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.     

Metal contamination of the environment by placer and primary gold mining in the Adola region of southern Ethiopia

Primary and placer gold mining sites in southern Ethiopia were studied to see the contribution of mining to the accumulation of metals in different environmental media. Sediment, water and plant samples were analyzed for Al, Mn, Fe, As, Ni, Cr, Cu, Co, Pb, W, Sb, Mo, Zn and V. Water parameters (pH, Eh, TDS, anions and cations) were also measured. The sediment analyses results show that the most abundant metals are Ni (average 224.7 mg/kg), Cr (199 mg/kg), Cu (174.2 mg/kg), V (167.3 mg/kg), Zn (105.5 mg/kg), Pb (61.5 mg/kg) and As (59.7 mg/kg) in the primary gold mining sites while the placer sites show high concentration of V (average 301.2 mg/kg), Cr (260.4 mg/kg), Zn (179 mg/kg), Ni (113.4 mg/kg), Cu (46.7 mg/kg), As (32.2 mg/kg) and Co (31 mg/kg). The metals Cu, Ni, W, Cr, As and Pb in primary and Sb, W, Cr, Ni, Zn, As and Mo in placer gold mining sites have geoaccumulation indexes (I _geo) from one to four indicating considerable accumulation of these metals. Waters from both primary and placer mining sites are near neutral to alkaline. Arsenic (average 92.8 μg/l), Ni (276.6 μg/l), Pb (18.7 μg/l), Sb (10.7 μg/l), Mn (1 mg/l), Fe (8.3 mg/l) and Al (23.8 mg/l) exceeded the guideline value for drinking water. Plants show high concentration of Cr (average 174.5 mg/kg), Ni (163.5 mg/kg), Zn (96 mg/kg) and W (48 mg/kg). Zinc, W, Mo, Ni and Cr show the maximum biological absorption coefficient (BAC) ranging 0.4–1.7, 0.1–104.6, 1.1–2.6, 0.2–1.6 and 0.2–3.6, respectively, and the results suggest bioaccumulation of these elements in plants. The minerals especially sulfides in the ore aggregate are the ultimate source of the metals. The release of the metals into the environmental media is facilitated (in addition to normal geologic processes) by human activities related to gold mining.     

Concentrations and solubility of heavy metals in muck sediments from the St. Lucie Estuary,U.S.A.

To evaluate muck sediments as a potential soil amendment, total and Mehlich III-extractable concentrations of Cd, Cu, Cr, Ni, Pb, Zn, and Co in 59 muck sediment samples from the St. Lucie Estuary were analyzed. A seven-step chemical fractionation procedure was used to assess the potential mobility of heavy metals. Except for Cd, the average total concentrations of the metals are lower than the reported average concentrations of these elements in municipal composts in the U.S.A. The concentrations were also below critical levels for the safe use of wastes and byproducts in agriculture, as established by the United States Environmental Protection Agency. The Cd, Cu, Cr, Ni, Pb, Zn and Co in the sediments were predominantly associated with silicate minerals in the residual form. Most metals in the muck sediments occur predominantly in weakly mobile or nonbioavailable forms. Use of mucks in neutral pH upland soils should not pose any significant hazards or risk to the environment. However, Cd, Cu, Cr, Ni, Pb, Zn, and Co, especially Zn, Cu, and Pb, could be more readily released from the muck sediments under acidic soil conditions.     

ICP-AES在新疆哈拉奇地区水系沉积物样品分析中的应用研究

本文采用四酸溶样ICP6300电感耦合等离子体发射光谱法测试了新疆哈拉奇地区水系沉积物样品中的Li P Ti V Cr Mn Co Ni Cu Zn Sr Y Nb Mo Ba La Pb B W Sn Cd 21种微量元素,明确了该方法测试样品中的Li P Ti V Cr Mn Co Ni Cu Zn Sr Y Nb Mo Ba La 16个元素的检出限、准确度、精密度满足规范（DZ/T0130.2006-2006）要求,而Pb B Cd Sn W5个元素测试质量不能满足规范要求,并对新疆哈拉奇地区水系沉积物采样粒度样品进行了分析测试,验证了该区化探扫面选择10-80目粒度是合适的,但在异常查证工作中要选择10-60目采样粒度更合理。     

