Microscale investigations of microbial communities in coastal surficial sediments

The upper millimeters of sediments are considered major locations of microbial colonization and activity. The goal of our study was to investigate variations of microbial communities in the uppermost sediment layers of the coastal Baltic Sea with emphasis on the complex interplay between microbiology and physico‐chemical sediment properties. We selected a high‐resolution methodological approach that combined the cryolanding sampling technique (spatial resolution of 250 μm) with microsensor‐, spectrophotometric and microscopic analyses. While the oxygen penetration depths in dark conditions ranged from 1.4 mm to 2.6 mm during the study period, this zone expanded by about 1 mm in light and could be divided into three micro‐horizons: (i) an upper zone with a high net O₂ production, (ii) an intermediate zone with increased O₂ consumption on account of light‐stimulated respiration and (iii) a lower zone with lower O₂ consumption. Time‐series experiments revealed a rapid response of the benthic microbial community to altered light intensities. In May and July, the net O₂ budget in the porewater of sediments was positive within 35 and 22 min after illumination, respectively, whereas in June O₂ production exceeded O₂ consumption after 112 min. The thickness of the O₂ production and O₂ consumption micro‐zones decreased from May to July coinciding with an increase in temperature. In May, sites of enhanced O₂ consumption were closely associated with subsurface maxima of microbial numbers and enzymatic activities indicating a tight coupling between photoautotrophic and heterotrophic processes between 1‐ and 2‐mm depth. In June and July, the microbial abundance and enzymatic activity hardly varied with depth. Spatial and temporal microheterogeneity of microbial distribution and activity in O₂ gradients was seen as a reflection of the complex interplay between microbiology and physico‐chemical sediment properties.     

The Multiscale TROPIcal CatchmentS critical zone observatory M-TROPICS dataset II: Land use,hydrology and sediment production monitoring in Houay Pano,northern Lao PDR

Mountain regions of the humid tropics are characterized by steep slopes and heavy rains. These regions are thus prone to both high surface runoff and soil erosion. In Southeast Asia, uplands are also subject to rapid land-use change, predominantly as a result of increased population pressure and market forces. Since 1998, the Houay Pano site, located in northern Lao PDR (19.85°N 102.17°E) within the Mekong basin, aims at assessing the long-term impact of the conversion of traditional slash-and-burn cultivation systems to commercial perennial monocultures such as teak tree plantations, on the catchment hydrological response and sediment yield. The instrumented site monitors hydro-meteorological and soil loss parameters at both microplot (1 m²) and small catchment (0.6 km²) scales. The monitored catchment is part of the network of critical zone observatories named Multiscale TROPIcal CatchmentS (M-TROPICS). The data shared by M-TROPICS in Houay Pano are (1) rainfall, (2) air temperature, air relative humidity, wind speed, and global radiation, (3) catchment land use, (4) stream water level, suspended particulate matter, bed particulate matter and stones, (5) soil surface features, and (6) soil surface runoff and soil detachment. The dataset has already been used to interpret suspended particulate matter and bed particulate matter sources and dynamics, to assess the impact of land-use change on catchment hydrology, soil erosion, and sediment yields, to understand bacteria fate and weed seed transport across the catchment, and to build catchment-scale models focused on hydrology and water quality issues. The dataset may be further used to, for example, assess the role of headwater catchments in large tropical river basin hydrology, support the interpretation of new variables measured in the catchment (e.g., contaminants other than faecal bacteria), and assess the relative impacts of both climate and land-use change on the catchment.     

