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.     

A geochemical survey of trace elements in agricultural and non-agricultural topsoil in Dexing area,China

In China, soil pollution is very serious, which has jeopardized the ecology, food safety, the people's health, and even the sustainable development of agriculture. In order to investigate the soil pollution situation, a total of 874 agricultural and non-agricultural topsoil samples were collected from Dexing area, northeast of Jiangxi Province, China. The total elemental concentrations of 17 elements (As, Hg, Mo, Cd, Cr, Zn, Cu, Mn, Ti, Pb, Fe, Ca, K, Si, Al, Mg, and Na) were determined. The geochemical background and threshold was predicted with the method of the median ± median absolute deviation (MAD). The agricultural soil median concentration of trace elements was similar to that of the non-agricultural soil. In contrast to Jiangxi soil background of trace elements, the geochemical background of the study area was obviously higher. The maps of the pollution indices for As, Cd, Cr, Cu, Hg, Mn, Mo, Pb, Ti and Zn of non-agricultural soil and agricultural soils in the study area, showed that the highest level of pollution is distributed near and along the Lean River, especially in the neighboring and surrounding Dexing and Leping mining area.     

Variations of trace elements under hydrological conditions in the Min River,Eastern Tibetan Plateau

In order to better understand the relative importance of hydrologic variation and anthropogenic disturbance and their complex interactions within the trace elemental geochemical cycle, water samples were collected monthly over 1 year in the Min River, eastern Tibetan Plateau, and analyzed for trace element composition. The dissolved trace elements exhibited different relationships with increasing discharge compared with major elements. The elements analyzed can be divided into three groups according to their behavior in response to changing discharge: (1) elements that showed weak positive correlation with discharge, e.g. Cu, V, and Ba; (2) elements that exhibited weak negative correlation with discharge, including Rb, Sr, Pb, Sb, Zn, Cr, Cd, and U; and (3) elements that displayed no significant correlation with variation in discharge, e.g. Ti, Fe, Co, Ni, and As. Cu was strongly affected by anthropogenic activities and flushed into the river with increasing discharge. Ba has a strong solubility in the terrestrial environment, dissolved quickly, and was released into the river. The positive relationship between V concentration and discharge may be attributed to secondary reactions, such as precipitation and adsorption on oxides and aluminosilicate clays. Conservative behavior had an impact on the geochemical behavior of Sr and Rb across hydrologic variation. Pb, Zn, Sb, Cd, and Cr underwent a mild dilution effect connected with anthropogenic activities. The chemostatic behavior of U was regulated by carbonate dissolution and biological uptake. In addition, higher temperatures enhanced biotic activities, affecting the concentrations of Fe and Ni. The relationship between power law slopes and coefficient of variation for discharge and solute concentration suggests that concentrations of trace elements vary significantly with increasing discharge compared with major elements. Silicate mineral weathering had less effect on the fluvial solutes with increasing discharge. Mining activity may exert an additional control on concentration–discharge dynamics of anthropogenic trace elements.     

Transport of trace elements under different seasonal conditions: Effects on the quality of river water in a Mediterranean area

Concentrations of total and dissolved elements were determined in 35 water samples collected from rivers in Sardinia, a Mediterranean island in Italy. The overall composition did not change for waters sampled in both winter and summer (i.e., January at high-flow condition and June at low-flow condition), but the salinity and concentrations of the major ions increased in summer. Concentrations of elements such as Li, B, Mn, Rb, Sr, Mo, Ba and U were higher in summer with only small differences between total and dissolved (i.e., in the fraction <0.4 μm) concentrations. The fact that these elements are mostly dissolved during low flow periods appears to be related to the intensity of water–rock interaction processes that are enhanced when the contribution of rainwater to the rivers is low, that is during low-flow conditions. In contrast, the concentrations of Al and Fe were higher in winter during high flow with total concentrations significantly higher than dissolved concentrations, indicating that the total amount depends on the amount of suspended matter. In waters filtered through 0.015 μm pore-size filters, the concentrations of Al and Fe were much lower than in waters filtered through 0.4 μm pore-size filters, indicating that the dissolved fraction comprises very fine particles or colloids. Also, Co, Ni, Cu, Zn, Cd and Pb were generally higher in waters collected during the high-flow condition, with much lower concentrations in 0.015 μm pore-size filtered waters; this suggests aqueous transport via adsorption onto very fine particles. The rare earth elements (REE) and Th dissolved in the river waters display a wide range in concentrations (∑REE: 0.1–23 μg/L; Th: <0.005–0.58 μg/L). Higher REE and Th concentrations occurred at high flow. The positive correlation between ∑REE and Fe suggests that the REE are associated with very fine particles (>0.015 and <0.4 μm); the abundance of these particles in the river controls the partitioning of REE between solution and solid phases.Twenty percent of the water samples had dissolved Pb and total Hg concentrations that exceeded the Italian guidelines for drinking water (>10 μg/L Pb and >1 μg/L Hg). The highest concentrations of these heavy metals were observed at high-flow conditions and they were likely due to the weathering of mine wastes and to uncontrolled urban wastes discharged into the rivers.     

