Serpentinization of abyssal peridotites from the MARK area, Mid-Atlantic Ridge: sulfur geochemistry and reaction modeling

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated δ³⁴S_sulfide (3.7 to 12.7‰). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high δ³⁴S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (∼400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ∼300°C. Serpentinization produces highly reducing conditions and significant amounts of H₂ and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in ¹³C (up to 4.5‰) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 × 10¹² g seawater S yr⁻¹. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.     

Iron partitioning and hydrogen generation during serpentinization of abyssal peridotites from 15°N on the Mid-Atlantic Ridge

Aqueous dihydrogen (H₂,aq) is produced in copious amounts when seawater interacts with peridotite and H₂O oxidizes ferrous iron in olivine to ferric iron in secondary magnetite and serpentine. Poorly understood in this process is the partitioning of iron and its oxidation state in serpentine, although both impose an important control on dihydrogen production. We present results of detailed petrographic, mineral chemical, magnetic and Mößbauer analyses of partially to fully serpentinized peridotites from the Ocean Drilling Program (ODP) Leg 209, Mid-Atlantic Ridge (MAR) 15°N area. These results are used to constrain the fate of iron during serpentinization and are compared with phase equilibria considerations and peridotite-seawater reaction path models. In samples from Hole 1274A, mesh-rims reveal a distinct in-to-out zoning from brucite at the interface with primary olivine, followed by a zone of serpentine + brucite ± magnetite and finally serpentine + magnetite in the outermost mesh-rim. The compositions of coexisting serpentine (Mg# 95) and brucite (Mg# 80) vary little throughout the core. About 30-50% of the iron in serpentine/brucite mesh-rims is trivalent, irrespective of subbasement depth and protolith (harzburgite versus dunite). Model calculations suggest that both partitioning and oxidation state of iron are very sensitive to temperature and water-to-rock ratio during serpentinization. At temperatures above 330 °C the dissolution of olivine and coeval formation of serpentine, magnetite and dihydrogen depends on the availability of an external silica source. At these temperatures the extent of olivine serpentinization is insufficient to produce much hydrogen, hence conditions are not reducing enough to form awaruite. At T < 330 °C, hydrogen generation is facilitated by the formation of brucite, as dissolution of olivine to form serpentine, magnetite and brucite requires no addition of silica. The model calculations suggest that the iron distribution observed in serpentine and brucite is consistent with formation temperatures ranging from <150 to 250 °C and bulk water-to-rock ratios between 0.1 and 5. These conditions coincide with peak hydrogen fugacities during serpentinization and are conducive to awaruite formation during main stage serpentinization. The development of the common brucite rims around olivine is either due to an arrested reaction olivine → brucite → serpentine + brucite, or reflects metastable olivine-brucite equilibria developing in the strong gradient in silica activity between orthopyroxene (talc-serpentine) and olivine (serpentine-brucite).     

Post-emplacement serpentinization and related hydrothermal metamorphism in a kimberlite from Venetia, South Africa

The common serpentine–diopside matrix assemblage in volcaniclastic kimberlite (VK) at the Venetia Mine, South Africa is ascribed to a secondary origin, because of post‐emplacement serpentinization and associated hydrothermal metamorphism. Volcaniclastic deposits with 20–30% porosity infill kimberlite pipes in the waning stages of kimberlite eruptions. Olivine macrocrysts are typically rimmed by talc and are pseudomorphed by lizardite, with minor magnetite. The fine matrix consists of mixtures of lizardite, chlorite, smectite, brucite, calcite, titanite and andradite, an assemblage which either pseudomorphed microcrysts or in‐filled voids. Locally we recognize microcryst pseudomorphs rich in sub‐microscopic mixtures of lizardite with smectite, and other microcryst pseudomorphs and void‐filling matrix rich in chlorite and lizardite. Interstitial lizardite and associated phyllosilicates (brucite, smectite and chlorite) crystallized progressively from meteoric or hydrothermally derived pore waters, and Si⁴⁺ and Mg²⁺ released into the fluid phase during serpentinization of olivine macrocrysts. Radial‐fibrous fringes of diopside microlites around crystals display void‐filling textures because of unrestricted growth into pore spaces. Secondary diopside is attributed to Si⁴⁺, Mg²⁺ and Ca²⁺ cations released into the fluid phase by interaction with olivine, calcite and plagioclase in siliceous xenoliths. The paucity of primary, fine‐grained groundmass phases resistant to alteration, for example, perovskite and spinel, precludes an origin for the intergrain matrix as altered interstitial ash, glass or a late‐stage kimberlite melt. Isovolumetric replacement of olivine results in a volume increase of 60% so that pore spaces in the original deposit can be easily filled up with serpentine. The source of Al³⁺ to form chlorite and smectite is attributed to alteration of plagioclase in xenoliths which comprise 20–30 vol.% of the deposit. Titanite, hydro‐andradite and second‐generation diopside precipitate as hydrothermal minerals from calcium‐bearing serpentinizing fluids in replacement reactions and as void‐filling minerals. Consideration of mineral equilibria in the CaO‐MgO‐SiO₂‐H₂O‐CO₂ system constrains the common matrix assemblage of lizardite and diopside in X_CO2)–T space. At 300 bar, the assemblage is stable only at temperatures below 370 °C and X_CO2 < 0.01. This upper limit on temperature is well below the plausible solidus of ultrabasic magmas. Furthermore, the requirement of trace CO₂ in the fluid phase implies a post‐emplacement external source rather than ‘autometamorphism’ from kimberlite‐derived fluids, because of high P_CO2 commonly inferred for kimberlite magmas.     

