Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works located in Guerrero Negro, Baja California Sur, Mexico. Included in the budget are measured rates of O2 production, sulfate reduction, and elemental exchange across the mat/brine interface, day and night, at various temperatures and times of the year. We infer from this data the various sinks for O2, as well as the sources of carbon for primary production. To summarize, although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Also, oxygenic photosynthesis was the most important process of carbon fixation, although anoxygenic photosynthesis may have been important at low light levels during some times of the year. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount. These mats are thus closely coupled systems where rapid rates of photosynthesis both require and fuel rapid rates of heterotrophic carbon oxidation.     

Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments

Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S-depletions associated with the lowest rates of sulfate reduction and the lowest 34S-depletions with the highest rates. However, at high sulfate reduction rates (>10 micromoles cm-3 d-1) the lowest fractionation was 20% independent of the rates. Overall, there was a similarity between the fractionation obtained by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate reduction (mass cell-1 time-1) and not by the absolute rate (mass volume-1 time-1). Sedimentary sulfides (mainly FeS2) were on average 40% depleted in 34S compared to seawater sulfate. This amount of depletion was more than could be explained by the isotopic fractionations that we measured during bacterial sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying elemental sulfur disproportionation contributes to the 34S depletion of sedimentary sulfides at our study sites.     

The Mees CCD imaging spectrograph

The Mees CCD (MCCD) instrument is an imaging spectroscopy device which uses the 25 cm coronagraph telescope and the 3.0 m Coudé spectrograph at Mees Solar Observatory (MSO) on Haleakala, Maui. The instrument works with resolving power up to R 200 000 with significant throughput from 3934 Å (Caii K) to 10 000 Å. A fast guiding active mirror stabilizes the image during observations. A rapidly writing magnetic tape storage system allows observations to be recorded at 256 kbytes s^–1. Currently, the MCCD is used for imaging spectroscopy of solar flares at 6563 Å (H), and velocity measurements of umbral oscillations; future plans include emission line studies of active region coronae, and photospheric studies of solar oscillations.     

The height variation of granular and oscillatory velocities

Previous observations of spatially-resolved vertical velocity variations in ten lines of Fe i spanning the height range 0 h 1000 km are re-analyzed using velocity weighting functions. The amplitudes and scale heights of granular and oscillatory velocities are determined, as well as those of the remaining unresolved velocities. I find that the optimal representation of the amplitude of the outward-decreasing granular velocities is an exponentially decreasing function of height, with a scale height of 150 km and a velocity at zero height of 1.27 km s^–1. The optimal representation of the same quantities for oscillatory velocities is an exponential increase with height, with a scale height of 1100 km and a velocity at zero height of 0.35 km s^–1. The remaining unresolved velocities decrease with height, with a scale height of 380 km and a velocity at zero height of 2.3 km s^–1.     

Temperature and its control of isotope fractionation by a sulfate-reducing bacterium

A synthesis of previous results, which we dub the “standard model,” provides a prediction as to how isotope fractionation during sulfate reduction should respond to physiological variables such as specific rate of sulfate reduction and environmental variables such as substrate availability and temperature. The standard model suggests that isotope fractionation should decrease with increasing specific rates of sulfate reduction (rate per cell). Furthermore, the standard model predicts that low fractionations should be found at both high and low temperatures whereas the highest fractionations should be found in the intermediate temperature range. These fractionation trends are controlled, as a function of temperature, by the balance between the transfer rates of sulfate into and out of the cell and the exchange between the sulfur pools internal to the organism. We test this standard model by conducting experiments on the growth physiology and isotope fractionation, as a function of temperature, by the sulfate-reducing bacterium Desulfovibrio desulfuricans (DSMZ 642). Our results contrast with the “standard model” by showing a positive correlation between specific rates of sulfate reduction and fractionation. Also by contrast with the standard model, we found the highest fractionations at low and high temperatures and the lowest fractionations in the intermediate temperature range. We develop a fractionation model which can be used to explain both our results as well as the results of the “standard model.” Differences in fractionation with temperature relate to differences in the specific temperature response of internal enzyme kinetics as well as the exchange rates of sulfate in and out of the cell. It is expected that the kinetics of these processes will show strain-specific differences.     

Models of oxic respiration, denitrification and sulfate reduction in zones of coastal upwelling

Coastal upwelling zones support some of the highest rates of primary production in the oceans. The settling and subsequent decomposition of this organic matter promotes oxygen depletion. In the Eastern tropical North and South Pacific and the Arabian Sea, large tracts of anoxic water develop, where intensive N₂ production through denitrification and anammox accounts for about 1/3 of the total loss of fixed nitrogen in the marine realm. It is curious that despite extensive denitrification in these waters, complete nitrate removal and the onset of sulfate reduction is extremely rare. A simple box model is constructed here to reproduce the dynamics of carbon, oxygen and nutrient cycling in coastal upwelling zones. The model is constructed with five boxes, where water is exchanged between the boxes by vertical and horizontal mixing and advection. These primary physical drivers control the dynamics of the system. The model demonstrates that in the absence of nitrogen fixation, the anoxic waters in a coastal upwelling system will not become nitrate free. This is because nitrate is the limiting nutrient controlling primary production, and if nitrate concentration becomes too low, primary production rate drops and this reduces rates of nitrate removal through N₂ production. With nitrogen fixation, however, complete nitrate depletion can occur and sulfate reduction will ensue. This situation is extremely rare in coastal upwelling zones, probably because nitrogen-fixing bacteria do not prosper in the high nutrient, turbid waters as typically in these areas. Finally, it is predicted here that the chemistry of the upwelling system will develop in a similar matter regardless whether N₂ production is dominated by anaerobic ammonium oxidation (anammox) or canonical heterotrophic denitrification.     

