Anthropogenic metal loads and their sources in stream sediments of the Me?a River catchment area (NE Slovenia)

The Me?a River Valley has been a center of mining, ore processing and iron- and steel-based metallurgical industry for more than 300 a. This paper deals with stream sediments draining this area. Loads of potentially toxic metals and metal-bearing phases were investigated 10 a after the cessation of Pb and Zn mining. Sediments in the upper Me?a River Valley show significant pollution with Pb and Zn as a consequence of mining and ore processing. The highest contents of Pb and Zn were found in the Me?a tributaries, which directly drain mine waste deposits (maximum values: 19,300 mg/kg Pb and 37,900 mg/kg Zn). These results reflect transport of contaminated material from mine waste sites and indicate that the inactive mine and its mine wastes are sources of metal contamination in the surrounding environment. Contents of Cr, Ni, Cu and Co are increased in the lower Me?a River Valley, in the area of Ravne, as a result of the iron and steel industry. The contribution of the Me?a River to the metal-load in the Drava River is evident.Metal-bearing phases, identified in stream sediments by SEM/EDS, are assigned to three areas, according to their source and genesis. The Me?ica mining district source area is characterized by ore minerals of geogenic/technogenic origin (cerussite, sphalerite, smithsonite and galena), the Ravne source area is characterized by technogenic trace metal-bearing Fe-alloys, Fe-oxides and spherical trace metal-oxides and the Me?a and Drava River catchment areas are represented by geogenic metal-bearing accessory and common rock-forming minerals, such as zircon, ilmenite, rutile, sphene, barite and monazite. SEM/EDS analyses of stream sediments agree well with the results of chemical analyses and they prove to be a very useful tool for identification of metal-bearing phases and their characterization according to source and genesis.     

The spatial distribution and source of arsenic, copper, tin and zinc within the surface sediments of the Fal Estuary, Cornwall, UK

ABSTRACT Estuarine sediments commonly form major sinks for contaminants released during industrial activity. Many industrial processes lead to the release of metals initially in solution, which can then be adsorbed on to, for example, Fe hydroxides or clay minerals. However, in the mining industry, there are two major contaminant waste streams: (1) metals discharged in solution via mine drainage; and (2) particulate grains of the ore‐forming or related minerals released after ore processing. The release of particulate waste can have a major long‐term impact on environmental geochemistry. In this study, we have mapped the distribution of arsenic, copper, tin and zinc within the surficial sediments of the Fal Estuary, Cornwall, UK, an area that drains a historically important polymetallic mining district. There are clear spatial variations in the contaminants, with the highest levels (> 2800 p.p.m. As, > 5000 p.p.m. Cu, > 3000 p.p.m. Sn and > 6000 p.p.m. Zn) within Restronguet Creek on the western side of the estuary. Mineralogical studies show that small (< 20 µm) grains of detrital arsenopyrite, chalcopyrite, cassiterite and sphalerite are very abundant within the surface sediments. Most of the sulphide grains are fractured, but mineralogically unaltered, although some grains show alteration rims caused by oxidation of the sulphides. The geochemistry and mineralogy are indicative of sediment supply from the discharge of particulate waste into the estuary during historical mining activity. Subsequently, this particulate waste has been largely physically and biologically reworked within the surface sediments. Although considerable effort has been made to minimize contaminants released via mine drainage into the estuary, the potential flux of contaminants present within the intertidal and subtidal sediments has not been addressed. Benthic invertebrates living within the area have adapted to be metal tolerant, and it is likely that the dominant source of bioavailable metals is a result of alteration of the particulate mine waste present within the intertidal and subtidal sediments.     

