川中丘陵区铁路旁土壤重金属含量及化学形态研究

对川中丘陵区成昆铁路的三圣段、吴场段和成渝铁路的五凤段3个典型路段铁路沿线土壤重金属Cd、Zn、Cu、Pb含量及其化学形态进行了研究,并运用次生相富集系数法对重金属的潜在生态风险进行评估。结果表明:铁路沿线土壤重金属Cd、Zn、Cu、Pb含量与对照点相比都有不同程度的升高。Cd不仅具有高的含量,且化学形态主要为酸可交换态和可还原态,残渣态含量很低,其有效态比例>75%,具有很强的生物活性和可迁移性。Cu、Pb、Zn的化学形态则主要为残渣态,酸可交换态比例很小,但是Pb和Zn的可还原态和可氧化态比例较高,所以有效态比例也较高,分别为51.1%~54.9%和36.2%~50%。土壤重金属Cu在各典型路段的次生相富集系数为1.4~4.2;Zn在三圣段、吴场段2个典型路段的次生相富集系数超过3.0,均具有较大的潜在生态风险。     

Determination of heavy metals (Pb, Cd, Cu, Zn, Cr) in sedimentary reference materials with IDMS: total concentration and aqua regia soluble portion

Summary The total concentration and the aqua regia soluble portion of traces of Pb, Cd, Cu, Zn, and Cr are determined with isotope dilution mass spectrometry (IDMS) in three different types of sediments using a thermal quadrupole instrument (THQ). The results are compared with those obtained by other methods during a certification project to establish these sediments (BCR 277, BCR 280, BCR 320) as standard reference materials. The IDMS (THQ) results are in good agreement with the preliminary certification values and the results of two other laboratories, which applied IDMS using magnetic sector field mass spectrometers. Significant differences between the different analytical methods were found for the total Pb concentration, which could be explained by adsorption and coprecipitation effects during the chemical pretreatment of samples. Using aqua regia instead of HF/HNO₃ for the decomposition of sediments, only 65%–95% of the total Pb and 60%–90% of the total Cr could be dissolved. On the other hand, only a small or negligible portion of Zn, Cd, and Cu could not be dissolved by aqua regia. The IDMS values for the aqua regia soluble Cr portion are significantly higher compared to the results of other methods. This can be explained by adsorption effects.

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Bestimmung von Schwermetallen (Pb, Cd, Cu, Zn, Cr) in sedimentären Standard-Referenzmaterialien mit massenspektrometrischer Isotopenverdünnungsanalyse: Totalgehalt sowie in Königswasser löslicher Anteil

     

Certification of the contents of some heavy metals (Cd, Cu, Hg, Ni, Pb and Zn) in three types of soils

Summary The element contents of Cd, Cu, Hg, Ni, Pb and Zn of three types of soil were certified. The preparation, homogeneity and stability are reported. The certified contents as well as values for Co, Cr, Mn and Se and for the aqua regia soluble contents Cd, Cr, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Cu, Hg, Ni, Pb und Zn) in drei Bodenproben

Zusammenfassung In drei verschiedenen Bodenproben wurden die Elementgehalte an Cd, Cu, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Bereitung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt an Cr, Co, Mn und Se und der Gehalt an königswasserlöslichem Cd, Cr, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Comparison of aqua regia and HNO3-H2O2 procedures for extraction of Tl and some other elements from soils

The relationship between aqua regia (ISO 11466) and HNO(3)-H(2)O(2) (ISO/CD 20279) extraction procedures for atomic emission spectrometric (ICP/OES and ICP/MS) determinations of Tl, P, Mn, Fe, Mg, Ca, Sr, Al, K, As, Bi, Zn, Pb, Co, Cd, Ni, V, Be, Cu and Cr was investigated. Soil samples (155) representing areas with different contents of the elements were selected for the comparison. Tl was the element of the highest interest and therefore the sampling sites were chosen to achieve as wide range of Tl contents as possible. Both extraction procedures are comparable in results (differences lower than 10% for the most of the elements) for all the tested elements. Statistically non-significant differences between the two extraction procedures were found for P, Zn, V and K (the slope was very close to 1 and the intercept included zero). Statistically significant values of intercepts were found for Fe, Al, Ca, Cd, Sr and Ni. Significantly higher results for aqua regia were found for Cu (12%), Pb (17%), Mn (11%) and lower results by aqua regia were found for Mg (4%), As (13%), Co (20%), Be (11%), Cr (4%) and Bi (6%). The results for Tl, the element of the highest interest, after HNO(3)-H(2)O(2) extraction procedure, were approximately 6% higher than the results after aqua regia extraction. Content of Tl in the soil samples was from 0.08 to 2.8 mg kg(-1). A highly significant linear relationship was found (R(2)=0.97).     

