土壤重金属生物有效性研究进展

土壤重金属污染具有巨大环境风险。笔者围绕土壤重金属元素生物有效性(可给性)概念、元素形态与有效性影响因素、有效态(可给态)实验技术,综述了国内外研究现状。土壤金属元素形态和生物有效性取决于其地球化学行为、元素成因来源、土壤理化条件(p H值、有机质、粘土矿物与化学活性矿物、土壤粒级组成等)以及植物根际效应等。选择性单步提取和连续提取是检测土壤元素形态、有效态的有效和可行方法。针对手—口是土壤铅等污染物在儿童群体暴露的重要途径,发展了生物可给态体外试验方法。土壤污染物生物有效性和可给性已成为土壤污染风险评价的重要指标参数,实验成果也为土壤污染修复提供了重要依据。     

德安锑矿区土壤中锑的形态分析及生物可给性初探

按Tessier连续浸提法对德安锑矿区土壤样品进行了分析,得出锑的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。矿区土壤中锑生物可利用态锑占0.52%~3.51%,其浓度一般在1.78~17.48μg/g,中等可利用态占1.04%~5.56%,生物难利用态锑的浓度占92.1%~98.4%。     

利用体外方法评估不同淋洗剂对土壤中砷的淋洗效果及其健康风险

土壤砷污染已成为我国严重的环境问题,淋洗法是修复土壤砷污染较为有效的手段之一。文中以砷污染土壤为研究对象,运用2种环境友好的淋洗剂KH2PO4和草酸进行振荡淋洗实验,探究两种淋洗剂对不同砷污染土壤的淋洗效果,在此基础上,通过2种不同的体外方法 (physiologically based extraction test,PBET;in vitro gastrointestinal,IVG),探索其生物可给性及对人体的健康风险。结果显示,KH2PO4和草酸对土壤中砷有不同程度的去除,草酸对土壤砷的去除率较高,平均去除率为54.3%。运用PBET方法得到的土壤砷的生物可给性高于IVG方法,KH2PO4淋洗后土壤砷的生物可给性高于草酸。与草酸相比,KH2PO4淋洗会在一定程度上增加土壤砷的健康风险。不同in vitro方法对不同淋洗剂修复后效果有不同的评估结果,应该根据不同的淋洗剂选择较为保守的体外方法来评估淋洗后土壤的生物可给性及健康风险。     

环境水样中砷的化学形态分析

由于砷的化学形态不同,在环境中的毒性、分布、生物效应亦不相同,因而砷的形态分析在环境监测治理中有着不可忽视的重要作用.砷的形态分析     

印染污泥中重金属形态分析及生物有效性

选取上海某印染厂的印染废水处理后的活性污泥样品,通过盆栽土培试验,用黑麦草对印染污泥进行修复,运用Tessier A连续提取法研究修复后黑麦草根际和非根际印染污泥中铅、铜、镍、锌、镉5种重金属形态的变化,以及重金属的生物有效性与植物中有效态含量之间的关系。结果表明,栽培后根际与非根际环境中各重金属元素具有典型的形态分布特征:铅主要以离子交换态和残渣态存在;铜主要以碳酸盐结合态和残渣态存在;镍由紧结合态(铁锰氧化物结合态+有机结合态)向离子交换态转移;锌的有机结合态和碳酸盐结合态有所增加;镉主要以离子交换态和铁锰氧化物结合态为主,说明镉元素较活泼,具有潜在的环境影响能力,应该给予更多的关注。印染污泥中重金属的生物有效性与重金属元素的性质有关,铜、锌的生物有效性较高,其次是铅,最低是镍、镉。     

大同盆地浅层含水层沉积物中砷的生物可利用性评价

以采自大同盆地野外试验场的含水层沉积物为研究对象,调查高砷含水层中生物可利用性砷的含量及其影响因素。经实验室测定,沉积物总体呈碱性,Al、Fe等金属元素含量较高。利用连续提取法发现沉积物中砷结合形态主要为无定形和低结晶铁铝氧化物结合态,其次是残余态砷。其中铁铝氧化物形态的砷所占比例达53.54%,非专性吸附态和专性吸附态占14.33%,生物可利用形态的砷较少,这与体外模拟方法测定的生物可利用性砷含量较低吻合。体外模拟实验还发现：肠阶段生物可利用性砷含量比胃阶段低,生理学提取法(PBET)和体外消化法(IVG)测定的生物可利用性砷差异较小。     

