电镀厂污染土壤重金属形态及淋洗去除效果

以某电镀厂污染场地重污染区域土壤为研究对象,对土壤中重金属全量和各形态含量进行分析,并研究筛选高效土壤淋洗剂,比较其淋洗去除效果。结果表明,该土壤以铬和镍污染最为严重,土壤铬和镍含量分别达1 564.00和679.00 mg.kg-1,土壤铜、锌和铅含量分别为297.00、276.00和51.40 mg.kg-1,铜、铬、镍、锌和铅的有效态比例分别为41.77%、13.16%、28.08%、21.50%和31.18%。去离子水、盐酸、乙酸、草酸、柠檬酸和EDTA 6种淋洗剂中,去离子水对5种重金属提取量均较少;草酸对铜、铬、镍和锌去除效果较好,去除率分别为55.1%、24.8%、47.5%和29.3%;柠檬酸对铜、铬、镍和锌去除效果较好,去除率分别为26.3%、25.7%、33.0%和21.6%;EDTA对铜、镍、锌和铅去除效果较好,去除率分别为31.5%、28.9%、21.4%和30.6%。综合考虑淋洗剂的提取效果、水溶性以及操作难度和成本,建议采用柠檬酸作为淋洗剂,最佳液土比〔V（液）∶m（土）〕为10∶1,最佳淋洗时间为6 h。     

两种螯合剂施用对污染土壤中叶用叶叶叶Cd富集的影响

为探讨螯合剂对植物吸收重金属的影响,采用盆栽试验,研究了螯合剂乙二胺四乙酸(EDTA)和柠檬酸(CA)对土壤重金属Cd的有效态以及叶用红菾菜(Beta vulgaris var.cicla L)富集Cd能力的影响.结果表明:EDTA的添加比柠檬酸更显著增加了土壤重金属镉的有效态含量,同时提高了叶用红菾菜茎叶的富集系数和转运能力;施用螯合剂促进了Cd从叶用红菾菜茎叶根部向茎叶的输送,叶用红菾菜茎叶含Cd量显著增加,EDTA的作用是柠檬酸的2～3倍.     

Spatial distribution of potentially bioavailable metals in surface soils of a contaminated sports ground in Galway, Ireland

Assessing the environmental risk of metal contamination in soils requires the determination of both total (TCs) and bioavailable (BCs) element concentrations. A total of 200 surface (0–10 cm) soil samples were collected from an urban sports ground (South Park) in Galway, Ireland, a former landfill and dumping site, which is currently under remediation. The potential BCs of metals were measured using ethylene-diamine-tetra-acetic acid (EDTA) extraction followed by inductively coupled plasma-optical emission spectrometry analysis, while the TCs were determined using portable X-ray fluorescence spectrometry. It was found that Zn was primarily present in the insoluble residue (EDTA un-extractable) fraction in soils, with the median ratio of BCs/TCs 0.27. However, Pb and Cu had higher ratios of BCs/TCs (median values of 0.60 and 0.39, respectively) suggesting that they are potentially more bioavailable in the soils. The spatial distribution maps showed that both TCs and BCs for Cu, Pb and Zn in the study area were spatially heterogeneous. It was found that the BCs exhibited generally similar spatial patterns as their TCs of Cu, Pb and Zn: high values were mainly located in the west, north-east and south-east portions of the study area, where only a thin layer of topsoil existed. It was recommended that the current remediation action for this site needs to be carried out on an urgent basis.     

微胶囊EDTA对2种土壤中铅释放的影响

选用不同铅污染程度及pH值的土壤,采用连续批浸提实验和土柱淋溶实验,比较研究微胶囊EDTA（Cap-EDTA）和未微胶囊化EDTA（Ncap-EDTA）对不同土壤溶液中pH值和铅离子浓度动态变化影响,以及土壤渗滤液中铅离子淋失特征。结果表明：施加2种不同形式的EDTA,可极显著地增加土壤溶液中铅离子浓度,Cap-EDTA能控制土壤溶液中铅浓度的突增幅度,且使土壤溶液中的铅持续保持在适度浓度的时间更长。同一种土壤不同处理间土壤pH值的变化趋势基本一致,无显著差异。施用2种不同形式EDTA可极显著地增加土壤渗滤液中铅离子含量,土壤铅累积淋失量呈对数曲线上升,但施用Cap-EDTA处理能显著降低土壤中铅的初始淋失量和淋失总量。在相同浓度及形式的EDTA下,高铅浓度和高pH值的土壤铅更易活化和淋失。因此,在进行污染土壤植物修复的EDTA调控时,采用微胶囊化EDTA,能降低其带来的污染地下水风险。     

Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO?) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0-5% powdered eggshell waste and curing the soil (1,246 mg Pb kg?1 soil and 17 mg Cd kg?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl?), 1 M CaCl?, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH?COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO? and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO? and eggshell waste, regardless of extractant. Using CaCl? extraction, the lowest Cd concentration was achieved upon both CaCO? and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH?COOH or EDTA in soils treated with CaCO? and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO? for the immobilization of heavy metals in soils.     

