外源铜在土壤中的老化研究进展

水溶性Cu添加到土壤后,其可浸提性、生物有效性或毒害随时间逐渐降低,这个过程称为老化过程.田间污染土壤中的Cu与人工新添加的Cu在生物有效性上存在着明显的差异,因此,在生态风险评价和环境质量标准制定中,考虑Cu的老化过程显得十分必要.而且,它对污染土壤的管理和修复也有重要的指导意义.本文详细综述了外源Cu在土壤中的老化机理及影响因素,指出老化过程主要受扩散作用、聚合/沉淀作用和包裹作用共同控制,而且在长期老化阶段,微孔扩散成主导作用机理;pH、温度、有机质和土壤类型是老化的主要影响因子,其中pH影响聚合/沉淀作用和扩散作用,温度主要影响扩散作用,而有机质对上述各个机理都有影响.     

耕型红壤和红壤性水稻土铜的化学形态及其有效性

对湖南省 1 0个有代表性红壤样品进行化学分组测定 .结果表明 ,土壤有机态、无定形铁态、晶形铁态和残留态铜分别占全铜量的 1 5 2 %、1 1 7%、1 7 2 %和 5 6 0 % .红壤性水稻土有机态和无定形铁态铜 ,明显高于耕型红壤 ,而晶形态、残留态铜则相反 ,供试土壤有效铜含量与土壤有机态铜和无定形铁态铜含量呈极显著性正相关     

蘑菇渣和鸡粪对土壤外源铜形态变化的影响

采用室内模拟培养的试验方法,研究添加不同用量(2%,4%和6%)蘑菇渣和鸡粪分解对土壤外源铜形态变化的影响.结果表明:与对照(不添加有机物料处理)相比,蘑菇渣和鸡粪两处理均降低了松结合态铜的百分含量,降低幅度为6%处理4%处理2%处理,蘑菇渣处理的降低幅度大于鸡粪处理.在培养过程中,添加蘑菇渣和鸡粪的处理土壤松结合态铜百分含量呈现下降-上升-下降的趋势.蘑菇渣和鸡粪两处理均增加了可交换态铜和铁锰氧化物结合态铜的百分含量,对可交换态铜的提高作用显著(P<0.01).提高幅度为4%处理2%处理6%处理.对铁锰氧化物结合态铜的提高幅度为4%处理6%处理2%处理,鸡粪处理提高幅度大于蘑菇渣处理;蘑菇渣处理和鸡粪处理显著降低了碳酸盐结合态铜的百分含量(P<0.01).降低幅度6 0A处理4%处理2%处理,蘑菇渣处理降低幅度大于鸡粪处理,碳酸盐结合态铜的降低,是松结合态铜含量降低的主要原因.蘑菇渣和鸡粪两处理显著增加了有机结合态铜百分含量(P<0.01),增加幅度为6%处理4%处理2%处理,蘑菇渣处理的增加幅度要大于鸡粪处理.     

土壤外源铜形态的动态变化：5年定位试验

土壤铜污染的危害性不仅取决于总量,还与其在土壤中的形态有关。选用未受污染的粘质壤土,设置对照（32mg·kg-1）、200、400mg·kg-1铜处理模拟土壤铜污染,进行持续5年（2006—2010年）的稻/麦轮作土培试验。参照Tessier的方法测定小麦和水稻成熟期土壤中不同形态铜含量,研究耕作层土壤中各种形态铜含量的动态变化。结果表明：（1）试验期内清洁土壤中总铜以及可交换态、碳酸盐结合态、铁锰氧化物结合态、有机物结合态、残渣态铜含量变化均很小,铜处理使上述参数均大幅增加。（2）污染土壤各形态铜含量随时间推移而变化,其中可交换态浓度持续下降最为显著,5年分别累计下降66%（200mg·kg-1）、67%（400mg·kg-1）。（3）土壤处于旱作条件有利于碳酸盐结合态和有机物结合态铜向铁锰氧化物结合态转化,淹水条件下转化方向相反。（4）铜处理改变了土壤中铜元素的形态分布,清洁土壤主要以残渣态存在（平均占57%）,污染土壤中碳酸盐结合态和铁锰氧化物结合态铜所占的比例明显增加（合计平均占58%）。本研究表明,外源铜进入土壤后,易被植物吸收利用的可交换态浓度持续大幅降低,其他形态则因不同年度和不同耕作方式而相互转化。     

