Through the PolarTREC program that pairs US educators with field researchers in polar regions, our team has been collaborating on K-12 and undergraduate curriculum development and outreach activities on Arctic amplification of climate change. We have created new lesson plans and activities focused on how organic carbon from thawing permafrost in the Arctic is turned into carbon dioxide, a greenhouse gas that amplifies climate change. This presentation will cover our collaboration to bring this knowledge and experience to high school science students through classroom activities and projects. The focus will be laboratory activities designed for the chemistry classroom: use of spectrophotometry to assess degree of photobleaching in organic samples and evaluation of data from high resolution mass spectrometry to characterize complex organic mixtures. We will also review lessons learned from our efforts to promote enthusiasm for polar science within the general public and discuss the benefits of the PolarTREC program to researchers, educators, students, and the public.

Earth’s internal heat drives its dynamic engine, causing mantle convection, plate tectonics, and the geodynamo. These renewing and protective processes, which make Earth habitable, are fueled by a primordial (kinetic) and radiogenic heat. For the past two decades, particle physicists have measured the flux of geoneutrinos, electron antineutrinos emitted during β − decay. These ghost-like particles provide a direct measure of the amount of heat producing elements (HPE: Th & U) in the Earth and in turn define the planet’s absolute concentration of the refractory elements. The geoneutrino flux has contributions from the lithosphere and mantle. Detector sensitivity follows a 1/r 2 (source detector separation distance) dependence. Accordingly, an accurate geologic model of the Near-Field Lithosphere (NFL, closest 500 km) surrounding each experiment is required to define the mantle’s contribution. Because of its proximity to the detector and enrichment in HPEs, the local lithosphere contributes ∼50% of the signal and has the greatest effect on interpreting the mantle’s signal. We re-analyzed the upper crustal compositional model used by Agostini et al. (2020) for the Borexino experiment. We documented the geology of the western Near-Field region as rich in potassic volcanism, including some centers within 50 km of the detector. In contrast, the Agostini study did not include these lithologies and used only a HPE-poor, carbonate-rich, model for upper crustal rocks in the surrounding ∼150 km of the Borexino experiment. Consequently, we report 3× higher U content for the local upper crust, which produces a 200% decrease in Earth’s radiogenic heat budget, when compared to their study. Results from the KamLAND and Borexino geoneutrino experiments are at odds with one another and predict mantle compositional heterogeneity that is untenable. Combined analyses of the KamLAND and Borexino experiments using our revised local models strongly favor an Earth with ∼20 TW present-day total radiogenic power. The next generation of geoneutrino detectors (SNO+, counting; and JUNO, under construction) will better constrain the HPE budget of the Earth.

The discipline of land change science has been evolving rapidly in the past decades. Remote sensing played a major role in one of the essential components of land change science, which includes observation, monitoring, and characterization of land change. In this paper, we proposed a new framework of the multifaceted view of land change through the lens of remote sensing and recommended five facets of land change including change location, time, target, metric, and agent. We also evaluated the impacts of spatial, spectral, temporal, angular, and data-integration domains of the remotely sensed data on observing, monitoring, and characterization of different facets of land change, as well as discussed some of the current land change products. We recommend clarifying the specific land change facet being studied in remote sensing of land change, reporting multiple or all facets of land change in remote sensing products, shifting the focus from land cover change to specific change metric and agent, integrating social science data and multi-sensor datasets for a deeper and fuller understanding of land change, and recognizing limitations and weaknesses of remote sensing in land change studies.

Many of the most important ecosystem services performed by streams occur in the benthic biolayer, the biologically active upper ( 10 cm) layer of the streambed. Here we develop and test a rigorous modeling framework, based on Duhamel’s Theorem, for the unsteady one-dimensional transport and mixing of a solute in the benthic biolayer of a turbulent stream. The modeling framework is novel in that it allows for depth-varying diffusivity profiles, accounts for the change in porosity across the sediment-water interface and captures the two-way feedback between evolving solute concentrations in both the overlying water column and interstitial fluids of the sediment bed. We apply this new modeling framework to an extensive set of previously published laboratory data, with the goal of evaluating four diffusivity profiles (constant, exponentially declining, and two hybrid models that account for molecular diffusion and enhanced turbulent mixing in the surficial portion of the bed). The exponentially declining and enhanced mixing profiles are superior (based on RMSE, coefficient of determination, and AICc) and their reference diffusivities scale with a dimensionless measure of stream turbulence and streambed permeability called the Permeability Reynolds Number, ReK. The dependence on ReK changes abruptly at ReK=1, reflecting different modes of mixing below (dispersion) and above (turbulent diffusion) this threshold value. Because our modeling framework can be applied to open systems (such as streams, lakes, reservoirs, estuaries, and coastal waters), it should inform the prediction and management of pollutant migration through a diverse array of aquatic ecosystems.

