Atrazine, isoproturon, mecoprop, 2,4-D, and bentazone adsorption onto iron oxides

Iron oxides are important components influencing the adsorption of various inorganic and organic compounds in soils and sediments. In this study the adsorption on iron oxides of nonionic and ionic pesticides was determined as a function of solution pH, ionic strength, and pesticide concentration. The investigated iron oxides included two-line ferrihydrite, goethite, and lepidocrocite. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide]. The adsorption of the nonionic pesticides (atrazine and isoproturon) was insignificant, whereas the adsorption of the acidic pesticides (mecoprop, 2,4-D, and bentazone) was significant on all investigated iron oxides. The adsorption capacity increased with decreasing pH, with maximum adsorption reached close to the pKa values. The addition of CaCl2 in concentrations from 0.0025 to 0.01 M caused the adsorption capacity to diminish. The adsorption of bentazone was significantly lower than the adsorption of mecoprop and 2,4-D, illustrating the importance of a carboxyl group in the pesticide structure. The adsorption capacity on the iron oxides increased in the order: lepidocrocite < goethite < two-line ferrihydrite. The maximum adsorption capacities of meco-prop and 2,4-D on goethite were found to be equivalent to the site density of singly coordinated hydroxyl groups on the faces of the dominant (110) form, suggesting that singly coordinated hydroxyl groups are responsible for adsorption. Differences in adsorption capacities between iron oxides can be explained by differences in the surface site density of singly coordinated hydroxyl groups. The maximum measured adsorption capacity of mecoprop on two-line ferrihydrite was equivalent to 0.2 mol/mol Fe.     

micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.     

Mobilization of trace metals and inorganic compounds during resuspension of anoxic sediments from Trepangier Bayou, Louisiana

The release of trace metals (Mn, Ni, Co, Cu, Zn, Pb, and Cd) and inorganic compounds (As) from initially anoxic Trepangier Bayou sediments, Louisiana and the sources of the released metals were investigated. After 1 to 2 d aeration, significant amounts of trace metals (Mn, Zn, Cd, Ni, and Co) were released to the aqueous phase with increased acidity, primarily due to the oxidation of acid-volatile sulfide and ferrous iron and iron sulfide minerals. The addition of a bacterial inhibitor, NaN,, to the Trepangier sediment during resuspension inhibited metal release, suggesting that microbial catalysis can regulate metal mobilization during sediment resuspension. In a well buffered system, oxidation of iron sulfides alone did not appear to induce trace metal release. Moreover, when Trepangier sediment was resuspended in anoxic conditions at neutral pH, <1% of the trace metal content was released, whereas a significant release of metal was observed under acidic anoxic conditions. Although oxidation of iron sulfide minerals is an essential prerequisite for the release of Zn, Co, Cd, and Ni, carbonates and oxides also play a role. The trace metals and inorganic compounds investigated could be classified into three groups according to their release characteristics: (i) Mn, Zn, Cd, Ni, and Co; (ii) Fe, Pb, and As; and (iii) Cu. The groupings appeared to depend on the sources of compounds and their relative affinity, after oxidation, to iron oxyhydroxides or organic matter.     

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

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

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.     

Fly ash and lime-stabilized biosolid mixtures in mine spoil reclamation: simulated weathering

The use of large quantities of neutral coal fly ash (NFA) may be facilitated by co-application with a lime-stabilized biosolid (LSB) for the reclamation of acid mine spoil (AMS). Although NFA may not aid in the mitigation of acid drainage, questions concerning the leachability and mineralogy of native and NFA- and LSB-born metals must be addressed. In this study, the potential long-term influence of LSB and NFA on AMS leachate chemistry and trace element mineralogy was evaluated using laboratory weathering and selective dissolution techniques. The application of LSB at a rate sufficient to neutralize the potential acidity of the AMS increased leachate pH from approximately 3 to 7.5 for the duration of the study. Fly ash rates (1X, 1.5X, and 2X LSB rate) did not affect leachate pH. The dominant electrolytes in all leachates were Ca and SO4, the concentrations of which were mirrored by solution electrical conductivity (EC). Leachate concentrations of Al, Fe, Mn, K, Cu, Ni, and Zn were significantly reduced by LSB application, whereas concentrations of Ca, SO4, Mg, Cl, F, B, and P were increased. Nitrate concentrations were not affected by LSB. With the exception of leachate B, which increased with increasing NFA rate and was regenerated during the weathering study, NFA did not affect leachate composition. Sequential selective dissolution indicated a transformation of Co, Cr, Cu, Ni, Pb, and Zn into less labile mineral pools with weathering. The results of these evaluations suggest that the application of NFA during AMS reclamation would have little effect on leachate chemistry or the mineralogy of trace elements. Thus, the high-volume application of NFA to AMS during reclamation may offer an additional opportunity for the use of this combustion by-product.     

