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At least 505 records · Page 28Linked to original sources
USGS2020

Zircon-hosted melt inclusion record of silicic magmatism in the Mesoproterozoic St. Francois Mountains terrane, Missouri: Origin of the Pea Ridge iron oxide-apatite rare earth element deposit and implications for regional crustal pathways of mineralization

Voluminous silicic magmatism was coeval with iron ore mineralization in the St. Francois Mountains terrane in southeast Missouri, part of the broader Mesoproterozoic Granite-Rhyolite province along the eastern margin of Laurentia. Some of the iron deposits contain extraordinary endowments of critical elements, such as the Pea Ridge iron oxide-apatite (IOA) deposit, which has an average grade of ~12 wt% rare earth oxides in breccia pipes that flank the ore body. To assess the role of silicic magmatism in the genesis of the Pea Ridge deposit, we present a high-spatial resolution study of zirconhosted melt inclusions from rhyolitic ash-flow tuffs. Melt inclusion data are combined with textural, geochemical, and geochronological analyses of zircon hosts to elucidate the magmatic-hydrothermal evolution of the Pea Ridge system. Two contemporaneous silicic igneous centers in the St. Francois Mountains terrane, Bourbon and Eminence, were studied for comparison. Pea Ridge melt inclusions are trachydacitic to rhyolitic (~63-79 wt% SiO2, ~5.6-11.7 wt% Na2O+K2O) with very high Cl in the least-evolved and most alkaline melt inclusions (~2,000-5,000 ppm Cl). Rare earth elements (REE) in melt inclusions have identical chondrite-normalized patterns to the mineralized breccia pipes, but with systematically lower absolute concentrations. Haplogranite ternary pressures range from ~0.5-10 kbar, with an average of ~2-3 kbar (7-12 km depth), and liquidus temperatures are ~850-950 °C, with an average of ~920 °C. Silicate and phosphate mineral inclusions have compositions that overlap minerals from the iron ore body and breccia pipes, recording a transition from igneous to hydrothermal zircon growth. Igneous iron oxide inclusions have compositions that indicate Pea Ridge magmas were reduced to moderately oxidized (log fO2 of -0.8 to -1.84 NNO). Zircons from two Pea Ridge samples have 207Pb/206Pb concordia ages of 1456 ± 9 Ma and 1467 ± 13 Ma that overlap published ages for the breccia pipes and iron ore zones of the Pea Ridge deposit. A population of texturally and chemically disrupted zircons have discordant domains that correspond to high Fe, U, and REE concentrations, consistent with the unique geochemical attributes of the IOA-REE ore body. Inherited cores in Pea Ridge and Bourbon zircons have concordant 207Pb/206Pb dates of 1550-1618 Ma, providing direct evidence of cratonic basement beneath these centers. Oxygen isotope data for inherited and autocrystic igneous zircons span from mantle to crustal values (18Ozircon=5.5-7.9‰). Our data are consistent with a model in which metasomatized mantle components were mixed with cratonic and accreted crustal material in a back-arc or rifted segment of a volcanic arc, with ore fluids derived from Cl-rich melts to transport Fe and REE in a long-lived (tens of Myr), pulsed, magmatic-hydrothermal system. Bourbon, which also possesses IOA mineralization, shares key petrologic similarities with the Pea Ridge system, whereas Eminence, which is not mineralized, has disparate geochemical and isotopic signatures that indicate it formed in a different crustal setting. The location of Pea Ridge and Bourbon along a cratonic margin may have been important in focusing silicic melts and mineralization in the upper crust, serving as a guide for future exploration efforts.

Missouri↗
USGS2020

A chemo-mechanical snapshot of in-situ conversion of kerogen to petroleum

Organic matter (OM) from various biogenic origins converts to solid bitumen in-situ when it undergoes thermal maturation. It is well documented that during this process, the ratios of both hydrogen and oxygen to carbon will decrease, resulting in an increase in OM aromaticity and molecular chemo-mechanical homogeneity. Although there have been extensive efforts to reveal molecular alteration occurring to OM during conversion, in-situ and continuous observation of such alterations on naturally occurring samples is missing. Therefore, evaluation of previous results cannot be made independent from natural sample variability. In this study, we identified OM particles ( Tasmanites ) that are evolving in-situ into solid bitumen in the Bakken Formation. This in-situ bituminization allows examination of a continuous transformation in OM molecular structure at micron-scale using AFM based IR spectroscopy applied at the transition/interface zone. Moreover, contact mode in the AFM was employed to reveal and relate changes in mechanical properties at a similar scale of measurement. Understanding these chemical and mechanical alterations is important to understand shale reservoir properties and better explain hydrocarbon generation, expulsion, and migration processes at the microscale.

