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At least 19 records

Retaining Geochemical Signatures during Aragonite-Calcite Transformation at Hydrothermal Conditions

Transformation of aragonite, a mineral phase metastable at Earth’s surface, to calcite widely occurs in both sedimentary and metamorphic systems with the presence of an aqueous phase. The transformation process can affect geochemical signatures of aragonite (a protolith). This study focused on quantification of the retention of Mg/Ca and Sr/Ca ratios, and δ18O during the transformation process as well as evaluation of the transformation rate. To investigate the effect of transformation from aragonite to calcite on elemental and stable isotope ratios, we conducted a series of experiments in NaCl solutions at temperatures between 120 and 184 °C. Two additional experiments at 250 °C were conducted to estimate the transformation rate of aragonite to calcite. Protolith materials consist of (1) synthetic (Mg; Sr-bearing or non-Mg; Sr bearing) needle-shaped microcrystals of aragonite (<5 µm in size) and (2) larger chips (>100 µm in size) of natural aragonite. X-ray diffraction (XRD) showed that microcrystals successfully transformed to calcite within 30 h and scanning electron microscopy (SEM) yielded a change in the crystal size to >10 µm in rhombohedral shape. Electron backscatter diffraction (EBSD) of the larger aragonite chips showed that transformation to randomly oriented calcite occurred at the rims and along the cracks while the core retained an aragonite crystal structure. Isotope-ratio mass spectrometry (IRMS) analyses showed that calcite δ18O was controlled by temperature and δ18O of the solution. The obtained calibration curve of isotope fractionation factor versus temperature is consistent with other studies. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses showed that calcite partially or completely retained Mg/Ca and Sr/Ca ratios through the transformation.

58 GEOSCIENCES↗

Geochemical signatures in fin rays provide a nonlethal method to distinguish the natal rearing streams of endangered juvenile Chinook Salmon Oncorhynchus tshawytscha in the Wenatchee River, Washington

Rebuilding fish populations that have undergone a major decline is a challenging task that can be made more complicated when estimates of abundance obtained from physical tags are biased or imprecise. Abundance estimates based on natural tags where each fish in the population is marked can help address these problems, but generally requires that the samples be obtained in a nonlethal manner. We evaluated the potential of using geochemical signatures in fin rays as a nonlethal method to determine the natal tributaries of endangered juvenile spring Chinook Salmon in the Wenatchee River, Washington. Archived samples of anal fin clips collected from yearling smolt in 2009, 2010 and 2011 were analyzed for Ba/Ca, Mn/Ba, Mg/Ca, Sr/Ca, Zn/Ca and 87Sr/86Sr by inductively coupled plasma mass spectrometry. Water samples collected from these same streams in 2012 were also quantified for geochemical composition. Fin ray and water Ba/Ca, Sr/Ca, and 87Sr/86Sr were highly correlated despite the samples having been collected in different years. Fin ray Ba/Ca, Mg/Ca, Sr/Ca, Zn/Ca and 87Sr/86Sr ratios differed significantly among the natal streams, but also among years within streams. A linear discriminant model that included Ba/Ca, Mg/Ca, Sr/Ca, and 87Sr/86Sr correctly classified 95% of the salmon to their natal stream. Our results suggest that fin ray geochemistry may provide an effective, nonlethal method to identify mixtures of Wenatchee River spring Chinook Salmon for recovery efforts when these involve the capture of juvenile fish to estimate population abundance.

Chinook salmon↗

HIMU geochemical signature originating from the transition zone

Plume volcanism may sample mantle sources deeper than mid-ocean ridge and arc volcanism. Ocean island basalts (OIBs) are commonly related to plume volcanism, and their diverse isotopic and elemental compositions can be described using a limited number of mantle endmembers. However, the origins and depths of these mantle endmembers are highly debated. Here we show that the HIMU (high μ, μ = 238 U/ 204 Pb) endmember may reside in the transition zone. Specifically, we report the geochemical signature of a high-pressure multiphase diamond inclusion, entrapped at 420–440 km depth and 1450 ±50 K, which matches exactly the geochemical patterns of the HIMU-rich OIBs. Since the HIMU component is variably sampled by almost all OIBs, our finding implies that the transition zone causes a major overprint of the geochemical features of mantle plumes. Furthermore, some mantle plumes, like those feeding Bermuda, St Helena, Tubuai and Mangaia, appear to be dominated by this source. Furthermore, our finding highlights the importance of the transition zone in highly incompatible element budget of the mantle.

