Carbon and Noble Gas Isotopes in the Tengchong Volcanic Geothermal Area, Yunnan, Southwestern China

Carbon and noble gas isotope analyses are reported for bubbling gas samples from the Tengchong volcanic geothermal area near the Indo-Eurasian suture zone. All samples contain a resolvable component of mantle-derived 3He. Occurrence of mantle-derived 3He coincides with surface volcanism. However, 3He occurs over a larger geographic areathan do surface volcanics. δ13C values for CO2 and CH4 vary from -33.4‰ to 1.6 ‰ and from -52.8‰ to -2.8‰, respectively. He and C isotope systematics indicate that CO2 and CH4 in the CO2-rich gases originated predominantly from magmatic component mixed with crustal CO2 produced from carbonate. However, breakdown of organic matter and near-surface processes accounts for the CH4 and CO2 in N2-rich gases. 3He/4He ratio distribution pattern suggests that mantle-derived He and heat sources of high-temperature system in central Tengchong originate from a hidden magma reservoir at subsurface. CO2-rich gases with the highest 3He/4He ratio (5.2 Ra) may be representative of the Tengchong magmatic component. Compared with MORB, this relative low 3He/4He ratio could be fully attributed to either deep crustal contamination, or radioactive aging, or past contamination of the local mantle by U- and Th-rich subducted crustal material. However, a combination of low 3He/4He, high radiogenic 4He/40Ar ratio and identical CO2/3He and δ13Cco2 relative to MORB may suggest addition of prior subductedd crsustal material (ca 1 %-2%) to the MORB reservoir around 1.3 Ga ago, which is essentially compatible with the LIL-elements, and Sr-Nd-Pb isotopes of volcanic rocks.

Constraints on granite-related uranium mineralization in the Sanjiu uranium ore field,SE China provided by pyrite mineralogy,major and trace elements,S-He-Ar isotopes

The Sanjiu uranium ore field,located in the central of Zhuguangshan granitic batholith,is a newly discovered granite-related uranium ore field in South China.The main sulfide in the ore field is pyrite,which is closely related to uranium mineralization.The textures major and trace elements,S-He-Ar isotopes compositions of pyrites in ores of different grade were observed and/or analyzed by optical microscope,scanning electron microscope,electron microprobe,laser ablation inductively coupled plasma mass spectrometry,and noble gas mass spectrometer(Helix-SFT).It is observed that these U-related pyrites are generally euhedral-subhedral with dissolution textures,anhedral variety with colloform texture veinlet and fine particles,and the color of the associated minerals is mostly dark hue,such as purple-black fluorite dark-red hematite,and dark-green chlorite,etc.The analytical results show that the average compositions of major elements in pyrite are FeS1.944.Pyrites are characterized by S-deficiency,low content of Co and Th,and Co/Ni>1which indicate that these ores are of low-temperature hydrothermal origin.We found that the higher the grade of ore,the more deficient in S,the more obvious negative δ^34S,and the higher REE content(close to U-rich granitic pluton)of pyrite.The S-He-Ar isotopic compositions of various varieties of pyrites indicate that the ore-forming fluids mainly come from crust-derived fluids and mixed with mantle-derived fluids.

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

Noble gas isotopic compositions of various layers in three-layered （outer, porous and compact layers） cobalt-rich ferromanganese crusts and their basaltic and phosphorite substrates from the western Pacific Ocean were analyzed by using a high vacuum gas mass spectrum. The analytical results show that the noble gases in the Co-rich crusts have derived mainly from the ambient seawater, extraterrestrial grains such as interplanetary dust particles （IDPs） and wind-borne continental dust grains, and locally formation water in the submarine sediments, but different noble gases have different sources. He in the crusts derives predominantly from the extraterrestrial grains, with a negligible amount of radiogenic He from the eolian dust grains. Ar is sourced mainly from the dissolved air in the seawater and insignificantly from radiogenic Ar in the eolian continental dust grains or the formation water. Xe and Ne derive mainly from the seawater, with minor amounts of extraterrestrial Xe and Ne in the IDPs. Compared with the porous and outer layers, the compact layer has a relatively high 4He content and lower 3He/4He ratios, suggesting that marine phosphatization might have greatly modified the noble gas isotopic compositions of the crusts. Besides, the 3He/4He values of the basaltic substrates of the cobalt-rich crusts are very low and their R/R. ratios are mostly 〈0.1 R., which are similar to that of phosphorite substrates （0.087 R.）, but much lower than that of fresh submarine MORB （8.75±14 Ra） or seamount basalts （3-43 Ra）, implying that the basaltic substrates have suffered strong water/rock interaction and reacted with radiogenic ^4He and P-rich upwelling marine currents during phosphatization. The trace elements released in the basalt/seawater interaction might favor the growth of cobalt-rich crusts. The relatively low ^3He/^4He values in the seamount basalts may be used as an important exploration criterion for the cobalt-rich ferromanganese crusts.