USE OF X-RAY FLUORESCENCE TO DETERMINE TRACE METALS IN WATER RESOURCES1

ABSTRACT. The X-ray fluorescence method was used to analyze trace metals collected in particulate form on filter papers and from the ionic state by ion exchange filter papers. The samples were prepared by allowing water to pass through these filter papers. The procedures necessary for using the X-ray fluorescence method are described. A number of samples were taken from the Great Miami River in Dayton, Ohio over one year showing the presence of the following metals, Ca, Ti, Cr, Fe, Cu, Zn, Sr, and Cd. Elements in the periodic table between Ti and Cs were detectable to a sensitivity limit of the order of 30 ppb for metals in the particulate form and 0.4 ppm for metals in the ionic form.     

Cadmium solubility and sorption in a long-term sludge-amended arable soil

Cadmium solubility and sorption in an arable clay loam soil that had received sewage sludge for 41 years were compared to an unsludged control in batch studies. Soil pH dominated Cd sorption, explaining >92% of the variation in Kd values in both treatments. At any pH, Cd sorption was apparently slightly but significantly (p < 0.05) smaller in the sludge-amended soil compared to the control, even though the organic carbon content was 70% larger and the ammonium oxalate-extractable iron content was roughly doubled. Correction for dissolved organic carbon (DOC) complexation with the speciation model WHAM reduced the difference in sorption between treatments, but the sludged soil still had significantly smaller Kd values (p < 0.01). Batch equilibrations without addition of Cd showed that there was no significant difference in the solubility of "native" cadmium (defined as EDTA-extractable Cd) in sludged and control soils. The reason for the lack of increase in Cd sorption in the sludge-amended soil has not been established, but it may be due to competition for sorption sites on humic compounds with sludge-derived Fe and trace metals such as zinc. The fact that the pyrophosphate-extractable (i.e., organically associated) iron content was seven times larger in the sludged soil provides some supporting evidence for this hypothesis.     

Solubilization of manganese and trace metals in soils affected by acid mine runoff

Manganese solubility has become a primary concern in the soils and water supplies in the Alamosa River basin, Colorado due to both crop toxicity problems and concentrations that exceed water quality standards. Some of the land in this region has received inputs of acid and trace metals as a result of irrigation with water affected by acid mine drainage and naturally occurring acid mineral seeps. The release of Mn, Zn, Ni, and Cu following saturation with water was studied in four soils from the Alamosa River basin. Redox potentials decreased to values adequate for dissolution of Mn oxides within 24 h following saturation. Soluble Mn concentrations were increased to levels exceeding water quality standards within 84 h. Soluble concentrations of Zn and Ni correlated positively with Mn following reduction for all four soils studied. The correlation between Cu and Mn was significant for only one of the soils studied. The soluble concentrations of Zn and Ni were greater than predicted based on the content of each of these metals in the Mn oxide fraction only. Increases in total electrolyte concentration during reduction indicate that this may be the result of displacement of exchangeable metals by Mn following reductive dissolution of Mn oxides.     

