Mineralogical Associations of Arsenic and Antimony in Thirty Five Geochemical Reference Materials by Sequential Extraction with Hydride Generation and Atomic Absorption Spectrometry

A method is described to estimate the chemical forms of arsenic (As) and antimony (Sb) in a variety of geochemical reference materials, combining a sequential extraction scheme with hydride generation and atomic absorption spectrometry (HG-AAS). The fractions dissolved by sequential extraction are empirically defined as the exchangeable, EDTA soluble, oxide, sulfide and residual fractions. The amount of As and Sb in the EDTA soluble fraction have been derived mainly from oxide phases, and partly from carbonate minerals. Most sulfide minerals in common geological samples were considered to be dissolved with the digestion of 0.7 mol l⁻¹ NaOCl, but only small fraction of arsenopyrite and loellingite in ores could be dissolved in this way. Satisfactory agreement was observed between the sum of the As or Sb values from exchangeable to residual fractions and the reported total As or Sb values, with a few exceptions. Analytical results of As and Sb for thirty five geochemical reference materials are tabulated, and geochemical and mineralogical features are discussed.     

电感耦合等离子体质谱法测定砂岩型铀矿样品中分步提取的铀

本文研究地质样品中铀形态的分析方法及应用技术,以进一步说明铀形态分析在地球化学找矿中的重要作用。该方法参考Tessier流程,将样品中的铀分为可交换离子态、碳酸盐结合态、铁锰氧化物结合态、硫化物及有机物结合态和结晶态,分别提取,提取溶液用高分辨率电感耦合等离子体质谱仪进行测量。设计的形态提取配方具有良好的可选择性和可重复性,经过国家标准物质、国际形态标准物质和人工模拟样品验证,证明形态提取试剂配方适合所定义的形态分析。通过对实际样品(总量铀为635μg/g)验证表明,碳酸盐结合态铀提取结果的可重复性最好(RSD为2.6%),其次为硫化物及有机物结合态铀(RSD为4.0%)、结晶态铀(RSD为6.0%)和铁锰氧化物结合态铀(RSD为6.1%),可交换离子态铀提取结果的可重复性最差(RSD为26%)。碳酸盐结合态铀与结晶态铀之比,可以用于反映地下铀矿的存在概率。     

Chemical Fractionation of Aluminium in the Sediments of El-Burullus Lagoon of Nile Delta,Egypt

A five step sequential extraction technique, following Tessier’s protocol has been applied to determine the chemical association of aluminium with major sedimentary phases (exchangeable, carbonate, manganese and iron oxides, organic and residual fraction) in four short sediment cores collected from El-Burullus lagoon of the Nile delta, Egypt. This study is a first approach of chemical fractionation of aluminium in one of the protective areas of the Mediterranean Sea of Egypt. The total metal content was also determined. The results of the fractionation study indicated that aluminium was mainly associated with the residual fraction (>95%). The organic and Fe–Mn oxide fractions were the next important phases. The exchangeable and carbonate fractions were less than 1%, limiting its potential toxicity as a pollutant. The geochemical analysis of aluminium forms reflected the lithogenic origin of this metal in the study area.     

Speciation and potential remobilization of heavy metals in sediments of the Taihu Lake, China

The species of Cu, Pb, Zn, Cd and Cr in sediments of the Taihu Lake, China, have been analyzed using the sequential chemical extraction method. Variations in the chemical fractions of these metals and their geographic distributions have also been studied. For all five metals, the residual fraction is highest but the exchangeable fraction is lowest among all the fractions. Compared to other metals, Cd has the highest percentage in the exchangeable fraction, and Cr is associated mainly with the residual fraction. Cu in the organic fraction and Pb in the Fe-Mn fraction are the important species, whereas the lowest percentages are found for Cd in the organic fraction, Cu in the Fe-Mn oxide fraction and Pb in the carbonate fraction. With respect to spatial differences, the total contents in the non-residual fractions of the metals in bay sediments are found to be higher than those in other sediments. The fractions of Cd, Cu and Cr showed significant variations in different regions. The fractions of Pb and Zn, however, did not show significant variations in spatial distribution, suggesting different amounts and different paths of anthropogenic input for the metals. Comparisons of the metal speciation indicated that Cd might be the most bioavailable metal, followed by Pb.     

