铅蓄电池企业废气中铅及其化合物便携式XRF检测方法

在企业污染源现场实现污染物排放浓度水平的快速判定和超标风险筛查,对生态环境管理部门提高执法效率、企业提高环境管理水平意义重大。铅是一种对人体危害极大的有毒重金属,目前缺少含铅废气中铅及其化合物的便携式直读检测设备和检测方法。探索性地将X射线荧光光谱(XRF)法应用于铅蓄电池企业含铅废气中铅及其化合物的便携式快速、直读检测。研究结果表明,基于XRF的面密度法适用于铅蓄电池企业含铅废气处理设施后铅及其化合物的快速、直读检测,相对国标方法具有快速、直读、对样品无损、便于复测等特点,可用于铅及其化合物排放浓度水平的快速判定和超标风险筛查。     

土壤中重金属可提取态(氯化钙法)分析质量控制样品的研制

为真实反映土壤中重金属的生态风险和环境效应,全国农用地土壤污染状况详查土壤检测要求测定土壤中重金属可提取态(氯化钙法)指标。针对农用地土壤污染状况详查分析质量控制工作要求,研制了土壤中重金属可提取态(氯化钙法)分析质量控制样品。土壤样品为采自江西省旱地农田的红壤,经除杂、干燥、球磨、筛分(0.250 mm)、混匀等加工处理后装瓶。采用重金属总量和重金属可提取态(氯化钙法)两大类指标评价土壤样品的均匀性,均匀性分析结果同时采用单因素方差分析法(F检验法)和相对标准偏差法(RSD法)评价。结果表明:土壤样品均匀性良好,样品最小取样量为4.0g。8家实验室对土壤中As、Cd、Cr、Cu、Hg、Ni、Pb和Zn等8种元素开展联合定值。标准值为联合定值结果的总平均值(X-),标准值上、下限值分别为(X-+3S)和(X--3S),S为联合测定平均值的标准偏差,低于《全国土壤污染状况详查土壤样品分析测试方法技术规定》中分析方法检出限的元素不做量值评定。As、Cd、Cu、Ni和Zn等5种元素评定了标准值,含量范围为0.190 ～ 13.6 mg/kg。Cr、Pb和Hg等3种元素分析结果低于分析方法检出限,未能定值。研制的土壤分析质量控制样品已应用于土壤详查工作,在保证土壤详查检测结果准确可比等方面发挥了重要作用。     

超声提取-电感耦合等离子体质谱法分析土壤中重金属化学形态

采用超声提取处理土壤样品,用ICP-MS分析样品中Cu、Zn、Pb、Cd、Ni、Cr等6种重金属元素形态,通过试验分析超声提取时土壤样品粒径、超声提取时间对提取效率的影响。方法在0.500μg/L~100μg/L之间线性良好,检出限为0.007μg/L~0.8μg/L,实际样品测定结果的RSD为4.7%~22.7%。土壤中重金属4种形态之和的总量与全量的相对偏差为11.0%~36.4%。将该方法与连续振荡法的试验结果比对,表明两方法对土壤样品的提取效率无显著性差异。     

WDXRF法测定污染土壤和沉积物中金属元素

采用土壤稀释〖CD*2〗波长色散X射线荧光光谱法（WDXRF）测定污染土壤和沉积物样品中的重金属和As,解决了由于元素含量高超出工作曲线测定范围产生较大误差的问题,确保测定结果的有效性。通过标准物质、实际样品的方法比对评估方法的准确度和精密度,该方法测定标准样品中多个无机元素的分析结果均满足国标准确度要求,与常规ICP OES法测定值一致,相对偏差均＜4.5%。     

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。     

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土壤重金属检测仪在环境应急监测中的应用探讨

系统评估了便携式XRF重金属检测仪的精密度、准确度及测定影响因素,开展了该方法测定土壤中Cu、Zn、As、Pb、Cr与国标分析方法的系统比对。结果表明:上述5种元素的方法检出限为5.7 mg/kg~16.0 mg/kg,土壤标准样品测定6次结果的RSD为1.0%~4.7%,Zn、Pb和As测定结果的相对误差10%;与国标法相比,便携式XRF重金属检测仪测定Cu、Zn、As、Pb的准确度较好,测定Cr的准确度波动较大。将该方法用于应急污染事故监测,可迅速锁定污染物及污染区域,实现野外分析的预判。     

