Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

Serpentinization of abyssal peridotites from the MARK area, Mid-Atlantic Ridge: sulfur geochemistry and reaction modeling

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated δ³⁴S_sulfide (3.7 to 12.7‰). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high δ³⁴S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (∼400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ∼300°C. Serpentinization produces highly reducing conditions and significant amounts of H₂ and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in ¹³C (up to 4.5‰) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 × 10¹² g seawater S yr⁻¹. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.     

Oxygen isotopic compositions of IVA iron meteorites: implications for the thermal evolution derived from in situ ultraviolet laser microprobe analyses

Oxygen isotopic compositions of silicate inclusions in IVA iron meteorites have been measured with an in situ UV laser microprobe technique. The homogeneity of oxygen isotopic compositions within and among individual mineral grains has also been examined. Oxygen isotope fractionations between coexisting mineral pairs were utilized in oxygen isotope thermometry. Our measured Δ¹⁷O values, ranging from 0.97 to 1.25‰, are characteristic of a single reservoir and fully confirm the oxygen isotopic similarity between IVA irons and L/LL chondrites. Steinbach and São João Nepomuceno, containing inclusions of two silicate minerals in mutual contact, exhibit a mass-dependent fractionation of ¹⁸O/¹⁶O between tridymite and bronzite with apparent oxygen isotopic heterogeneity. The SiO₂-bearing member, Gibeon, gives homogeneous oxygen isotopic compositions without detectable fractionation of ¹⁸O/¹⁶O between tridymite and quartz. Oxygen isotope equilibrium temperatures are estimated for coexisting tridymite and bronzite in the same sample slabs or clusters in Steinbach and São João Nepomuceno. The fractionations of ¹⁸O/¹⁶O between bronzite and tridymite range from 1.6 to 2.3‰ in different sample slabs or clusters. On the basis of the closure temperature concept, cooling rates are estimated at approximately 20 to 1000°C/Myr between 800 and 1000°C, a range of temperatures not accessible to other cooling rate methods. Using the Fast Grain Boundary diffusion model, we have demonstrated that significant oxygen heterogeneity both in tridymite and bronzite is probably due to isotope exchange during cooling between minerals with various grain sizes and mineral abundances in different regions of the samples. The new estimates of cooling rate by oxygen isotope thermometry refine previous cooling curves of IVA irons and support the breakup-reassembly model for the IVA parent body.     

Determination of part-per-trillion levels of atmospheric dimethyl sulfide by isotope dilution gas chromatography/mass spectrometry

Stable isotopic dilution was applied to the determination of dimethyl sulfide (DMS) in ambient air at the low part-per-trillion by volume (pptrv) levels. Perdeuterated DMS was used as an internal standard in the gas chromatography/mass spectrometry determination. The isotopically labelled internal standard provided insensitivity to possible losses of DMS in sampling and analysis. The lower limit of detection (LLD) was 1 pptrv with a sample acquisition time of 2 min.     

Eocene tectono-thermal rejuvenation of an upper Paleozoic-lower Mesozoic terrane in the Cordillera de Carabaya, Puno, southeastern Peru, revealed by K---Ar and Ar/Ar dating

K---Ar dates for muscovites and biotites in granitoid rocks and hydrothermal ore deposits of the northeastern parts of the plutons making up the Triassic Carabaya batholith, underlying the axial Cordillera Oriental of northern Puno Department, southeastern Peru, are markedly variable and mutually discordant. Steep transverse gradients are defined in the apparent ages of both micas, which decrease systematically from SW to NE, delimiting a ca. 25-km-wide, longitudinal zone of anomalously young Mesozoic to Paleocene dates. Age minima of 37±1 Ma are attained in three of the four studied transects. ⁴⁰Ar/³⁹Ar step-heating analyses of selected micas confirm the occurrence of a thermal disturbance, and modeling of the spectra suggests that argon loss in muscovites attains at least ca. 75% in the northeastern part of the zone. A single K-feldspar spectrum yielded a minimum at 31 Ma, and apatite fission-track age cluster at ca. 31 and 18.5 Ma. The affected granitoid rocks generally display little megascopic evidence of tectonism, but microscopic deformational fabrics increase in intensity with apparent decreasing K---Ar age, paralleling a marked increase in alkali feldspar ordering. Secondary fluid inclusions trapped within the microfabrics reveal that the plutonic rocks were penetrated by a homogeneous H₂O---CO₂---CH₄---NaCl fluid at ca. 300–400°C and 0.7–2 kbar. This fluid is implicated in the degassing of the rocks. These diverse data are interpreted as evidence for a major, but moderate-temperature (400°C) and brief, tectono-thermal event at ca. 37±1 Ma (biotite closure temperature)—i.e., at the Eocene-Oligocene boundary. The K-feldspar ⁴⁰Ar/³⁹Ar data and the Oligocene fission-track dates may record the later stages in the event, whereas the Miocene fission-track dates are tentatively ascribed to a distinct Neogene episode. Essentially identical geochronological and petrological relationships have been documented in the Cordillera Real of northwestern Bolivia by McBride et al. (1987), permitting the delimination of a disturbed belt paralleling the South American plate boundary and more than 450 km long. The tectono-thermal domain, which we term the Zongo-San Gabán Zone, constituted the foreland boundary of the Andean orogen in the vicinity of the Arica Deflection during the late Eocene Incaic orogeny. This regional thermal event, which involved the basement, appears to have resulted from compressional or, in some segments, transpressional tectonics.     

