The source of sulfur in sulfide deposits in the Siberian Platform traps (from isotope data)

The source of sulfur in giant Norilsk-type sulfide deposits is discussed. A review of the state of the problem and a critical analysis of existing hypotheses are made. The distribution of δ³⁴S in sulfides of ore occurrences and small and large deposits and in normal sedimentary, metamorphogenic, and hypogene sulfates is considered. A large number of new δ³⁴S data for sulfides and sulfates in various deposits, volcanic and terrigenous rocks, coals, graphites, and metasomatites are presented. The main attention is focused on the objects of the Norilsk and Kureika ore districts. The δ³⁴S value varies from -14 to + 22.5‰ in sulfides of rocks and ores and from 15.3 to 33‰ in anhydrites. In sulfide-sulfate intergrowths and assemblages, δ³⁴S is within 4.2-14.6‰ in sulfides and within 15.3-21.3‰ in anhydrites. The most isotopically heavy sulfur was found in pyrrhotite veins in basalts (δ³⁴S = 21.6‰), in sulfate veins cutting dolomites (δ³⁴S = 33‰), and in subsidence caldera sulfates in basalts (δ³⁴S = 23.2-25.2‰). Sulfide ores of the Tsentral’naya Shilki intrusion have a heavy sulfur isotope composition (δ³⁴S = + 17.7‰ (n = 15)). Thermobarogeochemical studies of anhydrites have revealed inclusions of different types with homogenization temperatures ranging from 685 °C to 80 °C. Metamorphogenic and hypogene anhydrites are associated with a carbonaceous substance, and hypogene anhydrites have inclusions of chloride-containing salt melts. We assume that sulfur in the trap sulfide deposits was introduced with sulfates of sedimentary rocks (δ³⁴S = 22-24‰). No assimilation of sulfates by basaltic melt took place. The sedimentary anhydrites were “steamed” by hydrocarbons, which led to sulfate reduction and δ³⁴S fractionation. As a result, isotopically light sulfur accumulated in sulfides and hydrogen sulfide, isotopically heavy sulfur was removed by aqueous calcium sulfate solution, and “residual” metamorphogenic anhydrite acquired a lighter sulfur isotope composition as compared with the sedimentary one. The wide variations in δ³⁴S in sulfides and sulfates are due to changes in the physicochemical parameters of the ore-forming system (first of all, temperature and P_ch4) during the sulfate reduction. The regional hydrocarbon resources were sufficient for large-scale ore formation.     

Diurnal variability of upper ocean temperature and heat budget in the southern Bay of Bengal during October–November, 1998 (BOBMEX-Pilot)

Time-series data on upper-ocean temperature, Vessel-Mounted Acoustic Doppler Current Profiler (VM-ADCP) measured currents and surface meteorological parameters have been obtained for the first time in the southern Bay of Bengal at 7‡N, 10‡N, and 13‡N locations along 87‡E during October–November, 1998 under BOBMEX-Pilot programme. These data have been analysed to examine the diurnal variability of upper oceanic heat budget and to estimate the eddy diffusivity coefficient of heat in the upper layer. Diurnal variation of near-surface temperature is typical at northern location (13‡N) with a range of 0.5‡C while the diurnal range of temperature is enhanced to 0.8‡C at the central location (10‡N) due to intense solar radiation (1050 W/m²), clear skies and low wind speeds. At the southern location (7‡N), the diurnal variation of temperature is atypical with the minimum temperature occurring at 2000 hrs instead of at early morning hours. In general, the diurnal curve of temperature penetrated up to 15 to 20 m with decreasing diurnal range with depth. The VM-ADCP measured horizontal currents in the upper ocean were predominantly easterly/northeasterly at southern location, north/northerly at central location and northwesterly at northern location, thus describing a large-scale cyclonic gyre with the northward meridional flow along 87‡E. The magnitudes of heat loss at the surface due to air-sea heat exchanges and in the upper 50 m layer due to vertical diffusion of heat are highest at the southern location where intense convective activity followed by overcast skies and synoptic disturbance prevailed in the lower atmosphere. This and the estimated higher value (0.0235 m²/s) of eddy diffusivity coefficient of heat in the upper ocean (0–50 m depth) suggest that 1-D processes controlled the upper layer heat budget at the southern location. On the other hand, during the fair weather conditions, at the central and northern locations, the upper layer gained heat energy, while the sea surface lost (gained) heat energy at northern (central) location. This and lower values of eddy diffusivity coefficient of heat (0.0045 and 0.0150 m²/s) and the northward intensification of horizontal currents at these locations suggest the greater role of horizontal heat advection over the 1-D processes in the upper ocean heat budget at these two locations.     

