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.     

On-line production of ferrate with an electrochemical method and its potential application for wastewater treatment – A review

A number of studies on the oxidation of various organic/inorganic contaminants by ferrate(VI) were reported in the 1980s and 1990s. The exploration of the use of ferrate(VI) for water and wastewater treatment has been well addressed recently. However, challenges have existed for the implementation of ferrate(VI) technology in practice due to the instability of a ferrate solution or high production cost of solid ferrate products. The research has been carried out aiming at the generation and application of ferrate(VI) in situ. This paper thus reviews ferrate chemistry and its overall performance as a water treatment chemical, discusses the factors affecting the ferrate yield efficiency using the electrochemical method, and finally, summarises the work on the production and use of ferrate in situ which is currently under study.     

Perfluorinated phosphine oxide and sulfides as extractants for heavy metals and radionuclides

New highly fluorinated monodentate and bidentate phosphine oxide compounds of the type {CF(3)(CF(2))(n)CH(2)CH(2)}(3)PO (n = 5, 9) and [{CF(3)(CF(2))(5)CH(2)CH(2)}(2)P(O)CH(2)CH(2)P(O){CH(2)CH(2)(CF(2))(5)CF(3)}] have been prepared. Their ability to extract a number of metals and radionuclides from aqueous solutions into perfluorinated solvents has been established and the extractable species investigated. All extractants extract the metals As(V), Cd(II), Co(II), Cr(VI), Hg(II), Pb(II), and Sn(II) with >75% removal. In addition, the radioisotopes (90)Sr(II), (133)Ba(II), and U(VI) have been investigated, whilst (59)Fe(III) has been used to model the extraction of plutonium. (133)Ba(II) shows a high distribution ratio for monodentate phosphine oxides, whilst for UO(2)(2+) and (59)Fe(III) bidentate phosphine oxides are superior.     

Inorganic nitrogen and phosphorus in Sierran forest O horizon leachate

High in situ concentrations of inorganic N and P have been reported in overland/litter interflow from Sierran forests, indicating that these nutrients are derived from the forest floor O horizons. To test this hypothesis, forest floor monoliths consisting of the combined O(e) and O(i) horizons were collected near the South Shore of Lake Tahoe, Nevada, for leaching experiments. Three monoliths were left intact, and three were hand-separated according to horizon for a total of three treatments (combined O(e)+O(i), O(e) only, and O(i) only) by three replications. Samples were randomized and placed into lined leaching bins. Initial leaching consisted of misting to simulate typical early fall precipitation. This was followed by daily snow applications and a final misting to simulate spring precipitation. Leachate was collected, analyzed for NH(4)(+)-N, NO(3)(-)-N, and PO(4)(3-)-P, and a nutrient balance was computed. There was a net retention of NH(4)(+)-N, but a net release of both NO(3)(-)-N and PO(4)(3-)-P, and a net release of inorganic N and P overall. Total contributions (mg) of N and P were highest from the O(e) and O(e)+O(i) combined treatments, but when expressed as per unit mass, significantly (p < 0.05) higher amounts of NO(3)(-)-N and PO(4)(3-)-P were derived from the O(i) materials. The nutrients in forest floor leachate are a potential source of biologically available N and P to adjacent surface waters. Transport of these nutrients from the terrestrial to the aquatic system in the Lake Tahoe basin may therefore play a part in the already deteriorating clarity of the lake.     

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.     

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.     

Gas dynamics in eutrophic lake sediments affected by oxygen, nitrate, and sulfate

In many freshwater ecosystems, the contents of NO3- and SO4(2-) have increased, whereas O2 has been depleted due to the increased acid and nutrient loads. These changes may affect carbon turnover and the dynamics of the major greenhouse gases CO2, CH4, and N2O. We studied the effects of O2, NO3-, and SO4(2-) availability on carbon mineralization, and fluxes of CO2, CH4, and N2O in the sediments of hyper-eutrophic Lake Kev?t?n, Finland. Undisturbed sediment cores from the deep (9 m) and shallow (4 m) profundal were incubated in a laboratory microcosm with oxic and anoxic water flows with NO3- or SO4(2-) concentrations of 0, 30, 100, 300, and 2000 microM. The carbon mineralization rate (i.e., the sum of released CO2-C and CH4-C) was not affected by the oxidants. However, the oxidants did change the pathways of carbon degradation and the release of CH4. All of the oxidants depressed CH4 fluxes in the shallow profundal sediments, which had low organic matter content. In the deep profundal sediments rich in organic matter, the CH4 release was reduced by O2 but was not affected by SO4(2-) (the effect of NO3- was not studied). There was an increase in N2O release as the overlying water NO3- concentration increased. Anoxia and highly elevated NO3- concentrations, associated with eutrophication, increased drastically the global warming potential (GWP) of the sedimentary gases in contrast to the SO4(2-) load, which had only minor effects on the GWP.     

