Morphological and physiological responses of barley plants grown on soils characterised by metal toxicity and metal deficiency

Aim of this work was to investigate which are the effects on barley crops grown on two different soils: a soil lacking in Cu, an essential micronutrient (A) and a naturally polluted soil rich in lead, zinc, copper (B). In particular we investigated the relationship between some ecophysiological parameters such as biomass, chlorophyll concentration and guaiacolo peroxidase activity and the chemical-physical properties of the soils like pH, organic matter and heavy metal content. Because metals uptake by plants is strongly correlated with the bioavailable fraction rather then their total amount in a soil, we have measured also metal exchangeable forms, using a single extraction method (MgCl2 as extractant). Plants grown on soil B showed a metal content higher than background limits, whereas plants grown on soil A were characterised by a background Fe and Zn concentrations and by a tolerant Pb concentration. Conversely, Cu content in tissues of plants grown in soil A is found to be under the background limits. Copper-deficiency plants present chlorotic leaves followed by a reduced clorophyll content, while plants grown on metals contaminated soil showed an increase of peroxidase activity.     

Quality and comparability of measurement of potentially toxic elements in urban soils by a group of European laboratories

A study has been conducted to assess the quality and comparability of measurement of aqua-regia-soluble cadmium, chromium, copper, iron, manganese, nickel, lead, and zinc in urban soils within a small cohort of European research laboratories specializing in soil science or environmental analytical chemistry. An initial survey indicated that highly variable levels of analytical quality control (e.g. use of certified reference materials) were routinely implemented in participant laboratories. When a set of soil samples—differing in metal contents and in characteristics such as pH and organic-matter content—were exchanged and analysed, approximately 20% of results differed from target values by more than 25%. A principal-component analysis was applied to data for chromium, copper, nickel, lead, and zinc, and proved successful in assessing overall laboratory performance. The study indicates that greater prominence needs to be given to quality assurance and control if comparable data are to be generated in international, collaborative research projects.     

高压密闭消解-原子吸收光度法同时测定土壤中的铜、锌、铅、镉、镍、铬

采用高压密闭消解-原子吸收光度法同时测定土壤中铜、锌、铅、镉、镍、铬6种重金属元素。通过剖析不同消解体系,选择了最佳消解条件和测定条件。测定土壤中各元素的回收率均在86%～110%之间,相对标准偏差均小于8.0%(n=6)。     

微波消解-电感耦合等离子体质谱法(ICP-MS)同时测定土壤中11种金属元素

称取0.25 g样品加入5ml硝酸和2ml氢氟酸,用微波消解技术对样品进行前处理。以Re作为As、Pb、Tl的内标,Rh作为Cd、Co、Cr、Ni的内标,Bi作为Be、Cu、Zn的内标,Tb作为V的内标,建立了KED模式下可同时测定土壤中Be、As、Cd、Co、Cr、Cu、Ni、Pb、Tl、V、Zn 11种金属元素的微波消解ICP-MS方法。该方法线性关系良好,线性相关系数均在0.9990以上,检出限为0.002mg/kg-0.054 mg/kg。检测土壤标准物质GSS-17、GSS-18验证方法准确性,结果显示测定值均在标准差允许范围内,相对标准偏差在0.29%-5.33%,是一种快速、可靠的土壤多种金属元素检测方法。     

Persistence of Metal Residues in Sewage Sludge Treated Soils Over Seventeen Years

Abstract

Results from two long-term sewage sludge experiments conducted on different soil types are presented. Sewage sludges highly contaminated with Cr, Cu, Ni or Zn and a relatively uncontaminated sludge were applied at both sites at the same rates and metal contents in 1968. The Cr-rich sludge also had a high Cd content. Plot soils were sampled in 1972, 1976 or 1977, 1981 and 1985 and total and extractable metal contents determined. Metals added in sewage sludge may change their form but persist in soils in an extractable and plant available form for many years. There is little difference in soil extractable contents or plant uptake of Cu and Zn whether sludge is applied as one single application or as its equivalent in four separate annual applications of one quarter the amount. The percentages of the total chromium contents extractable by both EDTA and acetic acid were small and this was reflected in a low uptake of this element by pasture herbage species (<0.3 mg Cr/kg DM).     

微波消解-电感耦合等离子体质谱(ICP-MS)法同时测定土壤中11种金属元素

称取0.25g样品加入5 mL硝酸和2 mL氢氟酸,用微波消解技术对样品进行前处理.以Re作为As、Pb、Tl的内标,Rh作为Cd、Co、Cr、Ni的内标,Bi作为Be、Cu、Zn的内标,Tb作为V的内标,建立了KED模式下微波消解电感耦合等离子体质谱(ICP-MS)法同时测定土壤中Be、As、Cd、Co、Cr、Cu、...     

