Development of Resin Membranes as a Sensitive Indicator of Heavy Metal Toxicity in the Soil Environment

Abstract

Ion exchange resins in contact with soil can act as a sink for metal cations, thereby simulate the action of plant roots. Ion exchange resins in membrane form offer additional advantages in ease of use and handling. A procedure was developed to assess the bioavailability of four heavy metals Cd, Cr, Ni and Pb via direct in soil burial. A growth chamber experiment with three representative crops (oats, radish and lettuce) was set up to determine the phytotoxic levels of the four heavy metals. The critical levels varied widely from crop to crop, and soil to soil. Lettuce was most sensitive to high concentration of metals. The toxic effects are more pronounced on sandier textured soils.     

Thermodynamic Characteristics and Mechanisms of Heavy Metals Adsorbed onto Urban Soil

The thermodynamic characteristics of heavy metals adsorbed onto urban soil and the relative adsorption mechanisms were studied by the batch experiment. The results show that there existed dynamic adsorption-desorption equilibrium processes of cationic and anionic ions of heavy metals onto urban soil, which may have an impact on the pH of the adsorption system. The amounts of heavy metals adsorbed onto urban soil increased with the increase of the equilibrium concentration, but their adsorption amounts were not the maximum adsorption amounts. The higher the pH was, the greater the adsorption capacity of the urban soil at the same equilibrium concentration was, and the adsorption amounts of heavy metals onto urban soil followed the order of Pb>Cu>Cd>Zn>Ni. There were coordination reaction, hydrolysis reaction, exchange reaction in the adsorption processes of heavy metals onto urban soil. With the increase of pH, the influencing degree of pH on the different reactions of heavy metals in the soil increased, meanwhile the effects of other physicochemical properties of soil on the adsorption of heavy metals were weakened.     

微塑料介导重金属在陆生植物中迁移及生物效应的影响

随着地膜在现代化农业中的广泛应用,微塑料在土壤中的残留问题日益严重。环境中释放的微塑料可能会与先前存在的重金属相互作用,导致生物效应(生物积累/毒性),并对人类健康和农产品安全构成威胁。目前,大多数研究集中于单一影响因素在土壤系统中的暴露和转化分析,有关微塑料和共存金属对环境联合影响的相当有限。本文综述了微塑料与重金属来源、相互作用机理与影响因素的研究现状,阐述了陆生植物对二者联合污染的生理响应。此外,未来的研究还应重点探讨微塑料与重金属共同在植物上暴露的具体分子机制、通过食物链对人类健康的影响、与其他混合污染物联合作用及微塑料老化过程对重金属迁移动态变化过程的影响。     

Quantitative determination of chelators and their degradation products in mixed hazardous wastes from Tank 241-SY-101 using derivatization GC/MS

Considerable attention has been focused on chelators such as ethylenediaminetetraacetic acid (EDTA) and N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), which form water-soluble complexes with most heavy metals. Most radionuclides are included in this class of constituents. As a result, chelator complexes have become very important environmentally because of their tendency to enhance the mobility of heavy metals through the soil and potentially contaminate groundwater. In addition, there is a correlation between chelator concentration and crust formation/gas release. The chelators are a class of compounds whose low volatility and high polarity preclude analysis by gas chromatography/mass spectrometry (GC/MS) without prior derivatization. Waste samples from a double-shell storage tank at Hanford were derivatized with BF₃/methanol and analyzed using GC/MS. Results indicate the presence of EDTA, HEDTA, nitrilotriacetic (NTA), and citric acid. Nitrosoiminodiacetic acid was identified and determined to be an artifact of the derivatization procedure; it is assumed to arise from nitrosation of iminodiacetic acid in the waste sample.     

