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),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.     

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...     

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。     

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。     

干旱区绿洲城郊排污渠沉积物重金属污染与释放特征

在白银市城郊东大沟沿程采集了8个沉积物样品,采用Tessier五步连续提取法和静态释放试验研究了沉积物中重金属的污染特征及在不同离子强度条件下沉积物中重金属的释放规律.结果表明:(1)东大沟沉积物中Cd、Cu、Pb、Zn的含量均超过了甘肃省土壤元素背景值,其平均值分别为背景值的128.83、12.71、26.90、17.99倍.(2)沉积物中Cd和Cu主要以残渣态和有机结合态存在,Zn主要以有机结合态和铁锰氧化物结合化态存在,Pb主要以铁锰氧化物结合态存在;沉积物中重金属的活性顺序为ZnPbCdCu.(3)随着离子强度的增大,沉积物中Cu、Pb、Zn的释放量随之增加,沉积物中Cd的释放量则是先增加后减少.     

青岛市表面土壤Cu的形态分布及潜在生态危害评价

研究了青岛市不同功能区表层土壤Cu的含量及其化学形态分布,并采用Hakanson潜在生态危害指数法对土壤中Cu的潜在生态危害进行评价。结果表明,Cu的含量为23.84-114.86 mg/kg,平均值为52.03 mg/kg,污染程度为工业区〉居民区〉风景区〉商业区〉农业区;土壤中Cu的化学形态总的分布趋势为：残渣态〉有机结合态〉铁锰氧化物结合态〉碳酸盐结合态〉可交换态,生物可利用态含量较低;青岛市表面土壤的Cu污染处于中等到强污染之间,达到轻微生态危害水平。     

重金属污染土壤属性区间识别模型的赋权分析

土壤重金属污染评价为土壤重金属污染的及时防范和综合治理提供重要的理论依据。文章在属性区间识别理论的基础上,构建土壤重金属污染评价的属性区间识别模型：选取土壤重金属污染中普遍存在的Hg、Cd、As、Pb、Cu、Zn作为评价指标,采用均化系数将各评价指标的属性测度区间转化为综合属性测度;为避免主观因素,利用主成分分析法、熵权法、CRITIC法对各评价指标进行3次客观赋权;最后根据置信度准则和分级标准进行土壤重金属污染的综合评价。对3种赋权法得到的权重和评价结果进行比较,表明：属性识别模型在土壤重金属污染评价中适用且有利于评价结果准确性的提高;3种客观赋权法算得的权重合理,且其优异程度为主成分分析法〈熵权法〈CRITIC法。     

神木煤矿区土壤重金属污染特征研究

通过对神府煤田开采区3个煤矿区周围土壤Cu、Cd、Cr、Mn、Ni质量分数进行测定及分析,评价了煤田开采对周围土壤的污染程度。结果表明,长期的煤炭资源开发、运输等活动,已导致周围土壤受到重金属不同程度的累积性污染,土壤中Cd、Ni质量分数高于陕西省土壤背景值,且Cd污染程度较高,Ni污染程度较低,而Cu、Cr、Mn基本不受污染。3个煤矿表层土壤各重金属元素质量分数均表现出污染区大于对照区,但这种变化幅度存在一定差异;Cu、Cr、Mn 3种重金属元素虽没有超出背景值,但已表现出一定程度的累积;煤矿周围土壤重金属污染受到开采年限、土壤质地、风向等因素的影响。3个煤矿污染区土壤剖面样品中,5种重金属元素质量分数基本上随着土壤深度的增加呈现降低的趋势,且这种趋势具有波动性。     

基于PCR-DGGE的重金属污染土壤微生物种群指纹分析

采用变性梯度凝胶电泳（DGGE）分析方法,研究沈阳市细河沿岸重金属污染土壤中微生物结构多样性、种群丰富度及种群结构的动态变化规律。结果表明：直接从土壤中抽提总DNA,对16SrRNAV3可变区序列进行扩增,DGGE指纹图谱分析,微生物种群结构和变化规律明显,同时也表现为重金属污染程度越重,多样性指数越低;其中细河底泥重金属含量严重超标,多样性指数最低。经方差分析,重金属污染情况与Shannon-wiener多样性指数呈负相关,其中重金属污染对微生物的均匀度指数影响最显著,并且锌污染对其影响最大为-0.985。表明PCR-DGGE技术可以用于污染环境下微生物多样性研究,也为污染环境下土壤微生物多样性研究提供了新的实验方法与依据。     

