The Isotopic Composition of Noble Gases in Gold Deposits and the Source of Ore- Forming Materials in the Region of North Hebei, China

1IntroductionOnthenorthernmarginoftheNorthChinaplatformislocatedoneofthemostimportantAu Ag polymetallicore concentratedzones,wherethereareavarietyoforetypes .Soithasbeenat tractingeverincreasingattentionofmanygeologists (PeiRongfuetal.,1 998;ShenBaofengetal.,1 994 ;LuSongnianetal.,1 997;HuShouxietal.,1 994 ;ChenYuchuan ,1 999;ZhaiYushengetal.,1 999) .Manyscholarspresentedtheirresearchresultsinvariousaspects.How ever ,thesourceofore formingmaterialshaslongbeenafocusofdiscussion .Studieso…     

Helium and argon isotopes in spinel lherzolite from Damaping, northern Zhangjiakou

Spinel lherzolite found in Damaping, northern Zhangjiakou, Hebei Province occurs as xenoliths in the Hannuoba basalts that consist of alkali basalt and tholeiite. Spinel lherzolites contain 50%–70% olivine (Fo: 90%), 10%–20% clinopyroxene (predominantly Di), 10%–30% orthopyroxene (predominantly En), and less than 5% spinel.³He/⁴He and⁴⁰Ar/³⁸Ar ratios in the olivine are 7.56×10⁻⁷ and 299.1, respectively.³He/⁴He and⁴⁰Ar/³⁸Ar ratios in the orthopyroxene (enstatite) are 9.1×10⁻⁷ and 307, respectively. Olivine grains are fractured irregularly, and pyroxene grains characterized by well developed cleavages, which would have resulted from explosion during the rapid eruption of lava from the deep interior to the surface. The lower isotope ratios of helium and argon may indicate that the spinel lherzolite xenoliths were derived from the strongly degassed and depleted upper mantle, and that the mantle is inhomogeneous.³He losses to some extent might affect the helium isotope ratios. The project was financially supported by the National Natural Science Foundation of China (No. 49273185).     

Helium and argon isotope geochemistry of natural gases in China’s petroliferous basins

The age-accumulation effect of 40Ar in hydrocarbon source rocks was discussed in accordance with the decay law of radioactive elements. In terms of the mean values of 40Ar/36Ar, the old Sinian gas reservoirs (mean values of 40Ar/36Ar: 7009) were definitely distinguished from the Permian gas reservoirs (mean values of 40Ar/36Ar: 1017) in Weiyuan, Sichuan Province, and the gas source of the Permian gas reservoir (mean values of 40Ar/36Ar: 5222) in well Wei-7 with the Weiyuan structure is defined as the Sinian system. Based on the values of 40Ar/36Ar, the coal-type gases (The source rocks are of the C-P system; mean values of 40Ar/36Ar: 1125) are definitely distinguished from the oil-type gases (The source rocks are of the Tertiary system; mean values of 40Ar/36Ar: 590) in the Tertiary reservoirs of the Zhongyuan Oilfield. Besides, 40Ar/36Ar values also have a positive effect on the oil-source correlation of oil reservoirs in ancient hidden mountains. According to the crust-mantle interchange information reflected by 3He/4He values, petroliferous provinces in China can be divided into three major tectonic regions. (1) The eastern active region: The crust-mantle volatile matter exchanges actively, and the 3He/4He values are mainly around 10-6, partly around 10-7. (2) The central stable region: The 3He/4He values are all around 10-8. (3) The western sub-stable region: The 3He/4He values are mainly around 10-8, and around 10-7 on the edges of the basins. Helium contents of some gas wells in China’s eastern petroliferous region reach the industrial abundance (He≈0.05%–0.1%), the 3He/4He values reach 10-6, and the equivalent values for the mantle-source components in helium gas can reach 30%–50%. As viewed from this, a new type of crust-mantle composite helium resources has been proposed. Geneses of some CO2 gas reservoirs in the east of China and some issues concerning mantle-source methane were discussed in the light of the helium and carbon isotopes of CO2 and CH4 in natural gases. In the discussion on helium isotopic characteristics of inclusions in the reservoirs, it was discovered that the 3He/4He values are close to those in natural gases. That is to say, this phenomenon is related to regional tectonism. The 3He/4He, CO2/3He and CH4/3He data were used to discuss the tectonic activities of fault zones in a certain number of regions in China.     

