Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

Field-scale remediation of a metolachlor-contaminated spill site using zerovalent iron

Pesticide spills are common occurrences at agricultural cooperatives and farmsteads. When inadvertent spills occur, chemicals normally beneficial can become point sources of ground and surface water contamination. We report results from a field trial where approximately 765 m3 of soil from a metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] spill site was treated with zerovalent iron (Fe0). Preliminary laboratory experiments confirmed metolachlor dechlorination by Fe0 in aqueous solution and that this process could be accelerated by adding appropriate proportions of Al2(SO4)3 or acetic acid (CH3COOH). The field project was initiated by moving the stockpiled, contaminated soil into windrows using common earth-moving equipment. The soil was then mixed with water (0.35-0.40 kg H2O kg(-1)) and various combinations of 5% Fe0 (w/w),2% Al2(SO4)3 (w/w), and 0.5% acetic acid (v/w). Windrows were covered with clear plastic and incubated without additional mixing for 90 d. Approximately every 14 d, the plastic sheeting was removed for soil sampling and the surface of the windrows rewetted. Metolachlor concentrations were significantly reduced and varied among treatments. The addition of Fe0 alone decreased metolachlor concentration from 1789 to 504 mg kg(-1) within 90 d, whereas adding Fe0 with Al2(SO4)3 and CH3COOH decreased the concentration from 1402 to 13 mg kg(-1). These results provide evidence that zerovalent iron can be used for on-site, field-scale treatment of pesticide-contaminated soil.     

Pilot-scale treatment of RDX-contaminated soil with zerovalent iron

Soils in Technical Area 16 at Los Alamos National Laboratory (LANL) are severely contaminated from past explosives testing and research. Our objective was to conduct laboratory and pilot-scale experiments to determine if zerovalent iron (Fe(0)) could effectively transform RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) in two LANL soils that differed in physicochemical properties (Soils A and B). Laboratory tests indicated that Soil A was highly alkaline and needed to be acidified [with H2SO4, Al2(SO4)3, or CH3COOH] before Fe(0) could transform RDX. Pilot-scale experiments were performed by mixing Fe(0) and contaminated soil (70 kg), and acidifying amendments with a high-speed mixer that was a one-sixth replica of a field-scale unit. Soils were kept unsaturated (soil water content = 0.30-0.34 kg kg(-1)) and sampled with time (0-120 d). While adding CH3COOH improved the effectiveness of Fe(0) to remove RDX in Soil A (98% destruction), CH3COOH had a negative effect in Soil B. We believe that this difference is a result of high concentrations of organic matter and Ba. Adding CH3COOH to Soil B lowered pH and facilitated Ba release from BaSO4 or BaCO3, which decreased Fe(0) performance by promoting flocculation of humic material on the iron. Despite problems encountered with CH3COOH, pilot-scale treatment of Soil B (12 100 mg RDX kg(-1)) with Fe(0) or Fe(0) + Al2(SO4)3 showed high RDX destruction (96-98%). This indicates that RDX-contaminated soil can be remediated at the field scale with Fe(0) and soil-specific problems (i.e., alkalinity, high organic matter or Ba) can be overcome by adjustments to the Fe(0) treatment.     

Effects of oxide coating and selected cations on nitrate reduction by iron metal

Under anoxic conditions, zerovalent iron (Fe(0)) reduces nitrate to ammonium and magnetite (Fe3O4) is produced at near-neutral pH. Nitrate removal was most rapid at low pH (2-4); however, the formation of a black oxide film at pH 5 to 8 temporarily halted or slowed the reaction unless the system was augmented with Fe(2+), Cu(2+), or Al(3+). Bathing the corroding Fe(0) in a Fe(2+) solution greatly enhanced nitrate reduction at near-neutral pH and coincided with the formation of a black precipitate. X-ray diffractometry and scanning electron microscopy confirmed that both the black precipitate and black oxide coating on the iron surface were magnetite. In this system, ferrous iron was determined to be a partial contributor to nitrate removal, but nitrate reduction was not observed in the absence of Fe(0). Nitrate removal was also enhanced by augmenting the Fe(0)-H2O system with Fe(3+), Cu(2+), or Al(3+) but not Ca(2+), Mg(2+), or Zn(2+). Our research indicates that a magnetite coating is not a hindrance to nitrate reduction by Fe(0), provided sufficient aqueous Fe(2+) is present in the system.     