High temperature alteration of Abyssal ultramafics from the Islas Orcadas Fracture Zone,South Atlantic

Ultramafic rocks dredged from the Islas Orcadas Fracture Zone, along the SW Indian Ocean Ridge (6° E and 54° S), show evidence of progressive hydration beginning at temperatures greater than 600° C (and perhaps as high as 900° C) and continuing to less than 50° C. There are two principal types of alteration present in the ultramafic rocks, both of which are the result of hydration reactions. The first type of alteration involves hydration of original clinopyroxene, orthopyroxene and olivine to amphibole, talc, secondary olivine, and serpentine. The second is a vein type of alteration and results in the formation of veins of amphibole, chlorite, talc and serpentine. — The alteration appears to be episodic. The sequence of events suggested by the petrography is: 1) clinopyroxene altering to amphibole; 2) orthopyroxene altering to talc, or talc + olivine; 3) supersolvus hornblende veining; 4) coexisting actinolite + hornblende veining; 5) chlorite, chlorite + actinolite, or chlorite + secondary clinopyroxene veining; 6) talc veining; 7) serpentine veining; and 8) pervasive serpentinization. — The alteration fluid is most likely seawater. It is suggested that the high temperature alterations may reflect seawater circulation into the upper mantle.     

Present day serpentinization in New Caledonia,Oman and Yugoslavia

Geochemical evidence for modern low-temperature serpentinization has been found in three new localities. Apparently the low-temperature reactions are a common mode of formation of the lizardite-chrysotile and brucite assemblage. Possibly the ¹⁸O content of serpentine formed at low temperatures is in part inherited from the pyroxene and olivine.     

Mineralogical, geochemical and isotopic characteristics of hydrothermal alteration processes in the active, submarine, felsic-hosted PACMANUS field, Manus Basin, Papua New Guinea

During ODP Leg 193, 4 sites were drilled in the active PACMANUS hydrothermal field on the crest of the felsic Pual Ridge to examine the vertical and lateral variations in mineralization and alteration patterns. We present new data on clay mineral assemblages, clay and whole rock chemistry and clay mineral strontium and oxygen isotopic compositions of altered rocks from a site of diffuse low-temperature venting (Snowcap, Site 1188) and a site of high-temperature venting (Roman Ruins, Site 1189) in order to investigate the water-rock reactions and associated elemental exchanges.The volcanic succession at Snowcap has been hydrothermally altered, producing five alteration zones: (1) chlorite ± illite-cristobalite-plagioclase alteration apparently overprinted locally by pyrophyllite bleaching at temperatures of 260-310°C; (2) chlorite ± mixed-layer clay alteration at temperatures of 230°C; (3) chlorite and illite alteration; (4) illite and chlorite ± illite mixed-layer alteration at temperatures of 250-260°C; and (5) illite ± chlorite alteration at 290-300°C. Felsic rocks recovered from two holes (1189A and 1189B) at Roman Ruins, although very close together, show differing alteration features. Hole 1189A is characterized by a uniform chlorite-illite alteration formed at ∼250°C, overprinted by quartz veining at 350°C. In contrast, four alteration zones occur in Hole 1189B: (1) illite ± chlorite alteration formed at ∼300°C; (2) chlorite ± illite alteration at 235°C; (3) chlorite ± illite and mixed layer clay alteration; and (4) chlorite ± illite alteration at 220°C.Mass balance calculations indicate that the chloritization, illitization and bleaching (silica-pyrophyllite assemblages) alteration stages are accompanied by different chemical changes relative to a calculated pristine precursor lava. The element Cr appears to have a general enrichment in the altered samples from PACMANUS. The clay concentrate data show that Cr and Cu are predominantly present in the pyrophyllites. Illite shows a significant enrichment for Cs and Cu relative to the bulk altered samples.Considerations of mineral stability allow us to place some constraints on fluid chemistry. Hydrothermal fluid pH for the chloritization and illitization was neutral to slightly acidic and relatively acidic for the pyrophyllite alteration. In general the fluids, especially from Roman Ruins and at intermediate depths below Snowcap, show only a small proportion of seawater mixing (<10%). Fluids in shallow and deep parts of the Snowcap holes, in contrast, show stronger seawater influence.     

