The nature and distribution of Cu,Zn, Hg,and Pb in urban soils of a regional city: Lithgow,Australia

This study investigates the concentration and spatial distribution of Cu, Zn, Hg and Pb in the surface (0–2 cm) soils of a regional city in Australia. Surface soils were collected from road sides and analysed for their total Cu, Zn, Hg and Pb concentrations in the <180 μm and <2 mm grain size fractions. The average metal concentration of surface soils, relative to local background soils at 40–50 cm depth, are twice as enriched in Hg, more than three times enriched in Cu and Zn, and nearly six times as enriched in Pb. Median surface soil metal concentration values were Cu – 39 mg/kg (682 mg/kg max), Zn – 120 mg/kg (4950 mg/kg max), Hg – 44 μg/kg (14,900 μg/kg max) and Pb – 46 mg/kg (3490 mg/kg max). Five sites exceeded the Australian NEPC (1999) 300 mg/kg guideline for Pb in residential soils. Strong positive correlations between Cu, Zn and Pb, coupled with the spatial distribution of elevated soil concentrations towards the city centre and main roads suggest traffic and older housing as major sources of contamination. No spatial relationships were identified between elevated metal loadings and locations of past or present industries.     

Metal species in a Boreal river system affected by acid sulfate soils

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations but on their chemical form. Consequently, knowledge of aqueous metal speciation is essential in investigating potential metal toxicity and mobility. Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic C (OC) and 18 metals/metalloids were investigated in the extremely acidic Vörå River system in Western Finland, which is strongly affected by acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these acidic waters. The most important finding of this study is that the very large amounts of elements known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si and U) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and particularly dissolved Al can be expected to have acute effects on fish and other organisms. In the study area, only the relatively forested upstream area (higher pH and contents of OC) had significant amounts of a few bioavailable elements (including Al, Cu, Ni and U) due to complexation with the more abundantly occurring colloidal OC in the upstream area. It is, however, notable that some of the colloidal/particulate metals were most likely associated with metal bearing phyllosilicates eroded from clay soils. Moreover, the mobilisation of Fe and As was small and As was predicted to be associated with Fe oxides, indicating a considerable influence of Fe oxides on the mobilisation/immobilisation processes of As. Elements will ultimately be precipitated in the recipient estuary, where the acidic metal-rich river water will gradually be diluted/neutralised with brackish seawater in the Gulf of Bothnia. According to speciation modelling, such a pH rise may first cause precipitation of Al, Cu and U together with organic matters closest to the river mouth, in line with previous sediment studies from the estuary.     

New insights on mobility and bioavailability of heavy metals in soils of the Padanian alluvial plain (Ferrara Province,northern Italy)

Heavy metals having both natural and anthropogenic origin are common contaminants in soils and sediments, and can be transferred and bioaccumulated at all levels of the food chain, posing serious environmental concern to the local population. In this paper, agricultural soils from the Province of Ferrara (easternmost part of the Padanian Plain, northern Italy) were investigated to assess the levels of potentially toxic metals in relation to their phytoavailability. Agricultural soils have been sampled in order to identify the origin, mobility and bioavailability of heavy metals, collecting superficial and deeper (depths of 20–30 and 100–120 cm, respectively) horizons. The “total” XRF analyses properly elaborated with a statistical approach reveal that soils evolved from two distinct types of alluvial sediments, in turn related to the Po and Reno rivers; the former type is distinctively enriched in heavy metals (particularly Cr and Ni), reflecting the presence of femic and ultrafemic rocks in the hydrological basin of River Po. The absence of Top Enrichment Factors for Ni, Co, Cr, V, and Pb suggests that the content of these elements is natural and unaffected by contamination, whereas superficial enrichments of Cu (and Zn) is ascribed to anthropogenic inputs related to agricultural activities. Multiple extraction tests using variously aggressive reactants (aqua regia, DTPA, EDTA, NH₄NO₃, and H₂O) analyzed by ICP gave insights on the specific mobility of the distinct elements, which decreases in the following order: Pb > Cu > Cd > Co > >Ni > Cr. Taking into consideration the elements that are inducing the main concerns, Cr appears scarcely mobile, whereas Ni could be more phytoavailable and has to be monitored in the local agricultural products. Cd although scarcely abundant has to be monitored for its mobility and toxicity, whereas Cu although abundant and extremely mobile doesn’t induce concerns as it is not hazardous for the living receptors.     

