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Treatment of world's largest and extensively hydrocarbon polluted environment: Experimental approach and feasibility analysis

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Abstract

This paper investigated approaches to treat the polluted groundwater in selected aquifers in Kuwait, which is the most extensive and second to none in terrestrial world case history. The selected aquifers are susceptible to pollution by oil spills during the first Gulf War. Experimental samplings of polluted soils were analysed. Results showed that granulated activated carbon is very effective in removing petroleum hydrocarbons from contaminated water. A pump-and-treat remediation scheme has been suggested for the affected parts of the freshwater fields. The cost estimates indicated that a treatment process involving carbon adsorption to remove petroleum hydrocarbons, followed by reverse osmosis to remove salt was highly likely to be the most cost-effective treatment system. The current treatment design and parametric costing approach can be applied elsewhere for the role of bioremediation in the treatment of petroleum contaminated environment, hazardous effects of petroleum hydrocarbon and genetic engineering in bioremediation.

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Mixed anaerobic microbial subcultures enriched from a multilayered aquifer at a former chlorinated solvent disposal facility in West Louisiana were examined to determine the organism(s) involved in the dechlorination of the toxic compounds 1,2-dichloroethane (1,2-DCA) and 1,1,2-trichloroethane (1,1,2-TCA) to ethene. Sequences phylogenetically related to Dehalobacter and Dehalococcoides, two genera of anaerobic bacteria that are known to respire with chlorinated ethenes, were detected through cloning of bacterial 16S rRNA genes. Denaturing gradient gel electrophoresis analysis of 16S rRNA gene fragments after starvation and subsequent reamendment of culture with 1,2-DCA showed that the Dehalobacter sp. grew during the dichloroelimination of 1,2-DCA to ethene, implicating this organism in degradation of 1,2-DCA in these cultures. Species-specific real-time quantitative PCR was further used to monitor proliferation of Dehalobacter and Dehalococcoides during the degradation of chlorinated ethanes and showed that in fact both microorganisms grew simultaneously during the degradation of 1,2-DCA. Conversely, Dehalobacter grew during the dichloroelimination of 1,1,2-TCA to vinyl chloride (VC) but not during the subsequent reductive dechlorination of VC to ethene, whereas Dehalococcoides grew only during the reductive dechlorination of VC but not during the dichloroelimination of 1,1,2-TCA. This demonstrated that in mixed cultures containing multiple dechlorinating microorganisms, these organisms can have either competitive or complementary dechlorination activities, depending on the chloro-organic substrate.
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Massive oil fires in Kuwait were the aftermath of the Gulf War. This resulted in the pollution of air, water, and soil, the magnitude of which is unparalleled in the history of mankind. Oil fires damaged several oil well heads, resulting in the flow of oil, forming large oil lakes. Products of combustion from oil well fires deposited over large areas. Infiltrating rainwater, leaching out contaminants from oil lakes and products of combustion at ground surface, can reach the water table and contaminate the groundwater. Field investigations, supported by laboratory studies and mathematical models, show that infiltration of oil from oil lakes will be limited to a depth of about 2 m from ground surface. Preliminary mathematical models showed that contaminated rainwater can infiltrate and reach the water table within a period of three to four days, particularly at the Raudhatain and Umm Al-Aish regions. These are the only regions in Kuwait where fresh groundwater exists. After reaching the water table, the lateral movement of contaminants is expected to be very slow under prevailing hydraulic gradients. Groundwater monitoring at the above regions during 1992 showed minor levels of vanadium, nickel, and total hydrocarbons at certain wells. Since average annual rainfall in the region is only 120 mm/yr, groundwater contamination due to the infiltration of contaminated rainwater is expected to be a long-term one.
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Historic spillages of chlorinated hydrocarbons at a vinyl chloride plant in the Rotterdam–Botlek area in The Netherlands has lead to deep-seated pollution of the underlying aquifer. The principal pollutant is 1,2-dichloroethane (1,2-DCA). As a temporary measure, the contamination is being contained using a pump and treat system. In the long term, in-situ bioremediation has been proposed using a biologically active zone where pollutants would be dechlorinated by microorganisms that simultaneously degrade other carbon sources. In order to investigate the suitability of this new technology, a programme of laboratory tests was carried out. The laboratory programme involved a series of anaerobic soil column tests, where the selection and delivery of different carbon substrates that stimulated 1,2-DCA dechlorination were investigated. The soil columns were prepared using soil and groundwater samples from boreholes. Groundwater was flushed through the columns under anaerobic conditions. A comparison was made between the transformation of 1,2-DCA without a carbon substrate and in the presence of sugars (molasses) and alcohol (methanol) respectively. In addition, different modes of delivery were investigated. In the case of molasses, the material was injected into the column as a plug to simulate grout injection in the field, whereas methanol was delivered as a constant flow dissolved in the influent. Both carbon substrates resulted in the biotransformation of 1,2-DCA. However, fermentation of molasses produced secondary effects that led to a drop in pH and an excessive production of carbon dioxide, which temporarily blocked the flow of groundwater.
