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.     

CO2 transfer between the upper mantle and the atmosphere: temporary storage in the lower continental crust

The CO₂ atmospheric content has shown large variations over geological times. High contents (up to one order of magnitude more than present-day values) ultimately correspond to discrete episodes of mantle degassing, either juvenile, or subduction-related (carbon recycling). A number of arguments (e.g. the continuous volume increase of carbonate-bearing sediments with time) suggest that, throughout the Earth's history, juvenile CO₂ has formed a major contribution to the global carbon budget of the Earth.
The absence of a direct relationship between major volcanic episodes and the average CO₂ atmospheric content suggests that volcanoes might not be the only way by which mantle CO₂ is transported to the surface. It is proposed that large quantities of juvenile CO₂ could temporarily be stored in the lower continental crust during major episodes of granulite formation. These are primarily caused by magmatic underplating and they result in a vertical accretion of the crust by accumulation of CO₂-bearing, mantle-derived magmas. Most of the CO₂ migrates through the crust during post-metamorphic evolution and isostatic restoration of the normal continental thickness. However, large quantities of CO₂ can still be present in some areas, notably as high-density fluids enclosed in minerals.     

Instrumental Neutron Activation Analysis Of French Geochemical Reference Samples

Instrumental neutron activation analytical data, for eighteen trace elements (Ba, Co, Cr, Cs, Hf, Rb), Sb, Sc, Ta, Th, La, Ce, Nd, Sm, Eu, Tb, Yb, Lu), Hd₂O and Fe₂0₃ in eleven French geoche-mical reference samples are presented and discussed briefly.     

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.     

The Abbey Evaluation of Reference Sample IF-G. The Significance of Abbey's Method For Laboratory Quality

Abbey's select laboratories method has been applied to the reported data for major and minor elements in the proposed GIT-IWG reference sample IF-G. The final values obtained by this method have been compared with the recommended values published by Govindaraju in 1984. Slightly different percentages are suggested for MgO, K₂O and Fe₂O₃T. The importance of applying the Abbey method by participants in co-operative studies is emphasized. Such an application gives a better understanding of data treatment and of the degree of reliability of published final values; furthermore the objective score obtained for laboratory quality will stimulate participating laboratories to improve their analytical methods and procedures. As an illustration some improvements in the laboratory of the authors are mentioned.     

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.     

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.     

On the origin of CO2-rich fluid inclusions in migmatites

Abstract Nearly pure CO₂ fluid inclusions are abundant in migmatites although H₂O-rich fluids are predicted from the phase equilibria. Processes which may play a role in this observation include (1) the effects of decompression on melt, (2) generation of a CO₂-bearing volatile phase by the reaction graphite + quartz + biotite + plagioclase = melt + orthopyroxene + CO₂-rich vapour, (3) selective leakage of H₂O from CO₂+ H₂O inclusions when the pressure in the inclusion exceeds the confining pressure during decompression, and (4) enrichment of grain-boundary vapour in CO₂ by subsolidus retrograde hydration reactions.     

Primary carbonate/CO2 inclusions in sapphirine-bearing granulites from central Sri Lanka

High-density CO₂-rich fluid inclusions from a sapphirine-bearing granulite (Hakurutale, Sri Lanka) have been studied by microthermometry, Raman spectrometry and SEM analysis. Based on textural evidence, two groups of inclusions can be identified: primary, negative crystal shaped inclusions (group I) and pseudo-secondary inclusions, which experienced a local, limited post-trapping modification (group II). Both groups contain magnesite as a daughter mineral, occurring in a relatively constant fluid/solid inclusion volume ratio (vol_solid =0.15 total volume). CO₂ densities for group I and II differ only slightly. Both groups contain a fluid, which was initially trapped at peak metamorphic conditions as a homogeneous (CO₂+MgCO₃) mixture. Thermodynamic calculations suggest that such a fluid (CO₂+15 vol% MgCO₃) is stable under granulite facies conditions. After trapping, magnesite separated upon cooling, while the remaining CO₂ density suffered minor re-adjustments. A model isochore based on the integration of the magnesite molar volume in the CO₂ fluid passes about 1.5–2 kbar below peak metamorphic conditions. This remaining discrepancy can be explained by the possible role of a small quantity of additional water.     

