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One of the prevailing hypotheses for the origin of the Younger Dryas (YD) cooling event is that it resulted from a bolide impact or airburst. Purported impact markers peak at or near the YD basal boundary layer at Northern Hemisphere locations. In this study, the 187Os/188Os ratios and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances in a well-dated sediment section through the Younger Dryas at the Debra L. Friedkin site, Texas are reported. Unradiogenic 187Os/188Os peaks, which could be mantle-derived or extraterrestrial, have been found above, within, and below the YD basal boundary layer. Mass balance mixing models using chondrites or iron meteorites with upper continental crust fail to duplicate the chondrite-normalized HSE patterns of the sediment samples. These HSE signatures in the Friedkin site section replicate those found in Hall’s Cave, Texas. The new results here thus independently confirm that the HSE abundances in the unradiogenic Os layers are likely a fingerprint of volcanic gas aerosols derived from large Plinian eruptions and not extra-terrestrial materials. To better constrain the lithological origins of YD sediments from the Friedkin and Hall’s Cave sites, Texas, trace elements are presented here. The rare earth elements (REE) patterns and Ir, Ni, Ti and Zr abundances are also characterized with terrestrial signatures as opposed to impact melt rocks. An age profile correlation between the two study sites, further shows that three unradiogenic Os peaks overlap in time. The results are inconsistent with the extraterrestrial hypothesis and support instead an episodic and volcanic origin for the observed geochemical anomalies at the Debra L. Friedkin and Hall’s Cave sites, Texas.

Professional engagement helps students develop professional judgment, connect their coursework to the “real world,” and explore accounting-related careers. Internships often provide a route to these benefits, but some students cannot complete internships. The Pathways Commission calls for new, creative approaches to professional engagement. In the ethics interview exercise, students engage with professionals for a single interview. Following the intentional learning model, students complete activities before and after the interview. They select the interviewee, prepare questions about ethics and topics of personal interest, organize and conduct the interview, and reflect on the experience. We implemented the exercise in different accounting courses at universities in the United States and Bolivia, using both face-to-face and virtual interviews. We applied principles of phenomenology for assessment. Results indicate the exercise helps students experience the benefits of professional engagement. The exercise requires little modification to existing courses and can be modified to support varied learning goals.

Why households eligible for SNAP do not participate has perplexed scholars. Explanations exist, but few explore whether SNAP nonparticipation coincides with private food assistance. Applying an inn...

Ocean anoxic events (OAE) are characterized by increased organic content of marine sediment on a global scale with accompanying positive excursions in sedimentary organic and inorganic δ 13C values. To sustain the increased C exports and burial required to explain the C isotope excursion, increased supplies of nutrients to the oceans are often invoked during ocean anoxic events. The potential source of nutrients in these events is investigated in this study for Oceanic Anoxic Event 2, which spans the Cenomanian-Turonian boundary. Massive eruptions of one or more Large Igneous Provinces (LIPs) are the proposed trigger for OAE 2. The global warming associated with volcanogenic loading of carbon dioxide to the atmosphere has been associated with increased continental weathering rates during OAE 2, and by extension, enhanced nutrient supplies to the oceans. Seawater interactions with hot basalts at LIP eruption sites can further deliver ferrous iron and other reduced metals to seawater that can stimulate increased productivity in surface waters and increased oxygen demand in deep waters. The relative importance of continental and submarine weathering drivers of expanding ocean anoxia during OAE 2 are difficult to disentangle. In this paper, a box model of the marine Sr cycle is used to constrain the timing and relative magnitudes of changes in the continental weathering and hydrothermal Sr fluxes to the oceans during OAE 2 using a new high-resolution record of seawater 87Sr/86Sr ratios preserved in a marl-limestone succession from the Iona-1 core collected from the Eagle Ford Formation in Texas. The results show that seawater 87Sr/86Sr ratios change synchronously with Os isotope evidence for the onset of massive LIP volcanism 60 kyr before the positive C isotope excursion that traditionally marks the onset of OAE 2. The higher temporal resolution of the seawater Sr isotope record presented in this study warrants a detailed quantitative analysis of the changes in continental weathering and hydrothermal Sr inputs to the oceans during OAE 2. Using an ocean Sr box model, it is found that increasing the continental weathering Sr flux by ∼1.8-times captures the change in seawater 87Sr/86Sr recorded in the Iona-1 core. The increase in the continental weathering flux is smaller than the threefold increase estimated by studies of seawater Ca isotope changes during OAE 2, suggesting that hydrothermal forcing may have played a larger role in the development of ocean anoxic events than previously considered

