Sulfosalt melts and heavy metal (As‐Sb‐Bi‐Sn‐Pb‐Tl) fractionation during volcanic gas expansion: the El Indio (Chile) paleo‐fumarole

High‐sulfidation vein gold deposits such as El Indio, Chile, formed in fracture arrays <1000 m beneath paleo‐solfatara in volcanic terranes. Stable isotope data have confirmed a predominance of magmatic vapor during the deposition of arsenic‐rich sulfide–sulfosalt assemblages in this deposit. These provide a unique opportunity to analyze the processes and products of high‐temperature volcanic gas expansion in fractures that form the otherwise inaccessible infrastructure deep inside equivalent present‐day fumaroles. We provide field emission scanning electron microscope and LA‐ICP‐MS micro‐analytical data for the wide range of heavy, semi‐metals and metalloids (arsenic, antimony, bismuth, tin, silver, gold, tellurium and selenium) in the complex pyrite‐enargite‐Fe‐tennantite assemblages from Copper Stage mineralization in the El Indio deposit. These data document the progressive fractionation of antimony and other heavy metals, such as bismuth, during crystallization from a sulfosalt melt that condensed from expanding vapor at about 15 MPa (150 bars) and >650°C following higher temperature vapor deposition of crystalline pyrite and enargite. The sulfosalt melt aggressively corroded the earlier enargite and pyrite and hosts clusters of distinctive euhedral quartz crystals. The crystallizing sulfosalt melt also trapped an abundance of vugs within which heavy metal sulfide and sulfosalt crystals grew together with K‐Al silicates and fluorapatite. These data and their geologic context suggest that, in high‐temperature fumaroles on modern active volcanoes, over 90% of the arsenic content of the primary magmatic vapor (perhaps 2000 mg kg^?1) was precipitated subsurface as sulfosalt. Subsurface fractionation may also account for the range of exotic Pb‐Sn‐Bi‐Se sulfosalts observed in fumarole sublimates on active volcanoes such as Vulcano, Italy, as well as on extra‐terrestrial volcanoes such as Maxwell Montes, Venus.     

Modelling the Lost City hydrothermal field: influence of topography and permeability structure

The Lost City hydrothermal field (LCHF) is hosted in serpentinite at the crest of the Atlantis Massif, an oceanic core complex close to the mid‐Atlantic Ridge. It is remarkable for its longevity and for venting low‐temperature (40–91°C) alkaline fluids rich in hydrogen and methane. IODP Hole U1309D, 5 km north of the LCHF, penetrated 1415 m of gabbroic rocks and contains a near‐conductive thermal gradient close to 100°C km^?1. This is remarkable so close to an active hydrothermal field. We present hydrothermal modelling using a topographic profile through the vent field and IODP site U1309. Long‐lived circulation with vent temperatures similar to the LCHF can be sustained at moderate permeabilities of 10^?14 to 10^?15 m² with a basal heatflow of 0.22 W m^?2. Seafloor topography is an important control, with vents tending to form and remain in higher topography. Models with a uniform permeability throughout the Massif cannot simultaneously maintain circulation at the LCHF and the near‐conductive gradient in the borehole, where permeabilities <10^?16 m² are required. A steeply dipping permeability discontinuity between the LCHF and the drill hole is required to stabilize venting at the summit of the massif by creating a lateral conductive boundary layer. The discontinuity needs to be close to the vent site, supporting previous inferences that high permeability is most likely produced by faulting related to the transform fault. Rapid increases in modelled fluid temperatures with depth beneath the vent agree with previous estimates of reaction temperature based on geochemical modelling.     

URANIUM‐SERIES AND LUMINESCENCE DATING OF VOLCANIC LITHIC ARTEFACTS*

U‐series dating was used to determine the growth rate of a feldspar‐to‐clay weathering rind in a mid‐Holocene Cascade–Olcott tradition andesite core, and luminescence dating (last exposure to sunlight) was used to date fine‐grained feldspars scraped from the surfaces of similar buried artefacts from a ¹⁴C‐sediment‐dated archaeological site (45KI464) on the wet western slope of the Cascade Mountains of Washington. For U‐series dating, we measured ²²⁶Ra excess (²²⁶Ra excess =²²⁶Ra –²³⁰Th) in five stratigraphic depth controlled rind scrapings. ²³⁸U, ²³²Th and ²³⁰Th were counted by alpha spectrometry, and ²²⁶Ra and ²¹⁰Pb were counted by gamma spectrometry on each sub‐sample.     

