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1.
Chromium(VI) concentrations in groundwater sampled from three contaminant plumes in aquifers in the Mojave Desert near Hinkley, Topock and El Mirage, California, USA, were as high as 2600, 5800 and 330 μg/L, respectively. δ53/52Cr compositions from more than 50 samples collected within these plumes ranged from near 0‰ to almost 4‰ near the plume margins. Assuming only reductive fractionation of Cr(VI) to Cr(III) within the plume, apparent fractionation factors for δ53/52Cr isotopes ranged from εapp = 0.3 to 0.4 within the Hinkley and Topock plumes, respectively, and only the El Mirage plume had a fractionation factor similar to the laboratory derived value of ε = 3.5. One possible explanation for the difference between field and laboratory fractionation factors at the Hinkley and Topock sites is localized reductive fractionation of Cr(VI) to Cr(III), with subsequent advective mixing of native and contaminated water near the plume margin. Chromium(VI) concentrations and δ53/52Cr isotopic compositions did not uniquely define the source of Cr near the plume margin, or the extent of reductive fractionation within the plume. However, Cr(VI) and δ53/52Cr data contribute to understanding of the interaction between reductive and mixing processes that occur within and near the margins of Cr contamination plumes. Reductive fractionation of Cr(VI) predominates in plumes having higher εapp, these plumes may be suitable for monitored natural attenuation. In contrast, advective mixing predominates in plumes having lower εapp, the highly dispersed margins of these plumes may be difficult to define and manage.  相似文献   

2.
A 2D horizontal reactive transport model of a chromate-contaminated site near Rivera, Switzerland, was developed using the computer code CrunchFlow to evaluate site remediation strategies. Transport processes were defined according to the results of an existing hydrological model, and the definition of geochemical (reactive) processes is based on the results of a detailed mineralogical and geochemical site characterization leading to a comprehensive conceptual site model. Kinetics of naturally occurring Cr(VI) reduction by Fe(II) and natural solid organic matter is quantified by fitting measured Cr isotope ratios to a modeled 1D section along the best constrained flow line. The simulation of Cr isotope fractionation was also incorporated into the 2D model. Simulation of the measured present day Cr(VI) plume and δ53Cr value distribution was used for the 2D model calibration and corresponds to a situation where only monitored natural attenuation (MNA) is occurring. Other 2D model runs simulate alternate excavation scenarios. The simulations show that with an excavation of the top 2–4 m the groundwater Cr(VI) plume can be minimized, and that a deeper excavation depth only diminishes the plume if all the contaminants can be removed. A combination of an excavation of the top 2–4 m and monitoring of the ongoing natural Cr(VI) reduction is suggested as the most ecological and economical remediation strategy, even though a remaining time period with ongoing subsoil Cr(VI) contamination in the order of 1 ka is predicted.  相似文献   

3.
Dissolved benzene was detected in the shallow unconfined Liwa aquifer, UAE, which represents the main freshwater source for the nearby residence Bu Hasa camp area. The main source of this contamination is believed to be the rejected water released from Bu Hasa liquid recovery plant. In this paper, a finite element model (METABIOTRANS) is used to simulate the fate and transport of the dissolved benzene plume in Liwa aquifer. Different remediation scenarios were simulated in which the slow-release oxygen source (SOS) technique is utilized to minimize benzene concentrations at the nearest camp supply wells downstream of the contamination zone. Results of the remediation scenarios show that the highest biodegradation rates occur when the oxygen source is placed near the plume center; where higher benzene concentrations exist. The nearest oxygen release source to the contamination zone caused higher stimulation to bacterial growth than further down-gradient oxygen sources. It also exhibited longer resident time of oxygen in the aquifer; and therefore, yielded higher reductions in benzene concentrations. However, using one central SOS proved to be insufficient as contaminant escaped laterally. Additional four transverse oxygen sources were necessary to capture benzene that laterally spread away from the contamination zone. These lateral SOSs were essential to reduce benzene concentrations at the supply wells that are located at the plume fringes. Finally, it was found that increasing oxygen release from one source did not always improve remediation; and that using several SOSs with lower release rates could be a more practical approach to enhance benzene biodegradation in the aquifer.  相似文献   

