Migration of trace elements from pyrite tailings in carbonate soils

In the carbonate soils contaminated by a toxic spill from a pyrite mine (Aznalcóllar, southern Spain), a study was made of a thin layer (thickness = 4 mm) of polluted soil located between the pyrite tailings and the underlying soil. This layer, reddish-yellow in color due to a high Fe content, formed when sulfates (from the oxidation of sulfides) infiltrated the soil, causing acidification (to pH 5.6 as opposed to 8.0 of unaffected soil) and pollution (in Zn, Cu, As, Pb, Co, Cd, Sb, Bi, Tl, and In). The less mobile elements (As, Bi, In, Pb, Sb, and Tl) concentrated in the uppermost part of the reddish-yellow layer, with concentration decreasing downward. The more mobile elements (Co, Cd, Zn, and Cu) tended to precipitate where the pH was basic, toward the bottom of the layer or in the upper part of the underlying soil. The greatest accumulations occurred within the first 6 mm in overall soil depth, and were negligible below 15 mm. In addition, the acidity of the solution from the tailings degraded the minerals of the clay fraction of the soils, both the phyllosilicates as well as the carbonates. Also, within the reddish-yellow layer, gypsum formed autigenically, together with complex salts of sulfates of Fe, Al, Zn, Ca, and Mn, jarosite, and oxihydroxides of Fe.     

Removal and distribution of iron, manganese, cobalt, and nickel within a Pennsylvania constructed wetland treating coal combustion by-product leachate

A flow-through wetland treatment system was constructed to treat coal combustion by-product leachate from an electrical power station at Springdale, Pennsylvania. In a nine-compartment treatment system, four cattail (Typha latifolia L.) wetland cells (designated Cells 1 through 4) successfully removed iron (Fe) and manganese (Mn) from the inlet water; Fe and Mn concentrations were decreased by an average of 91% in the first year (May 1996-May 1997), and by 94 and 98% in the second year (July 1997-June 1998), respectively. Cobalt (Co) and nickel (Ni) were decreased by an average of 39 and 47% in the first year, and 98 and 63% in the second year, respectively. Most of the metal removed by the wetland cells was accumulated in sediments, which constituted the largest sink. Except for Fe, metal concentrations in the sediments tended to be greater in the top 5 cm of sediment than in the 5- to 10- or 10- to 15-cm layers, and in Cell 1 than in Cells 2, 3, and 4. Plants constituted a much smaller sink for metals; only 0.91, 4.18, 0.19, and 0.38% of the Fe, Mn, Co, and Ni were accumulated annually in the aboveground tissues of cattail, respectively. A greater proportion of each metal (except Mn) was accumulated in cattail fallen litter and submerged Chara (a macroalga) tissues, that is, 2.81, 2.75, and 1.05% for Fe, Co, and Ni, respectively. Considerably higher concentrations of metals were associated with cattail roots than shoots, although Mn was a notable exception.     

Characterization of iron- and manganese-cemented redoximorphic aggregates in wetland soils contaminated with mine wastes

In wetlands, translocation of Fe and Mn from reducing to oxidizing zones creates localized enrichments and depletions of oxide minerals. In zones of enrichment, oxides cement matrix particles together into aggregates. In this paper, we describe the various Fe- and Mn-cemented features present in the 1 to 2-mm size fraction of mine-waste contaminated wetland soils of the Coeur d'Alene (CDA) River Basin in northern Idaho. These aggregates are categorized based on color and morphology. Total Fe and Mn concentrations are also reported. Distribution of the aggregates in soil profiles along an elevation transect with varying water table heights was investigated. Six distinct categories of aggregates were characterized in the 1 to 2-mm size fraction. The two most predominant categories were aggregates cemented by only Fe oxides and aggregates cemented by a mixture of Fe and Mn oxides. Iron-depleted aggregates, Fe and Mn-cemented sand aggregates, and root channel linings were also identified. The remaining aggregates were categorized into a catch-all category that consisted of primarily charcoal particles. The highest Fe content was in the root channel linings, and the highest Mn content was in the Fe/Mn cemented particles. Iron-cemented aggregates were most common in surface horizons at all sites, and root channels were most common in the 30 to 45-cm core at the lowland point, reflecting the presence of deep rooting vegetation at this site. Spatial distributions of other aggregates at the site were not significant.     