Barite–pyrite mineralization of the Wiesbaden thermal spring system, Germany: a 500-kyr record of geochemical evolution

Barite–(pyrite) mineralizations from the thermal springs of Wiesbaden, Rhenish Massif, Germany, have been studied to place constraints on the geochemical evolution of the hydrothermal system in space and time. The thermal springs, characterized by high total dissolved solids (TDS) contents and predominance of NaCl, ascend from aquifers at 3–4 km depth and discharge at a temperature of 65–70°C. The barite–(pyrite) mineralization is found in upflow and discharge zones of the present‐day thermal springs as well as at elevations up to 50 m above the current water table. Hence, this mineralization style constitutes a continuous record of the hydrothermal activity, linking the past evolution with the present state of this geothermal system. The sulphur isotope signatures of the mineralization indicate a continuous decrease of the δ³⁴S of sulphate from +16.9‰ in the oldest barite to +10.1‰ in the present‐day thermal water. The δ³⁴S values of barite closely resemble various recently active thermal springs along the southern margin of the Rhenish Massif and contrast strongly with different regional ground and mineral waters. The mineralogical and isotopic signatures, combined with calculations based on uplift rates and the regional geological history, indicate a minimum activity of the thermal spring system at Wiesbaden of about 500 000 years. This timeframe is considerably larger than conservative models, which estimate the duration of thermal spring systems in continental intraplate settings to last for several 10 000 years. The calculated equilibrium sulphur isotope temperatures of coexisting barite and pyrite range between 65 and 80°C, close to the discharge temperature of the springs, which would indicate apparent equilibrium precipitation. Kinetic modelling of the re‐equilibration of the sulphate–sulphide pair during water ascent shows that this process would require 220 Myr. Therefore, we conclude that pyrite is formed from precursor Fe monosulphide phases, which rapidly precipitate in the near‐surface environment, preserving the isotope fractionation between dissolved sulphate and sulphide established in the deep aquifer. Equilibrium modelling of water–mineral reactions shows slight supersaturation of barite at the discharge temperature. Pyrite is already strongly supersaturated at the temperatures estimated for the aquifer (110°C) and processes in the near‐surface environment are most probably related to contact of the thermal water with atmospheric oxygen, resulting in formation of oxidized intermediate sulphur species and precipitation of Fe monosulphide phases, which subsequently recrystallize to pyrite.     

Fluid mixing induced by hydrothermal activity in the ordovician carbonates in Tarim Basin,China

Permian hydrothermal activity in the Tarim Basin may have been responsible for the invasion of hot brines into Ordovician carbonate reservoirs. Studies have been undertaken to explain the origin and geochemical characteristics of the diagenetic fluid present during this hydrothermal event although there is no consensus on it. We present a genetic model resulting from the study of δ¹³C, δ¹⁸O, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr isotope values and fluid inclusions (FIs) from fracture‐ and vug‐filling calcite, saddle dolomite, fluorite, barite, quartz, and anhydrite from Ordovician outcrops in northwest (NW) Tarim Basin and subsurface cores in Central Tarim Basin. The presence of hydrothermal fluid was confirmed by minerals with fluid inclusion homogenization temperatures being >10°C higher than the paleo‐formation burial temperatures both in the NW Tarim and in the Central Tarim areas. The mixing of hot (>200°C), high‐salinity (>24 wt% NaCl), ⁸⁷Sr‐rich (up to 0.7104) hydrothermal fluid with cool (60–100°C), low‐salinity (0 to 3.5 wt% NaCl), also ⁸⁷Sr‐rich (up to 0.7010) meteoric water in the Ordovician unit was supported by the salinity of fluid inclusions, and δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr isotopic values of the diagenetic minerals. Up‐migrated hydrothermal fluids from the deeper Cambrian strata may have contributed to the hot brine with high sulfate concentrations which promoted thermochemical sulfate reduction (TSR) in the Ordovician, resulting in the formation of ¹²C‐rich (δ¹³C as low as ?13.8‰) calcite and ³⁴S‐rich (δ³⁴S values from 21.4‰ to 29.7‰) H₂S, pyrite, and elemental sulfur. Hydrothermal fluid mixing with fresh water in Ordovician strata in Tarim Basin was facilitated by deep‐seated faults and up‐reaching faults due to the pervasive Permian magmatic activity. Collectively, fluid mixing, hydrothermal dolomitization, TSR, and faulting may have locally dissolved the host carbonates and increased the reservoir porosity and permeability, which has significant implications for hydrocarbon exploration.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.     

