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At least 595 records · Page 33

Fe Oxidation and Species Distribution at the Rock–Fluid Interface of Marcellus Shale Reacted with Hydraulic Fracturing Fluid

Hydraulic fracturing of shale reservoirs resulted in significant opportunity for increased oil and gas production in the United States. Rock-fluid interactions can cause mineral dissolution and precipitation reactions that lead to permeability changes in the shale matrix, which ultimately may affect transport pathways and hydrocarbon production. Understanding the distribution of secondary precipitates, such as barite and Fe(III) (hydro)oxides, and cation leaching at the rock-fluid interface is an important step to further investigate how these geochemical processes can change permeability and transport pathways. In this study, thin sections of the fracture-matrix interface were made from reacted Marcellus shale cores. The thin sections were characterized using synchrotron X-ray fluorescence imaging and synchrotron X-ray absorption spectroscopy. Fe species with different oxidation states were identified in the maps, together with barite and Ca distribution. The results show that ferrihydrite, as newly formed Fe(III)-bearing precipitates, aligned well with the border of the Ca (e.g., calcite) leaching region in the reaction front. Some Fe-containing clay also dissolved, but the dissolution region for the clay was not as deep as the calcite. Further, the reaction front is about three times deeper in the direction parallel to the shale bedding than that perpendicular to the bedding. The Ca leaching region can be an index for reaction front detection for Marcellus shale. Reactive transport modeling was conducted and the predicted Ca leaching boarder align well with ferrihydrite precipitation, consistent with the experimental observation. The carbonate mineral dissolution can be crucial to promote fluid access into the shale matrix. Together with our previous study on the shale reactive surface, this follow-up study showed similar Ca leaching region and Fe(III) precipitates distribution in the reaction front regardless of barite precipitation on the surface, indicating that the barite coatings on the surface may not pose a significant impact on reactive transport at the shale-fluid interface.

04 OIL SHALES AND TAR SANDS↗

Geochemical constraints on bacteriophage infectivity in terrestrial environments

Abstract Lytic phages can be potent and selective inhibitors of microbial growth and can have profound impacts on microbiome composition and function. However, there is uncertainty about the biogeochemical conditions under which phage predation modulates microbial ecosystem function, particularly in terrestrial systems. Ionic strength is critical for infection of bacteria by many phages, but quantitative data is limited on the ion thresholds for phage infection that can be compared with environmental ion concentrations. Similarly, while carbon composition varies in the environment, we do not know how this variability influences the impact of phage predation on microbiome function. Here, we measured the half-maximal effective concentrations (EC50) of 80 different inorganic ions for the infection of E. coli with two canonical dsDNA and ssRNA phages, T4 and MS2, respectively. Many alkaline earth metals and alkali metals enabled lytic infection but the ionic strength thresholds varied for different ions between phages. Additionally, using a freshwater nitrate-reducing microbiome, we found that the ability of lytic phages to influence nitrate reduction end-products depended upon the carbon source as well as ionic strength. For all phage:host pairs, the ion EC50s for phage infection exceeded the ion concentrations found in many terrestrial freshwater systems. Thus, our findings support a model where phages most influence terrestrial microbial functional ecology in hot spots and hot moments such as metazoan guts, drought influenced soils, or biofilms where ion concentration is locally or transiently elevated and nutrients are available to support the growth of specific phage hosts.

Carlson, Hans K. (ORCID:0000000215835313)↗

The breakup of a long-period comet is not a likely match to the Chicxulub impactor

Since the discovery of Ir in the clay layer at the K-Pg boundary [1], scientists have sought to constrain the origin of the extraterrestrial impactor that triggered the end-Cretaceous mass extinction of the non-avian dinosaurs and other species. While the first proposal was for an asteroid, for a while some theories invoked a cometary impactor to explain perceived periodicities in mass extinctions. Such models have long been disfavored by the mass of Ir in the layer, inferred to be2.0−2.8×1011g. The size of Chicxulub crater leads to an estimated asteroid impactor diameter,D≈10 km. Comets typically impact at higher speeds, reducing the impactor mass for the same impact energy. Although it is increasingly recognized that a continuum exists between comets and asteroids, ’comets’ are considered to be more ice-rich (estimates for67P/ Churyumov-Gerasimenko are about 20%;), implying lower Ir contents per impactor mass. A carbonaceous chondrite-like asteroid of the appropriate size would likely deliver≈2.3×1011gof Ir, in the center of the estimated mass range of the global Ir layer; but a comet would only deliver∼0.1×1011g, because it would be less massive. Although these conclusions are long standing, Siraj & Loeb have recently argued anew in favor of a comet over an asteroid, based on dynamical and geochemical evidence. Here we demonstrate that their arguments are based on misinterpretations of the literature, and that an asteroid is in fact still highly favored over a comet.

