螯合剂对小麦幼苗吸收金属以及土壤金属形态的效应

本文通过盆栽试验研究三种螯合剂（EDTA、[s,s】-EDDS、DTPA）对小麦幼苗吸收土壤中重金属及其它微量元素的效应,并且通过改进的BCR连续提取法分析了种植后土壤样品中金属元素的形态。结果表明：EDTA、DTPA的添加导致小麦幼苗地上部分生物量以及叶片叶绿素a含量显著下降。螯合剂的存在明显增加了Pb和Mn在幼苗根部和茎叶的富集,并增加其由根部向茎叶的传输．但对Fe和Ni的作用比较小。小麦幼苗收获时,除Zn之外,其它元素酸溶／可交换态金属含量与对照组相比均有非常显著的增加,而各元素的可还原态由于EDTA等螯合剂的添加而有明显下降。添加螯合剂的情况下,富集量与酸溶／可交换态含量之间的相关系数大大提高,且各处理组茎叶富集量与酸溶／可交换态之间呈显著（P〈0．05）或极显著相关（P〈0．01）。因此,三种螯合剂的添加主要影响的是生物可利用形态以及潜在的生物可利用形态,并且可能导致可还原态以及可氧化态向酸溶／可交换态转变,增加金属的生物可利用性,从而也增加潜在生态风险。     

两种螯合剂施用对污染土壤中叶用红恭菜Cd富集的影响

为探讨螯合剂对植物吸收重金属的影响,采用盆栽试验,研究了螯合剂乙二胺四乙酸（EDTA）和柠檬酸（CA）对土壤重金属cd的有效态以及叶用红恭菜（Beta vulgaris var．cicla L）富集Cd能力的影响。结果表明：EDTA的添加比柠檬酸更显著增加了土壤重金属镉的有效态含量,同时提高了叶用红恭菜茎叶的富集系数和转运能力;施用螯合剂促进了Cd从叶用红恭菜茎叶根部向茎叶的输送,叶用红恭菜茎叶含Cd量显著增加,EDTA的作用是柠檬酸的2～3倍。     

两种螯合剂施用对污染土壤中叶用叶叶叶Cd富集的影响

为探讨螯合剂对植物吸收重金属的影响,采用盆栽试验,研究了螯合剂乙二胺四乙酸(EDTA)和柠檬酸(CA)对土壤重金属Cd的有效态以及叶用红菾菜(Beta vulgaris var.cicla L)富集Cd能力的影响.结果表明:EDTA的添加比柠檬酸更显著增加了土壤重金属镉的有效态含量,同时提高了叶用红菾菜茎叶的富集系数和转运能力;施用螯合剂促进了Cd从叶用红菾菜茎叶根部向茎叶的输送,叶用红菾菜茎叶含Cd量显著增加,EDTA的作用是柠檬酸的2～3倍.     

螯合剂对土壤中镉赋存形态及其生物有效性的影响

以胡萝卜作为试验植物,研究了EDTA,EGTA,DTPA和柠檬酸四种螯合剂对土壤中Cd的赋存形态及生物有效性的影响.结果表明,在碱性土壤中,加入螯合剂EDTA,EGTA和DTPA都能显著改变土壤中Cd的赋存形态,增加有效态Cd的百分比含量,改善Cd的生物有效性;但施加柠檬酸对Cd的赋存形态没有产生明显影响,各形态组成与对照组基本一致.同时,试验结果还显示,胡萝卜中Cd含量随着添加螯合剂浓度的增加先增大而后有所降低,但除柠檬酸处理组外,均明显高于对照组,表明四种螯合剂均能增强胡萝卜对Cd的吸收,且以EGTA效果最佳,EDTA和DTPA次之,柠檬酸最差.     

