Measurement of seafloor radioactivity at the Farallon Islands Radioactive Waste Dump Site, California
No abstract available.
California↗
Geology topics
Wayne C. Shanks
Publications and source records attributed to Wayne C. Shanks.
Oxygen and iron isotope studies of magnetite produced by magnetotactic bacteria
A series of carefully controlled laboratory studies was carried out to investigate oxygen and iron isotope fractionation during the intracellular production of magnetite (Fe3O4) by two different species of magnetotactic bacteria at temperatures between 4??and 35??C under microaerobic and anaerobic conditions. No detectable fractionation of iron isotopes in the bacterial magnetites was observed. However, oxygen isotope measurements indicated a temperature-dependent fractionation for Fe3O4 and water that is consistent with that observed for Fe3O4 produced extracellularly by thermophilic Fe3+-reducing bacteria. These results contrast with established fractionation curves estimated from either high-temperature experiments or theoretical calculations. With the fractionation curve established in this report, oxygen-18 isotope values of bacterial Fe3O4 may be useful in paleoenvironmental studies for determining the oxygen-18 isotope values of formation waters and for inferring paleotemperatures.
Science↗
Alteration and mineralization of an oceanic forearc and the ophiolite-ocean crust analogy
Mineralogical, chemical, and isotopic (O, C, S, and Sr) analyses were performed on minerals and bulk rocks from a forearc basement section to understand alteration processes and compare with mid-ocean ridges (MOR) and ophiolites. Ocean Drilling Program Hole 786B in the Izu-Bonin forearc penetrates 103 m of sediment and 725 m into volcanic flows, breccias, and basal dikes. The rocks comprise boninites and andesites to rhyolites. Most of the section was affected by low-temperature (<100°C) seawater alteration, with temperatures increasing downward. The rocks are partly (5–25%) altered to smectite, Fe-oxyhydroxide, calcite, and phillipsite, and exhibit gains of K, Rb, and P, loss of Ca, variable changes in Si, Na, Mg, Fe, Sr, and Y, and elevated δ 18 O and 87 Sr/ 86 Sr. Higher temperatures (∼150°C) in the basal dikes below 750 m led to more intense alteration and formation of chlorite-smectite, corrensite, albite, K-feldspar, and quartz (±chlorite). A 5 m thick hydrothermally altered and pyritized zone at 815 m in the basal dikes reacted with mixtures of seawater and hydrothermal fluids to Mg-chlorite, albite, and pyrite, and gained Mg and S and lost Si and Ca. Focused flow of hydrothermal fluids produced serialization halos (Na-K sericite, quartz, pyrophyllite, K-feldspar, and pyrite) along quartz veins at temperatures of 200°–250°C. High 87 Sr/ 86 Sr ratios of chloritized (∼0.7055) and sericitized (∼0.7065) rocks indicate involvement of seawater via mixing with hydrothermal fluids. Low δ 34 S of sulfide (−2 to −5.5‰) and sulfate (12.5‰) are consistent with input of magmatic SO 2 into hydrothermal fluids and disproportionation to sulfide and sulfate. Alteration processes were generally similar to those at MORs, but the arc section is more intensively altered, in part because of the presence of abundant glassy rocks and mafic phases. The increase in alteration grade below 750 m and the mineralization in the basal dikes are analogous to changes that occur near the base of the volcanic section in MOR and the Troodos ophiolite.
Journal of Geophysical Research B: Solid Earth↗
Sulfur in serpentinized oceanic peridotites: Serpentinization processes and microbial sulfate reduction
The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of <1 Ma peridotites at Hess Deep occurred at high temperatures (200°–400°C) and low water/rock ratios. Oxidation of ferrous iron to magnetite maintained low ƒO 2 and produced a reduced, low-sulfur assemblage including NiFe alloy. Small amounts of sulfate reduction by thermophilic microbes occurred as the system cooled, producing low-δ 34 S sulfide (1.5‰ to −23.7‰). In contrast, serpentinization of Iberian Margin peridotites occurred at low temperatures(∼20°–200°C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher ƒO 2 . Microbial reduction of seawater sulfate resulted in addition of low-δ 34 S sulfide (∼15 to ∼43‰) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO 4 /total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high δ 34 S of total sulfur (mean ∼8‰). In contrast, Iberian Margin serpentinites gained large amounts of 34 S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in δ 34 S of total sulfur (mean ≈ −5‰). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4–14 × 10 12 g S yr −1 from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.