Invasion of a karst aquifer by hydrothermal fluids: evidence from stable isotopic compositions of cave mineralization

Mineral deposits in the Cupp‐Coutunn/Promeszutochnaya cave system (Turkmenia, central Asia) record a phase of hydrothermal activity within a pre‐existing karstic groundwater conduit system. Hydrothermal fluids entered the caves through fault zones and deposited sulphate, sulphide and carbonate minerals under phreatic conditions. Locally, intense alteration of limestone wall rocks also occurred at this stage. Elsewhere in the region, similar faults contain economic quantities of galena and elemental sulphur mineralization. Comparisons between the Pb and S isotope compositions of minerals found in cave and ore deposits confirm the link between economic mineralization and hydrothermal activity at Cupp‐Coutunn. The predominance of sulphate mineralization in Cupp‐Coutunn implies that the fluids were more oxidized in the higher permeability zone associated with the karst aquifer. A slight increase in the δ³⁴S of sulphate minerals and a corresponding δ³⁴S decrease in sulphides suggest that partial isotopic equilibration occurred during oxidation. Carbonate minerals indicate that the hydrothermal fluid was enriched in ¹⁸O (δ¹⁸O_SMOW ～ + 10‰) relative to meteoric groundwater and seawater. Estimated values for δ¹³C_DIC (δ¹³C_PDB ～ ? 13‰) are consistent with compositions expected for dissolved inorganic carbon (DIC) derived from the products of thermal decomposition of organic matter and dissolution of marine carbonate. Values derived for δ¹³C_DIC and δ¹⁸O_water indicate that the hydrothermal fluid was of basinal brine origin, generated by extensive water–rock interaction. Following the hydrothermal phase, speleothemic minerals were precipitated under vadose conditions. Speleothemic sulphates show a bimodal sulphur isotope distribution. One group has compositions similar to the hydrothermal sulphates, whilst the second group is characterized by higher δ³⁴S values. This latter group may either record the effects of microbial sulphate reduction, or reflect the introduction of sulphate‐rich groundwater generated by the dissolution of overlying evaporites. Oxygen isotope compositions show that calcite speleothems were precipitated from nonthermal groundwater of meteoric origin. Carbonate speleothems are relatively enriched in ¹³C compared to most cave deposits, but can be explained by normal speleothem‐forming processes under thin, arid‐zone soils dominated by C4 vegetation. However, the presence of sulphate speleothems, with isotopic compositions indicative of the oxidation of hydrothermal sulphide, implies that CO₂ derived by reaction of limestone with sulphuric acid (‘condensation corrosion’) contributed to the formation of ¹³C‐enriched speleothem deposits.     

Regional groundwater flow and interactions with deep fluids in western Apennine: the case of Narni‐Amelia chain (Central Italy)

The elemental fluxes and heat flow associated with large aquifer systems can be significant both at local and at regional scales. In fact, large amounts of heat transported by regional groundwater flow can affect the subsurface thermal regime, and the amount of matter discharged towards the surface by large spring systems can be significant relative to the elemental fluxes of surface waters. The Narni‐Amelia regional aquifer system (Central Italy) discharges more than 13 m³ sec^?1 of groundwater characterised by a slight thermal anomaly, high salinity and high pCO₂. During circulation in the regional aquifer, groundwater reacts with the host rocks (dolostones, limestones and evaporites) and mixes with deep CO₂‐rich fluids of mantle origin. These processes transfer large amounts of dissolved substances, in particular carbon dioxide, and a considerable amount of heat towards the surface. Because practically all the water circulating in the Narni‐Amelia system is discharged by few large springs (Stifone‐Montoro), the mass and energy balance of these springs can give a good estimation of the mass and heat transported from the entire system towards the surface. By means of a detailed mass and balance of the aquifer and considering the soil CO₂ fluxes measured from the main gas emission of the region, we computed a total CO₂ discharge of about 7.8 × 10⁹ mol a^?1 for the whole Narni‐Amelia system. Finally, considering the enthalpy difference between infiltrating water and water discharged by the springs, we computed an advective heat transfer related to groundwater flow of 410 ± 50 MW.     