Geochimica et Cosmochimica Acta↗
USGS2020

Sulfur isotope composition of individual compounds in immature organic-rich rocks and possible geochemical implications

We applied compound-specific sulfur isotope analysis (CSSIA) to organic matter (OM) extracted from ancient and immature organic-rich rocks from the Cretaceous Ghareb (Shefela Basin locality, Israel) and Miocene Monterey (Naples Beach locality, California, USA) Formations. Large variations in the δ 34 S values of different organosulfur compounds (OSCs), that reach up to 28‰ and 36‰, were observed in the Ghareb and Monterey samples, respectively. Additionally, some common OSCs in both locations showed consistent 34 S trends relative to each other. The consistent enrichment in 34 S of C 35 hopane thiophene relative to iC 20 thiophene in the studied sections probably resulted from differences in the timing of OM sulfurization. Reactive organic precursors quickly consume the most 34 S-depleted reduced S, while less reactive species incorporate the heavier residual S at a later time. Despite the differences in the depositional environments, ages, and the initial δ 34 S values of the reduced S (represented by the δ 34 S of pyrite) between the Ghareb and the Monterey Formations, the sulfurization order of common organic compounds seems to be similar. All of the δ 34 S values of OSCs are 34 S enriched relative to that of the coexisting pyrite with the exception of the C 25 highly branched isoprenoid (HBI) thiophene in several samples from the Monterey Formation. The existence of 34 S-depleted sulfurized HBI may point to OM sulfurization that occurred at or near the sediment-water interface during the deposition of the Monterey. Moreover, the δ 34 S of steroid sulfides shows an inverse trend with the pristane/phytane ratio, which may indicate that the sulfurization mechanism of these OSCs are affected by redox conditions. Further investigation of CSSI values in immature rocks from other basins may help constrain the OM sulfurization process, timescale, and depositional conditions and their possible use as paleoenvironmental proxies.

California↗
USGS2020

Biomarker similarities between the saline lacustrine Eocene Green River and the Paleoproterozoic Barney Creek Formations

The Paleoproterozoic Barney Creek Formation, which is currently interpreted as a restricted, deep marine paleoenvironment, plays a disproportionate role in our understanding of Proterozoic ocean chemistry and the rise of complex life. The Barney Creek Formation hosts several unusual biomarker features, specifically its methylhopane and carotenoid signatures. Herein, we demonstrate that the saline lacustrine Eocene Green River Formation shares a similar distribution of methylhopanes and carotenoids, which is characteristic of saline lacustrine organic matter more generally. These distinct methylhopane and carotenoid patterns are not observed together in marine organic matter of any geologic age. These results imply a saline lacustrine depositional environment for the Barney Creek Formation, which agrees with earlier but now abandoned depositional models of this formation. As a result, models of Proterozoic ocean chemistry and emergence of complex life that rely on a marine Barney Creek Formation should be re-examined. Alternatively, if Paleoproterozoic marine biomarker signatures resemble those of younger saline lacustrine systems, then this must be recognized to accurately interpret geologic biomarker and paleoenvironmental records.

Colorado, Utah↗
USGS2020

An important biogeochemical link between organic and inorganic carbon cycling: Effects of organic alkalinity on carbonate chemistry in coastal waters influenced by intertidal salt marshes

Organic acid charge groups in dissolved organic carbon (DOC) contribute to total alkalinity (TA), i.e. organic alkalinity (OrgAlk). Its effect is often ignored or treated as a calculation uncertainty in many aquatic CO2 studies. This study evaluated the variability, sources, and characteristics of OrgAlk in estuarine waters exchanged tidally with a groundwater-influenced salt marsh in the northeast USA. Importantly, OrgAlk was found to serve as a biogeochemical medium linking organic and inorganic carbon cycling through its effects on pH, CO2 system speciation, and buffering capacity (H = -(∂pH/∂[H+])-1). Both the concentrations and characteristics of the identified organic acid charge groups, as well as water pH, influenced the magnitude and sign of the OrgAlk effects. The two main charge groups identified include carboxylic and phenolic or amine groups, with concentrations and pK values varying across tides and seasons. OrgAlk and DOC in the tidal creek were highly variable over tidal and seasonal cycles, and may be sourced from both terrestrial groundwater and in situ production in salt marsh sediments. OrgAlk seems to be more preserved over DOC in groundwater, although DOC and OrgAlk largely covaried in marsh tidal water, but with variable OrgAlk:DOC ratios. This highlights the insufficiency of using a fixed proportion of DOC to account for organic acid charge groups. OrgAlk was found to affect H+ concentrations by ~ 1 – 40 nmol kg-1 (equivalent to a pH change of ~ 0.03 – 0.26), pCO2 by ~ 30 – 1590 atm and buffering capacity by ~ 0.00 – 0.14 mmol kg-1 at relative OrgAlk contributions of 0.9 – 4.3% of TA observed in the marsh-influenced tidal water. Thus OrgAlk may have a significant influence on coastal inorganic carbon cycling. Further theoretical calculations confirm that these concentrations of OrgAlk would have sizable impacts on both carbonate speciation and, ultimately, air-sea CO2 fluxes in different coastal environments, ranging from estuarine to shelf waters. A new conceptual model linking organic and inorganic carbon cycling for coastal waters is proposed to highlight the sources and sinks of organic acid charge groups, as well as their biogeochemical behaviors and mechanistic control on the CO2 system.

