Meteoric Groundwater Research Articles

Fingerprinting dissolved organic compounds: a potential tool for identifying the surface infiltration environments of meteoric groundwaters

Current methods for tracing decades-old groundwaters rely on isotope geochemistry to determine groundwater age and altitude at the point of infiltration. Temporal and spatial variability in atmospheric conditions, and water–rock interactions, can make the interpretation of isotopes uncertain. Here, we propose a new method of groundwater tracing based on the fingerprinting of natural dissolved organics. We present our initial findings from the Grimsel Test Site in Switzerland, located within a fractured granite. Using 2D gas chromatography, we derive detailed organic fingerprints from surface soils at several locations and show that different soils produce distinctly different dissolved organic signatures. We then compare the soils with groundwater and lake water using a non-targeted approach employing principal component analysis and hierarchical cluster analysis. Our analysis finds three statistically significant clusters. Most groundwaters are clustered with the lake-water samples but two are clustered with soil from the highest altitude surface sampling location. We hypothesize that for samples to form a significant cluster, they must have been derived from a common environment, with a unique combination of organic compounds. For groundwaters to cluster with soil samples or lake water, we theorize there must be a hydraulic connection between the type of infiltration environment and the groundwater sampling locations within each cluster. Our research demonstrates that organic molecules derived from the surface environment can be used to discriminate near-surface environment(s) through which meteoric groundwater has infiltrated. Organic fingerprinting could prove a powerful tool for improved understanding of groundwater flow systems, particularly when combined with other complementary techniques. Supplementary material : Compound alignment data set and supplementary tables are available at https://doi.org/10.6084/m9.figshare.c.7129987 Thematic collection: This article is part of the Sustainable geological disposal and containment of radioactive waste collection available at: https://www.lyellcollection.org/topic/collections/radioactive

Spatiotemporal relationship between hydrocarbon fluid and sandstone‐hosted uranium deposits in the Qianjiadian area, Songliao Basin

The spatiotemporal coupling relationship between deep hydrocarbon fluid and sandstone uranium mineralization within the shallow buried red‐variegated clastic rocks in the Qianjiadian area of the Songliao Basin remains a topic of controversy. This paper aims to provide a comprehensive understanding of the source, nature and exudative age of deep exotic hydrocarbon, as well as the interaction mechanism and alteration process between hydrocarbon fluid and clastic rock. To achieve this, various methods were employed, including acidolysis hydrocarbon test (AHT), clay x‐ray diffraction (XRF), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), carbon isotope analysis (CIA) and LA‐ICP‐MS U–Pb isotopic dating. The results indicate that some tight sandstones from the Qingshankou Formation in Dalin uranium deposit exhibit high acidolysis hydrocarbon content (AHC), reaching n × 104 μL/kg, and predominantly consisting of low mature oil‐type gas. Local microscopic observations reveal pore fluorescence and hydrocarbon‐bearing inclusions with nattier blue tone. Furthermore, the kaolinites present in the ore area's sand‐bodies show a significantly higher content anomaly, commonly exceeding >50%, compared to the same layer in peripheral regions. Extensive dissolutions of lithic grains and feldspars are observed, along with the widespread occurrence of ferro‐dolomites and colloidal pyrites. Additionally, exotic asphaltenes are sporadically developed in localized areas. These findings provide evidence that the sand‐bodies experienced a significant exfiltration event of external gaseous fluids. The light carbon isotopes (δ13CV‐PDB ranging from −33.26‰ to −30.06‰) of group components and n‐Alkane suggest that the hydrocarbon originates from the source rock of the Lower Cretaceous Jiufotang Formation. A detailed two‐stage alteration sequence caused by acidic and reducing hydrocarbon is clarified, encompassing acidic corrosion, kaolinization, pyritization, silification and asphaltization during the exudation stage, followed by ferro‐dolomitization in the later cessation stage. Notably, vermicular secondary kaolinites, formed through the interaction between acidic hydrocarbon fluid and low‐temperature meteoric groundwater, serve as significant markers for the exfiltration of deep hydrocarbon fluid. In‐situ U–Pb dating of hydrocarbon‐bearing ferro‐dolomite yielded absolute exfiltration ages of 63.54 ± 4.13 and 65.93 ± 3.35 Ma. By integrating the tectonic–sedimentary–fluid evolution history and uranium mineralization characteristics in the study area, a three‐stage superimposed metallogenic model is proposed for the Upper Cretaceous red‐variegated layers: (1) the sedimentary and diagenetic stage of the target layer during the Late Cretaceous, (2) the predominant hydrocarbon exudation stage at the end of the Late Cretaceous, and (3) the main uranium mineralization stage since the Paleogene. This study enhances our understanding of coupled‐genetic sandstone‐type uranium deposit in a sedimentary basin and provides valuable guidance for prospecting similar red‐variegated beds in the Songliao Basin and other sedimentary basins worldwide.