Speciation analysis of metals （Tl, Cd and Pb） in Tl-containing pyrite and its cinder from Yunfu Mine, China, by ICP-MS with sequential extraction

The speciation of heavy metals such as thallium, cadmium and lead existing in pyrite and pyrite cinder was analyzed by ICP-MS with a sequential extraction procedure. The distribution patterns of these metals including exchangeable, reducible, oxidizable and residual fractions were obtained. Tl, Cd and Pb in pyrite and pyrite cinder samples from each extraction step were determined by inductively coupled plasma mass spectrometry (ICP-MS). Under the optimized instrumental conditions, detection limits of Tl, Cd and Pb in different matrices were within the range of 0.006–0.07 μg/L, and the relative standard deviations ranged from 0.8% to 1.2%. The accuracy of Tl, Cd and Pb determination was checked by analyzing two certified reference materials. The results demonstrate that trace Tl, Cd and Pb in the samples can be accurately determined. The sequential extraction results revealed that the percent contents of Tl, Cd and Pb in exchangeable, reducible and oxidizable fractions in pyrite cinder are different from those in pyrite and in pyrite cinder. Tl, Cd and Pb mostly are distributed in residual fraction. Therefore, the mobility of metals in pyrite is higher than that in pyrite cinder. Although distributions of Tl, Cd and Pb in the non-residual fraction are not dominant in pyrite cinder, the total concentrations of them could not be ignored. Consequently, attention must be paid to the risk of potential pollution by pyrite cinder.     

Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities

Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO₃), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.     

Speciation of trace metals in sediments of a tropical estuary

Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.     

改进BCR法-电感耦合等离子体发射光谱法测定矿产品堆场土壤中镉砷铅的化学形态

矿产品堆场土壤中重金属在环境中富集,随着元素的迁移、转化及地下水的循环,成为环境污染问题。本文将改进的顺序提取法(BCR)应用于矿产品堆场土壤中Cd、As、Pb的化学形态分析,结合这三种元素的性质,将堆场土壤中Cd、As、Pb分为可交换态、可还原态、可氧化态和残渣态,并利用电感耦合等离子体发射光谱法测定其含量。采用形态分析标准参考物质GBW 07436验证了三步提取态的准确性,并对6个矿产品堆场土壤中Cd、As、Pb形态含量进行分析,三步提取态加上残渣态质量分数之和与重金属总量进行了比较,回收率为85.54%~102.88%。通过对矿产品堆场土壤实际样品分析,Cd、As、Pb三种元素非残渣态含量顺序为Cd(79.40%~94.94%)Pb(24.27%~37.73%)As(22.89%~31.51%),表明Cd元素较为容易进入生物圈。该方法解决了港口堆场土壤中重金属化学形态提取问题,对污染土壤的治理具有指导意义。     

Selective chemical extraction of heavy metals in tailings and soils contaminated by mining activity: Environmental implications