Late Quaternary sea‐level change and evolution of Belfast Lough,Northern Ireland: new offshore evidence and implications for sea‐level reconstruction

The interplay of eustatic and isostatic factors causes complex relative sea‐level (RSL) histories, particularly in paraglacial settings. In this context the past record of RSL is important in understanding ice‐sheet history, earth rheology and resulting glacio‐isostatic adjustment. Field data to develop sea‐level reconstructions are often limited to shallow depths and uncertainty exists as to the veracity of modelled sea‐level curves. We use seismic stratigraphy, 39 vibrocores and 26 radiocarbon dates to investigate the deglacial history of Belfast Lough, Northern Ireland, and reconstruct past RSL. A typical sequence of till, glacimarine and Holocene sediments is preserved. Two sea‐level lowstands (both max. ?40 m) are recorded at c. 13.5 and 11.5k cal a bp . Each is followed by a rapid transgression and subsequent periods of RSL stability. The first transgression coincides temporally with a late stage of Meltwater Pulse 1a and the RSL stability occurred between c. 13.0 and c. 12.2k cal a bp (Younger Dryas). The second still/slowstand occurred between c. 10.3 and c. 11.5k cal a bp . Our data provide constraints on the direction and timing of RSL change during deglaciation. Application of the Depth of Closure concept adds an error term to sea‐level reconstructions based on seismic stratigraphic reconstructions.     

Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.     

Groundwater-level response to land-use change and the implications for salinity management in the West Moorabool River catchment, Victoria, Australia

The connection between the removal of native vegetation, rising water tables and increasing stream salinity has been established for many catchments across Australia. However, the West Moorabool River in south west Victoria is an example of a catchment where there has been little discernable effect on groundwater levels following land clearing. Over the past 150 years, a significant portion of the catchment has been cleared of dense forest for agricultural development. Historic standing water-level records from 1870–1871 and 1881 are compared with contemporary measurements (1970s to 2007) recorded in the government bore databases. The data show that the earliest recorded groundwater levels are well within the seasonal range of values observed today. By integrating geology and hydrogeology with historical observations of groundwater levels, climate data and land use, the contemporary field observations of stream salinity are linked to the changed water use and shift in rainfall. In contrast to the normally accepted axiom, reafforestation as a management strategy to mitigate the rising salinity in the West Moorabool River catchment would seem inappropriate.     

Deconvolution of teleseismic recordings for mantle structure

Delineation of detailed mantle structure frequently requires the separation of source signature and structural response from seismograms recorded at teleseismic distances. This deconvolution problem can be posed in a log-spectral domain where the operation of time-domain convolution is reduced to an additive form. The introduction of multiple events recorded at many stations leads to a system of consistency equations that must be honoured by both the source time functions and the impulse responses associated with propagation paths between sources and receivers. The system is inherently singular, and stabilization is accomplished through the supply of an initial estimate of the source time function. Although alternative choices exist, an effective estimate is derived from the eigenimage associated with the largest eigenvalue in a singular-value decomposition of the suite of aligned seismograms corresponding to a given event. The relation of the deconvolution scheme to simultaneous least-squares deconvolution is examined. Application of the methodology to broadband teleseismic P waveforms recorded on the Canadian National Seismograph Network demonstrates the retrieval of effective Green's functions including secondary phases associated with upper-mantle structure.     

