Effects of chloride,sulfate and natural organic matter (NOM) on the accumulation and release of trace-level inorganic contaminants from corroding iron

This study examined effects of varying levels of anions (chloride and sulfate) and natural organic matter (NOM) on iron release from and accumulation of inorganic contaminants in corrosion scales formed on iron coupons exposed to drinking water. Changes of concentrations of sulfate and chloride were observed to affect iron release and, in lesser extent, the retention of representative inorganic contaminants (vanadium, chromium, nickel, copper, zinc, arsenic, cadmium, lead and uranium); but, effects of NOM were more pronounced. DOC concentration of 1 mg/L caused iron release to increase, with average soluble and total iron concentrations being four and two times, respectively, higher than those in the absence of NOM. In the presence of NOM, the retention of inorganic contaminants by corrosion scales was reduced. This was especially prominent for lead, vanadium, chromium and copper whose retention by the scales decreased from >80% in the absence of NOM to <30% in its presence. Some of the contaminants, notably copper, chromium, zinc and nickel retained on the surface of iron coupons in the presence of DOC largely retained their mobility and were released readily when ambient water chemistry changed. Vanadium, arsenic, cadmium, lead and uranium retained by the scales were largely unsusceptible to changes of NOM and chloride levels. Modeling indicated that the observed effects were associated with the formation of metal–NOM complexes and effects of NOM on the sorption of the inorganic contaminants on solid phases that are typical for iron corrosion in drinking water.     

Characterization of elemental and structural composition of corrosion scales and deposits formed in drinking water distribution systems

Corrosion scales and deposits formed within drinking water distribution systems (DWDSs) have the potential to retain inorganic contaminants. The objective of this study was to characterize the elemental and structural composition of extracted pipe solids and hydraulically-mobile deposits originating from representative DWDSs. Goethite (α-FeOOH), magnetite (Fe₃O₄) and siderite (FeCO₃) were the primary crystalline phases identified in most of the selected samples. Among the major constituent elements of the deposits, iron was most prevalent followed, in the order of decreasing prevalence, by sulfur, organic carbon, calcium, inorganic carbon, phosphorus, manganese, magnesium, aluminum and zinc. The cumulative occurrence profiles of iron, sulfur, calcium and phosphorus for pipe specimens and flushed solids were similar. Comparison of relative occurrences of these elements indicates that hydraulic disturbances may have relatively less impact on the release of manganese, aluminum and zinc, but more impact on the release of organic carbon, inorganic carbon, and magnesium.     

Chemical speciation and distribution of arsenic in water, suspended solids and sediment of Xiangjiang River, China

The forms of arsenic in the Zuzou Zone of the Xiangjang River are evaluated. Nine fractions of arsenic, consisting of soluble arsenic(III) and total soluble arsenic, loosely bound arsenic, aluminium arsenate, iron arsenate, calcium arsenate, arsenic occluded on iron oxide, organic compounds of arsenic and residual arsenic, were separated from suspended solids and sediments by sequential chemical extraction. All arsenic fractions were determined by ASV and AFS. The distributions of arsenic and arsenic fractions in water, sediments and suspended solids are discussed in terms of the mechanisms of arsenic transport and deposition in aquatic ecosystems.     

Assessment of arsenic mobility in the soils of some golf courses in South Florida

High concentrations of arsenic have been detected in soils and underlying groundwater of some South Florida golf courses, indicating the possible impact of the application of arsenic-containing herbicides. The mobility of arsenic in the soils from selected golf courses was studied using a simple two-step sequential extraction procedure. Sodium nitrate (0.1 M), potassium dihydrogen phosphate (0.1 M) and concentrated nitric acid were used to obtain mobile, mobilizable, and pseudo total arsenic fractions. Soils were separated into fine (<0.25 mm) and large (0.25-0.75 mm) particle size fractions. Arsenic contents were correlated with the distribution of iron (R2=0.4827), manganese (R2=0.7674) and aluminum (R2=5459) in the particle size fractions, while such correlation was not observed for soil organic matter, indicating that the oxides/hydroxides of iron, manganese and aluminum control the distribution of arsenic in these soils. Sodium nitrate and potassium dihydrogen phosphate extractants used in this study extracted large portions of arsenic from most soil samples studied. This is especially true for the fine fraction where the extractable arsenic ranged from 9.2 to 51.3% with an average of 28.7 +/- 13.3%, whereas in the large fraction, arsenic ranged from 7.2 to 24.7% with an average of 15.4 +/- 6.4%. These extractants, however, release only small amounts of iron, manganese, and aluminum. It seems likely that arsenic can be released by sodium nitrate and potassium dihydrogen phosphate without significant dissolution of the oxides/hydroxides of iron, manganese, and aluminum in these soil samples.     

