便携式XRF在污染地块土壤金属元素调查中的应用

研究了便携式X荧光光谱仪（PXRF）测定土壤中砷、铅、铬、铜、锌和镍的性能,评估其检出限、精密度和准确度,探索了土壤水分和粒径对测定结果的影响程度,并与常规实验室分析方法测定结果进行比对。结果表明,PXRF测定土壤中砷、铅、铬、铜、锌和镍的检出限为5~15mg/kg,标准物质测定结果的相对标准偏差（RSD）≤8.6%,相对误差在±15%以内。随着土壤水分含量的增加,各金属元素测定结果均呈下降趋势,而RSD有上升趋势。土壤粒径对测定结果的影响较小,随着土壤粒径减少,各金属元素测定结果的RSD略有下降趋势。PXRF可以简单、快速地测定多种重金属元素,适用于污染地块重金属元素的现场实时监测。     

便携式XRF测定仪在土壤检测中的应用及其影响因素

研究了便携式X射线荧光光谱仪(PXRF)的仪器性能,评估了其检出限、准确度及精密度,并和常规实验室检测方法比对进一步评估其性能,分析两者间的相关性和差异性。进一步探究了影响PXRF测定的2个最主要因素(土壤含水量和粒径)。结果表明:PXRF具备良好的仪器性能,8种元素的检出限为0.62～8.01 mg/kg,除Cd和Hg外,精密度均低于7%,准确度范围为-7.5%～11.1%。Pb、Cr、Cu、Zn、Ni、As的PXRF测定值与常规实验室方法测定值有良好的相关性,特别是Cu、Zn,相关系数可达0.873、0.832,而Cd和Hg的相关性则较弱。土壤含水量和土壤粒径会影响PXRF的测定性能,鲜样测定检测值普遍小于干样,0.15、2 mm粒径下检测值具有较强的相关性。研究旨在为PXRF的现场应用提供 参考,该方法可应用于初步监测和应急监测,实现土壤重金属元素的快速测定。     

杭州地区农业土壤中重金属的分布特征及其环境意义

为了分析杭州地区农业土壤重金属的分布特征及其环境意义,通过现场采样和室内分析检测的方法,对杭州市各区县不同作物农业土壤表层土中的Hg、As、Cu、Pb、Cr、Cd 6种重金属元素进行检测,并对其分布特征进行了分析。结果表明,杭州地区农业土壤中除As外,其他5种重金属的平均含量均低于且接近浙江省土壤背景值,个别采样点的重金属含量超过了土壤环境质量国家二级标准。总体上,杭州地区农业土壤处于安全水平。通过重金属的区域分布特征分析表明,余杭区和富阳市农业土壤中重金属平均含量普遍高于其他区域。萧山区和建德市部分农业土壤则存在Cu和Hg含量较高的情况,而淳安县农业土壤中重金属含量差异较大,土壤中出现了As、Cr和Cd含量最大值。不同作物的农业土壤重金属含量存在一定的差异,但不明显。水稻田和蔬菜地的土壤中,重金属含量较其他作物种植类型的土壤中含量高;叶菜类(蔬菜、茶叶)作物土壤中的Cd含量要比根茎类(水稻)、茄果类(水果)及其他作物种植类型的土壤中的含量低。目前杭州地区土壤中6种重金属含量均对作物的直接危害不大,但由于萧山区个别采样点Cu含量严重超标,淳安县土壤中Cd受外源性来源影响也已较明显,需要相关部门加大监管力度,防止污染事件发生。同时,为防止农业土壤中重金属含量进一步升高,需要加大大气降尘监测与治理、废气污染监管与控制治理。     

