耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全,但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法,欧共体标准物质局提出的三步提取法（BCR法1,中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品,采用中国地质调查局地质连续提取法（DD2005．03）进行耕地中重金属元素（Cu、Cd、Zn）的形态分布,结果表明：Cu、Zn主要以残渣态存在,其残渣态分别占全量的55．80％和67．35％。Cd以离子交换态为主,占全量的27．30％。Cu、Cd、Zn各态含量占全量比例的顺序是,Cu：残渣态〉弱有机结合交换态〉铁锰氧化态〉碳酸盐结合态〉强有机结合态〉水溶态〉离子交换态。Cd：离子交换态〉弱有机结合交换态〉强有机结合态〉残渣态〉碳酸盐结合态〉铁锰氧化态〉水溶态。Zn：残渣态〉铁锰氧化态〉弱有机盐结合态〉离子交换态〉强有机结合态〉碳酸盐态〉水溶态。从生物可利用性系数k来看,Cd主要以活动性较大的状态存在,很容易被作物吸收。     

杭州城市土壤重金属的化学形态及环境效应

通过对杭州城市土壤重金属异常中Hg、Cd、Pb、Zn、Cu采用改进的连续浸提实验进行形态分析结果表明,表层土壤中Hg以残渣态和强有机态为主,Cd以铁锰氧化态、弱有机结合态、残渣态和离子交换态为主,Pb、Zn、Cu以残渣态、弱有机结合态和铁锰氧化态为主.相比之下,Cd与Cu的活性组分分别为最高和次高,部分蔬菜样品中重金属含量超标,对该地区农产品的安全已构成威胁.研究发现,上述重金属除与地质背景、土壤理化性质有关外,与人类经济活动关系尤为密切.     

子牙新河下游湿地土壤重金属垂直分布及形态特征

2014年秋季在子牙新河下游湿地采集柱状土壤样品,分析了Cd、Zn、Cu、Pb的垂向分布特征,利用Tessier连续浸提法,分析了典型湿地N1、N3、B3的重金属形态.研究结果表明,Cd、Zn、Cu、Pb含量垂向分布差异性比较大,波动幅度比较大,多数点位Cd、Cu、Zn在11—19 cm深度处出现峰值,可能与过去金属的输入和周期性淹水有关.Zn、Cu、Pb形态分布为残渣态铁锰氧化物结合态有机物结合态可交换态碳酸盐结合态,Cd形态分布为铁锰氧化物结合态可交换态残渣态有机物结合态碳酸盐结合态,Cd的生物有效性较高.湿地淹水条件影响到湿地重金属Cd的交换态和铁锰氧化物结合态的垂直分布.Cd主要以铁锰氧化物结合态的形式存在于湿地土壤中,其百分含量占53.2%,而重金属Zn、Cu、Pb主要以残渣态的形式存在于湿地土壤中,其百分含量均高于60%.根据风险评价编码法(RAC)对重金属的化学形态进行风险评价,风险顺序为:CdZnCuPb,因此重金属Cd应引起足够的重视.     

金昌市郊农田土壤Cu,Zn,Ni形态分布特征与生物有效性评价

通过野外调查和室内测试分析,研究了金昌市郊农田土壤重金属Cu,Zn和Ni的形态特征,并以麦粒中重金属含量为重点进行了Cu,Zn和Ni的生物有效性评价.结果表明,研究区域土壤重金属Cu和Ni污染严重;Cu的主要存在形态为有机结合态,Zn的主要存在形态为残渣态,而Ni的主要存在形态为潜在可利用态;三种元素的生物有效性大小顺序为NiZnCu.对麦粒中重金属健康风险进行评价反映出麦粒中Ni含量对人体健康风险较大,而Cu和Zn对人体健康风险较小.逐步回归分析结果表明,农田土壤中Cu可交换态和碳酸盐结合态对麦粒中Cu含量贡献最大,而对麦粒吸收Zn和Ni贡献最大的形态分别为Zn的碳酸盐结合态和Ni的可交换态、碳酸盐结合态、铁锰氧化态和有机结合态.土壤重金属Cu,Zn和Ni各形态分配系数较总量和各形态含量更适合表征本研究区域土壤重金属的生物有效性.     

