Immobilization and phytoavailability of cadmium in variable charge soils. II. Effect of lime addition

The effect of pH-increases due to Ca(OH)₂ and KOH addition on the adsorption of cadmium (Cd) was examined in two soils which varied in their variable-charge components. The effect of Ca(OH)₂ on immobilization and phytoavailability of Cd from one of the soils, treated with various levels of Cd (0–10 mg Cd kg^–1 soil), was further evaluated using mustard (Brassica juncea L.) plants. Cadmium immobilization in soil was evaluated by a chemical fractionation scheme. The addition of Ca(OH)₂ and KOH increased the soil pH, thereby increasing the adsorption of Cd, the effect being more pronounced in the soil dominated by variable charge components. There was a greater increase in Cd²⁺ adsorption in the KOH-treated than the Ca(OH)₂-treated soil, which is attributed to the greater competition of Ca²⁺ for adsorption. Increasing addition of Cd enhanced Cd concentration in plants, resulting in decreased plant growth (i.e., phytotoxicity). Although addition of Ca(OH)₂ effectively reduced Cd phytotoxicity, Cd uptake increased at the highest level, probably due to decreased Cd²⁺ adsorption resulting from increased Ca²⁺ competition. There was a significant inverse relationship between dry matter yield and Cd concentration in soil solution. Addition of Ca(OH)₂ decreased the concentration of the soluble + exchangeable Cd fraction but increased the concentration of inorganic-bound Cd fractions in soil. Since there was no direct evidence for CdCO₃ or Cd(OH)₂ precipitation in the variable charge soil used for the plant growth experiment, alleviation of phytotoxicity can be attributed primarily to immobilization of Cd by enhanced pH-induced increases in negative charge.     

Immobilization and phytoavailability of cadmium in variable charge soils. III. Effect of biosolid compost addition

We examined the effect of biosolid compost on the adsorption and complexation of cadmium (Cd) in two soils (Egmont and Manawatu) which varied in their organic matter content. The effect of biosolid compost on the uptake of Cd from the Manawatu soil, treated with various levels of Cd (0–10 mg Cd kg^–1 soil), was also examined using mustard (Brassica juncea L.) plants. The transformation of Cd in soil was evaluated by a chemical fractionation scheme. Addition of biosolid compost increased negative charge in soil. The effect of biosolid compost on Cd adsorption varied between the soils, with a large portion of the sorbed Cd remaining in solution as an organic complex. Increasing addition of Cd increased Cd concentration in plants, resulting in decreased plant growth at high levels of Cd (i.e., phytotoxicity). Addition of biosolid compost was effective in reducing the phytotoxicity of Cd as indicated by the decrease in the concentration of NH₄OAc extractable-Cd and soil solution-Cd. The solid-phase fractionation study indicated that the addition of biosolid compost decreased the concentration of the soluble and exchangeable Cd fraction but increased the concentration of organic-bound Cd fraction in soil. Alleviation of Cd phytotoxicity by biosolid compost can be attributed primarily to complexation of Cd by the organic matter in the biosolid compost.     

碱性土壤盐化过程中阴离子对土壤中镉有效态和植物吸收镉的影响

镉是土壤环境中对土壤质量有着极其重要影响的污染物之一,低含量下就能对人体和动物产生危害.镉在土壤中的有效态既决定了它的生物有效性及对环境的危害程度,又是人们对受污染土壤进行治理和修复的基础.作为盐化土壤中的典型组分,无机盐不可避免对镉的有效态及生物有效性等地球化学行为产生明显影响.研究了碱性土壤盐化过程中无机盐阴离子对土壤中镉有效态和植物吸收镉影响.研究方法为:以钠盐为例,实验研究了碱性土壤盐化过程中无机盐阴离子对土壤中镉有效态的影响;通过油菜种植试验,分析了无机盐阴离子对土壤中镉生物有效性的影响.研究结果表明,土壤盐化过程中,土壤溶液中Cl-浓度较低时,土壤中镉的有效态含量随Cl-浓度增加而增大,但当土壤中Cl-/Cd的比值大于100∶1时,土壤中镉的有效态含量达到最大值.土壤溶液中SO42-含量对土壤中镉有效态含量的影响不明显;随着土壤溶液中HCO3-含量的增加,土壤中镉的有效态含量明显减少.由于Cl-、SO42-是土壤溶液中的主要成分,随着盐度的增加,镉的有效态含量增加.油菜种植试验显示,当土壤中Cl-的含量增加时,土壤中镉的有效态含量增加,有利于植物对镉的吸收,因此油菜中镉的含量随土壤中Cl-的含量增加而增加,但当土壤有效态含量超过2 mg/kg后,油菜吸收镉已经达到最大.随着土壤溶液中SO42-浓度的增加,油菜中镉含量基本不变;土壤溶液中HCO3-的含量增加,植物中镉的含量随土壤中HCO3-含量增加而减少.这些特征与土壤镉有效态变化相吻合.通过各种措施控制土壤盐度和调节阴离子类型和含量,有利于降低土壤中镉的有效态含量,减轻镉的活化;农业生产中适当调整无机肥料的种类,可以减少农作物对镉的吸收.     

