干湿交替下生物炭对复合污染土壤中镉砷有效性的影响

为了明确活性炭工业的副产品——杏壳生物炭和水分管理模式对石灰性土壤重金属有效性的钝化效果,采用重度Cd、As复合污染的农田土壤,通过土壤培养方法探索了干湿交替水分管理模式下,添加不同用量生物炭对土壤中Cd、As有效性的影响。结果表明:从土壤溶液中Cd、As浓度的变化来看,干湿交替培养条件下,添加2%~10%生物炭处理的土壤溶液中Cd浓度均显著低于对照(P<0.05),降幅为33.1%~62.2%,说明干湿交替模式下添加生物炭显著促进了Cd由土壤液相向土壤固相的转移,而添加生物炭对土壤溶液中砷浓度的影响不稳定,其主要受土壤水分管理模式的影响;从土壤固相Cd、As提取态的变化来看,添加生物炭(6%,8%,10%)处理与CK相比,可显著降低土壤中DTPA提取态Cd和NH4H2PO4提取态As的含量(P<0.05),降幅分别为8.7%~16.8%,5.1%~7.9%,表明干湿交替下添加生物炭显著降低了土壤Cd、As有效性;土壤连续分级提取的结果显示,施用生物炭促进了土壤Cd由酸可提取态和可氧化态向残渣态转化,土壤As由专性吸附态和无定形—弱结晶铁铝或铁锰水化氧化物结合态向残渣态转化,显著降低了污染土壤Cd、As活性。因此,在重度Cd、As复合污染的石灰性土壤区,施用6%生物炭并保持干湿交替的水分管理模式能显著降低土壤镉砷的有效性。     

四种改良剂对铜和镉复合污染土壤的田间原位修复研究

研究了石灰、磷灰石、蒙脱石和凹凸棒石对冶炼厂周边Cu、Cd污染土壤的原位修复效果。以黑麦草(Lolium perenne L.)作为田间修复植物,采用植物重金属吸收性、土壤重金属化学提取性及土壤溶液重金属浓度变化等作指标来评价修复效果,并研究了黑麦草对Cu、Cd的吸收与土壤、土壤溶液中Cu、Cd含量的相关性。结果表明,石灰高添加剂量(石灰占污染土壤耕作层质量的0.4%)处理黑麦草对重金属的富集效果最好,显著降低了重金属毒性,促进了黑麦草的生长及其对重金属的富集;石灰和磷灰石各添加剂量均显著降低了污染土壤交换态Cu含量;石灰、磷灰石和蒙脱石各添加剂量均显著提高了土壤溶液pH并显著降低了其Cu、Cd浓度。黑麦草地上部、根中Cu浓度与土壤交换态Cu及土壤溶液Cu浓度呈显著或极显著正相关关系。     

重金属的土水分配行为研究——根际土壤溶液采样器的应用

采用根际土壤溶液采样器(Rhizon-SMS)原位采集河南平原耕地土壤溶液.用土壤溶液中重金属浓度对数作为因变量、土壤溶液理化性质作为自变量,进行多元线性逐步回归,结果表明:只有有机碳进入Cu的相关方程,pH进入Cd的相关方程.土壤溶液pH和土壤中的Zn都作为自变量进入Zn的相关方程.土壤溶液中的Cu与pH没有线性关系,而Cd和Zn与土壤溶液pH有显著的线性关系(p＜0.01).计算了土壤中Cu、Cd、Zn在土壤与土壤溶液中的分配系数Kd.本研究中,3种重金属的Kd大小顺序为:Cu＞Zn＞Cd.根据Freeze 和Cherry模型,联合log(Kd-Cd)、log(Kd-Zn)与pH的线性关系,估计了Cd和Zn在土壤中的迁移速度.     

