Persistent volcanic activity is thought to be linked to degassing, but volatile transport at depth cannot be observed directly. Instead, we rely on indirect constraints such as CO2-H2O concentrations in melt inclusions trapped at different depth, but this data is rarely straight-forward to interpret. In this study, we develop a multiscale model of conduit flow during passive degassing to identify how flow behavior in the conduit is reflected in melt-inclusion data and surface gas flux. During the approximately steady flow likely characteristic of passive-degassing episodes, variability in degassing arises primarily from two processes, the mixing of volatile-poor and volatile-rich magma and variations in CO2 influx from depth. To quantify how conduit-flow conditions alter mixing efficiency, we first model bidirectional flow in a conduit segment at the scale of tens of meters while fully resolving the ascent dynamics of intermediate-size bubbles at the scale of centimeters. We focus specifically on intermediate-size bubbles, because these are small enough not to generate explosive behavior, but large enough to alter the degree of magma mixing. We then use a system-scale volatile-concentration model to evaluate the joint effect of magma mixing and CO2 influx on volatile concentrations profiles against observations for Stromboli and Mount Erebus. We find that the two processes have distinct observational signatures, suggesting that tracking them jointly could help identify changes in conduit flow and advance our understanding of eruptive regimes.
Although adequately detailed kerosene chemical-combustion Arrhenius reaction-rate suites were not readily available for combustion modeling until ca. the 1990’s (e.g., Marinov ), it was already known from mass-spectrometer measurements during the early Apollo era that fuel-rich liquid oxygen + kerosene (RP-1) gas generators yield large quantities (e.g., several percent of total fuel flows) of complex hydrocarbons such as benzene, butadiene, toluene, anthracene, fluoranthene, etc. (Thompson ), which are formed concomitantly with soot (Pugmire ). By the 1960’s, virtually every fuel-oxidizer combination for liquid-fueled rocket engines had been tested, and the impact of gas phase combustion-efficiency governing the rocket-nozzle efficiency factor had been empirically well-determined (Clark ). Up until relatively recently, spacelaunch and orbital-transfer engines were increasingly designed for high efficiency, to maximize orbital parameters while minimizing fuels and structural masses: Preburners and high-energy atomization have been used to pre-gasify fuels to increase (gas-phase) combustion efficiency, decreasing the yield of complex/aromatic hydrocarbons (which limit rocket-nozzle efficiency and overall engine efficiency) in hydrocarbon-fueled engine exhausts, thereby maximizing system launch and orbital-maneuver capability (Clark; Sutton; Sutton/Yang). The combustion community has been aware that the choice of Arrhenius reaction-rate suite is critical to computer engine-model outputs. Specific combustion suites are required to estimate the yield of high-molecular-weight/reactive/toxic hydrocarbons in the rocket engine combustion chamber, nonetheless such GIGO errors can be seen in recent documents. Low-efficiency launch vehicles also need larger fuels loads to achieve the same launched mass, further increasing the yield of complex hydrocarbons and radicals deposited by low-efficiency rocket engines along launch trajectories and into the stratospheric ozone layer, the mesosphere, and above. With increasing launch rates from low-efficiency systems, these persistent (Ross/Sheaffer ; Sheaffer ), reactive chemical species must have a growing impact on critical, poorly-understood upper-atmosphere chemistry systems.
