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1.
Nineteen USGS GRSs were analyzed with a Dupont 903-H Moisture Analyzer at 110°C and 1000°C to obtain H2O-and H2O+, and by thermal neutron induced gamma-ray spectrometry to obtain total H2O. The values are compared with the current literature and the two techniques evaluated. Except for QLO-1 by coulometry, no significant differences were obtained when the results were compared to the the literature.  相似文献   

2.
Additional analytical data for the thirteen oxides usually determined in a rock analysis by wet methods and estimates and, conclusions from the analysis of variance are presented for the eight new USGS rock standards STM-1, RGM-1, QLO-1, SCo-1, MAG-1, SDC-1, BHVO-1 and SGR-1. The "single-solution" method of sample dissolution, and the "rapid methods" described by Shapiro were used. Three bottles of each standard were analyzed in duplicate, providing six replicate analyses of each sample. Relative standard deviations ranged from 0. 00 to 202 %, with only 12 of the possible 104 sample-oxide combinations exceeding 10 %. Most deviations exceeding 10 % occur with oxides at very low concentrations or with the determi-nation, of H2O+ and CO2, all of which often yield poor precision. These data indicate that the rapid wet chemical methods, except possibly for H2O+ and CO2, or when very low concentrations are present, can be considered reliable. Of the 104 F-ratios calculated during the analysis of variance for sample-oxide combinations, only eight equal or exceed the tabled value of 9. 55 for F0.95 (d. f. 2, 3). These data strongly support the conclusion that the contents of the bottles may be considered homogeneous for most oxides determined. When our data for an oxide in the several samples are plotted versus similar data in the USGS Prof. Paper 840 by several methods, the plots generally show good agreement for most sample-oxide combinations, but approximately thirty of the 104 show substantial differences, with no obvious correlation between the various methods used or the nature or magnitude of the differences.  相似文献   

3.
Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l−1. Bromine and I were measured by ICP-MS with detection limits of 1 μg l−1 for Br and 0.1 μg l−1 for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg−1 for F and Cl, 15 mg kg−1 for S, 0.2 mg kg−1 for Br and 0.02 mg kg−1 for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H2O degassing, reduction on zinc at 1000 °C and H2 manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.  相似文献   

4.
Abstract Two Archaean synvolcanic stocks with contact aureoles occur in the Wawa greenstone belt near Wawa, Ontario, Canada. The Gutcher Lake and Jubilee stocks consist mainly of granitoid trondhjemite with feldspar laths mottled by white mica + calcite + epidote and rimmed by clear albite. Biotite is partly or wholly pseudomorphosed by chlorite + sphene; some epidote is partly altered to calcite + chlorite. The granitoid phase grades into a foliated phase of quartz + albite + white mica + calcite + chlorite near fracture zones traversing the stocks.
The alteration of the Gutcher Lake stock along its foliated margin involved addition of K2O, H2O + CO2, MnO, plus Rb; loss of CaO plus Sr; and a shift in Fe+2/Fet from 0.66 to 0.81. The alteration of the Jubilee stock along the Darwin Shear involved addition of H2O + CO2; loss of Sr; and no significant shift in Fe+2/Fet. The greenschist alteration also modified the contact aureoles bordering both stocks.
One interpretation is that regional metamorphism in the Archaean overprinted a greenschist assemblage on both stocks. The alteration was intense near fracture zones and sporadic remote from fractures. Lower integrated water to rock ratios along the Darwin Shear compared to the margin of the Gutcher Lake stock may explain the comparatively lower perturbation of the element abundances and redox state of iron.  相似文献   

5.
Abstract A Hercynian charnockite occurs within high-grade gneisses in the Agly Massif, French Pyrenees. Its thermal history has been evaluated using the Fe-Mg distribution coefticient ( K D) between garnet and biotite. These minerals have different origins but similar compositions in the charnockites and host gneisses. In the charnockite, the Bi–Ga pairs are the retrograde products of Opx alteration. This Opx reaction with feldspar can be written. Opx + PI + Fluid 1(H2O + Al + K + Fe + Ti) = Bi + Ga + Q + Fluid 2(H2O + Na). The garnets are relatively Ca poor (4–2.5% grossular); they are automorphic and zoned in the gneisses and poikiloblastic in the charnockites. Both types show a retrograde rim (of few hundred microns'width) across which Fe and Mn increase as Mg decreases. The biotites show a good correlation between the octahedral cations (Ti4++ Fe2+) and (Mg2++ Al3+VI); Ti and Fe both increase, whereas Mg and AlVI decrease. There is an inverse linear correlation between Fe2+ and Mg2+ and the Fe/Mg ratio increases as Ti increases. The relation between Ti and K Ga-BiDFe-Mg is less clear: it seems that K D slightly decreases as Ti increases. The equilibration temperatures of Ga–Bi pairs are discussed: the charnockite Ga-Bi pairs have equilibrated between 550°C and 600°C; whereas those of the gneisses have equilibrated between 550°C and 650°C. Two main thermal steps appear: one in the gneisses between 600-650°C and a second one in both the gneisses and the charnockites between 550°C and 600°C.  相似文献   

6.
A method for the selective separation of Ag, Cd, Cr, Cu, Ni, Pb and Zn in traces from solutions of calcite (CaCO3), dolomite (CaMg(CO3)2) and gypsum (CaSO4.2H2O) before their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) is presented. The expected interferences of Ca and Mg on intensities of trace analytes were removed by collecting the elements of interest with cobalt(III) hexamethylenedithiocar-bamate, Co(HMDTC)3. The flotation of aqueous solutions (1 l) of calcite, dolomite and gypsum was performed at pH 6.0, by 1.5 mg l−1 Co and 0.6 mmol l−1 HMDTC. To minimise the effect of the reaction between Ca/Mg, which restrains the function of the surfactant, careful selection of the most suitable foaming reagent was necessary. The accuracy of the method was established by analysing natural alkaline-earth minerals by the standard addition method as well as using the dolomite reference materials GBW 07114 and GSJ JDo-1. The ICP-AES limits of detection following flotation on different minerals were found to be 0.080 μg g−1 for Cd, 0.105 μg g−1 for Ag, 0.142 μg g−1 for Cu, 0.195 μg g−1 for Cr, 0.212 μg g−1 for Ni, 0.235 μg g−1 for Zn and 0.450 μg g−1 for Pb.  相似文献   

7.
Abstract Late Archaean orthogneisses and aluminous and iron-rich metasedimentary rocks intruded by anorthosite and a ferrodiorite-granite suite were completely recrystallized during Proterozoic granulite facies metamorphism. Geobarometry and geothermometry indicate P-T conditions of around 7.5kbar. 700°C, with a CO2-rich fluid phase and logfO2 at or below -16. A two-stage high-grade history of near isochemical corona growth is preserved in metasediments with the reaction cycle opx + plag + H2O → hbl+gar+SiO2→ opx+plag+H2O. End product compositions resemble those of the initial phases, and the only mobile components were SiO2 and/or H2O. The coronas reflect shortlived fluctuations in chemical activity at essentially constant P and T, contrary to simple progressive change in equilibrium parameters recorded by most corona-bearing textures.  相似文献   

8.
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.  相似文献   

9.
Abstract In metapelitic schists of the north-eastern Weekeroo Inliers, Olary Block, Willyama Supergroup, South Australia, syn-S1 and syn-S2 assemblages involving staurolite, garnet, biotite and another mineral, most probably cordierite, were overgrown by large syn-S3 andalusite porphyroblasts, owing to isobaric heating from metamorphic conditions that existed during the development of S2. Conditions during the development of S3 probably just reached the andalusite—sillimanite transition. During the development of S4, at somewhat lower temperatures than those that accompanied the development of S3, the following reaction occurred:
staurolite + chlorite + muscovite ± biotite + andalusite + quartz + H2O.
The amount of retrogression is controlled primarily by the amount of H2O added by infiltration. As the syn-S3 matrix assemblage was stable during the development of S4, but the andalusite porphyroblasts were no longer stable with the matrix when H2O was added, the retrogression is focused in and around the porphyroblasts. With enough H2O available, and if quartz was consumed before biotite in a porphyroblast, then the following reaction occurred:
staurolite + chlorite + muscovite + corundum ± biotite + andalusite + H2O.
This reaction allowed corundum inclusions in the andalusite to grow, regardless of the presence of quartz in the matrix assemblage.  相似文献   

