Heavy metals in deep groundwater within coal mining area,northern Anhui province,China: concentration,relationship, and source apportionment

The present study was conducted to investigate the concentrations of heavy metals (HMs) in deep groundwater from coal mining area, including cadmium (Cd), chromium (Cr), copper (Cu), zinc (Zn), lead (Pb), and nickel (Ni). The samples were collected from different aquifers in four coal mines of northern Anhui province, China, which were unconsolidated formation (UF), coal measure aquifer (CA), Taiyuan limestone aquifer (TA), and Ordovician limestone aquifer (OA), respectively. HM concentrations from the four different sources were analyzed by atomic absorption spectrometer, and were found in the order of Zn>Ni>Pb>Cu>Cd>Cr (in UF), Ni>Zn>Pb>Cu>Cr>Cd (in CA), Ni>Zn>Pb>Cu>Cd>Cr (in TA), and Zn>Ni>Pb>Cu>Cr>Cd (in OA), respectively. Concentrations of Cu, Zn, and Cr were found within the quality guidelines set by Bureau of Quality and Technical Supervision of China (GB/T 14848-93) and World Health Organization, while the concentrations of Cd, Pb, and Ni were higher than their respective permissible limits. The enhanced concentrations of Ni, together with Cr, were considered to be affected by anthropogenic sources, since they both had high variable coefficient. Moreover, the inter-dependence of HMs and their pollution sources were further discussed using statistical techniques, including one-factor analysis of variance, Pearson correlation analysis, and principle component analysis.     

Distribution and speciation of heavy metals and their sources in Kumho River sediment,Korea

The interaction between heavy metals and river sediment is very important because river sediment is the sink for heavy metals introduced into a river and it can be a potential source of pollutants when environmental conditions change. The Kumho River, the main tributaries of the Nakdong River in Korea, can be one of the interesting research targets in this respect, because it runs through different geologic terrains with different land use characteristics in spite of its short length. Various approaches were used, including mineralogical, geochemical, and statistical analyses to investigate the distribution and behavior of heavy metals in the sediments and their sources. The effect of geological factor on the distribution of these metals was also studied. No noticeable changes in the species or relative amounts of minerals were observed by quantitative X-ray diffraction in the sediments at different stations along the river. Only illite showed a significant correlation with concentrations of heavy metals in the sediments. Based on an average heavy metal concentration (the average concentrations of Cd, Co, Cr, Cu, Ni, Pb, and Zn were 1.67, 20.9, 99.7, 125, 97.6, 149, 298 ppm, respectively), the sediments of the Kumho River were classified as heavily polluted according to EPA guidelines. The concentrations of heavy metals in the sediments were as follows: Zn > Pb > Cu > Ni > Cr > Co > Cd. In contrast, contamination levels based on the average I _geo (index of geoaccumulation) values were as follows: Pb > Cd > Zn > Cu > Co = Cr > Ni. The concentrations of heavy metals increased downstream (with the exception of Cd and Pb) and were highest near the industrial area, indicating that industrial activity is the main factor in increasing the concentrations of most heavy metals at downstream stations. Sequential extraction results, which showed increased heavy metal fractions bound to Fe/Mn oxides at the downstream stations, confirmed anthropogenic pollution. The toxicity of heavy metals such as Ni, Cu, and Zn, represented by the exchangeable fraction and the fraction bound to carbonate, also increased at the downstream stations near the industrial complexes. Statistical analysis showed that Pb and Cd, the concentrations of which were relatively high at upstream stations, were not correlated with other heavy metals, indicating other possible sources such as mining activity.     

