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811 geochemistry Preprints

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Please note: These are preprints and have not been peer reviewed. Data may be preliminary.
Paleovegetation dynamics in a montane vegetation mosaic in the Western Ghats, India:...
Prabhakaran Ramya Bala
Sarath Kavil

Prabhakaran Ramya Bala

and 6 more

September 05, 2020
Ecologists have proposed that montane grassland-shola (stunted evergreen forest) mosaics in the Western Ghats may represent alternative stable vegetation states. But paleoecology investigations seldom consider this framework, especially the role of short-term disturbances (fire, intense drought) other than long-term climatic changes, that can cause vegetation switches in landscapes with alternative vegetation states. The Sandynallah valley that hosts one of the oldest peat accumulations in the world at >50 kyr has been central to the reconstruction of paleovegetation in the montane Nilgiris, Western Ghats. Although the peat-forming vegetation here (dominated by sedges) is a unique vegetation state, its contribution to the paleovegetation signal has not been explicitly considered. We propose a conceptual framework of a tri-stability landscape with sedgeland on the valley floor, grassland on the hill slopes and shola vegetation in the boundary between sedgeland and grassland. While frost prevents shola saplings from establishing in grassland, waterlogging provides a barrier for their establishment in sedgeland, thus maintaining these distinct vegetation states under the same climate. We investigated the stable carbon isotope signatures of the cellulose fraction from two well-dated peat cores (Cores 1 and 2) collected from ~170m apart in the Sandynallah valley within the alternative stable states framework. We find that Core 1, which is closer to the boundary of valley and hill slope, shows dynamic switches between sedgeland and shola whereas Core 2, located in the centre of the valley floor, represents a stable sedgeland state. The vegetation switches and maintenance mechanisms at Core 1 is connected to a disturbance (fire) and to changing climate while Core 2 seems to be responding primarily to climatic changes. The simultaneously distinctive vegetation states in Cores 1 and 2 at such close proximity within the same valley is the first record of alternative stables states in the past in the Western Ghats.
Earthquakes and Volcanic Eruptions Driven by Magma Solitons
Caden Lin
Bjorn Birnir

Caden Lin

and 1 more

November 15, 2021
A magma soliton is used to compute the timing of earthquakes on the Reykjanes ridge, in Iceland, and the occurrence and duration of the volcanic eruption in Geldingadalir by Fagradalsfjall, in February 2021. The velocity of the magma soliton is computed using earthquakes observed underwater on the Reykjanes ridge in November 2019 and earthquakes that occurred by Fagradalsfjall in October 2020. This velocity also determines the shape, height and spatial extent, of the magma soliton. The volume of lava in the Geldingadalur-Fagradalsfjall eruption is computed, depending of the width of the magma soliton, and compared to measurements. The timing of subsequent earthquake clusters is then predicted, caused by the magma soliton passing by the remining three volcanic zones on the Reykjanes peninsula.
Parse, simulation, and prediction of NOx emission across the Midwestern United States
Huan Fang
Greg Michalski

Huan Fang

and 2 more

February 21, 2018
Accurately constraining N emissions in space and time has been a challenge for atmospheric scientists. It has been suggested that 15N isotopes may be a way of tracking N emission sources across various spatial and temporal scales. However, the complexity of multiple N sources that can quickly change in intensity has made this a difficult problem. We have used a SMOKE emission model to parse NOx emission across the Midwestern United States for a one-year simulation. An isotope mass balance methods was used to assign 15N values to road, non-road, point, and area sources. The SMOKE emissions and isotope mass balance were then combined to predict the 15N of NOx emissions (Figure 1). This δ15N of NOx emissions model was then incorporated into CMAQ to assess the role of transport and chemistry would impact the 15N value of NOx due to mixing and removal processes. The predicted 15N value of NOx was compared to those in recent measurements of NOx and atmospheric nitrate.
Chromophoric Dissolved Organic Matter (CDOM): chemical structure and PARAFAC analysis
Rossana Del Vecchio
Neil V Blough

Rossana Del Vecchio

and 5 more

March 02, 2018
The structure(s), distribution and dynamics of CDOM have been investigated over the last several decades largely through optical spectroscopy (including both absorption and fluorescence) due to the fairly inexpensive instrumentation and the easy-to-gather data (over thousands published papers from 1990-2016). Yet, the chemical structure(s) of the light absorbing and emitting species or constituents within CDOM has only recently being proposed and tested through chemical manipulation of selected functional groups (such as carbonyl and carboxylic/phenolic containing molecules) naturally occurring within the organic matter pool. Similarly, fitting models (among which the PArallel FACtor analysis, PARAFAC) have been developed to better understand the nature of a subset of DOM, the CDOM fluorescent matter (FDOM). Fluorescence spectroscopy coupled with chemical tests and PARAFAC analyses could potentially provide valuable insights on CDOM sources and chemical nature of the FDOM pool. However, despite that applications (and publications) of PARAFAC model to FDOM have grown exponentially since its first application/publication (2003), a large fraction of such publications has misinterpreted the chemical meaning of the delivered PARAFAC ‘components’ leading to more confusion than clarification on the nature, distribution and dynamics of the FDOM pool. In this context, we employed chemical manipulation of selected functional groups to gain further insights on the chemical structure of the FDOM and we tested to what extent the PARAFAC ‘components’ represent true fluorophores through a controlled chemical approach with the ultimate goal to provide insights on the chemical nature of such ‘components’ (as well as on the chemical nature of the FDOM) along with the advantages and limitations of the PARAFAC application.
Records of Himalayan Metamorphism and Contractional Tectonics in the central Himalaya...
Elizabeth Catlos