Assessment of trace metal and rare earth elements contamination in rivers around abandoned and active mine areas. The case of Lubumbashi River and Tshamilemba Canal,Katanga, Democratic Republic of the Congo

Active and abandoned mine activities constitute the sources of deterioration of water and soil quality in many parts of the world, particularly in the African Copperbelt regions. The accumulation in soils and the release of toxic substances into the aquatic ecosystem can lead to water resources pollution and may place aquatic organisms and human health at risk. In this study, the impact of past mining activity (i.e., abandoned mine) on aquatic ecosystems has been studied using ICP-MS analysis for trace metals and Rare Earth Elements (REE) in sediment samples from Lubumbashi River (RL) and Tshamilemba Canal (CT), Katanga, Democratic Republic of the Congo (DRC). Soil samples from surrounding CT were collected to evaluate trace metal and REE concentrations and their spatial distribution. The extent of trace metal contamination compared to the background area was assessed by Enrichment Factor (EF) and Geoaccumulation Index (I_geo). Additionally, the trace metal concentrations probable effect levels (PELs) for their potential environmental impact was achieved by comparing the trace metal concentrations in the sediment/soil samples with the Sediment Quality Guidelines (SQGs). Spearman's Rank-order correlation was used to identify the source and origin of contaminants. The results highlighted high concentrations of trace metals in surface sediments of CT reaching the values of 40152, 15586, 610, 10322, 60704 and 15152 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. In the RL, the concentrations reached the values of 24093, 2046, 5463, 3340, 68290 and 769 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. The ΣREE varied from 66 to 218 and 142–331 mg kg⁻¹ for CT and RL, respectively. The soil samples are characterized by variable levels of trace metals. The EF analysis showed “extremely severe enrichment” for Cu and Co. However, no enrichment was observed for REE. Except for Mo, Th, U, Eu, Mo, Ho and Tm for which Igeo is classified as “moderately polluted and/or unpolluted”, all elements in different sites are classified in the class 6, “extremely polluted”. The trace metal concentrations in all sampling sites largely exceeded the SQGs and the PELs for the Protection of Aquatic Life recommendation. Cu and Co had positive correlation coefficient values (r = 0.741, P < 0.05, n = 14). This research presents useful tools for the evaluation of water contamination in abandoned and active mining areas.     

Partitioning and mobility of trace metals in the Blesbokspruit: Impact assessment of dewatering of mine waters in the East Rand,South Africa

A suite of trace metals was analyzed in water and sediment samples from the Blesbokspruit, a Ramsar certified riparian wetland, to assess the impact of mining on the sediment quality and the fate of trace metals in the environment. Limited mobility of trace metals was observed primarily because of their high partition coefficient in alkaline waters. Nickel was most mobile with a mean K_d of 10^3.28 L kg⁻¹ whereas Zr was least mobile with a mean K_d of 10^5.47 L kg⁻¹. The overall trace metal mobility sequence, derived for the Blesbokspruit, in increasing order, is: Zr < Cr < Pb < Ba < V < Cu < Zn < Sr < Mn < U < Mo < Co < Ni. Once removed from the solution, most trace metals were preferentially associated with the carbonate and Fe–Mn oxide fraction followed by the exchangeable fraction of the sediments. Organic C played a limited role in trace metal uptake. Only Cu was primarily associated with the organic fraction whereas Ti and Zr were mostly found in the residual fraction. Compared to their regional background, Au and Ag were most enriched, at times by a factor of 20–400, in the sediments. Significant enrichment of U, Hg, V, Cr, Co, Cu and Zn was also observed in the sediments.The calculated geoaccumulation indices suggest that the sediments are very lightly to lightly polluted with respect to most trace metals and highly polluted with respect to Au and Ag. The metal pollution index (MPI) for the 20 sampled sites varied between 2.9 and 45.7. The highest MPI values were found at sites that were close to tailings dams. Sediment eco-toxicity was quantified by calculating the sediment quality guideline index (SQG-I). The calculated SQG-I values (0.09–0.69) suggest that the sediments at the study area have low to moderate potential for eco-toxicity.     