Impact of sample preparation on mineralogical analysis of zero-valent iron reactive barrier materials

Permeable reactive barriers (PRBs) of zero-valent iron (Fe(0)) are increasingly being used to remediate contaminated ground water. Corrosion of Fe(0) filings and the formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe(0) PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe(0) reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe(0) PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples. Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105 degrees C. We conclude that care must be taken during sample preparation of Fe(0) PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.     

Mineralogical characteristics and transformations during long-term operation of a zerovalent iron reactive barrier

Design and operation of Fe0 permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe0 filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe0 filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe0 section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants.     

Remediating munitions-contaminated soil with zerovalent iron and cationic surfactants

Soils contaminated from military operations often contain mixtures of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and TNT (2,4,6-trinitrotoluene) rather than a single explosive. Differences among explosives in solubility and reactivity make developing a single remediation treatment difficult. When Fe(0) was used to treat a munitions-contaminated soil, we observed high rates of destruction for RDX and TNT (98%) but not HMX. Our objective was to determine if HMX destruction by Fe(0) could be enhanced by increasing HMX solubility by physical (temperature) or chemical (surfactants) means. To determine electron acceptor preference, we treated RDX and HMX with Fe(0) in homogeneous solutions and binary mixtures. Increasing aqueous temperature (20 to 55 degrees C) increased HMX solubility (2 to 22 mg L(-1)) but did not increase destruction by Fe(0) in a contaminated soil slurry that also contained RDX and TNT. Batch experiments using equal molar concentrations of RDX and HMX demonstrated that RDX was preferentially reduced over HMX by Fe(0). By testing various surfactants, we found that the cationic surfactants (HDTMA [hexadecyltrimethylammonium bromide], didecyl, and didodecyl) were most effective in increasing HMX concentration in solution. Didecyl and HDTMA were also found to be highly effective in facilitating the transformation of HMX by Fe(0). Using HDTMA or didecyl solutions (3%, w/v) containing solid-phase HMX, we observed that 100% of the added HMX was transformed by Fe(0) in the didecyl matrix and 60% in the HDTMA matrix. These results indicate that cationic surfactants can increase HMX solubility and facilitate Fe(0)-mediated transformation kinetics but HMX destruction rates will be slowed when RDX is present.     

Drinking water treatment residuals: a review of recent uses

Coagulants such as alum [Al2(SO4)3 x 14H2O], FeCl3, or Fe2(SO4)3 are commonly used to remove particulate and dissolved constituents from water supplies in the production of drinking water. The resulting waste product, called water-treatment residuals (WTR), contains precipitated Al and Fe oxyhydroxides, resulting in a strong affinity for anionic species. Recent research has focused on using WTR as cost-effective materials to reduce soluble phosphorus (P) in soils, runoff, and land-applied organic wastes (manures and biosolids). Studies show P adsorption by WTR to be fast and nearly irreversible, suggesting long-term stable immobilization of WTR-bound P. Because excessive WTR application can induce P deficiency in crops, effective application rates and methods remain an area of intense research. Removal of other potential environmental contaminants [ClO4-, Se(+IV and +VI), As(+III and +V), and Hg] by WTR has been documented, suggesting potential use of WTR in environmental remediation. Although the creation of Al plant toxicity and enhanced Al leaching are concerns expressed by researchers, these effects are minimal at circumneutral soil pH conditions. Radioactivity, trace element levels, and enhanced Mn leaching have also been cited as potential problems in WTR usage as a soil supplement. However, these issues can be managed so as not to limit the beneficial use of WTR in controlling off-site P losses to sensitive water bodies or reducing soil-extractable P concentrations.     

Particulate and dissolved phosphorus chemical separation and phosphorus release from treated dairy manure