我国高速公路周边土壤重金属污染现状及研究进展

以我国高速公路周边土壤重金属为研究对象,综述了我国高速公路周边土壤重金属污染特征、影响因素、来源、环境风险及其研究进展。高速公路周边土壤主要受Pb、Cd、Cr、Cu、Zn等重金属污染,主要呈现指数分布、偏态分布和两者混合分布等特点,并且受到土地利用、风向、地形、车流量等多种因素的综合影响。土壤重金属的来源除了受成土母质等自然因素影响以外,公路交通和周边工农业活动也会对其来源产生较大影响。传统的土壤重金属评价方法主要采用单因子指数法、地累积指数法、生态风险评价法等对重金属的污染等级和环境风险进行评价。未来的研究应将重金属形态分析、空间和地统计分析、重金属稳定同位素示踪和源解析模型以及预测模型等多种手段相结合,开展高速公路周边土壤重金属的污染特征、时空分布、来源及预测预警研究等,为我国高速公路沿线工农业生产布局及其土壤重金属污染防控提供科学依据和决策支撑。     

Identification of heavy metal pollutants using multivariate analysis and effects of land uses on their accumulation in urban soils in Beijing, China

In order to evaluate the current state of the environmental quality of soils in Beijing, we investigated contents of 14 metals in Beijing urban soils inside the 5th ring road by even grids sampling. Statistic analyses were conducted to identify possible heavy metal pollutants, as well as the effects of land uses on their accumulation. Our results revealed that the urban soils in Beijing were contaminated by Cd, Pb, Cu, and Zn. Land uses and urbanization ages affected the accumulation of the four heavy metals in soils significantly. Soils in industrial areas have the highest average Cu and Zn contents, while Pb contents in park areas and Cd in agricultural areas are the highest. The accumulations of Pb and Zn in urban soils increase significantly with sampling plots approaching the city center. And Pb, Cd, and Zn contents in soils in traffic areas also tend to increase in the city center. However, residential areas have the lowest contents of all the four heavy metals.     

Distribution of heavy metals in agricultural soils near a petrochemical complex in Guangzhou, China

The aim of the study was to investigate influence of an industrialized environment on the accumulation of heavy metals in agricultural soils. Seventy soil samples collected from surface layers (0-20 cm) and horizons of five selected pedons in the vicinity area of petrochemical complex in Guangzhou, China were analyzed for Zn, Cu, Pb, Cd, Hg and As concentrations, the horizontal and vertical variation of these metals were studied and geographic information system (GIS)-based mapping techniques were applied to generate spatial distribution maps. The mean concentrations of these heavy metals in the topsoils did not exceed the maximum allowable concentrations in agricultural soil of China with the exception of Hg. Significant differences between land-use types showed that Cu, Pb, Cd, Hg and As concentrations in topsoils were strongly influenced by agricultural practices and soil management. Within a radius of 1,300 m there were no marked decreasing trends for these element concentrations (except for Zn) with the increase of distance from the complex boundary, which reflected little influence of petroleum air emission on soil heavy metal accumulation. Concentrations of Zn, Cu, Pb, Cd, Hg and As in the five pedons, particularly in cultivated vegetable field and orchard, decreased with soil depth, indicating these elements mainly originated from anthropogenic sources. GIS mapping was a useful tool for evaluating spatial variability of heavy metals in the affected soil. The spatial distribution maps allowed the identification of hot-spot areas with high metal concentration. Effective measures should be taken to avoid or minimize heavy metal further contamination of soils and to remediate the contaminated areas in order to prevent pollutants affecting human health through agricultural products.     

