Environmental geochemistry of an active Hg mine in Xunyang,Shaanxi Province,China

The Xunyang Hg mine (XMM) situated in Shaanxi Province is an active Hg mine in China. Gaseous elemental Hg (GEM) concentrations in ambient air were determined to evaluate its distribution pattern as a consequence of the active mining and retorting in the region. Total Hg (HgT) and methylmercury (MeHg) concentrations in riparian soil, sediment and rice grain samples (polished) as well as Hg speciation in surface water samples were measured to show local dispersion of Hg contamination. As expected, elevated concentrations of GEM were found, ranging from 7.4 to 410 ng m⁻³. High concentrations of HgT and MeHg were also obtained in riparian soils, ranged from 5.4 to 120 mg kg⁻¹ and 1.2 to 11 μg kg⁻¹, respectively. Concentrations of HgT and MeHg in sediment samples varied widely from 0.048 to 1600 mg kg⁻¹ and 1.0 to 39 μg kg⁻¹, respectively. Surface water samples showed elevated HgT concentrations, ranging from 6.2 to 23,500 ng L⁻¹, but low MeHg concentrations, ranging from 0.022 to 3.7 ng L⁻¹. Rice samples exhibited high concentrations of 50–200 μg kg⁻¹ in HgT and of 8.2–80 μg kg⁻¹ in MeHg. The spatial distribution patterns of Hg speciation in the local environmental compartments suggest that the XMM is the source of Hg contaminations in the study area.     

Mercury contamination due to zinc smelting and chlor-alkali production in NE China

Zinc smelting and chlor-alkali production are major sources of Hg contamination to the environment, potentially leading to serious impacts on the health of the local population. Huludao, NE China has been heavily contaminated by Hg due to long-term Zn smelting and chlor-alkali production. The aim of this work was to determine Hg accumulation in the aquatic and terrestrial environment, as well as in the human population of Huludao. The investigation included: (a) Hg accumulation in sediments, Spirogyra algae, crucian carp and shrimp, (b) Hg distribution in soil, vegetables and corn, and (c) assessment of potential health effects of Hg exposure associated with total Hg (T-Hg) concentrations in human hair. Measured T-Hg concentrations in sediments of Wuli River ranged from 0.15 to 15.4 mg kg⁻¹, with the maximum Hg concentration in sediment exceeding the background levels in Liaoning Province by 438 times. The maximum T-Hg levels in Spirogyra, crucian carp and shrimp were 13.6, 0.36, and 0.44 mg kg⁻¹, respectively. Total-Hg concentrations in hair of the human population varied from 0.05 to 3.25 mg kg⁻¹ (average 0.43 mg kg⁻¹). However, the frequency of paraesthesia to most inhabitants in Huludao was estimated to be lower than 5%, with only one person rated at 50%. The results indicated minimal adverse health effects of Hg exposure to the inhabitants of Huludao, despite the serious Hg contamination of the environment.     

Potentially harmful elements in rice paddy fields in mercury hot spots in Guizhou, China

Levels of the chalcophile metals Hg, Pb, Cd, Cu and Zn and the metalloid As in soils from rice paddy fields were assessed in two regions impacted by different industrial activities in Guizhou province, China. The two study areas (Wanshan and Qingzhen) have previously received attention in the international literature due to heavy Hg pollution, though levels of other potentially harmful elements have not previously been reported. The regions were selected as representing two important, but categorically different metal(loid) contaminated areas in China: Wanshan has been a major region for Hg production while Qingzhen is an important region for a large range of various heavy industries based on coal as an energy source.Within a limited distance of the Hg mine tailings in Wanshan the rice paddy fields are heavily contaminated by Hg (median concentration 25 μg g⁻¹, maximum 119 μg g⁻¹) and moderately contaminated by Zn and Cd (median concentrations of 86 and 0.9 μg g⁻¹, respectively). Zinc and Cd levels correlate well with Hg contamination, which indicates a similar source and mechanism of transport and accumulation. Other studies have concluded that the main sources of Hg contamination in Wanshan are the numerous Hg mine tailings. This is likely as these metals are all geochemically associated with the mineral cinnabar (HgS). The other chalcophile elements (Pb, Cu and As) are nevertheless found at background levels only. In Qingzhen the soils were found to contain elevated levels of As and Hg (median concentrations of 38 and 0.3 μg g⁻¹, respectively). These are elements that are known to be more associated with coal and released during coal combustion.     