Transfer characteristics of cobalt from soil to crops in the suburban areas of Fujian Province,southeast China

The bioavailability of cobalt and its transfer from soil to vegetables and rice were investigated. Among 312 soils collected from vegetable and paddy fields in the suburban areas of some major cities of Fujian Province, southeast China, total soil Co ranged from 3.5 to 21.7 mg kg^?1, indicating a slight accumulation compared with the background value of the province. DTPA extracted 0.1–8.5% of soil total Co. Total and DTPA-extractable Co correlated with soil pH, CEC, free Fe, total Mn, clay and silt content more significantly in paddy soils than in the soils from vegetable fields. The average Co concentrations in the edible parts of vegetables and rice were 15.4 μg kg^?1 and 15.5 μg kg^?1, respectively. The transfer factor (the ratio of plant Co to soil DTPA-extractable Co, TF_DTPA) ranged from 0.003 to 0.126 with a median of 0.049. The TF_DTPA decreased in the order of leafy vegetables > fruit vegetables > root vegetables > rice. The TF_DTPA of all crops decreased with increasing DTPA-extractable Co. Increase in pH, CEC, organic matter, clay, silt, free iron and total Mn limited the soil-to-plant transfer of Co to varying degrees. The transfer of Co from the soils to the edible parts of the crops was lower than that of Zn, Cu and Cd, but higher than that of Pb in the same areas. The concentrations of Co in rice and vegetables in the study areas were considered to be safe for the local residents because of the slight anthropogenic input and the low transfer potential to the edible parts of Co from the soils.     

Reduction of arsenic uptake by lettuce with ferrous sulfate applied to contaminated soil

Soil contamination by arsenic (As) presents a hazard in many countries and there is a need for techniques to minimize As uptake by plants. A proposed in situ remediation method was tested by growing lettuce (Lactuca sativa L. cv. Kermit) in a greenhouse pot experiment on soil that contained 577 mg As kg(-1), taken from a former As smelter site. All combinations of iron (Fe) oxides, at concentrations of 0.00, 0.22, 0.54, and 1.09% (w/w), and lime, at concentrations of 0.00, 0.27, 0.68, and 1.36% (w/w), were tested in a factorial design. To create the treatments, field-moist soil, commercial-grade FeSO4, and ground agricultural lime were mixed and stored for one week, allowing Fe oxides to precipitate. Iron oxides gave highly significant (P < 0.001) reductions in lettuce As concentrations, down to 11% of the lettuce As concentration for untreated soil. For the Fe oxides and lime treatment combinations where soil pH was maintained nearly constant, the lettuce As concentration declined in an exponential relationship with increasing FeSO4 application rate and lettuce yield was almost unchanged. Iron oxides applied at a concentration of 1.09% did not give significantly lower lettuce As concentrations than the 0.54% treatment. Simultaneous addition of lime with FeSO4, was essential. Ferrous sulfate with insufficient lime lowered soil pH and caused mobilization of Al, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn. At the highest Fe oxide to lime ratios, Mn toxicity caused severe yield loss.     

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.     

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.     

Phosphorus speciation in manure-amended alkaline soils

Two common manure storage practices are stockpiles and lagoons. The manure from stockpiles is applied to soils in solid form, while lagoon manure is applied as a liquid. Soil amendment with manure in any form introduces a significant amount of phosphorus (P) that exists in both organic and inorganic forms. However, little is known about P speciation in manure stored under different conditions, or the subsequent forms when applied to soils. We used solution (31)P nuclear magnetic resonance (NMR) spectroscopy and conventional P fractionation and speciation methods to investigate P forms in dairy manure and liquid lagoon manure, and to study how long-term amendment with these manures influenced surface and subsurface soil P speciation. Our results show that the P forms in solid and lagoon manure are similar. About 30% of the total P was organic, mostly as orthophosphate monoesters. On a dry weight basis, total P was much higher in the solid manure. In the manure-amended soils the total P concentrations of the surface soils were similar, regardless of manure type. Total P in the subsurface soil was greater in the lagoon-manure-amended soil than the solid-manure-amended subsurface soil. However, the fraction of organic P was greater in the subsurface of the solid-manure-amended soil. The NMR results indicate that the majority of organic P in the soils is phytic acid, which is enriched in the surface soils compared with the subsurface soils. These results provide insight into P speciation and dynamics in manure-amended soils that will further increase our understanding on how best to manage manure disposal on soils.     

