On the determination of total heavy metal content in saline soils and soils rich in organic matter

Abstract

Methods of soil decomposition for determination of heavy metal total content were considered. Two saline soils (chloride and sulphate solonchak solonetz) and one rich in organic matter were uzed for investigation. It has been established that decomposition by using HF‐HCl with a preliminary ignition at 500°C is a very suitable method. The type of the studied soils and the results obtained allow for this method to be recommended for decomposition of various soils.

On the basis of experiments with modelled soils it has been proved that possibilities for heavy metal losses on ignition are created when NaCl content and the percentage of weakly bound heavy metals (water‐soluble, exchangeable, etc.) are high. Under the conditions of the experiment (acid soils ‐ pH 4.3 and 5.0) losses of Zn and Pb but not of Cu have been incurred. Although these cases are not typical, this requires the applicability of the method for such particular occasions to be checked.     

Effects of heavy metals on the litter consumption by the earthworm Lumbricus rubellus in field soils

Aim of this study was to determine effects of heavy metals on litter consumption by the earthworm Lumbricus rubellus in National Park the “Brabantsche Biesbosch”, the Netherlands. Adult L. rubellus were collected from 12 polluted and from one unpolluted field site. Earthworms collected at the unpolluted site were kept in their native soil and in soil from each of the 12 Biesbosch sites. Earthworms collected in the Biesbosch were kept in their native soils. Non-polluted poplar (Populus sp.) litter was offered as a food source and litter consumption and earthworm biomass were determined after 54 days. Cd, Cu and Zn concentrations were determined in soil, pore water and 0.01 M CaCl₂ extracts of the soil and in earthworms. In spite of low available metal concentrations in the polluted soils, Cd, Cu and Zn concentrations in L. rubellus were increased. The litter consumption rate per biomass was positively related to internal Cd and Zn concentrations of earthworms collected from the Biesbosch and kept in native soil. A possible explanation is an increased demand for energy, needed for the regulation and detoxification of heavy metals. Litter consumption per biomass of earthworms from the reference site and kept in the polluted Biesbosch soils, was not related to any of the determined soil characteristics and metal concentrations.     

我国北方典型日光温室蔬菜生产系统土壤重金属积累趋势

本文以山东省寿光市日光温室蔬菜生产系统为例,研究了As、Cd、Cu、Hg、Pb和Zn等重金属元素在土壤中的积累趋势。结果表明：有机肥中Cu、Zn元素含量较高,而无机肥中Cd、Zn元素含量较高,但所有元素均未超过目前的相关标准。表层土壤中上述元素的平均含量均未超出《温室蔬菜产地环境质量评价标准》(HJ333-2006)相应的标准限值,但Cd平均含量已接近评价标准。除了As和Pb元素外,表层土壤中Cd、Cu、Hg和Zn的含量随着种植年限的增长而增加,出现积累。在目前的重金属积累状况下,主要蔬菜可食部分的重金属含量明显低于中国食品污染物限量标准,处于安全级别。由于蔬菜生产最初均是在底层土壤上开始的,加之封闭的生产环境,表明土壤中重金属主要来自各种农用投入品的输入,而各种肥料的高量输入是其积累的主要原因。今后对该地区设施蔬菜生产的环境管理,除了制定更严格的肥料重金属含量标准外,更重要的是要严格控制各种肥料的施用量,这样既可降低系统养分过量盈余,又可控制土壤重金属的积累。     

Sources of bioavailable trace metals for earthworms from a Zn-, Pb- and Cd-contaminated soil

The sources of bioavailable metals for earthworms were investigated in a Zn-, Pb- and Cd-contaminated soil. Selective sequential extractions (SSE) of metals were performed on soil samples with different amounts of contamination and compared with the body burden concentration of metals in two earthworm species: Aporrectodea caliginosa and Lumbricus rubellus. The most labile forms (water extractable and exchangeable) of metals were poorly related with metal accumulation by the earthworms, except for Cd, whereas the moderately available forms (acid-soluble, bound to iron oxides and organic matter) were related to the pattern of metal accumulation by earthworms. This indicates that the ingestion of metals bound to soil components is likely to be a more important uptake route than the dermal uptake of dissolved ions for metals entering the body tissue of earthworms.     

