Identifying when microbes biosilicify: The interconnected requirements of acidic pH, colloidal SiO2 and exposed microbial surface

This study demonstrates discernible biosilicification of natural microbial mats through batch laboratory experiments. Identification of the geochemical requirements for this process to occur includes thermodynamically favorable, but sluggish silica reaction kinetics associated with acidic conditions, and the necessity for colloidal silica rather than dissolved silicic acid species. This study provides the first results to bridge the apparent literature discrepancy between widespread, in-situ observations of microbial silicification, and the inability to demonstrate a detectable microbial impact in this process under well-constrained laboratory conditions. We compared the silica scavenging abilities of three natural microbial mats collected from Yellowstone National Park (YNP) hotsprings, relative to those of both abiotic particle (TiO₂) and solution controls at constant, near-saturated aqueous silica concentrations, while experimental pH and temperature conditions were varied, using both dissolved and colloidal SiO₂ forms. We specifically evaluated three microbial mats sampled from YNP sites all exhibiting saturation with respect to amorphous SiO₂, but possessing variable pH and temperature conditions that should reflect differential kinetics (and therefore biological opportunity) relative to silica polymerization: (1) most biologically favorable, acidic-mesophile (AM: pH 3, T = 35 °C); (2) biologically possible, but less opportune, alkaline, mesophile (ALK-M: pH 8, T = 35 °C) and (3) unlikely to be biologically favorable, alkaline-thermophile (ALK-T: pH 8, T = 80 °C). Comparison of field and laboratory results substantiates the requirements for thermodynamically favorable, but kinetically slower SiO₂ polymerization conditions. Results show that acidic moderate temperature conditions were required for an observable biosilicification impact. Moreover, they also identified for the first time, the necessity specifically for colloidal silica forms which are surface bound under acidic pH conditions, to distinguish discernible biosilicification compared to mineral particle controls. Results also highlight the important influence of mat surface characteristics in this process, specifically the extent of live, non-mineralized, exposed biological mat surface. Greater colloidal SiO₂ scavenging abilities are associated with non-mineralized microbial mat surfaces than with mineral particle surfaces or microbial mat surfaces encrusted with authigenic silica. These results are the first to demonstrate that biosilicification can be a microbially mediated, discernible geobiological process, shedding new light on the longstanding argument in the literature, and opening the door for more sensitive evaluation of this phenomenon in natural systems.     

History matching for exploring and reducing climate model parameter space using observations and a large perturbed physics ensemble

We apply an established statistical methodology called history matching to constrain the parameter space of a coupled non-flux-adjusted climate model (the third Hadley Centre Climate Model; HadCM3) by using a 10,000-member perturbed physics ensemble and observational metrics. History matching uses emulators (fast statistical representations of climate models that include a measure of uncertainty in the prediction of climate model output) to rule out regions of the parameter space of the climate model that are inconsistent with physical observations given the relevant uncertainties. Our methods rule out about half of the parameter space of the climate model even though we only use a small number of historical observations. We explore 2 dimensional projections of the remaining space and observe a region whose shape mainly depends on parameters controlling cloud processes and one ocean mixing parameter. We find that global mean surface air temperature (SAT) is the dominant constraint of those used, and that the others provide little further constraint after matching to SAT. The Atlantic meridional overturning circulation (AMOC) has a non linear relationship with SAT and is not a good proxy for the meridional heat transport in the unconstrained parameter space, but these relationships are linear in our reduced space. We find that the transient response of the AMOC to idealised CO₂ forcing at 1 and 2 % per year shows a greater average reduction in strength in the constrained parameter space than in the unconstrained space. We test extended ranges of a number of parameters of HadCM3 and discover that no part of the extended ranges can by ruled out using any of our constraints. Constraining parameter space using easy to emulate observational metrics prior to analysis of more complex processes is an important and powerful tool. It can remove complex and irrelevant behaviour in unrealistic parts of parameter space, allowing the processes in question to be more easily studied or emulated, perhaps as a precursor to the application of further relevant constraints.     

Diffusion of osmium in pyrrhotite and pyrite: implications for closure of the Re–Os isotopic system