Whether hydrogen incorporated in nominally anhydrous mantle minerals plays a role in the strength and longevity of the thick cratonic lithosphere is a matter of debate. In particular, the percolation of hydrogen-bearing melts and fluids could potentially add hydrogen to the mantle lithosphere, weaken its olivines (the dominant mineral in mantle peridotite), and cause delamination of the lithosphere's base. The influence of metasomatism on hydrogen contents of cratonic mantle minerals can be tested in mantle xenoliths from the Slave Craton (Canada) because they show extensive evidence for metasomatism of a layered cratonic mantle. Minerals from mantle xenoliths from the Diavik mine in the Lac de Gras kimberlite area located at the center of the Archean Slave craton were analyzed by FTIR for hydrogen contents. The 18 peridotites, two pyroxenites, one websterite and one wehrlite span an equilibration pressure range from 3.1 to 6.6 GPa and include samples from the shallow (≤145 km), oxidized ultra-depleted layer; the deeper (∼145–180 km), reduced less depleted layer; and an ultra-deep (≥180 km) layer near the base of the lithosphere. Olivine, orthopyroxene, clinopyroxene and garnet from peridotites contain 30–145, 110–225, 105–285, 2–105 ppm H2O, respectively. Within each deep and ultra-deep layer, correlations of hydrogen contents in minerals and tracers of metasomatism (for example light over heavy rare-earth-element ratio (LREE/HREE), high-field-strength-element (HFSE) content with equilibration pressure) can be explained by a chromatographic process occurring during the percolation of kimberlite-like melts through garnet peridotite. The hydrogen content of peridotite minerals is controlled by the compositions of the evolving melt and of the minerals and by mineral/melt partition coefficients. At the beginning of the process, clinopyroxene scavenges most of the hydrogen and garnet most of the HFSE. As the melt evolves and becomes enriched in hydrogen and LREE, olivine and garnet start to incorporate hydrogen and pyroxenes become enriched in LREE. The hydrogen content of peridotite increases with decreasing depth, overall (e.g., from 75 to 138 ppm H2O in the deep peridotites). Effective viscosity calculated using olivine hydrogen content for the deepest xenoliths near the lithosphere-asthenosphere boundary overlaps with estimates of asthenospheric viscosities. These xenoliths cannot be representative of the overall cratonic root because the lack of viscosity contrast would have caused basal erosion of lithosphere. Instead, metasomatism must be confined in narrow zones channeling kimberlite melts through the lithosphere and from where xenoliths are preferentially sampled. Such localized metasomatism by hydrogen-bearing melts therefore does not necessarily result in delamination of the cratonic root.

