绿洲土Cd、Pb、Zn、Ni复合污染下重金属的形态特征和生物有效性

通过模拟基于干旱区绿洲土壤Cd-Pb-Zn-Ni复合污染下的油菜盆栽试验,采用Tessier五步连续浸提法探究了重金属复合污染对油菜生长的影响及其各形态的转化归趋和生物有效性.结果显示,随着Cd-Pb-Zn-Ni复合胁迫水平的升高,油菜的干重先增加后减小,根系的生长由促进作用转变为抑制作用;对照土壤中4种重金属元素均以残渣态为主要赋存形态,可交换态的含量均很小;随着外源重金属的添加,油菜种植土壤中4种重金属元素的各形态含量随之增加,Cd、Pb、Zn的可交换态和Ni的碳酸盐结合态对外界胁迫响应强度最大,Cd、Pb、Zn、Ni的活性增加,且Cd、Pb的主要赋存形态迅速转变为碳酸盐结合态和铁锰氧化态,Zn的主要赋存形态由残渣态和碳酸盐结合态过渡到碳酸盐结合态和铁锰氧化态,Ni的主要赋存形态为碳酸盐结合态;Cd、Zn在茎叶中的含量大于根系,Pb、Ni反之,油菜能将Cd、Zn更多的运输至茎叶,Pb、Ni则主要积累在根系;油菜茎叶吸收Cd和油菜各部位吸收Zn的主要贡献形态为可交换态,根吸收Cd的主要贡献形态由可交换态转变为有机结合态,根吸收Pb和油菜各部位吸收Ni的主要贡献形态为碳酸盐结合态.     

根际环境中铅的形态转化

用根际箱试验研究了红壤植麦和植稻后根际中Pb的形态转化 ,讨论了与Cd复合处理对Pb形态的影响 .结果表明 ,Pb在红壤根际、非根际的主要形态为酸解态 +碳酸盐态、交换态和铁锰氧化物结合态 .交换态Pb都是根际 >非根际 ;不同Pb处理浓度和Pb Cd交互作用都对Pb的形态分布产生影响 ,小麦根际随加入Cd浓度增大 ,根际交换态Pb和铁锰氧化物结合态Pb下降 ;水稻根际交换态Pb与Cd复合处理浓度密切相关 ,5mgCd·kg-1复合处理 ,根际交换态Pb的活化较单元素弱 ,10mgCd·kg-1复合处理 ,根际交换态Pb的活化较单元素要强 .     

根际环境中铅的形态转化

用根际箱试验研究了红壤植麦和植稻后根际中Pb的形态转化,讨论了与Cd复合处理对Pb形态的影响.结果表明,Pb在红壤根际、非根际的主要形态为酸解态+碳酸盐态、交换态和铁锰氧化物结合态.交换态Pb都是根际>非根际;不同Pb处理浓度和PbCd交互作用都对Pb的形态分布产生影响,小麦根际随加入Cd浓度增大,根际交换态Pb和铁锰氧化物结合态Pb下降;水稻根际交换态Pb与Cd复合处理浓度密切相关,5mgCd·kg^-1复合处理,根际交换态Pb的活化较单元素弱,10mgCd·kg^-1复合处理,根际交换态Pb的活化较单元素要强.     

采用浇灌方式施用甲酸钙消减当季叶菜镉污染

中轻度Cd污染农业土壤修复多采用以pH调控为主的钝化措施,但在pH中性土壤中综合效果不佳。本研究提出在蔬菜生长时期用甲酸钙溶液强化根际土壤交换态Cd向碳酸盐结态Cd的转化,在基本不改变土壤pH的情况下,阻控蔬菜对pH中性土壤Cd的吸收。室内模拟实验表明,低浓度甲酸钙(1.3~3.9 g·L~(-1))可以促使土壤交换态Cd转化为水溶态Cd;24 h内甲酸根生物降解后,土壤碱度有所提高,但pH变化不大,利于土壤交换态Cd转化为水溶态Cd后继续转化为生物有效性相对更低的碳酸盐结合态Cd。采用全Cd含量为1.03 mg·kg~(-1)、pH为7.3的棕壤开展油菜盆栽实验,结果显示,在油菜生长中后期2次以灌溉形式按76、152或228 mg·kg~(-1)土的剂量添加甲酸钙后,收获时油菜Cd含量分别比对照组减少31.6%、32.7%和39.4%,但不同处理土壤pH变化很小;在第二茬盆栽实验中,不同处理油菜Cd含量差异消失。甲酸钙阻控当季蔬菜吸收土壤Cd的作用主要归因于其对土壤交换态Cd向碳酸盐结合态Cd转化的促进作用,但土壤交换性阳离子组成与含量、铁锰氧化物和有机质等因素对甲酸钙阻控效果的影响还有待进一步研究。     

