Spatial and temporal variability of surface water and groundwater before and after the remediation of a Portuguese uranium mine area

The old Senhora das Fontes uranium mine, in central Portugal, consists of quartz veins which penetrated along fracture shear zones at the contact between graphite schist and orthogneiss. The mine was exploited underground until a depth of 90 m and was closed down in 1971. The ores from this mine and two others were treated in the mine area by the heap-leach process which ended in 1982. Seven dumps containing a total of about 33,800 m³ of material and partially covered by natural vegetation were left in the mine area. A remediation process took place from May 2010 to January 2011. The material deposited in dumps was relocated and covered with erosion resisting covers. Surface water and groundwater were collected in the wet season just before the remediation, in the following season at the beginning of the remediation and also after the remediation in the following dry season. Before, at the beginning and after the remediation, surface water and groundwater have an acid-to-alkaline pH, which decreased with the remediation, whereas Eh increased. In general, before the remediation, uranium concentration was up to 83 μg/L in surface water and up to 116 μg/L in groundwater, whereas at the beginning of the remediation it increases up to 183 μg/L and 272 μg/L in the former and the latter, respectively, due to the remobilization of mine dumps and pyrite and chalcopyrite exposures, responsible for the pH decrease. In general, after the remediation, the U concentration decreased significantly in surface water and groundwater at the north part of the mine area, but increased in both, particularly in the latter up to 774 μg/L in the south and southwest parts of this area, attributed to the remobilization of sulphides that caused mobilization of metals and arsenic which migrated to the groundwater flow. Uranium is adsorbed in clay minerals, but also in goethite as indicated by the geochemical modelling. After the remediation, the saturation indices of oxyhydroxides decrease as pH decreases. The remediation also caused decrease in Cd, Co, Cr, Ni, Pb, Zn, Cu, As, Sr and Mn concentrations of surface water and groundwater, particularly in the north part of the mine area, which is supported by the speciation modelling that shows the decrease of most dissolved bivalent species. However, in general, after the remediation, Th, Cd, Al, Li, Pb, Sr and As concentrations increased in groundwater and surface water at south and southwest of the mine area. Before and after the remediation, surface water and groundwater are contaminated in U, Cd, Cr, Al, Mn, Ni, Pb, Cu and As. Remediation caused only some improvement at north of the mine area, because at south and southwest part, after the remediation, the groundwater is more contaminated than before the remediation.     

Contaminant dispersion at the rehabilitated Mary Kathleen uranium mine, Australia

This study reports on the transfer of contaminants from waste rock dumps and mineralised ground into soils, sediments, waters and plants at the rehabilitated Mary Kathleen uranium mine in semi-arid northwest Queensland. Numerous waste rock dumps were partly covered with benign soil and the open pit mine was allowed to flood. The mineralised and waste calc-silicate rock in the open pit and dumps has major (>1 wt%) Ca, Fe and Mg, minor (>1,000 ppm) Ce, La, Mn, P and S, subminor (>100 ppm) Ba, Cu, Th and U, and trace (<100 ppm) As, Ni, Pb, Y and Zn values. Consequently, chemical and physical weathering processes have acted on waste rock and on rock faces within the open pit, mobilising many elements and leading to their dispersion into soils, stream sediments, pit water and several plant species. Chemical dispersion is initiated by sulfide mineral breakdown, generation of sulfuric acid and formation of several soluble, transient sulfate minerals as evaporative efflorescent precipitates. Radiation doses associated with the open pit average 5.65 mSv year⁻¹; waste dumps commonly have lower values, especially where soil-covered. Surface pit water is slightly acid, with high sulfate values accompanied by levels of U, Cu and Ni close to or above Australian water guideline values for livestock. Dispersion of U and related elements into soils and stream sediments occurs by physical (erosional) processes and from chemical precipitation. Plants growing in the mine void, on waste dumps and contaminated soil display evidence of biological uptake of U, LREE, Cu and Th and to a lesser degree of As, Ni, Pb, Y and Zn, with values being up to 1–2 orders of magnitude above background sites for the same species. Although rehabilitation procedures have been partly successful in reducing dispersion of U and related elements into the surrounding environment, it is apparent that 20 years after rehabilitation, there is significant physical and chemical mobility, including transfer into plants.     