58 GEOSCIENCES↗

Chicxulub Impact Melts: Geochemical Signatures of Target Lithology Mixing and Post-Impact Hydrothermal Fluid Processes

Impact melts within complex impact craters are generally homogeneous, unless they differentiated, contain immiscible melt components, or were hydrothermally altered while cooling. The details of these processes, however, and their chemical consequences, are poorly understood. The best opportunity to unravel them may lie with the Chicxulub impact structure, because it is the world s most pristine (albeit buried) large impact crater. The Chicxulub Scientific Drilling Project recovered approx. 100 meters of impactites in a continuous core from the Yaxcopoil-1 (YAX-1) borehole. This dramatically increased the amount of melt available for analyses, which was previously limited to two small samples N17 and N19) recovered from the Yucatan-6 (Y-6) borehole and one sample (N10) recovered from the Chicxulub-1 (C-1) borehole. In this study, we describe the chemical compositions of six melt samples over an approx. 40 m section of the core and compare them to previous melt samples from the Y-6 and C-1 boreholes.

Kring, David A.↗

Integration of Omics into a New Comprehensive Rate Law for Competitive Terminal Electron-Accepting Processes in Reactive Transport Models: Application to N, Fe, S, and Contaminant Transformations in Stream and Wetland Sediments

Surface waters represent important sources of alternate energy and drinking water in the United States, and characterizing the biogeochemical processes that affect surface water quality is relevant to the DOE-BER mission. Sediment biogeochemical processes regulate the release of carbon (C), nutrients, and contaminants to surface waters and thus influence water quality. Sediment biogeochemical processes are dynamic and affected by the deposition and remobilization of solid material and changes in environmental conditions driven by water discharge variations. Wetlands are important natural filters of surface waters which may either trap, metabolize, or mobilize nutrients and contaminants. Despite their importance, biogeochemical processes regulating nutrient and contaminant release and C transformation in stream and wetland sediments cannot be predicted accurately by current mathematical models. These reactive transport models largely rely on detectable changes in geochemical conditions to activate metabolic processes, do not accurately account for the competition between microbial processes, and poorly constrain effects of hydrological perturbations on biogeochemical processes. In this BER-SBR exploratory project, metagenomic and geochemical signatures were combined to identify microbially-mediated redox processes in anaerobic stream and wetland sediments from the Savannah River Site (SRS, ANL SFA) and East Fork Poplar Creek (EFPC, ORNL SFA) that play important roles in C, uranium (U), and mercury (Hg) transformations. In addition, sediment incubations were conducted to examine the competition between anaerobic respiration processes Finally, new rate laws were developed for reactive transport models that rely on complementary metagenomic and geochemical signatures to identify the underlying anaerobic microbial processes in stream and wetland sediments, describe the competition between the dominant metabolic processes involved in nutrient release and U and Hg mobilization, and more accurately quantify carbon transformation and the response of microbial processes to changes in redox conditions associated with hydrological forcing. These rate laws were optimized in batch reactors with SRS wetland sediments, where iron and sulfate reduction dominate. Anaerobic carbon remineralization processes followed the expected thermodynamic sequence of microbial respiration with depth in both sediments, except that geochemical signals indicated that sulfate reduction was inactive in EFPC sediments and moderate in SRS wetland sediments. Estimates indicated that microbial iron reduction contributed to at least half of the production of reduced iron in these sediments. Incubations demonstrated that nitrate reduction, denitrification, and dissimilatory nitrate reduction to ammonium were active in the natural EFPC sediment and activated upon nitrate amendment in these nitrate-rich sediments. In turn, these processes were outcompeted by the addition of either iron oxides or sulfate as alternative terminal electron acceptors. Although geochemical products of sulfate reduction were not detected in the incubations, the abundance of sulfate reduction genes increased with depth in the sediment and was equally more pronounced in treatments amended with either iron oxides or sulfate. Simultaneously, anaerobic sulfide oxidizing bacteria coupling sulfide oxidation to DNRA (and not conventional denitrification) were apparently enriched over time, regardless of the treatments. These findings indicate that sulfate reduction is important in freshwater stream sediments and probably catalyzed by a cryptic sulfur cycle involving nitrogen species, in which the sulfur products from sulfate reduction are immediately removed by side reactions and not detectable by geochemical measurements alone. Similar experiments in SRS sediments, however, demonstrated little interaction between nitrogen and sulfur cycling microorganisms. Sulfate reduction was impacted by the addition of more thermodynamically favorable electron acceptors, suggesting either that iron-reducing microorganisms outcompeted sulfate-reducing microorganisms for organic substrate, depleting the stock of electron donor available for sulfate reduction, or that the cryptic sulfur cycle was shunted by the precipitation of FeS generated as a result of the abiotic reduction of iron oxides by dissolved sulfide. A diagnostic modeling exercise was conducted to further investigate the competition between terminal electron accepting processes. As conventional kinetic models typically do not account for cryptic cycles and used inaccurate formulations to describe competition between microbial communities, new metabolic rate laws were developed that explicitly express the electron acceptor-specific enzyme of each energetically favorable metabolic process based on gene abundance detected in the incubations. The model was tested with the sediment slurry incubation data to determine whether substrate competition could explain the decrease in sulfate reduction observed in the presence of iron oxide competitor. The model was able to reproduce geochemical concentrations really well in each treatment once the model was calibrated with the unamended control, suggesting that microbial competition was indeed driven by thermodynamic considerations. Overall, carbon remineralization processes and rates will be reproduced much more realistically with the new metabolic rate laws.

