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At least 469 records · Page 26

How life affects the geochemical cycle of carbon

Developing a quantitative understanding of the biogeochemical cycles of carbon as they have worked throughout Earth history on various time scales, how they have been affected by biological evolution, and how changes in the carbon content of ocean and atmosphere may have affected climate and the evolution of life are the goals of the research. Theoretical simulations were developed that can be tuned to reproduce such data as exist and, once tuned, can be used to predict properties that have not yet been observed. This is an ongoing process, in which models and results are refined as new data and interpretations become available and as understanding of the global system improves. Results of the research are described in several papers which were published or submitted for publication. These papers are summarized. Future research plans are presented.

Walker, James C. G.↗

The Colorado East River Community Observatory Data Collection

Abstract The U.S. Department of Energy's (DOE) Colorado East River Community Observatory (ER) in the Upper Colorado River Basin was established in 2015 as a representative mountainous, snow‐dominated watershed to study hydrobiogeochemical responses to hydrological perturbations in headwater systems. The ER is characterized by steep elevation, geologic, hydrologic and vegetation gradients along floodplain, montane, subalpine, and alpine life zones, which makes it an ideal location for researchers to understand how different mountain subsystems contribute to overall watershed behaviour. The ER has both long‐term and spatially‐extensive observations and experimental campaigns carried out by the Watershed Function Scientific Focus Area (SFA), led by Lawrence Berkeley National Laboratory, and researchers from over 30 organizations who conduct cross‐disciplinary process‐based investigations and modelling of watershed behaviour. The heterogeneous data generated at the ER include hydrological, genomic, biogeochemical, climate, vegetation, geological, and remote sensing data, which combined with model inputs and outputs comprise a collection of datasets and value‐added products within a mountainous watershed that span multiple spatiotemporal scales, compartments, and life zones. Within 5 years of collection, these datasets have revealed insights into numerous aspects of watershed function such as factors influencing snow accumulation and melt timing, water balance partitioning, and impacts of floodplain biogeochemistry and hillslope ecohydrology on riverine geochemical exports. Data generated by the SFA are managed and curated through its Data Management Framework. The SFA has an open data policy, and over 70 ER datasets are publicly available through relevant data repositories. A public interactive map of data collection sites run by the SFA is available to inform the broader community about SFA field activities. Here, we describe the ER and the SFA measurement network, present the public data collection generated by the SFA and partner institutions, and highlight the value of collecting multidisciplinary multiscale measurements in representative catchment observatories.

54 ENVIRONMENTAL SCIENCES↗

Simulating Micrometeoroid Bombardment on Mercury: Identifying New Space Weathering Features in the Laboratory

Airless bodies are continually exposed to the harsh interplanetary space environment, causing the alteration of their surfaces through a process known as space weathering (SW). SW is dominated by solar wind irradiation and micrometeoroid bombardment, which together alter the spectral, microstructural, and chemical characteristics of grains on the surface of airless bodies. The effects of SW are variable and depend on the heliocentric distance and the initial composition of the planetary surface, among other factors. On the Moon and S- type asteroids, it is well established that SW darkens and reddens the surface of these bodies and attenuates absorption bands across the Vis-NIR wavelengths. These spectral effects are largely the result of the production of metallic Fe nanoparticles (npFe). However, Mercury’s SW environment is unique compared to the Moon and S-type asteroids. Mercury is a geochemical endmember, with a surface composition low in Fe (<2 wt.%) and enriched in volatile components, including regions of the surface hypothesized to contain up to 4 wt.% graphite in the low reflectance material (LRM). In fact, the presence of graphite on Mercury has been hypothesized to act as a reducing agent for silicates during SW to produce Si-bearing Fe-rich metal. In addition, its location in the solar system exposes Mercury to an extreme SW environment, with the surface of the planet experiencing an intense solar wind flux and higher flux and velocity of micrometeoroid impactors compared to the Moon and S-type asteroids. The effects that such harsh SW has on materials with the unique compositional characteristics of Mercury are not well constrained. To better understand SW at Mercury, we must investigate these processes in the laboratory. Here, we present the results of our analyses of the spectral, microstructural and chemical characteristics of Mercury analog samples irradiated by pulsed laser to simulate the short duration, high temperature events associated with micrometeoroid impacts.

