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.     

Modeling the adsorption of Cd (II), Cu (II), Ni (II), Pb (II) and Zn (II) onto montmorillonite

The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X⁻), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.     

Geochemistry of highly acidic mine water following disposal into a natural lake with carbonate bedrock

Acid mine drainage (AMD) from the Zn–Pb(–Ag–Bi–Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of ∼1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO₃, 4330 mg/L Fe and 29,250 mg/L SO₄. Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO₄). The variations in the H and O isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI ∼ 0.25) and anglesite (SI ∼ 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI ∼ 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI ∼ −0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material (∼90 wt.% water) of pH ∼1 with a total organic C content of up to 4.40 wet wt.% originated from the kerosene discharge of the Cu-extraction plant and had contaminant element concentrations similar to the lake water. Below the organic layer followed a layer of gypsum with pH 1.5, which overlaid the dissolving carbonate sediments of pH 5.3–7. In these two layers the contaminant elements were enriched compared to lake water in the sequence As < Pb ≈ Cu < Cd < Zn = Mn with increasing depth. This sequence of enrichment was explained by the following processes: (i) adsorption of As on Fe-hydroxides coating plant roots at low pH (up to 3326 mg/kg As), (ii) adsorption at increasing pH near the gypsum/calcite boundary (up to 1812 mg/kg Pb, 2531 mg/kg Cu, and 36 mg/kg Cd), and (iii) precipitation of carbonates (up to 5177 mg/kg Zn and 810 mg/kg Mn; all data corrected to a wet base). The infiltration rate was approximately equal to the discharge rate, thus gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks.     

The Drenchwater deposit,Alaska: An example of a natural low pH environment resulting from weathering of an undisturbed shale-hosted Zn–Pb–Ag deposit

The Drenchwater shale-hosted Zn–Pb–Ag deposit and the immediate vicinity, on the northern flank of the Brooks Range in north-central Alaska, is an ideal example of a naturally low pH system. The two drainages, Drenchwater and False Wager Creeks, which bound the deposit, differ in their acidity and metal contents. Moderately acidic waters with elevated concentrations of metals (pH ? 4.3, Zn ? 1400 μg/L) in the Drenchwater Creek drainage basin are attributed to weathering of an exposed base-metal-rich massive sulfide occurrence. Stream sediment and water chemistry data collected from False Wager Creek suggest that an unexposed base-metal sulfide occurrence may account for the lower pH (2.7–3.1) and very metal-rich waters (up to 2600 μg/L Zn, ? 260 μg/L Cu and ?89 μg/L Tl) collected at least 2 km upstream of known mineralized exposures. These more acidic conditions produce jarosite, schwertmannite and Fe-hydroxides commonly associated with acid-mine drainage. The high metal concentrations in some water samples from both streams naturally exceed Alaska state regulatory limits for freshwater aquatic life, affirming the importance of establishing base-line conditions in the event of human land development. The studies at the Drenchwater deposit demonstrate that poor water quality can be generated through entirely natural weathering of base-metal occurrences, and, possibly unmineralized black shale.     

Assessing the concentration,speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine,Vermont, USA

The authors determine the composition of a river that is impacted by acid-mine drainage, evaluate dominant physical and geochemical processes controlling the composition, and assess dissolved metal speciation and toxicity using a combination of laboratory, field and modeling studies. Values of pH increase from 3.3 to 7.6 and the sum of dissolved base metal (Cd + Co + Cu + Ni + Pb + Zn) concentrations decreases from 6270 to 100 μg/L in the dynamic mixing and reaction zone that is downstream of the river’s confluence with acid-mine drainage. Mixing diagrams and PHREEQC calculations indicate that mixing and dilution affect the concentrations of all dissolved elements in the reach, and are the dominant processes controlling dissolved Ca, K, Li, Mn and SO₄ concentrations. Additionally, dissolved Al and Fe concentrations decrease due to mineral precipitation (gibbsite, schwertmannite and ferrihydrite), whereas dissolved concentrations of Cd, Co, Cu, Ni, Pb and Zn decrease due to adsorption onto newly formed Fe precipitates.     

Contamination of surface waters by mining wastes in the Milluni Valley (Cordillera Real,Bolivia): Mineralogical and hydrological influences

This study is one of very few dealing with mining waste contamination in high altitude, tropical-latitude areas exploited during the last century. Geochemical, mineralogical and hydrological characterizations of potentially harmful elements (PHEs) in surface waters and sediments were performed in the Milluni Valley (main reservoir of water supply of La Paz, Bolivia, 4000 m a.s.l.), throughout different seasons during 2002–2004 to identify contamination sources and sinks, and contamination control parameters. PHE concentrations greatly exceeded the World Health Organization water guidelines for human consumption. The very acidic conditions, which resulted from the oxidation of sulfide minerals in mining waste, favoured the enrichment of dissolved PHEs (Cd > Zn ? As ? Cu ∼ Ni > Pb > Sn) in surface waters downstream from the mine. Stream and lake sediments, mining waste and bedrock showed the highest PHE content in the mining area. With the exception of Fe, the PHEs were derived from specific minerals (Fe, pyrite; Zn, Cd, sphalerite, As, Fe, arsenopyrite, Cu, Fe, chalcopyrite, Pb, galena, Sn, cassiterite), but the mining was responsible for PHEs availability. Most of the PHEs were extremely mobile (As > Fe > Pb > Cd > Zn ∼ Cu > Sn) in the mining wastes and the sediments downstream from the mine. pH and oxyhydroxides mainly explained the contrasted availability of Zn (mostly in labile fractions) and As (associated with Fe-oxyhydroxides). Unexpectedly, Pb, Zn, As, and Fe were significantly attenuated by organic matter in acidic lake sediments.     

Geochemical processes and mobilization of toxic metals and metalloids in an As-rich base metal waste pile in Zimapán,Central Mexico

The geochemistry and mineralogy of samples collected along depth profiles from an As-rich tailing deposit with abundant calcite was studied to determine the processes that influence the mobility of Fe, Zn, Cu, Ni, Cd, As, Sb, Cr and Tl. In spite of their near neutral pH, almost all of them are acid potential generators. Total concentrations decreased as: Fe > As > Zn > Pb > Cu > Sb > Cd > Cr > Ni > Tl. Soluble contents were lower and followed a slightly different order. Mobility decreased as: Tl > Cd, Zn, Cu, Sb, Ni, As > Fe, Pb > Cr. Higher soluble concentrations of Fe, Cu, Zn, As, Pb, and Ni were found in low-pH samples and of Sb and Tl in near-neutral samples. Sulfide oxidation processes are developing in the tailing’s dam. These processes do not have a trend with depth but occur mainly in acid layers. Near neutral layers formed by primary sulfides and calcite probably correspond to wastes produced from the processing of ore coming mainly from pods within the skarn, and acid layers with abundant secondary minerals from material mined from chimneys and mantos. The presence of calcite influences speciation, neutralizes acid mine drainage (AMD), and decreases the mobility of most toxic metals and metalloids (TMMs). However, a hard-pan layer was not observed in the studied profiles. Retention of TMM within tailings probably occurs through the formation of low solubility metal carbonates and from elevation of pH that promotes Fe hydroxides precipitation that may retain As, Sb and metals. Calcite occurrence promotes As, Cd, Cu, Fe, Zn, Pb, Cd and Cr retention, does not play a role on Tl and Ni mobilization, and increases Sb release.     

Field multi-step limestone and MgO passive system to treat acid mine drainage with high metal concentrations

Passive treatment systems have become one of the most sustainable and feasible ways of remediating acid mine drainage (AMD). However, conventional treatments show early clogging of the porosity or/and coating of the reactive grains when high acidity and metal concentrations are treated. The performance of fine-grained reagents dispersed in a high porosity matrix of wood shavings was tested as an alternative to overcome these durability problems. The system consisted of two tanks of 3 m³ filled with limestone sand and wood shavings, and one tank of 1 m³ with caustic magnesia powder and wood shavings, separated by several oxidation cascades and decantation ponds. The system treated about 1.5 m³/day of AMD containing an average of 360 mg/L Fe, 120 mg/L Al, 390 mg/L Zn, 10 mg/L Cu, 300 μg/L As and 140 μg/L Pb, a mean pH of 3.08 and a net acidity of 2500 mg/L as CaCO₃ equivalent. The water reached pH 5 and 6 in the first and second limestone tanks, respectively (suitable to remove trivalent metals); and pH 8–9 in the MgO tank (suitable to remove divalent metals). After 9 months of operation, the system achieved an average removal of 100% Al, Cu, As, Pb, more than 70% Fe, about 25% Zn and 80% acidity. Goethite, schwertmannite, hydrobasaluminite, amorphous Al(OH)₃ and gypsum were the main precipitates in the two limestone tanks. Precipitation of divalent metals (Fe (II), Zn, and traces of Cd, Ni and Co) were complete inside the third tank of MgO, but preferential flow along the walls was responsible for its low treatment performance. Goethite, gypsum, Zn-schulenbergite and sauconite are the crystalline solid phases identified in the MgO tank.     

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).     

Hydrological and geochemical control of metals and arsenic in a Mediterranean river contaminated by acid mine drainage (the Amous River,France); preliminary assessment of impacts on fish (Leuciscus cephalus)

Dissolved and particulate concentrations of metals (Fe, Al, Mn, Co, Ni, Cu, Zn, Cd, Tl, Pb) and As were monitored over a 5 year period in the Amous River downstream of its confluence with a creek severely affected by acid mine drainage (AMD) originating from a former Pb–Zn mine. Water pH ranged from 6.5 to 8.8. Metals were predominantly in dissolved form, except Fe and Pb, which were in particulate form. In the particulate phase, metals were generally associated with Al oxides, whereas As was linked to Fe oxides. Metal concentrations in the dissolved and/or particulate phase were generally higher during the wet season due to higher generation of AMD. Average dissolved (size < 0.22 μm) metal concentrations (μg/L) were 1 ± 4 (Fe), 69 ± 49 (Al), 140 ± 118 (Mn), 4 ± 3 Co, 6 ± 4 (Ni), 1.3 ± 0.8 (Cu), 126 ± 81 (Zn), 1.1 ± 0.7 (Cd), 0.9 ± 0.5 (Tl), 2 ± 3 (Pb). Dissolved As concentrations ranged from 5 to 134 μg/L (30 ± 23 μg/L). During the survey, the concentration of colloidal metals (5 kDa < size < 0.22 μm) was less than 25% of dissolved concentrations. Dissolved metal concentrations were generally higher than the maximum concentrations allowed in European surface waters for priority substances (Ni, Cd and Pb) and higher than the environmental quality standards for other compounds. Using Diffusion Gradient in Thin Film (DGT) probes, metals were shown to be in potentially bioavailable form. The concentrations in Leuciscus cephalus were below the maximum Pb and Cd concentrations allowed in fish muscle for human consumption by the European Water Directive. Amongst the elements studied, only As, Pb and Tl were shown to bioaccumulate in liver tissue (As, Pb) or otoliths (Tl). Bioaccumulation of metals or As was not detected in muscle.     

Global distributions of Fe,Al, Cu,and Zn contained in Earth's derma layers

To improve the usefulness and accuracy of modeling Earth's anthrobiogeochemical metal cycles, global maps at approximately 1° × 1° are produced of the concentrations and masses of Fe, Al, Cu, and Zn contained in continental sediments and soils. The maps generated utilize inverse distance weighting (IDW) and cokriging to generate new estimates for geospatially weighted mean global concentrations for these metallic micronutrients. Sediment metal concentration maps are generated from IDW of sediment samples; global soil maps are produced via cokriging upon an underlying parent rock dataset composed of both surface bedrock and sediment samples. Derived are independent estimates for the global mean concentrations in continental sediments (Fe = 3.1 wt.%, Al = 6.1 wt.%, Cu = 45 μg/g, Zn = 86 μg/g) and soils (Fe = 2.5 wt.%, Al = 3.9 wt.%, Cu = 17 μg/g, Zn = 50 μg/g). While continental sediment concentrations for Cu are within the range of previous estimates, Zn concentrations are relatively higher, ~ 20 μg/g above previous estimates. Fe and Al are slightly depleted (~ 1 wt.%) in continental sediments relative to previous estimates, likely ascribable to sampling bias and error inherent in the comparative methodologies. Besides an estimated global mean, metal concentrations in soils are also broken down by FAO soil group. Metal masses in sediments and soils remain within 30% of previous, non-spatial estimates. These maps also illustrate the discernable spatial variability across the Earth's surface. Despite data gaps, maps of metal mass show regional patterns such as the high quantities of Al in the soils and biomass of the Amazonia and Congo regions. Concentrations of metals are relatively high in the anthrosols of China. Finally, this analysis highlights those areas for which generating and providing publically available geochemical data should be prioritized. For instance, gypsisols, lixisols, and nitisols have little to no analytical data available on metal contents. A sensitivity analysis suggests that the most poorly constrained soil metal concentrations occur in the thick, old tropical soils of central Africa and the anthrosols of eastern China.     

Metal mobilization from base-metal smelting slag dumps in Sierra Almagrera (Almería,Spain)

Smelting slags associated with base-metal vein deposits of the Sierra Almagrera area (SE Spain) show high concentrations of Ag (<5–180 ppm), As (12–750 ppm), Cu (45–183 ppm), Fe (3.2–29.8%), Pb (511–2150 ppm), Sb (22–620 ppm) and Zn (639–8600 ppm). The slags are mainly composed of quartz, fayalite, barite, melilite, celsian, pyrrhotite, magnetite, galena and Zn–Pb–Fe alloys. No glassy phases were detected. The following weathering-related secondary phases were found: jarosite–natrojarosite, cotunnite, cerussite, goethite, ferrihydrite, chalcanthite, copiapite, goslarite, halotrichite and szomolnokite. The weathering of slag dumps near the Mediterranean shoreline has contaminated the soils and groundwater, which has caused concentrations in groundwater to increase to 0.64 mg/L Cu, 40 mg/L Fe, 0.6 mg/L Mn, 7.6 mg/L Zn, 5.1 mg/L Pb and 19 μg/L As. The results of laboratory leach tests showed major solubilization of Al (0.89–12.6 mg/L), Cu (>2.0 mg/L), Fe (0.22–9.8 mg/L), Mn (0.85–40.2 mg/L), Ni (0.092–2.7 mg/L), Pb (>2.0 mg/L) and Zn (>2.5 mg/L), and mobilization of Ag (0.2–31 μg/L), As (5.2–31 μg/L), Cd (1.3–36.8 μg/L) and Hg (0.2–7 μg/L). The leachates were modeled using the numerical code PHREEQC. The results suggested the dissolution of fayalite, ferrihydrite, jarosite, pyrrhotite, goethite, anglesite, goslarite, chalcanthite and cotunnite. The presence of secondary phases in the slag dumps and contaminated soils may indicate the mobilization of metals and metalloids, and help to explain the sources of groundwater contamination.     

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.     

Computer simulations of the interactions of the (0 1 2) and (0 0 1) surfaces of jarosite with Al, Cd, Cu and Zn

Jarosite is an important mineral on Earth, and possibly on Mars, where it controls the mobility of iron, sulfate and potentially toxic metals. Atomistic simulations have been used to study the incorporation of Al³⁺, and the M²⁺ impurities Cd, Cu and Zn, in the (0 1 2) and (0 0 1) surfaces of jarosite. The calculations show that the incorporation of Al on an Fe site is favorable on all surfaces in which terminal Fe ions are exposed, and especially on the (0 0 1) [Fe₃(OH)₃]⁶⁺ surface. Incorporation of Cd, Cu or Zn on a K site balanced by a K vacancy is predicted to stabilize the surfaces, but calculated endothermic solution energies and the high degree of distortion of the surfaces following incorporation suggest that these substitutions will be limited. The calculations also suggest that incorporation of Cd, Cu and Zn on an Fe site balanced by an OH vacancy, or by coupled substitution on both K and Fe sites, is unfavorable, although this might be compensated for by growth of a new layer of jarosite or goethite, as predicted for bulk jarosite. The results of the simulations show that surface structure will exert an influence on uptake of impurities in the order Cu > Cd > Zn, with the most favorable surfaces for incorporation being (0 1 2) [KFe(OH)₄]⁰ and (0 0 1) [Fe₃(OH)₃]⁶⁺.     

Competitive adsorption of trace elements in calcareous soils as affected by sewage sludge,poultry manure,and municipal waste compost

The competitive adsorption of trace elements is a key issue in assessing the mobility of trace elements in calcareous soils and can be affected by disposal of sewage sludge, municipal waste, and poultry manure. The effect of municipal sewage sludge, poultry manure, and municipal waste compost on the sorption of cadmium (Cd), copper (Cu), zinc (Zn), and nickel (Ni) in surface samples of three calcareous soils was studied. As the applied concentrations increased, Cu and Cd adsorption increased, while Zn and Ni adsorption decreased in all treatments. Based on the distribution coefficient (K _d) values and proportion of increase or decrease in metal adsorption, the selectivity sequence in control and amended soils found was Cu ≫ Cd ≫ Ni > Zn and Cu ≫ Cd ≫ Zn > Ni, respectively. In general, among control and amended soils, control soils showed the highest K _d for Cd, Cu, and Ni, while sludge, poultry manure, and composted waste-amended soils had lowest K _d for Cd, Cu, and Ni, respectively. In the case of Zn, composted waste-amended and control soils had highest and lowest K _d, respectively. The present experimental results indicated that the addition of organic amendments to these calcareous soils reduced the sorption of Cd, Cu, and Ni. Thus, the effects of preferential adsorption and organic matter should be considered in assessing the risk associated with applying sewage sludge, poultry manure, and composted material to calcareous soils.     

Distribution of Cd,Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40–80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.     

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.     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.     

Isotopic fractionation of Cu in tektites

Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth’s surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation.Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < δ⁶⁵Cu < 6.99) in comparison to the terrestrial crust (δ⁶⁵Cu ≈ 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated (δ⁶⁵Cu ≈ 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (δ⁶⁵Cu ≈ 0).An increase of δ⁶⁵Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (δ^66/64Zn up to 2.49‰). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn²⁺ vs. Cu⁺), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity.