Sulfur Isotopic Composition of H2S and SO4 2− from Mineral Springs in the Polish Carpathians

Abstract

A number of springs in Carpathian Mts. contain dissolved H₂S and SO₄ ^2- in concentrations above 10 mg/dm³. In this study we have investigated the sulfur isotope composition (δ³⁴S) of the dissolved sulfur species in the springs from the flysch area in the Carpathian Mts. along the tectonic dislocation. It is believed that some of these springs may carry a major fraction of dissolved sulfur species of extremely deep sulfur (of mantle origin), which is subjected to SO₄ ^2-—H₂S isotope exchange at high temperatures. The original isotopic compositions may be modified by reduction/oxidation at low temperatures and by admixture of sulfur from other sources.

In order to distinguish the sulfur of mantle origin we investigated δ³⁴S of dissolved sulfide and sulfate and on the basis of known concentrations we calculated δ³⁴S of total dissolved sulfur. The isotope fractionation between sulfate and sulfide helped to distinguish the sulfur origin. Evaluating the sulfur isotope exchange, we selected 4 springs which likely have only weakly disturbed sulfur of mantle origin.     

A Modified Technique for the Preparation of SO2 from Sulphates and Sulphides for Sulphur Isotope Analyses

Abstract

A modified technique for the conversion of sulphates and sulphides to SO₂ with the mixture of V₂O₅—SiO₂ for sulphur isotopic analyses is described. This technique is more suitable for routine analysis of large number of samples. Modification of the reaction vessel and using manifold inlet system allows to analyse up to 24 samples every day. The modified technique assures the complete yield of SO₂, consistent oxygen isotope composition of the SO₂ gas and reproducibility of δ³⁴S measurements being within 0.10‰. It is observed, however, oxygen in SO₂ produced from sulphides differs in δ¹⁸O with respect to that produced from sulphates.     

Sulphur and oxygen isotopic composition of sulphates in springs feeding the Wieprz river and other springs of Lublin Upland and Roztocze

Springs on Roztocze and Lublin Upland have been studied. Isotopic data are compared with data of chemical analyses. The results of studies allow us to distinguish five types of groundwaters. The differentiation is based upon different lithology; opokas, gaizes, sandy-silty-clay deposits, sands with shell sandstones, marly opokas, marly limestones and 'soft limestones of chalk type. A correlation can be observed between delta34S and the concentration of Ca or Mg ions also a correlation between HCO3- ion concentration and delta18O in sulphates. Probably these correlations are the result of some simultaneous processes, which occur in groundwater. The seasonal variations of the isotopic composition and sulphate concentration were observed in four springs feeding the upper Wieprz. The variations were simultaneous and often similar in these springs. Probably, these variations are caused by the admixture of sulphates coming from shallow water layers (or leached from soil); however the variations of the groundwater level may also change chemical and isotopic composition in groundwater.     

Isotopic Assessment of Sources and Processes Affecting Sulfate and Nitrate in Surface Water and Groundwater of Luxembourg

Abstract

Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40mg/L, δ³⁴S_sulfate values between ?3.0 and ?20.0‰, and δ¹⁸O_sulfate values between +1.5 and +5.0‰ nitrate was characterized by concentrations varying between <0.5 and 10mg/L, δ¹⁵N_nitrate values of ～?0.5‰, and δ¹⁸O_nitrate values ～+3.0‰. In the shallow groundwater, sulfate concentrations ranged from 25 to 30mg/L, δ³⁴S_sulfate values from ?20.0 to +4.5‰, and δ¹⁸O_sulfate values from ～+0.5 to +4.5‰ nitrate concentrations varied between ～10 and 75mg/L, δ¹⁵N_nitrate values between +2.5 and +10.0‰, and δ¹⁸O_nitrate values between +1.0 and +3.0‰. In surface water, sulfate concentrations ranged from 10 to 210mg/L, δ³⁴S_sulfate values varied between ?9.3 and +10.9‰, and δ¹⁸O_sulfate values between +3.0 and +10.7‰ were observed. Nitrate concentrations ranged from 10 to 40mg/L, δ¹⁵N_nitrate values from +6.5 to +12.0‰, and δ¹⁸O_nitrate values from ?0.4 to +4.0‰. Based on these data, three sulfate sources were identified controlling the riverine sulfate load. These are soil sulfate, dissolution of evaporites, and oxidation of reduced S minerals in the bedrock. Both groundwater types were predominantly influenced by sulfate from the two latter lithogenic S sources. The deep groundwater and a couple shallow groundwater samples had nitrate derived mainly from soil nitrification. All other sampling sites were influenced by nitrate originating from sewage and/or manure. A decrease in nitrate concentration observed along one of the rivers was attributed to denitrification. It appears that sulfate within Luxembourg's aquatic ecosystem is mainly of lithogenic origin, whereas nitrate is often derived from anthropogenic activities.     