Microbes influence the fractionation of arsenic in paddy soils with different fertilization regimes

Sequential extraction procedures were used to investigate the influence of the microbes on the distribution of arsenic in a Chinese paddy soil under different long-term fertilization treatments. The paddy soil with four long-term fertilization treatments (CK, M, NPK and NPK + M) and three levels of arsenate addition (0, 50, 100 mg As kg^− 1 dry soil), were selected to construct microcosms for laboratory incubation. After the incubation, soil samples were sequentially extracted to determine As in various fractions, i.e. water soluble (F0), exchangeable (F1), bound to carbonates (F2), bound to Fe and Mn oxides (F3), bound to organic matter and sulfides (F4), and residual (F5, mineral matrix). Results showed that most of the As was fixed by mineral matrix (F5, ratios ranging from 46.22% to 96.37%), followed by As bound to Fe and Mn oxides (F3, ratios ranging from 3.14% to 28.18%), and the ratios of the other four fractions (F0, F1, F2 and F4) were mostly less than 10%. The microbes in the paddy soil could make As transform from inactive fraction (F5) to relatively active fractions (F0, F1, F2 and F3) and thus increase its environmental risk. With the increase of the As addition levels and with the application of manure or chemical NPK fertilizers, As was distributed more in the relatively active fractions (F0, F1, F2, F3 and F4) in the paddy soil mediated by the microbes. In addition, Fe and Mn oxides could play an important role in decreasing the As leaching potential from the mineral matrix to soil solution and thus abate the As risk to human health.     

Effect of redox potential on heavy metal binding forms in polluted canal sediments in Delft (The Netherlands)

Heavy metal binding forms for Cu, Zn and Pb were determined at four representative sediment sites in the canals of Delft (The Netherlands), using selective chemical extraction methods. Small differences (on average <5%) were found between duplicate extraction experiments. The dominant Cu binding form was always related to sulphide and organics in the sediment. Zn was mainly bound to iron+manganese (hydr)oxides, whereas Pb was rather evenly distributed over the different labile and non-labile binding fractions. A gradual (over about 1 month) increase in redox potentials of the anaerobic sediments led to a 7-37% sediment release of the above heavy metals; this could mainly be ascribed to oxidation of the heavy metal-sulphide bindings. Part of the released heavy metals was re-adsorbed by the labile binding phases ("exchangeable" and "carbonate bound"). Contrary to expectations, we found a decrease rather than an increase in the Fe+Mn (hydr)oxide binding forms. This can probably be ascribed to non-equilibrium reactions in the time span of the experiments, as well as side reactions such as complexation with humic acids and hindered precipitation reactions due to organic matter coatings.     

Partitioning of trace metals before and after biological removal of metals from sediments

Metal removal by biological solubilization in three strongly contaminated sediments was carried out in a two-liter stirred bioreactor. Biological treatment yielded metal removal efficiencies in the range of 11-30%, 43-57%, 60-79%, 61-90%, 18-21%, 0-10% for Pb, Cu, Zn, Cd, Ni and Cr, respectively. The treated sediments were then rinsed with a NaCl solution (0.5 M), resulting in an increase by nearly 47% in Pb removal for the three sediments, while for other metals (Cu, Zn, Cd, Ni, Cr), the NaCl rinse did not seem to allow any significant increase in metal solubilization. A standard procedure of sequential selective extraction (SSE) was applied to the sediments before and after each treatment. With regard to Pb, Zn and Cd, the carbonate bound fractions (2/3 sediments) represented 18-42% of metals prior to treatment, while the iron and manganese oxides bound fraction constituted 39-60% of metals for the three sediments. Between 90 and 100% of Pb, Zn and Cd removed by the process came from the fractions bound to carbonates and from those bound to Fe and Mn oxides. The organic matter and sulfide bound fractions contained 65-72% of total Cu present before treatment and the process removed, on average, 63% Cu present in this fraction. In contrast, Ni and Cr were found mainly in the residual fractions (50-80%). Finally, this biological treatment did not solubilize Cr appreciably, while removal of Ni mostly originated from the carbonate and Fe/Mn oxides fractions (70-80%).     

