pH neutralization and zonation in alkaline-saline tank waste plumes

At the Hanford Site in Washington State, the pH values of contaminant plumes resulting from leaking of initially highly alkaline-saline radioactive waste solutions into the subsurface are now found to be substantially neutralized. However, the nature of plume pH neutralization has not previously been understood. As a master geochemical variable, pH needs to be understood in order to predict the fate and transport of contaminants carried by the waste plumes. Through this laboratory study, we found that the plume pH values spanned a broad range from 14 (within the near-source region) down to the value of 7 (lower than the pH value of the initial soil solution) while the plume was still connected to an actively leaking source. We defined two zones within a plume: the silicate dissolution zone (SDZ, pH 14-10) and the neutralized zone (NZ, pH 10-7). Quartz dissolution at elevated temperature and precipitation of secondary silicates (including sodium metasilicate, cancrinite, and zeolites) are the key reactions responsible for the pH neutralization within the SDZ. The rapid and thorough cation exchange of Na+ replacing Ca2+/Mg2+, combined with transport, resulted in a dynamic Ca2+/Mg2+-enriched plume front. Subsequent precipitation of calcite, sodium silicate, and possibly talc led to dramatically reduced pH within the plume front and the neutralized zone. During aging (after the plume source became inactive), continued quartz dissolution and the secondary silicate precipitation drove the pH value lower, toward pH 11 at equilibrium within the SDZ, whereas the pH values in the NZ remained relatively unchanged with time. A pH profile of 11 from the plume source to pH 7 at the plume front is expected for a historical plume. This laboratory-based study provided realistic plume pH profiles (consistent with that measured from borehole samples) and identified underlying mechanisms responsible for pH evolution.     

Laboratory investigations of enhanced sulfate reduction as a groundwater arsenic remediation strategy

Landfills have the potential to mobilize arsenic via induction of reducing conditions in groundwater and subsequent desorption from or dissolution of arsenic-bearing iron phases. Laboratory incubation experiments were conducted with materials from a landfill where such processes are occurring. These experiments explored the potential for induced sulfate reduction to immobilize dissolved arsenic in situ. The native microbial community at this site reduced sulfate in the presence of added acetate. Acetate respiration and sulfate reduction were observed concurrent with dissolved iron concentrations initially increasing from 0.6 microM (0.03 mg L(-1)) to a maximum of 111 microM (6.1 mg L(-1)) and subsequently decreasing to 0.74 microM (0.04 mg L(-1)). Dissolved arsenic concentrations initially covaried with iron but subsequently increased again as sulfide accumulated, consistent with the formation of soluble thioarsenite complexes. Dissolved arsenic concentrations subsequently decreased again from a maximum of 2 microM (148 microg L(-1)) to 0.3 microM (22 microg L(-1)), consistent with formation of sulfide mineral phases or increased arsenic sorption at higher pH values. Disequilibrium processes may also explain this second arsenic peak. The maximum iron and arsenic concentrations observed in the lab represent conditions most equivalent to the in situ conditions. These findings indicate that enhanced sulfate reduction merits further study as a potential in situ groundwater arsenic remediation strategy at landfills and other sites with elevated arsenic in reducing groundwater.     

Modeling of microbial dynamics and geochemical changes in a metal bioprecipitation experiment

A biogeochemical transport modeling study was carried out to analyze large-scale laboratory column experiments in which ethanol was used as an electron donor to create favorable conditions for the immobilization of selected trace metals (Zn and Cu) in groundwater. Microbial activity was explicitly simulated to capture the dynamic changes of the redox zonation within the column (i) in the early phase of the experiment (microbial lag) and (ii) in response to a significant decrease in the pH of the feed solution introduced after 188 days. The simulated redox dynamics agreed well with the observations after the pH-dependency of microbial growth was incorporated into the microbial model. The study showed that residual minerals may have buffered the pH for a period after the pH of the feed solution was decreased. Where the buffering capacity was exhausted, the pH decreased, leading to a successive downstream movement of the redox boundaries. The simulations reproduced the Zn immobilization within the sulfate-reducing zone as well as its partial remobilization after this zone moved further downstream. The immobilization of Cu within the denitrifying zone could also be well explained by incorporating malachite (Cu2(OH)2CO3) precipitation in the simulations.     