长沙、株洲、湘潭三市土壤中重金属元素的来源

为追踪长沙、株洲、湘潭3个城市表层土壤中Cd、As、Pb等重金属元素的来源,分析了土壤、基岩、大气干湿沉降、水、悬浮物等介质之间重金属元素的质量平衡和土壤自身重金属元素含量随时间变化的特点。结果显示,除As外,区内基岩中的重金属元素含量低于克拉克值;残积物中Cd相对基岩贫化,As、Pb、Cu、Hg等重金属元素相对基岩的富集小于3倍;大气干湿沉降重金属元素相对土壤富集了数倍至数十倍;湘江水体主要向沿江潮土提供As、Cd物源:近50年内土壤重金属元素有较高的增加速率。不同介质间重金属元素的质量变化特点支持长沙、株洲、湘潭三市土壤重金属元素富集的主要物源为大气沉降,地表水及悬浮物是沿江湖土重金属元素的主要物源,基岩对土壤提供的物源有限的结论。     

Characterization of trace elements in sulphur-rich Late Permian coals in the Heshan coal field,Guangxi, South China

The concentration of trace elements and their distribution in the late Permian coal in the Heshan coal field, Guangxi Autonomous Region, were analysed in this paper. The late Permian coal of the Heshan mining district was developed in a low energy and shallow, confined carbonate platform. Heshan coal is a low volatile bituminous coal characterized by a high sulphur content, ranging between 2.0% and 8.2%. Compared with the worldwide average content of the trace elements in coal, the content of some trace element in the study coal is markedly high (Bi, Ce, Cr, Cs, Cu, Ga, Hf, Sr, Ta, Th, U, V, W, Y, Zr, La, Mo, Nb and Sc).The trace element associations were investigated by means of intracorrelation analysis. Some elements, such as Cl, F and Sr are found in coal in association with the carbonate minerals. V, Cr, Zn, Mo, Ni and As contents in coal vary significantly amongst the coal samples. They are mainly concentrated in the lower part of the coal #4 upper of Suhe and Lilan mines and the coal #4 lower of Dong mine, and these possibly occurring in minerals such as arsenide and sulphide. The content of U in Heshan coal is high and is mainly concentrated at the upper and the lower parts of the coal seam and it is associated with mineral assemblages with Ba, Mo, V, Ni, Zn, Rb and Cr. Furthermore, La and Ce are highly correlated with those found in phosphate minerals and Pb, Sc, Ga, Th, Y and Sn to those in aluminosilicate minerals. The enrichment of some elements such as V, Cr, Zn, Mo, Ni, Rb as well as total sulphur and iron in the lower part of most coal seams might be associated with the formation of soil horizon before the accumulation of peat in the basin. Some other elements such as Cl, F, Sr and Ca are locally concentrated in the top of specific coal seams as a result of the leaching from overlying carbonates.     

Spatial trends and losses of major and trace elements in agricultural acid sulphate soils distributed in the artificially drained Rintala area,W. Finland