Ti-content of high-Ca pyroxenes as a petrogenetic indicator: an experimental study of Mafic Alkaline Rocks from the Mt. Erebus volcanic region,Antarctica

We report chemical and mineralogical data for one atmosphere melting experiments conducted on alkalic rocks from the Mt. Erebus volcanic region: DVDP2 basanite, two hawaiites (DVDP2 and a nepheline-bearing variety), and an anorthoclase phonolite. Temperatures between 1,224 and 1,049°C were investigated at f_O2~QFM. DVDP2 basanite appears to be an intermediate pressure liquid or a cumulate, because only olivine coexists with melt from above 1,224–1,160°C. High-Ca pyroxene joins olivine in the crystallization sequence at 1,138°C. These minerals are joined by plagioclase at a temperature between 1,120 and 1,104°C. In contrast, DVDP2 hawaiite appears to be relatively evolved, because it is multiply saturated with olivine, plagioclase, and high-Ca pyroxene near its liquidus (between 1,120 and 1,104°C). Plagioclase crystallizes in the Ne-hawaiite by 1,160°C followed by olivine below 1,120°C. The liquidus of anorthoclase phonolite is between the lowest temperatures investigated, 1,089 and 1,049°C, and plagioclase is the liquidus mineral. Our results indicate that DVDP2 hawaiite can be derived from a DVDP2 basanitic parental magma by crystal fractionation at low pressures, that the nepheline hawaiite is an olivine cumulate, and that the liquids parental to the anorthoclase phonolite represent the end products of crystal fractionation. They also allow us to illustrate how the Ti-content of pyroxene may be used as a petrogenetic indicator of processes and events in the evolution of the Erebus volcanic system.     

Redox evolution and mass transfer during serpentinization: An experimental and theoretical study at 200 °C, 500 bar with implications for ultramafic-hosted hydrothermal systems at Mid-Ocean Ridges

Highly reducing and high-pH vent fluids characterize moderately low temperature ultramafic-hosted hydrothermal systems, such as the recently discovered Lost City hydrothermal field at 30°N Mid-Atlantic Ridge Ridge (MAR). To better understand the role of mineral reaction rates on changes in fluid chemistry and mineralization processes in these and similar systems, we conducted an experimental study involving seawater and peridotite at 200 °C, 500 bar. Time series changes in fluid chemistry were monitored and compared with analogous data predicted using experimental and theoretical data for mineral dissolution rates. Although there was qualitative agreement between predicted and measured changes in the chemical evolution of the fluid for some species, the rate and magnitude of increase in pH, dissolved chloride and H₂ did not agree well with predictions based on theoretical modeling results. Experimental data indicate that dissolved H₂ abruptly and intermittently increased, reaching a value only approximately 20% of that predicted assuming magnetite as the primary Fe-bearing alteration phase. The distribution and valence of Fe in primary and secondary minerals reveal that the most abundant secondary mineral, serpentine, contained significant amounts of both ferric and ferrous Fe, with the less abundant brucite, also being Fe-rich (X_Fe = 0.3). Surprisingly, magnetite was present in only trace amounts, indicating that H₂ generation was largely accommodated by the formation of Fe-chrysotile. Accordingly, the diversity of Fe-bearing secondary minerals together with rates of serpentinization less than theoretically predicted, account best for the relatively low dissolved H₂ concentrations produced. Thus, the experimental data can be used to obtain provisional estimates of thermodynamic data for Fe-bearing minerals, enhancing the application of reaction path models depicting mass transfer processes during serpentinization at mid-ocean ridges. Similarly, the observed differences between theoretically predicted and experimentally measured pH values result from constraints imposed by complex patterns of mass transfer inherent to the experimental system. In particular, the experimental observation of a late stage increase in Na/Cl ratio likely results from the dissolution of a Na₂O component of clinopyroxene, which causes pH to increase sufficiently to induce precipitation of a Ca-bearing phase, perhaps portlandite. As with the redox variability observed during the experiment, this event could not be predicted, underscoring the need to use caution when modeling alteration processes in the chemically complex ultramafic-hosted hydrothermal systems at elevated temperatures and pressures.     

