Influence of soil geochemical and physical properties on the sorption and bioaccessibility of chromium(III)

There are numerous Cr(III)-contaminated sites on Department of Defense (DoD) and Department of Energy (DOE) lands that are awaiting possible clean up and closure. Ingestion of contaminated soil by children is the risk driver that generally motivates the likelihood of site remediation. The purpose of this study was to develop a simple statistical model based on common soil properties to estimate the hioaccessibility of Cr(III)-contaminated soil upon ingestion. Thirty-five uncontaminated soils from seven major soil orders, whose properties were similar to numerous U.S. DoD contaminated sites, were treated with Cr(III) and aged. Statistical analysis revealed that Cr(III) sorption (e.g., adsorption and surface precipitation) by the soils was strongly correlated with the clay content, total inorganic C, pH, and the cation exchange capacity of the soils. Soils with higher quantities of clay, inorganic C (i.e., carbonates), higher pH, and higher cation exchange capacity generally sequestered more Cr(III). The amount of Cr(III) bioaccessible from the treated soils was determined with a physiologically based extraction test (PBET) that was designed to simulate the digestive process of the stomach. The bioaccessibility of Cr(III) varied widely as a function of soil type with most soils limiting bioaccessibility to <45 and <30% after I and 100 d soil-Cr aging, respectively. Statistical analysis showed the bioaccessibility of Cr(III) on soil was again related to the clay and total inorganic carbon (TIC) content of the soil. Bioaccessibility decreased as the soil TIC content increased and as the clay content decreased. The model yielded an equation based on common soil properties that could be used to predict the Cr(III) bioaccessibility in soils with a reasonable level of confidence.     

Risk assessment test for lead bioaccessibility to waterfowl in mine-impacted soils

Due to variations in soil physicochemical properties, species physiology, and contaminant speciation, Pb toxicity is difficult to evaluate without conducting in vivo dose-response studies. Such tests, however, are expensive and time consuming, making them impractical to use in assessment and management of contaminated environments. One possible alternative is to develop a physiologically based extraction test (PBET) that can be used to measure relative bioaccessibility. We developed and correlated a PBET designed to measure the bioaccessibility of Pb to waterfowl (W-PBET) in mine-impacted soils located in the Coeur d'Alene River Basin, Idaho. The W-PBET was also used to evaluate the impact of P amendments on Pb bioavailability. The W-PBET results were correlated to waterfowl-tissue Pb levels from a mallard duck [Anas platyrhynchos (L.)] feeding study. The W-PBET Pb concentrations were significantly less in the P-amended soils than in the unamended soils. Results from this study show that the W-PBET can be used to assess relative changes in Pb bioaccessibility to waterfowl in these mine-impacted soils, and therefore will be a valuable test to help manage and remediate contaminated soils.     

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.     

In situ stabilization of soil lead using phosphorus

In situ stabilization of Pb-contaminated soils can be accomplished by adding phosphorus. The standard remediation procedure of soil removal and replacement currently used in residential areas is costly and disruptive. This study was carried out to evaluate the influence of P and other soil amendments on five metal-contaminated soils and mine wastes. Seven treatments were used: unamended control; 2,500 mg of P/kg as triple superphosphate (TSP), phosphate rock (PR), acetic acid followed by TSP, and phosphoric acid (PA); and 5,000 mg of P/kg as TSP or PR. A significant reduction in bioavailable Pb, as determined by the physiologically based extraction test (PBET), compared with the control upon addition of P was observed in all materials tested. Increasing the amount of P added from 2,500 to 5,000 mg/kg also resulted in a significantly greater reduction in bioavailable Pb. Phosphate rock was equally or more effective than TSP or PA in reducing bioavailable Pb in four out of five soils tested. Preacidification produced significantly lower bioavailable Pb compared with the same amount of P from TSP or PR in only one material. Reductions in Pb bioavailability as measured by PBET were evident 3 d after treatment, and it may indicate that the reactions between soil Pb and P occurred in situ or during the PBET. No further reductions were noted over 365 d. X-ray diffraction data suggested the formation of pyromorphite-like minerals induced by P additions. This study suggests that P addition reduced bioavailable Pb by PBET and has potential for in situ remediation of Pb-contaminated soils.     