磷肥对土壤中镉的植物有效性影响及其机理

为寻求保障镉污染农田稻米质量安全的有效措施,采用盆栽方法研究了低镉磷肥(Cd＜0.2 mg·kg-1)及不同施磷量(0.10、0.20 g P2O5·kg-1)对污染稻田土壤中(潮泥田)镉的植物有效性影响,并探讨了相关机理.结果表明:在0.10 g·kg-1磷剂量水平下,与对照(无磷肥)相比,钙镁磷和磷酸二氢钾处理显著提高了土壤pH和降低了土壤镉活性,钙镁磷和过磷酸钙处理显著降低了水稻对镉的吸收累积;当施磷量增至0.20 g·kg-1时,磷酸氢钙处理显著提高了土壤pH和降低了土壤镉活性,钙镁磷、磷酸二氢钾和磷酸氢钙处理下DTPA提取态镉含量降低11.8％、9.8％和11.8％,NH4OAc提取态镉含量降低9.5％、7.1％和7.1％;5种磷肥处理均显著降低了水稻茎叶中镉含量(降幅24.9％ ～ 50.8％),除磷酸氢钙处理外,糙米镉含量的降幅均达到显著水平,钙镁磷和过磷酸钙处理下糙米镉含量接近国家粮食卫生标准(GB 2715-2005).5种供试磷肥中,能提高土壤pH的磷肥(钙镁磷、磷酸二氢钾和磷酸氢钙)降低土壤镉有效性的效果显著,含钙磷肥(钙镁磷和过磷酸钙)降低水稻镉积累的效果较好.磷肥化学性质的差异可能是影响其效果的主要原因,选择碱性含钙磷肥对控制污染农田中作物吸收累积镉更有效.     

Analysis of an engineered sulfate reduction pathway and cadmium precipitation on the cell surface

We previously have genetically engineered an aerobic sulfate reduction pathway in Escherichia coli for the generation of hydrogen sulfide and demonstrated the pathway's utility in the precipitation of cadmium. To engineer the pathway, the assimilatory sulfate reduction pathway was modified so that cysteine was overproduced. Excess cysteine was then converted by cysteine desulfhydrase to an abundance of hydrogen sulfide, which then reacted with aqueous cadmium to form cadmium sulfide. In this study, observations of various E. coli clones were combined with an analysis of kinetic and transport phenomena. This analysis revealed that cysteine production is the rate-limiting step in the engineered pathway and provided an explanation for the phenomenon of cell surface precipitation. An analytical model showed that cadmium sulfide must form at the cell surface because the rate of cadmium sulfide formation is extremely fast and the rate of sulfide transport is relatively slow.     