Acid sulphate soils, common in the coastal areas of Finland, contribute strongly to high acid, S and metal loadings on adjacent surface waters. This, in turn, is causing significant harm to the aquatic ecology. There is, however, limited knowledge on the total amounts of acidity and chemical elements leached from these soils. The overall objective of this study was to determine geochemical patterns in acid sulphate soils and their parent sediments and, based on the identified patterns assess the extent, mechanisms and present state of leaching of major and trace elements from these soils. The distribution of pH, aqua regia extractable concentrations of P and metals (Al, Ba, Ca, Co, Cr, Cu, Fe, K, La, Mg, Mn, Na, Ni, Sr, Th, Ti, V, Zn) and total concentrations of S and C were determined in 30 vertical profiles collected in the 23 km² large Rintala agricultural area (mid-western Finland) underlain largely with S-rich sediments. It was found that approximately 70% of the area consists of acid sulphate soils with a minimum pH<4.0, an average depth of 1.8 m, and S concentrations in the parent sediments varying from 0.24 to 1.04%. Acid sulphate soils have not developed where the S concentrations in the sediments are ⩽0.10% or where the concentrations of organic C in the soil zones are >4%. Four different methods were used to estimate the losses of chemical elements from the acid sulphate soils: (1) the concentrations in the soil were compared with those in the parent sediments, (2) due to indicated heterogeneities in several profiles, the vertical changes of the immobile Ti was used to re-calculate element losses, (3) element depletions in the acid sulphate soils (as compared to those in the parent sediments) were compared to the corresponding depletions in the non acid sulphate soils, (4) element concentrations in drainage waters were compared with those in the parent sediments. Based on these calculations, it was assessed that the percentual leaching of the aqua regia extractable fraction (total for S) has been as follows: S (40–50%), Na (30–50%), Mn (25–35%), Sr (15–20%), Ca–Ni–Co (approximately 10%), Mg–K–Zn (5–10%), Th–La–Cu–Al–P–Ti–Fe (<5%), and Ba–Cr–V (<1%). While it was possible to quite accurately estimate the percentages and thus the amounts of elements lost, it was not possible to estimate the rate of leaching as there is no available detailed information on dates when ditching activities and thus oxidation-acidification processes started. Other calculations indicated that the mobile S reservoir is still some 15 ton/hectare, which is huge but still smaller than the losses that have occurred since the area was drained (23–28 ton/hectare).     

Dissolved trace elements and heavy metals in the Danjiangkou Reservoir,China

Concentrations of trace elements and heavy metals (Al, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Se, Sr, V and Zn) in the Danjiangkou Reservoir, the water source area of the Middle Route of China’s interbasin South to North Water Transfer Project, were analyzed using an Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES) and compared with the national and international standards for drinking water. The results indicated that concentrations of As, Pb, Sb and Se in the Reservoir exceeded the standards and they would pose health risk for residents in the region and the water receiving areas of the interbasin water transfer project. Spatial and temporal variability of the trace elements and heavy metals in the Reservoir implies their mixed sources of natural processing and anthropogenic activities in the upper drainage of the Reservoir. The research results would help develop water resource management and conservation strategy for the interbasin water transfer project.     

Seasonal and spatial dynamics of trace elements in water and sediment from Pearl River Estuary, South China

In this study, spatial and seasonal dynamics of trace elements (Cu, Pb, Zn, Cd, As) in water and sediments were examined in the Pearl River Estuary (PRE), South China. The spatial variations of all the studied trace elements in sediments show the general decrease pattern from northwest to southeast side of the PRE, suggesting that the main sources of these trace elements may originate from terrestrial (rock and soil) weathering and human activities (e.g. agricultural, industrial and municipal wastewaters) via riverine inputs. The dissolved Cu, Pb, Cd, As, and Zn in PRE ranged from 0.34 to 3.26, 0.19 to 4.58, 0.0015 to 0.30, 0.16 to 8.18, 3.74 to 36.10 μg/L, respectively. There are obvious seasonal changes of dissolved trace elements in the PRE aquatic system. The maximum seasonal averages of all the dissolved trace elements excluding Zn were observed in summer, whereas dissolved Zn showed the minimum in this season. The overall spatial pattern of all the dissolved trace elements excluding Zn demonstrates decreasing trends from inshore to offshore, and the highest concentrations of dissolved Cu, Cd, As, and Zn appeared in the western part of PRE or the mouths of Pearl River, suggesting strong riverine and anthropogenic local inputs. PCA and correlation analysis show that the geochemical behavior of dissolved Cu and As are complicated and the dynamics of these two elements are controlled by various physicochemical parameters, whereas physicochemical parameters might play a relatively small role in the distributions of other studied trace elements.     

