Volatiles in pillows of the Mid-Ocean-Ridge-Basalt (MORB) and vitreous basaltic rims

Temperature-resolved analyses of volatiles from Mid-Ocean-Ridge-Basalt (MORB) and vitreous basaltic rims were carried out to investigate the total volatile contents of basaltic melts and the influence of magma contamination on the degassing behaviour of volcanic rocks.With respect to the sources of methane evolution from the MORB the investigations are taken into consideration, the hydrocarbon (HC) release especially from the melt.The current paper presents data for H₂O, CO₂, SO₂, He, H₂, HF, HCl, CO, N₂, O₂, and HC degassing profiles of samples from the MORB sampling cruise 02.10.1983-11.11.1983 with FS Sonne 28 during the GEMINO-1 project near the Carlsberg Ridge (CR) and the Mid-Indian-Ocean-Ridge (MIOR).It aims to estimate the magnitude and nature of source magma volatiles and contamination (crustal material, seawater, atmospheric gases).The degassing of H₂O, CO₂, HCs as well as sulphur and chlorine species, or O₂ from vitreous specimens shows characteristic differences associated with sample position with respect to the lava surface.From the water release by bubbling and diffusion above 700 °C it must be concluded that any assimilation of sea water in vitreous rim is very low. The water content in the vitreous rim is about 0.1-0.2 wt%. The low interaction of melt with sea water is supported by the missing of a significant release of chlorine species during the heat treatment of the sample up to 1450 °C.Mixed H₂O/CO₂ bubbles escape between 700 and 800 °C from the vitreous rim. The CO₂ release in the temperature range of 1060-1170 °C from the basalt and the vitreous rim is interpreted as an indication for the primary carbon-dioxide content in the melt.Above 1100 °C CO₂ and SO₂ are evolved by both diffusion and small bubbles. The quantities of CO₂ in the vitreous rim and the basalt are similar (between 0.05 and 0.15 wt%), whereas the quantities of SO₂ escaping both from the vitreous rim and the crystalline basalt are between 0.013 and 0.024 wt%.Simultaneous with the CO₂ release by bubbling, HC species, especially CH fragments, were observed. The fact that the temperature of release maxima are above 1050 °C in both the vitreous rim and in the basalt is an indication for a geogenetic origin of HCs, e.g. methane.A low temperature of release for methane, which is consistent with biogenetic HC, was observed from the gas-release profiles of the basalts only. The maxima of the low-temperature gas releases are between 80 and 200 °C with a high correlation between the fragments m/z 13 and m/z 15. This correlation is a significant indication for a methane release.The oxygen release profiles of vitreous and crystalline basalts give significant indications for oxygen fugacity below the (QMF) of basaltic magma.Secondary minerals, generated by alteration of basaltic rocks, can be characterized by gas release profiles (GRPs) due to their decomposition in the temperature range below 800 °C. Only in the basalt were there observed indications of alteration processes. Small traces of carbonates (<0.0001 wt%) were detected by the gas release during the decomposition.Processes of degassing at temperatures higher than 800 °C are correlated to volatiles in the melt and to fluid inclusions of the minerals. There are no obvious correlations in the degassing characteristics between H₂O, CO₂ and SO₂. The different maxima of the degassing velocity, especially of CO₂, and SO₂, are indications of the different bonding forces of the site occupancy of the volatiles in the melt and in the glass. A micelle model for bonding sites in the basaltic glass for dissolved volatiles is discussed.     

Mineralogy and proposed P-T paths of basaltic lavas from Rabaul caldera,Papua New Guinea