Geochimica et Cosmochimica Acta↗
USGS2020

Methane oxidation dynamics in a karst subterranean estuary

Chemical gradients between fresh, brackish and saline waters shape biogeochemical reactions and organic matter transformation within subterranean estuaries. In the Yucatán Peninsula’s karst subterranean estuary (KSE), methane and dissolved organic matter generated during the anaerobic decomposition of tropical forest vegetation are transported into flooded cave networks where microbial consumption greatly reduces their concentrations in the groundwater. To test the hypothesis that chemoclines associated with salinity gradients of the KSE are sites of methane oxidation, we obtained methane concentration and δ 13 C profiles of unprecedented vertical resolution from within a fully-submerged cave system located 6.6 km inland from the coastline using the ‘OctoPiPi’ (OPP) water sampler. Along a 12–24 cm thick low-salinity-halocline at ∼4.5 m water depth, salinity increased from fresh to brackish (0.2–1.8 psu), methane concentrations decreased, and δ 13 C values increased, as expected for microbial methane oxidation. The underlying brackish water had elevated oxygen concentrations compared to the always anoxic freshwater, suggesting that aerobic methane oxidation is the dominant process facilitating methane consumption. By contrast, as salinity increased from 1.8 to 36 psu through a 24–36 cm thick high-salinity-halocline between the meteoric lens and the saline groundwater at ∼20 m water depth, methane concentrations and δ 13 C values were constant. Conservative mixing and kinetic isotope models incorporating the methane data confirm a hotspot for microbial methane oxidation at the low-salinity-halocline. At least 98% of methane originating in the anoxic freshwaters was removed before its transport via channelized flow towards the coastline. These findings provide novel insight into the spatial constraints of methane dynamics within a karst subterranean estuary.

Ox Bel Ha cave system↗
USGS2020

Position-specific distribution of hydrogen isotopes in natural propane: Effects of thermal cracking, equilibration and biodegradation

Intramolecular isotope distributions, including isotope clumping and position specific fractionation, can provide proxies for the formation temperature and formation and destruction pathways of molecules. In this study, we explore the position-specific hydrogen isotope distribution in propane. We analyzed propane samples from 10 different petroleum systems with high-resolution molecular mass spectrometry. Our results show that the hydrogen isotope fractionation between central and terminal positions of natural propanes ranges from −102‰ to +205‰, a much larger range than that expected for thermodynamic equilibrium at their source and reservoir temperatures (36–63‰). Based on these findings, we propose that the hydrogen isotope structure of catagenic propane is largely controlled by irreversible processes, expressing kinetic isotope effects (KIEs). Kinetic control on hydrogen isotope composition of the products of thermal cracking is supported by a hydrous pyrolysis experiment using the Woodford Shale as substrate, in which we observed isotopic disequilibrium in the early stage of pyrolysis. We make a more general prediction of KIE signatures associated with kerogen cracking by simulating this chemistry in a kinetic Monte Carlo model for different types of kerogens. In contrast, unconventional shale fluids or hot conventional reservoirs contain propane with an isotopic structure close to equilibrium, presumably reflecting internal and/or heterogeneous exchange during high temperature storage (ca. 100–150 °C). In relatively cold (<100 °C) conventional gas accumulations, propane can discharge from its source to a colder reservoir, rapidly enough to preserve disequilibrium signatures even if the source rock thermal maturity is high. These findings imply that long times at elevated temperatures are required to equilibrate the hydrogen isotopic structure of propane in natural gas host rocks and reservoirs. We further defined the kinetics of propane equilibration through hydrogen isotope exchange experiments under hydrous conditions; these experiments show that hydrogen in propane is exchangeable over laboratory timescales when exposed to clay minerals such as kaolinite. This implies rather rapid transfer of propane from sources to cold reservoirs in some of the conventional petroleum systems. Propane is also susceptible to microbial degradation in both oxic and anoxic environments. Biodegradation of propane in the Hadrian and Diana Hoover oil fields (Gulf of Mexico) results in strong increases in central-terminal hydrogen isotope fractionation. This reflects preferential attack on the central position, consistent with previous studies.