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.     

Transfer of Metals from Soil to Crops in an Area near a Coal Gangue Pile in the Guqiao Coal Mine,China

A field survey was conducted to investigate the metal contamination in coal gangue, soils, and crops (rice and soybeans), and to evaluate the possible health risks to the local population through food chain transfer near a coal gangue pile in the Guqiao Coal Mine, China. Contamination levels of zinc, lead, cadmium, and copper in coal gangue, soils, and crops were measured, and bio-accumulation factors from soil to crops were determined; the health risks were calculated accordingly. Results showed that both coal gangue and soil contained high levels of cadmium (0.15 mg kg^?1and 0.20 mg kg^?1) exceeding the background value of the soil. The lead soil concentration was low (9.99 mg kg^?1), but lead in rice (0.38 mg kg^?1) exceeded the maximal permissible limit of 0.2 mg kg^?1. For some tissues of crops studied, there was a significant correlation between the bio-accumulation factor values and the corresponding soil metal concentrations that were best described by a power equation. Oral intake of zinc, cadmium, and copper through crops posed no health risk to local residents, although hazard indices for rice (0.87–2.88) and soybeans (0.06–0.09) suggested that ingestion of rice grains was unsafe for human health. Therefore, rice was inappropriate to be planted in the soil surrounding this coal mine.     

基于养分指标相关性的土壤有机质预测模型研究

为探究土壤间各养分指标间的相互关系,选取了天津市宁河区不同区域的种植土壤,基于行业标准规定的检测方法,对主要养分指标进行了测定,并研究各指标间的相关性。结果表明,各区域土壤pH值变异系数最小,整体均呈碱性;有机质、全氮及速效钾变异系数属于中等;有效磷的变异系数最高。各研究区域土壤有机质含量与全氮含量呈显著正相关(P<0.01),与pH值呈显著负相关(P<0.01),而与其他指标间不具备普遍且显著的相关性。基于多元线性回归分析建立了土壤有机质与全氮及pH值之间的预测模型,通过模型计算出的预测值与实际测定值的拟合性较好;另取土壤样品进行验证表明,预测模型具有良好的可靠性和准确性。     

Dispersive Liquid–Liquid Microextraction and Micro-Solid Phase Extraction for the Rapid Determination of Metals in Food and Environmental Waters

A rapid and novel two-step dispersive liquid–liquid microextraction and dispersive micro-solid phase extraction method was established for the separation and enrichment of trace cadmium, nickel, and copper in food and environmental water prior to determination by inductively coupled plasma-mass spectrometry (ICP-MS). In the first microextraction step, carbon tetrachloride was employed to extract metal-diethyldithiocarbamate chelates from aqueous solution with ultrasound. In the following step, Fe₃O₄ magnetic nanoparticles were added and used to collect the analytes in the organic solvent. The sample pH, type and volume of extraction solvent, mass of magnetic nanoparticles, concentration of the chelating agent, concentration of sodium chloride, and sonication time were optimized. The linear dynamic range was from 0.01 to 20 micrograms per liter with correlation coefficients between 0.9990 and 0.9992. Enrichment factors were 78, 79, and 81 for cadmium, nickel, and copper, respectively. The limits of detection for cadmium, nickel, and copper were 0.007, 0.009, and 0.017 micrograms per liter, with relative standard deviations from 1.1 to 2.6 percent. The developed method was validated by the determination of cadmium, nickel, and copper in rice and mussel certified reference materials, food, and environmental water with satisfactory results.     

Preparation of candidate certified reference materials for the quality control of EDTA-and acetic acid-extractable trace metal determinations in sewage sludge-amended soil and terra rossa soil

The determination of extractable trace metal contents in soil using single extraction procedures is currently performed in many laboratories to assess the bioavailable metal fraction (and related phytotoxic effects) and the accessability to the environment (e.g. contamination of ground waters). Owing to the need for validation of the extraction schemes used and of the analytical techniques, the EC Measurements and Testing Programme (formerly BCR) has organized a project for improving the quality of determination of extractable trace metal contents in soil, the first step being an interlaboratory study to adopt common extraction procedures and the second being a certification campaign to certify two soils for their extractable trace element contents following these procedures. This paper gives a brief overview of the project organisation and describes the preparation, homogeneity and stability studies of two soil candidate reference materials (sewage sludge-amended and terra rossa soils).     