Sulphur and Oxygen Isotopes in Sulphates in Natural Waters: (1) Surface Waters of Relatively Unpolluted Terrains

Abstract

The paper presents a whole-year study (1990) of an unique area in S-E Poland with numerous small rivers and streams carrying clean waters. We report the results of δ¹⁸O of waters and δ³⁴S of the sulphates sampled 4 times in 1990 from 20 rivers of the study area. The observations clearly show the impact of biological activity on the oxygen and sulphur isotopic compositions in sulphates. Attempts have been made to interpret the correlation between δ³⁴S and δ¹⁸O in sulphates. The highest correlation coefficient has been noticed for samples collected in April, whereas the lowest in August. The conclusion of this study is that the river sulphates are predominantly produced outside the river environment. We have distinguished three major sources of sulphates: (1) ones produced in the aquifer from which waters are discharged, (2) those produced in soils and marshes of forest environment, and (3) ones on anthropogenic origin.     

There is no Temperature Dependence of Net Biochemical Fractionation of Hydrogen and Oxygen Isotopes in Tree-Ring Cellulose

Abstract

The isotopic composition of tree-ring cellulose was obtained over a two-year period from small diameter, riparian zone trees along an elevational transect in Big Cottonwood Canyon, Utah, USA to test for a possible temperature dependence of net biological fractionation during cellulose synthesis. The isotope ratios of stream water varied by only 3.6‰ and 0.2‰ in δD and δ¹⁸O, respectively, over an elevation change of 810m. The similarity in stream water and macroenvironment over the short (13km) transect produced nearly constant stem and leaf water δD and δ¹⁸O values. In addition, what few seasonal variations observed in the isotopic composition of source water and atmospheric water vapor or in leaf water evaporative enrichment were experienced equally by all sites along the elevational transect. The temperature at each site along the transect spanned a range of ≥ 5°C as calculated using the adiabatic lapse rate. Since the δD and δ¹⁸O values of stem and leaf water varied little for these trees over this elevation/ temperature transect, any differences in tree-ring cellulose δD and δ¹⁸O values should have been associated with temperature effects on net biological fractionation. However, the slopes of the regressions of elevation versus the δD and δ¹⁸O values of tree-ring cellulose were not significantly different from zero indicating little or no temperature dependence of net biological fractionation. Therefore, cross-site climatic reconstruction studies using the isotope ratios of cellulose need not be concerned that temperatures during the growing season have influenced results.     

Sources and circulation of water and arsenic in the Giant Mine,Yellowknife, NWT,Canada

Recovery of gold from arsenopyrite-hosted ore in the Giant Mine camp, Yellowknife, NWT, Canada, has left a legacy of arsenic contamination that poses challenges for mine closure planning. Seepage from underground chambers storing some 237,000 tonnes of arsenic trioxide dust, has As concentrations exceeding 4000 ppm. Other potential sources and sinks of As also exist. Sources and movement of water and arsenic are traced using the isotopes of water and sulphate. Mine waters (16 ppm As; As^V/As^III ≈ 150) are a mixture of two principal water sources – locally recharged, low As groundwaters (0.5 ppm As) and Great Slave Lake (GSL; 0.004 ppm As) water, formerly used in ore processing and discharged to the northwest tailings impoundment (NWTP). Mass balance with δ¹⁸O shows that recirculation of NWTP water to the underground through faults and unsealed drillholes contributes about 60% of the mine water. ;[emsp]>Sulphate serves to trace direct infiltration to the As₂O₃ chambers. Sulphate in local, low As groundwaters (0.3–0.6 ppm As; δ³⁴S_SO4  ～ 4 ‰ and δ¹⁸O_SO4  ～ ? 10 ‰) originates from low-temperature aqueous oxidation of sulphide-rich waste rock. The high As waters gain a component of ¹⁸O-enriched sulphate derived from roaster gases (δ¹⁸O_SO4  = + 3.5 ‰), consistent with their arsenic source from the As₂O₃ chambers. High arsenic in NWTP water (～ 8 ppm As; δ¹⁸O_SO4  = ? 2 ‰) derived from mine water, is attenuated to close to 1 ppm during infiltration back to the underground, probably by oxidation and sorption by ferrihydrite.