Elizabeth Catlos

November 09, 2021
The Himalayan orogen exposes a range of metamorphosed assemblages, from low-grade Indian shelf sediments of the Tethyan Formation to eclogite and ultra-high pressure rocks documented near the suture zone between the Indian craton and Asian subcontinent. Barrovian-grade pelites and mafic protoliths are exposed in the Himalayan core and include the Greater Himalayan Crystallines and Lesser Himalayan Formations. These units are separated by the Main Central Thrust (MCT). This fault system accommodated a significant amount of India-Asia convergence and is the focus of several models that explore ideas about the development of the range and collisional belts in general. These units provide critical information regarding the mechanisms of heat transfer within collisional belts. Garnets collected across the MCT record their growth history through changes in chemistry. These chemical changes can be extracted and modeled using a variety of thermodynamic approaches. This paper reviews the geological framework of the Himalayas with a focus on the protolith of its metamorphosed assemblages. It describes and applies particular thermobarometric techniques to decipher the metamorphic history of several garnet-bearing rocks collected across the MCT in central Nepal. Comparisons are made between the results of previously-reported conventional rim P-T conditions and P-T paths extracted using the Gibb’s method to isopleth thermobarometry and high-resolution P-T path modeling using the same data and assemblages. Predictions of the paths on garnet zoning are also presented for the high-resolution P-T path modeling and Gibb’s method using the program TheriaG. Although the approaches yield different absolute conditions and P-T path shapes, all are consistent with the development of the MCT shear zone due to imbrication of distinct rock packages. Greater Himalayan Crystalline garnets experienced higher-grade conditions that make extracting its P-T conditions and paths a challenge. Lesser Himalayan garnets appear to behave as closed systems and are ideally suited for thermodynamic approaches.
To Split or to Lump? The Importance of Facies Analysis for Interpreting Stable Isotop...
Anne Fetrow
Kathryn Snell

Anne Fetrow

and 4 more

November 09, 2021
Stable isotope geochemistry of terrestrial carbonates provides important opportunities to answer questions about climates, environments, and ecosystems both in the present day and the geologic past. Here we present a case study from the Cretaceous Newark Canyon Formation (NCF) type section (~98–113 Ma), where we explore how climate and depositional settings influence the stable isotope record in highly variable lacustrine and palustrine carbonates. The NCF was deposited within the hinterland of the Sevier orogenic belt and allows us to examine how North American terrestrial climate changed during the mid-Cretaceous, a time of potentially significant regional surface uplift and increasing global temperatures related to the Cretaceous Thermal Maximum (Di Fiori et al., 2020; Huber et al., 2018). In this study, we find substantial inter- and intra-facies heterogeneity, despite having formed in the same overall climate setting, highlighting the differences between lacustrine and palustrine environments. Stable carbon, oxygen, and clumped isotopes (δ13C, δ18Ocarbonate, and Δ47) paired with optical and cathodoluminescence petrography from along-strike lateral and vertical stratigraphic sections show significant isotopic variability between and within seven carbonate facies (Fetrow et al., 2020). Palustrine deposition is interpreted to have occurred along a spectrum of shallow water depths preserved in two key palustrine sub-facies endmembers – shallower mottled micrite and deeper pebbly, peloid-rich micrite. These record mean Δ47 temperatures of 51ºC and 44°C, respectively. The mottled micrite has heavier calculated δ18O of formation water (δ18Owater) values indicating increased evaporative enrichment, which suggests more intense desiccation during deposition. Lacustrine sediments preserved in laminated biomicrite to massive micrite have mean Δ47 temperatures of 50ºC and 37°C, respectively. Elevated temperatures and δ13C, δ18Ocarb, and δ18Owater values more similar to values from NCF secondary spar veins indicate that the biomicrite sub-facies underwent diagenetic alteration. We will discuss the implications of these results for the NCF and the Cretaceous western USA paleoclimate record, as well as general lessons learned for interpreting mixed terrestrial carbonate facies records.
Seasonal variability in a warming climate: Lessons from the Pliocene Warm Period and...
Niels de Winter
Nina Wichern

Niels de Winter

and 6 more

December 06, 2021
One of the most worrisome aspects of anthropogenic climate change is its potential to enhance the frequency and severity of extreme weather events and seasonality (van der Wiel et al., 2021). More accurate reconstructions of short-term climate variability in past warm climates help improve our projections of this type of variability in future climate (IPCC, 2013). Here, we apply our recently developed clumped isotope methodology for absolute seasonal sea surface temperature and salinity reconstructions (de Winter et al., 2021a; b) on fossil mollusk shells from the Pliocene Warm Period (3.0 – 3.3 Ma) of northwestern Europe, an important analogue for equilibrium climate under present-day radiative forcing (pCO2 ≈ 400 ppmV; Haywood et al., 2016). Isotope records from well-preserved shells of four different bivalve species (Arctica islandica, Glycymeris radiolyrata, Angulus benedeni and Ostrea edulis) reveal warm sea surface temperatures and high seasonal variability during the key mid-Pliocene PRISM interval, allowing detailed comparison with long-term geological climate reconstructions and an ensemble of model simulations (Haywood et al., 2016). Moreover, our results shed light on sub-annual variability in water chemistry in the shallow European epicontinental seas during this crucial period. These new findings highlight the effect of a warming climate on shallow marine ecosystems and shed light on the seasonal response to global warming. Haywood, A. M. et al. Integrating geological archives and climate models for the mid-Pliocene warm period. Nat Commun 7, 10646 (2016). IPCC, 2013: Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change, 1535 pp. (Cambridge Univ. Press, Cambridge, UK, and New York, 2013). van der Wiel, K. & Bintanja, R. Contribution of climatic changes in mean and variability to monthly temperature and precipitation extremes. Commun Earth Environ 2, 1–11 (2021). de Winter, N. J. et al. Optimizing sampling strategies in high-resolution paleoclimate records. Climate of the Past 17, 1315–1340 (2021a). de Winter, N. J. et al. Absolute seasonal temperature estimates from clumped isotopes in bivalve shells suggest warm and variable greenhouse climate. Commun Earth Environ 2, 1–8 (2021b).
Challenges in scaling up greenhouse gas fluxes: experience from the UK Greenhouse Gas...
Peter Levy
Robert Clement

Peter Levy

and 8 more

December 06, 2021
The role of greenhouse gases (GHGs) in global climate change is now well recognised and there is a clear need to measure emissions and verify the efficacy of mitigation measures. To this end, reliable estimates are needed of the GHG balance at national scale and over long time periods, but these estimates are difficult to make accurately. Because measurement techniques are generally restricted to relatively small spatial and temporal scales, there is a fundamental problem in translating these into long-term estimates on a regional scale. The key challenge lies in spatial and temporal upscaling of short-term, point observations to estimate large-scale annual totals, and quantifying the uncertainty associated with this upscaling. Here, we review some approaches to this problem, and synthesise the work in the recent UK Greenhouse Gas Emissions and Feedbacks Programme, which was designed to identify and address these challenges. Approaches to the scaling problem included: instrumentation developments which mean that near-continuous data sets can be produced with larger spatial coverage; geostatistical methods which address the problem of extrapolating to larger domains, using spatial information in the data; more rigorous statistical methods which characterise the uncertainty in extrapolating to longer time scales; analytical approaches to estimating model aggregation error; enhanced estimates of C flux measurement error; and novel uses of remote sensing data to calibrate process models for generating probabilistic regional C flux estimates.
Negative Ce Anomaly in the Banded Iron Formation and Associated Clastic Rocks of the...
Pallabi Basu
Ishwar-Kumar C

Pallabi Basu

and 3 more

December 06, 2021
Banded Iron Formations (BIFs) are archives of Precambrian seawater composition. Presence or absence of negative Ce anomaly (Ce/Ce*) in BIFs has been widely used to understand paleo-redox conditions on the Earth’s surface in the Precambrian. However, whether the extremely negative Ce anomaly associated with the BIFs reflects a primarily depositional signature or not has been questioned and it has been suggested that such signatures could also arise from secondary alterations.1 We report elemental and Nd isotopic data for BIFs and associated clastic rocks from the Sirsi region in southern India. Major and trace element compositions of these BIFs were measured using an Inductively Coupled Plasma Mass Spectrometer (ICP-MS, X series II) while Nd isotope ratio (143Nd/144Nd) measurements were performed using a Thermal Ionization Mass Spectrometer (TIMS, Triton Plus), both at the Centre for Earth Sciences (CEaS), Indian Institute of Science Bangalore, India. The BIF samples are sub-divided into two groups based on their REE+Y (REY) compositions. The group-1 BIFs show seawater-like REY pattern with HREE enrichment over LREEs and super-chondritic Y/Ho (41-52). These BIF samples also lack significant negative Ce anomalies. In contrast, group-2 BIFs show high LREE/HREE enrichment, negative Ce anomaly, and sub-chondritic Y/Ho. Very high values of La/Yb in the group-2 BIFs cannot be explained by simple two-component mixing of basement rock (Dharwar TTG) and pristine Sirsi BIFs. Instead, fluid-rock alteration by LREE enriched, and Ce depleted fluid could explain the observed REY variations. We further utilized Sm-Nd isotope systematics to calculate the timing of this alteration event. These BIFs show lowest RSD (%) in their initial 143Nd/144Nd composition around 0.6 Ga, which we consider as the time of alteration event which affected the Sm/Nd of these rocks. The timing of alteration event coincides with the Pan-African orogeny which had regionally affected the Greater Dharwar Craton. The associated red shales are also characterized by high LREE/HREE ratios and negative Ce anomalies. These shales also show very high Chemical Index of Alteration (CIA) values (83-99) suggesting high degree of chemical weathering. [1] Bonnand et al, (2020) Earth and Planetary Science Letters
Reconciling volcanic deformation, degassing and petrological data using thermodynamic...
Stanley Tze Hou Yip
Juliet Biggs