Total concentrations of chemical elements in soils may not be enough to understand the mobility and bioavailability of the elements. It is important to characterise the degree of association of chemical elements in different physical and chemical phases of soil. Another geochemical characterisation methodology is to apply sequential selective chemical extraction techniques. A seven-step sequential extraction procedure was used to investigate the mobility and retention behaviour of Al, Fe, Mn, Cu, Zn, Pb, Cr, Co, Ni, Mo, Cd, Bi, Sn, W, Ag, As and U in specific physical–chemical and mineral phases in mine tailings and soils in the surroundings of the abandoned Ervedosa mine. The soil geochemical data show anomalies associated with mineralised veins or influenced by mining. Beyond the tailings, the highest recorded concentrations for most elements are in soils situated in mineralised areas or under the influence of tailings. The application of principal components analysis allowed recognition of (a) element associations according to their geochemical behaviour and (b) distinction between samples representing local geochemical background and samples representing contamination. Some metal cations (Mn, Cd, Cu, Zn, Co, Cr, Ni) showed important enrichment in the most mobilisable and bioavailable (i.e., water-soluble and exchangeable) fractions due likely to the acidic conditions in the area. In contrast, oxy-anions such as Mo and As showed lower mobility because of adsorption to Fe oxy-hydroxides. The residual fraction comprised largest proportions of Sn and Al and to a lesser extent Zn, Pb, Ni, Cr, Bi, W, and Ag, which are also present at low concentrations in the bioavailable fractions. The elements in secondary mineral phases (mainly Fe, Mn, Cu, Zn, Cd, Pb, W, Bi, Mo, Cr, Ni, Co, As and U) as well as in organic matter and sulphides are temporarily withheld, suggesting that they may be released to the environment by changes in physico-chemical conditions.     

Speciation of heavy metals in electroplating industry sludge and wastewater residue using inductively coupled plasma

The speciation of metals in environmental samples is a critical factor in assessing the potential environmental impacts, before their disposal. The distribution and speciation of toxic heavy metals in plating wastewater residues and sludge was investigated for four samples using sequential extraction method. Tessier method was used to fractionate the metal content into exchangeable, acid extractable, reducible and oxidizable fractions. Residual and total metal contents were determined in aqua regia digest. The extracts were analysed for metals using inductively coupled plasma -atomic emission spectrometry. The bioavailable fraction (exchangeable and acid extractable fractions) is comprised less than the other forms. The oxidisable and reducible forms are dominants for all the four samples studied. The major metal constitute in the samples is iron, the wastewater residue contains (12.3 and 7.4 g/Kg respectively on dry basis) and the sludge contains (31.5 and 41.6 g /Kg) respectively. Cr concentration is higher in wastewater residue of second electroplating industry. The descending order of the average total metal contents for these four samples were Fe > Cr > Sn > Zn >Cu > Ni > Mn > Pb > Cd > Ag. Based on the average of absolute values for the four samples the highest bioavailability order of metals is Cr (39 %) in wastewater residues and Zn (32 %) in sludge samples. Metal recovery was good, with < 10 % difference between the total metal recovered through the extractant steps and the total metal determined using aqua regia extract.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

Accumulation and partitioning of heavy metals in mangrove rhizosphere sediments

A field study was conducted to clarify the effect of rhizosphere processes on the accumulation and partitioning of heavy metals (Pb, Zn, Cu, Cr, Cd and Ni) in mangrove sediments. Metals were fractionated by a sequential extraction procedure into three chemically distinct fractions: water soluble, exchangeable and carbonate bound (B1), Fe–Mn oxide bound (B2), and organic and sulfide bound (B3). Results indicate that rhizosphere processes tend to increase the metal concentrations in the rhizosphere sediments. However, plant uptake may result in the decrease of the metal concentrations in the rhizosphere sediments when the metal concentrations are relatively low in the bulk sediments. Compared with the bulk sediments, the rhizosphere sediments have low concentrations of heavy metals in the B1 and B2 fractions and high concentrations in the B3 fraction. Either an increase or decrease in the residual fraction of heavy metals in the rhizosphere sediments may appear, depending on whether the formation of the refractory metal-organic compounds or the activation of the residual fractions dominates. Results also indicate that mangrove plants absorb and store non-essential metals in the perennial tissues, thus reducing the export of non-essential metals via leaf litter transport. Mangrove plants are excellent candidates for phytostabilization of heavy metals in intertidal substrates.     

