects on certain B‐metrics. Integr Environ Assess Manag 2021;17:911–925. © 2021 Concawe. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC), KEY POINTS The Bioaccumulation Assessment Tool (BAT) provides a transparent framework that follows Organisation for Economic Co‐operation and Development (OECD) principles for performing a weight of evidence approach.A critical review of bioaccumulation and toxicokinetic data for phenanthrene is described that includes a critical evaluation of 74 measurements in fish and invertebrate species from laboratory and field studies.The overwhelming majority of bioaccumulation metrics are below regulatory thresholds.Recommendations to improve the consistency of bioaccumulation assessments are provided.

Quantitative structure-property relationship (QSPR) models for predicting primary biodegradation of petroleum hydrocarbons have been previously developed. These models use experimental data generated under widely varied conditions, the effects of which are not captured adequately within model formalisms. As a result, they exhibit variable predictive performance and are unable to incorporate the role of study design and test conditions on the assessment of environmental persistence. To address these limitations, a novel machine-learning System-Integrated Model (HC-BioSIM) is presented, which integrates chemical structure and test system variability, leading to improved prediction of primary disappearance time (DT50) values for petroleum hydrocarbons in fresh and marine water. An expanded, highly curated database of 728 experimental DT50 values (181 unique hydrocarbon structures compiled from 13 primary sources) was used to develop and validate a supervised model tree machine-learning model. Using relatively few parameters (6 system and 25 structural parameters), the model demonstrated significant improvement in predictive performance (root mean square error = 0.26, R

The acute toxicity of dispersed oil is well understood, and oil dilutes to levels below those of acute concern within hours of dispersion whether oil is dispersed by waves or by lower energy turbulence in the presence of chemical dispersants. Once dispersed, the hydrocarbon components of the spilled oil are degraded promptly by the native microbes in seawater, typically with an apparent half-life of 7–30 days even under Arctic conditions. Nevertheless, concern has been raised that this biodegradation might increase the oil's acute toxicity by generating and releasing toxic by-products. We show here, using Americamysis bahia as the test species, that this does not occur when dispersed oil is present at environmentally-relevant concentrations (initially 3 ppm oil dispersed with Corexit 9500 at a dispersant to oil ratio of 1:20). The guidelines for this toxicity test mandate a temperature of 26 ± 1C, rather warmer than the temperature of collection of the seawater from the New Jersey shore that we used as our experimental medium, so it is not surprising that biodegradation was especially rapid with a half-life for the loss of detectable hydrocarbons of approximately 4 days. We conducted sequential 4-day acute toxicity tests for 20 days, by which time the indigenous microorganisms had removed almost 80% of the detectable hydrocarbons in the lightly weathered crude oil. We saw no mortality in any of the five sequential tests.

Heterocyclic aromatic compounds can be found in crude oil and coal and often co-exist in environmental samples with their homocyclic aromatic counterparts. The target lipid model (TLM) is a modeling framework that relates aquatic toxicity to the octanol-water partition coefficient (KOW ) that has been calibrated and validated for hydrocarbons. A systematic analysis of the applicability of the TLM to heterocyclic aromatic compounds has not been performed. The objective of the present study was to compile reliable toxicity data for heterocycles and determine whether observed toxicity could be successfully described by the TLM. Results indicated that the TLM could be applied to this compound class by adopting an empirically derived coefficient that accounts for partitioning between water and lipid. This coefficient was larger than previously reported for aromatic hydrocarbons, indicating that these heterocyclic compounds exhibit higher affinity to target lipid and toxicity. A mechanistic evaluation confirmed that the hydrogen bonding accepting moieties of the heteroatoms helped explain differences in partitioning behavior. Given the TLM chemical class coefficient reported in the present study, heterocyclic aromatics can now be explicitly incorporated in TLM-based risk assessments of petroleum substances, other products, or environmental media containing these compounds. Environ Toxicol Chem 2021;40:3000-3009. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Water solubility is perhaps the single most important physical–chemical property determining the environmental fate and effects of organic compounds. Its determination is particularly challenging for compounds with extremely low solubility, frequently referred to as “difficult-to-test” substances and having solubility’s generally less than 0.1 mg/L. The existing regulatory water solubility test for these compounds is the column elution method. Its applicability, however, is limited, to non-volatile solid or crystalline hydrophobic organic compounds. There currently exists no test guideline for measuring the water solubility of very hydrophobic liquid, and potentially volatile, difficult-to-test compounds. This paper describes a “slow-stir” water solubility methodology along with results of a ring trial across five laboratories evaluating the method’s performance. The slow-stir method was applied to n-hexylcyclohexane, a volatile, liquid hydrophobic hydrocarbon. In order to benchmark the inter-laboratory variability associated with the proposed slow-stir method, the five laboratories separately determined the solubility of dodecahydrotriphenylene, a hydrophobic solid compound using the existing column elution guideline. Results across the participating laboratories indicated comparable reproducibility with relative standard deviations (RSD) of 20% or less reported for each test compound – solubility method pair. The inter-laboratory RSD was 16% for n-hexylcyclohexane (mean 14 µg/L, n = 5) using the slow-stir method. For dodecahydrotriphenylene, the inter-laboratory RSD was 20% (mean 2.6 µg/L, n = 4) using the existing column elution method. This study outlines approaches that should be followed and the experimental parameters that have been deemed important for an expanded ring trial of the slow-stir water solubility method. Supplementary Information The online version contains supplementary material available at 10.1186/s13065-021-00778-7.