Heavy metal geochemistry of the acid mine drainage discharged from the Hejiacun uranium mine in central Hunan,China

The acid mine drainage (AMD) discharged from the Hejiacun uranium mine in central Hunan (China) was sampled and analyzed using ICP-MS techniques. The analyzing results show that the AMD is characterized by the major ions Fe_Total, Mn, Al and Si, and is concentrated with heavy metals and metalloids including Cd, Co, Ni, Zn, U, Cu, Pb, Tl, V, Cr, Se, As and Sb. During the AMD flowing downstream, the dissolved heavy metals were removed from the AMD waters through adsorption onto and co-precipitation with metal-oxhydroxides coated on the streambed. Among these metals, Cd, Co, Ni, Zn, U, Cu, Pb and Tl are negatively correlated to pH values, and positively correlated to major ions Fe, Al, Si, Mn, Mg, Ca and K. The metals/metalloids V, Cr, Se, As and Sb are conservative in the AMD solution, and negatively-correlated to major ions Na, Ca and Mg. Due to the above different behaviors of these chemical elements, the pH-negatively related metals (PM) and the conservative metals (CM) are identified; the PM metals include Cd, Co, Ni, Zn, U, Cu, Pb and Tl, and the CM metals V, Cr, Se, As and Sb. Based on understanding the geochemistry of PM and CM metals in the AMD waters, a new equation: EXT = (Acidity + PM)/pH + CM × pH, is proposed to estimate and evaluate extent of heavy-metal pollution (EXT) of AMD. The evaluation results show that the AMD and surface waters of the mine area have high EXT values, and they could be the potential source of heavy-metal contamination of the surrounding environment. Therefore, it is suggested that both the AMD and surface waters should be treated before they are drained out of the mine district, for which the traditional dilution and neutralization methods can be applied to remove the PM metals from the AMD waters, and new techniques through reducing the pH value of the downstream AMD waters should be developed for removal of the CM metals.     

Ordinary kriging and indicator kriging in the cartography of trace elements contamination in São Domingos mining site (Alentejo, Portugal)

The abandoned pyrite mine of São Domingos, in the southeast Portugal is still an acid mine drainage generator and a source for trace elements pollution. This study aims to evaluate and map the soils and sediments chemical pollution. With this purpose three test sites located in the vicinities of the mine were sampled for soils, sediments and mining waste materials. The samples were analysed for pH, organic carbon, iron oxides and total content of As, Cu, Cr, Hg, Pb, Sb, U, Zn, Mn, S, Fe Al, Ca, K, Mg and P. The hyperspectral image of the test sites was acquired using the aero transported sensor HymapTM. Chemical analysis and hyperspectral images data were processed to estimate the contamination maps by multivariate data analysis, ordinary kriging, cokriging and indicator kriging methodologies.The test sites located downstream the mine open pit, are highly contaminated mainly in As, Hg, Pb and Sb, but no contamination was found in the third test site, upstream the mining site. The acid mining drainage seems to be the main spreading agent of chemical contaminants mostly originating from the mine waste materials. Factorial analysis and the geostatistical methodologies allowed several approaches for the contamination cartography of mining areas.     

Source and remediation for heavy metals of soils at an iron mine of Ulsan City,Korea

Ulsan mine produced the iron ore minerals of magnetite, arsenopyrite, and scheelite in 1992, and serpentine was developed from 1977 to 2002. The soils of the mine were contaminated by heavy metals such as As, Zn, Ni, and Cd. Heavy metals of Ni and Zn came mostly from serpentinite, and As was derived mainly from arsenopyrite in the scan-type iron ore body. As, Zn, and Ni were major contaminants, but Cd was a minor contaminant on a basis of Korean standard. The heavy metals in the deep depth (>?5 m) came from the host rocks, and those in the shallow depth (<?5 m) were derived from the organic–mineral complexation soil. The remediation plan was a soil washing for highly contaminated soils and the containment of clay materials for less contaminated soils. Even though the remediation methods were successful, the continuous monitoring and the analysis of monitoring data are still necessary for the conservation of soil and groundwater around the study area.     

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.     

