磷酸盐、石灰和膨润土降低冶炼厂污染石灰性土壤重金属活性的研究

通过土壤培养试验探讨了磷酸盐配合石灰或膨润土对铅冶炼污染石灰性土壤(全铅和全镉含量分别为497和5.22 mg kg-1)中铅、镉等重金属的稳定效果。石灰和膨润土均可使土壤pH明显上升,而磷酸盐使土壤pH下降。各处理措施均使土壤EC上升。膨润土、石灰有利于土壤磷有效性下降。稳定剂施用后30 d时,与对照相比,磷酸盐单独施用、石灰单独施用、膨润土单独施用、磷酸盐配合膨润土施用处理土壤DTPA-Pb含量分别下降了5.92%、16.7%、9.24%和17.9%;培养60 d时,以上处理DTPA-Pb含量与对照相比下降比例分别为6.15%、17.6%、14.5%和16.4%,而磷酸盐施用30 d后再施用一半石灰的处理DTPA-Pb含量下降14.2%。与铅相比,稳定措施对镉的有效性影响较小,仅有石灰单独施用和磷酸盐施用30 d后再施用一半石灰处理DTPA-Cd含量显著低于对照(P 0.05),降低比例分别为2.54%和5.51%。以上结果表明,对于铅冶炼污染石灰性土壤,磷酸盐配合膨润土施用、磷酸盐施用后一段时间再施用石灰均可促进镉、铅的稳定,磷酸盐配合石灰施用可降低土壤磷的风险。     

重金属污染农田土壤化学钝化修复的稳定性研究进展

化学钝化修复是一种应用广泛的重金属污染农田土壤修复方法,但钝化修复只是暂时降低了土壤中重金属的移动性和生物有效性,随着时间的推移被固定的重金属有可能重新释放到土壤中,因此钝化修复重金属污染土壤的稳定性是重金属污染土壤原位钝化修复成功的关键。本文探讨了钝化修复剂的种类、修复机制、修复稳定性的影响因素以及修复稳定性的研究方法,深入分析了钝化修复稳定性的研究现状和存在问题,并提出今后应加强钝化修复稳定性机制和修复稳定性预测模型的研究,建立和完善科学的钝化修复稳定性的研究方法。     

重金属污染农田土壤修复效果评价指标体系分析

重金属污染农田土壤经修复后,是否达到了预期的目标,是否可以复垦为农田,生产的农作物是否达到了安全水平,这些问题均需要通过对修复后的效果进行评价来给出明确的答复。然而,目前,有关重金属污染农田土壤修复效果评价指标体系方面的研究还很少。从污染农田土壤修复效果评价的实际需求出发,本着全面性、客观性、易测性、可评性的原则,提出了一套推荐评价指标体系,并给出了各指标的分析方法及评价标准,以期为重金属污染农田土壤修复效果评价体系的建立及土壤修复标准的制定等提供参考依据。     

土壤重金属复合污染的化学固定修复研究

本文研究糠醛渣、磷矿粉、风化煤3 种修复剂对重金属复合污染土壤的化学固定修复效果.结果表明:糠醛渣、磷矿粉、风化煤3 种修复剂都可一定程度地降低复合污染土壤中的Cu、Zn、Pb、Cd含量,其中以风化煤降低土壤有效态Zn、Cu的效果较好,在风化煤添加量为80 g/kg时土壤有效态Zn的含量降低了37.22%,土壤有效态Cu的含量降低了31.22%;磷矿粉处理修复Pb的效果比糠醛渣、风化煤好,在磷矿粉添加量为80 g/kg时,土壤有效态Pb的含量降低了23.79%;3 种修复剂都能显著降低土壤有效态Cd,在磷矿粉添加量为40 g/kg时,土壤有效态Cd的含量降低最显著,较对照降低了83.09%.在本试验条件下,3 种修复剂对4 种重金属复合污染土壤的修复效果,以Cd 较好,其次是Zn,对Pb的修复效果较差.     