Deep Regolith Weathering on the Summit Surface of the Southern Mount Lofty Ranges,South Australia: a Contribution to the ‘Laterite’ Debate

Chemical and mineralogical analyses of samples from a 102 m deep borehole and from road cuts on the summit surface of the Mount Lofty Ranges near Willunga Hill, are used to assess critically the view that the regolith here developed as a result of tropical, so‐called ‘lateritic’ weathering processes that developed a standard ‘laterite’ profile of great antiquity. There is no evidence of a former surface crust that comprises the upper part of a ‘standard laterite profile’. Moreover, there is no dramatic variation in chemical composition down the profile, with largely in situ localised weathering transformations explaining mineralogical variability. The presence of 2:1 layer silicates and the absence of gibbsite do not favour the operation of former intense tropical weathering, but the possible presence of chloritised smectite may have inhibited gibbsite formation. An iron‐depleted pallid zone does not occur at depth in the profile, but is present on the plateau margin. Many of the weathering features exposed in the road cuts can be explained in terms of modifications and developments under environmental conditions similar to those of the present, arguing against the view that the summit surface and its associated weathering mantle have been preserved in pristine form since the Mesozoic.     

Analytical and numerical models of hydrothermal fluid flow at fault intersections

Fault intersections are the locus of hot spring activity and Carlin‐type gold mineralization within the Basin and Range, USA. Analytical and numerical solutions to Stokes equation suggest that peak fluid velocities at fault intersections increase between 20% and 47% when fracture apertures have identical widths but increase by only about 1% and 8% when aperture widths vary by a factor of 2. This suggests that fault zone intersections must have enlarged apertures. Three‐dimensional finite element models that consider intersecting 10‐ to 20‐m wide fault planes resulted in hot spring activity being preferentially located at fault zone intersections when fault zones were assigned identical permeabilities. We found that the onset of convection at the intersections of the fault zones occurred in our hydrothermal model over a narrow permeability range between 5 × 10^?13 and 7 × 10^?13 m². Relatively high vertical fluid velocities (0.3–3 m year^?1) extended away from the fault intersections for about 0.5–1.5 km. For the boundary conditions and fault plane dimensions used, peak discharge temperatures of 112°C at the water table occurred with an intermediate fault zone permeability of 5 × 10^?13 m². When fault plane permeability differed by a factor of 2 or more, the locus of hot spring activity shifted away from the intersections. However, increasing the permeability at the core of the fault plane intersection by 40% shifted the discharge back to the intersections. When aquifer units were assigned a permeability value equal to those of the fault planes, convective rolls developed that extend about 3 km laterally along the fault plane and into the adjacent aquifer.     

Br/Cl signature of hydrothermal fluids: liquid–vapour fractionation of bromine revisited

Br/Cl ratios of hydrothermal fluids are widely used as geochemical tracers in marine hydrothermal systems to prove fluid phase separation processes. However, previous results of the liquid–vapour fractionation of bromine are ambiguous. Here we report new experimental results of the liquid–vapour fractionation of bromine in the system H₂O–NaCl–NaBr at 380–450°C and 22.9–41.7 MPa. Our data indicate that bromine is generally more enriched than chlorine in the liquid phase. Calculated exchange coefficients K_D(Br‐Cl)^{liquid‐vapour} for the reaction Br^vapour + Cl^liquid = Br^liquid + Cl^vapour are between 0.94 ± 0.08 and 1.66 ± 0.14 within the investigated P–T range. They correlate positively with D_Cl^{liquid‐vapour} and suggest increasing bromine–chlorine fractionation with increasing opening of the liquid–vapour solvus, i.e. increasing distance to the critical curve in the H₂O–NaCl system. An empirical fit of the form K_D(Br‐Cl)^{liquid‐vapour} = a*ln[b*(D_Cl^{liquid‐vapour}?1) + e^1/a] yields a = 0.349 and b = 1.697. Based on this empirical fit and the well‐constrained phase relations in the H₂O–NaCl system we calculated the effect of fluid phase separation on the Br/Cl signature of a hydrothermal fluid with initial seawater composition for closed and open adiabatic ascents along the 4.5 and 4.8 J g^?1 K^?1 isentropes. The calculations indicate that fluid phase separation can significantly alter the Br/Cl ratio in hydrothermal fluids. The predicted Br/Cl evolutions are in accord with the Br/Cl signatures in low‐salinity vent fluids from the 9 to 10°N East Pacific Rise.     