Effect of cobalt sorption on metal fractionation in anaerobic granular sludge

A sequential extraction procedure was applied to two anaerobic methanogenic sludges (Eerbeek and Nedalco) to examine the speciation of micro- and macronutrients in the sludges after cobalt sorption by exposing the sludge to a 1 mM Co solution for 4 d at pH 7 and 30 degrees C. The effect of different physicochemical conditions on cobalt sorption was studied as well: effect of pH (6-8), effect of competition by a second trace element (Ni or Fe), modification of the granular matrix by glutaraldehyde or heat treatment, and EDTA (ethylenediaminetetraacetic acid) addition. Sorbed Co was found to distribute between the carbonates, organic matter + sulfides, and residual fractions. Cobalt adsorption resulted in an antagonistic interaction with other metals present in the granular matrix, evidenced by the solubilization of other trace elements (e.g., Ni, Cu, and Zn) as well as macronutrients (especially Ca and Fe). Modification of the sludge matrix by glutaraldehyde or heat treatment, or exposure to EDTA, led to serious modifications of the Co sorption capacity and strong interactions with multivalent cations (i.e., Ca(2+) and Fe(2+)).     

Distribution and speciation of metals in annual rings of black willow

Information on the spatial distribution and speciation of metals in nonhyperaccumulator plants is lacking. This study used synchrotron X-ray fluorescence (SXRF) compositional imaging to investigate the spatial distribution of Ni, Mn, Cu, Zn, and Fe in annual rings of black willow (Salix nigra L.) collected from a metal-contaminated area, and used X-ray absorption spectroscopy (XAS) to investigate Ni and Mn speciation in regions of the annual rings with elevated Ni concentrations. Annual rings were recollected in early 2003 from an individual known to be enriched with Ni from previous studies. Compositional imaging showed Ni and associated co-contaminants conservatively located in an annual ring. When compared with a corresponding photomicrograph, SXRF compositional images showed that metals were sharply constrained by the boundaries of the annual ring, indicating a sudden onset and cessation of uptake, and a lack of post-growth mobility of the metals. There was a particularly strong correlation between Ni and Mn in the metal-enriched annual ring (r = 0.8822), which suggested similar transport and binding behavior of these elements. X-ray absorption spectroscopy showed Ni and Mn to be present in the 2+ oxidation state. X-ray absorption near edge structure spectroscopy (XANES) fingerprinting of localized, highly Ni-enriched regions within the lumen of willow xylem vessels found similarities with Ni-pectic acid complexes, Ni-histidine, and NiSO4.     

Iron and Zinc status in soils, water and staple food cultivars in Itakpe, Kogi State of Nigeria

The levels of iron (Fe) and zinc (Zn) were quantitatively determined in soil and water samples as well as in staple food cultivars in Itakpe, Nigeria's major iron mining town. The survey was conducted to establish a baseline pollution index for Fe and Zn in the Itakpe environment and to evaluate the role of foods as an exogenous source of these metals among the inhabitants. Exceedingly high levels of both metals characterized the staple food cultivars in the town.     

Cobalt distribution and speciation: effect of aging, intermittent submergence, in situ rice roots

The speciation and distribution of Co in soils is poorly understood. This study was conducted using x-ray absorption spectroscopy (XAS) techniques to examine the influence of soluble cobalt in the +2 oxidation state (Co[II]) aging, submergence-dried cycling, and the presence of in vivo rice roots on the speciation and distribution of added Co(II) in soils. In the aging and submerged-dried cycling studies, Co was found to be associated with Mn oxide fraction (23 to 100% of total Co) and Fe oxide fractions (0 to 77% of total Co) of the soils as either Co(II) species or a mixed Co(II), and Co in the +3 oxidation state (Co[III]) species. The surface speciation of Co in the Mn oxide fraction suggests an innersphere complex was present and the speciation of Co in the Fe oxide fraction was an innersphere surface complex. The in vivo root box experiments showed similar Co speciation in the Mn oxide fraction (13 to 76% of total Co) as the aging and submerged-dried cycling studies. However, the Fe oxide fraction of the soil was unimportant in Co retention. A significant amount (24 to 87% of total Co) of the Co in root box treatments was identified as a Co precipitate. The importance of this finding is that in the presence of rice roots, the Co is redistributed to a Co precipitate. This work confirmed earlier macroscopic work that Mn oxides are important in the sequestration of Co in soils and the influence of roots needs to be taken into account when addressing Co speciation. The information gained from this study will be used to improve models to predict the lability and hence the availability of Co in terrestrial environments.     