Rabaul caldera is a large volcanic depression at the north-east tip of New Britain, Papua New Guinea. The lavas range in composition from basalt to rhyolite and have a calc-alkalic affinity but also display features typical of tholeiites, including moderate absolute iron enrichment in flows cropping out around the caldera. The basalts contain phenocrysts of plagioclase and clinopyroxene with less abundant olivine and titanomagnetite. In the basaltic andesites olivine is rare, while orthopyroxene and titanomagnetite are common along with plagioclase and clinopyroxene. Orthopyroxene is also found mantling olivine in some of the basalts while in both rock types pigeonitic augite is a fairly common constituent of the groundmass. Plagioclase in both basalt and basaltic andesite often exhibits sieve texture and analysis of the glass blebs show them to be of similar composition to the bulk rock. Phenocrystic clinopyroxene is a diopsidic augite in both basalt and basaltic andesite. Al₂O₃ content of the clinopyroxene is moderately high (4%) and often shows considerable variation in any one grain. Calculations show that the microphenocrysts probably crystallised near the surface, while phenocrysts crystallised at around 7 kb (21 km). Neither the basalts nor the basaltic andesites would have been in equilibrium at any geologically reasonable P and T with quartz eclogite. Equilibration between mantle peridotite and a. typical Rabaul basaltic liquid could have occurred around 35 kb and 1270 °C. A basaltic andesite liquid yields a temperature of 1263 °C and a pressure of 28 kb for equilibration with mantle peridotite.Partial melting of sufficient volumes of mantle peridotite at these P's and T's requires about 15% H₂O, but there is no evidence that these magmas ever contained large amounts of water. It is proposed that the Rabaul magmas were initially generated by partial melting of subducted lithosphere and subsequently modified by minor partial melting as they passed through the overlying mantle peridotite.     

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.     

Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity

XANES analyses at the sulfur K-edge were used to determine the oxidation state of S species in natural and synthetic basaltic glasses and to constrain the fO₂ conditions for the transition from sulfide (S²⁻) to sulfate (S⁶⁺) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, USA, showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as hauyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S²⁻ and S⁶⁺ species, emphasizing the relevance of S⁶⁺ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO₂ ranging from FMQ − 1.4 to FMQ + 2.7 showed systematic changes in the features related to S²⁻ and S⁶⁺ with changes in fO₂. No significant features related to sulfite (S⁴⁺) species were observed. These results were used to construct a function that allows estimates of S⁶⁺/ΣS from XANES data. Comparison of S⁶⁺/ΣS data obtained by S Kα shifts measured with electron probe microanalysis (EPMA), S⁶⁺/ΣS obtained from XANES spectra, and theoretical considerations show that data obtained from EPMA measurements underestimate S⁶⁺/ΣS in samples that are sulfate-dominated (most likely because of photo-reduction effects during analysis) whereas S⁶⁺/ΣS from XANES provide a close match to the expected theoretical values. The XANES-derived relationship for S⁶⁺/ΣS as a function of fO₂ indicates that the transition from S²⁻ to S⁶⁻ with increasing fO₂ occurs over a narrower interval than what is predicted by the EPMA-derived relationship. The implications for natural systems is that small variation of fO₂ above FMQ + 1 will have a large effect on S behavior in basaltic systems, in particular regarding the amount of S that can be transported by basaltic melts before sulfide saturation can occur.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

Carbonatization of oceanic crust by the seafloor hydrothermal activity and its significance as a CO2 sink in the Early Archean

Early Archean (3.46 Ga) hydrothermally altered basaltic rocks exposed near Marble Bar, eastern Pilbara Craton, have been studied in order to reveal geological and geochemical natures of seafloor hydrothermal carbonatization and to estimate the CO₂ flux sunk into the altered oceanic crust by the carbonatization. The basaltic rocks are divided into basalt and dolerite, and the basalt is further subdivided into type I, having original igneous rock textures, and type II, lacking these textures due to strong hydrothermal alteration. Primary clinopyroxene phenocrysts are preserved in some part of the dolerite samples, and the alteration mineral assemblage of dolerite (chlorite + epidote + albite + quartz ± actinolite) indicates that the alteration condition was typical greenschist facies. In other samples, all primary minerals were completely replaced by secondary minerals, and the alteration mineral assemblage of the type I and type II basalts (chlorite + K-mica + quartz + carbonate minerals ± albite) is characterized by the presence of K-mica and carbonate minerals and the absence of Ca-Al silicate minerals such as epidote and actinolite, suggesting the alteration condition of high CO₂ fugacity. The difference of the alteration mineral assemblages between basalt and dolerite is probably attributed to the difference of water/rock ratio that, in turn, depends on their porosity.Carbonate minerals in the carbonatized basalt include calcite, ankerite, and siderite, but calcite is quite dominant. The δ¹³C values of the carbonate minerals are −0.3 ± 1.2‰ and mostly within the range of marine carbonate, indicating that the carbonate minerals were formed by seafloor hydrothermal alteration and that carbonate carbon in the altered basalt was derived from seawater. Whole-rock chemical composition of the basaltic rocks is essentially similar to that of modern mid-ocean ridge basalt (MORB) except for highly mobile elements such as K₂O, Rb, Sr, and Ba. Compared to the least altered dolerite, all altered basalt samples are enriched in K₂O, Rb, and Ba, and are depleted in Na₂O, reflecting the presence of K-mica replacing primary plagioclase. In addition, noticeable CO₂ enrichment is recognized in the basalt due to the ubiquitous presence of carbonate minerals, but there was essentially neither gain nor loss of CaO. This suggests that the CO₂ in the hydrothermal fluid (seawater) was trapped by using Ca originally contained in the basalt. The CaO/CO₂ ratios of the basalt are generally the same as that of pure calcite, indicating that Ca in the basalt was almost completely converted to calcite during the carbonatization, although Mg and Fe were mainly redistributed into noncarbonate minerals such as chlorite.The carbon flux into the Early Archean oceanic crust by the seafloor hydrothermal carbonatization is estimated to be 3.8 × 10¹³ mol/yr, based on the average carbon content of altered oceanic crust of 1.4 × 10^-3 mol/g, the alteration depth of 500 m, and the spreading rate of 1.8 × 10¹¹ cm²/yr. This flux is equivalent to or greater than the present-day total carbon flux. It is most likely that the seafloor hydrothermal carbonatization played an important role as a sink of atmospheric and oceanic CO₂ in the Early Archean.     