EDTA与EDDS螯合诱导印度芥菜吸取修复重金属复合污染土壤研究

盆栽试验比较研究了EDTA和易降解的EDDS对复合污染土壤中Cu、Zn、Pb、Cd的活化能力及印度芥菜对4种重金属的吸收与转运特征。结果表明:施用量相同的条件下,EDDS活化土壤Cu的能力与EDTA相当;而EDDS活化土壤Zn、Pb、Cd,尤其是活化土壤Pb、Cd的能力小于EDTA,这与两种螯合剂与不同重金属形成螯合物的稳定常数相一致。向复合污染土壤中施入3mmol/kg和6mmol/kgEDDS均可诱导印度芥菜叶中超量积累Cu。本研究中3mmol/kgEDDS的不同施用方式(单次施,分2次和4次施)对印度芥菜叶片Cu含量的影响差异不显著。各处理印度芥菜叶中的重金属浓度要远高于茎中的浓度,茎中的Cu浓度随土壤溶液Cu浓度线性增加,而叶中Cu的浓度随土壤溶液Cu浓度先增加后下降。     

喀斯特林地土壤重金属形态特征及其评价

通过野外调查与室内分析,对喀斯特林地土壤重金属全量及形态构成进行了调查,对土壤重金属污染及其生物有效性进行了评价,并探讨分析了土壤重金属与土壤pH值的相关性。结果表明:中性土壤As,Cd,Cu,Ni,Pb,Zn及Cr全量均大于酸性土壤的全量;As以酸溶态为主,Cd,Cu,Ni,Pb,Zn及Cr以残渣态为主,残渣态土壤重金属比例为中性高于酸性土壤;酸性和中性土壤重金属Pb全量、中性土壤的As和Cu全量均高于贵州土壤背景值;中性和酸性土壤重金属As,Cd和Ni全量及酸性土壤重金属Cu全量超过土壤环境质量二级标准值;酸性土壤为轻度污染,中性土壤为中度污染;重金属生物有效性表现为AsCdCrNiPbZnCu,酸性土壤As生物有效性指数最高,与中性土壤相比,酸性土壤重金属生物有效性高;Cu全量、可氧化态Pb、残渣态Cu与pH值呈极显著正相关,酸溶态Zn与pH值呈极显著负相关,酸溶态Cr与pH值呈显著负相关,残渣态As与pH值呈显著正相关。喀斯特林地土壤主要受到As,Cd,Cu,Ni这4种重金属的影响,除As外,其余3种元素属于"高背境,低活性"状态。     

不同水分条件下外源菌剂对污染水稻土中硅、砷有效性的影响

采用砷污染区水稻土,通过土壤培养方法探索了淹水和干湿交替水分管理模式下,添加外源菌剂(含有胶质芽孢杆菌和巨大芽孢杆菌)对土壤中硅和砷有效性的影响。结果表明,干湿交替培养条件下,添加混合菌剂及其灭菌菌液处理的土壤溶液中硅浓度分别比对照(CK)增加了18.7%~23.2%和19.2%~43.0%,这说明外源菌剂促进了土壤固相中硅向液相的释放。同时,添加混合菌剂及其灭菌菌液处理的土壤溶液中砷浓度分别比CK降低了13.6%~25.0%和22.7%~29.6%,土壤中有效砷浓度比CK分别降低了21.0%和15.7%,这说明外源菌剂降低了土壤中砷的有效性;但是在淹水培养条件下,外源菌剂中的微生物对土壤中硅、砷有效性影响不明显;此外,研究结果还显示,土壤溶液中硅和砷浓度之间存在显著的负相关关系(r淹水=-0.853,r干湿交替=-0.455,P0.05)。综上所述,干湿交替的水分管理模式下外源添加含有胶质芽孢杆菌和巨大芽孢杆菌的菌剂可促进硅从土壤固相到土壤溶液的释放,并降低了土壤中砷的有效性。     

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.     

滨海开发带土壤重金属分布特征及来源分析

以江苏省大丰市为例,研究了土壤中8种重金属的空间分布特征及其与土地利用的关系,并通过主成分分析方法,对其可能的来源进行了探讨。结果表明:研究区8种土壤重金属Cu、Zn、Pb、Cd、Cr、As、Hg、Ni平均含量分别为17.40、74.38、18.14、0.105、55.58、8.33、0.074、25.73mg/kg,不同采样点之间变异不大。沿垂直海岸线方向,随距海岸线距离增加,Cu、Zn、Pb、Cr、Hg、Ni 6种重金属含量逐渐升高,As含量逐渐降低,Cd含量则先升高、后降低。Cu、Zn、Pb、Cr、Hg、Ni 6种重金属均在水田土壤中含量最高,Cd在旱地土壤中含量最高,As则在滩涂土壤中含量最高。相关分析表明,土壤As含量与其他重金属元素含量的相关性均不显著,土壤Cd含量与Zn、Pb、Hg、Cr含量的相关性显著,与Cu、As、Ni含量的相关性不显著,其他各元素间相关性均达极显著水平。基于主成分分析结果,认为研究区土壤Cu、Zn、Pb、Cr、Hg、Ni 6种重金属元素含量受土壤母质影响较大,Cd含量与农业生产中磷肥施用关系密切,As含量的累积受磷肥施用的影响,但以水稻种植为主的耕作土壤As含量总体上呈下降趋势。本研究可为滨海开发带土地利用规划提供指导。     