Oceanic Anoxic Event 2 (OAE-2) occurred at the Cenomanian-Turonian boundary (∼94.1 Ma) and was a time of profound global changes in ocean chemistry and the carbon cycle. This event was characterized by a positive carbon isotope excursion (CIE) caused by massive organic carbon burial, global greenhouse temperatures, ocean deoxygenation, and changes in ocean life driven by large igneous province (LIP) activity. LIPs throughout the Phanerozoic have had dynamic magma flux, with episodes of major eruptions interspersed with periods of relatively less intense eruptions. A possible trigger for LIP activity throughout the Phanerozoic has been attributed to extraterrestrial impacts because there are multiple contemporaneous occurrences of large craters, LIP activity, and mass extinctions in the geologic record. At the Cenomanian-Turonian boundary, there is a 25 km diameter (rim-to-rim) complex crater in NW Alberta, Canada known as the Steen River impact structure dated at 91 ± 7 Ma (Carrigy and Short, 1968). An alternative explanation for those craters found contemporaneous with LIP activity and mass extinctions is that they were created by large explosive events related to LIP activity. Explosive events associated with mantle plume incubation beneath cratonic lithosphere have been suggested to create geologic features commonly attributed to impacts (e.g., shocked quartz, microspherules, etc.). Currently, the trigger for LIP activity during OAE-2, as well as the duration of LIP activity and the temporal variation and magnitude of eruption rates are not well constrained. To address the issue of LIP eruption rates and the trigger for LIP activity, we examined osmium (Os) abundances and isotopes as well as highly siderophile element (HSE; for this study: Re, Ru, Pd, Os, Ir, Pt) abundance data from a continuous sedimentary section spanning OAE-2. The section is from the Eagle Ford Group in the Iona-1 core, deposited in the Cretaceous Western Interior Seaway (KWIS). We found three high Os concentration intervals with mantle-like initial Osi isotope (initial 187Os/188Os) values of ∼0.16. These intervals are interpreted to reflect high-flux LIP magmatic pulses. Between the pulses, lower Os abundances with more radiogenic Osi values of ∼0.20 are observed, which we interpret as low-flux LIP activity between the high-flux periods. This trend of high-and-low flux Os concentration pulses with mantle-like Osi values during the high flux periods is found in another KWIS core (USGS Portland #1) deposited to the north of Iona-1, and in core Deep Sea Drilling Project (DSDP) Site 530 Hole A (hereafter DSDP 530A; drilled off-shore Namibia in the Angola Basin) deposited in the Southern Hemisphere. Before and throughout the Iona-1 core OAE-2 interval, HSE abundance patterns indicate a mantle source for the unradiogenic Os, and are not consistent with an extraterrestrial impact trigger or contribution to LIP activity during OAE-2. This evidence for multiple high-flux pulses of LIP activity driving ocean deoxygenation has implications for the modern ocean, which is currently experiencing deoxygenation. These results provide new constraints on subsequent high-flux periods that extended the event. The first high-flux period started ∼60 Kyr after our selection of the onset of the CIE. The second and third high-flux periods started ∼270 and ∼400 Kyr after the onset of the CIE, respectively. After the third high-flux period, δ13Corg and Os isotope ratios shifted back to pre-excursion values over ∼585 kyr. In the Iona-1 core, OAE-2 lasted for 1.04 ± 0.12 Myr based on our selection of the CIE.

Roux-en-Y gastric bypass (RYGB) has been explored as a revisional option to failed paraesophageal hernia (PEH) repair with fundoplication, particularly in patients suffering from obesity. However, few studies have assessed long-term outcomes of RYGB with revisional PEH repairin regard to acid-suppressing medication use. We retrospectively identified 19 patients who underwent revisional PEH repair with RYGB between 2011 and 2018. The median operative time was 232 minutes with a median hospital length of stay of two days. The median length of follow-up was 24 months. Two patients (10.5%) had complications in the first 30 days, and five patients (26.3%) had complications within one year. Of the 12 patients on preoperative acid suppression, 6 (50%) were either off medication or on reduced dose at 12 months. The median BMI decrease was 14.4 kg/m2at 12 months and did not change significantly afterward. Although rates of acid-suppression medication use did not change overall after revisional PEH repair with RYGB, patients experienced successful long-term management of morbid obesity and sustained weight loss. Revisional PEH repair with RYGB is a safe and effective option, with a complication rate comparable with the reported rates after revisional foregut procedures such as revisional Nissen fundoplication.