Petrology,geochemistry and tectonic setting of the Khoy ophiolite,northwest Iran: implications for Tethyan tectonics

The Khoy ophiolite in northwestern Iran represents a remnant of oceanic lithosphere formed in the Mesozoic Neo-Tethys. This northwest–southeast trending ophiolite complex consists from bottom to top (east to west) of a well-defined basal metamorphic zone, peridotites (dunite, harzburgite) and serpentinized peridotite, gabbros, sheeted dikes, pillow and massive lava flows, and pelagic sedimentary rocks, including radiolarian chert. The rocks of the metamorphic zone have an inverse thermal gradient from amphibolite facies to greenschist facies. The high-grade metamorphic rocks are immediately adjacent to the peridotite and the gabbros and the low-grade rocks are in contact with the Precambrian Kahar Formation. Based on mantle-normalized incompatible trace element diagrams there are two distinct types of basalt flows present at the Khoy ophiolite: (1) massive basalts that have patterns virtually identical to E-MORB, and (2) pillow basalts that have more primitive chemical composition whose trace element patterns plot between E-MORB and N-MORB. The chondrite-normalized REE patterns for the pillow basalts are LREE-depleted [(La_N/Sm_N)_ave=0.70], similar to patterns for the mean diabase composition for the Oman ophiolite and LREE-depleted basalts of the Band-e-Zeyarat ophiolite of southern Iran. The REE patterns for the massive basalts are similar in general REE abundances to the pillow basalt patterns, but they are slightly LREE-enriched [(La_N/Sm_N)_ave=1.09] and their patterns cross those of the pillow basalts. The REE patterns for the gabbros and diorites indicates that the crustal-suite rocks were most likely derived by a process of fractional crystallization from a common basaltic melt. This basaltic melt was most likely generated by approx. 20–25% partial melting of a simple lherzolite source and had REE concentrations of roughly 10× chondrite. A comparison between the results from the Khoy ophiolite and the data from other Iranian ophiolites reveals geochemical evidence to suggest a tectonic link between the Khoy ophiolite and the rest of the Iranian ophiolites. Our results suggest that Khoy ophiolite is equivalent to the inner group of Iranian ophiolites (e.g. Nain, Shahr-Babak, Sabzevar, Tchehel Kureh and Band-e-Zeyarat) and was formed as a result of closure of the northwestern branch of a narrow Mesozoic seaway which once surrounded the Central Iranian microcontinent.     