Geochimica et Cosmochimica Acta↗
USGS2021

Development of soil radiocarbon profiles in a reactive transport framework

Today, there is a greater appreciation for the importance of the physical protection of carbon (C) through interactions with mineral surfaces, isolation from microbes, and the important role of transport in shaping soil properties and controlling moisture limitations on decomposition. As our paradigm for soil organic carbon (SOC) preservation changes, so too should our representation of the underlying processes in soil models. Reactive transport models (RTMs) provide a framework capable of assessing the interactive influence of soil chemistry and transport processes on the accumulation and turnover of SOC. In this study, we present new developments in the isotopically enabled RTM “CrunchTope,” which is capable of explicitly tracking the three isotopes of carbon ( 12 C, 13 C, and 14 C) and their fractionation between multiple coexisting and interacting solid, liquid and gas phases. This modeling framework opens the door to new applications of depth-resolved RTMs models in application to SOC and deeper subsurface carbon reservoirs. Here, we demonstrate SOC accumulation and radiocarbon aging for long-timescale models of soil development in CrunchTope. Our goal is to assess advantages and limitations of such an approach and to identify the type and complexity of reaction networks that are required to adequately apply this model to SOC dynamics. We assess the behavior of this model relative to a high-resolution dataset of SOC content, stable isotope composition, and radiocarbon ages as well as physical and hydrologic data measured from a chronosequence of soils located near Santa Cruz, California. Starting from a previously published model using a simplified reaction network with a single class of carbon, we sequentially incorporate multiple C reservoirs subject to both reactivity and transport pathways. Our results indicate that multiple SOC pools with different mean ages of C do not inherently emerge as a result of including reactions which are conventionally expected to provide a diversity of transit times, i.e., sorption and complexation of SOC on mineral surfaces. Instead, transit times emerge as a result of the timescales of the reactions represented in the reaction network. For mineral associated C, the RTM framework imposes dynamic equilibrium with the fluid phase dissolved organic C, such that no distinction in radiocarbon ages is achieved between these pools. Aged C can be produced by including a solid-phase C reservoir, with a rate-limited solubilization coefficient. Aging of SOC in this way is more akin to selective preservation than to mineral protection and, while such a mechanism may be at play in many soils, mineral protection is thought to be at least as important. As such, our results indicate that additional parameterization is required to reproduce the heterogeneity of carbon transit times that result from organo-mineral interactions. These efforts show the promise of a modeling approach where the varied transit time of soil C emerges from the dynamic physical and hydrologic properties of the model rather than from the a priori assignment of operationally defined pools.

Geochimica et Cosmochimica Acta↗
USGS2021

Origin of the isotopic composition of natural perchlorate: Experimental results for the impact of reaction pathway and initial ClOx reactant

Natural perchlorate (ClO 4 − ) exists in many places on Earth, in lunar regolith, meteorites, and on the surface of Mars. Terrestrial natural ClO 4 − has widely variable Cl and O stable isotopic compositions (δ 37 Cl, δ 18 O, Δ 17 O). The δ 18 O and Δ 17 O values of ClO 4 − from the most hyper-arid locations co-vary. ClO 4 − from less arid areas has relatively little 17 O excess and poor Δ 17 O-δ 18 O correlation. ClO 4 − from the Atacama Desert has unusually low δ 37 Cl (<−10‰) and exhibits a positive correlation between δ 37 Cl and δ 18 O, while the δ 37 Cl of ClO 4 − from all other locations varies between −5 and +7‰ with no δ 37 Cl-δ 18 O covariation. To evaluate the impact of different precursors (ClO x ) and reaction pathways on the isotopic composition of ClO 4 − , we measured the isotopic composition of ClO 4 − produced in the laboratory by UV or O 3 mediated aqueous oxidation of Cl − , OCl − , ClO 2 − , and ClO 2 ° as well as O 3 mediated oxidation of dry NaCl. ClO x oxidation in aqueous or dry systems enriched in O 3 produced ClO 4 − with Δ 17 O values that generally increased with the number of O atoms required and included evidence that the site-specific 17 O anomaly in O 3 was preferentially transferred to ClO 4 − . Based on the inferred number of O atoms sourced from O 3 , and known Cl and O reaction pathways, it appears that ClO 2 ° and ClO 3 * were required intermediates in the production of ClO 4 − in the O 3 experiments. ClO x aqueous oxidation by UV irradiation produced ClO 4 − with a large range of δ 18 O values and little or no 17 O anomaly. ClO 3 − was produced to a much greater extent than ClO 4 − in all experiments except dry oxidation of NaCl by O 3 . The isotopic composition of ClO 3 − was distinct from that of ClO 4 − produced from the same initial reactants. Combined results of O 3 and UV mediated reactions largely bracketed the range of natural ClO 4 − δ 18 O and Δ 17 O values as well as δ 37 Cl values of non-Atacama natural samples, but no conditions produced the low δ 37 Cl values of Atacama ClO 4 − . Our results indicate that variation in production mechanisms, possibly combined with isotopically variable precursors, could be responsible for much of the observed isotopic variation in natural ClO 4 − and ClO 3 − .

