废弃铅锌矿区复耕后土壤-作物重金属污染特征及修复措施

[目的]了解废弃铅锌矿区复耕农田耕作层土壤—作物污染特征及变化情况,探究最合理的植物修复系统。[方法]利用基于GIS的Tominson负荷指数法对不同耕地重金属污染分布格局及来源进行分析;采用富集系数法(BCF),复合质量影响指数法(ⅡCQ)探究土壤—作物污染特征。[结果]研究区耕作层土壤中Cd,Zn,Pb,Hg含量分别是贵州省背景值的100,45,18,18倍,Cu,As,Cr与背景值基本相同;蒟蒻种植地为重度污染。茎块类作物食用部分富集重金属能力最强,稻米次之,瓜类作物最弱,当地瓜类作物可做为抗富集重金属的先行植物。[结论] Cd为主要控制因子,蒟蒻种植地为主要控制区域;根据研究区重金属空间分布特征,重度污染区域建议采用超富集植物修复及活化剂共同作用;中度污染区域种植抗富集蔬菜及阻绝污染源的方式;轻度污染区域稻米种植区采用钝化措施,从而达到修复耕作层土壤重金属目的。     

天津地区土壤环境中有效态重金属的分布特征与生态意义

重金属是土壤环境中对土壤质量有着极其重要影响的的污染物之一,重金属在土壤中的有效态既决定了它的生物有效性及对环境的危害程度,又是人们对受污染土壤进行治理和修复的基础。文章在分析天津市土壤类型、土壤质地和土地利用类型的基础上,分析了不同类型、质地和土地利用类型等各种类型土壤环境中Cu、Pb、Zn、Cd、Ni、Cr、Mn等重金属元素有效态含量的分布特征及生态意义。     

基于多元统计和地统计的肇源县表层土壤重金属来源辨析

土壤圈是地圈系统中对人类健康影响最显著的圈层之一。土壤重金属的自然和人为来源辨析对土壤修复和保障人体健康有重要意义。本研究以黑龙江省肇源县为研究区域,通过空间插值分析、主成分分析和聚类分析等方法,对区域土壤表层和深层土壤重金属As、Hg、Cd、Cr、Cu、Ni、Zn的含量和空间分异特征进行分析,进而对区域表层土壤重金属来源进行辨析。结果表明:成土母质作为表层土壤的重要物质来源对表层土壤重金属含量及空间分布有显著影响;肇源县表层土壤中Hg元素表现出全局范围较明显的富集现象,局部区域Cd元素表现出一定的富集现象,富集原因是人为污染造成的;嫩江上游汇水区土壤重金属元素的迁入,是表层土壤重金属As、Cd、Cr、Cu、Ni、Zn等元素在研究区范围内轻度富集的主要原因。     

北京平原区土壤Cr空间分布及影响因素研究

以北京市平原区农田土壤为研究对象,针对不同功能区、不同种植模式及不同母质类型等因素,基于经典统计学、经验贝叶斯克里格插值法,从点与区域两个方面对不同土壤深度(0~25、25~50 cm)重金属Cr含量的水平和垂直分布及影响因素作了系统分析。结果表明:从整体看,不同土壤深度重金属Cr含量存在一定差异,不同区域比较以海淀和丰台平均含量为最高;空间分布上,不同土壤深度(0~25、25~50 cm)Cr含量水平分布格局基本一致,其分布以城区为中心向外逐渐降低。从单因子评价看,处于警戒线以内的区域面积仅占研究区总体的19.16%(0~25 cm)和14.81%(25~50 cm),存在明显富集现象。不同功能区重金属Cr含量在不同土壤深度中排序均为都市生活区农业保障区水源保护区,且对不同土壤深度Cr含量存在显著性影响;种植模式及母质类型对不同土壤深度Cr含量无显著影响,且组间无显著性差异。该研究成果可为农田土壤重金属污染进一步治理和管护提供科学依据。     

不同农业用地类型对土壤性质和土壤环境的影响——以北京市延庆县为例

选择北京市延庆县为研究区域,通过对不同农业用地类型的土壤进行采样和分析,研究了延庆县不同农业用地类型对土壤性质和环境的影响,以期为北京市土壤的农业可持续利用提供依据。结果表明,研究区域粮田、菜地、果园的土壤pH值、有机质和碱解氮含量均显著低于林地;4种不同农业用地类型中表层土壤的As,Cd,Cr含量平均值分别超出北京市土壤背景值0.93,0.09和15.3 mg/kg。粮田、菜地耕作层的重金属含量高于林地和果园,内梅罗指数和单项污染指数评价表明这4种土壤利用类型尚属清洁。尽管研究区目前重金属污染程度较低,最高值仅为警戒值的74%,但其单项污染指数显示该地区土壤重金属累积速度较快。粮田土壤中As,Cd元素含量较退耕林地分别增加了20.9%和38.5%。如不加以控制,土壤重金属污染状况会进一步加剧。     

