Multivariate geostatistical analysis of soil contaminations

Soil is one of the most endangered compartments of our environment. The input of pollutants into the soil caused by industrial production, agriculture, and other human activities is a problem of high relevance. A contour analysis of soil contamination is the first step to characterize the size and magnitude of pollution and to detect emission sources of heavy metals. The evaluation and assessment of the large number of measured samples and pollutants require the use of efficient statistical methods which are able to discover both spatial and multivariate relationships. The evaluation of the presented case study – soil contamination by heavy metals – is carried out by means of multivariate geostatistical methods, also described as theory of linear coregionalization. Multivariate geostatistics connects the advantages of common geostatistical methods (spatial correlation) and multivariate data analysis (multivariate relationships). In the given case study of soil pollution by heavy metal emissions it is excellently possible to detect multivariate spatial correlations between different heavy metals in the soil and to determine their common emission sources. These emission sources are located in the area under investigation. Received: 2 October 1997 / Revised: 22 January 1998 / Accepted: 27 January 1998     

矿区重金属污染土壤修复技术的研究现状和展望

矿区土壤重金属污染是当今世界面临的主要环境问题之一,其污染修复一直是环境科学领域研究的重要领域之一。对矿区土壤重金属污染的修复方法,包括物理化学技术、植物修复技术、动物修复技术的机理、优缺点以及实用性进行了综述,并对矿区土壤修复的研究进行了展望。     

某冶炼厂周边土壤重金属污染评价分析及源解析研究

有色金属矿产资源采选冶活动造成的土壤重金属污染已成为严重的环境问题。采用电感耦合等离子体质谱法和光谱法测定某冶炼厂周边不同区域内土壤中重金属Cu、Pb、Zn、As、Ni、Cr、Cd、Hg元素含量,采用Kriging空间插值方法对重金属空间分布特征进行分析,采用内梅罗指数法对其污染状况进行评价,采用多元统计分析对重金属元素的污染源进行分析。结果表明,研究区土壤采样点80%处于污染状态,且以重度污染为主,污染比较严重的区域受风向影响在冶炼厂的西部和南部方向,污染严重的重金属元素为Cu、Pb、Cd、Zn和As,土壤中各重金属元素的污染源除来自于冶炼厂外,Zn-Cd-PbCu-As、Ni-Cr、Hg分别还受到机动车辆排放、自然因素、燃煤及农药使用的影响。     

Geostatistical and multivariate statistical analysis of heavily and manifoldly contaminated soil samples

The surroundings of the former Kremikovtzi steel mill near Sofia (Bulgaria) are influenced by various emissions from the factory. In addition to steel and alloys, they produce different products based on inorganic compounds in different smelters. Soil in this region is multiply contaminated. We collected 65 soil samples and analyzed 15 elements by different methods of atomic spectroscopy for a survey of this field site. Here we present a novel hybrid approach for environmental risk assessment of polluted soil combining geostatistical methods and source apportionment modeling. We could distinguish areas with heavily and slightly polluted soils in the vicinity of the iron smelter by applying unsupervised pattern recognition methods. This result was supported by geostatistical methods such as semivariogram analysis and kriging. The modes of action of the metals examined differ significantly in such a way that iron and lead account for the main pollutants of the iron smelter, whereas, e.g., arsenic shows a haphazard distribution. The application of factor analysis and source-apportionment modeling on absolute principal component scores revealed novel information about the composition of the emissions from the different stacks. It is possible to estimate the impact of every element examined on the pollution due to their emission source. This investigation allows an objective assessment of the different spatial distributions of the elements examined in the soil of the Kremikovtzi region. The geostatistical analysis illustrates this distribution and is supported by multivariate statistical analysis revealing relations between the elements.     