Stanley Tze Hou Yip

and 4 more

February 28, 2022
Two of the most widely observed co-eruptive volcanic phenomena - ground deformation and volcanic outgassing - are fundamentally linked via the mechanism of magma degassing and the development of compressibility, which controls how the volume of magma changes in response to a change in pressure. Here we use thermodynamic models (constrained by petrological data) to reconstruct volatile exsolution and the consequent changes in magma properties. Co-eruptive SO2 degassing fluxes may be predicted from the mole fraction of exsolved SO2 that develops in magma whilst stored prior to eruption and during decompression. Co-eruptive surface deformation may be predicted given estimates of erupted volume and the ratio between chamber compressibility and magma compressibility. We conduct sensitivity tests to assess how varying magma volatile content, crustal properties, and chamber geometry may affect co-eruptive deformation and degassing. We find that magmatic H2O content has the most impact on both SO2 flux and volume change (normalised for erupted volumes). Our findings have general implications for typical arc and ocean island volcanic systems. The higher magmatic water content of arc basalts leads to a high pre-eruptive exsolved volatile content, making the magma more compressible than ocean island eruptions. Syn-eruptive gas fluxes are overall higher for arc eruptions, although SO2 fluxes are similar for both settings (SO2 flux for ocean island basalt eruptions is dominated by decompressional degassing). Our models are consistent with observation: deformation has been detected at 48% of ocean island eruptions (16/33) during the satellite era (2005-2020), but only 11% of arc basalt eruptions (7/61).
Hydrological Transport and Biological Degradation of Dissolved Organic Carbon in a He...
Maofei Ni

Maofei Ni

June 08, 2022
River systems represent important drivers of carbon loading, utilization and storage. However, underlying controls of hydrological transport and biological degradation on fluvial dissolved organic carbon (DOC) have yet to be revealed. Here, we explored spatiotemporal variability of DOC concentrations, components and sources, as well as its biodegradability in a headwater tributary of the Yangtze. We found that temporal rainfall stimulated terrestrial inputs and increased terrigenous DOC abundance. Hydrological transport was accompanied by biological generation and utilization of DOC, resulting in reduced labile components and accumulated recalcitrant components from tributaries to the main stem. Biodegradable DOC (BDOC) notably responded to temperature gradients over a 56-day laboratory incubation. Riverine DOC component, molecular weight and source highly predicted its biodegradation. Particularly, partial refractory (ultraviolet humic-like) fractions contributed to biological degradation of DOC, which was incompletely degraded from high-molecular to low-molecular weight compounds. The findings hope to supplement a new understanding of carbon fate under global change.
Distribution and yield of trace metals from the foot of Mount Kilimanjaro to the coas...
Juma Rajabu Selemani
Xunchi Zhu

Juma Rajabu Selemani

and 3 more

January 07, 2021
Cases of water related diseases due to metal pollution are increasing over the global. The condition is serious to most of developing countries as a results of industrialization and population growth. Dissolved and particulate trace elements influence drinking water, aquatic ecosystem health and climate change. Mt. Kilimanjaro is one of the sources of water and icon in Africa but miss studies on dissolved and particulate metals. Therefore, this study was conducted to investigate geochemistry, distribution and yield of dissolved and particulate metals from Mt. Kilimanjaro to Indian Ocean. Surface water was sampled in rainy season and analyzed by high resolution inductively coupled plasma mass spectrometry in State Key Laboratory of Estuaries and Coastal Research. Health assessment revealed that level of Aluminium, iron, vanadium and Manganese in some stations were above recommended level, that can pose health impact to human and aquatic ecosystem. Correlation of Cobalt, Copper, Manganese and Vanadium with dissolved silicate, sulphate, calcium and dissolved organic carbon indicates that these elements were predominantly found in silicate, sulphide, carbonate and organic bounds. Positive relation between magnetic susceptibility with Copper and zinc reflects that magnetic susceptibility can be used as indicator of Copper and Zinc pollution. Rock weathering and anthropogenic activities were main sources of metals whereas redox reactions, pH, temperature and dissolved organic carbon were some of biogeochemical factors influencing level of metals. The basin transported more elements in particulate than dissolved form. Yield from Pangani River to Indian Ocean was lower than most of other rivers in East Africa.
Formation, Accretion and Reworking of Continents
Rixiang Zhu
Guochun Zhao

