Enhancing metolachlor destruction rates with aluminum and iron salts during zerovalent iron treatment

Pesticide-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of zerovalent iron (Fe(0)) to dechlorinate metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methyl ethyl) acetamide] in the presence of aluminum and iron salts. By treating aqueous solutions of metolachlor with Fe(0), we found destruction kinetics were greatly enhanced when Al, Fe(II), or Fe(II) salts were added, with the following order of destruction kinetics observed: Al2(SO4)3 > AlCl3 > Fe2(SO4)3 > FeCl3. A common observation was the formation of green rusts, mixed Fe(II)-Fe(III) hydroxides with interlayer anions that impart a greenish-blue color. Central to the mechanism responsible for enhanced metolachlor loss may be the role these salts play in facilitating Fe(II) release. By tracking Al and Fe(II) in a Fe(0) + Al2(SO4)3 treatment of metolachlor, we observed that Al was readily sorbed by the corroding iron with a corresponding release of Fe(II). The manufacturing process used to produce the Fe(0) also profoundly affected destruction rates. Metolachlor destruction rates with salt-amended Fe(0) were greater with annealed iron (indirectly heated under a reducing atmosphere) than unannealed iron. Moreover, the optimum pH for metolachlor dechlorination in water and soil differed between iron sources (pH 3 for unannealed, pH 5 for annealed). Our results indicate that metolachlor destruction by Fe(0) treatment may be enhanced by adding Fe or Al salts and creating pH and redox conditions favoring the formation of green rusts.     

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。     

Nitrate losses in subsurface drainage from a corn-soybean rotation as affected by fall and spring application of nitrogen and nitrapyrin

Substantial amounts of NO3 from agricultural crop production systems on poorly drained soils can be transported to surface water via subsurface drainage. A field study was conducted from the fall of 1993 through 2000 on a tile-drained Canisteo clay loam soil (fine-loamy, mixed, superactive, calcareous, mesic Typic Endoaquoll) to determine the influence of fall vs. spring application of N and nitrapyrin [NP; 2-chloro-6-(trichloromethyl) pyridine] on NO3 losses from a corn (Zea mays L.)-soybean [Glycine max (L.) Merr.] rotation. Four anhydrous ammonia treatments (fall N, fall N + NP, spring preplant N, and spring N + NP) were replicated four times and applied at 135 kg N ha(-1) for corn on individual drainage plots. Drainage occurred in all seven years. Seventy-one percent of the annual drainage and 75% of the annual NO3 loss occurred in April, May, and June. Fifty-four percent of the NO3 lost in the drainage occurred during the corn phase and 46% during the soybean phase. Annual flow-weighted NO3-N concentrations for the fall, fall + NP, spring, and spring + NP treatments averaged 14.3, 11.5, 10.7, and 11.3 mg L(-1) during the corn phase but annual NO3-N concentrations were still > or =10 mg L(-1) in three of six years for the spring preplant treatment. Averaged across the six rotation cycles, flow-normalized NO3-N losses ranked in the order: fall N > spring N + NP > fall N + NP > spring N. Under these conditions, NO3 losses in subsurface drainage from a corn-soybean rotation can be reduced 14% by spring N and 10% by late fall N + NP compared with fall-applied N. Nitrate losses were not appreciably reduced by adding NP to spring preplant N.     

Dissolution of phosphate in a phosphorus-enriched ultisol as affected by microbial reduction