The driving processes responsible for producing the Central Atlantic Magmatic Province, the Large Igneous Province associated with end-Triassic rifting of Pangea, remain largely debated. Because their compositions encompass most of the Central Atlantic basalt spectrum, tholeiites from southern Eastern North America are considered pivotal for identifying magma origins. New 176Hf/177Hf measurements for 201 Ma Eastern North American tholeiites dominantly record a local petrogenetic history. Their εHf ratios, corrected to an emplacement age of 201 Ma (-7.85 to +5.86), form a positive but shallowly sloped array slightly deviating from the terrestrial array on a εHf vs. εNd diagram. Comparison of 176Hf/177Hf to other isotope ratios and trace elements helps to rule out several petrogenetic scenarios, particularly mixing of melts from global depleted or enriched mantle components. In contrast, partial melting of subduction-metasomatized mantle can explain the parental magma composition for southern Eastern North America. Such metasomatism likely occurred during Paleozoic subduction around Pangea and may have been dominated by sediment-derived fluid reactions. The observed 176Hf/177Hf vs. 143Nd/144Nd array may reflect subsequent assimilation of lower continental crust, perhaps together with limited direct melting of recycled continental crust in the asthenosphere. The proposed recycling scenario does not specifically support or preclude a mantle plume origin for the Central Atlantic Magmatic Province, but instead points toward the presence of a distinct local mantle source and crustal assimilation processes during magma transport. Detailed understanding of these local effects is needed in order to more accurately understand the origins of Large Igneous Provinces.

The Apollo 16 sample 66095, named „Rusty Rock”, is enriched in volatile and moderately volatile elements. The impact melt breccia is characterized by the abundant occurrence of Fe-rich sulfide and chloride alteration phases, including FeS, ZnS and FeCl2. These phases have previously been interpreted to be the result of fumarolic alteration of the breccia. Here we present the results of two different experimental approaches, which aim to constrain the temperature conditions and the process under which the „Rusty Rock” alteration formed. The first experimental set-up assumes that the metals Zn, Cu and Fe were introduced into the rock by a C-O-S-Cl gas phase, and that the Fe-rich sulfides and chlorides were deposited from this gas phase. This “gas deposition” experiment suggests that the alteration assemblage formed over the temperature range of 538-638±5 °C. The second experimental set-up simulates a scenario, where Fe metal particles in the lunar rock react with a Zn-C-O-S-Cl gas phase at six different temperatures between 396±5 °C and 1005±5 °C. This latter “metal reaction” experiment resulted in the formation of sulfide and chloride coatings on the Fe metal chips. The „Rusty Rock” alteration phases FeCl2 and (Zn,Fe)S were abundantly present in the coating of the Fe metal chip reacted at 580±5 °C. Both experiments lead to results which are in agreement, providing a temperature of 580 ± 50 °C for the fumarolic alteration on the Moon, as observed in the Apollo 16 „Rusty Rock”.