Rixiang Zhu

and 4 more

January 07, 2021
Felsic continental crust is unique to the Earth in the solar system, but it still remains controversial regarding its formation, accretion and reworking. The plate tectonics theory has been significantly challenged in explaining the origin of continents as Archean continents rarely preserve hallmarks of plate tectonics. In contrast, growing evidence emerges to support mantle plume-derived oceanic plateau models as the models can reasonably explain the origin of bimodal volcanic assemblages and nearly coeval emplacement of tonalite-trondjhemite-granodiorite (TTG) rocks, presence of ~1600ºC komatiites and dominant dome structures, and lack of ultra-high-pressure rocks, paired metamorphic belts and ophiolites in Archean continents. Although plate tectonics seems to fail in explaining the origin of continents, it has been successfully applied to interpret the accretion or outgrowth of continents along subduction zones where new mafic crust is generated at the base of continental crust through partial melting of the mantle wedge with addition of H2O-dominant fluids from the subducted oceanic slabs, and partial melting of the juvenile mafic crust results in the formation of new felsic continental crust, leading to the outside accretion of continents. Subduction processes also cause the softening, thinning and recycling of continental lithosphere due to the vigorous infiltration of volatile-rich fluids and melts especially along weak layers or weak belts, leading to the widespread reworking and even destruction of continental lithosphere. Reworking of continents also occurs in continental interiors due to plume-lithosphere interactions, which, however, leads to much less degrees of lithospheric modification than subduction-induced craton destruction.
Evaluation of carbon export from blue carbon ecosystems and allochthonous sequestrati...
Toshihiro Miyajima
Masami Hamaguchi

Toshihiro Miyajima

and 6 more

September 05, 2020
Blue carbon ecosystems such as mangroves and seagrass meadows (coastal marine ecosystems dominated by halophytic vascular plants) are regarded as a global carbon dioxide (CO2) sink supported by high net community production. A part of the excess organic carbon (OC) production by these ecosystems is stored for a long term as persistent OC in underlying sediments, while the rest is exported to outside the system (open ocean) without being remineralized. In order to properly assess the role of blue carbon ecosystems in the global carbon cycle, the fate of exported OC must be elucidated. A part of the OC exported to the open ocean may be decomposed and remineralized quickly while in the ocean surface and return to the atmosphere as CO2. In such a case, the export production cannot be regarded as a long-term carbon sink. On the other hand, the exported OC may either be (1) stored for a long term in the offshore sediment as detrital OC, (2) stored as refractory dissolved organic carbon (RDOC) in seawater, or (3) settled down in the bathypelagic layer and subsequently remineralized into CO2 there. In these cases, carbon does not return to the atmosphere in the short term and can be included in net CO2 sequestration. It is obvious that carbon pools corresponding to these three processes exits in the ocean. However, it is technically extremely difficult to clarify whether and to what extent carbon derived from the blue carbon ecosystems is contained in these pools. The purpose of this study is to demonstrate by using environmental DNA techniques that OC derived from the blue carbon ecosystems can be transported to and stored in open ocean sediments. As a case study, coastal area off the west coast of Busuanga Island, Philippines, was set as study site, where natural coral reefs, seagrass beds, and mangroves are relatively well preserved. DNA probes for MatK sequences (part of chloroplast DNA) of two mangrove species (Rhizophora mucronata, Sonneratia alba) and two seagrass species (Enhalus acoroides, Thalassia hemprichii) as well as ITS sequence (part of nuclear DNA) of R. mucronata were designed. Then, the DNA copy numbers of respective sequences contained in extracts from surface sediment samples were quantified by the qPCR method. In addition, the organic and inorganic carbon concentrations and the specific surface area of the surface sediment samples were determined, and the origin of the sediment OC was assessed using a carbon stable isotope mixing model. During sample collection, seismic profiling with a sub-bottom profiler was also conducted to evaluate thickness of sediment accumulated in the studied area. In this presentation, we summarize the results of these surveys to evaluate the areal extent to which seagrass- and mangrove-derived OC is transported and stored in relatively intact state, and identify environmental conditions that influence the accumulation in open ocean sediments of OC derived from blue carbon ecosystems. Difficulties in conve
Spectral diversity of rocks and soils in Mastcam observations along the Curiosity rov...
Melissa Susanne Rice
Christina Seeger

Melissa Rice

and 16 more

February 23, 2022
The Mars Science Laboratory (MSL) Curiosity rover has explored over 400 meters of vertical stratigraphy within Gale crater to date. These fluvio-deltaic, lacustrine, and aeolian strata have been well-documented by Curiosity’s in-situ and remote science instruments, including the Mast Camera (Mastcam) pair of multispectral imagers. Mastcam visible to near-infrared (VNIR) spectra can broadly distinguish between iron phases and oxidation states, and in combination with chemical data from other instruments, Mastcam spectra can help constrain mineralogy, depositional origin, and diagenesis. However, no traverse-scale analysis of Mastcam multispectral data has yet been performed. We compiled a database of Mastcam spectra from >600 multispectral observations and 1 quantified spectral variations across Curiosity’s traverse through Vera Rubin ridge (sols 0-2302). From principal component analysis and an examination of spectral parameters, we identified 9 rock spectral classes and 5 soil spectral classes. Rock classes are dominated by spectral differences attributed to hematite and other oxides (due to variations in grain size, composition, and abundance) and are mostly confined to specific stratigraphic members. Soil classes fall along a mixing line between soil spectra dominated by fine-grained Fe-oxides and those dominated by olivine-bearing sands. By comparing trends in soil vs. rock spectra, we find that locally derived sediments are not significantly contributing to the spectra of soils. Rather, varying contributions of dark, mafic sands from the active Bagnold Dune field is the primary spectral characteristic of soils. These spectral classes and their trends with stratigraphy provide a basis for comparison in Curiosity’s ongoing exploration of Gale crater.
Chemical speciation of trace metals in atmospheric deposition and impacts on soil geo...
Hailong Liu
Jun Zhou

