Concurrent low- and high-affinity sulfate reduction kinetics in marine sediment

Bacterial sulfate reduction in marine sediments generally occurs in the presence of high millimolar concentrations of sulfate. Published data indicate that low sulfate concentrations may limit sulfate reduction rates below 0.2-2 mM. Yet, high sulfate reduction rates occur in the 1-100 μM range in freshwater sediments and at the sulfate-methane transition in marine sediments. Through a combination of ³⁵S-tracer experiments, including initial velocity experiments and time course experiments, we searched for different sulfate affinities in the mixed community of sulfate reducers in a marine sediment. We supported the radiotracer experiments with a highly sensitive ion chromatographic technique for sulfate with a detection limit of 0.15 μM SO₄²⁻ in marine pore water. Our results showed that high and low affinities for sulfate co-occur and that the applied experimental approach may determine the observed apparent half saturation constant, K_m. Our experimental and model data both show that sulfate reduction in the studied marine sediment could be explained by two dominating affinities for sulfate: a low affinity with a mean half saturation constant, K_m, of 430 μM SO₄²⁻ and a high affinity with a mean K_m of 2.6 μM SO₄²⁻. The high-affinity sulfate reduction was thermodynamically un-constrained down to <1 μM SO₄²⁻, both in our experiments and under in situ conditions. The reduction of radio-labeled sulfate was partly reversible due to concurrent re-oxidation of sulfide by Fe(III) and possibly due to a reversibility of the enzymatic pathway of sulfate reduction. A literature survey of apparent K_m values for sediments and pure cultures is presented and discussed.     

Relative contributions of sulfate- and iron(III) reduction to organic matter mineralization and process controls in contrasting habitats of the Georgia saltmarsh

The objectives of this study were to partition out the predominant anaerobic respiration pathways coupled to C oxidation and to further elucidate the controls of anaerobic C respiration in three major saltmarsh habitats at Skidaway Island, GA; the short form of Spartina alterniflora (SS), the tall form of S. alterniflora (TS), and unvegetated, bioturbated creekbank (CB). Geochemical analysis of pore water and solid phase constituents revealed that the SS site experienced highly reducing conditions with two orders of magnitude higher pore water sulfide inventories (1.884 mmol m⁻²) than TS (0.003 mmol m⁻²) and CB (0.005 mmol m⁻²), respectively. Conversely, reactive Fe(III) inventories at TS (2208 mmol m⁻²) and CB (2881 mmol m⁻²) were up to 7–9 times higher than at SS (338 mmol m⁻²). Incubations and intact core experiments indicated that reduction accounted for 95% (SS), 37% (TS) and 66% (CB) of total anaerobic respiration. There was no detectable Fe(III) reduction at SS, while Fe(III) reduction accounted for up to 70% of C oxidation in the 3–6 cm depth interval at TS and 0–3 cm depth of CB, and on average, approximately 55% of C oxidation over two-thirds of marsh surface area. Laboratory manipulations provided further evidence for the importance of Fe(III) reduction as the accumulation rates of fermentation products were high when Fe(III) reduction was inhibited by removing the Fe(III) minerals from highly bioturbated CB sediments with higher Fe(III) mineral contents. Anaerobic C oxidation, - and Fe(III)-reduction rates appeared to be highest at the TS site during active plant growth in summer. Overall results suggest that bioturbation by macrofauna is the overriding factor in modulating the pathway of C mineralization in the saltmarsh, whereas availability of organic substrates from plants is a key factor in controlling the C oxidation rate.     

Hillslopes in humid-tropical climates aren't always wet: Implications for hydrologic response and landslide initiation in Puerto Rico

The devastating impacts of the widespread flooding and landsliding in Puerto Rico following the September 2017 landfall of Hurricane Maria highlight the increasingly extreme atmospheric disturbances and enhanced hazard potential in mountainous humid-tropical climate zones. Long-standing conceptual models for hydrologically driven hazards in Puerto Rico posit that hillslope soils remain wet throughout the year, and therefore, that antecedent soil wetness imposes a negligible effect on hazard potential. Our post-Maria in situ hillslope hydrologic observations, however, indicate that while some slopes remain wet throughout the year, others exhibit appreciable seasonal and intra-storm subsurface drainage. Therefore, we evaluated the performance of hydro-meteorological (soil wetness and rainfall) versus intensity-duration (rainfall only) hillslope hydrologic response thresholds that identify the onset of positive pore-water pressure, a predisposing factor for widespread slope instability in this region. Our analyses also consider the role of soil-water storage and infiltration rates on runoff generation, which are relevant factors for flooding hazards. We found that the hydro-meteorological thresholds outperformed intensity-duration thresholds for a seasonally wet, coarse-grained soil, although they did not outperform intensity-duration thresholds for a perennially wet, fine-grained soil. These end-member soils types may also produce radically different stormflow responses, with subsurface flow being more common for the coarse-grained soils underlain by intrusive rocks versus infiltration excess and/or saturation excess for the fine-grained soils underlain by volcaniclastic rocks. We conclude that variability in soil-hydraulic properties, as opposed to climate zone, is the dominant factor that controls runoff generation mechanisms and modulates the relative importance of antecedent soil wetness for our hillslope hydrologic response thresholds.     

