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。     

淋洗处理土壤的重金属冲刷量测定

利用人工淋洗的方法模拟自然径流对土壤的冲刷,测定城市不同区域的各类土壤中重金属的冲刷量。通过电感耦合等离子体发射光谱(ICP-OES)法对铜、锌、铅、铬、镍5种重金属元素进行连续测定,回收率为96%～103%,线性相关系数r均大于0.999,相对标准偏差(RSD)小于5%。该方法灵敏度、精密度、和准确度均能满足相关检测标准的质量控制要求,具有多元素同时分析、样品前处理简单、干扰少、测定快速、准确等优点。该方法可以提高工作效率,对于大批量或突发性土壤重金属污染的监测具有实际应用价值。     

电感耦合等离子体发射光谱法与原子吸收光谱法测定土壤中重金属元素的比较

文章采用电感耦合等离子体光谱法测定土壤中As、Cd、Cu、Cr、Hg、Ni、Pb、Zn共8种重金属元素,与传统标准方法原子吸收光谱法进行了结果比对、并且通过加标回收率以及标准物质的测试进行验证,得出:电感耦合等离子体光谱法满足HJ/T166-2004《土壤环境监测技术规范》以及GB15618-2018《土壤环境质量农用地土壤污染风险管控标准》中对重金属检测的要求,并且该方法的检出限较低,满足土壤中重金属污染风险筛选值的要求;标准曲线测量范围宽,达到两个数量级,可满足各种含量土壤中重金属的测试;精密度均小于1%,重复性好,结果稳定可靠;线性拟合系数R=0.999～0.99999;与原子吸收法检测结果比对良好,加标回收率以及标准物质测试准确度高。该方法一次进样同时得到所需元素的结果,极大地提高检测工作效率,降低检测工作成本,适用于大批量检测土壤中重金属的含量。     

基于PMF模型的矿区土壤重金属来源解析

通过在某矿区采集农田土壤和菠菜样品,分析其中重金属含量,基于相关性分析和PMF模型对该矿区农田土壤重金属来源进行解析。结果表明,研究区土壤中Cd、As、Zn、Cr和Cu 元素明显富集,分别是当地土壤背景值的5.7倍、4.4倍、2.4倍、1.5倍和1.3倍;相关性分析结果显示,研究区内Cu、Zn、As、Cd元素存在一定的相关性,可能具有同一污染源;PMF模型结果说明,研究区土壤中重金属主要来源分别为工业污染源、自然母质源、交通污染源和农业污染源,其对当地土壤重金属污染贡献率分别为39.8%、22.8%、21.6%和15.8%。     

土壤重金属元素检测国际实验室比对研究

IERM和CNAS合作组织开展了亚太实验室合作组织(APLAC)能力验证计划"APLAC T066土壤重金属元素检测",其目的是评价参加实验室定量分析土壤重金属元素总量的能力。研究所用的能力验证样品为IERM研制的土壤标准样品。结果表明,参加实验室检测土壤砷、铜、汞、镍、铅和锌的结果满意率分别为85.7%、95.8%、77.1%、83.3%、93.5%和91.7%。样品消解过程加入氢氟酸时,铅和锌的检测结果与标准值更加接近,说明检测土壤重金属元素总量时氢氟酸的加入非常关键。文章还对比对实验室结果评价的统计方法进行了探讨。     

