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.

Thermal stability of arsenic complexes in soils.

The release of soil arsenic (As) in an unsaturated zone under oxidative conditions and at two temperatures simulating the seasonal effect (15 °C and 23 °C) was studied in four cultivated soils from the Elbe River catchment (Czech Republic, Central Europe). The soils with a low geogenic As background contained from 10 to 50 µg.g-1 of As, mostly originating from atmospheric deposition in the past. The temperature effect on the stability of As in soils was studied in connection with the stability of hydrated iron (Fe) oxides and dissolved organic carbon (DOC), as essential binding partners of As in soils. The temperature impact on As release was related to the actual As binding in soil determined by the sequential leaching. With predominant As binding to amorphous and poorly crystalline Fe phases the higher temperature (23 °C) increased As release up to twice compare to 15 °C. In the soils with a low total Fe and the preferential As binding to well-crystallised Fe phases the temperature effect on As release was negligible. Unlike Fe, the release of DOC is strongly temperature dependent, therefore As mobilisation was controlled by the DOC concentration. A higher experimental temperature (23 °C) supported the formation of DOC and the consequent release of As and Fe into the soil solution.

Environmental interaction of antimony and arsenic near busy traffic nodes.

Antimony (Sb) and arsenic (As) are elements with similar chemistry, toxicity and binding properties, but different environmental risks and prevailing anthropogenic sources. A significant source of Sb contamination is associated with braking in extremely loaded traffic areas, where the produced abrasion dust contains up to 5% wt. of Sb2S3. In these same exposure areas, As still originates mostly from the combustion of fossil fuels. Heavily loaded crossroads from three different regions of the Czech Republic (Central Europe) were monitored for Sb content in road dusts, topsoils and reference soils during a two-year season (2016-2017). The same samples were also tested for As content to evaluate current contamination trends of both elements in exposed urban areas. The concentration of Sb varied from 5 to 70 µg g-1 in topsoils, and from 20 to 350 µg g-1 in road dusts with the preference for binding to the fine particle fraction (<0.1 mm). The average Sb concentration was up to 60 times the background value and decreased in the order: brake abrasion (103 µg g-1) > road dust (102 µg g-1)> topsoils (101 µg g-1) >> reference soils (<1 µg g-1). The concentration of As in road dust, topsoils and reference soils had about the same level, 101 µg g-1 indicating a more regional character of As pollution. Correlation factors for Sb/As versus iron (Fe)/organic matter (OM) indicated a more robust correlations in soils compared to road dusts and generally better correlations of Sb compared to As. While arsenic contamination has recently decreased thanks to a massive decline of arsenic emissions, antimony contamination indicates a dangerous trend due to growing automotive traffic.

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.

Retraction Statement: Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution.

"Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution" https://doi.org/10.1111/gcb.14505, by Martin Novak, Melanie A. Vile, Jan Curik, Bohuslava Cejkova, Jiri Barta, Marketa Stepanova, Ivana Jackova, Frantisek Buzek, Leona Bohdalkova, Eva Prechova, Frantisek Veselovsky, Marie Adamova, Ivana Valkova and Arnost Komarek. The above article, first published online in Wiley Online Library (wileyonlinelibrary.com) in Global Change Biology, has been retracted by agreement between the authors, the journal Editor-in-Chief, Stephen P. Long, and John Wiley & Sons Ltd. Since publication of the above article, it was brought to the attention of the authors that the peat accretion rates violate reasonable ranges of peatland C/N/P stoichiometry, placing the quantitative conclusions of the article in serious error. The authors apologize for any inconvenience the publication of this work may have caused our readers. REFERENCE Novak, M., Vile, M. A., Cejkova, B., Barta, J., Stepanova, M., Jackova, I., Buzek, F., Bohdalkova, L., Prechova, E., Veselovsky, F., Adamova, M., Valkova, I., & Komarek, A. (2018). Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution. Global Change Biology.. https://doi.org/10.1111/gcb.14505.