Broiler litter as a micronutrient source for cotton: concentrations in plant parts

Analytically, poultry litter contains nearly all essential micronutrients but the extent of phytoavailability of these nutrients and whether cotton (Gossypium hirsutum L.) and other crop plants can receive adequate amounts of these nutrients from litter is not fully known. The objective of this research was to determine whether cotton receives sufficient amounts of Fe, Cu, Mn, and Zn from litter and estimate the efficiency of cotton in extracting these metal nutrients from litter in the absence of any other source of the micronutrients. The greenhouse research used plastic pots filled with approximately 11 kg of a 2:1 (v/v) sand to vermiculite growing mix. Cotton (cv. Stoneville 474) was grown in the pots fertilized with broiler litter at rates of 30, 60, 90, or 120 g pot(-1) in a factorial combination with four supplemental nutrient solution (NS) treatments. The nutrient solutions consisted of full Hoagland's nutrient solution (NS-full); a solution of the macronutrients N, P, K, Ca, and Mg (NS-macro); a solution of the micronutrients Fe, Zn, Mn, Cu, B, and Mo (NS-micro); and water (NS-none). Based on tissue nutrient analysis, a one-time broiler litter application supplied adequate amounts of Fe, Cu, and Mn to bring the concentration of these nutrients in upper leaves within published sufficiency ranges. Zinc, with <17 mg kg(-1) concentration in the upper leaves, was the only micronutrient below the established sufficiency range regardless of the rate of applied litter. Cotton extracted Fe and Mn more efficiently than Cu or Zn, removing as much as 8.8% of Fe and 7.2% of Mn supplied by 30 g litter pot(-1). In contrast, the extraction efficiency was 1.7% for Cu and 1.9% for Zn. Roots accumulated 58% of the total absorbed Fe and 64% of Cu, and leaves accumulated 32% of the Fe and only 13% of the Cu supplied by litter. In contrast, only 16% of the total absorbed Mn and 23% of Zn accumulated in roots while leaves accumulated 64% of the total Mn and 37% of Zn. These results demonstrate that broiler litter is a valuable source of the metal nutrients supplying Fe, Cu, and Mn in full and Zn in part, but a very large fraction of the litter-supplied metal nutrients remained in the growing mix.     

Leachate characteristics,dry matter yield of Urochloa decumbens and properties of two contrasting soils irrigated with sludgewater in columns

Increasing demands on freshwater and challenges in disposal of wastewaters encourage their use for irrigation. The study evaluated the effects of irrigation of signal grass (Urochloa decumbens) with sludgewater on leaching, uptake and retention of a range of elements in two contrasting soils in columns. The grass was grown on a sandy loam and a clay soil packed in plastic columns and irrigated for 119 days with either undiluted, diluted sludgewater or tap water. The sludgewater had a pH of 6.9 and high aluminum (Al), manganese (Mn), iron (Fe), and boron (B). Analyses were conducted on leachates, above-ground plant biomass (two harvests), and soils at the end of the experiment. Sludgewater treatments increased grass biomass yield and uptake of nitrogen (N), phosphorus (P), potassium (K), and magnesium (Mg) in both soils with a greater nutrient uptake from the clay than the sandy loam. The application of sludgewater increased Mn and reduced P (sandy loam only) in the leachate with no effects on Al, Fe, or B. Uptake of Al, Fe, and B was increased by sludgewater application. Even when diluted, the sludgewater increased extractable Mn, particularly in the clay soil. The findings showed that irrigation of the soils with sludgewater increased Mn and B concentrations and uptake by signal grass, with no negative effects on biomass production. Leaching and accumulation in the soils of toxic elements were minimal in the short term. Sludgewater can therefore be used to grow signal grass in both soils although these effects need to be evaluated under field conditions.     

Total Contents and Sequential Extraction of Heavy Metals in Soils Irrigated with Wastewater,Akaki, Ethiopia