Contact metamorphism/hydrothermal alteration of Tertiary basalts from the Isle of Skye,northwest Scotland

Alkali olivine basalts from Skye were simultaneously contact metamorphosed by Tertiary gabbro and granite intrusions and altered by the hydrothermal convection system that the plutons induced. Four metamorphic zones were mapped around the plutons. Furthest from the intrusions, in the primary olivine zone, metabasalts are composed of combinations of igneous olivine, augite, plagioclase, titaniferous magnetite, ilmenite, zeolites, gyrolite, sulfides, and chlorite-smectite intergrowths. Closer to the plutons, in the smectite zone, saponite and carbonate appear, primary olivine and gyrolite disappear, and zeolites decrease dramatically in abundance. Still closer to the plutons, in the amphibole zone, actinolite, edenite, chlorite, sphene, epidote, andradite, and quartz appear and saponite and chlorite-smectite intergrowths disappear. Along parts of the contact between gabbro and basalt, in the orthopyroxeneolivine zone, orthopyroxene, metamorphic olivine, and biotite appear and amphibole, chlorite, sphene, epidote, andradite, carbonate, and quartz disappear. Whole-rock chemical data indicate only minor change in the major-element chemical composition of the metabasalts during progressive metamorphism/hydrothermal alteration. Two-pyroxene eothermometry and various mineral-fluid equilibria suggest the range of peak temperatures attained in the metamorphic zones: orthopyroxene-olivine zone, 900°1, 030° C; amphibole zone, 400°–900° C; smectite and primary olivine zones, < 400° C. Mineralogical and oxygen isotopic alteration of the metabasalts were closely coupled: Basalts from the primary olivine zone with nearly unaltered igneous mineralogies have normal or near-normal wholerock ¹⁸O>+5 (SMOW); mineralogically more altered basalts from the smectite zone have whole-rock ¹⁸O=+2 to +5; still more mineralogically altered basalts from the amphibole zone (with one exception) have ¹⁸O<+ 2; completely recrystallized hornfelses from the orthopyroxene-olivine zone have ¹⁸O<0. The principal mechanism of isotope exchange between basalt and metamorphic/ hydrothermal fluid probably was heterogeneous mineralfluid reaction.Metabasalts from the orthopyroxene-olivine zone are mineralogically fresh pyroxene hornfelses that record crystallization temperatures > 1,000° C yet have highly altered whole-rock oxygen isotope compositions, ¹⁸O<0%. The hornfelses chemically interacted with metamorphic/hydrothermal fluids either at very high temperatures or while they were heated to > 1,000° C or both. Their mineralogy, however, rules out significant water-rock interaction after they cooled below 900° C. Hydrothermal convection on Skye was a two-stage process: (a) fluid flow through wall rocks initially was pervasive while they are heated; (b) fluid flow after the thermal peak in the wall rocks was sufficiently channelized that rocks such as those in the orthopyroxeneolivine zone were isolated from further fluid-rock interaction during all or almost all of the cooling history of the hydrothermal system.     

Compositional controls on vent fluids from ultramafic-hosted hydrothermal systems at mid-ocean ridges: An experimental study at 400°C, 500 bars

Olivine (Fo₈₉), orthopyroxene (En₈₅), and clinopyroxene (Di₈₉) were reacted, individually and in combinations, with NaCl-MgCl₂ at 400°C, 500 bars to better assess alteration and mass transfer in ultramafic-hosted hydrothermal systems at mid-ocean ridges. Data indicate that temperature plays a key role in mineral solubility and kinetic processes, which influence the compositional evolution of the fluid. At the temperature and pressure of the experiments, the rate of olivine hydrolysis is sluggish as indicated by the limited extent of mass transfer between the fluid and mineral and absence of hydrous alteration phases. In contrast, reactions involving pyroxenes proceed rapidly, which result in significant increases in dissolved Ca, SiO₂, Fe and H₂, and formation of SiO₂-rich secondary minerals (talc and tremolite) and magnetite. SiO₂ release from pyroxene occurs in non-stoichiometric proportions and is a critical factor governing the stability of secondary minerals, with attendant effects on fluid chemistry.Magnetite and talc-fluid equilibria were used to calculate fluid pH at elevated temperatures and pressures. In general, pH is relatively low in the orthopyroxene- and clinopyroxene-bearing experiments due to constraints imposed by talc-fluid and talc-tremolite-fluid equilibria, respectively. Even in experiments where the olivine/pyroxene ratio is as great as 3, which is typical for abyssal peridotite, the low pH and high Fe concentrations are maintained. This is in sharp contrast to theoretical predictions assuming full equilibrium in the MgO-CaO-FeO-Fe₂O₃-SiO₂-Na₂O-H₂O-HCl system at 400°C, 500 bars.Ultramafic-hosted hydrothermal systems, such as the recently discovered Rainbow system at 36°13.80′N, 33°54.12′W on the Mid-Atlantic Ridge, indicate reaction processes in keeping with results of the present experiments, as suggested by vent fluid chemistry and temperature. In particular, relatively high SiO₂, Ca, H₂, and Fe concentrations characterize the Rainbow vent fluids. Indeed, Fe concentrations are the highest of any vent system yet discovered and require a relatively low pH in the subseafloor reaction zone from which the fluids are derived. This, together with the SiO₂ concentrations of the vent fluids, strongly indicates fluid buffering by silica-rich phases produced during pyroxene dissolution, the likely abundant presence of olivine notwithstanding. Time-series observations at Rainbow are clearly needed to better constrain the temporal evolution of hydrothermal alteration processes of ultramafic rocks in subseafloor reaction zones. In the absence of events permitting fluid continuous access to fresh rock, pyroxene will ultimately be consumed and vent fluids may then reflect changes imposed by bulk compositional constraints characteristic of ultramafic bodies at depth, which would be in better agreement with theoretical phase relations for the fully equilibrated system.     