Nick Bott↗

Facet-specific oxidation of Mn(II) and heterogeneous growth of manganese (oxyhydr)oxides on hematite nanoparticles

It is recognized that different facets of minerals vary distinctively in their chemical reactivity with aqueous solutions. However, detailed molecular and atomistic understandings of these phenomena are relatively limited. This study investigated the interaction of aqueous Mn2+ and dissolved oxygen on various facets of two morphology-types of iron oxide (hematite) nanocrystals. These interactions result in the oxidation of manganese and the heterogeneous nucleation and growth of Mn(II)/Mn(III), and Mn(III) oxides. The nanoscale morphology and atomic structure of the manganese oxide products were characterized in detail. Our results, for the first time, directly demonstrate the facet-dependent oxidation of Mn 2+ and nucleation of Mn(II/III) oxides, followed by their epitaxial growth on hematite. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron diffraction measurements reveal the growth of MnOx nanowires on {012} facets of both hematite nanoplates (HNP) and hematite nanocubes (HNC), while the basal {001} facets on the HNP particles do not produce precipitates. The average oxidation state of the MnO x on HNP and HNC determined using electron energy-loss spectroscopy (EELS) show that both Mn(II) and Mn(III) are present. The facet-dependent oxidation of Mn 2+ may be attributed to adsorption-induced electron transfer (ET), and hematite {001} facets generally exhibiting weaker ability in the uptake of ions relative to {012} facets, and the bulk ET from {012} to {001} facets through the conduction band of hematite. Nevertheless, the mineral composition and growth mechanisms of MnOx catalyzed by HNP and HNC are similar. High-resolution TEM analysis reveals the presence of both hausmannite and manganite on HNP and HNC. The nanoscale observations and thermodynamic considerations indicate that the growth mechanisms/processes of MnO x include heterogeneous nucleation of hausmannite nanoparticles, crystallization by particle attachment, transformation from hausmannite to manganite, and self-catalyzed MnO x growth. It is possible that all of these processes are concurrent. The crystallographic relationship between the heterogeneously formed manganite with hematite, which has not been reported before, proves that hematite provides reaction sites and functions as an atomic template for the formation of MnO x nanowires. These findings advance our understanding of the redox chemistry and heterogeneous growth of minerals as controlled by the surficial structure of the substrate mineral. This has important geochemical implications as the catalytic growth of less common, highly reactive phases like MnO x are known to be consequential in complex natural and anthropogenic environments.

36 MATERIALS SCIENCE↗

Microbially induced precipitation of silica by anaerobic methane-oxidizing consortia and implications for microbial fossil preservation

Authigenic carbonate minerals can preserve biosignatures of microbial anaerobic oxidation of methane (AOM) in the rock record. It is not currently known whether the microorganisms that mediate sulfate-coupled AOM—often occurring as multicelled consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB)—are preserved as microfossils. Electron microscopy of ANME-SRB consortia in methane seep sediments has shown that these microorganisms can be associated with silicate minerals such as clays [Chen et al., Sci. Rep. 4, 1–9 (2014)], but the biogenicity of these phases, their geochemical composition, and their potential preservation in the rock record is poorly constrained. Long-term laboratory AOM enrichment cultures in sediment-free artificial seawater [Yu et al., Appl. Environ. Microbiol. 88, e02109-21 (2022)] resulted in precipitation of amorphous silicate particles (~200 nm) within clusters of exopolymer-rich AOM consortia from media undersaturated with respect to silica, suggestive of a microbially mediated process. The use of techniques like correlative fluorescence in situ hybridization (FISH), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), and nanoscale secondary ion mass spectrometry (nanoSIMS) on AOM consortia from methane seep authigenic carbonates and sediments further revealed that they are enveloped in a silica-rich phase similar to the mineral phase on ANME-SRB consortia in enrichment cultures. Like in cyanobacteria [Moore et al., Geology 48, 862–866 (2020)], the Si-rich phases on ANME-SRB consortia identified here may enhance their preservation as microfossils. Finally, the morphology of these silica-rich precipitates, consistent with amorphous-type clay-like spheroids formed within organic assemblages, provides an additional mineralogical signature that may assist in the search for structural remnants of microbial consortia in rocks which formed in methane-rich environments from Earth and other planetary bodies.