Phosphorus dissolution often increases as soils become more reduced, but the mechanisms are not fully understood. The objectives of this research were to determine rates and mechanisms of P dissolution during microbial reduction of a surface soil from the North Carolina Coastal Plain. Duplicate suspensions of silt + clay fractions from a Cape Fear sandy clay loam (fine, mixed, semiactive, thermic Typic Umbraquult) were reduced in a continuously stirred redox reactor for 40 d. We studied the effects of three treatments on P dissolution: (i) 2 g dextrose kg(-1) solids added as a microbial carbon source at time 0 d; (ii) 2 g dextrose kg(-1) solids split into three additions at 0, 12, and 26 d; and (iii) no added dextrose. After 40 d of reduction, concentrations of dissolved reactive phosphorus (DRP) were similar for all treatments and increased up to sevenfold from 1.5 to 10 mg L(-1). The initial rate of reduction and dissolution of DRP was significantly greater for the 0-d treatment. A linear relationship (R(2) = 0.79) was found between DRP and dissolved organic carbon (DOC). Dissolved Fe and Al and pH increased, suggesting the formation of aqueous Fe- and Al-organic matter complexes. Separate batch experiments were performed to study the effects of increasing pH and citrate additions on PO(4) dissolution under aerobic conditions. Increasing additions of citrate increased concentrations of DRP, Fe, and Al, while increasing pH had no effect. Results indicated that increased dissolved organic matter (DOM) during soil reduction contributed to the increase in DRP, perhaps by competitive adsorption or formation of aqueous ternary DOM-Fe-PO(4) or DOM-Al-PO(4) complexes.     

Effect of peroxide on neutralization-potential values of siderite and other carbonate minerals

To assess quantitatively the effect of peroxide addition to standard static tests of the neutralization potential (NP) of mine wastes, 10 specimens of carbonate minerals, including five of siderite (FeCO3) and two of rhodochrosite (MnCO3), were analyzed by electron microprobe. The compositions of the siderite span a range from 60 to 86 mol % Fe. Tests of NP for the siderite diluted with 80% (w/w) kaolinite gave values of 647 to 737 kg CaCO3 equivalent per Mg for determinations by the standard Sobek method. However, if it is assumed that the ferrous carbonate component of the mineral does not contribute to NP in field situations because oxidation of Fe(II) to Fe(III) and the subsequent hydrolysis of Fe(III) leads to the release of an equivalent amount of acid, then the calculated NP for the samples ranges from 110 to 390 kg CaCO3 equivalent per Mg. Two different methods involving the addition of peroxide to the test solutions were successful in bringing the measured NP values closer to the theoretical ones. By contrast, the tests with rhodochrosite indicated the Mn(II) to be stable. For long-term environmental planning, especially for wastes from metalliferous sulfide-poor deposits in which gradual dissolution of silicate and aluminosilicate minerals may be involved in attenuating the acidity, consideration in the overall NP budget needs to be given to the ferrous iron content of those minerals. The presence of Fe2+-bearing minerals, especially carbonates, in tested mine-waste materials may lead to overestimated Sobek NP values, thus increasing the risk of poor-quality drainage and the need for costly remediation.     

Chemistry of inorganic arsenic in soils: II. Effect of phosphorus, sodium, and calcium on arsenic sorption

There are more than 10000 arsenic (As) contaminated sites in Australia. The ability of soils at these contaminated sites to sorb As is highly variable and appreciable amounts of As have been recorded in the subsurface soils. The potential risk of surface and ground water contamination by As at these sites is a major environmental concern. Factors that influence adsorption capacity of soils influence the bioavailability and subsequent mobility of As in soils. In the present study we investigated the effect of PO4(3-) and Na+ and Ca2+ on the sorption of AsV and AsIII by an Oxisol, a Vertisol, and two Alfisols. The presence of P (0.16 mmol L(-1)) greatly decreased AsV sorption by soils containing low amounts of Fe oxides (<100 mmol kg(-1)), indicating competitive adsorption between P and AsV for sorption sites. In contrast, the presence of a similar amount of P had little effect on the amount of AsV adsorbed by soils with high Fe content (>800 mmol kg(-1)). However, AsV sorption substantially decreased from 0.63 to 0.37 mmol kg(-1) as P concentration was increased from 0.16 to 3.2 mmol L(-1) in selected soils. This suggests increased competition between P and AsV for soil sorption sites, through either the higher affinity or the effect of mass action of the increasing concentration of P in solution. A similar effect of P on AsIII sorption was observed in the low sorbing Alfisol and high affinity Oxisol. However, the amount of AsIII sorbed by the Oxisol was much greater than the Alfisol for all treatments. The presence of Ca2+ increased the amount of AsV sorbed compared with that of Na+ and was manifested through changes in the surface charge characteristics of the soils. A similar trend in AsIII sorption was recorded with changes in index cation, although the effect was not as marked as recorded for AsV.     

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.     