土壤中重金属[S,S]-乙二胺二琥珀酸浸提及其对重金属形态分布的影响

采用螯合剂[S,S]-乙二胺二琥珀酸([S,S]-EDDS)对废弃矿区附近的农田土壤进行浸提,分析浸提前后残留土壤样品中重金属的形态.结果表明,[S,S]-EDDS对重金属元素的提取率在不同土壤之间有较大差异,对Cu的浸提率为13.4%-13.8%,对Pb的浸提率为2.28%-16.3%,对Zn的浸提率为2.73%-11.3%.[S,S]-EDDS在提取重金属的同时也造成了Fe和Mn的明显溶出,其中Fe的溶出率为0.090%-0.291%,Mn的溶出率为2.53%-6.31%,均远高于对照组.[S,S]-EDDS浸提后酸溶/可交换态金属含量的变化倚赖于金属种类,对于Cu和Zn,经[S,S]-EDDS浸提之后,其酸溶/可交换态含量远低于对照组;但对于Pb,经[S,S]-EDDS浸提之后,酸溶/可交换态含量略高于对照组.[S,S]-EDDS对Cu和Zn四种形态均有浸提作用,且对残渣态的影响小于其它形态.[S,S]-EDDS浸提导致土样中Cu和Zn残渣态比例上升,其它形态比例的变化则依赖于金属的种类以及土壤性质.     

生物炭和熟石灰对土壤镉铅生物有效性和微生物活性的影响

以南京近郊某蔬菜基地土壤为研究对象,采用盆栽试验方法,研究熟石灰和生物炭两种钝化剂对镉铅复合污染土壤修复效果以及对土壤微生物活性的影响.结果表明,施加熟石灰和生物炭能够增加土壤pH和有机碳等养分含量,促进Cd、Pb由酸溶态向还原态和残渣态转化,降低Cd、Pb有效态含量.与对照处理相比,熟石灰和生物炭5.0%用量下,Cd有效态含量(DTPA、TCLP和CaCl_2等3种提取态)分别下降37.74%—41.46%和22.22%—31.71%,Pb有效态含量分别下降45.59%—52.82%和35.47%—41.94%.生物炭的施用提高了土壤微生物量碳氮和微生物群落功能多样性,促进微生物对碳源的利用能力,其中生物炭5.0%用量下土壤微生物活性最高.熟石灰和生物炭的添加显著降低小白菜可食部位和根部对Cd、Pb的富集,与对照处理相比,可食部位Cd、Pb含量分别下降7.14%—47.62%和45.93%—74.82%,但所有添加钝化剂处理小白菜可食部位含量均超出国家安全食用标准.     

夹皮沟金矿区土壤汞的赋存形态及污染特征

使用改进的BCR连续提取法和电感耦合等离子质谱(ICP-MS),测定夹皮沟金矿区土壤样品中汞元素的赋存形态及含量。结果表明,三个深度的土壤汞元素形态分布趋势相似,均以残渣态为主,其次为可氧化态和可还原态,酸溶/可交换态和水溶态所占比例较少,各形态汞的分配系数依次为:残渣态(48.28%)可氧化态(25.68%)可还原态(13.35%)酸溶/可交换态(8.38%)水溶态(4.33%)。垂直方向上,20~40 cm的中层土壤中的汞含量略高于0~20 cm的表层土壤,40~60 cm的下层土壤则含量最低。不同深度土壤中的有效态汞与总汞的含量具有较高的相关性,但三层土壤不具有相同的相关趋势。     

绿洲土壤Cd-Ni复合污染对油菜生长及吸收的影响

以干旱区绿洲灰漠土为供试土壤,油菜(Brassica campestris L.)为供试蔬菜,采用盆栽试验及Tessier连续浸提形态分级方法,研究了Cd-Ni复合污染在干旱区绿洲土壤中的形态分布规律及其对油菜的生物有效性.结果表明,当土壤受外源Cd-Ni复合污染后,Cd、Ni的活性随着胁迫浓度的增加而增大.与对照相较,外源Cd-Ni复合胁迫后,Cd的主要赋存形态仍为碳酸盐结合态,而Ni的主要赋存形态由残渣态转化为铁锰氧化物结合态.Cd-Ni复合胁迫对油菜的生长表现为先促后抑;油菜各部位的Cd、Ni含量均随着Cd-Ni复合胁迫水平的升高而增加,Cd主要富集在油菜茎叶中,而Ni则主要富集在油菜根部.富集系数结果表明,油菜各部位Cd的富集系数均大于1,而Ni的富集系数均小于1;迁移系数结果表明,Cd的迁移系数大于Ni,Cd更易从土壤中进入油菜根部,并转运至茎叶,Ni的生物可利用性低于Cd.对油菜吸收Cd最重要的形态为碳酸盐结合态,根系和茎叶吸收Ni最重要的形态分别为有机结合态和可交换态.     