污泥土地利用研究II. 连续化学提取法研究施污泥土壤重金属的有效性和环境风险

本文采用连续化学提取法研究了施用污泥土壤中重金属的形态分配及有效性。铜和锌在2种土壤上施用污泥前、后的形态分配都有所差异,铜在河湖相水稻土上以可氧化态为主;红壤性水稻土可氧化态和可还原态含量都较高。锌在河湖相水稻土以可还原态为主,在红壤性水稻土以醋酸溶解态为主。两种土壤上,铜和锌的3种不同形态含量与污泥施用量之间都有很好的相关性。连续提取对于研究重金属的形态分配比单独提取更有价值。     

污泥土地利用研究：Ⅱ、连续化学提取法研究施污泥土壤重金属的有效性和环境风险

本文采用连续化学提取法研究了施用污泥土壤中重金属的形态分配及有效性。铜和在2种土壤上施用污泥前、后的形态分配都有所差异，铜在 湖相水稻土上可以氧化态为主：红壤性水稻土可氧化态和可还原态含量都较高。锌在河湖相水稻土以可还原态为主，在红壤性水稻土以醋酸溶解态为主，两种土壤上，铜和锌的3种不同形态含量与污泥施用量之间都有很好的相关性，连续提取对于研究重金属的形态分配比单独提取更有价值。     

施用猪粪对不同类型土壤中铜的赋存形态及小白菜吸收铜的影响

【目的】探讨猪粪中铜（Cu）的输入对土壤中Cu的赋存和生物有效性的影响。【方法】将1%和3%的腐熟猪粪（干猪粪∶秸秆=10∶1）添加到黄褐土、红壤、黑土、褐土中,分别老化0、1、2、3、5个月后,进行小白菜盆栽实验。【结果】与对照相比,施用猪粪使黄褐土、红壤、黑土和褐土土壤铜（Cu）全量分别显著增加了20.23%～50.43%、79.87%～142.6%、52.41%～76.43%和41.14%～92.24%。四种土壤中水溶态（F1）、碳酸盐结合态（F3）Cu占比均增加,施用3%猪粪的红壤未老化处理中F1-Cu和黄褐土未老化处理中F3-Cu增幅最大,分别达4.55%和16.47%。土壤铁锰氧化态（F5）、有机结合态（F6）Cu占比增加,残渣态（F7）占比降低。土壤有效态Cu的占比与猪粪老化时间呈显著负相关,3%猪粪老化5个月处理的黄褐土、黑土和褐土土壤有效态Cu占比分别降低12.85%、4.11%和3.68%,而红壤有效态Cu占比随老化时间变化不显著。在黄褐土中,腐殖酸结合态（F4）Cu的占比随猪粪老化时间的延长逐渐增加。施用猪粪显著增加小白菜对Cu的吸收,其中红壤的增幅最大,根系与地...     

外源铅胁迫对不同土壤上水稻生长及铅形态的影响

采用温室水稻盆栽试验研究2种土壤上水稻铅的生物有效性及土壤铅形态的变化。结果表明:铅对2种土壤水稻干物重和籽粒重量的影响表现为,随铅处理浓度升高,水稻干物重和籽粒重量明显下降。黄红壤上种植的水稻干物重和籽粒重量高于青紫泥。不同铅处理下水稻各器官铅含量表现为根>茎>叶>壳>籽粒。2种土壤上NH4OAc提取的有效态铅含量与外源铅的量呈显著正相关。随外源土壤铅含量增加土壤pH显著下降。随土壤铅含量增加土壤铅的生物有效性增强,水稻对铅的吸收明显增加,水稻可食部的铅含量升高。采用连续提取法分析了土壤铅的形态,结果表明,青紫泥铁锰氧化态和有机态的铅含量高于黄红壤,水溶态、交换态和碳酸盐态含量低于黄红壤。铅在黄红壤上的移动性较青紫泥高。     

Chemical transformation of copper in some sludge-amended soils

In a laboratory incubation study, the periodic changes in different chemical fractions of copper (Cu) in three sludge-amended soil types (acidic sandy clay loam, neutral clay loam and alkaline clay loam) of varying soil reaction were monitored under field capacity and flooding moisture regime over 16 months. The water soluble and exchangeable fraction of Cu was very low (≤1% of total Cu) in all three soil types. At the end of incubation (16 months), the sodium acetate extractable (carbonate sorbed)- and residual-Cu fractions transformed into Fe-Mn oxide fraction, irrespective of moisture regime in all three soil types. However, the extent of transformation varied among soils.     