贵阳污灌区菜地土壤团聚体中有机碳和重金属的含量特征及相关性分析

以贵阳某污灌区菜地土壤为研究对象,分别采用微波消解-电感耦合等离子体质谱(ICP-MS)法和水合热重铬酸钾氧化分光光度法分析不同粒径土壤团聚体中重金属和有机碳的含量特征,并对有机碳和重金属的相关性进行分析。结果表明,以2mm粒径团聚体的含量为最高,约占75%。Cu、Zn、Cd和Pb在0.25～0.5mm粒径团聚体中含量最高,Cr在5～8mm粒径团聚体中含量最高,As在不同粒径团聚体中的含量变化不大,重金属含量随土层深度增大而减小。土壤重金属富集因子表现为CuPbCdZnCrAs,Cu、Zn、Cd和Pb在0.25～0.5mm粒径团聚体中分布因子最高,而在5～8mm粒径团聚体中重金属的质量负载因子最大。土壤有机碳含量随团聚体粒径的增大表现为先增大后减小,不同粒径团聚体中Cu、Cd、Pb和As含量与有机碳含量均呈显著正相关(p0.05)。污灌区菜地土壤Cr、As在5～8mm粒径团聚体中富集现象显著,Cu、Zn、Cd、Pb在0.25～0.5mm粒径团聚体中均表现出显著的富集特征。6种重金属在5～8mm粒径团聚体中的质量负载因子均为最高,表明6种重金属在5～8mm粒径团聚体中的贡献最大。     

Colloidochemical Processes in the Biotechnology of Heavy Metal Removal from the Soil

The sorption processes of uranium(VI), copper, cobalt, and strontium by the native soil were studied. It was shown that, by their ability to be accumulated by the podsolized soil, these metals are arranged in the following sequence: U(VI) > Cu > Co > Sr. This selectivity sequence is retained during the sorption of metals from mixed solutions containing their equimolar concentrations. The possibility of the leaching of the studied metals from the contaminated soil by Basillus cereusVKM 4368 metal-resistant culture was demonstrated using glucose and sodium acetate as the sources of carbon and energy. In the first case, 90–99% of heavy metals was extracted from the soil as water-soluble citrate complexes. In the second case (during the metabolism of acetate by bacteria), the removal of heavy metals from the soil as hydroxide–carbonate precipitates and complexes was equal to 80–90%. Sedimentation of particles in the soil suspension is accelerated considerably after the treatment by the metal-resistant culture.     

The removal of Cu,Ni, and Zn in industrial soil by washing with EDTA-organic acids

In order to improve the heavy metal removal ability of traditional single washing agents and explore the removal mechanism of heavy metals. Then, the washing reagents that mixed by low-molecular weight organic acids (citric acid, oxalic acid, and tartaric acid) and artificial chelating compound ethylenediaminetetraacetic acid disodium (EDTA) were selected. Furthermore, the effect of soil washing parameters, the variation of leaching toxicity, mobility, stability and speciation of heavy metals were also considered. The results of soil washing experiments showed that mixing an equal volume of 0.05 M EDTA and 0.2 M organic acids (citric acid, oxalic acid, and tartaric acid) could remove more than about 80% heavy metals from soil under the optimal conditions. In addition, the soil leaching toxicity was decreased and the stability of remaining heavy metals was increased, indicating that EDTA-organic acid washing reagents could effectively reduce the ecological risk of contaminated soil. EDTA had a stronger chelating ability with heavy metals than the organic acids, and the organic acids could not only chelate heavy metals but also decrease the pH of the mixture for promoting the desorption of heavy metals. Thus, mixing EDTA and organic acids was advisable method to improve soil washing technology.     

Determination of Occurrence Characteristics of Heavy Metals in Soil and Water Environments in Tianshan Mountains,Central Asia

China has one of the fastest-growing economies in the world, but this economic development has important implications for environmental changes in this country. Our research was to quantify the presence of heavy metals in soil and water environments in the Tianshan Mountains region of China, associated with the economic development of this region. We used anomaly analysis, correlation analysis, and principal component analysis to assess the occurrence characteristics of heavy metals in this area. Results showed that Co, Cr, As, and Ni are more prevalent in water environments than in soil environments; in contrast, Cd, Zn, Pb, Hg, and Mn are more prevalent in soil samples than in water samples. This analysis grouped 10 heavy metals in soil and water environments into three principal components. In soil environments, the prevalence order was Co, Ni, Cr, As > Mn, Zn, Pb > Hg, Cd, Cu. In water environments, the order was Cu, Co, Ni, Cr, As > Hg, Mn, Zn > Cd, Pb. It is possible to distinguish between the natural and the anthropogenic sources of heavy metals in the Tianshan Mountains. With the current rapid economic development in the Tianshan Mountains, anthropogenic sources are playing principal roles in serious heavy metal accumulations in this region. This problem warrants immediate and widespread attention to prevent further deterioration of the soil and water environments.     