Although adequately detailed kerosene chemical-combustion Arrhenius reaction-rate suites were not readily available for combustion modeling until ca. the 1990’s (e.g., Marinov ), it was already known from mass-spectrometer measurements during the early Apollo era that fuel-rich liquid oxygen + kerosene (RP-1) gas generators yield large quantities (e.g., several percent of total fuel flows) of complex hydrocarbons such as benzene, butadiene, toluene, anthracene, fluoranthene, etc. (Thompson ), which are formed concomitantly with soot (Pugmire ). By the 1960’s, virtually every fuel-oxidizer combination for liquid-fueled rocket engines had been tested, and the impact of gas phase combustion-efficiency governing the rocket-nozzle efficiency factor had been empirically well-determined (Clark ). Up until relatively recently, spacelaunch and orbital-transfer engines were increasingly designed for high efficiency, to maximize orbital parameters while minimizing fuels and structural masses: Preburners and high-energy atomization have been used to pre-gasify fuels to increase (gas-phase) combustion efficiency, decreasing the yield of complex/aromatic hydrocarbons (which limit rocket-nozzle efficiency and overall engine efficiency) in hydrocarbon-fueled engine exhausts, thereby maximizing system launch and orbital-maneuver capability (Clark; Sutton; Sutton/Yang). The rocket combustion community has been aware that the choice of Arrhenius reaction-rate suite is critical to computer engine-model outputs. Specific combustion suites are required to estimate the yield of high-molecular-weight/reactive/toxic hydrocarbons in the rocket engine combustion chamber, nonetheless such GIGO errors can be seen in recent documents. Low-efficiency launch vehicles (SpaceX, Hanwha) therefore also need larger fuels loads to achieve the same launched/transferred mass, further increasing the yield of complex hydrocarbons and radicals deposited by low-efficiency rocket engines along launch trajectories and into the stratospheric ozone layer, the mesosphere, and above. With increasing launch rates from low-efficiency systems, these persistent (Ross/Sheaffer ; Sheaffer ), reactive chemical species must have a growing impact on critical, poorly-understood upper-atmosphere chemistry systems.
Self-organizing diffusion-reaction systems naturally form complex patterns under far from equilibrium conditions. A representative example is the rhythmic concentration pattern of Fe-oxides in Zebra rocks; these patterns include reddish-brown stripes, rounded rods, and elliptical spots. Similar patterns are observed in the banded iron formations which are presumed to have formed in the early earth under global glaciation. We propose that such patterns can be used directly (e.g., by computer-vision-analysis) to infer basic quantities relevant to their formation giving information on generalized chemical gradients. Here we present a phase-field model that quantitatively captures the distinct Zebra rock patterns based on the concept of phase separation that describes the process forming Liesegang stripes. We find that diffusive coefficients (i.e., the bulk self-diffusivities and the diffusive mobility of Cahn-Hilliard dynamics) play an essential role in controlling the appearance of regular stripe patterns as well as the transition from stripes to spots. The numerical results are carefully benchmarked with the well-established empirical spacing law, width law, timing law and the Matalon-Packter law. Using this model, we invert for the important process parameters that originate from the intrinsic material properties, the self-diffusivity ratio and the diffusive mobility of Fe-oxides, with a series of Zebra rock samples. This study allows a quantitative prediction of the generalized chemical gradients in mineralized source rocks without intrusive measurements, providing a better intuition for the mineral exploration space.
Here, we explore the importance of export productivity versus anoxia in the formation of sedimentary layers with enhanced total organic carbon (TOC) content. We use geochemical, sedimentological and micropaleontological records from two SW Sicily outcropping successions, Lido Rosello (LR) and Punta di Maiata (PM), over three mid-Pliocene precession-forced climate cycles (4.7 – 4.6 million years ago [Ma]). Grey marls, deposited during precession minima, show enhanced TOC in both records. We suggest that basin-wide, low-oxygenated bottom-waters, resulting from freshwater-induced stratification during precession minimum, was integral to preserving grey marl TOC. Furthermore, prolonged eastern Mediterranean stratification may have produced a deep chlorophyll maximum (DCM), leading to ‘shade-flora’ dominated productivity. The LR succession displays two unique laminated layers containing enhanced TOC. These laminations do not occur at specific times in the precession cycle or in time-equivalent PM samples. They are likely to have been produced by an intermittent dysoxic/anoxic pool at LR, caused by a local depression, which enhanced TOC preservation. Consequently, the laminations provide a rare window into ‘true’ eastern Mediterranean productivity conditions during precession maxima, as organic matter is typically poorly preserved during these period due to enhanced ventilation. The laminated ‘windows’ indicate that eastern Mediterranean export productivity may not have been significantly lower during precession maxima compared to precession minima, as previously thought. During these periods, productivity conditions are likely to have been comparable to the modern eastern Mediterranean, with a spring-bloom caused by enhanced winter/spring deep-water mixing preceding a summer ‘shade-flora’ bloom caused by a summer-stratification induced DCM.
