Pb chronology and trace metal geochemistry at Los Tuxtlas, Mexico, as evidenced by a sedimentary record from the Lago Verde crater lake

Lago Verde is a fresh-water maar found on the lower slopes of San Martin volcano, at the Sierra de Los Tuxtlas, Mexico, currently the northernmost remnant of the tropical rain forest in America. ²¹⁰Pb and ¹³⁷Cs analyzed in a sediment core were used to reconstruct the historical fluxes of Ag, Cd, Cu, Pb, Hg and Zn to the site during the last ∼ 150 yr. The ²¹⁰Pb_xs-derived sediment accumulation rates, the magnetic susceptibility, C/N ratios and δ¹³C data evidenced background conditions at the lake until 1960s, when enhanced erosion related to the clearing of large forested areas at Los Tuxtlas promoted higher accumulation rates of a heavier and more magnetic sedimentary material. Recent sediments from Lago Verde were found enriched by Pb (26-fold natural concentration level [NCLs]) and moderately enriched by Cd > Cu > Zn and Hg (6-, 5-, 4- and 4-fold corresponding NCLs, respectively). The fluxes of Cu, Hg, Pb and Zn have significantly increased since 1940s, with peak ratios of total modern to pre-industrial fluxes of 11, 11, 19 and 49, respectively. The lake occupies a relatively pristine, non-industrialized basin, and therefore the increased metal fluxes might be related to long-distance aeolian transport of trace metals.     

Uptake of Zn,Cu, Pb,and Cd by water hyacinth in the initial stage of water system remediation

The removal efficiency of water hyacinth for Zn, Cu, Pb and Cd after their entry into an undisturbed fresh water body was studied using minicosms placed within a reservoir. Variable parameters were water pH (6 or 8), single or multi-metal additions, and the plant biomass. The initial concentrations of Zn, Cu, Pb and Cd in water (500, 250, 250 and 50 μg/L, respectively) quickly decreased in the order Pb ≈ Cu ? Cd ≈ Zn in the first days. Metal removal was more efficient at pH 8 than at pH 6, and it was only slightly higher for single metals compared to multi-metal additions. After 8 days the remaining amounts of metals relative to their initial concentrations for multi-metal pollution treatments were 8% and 24% (Cu), 11% and 26% (Pb), 24% and 50% (Cd), and 18% and 57% (Zn) at pH 8 and pH 6, respectively. Increasing plant biomass promoted faster metal removal. The bioconcentration factor (the ratio of the metal concentration in whole plants to the initial metal concentration in water) exceeds 2000 for all metals (with the exception of Zn and Cd at pH 6). It was concluded that the water hyacinth can be successfully used for fast removal of metals in the initial stage of water body remediation.     

Iron,manganese and trace metal concentrations in seaweeds from the central west coast of the Gulf of California

Concentrations of Co, Cu, Fe, Mn, Ni, Pb and Zn in four macroalgae species (Ulva lactuca, Chondracanthus squarrulosus, Sargassum sinicola and Gracilariopsis lemaneiformis) were obtained for the first time from the central part of the west coast of the Gulf of California. Generally, no differences in metal concentrations were found among the different seaweed species, although spatial differences were apparent. Iron, Mn and Cu exhibited higher concentrations at the stations located in front of Angel de la Guarda Island, probably because of high vertical mixing processes present in the zone. The results were compared with dissolved metal concentrations reported for the Gulf of California (Cd, Mn and Fe) and the North Pacific Ocean. The resulting linear regression of the results vs. North Pacific Ocean concentrations indicated that the levels of Cu, Ni and Zn measured in this study were within its 95% confidence level. Furthermore, this comparison was capable of detecting dissolved Fe and Mn enrichments in Gulf of California waters relative to the North Pacific Ocean concentrations. Calculations of total masses of metals associated with algal biomass on the west coast of the Gulf of California indicated that the lowest masses were represented by Cu (108 ± 25 kg) and Ni (184 ± 52 kg), whereas Pb (1.1 ± 0.6 ton) and Fe (10.9 ± 8.5 ton) were the elements with the highest associated masses.     