熟污泥改良土壤中Cd的形态分布特征和生物有效性

通过苜蓿盆栽实验和Tessier五步提取法,研究了不同比例的堆肥污泥施入黄土后,土壤中Cd的形态分布和生物有效性及重金属在施污土壤-苜蓿中的迁移转化规律。结果表明：不同比例的污泥施入黄土后,随着污泥施入量的增加,土壤中Cd的主要赋存形态由对照组的不可利用态(残渣态)向潜在有效态(铁锰氧化态)转化,污泥的施入提高了重金属Cd的生物有效性;苜蓿的种植对施污根际土中Cd的活性产生了钝化作用,使施污黄土根际土壤中潜在有效态Cd主要向不可利用态的Cd转化;苜蓿各器官对Cd均有富集和转移能力,苜蓿各部位重金属Cd含量的分布规律为：根部>茎叶部;线性回归分析结果表明：碳酸盐结合态Cd是苜蓿茎叶部和根部吸收Cd的主要贡献形态;因此在实际生产时须严格控制污泥的施用量,以避免Cd在苜蓿体内富集危害动物和人体健康。     

生物炭对湘潭锰矿区土壤重金属的固化效应

通过室内培养实验,研究不同施用量(1%、2%、5%、10%、20%)的生物炭对锰矿区周边土壤中3种重金属锰(Mn)、铅(Pb)、铬(Cr)的固化效应。结果表明,生物炭施入土壤可使土壤中酸溶态、可还原态Mn、Pb、Cr含量分别降低1.18%~61.70%、2.38%~62.15%;而使土壤中可氧化态、残渣态Mn、Pb、Cr含量分别增加1.9%~224.41%、1.33%~44.5%;并且生物炭施入量与土壤中酸溶态、可还原态Mn、Pb、Cr含量呈显著负相关(r:-0.850~-0.526,P0.05),与土壤中可氧化态、残渣态Mn、Pb、Cr含量呈显著正相关(r:0.589~0.880,P0.05)。培养时间的延长对土壤中酸溶态、可还原态Mn、Pb、Cr向可氧化态、残渣态的转化有一定的促进作用。生物炭的施入也可极显著提高土壤p H值(P0.01),土壤p H值与土壤中酸溶态、可还原态Mn、Pb、Cr含量呈极显著负相关(r:-0.832~-0.559,P0.01),与土壤中可氧化态、残渣态Mn、Pb、Cr含量呈极显著正相关(r:0.634~0.878,P0.01),但培养时间对土壤p H值的变化无显著影响。该研究结果可为生物炭对湘潭锰矿区周边土壤中重金属Mn、Pb、Cr的固化效应研究提供一定的理论依据。     

填埋场内重金属总量及其形态分布对迁移性的影响

以杭州市天子岭填埋场为例,对不同深度填埋层中的重金属总量、重金属迁移率和重金属形态分布进行了研究．结果表明,尽管填埋层中的重金属总量是土壤背景值的数十倍,超出土壤环境质量标准,但是重金属的迁移率却很低．另外,重金属迁移率与可交换态含量相关;Cd,Cu,Pb,Cr,Ni和Zn在填埋层中均以残渣态为主,填埋场中重金属都得到了有效固定,迁移性很差;各元素的易还原态与难还原态是重金属除残渣态之外主要的结合态(除Cr),铁锰氧化物循环是控制填埋场中重金属转化行为的主要机制之一;Cu的酸可溶态与易还原态具有较好的相关性,说明cu这两种形态的转化行为相似．     

宝鸡城市街尘、土壤及河流沉积物重金属形态迁移特征

在宝鸡城市街尘、土壤及河流沉积物基本理化性质和重金属元素含量分析的基础上,重点研究了重金属元素在街尘、土壤及河流沉积物中的赋存形态和迁移特征.结果表明:在街尘中Cu主要以可氧化态和残余态形式存在,Pb主要以可还原态和可氧化态形式存在,Zn和Cd主要以乙酸可提取态形式存在,Mn、Fe、Co、Ni和Cr主要以残余态形式存在...     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