Principal features of impact-generated hydrothermal circulation systems: mineralogical and geochemical evidence

Any hypervelocity impact generates a hydrothermal circulation system in resulting craters. Common characteristics of hydrothermal fluids mobilized within impact structures are considered, based on mineralogical and geochemical investigations, to date. There is similarity between the hydrothermal mineral associations in the majority of terrestrial craters; an assemblage of clay minerals–zeolites–calcite–pyrite is predominant. Combining mineralogical, geochemical, fluid inclusion, and stable isotope data, the distinctive characteristics of impact‐generated hydrothermal fluids can be distinguished as follows: (i) superficial, meteoric and ground water and, possibly, products of dehydration and degassing of minerals under shock are the sources of hot water solutions; (ii) shocked target rocks are sources of the mineral components of the solutions; (iii) flow of fluids occurs mainly in the liquid state; (iv) high rates of flow are likely (10^?4 to 10^?3 m s^?1); (v) fluids are predominantly aqueous and of low salinity; (vi) fluids are weakly alkaline to near‐neutral (pH 6–8) and are supersaturated in silica during the entire hydrothermal process because of the strong predominance of shock‐disordered aluminosilicates and fusion glasses in the host rocks; and (vii) variations in the properties of the circulating solutions, as well as the spatial distribution of secondary mineral assemblages are controlled by temperature gradients within the circulation cell and by a progressive cooling of the impact crater. Products of impact‐generated hydrothermal processes are similar to the hydrothermal mineralization in volcanic areas, as well as in modern geothermal systems, but impacts are always characterized by a retrograde sequence of alteration minerals.     

Fluid flow and the Heart Mountain fault: a stable isotopic, fluid inclusion, and geochronologic study

Numerous studies have proposed that movement along the 3400‐km² low‐angle (<3°) Heart Mountain detachment fault of north‐western Wyoming and south‐western Montana was facilitated by the presence of lubricating fluids. A recent stable isotope study suggested that the fluids along the Heart Mountain fault originated from large hydrothermal systems associated with Eocene intrusive centers. Herein, we present results from a combined stable isotope, fluid inclusion, and ⁴⁰Ar/³⁹Ar geochronology study of the relationship between shallow crustal fluids from Eocene intrusive centers in the New World Mining district and fluids associated with the Heart Mountain fault. Our results suggest that: (i) Eocene intrusive bodies within the New World Mining District focused hydrothermal fluids along specific units and structures from the ore deposit centers along the Heart Mountain fault detachment surface; (ii) hydrothermal waters were focused along the Heart Mountain fault from the breakaway region near Silvergate, Montana toward Heart Mountain in Cody, Wyoming; and (iii) hydrothermal activity along the Heart Mountain fault occurred at the same time as emplacement of the Eocene intrusives, between 50.1 and 48.1 Ma. These data, taken together, suggest that the hydrothermal activity generated by intrusion of Eocene rhyodacites and dacites provided the source of fluids found along the Heart Mountain fault plane.     

Constraining groundwater flow in the glacial drift and saginaw aquifers in the Michigan Basin through helium concentrations and isotopic ratios

³He and ⁴He concentrations in excess of those in water in solubility equilibrium with the atmosphere by up to two and three orders of magnitude are observed in the shallow Glacial Drift and Saginaw aquifers in the Michigan Basin. A simplified He transport model shows that in situ production is negligible and that most He excesses have a source external to the aquifer. Simulated results show that ³He and ⁴He fluxes entering the bottom of the Saginaw aquifer are 7.5 × 10^?14 and 6.1 × 10^?7 cm³STPcm^?2 yr^?1, both of which are lower than fluxes entering the underlying Marshall aquifer, 1.0 × 10^?13 and 1.6 × 10^?6 cm³STPcm^?2 yr^?1 for ³He and ⁴He, respectively. In contrast, He fluxes entering the Saginaw aquifer are higher than fluxes entering the overlying Glacial Drift aquifer of 5.2 × 10^?14 and 1.5 × 10^?7 cm³STPcm^?2 yr^?1 for ³He and ⁴He, respectively. The unusually high He fluxes and their decreasing values from the lower Marshall to the upper Glacial Drift aquifer strongly suggest the presence of an upward cross‐formational flow, with increasing He dilution toward the surface by recharge water. These fluxes are either comparable to or far greater than He fluxes in deeper aquifers around the world. Model simulations also suggest an exponential decrease in the horizontal groundwater velocity with recharge distance. Horizontal velocities vary from 13 to 2 myr^?1 for the Saginaw aquifer and from 18 to 6 myr^?1 for the Marshall aquifer. The highly permeable Glacial Drift aquifer displays a greater velocity range, from 250 to 5 myr^?1. While Saginaw ⁴He ages estimated based on the simulated velocity field display an overall agreement with ¹⁴C ages, ¹⁴C and ⁴He ages in the Glacial Drift and Marshall aquifers deviate significantly, possibly due to simplifications introduced in the He transport model leading to calculation of first‐order approximation He ages and high uncertainties in Glacial Drift ¹⁴C ages.     