4.
The redox-sensitive stable isotope geochemistry of chromium bears the potential to monitor the attenuation of chromate pollution and to investigate changes in environmental conditions in the present and the past. The use of stable Cr isotope data as a geo-environmental tracer, however, necessitates an understanding of the reaction kinetics and Cr fractionation behaviour during redox transition and isotope exchange. Here, we report stable chromium isotope fractionation data for Cr(VI) reduction, Cr(III) oxidation and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous media. The reduction of Cr(VI) to Cr(III) with H2O2 under strongly acidic conditions shows a near-equilibrium isotope fractionation of Δ53/52Cr(Cr(III)-Cr(VI)) of −3.54 ± 0.35‰. At pH neutrality, however, the reduction experiments show a kinetic isotope fractionation Δ53/52Cr(Cr(III)-Cr(VI)) of −5‰ for the extent of reduction of up to 85% of the chromium. The oxidation of Cr(III) to Cr(VI) in alkaline media, using H2O2 as the oxidant, cannot be explained by a single, unidirectional reaction. Our experiments indicate that the involvement of the unstable intermediates Cr(IV) and Cr(V) and their disproportionation during redox reactions between Cr(III) and Cr(VI) influence the overall fractionation factor, depending on the prevailing pH conditions and the reaction rates. No detectable isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed over a timescale of days to weeks. This means that, at least within such a time frame, the isotopic composition of Cr(VI) in a natural system will not be influenced by equilibration with any Cr(III) and thus reveal the true extent of reduction, given that the Cr isotope composition of the source Cr(VI) and the fractionation factor for the prevailing conditions are known.  相似文献   

5.
《Applied Geochemistry》2005,20(11):1985-2002
Elevated levels of dissolved arsenic (∼300 μg L−1) have been detected beneath and in groundwater plumes extending away from a closed landfill in southern Maine. This study sought to determine the source of arsenic to the aquifer, the processes responsible for arsenic mobilization, and to evaluate the effectiveness of remediation efforts that have occurred at this site. The As appears to originate in the natural (glacial) aquifer solids, which contain ∼5 mg kg−1 As on a dry weight basis. This conclusion is supported by the relatively uniform distribution of As in sediment samples, results of laboratory batch incubation experiments, and comparisons with groundwaters in nearby wetlands, which also have high levels of dissolved As that do not appear to originate within the landfill. The As is mobilized in the subsurface by strongly reducing conditions beneath the landfill and in nearby wetlands. In the aquifer beneath the landfill, the average oxidation–reduction potential (ORP) is −95 mV (Eh + 105 mV), and these reducing conditions were primarily induced by landfill leachate. Remediation efforts at this site have included installation of a low permeability clay cap; groundwater extraction, oxidation, and re-injection; and subsurface oxidation by injection of magnesium peroxide. The natural source of arsenic within the aquifer solids, coupled with widespread reducing conditions, has severely limited the effectiveness of these interventions on groundwater arsenic concentrations.  相似文献   