Deciphering the ore-forming process of Sb-W deposits through scheelite and stibnite trace element geochemistry

Antimony (Sb) and tungsten (W) and deposits typically form in distinct and unrelated ore-forming environments. However, in rare cases, ore deposits may present combined Sb-W mineralization within a single deposit. These contrasting occurrences introduce uncertainty within the Sb-W ore deposit model, which ultimately guides mineral exploration strategies. Scheelite and stibnite are prevalent ore minerals in Sb-W deposits, making their trace element compositions valuable for enhancing our understanding of the genesis of Sb-W ore systems. In this study, we conducted a systematic investigation of trace element compositions in scheelite and stibnite samples from the Chashan and Zhazixi Sb-W deposits in South China to decipher the primary ore-forming processes. Scheelite from the Sb-W deposits is characterized by low Na, Nb, Ta and Mo contents, and variable Nb/Ta ratios. These results present a remarkably different geochemical signature when compared with granite-related W deposits, indicating that W mineralization in Sb-W deposits was derived from a non-magmatic origin. Moreover, when combining the trace element signature with reported fluid inclusion and isotopic data, it can be concluded that ore-forming fluids of the Chashan and Zhazixi Sb-W deposits were primarily composed of deep-circulating meteoric groundwater. Scheelite from the Chashan deposit presents relatively flat REE patterns with large positive Eu anomalies, whereas the Zhazixi deposit is characterized by bell-shaped REE patterns with weak Eu anomalies. This suggests that the two Sb-W deposits may differ slightly in their source rock composition, which is also supported by the different trace element compositions of stibnite. Stibnite from the Zhazixi deposit is relatively enriched in As, Se and Pb, whereas stibnite from the Chashan deposit contains higher Sn, Zn, Mo, Ag, In and Sr, further indicating that the initial fluids of the two deposits may have undergone different degrees of fluid-rock interaction with their distinctive source rocks. This study demonstrates that the genesis of the Zhazixi and Chashan Sb-W deposits significantly differ when compared to the ore-forming processes that control granite-related W or metamorphic W deposits. Moreover, the formation of these Sb-W deposits appears to share a similar genetic model consistent with low-temperature Sb deposits in South China. In this model, deep-circulating meteoric groundwater infiltrates and leaches Sb and W from fertile source rocks through fluid-rock interaction. Concealed granites may have solely served as a thermal source for the convection and upward migration of ore-forming fluids, while the fertility of source rocks and the intensity of fluid-rock interaction are expected to have played a crucial role in the formation of Sb-W deposits.

Active near-surface mobilisation of slab-derived geochemical signatures by hyperalkaline waters in brecciated serpentinites

Unusual hyperalkaline meteoric groundwaters on Troodos massif, Cyprus, issue from highly deformed and completely serpentinized ultramafic brecciated rock masses of the Artemis Diapir and have high salinity (25–30% seawater total dissolved solids) and some of the highest recorded pH values (11−13) for natural waters. These waters have elevated dissolved Na, K, Li, B, Ba, Rb, Cs, Cl and SO4 with ion/chloride substantially above seawater ratios, overprinting minor contributions from marine aerosols. For example, K concentrations are similar to seawater values. Water stable isotope ratios imply extensive water-rock interaction and 87Sr/86Sr is rock-dominated (0.705) and significantly lower than seawater. These rare fluids contrast with surface and shallow ground waters draining the ultramafic Troodos Mantle Sequence that have pH of 8.5–9, meteoric stable isotope ratios, 87Sr/86Sr similar to early Miocene seawater (0.7085) and low dissolved salts albeit with ion/chloride ratios also greater than seawater. The combination of high pH and salinity is unusual in ophiolites and these hyperalkaline waters are most similar to end-member fluids emanating from serpentine mud volcanoes in the Mariana forearc. Rainwater rapidly transiting terraces of asbestos mine tailings on Troodos mostly resemble the surface waters but show slight contamination by a saline component. We propose that inclusions within the serpentinite that contain highly soluble salts have been made accessible by tectonic deformation during uplift and diapirism, or comminution during mining activity. A multistage process is proposed whereby alkali and other signatures have been released from the stalled subducting slab beneath the Troodos massif and have infused the mantle wedge. Some of these rocks have been carried to the surface by diapiric uplift and erosion, where tectonic deformation or mining activities have enabled the near-surface mobilisation of slab-derived geochemical signatures by modern meteoric waters.