Hailong Liu

and 5 more

November 11, 2020
Atmospheric deposition is an important source of trace metals to surface environments, but knowledge about plant bioavailability of recently deposited metals is limited. We performed a fully factorial soil and atmosphere exposure experiment with three vegetables (radish, lettuce, and soybean), which allowed to effectively distinguish impacts of recently deposited metals (<1 year) from longer-term metal exposures in soils. Results showed that recently deposited Cu, Cd, and Pb accounted for 0.5-15.2% of total soil Cu, Cd, and Pb pools near emission source, while they contributed 15-76% of Cu, Cd, and Pb concentrations in edible parts of vegetables. The soil retention of recently deposited metals (52-73%) presented as higher mobile fractions than these previously present in soils (7-42%). These findings highlight a preferential uptake and high rates of bioaccumulation of deposited metals in vegetables and implicated that quick and potentially stronger reduction can be achieved by reducing current atmospheric source loads.
Eoarchean subduction-like magmatism recorded in ca. 3750 Ma mafic-ultramafic rocks of...
Thomas Grocolas
Pierre Bouilhol

Thomas Grocolas

and 3 more

November 10, 2020
Our understanding of the nature of crustal formation in the Eoarchean is severely curbed by the scarcity and poor preservation of the oldest rocks, and variable and imperfect preservation of protolith magmatic signatures. These limitations hamper our ability to place quantitative constraints on thermomechanical models for early crustal genesis and hence on the operative geodynamical regimes at that time. Controls on the liquid line of descent responsible for Eoarchean crust petrogenesis could help us understand more, but these remain vague. Growth of Archean crust may have occurred dominantly via processes akin to modern oceanic crustal genesis, coupled to a vertical geodynamic regime. Equally, convergent boundary processes, including subduction, are argued to be important in the development of the crust before about 3.8 Ga. The recently discovered ca. 3.75 Ga Ukaliq supracrustal enclave (northern Québec) is mainly composed of serpentinized ultramafic rocks and amphibolitized mafic schists. Inferred protoliths to the Ukaliq serpentinites include dunites, pyroxenites, and hornblendites with compositions similar to that of arc crust cumulates, whereas the mafic rocks were probably basalts to basaltic andesites. The Ukaliq cumulates record two liquid lines of descent: (i) a tholeiitic suite, partially hydrated, resulting from the fractionation of a basaltic liquid; and (ii) a boninitic suite documenting the evolution of an initially primitive basaltic to andesitic melt at ~0.5 GPa and containing >6 wt% H2O. Together with the presence of negative μ142Nd anomalies, this information points to a deep fluid input via recycling of Hadean crust in the Eoarchean via modern-style subduction.
Exploring the Sensitivity of Lunar Interior Structure from Geophysical and Geochemica...
Heidi Fuqua Haviland
Paul M. Bremner

Heidi Haviland

and 5 more

April 20, 2021
Abstract The key to evaluating the formation history and evolution of the Moon lies in understanding the current state of its interior. We used a multidisciplinary approach to explore the current day lunar structure and composition with the aim of identifying signatures of formation and early evolution. We constructed a large number of 1D lunar interior models to explore a wide range of potential structures and identified those models that match the present day mass, moment of inertia, and bulk silicate composition of the Moon. In an advance on previous studies, we explicitly calculate the physical and elastic properties of the varying mineral assemblages in the lunar interior using multicomponent equations of state. We considered models with either a compositionally homogeneous mantle or a stratified mantle that preserved remnants of magma ocean crystallization, and tested thermal profiles that span the range of proposed selenotherms. For the models that reproduced the observed mass and moment of inertia, we found a narrow range of possible metallic (iron) core radii (269-387 km) consistent with previous determinations. We explored the possibility of an ilmenite bearing layer both below the crust and at the core-mantle boundary as a potential tracer of magma ocean solidification and overturn. We observed a trade-off between the mass of the upper and lower ilmenite-bearing layers and structures that have undergone mantle overturn are both consistent with present observations. Plain Language Summary In order to understand how the Moon formed, along with the following history including the processes that change and shape it, the current state of the lunar interior offers a lot of valuable information or clues. We used several different computer simulation tools from different disciplines to calculate the Moon’s interior structure. We then compared our calculations with observations of the Moon’s mass and moment of inertia (a measure of how its weight is distributed through the interior) and the average composition and chemistry of the Moon. We considered a Moon that is well mixed and one that has preserved layers from its early history and tried different temperature structures. We find that the Moon has to have a small dense iron core and that it may have a hot soft layer just above the core that can dampen moonquakes.
A Unique Diel Pattern in Carbonate Chemistry in the Seagrass Meadows of Dongsha Islan...
Wen-Chen Chou
Lan-Feng Fan

