Occurrence of MTBE in Heating Oil and Diesel Fuel in Connecticut

The objective of this study was to confirm if MTBE, which is not intentionally added to fuels other than gasoline, is a contaminant in heating oil and diesel fuel. The study entailed conducting a statewide sampling program of heating oil and diesel fuel in Connecticut. An analytical method was developed to conduct analyses of heating oil and diesel fuel for MTBE in the milligram per liter (mg/L) range. The method involved equilibrating product with water to extract MTBE followed by static head-space analysis on aliquots of the water. Analyses were conducted using a gas chromatograph with a MTBE specific column. The statewide sampling program confirmed the widespread occurrence of MTBE in heating oil and diesel fuel. MTBE was detected in all samples collected during our sampling program at concentrations ranging from 9.7 to 906 mg/L in heating oil (26 samples), and from 74 to 120 mg/L in diesel fuel (five samples). Based on these ranges. MTBE concentrations in ground water in the vicinity of heating oil and diesel fuel releases could exceed thousands of micrograms per liter. Our analysis would suggest that the levels of heating oil and diesel fuel contamination observed could result from the commingling of only a few parts gasoline with thousands of parts of these fuels. The extent to which MTBE occurs in heating oil and diesel fuel nationwide is not known, but our data suggests that it may be widespread.     

NAPL source zone depletion model and its application to railroad-tank-car spills

We developed a new semi-analytical source zone depletion model (SZDM) for multicomponent light nonaqueous phase liquids (LNAPLs) and incorporated this into an existing screening model for estimating cleanup times for chemical spills from railroad tank cars that previously considered only single-component LNAPLs. Results from the SZDM compare favorably to those from a three-dimensional numerical model, and from another semi-analytical model that does not consider source zone depletion. The model was used to evaluate groundwater contamination and cleanup times for four complex mixtures of concern in the railroad industry. Among the petroleum hydrocarbon mixtures considered, the cleanup time of diesel fuel was much longer than E95, gasoline, and crude oil. This is mainly due to the high fraction of low solubility components in diesel fuel. The results demonstrate that the updated screening model with the newly developed SZDM is computationally efficient, and provides valuable comparisons of cleanup times that can be used in assessing the health and financial risk associated with chemical mixture spills from railroad-tank-car accidents.     

Natural Attenuation of Aromatic Hydrocarbons in a Shallow Sand Aquifer

Inadvertent release of petroleum products such as gasoline into the subsurface can initiate ground water contamination, particularly by the toxic, water-soluble and mobile gasoline components: benzene, toluene and xylenes (BTX). This study was undertaken to examine the processes controlling the rate of movement and the persistence of dissolved BTX in ground water in a shallow, unconfined sand aquifer.
Water containing about 7.6 mg/ L total BTX was introduced below the water table and the migration of contaminants through a sandy aquifer was monitored using a dense sampling network. BTX components migrated slightly slower than the ground water due to sorptive retardation. Essentially all the injected mass of BTX was lost within 434 days due to biodegradation. Rates of mass loss were similar for all monoaromatics; benzene was the only component to persist beyond 270 days. Laboratory biodegradation experiments produced similar rates, even when the initial BTX concentration varied.
A dominant control over BTX biodegradation was the availability of dissolved oxygen. BTX persisted at the field site in layers low in dissolved oxygen. Decreasing mass loss rates over time observed in the field experiment are not likely due to first-order deeradation rates, but rather to the persistence of small fractions of BTX mass in anoxic layers.     

Detection of aliphatic hydrocarbons derived by recent “bio-conversion” from fossil fuel oil in North Sea waters

The higher boiling point range of saturated aliphatic hydrocarbon fractions extracted from North Sea water have been re-investigated in detail with improved high resolution glass capillary columns suitable for high temperature gas-chromatography. The resulting chromatograms reveal hydrocarbon patterns, most of which have the same common feature: a smooth distribution of the long-chain n-alkanes combined with a lack of the branched alkanes normally expected for fossil fuel oil. Instead, two homologous series of iso- and anteiso-alkanes could be detected. Since this finding is always associated with traces of present or past fossil fuel oil contamination of the upper water column, these environmental n-, iso and anteisoalkanes are considered to be recently ‘bio-converted’ from fossil fuel oil hydrocarbons. They form a third group beside recent biogenic and fossil petrogenic hydrocarbons in the marine environment. Oil pollution records of the marine environment will have to take into account this group of microbial hydrocarbons.     