Contamination,bioaccessibility and human health risk of heavy metals in exposed-lawn soils from 28 urban parks in southern China's largest city,Guangzhou

The total concentrations and oral bioaccessibility of heavy metals in surface-exposed lawn soils from 28 urban parks in Guangzhou were investigated, and the health risks posed to humans were evaluated. The descending order of total heavy metal concentrations was Fe > Mn > Pb > Zn > Cu > Cr > Ni > Cd, but Cd showed the highest percentage bioaccessibility (75.96%). Principal component analysis showed that Grouped Cd, Pb, Cr, Ni, Cu and Zn, and grouped Cr and Mn could be controlled two different types of human sources. Whereas, Ni and Fe were controlled by both anthropogenic and natural sources. The carcinogenic risk probabilities for Pb and Cr to children and adults were under the acceptable level (<1 × 10⁻⁴). Hazard Quotient value for each metal and Hazard Index values for all metals studied indicated no significant risk of non-carcinogenic effects to children and adults in Guangzhou urban park soils.     

Competitive heavy metals adsorption on natural bed sediments of Jajrood River,Iran

The presence of heavy metal concentrations was examined in natural sediments from four sites along the Jajrood river in northeast of Tehran, the capital of Iran. Besides determination of elemental concentrations (Pb, Cu, Zn, Cd, Ni and Cr), X-ray fluorescence and X-ray diffraction tests were carried out to determine other chemical components in these adsorbents. Also the ability of sediments to adsorb these heavy metal ions from aqueous solutions was investigated. Results show that the extent of adsorption increases with increase in adsorbent concentration. The amount of adsorbed Pb, Cu and Zn in sediments was much greater than that of the other metals, and Cr was adsorbed much less than others. The adsorbabilities of sediments to heavy metals increased in the order of Pb > Cu > Zn > Cd > Ni > Cr. Based on the adsorption data, equilibrium isotherms were determined at selected areas to characterize the adsorption process. The adsorption data followed Freundlich and Langmuir isotherms in most cases. Correlation and cluster analysis was performed on heavy metals adsorption and sediment components at each site to evaluate main adsorbing compounds in sediments for each metal. Results demonstrated that heavy metals sorption is mostly related to load of organic matter in the Jajrood river sediments.     

Preliminary assessment of heavy metals levels of soils of an oil field in the Niger Delta, Nigeria

This communication presents the results of preliminary investigation of the characteristic levels of heavy metals in surface soils of an oilfield in the Niger Delta. The results indicate higher concentration of the following metals: Cd, Pb, Cu; Ni, Zn, Cr, Mn and Hg in soils around the gas plant than the pipeline areas. There is a significant temporal and spatial variation in the concentrations of the heavy metals. Samples collected during the wet season showed lower concentrations of heavy metals. The distribution pattern of heavy metals follows the following order Fe> Mn> Zn> V> Cr> Pb> Cu> Ni> Cd> Hg> As. The soils around the oilfield could be considered unpolluted since the concentrations of the metals fit into background levels and concentrations found in natural and agricultural soils. Since metal build up is a gradual process, farmland, fishing ponds and water bodies closer to these facilities will be at risk of heavy metal pollution over time.     

Heavy metal relationships in a Pennsylvania soil

Soils of loamy sand on weathered, sandy dolomite were cored from six holes up to 70 ft beneath a municipal waste landfill in central Pennsylvania. Mn, Fe, Ni, Co, Cu, Zn, Cd, Pb, and Ag were determined in exchangeable and non-exchangeable forms in total and < 15 μm soil samples. Most of these metals were bound in Mn oxides, non-exchangeable with 0.5 M CaCl₂. The Mn oxides (often X-ray amorphous) identified when crystalline as todorokite occurred chiefly as coatings on quartz grains.Somewhat higher amounts of acid leachable trace metals were found in the < 15 μm size fraction than in the total soil samples; however, trace metal/Mn ratios were similar in both. In general, the initial mild soil leaching, which dissolved chiefly Mn oxides, gave MnFeX>Co>Ni>Pb>Zn> Cu>Cd>Ag. The final leaching, which dissolved chiefly ferric oxides, gave Fe>Mn>Ni>Zn>Co> Cu>Pb>Cd>Ag. Samples taken from an unpolluted site and from the same soils affected for seven years by leachate from the refuse had similar metal contents.Soil extractable Co, Ni, Cu, and Zn could be predicted from the Mn extracted. Based in part on factor analysis of the data, Mn-rich oxides had at least tenfold higher heavy metal percentages than Fe-rich oxides (crystalline component goethite), reflecting their greater coprecipitation potential. Because of this potential and because of the generally higher solubility of Mn than Fe oxides, more heavy metals may be released from Mn-rich than from Fe-rich soils by disposal of organic-bearing wastes. However, leaching of the moisture-unsaturated soils in situ is rarely severe enough to completely dissolve both Mn and Fe oxides. Based on the Mn content, Cd, Cu, and Pb were depleted in soil moisture beneath the landfill relative to their amounts in the soil. This depletion may reflect factors including heterogeneity in metal content of the soil oxides; preferential resorption of these metals; and removal of the Cd, Cu, and Pb as organic precipitates or as inorganic precipitates such as carbonates.     