In confined animal feeding operations, liquid manure systems present special handling and storage challenges because of the large volume of diluted wastes. Water treatment polymers and mineral phosphorus (P) immobilizing chemicals [AI2(SO4)3 x 18H2O, FeCl3-6H2O, and Class C fly ash] were used to determine particulate and dissolved reactive phosphorus (DRP) reduction mechanisms in high total suspended solid (TSS) dairy manure and the P release from treated manure and amended soils. Co-application exceeded the aggregation level achieved with individual manure amendments and resulted in 80 and 90% reduction in metal salt and polymer rates, respectively. At marginally effective polymer rates between 0.01 and 0.25 g L(-1), maximal aggregation was attained in combination with 1 and 10 g L(-1) of aluminum sulfate (3 and 30 mmol Al3+ L(-1)) and iron chloride (3.7 and 37 mmol Fe3+ L(-1)) in 30 g L(-1) (TSS30) and 100 g L(-1) TSS (TSS100) suspensions, respectively. Fly ash induced particulate destabilization at rates > or = 50 g L(-1) and reduced solution-phase DRP at all rates > or = 1 g L(-1) by 52 and 71% in TSS30 and TSS100 suspensions, respectively. Aluminum and Fe salts also lowered DRP at rates < or = 10 g L(-1) and higher concentrations redispersed particulates and increased DRP due to increased suspension acidity and electrical conductivity. The DRP release from treated manure solids and a Typic Paleudult amended with treated manure was reduced, although the amendments increased Mehlich 3-extractable P. Therefore, the synergism of flocculant types allowed input reduction in aggregation aid chemicals, enhancing particulate and dissolved P separation and immobilization in high TSS liquid manure.     

Sorption and degradation of alachlor and metolachlor in ground water using green sands

Reactive barriers are used for in situ treatment of contaminated ground water. Waste green sand, a by-product of gray-iron foundries that contains iron particles and organic carbon, was evaluated in this study as a low-cost reactive material for treating ground water contaminated with the herbicides alachlor [2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide] and metolachlor [2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o-acetoluidide]. Batch and column tests were conducted with 11 green sands to determine transport parameters and reaction rate constants for the herbicides. Similar Fe-normalized rate constants (K(SA)) were obtained from the batch and column tests. The K(SA) values obtained for green sand iron were also found to be comparable with or slightly higher than K(SA) values for Peerless iron, a common reactive medium used in reactive barriers. Partition coefficients ranging between 3.6 and 50.2 L/kg were obtained for alachlor and between 1.0 and 54.8 L/kg for metolachlor, indicating that the organic carbon and clay in green sands can significantly retard the movement of the herbicides. Partition coefficients obtained from the batch and column tests were similar (+/-25%), but the batch tests typically yielded higher partition coefficients for green sands exhibiting greater sorption. Calculations made using transport parameters from the column tests indicate that a 1-m-thick reactive barrier will result in a 10-fold reduction in concentration of alachlor and metolachlor for seepage velocities less than 0.1 m/d provided the green sand contains at least 2% iron. This level of reduction generally is sufficient to reduce alachlor and metolachlor concentrations below maximum contaminant levels in the United States.     

Removal of selenate from water by zerovalent iron

Zerovalent iron (ZVI) has been widely used in the removal of environmental contaminants from water. In this study, ZVI was used to remove selenate [Se(VI)] at a level of 1000 microg L(-1) in the presence of varying concentrations of Cl-, SO(2-)4, NO(-)3, HCO(-)3, and PO(3-)4. Results showed that Se(VI) was rapidly removed during the corrosion of ZVI to iron oxyhydroxides (Fe(OH)). During the 16 h of the experiments, 100 and 56% of the added Se(VI) was removed in 10 mM Cl- and SO(2-)4 solutions under a closed contained system, respectively. Under an open condition, 100 and 93% of the added Se(VI) were removed in the Cl- and SO(2-)4 solutions, respectively. Analysis of Se species in ZVI-Fe(OH) revealed that selenite [Se(IV)] and nonextractable Se increased during the first 2 to 4 h of reaction, with a decrease of Se(VI) in the Cl- experiment and no detection of Se(VI) in the SO(2-)4 experiment. Two mechanisms can be attributed to the rapid removal of Se(VI) from the solutions. One is the reduction of Se(VI) to Se(IV), followed by rapid adsorption of Se(IV) to Fe(OH). The other is the adsorption of Se(VI) directly to Fe(OH), followed by its reduction to Se(IV). The results also show that there was little effect on Se(VI) removal in the presence of Cl- (5, 50, and 100 mM), NO(-)3 (1, 5, and 10 mM), SO(2-)4 (5 mM), HCO(-)3 (1 and 5 mM), or PO(3-)4 (1 mM) and only a slight effect in the presence of SO(2-)4 (50 and 100 mM), HCO(-)3 (10 mM), and PO(3-)4 (5 mM) during a 2-d experiment, whereas 10 mM PO(3-)4 significantly inhibited Se(VI) removal. This work suggests that ZVI may be an effective agent to remove Se from Se-contaminated agricultural drainage water.     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

Relationships between biosolids treatment process and soil phosphorus availability