The use of multivariate statistical analysis of geochemical data for assessing the spatial distribution of soil contamination by potentially toxic elements in the Aljustrel mining area (Iberian Pyrite Belt,Portugal)

Aljustrel mine is located in SW Portugal, in the western sector of the Iberian Pyrite Belt. The Aljustrel village was developed around the exploitations of massive polymetallic sulphides that occur in the area (4 orebodies mined, 2 in exploration phase). The pyrite ore was extensively exploited from 1850 to 1993, when production was discontinued. A mining restart occurred in 2008, only during a few months. The objectives of the study were to assess the levels of soil contamination, to determine associations between the different chemical elements and their spatial distribution, as well as to identify possible sources of contamination that can explain the spatial patterns of soil pollution in the area. Principal component analysis combined with spatial interpretation successfully grouped the elements according to their sources and provided evidence about their geogenic or anthropogenic origin. From this study, it is possible to conclude that soils around Algares/Feitais tailing deposits, Estéreis and Águas Claras mine dams and S. João mine show severe contamination. The highest concentrations of As (up to 3,936 mg kg^?1) and certain heavy metals (up to 321.7 mg kg^?1 for Bi, 5,414 mg kg^?1 for Cu, 20,000 mg kg^?1 for Pb, 980.6 mg kg^?1 for Sb, and 22 mg kg^?1 Cd) were obtained near Algares area while the highest concentration of Cd (up to 61.6 mg kg^?1) and Zn (up to 20,000 mg kg^?1) were registered in samples collected in the S. João area. The highest pollution load index (>4.0) was recorded at the Algares area where the metal concentrations exceed typical soil background levels by as much as two orders of magnitude.     

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.     

Heavy metal anomalies in the Tinto and Odiel River and estuary system,Spain

The Tinto and Odiel rivers drain 100 km from the Rio Tinto sulphide mining district, and join at a 20-km long estuary entering the Atlantic Ocean. A reconnaissance study of heavy metal anomalies in channel sand and overbank mud of the river and estuary by semi-quantitative emission dc-arc spectrographic analysis shows the following upstream to downstream ranges in ppm (μg g^?1): As 3,000 to <200, Cd 30 to <0.1, Cu 1,500 to 10, Pb 2,000 to <10, Sb 3000 to <150, and Zn 3,000 to <200. Organic-rich (1.3–2.6% total organic carbon, TOC), sandysilty overbank clay has been analyzed to represent suspended load materials. The high content of heavy metals in the overbank clay throughout the river and estuary systems indicates the importance of suspended sediment transport for dispersing heavy metals from natural erosion and anthropogenic mining activities of the sulfide deposit. The organic-poor (0.21–0.37% TOC) river bed sand has been analyzed to represent bedload transport of naturally-occurring sulfide minerals. The sand has high concentrations of metals upstream but these decrease an order of magnitude in the lower estuary. Although heavy metal contamination of estuary mouth beach sand has been diluted to background levels estuary mud exhibits increased contamination apparently related to finer grain size, higher organic carbon content, precipitation of river-borne dissolved solids, and input of anthropogenic heavy metals from industrial sources. The contaminated estuary mud disperses to the inner shelf mud belt and offshore suspended sediment, which exhibit metal anomalies from natural erosion and mining of upstream Rio Tinto sulphide lode sources (Pb, Cu, Zn) and industrial activities within the estuary (Fe, Cr, Ti). Because heavy metal contamination of Tinto-Odiel river sediment reaches or exceeds the highest levels encountered in other river sediments of Spain and Europe, a detailed analysis of metals in water and suspended sediment throughout the system, and epidemiological analysis of heavy metal effects in humans is appropriate.     

An evaluation of trace metal distribution and environmental risk in sediments from the Lake Kalimanci (FYR Macedonia)

Pollution from mining activities is a significant problem in several parts of the Republic of Macedonia. A geochemical study of the surficial sediments of Lake Kalimanci in the eastern part of the Republic of Macedonia was carried out to determine their elemental compositions and to evaluate the pollution status of lake sediments by employing an enrichment factor (EF). The major and trace element contamination in surficial lake sediments was studied to assess the effects of metalliferous mining activities. The mean concentrations of major elements (wt%) Si 23.5, Al 7.9, Fe 6.6, Mg 1.3, Ca 3.8, Na 1.1, K 2.3, Ti 0.4, P 0.2, Mn 0.6 and trace elements ranged within Mo 1.0–4.6 mg kg^?1, Cu 144.4–1,162 mg kg^?1, Pb 1,874–16,300 mg kg^?1, Zn 2,944–20,900 mg kg^?1, Ni 21.7–79.3 mg kg^?1, Cd 16.5–136 mg kg^?1, Sb 0.6–3.6 mg kg^?1, Bi 3.0–24,3 mg kg^?1 and Ag 1.4–17.3 mg kg^?1. The EF ranged within 0.12–590.3. Among which, Cd, Pb, Zn and As have extremely severe enrichment. The data indicate that trace elements had extremely high concentrations in Lake Kalimanci surficial sediments owing to the anthropogenic addition of contaminants.     