Geochimica et Cosmochimica Acta↗
USGS2021

A reactive transport approach to modeling cave seepage water chemistry II: Elemental signatures

Karst systems are useful for examining spatial and temporal variability in Critical Zone processes because they provide a window into the subsurface where waters have interacted with vegetation, soils, regolith, and bedrock across a range of length and timescales. These hydrologic pathways frequently include the precipitation of speleothems, which provide long-term archives of climate and environmental change. Trace element ratios in speleothems (Mg/Ca, Sr/Ca, Ba/Ca) have the potential to provide information about past changes in rainfall and infiltration, but controls on them can be complex and their interpretation must be based on an understanding of the modern cave system. Here we integrate observations of surface conditions, bedrock, soil, and drip water chemistry of Blue Spring Cave in Tennessee, USA with the reactive transport model CrunchTope, which we have calibrated for karst systems to investigate the primary controls on trace element variations in cave seepage waters. We find that measured drip water Mg/Ca and Sr/Ca are captured within the model through variable amounts of limestone dissolution followed by precipitation of secondary calcite that happens within the cave rather than the host limestone. However, strong spatial controls on drip water Mg/Ca and Sr/Ca likely reflect seepage water interactions with variable amounts of diagenetic phases in the host rock. In contrast, Ba/Ca values are consistent across the cave and vary with effective rainfall, suggesting that this parameter may be the most consistent metric for limestone dissolution and prior calcite precipitation and can act as a proxy for rainfall and infiltration in this cave system. Our findings emphasize the importance of evaluating spatial heterogeneity in cave drip waters and outline a novel modeling approach for determining the dominant controls on drip water chemistry in support of the interpretations of paleoclimate records.

Geochimica et Cosmochimica Acta↗
USGS2021

A reactive transport approach to modeling cave seepage water chemistry I: Carbon isotope transformations

The majority of Critical Zone research has emphasized silicate lithologies, which are typified by relatively slow rates of reactivity and incongruent weathering. However, the relatively simpler weathering of carbonate-dominated lithology can result in secondary mineral deposits, such as speleothems, which provide a long-term archive for Critical Zone processes. In particular, carbon isotopic variability in speleothems has the potential to provide records of changes in vegetation, soil respiration, carbon stabilization in deep soils, and/or chemical weathering in the host rock. Despite this opportunity to reconstruct many Critical Zone processes, multiple influences can also make interpretion of these speleothem carbon isotope records challenging. The integration of observational data and simulations specific to karst systems offers an interpretive framework for these unique time-averaged records accumulated through the evolution of carbonate landscapes. Here, we present a forward and process-based reactive transport simulation based on a multi-year monitoring study of Blue Spring Cave in central Tennessee, USA. The simulations describe the fluid-driven weathering of limestone including explicit tracking of dissolved calcium, stable carbon, and radiocarbon isotope ratios based on reaction rates calibrated through laboratory batch reaction data. We find that calcium concentrations and radiocarbon isotope ratios are strongly influenced by the combination of fluid flow rate and soil CO 2 content, and require rapid gas phase communication between the overlying soil boundary condition and interior karst to sustain both elevated limestone weathering rates and relatively modern radiocarbon signatures. Stable carbon isotopes are largely dictated by temperature-dependent equilibrium fractionation among contemporaneous species. These simulations are extended to a wide range of parameter space to demonstrate the environmental factors that these isotope proxies record.

Geochimica et Cosmochimica Acta↗
USGS2022

Juvenile continental crust evolution in a modern oceanic arc setting: Petrogenesis of Cenozoic felsic plutons in Fiji, SW Pacific

Viti Levu, Fiji, provides one of the best exposed Phanerozoic analogues for the formation of juvenile continental crust in an intra-oceanic setting. Tonalites and trondhjemites are present in several large (75–150 km 2 ) adjacent, mid-Cenozoic plutons. We report major and trace element data including rare earth element (REE) and high-precision high field strength element (HFSE) compositions, new Hf-Nd-Sr-Pb isotope data, and zircon U/Pb-ages, O-Hf isotopes, and trace elements, from five different plutons. The Eocene Yavuna pluton and the Miocene Colo plutons are mainly composed of tonalites and trondhjemites and represent the exposed middle crust of the former Vitiaz island arc. The plutons can be divided into three suites. One suite is light REE (LREE) depleted with some trace element ratios lower than average normal mid-ocean ridge basalts (N-MORB). A second suite has flat REE patterns similar to local island arc basalts. Both suites occur near the coast of Viti Levu, include a wide compositional spectrum from gabbro to tonalite, and can be produced mostly by fractional crystallization of mafic precursor melts. The third suite is characterized by LREE enrichments with higher La N /Yb N (2.3–4.9), higher Zr/Y (4.3–7.1), and lower Nb/Ta (9.6–12.4). They occur closer to the center of the island and are bimodal trondhjemite-gabbro intrusions. These characteristics are consistent with formation mostly by partial melting of mafic crust. Trace element modeling shows that the trace element ratios of the third suite can be produced by 10–20 % melting of the mafic crust in the presence of residual amphibole, resulting in the retention of the medium REE (MREE) and diagnostic trace element ratios including low Nb/Ta and high Zr/Y. Geochemical similarities of the LREE enriched suite to typical “low”-pressure Archean tonalites-trondhjemites-granodiorites (TTGs) imply a common petrogenetic origin and similar mechanisms for the generation of juvenile Archean and modern differentiated crust by partial melting of mafic crust with residual amphibole. In modern oceanic arcs, genetically unrelated felsic plutonic as well as volcanic rocks co-exist, and in this regard, the Fijian plutons accompany major tectonic disruptions to arc processes.

