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At least 289 records · Page 16

Effect of the nonlinearity of the carbonate system on partial pressure of carbon dioxide in the oceans

Partial pressure of CO2 is a nonlinear function of several seawater properties. Due to the nonlinearity in this relationship, the partial pressure of a uniform ocean would be different from that of a nonuniform ocean with the same bulk seawater properties. Assuming uniformity of seawater properties at some temporal and spatial scales in carbon models leads to systematic errors in partial pressure of CO2. In this paper we evaluate the magnitude of these errors. We partition the Geochemical Ocean Sections Study and Transient Tracers in the Oceans data according to the horizontal structure of several box models from the literature. Our results suggest that assumption of uniformity at large scales leads to understanding of underestimation of global surface ocean partial pressure of CO2 by at least 3 - 12 microatm. Nonlinear effects also introduce systematic errors in the buffer factor estimated from bulk seawater properties. We find the standard deviation of partial pressure of CO2 to be an indicator of the magnitude of the nonlinear effects. We discuss the implications of these errors for some conclusions drawn from carbon models. Biogeochemical processes, such as mixing, gas exchange, or biological activity, influence the distribution of the seawater properties. A shift in spatial or temporal patterns of these processes can modify the nonuniformity of the seawater properties and thus alter the partial pressure of the surface waters, even if the mean intensities of the processes remain constant.

Trela, Piotr↗

Melt rock components in KREEPy breccia 15205: Petrography and mineral chemistry of KREEP basalts and quartz-normative mare basalts

Many current models for the origin of lunar highland rocks feature as an essential component the assimilation of KREEPy material by primitive magmas parental to the Mg-rich suite and alkali suite plutonic rocks. Similar models have also been proposed for the origin of various mare basalt suites. However, any model which considers assimilation of KREEP an important petrologic process must sooner-or-later deal with the question: what is KREEP? Because pristine KREEP basalts are rare, and most known samples are small (e.g., 15382/15386), the geochemical variability of KREEP basalts is poorly known. Other KREEP compositions which are commonly used in these models include the hypothetical 'high-K KREEP' component of Warren and Wasson, which is derived from Apollo 14 soil data, and the 'superKREEP' quartz-monzodiorite 15405. Lunar breccia 15205 is a polymict regolith breccia that consists of approximately 20% KREEP basalt clasts and 20% quartz-normative basalt clasts in a KREEP-rich matrix. Bulk rock mixing calculations show that this sample comprises about 84% KREEP. The clasts range up to 1 cm in size, but most are considerably smaller. The primary aim is to characterize pristine KREEP basalts petrographically, to establish the range in chemical compositions of KREEP basalts, and to test models that were proposed for their origin. In addition, we may be able to extend the compositional range recognized in the quartz-normative basalt suite and cast some light on its origin as well. Preliminary whole rock geochemical data on the KREEP basalts are presented in a companion paper by M.M. Lindstrom and co-workers. Concentration is on petrography and mineral chemistry of these clasts, and the implications these data have for the origin of the different melt rock suites.

Shervais, John W.↗

Arctic Coastal Erosion: Modeling and Experimentation

Increasing Arctic coastal erosion rates have put critical infrastructure and native communities at risk while also mobilizing ancient organic carbon into modern carbon cycles. Although the Arctic comprises one-third of the global coastline and has some of the fastest eroding coasts, current tools for quantifying permafrost erosion are unable to explain the episodic, storm-driven erosion events. Our approach, mechanistically coupling oceanographic predictions with a terrestrial model to capture the thermo-mechanical dynamics of erosion, enables this much needed treatment of transient erosion events. The Arctic Coastal Erosion Model consists of oceanographic and atmospheric boundary conditions that force a coastal terrestrial permafrost environment in Albany (a multi-physics based finite element model). An oceanographic modeling suite (consisting of WAVEWATCH III, Delft3D-FLOW, and Delft3D-WAVE) produced time-dependent surge and run-up boundary conditions for the terrestrial model. In the terrestrial model, a coupling framework unites the mechanical and thermal aspects of erosion. 3D stress/strain fields develop in response to a plasticity model of the permafrost that is controlled by the frozen water content determined by modeling 3D heat conduction and solid-liquid phase change. This modeling approach enables failure from any allowable deformation (block failure, slumping, etc.). Extensive experimental work has underpinned the ACE Model development including field campaigns to measure in situ ocean and erosion processes, strength properties derived from thermally driven geomechanical experiments, as well as extensive physical composition and geochemical analyses. Combined, this work offers the most comprehensive and physically grounded treatment of Arctic coastal erosion available in the literature. The ACE model and experimental results can be used to inform scientific understanding of coastal erosion processes, contribute to estimates of geochemical and sediment land-to-ocean fluxes, and facilitate infrastructure susceptibility assessments.