黑龙江省海伦市农田土壤重金属分布特征及污染评价

海伦市是以农业为主导产业的黑龙江省县级市,为了解该市土壤重金属时空分布特征及其污染现状,对农田耕层及亚耕层土壤中Cd、Cr、Cu、Ni、Pb、Zn、Hg和As等重金属全量进行了分析,并采用单因子污染指数法和Nemerow综合污染指数法分别对土壤的重金属污染状况进行了评价。结果表明,该地区土壤重金属含量较低,总体表现为西南和西北含量较高、西部含量高于东部的空间分布特征。以松嫩平原土壤元素背景值为标准进行评价,已出现一定程度的污染。以GB15618-1995土壤环境质量标准二级标准进行评价,综合污染指数为0.504,所有样点土壤重金属均未达到污染水平。与耕层土壤相比,亚耕层土壤Hg和Cd含量显著下降,其他元素含量及分布特征则与耕层相似。从1980年到2008年,随着时间的变化,该区域土壤重金属含量增加趋势不明显,近期土壤出现重金属污染风险较小。     

基于地统计学的樱桃园土壤重金属污染评价及来源解析

为研究天水市樱桃园土壤重金属污染的空间分布特征,实地采集0~20 cm土壤样品,测定重金属Pb、Cd、Cr、Cu、Zn含量,并运用多元统计分析等方法定量分析了研究区土壤表层重金属污染程度。结果表明:以甘肃省土壤背景值作为评价标准,除Cd元素外,其他元素的均值都超过了甘肃省土壤背景值;从土壤重金属元素空间分布格局来看,研究区东北部土壤重金属污染较西南部严重;从土壤重金属元素污染源来看,造成樱桃园土壤重金属污染最主要的因素为成土母质、农药;5种重金属元素均存在不同来源的污染,污染来源不单一,属于混合源污染。     

路基边坡土壤重金属污染特征及评价

以盐淮高速公路沿线为研究区域,分析了路基边坡及附近土壤中Cr,Cu,Pb三种重金属的污染特征,并对污染现状进行了评价。结果表明,土壤中三种重金属含量在不同采样区均存在显著差异(P<0.05),填土来源和交通量是造成各采样区土壤重金属含量差异的主要原因;在一定区域内,土壤中各重金属元素的含量随着离路肩距离的增加总体上呈现先降后升的趋势;在所有采样区土壤中,三种重金属含量高低排序为Cr>Cu>Pb,三元素之间具有显著的相关关系(P<0.01);对重金属污染现状潜在生态风险的评价表明,研究区域的生态风险程度为轻微级。     

区域土壤Cd和Cr空间分布的影响因素研究

以种粮大县肇源为研究区,对土壤表层Cd、Cr两种元素水平空间变异及分布特征的影响因素进行深入探讨。结果表明:(1)肇源县土壤表层重金属Cd和Cr的平均含量分别为0.078、46.006 mg/kg,略高于松嫩平原土壤背景值。表层土壤Cd的块金效应为0.432,具有中等程度的空间自相关性;表层土壤Cr的块金效应为0.227,存在强烈的空间自相关性。Cd、Cr元素的空间自相关表现出较为明显的各向异性,均在45°(东北-西南)和135°(东南-西北)方向上空间自相关最强烈。(2)表层土壤和成土母质中Cd和Cr元素含量相关分析结果显示,相关系数分别为0.167、0.639,在P0.01水平上显著相关;不同成土母质类型区域表层土壤中Cd和Cr元素含量的方差分析结果显示,方差齐性检验显著性分别为0.627和0.975,表明成土母质是表层土壤重金属元素Cd和Cr水平空间分布的主要影响因素。(3)研究区内表层土壤Cd和Cr元素的空间分布还受土壤类型、pH、土地利用及覆被类型的影响。     