磷酸盐修复重金属污染土壤的研究进展

从研究方法、反应机理以及风险评价等方面综述了磷酸盐修复重金属污染土壤的研究进展,分析和讨论了其中存在的问题和不足,提出了今后加强研究的重点。目前磷酸盐修复重金属污染土壤时,使用的主要研究方法有化学形态提取法、化学平衡形态模型法和光谱及显微镜技术,各个方法都有其优缺点,应该结合使用并探索新方法。磷酸盐稳定重金属的作用机理主要有3个:磷酸盐诱导重金属吸附、磷酸盐和重金属生成沉淀或矿物和磷酸盐表面吸附重金属,但磷酸盐与重金属反应的机理十分复杂,人们尚不完全清楚,因此难以有效区分和评价诱导吸附机理和沉淀机理或其它固定机理,相应地对磷酸盐修复重金属的长期稳定性难以预测。磷酸盐修复重金属污染土壤时由于其较高的施用量可能会造成磷的积聚从而引发一些环境风险,如磷淋失造成水体富营养化,营养失衡造成作物必需的中量和微量元素缺乏以及土壤酸化等。所以应该谨慎选择磷肥种类和用量,最好是水溶性磷肥和难溶性磷肥配合、磷肥与石灰物质等配合施用。今后应着重研究磷酸盐与重金属相互作用的机理区分和评价;关注磷酸盐修复重金属污染土壤时存在的潜在风险,特别是加强植物长期不断吸收磷或其它环境条件变化致使土壤磷素持续减少过程中稳定的重金属溶解性和移动性的研究,磷酸盐修复重金属污染土壤的长期田间实践等。     

Effect of cadmium and calcium treatments on phytochelatin and glutathione levels in citrus plants

Industry residues, phosphate fertilisers and wastewater as a source of irrigation have considerably increased levels of heavy metals in the soil, mainly cadmium (Cd²⁺). To test the effects of a calcium (Ca²⁺) treatment on Cd²⁺ accumulation and plant tolerance to this heavy metal, plants of two citrus genotypes, Cleopatra mandarin (CM) and Carrizo citrange (CC), were watered with increasing concentrations of Cd²⁺, and phytochelatin (PC) and glutathione (GSH) content were measured. Both genotypes were able to synthesise PCs in response to heavy metal intoxication, although CM seems to be a better Cd²⁺ excluder than CC. However, data indicate that CC plants had a higher capacity for regenerating GSH than CM plants. In this context, the effects of Ca²⁺ treatment on Cd²⁺ accumulation, plant survival and PC, GSH and oxidised glutathione (GSSG) content were assessed. Data indicate that treatment with Ca²⁺ had two positive effects on citrus physiology: it reduced Cd⁺² uptake into roots and also increased GSH content (even in the absence of Cd²⁺). Overall, the data indicate that although Cd²⁺ exclusion is a powerful mechanism to avoid heavy metal build‐up into photosynthetic organs, the capacity to maintain optimum GSH levels to feed PC biosynthesis could also be an important factor in stress tolerance.     

镉对固定化小球藻除磷效果的影响

采用人工配制污水进行静态模拟实验,研究了镉对被海藻酸钙凝胶包埋固定的小球藻去除磷能力的影响.结果表明:在各光照及pH条件下,镉对固定化小球藻吸收磷的效果随着实验时间的推移而变化,在实验的第一天时影响最大;总体而言,镉抑制了固定化小球藻的除磷能力,但在某些条件下镉反而提高了藻对磷的吸收;固定化处理减弱了镉对小球藻除磷能力的影响.具体的光照、pH值与镉的影响效果的关系尚待进一步探讨.     

Effects of biochar and nitrogen addition on nutrient and Cd uptake of Cichorium intybus grown in acidic soil

Biochar is an organic amendment used for soil remediation, there are only a few studies documenting the effects of nitrogen on the role of biochar in contaminated soils. A pot experiment was conducted to investigate the impacts of biochar (0%, 1%, and 2.5%, w/w) and nitrogen (0, 100, and 200 mg N kg^?1) on plant growth, nutrient and cadmium (Cd) uptake of Cichorium intybus. N, P, Ca, Mg, and Cd concentrations increased with N level in 0% and 1% biochar treatments. In plants treated with 2.5% biochar, 200 mg N kg^?1 addition caused significant reductions of N, P, Ca, Mg, and Cd concentrations in comparison to 100 mg N kg^?1 treatments. Nitrogen promoted shoot biomass at all biochar treatments, while biochar had no effect on shoot biomass in 0 and 200 mg N kg^?1 addition treatments. Nitrogen also significantly increased N, P, K, Ca, Mg, and Cd contents in the 0% and 1.5% biochar addition treatments. Although soil DTPA-extractable Cd concentration showed the lowest values in 1% biochar in combination with 100 and 200 mg N kg^?1 addition treatments, lowest shoot Cd concentration, and relatively high shoot biomass occurred in the 2.5% biochar + 200 mg N kg^?1 treatment. Based on these results, biochar application at its highest rate (2.5%) in combination with high N supply (200 mg N kg^?1) contributed to both crop yield and agricultural product safety. N input alone might increase the risk of human health, and the optimum N dose should be determined during phytostabilization process.     