Geochronology of the Limu W–Sn–Nb–Ta‐Bearing Granite Pluton in South China

Limu W–Sn–Nb–Ta mining district is located in the Nanling Range W–Sn poly‐metallic mineralization belt in south China. The district includes a number of Sn–Nb–Ta and W–Sn ore occurrences; all of them are spatially associated with granite stocks of a largely‐unexposed pluton, the Limu granitic pluton. A granite sample collected from the Sn–Nb–Ta‐bearing Jinzhuyuan granite stock yields a zircon SHRIMP U–Pb age of 218.3 ± 2.4 Ma, a muscovite ⁴⁰Ar/³⁹Ar plateau age of 212.4 ± 1.4 Ma, and a muscovite ⁴⁰Ar/³⁹Ar isochron age of 213.2 ± 2.2 Ma. Another granite sample collected from the W–Sn‐bearing Sangehuangniu granite stock yields a zircon SHRIMP U–Pb age of 214 ± 5 Ma. The geochronological data provide new constraints on the age of the Limu granite pluton and the timing of the associated W–Sn–Nb–Ta mineralization—at least it sets a reasonable upper age limit for the mineralization of the W–Sn–Nb–Ta ores. The reported ages suggest an active Late Triassic granitic magmatism in Limu area which is part of a regional magmatic event near the end of the Indosinian orogeny in south China.     

Stable lead isotope ratios and metals in freshwater mussels from a uranium mining environment in Australia’s wet-dry tropics

Concentrations of Fe, Mn, Cu, Zn, U and Pb, and stable Pb isotopes ²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb were measured via inductively coupled plasma mass spectrometry in sediments, water and freshwater mussels (Velesunio angasi) from two catchments in the Alligator Rivers Region, Australia. Sediment U and Pb concentrations were higher in Magela Creek downstream than upstream of the Ranger U mine due to the mineralised nature of the catchment and potential local input of sediment from the mine site. Water metal concentrations were highest in Georgetown Creek, which is a tributary of Magela Creek and part drains the Ranger mine site, but there was little difference in concentrations between the Magela Creek upstream and downstream sites. Metal concentrations in mussels collected immediately upstream and downstream of the mine site also showed little difference, whereas Pb isotope ratios displayed a very distinct pattern. The ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb isotope ratios were more uranogenic downstream than upstream of the site and also more uranogenic than ratios measured in Sandy Billabong, a reference billabong in a catchment not influenced by U mineralisation. Isotope ratios were also more uranogenic in younger mussels, potentially due to the increasing footprint of the mine site over the past decade. The most uranogenic ratios were found in mussels from Georgetown Creek and at a site approximately 2 km downstream. At Mudginberri Billabong, approximately 12 km downstream of the Ranger mine, the relative contribution of uranogenic Pb to the total Pb concentration in mussels was small and overwhelmed by the input of industrial Pb with a Broken Hill type Pb signature. Whereas metal uptake by and thus concentrations in mussel flesh are influenced by water chemistry, mussel condition and metabolic rates, Pb isotope ratios are independent of these factors and provide a powerful means of source apportionment of contaminants in mussels and waterways, in particular in an U mining environment.     

Concentration of metals in surface water and sediment of Luilu and Musonoie Rivers,Kolwezi-Katanga,Democratic Republic of Congo