Journal of Geophysical Research B: Solid Earth↗
Hydrogen and oxygen isotope fractionation between brucite and aqueous NaCl solutions from 250 to 450°C
Hydrogen and oxygen isotope fractionation factors between brucite and aqueous NaCl solutions (1000lnα br-sw ) have been calibrated by experiment from 250 to 450°C at 0.5 Kb. For D/H fractionation, 1000lnα br-sw values are as follows: −32 ± 6‰ (250°C, 3.2 wt% NaCl), −21 ± 2‰ (350°C, 10.0 wt% NaCl), and −22 ± 2‰ (450°C, 3.2 wt% NaCl), indicating that brucite is depleted in D relative to coexisting aqueous NaCl solutions. These results are in good agreement with previous D/H fractionation factors determined in the brucite-water system, indicating that any effects of dissolved salt on D/H fractionation are relatively small, particularly in solutions with near seawater salinity. The maximum salt effect (+4‰) was observed in 10.0 wt% NaCl solutions at 350°C, suggesting that the addition of dissolved NaCl increases the amount of deuterium fractionated into mineral structures. For 18 O/ 16 O fractionation, 1000lnα br-sw values in 3.0 wt% NaCl solutions are −6.0 ± 1.3‰, −5.6 ± 0.7‰ and −4.1 ± 0.2‰, at 250, 350, and 450°C, respectively, and −5.8 ± 0.6‰ in 10.0 wt % NaCl at 350°C. These data indicate that brucite is depleted in 18 O relative to coexisting aqueous NaCl solutions and that the degree of depletion decreases slightly with increasing temperature and is not strongly dependent on salinity. We calculated 18 O/ 16 O brucite-water fractionation factors from available calibrations of the salt-effect on 18 O/ 16 O fractionation between coexisting phases. The resulting values were fit to the following equation that is valid from 250 to 450°C 1000ln α br-w = 9.54 × 10 6 T −2 − 3.53 × 10 4 T −1 + 26.58 where T is temperature in Kelvins. These new data have been used to improve the prediction of 18 O/ 16 O fractionation factors in the talc-water and serpentine-water systems by modifying existing empirical bond-water models. The results of this analysis indicate that the δ 18 O composition of talc-brucite and serpentine-brucite pairs could be used as a geothermometer and that these coexisting phases should display the following order of 18 O enrichment: talc > serpentine > brucite.
Geochimica et Cosmochimica Acta↗
The deep structure of a sea-floor hydrothermal deposit
Hydrothermal circulation at the crests of mid-ocean ridges plays an important role in transferring heat from the interior of the Earth. A consequence of this hydrothermal circulation is the formation of metallic ore bodies known as volcanic-associated massive sulphide deposits. Such deposits, preserved on land, were important sources of copper for ancient civilizations and continue to provide a significant source of base metals (for example, copper and zinc). Here we present results from Ocean Drilling Program Leg 169, which drilled through a massive sulphide deposit on the northern Juan de Fuca spreading centre and penetrated the hydrothermal feeder zone through which the metal-rich fluids reached the sea floor. We found that the style of feeder-zone mineralization changes with depth in response to changes in the pore pressure of the hydrothermal fluids and discovered a stratified zone of high-grade copper-rich replacement mineralization below the massive sulphide deposit. This copper-rich zone represents a type of mineralization not previously observed below sea-floor deposits, and may provide new targets for land-based mineral exploration.
