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。     

土壤环境中重金属生物有效性评价方法及其环境学意义

重金属生物有效性是衡量重金属元素迁移性和生态影响的关键参数,在生态地球化学评价中有重要的作用。国土资源部目前进行的新一轮多目标区域生态地球化学调查与评价,使重金属生物有效性受到进一步的重视。本文评述国际上基于化学和基于生物学两种对生物有效性概念理解及其分歧,评价各种生物有效性评价方法发生的背景、应用范围和优缺点。物理化学法和土壤生物学评价法是两类主要的生物有效性评价方法,经常使用的包括化学总量预测法、化学一步提取法、顺序提取法、自由离子活度法(唐南膜平衡法)、植物指示法、微生物学评价法等。各种方法间往往相互独立,尚未形成被一致接受的方法,从而影响了生物有效性在风险评价和污染治理等工作中的应用。未来发展的重点是,进一步加强重金属生物有效性的理论研究,实现土壤学、化学和生物学的融合,将评价方法统一化和标准化,提高数据的可靠性和对比性,同时将越来越多地应用于我国多目标生态地球化学调查与评价,提高调查质量和服务水平。     

污染水稻土中重金属的形态分布及其影响因素

通过BCR3步提取法研究了江西省贵溪铜冶炼厂污染区水稻土中重金属的形态分布。研究表明,废渣场渗滤液污染区域(渣场区)的污染较污水灌溉污染区(污灌区)严重,渣场区土壤中Cu、Pb、Cd的含量高于污灌区,而污灌区土壤Ni含量较高。在表层(0～20cm)水稻土中,Cu以可氧化态为主,Pb以可还原态和可氧化态为主,Cd以酸溶态为主,Ni以残渣态为主,不同重金属元素的有效态所占总量百分比大小顺序是Cd>Cu>Pb>Ni。土壤重金属不同形态之间也呈现一定的相关性,说明Cu与Pb、Cd、Ni之间具有同源性。土壤pH主要影响了污灌区中Cu的形态分布,以及渣场区土壤酸溶态Ni的分布。土壤有机质含量对各重金属形态分布的影响不明显。     

尾矿库尾砂及周边农田土壤重金属形态分布及其生物有效性

采用BCR（community bureau of reference）连续提取法对大宝山矿山槽对坑尾矿库尾砂和周边农田土壤重金属Cd、Pb、Cu和Zn的形态分布及其生物有效性进行了分析。结果表明,尾砂中Cd、Pb、Cu和Zn残渣态占绝对优势,占其总量的百分数均在85%以上。农田土壤中Cd、Cu和Zn都以残渣态为主,分别占其总量的60%、60%和90%以上,Pb以残渣态和可还原态为主,占其总量的93.44%。农田土壤重金属有效性较尾砂大,尾砂和农田土壤重金属生物有效性均以Pb为最高。     

Use of a Rhizosphere-Based Method for the Assessment of Heavy-Metal Bioavailability in Soils Amended with Polluted Sewage Sludge

A rhizosphere-based method (a low-molecular-weight organic acid solution) was evaluated for the assessment of cadmium (Cd), chromium (Cr), and lead (Pb) bioavailability to barley (Hordeum vulgare) roots from rhizosphere soils (n = 36) following a 15.71 g dry weight kg^?1 application of a metal-spiked sewage sludge under greenhouse conditions. Statistically significant correlation coefficients were found: r = 0.758, P < 0.001 for Cd, r = 0.762, P < 0.001 for Cr, and r = 0.723, P < 0.001 for Pb. The correlations were greater in acidic soils (n = 6; r = 0.983, P < 0.001 for Cd, r = 0.888, P < 0.01 for Cr, and r = 0.898, P < 0.01 for Pb). This extraction failed to assess heavy-metal bioavailability in basic soils (n = 30; r = 0.111, P > 0.05 for Cd, r = 0.002, P > 0.05 for Cr, and r = 0.037, P > 0.05 for Pb). The overall predictability was greatly improved when soil properties were considered (n = 36; r² = 0.730, P < 0.001 for Cd, r² = 0.800, P < 0.001 for Cr, and r² = 0.719, P < 0.001 for Pb), and texture was observed in all the prediction models.     