6.
Chromium(VI) concentrations in excess of the California Maximum Contaminant Level (MCL) of 50 μg/L occur naturally in alkaline, oxic ground-water in alluvial aquifers in the western Mojave Desert, southern California. The highest concentrations were measured in aquifers eroded from mafic rock, but Cr(VI) as high as 27 μg/L was measured in aquifers eroded from granitic rock. Chromium(VI) concentrations did not exceed 5 μg/L at pH < 7.5 regardless of geology. δ53Cr values in native ground-water ranged from 0.7 to 5.1‰ and values were fractionated relative to the average δ53Cr composition of 0‰ in the earth’s crust. Positive δ53Cr values of 1.2 and 2.3‰ were measured in ground-water recharge areas having low Cr concentrations, consistent with the addition of Cr(VI) that was fractionated on mineral surfaces prior to entering solution. δ53Cr values, although variable, did not consistently increase or decrease with increasing Cr concentrations as ground-water flowed down gradient through more oxic portions of the aquifer. However, increasing δ53Cr values were observed as dissolved O2 concentrations decreased, and Cr(VI) was reduced to Cr(III), and subsequently removed from solution. As a result, the highest δ53Cr values were measured in water from deep wells, and wells in discharge areas near dry lakes at the downgradient end of long flow paths through alluvial aquifers. δ53Cr values at an industrial site overlying mafic alluvium having high natural background Cr(VI) concentrations ranged from −0.1 to 3.2‰. Near zero δ53Cr values at the site were the result of anthropogenic Cr. However, mixing with native ground-water and fractionation of Cr within the plume increased δ53Cr values at the site. Although δ53Cr was not necessarily diagnostic of anthropogenic Cr, it was possible to identify the extent of anthropogenic Cr at the site on the basis of the δ53Cr values in conjunction with major-ion data, and the δ18O and δD composition of water from wells.  相似文献   

7.
Anomalous concentrations of Cr(VI) occur in groundwaters of the Adamantina Aquifer, in a large region in the western state of São Paulo, sometimes exceeding the potability limit (0.05 mg L−1). To identify the possible geochemical reactions responsible for the occurrence of Cr in groundwater in Urânia, borehole rock samples were collected in order to carry out mineralogical and chemical analyses. In addition, multilevel monitoring wells were installed and groundwater samples were analyzed. Analyses of the borehole rock samples show the occurrence of a geochemical anomaly of Cr in the quartzose sandstones (average concentrations of 221 ppm). Chrome-diopside is one of the main minerals contributing to this anomaly, having an average Cr content of 1505 ppm. Sequential extraction experiments indicated weakly adsorbed Cr in the order of 0.54 ppm, and this quantity is enough to provide the Cr concentrations observed in groundwater. Groundwaters from the monitoring wells proved to be stratified, with the highest concentrations of Cr(VI) (0.13 mg L−1) being associated with high redox and pH values (over 10) and high concentrations of Na. Geochemical reactions that may explain the release of Cr from the solid phase to groundwater involve the release of Cr(III) from minerals (like chrome-diopside and Cr-Fe hydroxide), followed by oxidation of Cr(III) to Cr(VI), probably related to the reduction of Mn oxides present in the aquifer. Then cation exchange occurs and dissolution of carbonates which increases the pH of groundwater, resulting in the desorption and mobilization of Cr(VI) into groundwater.  相似文献   

8.
The risk of groundwater contamination by chromate at a former chromite ore processing industrial site in Rivera (Switzerland) was assessed by determining subsoil Cr(VI) concentrations and tracking naturally occurring Cr(VI) reduction with Cr isotopes. Using a hot alkaline extraction procedure, a total Cr(VI) contamination of several 1000 kg was estimated. Jarosite, KFe3((SO4)x(CrO4)1−x)2(OH)6, and chromatite (CaCrO4) were identified as Cr(VI) bearing mineral phases using XRD, both limiting groundwater Cr(VI) concentrations. To track assumed Cr(VI) reduction at field scale δ53Cr values of contaminated subsoil samples in addition to groundwater δ53Cr data are used for the first time. The measurements showed a fractionation of groundwater δ53Cr values towards positive values and subsoil δ53Cr towards negative values confirming reduction of soluble Cr(VI) to insoluble Cr(III). Using a Rayleigh fractionation model, a current Cr(VI) reduction efficiency of approximately 31% along a 120 m long flow path was estimated at an average linear groundwater velocity of 3.3 m/d. Groundwater and subsoil δ53Cr values were compared with a site specific Rayleigh fractionation model proposing that subsoil δ53Cr values can possibly be used to track previous higher Cr(VI) reduction efficiency during the period of industrial activity. The findings strongly favor monitored natural attenuation to be part of the required site remediation measures.  相似文献   

