Effects of acid-sulfate weathering and cyanide-containing gold tailings on the transport and fate of mercury and other metals in Gossan Creek: Murray Brook mine,New Brunswick,Canada

Gossan Creek, a headwater stream in the SE Upsalquitch River watershed in New Brunswick, Canada, contains elevated concentrations of total Hg (Hg_T up to 60 μg/L). Aqueous geochemical investigations of the shallow groundwater at the headwaters of the creek confirm that the source of Hg is a contaminated groundwater plume (neutral pH with Hg and Cl concentrations up to 150 μg/L and 20 mg/L, respectively), originating from the Murray Brook mine tailings, that discharges at the headwaters of the creek. The discharge area of the contaminant plume was partially delineated based on elevated pH and Cl concentrations in the groundwater. The local groundwater outside of the plume contains much lower concentrations of Hg and Cl (<0.1 μg/L and 3.8 mg/L, respectively) and displays the chemical characteristics of an acid-sulfate weathering system, with low pH (4.1–5.5) and elevated concentrations of Cu, Zn, Pb and SO₄ (up to 5400 μg Cu/L, 8700 μg Zn/L, 70 μg Pb/L and 330 mg SO₄/L), derived from oxidation of sulfide minerals in the Murray Brook volcanogenic massive sulfide deposit and surrounding bedrock. The Hg_T mass loads measured at various hydrologic control points along the stream system indicate that 95–99% of the dissolved Hg_T is attenuated in the first 3–4 km from the source. Analyses of creek bed sediments for Au, Ag, Cu, Zn, Pb and Hg indicate that these metals have partitioned strongly to the sediments. Mineralogical investigations of the contaminated sediments using analytical scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM), reveal discrete particles (<1–2 μm) of metacinnabar (HgS), mixed Au–Ag–Hg amalgam, Cu sulfide and Ag sulfide.     

The transfer and fate of Cd, Cu, Pb and Zn from two historic metalliferous mine sites in the U.K.

Monitoring of heavy metal transfers, aerial deposition and fluvial transport to soil, stream sediment and vegetation compartments surrounding two former PbZn mines are reported. Results show that 80–100 a after the closure of the mines relatively large amounts of Cd, Pb, Zn and, in once case, Cu are entering the soil and fluvial systems.Aerial deposition of heavy metals within a 300 m radius of the centre of the tailings heaps is shown to be contributing up to 3.3 kg Cd, 71 kg Cu, 373 kg Pb and 1041 kg Zn annually to the surrounding soil and vegetation compartments. It is shown that more than 4.2 kg Cd/a and 1387 kg Zn/a are being transferred from the tailings heaps via the streams in the form of dissolved load. However, the greatest quantities of Cu (38 kg/a) and Pb (74 kg/a) are transported from the heaps as wash load. Transfers calculated as percentages of the total metal quantities in the tailings heaps highlight the greater relative mobility within the fluvial system of Cd and Zn compared to Cu and Pb. Outside of the tailings heaps, the greatest accumulation of metals is in the surrounding soil, while the smallest was observed to occur in the surrounding mixed grassland vegetation.The most important implications of these findings are in the long-term release and partitioning of pollutant metal species from historic metalliferous mine tailings within the terrestrial and fluvial environments. This information is of major ecotoxicological and agronomic importance and is necessary for the effective reclamation and remediation of such contaminated sites.     

Arsenic and metal mobility from Au mine tailings in Rodalquilar (Almería,SE Spain)