The fluvial geochemistry, contributions of silicate, carbonate and saline-alkaline components to chemical weathering flux and controlling parameters: Narmada River (Deccan Traps), India

The Narmada River in India is the largest west-flowing river into the Arabian Sea, draining through the Deccan Traps, one of the largest flood basalt provinces in the world. The fluvial geochemical characteristics and chemical weathering rates (CWR) for the mainstream and its major tributaries were determined using a composite dataset, which includes four phases of seasonal field (spot) samples (during 2003 and 2004) and a decade-long (1990-2000) fortnight time series (multiannual) data. Here, we demonstrate the influence of minor lithologies (carbonates and saline-alkaline soils) on basaltic signature, as reflected in sudden increases of Ca²⁺-Mg²⁺ and Na⁺ contents at many locations along the mainstream and in tributaries. Both spot and multiannual data corrected for non-geological contributions were used to calculate the CWR. The CWR for spot samples (CWR_spot) vary between 25 and 63 ton km⁻² year⁻¹, showing a reasonable correspondence with the CWR estimated for multiannual data (CWR_multi) at most study locations. The weathering rates of silicate (SilWR), carbonate (CarbWR) and evaporite (Sal-AlkWR) have contributed ∼38-58, 28-45 and 8-23%, respectively to the CWR_spot at different locations. The estimated SilWR (11-36 ton km⁻² year⁻¹) for the Narmada basin indicates that the previous studies on the North Deccan Rivers (Narmada-Tapti-Godavari) overestimated the silicate weathering rates and associated CO₂ consumption rates. The average annual CO₂ drawdown via silicate weathering calculated for the Narmada basin is ∼0.032 × 10¹² moles year⁻¹, suggesting that chemical weathering of the entire Deccan Trap basalts consumes approximately 2% (∼0.24 × 10¹² moles) of the annual global CO₂ drawdown. The present study also evaluates the influence of meteorological parameters (runoff and temperature) and physical weathering rates (PWR) in controlling the CWR at annual scale across the basin. The CWR and the SilWR show significant correlation with runoff and PWR. On the basis of observed wide temporal variations in the CWR and their close association with runoff, temperature and physical erosion, we propose that the CWR in the Narmada basin strongly depend on meteorological variability. At most locations, the total denudation rates (TDR) are dominated by physical erosion, whereas chemical weathering constitutes only a small part (<10%). Thus, the CWR to PWR ratio for the Narmada basin can be compared with high relief small river watersheds of Taiwan and New Zealand (1-5%) and large Himalayan Rivers such as the Brahmaputra and the Ganges (8-9%).     

Experimental study of the phase and melting relations of homogeneous basalt + peridotite mixtures and implications for the petrogenesis of flood basalts

Flood basalt provinces may constitute some of the most catastrophic volcanic events in the Earth's history. A popular model to explain them involves adiabatic ascent of plumes of anomalously hot peridotite from a thermal boundary layer deep in the mantle, across the peridotite solidus. However, peridotitic plumes probably require unreasonably high potential temperatures to generate sufficient volumes of magma and high enough melting rates to produce flood volcanism. This lead to the suggestion that low melting eclogitic or pyroxenitic heterogeneities may be present in the source regions of the flood basalts. In order to constrain petrogenetic models for flood basalts generated in this way, an experimental investigation of the melting relations of homogeneous peridotite + oceanic basalt mixtures has been performed. Experiments were conducted at 3.5 GPa on a fertile peridotite (MPY90)–oceanic basalt (GA1) compositional join. The hybrid basalt + peridotite compositions crystallised garnet lherzolite at subsolidus temperatures plus quenched ne-normative picritic liquids at temperatures just above the solidus, over the compositional range MPY90 to GA1₅₀MPY90₅₀. The solidus temperature decreased slightly from ∼1500 °C for MPY90 to ∼1450 °C for GA1₅₀MPY90₅₀. Compositions similar to GA1₃₀MPY90₇₀ have 100% melting compressed into a melting interval which is approximately 50–60% smaller than that for pure MPY90, due to a liquidus minimum. During adiabatic ascent of hybrid source material containing a few tens of percent basalt in peridotite, the lower solidus and compressed solidus–liquidus temperature interval may conspire to substantially enhance melt productivity. Mixtures of recycled oceanic crust and peridotite in mantle plumes may therefore provide a viable source for some flood volcanics. Evidence for this would include higher than normal Fe/Mg values in natural primary liquids, consistent with equilibration with more Fe-rich olivine than normal pyrolitic olivine (i.e. <Fo_89–92). Modelling of fractionation trends in West Greenland picrites is presented to demonstrate that melts parental to the Greenland picrites were in equilibrium at mantle P–T conditions with olivine with Fo_84–86, suggesting an Fe-enriched source compared with normal peridotite, and consistent with the presence of a basaltic component in the source. Received: 29 October 1999 / Accepted: 3 February 2000     

