Ionic association in H2O–CO2 fluids at mid-crustal conditions

The equilibrium constant, K _a, of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K _a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H₂O and CO₂ at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H₂O–CO₂ mixtures can be obtained and the change in log K _a with addition of CO₂ in aqueous solutions evaluated. These changes in log K _a with addition of CO₂ are consistent with measured changes of log K _a with addition of Ar in supercritical H₂O–Ar solutions.
Log K _a of KCl and NaCl increase to an increasing extent as the mole fraction of CO₂ increases in H₂O–CO₂ solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K _a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO₂ mole fraction increases from 0.0 to 0.35. Such changes in log K _a will have dramatic effects on the solubility of minerals in CO₂-rich environments.     

Observations on New Approaches for the Determination of Platinum-Group Elements, Gold and Silver in Different Geochemical Samples from Siberia and the Far East

Some recent experiments on the determination of Au and the platinum-group elements (PGE) in geochemical samples are reviewed. Emphasis is given to the determination of ultra-low levels of PGE concentrations in resistant matrices, including chromites, molybdenites and ultrabasic ores. The problems and features of PGE determination in samples of various chemical composition are considered. For each sample type studied, a series of sample preparation techniques are proposed. These techniques included acid digestion, fusion with sodium peroxide, cold sintering with an oxidizing mixture of Na₂O₂+ Na₂CO₃ and also oxidizing fluorination with bromine trifluoride. A new approach for preparing geochemical material prior to digestion, based on mechano-chemical activation with simultaneous hyperfine grinding, is proposed and studied. The instrumental determination of PGE contents was carried out directly by AAS from extracted organic phases. It was found that a combination of digestion processes was required to achieve geochemical background levels of Au and PGE concentrations with the following detection limits: Pd, Rh - 1 ng g⁻¹, Pt, Ru - 10 ng g⁻¹, Au - 0.2 ng g⁻¹, Ag - 0.1 ng g^−1. The uncertainty in PGE and Au determination in geochemical samples is dependent on metal concentration, and also on their distribution in samples. The total analytical uncertainty of the proposed method is between 15-30%.     

Concentrations of Trace Elements in Carbonate Reference Materials Coral JCp-1 and Giant Clam JCt-1 by Inductively Coupled Plasma-Mass Spectrometry

Trace elements in the Geological Survey of Japan carbonate reference materials Coral JCp-1 and Giant Clam JCt-1 were determined by inductively coupled plasma-mass spectrometry after digestion with 2% v/v HNO₃. A standard addition method was adopted in this determination in order to neutralise the Ca matrix effect. In addition, Sc, Y, In and Bi were used as internal standards to control the matrix effect and correct instrumental drift. Of the eighteen elements measured in JCp-1, precisions for fourteen elements, including Cu, Cd and Ba, were better than 10% RSD and concentrations ranged from 0.002 μg g^-1 (Cs) to 8.02 μg g^-1 (Ba). The concentrations of measured trace elements in JCt-1, except for Cu, were lower than those in JCp-1. Precisions for all elements with concentrations higher than 0.04 μg g^-1 in JCt-1 were also better than 10% RSD and concentrations were found to be between 0.001 μg g^-1 (Cs) and 4.84 μg g^-1 (Ba). The concentrations of more than fifteen trace elements in the aragonite reference materials are reported here for the first time. Both reference materials are suitable for use in geochemical studies of environmental reconstruction based upon biogenic carbonate materials.     

Refinements in BaSO4 to CO2 Preparation and δ18 O Calibration of the Sulfate Reference Materials NBS-127, IAEA SO-5 and IAEA SO-6

Refinements have been made to achieve over 99% yield in the conversion of CO to CO₂ in order to improve the reproducibility and accuracy of δ¹⁸ O measurements in sulfates. BaSO₄ (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO₂; the former gas was simultaneously converted to CO₂ by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ¹⁸ O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO₂ produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO₂ equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from ¹⁸O/¹⁶O of the working calibrator we used CO₂ gas prepared from ocean water sulfate for this purpose. The calibrated δ¹⁸ O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.     

