Polyaromatic hydrocarbon exposure: an ecological impact ambiguity

Polyaromatic hydrocarbons (PAHs) represent a fraction of petroleum hydrocarbons and are currently one of the foremost sources of generating energy in today’s contemporary society. However, evidence highlighted in this review show that PAH pollution, as a result of oil spills, hazardous PAH-contaminated working environments and technologies which do not efficiently utilise fuels, as well as natural sources of emissions (e.g. forest fires) may have significant health implications for all taxa. The extent of damage to organisms from PAH exposure is dependent on numerous factors including degree and type of PAH exposure, nature of the environment contaminated (i.e. terrestrial or aquatic), the ability of an organism to relocate to pristine environments, type and sensitivity of organism to specific hydrocarbon fractions and ability of the organism to metabolise different PAH fractions. The review highlights the fact that studies on the potential damage of PAHs should be carried out using mixtures of hydrocarbons as opposed to individual hydrocarbon fractions due to the scarcity of individual fractions being a sole contaminant. Furthermore, potential damage of PAH-contaminated sites should be assessed using an entire ecological impact outlook of the affected area.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

Fingerprinting of Gasoline and Coal Tar NAPL Volatile Hydrocarbons Dissolved in Groundwater

Accidental spills and chronic leaks of fuel oil or other hydrocarbon material (e.g., coal tar) often result in subsurface accumulation of nonaqueous phase liquid (NAPL), which can be a subsequent source of contamination in groundwater. Linking hydrocarbons in groundwater to a source NAPL has been difficult when using standard target analytes (e.g., BTEX) because of differences in partitioning properties of the analytes between the source NAPL and groundwater. Because aqueous solubility is predicted to be the controlling influence in the partitioning of hydrocarbons from NAPL to groundwater, a solubility-based approach to matching dissolved hydrocarbons in groundwater to their source NAPL has been developed and validated for two sites with commonly encountered types of NAPL contamination. Specifically, a gasoline LNAPL and a coal tar DNAPL from two separate sites (West Virginia and California) and groundwater interfaced with these NAPLs were analyzed for approximately 50 gasoline-range hydrocarbons consisting of paraffin, isoparaffin, (mono-) aromatic, naphthene, and olefin compounds (PIANO). Solubility characteristics of selected alkyl aromatic hydrocarbons from the PIANO analysis were used to identify a set of diagnostic hydrocarbons, expressed as hydrocarbon ratios, which were found to be useful in distinguishing the source(s) of hydrocarbons in groundwater. At the West Virginia site, the diagnostic ratios in a downgradient groundwater sample were similar to those of a gasoline NAPL at that site, indicating the source of hydrocarbons to the groundwater was the upgradient gasoline NAPL. The diagnostic ratios of the groundwater in contact with the gasoline NAPL and the remote groundwater were also similar, providing evidence that the diagnostic ratios were retained during transport in the aquifer. At the California site, diagnostic ratios in a cross-gradient groundwater sample differed from those of the coal tar NAPL at that site, indicating that the remote groundwater hydrocarbons did not originate from the coal tar contamination. Environmental factors such as selective degradation of specific isomers and various geological conditions (e.g., soil mineralogy, and organic content) may confound the application of this solubility-based fingerprinting approach. Thus, it is recommended that multiple diagnostic pairs be simultaneously evaluated when considering this fingerprinting approach for specific sites and product types.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

Mechanism of concentration addition toxicity: they are different for nonpolar narcotic chemicals, polar narcotic chemicals and reactive chemicals

According to the toxicity mechanism of the individual chemicals, the concentration addition toxicity mechanism is revealed for nonpolar-narcotic-chemical mixtures, polar-narcotic-chemical mixtures and reactive-chemical mixtures, respectively. For nonpolar-narcotic-chemical mixtures, the partitioning of individual chemicals from water to biophase was determined, and the result shows that their concentration additive effect results from no competitive partitioning among individual chemicals. For polar-narcotic-chemical mixtures, their toxicity are contributed by two factors (the total baseline toxicity and the hydrogen bond donor activity of individual chemicals), and it is the concentration additive effect for either of these two factors that leads to their concentration addition toxicity. In addition, the interactions between the reactive chemicals and the biological macromolecules are discussed thoroughly. The results suggest that the net effect of these interactions is zero, and it is this zero net effect that leads to the concentration addition toxicity mechanism for reactive-chemical mixtures.     