Groundwater geochemistry and its implications for arsenic mobilization in shallow aquifers of the Hetao Basin, Inner Mongolia

Arsenic concentrations in shallow groundwaters from the Hetao Basin of Inner Mongolia range between 0.6 and 572 microg/L. High As groundwaters generally occur in the shallow alluvial-lacustrine aquifers, which are mainly composed of black (or dark grey) fine sands in a reducing environment. They are characterized by high concentrations of dissolved Fe, Mn, HCO(3)(-), P and S(2-), and low concentrations of NO(3)(-) and SO(4)(2-). Low SO(4)(2-) coupled with high S(2-) suggests that SO(4)(2-) reduction has been an active process. In the reducing groundwaters, inorganic As(III) accounts for around 75% of total dissolved As. Total As contents in the sediments from three representative boreholes are observed to be 7.3-73.3 mg/kg (average of 18.9 mg/kg). The total As is mildly-strongly correlated with total Fe and total Mn, while a quite weak correlation exists between total As and total S, suggesting that the As is associated with Fe-Mn oxides, rather than sulfides in the sediments. It is found in the sequential extraction that chemically active As is mainly bound to Fe-Mn oxides, up to 3500 microg/kg. The mobilization of As under reducing conditions is believed to include reductive dissolution of Fe-Mn oxides and reduction of adsorbed As. Although exchangeable As is labile and very vulnerable to hydrogeochemical condition, the contribution is relatively limited due to the low concentrations. The competition between As and other anions (such as HPO(4)(2-)) for binding sites on Fe-Mn oxides may also give rise to the release of As into groundwater. Slow groundwater movement helps accumulation of the released As in the groundwaters.     

Natürliche Schadstoffrückhalteprozesse für Arsen und Kupfer am Standort einer ehemaligen Buntfarbenfabrik

The sharply confined pattern of arsenic groundwater contamination at the site of a historic dye factory suggests that natural attenuation processes are active and efficient. The supporting data included sequential soil extractions combined with analyses of other soil properties like carbonate content, the loss of ignition and cation exchange capacity and the extraction characteristics of the original dye pigment. The results point to iron oxides and iron hydroxides as the most important adsorbers for copper and arsenic. The attenuation of copper can be estimated to be very efficient mainly due to its pH-controlled low solubility. Besides the specific adsorption to iron oxides, however, arsenic exhibits a rather large, loosely bound and easily exchangeable fraction. The speciation of arsenic in groundwater is dominated by As(V). The oxidation state of the original pigment is As(III). In some parts of the aquifer where suboxic conditions prevail, this oxidation state is conserved. In oxic zones of the aquifer, oxidation to the pentavalent form As(V) takes place.     

Bedeutung und Verhalten von Arsen in der Hydrosphäre

The redox speciation of the inorganic arsenic species As(III) and As(V) has deep influence on the element's toxicity and mobility. In groundwater sorption and redox processes occur with respect to the solid phase and the soluble arsenic species. Thereby manganese oxides and iron hydroxides play an important role. Manganese(IV) oxides are known as effective oxidants of As(III), iron(III) hydroxides surface bind both species by surface complexation. The task of this article is to give a short overview concerning the global cycling and behavior of arsenic and then focus on the redox behavior in the aquatic system influenced by manganese oxides and iron hydroxides. Results of previous investigations are shown and expanded by new findings of own studies. Studies were carried out under controlled geochemical conditions using batch systems with arsenic and MnO ₂ and FeOOH, respectively. The sorption and redox processes were investigated using extraction methods combined with solid phase surface analyses by XANES. The results indicate a slow oxidation process of As(III) at the iron hydroxide surface.     

Binding of organic solutes to dissolved humic substances and its effects on adsorption and transport in the aquatic environment