Roles of calcium and cadmium on Cd-containing intra-and extracellular formation of Ca crystals in tobacco

Growth was severely inhibited when tobacco plants were exposed to toxic levels of cadmium (0.2 mM). However, when this treatment was combined with a high concentration of calcium (30 mM), the Cd-induced damage was strongly alleviated. Under these enhanced conditions, i.e., 30 mM Ca and 0.2 mM Cd, Ca crystals not only were heavily deposited in the leaves but were also actively excreted from the trichomes. The X-ray spectrum from our Energy Dispersive analysis revealed that both intra-and extracellular Ca crystals contained detectable amounts of Cd. Moreover, intracellular Ca deposition in the leaves was stimulated only by a high Ca concentration (30 mM); moderate levels of Ca (3 mM) or a toxic amount of Cd (0.2 mM) alone resulted in crystal deposition that was undetectable under a light microscope. In contrast, extracellular crystal formation on the trichomes was stimulated by toxic Cd treatment but not by high Ca concentrations alone. Finally, Inductively Coupled Plasma Spectroscopy revealed that a high level of Ca (30 mM) suppressed Cd accumulation while also increasing the endogeneous Ca concentration in the leaves. These observations imply that the amelioration of Ca against toxic Cd in tobacco plants is a result of not only the inhibition of Cd uptake, but also the extra-and intracellular sequestration of cadmium via Ca crystallization.     

超积累植物伴矿景天镉耐受基因SpMT2的分离及功能鉴定

超积累植物由于其对重金属具有地上部超积累以及超耐受等特性,不仅是研究植物离子转运及毒性耐受的理想模式,而且在植物修复的发展和应用中具有不可替代的作用。伴矿景天是近年在我国境内发现的一种景天科镉(Cd)/锌(Zn)超积累植物。为鉴定其富集和耐受Cd的关键基因,笔者构建了其酵母表达cDNA文库,利用酵母的遗传互补系统筛选到一个极大提高了酵母抗Cd能力的基因SpMT2。SpMT2属于富含半胱氨酸(Cys)的金属硫蛋白(Metallothionein)家族。亚细胞定位表明SpMT2表达于酵母细胞质中,并特异地提高酵母对Cd的抗性。进一步研究发现SpMT2的表达显著降低了酵母液泡中Cd含量,但酵母吸收的总Cd含量无显著变化。推测抗性增加是由于SpMT2在酵母细胞质中通过螯合Cd从而降低Cd对酵母的毒害。qRT-PCR分析表明SpMT2在伴矿景天的根和地上部都高丰度表达,且不受Cd诱导变化。鉴于SpMT2也定位于植物细胞质中,结合上述结果,推测SpMT2可能在伴矿景天细胞质中螯合Cd,在降低Cd毒害的同时可能还保持Cd在细胞质中的流动性,从而在Cd长途转运过程中也发挥重要作用。     

碳酸钙对土壤镉吸附及解吸的影响

采用等温吸附法,并以1mol/L KNO3进行解吸试验,研究CaCO3对3种土壤镉吸附和解吸的影响。结果表明,3种土壤的原状土样对镉吸附总趋势为：栗钙土＞棕壤＞淋溶褐土,均符合Langmuir方程、Frenudlich方程和Temink方程,其中以Freumdlich方程最佳。镉的专性吸附量表现为栗钙土＞淋溶褐土＞棕壤。添加CaCO3使3种土壤中镉的吸附量增加,增加幅度棕壤为4％－11％,淋溶褐土2％－11％,栗钙土2％－8％。外界加入的镉浓度越高,增加幅度越大。Freundlich方程（lgX=lgK lgC/n）拟合的参数结果表明：加入CaCO3后,K和n值均下降;Langmuir方程中镉最大吸附值增加,吸附平均常数减小。可以推测,CaCO3的存在之所以能够使土壤体系吸附镉能力增加,除CaCO3本身的吸附作用增加,吸附平衡常数减小。可以推测,CaCO3的存在之所以能够使土壤体系吸附镉能力增加,除CaCO3本身的吸附作用外,还可能影响反应体系的平衡系数。加入CaCO3,土壤对镉的专性吸附明显增加,尤其以棕壤专性吸附的镉最多,淋溶褐土其次,而栗钙土增加较少,栗钙土去除CaCO3后,镉的吸附减少了2.0%-26.0%,土壤专性吸附的镉减少4.0%-38.2%。3种土壤镉的解吸能力表现为：棕壤＞淋溶褐土＞栗钙土。添加CaCO3,土壤镉的解吸量下降。去除CaCO3后,栗钙土匐解吸量明显增加。     