A guideline supplement for determining the aquatic toxicity of poorly water-soluble complex mixtures using water-accommodated fractions

Regulatory guideline methods for aquatic toxicity testing have generally been developed for pure chemicals tested at concentrations below the limit of their water solubility where exposure concentration can be quantified in terms of a concentration in solution. The same methods may also be applied to testing products which are complex chemical mixtures at product: water ratios that do not exceed the water-solubility of any of the product components. A different approach is required for testing complex mixtures at ratios which exceed water-solubilities of some of the components.     

Abiotic behavior of entrapped petroleum products in the subsurface during leaching

Petroleum products are generally volatile hydrocarbon mixtures. These mixtures may contaminate land surfaces, the unsaturated zone and ground waters at numerous sites and thus represent a long-term source of environmental subsurface pollution. Based on laboratory and field evidence obtained by our research groups and others we emphasize in the present review paper the effect of leaching on the abiotic processes controlling the fate of volatile petroleum hydrocarbon mixtures (VPHMs) in the soil environment. The modification of petroleum hydrocarbon mixtures due to changes in the soil water content is considered the result of a “leaching phenomenon”. The experimental evidence of VPHM behavior in the porous media is linked to four major processes: retention, redistribution and attenuation in the subsurface, and dissolution in the soil water.

Once VPHMs reach the soil surface, their residual concentration and composition is influenced by the amount and quality of the leaching water. The transport and natural attenuation of the VPHMs in the unsaturated zone is affected by the amount and rate of leaching. Since VPHM are a mixture of volatile and non-volatile hydrocarbons whose components differ by several orders of magnitude in their vapor pressure and water solubility, their fates in the soil environment under leaching will be diverse too. This will influence the temporal concentrations of the VPHM components and their distributions with depth, as vapors, solutes, or water-immiscible solutions. Wetting the soil before or after the VPHMs reach it, differentially affects the abiotic processes governing petroleum products behavior into the porous media.     

Towards optimal sampling schedules for integral pumping tests

Ethanol use as a gasoline additive is increasing, as are the chances of groundwater contamination caused by gasoline releases involving ethanol. To evaluate the impact of ethanol on dissolved hydrocarbon plumes, a field test was performed in which three gasoline residual sources with different ethanol fractions (E0: no ethanol, E10: 10% ethanol and E95: 95% ethanol) were emplaced below the water table. Using the numerical model BIONAPL/3D, the mass discharge rates of benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene were simulated and results compared to those obtained from sampling transects of multilevel samplers. It was shown that ethanol dissolved rapidly and migrated downgradient as a short slug. Mass discharge of the hydrocarbons from the E0 and E10 sources suggested similar first-order hydrocarbon decay rates, indicating that ethanol from E10 had no impact on hydrocarbon degradation. In contrast, the estimated hydrocarbon decay rates were significantly lower when the source was E95. For the E0 and E10 cases, the aquifer did not have enough oxygen to support complete mineralization of the hydrocarbon compounds to the extent suggested by the field-based mass discharge. Introducing a heterogeneous distribution of hydraulic conductivity did little to overcome this discrepancy. A better match between the numerical model and the field data was obtained assuming partial degradation of the hydrocarbons to intermediate compounds. Besides depending on the ethanol concentration, the impact of ethanol on hydrocarbon degradation appears to be highly dependent on the availability of electron acceptors.     