Gases and trace elements in soils at the North Silver Bell deposit, Pima County, Arizona

Soil samples were collected over the North Silver Bell porphyry copper deposit near Tucson, Arizona. Volatile elements and compounds in gases derived from the soils and metallic elements in the soils were analyzed in order: (1) to see which volatile constituents of the soils might be indicative of the ore body or the alteration zones; and (2) to distinguish the ore and alteration zones by comparison of trace elements in the soil.Plots of analytical data on trace elements in soils indicated a typical distribution pattern for metals around a porphyry copper deposit, with copper, molybdenum, and arsenic concentrations higher over the ore body, and zinc, lead, and silver concentrations higher over the alteration zones.Higher than average concentrations of helium, carbon disulfide, and sulfur dioxide adsorbed on soils were found over the ore body, whereas higher concentrations of carbon dioxide and carbonyl sulfide were found over the alteration zones.     

水位动态变化下水体驳岸渗流场及稳定性研究

目前水体驳岸设计只注重景观性与生态性,缺乏水位动态变化对驳岸渗流场及稳定性影响的研究。以澧水河2007-2012年水文地质资料为基础,从驳岸水位动态变化速度、岸坡安全系数两个角度,研究不同水位升降速度的驳岸稳定性变化规律。研究表明:水位动态变化对驳岸渗流场有明显影响,水位变化速度快,驳岸自由水面变化滞后越明显;驳岸水位上升时,其安全系数由大变小再到稳定;随着水位逐渐下降,驳岸安全系数先减小,当水位达到一定高度(此时安全系数最小)时,安全系数逐渐回升。研究结论用以指导水体驳岸设计,对水体驳岸在水位动态变化条件下安全运行具有现实意义。     

Geochemical baseline of trace elements in the sediment in Dexing area,South China

A baseline might be used as a point of reference to monitor change from some specific data without concern for whether the baseline determination is natural or has been changed by human activity. We selected 326 sediment samples from Dexing area, South China, and analyzed for 17 chemical elements. The geochemical baseline was predicted with the method of the normalization procedure combined with the relative cumulative frequency curve. The results indicate Al was the best reference element for the normalization procedure among four potential reference elements (Al, Fe, Ti, and Mn). The baseline value range obtained from the normalization procedure method included both the regional geochemical background of the sediment and the median value of the measured contents. The median value of baselines obtained from relative cumulative frequency method was lower than that obtained from normalization procedure method. In contrast to the geochemical patterns of heavy metals in 1987, the spatial distribution of anomalies sprawled in 2004 in study area, especially for Cu, Pb, Zn, Cd, As, Fe, and Cr.     

Mobility of some potentially toxic trace elements in the coal of Guizhou, China

 The mobility of 10 potentially toxic trace elements (PTTE), As, Cd, Cr, Cu, Hg, Ni, Pb, Se, Tl, and Zn from 32 coals of the Longtan Group formed in Permian Period in Guizhou Province, China was investigated using sequential extraction procedures. The results demonstrate that PTTEs such as Hg, As, Se, Cd, Cu, and Pb have the highest mobility at surface conditions, and the average extractable fractions of them are 86%, 95%, 79%, 76%, 69%, and 69% of the total amount in coal, respectively. The elements in coal with the lowest leachability include Tl, Cr, and Ni, and the average extractable fractions of them are 30%, 20%, and 29% of the total amount in coal respectively. Zinc has an intermediate behavior, and the average leachable fraction of it accounts for 46% of the total amount in coal. The results demonstrate that mobility of PTTE in coal depends on the speciation of these elements. The elements associated with sulfates, carbonates, sulfides and some organic matter in coal show the highest extraction rates during the weathering process, while elements with silicate affinities are inert at surface conditions. Received: 29 December 1998 · Accepted: 10 November 1998     

安徽江淮地区土壤微量元素分布特征及成因分析

多目标区域地球化学调查作为生态地球化学调查的基础工作,以快速查明表层土壤及其背景地球化学元素分布为目的.本文以安徽江淮地区多目标区域地球化学调查结果为基础,对安徽江淮地区耕地土壤及其母质中主要元素分布特征及其成因进行了分析研究,结果得出:(1)大多数地区表层土壤微量元素含量与深层具有一致性和继承性;(2)各地土壤微量元素分布特征主要受成土母质类型控制,说明其成因与成土母质和成土过程等因素有关;(3)耕地土壤微量元素含量的变异受施肥、灌溉和耕作方式等人为因素影响较大,且存在较大的地区差异性.     