Nature↗
Oxygen and hydrogen isotope systematics of Lake Baikal, Siberia: Implications for paleoclimate studies
We interpret oxygen and hydrogen isotope data for water samples from Lake Baikal, Siberia, its tributaries and other local rivers, and local precipitation in terms of the known water budget for the modem lake in order to gain insight into past limnological and climatic processes that influenced the lake. Lake Baikal is remarkably uniform in its isotopic composition (??18O = -15.8 ?? 0.2???; ??D = -123 ?? 2???) and lies slightly to the right of the global meteoric water line, which suggests significant evaporation. Water is supplied to the lake by over 300 rivers and streams. The oxygen isotope values (??18O) of the rivers in the Baikal catchment range from -13.4 to -21.2???. The hydrogen isotope values (??D) for the same area range from -103 to -156???. Both these ranges generally conform to the global meteoric water line. The weighted average isotopic composition of input to the lake (rivers plus precipitation) is -15.2??? for ??18O and -116??? for ??D, values higher than those of the modem lake. Therefore, the isotopic composition of the modem lake cannot be related to the modem input through simple evaporation. Instead, modeling of the isotopic mass balance of the lake suggests that inputs (precipitation and influx from rivers) and outputs (evaporation and outflow) are not at a steady-state equilibrium under current climate conditions. We found previous input to the lake had lower ??18O and ??D values than modem input, which reflects cooler climates in the past compared with modern conditions. Under constant climate conditions, steady-state conditions are not expected to be reached by the lake for at least 700 yr because of its large size and the long residence time of water in the lake.
Limnology and Oceanography↗
Direct observation of the evolution of a seafloor 'black smoker' from vapor to brine
A single hydrothermal vent, ‘F’ vent, occurring on very young crust at 9°16.8′N, East Pacific Rise, was sampled in 1991 and 1994. In 1991, at the measured temperature of 388°C and seafloor pressure of 258 bar, the fluids from this vent were on the two-phase curve for seawater. These fluids were very low in chlorinity and other dissolved species, and high in gases compared to seawater and most sampled seafloor hydrothermal vent fluids. In 1994, when this vent was next sampled, it had cooled to 351°C and was venting fluids ∼ 1.5 times seawater chlorinity. This is the first reported example of a single seafloor hydrothermal vent evolving from vapor to brine. The 1991 and 1994 fluids sampled from this vent are compositionally conjugate pairs to one another. These results support the hypothesis that vapor-phase fluids vent in the early period following a volcanic eruption, and that the liquid-phase brines are stored within the oceanic crust, and vent at a later time, in this case 3 years. These results demonstrate that the venting of brines can occur in the same location, in fact from the same sulfide edifice, where the vapor-phase fluids vented previously.
Earth and Planetary Science Letters↗
Hydrogen isotope systematics of phase separation in submarine hydrothermal systems: Experimental calibration and theoretical models
Hydrogen isotope fractionation factors were measured for coexisting brines and vapors formed by phase separation of NaCl/H2O fluids at temperatures ranging from 399-450??C and pressures from 277-397 bars. It was found that brines are depleted in D compared to coexisting vapors at all conditions studied. The magnitude of hydrogen isotope fractionation is dependent on the relative amounts of Cl in the two phases and can be empirically correlated to pressure using the following relationship: 1000 ln ??(vap-brine) = 2.54(??0.83) + 2.87(??0.69) x log (??P), where ??(vap-brine) is the fractionation factor and ??P is a pressure term representing distance from the critical curve in the NaCl/H2O system. The effect of phase separation on hydrogen isotope distribution in subseafloor hydrothermal systems depends on a number of factors, including whether phase separation is induced by heating at depth or by decompression of hydrothermal fluids ascending to the seafloor. Phase separation in most subseafloor systems appears to be a simple process driven by heating of seawater to conditions within the two-phase region, followed by segregation and entrainment of brine or vapor into a seawater dominated system. Resulting vent fluids exhibit large ranges in Cl concentration with no measurable effect on ??D. Possible exceptions to this include hydrothermal fluids venting at Axial and 9??N on the East Pacific Rise. High ??D values of low Cl fluids venting at Axial are consistent with phase separation taking place at relatively shallow levels in the oceanic crust while negative ??D values in some low Cl fluids venting at 9??N suggest involvement of a magmatic fluid component or phase separation of D-depleted brines derived during previous hydrothermal activity.