10.
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%.  相似文献   

11.
Abstract The hornblende-bearing basic gneisses in the Uvete area, central Kenya, were metamorphosed under a narrow range of P and T (6.5 ± 0.5kbar and 530 ± 40°C) of the staurolitekyanite zone in the Mozambique metamorphic belt. They show a wide variety of divariant and trivariant mineral assemblages consisting of hornblende, cumminatonite, gedrite, anthophyllite, chlorite, garnet, epidote, clinopyroxene, plagio-clase and quartz. The bulk and mineral chemistries and the graphical representation of phase relations show that each mineral assemblage approaches chemical equilibrium and defines a unique composition volume in the A'(Al + Fe3+− (13/7)Na)-F(Fe2+)-M'(Mg)-C'(Ca-(3/7)Na) tetrahedron. The composition volumes are distributed quite regularly and do not overlap each other.
The phase relations in the Uvete area are in contrast with those in the staurolite-kyanite zone amphibolites in the Mt. Cube quadrangle, Vermont. The amphibolites there contain low-variance mineral assemblages formed under different values of μH2O and μCO2. These assemblages define overlapping composition volumes in the A'-F'-M'-C'tetrahedron.
The mineral assemblages in the Uvete area are interpreted as having formed in equilibrium with fluid at a high and nearly constant μH2O value. Such a fluid composition was externally controlled by the supply of H2O-rich fluid expelled from the surrounding pelitic and psammitic rocks. The body size of the basic gneisses in the Uvete area (less than 400m in thickness) was small enough for the fluid to migrate completely.  相似文献   

12.
This paper presents a two-stage anion-exchange procedure for tungsten extraction, an improved mass spectrometric procedure for tungsten analysis and a simplified chemical separation and TIMS procedure for the determination of Hf concentrations. The chemical separation of tungsten is based on its complexing properties with HF and H2O2. The blank level for a sample size of 300 mg is about 80 pg for tungsten. The procedure is designed for the high sensitivity of negative thermal ionisation mass spectrometry (NTIMS) provided by the use of Mg oxide as an emitter on Ir filaments. Tungsten can be readily measured with a high precision in various meteoritical material and especially in small W-poor silicate fractions. Samples containing as little as a few ng g-1 tungsten can be analysed reliably with this method.  相似文献   

13.
Results of electron microprobe and microthermometric studies of samples collected from the Bouvet Triple Junction Region (BTJR) during a joint Russian-Italian geological expedition on the R/V Academician Nikolaj Strakhov (1994) have revealed new data on the composition of basaltic magmas and oceanic hydrothermal fluids connected with magmatic processes. Detailed analysis of basaltic glasses shows that the modem Mid-Atlantic Ridge (MAR) rift valley is composed of normal mid-ocean ridge basalts with low concentrations of K2 O and TiOz (N-MORB), while its flanks are more enriched with these components approaching E-MORB. A marked influence of the Bouvet hot spot volcanism on magma generation on the South-West Indian Ridge (SWIR) near Bouvet Island is observed. Basaltic melts in this area belong to alkalic and transitional series and have maximum contents of K2O, TiO2, H2O.
Microthermometric analyses of fluid inclusions in the samples from the BTJR have revealed major differences in the oceanic hydrothermal fluid systems on the MAR and near SWIR, which depends on the peculiarities of magma. In the area of the MAR (with dry melts) only H2O solution inclusions in quartz were found; thus, seawater is probably the only primary source of hydrothermal fluids (NaCl + MgCl2+ H2O; T = 170–200°C). In the SWIR area (with the high content of water in melts) syngenetic liquid CO2 and H2O solution inclusions in quartz indicate the influence of the magmatic fluid component on the ore-forming water/carbon dioxide solutions (NaCl + CaC12+ H2O + CO2; T = 200–310 °C; P = 900–1700 bar).  相似文献   