54 ENVIRONMENTAL SCIENCES↗

Post-landing major element quantification using SuperCam laser induced breakdown spectroscopy

The SuperCam instrument on the Perseverance Mars 2020 rover uses a pulsed 1064 nm laser to ablate targets at a distance and conduct laser induced breakdown spectroscopy (LIBS) by analyzing the light from the resulting plasma. SuperCam LIBS spectra are preprocessed to remove ambient light, noise, and the continuum signal present in LIBS observations. Prior to quantification, spectra are masked to remove noisier spectrometer regions and spectra are normalized to minimize signal fluctuations and effects of target distance. In some cases, the spectra are also standardized or binned prior to quantification. To determine quantitative elemental compositions of diverse geologic materials at Jezero crater, Mars, we use a suite of 1198 laboratory spectra of 334 well-characterized reference samples. The samples were selected to span a wide range of compositions and include typical silicate rocks, pure minerals (e.g., silicates, sulfates, carbonates, oxides), more unusual compositions (e.g., Mn ore and sodalite), and replicates of the sintered SuperCam calibration targets (SCCTs) onboard the rover. For each major element (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O), the database was subdivided into five “folds” with similar distributions of the element of interest. One fold was held out as an independent test set, and the remaining four folds were used to optimize multivariate regression models relating the spectrum to the composition. We considered a variety of models, and selected several for further investigation for each element, based primarily on the root mean squared error of prediction (RMSEP) on the test set, when analyzed at 3 m. In cases with several models of comparable performance at 3 m, we incorporated the SCCT performance at different distances to choose the preferred model. Shortly after landing on Mars and collecting initial spectra of geologic targets, we selected one model per element. Subsequently, with additional data from geologic targets, some models were revised to ensure results that are more consistent with geochemical constraints. The calibration discussed here is a snapshot of an ongoing effort to deliver the most accurate chemical compositions with SuperCam LIBS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Composition of Orientale basin deposits and implications for the lunar basin-forming process

The geologic, spectral and geochemical characteristics of the lunar Orientale basin are discussed, and a model is defined for the generation of Orientale basin deposits. The data indicate that the basin ejecta is composed mainly of anorthositic deposits and no crustal material. The crater was originally 500-600 km across and 50-60 km deep, the latter being too shallow to reach the projected 100 km crustal depth. A proportional growth model is judged acceptable for the Orientale basin. Finally, it is concluded that neither the Apollo 14 nor 16 missions obtained Orientale ejecta material, which could in any case be unidentifiable until more thorough samplings are made of a large portion of the lunar surface.

Spudis, P. D.↗

Materials and formation of the Imbrium basin

A study of Imbrium basin deposits has been conducted, including geologic mapping, analysis of orbital geochemical data, earth-based near-IR spectroscopy, and analytical modeling. The morphologic facies of the deposits display an unusual bilateral symmetry with respect to the main rim of the basin, which is thought to be 1160 km in diameter and composed of Apennine-Carpathian-Alpes mountain ranges. The Imbrium ring structure consists of six concentric rings ranging from 550-3200 km in diameter. The evolution of the target for the Imbrium basin impact is discussed. It is suggested that the Imbrium impact, which occurred 3.85 Gyrs ago, formed a basin predominantly by a proportional-growth crater-forming mechanism.