Steven J Desch↗

Assessment of CO 2 trapping mechanisms in partially depleted oil-bearing sands

The goal of this work is to evaluate various CO 2 sequestration mechanisms occurring in the Morrow B Sandstone in the Farnsworth Unit. A history-matched numerical simulation model was created using extensive geological, petrophysical, and operational data collected from the field. The numerical model is competent to investigate the impact of residual, structural-stratigraphic, solubility, and mineral trapping mechanisms on the fluid transportation dynamics and petrophysical property variations. The model forecasts the field response of 20 years of WAG injections. Afterward, all wells were shut-in, and the reservoir was allowed to evolve for 1000 years to investigate the fate of injected CO 2 . In this paper, we assess the impacts of various trapping mechanisms on oil recovery and CO 2 storage efficacy. By analyzing the results reported from the numerical simulation model, the in-situ fluid composition and mineralogy changes are also investigated. More importantly, we seek to confirm the petrophysical property variations due to the CO 2 injection with observations from laboratory measurements. The experiences gained from this study provide valuable insights regarding physiochemical storage induced by the CO 2 injection activities and serve as a benchmark case for future CO 2 enhanced oil recovery (EOR) projects involving reactive solute transport.

42 ENGINEERING↗

Distinct Fracture Mineralogy That is Out of Equilibrium With Modern Groundwaters Provides Important Context for Subsurface Life

Rock fracture surfaces in the crust are essential habitat for microorganisms. Fracture‐groundwater interfaces provide physical substrates for biofilm growth and are sources of carbon, nutrients, and electron donors and acceptors. To better understand geochemical processes impacting fracture surfaces and the subsurface microbiome, we identified fractures in archived rock cores from the Soudan formation, which is known to host saline groundwaters and isolated microbial communities dependent on rock‐water interactions. Cores with open fractures were thin sectioned and studied via electron microprobe and synchrotron X‐ray fluorescence microprobe. Most fracture surfaces had mineralogy distinct from that of the bulk rock. Chlorite minerals were abundant on fracture surfaces and had elemental compositions suggesting deposition during late‐stage hydrothermal alteration. Fracture‐lining chlorites likely limit access to iron oxide and sulfide minerals that are active in subsurface biogeochemical cycles. Calcium‐rich rinds were also observed along fracture edges. These rinds were too thin and poorly ordered to be identified via light microscopy or X‐ray diffraction; however, Ca K‐edge micro‐X‐ray absorption near‐edge structure spectroscopy identified them as carbonates, minerals not observed in the bulk rock. Thermodynamic modeling shows that carbonate precipitation is largely unfavorable in Soudan groundwaters, indicating that fracture edge conditions differed from those in modern water samples. Because of the low carbon concentrations in Soudan groundwaters, carbonate rinds likely play an important role in subsurface carbon cycling and may mark fracture surfaces that once hosted biofilms. Overall, this study suggests that fracture alteration can both play an active role in and suppress rock‐water interactions essential to subsurface life.

36 MATERIALS SCIENCE↗

Constraints on the Composition and Evolution of the Lunar Crust from Meteorite NWA 3163

