The flux of Cd,Cu, Pb and Zn in mining polluted soils

The monitoring of heavy metal deposition onto soils surrounding old Pb-Zn mines in two locations in the UK has shown that relatively large amounts of Cd, Pb, Zn and, in one case, Cu are entering the soil annually. Small particles of ore minerals in windblown mine tailings were found to be contributing up to 1.46 g m^?2 yr^?1 of Pb, 1.41 g m^?2 yr^?1 of Zn and 0.027 g m^?2 yr^?1 of Cd. However, when these inputs from bulk deposition are compared with the concentrations of the same metals within the soil profiles it is apparent that relatively little long-term accumulation is occurring. Metals are being lost from the soil profiles, probably through leaching. A calculated relative retention parameter gave values that ranged from 0.01 to 0.17 for Cd, 0.11 to 0.19 for Zn, 0.32 to 0.63 for Cu and over 1 for Pb. These relative retention values were found to follow the order of electronegativity of the elements concerned: Pb>Cu>Zn>Cd. Distribution coefficient (Kd) values quantifying the adsorptive capacity of the mine soils for Cd and Pb showed marked differences for the two metals (12 to 69 cm³ g^?1 for Cd and 14 to 126 cm³ g^?1 for Pb) and may, in part, account for the two to one hundred-fold variation in the relative retention parameter for the different metals within these soils.     

人为污染土壤中Cd、Pb、和Zn的化学有效性：地球化学反应与口服生物有效性评价

The most recent in vitro tests used to determine metal bioaccessiblility are generally time-consuming and expensive.This study aimed at determining potential relationships between the concentrations of metals extracted using single-extraction methods and the concentrations of bioaccessible metals assessed by a harmonised in vitro test,the Unified BARGE Method (UBM).A total number of 27 soil samples were collected from kitchen gardens and lawns with various physicochemical parameters and contamination levels.Significant relationships were obtained between Cd,Pb and Zn extracted in gastric and gastrointestinal phases and using single extractions.The best relationhips were established using acetic and citric acids for Cd,whereas for Pb,citric acid and ethylenediaminetetraacetic acid (EDTA) were identified as the best extractants.These relationships were improved by means of a linear multiple regression with a downward stepwise procedure involving agronomic parameters (soil cation exchange capacity and assimilated P).This method highlighted the fact that the cation exchange capacity and P contents in soils were the two main parameters that controlled the human bioaccessibility of Cd,Pb and Zn in the gastric phase.Besides,the metal concentrations extracted with the acetic and citric acids correlated well with the metal concentrations in the gastric and gastrointestinal phases,suggesting that the bioaccessible metals were mainly in a soluble form,weakly bound to the organic matter and associated with the carbonates and the Fe and Mn oxides/hydroxides in soils.     

Distribution of different fractions of cadmium,zinc, lead,and copper in unpolluted and polluted soils

McLaren and Crawford's method for fractionating soil Cu was modified, and used to fractionate soil Cd, Zn, Pb, and Cu in 38 soil samples from 11 soil profiles from industrially polluted and nearby unpolluted areas. Pollutant metals, especially Cd and Zn, were more soluble than the native soil metals. On average, approximately 45% of Cd was present in the CaCl₂ soluble (CA) fraction, whereas corresponding values for the other metals were below 10%. The percentages of each metal in the CA fraction followed the order Cd > Zn > Pb > Cu. The same order was observed for the acetic acid soluble (AAC) fraction. Approximately 30% of total Pb and Cu were present in the pyrophosphate soluble (PYR) fraction, and only 10% of total Cd and Zn. Approximately 20% of total Zn or Pb and 10% of Cd or Cu were present in the free oxide (OX) fraction. Only 20% of Cd and between 40–50% of the other 3 metals were present in the residual (RES) fraction. The results show that Cd is more labile than the other 3 metals.     