Humic substances constitute a major fraction of dissolved organic matter in natural water and effluents. Their effect on the adsorption of organic contaminants to aquifer material was elucidated, and a model was proposed for the adsorption of organic solutes to aquifer solids in the presence of dissolved humic substances. The model is based on the assumption that organic solute binds to dissolved humic substances in a reversible manner to form a solute-humate complex. Following binding, both free and bound fractions of the organic solute are independently adsorbed onto the solid phase. In order to evaluate the validity of the model, the following parameters were determined: (1) the adsorption coefficient of the organic solute to clay; (2) the binding constant of the solute-humate complex; and (3) the adsorption of humic acid (HA) to clay, assuming that the solute-humate complex is adsorbed similarly to humic acid itself. Using these parameters in the model enabled the effect of dissolved humic substances on adsorption to be evaluated. Experimental results obtained for the adsorption of fluoranthene (a model compound of the PAH group) to clay in the presence of dissolved HA were compared with calculated values derived from the model described above. The sensitivity of the model to various parameters was evaluated and a prediction was made with respect to the effect of dissolved humic substances on the adsorption of a variety of organic solutes. It appears that dissolved humic substances solubilize organic solutes which have higher adsorption coefficients to clay than humic substances, but increase the adsorption of solutes having lower adsorption coefficients relative to humic substances.     

Environmental chemistry of chromium

The processes that control the environmental chemistry of chromium include redox transformation, precipitation/dissolution, and adsorption/desorption reactions. Commonly occurring reductants, such as ferrous iron and organic material, can transform Cr(VI) to Cr(III), but manganese oxides are the only inorganic oxidants found in the environment that cause the rapid oxidation of Cr(III) to Cr(VI). In the trivalent state, chromium readily forms compounds such as Cr(OH)3 and (Cr,Fe)(OH)3. These solids show amphoteric solubility behavior, with hydroxo complexes being the dominant aqueous species of Cr(III). The relatively low solubilities of Cr(OH)3 and (Cr,Fe)(OH)3 limit Cr(III) concentrations to less than the drinking water limit over much of the pH range of environmental interest. In the hexavalent state, the formation of the Ba(S,Cr)O4 solid solution controls the dissolved chromium concentrations in environments that contain BaSO4. In the absence of solubility-controlling Cr(VI) solids, Cr(VI) concentrations in acidic to slightly alkaline conditions are expected to be limited by adsorption. Iron oxides are the most important absorbents for aqueous Cr(VI) species in most soil environments. Although these processes are complex and interrelated, each must be considered to predict the aqueous concentrations, mobility, and toxicity of chromium in the environment.     

Composition and particle size of superparamagnetic corrosion products in tap water

Chemical analyses, magnetization, Mössbauer spectrum, and x-ray diffraction measurements were made on solids removed from tap water by means of membrane filters. The taps from which this water was obtained had previously been unused for prolonged periods of time. When these taps were reactivated and water was first drawn, it was observed that the quantity of coarse solids in the water gradually decreased with flow, while at the same time the quantity of fine solids gradually increased. The magnetization, Mössbauer spectra, and x-ray diffraction patterns of the solids showed the presence of a significant number of superparamagnetic particles of magnetite. In the temperature range of our measurements (77 K < T < 300 K), paramagnetic iron-based species, particularly lepidocrocite, were also present in the solids. Contaminants such as Pb, Cu, and As were observed to be present in significant amounts, and it is shown that these are adsorbed to the magnetic nanoparticles. It was observed that almost all of the solid particles could be removed by means of 5-μm filters. This removal process can be explained by means of a model which assumes that initial deposition of coarse aggregates of corrosion products on the filters forms a coating, rich in extremely fine iron oxides. The coating has a high capacity for sorption of very small individual particles.     

Adsorption of arsenic by hybrid anion–exchanger based on titanium oxyhydrate

The article has investigated the removal of anion–exchange forms of As(V) by organic anion–exchangers Dowex Marathon 11, Dowex SBR-P and organoinorganic anion–exchangers containing titanium oxyhydrate, from 0.2–2.0 mM solutions of NaH₂AsO₄ in the range of equilibrium values pH 3–10. It has been found that introduction of an inorganic component in the amount of 7 fractions of total mass, % results in non-additive (up to 50 fractions of total mass, %) increase of absorption of ions of As(V) in adsorption from weakly alkaline solutions. It was assumed that nonadditive change of the value of absorption may be caused by the influence of the negative charge of the surface of oxide component of organic anion–exchangers. It is shown that in acid media and also at an increase of the amount of the introduced titanium oxyhydrate the values of adsorption and distribution coefficient of As(V) ions approaches additive ones.     