土壤重金属污染来源及其解析研究进展

土壤重金属污染问题是环境和土壤科学研究者关注的热点问题。对土壤重金属污染物来源的鉴别是准确、有效控制和治理污染源的前提。根据近年来国内外对土壤重金属污染的相关研究报道,综述了土壤中污染物的工业、农业和交通因子三大主要来源,重点阐述了目前解析土壤重金属污染来源所运用的化学形态研究、剖面分布、同位素示踪、空间分析和多元统计等方法,并就存在的问题和今后的研究重点进行了总结。     

长株潭地区土壤环境地球化学研究

通过长株潭地区环境地球化学调查工作的实施,对长株潭地区土壤环境地球化学研究的工作方法进行了初步研究。结果显示,工业区重金属中Cu、Zn、Pb、As、Cd的污染较严重,尤其是Cd,这说明工业生产所产生的废水、废气、废渣是引起土壤中重金属污染的主要原因;各功能区重金属含量由高到低顺序为:工业区,居民区,商业办公区,休闲区,居民区和休闲区中重金属超标可能是由生活废水、生活垃圾和汽车尾气引起的。     

泰安市城区土壤重金属污染特征及风险评价

为了解泰安市城区土壤重金属污染特征,对采集的30件土壤样品中6种重金属含量进行测定,利用单因子污染指数法、内梅罗综合污染指数法、地累积指数法和潜在生态风险指数法开展污染状况评价。结果表明：土壤中As、Cd、Cu、Pb、Hg、Ni的平均含量分别为6.72、0.066、20.33、18.19、0.031和19.92 mg.kg^-1,其中As、Cd、Cu、Pb、Ni的平均含量均低于泰安市和山东省土壤背景值,Hg的平均含量略高于泰安市土壤背景值,变异系数大于0.6,其含量受人类活动影响较大,空间分布差异性较大;除Hg的单因子污染指数为1.03,严重污染、中度污染、轻微污染和无污染采样点数量占比分别为3%、7%、23%和67%,其他重金属单因子污染指数平均值小于1,为无污染状态;重金属内梅罗综合污染指数平均为1.58～1.64,整体属于轻污染水平;土壤重金属累积较轻,多数为无污染状态,Hg的最大地累积指数为1.29,达中等-强污染(3级);综合生态风险指数RI的范围为39.96～191.81,平均值为77.60,综合生态风险等级为轻微,为低生态风险区,Hg为引起风险的主要因子;Cu、Ni含量较低,富集主要受土壤母质和自然过程的控制;Pb、Cd、As主要来源于自然背景因素,部分受人类活动影响;Hg的污染来源于化肥、塑料地膜和含重金属的无机农药使用,受农业活动和居民生活影响较大。     

冶炼厂烟囱降尘农田土壤重金属含量及潜在生态风险评价

摘要：为了研究冶炼厂下风向烟囱降尘对农田土壤重金属污染影响程度,以济源市某一冶炼厂工业烟囱下风向降尘覆盖农田土壤为研究对象,依次对距离该厂烟囱大约为750m-3000m的7个农田研究区（P1-P7）土壤中重金属（Hg、As、Pb、Cd、Cu、Zn、Ni、Cr、）含量进行污染状况分析,采用了单项潜在生态风险指数法和综合潜在生态风险指数法对冶炼厂下风向烟囱降尘土壤中重金属的潜在生态风险进行评价。结果表明：在3 km2研究区域范围内,距离冶炼厂越近土壤重金属含量越高,Pb、Cd为重度污染,超过了《土壤环境质量农用地土壤污染风险管控标准》（GB15618-2018）农用地土壤污染风险管制值的1.2倍,距离冶炼厂烟囱下风向P1区土壤中重金属As、Pb、Cd、Cu、Zn超过土壤环境质量农用地土壤风险筛选值,Cd 在浓度值均超过农用土壤污染风险管制值1.8倍,As元素平均浓度值超农用土壤污染风险管制值1.7倍,Pb、Cu和Zn污染较严重,Cd、Hg对综合指数（RI）贡献值较大分别为68.63和22.4。单项潜在生态风险指数评价结果显示Cd存在极严重的潜在生态风险,Pb、Cu存在较严重潜在生态风险,冶炼厂下风向土壤中综合潜在生态风险指数评价显示,冶炼厂下风向降尘土壤重金属具有较强的生态风险。     