Noble gas and carbon isotopes in Mariana Trough basalt glasses

Noble gas elemental and isotopic compositions have been measured as well as the abundance of C and its isotopic ratios in 11 glasses from submarine pillow basalts collected from the Mariana Trough. The ³He/⁴He ratios of 8.22 and 8.51 R_atm of samples dredged from the central Mariana Trough (∼18°N) agree well with that of the Mid-Ocean Ridge Basalt (MORB) glasses (8.4±0.3 R_atm), whereas a mean ratio of 8.06±0.35 R_atm in samples from the northern Mariana Trough (∼20°N) is slightly lower than those of MORB. One sample shows apparent excess of ²⁰Ne and ²¹Ne relative to atmospheric Ne, suggesting incorporation of solar-type Ne in the magma source. There is a positive correlation between ³He/⁴He and ⁴⁰Ar/³⁶Ar ratios, which may be explained by mixing between MORB-type and atmospheric noble gases. Excess ¹²⁹Xe is observed in the sample which also shows ²⁰Ne and ²¹Ne excesses. Observed δ¹³C values of ∼20°N samples vary from −3.76‰ to −2.80‰, and appear higher than those of MORB, and the corresponding CO₂/³He ratios are higher than those of MARA samples at ∼18°N, suggesting C contribution from the subducted slab.     

Rare-earth elements as source indicators of Pan-African granites from Obudu Plateau,Southeastern Nigeria

The rare-earth element （REE） concentrations of representative granite samples from the southeast of the Obudu Plateau, Nigeria, were analyzed with an attempt to determine the signatures of their source, evolutionary history and tectonic setting. Results indicated that the granites have high absolute REE concentrations （190×10^-6-1191×10^-6; av.=549×10^-6） with the chondrite-normalized REE patterns characterized by steep negative slopes and prominent to slight or no negative Eu anomalies. All the samples are also characterized by high and variable concentrations of the LREE （151×10^-6-1169×10^-6; av.= 466×10^-6）, while the HREE show low abundance （4×10^-6-107×10^-6; av.=28×10^-6）. These are consistent with the variable levels of REE fractionation, and differentiation of the granites. This is further supported by the range of REE contents, the chondrite-normalized patterns and the ratios of LaN/YbN （2.30-343.37）, CeN/YbN （5.94-716.87）, LaN/SmN （3.14-11.68） and TbN/YbN （0.58-1.65）. The general parallelism of the REE patterns, suggest that all the granites were comagmatic in origin, while the high Eu/Eu＊ ratios （0.085-2.807; av.=0.9398） indicate high fo2 at the source. Similarly, irregular variations in LaN/YbN, CeN/YbN and Eu/Eu＊ ratios and REE abundances among the samples suggest behaviors that are related to mantle and crustal sources.     

Early Paleozoic adakite in the Liuyuan area from the Beishan orogenic belt,NW Gansu Province: Petrogenesis and implication for tectonic setting

The Liuyuan area,which is located on the southern margin of the Beishan orogenic belt,develops abundant Early Paleozic granitoids.SHRIMP zircon U-Pb dating yielded a weighted mean 206Pb/238U age of 421±8 Ma for the Liuyuan granodiorite(Zhao Zehui et al.,2007),implying its Late Silurian intrusion.Geochemical compositions showed that the Liuyuan granodiorite is characterized by high SiO2(65.01%-67.31%),A12O3(17.17%-18.05%) and Na2O(Na2O/K2O=1.67-1.87) but low Mg# contents calculated as 100×Mg2+/(Mg2++∑Fe2+) from 28.77 to 31.15,as well as being enriched in Sr(472×10-6-517×10-6) but depleted in Yb(1.2×10-6-1.42×10-6) and Y(12.8×10-6-14×10-6).The REEs are characterized by right-inclined patterns with LREE enrichment,HREE depletion and slightly negative Eu anomalies(Eu/Eu*=0.91-0.97).Major and trace elements indicate that the granodiorite is an adakite.The Nb/Ta values of the granodiorite vary from 10.80 to 18.01 and Nb/U from 6.32 to 10.09,both lying between the values of the crust and the mantle.The rock has low εNd(t) values(-2.5--0.8) and high ISr(0.706321-0.706495).Geochemical and Sr-Nd isotopic compositions indicate that the Liuyuan granodiorite is possibly derived from partial melting of thickening lower crust,related to mantle underplating.The Yb-Ta and Y+Nb-Rb discriminant diagrams imply the Liuyuan granodiorite intruded in a local extensional tectonic setting during late collision.Combined with previous studies on geochronology,geochemistry and tectonic setting of granitoids,we interprete that the constraint of this adakite in the Liuyuan area indicates that the tectonic setting may have transformed from collision to extension during the Early Devonian.     