Assessment of Heavy Metal Pollution and Ecological Risk of Roadside Soils in Tlemcen (Algeria) Using Flame-Atomic Absorption Spectrometry

In Algeria, few studies have been conducted on the evaluation of roadside soil pollution. A total of 34 soil samples (28 roadside and 6 off-road) was obtained at 0–20?cm depth along the RN 35 national road. Heavy metal (Cd, Cr, Cu, Fe, Ni, Pb, and Zn) contents were extracted using aqua regia digestion and determined using atomic absorption spectrometry. Background values of heavy metal contents were determined using the robust statistical method of median plus two times the median absolute deviation. Single- and multi-element pollution and ecological risk indices were calculated. The results showed that background values were 2.5?±?0.3, 64.9?±?8.1, 28.0?±?4.1, 29371.5?±?4403.0, 32.9?±?4.4, 72.2?±?12.8, and 445.1?±?62.9?mg/kg for Cd, Cr, Cu, Fe, Ni, Pb, and Zn, respectively. The results were all higher than their corresponding median values. Single-element pollution indices (enrichment factor and geoaccumulation index) showed that the pollution is primarily due to Pb and Zn. Multi-element pollution index (Nemerow index) indicated that only 3% of the soil samples are strongly contaminated, whereas 23% are seriously contaminated. The potential ecological risk index showed that Cd is the most harmful element, followed by Pb and Zn. 65% of the soil samples had moderate potential ecological risk, while only 3% had considerable potential ecological risk. This study may be used as a baseline for future monitoring and as a tool for decision-making regarding environmental protection policies and sustainability of this semiarid agroecosystem.     

Competitive sorption and desorption of heavy metals in mine soils: influence of mine soil characteristics

Many mine soils are chemically, physically, and biologically unstable and deficient. They are sometimes amended with sewage sludge and ashes but often contain heavy metals that increase the already high mine soils' heavy metal contents. Cd, Cr, Cu, Ni, Pb, and Zn in mutual competition were added to five mine soils (Galicia, Spain). Soil capacities for heavy metal sorption and retention were determined by means of distribution coefficients and selectivity sequences among metals. Influence of soil characteristics on sorption and retention was also examined. Retention selectivity sequences indicate that, in most of the soils, Pb is the preferred retained metal, followed by Cr. The last metals in these sequences are Ni, Cd, and Zn. Soil organic matter content plays a fundamental role in control of Pb sorption. Gibbsite, goethite, and mica influence Cr retention. Soil organic matter, oxides, and chlorite contents are correlated with K(d sigma sp medium). Heavy metals are weakly adsorbed by soils and then desorbed in high amounts. To recover these soils it is necessary to avoid the use of residues or ashes that contain heavy metals due to their low heavy metal retention capacity.     

Determination of heavy metal traces in metallic materials with IDMS

Summary Two pure copper samples were analysed for Cr, Ni, Zn, Cd, and Pb with isotope dilution mass spectrometry (IDMS) as a part of a certification campaign of the European Community Bureau of Reference in Brussels. Additionally, one commercially available copper powder was determined for Zn, Cd, and Pb. After dissolution of the sample in aqua regia Pb was separated from the matrix by anodic electrodeposition, the other elements by anion-exchange chromatography. Positive thermal ions were produced in a single-filament ion source using the silica gel technique with phosphoric acid for Zn, Cd, and Pb and with boric acid for Cr and Ni. Most of the heavy metals could be determined with relative standard deviations of about 1% down to the ng/g level. The detection limits were 13 ng/g for Zn, 4 ng/g for Ni, 2 ng/g for Cr, 1 ng/g for Pb, and 0.03 ng/g for Cd. The results were compared with those obtained by another IDMS laboratory and by other methods applied during the certification campaign.

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Bestimmung von Schwermetallspuren in metallischen Werkstoffen mit der massenspektrometrischen IsotopenverdünnungsanalyseTeil 1. Bestimmung von Cr, Ni, Zn, Cd und Pb in reinem Kupfer

     

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。     

采集的生物膜中痕量重金属的形态分布特征

采用改进的Tessier连续萃取方法对从松花江中采集的生物膜中锰、 铁、 铜、 铅、 锌及镉的化学形态进行分析, 考察了生物膜上铁、 锰氧化物和有机质吸附重金属的相对作用, 同时讨论了在研究培养的生物膜吸附痕量重金属时所建立的选择性萃取方法对于采集的生物膜组分分离的适用性. 研究结果表明, 在采集的生物膜上痕量重金属以铁、 锰的氧化物为主要结合形态存在, 以此种形态存在的铜、 锌、 铅和镉分别占其总含量的62.9%, 58.3%, 53.8%和32.6%, 而以有机结合态存在的铜、 锌、 铅和镉, 分别占其总含量的1.1%, 0.6%, 9.9%和1.8%, 表明采集的生物膜上铁、 锰氧化物在吸附重金属的过程中起主要的控制作用, 而有机质的作用相对较小, 与以往利用选择性萃取技术研究培养的生物膜吸附重金属的规律一致. 进一步分析表明, 如扣除生物膜上铁的残渣态部分, 则选择性萃取分离技术可以有效地将采集的生物膜上的铁、 锰氧化物及有机质分离开.     