Laboratory study of calcite–gypsum sludge–water interactions in a flooded tailings impoundment at the Kristineberg Zn–Cu mine,northern Sweden

Due to liming of acid mine drainage, a calcite–gypsum sludge with high concentrations of Zn (24,400 ± 6900 μg g⁻¹), Cu (2840 ± 680 μg g⁻¹) and Cd (59 ± 20 μg g⁻¹) has formed in a flooded tailings impoundment at the Kristineberg mine site. The potential metal release from the sludge during resuspension events and in a long-term perspective was investigated by performing a shake flask test and sequential extraction of the sludge. The sequentially extracted carbonate and oxide fractions together contained ⩾97% of the total amount of Cd, Co, Cu, Ni, Pb and Zn in the sludge. The association of these metals with carbonates and oxides appears to result from sorption and/or coprecipitation reactions at the surfaces of calcite and Fe, Al and Mn oxyhydroxides forming in the impoundment. If stream water is diverted into the flooded impoundment, dissolution of calcite, gypsum and presumably also Al oxyhydroxides can be expected during resuspension events. In the shake flask test (performed at a pH of 7–9), remobilisation of Zn, Cu, Cd and Co from the sludge resulted in dissolved concentrations of these metals that were significantly lower than those predicted to result from dissolution of the carbonate fraction of the sludge. This may suggest that cationic Zn, Cu, Cd and Co remobilised from dissolving calcite, gypsum and Al oxyhydroxides were readsorbed onto Fe oxyhydroxides remaining stable under oxic conditions. In a long-term perspective (≳10² a), ⩾97% of the Cd, Co, Cu, Ni, Pb and Zn content of the sludge potentially is available for release by dissolution of calcite and reductive dissolution of Fe oxyhydroxides if the sludge is subject to a soil environment with lower dissolved Ca concentrations, pH and redox than in the impoundment.     

Total concentration,speciation and mobility of potentially toxic elements in soils around a mining area in central Iran

The current study was designed to investigate the extent and severity of contamination as well as the fractionation of potentially toxic elements (As, Cd, Cr, Cu, Pb, Zn, Ni) in minesoils and agricultural soils around a Pb–Zn mine in central Iran. For this purpose, 20 agricultural soils and eight minesoils were geochemically characterized. Results showed that minesoils contained elevated concentrations of As (12.9–254 mg kg⁻¹), Cd (1.2–55.1 mg kg⁻¹), Pb (137–6239 mg kg⁻¹) and Zn (516–48,889 mg kg⁻¹). The agricultural soils were also polluted by As (5.5–57.1 mg kg⁻¹), Cd (0.2–8.5 mg kg⁻¹), Pb (22–3451 mg kg⁻¹) and Zn (94–9907 mg kg⁻¹). The highest recorded concentrations for these elements were in soils influenced directly by tailing ponds. Chromium, Cu and Ni content in agricultural soils (with average value of 74.1, 34.6 and 50.7 mg kg⁻¹, respectively) were slightly higher than the minesoils (with average value of 54.5, 33.1 and 43.4 mg kg⁻¹, respectively). Sequential extraction data indicated that there were some differences between the speciation of PTEs in soil samples. In the agricultural soils, Zn and Cd were mainly associated with carbonate bound fraction, As and Pb with reducible fraction, Cu with oxidisable fraction and Cr and Ni with residual phase. With respect to mobility factor values, Zn and Cd in the agricultural soils have been found to be the most mobile while As mobility is negligible. Also, the mobility factor of As, Cd and Pb in agricultural soils adjoining tailing ponds was high. In minesoil sample Cd was most abundant in the carbonate form, whereas other studied elements were mainly present in the reducible and residual fractions; therefore, despite the high total concentrations of As, Pb and Zn in the minesoils, the environmental risk of these elements was low. Based on the obtained data, a portion of Cu, Cr and Ni input was from agricultural activities.     

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 spatial characteristics and pollution levels of metals in urban street dust of Beijing,China

The components and concentrations of metals in street dust are indictors of environmental pollution. To explore the pollution levels of Cd, Cr, Cu, Mn, Ni and Pb in street dust and their spatial distribution characteristics, 220 dust samples were collected in a grid pattern from urban street surfaces in Beijing. Multivariate statistics and spatial analyses were adopted to investigate the associations between metals and to identify their pollution patterns. In comparison with the soil background values, elevated metal concentrations were found, except those for Mn and Ni. The results of the geo-accumulation index (I_geo) and the potential ecological risk index (Erⁱ) of the metals revealed the following orders: Cd > Cu > Cr > Pb > Ni > Mn and Cd > Cu > Pb > Cr > Ni. Levels of I_geo ranging from 0 to 5 were found and about 80% of the samples were below the moderately polluted level. The Erⁱ values of single elements were within the low ecological risk level in most sampling sites. Most of the metals in the street dust of Beijing were statistically significantly correlated. It is hard to clearly identify the sources of each metal in the street dust since local environments are very complex. Cadmium, Cu, Cr, Mn and Pb showed medium spatial autocorrelations within the sampling region. Similar spatial distribution patterns were observed for Cu, Cr and Pb, and these metals had relatively high spatial variabilities and were enriched in the center of the city with several peaks scattered in the suburbs. Metal pollution anomalies were identified by using cluster and outlier analyses. Locations identified as clusters with high values indicated non-point source pollution, while locations identified as outliers with high values indicated point source pollution. Traffic, construction, and other human activities influenced these high values. In addition, the locations identified as outliers with low values in urban areas might benefit from less transportation and better management.     