Knowing the distribution and origin of water in terrestrial planets is crucial to understand their formation, evolution and the source of their atmospheres and surface water. The nakhlites represent a suite of minimally shocked meteorites that likely originated from lava flows from a single volcano or from a shallow intrusion or sill complex on Mars. Measuring the water contents and D/H ratios of their igneous minerals allows identification of phases that have preserved their magmatic hydrogen, and therefrom permits estimation of the water content of their mantle source. Pyroxene, olivine, melt inclusions and mesostasis of five nakhlites (NWA 998, Nakhla, Y 000593, MIL 03346 and NWA 6148) were analyzed in situ for water contents and H isotopes, and major and trace element contents. No water was detected in olivine grains except in Y 000593. The water content of pyroxenes is highly heterogeneous within individual grains and between grains within a single meteorite. Water concentrations in pyroxene ( After ruling out significant influence from spallation, exchange with the martian atmosphere, shock, surface alteration, and hydrothermal processes, the H data of the pyroxenes can be explained by degassing and crystallization processes. Degassing is consistent with a decrease of water content from pyroxene interior to edge. Fractionation of H isotopes during degassing results in increases of δD during H loss from pyroxene but in decreases in δD during H2O-OH loss from a melt. Consequently, the low-water content, high-δD of most pyroxenes is best explained by degassing after the pyroxenes had crystallized. All melt and plagioclase inclusions analyzed are located in degassed pyroxenes and are also degassed. The lower δD of the mesostasis (24 ± 131‰) compared to that of the least-degassed pyroxenes (430 ± 172‰) is likely the result of melt degassing and interaction with hydrothermal fluids. Magmatic H, however, has been preserved in each nakhlite in some pyroxenes that are characterized by >15 ppm H2O and δD

The distribution of water in the upper mantle plays a crucial role in the Earth's deep water cycle, magmatism, and plate tectonics. To better constrain how these large-scale geochemical systems operate, peridotite and pyroxenite mantle xenoliths from Kilbourne Hole (KH) and Rio Puerco (RP) along the Rio Grande Rift (NM, USA) were analyzed for water, and major and trace element contents. These xenoliths sample a lithosphere whose composition was influenced by subduction and rifting, and can be used to examine the effects of melting, metasomatism, and sub-solidus equilibration on the behavior of water. The first result is that in KH xenoliths, olivines underwent negligible H loss during xenolith ascent, i.e. preserved their mantle water contents. These olivine water contents are used to calculate mantle viscosities of 0.5–184 · 1021 Pa·s. These viscosity values are more than 40 times higher than those of the asthenosphere and show that KH peridotites represent samples from the lithosphere. The preservation of olivine water contents is exceptional for off-cratonic xenoliths, and the KH peridotites provide the first estimate of the average concentration of water in Phanerozoic continental mantle lithosphere at 81 ± 30 ppm H2O. The mantle lithosphere beneath the Rio Grande rift is nevertheless heterogeneous with water contents ranging from

The first day of lab was traditionally a day to check into lab drawers, discuss lab safety, and perform a basic primer in graphing with Microsoft (MS) Excel, but it now includes an activity that involves reproducing a rather complex graph from the scientific literature. The activity is designed to give the students a brief introduction to the layout of a scientific article; its similarity to the scientific process; and basic statistics, including mean and standard deviation. The task of reproducing the graph from the literature requires students to demonstrate their ability to perform calculations using MS Excel, plot multiple series on one graph, display trendlines, use a secondary axis, and employ custom error bars. The mastery of these skills is apparent to the students and instructors by inspection of the completed graph and grading of the spreadsheet and postactivity questions using a rubric that is specific to the learning outcomes (96.3% class average). Furthermore, the graph to be duplicated is chosen from a paper coauthored by an undergraduate from our university, which creates a sense of relevance to the students. Using an article from our institution also provides the advantage of having access to the raw data, which are not always found in the literature. The incorporation of this activity into the first lab session of our introductory first-year chemistry course has resulted in the instructors of this and subsequent courses to rarely need to assist students in creating graphs, which are the routine conclusion to many lab sessions.