南京市大气降尘重金属含量特征及来源研究

文中对南京市大气降尘重金属含量水平进行了研究,从2006年12月起连续收集一年的大气降尘样品,分析了As、Cd、Cr、Cu、Hg、Mn、Mo、Ni、Pb、Se、Zn等11个元素。结果表明,与土壤背景值相比,南京市大气降尘中除Cr、Fe、Mn外的重金属含量总体明显升高。采用相关分析和主成分分析,对降尘重金属元素来源进行解析,认为有三种主要来源:一是As、Cu、Hg、Pb、Se与燃煤活动、汽车尾气排放有关。二是Cd、Ni、Zn、Mo可能与化学工业有关,但Mo还受工业活动、土壤颗粒物的影响。分析还表明,在化工业园附近的样点,这些元素含量普遍较高。三是Mn、Cr主要与土壤颗粒物有关(自然来源)。以Fe作为参考元素计算重金属的富集因子表明,自然来源的Cr、Mn具有较小的富集因子,而受工业活动影响的Cd、Pb、Se、Zn具有较大的富集因子。     

西天山夏特乡南部一带地球化学、空间分布及元素组合特征

对区内元素在各地质体的分配与分布特征进行了初步归纳总结,区内15种元素全域分布水平中Au、Pb、Cr、Ni、Mo、As高于西天山背景值,Ag、Cu、Zn、Sb、Hg、W、Sn、Bi、Mn低于西天山背景值。其空间分布特征中,与区内深大断裂构造、地层、岩浆均有不同程度的关联。     

Application of multivariate statistical methods to indicate the origin and geochemical behavior of potentially hazardous elements in sediment around the Sarcheshmeh copper mine,SE Iran

Multivariate statistical techniques, i.e., correlation coefficient analysis, principal components analysis (PCA), and hierarchical cluster analysis (CA), were applied to the total and water-soluble concentrations of potentially hazardous metals in sediments associated with the Sarcheshmeh mine, one of the largest Oligo-Miocene porphyry copper deposits in the world. The samples were analyzed for hazardous metal concentration levels by inductively coupled plasma mass spectrometry method. Results indicate that the contaminant metals As, Cd, Cu, Mo, S, Sb, Sn, Se, Pb, and Zn were positively correlated with the total concentrations. These hazardous metals also have strong association in the PCA and CA results. Different anthropic versus natural sources of contaminant metals were distinguished by using CA method. Water-soluble fraction of hazardous metals showed that the hydro-geochemical behavior of these metals in sediments is different considerably. Elements such as Cd, Co, Cr, Cu, Fe, Mn, Ni, S, and Zn are readily water soluble from contaminated samples, especially from evaporative mineral phases, while the release of As, Mo, Sb, and Pb into the water is limited by adsorption processes. Results obtained from the application of multivariate techniques on the water-soluble fraction data set show that the hazardous metals are categorized into three groups including (1) Ni, S, Co, Cu, Cr, and Fe; (2) Se, Mn, Cd, and Zn; and (3) Sb, As, Mo, and Sn. This classification describes the hydro-geochemical behavior of hazardous metals in water–sediment environments of the Sarcheshmeh porphyry copper mine and can be used as a basis in remedial and treatment strategies.     

甘肃北山金、铜矿床红沙的植物地球化学特征及其找矿意义

北山地区植被属戈壁荒漠植被类型，主要植物群落为红沙，红沙中多数元素特别是成矿元素及其伴生元素的含量和变化系数矿区大于背景区，元素含量背景区呈对数正态分布，矿区呈偏对数正态或多峰分布，红沙中的元素组合分类背景区为Au,Cu,Pb,Zn,As,Sb,Mo,V,Mn和Ag,Sn,Sr,Ba及Ti,Cr,Co,Ni,金矿区为Au,Ag,As,Sb,Mo,Mn,Sr和Cu,Pb,Zn,Sn,Ba及Co,Ni,Ti,V,Cr,铜矿区为Cu,Pb,Zn,Mo,Au,Ag,Ba和As,Sb,Sn,Mn及Ti,V,Cr,Co,Ni,Sr，矿区红沙中浓集系数较大的元素多数在矿区岩石中的浓集系统亦较大，金，铜矿床红沙和岩石中的特征元素分别都有Au,Ag,Ag,Sb,Mo,(Mn)和Cu,Pb,(Ba,Ti,Cr)。在金，铜矿床（体上方分别发育有良好的Au和Cu的生物地球化学异常和元素组合及分带，根据红沙的地球化学特征能，判断金或铜矿种类型，并能对掩埋，隐伏金，铜矿床（体）进行定位预测。     

Reconnaissance geochemistry of the nechako plateau, British Columbia, using lake sediments

A lake sediment geochemical survey was undertaken over the Nechako plateau, British Columbia, to test application of the technique to regional exploration and compare its effectiveness with results obtained elsewhere. Organic-rich lake sediment samples were collected towards the centre of approximately 500 lakes on a helicopter-assisted survey covering some 16,000 km². Lakes overlying each of five major lithologies contain a distinctive suite of trace metals. Regional variations of Cu, Mo, Pb, Zn, Ni, Cr, Sr, Ba, Ag, Co, V and Ga can be related to differences in underlying geology. In addition, levels of Cu, Mo, Pb and Zn which exceed their regional thresholds are related to mineralization or lithologies favourable to mineralization. Although metal concentrations within a lake may vary up to 12x, anomalous conditions are not masked by this variability and the survey outlined all major sulphide occurrences known in the region.     

Heavy metals contamination in road dust in Delhi city,India

Road dust samples were collected from four different areas having different landuse patterns: industrial, heavy traffic, residential and mixed use in Delhi city of India. The samples were analyzed for Ba, Co, Cr, Cu Fe, Mn, Ni, Pb and Zn by ICP-AES. Results indicate high levels of Co, Cr, Cu, Mn and Ni in samples collected from industrial area. Ba, Pb and Zn showed higher concentration levels in heavy traffic area while Fe did not show any discernible variation between the localities. The concentrations of Fe, Mn, Ba, Zn, Cr, Cu, Pb, Ni and Co showed a decreasing trend. The content of heavy metals was comparable to those in other cities in the world. A multivariate statistical approach which includes Pearson’s correlations and principal component analysis was used to identify the possible sources of metals in the road dust. Enrichment factors were estimated for further confirming the sources of contamination. Significant positively correlations between road dust metals Cu–Mn–Co–Cr–Ni suggest that major common source of origin is industrial activities. A meaningful correlation between Ba and Zn, and a moderate positive correlation between Pb and Ba indicate the influence of traffic activities. Enrichment factors calculation indicated that Pb, Cu, Cr and Zn are moderately enriched whereas Co, Ni and Mn are less enriched while Ba exhibited very low enrichment in the dust samples. The results indicate that industrial and vehicular traffic are the two major sources. Traffic appears to be responsible for the high levels of Zn, Cu and Ba. High concentration of Co, Cr, Cu and Mn may be due to industrial sources.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Comparison of arsenic and heavy metals contamination between existing wetlands and wetlands created by river diversion in the Yellow River estuary,China

Samples were collected at 71 sites in the Yellow River Delta Natural Reserve in December 2010 to represent soil conditions before and after the Yellow River (YR) diversion. The As, Cd, Cu, Pb, Zn, and Ni concentrations were measured to determine metal contamination levels. Results suggest that Cd concentrations were significantly higher after the YR diversion than before. The As, Cd, Cr, Cu, Ni, Pb, and Zn soil contamination indices did not exceed contamination levels, although the heavy metal content increased after the YR diversion. The mean concentrations of these heavy metals were lower than the Class I criteria. Correlation analysis shows significant correlations between As and Cr, Cu, Ni, Pb, and Zn concentrations both before and after the YR diversion. However, no significant correlations were observed between heavy metal concentration and pH before the diversion, and no heavy metal concentration was correlated with salinity. The principal component analysis indicates that these trace elements, including As, were closely correlated with each other and therefore likely originated from shared pollution sources before the diversion. These results are useful for assessing the heavy metal contamination and proposing feasible suggestions to improve soil quality.     