Rhyolites contaminated with metapelite and gabbro,Lipari, Aeolian Islands,Italy: products of lower crustal fusion or of assimilation plus fractional crystallization?

Pleistocene lavas from Monte S. Angelo and Chiesa Vecchia volcanoes on Lipari contain two suites of inclusions. A metapelitic suite consists of gneisses and granulites with combinations of cordierite, garnet, corundum, hercynite, andalusite, sillimanite, orthopyroxene, ilmenite, magnetite, biotite, plagioclase, and quartz. A gabbroic suite has cumulus texture and contains plagioclase, orthopyroxene, clinopyroxene, and magnetite. All megacryst phases in the lavas appear to be derived from rock fragments, with the exception of euhedral strongly zoned calcic plagioclase, and none has grown by homogeneous nucleation from liquid represented by the groundmass, which is peraluminous rhyolite (>70 wt% SiO₂, >6 wt% K₂O). Ground-mass microcrysts were nearly all derived from disaggregated metapelites; overgrowths of alkali feldspar on plagioclase and of orthopyroxene on clinopyroxene, and quartz intergrown with alkali feldspar, are the only phases that grew from the rhyolitic liquid. Euhedral cordierite, hercynite, and plagioclase at the margins of some rock fragments grew by reaction of metapelite with liquid.For grains in contact within metapelite inclusions, geothermometers and geobarometers yield estimates of equilibration conditions in the range of 800±100° C and 5±1 kbar. Compositions of phases in the same thin section, but not in the same inclusion, yield broadly erratic P and T estimates indicating disequilibrium among metapelite inclusions. Pyroxene thermometry in the gabbro suite indicates a crystallization temperature of 1020±50° C and a lack of subsequent thermal equilibration with the rhyolitic liquid.The metapelite suite may partly be restite, but much is xenolithic, derived from a vertical interval of perhaps several kilometers, and may have undergone a much earlier episode of melting. The gabbro fragments are accidental xenoliths incorporated as the magma rose. Contaminants (metapelite and gabbro) account for 50 vol.% of the lavas, and cause them to be classified as high-K andesite according to whole-rock major element analysis.The rhyolitic liquid may have originated by partial fusion of metapelites in the lower crust, or by fractional crystallization of mafic mantle-derived magma combined with assimilation of metapelite; the bulk of the evidence favors assimilation-fractional crystallization. Miocene and younger metapelite-contaminated rhyolites also occur in Tuscany, SE Spain, E Morocco, and NW Tunisia, and are associated in each region with mafic silica-undersaturated lavas, implying crustal underplating around the western Mediterranean before, during, and after formation of the Tyrrhenian basin.     

Performance of the WRF model to simulate the seasonal and interannual variability of hydrometeorological variables in East Africa: a case study for the Tana River basin in Kenya

This study investigates the ability of the regional climate model Weather Research and Forecasting (WRF) in simulating the seasonal and interannual variability of hydrometeorological variables in the Tana River basin (TRB) in Kenya, East Africa. The impact of two different land use classifications, i.e., the Moderate Resolution Imaging Spectroradiometer (MODIS) and the US Geological Survey (USGS) at two horizontal resolutions (50 and 25 km) is investigated. Simulated precipitation and temperature for the period 2011–2014 are compared with Tropical Rainfall Measuring Mission (TRMM), Climate Research Unit (CRU), and station data. The ability of Tropical Rainfall Measuring Mission (TRMM) and Climate Research Unit (CRU) data in reproducing in situ observation in the TRB is analyzed. All considered WRF simulations capture well the annual as well as the interannual and spatial distribution of precipitation in the TRB according to station data and the TRMM estimates. Our results demonstrate that the increase of horizontal resolution from 50 to 25 km, together with the use of the MODIS land use classification, significantly improves the precipitation results. In the case of temperature, spatial patterns and seasonal cycle are well reproduced, although there is a systematic cold bias with respect to both station and CRU data. Our results contribute to the identification of suitable and regionally adapted regional climate models (RCMs) for East Africa.

     

A new estimate of volatile outgassing on Mars

The presence of 28% argon on Mars as calculated by Levine and Riegler and indirectly inferred from Soviet Mars-6 lander data has important implications for the outgassing history of H₂O, CO₂, and N₂ on Mars. Even if the terrestrial volatile outgassing ratio is only approximately valid for Mars, then large quantities of H₂O [of the order of 10⁵ gcm^?2 (about 10⁸ more H₂O than is currently present in the Martian atmosphere)] and about 10⁴ gcm^?2 of CO₂ (about 10³ times more CO₂ than found at present in the Martian atmosphere) and some 450 gcm^?2 of N₂ may have outgassed over the history of Mars.     