In the old mining area of Rodalquilar, mine wastes, soil and sediments were characterized and the results revealed high concentration of Au, Ag, As, Bi, Cu, Fe, Mn, Pb, Se, Sb and Zn in tailings and sediments. The contaminant of greatest environmental concern is As. The mean concentration in the tailings was 679.9, and 345 mg/kg in the sediments of Playazo creek. The groundwater samples from the alluvial aquifer showed high concentration of Al, As, Cd, Fe, Hg, Mn, Ni, Pb, Se, Sb and Zn and very high concentration of chloride and sulfate, which were above the concentration defined in the European standards for drinking water. The presence of As in groundwater may be caused by the oxidation of arsenian pyrite, the possible As desorption from goethite and ferrihydrite and the jarosite dissolution. Groundwater concentrations of Cd, Fe, Mn, and possibly Cu, were associated with low values of Eh, indicating the possible dissolution of oxy-hydroxides of Fe and Mn. The mobility of metals in the column experiments show the release of Al, Fe, Mn, Cr, Cu, Ni, V and Zn in significant concentrations but below the detected values in groundwater. However, As, Cd, Sb, Se Pb and Au, are generally mobilized in concentrations above the detected values in groundwater. The possible mass transfer processes that could explain the presence of the contaminants in the aquifer and the leachates was simulated with the PHREEQC numerical code and revealed the possible dissolution of the following mineral phases: jarosite, natrojarosite, arsenian pyrite, alunite, chlorite, kaolinite and calcite.     

Heavy metal contamination of soils and waters in and around the Imcheon Au–Ag mine,Korea

The heavy metal contamination of soils and waters by metalliferous mining activities in an area of Korea was studied. In the study area of the Imcheon Au–Ag mine, soils and waters were sampled and analyzed using AAS for Cd, Cu, Pb and Zn. Analysis of HCO₃⁻, F⁻, NO₃⁻ and SO₄²⁻ in water samples was also undertaken by ion chromatography. Elevated concentrations of the metals were found in tailings. The maximum contents in the tailings were 9.4, 229, 6160 and 1640 mg/kg extracted by aqua regia and 1.35, 26.4, 70.3 and 410 mg/kg extracted by 0.1 N HCl solution for Cd, Cu, Pb and Zn, respectively. These metals are continuously dispersed downstream and downslope from the tailings by clastic movement through wind and water. Because of the existence of sulfides in the tailings, a water sample taken on the tailings site was very acidic with a pH of 2.2, with high total dissolved solids (TDS) of 1845 mg/l and electric conductivity (EC) of 3820 μS/cm. This sample also contained up to 0.27, 1.90, 2.80, 53.4, 4,700 mg/l of Cd, Cu, Pb, Zn and SO₄²⁻, respectively. TDS, EC and concentrations of metals in waters decreased with distance from the tailings. The total amount of pulverized limestone needed for neutralizing the acid tailings was estimated to be 46 metric tons, assuming its volume of 45,000 m³ and its bulk density of 1855 kg/m³.     

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.     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Metals in the river waters of Primorye

New data are presented on the contents of Fe, Mn, Zn, Cu, Pb, Cd, and Ni in dissolved and particulate modes of occurrence in unpolluted or anthropogenically contaminated major rivers of Primorye. The background contents of dissolved metals are as follows: 0.1–0.5 μg/l for Zn and Ni, 0.3–0.7 μg/l for Cu, 0.01–0.04 μg/l for Pb and Cd, and 2–20 μg/l for Fe and Mn. Common anthropogenic loading (communal wastewaters) notably increases the dissolved Fe and Mn concentrations Industrial wastes lead to a local increase in the contents of dissolved metals in river waters by one to three orders of magnitude. The effect of hydrological regime is expressed most clearly in the areas of anthropogenic impact. The metal contents in the particulate matter are controlled mainly by its granulometric composition. Original Russian Text ? V.M. Shulkin, N.N. Bogdanov, V.I. Kiselev, 2007, published in Geokhimiya, 2007, No. 1, pp. 79–88.     

Impact of historical metalworks on the concentrations of major and trace elements in sediments: a case study in Finland

The concentrations of major and trace elements were determined (aqua regia leach and ICP-AES analyses) in stream, lake and dredged sediments downstream of the historical Antskog iron- and copperworks, S.Finland. The levels of Ag, Cd, Cu, Pb and Zn are highly elevated in all studied sediment types: roughly half of the studied lake-sediment samples contain >5 ppm Ag, >15 ppm Cd, >0.1% Cu, >0.1% Pb and >0.3% Zn. In the dredged sediment material located onshore, the concentrations of Ag, Cu and Pb are comparable to those in the polluted lake-sediment samples, while in stream sediments elevated metal concentrations are found especially in samples characterised by high concentrations of organic material. The source of the elevated metal concentrations is the historical metalworks at Antskog, mainly the copperworks of the 19th century. Compared to the limit values for contaminated soils in Finland, the concentrations of Cu, Pb and Zn are on average elevated by factors >10 in the polluted horizons of lake sediments, >5 in the dredged sediment located onshore and >2 at the most heavily contaminated site in the stream. Since the surface waters in the area are used for agricultural purposes and for various leisure activities, it is necessary to make further detailed investigations into the extent of the metal pollution and to determine species, mobility and bioavailability of the metals.     