土壤中硒的生物有效性表征方法及影响因素研究进展

硒是人体必需的微量元素之一。土壤-植物体系是人体摄入硒的主要途径,但尚缺乏准确评价土壤中硒生物有效性的通用方法,且影响因素也复杂多样, 这些问题制约了富硒土地资源的利用。本文通过追踪近年来国内外研究成果,系统地总结及比较了化学提取法、梯度扩散薄膜法、区域尺度硒生物有效性评价方法的优缺点。传统的化学提取法如单一提取和顺序提取在一定程度上能够表征土壤中生物有效性硒,但提取过程中存在影响因素多和提取不完全等问题。梯度扩散薄膜技术(DGT)能够模拟植物的根系吸收过程,相比顺序提取能更好地表征硒的生物有效性,但由于复杂的自然体系和不同元素结合相的差异,野外原位表征技术上仍存在难度。通过大规模的农作物-根系土样本,建立土壤-农作物硒元素评价模型,模型参数为影响土壤硒有效性的理化指标(如土壤酸碱度、有机质含量、土壤硒总量等),能较好地预测区域尺度上硒生物有效性。本文还总结了影响植物吸收土壤中硒的因素如地形、土壤类型、硒的存在形态、土壤理化性质、植物种类、土壤老化等,认为地形和土壤类型、硒的存在形态、酸碱度和有机质是影响有效硒的主要因素,植物种类与土壤老化为次要因素。完善DGT等原位分析检测技术、改进元素形态分析方法是未来发展的重要方向。     

浙西水田土壤镉形态与有效性研究

土壤镉(Cd)的生物有效性受多种因素影响,化学形态分布是决定其有效性的重要因素。为查明浙西水稻土Cd的生物有效性,分析土壤形态Cd与稻谷Cd含量关系,采集了32个田块土壤样及其中15个田块水稻样品,测试了土壤pH值、Cd总含量及各形态Cd含量和稻谷Cd含量,讨论了不同酸碱度及成土母质条件下土壤Cd形态分布特征及其生物有效性,研究了稻谷Cd含量与土壤不同形态Cd含量的相关性。结果表明,研究区水稻土Cd以离子交换态为主(约占全量的35%),水溶态Cd含量最小(约占全量的1%),其他形态Cd介于二者之间。酸性(pH 5.0～<6.5)条件下,土壤中离子交换态Cd含量最高,Cd生物有效性也最高。不同母质形成的土壤Cd形态分布特征不同,灰岩类风化物形成的土壤Cd形态分布特征与其他成母质区土壤差异明显,不同母质区的Cd污染应采取不同的治理措施。相关分析表明,稻谷Cd含量与土壤离子交换态Cd含量呈极显著相关性(P<0.01),而与其他形态Cd相关性不显著。     

北京平原区两年内土壤中五种重金属元素化学形态变化及生物有效性

为了监测北京市平原区2015年和2016年土壤中5种重金属As、Cd、Hg、Pb、Zn化学形态的变化趋势,运用Tessier连续提取法对土壤重金属进行了形态分析,并对影响重金属元素生物有效性的因素进行研究。结果表明,2年内研究区表层土壤重金属元素的形态变化微弱,有效态含量以Cd元素最高,达到45.67%,故潜在生态危害性最大;其次为Zn元素,达12.16%,其中碳酸盐结合态占比虽大,但由于研究区土壤呈偏碱性,Zn元素的迁移能力较弱,潜在危害性较小;As、Hg、Pb均以难迁移态存在,故潜在危害性也较小。土壤重金属元素的生物活性系数及迁移系数分别为:CdZnPbAsHg和CdAsZnPb=Hg,其中Cd元素2年的生物活性系数和迁移系数最高,展现出较强的生物活性和迁移能力,其余重金属元素的活性系数和迁移系数较低,潜在危害性较弱。影响重金属元素生物有效性的因素较复杂,以重金属元素全量为主,p H、有机质、CEC等理化性质次之。     

Arsenic contamination of groundwater: Mitigation strategies and policies

Contamination of groundwater by arsenic from natural geochemical sources is at present a most serious challenge in the planning of large-scale use of groundwater for drinking and other purposes. Recent improvements in detection limits of analytical instruments are allowing the correlation of health impacts such as cancer with large concentrations of arsenic in groundwater. However, there are at present no known large-scale technological solutions for the millions of people—mostly rural—who are potentially affected in developing countries. An overall framework of combating natural resource degradation is combined with case studies from Chile, Mexico, Bangladesh and elsewhere to arrive at a set of strategic recommendations for the global, national and local dimensions of the arsenic crisis. The main recommendations include: the need for flexibility in the elaboration of any arsenic mitigation strategy, the improvement and large-scale use of low-cost and participatory groundwater quality testing techniques, the need to maintain consistent use of key lessons learned worldwide in water supply and sanitation and to integrate arsenic as just one other factor in providing a sustainable water supply, and the following of distinct but communicable tracks between arsenic-related developments and enhanced, long-term, sustainable water supplies.