Relationship between hydrocarbon measurements and toxicity to a chironomid, fish larva and daphnid for oils and oil spill chemical treatments in laboratory freshwater marsh microcosms

This research investigated the extent to which various common hydrocarbon measures can be used to predict toxicity to freshwater aquatic organisms due to fouling by oil. Actual toxicity results, on laboratory freshwater marsh microcosms using two water-column species and a benthic species, were described earlier. The hydrocarbon measures used were TPH(g), TPH(FID), TPH(MS), TTAH (sum of 41 target aromatic hydrocarbons), principal components of 41 TAHs, and each individual TAH. In general, toxicity was more closely related to TPH(MS) levels than to TPH(FID) and (especially) TPH(g) levels. The strongest relationships were found for TTAH levels and for the principal components of the TAHs. Regressions of toxicity on many individual TAHs were also strong, with a single group of compounds explaining as much as 59% of the variation in survival. While the various regressions were highly significant statistically and at times able to accurately predict broad differences in toxicity, the high variation in survival at a specific hydrocarbon concentration indicates that these hydrocarbon measures can not substitute for actual toxicity determinations in accurately ranking the toxicity of samples from oiled freshwater marshes.     

NAPL migration and ecotoxicity of conventional and renewable fuels in accidental spill scenarios

Fuels derived from non-petroleum renewable resources have raised interest due to their potential in replacing petroleum-based fuels, but information on their fate and effects in the terrestrial and aquatic environments in accidental spill scenario is limited. In this study, migration of four fuels (conventional diesel, conventional gasoline, renewable diesel NExBTL, and ethanol-blended gasoline RE85 containing maximum 85 % ethanol) as non-aqueous phase liquids (NAPL) in soil was demonstrated in a laboratory-scale experiment. Ecotoxicity data was produced for the same fuels. There was no significant difference in migration of conventional and renewable diesel, but gasoline migrated 1.5 times deeper and 7–9 times faster in sand than diesel. RE85 spread horizontally wider but not as deep (p?Eisenia fetida followed by ethanol-blended gasoline (LC50 1,643 mg/kg THC) and conventional diesel (LC50 2,432 mg/kg THC), although gasoline evaporated fast from soil. For comparison, the toxicity of the water-accommodated fractions (WAF) of the fuels was tested with water flea Daphnia magna and Vibrio fischeri, also demonstrating groundwater toxicity. The WAF of conventional gasoline and RE85 showed almost similar toxicity to both the aquatic test species. EC50 values of 1:10 (by volume) WAF were 9.9 %WAF (gasoline) and 9.3 %WAF (RE85) to D. magna and 9.3 %WAF (gasoline) and 12.3 %WAF (RE85) to V. fischeri. Low solubility decreased toxicity potential of conventional diesel in aquatic environment, but direct physical effects of oil phase pose a threat to organisms in nature. Renewable diesel NExBTL did not show clear toxicity to any test species.     

Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: concentrations, composition, and associated risks to protected sea otters

Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume ∼25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills.     

Modeling the partitioning of BTEX in water-reformulated gasoline systems containing ethanol

The objectives of this research were to quantify the extent of cosolvency for water–gasoline mixtures containing ethanol and to identify appropriate modeling tools for predicting the equilibrium partitioning of BTEX compounds and ethanol between an ethanol-bearing gasoline and water. Batch-equilibrium experiments were performed to measure ethanol and BTEX partitioning between a gasoline and aqueous phase. The experiments incorporated simple binary and multicomponent organic mixtures comprised of as many as eight compounds as well as highly complex commercial gasolines where the composition of the organic phase was not completely defined. At high ethanol volume fractions, the measured partition coefficients displayed an approximate linear relationship when plotted on semi-log scale as a function of ethanol volume fraction. At lower concentrations, however, there was a distinctly different trend which is attributed to a change in solubilization mechanisms at these concentrations. Three mathematical models were compared with or fit to the experimental results. Log-linear and UNIFAC-based models were used in a predictive capacity and were capable of representing the overall increase in partition coefficients as a function of increasing ethanol content in the aqueous phase. However, neither of these predicted the observed two-part curve. A piecewise model comprised of a linear relationship for low ethanol volume fractions and a log-linear model for higher concentrations was fit to data for a surrogate gasoline comprised of eight compounds and was then used to predict BTEX concentrations in the aqueous phase equilibrated with three different commercial gasolines. This model was superior to the UNIFAC predictions, especially at the low aqueous ethanol concentrations.     