Microbial and nutrient investigations into the use of in situ layers for treatment of tailings effluent

The release of acidic drainage, containing high concentrations of dissolved metals, is associated with mining districts throughout the world. Remediation of acidic drainage at active and abandoned mines remains a significant challenge. A potential alternative technique to prevent the release of acidic drainage is the addition of labile organic carbon to mine wastes during deposition, creating large in situ treatment systems. Organic carbon can enhance bacterially mediated sulfate reduction and subsequent metal sulfide precipitation, treating metal-contaminated water prior to discharge from the impoundment. Two laboratory column experiments were conducted using simulated mine drainage water. The columns contained tailings derived from the Kidd Creek Metallurgical site in Timmins, Ontario, and reactive materials mixed to a 4:1 volumetric ratio. The average sulfate reduction rate observed in the woodchip column was 0.009 mmol L(-1) day(-1) g(-1) organic matter and in the pulp waste column 0.018 mmol L(-1) day(-1) g(-1) organic matter. Residence times were 14 days in the woodchip column, resulting in the average removal of 500 mg L(-1) (5.2 mmol L(-1)) SO4 and 60 mg L(-1) (1.1 mmol L(-1)) Fe, and 13 days in the pulp waste column, resulting in the average removal of 600 mg L(-1) (6.2 mmol L(-1)) SO4 and the complete removal of 100 mg L(-1) (1.8 mmol L(-1)) Fe. In both columns, sulfate reduction was coupled with an increase in alkalinity and pH and the complete removal of 80 mg L(-1) (1.2 mmol L(-1)) Zn and other metals. Populations of sulfate-reducing bacteria within both columns increased by 3-4 orders of magnitude, and bacterial activity was up to 5 times greater than in the unamended tailings. The woodchip material contained lower concentrations of labile C, N, and P than the pulp waste, possibly accounting for the lower sulfate reduction rates and metal removal capacity observed.     

In situ metal precipitation in a zinc-contaminated, aerobic sandy aquifer by means of biological sulfate reduction

The applicability of in situ metal precipitation (ISMP) based on bacterial sulfate reduction (BSR) with molasses as carbon source was tested for the immobilization of a zinc plume in an aquifer with highly unsuitable initial conditions (high Eh, low pH, low organic matter content, and low sulfate concentrations), using deep wells for substrate injection. Batch experiments revealed an optimal molasses concentration range of 1-5 g/L and demonstrated the necessity of adding a specific growth medium to the groundwater. Without this growth medium, even sulfate, nitrogen, phosphorus, and potassium addition combined with pH optimization could not trigger biological sulfate reduction. In column experiments, precipitation of ZnS(s) was induced biologically as well as chemically (by adding Na2S). In both systems, zinc concentrations dropped from about 30 mg/L to below 0.02 mg/L. After termination of substrate addition the biological system showed continuation of BSR for at least 2 months, suggesting the insensitivity of the sulfate reducing system for short stagnations of nutrient supply, whereas in the chemical system an immediate increase of Zn concentrations was observed. A pilot experiment conducted in situ at the zinc-contaminated site showed a reduction of zinc concentrations from around 40 mg/L to below 0.01 mg/L. Termination of substrate supply did not result in an immediate stagnation of the BSR process, but continuation of BSR was observed for at least 5 weeks.     

