Modeling the Kinetics of Hydrogen Formation by Zerovalent Iron: Effects of Sulfidation on Micro- and Nano-Scale Particles.

The hydrogen evolution reaction (HER) that generates H2 from the reduction of H2O by Fe0 is among the most fundamental of the processes that control reactivity in environmental systems containing zerovalent iron (ZVI). To develop a comprehensive kinetic model for this process, a large and high-resolution data set for HER was measured using five types of ZVI pretreated by acid-washing and/or sulfidation (in pH 7 HEPES buffer). The data were fit to four alternative kinetic models using nonlinear regression analysis applied to the whole data set simultaneously, which allowed some model parameters to be treated globally across multiple experiments. The preferred model uses two independent reactive phases to match the two-stage character of most HER data, with rate constants ( k's) for each phase fitted globally by iron type and phase quantities ( S's) fitted as fully local (independent) parameters. The first, faster stage was attributed to a reactive mineral intermediate (RMI) phase like Fe(OH)2, which may form in all experiments during preequilibration, but is rapidly consumed, leaving the second, slower stage of HER, which is due to reaction of Fe0. In addition to providing a deterministic model to explain the kinetics of HER by ZVI over a wide range of conditions, the results provide an improved quantitative basis for comparing the effects of sulfidation on ZVI.

Sulfidation of Iron-Based Materials: A Review of Processes and Implications for Water Treatment and Remediation.

Iron-based materials used in water treatment and groundwater remediation-especially micro- and nanosized zerovalent iron (nZVI)-can be more effective when modified with lower-valent forms of sulfur (i.e., "sulfidated"). Controlled sulfidation for this purpose (using sulfide, dithionite, etc.) is the main topic of this review, but insights are derived by comparison with related and comparatively well-characterized processes such as corrosion of iron in sulfidic waters and abiotic natural attenuation by iron sulfide minerals. Material characterization shows that varying sulfidation protocols (e.g., concerted or sequential) and key operational variables (e.g., S/Fe ratio and sulfidation duration) result in materials with structures and morphologies ranging from core-shell to multiphase. A meta-analysis of available kinetic data for dechlorination under anoxic conditions, shows that sulfidation usually increases dechlorination rates, and simultaneously hydrogen production is suppressed. Therefore, sulfidation can greatly improve the efficiency of utilization of reducing equivalents for contaminant removal. This benefit is most likely due to inhibited corrosion as a result of sulfidation. Sulfidation may also favor desirable pathways of contaminant removal, such as (i) dechlorination by reductive elimination rather than hydrogenolysis and (ii) sequestration of metals as sulfides that could be resistant to reoxidation. Under oxic conditions, sulfidation is shown to enhance heterogeneous catalytic oxidation of contaminants. These net effects of sulfidation on contaminant removal by iron-based materials may substantially improve their practical utility for water treatment and remediation of contaminated groundwater.

Sulfidation of Nano Zerovalent Iron (nZVI) for Improved Selectivity During In-Situ Chemical Reduction (ISCR).

The high reactivity of nano zerovalent iron (nZVI) leads to inefficient treatment due to competition with various natural reductant demand (NRD) processes, especially the reduction of water to hydrogen. Here we show that this limitation can be alleviated by sulfidation (i.e., modification by reducing sulfur compounds). nZVI synthesized on carboxylmethylcelluose (CMC-nZVI) was sulfidated with either sulfide or dithionite. The reactivity of the resulting materials was examined with three complementary assays: (i) direct measurement of hydrogen production, (ii) reduction of a colorimetric redox probe (indigo disulfonate, I2S), and (iii) dechlorination of trichloroethylene (TCE). The results indicate that sulfidation at S/Fe molar ratios of ≥0.3, effectively eliminates reaction with water, but retains significant reactivity with TCE. However, sulfidation with sulfide leaves most of the nZVI as Fe(0), whereas dithionite converts a majority of the nZVI to FeS (thus consuming much of the reducing capacity originally provided by the Fe(0)). Simplified numerical models show that the reduction kinetics of I2S and TCE are mainly dependent on the initial reducing equivalents and that the TCE reduction rate is affected by the aging of FeS. Overall, the results suggest that pretreatment of nZVI with reducing sulfur compounds could result in substantial improvement in nZVI selectivity.

Chemical Reactivity Probes for Assessing Abiotic Natural Attenuation by Reducing Iron Minerals.