9.
The effective influence of industry or ultramafic rocks by natural processes to soil, plants and groundwater contamination by chromium, which is often a subject of debate, was investigated for the case of the Assopos basin, Greece. The Neogene Assopos basin, is mainly composed by Tertiary and Quaternary sediments of more than 400 m thick and is characterized by brittle type deformation (fault zones, faults). Chromium in soil, ranging from 67 to 204 ppm, is mostly hosted in chromite, Fe-chromite, Cr-bearing goethite and silicates.Special attention was given to the plants, which are a major source of organic matter that serves as the driving force for Cr(VI) reduction. The increase of the Fe, Mn and Ni contents, with the increasing Cr content in the plant-roots, in particular at the external parts of roots and those of bulb-type plants, suggest reduction and immobilization of Cr(VI) and that redox reactions play a significant role to the translocation processes from root to shoot.Groundwater samples from the Assopos aquifer showed a wide spatial variability, ranging from <2 to 180 ppb Crtotal content [almost same to the Cr(VI)-values] despite their spatial association. The presence of Cr(VI)-contaminated groundwater at depths >200 m is attributed to a direct injection of Cr(VI)-rich industrial wastes at depth rather than that Cr(VI) is derived from the Assopos river or by the interaction between water and Cr-bearing rocks. The heterogeneous distribution of Cr in groundwater may be related with the intense neotectonic deformation, as is exemplified by several sharp tectonic contacts between sediment types, while the Cr content in soil is mostly depend on the transported chromite grains.  相似文献   

10.
An investigation was conducted at Astrolabe Park landfill, a decommissioned municipal landfill in Sydney, Australia, to assess the physical and chemical processes affecting the distribution of inorganic constituents in the leachate plume. The plume is migrating from the landfill towards a groundwater-fed pond into which leachate-impacted groundwater discharges. Borehole geophysical logging and depth-discrete groundwater sampling were used to delineate the distribution of the leachate plume along two groundwater flow paths between the landfill and the shore of the pond. Borehole geophysical logs indicate a strong correlation between bulk and fluid electrical conductivity (EC) values, and help to identify small-scale heterogeneities that comprise a major constraint on contaminant transport within the aquifer. Variations in the distribution of several indicator parameters (EC, HCO3–, pH, Eh, NH4+/NO3–, S2–/SO42–) are used to assess the dominant processes affecting contaminant distribution along the flow path, including mixing of fresh and contaminated groundwater, oxidation/reduction reactions and ion exchange.  相似文献   

11.
地下水中稳定铬同位素的生物地球化学作用   总被引：2，自引：0，他引：2  
铬是地下水中常见的一种变价重金属污染物,在自然界中广泛分布且应用广泛。将Cr(Ⅵ)还原为Cr(Ⅲ)是地下水铬污染防治中的主要策略。在Cr(Ⅵ)的非生物还原过程中存在铬同位素分馏现象,通过地下水中铬同位素组成的变化情况可以定量地指示Cr(Ⅵ)的还原程度和速率。这被认为是一个重要发现,在地下水铬污染防治中有着广阔的应用前景。文中对铬与铬的来源、地下水中铬同位素的测定方法、铬同位素的生物地球化学作用、铬同位素在地下水污染防治中的应用等进行了系统综述。研究认为：微生物广泛参与地下水中铬的氧化与还原作用,并有可能产生显著的铬同位素分馏。地下水中被还原的Cr(Ⅵ)在微生物作用下有可能被活化,用非生物还原条件下的铬同位素分馏规律指示地下水中Cr(Ⅵ)还原程度可能会产生较大的误差。开展地下水中铬同位素的生物地球化学作用研究,特别是生物氧化Cr(Ⅲ)过程中的铬同位素分馏规律研究,对于更全面地认识铬同位素的指示作用具有重要意义。  相似文献   