Geochimica et Cosmochimica Acta↗
Variations in the chemical and stable isotope composition of carbon and sulfur species during organic-rich sediment alteration: An experimental and theoretical study of hydrothermal activity at Guaymas Basin, Gulf of California
Organic-rich diatomaceous ooze was reacted with seawater and a Na-Ca-K-Cl fluid of seawater chlorinity at 325–400°C, 400–500 bars, and fluid/sediment mass ratios of 1.56–2.35 to constrain factors regulating the abundance and stable isotope composition of C and S species during hydrothermal alteration of sediment from Guaymas Basin, Gulf of California. Alteration of inorganic and organic sedimentary components resulted in extensive exchange reactions, the release of abundant H 2 S, CO 2 , CH 4 , and C organic , to solution, and recrystallization of the sediment to an assemblage containing albitic plagioclase, quartz, pyrrhotite, and calcite. The δ 34 S cdt "> δ 34 S cdt values of dissolved H 2 S varied from −10.9 to +4.3‰ during seawater-sediment interaction at 325 and 400°C and from −16.5 to −9.0‰ during Na-Ca-K-Cl fluid-sediment interaction at 325 and 375°C. In the absence of seawater SO 4 , H 2 S is derived from both the transformation of pyrite to pyrrhotite and S released during the degradation of organic matter. In the presence of seawater SO 4 , reduction of SO 4 contributes directly to H 2 S production. Sedimentary organic matter acts as the reducing agent during pyrite and SO 4 reduction. Requisite acidity for the reduction of SO 4 is provided by Mg fixation during early-stage sediment alteration and by albite and calcite formation in Mg-free solutions. Organically derived CH 4 was characterized by δ 13 C pdb "> δ13Cpdb values ranging between −20.8 and −23.1‰, whereas δ 13 C pdb "> δ 13 C pdb values for dissolved C organic ranged between −14.8 and −17.7%. Mass balance calculations indicate that δ 13 C values for organically derived CO 2 were ≥ − 14.8%. Residual solid sedimentary organic C showed small (≤ 0.7‰) depletions in 13 C relative to the starting sediment. The experimental results are consistent with the isotopic and chemical composition of natural hydrothermal fluids and minerals at Guaymas Basin and permit us to better constrain sources and sinks for C and S species in subseafloor hydrothermal systems at sediment-covered spreading centers. Our data show that the sulfur isotope composition of hydrothermal Sulfide minerals in Guaymas Basin can be explained by derivation of S from diagenetic sulfide and seawater sulfate. Basaltic S may also contribute to hydrothermal sulfide precipitates but is not required to explain their isotopic composition. Estimates of seawater/ sediment mass ratios based on sulfur isotopic composition of sulfide minerals and the abundance of dissolved NH 3 in vent fluids range from 3–29 during hydrothermal circulation. Sources of C in Guaymas Basin hydrothermal fluids include thermal degradation of organic matter, bacteriogenic methane production, and dissolution of diagenetic carbonate.
Baja California Sur↗
Karstification without carbonic acid: Bedrock dissolution by gypsum- driven dedolomitization
Aggressive karstification can take place where dolomite and gypsum are in contact with the same aquifer. Gypsum dissolution drives the precipitation of calcite, thus consuming carbonate ions released by dolomite. Lake Banyoles, in northeastern Spain, is a karst lake supplied by sublacustrine springs, and karstic collapse is occurring in the immediate vicinity of the lake. Lake water is dominated by Mg-Ca and SO 4 -HCO 3 , and is supersaturated with calcite that is actively accumulating in lake sediments. Water chemistry, sulfur isotope composition, local stratigraphy, and mass-balance modelling suggest that the primary karst-forming process at at Lake Banyoles is dedolomitization of basement rocks driven by gypsum dissolution. Karstification takes place along the subsurface contact between the gypsiferous Beuda Formation and the dolomitic Perafita Formation. This process is here recognized for the first time to cause karstification on a large scale; this is significant because it proceeds without the addition of soil-generated carbonic acid. Gypsum-driven dedolomitization may be responsible for other karstic systems heretofore attributed to soil-generated carbonic acid.
Geology↗
Genesis of massive sulfide deposits on a sediment-covered spreading center, Escanaba Trough, southern Gorda Ridge
No abstract available.
