Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: Dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130)

Microbially mediated sulfate reduction affects the isotopic composition of dissolved and solid sulfur species in marine sediments. Experiments and field data show that the composition is also modified in the presence of sulfate-reducing microorganisms. This has been attributed either to a kinetic isotope effect during the reduction of sulfate to sulfite, cell-internal exchange reactions between enzymatically-activated sulfate (APS), and/or sulfite with cytoplasmic water. The isotopic fingerprint of these processes may be further modified by the cell-external reoxidation of sulfide to elemental sulfur, and the subsequent disproportionation to sulfide and sulfate or by the oxidation of sulfite to sulfate. Here we report values from interstitial water samples of ODP Leg 182 (Site 1130) and provide the mathematical framework to describe the oxygen isotope fractionation of sulfate during microbial sulfate reduction. We show that a purely kinetic model is unable to explain our data, and that the data are well explained by a model using oxygen isotope exchange reactions. We propose that the oxygen isotope exchange occurs between APS and cytoplasmic water, and/or between sulfite and adenosine monophosphate (AMP) during APS formation. Model calculations show that cell external reoxidation of reduced sulfur species would require up to 3000 mol/m³ of an oxidant at ODP Site 1130, which is incompatible with the sediment geochemical data. In addition, we show that the volumetric fluxes required to explain the observed data are on average 14 times higher than the volumetric sulfate reduction rates (SRR) obtained from inverse modeling of the porewater data. The ratio between the gross sulfate flux into the microbes and the net sulfate flux through the microbes is depth invariant, and independent of sulfide concentrations. This suggests that both fluxes are controlled by cell density and that cell-specific sulfate reduction rates remain constant with depth.     

Non-isothermal scavenging of highly soluble gaseous pollutants by rain in the atmosphere with non-uniform vertical concentration and temperature distributions

We suggest a non-isothermal one-dimensional model of precipitation scavenging of highly soluble gaseous pollutants in inhomogeneous atmosphere. When gradients of soluble trace gases’ concentrations and temperature in the atmosphere are small, scavenging of gaseous pollutants is governed by two linear wave equations that describe propagation of a scavenging and temperature waves in one direction. If wash-down front velocity is much larger than the velocity of the temperature front, scavenging is determined by propagating scavenging front in the atmosphere with inhomogeneous temperature distribution. We solved the derived equation by the method of characteristics and determined scavenging coefficient and the rates of precipitation scavenging for wet removal of sulfur dioxide using measured initial distributions of trace gases and temperature in the atmosphere. It is shown that in the case of exponential initial distribution of soluble trace gases and linear temperature distribution in the atmosphere, scavenging coefficient in the region between the ground and the position of a scavenging front is proportional to rainfall rate, solubility parameter in the under-cloud region, adjacent to a bottom of a cloud and to the growth constant in the formula for the initial profile of a soluble trace gas in the atmosphere. The derived formula yields the same value of scavenging coefficient for sulfur dioxide scavenging by rain as field estimates presented by McMahon and Denison (Atmos Environ 13:571–585, 1979). It is demonstrated that in the case when the altitude variation of temperature in the atmosphere is determined by the environmental lapse rate, scavenging coefficient increases with height in the region between the scavenging front and the ground. In the case when altitude temperature variation in the atmosphere is determined by temperature inversion, scavenging coefficient decreases with height in a region between the scavenging front and the ground. Theoretical predictions of the value of the scavenging coefficient for sulfur dioxide washout by rain and of the dependence of the magnitude of the scavenging coefficient on rain intensity are in good agreements with the atmospheric measurements of Martin (Atmos Environ 18:1955–1961, 1984).     

Middle Pleistocene environments,landscapes and tephrostratigraphy of the Armenian Highlands: evidence from Bird Farm 1, Hrazdan Valley

The significance of the southern Caucasus in understanding Pleistocene hominin expansions is well established. However, the palaeoenvironments in which Palaeolithic occupation of the region took place are presently poorly defined. The Hrazdan river valley, Armenian Highlands, contains a rich Palaeolithic record alongside Middle Pleistocene volcanic, fluvial and lacustrine strata, and thus offer exciting potential for palaeoenvironmental reconstruction. We present the first results of sedimentological, geochemical, tephrostratigraphical and biological (diatoms) study of the sequence of Bird Farm 1, located in the central part of the valley. These data show six phases of landscape development during the interval 440–200 ka. The sequence represents the first quantitative Pleistocene diatom record from the Armenian Highlands and the southern Caucasus, and indicates the persistence of a deep, stratified lacustrine system, with evidence for changing lake productivity that is tentatively linked to climate. Furthermore, major element chemical characterization of visible and crypto-tephra horizons in the sequence enables the first stages of the development of a regional tephrostratigraphy. Together, the evidence from Bird Farm 1 demonstrates the importance of lacustrine archives in the region for palaeoenvironmental reconstruction and highlights the potential for linkages between archives on both a local and regional scale.