Geochemistry of gas emanations: A case study of the Réunion Hot Spot,Indian Ocean

The results of analysis of natural emanations in Réunion Island show a clear magmatic origin for CO₂ and He, while N₂ and Ar are predominantly derived from the atmosphere. The distribution of magmatic gases in the Piton des Neiges massif fits the local volcanotectonic context well and suggests that the areas concerned are still subject to volcanic activity at depth. A simple method is proposed for correcting gas concentration and isotope composition for water degassing. In doing so, the isotope and elemental (C, He) composition of gases is homogeneous for the two volcanoes. The isotope ratio of He (12.5 ± 0.5R/Ra) in the present discharges is in agreement with the results of previous studies on rocks of various ages from the two volcanoes. The isotope ratio of C(δ¹³C= −5 ‰ to −4 ‰ vs PDB) and the C/³ He ratio (∼4 × 10⁹) are similar to those found in other Hot Spot volcanic systems such as Kilauea (Hawaii) and Hengill (Iceland). These similarities suggest comparable volatile history for the respective mantle sources, the main differences being in the relative proportions of radiogenic ⁴He. In detail, Hot Spots appear enriched in C having a light composition with respect to MORB, possibly due to the addition of a C-rich (e.g. subducted) component, in addition to a relatively undegassed, ³He-rich, component.     

Origin of hydrogen-nitrogen gas seeps,Oman

Six gas samples were collected from five thermal springs in the Semail Nappe ophiolite and the calcareous (calcite and dolomite) Hajar Formation, northern Oman. The³He/⁴He,⁴He/²⁰Ne,⁴⁰Ar/³⁶Ar and³⁸Ar/³⁶Ar ratios, chemical compositions (H₂, N₂, CO₂, CH₄, O₂, Ar and He), and stable isotope compositions (δD_H2, δD_H2O, δ¹³C_CO2, δ¹³C_CH4, and δ¹⁵N_N2) are reported. Samples from the ophiolite region are significantly anoxic with major constituents of H₂, CH₄ and N₂, while those from calcite and dolomite regions are ordinary gas seeps, consisting of N₂, CO₂ and/or O₂. The former H₂-rich gas is characterized by relatively high³He/⁴He ratio (0.4–0.8 R_atm) with low He content (<5 ppm), atmospheric⁴⁰Ar/³⁶Ar ratio, low N₂/Ar ratio (<55) and high δ¹⁵N_N2 value (∼1 ‰). On the other hand, the latter N₂-rich gas shows relatively low³He/⁴He ratio (0.1–0.4 R_atm) with high He concentration (>300 ppm), slight radiogenic⁴⁰Ar/³⁶Ar ratio, high N₂/Ar ratio (77–97) and low δ¹⁵N_N2 value (<0‰). Observed δD_H2 value of −536‰ in H₂-rich gas is distinguished from the literature value of −699‰ in the ophiolite region, giving discrepant isotope formation temperatures.     