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%。     

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。     

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。     

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%。     

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。     

Heavy metal contamination of urban soils and dusts in Guangzhou, South China

The heavy metal concentrations of soil and dust samples from roadside, residential areas, parks, campus sport grounds, and commercial sites were studied in Guangzhou, South China. Heavy metals in samples were determined by inductively coupled plasma atomic emission spectrophotometer following acidic digestion with HClO₄ + HF + HNO₃. High concentrations, especially of Cd, Pb, and Zn, were found with mean concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in the urban dusts being 4.22?±?1.21, 62.2?±?27.1, 116?±?30, 31.9?±?12.6, 72.6?±?17.9, and 504?±?191 mg/kg dry weight, respectively. The respective levels in urban soils (0.23?±?0.19, 22.4?±?13.8, 41.6?±?29.4, 11.1?±?5.3, 65.4?±?40.2, and 277?±?214 mg/kg dry weight, respectively), were significantly lower. The integrated pollution index of six metals varied from 0.25 to 3.4 and from 2.5 to 8.4 in urban soils and dusts, respectively, with 61 % of urban soil samples being classified as moderately to highly polluted and all dust samples being classified as highly polluted. The statistical analysis results for the urban dust showed good agreement between principal component analysis and cluster analysis, but distinctly different elemental associations and clustering patterns were observed among heavy metals in the urban soils. The results of multivariate statistic analysis indicated that Cr and Ni concentrations were mainly of natural origin, while Cd, Cu, Pb, and Zn were derived from anthropogenic activities.     

The occurrence of heavy metals in irrigated and non-irrigated arable soils,NW Albania

The study analysed the content of heavy metals in surface soil and sediment samples from the Bregu i Matit Plain in NW Albania in relation to irrigation in order to evaluate the soil pollution and the potential risk to human health. Evaluation of soil pollution was performed using the enrichment factor and geo-accumulation index. Contents of cadmium, chromium and nickel of irrigated soils were significantly higher than those of non-irrigated soil, while contents of lead (in three of the irrigated locations), zinc and arsenic (in one of the irrigated locations) were significantly lower. Correlation analysis (CA) and principal component analysis (PCA) indicated that the primary source of the first three metals was irrigation, and the last three metals were originated from other anthropic sources, like the use of chemicals, etc. Enrichment factor (E _f) calculation showed that irrigated soils were most enriched in cadmium, chromium, copper and nickel. Index of geo-accumulation (I _geo) revealed that arable soils of Bregu i Matit are unpolluted to moderately polluted with cadmium, chromium, copper and zinc and moderately to strongly polluted with nickel and arsenic. The presence of heavy metals in the studied soils indicates a potential risk of transfer of these elements in the food chain. Therefore, further studies on the speciation of heavy metals in the studied soils in order to evaluate their mobility are needed.     

Pollution characteristics and ecological risk assessment of heavy metals in three land-use types on the southern Loess Plateau,China

The accumulation of heavy metals in agricultural soils has been the subject of great concern because these metals have the potential to be transferred to soil solutions and subsequently accumulate in the food chain. To study the persistence of trace metals in crop and orchard soils, representative surface soil samples were collected from terrace farmland that had been cultivated for various numbers of years (3, 8, 12, 15, and >20 years), terrace orchard land that had been cultivated for various numbers of years (4, 7, 10, 12, 15, 18, 25, and >30 years), and slope farmland with various gradients (3°, 5°, 8°, 12°, 15°, and 25°) and analyzed for heavy metals (As, Cr, Cu, Hg, Ni, and Zn). These samples were collected from Nihegou catchment of Chunhua county in the southern Loess Plateau of China. The six heavy metals demonstrated different trends with time or gradient in the three land-use types. The Cu and Zn contents of the soil were higher than the referee background values of the loessal soil, and the contents of Cr and Ni, and especially those of As and Hg, were lower. Cu was the only heavy metal that just met the Grade III Environmental Quality Standard for Soils of China, while the others reached grade I. Cu and Hg were considered contaminant factors and Hg was a moderate potential ecological risk factor in the catchment. Of the sites investigated, 89.5% fell into the category with a low degree of contamination (C _d ) and rest were moderate, while all three land-use types had low potential ecological risk (RI). Changes of C _d and RI were consistent with the cultivated time in the terrace farmland and terrace orchard land. Values of RI increased while C _d decreased with the increasing of slope gradient in the slope farmland. Evaluating the ecological risk posed by heavy metals using more soil samples in a larger study area is necessary on the Loess Plateau of China.     