湛江湾红树林湿地土壤重金属含量分析及污染评价

采用电感耦合等离子体发射光谱仪(ICP-AES)和电感耦合等离子体质谱仪(ICP-MS)对湛江湾红树林湿地土壤中8种重金属(As、Cu、Cd、Cr、Hg、Ni、Pb、Zn)含量进行测定,采用单因子污染指数法、内梅罗综合污染指数法和地累积指数法进行污染评价,并结合相关性分析和因子分析方法探讨重金属来源。结果表明:除Ni外,其余7种重金属元素含量平均值均未超过国家土壤环境质量标准(GB15618-2018);但Ni、Zn、Cu、Hg、As和Cd元素均超过广东砖红壤环境背景值,其中As、Ni、Hg和Zn元素超标情况严重。8种重金属元素内梅罗综合污染指数评价结果为0.373~22.576,平均值为3.378,整体处于重度污染;单因子污染指数依次为Ni>Hg>Zn>Cd>As>Cu>Pb>Cr。单个重金属元素地累积指数评价结果与内梅罗综合污染评价相一致,均显示红树林土壤中Hg、Zn和Ni元素污染严重,是影响研究区土壤环境质量的重要因素。从站位看,位于湾内北部的北涯村、观海长廊以及西部的世乔村站位污染较严重,高污染站位约占总站位数的33%,主要为Cd、Hg和Zn。统计分析结果显示,除Ni外,湛江湾红树林土壤中7种重金属元素之间显著相关;结合实地调查结果推测重金属污染主要来自工业污染、船舶排污、养殖排污、生活排污及农业面源污染等人为活动的输入,其次为自然因子的输入。     

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。     

Information theory for evaluating environmental classification systems

Environmental pollution data are often ranked in rule-based classification systems. These environmental data are separated in predetermined classes of a classification system for a better and smarter characterization of the state of pollution. Often the measured values are transformed, e.g. in pseudocolor maps, and can then be presented in maps. For some environmental compartments different classification systems for evaluating environmental loadings are used. Because of the dissimilarity of the various classification systems direct visual comparison is difficult. However, by means of information theory an objective comparison of these various classification systems based on their information content enables a decision to be made about which system is the most informative for objective assessment of the state of pollution. By means of the new measure multiple medium information content (multiple entropy) objective and simultaneous comparison of all channels (in an environmental classification system: pollutants) of each classification system is now possible. Furthermore the development of the state of pollution over the whole investigation period can be detected by means of information theory. On the basis of the conditions of the established rule-based systems the use of information theory enables definition of new ranges of classes in order to reach the optimum of information during conversion into the environmental classification system.     

山西省马铃薯主产区土壤重金属含量状况评价与膳食暴露评估

【目的】探明山西马铃薯种植区域土壤重金属污染状况,并对马铃薯进行重金属摄入健康风险评价。【方法】选取山西省境内马铃薯优势产业基地县(区)作为调查研究对象,用电感耦合等离子体质谱仪分析了马铃薯产地土壤及产品中铅、镉、砷、铬、镍、铜、锌等七种重金属元素含量状况,并采用单因子指数法、内梅罗综合指数法和潜在生态危害指数法对土壤中重金属进行生态风险评价,采用目标危险系数法对马铃薯进行重金属摄入健康风险评价。【结果】山西省马铃薯主产区土壤中7种重金属单项污染指数均小于1,综合污染指数小于0.5,潜在生态危害为轻微,土壤环境质量总体属于非污染水平,成人和儿童因食用马铃薯而摄入重金属的健康风险指数均小于1。【结论】山西省马铃薯主产区土壤中重金属污染程度较低,而马铃薯中重金属的残留对人体健康存在隐患,建议制定预防性手段,加强对马铃薯及其他蔬菜等土壤中重金属的跟踪与监测,确保农产品产地环境质量,从而确保农产品质量安全。     