Distribution and environmental geochemistry of some heavy metals in stream sediments of Wadi Allaqi, South Eastern Desert of Egypt

The study focuses on the lateral distribution and the environmental geochemistry of seven heavy metals: Fe, Mn, Cu, Co, Ni, Pb, and Zn in addition to Al in the stream sediments of Wadi Allaqi. Forty-two samples were collected from the upstream, the midstream, and the downstream of this Wadi. Results of the grain size analysis show that the sediments of Wadi Allaqi are fine to medium sand. The heavy metals content reflects the weathering impact on the hinterland. The highest concentrations of Fe, Al, Mn, Cu, Pb, and Zn are recorded in the midstream that is dominated by clastics of felsic and intermediate composition. Moreover, the downstream, occupied by ultrabasic–basic rocks, shows the highest averages of Co and Ni. These results suggest that the felsic and intermediate rocks are the main source of the former metals, whereas the ultrabasic–basic rocks are the source of later two metals. All the analyzed heavy metals have average concentrations lower than their backgrounds, except for Co and Pb. The pollution level by these heavy metals has been evaluated using enrichment ratio (ER), pollution load index (PLI), and index of geoaccumulation (Igeo). The calculated values of ER, CF, PLI, and Igeo indicate that Wadi Allaqi sediments are almost pristine except occasional feeble pollution level by Co and Pb.     

湘江入湖河段沉积物重金属污染及其Pb同位素地球化学示踪

湘江是我国重金属污染最严重的河流之一.本次工作利用等离子质谱(ICP-MS)和多接收同位素质谱(MC-ICP-MS)等技术,对湘江入湖河段沉积物进行了系统的重金属微量元素和Pb同位素分析.结果表明,湘江河床沉积物明显富集Bi、Sc、V、Mn、Ni、Cu、Zn、Pb、Cd、Sn、Sb等多种重金属微量元素,而湖盆沉积物重金...     

Geochemical comparison of waters and stream sediments close to abandoned Sb-Au and As-Au mining areas,northern Portugal

Waters from abandoned Sb-Au mining areas have higher Sb (up to 2138 μg L⁻¹), As (up to 1252 μg L⁻¹) and lower Al, Zn, Li, Ni and Co concentrations than those of waters from the As-Au mining area of Banjas, which only contain up to 64 μg L⁻¹ As. In general, Sb occurs mainly as SbO₃⁻ and As H₂AsO₄⁻. In general, waters from old Sb-Au mining areas are contaminated in Sb, As, Al, Fe, Cd, Mn, Ni and NO₂⁻, whereas those from the abandoned As-Au mining area are contaminated in Al, Fe, Mn, Ni, Cd and rarely in NO₂⁻. Waters from the latter area, immediately downstream of mine dumps are also contaminated in As. In stream sediments from Sb-Au and As-Au mining areas, Sb (up to 5488 mg kg⁻¹) and As (up to 235 mg kg⁻¹) show a similar behaviour and are mainly associated with the residual fraction. In most stream sediments, the As and Sb are not associated with the oxidizable fraction, while Fe is associated with organic matter, indicating that sulphides (mainly arsenopyrite and pyrite) and sulphosalts containing those metalloids and metal are weathered. Arsenic and Sb are mainly associated with clay minerals (chlorite and mica; vermiculite in stream sediments from old Sb-Au mining areas) and probably also with insoluble Sb phases of stream sediments. In the most contaminated stream sediments, metalloids are also associated with Fe phases (hematite and goethite, and also lepidocrocite in stream sediments from Banjas). Moreover, the most contaminated stream sediments correspond to the most contaminated waters, reflecting the limited capacity of stream sediments to retain metals and metalloids.     

Heavy-metal loadings related to urban contamination in the Kooloonbung Creek catchment,Port Macquarie,New South Wales

Urbanisation and industrial development lead to contamination of estuaries and streams with dispersed loadings of heavy metals and metalloids. Contributions of these elements also occur from natural sources. This study provides baseline geochemical data on the respective natural and anthropogenic inputs of Cu, Pb, Zn, Cd, As, Sb, Cr, Ni, Mn and S to estuarine, fluvial and wetland sediments, and adjacent soils, in the Kooloonbung Creek catchment that drains the Port Macquarie urban area in north coastal New South Wales. There have been anthropogenic additions of Cu, Pb, Zn and As from dispersed urban sources at Port Macquarie, but they are restricted to the local catchment and do not impact on the adjacent Hastings River estuary. The most contaminated sediments display enrichment factors up to 20 × for Cu and Pb, 9 × for Zn and 5 × for As relative to local background values. However, only one value (for Pb) exceeds National Water Quality Management Strategy interim sediment quality guideline (high) values. On the other hand, sediments and local soils are commonly strongly enriched in Cr, Ni and Mn, reflecting adjacent ultramafic and mafic rock substrate and lateritic regolith. Concentrations of Cr and Ni are commonly well above interim sediment quality guideline (high) values for sediments, but are in mineralogical forms that are not readily bioavailable. Sediment and soil quality guideline values consequently need to recognise natural enrichments and the mineralogical siting of heavy metals. Although dissolved concentrations of heavy metals in stream waters are commonly low, there is evidence for mobility of Cu, Zn, Fe and Al. Parts of the Kooloonbung Creek wetland area lie on sulfidic estuarine sediments (potential acid sulfate soils). Experimental oxidation of uncontaminated and contaminated sulfidic sediments leads to substantial dissolution of heavy metals under acid conditions, with subsequent aquatic mobility. The results warn about disturbance and oxidation of potential acid sulfate soils that have been contaminated by urban and natural heavy-metal sources.     