Geochemical speciation of trace metals in sediments of the northern Nile Delta Lake by sequential extraction technique

ABSTRACT

The present study was performed to investigate surface sediment samples from Lake Edku of the Nile Delta Lagoons, Egypt. The Lake is important for fishing in the region. The importance of research is to understand the mobility and bioavailability of each studied metal. The study was carried out on 10 sampling sites during 2017. The sediments were subjected to the technique of sequential extraction to examine the chemical forms of some trace metals (Fe, Mn, Zn, Cu, Pb and Ni). Five stage extractions were done as the following order: soluble and exchangeable, carbonate, iron and manganese oxides, organic matter fraction and residual fraction. Attained results from the five fractions showed variations in the concentrations of metal contents of different sites under study. The overall metal concentrations (%) in the initial four extractable fractions (exchangeable, carbonate, oxides and organic matter fractions) were assessed to configure the mobility of each studied metal. The risk assessment code (RAC) represents the summation of exchangeable and carbonate fractions, it was between low and medium risk for aquatic environment. The range percentage of RAC for the metals was in the following order: 1.8–13, 4–23.5, 15–26, 5.7–19.5, 9–25 and 4.8–18.2 for Fe, Mn, Zn, Cu, Pb and Ni, respectively. Approximately 30% of the total copper was associated to the organic fraction, which may represent a high mobility of copper in these sediments. The highest mobility of metals in the sediments could be confirmed by its bioavailability factor (BF), which was within the ranges of 0.32–0.61, 0.36–0.59, 0.64–0.83, 0.36–0.72, 0.37–0.62 and 0.52–0.78 for Fe, Mn, Zn, Cu, Pb and Ni, respectively. The BF exhibited the following order: Zn > Ni > Cu > Pb ≈ Mn?>?Fe. The high levels of BF for the studied metals may represent the potentiality for toxic metals to be easily released into the aquatic environment.     

Distribution and speciation of heavy metals in Apulian coastal sediments

In the framework of the Interreg II Project Italy–Greece, distribution and speciation of trace metals in surface coastal sediments of Apulian regions were studied. A sequential extraction technique was used to determine the chemical association of heavy metals (Zn, Pb, Ni, Fe, Cr, Mn, Cu and Cd) with major sedimentary phases (acid soluble phases, easily reducible fraction and oxidizable matter). The relationship between the metals' content and the grain-size composition of the sediments was also considered: generally the elements resulted associated with the fine fraction, even if in some cases (Cu in the oxidizable phase) the opposite behaviour was observed. The studied area is not particularly polluted, except for some defined zones, as for example Brindisi's harbour. Speciation analysis revealed that the major part of the heavy metals are not easily mobilizable and bioavailable. Even in this case, there are some exceptions to the general behaviour: Cu and Pb in several samples are largely present in the oxidizable phase, which even if not immediately available can become a source of associated elements when redox conditions change.     

Speciation of Heavy Metals in Floodplain and Flood Sediments: a Reconnaissance Survey of the Aire Valley, West Yorkshire, Great Britain

A five-step sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Zn, Cu and Cd), with major sedimentary phases (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions), in samples from floodplain and recent flood sediments of the River Aire, West Yorkshire. Analysis indicates that metals Pb and Zn are primarily associated with the Fe and Mn oxides, Cu with the organic fraction and Cd with exchangeable and surface oxide and carbonate metal ions. Knowledge of the chemical speciation of heavy metals in river sediment, despite the procedure's inherent limitations, facilitates an understanding of their bioavailability, storage and remobilisation in floodplain and river channel environments.     