Mantle-derived CO_(2) in Hot Springs of the Rehai Geothermal Field,Tengchong,China

Gas concentrations and isotopic compositions of He and CO2 were determined on free gas samples from ten hot springs of the Rehai geothermal field, Tengchong, China. The results showed that hot-spring CO2 gas, together with He, was derived mainly from the mantle, indicating the accumulation of mantle-derived volatiles beneath the survey area. The δ 13C values of CO2, higher than those of the typical mantle-derived carbon and the isotopic composition of hot-spring-free CO2 in unequilibrium with dissolved CO2, are recognized only in the Rehai geothermal field, suggesting that there seems to be a still-degassing magmatic intrusion at depths, which provides mantle-derived volatiles to the hydrothermal system above. The accumulation of those volatiles has probably played an important role in triggering earthquakes in this region. In addition, the isotopic characteristics of He and C also indicate that the magmatic intrusion seems to have been derived from the MORB source, and could be contaminated by crustal materials during its upwelling through the continental crust.

Surface geochemical data evaluation and integration with geophysical observations for hydrocarbon prospecting,Tapti graben,Deccan Syneclise,India

The Deccan Syneclise is considered to have significant hydrocarbon potential. However, significant hydrocarbon discoveries, particularly for Mesozoic sequences, have not been established through conventional exploration due to the thick basalt cover over Mesozoic sedimentary rocks. In this study, near-surface geochemical data are used to understand the petroleum system and also investigate type of source for hydrocarbons generation of the study area. Soil samples were collected from favorable areas identified by integrated geophysical studies. The compositional and isotopic signatures of adsorbed gaseous hydrocarbons （methane through butane） were used as surface indicators of pe- troleum micro-seepages. An analysis of 75 near-surface soil-gas samples was carried out for light hydrocarbons （C_1-C_4） and their carbon isotopes from the western part of Tapti graben, Deccan Syneclise, India. The geochemical results reveal sites or clusters of sites containing anomalously high concentrations of light hydrocarbon gases. High concentrations of adsorbed thermogenic methane （C1 518 ppb） and ethane plus higher hydrocarbons （∑C2＋ = 977 ppb） were observed. Statistical analysis shows that samples from 13% of the samples contain anomalously high concentrations of light hydrocarbons in the soil-gas constituents. This seepage suggests largest magnitude of soil gas anomalies might be generated/source from Mesozoic sedimentary rocks, beneath Deccan Traps. The carbon isotopic composition of methane, ethane and propane ranges are from 22.5‰to -30.2‰ PDB, -18.0‰ to 27.1‰,, PDB and 16.9‰-32.1‰ PDB respectively, which are in thermogenic source. Surface soil sample represents the intersection of a migration conduit from the deep subsurface to the surface connected to sub-trappean Mesozoic sedimentary rocks. Prominent hydrocarbon concentra- tions were associated with dykes, lineaments and presented on thinner basaltic cover in the study area, which probably acts as channel for the micro-seepage of hydrocarbons.

Abnormal Concentration and Origin of Heavy Hydrocarbon in Upper Permian Coal Seams from Enhong Syncline,Yunnan,China

Coalbed gas （CBG） in Enhong syncline, eastern Yunnan China, is character- ized by high concentration of heavy hydrocarbon with the highest content of ethane, which is more than 30%. Some previous investigators paid much attention to the abnormal concentration of heavy hydrocar- bon in the CBG of Enhong, but few have researched on its origin. This article describes the characteristics of abnormal high concentration of heavy hydrocarbon in Enhong syncline and analyzes its reason from the aspects of origin and evolution of heavy hydrocarbon by carbon isotope, coal petrography, and coal rank. Features of gas carbon isotope composition display that there is no inorganic gas or off components in the CBG, which is classified to thermogenetic gas produced by humic material, with characteristic of secondary biogenic gas in shallow coal seam. The concentration of heavy hydrocarbon in Enhong syncline increases with the increase of vitrinite, vitrinite/inertinite ratio, and hydrogen/carbon ratio and decreases with the increase of inertinite, so hydrogen-rich vitrinite may be a very important factor resulting in the abnormal concentration of heavy hydrocarbon. It also increases with the increase of degree of coalifica-tion of coking to lean coals during which the peak of heavy hydrocarbon generation is reached. Therefore, we think that high concentration of heavy hydrocarbon originated from the coupling effect of higher content of the hydrogen-rich vitrinite in the coal and the coal rank of coking to lean coals.

Developing an authentication approach using SPME-GC-IRMS based on compound-specific δ^(13)C analysis of six typical volatiles in wine

An analytical method using gas chromatography isotope ratio mass spectrometry(GC-IRMS)combined with solid phase micro-extraction(SPME)was developed to measure the 613C values of six typical volatiles commonly occurring in wine(isoamyl acetate,2-octanone,limonene,2-phenylethanol,ethyl octanoate and ethyl decanoate)for the first time.SPME selected with a divinylbenzene/carboxen/polydimethylsiloxane fiber was combined with the GC-IRMS for pretreatment optimization.The optimized SPME parameters of extraction time,extraction temperature and salt concentration were 40 min,40℃ and 10%,respectively.The 613C values measured by SPME-GC-IRMS were in good agreement with those measured via elemental analyzer(EA)-IRMS and GC-IRMS.The differences range from 0.02‰to 0.44‰ with EA-IRMS and from 0 to 0.28‰ with GC-IRMS,indicating the high accuracy of the method.This newly established method measured the precision within 0.30‰ and was successfully validated to discriminate imported real wine samples with identical label but amazing price differences from different importers.