Birds are some of the most diverse organisms on Earth, with species inhabiting nearly every conceivable niche in every major biome. As such, birds are vital to our understanding of modern ecosystems. Unfortunately, this is hampered by knowledge gaps relating to the origin of this modern diversity and its role in ecosystems. A crucial part of addressing these shortcomings is improving our understanding of the earliest birds, the non-avian avialans i.e. non-crown birds. The diet of non-avian avialans has been a matter of substantial debate, partly related to some of the ambiguous qualitative approaches that have been used to reconstruct it. Here we review the methods of determining diet in both modern avians and fossil avian and non-avian theropods, and comment on their usefulness when applied to non-avian avialans. We use this to propose a set of comparable, quantitative approaches to ascertain fossil bird diet and on this basis provide a consensus of what we currently know about fossil bird diet. While no single approach can precisely predict diet in birds, each can exclude some diets and narrow the dietary possibilities. We recommend combining [1] dental microwear, [2] landmark-based muscular reconstruction, [3] stable isotope geochemistry, [4] body mass estimations, [5] traditional and/or geometric morphometric analysis, and [6] finite element analysis to accurately reconstruct fossil bird diet. Our review provides specific methodologies to implement each approach and discusses complications future researchers should keep in mind. On this basis we report the current state of knowledge of non-avian avialan diet which remains very incomplete. The ancestral dietary condition in non-avian avialans remains unclear due to a scarcity of data and contradictory evidence in Archaeopteryx. Among early non-avian pygostylians, Confuciusornis has finite element analysis and mechanical advantage evidence pointing to herbivory, whilst Sapeornis only has mechanical advantage evidence indicating granivory, which agrees with fossilised ingested material known for this taxon. The enantiornithine ornithothoracine Shenqiornis has mechanical advantage and pedal morphometric evidence pointing to carnivory. In the hongshanornithid ornithuromorph Hongshanornis, only mechanical advantage evidence indicates granivory, but this is congruent with evidence of fossilised ingested material in this taxon. The same is true for the songlingornithid ornithuromorph Yanornis and its inferred carnivorous diet. Due to the sparsity of robust dietary assignments, no clear trends in non-avian avialan dietary evolution have yet emerged. Dietary diversity may seem to increase through time, but this is a preservational bias associated with a predominance of data from the Early Cretaceous Jehol Lagerstatte. With this new framework and our current synthesis of current knowledge of non-avian non-avialan diet, we expect dietary knowledge and evolutionary trends to become much clearer[…]

The isotopic composition of dissolved oxygen offers a family of potentially unique tracers of respiration and transport in the subsurface ocean. Uncertainties in transport parameters and isotopic fractionation factors, however, have limited the strength of the constraints offered by 18O/16O and 17O/16O ratios in dissolved oxygen. In particular, puzzlingly low 17O/16O ratios observed for some low-oxygen samples have been difficult to explain. To improve our understanding of oxygen cycling in the ocean’s interior, we investigated the systematics of oxygen isotopologues in the subsurface Pacific using new data and a 2-D isotopologue-enabled isopycnal reaction-transport model. We measured 18O/16O and 17O/16O ratios, as well as the “clumped” 18O18O isotopologue in the northeast Pacific, and compared the results to previously published data. We find that transport and respiration rates constrained by O2 concentrations in the oligotrophic Pacific yield good measurement-model agreement across all O2 isotopologues only when using a recently reported set of respiratory isotopologue fractionation factors that differ from those most often used for oxygen cycling in the ocean. These fractionation factors imply that an elevated proportion of 17O compared to 18O in dissolved oxygen―i.e., its triple-oxygen isotope composition―does not uniquely reflect gross primary productivity and mixing. For all oxygen isotopologues, transport, respiration, and photosynthesis comprise important parts of their respective budgets. Mechanisms of oxygen removal in the subsurface ocean are discussed.

With plate tectonics operating on Earth, the preservation potential for mantle reservoirs from the Hadean Eon (>4.0 Ga) has been regarded as very small. The quest for such early remnants has been spurred by the observation that many Archean rocks exhibit excesses of 182W, the decay product of short-lived 182Hf. However, it remains speculative, if Archean 182W anomalies and also 182W deficits found in many young ocean island basalts (OIBs) mirror primordial Hadean mantle differentiation or just variable contributions from older meteorite building blocks delivered to the growing Earth. Here, we present a high-precision 182W isotope dataset for 3.22-3.55 Ga old rocks from the Kaapvaal Craton, southern Africa. In expanding previous work, our study reveals widespread 182W deficits in different rock units from the Kaapvaal Craton and also the very first discovery of a negative co-variation between short-lived 182W and long-lived 176Hf-143Nd-138Ce patterns, a trend of global significance. Amongst different models, these distinct patterns can be best explained by the presence of recycled mafic restites from Hadean protocrust in the ancient mantle beneath the Kaapvaal Craton. Further, the data provide unambiguous evidence for the operation of silicate differentiation processes on Earth during the lifetime of 182Hf, i.e., the first 60 million years after solar system formation. The striking isotopic similarity between recycled protocrust and the low 182W endmember of modern OIBs might also constitute the missing link bridging 182W isotope systematics in Archean and young mantle-derived rocks.