嘉兴市蔬菜土壤重金属含量的初步调查分析

对嘉兴市蔬菜土壤中Cu、Zn、Pb、Cd、Cr、As、Ni进行测定分析,利用单因子污染指数法和2种不同评价标准评价土壤重金属的环境质量状况。结果发现,各重金属平均含量均高于其背景含量;Cu、Zn、Cd、Ni和As的浓度均有个别地方的含量超过了国家《土壤环境质量标准》(GB15618—1995)二级标准限值;土壤质量受到各种重金属不同程度的影响,存在着显著的空间分异,而Pb、Zn、Cu、Cd的污染是引起嘉兴地区土壤质量下降的主要原因。随着嘉兴地区城镇化空间扩展的推进与土地利用方式的变化,可能会导致新污染区的出现与土壤质量的下降。     

有机络合强化植物修复的环境风险研究I. EDTA对复合污染土壤中TOC和重金属动态变化的影响

采用盆栽试验研究了EDTA存在条件下的土壤溶液总有机碳(TOC)和重金属浓度的动态变化。结果表明,施用3 mmol/kg EDTA极显著地增加了土壤溶液中TOC的含量。土壤溶液TOC随培养时间呈指数曲线下降。在加入EDTA 52天后土壤溶液TOC仍然高于对照处理。施用EDTA大幅度地提高了土壤溶液Cu、Zn、Cd和Pb的浓度,这些重金属的浓度在一个月内迅速下降,以后趋向稳定。EDTA活化土壤重金属存在淋溶迁移的潜在环境风险。     

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.     

Protozoan bioassays of soil amended with sewage sludge and heavy metals,using the common soil ciliate Colpoda steinii

The common soil protozoan Colpoda steinii was used to study the toxicity of sulphate solutions of Ni, Cd, Cu, and Zn. The growth of C. steinii was reduced by 50% in the presence of 0.10, 0.22, 0.25, and 0.85 mg litre^-1 of Ni, Cd, Cu and Zn, respectively, during 24 h of incubation at 25°C, as calculated from a regression analysis of probit-transformed data. The same growth assay was used to assess the toxicity of soil solution extracted by centrifugation from soil samples of field plots of a grass/clover ley on a sandy loam treated with sewage sludge spiked with additional Cd, Cu, Cr, Ni, Pb, or Zn at concentrations either equivalent to or twice the limits for heavy metals recommended in recent EC guidelines (Commission of European Communities directive 86/278/EEC). The toxicity of these soil solutions varied with the season of the year. None of the soil solutions extracted in winter (February 1991) inhibited the growth of C. steinii. In summer (July 1991), the growth was reduced in solutions extracted from plots that were amended with sludge plus additional Zn or Ni at twice the maxima recommended by the EC. The changes in toxicity to C. steinii of the soil solutions between February and July were positively correlated with increases in heavy metal concentrations of Zn and Ni between winter and summer. These preliminary results suggest that regular protozoan bioassays may be used to monitor the biological availability of heavy metals in soils, especially when combined with other microbial assays and with chemical analyses of soil solutions.     