Under the European REACH regulation, chemicals are assessed for persistence as part of weight-of-evidence determinations of persistence, bioaccumulation and toxicity (PBT), as required under Annex XIII and supported by an Integrated Assessment and Testing Strategy (ITS). This study describes the persistence assessment of phenanthrene, a data-rich polycyclic aromatic hydrocarbon (PAH), in accordance with this framework. All available data from screening and simulation tests, for water, soil and sediment compartments, plus other relevant information, have been compiled. These have been evaluated for reliability and relevance, and a weight-of-evidence determination of persistence has been carried out. Aspects relevant to the assessment, such as degradation metabolites, non-extractable residues (NER), test temperature and bioavailability, have also been considered. The resulting assessment considered a wide range of evidence, including 101 experimental data points. Phenanthrene was demonstrated to be readily biodegradable, a first-tier screen for non-persistence in the ITS. Furthermore, weight-of-evidence assessment of data for water, soil and sediment compartments supported a conclusion of “not persistent” (not P). In non-standard soil studies with sludge-amended soils, longer half-lives were observed. This was attributable to pyrogenic sources of and significantly reduced bioavailability of phenanthrene, highlighting the importance of bioavailability as a major source of variability in persistence data. Available simulation test data for the sediment compartment were found to be unreliable due to the anoxic impact of the use of a biodegradable solvent in a closed system, and were inconsistent with the broader weight of evidence. Estimation of photodegradation using AOPWIN and the APEX model demonstrated this to be an important fate process not currently considered in persistence assessments under REACH. The assessment is not in agreement with a recent regulatory decision in which phenanthrene was determined to be very persistent (vP). This assessment provides a case study for persistence assessment using the REACH ITS and highlights the need for improved guidance to improve consistency and predictability of assessments. This is particularly important for complex cases with data-rich chemicals, such as phenanthrene.

This work describes a novel application of atmospheric pressure gas chromatography time-of-flight mass spectrometry (APGC-TOF-MS) combined with solid-phase microextraction (SPME) for the simultaneous analysis of hydrocarbons and naphthenic acids (NAs) species in raw and ozone-treated oil sands process water (OSPW). SPME method using polydimethylsiloxane (PDMS)-coated fibers was validated using gas chromatography with flame ionization detector (GC-FID) to ensure the SPME extractions were operated appropriately. The ionization pathways of the hydrocarbon species in OSPW in the APGC source were verified by analyzing a mixture of eight polyaromatic hydrocarbons which were ionized primarily via charge transfer to produce [M+] while NAs in OSPW were found to be ionized through protonation to generate [MH+] in the wet APGC source. SPME/APGC-TOF-MS analysis demonstrated a different composition profile in OSPW #1, with 74.5% of hydrocarbon species, 23.4% of O2–NAs, and 2.1% of the oxidized NA species at extraction pH 2.0 compared with that obtained by UPLC-TOF-MS analysis (36.9% of O2–NAs, 26.8% of O3–NAs, 24.9% of O4–NAs, 9.1% of O5–NAs, 2.3% of O6–NAs). Moreover, the peak areas of the total NAs and the total peak areas of NAs + hydrocarbons measured by SPME/APGC-TOF-MS correlated excellently with the total NA concentration determined by UPLC-TOF-MS (R2 = 0.90) and the concentrations of the total acid-extractable organics determined by SPME/GC-FID (R2 = 0.98), respectively. APGC-TOF-MS integrated with the SPME techniques could extend the range of target compounds and be a promising alternative to evaluate and characterize NAs and hydrocarbon in different water types.

Hazard assessment of refinery effluents is challenging because of their compositional complexity. Therefore, a weight-of-evidence approach using a combination of tools is often required. Previous research has focused on several predictive tools for sophisticated chemical analyses: biomimetic extraction to quantify the potentially bioaccumulative substances, 2-dimensional gas chromatography, modeling approaches to link oil composition to toxicity (PETROTOX), and whole-effluent toxicity assessments using bioassays. The present study investigated the value of these tools by comparing predicted effects to actual effects observed in stream mesocosm toxicity studies with refinery effluents. Three different effluent samples, with and without fortification by neat petroleum substances, were tested in experimental freshwater streams. The results indicate that the biological community shifted at higher exposure levels, consistent with chronic toxicity effects predicted by both modeled toxic units and potentially bioaccumulative substance measurements. The present study has demonstrated the potential of the predictive tools and the robustness of the stream mesocosm design to improve our understanding of the environmental hazards posed by refinery effluents. Environ Toxicol Chem 2019;38:650-659. © 2018 SETAC.

Applying dispersants to spilled crude oil results in an oil in water dispersion of microscopic oil droplets that soon dilutes to levels below 1 ppm oil. These levels are substantially below those known to induce acute toxicity in 96-hour tests. We show here that oil hydrocarbons are biodegraded very rapidly in such situations (50% loss in 4 days in this experiment), and that no increase in acute toxicity to mysids (Americamysis bahia) is seen during this biodegradation, or over the following 20 days as the oil is further degraded (78% loss of detectable hydrocarbons in this experiment).