Characterization of Heavy Metals in Soil Near Coal Mines and a Power Plant in Huainan,China

The environmental and health hazards posed by heavy metals are significant due to their toxicity and bioavailability. Thirty-two soil samples were collected from residential areas around three coal mines and a power plant to assess the environmental and health implications caused by mining activities. The concentrations of heavy metals in soil were determined by inductively coupled plasma mass spectrometry. To evaluate the risk levels, the geo-accumulation index and health risk assessment were determined. The concentrations of metals in power plant soil were generally higher than those in coal mine soil, suggesting a higher release during coal combustion. The results demonstrate that the soils in the vicinity of Xinzhuangzi Mine and Luohe Power Plant are moderately contaminated by arsenic and cadmium. The analysis of the health risk of the metals indicated that the non-carcinogenic and carcinogenic adverse effects to residents due to heavy metal exposure are negligible. However, more attention should be paid around the power plant for the unacceptable level of carcinogenic risk. Based on the results of the environmental and health risk assessment, priority control components in Huaian have been identified. The study provides a comprehensive assessment of soil heavy metal implications derived from mining activity in this region in China and is helpful for pollution control and environmental management.     

金华市土壤磁化率与重金属的空间变异特征

工业化、城市化的进程对城市土壤产生了巨大的环境压力。以浙江省金华市为典型区,采用地统计学方法对表层土壤的磁化率和Cr、Co、Ni、Cu、Pb等5种重金属结构特征和空间分布格局进行了分析,并从空间上寻找磁化率与重金属的关系。结果表明,(1)低频磁化率总体较低,频率磁化率总体偏高,都属于强变异,两者呈负相关。重金属Cu、Pb、Ni含量大多在土壤背景值之内,Cr、Co则有较多土样超过背景值。(2)从总体上看,磁化率与5种重金属相关性较弱。(3)低频磁化率、Pb、Co具有很强的空间相关性,频率磁化率、Ni、Cu具有中等的空间相关性,Cr的空间相关性较弱。(4)在空间上,低频磁化率与频率磁化率负相关明显;在城区西部和西北部,重金属Cr、Ni、Pb、Cu含量均相对较高,在城市中心,重金属Pb、Cu含量较高;Cr、Co与低频磁化率从空间上更多地表现出负相关,Co与频率磁化率在空间上正相关较明显。     

The potential of flow-through microdialysis for probing low-molecular weight organic anions in rhizosphere soil solution

In this paper, flow-through microdialysis is presented as a novel analytical tool for automatic sampling of low molecular weight organic anions (LMWOA), such as oxalate and citrate, in solid samples of environmental concern. The microsampling methodology involves the implantation of dedicated capillary-type probes offering unrivalled spatial resolution (ca. 200 μm) in definite soil sites. These passive samplers are aimed at monitoring local processes, such as the release of organic acids occurring in the rhizosphere environment, in nearly real-time.The influence of chemical and physical variables (composition and flow rate of the perfusion liquid, ionic strength and pH of the outer medium and presence of metal ions therein) was assessed in vitro using liquid-phase assays. On the other hand, the resistance of the external solid medium to mass transfer, and the actual applicability of in vivo calibration methods were investigated using quartz sand as an inert model soil. Microdialysers furnished with 3 cm long semipermeable tubular membranes were perfused with 0.01 M NaNO₃ at a flow rate of 2.0 μl/min, yielding dialysis recoveries ≥45% for both assayed LMWOAs in simulated background soil electrolyte solutions, and ≥24% in the interstitial liquid of complex solid samples.Full knowledge of the fate of LMWOAs in soils was obtained through the application of stimulus-response approaches that mimic the discrete exudation pulses of roots. Highly time-resolved microdialysates were used to discern readily available species such as free carboxylic anions and LMW metal-organic acid complexes from adsorbed, precipitated or mineralised analyte species in a variety of soil samples containing variable amounts of organic matter, exchangeable cations and different levels of metal pollution.     