Reactive transport modeling of column experiments for the remediation of acid mine drainage

Reactive transport modeling was used to evaluate the performance of two similar column experiments. The experiments were designed to simulate the treatment of acid mine drainage through microbially mediated sulfate reduction and subsequent sulfide mineral precipitation by means of an organic carbon permeable reactive barrier. Principal reactions considered in the simulations include microbially mediated reduction of sulfate by organic matter, mineral dissolution/precipitation reactions, and aqueous complexation/hydrolysis reactions. Simulations of column 1, which contained composted leaf mulch, wood chips, sawdust, and sewage sludge as an organic carbon source, accurately predicted sulfate concentrations in the column effluent throughout the duration of the experiment using a single fixed rate constant for sulfate reduction of 6.9 x 10(-9) mol L(-1) s(-1). Using the same reduction rate for column 2, which contained only composted leaf mulch and sawdust as an organic carbon source, sulfate concentrations at the column outlet were overpredicted at late times, suggesting that sulfate reduction rates increased over the duration of the column experiment and that microbial growth kinetics may have played an important role. These modeling results suggest that the reactivity of the organic carbon treatment material with respect to sulfate reduction does not significantly decrease over the duration of the 14-month experiments. The ability of the columns to remove ferrous iron appears to be strongly influenced by the precipitation of siderite, which is enhanced by the dissolution of calcite. The simulations indicate that while calcite was available in the column, up to 0.02 mol L(-1) of ferrous iron was removed from solution as siderite and mackinawite. Later in the experiments after approximately 300 d, when calcite was depleted from the columns, mackinawite became the predominant iron sink. The ability of the column to remove ferrous iron as mackinawite was estimated to be approximately 0.005 mol L(-1) for column 1. As the precipitation of mackinawite is sulfide limited at later times, the amount of iron removed will ultimately depend on the reactivity of the organic mixture and the amount of sulfate reduced.     

Sources of sulfate supporting anaerobic metabolism in a contaminated aquifer

Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis-Menten-like relationship with an apparent Km and Vmax of approximately 80 and 0.83 microM SO4(-2) x day(-1), respectively. The concentration of sulfate in the core of the leachate plume was well below 20 microM and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (approximately 100 microM) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.     

嗜酸乳杆菌胆盐水解酶的分离纯化及酶学性质

对嗜酸乳杆菌La-XH1产生的胆盐水解酶进行分离纯化,并对其部分酶学性质进行研究。结果表明：嗜酸乳杆菌La-XH1胆盐水解酶的粗酶液经硫酸铵沉淀、DEAE-Sepharose CL-6B柱层析后的酶比活力分别为47.82 U/mg和115.85 U/mg,纯化倍数分别为4.46 倍和10.82 倍,酶的回收率分别为59.89%和25.11%;通过十二烷基硫酸钠-聚丙烯酰胺凝胶电泳（sodium dodecylsulfate polyacrylamide gel electrophoresis,SDS-PAGE）电泳分析,该酶的分子质量约为43 kD,最适温度为40 ℃,最适pH值为6.0,Fe3+、Ca2+、Mg2+、Mn2+、Zn2+对该酶有激活作用,其中Fe3+的激活作用最强,Na+、K+对该酶几乎无作用,而Cu2+、Ba2+对该酶有很强的抑制作用。     

Post-depositional behavior of Cu in a metal-mining polishing pond (East Lake, Canada)