Distribution and mobility of heavy metals in paddy soils of the Kočani Field in Macedonia

Contamination of soils with heavy metals is widespread and poses a long-term risk to ecosystem health. Abandoned and active mining sites contain residues from ore-processing operations that are characterised by high concentrations of heavy metals. The distribution and mobility characteristics of heavy metals (As, Cd, Cu, Pb, and Zn) in paddy soil samples from Kočani Field (Macedonia) using ICP-EAS and a sequential extraction procedure was evaluated. The results indicate that highly elevated concentrations of As, Cd, Cu, Pb, and Zn were detected in the paddy soil sample from location VII-2 in the vicinity of Zletovo mine and Zletovska river in the western part of Kočani Field, which drains the untreated acid mine waters and mine wastes from the active Zletovo mine. The degree of contamination based on index of geoaccumulation (I _geo) from strong to weak in the paddy soils samples is Pb > As > Cd > Zn > Cu. The mobility potential of heavy metals in all paddy soil samples increases in the order As < Cu < Pb < Zn < Cd. According to the results of the anthropogenic impact on the paddy soils, a further study on the heavy metal concentrations in rice and other edible crops, the remediation process of the paddy soils and a dietary study of the local population are needed.     

Contamination of surface waters by mining wastes in the Milluni Valley (Cordillera Real,Bolivia): Mineralogical and hydrological influences

This study is one of very few dealing with mining waste contamination in high altitude, tropical-latitude areas exploited during the last century. Geochemical, mineralogical and hydrological characterizations of potentially harmful elements (PHEs) in surface waters and sediments were performed in the Milluni Valley (main reservoir of water supply of La Paz, Bolivia, 4000 m a.s.l.), throughout different seasons during 2002–2004 to identify contamination sources and sinks, and contamination control parameters. PHE concentrations greatly exceeded the World Health Organization water guidelines for human consumption. The very acidic conditions, which resulted from the oxidation of sulfide minerals in mining waste, favoured the enrichment of dissolved PHEs (Cd > Zn ? As ? Cu ∼ Ni > Pb > Sn) in surface waters downstream from the mine. Stream and lake sediments, mining waste and bedrock showed the highest PHE content in the mining area. With the exception of Fe, the PHEs were derived from specific minerals (Fe, pyrite; Zn, Cd, sphalerite, As, Fe, arsenopyrite, Cu, Fe, chalcopyrite, Pb, galena, Sn, cassiterite), but the mining was responsible for PHEs availability. Most of the PHEs were extremely mobile (As > Fe > Pb > Cd > Zn ∼ Cu > Sn) in the mining wastes and the sediments downstream from the mine. pH and oxyhydroxides mainly explained the contrasted availability of Zn (mostly in labile fractions) and As (associated with Fe-oxyhydroxides). Unexpectedly, Pb, Zn, As, and Fe were significantly attenuated by organic matter in acidic lake sediments.     