Laws mandating phosphorus (P)-based nutrient management plans have been passed in several U.S. Mid-Atlantic states. Biosolids (sewage sludge) are frequently applied to agricultural land and in this study we evaluated how biosolids treatment processes and biosolids P tests were related to P behavior in biosolids-amended soils. Eight biosolids generated by different treatment processes, with respect to digestion and iron (Fe), aluminum (Al), and lime addition, and a poultry litter (PL), were incubated with an Elkton silt loam (fine-silty, mixed, active, mesic Typic Endoaquult) and a Suffolk sandy loam (fine-loamy, siliceous, semiactive, thermic Typic Hapludult) for 51 d. The amended soils were analyzed at 1 and 51 d for water-soluble phosphorus (WSP), iron-oxide strip--extractable phosphorus (FeO-P), Mehlich-1 P and pH. The biosolids and PL were analyzed for P, Fe, and Al by USEPA 3050 acid-peroxide digestion and acid ammonium oxalate, Mehlich-1, and Mehlich-3 extractions. Biosolids and PL amendments increased extractable P in the Suffolk sandy loam to a greater extent than in the Elkton silt loam throughout the 51 d of the incubation. The trend of extractable WSP, FeO-P, and Mehlich-1 P generally followed the pattern: [soils amended with biosolids produced without the use of Fe or Al] > [PL and biosolids produced using Fe or Al and lime] > [biosolids produced using only Fe and Al salts]. Mehlich-3 P and the molar ratio of P to [Al + Fe] by either the USEPA 3050 digestion or oxalate extraction of the biosolids were good predictors of changes in soil-extractable P following biosolids but not PL amendment. Therefore, the testing of biosolids for P availability, rather than total P, is a more appropriate tool for predicting extractable P from the biosolids-amended soils used in this study.     

Matrix based fertilizers reduce nitrogen and phosphorus leaching in three soils

We compared the efficacy of matrix based fertilizers (MBFs) formulated to reduce NO3-, NH4+, and total phosphorus (TP) leaching, with Osmocoate 14-14-14, a conventional commercial slow release fertilizer (SRF) and an unamended control in three different soil textures in a greenhouse column study. The MBFs covered a range of inorganic N and P in compounds that are relatively loosely bound (MBF 1) to more moderately bound (MBF 2) and more tightly bound compounds (MBF 3) mixed with Al(SO4)3H2O and/or Fe2(SO4)3 and with high ionic exchange compounds starch, chitosan and lignin. When N and P are released, the chemicals containing these nutrients in the MBF bind N and P to a Al(SO4)3H2O and/or Fe2(SO4)3 starch-chitosan-lignin matrix. One milligram (8000 spores) of Glomus intradices was added to all formulations to enhance nutrient uptake. In all three soil textures the SRF leachate contained a higher amount of NH4+, NO3- and TP than leachate from all other fertilizers. In all three soils there were no consistent differences in the amount of NH4+, NO3- and TP in the MBF leachates compared to the control leachate. Plants growing in soils receiving SRF had greater shoot, root and total biomass than all MBFs regardless of Al(SO4)3H2O or Fe2(SO4)3 additions. Arbuscular mycorrhizal infection in plant roots did not consistently differ among plants growing in soil receiving SRF, MBFs and control treatments. Although the MBFs resulted in less plant growth in this experiment they may be applied to soils growing plants in areas that are at high risk for nutrient leaching to surface waters.     

Aluminum output fluxes from forest ecosystems in Europe: a regional assessment

Data from 89 forested catchments and plots across Europe were used to define empirical relationships between aluminum leaching and input fluxes of major ions, output fluxes of major ions, ecosystem parameters such as soil pH, and combinations of these. Forests that release dissolved Al to seepage or surface waters are located primarily in areas receiving the highest loading of acid rain, and the output flux of Al shows the highest correlations to the throughfall flux of inorganic nitrogen, the output fluxes of NO3-, H+, and SO4(2-), and the mineral soil pH. If the speciation of Al is taken to be Al3+ (an overestimate), Al is released in a nearly 1:1 molar charge ratio with the sum of NO3- and SO4(2-) in runoff or seepage water over a wide range of basepoor bedrock types and acid deposition across Europe. The empirical data point to a threshold range of N deposition of 80 to 150 mmolc N m(-2) yr(-1) and a (less clearly defined) range of S deposition of 100 to 200 mmolc SO4(-2) m(-2) yr(-1) above which Al released from forests exceeds 100 mmolc Al m(-2) yr(-1). Within this threshold range, the sites that release little or no dissolved Al are those that continue to assimilate input N and/or have high soil pH (>4.5).     