In order to better constrain the extent to which common sulfide minerals will retain their osmium isotopic composition subsequent to crystallization, we have conducted experiments to quantify the diffusion behavior of osmium in pyrite and pyrrhotite. Experiments consisted of either (1) isothermal soaking of diffusion couples consisting of natural pyrite or pyrrhotite crystals packed against powdered Os-bearing Fe-sulfide or (2) ‘relaxation’ of initially high near-surface osmium concentrations produced in the latter experiments (pyrite only). Osmium penetration into samples was characterized by depth profiling using Rutherford backscattering spectroscopy (RBS) (pyrite) or electron microprobe analyses across sectioned run products (pyrrhotite). Results of the first type of diffusion experiment involving pyrite show only limited osmium penetration into sample surfaces, with the extent of penetration uncorrelated with run duration. Images of pyrite samples using atomic force microscopy show roughening of initially smooth surfaces as a consequence of step formation and suggest that osmium incorporation into the near-surface occurred by solute uptake during step growth and not by volume diffusion. Prolonged (1000⁺ h) ‘relaxation’ experiments revealed no additional osmium penetration into pyrite surfaces and based on the depth resolution for RBS, a maximum diffusion coefficient of 2.5×10⁻²³ m²/s at 500°C was calculated. Experiments involving pyrrhotite over the temperature range of 950–1100°C showed extensive osmium uptake and osmium concentration gradients that conform with Fickian diffusion behavior. We found that pyrrhotite Fe/S could be varied by changes in the composition of the starting material and osmium source and over the range of Fe/S produced in experiments (molar Fe/S=0.83–0.90), we observed no systematic variation in the osmium diffusion coefficient. Diffusion coefficients measured parallel to the a crystallographic axis were on average 1.4× higher than values measured parallel to c and regression of the c-axis data yielded the Arrhenius relation:

The application of these diffusion data to simple models of diffusive exchange during static or polythermal time–temperature histories is used to assess the conditions under which radiogenic osmium will be retained. During isothermal annealing, calculations indicate that the cores of millimeter-sized spherical pyrrhotite crystals undergoing diffusive exchange with an external osmium reservoir will have their initial compositions perturbed in ≤0.5 Ma at temperatures exceeding 400°C. Pyrite undergoing the same process at 500°C requires in excess of 10 Ma before crystal cores are affected. The relatively short ‘core retention’ time-scales for pyrrhotite indicates that this mineral may be prone to isotopic resetting following relatively brief crustal thermal events, thus possibly accounting for the scatter that commonly occurs in Re–Os isochrons generated from massive sulfide samples. Calculated closure temperatures (T_c) for osmium exchange in pyrrhotite yielded values of 300–400°C for grain sizes ranging from 10 to 1000 μm. These values of T_c are similar to those calculated for Ar retention in biotite, and considerably lower than for Sr in apatite and plagioclase, for example. Such low closure temperatures for pyrrhotite suggest this mineral will date the final stage in the cooling of a magmatic system and possibly be susceptible to open system osmium exchange in the presence of late-stage hydrothermal fluids. This latter result infers that caution be applied when interpreting elevated initial osmium isotopic ratios as a product of crustal assimilation at the magmatic stage.     

The GSFC EUV and X-ray spectroheliograph on OSO-7

The Goddard Space Flight Center instrument carried on the pointed section of the OSO-7 satellite is described. This instrument contains: An extreme ultraviolet spectroheliograph using glancing incidence optics of Wolter's Type II to focus the Sun's light on the entrance slit of a concave grating spectrometer; an auxiliary H system; two X-ray spectroheliographs using mechanical collimators for spatial resolution and Ross filters to isolate spectral bands of interest, and a flare polarimeter operating in the 15–40 keV X-ray region. These subsystems may be operated in a number of modes which, when combined with the spacecraft modes, give the instrument great flexibility for making solar observations. Representative results from each of the subsystems are presented.     

Algal blooms and climate anomalies in north‐east New Zealand,August ‐December 1992

A raphidophyte‐dominated phytoplankton bloom extended discontinuously along the northeastern coastline of New Zealand, from Bream Tail, north of Leigh, to the western coast of the Coromandel Peninsula from late August until December 1992. The bloom was associated with an “El‐Niño” phase of the Southern Oscillation, resulting in unusually cold sea temperatures. The dominant bloom species in the north was Fibrocapsa japonica and in the south Heterosigma akashiwo. Associated species included the coccolithophorid Gephyrocapsa oceanica and the naked form of the silicoflagellate Dictyocha speculum. By December, numbers of the armoured form of D. speculum had increased, as those of raphidophytes and coccolithophorids declined. Bioassays to test for shellfish biotoxins were negative and Artemia salina bioassays, indicators of ichthyotoxicity, were negative except for Heterosigma akashiwo cultures, isolated from Coromandel water samples.     

A multi‐scale statistical approach to assess the effects of connectivity of road and stream networks on geomorphic channel condition

Roads in rural, upland landscapes are important sources of runoff and sediment to waterways. The downstream effects of these sources should be related to the connectivity of roads to receiving waters. Recent studies have explored this idea, but only simple metrics have been used to characterize connectivity and few studies have quantified the downstream effects of road–stream connectivity on sediment or solute budgets and channel morphology. In this study, we evaluated traditional and newly developed connectivity metrics that utilized features of landscape position and delivery pathway to characterize road–stream connectivity in upland settings. Using data on stream geomorphic conditions developed by the Vermont Agency of Natural Resources (Montpelier, VT), we related road connectivity metrics to channel condition on a set of 101 forested, upland streams with minimal development other than predominantly gravel road networks. Logistic regression indicated that measures of road density, proximity and orientation successfully distinguished among categories of stream geomorphic condition at multiple geographic scales. Discriminant function analysis using a set of inherent channel characteristics combined with road connectivity metrics derived at the reach corridor scale successfully distinguished channel condition for over 70% of the channels evaluated. This research contributes to efforts to evaluate the cumulative downstream effects of roads on stream channels and aquatic resources and provides a new means of watershed assessment to derive metrics that can be used to predict channel condition. Copyright © 2014 John Wiley & Sons, Ltd.     