Genetic Nature of Mineralization with Native and Intermetallic Compounds in the Bobruisk Ring Structure (Republic of Belarus)

The results of study of the Bobruisk ring structure (Republic of Belarus) containing ~80 rare rockforming and accessory minerals are reported. Among them are native (Fe, Cu, Sn, Zn, Pb, Ag, Mo, W, Al) and intermetallic (Fe, Cr, Ni, Mo, B, N, C, Si) compounds, natural alloys (Fe–Cr, Fe–Cr–Mo–W–B; brass (Cu–Zn–Pb); and bronze (Sn–Pb–Zn–Cu)). They are observed as segregations of various shapes and sizes, as well as their aggregates. The formation of mineralization is controlled by reduced mantle fluids enriched in H₂, CH₄, CO, Si, N, and O and stimulating accumulation of rare elements as native and intermetallic phases, alloys, rather than isomorphic impurities in minerals.     

石家庄市大气降尘重金属元素来源分析

本文对石家庄市大气降尘重金属含量水平进行了研究,从2007年11月起连续收集一年的大气降尘样品,分析了As、Cd、Hg、Pb、Cr、Cu、Zn、Ni、Mo、Mn、Al2O3、K2O等12项。结果表明,与土壤背景值相比,石家庄市大气降尘中除Al2O3外的重金属含量总体明显升高。采用相关分析和主成分分析,对降尘重金属元素来源进行解析,认为有3种主要来源:一是Pb、Cr、As、Hg、Mo、Cd、Mn与燃煤活动、道路交通有关;二是Ni、Cu、Zn除与燃煤活动有关外,还与工矿企业废气排放有关;三是Al2O3主要与土壤颗粒物有关(自然来源)。以Al作为参考元素计算重金属的富集因子表明,受工业活动影响的Cd、Hg、Zn具有较大的富集因子,大气降尘中的重金属含量高值区与工业区域的分布相吻合。     

包头市典型工业区表层土壤中重金属污染状况及其潜在生态风险研究

为了解包头市典型工业企业对其所在地土壤中重金属含量的影响及污染现状,利用相关性系数对其表层土壤中7种重金属(Cu、Zn、Pb、Cr、Cd、Mn、Ni)来源进行研究,并采用内梅罗综合污染指数法和潜在生态危害指数对其污染状况进行评价。结果表明,7种重金属含量平均值均高于内蒙古土壤背景值,其中Cd、Mn、Ni超标率已达100%,而Cu、Pb、Zn的超标率分别为97%、93%和93%,只有Cr超标率较低(53%),污染程度依次为CdPbCuNiZnMnCr,其中Pb和Cd为重度污染,Cu、Zn、Ni为中度污染,Cr、Mn为轻度污染;Cu、Zn、Cr、Mn、Ni可能同时来自工业生产和交通运输两个源,而Pb和Cd除上述来源外,燃煤烟气的排放有较大贡献。潜在生态危害依次为CdPbCuNiCrZnMn,其中Cd的潜在生态风险最大,应予以高度重视,其他金属的风险均为轻微。     

Contamination levels assessment of potential toxic metals in road dust deposited in different types of urban environment