Potential negative consequences of adding phosphorus-based fertilizers to immobilize lead in soil

A study of the potential negative consequences of adding phosphate (P)-based fertilizers as amendments to immobilize lead (Pb) in contaminated soils was conducted. Lead-contaminated firing range soils also contained elevated concentrations of antimony (Sb), a common Pb hardening agent, and some arsenic (As) of unknown (possibly background) origin. After amending the soils with triple superphosphate, a relatively soluble P source, column leaching experiments revealed elevated concentrations of Sb, As, and Pb in the leachate, reflecting an initial spike in soluble Pb and a particularly dramatic increase in Sb and As mobility. Minimal As, Sb, and Pb leaching was observed during column tests performed on non-amended control soils. In vitro extractions tests were performed to assess changes in Pb, As, and Sb bioaccessibility on P amendment. Lead bioaccessibility was systematically lowered with increasing P dosage, but there was much less of an effect on As and Sb bioaccessibility than on mobility. Our results indicate that although P amendments may aid in lowering the bioaccessibility of soil-bound Pb, it may also produce an initial increase in Pb mobility and a significant release of Sb and As from the soil, dramatically increasing their mobility and to a lesser extent their bioavailability.     

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.     

Bioaccessibility of lead sequestered to corundum and ferrihydrite in a simulated gastrointestinal system

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (alpha-Al(2)O(3)) and ferrihydrite (Fe(5)HO(8).4H(2)O). The Pb-sorbed minerals were placed in a simulated gastrointestinal tract (in vitro) to simulate ingestion of Pb-contaminated soil. The changes in Pb speciation were determined using extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES). Both corundum (sorption maximum of 2.13 g kg(-1)) and ferrihydrite (sorption maximum of 38.6 g kg(-1)) have been shown to sorb Pb, with ferrihydrite having a very high affinity for Pb. The gastric bioaccessible Pb for corundum was >85% for corundum when the concentration of Pb was >200 mg kg(-1). Bioaccessible Pb was not detectable at 4. However, much of the sorbed Pb will become bioaccessible under gastric conditions (pH 1.5-2.5) if this soil is ingested. Caution should be used before using these materials to remediate a soil where soil ingestion is an important exposure pathway.     

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.     

Decreasing lead bioaccessibility in industrial and firing range soils with phosphate-based amendments

In-situ stabilization using phosphate (P) amendments, such as P-based fertilizers and rock, are a potentially cost-effective and minimally disruptive alternative for stabilizing Pb in soils. We examined the effect of time (0-365 d), in vitro extraction pH (1.5 vs. 2.3), and dosage of three P-based amendments on the bioaccessibility (as a surrogate for oral bioavailability) of Pb in 10 soils from U.S. Department of Defense facilities. Initial untreated soil bioaccessibility consistently exceeded the U.S. Environmental Protection Agency default value of 60% relative bioavailability, with higher bioaccessibility consistently observed at an in vitro extraction pH of 1.5 vs. 2.3. Although P-based amendments statistically (P < 0.05) reduced bioaccessibility in many instances, with reductions dependent on the amendment and dosage, large amendment dosages (approximately 20-25% by mass to yield 5% P by mass) were required to reduce average bioaccessibility by approximately 25%. For most amendment combinations, reductions continued to occur for periods up to 1 yr, indicating that the observed reductions were not merely experimental artifacts of the in vitro extraction procedure. Although our results indicated that reductions in Pb bioaccessibility with P amendments are technically feasible, relatively large amendment masses were required to achieve relatively modest reductions in bioaccessibility. The cost and potential environmental implications of adding such large amounts of P may limit the practicality of in situ immobilization for some Pb-contaminated soils, industrial and firing range soils in particular.     