Distribution and elimination of petroleum products can be predicted in aerobic wastewater treatment plants (WWTPs) using models such as multimedia fate model SimpleTreat. An advantage of the SimpleTreat model is that it only requires a few basic properties of a chemical in wastewater to calculate partitioning, biodegradation and ultimately emissions to air, surface water and produced sludge. The SimpleTreat model structure reflects a WWTP scheme. However, refinery WWTPs typically incorporate more advanced treatment processes such as dissolved air flotation (DAF), a process that clarifies wastewaters by the removal of suspended matter such as oil or solids. The objective of this work was to develop a WWTP removal model that includes DAF treatment. To understand how including a DAF in the model affects the predicted concentrations of petroleum constituents in effluent, we replaced the primary sedimentation module in SimpleTreat with a module simulating DAF. Subsequently, we compared results from the WWTP-DAF model with results obtained with the original SimpleTreat model for a library of over 1500 representative hydrocarbon constituents. The increased air-water exchange in a WWTP-DAF unit resulted in higher predicted removal of volatile constituents. Predicted removal with DAF was on average 17% larger than removal with primary sedimentation. We compared modelled results with measured removal data from the literature, which supported that this model refinement continues to improve the technical basis of assessment of petroleum products.

The Chemical Response to Oil Spill: Ecological Effects Research Forum's water accommodated fraction procedure was compared with 2 alternative techniques in which crude oil was passively dosed from silicone tubing or O-rings. Fresh Macondo oil (MC252) was dosed at 30 mg/L using each approach to investigate oil dissolution kinetics, which was monitored by fluorometry as estimated oil equivalents (EOEs). Subsequent experiments with each dosing method were then conducted at multiple oil loadings. Following equilibration, test media were analytically characterized for polyaromatic hydrocarbons (PAHs) using gas chromatography (GC)-mass spectrometry and dissolved oil using biomimetic solid-phase microextraction (SPME). The results showed that equilibrium was achieved within 72 h for all methods. Measured PAH concentrations were compared with oil solubility model predictions of dissolved exposures. The concentration and composition of measured and predicted dissolved PAHs varied with oil loading and were consistent between dosing methods. Two-dimensional GC compositional data for this oil were then used to calculate dissolved toxic units for predicting MC252 oil acute toxicity across the expected range of species sensitivities. Predicted toxic units were nonlinear with loading and correlated to both EOE and biomimetic SPME. Passive dosing methods provide a practical strategy to deliver and maintain dissolved oil concentrations while avoiding the complicating role that droplets can introduce in exposure characterization and test interpretation. Environ Toxicol Chem 2018;37:2810-2819. © 2018 SETAC.

A predominant concern following oil spills is toxicity to aquatic organisms. However, few data are available on effects in deep-sea cold water fishes. The present study had 3 major objectives. The first was to investigate the relative sensitivity of the deep-sea species Anoplopoma fimbria (sablefish) to acute effects of 3 aromatic compounds (toluene, 2-methylnaphthalene, and phenanthrene), dispersant alone, and chemically enhanced water accommodated fractions (CEWAFs) of Alaskan North Slope crude oil. The second was to determine the critical target lipid body burden (CTLBB) for sablefish by fitting aromatic hydrocarbon toxicity data to the target lipid model (TLM), which then allowed expression of CEWAF exposures in terms of dissolved oil toxic units. The final aim was to apply a passive sampling method that targets bioavailable, dissolved hydrocarbons as an alternative analytical technique for improved CEWAF exposure assessment. The results indicate that sablefish exhibit sensitivity to Corexit 9500 (96-h median lethal concentration [LC50] = 72.2 mg/L) within the range reported for other fish species. However, the acute CTLBB of 39.4 ± 2.1 μmol/goctanol lies at the lower end of the sensitivity range established for aquatic species. The utility of both toxic units and passive sampling measurements for describing observed toxicity of dispersed oil is discussed. The present study is novel in that a new test species is investigated to address the uncertainty regarding the sensitivity of deep-sea fishes, while also employing modeling and measurements to improve exposure characterization in oil toxicity tests. Environ Toxicol Chem 2018;37:2210-2221. © 2018 SETAC.

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. © 2017 SETAC.

Ionizable organic chemicals (IOCs) such as organic acids and bases are an important substance class requiring aquatic hazard evaluation. Although the aquatic toxicity of IOCs is highly dependent on the water pH, many toxicity studies in the literature cannot be interpreted because pH was not reported or not kept constant during the experiment, calling for an adaptation and improvement of testing guidelines. The modulating influence of pH on toxicity is mainly caused by pH-dependent uptake and bioaccumulation of IOCs, which can be described by ion-trapping and toxicokinetic models. The internal effect concentrations of IOCs were found to be independent of the external pH because of organisms' and cells' ability to maintain a stable internal pH milieu. If the external pH is close to the internal pH, existing quantitative structure-activity relationships (QSARs) for neutral organics can be adapted by substituting the octanol-water partition coefficient by the ionization-corrected liposome-water distribution ratio as the hydrophobicity descriptor, demonstrated by modification of the target lipid model. Charged, zwitterionic and neutral species of an IOC can all contribute to observed toxicity, either through concentration-additive mixture effects or by interaction of different species, as is the case for uncoupling of mitochondrial respiration. For specifically acting IOCs, we recommend a 2-step screening procedure with ion-trapping/QSAR models used to predict the baseline toxicity, followed by adjustment using the toxic ratio derived from in vitro systems. Receptor- or plasma-binding models also show promise for elucidating IOC toxicity. The present review is intended to help demystify the ecotoxicity of IOCs and provide recommendations for their hazard and risk assessment. Environ Toxicol Chem 2020;39:269-286. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Water solubility is one of the most important and frequently used physical-chemical properties of chemicals. It is crucial within several industrial sectors, in research and in the regulatory sector e.g. for the risk and hazard assessment of chemicals. The most recent OECD guideline (Test No. 105) for measuring solubility is from 1995 and limited to mono-constituent, stable and non-volatile substances. This OECD guideline and the described methods are not suited for several groups of difficult-to-test substances, such as highly hydrophobic chemicals, volatile chemicals, surfactants and mixtures. The aim of this paper is to review solubility measurement methods for difficult-to-test substances on a technical, analytical and scientific level. Methods to handle highly hydrophobic chemicals and volatile chemicals, and methods to rapidly saturate water with fast degrading chemicals are reviewed. A decision tree is presented outlining the preferred choice of method for each chemical group. This review also includes measurement methods for critical micelle concentrations that set the upper concentration limit for freely dissolved surfactants. Finally, concepts and strategies to measure solubility parameters for mixtures, including multi-constituent substances and chemical substances of unknown or variable composition, are discussed.

