湘南某矿区菜园土中典型重金属的形态分析

分别运用Tessier连续提取法和Leleyter连续提取法研究湘南某矿区菜园土中Pb,Zn,Cu和Cd的形态分布特征.结果表明：菜园土中Pb,Zn,Cu和Cd的总浓度严重超过国家土壤环境质量标准.Pb,Zn,Cu和Cd的主要形态是残渣态,水溶态和交换态所占比例较小.重金属生物可利用性的研究表明,Pb,Zn,Cu和Cd生物可利用的含量较少;在Tessier方法中,除Cu之外,生物不可利用态是主要形态,其次是潜在生物可利用态,而在Leleyter方法中,潜在生物可利用态是主要形态,其次是生物不可利用态.     

赣南富稀土矿区农田土壤中稀土元素的环境化学特征

选择江西赣县大田稀土矿区，研究了矿区耕作农田土壤中稀土元素的含量、分布及赋存形态特征。结果表明，该区土壤中稀土元素含量明显高于对照区和全国土壤平均含量，且相对富含重稀土元素。土壤中稀土元素的分布模式受成土母岩及元素性质控制，呈现Eu和Ce负异常。稀土元素主要以可交换态和有机结合态（特别是松结有机态）形式存在，具有较高的活性和生物有效性，可能影响生态环境安全。     

锑矿土壤中As和Sb的分布、形态及生物可利用性

采用微波消解-氢化物发生-原子荧光光谱法测定了晴隆锑矿区土壤中总砷和总锑,利用Tessier连续提取法分析土壤中不同形态砷和锑.结果表明,各采样点土壤As、Sb含量分别为17.98—127.85 mg·kg-1、171.93—601.59 mg·kg-1,远高于贵州省背景值;土壤中砷和锑的存在形态均以残渣态为主,其次是有机结合态、铁锰氧化物结合态和碳酸盐结合态,可交换态很少;土壤中生物可利用态锑占总和0.33%—1.72%,其含量为0.60—3.91 mg·kg-1,而土壤中生物可利用态砷占总和0.09%—0.57%,其含量为0.15—0.48 mg·kg-1.     

伴随阴离子对土壤Cd形态转化的影响

化学性质各异的伴随阴离子通过影响进入土壤的外源Cd2+后的形态转化,而影响其迁移特性和生物毒性。对此进行了解将有助于采取相应的防治镉污染的技术措施。通过室内连续培养试验(0~70 d),研究了伴随阴离子(NO3-、C1-、SO42-)对Cd2+在土壤中的吸附特性、形态分配与转化特性的影响。结果表明,伴随阴离子对添加外源Cd2+溶液后的土壤Cd吸附作用能力表现为:SO42-NO3-C1-;SO42-处理在20 d时吸附率达最大值(93.61%);NO3-与C1-处理在30 d时吸附率达最大值,分别为82.25%、67.97%。初始状态土壤中Cd主要以残渣态存在,可交换态Cd含量与比例最低,占总Cd含量不到10%。添加1.0 mmol·L-1外源Cd2+处理后,在培养期内(0~70 d),表现为可交换态Cd含量铁锰氧化物结合态Cd含量碳酸盐结合态Cd含量残渣态Cd含量有机结合态Cd含量。土壤可交换态Cd在0~70 d分配系数达到38%~61%,其中SO42-处理培养10 d达到最大值(61.09%),NO3-与C1-处理30 d时达到最大值(分别为43.74%和41.80%)。土壤碳酸盐结合态Cd含量在30 d时趋于饱和,其含量(0~70 d)表现为SO42-C1-NO3-。3种伴随阴离子处理的土壤铁锰氧化物结合态Cd含量在0~50d无显著性差异。有机结合态Cd和残渣态Cd含量随着培养周期延长而逐渐增加,但其吸收转化分配比例相对可交换态、碳酸盐结合态和铁锰氧化物结合态低。从生物利用度系数来评价镉形态的危害程度,初始状态土壤中其危害程度表现为生物潜在可利用态生物难利用态生物易利用态。添加1.0 mmol·L-1的外源Cd2+溶液后,SO42-处理的表现为:生物易利用态生物潜在可利用态生物难利用态;C1-和NO3-处理的表现为生物潜在可利用态生物易利用态生物难利用态。这表明,镉形态在SO42-处理伴随下对土壤造成的危害程度相对C1-和NO3-处理严重。外源Cd2+溶液进入土壤主要转化为可交换态Cd(SO42-NO3-C1-),SO42-处理培养10 d达到最大值(转化系数为61.09%)。可交换态Cd在土壤中具有较强的迁移性,容易被生物吸收利用,对环境影响最大。     