设施蔬菜生产系统重金属积累特征及生态效应

研究土壤重金属的空间变异特征,可以揭示人为活动对土壤中重金属积累特征的影响,进而为土壤利用、污染风险评价提供重要的基础资料.选取南京市郊区一处典型的设施蔬菜生产系统为研究对象,测定了土壤、灌溉用水、肥料、蔬菜等介质中重金属砷(As)、镉(Cd)、铜(Cu)、汞(Hg)、铅(Pb)、锌(Zn)含量,研究了土壤中重金属的空间变异及积累特征,分析了积累产生的原因,讨论了系统中作物的重金属积累效应.结果表明:(1)与露天蔬菜地相比,设施蔬菜地土壤重金属Cu、Hg、Pb、Zn均产生明显的累积,且土壤中Cu、Hg、Pb平均含量超过温室蔬菜产地环境质量评价标准.(2)农用投入品的大量输入对土壤性质的空间变异产生了明显影响,而土壤Cu、Hg、Pb、Zn也呈现与之一致的空间变异特征,且这些元素与土壤性质存在显著相关性.(3)土壤性质的变化和重金属的积累对叶菜类作物重金属吸收影响较大,且前者更为重要.     

根际促生菌及其在污染土壤植物修复中的应用

植物对重金属吸收、转运和积累以及植物生物学特征使其成为修复重金属污染土壤的重要手段之一。然而,由于植物对重金属的耐受性有限而限制其广泛实际应用,因而探讨植物修复技术强化措施就显得尤为重要。随着自然资源的开发和技术的发展,微生物调控使植物修复技术变得更为可行和更有价值。回顾近年来新兴的微生物调控技术,植物根际促生菌资源因其对环境无污染,可利用自身的抗性系统减缓重金属对植物的毒性,促进植物的生长和影响重金属的迁移等优势,在修复过程中发挥着重要作用。目前,国内外就植物根际促生菌的筛选、鉴定和应用价值等方面已经做了大量的相关研究。本文综述了根际促生菌-植物相互作用的机制及其促进植物修复重金属污染土壤的作用原理。     

Short-term responses of two contrasting species of earthworms in an agricultural soil amended with coal fly-ash

With the renewed interest in the use of coal fly-ash for amendment of agricultural soils in Australia, we assessed how earthworms, as indicators of soil health, responded to this ameliorant. We assessed survival, weight, burrowing and elemental concentrations for earthworms of a native unnamed Megascolecid species and of exotic Aporrectodea trapezoides in intact soil cores treated with an alkaline fly-ash at rates equivalent to 0, 5 and 25 t/ha over 6 weeks. Fly-ash did not affect survival, growth, number of burrows created or phosphorus solubilisation. Transfer of the earthworms to the new environment having vastly different pH from where they were collected, and possibly overcrowding, caused mortality in the soil cores for all treatments. A. trapezoides that had smaller individuals suffered mortality of 12% compared with 23% for the larger earthworms of Megascolecids. Earthworms of Megascolecids each increased their weight by 0.24g (25% of their original weight) while those of A. trapezoides lost 0.18g each (21% of their original weight). The difference in growth between the two earthworms was associated with grazing habit and probably with the large difference in the pH between source soil and that of the core soil. Megascolecids appeared to minimize grazing on ash-tainted soil and so ingested less Zn, which was more abundant in the fly-ash than in the soil, compared with A. trapezoides that had elevated concentration of this metal. Extractable P in the soil was increased with both species of earthworms, more so with the exotic species that solubilized 11% more P than the native Megascolecids. The benign influence of fly-ash on survival and growth of worms was associated with the pH of soil remaining unchanged during the six weeks of incubation.     

南京沿江典型蔬菜生产系统土壤重金属异常的源解析

以南京沿江典型蔬菜生产系统为研究对象,通过测定并分析表层土壤、剖面土壤、肥料及大气降尘中重金属含量,揭示了土壤重金属异常的空间变异特征以及土壤重金属的来源。结果表明,(1)研究区表层土壤镉(Cd)、砷(As)、汞(Hg)、铅(Pb)、铜(Cu)、锌(Zn)和铬(Cr)平均含量均高于南京市土壤背景值,部分样点土壤Cd含量超过了国家土壤环境质量标准的二级标准,在土壤中呈现较高的累积;(2)除Cr以外,其他表层土壤重金属均呈现东南偏高西北偏低的空间分布特征,与土壤有机质的空间分布规律一致;(3)土壤重金属累积和分布状况与研究区的地形、周边工农业布局以及风向有关;(4)除土壤重金属累积的自然背景原因以外,农业施肥和大气沉降对土壤重金属的累积具有非常重要的贡献。     