Time effects of rice straw and engineered bacteria on reduction of exogenous Cu mobility in three typical Chinese soils

Globally, copper (Cu) accumulation in soils is a major environmental concern. Agricultural organic waste and some bacterial species can readily absorb metals in an eco-friendly manner, and thus are commonly used in metal-contaminated soil remediation. This study investigates the change in Cu fractions during the aging process and the time effects of rice straw (RS) and engineered bacteria (EB) (Pseudomonas putida X4/pIME) on reduction of Cu mobility. Three typical Chinese soils (red, cinnamon, and black soils) were incubated with RS or RS + EB in the presence of exogenous Cu for 24 months. The soil physicochemical properties, reactive soil components, Cu fractions, and Cu mobility were determined over time. The Cu mobility factor (MF) values were the lowest in the black soil (6.4-9.2) because of its high organic carbon and clay contents. The additions of both RS and RS + EB accelerated Cu stabilization during the aging process in all three soils. The Cu MF values decreased with time during the initial 20 months; however, the MF values increased thereafter in all soils, which might be due to the reduction of humic substances and amorphous iron oxides and the increase in iron oxides complexed on the organic matter. The reduction rates of Cu MF were similar after 16, 24, and more than 24 months in the red, cinnamon, and black soils, respectively, indicating that RS and RS + EB could limit Cu mobility at different times in various soils. The RS treatment showed the greatest efficiency in reducing Cu mobility in the red, cinnamon, and black soils after 12, 12, and 8 months of incubation, respectively. The RS + EB treatment was more efficient than the RS treatment in the red soil during the initial 8 months of the incubation period. Our study provides theoretical support for Cu risk assessments and RS supplementation for Cu remediation in different soils.     

Concentrations and forms of heavy metals in Slovak soils

The risk assessment of heavy‐metal contamination in soils requires knowledge of the controls of metal concentrations and speciation. We tested the relationship between soil properties (pH, CEC, C_org, oxide concentrations, texture) and land use (forest, grassland, arable) and the partitioning of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn among the seven fractions of a sequential extraction procedure in 146 A horizons from Slovakia. Using a cluster analysis, we identified 92 soils as representing background metal concentrations while the remaining 54 soils showed anthropogenic contamination. Among the background soils, forest soils had the lowest heavy‐metal concentrations except for Pb (highest), because of the shielding effect of the organic layer. Arable soils had the highest Cr, Cu, and Ni concentrations suggesting metal input with agrochemicals. Grassland soils had the highest Cd and Zn concentrations probably for geogenic reasons. Besides the parent material (highest metal concentrations in soils from carbonatic rock, lowest in quartz‐rich soils with sandy texture), pedogenic eluviation processes controlled metal concentrations with podzols showing depletion of most metals in E horizons. Partitioning among the seven fractions of the sequential extraction procedure was element‐specific. The pH was the overwhelming control of the contributions of the bioavailable fractions (fractions 1–4) of all metals and even influenced the contributions of Fe oxide‐associated metals (fractions 5 and 6) to total metal concentrations. For fractions 5 and 6, Fe concentrations in oxides were the most important control of contributions to total metal concentrations. After statistically separating the pH from land use, we found that the contributions of Cu in fractions 1–4 and of NH₄NO₃‐extractable Al, Cd, Pb, and Zn to total metal concentrations were significantly higher under forest than under grassland and in some cases arable use. Our results confirm that metal speciation in soils is mainly controlled by the pH. Furthermore, land use has a significant effect.     

Chemical forms and stability of selenium in soil

The chemical forms of selenium (Se) in soils derived from different parent rocks, and the stability of Se species in soils were investigated. Around 40% of the total Se occurred as organic Se on the average. Total selenite content was higher than that of total selenate. The content of organic Se decreased with heating of the soils at high temperatures, and most of it disappeared at heating temperatures above 500°C. However, the results of incubation experiments indicated that Se species were stable in soil, and that their chemical forms did not change appreciably with the variation of soil conditions. In soluble Se, organic Se accounted for about 50%, and in contrast to the total Se, the selenate content was higher than that of selenite.     