The pollution and deterioration of most important vital rivers in the Katanga region, Democratic Republic of Congo (DRC) are mainly due to the discharge of untreated industrial effluents as well as to the mining and artisanal mineral exploitation activities. In this study, the concentrations of metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, and Pb) and major elements (Na, Mg, and K) in mining effluents, water and sediment samples of two main rivers of the district of Kolwezi (Katanga, DRC) were subjected to analysis by Inductive Coupled Plasma-Mass Spectroscopy (ICP-MS). The results showed that, in general, the metal concentrations in the sampling sites from the mining effluent and river waters exceed largely the World Health Organization and the Aquatic Quality Guidelines for the Protection of Aquatic Life recommendation limits. The highest metal concentrations in water and sediment samples were detected surrounding the mining effluents discharge. In the surface sediments of Luilu River, the values of 47,468 and 13,199 mg kg⁻¹ were observed for Cu and Co, respectively. For the sediment samples from Musonoie River, the maximum values of 370.8 and 240.6 mg kg⁻¹ for Cu and Co, respectively were observed. The results of this study suggest that the mining effluents being discharged into the rivers and the accumulation of pollutants in sediments might represent a source of toxicity for aquatic living organisms and could pose significant human health risks. The measures to establish a monitoring program and the application of wastewater treatment techniques to the mining effluents prior to discharge are recommended to reduce the load of contaminants into the receiving systems.     

Heavy metal concentrations in sultana-cultivation soils and sultana raisins from Manisa (Turkey)

This paper describes the concentrations of heavy metals in soils and in raisins (sultanas) cultivated upon the Gediz Plain (Manisa), western Turkey, which is cut by major roads from ?zmir to ?stanbul and ?zmir to Ankara. A total of 212 samples of surface soil and 82 raisin samples were analysed. Soil samples have nearly same mineralogy, quartz, calcite, magnetite, pseudo-rutile and clay minerals. Dolomite is seen especially in areas close to Neogene sediments. Clay minerals are mainly mica (illite?Cmuscovite), chlorite/kaolinite, smectite and mixed layers (Sm-Il). The concentrations of 21 elements (Ba, Ni, Mo, Cu, Pb, Zn, Co, Mn, As, U, Sr, Cd, Sb, Bi, Cr, B, W, Hg, Sn, Li and organic C) were determined in the surface soils. The degree of element enrichment in soil can be measured in many ways, the most common of which are the geoaccumulation index (Igeo), enrichment factor and the pollution index. Arsenic and Sb showed the highest Igeo values, corresponding to Igeo classes 3?C4. Hence, the area is characterised as ??being heavily contaminated to polluted?? by As and Sb. Arsenic contamination has been reported from all over world. Arsenic-related pollutants enter the groundwater system by gradually moving with the flow of groundwater from rains and irrigation. Gediz Plain forms the main groundwater supply of ?zmir city. The enrichment factor (EF_arsenic) of the analysed soil samples is around 76, which corresponds to ??extremely high enrichment??. The concentrations of 33 elements (Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cu, Fe, Pb, Li, Mg, Mn, Hg, Mo, Ni, K, Se, Ag, Na, Sr, Ta, Th, Sn, Ti, U, V, Zn and Zr) were determined in the raisin samples. The Pb and Cd contents of raisins are of great concern due to their toxicity. Pb contents ranged between 0.05 and 0.46?mg?kg^?1, and average Cd content was 0.04?mg?kg^?1. Only one sample contained high level of Cd, 0.23?mg?kg^?1. After cleaning the raisins, the heavy metal concentrations were low as in the European Community (EC) regulation No: 466/2001 for allowable levels of Pb (0.2?mg?kg^?1) and Cd (0.05?mg?kg^?1).     

Mineral components in a peat deposit: looking for signs of early mining and smelting activities in Silesia–Cracow region (Southern Poland)

The results of investigations (SEM/EDS and AAS) of a peat deposit, spanning 13,000 years of peat accumulation, are shown. The peat deposit is located in a region of shallow occurrence of Zn–Pb ores, near Tarnowskie Góry town, within the Cracow–Silesia district (southern Poland). Exploitation of lead, silver and iron during the medieval times (Twelfth and thirteenth century) was confirmed by historical documents whereas there are no unambiguous data showing that there was metal mining during the Romanian or earlier times in the region. The peat deposit is located within the influence of atmospheric Pb and Zn emission from a nearby Zn–Pb smelter. Two vertical peat profiles were investigated (120 and 140 cm depth of profile) showing variable concentrations of Zn up to 713 mg kg^?1, Pb up to 317 mg kg^?1, Cd up to 13 mg kg^?1 and Tl up to 31 mg kg^?1. The highest concentrations were recorded for the uppermost peat layers. SEM and EDS investigations revealed the occurrence of metalbearing, submicroscopic mineral components: Fe, Mn, Ti and Zn oxides and Zn and Pb carbonates. The top layer of the deposit contained Zn, Pb and Cd sulphides. The occurrence of aggregates of Au–Ag, Cu–Zn and Au–Ag–Cu alloys can be possibly related to pre-historical mining and smelting or be explained by geochemical transformations. The preservation of carbonates and oxides in the peat is discussed, indicating a generally neutral to alkaline peat water chemistry and maintenance of an oxidized environment in the fen.     