Chemical fractionation of transition elements in Pacific pelagic sediments

Partitioning of transition elements in Pacific pelagic sediments (35 samples) was performed by sequential chemical leaching with barium chloride/triethanolamine (easily extractable fraction), acidic cation exchange resin (carbonate phases), and hydroxylamine hydrochloride and dilute hydrochloric acid solutions (hydrous oxides). Residual metal percentages are highest in red-brown clays and siliceous ooze, intermediate in calcareous materials and low in micronodules (2 samples, > 125 μm): residual metal contents seem to be controlled predominantly by the rate of admixture of volcanoclastic materials. At higher bulk metal concentrations, the non-residual fractions of Mn, Cu, Ni and Zn generally increase both in red-brown pelagic clays and in siliceous ooze. Mn, Ni, and Co concentrations are mainly associated with the easily reducible fraction (0.1 M NH₂OH·HCl), whereas Fe, Cu, and Zn exhibit higher percentages in the hydrochloric acid soluble fractions (0.3 M HCl); Zn and Cu are associated to some extent with the carbonate phase, copper with the easily extractable fraction.     

Spring and conduit sediments as storage reservoirs for heavy metals in karst aquifers

Sediment samples were collected from six springs draining the karst aquifer at Fort Campbell, Kentucky/Tennessee. These were analyzed by ICP-MS following an extraction procedure that separates the metals into exchangeable, carbonate, oxide, organic and residual fractions. Aluminum and iron are primarily present in the residual fraction while manganese may be dominantly in either the oxide or carbonate fraction. The redox-sensitive metals (Fe and Mn) have the greatest fractional distribution in the spring with the thickest sediments. Trace metals detected include Cr, Cd, Ni, Pb, and Zn in the range of a few to 200 mg/kg. In Beaver Spring, nickel is distributed between the exchangeable, carbonate and organic fractions, while in Gordon Spring, nickel is largely residual. Chromium is almost entirely associated with the organic fraction in Beaver Spring while it is largely residual in Gordon Spring.     

Trace Metal Speciation of USGS Reference Sample MAG-I

The USGS reference sample marine mud MAG-1 has been subjected to a sequential extraction procedure designed to partition the constituent trace metals into five fractions: I-exchangeable; II- bound to carbonates; III-bound to Fe-Mn oxides; IV- bound to organic matter; V- residual. The analytical approach involved successive chemical extractions and the subsequent determination of trace metal concentrations (Co, Cu, Ni, Pb, Zn; Fe, Mn) in the leachates by atomic absorption spectrophotometry. The chemical speciation results obtained on four replicate sub-samples demonstrate that the coefficients of variation for metal concentrations in the individual fractions are generally better than + 10%. Comparison with published values for total trace metal concentrations in the MAG-1 sample suggests that the overall accuracy of the chemical extraction procedure is satisfactory.     

Screening of extraction methods for Cd and As bioavailability prediction in rhizospheric soil using multivariate analyses

Heavy metals in tailings and mining wastes from abandoned mines can be released into adjacent agricultural field and bioaccumulated in crops or vegetables. Therefore, prediction of metal bioavailability has become an important issue to prevent adverse effect of bioaccumulated metals on human health. In this study, single and sequential extraction methods were compared using multivariate analysis to predict the bioavailability of Cd and As in contaminated rhizosphere soils. Single extraction using 0.1 M HCl for Cd and 1.0 M HCl for As had an extraction efficiency of 8–12% for soil Cd and 14–17% for soil As compared to total concentration extracted with aqua regia. Using sequential extraction, Fe–Mn-bound Cd (FR3) and residual Cd (FR5) were the dominant fractions representing 43 and 41% of total Cd concentration. For As, the strongly absorbed form (FR2) was the most abundant chemical fraction showing 45–54% of the total As concentration in soil. Multivariate analyses showed that single extraction with HCl and total concentration of Cd and As in soil were significantly correlated to potato and green onion plant tissue metal concentration. Although little information was obtained with multiple regression analysis because of multicollinearity of variables, the result of principle component analysis (PCA) revealed that the highest positive loading was obtained using total concentration of Cd and As in soil in the first principle component (PC1). In addition, total concentration of Cd and As in soil was independently grouped with other chemical fractions by cluster analysis. Therefore, the overall result of this research indicated that total concentrations of Cd and As in rhizosphere soils were the best predictors of bioavailability of heavy metals in these contaminated soils.     