Mobility of heavy metals in polluted soils near zinc smelters

The distribution and the availability of Cd, Zn, Cu, and Pb along the entire profile of two highly polluted soils located near Zn smelters have been related to the chemical and mineralogical composition of the soil. Lead and Cu deposits always remain in the surface layers and their availability measured by neutral ammonium acetate extraction was very weak. The behavior of Cd and Zn appears different in sandy acidic podzolic soils and in neutral loamy soils. These metals are associated with the organic matter migration in podzolic soils, while they remain in the upper layers in loamy soils provided that the pH is higher than 6. When the pH drops below 6, the mobility of Cd increases while that of Zn increases only below pH 5. The availability of heavy metals is lower in neutral loamy soils than in sandy acidic soils due to precipitation of carbonates and phosphates. With increasing depth, Cd and Zn are more available if the soil is acid; but, if the soil is neutral and loamy the availability is kept low by adsorption on clays and free oxides. The results of the complex trace metals interactions with the soil components show a higher accumulation capacity for loamy soils than for sandy soils notwithstanding the fact that their CEC is similar.     

Cd/Zn 及Cd /Zn/Ni复合污染对胡萝卜生长吸收特征的影响

利用盆栽试验对胡萝卜在不同浓度Cd/Zn及Cd/Zn/Ni复合作用下的重金属吸收效应进行了研究。结果表明,在Cd/Zn/Ni和Cd/Zn复合污染条件下,胡萝卜茎叶和块茎干重与对照土壤比较均受到显著影响（P＜0.05）,尤其是含Ni组合,在Ni浓度达到250 mg·kg-1后,胡萝卜块茎和茎叶生物量都锐降（P＜0.01）。对比不同剂量下两组合富集系数（EF）和转运系数（TF）的结果发现,含Ni组合中, Cd、Zn、Ni 3种重金属在不同迁移界面以及不同浓度水平时的活性不同：在土壤-胡萝卜块茎迁移界面,当土壤中Cd、Zn、Ni浓度分别在0.35～1.8、50～300 mg·kg-1以及60～250 mg·kg-1之间时,活性大小为Cd〉Zn〉Ni;当其浓度分别达到3.5 mg·kg-1（Cd）、600 mg·kg-1（Zn）以及500 mg·kg-1（Ni）时,活性大小变为 Zn〉 Ni 〉Cd ;而在胡萝卜块茎－茎叶界面,Cd的活性在任何浓度水平下始终最大,当Zn、Ni浓度分别在50～180 mg·kg-1以及 60～170 mg·kg-1之间时,活性大小为Zn＞Ni ,但在此浓度之后Ni的作用突显,活性大小变为Ni＞Zn。非含Ni组合中,在两迁移界面和不同浓度水平下,两种重金属的迁移能力始终为Cd＞Zn。此外,在碱性较高的绿洲灌淤土中,Cd、Zn、Ni之间的交互作用表     

Influence of different temperatures on metal tolerance measurements and growth response in bacterial communities from unpolluted and polluted soils

The effects of temperature on the growth rate and metal toxicity in soil bacterial communities extracted from unpolluted and polluted soils were investigated using the thymidine and leucine incorporation techniques. An agricultural soil, which was contaminated in the laboratory with Cu, Cd, Zn, Ni or Pb, and an uncontaminated forest soil were used. Measurements were made at 0°C and 20°C. Leucine incorporation was found to be as sensitive to heavy metals as thymidine incorporation in the short-term trial used to indicate heavy metal tolerance. Similar IC₅₀ values (the log of the metal concentration that reduced incorporation to 50%) were also obtained at 0 and 20°C, independently of the technique used. Metal tolerance could thus be measured using both techniques at any temperature in the range 0–20°C. In the long-term experiment different temperature-growth relationships were obtained on the basis of the rate of thymidine or leucine incorporation into bacterial assemblages from unpolluted and polluted soils, as judged from the minimum temperature values. This could not be attributed to the metal addition alone since different patterns were observed when different metals were added to the soil. Thus, the minimum temperature for thymidine incorporation was similar in Cu-polluted and unpolluted soil, while in soils polluted with Cd and Zn the minimum temperature increased by 2°C, and Ni and Pb additions increased the minimum temperature by 4°C compared to the unpolluted soil. This suggested that heavy metal pollution led to bacterial communities showing different temperature characteristics to those in the corresponding unpolluted soil. Similar observations were deduced from the minimum temperatures required for leucine incorporation. Three groups of bacterial communities were distinguished according to the growth response to temperature in polluted soils, one group in Cu-polluted soil, a second group in soil polluted with Zn and Cd, and a third group in soils polluted with Ni and Pb.     