Wen-Chen Chou

and 11 more

November 10, 2020
In contrast to most seagrass meadows where seawater carbonate chemistry generally shows strong diel variations with a higher pH during the daytime and a lower pH during nighttime due to the alternation in photosynthesis and respiration, the seagrass meadows of the inner lagoon on Dongsha Island had a unique diel pattern with an extremely high pH across a diel cycle. We suggest that this distinct diel pattern in pH was a result of a combination of total alkalinity (TA) production through the coupling of aerobic/anaerobic respiration and carbonate dissolution in the sediments and dissolved inorganic carbon consumption through the high productivity of seagrasses in overlying seawaters. The confinement of the semienclosed inner lagoon may hamper water exchange and seagrass detritus export to the adjacent open ocean, which may provide an ideal scenario for sedimentary TA production and accumulation, thereby forming a strong capacity for seagrass meadows to buffer ocean acidification.
Application of Continuous Ramped Heating to Assess Dispersion in Apatite (U-Th)/He Ag...
Hongcheng Guo
Peter Zeitler

Hongcheng Guo

and 5 more

April 20, 2021
Application of apatite (U-Th)/He thermochronology has been hindered by incomplete understanding of single-grain age dispersion often displayed by samples, particularly those from older, slowly cooled settings. To assess the capability of continuous ramped heating (CRH) to explain dispersion, we performed a study on an apatite suite from Cathedral Rocks in the Transantarctic Mountains (TAM) that have high age dispersion. Examining 132 apatite grains from a total of six samples, we confirmed earlier apatite (U-Th)/He results showing that measured AHe ages have at least three-fold intra-sample dispersion with no obvious relationships between ages and effective uranium concentration (eU) or grain size. CRH results on these apatites yielded two groups. Those with younger ages, characterized by single-peak incremental 4He gas-release curves, displayed simple volume diffusion behavior. In contrast, grains with older ages generally show anomalous gas release in the form of sharp spikes and / or extended gas-release at high temperatures (i.e., >= 800 °C). Well-behaved apatites still show considerable age dispersion that exceeds what grain size, radiation damage, and analytical uncertainty can explain, but this dispersion appears to be related to variations in 4He diffusion kinetics. The screened AHe ages from well-behaved younger apatite grains together with kinetic information from these grains suggest that the sampled region experienced slow cooling prior to rapid cooling (rock exhumation) beginning ca. 35 Ma. This interpretation is consistent with other studies indicative of an increase in exhumation rates at this time, possibly related to the initiation of glaciation at the Eocene-Oligocene climate transition. An attempt to correct anomalous older apatite ages by simply removing extraneous gas-release components is proposed yielded some ages that are too young for the samples’ geologic setting, suggesting that the factors that lead to anomalous laboratory release behavior can impact both the expected radiogenic component as well as those that are extraneous. From our observations we conclude that: (1) CRH analysis can serve as a routine screening tool for AHe dating and offers opportunities to reveal first-order kinetic variations; (2) model-dependent age correction may be possible but would require some means of estimating the broad proportions of 4He components incorporated into grains before and after closure to diffusion, and (3) interpretation of highly dispersed AHe ages requires assessment of individual-grain diffusion kinetics beyond that predicted by radiation-damage models. We also infer that many apatite grains contain imperfections of varying kinds that contribute significantly to kinetic variability beyond that associated with radiation damage.
Modeling Coupled Reactive Transport Through Fault-zones: A Critical Review
Vivek Patil
Brian McPherson

Vivek Patil

and 1 more

September 29, 2020
Fault-zones significantly influence the migration of fluids in the subsurface and can be important controls on the local as well as regional hydrogeology. Hence, understanding the evolution of fault porosity-permeability is critical for many engineering applications (like geologic carbon sequestration, enhanced geothermal systems, groundwater remediation, etc.) as well as geological studies (like sediment diagenesis, seismic activities, hydrothermal ore deposition, etc.). The highly heterogeneous pore structure of fault-zones along with the wide range of hydrogeochemical heterogeneity that a fault-zone can cut through make conduit fault-zones a dynamic reactive transport environment that can be highly complex to accurately model. In this paper, we present a critical review of the possible ways of modeling reactive fluid flow through fault-zones, particularly from the perspective of chemically driven “self-sealing” or “self-enhancing” of fault-zones. Along with an in-depth review of the literature, we consider key issues related to different conceptual models (e.g. fault-zone as a network of fractures or as a combination of damaged zone and fault core), modeling approaches (e.g. multiple continua, discrete fracture networks, pore-scale models) and kinetics of water-rock interactions. Inherent modeling aspects related to dimensionality (e.g. 1D vs 2D) and the dimensionless Damköhler number are explored. Moreover, we use a case-study of the Little Grand Wash Fault-zone from central Utah as an example in the review. Finally, critical aspects of reactive transport modeling 2 like multiscale approaches and chemo-mechanical coupling are also addressed in the context of fault-zones.
Strontium and uranium isotopes from lacustrine carbonates as a paleohydrologic tracer...
Kevin Theissen
James Paces