54 ENVIRONMENTAL SCIENCES↗

Using Chemcam Derived Geochemistry to Identify the Paleonet Sediment Transport Direction and Source Region Characteristics of the Stimson Formation in Gale Crater, Mars

The NASA Curiosity rover has encountered both ancient and modern dune deposits within Gale crater. The modern dunes are actively migrating across the surface within the Bagnold Dune field of which Curiosity conducted analysis campaigns at two different localities. Variations in mafic-felsic mineral abundances between these two sites have been related to the aeolian mineral sorting regime for basaltic environments identified on the Earth which become preferentially enriched in olivine relative to plagioclase feldspar with increasing distance from the source. This aeolian mineral sorting regime for basaltic minerals has also been inferred for Mars from orbital data. The aim of this study is to investigate whether this aeolian mafic-felsic mineral sorting trend has left a geochemical signature in the ancient dune deposits preserved within the Stimson formation. The Stimson formation unconformably overlies the Murray formation and consists of thickly laminated, cross-bedded sandstone. Stimson outcrops have a variable thickness up to 5 meters covering a total area of 17 square kilometers. A dry, aeolian origin was determined for this sandstone due to the high sphericity and roundness of the grains, uniform bimodal grain size distribution (250-710 microns), and 1-meter-thick cross-beds. Identifying the geochemical signature of mineral sorting can provide insights about the paleo-net sediment transport direction of the dunes and prevailing wind direction at the time of deposition.

Bedford, C. C.↗

Contaminant source identification using semi-supervised machine learning

Identification of the original groundwater types present in geochemical mixtures observed in an aquifer is a challenging but very important task. Frequently, some of the groundwater types are related to different infiltration and/or contamination sources associated with various geochemical signatures and origins. The characterization of groundwater mixing processes typically requires solving complex inverse models representing groundwater flow and geochemical transport in the aquifer, where the inverse analysis accounts for available site data. Usually, the model is calibrated against the available data characterizing the spatial and temporal distribution of the observed geochemical types. Numerous different geochemical constituents and processes may need to be simulated in these models which further complicates the analyses. In this paper, we propose a new contaminant source identification approach that performs decomposition of the observation mixtures based on Non-negative Matrix Factorization (NMF) method for Blind Source Separation (BSS), coupled with a custom semi-supervised clustering algorithm. Our methodology, called NMFk, is capable of identifying (a) the unknown number of groundwater types and (b) the original geochemical concentration of the contaminant sources from measured geochemical mixtures with unknown mixing ratios without any additional site information. NMFk is tested on synthetic and real-world site data. Finally, the NMFk algorithm works with geochemical data represented in the form of concentrations, ratios (of two constituents; for example, isotope ratios), and delta notations (standard normalized stable isotope ratios).

54 ENVIRONMENTAL SCIENCES↗

Nonnegative tensor factorization for contaminant source identification

Unsupervised Machine Learning (ML) is becoming increasingly popular for solving various types of data analytics problems including feature extraction, blind source separation, exploratory analyses, model diagnostics, etc. In this work, we have developed a new unsupervised ML method based on Nonnegative Tensor Factorization (NTF) for identification of the original groundwater types (including contaminant sources) present in geochemical mixtures observed in an aquifer. Frequently, groundwater types with different geochemical signatures are related to different background and/or contamination sources. The characterization of groundwater mixing processes is a challenging but very important task critical for any environmental management project aiming to characterize the fate and transport of contaminants in the subsurface and perform contaminant remediation. This task typically requires solving complex inverse models representing groundwater flow and geochemical transport in the aquifer, where the inverse analysis accounts for available site data. Usually, the model is calibrated against the available data characterizing the spatial and temporal distribution of the observed geochemical types. Numerous different geochemical constituents and processes may need to be simulated in these models which further complicates the analyses. Additionally, the application of inverse methods may introduce biases in the analyses through the assumptions made in the model development process. Here, we substitute the model inversion with unsupervised ML analysis. The ML analysis does not make any assumptions about underlying physical and geochemical processes occurring in the aquifer. Our ML methodology, called NTFk, is capable of identifying (1) the unknown number of groundwater types (contaminant sources) present in the aquifer, (2) the original geochemical concentrations (signatures) of these groundwater types and (3) spatial and temporal dynamics in the mixing of these groundwater types. These results are obtained only from the measured geochemical data without any additional site information. In general, the NTFk methodology allows for interpretation of large high-dimensional datasets representing diverse spatial and temporal components such as state variables and velocities. NTFk has been tested on synthetic and real-world site three-dimensional datasets. Finally, the NTFk algorithm is designed to work with geochemical data represented in the form of concentrations, ratios (of two constituents; for example, isotope ratios), and delta notations (standard normalized stable isotope ratios).