The post-depositional behavior of Cu in a gold-mining polishing pond (East Lake, Canada) was assessed after mine closure by examination of porewater chemistry and mineralogy. The near-surface (upper 1.5 cm) sediments are enriched in Cu, with values ranging from 0.4 to 2 wt %. Mineralogical examination revealed that the bulk of the Cu inventory is present as authigenic copper sulfides. Optical microscopy, energy-dispersion spectra, and X-ray data indicate that the main Cu sulfide is covellite (CuS). The formation of authigenic Cu-S phases is supported by the porewater data, which demonstrate that the sediments are serving as a sink for dissolved Cu below sub-bottom depths of 1-2 cm. The zone of Cu removal is consistent with the occurrence of detectable sulfide and the consumption of sulfate. The sediments can be viewed as a passive bioreactorthat permanently removes Cu as insoluble copper sulfides. This process is not unlike that which occurs in other forms of bioremediation, such as wetlands and permeable reactive barriers. Above the zone of Cu removal, dissolved Cu maxima in the interfacial porewaters range from 150 to 450 microg L(-1) and reflect the dissolution of a Cu-bearing phase in the surface sediments. The reactive phase is thought to be a component of treatment sludges delivered to the lake as part of cyanide treatment. Flux calculations indicate that the efflux of dissolved Cu from the sediments to the water column (14-51 microg cm(-2) yr(-1)) can account for the elevated levels of dissolved Cu in lake waters (approximately 50 microg L(-1)). Implications for lake recovery are discussed.     

Remediation of a marine shore tailings deposit and the importance of water-rock interaction on element cycling in the coastal aquifer

We present the study of the geochemical processes associated with the first successful remediation of a marine shore tailings deposit in a coastal desert environment (Bahi?a de Ite, in the Atacama Desert of Peru). The remediation approach implemented a wetland on top of the oxidized tailings. The site is characterized by a high hydraulic gradient produced by agricultural irrigation on upstream gravel terraces that pushed river water (～500 mg/L SO(4)) toward the sea and through the tailings deposit. The geochemical and isotopic (δ(2)H(water) and δ(18)O(water), δ(34)S(sulfate), δ(18)O(sulfate)) approach applied here revealed that evaporite horizons (anhydrite and halite) in the gravel terraces are the source of increased concentrations of SO(4), Cl, and Na up to ～1500 mg/L in the springs at the base of the gravel terraces. Deeper groundwater interacting with underlying marine sequences increased the concentrations of SO(4), Cl, and Na up to 6000 mg/L and increased the alkalinity up to 923 mg/L CaCO(3) eq. in the coastal aquifer. These waters infiltrated into the tailings deposit at the shelf-tailings interface. Nonremediated tailings had a low-pH oxidation zone (pH 1-4) with significant accumulations of efflorescent salts (10-20 cm thick) at the surface because of upward capillary transport of metal cations in the arid climate. Remediated tailings were characterized by neutral pH and reducing conditions (pH ～7, Eh ～100 mV). As a result, most bivalent metals such as Cu, Zn, and Ni had very low concentrations (around 0.01 mg/L or below detection limit) because of reduction and sorption processes. In contrast, these reducing conditions increased the mobility of iron from two sources in this system: (1) The originally Fe(III)-rich oxidation zone, where Fe(III) was reduced during the remediation process and formed an Fe(II) plume, and (2) reductive dissolution of Fe(III) oxides present in the original shelf lithology formed an Fe-Mn plume at 10-m depth. These two Fe-rich plumes were pushed toward the shoreline where more oxidizing and higher pH conditions triggered the precipitation of Fe(III)hydroxide coatings on silicates. These coatings acted as a filter for the arsenic, which naturally infiltrated with the river water (～500 μg/L As natural background) into the tailings deposit.     

韦伯灵芝漆酶的分离纯化及其性质

采用硫酸铵分级盐析、透析、聚乙二醇浓缩和高效液相色谱柱层析从韦伯灵芝TZC-1 发酵液中分离纯化得到电泳纯漆酶,其纯化倍数为37.1 倍,酶活性回收率为21.3%。活性-PAGE(聚丙烯酰胺凝胶电泳)结果表明该漆酶由一种同工酶组成,纯化漆酶经SDS-PAGE 检测显示为单一条带,其分子质量约为40kD。该漆酶催化底物ABTS 的最适反应温度为50～60℃,最适反应pH 值为4.6,在60℃以下和pH3.0～5.0 范围内保持稳定,以ABTS为底物的表观Km 值为13.8μmol/L。Fe2+ 完全抑制酶活,Al3+ 和Mn2+ 对该漆酶也有明显抑制作用,Hg+、Cu2+ 和Mg2+ 对该酶有明显激活作用,而Zn2+、Ba2+ 及K+ 对该酶活性影响不大。     