Mobilization of Zn upon waterlogging riparian Spodosols is related to reductive dissolution of Fe minerals

Contaminated riparian soils can release metals to surface water. Periodic waterlogging affects metal mobility but the processes and soil factors governing net trends are not well understood. Experiments were combined with geochemical modelling to identify processes explaining the dynamics of zinc (Zn) in contaminated soils following waterlogging. Samples were collected from 12 Spodosols near streams in a metal‐contaminated area and four similar but uncontaminated soils were sampled in a reference area. Air‐dried samples were submerged and incubated under N₂. The soil redox potential decreased from 470 mV initially to approximately 30 mV over 2 months. The pore‐water Zn concentrations surprisingly increased over the same period by, on average, a factor of 18 (range 0.6–80; immobilization in one soil only) despite an increase in pH of 1.8 units, on average. Dissolved organic matter (DOM) in the soil solution increased during waterlogging but the observed increase in Zn solubility could not be explained by increased complexation with DOM, because the estimated Zn²⁺ activity also increased by a factor of 18 on average (range 0.2–82). Speciation modelling suggests that Zn mobilization during waterlogging results from Fe²⁺ displacing sorbed Zn²⁺ from particulate organic matter and from dissolution of Zn‐bearing Fe/Mn oxyhydroxides. This hypothesis is supported by the significant positive correlation (r = 0.87, n = 13) between the factor change in pore‐water Zn concentration and the ratio of dithionite‐extractable Fe to organic carbon content. These results show that Fe dynamics are important for predicting the fate of trace metals in anoxic soils.     

Transfer of Cd, Pb, and Zn to water spinach from a polluted soil amended with lime and organic materials

Purpose

The transfer of heavy metals from soil to crops comprises several steps, including soil-to-root and subsequent root-to-shoot tranfer. The purpose of this study was to investigate the different steps of soil-to-crop transfer of Cd, Pb, and Zn.

Materials and methods

This study was carried out with a greenhouse pot experiment using a soil polluted with Cd, Pb, and Zn which was amended with rice straw, pig manure, sheep dung, or peat, with and without lime. Water spinach (Ipomoea aquatica) was used as the test crop and was grown after a season of rice cultivation.

Results and discussion

The results showed that all the amendments promoted the root-to-shoot transfer of Cd, Pb, and Zn. The soil-to-root transfer factors (TFs) of Pb and Zn tended to increase with increasing available Pb and Zn in the soils, while no clear relationship between the TF of Cd and available soil Cd was observed. The root-to-shoot TF of Cd, Pb, and Zn tended to decrease with increasing available amounts in the soils and were negatively correlated with the concentrations of the metals in the roots (r _Cd?=?0.820, r _Pb?=?0.789, r _Zn?=?0.769).

Conclusions

The soil-to-root transfer of Cd, Pb, and Zn was significantly different from the root-to-shoot transfer. The soil-to-root transfer was mainly influenced by the amount of available metal in soil, whereas the root-to-shoot transfer was mainly controlled by the concentrations of the metals in the root.     

几种土壤在单一Zn及Cd Cu共存条件下对Zn的吸附

研究了Zn2+在单一及与Cd2+、Cu2+共存条件下在塿土、黄绵土、黑垆土、黄褐土、砂土5种土壤中的吸附特征,并探讨了其吸附机制。结果表明,在20℃、30℃下,Zn2+在各供试土样中吸附等温线总体上均呈I或III型等温线形式,总体上黑垆土、塿土对Zn2+吸附最强,而砂土的吸附总是最差;塿土、黄绵土和黄褐土中Zn2+吸附的温度效应呈现升温正效应特征,砂土中则总体上表现出随温度上升呈下降趋势,黑垆土中Zn2+吸附的温度效应则与重金属处理有关。Freundlich模型是描述Zn2+吸附等温线最佳模型。Cd2+、Cu2+的共存对Zn2+的吸附均具有显著的拮抗作用,但对Zn2+吸附规律的影响不同。机理分析表明,Zn2+在土壤中的吸附主要以化学吸附为主,Cu2+由于其与Zn2+相似的化学吸附特点而竞争Zn2+化学吸附点位,但Cd2+吸附主要竞争以电性引力形式吸附的Zn2+,因而Cu2+对Zn2+吸附的影响较大,而Cd2+影响较小。     