The low viscosity of mafic magmas generally promotes effusive to mildly explosive eruptions; however, highly explosive mafic volcanic activity does occur. Recent models suggest that rapid ascent rates leading to significant disequilibrium drastically impact the rheology leading to fragmentation of the mafic magma. However, the magmatic conditions preceding magma ascent initiation are primarily unknown. There is a rich rock and mineral record for understanding melt generation in the mantle wedge and open system processes stored in the juvenile products of these highly explosive mafic eruptions. This study uses the pyroclasts from the Curacautin ignimbrite, a large volume (3.5–4.5 km3 DRE), mafic (50.4-57.3 wt% SiO2) ignimbrite at Llaima volcano in Chile.Of the 68 ignimbrite samples collected and previously analyzed, we targeted four for small volume (5 mg vs. standard 50 mg) characterization via ICPMS: (1) the top and (2) base of the ignimbrite, and the most (3) depleted and (4) enriched samples. We prepped and analyzed ten randomly selected pyroclasts from the highlighted samples (a total of 40 analyses). This study aimed to determine how sampling (e.g., composite vs. individual and the number of samples) impacts the signal of geological processes in trace element compositions. We used the χ2 distribution to test if the observed standard deviation (corrected for noise by subtracting analytical error) of all 40 samples, as well as each sample set’s ten analyzed pyroclasts, is larger than the analytical error. We identified true variability for at least 13 of the 30 trace elements measured for the base of the ignimbrite and enriched end member sample sets and the combined 40 analyses. For the top of the ignimbrite sample and the depleted end member sample, there is true variability in almost all 30 trace elements. Small volume whole rock geochemical characterization of individual pyroclasts detects previously unseen small-scale geochemical variability in compatible and REE elements and constrains new enrichment end-member compositions for geochemical models. Using principal component analysis, we investigate melt source heterogeneity and fractional crystallization as controls on the observed variability.
Antarctic landfast sea ice (fast ice) is stationary sea ice that is attached to the coast, grounded icebergs, ice shelves, or other protrusions on the continental shelf. Fast ice forms in narrow (generally up to 200 km wide) bands, and ranges in thickness from centimeters to tens of meters. In most regions, it forms in autumn, persists through the winter and melts in spring/summer, but can remain throughout the summer in particular locations. Despite its relatively limited horizontal extent (comprising between about 4 and 13 \% of overall sea ice), its presence, variability and seasonality are drivers of a wide range of physical, biological and biogeochemical processes, with both local and far-ranging ramifications for various Earth systems. Antarctic fast ice has, until quite recently, been overlooked in studies, likely due to insufficient knowledge of its distribution, leading to its reputation as a “missing piece of the Antarctic puzzle”. This review presents a synthesis of current knowledge of the physical, biogeochemical and biological aspects of fast ice, based on the sub-domains of: fast ice growth, properties and seasonality; remote-sensing and distribution; interactions with the atmosphere and the ocean; biogeochemical interactions; its role in primary production; and fast ice as a habitat for grazers. Finally, we consider the potential state of Antarctic fast ice at the end of the 21st Century, underpinned by Coupled Model Intercomparison Project model projections. This review also gives recommendations for targeted future work to increase our understanding of this critically-important element of the global cryosphere.
During the first 2934 sols of the Curiosity rover’s mission 33,468 passive visible/near-infrared reflectance spectra were taken of the surface by the mast-mounted ChemCam instrument on a range of target types. ChemCam spectra of bedrock targets from the Murray and Carolyn Shoemaker formations on Mt. Sharp were investigated using principal component analysis (PCA) and various spectral parameters including the band depth at 535 nm and the slope between 840 nm and 750 nm. Four endmember spectra were identified. Passive spectra were compared to Laser Induced Breakdown Spectroscopy (LIBS) data to search for correlations between spectral properties and elemental abundances. The correlation coefficient between FeOT reported by LIBS and BD535 from passive spectra was used to search for regions where iron may have been added to the bedrock through oxidation of ferrous-bearing fluids, but no correlations were found. Rocks in the Blunts Point-Sutton Island transition that have unique spectral properties compared to surrounding rocks, that is flat near-infrared (NIR) slopes and weak 535 nm absorptions, are associated with higher Mn and Mg in the LIBS spectra of bedrock. Additionally, calcium-sulfate cements, previously identified by Ca and S enrichments in the LIBS spectra of bedrock, were also shown to be associated with spectral trends seen in Blunts Point. A shift towards steeper near-infrared slope is seen in the Hutton interval, indicative of changing depositional conditions or increased diagenesis.