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Cationic surfactants can be used to modify surfaces of soils and subsurface materials to promote adsorption of hydrophobic organic compounds (HOC). Batch and column experiments were performed to investigate this phenomenon with the cationic surfactant dodecylpyridinium (DP), a series of chlorobenzenes as representative HOC, and a low organic carbon aquifer material (Lula). The adsorption isotherm of DP was highly nonlinear; at micromolar concentrations, DP was adsorbed strongly but not irreversibly; at millimolar concentrations, adsorption was relatively weak. Distribution ratios of the chlorobenzenes varied nonlinearly with DP loading. The elution of chlorobenzenes from columns packed with DP-treated aquifer material was examined; a transport model based on the results of the batch experiments and the local equilibrium assumption yielded an acceptable approximation for the coelution of DP and HOC from the column. It is concluded that treatment of surfaces with cationic surfactants shows promise as a means of promoting HOC sorption in a variety of treatment processes.
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Laboratory experiments have been carried out with and without groundwater flow in a two-dimensional laboratory-scale tank to assess the influence of layered media and hydraulic gradient on DNAPL infiltration and redistribution processes. Hydrofluoroether has been used as DNAPL and glass beads have been utilized as porous medium. An image analysis procedure has been used to determine saturation distribution during infiltration and redistribution processes. This method allows quantitative time dependent full fields mapping of the DNAPL saturation, as well as the monitoring of DNAPL saturation variation. By means of performed experiments important information were obtained about the migration and redistribution process, the infiltration and migration velocity, the characteristics of migration body. The experimental results show that the hydraulic gradient promotes the infiltration process, increasing the infiltration rate. It hampers DNAPL spread and fingering bringing to a reduction of residual DNAPL and it also promotes the DNAPL redistribution, and it reduces the amount remaining at residual saturation. Furthermore the hydraulic gradient promotes downward and down-gradient migration. DNAPL migration in the direction of water flow, can be considered important due to significant errors in the location of sources in the case of high gradients and high aquifer thicknesses, and for high water flow velocities, such as those which can be expected during pumping actions in water supply or in remediation activities.
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Accumulation of vinyl chloride (VC) is often a main concern at sites contaminated with chlorinated ethenes and ethanes due to its high toxicity. Since there can be several possible sources of VC and ethene at such sites, assessing the origin and fate of VC can be complicated. Aim of this study was to evaluate carbon isotope fractionation associated with various anaerobic processes that lead to the production of VC and ethene in view of using isotopes to evaluate the origin and fate of these compounds in groundwater. Microcosms were constructed using sediments and groundwater from a contaminated site and amended with potential precursors for VC and ethene production. In the microcosms with dichloroethene isomers, sequential reductive dechlorination was observed, and isotopic enrichmentfactors of -19.9 +/- 1.5 per thousand for cis-1,2-dichloroethene, -30.3 +/- 1.9 per thousand for trans-1,2-dichloroethene, and -7.3 +/- 0.4 per thousand for 1,1-dichloroethene were obtained. In microcosms with chlorinated ethanes, 1,2-dichloroethane (1,2-DCA) and 1,1,2-trichloroethane (1,1,2-TCA) were predominantly transformed by dichloroelimination to ethene and VC, respectively, and enrichmentfactors of -32.1 +/- 1.1 per thousand for 1,2OCA and -2.0 +/- 0.2 per thousand for 1,1,2-TCA were observed. Except for 1,1,2-TCA, a strong 13C enrichment in each of the potential precursor of VC was observed, which opens the possibility to trace the origin of VC based on the isotope ratio of potential precursors. Furthermore, it was possible to model the isotope evolution of VC present as substrate or intermediate product as a function of time. The study demonstrates that carbon isotope ratios can potentially be used for qualitative and possibly quantitative evaluation of the origin and fate of VC at sites with complex contaminant mixtures.
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The demonstration of monitored natural attenuation (MNA) of chlorinated hydrocarbons in groundwater is typically conducted through the evaluation of concentration trends and parent-daughter product relationships along prevailing groundwater flow paths. Unfortunately, at sites contaminated by mixtures of chlorinated ethenes, ethanes, and methanes, the evaluation of MNA by using solely concentration data and parent-daughter relationships can result in erroneous conclusions regarding the degradation mechanisms that are truly active at the site, since many of the daughter products can be derived from multiple parent compounds. Stable carbon isotope analysis was used, in conjunction with concentration data, to clarify and confirm the active degradation pathways at a former waste solvent disposal site where at least 14 different chlorinated hydrocarbons have been detected in the groundwater. The isotope data indicate that TCE, initially believed to be present as a disposed product and/or a PCE dechlorination intermediate, is attributable to dehydrochlorination of 1,1,2,2-PCA. The isotope data further support that vinyl chloride and ethene in the site groundwater result from dichloroelimination of 1,1,2-trichlorethane and 1,2-dichloroethane, respectively, rather than from reductive dechlorination of the chlorinated ethenes PCE, TCE, or 1,2-DCE. The isotope data confirm that the chlorinated ethanes and chlorinated methanes are undergoing significant intrinsic degradation, whereas degradation of the chlorinated ethenes may be limited. In addition to the classical trend of enriched isotope values of the parent compounds with increasing distance associated to biodegradation, shifts of isotope ratios of degradation byproduct in the opposite direction due to mixing of isotopically light byproducts of biodegradation with compounds from the source are shown to be of high diagnostic value. These data underline the value of stable isotope analysis in confirming transformation processes at sites with complex mixtures of chlorinated compounds.
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