Economic Geology↗
Volcanic eruption of the mid-ocean ridge along the East Pacific Rise crest at 9°45-52'N: direct submersible observations of seafloor phenomena associated with an eruption event in April, 1991
In April, 1991, we witnessed from the submersible Alvin a suite of previously undocumented seafloor phenomena accompanying an in-progress eruption of the mid-ocean ridge on the East Pacific Rise crest at 9°45′N–52′N. The volume of the eruption could not be precisely determined, although comparison of pre- and post-eruption SeaBeam bathymetry indicate that any changes in ridge crest morphology resulting from the eruption were < 10 m high. Effects of the eruption included: (1) increased abundance and redistribution of hydrothermal vents, disappearance of numerous vent communities, and changes in characteristics of vent fauna and mineral deposits within the eruption area since December, 1989; (2) murkiness of bottom waters up to tens of meters above the seafloor due to high densities of suspended mineral and biogenic particulates; (3) destruction of a vent community by lava flows, mass wasting, and possible hydrovolcanic explosion at a site known as ‘Tubeworm Barbecue’ in the axial summit caldera (ASC) at 9°50.6′N; (4) near-critical temperatures of hydrothermal vent fluids, ranging up to 403°C; (5) temporal variations over a 2 week interval in both temperatures and chemical/isotopic compositions of hydrothermal fluids; (6) unusual compositions of end-member vent fluids, with pH values ranging to a record low of 2.5, salinities ranging as low as 0.3 wt% NaCl (one-twelfth that of seawater), and dissolved gases reaching high concentrations (> 65 mmol/l for both CO 2 and H 2 S); (7) venting at temperatures above 380°C of visually detectable white vapor that transformed to plumes of gray smoke a few centimeters above vent orifices; (8) disorganized venting of both high-temperature fluids (black and gray smoke) and large volumes of cooler, diffuse hydrothermal fluids directly from the basaltic seafloor, rather than from hydrothermal mineral constructions; (9) rapid and extensive growth of flocculent white bacterial mats (species unknown) on and under the seafloor in areas experiencing widespread venting of diffuse hydrothermal fluid; and (10) subseafloor downslope migration of magma normal to the ridge axis in a network of small-scale (1–5 m diameter) lava tubes and channels to distances at least 100–200 m outside the ASC. We suggest that, in April, 1991, intrusion of dikes in the eruption area to < 200 m beneath the ASC floor resulted in phase separation of fluids near the tops of the dikes and a large flux of vapor-rich hydrothermal fluids through the overlying rubbly, cavernous lavas. Low salinities and gas-rich compositions of hydrothermal fluids sampled in the eruption area are appropriate for a vapor phase in a seawater system undergoing subcritical liquid-vapor phase separation (boiling) and phase segregation. Hydrothermal fluids streamed directly from fissures and pits that may have been loci of lava drainback and/or hydrovolcanic explosions. These fissures and pits were lined with white mats of a unique fast-growing bacteria that was the only life associated with the brand-new vents. The prolific bacteria, which covered thousands of square meters on the ridge crest and were also abundant in subseafloor voids, may thrive on high levels of gases in the vapor-rich hydrothermal fluids initially escaping the hydrothermal system. White bacterial particulates swept from the seafloor by hydrothermal vents swirled in an unprecedented biogenic ‘blizzard’ up to 50 m above the bottom. The bacterial proliferation of April, 1991 is likely to be a transient bloom that will be checked quickly either by decline of dissolved gas concentrations in the fluids as rapid heat loss brings about cessation of boiling, and/or by grazing as other organisms are re-established in the biologically devastated area.
Earth and Planetary Science Letters↗
Cycling of sulfur in subduction zones: The geochemistry of sulfur in the Mariana Island Arc and back-arc trough
The sulfur contents and sulfur isotopic compositions of 24 glassy submarine volcanics from the Mariana Island Arc and back-arc Mariana Trough were determined in order to investigate the hypothesis that subducted seawater sulfur (δ 34 S= 21‰) is recycled through arc volcanism. Our results for sulfur are similar to those for subaerial arc volcanics: Mariana Arc glasses are enriched in 34 S (δ 34 S=up to10.3‰,mean= 3.8‰) and depleted in S (20–290 ppm, mean = 100 ppm) relative to MORB (850 ppm S,δ 34 S= 0.1 ± 0.5‰). The back-arc trough basalts contain 200–930 ppm S and haveδ 34 S values of1.1 ± 0.5‰, which overlap those for the arc and MORB. The low sulfur contents of the arc and some of the trough glasses are attributed to (1) early loss of small amounts of sulfur through separation of immiscible sulfide and (2) later vapor-melt equilibrium control of sulfur contents and loss of sulfur in a vapor phase from sulfide-undersaturated melts near the minimum in sulfur solubility atƒO 2 ≈NNO (nickel-nickel oxide). Although these processes removed sulfur from the melts their effects on the sulfur isotopic compositions of the melts were minimal. Positive trends ofδ 34 S with 87 Sr/ 86 Sr, LILE and LREE contents of the arc volcanics are consistent with a metasomatic seawater sulfur component in the depleted sub-arc mantle source. The lack of a 34 S-rich slab signature in the trough lavas may be attributed to equilibration of metasomatic fluid with mantle material along the longer pathway from the slab to the source of the trough volcanics. Sulfur is likely to have been transported into the mantle wedge by metasomatic fluid derived from subducted sediments and pore fluids.