不同种植年限下山银花产地土壤及花蕾重金属污染特征

以喀斯特山区不同种植年限山银花及其产地土壤为研究对象,并以附近荒地土壤作为对照,通过野外调查和室内分析,测定了绥阳县不同种植年限土壤和山银花的重金属含量,并应用单因子污染指数和综合污染指数法,对土壤和山银花中重金属含量进行评价分析。明确了不同种植年限山银花及其产地土壤重金属含量水平,揭示了种植年限对土壤中重金属含量的影响及土壤重金属污染的程度,分析了土壤中Cr,Cd,As,Pb,Hg和Cu与花蕾6种重金属元素的相关关系。结果表明:随着种植年限的增加,土壤中Cu,Cr,Cd和As含量均有不同程度的增加,Hg变化不明显,Pb含量降低,总体综合污染指数为0.72,处于警戒线等级;山银花重金属平均含量和污染指数随种植年限的增加而增加,但均未超标,处于安全等级和警戒线等级;土壤中Cr,Cu,As之间存在极显著正相关性,Pb与Cr,Cu,As均存在显著负相关性,土壤中Cu,Cr,Cd和As与山银花中6种重金属元素均存在显著或极显著的正相关性,土壤中Hg和Pb与花蕾中各重金属元素存在不同程度的负相关性。本项研究对于了解种植山银花对土壤环境的效应、防控产地土壤重金属污染、保障山银花品质,具有重要的意义。     

Addition of Calcareous Metal Waster to Acid Soils: Consequences for Metal Solubility

A model was tested which predicts the pH and solution metal concentration in the solution phase of soil amended with (waste-) incinerator fly ash (FA). Graded quantities of calcareous metal-rich FA were equilibrated with an acid clay soil, in aerated CaCl2 suspensions (0.01 M), to give a pH range of 3.1 (100% soil) to 7.5 (100% FA). As the FA loading was increased, the concentrations of Zn, Cd and Pb in solution passed through a maximum and then declined until the pH of the soil/ash mixtures approximated that of the pure FA (pHFA). This apparently complex pattern was accurately described by a simple pH- dependent adsorption equation relating adsorbed metal (Mads) to divalent metal concentration in solution (M2+) and pH through 3 constants designated n, Kads} and m: For pH < pHFA, log (Mads (M2+)n) = Kads + m pH However, at greater ash loadings the solution metal concentration and pH remained constant with FA addition and a solubility product (Ks) could be applied: For pH ≥ pHFA, og(M2+) = log Ks - 2 pH Metal concentrations in solution [Msoln] were greatest at very low FA loadings (around 2%); at lower FA additions [Msoln] was limited by total metal concentration while at higher additions of ash the solubility of metals was suppressed by the liming effect of the fly ash. It was therefore concluded that low levels of dust transfer from disposal sites to surrounding acidic soils may be the greatest source of metal pollution to biological and aquatic systems.     

Heavy Metal Uptake by Rape

Abstract

In pot experiments, the effect of single and combined pollution of soil by lead (Pb), cadmium (Cd), and zinc (Zn) and uptake of heavy metals in Brassica napus L. were investigated. There were two main factors that affected the assimilation of Pb, Cd, and Zn by rape: (i) level of soil pollution by the particular element and (ii) the combined influence of Pb, Cd, and Zn. In general, with the increase of the concentrations of Pb, Cd, and Zn in the soil, there were increases in the concentrations of those elements in the roots, stems, and seeds. The main part of the Pb and Zn amounts taken up by the roots from the soil are fixed and accumulated in the roots, and small amounts of them move through the conductive system to the seeds. Cadmium moves relatively easily from root to stem and is accumulated in higher concentrations in the top of the plant.

There is a well‐expressed synergistic interaction between Pb²⁺ and Cd²⁺, as well as of Cd²⁺ and Zn²⁺. Zinc has a highly depressing effect on the assimilation of Cd²⁺, as does Pb²⁺ on the assimilation of Zn²⁺. The combined pollution by Pb, Cd, and Zn stimulated the assimilation of these elements by the roots and foliage and eliminated the effect of Zn²⁺ on Cd²⁺ and of Pb²⁺ on Zn²⁺.     