Isotopic Geochemistry of Non—hydrocarbons in Natural Gases from the Sanshui Basin,Guangdong Province,China

This study is focused on geothermal heat flow and the origin of non-hydrocarbons in natural gases in terms of the isotope geochemical characteristics of Ar, He, CO₂ and N₂ in natural gases from the Sanshui Basin, Guangdong Province. China.³He/⁴He ratios are of (1.60-6.39) × 10^-6, and⁴⁰Ar/³⁶Ar ratios of 450–841. The carbon isotopic composition (δ_l3C PDB) of carbon dioxide ranges from -20‰ to -2‰. δ^l5N(air) ratios have a wider range of-57 ‰- +95 ‰. The isotope geochemical characteristics of non-hydrocarbons indicate that He, Ar and N₂ in the gas reservoirs enriched in non-hydrocarbons were derived largely from the upper mantle. Non-hydrocarbons in gaseous hydrocarbon reservoirs consist mainly of crustal radiogenic He and⁴⁰Ar and some mantle-derived He and Ar, as well as of¹³C-depleted carbon dioxide and nitrogen generated as a result of thermal decomposition of organic matter in strata. Carbon dioxide enriched in¹³C was derived largely from carbonate rocks and partially from the lower crust and upper mantle. Based on the relationship between geothermal heat flow (Q) and³He/⁴ He ratio in natural gases, the Q values for the area studied have been calculated. Similar Q values are reported from the upper mantle uplift area (77 mWm^-2) in Huabei and the Tancheng-Lujiang Rift Zone (88 mWm^-2). More than 60 percent of geothermal heat flow in the Sanshui Basin may have been derived from the upper mantle. The project is financially supported by the National Natural Science Foundation of China.     

Metamorphic fluid origins in the Osborne Fe oxide–Cu–Au deposit,Australia: evidence from noble gases and halogens

The Osborne iron oxide–copper–gold (IOCG) deposit is hosted by amphibolite facies metasedimentary rocks and associated with pegmatite sheets formed by anatexis during peak metamorphism. Eleven samples of ore-related hydrothermal quartz and two pegmatitic quartz–feldspar samples contain similarly complex fluid inclusion assemblages that include variably saline (<12–65 wt% salts) aqueous and liquid carbon dioxide varieties that are typical of IOCG mineralisation. The diverse fluid inclusion types present in each of these different samples have been investigated by neutron-activated noble gas analysis using a combination of semi-selective thermal and mechanical decrepitation techniques. Ore-related quartz contains aqueous and carbonic fluid inclusions that have similar ⁴⁰Ar/³⁶Ar values of between 300 and 2,200. The highest-salinity fluid inclusions (47–65 wt% salts) have calculated ³⁶Ar concentrations of approximately 1–5 ppb, which are more variable than air-saturated water (ASW = 1.3–2.7 ppb). These fluid inclusions have extremely variable Br/Cl values of between 3.8 × 10⁻³ and 0.3 × 10⁻³, and I/Cl values of between 27 × 10⁻⁶ and 2.4 × 10⁻⁶ (all ratios are molar). Fluid inclusions in the two pegmatite samples have similar ⁴⁰Ar/³⁶Ar values of ≤1,700 and an overlapping range of Br/Cl and I/Cl values. High-salinity fluid inclusions in the pegmatite samples have 2.5–21 ppb ³⁶Ar, that overlap the range determined for ore-related samples in only one case. The fluid inclusions in both sample groups have ⁸⁴Kr/³⁶Ar and ¹²⁹Xe/³⁶Ar ratios that are mainly in the range of air and air-saturated water and are similar to mid-crustal rocks and fluids from other settings. The uniformly low ⁴⁰Ar/³⁶Ar values (<2,200) and extremely variable Br/Cl and I/Cl values do not favour a singular or dominant fluid origin from basement- or mantle-derived magmatic fluids related to A-type magmatism. Instead, the data are compatible with the involvement of metamorphic fluids that have interacted with anatectic melts to variable extents. The ‘metamorphic’ fluids probably represent a mixture of (1) inherited sedimentary pore fluids and (2) locally derived metamorphic volatilisation products. The lowest Br/Cl and I/Cl values and the ultra-high salinities are most easily explained by the dissolution of evaporites. The data demonstrate that externally derived magmatic fluids are not a ubiquitous component of IOCG ore-forming systems, but are compatible with models in which IOCG mineralisation is localised at sites of mixing between fluids of different origin. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorised users.     