Earth and Planetary Science Letters↗
Origin of stratiform sediment-hosted manganese carbonate ore deposits: Examples from Molango, Mexico, and TaoJiang, China
Carbonate and sulfide minerals from the Molango, Mexico, and TaoJiang, China, Mn deposits display similar and distinctive ??34S and ??13C patterns in intervals of manganese carbonate mineralization. ??13C-values for Mn-bearing carbonate range from -17.8 to +0.5??? (PDB), with the most negative values occurring in high-grade ore zones that are composed predominantly of rhodochrosite. In contrast, calcite from below, within and above Mn-carbonate zones at Molango has ??13C???0??? (PDB). Markedly negative ??13C data indicate that a large proportion of the carbon in Mn-carbonates was derived from organic matter oxidation. Diagenetic reactions using MnO2 and SO2-4 to oxidize sedimentary organic matter were the principle causes of such 12C enrichment. Pyrite content and sulfide ?? 34S-values also show distinctive variations. In unmineralized rocks, very negative ??34S-values (avg. < -21??? CDT) and abundant pyrite content suggest that pyrite formed from diagenetic, bacteriogenic sulfate reduction. In contrast, Mn-bearing horizons typically contain only trace amounts of pyrite (e.g., <0.5 wt% S with ??34S-values 34S-enriched, in some cases to nearly the value for contemporaneous seawater. 34S-enriched pyrite from the Mn-carbonate intervals indicates sulfide precipitation in an environment that underwent extensive SO2-4 reduction, and was largely a closed system with regard to exchange of sulfate and dissolved sulfide with normal seawater. The occasional occurrence of 34S-depleted pyrite within Mn-carbonate zones dominated by 34S-enriched pyrite is evidence that closed-system conditions were intermittent and limited to local pore waters and did not involve entire sedimentary basins. Mn-carbonate precipitation may have occluded porosity in the surficial sediments, thus establishing an effective barrier to SO2-4 exchange with overlying seawater. Similar isotopic and mineralogic characteristics from both the Molango and TaoJiang deposits, widely separated in geologic time and space, suggest they were formed similarly by MnO2 precipitation at the margins of dysaerobic to anoxic marine basins. Mn-carbonate formed predominantly by early-diagenetic reduction of Mn-oxides via oxidation of organic matter in near-surface sediments. In addition to MnCO3 precipitation, organic matter oxidation reactions resulted in oxidation of FeS to Fe-oxides such as magnetite, maghemite and hematite. The latter process explains anomalously low pyrite content and abundant Fe-oxide minerals in ore zones dominated by rhodochrosite. ?? 1992.
Chemical Geology↗
Sulfur isotopic disequilibrium and fluid-rock interaction during metamorphism of sulfidic black shales from the Waterville-Augusta area, Maine, USA
Sulfur isotope ratios of pyrite (py) and pyrrhotite (po) from regionally metamorphosed graphitic sulfidic schists and related rocks from south-central Maine, USA, were analysed using SO 2 and SF 6 techniques. There is a broad range in δ 34 S values for both pyrite and pyrrhotite at most outcrops, up to 8%. and overall the values are isotopically light, averaging ~ −27‰ for the entire data set, suggesting that the rocks have not been grossly isotopically disturbed by regional metamorphism from their inferred organic-rich sedimentary origins. At all temperatures from chlorite to sillimanite grades, sulfide analysed from veins and blebs within the schists show predominantly disequilibrium fractionations ranging from Δ 34 S py-po −3.0 to +3.5‰ "> Δ 34 S py-po −3.0to+3.5‰ , as do matrix sulfides from rocks that attained temperatures <500°C. Only at T > 500° C do matrix pyrite-pyrrhotite pairs with polygonal or aligned granoblastic microstructures approach isotopic equilibrium at millimeter to centimeter scales, suggesting that the process that favoured equilibration was recrystallization accompanying metamorphism and deformation. This disequilibrium may be a function of preferential interaction of one of the phases with an infiltrating fluid, but the lack of any systematic trends in the data, particularly with both negative and positive Δ 34 S py-po at some outcrops, does not permit ready identification of fluid sources, fluxes, or compositions. By combining published fluid fluxes for the area and a knowledge of the mass of sulfur contained in the rocks and the inferred infiltrating fluid, it appears that sulfur should have been homogenized over at least 10's to 1000's of meters, if equilibrium had been attained between rock sulfides and an infiltrating fluid of constant composition. That this did not occur was probably due to lack of equilibration between sulfides and the fluid but may also have arisen because of channelling of fluid flow along rather than across layers, or a lack of fluid infiltration through this unit.