农田重金属污染原位钝化修复研究进展

污染土壤重金属原位钝化修复是通过向土壤中施加一些活性钝化修复材料,通过溶解沉淀、离子交换吸附、氧化还原、有机络合等反应来改变重金属在土壤中的赋存状态,降低土壤中重金属的有效浓度、迁移性和生物有效性。这种方法成本较低、操作简单、见效快且适合大面积推广,在重金属污染土壤修复中有着不可替代的作用。尤其对主要由污水灌溉、大气沉降等造成的农田土壤面源污染,一些具有吸附固定土壤中重金属离子特性的天然物质和工业副产品都可运用在实地的钝化修复中,且不同类型的钝化修复剂对重金属污染土壤的钝化修复效果各不相同。采用实验室评价和实地应用评价,一方面可以评估钝化修复材料对污染土壤中重金属离子的固定效率;另一方面可以评估钝化修复材料对土壤理化性状、养分状况和生物活性的影响。对重金属污染土壤原位钝化修复中不同来源的钝化剂进行了分类,目前广泛使用的钝化修复剂主要包括硅钙物质、含磷材料、有机物料、黏土矿物、金属及金属氧化物、生物碳及新型材料等,概述了它们各自对重金属污染土壤的钝化修复效果。从研究方法、评价指标、环境影响因子、钝化机制以及环境风险评价等方面分析了该领域的研究现状以及存在的主要问题,今后应重点关注钝化修复剂对土壤-作物系统的潜在环境风险以及钝化材料修复效果的田间长期稳定性评价。     

Simple assessment of the reactive aluminium in sediments

The mobility of aluminium in sediments was evaluated through a one-step extraction with a strong chelating agent. Single and sequential extraction procedures for the extraction of Al were applied to four sediments from a polluted region. A single-step extraction with 0.05 mol L⁻¹ ethylenediaminetetraacetic acid (EDTA) was used, and compared with a standardized SEP as reference. The Al contents extracted into Na₂EDTA were in good agreement with the sequential extraction that yeilds mobile and potentially mobile portion of Al. Extracted EDTA contents make up more than 70% of the first-three-step sum of the five-step extraction procedure. Thus, Na₂EDTA extraction of Al could be applied to assess aluminium mobility changes in sediments and soils.     

2种毒性评估方法对PAHs污染场地人体健康风险的比较研究

毒性评估是人体健康风险评价的重要部分,目前主要存在2种方法,一种基于PAHs相对于苯并[a]芘(BaP)的毒性当量因子,采用Ba P致癌斜率因子参数(方法 1),另一种直接采用各PAHs致癌斜率因子和非致癌参考剂量等参数(方法 2)。然而2种毒性评估方法得到的风险及修复量是否存在差异以及引起差异的原因等问题鲜有讨论。针对苏南某焦化厂PAHs污染土壤,采用分层土壤健康风险评价模型,对比了2种毒性评估方法确定的PAHs风险、修复目标污染物及土方量的差异,并对引起差异的关键因素进行探讨。结果表明:对于0.0~1.0 m表层土壤,方法 1和方法 2确定的致癌风险最大值分别1.48E-05和1.32E-05,均超过可接受致癌风险,修复土方量分别为27 846 m~3和28 667 m3,修复目标污染物均为Ba P和二苊烃(Acy)。对于1.0~3.0 m深层土壤,方法 1确定的致癌风险最大值为3.36E-08,低于可接受致癌风险,不需要修复;而方法 2确定的致癌风险最大值为3.73E-04,非致癌危害指数最大值为6.96E+01,分别超过可接受致癌风险和非致癌危害商,需要修复,修复目标污染物为萘(NaP),修复土方量为35 944 m~3。最终,方法 2确定的总修复土方量(64 611 m~3)为方法 1确定土方量(27 846 m~3)的2.45倍,而这种差异主要是由于方法 1低估了深层土壤中高挥发性PAH单体尤其是NaP的风险所致。因此,从保守角度建议采用方法 2进行PAHs风险评价。     