Effect of hydrogen limitation and temperature on the fractionation of sulfur isotopes by a deep-sea hydrothermal vent sulfate-reducing bacterium

The fractionation of sulfur isotopes by the thermophilic chemolithoautotrophic Thermodesulfatator indicus was explored during sulfate reduction under excess and reduced hydrogen supply, and the full temperature range of growth (40-80 °C). Fractionation of sulfur isotopes measured under reduced H₂ conditions in a fed-batch culture revealed high fractionations (24-37‰) compared to fractionations produced under excess H₂ supply (1-6‰). Higher fractionations correlated with lower sulfate reduction rates. Such high fractionations have never been reported for growth on H₂. For temperature-dependant fractionation experiments cell-specific rates of sulfate reduction increased with increasing temperatures to 70 °C after which sulfate-reduction rates rapidly decreased. Fractionations were relatively high at 40 °C and decreased with increasing temperature from 40-60 °C. Above 60 °C, fractionation trends switched and increased again with increasing temperatures. These temperature-dependant fractionation trends have not previously been reported for growth on H₂ and are not predicted by a generally accepted fractionation model for sulfate reduction, where fractionations are controlled as a function of temperature, by the balance of the exchange of sulfate across the cell membrane, and enzymatic reduction rates of sulfate. Our results are reproduced with a model where fractionation is controlled by differences in the temperature response of enzyme reaction rates and the exchange of sulfate in and out of the cell.     

The behavior of molybdenum and its isotopes across the chemocline and in the sediments of sulfidic Lake Cadagno, Switzerland

Molybdenum (Mo) isotope studies in black shales can provide information about the redox evolution of the Earth’s oceans, provided the isotopic consequences of Mo burial into its major sinks are well understood. Previous applications of the Mo isotope paleo-ocean redox proxy assumed quantitative scavenging of Mo when buried into sulfidic sediments. This paper contains the first complete suite of Mo isotope fractionation observations in a sulfidic water column and sediment system, the meromictic Lake Cadagno, Switzerland, a small alpine lake with a pronounced oxygen-sulfide transition reaching up to H₂S ∼ 200 μM in the bottom waters (or about 300 μM total sulfide: ΣS²⁻ = H₂S + HS⁻ + S²⁻). We find that Mo behaves conservatively in the oxic zone and non-conservatively in the sulfidic zone, where dissolved Mo concentrations decrease from 14 nM to 2-8 nM across this transition. Dissolved Mo in the upper oxic waters has a δ⁹⁸Mo_oxic = 0.9 ± 0.1‰, which matches that of the riverine input, δ⁹⁸Mo_river = 0.9 ± 0.1‰. In the deeper sulfidic waters, a subaquatic source delivers Mo at 1.55 ± 0.1‰, but the dissolved Mo is even heavier at δ⁹⁸Mo_sulfidic = 1.8‰. Sediment traps in the sulfidic zone of the lake collect particles increasingly enriched in Mo with depth, with δ⁹⁸Mo values significantly fractionated at −0.8‰ to −1.2‰ both near the chemocline and in the deepest trap. Suspended particulates in the sulfidic waters carry lighter Mo than the ambient dissolved Mo pool by ∼0.3-1.5‰. Sedimentary Mo concentrations correlate with total organic carbon and yield Mo levels which are two orders of magnitude higher than typical crustal values found in rocks from the catchment area. Solid-phase Mo in the sediment shows a slightly positive δ⁹⁸Mo trend with depth, from δ⁹⁸Mo = 1.2‰ to 1.4‰ while the pore waters show dramatic enrichments of Mo (>2000 nM) with a relatively light isotope signature of δ⁹⁸Mo = 0.9-1.0‰.These data are explained if Mo is converted to particle-reactive oxythiomolybdates in the sulfidic waters and is fractionated during removal from solution onto particles. Isotope fractionation is expressed in the water column, despite the high sulfide concentrations, because the rate of Mo removal is fast compared to the slow reaction kinetics of thiomolybdate formation. However, elemental and isotopic mass balances show that Mo is indeed quantitatively removed to the lake sediments and thus the isotopic composition of the sediments reflects sources to the sulfidic water. This efficient Mo drawdown is expected to occur in settings where H₂S is very much in excess over Mo or in a restricted setting where the water renewal rate is slow compared to the Mo burial rate. We present a model for the Mo isotope fractionation in sulfidic systems associated with the slow reaction kinetics and conclude that quantitative removal will occur in highly sulfidic and restricted marine systems.     

Observations of photospheric pole-equator temperature differences

Using photoelectric methods we have repeated Plaskett's (1970) measurements of poleequator temperature differences. We average many limb-darkening scans to reduce statistical errors. We then analyze the differences between the average polar and equatorial scans. Plaskett's large poleequator temperature differences are not confirmed. Our data yield a pole-equator temperature difference of 1.5K±0.6K, although we cannot rule out systematic errors of 3–4 K.