锑矿区土壤中锑的形态及生物有效性

通过室内模拟对锑矿区土壤中锑的分布、存在形态及生物有效性进行了研究 .结果表明 :在锑矿区土壤中含有高浓度锑污染 ,其存在状态主要以残渣态为主 ,其次是Fe/Mn结合态、有机 /硫化物结合态和碳酸盐结合态 ,可交换态和水溶态占的比率最小 .不同溶剂对锑的提取率不同 ,NH4NO3对锑的提取率最高 ,其次是EDTA ,HAc和H2 O ,NH4OAc对锑的提取率最小 .土壤中锑主要以五价锑的形态存在 ,几乎占总锑量的 90 %以上 .土壤中生物可利用态锑的浓度比较高 ,一般在 2 5— 1 3 2mg·kg- 1 ,中等可利用态占土壤总锑的1 6 2— 8 2 6 % ,生物不可利用态锑的浓度占 88 2— 97 91 % .     

生物炭对重污染土壤镉形态及油菜吸收镉的影响

为了解不同种类和用量的生物炭对土壤镉形态及油菜吸收镉的影响,通过室外盆栽试验,以湖南某冶炼区周边重镉污染土壤为供试土壤,湘油27号为供试作物,于油菜移栽前7d分别添加w为0.1％和1％的竹炭和柠条炭,分析土壤镉形态和成熟期油菜各器官镉含量.结果表明,添加生物炭能降低土壤镉的有效性和油菜各器官中镉含量.柠条炭降低油菜吸收累积镉的效果比竹炭更明显,且随着生物炭量的增加阻控效果更明显.相比于对照组,施用生物炭后土壤中w(可交换态镉)最大可降低16.64％;油菜根部、茎秆、油荚和籽粒w(镉)最大可分别降低34.06％ 、39.74％、33.15％和49.81％.综合结果表明,添加w=1％柠条炭处理组处理效果最佳.     

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。     

外源铅铜镉在长三角和珠三角农业土壤中的转化

选择了我国经济发达地区的长江三角洲和珠江三角洲10个代表性农业土壤，采用室内培养和化学分级方法研究了加入外源铅、铜、镉在土壤中的动态变化及转化趋势，探讨了碳酸钙、粉煤灰、猪粪和钢渣等土壤改良剂对土壤重金属形态的影响。结果表明，随着土壤重金属负荷的提高，土壤中交换态重金属的比例增大，残余态比例下降，有效性提高，对环境威胁增大。当重金属加入最较低时，重金属优先向氧化物结合态、有机质结合态转化；而当加入最较高时，向交换态和碳酸盐结合态转化的比例明皿增加。pH和土壤组分对重金属在土壤中的转化有显著的影响，土壤pH下降可使交换态Cd、Cu、Pb的比例递增。加入碳酸钙、粉煤灰、猪粪和钢渣等改良剂可显著地降低土壤中交换态重金属比例，增加其它形态的重金属比例。     

温度对外源性重金属镉在土-水界面间形态转化的影响

通过室内培养试验、采用逐级提取法研究了不同温度(-30℃、10℃、30℃)对土壤中不同剂量外源重金属镉形态转化的影响。结果表明:在30℃和10℃条件下外源加入土壤中的镉以交换态为主,且在30℃条件下镉的活性要强于10℃。在-30℃条件下,当土壤中镉总量较高时,冷冻导致镉在短期内存在形态以残渣态为主,而在培养后期交换态镉的分配系数较大;当土壤中镉总量较低时冷冻过程使镉活性增强,交换态镉的分配系数较大。冷冻过程中有机质结合态镉的含量未检测出来,说明有机质与镉的螯合作用减弱。土壤中镉含量越多,非残渣态镉的相对含量也随之增高,镉的毒性相对也增强。     

土壤重金属化学形态的生物可利用性评价

重金属化学形态是近年来土壤化学、植物营养和环境科学研究领域的一个热点和难点,利用重金属的化学形态分布和含量变化来评价重金属的生物可利用性,有利于全面研究重金属的危害性和治理重金属污染土壤。结果表明,水溶态和交换态的重金属易被生物吸收利用,而残留态重金属一般不被生物利用,其它形态如碳酸盐结合态、铁锰氧化物结合态和有机物结合态的生物可利用性主要取决于外界环境的变化。     