Antarctic lunar meteorites Yamato-793169, Asuka-881757, MIL 05035, and MET 01210 (YAMM): Launch pairing and possible cryptomare origin

The Antarctic lunar meteorite Meteorite Hills (MET) 01210 is a polymict regolith breccia, dominantly composed of mare basalt components. One relatively large (2.7 × 4.7 mm) basalt clast in MET 01210 (MET basalt) shows remarkable mineralogical similarities to the lunar-meteorite crystalline mare basalts Yamato (Y)-793169, Asuka (A)-881757, and Miller Range (MIL) 05035. All four basalts have similar rock texture, mineral assemblage, mineral composition, pyroxene crystallization trend, and pyroxene exsolution lamellae. The estimated TiO₂ contents (∼2.0 wt%) of the MET basalt and MIL 05035 are close to the bulk-rock TiO₂ contents of Y-793169 and A-881757. These similarities suggest that Y-793169, A-881757, MIL 05035, and the MET basalt came from the same basalt flow, which we designate the YAMM basalt. The source-basalt pairing of the YAMM is also supported by their similar REE abundances, crystallization ages (approx. 3.8-3.9 Ga), and isotopic compositions (low U/Pb, low Rb/Sr, and high Sm/Nd). The pyroxene exsolution lamellae, which are unusually coarse (up to a few microns) by mare standards, imply a relatively slow cooling in an unusually thick lava and/or subsequent annealing within a cryptomare. Reported noble gas and CRE data with close launch ages (∼1 Ma) and ejection depths (deeper than several meters) among the four meteorites further indicate their simultaneous ejection from the moon. Despite the marginally close terrestrial ages, pairing in the conventional Earth-entry sense seems unlikely because of the remote recovery sites among the YAMM meteorites.The high abundance (68%) of mare components in MET 01210 estimated from a two-component mixing model calculation could have resulted from either lateral mixing at a mare-highland boundary or vertical mixing in a cryptomare. The proportion of mare materials in MET 01210 is greater than in Apollo core samples at the mare-highland boundary. The burial depth (>several meters deep) inferred from the lack of surface irradiation of MET 01210 exceeds the typical mare regolith thickness (a few meters). Thus, the source of the YAMM meteorites is likely a terrain of locally high mare-highland mixing within a cryptomare. We searched for a possible source crater of the YAMM meteorites within the well-defined cryptomare, based on the multiple constraints obtained from this study and published data. An unnamed 1.4 km-diameter crater (53°W, 44.5°S) on the floor of the Schickard crater is the most suitable source for the YAMM meteorites.The ²³⁸U/²⁰⁴Pb (μ) value of the YAMM basalts is extremely low, relative to those of the Apollo mare basalts, but comparable to those of the Luna 24 very low-Ti basalts. The low-μ source indicates a derivation from a less differentiated mantle with a lack of KREEP components. Although the chemical sources of materials and heat source of melting might be independent, the heat source that generated the source magma of the YAMM and Luna 24 basalts may not be related to KREEP, unlike the case of the Apollo basalts. The distinct chemical and isotopic compositions of mantle sources between the Apollo basalts and the YAMM/Lunar 24 basalts imply differences in mantle composition and thermal evolution between the Procellarum KREEP Terrane (PKT) and non-PKT regions of the nearside.     

The mineral chemistry and origin of xenoliths from the lavas of Anjouan,Comores Archipelago,Western Indian Ocean

Mineralogical data for xenoliths occurring as inclusions in the fissure erupted alkali basalts and the basanitic tuffs of Anjouan reveal three xenolith suites: 1) the lherzolites, 2) the dunites and wehrlites, 3) the gabbros and syenites. The dunite-wehrlite suite and the gabbro suite are shown to represent high-level cumulate sequences resulting from ankaramitic fractionation of the hy-normative shield-building lavas and cotecictic fractionation of the alkali basalt lavas respectively, whilst the syenitic xenoliths represent evolved high-level intrusions. Mineralogical and rare earth element (REE) data indicate that the most likely origin for the spinel lherzolite xenoliths is by extraction of a basaltic phase from spinel peridotite, leaving a light REE-poor spinel lherzolite residuum. REE models, constructed using model peridotite assemblages, imply that the hy-normative basalt lavas may be derived by partial melting of spinel peridotite at pressures of <20–25 kb leaving a residual lherzolite, and that the alkali basalt and basanite melts are formed by small degrees of melting of a garnet-peridotite source at pressures of >20–25 kb. The spinel lherzolite source for the hy-normative basalts has been accidentally sampled during explosive eruption of the alkali basalt and basanite magmas.     