The Akaki River, laden with untreated wastes from domestic, industrial, and commercial sources, serves as a source of water for irrigating vegetable farms. The purpose of this study is to identify the impact of waste-water irrigation on the level of heavy metals and to predict their potential mobility and bioavailability. Zn and V had the highest, whereas Hg the lowest, concentrations observed in the soils. The average contents of As, Co, Cr, Cu, Ni, Zn, V, and Hg of both soils; and Pb and Se from Fluvisol surpassed the mean + 2 SD of the corresponding levels reported for their uncontaminated counterparts. Apparently, irrigation with waste water for the last few decades has contributed to the observed higher concentrations of the above elements in the study soils (Vertisol and Fluvisol) when compared to uncontaminated Vertisol and Fluvisol. On the other hand, Vertisol accommodated comparatively higher average levels of Cr, Cu, Ni, Zn, etc V, and Cd, whereas high contents of Pb and Se were observed in Fluvisol. Alternatively, comparable levels of Co and Hg were found in either soil. Except for Ni, Cr, and Cd in contaminated Vertisol, heavy metals in the soils were not significantly affected by the depth (0–20 and 30–50 cm). When the same element from the two soils was compared, the levels of Cr, Cu, Ni, Pb, Se, Zn, V, Cd at 0–20 cm; and Cr, Ni, Cu, Cd, and Zn at 30–50 cm were significantly different. Organic carbon (in both soils), CEC (Fluvisol), and clay (Vertisol) exhibited significant positive correspondences with the total heavy metal levels. Conversely, Se and Hg contents revealed perceptible associations with carbonate and pH. The exchangeable fraction was dominated by Hg and Cd, whereas the carbonate fraction was abounded with Cd, Pb, and Co. conversely, V and Pb displayed strong affinity to reducible fraction, where as Cr, Cu, Zn, and Ni dominated the oxidizable fraction. Cr, Hg, Se, and Zn (in both soils) showed preference to the residual fraction. Generally, a considerable proportion of the total levels of many of the heavy metals resided in non residual fractions. The enhanced lability is generally expected to follow the order: Cd > Co > Pb > Cu > Ni > Se > V and Pb > Cd > Co > Cu > Ni > Zn in Vertisol and Fluvisol, respectively. For the similar wastewater application, the soil variables influence the status and the distribution of the associated heavy metals among the different soil fractions in the study soils. Among heavy metals that presented relatively elevated levels and with potential mobility, Co, Cu, Ni (either soil), V (Vertisol), Pb, and Zn (Fluvisol) could pose health threat through their introduction into the food chain in the wastewater irrigated soils.     

Zinc fractionation in contaminated soils by sequential and single extractions: influence of soil properties and zinc content

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.     

Cupric ion activity in peat soil as a toxicity indicator for maize

Copper phytotoxicity in soils is difficult to assess because Cu accumulates at and damages roots, and is not readily transferred to shoots. Soil chemical properties strongly influence Cu speciation, so that total soil Cu alone is not a broadly useful indicator of potential toxicity to plants. The present study measured free Cu2+ activity in Cu-enriched peat soils using the ion selective electrode. The soil Cu2+ activity was related to the severity of phytotoxicity as measured by several indicators in a maize (Zea mays L.) bioassay, including leaf chlorosis, root stunting, and reduced shoot growth and Fe concentration. A soil Cu2+ activity of 10(-7.0) to 10(-7.5), corresponding to total Cu of about 275 mg/kg in the peat soil, caused phytotoxicity in maize seedlings. It is proposed that Cu2+ activity is more directly related to phytotoxic effects than other soil tests, such as extractions with strong acids or chelating agents, because it is the free Cu2+ in soil solution that has the most direct toxic effects on roots. There was very limited uptake of Cu into maize shoots, and even when Cu2+ activity and total soil Cu were raised into the extreme toxicity range of 10(-5) and 4,000 mg/ kg, respectively, shoot Cu remained less than 35 mg/kg. These results indicate the inadequacy of the USEPA risk assessment of potential for Cu toxicity to crops amended with sewage sludge, which assumed a no-effect level of maize shoot Cu of 40 mg/kg.     

Nutrients and nonessential elements in soil after 11 years of wastewater irrigation

Irrigation of citrus (Citrus aurantium L. × Citrus paradise Macf.) with urban reclaimed wastewater (RWW) can be economical and conserve fresh water. However, concerns remain regarding its deleterious effects on soil quality. We investigated the ionic speciation (ISP) of RWW and potential impacts of 11 yr of irrigation with RWW on soil quality, compared with well-water (WW) irrigation. Most of nutrients (～53-99%) in RWW are free ionic species and readily available for plant uptake, such as: NH(4+), NO(3-), K(+), Ca(2+), Mg(2+), SO(4)(2-), H(3)BO(3), Cl(-), Fe(2+), Mn(2+), Zn(2+), Co(2+), and Ni(2+), whereas more than about 80% of Cu, Cr, Pb, and Al are complexed with CO(3-), OH(-), and/or organic matter. The RWW irrigation increased the availability and total concentrations of nutrients and nonessential elements, and soil salinity and sodicity by two to three times compared with WW-irrigated soils. Although RWW irrigation changed many soil parameters, no difference in citrus yield was observed. The risk of negative impacts from RWW irrigation on soil quality appears to be minimal because of: (i) adequate quality of RWW, according to USEPA limits; (ii) low concentrations of metals in soil after 11 yr of irrigation with RWW; and (iii) rapid leaching of salts in RWW-irrigated soil during the rainy season.     

Chemical extraction methods to assess bioavailable arsenic in soil and solid media

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.     