Geochimica et Cosmochimica Acta↗
USGS2022

Barium enrichment in the non-spinose planktic foraminifer, Globorotalia truncatulinoides

Observations of elevated barium-to-calcium ratios (Ba/Ca) in Globorotalia truncatulinoides have been attributed to contaminant phases, deep calcification depth and diagenetic processes. Here we investigate intra- and inter-test Ba/Ca variability in the non-spinose planktic foraminifer, G. truncatulinoides , from a sediment trap time series in the northern Gulf of Mexico to gain insights into the environmental influences on barium enrichment in this and other non-spinose species. We use laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to differentiate between the elemental composition of the crust and lamellar calcite in non-encrusted (<150 m calcification depth) and encrusted (>150 m calcification depth) specimens of G. truncatulinoides . We find that the Ba/Ca ratio in lamellar calcite is between two and three orders of magnitude higher (10–280 μmol/mol) than that of the crust (0–3 μmol/mol). We include seasonal water column profiles of the Ba/Ca ratio in the northern Gulf of Mexico and determine that the vertical gradient in seawater barium concentration cannot account for the intra-test Ba/Ca variations in G. truncatulinoides . We find the Ba/Ca ratio of the crust to be within the range observed in co-occurring spinose species of foraminifera (pink and white chromotypes of Globigerinoides ruber , and Orbulina universa ) while the range of Ba/Ca in lamellar calcite is consistent with co-occurring non-spinose foraminifera ( Pulleniatina obliquiloculata , Globorotalia menardii , G. tumida , and Neogloboquadrina dutertrei ). Our data are consistent with the hypothesis that G. truncatulinoides calcifies in a marine snow aggregate microenvironment that is enriched in barium relative to ambient seawater. We suggest that G. truncatulinoides crust is formed after the rhizopodia retract and the foraminifer detaches from its marine snow substrate.

Geochimica et Cosmochimica Acta↗
USGS2022

Hydrogen isotope behavior during rhyolite glass hydration under hydrothermal conditions

The diffusion of molecular water (H 2 O m ) from the environment into volcanic glass can hydrate the glass up to several wt% at low temperature over long timescales. During this process, the water imprints its hydrogen isotope composition (δD H2O ) to the glass (δD gl ) offset by a glass-H 2 O fractionation factor (ΔD gl-H2O = δD gl – δD H2O ) which is approximately −33‰ at Earth surface temperatures. Glasses hydrate much more rapidly at higher, sub-magmatic temperatures as they interact with H 2 O during eruption, transport, and emplacement. To aid in the interpretation of δD gl in natural samples, we present hydrogen isotope results from vapor hydration experiments conducted at 175–375 °C for durations of hours to months using natural volcanic glasses. The results can be divided into two thermal regimes: above 250 °C and below 250 °C. Lower temperature experiments yield raw ΔD gl-H2O values in the range of −33 ± 11‰. Experiments at 225 °C using both positive and negative initial ΔD gl-H2O values converge on this range of values, suggesting this range represents the approximate equilibrium fractionation for H isotopes between glass and H 2 O vapor (10 3 lnα gl-H2O ) below 250 °C. Variation in ΔD gl-H2O (−33 ± 11‰) between different experiments and glasses may arise from incomplete hydration, analytical uncertainty, differences in glass chemistry, and/or subordinate kinetic isotope effects. Experiments above 250 °C yield unexpectedly low δD gl values with ΔD gl-H2O values of ≤–85‰. While alteration alone is incapable of explaining the data, these run products have more extensive surface alteration and are not interpreted to reflect equilibrium fractionation between glass and H 2 O vapor. Fourier transform infrared spectroscopy (FTIR) shows that glass can hydrate with as much as 5.9 wt% H 2 O m and 1.0 wt% hydroxl (OH − ) in the highest P-T experiment at 375 °C and 21.1 MPa. Therefore, we employ a 1D isotope diffusion–reaction model of glass hydration to evaluate the roles of equilibrium fractionation, isotope diffusion, water speciation reactions internal to the glass, and changing boundary conditions (e.g. alteration and dissolution). At lower temperatures, the best fitting model results to experimental data for low silica rhyolite (LSR) glasses require only an equilibrium fractionation factor and yield 10 3 lnα gl-H2O values of −33‰ ± 5‰ and −25‰ ± 5‰ at 175 °C and 225 °C, respectively. At higher temperatures, ΔD gl-H2O is dominated by boundary layer effects during glass hydration and glass surface alteration. The modeled bulk δD gl value is highly responsive to changes in the δD gl boundary condition regardless of the magnitude of other kinetic effects. Observed glass dissolution and surficial secondary mineral formation are likely to impose a disequilibrium boundary layer that drives extreme δD gl fractionation with progressive glass hydration. These results indicate that the observed ΔD gl-H2O of ∼−33 ± 11‰ can be cautiously applied as an equilibrium 10 3 lnα gl-H2O value to natural silicic glasses hydrated below 250 °C to identify hydration sources. This approximate ΔD gl-H2O may be applicable to even higher temperature glasses hydrated on short timescales (of seconds to minutes) in phreatomagmatic or submarine eruptions before H 2 O in the glass is primarily affected by boundary layer effects associated with alteration on the glass surface.