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.     

油田含油污水高级氧化技术研究

以气浮—过滤预处理后的污水为处理对象,通过臭氧氧化与Fenton氧化两种方法处理油田含油污水。经实验验证:Fenton在pH为4,H2O2初始浓度为0.08mol/L,Fe2+与H2O2的摩尔比为1:10,H2O2与CODCr的质量比为1:1,反应时间为60min的条件下,去除率达54.3%(CODCr100mg/L),可达到GB8978-1996《污水综合排放标准》二级标准。     

Solid phosphorus phase in aluminum- and iron-treated biosolids

Stabilization of phosphorus (P) in sewage sludge (biosolids) to reduce water-soluble P concentrations is essential for minimizing P loss from amended soils and maximizing the capacity of the soil to safely serve as an outlet for this waste material. The chemical form at which P is retained in biosolids stabilized by Al(2)(SO(4))(3) x 18H(2)O (alum) or FeSO(4) x 7H(2)O (FeSul) was investigated by scanning electron microscopy (SEM) equipped with energy-dispersive X-ray elemental spectrometry (EDXS) and by X-ray diffraction (XRD). Both treatments resulted in the formation of a Ca-P phase, probably brushite. Phosphorus was further retained in the alum-treated biosolids by precipitation of an Al-P phase with an Al/P molar ratio of about 1:1, while in the FeSul-treated biosolids, P was retained by both precipitation with Fe/P molar ratios of 1:1 or 1.5:1, and by adsorption onto newly formed Fe hydroxides exhibiting an Fe/P molar ratio of up to 11:1. All of these mechanisms efficiently reduced P solubility and are crucial in biosolids environmentally safe agronomic beneficial use for this waste product; however, each P phase formed may react differently in the amended soil, depending on soil properties. Thus, the proper P stabilization method would depend on the target soil.     

Quantitative,chemical, and mineralogical characterization of flue gas desulfurization by-products

The objective of this study was to demonstrate that simple fractionation and selective dissolution techniques can be used to provide detailed chemical and mineralogical analyses of flue gas desulfurization by-products. The material studied was a mine grout prepared as a 1:1 mixture (wt./wt.) of fly ash (FA) and filter cake (FC) with hydrated lime (50 g kg(-1)) added to improve handling. The hydrated lime was composed mostly of calcite (CaCO3), portlandite [Ca(OH)2], lime (CaO), and brucite [Mg(OH)2] (515, 321, 55, and 35 g kg(-1), respectively) and had low (<6 g kg(-1)) concentrations of most trace elements. The FC contained hannebachite (CaSO3 x 0.5H2O) (786 g kg(-1)) with smaller quantities (<10 g kg(-1)) of calcite, quartz (SiO2), brucite, and gypsum (CaSO4 x 2H2O). Except for B and Cu, trace element concentrations were comparable to those in the hydrated lime. The FA contained both magnetic (222 g kg(-1)) and nonmagnetic (778 g kg(-1)) fractions. The former was composed mostly of hematite (Fe2O3), magnetite (Fe3O4), and glass (272, 293, and 287 g kg(-1), respectively), whereas the latter was enriched in glass, quartz, and mullite (Al6Si2O13) (515, 243, and 140 g kg(-1), respectively). Etching with 1% HF showed that 60 to 100% of trace elements were concentrated in the glass, although some metals (Co, Cr, and Mn) were clearly enriched in the magnetic phase. The aged grout contained 147 g kg(-1) ettringite [Ca6Al2(SO4)3(OH)12 x 26H2O] in addition to 314 g kg(-1) hannebachite and 537 g kg(-1) insoluble phases (mullite, quartz, hematite, magnetite, and glass).     

Comparison of Diuron degradation by direct UV photolysis and advanced oxidation processes

The rates of Diuron elimination by some advanced oxidation processes (AOPs) such as Fe(III)/UV, Ferrioxalate/UV, Fe(III)/H(2)O(2)/UV, Ferrioxalate/UV/H(2)O(2) and Fe(III)/H(2)O(2) have been compared. Experiments have been conducted at pH=2.3+/-0.1 with a batch reactor equipped with a low-pressure mercury lamp emitting mainly at 253.7nm. Data obtained under the following experimental conditions ([H(2)O(2)](0)=10(-3)M, [Diuron](0)=5x10(-5)M and [Fe(III)](0)=10(-3)M) have shown that rates of Diuron oxidation were higher with the systems Fe(III)/H(2)O(2)/UV and Ferrioxalate/UV/H(2)O(2) than with Fe(III)/UV and Fe(III)/H(2)O(2). On the other hand, Fe(III)/UV was found to be very efficient in mineralization of Diuron solution in comparison to direct UV photolysis. The experimental results showed that radical ()OH is the major pathway in the process of Diuron degradation.     