有机物料对滨海盐渍土重金属根际效应的影响Ⅰ.土壤内源Zn形态分布

研究了排水条件下施用腐熟有机物料、种稻改良滨海盐渍土内源Ｚｎ形态分布．结果表明,单淹水使土中各形态Ｚｎ一定程度上向生物有效性较低的Ｚｎ形态转化,有效态Ｚｎ降低．土壤盐分量不同,明显影响无定形氧化铁结合态、紧结有机态以及硅酸盐矿物态Ｚｎ变化．种稻不施有机物料,根际交换态和硅酸盐矿物态Ｚｎ亏缺;碳酸盐结合态、氧化锰结合态和无定形氧化铁结合态Ｚｎ富集．根际Ｚｎ形态转化强度大于非根际,其有效态Ｚｎ量接近临界值并高于非根际．有机物料利于根际内外土壤中硅酸盐矿物态Ｚｎ的转化,低盐土壤根际更强烈．随有机物料用量增加,促使根际硅酸盐矿物态、碳酸盐结合态及氧化锰结合态Ｚｎ向交换态、紧结有机态和无定形氧化铁结合态Ｚｎ转化,低盐土壤较明显．     

有机物料对滨海盐渍土重金属根际效应的影响 Ⅰ.土壤内源Zn形态分布

研究了排水条件下施用腐熟有机物料、种稻改良滨海盐渍土内源Zn形态分布。结果表明,单淹水使土中各形态Zn一定程度上向生物有效性较低的Zn形态转化,有效态Zn降低。土壤盐分量不同,明显影响无定形氧化铁结合态、紧结有机态以及硅酸盐矿物态Zn变化。种稻不施有机物料,根际交换态和硅酸盐矿物态Zn亏缺;碳酸盐结合态、氧化锰结合态和无定形氧化铁结合态Zn富集。根际Zn形态转化强度大于非根际,其有效态Zn量接近临界值并高于非根际。有机物料利于根际内外土壤中硅酸盐矿物态Zn的转化,低盐土壤根际更强烈。随有机物料用量增加,促使根际硅酸盐矿物态、碳酸盐结合态及氧化锰结合态Zn向交换态、紧结有机态和无定形氧化铁结合态Zn转化,低盐土壤较明显。     

菌根植物根际环境对污染土壤中Cu、Zn、Pb、Cd形态的影响

采用根垫法和连续形态分析技术,分析了生长在污灌土壤中菌根小麦和无菌根小麦根际Ｃｕ、Ｚｎ、Ｐｂ、Ｃｄ的形态分布和变化趋势。结果表明,下对照土壤相比,菌根际土壤中交换态Ｃｕ含量显著增加,交换态Ｃｄ呈减少的趋势;与非菌根际相比,Ｃｕ、Ｚｎ、Ｐｂ的有机结合态在菌根根际中显著增加,而４种测定金属２的碳酸盐态和铁锰氧化态都没有显著改变,该结果表明,植物根系能影响根际中金属形态的变化,且菌根比无菌根的影响程度大     

稻麦轮作下水稻土重金属形态特征及其生物有效性

在成都平原稻麦轮作下86个土样中重金属全量和各形态含量分析的基础上,采集分析相应点位上种植的主要粮食作物小麦和水稻籽粒的重金属含量,通过描述性统计分析、相关性分析及线性回归方程的模拟,研究了土壤中重金属的形态分布特征及其生物有效性。统计分析结果表明：土壤中Cr、Cu、Pb、Zn各形态含量的分配顺序为：残渣态〉有机物结合态〉铁锰氧化物结合态〉碳酸盐结合态〉可交换态,而Cd各形态含量的分配顺序为：铁锰氧化物结合态〉残渣态〉碳酸盐结合态〉有机物结合态〉可交换态。若以活性态（非残渣态含量）而论,Cd的活性最高,Cr的活性最低。除Cr外,各元素全量与各活性形态之间的关系较为密切。土壤中全Cd含量与4种活性形态Cd含量间的相关性均达极显著水平;Cu、Zn全量分别与其铁锰氧化物和有机物结合态含量,Pb全量分别与其可交换态和铁锰氧化物含量间的相关系数达显著或极显著水平。用卫生部颁布的食品中重金属限量卫生标准评价稻麦籽粒重金属累积情况,其结果表明,小麦籽粒（旱作）中的Cd、Cr、Cu、Pb分别超标14.71%、8.70%、6.50%和17.40%,而水稻籽粒（水作）仅有Pb和Cd含量超标10.90%和8.70%。不同形态重金属对水稻和小麦籽粒中重金属累积的影响效应不同，从多元线性回归方程的回归系数来看：稻一麦籽粒中Cd含量受到土壤中各活性形态Cd含量的影响。除铁锰氧化态Cd和有机物结合态Cd含量分别对小麦和水稻籽粒中Cd的累积表现出负效应外，其余均为正效应。可交换态Cu含量对稻-麦籽粒Cu累积的效应最大，其次受碳酸盐结合态Cu含量的影响。稻一麦籽粒Pb含量的累积受土壤各活性态Pb含量影响效应的差异不甚明显。稻-麦籽粒Zn含量与土壤各活性态Zn含量间无显著线性关系。     