土壤中稀土元素地球化学研究进展

综述了土壤中稀土元素含量、稀土赋存形态、稀土生物有效性、稀土在土壤环境中的分布规律、迁移方式及其影响因子。讨论了稀土微肥应用中应注意的问题以及由此带来的环境效应，并探讨了建立具有普遍适用性的稀土生物有效性方法学的途径等。     

Evaluation of aluminum speciation in surface waters in China and its environmental risk assessment

As the ongoing global research on acid precipitation is developing in depth, more and more attention has been paid to the ecological effects of aluminum (Al) due to its toxicity to plants and animals, which is caused by acid precipitation. As a very serious problem of terrestrial and aquatic environmental acidification occurs in China, especially in southwestern China, a systematic investigation of Al speciation in these regions is very important. In this paper, the Al speciation results of surface waters in China are reported and its ecological impacts is evaluated. More than 100 water samples were collected from about twenty provinces of China. Driscoll's Al speciation scheme combined with the modified MINQEL computer model is used for speciation of Al. This study shows that the ecological impacts of acidification are quite different between China and Western countries, because of different geographical environments and geological settings. In Western countries, acidification is mainly caused by NO₂^-. Due to low concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺, the buffer capacities of soil and water are weak. Therefore, natural waters can be acidified to pH<5 very easily, resulting in a considerable mobilization of Al and worsening of the ecological environment. In China, acid precipitation is mainly in the form of sulfuric acid. In northwestern China, concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺ are high in soil and surface waters. This leads to much higher capacity and a high resistance ability to acidification. The pH values of waters in this region are high (around 7) and no serious Al toxicity is found at present. However, in northeastern and southeastern China, the soil is rich in Al (unsaturated aluminosilicates in northeastern China, saturated aluminosilicates in north and central China, aluminum-rich soil in southeastern and southwestern China). The concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺ in soil and waters are lower than those of northwestern China. Therefore the buffer capacity is limited. Numerous surface waters have already been acidified and pH values declined to 5. The impacts of Al toxicity on ecological systems in these regions are very serious, especially in Jiangxi, Hubei Provinces and Chongqing Municipality.     

Arsenic Geochemistry of the Great Dismal Swamp,Virginia, USA: Possible Organic Matter Controls

Surface water samples for arsenic (As) concentration and speciation analysis were collected from organic matter-rich blackwaters of the Lake Drummond portion of the Great Dismal Swamp in southeastern Virginia, USA. Arsenic concentrations and speciation were determined by selective hydride generation, gas chromatography with photoionization detection. Surface waters from the Great Dismal Swamp are high in dissolved organic carbon (DOC) concentrations (445–9,600 μmol/kg) and of low pH (4.2–6.4). Total dissolved As concentrations [i.e., As(III) + As(V)], hereafter As_T, range from 2.2 nmol/kg to 21.4 nmol/kg. Arsenite, As(III), concentrations range from ∼1 nmol/kg to 17.7 nmol/kg, and As(V) ranges from ∼1 nmol/kg to 14.1 nmol/kg. Arsenate, As(V), is the predominant form of dissolved As in the inflow waters to the Great Dismal Swamp, whereas within the swamp proper arsenite, As(III), dominates. Arsenite accounts for 8–37% of As_T in inflow waters west of the Suffolk Scarp, and between 54% and 81% of As_T in Lake Drummond and Great Dismal Swamp waters east of the scarp. Arsenite is strongly correlated to DOC (r = 0.94) and inversely related to pH (r = −0.9), both at greater than the 99% confidence level. Arsenate is weakly related to pH and DOC (r = 0.4 and −0.37, respectively), and neither relationship is statistically significant. No statistical relationships exist between As(V) or As(III) and PO₄ concentrations. The predominance of As(III) and its strong correlation with DOC in Great Dismal Swamp waters suggest that DOC may inhibit As(III) adsorption or form stable aqueous complexes with As(III) in these waters. Alternatively, phytoplankton and/or bacterially mediated reduction of As(V) may be important processes in the organic-rich blackwaters and/or sediment porewaters of the swamp, leading to the prevalence of As(III) in the water column.     