Geomorphic controls on mercury accumulation in soils from a historically mined watershed, Central California Coast Range, USA

Historic Hg mining in the Cache Creek watershed in the Central California Coast Range has contributed to the downstream transport of Hg to the San Francisco Bay-Delta. Different aspects of Hg mobilization in soils, including pedogenesis, fluvial redistribution of sediment, volatilization and eolian transport were considered. The greatest soil concentrations (>30 mg Hg kg⁻¹) in Cache Creek are associated with mineralized serpentinite, the host rock for Hg deposits. Upland soils with non-mineralized serpentine and sedimentary parent material also had elevated concentrations (0.9–3.7 mg Hg kg⁻¹) relative to the average concentration in the region and throughout the conterminous United States (0.06 mg kg⁻¹). Erosion of soil and destabilized rock and mobilization of tailings and calcines into surrounding streams have contributed to Hg-rich alluvial soil forming in wetlands and floodplains. The concentration of Hg in floodplain sediment shows sediment dispersion from low-order catchments (5.6–9.6 mg Hg kg⁻¹ in Sulphur Creek; 0.5–61 mg Hg kg⁻¹ in Davis Creek) to Cache Creek (0.1–0.4 mg Hg kg⁻¹). These sediments, deposited onto the floodplain during high-flow storm events, yield elevated Hg concentrations (0.2–55 mg Hg kg⁻¹) in alluvial soils in upland watersheds. Alluvial soils within the Cache Creek watershed accumulate Hg from upstream mining areas, with concentrations between 0.06 and 0.22 mg Hg kg⁻¹ measured in soils 90 km downstream from Hg mining areas. Alluvial soils have accumulated Hg released through historic mining activities, remobilizing this Hg to streams as the soils erode.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Assessment of heavy metal contamination levels of street dust in the city of Lublin,E Poland

Heavy metals are constantly emitted into the environment and pose a major threat to human health, particularly in urban areas. The threat is linked to the presence of Cd, Cr, Cu, Ni, Pb, and Zn in street dust, which consists of mineral and organic particles originating from the soil, industrial emitters, motor vehicles, and fuel consumption. The study objective was to determine the level of street dust contamination with trace metals in Lublin and to indicate their potential sources of origin. The analyses were carried out with an energy-dispersive X-ray fluorescence spectrometer. The sampling sites (49) were located within the city streets characterised by varying intensity of motor traffic. The following mean content values and their variation (SD) were determined: Cd: 5.1?±?1.7 mg kg^?1, Cr: 86.4?±?23.3 mg kg^?1, Cu: 81.6?±?69.2 mg kg^?1, Ni: 16.5?±?3.9 mg kg^?1, Pb: 44.1?±?16.4 mg kg^?1, and Zn: 241.1?±?94.6 mg kg^?1. The level of pollution was assessed with several widely used geochemical indices (geoaccumulation index, enrichment factor, pollution index, index of ecological risk, and potential ecological risk index). For most of the indices, the mean (median) values are arranged in the following manner: Zn?>?Cu(or Cd)?>?Pb?>?Ni?>?Cr. In general, street dust in Lublin does not show pollution with Cr, Ni, and Pb. I_geo and EF indices show moderate levels for Cu, Cd, and Zn; their presence in street dust is linked with anthropogenic factors (motor traffic). A significant threat is posed by Cd, and more than half of the samples show considerable pollution with cadmium (median for the index of ecological risk: 151). The spatial pattern of indices and the results of statistical analyses (CA, PCA) indicate three groups of elements: (1) Cr and Ni: natural origin; (2) Pb: mixed origin; and (3) Cd, Cu, and Zn: anthropogenic origin (mainly motor vehicle traffic). Higher content values for metals of anthropogenic origin in street dust indicate that it is a source of pollution of soil and air in the city.     