典型涉污企业周边土壤重金属污染特征及潜在生态风险评价

分析和评价典型涉污企业周边土壤环境质量,对于加强企业用地环境风险管控,实施土壤重金属污染精准防控,进一步保障农产品质量安全具有重要意义。以18类典型涉污企业周边土壤为研究对象,对475家企业周边的2 017个监测样点进行土壤重金属Cd、As、Pb、Hg、Cr、Cu、Zn和Ni元素含量测定,并采用主成分分析法、Hakanson 潜在生态风险指数法进行分析及评价。结果表明:典型涉污企业周边土壤重金属污染以Cd、Pb和As元素为主,各元素含量超过土壤污染风险筛选值的样品比例为9.82%~31.0%,超过土壤污染风险管控值的样品比例为4.46%~13.1%,其次是Zn、Cu、Hg和Ni,Cr无明显污染;主要污染元素Cd、Pb、As、Zn和Cu来自相同污染源且主要分布在有色金属矿采选业(B9)、黑色金属冶炼和压延加工业(C31)、有色金属冶炼和压延加工业(C32)、生态保护和环境治理业(N77)等行业企业周边;黑色金属冶炼和压延加工业(C31)、有色金属矿采选业(B9)、有色金属冶炼和压延加工业(C32)等行业企业周边土壤重金属潜在生态风险等级较高,中等风险及以上比例分别为76.0%、53.0%和54.1%。可见,典型涉污企业周边土壤重金属存在一定程度的污染,尤其是有色金属矿采选业(B9)等采矿业以及黑色金属冶炼和压延加工(C31)等制造业等,污染程度高,潜在生态风险大,需要加强监测和管控。     

Multi-scale spatial structure of heavy metals in agricultural soils in Beijing

To effectively investigate the spatial variability of heavy metals in soil, produce a higher quality spatial distribution map, and identify the potential pollution sources of heavy metals, geostatistics was employed to evaluate the effect of scale on spatial variability of heavy metals in Beijing agricultural soils. The results revealed that spatial variability of Cr, Ni, Zn, and Hg was dependent on scale. Validation of the optimality of theoretical semivariance and comparative analysis of the estimation accuracy demonstrated that the multi-scale nested model can reveal the spatial structure of heavy metals effectively and improve the estimation accuracy better than the single-scale method, thereby enabling production a higher quality spatial interpolation map. Thus, the multi-scale kriging nested model is a useful tool for revealing spatial variability of heavy metals in soils, while the spatial distribution maps allow the identification of hot spots with high concentrations of heavy metals.     

Geochemical characterization and biomonitoring of reclaimed soils in the Po River Delta (Northern Italy): implications for the agricultural activities

This geochemical study is focused on the easternmost part of the Po River alluvial plain in Northern Italy, which is interested by widespread agricultural activities, investigating a reclaimed sector of the Province of Ferrara, known as “Valle del Mezzano” (Mezzano Low Land, hereafter reported as MLL) characterized by peat-rich soils. The chemical–mineralogical characterization of these reclaimed soils is important to compare the local geochemical backgrounds with those recorded in other sectors of the River Po plain and to monitor if the observed concentration exceeds critical thresholds. The reported analyses include (a) measurement of the soil salinity, (b) nutrient evaluation, (c) major and trace element concentrations carried out on bulk soils, (d) tests of metal extraction with both aqua regia and EDTA to highlight the distinct elemental mobility and (e) phyto-toxicological measurement of heavy metal concentrations in plants (Lactuca sativa acephala) grown on the studied soils. The results indicate (1) high soil salinity, often with drastic increase of sodium and chloride along the soil profiles, (2) high nitrogen content (in part related to anthropogenic activities) on superficial horizons and nitrate decrease along the soil profiles and (3) comparative enrichments in heavy metals with respect to other soils of the province, which indicate that peat deposits are effective in trapping metals from anthropogenic sources. This, in turn, implies potential geochemical risks for the agricultural activities. In this regard, specific concerns are related to the high nickel and arsenic content of MLL soils due to the mobility of these elements and their attitude to be taken up by plants.     