Do aquatic effects or human health end points govern the development of sediment-quality criteria for nonionic organic chemicals ?

The equilibrium partitioning theory may be used to describe the partitioning of nonionic organic chemicals between water, sediment, and aquatic biota. This paradigm was employed to compare the relative magnitudes of organic carbon-normalized sediment-quality criteria that are intended to protect either benthic organisms from the direct toxic effects of sediment-associated chemicals or humans from the indirect health effects posed by the ingestion of contaminated aquatic animals. Comparison of calculated sediment-quality criteria for a variety of hydrophobic chemicals suggests that human health-based end points often result in more restrictive criteria than aquatic effects-based values. Review of published field data indicates that the equilibrium partitioning paradigm may, depending on contaminant class, either over- or underestimate the extent to which sediment-associated contaminations are bioaccumulated. Despite the limitations of adopting this simple theory for criteria development, calculations reveal that regulatory decisions involving sediments contaminated with such chemicals may be dictated by human health concerns if current risk assessment methodologies are applied.     

Predicting bioconcentration factors (BCFs) of polychlorinated bornane (Toxaphene) congeners in fish and comparison with bioaccumulation factors (BAFs) in biota from the aquatic environment.

Polychlorinated bornanes, the main components of Toxaphene, are bioconcentrated in aquatic organisms to a high extent. However, up to this time no bioconcentration tests with individual chlorinated bornanes in aquatic organisms have been performed. Therefore, the bioconcentration factors (BCFs) of seven selected persistent chlorinated bornane congeners which are regularly found in aquatic organisms, were predicted from their n-octanol/water partition coefficients (log Kow). Furthermore, these BCF values were compared with the measured bioaccumulation factors (BAFs) in zooplankton and different fish species from the aquatic environment.     

Modeling time-dependent toxicity to aquatic organisms from pulsed exposure of PAHs in urban road runoff

Understanding of the magnitude of urban runoff toxicity to aquatic organisms is important for effective management of runoff quality. In this paper, the aquatic toxicity of polycyclic aromatic hydrocarbons (PAHs) in urban road runoff was evaluated through a damage assessment model. Mortality probability of the organisms representative in aquatic environment was calculated using the monitored PAHs concentration in road runoff. The result showed that the toxicity of runoff in spring was higher than those in summer. Analysis of the time-dependent toxicity of series of runoff water samples illustrated that the toxicity of runoff water in the final phase of a runoff event may be as high as those in the initial phase. Therefore, the storm runoff treatment systems or strategies designed for capture and treatment of the initial portion of runoff may be inappropriate for control of runoff toxicity.     

Distribution of Light Hydrocarbons in Ambient Air

The diversity of hydrocarbons which are present in ambient polluted air provide a potentially rich source of information concerning the nature of this type of pollution. Measurements of the relative amounts of various hydrocarbons can be correlated with the various possible sources. Since hydrocarbon reactivities vary widely it is also possible to estimate the extent to which various individual hydrocarbons have reacted. Except for samples taken deliberately near sources of hydrocarbon pollution these air samples invariably resemble auto exhaust with an addition of natural gas and of C₃–C₅ paraffins which resemble gasoline vapor. Samples taken in industrial areas and near the smoke plume from a brush fire showed distinctive differences in composition. During the smog season in the fall of 1968 good data were obtained of “typical” or “representative” samples of light, medium and heavy smog. These show the expected depletion of more reactive hydrocarbons in a much more convincing way than before. By comparing these distributions with composition in unreacted samples and by making use of data from bottle irradiations, it was possible to estimate the contribution of the various hydrocarbons in terms of “amount reacted.” The amounts of higher hydrocarbons present and reacted were also estimated from gasoline composition.     