Spudis, Paul D.↗

Post-Landing Major Element Quantification Using SuperCam Laser Induced Breakdown Spectroscopy

The SuperCam instrument on the PerseveranceMars 2020 rover uses a pulsed 1064 nm laser to ablate targets at a distance and conduct laser induced breakdown spectroscopy (LIBS) by analyzing the light from the resulting plasma. SuperCam LIBS spectra are preprocessed to remove ambient light, noise, and the continuum signal present in LIBS observations. Prior to quantification, spectra are masked to remove noisier spectrometer regions andspectra are normalized to minimize signal fluctuations and effectsof target distance.In some cases, the spectra are also standardized or binned prior to quantification. To determine quantitative elemental compositionsof diverse geologic materials at Jezero crater, Mars, we use a suite of 1198 laboratory spectra of 334 well-characterized reference samples. The samples were selected to span a wide range of compositions and include typical silicate rocks, pure minerals (e.g.,silicates, sulfates, carbonates, oxides),more unusual compositions (e.g.,Mn oreand sodalite), andreplicates of the sintered SuperCam calibration targets (SCCTs) onboardthe rover. For each major element (SiO2, TiO2, Al2O3, FeOT, MgO, CaO, Na2O, K2O), the database was subdivided into five“folds” with similar distributions of the element of interest. One fold was held out as an independent test set, and the remaining fourfolds were used to optimize multivariate regression models relating the spectrum to the composition. We considered a variety of models, and selected several for further investigation for each element, based primarily on the root mean squared error of prediction (RMSEP) on the test set, when analyzed at 3m. In cases with several models of comparable performance at 3 m, we incorporated the SCCT performance at different distances to choose the preferred model. Shortly after landing on Mars and collecting initial spectra of geologic targets, we selected one model per element. Subsequently, with additional data from geologic targets, some models were revised to ensure results that are more consistent with geochemical constraints. The calibration discussed here is a snapshot of an ongoing effort to deliver the most accurate chemical compositions with SuperCam LIBS.

Mars 2020↗

The Co-Transport of PFAS and Cr(VI) in porous media

PFAS and Cr are present at some sites as co-contaminants. Here, the objective of this research was to investigate the co-transport behavior of per- and polyfluoroalkyl substances (PFAS) and hexavalent chromium (Cr(VI)) in porous media. Miscible-displacement experiments were conducted using two soils and an aquifer sediment with different geochemical properties. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were employed as model PFAS. The retardation of PFOS was decreased in the presence of Cr(VI). Conversely, the transport and retardation of PFOA was not affected by the presence of Cr(VI). The reduction of PFOS retardation caused by Cr(VI) is likely due to sorption competition for both organic-carbon and inorganic (metal-oxides and clay minerals) domains. The relative contributions of the three soil constituents to PFOS sorption and the potential for competition between PFOS and Cr(VI) is a function of the geochemical composition of the porous media (i.e., organic carbon, metal-oxides and clay minerals). The PFAS had minimal impact on the retention and transport of Cr(VI). To our knowledge, the results presented herein represent the first reported data for PFOS and Cr(VI) co-transport in porous media. The results of this study indicate that the presence of Cr(VI) has the potential to increase the migration potential of PFOS in soil and groundwater, which should be considered when characterizing electroplating facilities, leather tanning facilities, and other co-contaminated sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of Hydrology and Interim Measure Performance in the Chromium Plume at Los Alamos National Laboratory - 20498