Mercury and other metal and metalloid soil contamination near a Pb/Zn smelter in east Hunan province, China

The spatial distributions of contaminant metals (Hg, Pb, Zn, Cd, Cu) and a metalloid (As) in vegetable plots and paddy fields located near a large scale Pb/Zn smelter in Hunan province, China, were investigated. Soil located 4 km from the smelter was severely contaminated, with maximum concentrations of Hg, Pb, Zn, Cd, Cu and As as high as 2.89, 1200, 3350, 41.1, 157 and 93 mg kg⁻¹, respectively. Concentrations of soil metal and As decreased with distance in the dominant wind direction. Single-factor assessment indicated pollution levels of Hg, Pb, Zn and Cd were most severe, while pollution levels for Cu and As were less severe. Results from a potential ecological risk assessment indicated high risk associated with the soil within a 4 km radius, with the contribution for each contaminant calculated as follows: Cd (70.0%), Hg (19.4%), Pb (4.8%), As (3.0%), Cu (1.7%) and Zn (1.1%). The forest soil in the nearby city park was also affected by the atmospheric depositions from smelting activities. Soil profiles demonstrated the pollutants were mostly accumulated in the upper 20 cm layer. Contamination of the topsoil with Hg, Pb, Zn, Cd, Cu and As indicated remediation should be considered.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Particulate-associated potentially harmful elements in urban road dusts in Xi’an,China

Sixty five urban road dust samples were collected from different land use areas of ∼240 km² in Xi’an, China. The concentrations of Ag, As, Cr, Cu, Hg, Pb, Sb and Zn were determined to investigate potentially harmful element (PHE) contamination, distribution and possible sources. In addition, the concentrations in different size fractions were measured to assess their potential impact on human health. The highest concentrations were found in the fraction with particle diameters between 80 μm and 101 μm, the finest particles (<63 μm) were not the most important carriers for Ag, As, Cd, Cr, Cu, Hg, Pb and Zn. The percentages of these elements in particles with diameters less than 63 μm (PM₆₃) and less than 101 μm (PM₁₀₁) were in the range of 7–15%, and 30–55%, respectively. Three main factors influencing element distributions have been identified: (a) industrial activities; (b) prior agricultural land use; and (c) other activities commonly found in urban areas, such as traffic, coal combustion, waste dumping, and building construction/renovation. The highest concentrations were found in industrial areas for As (20 mg kg⁻¹), Cr (853 mg kg⁻¹), Cu (1071 mg kg⁻¹), Pb (3060 mg kg⁻¹) and Zn (2112 mg kg⁻¹), and in previous agricultural areas for Ag and Hg, indicating significant contributions from industrial activities and prior agricultural activities.     

The mobility,bioavailability, and human bioaccessibility of trace metals in urban soils of Hong Kong

Trace metals in soils may pose risks to both ecosystem and human health, especially in an urban environment. However, only a fraction of the metal content in soil is mobile and/or available for biota uptake and human ingestion. Various environmental availabilities of trace metals (Cu, Pb and Zn) in topsoil from highly urbanized areas of Hong Kong to plants, organisms, and humans, as well as the leaching potential to groundwater were evaluated in the present study. Forty selected soil samples were extracted with 0.11 M acid acetic, 0.01 M calcium chloride, 0.005 M diethylenetriaminepentaacetic acid, and simplified physiologically based extraction tests (PBET) for the operationally defined mobilizable, effectively bioavailable, potentially bioavailable, and human bioaccessible metal fractions, respectively. The metals were generally in the order of Zn > Cu ∼ Pb for both mobility (24%, 7.6%, 6.7%) and effective bioavailability (2.8%, 0.9%, 0.6%), Pb (18%) > Cu (13%) > Zn (7.4%) for potential bioavailability, and Pb (59%) ∼ Cu (58%) > Zn (38%) for human bioaccessibility. Although the variations in the different available concentrations of metals could mostly be explained by total metal concentrations in soil, the regression model predictions were further improved by the incorporation of soil physicochemical properties (pH, OM, EC). The effectively bioavailable Zn and Pb were mostly related to soil pH. Anthropogenic Pb in urban soils tended to be environmentally available as indicated by Pb isotopic composition analysis. Combining various site-specific environmental availabilities might produce a more realistic estimation for the integrated ecological and human health risks of metal contamination in urban soils.     

