Origin and distribution of sulphate in surface waters of the Mansfeld mining district (Central Germany)--a sulphur isotope study.

In the Mansfeld region (Central Germany) copper mining contributed to an enormous pollution of the environment. Metal- and sulphate-bearing sediments and leachates emerge from the former copper smelters and mining waste heaps, spread along local rivers and finally reach the Saale river. A sulphur isotope study on water and stream sediments was performed along the River "B?se Sieben" and from its tributaries to determine the different sulphur sources. Four major sulphur sources exist in the area: metal sulphide mineralisations (Kupferschiefer), met alliferous sulphidic flue dust, slag, and anhydrite and gypsum of Permian and Triassic age. We obtained delta34S(SO4)-values in water samples varying from +4 per thousand to -18 per thousand CDT, clearly reflecting the input of sulphate from different sources. Sulphate from the oxidation of sulphidic mining residues is restricted to the mining area and cannot be traced for more than 5 km downstream. The major source for sulphate is the dissolution of gypsum and anhydrite. The sulphur isotope composition in dissolved and sedimentary adsorbed sulphate differs only slightly from each other. Microbial dissimilatory sulphate reduction can not be excluded in the shallow sediment layers.     

Stable isotope biogeochemistry of the sulfur cycle in modern marine sediments: I. Seasonal dynamics in a temperate intertidal sandy surface sediment

A biogeochemical and stable isotope geochemical study was carried out in surface sediments of an organic-matter poor temperate intertidal sandy surface sediment (German Wadden Sea of the North Sea) to investigate the activity of sulfate-reducing bacteria and the dynamics of the vertical partitioning of sedimentary sulfur, iron, and manganese species in relation to the availability of total organic carbon (TOC) and mud contents. The contents and stable isotopic compositions ((34)S/(32)S) of total reduced inorganic sulfur species (TRIS) and dissolved sulfate were measured. Maximum oxygen penetration depths were estimated from the onset of a blackening of the sediments due to FeS accumulation and ranged from 5 to 10 mm below surface (mmbsf). A zone of relatively moderate relative organic-matter enrichment was found between 5 and 20 mmbsf leading to enhanced activities of sulfate-reducing bacteria with sulfate-reduction rates (SRR) up to 350 nmol cm(-3) d(-1). Below this zone, microbial SRR dropped significantly. Depth integrated SRR seem to depend not only on temperature but also on the availability of reactive organic matter. The sulfur-isotopic composition of TRIS was depleted in (34)S by 33-40 per thousand with respect to coexisting dissolved sulfate (constant at about +21 per thousand vs. Vienna-Canyon Diablo Troilite (V-CDT)). Since sulfate reduction is not limited by dissolved sulfate (open system), depth variations of the isotopic composition of TRIS reflect changes in overall isotope effect due to superimposed microbial and abiotic reactions. Most of the solid-phase iron and manganese was bonded to (non-reactive) heavy minerals. However, a layer of reactive Fe(III) and Mn(IV) oxi(hydroxi)des was found in the uppermost sediment section due to re-oxidation of dissolved Fe(II) and Mn(II) species at the sediment-water interface. Metal cycling below the surface is at least partially coupled to intense sulfur cycling.     

Stable isotope ratios and uric acid preservation in termites belonging to three feeding habits in Thailand

Nitrogen and carbon stable isotope ratios and uric acid concentrations in termites sampled from a dry evergreen forest in Thailand, were determined across three kinds of feeding habits. Feeding habits of Microcerotermes crassus, which is an abundant wood-feeder, and Dicuspiditermes makhamensis, a common soil-feeding termite, were confirmed by isotopic signatures. Lichen feeding termites (Hospitalitermes birmanicus, H. bicolor and H. ataramensis) were characterized by low delta15N values, suggesting that they assimilated nitrogen deposited from the atmosphere. There was also a significant difference in uric acid concentrations between termites representing different feeding habits. No significant relationships were found between uric acid concentrations and delta15N or delta13C in Hospitalitermes. However, delta15N values were correlated with C/N ratios in H. birmanicus, except in one colony of H. ataramensis. delta13C values in both species were negatively correlated with C/N ratios.     