Assessing oil spill toxicity in real time is challenging due to dynamic field exposures and lack of simple, rapid, and sensitive tests. We investigated the relative sensitivity of two commercially available marine toxicity tests to aromatic hydrocarbons using the target lipid model (TLM). State of the art passive dosing in sealed vials was used to assess the sensitivity of brine shrimp (Artemia franciscana) and rotifer (Brachionus plicatilis). Organisms were exposed to toluene, 1-methylnaphthalene and phenanthrene for 24 h. Toxicity results were analysed using the TLM to estimate the critical target lipid body burden and support comparison to empirical data for 79 other aquatic organisms. Our findings demonstrate the applicability of passive dosing to test small volumes and indicate that the two rapid cyst-based assays are insensitive in detecting hydrocarbon exposures compared to other aquatic species. Our results highlight the limitations of applying these tests for oil pollution monitoring and decision-making.

Reliable delineation of aquatic toxicity cut-offs for poorly soluble hydrocarbons is lacking. In this study, vapor and passive dosing methods were applied in limit tests with algae and daphnids to evaluate the presence or absence of chronic effects at exposures corresponding to the water solubility for representative hydrocarbons from five structural classes: branched alkanes, mono, di, and polynaphthenic (cyclic) alkanes and monoaromatic naphthenic hydrocarbons (MANHs). Algal growth rate and daphnid immobilization, growth and reproduction served as the chronic endpoints investigated. Results indicated that the dosing methods applied were effective for maintaining mean measured exposure concentrations within a factor of two or higher of the measured water solubility of the substances investigated. Chronic effects were not observed for hydrocarbons with an aqueous solubility below approximately 5 μg/L. This solubility cut-off corresponds to structures consisting of 13–14 carbons for branched and cyclic alkanes and 16–18 carbons for MANHs. These data support reliable hazard and risk evaluation of hydrocarbon classes that comprise petroleum substances and the methods described have broad applicability for establishing empirical solubility cut-offs for other classes of hydrophobic substances. Future work is needed to understand the role of biotransformation on the observed presence or absence of toxicity in chronic tests.

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.

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. © 2016 SETAC.

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. © 2016 SETAC.

Aqueous solubility is a fundamental physical-chemical substance property that strongly influences the distribution, fate and effects of chemicals upon release into the environment. Experimental water solubility was determined for 18 selected C9-C18 normal, branched and cyclic alkanes. A slow-stir technique was applied to obviate emulsion formation, which historically has resulted in significant overestimation of the aqueous solubility of such hydrophobic liquid compounds. Sensitive GC-MS based methods coupled with contemporary sample extraction techniques were employed to enable reproducible analysis of low parts-per billion aqueous concentrations. Water solubility measurements for most of the compounds investigated, are reported for the first time expanding available data for branched and cyclic alkanes. Measured water solubilities spanned four orders of magnitude ranging from 0.3 μg/L to 250 μg/L. Good agreement was observed for selected alkanes tested in this work and reported in earlier literature demonstrating the robustness of the slow-stir water solubility technique. Comparisons of measured alkane water solubilities were also made with those predicted by commonly used quantitative structure-property relationship models (e.g. SPARC, EPIWIN, ACD/Labs). Correlations are also presented between alkane measured water solubilities and molecular size parameters (e.g. molar volume, solvent accessible molar volume) affirming a mechanistic description of empirical aqueous solubility results and prediction previously reported for a more limited set of alkanes.