Metal contamination and solid phase partitioning of metals in the stream and bottom sediments in a reservoir receiving mine drainage

This study was conducted to assess the anthropogenic impact on metal concentrations in the bottom sediments of the Juam reservoir, Korea, and in stream sediments in its catchment, and to estimate the potential mobility of selected metals (Fe, Mn, Cu, Ni, Pb and Zn) using sequential extraction. A comparison of the metal concentrations in the stream sediments with mean background values in sediments collected from first- or second-order creeks shows that Pb, Cu and Ni are the most affected by anthropogenic inputs. The ²⁰⁶Pb/²⁰⁷Pb ratios of the bottom and core sediments (means: 1.2320 ± 0.0502 and 1.2212 ± 0.0040, respectively) suggest that Pb contamination is mainly due to the waste discharge of abandoned coal and metal mines rather than industrial and airborne sources. Considering the proportion of metals bound to the exchangeable, carbonate and reducible fractions, the comparative mobility of metals is suggested to decrease in the order Mn > Pb > Zn > Ni > Fe ≫ Cu.     

Bioavailability and mobility of trace metals in phosphogypsum from Aqaba and Eshidiya,Jordan

As, Cd, Cr, Cu, U, and Zn in Aqaba and Eshidiya phosphogypsum showed relative uniformity in particle size presented by coarse (>0.212 mm); medium (0.212–0.053 mm); and fine (<0.053 mm) in the stacks by age of deposition. Jordan phosphogypsum contains low concentrations of As, Cd, Cr, Cu, U, and Zn compared to those reported worldwide. The bioavailability and mobility of trace metals were estimated using aqua regia leaching experiments. Leaching results have shown that around 3% of the As, 1% of the Cd, 5% of the Cr, 9% of the Cu, 4% of the U, and 3% of the Zn are transferred to the surrounding aquatic environment and/or soils. Mobility of trace metals in phosphogypsum was classified into three degrees: elements with high mobility were Cu and U; those with moderate mobility were As and Zn; and those with low mobility were Cd and Cr. It can be concluded that As, Cd, Cr, Cu, U, and Zn were not only uniformly distributed in the stack, but they are not leached from the phosphogypsum stacks in any significant amount, and then they are not easily transferred to the surrounding aquatic environment and/or soils.     

Geochemical challenges of diverse regolith-covered terrains for mineral exploration in China

In recent years mineral exploration has concentrated on concealed deposits in regolith-covered terrains. In China, the regolith-covered landscapes mainly include desert windblown sand basins, desert peneplains, semi-arid grassland, loess plateaus, forestry land, alluvial plains and laterite terrains. These diverse regolith-covered areas represent geochemical challenges for mineral exploration in China. This paper provides an overview of recent progress on mechanisms of metal dispersion from the buried ore deposits through the transported cover to the surface and penetrating geochemical methods to detect the anomalies. Case studies show that, in arid and semi-arid desert sand-covered terrains, sampling of fine-fraction (− 120 mesh, < 0.125 mm) clay-rich horizon soil is cost-effective for regional geochemical surveys for sandstone-type uranium, gold, and base metal deposits. Fine-fraction sampling, selective-leaching and overburden drilling geochemical methods can effectively indicate the 210 gold ore body at Jinwozi goldfield. In alluvium-covered terrains, fine-grained soil sampling (− 200 mesh, < 0.074 mm) combined with selective leaching geochemistry shows clear ring-shaped anomalies of Cu and Ni over the Zhouan concealed Cu–Ni deposit. In laterite-covered terrains, the anomalies determined by the fine-fraction soils and selective leaching of absorbed metals on coatings of Fe–Mn oxides coincide well with the concealed deposit over the Yueyang ore deposits at the Zijin Au–Cu–Ag field. Nanoparticles of hexagonal crystals mainly native copper, gold and alloys of Cu–Fe, Cu–Fe–Mn, Cu–Ti, and Cu–Au were observed in gases, soils and ores using a transmission electron microscope (TEM). The findings imply that nanoparticles of gold and copper may migrate through the transported cover to the surface. Uranium is converted to uranyl ions [UO₂^2 +] under oxidizing conditions when migrating from ore bodies to the surface. The uranyl ions are absorbed on clay minerals, because clay layers have a net negative charge, which needs to be balanced by interlayer cations. Nanoparticles of Au and Cu and ion complexes of U are more readily absorbed onto fine fractions of soils containing clays, colloids, oxides and organic matters. Thus, fine-grained soils enriched with clays, oxides and colloids are useful media for regional geochemical surveys in regolith-covered terrains and in sedimentary basins. Fine-fraction soil sampling combined with selective leaching geochemistry is effective for finding concealed ore bodies in detailed surveys. Penetrating geochemistry at surface sampling provides cost-effective mineral exploration methods for delineation of regional and local targets in transported cover terrains.     