Occurrence and migration of hazardous trace elements in coals from Guizhou Province, China

Coals from Guizhou Province, Southwest China, attract many researchers＇ attention for their high concentrations of hazardous trace elements, sulphur and mineral components. Trace elements in coals have diverse modes of occurrence that will greatly influence their migration in the process of coal preparation. Mode of occurrence is also important in determining the partitioning during coal combustion. The coal floatation test by progressive release was used to study the migration of trace elements and mineral components in the process of froth floatation. Inductively coupled plasma mass spectrometry （ICP-MS） was used to determine the absolute concentrations of trace elements including As, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Th, U, V and Zn in the parent coals and the floatation fractions. Precise determination of the mineral matter percentage in coals was obtained by low-temperature ashing. The mineral compositions in coals were quantified using Rietveld-based X-ray diffraction analysis package on low-temperature ash. Scanning electron microscope equipped with energy dispersive X-ray detector was used to provide information on the forms of occurrence of mineral components in coal. Five floatation fractions were obtained from the pulverized coal samples. The contents of trace elements and mineral components decrease from the first tailings to the last cleaned coal. The concentrations of trace elements and mineral components in parent coals and different floatation samples show that trace elements and mineral components are mainly concentrated in the first tailings samples. Nearly 60% of mineral components are enriched in the first tailings, whereas less than 1.3% remains in the cleaned coal. The ratio of sixteen trace elements concentrations in the first tailings to the corresponding concentrations in the cleaned coal ranges from 1.6 to 22.7. Quantitative mineralogical analysis results using the full-profile general structure analysis system （GSAS） showed that the main compositions of LTA include quartz, calcite, kaolinite, pyrite, chlorite, montmorillonite, illite, anatase and pyrite.     

Dissolved trace elements in river water: spatial distribution and the influencing factor, a study for the Pearl River Delta Economic Zone, China

Twenty-nine water samples were collected from different river channels of the Pearl River Delta Economic Zone, China. An inductively coupled plasma-mass spectromonitor (ICP-MS) was used to measure concentrations of the trace elements in these samples. The results suggest that the average concentrations of rare earth elements in river water show an increasing trend from the West River, the North River, the rivers of the Pearl River Delta, and the Shenzhen River to the East River. Relatively high concentrations of heavy metals appear in the East River, the rivers of the Pearl River Delta and the Shenzhen River, while the West River and the North River have relatively low heavy metal concentrations. Trace element concentrations in samples collected near urban or industrial areas are much higher than those of samples collected from distant areas, away from urban and industrial areas. After natural conditions, human activities have significant influence on the trace element concentrations in river water. This trace element concentration’s spatial distribution in the river water from the Pearl River Delta Economic Zone is actually an integrated effect of natural conditions and human activity.     

Spatial distribution and geochemical baselines of major/trace elements in soils of Medak district,Andhra Pradesh,India

Regional-scale variations in soil geochemistry were investigated with special reference to differences among soil groups and lithology in an area of 9,699 km² in Medak district, Andhra Pradesh, India. The concentrations of 29 elements (major: Si, Al, Fe, Mn, Mg, Ca, Na, K, Ti, P and trace: As, Ba, Cd, Co, Cr, Cu, F, Mo, Ni, Pb, Rb, Se, Sr, Th, U, V, Y, Zn, Zr) in 878 soil samples collected (557-topsoil, 321-subsoil) at a sampling density of 1 site/17 km² from 557 sites representative of all the soil types present in studied area were determined, and their elemental composition are discussed. The baseline levels of these elements in soils are determined over different lithological units for the identification of anomalous values relative to these. For the first time, geochemical maps for Medak district are prepared on 1:50,000 scale and the lithogeochemical database generated provides information on the lateral and vertical distribution of elements in soil. The spatial variations in the distribution of elements reflect underlying geologic characteristics. Box-plots reveal that the concentration of most of the elements in soils were not strongly dependent on the soil group but the soil-geochemistry abruptly changes with the change in the soil parent materials indicating that the distribution of elements is mostly influenced by the bedrock lithology and other natural processes acting on them. For instance, the concentrations of Co, Cu, Fe, Mn, Ti, V and Zn are high in soils developed on basaltic terrain while the soils developed on granitic and gneissic terrain exhibit high elemental concentrations of K, Pb, Rb, Si, Th and Y. Alfisols had relatively high contents of elements while entisols had lower concentrations of most of the elements. The database can be used in the chemical characterisation of different geological units as well as applications in various environmental and agricultural fields. The results indicate that regional geology is an important determinant of soil geochemical baselines for soil pollution assessment and further emphasizes the importance of determining background levels locally. The defined baselines can be used to establish background values for future soil surveys.