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO₃ electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (⁶⁵Cu/⁶³Cu) and Zn (⁶⁶Zn/⁶⁴Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (α_soln-solid) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors (Δ_soln-solid) are −0.73 ± 0.08‰ for Cu and −0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).     

Effect of citrate on the local Fe coordination in ferrihydrite, arsenate binding, and ternary arsenate complex formation

In oxic environments contaminated with arsenate (As(V)), small polyhydroxycarboxylates such as citrate may impact the structure of precipitating ferrihydrite (Fh) and thus the surface speciation of As(V). In this study, ‘2-line’ Fh was precipitated from ferric nitrate solutions that were neutralized to pH 6.5 in the presence of increasing citrate concentrations and in the absence or presence of As(V). The initial citrate/Fe and As/Fe ratios were 0-50 mol% and 5 mol%, respectively. The reaction products, enriched with up to 0.32 mol citrate per mole Fe, were characterized by X-ray diffraction, transmission electron microscopy, and Fe and As K-edge X-ray absorption spectroscopy. Citrate decreased the particle size of Fh by impairing the polymerization of Fe(O,OH)₆ octahedra via edge and corner linkages. In the presence of citrate and As(V), coordination numbers of Fe decreased by up to 28% relative to pure Fh. Citrate significantly reduced the static disorder of Fe-O bonds, implying a decreased octahedral distortion in Fh. Mean bond distances in Fh were not affected by citrate and remained constant within error at 1.98 Å for Fe-O, 3.03 Å for Fe-Fe1, and 3.45 Å for Fe-Fe2. Likewise, citrate had no effect on the As-Fe (3.31 Å) bond distance in As(V) coprecipitated with Fh. The As K-edge EXAFS data comply with the formation of (i) only monodentate binuclear (²C) As(V) surface complexes and (ii) combinations of ²C, monodentate mononuclear (¹V), and outersphere As(V) surface complexes. Our results suggest that increasing citrate concentrations led to a decreasing ¹V/²C ratio and/or that citrate increasingly impaired the formation of outersphere As(V) complexes. Moreover, citrate stabilized colloidal suspensions of Fh (pH 4.3-6.6, I ∼0.45 M) and reduced Fh formation at the expense of soluble Fe(III)-citrate complexes. At initial citrate/Fe ratios ?25 mol%, between 8% and 41% of total Fe was bound in Fe(III)-citrate complexes after Fh formation. Polynuclear Fe(III)-citrate species were found to bind As(V) via surface complexes indistinguishable by EXAFS from those of As(V) adsorbed to or coprecipitated with Fh. Our study implies that low molecular weight polyhydroxycarboxylates may enhance the mobility of As(V) in aqueous systems of high ionic strength (e.g., neutralizing acid mine drainage) by colloidal stabilization of suspended Fh particles and the formation of ternary As(V) complexes.     

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

The maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies such as phytoremediation. In the present work, the mineralogical transformations of Zn-containing phases induced by two graminaceous plants (Agrostis tenuis and Festuca rubra) in a contaminated sediment ([Zn] = 4700 mg kg⁻¹, [P₂O₅] = 7000 mg kg⁻¹, pH = 7.8), untreated or amended with hydroxylapatite (AP) or Thomas basic slag (TS), were investigated after two yr of pot experiment by scanning electron microscopy coupled with energy-dispersive spectrometry (SEM-EDS), synchrotron-based X-ray microfluorescence (μ-SXRF), and powder and laterally resolved extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. The number and nature of Zn species were evaluated by principal component (PCA) and least-squares fitting (LSF) analysis of the entire set of μ-EXAFS spectra, which included up to 32 individual spectra from regions of interest varying in chemical composition. Seven Zn species were identified at the micrometer scale: sphalerite, gahnite, franklinite, Zn-containing ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted kerolite-like trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra.In the untreated and unvegetated sediment, Zn was distributed as ∼50% (mole ratio of total Zn) sphalerite, ∼40% Zn-ferrihydrite, and ∼10 to 20% (Zn-Al)-hydrotalcite plus Zn-phyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20% and were replaced by Zn-phosphate (∼30∼40%). In the presence of plants, ZnS was almost completely dissolved, and the released Zn bound to phosphate (∼40-60%) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite (∼20-40%). Neither the plant species nor the coaddition of mineral amendment affected the Zn speciation in the vegetated sediment. The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)-hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result from heterogeneous precipitation on mineral surface.     