An Investigation Into the Mechanism by Which Synthetic Zeolites Reduce Labile Metal Concentrations in Soils

The addition of synthetic zeolites and similar materials to metal contaminated soils has been shown to reduce soil phytotoxicity and to improve the quality of plant growth on such amended soils. To gain an understanding of the mechanism by which the phytotoxicity of contaminated soils is reduced when treated with synthetic zeolites, sequential extraction procedures and soil solution techniques have been used to identify changes associated with metal speciation in amended soils. Sequential extraction data and changes in soil solution composition are presented for three different contaminated soils, amended with three synthetic zeolites (P, 4A and Y) at concentrations of 0.5%, 1% and 5% w/w, or lime at 1%. The soils were collected from the site of a metal refinery, an old lead zinc mine spoil tip and from a field which had been treated with sewage sludge. After incubation of the zeolite treated soils for between one and three months, results showed a reduction in the metal content of the ammonium acetate fraction between 42% and 70%, depending on soil, zeolite and rate of addition, compared with the unamended soils. In addition, soil solution experiments indicated that synthetic zeolite amendments were more efficient at reducing metal content than comparable lime treatment. The mechanism by which synthetic zeolites reduce metal bioavailability in contaminated soils is discussed and compared to other amendments.     

Total and bioavailable metals in two contrasting mining regions (Sudbury in Canada and Lubumbashi in DR-Congo): relation to genetic variation in plant populations

Knowledge of total and bioavailable metal contents in soil is important for regional risk assessment and management. The main objective of the present study was to analyse the concentrations of metals in soils in two contrasting mining regions (Sudbury in Canada and Lubumbashi in DR-Congo). Genetic variation of plant populations was investigated to assess the potential impact of metal contamination on forest sustainability. The levels of copper, cobalt, zinc, arsenic, and lead were significantly higher (up to 200-fold) in mining sites in the Lubumbashi compared to the most highly contaminated Sudbury sites. The nickel content in soil samples from Lubumbashi was much lower compared to Sudbury region samples. Only 3.5% and 4 % of total copper and nickel, respectively, were phytoavailable, with values of 6%, 5.7%, 3.6%, and 5.4% for cobalt, magnesium, manganese, and zinc, respectively. There were significant positive correlations between total metal and phytoavailable metal concentrations for copper (r=0.99), nickel (r=0.86), cobalt (r=0.72), strontium (r=0.71), and zinc (r=0.66). Although genetic variation was high in Picea glauca populations from the Sudbury region, no association was found between metal contamination levels and genetic variation within and among the P. glauca populations.     

贵州省典型矿区土壤重金属污染对蚯蚓的毒性效应评估

选取我国贵州省某矿区典型的重金属复合污染土壤开展28 d慢性毒性暴露试验,以蚯蚓体内2种抗氧化酶活性——过氧化氢酶(CAT)和超氧化物歧化酶(SOD)、8-羟基脱氧鸟苷(8-ODHG)和金属硫蛋白(MT)含量为生物指标,评估了以上生物指标与土壤重金属含量的相关性,探讨该研究方法用于矿区土壤重金属生态风险评估的可行性。结果表明,CAT和SOD在暴露周期内均出现先诱导后抑制的动态响应过程,表明蚯蚓通过提高CAT和SOD的活性来清除机体因污染胁迫而产生的自由基,以适应环境变化,在毒性缓解后,蚯蚓体内代谢产物的积累抑制了抗氧化氢酶活性,CAT和SOD活性下降并趋于稳定。暴露于重金属污染亚致死浓度时,蚯蚓体内的8-OHDG含量随着暴露时间的延长显著降低,随着暴露浓度的增加,损伤存在由低到高的转变。在28 d暴露周期内,蚯蚓体内MT在重金属胁迫下发挥了解毒作用,MT含量在蚯蚓暴露后第7天增加,随后逐渐降低。本文基于生物毒性试验综合评估了矿区典型重金属污染土壤的生态风险,研究结果对指导重金属复合污染土壤的修复与再利用具有重要意义。     

Mapping Soil Lead and Remediation Needs in Contaminated Soils

For the past two decades, the Taiwan Environmental Protection Administration has made a systematic investigation of As, Cd, Cr, Cu, Pb, Hg, Ni and Zn in agricultural soils to identify soil pollution from industrial production. The EPA has cooperated with local governmental agencies to establish a soil quality monitoring system that would upgrade the land recovery ability and prohibit polluted lands from being cultivated or turned over to other uses. Based on an island-wide soil survey, more than 1,000 hectares of arable soils in Taiwan were found to be considerably contaminated by heavy metals. One of the heavy metal contaminated sites, located near a ceramic product manufacturing factory in Nantou County, was identified as lead contaminated. According to the Nantou Environmental Protection Bureau, the lead content in contaminated sites showed a great variation of several mg Pbkg^–1 soil to several thousands mg Pbkg^–1 soil. Therefore, it is appropriate to estimate the lead spatial distribution through geostatistics such as Kriging. The soil lead concentration contour maps obtained by Kriging can help us to identify the pollution patterns and delineate the range of contaminated sites. The purpose of this study is to determine the Pb concentrations at each location by performing detailed soil sampling on those Pb contaminated sites and estimating the lead spatial distributions by Kriging. A total of 70 soils were sampled from different locations at two experiment sites. Lead contents were determined with 0.1M HCl extractable lead content of the soils. The results obtained by investigating the lead contents in each 15cm segment down to a 60cm depth, revealed that lead contents were greater in arable land near the ceramic products manufacturing factory, and lead concentrations decreased with depth. In addition, Pb concentrations in heavily contaminated soils showed heavy concentrations of Pb in specific locations. Results from Pb content spatial distributions indicated that the Kriging model is a useful tool and can provide decision-makers with critical information for delineating hazardous areas in heavy metal contaminated sites.     

基于GGE双标图和BLUP分析筛选镉砷同步低累积水稻品种

种植重金属低累积水稻品种是中国耕地重金属污染稻田安全生产的有效措施,为筛选镉砷同步低累积水稻品种,该研究通过测定盆栽、早稻季、晚稻季3个试验环境中18个水稻品种稻米镉砷含量,利用基因型主效加基因型——环境互作效应(GGE)双标图分析品种稻米镉砷低累积能力、稳定性、环境适应性,进一步通过最佳线性无偏预测(BLUP)法验证和筛选出镉砷同步低累积水稻品种。研究结果表明,3个试验中稻米镉砷含量差异显著,稻米镉含量为0.20—4.21 mg·kg^?1,稻米砷含量为0.03—4.24 mg·kg^?1,稻米镉差异来源主要受品种与环境互作的影响,占总影响的45.4%,稻米砷差异主要受环境和品种与环境互作的影响,分别占总影响的39.8%和33.6%。GGE分析稻米镉、砷低积累能力及稳定性好的品种分别为品种14、15与9和品种9、14与17。根据稻米镉砷含量综合BLUP值筛选出镉砷同步低累积最优品种为品种14(Y两优19),其次是品种9(晶两优华占),和GGE模型评价的结果基本一致。该研究结果表明利用GGE双标图和BLUP分析筛选镉砷同步累积水稻品种是一种可行的新方法。     

Chelant-assisted pulse flushing of a field Pb-contaminated soil

Laboratory experiments on a lead-contaminated soil were carried out to test the effects of chelant addition on metal leachability using column tests. Tests were aimed at studying metal mobilisation upon application of two different chelating agents (ethylenediaminetetraacetic acid [EDTA] and ethylenediaminedisuccinic acid [EDDS]). Column operation was arranged to simulate a flushing treatment in which the chelating agent is applied in a pulse mode to the soil for one bed volume, while deionised water was continuously introduced for the rest of the experiment. Two different concentrations (3 and 5 mmol·kg ^?1 respectively) of the two chelating agents and a control solution (deionised water) were tested in separate experiments; pH, total organic carbon and the total concentrations of Pb, Zn, Fe, Cd, Cu and Ni were monitored during each run. A seven-step sequential extraction procedure was used to evaluate metal partitioning and concentration in the contaminated soil after treatment as a function of depth. The results showed the effect of the nature of flushing solution on the hydraulic behaviour of the columns. Metal concentrations in the leachate increased considerably upon the application of chelants, thus indicating their suitability for metal extraction from contaminated soils. In view of full-scale application of soil flushing, particular concern should also be devoted to ensuring a homogeneous distribution of the solution within the contaminated area and an efficient collection of the exhausted extracting solution, as well as to recovering and recycling the chelating agent used.