Environmental contamination of trace elements in the vicinity of Okpara coal mine, Enugu, Southeastern Nigeria

Water, sediment, and mine spoil samples were collected within the vicinity of the Okpara coal mine in Enugu, Southeastern Nigeria, and analyzed for trace elements using ICP-MS to assess the level of environmental contamination by these elements. The results obtained show that the mine spoils and sediments are relatively enriched in Fe, with mean values of 1,307.8(mg/kg) for mine spoils and 94.15% for sediments. As, Cd, Cr, Mn,Ni, Pb, and Zn in the sediments were found to be enriched relative to the mean values obtained from the study area, showing contamination by these elements. The mean values of Fe, Mn, Cu, and Cr in the mine spoils and mean values of Fe, Cu, Pb, Zn, Ni, Cr, and Mn in sediments, respectively, are above the background values obtained from coal and shale in the study area, indicating enrichment with these elements. The water and sediments are moderately acidic, with mean pH values of 4.22?±?1.06 and 4.66?±?1.35, respectively. With the exception of Fe, Mn, and Ni, all other elements are within the Nigerian water quality standard and WHO limits for drinking water and other domestic purposes. The strong to moderate positive correlation between Fe and Cu (r?=?0.72), Fe and Zn (r?=?0.88), and Fe and As (r?=?0.60) at p?<?0.05 as obtained for the sediments depict the scavenging effect of Fe on these mobile elements. As also shows a strong positive correlation with Mn (r?=?≥ 0.70, p?<?0.05), indicating that Mn plays a major role in scavenging elements that are not co-precipitated with Fe. In water, the strong positive correlation observed between Cr and Cd (r?=?1.00), Cu and Ni (r?=?0.94), Pb and Cu (r?=?0.87) and Zn and Cu (r?=?0.99); Ni and Pb (r?=?0.83) and Zn and Ni (r?=?0.97); and between Pb and Zn (0.84) at p?<?0.05 may indicate similar element–water reaction control on the system due to similarities in chemical properties as well as a common source. Elevated levels of heavy metals in sediments relative to surface water probably imply that sorption and co-precipitation on Al and Fe oxides are more effective in the mobilization and attenuation of heavy metals in the mine area than acid-induced dissolution. The level of concentration of trace elements for the mine spoils will serve as baseline data for future reference in the study area.     

Arsenic contamination at the Mole River mine,northern New South Wales

Mining and processing of arsenopyrite ore at the Mole River mine in the 1920–1930s resulted in abandoned mine workings, waste dumps and an arsenic oxide treatment plant. Weathering of waste material (2.6–26.6 wt% As) leads to the formation of water soluble, As‐bearing mineral salts (pharmacolite, arsenolite, krautite) and sulfates which affect surface waters after rainfall events. Highly contaminated soils, covering about 12 ha at the mine, have extreme As (mean 0.93 wt%) and elevated Fe, Ag, Cu, Pb, Sb and Zn values compared with background soils (mean 8 ppm As). Regionally contaminated soils have a mean As content of 55 ppm and the contaminated area is estimated to be 60 km². The soils have acquired their metal enrichments by hydromorphic dispersion from the dissolution of As‐rich particulates, erosion of As‐rich particulates from the dumps, and atmospheric fall‐out from processing plant emissions. Stream sediments within a radius of 2 km of the mine display metal enrichments (62 ppm to 27.5 wt% As) compared with the mean background of 23 ppm As. This enrichment has been caused by erosion and collapse of waste‐dump material into local creeks, seepages and ephemeral surface runoff, and erosion and transportation of contaminated soil into the local drainage system. Water samples from a mine shaft and waste‐dump seepages have the lowest pH (4.1) and highest As values (up to 13.9 mg/L), and contain algal blooms of Klebsormidium sp. The variable flow regime of the Mole River causes dilution of As‐rich drainage waters to background values (mean 0.0086 mg/L As) within 2.5 km downstream. Bioaccumulation of As and phytotoxicity to lower plants has been observed in the mine area, but several metal‐tolerant plant species (Angophora floribunda, Cassinia laevis, Chrysocephalum apiculatum, Cymbopogon refractus, Cynodon dactylon, Juncus subsecundus and Poa sieberiana) colonise the periphery of the contaminated site.     