Iron and aluminium based adsorption strategies for removing arsenic from water

Arsenic is a commonly occurring toxic metal in natural systems and is the root cause of many diseases and disorders. Occurrence of arsenic contaminated water is reported from several countries all over the world. A great deal of research over recent decades has been motivated by the requirement to lower the concentration of arsenic in drinking water and the need to develop low cost techniques which can be widely applied for arsenic removal from contaminated water. This review briefly presents iron and aluminium based adsorbents for arsenic removal. Studies carried out on oxidation of arsenic(III) to arsenic(V) employing various oxidising agents to facilitate arsenic removal are briefly mentioned. Effects of competing ions, As:Fe ratios, arsenic(V) vs. arsenic(III) removal using ferrihydrite as the adsorbent have been discussed. Recent efforts made for investigating arsenic adsorption on iron hydroxides/oxyhydroxides/oxides such as granular ferric hydroxide, goethite, akaganeite, magnetite and haematite have been reviewed. The adsorption behaviours of activated alumina, gibbsite, bauxite, activated bauxite, layered double hydroxides are discussed. Point-of-use adsorptive remediation methods indicate that Sono Arsenic filter and Kanchan™ Arsenic filter are in operation at various locations of Bangladesh and Nepal. The relative merits and demerits of such filters have been discussed. Evaluation of kits used for at-site arsenic estimation by various researchers also forms a part of this review.     

Iron and arsenic release from aquifer solids in response to biostimulation

Biostimulation has been used at various contaminated sites to promote the reductive dechlorination of trichloroethylene (TCE), but the addition of carbon and energy donor also stimulates bacteria that use Fe(III) as the terminal electron acceptor (TEA) in potential competition with dechlorination processes. Microcosm studies were conducted to determine the influence of various carbon donors on the extent of reductive dissolution of aquifer solids containing Fe(III) and arsenic. Glucose, a fermentable and respirable carbon donor, led to the production of 1500 mg Fe(II) kg(-1), or 24% of the total Fe in the aquifer sediment being reduced to Fe(II), whereas the same concentration of carbon as acetate resulted in only 300 mg Fe(II) kg(-1) being produced. The biogenic Fe(II) produced with acetate was exclusively associated with the solid phase whereas with fermentable carbon donors as whey and glucose, 22 and 54% of the Fe(II) was in solution. With fermentation, some of the metabolites appear to be electron shuttling chemicals and chelating agents that facilitate the reductive dissolution of even crystalline Fe(III) oxides. Without the presence of electron shuttling chemicals, only surficial Fe in direct contact with the bacteria was bioavailable, as illustrated when acetate was used. Regardless of carbon donor type and concentration, As concentrations in the water exceeded drinking water standards. The As dissolution appears to have been the result of the direct use of As as an electron acceptor by dissimilatory arsenic reducing bacteria. Our findings indicate that selection of the carbon and energy donor for biostimulation for remediation of chlorinated solvent impacted aquifers may greatly influence the extent of the reductive dissolution of iron minerals in direct competition with dechlorination processes. Biostimulation may also result in a significant release of As to the solution phase, contributing to further contamination of the aquifer.     

Kinetics of chromate adsorption on goethite in the presence of sorbed silicic acid

