Search

The migration of petroleum hydrocarbons in vadose zone involves complex coupled processes such as downward displacement and natural attenuation. Despite its significance in determining groundwater vulnerability to petroleum contamination and optimizing the remedial strategy, it has not been comprehensively studied in terms of overall processes under field-relevant conditions. In this study, a series of unsaturated soil column experiments were conducted by simulating subsurface diesel contamination within a vadose zone using different soil textures at different soil bulk densities and initial diesel concentrations, while partly exposing them to simulated precipitation. The results showed that the soil column with less fine fraction was favorable for the downward migration of diesel but unfavorable for its natural degradation. However, precipitation complicated the relative conductivities of multiple fluids (water, air, and diesel) through the pore network, therby decreasing diesel migration and degradation. For example, the downward migration of diesel in the SL column decreased by 8.4% under precipitation, while the overall attenuation rate dropped to almost 0.24% of its original state. Lowering bulk density (from 1.5 to 1.23 g/cm3), however, could enhance the attenuation rate presumably due to the secured void space for the incoming fluids. A high initial concentration of diesel (2%; w/w) inhibited its natural attenuation, while its influence on its vertical propagation after the precipitation was not significant. The present findings provide a mechanistic basis for approximating the behavior of petroleum hydrocarbons in a random vadose zone., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Assessment of Zn toxicity/mobility based on its speciation and transformations in soils is critical for maintaining human and ecosystem health. Zn-concentrate (56 % Zn as ZnS, sphalerite) has been imported through a seaport and transported to a Zn-smelter for several decades, and smelting processes resulted in aerial deposition of Zn and sulfuric acids in two geochemically distinct territories around the smelter (mountain-slope and riverside). XAFS analysis showed that the mountain-slope soils contained franklinite (ZnFe 2 O 4 ) and amorphous (e.g., sorbed) species of Zn(II), whereas the riverside sediments contained predominantly hydrozincite [Zn 5 (OH) 6 (CO 3 ) 2 ], sphalerite, and franklinite. The mountain-slope soils had low pH and moderate levels of total Zn (~ 1514 ppm), whereas the riverside sediments had neutral pH and higher total Zn (12,363 ppm). The absence of sphalerite and the predominance of franklinite in the mountain-slope soils are attributed to the susceptibility of sphalerite and the resistance of franklinite to dissolution at acidic pH. These results are compared to previous Zn analyses along the transportation routes, which showed that Zn-concentrate spilled along the roadside in dust and soils underwent transformation to various O-coordinated Zn species. Overall, Zn-concentrate dispersed in soils and sediments during transportation and smelting transforms into Zn phases of diverse stability and bioavailability during long-term weathering., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The natural attenuation potential of a vadose zone against diesel is critical for optimizing remedial actions and determining groundwater vulnerability to contamination. Here, diesel attenuation in unsaturated soils was systematically examined to develop a qualitative relationship between physical soil properties and the natural attenuation capacity of a vadose zone against diesel. The uniformity coefficient (C u ) and water saturation (S w , %) were considered as the proxies reflecting the degree of effects by porous network and water content in different soils, respectively. These, in turn, are related to the primary diesel attenuation mechanisms of volatilization and biodegradation. The volatilization of diesel was inversely proportional to C u and S w , which could be attributed to effective pore channels facilitating gas transport. Conversely, biodegradation was highly proportional to C u under unsaturated conditions (S w  = 35-71%), owing to nutrients typically associated with fine soil particles. The microbial community in unsaturated soils was affected by S w rather than C u . The overall diesel attenuation including volatilization and biodegradation was optimized at S w  = 35% for all tested soils., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Identifying the cause of inconsistent landfarming efficacy is critical to designing optimal remedial strategies for petroleum-contaminated sites. We assessed contaminated soils collected from two former military bases in South Korea to better understand the role and influence of different factors. Landfarming remediation was simulated in the laboratory by applying