Controls on Fe reduction and mineral formation by a subsurface bacterium

The reductive dissolution of FeIII (hydr)oxides by dissimilatory iron-reducing bacteria (DIRB) could have a large impact on sediment genesis and Fe transport. If DIRB are able to reduce FeIII in minerals of high structural order to carry out anaerobic respiration, their range could encompass virtually every O₂-free environment containing FeIII and adequate conditions for cell growth. Previous studies have established that Shewanella putrefaciens CN32, a known DIRB, will reduce crystalline Fe oxides when initially grown at high densities in a nutrient-rich broth, conditions that poorly model the environments where CN32 is found. By contrast, we grew CN32 by batch culture solely in a minimal growth medium. The stringent conditions imposed by the growth method better represent the conditions that cells are likely to encounter in their natural habitat. Furthermore, the expression of reductases necessary to carry out dissimilatory Fe reduction depends on the method of growth. It was found that under anaerobic conditions CN32 reduced hydrous ferric oxide (HFO), a poorly crystalline FeIII mineral, and did not reduce suspensions containing 4 mM FeIII in the form of poorly ordered nanometer-sized goethite (α-FeOOH), well-ordered micron-sized goethite, or nanometer-sized hematite (α-Fe₂O₃) crystallites. Transmission electron microscopy (TEM) showed that all minerals but the micron-sized goethite attached extensively to the bacteria and appeared to penetrate the outer cellular membrane. In the treatment with HFO, new FeII and FeIII minerals formed during reduction of HFO-Fe in culture medium containing 4.0 mmol/L P_i (soluble inorganic P), as observed by TEM with energy-dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The minerals included magnetite (Fe₃O₄), goethite, green rust, and vivianite [Fe₃(PO₄)₂ · 8H₂O]. Vivianite appeared to be the stable end product and the mean coherence length was influenced by the rate of FeIII reduction. When P_i was 0.4 mol/L under otherwise identical conditions, goethite was the only mineral observed to form, and less Fe²⁺ was produced overall. Hence, the ability of DIRB to reduce Fe (hydr)oxides may be limited when the bacteria are grown under nutrient-limited conditions, and the minerals that result depend on the vigor of FeIII reduction.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.     

Turbulence Statistics Above And Within Two Amazon Rain Forest Canopies

The turbulence structure in two Amazon rain forestswas characterised for a range of above-canopystability conditions, and the results compared withprevious studies in other forest canopies and recenttheory for the generation of turbulent eddies justabove forest canopies. Three-dimensional wind speedand temperature fluctuation data were collectedsimultaneously at up to five levels inside and abovetwo canopies of 30–40 m tall forests, during threeseparate periods. We analysed hourly statistics, jointprobability distributions, length scales, spatialcorrelations and coherence, as well as power spectraof vertical and horizontal wind speed.The daytime results show a sharp attenuation ofturbulence in the top third of the canopies, resultingin very little movement, and almost Gaussianprobability distributions of wind speeds, in the lowercanopy. This contrasts with strongly skewed andkurtotic distributions in the upper canopy. At night,attenuation was even stronger and skewness vanishedeven in the upper canopy. Power spectral peaks in thelower canopy are shifted to lower frequencies relativeto the upper canopy, and spatial correlations andcoherences were low throughout the canopy. Integrallength scales of vertical wind speed at the top of thecanopy were small, about 0.15 h compared to avalue of 0.28 h expected from the shear lengthscale at the canopy top, based on the hypothesis that theupper canopy air behaves as a plane mixing layer. Allthis suggests that, although exchange is not totallyinhibited, tropical rain forest canopies differ from other forests in that rapid, coherentdownward sweeps do not penetrate into the lowercanopy, and that length scales are suppressed. This isassociated with a persistent inversion of stability inthat region compared to above-canopy conditions. Theinversion is likely to be maintained by strong heatabsorption in the leaves concentrated near thecanopy top, with the generally weak turbulence beingunable to destroy the temperature gradients over thelarge canopy depth.     

The High Concentration Tails Of The Probability Density Function Of A Dispersing Scalar In The Atmosphere

The distribution function for concentrations of a scalar pollutant dispersing in the turbulent atmosphere has a finite domain that is bounded above and below. Three methods, based on extreme value statistics, are used to obtainestimates for the upper bound and to describe the high concentration tailbehaviour of the distribution; all three methods are applied to concentrationdata obtained from experimental atmospheric releases. Quantile quantile (QQ)plots are used to assess the goodness of fit of the resulting estimates of thedistribution, and also to compare the performance of the three methods. Thepredicted values for the upper bound are orders of magnitude less than thesource concentration, illustrating that molecular diffusion has a large effecton the high concentrations.     