紫色红曲霉中新型酯酶ESM1的纯化及其酶学特性研究

该研究以白酒大曲中筛选出的一株高产酯酶菌株HQ为研究对象,采用分子生物学对其进行菌种鉴定。通过硫酸铵二级沉淀、丁基琼脂糖凝胶柱和Superdex G-200柱对其所产的酯酶进行纯化,并进行N-端序列、质谱和酶学性质分析。结果表明,菌株HQ被鉴定为紫红曲霉（Monascus purpureus）,经纯化获得一个分子质量为60 kDa的酯酶,命名为ESM1。酯酶ESM1具有一段酸性蛋白酶的肽段序列,最适温度为60 ℃、最适pH值为7.0,在温度为50 ℃的环境和中性环境中表现出良好的稳定性。Zn2+、Ca2+和Na+对ESM1有促进作用,其中Zn2+促进作用最高,Cu2+、Mg2+、Fe2+和Mn2+有抑制作用,其中Cu2+的抑制作用最强。     

Structural study of the incorporation of heavy metals into solid phase formed during the oxidation of EDTA by permanganate at high pH

Properties of solid phases formed during the oxidation of EDTA by permanganate in a high-pH, high-ionic strength solution, and the retention of Cu2+, Ni2+, and Zn2+ by them were examined. Morphologically, the solids were agglomerates of particles with sizes <100 nm. X-ray absorption spectroscopy (XAS) analysis indicated that these particles were birnessite. Its precipitation was accompanied by the removal of Zn2+ and Cu2+ released as a result of the breakdown of their complexes with EDTA. However, Ni2+ was not removed from the supernatant. Cu2+ was strongly bound by birnessite and exhibited little mobility in the pH range from 3 to 14. Zn2+ was more mobile, especially at pH > 12. XAS showed that Cu2+ binding sites were located within MnO6 octahedra-comprised sheets that constitute birnessite while Zn2+ was positioned between them.     

植物乳杆菌亚油酸异构酶的分离纯化及其性质研究

经硫酸铵分级沉淀、阴离子交换层析和凝胶过滤,由植物乳杆菌(LactobacillusplantarumL 2 9)分离纯化得到亚油酸异构酶,分子量为4 3ku。对其酶学性质进行研究,结果表明,温度37℃、pH 6 0时酶活性较高;Co2 + 、Fe2 + 可提高酶的活性,Cu2 + 、Zn2 + 则对酶活力有抑制作用;该酶作用于亚油酸的Km=2 5 3×10 -5mol/L ,Vmax=2 5 7×10 -8mol/ (min·mg)。     

Simultaneous release of metals and sulfide in lacustrine sediment

A single DGT (diffusive gradient in thin films) probe that could measure metals and sulfide simultaneously and at the same location was deployed in the surface sediment of a productive lake (Esthwaite Water). It contained a layer of AgI that binds sulfide overlying a layer of chelating resin that binds metals. Analysis for sulfide in two dimensions showed local sources of sulfide, 1-5 mm in diameter, at 8-11 cm depth within the sediment. A transect of trace metals measured at 100-microm intervals through the largest sulfide "hot spot" demonstrated concomitant release of Fe, Mn, Cu, Ni, and Co. Substantial supersaturation with respect to metal sulfides was observed for Fe and Co at the site of metal generation, but at a distance of less than 1 mm, solution concentrations were consistent with equilibration with amorphous FeS and CoS phases. Simple mass balance calculations were consistent with Fe being supplied from reductive dissolution of its oxides and with sulfide being supplied from reduction of sulfate. The observed concentrations of Cu, Ni, Co, and Mn could be accounted for by their release from iron oxides without invoking Mn reduction. The metals are removed rapidly (approximately 1 min) at the edge of the hot spot. These first observations of the simultaneous release of trace metals and sulfide are consistent with the known removal of metals by formation of their insoluble sulfides if the in situ kinetics of metal sulfide formation is on this time scale. The coproduction of reduced Fe and S suggests that iron- and sulfate-reducing bacteria may exist together in the same localized zone of actively decomposing organic matter.     