Geochemical characteristics of stream sediments,sediment fractions,soils, and basement rocks from the Mahaweli River and its catchment,Sri Lanka

Geochemical variations in stream sediments (n = 54) from the Mahaweli River of Sri Lanka have been evaluated from the viewpoints of lithological control, sorting, heavy mineral concentration, influence of climatic zonation (wet, intermediate, and dry zones), weathering, and downstream transport. Compositions of soils (n = 22) and basement rocks (n = 38) of the catchment and those of <180 μm and 180–2000 μm fractions of the stream sediments were also examined. The sediments, fractions, soils and basement rocks were analyzed by X-ray fluorescence to determine their As, Pb, Zn, Cu, Ni, Cr, V, Sr, Y, Nb, Zr, Th, Sc, Fe₂O₃, TiO₂, MnO, CaO, P₂O₅ and total sulfur contents. Abundances of high field strength and ferromagnesian elements in the sediments indicate concentration of durable heavy minerals including zircon, tourmaline, rutile, monazite, garnet, pyriboles, and titanite, especially in <180 μm fractions. The sediments show strong correlation between Ti and Fe, further suggesting presence of heavy mineral phases containing both elements, such as ilmenite and magnetite. The basement rocks range from mafic through to felsic compositions, as do the soils. The river sediments lack ultrabasic components, and overall have intermediate to felsic compositions. Elemental spikes in the confluences of tributary rivers and high values in the <180 μm fractions indicate sporadic inputs of mafic detritus and/or heavy minerals to the main channel. Al₂O₃/(K₂O + Na₂O) and K₂O/Na₂O ratios of the sediments and LOI values of the soils correlate well with the climatic zones, suggesting intense weathering in the wet zone, lesser weathering in the intermediate zone, and least weathering in the dry zone. Low Sr and CaO contents and Cr/V ratios in stream sediments in the wet zone also suggest climatic influence. Fe-normalized enrichment factors (EFs) for As, Pb, Zn, Cu, Ni and Cr in stream sediments in the main channel are nearly all <1.5, indicating there is no significant environmental contamination. The chemistry of the sediments, rocks and the soils in the Mahaweli River are thus mainly controlled by source lithotype, weathering, sorting, and heavy mineral accumulation.     

An assessment of selected heavy metal contamination in the surface sediments from the South China Sea before 1998

Rapid economic development in East Asian countries has inevitably resulted in environmental degradation in the surrounding seas, and concern for both the environment and protection against pollutants is increasing. Identification of sources of contaminants and evaluation of current environmental status are essential to environmental pollution management, but relatively little has been done in the South China Sea (SCS). In order to investigate the metal pollution status and source within the SCS, a total of 52 surface sediment samples were collected in 1998 from the SCS for the selected heavy metal measurements such as Pb, Zn, Cu, V, Cr, Cd and Sc. The total concentrations (in mg kg^− 1 dry weight) in sediments ranged and averaged (mean ± S.D.): Pb, 4.18 to 58.7 (23.6 ± 8.93); Zn, 10.7 to 346 (87.4 ± 47.7); Cu, 5.29 to 122 (38.1 ± 24.6); V, 0.03 to 148 (78.0 ± 37.0); Cr, 4.48 to 589 (105 ± 86); Cd, 0.08 to 2.14 (0.40 ± 0.40) and Sc, 0.33 to 20.6 (10.6 ± 4.4), respectively. Enrichment factor (EF) values and geoaccumulation indexes (I_geo) suggest that Cu, Pb, Zn and V contamination exists only in few localized areas, but Cr and Cd contamination can be found in large-scale area of the SCS before 1998. Further studies are needed to reconstruct deposition history and for trend analysis.     