朝天委陵菜的重金属耐性与吸收性研究

利用植物生长室水培试验和温室土培盆栽试验的方法,研究了朝天委陵菜在不同浓度Pb水培条件下和Cu、Zn、Pb、Cd复合污染土壤条件下的重金属耐性和吸收性,结果表明,水培条件下随着处理浓度的增加,朝天委陵菜均生长良好,虽高浓度Pb处理下出现植株矮小、叶渐黄、根系变黑等毒害症状,但植株并未死亡,表明在水培条件下朝天委陵菜对Pb具有极强的耐性;在最高浓度3 600μmol/L Pb处理下地上部和根中Pb浓度达到最大值,分别为947 mg/kg和71 053 mg/kg。在温室土培盆栽条件下,朝天委陵菜在外加Cu、Zn、Pb和Cd分别为200、1 000、1 000和5 mg/kg的土壤上较对照生长受到抑制,地上部Cu、Zn、Pb和Cd浓度分别达到741±164、18 248±2 222、1 543±483和29.4±5.2 mg/kg;外加重金属更高时则导致植株死亡。朝天委陵菜对Pb胁迫和Cu、Zn、Pb、Cd复合污染土壤具有较强的耐受性,可作为重金属尤其是Pb污染土壤的修复植物。     

Microbial biomass,activity, and organic matter accumulation in soils contaminated with heavy metals

Chemical characteristics and some parameters related to biological components were determined in 16 soils from a fairly homogeneous area in the north of Italy, contaminated with different levels of heavy metals. Correlation analysis of the parameters studied showed close positive relationships among the metals and with the organic C content in the soils studied. Negative relationships were observed among the heavy metals, soil respiration, and the ratio between evolved CO₂–C and microbial biomass C per unit time (specific respiratory activity). This was ascribed to an adverse heavy metal effect on the soil microflora, which appeared to increase the accumulation of organic matter as the heavy metal content increased, probably because the biomass was less effective in mineralising soil organic matter under these conditions.     

典型乡镇企业密集区土壤-蔬菜系统重金属分布与关联特征

土壤中有毒污染物的生物有效性及其在土壤－植物系统的迁移富集是当前研究的热点问题。该研究对乡镇企业密集地——东莞地区常见的7种叶菜类蔬菜及其相应土壤样品中的Cu、Zn、Cr、Ni、Pb等重金属元素的全量和稀盐酸可提取态进行了分析。结果表明：研究区蔬菜存在明显的有毒金属元素（Ni、Pb）超标和有益金属元素（Cu、Zn）缺乏问题,蔬菜重金属含量与土壤重金属总量和可提取态重金属含量均无显著的相关性,但可提取态含量的富集系数与蔬菜重金属含量具有显著相关性,其可以较好地指示土壤可提取态重金属向蔬菜系统的转移规律。不同品种蔬菜对各重金属的富集系数随可提取态重金属含量增加呈幂函数形式递减,且递减趋势与土壤中可提取态重金属含量范围密切相关。当数据量有限时,利用富集系数与对应可提取态重金属含量之间的回归模型对富集系数定量估值,其准确性要高于取相应的均值或中值。     

红透山铜尾矿重金属分布及其对土壤重金属污染的影响

通过对红透山铜尾矿重金属分布及尾矿区和农田区土壤重金属污染状况进行研究,结果显示:尾矿中四种重金属Cu、Zn、Pb、Cd均出现不同程度的淋滤-富集现象,对周围土壤存在较大的环境威胁。尾矿区土壤综合污染指数16.27,达重污染程度;周围农田土壤为轻度污染,综合污染指数1.29。四种重金属的污染状况分别为:Cd、Cu为重度污染,Zn为轻度污染,Pb为安全级别。     

Assessing heavy metal contamination in soils of the Zagreb region (Northwest Croatia) using multivariate geostatistics

The assessment of soil contamination and location of pollution sources represent a crucial issue in soil remediation. Topsoil samples were collected in the Zagreb area (Northwest Croatia) and the total contents of trace and major elements were determined. A multivariate geostatistical analysis was used to estimate soil chemical composition variability. Factorial Kriging Analysis (FKA) was used to investigate the scale-dependent correlation structure of some variables by modelling co-regionalization of ten chemical variables, co-kriging specific factors and mapping them. The FKA provided two regionalized factors at different spatial scales of variability: the first factor at shorter range for Zn, Pb, Cd, Cu and Ni indicated different sources of anthropogenic contamination, whereas Ca (mainly loading on the longer range factor) was related to the lithology and parent material composition. The methodology used has proved to be a useful tool to separate geological and anthropogenic causes of variation in soil heavy metal content and to identify common pollution sources.     