Helium,neon, and argon in the iron meteorites Dongling,Nantan and Ningbo

The light noble gases He, Ne and Ar have been measured in the iron meteorites Dongling, Nantan and Ningbo. Dongling and Ningbo show a deficit of cosmic-ray that produced³He of ca. 30% and 10%, respectively, which is argued to be caused by the loss of³H (tritium) from the meteoroids during the time of their exposure to the cosmic radiation. Nantan has the lowest content of noble gases as yet reported for any iron meteorite. Cosmogenic³He and³⁸Ar are only about 1/5000 of those in Dongling which has particularly interesting implications if the two meteorites belong to the same fall^[2]. In addition, Nantan contains nonspallogenic⁴He which we believe to be of radiogenic origin. This radiogenic⁴He, together with a U-content of 2.6×10⁻¹¹ g/g^[20] yields a⁴He retention age close to the cosmic-ray exposure age of Dongling. If Dongling and Nantan were part of the same meteoroid^[2], this result would indicate that He retention in the meteoroid age were 4,500 Ma, a U-content of less than 7.2×10⁻¹³ g/g is required to explain the non-cosmogenic₄He present. An upper limit to the number of transuranium or superheavy-element atoms which have decayed by α-emission in Nantan since onset of He retention is 2×10¹⁰ per gram.     

Geochemistry and origin of gas pools in the Gaoqing-Pingnan fault zone,Jiyang Depression

In the surroundings of the Gaoqing-Pingnan fault zone are developed quite a number of gas reservoirs. Based on gas compositions, they can be divided into two groups, i.e., CO2 and CH4. Their composition and isotope geochemistry were dealt with in this study. The CO2 contents range from 60.72%–99.99%, the δ13CCO2 values from -3.41‰– -9.8‰, and the 3He/4He ratios from 4.35×10-6–6.35×10-6 (i.e. R/Ra=4.45–4.35). Based on the data on composition and isotope geochemistry, deep geological background, deep faults and volcanic rocks, it is shown that CO2 ,distributed in the Gaoqing area, mostly originated from mantle-source inorganic matter which is associated with magmatic rocks. The favorable tectonic environment for the formation of CO2 reservoirs is the rift, which is related to great fault-magmatic activity, the formation of CO2 gas pools and their space-time correlation to the most recent magmatic activities. Hydrocarbon gas pools occur in the Huagou area. The CH4 contents are within the range of 88.83%–99.12%, and the δ13CCH4 values, -44.7‰– -54.39‰. This indicates that the hydrocarbon gas resulted from the decomposition of oil-type gas at high temperatures. Volcanic rocks in the CO2 gas pool-and CH4 gas pool-distributed areas show significant differences in Fe2O3 and FeO contents. This has proven that the hydrocarbon gas may have resulted from various chemical reactions. Magmatic activities are the primary reason for the distribution of CO2 and CH4 gas pools in the Gaoqing-Pingnan fault zone.     

Fluid origin and structural enhancement during mineralization of the Jinshan orogenic gold deposit, South China

The Jinshan orogenic gold deposit is a world-class deposit hosted by a ductile shear zone caused by a transpressional terrane collision during Neoproterozoic time. Ore bodies at the deposit include laminated quartz veins and disseminated pyrite-bearing mylonite. Most quartz veins in the shear zone, with and without gold mineralization, were boudinaged during progressive shear deformation with three generations of boudinage structures produced at different stages of progressive deformation. Observations of ore-controlling structures at various scales indicate syn-deformational mineralization. Fluid inclusions from pyrite intergrown with auriferous quartz have ³He/⁴He ratios of 0.15–0.24 Ra and ⁴⁰Ar/³⁶Ar ratios 575–3,060. δ¹⁸O_fluid values calculated from quartz are 5.5–8.4‰, and δD values of fluid inclusions contained in quartz range between −61‰ and −75‰. The δ¹³C values of ankerite range from −5.0‰ to −4.2‰, and ankerite δ¹⁸O values from 4.4‰ to 8.0‰. The noble gas and stable isotope data suggest a predominant crustal source of ore fluids with less than 5% mantle component. Data also show that in situ fluids were generated locally by pervasive pressure solution, and that widespread dissolution seams acted as pathways of fluid flow, migration, and precipitation. The in situ fluids and fluids derived from deeper levels of the crust were focused by deformation and deformation structures at various scales through solution-dissolution creep, crack-seal slip, and cyclic fault-valve mechanisms during progressively localized deformation and gold mineralization.     