外源水溶性有机物及温度对红壤铜形态的影响

利用模拟培养试验研究了外源水溶性有机物（DOM）添加量和培养温度对红壤中Cu形态的影响. 结果表明: 与不添加DOM比较, 添加不同量的DOM均可提高土壤中交换态Cu的含量、降低铁锰结合态Cu含量; 随着培养时间的延长,不同DOM添加量下土壤交换态Cu含量呈逐渐下降趋势;至试验结束时,DOM添加量为250 mg·L^-1时土壤交换态和碳酸盐结合态Cu含量最高, 添加量为500 mg·L^-1时铁锰结合态Cu含量最高;不同DOM添加量下, 土壤中有机结合态Cu含量较CK增加10.67%～23.66%. 在25 ℃和45 ℃温度条件下, 添加DOM后土壤交换态和铁锰结合态Cu含量均随培养时间的延长呈下降趋势, 但在5 ℃下变化趋势相反; 3种温度下添加DOM后土壤碳酸盐结合态Cu含量有随培养时间延长而增加的趋势. 随着培养温度的升高,土壤有机结合态Cu含量增加, 但在温度较低(5 ℃)时土壤残渣态Cu含量下降.     

玉米根际土壤中铜形态的动态变化

采用根垫法研究玉米根际土壤形态动态变化。结果表明：玉米生长过程中根际土壤铜形态发生显著变化。植物生长前期交换态和碳酸盐结合态铜含量逐渐增加,随后增加量减少。植物生长后期根际交换态和碳酸盐结合态铜含量低于非根际土壤。这种变化主要由根际环境变化与植物吸收引起。与根限土壤中铜形态变化,特别是交换态铜含量变化关系密切的因素包括土壤溶解性有机碳、pH和土壤微生物。随着植物生物量的增加,对铜的吸收速率不断增加,导致根限土壤中有效态铜的先增后减。     

河北主要土壤中Cd、Pb形态与油菜有效性的关系

当今土壤重金属污染日趋严重而表征土壤污染程度 的指标不够完善、相关性亦较差。为此,采用网室盆栽试验,研究了河北平原主要土壤类型潮土和潮褐土上Cd、Pb的化学形态特征及其与油菜植株干物重、油菜吸收重金属含量的关系。结果表明Cd对油菜的毒害作用大于Pb。总量及各形态Cd、Pb含量与油菜可食部分干物重呈负相关,对油菜干物重影响最大的是交换态Cd、Pb。而对油菜吸收Cd、Pb贡献最大的形态是碳酸盐结合态和铁锰氧化物结合态。深入研究重金属形成与植物有效性间的关系,可为进一步揭示重金属的生物有效性,为更准确评价土壤重金属污染程度提供理论依据,具有重要的理论意义和实际应用价值。     

Cd、Pb投加浓度对其在黑土中化学形态分布及油菜生长和吸收Cd、Pb的影响

采用室内模拟实验和连续形态分级方法研究了Cd、Pb投加浓度对其在黑土中化学形态分布及油菜生长和吸收Cd、Pb量的影响.结果表明:随Cd、Pb投加量的增加,土壤中Cd交换态含量增幅较大,Pb碳酸盐结合态、Fe-Mn氧化物结合态含量增幅较大;外源Cd在土壤中的存在形态以交换态和残留态为主,Pb的交换态比例相对较低,其存在形态主要为残留态;土壤Cd、Pb投加浓度较低时,促进了油菜的生长,投加浓度较高时,对油菜生长的抑制作用较为明显;地下部分Cd、Pb含量远高于地上部分,与Cd相比,Pb向地上部的迁移率相对较小;土壤中Cd、Pb各形态含量与油菜地下、地上部分吸收的Cd、Pb量均呈显著正相关,与干质量呈负相关;交换态Cd、Pb对油菜干质量影响最大,碳酸盐结合态对油菜吸收Cd、Pb的贡献最大.     