Bioaccumulation and histopathological effects of oil on a stony coral

Colonies of the shallow-water Caribbean coral Manicina areolata incorporated petroleum hydrocarbons into their tissues during exposure to water accommodated fractions of No. 2 fuel oil for three months. This contamination was not removed after depuration periods of up to two weeks. Although these corals remained alive, evidence of pathological responses was found which included impaired development of reproductive tissues, degeneration and loss of symbiotic zooxanthellae, and atrophy of mucous secretory cells and muscle bundles.     

Sampling VOCs with Porous Suction Samplers in the Presence of Ethanol: How Much Are We Losing?

Porous suction samplers have been widely used to obtain ground water samples from the vadose zone. However, previous studies identified different mechanisms that may compromise the sample's representativeness, such as volatilization and sorption. This issue is particularly important when dealing with volatile organic compounds (VOCs) as in gasoline spills. Ethanol is common in modern fuels and so may be present in ground water contamination from fuel releases. The objective of this work was to evaluate the losses of VOCs in the presence of ethanol when using porous suction samplers. Laboratory experiments were performed using a ceramic porous suction sampler to sample test solution containing benzene, toluene, xylenes, trimethylbenzenes, naphthalene, and different volumetric fractions of ethanol. Significant losses were found up to 30% for ethylbenzene. Ethanol was found to affect the accuracy of the readings by two main mechanisms: first, negatively, by increasing the headspace in the sampling tube, and second, positively, increasing partition to the aqueous phase due to the cosolvent effect and therefore decreasing the mass loss by volatilization. As a consequence, the highest losses of VOCs were found at intermediate ethanol volume fractions: 10% and 20% (v/v). The losses can be anticipated by measuring the ratio of gas to water in the sampling line and then by applying simple partition models considering cosolvency by ethanol. The importance of adequate purging when using porous suction samplers was also shown.     

Polar Compounds from the Dissolution of Weathered Diesel

Hydrocarbon and nonhydrocarbon components dissolving in water from fresh diesel and field samples of highly weathered diesel (spilled up to 50 years ago) from two sites were investigated. The fresh and weathered diesels were equilibrated with water using a slow-stirring method, and the product and equilibrated aqueous water samples analyzed by a range of analytical procedures. The water phase equilibrated with weathered diesels had higher total dissolved organics concentrations (96 and 8.6 mg/L at the two sites) compared to the water phase equilibrated with fresh diesel (average of 3.4 mg/L). Compound class characterization of dissolved organics in water from the weathered diesel showed that polar components were a significant compound class (98% and 42% at the two sites) and appeared largely as an unresolved complex mixture (UCM) in the total ion chromatograms (TICs). Identification of 1-adamantanol in the polar fraction of both weathered diesel samples (3.6 and 0.3 μg/L at the two sites) suggested that at least some of the associated polar components are from a petroleum source. The analysis of total petroleum hydrocarbons (TPH) is aimed at measuring only dissolved carbon and hydrogen-containing compounds, and dissolved polar compounds present as a UCM are often assumed to be from natural organic matter (NOM) and removed. This may result in a gross underestimation of the total soluble organic material in water associated with weathered diesels. In addition, the risk posed by these fuel-derived polar compounds is unknown.     

Biodegradation of Petroleum Hydrocarbons in Fractured, Unsaturated Dolomite at a Field Site

Gasoline constituents were detected in unsaturated soil and rock during abandonment of a leaky underground storage tank (UST). The unsaturated sequence beneath the former UST consists of 90 feet of silty till, fractured dolomite, and friable sand-stone. Pore gas probes were installed in each of the unsaturated units, both in the source area and in a background on-site location. Pore gas samples were collected to evaluate the nature, extent, and fate of residual hydrocarbons in the vadose zone. Pore gas from the till and dolomite in the source area was enriched in petroleum hydrocarbons and carbon dioxide, and was depleted in oxygen, relative to pore gas from the background area. During two years of ground water monitoring at the site, methyl tertiary butyl ether was periodically detected in the ground water beneath the source area as pulses of recharge passed through the unsaturated zone, but no other gasoline constituents were detected. Apparently, the most degradable fraction of the gasoline (aromatic hydrocarbons) is being attenuated in the vadose zone before the water table is reached.     