Pollution, fractionation, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils from a Pb/Zn mining area

This study was conducted to investigate the pollution load index, fraction distributions, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils collected from a Pb/Zn mine in Chenzhou City, China. The samples were analyzed using Leleyter and Probst’s sequential extraction procedures. Total metal concentrations including Pb, Cd, Cu, and Zn exceeded the maximum permissible limits for soils set by the Ministry of Environmental Protection of China, and the order of the pollution index was Cd > Zn > Pb > Cu, indicating that the soils from both sites seriously suffered from heavy metal pollution, especially Cd. The sums of metal fractions were in agreement with the total contents of heavy metals. However, there were significant differences in fraction distributions of heavy metals in garden and paddy soils. The residual fractions of heavy metals were the predominant form with 43.0% for Pb, 32.3% for Cd, 33.5% for Cu, and 44.2% for Zn in garden soil, while 51.6% for Pb, 40.4% for Cd, 40.3% for Cu, and 40.9% for Zn in paddy soil. Furthermore, the proportions of water-soluble and exchangeable fractions extracted by the selected analytical methods were the lowest among all fractions. On the basis of the speciation of heavy metals, the mobility factor values of heavy metals have the following order: Cd (25.2–19.8%) > Cu (22.6–6.3%) > Zn (9.6–6.0%) > Pb (6.7–2.5%) in both contaminated soils.     

Quality assurance and quality control data validation procedures used for the Love Canal and Dallas lead soil monitoring programs

Public awareness of soils contamination has increased in recent years due in part to the notoriety associated with the indiscriminate release, packaging, transporting and disposal of hazardous materials. In 1980, and again in 1982, the U.S. Environmental Protection Agency (EPA) was responsible for designing, implementing and conducting environmental monitoring programs at Love Canal in Niagara Falls, New York, and in Dallas, Texas, that dealt with suspected contaminated soils. Both of these monitoring programs were conducted over a relatively short time with the collection and analysis of over 4000 soil samples. The methods employed by the Environmental Protection Agency for providing soil data that was scientifically valid and of defensible quality for each of these monitoring programs are presented. Also, methods for identifying data bias, its precision and its uncertainty are identified.     

Characterization, Source Identification and Apportionment of Selected Metals in TSP in an Urban Atmosphere

To understand the metal distribution characteristics in the atmosphere of urban Islamabad, total suspended particulate (TSP) samples were collected on daily 12 h basis, at Quaid-i-Azam University campus, using high volume sampler. The TSP samples were treated with HNO₃/HClO₄ based wet digestion method for the quantification of eight selected metals; Fe, Zn, Pb, Mn, Cr, Co, Ni and Cd by FAAS method. The monitoring period ran from June 2001 to January 2002, with a total of 194 samples collected on cellulose filters. Effects of different meteorological conditions such as temperature, relative humidity, wind speed and wind direction on selected metal levels were interpreted by means of multivariate statistical approach. Enhanced metal levels for Fe (930 ng/m³), Zn (542 ng/m³) and Pb (210 ng/m³) were found on the mean scale while Mn, Cr, Co and Ni emerged as minor contributors. Statistical correlation study was also conducted and a strong correlation was observed between Pb-Cr (r=0.611). The relative humidity showed some significant influence on atmospheric metal distribution while other meteorological parameters showed weak relationship with TSP metal levels. Regarding the origin of sources of heavy metals in TSP, the statistical procedure identified three source profiles; automobile emissions, industrial/metallurgical units, and natural soil dust. The metal levels were also compared with those reported for other parts of the world which showed that the metal levels in urban atmosphere of Islamabad are in exceedence than those of European industrial and urban sites while comparable with some Asian sites.     