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.     

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.     

Determination of Carbonate Carbon in 41 International Geochemical Reference Samples by Coulometric Method

The carbonate-carbon (CO₂) content of forty-one geochemical reference samples has been determined by coulometric method following acid treatment of the sample for releasing CO₂. The method is superior to the conventional methods in speed, accuracy, sensitivity, specificity, and the coverage of CO₂ range. The results on NBS limestone samples agree well with the certified values. The precision of the method is 0.5 % r.s.d., and the practical detection limit is 10 ppm C.     

The Preparation and Characterisation of Two New Geological Survey of Japan Geochemical Reference Materials: Copper ore JCu-1 and Zinc ore JZn-1

Two new geochemical reference materials, copper ore JCu-1 and zinc ore JZn-1 have been prepared by the Geological Survey of Japan (GSJ) for the determination of major and minor elements and isotopic compositions. JCu-1 is a sample of Cu-bearing sulfide ore typical of the Kamaishi mine in Iwate Prefecture, Japan, and is composed mainly of hedenbergite, chalcopyrite, quartz and calcite. Pyrrhotite, magnetite and actinolitic amphibole were also commonly found. The Zn-rich ore, JZn-1 is a crude ore from the Kamioka Pb-Zn mine in Gifu Prefecture, Japan. The sample consists of hedenbergite, quartz, calcite, sphalerite and epidote as main crystalline phase. Homogeneity test results showed that all studied constituents including ore elements such as Cu, Pb and Zn can be considered to be homogeneously distributed. Provisional collaborative analyses were carried out in ten laboratories, and the data were evaluated using a robust statistical method using z-scores. Recommended values for a number of major elements including TiO₂, Al₂O₃, MnO, MgO, CaO, Na₂O, K₂O, Fe (total), Zn, Cu and Pb were established. In addition, information values for eighteen major, minor and trace elements are presented to support future collaborative analyses.     

Grain boundary migration of water and carbon dioxide during uplift of garnet-zone Alpine Schist, New Zealand

Abstract Deformed quartz veins in garnet-zone schist adjacent to the active Alpine Fault, New Zealand, have fluid inclusions trapped along quartz grain boundaries. Textures suggest that the inclusions formed in their present shapes during annealing of the deformed veins. Many of the inclusions are empty, but some contain carbon dioxide with densities that range from 0.16 to 0.80 g cm⁻³. No water, nitrogen or methane was detected. The inclusions are considerably more CO₂-rich than either the primary metamorphic fluid (<5% CO₂) or fluids trapped in fracture-related situations in the same, or related, rocks (<50% CO₂). Enrichment of CO₂ is inferred to have resulted from selective migration (wicking) of saline water from the inclusions along water-wet grain boundaries after cooling-induced immiscibility of a water-CO₂ mixture. Inclusion volumes changed after loss of water. Non-wetting CO₂ remained trapped in the inclusions until further percolation progressively removed CO₂ in solution. This mechanism of fluid migration dominated in ductile quartz-rich rocks near, but below, the brittle-ductile transition. At deeper levels, hydraulic fracturing is also an important mechanism for fluid migration, whereas at shallower levels advection through open fractures dominates the fluid flow regime.     

Infrared spectroscopy of Triassic conodonts: a new tool for assessing conodont diagenesis

The Fourier transform infrared spectra of individual conodonts with various CAI values indicate definite changes in conodont francolite during diagenesis. Steady decarbonation can be observed in the increasing intensity of the band with the wavenumber 2340 an^-1, which is assigned to trapped molecular CO₂. Carbon dioxide originates from decomposing CO^2-₃-ions occupying the B-site in francolite. Furthermore, the intensity of the water-deformation band at 1644 cm^-1 decreases with higher CAI values. These changes of intensity can be quantified by calculating the maximum extinction (E_max) for the corresponding absorption maxima and correlated with the CAI. Unaltered conodonts have a relative variable water 'content' and very little CO₂. Up to a CAI value of 4 conodont francolite continuously expells water and carbon dioxide is trapped. Conodonts with CAI = 5 have similar water 'contents' to CAI = 4 conodonts, but decarbonation continues to take place during this stage of diagenesis.     