Mountain System Recharge (MRS) processes are the natural recharge pathways in arid and semi-arid mountainous regions. However, MSR processes are often poorly understood and characterized in hydrologic models. Mountains are the primary source of water supply to valley aquifers via multiple pathways including lateral groundwater flow from the mountain block (Mountain-block Recharge, MBR) and focused recharge from mountain streams contributing to mountain front recharge (MFR) at the piedmont zone. Here, we present a multi-tool isogeochemical approach to characterize mountain flow paths and MSR processes in the northern Tulare basin, California. We used groundwater chemistry data to delineate hydrochemical facies and explain the chemical evolution of groundwater from the Sierra Nevada to the Central Valley aquifer. Isotope tracers helped to validate MSR processes. Novel application of End-Member Mixing Analysis (EMMA) using conservative chemical components revealed three MSR end-members: (1) evaporated Ca-HCO3 water type associated with MFR, (2) non-evaporated Ca-HCO3 and Na-HCO3 water types with short residence times associated with shallow MBR, and (3) Na-HCO3 groundwater type with long residence time associated with deep MBR. We quantified the contribution of each MSR process to the valley aquifer using mixing ratio calculation (MIX). Our results show that deep MBR is a significant component of recharge representing more than 50% of the valley groundwater. Greater hydraulic connectivity between the Sierra Nevada and Central Valley has significant implications for parameterizing Central Valley groundwater flow models and improving groundwater management. Our framework is useful for understanding MSR processes in other snow-dominated mountain watersheds.
Pulsing seepages of native hydrogen (H2) have been observed at the surface on several emitting structures. It is still unclear whether this H2 pulsed ﬂux is controlled by deep migration processes, atmosphere/near-surface interactions or by bacterial fermentation. Here, we investigate mechanisms that may trigger pulsating fluid migration at depth and the resulting periodicity. We set up a numerical model to simulate the migration of a deep constant fluid flow. To verify the model’s formulation to solve complex fluid flows, we first simulate the morphology and amplitude of 2D thermal anomalies induced by buoyancy-driven water ﬂow within a fault zone. Then, we simulate the H2 gas flow along a 1-km draining fault, crosscut by a lower permeable rock layer to investigate the conditions for which a pulsing system is generated from a deep control. For a constant incoming flow of H2 at depth, persistent bursts at the surface only appear in the model if: (I) a permeability with an effective-stress dependency is used, (II) a strong contrast of permeability exists between the different zones, (III) a sufficiently high value of the initial effective stress state at the base of the low permeable layer exists, and (IV) the incoming and continuous fluid flow of H2 at depth remains low enough so that the overpressure does not “open” instantly the low permeability layer. The typical periodicity expected for this type of valve-fault control of H2 pulses at the surface is at a time scale of the order of 100 to 300 days.
The biogeochemical cycles of iron (Fe) and manganese (Mn) in lakes and reservoirs have predictable seasonal trends, largely governed by stratification dynamics and redox conditions in the hypolimnion. However, short-term (i.e., sub-weekly) trends in Fe and Mn cycling are less well-understood, as most monitoring efforts focus on longer-term (i.e., monthly to yearly) time scales. The potential for elevated Fe and Mn to degrade water quality and impact ecosystem functioning, coupled with increasing evidence for high spatiotemporal variability in other biogeochemical cycles, necessitates a closer evaluation of the short-term Fe and Mn cycling dynamics in lakes and reservoirs. We adapted a UV-visible spectrophotometer coupled with a multiplexor pumping system and PLSR modeling to generate high spatiotemporal resolution predictions of Fe and Mn concentrations in a drinking water reservoir (Falling Creek Reservoir, Vinton, VA, USA) equipped with a hypolimnetic oxygenation (HOx) system. We quantified hourly Fe and Mn concentrations during two distinct transitional periods: reservoir turnover (Fall 2020) and initiation of the HOx system (Summer 2021). Our sensor system was able to successfully predict mean Fe and Mn concentrations as well as capture sub-weekly variability, ground-truthed by traditional grab sampling and laboratory analysis. During fall turnover, hypolimnetic Fe and Mn concentrations began to decrease more than two weeks before complete mixing of the reservoir occurred, with rapid equalization of epilimnetic and hypolimnetic Fe and Mn concentrations in less than 48 hours after full water column mixing. During the initiation of hypolimnetic oxygenation in Summer 2021, we observed that Fe and Mn were similarly affected by physical mixing in the hypolimnion, but displayed distinctly different responses to oxygenation, as indicated by the rapid oxidation of soluble Fe but not soluble Mn. This study demonstrates that Fe and Mn concentrations are highly sensitive to shifting DO and stratification and that their dynamics can substantially change on hourly to daily time scales in response to these transitions.