Heavy metal pollution in surface soils of Pearl River Delta,China

Heavy metal pollution is an increasing environmental problem in Chinese regions undergoing rapid economic and industrial development, such as the Pearl River Delta (PRD), southern China. We determined heavy metal concentrations in surface soils from the PRD. The soils were polluted with heavy metals, as defined by the Chinese soil quality standard grade II criteria. The degree of pollution decreased in the order Cd?>?Cu?>?Ni?>?Zn?>?As?>?Cr?>?Hg?>?Pb. The degree of heavy metal pollution by land use decreased in the order waste treatment plants (WP)?>?urban land (UL)?>?manufacturing industries (MI)?>?agricultural land (AL)?>?woodland (WL)?>?water sources (WS). Pollution with some of the metals, including Cd, Cu, Ni, and Zn, was attributed to the recent rapid development of the electronics and electroplating industries. Cd, Hg, and Pb (especially Cd) pose high potential ecological risks in all of the zones studied. The soils posing significantly high and high potential ecological risks from Cd covered 73.3 % of UL, 50 % of MI and WP land, and 48.5 % of AL. The potential ecological risks from heavy metals by land use decreased in the order UL?>?MI?>?AL?>?WP?>?WL?>?WS. The control of Cd, Hg, and Pb should be prioritized in the PRD, and emissions in wastewater, residue, and gas discharges from the electronics and electroplating industry should be decreased urgently. The use of chemical fertilizers and pesticides should also be decreased.     

Soil heavy metal contamination in an industrial area: analysis of the data collected during a decade

Soil contamination by heavy metals has become a serious problem mainly because, above certain concentrations, all metals have adverse effects on human health. In particular, the accumulation of heavy metals in agricultural soils leads to elevated uptake by crops and affects food quality and safety. In this paper, we present the results of a study carried out over a decade for evaluating the impact of a new industrial settlement in an area geared to agriculture and livestock and far from urban sites. We focus our study on the bioavailable fraction of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in soil samples. Heavy metal concentrations in soil are analysed with both univariate and multivariate statistical procedures. The main goal of this paper is the development of a statistical procedure, based on a mix of multivariate analysis, able to compare field surveys carried out during different years and to characterize spatial and temporal changes in soil heavy metals concentrations.     

Metal Contamination in Urban Soils of Coastal Tuscany (Italy)

Urban soils are often contaminated by metals deriving from human activities. Urban polluted soils can affect human health through direct physical contact or through the food chain. The behaviour of metals is affected by chemical and physical soil properties. Heavy metal concentration was determined in some soils of three medium sized towns of coastal Tuscany, Central Italy. Soil samples were collected in roadsides, urban agricultural soils (allotments), playgrounds and public parks. The analysis included total metal content (Pb, Cu, Zn, Ni, Cd), and sequential extraction. Lead reached the highest levels in the soils and was higher near roads. In urban agricultural soils and in allotments Cu was present in noticeable quantities (300 mg kg⁻¹). The presence of Cu in urban soils seems to be typical of soils used for a long period as agricultural land, especially vineyards in the area covered by this study. Sequential extraction was performed to evaluate the mobility of the metals and to better understand the impact of the anthropogenic activity on urban sites. In the present study principal components analysis (PCA) is employed to describe the characteristics of urban soils.     

Magnetic susceptibility measurements as proxy method to monitor soil pollution: development of experimental protocols for field surveys

In the framework of the development of new methods for measuring and monitoring soil pollution, this paper deals with the use of magnetic methodologies to monitor the heavy metals presence in soils. In particular it shows a procedure for collecting magnetic susceptibility measurements in order to interpret them as proxy variable for monitoring heavy metals in soils. Magnetic measurements are carried out using a magnetic susceptibility meter with two different probes for in situ field surveys. The experimental procedure is divided in two parts. In the first part we carry out laboratory tests aimed to evaluate, for both the probes, the effective investigation depth for soil, the measurement reproducibility under different conditions, and the influence of water content. We complete this part comparing in situ measurements obtained by means of two probes with different characteristics. In the second part we carry out tests to evaluate the relationships between heavy metal levels and magnetic susceptibility values of soil samples. We investigate the variability of the magnetic susceptibility measurements contaminating different soil samples with well known concentration of heavy metals. Moreover we study the correlation between magnetic susceptibility values and metal concentrations, determined by means of AAS, in soil samples collected during a field survey. Results suggest that a careful check of the experimental procedure play a crucial role for using magnetic susceptibility measurements for heavy metals in situ monitoring. This is very helpful both for improving the quality of data and for making simpler data interpretation.     