Chemical forms and sorption of copper and zinc in soils of central Chile

Abstract

Soil samples from a field irrigated with untreated industrial and municipal wastewater for several decades and from a field not receiving wastewater (control) were analyzed for total copper (Cu) and zinc (Zn) and for the amount of these elements removed in sequential extractions with MgCl₂, NaOAc, NH₂OH#lbHCl, 6H₂O₂‐HNO₃‐NH₄OAc, and HNO₃‐HF‐HCl. Organically‐bound Cu forms predominated in the wastewater‐affected soil while in the control soil both residual and organic forms yielded the same proportion of Cu. Distribution of Zn was different in the diverse fractions, and in the polluted soil the reducible and the residual forms predominated while in the control soil the residual form accounted for the highest proportion of recovered Zn. Sequential extraction of Cu from a copper sulfate‐treated soil incubated for 32 days at constant temperature resulted in the same proportional distribution of Cu forms in the polluted soil. In the control soil the oxidizable form decreased and the residual one increased noticeably. The two‐surface Langmuir adsorption model was used to adjust data and to interpret Cu and Zn adsorption by soils excepting Cu sorption by the polluted soil, where the one‐surface model was applied.     

Labile pools of copper and zinc in calcareous soils as measured by DTPA and plant extraction

Abstract

Labile pools of Cu and Zn were measured on two calcareous soils from Saudi Arabia, using successive extraction with DTPA, and successive cropping followed by extraction with DTPA after cropping. The examined soils differed in their ability to supply Cu and Zn. The first DTPA extraction removed a major proportion of the labile pool, particularly in the sandy soil. The two soils showed a general decrease in extractable Cu and Zn with progressive extractions, with DTPA extractable Cu declining more rapidly than Zn. DTPA extractable Cu and Zn determined after cropping were highly correlated with DTPA extractable Cu and Zn values obtained after successive extractions. The results gave evidence on both the contribution of element dissolution from insoluble forms with progressive extraction or cropping, and the usefulness of the DTPA extractant for monitoring the availability of Cu and Zn in these calcareous soils.     

Comparisons of Various Chemical Extracts as Quantity Factors to Determine Metal-Buffering Capacity of Soils

Applicability of various chemical extracts was investigated as quantity (Q) factors to determine cadmium (Cd), zinc (Zn), and copper (Cu) desorption quantity–intensity (Q/I) relationships in soils. The metal extracts were sums of sequential metal fractions (except the residual fraction) using Tessier's (TSE) and Community Bureau of Reference (BCR) procedures and various single chemical extracts: 1.0 M potassium nitrate (KNO₃), 1.0 M magnesium nitrate [Mg(NO₃)₂], 1.0 M magnesium chloride (MgCl₂), and 0.11 M acetic acid (CH₃COOH) solutions. Water-extractable metal was applied as a fixed intensity (I) factor. The TSE or BCR metal fractions were significantly correlated with diethylenetriaminepentaacetic acid (DTPA)–extractable metals, and all the metal desorption Q/I curves were linearly fitted. However, most of metal BC values estimated by using the single chemical extracts were very low and did not have consistent trends for target metals. Only 0.11 M CH₃COOH-extractable metals might be reliable. Therefore, TSE and BCR metal fractions can be applicable to replace DTPA-extractable metals, and 0.11 M CH₃COOH-extractable metals might also be useful.     

Accumulation and distribution of copper and zinc in soils following the application of pig slurry for three to thirty years in a microwatershed of southern Brazil

The application of pig slurry to soil can result in the accumulation of soil Cu and Zn, alter soil Cu and Zn fractions, and result in soil, surface water, and subsurface water contamination. This study evaluated the accumulation and distribution of Cu and Zn in soil profiles from 10 areas treated with pig slurry for 3–30 yr. A microwatershed within the municipality of Braço do Norte in the state of Santa Catarina and in the southern region of Brazil was studied. Hapludalf soil samples were collected at depths of 0.0–0.05, 0.05–0.10, 0.10–0.20, 0.20–0.30, and 0.30–0.40 m from 10 areas where pig slurry had been applied for 3–30 yr. The soil samples were dried, prepared, and analyzed to determine their chemical characteristics, particularly to quantify their Cu and Zn fractions. Although long-term pig slurry application resulted in greater available Cu and Zn concentrations in the surface soil layer, the migration of available Cu in the soil profile only occurred in areas that were subjected to more than 17 yr of slurry application. The application of pig slurry increased the available Cu and Zn contents in the surface soil layer; however, the available Cu in the soil profile increased in the areas with more than 17 yr of slurry application. Cu accumulation mainly occurred in the organic and mineral soil fractions, and Zn accumulation mainly occurred in the mineral fraction. Overall, Cu posed a greater risk for surface water contamination than Zn, especially in areas with more than 17 yr of pig slurry application.