Surface phenomena related to mirror degradation in extreme ultraviolet (EUV) lithography

One of the most promising methods for next generation device manufacturing is extreme ultraviolet (EUV) lithography, which uses 13.5 nm wavelength radiation generated from freestanding plasma-based sources. The short wavelength of the incident illumination allows for a considerable decrease in printed feature size, but also creates a range of technological challenges not present for traditional optical lithography. Contamination and oxidation form on multilayer reflecting optics surfaces that not only reduce system throughput because of the associated reduction in EUV reflectivity, but also introduce wavefront aberrations that compromise the ability to print uniform features. Capping layers of ruthenium, films ∼2 nm thick, are found to extend the lifetime of Mo/Si multilayer mirrors used in EUV lithography applications. However, reflectivities of even the Ru-coated mirrors degrade in time during exposure to EUV radiation. Ruthenium surfaces are chemically reactive and are very effective as heterogeneous catalysts. In the present paper we summarize the thermal and radiation-induced surface chemistry of bare Ru exposed to gases; the emphasis is on H₂O vapor, a dominant background gas in vacuum processing chambers. Our goal is to provide insights into the fundamental physical processes that affect the reflectivity of Ru-coated Mo/Si multilayer mirrors exposed to EUV radiation. Our ultimate goal is to identify and recommend practices or antidotes that may extend mirror lifetimes.     

Methane-derived carbonates in a native sulfur deposit: stable isotope and trace element discriminations related to the transformation of aragonite to calcite

Abstract Stable isotope ((13)C, (18)O, (34)S) and trace element (Sr(2+), Mg(2+), Mn(2+), Ba(2+), Na(+)) investigations of elemental sulfur, primary calcites and mixtures of aragonite with secondary, post-aragonitic calcite from sulfur-bearing limestones have provided new insights into the geochemistry of the mineral forming environment of the native sulfur deposit at Machów (SE-Poland). The carbon isotopic composition of carbonates (δ(13)C = -41 to -47‰ vs. PDB) associated with native sulfur (δ(34)S = + 10 to + 15‰ vs. V-CDT) relates their formation to the microbiological anaerobic oxidation of methane and the reduction of sulfate derived from Miocene gypsum. From a comparison with experimentally derived fractionation factors the element ratios of the aqueous fluids responsible for carbonate formation are estimated. In agreement with field and laboratory observations, ratios near seawater composition are obtained for primary aragonite, whereas the fluids were relatively enriched in dissolved calcium during the formation of primary and secondary calcites. Based on the oxygen isotope composition of the carbonates (δ(18)O = -3.9 to -5.9‰ vs. PDB) and a secondary SrSO(4) (δ(18)O = + 20‰ vs. SMOW; δ(34)S = + 59‰ vs. V-CDT), maximum formation temperatures of 35°C (carbonates) and 47°C (celestite) are obtained, in agreement with estimates for West Ukraine sulfur ores. The sulfur isotopic composition of elemental sulfur associated with carbonates points to intense microbial reduction of sulfate derived from Miocene gypsum (δ(34)S ≈ + 23‰) prior to the re-oxidation of dissolved reduced sulfur species.     

Stable isotope signatures of meteoric water in the Cuvelai-Etosha Basin,Namibia: Seasonal characteristics,trends and relations to southern African patterns

ABSTRACT

The study area is the Namibian part of the Cuvelai-Etosha Basin (CEB), located in central northern Namibia. The CEB is home to 40 % of Namibia’s population, and most of the people live in rural areas. These people depend on both surface and groundwater resources which are limited in this dryland (mean annual rainfall ranging from 250 to 550?mm/a). The isotopic signatures of δ¹⁸O and δ²H from water samples (n?=?61) collected over a course of 9 years from various research projects and existing (but mainly unpublished) data of meteoric water of the CEB (10 sites) were evaluated and local meteoric water lines (LMWLs) developed. Further, the data is discussed in the context of seasonal characteristics and trends and compared to available data from the Global Network of Isotopes in Precipitation (GNIP) for the southern African region. Our results extend the portfolio of previously published LMWLs for southern Africa and provide a more precise baseline for any isotope-based study in that region. The slope of the LMWL from the GNIP stations correlates with latitude. This correlation cannot be found within the CEB. The dominant control on the isotopic signature of the CEB of precipitation is seasonal.