Modeling aqueous perchlorate chemistries with applications to Mars

NASA’s Phoenix lander identified perchlorate and carbonate salts on Mars. Perchlorates are rare on Earth, and carbonates have largely been ignored on Mars following the discovery by NASA’s Mars Exploration Rovers of acidic precipitated minerals such as jarosite. In light of the Phoenix results, we updated the aqueous thermodynamic model FREZCHEM to include perchlorate chemistry. FREZCHEM models the Na-K-Mg-Ca-Fe(II)-Fe(III)-Al-H-Cl-Br-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-O₂-CH₄-Si-H₂O system, with 95 solid phases. We added six perchlorate salts: NaClO₄·H₂O, NaClO₄·2H₂O, KClO₄, Mg(ClO₄)₂·6H₂O, Mg(ClO₄)₂·8H₂O, and Ca(ClO₄)₂·6H₂O. Modeled eutectic temperatures for Na, Mg, and Ca perchlorates ranged from 199 K (−74 °C) to 239 K (−34 °C) in agreement with experimental data.We applied FREZCHEM to the average solution chemistry measured by the Wet Chemistry Laboratory (WCL) experiment at the Phoenix site when soil was added to water. FREZCHEM was used to estimate and alkalinity concentrations that were missing from the WCL data. The amount of is low compared to estimates from elemental abundance made by other studies on Mars. In the charge-balanced solution, the dominant cations were Mg²⁺ and Na⁺ and the dominant anions were , and alkalinity. The abundance of calcite measured at the Phoenix site has been used to infer that the soil may have been subject to liquid water in the past, albeit not necessarily locally; so we used FREZCHEM to evaporate (at 280.65 K) and freeze (from 280.65 to 213.15 K) the WCL-measured solution to provide insight into salts that may have been in the soil. Salts that precipitated under both evaporation and freezing were calcite, hydromagnesite, gypsum, KClO₄, and Mg(ClO₄)₂·8H₂O. Epsomite (MgSO₄·7H₂O) and NaClO₄·H₂O were favored by evaporation at temperatures >0 °C, while meridianite (MgSO₄·11H₂O), MgCl₂·12H₂O, and NaClO₄·2H₂O were favored at subzero temperatures. Incongruent melting of such highly hydrated salts could be responsible for vug formation elsewhere on Mars.All K⁺ precipitated as insoluble KClO₄ during both evaporation and freezing simulations, accounting for 15.8% of the total perchlorates. During evaporation, 35.8% of perchlorates precipitated with Na⁺ and 48.4% with Mg²⁺. During freezing, 58.4% precipitated with Na⁺ and 24.8% with Mg²⁺. Given its low eutectic temperature, the existence of Mg(ClO₄)₂ in either case allows for the possibility of liquid brines on Mars today. FREZCHEM also showed that Ca(ClO₄)₂ would likely not have precipitated at the Phoenix landing site due to the strong competing sinks for Ca as calcite and gypsum. Overall, these results help constrain the salt mineralogy of the soil. Differences between evaporites and cryogenites suggest ways to discriminate between evaporation and freezing during salt formation. Future efforts, such as sample return or in situ X-ray diffraction, may make such a determination possible.     

Br/Cl partitioning in chloride minerals in the Burns formation on Mars

Within Gusev Crater and Meridiani Planum on Mars, the Mars exploration rovers have found Br concentrations in soils and rocks in the hundreds of ppm range. Relative to Earth compositions, these are high Br concentrations. Because of low Br concentrations on Earth, Br largely precipitates from seawater as a minor constituent in halite crystals rather than as a separate phase mineral. This is also likely to be the case for Mars. But given that the surface chemistries on Mars are significantly different than on Earth, minerals other than halite could serve as sinks for Br. The specific objectives of this paper were to (1) incorporate Br solution phase chemistries into the FREZCHEM model, (2) integrate the Siemann–Schramm Br/Cl mineral model into FREZCHEM, and (3) apply this mineral model to Br/Cl partitioning in Burns formation rocks as an indicator of past environments in the Meridiani Planum region of Mars. We showed that: (1) a molar-based model for Br substitution into halite and bischofite provided a better fit to experimental data than the standard mass-based model; (2) the concentrations of all of the soluble salts (mainly of Na, Mg, Ca, Cl, Br, and SO₄) in the Burns formation, except for Ca, were significantly related to stratigraphic depth; (3) the likely precipitation of Ca as gypsum on Mars precluded Ca precipitating as a CaCl₂ salt and thus impacts the possible minimum eutectic brine temperatures relevant to the Burns formation; (4) bischofite (MgCl₂⋅6H₂O) was a much more important sink for Br than halite; (5) Br/Cl patterns in the Burns formation, and within the three formation layers, argued in support of salt upwelling through groundwater evaporation; and (6) the high concentrations of Br in the surface layers of the Burns formation suggested that there was little water leaching and removal of soluble phases from the upper part of the stratigraphic succession.     

Modeling aluminum-silicon chemistries and application to Australian acidic playa lakes as analogues for Mars