Offshore Atlas Project: Methodology and Results

The Offshore Atlas Project (OAP) grouped 4,325 Miocene and older and 5,622 Pliocene and Pleistocene productive sands in the Gulf of Mexico into 91 chronostratigraphic hydrocarbon plays to aid the oil and gas industry with regional hydrocarbon exploration and field development. OAP has produced a two-volume atlas series entitled Atlas of Northern Gulf of Mexico Gas and Oil Reservoirs. Volume 1 comprises Miocene and older reservoirs, while volume 2 comprises Pliocene and Pleistocene reservoirs. Chronozones (Reed et al., 1987) were used to define geologic ages in the Gulf of Mexico. A chronozone is a time-stratigraphic unit defined by a particular benthic foraminifera biostratigraphic zone. The 26 chronozones identified by Reed et al. (1987) were further grouped into 14 Cenozoic and 2 Mesozoic chronozones for OAP. A composite type log (CTL), which shows the chronostratigraphic relationship of all productive sands in a field, was constructed for each of the 876 proved federal fields in the Gulf of Mexico. Depositional facies (retrogradational, aggradational, progradational, and submarine fan)were next identified on each CTL. The four facies were identified primarily according to characteristic SP-curve shapes, paleoecozones, and sand content. The chronozones and depositional facies identified on each CTL were then correlated among fields across the Gulf of Mexico. All productive sands correlated to the same chronozone and depositional facies were then identified as a unique play. Both federal and state fields in the Gulf of Mexico contain original proved reserves (sum of cumulative production and remaining proved reserves) estimated at 12.481 Bbbl of oil and condensate and 156.466 Tcf of gas (40.322 Bboe [sum of liquids and energy equivalent gas]). Of this, 9.943 Bbbl of oil and condensate and 122.263 Tcf of gas (31.698 Bboe) have been produced. Miocene plays contain the most total original proved reserves with 41.9 %, followed by Pleistocene plays (36.2 %), Pliocene plays (18.6 %), Mesozoic plays (2.9 %), and Oligocene plays (0.4 %). Miocene plays have produced the largest amount of total hydrocarbons, as well, at 43.5 % followed by Pleistocene plays (36.5 %), Pliocene plays (19.1 %), Oligocene plays (0.5 %), and Mesozoic plays (0.4 %). Just over two-thirds of the Gulf of Mexico's total original proved reserves are contained in progradational facies (67.4 %),with the remainder comprising submarine-fan facies (18.5 %), aggradational facies (9.9 %), retrogradationalfacies (2.4 %), combination facies (1.7 %), and caprock and reef reservoirs (0.1 %). Total cumulative production from the different facies closely mimics the distribution of original proved reserves. Of the 91 plays, the lower Pleistocene progradational play (LPL P.1) contains the most original proved gas reserves (10.5 %) and has produced the most gas (11.4 %). However, the upper upper Miocene eastern progradational play (UM3 P.1B) contains the most original proved oil and condensate reserves (18.9 %) and has produced the most oil and condensate (21.4%). Several technical studies resulting from OAP have been published. Hunt and Burgess (1995) described the distribution of OAP plays deposited by the ancestral Mississippi River delta system in the north-central Gulf of Mexico over the past 24 million years. The lower Miocene plays are restricted to the westernmost portion of the Louisiana shelf. In the late middle Miocene, the depocenter migrated east of the present-day Mississippi River delta. During the late upper Miocene, the depocenter began migrating back to the west and prograded basinward, and it continued to do so throughout the Pliocene and Pleistocene. Lore and Batchelder (1995) discussed how OAP plays can be used to find exploration targets and assess undiscovered resources. As an exploration tool, OAP play maps can be used to identify conceptual submarine-fan plays downdip of established shallow water producing facies, and to identify wells where a known producing facies or chronozone has not yet been reached. As an assessment tool, the extensive data sets associated with each OAP play can be used to infer statistically the size of undiscovered resources in a play to determine if exploration in that play is economically justifiable. Lore et al. (1995) estimated the amount of undiscovered conventionally recoverable resources in the Gulf of Mexico, basing their assessment on previous work performed for OAP. Mean level estimates show that, by far, submarine-fan plays have the greatest potential for additional oil and gas in the Gulf of Mexico, with 75.1 % and 70.4 % of the total oil and gas resources, respectively. Mean level estimates for the 13 OAP Miocene, Pliocene, and Pleistocene chronozones show that upper Pleistocene plays have the most oil resource potential (24.3 %), while lower Pleistocene plays have the most gas resource potential (20.6 %).