Biogeochemistry of Pb–Zn gossans,northwest Queensland,Australia: Implications for mineral exploration and mine site rehabilitation

The concentration and distribution of metals were studied in metallophytes, growing on and in the vicinity of Pb–Zn gossans, NW Queensland. The study investigated the accumulation of metals in plant species and assessed their potential use as indicators in geobotanical and biogeochemical prospecting and as metal excluders in mine site rehabilitation. Plant species colonising the gossans tolerate high concentrations of metals. Total mean metal concentrations of soils ranged from minima of 14 ppm Cu, 28 ppm Pb and 34 ppm Zn in background areas to maxima of 660 ppm Cu, 12000 ppm Pb and 2100 ppm Zn over mineralised soils. Over the gossans, the grass species Eriachne mucronata forma, Enneapogon lindleyanus and Paraneurachne muelleri replace the characteristic grass Triodia molesta where the soils have high Pb and Zn concentrations. Of the 16 plant species identified, 3 of them, Hybanthus aurantiacus, Clerodendrum tomentosum and Bulbostylis barbata, were confined to the gossan sites. B. barbata appears to be of particular use in geobotanical prospecting as it indicates base metal mineralisation in the region.     

Spatial variability of topsoil contamination with trace elements in preschools in Vilnius,Lithuania

An investigation of the spatial variability of topsoil contamination level was performed in 49 preschool playgrounds located in Vilnius city and correlated with urban (height and age of the preschools and height of surrounding buildings) and natural (altitude) factors. Composite samples, consisting of 20–30 sub-samples, were collected from 10 cm topsoil layer with a 3–5 m distance from each other. Sieved fraction (< 0.63 mm) was ashed at 400 °C, ground to < 1.0 μm and analysed for the real total concentrations of 22 trace elements (Ag, B, Ba, Co, Cr, Cu, Ga, Li, Mn, Mo, Nb, Ni, Pb, Sc, Sn, Sr, Ti, V, Y, Yb, Zn and Zr) using optical atomic emission spectrophotometry. Information on construction year and height (number of building stories) of preschool and surrounding buildings was acquired from the Centre of Registers of Lithuania. Out of 22 analysed elements, 13 to a greater extent exceeded the background values in several areas and were used to calculate the total contamination index (Z_s13). Out of 49 analysed areas, 21 had moderately hazardous to hazardous levels of contamination as indicated by Z_s13. The main contaminating elements, exceeding the permissible concentrations were Ag, Cu, Mo, Pb, Sn and Zn, the origins of which coincide with city industry and traffic. Topsoil around the newer preschool buildings, despite their location, contained lower concentrations of contaminants, while areas at higher altitudes were more contaminated than those located at lower altitudes. The latter causality is biased, as the city industry, and hence the highest contamination, is in districts located higher above sea level than the remaining studied sites.     

Immobilization of heavy metals in a contaminated soil in Iran using di-ammonium phosphate,vermicompost and zeolite

Fractionation of heavy metals (HMs) in amended soils is needed to predict elemental mobility in soil and phytoavailability to plants. A study was conducted to determine the effects of different amendments on HMs availability and their redistribution among soil fractions. A contaminated soil was selected from around a Zn mine and amended with 0, 2, 4, and 6 g kg⁻¹ of vermicompost (VC), zeolite (ZE), and di-ammonium phosphate (DP) and incubated at field moisture. The amounts of Cd, Pb, Zn, and Cu were determined from the soil after 6 months of incubation time using DTPA and sequential extraction procedures. The total concentrations of Cd, Pb, Zn, and Cu were 41, 3,099, 1,997, and 83 mg kg⁻¹ of soil, respectively. All amendments decreased significantly [probability (p) ≤ 0.05] DTPA-extractable Cd, Pb, and Cu, but not Zn, in the soil. For instance, DTPA-extractable Cd, Pb, and Cu decreased by 40, 290, and 20%, respectively, and that of Zn increased by 18% with DP₁ (2 g kg⁻¹ of di-ammonium phosphate) application. The concentrations of Pb and Cd decreased mainly in the specifically sorbed (SS) but increased in the amorphous Fe oxide (AFeO) fraction with DP application, indicating redistribution of Pb and Cd in the fractions with less mobility. Lead immobilization by DP was mainly attributed to the P-induced formation of chloropyromorphite, which was identified in the DP treatment using X-ray diffraction technique. It was concluded that DP was the most effective amendment in immobilizing Pb and Cd, though it increased Zn mobility.     

Early diagenetic vivianite [Fe3(PO4)2 · 8H2O] in a contaminated freshwater sediment and insights into zinc uptake: A μ-EXAFS, μ-XANES and Raman study

The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe₃(PO₄)₂ · 8H₂O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe–O and Fe–P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99–2.05 Å; 2P atoms at 3.17–3.25 Å). One analysed grain displays evidence of a significant Fe³⁺ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 Å; 2P atoms at 3.17 Å). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption.     