Alkalinization of natural waters by the dissolution of natural or artificial minerals is a promising solution to sequester atmospheric CO$_2$ and counteract acidification. Here we address the alkalinization carbon capture efficiency (ACCE) by deriving an analytical factor that quantifies the increase in dissolved inorganic carbon in the water due to variations in alkalinity. We show that ACCE strongly depends on the water pH, with a sharp transition from minimum to maximum in a narrow interval of pH values. We also compare ACCE in surface freshwater and seawater and discuss potential bounds for ACCE in the soil water. Finally, we present two applications of ACCE. The first is a local application to 156 lakes in an acid-sensitive region, highlighting the great sensitivity of ACCE to the lake pH. The second is a global application to the surface ocean, revealing a latitudinal pattern of ACCE driven by differences in temperature and salinity.

Deep meteoric waters comprise a key component of the hydrologic cycle, transferring water, energy, and life between the earth's surface and deeper crustal environments, yet little is known about the nature and extent of meteoric water circulation. Using water stable isotopes, we show that maximum circulation depths of meteoric waters across North America vary considerably from 1 to 5 km, with the deepest circulation in western North America in areas of greater topographic relief. Shallower circulation occurs in sedimentary and shield-type environments with subdued topography. The amount of topographic relief available to drive regional groundwater flow and flush saline fluids is an important control on the extent of meteoric water circulation, in addition to permeability. The presence of an active flow system in the upper few kilometers of the Earth's crust and stagnant brines trapped by negative buoyancy offers a new framework for understanding deep groundwater systems.

Tropical rivers constitute a major portion of the global aquatic C flux entering the ocean, and the Rio Negro is one of the largest single C exporters with a particularly high export of terrestrial C. We investigated the role of whitesand ecosystems (WSEs) in blackwater formation in the Rio Negro basin to develop novel constraints for the terrestrial carbon export from land to the aquatic continuum. To this end, we used ultrahigh resolution mass spectrometry (FT-MS, Orbitrap) to identify markers in dissolved organic carbon (DOC) from ground- and surface waters of two contrasting WSEs feeding Rio Negro tributaries, and compared them with known Rio Negro marker from two openly available FT-MS datasets. Tributaries were fed by a whitesand riparian valley connected to terra firme plateau, and a typical upland whitesand Campina. WSE-DOC molecular composition differed by 80% from plateau DOC, which was characterized by reworked, highly unsaturated N- and S-containing molecules. WSE-DOC contained mainly condensed aromatics and polyphenols. WSE samples differed by 10% in molecular DOC composition and also by their isotopic content (14C, 18O, 2H). Upland WSE-DOC was exported by fresh precipitation and had maximum age of 13 years, being five years older than riparian valley WSE-DOC. Unexpectedly, only markers from the upland WSE, which cover a small proportion of the landscape, were identical to Negro markers. Markers of the riparian valley WSE, which are widespread and known for high DOC export, surprisingly showed lower coverage with Negro markers. Analysis of robust matching WSE markers between FT-MS datasets by Pubchem suggested well-known plant metabolites (chromenes and benzofurans) as promising candidates for targeted approaches and calibration. Our results suggest that terrestrial DOC from upland WSEs is a main source of specific blackwater molecules missing in the regional ecosystem C balance, whereas C export from the riparian valley and especially from terra firme plateaus represents mainly recycled and transformed carbon not directly affecting the ecosystem C balance. Our study highlights the potential of high-resolution techniques to constrain carbon balances of ecosystems and landscapes. Comparisons of FT-MS datasets and complementary isotopic information shows high potential to identify robust molecular markers that link forests, soils, aquifers and aquatic systems, and are needed for a deeper understanding of the regional C cycle in tropical blackwater catchments.

Geologists have documented at least fourteen occurrences of “giant ooids”, a geologically rare type of carbonate allochem, in Neoproterozoic successions at low paleo-latitudes. Recent experiments and modeling demonstrated that ooid size reflects an equilibrium between precipitation and abrasion rates, such that ooid size could be used as a geological proxy for CaCO3 mineral saturation state (Ω). Here, the documented sizes of Neoproterozoic giant ooids were applied to estimate seawater , which provided a novel approach to constraining temperature, partial pressure of CO2, and alkalinity preceding Neoproterozoic glaciations. The results suggest that giant ooid formation was most plausible with seawater alkalinity elevated over its present value by at least a factor of two, and either much warmer (40C) or much colder (0C) climate than modern tropical carbonate platforms, which have important and divergent implications for climate states and ecosystem responses prior to the initiation of each Neoproterozoic glaciation.

Geothermal activity in the Chilean Southern Volcanic Zone is strongly controlled by the regional Liquiñe-Ofqui Fault System (LOFS) and the Andean Transverse Faults (ATF). We analyzed fifteen thermal springs in the Liquiñe area to assess the origin and the main physicochemical processes related to the LOFS and ATF. Major, minor and trace elements identify two defined clusters spatially related to the regional fault systems. In both clusters, ionic relationships suggest that the principal hydrogeochemical processes are mainly dominated by water-rock interactions. Factorial analysis provided two factors: i) F1 (65.1%), saturated by Cl, HCO, Na, SiO, Li, B and Cs, represents water-rock interaction processes driven by temperature in presence of CO; ii) F2 (28.5%) represented by SO and Mo, represents a minor water-rock interaction enhanced by the presence of HS. Samples associated to the LOFS have high scores of both factors, while those from the ATF have only high factor 1 scores. Ionic ratios compared with literature data, clearly identify the samples spatially associated to the LOFS from the ones associated to the ATF with a fuzzy pattern. Water stable isotopes values suggest a meteoric origin with small deviations from local meteoric isotopic line. CO exchange with slightly high and low temperature water rocks interaction is present in most of the samples. Our results indicate that groundwater circulation along faults is a complex process where different constraints influence the final hydeogeochemistry and reaction intensity. Finally, the established processes at Liquiñe area are not upscalable at the whole Southern Volcanic Zone.

North African dust is known to be deposited in the Gulf of Mexico, but its deposition rate and associated supply of lithogenic dissolved metals, such as the abiotic metal thorium or the micronutrient metal iron, have not been well-quantified. 232Th is an isotope with similar sources as iron and its input can be quantified using radiogenic 230Th. By comparing dissolved 232Th fluxes at three sites in the northern Gulf of Mexico with upwind sites in the North Atlantic, we place an upper bound on North African dust contributions to 232Th and Fe in the Gulf of Mexico, which is about 30% of the total input. Precision on this bound is hindered by uncertainty in the relative rates of dust deposition in the North Atlantic and the northern Gulf of Mexico. Based on available radium data, shelf sources, including rivers, submarine groundwater discharge and benthic sedimentary releases are likely as important if not more important than dust in the budget of lithogenic metals in the Gulf of Mexico. In other words, it is likely there is no one dominant source of Th and Fe in the Gulf of Mexico. Finally, our estimated Fe input in the northern Gulf of Mexico implies an Fe residence time of less than 6 months, similar to that in the North Atlantic despite significantly higher supply rates in the Gulf of Mexico.

A thermodynamic model to calculate the “Sulfide Content at Sulfide Saturation” or SCSS of basaltic and intermediate composition silicate melts has been built from four independently measurable thermodynamic entities, namely the standard state Gibbs free energy of the saturation reaction, the “sulfide capacity”, and the activities of FeO in the silicate melt and of FeS in the coexisting sulfide: ln [S2-]SCSS = ∆G(FeO-FeS)/RT + ln C(S2- )- ln a(FeO)(sil melt) + ln a(FeS)sulf The model was calibrated for silicate melts of basic and intermediate composition from published experimental results as a function of temperature, silicate melt composition, and sulfide matte composition in the system Fe-Ni-Cu-S-O at 1 bar. The likely effects of pressure and H2O content on SCSS were included in an exploratory way. The model was tuned against the large dataset of S contents in OFB glasses of Jenner and O’Neill (2012), giving it a precision comparable to that of the S analyses themselves, which is ~ 5%. All but 3% the OFB glasses were found to be sulfide saturated within uncertainty; these 3% have lost S by devolatization, revealed by their low S/Se. Applying the model to other OFB datasets suggests sulfide saturation is ubiquitous, including olivine-hosted melt inclusions proposed previously to be sulfide undersaturated. The sulfur fugacity (fS2) of undegassed Ocean Floor Basalts varies proportionally to fO2, with log10fS2 typically within the range -0.6 to +0.4.