文山三七(Panax notoginseng)种植区三七与土壤中Pb、Cd、Cu和Zn的分布特征及评价

为了调查文山州三七(Panax notoginseng)主要种植区(丘北县、砚山县、文山县和广南县)土壤和三七Pb、Cd、Cu和Zn含量,通过GPS定位采集三七根区0~15 cm深度土壤样品和三七样品各30个,分析土壤中重金属总量和不同形态含量及三七中对应重金属含量,并进行空间分布分析。结果表明:(1)土壤Pb、Cd、Cu和Zn平均含量分别为55.56、0.36、43.53和119.62 mg·kg~(-1),超标率分别为6.67%、53.3%、13.33%和0。各形态Pb、Cu和Zn含量表现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。各形态Cd含量表现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。(2)三七和土壤Pb、Cd、Cu和Zn总量和不同形态含量均以丘北县最高,广南县最低。(3)三七根系Pb、Cd、Cu和Zn平均含量分别为2.93、0.35、5.21和11.11mg·kg~(-1),三七植株各部位重金属含量表现为根系剪口茎叶花果。调查区三七和土壤重金属含量存在空间差异,且以土壤Cd污染为主,应采取一定措施降低三七Cd含量。     

黔西北炼锌矿区土壤重金属形态分析及风险评价

为研究黔西北炼锌矿区土壤和矿渣中重金属总量及形态分布特征,采用Tessier五步连续提取法和风险评价编码法(RAC)探讨其污染程度。结果表明,除Cr和Ni外,其他各重金属平均值均超出贵州省的土壤背景值,其中Pb、Zn、Cd污染严重。形态分析表明,土壤和矿渣样品中Pb、Zn、Mn以残渣态(分别占其总量的45.91%、55.11%、42.71%)和铁锰结合态(分别占其总量的33.33%、28.26%、41.78%)为主;Cd的可交换态和碳酸盐结合态之和占总量的30.63%;Cu的有机结合态为65.11%,其次是残渣态30.79%;Cr和As则以残渣态为主要形态,平均占比均超过90%。RAC评价结果表明,矿区周边土壤中Cd元素具有极高的潜在生态风险,其他重金属潜在生态风险水平较低。     

青岛城市土壤重金属的形态分布及影响因素分析

选取青岛市不同功能区63个代表性的表层土壤样品,分析了其重金属元素的含量和存在形态.结果表明,青岛城市土壤中Cu、Zn、Pb、Cd均受到不同程度的污染,其中Cd属于重度污染,土壤重金属累积污染程度为Cd>Zn>Cu>Pb.Cu和Zn主要以残渣态为主,Pb主要以残渣态和铁锰氧化态为主,Cd主要以残渣态和有机结合态为主;土...     

西安市公园大气降尘中Cu、Pb、Zn、Ni、Cd的化学形态特征及其生物有效性

采用连续提取法和原子吸收光谱法测定了西安市11个公园降尘中Cu、Pb、Zn、Ni、Cd等元素化学形态的含量,结果表明,各公园降尘中Cu和Pb含量均超过该市道路灰尘平均含量的7倍和3倍以上,有机态、铁锰氧化物态、碳酸盐态和可交换态分别为Cu总量的38%、31%、15%和13%;有机态、铁锰氧化态、碳酸盐态和交换态分别为P...     

北京市西城区雨水管道沉积物中重金属特征

在对北京市西城区部分排水管道调研的基础上,对几个典型雨水检查井连接雨水管道沉积物中赋存的主要重金属污染物污染水平及形态分布进行了研究,分析了沉积物粒径及有机质含量对重金属污染物赋存水平的影响.结果表明,排水管道沉积物中:Cr主要以残渣态存在;Cu和Zn以具有活性潜力的铁锰氧化物形态及碳酸盐结合态两种形态为主;Pb的残渣态含量平均值达到了56.4%;Ni的可交换态和碳酸盐结合态含量相对较大;可交换态Cd占其总量的比例最高值达22.4%,而残渣态的Cd含量极小.     