重金属镉(Cd)在植物体内的转运途径及其调控机制

重金属镉(Cd)的毒害效应与其由土壤向植物地上部分运输有关,揭示Cd~(2+)转运途径及其调控机制可为提高植物抗镉性以及镉污染的植物修复提供依据。对Cd~(2+)在植物体内的转运途径,特别是限制Cd~(2+)移动的细胞结构和分子调控机制研究进展进行了回顾。Cd~(2+)通过共质体和质外体途径穿过根部皮层进入木质部的过程中,大部分在皮层细胞间沉积,少部分抵达中柱后转移到地上部分。为了免受Cd~(2+)的危害,植物体产生了多种限制Cd~(2+)吸收和转移的生理生化机制:1)环绕在内皮层径向壁和横向壁上的凯氏带阻止Cd~(2+)以质外体途径进入木质部;2)螯合剂与进入根的Cd~(2+)螯合形成稳定化合物并区隔在液泡中;3)通过H+/Cd~(2+)离子通道等将Cd~(2+)逆向转运出根部。植物共质体和质外体途径转运重金属镉的能力以及两条途径的串扰尚待进一步明晰和阐明。     

Effect of cadmium on growth and the activity of H2O2 scavenging enzymes in Colocassia esculentum

Cadmium is a non-essential heavy metal that can be harmful even at low concentrations to plants. Colocassia esculentum (Araceae) plant was studied to know its tolerance capability to cadmium. Colocassia esculentum plants grown in pots containing different concentrations of cadmium (Cd) were analyzed for dry matter, fresh weight and total metal content. Cadmium depressed dry matter production of the plant up to 33%. Plant accumulated larger portion of the heavy metal in the roots followed by stem and leaf. Chlorophyll content of the plant declined on treatment with heavy metal while the activity of antioxidative enzymes catalase and peroxidase increased. Colocassia esculentum also showed an increase in total protein along with greater A₂₅₀/A₂₈₀ value suggesting an increase in metal protein complexes. Cadmium elicited anatomical changes in the root of C. esculentum. These changes under heavy metal stress indicate the adaptive properties of this plant species.     

微生物镉解毒机制及微生物-植物互作修复研究进展

镉(cadmium,Cd)是引起粮食减产的主要金属之一,具有高溶解性及高迁移性,易被植物吸收和积累。微生物长期在镉胁迫的条件下进化出一系列的镉解毒机制。微生物对镉的解毒包括抑制Cd(Ⅱ)的进入、促进Cd(Ⅱ)的外排,以及将进入胞内的Cd(Ⅱ)进行“扣押”。微生物的Cd(Ⅱ)钝化是通过细胞吸附和胞外沉淀将游离态的Cd(Ⅱ)进行钝化,这类微生物具有较强的土壤镉污染治理潜力。本文主要介绍微生物的镉解毒机制、微生物-微生物互作、微生物-植物互作机制及其在镉污染生物修复中应用的最新研究进展。     

Effect of acidulation of high cadmium containing phosphate rocks on cadmium uptake by upland rice