Increasing recognition that abiotic natural attenuation (NA) of chlorinated solvents can be important has created demand for improved methods to characterize the redox properties of the aquifer materials that are responsible for abiotic NA. This study explores one promising approach: using chemical reactivity probes (CRPs) to characterize the thermodynamic and kinetic aspects of contaminant reduction by reducing iron minerals. Assays of thermodynamic CRPs were developed to determine the reduction potentials (ECRP) of suspended minerals by spectrophotometric determination of equilibrium CRP speciation and calculations using the Nernst equation. ECRP varied as expected with mineral type, mineral loading, and Fe(II) concentration. Comparison of ECRP with reduction potentials measured potentiometrically using a Pt electrode (EPt) showed that ECRP was 100-150 mV more negative than EPt. When EPt was measured with small additions of CRPs, the systematic difference between EPt and ECRP was eliminated, suggesting that these CRPs are effective mediators of electron transfer between mineral and electrode surfaces. Model contaminants (4-chloronitrobenzene, 2-chloroacetophenone, and carbon tetrachloride) were used as kinetic CRPs. The reduction rate constants of kinetic CRPs correlated well with the ECRP for mineral suspensions. Using the rate constants compiled from literature for contaminants and relative mineral reduction potentials based on ECRP measurements, qualitatively consistent trends were obtained, suggesting that CRP-based assays may be useful for estimating abiotic NA rates of contaminants in groundwater.

Field Deployable Chemical Redox Probe for Quantitative Characterization of Carboxymethylcellulose Modified Nano Zerovalent Iron.

Nano zerovalent iron synthesized with carboxymethylcelluose (CMC-nZVI) is among the leading formulations of nZVI currently used for in situ groundwater remediation. The main advantage of CMC-nZVI is that it forms stable suspensions, which are relatively mobile in porous media. Rapid contaminant reduction by CMC-nZVI is well documented, but the fate of the CMC-nZVI (including "aging" and "reductant demand") is not well characterized. Improved understanding of CMC-nZVI fate requires methods with greater specificity for Fe(0), less vulnerability to sampling/recovery artifacts, and more practical application in the field. These criteria can be met with a simple and specific colorimetric approach using indigo-5,5'-disulfonate (I2S) as a chemical redox probe (CRP). The measured stoichiometric ratio for reaction between I2S and nZVI is 1.45 ± 0.03, suggesting complete oxidation of nZVI to Fe(III) species. However, near pH 7, reduction of I2S is diagnostic for Fe(0), because aqueous Fe(II) reduces I2S much more slowly than Fe(0). At that pH, adding Fe(II) increased I2S reduction rates by Fe(0), consistent with depassivation of nZVI, but did not affect the stoichiometry. Using the I2S assay to quantify changes in the Fe(0) content of CMC-nZVI, the rate of Fe(0) oxidation by water was found to be orders of magnitude faster than previously reported values for other types of nZVI.

Assessment of anaerobic toluene biodegradation activity by bssA transcript/gene ratios.

Benzylsuccinate synthase (bssA) genes associated with toluene degradation were profiled across a groundwater contaminant plume under nitrate-reducing conditions and were detected in significant numbers throughout the plume. However, differences between groundwater and core sediment samples suggested that microbial transport, rather than local activity, was the underlying cause of the high copy numbers within the downgradient plume. Both gene transcript and reactant concentrations were consistent with this hypothesis. Expression of bssA genes from denitrifying toluene degraders was induced by toluene but only in the presence of nitrate, and transcript abundance dropped rapidly following the removal of either toluene or nitrate. The drop in bssA transcripts following the removal of toluene could be described by an exponential decay function with a half-life on the order of 1 h. Interestingly, bssA transcripts never disappeared completely but were always detected at some level if either inducer was present. Therefore, the detection of transcripts alone may not be sufficient evidence for contaminant degradation. To avoid mistakenly associating basal-level gene expression with actively degrading microbial populations, an integrated approach using the ratio of functional gene transcripts to gene copies is recommended. This approach minimizes the impact of microbial transport on activity assessment and allows reliable assessments of microbial activity to be obtained from water samples.

Field-scale transport and transformation of carboxymethylcellulose-stabilized nano zero-valent iron.