Mobility and ecological risk assessment of heavy metals in surface sediments of Xiamen Bay and its adjacent areas,China

Xiamen Bay (XMB) has received substantial loadings of pollutants from industrial and municipal wastewater discharged since the 1980s. To assess ecological risks and the current spatial changes of metal contaminants in bottom surface sediments, 12 samples were collected. Samples were subjected to a total digestion technique and analyzed by ICP–OES for Cu, Pb, Zn, Cr, and Cd, and by AFS for Hg and As. Among these metals, Zn had the highest values (68–268 mg kg⁻¹), followed by Pb (27–71 mg kg⁻¹), and lower concentrations were found for Cd (42–1,913 μg kg⁻¹) and Hg (0–442 μg kg⁻¹). In comparison with the average crustal abundance values, the results indicated that nearly half of the sediment samples of XMB and its adjacent areas were contaminated by Cd, Pb, Zn, and As. Furthermore, based on the modified BCR sequential extraction procedure, the chemical speciation of heavy metals (Cd, Cr, Cu, Pb, Zn, Hg, and As) in selected sediment samples were evaluated in this study. Data from BCR sequential extractions indicated that Cd posed a medium ecological risk, whereas, Cr posed low risk since its exchangeable and carbonate fractions were below 4%, and the mobility of heavy metals in XMB decreased in the order Cd > Pb > Cu > Zn > Hg > As > Cr. By applying mean effects range median quotients (mERMQ), the results showed that Yuandang Lagoon with mERMQ value >0.5 would be expected to have the greatest potential toxic risk in amphipod within XMB and its adjacent areas.     

Heavy metals accumulation and ecophysiological effect on <Emphasis Type="Italic">Typha angustifolia</Emphasis> L. and <Emphasis Type="Italic">Cyperus esculentus</Emphasis> L. growing in distillery and tannery effluent polluted natural wetland site,Unnao, India

Distillery and tanneries are major source of heavy metals pollution in natural wetland sites in India. Present study deals with the heavy metals accumulation potential of Typha angustifolia and Cyperus esculentus growing in distillery and tannery effluent polluted wetland sites. The metal accumulation pattern in both macrophytes showed direct correlation with the metal content in sediments. Both macrophytes were observed root accumulator for Fe, Cr, Pb, Cu, and Cd. The metal accumulation in T. angustifolia was found higher than C. esculentus, and accumulation pattern was Fe > Mn > Cr > Zn > Pb > Cu > Ni > Cd. Simultaneously, chlorophyll, protein, cysteine, and ascorbic acid were also induced in T. angustifolia than C. esculentus. In addition, formation of multinucleolus in shoot of T. angustifolia was found an evidence of extra protein synthesis for tolerance under stress conditions. Hence, C. esculentus was observed potential but less tolerance for metals than T. angustifolia. Therefore, these wetland plants could be used for phytoremediation of heavy metals from wastewater.     

Heavy metal mobility assessment in sediments from the Odiel River (Iberian Pyritic Belt) using sequential extraction

The Tessier sequential extraction scheme (SES) was applied to sediments from the Odiel river catchment (Iberian Pyritic Belt, SW of Spain), one of the most acid rivers on Earth, to assess the chemical association (exchangeable, carbonatic, bound to manganese and iron oxides, bound to organic matter and residual mineral) of heavy metals (Zn, Cd, Pb, Cu, Cr, Mn, Ni, Fe, and Hg). Sediments are very heterogeneous in their textural characteristics, showing different grain size. Twenty-seven samples were studied from from areas along the Odiel River, from the source to the mouth, with special interest in the Odiel Marshes Natural Park due to its ecological significance. Samples were classified as sandy (especially at the river mouth with low iron oxide and organic matter content) and clay-silty (in the middle of the river catchment with high iron oxide content). The numerous sandy samples with low pH values explain the low levels of metals upstream, although potential metals contributions arise from mining and ore. However, the presence of sulfate in the mining area and carbonate at the mouth may explain the high presence of lead and iron in these sandy zones. Some percentage of mobile Ni, Cu, and Zn were detected in the mining area, but the elevated relative percentage of exchangeable Cd in the estuary is even more remarkable. The percentage of Zn bound to carbonate is considerable in the catchment but especially in the estuary. However, Cu is only detected in the carbonate phase downstream, in spite of the low concentration of carbonate, which represents a drawback in the application of the Tessier SES to these types of samples. Finally, relatively high percentages of residual, non-mobile, Hg and Pb were observed, in the estuarine and mining areas, respectively. Sand, lime, and clay fractions of representative samples from Areas I, II, and III were used in a metal speciation study. Mainly, the elements analyzed had accumulated in the non-residual fractions. In the mining area of the Pyrite Belt, the elements analyzed are mainly bound to Fe–Mn oxides (Fe + Mn + Cu + Cr + Pb + Mn ± Zn) and the organic matter/sulfide fraction (Ni + Zn + Hg ± Cd), independent of sediment grain size. In conclusion, we show that the results of the study of chemical speciation in sediments from acid rivers are independent of the sediment grain size considered.     