Kolmogoroff constants at the 1976 ITCE

The high-frequency data from 12 sensors at the ITCE 1976^* are analysed to determine the Kolmogoroff constants for velocity, temperature and humidity fluctuation, _u , _T , and _q . The occurrence of aliasing in the spectral analysis in some cases together with the limited response of some sensors at the higher frequencies introduces some uncertainties into the analysis. The Soviet sonic anemometer, fine-wire thermometer and infrared hygrometer and the Australian infrared hygrometer provide the best information, namely that% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9qq-f0-yqaqVeLsFr0-vr% 0-vr0db8meaabaqaciGacaGaaeqabaWaaeaaeaaakeaacqaHXoqyda% WgaaWcbaGaamyDaaqabaGccqGH9aqpcaaIWaGaaiOlaiaaiwdacaaI% 5aGaeyySaeRaaGimaiaac6cacaaIWaGaaGymaiaacYcacaqGGaGaae% iiaiaabccacaqGGaGaeqySde2aaSbaaSqaaiaadsfaaeqaaOGaeyyp% a0JaaGimaiaac6cacaaI2aGaaGioaiabgglaXkaaicdacaGGUaGaaG% imaiaaikdacaGGSaGaaeiiaiaabccacaqGGaGaaeiiaiabeg7aHnaa% BaaaleaacaWGXbaabeaakiabg2da9iaaicdacaGGUaGaaG4naiaaiA% dacqGHXcqScaaIWaGaaiOlaiaaicdacaaIZaaaaa!6248!\[\alpha _u = 0.59 \pm 0.01,{\text{ }}\alpha _T = 0.68 \pm 0.02,{\text{ }}\alpha _q = 0.76 \pm 0.03\]where the errors quoted refer solely to statistical errors. The other instruments provide general support to these values.The technique of using spectral density measurements to determine eddy fluxes is illustrated.International Turbulence Comparison Experiment.     

MAROS: a decision support system for optimizing monitoring plans

The Monitoring and Remediation Optimization System (MAROS), a decision-support software, was developed to assist in formulating cost-effective ground water long-term monitoring plans. MAROS optimizes an existing ground water monitoring program using both temporal and spatial data analyses to determine the general monitoring system category and the locations and frequency of sampling for future compliance monitoring at the site. The objective of the MAROS optimization is to minimize monitoring locations in the sampling network and reduce sampling frequency without significant loss of information, ensuring adequate future characterization of the contaminant plume. The interpretive trend analysis approach recommends the general monitoring system category for a site based on plume stability and site-specific hydrogeologic information. Plume stability is characterized using primary lines of evidence (i.e., Mann-Kendall analysis and linear regression analysis) based on concentration trends, and secondary lines of evidence based on modeling results and empirical data. The sampling optimization approach, consisting of a two-dimensional spatial sampling reduction method (Delaunay method) and a temporal sampling analysis method (Modified CES method), provides detailed sampling location and frequency results. The Delaunay method is designed to identify and eliminate redundant sampling locations without causing significant information loss in characterizing the plume. The Modified CES method determines the optimal sampling frequency for a sampling location based on the direction, magnitude, and uncertainty in its concentration trend. MAROS addresses a variety of ground water contaminants (fuels, solvents, and metals), allows import of various data formats, and is designed for continual modification of long-term monitoring plans as the plume or site conditions change over time.     

Secondary chaotic terrain formation in the higher outflow channels of southern circum-Chryse, Mars

Higher outflow channel dissection in the martian region of southern circum-Chryse appears to have extended from the Late Hesperian to the Middle Amazonian Epoch. These outflow channels were excavated within the upper 1 km of the cryolithosphere, where no liquid water is expected to have existed during these geologic epochs. In accordance with previous work, our examination of outflow channel floor morphologies suggests the upper crust excavated by the studied outflow channels consisted of a thin (a few tens of meters) layer of dry geologic materials overlying an indurated zone that extends to the bases of the investigated outflow channels (1 km in depth). We find that the floors of these outflow channels contain widespread secondary chaotic terrains (i.e., chaotic terrains produced by the destruction of channel-floor materials). These chaotic terrains occur within the full range of outflow channel dissection and tend to form clusters. Our examination of the geology of these chaotic terrains suggests that their formation did not result in the generation of floods. Nevertheless, despite their much smaller dimensions, these chaotic terrains are comprised of the same basic morphologic elements (e.g., mesas, knobs, and smooth deposits within scarp-bound depressions) as those located in the initiation zones of the outflow channels, which suggests that their formation must have involved the release of ground volatiles. We propose that these chaotic terrains developed not catastrophically but gradually and during multiple episodes of nested surface collapse. In order to explain the formation of secondary chaotic terrains within zones of outflow channel dissection, we propose that the regional Martian cryolithosphere contained widespread lenses of volatiles in liquid form. In this model, channel floor collapse and secondary chaotic terrain formation would have taken place as a consequence of instabilities arising during their exhumation by outflow channel dissection. Within relatively warm upper crustal materials in volcanic settings, or within highly saline crustal materials where cryopegs developed, lenses of volatiles in liquid form within the cryolithosphere could have formed, and/or remained stable.In addition, our numerical simulations suggest that low thermal conductivity, dry fine-grained porous geologic materials just a few tens of meters in thickness (e.g., dunes, sand sheets, some types of regolith materials), could have produced high thermal anomalies resulting in subsurface melting. The existence of a global layer of dry geologic materials overlying the cryolithosphere would suggest that widespread lenses of fluids existed (and may still exist) at shallow depths wherever these materials are fine-grained and porous. The surface ages of the investigated outflow channels and chaotic terrains span a full 500 to 700 Myr. Chaotic terrains similar in dimensions and morphology to secondary chaotic terrains are not observed conspicuously throughout the surface of Mars, suggesting that intra-cryolithospheric fluid lenses may form relatively stable systems. The existence of widespread groundwater lenses at shallow depths of burial has tremendous implications for exobiological studies and future human exploration. We find that the clear geomorphologic anomaly that the chaotic terrains and outflow channels of southern Chryse form within the Martian landscape could have been a consequence of large-scale resurfacing resulting from anomalously extensive subsurface melt in this region of the planet produced by high concentrations of salts within the regional upper crust. Crater count statistics reveal that secondary chaotic terrains and the outflow channels within which they occur have overlapping ages, suggesting that the instabilities leading to their formation rapidly dissipated, perhaps as the thickness of the cryolithosphere was reset following the disruption of the upper crustal thermal structure produced during outflow channel excavation.     