Metal contents of phosphate rocks

Abstract

Significant amounts of phosphate rocks (PRs) are mined around the world annually. The rocks are either applied directly to soils or manufactured to produce water‐soluble phosphorus (P) fertilizers. In this study, we analyzed 12 PRs obtained from various deposits in Africa, United States, and Peru for total P, ten trace metals [cadmium (Cd), cobalt (Co), copper (Cu), chromium (Cr), lithium (Li), manganese (Mn), nickel (Ni), lead (Pb), rubidium (Rb), and zinc (Zn)] and eight nontrace metals [aluminum (Al), barium (Ba), calcium (Ca), iron (Fe), potassium (K), magnesium (Mg), sodium (Na), and strontium (Sr)]. The empirical formulae and the unit‐cell a dimension of the apatite contents were also determined. Results showed that the values of the unit‐cell a dimension ranged from 9.324 Å for North Carolina PR to 9.365 Å for Tahoua PR. The total P contents ranged from 109 g/kg for Kodjari PR to 176 g/kg for Parc W PR. The concentration of the trace metals in the PRs varied considerably. Expressed in mg/kg PR, the ranges and median values were: Cd (5–47, 10), Co (6–104, 22), Cu (5–41, 8), Cr (18–331, 46), Li (2–9, 2), Mn (11–6553, 263) , Ni (1–61, 10) , Pb (7–43, 14), Rb (3–18, 6), and Zn (54–576, 124). The corresponding values of the nontrace metals expressed in g/kg were: Al (1.7–20.0, 5.6), Ba (0–4.4, 0.4), Ca (211–330, 298), Fe (1.4–45.7, 6.8), K (0.3–10.9, 1.4), Mg (0.6–16.9, 2.2), Na (1.0‐ 22 .8, 10.4), and Sr (0.3–6.7, 1.0). At the detection limit of 5 ng/mL, no cesium (Cs) was found in the PR analyzed.     

Crystallization of Metal Substituted Ferrihydrites

The effects of a series of divalent, first row transition elements, i.e. Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ on the crystallization of ferrihydrite have been compared. With the exception of Mn²⁺, the metal ions considered, stabilized ferrihydrite and enhanced the amount of haematite in the reaction product. The stabilizing ability of these ions could be related to the increase in covalency of these metals along the series. With more than 15 mole% divalent metal ion present, ferrihydrite transformed to a spinel phase by a dissolution/reprecipitation mechanism. These metals can replace some Fe³⁺ in the structures of the crystallization products. Factors that influence the extent of isomorphous substitution are the match between the radii and charges of Fe³⁺ and the substituent ions and also, the congruency of dissolution of the M/ferrihydrite coprecipitate.     

西北地区金属尾矿地根瘤菌的重金属抗性及其系统发育研究

对分离自陕西、甘肃金属尾矿废弃地寄主为刺槐、鸡眼草、草木樨等23种豆科植物的188株根瘤菌进行了7种重金属的抗性分析、最大抗性水平（MRL）的确定和抗性菌株的系统发育研究。结果表明,菌株之间对重金属的耐受性存在较大差异,大部分菌株表现出对Hg^2＋、Cd^2＋、Cr^6＋（〈0.5 mmol·L^-1）敏感,而对Pb^2＋（〈2.5 mmol·L^-1）不敏感。在液体培养基中,CCNWSX0403和CCNWSX0360可耐受4.0 mmol·L^-1 Zn^2＋,分别可耐受2.4 mmol·L^-1 和2.8 mmol·L^-1 Cu^2＋,CCNWGS0139可耐受0.4 mmol·L^-1 Hg^2＋,CCNWSX0003可耐受2.4 mmol·L^-1 Ni^2＋,CCNWGS0284和CCNWGS0142可耐受4.8 mmol·L^-1 Pb^2＋。9株抗性菌株的16S rDNA全序列分析表明：CCNWGS0122和CCNWSX0003分别属于中慢生根瘤菌属（Mesorhizobium）和中华根瘤菌属（Sinorhizobium）;4株对Pb^2＋、Hg^2＋耐受性较强的菌株CCNWSX0386、CCNWGS0139、CCNWGS0284和CCNWGS0142均属于土壤杆菌属（Agrobacterium）;而属于慢生根瘤菌属（Bradyrhizobium）的3株菌CCNWGS0309、CCNWSX0403和CCNWSX0360对Cu^2＋、Zn^2＋耐受性较好。总体上Agrobacterium对Hg^2＋和Pb^2＋的耐受性较好,Bradyrhizobium比Rhizobium、Sinorhizobium、Mesorhizo     