54 ENVIRONMENTAL SCIENCES↗

Ground Truthing Orbital Clay Mineral Observations with the APXS Onboard Mars Exploration Rover Opportunity

NASA's Mars Exploration Rover Opportunity has been exploring approximately 22 km diameter Endeavour crater since 2011. Its rim segments predate the Hesperian-age Burns formation and expose Noachian-age material, which is associated with orbital Fe3+-Mg-rich clay mineral observations [1,2]. Moving to an orders of magnitude smaller instrumental field of view on the ground, the clay minerals were challenging to pinpoint on the basis of geochemical data because they appear to be the result of near-isochemical weathering of the local bedrock [3,4]. However, the APXS revealed a more complex mineral story as fracture fills and so-called red zones appear to contain more Al-rich clay minerals [5,6], which had not been observed from orbit. These observations are important to constrain clay mineral formation processes. More detail will be added as Opportunity is heading into her 10th extended mission, during which she will investigate Noachian bedrock that predates Endeavour crater, study sedimentary rocks inside Endeavour crater, and explore a fluid-carved gully. ESA's ExoMars rover will land on Noachian-age Oxia Planum where abundant Fe3+-Mg-rich clay minerals have been observed from orbit, but the story will undoubtedly become more complex once seen from the ground.

Schroeder, C.↗

A Critical Review of the Physicochemical Impacts of Water Chemistry on Shale in Hydraulic Fracturing Systems

Hydraulic fracturing of unconventional hydrocarbon resources involves the sequential injection of a high-pressure, particle-laden fluid with varying pH’s to make commercial production viable in low permeability rocks. This process both requires and produces extraordinary volumes of water. The water used for hydraulic fracturing is typically fresh, whereas “flowback” water is typically saline with a variety of additives which complicate safe disposal. As production operations continue to expand, there is an increasing interest in treating and reusing this high-salinity produced water for further fracturing. Here in this paper we review the relevant transport and geochemical properties of shales, and critically analyze the impact of water chemistry (including produced water) on these properties. We discuss five major geochemical mechanisms that are prominently involved in the temporal and spatial evolution of fractures during the stimulation and production phase: shale softening, mineral dissolution, mineral precipitation, fines migration, and wettability alteration. A higher salinity fluid creates both benefits and complications in controlling these mechanisms. For example, higher salinity fluid inhibits clay dispersion, but simultaneously requires more additives to achieve appropriate viscosity for proppant emplacement. In total this review highlights the nuances of enhanced hydrogeochemical shale stimulation in relation to the choice of fracturing fluid chemistry.

54 ENVIRONMENTAL SCIENCES↗

Role of eddy pumping in enhancing primary production in the ocean

Eddy pumping is considered to explain the disparity between geochemical estimates and biological measurements of exported production. Episodic nutrient injections from the ocean into the photic zone can be generated by eddy pumping, which biological measurements cannot sample accurately. The enhancement of production is studied with respect to a cyclonic eddy in the subtropical Pacific. A pump-and-probe fluorimeter generates continuous vertical profiles of primary productivity from which the contributions of photochemical and nonphotochemical processes to fluorescence are derived. A significant correlation is observed between the fluorescence measurements and radiocarbon measurements. The results indicate that eddy pumping has an important effect on phytoplankton production and that this production is near the maximum relative specific growth rates. Based on the production enhancement observed in this case, eddy pumping increases total primary production by only 20 percent and does not account for all enhancement.