重金属污染土壤清洗导致几种营养元素流失的研究

通过HCl、柠檬酸、EDTA这3种提取剂对Pb、Cd、Cu、Zn污染土壤的漫提试验，研究了土壤清洗洗脱重金属的效果，并探讨了土壤清洗导致K、Ca、Mg、Fe、Mn这几种营养元素的流失和有效性的改变。试验结果表明，土壤清洗能有效地洗脱土壤中的Ph、Cd、Cu、Zn，伺时也造成了土壤中K、Ca、Mg、Fe、Mn的流失，降低了其中部分营养元素的有效性。EDTA对重金属的洗脱能力大于HCl和柠檬酸。HCl漫提造成的K、Ca、Mg的流失量大于柠檬酸和EDTA，柠檬酸浸提造成的Fe流失量大于HCl和EDTA，EDTA漫提造成的Mn流失量大于HCl和柠檬酸。HCl和柠檬酸浸提降低了土壤K、Ca、Mg的有效性EDTA浸提提高了土壤K的有效性。降低了土壤Ca的有效性。在高浓度时（50mmol／L），EDTA显著地降低了土壤Mg的有效性。HCl漫提导致土壤K的有效性下降比柠檬酸严重，高浓度的EDTA浸提导致土壤Ca的有效性下降比HCl和柠檬酸严重。HCl、柠檬酸、EDTA浸提都能提高土壤中Fe的有效性．且EDTA的效应大于其它2种萃取剂；在低浓度时，3种提取剂都能提高土壤中Mn的有效性，且以柠檬酸的作用最为明显，当提取剂浓度增加时，Mn的有效性有所回落。     

低分子有机酸去除土壤中重金属条件的研究

采用化学萃取实验,以湖南郴州柿竹园和湖南衡阳水口山矿区的重金属污染农田土壤为研究对象,采用柠檬酸、草酸、酒石酸作为低分子有机酸萃取剂,在一定的条件下对污染土壤中重金属进行萃取实验,确定各个单因素的适宜条件。结果表明,对于湖南郴州和衡阳两个污染地区土壤运用化学萃取技术萃取重金属来进行土壤修复是实际可行的;柠檬酸、酒石酸、草酸对各种土壤中的重金属都表现出了良好的萃取能力,是高效的土壤重金属萃取剂;单因素的适宜萃取条件为100mmol·L^-1有机酸溶液,固液比1∶5,恒定温度35℃,pH为3,反应时间24h,且萃取率随着电解质浓度的增大而提高;土壤中重金属存在形态与萃取效果有一定的相关性,稳定态（残渣态、硫化物和有机结合态、铁-锰氧化物结合态）金属含量高,表现为较低的萃取率;反之,萃取率高;柠檬酸、草酸、酒石酸3种萃取剂均能有效地降低衡阳污染土壤中的重金属浓度,3种萃取剂的萃取效率依次为酒石酸〉草酸〉柠檬酸。     

Assessment of Ecotoxicity of Soils Contaminated by Heavy Metals

Eurasian Soil Science - The experiment has shown that in soils contaminated by heavy metals, the boundary metal concentrations, above which ecotoxicity evidences are recorded, are different for the...     

模拟降雨条件下污染土壤中重金属元素径流迁移特征

探明污染土壤中重金属元素随地表径流迁移特征,对于防控重金属污染物的迁移扩散具有重要意义。通过室内模拟降雨试验,研究不同降雨强度下(55,100,120mm/h)污染土壤中Cd、Pb和Cr随地表径流迁移的特征。结果表明:径流中3种重金属元素总量在产流的前20min内逐渐降低,随后趋于稳定;产流初期(产流10min内)颗粒态重金属占径流重金属总量的比例均在80%以上;随产流时间延长,颗粒态Cd和Cr对径流重金属的贡献率快速降低,其颗粒态/溶解态的比值范围分别为47.0～0.4和12.9～0.4,而Pb则主要以颗粒态的形式存在,溶解态Pb对其随径流迁移的贡献率可忽略不计;随降雨强度增大,径流中总Cd和Pb含量显著降低,而径流中总Cr含量以及溶解态重金属含量无明显变化规律。     