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。     

新乡市寺庄顶污灌区土壤中重金属的形态分布及生物有效性研究

对长期电池废水灌溉的新乡市寺庄顶污灌区和对照区土壤重金属进行取样分析,结果表明,对照区土壤中Cd,Ni,Zn,Cu和Cr含量都能达标,污灌区土壤中Cr含量能达标,Cd,Ni,Zn和Cu的含量超标,其平均含量分别为65.31,1 196.64,2 799.25,145.78 mg/kg,是国家土壤环境质量二级标准的108.85,19.94,9.33和1.46倍。形态分析结果表明,污灌区污染最严重的Cd主要以铁-锰氧化物结合态存在,所占比例平均为56.84%;Ni主要以铁-锰氧化物结合态和残余态存在,所占比例平均为37.44%和39.55%;Zn主要以残余态存在,所占比例平均为78.24%;Cu主要以有机结合态存在,所占比例平均为57.70%;Cr主要以有机结合态和残余态存在,所占比例平均为45.55%和34.18%。与对照相比,污灌降低了Cd,Ni,Zn,Cu和Cr残余态所占比例,提高了重金属迁移能力和生物有效性。在4种超标重金属中Cd可交换态所占比例最高,平均为24.54%,由于其生物有效性最高,Cd迁移能力和植物毒性最值得关注。     

土壤表面电荷特征与重金属吸附解吸的相互关系

土壤对重金属的吸附 解吸与土壤性质特别是土壤表面电荷性质密切相关。本文概述了恒电荷土壤与可变电荷土壤表面电荷特征与重金属吸附 解吸的相互关系及研究进展。     

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。     

Investigation of Heavy Metals using Various Extraction Methods in Livestock Manures

The use of animal waste for a soil amendment is a viable option for waste management. For safe and sustainable management of waste, it is important to assess the concentrations of heavy metals (HM). An experiment was conducted to compare metals [copper (Cu), zinc (Zn), and manganese (Mn)] in cow manure (CM), duck litter (DL), poultry litter (PL), and poultry litter ash (PLA) using eight extraction solutions. Extractability of HM was highly dependent upon the type of waste as well as extracting agent. Manures differed for the release of HM in the order of PL > DL > CM. Marked decreases in extractable trace elements were observed after ashing of PL irrespective of extraction method. Except for water, extractions released HM in the order of Mn > Cu > Zn. For Zn and Mn, the amount extracted varied in the order 1 M nitric acid (HNO₃) > 0.1 M HNO₃ > 0.01 M HNO₃ ≈ ethylenediaminetetraacetic acid (EDTA) > ammonium nitrate (NH₄NO₃) > calcium chloride (CaCl₂) > ammonium acetate (NH₄OAc) > H₂O in PL and PLA. Peak concentration of Cu was achieved in 1 M HNO₃ solution and the lowest Cu was found in NH₄OAc solution. On the basis of these results, the low extractability of HM in ash could suggest that the use of burned PL would be less of a water-pollution problem in the fields.     

西南某矿区土壤重金属的人体生物有效性及健康风险评估

利用生物可给性修正后土壤重金属经口摄入的人体健康风险值也可能被高估,而应用体内实际摄入剂量（生物有效性）作为健康风险评价指标将更为准确,但是基于生物有效性的矿区土壤重金属污染健康风险评估报道较少。以云南文山某矿区为研究对象,分析了5个土壤样点中镉（Cd）、铅（Pb）、锌（Zn）和铜（Cu）的含量,通过体外消化法测定了4种重金属的生物可给性,并结合BALB/c白变种实验室小鼠实验分析了重金属Cd的相对生物有效性（RBA）,基于此探讨该矿区土壤重金属Cd、Pb、Zn和Cu对人体产生的健康风险。结果表明,本研究区域土壤Cd污染较为严重,含量为2.06 mg·kg-1。四种重金属的生物可给性在胃相中的范围分别为24.29%～50.55%、7.68%～17.87%、24.61%～32.18%、7.75%～37.87%,在肠相中分别下降至22.78%～44.32%、1.64%～5.22%、14.10%～28.11%、8.51%～31.49%。动物实验测得的Cd在肝脏中RBA为1.31%～48.39%,肾脏中为2.83%～8.58%,肝和肾复合器官中为4.60%～50.95%,且肝和肾复合器官是测定...     