Modeling basin-scale hydrology in support of physical climate and global biogeochemical studies: An example using the Zambezi River

Human activity is an important agent defining the contemporary hydrologic cycle. We have documented the potential impacts of impoundment, land use change and climate change on the Zambezi River system in southern Africa and found that they can be substantial. A full analysis requires construction and parameterization of a simulation for the entire catchment. This paper develops a strategy for implementing catchment-scale models of the major hydrologic processes operating within the basin. A coherent data set for calibrating the models has also been assembled. The algorithms consist of a Water Balance (WBM) and a Water Transport (WTM) operating at 1/2^o spatial scale and at monthly timesteps. These models transform complex patterns of regional climatology into estimates of soil water, evapotranspiration, runoff, and discharge through rivers of various size. The models are dependent on the characteristics of the terrestrial surface, principally soil texture and land cover. A simulated river network is also required. Additional tabular data sets are essential for model testing and calibration. These include subcatchment areas; observed river discharge at selected points; flooding, storage and loss characteristics of major wetlands; floodwave translation; and, volume, surface area, withdrawal and evaporative losses from impoundments. An important design consideration for the numerous impoundments in the Zambezi requires an understanding of the seasonal variation in discharge, in particular how it might respond to climate and land use change. The research strategy offered here lays a framework for addressing such issues. Although the primary focus of this work is hydrologic, we discuss how the model can be extended to consider constituent transport and biogeochemical cycling issues at the continental scale.     

Hydrogeochemical exploration for Mississippi valley-type deposits, Arkansas, U.S.A.

Three areas located in northern Arkansas, U.S.A., representing differing host rock and mineralization, were selected to investigate the usefulness of hydrogeochemical exploration for Mississippi Valley-type Pb-Zn mineralization. Despite the geologic differences among the areas, there were no great differences in groundwater chemistry and threshold values. Anomalous Pb concentrations, and also anomalous Zn concentrations to a lesser extent, are useful in detecting the Pb-Zn mineralized areas; however, specific deposits could not be located. Because of the low threshold values (about 20 μg/1) for Pb and Zn, spring water must be utilized in order to avoid plumbing contamination.     

Holocene climatic change in the northern Midwest: Pollen-derived estimates

Mapping of Holocene pollen data in the midwestern United States has revealed several broadscale vegetational changes that can be interpreted in climatic terms. These changes include (1) the early Holocene northward movement of the spruce-dominated forest and its later southward movement after 3000 yr B.P. and (2) the eastward movement of the prairie/forest border into southwestern Wisconsin by 8000 yr B.P. and its subsequent westward retreat after 6000 yr B.P. When certain basic assumptions are met, multiple regression models can be derived from modern pollen and climate data and used to transform the pollen record of these vegetational changes into quantitative estimates of temperature or precipitation. To maximize the reliability of the regression equations, we followed a sequence of procedures that minimize violations of the assumptions that underlie regression analysis. Reconstructions of precipitation during the Holocene indicated that from 9000 to 6000 yr B.P. precipitation decreased by 10 to 25% over much of the Midwest, while mean July temperature increased by 0.5° to 2.0°C. At 6000 yr B.P. precipitation was less than 80% of its modern values over parts of Wisconsin and Minnesota. After 6000 yr B.P. precipitation generally increased, while mean July temperature decreased in the north, and increased in the south. The time of the maximum temperature varies within the Midwest and is earlier in the north and later in the south.