Hexavalent chromium, Cr(VI), is present in the regional aquifer beneath Los Alamos National Laboratory (LANL) at concentrations greater than the New Mexico groundwater standard (50 ppb). The source of the Cr is blowdown from a power plant where potassium dichromate was used as a corrosion inhibitor from 1956 to 1972. Blowdown comingled with effluent from another source and migrated approximately 3 miles down a canyon, primarily as surface flow, until reaching an alluvial infiltration zone. The infiltrating water moved vertically through a thick (approximately 900 ft), complex stratigraphic sequence of unsaturated tuffs, basalt, and unconsolidated alluvial deposits. Horizontal transport also took place within spatially limited perched groundwater horizons in the vadose zone (VZ). Breakthrough at the regional aquifer water table is thought to have occurred in multiple hydraulic windows or 'drip points' located approximately 3 miles from the initial release site at the power plant. The regional aquifer is highly heterogeneous and anisotropic, and displays unconfined behavior in an upper zone and confined behavior at depth. The Cr(VI) contamination has so far remained confined to the upper approximately 25 m of the aquifer. The ambient hydraulic gradient in the regional aquifer is toward the east/southeast, but the water table is extremely flat in the Cr plume area compared to surrounding areas. There is some local variability in flow direction, potentially related to effects of seasonal pumping from nearby Los Alamos county water-supply wells, which draw from the regional aquifer several hundred feet below the water table. An interim measure (IM) is currently operating at the site to achieve hydraulic control of plume migration using a series of extraction wells, ion-exchange treatment, and injection along the downgradient portion of the plume. The migration of Cr contamination in the aquifer has been previously evaluated using a calibrated probabilistic numerical model, which has also been used to design the spatial configuration of extraction and injection wells for the IM, and to identify locations for monitoring wells. The model is built using the Finite Element Heat and Mass (FEHM) transfer code, and the Model Analysis and Decision Support (MADS) software is used for analyses. To date, the portion of the IM system that has operated in a continuous manner has been very effective at hydraulic control. Modifications to the flow field associated with the influence of IM pumping and injection are evaluated here, with modeling constraints to be provided by recent observations of tracers injected into both monitoring wells and IM injection wells, as well as opportunistic observations of geochemical signatures of treated ion-exchange effluent injected into IM injection wells. The tracer and geochemical data provide insights into modified flow directions within the Cr plume area that cannot be otherwise obtained. Results of the modeling work are being used to inform adaptive management of IM operations and will be a valuable tool for development and refinement of long-term remediation strategies. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Editorial for Special Issue “Environmentally Sound In Situ Recovery Mining of Uranium”

This Special Issue features seven articles that cover a range of topics pertaining to the environmentally sound in situ recovery mining of uranium (U ISR). The topics include: (1) methods for assessing the potential environmental impacts of future U ISR operations using historical operational records and available geohydrologic, geochemical and climate data in a specific regional setting; (2) laboratory column studies to parameterize a uranium surface complexation model that can be used to predict uranium fate and transport in groundwater; and (3) a field evaluation of both a chemical reductant and a biostimulant to promote reducing geochemical conditions after oxidative mining at a U ISR facility.

54 ENVIRONMENTAL SCIENCES↗

Geochemical aspect of impact cratering: Studies in Vernadsky Institute

Studies of the geochemical effects of impact cratering at the Vernadsky Institute in collaboration with the Institute of Dynamics of Geospheres, Moscow State University, Leningrad State University, and some other institutions were fulfilled by several approaches. At the initial stage, three approaches were used: (1) experimental studies of high-temperature vaporization of geological materials (basalts, granites, and so on) in vacuum that was considered as a model of behavior of impact melt and vapor; (2) search of impact-induced geochemical effects in the rock from terrestrial impact craters; and (3) studies of samples of lunar regolith. The next stage of the studies included experiments on quasi-equilibrium vaporization of geological material in Knudsen cells. The results of this investigation are discussed.

Yakovlev, O. I.↗

The Water Table Model (WTM) (v2.0.1): coupled groundwater and dynamic lake modelling

Abstract. Ice-free land comprises 26 % of the Earth's surface and holds liquid water that delineates ecosystems, affects global geochemical cycling, and modulates sea levels. However, we currently lack the capacity to simulate and predict these terrestrial water changes across the full range of relevant spatial (watershed to global) and temporal (monthly to millennial) scales. To address this knowledge gap, we present the Water Table Model (WTM), which integrates coupled components to compute dynamic lake and groundwater levels. The groundwater component solves the 2D horizontal groundwater flow equation using non-linear equation solvers from the C++ PETSc (Portable, Extensible Toolkit for Scientific Computation) library. The dynamic lake component makes use of the Fill–Spill–Merge (FSM) algorithm to move surface water into lakes, where it may evaporate or affect groundwater flow. In a proof-of-concept application, we demonstrate the continental-scale capabilities of the WTM by simulating the steady-state climate-driven water table for the present day and the Last Glacial Maximum (LGM; 21 000 calendar years before present) across the North American continent. During the LGM, North America stored an additional 14.98 cm of sea-level equivalent (SLE) in lakes and groundwater compared to the climate-driven present-day scenario. We compare the present-day result to other simulations and real-world data. Open-source code for the WTM is available on GitHub and Zenodo.