偏振能量色散X-射线荧光光谱法测定土壤中Ni、Cu、Zn、Pb四种重金属元素

以土壤和水系沉积物标准物质为校准样品,采用粉末样品压片制样,建立了偏振能量色散X-射线荧光光谱仪测定土壤中Ni、Cu、Zn、Pb四种重金属元素的方法。该方法分别采用Ge,Zn,Zr等3个不同二次靶对被分析元素进行选择性激发和测定,利用经验系数和康普顿散射线作内标校正基体效应,优化了元素校准曲线方程,实验结果表明,土壤和水系沉积物标准物质准确度实验结果符合定值要求,方法精密度RSD在1.12%~6.09%之间(n=10),Ni、Cu、Zn、Pb四种重金属元素的检出限分别达到2.54、0.93、0.96、0.98 mg/kg。土壤样品测定值与原子吸收法测定结果一致,该方法准确度、精密度、检出限均能满足土壤检测的需要。     

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。     

水系沉积物重金属分析前处理方法

建立了水系沉积物中6种重金属分析的前处理方法,研究了样品粒径、消解前处理对测定结果的影响,对方法适用性作出评价,并对实际样品进行测定。结果表明:通过Hg元素含量的测定,粒径为0.147 mm的沉积物粒径可满足分析要求;采用微波-硝酸-盐酸-氢氟酸消解、ICP-MS法,对5种不同类型沉积物标准样品的6种重金属的测定结果显示,该方法精密度好、准确度高。利用建立的方法测定广西某河流湖库沉积物样品,6种元素测定结果 RSD为1.57%~11.1%,加标回收率大于74.4%。     

大冶龙角山地区土壤中重金属污染现状与评价

为了研究大冶龙角山地区尾砂坝内尾砂排放对下游耕地土壤中重金属含量的影响，本文对尾矿坝及河流两岸的耕地进行布点采样，通过等离子体发射光谱仪（ICP—OES）测定土壤中A5、Cd、Cr、Cu、Pb、Zn6种重金属的含量，并用污染指数法进行分析评价。旨在调查研究的基础上，使人们认识当地重金属污染的严重性，加大环境保护力度。     

典型重金属污染农田能源植物示范种植研究

为探索安全经济利用重金属中度-重度污染农田的模式,在浙江某典型重金属复合污染农田开展了能源植物(甜高粱Sweet sorghum、甘蔗Saccharum sinensisRoxb.、香根草Vetiveria和盐肤木Rhus chinensis)种植示范研究.结果表明,经施加0.1%的石灰和0.2%的磷矿粉改良后,土壤p...     

基于区间数排序法的农田土壤重金属生态风险分析

将土壤中重金属浓度以区间形式表示,运用土壤重金属生态风险分析模型得出风险区间。为区分风险等级并引入区间数排序法,建立了一种基于不确定性的区间数排序法的土壤重金属污染风险评价模型。运用该模型对不同研究区域土壤重金属生态风险和同一研究区域土壤中不同重金属生态风险进行分析。结果表明,A采样区的风险最大,其区间排序向量为0.275 5,区间向量排序为ABDEC,与内梅罗综合污染指数排序结果一致。区间数排序法考虑到评价过程中的不确定性,避免主观因素的影响。因此,土壤重金属生态风险量化结果更加客观直观,为风险管理提供较为精确的理论依据。     

Study on the law of heavy metal leaching in municipal solid waste landfill

Comparative leaching experiments were carried out using leaching medium with different pH to municipal solid waste in the landfill columns in order to investigate the mobility of heavy metals. The leachate pH and oxidation–reduction potential were measured by oxidation–reduction potential analyzer; the contents of heavy metals were measured by inductively coupled plasma mass spectrometry. It is very different in leaching concentrations of heavy metals; the dynamic leaching of heavy metals decreased with the rise of the leaching amount on the whole. Acid leaching medium had definite influence on the leaching of heavy metals in the early landfill, but it had the obvious inhibition effect on the leaching in the middle and late period of landfill; the neutral and alkaline leaching medium are more beneficial to the leaching of heavy metals. Due to the influence of the environment of landfill, the differences of the results in cumulative leaching amount, leaching rate, and leaching intensity of heavy metals are very big. The calculation results of the release rates of heavy metals prove that the orders of the release rates are not identical under different leaching conditions. Acid rain made heavy metals migrate from municipal solid waste to soil and detain in soil more easily; approached neutral and alkaline leaching mediums are more beneficial to leaching of heavy metals in the municipal solid waste and soil with leachate. The field verification of experimental data showed that the law of heavy metal leaching in municipal solid waste revealed by the experiment has a good consistency with the data obtained by municipal solid waste landfill.     