The fate of nano zerovalent iron (nZVI) during subsurface injection was examined using carboxymethylcellulose (CMC) stabilized nZVI in a very large three-dimensional physical model aquifer with detailed monitoring using multiple, complementary detection methods. A fluorescein tracer test in the aquifer plus laboratory column data suggested that the very-aggressive flow conditions necessary to achieve 2.5 m of nZVI transport could be obtained using a hydraulically constrained flow path between injection and extraction wells. However, total unoxidized nZVI was transported only about 1 m and <2% of the injected nZVI concentration reached that distance. The experimental data also indicated that groundwater flow changed during injection, likely due to hydrogen bubble formation, which diverted the nZVI away from the targeted flow path. The leading edge of the iron plume became fully oxidized during transport. However, within the plume, oxidation of nZVI decreased in a fashion consistent with progressive depletion of aquifer "reductant demand". To directly quantify the extent of nZVI transport, a spectrophotometric method was developed, and the results indicated that deployment of unoxidized nZVI for groundwater remediation will likely be difficult.

Effects of cryogenic preservation and storage on the molecular characteristics of microorganisms in sediments.

Sediment samples from a large physical-model aquifer and laboratory-generated samples were used to systematically assess the effects of whole-sample freezing on the integrity of biomolecules relevant to bioremediation. Impacts of freezing on DNA and RNA were assessed using quantitative polymerase chain reaction (PCR) as well as the community fingerprinting method, PCR single-strand conformation polymorphism (PCR-SSCP). We did not observe any significant degradation of a suite of genes and gene transcripts, including short-lived mRNA transcripts, from P. putida F1 or from B. subtilis JH642 in single-species samples, or from archaea in enrichment culture samples that also contained members of diverse bacterial phyla. Similarly, freezing did not change the relative abundance of dominant phylotypes in enrichment culture samples as measured by PCR-SSCP of bacterial 16S rDNA. Additionally, freezing and storage for 5 months at -80 °C did not affect the microbial community composition of samples from the model aquifer. Of even greater significance is that freezing and storage did not affect the relative abundance of 16S rRNA phylotypes, since in vivo rRNA content is often correlated with cellular growth rate. Thus, we conclude that cryogenic preservation and storage of intact sediment samples can be used for accurate molecular characterization of microbial populations and may facilitate high-resolution capture of biogeochemical interfaces important to bioremediation.

Cryogenic soil coring reveals coexistence of aerobic and anaerobic vinyl chloride degrading bacteria in a chlorinated ethene contaminated aquifer.

Vinyl chloride (VC) is a common groundwater contaminant and known human carcinogen. Three major bacterial guilds are known to participate in VC biodegradation: aerobic etheneotrophs and methanotrophs, and anaerobic organohalide-respiring VC-dechlorinators. We investigated the spatial relationships between functional genes representing these three groups of bacteria (as determined by qPCR) with chlorinated ethene concentrations in a surficial aquifer at a contaminated site. We used cryogenic soil coring to collect high-resolution aquifer sediment samples and to preserve sample geochemistry and nucleic acids under field conditions. All samples appeared to be anaerobic (i.e., contained little to no dissolved oxygen). VC biodegradation associated functional genes from etheneotrophs (etnC and/or etnE), methanotrophs (mmoX and/or pmoA), and anaerobic VC-dechlorinators (bvcA and/or vcrA) coexisted in 48% of the samples. Transcripts of etnC/etnE and bvcA/vcrA were quantified in contemporaneous groundwater samples, indicating co-located gene expression. Functional genes from etheneotrophs and anaerobic VC-dechlorinators were correlated to VC concentrations in the lower surficial aquifer (p < 0.05). Methanotroph functional genes were not correlated to VC concentrations. Cryogenic soil coring proved to be a powerful tool for capturing high-spatial resolution trends in geochemical and nucleic acid data in aquifer sediments. We conclude that both aerobic etheneotrophs and anaerobic VC-dechlorinators may play a significant role in VC biodegradation in aquifers that have little dissolved oxygen.

Economic grand rounds: A pay-for-performance program for behavioral health care practitioners.

This column describes a pay-for-performance program for behavioral health care practitioners. Implemented in 1996 by a large national health insurer, the program's goals are to improve the quality of care, recognize the practitioners who provide higher-quality care, demonstrate the value of behavioral health services to purchasers, and help providers align their practices with national standards. A future goal is to provide patients with data on provider quality to improve their treatment decisions. Important considerations in measure development include application of the measure to all disciplines, feasible data collection processes for providers, creation of clinically meaningful and fair measures, and selection of measures with large baseline variability.

Evaluation of groundwater flow patterns around a dual-screened groundwater circulation well.