Metal and arsenic distribution in soil particle sizes relevant to soil ingestion by children

Ingestion of soil is a common behaviour in young children as a means of exploring their surroundings. Much attention has been given to remediation of point-source polluted sites with regard to potential health risks for children. However, because of diffuse pollution and long-range atmospheric deposition, soil contaminant levels are generally increased in urban areas compared to their rural counterparts, even in areas located away from any point sources of pollution. Intake of urban soil can thereby result in significant amounts of the child’s daily metal intake. In the present study, soil samples were collected from 25 playgrounds around urban Uppsala, Sweden and analysed for contents of Al, As, Fe, Cr, Cu, Cd, Hg, Mn, Ni, Pb, W and Zn. Prior to aqua regia digestion, the samples were wet-sieved in order to separate soil particle fractions representing deliberate (<4 mm) and involuntary (<50 μm) soil ingestion by children, as well as a third size fraction of 50–100 μm representing soil that is easily transported by suspension. While the metal and As contents in the 50–100 μm fraction were similar to those of the <4 mm fraction, the <50 μm fraction had metal and As contents on average one and a half times higher than those of the <4 mm fraction. The metal and As contents correlated negatively with the sand content in both particle size fractions <4 mm and 50–100 μm, suggesting a general decrease in metal and As content with increasing sand content. However, a positive correlation was found between sand content and the metal and As contents of the finest fraction (<50 μm), suggesting that when the sand content is high, the bulk of the sorbed elements are on the finest particles. The difference between metal and As contents in the different size fractions was greater in the soil sample with the highest sand content than in the sample with the lowest sand content. This implies that texture is a significant factor in metal and As distribution in soils with moderate metal and As contents, when the number of binding sites associated with small particles is low. Tolerable daily intake (TDI) values for Pb and As were exceeded at all sites, and at two sites for Cd, for children with pica behaviour. A high ingestion rate of mainly small particles could also result in the TDI value for Pb being exceeded at 10 sites and that for As at one site. This study also found that soil analysis by the procedure recommended by Swedish authorities accurately represents the metal intake from deliberate soil ingestion, whereas involuntary soil ingestion of mainly small particles could result in metal intakes which are up to twice as high.     

Measurement of labile metals in acid rock drainage springs,New Zealand: Field application of anodic stripping voltammetry

Spring waters were analysed in the field by anodic stripping voltammetry, using equipment which is sufficiently portable to be useful in a remote heavily forested area accessible by foot only. The equipment and techniques are capable of producing analyses on site to the μg/L level for labile metals. Field analysis avoids issues of sample storage and transport protocols that limit confidence in laboratory measurements of labile elements. Samples were taken as a feedback to immediate analysis resulting in a fine grid map of the geological site. Acid rock drainage emanates from a New Zealand historic mine site, with elevated concentrations of metals. However, ground water and surface water discharging naturally from mineralised rocks in the same area also have elevated levels of metals. This study quantifies natural metalliferous discharges from a single site, and compares this to the overall metal flux from the mine area. Acid (pH 3) metalliferous springs emanate from colluvium and bedrock in a young (months-old) landslide. Labile Cu, Pb, Zn and Cd are the environmentally most significant metals in the studied area. Labile metal concentrations observed in the natural springs are up to 24 μg/L Cu, up to 50 μg/L Pb, up to 5 μg/L Cd and up to 9 mg/L Zn. Labile Cu and Zn concentrations are similar to laboratory-determined total concentrations, whereas labile Pb and Cd concentrations are generally distinctly lower than total Pb and Cd concentrations. Four different spring water compositions occur within metres of each other: acid metalliferous water with high Pb, acid metalliferous water with low Pb, high Cu, Pb, Zn acid water and high pH water with elevated Cu. High metal concentrations in these waters are readily attenuated by adsorption to Fe oxyhydroxides (HFO), especially when rain raises spring water pH at the surface. Copper, Pb and Cd are >99% adsorbed, and Zn >95% adsorbed, during this rainfall dilution. Natural spring waters have potential to contribute up to 10% of the total Zn flux from the catchment, but negligible proportions of Cu, Pb and Cd.     