Isotope geochemistry of ore fluids for the Dongsheng sandstone-type uranium deposit, China

The Dongsheng sandstone-type uranium deposit is one of the large-sized sandstone-type uranium deposits discovered in the northern part of the Ordos Basin of China in recent years. Geochemical characteristics of the Dongsheng uranium deposit are significantly different from those of the typical interlayered oxidized sandstone-type uranium ore deposits in the region of Middle Asia. Fluid inclusion studies of the uranium deposit showed that the uranium ore-forming temperatures are within the range of 150–160℃. Their 3He/4He ratios are within the range of 0.02–1.00 R/Ra, about 5–40 times those of the crust. Their 40Ar/36Ar ratios vary from 584 to 1243, much higher than the values of atmospheric argon. The δ18OH2O and δD values of fluid inclusions from the uranium deposit are -3.0‰– -8.75‰ and -55.8‰– -71.3‰, respectively, reflecting the characteristics of mixed fluid of meteoric water and magmatic water. The δ18OH2O and δD values of kaolinite layer at the bottom of the uranium ore deposit are 6.1‰ and -77‰, respectively, showing the characteristics of magmatic water. The δ13CV-PDB and δ18OH2O values of calcite veins in uranium ores are -8.0‰ and 5.76‰, respectively, showing the characteristics of mantle source. Geochemical characteristics of fluid inclusions indicated that the ore-formation fluid for the Dongsheng uranium deposit was a mixed fluid of meteoric water and deep-source fluid from the crust. It was proposed that the Jurassic-Cretaceous U-rich metamorphic rocks and granites widespread in the northern uplift area of the Ordos Basin had been weathered and denudated and the ore-forming elements, mainly uranium, were transported by meteoric waters to the Dongsheng region, where uranium ores were formed. Tectonothermal events and magmatic activities in the Ordos Basin during the Mesozoic made fluids in the deep interior and oil/gas at shallow levels upwarp along the fault zone and activated fractures, filling into U-bearing clastic sandstones, thus providing necessary energy for the formation of uranium ores.     

Determination of denitrification in the Chesapeake Bay from measurements of N2 accumulation in bottom water

This study demonstrates the feasibility of using direct N₂ measurements in an estuary for determination of denitrification. High precision measurements of dinitrogen: argon ratios (N₂∶Ar) were made by membrane inlet mass spectrometry on water samples taken along the length of the Chesapeake Bay in July and October 2004. The N₂∶Ar ratio in low salinity surface water was elevated relative to air saturation by 0.3–0.5% with no systematic change along the length of the Bay. N₂∶Ar in high salinity bottom water exhibited a linear increase in the landward direction along a 144-km longitudinal section. In this section of the Bay covering 20% of the main stem, the bottom water salinity was statistically uniform and the increase in N₂∶Ar was in the direction of net residual current flow. The system was analyzed as a capped river with the assumption that N₂ entered the water from the underlying sediment where denitrification is known to take place. The rate of denitrification needed to support the measured increase in N₂ was calculated using an average residual current velocity and water column depth. The increase in N₂ with distance (0.046μmol N l⁻¹ km⁻¹) equated to an average denitrification flux of 73 μmol N m⁻² h⁻¹. N₂ fluxes determined on sediment cores taken from the source and terminus regions of the delineated water mass were 45±23 and 83±39 μmol N m⁻² hr⁻¹, respectively, which were not statistically different from the whole system estimate. The measured change in oxygen concentration within the bottom water was used to estimate nitrogen remineralization and the efficiency of denitrification. Denitrification efficiency (nitrogen denitrified/nitrogen remineralized) was estimated to be in the range of 22–28% for the bottom water sediment system and 30–37% considering the sediment zone alone.     