西南山地煤矿区耕地土壤-农作物重金属富集及健康风险评价

为了解西南某典型山地煤矿区周边农田土壤、农作物重金属的富集情况及对当地人群健康的影响程度,采集矿区周边农田土壤样品和对应的农作物样品,测定重金属Cr、Mn、Zn、As、Pb的含量。运用Nemero指数法、潜在风险指数法对土壤重金属的污染程度进行评价;采用靶标危害系数法(THQ)评价农作物重金属对人体的健康风险。结果显示,Cr、Mn、Zn、As、Pb分别是背景值的1.81、1.90、2.89、1.30、0.86倍,处于轻度污染级别,轻微危害程度。农作物重金属Cr、Pb和As含量的超标情况较严重,Zn的含量超标相对较小。各农作物富集的重金属对人体的健康风险大小为：高粱>玉米>白菜>葱>辣椒。农作物重金属对儿童健康的危害均达到了慢性中毒;对成人健康的影响,高粱处于慢性中毒,其它农作物重金属处于产生较大影响的危害程度。农作物重金属与土壤重金属的相关性分析表明,农作物重金属的含量与土壤重金属全量并无线性关系;各重金属在农作物中的转移能力不同;Pb,As在农作物中的转移能力较大,而Cr相对较小。鉴于矿区重金属的富集情况,应尽快采取修复治理措施,为保证当地人群健康,建议当地居民不再食用和种植富集重金属严重的高粱、玉米农作物。     

Speciation of Heavy Metals in Sewage Sludge and Sludge-Amended Soil

Abstract

The presence of heavy metals in sewage sludge restricts their agricultural use. Sequential extraction procedures may provide an assessment of the mobility of these elements in sludge and sludge-amended soil, and may help to predict the release of metals in soil solution. Nevertheless, the “phases” in which an element occurs are operationally defined and it is necessary to standardize a procedure in order to allow the comparison of result from different laboratories.     

澜沧江中上游流域矿区土壤重金属含量的调查

为了解澜沧江中上游流域矿区的开采和利用对周围生态环境的影响因素,通过选择对该矿区中3种重金属污染物Pb、Cd、Mn进行了调查和实验。确定澜沧江中上游流域的相应采样面,通过湿消化法处理样品,原子吸收光谱法测定了重金属的含量,并作了重金属污染评价。结果表明,澜沧江中上游流域矿区土壤Cd平均值为21.89 mg/kg,超标率为100%,土壤中重金属含量由高到低为Cd,Mn,Pb,重金属之间相关性不显著(P>0.05)。研究区土壤已经被严重污染,单项污染指数由高到低为Cd(21),Pb(0.87),Mn(0.81)。可见澜沧江中上游流域矿区土壤中Pb、Cd、Mn的污染已经呈现出了危害人群健康的趋势,其中Pb、Cd污染最严重,对于重金属污染应采取综合治理措施。     

Evaluation of heavy metal bioavailability in soil amended with poultry manure using single and BCR sequential extractions

In the present study, three-step Community Bureau of Reference sequential extraction scheme (BCR-SES) and single extraction methods were performed to assess the mobility and availability of heavy metals (Cd, Cu, Pb, Fe and Zn) in an agricultural soil before and after amendment with poultry waste (PW).The PW samples were collected from poultry farms, situated in Hyderabad Sindh, Pakistan. The extractable heavy metals were measured by flame and electrothermal atomic absorption spectrometry. The validation of the method was carried out by analysis of a certified reference material of soil amended with sewage sludge (BCR-483). The single extractions using calcium chloride and EDTA, separately, while BCR-SESs were developed to evaluate the available heavy metals to plants and their environmental accessibility for control soil (CS), PW and soil amended with PW (SPW).The pH of the PW and SPW were found to be < 6.0, which may enhance the leaching of heavy metals to agricultural soil. The results from the partitioning study indicated that easily mobilised forms (acid exchangeable) of Cd were higher than other heavy metals. The oxidisable fractions of all heavy metals were dominant in PW and SPW as compared to found in CS samples. The EDTA- and CaCl₂-extractable heavy metals correspond to 5.0 to 10 and 0.5 to 3.0%, respectively of total contents in all three solid samples. Contamination factors revealed that the retention of Pb and Zn were higher compared with Cu, Cd and Fe in CS, PW and SPW samples.     