应用脂肪酸甲酯淋洗去除土壤中多环芳烃

针对煤气厂土壤等高浓度多环芳烃污染土壤修复困难的现实,采用易生物降解的新型淋洗剂脂肪酸甲酯淋洗修复高浓度多环芳烃污染的土壤,同时进行了以甲醇、植物油(大豆油)作为淋洗剂的淋洗实验,比较不同淋洗剂的淋洗效果.结果证明脂肪酸甲酯对人工模拟污染土壤中蒽、荧蒽、芘、苯并(a)芘的去除率可以达到80%—95%,对煤气厂土壤中多环芳烃的去除效果也非常明显,总多环芳烃的去除率达到41%.脂肪酸甲酯的淋洗效果要优于其它两种淋洗剂.     

厌氧微生物作用下土壤中砷的形态转化及其分配

厌氧微生物作用下土壤中砷的形态转化及分配比例对砷的环境行为与归趋具有重要影响。实验利用张士污灌区土壤负载低浓度砷,研究了厌氧微生物作用下砷的形态转化过程,并通过磷酸盐及盐酸提取土壤中的砷、铁和硫,探讨了砷在土壤中结合形态的变化及土壤矿物结构转化与砷环境行为的关联。实验结果表明,微生物作用下土壤负载的砷被迅速还原为As(III)并释放进入液相,培养24h后液相累积的As(T)量达到16.9μmol·L-1,其中As(III)占液相总砷含量的91%以上;48h后释放的砷被再次固持,液相残留的As(III)浓度仅为1.5μmol·L-1。尽管微生物还原作用造成土壤中铁氧化物的活化,但固相中磷酸盐提取态与盐酸提取态砷所占的比例分别从载砷量的45.3%和49.8%降低到22.0%与0.22%,而体系中硫酸盐还原产生的硫离子的量与砷的释放量保持负相关。可见微生物还原作用下砷发生了活化,释放和再固定的过程,土壤负载的砷从溶解态、吸附态及铁氧化物结合态逐渐被转化为更稳定的硫化物结合态。此研究对于预测土壤中砷的行为与归趋及污染土壤修复具有一定意义。     

Assessment of mobile and potential mobile trace elements extractability in calcareous soils using different extracting agents

• DTPA and NH₄OAc, HNO₃ and EDTA, and MgCl₂ and NH₄NO₃ had similar behavior. • In NH₄OAc, DTPA, and EDTA, the possibility of re-adsorption of trace elements is low. • CaCl₂ may be more suitable than other extracts in calcareous soils. Understanding trace elements mobility in soils, extracting agents, and their relationships with soil components, are essential for predicting their movement in soil profile and availability to plants. A laboratory study was conducted to evaluate extractability of cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), and zinc (Zn) from calcareous soils utilizing various extracting agents to be specific CaCl₂, DTPA, EDTA, HNO₃, MgCl₂, NaNO₃, NH₄NO₃, and NH₄OAc. Cluster analysis indicated that DTPA and NH₄OAc, HNO₃ and EDTA, and MgCl₂ and NH₄NO₃ extracting agents yielded comparative values, whereas NaNO₃ and CaCl₂ have shown different behavior than other extracting agents for all studied trace elements. The speciation of extracted trace elements in solutions indicated that in the CaCl₂, NaNO₃, NH₄NO₃, and MgCl₂ extracting agents most extracted Cd, Co, Ni, Zn, and part of Cu were as free ions and may be re-adsorbed on soils, leading to lower extractability, whereas, in the case of HNO₃ extracting agent, the likelihood of re-adsorption of trace elements may be little. The results of speciation of trace elements using NH₄OAc, DTPA, and EDTA extracting agents showed that Me-(Acetate)₃^–, Me-(Acetate)₂(aq), Me(DTPA)³⁻, Me(EDTA)²⁻, and MeH(EDTA)^– complexes dominated in solutions indicating that the extracted trace elements may not be re-adsorbed on soils, leading to higher extractability. The results of this study are useful for short and long-term evaluations of trace elements mobility and further environmental impacts.     

Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO₃) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0–5% powdered eggshell waste and curing the soil (1,246 mg Pb kg^?1 soil and 17 mg Cd kg^?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl₂), 1 M CaCl₂, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH₃COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO₃ and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO₃ and eggshell waste, regardless of extractant. Using CaCl₂ extraction, the lowest Cd concentration was achieved upon both CaCO₃ and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH₃COOH or EDTA in soils treated with CaCO₃ and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO₃ for the immobilization of heavy metals in soils.     

Chemical reclamation of crude-oil-inundated soils from Niger Delta, Nigeria

Crude-oil-inundated soils were collected from the Agbada oil field in the Niger Delta region of Nigeria 2 months after the recorded incidence of oil spillage. The soils were taken on the second day of reconnaissance from three replicate quadrats, at surface (0-15 cm) and subsurface (15-30 cm) depths, using the grid sampling technique. The total extractable hydrocarbon content (THC) of the polluted soils ranged from 1.24 × 10² to 3.86 × 10⁴ mg/kg at surface and subsurface depths (no overlap in standard errors at a 95% confidence level). Greenhouse trials for possible reclamation were later carried out using 10-100 g of (NH₄)₂SO₄, KH₂PO₄ and KCl (NPK) fertilizer as nutrient supplements. Nitrogen as NO₃-N and potassium were optimally enhanced at 2% (w/w) and 3% (w/w) of the NPK supplementation, respectively. Phosphorus, which was inherently more enhanced in the soils than the other nutrients, maintained the same level of impact after treatment with 20 g of NPK fertilizer. Total organic carbon (%TOC), total organic matter (%TOM), pH, and percentage moisture content all provided evidence of enhanced mineralization in the fertilizer-treated soils. If reclamation of the crude-oil-inundated soils is construed as the return to normal levels of metabolic activities of the soils, then the application of the inorganic fertilizers at such prescribed levels would duly accelerate the remediation process. However, this would be limited to levels of pollution empirically defined by such THC values obtained in this study.     

新乡市公园土壤重金属污染

通过对新乡市区6个有代表性公园土壤重金属含量的调查,结果发现市区公园表层土壤Pb、Cr、Cd和Zn的平均含量分别为63.22 mg/kg、91.35 mg/kg、0.57 mg/kg、115.63 mg/kg。以河南省土壤背景值为标准,用内梅罗指数法综合评价,结果表明:6个公园土壤中重金属Cr、Zn为轻度污染;Pb为中度污染;Cd为重度污染。所有公园土壤都存在Pb、Cd和Zn污染。     

An evaluation of heavy metals contamination in soils from Ganzhou navel orange orchards by geoaccumulation indexes and statistical analysis

Heavy metal pollution in orchard soils is of increasing concern owing to the potential health risk via the food chain. The evaluations of the degree of heavy metal contamination and the potential sources in soils from navel orange orchards in the Ganzhou district were investigated in the present study with the geoaccumulation index and hierarchical cluster analysis. The soil samples were collected from 280 navel orange orchards located in the 18 counties of the Ganzhou district. The concentrations of heavy metals in the samples were determined using atomic fluorescence spectrometry and inductively coupled plasma atomic emission spectrometry with sample preparation by microwave digestion system. The results of the geoaccumulation index showed that the Ganzhou navel orange orchards were practically uncontaminated with Hg, As, Pb, Cd, Cr, Zn, and Cu, while uncontaminated to moderately contaminated with Ni. The results of cluster analysis indicated that four distinct clusters emerged for 18 sampling counties, and the considerable differences between clusters were derived from the different kinds of polluted substances. Results of the assessment of geoaccumulation index of heavy metals in soils will be helpful for the formulation of strategic sustainable agriculture in Ganzhou navel orchards and improvement of the navel orange yield and quality.     

有机酸对根际土壤中铅形态及其生物毒性的影响

采用根袋盆栽试验和连续浸提方法研究外源柠檬酸、EDTA对根际土壤中Pb形态转化及其生物毒性的影响。结果表明，有机酸能明显活化根际土壤中的Pb，高浓度(3mmol／L)比低浓度(0．5mmol／L)的柠檬酸对Pb的活化能力强；EDTA在低浓度(0．5mmol／L)时对Pb的活化能力就很强。柠檬酸、EDTA能增强土壤Pb的毒性，提高小麦根部对Pb的吸收，并促进Pb由根部向地上部转移。     

Sulfate pollution: evidence for electrochemical production of persulfate by oxidizing sulfate released by the surfactant sodium dodecyl sulfate

Environmental Chemistry Letters - There is increasing concern about contamination by surfactants that are used to extract organic pollutants during remediation of polluted soils and aquifers. For...     