连续浸提技术测定土壤和沉积物中硒的形态

本文建立了土壤和沉积物中硒的形态分析方法，应用连续化学浸提技术将土壤和沉积物进行连续五次抽提，根据不同形态硒的溶解度，将土壤和沉积中的硒分为可溶态（水溶态）、可交换态及碳酸盐结合态、铁－锰氧化物结合态、有机物－硫化物结合态及元素态、残渣态五种结合形态。种形态硒分级浸提的相对标准偏差均小于４．０％，总回收率（即：五种形态和与总硒的比值）为９３．２－９４．４％。     

模拟酸雨条件下降尘中Cu,Pb,Zn,Cr各形态的溶出和转化研究

本文用Ｔｅｓｓｌｅｒ方法，研究了模拟酸雨条件下，降尘中Ｃｕ，Ｐｂ，Ｚｎ，Ｃｒ各形态的溶出和相互转化。试验表明：（１）降尘中Ｃｕ，Ｃｒ的溶出量随酸雨酸度的增大而增加；Ｐｂ，Ｚｎ没分别在ＰＨ＝３．５和ＰＨ＝４．５时溶出量最大，溶出的金属多源于可交换态和碳酸盐结合态，说明这两种形态的稳定性较差。（２）在模拟酸雨条件下，Ｃｕ，Ｐｂ，Ｚｎ，Ｃｒ各形态的含量发生了较大变化；Ｃｕ从其优势形态有机结合态向可交换态     

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。     

Speciation of heavy metals in suspended particulates in urban air†

An anayltical procedure based on a sequential extraction scheme is applied to samples of suspended particulates from an urban area of Barcelona. This area presents high levels of air pollution owing to automotive emissions and industrial activity.

The procedure allows the partitioning of particulate trace metals into four fractions: soluble and exchangeable, bound to carbonates and iron‐manganese oxides, bound to organic matter and residual. In this work, the chemical associations of Fe, Pb, Cu, Mn, Cr and Cd have been investigated.

In the analysed samples, only the cadmium is predominantly in the first fraction whereas the other metals are largely associated to carbonates and Fe‐Mn oxides.     

污染黑土中重金属的形态分布与生物活性研究

通过对污染和清洁黑土的耕层、非耕层分层采样分析,比较了Cd,Pb,Cu和Zn等在同一土壤耕层和非耕层以及不同采样点土壤中的形态分布和生物活性.结果表明,无污染黑土中这些重金属的形态分布一般为:残渣态>有机结合态>铁锰结合态>碳酸盐结合态>可交换态,外源污染则使可交换态重金属的含量增加.以生物有效性系数和迁移系数进行重金属生物活性评价,其在黑土中生物活性大小的顺序为:Cd>Cu>Zn>Pb.污染愈严重的土壤,重金属的生物活性和自身的淋溶能力相对较强,在非耕层中也表现出较高的生物活性.综合重金属在土壤中的含量和生物活性,发现2个污染点的黑土中Cd和Pb对当地农业生产和地下水安全已构成潜在的威胁.     

Aluminum fractionation in acidic soils and river sediments in the Upper Mero basin (Galicia,NW Spain)

This study aims to determine aluminum fractions in the fine earth of acidic soils under different land uses (forest, pasture and cultivation) and in the river bed sediments of the headwater of the Mero River in order to identify and quantify Al-bearing phases to assess Al mobility and potential bioavailability (environmental availability) in the monitoring area. Sequential extraction is used to evaluate the Al partitioning into six fractions operationally defined: soluble/exchangeable/specifically adsorbed, bound to manganese oxides, associated with amorphous compounds, aluminum bound to oxidizable organic matter, associated with crystalline iron oxides, and residual fraction (aluminum within the crystal lattices of minerals). The mean concentration of total aluminum (24.01 g kg^?1) was similar for the three considered uses. The mean percentage of the aluminum fractions, both in soils and sediments, showed the following order: residual fraction ? amorphous compounds ≈ crystalline iron oxides > water-soluble/exchangeable/specifically adsorbed > bound to oxidizable organic matter ≈ Mn oxides. However, in the soils, the amorphous compounds and water-soluble/exchangeable/specifically adsorbed fraction showed considerable differences between some types of uses, the percentage of aluminum linked to amorphous compounds being higher in forest soils (16% of total Al) compared to other uses (mean about 8% of total Al). The highest values of water-soluble/exchangeable/specifically adsorbed Al were also found in forest soils (mean 8.6% of the total Al versus about 4% of pasture and cultivation), which is consistent with the lower pH and higher organic matter content in forest soils. Nevertheless, the potentially bioavailable fraction (sum of the first three fractions) is low, suggesting very low geoavailability of this element in both soils and sediments; hence, the possibility to affect the crops and water quality is minimal.     

青岛城市公园灰尘重金属的形态分布及健康风险评价

对青岛市南、市北、四方和李沧四区的公园灰尘样品的重金属全量和形态分布进行分析,并对公园灰尘重金属的污染状况进行了健康风险评价。结果表明：青岛城市公园土壤和灰尘均在不同程度上受到Cu、Zn、Pb、cd的污染,李沧区4种重金属含量均在四区最高。市南区公园灰尘中的Cu、Pb、cd的含量最低,市北区的Zn含量最低;Cu主要以有...     

Changes in chemical forms of lead in temperate and semiarid soils in sterile and unsterile conditions

Sequential extraction has been used as a suitable method for fractionation of chemical forms of trace elements and study of their plant availability. Surface soils were sampled from Guilan and Hamadan provinces in north and northwest of Iran with temperate and semiarid climates. The chemical forms of Pb in the Pb(NO₃)₂-treated (400 μg Pb g⁻¹) soils have been studied in solid state incubation (FC) at 27°C in sterile and unsterile conditions. After 20 min and 3600 h a sequential extraction scheme was also used to fractionate Pb of incubated samples into soluble-exchangeable (Sol-Exch), carbonates associated (ACar), organic matter associated (AOM), Mn oxide associated (AMnOx), Fe oxide associated (AFeOx), and residual (Res) forms. Temperate soil samples had higher clay content, cation exchange capacity (CEC), dichromate oxidable organic carbon (OC), total Kjeldahl-nitrogen (TN), biological activity, amorphous and crystalline Fe and Al, but semiarid soil samples had higher sand content, pH, equivalent calcium carbonate (ECC), available P and K. Soil lead fractionation revealed that in both groups of soils Pb largely changed to exchangeable, carbonates associated and organic associated forms after 20 min. The chemical forms of Pb differed widely among soils after 3600-h incubation. The conversion rate of Pb from more available forms to less available forms was higher in temperate soils with higher Fe–Mn oxides and OM contents compared to semiarid soils. In temperate soils after 3600-h incubation, greater content of Pb was observed in Res (68%), AOM (14%), ACar (7%), and AMnOx (5%) fractions. However, in semiarid soils greater content of Pb was observed in Res (61%), ACar (16%), Sol-Exch (8%), and AOM (8%) fractions. The sum of AMnOx and AFeOx chemical forms for Pb in semiarid soils compared to temperate soils was lower. It was only 7% against 9% in temperate soils. Soil microorganisms in unsterile soils had significant effect on AOM, AFeOx and Res fractions of Pb. They not only increased AOM and AFeOx fractions of Pb in soils but also decreased Res fraction of Pb significantly.     

碳酸盐岩矿区河流沉积物中重金属的形态特征及潜在生态风险

黔西北土法炼锌及铅锌选矿厂对河流造成严重的重金属污染。河流沉积物中重金属的化学形态研究表明,同一采样点中不同重金属的形态分布和同一重金属在不同采样点中的形态分布均有较大差异。这可能与沉积物组分的不同亲和力,不同河段沉积物中粘土矿物、有机质、Fe Mn氧化物含量的不同以及人为活动(生活污水、选矿剂、矿渣等)的加入等有关,而碳酸盐岩地质背景的河床本身可能也有较大影响。潜在生态危害指数法研究表明,沉积物中重金属表现出强生态风险性,产生生态危害的主要重金属污染物是Pb,其后依次是Cd、Cu和Zn。     

Lead redistribution in a mine soil treated with three manures and incubated at two different temperatures

The study of heavy metals’ redistribution between different fractions allows to know their bioavailability and mobility in soils. Soil samples were collected from a lead mine in Hamadan provinces, NW Iran. In a factorial experiment soil was treated with cow, sheep and poultry manures (20?g?kg^?1 soil) separately and incubated near field capacity at 10°C and 37°C. An untreated soil (as control) was also incubated at the same temperatures. After 0 and 120 days, a sequential extraction scheme was used to fractionate Pb of incubated samples into soluble-exchangeable (Sol-Exch), organic matter associated (AOM), carbonates associated (ACar), and residual (Res) forms. Soil Pb in Sol-Exch and AOM fractions were increased by manure application significantly. The AOM and ACar forms of Pb were higher in soils treated with the manures and incubated in lower temperature. In contrast, the Sol-Exch and Res chemical forms of Pb were higher in the soils incubated at 37°C. These results may be related to the higher calcium carbonate dissolution and organic matter decomposition because of better biological activity in the soils incubated in higher temperature. The increase of the Res fraction (stable form) in this condition may resulted in lower toxicity and mobility in soil environment.