The recognition of biodegraded petroleum-derived aromatic hydrocarbons in recent marine sediments

Aromatic hydrocarbon fractions isolated from sediments polluted with crude oil, from sampling stations in and around Sullom Voe, Shetland Islands, were found to exhibit, as the major feature in their gas chromatograms, an unresolved complex mixture or ‘hump’. This feature was absent from the gas chromatograms of the aromatic hydrocarbon fractions isolated from corresponding unpolluted sediments in the region. The observed aromatic hump had little resemblance to the distribution of aromatic hydrocarbons in a typical North Sea crude oil. Incubation studies, however, showed that such a hump was appearing when oil-spiked sediments were aerobically biodegraded. From these incubation studies it was also evident that alkylaromatic hydrocarbons in the crude oil were biodegraded before any change in the normal alkanes was apparent. Therefore, the presence of an unresolved complex mixture in the gas chromatograms of aromatic hydrocarbon fractions from recent sediments can act as a marker to recognize contamination by crude oil.     

Identification of major water-soluble fluorescent components of some petrochemicals.

The chemical identities of several organic compounds that dominate the ultraviolet (UV) fluorescence of water after exposure to gasoline, diesel fuel and crude oil are presented. A combination of high-performance liquid chromatography with UV-fluorescence detection, fluorescence spectroscopy and gas chromatography-mass spectrometry (GC-MS) is used to show that naphthalene, methylnaphthalene and methylstyrene are the major fluorescent species in water following exposure to gasoline. These compounds are not dominant in water exposed to other petrochemicals we studied.     

Application of the luciferase cell culture bioassay for the detection of refined petroleum products

A luciferase cell culture-based bioassay, developed to detect 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-like activity of halo-genated and polycyclic aromatic hydrocarbons, was optimized to detect refined petroleum products and to determine their relative inducing potency. Quality control standards from 32 refined products (gasolines and diesels, jet fuels, lubricating oils, fuel oils and weathered products) and three commercial products were evaluated. Induction equivalents (I-EQs) were determined by direct comparison of the EC50 and EC20 values (based on the median and 20% TCDD maximal response, respectively) from dose-response curves for each product to those obtained with TCDD. Most petroleum products were active in the luciferase bioassay, with those products composed of fractions produced later in the distillation process (i.e. fuel oils) inducing higher levels. Additionally, weathering of products reduced their induction potency. Based on the high I-EQ estimates of many products, biological effects associated with exposure may have been previously underestimated using other diagnostic methods.     

Application of the Mussel Watch concept in studies of the distribution of hydrocarbons in the coastal zone of the Ebro Delta

The Mussel Watch concept was applied in a study of man-induced chemical changes in the Ebro Delta on the Catalonian coast to obtain a preliminary assessment of the distribution of synthetic organic compounds, petroleum and biogenic hydrocarbons in the local coastal zone. Mussels, oysters and clams were selected as the indicator organisms. Levels of petroleum accumulated by mussels were generally high, in the order of 100–800 μg^?1 dry weight, equivalent to those in mussels in the most polluted harbours and bays of California. The relative distributions of the steranes and pentacyclic triterpanes in the mussels were significantly different from those found in petroleum from a local field, indicating that local petroleum was not contributing to the present contamination. The composition of biogenic compounds was variable, probably reflecting differences in the composition of local plankton communities, PCB levels were high in relation to current levels in mussels from US sites, reflecting continuing PCB use in Spain. The Delta appears to be a point source of a number of organochlorine compounds, including HCB, the DDT compounds, endrin and γ-chlordane. Levels of the DDT compound o,p′-DDD, a pharmacologically active substance, were unexpectedly high; identification was confirmed by GS/MS. Many unidentified peaks were present on EC chromatograms, indicating a more complex pattern of contamination than might be suggested by printed summaries of data.     