Removal of organic matter and nitrogen from river water in a model floodplain

A significant improvement in river water quality cannot be expected unless nonpoint-source contaminants are treated in addition to the further treatment of point-source contaminants. If river water is sprayed over a floodplain, the consequent water filtration through the sediment profile can simultaneously remove organic matter and nitrogen in the water through aerobic and denitrifying reactions. This hypothesis was tested using lysimeters constructed from polyvinyl chloride (PVC) pipe (150 cm long, 15 cm in diameter) packed with loamy sand floodplain sediment. Water was applied to the top of the lysimeters at three different flow rates (48, 54, and 68 mm d(-1)). Concentrations of NO3 and dissolved oxygen (DO), chemical oxygen demand (COD), and redox potential (Eh) in the water were measured as functions of depth after the system reached steady states for both water flow and reactions. At the rate of 68.0 mm d(-1), a reducing condition for denitrification developed below the 5-cm depth due to the depletion of O2 by organic matter degradation in the surface oxidizing layer; Eh and DO were below 205 mV and 0.4 mg L(-1), respectively. At a depth of 70 cm, COD and NO3-N concentration decreased to 5.2 and 3.8 mg L(-1) from the respective influent concentrations of 17.1 and 6.2 mg L(-1). Most biodegradable organic matter was removed during flow and further removal of NO3 was limited by the lack of an electron donor (i.e., organic matter). These results indicate that the floodplain filtration technique has great promise for treatment of contaminated river water.     

Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI)

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.     

Characteristics of major secondary ions in typical polluted atmospheric aerosols during autumn in central Taiwan

In autumn of 2008, the chemical characteristics of major secondary ionic aerosols at a suburban site in central Taiwan were measured during an annually occurring season of high pollution. The semicontinuous measurement system measured major soluble inorganic species, including NH(4)(+), NO(3)(-), and SO(4)(2-), in PM(10) with a 15 min resolution time. The atmospheric conditions, except for the influences of typhoons, were dominated by the local sea-land breeze with clear diurnal variations of meteorological parameters and air pollutant concentrations. To evaluate secondary aerosol formation at different ozone levels, daily ozone maximum concentration (O(3,daily max)) was used as an index of photochemical activity for dividing between the heavily polluted period (O(3,daily max) ≧80 ppb) and the lightly polluted period (O(3,daily max)<80 ppb). The concentrations of PM(10), NO(3)(-), SO(4)(2-), NH(4)(+) and total major ions during the heavily polluted period were 1.6, 1.9, 2.4, 2.7 and 2.3 times the concentrations during the lightly polluted period, respectively. Results showed that the daily maximum concentrations of PM(10) occurred around midnight and the daily maximum ozone concentration occurred during daytime. The average concentration of SO(2) was higher during daytime, which could be explained by the transportation of coastal industry emissions to the sampling site. In contrast, the high concentration of NO(2) at night was due to the land breeze flow that transport inland urban air masses toward this site. The simulations of breeze circulations and transitions were reflected in transports and distributions of these pollutants. During heavily polluted periods, NO(3)(-) and NH(4)(+) showed a clear diurnal variations with lower concentrations after midday, possibly due to the thermal volatilization of NH(4)NO(3) during daytime and transport of inland urban plume at night. The diurnal variation of PM(10) showed the similar pattern to that of NO(3)(-) and NH(4)(+) aerosols. This indicated that the formatted secondary aerosols in the inland urban area could be transported to the coastal area by the weak land breeze and deteriorated the air quality in the coastal area at night.     

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.     