X-ray diffraction study of magnesite at high pressure and high temperature

 P–V–T measurements on magnesite MgCO₃ have been carried out at high pressure and high temperature up to 8.6 GPa and 1285 K, using a DIA-type, cubic-anvil apparatus (SAM-85) in conjunction with in situ synchrotron X-ray powder diffraction. Precise volumes are obtained by the use of data collected above 873 K on heating and in the entire cooling cycle to minimize non-hydrostatic stress. From these data, the equation-of-state parameters are derived from various approaches based on the Birch-Murnaghan equation of state and on the relevant thermodynamic relations. With K′₀ fixed at 4, we obtain K₀=103(1) GPa, α(K⁻¹)=3.15(17)×10⁻⁵ +2.32(28)×10⁻⁸ T, (∂K_T/∂T)_P=−0.021(2) GPaK⁻¹, (dα/∂P)_T=−1.81×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V= −0.007(1) GPaK⁻¹; whereas the third-order Birch-Murnaghan equation of state with K′₀ as an adjustable parameter yields the following values: K₀=108(3) GPa, K′₀=2.33(94), α(K⁻¹)=3.08(16)×10⁻⁵+2.05(27) ×10⁻⁸ T, (∂K_T/∂T)_P=−0.017(1) GPaK⁻¹, (dα/∂P)_T= −1.41×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V=−0.008(1) GPaK⁻¹. Within the investigated P–T range, thermal pressure for magnesite increases linearly with temperature and is pressure (or volume) dependent. The present measurements of room-temperature bulk modulus, of its pressure derivative, and of the extrapolated zero-pressure volumes at high temperatures, are in agreement with previous single-crystal study and ultrasonic measurements, whereas (∂K_T/∂T)_P, (∂α/∂P)_T and (∂K_T/∂T)_V are determined for the first time in this compound. Using this new equation of state, thermodynamic calculations for the reactions (1) magnesite=periclase+CO₂ and (2) magnesite+enstatite=forsterite+CO₂ are consistent with existing experimental phase equilibrium data. Received September 28, 1995/Revised, accepted May 22, 1996     

Thermal equations of state of dioctahedral micas on the join muscovite–paragonite

 Powder diffraction measurements at simultaneous high pressure and temperature on samples of 2M1 polytype of muscovite (Ms) and paragonite (Pg) were performed at the beamline ID30 of ESRF (Grenoble), using the Paris-Edinburgh cell. The bulk moduli of Ms, calculated from the least-squares fitting of V–P data on each isotherm using a second-order Birch–Murnaghan EoS, were: 57.0(6), 55.1(7), 51.1(7) and 48.9(5) GPa on the isotherms at 298, 573, 723 and 873 K, respectively. The value of (∂K _T /∂T) was −0.0146(2) GPa K⁻¹. The thermal expansion coefficient α varied from 35.7(3) × 10⁻⁶ K⁻¹ at P ambient to 20.1(3) × 10⁻⁶ K⁻¹ at P = 4 GPa [(∂α/∂P) _T = −3.9(1) × 10⁻⁶ GPa⁻¹ K⁻¹]. The corresponding values for Pg on the isotherms at 298, 723 and 823 K were: bulk moduli 59.9(5), 55.7(6) and 53.8(7) GPa, (∂K _T /∂T) −0.0109(1) GPa K⁻¹. The thermal expansion coefficient α varied from 44.1(2) × 10⁻⁶ K⁻¹ at P ambient to 32.5(2) × 10⁻⁶ K⁻¹ at P = 4 GPa [(∂α/∂P) _T = −2.9(1) × 10⁻⁶ GPa⁻¹ K⁻¹]. Thermoelastic coefficients showed that Pg is stiffer than Ms; Ms softens more rapidly than Pg upon heating; thermal expansion is greater and its variation with pressure is smaller in Pg than in Ms. Received: 28 January 2002 / Accepted: 5 April 2002     

Phosphorus – an omnipresent minor element in garnet of diverse textural types from leucocratic granitic rocks