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.     

Speciation and mobility of heavy metals in mud in coastal reclamation areas in Shenzhen,China

Coastal reclamation has been carried out along the coastal areas near Shenzhen, China in a large scale since 1980s by dumping fill materials over the marine mud at the sea bottom. Usually the area to be reclaimed is drained first and some of the mud is air-dried for a few weeks before it is buried by fill. After reclamation, the terrestrial groundwater, which is relatively acidic and with high dissolved oxygen, gradually displaces the seawater, which is alkaline with high salinity. The changes in the burial conditions of mud and the properties of the pore water in the mud may induce the release of some heavy metals into the mud. Field survey confirms that the pH and salinity of the groundwater in the reclamation site are much lower than the seawater. Chemical analyses of mud and groundwater samples collected from the reclamation sites reclaimed in different years indicate that most of the heavy metals in the mud decrease gradually with time, but the heavy metals in the groundwater are increased. The release of heavy metals into pore water due to reactivation of heavy metals in the mud is of environmental concern. To understand why some of the heavy metals can be released from the mud more easily than others, a sequential extraction method was used to study the operationally determined chemical forms of five heavy metals (Cu, Ni, Pb, Zn, and Cd) in the mud samples. Heavy metals can be presented in five chemical forms: exchangeable, carbonate, Fe–Mn oxide, organic, and residual. Ni and Pb were mainly associated with the Fe–Mn oxide fraction and carbonate fraction; Zn was mainly associated with organic fraction and Fe–Mn oxide fraction, while Cu and Cd were associated with organic fraction and carbonate fraction, respectively. If the residual fraction can be considered as an inert phase of the metal that cannot be mobilized, it is the other four forms of heavy metal that cause the noticeable changes in the concentration of heavy metals in the mud. On the basis of the speciation of heavy metals, the mobility of metals have the following order: Pb (36.63%) > Cu (31.11%) > Zn (20.49%) > Ni (18.37%) > Cd (13.46%). The measured metal mobility fits reasonably well with the degree of concentration reduction of the metals with time of burial observed in the reclamation site.     

The effects of the San Francisco Bay plume on trace metal and nutrient distributions in the Gulf of the Farallones

The distributions of particulate elements (Al, P, Mn, Fe, Co, Cu, Zn, Cd, and Pb), dissolved trace metals (Mn, Fe, Co, Cu, Zn, and Cd), and dissolved nutrients (nitrate, phosphate, and silicic acid) were investigated in the Gulf of the Farallones, a region of high productivity that is driven by the dynamic mixing of the San Francisco Bay plume, upwelled waters, and California coastal surface waters. Particulate metals were separated into >10 and 0.4-10 μm size-fractions and further fractionated into leachable (operationally defined with a 25% acetic acid leach) and refractory particulate concentrations. Dissolved metals (< 0.4 μm pore-size filtrate) were separated into colloidal (0.03-0.4 μm) and soluble (<0.03 μm) fractions. The percent leachable particulate fractions ranged from 2% to 99% of the total particulate concentration for these metals with Mn and Cd being predominantly leachable and Fe and Al being predominantly refractory. The leachable particulate Pb concentration was associated primarily with suspended sediments from San Francisco Bay and was a tracer of the plume in coastal waters. The particulate trace metal data suggest that the leachable fraction was an available source of trace metal micronutrients to the primary productivity in coastal waters. The dissolved trace metals in the San Francisco Bay plume and freshly upwelled surface waters were similar in concentration, with the exception of Cu and Co, which exhibited relatively high concentrations in plume waters and served as tracers of this water mass. The dissolved data and estimates of the plume dynamics suggest that the impact of anthropogenic inputs of nutrients and trace metals in the San Francisco Bay plume contributes substantially to the concentrations found in the Gulf of the Farallones (10-50% of estimated upwelled flux values), but does not greatly disrupt the natural stoichiometric balance of trace metal and nutrient elements within coastal waters given the similarity in concentrations to sources in upwelled water. In all, the data from this study demonstrate that the flux of dissolved nutrients and bioactive trace metals from the San Francisco Bay plume contribute to the high and relatively constant phytoplankton biomass observed in the Gulf of the Farallones.     