中南大型有色金属冶炼厂周边农田土壤重金属污染特征研究

以中南地区某大型有色金属冶炼厂周边耕地为对象,采集0~20 cm表层土壤,测定其基本性质及重金属浓度,分析了重金属元素间及重金属污染程度与距冶炼厂远近的相关关系,以判别研究区土壤重金属污染来源及空间分布规律。结果表明,研究区土壤呈酸性,土壤重金属污染以Cd为主,与当地土壤环境背景值和国家土壤环境质量二级标准相比,超标率分别达60.9%、86.1%。Cu、Zn、Cr、Ni等元素的污染较轻,Pb则未超标。内梅罗综合污染指数法对水田土壤重金属的风险评价显示该区属于安全的点位仅占8.7%,农产品生产存在较高风险。单因素方差分析显示旱地与水田土壤重金属浓度差异不显著,说明耕作方式不是造成该区重金属分布差异的主要原因。土壤Cd与Pb、Zn浓度显著相关,且与距冶炼厂的距离呈显著负相关,指数和幂函数均能很好地拟合重金属浓度随距离变化的分布模式,说明三者可能均来源于冶炼厂的降尘污染。     

A Single Metal, Metal Mixture, and Whole-Effluent Approach to Investigate Causes of Metal Mine Effluent Effects on Fathead Minnows (Pimephales promelas)

Although many studies have examined effects of metal mine effluents (MMEs) on receiving environments, few have compared the roles of individual and mixed metals relative to whole effluents. The objective of the present set of studies was to examine whether Cu, Ni, or Se, alone or in a mixture, causes comparable effects to those observed in fathead minnows (Pimephales promelas) exposed to an environmentally relevant MME (45 % process water effluent [PWE]). Metal bioaccumulation, fathead minnow (FHM) morphometrics, and egg production were compared between treatments over a 21-day exposure. FHMs were exposed to similar waterborne concentrations and species of metals in single and mixed metal treatments relative to 45 % PWE. FHMs were also exposed to similar concentrations of metals in single and mixed metal treatments relative to 45 % PWE through the diet (Chironomus dilutus — a representative prey species). However, only FHMs exposed to 45 % PWE had reduced egg production (60–80 % less than controls). Our findings indicate that Cu, Ni, and Se exposures and bioaccumulation did not contribute to decreased reproductive output in FHMs under the conditions that were examined. We also found no evidence to believe that these metals were responsible for decreased egg production in PWE. It is therefore reasonable to suggest that these metals have limited potential to cause reproductive effects in MMEs with similar composition and water chemistry conditions. Overall, this study highlights the importance of examining single and mixed metal exposures prior to suggesting that adverse effects in fish exposed to MMEs occur due to bioaccumulation of metal(s).     

Metal plant and soil pollution indexes

Micro-constituent ionic impulsion, a parameter related to metal content and introduced to explain plant uptake, is now used to propose a plant global pollution index for an industrialized area. Plant toxic levels and previous analytical results (Pb, Co, Ni, Cr, Cd, Cu, Fe, and Zn) for five wild plant species and whole herbage from 14 sampling points with rural, industrial or urban character within Bilbao (Spain) zone, are used to calculate this index. On similar bases a soil pollution index is also suggested, excluding Fe as it is a natural and very variable macrocomponent. Comparisons between these two indexes are included; differences are discussed through leaf uptake or strong retention of metals by soils.     

Metal binding properties of Klebsiella oxytoca

Bacterial surfaces are generally negatively charged in the environmental pH-range and may therefore interact with metal cations, thus influencing the mobility of metals in soil and natural waters. In the present work the acid capacity and metal binding properties of Klebsiella oxytoca have been studied. A total acid capacity of 120 meq kg^–1 was determined from potentiometric titrations of a suspension of starved bacteria in 0.1 M KC1. The adsorption of trace elements (Cs, Sr, Eu, serving as model systems, as well as Hg, Zn, and As) on starved bacteria was determined by a batch technique using radio tracers and with variation of pH (3 to 9). The adsorption followed the order Cs < sr,=" as=">< zn=">< hg=">< eu=" (at=" ph=" 5=" to=" 7).=" the=" uptake=" of=" eu=" was=" drastically=" increased=" when=" ph=" increased=" from=" 3.5=" to=" 4.5,=" indicating=" a=" surface=" complexation=" (with=" carboxylic=" or=" phosphate=" groups).=" a=" desorption=" of=" eu=" at=" ph=" above=" the=" acid=" equivalence=" point=" (ph=" 6.9)=" could=" be=" an=" indication=" of=" the=" release=" of=" a=" metal=" complexing=" exudate=" from=" the=">