Soil Factors Affecting Heavy Metal Solubility in Some New Zealand Soils

Heavy metal contamination of soils is usually quantified and guidelines set solely on the basis of total heavy metal content. However, it is recognised that water soluble heavy metal concentrations may provide a better indication of the potential risk that heavy metals may pose to the soil environment. The aim of this study was to use a semi-empirical model based on the competitive adsorption of metal and H⁺ ions [dependent on solution pH, total metal content, total carbon content and soil oxide content] to predict water soluble Cu, Cr, Cd, Pb, Ni and Zn concentrations in a range of field contaminated soils. The results of multiple linear regressions showed that basic soil properties could predict 85, 72, 66, 78, 50 and 75% of the variation in soluble Ni, Cu, Cr, Pb, Cd and Zn concentrations respectively. Water soluble metal concentrations were best predicted using empirical linear regressions which included total metal content, while the importance of other soil properties such as soil pH, total carbon and oxalate extractable Fe and Al oxides varied between metals. The models have the potential to provide valuable information on metal availability in contaminated soils and offer an indication of the potential risk a metal may pose to a given soil environment, along with providing a basis for developing soil quality guidelines for the prevention, investigation and clean-up of soil metal contamination.     

泉州走马埭典型土壤重金属的赋存形态分析

采用改进的Tessier连续萃取方法研究了泉州走马埭国家农田示范保护区典型土壤中重金属(Cr、Ni、Cu、Zn、Cd、Pb)的化学形态分布,通过土壤重金属的赋存形态分析比较了6种重金属的生物可利用性。研究结果表明,土壤中不同重金属元素化学形态分布具有不同的特点:Cr和Ni主要以残渣态存在,其余形态所占的比例很小;Cu以残渣态含量最高,碳酸盐结合态含量最低;Zn以残渣态为主,可交换态含量最低;Cd以可交换态和碳酸盐结合态为主,水溶态含量最低;Pb以残渣态和铁锰氧化物结合态为主,水溶态含量最低。土壤中除Cd外,Zn、Cu、Cr、Pb、Ni在正常自然条件下相对比较稳定。     

华北地区有机种植与常规种植土壤质量比较研究

为探讨有机种植与常规种植两种不同种植方式对土壤质量的影响,本文在华北地区选取典型的有机种植基地与附近相似条件的常规种植地块,比较了不同种植方式下土壤体积质量、土壤中水稳性团聚体及土壤中各养分含量和土壤中7种重金属含量。结果表明:相比常规种植,有机种植降低了土壤体积质量,提高土壤中水稳性大团聚体数量,提高了土壤中水稳性团聚体的MWD值和GMD值,降低了分形维数D,提升了土壤水稳性团聚体稳定性,提高了土壤抗侵蚀的能力。有机种植方式下土壤中有机质含量相比常规种植提高了20%~80%,土壤中速效磷、速效钾、碱解氮和全氮、全磷等养分含量也显著提高,说明有机种植有利于土壤培肥,提高土壤肥力。与土壤背景值相比,土壤中重金属含量有不同程度的增加和积累,曹县有机基地As含量超过土壤环境质量国家一级标准,肃宁有机基地土壤中Cu、Zn含量接近国家一级标准。在调查地区,有机种植降低了土壤中Cr、Cd、Hg污染的威胁,但由于施入有机肥的质量差异,存在重金属Cu、Zn、As富集的风险。相比常规种植,有机种植有利于改善土壤结构,提高土壤综合肥力,土壤中重金属污染的风险主要与施入的有机肥质量有关,有机种植应加强对有机肥源的监控,合理施肥。     

Measuring bioavailable trace metals by diffusive gradients in thin films (DGT): soil moisture effects on its performance in soils

Conventional methods of measuring labile chemical species of trace metals in soil solutions, such as chemical competition following centrifuging, are inadequate if the speciation changes during sampling and extraction. A new technique, diffusive gradients in thin films (DGT), measures labile species of trace metals in natural waters and sediments in situ. A well-defined diffusive gel layer distinguishes it from other resin-based techniques. It perturbs the soil in a controlled way by introducing an in situ local sink for metal ions. Resulting fluxes to the device are quantitatively measured, allowing assessment of re-supply kinetics and in some cases measurement of in situ soil solution concentrations. We used DGT to measure fluxes of Cd, Co, Cu, Ni, Pb and Zn in a sludge-treated soil at various moisture contents (27–106%). Replicate measurements showed that the precision of DGT-measured fluxes was within 10%. For moisture contents exceeding the field capacity (42%), the DGT response reflected soil water concentrations. At smaller moisture contents, changes related to tortuosity and dilution were reflected in the measurements. This technique has the potential for in situ measurements in the field where it should provide quantitative flux data on individual soils and provide a good surrogate for bioavailable metal.     