Assessment to the potential mobility and toxicity of metals and metalloids in soils contaminated by old Sb–Au and As–Au mines (NW Portugal)

The main purpose of this study is to assess arsenic and antimony availability in soils, as well as Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn availability in soils derived from the schist–metagraywacke complex close to old Sb–Au mines and in soils developed from Ordovician slates and close to an old As–Au mine in Portugal. The availability was determined using a European certified sequential extraction procedure (BCR). The results demonstrated that metalloids are not readily bioavailable, because they are mainly associated with the residual fraction. Arsenic and antimony proportions in exchangeable fractions are up to 3 and 1%, respectively. However, arsenic is up to 24% in oxy-hydroxide fractions, while antimony is up to 4% in them, demonstrating the highest bioavailability of arsenic compared to that of antimony, as metalloids are weakly bound to the soils in that fraction. Therefore, arsenic tends to be more toxic than antimony in all soils studied. However, the pseudo-total contents show that both metalloids are above the Italian and Dutch guidelines. Therefore, if physico-chemical changes occur arsenic and antimony will show higher potential environmental risk than evidenced by Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn.     

深港西部通道填海区淤泥重金属化学形态分析

以深港西部通道填海区淤泥为研究对象,研究了重金属的化学形态特征,分析了填海工程活动带来的填海区地下水物理化学条件变化对重金属各个形态的影响。结果表明:除残留态外,填海区重金属存在形态主要为铁锰结合态、碳酸盐结合态和硫化物及有机结合态,其中,Pb和Ni以铁锰氧化物结合态和碳酸盐结合态为主,Cu以碳酸盐结合态和有机结合态为主,Zn以有机结合态和铁锰氧化物结合态为主,而Cd则以碳酸盐结合态为主。各金属在深港西部通道填海区淤泥的潜在迁移能力序列如下:Pb(39.68%)>Cu(31.59%)>Zn(20.49%)>Cd(12.80%)>Ni(10.98%)。     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

The distribution and elevated solubility of lead,arsenic and cesium in contaminated paddy soil enhanced with the electrokinetic field

The objectives of this study were to investigate fractionation, solubility and potential bioavailability of Pb, As and Cs in Mississippi River Delta paddy soil under an electrokinetic field (EKF). Effects of EKF on soil pH changes and solid-phase distributions of metal(loid)s were examined. Results showed that fractionation of Pb, As and Cs was largely determined by the nature of elements, loading levels and EKF treatment. Native Pb in the soil was mostly in the amorphous iron oxide, organic matter and residual fractions, native As in the amorphous iron oxide, easily reducible oxide and residue fractions while native Cs in the residue fraction. Added Pb, As and Cs showed distinguished solid-phase distributions: Pb dominantly in the organic matter fraction; As in the amorphous iron oxide fraction, and Cs in the residue with a significant water-soluble plus exchangeable fraction. EKF treatment is effective on lowering soil pH to 1.5 near the anode due to water electrolysis releasing proton which is beneficial for dissolution of metal(loid)s, increasing their overall solubility. The acidification in the anode soil efficiently increased the water-soluble Pb and the exchangeable Cs, implying enhanced solubility and elevated their overall potential bioavailability in the anode region while lower solubility in the cathode area. The building up of water-soluble As in the anode region may be from electromigration of As anion from the cathode. This study shows significant enhancement of redistribution, elevated solubility and overall bioavailability of Pb, As and Cs in Mississippi Delta paddy soil under the EKF.