亚热带土壤不同矿物组分中铬的吸附

Safe application of chromium (Cr)-containing organic industrial wastes to soil requires considering the ability of the soil to adsorb Cr.In this study,the maximum Cr adsorption capacity was assessed for the bulk samples and their clay and iron-free clay fractions of four subtropical soils differing in mineralogy.To this end,the samples were supplied with Cr(Ⅲ) nitrate solutions at pH 4.5 or 5.5.The results of Cr(Ⅲ) adsorption fitted to a Freundlich equation and the adsorption capacity was positively correlated with soil organic matter and iron oxide contents.The clay fractions adsorbed more Cr per unit mass than the bulk soils and the iron-free clay fractions.The Cr(Ⅲ) adsorption capacity increased with increasing soil pH due to more charges on adsorbing surfaces.Our results suggest that the soils rich in organic matter and iron oxides and having a pH above 4.5 are suitable for application of Cr(Ⅲ)-loaded industrial wastes.     

有机配体、竞争阳离子和pH对土壤中Zn分解的影响

A series of experiments were conducted to examine the interactive effects of an organic ligand, a competing cation, and pH on the dissolution of zinc （Zn） from three California soils, Maymen sandy loam, Merced clay, and Yolo clay loam. The concentrations of soluble Zn of the three soils were low in a background solution of Ca（NO3）2. Citric acid, a common organic ligand found in the rhizosphere, was effective in mobilizing Zn in these soils; its presence enhanced the concentration of Zn in soil solution by citrate forming a complex with Zn. The ability of Zn to form a complex with citric acid in the soil solution was dependent on the concentration of citric acid, pH, and the concentration of the competing cation Ca^2＋. The pH of the soil solution determined the extent of desorption of Zn in solid phase in the presence of citric acid. The amounts of Zn released from the solid phase were proportional to the concentration of citric acid and inversely proportional to the concentration of Ca（NO3）2 background solution, which supplied the competing cation Ca^2＋ for the formation of a complex with citrate. When the soil suspension was spiked with Zn, the adsorption of Zn by the soils was retarded by citric acid via the formation of the soluble Zn-citrate complex. The dissolution of Zn in the presence of citric acid was pH dependent in both adsorption and desorption processes.     

铵、钾同时存在时, 土壤对铵的优先吸附

The water stability of aggregates in various size classes separated from 18 samples of red soils under different managements, and the mechanisms responsible for the formation of water-stable soil aggregates were studied. The results showed that the water stability of soil aggregates declined with increasing size, especially for the low organic matter soils. Organic matter plays a key role in the formation of water-stable soil aggregates. The larger the soil aggregate size, the greater the impact of organic matter on the water stability of soil aggregates. Removal of organic matter markedly disintegrated the large water-stable aggregates (> 2.0 mm) and increased the small ones (< 0.25-0.5mm) to some extent, whereas removal of free iron(aluminium) oxides considerably destroyed aggregates of all sizes, especially the < 0.25-0.5 mm classes. The contents of organic matter in water-stable aggregates increased with aggregate sizes. It is concluded from this study that small water-stable aggregates (< 0.25-0.5 mm) were chiefly cemented by Fe and Al oxides whilst the large ones (> 2.0 mm) were mainly glued up by organic matter. Both free oxides and organic matter contribute to the formation and water stability of aggregates in red soils.     

连续三年添加制革厂堆肥后土壤微生物生物量研究

Brazilian industry produces huge amounts of tannery sludge as residues, which is often disposed by landfilling or land application. However, consecutive amendment of such composted industrial wastes may cause shifts in soil microbial biomass （SMB） and enzyme activity. This study aimed to evaluate SMB and enzyme activity after 3-year consecutive composted tannery sludge （CTS） amendment in tropical sandy soils. Different amounts of CTS （0.0, 2.5, 5.0, 10.0, and 20.0 t ha-1） were applied to a sandy soil. The C and N contents of SMB, basal and substrate-induced respiration, respiratory quotient （qCO2）, and enzyme activities were determined in the soil samples collected after CTS amendment for 60 d at the third year. After 3 years, significant changes were found in soil microbial properties in response to different CTS amounts applied. The organic matter and Cr contents significantly increased with increasing CTS amounts. SMB and soil respiration peaked following amendment with 10.0 and 20.0 t ha-1 of CTS, respectively, while qCO2 was not significantly affected by CTS amendment. However, soil enzyme activity decreased significantly with increasing CTS amounts. Consecutive CTS amendment for 3 years showed inconsistent and contrasting effects on SMB and enzyme activities. The decrease in soil enzyme activities was proportional to a substantial increase in soil Cr concentration, with the latter exceeding the permitted concentrations by more than twofold. Thus, our results suggest that a maximum CTS quantity of 5.0 t ha-1 can be applied annually to tropical sandy soil, without causing potential risks to SMB and enzyme activity.     