膨润土、褐煤及其混合添加对铅、镉复合污染土壤重金属形态的影响

为研究膨润土与褐煤对铅镉复合污染土壤重金属形态变化的影响,以河南济源某铅冶炼企业周边重金属污染土壤为研究材料,将膨润土(S)、褐煤(P)按1.5%、3.0%、5.0%单独添加和两者混合添加,进行60天的室内培养后,用BCR连续提取法,研究了添加不同含量的膨润土和褐煤对重金属污染土壤中Pb、Cd形态的影响。结果表明,单一添加褐煤能显著降低土壤中Pb、Cd的有效态含量,褐煤添加量5.0%时土壤中铅和镉弱酸提取态含量分别降低了42.60%和25.20%。单一添加膨润土能显著降低土壤中Pb的有效态含量,而对Cd的有效态含量影响不明显。膨润土5.0%和褐煤(1.5%、3.0%、5.0%)混合处理土壤中铅的弱酸提取态含量降幅达44.50%～46.00%,铅的残渣态含量增幅达30.90%～66.80%。褐煤5.0%和膨润土(1.5%、3.0%、5.0%)的混合添加使土壤中镉的弱酸提取态含量降低、降幅达21.70%～26.00%,镉的残渣态含量增幅达81.60%～110.9%。褐煤单一施用对复合污染土壤中Pb、Cd的钝化效果整体优于膨润土,两者配施的修复效果优于其中一种单一施用的效果,且因配施比例而异...     

Restoration of Vegetation in Relation to Soil Properties of Spoil Heap Heavily Contaminated with Heavy Metals

The main objectives of our study were to evaluate soil contamination on a zinc-lead spoil heap in the Upper Silesian Industrial Region in southern Poland using pollution indices, and to investigate the relation between soil properties and the natural succession of vegetation. Organic carbon and nitrogen, pH, soil texture, base cations, and heavy metal content were analyzed in soil samples at depths of 0–15 cm below the organic horizon over a regular grid of 14 sampling plots. The contents of Zn, Pb, and Cd exceeded by several times the acceptable thresholds. Measurements of soil enzyme activity were used to evaluate the progress of vegetation development in relation to soil chemical properties. The results indicate that heavy metals had a significant impact on soil enzyme activity and the development of vegetation cover. High contents of Pb and Cd reduced enzyme activity, while this activity increased with increasing amounts of soil organic matter. Further, the accumulative capacities of heavy metals in needles of Scots pine (Pinus sylvestris L.) and aboveground biomass of bladder campion (Silene vulgaris (Moench) Garcke) were examined. A high accumulation of Zn, Pb, and Cd in the aboveground tissues of S. vulgaris indicated an unusual tolerance of this species to heavy metals and the possibility of using this species in phytoremediation of post-industrial sites.     

茶皂素对污染土壤中重金属的修复作用

采用振荡离心的方法研究了生物表面活性剂茶皂素在不同浓度、pH值和离子强度下对污染土壤中重金属去除效果的影响;并采用BCR法研究了茶皂素处理前后土样中各形态的重金属含量变化。试验结果表明:随着茶皂素浓度的增加,重金属的去除率随之增加,在茶皂素浓度为7%时,对供试土样中重金属的去除率达到最大值,去除率分别为Cd 96.36%,Zn 71.73%,Pb 43.71%,Cu 20.56%;随着土壤环境pH值的增加,重金属的去除率随之减少,适宜的pH范围在5.0左右;离子强度对Pb,Cu的去除效率影响不大,Zn,Cd的去除率随着离子强度的增加而减少。比较茶皂素处理前后土样中重金属各形态含量的变化,发现酸溶态的重金属更易被茶皂素去除,其次为可还原态、可氧化态和残渣态的重金属很难被去除。     

混合试剂在不同电解质条件下对土壤重金属淋洗效果的影响

为了得出不同电解质(CaCl2和KCl)对混合试剂(EDTA和柠檬酸)去除土壤重金属的影响,对重金属污染土壤进行盆栽淋洗实验.结果表明,含电解质CaC12的混合试剂有利于去除酸性污染土壤中重金属;而含KC1的混合试剂有利于去除中性污染土壤中重金属.含电解质CaC12和KC1混合试剂[EDTA-+-CA+ 1/2(CaC12+KCl)]对土壤重金属的淋洗效果不明显;但电解质用量的增加(如EDTA+ CA+ CaCl2+KCl)提高了酸性土壤中Cd、Zn、Pb和Cu的去除率,提高幅度分别达22％,16％,18％和9％.Cd和Zn污染的酸性土壤,可用CA+ CaCl2+KCl混合试剂淋洗;但Pb和Cu的去除还要靠EDTA.中性重金属污染土壤可采用EDTA+ CaCl2+ KCl混合试剂淋洗.     