Depositing >1.5 Mt of Tin Within <1 m.y. of Initial Granitic Intrusion in the San Rafael Tin (-Copper) Deposit, Southeastern Peru

Abstract The San Rafael Sn (-Cu) deposit, located in the Eastern Cordillera of southeast Peru, is one of the world’s largest cassiterite-bearing vein systems (>1 Mt Sn produced since 1969). The deposit consists of a quartz-cassiterite-chlorite-sulfide lode system spatially associated with an upper Oligocene (ca. 24 Ma) S-type granitic pluton. Based on a revised paragenetic sequence for the deposit, we interpret the temporal setting of both magmatic (biotite, K-feldspar) and hydrothermal (muscovite, adularia, cassiterite) minerals analyzed by 40Ar/39Ar step-heating and U-Pb laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) geochronology. The least-disturbed biotite sample from the megacrystic monzogranite yielded a 40Ar/39Ar plateau age of 24.10 ± 0.26 Ma (2σ), which constrains the time of cooling of the upper part of the pluton to below 300°C. Greisen developed on top of the granitic cupola and its immediate metamorphic aureole dated at 24.24 ± 0.24 Ma (2σ; 40Ar/39Ar muscovite average plateau age) is interpreted to be contemporaneous with the emplacement of pre-ore quartz-tourmaline veins and breccias. In situ U-Pb dating of cassiterite, including both botryoidal cassiterite (“wood tin”) and coarse-grained cassiterite in quartz-chlorite veins and breccias, constrains the timing of the main Sn ore stage to between 24.10 ± 0.37 and 23.47 ± 0.53 Ma (2σ). Botryoidal and coarse-grained cassiterite are characterized by similar trace element compositions with fluctuating metal concentrations across growth banding, suggesting significant changes of physicochemical conditions of the hydrothermal system during cassiterite precipitation, likely caused by rapid and repeated mixing between magmatic fluids and meteoric groundwaters. Polymetallic sulfide-rich veins and quartz-carbonate veins are constrained to have formed between 22.72 ± 0.11 and 22.29 ± 0.24 Ma (2σ), based on adularia 40Ar/39Ar plateau ages. The latter overlap partially reset 40Ar/39Ar age spectra for K-feldspar megacrysts in the host granite and thus reflect pervasive alteration by hydrothermal fluids. Collectively, the results show the magmatic-hydrothermal system spanned at least 2 m.y. with the main Sn ore stage representing <1 m.y. in the lifetime of the deposit. The latest polymetallic stages postdate the main Sn ore stage by ca. 1 m.y. and reflect the waning of the hydrothermal system, accompanied by additional incursion of meteoric groundwaters. This study provides further evidence that the present-day exposed level of the San Rafael granite was a passive host for the Sn mineralization and only provided the structural focusing for the mineralizing fluids derived from a deeper part of the magmatic system.

Redox-zoning in high-energy subterranean estuaries as a function of storm floods, temperatures, seasonal groundwater recharge and morphodynamics

Redox conditions are a major control for the concentrations and mass fluxes of water constituents, e.g., nutrients, metals and organic molecules within subterranean estuaries (STE). Due to the transient flow and transport processes in STEs as well as the variable temperatures and input of redox reactants, redox zoning in the STE is believed to be highly dynamic. In the present study we analyzed the individual and combined effects of storm floods, seasonal changes of temperatures and groundwater recharge rates, as well as beach morphodynamics on the redox zoning in the STE. For this purpose, a 2D cross-shore density-dependent flow and reactive transport model was set up representing a beach aquifer exposed to high-mesotidal and medium-to high-energy wave conditions, as well as to storm floods. The simulation results show that under the given conditions, redox dynamics may occur down to a depth of 20 m. Morphodynamics appear to be the most important factor for the transience of redox zones compared to the other factors. Seasonal changes in meteoric groundwater recharge rates appear to be least relevant for the redox dynamics in STEs.

Estimation of nitrogen and phosphorus fluxes into a Barrier Island lagoon via meteoric groundwater discharge

Meteoric groundwater discharge (MGD) to coastal regions transports terrestrial freshwater and nutrients that may alter coastal ecosystems by supporting harmful algal blooms. Estimation of MGD-driven nutrients is crucial to assess potential effects on coastal zones. These estimates require a reliable assessment of MGD rates and pore water nutrient concentrations below subterranean estuaries. To estimate nutrient delivery into a subterranean estuary in the Indian River Lagoon, FL., pore water and surface water samples were collected from nested piezometers along a selected transect on five sampling episodes. Groundwater hydraulic head and salinity were measured in thirteen onshore and offshore piezometers. Numerical models were developed, calibrated, and validated using SEAWAT to simulate MGD flow rates. Lagoon surface water salinity exhibits no spatial but mild temporal variation between 21 and 31. Pore water salinity shows tremendous variation in time and space throughout the transect except in the middle region of the lagoon which exhibits uniform but elevated salinities up to 40. Pore water salinity as low as that of freshwater happens to occur in the shoreline regions during most of the sampling episodes. Both pore water and surface water show remarkably higher total nitrogen TN than total phosphorus TP concentrations and most TN is exported as NH4, reflecting the effect of mangroves on the geochemical reactions that reduce NO3 into NH4. Nutrient contributions of pore water and lagoon water exceed the Redfield TN/TP molar ratio in all sampling trips by up to a factor of 48 and 4, respectively. Estimated TP and TN fluxes receives by the lagoon via MGD are 41–106 and 113–1478 mg/d/m of shoreline. The molar TN/TP ratio of nutrient fluxes exceeds the Redfield ratio by a factor of up to 3.5 which indicates the potential of MGD-driven nutrients to alter the lagoon water quality and support harmful algal blooms.