Dual-screened groundwater circulation wells (GCWs) can be used to remove contaminant mass and to mix reagents in situ. GCWs are so named because they force water in a circular pattern between injection and extraction screens. The radial extent, flux and direction of the effective flow of this circulation cell are difficult to measure or predict. The objective of this study is to develop a robust protocol for assessing GCW performance. To accomplish this, groundwater flow patterns surrounding a GCW are assessed using a suite of tools and data, including: hydraulic head, in situ flow velocity, measured hydraulic conductivity data from core samples, chemical tracer tests, contaminant distribution data, and numerical flow and transport models. The hydraulic head data show patterns that are consistent with pumping on a dual-screened well, however, many of the observed changes are smaller than expected. In situ thermal perturbation flow sensors successfully measured horizontal flow, but vertical flow could not be determined with sufficient accuracy to be useful in mapping flow patterns. Two types of chemical tracer tests were utilized at the site and showed that much of the flow occurs within a few meters of the GCW. Flow patterns were also assessed based on changes in contaminant (trichloroethylene, TCE) concentrations over time. The TCE data clearly showed treated water moving away from the GCW at shallow and intermediate depths, but the circulation of that water back to the well, except very close to the well, was less clear. Detailed vertical and horizontal hydraulic conductivities were measured on 0.3 m-long sections from a continuous core from the GCW installation borehole. The measured vertical and horizontal hydraulic conductivity data were used to construct numerical flow and transport models, the results of which were compared to the head, velocity and concentration data. Taken together, the field data and modeling present a fairly consistent picture of flow and transport around the GCW. However, the time and expense associated with conducting all of those tests would be prohibitive for most sites. As a consequence, a sequential protocol for GCW characterization is presented here in which the number of tools used can be adjusted to meet the needs of individual sites. While not perfect, we believe that this approach represents the most efficient means for evaluating GCW performance.

Methods for characterizing the fate and effects of nano zerovalent iron during groundwater remediation.

The emplacement of nano zerovalent iron (nZVI) for groundwater remediation is usually monitored by common measurements such as pH, total iron content, and oxidation-reduction potential (ORP) by potentiometry. However, the interpretation of such measurements can be misleading because of the complex interactions between the target materials (e.g., suspensions of highly reactive and variably aggregated nanoparticles) and aquifer materials (sediments and groundwater), and multiple complications related to sampling and detection methods. This paper reviews current practice for both direct and indirect characterizations of nZVI during groundwater remediation and explores prospects for improving these methods and/or refining the interpretation of these measurements. To support our recommendations, results are presented based on laboratory batch and column studies of nZVI detection using chemical, electrochemical, and geophysical methods. Chemical redox probes appear to be a promising new method for specifically detecting nZVI, based on laboratory tests. The potentiometric and voltammetric detections of iron nanoparticles, using traditional stationary disc electrodes, rotating disc electrodes, and flow-through cell disc electrodes, provide insight for interpreting ORP measurements, which are affected by solution chemistry conditions and the interactions between iron nanoparticles and the electrode surface. The geophysical methods used for characterizing ZVI during groundwater remediation are reviewed and its application for nZVI detection is assessed with results of laboratory column experiments.

An analysis of a mixed convection associated with thermal heating in contaminated porous media.

The occurrence of subsurface buoyant flow during thermal remediation was investigated using a two dimensional electro-thermal model (ETM). The model incorporated electrical current flow associated with electrical resistance heating, energy and mass transport, and density dependent water flow. The model was used to examine the effects of heating on sixteen subsurface scenarios with different applied groundwater fluxes and soil permeabilities. The results were analyzed in terms of the ratio of Rayleigh to thermal Peclet numbers (the buoyancy ratio). It was found that when the buoyancy number was greater than unity and the soil permeability greater than 10(-12) m(2), buoyant flow and contaminant transport were significant. The effects of low permeability layers and electrode placement on heat and mass transport were also investigated. Heating under a clay layer led to flow stagnation zones resulting in the accumulation of contaminant mass and transport into the low permeability layer. The results of this study can be used to develop dimensionless number-based guidelines for site management during subsurface thermal activities.

Degradation of 1,2,3-trichloropropane (TCP): hydrolysis, elimination, and reduction by iron and zinc.