EDTA和柠檬酸对污染土壤中重金属的解吸动力学及其形态的影响

利用批处理振荡解吸平衡法研究了0.05 mol/L的乙二胺四乙酸钠(EDTA)和柠檬酸对污染土壤中Cd,Pb,Cu,Zn的解吸动力学特征,并采用优化的BIER(European Community Bureau of Reference)连续提取法分析了EDTA和柠檬酸处理前后土壤中重金属形态和生物有效性的变化.结果表明,污染土壤中重金属Cd,Pb,Cu,Zn的解吸率随着解吸时间的延长而不断增加,但解吸速率随解吸时间的延长而不断降低.EDTA对Pb,Cu的解吸能力显著大于柠檬酸,柠檬酸对Zn的解吸能力显著大于EDTA,柠檬酸和EDTA对Cd的解吸能力相差不大.EDTA和柠檬酸对4种重金属解吸能力的顺序分别为:Pb＞Cd＞Zn＞Cu和CA＞Zn＞Pb＞Cu.双常数方程是描述污染土壤中Cd,Pb,Cu,Zn解吸动力学过程的最佳方程.EDTA去除的重金属主要以酸提取态和可还原态存在,柠檬酸去除的重金属主要以酸提取态存在.EDTA和柠檬酸处理后.污染土壤中Cd,Pb,Cu,Zn的生物有效性降低.     

重金属污染土壤毒性的发光菌法与斜生栅藻法诊断

应用斜生栅藻(Scenedesmus obliquus)和明亮发光杆菌T3(Phyotobacterium Phosphoreum)对重金属污染土壤的毒性进行诊断,结果表明,斜生栅藻的增长率和发光菌的相对发光度与土壤中的重金属含量明显相关,并且随重金属投加量的增加,其增长率和发光度逐渐降低,对3种测试参数进行比较,发现采用细胞数增长率作为土壤毒性的检测指标比采用光密度增长率和相对发光度更为敏感。复合污染情况下,由于金属间的协同作用,使土壤的毒性比单一重金属污染时有明显的增强,从而为污染土壤的优先修复提供了理论依据。     

Removal of Heavy Metals from Calcareous Contaminated Soils by EDTA Leaching

The performance of EDTA for the treatment of calcareous soils contaminated with heavy metals from mining and smelting activities was evaluated in this study. Soil samples containing variable levels of contamination, from 500 to 35 000 mg kg^-1 Pb and 700 to 20 000 mg kg^-1 Zn, were subjected to EDTA treatment and the extraction of heavy metals was found to vary, ranging between 50 and 98% for Pb and 50 to 100% for Zn. Total residual concentrations were above the limits set by regulatory authorities; leachable metals, however, were efficiently removed and treated soils were all acceptable in terms of toxicity. The effect of EDTA concentration and pulp density was studied on a soil sample containing 12 000 mg kg^-1 Pb and 10 000 mg kg^-1 Zn. Heavy metals removal was improved at low pulp densities and when EDTA concentration was increased from 0.025 to 0.25 M. The tetrasodium salt Na₄-EDTA was found to be less effective for metals removal compared to the disodium salt Na₂-EDTA, though applied at higher concentrations. This experimental work has also demonstrated the great importance of soil matrix for the overall evaluation of the EDTA leaching as a cost effective remedial option. The simultaneous dissolution of calcite was found to consume approximately 90% of the available EDTA. It was thus concluded that for the treatment of calcareous soils the design criteria and cost estimations should be based on the calcite content of the soil.     