Falkowski, Paul G.↗

Task 10: an ERTS Experiment for Mapping Iron Compounds, 1383

The author has identified the following significant results. Preliminary results of a spectral ratioing technique are shown for a region at the southern end of the Wind River Range, Wyoming. Digital ratio graymaps and analog ratio images have been produced for the test site, but ground truth is not yet available for thorough interpretation of these products. ERTS-1 analog ratio images were found generally better than either ERTS-1 single channel images or high altitude aerial photos for the discrimination of vegetation from non-vegetation in the test site region. Some linear geological features smaller than the ERTS-1 spatial resolution are seen as well in ERTS-1 ratio and single channel images as in high altitude aerial photography. Geochemical information appears to be extractable from ERTS-1 data. Good preliminary quantitative agreement between ERTS-1 derived ratios and laboratory derived reflectance ratios of rocks and minerals encourage plans to use lab data as training sets for a simple ratio gating logic approach to automatic recognition maps. Empirical atmospheric corrections indicate that atmospheric corrections are needed to make the ratio method, and possibly other types of data processing, consistent over large geographical and temporal displacements.

Vincent, R. K.↗

Dawn Mission: A Journey in Space and Time

By successively orbiting both 4 Vesta and 1 Ceres the Dawn mission directly addresses the longstanding goals of NASA and the planetary community to understand the origin and evolution of the solar system by obtaining geophysical and geochemical data on diverse main belt asteroids. Ceres and Vesta are two complementary terrestrial protoplanets (one apparently "wet" and one "dry"), whose accretion was terminated by the formation of Jupiter. Ceres is little changed since it formed in the early solar system, while Vesta has experienced significant heating and differentiation. Both have remained intact over the age of the solar system, thereby retaining a record of events and processes from the time of planet formation. Detailed study of the geophysics and geochemistry of these two bodies provides critical benchmarks for the early solar system conditions and processes that shaped its subsequent evolution. Dawn provides the missing context for both primitive and evolved meteoritic data, thus playing a central role in understanding terrestrial planet formation and the evolution of the asteroid belt. Dawn is to be launched in May 2006 arriving at Vesta in 2010 and Ceres in 2014, stopping at each to make 11 months of orbital measurements. The spacecraft uses solar electric propulsion both in cruise and in orbit to make most efficient use of its xenon propellant. The spacecraft carries a framing camera, visible and infrared mapping spectrometer, gamma ray/neutron spectrometer, a laser altimeter, magnetometer, and radio science.

Russell, C. T.↗

Platinum group elements in a 3.5 Ga nickel-iron occurrence - Possible evidence of a deep mantle origin

This paper reports the results of new field observations and the geochemical analyses for the area of the Bon Accord (BA) (the Kaapvaal craton, South Africa) Ni-Fe deposit, with particular consideration given to the trace element, platinum-group element, and isotopic (Pb, Nd, and Os) compositions. On the basis of these data, an interpretation of BA is suggested, according to which the BA deposit is a siderophile-rich heterogeneity remaining in the deep mantle after a process of incomplete core formation. The implications of such a model for the study of core-mantle segregation and the geochemistry of the lowermost mantle are discussed.

Tredoux, Marian↗

The Wisconsin magmatic terrane: An Early Proterozoic greenstone-granite terrane formed by plate tectonic processes

The Wisconsin magmatic terrane (WMT) is an east trending belt of dominantly volcanic-plutonic complexes of Early Proterozoic age (approx. 1850 m.y.) that lies to the south of the Archean rocks and Early Proterozoic epicratonic sequence (Marquette Range Supergroup) in Michigan. It is separated from the epicratonic Marquette Range Supergroup by the high-angle Niagara fault, is bounded on the south, in central Wisconsin, by Archean gneisses, is truncated on the west by rocks of the Midcontinent rift system, and is intruded on the east by the post-orogenic Wolf river batholith. The overall lithologic, geochemical, metallogenic, metamorphic, and deformational characteristics of the WMT are similar to those observed in recent volcanic arc terranes formed at sites of plate convergence. It is concluded that the WMT represents an evolved oceanic island-arc terrane accreated to the Superior craton in the Early Proterozoic. This conclusion is strengthened by the apparent absence of Archean basement from most of the WMT, and the recent recognition of the passive margin character of the epicratonic Marquette Range Supergroup.