Phosphate amendment of metalliferous waste rocks, Century Pb-Zn mine, Australia: Laboratory and field trials

The aim of the study was to determine whether the application of phosphate compounds (phosphorite rock, phosphate fertilizer) to polyminerallic waste rocks can inhibit sulfide oxidation and metal mobility (Cu, Pb, Zn, Cd, Ni, Mn, Mg). Waste rocks comprised sulfidic carbonaceous shales and were sourced from the Century Pb-Zn mine, NW Queensland, Australia. The acid producing, Pb-Zn rich rocks consisted of major quartz, muscovite/illite, dolomite, siderite and kaolinite as well as smaller amounts of sulfide minerals (e.g. galena, sphalerite, pyrite). Laboratory leach experiments were conducted on finely granulated phosphate-treated waste rocks (>2 to <30 mm) over 13 weeks, whereas phosphate amendment of coarsely granulated waste rocks (sand to boulder size) was investigated using heap leach piles at the mine site over an 11 months period. Results of the laboratory experiments demonstrate that the treatment of finely granulated waste rocks with phosphorite rock produced leachates with near-neutral pH values due to calcite dissolution. This in turn did not allow the leaching of apatite, formation of secondary phosphate phases and phosphate stabilization to occur. Metal mobility in these amended wastes was restricted by the dissolution of calcite and the resultant near-neutral pH conditions. By contrast, the application of the water-soluble phosphate fertilizer MKP (KH₂PO₄) to polyminerallic sulfidic waste rocks during the short-term laboratory experiments led to the formation of phosphate coatings and precipitates and inhibited acid and metal release (Cd, Mn, Ni, Pb, Zn). At least in the short term, the application of phosphate fertilizers proved to be an effective method. However, results of the long-term field trials demonstrate that coarsely granulated waste rocks were not coated by secondary phosphate phases and that amendment by phosphorite rock or superphosphate fertilizer did not improve leachate quality compared to the unamended waste. Thus, phosphate stabilization appears ineffective in suppressing oxidation of sulfides in coarsely granulated mine wastes.     

Soil Cd,Cu, Pb and Zn contaminants around Mount Isa city,Queensland, Australia: Potential sources and risks to human health

This article investigates the relationship between soil Cd, Cu, Pb and Zn contaminants and the location and activities of the Pb–Zn–Ag and Cu mines at Mount Isa, Queensland, Australia. Analysis of the data focuses primarily on soil Pb distributions and concentrations because of their potential impact on children’s health. The Xstrata Mount Isa Mines lease (XMIM) is Australia’s leading emitter of numerous contaminants to the environment, including Cu and Pb, and the mining-related activities have been linked causally to the findings of a 2008 study that showed 11.3% of local children (12–60 months) have blood Pb levels >10 μg/dL. Queensland government authorities and Xstrata Mount Isa Mines Pty Ltd maintain that contaminants within environmental systems around Mount Isa are largely the result of near-surface mineralization. The evidence for whether the contamination is derived from XMIM or other possible sources, such as the natural weathering of ore-rich bedrock, is investigated using data from surface and subsurface soil chemistry, atmospheric modelling of metal contaminants from mining and smelting operations and local geological and associated geochemical studies. Sixty surface soil samples collected from sites adjacent to houses, parks and schools throughout Mount Isa city were analyzed for their total extractable Cd, Cu, Pb and Zn concentrations in the <2 mm to >180 μm (coarser) and <180 μm (finer) grain size fractions. Concentrations in the finer size fraction reveal a range of values: Cd – 0.7–12.5 ppm; Cu – 31–12,100 ppm; Pb – 8–5770 ppm; Zn – 26–11,100 ppm, with several samples exceeding Australian residential health investigation guidelines. Spatial analysis shows that surface soil metal concentrations are significantly higher within 2 km of XMIM compared to more distant samples, and that more than 1000 property lots are at risk of having detrimentally high soil Pb levels. Determination of metal concentrations in 49 samples from eight soil pits shows that surface samples (0–2 cm) are enriched significantly relative to those at depth (10–20 cm), suggesting an atmospheric depositional origin. AUSPLUME air dispersal modelling of Pb originating from the Cu and Pb smelter stacks and mine site fugitive sources confirms that Pb is deposited across the urban area, during periods of the year (∼20%/a) when the wind blows from the direction of XMIM towards the urban area and disperses dusts from the uncovered spoil and road surfaces, as well as from stack emission sources. Although there are some spatially restricted outcrops of Pb close to the surface in parts of the urban area, the Cu-ore body is ∼244 m below the surface. However, enriched and significantly correlated surface soil concentrations of Cu and Pb (Pearson correlation 0.879, p = 0.000) in and around the urban area of Mount Isa can only be explained by atmospheric transport and deposition of metals from the adjoining mining and smelting operations. The results from this study provide unequivocal evidence that both historic and ongoing emissions from XMIM are contaminating the urban environment. Given the ongoing Pb poisoning issues in Mount Isa children, it is clear that remediation, reductions in mine emissions and more stringent regulatory actions are warranted.     

Particulate air pollution in a small settlement: The effect of local heating

Mass concentrations of PM₁₀, PM_2.5, and black smoke (BS) were measured in April 2003 during a 3-week campaign in a small village and at a nearby background location in the central part of the Czech Republic. In a pilot analysis, concentrations of selected trace elements (Al, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Sb, Cs, Pb) in the collected aerosol were determined by means of ICP-MS. Average concentrations of both PM fractions and BS were higher in the village (37, 26 and 26 μg m⁻³) than at the background location (26, 19 and 11 μg m⁻³) for PM₁₀, PM_2.5 and BS, respectively. Both PM₁₀ and PM_2.5 were reasonably correlated in the village (r = 0.80) and also at the background location (r = 0.79). Correlation between same fractions from the village and from the background site were even higher (r = 0.97 and r = 0.95 for the PM₁₀ and PM_2.5, respectively) suggesting that most of the aerosol in both locations may be influenced by similar sources. The ratio between PM₁₀ and PM_2.5 showed that sources in the village contributed about 33% and 35% to local aerosol concentration for PM₁₀ and PM_2.5, respectively. When the data from the two rural locations were compared with corresponding 24-h averages of PM₁₀ concentrations obtained for the period of the campaign from fixed site monitors situated near larger towns, the highest concentration was found in Prague the Czech capital (49 μg m⁻³) followed by a district town Beroun (41 μg m⁻³) and the village (37 μg m⁻³). The lowest PM₁₀ concentration was found in the village background (26 μg m⁻³). Elemental analysis revealed higher concentrations for most of the elements characteristic of combustion aerosol (namely Zn, Pb, As, Mn and Ti) in the PM collected in the village. The results support the idea that traditional heating in villages may contribute a great extent to local air pollution and may represent an important problem.     

Field application of calcite Dispersed Alkaline Substrate (calcite-DAS) for passive treatment of acid mine drainage with high Al and metal concentrations

Passive treatment systems are widely used for remediation of acid mine drainage (AMD), but existing designs are prone to clogging or loss of reactivity due to Al- and Fe-precipitates when treating water with high Al and heavy metal concentrations. Dispersed alkaline substrate (DAS) mixed from a fine-grained alkaline reagent (e.g. calcite sand) and a coarse inert matrix (e.g. wood chips) had shown high reactivity and good hydraulic properties in previous laboratory column tests. In the present study, DAS was tested at pilot field scale in the Iberian Pyrite Belt (SW Spain) on metal mine drainage with pH near 3.3, net acidity 1400–1650 mg/L as CaCO₃, and mean concentrations of 317 mg/L Fe (95% Fe(II)), 311 mg/L Zn, 74 mg/L Al, 20 mg/L Mn, and 1.5–0.1 mg/L Cu, Co, Ni, Cd, As and Pb. The DAS-tank removed an average of 870 mg/L net acidity as CaCO₃ (56% of inflow), 25% Fe, 93% Al, 5% Zn, 95% Cu, 99% As, 98% Pb, and 14% Cd, but no Mn, Ni or Co. Average gross drain pipe alkalinity was 181 mg/L as CaCO₃, which increased total Fe removal to 153 mg/L (48%) in subsequent sedimentation ponds. Unfortunately, the tank suffered clogging problems due to the formation of a hardpan of Al-rich precipitates. DAS lifetime could probably be increased by lowering Al-loads.