Natural attenuation of residual heavy metal contamination in soils affected by the Aznalcóllar mine spill, SW Spain

Non-amended soils affected by pyritic sludge residues were monitored for 7 years to assess the long-term natural attenuation ability of these soils. The decrease in both the total concentration of elements (particularly As) and (NH(4))(2)SO(4)-extractable fractions of Mn, and Zn, below the maximum permissible levels indicate a successful natural ability to attenuate soil pollution. Soil acidification by pyrite oxidation and rainfall-enhanced leaching were the largest contributors to the reduction of metals of high (Mn, Cu, Zn and Cd) and low (Fe, Al, and As) availability. Periodic use of correlation and spatial distribution analysis was useful in monitoring elemental dispersion and soil property/element relationships.     

Sorption and desorption of cadmium by different fractions of biosolids-amended soils

To evaluate the importance of both the inorganic and organic fractions in biosolids on Cd chemistry, a series of Cd sorption and desorption batch experiments (at pH 5.5) were conducted on different fractions of soils from a long-term field experimental site. The slope of the Cd sorption isotherm increased with rate of biosolids and was different for the different biosolids. Removal of organic carbon (OC) reduced the slope of the Cd sorption isotherm but did not account for the observed differences between biosolids-amended soils and a control soil, indicating that the increased adsorption associated with biosolids application was not limited to the increased OC from the addition of biosolids. Removal of both OC and Fe/Mn further reduced the slopes of Cd sorption isotherms and the sorption isotherm of the biosolids-amended soil was the same as that of the control, indicating both OC and Fe/Mn fractions added by the biosolids were important to the increased sorption observed for the biosolids-amended soil samples. Desorption experiments failed to remove from 60 to 90% of the sorbed Cd. This "apparent hysteresis" was higher for biosolids-amended soil than the control soil. Removal of both OC and Fe/Mn fractions was more effective in removing the observed differences between the biosolids-amended soil and the control than either alone. Results show that Cd added to biosolids-amended soil behaves differently than Cd added to soils without biosolids and support the hypothesis that the addition of Fe and Mn in the biosolids increased the retention of Cd in biosolids-amended soils.     

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.     

Sample drying effects on lead bioaccessibility in reduced soil

Risk-assessment tests of contaminated wetland soils often use experimental protocols that artificially oxidize the soils. Oxidation may impact bioavailability of contaminants from the soils, creating erroneous results and leading to improper management and remediation. The goal of this study was to determine if oxygenation of reduced sediments and soils influences Pb bioaccessibility measurements. The study site is located on the Coeur d'Alene River floodplain, downstream from the Silver Valley Mining District in Idaho. A physiologically based extraction test designed to simulate the gastrointestinal tract of waterfowl (W-PBET) was used to measure relative Pb bioavailability (bioaccessibility) from the soils. The soils were collected from a submerged wetland. One set of samples was allowed to air-dry, another set was freeze-dried, and a third set was analyzed wet. The wet soil showed decreased Pb bioaccessibility compared with the air- and freeze-dried soils. The changes in extractability of Fe and Mn on air-drying were opposite from each other: Fe extractability decreased while Mn increased. The results from this study show that redox changes may have significant impacts on Pb bioavailability, and should be considered when assessing Pb contamination risks in reduced soils.     

Combined application of QEM-SEM and hard X-ray microscopy to determine mineralogical associations and chemical speciation of trace metals

We describe the application of quantitative evaluation of mineralogy by scanning electron microscopy in combination with techniques commonly available at hard X-ray microprobes to define the mineralogical environment of a bauxite residue core segment with the more specific aim of determining the speciation of trace metals (e.g., Ti, V, Cr, and Mn) within the mineral matrix. Successful trace metal speciation in heterogeneous matrices, such as those encountered in soils or mineral residues, relies on a combination of techniques including spectroscopy, microscopy, diffraction, and wet chemical and physical experiments. Of substantial interest is the ability to define the mineralogy of a sample to infer redox behavior, pH buffering, and mineral-water interfaces that are likely to interact with trace metals through adsorption, coprecipitation, dissolution, or electron transfer reactions. Quantitative evaluation of mineralogy by scanning electron microscopy coupled with micro-focused X-ray diffraction, micro-X-ray fluorescence, and micro-X-ray absorption near edge structure (mXANES) spectroscopy provided detailed insights into the composition of mineral assemblages and their effect on trace metal speciation during this investigation. In the sample investigated, titanium occurs as poorly ordered ilmenite, as rutile, and is substituted in iron oxides. Manganese's spatial correlation to Ti is closely linked to ilmenite, where it appears to substitute for Fe and Ti in the ilmenite structure based on its mXANES signature. Vanadium is associated with ilmenite and goethite but always assumes the +4 oxidation state, whereas chromium is predominantly in the +3 oxidation state and solely associated with iron oxides (goethite and hematite) and appears to substitute for Fe in the goethite structure.