1,2,3-Trichloropropane (TCP) is an emerging contaminant because of increased recognition of its occurrence in groundwater, potential carcinogenicity, and resistance to natural attenuation. The physical and chemical properties of TCP make it difficult to remediate, with all conventional options being relatively slow or inefficient. Treatments that result in alkaline conditions (e.g., permeable reactive barriers containing zerovalent iron) favor base-catalyzed hydrolysis of TCP, but high temperature (e.g., conditions of in situ thermal remediation) is necessary for this reaction to be significant. Common reductants (sulfide, ferrous iron adsorbed to iron oxides, and most forms of construction-grade or nano-Fe(0)) produce insignificant rates of reductive dechlorination of TCP. Quantifiable rates of TCP reduction were obtained with several types of activated nano-Fe(0), but the surface area normalized rate contants (k(SA)) for these reactions were lower than is generally considered useful for in situ remediation applications (10(-4) L m(-2) h(-1)). Much faster rates of degradation of TCP were obtained with granular Zn(0), (k(SA) = 10(-3) - 10(-2) L m(-2) h(-1)) and potentially problematic dechlorination intermediates (1,2- or 1,3-dichloropropane, 3-chloro-1-propene) were not detected. The advantages of Zn(0) over Fe(0) are somewhat peculiar to TCP and may suggest a practical application for Zn(0) even though it has not found favor for remediation of contamination with other chlorinated solvents.

Ammonia removal from air stream and biogas by a H2SO4 impregnated adsorbent originating from waste wood-shavings and biosolids.

A new and cost-effective adsorbent N-TRAP, made from waste wood-shavings and anaerobically digestion biosolids and impregnated with H(2)SO(4), was applied for the ammonia removal from air stream and biogas with high efficiency and effectiveness. Bearing a 75-80 and 65 wt.% sulfuric acid, the N-TRAPs mediated with wood shavings and biosolids showed the maximum ammonia adsorption capacity of 260-280 and 230 mg g(-1), respectively. Gas temperatures (20 and 60 degrees C) and moisture content (100% relative humidity) had no significantly negative effect on ammonia capture performance when temperature in the fixed-bed column was kept equalled to or slightly above the feed gas temperature. The pressure drop increased significantly when NH(3) began to break through the N-TRAP stripper due to the formation of ammonium sulfate blocking the vacuum space of packed adsorbent. At last, an alternative N-TRAP filter bed design was proposed to resolve the problem of pressure drop evolution.

Natural organic matter enhanced mobility of nano zerovalent iron.

Column studies showed that the mobility of nanometer-sized zerovalent iron (nZVI) through granular media is greatly increased in the presence of natural organic matter (NOM). At NOM concentrations of 20 mg/L or greater, the nZVI was highly mobile during transport experiments in 0.15-m long columns packed with medium sand. Below 20 mg/L NOM, mobility of the nZVI was less; however, even at 2 mg/L the nZVI showed significantly increased mobility compared to the no-NOM case. Spectrophotometric and aggregation studies of nZVI suspensions in the presence of NOM suggest that sorption of the NOM onto the nZVI, resulting in a reduced sticking coefficient, may be the primary mechanism of enhanced mobility. Modeling the mobility of nZVI in porous media with filtration theory is challenging, but calibration of a simple model with experimental results from the column experiments reported here allows simulation of transport distances during injection. The simulation results show that the increased mobility due to NOM combined with the decrease in mobility due to decreased velocity with distance from an injection well could produce an injection zone that is wide enough to be useful for remediation but small enough to avoid reaching unwanted receptors.

Persulfate persistence under thermal activation conditions.

Contaminant destruction with in situ chemical oxidation (ISCO) using persulfate (peroxydisulfate, S2O8(2-)) can be enhanced by activation, which increases the rate of persulfate decomposition to sulfate radicals (SO4*-). This step initiates a chain of radical reactions involving species (including SO4*- and OH*) that oxidize contaminants more rapidly than persulfate does directly. Among current activation methods, thermal activation is the least well studied. Combining new data for environmentally relevant conditions with previously published data, we have computed three sets of Arrhenius parameters (In A and Eact) that describe the rate of persulfate decomposition in homogeneous solutions over a wide range of temperature and pH. The addition of soil increases the decomposition rate of persulfate due to reactions with organic matter and possibly mineral surfaces, but the kinetics are still pseudo-first-order in persulfate and conform to the Arrhenius model. A series of respike experiments with soil at 70 degrees C demonstrate that once the oxidant demand is met, reaction rates return to values near those observed in the homogeneous solution case. However, even after the oxidant demand is met, the relatively short lifetime of the persulfate at elevated temperatures (e.g., >50 degrees C) will limit the delivery time over which persulfate can be effective.