14.
Calc-silicate granulites from the Bolingen Islands, Prydz Bay, East Antarctica, exhibit a sequence of reaction textures that have been used to elucidate their retrograde P–T path. The highest temperature recorded in the calc-silicates is represented by the wollastonite- and scapolite-bearing assemblages which yield at least 760°C at 6 kbar based on experimental results. The calc-silicates have partially re-equilibrated at lower temperatures (down to 450°C) as evidenced by the successive reactions: (1) wollastonite + scapolite + calcite = garnet + CO2, (2) wollastonite + CO2= calcite + quartz, (3) wollastonite + plagioclase = garnet + quartz, (4) scapolite = plagioclase + calcite + quartz, (5) garnet + CO2+ H2O = epidote + calcite + quartz, and (6) clinopyroxene + CO2+ H2O = tremolite + calcite + quartz.
The reaction sequence observed indicates that a CO2 was relatively low in the wollastonite-bearing rocks during peak metamorphic conditions, and may have been further lowered by local infiltration of H2O from the surrounding migmatitic gneisses on cooling. Fluid activities in the Bolingen calc-silicates were probably locally variable during the granulite facies metamorphism, and large-scale CO2 advection did not occur.
A retrograde P–T path, from the sillimanite stability field ( c. 760°C at 6 kbar) into the andalusite stability field ( c. 450°C at <3 kbar), is suggested by the occurrence of secondary andalusite in an adjacent cordierite–sillimanite gneiss in which sillimanite occurs as inclusions in cordierite.  相似文献   

15.
The cathodoluminescence analyses of the trigonal carbonates calcite and dolomite have been applied intensively in sedimentary petrology for a long time and the properties of these minerals are well-known, but much less attention has been paid to aragonite. In this study, the cathodoluminescence behaviour and the trace element composition of natural and synthetic aragonite have been studied employing trace element analyses (proton induced X-ray emission) and luminescence spectroscopy. Aragonite doped with Mn2+ has been synthesized in a NH4+–Mg2+–Ca2+–Cl solution in contact with a CO2–H2O–NH3 atmosphere. The low effective distribution coefficients indicate a rapid growth of the crystals of millimetre size which occurred within hours or days. The natural aragonite samples contain Mn, Fe and Sr in different concentrations. The Mn-bearing aragonites exhibit a bright green luminescence which is caused by a strong emission band at 575 nm with a half-width of about 84 nm. The luminescence intensity shows a strong positive correlation with Mn in aragonite when Fe and Mn do not exceed 2000 p.p.m. The intensity is depressed if the concentration of these elements exceeds the critical values. In the shell of a recent Unio sp., the luminescence intensity deviates from the linear correlation, although the trace element contents are not too high; this is probably an effect of quenching by organic material between the crystallites of the biogenic aragonite.  相似文献   

16.
A reaction producing jadeitic pyroxene in metagreywackes of the northern Diablo Range has been identified on the basis of mineral distribution, isograd patterns and composition of coexisting minerals. The appearance of jadeitic pyroxene (∼Jd80) is closely followed by the disappearance of pumpellyite, which indicates that pumpellyite plays a major role in the pyroxene-producing reaction. A new projection from hematite, lawsonite, chlorite, quartz and H2O on to the NaAlO2-FeO-MgO ternary confirms the role of pumpellyite in pyroxene production and suggests a reaction of the form: 1.00 pumpellyite + 0.31 chlorite + 8.71 albite + 0.70 hematite + 2.00 H2O = 8.54 jadeite + 0.57 glaucophane + 3.09 lawsonite + 5.26 quartz. Metagreywackes of the northern Diablo Range were metamorphosed under conditions of P H2O= P total at 200-300 °C and 7.5-10.0 kbar. Despite the low temperatures attained during metamorphism, the assumption of equilibrium yields results consistent with field observations and phase relations.  相似文献   