Anthropogenic CO2 in Southern Ocean surface waters: evidence from stable organic carbon isotopes

We present an approach for tracing the fate of anthropogenic CO₂, compiling a large data set of stable organic carbon isotope ratios from surface sediments, plankton, and sinking matter in the Atlantic Ocean. The δ¹³C values of sinking matter are generally lower by 0.5–4.6‰ compared to the surface sediments. This difference increases with increasing latitude, which is explained by a stronger modern increase in surface water [CO₂ (aq)] in the Southern Ocean relative to the Tropical/Subtropical Ocean. Preindustrial dissolved CO₂ concentrations in Atlantic surface waters, estimated from the δ¹³C_org of surface sediments, are compared to recently measured surface water [CO₂ (aq)] values taken from literature. We obtain only a slight increase in [CO₂ (aq)] at lower latitudes but a significant change of about 7 ± 2 μ m in high latitudinal surface waters which we attribute to anthropogenic perturbation. Our results suggest that CO₂ released by human activities has been stored in Southern Ocean surface waters.     

Synthetic Fluid Inclusions in the Systems NaCl-H2O and NaCl-CO2-H2O: Dissolution Temperatures of Halite

Abstract. This study examined the effect of CO₂ on NaCl solubility in hydrothermal fluid, with the synthetic fluid inclusion technique. Fluid inclusions of 30–40 wt% NaCl and 5 mol % CO₂ were synthesized, and their halite dissolution temperatures, T_m(halite), were measured. The solubilities of NaCl in CO₂-bearing aqueous fluid were obtained at 160–320C under vapor-saturated pressures. The T_m(halite) value in aqueous fluid with 5 mol % CO₂ obtained in this study agrees with that of Schmidt et al. (1995), showing that 5 mol % CO₂ reduces the solubility of NaCl by about 1 wt%.
Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2-free solution. Therefore, an increase of CO2 content in ore-forming solutions may cause deposition of iron minerals and produce ore deposits.     

DETERMINATION OF PHOSPHOROUS IN FIFTY-NINE GEOCHEMICAL REFERENCE SAMPLES BY EXTRACTIVE SPECTROPHOTOMETRY

A digestion procedure with sequential use of HF-HCl and HNO₃-HClO₄ involving yellow vanadium molybdophosphate complex and its extraction into isobutylmethylketone (IBMK) has been employed for estimation of phosphorus in 59 geochemical reference samples. The agreement between the results obtained from IBMK-extraction and the recommended values has been found to be better than those available from the usual procedures (i.e., estimation in the aqueous phase).     

Ijolite versus carbonatite as sources of fenitization

Ijolite-carbonatite complexes are ubiquitously surrounded of an aureole of metasomatically altered rocks. The process of alteration is termed fenitization and is generally caused by peralkaline fluids emanating from cooling alkaline, i.e. ijolite and carbonatite magmas. Ijolites and carbonatites normally occur together and attempts to determine the source of the fenitizing fluids may therefore lead to controversial, if not erroneous, conclusions.
Mineralogical and chemical data of fenites from Oldoinyo Lengai (Tanzania), Fen (Norway), and Alnö (Sweden) are reviewed in the present paper in order to reveal the main factors controlling the fenitization around ijolite and carbonatite. Despite the overall alkaline nature of the process, variables such as XCO₂ of the fluid, activity gradients of SiO₂, Al₂O₃ and CaO, FeO/MgO ratio, f O₂ and temperature gradients may differ, producing distinctive patterns of fenitization around the two magmatic sources. The ijolitic-type fluid has low XCO₂, high activities of alkalies, SiO₂ and Al₂O₃, and low activity of CaO. The f O₂ evolves along the hm-mt buffer conditions and the temperature falls gradually with distance from the magmatic source. The carbonatitic-type fluid has high XCO₂, high activities of alkalies and CaO, and low activities of SiO₂ and Al₂O₃. Temperatures and f O₂ are initially high, but decrease sharply with distance from the source. Moreover, the CO₂-rich fluid may complex and transport the REE.     

The evolution of fluorine-rich felsic magmas: source dichotomy, magmatic convergence and the origins of topaz granite