Accumulation of heavy metals in wild commercial fish from the Baotou Urban Section of the Yellow River,China

In this work we studied the accumulation of heavy metals in nine species of fish with different life and feeding habitats which are native and major commercial fish in the Baotou Urban Section of the Yellow River. The results showed that the concentration of heavy metals was significantly dependent on fish species; the pollution index of heavy metals in different species were ranked as Hemiculter leucisclus > Carassius auratus auratus > Hemibarbus maculatus > Megalobrama amblycephala > Abbottina rivularis > Cyprinus carpio > Squaliobarbus curriculus > Perccottus glehni > Saurogobio dabryi. Product–moment correlation coefficients among the metal pairs Pb–Zn, Cu–Cd, Cu–Zn, Cu–Pb, Pb–Cd, and Zn–Cd revealed there was no competitions between metals in each tissue. Correlations between heavy metal concentrations and fish length or weight indicated that accumulation of the heavy metals by the different fish species was related to their surrounding environments and their life and feeding habitats. According to the mean bioconcentration factors (BCFs), the heavy metal concentrations in these nine species were ranked Zn ≫ Cu > Cd ≈ Pb. In this work, the bioaccumulation factors (BAFs) were developed by using the sum of exchangeable and bound-to-carbonate heavy metals as Cs values. It was found that BAFs better reveal the accumulation characteristics of the heavy metals in the fish, which might provide an effective method for assessing bioaccumulation of heavy metals.     

Contamination and potential mobility assessment of heavy metals in urban soils of Hangzhou,China: relationship with different land uses

Concentration and distribution of heavy metals (Cd, Cu, Pb and Zn) in urban soils of Hangzhou, China, were measured based on different land uses. The contamination degree of heavy metals was assessed on the basis of pollution index (PI), integrated pollution index (IPI) and geoaccumulation index (I _geo). The 0.1 mol l⁻¹ HCl extraction procedure and gastric juice simulation test (GJST) were used to evaluate the potential mobility and environmental risk of heavy metals in urban soils. The average concentration of Cd, Cu, Pb and Zn in urban soils was measured at 1.2 (with a range of 0.7–4.6), 52.0 (7.4–177.3), 88.2 (15.0–492.1) and 206.9 (19.3–1,249.2) mg kg⁻¹, respectively. The degree of contamination increased in the order of industrial area (IA) > roadside (RS) > residential and commercial areas (RC) > public park and green areas (PG). The PIs for heavy metals indicated that there is a considerable Cd, Cu, Pb and Zn pollution, which originate from traffic and industrial activities. The IPI of these four metals ranged from 1.6 to 11.8 with a mean of 3.5, with the highest IPI in the industrial area. The assessment results of I _geo also supported that urban soil were moderately contaminated with Cd and to a lesser extent also with Cu, Pb and Zn. The IP and I _geo values reveal the pollution degree of heavy metal was the order of Cd > Pb > Zn ≈ Cu. It was shown that mobility and bioavailability of the heavy metals in urban soils increased in the order of Cd > Cu > Zn ≈ Pb. Owing to high mobility of Cd and Cu in the urban soils, further investigations are needed to understand their effect on the urban environment and human health. It is concluded that industrial activities and emissions from vehicles may be the major source of heavy metals in urban contamination. Results of this study present a rough guide about the distribution and potential environmental and health risk of heavy metals in the urban soils.     