矿区植物根内嗜鱼外瓶霉对重金属的耐性和超积累作用

从云南会泽铅-锌矿区自然生长植物密序野古草(Arundinella bengalensis(Spreng.)Druce)的健康根内分离得到一株深色有隔内生真菌(dark septate endophytes,DSE)。据其形态学特征和ITS1-5.8S-rDNA-ITS2序列分析,鉴定为一株嗜鱼外瓶霉(Exophiala pisciphila)。纯培养条件下研究了其对Pb2+、Zn2+、Cd2+的耐性和超积累作用。结果表明,此菌株在液体合成培养基上可以分别耐受2、3和0.5 g/L的Pb2+、Zn2+和Cd2+;在含Pb2+、Cd2+培养基中生长其菌丝可以富集超过其干重25%以上的Pb2+和5%以上的Cd2+;显示此菌株属于极端耐性并具有超积累作用的真菌。此真菌在植物根系的定殖或许可以通过菌丝体对金属离子的固持作用缓解植物根围土壤微环境中超量金属离子对植物的毒害作用。     

Comparative evaluation of residual and total metal analyses in polluted soils

Abstract

Two digestion procedures, employing aqua regia‐HF (ARHF) and HNO₃‐HCIO4‐HF (HHH), were used to analyze residual metals (following a chemical fractionation scheme) and total metal content of two soils, one moderately polluted by municipal sludge applications and the other a grossly‐contaminated sample (20.8% Pb) from a battery recycling site. Although commonly used in sequential extraction analyses, the ARHF method solubilized only 53% (significant at p = 0.05) of the HHH‐determined residual Pb in the battery soil. For the sludge‐amended soil, residual Cd, Pb, and Zn were not statistically different by the two methods. For the battery soil, a single ARHF extraction also underestimated total Pb and Cu relative to HHH, but both methods gave statistically‐similar total Cd, Cu, Pb, and Zn for the sludge‐amended soil. As the sample metal concentration increased, the ability of ARHF to solubilize HHH‐equivalent metal quantities generally decreased. Since the degree of contamination is often unknown for environmental samples, the HHH method is more reliable for assessing residual and total metals in polluted soils     

畜禽固废沼肥中重金属来源及其生物有效性研究进展

畜禽养殖业的规模化快速发展给环境带来大量的畜禽固废,通过沼气工程,不仅可以得到沼气这一能源,其发酵产物-沼肥还可以作为有机肥施用于农田,这一模式,被我国众多的规模畜禽养殖场采用。然而,由于畜禽粪便中重金属含量的不断增加,沼渣、沼液中的重金属含量及其施入土壤中的生物有效性逐渐受到人们的关注。本文将从畜禽固废沼渣、沼液中重金属的主要来源、含量、生物有效性及其可能的风险等方面进行论述,以期为深入研究沼肥的使用安全提供借鉴,并为合理利用沼肥,采取相关措施降低生态危险提供依据。     

污泥与施污土壤重金属生物活性及生态风险评价

将城市污泥以不同质量比施于土壤中构成污泥混合土壤,研究各污泥配比土壤中重金属的生物活性,并采用三种重金属评价方法(地累积指数法、潜在生态风险指数法、综合毒性指数模型)和黑麦草对重金属的吸收富集效果来对施污土壤中重金属具有的生态风险性进行评价。结果表明:污泥的添加使土壤中生物活性态Cd、Cu和Zn含量显著增加,对三种重金属具有活化作用,但对Pb却起到钝化作用。生态风险评价结果表明:污泥的添加使土壤中Pb呈现无污染和低生态风险;Cu和Zn呈现中度污染和低生态风险;Cd达到强度污染和重度生态风险,重金属潜在生态风险(RI)总体处于强度生态风险水平。当污泥添加比例大于6:10(污泥S3处理)时,施污土壤中重金属的综合毒性指数高于土壤对照。黑麦草对Cd、Pb、Cu和Zn的富集浓度与施污土壤中对应重金属的生物活性态含量存在显著正幂指数关系,同时黑麦草对施污土壤中Cd、Cu和Pb的富集能力大小与地累积指数法和潜在生态风险指数法对三种重金属具有的生态风险性的评价结果具有一致性。     