Geochimica et Cosmochimica Acta↗
USGS2023

Mineralogical, magnetic and geochemical data constrain the pathways and extent of weathering of mineralized sedimentary rocks

The oxidative weathering of sulfidic rock can profoundly impact watersheds through the resulting export of acidity and metals. Weathering leaves a record of mineral transformation, particularly involving minor redox-sensitive phases, that can inform the development of conceptual and quantitative models. In sulfidic sedimentary rocks, however, variations in depositional history, diagenesis and mineralization can change or overprint the distributions of these trace minerals, complicating the interpretation of weathering signatures. Here we show that a combination of bulk mineralogical and geochemical techniques, micrometer-resolution X-ray fluorescence microprobe analysis and rock magnetic measurements, applied to drill core samples and single weathered fractures, can provide data that enable the development of a geochemically consistent weathering model. This work focused on one watershed in the Upper Colorado River Basin sitting within the Mesaverde Formation, a sedimentary sandstone bedrock with disseminated sulfide minerals, including pyrite and sphalerite, that were introduced during diagenesis and subsequent magmatic-hydrothermal mineralization. Combined analytical methods revealed the pathways of iron (Fe), carbonate and silicate mineral weathering and showed how pH controls element retention or release from the actively weathering fractured sandstone. Drill core logging, whole rock X-ray diffraction, and geochemical measurements document the progression from unweathered rock at depth to weathered rock at the surface. X-ray microprobe analyses of a 1-cm size weathering profile along a fracture surface are consistent with the mobilization of Fe(II) and Fe(III) into acidic pore water from the dissolution of primary pyrite, Fe-sphalerite, chlorite, and minor siderite and pyrrhotite. These reactions are followed by the precipitation of secondary minerals such as of goethite and jarosite, a Fe-(oxyhydr)oxide and hydrous Fe(III) sulfate, respectively. Microscale analyses also helped explain the weathering reactions responsible for the mineralogical transformations observed in the top and most weathered section of the drill core. For example, dissolution of feldspar and chlorite neutralizes the acidity generated by Fe and sulfide mineral oxidation, oversaturating the solution in both Fe-oxides. The combination of X-ray spectromicroscopy and magnetic measurements show that the Fe(III) product is goethite, mainly present either as a coatings on fracture surfaces in the actively weathering region of the core or more homogeneously contained within the unconsolidated regolith at the top of the core. Low-temperature magnetic data reveal the presence of ferromagnetic Fe-sulfide pyrrhotite that, although it occurs at trace concentrations, could provide a qualitative proxy for unweathered sulfide minerals because the loss of pyrrhotite is associated with the onset of oxidative weathering. Pyrrhotite loss and goethite formation are detectable through room-temperature magnetic coercivity changes, suggesting that rock magnetic measurements can determine weathering intensity in rock samples at many scales. This work contributes evidence that the weathering of sulfidic sedimentary rocks follows a geochemical pattern in which the abundance of sulfide minerals controls the generation of acidity and dissolved elements, and the pH-dependent mobility of these elements controls their export to the ground- and surface-water.

Colorado↗
USGS2023

Triple oxygen isotope compositions of globally distributed soil carbonates record widespread evaporation of soil waters

The stable isotopic composition of pedogenic carbonates is central to many studies of past climate and topography, providing a basis for our understanding of Earth's terrestrial history. A core assumption of many applications of oxygen isotope values (δ18O) of pedogenic carbonate is that they reflect the δ18O value of precipitation (rain/snow). This assumption is violated if soil carbonates form in evaporated soil waters. In this work, we develop a means to identify evaporation in ancient soils using the triple oxygen isotope composition (16O-17O-18O) of pedogenic carbonates. Both theoretical predictions of isotope kinetics during evaporation and studies of triple oxygen isotopes in other geological materials show that the deviation in the relationship between δ17O and δ18O from a reference line, evaluated using the parameter Δ'17O, is sensitive to evaporation. As a first step in developing the use of Δ'17O in ancient pedogenic carbonates, we report Δ'17O values from 47 near-modern pedogenic carbonate samples from globally distributed environments that vary in aridity (hyper-arid to humid). The Δ'17O values of pedogenic carbonate range from -154 to -60 per meg (as CaCO3, measured via O2, VSMOW-SLAP), corresponding to calculated soil water values of -66 to +27 per meg (VSMOW-SLAP) (using a carbonate-water triple oxygen isotope fractionation exponent of 0.5250 and clumped isotope-derived carbonate growth temperatures). The Δ'17O values indicate that evaporative modification of soil water from which pedogenic carbonate forms is common, especially in arid environments. Arid environments host pedogenic carbonates formed from soil waters ranging from highly to minimally evaporated, while humid environments host pedogenic carbonates formed from waters that are only minimally evaporated. The variability in Δ'17O within environments classified by the same aridity may relate to the fact that pedogenic carbonates record soil conditions only during times of carbonate mineralization, which may deviate from annual conditions. Thus, Δ'17O may be useful in understanding the specific circumstances of pedogenic carbonate formation but may not provide incontrovertible evidence of the magnitude of environmental aridity. Evaporative modification of δ18O values of pedogenic carbonates can be detected with Δ'17O, thereby improving estimates of δ18O of unevaporated waters. Our data show that evaporation must be (re)considered for all paleoclimate inferences based on the δ18O of pedogenic carbonate. The addition of Δ'17O will re-energize paleoclimate studies that use (or have avoided using) δ18O of pedogenic carbonate.