While Hg in sediments is increasingly used as a proxy for deep-time volcanic activity, the behaviour of Hg in OM-rich sediments as they undergo thermal maturation is not well understood. In this study, we evaluate the effects of thermal maturation on sedimentary Hg contents and, thereby, the impact of thermal maturity on the use of the Hg/TOC proxy for large igneous province (LIP) volcanism. We investigate three cores (marine organic matter) with different levels of thermal maturity in lowermost Toarcian sediments (Posidonienschiefer) from the Lower Saxony Basin in Germany. We present Hg content, bulk organic geochemistry, and total sulfur in three cores with different levels of thermal maturity. The comparison of Hg data between the three cores indicates that Hg content in the mature/overmature sediments have increased > 2-fold compared to Hg in the immature deposits. Although difficult to confirm with the present data, we speculate that redistribution within the sedimentary sequence caused by the mobility and volatility of the element under relatively high temperatures may have contributed to Hg enrichment in distinct stratigraphic levels of the mature cores. Regardless of the exact mechanism, elevated Hg content together with organic-carbon loss by thermal maturation exaggerate the value of Hg/TOC in mature sediments, suggesting that thermal effects have to be considered when using TOC-normalised Hg as a proxy for far-field volcanic activity.
The Ethiopia-Yemen flood basalts are spatially zoned with progressively lower TiO2 lavas from near the Afar depression toward the margins. The timing and rate of emplacement of low TiO2 (LT) lavas are poorly known compared with the ultra-high TiO2 (HT2) lavas. We measured two high-precision 40Ar/39Ar ages of 29.63 ± 0.14 and 30.02 ± 0.22 Ma (2σ) from basalts of the 2-km-thick LT lava sequence at the Afar plume head margin. Using our eruption age model constructed from our and previous 40Ar/39Ar ages with the paleomagnetic directions, we estimate that the LT lava eruption continued over Chrons C12r-C12n-C11r. The eruption of the plume head margin started earlier than the plume head axis emplacement in C12n. Also, the eruption rate was low at the margin, high at the axis. We estimate that the LT lavas are induced by the edge-driven convection, the result of a plume-lithosphere interaction, not a plume head.
Stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope measurements in lacustrine ostracodes are widely used to infer past climatic conditions. Previous work has used individual ostracode valves to resolve seasonal and subdecadal climate signals, yet environmental controls on geochemical variability within co-occurring specimens from modern samples are poorly constrained. Here we focus on individual ostracode valves in modern-aged Lake Turkana sediments, an alkaline desert lake in tropical East Africa. We present individual ostracode valve analyses (IOVA) of δ¹³C and δ¹⁸O measurements (n = 329) of extant species Sclerocypris clavularis from 17 sites spanning the entire lake (n-avg ~19 specimens per site). We demonstrate that the pooled statistics of individual valve measurements at each site overcome inter-specimen isotopic variance and are driven by hydrological variability in the lake. Mean IOVA-δ¹³C and -δ¹⁸O across the sites exhibit strong spatial trends with higher values at more southerly latitudes, modulated by distance from the inflow of the Omo River. Whereas the latitudinal δ¹³C gradient reflects low riverine δ¹³C and decreasing lacustrine productivity towards the southern part of the lake, the δ¹⁸O gradient is controlled by evaporation superimposed on the waning influence of low-δ¹⁸O Omo River waters, sourced from the Ethiopian highlands. We show that ostracode δ¹⁸Oproximal to Omo River inflow is deposited under near-equilibrium conditions and that inter-specimen δ¹⁸O variability across the basin is consistent with observed temperature and lake water δ¹⁸O variability. IOVA can provide skillful constraints on high-frequency paleoenvironmental signals and, in Omo-Turkana sediments, yield quantitative insights into East African paleohydrology.