Distribution of heavy metals of agricultural soils of central Greece using the modified BCR sequential extraction method

The state of heavy metal (Cd, Cu, Ni, Zn, Pb, and Cr) pollution was studied, in 440 texturally different soil profiles in Thessaly, an intensely cultivated region in Central Greece. The study was carried out in 2004 and 2005 on 220 soil samples for each year. Soil samples were classified in three soil orders: Endisols, Alfisols, and Vertisols according to the Soil Taxonomy System. The pseudo-total concentrations of heavy metals were determined by the aqua regia procedure. Heavy metals were also determined after division into four fractions by sequential extraction with (a) acetic acid (exchangeable and specifically adsorbed metals), (b) a reducing agent (bound to Fe/Mn hydroxides), (c) an oxidizing agent (bound to soil organic matter), and (d) aqua regia (bound to mineral structures, residual). The concentrations of all the metals studied were higher in the topsoil (0–30?cm) and lower in the second soil layer (30–60?cm). Concentrations of 70–82% of Cd, 39–64% of Cu, 41–69% of Ni, 29–51% of Zn, 75–89% of Pb, and 52–87% of Cr were found in the first two fractions. Cd appeared to be the most mobile of the metals studied, while Cu and Zn were found in forms associated with soil organic matter. The chemical partitioning patterns of Pb and Cr indicated that these metals are largely associated with the Fe–Mn hydroxides, while Cr was also found in the residual fractions. Significant correlations between heavy metals fractions and soil physicochemical parameters were obtained and discussed.     

Assessment of heavy metals leachability from metallo-organic sorbent-iron humate-with the aid of sequential extraction test

The sequential extraction test, known as a BCR procedure, was used to assess a leachability of heavy metals (Zn, Cd, Pb, Cu) from the metallo-organic sorbent—iron humate—loaded with these metals. The sequential test allowed to discriminate between various fractions of heavy metals, namely the acid-extractable fraction, the fraction bound to Fe oxides, and the fraction bound to organic matter. It was proven that the heavy metals are bound mainly to Fe oxides and organic matter, and thus they may be relatively hardly liberated into the environment. The BCR sequential extraction test exhibited a very good repeatability, when it was applied to the loaded sorbent—relative standard deviations were typically lower than 10%.     

Relationship between vegetable metal and soil-extractable metal contents by the BCR sequential extraction procedure: chemometrical interpretation of the data

The contents of heavy metals in soil and vegetable samples collected from an urban garden in Kayseri, Turkey, were investigated. Both wet- and dry-ashing methods were used for dissolving vegetable samples. A sequential extraction procedure proposed by the Commission of the European Communities, Community Bureau of Reference (now superseded by the Standards, Measurement and Testing Programme, SM&T) was applied to the soil samples to extract the metals which are present in exchangeable and acid soluble (i.e. bound to carbonates), reducible (bound to Fe/Mn oxides), and oxidisable forms (bound to organic matter and sulphides) in the soil samples. Trace metals in the soil and vegetable samples were determined using flame atomic absorption spectrometry (FAAS). The total metal contents acquired by summing of metal levels in all the sequential extraction steps were compared with pseudo-total metal levels obtained with aqua regia for all the soil samples. The recovery values obtained by proportioning the results obtained by the BCR procedure to those of the pseudo-total digestion were found to be satisfactory. The limits of detection for the elements investigated were in the range of 0.04 to 0.59?µg?mL^?1 for all the extraction stages of the BCR procedure. Similarities among the variables were identified by correlation analysis, principal component analysis and hierarchical cluster analysis. The relationship between the vegetable metal and soil-extractable metal concentrations was examined in order to evaluate the bioavailability of metals.     