Schulz, K. J.↗

Aqueous Processes and Microbial Habitability of Gale Crater Sediments from the Blunts Point to the Glenn Torridon Clay Unit

A driving factor for sending the Mars Science Laboratory, Curiosity rover to Gale Crater was the orbital detection of clay minerals in the Glen Torridon (GT) clay unit. Clay mineral detections in GT suggested a past aqueous environment that was habitable, and could contain organic evidence of past microbiology. The mission of the Sample Analysis at Mars (SAM) instrument onboard Curiosity was to detect organic evidence of past microbiology and to detect volatile bearing mineralogy that can inform on whether past geochemical conditions would have supported microbiological activity. The objective of this work was to 1) evaluate the depositional/alteration conditions of Blunt’s Point (BP) to GT sediments 2) search for evidence of organics, and 3) evaluate microbial habitability in the BP, Vera Rubin Ridge (VRR), and GT sedimentary rock.

Sutter, Brad↗

Regional geology of the Venera landing sites: Tentative results of photogeologic mapping

The regional geology of the five Venera landing sites, where geochemical measurements and TV observations on the Venusian surface were made, was studied based on the photogeologic analysis of the Magellan C1-MIDRP imagery for the large area that we will call the Venera region (38 deg. N to 22.6 deg. S and 268 to 344 deg. E). The results of the analysis were compiled in the form of a synoptical geologic map at about 1:10 M scale. MIT-processed Magellan altimetry was also used for the analysis.

Basilevsky, A. T.↗

A Perspective on the Successes of the NNSS Underground Test Area (UGTA) Activity - 20221

Between 1951 and 1992, 828 underground nuclear tests were performed at the Nevada National Security Site (NNSS). Underground testing was done in five major testing areas, which included (1) Frenchman Flat, (2) Rainier Mesa/Shoshone Mountain, (3) Yucca Flat/Climax Mine (4) Central Pahute Mesa, and (5) Western Pahute Mesa. About one third of the underground tests were detonated near, at or below the water table, and thus radioactive contamination was introduced to the groundwater system. The U.S. Department of Energy's Underground Test Area (UGTA) Activity was established in the late 1990's to address the fate and movement of residual radioactivity in groundwater, and characterize the risk that it may pose to NNSS workers and the offsite public. It has accomplished this goal through a process of iterative groundwater sampling and numerical groundwater flow and transport modeling, and long-term monitoring. The UGTA Activity draws on the expertise of scientists in the fields of geology, hydrology, radiochemistry, and risk assessment from the U.S. DOE staff, the lead contractor (currently Navarro) and many other organizations, in cooperation with the governing regulatory body, the State of Nevada's Division of Environmental Protection (NDEP). Los Alamos National Laboratory (LANL) is one of the participating research organizations involved with the UGTA Activity. Under the direction of DOE and the lead contractor, LANL's role in UGTA has evolved over time from an initial focus on geologic characterization, to conducting field and laboratory experiments, and finally to its current role of providing modeling and geochemistry expertise to characterize the rates and directions of groundwater and radionuclide movement. In its current role, LANL has either developed or provided the numerical tools for developing flow and transport models in each of the four major testing areas. In addition, LANL has provided an independent assessment of future groundwater flow and transport behavior through the analysis of naturally-occurring geochemical and isotopic tracers in groundwater. The five major testing areas are now in different stages of investigation or closure: (1) Frenchman Flat is in its fifth year of post closure modeling; (2) The Rainier Mesa/Shoshone Mountain Closure Report has been submitted to NDEP and is awaiting approval; (3) The Yucca Flat/Climax Mine Closure Report is under development; and (4) Central and (5) Western Pahute Mesa is still undergoing investigation and flow and transport model development. The success of the UGTA Activity in reaching or approaching closure in three of the five major testing areas is primarily due to the DoE's focus on regulatory closure requirements, but also is in part attributable to a rigorous internal review process and the involvement of NDEP and Nye County water professionals as participants and observers in the reviews. County and state involvement in the internal review process has promoted trust that the U.S. DOE is deeply committed to ensuring the present and future safely of NNSS workers and the surrounding communities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The evolution of soil microstructure and micromineralogy along a soil age gradient on the Galápagos Islands (Ecuador)