Biodegradation is a major determinant of chemical persistence in the environment and an important consideration for PBT and environmental risk assessments. It is influenced by several environmental factors including temperature and the microbial community structure. According to REACH guidance, a temperature correction based on the Arrhenius equation is recommended for chemical persistence data not performed at the recommended EU mean surface water temperature. Such corrections, however, can lead to overly conservative P/vP assessments. In this paper, the relevance of this temperature correction is assessed for petroleum hydrocarbons, using measured surface water (marine and freshwater) degradation half-time (DT50) and degradation half-life (HL) data compiled from relevant literature. Stringent screening criteria were used to specifically select data from biodegradation tests containing indigenous microbes and conducted at temperatures close to their ambient sampling temperature. As a result, ten independent studies were identified, with 993 data points covering 326 hydrocarbon constituents. These data were derived from tests conducted with natural seawater, or freshwater, at temperatures ranging from 5 to 21 °C. Regressions were performed on the full hydrocarbon dataset and on several individual hydrocarbons. The results were compared to the trend as predicted by the Arrhenius equation and using the activation energy (Ea) as recommend in the REACH Guidance. The comparison shows that the correction recommended in REACH Guidance over predicts the effect of temperature on hydrocarbon biodegradation. These results contrast with temperature manipulated inocula where the test temperature is different from the ambient sampling temperature. In these manipulated systems, the effect of temperature follows the Arrhenius equation more closely. In addition, a more striking effect of temperature on the lag phase was observed with longer lag phases more apparent at lower temperatures. This indicates that the effect of temperature may indeed be even lower when considering hydrocarbon biodegradation without the initial lag phase.

The extraction of oil sands from mining operations in the Athabasca Oil Sands Region uses an alkaline hot water extraction process. The oil sands process water (OSPW) is recycled to facilitate material transport (e.g., ore and tailings), process cooling, and is also reused in the extraction process. The industry has expanded since commercial mining began in 1967 and companies have been accumulating increasing inventories of OSPW. Short- and long-term sustainable water management practices require the ability to return treated water to the environment. The safe release of OSPW needs to be based on sound science and engineering practices to ensure downstream protection of ecological and human health. A significant body of research has contributed to the understanding of the chemistry and toxicity of OSPW. A multistakeholder science workshop was held in September 2017 to summarize the state of science on the toxicity and chemistry of OSPW. The goal of the workshop was to review completed research in the areas of toxicology, chemical analysis, and monitoring to support the release of treated oil sands water. A key outcome from the workshop was identifying research needs to inform future water management practices required to support OSPW return. Another key outcome of the workshop was the recognition that methods are sufficiently developed to characterize chemical and toxicological characteristics of OSPW to address and close knowledge gaps. Industry, government, and local indigenous stakeholders have proceeded to utilize these insights in reviewing policy and regulations. Integr Environ Assess Manag 2019;15:519-527. © 2019 SETAC.

The Organisation for Economic Co‐operation and Development (OECD) test guideline 236 (fish embryo acute toxicity test; 2013) relies on 4 endpoints to describe exposure‐related effects (coagulation, lack of somite formation, tail‐bud detachment from the yolk sac, and the presence of a heartbeat). Danio rerio (zebrafish) embryos were used to investigate these endpoints along with a number of additional sublethal effects (cardiac dysfunction, pericardial edema, yolk sac edema, tail curvature, hatch success, pericardial edema area, craniofacial malformation, swim bladder development, fin development, and heart rate) following 5‐d exposures to 7 petroleum substances. The substances investigated included 2 crude oils, 3 gas oils, a diluted bitumen, and a petrochemical containing a mixture of branched alcohols. Biomimetic extraction–solid‐phase microextraction (BE–SPME) was used to quantify freely dissolved concentrations of test substances as the exposure metric. The results indicated that the most prevalent effects observed were pericardial and yolk sac edema, tail curvature, and lack of embryo viability. A BE–SPME threshold was determined to characterize sublethal morphological alterations that preceded embryo mortality. Our results aid in the understanding of aquatic hazards of petroleum substances to developing zebrafish beyond traditional OECD test guideline 236 endpoints and show the applicability of BE–SPME as a simple analytical tool that can be used to predict sublethal embryo toxicity. Environ Toxicol Chem 2019;38:1302–1312. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

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.

Toxicity of weathered oil was investigated using Atlantic cod (Gadus morhua) larvae. A novel exposure system was applied to differentiate effects associated with dissolved and droplet oil with and without dispersant. After a 4-day exposure and subsequent 4-day recovery period, survival and growth were determined. Analytical data characterizing test oil composition included polyaromatic hydrocarbons (PAH) based on GC/MS and unresolved hydrocarbon classes obtained by two-dimensional chromatography coupled with flame ionization detection was used as input to an oil solubility model to calculate toxic units (TUs) of dissolved PAHs and whole oil, respectively. Critical target lipid body burdens derived from modeling characterizing the sensitivity of effect endpoints investigated were consistent across treatments and within the range previously reported for pelagic species. Individually measured PAHs captured only 3-11% of the TUs associated with the whole oil highlighting the limitations of traditional total PAH exposure metrics for expressing oil toxicity data.

The complex nature and limited aqueous solubility of petroleum substances pose challenges for consistently characterizing exposures in aquatic life hazard assessments. This paper reviews important considerations for the design, conduct and interpretation of laboratory toxicity tests with physically and chemically dispersed oils based on an understanding of the behavior and toxicity of the hydrocarbons that comprise these substances. Guiding principles are provided that emphasize the critical need to understand and, when possible, characterize dissolved hydrocarbon exposures that dictate observed toxicity in these tests. These principles provide a consistent framework for interpreting toxicity studies performed using different substances and test methods by allowing varying dissolved exposures to be expressed in terms of a common metric based on toxic units (TUs). The use of passive sampling methods is also advocated since such analyses provide an analytical surrogate for TUs. The proposed guidance is translated into a series of questions that can be used in evaluating existing data and in guiding design of future studies. Application of these questions to a number of recent publications indicates such considerations are often ignored, thus perpetuating the difficulty of interpreting and comparing results between studies and limiting data use in objective hazard assessment. Greater attention to these principles will increase the comparability and utility of oil toxicity data in decision-making.