Environmental Implications of Heavy Metals in Soil from Huainan,China

Soil metal contamination is of great concern due to these elements’ bioavailability, toxicity, and persistence. A total of forty soil samples were collected from mining, industrial, agricultural, and residential areas. Inductively coupled plasma–mass spectrometry (ICP–MS) was employed to determine the concentrations of the heavy metals (As, Cd, Cr, Cu, Pb, and Zn). Geoaccumulation indices and health risk assessment models were employed to evaluate the potential ecological and health implications. The concentrations of As, Cr, and Zn in the industrial zone were higher than the values from the other areas, whereas the concentrations of Cd, Cu, and Pb were highest in the residential area. The distribution of metals may be attributed to different anthropogenic sources. The soils in the industrial area were moderately contaminated by As. The noncarcinogenic risk due to metals was determined to be negligible in these areas, while a high carcinogenic risk was obtained in the industrial area. The priority controls should be As, Cd, and Cr in the industrial area. However, the ecological, environmental, and health implications in the mining and residential areas should also be monitored. This study provides a comprehensive investigation of soil metals in industrial, mining, residential, and agricultural areas in China that may be employed for future environmental management and regularization.     

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.     

成都市农业土壤重金属污染特征初步研究

对成都市农业土壤中七种重金属元素Pb、Hg、Cr、As、Cu、Zn和Cd进行了测定和研究,并进行了潜在生态风险评价。结果表明,成都市农业土壤重金属元素含量分别为:Pb 77.27mg/kg,Hg 0.31 mg/kg,Cr 59.50 mg/kg,As 11.27 mg/kg,Cu 42.52 mg/kg,Zn 227.00 mg/kg,Cd0.36 mg/kg;重金属潜在的生态危害因子表明,Hg和Cd达到中等生态危害程度,Pb、As、Cu、Zn、Cr达到轻微生态危害;多种重金属的生态系统的潜在生态风险指数(RI)表明,成都市农业土壤生态危害级别为中等生态危害。     

贵阳污灌区菜地土壤团聚体中有机碳和重金属的含量特征及相关性分析

以贵阳某污灌区菜地土壤为研究对象,分别采用微波消解-电感耦合等离子体质谱(ICP-MS)法和水合热重铬酸钾氧化分光光度法分析不同粒径土壤团聚体中重金属和有机碳的含量特征,并对有机碳和重金属的相关性进行分析。结果表明,以2mm粒径团聚体的含量为最高,约占75%。Cu、Zn、Cd和Pb在0.25～0.5mm粒径团聚体中含量最高,Cr在5～8mm粒径团聚体中含量最高,As在不同粒径团聚体中的含量变化不大,重金属含量随土层深度增大而减小。土壤重金属富集因子表现为CuPbCdZnCrAs,Cu、Zn、Cd和Pb在0.25～0.5mm粒径团聚体中分布因子最高,而在5～8mm粒径团聚体中重金属的质量负载因子最大。土壤有机碳含量随团聚体粒径的增大表现为先增大后减小,不同粒径团聚体中Cu、Cd、Pb和As含量与有机碳含量均呈显著正相关(p0.05)。污灌区菜地土壤Cr、As在5～8mm粒径团聚体中富集现象显著,Cu、Zn、Cd、Pb在0.25～0.5mm粒径团聚体中均表现出显著的富集特征。6种重金属在5～8mm粒径团聚体中的质量负载因子均为最高,表明6种重金属在5～8mm粒径团聚体中的贡献最大。     

成都市东郊土壤中重金属元素垂直分布研究

采用王水消解样品,利用原子吸收分光光度法,对重金属元素(Cu、Pb、Zn、Cd)在成都市东郊土壤中的垂直分布进行了研究。该法对Cu的回收率为98%~104%,精密度为2.75%;Pb的回收率为95~97%,精密度为3.11%;Zn的回收率为99%~101%,精密度为2.31%;Cd的回收率为97%~102%,精密度为3.32%,测定方法简单、准确。     

Comparative study of optimised BCR sequential extraction scheme and acid leaching of elements in the certified reference material NIST 2711