EDTA and citric acid mediated phytoextraction of Zn, Cu, Pb and Cd through marigold (Tagetes erecta)

Phytoextraction is an emerging cost-effective solution for remediation of contaminated soils which involves the removal of toxins, especially heavy metals and metalloids, by the roots of the plants with subsequent transport to aerial plant organs. The aim of the present investigation is to study the effects of EDTA and citric acid on accumulation potential of marigold (Tagetes erecta) to Zn, Cu, Pb, and Cd and also to evaluate the impacts of these chelators (EDTA and citric acid) in combination with all the four heavy metals on the growth of marigold. The plants were grown in pots and treated with Zn (7.3 mg l(-1)), Cu (7.5 mg I(-1)), Pb (3.7 mg l(-1)) and Cd (0.2 mg l(-1)) alone and in combination with different doses of EDTA i.e., 10, 20 and 30 mg l(-1). All the three doses of EDTA i.e., 10, 20 and 30 mg l(-1) significantly increased the accumulation of Zn, Cu, Pb and Cd by roots, stems and leaves as compared to control treatments. The 30 mg l(-1) concentration of citric acid showed reduced accumulation of these metals by root, stem and leaves as compared to lower doses i.e., 10 and 20 mg l(-1). Among the four heavy metals, Zn accumulated in the great amount (526.34 mg kg(-1) DW) followed by Cu (443.14 mg kg(-1) DW), Pb (393.16 mg kg(-1) DW) and Cd (333.62 mg kg(-1) DW) in leaves with 30 mg l(-1) EDTA treatment. The highest concentration of EDTA and citric acid (30 mg l(-1)) caused significant reduction in growth of marigold in terms of plant height, fresh weight of plant, total chlorophyll, carbohydrate content and protein content. Thus EDTA and citric acid efficiently increased the phytoextractability of marigold which can be used to remediate the soil contaminated with these metals.     

A review of combinations of electrokinetic applications

Anthropogenic activities contaminate many lands and underground waters with dangerous materials. Although polluted soils occupy small parts of the land, the risk they pose to plants, animals, humans, and groundwater is too high. Remediation technologies have been used for many years in order to mitigate pollution or remove pollutants from soils. However, there are some deficiencies in the remediation in complex site conditions such as low permeability and complex composition of some clays or heterogeneous subsurface conditions. Electrokinetic is an effective method in which electrodes are embedded in polluted soil, usually vertically but in some cases horizontally, and a low direct current voltage gradient is applied between the electrodes. The electric gradient initiates movement of contaminants by electromigration (charged chemical movement), electro-osmosis (movement of fluid), electrolysis (chemical reactions due to the electric field), and diffusion. However, sites that are contaminated with heavy metals or mixed contaminants (e.g. a combination of organic compounds with heavy metals and/or radionuclides) are difficult to remediate. There is no technology that can achieve the best results, but combining electrokinetic with other remediation methods, such as bioremediation and geosynthetics, promises to be the most effective method so far. This review focuses on the factors that affect electrokinetic remediation and the state-of-the-art methods that can be combined with electrokinetic.     

Changes in chromium distribution during the electrodialytic remediation of a Cr (VI)-contaminated soil

A laboratory study has been carried out to determine the feasibility of in situ remediation of chromium (VI)-contaminated soil using electrodialysis in relation to its speciation in soil. This technique is best suited for low-permeability soils or sediments, which may be difficult to remediate by other means and implies the application of a low-intensity direct current to the soil, which is separated from the electrode compartments by ion-exchange membranes. A clayey soil was prepared for use in the experiments and was characterized before being mixed with a solution of potassium dichromate for several days to produce a final Cr content of 4,056 mg/kg of soil dry wt. Remediation tests were carried out under constant-voltage conditions for periods of 7–14 days and the evolution of applied current to the cell, pH, and conductivity of the electrolytes were recorded periodically. Fractionation of chromium was determined for soil samples before and after remediation using a standardized four-step sequential extraction procedure (SEP) with acetic acid, hydroxylamine, hydrogen peroxide, and aqua regia solutions. Results show that chromium is mobilized from the most labile phases (soluble/exchangeable/carbonate). In a 15 V test, SEP results show that the amount of chromium extracted in the first step drops from 80% to 9%, but also that changes in the total chromium distribution occur during the treatment with some transferred to other soil phases that are more difficult to mobilize.