A total of 42 samples of road dust were collected along ring road, city centre, city side, and freeway in Urumqi, China. Total concentrations of Cd, Cr, Cu, Ni, Pb, Mn, Be, Co, Zn, and U were determined by using the inductively coupled plasma-mass spectrometry in order to assess and to compare road dust contamination levels of metals among the four roads. The results show that, among the four categories of roads, mean concentrations of Co and U vary little. City centre locations show strong enrichments of Cd, Cu, Pb, and Be. Along the ring road, the highest mean concentrations were found for Cr, Ni, Mn, and Co. However, the highest concentrations of Zn and U were found along the freeway. The cluster analysis shows that three main groups can be distinguished. Every group may be associated with different main sources and concentrations of the metals. The results of contamination assessment reveal that, among all of the potential toxic metals, Cd, Cu, and Zn pollution were obviously heavier with moderate or high contamination indices for most road dust samples, while Cr, Ni, and Pb contamination were lower along the four categories of roads. Compared with the city side, Cd, Cu, Pb, Ni, and Zn contamination were heavier along the ring road, the city centre, and the freeway with high traffic density. Low Pb contamination or no contamination in all the road dust samples may be related to the increasing usage of lead-free petrol.     

Heavy metal distribution in karst soils from Croatia and Slovakia

With the use of the optimised three-step BCR sequential-extraction procedure it was possible to assess the mobility of selected elements in soil profiles from Croatian and Slovakian karst terrains. The soils in the Croatian karst were enriched in Cr, Ni, V, Mn, Cu, Cd and Mo, while soils from the Slovak Karst had high Pb and Zn concentrations. It was determined that the elements were most readily mobilised from the topsoil and the degree of mobility decreased with depth. Cr and Ni were mainly bound to the residual fraction, and Pb in the oxidisable fraction. Cu mobility was high in samples treated with agrochemicals throughout the soil profile.     

Spatial distribution patterns and temporal trends of heavy-metal concentrations in a petroleum hydrocarbon-contaminated site: Karaduvar coastal aquifer (Mersin, SE Turkey)

The aim of this study was to investigate spatiotemporal variations in groundwater heavy-metal concentrations at the Karaduvar agricultural-industrial district (Mersin, SE Turkey), where parts of the underlying coastal aquifer has been polluted by petroleum hydrocarbons (PHCs) from diverse sources. The water chemistry data for the present study is comprised of 275 samples collected during 2006–2010 from 55 water-supply wells. The samples were analyzed in situ for physical parameters (EC, DO, pH, and temperature) and in the laboratory for As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb and Zn using the ICP-MS method. Box–whisker plots and principal components analysis (PCA) method were employed to determine the seasonal changes occurring in heavy-metal concentrations and to identify source apportionment of pollution parameters in groundwater. During the monitoring period, in many wells, heavy-metal concentrations (except for Cd) exceeded the limit values set by Turkish Water Pollution Control Directive (No: 25687). Results from the PCA suggest that elevated Mn, Fe, Co, Ni and As concentrations may be linked to oxidation–reduction of geogenic Mn/Fe oxyhydroxides in PHC-contaminated parts. The high concentrations of Cu, Mo and probably Cd in background areas result from the agricultural and petrochemical activities conducted in the recent past. At the site, high Pb and Zn concentrations are probably related to agricultural activities in PHC-contaminated areas, whereas Cr can be solely attributed to lithogenic sources. At the Karaduvar site, heavy-metal pollution in groundwater is found to be much more persistent than PHC contamination.     

固体聚合膜电解浓集法测量天然水中低含量氚的化学淬灭效应研究

固体聚合膜电解浓集法是浓缩氚含量较低(1 Bq/m~3)的天然水样的常用方法,但因水样自身含有杂质离子或电解装置聚合膜带入杂质进入浓集液,使浓集液偏酸性,在测量过程中易产生化学淬灭效应,导致氚的测量值偏低。本文研究了水样自身存在的杂质离子和聚合膜上残留的杂质离子、样品溶液的pH值及其电导率所产生的化学淬灭效应的影响,实验表明,为减少化学淬灭效应,提高测量低含量氚的准确性,需保证水样溶液呈中性,电导率≤1μS/cm,同时避免杂质沉积在聚合膜上。如果水样溶液的pH值偏酸性、电导率大于1μS/cm,可采用酸碱混合型离子交换树脂去除水样中自身的杂质;对于聚合膜引入的杂质,可在电解后的水样中加入微量氨水将其pH值调节至中性。