Soil and tree-ring chemistry response to liming in a sugar maple stand

An evaluation of the impact of dolomitic lime [CaMg(CO3)2] on soils (five years after treatment) and sapwood chemistry (after four growing seasons) was realized for a Ca-deficient sugar maple stand at the lake Clair watershed. The effect on humus chemistry was significant: exchangeable Mg and Ca, effective acidity (EA), base saturation (BSe), pH, and effective cation exchange capacity (CECe) significantly increased, while exchangeable Fe significantly decreased. In the B horizon, liming increased exchangeable Ca, Mg, and Mn concentrations while decreasing other acid cations. No significant temporal trends in element concentrations in tree rings could be detected, although the lime treatment significantly changed the average xylem Mg and Mn concentrations as well as the average Mg/Mn and Ca/Mn ratios of the sapwood. The absence of temporal trends in rings from the last 20 yr implied a significant re-equilibration of elements through the sapwood. Significant relationships were found between averaged xylem Ca/Mn and Mg/Mn ratios and exchangeable humus Ca, Mg, Mn, Al, Fe, and H+ concentration, EA, CECe, and BSe, suggesting that the average xylem Ca/Mn and Mg/Mn ratios are strong indicators of the soil acid-base status.     

Sorption and stability of the polycyclic nitramine explosive CL-20 in soil

The polycyclic nitramine CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is being considered for use as a munition, but its environmental fate and impact are unknown. The present study consisted of two main elements. First, sorption-desorption data were measured with soils and minerals to evaluate the respective contributions of organic matter and minerals to CL-20 immobilization. Second, since CL-20 hydrolyzes at a pH of >7, the effect of sorption on CL-20 degradation was examined in alkaline soils. Sorption-desorption isotherms measured using five slightly acidic soils (5.1 < pH < 6.9) containing various amounts of total organic carbon (TOC) revealed a nonlinear sorption that increased with TOC [K(d) (0.33% TOC) = 2.4 L kg(-1); K(d) (20% TOC) = 311 L kg(-1)]. Sorption to minerals (Fe(2)O(3), silica, kaolinite, montmorillonite, illite) was very low (0 < K(d) < 0.6 L kg(-1)), suggesting that mineral phases do not contribute significantly to CL-20 sorption. Degradation of CL-20 in sterile soils having different pH values increased as follows: sandy agricultural topsoil from Varennes, QC, Canada (VT) (pH = 5.6; K(d) = 15 L kg(-1); 8% loss) < clay soil from St. Sulpice, QC, Canada (CSS) (pH = 8.1; K(d) = 1 L kg(-1); 82% loss) < sandy soil provided by Agriculture Canada (SAC) (pH = 8.1, K(d) = approximately 0 L kg(-1); 100% loss). The faster degradation in SAC soil compared with CSS soil was attributed to the absence of sorption in the former. In summary, CL-20 is highly immobilized by soils rich in organic matter. Although sorption retards abiotic degradation, CL-20 still decomposes in soils where pH is >7.5, suggesting that it will not persist in even slightly alkaline soils.     

Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT)

Munitions wastes such as TNT are widespread contaminants in soils and ground waters. We investigated a coupled abiotic-biotic treatment scheme for remediation of aqueous solutions of TNT. Mineralization of aqueous TNT (0.22 mM) was initially optimized with minimum reactant use (Fe3+ and H2O2) in light-assisted and dark, modified Fenton reactions at acidic and neutral pH. Complete TNT degradation occurred under all reaction conditions within 24 h. Using the optimum reactant concentrations, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 47 to 80%, after biomass addition to the acidic, dark Fenton-like reaction. Comparable increases of TNT mineralization were observed under neutral pH with similar reaction conditions. In light-assisted Fenton-like reactions at neutral pH, no increase in cumulative TNT mineralization (66%) was seen in coupled abiotic-biotic reactions. Abiotic photo-Fenton-like reactions alone, at acidic pH, produced complete TNT mineralization and required no biotic assistance. While light-enhanced Fenton reactions alone can provide high levels of TNT mineralization, the dark abiotic-biotic reaction scheme has perhaps a wider use due to a similar extent of TNT mineralization in the absence of light, leading to possible applications in soil slurry and in situ processes in the subsurface.     