耕作方式对稻-油轮作系统土壤理化性质及重金属有效性的影响

为探明不同耕作方式下稻-油轮作系统中土壤重金属有效性的变化规律,测定了21年长期定位试验稻-油轮作系统中土壤及其剖面的主要理化性质和重金属有效含量,分析了二者间的关系。结果表明,与翻耕相比,垄作免耕使各土层土壤有机质含量和阳离子交换量显著提高,并具有明显的表层聚集现象,土壤pH值明显降低。耕层土壤Cd、Cu和Zn有效量以垄作免耕处理最高,土壤Pb的有效量则以常规平作处理最高,不同耕作方式下,土壤有效Cd和Pb出现表聚现象,但有效Zn和Cu随土壤深度的变化无明显规律。相关分析表明,土壤有机质含量与土壤Cd、Zn有效量呈极显著正相关关系,与土壤Pb、Cu有效量呈显著正相关,土壤pH值与土壤Pb有效量呈显著正相关,而土壤阳离子交换量与4种重金属有效量间的相关性不显著。由此推测,耕作方式主要是通过影响土壤有机质含量而影响重金属元素的有效性,垄作免耕较翻耕在改良土壤理化性质上有较大优势,却使0-20cm和20-40cm土层重金属有效量显著增加,表现出明显的表层富集趋势。     

Evaluation of Different Extraction Methods for the Assessment of Heavy Metal Bioavailability in Various Soils

The main objective of this study was to compare the effectiveness of different methods (heavy metals in pore water (PW), diffusive gradients in thin films (DGT), diethylene triamine pentaacetic acid (DTPA) extraction, and total heavy metals (THM) in soil) for the assessment of heavy metal bioavailability from soils having various properties and heavy metal contents. The effect of soil heavy metal pollution on shoot yield and sulfatase enzyme activity was also studied. Wheat (Triticum aestivum) was grown in different soils from Spain (n?=?10) and New Zealand (n?=?20) in a constant environment room for 25 days. The bioavailabilities of Cd, Cr, Cu, Ni, Pb, and Zn were assessed by comparing the metal contents extracted by the different methods with those found in the roots. The most widely applicable method was DGT, as satisfactory Cu, Ni, Pb, and Zn root concentrations were obtained, and it was able to distinguish between low and high Cr values. The analysis of the metal concentrations in PW was effective for the determination of Cr, Ni, and Zn content in root. Copper and Pb root concentrations were satisfactorily assessed by DTPA extraction, but the method was less successful with determining the Ni and Cr contents and suitable just to distinguish between high and low concentrations of Zn. The THM in soil method satisfactorily predicted Cu and Pb root concentrations but could only be used to distinguish between low and high Cr and Zn values. The Cd root concentration was not successfully predicted for any of the used methods. Neither shoot yield nor sulfatase enzyme activity was affected by the metal concentrations.     

浙江省优势农产区土壤重金属分异特征及评价

通过详细的调查分析，研究了浙江省优势农产区表层土壤重金属分异特征及其现状，并探讨了各种影响因素。904个代表性样品的分析结果表明，除As和Hg以外，Cd、Cr、Pb、Zn、Cu及Ni的含量均高于浙江省第2次土壤普查得到的表层土壤重金属含量；与杭嘉湖平原、浙江省、中国及世界土壤背景值的对比发现，研究区土壤大部分重金属元素的含量明显偏高，根据国家二级标准限值得出的单项评价结果表明，Cd和Ni的超标指数较高，分别达到lO．72％和9．7％。Hg、Pb、Cu和Cr次之，分别为6．80％，5，35％，3．43％和3．03％，Zn和As较小，分别为1．80％和1．04％。此外．通过对不同的土地利用类型、不同母质及土壤类型土壤中重金属含量的方差分析，研究了这些因子对浙江省农业土壤重金属含量的影响程度及其原因。     

Use of Drinking Water Treatment Residuals in Reducing Bioavailability of Metals in Biosolid-Amended Alkaline Soils

This greenhouse study evaluated the use of drinking-water-treatment residuals (WTRs) to reduce the bioavailability of metals in the biosolid-amended agricultural alkaline soils. Results showed that increasing the application rate of biosolids increased the accumulation of lead (Pb), nickel (Ni), copper (Cu), and cadmium (Cd) in corn (Zea mays cv. single hybride 10), with greater metal concentrations in roots than in shoots. However, the addition of WTRs (1–4%, w/w) to the soil amended with 3% biosolids significantly (P < 0.05) decreased the concentrations of soil diethylenetriaminepentaacetic acid (DTPA)–extractable metals. The accumulation of Pb, Ni, Cu, and Cd in corn significantly correlated with the DTPA-extractable metal concentrations in the soils. Plant metal concentrations were significantly affected by the soil type, application rates of biosolids and WTRs, and the ratio of WTRs to biosolids in the soils. The 1:1 application ratio of WTRs to biosolids at the 3% application rate effectively reduced the accumulation of metals in corn tissues.     

Bioavailability of Silicon from Different Sources and Its Effect on the Yield of Rice in Acidic,Neutral, and Alkaline soils of Karnataka,South India

Several silicon (Si) sources have been reported to be effective in terms of their effectiveness on rice growth and yield. Apart from that, it is crucial to understand the bioavailability of silicon from different silicon sources for adequate plant uptake and its performances in varying types of soils. In this point of view, a pot experiment was conducted to assess the bioavailability of silicon from three Si sources and its effect on yield of rice crop in three contrasting soils. Acidic (pH 5.86), neutral (pH 7.10), and alkaline (pH 9.38) soils collected from different locations in Karnataka were amended with calcium silicate, diatomite, and rice husk biochar (RHB) as Si sources. Silica was applied at 0, 250, and 500 kg Si ha^?1, and the pots were maintained under submerged condition. There was a significant increase in the yield parameters such as panicle number pot^?1, panicle length pot^?1, straw dry weight pot^?1, and grain weight pot^?1 in acidic and neutral soils with the application of Si over no Si treatment, whereas only straw dry weight pot^?1 increased significantly with the application of Si sources over control in alkaline soil. Higher Si content and uptake was noticed in neutral soil followed by acidic and alkaline soils. The bioavailability of Si increased with the application of Si sources but varied based on the types of soil. Application of calcium silicate followed by diatomite performed better in acidic and neutral soils whereas RHB was a better source of Si in alkaline soil. A significant difference in plant-available silicon status of the soil was noticed with the application of Si sources over control in all three studied soils.     

长期秸秆还田对污染农田土壤与农产品重金属的影响

在浙东某地选择一污染农田,布设了秸秆还田、秸秆不还田、秸秆还田+石灰及秸秆不还田+石灰4个处理试验,进行了为期9年的土壤、秸秆、谷物、蔬菜等农产品中重金属动态监测。结果表明,污染农田中施用石灰可明显降低水稻秸秆和谷物及蔬菜中重金属的积累,但对土壤重金属含量影响不明显;施用石灰对水稻秸秆和谷物及蔬菜中重金属降低作用随试验时间逐渐减弱。与秸秆不还田比较,秸秆还田在短期内对土壤、水稻秸秆和蔬菜重金属积累的影响较小,但4~5年后秸秆不还田农田土壤镉、汞积累及水稻秸秆和蔬菜中镉、铅、汞积累明显低于秸秆还田农田,对土壤中铅积累的影响较小;随着试验时间的增加,秸秆还田与秸秆不还田农田之间土壤、水稻谷物及蔬菜中重金属积累的差异逐渐加大。秸秆还田农田土壤有机质和速效钾含量高于秸秆不还田农田。研究结果表明,在镉、汞污染农田中长期推行秸秆还田不利于农产品质量的提高,应控制重污染水稻秸秆还田。     

