Groundwater geochemistry evolution and geogenic contaminants in the Sulaimani-Warmawa Sub-basin, Sulaimani, Kurdistan Region, Iraq.

Evolution of groundwater geochemistry in the Sulaimani-Warmawa Sub-basin in the Kurdistan Region of Iraq has been investigated using hydrogeochemical and isotopic methods. This is a semiarid region with seasonal precipitation in winter. Water chemistry generally evolves from Ca-HCO3 groundwater type close to the basin boundaries towards Ca-Mg-HCO3 groundwater type close to the Tanjero River along the axis of the basin. Some samples have increased concentrations of Na, Cl, and SO4 as a consequence of dissolution of halite and gypsum embedded in carbonates. Values of pH are slightly alkaline or alkaline, and redox parameters indicate a moderately reducing environment. Isotopes δ2H and δ18O indicate recharge from winter precipitation with no evaporation. Values of dissolved 13C(DIC) correspond to equilibrium with carbonates and C4 plants as the source of CO2. Values of 87Sr/86Sr in groundwater are in a good agreement with carbonate dissolution as a principal process. The principal geogenic contaminant is Ba with concentrations up to 0.383 mg/L. Dissolved concentrations of other geogenic contaminants such as As, F, Mn, and Cr are low or below the detection limit as expected based on their low contents in carbonate rocks. Inverse geochemical modeling on selected profiles calibrated using δ13C values provided mass transfer coefficients for possible geochemical reactions. Future work should focus on interactions in the hyporheic zone of the Tanjero River.

Rapid determination of carbon isotope composition in carbonatites using isotope ratio mass spectrometry - Comparison of dual-inlet, elemental-analyzer and continuous-flow techniques.

RATIONALE: Applications where stable C and O isotope compositions are useful require routine instrumental techniques with a fast sample throughput which should also produce accurate and precise results. We present a comparison of three different instrumental isotope ratio mass spectrometry (IRMS) approaches (Dual Inlet - DI; Elemental Analyzer - EA; Continuous Flow - CF) to determine the stable isotope composition of carbon in carbonate matrices, with a focus on evaluating the optimum approach for less complex instrumental techniques. METHODS: The DI-IRMS method is taken as an absolute method for obtaining accurate and precise 13 C/12 C ratios with internal errors usually < ±0.01‰ (2SD) and long-term reproducibility better than ±0.03‰ (2SD). The drawbacks of DI-IRMS are that it requires extensive offline sample preparation, rather large sample sizes (commonly >20 mg) and extended analysis times. RESULTS: EA-IRMS provides rapidity of analysis, relatively non-complex technique optimization and large sample throughput sufficient to distinguish natural trends although the larger internal errors and poorer reproducibility must be considered. The major disadvantage of EA-IRMS lies in a constant offset of the 13 C/12 C ratios against DI-IRMS, large internal errors (±0.2‰, 2SD) and the worst reproducibility (±0.3‰, 2SD) of all the explored methods. The results acquired using CF-IRMS are comparable with those obtained by employing DI-IRMS with an external reproducibility better than ±0.2‰ (2SD). Compared with EA-IRMS, however, this technique requires more elaborate sample preparation - more akin to DI-IRMS. None of these two latter techniques can provide C isotope results for coexisting phases such as calcite, dolomite and ankerite unless they are physically separated and analyzed independently. CONCLUSIONS: All methods are appropriate for 13 C/12 C determinations with CF-IRMS and EA-IRMS less applicable to high-precision measurements but relevant for studies requiring high sample throughput. Periodical analysis of matrix-matched reference materials during the analytical sequence is warranted for both EA-IRMS and CF-IRMS.

Silver isotopes: A tool to trace smelter-derived contamination.

Here, for the first time, we report the concentrations and isotopic data of Ag in a variety of ore and metallurgical samples and forest soils that have been polluted due to Ag-Pb smelter emissions. Similar to the Ag concentrations, we identified a large range of δ109Ag values (from -0.8 to +2.4‰), a ∼3‰ spread, within the primary and secondary materials (i.e., galena, fly ash, slag and matte). This phenomenon, however, is evidently unrelated to Ag isotopic fractionation during the smelting process, but it reflects the starting 109Ag/107Ag signal in ore mineral and/or the specific type of ore genesis. The two studied soil profiles differed in Ag isotopic composition, but on the other hand, they consistently showed significantly lighter Ag (≤+0.8‰) of metallurgical origin in the upper horizons compared to the bottom horizons and bedrocks, with low Ag amounts depleted of 107Ag (≤+2.9‰). This isotopic pattern can be attributed to a ternary mixing relationship involving two major anthropogenic Ag components and a minor contribution from geogenic Ag. Accordingly, we did not observe any post-depositional isotopic fractionation in our soils, since Ag was geochemically stable and it was not subjected to leaching. In summary, the Ag isotopes have a potential to trace variations in anthropogenic phases, to monitor specific geochemical processes, and are clearly applicable as anthropogenic Ag source and Ag load proxies.

Increasing water-use efficiency mediates effects of atmospheric carbon, sulfur, and nitrogen on growth variability of central European conifers.

Climate controls forest biomass production through direct effects on cambial activity and indirectly through interactions with CO2, air pollution, and nutrient availability. The atmospheric concentration of CO2, sulfur and nitrogen deposition can also exert a significant indirect control on wood formation since these factors influence the stomatal regulation of transpiration and carbon uptake, that is, intrinsic water use efficiency (iWUE). Here we provide 120-year long tree-ring time series of iWUE, stem growth, climatic and combined sulfur and nitrogen (SN) deposition trends for two common tree species, Pinus sylvestris (PISY) and Picea abies (PCAB), at their lower and upper distribution margins in Central Europe. The main goals were to explain iWUE trends using theoretical scenarios including climatic and SN deposition data, and to assess the contribution of climate and iWUE to the observed growth trends. Our results showed that after a notable increase in iWUE between the 1950s and 1980s, this positive trend subsequently slowed down. The substantial rise of iWUE since the 1950s resulted from a combination of an accelerated increase in atmospheric CO2 concentrations (Ca) and a stable level of leaf intercellular CO2 (Ci). The offset of observed iWUE values above the trajectory of a constant Ci/Ca scenario was explained by trends in SN deposition (all sites) together with the variation of drought conditions (low-elevation sites only). Increasing iWUE over the 20th and 21st centuries improved tree growth at low-elevation drought-sensitive sites. In contrast, at high-elevation PCAB sites, growth was mainly stimulated by recent warming. We propose that SN pollution should be considered in order to explain the steep increase in iWUE of conifers in the 20th century throughout Central Europe and other regions with a significant SN deposition history.