Nonlinear FE model updating and reconstruction of the response of an instrumented seismic isolated bridge to the 2010 Maule Chile earthquake

Nonlinear finite element (FE) modeling has been widely used to investigate the effects of seismic isolation on the response of bridges to earthquakes. However, most FE models of seismic isolated bridges (SIB) have used seismic isolator models calibrated from component test data, while the prediction accuracy of nonlinear FE models of SIB is rarely addressed by using data recorded from instrumented bridges. In this paper, the accuracy of a state‐of‐the‐art FE model is studied through nonlinear FE model updating (FEMU) of an existing instrumented SIB, the Marga‐Marga Bridge located in Viña del Mar, Chile. The seismic isolator models are updated in 2 phases: component‐wise and system‐wise FEMU. The isolator model parameters obtained from 23 isolator component tests show large scatter, and poor goodness of fit of the FE‐predicted bridge response to the 2010 Mw 8.8 Maule, Chile Earthquake is obtained when most of those parameter sets are used for the isolator elements of the bridge model. In contrast, good agreement is obtained between the FE‐predicted and measured bridge response when the isolator model parameters are calibrated using the bridge response data recorded during the mega‐earthquake. Nonlinear FEMU is conducted by solving single‐ and multiobjective optimization problems using high‐throughput cloud computing. The updated FE model is then used to reconstruct response quantities not recorded during the earthquake, gaining more insight into the effects of seismic isolation on the response of the bridge during the strong earthquake.     

Surface evolution of dissolving minerals investigated with a kinetic Ising model

In natural weathering systems, both the chemistry and the topography of mineral surfaces change as rocks and minerals equilibrate to surface conditions. Most geochemical research has focused on changes in solution chemistry over time; however, temporal changes in surface topography may also yield information about rates and mechanisms of dissolution. We use stochastic dissolution simulations of a regular 2-D lattice with reaction mechanisms defined in terms of nearest neighbor interactions to elucidate how the surface area and reactivity of a crystal evolve during dissolution. Despite the simplicity of the model, it reproduces key features observed or inferred for mineral dissolution. Our model results indicate that: (i) dissolving surfaces reach a steady-state conformation after sufficient dissolution time, (ii) linear defects cause surface area and dissolution rate to vary in concert with one another, (iii) sigmoidal and non-sigmoidal rate vs. free-energy of reaction (ΔG_rxn) behavior can be rationalized in terms of the multiple steps occurring during dissolution, and (iv) surface roughness as a function of ΔG_rxn is highly sensitive to the reaction mechanism. When simulated times to reach steady-state are compared to published time series rate data using suitable scaling, good agreement is found for silicate minerals while the model significantly over-predicts the duration of the transient for Fe and Al oxides. The implication of our simple model is that many aspects of mineral dissolution behavior, including approach to steady-state, sigmoidal vs. non-sigmoidal rate vs. ΔG_rxn behavior, and development of rougher surfaces in conditions further from equilibrium can be explained by nearest neighbor interactions and simple Kossel-type models where reactivity of a surface is defined in terms of perfect surface, step, and kink sites.     

Comparison of ground-based and Viking Orbiter measurements of Martian water vapor: Variability of the seasonal cycle

Earth-based observations of Mars atmospheric water vapor, made from McDonald Observatory, are presented for the 1975–1976, 1977–1978, and 1983 apparitions. Comparisons are made with near-simultaneous spacecraft measurements made from the Viking Orbiter MarsAtmospheric Water Detection experiment during 1976–1978 and with previous Earth-based measurements (made since 1964). Differences occur between the behavior in the different years, and may be related to the Mars climate. Measurements during the southern summer in 1969 indicate a factor of three times as much water as is present at this same season in other years.This difference may have resulted from the sublimation of water from the south polar residual cap upon removal of most or all of the CO₂ ice present; sublimation of all the CO₂ ice during some years could be a result of a greater thermal load being placed on the cap due to the presence of differing amounts of atmospheric dust. If substantiated, the water vapor variability will turn out to be a very sensitive indicator of yearly variability in the Martian climate.     

Organic matter: size fraction relationships for recent sediments from the Orinoco Delta,Venezuela

Fifteen recent sediment samples from the offshore Orinoco Delta, Venezuela, were separated by sieving and pipette analysis into seven size fractions ranging from 4ø to 10ø, in 1 ø units. Total organic carbon was determined for each size fraction and the organic matter characterized by pyrolysis and pyrolysis-gas chromatography. The sediments average 0.98% organic matter with somewhat higher values nearshore. Nearshore sediments also had higher organic contents in the coarsest fractions and a decrease in organic matter from coarse to fine sediment fractions. Sediments from further offshore generally show the highest organic contents in the finer fractions. Pyrolysis showed a low bitumen content and confirmed that the kerogen was dominantly terrestrial and gas prone. The observed trends were attributed to sorting of organic matter by its physical characteristics, with the denser, coarse-grained material settling out nearshore and the Finer-grained material being carried further from shore and settling out with finer-grained sediments.