镉污染土壤的植物修复及其EDTA调控研究：Ⅰ、镉对富集植物印度芥菜的毒性

本通过温控盆栽试验研究在10－190mg/kg共10个浓度梯度的Cd处理下，印度芥菜生长对Cd的响应，Cd在根与地上部的积累以及在Cd胁迫和毒害条件下对Ca和Zn吸收的影响，结果表明，Cd对印度芥菜生长的毒害浓度在各个生育期各有不同：幼功期与营养生长前期在70－110mg/kg左右；营养生长后期在110mg/kg以上；成熟期在150mg/kg左右。植物吸收的镉随土壤镉处理浓度的增加而增加，本试验中印度茶菜根和叶积累镉最高浓度分别为300和160mg/kg，在Cd胁迫下，印度芥菜吸收的Ca和Zn增加，在Cd毒害条件下，印度芥菜吸收的Ca和Zn下降。认为高浓度的Cd对印度芥菜生产有抑制，但印度芥菜对镉也表现出很强的耐性，这种耐性可与植物体内Cd和Ca，Zn之间的平衡有关。     

难溶态锌、镉对香根草抗氧化酶活性及锌、镉吸收的影响

采用土培根袋试验,研究了难溶态锌、镉对香根草生长、抗氧化酶活性、MDA含量及锌、镉吸收累积的影响.结果表明,锌、镉均不同程度抑制了香根草的生长,抑制作用均以锌镉交互＞镉＞锌,以锌、镉复合污染更加剧了对植物的胁迫,不同生长期(75 d和90 d)锌锅处理的香根草地上部和根系的SOD、POD、CAT活性及MDA含量均显著增加,且随重金属毒性增强,酶活性和MDA含量亦增加,香根草根系膜脂过氧化的程度大于地上部,香根草体内锌镉含量以地上部＜根系,但吸收的锌主要富集在地上部,吸收的镉则主要富集在根系,且随着生长期的延长,各锌镉处理的锌镉积累量明显增加.     

大田蔬菜Pb、Cd污染途径的研究

大田蔬菜土壤监测结果表明 ,污染区土壤全Pb、全Cd和有效铅、有效镉含量均低于非污染区 ,但蔬菜莴笋、大葱和小葱Pb、Cd含量明显高于非污染区。土壤全Pb、全Cd和有效铅、有效镉呈相关性 ,蔬菜干物质量和鲜物质量Pb、Cd呈相关性 ,表明重金属Pb、Cd污染有同步性。而同一地点土壤有效铅与蔬菜Pb含量、土壤有效镉与蔬菜Cd含量均无相关性 ,表明蔬菜Pb、Cd污染与土壤关系较小。非污染区蔬菜均无超标样本 ,污染区蔬菜样本超标率为 4 0 .0 % ,且以莴笋、大葱、苋菜和芹菜等叶菜类为主 ,大田蔬菜Pb、Cd主要污染途径源于大气污染     

基于籽粒Cd消减率与边际效率评价Cd污染稻田的修复效果

高效、低成本钝化材料的研发及盆栽与田间试验结果的一致性仍然是目前重金属污染土壤原位钝化修复的技术难点。该文以镉(Cd)污染的湖南红壤与浙江水稻土为对象,以2种不同Cd敏感性水稻(Cd低吸收品种JH212、Cd高富集品种XS09)为试材,通过盆栽与田间对比试验,基于水稻籽粒Cd消减率、修复边际效率及土壤中Cd有效态含量的变化等对不同钝化剂的修复效果进行了测定。结果表明:不同钝化剂对2种不同Cd敏感性水稻籽粒Cd的吸收、转运均有显著(P0.05)降低作用。盆栽试验条件下,与对照相比,不同钝化剂处理后湖南红壤中水稻籽粒Cd浓度最大降低65.3%,浙江水稻土中籽粒Cd浓度最大降低61.4%;在田间试验条件下,不同钝化剂处理的红壤中水稻籽粒Cd浓度最大降低61.8%,水稻土中籽粒Cd浓度最大降低60.1%。就2种不同的Cd敏感性水稻品种而言,不同钝化剂对Cd高富集品种XS09的钝化效果要优于Cd低吸收品种JH212。总体而言,不同钝化剂对2种不同Cd敏感性水稻籽粒Cd消减率为41.6%~65.3%,对XS09的籽粒Cd消减率略高于JH212,在酸性红壤的钝化效果高于水稻土;不同钝化剂对水稻籽粒Cd消减效果依次为黏土矿物钝化剂AT腐殖质钝化剂WG≈岩基钝化剂FS。不同钝化剂对Cd污染红壤与水稻土的修复边际效率为9.10%~15.4%,最高为AT处理,其次为WG与FS处理;综合籽粒Cd消减率与修复边际效率2个指标进行考虑,不同钝化剂对Cd污染土壤的修复效果顺序为ATWGFS。     

