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%. 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. 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. 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.
The Yucatan Peninsula (YP) has a complex hydroclimate with many proposed drivers of interannual and longer-term variability, ranging from coupled ocean-atmosphere processes to frequency of tropical cyclones. The mid-Holocene, a time of higher Northern Hemisphere summer insolation, provides an opportunity to test the relationship between Yucatan Peninsula precipitation and ocean temperature. Here we present a new, ~annually resolved speleothem record of stable isotope (δ18O and δ13C) and trace element (Mg/Ca and Sr/Ca) ratios for a section of the mid-Holocene (5.2-5.7 kyr BP), before extensive agriculture began in the region. A meter-long stalagmite from Rio Secreto, a cave system in Playa del Carmen, Mexico, was dated using U-Th geochronology and layer counting, yielding multidecadal age uncertainty (median 2SD of +/- 70 years). New proxy data were compared to an existing late Holocene stalagmite record from the same cave system, allowing us to examine changes in hydrology over time, and to paleoclimate records from the southern YP. The δ18O, δ13C and Mg/Ca data consistently indicate higher mean precipitation and lower precipitation variability during the mid-Holocene compared to the late Holocene. Despite this reduced variability, multidecadal precipitation variations were persistent in regional hydroclimate during the mid-Holocene. We therefore conclude that higher summer insolation led to increased mean precipitation and decreased precipitation variability in the northern YP, but that the region is susceptible to dry periods across climate mean states. Given projected decreases in wet season precipitation in the YP’s near future, we suggest that climate mitigation strategies emphasize drought preparation.
Serpentinite subduction and the associated formation of dehydration veins is important for subduction zone dynamics and water cycling. Field observations suggest that en-échelon olivine veins in serpentinite mylonites formed by dehydration during simultaneous shearing of ductile serpentinite. Here, we test a hypothesis of shear-driven formation of dehydration veins with a two-dimensional hydro-mechanical-chemical numerical model. We consider the reaction antigorite + brucite = forsterite + water. Shearing is viscous and the shear viscosity decreases exponentially with porosity. The total and fluid pressures are initially homogeneous and in the antigorite stability field. Initial perturbations in porosity, and hence viscosity, cause fluid pressure perturbations. Dehydration nucleates where the fluid pressure decreases locally below the thermodynamic pressure defining the reaction boundary. Dehydration veins grow during progressive simple-shearing in a direction parallel to the maximum principal stress, without involving fracturing. The porosity evolution associated with dehydration reactions is controlled to approximately equal parts by three mechanisms: volumetric deformation, solid density variation and reactive mass transfer. The temporal evolution of dehydration veins is controlled by three characteristic time scales for shearing, mineral-reaction kinetics and fluid-pressure diffusion. The modelled vein formation is self-limiting and slows down due to fluid flow decreasing fluid pressure gradients. Mineral-reaction kinetics must be significantly faster than fluid-pressure diffusion to generate forsterite during vein formation. The self-limiting feature can explain the natural observation of many, small olivine veins and the absence of few, large veins. We further discuss implications for transient weakening during metamorphism and episodic tremor and slow-slip in subduction zones.