The optimised BCR sequential extraction procedure and a 4 h 1 mol L⁻¹ HCl partial extraction have been performed on the NIST 2711 reference material for a suite of 12 elements (Cd, Sb, Pb, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As) using magnetic sector ICP-MS. A pseudo-total aqua regia digest of NIST 2711 has also been undertaken for quality assurance purposes, and comparison of the sum of the four BCR fractions, which included an aqua regia digest on the residue, with the pseudo-total aqua regia digest has been used to assess the accuracy of the BCR partitioning approach. As a result of this work, discrepancies between previous studies about BCR partitioning of elements in NIST 2711 have been discussed and an increase in confidence about the use of BCR partitioning scheme on seven elements (Cd, Pb, Al, Mn, Fe, Cu, Zn) in this standard material has been obtained. On the other hand, BCR partitioning for Sb, Cr, Co, Ni and As has been provided for the first time. Partial extraction results are also reported for the same 12 elements analysed by the optimised BCR procedure, with the partial extraction results exhibiting a strong correlation with the sum of the three labile steps of the BCR procedure.     

Certification of the contents of some heavy metals (Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn) in three types of sewage sludge

Summary The element contents of Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn of three different types of sewage sludge were certified. The preparation, the homogeneity and the stability are reported. The certified contents as well as values for Cr and Se and for the aqua regia soluble contents of Cd, Cr, Co, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn) in drei Klärschlammproben

Zusammenfassung In drei verschiedenen Klärschlammproben wurden die Elementgehalte an Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Herstellung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt von Cr, Se und der Gehalt an königswasserlöslichem Cd, Cr, Co, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Statistical Evaluation of Bioavailability of Metals to Grapes Growing in Contaminated Vineyard Soils using Single Extractants

This article describes the statistical evaluation of concentrations of Cd, Co, Cr, Cu, Fe, Mn. Ni, Pb. Zn, Ca. and Mg metals determined in twenty-two grape and corresponding soil samples from around a zinc smelter in Kayseri. Turkey. In the analyses of soil samples. three different extraetants. 0.1 M HCl in 0.025 M H₂SO₄, 1 M NH₄OAc, and aqua regia (1HNO₃ + 3HCl), were used to extract and determine the leachable metal contents which are acid soluble, exchangeable, and total. respectively. A mixture of HNO₃ and HCIO₄ was used to dissolve grape samples. The determinations of metals were performed by flame atomic absorption spectrometry (FAAS). The analytical data were evaluated by using principal component analysis (PCA). hierarchial cluster analysis (HCA), correlation analysis (CA), and enrichment factors (EF). The relationship between the grapemetal and soil-extractable-metal concentrations was examined to evaluate the bioavailability of metals in soil to grape samples. As a consequence of statistical evaluations. Cd, Pb, Zn. Mn. and Fe labile levels in soil were related to total grape-metal contents indicating the method’s suitability for bioavailability studies in polluted soil–plant systems.     

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。     

煎煮对几种特色南药中重金属元素含量和形态影响

考察了几种特色南药中重金属(Cd,Cr,Cu,Fe,Mn,Ni,Pb,Sr,Zn)的含量状况,并采用形态连续萃取法分析重金属在药材中的形态分布,研究了药材煎煮时药材中重金属的释放及煎煮过程对药材中重金属形态分布的影响。结果表明,几种南药中Cr,Pb,Zn的含量较高,且巴戟天中的重金属总量高于限量标准;原药材中Cr,Cu,Mn,Ni,Pb和Zn主要存在于有机态和残留态,Fe和Sr主要存在于残留态。煎煮使南药中大量重金属迁移到药汤中;药汤中Cu,Mn,Cr,Pb和Zn主要来自于其在药材中的可交换态、碳酸盐结合态和有机态,而药汤中Sr,Ni和Fe不仅包含其非残留态,更多来自于它们的残留态。为减少药汤中重金属,对于Cu,Mn,Cr,Pb和Zn既要控制在药材中的总量,且需降低它们在药材中的非残留态含量;对于Fe,Ni和Sr则主要是控制其在药材中的总量。     

Use of INAA in the preparation of a set of soil reference materials with certified values of total element contents

A set of certified Reference Materials was prepared consisting of four natural agricultural soils with normal (n) and elevated (e) levels of element contents: CRM 7001 Light Sandy Soil (n), CRM 7002 Light Sandy Soil (e), CRM 7003 Silty Clay Loam (n), and CRM 7004 Loam (e). In these materials, certified and/or information values of the total contents of the elements As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, V and Zn, and their fractions extractable by aqua regia, boiling and cold 2M nitric acid were derived from an interlaboratory comparison in which 28 laboratories participated. Highly precise and accurate procedures of instrumental neutron activation analysis (INAA) were employed for homogeneity testing and also for certification of the total element contents. For comparation purposes, NIST SRM-2704 Buffalo River Sediment was analyzed by INAA, as well. The INAA results obtained compared very well with the certified and/or information values for four soil CRMs and also with NIST values for SRM-2704. From this agreement, a very high reliability of the new soil CRMs can be inferred.