12.
The historical disposal of acidic chromium sulfate solutions into unlined lagoons between 1953 and 1970 at an industrial site resulted in formation of a dense aqueous phase liquid (DAPL) plume [specific gravity 1.11 g/cm3, pH 3, up to 4700 mg/L Cr(III), and up to 90,000 mg/L SO4]. The DAPL sank through the shallow glacial till aquifer to an underlying impermeable gneissic bedrock from where it migrated downgradient along buried channels incised in the bedrock. Because of its high density, the plume chemistry is sharply stratified vertically. Chromium(III) predominates in the DAPL because excess Cr(VI) not reduced in the original process has been reduced by Fe(II) derived from silicates, while Cr(OH)3(am) occurs as surface coatings on silicate minerals and as discrete particles mixed with Fe(OH)3(am) and Al(OH)3(am). The solubility of Cr(OH)3(am) accurately describes Cr(III) concentrations in the plume and nearby groundwater, while Al and Fe in solution are also consistent with solubility-controlling oxyhydroxides. Because of these solubility controls, metal cations are attenuated relative to more mobile Cl and SO4, resulting in a chromatographic separation of solutes downgradient from the plume origin. The good agreement between predicted and observed solution concentrations illustrates the utility of equilibrium modeling when interpreting metal transport characteristics and in determining the efficacy of natural attenuation in subsurface systems.  相似文献   

13.
Groundwater is the most important source of water supply in southern Tunisia. Previous hydrogeologic and isotopic studies carried out in this region revealed the existence of two major aquifer systems: the “Complex Terminal” (CT) and the “Continental Intercalaire” (CI). Turonian carbonates constitute one of the major aquifer levels of the CT multilayered aquifer. It extends over most of southern Tunisia, and its hydrodynamic regime is largely influenced by tectonics, lithology and recharge conditions. Forty-eight groundwater samples from the CI and Turonian aquifers were collected between January and April 2004 for chemical and isotopic analyses. Hydrochemistry and isotopic tools were combined to get an insight into the processes controlling chemical composition of groundwater and wide-scale interaction of these two aquifer systems. Analysis of the dissolved constituents revealed that several processes control the observed chemical composition: (i) incongruent dissolution of carbonate minerals, (ii) dissolution of evaporitic minerals, and (iii) cation exchange. Dissolution alone cannot account for the observed high supersaturation states of groundwater with respect to calcite and dolomite. The observed supersaturation is most probably linked to geogenic CO2 entering water-bearing horizons of the CT and CI aquifers via deep tectonic faults and discontinuities and subsequent degassing in the exploitation wells. Presence of geogenic CO2 in the investigated region was confirmed by C isotope data of the DIC reservoir. The radiocarbon content of the Turonian samples varied between 9.5 and 43 pmc. For CI samples generally lower values were recorded, between 3.8 and 22.5 pmc. Stable isotope composition of Turonian groundwater samples varied from −8.3 to −5.3‰ for δ18O and from −60 to −25‰ for δ2H. The corresponding ranges of δ values for the Continental Intercalaire samples were from −8.9‰ to −6.9‰ for δ18O and from −68.2‰ to −45.7‰ for δ2H. Stable isotope composition of groundwater representing CT and CI aquifers provide strong evidence for regional interaction between both systems.  相似文献   