Carbonate diagenesis: A celebration of the work of John Anthony Dawson (Tony) Dickson

Carbonate diagenesis: A celebration of the work of John Anthony Dawson (Tony) Dickson

Unveiling the nitrogen transport and transformation in different karst aquifers media

Karst aquifers, a significant source of drinking water worldwide, are vulnerable to anthropogenic pollutants because of their special hydrogeological conditions. However, distinguishing the nitrogen transformation process is difficult owing to the heterogeneity of karst media. Therefore, the process of nitrogen transformation in different karst aquifer media remains poorly understood. In this study, multiple stable isotopic and physicochemical indicators are combined, the sources of water and nitrogen are analysed, and the degree of openness and redox conditions of different media are discussed to elucidate the nitrate sources and N transformation in groundwater with different degrees of openness. Water isotopes indicate local meteoric groundwater origin. However, different karst aquifer media have different degrees of openness, resulting in the highest deuterium–oxygen isotope values in surface water, followed by conduit water, fissure water, and isolated cave water. Based on the evidence from isotope and physicochemical indicators, different karst aquifer media have different redox processes. Isolated cave water environments were under anoxic conditions dominated by sulfate reduction reactions. Fissure water was under temporary anoxic or sub-anoxic conditions dominated by denitrification reactions. Conduit water and karst surface water were between micro-oxygen and oxidising conditions, and nitrification was the key process. This phenomenon was observed because the diversity of karst media produces different conservation conditions and openness. The nitrate isotope and Bayesian mixing model indicate that the main sources of nitrate in karst groundwater in the study area are mostly associated with manure and sewage wastes, and a few are from soil organic nitrogen, atmospheric deposition, and chemical fertilizer. This study helps identify the migration and transformation patterns and processes of nitrogen in different karst aquifer media, providing a scientific basis for the restoration and remediation of contaminated karst groundwater.

Can Offshore Meteoric Groundwater Generate Mechanical Instabilities in Passive Continental Margins?

AbstractOffshore meteoric groundwater (OMG) has long been hypothesized to be a driver of seafloor geomorphic processes in continental margins worldwide. Testing this hypothesis has been challenging because of our limited understanding of the distribution and rate of OMG flow and seepage, and their efficacy as erosive/destabilizing agents. Here we carry out numerical simulations of groundwater flow and slope stability using conceptual models and evolving stratigraphy—for passive siliciclastic and carbonate margin cases—to assess whether OMG and its evolution during a late Quaternary glacial cycle can generate the pore pressures required to trigger mechanical instabilities on the seafloor. Conceptual model results show that mechanical instabilities using OMG flow are most likely to occur in the outer shelf to upper slope, at or shortly before the Last Glacial Maximum sea‐level lowstand. Models with evolving stratigraphy show that OMG flow is a key driver of pore pressure development and instability in the carbonate margin case. In the siliciclastic margin case, OMG flow plays a secondary role in preconditioning the slope to failure. The higher degree of spatial/stratigraphic heterogeneity of carbonate margins, lower shear strengths of their sediments, and limited generation of overpressures by sediment loading may explain the higher susceptibility of carbonate margins, in comparison to siliciclastic margins, to mechanical instability by OMG flow. OMG likely played a more significant role in carbonate margin geomorphology (e.g., Bahamas, Maldives) than currently thought.