A comparison of winter mercury accumulation at forested and no-canopy sites measured with different snow sampling techniques

Atmospheric mercury (Hg) is delivered to ecosystems via rain, snow, cloud/fog, and dry deposition. The importance of snow, especially snow that has passed through the forest canopy (throughfall), in delivering Hg to terrestrial ecosystems has received little attention in the literature. The snowpack is a dynamic system that links atmospheric deposition and ecosystem cycling through deposition and emission of deposited Hg. To examine the magnitude of Hg delivery via snowfall, and to illuminate processes affecting Hg flux to catchments during winter (cold season), Hg in snow in no-canopy areas and under forest canopies measured with four collection methods were compared: (1) Hg in wet precipitation as measured by the Mercury Deposition Network (MDN) for the site in Acadia National Park, Maine, USA, (2) event throughfall (collected after snowfall cessation for accumulations of >8 cm), (3) season-long throughfall collected using the same apparatus for event sampling but deployed for the entire cold season, and (4) snowpack sampling. Estimates (mean ± SE) of Hg deposition using these methods during the 91-day cold season in 2004–2005 at conifer sites showed that season-long throughfall Hg flux (1.80 μg/m²) < snowpack Hg (2.38 ± 0.68 μg/m²) < event throughfall flux (5.63 ± 0.38 μg/m²). Mercury deposition at the MDN site (0.91 μg/m²) was similar to that measured at other no-canopy sites in the area using the other methods, but was 3.4 times less than was measured under conifer canopies using the event sampling regime. This indicates that snow accumulated under the forest canopy received Hg from the overstory or exhibited less re-emission of Hg deposited in snow relative to open areas. The soil surface of field-scale plots were sprayed with a natural rain water sample that contained an Hg tracer (²⁰²Hg) just prior to the first snowfall to explore whether some snowpack Hg might be explained from soil emissions. The appearance of the ²⁰²Hg tracer in the snowpack (0–64% of the total Hg mass in the snowpack) suggests that movement of Hg from the soil into the snowpack is possible. However, as with any tracer study the ²⁰²Hg tracer may not precisely represent the reactivity and mobility of natural Hg in soils.     

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.     

The geochemical behavior and isotopic composition of Hg in a mid-Pleistocene western Mediterranean sapropel

The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average δ²⁰²Hg value of −0.91‰ ± 0.15‰ (n = 5, 1 SD) and Δ¹⁹⁹Hg value of 0.11‰ ± 0.03‰ (n = 5, 1 SD). Background sediments have an average δ²⁰²Hg of −0.76‰ ± 0.16‰ (n = 5, 1 SD) and Δ¹⁹⁹Hg of 0.05‰ ± 0.01‰ (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.     

Atmospheric deposition and isotope biogeochemistry of zinc in ombrotrophic peat

Zinc isotope ratios were measured in the top sections of dated ombrotrophic peat cores in Finland to investigate their potential as proxies for atmospheric sources and to constrain post depositional processes affecting the geochemical record. The peat deposits were located in Hietajärvi, a background site well away from any point pollution source and representing ‘background’ conditions, in Outokumpu, next to a mining site, and in Harjavalta, next to a smelter. Measured total concentrations, calculated excess concentrations and mass balance considerations suggest that zinc is subjected to important biogeochemical cycling within the peat. Significant isotopic variability was found in all three peat bogs, with heavier zinc in the deeper and lighter zinc in the upper sections. Isotope ratios and concentrations correlated in the two peats located next to dominant point sources, i.e. the smelting and mining site, suggesting that zinc isotopes trace pollution sources. Concentration and isotope peaks were offset from the period of mining and smelting activity, supporting migration of zinc down the profile. The δ⁶⁶Zn_JMC (where δ⁶⁶Zn = [(⁶⁶Zn/⁶⁴Zn)_sample/(⁶⁶Zn/⁶⁴Zn)_JMC-standard − 1] × 10³) of the top section sample at the remote Hietajärvi site was 0.9‰ and we suggest this represents the regional background isotope signature of atmospheric zinc. The deeper sections of the peat cores show isotopically heavier zinc than any potential atmospheric source, indicating that post depositional processes affected the isotopic records. The large variations encountered (up to 1.05‰ for δ⁶⁶Zn) and Rayleigh modelling imply that multiple fractionation of zinc during diagenetic alterations occurs and nutrient recycling alone cannot explain the fractionation pattern.We propose that zinc isotopes are amenable to identify different atmospheric zinc sources, including zinc derived from anthropogenic activities such as mining and smelting, but multiple biogeochemical processes seriously affect the record and they need to be evaluated and assessed carefully if zinc isotopes are used in terrestrial paleorecords.     