淹水条件下生物炭对污染土壤重金属有效性及养分含量的影响

以生物炭为改良剂,采用淹水培养方法研究不同添加量生物炭(BC)处理(1%,3%和5%)对污染土壤Zn、Cd、Pb、Cu有效性及养分含量的影响,并用毒性淋出试验(TCLP)法对其生态风险进行评价。结果表明:与对照相比,添加生物炭土壤中交换态Zn、Cd、Pb、Cu分别降低0.15%～24.11%,1.22%～16.09%,0.47%～21.51%,3.05%～77.30%,且表现为随生物炭施用量的增加其降低程度增大。TCLP态Zn、Cd、Pb、Cu含量分别降低0.74%～21.47%,6.67%～47.62%,2.02%～16.74%,0.29%～21.20%,且表现为随生物炭施用量的增加其降低程度增大。与对照相比,添加生物炭后土壤pH上升(-0.01)～0.35个单位,有机质、铵态氮和硝态氮分别增加0.09%～20.02%,1.59%～38.28%和2.74%～90.14%。土壤pH值与土壤交换态Cu含量呈显著负相关,有机质含量与交换态Zn含量呈显著负相关。淹水条件下污染土壤中施用生物炭可降低重金属Zn、Cd、Pb和Cu的有效性和生态风险,提高土壤养分含量,起到改良土壤作用。     

沘江流域耕地土壤重金属分布及生态风险评价

地处兰坪铅锌矿下游的沘江流域土壤重金属污染问题倍受关注。本文在沘江流域采集了35个耕地土壤样品,分析测定了砷、铜、锌、镉、铅、汞6种重金属污染物累积量,并应用内梅罗综合污染指数法及Hacanson潜在生态风险指数法,对耕地土壤污染状况及生态风险进行评价。结果表明:(1)沘江流域沿岸耕地重金属铅、锌、镉累积量相对处于极高水平,均值分别为1 146.97、579.15、4.85 mg·kg~(-1),污染十分严重;砷的累积量也较大,均值为26.85 mg·kg~(-1);铜、汞累积量较小,污染程度轻;(2)地统计分析结果表明,兰坪周边流域是土壤重金属砷、锌、铅、镉污染的一个主要点源污染源,而铜、汞污染没有显著点源污染源,均来自不同面源污染;(3)流域内梅罗指数均值为17.69(远大于3),存在极其严重重金属污染,同时综合潜在生态风险指数均值为773.38,有很强潜在生态风险。污染物贡献表现为镉铅锌砷汞铜;(4)沘江流域耕地土壤总体表现为水田重金属污染略高于旱地。     

细菌-矿物互作及其复合体在重金属修复中的应用

利用功能细菌辅助植物固定重金属是目前农田土壤污染修复中高效且环境友好的方式,其中细菌与矿物间相互作用广泛存在,包括细菌对矿物的溶解作用、矿物对细菌活性的影响以及细菌-矿物复合体的形成等,并贯穿整个修复过程。一方面,细菌与矿物互作会影响细菌的活性和表面特性,如带电性、表面官能团位点类型及浓度等,进而影响细菌对重金属的生物吸附行为以及辅助植物修复作用的发挥;另一方面,细菌-矿物结合形成的复合体较单一细菌、矿物组分对重金属的固定行为不同,在重金属修复过程中发挥不可忽视的作用。本文综合分析细菌与矿物的结合作用、细菌对矿物的溶解作用以及矿物对细菌活性的影响,阐述细菌-土壤矿物(矿物材料)复合体在重金属污染修复中的应用潜能,为复合体应用于重金属污染土壤环境提供理论依据。