Prediction of the long-term performance of abandoned lead zinc mine tailings in a Welsh catchment

In this study we investigated the sulphidic mine tailings from Frongoch and Grogwynion, two abandoned lead zinc mines in mid-Wales, UK. Despite falling within the same ore field the mine waste characterisation has identified differences in the tailings from the two sites. Bulk concentrations range from 10 to 52 g kg^− 1 for Pb, 1.1 to 2.9 g kg^− 1 for Zn in Grogwynion and from 1.0 to 130 g kg^− 1 for Pb, 11 to 110 g kg^− 1 for Zn in Frongoch. An experimental (European standard leaching tests TS 14429 and TS 14405) and geochemical modelling approach was used to study the leaching composition as a function of pH and liquid/solid ratio. There was little correlation between the tailings bulk metal concentrations and the leachate composition, but variations in Pb and Zn concentrations were found to be consistent with control of dissolved Pb and Zn by secondary minerals and the mechanisms of dissolution/precipitation/sorption involving them. Specifically, the Grogwynion mine tailings with near-neutral pH have predominantly lead and zinc carbonates controlling Pb and Zn solubility in the leachates, whereas the Pb and Zn concentrations in Frongoch leachates are best modelled with a surface complexation model for metal sorption to oxyhydroxides. The different speciation results in a greater sensitivity of Grogwynion tailings to acidification with a potential release of Pb in solution up to 10 times higher than in Frongoch, despite similar bulk Pb concentrations. At acid pH, Zn is similarly dissolved to a greater extent in Grogwynion than in Frongoch tailings. There was no evidence of sulphide oxidation during the batch and column leaching tests and the suitability of using these European leaching standards for the characterisation of sulphidic mine waste materials for waste management purposes has been considered.     

Pb isotope evidence for contaminant-metal dispersal in an international river system: The lower Danube catchment,Eastern Europe

Lead isotope signatures (²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb), determined by magnetic sector ICP-MS in river channel sediment, metal ores and mine waste, have been used as geochemical tracers to quantify the delivery and dispersal of sediment-associated metals in the lower Danube River catchment. Due to a diverse geology and range of ore-body ages, Pb isotope signatures in ore-bodies within the lower Danube River catchment show considerable variation, even within individual metallogenic zones. It is also possible to discriminate between the Pb isotopic signatures in mine waste and river sediment within river systems draining individual ore bodies. Lead isotopic data, along with multi-element data; were used to establish the provenance of river sediments and quantify sedimentary contributions to mining-affected tributaries and to the Danube River. Data indicate that mining-affected tributaries in Serbia and Bulgaria contribute up to 30% of the river channel sediment load of the lower Danube River. Quantifying relative sediment contributions from mining-affected tributaries enables spatial patterns in sediment-associated metal and As concentrations to be interpreted in terms of key contaminant sources. Combining geochemical survey data with that regarding the provenance of contaminated sediments can therefore be used to identify foci for remediation and environmental management strategies.     

Quantification of oxygen consumption and sulphate release rates for waste rock piles using kinetic cells: Cluff lake uranium mine,northern Saskatchewan,Canada

Oxidation rates of low sulphide (<0.5 wt.%) gneissic waste rock from the Cluff lake U mine, northern Saskatchewan, Canada were determined using 3 independent methods: O₂ consumption rates in kinetic cells, SO₄ measurements of kinetic cell effluent and humidity cell SO₄ release rates. The O₂ consumption measurements demonstrated that the oxidation of pyrite was strongly dependent on grain size and moderately dependent on water content, temperature and microbiology. Oxygen consumption rates were highest at water contents of 5–10 wt.% (12–25% saturation). Measured SO₄ release rates (3.1–91 mg SO₄ kg⁻¹ wk⁻¹) for the kinetic cells were comparable to rates calculated from the O₂ consumption values (6.9–70 mg SO₄ kg⁻¹ wk⁻¹). Sulphate release rates determined from humidity cells were generally higher than those obtained from the kinetic cells, ranging from 6 to 64 mg SO₄ kg⁻¹ wk⁻¹ for the coarsest and finest fraction, respectively. These differences were attributed to sample heterogeneity.     