Seasonal and Spatial patterns in sheep grazing on a high‐level plateau in the Grampian Mountains,Scotland

Sheep usage of part of the summit of Glas Maol was monitored by pellet‐group counts to determine impact on Carex bigelowii‐Racomitrium lanuginosum moss heath. The effects of a fenced skiing corridor in giving shelter and disrupting ranging movements were assessed. Dung deposition was appreciable only from June to September each year, and heaviest in July and August; occupance seemed to depend on the presence of substantial quantities of green herbage. Dung deposition was much greater within 5 m of the fence, probably because of its sheltering effect. The estimated May‐October stocking of 1.1 sheep ha^‐1 on the main plateau is surprisingly heavy for the altitude, whereas usage by red deer was negligible.     

Modeling of hydrogen production by serpentinization in ultramafic‐hosted hydrothermal systems: application to the Rainbow field

The production of hydrogen by serpentinization in ultramafic‐hosted hydrothermal systems is simulated by coupling thermodynamic and dynamic modeling in the framework of a thermo‐hydraulic single‐pass model where a high‐temperature hydrothermal fluid moves preferentially through a main canal of high permeability. The alteration of ultramafic rocks is modeled with a first‐order kinetic formulation, wherein the serpentinization rate coefficient, K_r, takes the form: K_r = A exp(?α(T ? T₀)²). In this formulation, α determines the temperature range of the reaction and T₀ is the temperature at which the serpentinization rate reaches its maximum. This model is applied to the Rainbow hydrothermal system, which is situated on the Mid‐Atlantic Ridge, and characterized by a high temperature, a high mass flux, and a very high hydrogen concentration. The results show that a first‐order kinetic law gives a useful representation of the kinetics of serpentinization. The estimated value for the parameter A in the temperature‐dependent formulation of the serpentinization rate coefficient lies in the range (1–5) × 10^?11 s^?1. This effective parameter is several orders of magnitude lower than the values obtained from small grain‐size experiments, but in agreement with other published modeling studies of natural systems. Numerical simulations show that the venting site is able to produce the observed high concentration of hydrogen during the whole continuous lifetime of the Rainbow site.     

Hydrogeochemical dynamics affecting steam‐heated pools at El Chichón Crater (Chiapas – Mexico)

El Chichón is an active volcano located in the north‐western Chiapas, southern Mexico. The crater hosts a lake, a spring, named Soap Pool, emerging from the underlying volcanic aquifer and several mud pools/hot springs on the internal flanks of the crater which strongly interact with the current fumarolic system (steam‐heated pools). Some of these pools, the crater lake and a cold spring emerging from the 1982 pumice deposits, have been sampled and analysed. Water–volcanic gas interactions determine the heating (43–99°C) and acidification (pH 2–4) of the springs, mainly by H₂S oxidation. Significantly, in the study area, a significant NH₃ partial pressure has been also detected. Such a geochemically aggressive environment enhances alteration of the rock in situ and strongly increases the mineralization of the waters (and therefore their electrical conductivity). Two different mineralization systems were detected for the crater waters: the soap pool‐lake (Na⁺/Cl^? = 0.4, Na/Mg>10) and the crater mud pools (Na⁺/Cl^? > 10, Na/Mg < 4). A deep boiling, Na⁺‐K⁺‐Cl^?‐rich water reservoir generally influences the Soap Pool‐lake, while the mud pool is mainly dominated by water‐gas–rock interactions. In the latter case, conductivity of sampled water is directly proportional to the presence of reactive gases in solution. Therefore, chemical evolution proceeds through neutralization due to both rock alteration and bacterial oxidation of ammonium to nitrate. The chemical compositions show that El Chichón aqueous fluids, within the crater, interact with gases fed by a geothermal reservoir, without clear additions of deep magmatic fluids. This new geochemical dataset, together with previously published data, can be used as a base line with which to follow‐up the activity of this deadly volcano.     