Geochimica et Cosmochimica Acta↗
USGS2023

Potassium-39-derived 36Ar production during fission-neutron irradiation and its effect on 40Ar/39Ar ages

Various interference reactions producing unwanted Ar isotopes from K, Ca, Cl and Ar require correction to satisfy the 40 Ar/ 39 Ar age equation. Using GEANT4, we design and build a model Cadmium Lined In Core Irradiation Tube (CLICIT) irradiation facility, as used in the Oregon State TRIGA Reactor (OSTR). We illustrate the complexity of the irradiation of geologic samples within this framework and determine an overlooked production channel of 36 Ar. The production of 36 Ar is fed from the 39 K(n, α ) 36 Cl nuclear channel, 36 Cl subsequently decays to 36 Ar ( 39 K(n, α, β ) 36 Ar). Simulations in this work using a 235 U fission neutron energy spectrum and modelled CLICIT facility, determine a production ratio for this reaction ( 36 Cl/ 39 Ar) K = 0.40 ± 0.01 (1 σ ); greater than an order of magnitude larger than any other K interference. The magnitude of the resulting age bias for an unknown sample will be a function of the integrated neutron flux, the length of irradiation (fluence), the time elapsed since irradiation, and the age relationship between the unknown and neutron fluence monitor. We show using the raw data of (Niespolo et al., 2017) that the age of Alder Creek sanidine can be modified to be ca. 0.1% older (1 σ ), at the 2σ level of current analytical precision for the Alder Creek age for this study. The 39 K(n, α , β ) 36 Ar inference should be incorporated into routine data analysis and may be especially important in the intercalibration of the 40 Ar/ 39 Ar system with other chronometers (e.g., 206 Pb/ 238 U).

Geochimica et Cosmochimica Acta↗
USGS2023

Intramolecular carbon isotope geochemistry of butane isomers from laboratory maturation and Monte-Carlo simulations of kerogen types I, II, and III

Position-specific (PS) carbon isotope compositions of light hydrocarbons such as propane and butane isomers (n-butane and i-butane) can provide a wealth of information on the history of natural gases in the subsurface reservoirs and other environments. For PS carbon isotope analysis of butane isomers, we have established a GC-pyrolysis-GC-isotope ratio mass spectrometry method with demonstrated accuracy. With this method, we analyzed PS δ 13 C values of butane isomers generated from the systematic laboratory pyrolysis experiments of three different kerogen types (I, II, and III) at temperatures of 310–430 °C with corresponding thermal maturity (Easy %R o ) ranging from 0.7 to 3.3. The observed evolution in the abundances of butane isomers can be interpreted and semi-quantitatively modeled based on the abundances of different C C bonds within the kerogens at low maturity and thermal degradation of butane isomers at high maturity. The δ 13 C values at the central sites of both nC 4 and iC 4 were heavier than those at the terminal positions, similar to our previous observations of propane. Their isotopic evolution with the maturity were controlled largely by kinetic isotope effects associated with breaking of different C C bonds during the generation and degradation of butane isomers. Kinetic Monte Carlo (kMC) simulations of n-butane generated from thermal cracking of model kerogens (I, II, and III) and an oil with a series of reactions (homolytic cleavage, β-scission, radical isomerization, H-abstraction, and termination by radical recombination) provided generally consistent results with the experimental observations, although the difference in PS δ 13 C values between the central and terminal positions are somewhat overestimated. On the other hand, the kMC simulation with homolytic cleavage and capping reactions alone produced significant deviations from the experimental results. Re-assessment of very limited data of PS δ 13 C values of natural butanes with our experimental and simulation results show that biodegradation significantly increased δ 13 C values at the central positions, not only of propane, but also of both butane isomers. This study lays a foundation and demonstrates the potential of PS isotope geochemistry of butane isomers to further improve our understanding of the sources, and geochemical and microbial processes of light hydrocarbons in the subsurface and other natural environments.

Geochimica et Cosmochimica Acta↗