生态修复后某矿区下游农田土壤金属污染特征与风险评价

为研究广东省某矿区开展生态修复多年后下游农田土壤的金属污染状况，选取该矿区下游某村周边农田土壤及灌溉水渠作为研究对象，对该区域采集了40个土壤表层样本和8个水体样本，利用Arcgis软件对农田土壤样品中As、Cu、Cd、Pb、Zn、Mn和Fe₂O₃的质量分数进行克里金空间插值，解析该区域农田土壤金属的空间分布特征；采用综合污染指数法和潜在生态风险指数法对该区域耕作层土壤中As、Cu、Cd、Pb、Zn和Mn进行风险评价。结果表明，40个土壤样品中As、Cd、Cu、Zn和Pb的超标率分别为77.5%、70%、87.5%、27.5%和67.5%,说明调查区域农田土壤污染属于多金属复合污染，且对农作物的生产和安全产生巨大的威胁。部分土壤样品中As、Pb和Cd含量超过了中国农用地土壤污染风险管制值，需采取严格管控措施。通过分析土壤金属的空间分布，发现土壤金属含量超标点位主要位于灌溉口与受污染河流周边，且含量与离灌溉口距离成反比。结合目前灌溉水样中的金属均未超标的情况，得出该区域农田土壤污染是由该矿区生态环境修复前所产生的含金属灌溉水导致土壤中金属的积累...     

Inorganic Ion Levels of Soils and Streams in some Areas of Ogoniland, Nigeria as Affected by Crude Oil Spillage

The inorganic ion concentrations of soils and streams in the three locations (Yorla, Zaakpon and Goi) in Ogoniland,Nigeria affected by crude oil spillage were investigated. In general, inorganic ion concentrations of polluted soilsand streams varied significantly (p = 0.05) from those of unpolluted soils and streams. Anions such as nitrate (NO ₃ ^- ), sulphate (SO ₄ ^2- ) and chloride(Cl^-) showed significantly (p = 0.05) higher values inthe polluted soils and steams than in the unpolluted controls. The phosphate (PO ₄ ^3- ) values were lowerin the polluted soils and streams than in the unpolluted controls.PO ₄ ^3- , NO ₃ ^- , SO ₄ ^2- and Cl^- concentrations were generally significantly (p = 0.05) higher in soils and streams from Yorla, Zaakpon and their control than in Goi North, Goi South and Goi control.Exchangeable cations and trace metal concentrations weresignificantly (p = 0.05) higher in the polluted soils andstreams than in the unpolluted controls. Yorla and Zaakponpolluted soils and streams had higher concentrations of theexchangeable cations and trace metals compared to valuesfrom Goi, except for Na. Results also showed significantlyhigher values of heavy metals (Pb, Cd, Cr and Ni) in the polluted soils compared to their controls, and values werealso significantly (p = 0.05) higher in Yorla, Zaakpon andtheir control compared to Goi North, Goi South and Goicontrol. Values obtained in polluted streams were higherthan in the unpolluted though not significant at the 5%level (p = 0.05). The anionic and cationic concentrationsof Yorla and Zaakpon soils and streams were generally higherthan those of Goi, indicating that Yorla and Zaakpon areaswere more polluted than Goi.Although the concentrations of most of the anions andcations analysed in the polluted soils and streams werewithin the World Health Organisation's permissible valuesfor the protection of humans and environment, the streams ofYorla, Zaakpon and Goi are in general being polluted withinorganic ions. This may make these soils and streamsunacceptable for domestic and industrial uses if not treated,and soils (farmlands) may also become unsuitable for agricultural purposes.     

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。     

微波消解法测定铅锌冶炼厂废旧除尘布袋及其飞灰中重金属的应用研究

以广东某铅锌冶炼厂的废旧除尘布袋及其布袋上的飞灰为实验材料,以HNO3-H2O2-HF对布袋及飞灰进行微波全量消解,采用BCR三步浸提法提取飞灰中Cu、Zn、Pb、Cr、Ni、Cd 6种重金属,并利用火焰原子吸收仪器检测布袋及飞灰中6种重金属的含量及飞灰中各形态含量。结果表明,铅锌冶炼厂废旧布袋和飞灰中重金属含量较高,远大于《国家土壤环境质量标准》(GB 15168—1995)三级标准值。不同重金属在飞灰中的形态分布差异较大,Ni主要以残渣态和酸可交换态为主,Cu和Pb以残渣态为主,Zn的4种形态分布都较均匀,Cd、Zn潜在的迁移性最强。