Origin of a mixed brominated ethene groundwater plume: contaminant degradation pathways and reactions

On the basis of a combination of laboratory microcosm experiments, column sorption experiments, and the current spatial distribution of groundwater concentrations, the origin of a mixed brominated ethene groundwater plume and its degradation pathway were hypothesized. The contaminant groundwater plume was detected downgradient of a former mineral processing facility, and consisted of tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE), and vinyl bromide (VB). The combined laboratory and field data provided strong evidence that the origin of the mixed brominated ethene plume was a result of dissolution of the dense non-aqueous-phase liquid 1,1,2,2-tetrabromoethane (TBA) atthe presumed source zone, which degraded rapidly (half-life of 0.2 days) to form TriBE in near stoichiometric amounts. TriBE then degraded (half-life of 96 days) to form c-DBE, t-DBE, and VB via a reductive debromination degradation pathway. Slow degradation of c-DBE (half-life >220 days), t-DBE (half-life 220 days), and VB (half-life >220 days) coupled with their low retardation coefficients (1.2, 1.2, and 1.0 respectively) resulted in the formation of an extensive mixed brominated ethene contaminant plume. Without this clearer understanding of the mechanism for TBA degradation, the origin of the mixed brominated ethene groundwater contamination could have been misinterpreted, and inappropriate and ineffective source zone and groundwater remediation techniques could be applied.     

Treatment of mine drainage using permeable reactive barrers: column experiments

Permeable reactive barriers designed to enhance bacterial sulfate reduction and metal sulfide precipitation have the potential to prevent acid mine drainage and the associated release of dissolved metals. Two column experiments were conducted using simulated mine-drainage water to assess the performance of organic carbon-based reactive mixtures under controlled groundwater flow conditions. The simulated mine drainage is typical of mine-drainage waterthat has undergone acid neutralization within aquifers. This water is near neutral in pH and contains elevated concentrations of Fe(II) and SO4. Minimum rates of SO4 removal averaged between 500 and 800 mmol d(-1) m(-3) over a 14-month period. Iron concentrations decreased from between 300 and 1200 mg/L in the influent to between <0.01 and 220 mg/L in the columns. Concentrations of Zn decreased from 0.6-1.2 mg/L in the input to between 0.01 and 0.15 mg/L in the effluent, and Ni concentrations decreased from between 0.8 and 12.8 mg/L to <0.01 mg/L. The pH increased slightly from typical input values of 5.5-6.0 to effluent values of 6.5-7.0. Alkalinity, generally <50 mg/L (as CaCO3) in the influent, increased to between 300 and 1,300 mg/L (as CaCO3) in the effluent from the columns. As a result of decreased Fe(II) concentrations and increased alkalinity, the acid-generating potential of the simulated mine-drainage water was removed, and a net acid-consuming potential was observed in the effluent water.     

Use of polymer mats in series for sequential reactive barrier remediation of ammonium-contaminated groundwater: laboratory column evaluation