Geoarchaeological evidence on a Late Bronze Age earthquake,Ohrid Basin (North Macedonia)

Geoarchaeological investigations on the northeastern shore of Lake Ohrid revealed 3.5 m thick deepwater lacustrine sediments overlying terrestrial vegetation macrofossils, worked wood and abundant potsherds dated to the Late Bronze Age (LBA). Distinct contact of deepwater sediment with the sub-aerial weathered limestone bedrock point to a sudden increase in lake level. According to radiocarbon data, catastrophic flooding occurred shortly after 1214 yr bc. Because the area is located in a highly active seismic zone, we propose that this event was caused by tectonically induced, metre-scale coseismic subsidence related to faults bordering the Ohrid alluvial plain. Moreover, this event coincides well with a dramatic switch in the habitation and settlement strategy in the region. More important, however, is the finding that the age of the proposed massive tectonic event and change in habitation lies within the interval of the proposed ‘earthquake storm’ in the eastern Mediterranean dated to 1225–1175 bc. As the Ohrid-Korça zone belongs to the same tectonic province, a relationship between the abovementioned earthquakes and the proposed event can be expected. This research therefore might provide the first direct evidence of a large-scale earthquake event linkable to the LBA collapse of Europe's first urban civilisation in the Aegean.     

Numerical Simulation Of Oil/Oily-Contaminant Migration And Entrapment In A Lenticular Reservoir

Numerical simulations show that water and oil/oily-contaminant migration are controlled by regional fluid-potential fields which may be modified locally by highly permeable lenses and buoyancy. In addition, fluid potentials are coupled to the distribution of oil/oily-contaminant via relative permeability and capillary-pressure curves. As saturation distributions evolve through space and time, so do the water and oil fluid-potential surfaces. The importance of capillary forces in oil contaminant migration and entrapment is illustrated by the fact that, in certain cases, lenses fill from above, even when the migrating fluid is lighter than water. Capillary forces operating in conjunction with lenticular reservoirs create excellent dynamic oil traps by allowing free passage of water, while retaining and concentrating oil. The analysis of oil (oily-contaminant) migration using numerical modeling and potentiometric-surface techniques is useful for the prediction of migration pathways and potential accumulation sites. On the other hand, identifying acatual accumulations from fluid-potential measurements (via inverse modeling) is not possible because fluid potentials are not uniquely dependent on saturation.     

X-ray absorption contrast images of binary chemical reactions

Low-divergence synchrotron-sourced X-rays enable a radiographic imaging scheme for full characterization of binary chemical reactions and characterization by type of more complex reactions, in situ, in diamond anvil cells (DAC). Spatially resolved reactants are induced to react by laser heating of their interface. The spatially intermediate products are observed through X-ray absorption contrast. Limits to the technique include the ability to maintain controlled experiment geometry during compression and the ability to resolve chemical differences between reactants and products by X-ray absorption. The ability to make in situ observations at experimental pressure and temperature obviates the problem with quenching techniques for capturing liquid compositions in experiments with dimensions smaller than the diffusion length during quenching time. Partially molten Fe-alloy systems, of poor quenchability, are examined at DAC pressures and temperatures for relevance to Earth's core constitution and evolution. Determinations of eutectic melting in Fe–FeS match known results. Of the probable light elements that may alloy with Fe in the Earth's liquid outer core, Fe–FeS experiments show only modest quenching problems, but C and Si alloy experiments are highly vulnerable to quenching artifacts. The observed reactivity of FeS, Fe₃C, FeSi, and FeO(OH) with Fe in DAC makes the observed non-reactivity between Fe and FeO more significant, reducing the probability that oxygen alone is the major alloy in Earth's molten outer core.