Portable X-ray fluorescence in the characterisation of arsenic contamination associated with industrial buildings at a heritage arsenic works site near Redruth,Cornwall, UK

An investigation using in situ analysis by portable X-ray fluorescence (PXRF) has shown that contamination present on industrial buildings at a heritage arsenic works site near Redruth, Cornwall, UK results from the absorption of arsenic by porous and semi-porous building materials that were in contact with arsenic-rich flue gases. Results from a preliminary survey indicate that arsenic remains locked in these materials and is being gradually leached out by weathering processes. This weathering causes general contamination of the adjacent building surfaces averaging 1845 microg g(-1) arsenic, presumably caused by evaporation of leach solutions in contact with air at the surface of the building materials. More extensive crystalline deposits were found under arches protected from dissolution and further dispersion by rain water. These deposits appeared to comprise calcium sulfate (gypsum), associated with on average between 1.2 and 6.8% m/m As. In situ PXRF proved to be highly effective in locating sources of contamination at the site and in providing data that allowed a hypotheses for the origin of this contamination to be formulated and tested in the field.     

An approach to partition the anthropogenic and natural components of heavy metal accumulations in roadside agricultural soil

This paper describes a new approach that allows us to partition the anthropogenic and natural contributions to heavy metal accumulations in roadside agricultural soils. This approach, combining trend analysis and multivariate statistical analysis, partitions total heavy metals into three components: anthropogenic, natural, and unexplained residual. The approach was applied in a case study in Yixing City, China, to determine the spatial distributions of heavy metal accumulations. The results show that anthropogenic components of Pb, Cu, Zn, and Cd account for 52.4%, 23.04%, 5.09%, and 10.9% of total content, respectively. Spatial distributions of anthropogenic components are characterized by decreasing accumulation with increasing distance from the road. Ranges of influence of traffic for Pb, Cu, and Cd are beyond 300 m, whereas the range of Zn is less than 200 m. The spatial distributions of the four elements?? natural components show relatively similar distribution patterns. Assessments of variable partition methods show that the predicted values of Pb, Cu, Zn, and Cd are consistent with their measured values. The anthropogenic components extracted from total contents of heavy metal will be useful for modeling heavy metal accumulations produced by human activities.     

基于GIS的南京市典型蔬菜基地土壤重金属污染现状与评价

对南京市八卦洲蔬菜基地土壤中的铅、铬、铜和镉进行测定分析,利用不同的评价标准来评价其环境质量状况,同时借助GIS软件研究了污染指数的空间分布状况,并解析了其重金属污染的来源.结果表明,以自然背景值为评价标准,则蔬菜地土壤中的重金属都超过污染指标,其中镉为首要污染因子;以国标二级为评价标准,则除镉以外的三种重金属的单项污染指数值全都小于1,但其综合污染指数迭1.50,总体上属轻污染状况.南京化工因区、南京长江二桥和各种农业生产活动等可能是主要污染源.     

Deposition and storage of solid-bound heavy metals in the floodplains of the River Geul (the Netherlands)

Because of past mining activities, the floodplains of the River Geul are polluted with heavy metals. The continuous supply of fresh sediments during floods has caused the floodplain soils to exhibit large quality variations in time. By measurements of ¹³⁷Cs deposition rates in part of the floodplain area were determined at 0.4 to 2.7 cm yr^–1. Analysis of soil metal concentrations at various depths at 65 locations, revealed that the upper 40 cm of the soil profile deposited during the past 30–45 yr, exhibit the highest metal levels. The geostatistical interpolation technique kriging was used to map actual and past pollution patterns. It was shown that, as a result of variable deposition rates, the spatial correlation structure of soil metal concentrations becomes less clear with increasing depth/age. Kriged maps of average metal concentrations in the upper 100 cm of the soil profile provided the basis for the calculation of the mass storage of heavy metals.     