Fungal growth and effects of different wood decomposing fungi on the indigenous bacterial community of polluted and unpolluted soils

Thirty-two different basidiomycete isolates were inoculated separately into contaminated soil and the soil colonization ability was assessed visually. Large differences in the colonization ability and growth patterns were found between the different fungi. Phospholipid fatty acids (PLFAs) were extracted from the soils of the seven isolates with the best colonizing ability. All PLFAs that were not found in pure cultures of the seven fungi were considered as bacterial PLFAs. The bacterial PLFA data were subjected to principal component analysis (PCA) to indicate changes in the indigenous bacterial community. The experiment was repeated in a sandy agricultural soil. The bacterial PLFA patterns were altered when fungi were inoculated into soil, irrespective of whether it was polluted or not. In particular the PLFA cy19:0, indicative of Gram-negative bacteria, was higher in fungal-inoculated soil than in uninoculated controls. The PLFA patterns for each fungal treatment were distributed more or less similarly in the PCA plots of both contaminated and sandy agricultural soil. Soil inoculated with Antrodia vaillantii, Hypholoma fasciculare or Recinicium bicolor was considerably different from the control along PC 1. Soil inoculated with Phanerochaete chrysosporium was characterized by different values along PC 2 compared with the other fungal soils.     

Phytoextraction of Cd and Zn with Thlaspi caerulescens in field trials

Abstract. Phytoextraction is the remediation of heavy metal contaminated soils using plants that take up metals. Hyperaccumulating plants such as Thlaspi caerulescens are often studied for their possible use for decontamination of Cd and Zn rich soils, but few field trials have been reported, although they are necessary to validate the results of hydroponic and pot studies. This article reports field data for T . caerulescens grown on a calcareous and an acidic soil, both contaminated 20 years ago by either atmospheric depositions or septic-tank wastes. Accelerated cropping using transplants grown three times in eight months was compared to Thlaspi sown twice during the same period. Both were followed by one crop of sown Thlaspi . High Cd and Zn concentrations in the plant shoots compensated for the low biomass production. Annual metal exports with transplanted Thlaspi were 130 g Cd ha⁻¹ and 3.7 kg Zn ha⁻¹ on the calcareous soil and 540 g Cd ha⁻¹ and 20 kg Zn ha⁻¹ on the acidic soil. We concluded that within the framework of the Swiss legislation, remediation of Cd-contaminated soils could be achieved within less than 10 years with one crop of Thlaspi per year, but differences in soil properties could affect the rate of phytoextraction significantly. Total Zn content in both soils was too high to be remediated by T . caerulescens in a realistic time span. Thlaspi did not decrease the NaNO₃-extractable fraction of Cd or Zn in either of the soils.     

Phytoextraction of Cd and Zn with Salix viminalis in field trials

Abstract. Use of high biomass crops such as the willow Salix viminalis to extract metals for soil remediation has been proposed as an alternative to the low biomass-producing hyperaccumulating plants. High yields compensate for the moderate heavy-metal concentrations in the shoots of such species. We report the first long-term trials using Salix viminalis to extract heavy metals from two contaminated soils, one calcareous (5 years) and one acidic (2 years). Total metals extracted by the plants were 170 g Cd ha⁻¹ and 13.4 kg Zn ha⁻¹ from the calcareous soil after 5 years, and 47 g Cd ha⁻¹ and 14.5 kg Zn ha⁻¹ from the acidic soil after 2 years; in the first year outputs were negligible. After 2 years, Salix had performed better on the acidic soil because of larger biomass production and higher metal concentrations in shoots. Addition of elemental sulphur to the soil did not yield any additional benefit in the long term, but application of an Fe chelate improved the biomass production. Cd and Zn concentrations were significantly higher in leaves than stems, highlighting the necessity to collect leaves as well as shoots. On both soils, concentration in shoots decreased with time, indicating a decrease in extraction efficiency.     