The geochemistry of trace elements in geothermal fluids,Iceland

Trace element geochemistry was studied in geothermal fluids in Iceland. The major and trace element compositions of hot springs, sub-boiling, and two-phase (liquid and vapor) wells from 10 geothermal areas were used to reconstruct the fluid composition in the aquifers at depth. Aquifer fluid temperatures ranged from 4 to 300 °C, pH values between 4.5 and 9.3, and fluids typically contained total dissolved solids <1000 ppm, except in geothermal areas that have seawater and seawater-meteoric water mixtures. Trace alkali elements Li, Rb and Cs are among the most mobile elements in aquifer fluids, with concentrations in the range of <1 ppb to 3.49 ppm Li, <0.01 to 57 ppb Cs, and <1 ppb to 3.77 ppm Rb. Their chemistry is thought to be dominated by rock leaching and partitioning into Na- and K-containing major alteration minerals. Arsenic, Sb, Mo and W are typically present in concentrations in the range of 1–100 ppb. They are relatively mobile, yet Mo may be limited by molybdenite solubility. The alkaline earth elements Ba and Sr are quite immobile with concentrations in the range of <0.1–10 ppb Ba and <1–100 ppb Sr in the dilute fluids, but up to 5.9 ppm Ba and 8.2 ppm Sr in saline fluids. These elements show a systematic relationship with Ca, possibly due to substitution for Ca in Ca-containing major alteration minerals like calcite, epidote and anhydrite. Incorporation into major Ca-minerals may also be important for Mn. Many metals including Fe, Cr, Ni, Zn, Cu, Co, Pb and Ag have low mobility and concentrations, typically <1 ppb for Ag, Cd, Co, Cr, Cu, Ni, and Pb, <10 ppb for Zn and < 100 ppb for Fe, although for some metals higher concentrations are associated with saline fluids. Based on the metals assessed, saturation is approached with respect to many sulfide minerals and in some cases oxide minerals but Cu, Ni and Pb minerals are slightly but systematically undersaturated, and Ag phases significantly undersaturated. Evaluation of mineral-fluid equilibria for these metals is problematic due to their low concentrations, problems associated with assessing the aqueous species distribution by thermodynamic calculations, and uncertainties concerning the exact minerals possibly involved in such reactions. Reaction path calculations, poor comparison of concentrations measured in the samples collected at the wellhead and published downhole data as well as boiling, cooling and mass precipitation calculations suggest removal of many metals due to changes upon depressurization boiling and conductive cooling of the aquifer fluids as they ascend in wells. These results imply that processes such as mass precipitation upon fluid ascent may be highly important and emphasize the importance of considering mass movement in geothermal systems.     

The use of vetiver grass (Vetiveria zizanioides) in the phytoremediation of soils contaminated with heavy metals

Recent research has shown that phytoextraction approaches often require soil amendments, such as the application of EDTA, to increase the bioavailability of heavy metals in soils. However, EDTA and EDTA–heavy metal complexes can be toxic to plants and soil microorganisms and may leach into groundwater, causing further environmental pollution. In the present study, vetiver grass (Vetiveria zizanioides) was studied for its potential use in the phytoremediation of soils contaminated with heavy metals. In the pot experiment, the uptake and transport of Pb by vetiver from Pb-contaminated soils under EDTA application was investigated. The results showed that vetiver had the capacity to tolerate high Pb concentrations in soils. With the application of EDTA, the translocation ratio of Pb from vetiver roots to shoots was significantly increased. On the 14th day after 5.0 mmol EDTA kg⁻¹ of soil application, the shoot Pb concentration reached 42, 160, 243 mg kg⁻¹ DW and the root Pb concentrations were 266, 951, and 2280 mg kg⁻¹ DW in the 500, 2500 and 5000 mg Pb kg⁻¹ soils, respectively. In the short soil leaching column (9.0-cm diameter, 20-cm height) experiment, about 3.7%, 15.6%, 14.3% and 22.2% of the soil Pb, Cu, Zn and Cd were leached from the artificially contaminated soil profile after 5.0 mmol EDTA kg⁻¹ of soil application and nearly 126 mm of rainfall irrigation. In the long soil leaching experiment, soil columns (9.0-cm diameter, 60-cm height) were packed with uncontaminated soils (mimicking the subsoil under contaminated upper layers) and planted with vetiver. Heavy metal leachate from the short column experiment was applied to the surface of the long soil column, the artificial rainwater was percolated, and the final leachate was collected at the bottom of the soil columns. The results showed that soil matrix with planted vetiver, could re-adsorb 98%, 54%, 41%, and 88% of the initially applied Pb, Cu, Zn, and Cd, respectively, which may reduce the risk of heavy metals flowing downwards and entering the groundwater.     