Recent Mars missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major relevant findings are the presence in Meridiani Planum sediments of the mineral jarosite (a ferric sulfate salt) and related minerals that require formation from an acid-salt brine and oxidizing environment. Similar mineralogies have been observed in acidic saline lake sediments in Western Australia (WA), and these lakes have been proposed as analogues for acidic sedimentary environments on Mars. The prior version of the equilibrium chemical thermodynamic FREZCHEM model lacked Al and Si chemistries that are needed to appropriately model acidic aqueous geochemistries on Earth and Mars. The objectives of this work were to (1) add Al and Si chemistries to the FREZCHEM model, (2) extend these chemistries to low temperatures (<0 °C), if possible, and (3) use the reformulated model to investigate parallels in the mineral precipitation behavior of acidic Australian lakes and hypothetical Martian brines.FREZCHEM is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Aluminum chloride and sulfate mineral parameterizations were based on experimental data. Aluminum hydroxide and silicon mineral parameterizations were based on Gibbs free energy and enthalpy data. New aluminum and silicon parameterizations added 12 new aluminum/silicon minerals to this Na-K-Mg-Ca-Fe(II)-Fe(III)-Al-H-Cl-Br-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-O₂-CH₄-Si-H₂O system that now contain 95 solid phases.There were similarities, differences, and uncertainties between Australian acidic, saline playa lakes and waters that likely led to the Burns formation salt accumulations on Mars. Both systems are similar in that they are dominated by (1) acidic, saline ground waters and sediments, (2) Ca and/or Mg sulfates, and (3) iron precipitates such as jarosite and hematite. Differences include: (1) the dominance of NaCl in many WA lakes, versus the dominance of Fe-Mg-Ca-SO₄ in Meridiani Planum, (2) excessively low K⁺ concentrations in Meridiani Planum due to jarosite precipitation, (3) higher acid production in the presence of high iron concentrations in Meridiani Planum, and probably lower rates of acid neutralization and hence, higher acidities on Mars owing to colder temperatures, and (4) lateral salt patterns in WA lakes. The WA playa lakes display significant lateral variations in mineralogy and water chemistry over short distances, reflecting the interaction of acid ground waters with neutral to alkaline lake waters derived from ponded surface runoff. Meridiani Planum observations indicate that such lateral variations are much less pronounced, pointing to the dominant influence of ground water chemistry, vertical ground water movements, and aeolian processes on the Martian surface mineralogy.     

Seasonal variation in the toxicity of sediment-associated contaminants in Corpus Christi Bay, TX

Seasonal variation in pore water and sediment-water interface (SWI) toxicity at two sites of suspected contamination was investigated using sea urchin embryological development (Arbacia punctulata) and copepod hatching success (Schizopera knabeni). Site S1, located inside a marina, was fine-grained and S2, located near a neighboring stormwater outfall, was sandy. Both sites were cored in summer and winter, along with reference sites of equivalent grain sizes. Whereas the muddy contaminated site displayed a slight decrease in sea urchin toxicity from summer to winter, pore water from the sandy contaminated site exhibited an increase in sea urchin toxicity. The sandy sites displayed slight toxicity increase to copepod hatching success in winter, which occurred in the SWI of S2 and in the pore water from the reference site, R2, where it coincided with sedimentation. Cu was the most prevalent metal in the sediment samples. Although Cu concentration increased in the whole sediments and pore waters from summer to winter, its concentration in overlying SWI exposure decreased from summer to winter. Organic compounds exhibited opposite behavior, with smaller variety identified in the winter pore water samples, but more chemicals detected in the SWI samples in winter.     

Skill assessment of three earth system models with common marine biogeochemistry

We have assessed the ability of a common ocean biogeochemical model, PISCES, to match relevant modern data fields across a range of ocean circulation fields from three distinct Earth system models: IPSL-CM4-LOOP, IPSL-CM5A-LR and CNRM-CM5.1. The first of these Earth system models has contributed to the IPCC 4th assessment report, while the latter two are contributing to the ongoing IPCC 5th assessment report. These models differ with respect to their atmospheric component, ocean subgrid-scale physics and resolution. The simulated vertical distribution of biogeochemical tracers suffer from biases in ocean circulation and a poor representation of the sinking fluxes of matter. Nevertheless, differences between upper and deep ocean model skills significantly point to changes in the underlying model representations of ocean circulation. IPSL-CM5A-LR and CNRM-CM5.1 poorly represent deep-ocean circulation compared to IPSL-CM4-LOOP degrading the vertical distribution of biogeochemical tracers. However, their representations of surface wind, wind stress, mixed-layer depth and geostrophic circulations (e.g., Antarctic Circumpolar Current) have been improved compared to IPSL-CM4-LOOP. These improvements result in a better representation of large-scale structure of biogeochemical fields in the upper ocean. In particular, a deepening of 20–40 m of the summer mixed-layer depth allows to capture the 0–0.5 μgChl L^?1 concentrations class of surface chlorophyll in the Southern Ocean. Further improvements in the representation of the ocean mixed-layer and deep-ocean ventilation are needed for the next generations of models development to better simulate marine biogeochemistry. In order to better constrain ocean dynamics, we suggest that biogeochemical or passive tracer modules should be used routinely for both model development and model intercomparisons.     