The lunar meteorite NWA 3163 (paired with NWA 4881, 4483) is a ferroan, feldspathic granulitic breccia characterized by pigeonite, augite, olivine, maskelynite and accessory Tichromite, ilmenite and troilite. Bulk rock geochemical signatures indicate the lack of a KREEP- derived component (Eu/Eu* = 3.47), consistent with previously studied lunar granulites and anorthosites. Bulk rock chondrite-normalized signatures are however distinct from the anorthosites and granulites sampled by Apollo missions and are relatively REE-depleted. In-situ analyses of maskelynite reveal little variation in anorthite content (average An% is 96.9 +/- 1.6, 2 sigma). Olivine is relatively ferroan and exhibits very little variation in forsterite content with mean Fo% of 57.7 +/- 2.0 (2 sigma). The majority of pyroxene is low-Ca pigeonite (En57Fs33Wo10). Augite (En46Fs21Wo33) is less common, comprising approximately 10% of analyzed pyroxene. Two pyroxene thermometry on co-existing orthopyroxene and augite yield an equilibrium temperature of 1070C which is in reasonable agreement with temperatures of 1096C estimated from pigeonite compositions. Rb-Sr isotopic systematics of separated fractions yield an average measured Sr-87/Sr-87 of 0.699282+/-0.000007 (2 sigma). Sr model ages are calculated using a modern day Sr-87/Sr-86 Basaltic Achondrite Best Initial (BABI) value of 0.70475, from an initial BABI value Sr-87/Sr-86 of 0.69891 and a corresponding Rb-87/Sr-97 of 0.08716. The Sr model Thermomechanical analysis (TMA) age, which represents the time of separation of a melt from a source reservoir having chondritic evolution, is 4.56+/-0.1 Ga. A Sr model T(sub RD) age, which is a Rb depletion age and assumes no contribution from Rb in the sample in the calculation, yields 4.34+/-0.1 Ga (i.e. a minimum age). The Ar-Ar dating of paired meteorite NWA 4881 reveals an age of c. 2 Ga, likely representing the last thermal event this meteorite experienced. An older Ar-40/Ar-39 age of c. 3.5 Ga may record the thermal event which produced the granulitic texture. Additional chronological constraints will be provided by Sm-Nd systematics. Ferroan Anorthosites like NWA 3163 have been interpreted to represent direct lunar magma ocean (LMO) crystallization products. If this is the case, trace element concentrations in NWA 3163 primary mineral phases should be in equilibrium with residual LMO liquids present during crystallization of those phases. Results from petrogenetic modeling suggest that the NWA 3163 protolith did not form from crystallization of an initially LREE depleted LMO but rather require an initially chondritic LMO with early garnet crystallization. Furthermore, a two-stage crystallization model where plagioclase crystalized prior to pyroxene (93% vs. 99.5% of LMO crystallization) is implied.

McLeod, C. L.↗

The Hadean, Through a Glass Telescopically: Observations of Young Solar Analogs

Investigations into the Earth's surface environment during the Hadean eon (prior to 3.8 Ga) are hampered by the paucity of the geological and geochemical record and the relative inaccessibility of better-preserved surfaces with possibly similar early histories (i.e., Mars). One approach is to observe nearby, young solar-mass stars as analogs to the Hadean Sun and its environment. A catalog of 38 G and early K stars within 25 pc was constructed based on main-sequence status, bolometric luminosity, lack of known stellar companions within 800 AU, and coronal X-ray luminosities commensurate with the higher activity of solar-mass stars <0.8 b.y. old. Spectroscopic data support the assignment of ages of 0.2 - 0.8 Ga for most of these stars. Observations of these objects will provide insight into external forces that influenced Hadean atmosphere, ocean, and surface evolution (and potential ecosystems), including solar luminosity evolution, the flux and spectrum of solar ultraviolet radiation, the intensity of the solar wind, and the intensity and duration of a late period of heavy bombardment. The standard model of solar evolution predicts a luminosity of 0.75 solar luminosity at the end of the Hadean, implying a terrestrial surface temperature inconsistent with the presence of liquid water and motivating atmospheric greenhouse models. An alternative model fo solar evolution that invokes mass loss, constructed to explain solar Li depletion, attenuates or reverses this luminosity evolution of the atmospheres of Earth and the other terrestrial planets. This model can be tested by Li abundance measurements. The continuum emission from stellar wind plasma during significant mass loss may be detectable at millimeter and radio wavelengths. The Earth (and Moon) experienced a period of intense bombardment prior to 3.8 Ga, long after accretion was completed in the inner solar system and possibly associated with the clearing of residual planetesimals in the outer solar system. Such a bombardment may have contributed volatiles and organics to the surface, but also have limited the appearacne of a biosphere. While planetary systems around solar systems cannot be detected directly with present technology, the thermal emission from the interplanetary dust generated during a similar heavy bombardment period can be. Midinfrared observations of a large uniform sample of solar analogs are used to constrain the frequency and duration of such events.

Gaidos, E. J.↗

Spatial and temporal metagenomics of river compartments reveals viral community dynamics in an urban impacted stream

Although river ecosystems constitute a small fraction of Earth’s total area, they are critical modulators of microbially and virally orchestrated global biogeochemical cycles. However, most studies either use data that is not spatially resolved or is collected at timepoints that do not reflect the short life cycles of microorganisms. To address this gap, we assessed how viral and microbial communities change over a 48-hour period by sampling surface water and pore water compartments of the wastewater-impacted River Erpe in Germany. We sampled every 3 hours resulting in 32 samples for which we obtained metagenomes along with geochemical and metabolite measurements. From our metagenomes, we identified 6,500 viral and 1,033 microbial metagenome assembled genomes (MAGs) and found distinct community membership and abundance associated with each river compartment (e.g., Competibacteraceae in surfacewater and Sulfurimonadaceae in pore water). We show that 17% of our viral MAGs clustered to viruses from other ecosystems like wastewater treatment plants and rivers. Our results also indicated that 70% of the viral community was persistent in surface waters, whereas only 13% were persistent in the pore waters taken from the hyporheic zone. Finally, we predicted linkages between 73 viral genomes and 38 microbial genomes. These putatively linked hosts included members of the Competibacteraceae, which we suggest are potential contributors to river carbon and nitrogen cycling via denitrification and nitrogen fixation. Together, these findings demonstrate that members of the surface water microbiome from this urban river are stable over multiple diurnal cycles. These temporal insights raise important considerations for ecosystem models attempting to constrain dynamics of river biogeochemical cycles.

54 ENVIRONMENTAL SCIENCES↗

The bulk-Moon MgO/FeO ratio: A highlands perspective

Compositional data for nonmare (highlands) samples suggest that the Moon's mg ratio (MgO/FeO) is higher than general estimates. Geochemically representative highlands soils have mg ratios of 0.66 (Apollo 16), 0.69 (Luna 20) and 0.73 (ALHA81005). These soils are mixtures of unrelated pristine nonmare rocks, of which there are at least three groups: Mg-rich rocks, ferroan anorthosites, and KREEP. Other than Mg-rich rocks, virtually all pristine rocks have mg 0.65. Thus, assuming the mixing process that sampled Mg-rich materials was random, the average mg of Mg-rich parent magmas was probably at least 0.70. More direct evidence can be derived from the Mg-rich rocks themselves. Nine of them have bulk-rock mg 0.87. Two (15445 A and 67435 PST) contain Fo(92) olivine. Production of melts that crystallized Fo(92) olivine implies that the mg ratios of source regions in lunar mantle were commensurably high. A quantification of this constraint is developed assuming that the parent melts formed by equilibrium (batch) partial melting. Implications of the model are discussed.

Warren, P. H.↗

A tale of two planets: Disparate evolutionary models for Mars inferred from radiogenic isotope compositions of Martian meteorites

The radiogenic isotopic compositions of basaltic Martian meteorites (shergottites) and clinopyroxene/olivine cumulate meteorites (nakhlite/chassignites) are used to define the global evolution of Mars. However, the two main groups of meteorites demonstrate that their sources underwent divergent styles of magmatic evolution. The shergottites portray a planet that differentiated ~4.52 billion years ago via solidification of a magma ocean, producing incompatible element-depleted and -enriched reservoirs that remained isolated until melt production. In contrast, the reservoir from which the nakhlite/chassignites derive may have formed earlier, produced melts that fractionated Sm/Nd and Hf/W differently, was compositionally less variable, and experienced a significantly more complex history following primordial differentiation than the shergottite sources. The disparate histories recorded by these two groups of meteorites elucidate important questions that could be addressed by acquiring additional samples. Obtaining samples that shared the isotopic systematics of the shergottites would provide confidence that extrapolating the primordial differentiation history of Mars from shergottite radiogenic isotope systematics is reasonable. Returned samples from Mars will also constrain the physical locations of the meteorite source regions, providing insights into the general structure of the Martian mantle. In addition, they will help constrain the phases present in the martian mantle during melting and the conditions under which they are stable. Finally, identifying an evolved lithology that satisfies the geochemical and isotopic constraints placed on the incompatible element-enriched endmember observed in the shergottites would define the nature of magmatic evolution on Mars and whether it is more akin to processes on the Earth or the Moon.

Mars↗

The breakup of a long-period comet is not a likely match to the Chicxulub impactor

Since the discovery of Ir in the clay layer at the K-Pg boundary, scientists have sought to constrain the origin of the extraterrestrial impactor that triggered the end-Cretaceous mass extinction of the non-avian dinosaurs and other species. While the first proposal was for an asteroid, for a while some theories invoked a cometary impactor to explain perceived periodicities in mass extinctions. Such models have long been disfavored by the mass of Ir in the layer, inferred to be 2.0−2.8×10^(11)cu.g. The size of the Chicxulub crater leads to an estimated asteroid impactor diameter, D≈10km. Comets typically impact at higher speeds, reducing the impactor mass for the same impact energy. Although it is increasingly recognized that a continuum exists between comets and asteroids, ’comets’ are considered to be more ice-rich (estimates for 67P/Churyumov-Gerasimenko are about 20%;), implying lower Ir contents per impactor mass. A carbonaceous chondrite-like asteroid of the appropriate size would likely deliver ≈2.3×10^(11)g of Ir, in the center of the estimated mass range of the global Ir layer; but a comet would only deliver ∼0.1×10^(11)g, because it would be less massive. Although these conclusions are long standing, Siraj and Loeb have recently argued anew in favor of a comet over an asteroid, based on dynamical and geochemical evidence. Here we demonstrate that their arguments are based on misinterpretations of the literature, and that an asteroid is in fact still highly favored over a comet.

Steven J. Desch↗

From legacy contamination to watershed systems science: a review of scientific insights and technologies developed through DOE-supported research in water and energy security

Abstract Water resources, including groundwater and prominent rivers worldwide, are under duress because of excessive contaminant and nutrient loads. To help mitigate this problem, the United States Department of Energy (DOE) has supported research since the late 1980s to improve our fundamental knowledge of processes that could be used to help clean up challenging subsurface problems. Problems of interest have included subsurface radioactive waste, heavy metals, and metalloids (e.g. uranium, mercury, arsenic). Research efforts have provided insights into detailed groundwater biogeochemical process coupling and the resulting geochemical exports of metals and nutrients to surrounding environments. Recently, an increased focus has been placed on constraining the exchanges and fates of carbon and nitrogen within and across bedrock to canopy compartments of a watershed and in river–floodplain settings, because of their important role in driving biogeochemical interactions with contaminants and the potential of increased fluxes under changing precipitation regimes, including extreme events. While reviewing the extensive research that has been conducted at DOE’s representative sites and testbeds (such as the Oyster Site in Virginia, Savannah River Site in South Carolina, Oak Ridge Reservation in Tennessee, Hanford in Washington, Nevada National Security Site in Nevada, Riverton in Wyoming, and Rifle and East River in Colorado), this review paper explores the nature and distribution of contaminants in the surface and shallow subsurface (i.e. the critical zone) and their interactions with carbon and nitrogen dynamics. We also describe state-of-the-art, scale-aware characterization approaches and models developed to predict contaminant fate and transport. The models take advantage of DOE leadership-class high-performance computers and are beginning to incorporate artificial intelligence approaches to tackle the extreme diversity of hydro-biogeochemical processes and measurements. Recognizing that the insights and capability developments are potentially transferable to many other sites, we also explore the scientific implications of these advances and recommend future research directions.