Fractionation of potentially toxic elements in urban soils from five European cities by means of a harmonised sequential extraction procedure

The revised (four-step) BCR sequential extraction procedure has been applied to fractionate the chromium, copper, iron, manganese, nickel, lead and zinc contents in urban soil samples from public-access areas in five European cities. A preliminary inter-laboratory comparison was conducted and showed that data obtained by different laboratories participating in the study were sufficiently harmonious for comparisons to be made between cities and land types (e.g. parks, roadside, riverbanks, etc.). Analyte recoveries by sequential extraction, with respect to direct aqua regia digestion, were generally acceptable (100 ± 15%). Iron, nickel and, at most sites, chromium were found mainly in association with the residual phase of the soil matrix. Copper was present in the reducible, oxidisable and residual fractions, whilst zinc was found in all four sequential extracts. Manganese was strongly associated with reducible material as, in some cities, was lead. This is of concern because high lead concentrations were present in some soils (>500 mg kg⁻¹) and the potential exists for remobilisation under reducing conditions. As would be expected, extractable metal contents were generally highest in older, more heavily industrialised cities. Copper, lead and zinc showed marked (and often correlated) variations in concentrations between sites within the same city whereas manganese and, especially, iron, did not. No overall relationships were, however, found between analyte concentrations and land use, nor between analyte partitioning and land use.     

The sequential analytical procedure as a tool for evaluation of As, Cd and Zn mobility in soil

The BCR EUR 14763 EN sequential extraction method, developed for the analysis of heavy metals in sediments, was applied to 35 soil samples covering the area of the Czech Republic. The soils varied in their physical-chemical properties and total element contents. While the residual fraction in the case of cadmium was only 18% of total Cd, for Zn and As the residual fraction was dominant (55 and 75%, respectively). The decreasing concentrations of extractable elements in the order Cd > Zn > As correspond to their availability in plants. The influence of selected soil properties (pH, sorption capacity, organic matter, and clay-silt-sand content) on the distribution of As, Cd and Zn was evaluated. Received: 3 August 1998 / Revised: 18 November 1998 / Accepted: 20 November 1998     

Cadmium analysis in soil by microwave acid digestion and graphite furnace atomic absorption spectrometry

The need to determine micronutrients and toxic elements in soils has grown in recent years and cadmium is of special interest. A method has been developed for the determination of cadmium in soils based on a prior acid digestion of the samples with nitric acid in closed Teflon vessels, into a microwave over. The cadmium determination was carried out by graphite furnace atomic absorption spectrometry (GFAAS) with Lvov platform. Optimum operating conditions, analyte modifiers and matrix interferences have been investigated. The best matrix modifier was found to be ammonium dihydrogen phosphate. The interferences are greatly reduced under these operating conditions and calibration can be performed with simple aqueous solutions of the metal standard. The method is rapid and provides accurate and precise results that agree with certified values for two reference materials: BCR 141 (calcareous loam soil) and BCR 277 (estuarine sediment).     

Analysis of Tea for Metals by Flame and Graphite Furnace Atomic Absorption Spectrometry with Multivariate Analysis

The concentrations of iron, zinc, manganese, copper, chromium, nickel, lead, arsenic, and cadmium were determined using flame and graphite furnace atomic absorption spectrometry in nine herbal tea samples. Hawthorn, yarrow, elderflower, and bearberry are herbal teas for which the metal content has been rarely determined. The concentration of cadmium in St John’s wort exceeded the maximum permissible limit of 0.3?mg/kg. The metals were also determined in aqueous extracts following 5, 10, and 20?min of boiling and using different preparations, including acidification with lemon juice. The influence of these factors on metal release was demonstrated using multivariate analyses by redundancy analysis and principal component analysis. The metal release was not considerably affected by the boiling time, while the acidity of the medium was generally positively correlated. For the infusions, arsenic was detected only in acidified mint tea. The extraction efficiencies of metals were determined and classified as highly, moderately, and poorly extractable, with chromium showing largest variations.     

Extraction procedures for the determination of heavy metals in contaminated soil and sediment

Extraction tests are commonly used to study the mobility of metals in soils and sediments by mimicking different environmental conditions or dramatic changes on them. The results obtained by determining the extractable elements are dependent on the extraction procedure applied. The paper summarises state of the art extraction procedures used for heavy metal determination in contaminated soil and sediments. Two types of extraction are considered: single and sequential. Special attention is paid to the Standard, Measurement and Testing projects from the European Commission which focused on the harmonisation of the extraction procedures and on preparing soil and sediment certified reference materials for extractable heavy metal contents.     