Topaz granite is alkali-feldspar granite that contains essential albite, quartz, K-feldspar, lithium-mica, and topaz. As a group topaz granites are characterized by their extreme enrichment in F (up to 3 wt%) and a wide variety of lithophile elements. They can be subdivided into a 'low-P₂O₅ subtype' (P₂O₅ < 0.1 wt%, Al₂O₃ < 14.5 wt%, SiO₂ > 73 wt%) and a 'high-P₂O₅ subtype' (P₂O₅ > 0.4 wt%, Al₂O₃ > 14.5 wt%, SiO₂ < 73 wt%), the δ¹⁸O values of which indicate a dichotomy of source rock: the low-P₂O₅ subtype (δ¹⁸O < 10‰) having a meta-igneous protolith and the high-P₂O₅ subtype (δ¹⁸O > 10 ‰) a source with a significant component of pelitic material. The unusually high F contents enhance the efficacy of melt segregation and crystal-melt fractionation and so facilitate extreme differentiation in topaz granite magmas. Very low melt volumes restrict the bulk composition of the partial melts regardless of the nature of the source; and extreme fractionation forces them along a path of magmatic convergence, to produce a group of granitic rocks with near-minimum compositions so enriched in a variety of lithophile elements (Li, Nb, Ta, Sn) that economic mineralization often results.     

Hydrogen, Oxygen and Sulfur Isotope Studies of Seafloor Hydrothermal System at the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea: An Analogue of Terrestrial Acid Hot Crater-lake

Abstract. The Onsen site is an active submarine hydrothermal system hosted by the Desmos caldera in the Eastern Manus Basin, Papua New Guinea. The hydrothermal fluid is very acidic (pH=1.5) and abundant native sulfur is deposited around the vent. The δ³⁴S values of native sulfur range from -6.5 to -9.3 %o. δ³⁴S values of H₂S and SO₄ in the hydrothermal fluid are -4.3 to -9.9 %o and +18.6 to +20.0 %o, respectively. These δ³⁴S values are significantly lower than those of the other hydrothermal systems so far reported. These low δ³⁴S values and the acidic nature of the vent fluids suggest that volcanic SO₂ gas plays an important role on the sulfur isotope systematic of the Onsen hydrothermal system. Relationship among the δ³⁴S values of S-bearing species can be successively explained by the model based on the disproportionation reaction starting from the volcanic SO₂ gas. The predicted δ³⁴S values of SO₂ agree with the measured whole rock δ³⁴S values. δD and δ¹⁸O values of clay minerals separated from the altered rock samples also suggest the contribution of the magmatic fluid to the hydrothermal system. Present stable isotopic study strongly suggests that the Onsen hydrothermal site in the Desmos caldera is a magmatic submarine hydrothermal system.     

Major Element Data (1966–1978) for The Six "Nimroc" Reference Samples

The results are given for all the determinations made by the co-operating laboratories of major elements in the six NIMROC rock samples (granite, syenite, lujavrite, norite, pyroxenite and dunite) prepared by the National Institute for Metallurgy in 1966. Relevant statistical data are given for the sets of results for each major constituent, and recommended values for all constituents except Al₂0₃, Na₂0, K₂0and CO₂ in dunite, Fe₂O₃, MgO and CO₂ in the granite, Fe₂₃ and CO₂ in the norite and CO₂ in the pyroxenite.
This report and that on the trace and minor elements issued in 1978 complete the revision of the recommended values. It is suggested that analysts should concentrate rather on those constituents for which the results have shown such a wide scatter that they can be of no usc for reference purposes, than on those for which the ualues are fairly well established.     

Dating cleavage formation in slates and phyllites with the 40Ar/39Ar laser microprobe: an example from the western New England Appalachians, USA

Determinations of the absolute age of cleavage formation can provide fundamental information about the evolution of orogenic belts. However, when applied to cleavages in slates and phyllites, conventional dating methods are complicated by problems related to mineral separation and the presence of multiple cleavage generations. In situ high-spatial-resolution ⁴⁰Ar/³⁹Ar laser microprobe geochronology and microstructural observations indicate that the age of cleavage formation in slates and phyllites can be constrained by analysing zones of tightly packed cleavage domains. Three regionally developed cleavages (S₂, S₃, and S₄) are present in the northern Taconic Allochthon of Vermont and New York. Representative samples were studied from a variety of localities where these cleavages, which are defined by white micas, are well developed. In the suite of samples, only S₃ and S₄ are expressed as domains that are sufficiently wide and spatially isolated in thin section to permit quantitative ⁴⁰Ar/³⁹Ar geochronology. Mean ⁴⁰Ar/³⁹Ar laser microprobe ages for these domains are 370.7 ± 1.0 Myr for S₃ and 345.5 ± 1.7 Myr for S₄. Because estimates of the Ar closure temperature for white micas are substantially higher than the inferred growth temperatures of the micas defining S₃ and S₄, these values are interpreted as periods since cleavage formation. This interpretation is consistent with independent geochronological constraints on the age of the Acadian orogeny in the region.     