14.
We present some of the first analyses of the stable isotopic composition of dissolved silicon (Si) in groundwater. The groundwater samples were from the Navajo Sandstone aquifer at Black Mesa, Arizona, USA, and the Si isotope composition of detrital feldspars and secondary clay coatings in the aquifer were also analyzed. Silicon isotope compositions were measured using high-resolution multi-collector inductively coupled mass spectrometry (HR-MC-ICP-MS) (Nu1700 & NuPlasma HR). The quartz dominated bulk rock and feldspar separates have similar δ30Si of −0.09 ± 0.04‰ and −0.15 ± 0.04‰ (±95% SEM), respectively, and clay separates are isotopically lighter by up to 0.4‰ compared to the feldspars. From isotopic mass-balance considerations, co-existing aqueous fluids should have δ30Si values heavier than the primary silicates. Positive δ30Si values were only found in the shallow aquifer, where Si isotopes are most likely fractionated during the dissolution of feldspars and subsequent formation of clay minerals. However, δ30Si decreases along the flow path from 0.56‰ to −1.42‰, representing the most negative dissolved Si isotope composition so far found for natural waters. We speculate that the enrichment in 28Si is due to dissolution of partly secondary clay minerals and low-temperature silcretes in the Navajo Sandstone. The discovery of the large range and systematic shifts of δ30Si values along a groundwater flow path illustrates the potential utility of stable Si isotopes for deciphering the Si cycling in sedimentary basins, tracing fluid flow, and evaluating global Si cycle.  相似文献   

15.
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16.
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17.
The Blackwell site in northeastern Illinois was a classic sequential-use project combining land reclamation, a sanitary landfill, and a recreational park. This paper adds a recent assessment of leachate generation and groundwater contamination to the site's unfinished record. Hydrogeological studies show that (1) the landfill sits astride an outwash aquifer and a till mound, which are separated from an underlying dolomite aquifer by a thin, silty till; (2) leachate leaks from the landfill at an estimated average rate between 48 and 78 m3/d; (3) the resultant contaminant plume is virtually stagnant in the till but rapidly diluted in the outwash aquifer, so that no off-site contamination is detected; (4) trace VOC levels in the dolomite probably indicate that contaminants have migrated there from the landfill-derived plume in the outwash. Deviations from the original landfill concepts included elimination of a leachate collection system, increased landfill size, local absence of a clay liner, and partial use of nonclay cover. The hydrogeological setting was unsuitable for the landfill as constructed, indicating the importance of detailed geological consideration in landfill and land-use planning.  相似文献   

18.
At a Cr(VI) contaminated site in Thun, Switzerland, a permeable reactive barrier (PRB) was installed in 2008. Downstream Cr(VI) concentrations did not indicate any sign of its successful operation more than 2 years after PRB installation. The cause for this potential PRB failure was investigated by performing Cr isotope measurements and a multi-tracer experiment. The combination of reactive (Cr isotopes) and non-reactive tracers allowed characterizing the groundwater flow regime in the vicinity of the PRB in detail. In particular, it could be confirmed that most of the Cr(VI) load is currently bypassing the barrier, whereas only a minor Cr(VI) load is flowing through the PRB. Fitting of observed breakthrough curves using a conventional advection dispersion model resulted in average linear flow velocities of 13–15 m/day for the bypassing Cr(VI) load and 4–5 m/day for the Cr(VI) flowing through the barrier. Using a Rayleigh fractionation model a Cr(VI) reduction efficiency of 77–98% was estimated for the Cr(VI) load that is flowing through the barrier. In contrast, a value of 0–23% was estimated for the current overall PRB reduction efficiency. It is concluded that the PRB bypass and the low overall Cr(VI) reduction efficiency are caused by a limited PRB permeability inherited from skin effects that occurred during PRB emplacement.  相似文献   

19.
A small-scale field test was initiated in September 1994 to evaluate the in situ remediation of groundwater contaminated with chromate using a permeable reactive barrier composed of a mixture of zero-valent Fe, sand and aquifer sediment. The site used was an old chrome-plating facility located on a U.S. Coast Guard air base near Elizabeth City, North Carolina. Dissolved chromate concentrations were reduced to less than 0.01 mg/L via reduction from Cr(VI) to Cr(III) as a result of the corrosion of the Fe. As the Fe corrodes, pH increases, oxidation-reduction potential declines, dissolved oxygen is consumed, and Fe(II) is generated. Mineral phases formed as a result of the Fe corrosion include ferrous sulfides and various Fe oxides, hydroxides, and oxyhydroxides.  相似文献   

20.
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