Alteration and mass transfer in cataclasites and mylonites in 6.6 km of granitic crust at the Siljan impact structure,central Sweden

Granitic rocks deformed by cataclasis and mylonitization on macro- (a few meters) and micro- (thin section) scales are found at depths down to 6.6km in the Siljan impact structure in central Sweden. Granites near fault planes exhibit: (1) fracturing, kinking, fragmentation, and recrystallization of feldspars into pure K and Na endmember varieties, (2) fragmentation, polygonization and development of undulose extinction in quartz, and (3) kinking, appearance of wavy extinction and alteration of biotite, chlorite, amphibole, and alteration of ilmenite and magnetite. Whole-rock chemical analyses of deformed and undeformed rocks show that deformed rocks are enriched in SiO₂ (by about 5 wt.%) and depleted in other oxides by variable percentages. Apart from Rb and Co, the concentrations of other trace elements (including Ba, Sr, Zn, Zr, Pb, Cd, Cu, Cr, Ni, V, U, Th, La, and Li) are lower in deformed relative to undeformed rocks. Mass-balance calculations for a 1000 cm³ model granite which were based on modal mineralogy, whole-rock chemistry, and mineral analyses suggest that the break down of primary biotite, chlorite, and amphibole in deformed zones released elements to circulating fluids. These calculations also indicate liberation of water and a doubling of porosity (from 1 to 2%) during the deformation episodes. Later precipitation of minerals in shear and tension fractures reduced this porosity. Within the upper 2000 m of the Gravberg-1 well, the formation of fracture-filling minerals (smectite, calcite, hematite, chlorite, and albite) is impact-related, and was favored by active circulation of meteoric water. Fracture-filling minerals in the upper 2000 m of the borehole formed at temperatures of 70° to 200°C. Between depths of 2000 and 3500 m, fracture-filling mineral assemblages (dominated by Fe–Mg chlorite, sphene and epidote) suggest formation temperatures in the range of 150° to 300°C. Occurrence of pumpellyite and prehnite in some altered biotite and chlorite of the deformed zones between 3500 and 5500 m suggest preimpact metamorphism and formation temperature above 150°C. Below 5500 m, the mineral assemblages in the fractures are dominated by quartz, sphene, epidote, and some muscovite and chlorite, indicating a temperature range between 300° and 450°C. One of the possible origins for the CH₄ and H₂ gases detected in the Gravberg-1 well is a combination of hydrogen ions released by decomposition of hydrated silicates (biotite, chlorite, hornblende) with carbon. The presence of iron in the deformed granitic rocks prevented the resulting CH₄ from being oxidized.     

The production of iron oxide during peridotite serpentinization: Influence of pyroxene

Serpentinization produces molecular hydrogen(H2)that can support communities of microorganisms in hydrothermal fields;H2 results from the oxidation of ferrous iron in olivine and pyroxene into ferric iron,and consequently iron oxide(magnetite or hematite)forms.However,the mechanisms that control H2 and iron oxide formation are poorly constrained.In this study,we performed serpentinization experiments at 311℃ and 3.0 kbar on olivine(with 5% pyroxene),orthopyroxene,and peridotite.The results show that serpentine and iron oxide formed when olivine and orthopyroxene individually reacted with a saline starting solution.Olivine-derived serpentine had a significantly lower FeO content(6.57±1.30 wt.%)than primary olivine(9.86 wt.%),whereas orthopyroxene-derived serpentine had a comparable FeO content(6.26±0.58 wt.%)to that of primary orthopyroxene(6.24 wt.%).In experiments on peridotite,olivine was replaced by serpentine and iron oxide.However,pyroxene transformed solely to serpentine.After 20 days,olivine-derived serpentine had a FeO content of 8.18±1.56 wt.%,which was significantly higher than that of serpentine produced in olivine-only experiments.By contrast,serpentine after orthopyroxene had a slightly higher FeO content(6.53±1.01 wt.%)than primary orthopyroxene.Clinopyroxene-derived serpentine contained a significantly higher FeO content than its parent mineral.After 120 days,the FeO content of olivine-derived serpentine decreased significantly(5.71±0.35 wt.%),whereas the FeO content of orthopyroxene-derived serpentine increased(6.85±0.63 wt.%)over the same period.This suggests that iron oxide preferentially formed after olivine serpentinization.Pyroxene in peridotite gained some Fe from olivine during the serpentinization process,which may have led to a decrease in iron oxide production.The correlation between FeO content and SiO_2 or AI_2 O_3 content in olivine-and orthopyroxene-derived serpentine indicates that aluminum and silica greatly control the production of iron oxide.Based on our results and data from natural serpentinites reported by other workers,we propose that aluminum may be more influential at the early stages of peridotite serpentinization when the production of iron oxide is very low,whereas silica may have a greater control on iron oxide production during the late stages instead.     