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.     

The Precision of Classical Rock Analysis

Three rock reference samples. W-2, DNC-1, and BIR-1, were analysed five times over several months by classical chemical methods using a Youden Square as the experimental design. A significant variation for the data classified by months was found for SiO₂, CaO, H₂O^-, and TiO₂ among the 15 constituents determined. Nevertheless, most standard deviations for the five data for each oxide in any sample, as well as the error standard deviations from the analyses of variance, are less than or approximately equal to the allowable difference between duplicate determinations traditionally used as limits of error. We also determined nine constituents in three portions each of two samples, W-2 and DNC-1, the six portions being analysed concurrently. F ratios for 16 comparisons of the variances of the five data for an oxide obtained over several months and of the three data determined as a group were significant for only one oxide, total iron as Fe₂O₃ in W-2. We conclude that, if a chemist analyses rock samples carefully, the variation of the determinations will be the same for portions analysed as a group, or analysed over a time interval.     

新疆阿尔泰东南缘哈拉乔拉镁铁质岩体地球化学特征与地质意义

哈拉乔拉镁铁质岩体位于新疆阿尔泰造山带东南缘, 主要岩石类型有辉长岩、辉长苏长岩、含长辉石岩、橄榄辉长岩和橄长岩.哈拉乔拉岩体具有低TiO₂(0.09%~1.28%)、低碱(Na₂O+K₂O=0.37%~0.78%)的特点, 属于拉斑玄武岩系列; 富集大离子亲石元素和轻稀土元素, 亏损高场强元素(Nb、Ta等), ε_Nd(t)为-2.62~-0.78, ε_Sr(t)为37.49~45.28.元素地球化学和Nd-Sr同位素组成表明, 岩浆源区为被消减板片交代改造过的富集型岩石圈地幔.原生岩浆为高镁拉斑玄武岩浆, 岩浆演化过程中主要发生了橄榄石、单斜辉石以及斜长石的分离结晶/堆晶, 后期有钛铁矿的析出.      

Heavy Mineral Placer Deposits of Ekakula Beach, Gahiramatha Coast, Orissa, India

Abstract: Ilmenite, hematite, garnet, monazite, zircon, rutile, magnetite, sillimanite, pyroxene and amphibole from the beach sands of Ekakula, Gahiramatha coast, Orissa, India are reported here for the first time. Their total concentration varies from 26. 4 to 100%. Ilmenite, monazite and zircon are between 100 and 300 um in size and are well rounded in shape. Ilmenite-hematite intergrowth is common. Ilmenite has 50. 02–54. 73% TiO₂, 42. 42–46. 90% FeO (total Fe) and small amounts of Al, Mn, Mg, Ca, Ba, Si, V, Cr, and Zn. The bulk samples contain 10. 63–41. 42 % TiO₂, 6. 15–26. 07 % FeO, 5. 86–16. 75 % Fe₂O₃, 7. 41–61. 74 % SiO₂, 1. 39–12. 83% A1₂O₃, 0. 32–4. 97% CaO, 0. 53–4. 24% P₂O₅, 0. 17–3. 27% MgO, 0. 15–2. 97% Na₂O, 0. 07–2. 34% K₂O, and 0. 05–0. 71% V₂O₅ together with appreciable amounts of La, Ce, Pr, Nd, Sm, Eu, Y, U, Th, Zr, and trace amounts of Pb, Zn, Cu, Ni, Co, and Cr. Khondalite, charnockite, calc-silicate granulite, leptynite, migmatite, gneiss, basic granulite and pegmatite of the Eastern Ghats appear to be the major source for the above heavy mineral assemblages. The samples are amenable to gravity and magnetic methods of beneficiation.