Gold solubility in oxidized and reduced, water-saturated mafic melt

We have performed experiments to evaluate Au solubility in natural, water-saturated basaltic melts as a function of oxygen fugacity. Experiments were carried out at 1000 °C and 200 MPa, and oxygen fugacity was controlled at the fayalite-magnetite-quartz (FMQ) oxygen fugacity buffer and FMQ + 4. All experiments were saturated with a metal-chloride aqueous solution loaded initially as a 10 wt% NaCl eq. fluid. The stable phase assemblage at FMQ consists of basalt melt, olivine, clinopyroxene, a single-phase aqueous fluid, and metallic Au. The stable phase assemblage at FMQ + 4 consists of basalt melt, clinopyroxene, magnetite-spinel solid solution, a single-phase aqueous fluid, and metallic Au. Silicate glasses (i.e., quenched melt) and their contained crystalline material were analyzed by using both electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Measured Au concentrations in the quenched melt range from 4.8 μg g⁻¹ to 0.64 μg g⁻¹ at FMQ + 4, and 0.54 μg g⁻¹ to 0.1 μg g⁻¹ at FMQ. The measured solubility of Au in olivine and clinopyroxene was consistently below the LA-ICP-MS limit of detection (i.e., 0.1 μg g⁻¹). These melt solubility data place important limitations on the dissolved Au content of water-saturated, Cl- and S-bearing basaltic liquids at geologically relevant fO₂ values. The new data are compared to published, experimentally-determined values for Au solubility in dry and hydrous silicate liquids spanning the compositional range from basalt to rhyolite, and the effects of melt composition, oxygen fugacity, pressure and temperature are discussed.     

Insights into C and H storage in the altered oceanic crust: Results from ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with δD values from −64‰ to −25‰. All samples are enriched in water relative to fresh basalts. The δD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO₂, extracted by step-heating technique, ranges between 564 and 2823 ppm with δ¹³C values from −14.9‰ to −26.6‰. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with δ¹³C = −4.5‰ and (2) an organic compound with δ¹³C = −26.6‰. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO₂ yield after H₃PO₄ attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO₂ degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO₂ is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when “fresh” oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO₂, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ∼ −4.7‰, similar to the δ¹³C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 × 10¹² molC/yr.     

Liquidus phase relationships on the join anorthite-forsterite-quartz at 10 kbar with applications to basalt petrogenesis

Liquidus phase relationships determined on the join CaAl₂Si₂O₈ (anorthite)-Mg₂SiO₄ (forsterite)-SiO₂ (quartz) at 10 kbar show that increasing pressure causes the forsterite and anorthite primary phase fields to shrink and the spinel, enstatite and silica fields to expand. The boundary line between the enstatite and forsterite fields and that between the enstatite and quartz fields both move away from the SiO₂ apex as pressure increases. Therefore, simplified source peridotite would yield simplified basaltic partial melts with decreasing silica as pressure increases, as has been found in other studies. Also, increasing pressure decreases the amount of silica enrichment in residual liquids produced by fractional crystallization. Although anorthite is unstable in simplified peridotite above 9 kbar in the system CaO-MgO-Al₂O₃-SiO₂, it is an important phase in the fractional crystallization of simplified basalts at 10 kbar and probably also in natural basalts.Contribution no. 419, Department of Geosciences, University of Texas at Dallas     

Experimental investigations of the role of H2O in calc-alkaline differentiation and subduction zone magmatism