Sequential extraction and leaching characteristics of heavy metals in abandoned tungsten mine tailings sediments

The chemical speciation of potentially toxic elements (As, Cd, Cu, Pb, and Zn) in the contaminated soils and sulfides-rich tailings sediments of an abandoned tungsten mine in Korea was evaluated by conducting modified BCR sequential extraction tests. Kinetic and static batch leaching tests were also conducted to evaluate the potential release of As and other heavy metals by acidic rain water and the leaching behaviors of these heavy metals. The major sources of the elements were As-, Zn- and Pb-bearing sulfides, Pb carbonates (i.e., cerussite), and Pb sulfates (i.e., anglesite). The biggest pollutant fraction in these soil and tailing samples consists of metals bound to the oxidizable host phase, which can be released into the environment if conditions become oxidative, and/or to residual fractions. No significant difference in total element concentrations was observed between the tailings sediments and contaminated soils. For both sample types, almost no changes occurred in the mobility of As and the other heavy metals at 7 days, but the mobility increased afterwards until the end of the tests at 30 days, regardless of the initial pH. However, the mobility was approximately 5–10 times higher at initial pH 1.0 than at initial pHs of 3.0 and 5.0. The leached amounts of all the heavy metal contents were higher from tailings sediments than from contaminated soils at pH > 3.0, but were lower at pH < 3.0 except for As. Results of this study suggest that further dissolution of heavy metals from soil and tailing samples may occur during extended rainfall, resulting in a serious threat to surface and groundwater in the mine area.     

鄂东南铁山地区土壤-植物系统中重金属元素分布及富集特征

采用原子荧光光谱法和等离子体质谱法(ICP-MS)对鄂东南铁山地区主要河流流经区土壤、植物中重金属元素质量分数及其富集特征的研究表明,研究区西港河流域下游局部地段形成Cu、Zn、Ni、Cd、As重金属元素的土壤污染,东港河流域下游局部地段形成Cd、Cu、As、Pb、Zn重金属元素的土壤污染,植物中已经形成Cd、Zn元素的超量富集.其中土壤中重金属元素的富集主要与冶炼厂废水和尾矿坝渗漏水有关,而植物中重金属元素的富集则受土壤中重金属元素质量分数和植物吸收性能的双重控制.     

The impact of tailings dam spills and clean-up operations on sediment and water quality in river systems: the Rı́os Agrio–Guadiamar,Aznalcóllar,Spain