Hydrocarbon gases (C1–C5) and organic matter in bottom sediments of the Ivankovo Reservoir on the Volga River

The results of studying the composition of hydrocarbon gases (C₁–C₅) and organic matter in bottom sediments of the Ivankovo Reservoir in 1995, 2004, and 2005 are given. The methods used in the study include vapor-phase gas chromatography, instrumental pyrolysis gas chromatography, and mass-spectrometry for determining organic carbon δ ¹³C_org. The gas field of bottom sediments in different regions of the reservoir varies widely in terms of gas saturation and the spectrum of hydrocarbon gases. This suggests the heterogeneous composition of organic matter in the sediments and different conditions of its input and transformation processes. The gases were found to contain saturated hydrocarbons from methane to pentane C₁–C₅, including isomers i-C₄ and i-C₅ and unsaturated compounds C₂–C₄. A correlation was found to exist between methane distribution and the distribution of its more high-molecular homologues, which confirms their genetic relationship in bottom sediments. The obtained results show an increase in the rate of microbiological processes and organic matter transformation for most regions in the Ivankovo Reservoir. The only exceptions are the zones of Moshkovichskii Bay and the sections at Gorodnya and Konakovo, where technogenic organic matter is being accumulated. The high information value of hydrocarbon gases as biogeochemical markers of the sources of organic matter and the rates of its transformation is demonstrated. The isotopic composition of organic-matter carbon in the bottom sediments of the Ivankovo Reservoir δ ¹³C varies from ?26.21 to ?30.86‰.     

An answer to an important controversy and the need for caution when using simple models to predict inelastic earthquake response of buildings with torsion

This paper presents evidence that the extension of conclusions based on the widely used simplified, one story, eccentric systems of the shear‐beam type, to actual, nonsymmetric buildings and consequent assessments of the pertinent code provisions, can be quite erroneous, unless special care is taken to match the basic properties of the simplified models to those of the real buildings. The evidence comes from comparisons of results obtained using three variants of simplified models, with results from the inelastic dynamic response of three‐ and five‐story eccentric buildings computed with detailed MDOF systems, where the members are idealized with the well‐known plastic hinge model. In addition, a convincing answer is provided on a pertinent hanging controversy: For frame‐type buildings, designed in accordance with the dynamic provisions of modern codes (such as EC8 or IBC2000), which allow reduced shears at the stiff edge due to torsion, the frames at the flexible sides are the critical elements in terms of ductility demands. Copyright © 2009 John Wiley & Sons, Ltd.     

Simulation of scree‐slope dynamics: investigating the distribution of debris avalanche events in an idealized two‐dimensional model

We present a two‐dimensional model of the development of scree slopes using the discrete‐element method. We concentrate on the dynamics of the accumulating debris at the cliff foot rather than on the failure modes of the cliff‐face or shape of the underlying rock surface. The evolution of this unconsolidated material is intermittent and systematically changing over time, with an early high disturbance regime, dominated by a characteristic event size (where 65% of particles in the debris are in motion to some extent), replaced at later times by many shallow slides interspersed with infrequent large events that involve motion through almost the full scree depth. These large slides lead to a stratigraphy in which the layers of material are stretched almost horizontal near the base of the slope. The scree surface thus shows a gradient in age with most recent rock‐fall close to the cliff and the oldest rock‐fall debris outcropping at the foot. The final surface slope tends to show little curvature, and the final mean slope is well correlated with the angle of internal friction of the particles, although the change is very small over a wide range of friction angles [final slope (in degrees relative to horizontal) ~ 0.043 × internal friction angle + 17.49, with a correlation coefficient of 0.89, p‐value 0.0001]. Some weak size‐segregation of the debris is found, but this seems to have little to do with individual particles bounding down the slope. The shape of the rock core agrees largely with the analytic forms given by Fisher–Lehmann and Bakker–Le Heux expressions, but the original simple Fisher quadratic can give the best fit. Overall the evolution shows a remarkable insensitivity to the model parameters, suggesting that the controls on dry scree‐slope evolution are primarily geometric in character. Copyright © 2014 John Wiley & Sons, Ltd.