Sorption and degradation characteristics of phosmet in two contrasting Australian soils

The organophosphate insecticide phosmet [phosphorodithioic acid, s-((1,3-dihydro-1,3-dioxo-2H-isoindol-2yl)methyl), o,o-dimethyl ester] is used to control red-legged earth mites (Halotydeus destructor), lucerne flea (Sminthurus viridis), and Oriental fruit moth (Cydia molesta) in horticulture and vegetable growing. This study was undertaken with two soils of contrasting properties to determine the extent to which sorption and degradation of the insecticide might influence its potential to leach from soil into receiving waters. Two soils were used: a highly organic, oxidic clay soil (Ferrosol) and a sandy soil low in organic matter (Podosol), sampled to 0.3 m depth. The extent of sorption and decomposition rate of a phosmet commercial formulation were measured in laboratory experiments. Sorption followed a Freundlich isotherm at all depths. The Freundlich coefficient K was significantly correlated (p = 0.005) with organic C content in the Podosol, and significantly correlated (p = 0.005) with organic C and clay content in the Ferrosol. K was highest (48.8 L kg-1) in the 0- to 0.05-m depth of the Ferrosol, but lowest (1.0 L kg-1) at this depth in the Podosol. Degradation followed first-order kinetics, with the phosmet half-life ranging from 14 h (0-0.05 m depth) to 187 h (0.2-0.3 m depth) in the Ferrosol. The half-life was much longer in the sandy Podosol, ranging from 462 to 866 h, and did not change significantly with depth. Soil organic C and to a lesser degree clay content influenced phosmet sorption and degradation, but the interaction was complex and possibly affected by co-solvents present in the commercial formulation.     

Major and trace elements of selected pedons in the USA

Few studies of soil geochemistry over large geographic areas exist, especially studies encompassing data from major pedogenic horizons that evaluate both native concentrations of elements and anthropogenically contaminated soils. In this study, pedons (n = 486) were analyzed for trace (Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Zn) and major (Al, Ca, Fe, K, Mg, Na, P, Si, Ti, Zr) elements, as well as other soil properties. The objectives were to (i) determine the concentration range of selected elements in a variety of U.S. soils with and without known anthropogenic additions, (ii) illustrate the association of elemental source and content by assessing trace elemental content for several selected pedons, and (iii) evaluate relationships among and between elements and other soil properties. Trace element concentrations in the non-anthropogenic dataset (NAD) were in the order Mn > (Zn, Cr, Ni, Cu) > (Pb, Co) > (Cd, Hg), with greatest mean total concentrations for the Andisol order. Geometric means by horizon indicate that trace elements are concentrated in surface and/or B horizons over C horizons. Median values for trace elements are significantly higher in surface horizons of the anthropogenic dataset (AD) over the NAD. Total Al, Fe, cation exchange capacity (CEC), organic C, pH, and clay exhibit significant correlations (0.56, 0.74, 0.50, 0.31, 0.16, and 0.30, respectively) with total trace element concentrations of all horizons of the NAD. Manganese shows the best inter-element correlation (0.33) with these associated total concentrations. Total Fe has one of the strongest relationships, explaining 55 and 30% of the variation in total trace element concentrations for all horizons in the NAD and AD, respectively.     

Organic ligand effects on enzymatic dephosphorylation of myo-inositol hexakis dihydrogenphosphate in dairy wastewater