The Aznalcóllar tailings dam at Boliden Apirsa's Aznalcóllar/Los Frailes Ag–Cu–Pb–Zn mine 45 km west of Seville, Spain, was breached on 25 April 1998, flooding approximately 4600 hectares of land along the Rı́os Agrio and Guadiamar with approximately 5.5 million m³ of acidic water and 1.3×10⁶ m³ of heavy metal-bearing tailings. Most of the deposited tailings and approximately 4.7×10⁶ m³ of contaminated soils were removed to the Aznalcóllar open pit during clean-up work undertaken immediately after the spill until January 1999. Detailed geomorphological and geochemical surveys of the post-clean-up channel, floodplain and valley floor, and sediment and water sampling, were carried out in January and May 1999 at 6 reaches representative of the types of river channel and floodplain environments in the Rı́o Guadiamar catchment affected by the spill. The collected data show that the clean-up operations removed enough spill-deposited sediment to achieve pre-spill metal (Ag, As, Cd, Cu, Pb, Sb, Tl, Zn) concentrations in surface sediment. These concentrations, however, are still elevated above pre-mining concentrations, and emphasise that mining continues to contaminate the Agrio-Guadiamar river system. Dilution by relatively uncontaminated sediment appears to reduce metal concentrations downstream but increases in metal and As concentrations occur downstream, presumably as a result of factors such as sewage and agriculture. River water samples collected in May 1999 have significantly greater dissolved concentrations of metals and As than those from January 1999, probably due to greater sulphide oxidation from residual tailings with concomitant release of metals in the warmer early summer months. These concentrations are reduced downstream, probably by a combination of dilution and removal of metals by mineral precipitation. Single chemical extractions (de-ionised water, CaCl₂ 0.01 mol l⁻¹, CH₃COONH₄ 1 M, CH₃COONa 1 M and ammonium oxalate 0.2 M) on alluvial samples from reaches 1 and 6, the tailings, pre-spill alluvium and marl have shown that the order of sediment-borne contaminant mobility is generally Zn>Cd>Cu>Pb>As. Pb and As are relatively immobile except possibly under reducing conditions. Much of the highly contaminated sediment remaining in the floodplain and channel still contains a large proportion of tailings-related sulphide minerals which are potentially reactive and may continue to release contaminants to the Agrio–Guadiamar river system. Our work emphasises the need for pre-mining geomorphological and geochemical data, and an assessment of potential contributions of contaminants to river systems from other, non-mining sources.     

Trace element speciation and behavior in the tidal Delaware River

Measurements of dissolved As, Cr, Cu, and Se using species-selective techniques were made in the tidal freshwater Delaware River at four sites in July 1991, January 1992, and March 1992. Concentrations of dissolved As, Cr, and Se were generally higher in July than in March or January. Copper concentrations were relatively constant. Both As and Cu increased in concentration in the region of Philadelphia. Measurements of As, Cd, Cr, Cu, Pb, Ni, Se, and Zn in seston were made during the July 1991 and March 1992 sampling using both a total digest and a series of sequential leaches. A large fraction of most of the elements, in the order Cd>Zn>Pb≥Cu>Ni≥As>Cr>Se, was solubilized by weak acid. The remainding fraction, for elements where the acid leach was not complete, was released by a rigorous digestion with concentrated acids. Based on estimates of similar rivers, Pb and Zn appear to be substantially enriched in Delaware River seston compared to other rivers draining the same geological provinces. Arsenic, Se, and Cd in seston may be moderately enriched.     

Interactions between Cd,Cu, Pb,and Zn and four different mine soils

The chemical associations of Cd, Cu, Pb, and Zn in four mine soil samples from the Amizour-Bejaia Pb/Zn mine (Algeria) have been investigated by a five-step sequential extraction procedure. Although Cd preferentially binds to carbonates, Cu, Pb, and Zn are mainly associated with the organic and reducible fractions. Batch adsorption experiments with either mono- or multi-metallic solutions are described with the Freundlich isotherm model. Whatever the nature of the soil sample, the sorption behavior for each given metal except Pb is very similar, indicating that the binding sites at the soil surface are progressively occupied by the metal from the solution. On each soil sample, the decreasing order of sorption can be established as Pb >> Cu > Cd > Zn. When the four metals are simultaneously applied to each soil sample, their specific behavior is strongly affected by their interactions and/or competition for the available surface sites: we generally observed isotherm curves with a slight maximum before the plateau at higher solution concentration. Although Cu is only slightly affected by the other metals, in the case of Pb, Cd, and Zn, the sorbed amounts strongly decreased.     

Environmental geochemistry of the derelict Webbs Consols mine,New South Wales,Australia