Organic complexation and total dissolved trace metal analysis in estuarine waters: comparison of solvent-extraction graphite furnace atomic absorption spectrometric and chelating resin flow injection inductively coupled plasma-mass spectrometric analysis

The measured concentrations of cadmium, cobalt, copper, nickel, lead, zinc, and manganese in acidified (pH<2) estuarine water samples analyzed for total dissolved trace metal concentrations using on-line chelating resin column partitioning with inductively coupled plasma-mass spectrometry (CRCP-ICP-MS) were compared to those analyzed by graphite furnace atomic absorption spectrometry (GFAAS) after liquid-liquid extraction using a combination of 1-pyrrolidinedithiocarbamate/diethyldithiocarbamate (PDC/DDC). Although there was good agreement between the two sets of analyses for cadmium, lead, manganese, and zinc concentrations, those of cobalt, copper, and nickel determined by CRCP-ICP-MS were found to be 10-20% lower than those determined by solvent-extraction GFAAS. The different yields were positively correlated (R>0.961, simple linear regression) to the dissolved organic carbon (DOC) concentration of the samples. Good agreement between the two methods for cobalt and copper was achieved after ultraviolet (UV) digestion of the acidified samples. Samples collected from the South Bay of the San Francisco Estuary with high DOC showed the greatest difference for cobalt, copper, and nickel which is tentatively attributed to complexation with humic material for copper and cobalt and strong synthetic chelating agents such as ethylenediaminetetraacetic acid (EDTA) for nickel. This is consistent with previous studies on copper, nickel and cobalt complexation in this region. We recommend UV digestion of acidified estuarine samples prior to multi-element analysis by chelating resin flow injection ICP-MS methods.     

川芎栽培土壤中重金属镉的动态监测

目的：连续多年监测彭州敖平镇川芎药材栽培土壤中重金属镉的含量,分析其对川芎药材中镉含量的影响。方法根据前期研究结果选取敖平镇部分川芎种植地固定采集样品。按照国家标准方法,采取0～20 cm连续根系土柱和川芎药材。采用火焰法对抽样土壤及川芎药材中镉的含量进行检测分析。结果采样区域内土壤中镉含量均符合国家二级土壤环境质量标准;部分土壤中镉的含量呈明显增长趋势。结论川芎种植土壤中镉含量与环境有较高关联,水泥厂粉尘等污染源是土壤中镉含量增加的重要来源。     

Investigation of heavy-metal uptake by vegetables growing in contaminated soils using the modified BCR sequential extraction method

The heavy metal (Cu, Fe, Co, Ni, Cd, Cr, Pb, Zn, and Mn) concentrations in soils and in vegetable samples, i.e. lettuce (Lactuca sativa L.), parsley (Petroselinum crispum), dill (Anethum graveolens), and onion (Allium cepa L.), taken from three urban vegetable gardens in Kayseri, Turkey, were determined by FAAS. The modified three-step sequential extraction procedure proposed by the European Bureau of References (BCR), now the Standards, Measurements and Testing Programme, was used in order to evaluate trace elements mobility in soil samples, and heavy-metal uptake by vegetables. Three operationally defined fractions were isolated using the BCR procedure: acid extractable (i.e. bound to carbonates), reducible (bound to Fe/Mn oxides), and oxidizable (bound to organic matter and sulphides). The vegetable samples were prepared to analysis using the wet-ashing procedure. To estimate the accuracy of the method used in analysis of the vegetable samples, the standard reference material (NIST SRM 1573a, Tomato leaves) was used. The results of recovery for all the elements were relatively satisfactory (87.7–108%). For the soil samples, the recovery values were calculated by proportioning the sum of the steps of the BCR procedure to those of the pseudototal digestion (i.e. aqua regia). In soils, the mobility of heavy metals followed the order Mn>Cd>Cu>Pb>Zn>Cr>Ni>Co>Fe. The relationship between the vegetable–metal and soil–extractable metal concentrations was examined in order to evaluate the bioavailability of metals, and the positive correlation, especially for the first (i.e. water, acid-soluble and exchangeable fraction) and for the third (i.e. oxidizable fraction) extraction steps, was obtained.     

洛阳市郊区叶菜中重金属含量抽样分析及评价

为了研究洛阳市郊区蔬菜中重金属污染状况,采用火焰原子吸收法对郊区李楼乡和孙旗屯乡抽取的叶菜样品中重金属Cu、Zn、Pb、Cd含量进行了测定。结果表明,8个蔬菜样品中Cu含量在0.393 9～0.970 7 mg/kg之间,Zn含量在1.395 0～10.080 0 mg/kg之间,均未超过国家蔬菜卫生限量标准;Pb含量在0.100 0～0.248 6 mg/kg之间,其中有3个样品Pb含量超出国家蔬菜卫生限量标准;Cd含量有5个样品未检出,其余3个样品也不超国标。经用单因子和综合因子污染指数评价,洛阳市郊区叶菜类蔬菜重金属污染大部分已处于警戒级到轻度污染,因此,应加强蔬菜中重金属污染的预防与治理工作。