Geology,fluid inclusion and stable isotope study of the Yueyang Ag-Au-Cu deposit,Zijinshan orefield,Fujian Province,China

The large Yueyang Ag-Au-Cu deposit is commonly regarded as a low-sulfidation epithermal deposit in the Zijinshan orefield, Fujian Province, southeastern China. The Ag-Ag-Cu orebodies hosted in the Zijinshan granitic batholith are mainly stratoid and lens in shape, and controlled by a series of NW-trending listric faults with shallow dip angles. Four mineralization stages are recognized on the basis of mineral assemblage, ore fabrics, and crosscutting relationships of the ore veins, namely: pre-ore (pyrite + sericite + quartz ± chlorite), main Cu (chalcopyrite + pyrite + sericite + quartz ± bornite), main Ag-Au (Ag and Au minerals + pyrite + quartz + adularia ± calcite ± apatite ± chalcopyrite ± galena ± sphalerite) and post-ore (quartz ± chalcedony ± calcite) stages. Fluid inclusions (FIs) in the deposit include aqueous liquid-rich (WL-), aqueous vapor-rich (WV-), and minor carbonic (C-) and daughter mineral-bearing (S-) type ones. WL-subtype is the main inclusion type in the Yueyang deposit, accounting for more than 90% in proportion in each stage. Minor WV-subtype inclusions occur in both the main Cu and Ag stages, while the C-type and S-type ones are only observed in the main Cu stage. Fluid inclusion and H-O isotope study indicated that the ore-forming fluid of the main Cu stage is primarily magmatic vapor, which further underwent fluid boiling and mixing with meteoric water, while the ore-forming fluid of the main Ag stage is meteoric water-dominated, and the precipitation of silver and gold was mainly resulted from fluid boiling and the precipitation of other sulfides. On the basis of the aforementioned geological, fluid inclusion and stable isotope studies, we proposed a two-stage model for the Yueyang deposit, including a magmatic vapor-related porphyry type Cu mineralization and meteoric water-related low-sulfidation epithermal Ag-Au-Cu mineralization, although the porphyry Cu mineralization is very limited in scale. The mineralization and exhumation depths of the Yueyang deposit are estimated to be 448‒527 m and 18‒97 m, respectively. By comparison with the exhumation depths of other deposits in the Zijinshan orefield, it is suggested that more epithermal deposits could be found in the southwest of the orefield due to less uplift and exhumation therein.     

Metal speciation in coastal marine sediments from Singapore using a modified BCR-sequential extraction procedure

The chemical speciation of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in marine sediments from two coastal regions of Singapore (Kranji in the NW, and Pulau Tekong in the NE) was determined using the latest version of the 3-step sequential extraction procedure, as described by the European Community Bureau of Reference (1999). To obtain a mass balance, a fourth step, i.e., digestion and analysis of the residue was undertaken using a microwave-assisted acid digestion procedure. The total content of all metals except for Pb in sediments was greater in Kranji than in Pulau Tekong. All metals, except Cd were more mobile and bio-available in Kranji, where metals were present at higher percentages in the acid-soluble fractions (the most labile fraction). In sediments from Kranji, the mobility order of the heavy metals studied was Cd > Ni > Zn > Cu > Pb > Cr, whereas sediments from Pulau Tekong showed the same order for Cd, Ni, Pb and Cr, but had a reverse order for Cu and Zn (Cu > Zn). The highest percentages of Cr, Ni and Pb were found in the residual fractions in both Kranji (78.9%, 54.7%, 55.9%, respectively) and Pulau Tekong (82.8%, 77.3%, 62.2%, respectively), meaning that these metals were strongly bound to the sediments. Results are consistent with findings from Barcelona, Spain where similar results for Cr and Ni have also been reported for marine sediments. The sum of the 4 steps (acid-soluble + reducible + oxidizable + residual) was in good agreement with the total content, which implies that the accuracy of the microwave extraction procedure in conjunction with the GFAAS analytical method is assured.     