Spatial Variation and Fractionation of Bed Sediment-Borne Copper,Zinc, Lead,and Cadmium in a Stream System Affected by Acid Mine Drainage

An investigation was conducted to examine the spatial variation and fractionation of bed sediment-borne Cu, Zn, Pb, and Cd in a stream system affected by acid mine drainage. The pH had a major control on the spatial variation pattern of soluble, exchangeable, and carbonate-bound Cu, Zn, and Cd. There was a prominent concentration peak of carbonate-bound, oxide-bound, and organic-bound metals at the 29 km station, as controlled by the abundance of organic C, carbonate C, and oxides of manganese and iron. In general, the residual fraction was the dominant form for all four investigated metals. It was likely that oxide-Mn played a more important role in binding Zn and Cd than oxide-Fe did. In contrast, Cu had a higher affinity for iron hydrous oxides than for manganese oxide. Pb had a higher affinity for oxides of iron and manganese than for carbonates and organic matter. The presence of organic-bound metals in both the acidic upstream reach and non-acidic downstream reach suggests that the binding of these metals by organic matter was not markedly affected by pH, while the correspondence of organic C peak and organic-bound metal peaks at the 29 km station indicates a strong control by organic matter abundance on the quantity of organic-complexed metals.     

硅对土壤-烟草系统中铅迁移及形态分布的影响

通过盆栽试验,以烟草为对象,研究了硅对土壤 烟草系统中铅的迁移以及土壤、烟草中铅形态分布的影响.结果表明： 施硅使非根际土壤可交换态铅向铁锰氧化物结合态转化,使根际土中交换态铅向铁锰氧化物结合态和残渣态转化,降低了土壤中铅的植物有效性与迁移性.施硅显著提高了烟草根部和叶部的生物量,显著降低了烟草铅的总吸收量和烟草各器官的铅含量,其中烟草铅的总吸收量降低了6.5%～44.0%,烟叶铅含量降低了3.1%～60.4%.施硅使烟草根、茎和叶中乙醇提取态、去离子水提取态和氯化钠提取态向盐酸提取态和残渣态转化,降低了烟草体内铅的毒性与迁移性.土壤-烟草系统中土壤向烟草根部的移动指数和根部向茎部的移动指数随施硅量的增加而降低,烟草茎部向叶部的移动指数随着施硅量的增加呈先增高后降低的趋势.硅通过降低土壤铅有效性、缓解铅对烟草的毒害、改变烟草体内铅的形态分布,进而抑制土壤中铅向烟草叶部的迁移,降低烟叶中的铅含量.施硅是降低土壤铅的迁移性及烟叶铅含量的有效措施.     

芜湖钢铁厂周边土壤及油菜籽中镉、铜、锌、铅含量和形态分布研究

研究了污染土壤、油菜籽中Cd、Cu、Zn、Pb含量、形态分布特征和重金属富集状况及可能存在的生物毒性.结果表明,土壤中Cd、Zn、Pb以铁锰氧化物结合态、Cu以残留态占5种形态最高比例,分别为31.1%、39.3%、53.79%、46.24%;Cd、Pb交换态比例较高,为23.47%、16.32%,Cu、Zn的交换态比例较小,为3.14%、0.54%;土壤中不同重金属与各重金属形态相关关系有差别,5种重金属形态转化为有效态重金属难易程度不同;油菜籽和油菜籽壳中不同重金属累积趋势有差异,Cu易在油菜籽壳中累积,Cd、Zn、Pb易在油菜籽中累积;油菜籽中不同重金属累积率不同,Cd累积率最高,为0.56.油菜籽中重金属累积率与土壤中重金属总量呈显著负相关关系(P＜0.05),土壤中重金属的形态、转化差异是此种负相关关系的主要原因;油菜籽中Cd、Cu、Pb以氯化钠态为主,分别为32.50%、22.94%、34.69%,Zn以EDTA态为主,为45.97%.油菜籽中重金属形态可能影响其毒性,但其毒性的人类膳食风险还需进一步研究证实.油菜籽中重金属形态与油菜中重金属总量相关性不好.     