58 GEOSCIENCES↗

Geological implications of impacts of large asteroids and comets on the earth

The present conference discusses such topics as large object fluxes in near-earth space and the probabilities of terrestrial impacts, the geological record of impacts, dynamics modeling for large body impacts on continents and oceans, physical, chemical, and biological models of large impacts' atmospheric effects, dispersed impact ejecta and their signatures, general considerations concerning mass biological extinctions, the Cretaceous/Tertiary boundary event, geochemical signatures in the stratigraphic record, and other phanerozoic events. Attention is given to terrestrial impact rates for long- and short-period comets, estimates of crater size for large body impact, a first-order estimate of shock heating and vaporization in oceanic impacts, atmospheric effects in the first few minutes after an impact, a feasibility test for biogeographic extinction, and the planktonic and dinosaur extinctions.

Silver, L. T.↗

A record of deep-ocean dissolved O 2 from the oxidation state of iron in submarine basalts

The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O 2 ) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe 3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

58 GEOSCIENCES↗

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)

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Impact Crises, Mass Extinctions, and Galactic Dynamics: A Unified Theory

A general hypothesis linking mass extinctions of life with impacts of large asteroids and comets is based on astronomical data, impact dynamics, and geological information. The waiting times of large-body impacts on the Earth, derived from the flux of Earth-crossing asteroids and comets, and the estimated size of impacts capable of causing large-scale environmental disasters predict that impacts of objects (sup 3)5 km in diameter ((sup 3)10(exp 7) Mt TNT equivalent) could be sufficient to explain the record of about 25 extinction pulses in the last 540 m.y., with the five recorded major mass extinctions related to the impacts of the largest objects of (sup 3)10 km in diameter ( (sup 3)10(exp 8) Mt events). Smaller impacts (about 10(exp 6)-10(exp 7) Mt), with significant regional and even global environmental effects, could be responsible for the lesser boundaries in the geologic record. Tests of the "kill curve" relationship for impact-induced extinctions based on new data on extinction intensities and several well-dated large impact craters suggest that major mass extinctions require large impacts, and that a step in the kill curve may exist at impacts that produce craters of -100 km diameter, with smaller impacts capable of only relatively weak extinction pulses. Single impact craters < about 60 km in diameter should not be associated with global extinction pulses detectable in the Sepkoski database (although they may explain stage and zone boundaries marked by lesser faunal turnover), but multiple impacts in that size range may produce significant stepped extinction pulses. Statistical tests of the last occurrences of species at mass-extinction boundaries are generally consistent with predictions for abrupt or stepped extinctions, and several boundaries are known to show "catastrophic" signatures of environmental disasters and biomass crash, impoverished postextinction fauna and flora dominated by stress-tolerant and opportunistic species, and gradual ecological recovery and radiation of new taxa. Isotopic and other geochemical signatures are also generally consistent with the expected after-effects of catastrophic impacts. Seven of the recognized extinction pulses are associated with concurrent (in some cases multiple) stratigraphic impact markers (e.g., layers with high Ir, shocked minerals, microtektites), and/or large, dated impact craters. Other less-well-studied crisis intervals show elevated Ir, still well below that of the K/T spike, which might be explained by low-Ir impactors, ejecta blowoff, or the sedimentary reworking and dilution of impact signatures. The best explanation for a possible periodic component of about 30 m.y. in mass extinctions and clusters of impacts is the modulation of the comet flux associated with the solar system's periodic passage through the plane of the Milky Way Galaxy. The quantitative agreement among paleontological, geological, and astronomical data suggests an important underlying unification of the processes involved.