Animal manure contains partially digested feed fiber and grains where phosphorus (P) is bound in organic compounds that include myo-inositol 1,2,3,5/4,6-hexakis dihydrogenphosphate or phytic acid (IP6). Information is needed on the effects of other (non-IP6) organic ligands (LIGND) on the enzymatic dephosphorylation of IP6, which is a potential source of dissolved orthophosphate P (PO4-P) in the soil-manure-water system. The effects of 1,2-cyclohexane diamino-tetraacetate (CDTA), diethylenetriamine-N,N,N',N',N'-pentaacetate (DTPA), ethylenediamine-N,N,N',N'-tetraacetate (EDTA), oxalate (OXA), and phthalate (PHTH) and LIGND to IP6 molar ratio and charge concentration ratio on IP6 dephosphorylation were studied to determine controlling mechanisms of IP6 persistence in manure. Solution PO4-P concentrations were analyzed by ion chromatography as the phosphomolybdate-ascorbic acid method partly includes IP6-P. Uncomplexed IP6 dephosphorylation by Aspergillus ficuum (Reichardt) Henn. phytase EC 3.1.3.8 at pH 4.5 and 6 is unaffected by the presence of LIGNDs. As the concentrations of Ca2+, Al3+, or Fe3+ increase, dephosphorylation is reduced. Their inhibitory effect lessens in the presence of LIGNDs, in the following order: CDTA = EDTA > DTPA > OXA > or = PHTH. Whether CDTA or EDTA is the most effective LIGND depends upon the acidity of the suspension and LIGND charge concentration, reducing the inhibitory effect of polyvalent counterions to the point of promoting the hydrolysis of a manure phytase-hydrolyzable phosphorus (PHP) fraction that is otherwise unavailable. Therefore, ligand-induced changes increase the mobilization and dephosphorylation of complexed organic P, above and beyond the simple dissolution of inorganic phosphates. An analytical method for potentially bioavailable PHP in animal manure should include a LIGND as extracting reagent. Also, potential LIGNDs in an organic carbon-rich dairy wastewater may increase the release of PHP and environmental dispersion of PO4-P.     

Tillage and nutrient source effects on surface and subsurface water quality at corn planting

This study quantified the effects of tillage (moldboard plowing [MP], ridge tillage [RT]) and nutrient source (manure and commercial fertilizer [urea and triple superphosphate]) on sediment, NH4+ -N, NO3- -N, total P, particulate P, and soluble P losses in surface runoff and subsurface tile drainage from a clay loam soil. Treatment effects were evaluated using simulated rainfall immediately after corn (Zea mays L.) planting, the most vulnerable period for soil erosion and water quality degradation. Sediment, total P, soluble P, and NH4+ -N losses mainly occurred in surface runoff. The NO3- -N losses primarily occurred in subsurface tile drainage. In combined (surface and subsurface) flow, the MP treatment resulted in nearly two times greater sediment loss than RT (P < 0.01). Ridge tillage with urea lost at least 11 times more NH4+ -N than any other treatment (P < 0.01). Ridge tillage with manure also had the most total and soluble P losses of all treatments (P < 0.01). If all water quality parameters were equally important, then moldboard plow with manure would result in least water quality degradation of the combined flow followed by moldboard plow with urea or ridge tillage with urea (equivalent losses) and ridge tillage with manure. Tillage systems that do not incorporate surface residue and amendments appear to be more vulnerable to soluble nutrient losses mainly in surface runoff but also in subsurface drainage (due to macropore flow). Tillage systems that thoroughly mix residue and amendments in surface soil appear to be more prone to sediment and sediment-associated nutrient (particulate P) losses via surface runoff.     

Neutralization potential determination of siderite (FeCO3) using selected oxidants

Siderite (FeCO3) is commonly found in coal overburden and, when present, can cause interference in the determination of neutralization potential (NP). Under acidic testing conditions, FeCO3 reacts to neutralize acid, which contributes to the NP. However, continued weathering of FeCO3 (oxidation of Fe2+ and hydrolysis of Fe3+) produces a neutral to slightly acidic solution. The effects of hydrogen peroxide (H2O2), potassium permanganate (KMnO4), and O2 on the laboratory measurement of NP of siderite samples taken from overburden were examined. All oxidation treatments lowered the NP values of the siderite samples as compared with the standard USEPA method. However, oxidation with H2O2 produced variable results depending on the amount of H2O2 added. Neutralization potential values obtained after oxidation treatments were highly correlated with Mn concentration. Reaction products (i.e., 2-line ferrihydrite) of siderite samples with H2O2 and KMnO4 were not representative of natural siderite weathering. Oxidation with O2 produced the lowest NP values for siderite samples. The reaction products produced by oxidation with O2 most closely represent those intermediate products formed when siderite is exposed to atmospheric weathering conditions. Oxidation with O2 also proved to be the most reproducible method for accurately assessing NP when siderite is present in overburden samples.     