The islands of the Galápagos archipelago are of different ages due to the combination of a geostationary volcanic hotspot and the eastward movement of the Nazca tectonic plate. Taking advantage of this, a soil chronosequence (1.5–1070 ka) has recently been established covering four of the islands. This was used to investigate the temporal development of soil microstructure and micromineralogy using micromorphological methods in combination with synchrotron-based mineralogical and geochemical microanalyses. Along the chronosequence, the microstructure changed from intergrain microaggregates in the young soils to angular blocky microaggregates in the older soils. In the young soils, a high amount of vitric scoria and weatherable minerals occur, but they quickly disappear with age, and micromass increased fast. The micromorphological studies as well as micro-XRD and micro-XRF revealed increasing heterogeneity of soil microstructure and micromineralogy due to weathering and pedogenic processes until intermediate soil age. In the oldest soils, the microstructure became more uniform again, de-mixing pedofeatures like clay coatings have completely disappeared, and kaolinite, hematite and gibbsite dominate the mineralogical composition. Our study shows that the development of soil microstructure mirrors macroscopic soil profile development showing increasing differentiation until intermediate developmental stages and receding heterogeneity in highly weathered soils.

54 ENVIRONMENTAL SCIENCES↗

Recycling of volatiles at subduction zones: Noble gas evidence from the Tabar-Lihir-Tanga-Feni arc of papua New Guinea

Convergent margin processes play an important but poorly understood role in the distribution of terrestrial volatile species. For example, subduction processes filter volatiles from the subducting package, thereby restricting their return to the mantle. In addition, once extracted from the downgoing slab, volatiles become an essential component in the petrogenesis of island arc magmas. The noble gases, with their systematic variation in physical properties and diversity of radiogenic isotopes, should carry a uniquely valuable record of these processes. However, thus far studies of noble gases in arc volcanics have achieved only limited success in this regard. Subduction-related lavas and geothermal fluids carry (3)He/(4)He ratios equal to or slightly lower than those found in the depleted upper mantle source of mid-ocean ridge basalts. Apparently slab-derived helium (which should have (3)He/(4)He much less than MORB) is extensively diluted by MORB-like helium from the mantle wedge, making it difficult to use helium as a tracer of convergent margin processes. Interpretation of the heavier noble gases (Ne-Ar-Kr-Xe) in arc lavas has also proven difficult, because the lavas carry low noble gas concentrations and hence are subject to pervasive atmospheric contamination. The low noble gas concentrations may be a consequence of degassing in the high level magma chambers characteristic of arc stratovolcanos. We have recently initiated a project to better constrain the behavior of volatiles in subduction zones through geochemical studies of the tectonically unusual volcanoes of the Tabar-Lihir-Tanga-Feni (TLTF) arc in the Bismarck Archipelago, Papua New Guinea.

Farley, Kenneth↗

Iron-activated persulfate oxidation degrades aqueous Perfluorooctanoic acid (PFOA) at ambient temperature

Perfluorooctanoic acid (PFOA, C 8 HF 15 O 2 ) is an industrial surfactant that is highly resistant to natural breakdown processes such as those mediated by heat, hydrolysis, photolysis, and biodegradation. Many efforts have been developed to breakdown PFOA to less harmful species due to its widespread human exposure and potential toxicity. However, these methods require high temperature or specialized equipment with serious disadvantages of high energy cost for long-term use. For this paper, we investigated the effectiveness of PFOA degradation by ferrous iron-activated persulfate oxidation (IAPO) under various aqueous geochemical conditions. Approximately 64% of PFOA (initial concentration = 1.64 μmol L –1 ) was degraded after 4 h under illuminated anoxic conditions at ambient temperature. This degradation rate and magnitude support the potential use of IAPO as a novel inexpensive and environmentally friendly method to remediate PFOA in soil and groundwater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