The (Na–Ca)amphibole–albite–chlorite–epidote–quartz geothermobarometer in the system S–A–F–M–C–N–H2O. 1. An empirical calibration

The proposed geothermobarometer is based on an empirical calibration which takes account of two equilibria involving the tremolite, edenite, pargasite and hastingsite components in amphiboles. It has applications to assemblages found in metabasic rocks of widely different chemical compositions (magnesian to Fe-rich metabasalts), and for metamorphism ranging from lower greenschist to highest amphibolite facies. Knowing the Si_(T1), Al^iv, Al^vi, Fe³⁺, Fe²⁺, Mg, Ca, Na_M4, Na_A and A vacancy in an amphibole, and the Al³⁺ and X _Mg in coexisting epidote and chlorite, it is possible to calculate two values of In K _d for this assemblage. These equilibria involve edenite-tremolite and (pargasite/hastingsite)-tremolite end-members in amphibole (the calculation program is given). For these equilibria, the isopleths (iso-values of K _d) have been calculated for 0.27 < X _Mg < 0.75 and 0 < X _Fe3+= Fe³⁺/(Fe³⁺+ Al^vi) < 0.8. It is then possible to determine pressure and temperature directly when X _Mg, X _Fe3+, In K _d for tremoliteedenite and In K _d for (pargasite/hastingsite)-tremolite are known. Application of this geothermobarometer is limited to Ca-free plagioclase assemblages, and complete P–T paths can be drawn only if all the minerals are considered together. Phase relations at successive stages of crystallization can be constrained by studying the relationships between the coexisting minerals, their zoning and the metamorphic fabrics.     

TEM observations of several spinel-garnet assemblies: toward the rheology of the transition zone

In order to better identify the mineral phase which controls the rheology of the transition zone (between 410 and 660 km depth) transmission electron microscopy observations were made on several coexisting spinel-garnet assemblies: alkremite xenolith; pyrope-rich – MgO:1.1Al₂O₃ spinel assembly deformed at 1173K, 800 MPa in a Griggs apparatus; (Mg,Fe)₃(Al,Mg,Si)₂Si₃O₁₂ majorite – (Mg,Fe)₂SiO₄ spinel assembly synthesized in a laser heated diamond anvil cell. It was found that garnet crystals systematically remain undeformed while spinel crystals are plastically deformed. These results are in accord with the assumption that the rheology of majorite is stronger than the rheology of spinel, in the conditions of the transition zone.     

Metamorphic decarbonation, silicate weathering and the long-term carbon cycle

The seawater ⁸⁷Sr/⁸⁶Sr curve implies a 50–100 Myr episodicity in weathering rate which requires a corresponding variation in CO₂ degassing from the solid earth to the atmosphere. It is proposed that this is caused by orogenesis, which both produces CO₂ as a result of metamorphic decarbonation reactions, and consumes extra CO₂ as a consequence of erosion-enhanced weathering. Global climate on the geological time-scale is therefore contTolled by the difference between the relatively large and variable orogenic-moderated degassing and weathering CO₂ fluxes.     

Stable isotopic and fluid inclusion evidence for meteoric fluid penetration into an active mountain belt; Alpine Schist, New Zealand

Calcite and quartz veins have formed, and are forming, in steeply dipping fissures in the actively rising Alpine Schist metamorphic belt of New Zealand. The fluids that deposited these minerals were mostly under hydrostatic pressure almost down to the brittle-ductile transition, which has been raised to 5-6 km depth by rapid uplift. Some fluids were trapped under lithostatic pressures. Fluids in the fissure veins were immiscible H₂O + NaCl-CO₂ mixtures at 200-350 C. Bulk fluid composition is 15-20 mol% CO₂ and <4.3 total mol CH₄+ N₂+ Ar/100mol H₂O. Water hydrogen isotopic ratio δD_H2O in the fissure veins spans -29 to -68‰, δ¹⁸O_H2O -0.7 to 8.5‰, and bulk carbon isotopic ratio δ¹³C ranges from -3.7 to -11.7‰. The oxygen and hydrogen isotopic data suggest that the water has a predominantly meteoric source, and has undergone an oxygen isotope shift as a result of interaction with the host metamorphic rock. Similar fluids were present during cooling and uplift. Dissolved carbon is not wholly derived from residual metamorphic fluids; part may be generated by oxidation of graphite.     