锰氧化物对三价铬氧化的影响因子

The high oxidation ability of manganese oxides or soils was used to study effects of PH and coating on Cr（Ⅲ） oxidation,The results indicated that Cr（Ⅲ） oxidation peaked in PH 4.0-6.5,The amount and rate of Cr（Ⅲ） being oxidized by uncoated δ-MnO2 were larger than those by Fe oxide- of CaCo3-coated one.Inorganic Cr（Ⅲ） wa more easily oxidzed by MnO2 than organic complex Cr（Ⅲ） due to different surface affinities. Precipitated Cr（Ⅲ） and adsorbed Cr（Ⅲ） might be transferred onto MnO2 surface and then oxidized to Cr(Ⅵ）     

施用碱稳定固体的酸性土壤的Cu和Zn的形态分布

Fractionation of metals in a granite-derived acid sandy loam soil amended with alkaline-stabilised sewagesIudge biosolids was conducted in order to assess metal bioavailability and environmental mobility soil solution was extracted by a centrifugation and filtration technique. Metal speciation in the soil solution wasdetermined by a cation exchange resin method. Acetic acid and EDTA extracting solutions were used forextraction of metals in soil solid surfaces. Metal distribution in different fractions of soil solid phase was determined using a three-step sequential extraction scheme. The results show that the metals in the soilsolution existed in different fractions with variable lability and metals in the soil solid phase were also presentin various chemical forms with potentially different bioavail ability and environmental mobility Alkaline-stabilised biosolids could elevate solubility of Cu and proportion of Cu in organically complexed fractionsboth in soil liquid and solid phases, and may therefore increase Cu mobility. In contrast, the biosolids lowered the concentrations of water-soluble Zn (labile fraction) and exchangeable Zn and may hence decrease bioavailability and mobility of Zn. However, Fe and Mn oxides bound and organic matter bound fractions are likely to be Zn pools in the sludge-amended soil. These consequences possibly result from the liming effect and metal speciation of the sludge product and the difference in the chemistry between the metals in soil.     

Composition and Characteristics of Organo—Mineral Complexes of Red Soils in South China

The objective of the present study is to reveal the composition and characteristics of organo-mineral complexes in red soils (red soil,lateritic red soil and latosol) of south China in terms of chemical dissolution and fractional peptization methos.In the combined humus,most of the extractable humus could dissolve in 0.1 M NaOH extractant and belonged to active humus (H1),and there was only a small amount of humus which could be further dissolved in 0.1 M Na4P2O7 extractant at pH 13 and was stably combined humus (H2).The H1/H2 ratio ranged from 3.3 to 33.8 in red soils,and the proportions of both H1 and total extractable organic carbon (H1 H2) in total soil organic carbon and the ratios of H1 to H2 and H1 to (H1 H2) were all higher in lateritic red soil and latosol than in red soil.The differences of combined humus composition in various red soils were directly related to the content of Fe and Al oxides.In organo-mineral complexes,the ratio of Na-dispersed fraction (G1) to Na-ground-dispersed fraction (G2) was generally smaller than 1 for red soils,but there was a higher G1/G2 ratio in red soil than in lateritic red soil and latosol.G1 fraction had a higher content of fulvic acid (FA),but G2 fraction had a higher content of humic acid (HA).The ratios of H1 to H2 and HA to FA were higher in G2 than in G1.The differences in the composition and activity of humus between G1 and G2 fractions were related to the content of free Fe and Al oxides.The quantities of complex Fe and Al,the Fe/C and Al/C atomic ratios were higher in G2 than in G1,and the ratio of Al/C was much higher than that of Fe/C.It may be deduced that aluminum plays a more important role than iron in the formation process of organo-mineral complexes in red soils.     