Callaghan, Kerry L. (ORCID:0000000226740838)↗

Improved Hypoxia Modeling for Nutrient Control Decisions in the Gulf of Mexico

As required by the Harmful Algal Bloom and Hypoxia Research Control Act of 1998, the Mississippi River/Gulf of Mexico Watershed Nutrient Task Force issued the 2001 Gulf Hypoxia Action Plan (updated in 2008). In response to the Gulf Hypoxia Action Plan of 2001 (updated in 2008), the EPA Gulf of Mexico Hypoxia Modeling and Monitoring Project has established a detailed model for the Mississippi-Attchafalaya River Basin which provides a capability to forecast the multi-source nutrient loading to the Gulf and the subsequent bio-geochemical processes leading to hypoxic conditions and subsequent effects on Gulf habitats and fisheries. The primary purpose of the EPA model is to characterize the impacts of nutrient management actions, or proposed actions on the spatial and temporal characteristics of the Gulf hypoxic zone. The model is expected to play a significant role in determining best practices and improved strategies for incentivizing nutrient reduction strategies, including installation of on-farm structures to reduce sediment and nutrient runoff, use of cover crops and other agricultural practices, restoration of wetlands and riparian buffers, improved waste water treatment and decreased industrial nitrogen emissions. These decisions are currently made in a fragmented way by federal, state, and local agencies, using a variety of small scale models and limited data. During the past three years, EPA has collected an enormous amount of in-situ data to be used in the model. We believe that the use of NASA satellite data products in the model and for long term validation of the model has the potential to significantly increase the accuracy and therefore the utility of the model for the decision making described above. This proposal addresses the Gulf of Mexico Alliance (GOMA) priority issue of reductions in nutrient inputs to coastal ecosystem. It further directly relates to water quality for healthy beaches and shellfish beds and wetland and coastal conservation restoration.

Habib, Shaid↗

Geochemistry and Multiomics Data Differentiate Streams in Pennsylvania Based on Unconventional Oil and Gas Activity

Unconventional oil and gas (UOG) extraction is increasing exponentially around the world, as new technological advances have provided cost-effective methods to extract hard-to-reach hydrocarbons. While UOG has increased the energy output of some countries, past research indicates potential impacts in nearby stream ecosystems as measured by geochemical and microbial markers. Here, we utilized a robust data set that combines 16S rRNA gene amplicon sequencing (DNA), metatranscriptomics (RNA), geochemistry, and trace element analyses to establish the impact of UOG activity in 21 sites in northern Pennsylvania. These data were also used to design predictive machine learning models to determine the UOG impact on streams. We identified multiple biomarkers of UOG activity and contributors of antimicrobial resistance within the order Burkholderiales. Furthermore, we identified expressed antimicrobial resistance genes, land coverage, geochemistry, and specific microbes as strong predictors of UOG status. Of the predictive models constructed (n = 30), 15 had accuracies higher than expected by chance and area under the curve values above 0.70. The supervised random forest models with the highest accuracy were constructed with 16S rRNA gene profiles, metatranscriptomics active microbial composition, metatranscriptomics active antimicrobial resistance genes, land coverage, and geochemistry (n = 23). The models identified the most important features within those data sets for classifying UOG status. These findings identified specific shifts in gene presence and expression, as well as geochemical measures, that can be used to build robust models to identify impacts of UOG development.

16S rRNA↗

Omics-to-Reactive-Transport (ORT): A workflow linking genome-scale metabolic models with reactive transport codes