Origin of zoned spinel by coupled dissolution–precipitation and inter-crystalline diffusion: evidence from serpentinized wehrlite, Bangriposi, Eastern India

Textural and mineral–chemical characteristics in the Bangriposi wehrlites (Eastern India) provide insight into metamorphic processes that morphologically and chemically modified magmatic spinel during serpentinization of wehrlite. Aluminous chromite included in unaltered magmatic olivine is chemically homogenous. In sub-cm to 10s-of-micron-wide veins, magnetite associated with antigorite and clinochlore comprising the serpentine matrix is near-stoichiometric. But Al–Cr–Fe³⁺ spinels in the chlorite–magnetite veins are invariably zoned, e.g., chemically homogenous Al-rich chromite interior successively mantled by ferritchromite/Cr-rich magnetite zone and magnetite continuous with vein magnetite in the serpentine matrix. In aluminous chromite, ferritchromite/Cr-rich magnetite zones are symmetrically disposed adjacent to fracture-controlled magnetite veins that are physically continuous with magnetite rim. The morphology of ferritchromite–Cr-rich magnetite mimics the morphology of aluminous chromite interior but is incongruous with the exterior margin of magnetite mantle. Micropores are abundant in magnetite veins, but are fewer in and do not appear to be integral to the adjacent ferritchromite–Cr-rich magnetite zones. Sandwiched between chemically homogenous aluminous chromite interior and magnetite mantle, ferritchromite–Cr-rich magnetite zones show rim-ward decrease in Cr₂O₃, Al₂O₃ and MgO and complementary increase in Fe₂O₃ at constant FeO. In diffusion profiles, Fe₂O₃–Cr₂O₃ crossover coincides with Al₂O₃ decrease to values <0.5 wt% in ferritchromite zone, with Cr₂O₃ continuing to decrease within magnetite mantle. Following fluid-mediated (hydrous) dissolution of magmatic olivine and olivine + Al–chromite aggregates, antigorite + magnetite and chlorite + magnetite were transported in 10s-of-microns to sub-cm-wide veins and precipitated along porosity networks during serpentinization (T: 550–600 °C, f(O₂): ?19 to ?22 log units). These veins acted as conduits for precipitation of magnetite as mantles and veins apophytic in chemically/morphologically modified magmatic Al-rich chromite. Inter-crystalline diffusion induced by chemical gradient at interfaces separating aluminous chromite interiors and magnetite mantles/veins led to the growth of ferritchromite/Cr-rich magnetite zones, mimicking the morphology of chemically modified Al–Cr–Fe–Mg spinel interiors. Inter-crystalline diffusion outlasted fluid-mediated aluminous chromite dissolution, mass transfer and magnetite precipitation.     

Thermodynamic constraints on hydrogen generation during serpentinization of ultramafic rocks

In recent years, serpentinized ultramafic rocks have received considerable attention as a source of H₂ for hydrogen-based microbial communities and as a potential environment for the abiotic synthesis of methane and other hydrocarbons within the Earth’s crust. Both of these processes rely on the development of strongly reducing conditions and the generation of H₂ during serpentinization, which principally results from reaction of water with ferrous iron-rich minerals contained in ultramafic rocks. In this report, numerical models are used to investigate the potential influence of chemical thermodynamics on H₂ production during serpentinization. The results suggest that thermodynamic constraints on mineral stability and on the distribution of Fe among mineral alteration products as a function of temperature are likely to be major factors controlling the extent of H₂ production. At high temperatures (>∼315 °C), rates of serpentinization reactions are fast, but H₂ concentrations may be limited by the attainment of stable thermodynamic equilibrium between olivine and the aqueous fluid. Conversely, at temperatures below ∼150 °C, H₂ generation is severely limited both by slow reaction kinetics and partitioning of Fe(II) into brucite. At 35 MPa, peak temperatures for H₂ production occur at 200-315 °C, indicating that the most strongly reducing conditions will be attained during alteration within this temperature range. Fluids interacting with peridotite in this temperature range are likely to be the most productive sources of H₂ for biology, and should also produce the most favorable environments for abiotic organic synthesis. The results also suggest that thermodynamic constraints on Fe distribution among mineral alteration products have significant implications for the timing of magnetization of the ocean crust, and for the occurrence of native metal alloys and other trace minerals during serpentinization.     