The adsorption of chromate on mineral surfaces has received much attention due to its toxicity in natural systems. Spectroscopic studies have demonstrated that chromate forms inner-sphere complexes on variable-charge surfaces. However, in natural systems chromate has been observed to be fairly mobile, which has been explained by the presence of naturally occurring ligands competing with chromate for mineral surface sites. Silicic acid is a ubiquitous ligand in soil and water environments and also sorbs strongly to variable-charge surfaces. Yet little research has examined its influence on chromate adsorption to variable-charge surfaces such as goethite. This study examined the influence of silicic acid (0.10 and 1.0 mM) on the adsorption kinetics of chromate (0.05 and 0.10 mM) on goethite over a range of common soil pH values (4, 6, and 8). The rate and total quantity of chromate adsorption decreased in all the experiments except at a pH value of 4 and a chromate concentration of 0.05 mM. The inhibition of chromate adsorption ranged from 3.1% (pH = 4, Si = 0.10 mM, chromate = 0.10 mM) to 83.3% (pH = 8, Si = 1.0 mM, chromate = 0.05 mM). The rate of chromate adsorption decreased with an increase in pH and silicic acid concentration. This was attributed to a reduction in the surface potential of goethite on silicic acid adsorption as well as a competition for surface sites. The presence of naturally occurring ligands such as silicic acid may be responsible for the enhanced mobility of chromate in natural systems and demonstrates the importance of competitive adsorption for evaluating the mobility of trace elements.     

土壤环境汞形态及吸附解吸研究进展

汞污染一直是全球备受关注的问题,由于土壤是环境汞的源和汇,因此已经开展了大量相关的研究工作。本论文系统总结了土壤环境汞形态及吸附解吸特征的研究现状,综述了不同类型土壤汞的背景含量,以及汞在土壤中的赋存形态,分析了土壤汞吸附特征及几种典型的土壤吸附剂（粘土矿物、铁锰氧化物、硫化物和土壤有机质）对汞吸附的作用机制。     

Distribution of heavy metals in sediments of Igbede, Ojo and Ojora rivers of Lagos, Nigeria

The distribution of some heavy metals, namely Cd, Pb, Zn, Fe, Cu, Cr and Mn in epipellic sediments of Igbede, Ojo and Ojora rivers of Lagos was studied weekly in the early summer (November) of 2003. The levels of selected trace metals were determined using Atomic Absorption Spectrophotometer (UNICAM 969 AAS SOLAR). Trends in heavy metal burdens in the sediments revealed weekly variations in all the rivers assessed. Statistical analyses also showed different mean levels of trace metals in the aquatic environments, the distribution of which followed the sequence Fe > Zn > Mn > Pb > Cu > Cr > Cd, Fe > Zn > Cu > Mn > Pb > Cr > Cd and Fe > Zn > Mn > Cu > Cr > Pb > Cd in Igbede, Ojo and Ojora rivers respectively. Fe recorded the highest concentration levels (1,582.95 ± 96.57 μ g/g–1,910.34 ± 723.19 μ g/g) in all the sediments investigated while the Cd levels (0.06 ± 0.10 μ g/g–0.47 ± 0.36 μ g/g) were the lowest. Expectedly, trace metal concentrations in fine grain muddy sediments of the Igbede and Ojo coastline were much higher than those of Ojora which consist of coarse and sandy deposits covering the near shore area. Generally, the results obtained fell within tolerable limits stipulated by World Health Organization (WHO).     

Evidence for struvite in poultry litter: effect of storage and drying

The use of spectroscopic techniques (especially phosphorus-31 nuclear magnetic resonance [(31)P-NMR] and X-ray absorption near edge structure spectroscopy) has recently advanced the analysis of the speciation of P in poultry litter (PL) and greatly enhanced our understanding of changes in P pools in PL that receive alum (aluminum sulfate) to reduce water-soluble P and control ammonia emissions from poultry houses. Questions remain concerning changes of P species during long-term storage, drying, or after application of PL to cropland or for other uses, such as turfgrass. In this study, we investigated a set of six PL samples (of which three were alum-amended and three were unamended) that had been characterized previously. The P speciation was analyzed using solid-state (31)P-NMR spectroscopy, and the mineralogy was analyzed by powder X-ray diffraction (XRD) after storing the samples moist and dried for up to 5 yr under controlled conditions. The magnesium ammonium phosphate mineral struvite was identified in all but one PL samples. Struvite concentrations were generally lower in dried samples (< or = 14%) than in samples stored moist (23 and 26%). The moist samples also had higher concentrations of phosphate bound to aluminum hydroxides. Solid-state NMR spectroscopy was in general more sensitive than XRD in detecting and quantifying P species. Although phosphate associated with calcium and aluminum made up a large proportion of P species, they were not detected by XRD.     

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

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