comparable practices (such as tillage and bioaugmentation) and the relevant mechanism was examined. We then systematically examined potential factors affecting petroleum-removal efficacy, including the content of fine soil particles, the initial concentration and composition of petroleum contaminants, and the degree of soil-contaminant interaction. The distribution range of total petroleum hydrocarbons (TPHs) and the size of unresolved complex mixture (UCM) found in gas chromatography data showed that petroleum composed of TPHs with lower carbon numbers and having smaller size of UCM could be treated more effectively by landfarming. Incorporating the evaluation of the distribution range and UCM properties of petroleum, rather than simply considering its total concentration, is a more accurate and efficient method for determining the site-specific suitability of landfarming as a remedial option, as well as for assessing the necessity of supplementary processes., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The water and oxygen contents of the vadose zone change cyclically depending upon the meteorological condition (e.g., intermittent rainfall), which can affect the biogeochemical reactions that govern the fate of arsenic (As). To simulate and evaluate the transient behavior of As in this zone when subjected to repeated wet and dry conditions, soil column experiments with different soil properties were conducted. Three wetting-drying cycles resulted in the fluctuation of water and dissolved oxygen contents, and consequently, the reduction-oxidation potential in the soil columns. Under these circumstances, the biotic reduction of As(V) to As(III) was observed, especially in the column filled with soils enriched in organic matter. Most of the As was found to be associated with soil particles rather than to be dissolved in the pore water in all of the columns tested. Retention of As was more preferable in the soil column with a higher Fe content and bulk density, which provided more sorption sites and reaction time, respectively. However, a considerable amount of soil-bound As could be remobilized and released back to the pore water with the repetition of wetting and drying due to the transformation of As(V) to As(III)., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Zinc contamination in near- and sub-surface environments is a serious threat to many ecosystems and to public health. Sufficient understanding of Zn speciation and transport mechanisms is therefore critical to evaluating its risk to the environment and to developing remediation strategies. The geochemical and mineralogical characteristics of contaminated soils in the vicinity of a Zn ore transportation route were thoroughly investigated using a variety of analytical techniques (sequential extraction, XRF, XRD, SEM, and XAFS). Imported Zn-concentrate (ZnS) was deposited in a receiving facility and dispersed over time to the surrounding roadside areas and rice-paddy soils. Subsequent physical and chemical weathering resulted in dispersal into the subsurface. The species identified in the contaminated areas included Zn-sulfide, Zn-carbonate, other O-coordinated Zn-minerals, and Zn species bound to Fe/Mn oxides or clays, as confirmed by XAFS spectroscopy and sequential extraction. The observed transformation from S-coordinated Zn to O-coordinated Zn associated with minerals suggests that this contaminant can change into more soluble and labile forms as a result of weathering. For the purpose of developing a soil washing remediation process, the contaminated samples were extracted with dilute acids. The extraction efficiency increased with the increase of O-coordinated Zn relative to S-coordinated Zn in the sediment. This study demonstrates that improved understanding of Zn speciation in contaminated soils is essential for well-informed decision making regarding metal mobility and toxicity, as well as for choosing an appropriate remediation strategy using soil washing., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The effects of extreme geochemical conditions on microbial community composition were investigated for two distinct sets of sediment samples collected near weathered mine tailings. One set (SCH) showed extraordinary geochemical characteristics: As (6.7-11.5%), Pb (1.5-2.1%), Zn (0.1-0.2%), and pH (3.1-3.5). The other set (SCL) had As (0.3-1.2%), Pb (0.02-0.22%), and Zn (0.01-0.02%) at pH 2.5-3.1. The bacterial communities in SCL were clearly different from those in SCH, suggesting that extreme geochemical conditions affected microbial community distribution even on a small spatial scale. The clones identified in SCL were closely related to acidophilic bacteria in the taxa Acidobacterium (18%), Acidomicrobineae (14%), and Leptospirillum (10%). Most clones in SCH were closely related to Methylobacterium (79%) and Ralstonia (19%), both well-known metal-resistant