Techniques in chemometrical modeling for micro-pollutants assessment

Summary Chemometrics have been described as effective tools for exploring chemical data, and many software packages are now available on micro-computers. This work evaluate their suitability for environmental analytical chemistry. Guidelines for multivariate method selection are proposed. They are based on the type of variables and the goal of the study. Two examples are proposed to illustrate these methods and their efficiency. Firstly it is shown that a global assessment of Rhine basin mercuric pollution in the Alsace region is possible with Multiple Correspondence Factor Analysis. Several goals are simultaneously reached: a mapping of pollution, a detection of pollution changes during the study period and an evaluation of bio-accumulation as a function of fish species. Secondly the modeling of industrial soil pollution by heavy metals is studied by Multiple Linear Regression. It demonstrates that chemometrics provide us with necessary tools for environmental analytical chemistry but also for toxicological studies or ecosystem modeling.     

环境领域铊元素的分析技术研究进展EI北大核心CSCD

铊是一种剧毒的蓄积性重金属元素。伴随着含铊矿物资源的开发利用,铊向环境中的迁移已不容忽视,环境铊污染事件时有发生。铊的分析技术对铊污染的防治具有重要意义。环境领域铊的分析技术近年来也有了新的发展。重点对环境水体、土壤、大气中铊元素分析技术的近期发展进行了综述。在电感耦合等离子体-质谱(ICP-MS)、石墨炉原子吸收光谱(GF-AAS)法为主流分析手段的同时,随着铊新型富集技术的应用以及仪器性能的提升,环境铊分析技术呈现出高灵敏、高稳定性的趋势。针对环境领域铊元素分析技术的发展,提出环境样品铊的化学及赋存形态分析、铊的在线监测、与铊高效富集技术的联用以及环境固体废物中铊的分析是其重要的发展方向。     

农田土壤中重金属对抗生素抗性基因及细菌群落的影响

抗生素滥用及其诱导产生的抗生素抗性基因(ARGs)污染是环境领域研究的新兴热点,农田土壤成为ARGs的潜在储库,同时重金属的胁迫不仅对ARGs产生持续性选择压力,也显著影响土壤细菌群落结构和功能。本文重点综述了土壤中重金属对ARGs和细菌群落丰度、多样性的影响,进一步揭示重金属污染造成ARGs水平转移的风险,最后讨论了如今研究中的不足,并对抗生素与重金属的复合污染研究进行了展望,以期为重金属与ARGs防控政策的制定提供理论依据和科学支撑。     

洛阳市蔬菜基地土壤中重金属含量抽样分析及评价

为了解洛阳市蔬菜基地土壤中重金属污染状况,对郊区白马寺镇蔬菜基地靠近公路、铁路、社区边和远离这些区域的菜地土壤抽样,采用原子吸收分光光度法测定了样品中的Cu、Zn、Pb、Cd、Cr 5种重金属元素含量,并根据国家土壤环境质量二级标准对检测结果进行单因子污染指数和综合污染指数评价。结果表明,土样中重金属Cu、Zn、Pb、Cd、Cr的平均含量分别为37.09、106.09、50.10、0.56、16.13 mg.kg-1。其中Cu、Zn、Pb、Cr含量均能达到清洁级,而Cd含量在靠近公路边、铁路边和社区边的抽样中明显高,接近或超出国家土壤环境质量二级标准值,在远离交通和社区的抽样中处于清洁级。由综合评价可知,在所采集的11个土壤样品中,4个样处于安全级水平,5个样处于警戒级水平,2个样处于轻度污染状态。可见,交通运输和社区生活是引起土壤重金属污染的重要因素。