Field-Scale Assessment of Phytotreatment of Soil Contaminated with Weathered Hydrocarbons and Heavy Metals (9 pp)

Background, Aim and Scope   Phytoremediation is a remediation method which uses plants to remove, contain or detoxify environmental contaminants. Phytoremediation has successfully been applied for the removal of fresh hydrocarbon contamination, but removal of aged hydrocarbons has proven more difficult. Biodegradation of hydrocarbons in the subsurface can be enhanced by the presence of plant roots, i.e. the rhizosphere effect. Phytostabilization reduces heavy metal availability via immobilization in the rhizosphere. Soils contaminated by both hydrocarbons and heavy metals are abundant and may be difficult to treat. Heavy metal toxicity can inhibit the activity of hydrocarbon-degrading microorganisms and decrease the metabolic diversity of soil bacteria. In this experiment, weathered hydrocarbon- and heavy metal- contaminated soil was treated using phytoremediation in a 39- month field study in attempts to achieve both hydrocarbon removal and heavy metal stabilization. Materials and Methods: A combination of hydrocarbon degradation and heavy metal stabilization was evaluated in a field-scale phytoremediation study of weathered contaminants. Soil had been contaminated over several years with hydrocarbons (11400±4300 mg kg dry soil)-1 and heavy metals from bus maintenance activities and was geologically characterized as till. Concentrations of soil copper, lead and zinc were 170±50 mgkg-1, 1100±1500 mg kg-1 and 390±340 mg kg-1, respectively. The effect of contaminants, plant species and soil amendment (NPK fertilizer or biowaste compost) on metabolic activity of soil microbiota was determined. Phytostabilization performance was investigated by analyses of metal concentrations in plants, soil and site leachate as well as acute toxicity to Vibrio fischeri and Enchtraeus albidus. Results: Over 39 months hydrocarbon concentrations did not decrease significantly (P=0.05) in non-amended soil, although 30% of initial hydrocarbon concentrations were removed by the last four months of study. In soil amended with NPK fertilizer and municipal biowaste compost, 65 % and 60 % of hydrocarbons were removed, respectively. The soil contained metabolically diverse bacteria, measured as carbon source utilization and extracellular enzymatic activities. Compost addition resulted in a slight increase in enzymatic activities. Diesel fuel utilization potential in Biolog MT2 plates inoculated with a soil suspension was enhanced by both compost and NPK compared to non-amended soil. Soil toxicity to V. fischeri and E. albidus was low. The leachate was not toxic to V. fischeri. Pine (Pinus sylvestris), poplar (Populus deltoides x Wettsteinii), grasses and clover (Trifolium repens) survived to varying degrees in the contaminated soil. All plants suffered from phytotoxicity symptoms and some trees died during the study period. Plants formed a dense cover over the compost-amended soil, whereas non-amended soil had areas devoid of vegetation throughout the study. Vegetation coverage in the NPK-amended quarter was about 50 % after the first four months of study, but increased gradually to 100 %. Heavy metals did not accumulate in plant tissue. Discussion: Removal of hydrocarbons from weathered unfertilized hydrocarbon-contaminated soil was not statistically significant despite the presence of a viable hydrocarbon-degrading microbial community. This effect is attributed to soil heterogeneity and low bioavailability of hydrocarbons. Hydrocarbon concentrations were not reduced to the desired level, i.e., 1500 mg hydrocarbons (kg of dry soil)-1, in any treatment. . The presence of clay minerals and organic matter within the compost may have limited heavy metal transfer to leachate and plant tissue. Conclusions: Weathered hydrocarbons were partly decomposed in soil fertilized with NPK fertilizer or biowaste compost, but not from unfertilized soil. The active hydrocarbon-degrading microbiota and low toxicity of soil to V. fischeri and E. albidus indicates low availability of contaminants to microorganisms. Despite high heavy metal concentrations, the soil contained metabolically diverse bacteria, measured as carbon source utilization and extracellular enzymatic activities. Heavy metals did not accumulate in test plants. Pine and poplar suffered from phytotoxicity symptoms in the soil and could not enhance hydrocarbon removal in compost-amended soil. Compost addition combined with a grass and legume crop is suggested for stabilization of combined hydrocarbon- and metal-contaminated soil. Recommendations and Perspectives: Both compost and NPK fertilizers can be used to enhance phytoremediation of soil contaminated with weathered hydrocarbons in the presence of heavy metals; however, compost addition is recommended since it enables greater vegetative coverage. This in turn may decrease heavy metal mobility. Phytoremediation can be used for remediation of soil contaminated with weathered hydrocarbons in the presence of heavy metals. However, phytoremediation of weathered contaminants requires extended periods of time; thus, other remediation methods should be considered in the event of soil contamination posing an immediate public health and/or environmental threat.     