Phase relations of natural aphyric high-alumina basalts and their intrusive equivalents were determined through rock-melting experiments at 2 kb, H₂O-saturated with fO₂ buffered at NNO. Experimental liquids are low-MgO high-alumina basalt or basaltic andesite, and most are saturated with olivine, calcic plagioclase, and either high-calcium pyroxene or hornblende (±magnetite). Cr-spinel or magnetite appear near the liquidus of wet high-alumina basalts because H₂O lowers the appearance temperature of crystalline silicates but has a lesser effect on spinel. As a consequence, experimental liquids follow calcalkaline differentiation trends. Hornblende stability is sensitive to the Na₂O content of the bulk composition as well as to H₂O content, with the result that hornblende can form as a near liquidus mineral in wet sodic basalts, but does not appear until liquids reach andesitic compositions in moderate Na₂O basalts. Therefore, the absence of hornblende in basalts with low-to-moderate Na₂O contents is not evidence that those basalts are nearly dry. Very calcic plagioclase (>An₉₀) forms from basaltic melts with high H₂O contents but cannot form from dry melts with normal are Na₂O and CaO abundances. The presence of anorthite-rich plagioclase in high-alumina basalts indicates high magmatic H₂O contents. In sum, moderate pressure H₂O-saturated phase relations show that magmatic H₂O leads to the early crystallization of spinel, produces calcic plagioclase, and reduces the total proportion of plagioclase in the crystallizing assemblage, thereby promoting the development of the calc-alkaline differentiation trend.     

Recycled crust controls contrasting source compositions of Mesozoic and Cenozoic basalts in the North China Craton

We explore Fe/Mn and Nb/Ta ratios of basalts as potential tracers for differentiating melts of recycled mafic crustal lithologies from peridotitic melts. Trace elements and Fe/Mn ratios of the Mesozoic and Cenozoic basalts from East China were analyzed by ICP-MS. Low Nb/Ta ratios (15.4 ± 0.3 (2σ, n = 45)), high Nb and Ta contents (60.1 and 4.01 ppm) and high Fe/Mn ratios (64.7 ± 1.5 (2σ, n = 45)) characterize the <110 Ma basalts. Mesozoic basalts with ages >110 Ma are characterized by superchondritic Nb/Ta ratios (20.1 ± 0.3 (2σ, n = 25)), low Nb and Ta contents (10.8 and 0.54 ppm) and slightly lower Fe/Mn ratios (60.0 ± 1.1 (2σ, n = 25)). Both the Mesozoic and Cenozoic basalts have Fe/Mn ratios higher than basaltic melt formed by partial melting of peridotite at the same MgO and CaO levels. Although both the Mesozoic and Cenozoic basalts are characterized by highly fractionated REE patterns, the >110 Ma basalts have island arc-type trace element patterns (i.e., depletion in Nb and Ta), whereas OIB-type trace element patterns (e.g., no depletion in Nb and Ta) are characteristic of the <110 Ma basalts. Based on D_Fe/Mn values for olivine, clinopyroxene, orthopyroxene and garnet, high Fe/Mn ratios and negative correlations of Fe/Mn with Yb (Y) of the <110 Ma basalts suggest clinopyroxene/garnet-rich mantle sources. The lower Fe/Mn ratios and positive correlations of Fe/Mn with Y and Yb in the >110 Ma basalts suggest orthopyroxene/garnet-rich mantle sources. Combining these data with Sr-Nd isotopes, we present a conceptual model to explain the Nb/Ta ratios and PM-normalized trace element patterns of the >110 and <110 Ma basalts. Preferential melting of recycled ancient lower continental crust during Mesozoic lithospheric thinning resulted in (1) peridotite-melt/fluid reaction that formed the orthopyroxene/garnet-rich mantle sources for the >110 Ma basalts, and (2) peridotite + rutile-bearing eclogite mixing that formed the clinopyroxene/garnet-rich mantle sources for the <110 Ma basalts. The choice of models may indeed be arbitrary and non-unique, but the goal is to seek relatively simple forward models that explain the characteristics of the lavas, and the differences between the >110 and <110 Ma basalts, in a relatively consistent geodynamic framework.     