Bioavailability of petroleum substances is a complex issue that is affected by substance composition, the physicochemical properties of the individual constituents, and the exposure preparation system. The present study applies mechanistic fate and effects models to characterize the role of droplet oil on dissolved exposure and predicted effects from both neat and weathered crude oils, and refined fuel oils. The main effect from droplet oil is input of additional dissolved hydrocarbons to the exposure system following preparation of the initial stock solution. Toxicity was characterized using toxic units (TU) and shows that replenishment of bioavailable hydrocarbons by droplets in toxicity tests with low droplet content (e.g.,1mg/L) is negligible, consistent with typical exposure conditions following open ocean oil spills. Further, the use of volumetric exposure metrics (e.g., mg/L) introduces considerable variability and the bioavailability-based metrics (e.g., TUs) provide a more consistent basis for understanding oil toxicity data.

A predominant concern following oil spills is toxicity to aquatic organisms. However, few data are available on effects in deep-sea cold water fishes. The present study had 3 major objectives. The first was to investigate the relative sensitivity of the deep-sea species Anoplopoma fimbria (sablefish) to acute effects of 3 aromatic compounds (toluene, 2-methylnaphthalene, and phenanthrene), dispersant alone, and chemically enhanced water accommodated fractions (CEWAFs) of Alaskan North Slope crude oil. The second was to determine the critical target lipid body burden (CTLBB) for sablefish by fitting aromatic hydrocarbon toxicity data to the target lipid model (TLM), which then allowed expression of CEWAF exposures in terms of dissolved oil toxic units. The final aim was to apply a passive sampling method that targets bioavailable, dissolved hydrocarbons as an alternative analytical technique for improved CEWAF exposure assessment. The results indicate that sablefish exhibit sensitivity to Corexit 9500 (96-h median lethal concentration [LC50] = 72.2 mg/L) within the range reported for other fish species. However, the acute CTLBB of 39.4 ± 2.1 μmol/g

The target lipid model (TLM) has been previously applied to predict the aquatic toxicity of hydrocarbons and other nonionic organic chemicals and for deriving the concentrations above which 95% of species should be protected (HC5 values). Several concerns have been identified with the TLM-derived HC5 when it is applied in a substance risk assessment context. These shortcomings were addressed by expanding the acute and chronic toxicity databases to include more diverse taxonomic groups and increase the number of species. The TLM was recalibrated with these expanded databases, resulting in critical target lipid body burdens and acute-to-chronic ratios that met the required guidelines for using species sensitivity distributions in substance risk assessment. The HC5 equation was further revised to consider covarying model parameters. The calculated HC5 values derived from the revised TLM framework were validated using an independent data set for hydrocarbons comprising 106 chronic values across plants, invertebrates, and fish. Assuming a sum binomial distribution, the 95% confidence limit for a 5% failure is between 0.8 and 9.2%. Eight chronic values fell below the HC5, corresponding to an excursion of 7.5%, which falls within the expected uncertainty bounds. Thus, calculated HC5s derived from the revised TLM framework were found to be consistent with the intended protection goals. Environ Toxicol Chem 2018;37:1579-1593. © 2018 SETAC.

Substance risk assessments require estimation of predicted no-effect concentrations (PNECs) in soil and sediment. The present study applies the target lipid model (TLM) and equilibrium partitioning (EqP) model to toxicity data to evaluate the extrapolation of the TLM-derived aquatic PNECs to these compartments. This extrapolation assumes that the sensitivity of aquatic species is similar to that of terrestrial and benthic species. The acute species sensitivity distribution, expressed in terms of species-specific critical target lipid body burdens, was computed using the TLM-EqP framework and found to span a similar range as the aquatic organism species sensitivity distribution but with a slightly lower median value (less than 2 times). The species sensitivity distribution for acute-to-chronic ratios also exhibited a similar range and distribution across species, suggesting similar mechanisms of action. This hypothesis was further tested by comparing empirical soil/sediment chronic effect levels to the calculated PNEC derived using TLM-EqP. The results showed that 95% of the compiled chronic effects data fell above the PNEC, confirming an adequate protection level. These findings support the conclusion that TLM-derived aquatic PNECs can be successfully extrapolated to derive credible PNECs for soil and sediment compartments. Environ Toxicol Chem 2014;33:2679–2687. © 2014 SETAC