Calcite‐cemented concretions in non‐marine sandstones: An integrated study of outcrop sedimentology, petrography and clumped isotopes

AbstractCalcite‐cemented concretions can reduce reservoir quality and form important low‐permeability baffles for fluid flow in sandstone hydrocarbon carrier beds/reservoirs. Understanding the origin and distribution patterns of concretions has important implications for characterizing reservoir heterogeneity and developing fields. The origin of calcite concretions in non‐marine sandstones lacking detrital carbonate to source the cement is poorly studied. The practical difficulty of obtaining the precipitation temperature of the concretions prevents the precise determination of the source of cement components, solute flux, pore water type and the geochemical microenvironments in which cement precipitated. Carbonate clumped isotope thermometry can give unique constraints to the temperature of concretionary cement precipitation. This study focused on outcrops of the Lower Cretaceous non‐marine Qingshuihe Formation in the Urho area, on the north‐western margin of the Junggar Basin (West China). Four depositional facies associations were recognized, corresponding to channel, mid‐channel bar, abandoned channel and overbank floodplain environments. Calcite concretions occur only in sandstones and include spherical, ellipsoidal and tabular forms. They are isolated and/or mutually aligned in layers that tend to be either at the top, base, or within channel and mid‐channel sand bodies. The clumped isotope temperatures for the concretionary calcite range from 31 to 45°C with a standard error of <3°C. The calcite has highly variable, low δ13C values ranging from −16.91 ± 0.01 to −2.93 ± 0.02‰ (Vienna Pee Dee Belemnite). The 13C‐depleted bicarbonate source was linked to biodegradation of migrated oils at shallow burial owing to tectonic uplift and erosion. Calcite δ18O values are very consistent and fall between −12.30 ± 0.04 to −9.79 ± 0.31‰ (Vienna Pee Dee Belemnite). Introduction of meteoric water was a dominant mechanism for the pronounced 18O‐depletion in the oxygen isotopes of pore water, along with water–rock interaction during alteration of volcaniclastic materials in sandstones. Meteoric groundwater flushed the Qingshuihe sandstones as confined aquifers down the regional palaeo‐slope, biodegrading the migrated oils and enabling a sufficient solute flux for precipitation of concretions.

The history of calcite diagenesis and origin of exceptionally negative oxygen isotope values in chalks of the Niobrara Formation, Denver Basin, USA

AbstractThe Niobrara Formation of north‐east Colorado, USA, has anomalously negative δ18O values compared to all other Cretaceous chalks. These unique δ18O values have been attributed to elevated heat flow and/or freshening of the Cretaceous Western Interior Seaway. This work utilises clumped isotopes of calcite (Δ47), peak burial temperatures estimated from pyrolysis data, and strontium and neodymium isotopes of carbonate to re‐evaluate the origin of the calcite's18O‐depletion. Peak temperatures indicate lateral variability in geothermal gradients ofca20°C/km at the tens of kilometre scale, and corroborate prior studies proposing locally elevated palaeotemperatures. Greater insight is provided by numerical models of calcite recrystallisation and oxygen isotope evolution that are constrained by measured Δ47‐derived temperatures, calcite δ18O values and inferences from the87Sr/86Sr and εNd values. The models indicate that (1) sea water in the seaway had normal marine δ18O values of −1 (VSMOW) except on the eastern margin of the basin where some freshwater dilution yielded −2 to −3‰ (VSMOW) water, and (2) the main driver of the anonymously negative calcite δ18O values was a semi‐open hydrologic system that provided a few percent by pore volume of meteoric groundwater derived from post‐Laramide recharge into the basin. Minor contributions were a Laramide‐aged heat pulse related to the underlying Colorado Mineral Belt, the thermal insulating effects of now eroded coals, and a small flux of compaction‐driven Cretaceous sea water evolved by smectite dehydration. However, those three factors alone were insufficient drivers of the calcites'18O depletion. High burial temperatures are interpreted to have caused clumped isotope reordering in at least one well, but those temperatures cannot yield the observed calcite δ18O values. The study illustrates the unique attributes of the Niobrara's diagenetic system that results in its anomalous δ18O values, and reaffirms the value of clumped isotopes in unravelling the diagenetic history of chalk systems.

A case of Te-rich low-sulfidation epithermal Au-Ag deposits in a calc-alkaline magmatic arc, NE China