土壤重金属污染评价指标的研究进展

土壤重金属污染评价指标主要有：土壤重金属总含量，有效含量，土壤酶活性以及植物中毒临界含量等。由于受重金属污染的土壤中往往伴有多种重金属元素以及元素之间的交互作用，使得临界值的确定更为复杂，目前评价土壤重金属复合污染的方法主要是综合指数法。     

The Analysis of Inorganic and Organic Pollutants in Soil with Special Regard to Their Bioavailability

Abstract

The most important inorganic pollutants in soil are the heavy metals. Problems related to the determination of the total and soluble content are discussed. Soluble contents are of interest in connection with studies about bioavailability. Because some of the heavy metals are essential for plant growth, most of the work about bioavailability has been done in the field of plant nutrition. Much less is known about the situation in polluted soils.

It was shown that neutral salt solutions which do not really change the pH of soil during the extraction procedure are best suited to define thresholds of excess. This is in contrast to much stronger extractants like EDTA or DTPA often proposed for the analysis of soils which are deficient in trace elements.

With three sets of experiments the correlation between the contents of cadmium, copper, nickel and zinc extracted by 0.1 M NaNO₃ (as an example of a neutral salt solution) and the plant response (phyto- or zootoxicity) are shown:

—pot experiments using soils which were contaminated by metal salt solutions

—pot experiments using soils from contaminated areas

—field studies in polluted areas. In these studies the aspect of heavy metal leaching was also considered.

The results were converted to indicative values in the Swiss Ordinance of Pollutants in the Soil. These indicative values derived from plant reactions were checked by the carbon mineralisation as an example of a soil microbiological process.

As it was found that organic pollutants are not easily taken up by plant roots the problem of bioavailability is much less important. However, the biodegradation and formation of metabolites has to be considered.     

环江县大环江下游沿岸重金属污染区农作物污染评价

采样分析了广西环江县大环江河下游沿岸受重金属污染的4块农田土壤及农作物可食用部分重金属含量,并进行了污染评价。结果表明,4块受污染农田土壤重金属污染级别均为轻污染,受污染农田土壤上种植的油麦菜、茼蒿、生菜、小白菜、稻米等农作物可食用部分为重污染,污染水平远远超过国家食品卫生限值标准。建议在未经改良的情况下,不宜在重金属污染的土壤上种植此类农作物。     

Simultaneous determination of traces of heavy metals by solid-phase spectrophotometry

A coupling sensitive solid phase spectrophotometric (SPS) procedure for determination of traces of heavy metals (Me-SPS) and multicomponent analysis by multiple linear regressions (MA), a simple methodology for simultaneous determination of metals in mixtures was inaugurated. The Me-SPS procedure is based on sorption of heavy metals on PAN-resin and direct absorbance measurements of colour product Me-PAN sorbed on a solid carrier in a 1-mm cell. This methodology (Me-SPS-MA) was checked by simultaneous determination of metals in synthetic mixtures with different compositions and contents of metals important in pharmaceutical practice: Zn, Pb, Cd, Cu, Co, and Ni. Good agreement between experimental and theoretical amounts of heavy metals is obtained from the recovery test (78.3–110.0%). The proposed method enables determination of particular metal ion at the ng mL⁻¹ level and it was successfully applied to the determination impurities from heavy metal traces in pharmaceutical substances (Cu in ascorbic acid, Pb in glucose, and Zn in insulin). The proposed procedure could be possible contribution to the development of pharmacopoeial methodology for a heavy metals test.     

Assessment of mobility of heavy metals in two soil types by use of column leaching experiments and chemometric evaluation of elution curves

The objectives of this study were to evaluate the mobility of heavy metals (HMs) in two types of soils (acidic forest soil and neutral agricultural soil) by leaching with calcium chloride solution in column experiments. The screening properties of neutral agricultural soil towards pollution by heavy metals (Ni, Cu, Zn and Cd) are approximately 10 times higher than those of acid forest soil. The neutral agricultural soil, polluted artificially by one pore volume (PV) of an HMs solution of concentration 200 mg L^?1, can screen the leaching of these metals over several hundreds of years. The higher apparent desorption rate and per cent desorption of HMs (especially Cd) in acid forest soil indicated a higher potential of intensive migration of the metals across the profile and indicated potential risk of Cd pollution for this type of soil. The latest approach of artificial neural networks to describe transport of HMs in soil has been also evaluated. Using a simple three-layer perceptron topology with three hidden neurons, the experimental data could be simulated. The results suggested that the pH of soil is a major factor controlling the retention of the heavy metals in the soils.