Extraction of sulfides from the partially molten mantle is vital to elucidate the cycling of metal and sulfur elements between different geochemical circles but has not been investigated systematically. Using laboratory experiments and theoretical calculations, this study documents systematical variations in lithologies and compositions of silicate minerals and melts, which are approximately consistent with the results of the thermodynamically-constrained model. During a melt-peridotite reaction, the dissolution of olivine and precipitation of new orthopyroxene generate an orthopyroxene-rich layer between the melt source and peridotite. With increasing reaction degree, more melt is infiltrated into and reacts with upper peridotite, which potentially enhances the concomitant upward transport of dense sulfide droplets. Theoretical analyses suggest an energetically focused melt flow with a high velocity (~ 170.9 μm/h) around sulfide droplets through the pore throat. In this energic melt flow, we, for the first time, observed the mechanical coalescence of sulfide droplets, and the associated drag force was likely driving upward entrainment of fine μm-scale sulfide. For coarse sulfide droplets whose sizes are larger than the pore throat in the peridotite, their entrainment through narrow constrictions in crystal framework seems to be physically possible only when high-degree melt-peridotite reaction drives high porosity of peridotite and channelized melt flows with extremely high velocity. Hence, the melt-rock reaction could drive and enhance upward entrainment of μm- to mm-scale sulfide in the partially molten mantle, potentially contributing to the fertilization of the sub-continental lithospheric mantle and the endowment of metal-bearing sulfide for the formation of magmatic sulfide deposits.
Nickel (Ni) is a micronutrient that plays a role in nitrogen uptake and fixation in the modern ocean may have impacted rates of methanogenesis on geological timescales. Here we present the results of a diagnostic model of global ocean Ni fluxes which addresses key questions about the biogeochemical processes which cycle Ni in the modern oceans. Our approach starts with extrapolating the sparse available observations of Ni data from the GEOTRACES project into a global gridded climatology of ocean Ni concentrations. Three different machine learning techniques were tested, each relying on marine tracers with better observational coverage such as macronutrient concentrations and physical parameters. The ocean transport of this global Ni concentration field is then estimated using the OCIM2 ocean circulation inverse model, revealing regions of net convergence or divergence. These diagnostics are not based on any assumption about Ni biogeochemical cycling, but their spatial patterns can be interpreted as reflecting biogeochemical processes. We find that the spatial pattern of Ni uptake in the surface ocean is similar to phosphate (P) uptake, but not silicate (Si) uptake, suggesting that Ni is not incorporated into diatom frustules. We find that Ni:P ratios at uptake do not decrease with Ni concentrations approaching 2 nM, which challenges the hypothesis of a ~2 nM pool of non-bioavailable Ni in the surface ocean. Finally, the net regeneration of Ni occurs deeper in the ocean than P remineralization, which could be explained by reversible scavenging or the presence of a refractory Ni phase.
Mass recycling from subduction to magmatic extrusion shapes our habitable environment and Earth’s interior. Subducted igneous crust may form pyroxenites before participating magmatism, but the deep journey of associated carbonates remains unclear. Here we report new Mg-isotope data for ~89 to 81 Ma basaltic rocks in Langshan area, central Asia (δ26Mg = -0.391 to -0.513 ‰) with a synthesis for post-110 Ma basalts across eastern Asian continent. The merged low-δ26Mg basaltic province normally interpreted as derivations from carbonated sources paradoxically displays geochemical signatures (low Ca/Al and high K2O contents) resembling partial melts of uncarbonated sources. Negative correlations of δ26Mg vs TiO2 and FCKANTMS, the proxy of pyroxenitic melts, and adiabatic melting modeling suggest presence of Mg-isotopically light source pyroxenites transformed from decarbonated altered oceanic crust. This may explain ubiquitous pyroxenitic contributions in many low-δ26Mg basaltic suites and has significant implication for deep carbon cycling.