Studies on soil rhizosphere: speciation and availability of Cd

ABSTRACT

The rhizosphere soils of two durum wheat (Triticum turgidum var. durum L.) cultivars Kyle and Areola grown in two selected soils of southern Saskatchewan were collected both at 2-week and 7-week plant growth stages. The cadmium availability index (CAI), determined as M NH₄CI-extractable Cd, pH and the distribution of the particulate- bound Cd species of the soils were carried out and the data were discussed in comparison with those of the corresponding bulk soil. At the 2-week growth stage, the pH of the rhizosphere soil was less than that of the corresponding bulk soil and the CAI values were higher in the rhizosphere soil, indicating that more Cd was complexed with the low-molecular-weight organic acids (LMWOAs) at the soil-root interface and was extractable by M NH₄CI. Compared with the bulk soils, the CAI values were 2–9 times higher in the soil rhizosphere of the plots fertilized with Idaho monoammonium phosphate fertilizer at 2-week growth stage, which is attributed to the combined effects of the Cd introduced into the soil rhizosphere from the fertilizer (Cd content of the fertilizer was 144 mg kg^?1) and complexation reactions of phosphate and LMWOAs with soil Cd. At 7-week plant growth stage, such differences were not observed. The increased amounts of carbonate-bound and metal-organic complex-bound Cd species of the rhizosphere soils are due to the increased amounts of carbonate, a product of plant respiration, and the LMWOAs at the soil-root interface, respectively. Simple correlation analysis of the data showed that the CAI of the rhizosphere soils of the control plots correlated at least two orders of magnitude better with the metal-organic complex-bound Cd whereas the CAI of the rhizosphere soils treated with Idaho phosphate correlated better with carbonate-bound Cd species in comparison to other species.     

Cd uptake by intact wheat plants

Abstract. An investigation of the uptake of Cd by intact wheat plants has been carried out. The accumulation of Cd in the roots as a function of time and external Cd concentration was determined. Since the transport of Cd to the grains and shoots was found to be small, only uptake into the root was examined further. An appreciable fraction of the Cd absorbed by the roots can be desorbed and consequently constitutes the freely diffusible and exchangeable fraction.
The effect of temperature and of metabolic inhibitors on the absorption provides evidence that another Cd fraction is taken up by metabolically mediated processes. The absorption of this Cd fraction was found to be inhibited by Cu and Zn. The inhibitory effect of Cu and Zn on Cd absorption was comparable.     

模拟酸雨对污染土壤中Cd、Cu和Zn释放及其形态转化的影响

研究了模拟酸雨连续浸泡下污染红壤和黄红壤中重金属释放及形态转化．结果表明。随着模拟酸雨pH值下降,污染土壤中重金属释放强度明显增大;Cd、Zn释放量与酸雨pH值呈线性极显著负相关．Cu与酸雨pH值呈线性显著负相关．模拟酸雨作用下,污染红壤和黄红壤中Cd均以交换态为主;Cu则以有机结合态和氧化锰结合态为主;Zn在污染红壤中以残留态和交换态为主．在污染黄红壤中以残留态和有机结合态为主．土壤有机质含量和阳离子交换量对Cd、Cu、Zn的释放产生一定的影响并影响Cd、Zn的形态转化,但对Cu形态转化影响不明显,随着模拟酸雨酸度增大,污染红壤和黄红壤中重金属Cd、Cu的生物可利用态明显增多,但难解吸态Zn向生物有效态转化效应不明显．     

The migration and transformation regular study of metal manganese in surface soil of Yiwang Industrial Park in Shanxi Province,China

All kinds of industries can produce a large amount of the heavy metal Mn emission, especially in the Mn steel plant production process. The assessment of Mn pollution in industrial areas is vital to human health and soil conservation. First, there are 120 samples of 0–5 cm and samples 9 of 0–40 cm of the surface soil collected from outside. Next, the soil column test is applied to study the migration and speciation regularity of Mn in 0–40 cm of soil layer, and then a forecasting model is established to verify and evaluate the Mn pollution in the study area. After the exogenous Mn enters the soil, Mn soon transforms into a more stable form in soil at 0–20 cm depth. But the residual amounts of Mn in deep soil increases with the increase of exogenous Mn. The main speciation of Mn in surface soil includes residual, oxide-bound, and organic-bound forms. Carbonate-bound form is sensitive to the increase of exogenous Mn. The exogenous Mn content has less influence on the content of oxide-bound and organic-bound forms in soils below 20 cm. The prediction model can be used to evaluate the degree of pollution of Mn in surface soil of the study area.