Decompressional coronas and symplectites in granulites of the Musgrave Complex, central Australia

Abstract In granulite facies metapelitic rocks in the Musgrave Complex, central Australia, reaction between S1 garnet and sillimanite involves the development in S2 of both garnet + cordierite + hercynitic spinel + biotite and hercynitic spinel + cordierite + sillimanite + biotite. The S2 assemblages occur either in coronas and symplectites, mainly around garnet, or, in rocks in which S2 is more strongly developed, as recrystallized assemblages. Ignoring the presence of biotite and ilmenite, the mineral textures can be accounted for qualitatively by a consideration of the model system FeO-MgO-Al₂O₃-SiO₂ (FMAS); the textural relationships accord with decompression accompanying the change from S1 to S2. However, since biotite and ilmenite are involved in the assemblages, the parageneses are better accounted for in terms of equilibria in the expanded model system K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂-TiO₂-Fe₂O₃ (KFMASHTO), i.e. AFM + TiO₂+ Fe₂O₃. The coronas reflect the tectonic unroofing of at least part of the Musgrave Complex from peak S1 conditions of about 8 kbar to S2 conditions of about 4 kbar.     

Fluid-mineral equilibria in prehnite-pumpellyite to greenschist facies metabasites near Flin Flon, Manitoba, Canada: implications for petrogenetic grids

A sequence of regional metamorphic isograds indicating a range from prehnite-pumpellyite to lower amphibolite facies was mapped in metabasites near Flin Flon, Manitoba. The lowest grade rocks contain prehnite + pumpellyite and are cut by younger brittle faults containing epidote + chlorite + calcite. Isobaric temperature- X _CO2 and pressure-temperature (constant X _CO2) diagrams were calculated to quantify the effects of CO₂ in the metamorphic fluid on the stability of prehnite-pumpellyite facies minerals in metabasites containing excess quartz and chlorite. Prehnite and, to a lesser extent, pumpellyite are stable only in fluids with X _co2 <0.002. For X _co2>0.002, epidote + chlorite + calcite assemblages are stable. Our calculated phase relations are consistent with regional metamorphism in the Flin Flon area in the presence of an H₂O-rich fluid and a more CO₂-rich fluid in the later fault zones. We believe that the potential effects of small amounts of CO₂ in the metamorphic fluid should be assessed when considering the pressure-temperature implications of mineral assemblages in low-grade metabasites.     

Carbon sources in arc volcanism, with implications for the carbon cycle

New CO₂/³ He data from the East Sunda Arc (Indonesia) confirm earlier observations that arc volcanic gases have higher CO₂/³ He ratios than MOR environments.On average, > 80% of arc volcanic CO₂ is recycled, exogene carbon. Addition of a few percent of carbonate-bearing sediments to the mantle wedge explains much of the carbon abundance andcarbon isotopic data of arc gases, but can not explain the He isotope observations. The CO₂/³He in arc volcanoes is not strongly dependent on the composition of modem trough sediments (e.g. deep sea clays vs carbonate-rich sequences), and calcite veins in the hydrothermally altered subducted slab may provide a contribution to the recycled carbon flux of, arcs. The sum of globally deep-subducted sediment and slab carbon exceeds the estimated arc CO₂ flux, and approximately 3.5 teramole of carbon may return annually to the mantle in convergent zones. The modem combined processes of MOR volcanism, slab alteration, and subduction volcanism do not produce a substantial carbon flux into the exosphere, and rate-changes in ocean floor spreading are unlikely to cause major changes in atmospheric CO₂ as a result of changes in the volcanic CO₂ fluxes. Intense pulses of flood basalt volcanism, however, may alter the CO₂ contents of the atmosphere over the course of a millenium or so, and influence global climate.     

Determination of Traces of Rare-Earth elements, Yttrium and Thorium in Several International Geological Reference Samples and Comparison Of Data with Other Published Values

Experimental results for most rare-earth elements, yttrium and thorium in several international geological reference samples are presented and compared with other published values, where available. The analytical method used to obtain these results involved a preliminary concentration of the rare-earths On milligram quantities of iron as carrier for atomic-absorption, flame-emission and spectrophotometric determinations, or on milligram quantities of Fe₂O₃, Al₂O₃ and SiO₂ as carriers for optical-emission spectrometric determination.