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.     

Sources and the distribution of heavy metals in the particle size of soil polluted by gold mining upstream of Miyun Reservoir,Beijing: implications for assessing the potential risks

Mining has been carried out upstream of Miyun Reservoir, Beijing, for several decades, and has caused metal emissions to the environment, threatening human health. We conducted a soil survey to assess metal contamination in this area and to determine distribution of heavy metals in the particle size. We attempted to determine the possible sources of the metals and the significance of metals in the fine particle fractions to soil risk assessments. Thirty-four soil samples were collected, and eight samples were partitioned into seven size fractions. Most of the metal concentrations in the soils were higher than the background levels in Beijing, and the metal concentrations and total organic matter (TOC) contents generally increased as the particle size decreased. Each metal except Hg significantly positively correlated with the TOC. The metals in the coarse-grained soils were mainly derived from parent materials, but the metals in the fine fractions were mostly anthropogenic. Statistical analyses showed that there were three metal sources: Cd, Cu, Hg, Pb, and Zn had anthropogenic sources; Co, Cr, Ni, and V had mixed anthropogenic and natural sources; and As and Be had natural sources. The trace metals were primarily in the clay and fine silt fractions, and they might pose health risks through the inhalation of resuspended soil particles (PM10 and PM2.5). The elevated accumulation factors, enrichment factors, and ecological risk indices for the metals in the fine fractions suggest that risk assessments should be based on the fine particle size.     

Laboratory-polluted soils: a methodological approach to establish equilibrium conditions for different metal chemical forms in soils

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.     

Further studies using X-ray fluorescence to sample lead contaminated carpeted surfaces

The sampling of carpeted surfaces to test for lead contamination primarily focuses upon vacuum techniques. Vacuum sampling techniques, however, require time-consuming, expensive laboratory analysis of the dusts obtained and are unable to determine total lead load on the carpet. X-ray fluorescence (XRF) analysis is an on-site, inexpensive, non-destructive, quick technique for predicting metals levels in a variety of media, such as water, soil, filter paper and painted surfaces. A 1992 study of the feasibility of XRF to analyze for lead and soil loadings on carpeted surfaces indicated that XRF can detect lead at a low enough level to warrant further study. This paper expands this earlier study and developes lead and soil loading calibration curves for three different carpet types based upon XRF lead L-beta peak areas and XRF iron and barium K-alpha peak and background areas. Results indicate that variation in the data can be reduced through modifications of the XRF analysis technique, thus reducing the statistically determined detection level, and that carpet type does affect the calibration. Detection levels of approximately 70 mg/m² for lead and 5 g/m² for soil were obtained. Overall, good agreement was found between results of this study and the earlier one. XRF shows excellent potential for quantitative analysis of lead on carpeted surfaces.     

Bioindication of a surplus of heavy metals in terrestrial ecosystems

A survey of the methods of boindication of heavy metals in terrestrial ecosystems and their effectiveness for predicting the consequences of environmental stress on organisms is presented. Two main inputs of heavy metals for terrestrial ecosystems have been considered: airborne and soil-borne. Airborne metals can be monitored due to physical adsorption on plant surfaces or due to chemical exchange processes in cell walls. Active biomonitoring widely uses both aspects, however, without predictive values. Meaningful bioindication of soilborne heavy metals can only be achieved by passive monitoring. Due to the different functions of heavy metals in organisms-micronutrients and trace elements-the knowledge of natural background values is important, considering the qualitative aspects of metals in the soil. In exceptional situations morphological and anatomical changes of plant organs will facilitate bioindication; in every case chemical analysis of the concentration of heavy metals is an essential part of the monitoring program. A long-term exposure of organisms to heavy metals will influence the genetic structure of populations. Therefore measurement of heavy metal tolerance of plants has to be a standard procedure in monitoring programs.