Dissolution of trace element contaminants from two coastal plain soils as affected by pH

Trace element mobility in soils depends on contaminant concentration, chemical speciation, water movement, and soil matrix properties such as mineralogy, pH, and redox potential. Our objective was to characterize trace element dissolution in response to acidification of soil samples from two abandoned incinerators in the North Carolina Coastal Plain. Trace element concentrations in 11 soil samples from both sites ranged from 2 to 46 mg Cu kg(-1), 3 to 105 mg Pb kg(-1), 1 to 102 mg Zn kg(-1), 3 to 11 mg Cr kg(-1), < 0.1 to 10 mg As kg(-1), and < 0.01 to 0.9 mg Cd kg(-1). Acidified CaCl2 solutions were passed through soil columns to bring the effluent solution to approximately pH 4 during a 280-h flow period. Maximum concentrations of dissolved Cu, Pb, and Zn at the lowest pH of an experiment (pH 3.8-4.1) were 0.32 mg Cu L(-1), 0.11 mg Pb L(-1), and 1.3 mg Zn L(-1) for samples from the site with well-drained soils, and 0.25 mg Cu L(-1), 1.2 mg Pb L(-1), and 1.4 mg Zn L(-1) for samples from the site with more poorly drained soils. Dissolved Cu concentration at pH 4 increased linearly with increasing soil Cu concentration, but no such relationship was found for Zn. Dissolved concentrations of other trace elements were below our analytical detection limits. Synchrotron X-ray absorption near edge structure (XANES) spectroscopy showed that Cr and As were in their less mobile Cr(III) and As(V) oxidation states. XANES analysis of Cu and Zn on selected samples indicated an association of Cu(II) with soil organic matter and Zn(II) with Al- and Fe-oxides or franklinite.     

In situ stabilization of soil lead using phosphorus and manganese oxide: influence of plant growth

In situ stabilization of Pb contaminated soils can be accomplished by adding P and Mn(IV) oxide. However, the long-term efficacy of in situ stabilization under continual P removal through plant growth is unknown. Moreover, the effects these treatments have on phytoavailability of other metals (Cd and Zn) commonly associated with Pb in soil are not well understood. Greenhouse experiments using sudax [Sorghum vulgare (L.) Moench] and Swiss chard [Beta vulgaris (L.) Koch] were carried out to evaluate the effects of plant growth on soil Pb bioavailability to humans after addition of P and other amendments, and the effects of these treatments on Pb, Cd, and Zn phytoavailability in three metal-contaminated soils. Eight treatments were used: zero P; 2500 mg of P as triple superphosphate (TSP); 5000 mg of P as TSP or phosphate rock (PR); 5000 mg of Mn oxide/kg; and combinations of Mn oxide and P as TSP or PR. The addition of P and/or Mn oxide significantly reduced bioavailable Pb, as measured by the physiologically based extraction test (PBET), in soils compared with the control even after extensive cropping. The PBET data also suggested that removal of P from soluble P sources by plants could negate the beneficial effects of P on bioavailable Pb, unless sufficient soluble P was added or soluble P was combined with Mn oxide. In general, Ph, Cd, and Zn concentrations in shoot tissues of sudax and Swiss chard were reduced significantly by TSP and did not change with the addition of PR. The combination of PR and Mn oxide significantly reduced Pb concentrations in plants compared with the control.     