河北平原农田土壤重金属形态分布特征及控制因素研究

土壤重金属污染防治已迫在眉睫,国内外对重金属污染研究热度不减。本文选择河北平原农田为研究区,对采集325个根系土样品中的Cd、Cr、Pb、As、Hg等5种重金属进行了各形态含量统计与分析,并用Arc GIS制作了有效态空间分布图。最后运用相关性分析法探讨了5种重金属各形态与全量及pH值、Fe_2O_3、总有机碳(TOC)、阳离子交换容量(CEC)、粘粒的相关性。研究表明:Cd的有效态(水溶态和离子交换态)含量占全量比重最大,为18.06%,Cr、Pb、As、Hg均低于10%,这4种金属以残渣态为主,占全量的50%以上;As元素各形态与全量、pH值、Fe_2O_3、TOC、CEC、粘粒的相关程度最高,成正相关关系;Cr的3种形态(铁锰氧化态、强有机结合态、残渣态)与Fe_2O_3、TOC、CEC、粘粒呈显著正相关关系,Cr碳酸盐结合态、腐殖酸结合态与pH呈正相关关系,与Fe_2O_3、TOC、CEC、粘粒呈显著负相关关系;5种重金属铁锰氧化态与pH均呈正相关关系。     

Comparative study of the fate and mobility of metals discharged in mining and urban effluents using sequential extractions on suspended solids

The fate, bioavailability and environmental impacts of metals discharged in municipal and mining wastewater discharge will depend to a large extent on chemical speciation and distribution. Previous studies on metal bioaccumulation have shown that total metal concentrations are not a good predictor of bioavailability in the dispersion plumes of municipal effluents. The objective of this study was to determine the solid phase speciation of metals in surface waters receiving urban and mining effluents in order to assess their fate and relative mobility in the receiving environment. Suspended particulate matter was sampled using sediment traps at several sites downstream of effluent outfall plumes as well as at reference upstream sites. Particulate metal in operationally defined fractions—exchangeable/carbonates, reducible, oxidisable and residual—were determined in suspended particulate matter with a series of selective chemical extractions. Metal enrichment in suspended particles was generally observed in both mining and urban effluent discharges. When compared to its receiving environment, the mining effluent appeared to release more particulate metals (Cu, Fe, Zn) in the most reactive fractions (i.e. exchangeable/carbonates + reducible forms, 23–43%), while other released metals, such as Cd and Mn, were predominantly in the least reactive forms (i.e., oxidisable + residual, 73–97%). In contrast, the reactivity of all particulate metals, with the exception of Mn, from the urban effluent was much higher, with up to 65, 42, 30 and 43% for Cd, Cu, Fe and Zn, respectively, in the two most reactive fractions. As expected in effluent dispersion plumes, parameters such as the organic carbon, Fe oxide and carbonate contents have specific effects on the partitioning of several trace metals, particularly Cd, Cu and Zn. Our results indicated that the relative distributions of metals among geochemical fractions varied in the effluent receiving waters where organic carbon and Fe oxides appeared as the most important parameters. This could therefore decrease the exposure for aquatic organisms that are exposed to those contaminated sediments as well as the risk to human health.     

Speciation of heavy metals in sediments from the Scheldt estuary,Belgium

A simple three-step sequential extraction procedure was applied to study the speciation of heavy metals in sediment from Scheldt estuary, and their relationship to sediment grain size and organic matter content. The sedimentary metal content was fractionated into carbonate and exchangeable, metals bound to organic matter and residual fractions. Sedimentary total metal content was also determined using an industrial microwave (ETHOS 900) HF/HNO₃ extraction method. The extracts were analysed for metals using inductively coupled plasma atomic emission spectrometry. The bioavailable fraction (exchangeable and metals bound to organic matter) comprised less than the other forms. Residue metals were the dominant form of metals in almost all studied sites. The average total metal content for the studied sites decreased in the order Fe>Cr>Cu>Co>Zn>Pb>Cd. Based on average values for the studied sites, the highest bioavailable metals in sediments were Cd (38%) from Westkapelle, Zn (17%) from Yerseke, Co (12%) from Domburg, Cr (9%) from Vlissingen, Fe and Pb each (2%) from Yerseke, and Cu (1%) from Domburg. Metal recovery was good, with<10% difference between the total metal recovered through the extractant steps and the total metal determined using HF/HNO₃ extract.     