Meaningful analysis of uranium-series isotopic disequilibria in basaltic lavas relies on the use of complex forward numerical models like dynamic melting (McKenzie, 1985) and equilibrium porous flow (Spiegelman and Elliott, 1993). Historically, such models have either been solved analytically for simplified scenarios, such as constant melting rate or constant solid/melt trace element partitioning throughout the melting process, or have relied on incremental or numerical calculators with limited power to solve problems and/or restricted availability. The most public numerical solution to reactive porous flow, UserCalc (Spiegelman, 2000) was maintained on a private institutional server for nearly two decades, but that approach has been unsustainable in light of modern security concerns. Here we present a more long-lasting solution to the problems of availability, model sophistication and flexibility, and long-term access in the form of a cloud-hosted, publicly available Jupyter notebook. Similar to UserCalc, the new notebook calculates U-series disequilibria during time-dependent, equilibrium partial melting in a one-dimensional porous flow regime where mass is conserved. In addition, we also provide a new disequilibrium transport model which has the same melt transport model as UserCalc, but approximates rate-limited diffusive exchange of nuclides between solid and melt using linear kinetics. The degree of disequilibrium during transport is controlled by a Damköhler number, allowing the full spectrum of equilibration models from complete fractional melting (Da = 0) to equilibrium transport (Da = ∞).

Cretaceous - Miocene sedimentary rocks of northern Borneo preserve records of subduction of the Paleo-Pacific and Proto-South China Sea, providing important evidence for reconstructing the tectonic evolution of Southeast Asia since the Mesozoic. However, the genesis and tectonic setting of these sediments remain controversial. In this study, new Sr isotope, combined with Nd isotope data were used to determine the provenance contribution of the Cretaceous – Late Eocene Lubok Antu mélange and the Rajang Group. Detrital zircon ages and sedimentary geochemistry data of the Cretaceous - Miocene strata are also used to better understand the tectonic evolution of Borneo. Results show that more than 60% of the sediments came from a magmatic belt during the Late Cretaceous to Early Paleocene, and more than 50% from the Malay Peninsula during the Paleocene to the Late Eocene. The proportion of different detrital zircon ages and sedimentary geochemical characteristics in Borneo changed from west to east during the Cretaceous to the Miocene, which may be related to drainage changes caused by the gradual closure of an ocean basin. Subduction ceased in central Borneo during the Early Paleocene, slightly later than Late Cretaceous cessation in western Borneo. The collapse of magmatic belt lead river drainages from the Malay Peninsula to flow into Borneo. Whereas subduction continued in Eastern Borneo until the Miocene. Opening of the South China Sea cut off the drainage from the Malay Peninsula, and the inner rocks in Borneo once again became the main source of sediments.

Located in northern Dominican Republic, the Early Cretaceous Rio Boba mafic-ultramafic plutonic sequence constitutes a lower crust section of the Caribbean island arc, made up by gabbroic rocks and subordinate pyroxenite. Modal compositions, mineral chemistry, whole-rock compositions and thermobarometric calculations indicate that pyroxenites and gabbronorites represent a cumulate sequence formed by fractionation of tholeiitic magmas with initially very low H2O content in the lower crust of the arc (0.6-0.8 GPa). Melts evolved along a simplified crystallization sequence of olivine ® pyroxenes ® plagioclase ® Fe-Ti oxides. The magmatic evolution of the Rio Boba sequence and associated supra-crustal Puerca Gorda metavolcanic rocks is multi-stage and involves the generation of magmas from melting of different sources in a supra-subduction zone setting. The first stage included the formation of a highly depleted substrate as result of decompressional melting of a refractory mantle source, represented by a cumulate sequence of LREE-depleted IAT and boninitic gabbronorites and pyroxenites. The second stage involved volumetrically subordinate cumulate troctolites and gabbros, which are not penetratively deformed. The mantle source was refractory and enriched by a LILE-rich hydrous fluid derived from a subducting slab and/or overlying sediments, and possibly by a LREE-rich melt. The third stage is recorded in the upper crust of the arc by the Puerca Gorda ‘normal’ IAT protoliths, which are derived from an N-MORB mantle source enriched with a strong subduction component. This magmatic evolution has implications for unravelling the processes responsible for subduction initiation and subsequent building of the Caribbean island arc.