Multivariate statistics to investigate metal contamination in surface soil

The modification of soil composition in the urbanized area of Ankara due to wet-dry deposition and pollution-derived particles from the atmosphere is investigated by analyzing 120 surface soil samples, collected from the urbanized area and its un-urbanized surrounding, for major, minor and trace elements. Concentrations of elements from human activity (e.g. Cd, Pb, Cr, Zn, Cu and Ca) in the urbanized area were higher than their corresponding concentrations in global average soil and soil in un-urbanized areas outside the urbanized area. Metal contents in soil were very high in densely populated districts and around some industrial facilities. The only exception was Pb distribution, which was more dispersed, due to the nature of motor vehicle emissions. Alteration of the Cd, Zn, Cu and Cr content of soil was confined to the inhabited and industrial areas, whereas enrichment factors of these elements were close to unity in the remaining study area. Factor analysis identified two polluted soil factor associations. One factor includes elements, such as Zn and Cd, which had high factor scores in inhabited areas and the other factor (high loading of Pb) represents soil polluted by motor vehicle emissions.     

An inventory of trace element inputs to agricultural soils in China

It is important to understand the status and extent of soil contamination with trace elements to make sustainable management strategies for agricultural soils. The inputs of trace elements to agricultural soils via atmospheric deposition, livestock manures, fertilizers and agrochemicals, sewage irrigation and sewage sludge in China were analyzed and an annual inventory of trace element inputs was developed. The results showed that atmospheric deposition was responsible for 43–85% of the total As, Cr, Hg, Ni and Pb inputs, while livestock manures accounted for approximately 55%, 69% and 51% of the total Cd, Cu and Zn inputs, respectively. Among the elements concerned, Cd was a top priority in agricultural soils in China, with an average input rate of 0.004 mg/kg/yr in the plough layer (0–20 cm). Due to the spatial and temporal heterogeneity of the sources, the inventory as well as the environmental risks of trace elements in soils varies on a regional scale. For example, sewage sludge and fertilizers (mainly organic and phosphate-based inorganic fertilizers) can also be the predominant sources of trace elements where these materials were excessively applied. This work provides baseline information to develop policies to control and reduce toxic element inputs to and accumulation in agricultural soils.     

Prediction of microbial accessibility of carbon-14-phenanthrene in soil in the presence of pyrene or benzo[a]pyrene using an aqueous cyclodextrin extraction technique

Traditionally, solvent extractions are routinely used in the assessment of contaminated land. However, vigorous solvent extractions only give total concentrations rather than that relating to the bioaccessible fraction. Recently, less harsh, aqueous-based extraction methods have been shown to be a better estimate of the microbial degradation of polycyclic aromatic hydrocarbons (PAHs). The aqueous-based hydroxypropyl-beta-cyclodextrin (HPCD) extraction technique was tested using 14C-PAHs in soils and compared against indigenous microbial mineralization (a measure of bioaccessibility) of 14C-phenanthrene in the presence of pyrene or benzo[a]pyrene (B[a]P) over a range of concentrations (0, 5, 10, or 50 mg kg(-1)) and aged for 0, 25, 50, and 100 d in four soils. At each time point, the total loss, extractability, and mineralization of 14C-phenanthrene was measured in each of the soils. The presence of the other PAHs had little effect on the behavior of 14C-phenanthrene in any of the soils. Comparisons between the amounts of 14C-phenanthrene extracted using HPCD and mineralized were made and showed that there was a correlation (1:1). This study demonstrates that HPCD extraction is able to predict the microbial accessibility fraction of 14C-phenanthrene in the presence of other PAHs in a range of soils, further supporting the applicability of this technique.     

Field test of in situ soil amendments at the Tar Creek National Priorities List Superfund site