Chemical fractionation of metals in core sediments of Orogodo River,southern Nigeria

Sequential chemical extraction of metals (Cu, Ni, Mn, Fe, Pb, Cr, and Zn) from core sediments of the Orogodo River was carried out with a view of providing information on the phase distribution of these metals with respect to depths and seasons. The results indicate that copper was speciated into organic matter/sulfide, Fe–Mn oxides, and residual forms at 0–5?cm depth while at deeper sections copper was predominantly in the residual form. Nickel was speciated mainly into Fe–Mn oxides and residual forms. The average of lead in various particulate phases of the sediment are 0–100% for residual; 0–8% for carbonate; 0–16.2% for exchangeable; 0–10% for organic matter/sulfide form and 22–56% for Fe–Mn oxides bound metals. Manganese was speciated into exchangeable (10–36%) and Fe–Mn oxides bound (10–48%) at the surface layers of 0–20?cm depths and predominantly in the residual form in deeper sections implying partitioning into trioctahydral clay and/or well-defined crystalline oxides. Iron was predominantly in the Fe–Mn oxides and residual fractions, less than 8% in the organic fraction, and 24.4–37.3% in the exchangeable and carbonates fractions at the surface. The percentage contributions of iron in the exchangeable and carbonate fractions decreased to 3.2% at 55–60?cm depth. The amount of chromium in the exchangeable fraction ranged from 0% to 7% for exchangeable; 0–26.5% for organic matter/sulfide bound; 3.8–17.9% for Fe–Mn oxides; and 46.8–100% for residual fraction. The mobility factors of the metals indicated that these metals were relatively mobile at top sections as compared with deeper sections. The overall picture of metal mobility and availability indicates potential contamination risk by Fe, Zn, Mn, and Pb in the Orogodo River sediment system.     

Fractionation of trace metals (Mn,Zn, Cu,Pb) in Red Sea sediments,Gulf of Aden,Yemen

A sequential extraction technique was applied to estimate the chemical association of Mn, Zn, Cu and Pb in five chemical phases (exchangeable, carbonate, Fe–Mn oxides, organic matter and residual) in sediments of the Gulf of Aden, Yemen. The results indicated that a higher level of Mn was associated with the residual fraction (natural sources) than the non-residual fraction (anthropogenic sources). Zn fractionations revealed that it was associated more with Fe–Mn oxides and organic fractions than exchangeable and carbonate fractions. Most of the Cu was present in the residual form (60–72%) except for in the main port area (zone III), where it was associated with the organic phase (77% of the total Cu content, the organic matter content was 5%). Similarly, most Pb was bound in the residual fraction (56–71%) except the main port area where ～ 62% of the total Pb was bound in non-residual fractions. It was also found that the Pb concentration in the exchangeable fraction was very high compared with other metals. The risk assessment code for the metals showed a low risk for Zn and Cu, but low to medium risk for Mn. Fractionation of Pb showed medium risk at most of the regions except at the eastern area, which revealed a high risk for the aquatic environment.     

Heavy Metals in the Bed and Suspended Sediments of Anyang River, Korea: Implications for Water Quality

The objective of this study is to compare Anyang River bed sediments with water chemical composition and to assess the anthropogenic chemical inputs into the river system. Eight sampling locations were chosen along the river channel. Bed and suspended river sediments and water samples were collected, and analyzed for their chemical and physical composition. Data revealed that trace element concentrations in the river water were generally below world average, except for As, Mn, Ni and Cr. Among the three phases: water, bed and suspended sediment, more than 99% of the trace elements was associated with the bed sediment. Concentrations of trace elements in the sediment were a function a particle size distribution and organic content. The calculated degrees of enrichment based on the least influenced sample (ASD 1) indicated the river sediments were enriched with respect to background. The enrichment factors for Pb, Zn and As were relatively lower than for Cr, Co, Ni and Zn. The difference in the enrichment seems to reflect the human activities influence in the basin, and specially for Cd. Speciation of the elements in the five different chemical forms in the sediment by sequential extraction indicated that the reducible fraction was predominant for Fe, Zinc and Cu showed an irregular variation among the different fractions; whereas, Cd and Pb were more regular. Zinc and Cu highly existed mostly in exchangeable forms. Acid soluble and reducible forms were also important for most metals. The speciation implies that the metals associated with the sediment are subject to release into water bodies as goechemical variables (pH and Eh) change. Currently, the introduced metals are deposited near the source area and are mostly associated with the sediment, implying that the river bed sediment acts mainly as a sink, rather than a pool. The accumulated and enriched toxic trace elements can pose a potential pollution of river water.