bacteria. Although total As was extremely high, over 95% was in the form of scorodite (FeAsO4·2H2O). Acid-extractable As was only ∼118 and ∼14 mg kg(-1) in SCH and SCL, respectively, below the level known to be toxic to bacteria. Meanwhile, acid-extractable Pb and Zn in SCH were above toxic concentrations. Because As was present in an oxidized, stable form, release of Pb and/or Zn (or a combination of toxic metals in the sediment) from the sediment likely accounts for the differences in microbial community structure. The results also suggest that care should be taken when investigating mine tailings, because large differences in chemical/biological properties can occur over small spatial scales., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Hydrocarbons found in the environment are typically characterized by gas chromatography (GC). The shape of the GC chromatogram has been used to identify the source of petroleum contamination. However, the conventional practice of simply comparing the peak patterns of source products to those of environmental samples is dependent on the subjective decisions of individual analysts. We have developed and verified a quantitative analytical method for interpreting GC chromatograms to distinguish refined petroleum products in contaminated soils. We found that chromatograms for gasoline, kerosene, and diesel could be divided into three ranges with boundaries at C6, C8, C16, and C26. In addition, the relative peak area (RPA(GC)) of each range, a dimensionless ratio of the peak area within each range to that of the total range (C6-C26), had a unique value for each petroleum product. An identification index for GC chromatograms (ID(GC)), defined as the ratio of RPA(GC) of C8-C16 to that of C16-C26, was able to identify diesel and kerosene sources in samples extracted from artificially contaminated soils even after weathering. Thus, the ID(GC) can be used to effectively distinguish between refined petroleum products in contaminated soils.

Partitioning tracer method has been studied as an effective technique for estimating the light nonaqueous-phase liquid (LNAPL) contamination in the subsurface. This study is for investigating the effect of soil organic contents on the LNAPL quantification using partitioning tracer method. The sorption characteristics of alcohol tracers to the soils having different organic carbon contents were evaluated by sorption isotherm experiments. In the column tests, the soils were contaminated with jet-fuel and the average saturations of residual jet-fuel were estimated by partitioning tracer method and compared with that by the volume measurement. The sorption results indicated that considerable amount of 4-methyl-2-pentanol and hexanol could be sorbed to the soils and the sorption amount of 2-ethyl-1-butanol was relatively smaller than those of the other alcohol tracers. The column experiments demonstrated that the accuracy of quantification for the jet-fuel by partitioning tracer method should decrease with increasing the soil organic carbon contents. However, the accuracy could be enhanced by considering the sorption of tracer to the soils, especially for the tracer of 2-ethyl-1-butanol., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Transmissible spongiform encephalopathies (TSEs) are progressive neurodegenerative diseases and include bovine spongiform encephalopathy of cattle, chronic wasting disease (CWD) of deer and elk, scrapie in sheep and goats, and Creutzfeldt-Jakob disease in humans. An abnormally folded form of the prion protein (designated PrP(TSE)) is typically associated with TSE infectivity and may constitute the major, if not sole, component of the infectious agent. Transmission of CWD and scrapie is mediated in part by an environmental reservoir of infectivity. Soil appears to be a plausible candidate for this reservoir. The transport of TSE agent through soil is expected to influence the accessibility of the pathogen to animals after deposition and must be understood to assess the risks associated with burial of infected carcasses. We report the results of saturated column experiments designed to evaluate PrP(TSE) transport through five soils with relatively high sand or silt contents and low organic carbon content. Protease-treated TSE-infected brain homogenate was used as a model for PrP(TSE) present in decomposing infected tissue. Synthetic rainwater was used as the eluent. All five soils retained PrP(TSE); no detectable PrP(TSE) was eluted over more than 40 pore volumes of flow. Lower bound apparent attachment coefficients were estimated for each soil. Our results suggest that TSE agent released from decomposing tissues to soils with low organic carbon content would remain near the site of initial deposition. In the case of infected carcasses deposited on the land surface, this may result in local sources of infectivity to other animals.