Metal distribution and stability in constructed wetland sediment

The A-01 wetland treatment system (WTS) is a surface flow wetland planted with giant bulrush [Schoenoplectus californicus (C.A. Mey.) Palla] that is designed to remove Cu and other metals from the A-01 National Pollution Discharge Elimination System (NPDES) effluent at the Savannah River Site near Aiken, SC. Copper, Zn, and Pb concentrations in water were usually reduced 60 to 80% by passage through the treatment system. The Cu concentrations in the wetland sediments increased from about 4 to 205 and 796 mg kg(-1), respectively, in the organic and floc sediment layers in cell 4A over a 5-yr period. Metal concentrations were higher in the two top layers of sediment (i.e., the floc and organic layers) than in the deeper inorganic layers. Sequential extraction was used to evaluate remobilization and retention of Cu, Pb, Zn, Mn, and Fe in the wetland sediment. Metal remobilization was determined by the potentially mobile fraction (PMF) and metal retention by the recalcitrant factor (RF). The PMF values were high in the floc layer but comparatively low in the organic and inorganic layers. High RF values for Cu, Zn, and Pb in the organic and inorganic layers indicated that these metals were strongly bound in the sediment. The RF values for Mn were lower than for the other elements especially in the floc layer, indicating low retention or binding capacity. Retention of contaminants was also evaluated by distribution coefficient (Kd) values. Distribution coefficient (Kd) values were lower for Cu and Zn than for Pb, indicating a smaller exchangeable fraction for Pb.     

Removal of Cr(VI) from Cr-contaminated groundwater through electrochemical addition of Fe(II)

The conventional chemical reduction-precipitation technique in the removal of Cr(VI) from contaminated groundwater involves a two-step process whereby Cr(VI) is first reduced to Cr(III) at an acidic pH by a reducing agent and in a subsequent step, Cr(III) is precipitated as insoluble hydroxide at an alkaline pH. In a variation of this method, Fe(II) is added electrochemically to the Cr(VI) containing water. From a pure iron electrode, Fe(2+) ions are released into the solution and bring forth the reduction of Cr(VI). At the cathode, H(2)O is reduced whereby the OH(-) ions entering the solution keep the pH of the solution in the alkaline range. This latter fact greatly facilitates simultaneous reduction of Cr(VI) to Cr(III) and co-precipitation of hydroxides of trivalent Cr and Fe. On the basis of a set of experimental data, it is shown that this process is both thermodynamically and kinetically efficient, meaning, with the electrochemical method, rapid and nearly complete removal of Cr(VI) from a groundwater source with both high and low levels of Cr-contamination can be achieved. These factors make the electrochemical process superior to the conventional chemical process in remediation of Cr-contaminated groundwater.     

Comparison of zinc complexation properties of dissolved natural organic matter from different surface waters

The zinc binding characteristics of natural organic matter (NOM) from several representative surface waters were studied and compared. NOM samples were concentrated by reverse osmosis. The samples were treated in the laboratory to remove trace metals. Square wave anodic stripping voltammetry (SWASV) was used to study zinc complexing properties of those NOM samples at fixed pH, ionic strength, and dissolved organic carbon (DOC) concentrations. Experimental data were compared to the predictions from the Windermere Humic Aqueous Model (WHAM) Version VI. At the same pH, ionic strength, and temperature, the zinc titration curves for NOM samples from different surface water sources tested in our study almost overlapped each other, indicating similarity in zinc binding properties of the NOM. A discrete two-site model gave good fits to our experimental titration data. Non-linear fitting by FITEQL 4.0 shows that the conditional zinc binding constants at the same pH are similar for NOM from different sources, indicating that zinc complexation characteristics of the NOM used in our study do not depend on their origin and one set of binding parameters can be used to represent Zn-NOM complexation for NOM samples from those different surface water sources representing geographically diverse locations. In addition, the total ligand concentrations (L(1,T), L(2,T), and L(T)) of all NOM show no observable gradation with increasing pH (L(1,T)=2.06+/-0.80 mmol/g carbon; L(2,T)=0.12+/-0.04 mmol/g carbon; L(T)=2.18+/-0.78 mmol/g carbon), while the conditional binding constants of zinc by NOM (logK(ZnL)(c)) show a linear increase with increasing pH(logK(1)(c)(pH=6.0)=4.69+/-0.25; logK(1)(c)(pH=7.0)=4.94+/-0.10; logK(1)(c)(pH=8.0)=5.25+/-0.006; logK(2)(c)(pH=6.0)=6.29+/-0.13; logK(2)(c)(pH=7.0)=6.55+/-0.08; logK(2)(c)(pH=8.0)=6.86+/-0.023) with a slope of ca. 0.28, indicating the zinc-NOM complexes become more stable at higher pH. The WHAM VI predicted free zinc ion activities at high zinc concentrations agree with our experimental results at pH 6.0, 7.0, and 8.0. However, the zinc binding of these NOM samples is over estimated by WHAM VI at zinc concentrations below 10(-6) M at pH 8.0.     

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.