Hydrological properties of a clay loam soil after long-term cattle manure application

Limited information exists on the effect of long-term application of beef cattle (Bos taurus) manure on soil hydrological properties in the Great Plains region of North America. A site on a clay loam soil (Typic Haploboroll) was used to examine the effect of manure addition on selected soil hydrological properties in 1997 and 1998. The manure was annually applied in the fall for 24 yr at one, two, and three times the recommended rates (in 1973) under dryland (0, 30, 60, and 90 Mg ha(-1) wet basis) and irrigation (0, 60, 120, and 180 Mg ha(-1)). Manure significantly (P < or = 0.05) increased soil water retention (0-5 and 10-15 cm) by 5 to 48% compared with the control at most potentials between 0 and -1500 kPa. Field soil water content (0-5 and 10-15 cm) was increased by 10 to 22% in the summers of 1997 and 1998. Manure increased ponded infiltration by more than 200% at 90 Mg ha(-1) under dryland (1998) and at rates > or = 120 Mg ha(-1) under irrigation (1997). Field-saturated hydraulic conductivity (Kfs) of surface soil (1-cm depth) was significantly increased by 76 to 128% under dryland (1998) and irrigation (1997), as were number of pores > 1120 microm in diameter (37-128% increase). In contrast, manure rate had little or no effect on unsaturated hydraulic conductivity [K(psi)] values (-0.3, -0.5, -0.7, and -1.0 kPa) in 1997 and 1998. Overall, soil hydrological parameters generally had a neutral or positive response to 24 yr of annual manure addition.     

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.     

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.     

Removal of Fe(II) from the wastewater of a galvanized pipe manufacturing industry by adsorption onto bentonite clay

Bentonite clay has been used for the adsorption of Fe(II) from aqueous solutions over a concentration range of 80-200 mg/l, shaking time of 1-60 min, adsorbent dosage from 0.02 to 2 g and pH of 3. The process of uptake follows both the Langmuir and Freundlich isotherm models and also the first-order kinetics. The maximum removal (>98%) was observed at pH of 3 with initial concentration of 100 mg/l and 0.5 g of bentonite. The efficiency of Fe(II) removal was also tested using wastewater from a galvanized pipe manufacturing industry. More than 90% of Fe(II) can be effectively removed from the wastewater by using 2.0 g of the bentonite. The effect of cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium and copper) on the removal of Fe(II) was studied in the concentration range of 10-500 mg/l. All the added cations reduced the adsorption of Fe(II) at high concentrations except Zn. Column studies have also been carried out using a certain concentration of wastewater. More than 99% recovery has been achieved by using 5 g of the bentonite with 3M nitric acid solution.     

Can assessing for potential contribution of soil organic and inorganic components for butachlor sorption be improved?

Sorption of butachlor to various types of common soil components was investigated. Six pure minerals (montmorillonite [Mont], kaolinite [Kaol], Ca homoionic montmorillonite [Ca-Mont] and kaolinite [Ca-Kaol], amorphous hydrated Al and Fe oxides [AHOs-Al, AHOs-Fe]), four soil alkali-extractable pure humic acids (HAs), and the four corresponding HAs originated real unmodified and HO-treated soils were selected as the representative sorbents. Results showed that the HAs played a crucial role, and clay minerals (especially Mont) also showed an important effect in butachlor sorption. The AHOs may likely influence only in a mediator way by enhancing the availability of sorption domains of HAs. By removing 78% (on average) of the total organic carbon (TOC) from the soils with HO, the content ratio of clay to TOC (RCO) increased by an average of 367% and became >60. This change simultaneously decreased the sorption capacity of soils (40%, on average). Considering that the surface sorption domain on clay minerals may be highly exposed and more competitive after the partial removal of soil organic matter (SOM), this reaffirmed the potential contribution from clay minerals. It can thus be inferred that in the real soil where SOM and clay minerals are associated, the coating of clay minerals may have weakened the partition function of SOM or blocked some sorption domain within SOM, resulting in a decreased sorption of butachlor. Therefore, clay minerals, especially 2:1 type expanding minerals, may play a dual function vs. SOM content for the sorption of butachlor in soil.