Origin of ultramafic xenoliths containing exsolved pyroxenes from Hualalai Volcano,Hawaii

Hualalai Volcano, Hawaii, is best known for the abundant and varied xenoliths included in the historic 1800 Kaupulehu alkalic basalt flow. Xenoliths, which range in composition from dunite to anorthosite, are concentrated at 915-m elevation in the flow. Rare cumulate ultramafic xenoliths, which include websterite, olivine websterite, wehrlite, and clinopyroxenite, display complex pyroxene exsolution textures that indicate slow cooling. Websterite, olivine websterite, and one wehrlite are spinel-bearing orthopyroxene +olivine cumulates with intercumulus clinopyroxene +plagioclase. Two wehrlite samples and clinopyroxenite are spinel-bearing olivine cumulates with intercumulus clinopyroxene+orthopyroxene + plagioclase. Two-pyroxene geothermometry calculations, based on reconstructed pyroxene compositions, indicate that crystallization temperatures range from 1225° to 1350° C. Migration or unmixing of clinopyroxene and orthopyroxene stopped between 1045° and 1090° C. Comparisons of the abundance of K₂O in plagioclase and the abundances of TiO₂ and Fe₂O₃in spinel of xenoliths and mid-ocean ridge basalt, and a single ⁸⁷Sr/ ⁸⁶Sr determination, indicate that these Hualalai xenoliths are unrelated to mid-ocean ridge basalt. Similarity between the crystallization sequence of these xenoliths and the experimental crystallization sequence of a Hawaiian olivine tholeiite suggest that the parental magma of the xenoliths is Hualalai tholeiitic basalt. Xenoliths probably crystallized between about 4.5 and 9 kb. The 155°–230° C of cooling which took place over about 120 ka — the age of the youngest Hualalai tholeiitic basalt — yield maximum cooling rates of 1.3×10^–3–1.91×10^–3 °C/yr. Hualalai ultramafic xenoliths with exsolved pyroxenes crystallized from Hualalai tholeiitic basalt and accumulated in a magma reservoir located between 13 and 28 km below sealevel. We suspect that this reservoir occurs just below the base of the oceanic crust at about 19 km below sealevel.     

Metamorphism of the Basement of the Qilian Fold Belt in the Minhe-Ledu Area, Qinghai Province, NW China

The basement of the central Qilian fold belt exposed along the Minhe-Ledu highway consists of psammitic schists, metabasitic rocks, and crystalline limestone. Migmatitic rocks occur sporadically among psammitic schist and metabasitic rocks. The mineral assemblage of psammitic schist is muscovite + biotite + feldspar + quartz ± tourmaline ± titanite ± sillimanite and that of metabasitic rocks is amphibole + plagioclase + biotite ± apatite ± magnetite ± pyroxene ± garnet ± quartz. The migmatitic rock consists of leucosome and restite of various volume proportions; the former consists of muscovite + alkaline feldspar + quartz ± garnet ± plagioclase while the latter is either fragments of psammitic schist or those of metabasitic rock. The crystalline limestone consists of calcite that has been partly replaced by olivine. The olivine was subsequently altered to serpentine. Weak deformations as indicated by cleavages and fractures were imposed prominently on the psammitic schists, occasionally on me     

Metamorphism of peritotites in the mantle wedge above the subduction zone: Hydration of the lithospheric mantle

Two areas with different types of hydration (serpentinization), which occurred in two settings distinct in temperatures, pressures, and stresses, are spatially individualized in the ophiolitic ultramafic massifs of the Polar Urals. The high-temperature hydration of ultramafic rocks occurred in the lithosphere of the mantle wedge directly above the subducted slab. The initial conditions of hydration are limited to 1.2–2 GPa and 650–700°C; a stable assemblage of olivine + antigorite + magnetite → amphibole → talc → chlorite was formed at 0.9–1.2 GPa and 550–600°C. The low-temperature mesh lizardite–chrysotile serpentinization occurred in the crustal, near-surface conditions. Both types of hydration were accompanied by release of hydrogen, which participates in abiogenic CH₄ synthesis in the presence of CO₂ dissolved in water.     