Environmental geochemistry of the Gulf Creek copper mine area, north-eastern New South Wales, Australia

 Past mining and smelting of sulphide ore (pyrite-chalcopyrite-sphalerite) at the abandoned Gulf Creek mine has resulted in a stream highly contaminated by acid mine drainage (pH: 2.2–3.4), as well as degradation of local soil and vegetation. Physical dispersion of secondary metal-bearing minerals from abandoned ore and waste dumps into Gulf Creek and adsorption and coprecipitation of dissolved metals and metalloids in the stream bed cause elevated Ag, As, Cd, Cu, Fe, Pb and Zn values in stream sediments. The bioavailability of individual heavy metals to freshwater organisms changes downstream, however, selective bioaccumulation processes in algae reject readily bioavailable Zn and concentrate less bioavailable Cu. Polluted soils in the vicinity of the mine and smelter sites are subject to continuing soil erosion and either support no vegetation, or a depauperate flora with certain species showing bioaccumulation of metals and resistance to high metal contents. Rehabilitation of disturbed areas should involve covering and sealing sulphidic mine waste or removal of ore and waste dumps, installation of a physical and chemical plant or construction of a wetland environment (plus anoxic lime drains), and import of topsoil and planting of local, metal-tolerant plant species. Received: 17 March 1998 / Accepted: 6 October 1998     

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.     

AB-DTPA提取法在重金属污染土壤修复模拟试验中的应用可行性

将碳酸氢铵-二乙三胺五乙酸(AB-DTPA)提取重金属生物有效态的方法应用于重金属污染土壤修复的模拟试验中,该土壤的污染元素主要是铜、锌和镉,试验所用修复材料是钠化膨润土。研究表明,AB-DTPA提取法具有很好的稳定性,而且能准确指示铜、锌、镉元素在土壤中的有效态含量,同时AB-DTPA对土壤中铜、锌、镉元素的提取率也适用于模拟试验中修复效果的平行对比。AB-DTPA提取法在重金属污染土壤修复模拟试验中的应用是可行的。     

Geochemical background of potentially toxic trace elements in reclaimed soils of the abandoned pyrite–uranium mine (south-central Poland)

Spatial distribution patterns of As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, U and Zn were determined in topsoil samples collected after 40 years of chemical remediation conducted in the inoperative “Staszic” pyrite–uranium mine in the Holy Cross Mountains, south-central Poland. Soil samples were taken from 58 sites using a systematic random sampling design. Selected samples were subjected to an X-ray diffractometry analysis on bulk soils and separated clay fractions. Hematite, goethite and gypsum are common mineral phases in soil samples. Technogenic soils developed on reclaimed mine spoils show uniform spatial element distribution patterns and additionally a distinct enrichment in As, Pb, Mn, U and Zn. Mineral and chemical composition of soils vs. rocks points to the lithogenic source of the determined elements. The results of chemical analysis have been used for evaluation of geochemical background of trace elements in the study area with the iterative 2σ-technique. This investigation shows that using mean crustal element concentrations (Clarke values) as proxies of threshold values in soils are not useful for determination of strongly positive geochemical anomalies. A modified enrichment factor, i.e. a local enrichment factor, is proposed for identification of sites where soils are contaminated.     

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.     

Mobilization and attenuation of metals downstream from a base-metal mining site in the Mátra Mountains, northeastern Hungary