The toxicity of chemically dispersed heavy fuel oil (HFO) and 3 distillate fractions to rainbow trout (Oncorhynchus mykiss) embryos was evaluated using the PETROTOX model and a biomimetic extraction technique that involved passive sampling of oil- contaminated test media with solid-phase microextraction (SPME) fibers. Test solutions for toxicity testing were generated using a combination of dispersant and high-energy mixing. The resulting water accommodated fractions (WAF) provided complex exposure regimens that included both dissolved hydrocarbons and oil droplets. The toxicity of the various fractions differed by approximately 3 orders of magnitude when expressed on the basis of WAF dilution. Using detailed compositional data, the PETROTOX model predicted the speciation of hydrocarbons between dissolved and oil droplet phases and explained observed toxicity based on computed dissolved phase toxic units (TUs). A key finding from model calculations was that dissolved hydrocarbon exposures and associated TUs were a nonlinear function of WAF dilution, because dissolved hydrocarbons were largely controlled by the dissolution of oil droplets that were transferred in WAF dilutions. Hence, oil droplets served to "buffer" dissolved concentrations in WAF dilutions at loadings greater than 1mg/L, resulting in higher dissolved concentrations and TUs than expected based on dilution. The TUs computed at each WAF dilution explained the observed toxicity among the HFO and fractions to within a factor of 3. Dissolved material measured by SPME showed a consistent relationship with model-predicted TUs, confirming the utility of this approach for providing an integrated measure of exposure to bioavailable hydrocarbons. These 2 approaches provide complementary tools for better defining bioavailability of complex petroleum substance. Environ Toxicol Chem 2014;33:2094-2104. # 2014 SETAC

PETRORISK is a modeling framework used to evaluate environmental risk of petroleum substances and human exposure through these routes due to emissions under typical use conditions as required by the European regulation for the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH). Petroleum substances are often complex substances comprised of hundreds to thousands of individual hydrocarbons. The physicochemical, fate, and effects properties of the individual constituents within a petroleum substance can vary over several orders of magnitude, complicating risk assessment. PETRORISK combines the risk assessment strategies used on single chemicals with the hydrocarbon block approach to model complex substances. Blocks are usually defined by available analytical characterization data on substances that are expressed in terms of mass fractions for different structural chemical classes that are specified as a function of C number or boiling point range. The physicochemical and degradation properties of the blocks are determined by the properties of representative constituents in that block. Emissions and predicted exposure concentrations (PEC) are then modeled using mass-weighted individual representative constituents. Overall risk for various environmental compartments at the regional and local level is evaluated by comparing the PECs for individual representative constituents to corresponding predicted no-effect concentrations (PNEC) derived using the Target Lipid Model. Risks to human health are evaluated using the overall predicted human dose resulting from multimedia environmental exposure to a substance-specific derived no-effect level (DNEL). A case study is provided to illustrate how this modeling approach has been applied to assess the risks of kerosene manufacture and use as a fuel.

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 (K

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 of10. 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.

A spreadsheet model (PETROTOX) is described that predicts the aquatic toxicity of complex petroleum substances from petroleum substance composition. Substance composition is characterized by specifying mass fractions in constituent hydrocarbon blocks (HBs) based on available analytical information. The HBs are defined by their mass fractions within a defined carbon number range or boiling point interval. Physicochemical properties of the HBs are approximated by assigning representative hydrocarbons from a database of individual hydrocarbons with associated physicochemical properties. A three-phase fate model is used to simulate the distribution of each structure among the water-, air-, and oil-phase liquid in the laboratory test system. Toxicity is then computed based on the predicted aqueous concentrations and aquatic toxicity of each structure and the target lipid model. The toxicity of the complex substance is computed assuming additivity of the contribution of the individual assigned hydrocarbons. Model performance was evaluated by using direct comparisons with measured toxicity data for petroleum substances with sufficient analytical characterization to run the model. Indirect evaluations were made by comparing predicted toxicity distributions using analytical data on petroleum substances from different product categories with independent, empirical distributions of toxicity data available for the same categories. Predictions compared favorably with measured aquatic toxicity data across different petroleum substance categories. These findings demonstrate the utility of PETROTOX for assessing environmental hazards of petroleum substances given knowledge of substance composition.

Cyanide can be toxic to aquatic organisms, and the U.S. Environmental Protection Agency has developed ambient water- quality criteria to protect aquatic life. Recent work suggests that considering free, rather than total, cyanide provides a more accurate measure of the biological effects of cyanides and provides a basis for water-quality criteria. Aquatic organisms are sensitive to free cyanide, although certain metals can form stable complexes and reduce the amount of free cyanide. As a result, total cyanide is less toxic when complexing metals are present. Cyanide is often present in complex effluents, which requires understanding how other components within these complex effluents can affect cyanide speciation and bioavailability. The authors have developed a model to predict the aqueous speciation of cyanide and have shown that this model can predict the toxicity of metal-cyanide complexes in terms of free cyanide in solutions with varying water chemistry. Toxicity endpoints based on total cyanide ranged over several orders of magnitude for various metal-cyanide mixtures. However, predicted free cyanide concentrations among these same tests described the observed toxicity data to within a factor of 2. Aquatic toxicity can be well-described using free cyanide, and under certain conditions the toxicity was jointly described by free cyanide and elevated levels of bioavailable metals. Environ. Toxicol. Chem. 2012;31:1774- 1780. # 2012 SETAC Keywords—Water-quality criteria Mixture Cyanide Bioavailability Biotic ligand model

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. © 2016 SETAC.

Substance risk assessments require estimation of predicted no-effect concentrations (PNECs) in soil and sediment. The present study applies the target lipid model (TLM) and equilibrium partitioning (EqP) model to toxicity data to evaluate the extrapolation of the TLM-derived aquatic PNECs to these compartments. This extrapolation assumes that the sensitivity of aquatic species is similar to that of terrestrial and benthic species. The acute species sensitivity distribution, expressed in terms of species-specific critical target lipid body burdens, was computed using the TLM-EqP framework and found to span a similar range as the aquatic organism species sensitivity distribution but with a slightly lower median value (less than 2 times). The species sensitivity distribution for acute-to-chronic ratios also exhibited a similar range and distribution across species, suggesting similar mechanisms of action. This hypothesis was further tested by comparing empirical soil/sediment chronic effect levels to the calculated PNEC derived using TLM-EqP. The results showed that 95% of the compiled chronic effects data fell above the PNEC, confirming an adequate protection level. These findings support the conclusion that TLM-derived aquatic PNECs can be successfully extrapolated to derive credible PNECs for soil and sediment compartments.