Significance of weathering and regolith/landscape evolution for mineral exploration in the NE Albany-Fraser Orogen,Western Australia

The Albany-Fraser Orogen (AFO), southeast Western Australia, is an underexplored, deeply weathered regolith-dominated terrain that has undergone complex weathering associated with various superimposed climatic events. For effective geochemical exploration in the AFO, integrating landscape evolution with mineralogical and geochemical variations of regolith and bedrock provides fundamental understanding of mechanical and hydromorphic dispersion of ore and pathfinder elements associated with the different weathering processes.In the Neale tenement, northeast of the AFO, a residual weathering profile that is 20-55 m thick was developed under warm and humid climatic conditions over undulating Proterozoic sheared granitoids, gneisses, schists and Au-bearing mafic rocks. From the base, the typical weathering profile consists of saprock, lower ferruginous saprolite, upper kaolinitic saprolite and discontinuous silcrete duricrust or its laterally coeval lateritic residuum. These types of duricrusts change laterally into areas of poorly-cemented kaolinitic grits or loose lateritic pisoliths and nodules.Lateritic residuum probably formed on remnant plateaus and was transported mechanically under arid climatic conditions over short distances, filling valleys to the southeast. Erosion of lateritic residuum exposes the underlying saprolite and, together with dilution by aeolian sands, constitutes the transported overburden (2-25 m thick). The reworked lateritic materials cover the preserved silcrete duricrusts in valleys. The lower ferruginous saprolite and lateritic residuum are well developed over mafic and sulphide-bearing bedrocks, where weathering of ferromagnesian minerals and sulphides led to enrichment of Fe, Cu, Ni, Cr, Co, V and Zn in these units. Kaolinitic saprolite and the overlying pedogenic silcrete are best developed over alkali granites and quartzofeldspathic gneisses, which are barren in Au and transition elements, and enriched in silica, alumina, rare earth and high field strength elements.A residual Au anomaly is formed in the lower ferruginous saprolite above a Au -bearing mafic intrusion at the Hercules prospect, south of the Neale tenement, without any expression in the overlying soil (< 20 cm). Conversely, a Au anomaly is recorded in the transported cover, particularly in the uppermost 3 m at the Atlantis prospect, 5 km southwest of the Hercules prospect. No anomalies have been detected in soils using five different size fractions (> 2,000 μm, 2,000-250 μm, 250-53 μm, 53-2 μm and < 2 μm). Therefore, soil cannot be efficiently applied as a reliable sampling medium to target mineralization at the Neale tenement. This is because mechanical weathering was interrupted by seasonal periods of intensive leaching under the present-day surface conditions and/or dilution by recently deposited aeolian sediments which obscure any signature of a potential Au anomaly in soils. Therefore, surface soil sampling should extend deeper than 20 cm to avoid dilution by aeolian sands and seasonal leaching processes. Regolith mapping and the distinction between the residual and transported weathering products are extremely significant to follow the distal or proximal mineralization.     

Correlations between metals in tree-rings of Prosopis julifora as indicators of sources of heavy metal contamination

Heavy-metals (Cu, Pb and Zn) in tree-ring sequences of Prosopis juliflora, a tree species native to arid environments, were analyzed by ICP-MS. The tree-ring sequences were obtained from three specimens growing in an urban area previously reported as contaminated by the activity of a Cu smelter facility. The metal found in highest concentration in the wood was Zn, with concentrations up to 120 mg/kg and an enrichment factor up to 26; followed by Cu (up to 9.6 mg/kg, enrichment factor up to 8.6) and Pb (up to 1.4 mg/kg, enrichment factor up to 3). By assessing the correlation between different metal concentration trends, it was possible to infer two main pollution sources: vehicle traffic and Cu smelter emissions. Vehicle traffic is indicated by a correlation between Pb and Zn over time within individual trees, whereas contamination from the Cu-smelting facility is indicated by a correlation of Cu over time between trees. In tree A there was a significant within-tree correlation between Pb and Zn concentration trends (r = 0.856, P < 0.001), whereas Cu showed no correlation with the other metals. For tree B, there were no within-tree correlations between these metals, but when comparing the concentration–time trends between trees A and B, there was a significant correlation for Cu (r = 0.768, P < 0.01). The tree-ring sequence from tree C showed significant within-tree correlation for Cu:Zn (r = 0.430, P < 0.01) and for Pb:Zn (r = 0.753, P < 0.001). The highest enrichment values were found in tree A, located along the path of the growing-season dominant wind direction from the smelter facility, and not in the tree growing closer to the smelter (tree C), suggesting that the smelter’s emissions are dispersed to longer distances through the tall chimneys, attenuating the impact to the area directly closest to the smelter facility. It is concluded that Prosopis juliflora appears as a good bioindicator based on its metal accumulation capacity and lack of metal mobility among tree rings, thus providing information on the chronology and sources of heavy-metal pollution in urban and industrial areas.