Summary Elevated P contents of up to 0.086 apfu (1.21 wt.% P₂O₅) were found in garnet from leucocratic granitic rocks (orthogneisses, granites, barren to highly evolved pegmatites) in the Moldanubicum and Silesicum, Czech Republic, and in complex granitic pegmatites from southern California, USA, and Australia. Minor concentrations (0.15–0.55 wt.% P₂O₅) appear ubiquitous in garnet from leucocratic granitic rocks of different origins and degrees of fractionation. Concentrations of P are not related to Mn/(Mn + Fe) that vary from 0.12–0.86 and to textural types of garnet (i.e., isolated anhedral to euhedral grains and nodules, graphic and random garnet–quartz aggregates, subsolidus veins of fine-grained garnet). Garnet compositions exhibit negative correlations for P/Si and P/R²⁺ where R²⁺ = Fe + Mn + Mg + Ca, while Al is constant at ∼2.05 apfu. Concentrations of Na are largely below 0.02 apfu but positively correlate with P. The main substitution may involve A-site vacancy and/or the presence of some light element(s) in the crystal structure. The substitution □P₂ R²⁺ ₋₁Si₋₂ and/or alluaudite-type Na□P₃ R²⁺ ₋₁Si₋₃ seem the most likely P-incorporating mechanisms. The partitioning of P among garnet and associated minerals in granitic systems remains unclear; however, it directly affects the distribution of Y and REEs.     

Thermal expansion of new arsenate minerals,bradaczekite, NaCu<Subscript>4</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>3</Subscript>, and urusovite,Cu(AsAlO<Subscript>5</Subscript>)

Thermal behavior of two new exhalation copper-bearing minerals, bradaczekite and urusovite, from the Great Tolbachik Fissure Eruption (1975–1976, Kamchatka Peninsula, Russia) has been studied by X-ray thermal analysis within the range 20–700°C in air. The following major values of the thermal expansion tensor have been calculated for urusovite: α₁₁ = 10, α₂₂ = α_b = 7, α₃₃ = 4, α_V = 21 × 10⁻⁶°C⁻¹, μ = c∧α₃₃ = 49° and bradaczekite: α_11aver = 23, α₂₂ = 8, α_33aver = 6 × 10⁻⁶°C⁻¹, μ(c∧α₃₃) = 73°. The sharp anisotropy of thermal deformations of these minerals, absences of phase transitions, and stability of the minerals in the selected temperature range corresponding to conditions of their formation and alteration during the posteruption period of the volcanic activity are established.     

Primary and secondary processes constraining the noble gas isotopic signatures of carbonatites and silicate rocks from Brava Island: evidence for a lower mantle origin of the Cape Verde plume

We present and discuss noble gas compositions of minerals from silicate rocks (olivines) and carbonatites (apatites and calcites) from Brava Island. The presence of an almost ubiquitous atmosphere-derived fingerprint is explained as reflecting contamination by seawater. Because of the high U and Th content in apatites, which are responsible for ⁴He production by α-decay, the high measured ⁴He/³He ratios do not represent magmatic signatures. In contrast, low values of ⁴He/³He in calcites (≥61,223; R/R _a ≤ 11.80) and olivines (≥56,240; R/R _a ≤ 12.85) are considered to be representative of signatures trapped at the time of crystallization, given that there are no evidences for significant cosmogenic additions. These relatively low ⁴He/³He ratios depicted by silicate and carbonatite rocks imply the contribution of a reservoir that evolved under low (U + Th)/³He; this is considered a strong evidence for the genesis of Brava by a mantle plume deeply anchored in the lower mantle. The inferred low ⁴He/⁴⁰Ar* ratio (≈0.3), before degassing, is thought to reflect the contribution to the carbonatites source of a mantle domain evolving under high K/U, which cannot be explained by recycling of crustal components. The possible link between the low ⁴He/⁴⁰Ar* source and the “missing Ar reservoir” is discussed. The usually referred geochemical dichotomy between Northern and Southern Cape Verde islands, which is markedly evident from Sr, Nd, and Pb isotope signatures, is not apparent from Brava Island (Southern Cape Verde), where some samples present relatively unradiogenic ⁴He/³He signatures, similar to those reported for the Northern islands of the archipelago.