Soil Contamination Due to Heavy Metals from an Industrial Area of Surat, Gujarat, Western India

The pollution of soil is a source of danger to the health of people, even to those living in cities. The anthropogenic pollution caused by heavy industries enters plants then goes through the food chain and ultimately endangers human health. In the context, the knowledge of the regional variability, the background values and anthropogenic vs. natural origin of potentially harmful elements in soils is of critical importance to assess human impact. The present study was undertaken on soil contamination in Surat, Gujarat (India). The aims of the study were: i) to determine extent and distribution of heavy metals (Ba, Cu, Cr, Co, Ni, Sr, V and Zn) ii) to find out the large scale variability, iii) to delineate the source as geogenic or anthropogenic based on the distribution maps and correlation of metals in soils. Soil samples were collected from the industrial area of Surat from top 10 cm layer of the soil. These samples were analysed for heavy metals by using Philips PW 2440 X-ray fluorescence spectrometer. The data reveal that soils in the area are significantly contaminated, showing higher levels of toxic elements than normal distribution. The heavy metal loads of the soils in the study area are 471.7 mg/kg for Ba, 137.5 mg/kg for Cu, 305.2 mg/kg for Cr, 51.3 mg/kg for Co, 79.0 mg/kg for Ni, 317.9 mg/kg for Sr, 380.6 mg/kg for V and 139.0 mg/kg for Zn. The higher concentrations of these toxic metals in soils need to be monitored regularly for heavy metal enrichment.     

Use of sequential extraction to assess the influence of sewage sludge amendment on metal mobility in Chilean soils

In Chile, the increasing number of plants for the treatment of wastewater has brought about an increase in the generation of sludge. One way of sludge disposal is its application on land; this, however involves some problems, some of them being heavy metal accumulation and the increase in organic matter and other components from sewage sludge which may change the distribution and mobility of heavy metals. The purpose of the present study was to determine the effect of sewage sludge application on the distribution of Cr, Ni, Cu, Zn and Pb in agricultural soils in Chile. Three different soils, two Mollisols and one Alfisol, were sampled from an agricultural area in Central Chile. The soils were treated with sewage sludge at the rates of 0 and 30 ton ha(-1), and were incubated at 25 degrees C for 45 days. Before and after incubation, the soils were sequentially extracted to obtain labile (exchangeable and sodium acetate-soluble), potentially labile (soluble in moderately reducing conditions, K4P2O7-soluble and soluble in reducing conditions) and inert (soluble in strong acid oxidizing conditions) fractions. A two-level factored design was used to assess the effect of sludge application rate, incubation time and their interaction on the mobility of the elements under study. Among the metals determined in the sludge, zinc has the highest concentration. However, with the exception of Ni, the total content of metals was lower than the recommended limit values in sewage sludge as stated by Chilean regulations. Although 23% of zinc in sludge was in more mobile forms, the residual fraction of all metals was the predominant form in soils and sludge. The content of zinc only was significantly increased in two of the soils by sewage sludge application. On the other hand, with the exception of copper, the metals were redistributed in the first four fractions of amended soils. The effect of sludge application rate, incubation time and their interaction depended on the metal or soil type. In most cases an increase in more mobile forms of metals in soils was observed as the final effect.     

土壤重金属快速监测技术研究与应用进展

土壤重金属污染已经日益成为社会的主要环境污染问题之一,土壤重金属快速监测技术对于土壤重金属污染的快速有效筛查与监控具有重要意义。介绍了近年来国内外土壤重金属快速监测方法,并阐述了相关土壤重金属快速监测仪器的研究现状。在土壤重金属快速监测领域,X射线荧光光谱技术优势明显,激光诱导击穿光谱技术亦发展迅速,基于免疫学、酶抑制原理的快速监测技术正处于发展阶段。随着快速监测技术理论和方法的不断完善,土壤重金属快速监测仪器朝着高精度、小型化、智能化的方向发展,在区域性土壤重金属含量评估方面的应用将逐步拓展。