Groundwater derived arsenic in high carbonate wetland soils: sources, sinks, and mobility

Wetlands and organic soils have been recognized as important sinks for arsenic in the environment, yet sources and immobilization mechanisms of As are often unclear. To begin rectifying this deficiency, we investigated As retention and binding mechanisms at a degraded, minerotrophic wetland site in contact with groundwater rich in As and Fe. Arsenic occurred in high dissolved concentrations of up to 467 microg L(-1) in the groundwater, but dropped to values below 10 microg L(-1) towards the surface. The solid phase As content instead was high in the topsoil with up to 3400 mg kg(-1) and decreased with depth to 15 mg kg(-1). A similar pattern was observed with respect to Fe. Amorphous and crystalline iron precipitates were the main sorbents for arsenic in the soil horizons according to results from wet chemical sequential extractions. Arsenic was apparently not associated with inorganic carbon phases, but a substantial portion of up to 31% of As(tot) could be mobilized by dispersion of soil organic matter. Ratios of dissolved As(III)/As(V) decreased from the deeper As(III) dominated groundwater to the As(V) dominated soil porewaters, where As was apparently immobilized in its oxidized form. Concentrations of the organic species DMA and MMA were negligible. According to the results of simple one-dimensional estimates the vertical arsenic transport from the source in the groundwater to the topsoil was slow given an extrapolation of current conditions. These results suggest that As accumulation started before the beginning of drainage in the now degraded peatland soils and the degradation and mass loss of organic matter under oxic conditions caused the very high As concentrations found in the topsoil horizon today.     

Arsenic removal using steel manufacturing byproducts as permeable reactive materials in mine tailing containment systems

Steel manufacturing byproducts were tested as a means of treating mine tailing leachate with a high As concentration. Byproduct materials can be placed in situ as permeable reactive barriers to control the subsurface release of leachate from tailing containment systems. The tested materials had various compositions of elemental Fe, Fe oxides, Ca-Fe oxides and Ca hydroxides typical of different steel manufacturing processes. Among these materials, evaporation cooler dust (ECD), oxygen gas sludge (OGS), basic oxygen furnace slag (BOFS) and to a lesser degree, electrostatic precipitator dust (EPD) effectively removed both As(V) and As(III) during batch experiments. ECD, OGS and BOFS reduced As concentrations to <0.5mg/l from 25mg/l As(V) or As(III) solution in 72 h, exhibiting higher removal capacities than zero-valent iron. High Ca concentrations and alkaline conditions (pH ca. 12) provided by the dissolution of Ca hydroxides may promote the formation of stable, sparingly soluble Ca-As compounds. When initial pH conditions were adjusted to 4, As reduction was enhanced, probably by adsorption onto iron oxides. The elution rate of retained As from OGS and ECD decreased with treatment time, and increasing the residence time in a permeable barrier strategy would be beneficial for the immobilization of As. When applied to real tailing leachate, ECD was found to be the most efficient barrier material to increase pH and to remove As and dissolved metals.     

Incorporation of inorganic material in anoxic/aerobic-activated sludge system mixed liquor

In the bioreactor of the nitrification denitrification (ND)-activated sludge system, the mixed liquor is made up of organic and inorganic materials. In the current design procedures and simulation models, the influent wastewater characteristics and biological processes that influence the bioreactor mixed liquor organic solids (as volatile suspended solids, VSS, or COD) are explicitly included. However, the mixed liquor total suspended solids (TSS, i.e. organic+inorganic solids) are calculated simply from empirical ratios of VSS/TSS. The TSS concentration is fundamental in the design of secondary settling tanks and waste activated sludge disposal. Clearly, the empirical approach to obtaining an estimate for TSS is not satisfactory within the framework of a fundamentally based model. Accordingly, the incorporation of the inorganic material present in the influent wastewater into ND-activated sludge system mixed liquor was investigated. From an experimental investigation into the distribution of inorganics in the influent, mixed liquor and effluent of a laboratory-scale ND-activated sludge system, it was concluded inter alia that (i) of the total inorganic solids in the influent, only a small fraction (2.8–7.5%) is incorporated into the mixed liquor, (ii) most of the inorganics in the influent (mean 88%) and effluent (mean 98.5%) are in the dissolved form, the balance being particulate, and (iii) the influent and effluent inorganic dissolved solids concentrations are closely equal (mean effluent to influent ratio 100%). Further, a number of models were developed to quantify the mixed liquor inorganic, and, hence, total solids. From an evaluation of these models against the experimental data, it would appear that the best approach to model the incorporation of inorganics into the activated sludge mixed liquor is to follow the concepts and principles used to develop the existing models for organic materials. With this approach, reasonably close correlation between predicted and measured data for mixed liquor and effluent inorganic concentrations were obtained.     