Patterns of Chemical Changes During Environmental Alteration of Hydrocarbon Fuels

This paper discusses major environmental alteration processes and describes a set of chemical tests that have been developed to monitor compositional changes in hydrocarbon fuels released into the environment. The methods examine various homologous series of hydrocarbons including straight chain (paraffins or n-alkanes), branched chain (isoparaffins or isoprenoids), alicyclic (naphthenes or alkylated cyclohexanes), polycyclic (steranes and terpanes), and aromatic structures (benzene, toluene, ethylbenzene. xylenes, alkylated benzenes, polycyclic aromatic hydrocarbons, and aromatic steranes). Each one of these groups of hydrocarbons has a different tolerance to environmental alteration by evaporation, dissolution (water washing), and biodegradation. When used as an analytical system on environmental samples, the data obtained provide information on fuel type recognition patterns and on degradation levels of the various fuels, allowing for an estimate of residence time.     

Oxygen-Containing Compounds Identified in Groundwater from Fuel Release Sites Using GCxGC-TOF-MS

This research continues a 7-year study of oxygen-containing organic compounds present in groundwater at gasoline and diesel fuel release sites that are quantified as diesel-range “total petroleum hydrocarbons” when measured by methods utilizing solvent extraction and gas chromatography. Two-dimensional gas chromatography with time-of-flight mass spectrometry was used to tentatively identify 1162 compounds (TICs) in 113 groundwater samples from 22 sites. Samples were collected from wells either upgradient of the release, within the source zone, or downgradient of the source but still within the plume of dissolved organics associated with release. The names and formulas of all TICs found in samples from each well type are presented and the results from upgradient and downgradient locations are compared in detail. About 60% of the most frequently detected TICs in downgradient wells were also detected in upgradient wells. A majority of these were saturated straight chain alkyl acids, commonly called fatty acids, or fatty acid esters. Of TICs frequently detected in downgradient wells but not upgradient wells, over half were branched alkyl alcohols. Hierarchical cluster analysis results suggest about 80% of the chemical composition of downgradient samples is more similar to upgradient samples than to source area samples. This similarity is due to the presence of the same types of fatty acids and esters. Principal component analysis indicates a continuum of biodegradation between the source area and downgradient samples with the latter becoming more consistent with upgradient samples. Results suggest some TICs may not be petroleum degradation intermediates but compounds synthesized by microorganisms through secondary production and carbon cycling.     

Interpretation of Gas Chromatographic Data in Subsurface Hydrocarbon Investigations

Capillary column gas chromatography (GC) is extremely useful in investigations of subsurface contamination by petroleum hydrocarbons. Fluid samples collected from observation wells are evaluated by GC methods to detect and analyze petroleum hydrocarbons in dissolved and liquid phases. The presence, types and concentrations of many petroleum-derived hydrocarbons dissolved in ground water can be determined. GC analysis can also be used to determine the composition of liquid hydrocarbon products, including gasoline, distillates and heavier oils. The degree of degradation of sampled liquid hydrocarbon product can be estimated from GC information, and this information can be helpful in estimating the length of time the product has been in the subsurface. Determination of the hydrocarbon source and migration path can be made from GC analysis of fluid samples collected at two or more locations.
This paper is intended to demonstrate interpretative techniques that can be used by hydrogeologists to facilitate the detection, identification and mitigation of subsurface hydrocarbons.     

Ground Water Contamination in Kuwait Resulting from the 1991 Gulf War: A Preliminary Assessment

A large number of oil wells in Kuwait were damaged and ignited by the retreating Iraqi troops during the 1991 Gulf War. The resulting spillage of huge volumes of crude oil on the surface gave rise to oil lakes and crude oil–impregnated soil. Moreover, products of crude oil combustion had spread over a large tract of the ground surface, causing widespread contamination of soil. Hydrocarbon contamination of ground water by the infiltrating runoff water carrying the contaminants from the surface soil to the water table and/or through direct contact with the crude oil leaking through the damaged casing in the subsurface was feared. This preliminary study was carried out to investigate the extent and nature of this possible contamination of ground water. The results indicate that the shallow fresh water lenses present under the Umm Al-Aish water field and in the southeastern parts of the Raudhatain water field in North Kuwait were affected by hydrocarbon pollution. Standard methods like the determination of the contents of the total petroleum hydrocarbon by the Fourier transform infrared method and 16 polyaromatic hydrocarbons using the gas chromatography-mass spectrometry method did not work well, possibly due to the environmental degradation of the crude oil over time. The fluorescence methods and the total organic carbon and total organic matter gave better indications of the intensity and the extent of ground water pollution. The brackish water fields of South and Central Kuwait were, however, free of any indications of hydrocarbon contamination.     