Effect of lime on speciation of heavy metals during composting of water hyacinth

Composting is attractive and inexpensive method for treatment and biomass disposal of water hyacinth. However, the major disadvantage of water hyacinth composting is the high content of heavy metals in the final compost. Addition of lime sludge significantly reduced most bioavailable fractions (exchangeable and carbonate) of heavy metals. Studies were carried on composting of water hyacinth (Eichhornia crassipes) with cattle manure and sawdust (6:3:1 ratio) and effects of addition of lime (1%, 2% and 3%) on heavy metal speciation were evaluated during 30 days of composting period. The Tessier sequential extraction method was employed to investigate the changes in speciation of heavy metals such as Zinc (Zn), Copper (Cu), Manganese (Mn), Iron (Fe), Lead (Pb), Nickel (Ni), Cadmium (Cd) and Chromium (Cr) during water hyacinth composting. Effects of physicochemical parameters such as temperature, pH and organic matter on speciation of heavy metals were also studied during the process. Results showed that, the total metal content was increased during the composting process. The higher reduction in bioavailability factor (BF) of Cu, Fe, Ni, Cd and Cr was observed in lime 2 treatment about 62.1%, 64.4%, 71.9%, 62.1% and 58.9% respectively; however higher reduction in BF of Zn and Pb was observed in lime 1 treatment during the composting process. Reducible and oxidizable fractions of Ni, Pb and Cd were not observed during the process. Addition of lime was very effective for reduction of bioavailability of heavy metals during composting of water hyacinth with cattle manure and sawdust.     

Metal distribution in marine sediments of the Mar Piccolo in Taranto (Ionic Sea,southern Italy)

The spatial distribution of selected metals (Fe, Ni, Mn, Zn, Cu, Pb, Hg and Cd) and their partition in the different chemical forms (speciation) were determined in benthic sediments from Mar Piccolo, Taranto (Ionic Sea, southern Italy). The aim of this study was to assess the degree of sediment contamination and bioavailability of metals, very important for Italian mussel culture, in a semi-enclosed marine ecosystem. In sediments, grain size distribution, total organic carbon (TOC), and humic (HA) and fulvic (FA) acids contents were also determined. The compounds TOC, HA and FA, in fact, have a great influence on metal complexation. High concentrations of copper, lead, zinc and mercury were found, especially in sediments of the first inlet of Mar Piccolo. Statistical analysis of results shows significant correlation among Cu, Pb and Zn concentrations and the influence of organic matter on the sediment distribution of Cu, Pb and Zn. Metal speciation analysis, carried out with sequential extraction method, shows that Fe and Ni are present in sediments mainly as sulphides. Mn and Pb are present principally in an ion-exchangeable form or bound to carbonate and Cu is associated to organic matter. Metal pollution index (MPI), calculated as a weighed mean of the metal contamination factors in each station, shows that with regard to Cu, Ni, Pb and Zn, some stations investigated are unpolluted (MPI <1), whereas in other areas, pollution level is not very high. On the contrary, for mercury, the pollution level in the first inlet of the basin is very high.     

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.     

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.     

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.     

Accumulation and translocation of heavy metals in soil and plants from fly ash contaminated area

The present investigation deals with the accumulation of heavy metals in fields contaminated with fly ash from a thermal power plant and subsequent uptake in different parts of naturally grown plants. Results revealed that in the contaminated site, the mean level of all the metals (Cd, Zn, Cr, Pb, Cu, Ni, Mn and Fe) in soil and different parts (root and shoots) of plant species were found to be significantly (p<0.01) higher than the uncontaminated site. The enrichment factor (EF) of these metals in contaminated soil was found to be in the sequence of Cd (2.33) > Fe (1.88) > Ni (1.58) > Pb (1.42) > Zn (1.31) > Mn (1.27) > Cr (1.11) > Cu (1.10). Whereas, enrichment factor of metals in root and shoot parts, were found to be in the order of Cd (7.56) > Fe (4.75) > Zn (2.79) > Ni (2.22) > Cu (1.69) > Mn (1.53) > Pb (1.31) > Cr (1.02) and Cd (6.06) approximately equal Fe (6.06) > Zn (2.65) > Ni (2.57) > Mn (2.19) > Cu (1.58) > Pb (1.37) > Cr (1.01) respectively. In contaminated site, translocation factor (TF) of metals from root to shoot was found to be in the order of Mn (1.38) > Fe (1.27) > Pb (1.03) > Ni (0.94) > Zn (0.85) > Cd (0.82) > Cr (0.73) and that of the metals Cd with Cr, Cu, Mn, Fe; Cr with Pb, Mn, Fe and Pb with Fe were found to be significantly correlated. The present findings provide us a clue for the selection of plant species, which show natural resistance against toxic metals and are efficient metal accumulators.     

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.