肥料重金属含量状况及施肥对土壤和作物重金属富集的影响

本文对肥料中重金属的含量状况以及施肥对土壤和农作物重金属累积影响的研究进展进行了系统分析和总结。过磷酸钙中锌（Zn）、 铜（Cu）、 镉（Cd）、 铅（Pb）含量高于氮肥、 钾肥和三元复合肥,有机-无机复混肥料中的Pb含量高于其他化肥。有机肥如畜禽粪便、 污泥及其堆肥中的重金属含量高于化肥,猪粪中的Cu、 Zn、 砷（As）、 Cd含量明显高于其他有机废弃物,鸡粪中铬（Cr）含量高;污泥和垃圾堆肥中Pb或汞（Hg）含量高。商品有机肥Zn、 Pb和镍（Ni）含量高于堆肥,Hg含量高于畜禽粪便。多数研究表明,氮磷钾配施与不施肥相比土壤Cd和Pb含量增加,施用有机肥比不施肥提高土壤Cu、 Zn、 Pb、 Cd含量。施用化肥对农作物重金属富集的影响不明确,而施用有机肥可提高作物可食部位Cu、 Zn、 Cd、 Pb 的含量,影响大小与有机肥种类、 用量、 土壤类型和pH以及作物种类等有很大关系。在今后的研究中应着重以下几个方面, 1）典型种植体系下土壤重金属的投入/产出平衡; 2）不同种植体系下长期不同施肥措施对土壤重金属含量、 有效性影响的动态趋势; 3）典型种植体系和施肥措施下土壤对重金属的最高承载年限; 4）现有施肥措施下肥料中重金属的最高限量标准。     

Inhibitory effects of the total and water-soluble concentrations of nine different metals on the dehydrogenase activity of a loess soil

 This study focuses on a comparison of the microbial toxicity of nine metals, including As as a metalloid and two species of Cr. A loess soil [Ap horizon, clay 15.2%, organic C 1.12%, pH(CaCl₂) 7.02] was spiked with 8–12 geometrically increasing doses of the metals. The dehydrogenase assay (2-p-iodophenyl-3-p-nitrophenyl-5-phenyltetrazoliumchloride method) was combined with sorption and solubility experiments. The resulting dose-response curves and sorption isotherms were used to derive total doses that caused definite percentage inhibitions [i.e. effective doses (ED) causing a 10–90% reduction in dehydrogenase activity (dha)] as well as the corresponding toxic solution concentrations causing the same reductions in dha (i.e. effective concentrations; EC₁₀–EC₉₀). Based on total doses, the toxicity decreased in the following order with ED₅₀ values (mg kg^–1) given in brackets: Hg (2.0)>Cu (35)>Cr(VI) (71)>Cr(III) (75)>Cd (90)>Ni (100)>Zn (115)>As (168)>Co (582)>Pb (652). With regard to solution concentrations, toxicity decreased in the order (EC₅₀ in mg l^–1): Hg (0.003)>Pb (0.04)>Cu (0.05)>Cd (0.14)>Zn (0.19)>Cr(III) (0.62)>Ni (0.69)>Co (30.6)>As (55.5)>Cr(VI) (78.1). The retention of the metals by the soil differed strongly. Pb, Cu, and Hg exhibited the highest and Ni, As, and Cr(VI) the lowest sorption constants (Freundlich K values: 2455, 724, 348, 93, 13, and 0.06 mg kg^–1, respectively). The sorptivity of the metals and their microbial toxicity in the aqueous phase were characteristically related: metals with a strong toxic action in the soil solution were adsorbed by the soil to a high degree and vice versa. Therefore, especially for metals with a high inherent toxicity, sorption is an effective way of immobilizing them and temporarily detoxifying soil. Received: 2 July 1998     

东莞石马河沿岸土壤重金属污染及生态毒性研究

为研究河水-地下水交互作用对河流沿岸土壤环境质量的影响,以东莞石马河沿岸土壤为研究对象,采集沿岸距离河道不等的6个土壤剖面共31个土样,测定土壤重金属(As、Cd、Cr、Cu、Fe、Mn、Ni、Pb和Zn)含量和土壤水提取液对发光菌的抑制率。结果表明,Cd、Cu、Ni和Zn的含量分别为2.80~11.2mg kg-1、9.70~298mg kg-1、11.4~69.7mg kg-1和40.4~465mg kg-1;Cd的地累积系数为6.06,达到极度污染水平;土壤重金属污染的地累积系数排序为CdZnCuNiCrMnAsPbFe;重金属含量差异与土壤有机质(SOM)含量和土壤微粒组分(63μm)有关,Cr、Cu、Ni、Zn、Mn和Cr、Ni与SOM含量和微粒组分分别呈显著正相关(p0.05或p0.01);土壤剖面毒性单位(∑TU)评价结果为剖面S3S2SbS1S4Sa,其中剖面S3的值最大,为5.51,属于中毒;土壤水提取液对发光菌的抑制率为2.45%~16.5%,为无毒或低毒。