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.     

The gold content of volcanogenic massive sulfide deposits

Volcanogenic massive sulfide deposits contain variable amounts of gold, both in terms of average grade and total gold content, with some VMS deposits hosting world-class gold mines with more than 100?t Au. Previous studies have identified gold-rich VMS as having an average gold grade, expressed in g/t, exceeding the total abundance of base metals, expressed in wt.%. However, statistically meaningful criteria for the identification of truly anomalous deposits have not been established. This paper presents a more extensive analysis of gold grades and tonnages of 513 VMS deposits worldwide, revealing a number of important features in the distribution of the data. A large proportion of deposits are characterized by a relatively low gold grade (<2?g/t), with a gradual decrease in frequency towards maximum gold grades, defining a log-normal distribution. In the analysis presented in this paper, the geometric mean and geometric standard deviation appear to be the simplest metric for identifying subclasses of VMS deposits based on gold grade, especially when comparing deposits within individual belts and districts. The geometric mean gold grade of 513 VMS deposits worldwide is 0.76?g/t; the geometric standard deviation is +2.70?g/t Au. In this analysis, deposits with more than 3.46?g/t Au (geometric mean plus one geometric standard deviation) are considered auriferous. The geometric mean gold content is 4.7?t Au, with a geometric standard deviation of +26.3?t Au. Deposits containing 31?t Au or more (geometric mean plus one geometric standard deviation) are also considered to be anomalous in terms of gold content, irrespective of the gold grade. Deposits with more than 3.46?g/t Au and 31?t Au are considered gold-rich VMS. A large proportion of the total gold hosted in VMS worldwide is found in a relatively small number of such deposits. The identification of these truly anomalous systems helps shed light on the geological parameters that control unusual enrichment of gold in VMS. At the district scale, the gold-rich deposits occupy a stratigraphic position and volcanic setting that commonly differs from other deposits of the district possibly due to a step change in the geodynamic and magmatic evolution of local volcanic complexes. The gold-rich VMS are commonly associated with transitional to calc-alkaline intermediate to felsic volcanic rocks, which may reflect a particularly fertile geodynamic setting and/or timing (e.g., early arc rifting or rifting front). At the deposit scale, uncommon alteration assemblages (e.g., advanced argillic, aluminous, strongly siliceous, or potassium feldspar alteration) and trace element signatures may be recognized (e.g., Au?CAg?CAs?CSb ± Bi?CHg?CTe), suggesting a direct magmatic input in some systems.     

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.     

Recent paleorecords document rising mercury contamination in Lake Tanganyika

Recent Lake Tanganyika Hg deposition records were derived using ¹⁴C and excess ²¹⁰Pb geochronometers in sediment cores collected from two contrasting depositional environments: the Kalya Platform, located mid-lake and more removed from watershed impacts, and the Nyasanga/Kahama River delta region, located close to the lake’s shoreline north of Kigoma. At the Kalya Platform area, pre-industrial Hg concentrations are 23 ± 0.2 ng/g, increasing to 74 ng/g in modern surface sediment, and the Hg accumulation rate has increased from 1.0 to 7.2 μg/m²/a from pre-industrial to present, which overall represents a 6-fold increase in Hg concentration and accumulation. At the Nyasanga/Kahama delta region, pre-industrial Hg concentrations are 20 ± 3 ng/g, increasing to 46 ng/g in surface sediment. Mercury accumulation rate has increased from 30 to 70 μg/m²/a at this site, representing a 2–3-fold increase in Hg concentration and accumulation. There is a lack of correlation between charcoal abundance and Hg accumulation rate in the sediment cores, demonstrating that local biomass burning has little relationship with the observed Hg concentration or Hg accumulation rates. Examined using a sediment focusing-corrected mass accumulation rate approach, the cores have similar anthropogenic atmospheric Hg deposition profiles, suggesting that after accounting for background sediment concentrations the source of accumulating Hg is predominantly atmospheric in origin. In summary, the data document an increase of Hg flux to the Lake Tanganyika ecosystem that is consistent with increasing watershed sediment delivery with background-level Hg contamination, and regional as well as global increases in atmospheric Hg deposition.     

Interaction between zinc and freshwater and marine diatom species: Surface complexation and Zn isotope fractionation

This work is devoted to characterization of zinc interaction in aqueous solution with two marine planktonic (Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species (Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption and electrophoretic measurements with surface complexation modeling and by assessing Zn isotopes fractionation during both long term uptake and short term adsorption on diatom cells and their frustules. Reversible adsorption experiments were performed at 25 and 5 °C as a function of exposure time (5 min to 140 h), pH (2 to 10), zinc concentration in solution (10 nM to 1 mM), ionic strength (I = 0.001 to 1.0 M) and the presence of light. While the shape of pH-dependent adsorption edge is almost the same for all four species, the constant-pH adsorption isotherm and maximal Zn binding capacities differ by an order of magnitude. The extent of adsorption increases with temperature from 5 to 25 °C and does not depend on light intensity. Zinc adsorption decreases with increase of ionic strength suggesting competition with sodium for surface sites. Cell number-normalized concentrations of sorbed zinc on whole cells and their silica frustules demonstrated only weak contribution of the latter (10-20%) to overall zinc binding by diatom cell wall. Measurements of electrophoretic mobilities (μ) revealed negative diatoms surface potential in the full range of zinc concentrations investigated (0.15-760 μmol/L), however, the absolute value of μ decreases at [Zn] > 15 μmol/L suggesting a change in surface speciation. These observations allowed us to construct a surface complexation model for Zn binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Zn complexation with carboxylate and silanol groups. Thermodynamic and structural parameters of this model are based on previous acid-base titration and spectroscopic results and allow quantitative reproduction of all adsorption experiments. Although Zn adsorption constants on carboxylate groups are almost the same, Zn surface adsorption capacities are very different among diatom species which is related to the systematic differences in their cell wall composition and thickness. Measurements of Zn isotopic composition (⁶⁶Zn/(⁶⁴Zn)) performed using a multicollector ICP MS demonstrated that irreversible incorporation of Zn in cultured diatom cells produces enrichment in heavy isotope compared to growth media (Δ⁶⁶Zn(solid-solution) = 0.27 ± 0.05, 0.08 ± 0.05, 0.21 ± 0.05, and 0.19 ± 0.05‰ for TW, SC, NMIN, and AMIN species, respectively). Accordingly, an enrichment of cells in heavy isotopes (Δ⁶⁶Zn(solid-solution) = 0.43 ± 0.1 and 0.27 ± 0.1‰ for NMIN and AMIN, respectively) is observed following short-term Zn sorption on freshwater cells in nutrient media at pH ∼ 7.8. Finally, diatoms frustules are enriched in heavy isotopes compared to solution during Zn adsorption on silica shells at pH ∼ 5.5 (Δ⁶⁶Zn(solid-solution) = 0.35 ± 0.10‰). Measured isotopes fractionation can be related to the structure and stability of Zn complexes formed and they provide a firm basis for using Zn isotopes for biogeochemical tracing.     

Mercury emission from terrestrial background surfaces in the eastern USA. II: Air/surface exchange of mercury within forests from South Carolina to New England

Mercury air/surface exchange was measured over litter-covered soils with low Hg concentrations within various types of forests along the eastern seaboard of the USA. The fieldwork was conducted at six forested sites in state parks in South Carolina, North Carolina, New Jersey, Pennsylvania, New York and Maine from mid-May to early June 2005. The study showed that the Hg air/surface exchange was consistently very low and similar (overall daytime mean flux = 0.2 ± 0.9 ng m⁻² h⁻¹, n = 310, for all six sites monitored) with the various forest types. These flux values are comparable with those found in a year-long study in Tennessee (yearly daytime mean = 0.4 ± 0.5 ng m⁻² h⁻¹), but lower than many previous flux results reported for background soils. The Hg fluxes at all sites oscillated around zero, with many episodes of deposition (negative fluxes) occurring in both daytime and nighttime. While there were particular days showing significant correlations among the Hg air/surface exchange and certain environmental parameters, perhaps because of the low fluxes encountered, few significant correlations were found for any particular day of sampling between the Hg flux and environmental parameters such as solar radiation, soil temperature, air temperature (little variability seen), relative humidity, and ambient air Hg concentrations. Factors driving the Hg exchange as previously found for enriched soils may not hold for these background litter-covered forest soils. The results suggest that spatial variations of the Hg air/surface exchange were small among these different forest types for this particular time of year.     

Evidence for the nucleation and epitaxial growth of Zn phyllosilicate on montmorillonite

Zinc uptake in suspensions (?3.7 g L⁻¹) of MX80 montmorillonite was investigated at pH 4.0 and 7.3, a total Zn concentration ([Zn]_total) of 500 μM, and dissolved Si concentrations ([Si]_aq) of ∼70 and ∼500 μM in 0.5 M NaCl, by kinetics experiments and polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Differential thermogravimetric analysis verified the cis-vacant character of the montmorillonite. No Zn uptake occurred at pH 4.0, confirming that cation exchange was hampered by the high ionic strength of the suspension. At pH 7.3 and low [Si]_aq (∼70 μM), Zn uptake occurred rapidly during the first hour of reaction, and then leveled off to 50 μmol/g montmorillonite at 168 h. The uptake rate is consistent with Zn sorption on pH-dependent edge sites. At pH 7.3 and high [Si]_aq (∼500 μM), the initial sorption rate was similar, but Zn sorption continued, reaching 130 μmol/g at 168 h, and was paralleled by Si uptake with a Si/Zn uptake ratio of 1.51(10), suggesting formation of a Zn (hydrous) silicate. P-EXAFS data indicated that the first oxygen coordination shell of sorbed Zn is split into two subshells at 1.97(2) and 2.08(3)-2.12(2) Å for all EXAFS samples. These two distances are assigned to a mixture of tetrahedral (^IVZn) and octahedral (^VIZn) Zn complexes. The proportion of ^IVZn was lower in the high [Si]_aq samples and decreased with reaction time. Al low [Si]_aq and 216 h of reaction, nearest cationic shells of 0.6(4) Al in the film plane and 0.5(4) Si out of the film plane were detected at 3.00(2) and 3.21(2) Å, respectively, and were interpreted as the formation of ^IVZn and ^VIZn mononuclear complexes at the edges of montmorillonite platelets, in structural continuity to the (Al, Mg) octahedral sheets. At high [Si]_aq, in-plane Zn and Al and out-of-plane Si neighbors were detected at 4 h, indicating the formation of Zn phyllosilicate nuclei at the layer edges. At 313 h, Zn-Al pairs were no longer detected, and Zn atoms were surrounded on average by 3.4(5) in-plane Zn at 3.10(1) Å and 1.7(9) out-of-plane Si at 3.30(2) Å, supporting the precipitation of a Zn phyllosilicate. Thus, dioctahedral Al phyllosilicate may act as a nucleating surface for the heterogeneous formation of trioctahedral Zn phyllosilicate at [Si]_aq relevant to natural systems.     

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.     

50-year record and solid state speciation of mercury in natural and contaminated reservoir sediment

Contaminated fluvial sediments represent both temporary sinks for river-borne pollutants and potential sources in case of natural and/or anthropogenic resuspension. Reservoir lakes play a very important role in sediment dynamics of watersheds and may offer great opportunities to study historical records of river-borne particles and associated elements transported in the past. The fate and potential environmental impact of Hg depends on its abundance, its carrier phases and its chemical speciation. Historical Hg records and solid state Hg speciation were compared in sediments from two contrasting reservoirs of the Lot River (France) upstream and downstream from a major polymetallic pollution (e.g. Cd, Zn) source. Natural (geochemical background) and anthropogenic Hg concentrations and their relationships with predominant carrier phases were determined. The results reveal important historical Hg contamination (up to 35 mg kg⁻¹) of the downstream sediment, reflecting the historical evolution of industrial activity at the point source, i.e. former coal mining, Zn ore treatment and post-industrial remediation work. Single chemical extractions (ascorbate, H₂O₂, KOH) suggest that at both sites most (∼75%) of the Hg is bound to organic and/or reactive sulphide phases. Organo-chelated (KOH-extracted) Hg, representing an important fraction in the uncontaminated sediment, shows similar concentrations (∼0.02 mg kg⁻¹) at both sites and may be mainly attributed to natural inputs and/or processes. Although, total Hg concentrations in recent surface sediments at both sites are still very different, similar mono-methylmercury concentrations (up to 4 μg kg⁻¹) and vertical distributions were observed, suggesting comparable methylation-demethylation processes. High mono-methylmercury concentrations (4–15 μg kg⁻¹) in 10–40 a-old, sulphide-rich, contaminated sediment suggest long-term persistence of mono-methylmercury. Beyond historical records of total concentrations, the studied reservoir sediments provided new insights in solid state speciation and carrier phases of natural and anthropogenic Hg. In case of sediment resuspension, the major part of the Hg historically stored in the Lot River sediments will be accessible to biogeochemical recycling in the downstream fluvial-estuarine environment.     

Methylmercury cycling in sediments on the continental shelf of southern New England

Exposure of humans to monomethylmercury (MMHg) occurs primarily through consumption of marine fish, yet there is limited understanding concerning the bioaccumulation and biogeochemistry of MMHg in the biologically productive coastal ocean. We examined the cycling of MMHg in sediments at three locations on the continental shelf of southern New England in September 2003. MMHg in surface sediments is related positively to inorganic Hg (Hg(II) = total Hg − MMHg), the geographical distribution of which is influenced by organic material. Organic matter also largely controls the sediment-water partitioning of Hg species and governs the availability of dissolved Hg(II) for methylation. Potential gross rates of MMHg production, assayed by experimental addition of ²⁰⁰Hg to intact sediment cores, are correlated inversely with the distribution coefficient (K_D) of Hg(II) and positively with the concentration of Hg(II), most probably as HgS⁰, in 0.2-μm filtered pore water of these low-sulfide deposits. Moreover, the efflux of dissolved MMHg to overlying water (i.e., net production at steady state) is correlated with the gross potential rate of MMHg production in surface sediments. These results suggest that the production and efflux of MMHg from coastal marine sediments is limited by Hg(II), loadings of which presumably are principally from atmospheric deposition to this region of the continental shelf. The estimated diffusive flux of MMHg from the shelf sediments averages 9 pmol m⁻² d⁻¹. This flux is comparable to that required to sustain the current rate of MMHg accumulation by marine fish, and may be enhanced by the efflux of MMHg from near-shore deposits contaminated more substantially with anthropogenic Hg. Hence, production and subsequent mobilization of MMHg from sediments in the coastal zone may be a major source of MMHg to the ocean and marine biota, including fishes consumed by humans.     

Genesis of the Zinkgruvan stratiform Zn-Pb-Ag deposit and associated dolomite-hosted Cu ore,Bergslagen, Sweden

Zinkgruvan, a major stratiform Zn-Pb-Ag deposit in the Paleoproterozoic Bergslagen region, south-central Sweden, was overprinted by polyphase ductile deformation and high-grade metamorphism (including partial melting of the host succession) during the 1.9–1.8 Ga Svecokarelian orogeny. This complex history of post-ore modification has made classification of the deposit difficult. General consensus exists on a syngenetic-exhalative origin, yet the deposit has been variably classified as a volcanogenic massive sulfide (VMS) deposit, a sediment-hosted Zn (SEDEX) deposit, and a Broken Hill-type (BHT) deposit. Since 2010, stratabound, cobaltiferous and nickeliferous Cu ore, comprising schlieren and impregnations of Cu, Co and Ni sulfide minerals in dolomitic marble, is mined from the stratigraphic footwall to the stratiform Zn-Pb-Ag ore. This ore type has not been fully integrated into any of the existing genetic models. Based on a combination of 1) widespread hematite-staining and oxidizing conditions (Fe₂O₃ > FeO) in the stratigraphic footwall, 2) presence of graphite and reducing conditions (Fe₂O₃ < FeO) in the ore horizon and hangingwall and 3) intense K-feldspar alteration and lack of feldspar-destructive alteration in the stratigraphic footwall, we suggest that both the stratiform Zn-Pb-Ag and the dolomite-hosted Cu ore can be attributed to the ascent and discharge of an oxidized, saline brine at near neutral pH. Interaction of this brine with organic matter below the seafloor, especially within limestone, formed stratabound, disseminated Cu ore, and exhalation of the brine into a reduced environment on the sea floor produced a brine pool from which the regionally extensive (>5 km) Zn-Pb-Ag ore was precipitated.Both ore types are characterized by significant spread in δ³⁴S, with the sulfur in the Cu ore and associate marble-hosted Zn mineralization on average being somewhat heavier (δ³⁴S = −4.7 to +10.5‰, average 3.9‰) than that in the stratiform Zn-Pb-Ag ore (δ³⁴S = −6 to +17‰, average 2.0‰). The ranges in δ³⁴S are significantly larger than those observed in syn-volcanic massive sulfide deposits in Bergslagen, for which simple magmatic/volcanic sulfur sources have been invoked. Mixing of magmatic-volcanic sulfur leached from underlying volcanic rocks and sulfur sourced from abiotic or bacterial sulfate reduction in a mixing zone at the seafloor could explain the range observed at Zinkgruvan.A distinct discontinuity in the stratigraphy, at which key stratigraphic units stop abruptly, is interpreted as a syn-sedimentary fault. Metal zonation in the stratiform ore (decreasing Zn/Pb from distal to proximal) and the spatial distribution of Cu mineralization in underlying dolomitic marble suggest that this fault was a major feeder to the mineralization. Our interpretation of ore-forming fluid composition and a dominant redox trap rather than a pH and/or temperature trap differs from most VMS models, with Selwyn-type SEDEX models, and most BHT models. Zinkgruvan has similarities to both McArthur-type SEDEX deposits and sediment-hosted Cu deposits in terms of the inferred ore fluid chemistry, yet the basinal setting has more similarities to BHT and felsic-bimodal VMS districts. We speculate that besides an oxidized footwall stratigraphy, regionally extensive banded iron formations and limestone horizons in the Bergslagen stratigraphy may have aided in buffering ore-forming brines to oxidized, near-neutral conditions. In terms of fluid chemistry, Zinkgruvan could comprise one of the oldest known manifestations of Zn and Cu ore-forming systems involving oxidized near-neutral brines following oxygenation of the Earth’s atmosphere.     

Major, trace element and oxygen isotope study of glass cosmic spherules of chondritic composition: The record of their source material and atmospheric entry heating

New geochemical data on cosmic spherules (187 major element, 76 trace element, and 10 oxygen isotope compositions) and 273 analyses from the literature were used to assess the chemical diversity observed among glass cosmic spherules with chondritic composition. Three chemical groups of glass spherules are identified: normal chondritic spherules, CAT-like spherules (where CAT refers to Ca-Al-Ti-rich spherules), and high Ca-Al spherules. The transition from normal to high Ca-Al spherules occurs through a progressive enrichment in refractory major elements (on average from 2.3 wt.% to 7.0 wt.% for CaO, 2.8 wt.% to 7.2 wt.% for Al₂O₃, and 0.14 wt.% to 0.31 wt.% for TiO₂) and refractory trace elements (from 6.2 μg/g to 19.3 μg/g for Zr and 1.6CI-4.3CI for Rare Earth Elements-REEs) relative to moderately refractory elements (Mg, Si) and volatile elements (Rb, Na, Zn, Pb). Based on a comparison with experimental works from the literature, these chemical groups are thought to record progressive heating and evaporation during atmospheric entry. The evaporative mass losses evaluated for the high Ca-Al group (80-90%) supersede those of the CAT spherules which up to now have been considered as the most heated class of stony cosmic spherules. However, glass cosmic spherules still retain isotopic and elemental evidence of their source and precursor mineralogy. Four out of the 10 normal and high Ca-Al spherules analysed for oxygen isotopes are related to ordinary chondrites (δ¹⁸O = 13.2-17.3‰ and δ¹⁷O = 7.6-9.2‰). They are systematically enriched in Ni and Co (Ni = 24-500 μg/g) with respect to spherules related to carbonaceous chondrites (Ni < 1.2 μg/g, δ¹⁸O = 13.1-28.0‰ and δ¹⁷O = 5.1-14.0‰). REE abundances in cosmic spherules, which are not fractionated according to parent body or atmospheric entry heating, can then be used to unravel the precursor mineralogy. Spherules with flat REE pattern close to unity when normalized to CI are the most abundant in our dataset (54%) and likely derive from homogeneous, fine-grained chondritic precursors. Other REE patterns fall into no more than five categories, a surprising reproducibility in view of the mineralogical heterogeneity of chondritic lithologies at the micrometeorite scale.     

Distribution of Cu,Co, As,and Fe in mine waste,sediment, soil,and water in and around mineral deposits and mines of the Idaho Cobalt Belt,USA

The distribution of Cu, Co, As and Fe was studied downstream from mines and deposits in the Idaho Cobalt Belt (ICB), the largest Co resource in the USA. To evaluate potential contamination in ecosystems in the ICB, mine waste, stream sediment, soil, and water were collected and analyzed for Cu, Co, As and Fe in this area. Concentrations of Cu in mine waste and stream sediment collected proximal to mines in the ICB ranged from 390 to 19,000 μg/g, exceeding the USEPA target clean-up level and the probable effect concentration (PEC) for Cu of 149 μg/g in sediment; PEC is the concentration above which harmful effects are likely in sediment dwelling organisms. In addition concentrations of Cu in mine runoff and stream water collected proximal to mines were highly elevated in the ICB and exceeded the USEPA chronic criterion for aquatic organisms of 6.3 μg/L (at a water hardness of 50 mg/L) and an LC50 concentration for rainbow trout of 14 μg/L for Cu in water. Concentrations of Co in mine waste and stream sediment collected proximal to mines varied from 14 to 7400 μg/g and were highly elevated above regional background concentrations, and generally exceeded the USEPA target clean-up level of 80 μg/g for Co in sediment. Concentrations of Co in water were as high as in 75,000 μg/L in the ICB, exceeding an LC50 of 346 μg/L for rainbow trout for Co in water by as much as two orders of magnitude, likely indicating an adverse effect on trout. Mine waste and stream sediment collected in the ICB also contained highly elevated As concentrations that varied from 26 to 17,000 μg/g, most of which exceeded the PEC of 33 μg/g and the USEPA target clean-up level of 35 μg/g for As in sediment. Conversely, most water samples had As concentrations that were below the 150 μg/L chronic criterion for protection of aquatic organisms and the USEPA target clean-up level of 14 μg/L. There is abundant Fe oxide in streams in the ICB and several samples of mine runoff and stream water exceeded the chronic criterion for protection of aquatic organisms of 1000 μg/L for Fe. There has been extensive remediation of mined areas in the ICB, but because some mine waste remaining in the area contains highly elevated Cu, Co, As and Fe, inhalation or ingestion of mine waste particulates may lead to human exposure to these elements.