生物活性元素Fe来源及其溶解度影响因素研究综述

具有生物活性的元素Fe被认为限制了海洋生物生产力,其在海洋生态系统中的生物地球化学循环对全球碳循环起到调节作用,全球40％～50％的海洋因“高叶绿素低营养盐”(HNLC)“缺Fe”而初级生产力较低.然而,关于生物活性元素Fe的研究不仅涉及海洋科学,还与大气科学、环境科学、地球科学等学科紧密联系.近些年,围绕生物活性元素“Fe”开展的研究不仅是地球科学领域的前沿问题,还是海洋学家与环境学家共同关注的热点问题.目前,尽管对于生物活性元素Fe的研究已取得很大的进展,但模型、室内实验及野外观测之间仍存在很大的挑战与不确定性.系统地总结了生物活性元素Fe最重要的自然来源方式,详细介绍了影响生物活性元素Fe溶解度的主要因素,最后,对将来的工作提出建议,为我国未来开展类似的研究提供参考.     

高砷地下水研究的热点及发展趋势

全球范围内广泛分布的高砷地下水给人们的健康造成了极大的威胁.高砷地下水的形成机理是一项世界性的科学问题.介绍了高砷地下水的分布特点、富集机理,阐明了溶解性有机物、地下水流动特征对高砷地下水形成的影响机制.现今的研究揭示了有机物和微生物协同作用下高砷地下水的形成过程,并且在高砷地下水的空间分布、时间变化特征以及人类活动对高砷地下水形成的影响等方面取得了一些创新性成果.这3方面的研究也逐渐成为近些年高砷地下水研究的热点.这些研究不仅丰富了砷迁移转化的理论成果,而且有助于开辟低砷水源,保障水资源的可持续利用,具有重要的理论和现实意义.     

Arsenic, antimony and other toxic elements in the drinking water of Eastern Thessaly in Greece and its possible effects on human health

Twenty-six groundwater samples were collected from the Eastern Thessaly region and analysed by ICP-ES for these elements: Al, As, P, Pb, Zn, Mn, Fe, Cr, Sb, Cu, Na, Br, Cl, Si, Mg, Ag, Be, Bi, Dy, Er, Eu, Au, Ge, Ho, In, Ir, Os, Pt, Re, Rh, Ru, Lu, Hf, Hg, Tm, Zr and Nb. The objectives of the study were to assess the level of water contamination with respect to the EC and the USEPA health-based drinking water criteria. The geology of the studied area includes schists, amphibolites, marbles of Palaeozoic age, ophiolites, limestones of Triassic and Cretaceous age, Neogene and Quaternary deposits. The element ranges for groundwater samples are: Al 7–56 μg l⁻¹, As 1–125 μg l⁻¹, Br 6–60 μg l⁻¹, Cl 500–25,000 μg l⁻¹, Cr 1–6 μg l⁻¹, Cu 1–15 μg l⁻¹, Fe 10–352 μg l⁻¹, Mg 2,940–40,100 μg l⁻¹, Mn 0–8 μg l⁻¹, Na 3,650–13,740 μg l⁻¹, P 20–48 μg l⁻¹, Pb 0–7 μg l⁻¹, Sb 0–21 μg l⁻¹, Si 3,310–13,240 μg l⁻¹ and Zn 7–994 μg l⁻¹. The results of groundwater analyses from the region of Eastern Thessaly showed elevated concentrations of As and Sb. Factor analysis explained 77.8% of the total variance of the data through five factors. Concentration of Br, Cl, Mg, Na and Si is directly related to the presence of saltwater in the aquifer, so grouping of these variables in factor 1 probably reflects the seawater intrusion. Al, As and Sb are known to form complexes in the environment, so grouping of these elements in factor 2 indicates their similar geochemical behaviour in the environment. The high negative loading of Mn in factor 2 indicates the presence of manganese oxides–hydroxides in the study area. Pb and Zn are associated together in sulphide mineralisation; so grouping of these elements in factor 3 reflects the sulphide mineralization paragenesis in the Melivoia area. P and Cu are associated together in phosphate fertilizers; so grouping of these variables in factor 4 could be related to agricultural practices. Cr, Fe, Mn and Mg are associated together in iron and manganese oxides–hydroxides and the weathering products of the olivine of the ultrabasic rocks; so grouping of these elements in factor 5 reflects the lithology of the area. There is a natural contamination of groundwaters with elevated concentrations of As and Sb due to the presence of the arsenopyrite and stibnite mineralisation in the Melivoia, Sotiritsa and Ano Polydendri areas. Contamination over the health-based drinking water guidelines given by EC and EPA has been investigated from nine sampling sites out of 26 of Eastern Thessaly region.