Small-scale mining and mineral processing at the Webbs Consols polymetallic PbZnAg deposit in northern New South Wales, Australia has caused a significant environmental impact on streams, soils and vegetation. Unconfined waste rock dumps and tailings dams are the source of the problems. The partly oxidised sulphidic mine wastes contain abundant sulphides (arsenopyrite, sphalerite, galena) and oxidation products (scorodite, anglesite, smectite, Fe-oxyhydroxides), and possess extreme As and Pb (wt% levels) and elevated Ag, Cd, Cu, Sb and Zn values. Contemporary sulphide oxidation, hardpan formation, crystallisation of mineral efflorescences and acid mine drainage generation occur within the waste repositories. Acid seepages (pH 1.9–6.0) from waste dumps, tailings dams and mine workings display extreme As, Pb and Zn and elevated Cd, Cu and Sb contents. Drainage from the area is by the strongly contaminated Webbs Consols Creek and although this stream joins and is diluted by the much larger Severn River, contamination of water and stream sediments in the latter is evident for 1–5 km, and 12 km respectively, downstream of the mine site. The pronounced contamination of local and regional soils and sediments, despite the relatively small scale of the former operation, is due to the high metal tenor of abandoned waste material and the scarcity of neutralising minerals. Any rehabilitation plan of the site should include the relocation of waste materials to higher ground and capping, with only partial neutralisation of the waste to pH 4–5 in order to limit potential dissolution of scorodite and mobilisation of As into seepages and stream waters.     

珠江三角洲污灌区地下水重金属含量及其相互关系

为了解污灌区地下水重金属含量特征,采集地表水样5组、地下水样14组进行化学组分定量分析。结果表明：污灌区地下水8种重金属元素中,仅有Ni和As两种元素超标,超标率分别为14.3％和42.9％。8种重金属含量在污灌区地表水、工厂废水以及地下水中存在明显的对应关系。Ni、Zn、Se、Cd这4种元素间存在显著或极显著的正相关关系,Cu与Pb和Cd分别呈极显著和显著的正相关关系,Cr仅与Ni呈显著的正相关关系,As与其它7种元素的相关性均不明显。聚类分析结果显示8种重金属可分为4类：Pb和Cu一类,Se、Cd、Ni、Zn一类,Cr和As均单独一类。Pb和Cu与Fe的相似性最好,Se、Cd、Ni、Zn与Mg²⁺存在较好的相似性,Cr与HCO^－₃的相似性最好,As与SO^2－₄存在一定的相似性。     

Accumulation and risk assessment of heavy metals in dust in main living areas of Guiyang City,Southwest China

Guiyang is a famous tourist city located in southwestern China. In this study, dust from eleven residential areas, seven city squares, and nine schools was collected to measure the heavy metal levels and evaluate its risk. At each sampling site, 4-5 sub-samples were taken as a bulk sample. All samples were air-dried, ground, passed through a 0.105 mm nylon sieve, digested with HNO3-HC104 to determine the concentrations of Cd, Cu, Ni, Pb and Zn by ICP-MS, and digested with 1：1 aqua regia to determine As by AFS. The results show that the concentrations of As, Cd, Cu, Ni, Pb and Zn in dust of Guiyang City follow normal distribution with means of 16.1, 1.54, 138, 47.7, 129 and 479 mg/kg, respectively. Levels of As, Cd, Cu, Ni, Pb and Zn exceed the background level of soil in Guizhou Province by 33%, 96%, 100%, 78%, 96%, and 100%, respectively. Cd, Cu, Pb and Zn are heavily accumu- lated in dust of living areas with accumulation factors of 4.10, 5.12, 4.12 and 5.51, respectively. City square pos- sesses the highest geometric means of As, Cd, Cu, Pb, and Zn. The risks of heavy metal exposure to teenagers are not obvious and in an order ofAs〉Pb〉Cu〉Ni〉Zn （Cd）.     

Secondary copper enrichment in tailings at the Laver mine, northern Sweden

 Field and laboratory studies of the sulphide-bearing tailings at Laver, northern Sweden, show that the present release of metals from the tailings is low, especially with regard to Cu. A large part of the Cu released by sulphide oxidation is enriched in a distinct zone just below the oxidation front. The enrichment zone occurs almost all over the tailings area except in areas with a shallow groundwater table. The Cu enrichment is caused by formation of covellite and adsorption onto mineral surfaces. The transport of Zn, Co, Cd, Ni and S seems to be controlled mainly by adsorption. No secondary zone or secondary minerals containing these metals have been found. Just below the groundwater table, metals are released into solution when the enrichment zone reaches the groundwater due to the low pH. An increased release of metals, especially Cu, can be expected in the future, since the enrichment zone is moving towards the groundwater table. Received: 4 December 1997 · Accepted: 17 December 1998