Tracing sources of pollution in soils from the Jinding Pb–Zn mining district in China using cadmium and lead isotopes

Systematic variations in the Cd and Pb isotope ratios in polluted topsoils surrounding the Jinding Pb–Zn mine in China were measured so that the sources of the metals could be traced. The average δ^114/110Cd value and ²⁰⁶Pb/²⁰⁷Pb isotope ratio in background soils from the region were +0.41‰ and 1.1902, respectively, whereas the contaminated soil samples had different values, with the δ^114/110Cd values varying between −0.59‰ and +0.33‰ and the ²⁰⁶Pb/²⁰⁷Pb isotope ratios varying between 1.1764 and 1.1896. We also measured the Cd and Pb isotopic compositions in oxide ores, sulfide ores, and slags, and found that binary mixing between ores and background soils could explain almost all of the variations in the Cd and Pb isotope ratios in the contaminated soils. This suggests that Cd and Pb pollution in the soils was mainly caused by the deposition of dust emitted during anthropogenic activities (mining and refining). The Pb and Cd isotope ratios clearly showed that contamination in soils in the northeastern part of the area was caused by surface mines and zinc smelters and their slagheaps, while contamination in soils in the southwestern part of the area also came from tailing ponds and underground mines. The main area of soil polluted by dust from Pb–Zn mining processes roughly extended for up to 5 km from the mine itself.     

Heavy metal pollution of coastal river sediments, north-eastern New South Wales, Australia: lead isotope and chemical evidence

 Heavy metal and metalloid concentrations within stream-estuary sediments (<180-μm size fraction) in north-eastern New South Wales largely represent natural background values. However, element concentrations (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn) of Hunter River sediments within the heavily industrialized and urbanized Newcastle region exceed upstream background values by up to one order of magnitude. High element concentrations have been found within sediments of the Newcastle Harbour and Throsby Creek which drains into urbanized and light industry areas. Observed Pb enrichments and low ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb ratios are likely caused by atmospheric deposition of Pb additives from petrol and subsequent Pb transport by road run-off waters into the local drainage system. Sediments of the Richmond River and lower Manning, Macleay, Clarence, Brunswick and Tweed River generally display no evidence for anthropogenic heavy metal and metalloid contamination (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn). However, the rivers and their tributaries possess localized sedimentary traps with elevated heavy metal concentrations (Cu, Pb, Zn). Lead isotope data indicate that anthropogenic Pb provides a detectable contribution to investigated sediments. Such contributions are evident at sample sites close to sewage outlets and in the vicinity of the Pacific Highway. In addition, As concentrations of Richmond River sediments gradually increase downstream. This geochemical trend may be the result of As mobilization from numerous cattle-dip sites within the region into the drainage system and subsequent accumulation of As in downstream river and estuary sediments. Received: 5 September 1997 · Accepted: 4 November 1997     

Effects of copper mining on heavy metal contamination in a rice agrosystem in the Xiaojiang River Basin,southwest China

Metallic ore mining causes heavy metal pollution worldwide. However, the fate of heavy metals in agrosystems with long-term contamination has been poorly studied. Dongchuan District (Yunnan, southwest China), located at the middle reaches of the Xiaojiang River, is a well-known 2000-year-old copper mining site. In this work, a survey on soil heavy metal contents was conducted using a handheld X-ray fluorescence instrument to understand the general contamination of heavy metals in the Xiaojiang River Basin. Furthermore, river water, soil, and rice samples at six sites along the fluvial/alluvial fans of the river were collected and analyzed to implement an environmental assessment and an evaluation of irrigated agrosystem. V, Zn, and Cu soil levels (1724, 1047, and 696 mg·kg⁻¹, respectively) far exceeded background levels. The geo-accumulation indexes (I_geo) showed that cultivated soils near the mining sites were polluted by Cd and Cu, followed by Zn, V, Pb, Cr, Ni, and U. The pollution index (Pi) indicated that rice in the area was heavily polluted with Pb, Cr, Cd, Ni, Zn, and Cu. The difference in orders of metal concentrations between the soil and rice heavy metal contamination was related to the proportion of bioavailable heavy metals in the soil. The crop consumption risk assessment showed that the hazard quotient exceeded the safe threshold, indicating a potential carcinogenic risk to consumers. The Nemerow integrated pollution index and health index indicated that the middle of the river (near the mining area) was the heaviest polluted site.