A range of soil amendments including diammonium phosphate fertilizer (DAP), municipal biosolids (BS), biosolids compost, and Al- and Fe-based water treatment residuals were tested on Pb-, Zn-, and Cd-contaminated yard soils and tailings at the Tar Creek NPL site in Oklahoma to determine if amendments could restore a vegetative cover and reduce metal availability in situ. For the yard soils, all amendments reduced bioaccessible (assessed with a physiologic-based extraction method) Pb, with reductions ranging from 35% (BS+Al, DAP 0.5%, DAP+Compost+Al) to 57% (Compost+Al). Plant Zn (Cynadon dactylon L.) and NH4 NO3-extractable Cd and Zn were also reduced by a number of amendments. For the tailings, all amendments excluding BS reduced bioaccessible Pb, with the largest reductions observed in the DAP 3% and DAP3%+BS treatments (75 and 84%). Plant growth was suppressed in all treatments that contained DAP for the first season, with the highest growth in the treatments that included compost and biosolids. In the second year, growth was vigorous for all treatments. Plant Zn and Cd and extractable metal concentration were also reduced. A number of treatments were identified that reduced bioaccessible Pb and sustained a healthy plant with reduced metal concentrations. For the yard soil, Compost+Al was the most effective treatment tested. For the tailings, BS+DAP 1% was the most effective treatment tested. These results indicate that in situ amendments offer a remedial alternative for the Tar Creek site.     

Response of soil microbiological activities to cadmium,lead, and zinc salt amendments

Heavy metal pollution of soil has been recognized as a major factor impeding soil microbial processes. From this perspective, we studied responses of the soil biological activities to metal stress simulated by soil amendment with Zn, Pb, and Cd chlorides. The amounts of heavy metal salts added to five metal-polluted soils and four nonpolluted soils were selected to match the total metal concentrations typically found in polluted soils of the Silesia region of Poland. From the perspective of soil quality, metal mobility in amended soils could not be described by simple functions of pH or organic matter. Reaction of Pb with the soil caused strong immobilization with less than 1% of the Pb amendment recovered by 0.01 M CaCl2 extractions. Immobilization of Cd was also significant, whereas immobilization of the Zn amendment was much weaker than that of Cd or Pb. The Zn amendment had substantial inhibitory effect on soil dehydrogenase, acid and alkaline phosphatase, arylsulfatase, urease, and nitrification potential. Generally, Cd and Pb had limited or stimulatory effect on most of these biological activities, with an exception of Pb strongly inhibiting soil urease. The effect of the metal amendments on biological activities could not be satisfactorily accounted for by metal toxicity because no strong relationship was observed between extractable metal content and the degree of inhibition. The Zn amendment had a significant effect on soil pH, resulting in confounding effects of pH and Zn toxicity on activities. Metal amendment experiments seem to be of limited utility for meaningful assessment of metal contamination effects on soil quality.     

Distribution of chromium contamination and microbial activity in soil aggregates

Biogeochemical transformations of redox-sensitive chemicals in soils can be strongly transport-controlled and localized. This was tested through experiments on chromium diffusion and reduction in soil aggregates that were exposed to chromate solutions. Reduction of soluble Cr(VI) to insoluble Cr(II) occurred only within the surface layer of aggregates with higher available organic carbon and higher microbial respiration. Sharply terminated Cr diffusion fronts develop when the reduction rate increases rapidly with depth. The final state of such aggregates consists of a Cr-contaminated exterior, and an uncontaminated core, each having different microbial community compositions and activity. Microbial activity was significantly higher in the more reducing soils, while total microbial biomass was similar in all of the soils. The small fraction of Cr(VI) remaining unreduced resides along external surfaces of aggregates, leaving it potentially available to future transport down the soil profile. Using the Thiele modulus, Cr(VI) reduction in soil aggregates is shown to be diffusion rate- and reaction rate-limited in anaerobic and aerobic aggregates, respectively. Thus, spatially resolved chemical and microbiological measurements are necessary within anaerobic soil aggregates to characterize and predict the fate of Cr contamination. Typical methods of soil sampling and analyses that average over redox gradients within aggregates can erase important biogeochemical spatial relations necessary for understanding these environments.     