Fracture mineralization and fluid flow evolution: an example from Ordovician–Devonian carbonates,southwestern Ontario,Canada

Petrography, geochemistry (stable and radiogenic isotopes), and fluid inclusion microthermometry of matrix dolomite, fracture‐filling calcite, and saddle dolomite in Ordovician to Devonian carbonates from southwestern Ontario, Canada, provide useful insights into fluid flow evolution during diagenesis. The calculated δ¹⁸O_fluid, ΣREE, and REE_SN patterns of matrix and saddle dolomite suggest diverse fluids were involved in dolomitization and/or recrystallization of dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of dolomite of each succession vary from values in the range of coeval seawater to values more radiogenic than corresponding seawater, which indicate diagenetic fluids were influenced by significant water/rock interaction. High salinities (22.4–26.3 wt. % NaCl + CaCl₂) of Silurian and Ordovician dolomite–hosted fluid inclusions indicate involvement of saline waters from dissolution of Silurian evaporites. High fluid inclusion homogenization temperatures (>100°C) in all samples from Devonian to Ordovician show temperatures higher than maximum burial (60–90°C) of their host strata and suggest involvement of hydrothermal fluids in precipitation and/or recrystallization of dolomite. A thermal anomaly over the mid‐continent rift during Devonian to Mississippian time likely was the source of excess heat in the basin. Thermal buoyancy resulting from this anomaly was the driving force for migration of hydrothermal fluids through regional aquifers from the center of the Michigan Basin toward its margin. The decreasing trend of homogenization temperatures from the basin center toward its margin further supports the interpreted migration of hydrothermal fluids from the basin center toward its margin. Hydrocarbon‐bearing fluid inclusions in late‐stage Devonian to Ordovician calcite cements with high homogenization temperatures (>80°C) and their ¹³C‐depleted values (approaching ?32‰ PDB) indicate the close relationship between hydrothermal fluids and hydrocarbon migration.     

Can argillaceous formations isolate nuclear waste? Insights from isotopic,noble gas,and geochemical profiles

There is considerable interest in the use of thick argillaceous geologic formations to contain nuclear waste. Here, we show that diffusion can be the controlling transport process in these formations and diffusional time scales for δ¹⁸O and δ²H in water, dissolved He, and Cl transport in shale‐dominated aquitards are typically over 10⁶ years, well exceeding the regulatory requirements for isolation in most countries. Our scientific understanding of diffusive solute transport processes through argillaceous formations would benefit from the application of additional isotopic tracers (e.g., using new ⁴He sampling technology), multidimensional diffusive‐dispersive modeling of groundwater flow and diffusive‐dispersive solute transport over long geologic time scales, and an improved understanding of spatial heterogeneity as well as time‐dependent changes in the subsurface conditions and properties of argillaceous formations in response to events such as glaciation. Based on our current isotopic and geochemical understanding of transport, we argue that argillaceous formations can provide favorable long‐term conditions for isolating nuclear wastes.     

Groundwater discharges in the Baltic Sea: survey and quantification using a schlieren technique application

Groundwater seeps are known to occur in Eckernförde Bay, Baltic Sea. Their discharge rate and dispersion were investigated with a new schlieren technique application, which is able to visualize heterogeneous water parcels with density anomalies down to Δσ_t = 0.049 on the scale of millimeters. With the use of an inverted funnel, discharged fluids can be captured and the outflow velocity can be determined. Overall, 46 stations could be categorized by three different cases: active vent sites, seep‐influenced sites, and non‐seep sites. New seep locations were discovered, even at shallow near‐shore sites, lacking prominent sediment depression, which indicate submarine springs. The detection of numerous seeps was possible and the groundwater‐influenced area was defined to be approximately 6.3 km². Flow rates of between 0.05 and 0.71 l m^?2 min^?1 were measured. A single focused fluid plume, which was not disturbed by the funnel was recorded and revealed a flux of 59.6 ± 20 ml cm^?2 min^?1 and it was calculated that this single focused plume would be strong enough to produce a flow rate through the funnel of 1.32 ± 0.44 l m^?2 min^?1. The effect of different seep‐meter funnel sizes is discussed.