包头市铜厂周边土壤中重金属垂直分布特征与形态分析

为了解包头市铜厂周边地区土壤剖面中重金属污染状况,采用火焰原子吸收分光光度法和Tessier连续提取法,对土壤中6种重金属（Cu,Zn,Mn,Ni,Pb和Cd）的垂直分布特征、形态及潜在生物可利用性进行了分析。结果表明:研究区土壤剖面各层土壤中6种重金属含量均超过内蒙古土壤背景值,Cu,Pb和Cd为主要污染物。随采样深度的增加,Cu,Zn,Pb和Mn的含量呈现下降趋势,且由相关性系数可知重金属Cu,Zn和Pb可能有相同人为或自然污染源;土壤剖面中6种重金属均主要以残渣态存在,含量均在50%以上,对生物危害较小;潜在生物可利用性分析结果为:Cu（32.61%） > Mn（31.85%） > Ni（24.90%） > Zn（16.60%） > Cd（15.23%） > Pb（14.87%）,Cu和Mn的潜在生物可利用性较大,其次为Ni,Zn,Cd和Pb潜在生物可利用性较小。     

重金属复合处理对小麦锌铜镍镉积累和分布的影响

为增加粮食可食用部分有益元素的浓度,同时减少有毒重金属元素的含量,需要更好地了解元素在植株和籽粒内的运输和分布。在温室盆栽条件下,以春小麦为供试材料,设置对照（不添加重金属）和重金属复合处理（同时添加铜、锌、镍、镉,以不影响小麦生长为前提）,研究锌（Zn）、铜（Cu）、镍（Ni）、镉（Cd）在成熟植株和籽粒不同部位的分布特点。结果表明,重金属复合处理对小麦成熟期籽粒和秸秆产量、收获指数以及粒重均无显著影响,但使小麦各器官重金属浓度均显著增加,增幅因不同器官和不同元素而异,籽粒中Zn、Cu、Ni和Cd浓度分别增加1.8、0.5、48.1倍和45.3倍。重金属复合处理还显著改变了Zn和Ni在地上部各器官中的分配模式：对照小麦吸收的Zn更易向生殖器官中转运,处理植株则更多地滞留在营养器官中,而Ni呈相反的趋势。激光剥蚀电感耦合等离子体质谱仪（LA-ICP-MS）对籽粒糊粉层和胚乳的定量分析表明,重金属复合处理使糊粉层Zn和Cu浓度仅增加了78%和86%,而糊粉层Ni和Cd浓度分别增加了30倍和121倍。重金属复合处理使胚乳Zn和Cu浓度分别增加了49%和48%,使Ni和Cd浓度均超出小麦标准中Ni和Cd的最大允许浓度（对照籽粒胚乳中没有检验到Ni和Cd）。以上结果表明,在小麦生物强化实践中,在增加有益营养元素（如Cu和Zn）的同时亦存在有毒重金属（如Ni和Cd）超标的巨大风险。     

Effect of controlled-release urea on heavy metal mobility in a multimetal-contaminated soil

Controlled-release N fertilizers can affect the availability of heavy metals in the contaminated paddy soil.A soil incubation experiment was conducted to investigate the effects of prilled urea(PU),S-coated urea(SCU),and polymer-coated urea(PCU)on the solubility and availability of heavy metals Cd,Pb,Cu,and Zn in a multimetal-contaminated soil.The results showed that the application of different coated urea significantly affected the solubility and availability of heavy metals.At 5 d of incubation,the application of PU,SCU,and PCU had significantly decreased the concentrations of water-soluble and available Cd,Pb,Cu,and Zn,when compared with the control.At 60 d of incubation,the depletory effects of PU on water-soluble and available heavy metals had reduced,and the initial decrease in the concentrations of water-soluble Cd,Pb,Cu,and Zn caused by SCU had changed to an increase.The concentrations of water-soluble Pb,Cu,and Zn in the SCU-treated soil were higher than those in the control.Application with PCU led to a higher water-soluble Cu than that in the control,while the available Cd,Pb,and Zn were lower than those in the control.The effect of different coated urea was much stronger on the water solubility of the heavy metals than on their availability.The effects of controlled-release urea on the transformation of heavy metals resulted in changes in the concentrations of NH4^+,water-soluble SO4^2-,and soil p H.The results further suggested that PCU could be used in dry farming operations in multimetal-contaminated acid soils.