Kevin Theissen

and 2 more

December 12, 2018
The combination of strontium (87Sr/86Sr) and uranium (234U/238U) isotopes is an especially useful tool to track and quantify mixtures of water sources in arid wetlands, where chemistry and lighter isotopic tracers are strongly influenced by evaporation and transpiration. Those isotopes were used to understand modern water supply to the Pahranagat National Wildlife Refuge (PNWR) in southern Nevada (Paces & Wurster, 2014, J. Hydrol. 517). We investigate the possibility that this isotopic combination might also track paleohydrological changes in such settings. Here, we present Sr and U isotope data for authigenic carbonates in a sediment core spanning 5800 14C cal years from Lower Pahranagat Lake (LPAH), a shallow, alkaline lake within the PNWR. Modern surface waters in the PNWR are comprised of mixtures of discharge from two high volume springs from the regional carbonate aquifer in the northern valley, and smaller amounts of local discharge from the shallow volcanic aquifer in the southern valley. Modern surface water from LPAH has U isotopic values similar to the most recently formed LPAH carbonates; however, Sr isotopic values in LPAH surface water are somewhat lower than values in those same carbonates. Combined Sr and U isotope values in Holocene LPAH carbonates fall within the range defined by the three primary spring sources and reflect varying mixtures of those sources supplying LPAH from mid-Holocene to modern time. Values in the oldest samples (~5800 14C cal yr BP) have distinct 87Sr/86Sr and 234U/238U values that nearly match the local spring end member, suggesting that LPAH water at that time was dominated by proximal volcanic aquifer sources. By ~5300–5200 14C cal yr BP, LPAH water was comprised of a nearly equal mixture of the three spring sources, marking a dramatic shift in hydrologic conditions that allowed contributions of surface flow from distal carbonate springs to the north. Values in samples from ~1,000–3,000 14C cal yr BP indicate decreased contributions from distal carbonate springs during two drought intervals; however, by 730 14C cal yr BP, surface flow from carbonate springs had resumed. Our results indicate that combined Sr and U isotopes preserve evidence of past changes in water sources in arid wetlands useful for interpreting evolving hydrologic conditions.
Thaw dynamics of a rapidly degrading isolated permafrost plateau in south-central Ala...
Joel Eklof
Mark Waldrop

Joel Eklof

and 3 more

January 14, 2020
Northern high latitudes are projected to get warmer and wetter in the future which will affect rates of permafrost thaw and the mechanisms by which thaw occurs. To better understand these changing thaw dynamics, we instrumented an isolated permafrost plateau in south-central Alaska with climate conditions that currently mirror those expected in more northern permafrost regions in the future. Using preliminary 2019 measurements of temperature from the soil surface into permafrost, depth to frost table, water level, groundwater temperature, and meteorological variables, we tracked soil and permafrost warming throughout the season, and identified how environmental factors, such as water table elevation, microtopography, and warm rain events, affected rates of warming and thaw. Additionally, we present the extent of permafrost degradation since the last observations at this site in 2015. Permafrost thaw and resultant landscape change has a net warming effect on the climate. Understanding of the environmental factors that lead to thaw and rates at which permafrost will thaw under future climate conditions will allow for better preparation, modeling, and policy making for the future.
Development and use of garnet-based high-resolution P-T-t paths to constrain the dyna...
Elizabeth Catlos
Theresa Perez

Elizabeth Catlos

and 3 more

January 14, 2020
Tectonic models as a universal outcome generate predictions regarding the travel time paths of rocks as they are displaced due to the application of particular input parameters and boundary conditions. A need for most of these models, either as a constraint for realistic input conditions or to gauge their relevance to a particular natural system, is pressure‐temperature‐time (P‐T‐t) paths from individual rock samples that track the conditions they experienced during displacement. Although arguments can be made that P‐T paths and absolute peak P‐T conditions may not necessarily be diagnostic of processes involved, this type of information is clearly a valuable addition to other types of data, such as timing and microstructural information regarding strain recorded during rock deformation. Low‐resolution P‐T paths can be limited in their ability to test ideas regarding lithospheric response to perturbations, including motion within fault zones. Here we apply advances in thermodynamic modeling to acquire high‐resolution P‐T paths that show the conditions responsible for garnet growth within one of the Himalayas’ major fault systems. The approach we outline can be applied to any garnet‐bearing assemblage using bulk rock and mineral compositions and have the potential to significantly increase the understanding of the dynamics of field areas that contain garnet, from the mineral’s crystallization to erosion‐driven or tectonically-driven exhumation. Overall, high-resolution garnet-based P-T paths were generated for two transects across the Himalayan Main Central Thrust (MCT) spaced ~850 km apart (along the Bhagirathi and Marsyangdi drainages) and monazite grains were dated in situ to help constrain crystallization time. Rocks collected at equivalent structural positions to the MCT along both transects show similar paths and a shear zone imbrication model suggest the MCT zone has very high exhumation rates, up to 12 mm/yr since the Pliocene.
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