Ferron逐时络合比色法研究聚硅硫酸铁中铁的形态

通过实验制备了一种新型无机高分子絮凝剂聚硅硫酸铁（PFSS），用Ferron逐时络合比色法测定了PFSS中铁的形态，考察了熟化时间、Fe3+／SiO2摩尔比对铁的形态分布及转化规律的影响。不同Fe3+／SiO2摩尔比的PFSS中Fe（a）的量最多、占50％以上，Fe（c）在35％～50％之间，Fe（b）在0～5％之间。研究表明：铁的形态分布及其转化规律与溶液的高酸度及聚硅酸的存在有关。     

Oxidative remobilization of biogenic uranium(IV) precipitates: effects of iron(II) and pH

The oxidative remobilization of uranium from biogenic U(IV) precipitates was investigated in bioreduced sediment suspensions in contact with atmospheric O2 with an emphasis on the influence of Fe(II) and pH on the rate and extent of U release from the solid to the aqueous phase. The sediment was collected from the U.S. Department of Energy Field Research Center (FRC) site at Oak Ridge, Tennessee. Biogenic U(IV) precipitates and bioreduced sediment were generated through anaerobic incubation with a dissimilatory metal reducing bacterium Shewanella putrefaciens strain CN32. The oxidative remobilization of freshly prepared and 1-yr aged biogenic U(IV) was conducted in 0.1 mol/L NaNO3 electrolyte with variable pH and Fe(II) concentrations. Biogenic U(IV)O2(s) was released into the aqueous phase with the highest rate and extent at pH 4 and 9, while the U remobilization was the lowest at circumneutral pH. Increasing Fe(II) significantly decreased U remobilization to the aqueous phase. From 70 to 100% of the U in the sediments used in all the tests was extractable at the experiment termination (41 d) with a bicarbonate solution (0.2 mol/L), indicating that biogenic U(IV) was oxidized regardless of Fe(II) concentration and pH. Sorption experiments and modeling calculations indicated that the inhibitive effect of Fe(II) on U(IV) oxidative remobilization was consistent with the Fe(III) oxide precipitation and U(VI) sorption to this secondary phase.     

Nitrate reduction in the presence of wüstite

Recent strategies to reduce elevated nitrate concentrations employ metallic Fe0 as a reductant. Secondary products of Fe0 corrosion include magnetite (Fe3O4), green rust [Fe6(OH)12SO4], and wüstite [FeO(s)]. To our knowledge, no studies have been reported on the reactivity of NO3- with FeO(s). This project was initiated to evaluate the reactivity of FeO(s) with NO3- under abiotic conditions. Stirred batch reactions were performed in an anaerobic chamber over a range of pH values (5.45, 6.45, and 7.45), initial FeO(s) concentrations (1, 5, and 10 g L(-1)), initial NO3- concentrations (1, 10, and 15 mM), and temperatures (3, 21, 31, and 41 degrees C) for kinetic and thermodynamic determinations. Suspensions were periodically removed and filtered to measure dissolved nitrogen and iron species. Solid phases were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Nitrate reduction by FeO was rapid and characterized by nearly stoichiometric conversion of NO3- to NH4+. Transient NO2- formation also occurred. The XRD and SEM results indicated the formation of Fe3O4 as a reaction product of the heterogeneous redox reaction. Kinetics of NO3- reduction suggested a rate equation of the type: -d[NO3-]/dt = k[FeO]0.57[H]0.22[NO3-]1.12 where k = 3.46 x 10(-3) +/- 0.38 x 10(-3) M(-1) s(-1), at 25 degrees C. Arrhenius and Eyring plots indicate that the reaction is surface chemical-controlled and proceeds by an associative mechanism involving a step where both NO3- and FeO(s) bind together in an intermediate complex.     

酞菁绿染料排放废渣的处理技术

酞菁绿废渣中含有较多的铝化合物和少量的铜化合物及染料残渣,本文采用H2SO4除Ca2^ 、Al灰除Cu^2 或NaOH浸取Al^3 的反应条件和工艺过程,制得Al(OH)3产品,并进一步合成性能优良的聚合铝产品。废渣经处理后不仅回收了利用价值较高的铝,取得了一定的经济效益,同时不产生二次污染,也取得了明显的环境效益。     

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT.