Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ⁶⁵Cu, δ⁶⁶Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g⁻¹ Cu and 2084 μg g⁻¹ Zn in the organic horizons. The δ⁶⁵Cu values varied little (−0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ⁶⁶Zn_IRMM values were isotopically lighter in ash (−0.41‰) and organic horizons (−0.85‰ to −0.47‰) than in bedrock (−0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ⁶⁶Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ⁶⁶Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ⁶⁶Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.     

Geochronological and isotopic records of crustal storage and assimilation in the Wolverine Creek–Conant Creek system,Heise eruptive centre,Snake River Plain

Understanding the processes of differentiation of the Yellowstone–Snake River Plain (YSRP) rhyolites is typically impeded by the apparent lack of erupted intermediate compositions as well as the complex nature of their shallow interaction with the surrounding crust responsible for their typically low O isotopic ratios. A pair of normal-δ¹⁸O rhyolitic eruptions from the Heise eruptive centre in eastern Idaho, the Wolverine Creek Tuff and the Conant Creek Tuff, represent unique magmatic products of the Yellowstone hotspot preserving abundant vestiges of the intermediate differentiation steps leading to rhyolite generation. We address both shallow and deep processes of magma generation and storage in the two units by combining high-precision ID–TIMS U–Pb zircon geochronology, trace element, O and Hf isotopic studies of zircon, and Sr isotopic analyses of individual high-Mg# pyroxenes inherited from lower- to mid-crustal differentiation stages. The zircon geochronology confirms the derivation of both tuffs from the same rhyolitic magma reservoir erupted at 5.5941 ± 0.0097 Ma, preceded by at least 92 ± 14 ky of continuous or intermittent zircon saturation approximating the length of pre-eruptive magma accumulation in the upper crust. Some low-Mg# pyroxenes enclosing zircons predate the eruption by at least 45 ± 27 ky, illustrating the co-crystallisation of major and accessory phases in the near-liquidus rhyolitic melts of the YSRP over a significant period of time. Coeval zircon crystals are isotopically heterogeneous (two populations at εHf ~?5 and ?13), requiring the assembly of isotopically distinct melt pockets directly prior to, or during, the eruption. The primitive Mg# 60–90 pyroxenes are out of isotopic equilibrium with the host rhyolitic melt (⁸⁷Sr/⁸⁶Sr_i = 0.70889), covering a range of ⁸⁷Sr/⁸⁶Sr_i = 0.70705–0.70883 corresponding to ratios typical of the most radiogenic YSRP basalts to the least radiogenic YSRP rhyolites. Together with the low εHf in zircon, the Sr isotopic ratios illustrate limited assimilation dominated by radiogenic Archean crustal source materials incorporated into variably evolved YSRP melts as they progress towards rhyolitic compositions by assimilation–fractional crystallisation.     

High-frequency climatic oscillations during the last deglaciation as revealed by oxygen-isotope records of benthic organisms (Ammersee,southern Germany)

High-resolution oxygen-isotope records of benthic ostracods and molluscs from Ammersee, southern Germany, show high-frequency climatic changes during the last deglaciation and parallel in great detail published faunal and floral variations reconstructed from Norwegian Sea sediments and isotope variations in Greenland ice cores. The marine and the terrestrial records give evidence of a synchronous late glacial climatic development in Greenland, NW- and Mid-Europe. However,¹⁴C-ages of the supraregional climatic events and of two tephra layers in the marine sediments of the northeastern Atlantic Ocean are significantly older than the¹⁴C-ages of the corresponding horizons on land. These differences strongly suggest that major short-term events have affected the exchangeable carbon on earth during the dramatic environmental changes related to the deglaciation and in particular have affected the CO₂-distribution within the ocean and between ocean and atmosphere. Dating methods independent of climatic variations and of the global carbon budget should be given priority to refine the timescales of the marine and atmospheric processes during the last deglaciation.This is the fourth paper in a series of papers published in this issue on high-resolution paleolimnology. These papers were presented at the Sixth International Palaeolimnology Symposium held 19–21 April, 1993 at the Australian National University, Canberra, Australia. Dr. A. F. Lotter and Dr. M. Sturm served as guest editors for these papers.     

Polar Low genesis over the North Pacific under different global warming scenarios

Following an earlier climatological study of North Pacific Polar Lows by employing dynamical downscaling of NCEP1 reanalysis in the regional climate model COSMO-CLM, the characteristics of Polar Low genesis over the North Pacific under different global warming scenarios are investigated. Simulations based on three scenarios from the Special Report on Emissions Scenarios were conducted using a global climate model (ECHAM5) and used to examine systematic changes in the occurrence of Polar Lows over the twenty first century. The results show that with more greenhouse gas emissions, global air temperature would rise, and the frequency of Polar Lows would decrease. With sea ice melting, the distribution of Polar Low genesis shows a northward shift. In the scenarios with stronger warming there is a larger reduction in the number of Polar Lows.     

Spatiotemporal variability in hydrochemistry of shallow groundwater in a small pre‐alpine catchment: The importance of landscape elements

Topography and landscape characteristics affect the storage and release of water and, thus, groundwater dynamics and chemistry. Quantification of catchment scale variability in groundwater chemistry and groundwater dynamics may therefore help to delineate different groundwater types and improve our understanding of which parts of the catchment contribute to streamflow. We sampled shallow groundwater from 34 to 47 wells and streamflow at seven locations in a 20‐ha steep mountainous catchment in the Swiss pre‐Alps, during nine baseflow snapshot campaigns. The spatial variability in electrical conductivity, stable water isotopic composition, and major and trace ion concentrations was large and for almost all parameters larger than the temporal variability. Concentrations of copper, zinc, and lead were highest at sites that were relatively dry, whereas concentrations of manganese and iron were highest at sites that had persistent shallow groundwater levels. The major cation and anion concentrations were only weakly correlated to individual topographic or hydrodynamic characteristics. However, we could distinguish four shallow groundwater types based on differences from the catchment average concentrations: riparian zone‐like groundwater, hillslopes and areas with small upslope contributing areas, deeper groundwater, and sites characterized by high magnesium and sulfate concentrations that likely reflect different bedrock material. Baseflow was not an equal mixture of the different groundwater types. For the majority of the campaigns, baseflow chemistry most strongly resembled riparian‐like groundwater for all but one subcatchment. However, the similarity to the hillslope‐type groundwater was larger shortly after snowmelt, reflecting differences in hydrologic connectivity. We expect that similar groundwater types can be found in other catchments with steep hillslopes and wet areas with shallow groundwater levels and recommend sampling of groundwater from all landscape elements to understand groundwater chemistry and groundwater contributions to streamflow.     

An experimental study of Fe–Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

The behavior of nickel in the Earth’s mantle is controlled by sulfide melt–olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe–Ni composition of molten sulfide in the Earth’s upper mantle via sulfide melt–olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt \(X_{{{\text{Ni}}}}^{{{\text{Sulfide}}}}=\frac{{{\text{Ni}}}}{{{\text{Ni}}+{\text{Fe}}}}\) (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of \({f_{{{\text{O}}_{\text{2}}}}}\) on Fe–Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31–46, 1995), “zero time” experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0?±?1.0 log units more reduced than the fayalite–magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ ??1 or more oxidized (suite 4). For the reduced (suites 1–3) experiments, Fe–Ni distribution coefficients \(K_{{\text{D}}}^{{}}=\frac{{(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}/X_{{{\text{Fe}}}}^{{{\text{sulfide}}}})}}{{(X_{{{\text{Ni}}}}^{{{\text{olivine}}}}/X_{{{\text{Fe}}}}^{{{\text{olivine}}}})}}\) are small, averaging 10.0?±?5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K_D (21.1–25.2). Compared to previous determinations at 100 kPa, values of K_D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.4–0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6–0.7) at depths near 80–120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.28)?>?140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.