Radiogenic lead (Pb) and neodymium (Nd) isotope compositions extracted from authigenic phases in marine sediments are sensitive tracers to reconstruct past ocean circulation and water mass mixing. Chemical reductive leaching of hydrogenetic ferromanganese oxyhydroxides from bulk sediments is the most practical way to recover past seawater Pb and Nd isotope signatures in the Southern Ocean, due to the scarcity of alternative archives. However, the leached signal could be compromised if substantial quantities of Pb and Nd were released from non-hydrogenetic sediment fractions during chemical extraction. Here we developed a very short 10-seconds leaching method to extract reliable seawater Pb and Nd isotope signals from sediments in the Atlantic sector of Southern Ocean. The effect of a previously recommended MgCl prewash, the role of chelate ligands in the leaching solution and length of leaching time were investigated. The results show that 10 seconds exposure time of sediments to reductive leaching extracted sufficient and more reliable hydrogenetic Pb and Nd compared with the commonly used 30-minute leaching approaches. The robustness of our improved leaching method was validated via direct comparison of Pb and Nd isotope signatures with actual seawater, porewater and corresponding sediment leachates from three stations in front of the Antarctic Filchner-Rønne Ice Shelf. Our findings suggest that in contrast previously studied sites on the West Antarctic continental shelf, the southern Weddell Sea shelf is not a location of pronounced benthic Nd fluxes to the water column.

Between 81º30’ E and 83ºE the Himalayan range’s “perfect” arcuate shape is interrupted by an embayment. We hypothesize that thrust geometry and duplexing along the megathrust at mid-lower crustal depths plays a leading role in growth of the embayment as well the southern margin of the Tibetan plateau. To test this hypothesis, we conducted thermokinematic modeling of published thermochronologic data from the topographic and structural embayment in the western Nepal Himalaya to investigate the three-dimensional geometry and kinematics of the megathrust at mid-lower crustal depths. Models that can best reproduce observed cooling ages suggest that the megathrust in the western Nepal Himalaya is best described as two ramps connected by a long flat that extends further north than in segments to the east and west. These models suggest that the high-slope zone along the embayment lies above the foreland limb of an antiformal crustal accretion zone on the megathrust with lateral and oblique ramps at mid-lower crustal depths. The lateral and oblique ramps may have initiated by ca. 10 Ma. This process may have controlled along-strike variation in Himalayan-plateau growth and therefore development of the topographic embayment. Finally, we analyze geological and morphologic features and propose an evolution model in which landscape and drainage systems across the central-western Himalaya evolve in response to crustal accretion at depth and the three-dimensional geometry of the megathrust. Our work highlights the importance of crustal accretion at different depths in orogenic-wedge growth and that the mid-lower crustal accretion determines the location of plateau edge.

Drylands occupy ~40% of the land surface and are thought to dominate global carbon (C) cycle inter-annual variability (IAV). Therefore, it is imperative that global terrestrial biosphere models (TBMs), which form the land component of IPCC earth system models, are able to accurately simulate dryland vegetation and biogeochemical processes. However, compared to more mesic ecosystems, TBMs have not been widely tested or optimized using in situ dryland CO2 fluxes. Here, we address this gap using a Bayesian data assimilation system and 89 site-years of daily net ecosystem exchange (NEE) data from 12 southwest US Ameriflux sites to optimize the C cycle parameters of the ORCHIDEE TBM. The sites span high elevation forest ecosystems, which are a mean sink of C, and low elevation shrub and grass ecosystems that are either a mean C sink or “pivot” between an annual C sink and source. We find that using the default (prior) model parameters drastically underestimates both the mean annual NEE at the forested mean C sink sites and the NEE IAV across all sites. Our analysis demonstrated that optimizing phenology parameters are particularly useful in improving the model’s ability to capture both the magnitude and sign of the NEE IAV. At the forest sites, optimizing C allocation, respiration, and biomass and soil C turnover parameters reduces the underestimate in simulated mean annual NEE. Our study demonstrates that all TBMs need to be calibrated for dryland ecosystems before they are used to determine dryland contributions to global C cycle variability and long-term carbon-climate feedbacks.