以Mg2+/Co2+为模板, 钴掺杂对层状锰氧化物向钙锰矿转化的影响

Cobalt(Co)exists in significant quantities in naturally occurring manganese(Mn)oxides and alters the growth of Mn oxide crystals.Four-layered Mn oxides,Na-buserite(Na-bus)and three Co-doped Na-buserite samples prepared from oxidation of Mn(OH)2 with 5%,10%,and 20% Co/(Mn+Co)molar ratios(5Co-Na-bus,10Co-Na-bus,and 20Co-Na-bus),were used to prepare todorokite,a common Mn oxide on the Earth’s surface,using Mg2+/Co2+ ions as a template.The results showed that todorokites could be obtained by reflux treatment of Mg2+-exchanged non-doped Na-buserite and three Co-doped Na-buserites at atmospheric pressure.However,the formation of todorokites was prohibited by reflux treatment of Co2+-exchanged Na-bus,5Co-Na-bus,and 10Co-Na-bus samples.Instead,todorokite was obtained by the reflux treatment of Co2+-exchanged 20Co-Na-bus samples under atmospheric pressure.X-ray photoelectron spectroscopy analysis showed that doped Co existed as Co3+in the MnO6 layers of doped Na-buserites.The amount of substituted Co3+ in the MnO6 layers may play a key role in the conversion of buserite to todorokite using Co2+ ions as a template.     

有机物料对淹水土壤中施入的镉形态的影响

The effect of three organic materials(rice straw,Chinese milk vetch and pig manure)on the fractionation of cadmium added into two soils(a red soil and a fluvo-aquic soil) was studied using submerged incubation experiment.The organic materials increased soil soild organic carbon(SOC),pH value,the concentration of active Si in all the treatments and active Fe and Mn in some treatments.Accumulated SOC caused directly the increase of Cd bound to solid organic matter and consequently the decrease of exchangeable Cd.Higher active Si and pH,as well as lower Eh,were also responsible for the reduction of exchangeable Cd.Cd bound to mn oxide was positively correlated with pH values and rose significantly after one-month incubation,but decreased after three-month incubation.Cd bound to amporphous Fe oxide increased with the incubation time,but was not affected significantly by adding organic materials.     

高岭石和氧化土悬液中铝的水解行为及有机酸对铝水解反应的影响

To evaluate the role of kaolinite and variable charge soils on the hydrolytic reaction of Al, the hydrolysis of Al ions in suspensions of a kaolinite and an Oxisol influenced by organic anions was investigated using changes of pH, Al adsorption, and desorption of pre-adsorbed Al. Kaolinite and the Oxisol promoted the hydrolytic reaction of Al above a certain initial Al concentration (0.1 mmol L^-1 for kaolinite and 0.3 mmol L^-1 for the Oxisol). The Al hydrolysis accelerated by kaolinite and the Oxisol increased with an increase in initial concentration of Al and was observed in the range of pH from 3.7 to 4.7 for kaolinite and 3.9 to 4.9 for the Oxisol. The acceleration of Al hydrolysis also increased with the increase of solution pH, reached a maximum value at pH 4.5, and then decreased sharply. Al hydrolysis was promoted mainly through selective adsorption for hydroxy-Al. Soil free iron oxides compensated a portion of the soil negative charge or masked some soil surface negative sites leading to a decrease in Al adsorption, which retarded acceleration to some extent. For the Oxisol organic anions increased the proportion of adsorbed Al³⁺ in total adsorbed Al with the increase in soil negative surface charge and eliminated or reduced the acceleration of Al hydrolysis. Different organic anions inhibited the hydrolysis of Al in the order: citrate > oxalate > acetate (under initial pH of 4.5). The formation of Al-organic complexes in solution also inhibited the hydrolysis of Al.     

Development of Analytical Procedure for the Determination of Exchangeable Cr(VI) in Soils by Anion-exchange Fast Protein Liquid Chromatography with Electrothermal Atomic Absorption Spectrometry Detection

Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄–K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l^?1), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l^?1 and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g^?1 of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g^?1.     

Cr(III) oxidation coupled with Mn(II) bacterial oxidation in the environment

Purpose  

Cr(III) oxidation to Cr(VI) significantly increases Cr mobility and toxicity and thus its environmental risks. Manganese (Mn) oxides may serve as the potential oxidants of Cr(III) in environment. Natural Mn oxides in the environment are believed to be derived from bacterial oxidation. The objective of this study was to examine the Cr(III) oxidation capacity of biogenic Mn oxide and the role of Mn-oxidizing bacteria in Cr(III) oxidation.     