Chemical evolution of the Mt. Hekla,Iceland, groundwaters: A natural analogue for CO2 sequestration in basaltic rocks

A detailed study of the chemical composition of the groundwater surrounding the Mt. Hekla volcano in south Iceland was performed to assess fluid evolution and toxic metal mobility during CO₂-rich fluid basalt interaction. These fluids provide a natural analogue for evaluating the consequences of CO₂ sequestration in basalt. The concentration of dissolved inorganic C in these groundwaters decreases from 3.88 to 0.746 mmol/kg with increasing basalt dissolution while the pH increases from 6.9 to 9.2. This observation provides direct evidence of the potential for basalt dissolution to sequester CO₂. Reaction path calculations suggest that dolomite and calcite precipitation is largely responsible for this drop in groundwater dissolved C concentration. The concentrations of toxic metal(loid)s in the waters are low, for example the maximum measured concentrations of Cd, As and Pb were 0.09, 22.8 and 0.06 nmol/kg, respectively. Reaction path modelling indicates that although many toxic metals may be initially liberated by the dissolution of basalt by acidic CO₂-rich solutions, these metals are reincorporated into solid phases as the groundwaters are neutralized by continued basalt dissolution. The identity of the secondary toxic metal bearing phases depends on the metal. For example, calculations suggest that Sr and Ba are incorporated into carbonates, while Pb, Zn and Cd are incorporated into Fe (oxy)hydroxide phases.     

Dissolution of Columbia River Basalt under mildly acidic conditions as a function of temperature: Experimental results relevant to the geological sequestration of carbon dioxide

Increasing attention is being focused on the rapid rise of CO₂ levels in the atmosphere, which many believe to be the major contributing factor to global climate change. Sequestering CO₂ in deep geological formations has been proposed as a long-term solution to help stabilize CO₂ levels. However, before such technology can be developed and implemented, a basic understanding of H₂O–CO₂ systems and the chemical interactions of these fluids with the host formation must be obtained. Important issues concerning mineral stability, reaction rates, and carbonate formation are all controlled or at least significantly impacted by the kinetics of rock–water reactions in mildly acidic, CO₂-saturated solutions. Basalt has recently been identified as a potentially important host formation for geological sequestration. Dissolution kinetics of the Columbia River Basalt (CRB) were measured for a range of temperatures (25–90 °C) under mildly acidic to neutral pH conditions using the single-pass flow-through test method. Under anaerobic conditions, the normalized dissolution rates for CRB decrease with increasing pH (3 ? pH ? 7) with a slope, η, of −0.15 ± 0.01. Activation energy, E_a, has been estimated at 32.0 ± 2.4 kJ mol⁻¹. Dissolution kinetics measurements like these are essential for modeling the rate at which CO₂-saturated fluids react with basalt and ultimately drive conversion rates to carbonate minerals in situ.     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

Geology, petrochemistry, and genesis of the bimodal lavas of Osham Hill, Saurashtra, northwestern Deccan Traps

The Saurashtra region in the northwestern Deccan continental flood basalt province (India) is notable for compositionally diverse volcano-plutonic complexes and abundant rhyolites and granophyres. A lava flow sequence of rhyolite-pitchstone-basaltic andesite is exposed in Osham Hill in western Saurashtra. The Osham silicic lavas are Ba-poor and with intermediate Zr contents compared to other Deccan rhyolites. The Osham silicic lavas are enriched in the light rare earth elements, and have ε_Nd (t = 65 Ma) values between −3.1 and −6.5 and initial ⁸⁷Sr/⁸⁶Sr ratios of 0.70709-0.70927. The Osham basaltic andesites have initial ε_Nd values between +2.2 and −1.3, and initial ⁸⁷Sr/⁸⁶Sr ratios of 0.70729-0.70887. Large-ion-lithophile element concentrations and Sr isotopic ratios may have been affected somewhat by weathering; notably, the Sr isotopic ratios of the silicic and mafic rocks overlap. However, the Nd isotopic data indicate that the silicic lavas are significantly more contaminated by continental lithosphere than the mafic lavas. We suggest that the Osham basaltic andesites were derived by olivine gabbro fractionation from low-Ti picritic rocks of the type found throughout Saurashtra. The isotopic compositions, and the similar Al₂O₃ contents of the Osham silicic and mafic lavas, rule out an origin of the silicic lavas by fractional crystallization of mafic liquids, with or without crustal assimilation. As previously proposed for some Icelandic rhyolites, and supported here by MELTS modelling, the Osham silicic lavas may have been derived by partial melting of hot mafic intrusions emplaced at various crustal depths, due to heating by repetitively injected basalts. The absence of mixing or mingling between the rhyolitic and basaltic andesite lavas of Osham Hill suggests that they reached the surface via separate pathways.