Motivation: Nutrient and contaminant behavior in the subsurface are governed by multiple coupled hydrobiogeochemical processes which occur across different temporal and spatial scales. Accurate description of macroscopic system behavior requires accounting for the effects of microscopic and especially microbial processes. Microbial processes mediate precipitation and dissolution and change aqueous geochemistry, all of which impacts macroscopic system behavior. As `omics data describing microbial processes is increasingly affordable and available, novel methods for using this data quickly and effectively for improved ecosystem models are needed. Results: We propose a workflow (`Omics to Reactive Transport – ORT) for utilizing metagenomic and environmental data to describe the effect of microbiological processes in macroscopic reactive transport models. This workflow utilizes and couples two open-source software packages: KBase (a software platform for systems biology) and PFLOTRAN (a reactive transport modeling code). We describe the architecture of ORT and demonstrate an implementation using metagenomic and geochemical data from a river system. Our demonstration uses microbiological drivers of nitrification and denitrification to predict nitrogen cycling patterns which agree with those provided with generalized stoichiometries. While our example uses data from a single measurement, our workflow can be applied to spatiotemporal metagenomic datasets to allow for iterative coupling between KBASE and PFLOTRAN. Live, interactive models, which incorporate the results from this narrative into a PFLOTRAN simulation, are available (without login) at https://pflotranmodeling.paf.subsurfaceinsights.com/pflotran-simple-model/.

Rubinstein, Rebecca L↗

Advanced Geomechanical Model to Predict the Impact of CO2-Induced Microstructural Alterations on the Cohesive-Frictional Behavior of Mt. Simon Sandstone

We investigated the influence of CO2-induced geochemical reactions on the cohesive-frictional properties of host rock within the context of CO2 storage in a saline aquifer and focused on the Mt. Simon sandstone. The research objective was to model geo-mechanical changes due to host rock exposure to CO2-saturated brine while accounting for heterogeneity, double-scale porosity, and granular structure. We formulated a three-level multi-scale model for host rocks. We conducted scanning electron microscopy analyses to probe the microstructure and grid nanoindentation to measure the mechanical response. We derived new nonlinear strength upscaling solutions to correlate the effective strength characteristics and the macroscopic yield surface to the micro-structure at the nano-, micro-, and meso-scales. Specifically, our theoretical model links CO2-induced microstructural alterations to a reduction in the size of the yield surface, and a drop in the value of the friction coefficient. In turn, regarding the Illinois Basin Decatur Project, the CO2-induced drop in friction coefficient is linked to an increase in the risk of fault slip and a higher probability of induced microseismicity during and after the end of CO2 underground injection operations. The theoretical model presented is essential for the geo-mechanical modeling of CO2 underground injection operations at multiple length-scales.

58 GEOSCIENCES↗

High-temperature life without photosynthesis as a model for Mars

Discoveries in biology and developments in geochemistry over the past two decades have lead to a radical revision of concepts relating to the upper temperature at which life thrives, the genetic relationships among all life on Earth, links between organic and inorganic compounds in geologic processes, and the geochemical supply of metabolic energy. It is now apparent that given a source of geochemical energy, in the form of a mixture of compounds that is far from thermodynamic equilibrium, microorganisms can take advantage of the energy and thrive without the need for photosynthesis as a means of primary productivity. This means that life can exist in the subsurface of a planet such as Mars without necessarily exhibiting a surface expression. Theoretical calculations quantify the geochemically provided metabolic energy available to hyperthermophilic organisms in submarine hydrothermal systems on the Earth, and help to explain the enormous biological productivity of these systems. Efforts to place these models in the context of the early Earth reveal that substantial geochemical energy would have been available and that organic synthesis would have been thermodynamically favored as hydrothermal fluids mix with seawater.

Non-NASA Center↗

Modeling and Assimilating Ocean Color Radiances

Radiances are the source of information from ocean color sensors to produce estimates of biological and geochemical constituents. They potentially provide information on various other aspects of global biological and chemical systems, and there is considerable work involved in deriving new information from these signals. Each derived product, however, contains errors that are derived from the application of the radiances, above and beyond the radiance errors. A global biogeochemical model with an explicit spectral radiative transfer model is used to investigate the potential of assimilating radiances. The results indicate gaps in our understanding of radiative processes in the oceans and their relationships with biogeochemical variables. Most important, detritus optical properties are not well characterized and produce important effects of the simulated radiances. Specifically, there does not appear to be a relationship between detrital biomass and its optical properties, as there is for chlorophyll. Approximations are necessary to get beyond this problem. In this reprt we will discuss the challenges in modeling and assimilation water-leaving radiances and the prospects for improving our understanding of biogeochemical process by utilizing these signals.

Gregg, Watson↗