Heavy metal concentrations in marine green,brown, and red seaweeds from coastal waters of Yemen,the Gulf of Aden

The purpose of this study was to investigate the concentration levels of heavy metals in different species of the main three marine algal divisions from the Gulf of Aden coastal waters, Yemen. The divisions included Chlorophyta—green plants (Halimeda tuna, Rhizoclonium kochiamum, Caldophora koiei, Enteromorpha compressa, and Caulerpa racemosa species), Phaeophyta—brown seaweeds (Padina boryana, Turbinaria elatensis, Sargassum binderi, Cystoseira myrica, and Sargassum boveanum species), and Rhodophyta—red seaweeds (Hypnea cornuta, Champia parvula, Galaxaura marginate, Laurencia paniculata, Gracilaria foliifere, and species). The heavy metals, which included cadmium (Cd), cobalt (Co), copper (Cu), chromium (Cr), Iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), zinc (Zn), and vanadium (V) were measured by Atomic Absorption Spectrophotometer (AAs). The concentrations of heavy metals in all algal species are in the order of Fe >> Cu > Mn > Cr > Zn > Ni > Pb > Cd > V > Co. The results also showed that the uptake of heavy metals by different marine algal divisions was in the order of Chlorophyta > Phaeophyta > Rhodophyta. These heavy metals were several order of magnitude higher than the concentrations of the same metals in seawater. This indicates that marine alga progressively uptake heavy metals from seawater.     

A study on hydrochemical elucidation of coastal groundwater in and around Kalpakkam region, Southern India

The chemical composition of 29 bore well water samples throughout the Kalpakkam region, South India, was determined to identify the major hydrogeochemical processes and the suitability of groundwater for domestic and irrigation purposes. The hydrochemical data were analyzed with reference to World Health Organization (WHO) standards and their hydrochemical facies were determined. The Piper plot shows that most of the groundwater samples fall in the field of mixed calcium–sodium–bicarbonate type followed by sodium–chloride, calcium–bicarbonate and mixed calcium–magnesium–chloride water types. The concentration of total dissolved solids exceeds the desirable limit in about 14% of samples; alkalinity values exceed the desirable limit in about 34% of the samples. The concentration of sulphate is well within the desirable limit at all the locations. The dominance of various heavy metals in the groundwater followed the sequence: Zn > Fe > Mn > Cu > Ni > Pb > Cr > Cd. Among the metal ions, the concentration of chromium and cadmium are within the permissible limit. Data are plotted on the US Salinity Laboratory diagram, which illustrates that most of the samples fall in the field of high salinity and low sodium hazard, which can be used to irrigate salt tolerant and semi-tolerant crops under favorable drainage conditions. Based on the analytical results, chemical indices like sodium adsorption ratio and residual sodium carbonate were calculated which show that most of the samples are good for irrigation.     

Heavy metal contamination of soils and tea plants in the eastern Black Sea region,NE Turkey

The study area covers two geologically different regions which have intensively been carpeted by tea plants in the eastern Black Sea. The rocks exposed in the region contain considerable amount of trace metals due to Upper Cretaceous massive sulfide formations and tertiary epithermal mineralizations. Tea plants that grow in soils derived from such mineralized rocks contain different concentrations of Cu, Pb, Zn, Fe, Cd, P, Al, Na, K, and S. The content ratios of most of the analyzed elements except Al are higher in basaltic and sedimentary rocks. To describe the transfer of metals from soil to tea leaf, the Freundlich-type model (log c _plant = ac _soil + log b) is used. The metal concentrations in leaves of tea plant in the studied soils are ranked as Zn > Cu > Pb > Al > Cd > Fe. The capacity of the plant to affect the metal accumulation decreased as follows: Fe > Cd > Pb > Cu > Zn > Al. Negative correlations were found between pH and availability of Cu, Pb, Zn, Mn, and Al elements by the tea plant. Experimental applications indicated that tea plant leaves growing on soils with high metal contents show some signs of toxicity. In soils where, particularly, ammonium sulfate fertilizer is used, metal uptake by the tea plant was found to be significantly higher as a result of extremely acidic character of the soil.     