钙镁磷肥可以减少复合污染农田不同品种玉米Cd、As吸收

因长期施用化肥致使农田土壤在不同程度上存在着肥力下降、酸化、板结、砷镉等元素含量超标等问题,严重影响耕地质量。钙镁磷肥呈碱性,可以改良酸性土壤,同时可以钝化土壤中的重金属,调节元素失衡,减少有机质流失等问题。以云南省个旧市大屯镇污染农田为背景,探究施用钙镁磷肥对当地4种玉米品种(路单12号、足玉7号、红育2号、华兴单88号)的产量,以及对籽粒中As、Cd含量和土壤有效态As、Cd及pH的影响。结果表明:(1)在钙镁磷肥的处理下,与裸地相比,红育2号土壤pH的改良效果最好;(2)综合考虑玉米对土壤中有效态As、Cd含量的影响,红育2号具有较好的效果,而路单12号无显著效果;(3)施用钙镁磷肥,红育2号的产量达到最大,采用红育2号是增加玉米产量的最佳选择;(4)综合考虑钙镁磷肥对玉米籽粒中As、Cd含量的影响,红育2号具有较好的效果,而路单12号仅在降低玉米籽粒中As含量效果较好。     

磷灰石等改良剂对重金属铜镉污染土壤的田间修复研究

通过田间小区试验,研究了磷灰石、石灰、木炭、猪粪、铁粉5种改良剂对Cu、Cd复合污染土壤的改良效果。结果表明,石灰、磷灰石、木炭、猪粪降低了土壤溶液中重金属Cu、Cd的含量,提高了土壤溶液的pH,但改良效果随着时间的推移不断降低。磷灰石、石灰、木炭的加入显著降低了有效态Cu含量,但对有效态Cd含量影响较小。与猪粪相比,磷灰石、石灰、木炭显著增加了黑麦草生物量,提高了对重金属Cu、Cd的吸收能力,对该污染土壤的修复具有实践应用价值。     

施肥对铅镉污染土壤上芥菜铅镉含量及生理的影响

盆栽试验研究了不同化学肥料组合处理对铅镉污染土壤上芥菜(Brassica juncea)Pb、Cd含量及其生理特性的影响。结果表明, 与对照相比, 各肥料处理在显著提高芥菜生物量的基础上, 显著降低了芥菜地上部Cd含量(P<0.05), 其中碳酸氢铵+磷酸二氢铵+硫酸钾处理的效果最佳, 芥菜Cd含量仅为对照的41.0%; 施肥处理提高了芥菜地上部Pb含量, 但Pb没有健康风险; 施肥提高了叶菜的叶绿素含量, 但丙二醛、脯氨酸、细胞质膜透性与芥菜地上部Pb、Cd含量无显著相关性。重金属污染土壤施肥处理是一种值得推广的降低叶菜有害重金属含量的有效技术。     

Retention of Ni,Zn and Cd by Si-associated goethite

Synthetic goethite used to study the effects of reaction time and temperature on the pH-dependent sorption of Ni, Zn and Cd was associated with amorphous silica. Ni interacted with dissolved Si and formed a Ni/Si precipitate on the goethite surface. Individual metals added at a concentration of 0.5 μmol g^?1 and sorbed during a reaction period of 504 hours (21 days) at 35°C were extracted by 0.7 M HNO₃ for 14 days. At the end of this period 11,28 and 40 percent of Ni, Cd and Zn, respectively, were not extracted whereas 20 percent of the total Fe content of the goethite and 39 percent of the associated Si were dissolved. During the sorption process metals became immobilized in the goethite particles. This effect can be related to a diffusion of metal ions into micropores. A total mobilization of sorbed metals can only be achieved by a complete dissolution of the goethite. The strong fixation of Ni, Zn and Cd by goethite suggests that additions of this Fe oxide could be used to ameliorate highly contaminated sludges or soils.