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats (installed in series) to be used as permeable reactive barriers for delivery of oxidants and reductants to induce sequential bioremediation of ammonium-contaminated groundwater (approximately 120mg L(-1) NH4+-N), without bioaugmentation. The strategy was for the first group of polymer mats to deliver oxygen to induce bacterial nitrification of the ammonium to nitrite/ nitrate as the groundwater moved past and for the second group of polymer mats to deliver hydrogen or ethanol, to induce bacterial denitrification of the nitrite/nitrate to produce nitrogen gas. Once purging of the first polymer mat commenced, ammonium concentrations decreased downgradient from the polymer mats. Nitrification rates increased and stabilized over the 6-month experiment, with stable nitrification half-lives in the range 0.07-0.25 days. Nitrification most likely occurred in a biologically active zone at the polymer wall/aqueous interface. With hydrogen delivery via the polymer mats, a denitrification half-life (nitrate plus nitrite removal) of 3.5 days was induced. Denitrification rates were significantly enhanced when ethanol was delivered via a polymer mat, with denitrification half-lives in the range of 0.12-0.34 days. Nitrification/ denitrification rates were maintained for groundwater flow rates up to 300 m yr(-1), suggesting oxygen and ethanol delivery rates via the polymer mats were sufficient not to limit nitrification or denitrification. In soil columns, the polymer mat delivery system provided an effective and reliable technique for delivery of oxygen and hydrogen or ethanol for sequential nitrification/denitrification of ammonium-contaminated groundwater. Scale-up of this concept to a field pilot-scale is currently underway.     

Examining mechanisms of groundwater Hg(II) treatment by reactive materials: an EXAFS study

Laboratory batch experiments were conducted to examine mechanisms of Hg(II) removal by reactive materials proposed for groundwater treatment. These materials included granular iron filings (GIF), 1:1 (w/w) mixtures of metallurgical granular Fe powder + elemental S (MGI+S) and elemental Cu + elemental S (Cu+S), granular activated carbon (GAC), attapulgite clay (ATP), ATP treated with 2-amino-5-thiol-1,3,4-thiadiazole (ATP-a), and ATP treated with 2,5-dimercapto-1,3,4-thiadiazole (ATP-d). Following treatment of simulated groundwater containing 4 mg L(-1) Hg for 8 or 16 days, the solution pH values ranged from 6.8 to 8.8 and Eh values ranged from +400 to -400 mV. Large decreases in aqueous Hg concentrations were observed for ATP-d (>99%), GIF (95%), MGI+S (94%), and Cu+S (90%). Treatment of Hg was less effective using ATP (29%), ATP-a (69%), and GAC (78%). Extended X-ray absorption fine structure (EXAFS) spectra of Hg on GIF, MGI+S, and GAC indicated the presence of an Hg-O bond at 2.04-2.07 ?, suggesting that Hg was bound to GIF corrosion products or to oxygen complexes associated with water sorbed to activated carbon. In contrast, bond lengths ranging from 2.35 to 2.48 ? were observed for Hg in Cu+S, ATP-a, and ATP-d treatments, suggesting the formation of Hg-S bonds.     

Multicomponent reactive transport in an in situ zero-valent iron cell

Data collected from a field study of in situ zero-valent iron treatment for TCE were analyzed in the context of coupled transport and reaction processes. The focus of this analysis was to understand the behavior of chemical components, including contaminants, in groundwater transported through the iron cell of a pilot-scale funnel and gate treatment system. A multicomponent reactive transport simulator was used to simultaneously model mobile and nonmobile components undergoing equilibrium and kinetic reactions including TCE degradation, parallel iron dissolution reactions, precipitation of secondary minerals, and complexation reactions. The resulting mechanistic model of coupled processes reproduced solution chemistry behavior observed in the iron cell with a minimum of calibration. These observations included the destruction of TCE and cis-1,2-DCE; increases in pH and hydrocarbons; and decreases in EH, alkalinity, dissolved O2 and CO2, and major ions (i.e., Ca, Mg, Cl, sulfate, nitrate). Mineral precipitation in the iron zone was critical to correctly predicting these behaviors. The dominant precipitation products were ferrous hydroxide, siderite, aragonite, brucite, and iron sulfide. In the first few centimeters of the reactive iron cell, these precipitation products are predicted to account for a 3% increase in mineral volume per year, which could have implications for the longevity of favorable barrier hydraulics and reactivity. The inclusion of transport was key to understanding the interplay between rates of transport and rates of reaction in the field.