Regional geochemical baseline values have been established for Hungary by the use of low-density stream-sediment surveys of flood-plain deposits of large drainage basins and of the fine fraction of stream sediments. The baseline values and anomaly thresholds thus produced helped to evaluate the importance of high toxic element concentrations found in soils in a valley downstream of a polymetallic vein-type base-metal mine. Erosion of the mine dumps and flotation dump, losses of metals during filtering, storage and transportation, human neglects, and operational breakdowns, have all contributed to the contamination of a small catchment basin in a procession of releases of solid waste. The sulfide-rich waste material weathers to a yellow color; this layer of `yellow sand' blankets a narrow strip of the floodplain of Toka Creek in the valley near the town of Gyöngyösoroszi. Contamination was spread out in the valley by floods. Metals present in the yellow sand include Pb, As, Cd, Cu, Zn, and Sb. Exposure of the local population to these metals may occur through inhalation of airborne particulates or by ingestion of these metals that are taken up by crops grown in the valley. To evaluate the areal extent and depth of the contamination, active stream sediment, flood-plain deposits, lake or reservoir sediments, soils, and surface water were sampled along the erosion pathways downstream of the mine and dumps. The flood-plain profile was sampled in detail to see the vertical distribution of elements and to relate the metal concentrations to the sedimentation and contamination histories of the flood plain. Downward migration of mobile Zn and Cd from the contaminated upper layers under supergene conditions is observed, while vertical migration of Pb, As, Hg and Sb appears to be insignificant. Soil profiles of ¹³⁷Cs which originated from above-ground atomic bomb tests and the Chernobyl accident, provide good evidence that the upper 30–40 cm of the flood-plain sections, which includes the yellow sand contamination, were deposited in the last 30–40 years.     

Heavy metal contamination of coastal lagoon sediments by anthropogenic activities: the case of Nador (East Morocco)

Nador lagoon sediments (East Morocco) are contaminated by industrial iron mine tailings, urban dumps and untreated wastewaters from surrounding cities. The lagoon is an ecosystem of biological, scientific and socio-economic interests but its balance is threatened by pollution already marked by biodiversity changes and a modification of foraminifera and ostracods shell structures. The aim of the study is to assess the heavy metal contamination level and mobility by identifying the trapping phases. The study includes analyses by ICP-AES and ICP-MS, of, respectively, major (Si, Al, Mg, Ca, Fe, Mn, Ti, Na, K, P) and trace elements (Sr, Ba, V, Ni, Co, Cr, Zn, Cu, As, Pb, Cd) in sediments and suspended matter, heavy metals enrichment factors calculations and sequential extractions. Results show that sediments contain Zn, Cu, Pb, V, Cr, Co, As, Ni with minimum and maximum concentrations, respectively, of 4–1190 μg/g, 4–466 μg/g, 11–297 μg/g, 11–194 μg/g, 9–139 μg/g, 1–120 μg/g, 4–76 μg/g, 2–62 μg/g. High concentrations in Zn are also present in suspended matter. The enrichment factors show contamination in Zn, Pb and As firstly induced by the mining industry and secondly by unauthorized dumps and untreated wastewaters. Cr and Ni are bound to clays, whereas V, Co, Cu and Zn are related to oxides. Thus, the risk in metal mobility is for the latter elements and lies in the oxidation–reduction-changing conditions of sediments.     

The mineralized veins and the impact of old mine workings on the environment at Segura, central Portugal

At Segura, granitic pegmatite veins with cassiterite and lepidolite, hydrothermal Sn–W quartz veins and Ba–Pb–Zn quartz veins intruded the Cambrian schist–metagraywacke complex and Hercynian granites. Cassiterite from Sn–W quartz veins is richer in Ti and poorer in Nb and Nb+Ta than cassiterite from granitic pegmatite. Wolframite from Sn–W quartz veins is enriched in ferberite component. The Sn–W quartz veins contain pyrrhotite, arsenopyrite, sphalerite, chalcopyrite, stannite, matildite and schapbachite and the Ba–Pb–Zn quartz veins have cobaltite, pyrite, sphalerite, chalcopyrite, galena and barite, which were analyzed by electron microprobe. The presently abandoned mining area was exploited for Sn, W, Ba and Pb until 1953. Stream sediments and soils have higher concentrations of metals than parent granites and schists. Sn, W, B, As and Cu anomalies found in stream sediments and soils are associated with Sn–W quartz veins, while Ba, Pb and Zn anomalies in stream sediments and soils are related to Ba–Pb–Zn quartz veins. Sn, W, B, As, Cu, Ba, Pb and Zn anomalies in stream sediments and soils are also related to the respective old mining activities, which increased the mobility of trace metals from mineralized veins to soils, stream sediments and waters. Stream sediments and soils are sinks of trace elements, which depend on their contents in mineralized veins and weathering processes, but Sn, W and B depend mainly on a mechanic process. Soils must not be used for agriculture and human residence due to their Sn, B, As and Ba contents. Waters associated with mineralized veins were analyzed by flame atomic absorption spectroscopy (FAAS) and ICP-AES have high As, Fe and Mn and should not be used for human consumption and agriculture activities. The highest As values in waters were all related to Sn–W quartz veins and the highest Fe and Mn values were associated with the Ba–Pb–Zn quartz veins. No significant acid drainage was found associated with the old mine workings.