The effect of hydrocarbon mixtures on adsorption of substituted naphthalenes by clay and sediment from water

Adsorption of methyl and dimethyl naphthalenes, and of these compounds as components of JP8 and synthetic jet fuel mixtures, has been measured on two sediments and montmorillonite clay in water. Isotherms were linear, and hydrocarbons of similar structure gave similar adsorption coefficients on a particular clay or sediment. Individual component adsorption coefficients were dependent upon mixture composition, but coefficients usually varied by less than a factor of two. This implies that single component adsorption coefficients may be adequate for use in environmental fate models of hydrocarbon mixtures.     

Oil pollution in the Caspian Sea coastal waters

The study aims to investigate hydrocarbon and pollutant concentrations in the southern coastal waters of the Caspian Sea to trace their origins and nature, including the effect of the beach materials on hydrocarbons for 11 sites in Golestan, Mazandaran, and Guilan provinces. Samples were collected from sandy and rocky sites for gas chromatography in five carbon ranges of gasoline, diesel oil, engine oil, BTEX, and PAH. The GC analysis revealed the highest pollutant concentration levels in autumn and the lowest in summer; moreover in rocky beaches analysis indicated that a major portion of the oil pollution in the region consists of hydrocarbons.     

Factors affecting the distribution of hydrocarbon contaminants and hydrogeochemical parameters in a shallow sand aquifer

The distributions of hydrocarbon contaminants and hydrogeochemical parameters were investigated in a shallow sand aquifer highly contaminated with petroleum hydrocarbons leaked from solvent storage tanks. For these purposes, a variety of field investigations and studies were performed, which included installation of over 100 groundwater monitoring wells and piezometers at various depths, soil logging and analyses during well and piezometer installation, chemical analysis of groundwater, pump tests, and slug tests. Continuous water level monitoring at three selected wells using automatic data-logger and manual measuring at other wells were also conducted. Based on analyses of the various investigations and tests, a number of factors were identified to explain the distribution of the hydrocarbon contaminants and hydrogeochemical parameters. These factors include indigenous biodegradation, hydrostratigraphy, preliminary pump-and-treat remedy, recharge by rainfall, and subsequent water level fluctuation. The permeable sandy layer, in which the mean water table elevation is maintained, provided a dominant pathway for contaminant transport. The preliminary pump-and-treat action accelerated the movement of the hydrocarbon contaminants and affected the redox evolution pattern. Seasonal recharge by rain, together with indigenous biodegradation, played an important role in the natural attenuation of the petroleum hydrocarbons via mixing/dilution and biodegradation. The water level fluctuations redistributed the hydrocarbon contaminants by partitioning them into the soil and groundwater. The identified factors are not independent but closely inter-correlated.     

The evaluation of the equilibrium partitioning method using sensitivity distributions of species in water and soil

The equilibrium partitioning method (EqP-method) can be used to calculate soil quality standards (expressed in mg/kg) from aquatic quality standards (expressed in microg/l) using a partitioning coefficient. The validity of this application of the EqP-method was studied comparing aquatic with terrestrial toxicity data. The data set collected for deriving environmental quality standards in the Netherlands, was used for this study. For 10 organic substances (chlorpyrifos, atrazine, carbofuran, pentachlorophenol, chlordane, aldrin, trichlorobenzene, heptachlor, trichlorophenol and trichloroethene) and for 8 metals, sufficient data were available. The aquatic toxicity data were multiplied by the partitioning coefficient in order to obtain aquatic data expressed in mg/kg. For some compounds the terrestrial toxicity data were significantly higher than the aquatic data but for other compounds it was the other way around. These differences indicate that the EqP-method can give significant over-or underestimations, due to inaccurate partitioning coefficients or differences in species sensitivities. These over- or underestimations can have an impact on the setting of environmental quality standards which are based on the hazardous concentration 5% (HC5) values. The uncertainty in the calculation of HC5 values attributed to the use of the EqP-method, was quantified. The HC5 values derived using the EqP-method were in 5% of the cases more than 20 times higher than the corresponding HC5 values that were derived directly from soil toxicity tests. Despite of this uncertainty the use of the EqP-method can still be advocated for setting soil quality guidelines when only a very limited number of terrestrial toxicity data are available.