Stratigraphic Trapping of Spilled Jet Fuel Beneath the Water Table

Environmental conditions and the initial attempt to recover JP-4 jet fuel from a shallow aquifer at a tank farm in Hanahan, South Carolina, in 1975. allowed the jet fuel to become stratigraphically trapped below the water table. The trapped jet fuel remained an undetected source of dissolved hydrocarbon contamination in shallow ground water in the area for 17 years. The trapped jet fuel was located when a variety of chemical, hydrologic. geologic, and historical evidence led investigators to install and sample deeper wells. These findings emphasize the need to use an integrated approach lo evaluating the data when determining the extent of contamination and planning fuel recovery operations in a lithologically heterogeneous aquifer.     

The Application of Petroleum Hydrocarbon Fingerprint Characterization in Site Investigation and Remediation

Tremendous resources have been and continue to be spent investigating and remediating petroleum hydrocarbon compounds (PHCs) in soil and ground water. Investigating and planning a remedial strategy for sites affected by PHCs is often a challenging task because of the complex chemical nature of the PHCs. the complex regulatory environment related to PHC cleanup, and the use of analytical methods that provide quantitation but not identification of PHCs. From a technical standpoint, the PHC impacting soil and/or ground water is frequently inadequately characterised, both in identification as well as in is general properties (solubility, toxicity). From a regulatory standpoint, promulgated or recommended total petroleum hydrocarbon (TPH) cleanup levels generally relate to assumed properties of specific unweathered products and are inconsistent among different agencies and regions. This produces a prime situation for unwillingly spending more resources on investigation or remediation than may be necessary, especially when the PHC in the subsurface has different properties from unweathered products such as gasoline or diesel.
Accurately identifying the PHC and its nature, a process known as fingerprint characterization, is critical to the determination of appropriate regulatory goals and design of cost-effective remedial approaches. This paper presents several case studies in which fingerprint characterization made a significant difference in the project outcome. In each instance the nature of the organic material was better understood, the regulatory cleanup levels were negotiated based on the nature of the material, and a remedial approach was implemented that differed significantly from and was generally less costly than what would have been required without fingerprint characterization data.     

Bioventing for in situ remediation

Abstract

The availability of oxygen generally controls the rate at which aerobic in situ bioremediation proceeds. Bioventing, which couples soil venting with bioremediation, is often the most effective means of supplying oxygen to unsaturated zone soil. Laboratory treatability studies were conducted which showed that bioventing could be successfully applied to compounds ranging from light hydrocarbons, such as gasoline or diesel, to heavier hydrocarbons, such as fuel oils, as well as other volatile and semivolatile compounds. In many cases, the promotion of biological activity through the addition of nutrients and moisture, and optimization of the bioventing flow rates, may achieve greater contaminant reductions than venting alone.     

Chromatographic separation of diasteriomeric isoprenoids for the identification of fossil oil contamination

In aliphatic hydrocarbon fractions of crude oils eight acyclic isoprenoid alkanes were separated from accompanying n-alkanes and iso-alkanes by high-performance glasscapillary gas chromatography. Four of these: 2,6,10-trimethyltetradecane (V), norpristane (IV), pristane (III), and phytane (II) could be resolved further to reveal a doublet produced by the different diastereoisomers.In these doublets the front peak represents stereoisomers formed during maturation of crude oil while the rear peak indicates the respective hydrocarbons carrying the original biogenic precursor configuration. This appearance of doublets demonstrates the loss of stereospecificity in hydrocarbons derived from phytol (I). By using the front peaks as diagenetic ‘maturity markers’ attributable to fossil fuels, hydrocarbon mixtures extracted from sea water samples contaminated with fossil oil could be investigated in detail. The quantitative relationship between recent biogenic and fossil fuel hydrocarbons could be determined in extracts in the lower boiling point range.