Environmental contamination of Zn,Cd, Ni,Cu, and Pb from industrial areas in Hamadan Province,western Iran

Eleven surface soil samples from calcareous soils of industrial areas in Hamadan Province, western Iran were analyzed for total concentrations of Zn, Cd, Ni, Cu and Pb and were sequentially extracted into six fractions to determine the bioavailability of various heavy metal forms. Total Zn, Cd, Ni, Cu and Pb concentrations of the contaminated soils were 658 (57–5,803), 125.8 (1.18–1,361), 45.6 (30.7–64.4), 29.7 (11.7–83.5) and 2,419 (66–24,850) mg kg⁻¹, respectively. The soils were polluted with Zn, Pb, and Cu to some extent and heavily polluted with Cd. Nickel values were not above regulatory limits. Copper existed in soil mainly in residual (RES) and organic (OM) fractions (about 42 and 33%, respectively), whereas Zn occurred essentially as RES fraction (about 69%). The considerable presence of Cd (30.8%) and Pb (39%) in the CARB fraction suggests these elements have high potential biavailability and leachability in soils from contaminated soils. The mobile and bioavailable (EXCH and CARB) fractions of Zn, Cd, Ni, Cu, and Pb in contaminated soils averaged (7.3, 40.4, 16, 12.9 and 40.8%), respectively, which suggests that the mobility and bioavailability of the five metals probably decline in the following order: Cd = Pb > Ni > Cu > Zn.     

Modeling the adsorption of Cd (II), Cu (II), Ni (II), Pb (II) and Zn (II) onto montmorillonite

The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X⁻), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.     

Pb isotopic constraints on the formation of the Dikulushi Cu–Pb–Zn–Ag mineralisation, Kundelungu Plateau (Democratic Republic of Congo)

Base metal–Ag mineralisation at Dikulushi and in other deposits on the Kundelungu Plateau (Democratic Republic of Congo) developed during two episodes. Subeconomic Cu–Pb–Zn–Fe polysulphide ores were generated during the Lufilian Orogeny (c. 520 Ma ago) in a set of E–W- and NE–SW-oriented faults. Their lead has a relatively unradiogenic and internally inhomogeneous isotopic composition (²⁰⁶Pb/²⁰⁴Pb = 18.07–18.49), most likely generated by mixing of Pb from isotopically heterogeneous clastic sources. These sulphides were remobilised and enriched after the Lufilian Orogeny, along reactivated and newly formed NE–SW-oriented faults into a chalcocite-dominated Cu–Ag mineralisation of high economic interest. The chalcocite samples contain only trace amounts of lead and show mostly radiogenic Pb isotope signatures that fall along a linear trend in the ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram (²⁰⁶Pb/²⁰⁴Pb = 18.66–23.65; ²⁰⁷Pb/²⁰⁴Pb = 15.72–16.02). These anomalous characteristics reflect a two-stage evolution involving admixture of both radiogenic lead and uranium during a young fluid event possibly c. 100 Ma ago. The Pb isotope systematics of local host rocks to mineralisation also indicate some comparable young disturbance of their U–Th–Pb systems, related to the same event. They could have provided Pb with sufficiently radiogenic compositions that was added to less radiogenic Pb remobilised from precursor Cu–Pb–Zn–Fe polysulphides, whereas the U most likely originated from external sources. Local metal sources are also suggested by the ²⁰⁸Pb/²⁰⁴Pb–²⁰⁶Pb/²⁰⁴Pb systematics of combined ore and rock lead, which indicate a pronounced and diversified lithological control of the immediate host rocks on the chalcocite-dominated Cu–Ag ores. The Pb isotope systematics of polysulphide mineralisation on the Kundelungu Plateau clearly record a diachronous evolution.     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.