Nickeliferous pyrite tracks pervasive hydrothermal alteration in Martian regolith breccia: A study in NWA 7533

Martian regolith breccia NWA 7533 (and the seven paired samples) is unique among Martian meteorites in showing accessory pyrite (up to 1% by weight). Pyrite is a late mineral, crystallized after the final assembly of the breccia. It is present in all of the lithologies, i.e., the fine‐grained matrix (ICM), clast‐laden impact melt rocks (CLIMR), melt spherules, microbasalts, lithic clasts, and mineral clasts, all lacking magmatic sulfides due to degassing. Pyrite crystals show combinations of cubes, truncated cubes, and octahedra. Polycrystalline clusters can reach 200 μm in maximum dimensions. Regardless of their shape, pyrite crystals display evidence of very weak shock metamorphism such as planar features, fracture networks, and disruption into subgrains. The late fracture systems acted as preferential pathways for partial replacement of pyrite by iron oxyhydroxides interpreted as resulting from hot desert terrestrial alteration. The distribution and shape of pyrite crystals argue for growth at moderate to low growth rate from just‐saturated near neutral (6 < pH<10), H₂S‐HS‐rich fluids at minimum log fO₂ of >FMQ + 2 log units. It is inferred from the maximum Ni contents (4.5 wt%) that pyrite started crystallizing at 400–500 °C, during or shortly after a short‐duration, relatively low temperature, thermal event that lithified and sintered the regolith breccias, 1.4 Ga ago as deduced from disturbance in several isotope systematics.     

Modelling time varying scouring at bed sills

In this paper a modelling approach is presented to predict local scour under time varying flow conditions. The approach is validated using experimental data of unsteady scour at bed sills. The model is based on a number of hypotheses concerning the characteristics of the flow hydrograph, the temporal evolution of the scour and the geometry of the scour hole. A key assumption is that, at any time, the scour depth evolves at the same rate as in an equivalent steady flow. The assumption is supported by existing evidence of geometrical affinity and similarity of scour holes formed under different steady hydraulic conditions. Experimental data are presented that show the scour hole development downstream of bed sills due to flood hydrographs follow a predictable pattern. Numerical simulations are performed with the same input parameters used in the experimental tests but with no post‐simulation calibration. Comparison between the experimental and model results indicates good correspondence, especially in the rising limb of the flow hydrograph. This suggests that the underlying assumptions used in the modelling approach are appropriate. In principle, the approach is general and can be applied to a wide range of environments (e.g. bed sills, step‐pool systems) in which scouring at rapid bed elevation changes caused by time varying flows occurs, provided appropriate scaling information is available, and the scour response to steady flow conditions can be estimated. Copyright © 2011 John Wiley & Sons, Ltd.     

Sphalerite oxidation pathways detected by oxygen and sulfur isotope studies

Sphalerite oxidation is a common process under acid-mine drainage (AMD) conditions and results in the release of , Zn and potentially toxic trace metals, which can pollute rivers and oceans. However, there are only a few studies on the mechanisms of aerobic sphalerite oxidation. Oxygen and S isotope investigations of the produced may contribute to the understanding of sphalerite oxidation mechanisms so helping to interpret field data from AMD sites. Therefore, batch oxidation experiments with an Fe-rich sphalerite were performed under aerobic abiotic conditions at different initial pH values (2 and 6) for different lengths of time (2–100 days). The O and S isotope composition of the produced indicated changing oxidation pathways during the experiments. During the first 20 days of the experiments at both initial pH values, molecular O₂ was the exclusive O source of . Furthermore, the lack of S isotope enrichment processes between and sphalerite indicated that O₂ was the electron acceptor from sphalerite S. As the oxidation proceeded, a sufficient amount of released Fe(II) was oxidized to Fe(III) by O₂. Therefore, electrons could be transferred from sphalerite S sites to adsorbed hydrous Fe(III) and O from the hydration sphere of Fe was incorporated into the produced as indicated by decreasing δ¹⁸O_SO4 values which became more similar to the δ¹⁸O_H2O values. The enrichment of ³²S in relative to the sphalerite may also result from sphalerite oxidation by Fe(III).The incorporation of O₂ into during the oxidation of sphalerite was associated with an O isotope enrichment factor ε_SO4–O2 of ca. −22‰. The O isotope enrichment factor ε_SO4–H2O was determined to be ?4.1‰. A comparison with O and S studies of other sulfides suggests that there is no general oxidation mechanism for acid-soluble sulfides.