Apatite fission track (AFT) analyses for granitoid and metamorphic bedrock samples from the Western Superior Province (Ontario), the Churchill-Rae Province (Melville Peninsula and Southampton Island, Nunavut), and the Slave Province (Northwest Territories) show a broad range of single grain effective uranium concentrations (eU) (<1 to ~300 ppm) and some of the oldest reported AFT ages in North America. Although most of our samples are characterized by near-endmember fluorapatite composition with implied low track retentivity (<0.1 apfu Cl, rmr0 ~0.85-0.82), single-grain AFT ages are statistically overdispersed and ages decrease with increasing eU content. This eU-age relationship is resonant of the Hendriks and Redfield (2005) Earth Planet. Sci. Lett. 236 (443-458) argument for α-radiation enhanced fission track annealing (REA) and is analogous to the negative age-eU correlations observed in published zircon and titanite (U-Th)/He data from slowly-cooled cratonic rocks. In all cases, the samples fail the canonical χ2 test (<5%), generally considered to indicate that the ages are unlikely to be drawn from a single Poissonian distribution with a discrete mean value and may represent multiple populations. The high intra-sample age variability for low-Cl bedrock apatites with protracted histories (>200-500 m.y.) at <100°C since the Precambrian suggests strong REA control on AFT ages. Conversely, some low Cl AFT samples with a narrower eU range show less age dispersion and a weak apparent age-eU correlation. A complex trade-off between radiation damage, chemical composition (e.g. low Cl and REE enrichment), and thermal history is implied when eU and rmr0 are positively correlated. Previous assessments of the influence of REA on AFT age were based on evaluating central age and mean track length, which potentially mask high single-grain age scatter and REA effects due to the modal nature of central age determination. REA is also supported by and compatible with materials science and nuclear waste studies of radiation damage in different apatite groups, therefore it is crucial that bedrock samples exhibiting high age scatter are evaluated in terms of intra-sample compositional heterogeneity. AFT samples with relatively low Cl concentrations are especially prone to greater REA control of cooling ages and this underscores the need for routine acquisition of compositional data for AFT datasets. Our broad range in single-grain AFT ages (with no other clear, strong compositional controls) supports the notion that radiation damage affects both the AFT and (U-Th)/He thermochronometers in slowly-cooled settings and must be accounted for during thermal history modeling and interpretation.

Clumped-isotope measurements in CO2 and carbonates (Δ47) present a number of technical challenges and require correcting for various sources of analytical non-linearity. For now we lack a formal description of the analytical errors associated with these correction steps, which are not accounted for in most data processing methods currently in use. Here we formulate a quantitative description of Δ47 error propagation, fully taking into account standardization errors and their properties. We find that standardization errors are highly sensitive to the isotopic compositions (δ47, Δ47) of unknown samples relative to the standards used for analytical corrections, and in many cases constitute a non-negligible source of uncertainty, causing true measurements errors to exceed traditionally reported error estimates by a factor of 1.5 (typically) to 3.5 (in extreme cases). Using Monte Carlo simulations based on the full InterCarb data set, we find that this model yields accurate error estimates in spite of small non-Gaussian effects which remain entirely negligible in practice. We also describe various standardization strategies, along with the assumptions they rely on, in the context of this model, and propose a new, “pooled” standardization approach designed to yield more robust/accurate corrections. Among other uses, the mathematical framework described here may be helpful to improve standardization protocols (e.g., anchor/unknown ratios) and inform future efforts to define community reference materials. What’s more, these models imply that the inter-laboratory scatter (N = 5329) observed in the InterCarb exercise [Bernasconi et al., 2021] can be entirely explained as the effects of current standardization procedures. Based on these findings, we recommend that future studies systematically report full analytical uncertainties taking standardization errors into account. In line with this recommendation, we provide user-friendly online resources and an open-source Python library designed to facilitate the use of these error models.