Tellurium-bearing low-sulfidation epithermal Au-Ag deposits are significant producers of gold, silver, and potentially strategic elements if mineral processing methods are optimized for recovery. Although these deposits are generally related to alkaline magmatism, our study documents an unusual occurrence of Te-rich low-sulfidation epithermal systems in the North Heilongjiang Belt in northeast China that is spatially and temporally associated with calc-alkaline magmatism and tectonic extension in a continental arc‐setting.In the North Heilongjiang Belt, Te-bearing Au-Ag deposits are usually sited in dilatant zones, mostly along extensional NW structures or at their intersections with deep‐seated NE-striking faults such as the Nenjiang-Heihe and Jiayin-Mudanjiang lineaments. Of these deposits, Sandaowanzi is well‐known for its bonanza gold grades. These faults localized andesitic to rhyolitic volcano-plutonic centers that evolved from mantle‐derived mafic melts to intermediate compositions due to differentiation and crustal assimilation as documented by their mineralogy and Sr, Nd, and Pb isotope compositions. During assimilation of country rocks, fluids containing 3He and other volatiles derived from mantle magmas displaced or mixed with external groundwater containing radiogenic 4He derived from country rocks. In this belt, the bulk metal content of Au, Ag and Te was probably introduced by deep mantle‐derived mafic‐intermediate calc‐alkaline intrusions. However, our study does not exclude input of metals leached from underlying metasedimentary rocks and older Te‐bearing Au mineralization. The noble gas, hydrogen, oxygen and lead isotope compositions of fluid inclusions and ore minerals suggest that the deposits formed by mixing between magmatic fluids and convecting meteoric ground waters containing lead leached from surrounding country rocks. At deeper levels, isotopic evidence suggests that Au-Ag-Te (Bi) precipitated with pyrite, quartz, sericite, and carbonate minerals due to mixing with Te-rich fluids. At shallower levels, Au and Ag precipitated contemporaneously with base‐metal sulfides, hydrothermal quartz and sericite during episodic boiling as evidenced by silica morphology and mineral textures.The relatively uniform spacing of epithermal systems along NW- and NE-trending structures in the North Heilongjiang Belt was used to identify unexplored spaces within this mineral belt that are prospective for concealed low-sulfidation epithermal gold deposits. Although some of the Au-Ag deposits in this belt are enriched in Te, there is a lack of coeval alkaline igneous rocks that are commonly associated with Te-bearing gold deposits elsewhere in the world (e.g., Cripple Creek, Emperor, and Lihir Island).

Equilibrium-Kinetic Modeling of Uranium Behavior in the System Meteoric Groundwater–U-Containing Siltstone at Active Water Exchange

Equilibrium-Kinetic Modeling of Uranium Behavior in the System Meteoric Groundwater–U-Containing Siltstone at Active Water Exchange

A comprehensive genetic model for the world’s largest Sb deposit (Xikuangshan, China)

AbstractThe Mesozoic (160–130 Ma), fault-controlled Xikuangshan Sb deposit within Devonian limestone strata of Hunan Province, Southern China is the world’s largest Sb deposit containing a proven reserve of ~2.5 m Sb. Although mined for over a century, its genesis remains poorly understood. Here we use new He-Ar isotope data of hydrothermal stibnite and both new and existing C-O-Sr-Nd isotopes of hydrothermal calcite with known stages to decipher its genesis and the major constraints on mineralization intensity. The 3He/4He and 40Ar/36Ar ratios of fluid inclusions trapped in stibnite are from 0.01 to 0.04 Ra (Ra: atmospheric 3He/4He ratio) and 304–1077, respectively, indicating the ore-forming fluids at Xikuangshan were dominated by air-saturated meteoric groundwater after interaction with crustal rocks. Ore-stage calcite C and O isotopes indicated that most CO2 in the fluids was acquired from marine carbonate rocks by dissolution; whereas Sr and Nd isotopes differed from deposited Devonian country rocks but were similar to the underlying regional Proterozoic clastic rocks in the region. Calcite from early and late stages showed a strong positive correlation between δ18O and 87Sr/86Sr, consistent with the mixing between the circulating groundwater and compounds released from the Proterozoic rocks due to extensive fluid-rock interaction. The 3He/Q ratios of the fluid inclusions are low, varying from 4.3 to 18.5 × 10−15 cm3 standard temperature and pressure (STP) J−1, indicating deep-seated magma could have provided heat by conduction but no volatiles into the ore-forming fluids. Based on these new results, we suggest that deep-seated granitic magma heated the down-going meteoric groundwater along fault zones, after which the groundwater extensively interacted with and extracted Sb from the Proterozoic Sb-rich rocks to form Sb-rich fluids. The Sb-rich fluids then ascended through regional faults and deposited Sb as stibnites at favorable structural traps to form the Xikuangshan Sb deposit. This study highlights that extensive water-rock interaction is essential to form the deposit, and more intensive water-rock interaction at an early stage allowed for early-stage mineralization yielding higher Sb reserves (>80%) at Xikuangshan.

Drivers and Seasonal Variability of Redox-Sensitive Metal Chemistry in a Shallow Subterranean Estuary