Little information is available in literature on Cd uptake by crops from either phosphate rock (PR) or partially acidulated PR (PAPR). The purpose of this greenhouse experiment was to study the effect of acidulation of two PRs having high Cd content (highly reactive North Carolina PR and low-reactive Togo PR) on Cd uptake by upland rice. The degrees of acidulation with H₂SO₄ were 100% for North Carolina PR (NC-single superphosphate [SSP]) and 50% or 100% for Togo-PR (i.e., Togo PAPR or Togo-SSP). Separation of the confounding effect between P uptake and Cd uptake from various P sources was made by adding 200 mg P/kg as KH₂PO₄ to all the treatments. Rates of Cd added from various P sources were 50–400 µg Cd/kg. Upland rice (Oryza sativa L.) was grown on two acid soils (Hartsells, pH 5.0 and Waverly, pH 5.6) to maturity.The results show that Cd uptake by rice grains followed the order of NC-SSP> NC-PR and Togo SSP> Togo PAPR> Togo PR. The results also showed that most of the Cd uptake was retained in rice roots and straw. Total uptake of Cd, Ca, and P by rice plant (root, straw, and grain) was higher from NC-PR than from Togo-PR. Cd concentration in rice grains showed no significant difference between NC-PR and Togo-PR, whereas Cd concentrations in root and straw were higher with NC-PR than that with Togo-PR. There was a significant relationship between total Cd uptake by rice plant and Cd extracted by DTPA from soils treated with various P sources at 400 µg Cd/kg.     

Distribution of cadmium in leaves of cadmium tolerant and sensitive ecotypes of Silene vulgaris

It has been postulated that vacuolar compartmentation might play an important role in naturally selected cadmium tolerance in Silene vulgaris (Moench.) Garcke (Bladder campion). Additionally, a tendency of heavy metals to accumulate in the epidermis has been reported. Since these factors would affect the distribution of cadmium in leaves, we determined the distribution of cadmium in leaves of cadmium tolerant and sensitive ecotypes of Silene vulgaris at different levels of exposure and at different time intervals. Cadmium concentrations were higher in leaves of sensitive plants than in those of cadmium tolerant ones after identical exposure to cadmium for a period of 8 days. The highest cadmium concentrations were found in the lower epidermis of plants of both ecotypes. The amount of cadmium located at the lower epidermis was highest for sensitive plants, although the stomatal density was lower in the sensitive ecotype than in the tolerant one. A possible explanation for this phenomenon is the weak relationship between transpiration (water flow) and element allocation. Our results support the hypothesis that vacuolar storage of cadmium plays an important role in the mechanism of cadmium tolerance in Silene vulgaris .     

Characterization of cadmium desorption in soils and its relationship to plant uptake and cadmium leaching

Experiments on Cd desorption were conducted with a range of water-to-soil ratios to assess the desorption characteristics of Cd in soils and the availability of Cd for absorption by plant roots and leaching to groundwater, Soil samples were collected from sites contaminated by a former Pb and Zn smelter, by sewage irrigation, or with artificial additions of Cd and sewage sludge. Glasshouse pot experiments were conducted in which the yield and Cd uptake of crop plants were determined. Cadmium leached from soil columns was also studied using soil lysimeters. The soil solution Cd concentration decreased with increasing solution-to-soil ratio and followed a negative power function. Two constants obtained from logarithmic linear regression were identified. The intercept (C₁) was Cd concentration in the soil solution where the solution/soil ratio was equal to 1 and this constant was the intensity factor of the initial element supply in the soil. The slope (a) showed a decreasing trend for Cd concentration in the soil solution which was related to the soil buffering capacity. A corrected concentration (C₁/a) is proposed for expressing soil desorption ability. This combined index was significantly correlated with Cd uptake by plants and also with Cd leached from soil columns.     

Cadmium resistant Enterobacter cloacae and Klebsiella sp. isolated from industrial effluents and their possible role in cadmium detoxification

Three bacterial strains, two of Klebsiella sp. and one Enterobacter cloacae were isolated from industrial effluents of chemical and textile industries. They showed high efficiency in removing cadmium (Cd²⁺) from the medium. When 100 g/ml of Cd was added to the medium, the three isolates namely CMBL-Cd1, CMBL-Cd2 and CMBL-Cd3 removed or accumulated 86%, 87% and 85% of Cd, respectively, from the medium within 24h. Plasmids were detected in all the three strains. Plasmids of E. cloacae (pCBL1) and Klebsiella sp. (pCBL2 and pCBL3), estimated to be 6.6kb, were used to transform Escherichia coli C600. The transformed E. coli cells showed elevated resistance to Cd. Ethidium bromide curing indicated the presence of the Cd resistance gene on the plasmid. Resistance of the isolated strains against other metals like chromium (cr⁶⁺) and lead (pb²⁺) and a number of antibiotics was also checked. Cured strains showed lowered resistance against Cr and some antibiotics. This again supported the indication of the presence of Cd, Cr and some antibiotics resistance genes on plasmids.