Geochimica et Cosmochimica Acta↗
Sulfur, carbon, and oxygen isotope variations in submarine hydrothermal deposits of Guaymas Basin, Gulf of California, USA
Sulfur, carbon, and oxygen isotope values were measured in sulfide, sulfate, and carbonate from hydrothermal chimney, spire, and mound samples in the southern trough of Guaymas Basin, Gulf of California, USA. δ 34 S values of sulfides range from −3.7 to 4.5%. and indicate that sulfur originated from several sources: 1. (1) dissolution of 0‰ sulfide contained within basaltic rocks, 2. (2) thermal reduction of seawater sulfate during sediment alteration reactions in feeder zones to give sulfide with positive δ 34 S , and 3. (3) entrainment or leaching of isotopically light (negative- δ 34 S ) bacteriogenic sulfide from sediments underlying the deposits. δ 34 S of barite and anhydrite indicate sulfur derivation mainly from unfractionated seawater sulfate, although some samples show evidence of sulfate reduction and sulfide oxidation reactions during mixing within chimneys. Oxygen isotope temperatures calculated for chimney calcites are in reasonable agreement with measured vent fluid temperatures and fluid inclusion trapping temperatures. Hydrothermal fluids that formed calcite-rich chimneys in the southern trough of Guaymas Basin were enriched in 18 O with respect to seawater by about 2.4‰ due to isotopic exchange with sedimentary and/or basaltic rocks. Carbon isotope values of calcite range from −9.6 to −14.0‰ δ 34 C pDB , indicating that carbon was derived in approximately equal quantities from the dissolution of marine carbonate minerals and the oxidation of organic matter during migration of hydrothermal fluid through the underlying sediment column. Statistically significant positive, linear correlations of δ 34 S , δ 34 C , and δ 18 O of sulfides and calcites with geographic location within the southern trough of Guaymas Basin are best explained by variations in water/rock ( w r "> wr ) ratios or sediment reactivity within subsurface alteration zones. Low w r "> wr ratios and the leaching of detrital carbonates and bacteriogenic sulfides at the southern vent sites result in relatively high δ 13 C and low δ 34 S in chimney carbonates and sulfides, respectively. In the north, where the depletion of alkalis in vent fluids indicates higher w r "> wr ratios, positive δ 34 S and more negative δ 13 c are due to increased contributions from organic matter oxidation and sulfate reduction reactions.
Geochimica et Cosmochimica Acta↗
Thermal springs in Lake Baikal
Pore waters extracted from sediment cores were analyzed for their oxygen and hydrogen isotopic compositions and major ion chemistry to determine the source of water from a vent area for diffuse lake-bottom thermal springs or seeps in Frolikha Bay, northeastern Lake Baikal. The δ 18 O values of pore waters range from -15.2‰ to -16.7‰, and δD values range from -119‰ to -126‰ (both isotopes determined relative to standard mean ocean water [SMOW]). Bottom water in Lake Baikal has a δ 18 O value of -5.6‰ and a δD value of -120‰ Pore waters in the vent area are significantly enriched in Mg, B, Ca, and especially Na and have the lowest δD and δ 18 O values; these pore waters are isotopically and chemically distinct from pore waters in other, more typical parts of the lake. The pore-water isotopic data fall on a local meteoric water line, and covariations in water isotopes and chemistry are not consistent with evaporation or hydrothermal water-rock interaction. The thermal springs represent discharging meteoric waters that have been gently heated during subsurface circulation and are largely unaltered isotopically. Chemical variations are most likely due to dissolution of subsurface evaporites.
Geology↗