The subterranean estuary (STE) has been historically defined in terms of the mixing of saline and fresh water, in an analogy to surface estuaries. However, redox gradients are also a defining characteristic of the STE and influence its role as a source or sink for metals in the environment. Approaching the STE from a redox-focused biogeochemical perspective (e.g., considering the role of microbial respiration and availability of organic matter) provides the ability to quantify drivers of metal transport across spatial and temporal scales. This study measured the groundwater composition of a shallow STE over 2 years and used multiple linear regression to characterize the influence of salinity and redox chemistry on the behavior of redox-sensitive metals (RSMs) including Mo, U, V, and Cr. Molybdenum and uranium were both supplied to the STE by surface water, but differed in their removal mechanisms and seasonal behavior. Molybdenum showed non-conservative removal by reaction with sulfide in all seasons. Sulfide concentrations at this site were consistently higher than required for quantitative reaction with Mo (10 µM sulfide), evidently leading to quantitative removal at the same depth regardless of season. In contrast, U appeared to depend directly on microbial activity for removal, and showed more extensive removal at shallower depths in summer. Both V and Cr were elevated in meteoric groundwater (2.5–297 nM and 2.6–236 nM, respectively), with higher endmember concentrations in summer. Both V and Cr also showed non-conservative addition within the STE relative to conservative mixing among the observed endmembers. The mobility of V and Cr in the STE, and therefore their supply to the coastal ocean, was controlled by the availability of dissolved organic matter and Fe, suggesting V and Cr were potentially complexed in the colloidal fraction. Complexation by different organic matter pools led to seasonal variations in V but greater interannual variability of Cr. These results reveal distinct behaviors of RSMs in response to seasonal biogeochemical processes that drive microbial activity, organic matter composition, and complexation by inorganic species.

Statistical Relationship Between the Decrease of Major Seismicity and Drought in Southern California Since 1900

The seismicity in Southern California significantly decreased over the last decades. The decrease went in parallel with the reduction of meteoric groundwater recharge, which is a well-known factor capable of affecting seismicity. In this work the existence of a systematic statistical relationship was investigated by comparing the time density of Mw ≥ 5.7 earthquakes since 1900 with the time series of the Palmer Drought Severity Index (PDSI), an indicator of soil moisture roughly correlated with groundwater recharge. Given the non-stationarity of the two signals, the formal comparison was performed using both binomial logistic regression and cointegration testing. The analysis showed a significant statistical relationship, with peaks of seismicity 8 years behind those of PDSI. This finding suggests the hypothesis that groundwater recharge might affect earthquakes at a multi-year time scale. Proving this theory requires accurate measures and hydrogeological modeling, which is behind the scope of this work. Nonetheless, according to previous studies, the observed time lag might be explained by the slow propagation of pore pressure from the surface to the seismogenic volume. The ongoing trend towards an arid climate, made more evident by the recent severe droughts, might have contributed to the earthquake reduction of the last decades. The connection is particularly evident in the Salton Trough, with possible implications for the interpretation of its paleoseismicity.

Spatial and Temporal Constraints on the Composition of Microbial Communities in Subsurface Boreholes of the Edgar Experimental Mine.

ABSTRACTThe deep biosphere hosts uniquely adapted microorganisms overcoming geochemical extremes at significant depths within the crust of the Earth. Attention is required to understand the near subsurface and its continuity with surface systems, where numerous novel microbial members with unique physiological modifications remain to be identified. This surface-subsurface relationship raises key questions about networking of surface hydrology, geochemistry affecting near-subsurface microbial composition, and resiliency of subsurface ecosystems. Here, we apply molecular and geochemical approaches to determine temporal microbial composition and environmental conditions of filtered borehole fluid from the Edgar Experimental Mine (∼150 m below the surface) in Idaho Springs, CO. Samples were collected over a 4-year collection period from expandable packers deployed to accumulate fluid in previously drilled boreholes located centimeters to meters apart, revealing temporal evolution of borehole microbiology. Meteoric groundwater feeding boreholes demonstrated variable recharge rates likely due to a complex and undefined fracture system within the host rock. 16S rRNA gene analysis determined that unique microbial communities occupy the four boreholes examined. Two boreholes yielded sequences revealing the presence of Desulfosporosinus, Candidatus Nitrotoga, and Chelatococcus associated with endemic subsurface communities. Two other boreholes presented sequences related to nonsubsurface-originating microbiota. High concentration of sulfate along with detected sulfur reducing and oxidizing microorganisms suggests that sulfur related metabolic strategies are prominent within these near-subsurface boreholes. Overall, results indicate that microbial community composition in the near-subsurface is highly dynamic at very fine spatial scales (<20 cm) within fluid-rock equilibrated boreholes, which additionally supports the role of a relationship for surface geochemical processes infiltrating and influencing subsurface environments.IMPORTANCE The Edgar Experimental Mine, Idaho Springs, CO, provides inexpensive and open access to borehole investigations for subsurface microbiology studies. Understanding how microbial processes in the near subsurface are connected to surface hydrological influences is lacking. Investigating microbial communities of subsurface mine boreholes provides evidence of how geochemical processes are linked to biogeochemical processes within each borehole and the geochemical connectedness and mobility of surface influences. This study details microbial community composition and fluid geochemistry over spatial and temporal scales from boreholes within the Edgar Mine. These findings are relevant to biogeochemistry of near-surface mines, caves, and other voids across planetary terrestrial systems. In addition, this work can lead to understanding how microbial communities relate to both fluid-rock equilibration, and geochemical influences may enhance our understanding of subsurface molecular biological tools that aid mining economic practices to reflect biological signals for lucrative veins in the near subsurface.