Hydrogeochemical behavior of chromium in the unsaturated zone and in the aquifer of leon valley,Mexico

The ground water of Leon valley, Central Mexico, is contaminated with chromium. A study was carried out to determine the main physico-chemical interactions between chromium and the aquifer solid matrix in the most polluted area. Five boreholes, 30 m deep, were drilled and used as piezometers. Unaltered solid cores were analyzed for Cr(VI), total Cr, Fe and Mn. Cr(VI) was determined in the water from the piezometers. We conclude that reduction of Cr(VI) by iron is important, adsorption of Cr(VI) by sand and gravel layers is negligible, and adsorption by silt and clay layers is significant in the saturated and unsaturated zones. In the saturated zone hexavalent chromium distributes preferentially in the water phase oxidation of chromium by manganese was not detected. A correlation between chromium, manganese and iron concentrations was observed for the aquifer solid matrix in this area, when the source of chromium was not anthropogenic.     

Chromate Generation by Chromate Depleted Subsurface Materials

Soluble chromate concentrations as high as 200 μg Cr L^-1 have been reported in water samples from monitoringwells tapping alluvial deposits allegedly contaminated bylaboratory waste as well as control wells off site andupgradient (shallow aquifer) near Davis California, U.S.A. In this report we present evidence that these Cr(VI) levelscould have been generated by geogenic processes rather thanby anthropogenic inputs. We tested the hypothesis thatnative Cr(III) has been and can be oxidized to chromate bynative manganese oxides. Twenty-three drill core samples(all unsaturated) were retrieved from depths varying from1.5 to 22.5 m in 6 different wells. Visible nodules ofMnO₂ were dispersed throughout many of the samples andcarbonates were also present. Sample pH values averagedabout 8.0 and organic C was mostly less than 1.0 g kg^-1. Total Mn and Cr averaged 835 and 191 mg kg^-1respectively. All samples had the capability to oxidizeadded Cr(III) to Cr(VI). To determine the inherent capabilityof the samples to produce Cr(VI) from native Cr(III), subsamples were extracted with 5 mM CaSO₄ plus 5 mM MgSO₄ until Cr(VI) was no longer detected. After freeze-drying, deionized-distilled water was added to theleached samples to approximately field capacity (0.03 MPa). Freeze drying did not generate Cr(VI). These samples wereincubated in polyethylene film bags at room temperature inthe dark. After 1 week incubation, water in the samples wasextracted by centrifugation and the extracts were analyzedfor Cr(VI). All of the samples generated Cr(VI), and theconcentrations in the extracts ranged from 20 to 100 μg Cr L^-1. Total chromium, endemic chromium VI and chromium VI generated in leached samples were not statistically different between samples from onsite and control samples taken offsite and upgradient in respect to the shallowest aquifer.     

Chromium and arsenic in contaminated soils (Review of publications)

In the last decades, the chromium clarke in the world’s soils has been revised and reduced; at present, it is equal to 70 mg/kg. No maximal permissible concentration is accepted for the total chromium content in the soils of Russia; it appears reasonable to use the Western European and North American standards in Russia and to take the average value of the maximal permissible concentration equal to 200 mg Cr/kg. Chromium toxicity depends on its oxidizing status. The hazardous effect decreases with the reduction of Cr(VI) to Cr(III). There are various chemical reducers of Cr(VI), including sulfides, dissolved organic substance, aqueous Fe(II) and minerals enriched in Fe(II), and Fe(0). As-containing ore tailings represent a powerful source of technogenic arsenic. Significant environment contamination with natural As is registered in a number of Asian countries. The maximal permissible concentration of total arsenic is equal to 2 mg/kg in Russian soils; it is probably underestimated, because it is lower than the As clarke in soil (5 mg/kg). The approximately permissible concentration (APC) values for As look more reasonable. Arsenic toxicity depends on its oxidation degree: As(III) is 2–3 times more toxic than As(V).     

Plant heavy metal concentrations and soil biological properties in agricultural serpentine soils

Abstract

Soils developed on serpentinitic rocks have serious limitations for agriculture. They have high levels of magnesium (Mg) and heavy metals [copper (Cu), manganese (Mn), nickel (Ni), and chromium (Cr)] and are deficient in some macronutrients. In parts of Northwestern Spain, serpentine soils have been subjected to intensive management, based on the use of manure and harvesting residues. Although these practices have allowed the growth of crops, plants may have accumulated high amounts of metals. This study was carried out to assess the effect of the management practices on the uptake of heavy metals by crops, and to analyze the relationship between the concentrations of these metals in plants, and soil properties. Moderate levels of Ni and Mn and low levels of Cr and Cu were found in soil extractable fractions of these metals. In spite of this, analysis of plant tissues revealed high levels of Cr and Ni and moderate contents of Mn. Concentrations of Mn and Ni in foliage were correlated to soil extractable contents, whereas simple linear regression between concentration of Cr in plants and the soil‐extractable Cr showed a poor relationship, possibly because the availability of this metal, as Cr(VI), is determined by temporal environmental conditions. To assess the effects of the management on the uptake of heavy metals by plants, a complementary bioassay experiment was carried out in the laboratory in which Festuca rubra and Agrostis stolonifera were sown on serpentine soil with low organic matter content, and amended with peat and/or lime. This experiment confirmed that there is a reduction in heavy metal concentration in plants after organic amendment and suggested that the lower metal availability is partly due to the higher soil microbial activity, produced as a consequence of addition of organic matter.     