不同降雨强度下污染土重金属元素随径流迁移转化特征

通过室内模拟降雨试验,研究了不同降雨降雨强度下(29.9,55.2,78.5mm/h)空白土和污染土Cu、Pb和Zn随地表径流的迁移转化特征。结果表明,空白土与污染土径流携带的泥沙量均随降雨强度的增大而增大,土壤受重金属污染对侵蚀泥沙量的变化影响不大;污染土径流中水溶态Cu、Zn含量明显高于空白土含量,且基本不受降雨强度影响,其大小主要由土壤酸溶态中的可交换态含量决定,3种重金属水溶性含量大小为ZnCuPb;不管对于空白土还是污染土,径流中重金属总浓度都随降雨强度的增大而增大,但污染土增加的幅度明显比空白土大,且与泥沙量变化趋势基本一致,而空白土无此规律。     

粉煤灰对污染土壤中铜镉的稳定化

采用批衡量吸附和室内培养实验,考察了粉煤灰对Cu和Cd的吸附等温线及0.2%、0.5%、1%和2%用量的粉煤灰对土壤pH、有效态Cu和Cd、以及5种化学形态Cu和Cd分布的影响。结果表明:粉煤灰对Cu和Cd的吸附等温线均可以用Langmuir和Freundlich方程进行拟合,其对Cu的最大吸附量(9.90 mg/g)高于对Cd的最大吸附量(9.43 mg/g)。随着粉煤灰用量的增加,土壤pH显著增加,有效态Cu和Cd显著降低。同时,粉煤灰处理显著降低了离子交换态Cu和Cd含量,增加了铁锰氧化物结合态Cu和Cd含量,降低了Cu和Cd活性,使活性态Cu和Cd逐渐向潜在活性态和非活性态转化。其中培养60天后,2%处理的粉煤灰处理较对照pH提高了0.44个单位,离子交换态Cu和Cd分别降低了35.7%和35.9%。因此,粉煤灰能够有效吸附Cu和Cd,显著降低土壤有效态和离子交换态Cu和Cd的含量,在重金属稳定化修复应用中具有较好的应用前景。     

CO2浓度升高对重金属污染下稻米品质影响的研究进展

目前研究CO2浓度升高对农作物的影响主要集中在光合作用、生理生态反应和产量形成等方面,对重金属污染胁迫下CO2浓度升高对水稻生长发育和品质影响的研究甚少。本文通过详述Cu、Cd等重金属污染条件下,CO2浓度升高对水稻生长发育及稻米品质的影响,揭示重金属污染条件下CO2浓度升高影响Cu、Cd在土壤-水稻系统中的运移状况及其稻米营养品质方面的相关机制,为CO2浓度持续升高背景下复合污染农田风险评估、农产品安全调控提供科学依据,也对于预测未来气候条件下人类稻米品质变化及水稻品种的选育意义重大。     

石灰水对混合试剂洗脱土壤重金属淋洗效果的影响

为了探索石灰水对混合试剂(MC)洗脱后土壤中重金属的淋洗效果,对重金属污染土壤进行了盆栽淋洗试验研究。结果表明:石灰水淋洗MC洗脱土壤,淋出液中Cd、Zn、Pb和Cu浓度均显著高于去离子水淋洗MC洗脱土壤,这主要由于石灰水提高土壤pH,释放土壤所吸附的络合态重金属,这种现象在酸性污染土壤中表现更明显。对于酸性污染土壤,可采用MC+石灰水+去离子水依次进行淋洗处理,其Cd和Zn去除率与MC+去离子水+去离子水依次淋洗处理相比提高22.6%和28.8%;对于中性重金属污染土壤,两处理间重金属去除率差异不显著。石灰水淋洗可提高土壤重金属去除率,并提高土壤pH,改善MC洗脱对土壤的酸化,有利于淋洗后土壤的农业利用。