Stability and solubility of arsenopyrite, FeAsS, in crustal fluids

The stability and solubility of natural arsenopyrite (FeAsS) in pure water and moderately acid to slightly basic aqueous solutions buffered or not with H₂ and/or H₂S were studied at temperatures from 300 to 450°C and pressures from 100 to 1000 bar. The solubilities of FeAsS in pure water and dilute HCl/NaOH solutions without buffering are consistent with the formation of the As(OH)₃⁰(aq) species and precipitation of magnetite. At more acid pH (pH ≤2), arsenopyrite dissolves either stoichiometrically or with formation of the As-FeAsS assemblage. In H₂S-rich and H₂-rich aqueous solutions, arsenopyrite dissolution results in the formation of pyrrhotite (±pyrite) and iron arsenide(s), respectively, which form stable assemblages with arsenopyrite.Arsenic concentrations measured in equilibrium with FeAsS in slightly acid to neutral aqueous solutions with H₂ and H₂S fugacities buffered by the pyrite-pyrrhotite-magnetite assemblage are 0.0006 ± 0.0002, 0.0055 ± 0.0010, 0.07 ± 0.01, and 0.32 ± 0.03 mol/kg H₂O at 300°C/400 bar, 350°C/500 bar, 400°C/500 bar, and 450°C/500 bar, respectively. These values were combined with the available thermodynamic data on As(OH)₃⁰(aq) (Pokrovski et al., 1996) to derive the Gibbs free energy of FeAsS at each corresponding temperature and pressure. Extrapolation of these values to 25°C and 1 bar, using the available heat capacity and entropy data for FeAsS (Pashinkin et al., 1989), yields a value of −141.6 ± 6.0 kJ/mol for the standard Gibbs free energy of formation of arsenopyrite. This value implies a higher stability of FeAsS in hydrothermal environments than was widely assumed.Calculations carried out using the new thermodynamic properties of FeAsS demonstrate that this mineral controls As transport and deposition by high-temperature (>∼300°C) crustal fluids during the formation of magmatic-hydrothermal Sn-W-Cu-(Au) deposits. The equilibrium between As-bearing pyrite and the fluid is likely to account for the As concentrations measured in modern high- and moderate-temperature (150 ≤ T ≤ 350°C) hydrothermal systems. Calculations indicate that the local dissolution of arsenopyrite creates more reducing conditions than in the bulk fluid, which is likely to be an effective mechanism for precipitating gold from hydrothermal solutions. This could be a possible explanation for the gold-arsenopyrite association commonly observed in many hydrothermal gold deposits.     

Melt inclusions in olivine and pyroxene phenocrysts from lamprophyres of Chhaktalao Area,Madhya Pradesh,India

Melt inclusions in olivine and pyroxene phenocrysts in kersantite and camptonite at Chhaktalao in Madhya Pradesh, India are mainly of the evolved type forming daughter minerals of olivine, pyroxene, plagioclase, spinel, mica, titanomagnetite and sulphides. Heating studies exhibit a temperature range from 1215° to 1245°C for the melt inclusions in olivine in camptonite and 1220–1245°C for olivine in kersantite. The temperature for melt inclusions in pyroxene ranged from 1000° to 1150°C in camptonite and 850–1100°C for pyroxene in kersantite. The bubble inside these melt inclusions is mainly CO₂. The T_h°C of CO₂ into liquid phase occurred between 26° and 31°C in olivine and 25–30°C in pyroxene from kersantite and camptonite. The maximum density estimated is 0.72 g/cm³ and the minimum is 0.45 g/cm³. The depth of entrapment of the melt inclusion is estimated between 10–15 km. The pressure of entrapment of melt inclusion in olvine is 4.6 kbar where as that in pyroxene is 3.7 kbar. The lamprophyres in the Chhaktalao area are considered to be derived from low depth and low pressure region, possibly within spinel lherzolite zone.     

An experimental study of crystalline basalt dissolution from 2 ? pH ? 11 and temperatures from 5 to 75 °C

Steady-state element release rates from crystalline basalt dissolution at far-from-equilibrium were measured at pH from 2 to 11 and temperatures from 5 to 75 °C in mixed-flow reactors. Steady-state Si and Ca release rates exhibit a U-shaped variation with pH where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Silicon release rates from crystalline basalt are comparable to Si release rates from basaltic glass of the same chemical composition at low pH and temperatures ?25 °C but slower at alkaline pH and temperatures ?50 °C. In contrast, Mg and Fe release rates decrease continuously with increasing pH at all temperatures. This behaviour is interpreted to stem from the contrasting dissolution behaviours of the three major minerals comprising the basalt: plagioclase, pyroxene, and olivine. Calcium is primarily present in plagioclase, which exhibits a U-shaped dissolution rate dependence on pH. In contrast, Mg and Fe are contained in pyroxene and olivine, minerals whose dissolution rates decrease monotonically with pH. As a result, crystalline basalt preferentially releases Mg and Fe relative to Ca at acidic conditions. The injection of acidic CO₂-charged fluids into crystalline basaltic terrain may, therefore, favour the formation of Mg and Fe carbonates rather than calcite. Element release rates estimated from the sum of the volume fraction normalized dissolution rates of plagioclase, pyroxene, and olivine are within one order of magnitude of those measured in this study.