Geochemical influences on methanogenic groundwater from a low rank coal seam gas reservoir: Walloon Subgroup, Surat Basin

Hydrochemical data responds at a much slower rate to changes in groundwater conditions than does the propagation of hydraulic pressure, and therefore may provide more insight to groundwater flow paths. In low rank coal measures, where gas is biogenic, it is important to understand the fluid-rock and microbial interactions that affect the spatial and temporal distribution of groundwater composition. Pressure data may not reflect true groundwater conditions pre-anthropogenic influence, nor does it provide information on the main drivers of groundwater composition, actual aquifer behaviour or even prove groundwater flow.This study uses a process-based approach to interpret a combination of tracer (36Cl, 14C, 87Sr/86Sr, 18O/16O) and hydrochemical data obtained from coal seam gas production wells to identify the main geochemical processes and thus controls on the groundwater composition in different coal seam producing areas of the Walloon Subgroup, Surat Basin, Australia. This is arguably one of the largest coal seam gas producing regions in the world. Tracer data measured in this study show that the Walloon Subgroup behaves as a stagnant aquitard, as indicated by the almost total loss of cosmogenic tracers over relatively short groundwater flow distances (~15 km), suggestive of very low ground water flow velocities. The range of 36Cl is 9.0 to 23.8 (x 10−15) while the 36Cl values across the Undulla anticline in the eastern edge of the basin, are essentially the same (12.2–14.7) within analytical error. It is argued that these isotopic values represent secular equilibrium for the Walloon Subgroup. Radiometric carbon (14C) levels across all three production areas (Roma, Undulla Nose, Kogan Nose) are also too low (range = 0.12–1.95 pMC) for viable field interpretation largely owing to the long residence time of the groundwater and the local activity of methanogens. Groundwater flow velocity was estimated to be <0.1 m/y, which is significantly less than the 0.7 m/y recently reported for the underlying Hutton Sandstone.As a result of the low groundwater flow velocities, trends in geochemistry are visible only in production regions proximal to the subcrop. At flow distances greater than 10–15 km from subcrop, several low-temperature interactions (cation exchange, silicate weathering, matrix diffusion and hyperfiltration) start to influence groundwater composition. Shallow subsurface chemical and microbial reactions may initially dominate the geochemical composition of the meteoric groundwater, but this is then overprinted by the actions of sulfate reducers and methanogens, resulting in groundwater with the typical geochemical characteristics similar to other coal bed methane groundwater in basins across the world (low SO4, Ca, Mg and high HCO3, Na, Cl). As distance and depth increase further, low temperature fluid-rock interactions then begin to influence the groundwater composition.This holistic, process-based approach applied to a combination of cosmogenic and stable isotopes, and standard hydrochemical data interpreted against basin lithology has enabled a more comprehensive picture on the behaviour of the groundwater of the Walloon Subgroup and is applicable to the study of other sedimentary basins.

Fluid mixing as primary trigger for cassiterite deposition: Evidence from in situ δ18O-δ11B analysis of tourmaline from the world-class San Rafael tin (-copper) deposit, Peru

We present a high-resolution in situ study of oxygen and boron isotopes measured in tourmaline from the world-class San Rafael Sn (–Cu) deposit (Central Andean tin belt, Peru) aiming to trace major fluid processes at the magmatic-hydrothermal transition leading to the precipitation of cassiterite. Our results show that late-magmatic and pre-ore hydrothermal tourmaline has similar values of δ18O (from 10.6‰ to 14.1‰) and δ11B (from −11.5‰ to −6.9‰). The observed δ18O and δ11B variations are dominantly driven by Rayleigh fractionation, reflecting tourmaline crystallization in a continuously evolving magmatic-hydrothermal system. In contrast, syn-ore hydrothermal tourmaline intergrown with cassiterite has lower δ18O values (from 4.9‰ to 10.2‰) and in part higher δ11B values (from −9.9‰ to −5.4‰) than late-magmatic and pre-ore hydrothermal tourmaline, indicating important contribution of meteoric groundwater to the hydrothermal system during ore deposition. Quantitative geochemical modeling demonstrates that the δ18O-δ11B composition of syn-ore tourmaline records variable degrees of mixing of a hot Sn-rich magmatic brine with meteoric waters that partially exchanged with the host rocks. These results provide thus direct in situ isotopic evidence of fluid mixing as a major mechanism triggering cassiterite deposition. Further, this work shows that combined in situ δ18O and δ11B analyses of tourmaline is a powerful approach for understanding fluid processes in dynamic magmatic-hydrothermal environments.