Changes in arsenic speciation through a contaminated soil profile: a XAS based study

An impacted soil located near an industrial waste site in the Massif Central near Auzon, France, where arsenical pesticides were manufactured, has been studied in order to determine the speciation (chemical forms) of arsenic as a function of soil depth. Bulk As concentrations range from 8780 mg kg(-1) in the topsoil horizon to 150 mg kg(-1) at 60 cm depth. As ores (orpiment As2S3, realgar AsS, arsenopyrite FeAsS) and former Pb- and Al-arsenate pesticides have been identified by XRD at the site and are suspected to be the sources of As contamination for this soil. As speciation was found to vary with depth, based on XRD, SEM-EDS, EPMA measurements and selective chemical extractions. Based on oxalate extraction, As is mainly associated with amorphous Fe oxides through the soil profile, except in the topsoil horizons where As is hosted by another phase. SEM-EDS and EPMA analyses led to the identification of arseniosiderite (Ca2Fe3+3(AsVO4)3O2.3H2O), a secondary mineral that forms upon oxidation of primary As-bearing minerals like arsenopyrite, in these topsoil horizons. These mineralogical and chemical results were confirmed by synchrotron-based X-ray absorption spectroscopy. XANES spectra of soil samples indicate that As occurs exclusively as As(V), and EXAFS results yield direct evidence of changes in As speciation with depth. Linear combination fits of EXAFS spectra of soil samples with those of various model compounds indicate that As occurs mainly As-bearing Fe(III)-(hydr)oxides (65%) and arseniosiderite (35%) in the topsoil horizon (0-5 cm depth). Similar analyses also revealed that there is very little arseniosiderite below 15 cm depth and that As(V) is associated primarily with amorphous Fe oxides below this depth. This vertical change of As speciation likely reflects a series of chemical reactions downward in the soil profile. Arseniosiderite, formed most likely by oxidation of arsenopyrite, is progressively dissolved and replaced by less soluble As-bearing poorly ordered Fe oxides, which are the main hosts for As in well aerated soils.     

Synergistic effect of coupling zero-valent iron with iron oxide-coated sand in columns for chromate and arsenate removal from groundwater: Influences of humic acid and the reactive media configuration

A column study was conducted using a combination of zero-valent iron (Fe⁰) and iron oxide-coated sand (IOCS) for removing Cr(VI) and As(V) from groundwater. The removal efficiency and mechanism of Cr(VI) and As(V), the effects of humic acid (HA), and the various configurations of Fe⁰ and IOCS were investigated. The results showed that the use of an Fe⁰ and IOCS mixture in a completely mixed configuration can achieve the highest removal of both Cr(VI) and As(V), whilst the effects of HA were marginal in using these reactive materials. The solid phase analysis revealed the occurrence of the synergistic effect in these reactive materials as Fe²⁺ can be adsorbed onto the IOCS and transform the iron oxides to magnetite, providing more reactive surface area for Cr(VI) reduction and reducing the passivation on the Fe⁰. As(V) can then be removed by adsorption onto these iron corrosion products. HA can be adsorbed onto the IOCS so that the impacts of the deposition of HA aggregates on the Fe⁰ surface can be reduced, thus enhancing the Fe⁰ corrosion.     

Displacement of five metals sorbed on kaolinite during treatment with modified Fenton's reagent

The displacement of sorbed metals during the treatment of soils and groundwater with modified Fenton's reagent was investigated using five common metal contaminants (cadmium, copper, lead, nickel, and zinc) and kaolinite as a model sorbent. Modified Fenton's conditions included three H(2)O(2) concentrations (0.9, 1.8, 2.7 M) and two catalysts: soluble iron (III) at pH 3 and iron (III)-NTA chelate at pH 6. Iron (III)-catalyzed Fenton's reactions released significant amounts of zinc, cadmium, and copper. Modified Fenton's reactions catalyzed by iron (III)-NTA released zinc, cadmium, copper, and lead, and resulted in greater amounts of metals release than the iron (III)-catalyzed reactions. Metals release may have been mediated by transient oxygen species, such as superoxide, generated by propagation reactions, which become dominant at the relatively high hydrogen peroxide concentrations used. Metals release from kaolinite was undetectable when sufficiently low hydrogen peroxide concentrations were maintained to minimize propagation reactions. These results indicate that using dilute concentrations of hydrogen peroxide for Fenton's ISCO may minimize potential metals mobility when treating contaminated soils and groundwater containing a mixture of organic and metal contaminants.