54 ENVIRONMENTAL SCIENCES↗

Magma Reservoirs Feeding Giant Radiating Dike Swarms: Insights from Venus

Evidence of lateral dike propagation from shallow magma reservoirs is quite common on the terrestrial planets, and examination of the giant radiating dike swarm population on Venus continues to provide new insight into the way these complex magmatic systems form and evolve. For example, it is becoming clear that many swarms are an amalgamation of multiple discrete phases of dike intrusion. This is not surprising in and of itself, as on Earth there is clear evidence that formation of both magma reservoirs and individual giant radiating dikes often involves periodic magma injection. Similarly, giant radiating swarms on Earth can contain temporally discrete subswarms defined on the basis of geometry, crosscutting relationships, and geochemical or paleomagnetic signatures. The Venus data are important, however, because erosion, sedimentation, plate tectonic disruption, etc. on Earth have destroyed most giant radiating dike swarm's source regions, and thus we remain uncertain about the geometry and temporal evolution of the magma sources from which the dikes are fed. Are the reservoirs which feed the dikes large or small, and what are the implications for how the dikes themselves form? Does each subswarm originate from a single, periodically reactivated reservoir, or do subswarms emerge from multiple discrete geographic foci? If the latter, are these discrete foci located at the margins of a single large magma body, or do multiple smaller reservoirs define the character of the magmatic center as a whole? Similarly, does the locus of magmatic activity change with time, or are all the foci active simultaneously? Careful study of giant radiating dike swarms on Venus is yielding the data necessary to address these questions and constrain future modeling efforts. Here, using giant radiating dike swarms from the Nemesis Tessera (V14) and Carson (V43) quadrangles as examples, we illustrate some of the dike swarm focal region diversity observed on Venus and briefly explore some key implications for the questions framed above.

Grosfils, E. B.↗

The Cretaceous-Tertiary Impact Crater and the Cosmic Projectile that Produced it

Evidence gathered to date from topographic data, geophysical data, well logs, and drill-core samples indicates that the buried Chicxulub basin, the source crater for the approximately 65 Ma Cretaceous-Tertiary (K/T) boundary deposits, is approximately 300 km in diameter. A prominent topographic ridge and a ring of gravity anomalies mark the position of the basin rim at approximately 150 km from the center. Wells in this region recovered thick sequences of impact-generated breccias at 200-300 m below present sea level. Inside the rim, which has been severely modified by erosion following impact, the subsurface basin continues to deepen until near the center it is approximately 1 km deep. The best planetary analog for this crater appears to be the 270 km-diameter Mead basin on Venus. Seismic reflection data indicate that the central zone of downward displacement and excavation (the transient crater is approximately 130 km in diameter, consistent with previous studies of gravity anomaly data). Our analysis of projectile characteristics utilizes this information, coupled with conventional scaling relationships, and geochemical constraints on the mass of extraterrestrial material deposited within the K/T boundary layer. Results indicate that the Chicxulub crater would most likely be formed by a long-period comet composed primarily of nonsilicate materials (ice, hydrocarbons, etc.) and subordinate amounts (less than or equal to 50 percent) primitive chondritic material. This collision would have released the energy equivalent to between 4 x 10(exp 8) and 4 x 10(exp 9) megatons of TNT. Studies of terrestrial impact rates suggest that such an event would have a mean production rate of approximately 1.25 x 10(exp -9) y(exp -1). This rate is considerably lower than that of the major mass extinctions over the last 250 million years (approximately 5 x 10(exp -7) y(exp -1). Consequently, while there is substantial circumstantial evidence establishing the cause-effect link between the Chicxulub basin forming event and the K/T biological extinctions, the results of our analysis do not support models of impact as a common or singular causative agent of mass extinctions on Earth.

Sharpton, Virgil L.↗

Methyl bromide: ocean sources, ocean sinks, and climate sensitivity

The oceans play an important role in the geochemical cycle of methyl bromide (CH3Br), the major carrier of O3-destroying bromine to the stratosphere. The quantity of CH3Br produced annually in seawater is comparable to the amount entering the atmosphere each year from natural and anthropogenic sources. The production mechanism is unknown but may be biological. Most of this CH3Br is consumed in situ by hydrolysis or reaction with chloride. The size of the fraction which escapes to the atmosphere is poorly constrained; measurements in seawater and the atmosphere have been used to justify both a large oceanic CH3Br flux to the atmosphere and a small net ocean sink. Since the consumption reactions are extremely temperature-sensitive, small temperature variations have large effects on the CH3Br concentration in seawater, and therefore on the exchange between the atmosphere and the ocean. The net CH3Br flux is also sensitive to variations in the rate of CH3Br production. We have quantified these effects using a simple steady state mass balance model. When CH3Br production rates are linearly scaled with seawater chlorophyll content, this model reproduces the latitudinal variations in marine CH3Br concentrations observed in the east Pacific Ocean by Singh et al. [1983] and by Lobert et al. [1995]. The apparent correlation of CH3Br production with primary production explains the discrepancies between the two observational studies, strengthening recent suggestions that the open ocean is a small net sink for atmospheric CH3Br, rather than a large net source. The Southern Ocean is implicated as a possible large net source of CH3Br to the atmosphere. Since our model indicates that both the direction and magnitude of CH3Br exchange between the atmosphere and ocean are extremely sensitive to temperature and marine productivity, and since the rate of CH3Br production in the oceans is comparable to the rate at which this compound is introduced to the atmosphere, even small perturbations to temperature or productivity can modify atmospheric CH3Br. Therefore atmospheric CH3Br should be sensitive to climate conditions. Our modeling indicates that climate-induced CH3Br variations can be larger than those resulting from small (+/- 25%) changes in the anthropogenic source, assuming that this source comprises less than half of all inputs. Future measurements of marine CH3Br, temperature, and primary production should be combined with such models to determine the relationship between marine biological activity and CH3Br production. Better understanding of the biological term is especially important to assess the importance of non-anthropogenic sources to stratospheric ozone loss and the sensitivity of these sources to global climate change.

NASA Discipline Exobiology↗

The Chlorine Isotopic Composition Of Lunar UrKREEP

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

Barnes, J. J.↗

Seismic Visibility of Eclogite in the Earth’s Upper Mantle—Implications From High Pressure‐Temperature Single‐Crystal Elastic Properties of Omphacite

Abstract Identifying and locating the geochemical and geophysical heterogeneities in the Earth’s interior is one of the most important and challenging tasks for the deep Earth scientists. Subducted oceanic crust metamorphizes into the dense eclogite in the upper mantle and is considered as a major cause of geochemical and geophysical heterogeneities in the deep Earth. In order to detect eclogitic materials inside the Earth, precise measurements of the high pressure‐temperature single‐crystal elasticity of major minerals in eclogite are thus exceedingly important. Omphacite, a Na,Al‐bearing clinopyroxene, constitutes up to 75 vol% of eclogite. In the present study, we performed the first high pressure‐temperature single‐crystal elasticity measurements of omphacite using Brillouin spectroscopy. Utilizing the finite‐strain approach, we obtained the following thermoelastic parameters for omphacite: K S0 ’ = 4.5(1), G 0 ’ = 1.53(5), ∂K S0 /∂ T = −0.029(5) GPa/K, ∂G 0 /∂ T = −0.013(5) GPa/K, with K S0 = 123(3) GPa, G 0 = 74(2) GPa, and ρ 0 = 3.34(1) g/cm 3 . We found that the seismic velocities of undeformed eclogite are similar to pyrolite at the depths of 200–300 and 410–500 km, thus eclogite is seismically invisible at these depths. Combined with the lattice‐preferred orientations of the omphacite in naturally deformed eclogites, we also modeled seismic anisotropy of eclogite at various pressure‐temperature conditions. A 10 km thick subducted eclogitic crust can result in ∼0.2 s shear wave splitting in the Earth’s upper mantle.

Hao, Ming↗

Geochemistry, volumetric water content, and active layer depths from rainfall simulations at the Kougarok Fire Site, Seward Peninsula, Alaska, 2022

Rainfall frequency and intensity is expected to increase in the Arctic, with potential implications for permafrost thaw and geochemical fluxes in soils. To conduct controlled rainfall experiments at remote field sites in the Arctic, the Next-Generation Ecosystem Experiments Arctic Rainfall Simulator (NARS) was developed at Los Alamos National Laboratory as part of the NGEE Arctic project. To better understand how rainfall may affect interflow biogeochemistry and permafrost thaw, rainfall simulations were performed on the Seward Peninsula of Alaska during late September and early October 2022 at the Kougarok Fire Site near mile marker 86 of the Nome-Taylor Highway. Water samples were collected before, during, and after rainfall simulations until interflow had ceased. Additional data collected included soil pore water samples from macrorhizons, active layer depths, and volumetric water content at each of the experimental plots. This dataset contains one *.csv file of water sample properties, one *.csv file of thaw depths, one *.csv file of soil moisture measurements, and one *.kml file of the locations where samples were collected.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy’s Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy’s Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