Methods that quantify dissolved hydrocarbons are needed to link oil exposures to toxicity. Solid phase microextraction (SPME) fibers can serve this purpose. If fibers are equilibrated with oiled water, dissolved hydrocarbons partition to and are concentrated on the fiber. The absorbed concentration (Cpolymer) can be quantified by thermal desorption using GC/FID. Further, given that the site of toxic action is hypothesized as biota lipid and partitioning of hydrocarbons to lipid and fibers is well correlated, Cpolymer is hypothesized to be a surrogate for toxicity prediction. To test this method, toxicity data for physically and chemically dispersed oils were generated for shrimp, Americamysis bahia, and compared to test exposures characterized by Cpolymer. Results indicated that Cpolymer reliably predicted toxicity across oils and dispersions. To illustrate field application, SPME results are reported for oil spills at the Ohmsett facility. SPME fibers provide a practical tool to improve characterization of oil exposures and predict effects in future lab and field studies.

The toxicity of chemically dispersed heavy fuel oil (HFO) and 3 distillate fractions to rainbow trout (Oncorhynchus mykiss) embryos was evaluated using the PETROTOX model and a biomimetic extraction technique that involved passive sampling of oil-contaminated test media with solid-phase microextraction (SPME) fibers. Test solutions for toxicity testing were generated using a combination of dispersant and high-energy mixing. The resulting water accommodated fractions (WAF) provided complex exposure regimens that included both dissolved hydrocarbons and oil droplets. The toxicity of the various fractions differed by approximately 3 orders of magnitude when expressed on the basis of WAF dilution. Using detailed compositional data, the PETROTOX model predicted the speciation of hydrocarbons between dissolved and oil droplet phases and explained observed toxicity based on computed dissolved phase toxic units (TUs). A key finding from model calculations was that dissolved hydrocarbon exposures and associated TUs were a nonlinear function of WAF dilution, because dissolved hydrocarbons were largely controlled by the dissolution of oil droplets that were transferred in WAF dilutions. Hence, oil droplets served to "buffer" dissolved concentrations in WAF dilutions at loadings greater than 1 mg/L, resulting in higher dissolved concentrations and TUs than expected based on dilution. The TUs computed at each WAF dilution explained the observed toxicity among the HFO and fractions to within a factor of 3. Dissolved material measured by SPME showed a consistent relationship with model-predicted TUs, confirming the utility of this approach for providing an integrated measure of exposure to bioavailable hydrocarbons. These 2 approaches provide complementary tools for better defining bioavailability of complex petroleum substance.

PETRORISK is a modeling framework used to evaluate environmental risk of petroleum substances and human exposure through these routes due to emissions under typical use conditions as required by the European regulation for the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH). Petroleum substances are often complex substances comprised of hundreds to thousands of individual hydrocarbons. The physicochemical, fate, and effects properties of the individual constituents within a petroleum substance can vary over several orders of magnitude, complicating risk assessment. PETRORISK combines the risk assessment strategies used on single chemicals with the hydrocarbon block approach to model complex substances. Blocks are usually defined by available analytical characterization data on substances that are expressed in terms of mass fractions for different structural chemical classes that are specified as a function of C number or boiling point range. The physicochemical and degradation properties of the blocks are determined by the properties of representative constituents in that block. Emissions and predicted exposure concentrations (PEC) are then modeled using mass-weighted individual representative constituents. Overall risk for various environmental compartments at the regional and local level is evaluated by comparing the PECs for individual representative constituents to corresponding predicted no-effect concentrations (PNEC) derived using the Target Lipid Model. Risks to human health are evaluated using the overall predicted human dose resulting from multimedia environmental exposure to a substance-specific derived no-effect level (DNEL). A case study is provided to illustrate how this modeling approach has been applied to assess the risks of kerosene manufacture and use as a fuel.

Copper is used as an antimicrobial agent in building materials such as algae-resistant roofing shingles and treated wood products for decks, fences, and utility poles used in urbanized areas. Releases from these materials may pose risks to aquatic and terrestrial organisms. Copper exposures in surface water, sediment, and soil were estimated for a hypothetical urban setting using the TREX watershed model. Drainage and soil characteristics were based on an existing watershed. Urban landscape characteristics were developed from data regarding housing densities and copper use in building materials. This setting provides a spatially distributed, upper-bound assessment scenario. Release rates from algae-resistant shingles and treated wood were defined based on surface area and rainfall. Simulations for the urban landscapes were performed for a 10-year period. Simulation results were used to evaluate exceedences of benchmark concentrations for water, sediment, and soil. For algae-resistant shingles, exposures did not exceed benchmarks in any media. For treated wood, exposures did not exceed sediment and soil benchmarks, and surface water benchmarks were exceeded on 2 days in 10 years. Based on this analysis, copper use as an antimicrobial agent in algae resistant shingles and treated wood is not expected to pose significant adverse environmental risks on an individual use basis.