Availability of arsenic, copper, lead, thallium, and zinc to various vegetables grown in slag-contaminated soils

To anticipate a possible hazard resulting from the plant uptake of metals from slag-contaminated soils, it is useful to study whether vegetables exist that are able to mobilize a given metal in the slag to a larger proportion than in an uncontaminated control soil. For this purpose, we studied the soil to plant transfer of arsenic, copper, lead, thallium, and zinc by the vegetables bean (Phaseolus vulgaris L. 'dwarf bean Modus'), kohlrabi (Brassica oleracea var. gongylodes L.), mangold (Beta vulgaris var. macrorhiza ), lettuce (Lactuca sativa L. 'American gathering brown'), carrot (Daucus carota L. 'Rotin', 'Sperlings's'), and celery [Apium graveiolus var. dulce (Mill.) Pers.] from a control soil (Ap horizon of a Entisol) and from a contaminated soil (1:1 soil-slag mixtures). Two types of slags were used: an iron-rich residue from pyrite (FeS2) roasting and a residue from coal firing. The metal concentrations in the slags, soils, and plants were used to calculate for each metal and soil-slag mixture the plant-soil fractional concentration ratio (CRfractional,slag), that is, the concentration ratio of the metal that results only from the slag in the soil. With the exception of TI, the resulting values obtained for this quantity for As, Cu, Pb, and Zn and for all vegetables were significantly smaller than the corresponding plant-soil concentration ratios (CRcontrol soil) for the uncontaminated soil. The results demonstrate quantitatively that the ability of a plant to accumulate a given metal as observed for a control soil might not exist for a soil-slag mixture, and vice versa.     

河南农田土壤重金属污染状况及其评价

在河南境内取自农田土壤102例表层样品，分析了其中的Cr、Zn、Cu、Pb、Ni、As等8种重金属元素的含量。结果表明：河南农田土壤中除Cr偶有超出我国《土壤环境质量标准》（GB15618—1995）二级标准的土样外，其他项目均不超标，重金属污染由高到低排序为Cr〉Zn〉Ni〉Cd〉Hg〉Cu〉Pb〉As。重金属元素在河南各土壤利用类型中分布规律不明显，按4种主要土壤利用类型考查来看，重金属污染程度大小排序为：果园地〉水田〉菜地〉其他粮田；河南农田土壤综合污染指数总平均为0．981，土壤总体为尚清洁，重金属污染处于警戒水平；河南农田土壤中Cr含量较高的土壤主要是粗骨土与石质土，其天然本底值较高。     

Assessment of the use of industrial by-products to remediate a copper- and arsenic-contaminated soil

Two water treatment sludges (WTS-A, WTS-B), two red muds (RM), and red gypsum (RG), all rich in iron oxy-hydroxides, were added to a soil highly polluted with As and Cu at 2% (w/w) to reduce metal bioavailability. Because the amendments increased soil pH to approximately 6, a lime treatment to the same pH and an unamended treatment were included for comparison. All the amendments had significant positive effects on the soil microbial biomass and growth of ryegrass (Lolium multiflorum Lam. cv. Avance), but only WTS-A improved lettuce (Lactuca sativa L. cv. Tom Thumb) growth. The mineralization of added ammonium nitrogen was not significantly affected by the treatments, while a physiologically based extraction test (PBET) showed that bioaccessibility of As was low (< 5%) and decreased only in the WTS-A treatment. Concentrations of As in soil pore water and extractable As only decreased in the WTS and RG treatments. In contrast, Cu concentrations in soil pore water and extractable Cu decreased in all treatments, by more than 84% in the WTS, RM, and RG treatments. Non-isotopically exchangeable As and Cu were present in colloids in the soil pore water. Untreated soil had < 4% isotopically exchangeable As and this decreased by approximately 50%, with WTS, RM, and RG. The labile Cu pool represented a large proportion (34%) of the total Cu pool, and the isotopically exchangeable and soluble Cu were strongly correlated with soil pH. Acidification of the treated soils showed that the labile As and Cu both increased in the treated soils compared with untreated soils. The significance of the treatment effects on soil fertility and potential off-site transport of As and Cu to ground water are discussed.