International audience; Tungsten isotopes are the ideal tracers of core-mantle chemical interaction. Given that W is moderately siderophile, it preferentially partitioned into the Earth’s core during its segregation, leaving the mantle depleted in this element. In contrast, Hf is lithophile, and its short-lived radioactive isotope 182Hf decayed entirely to 182W in the mantle after metal-silicate segregation. Therefore, the 182W isotopic composition of the Earth’s mantle and its core are expected to differ by about 200 ppm. Here, we report new high precision W isotope data for mantle-derived rock samples from the Paleoarchean Pilbara Craton, and the Réunion Island and the Kerguelen Archipelago hotspots. Together with other available data, they reveal a temporal shift in the 182W isotopic composition of the mantle that is best explained by core-mantle chemical interaction. Core-mantle exchange might be facilitated by diffusive isotope exchange at the core-mantle boundary, or the exsolution of W-rich, Si-Mg-Fe oxides from the core into the mantle. Tung-sten-182 isotope compositions of mantle-derived magmas are similar from 4.3 to 2.7 Ga and decrease afterwards. This change could be related to the onset of the crystallisation of the inner core or to the initiation of post-Archean deep slab subduction that more efficiently mixed the mantle.

The geochemical behavior of Pb in terrestrial and coastal water systems significantly influences Pb biogeochemical cycling and pollutant exchange at the land-sea continuum. An ideal case study of Pb environmental geochemistry is Galveston Bay, an anthropogenic estuary exposed to industrial runoff, wastewater and shipping vessel spills but also fed by natural rivers. Here, sediments from Galveston Bay were measured for Pb isotope ratios and abundances to constrain Pb sources and fluxes and understand Pb pollution history in the bay. Lead isotopes have been established as source tracers of environmental pollution and allow Pb sources to be reliably fingerprinted and identified. Sediments were leached to distinguish authigenic sediment coatings from lithogenic residual sediments, in addition to bulk sediment digestions. Total Pb concentrations ranged from 1.76 µg/g–29.19 µg/g in bulk digests, which are below federal toxicity thresholds and aligns well with prior measurements of Pb in Galveston Bay sediments in the 20th century. Lead concentrations are spatially constrained by flocculation in eastern bay areas where the Trinity River enters the bay and positively temporally correlated to freshwater discharge. Sediment 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios range between 18.338–19.777±0.002, 15.557–15.755±0.002 and 37.913–43.340±0.005, respectively, and were used in an advanced Bayesian isotope mixing model to identify Pb sources in the Galveston Bay sediment fractions analyzed. Anthropogenic sources supply approximately 83.8%, 16.6% and 25.5% of Pb to the leachates, residues and bulk sediments, respectively. This study showcases the importance of estuaries in moderating terrestrial and marine Pb distribution and provides insight for future contaminant studies in Galveston Bay and other estuarine systems around the world. MAIN FINDINGS Pb isotope ratio and abundance measurements of Galveston Bay sediments demonstrate significant anthropogenic Pb inputs to the estuary despite low Pb levels.

Galveston Bay is an anthropogenic-influenced estuary where industrial runoff, wastewater, and shipping vessel discharges enter the bay alongside natural freshwaters. Here, heavy metal concentrations in Galveston Bay surface sediment (2-year quarterly time-series) and a single sediment core are presented to explore the anthropogenic and geochemical controls on the spatiotemporal distributions, fluxes, sources, and potential toxicity of metals within this estuary. Samples were leached to distinguish authigenic sediment coatings from geogenic crystalline material. Spatial differences dominate the observed concentration variability, with higher metal concentrations in eastern vs. western bay sediments, as the eastern bay is where metals are flocculated from the dissolved phase and/or sediments are hydrodynamically trapped. Temporal variations are a secondary controlling factor, with sediment metal concentrations positively correlated with Trinity River discharge. Core data indicate stable Fe, Pb Ni, Cd and Hg levels during the 20th century but increasing Cu and Zn levels in recent years. Galveston Bay sediments are potentially toxic for As, Cd, Cr, Cu, Ni, Sb, Zn and Hg, based on federal toxicity standards. Enrichment factors and statistical analyses suggest that Ni and Cr originate from natural sources, while anthropogenic sources dominate supply of As, Cd, Hg, Ni, Pb, Sb, and Zn. This unique time-series shows that major flooding events, such as Hurricane Harvey in 2017, affect surface sediment metal distributions in Galveston Bay, but not any more than the natural geochemical controls on spatiotemporal distributions of metals in anthropogenic-influenced estuaries.