Chemical oxidation of arsenic in the environment and its application in remediation: A mini review

Arsenic(As) contamination in soil and water poses a serious threat to the ecosystem health and human beings, and is of widespread concern. The main As species found in soil and water are arsenite As(Ⅲ) and arsenate As(Ⅴ). Because As(Ⅲ) is more toxic and often more mobile than As(Ⅴ), many remediation strategies aim to oxidize As(Ⅲ) to As(Ⅴ). In the environment, the reduction of As(Ⅴ) under anaerobic conditions is mainly mediated by microorganisms, but the oxidation of As(Ⅲ) under aerobic conditio...     

Assessment of Heavy Metals in Spinach (Spinacia oleracea L.) Grown in Sewage Sludge–Amended Soil

The assessment of heavy metals in spinach (Spinacia oleracea) grown in sewage sludge–amended soil was investigated. The results revealed that sewage sludge significantly (P < 0.01) increased the nutrients and heavy metals such as cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn) in the soil. The contents of metals were found to be below the maximum levels permitted for soils in India. The most agronomic performance and biochemical components of S. oleracea were found at 50% concentrations of sewage sludge in both seasons. The contents of Cd, Cr, Cu, Mn, and Zn in S. oleracea were increased from 5% to 100% concentrations of sewage sludge in both seasons. The order of contamination factor (Cf) of different heavy metals was Mn > Cd > Cr > Zn > Cu for soil and Cr > Cd > Mn > Zn > Cu for S. oleracea plants after application of sewage sludge. Therefore, use of sewage sludge increased concentrations of heavy metals in soil and S. oleracea.     

Mineralogy and geochemistry of manganese: A review of publications

The relatively low hydrolyzing capacity of Mn(II) leads to the formation of oxides rather than hydroxides of this element in soils. The formation of vernadite, birnessite, todorokite, and lithiophorite was recently proved in soils. Vernadite with an Fe admixture and Mn-containing iron minerals, i.e., ferroxyhyte, ferrihydrite, and magnetite, were also found. Fe-vernadite and Mn-ferroxyhyte are the most abundant in soils. Manganese oxidogenesis is the most intensely pronounced in the soils of steppe and forest-steppe zones, in which the assemblage of Mn-containing minerals is wider than in taiga soils. Carbonates are able to inhibit the development of Mn oxidogenesis. The bulk of Mn compounds are confined to the silt rather than to the clay fraction, since manganese oxides are negatively charged in the pH interval typical of the bulk of soils. Manganese oxides are able to retain heavy metals, i.e., Co, Ni, Zn, and others. The active participation of Mn oxides in Cr(III) oxidation raises its mobility and toxicity. Manganese oxides may favor humus formation by taking part in phenol oxidation.     

Reactions of chrome tannery sludge with organic and mineral soils

Chrome tannery sludge applied to agricultural land may have benefits in terms of added N for crop growth. An experiment was designed to compare tannery waste with commercial N fertilizer and investigate the potential of the waste as an alternative or supplement to commercial fertilizer. Soils with 38% and 7% organic C and N content of 1.3% and 0.2%, respectively, were amended with lime, commercial N fertilizer, or tannery sludge containing 1.6% Cr. A portion of the tannery waste was supplemented with additional Cr 3⁺ salt before adding to the soils. The amended soils were analyzed for total Cr, ammonium acetate extractable Cr, selected nutrient and trace element concentrations. The tannery sludge increased soil pH, total Cr and N, S, Ca, P, Mg, and Na concentrations. DTPA extractable Cr increased only when Cr³⁺ salt was added, but soil pH decreased markedly. Electroconductivity of the soils increased with the waste application rate and, at the highest rate of Cr³⁺ salt addition, far exceeded values recommended for successful crop production. The acidic, high salt conditions complicated interpretation of the Cr³⁺ salt addition results. Tannery sludge may be applied to agricultural land as a fertilizer amendment without adversely affecting soil chemical properties. The amount and frequency of application should be determined by (1) total and available N, (2) total salt content, (3) total and available Cr, and (4) soil organic matter.