Rampino, M.R.↗

A New Coordinated NanoSIMS, Transmission Electron Microscopy and Atom Probe Tomography Approach For the Characterization of Primitive Astromaterials

Presolar grains are remnants of evolved stellar systems preserved within primitive extraterrestrial materials. They are important for studying physical and chemical processing, and formation mechanisms occurring within the interstellar medium, Solar Nebula and their parent stellar environments [1]. Our recent work has shown coordinated nano-scale Secondary Ion Mass Spectrometry (NanoSIMS) and Atom Probe Tomography (APT) can show isotopic and chemical signatures at major to trace levels, morphological signatures, and regional contextual relationships [2,3]. Previous studies have shown Transmission Electron Microscopy (TEM) of Focus Ion Beam (FIB) TEM lamella, can provide localized contextual relationships, crystallographic information and chemical information [1]. Coordinating NanoSIMS, TEM, and APT could gain access to almost all contextual, structural and geochemical signatures within each presolar grain. However, this has proved challenging owing to the preparation requirements for TEM and APT. For example, studying specimen prepared as APT needles in TEM removes the local context, the higher degree of surface exposure can alter the chemistry of beam sensitive materials, and the shank angle of the needle can impact the quality of TEM diffraction images. We designed a new FIB method which takes a 100 nm thick FIB-TEM lamella and sandwiches it between two indium slices (5 μm x ~300 nm x 3 μm). The indium is melted onto the lamella surface using the electron beam (Fig 1). This process adds bulk to the lamella, making it more amenable to APT needle formation (Fig 2). Consequently, samples can be prepared per the optimal requirements for each technique improving data quality, acquisition stability, and access to the signatures and relationships summarised earlier. This technique can be used for measuring multiple phases across a TEM lamella and targeting an individual phase. For example, a presolar grain identified in NanoSIMS could be targeted, studied in TEM and then indium sandwiched with its precise location in the TEM lamella marked using a Pt button for preparation of an APT needle and atomic scale acquisition. [1] A. M. Davis (2014) Meteorites and cosmochemical processes, 1. [2] Nevill N. et al. (2023) LPSC, 54, #1707. [3] Nevill N. et al. (2023) LPSC, 54, #1714.

NanoSIMS↗

Pump and Treat Impacts on Aquifer Conditions and the Development of System-wide Performance Strategies - 19077

The 200 West pump-and-treat (P and T) system on the Hanford Site's Central Plateau currently treats multiple contaminants within the 200-ZP-1 Operable Unit (OU). Initially designed to support the 200-ZP1 Remedial Action Objectives, the use of the P and T system has evolved over time to address contaminants from other regions of the aquifer as well. The P and T system currently receives water from other regions within the Central Plateau that are biogeochemically distinct, treating groundwater with elevated concentrations of carbon tetrachloride, cyanide, uranium, technetium-99, and nitrate. Given the varying geochemical signatures from current and potential future sources, combined with the operational conditions and amendments used for treatment processes, there is a need to identify the impacts of the P and T system on the aquifer and aquifer impacts on P and T performance. To this end, initial laboratory analyses and geochemical modeling efforts focused on characterizing the baseline geochemical environment for the aquifer in the 200-ZP-1 OU. Several sediment characterization techniques, including geologic descriptions, water and acid extractions, and microbiological measurements were selected to determine key geochemical and microbiological constituents for the baseline, prior to injection of the effluent from the treatment plant. Different geochemical components within sediment samples from the aquifer were identified that may significantly affect how the sediments react to P and T injection water. Batch experiments were also used to identify aquifer impacts on operational performance and support development of some column studies. These experiments were designed to test and evaluate variable P and T effluents using actual effluent solutions from the treatment plant as well as simulated Hanford groundwater at different temperatures to identify the important geochemical and biological reactions that might occur within the aquifer. Initial results were used for geochemical modeling of the effluents and batch experiments. These results, along with the baseline data obtained from the initial sediment characterization, are intended to feed into the design of the column studies and inform conceptual models and modeling efforts for evaluating the fate and transport of introduced contaminants and co-injectates, and their short- and long-term impact on the aquifer-system injection capacity. This evaluation is designed to provide additional information on the major geochemical and microbiological reactions that are driven by the injection of the P and T effluent into the aquifer. Reactive transport modeling of the laboratory experiments and extrapolation to a larger-scale modeling domain provide information that can be used for predictive evaluations of system performance based on P and T operational changes and aquifer mass loading and capacity estimates. This information can be used to address combined subsurface and operational challenges, such as the need for frequent well redevelopment to maintain injection capacity. This information also provides the technical basis for decisions related to the P and T system operations that support remedy optimization efforts and short- and long-term remedy decisions related to multiple OUs on the Hanford Site Central Plateau. (authors)

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