17.
A ternary solid solution model for omphacite with the end-members jadeite (NaAlSi2O6), diopside (CaMgSi2O6) and hedenbergite (CaFeSi2O6) was derived from experimental data from the literature. The subregular solution model, fitted by linear programming, is best suited to omphacites with very little aegirine component in common eclogites. Applying this solution model to the calculation of equilibrium phase diagrams of eclogites from the Adula nappe (Central Alps, Switzerland) results in large stability fields for common eclogite assemblages (garnet+omphacite+quartz+H2O±kyanite). Within this field the compositions of garnet and omphacite show very little variation. A precise determination of the peak-pressure and temperature is not possible. The occurrence of amphibole, overgrowing the peak-pressure assemblage in fresh eclogite, suggests retrograde re-equilibration, still under eclogite facies conditions. The computation of isopleths for garnet and pyroxene end-members allows the estimation of the pressure and temperature conditions of this re-equilibration event (19–21  kbar, c .  700 °C).  相似文献   

18.
A single-column suppressed ion chromatography technique was employed for the simultaneous determination of major and trace anions in sulfaterich groundwater samples. An analytical column, a self regenerating suppressor and sodium carbonate as the eluent were used to separate the anions. Method detection limits for the anions of interest were 10.4, 15.9, 36.8, 62, 60, 61 and 67 μg l−1 for F, Cl, NO2, Br, NO3, PO43− and SO42− respectively. The precision of the method was tested at five different concentration levels for each anion reference sample to evaluate the effectiveness of the method for groundwater analysis. Recovery studies were performed between two successive months by adding reference samples to the geothermal groundwater and drinking water samples. Precision was also assessed as the relative standard deviation of both repeatability (within-day) and reproducibility (between-day and different concentrations) for groundwater samples. Standard deviation and RSD values of 220 groundwater samples acquired over 8 months were evaluated. The suppressed ion chromatography technique was found to be a suitable method for determining major anions in sulfate-rich geothermal water samples.  相似文献   

19.
Strontium isotopic composition is a potentially powerful tracer in studies of kimberlitic rocks but the results from even the most carefully collected and stringently prepared bulk-rock samples are still hampered by contamination and alteration effects. Here we describe a LA-MC-ICP-MS technique which can obtain accurate, high precision Sri ratios from 50–150 μm kimberlitic groundmass perovskite without requiring time-consuming mineral separation procedures. Since perovskite is a robust magmatic phase with an extremely low Rb/Sr ratio, the effects of late-stage crustal contamination, post-emplacement alteration and age correction are minimised and results are more representative of primary melt compositions, while additionally preserving powerful grain-scale spatial and textural information. We demonstrate that the adopted protocol overcomes isobaric interferences from Kr+, Rb+, Er2+ and Yb2+, and that Ca dimers and Ca argides do not detectably affect the quality of 87Sr/86Sr ratios produced. To illustrate the utility of the technique, contrasting bulk-rock and in situ perovskite results from eleven Proterozoic kimberlites are documented.  相似文献   

20.
A simple and accurate method to determine fluorine and chlorine contents in small amounts (∼ 30 mg) in rock has been developed using ion chromatography after extraction by alkaline fusion. Powdered sample was mixed with sodium carbonate and zinc oxide at a mass ratio of 1:3:1, and was fused in an electric furnace at 900 °C for 30-40 minutes. An aqueous solution obtained by dissolving the fused silicate rock was diluted to the appropriate concentration of sodium carbonate (< ∼ 24 mmol l-1) to minimise the tailing effect on F- during ion chromatography caused by the large amount of carbonate species originating from the flux. Fluorine and chlorine contents were then determined by a standard additions method. Based on the relative standard deviation of the backgrounds, detection limits of both fluorine and chlorine were ∼ 4 μg g-1, when 30 mg test portions were fused and diluted by a factor of 1200. We also report new fluorine and chlorine contents in nine GSJ (Geological Survey of Japan) reference materials, including peridotite (JP-1), granite (JG-1a), basalts (JB-1b, 2 and 3), andesites (JA-1 and 2) and rhyolites (JR-1 and 2). Fluorine and chlorine contents in the reference materials in this study were consistent with previously reported values. Reproducibilities were < 10 % for samples with F and Cl concentrations of > 20 μg g-1 and < 20 % with F and Cl < 20 μg g-1.  相似文献   

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