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1.
A massive ground-ice body was found exposed in the headwall of a thaw flow developed within the Chapman Lake terminal moraine complex on the Blackstone Plateau (Ogilvie Mountains, central Yukon Territory), which is contemporaneous to the Reid glaciation. Based on visible cryostructures in the 4-m-high headwall, two units were identified: massive ground ice, overlain sharply by 2 m of icy diamicton. The nature and origin of the Chapman Lake massive ground ice was determined using cryostratigraphy, petrography, stable O-H isotopes and the molar concentration of occluded gases (CO2, O2, N2 and Ar) entrapped in the ice, a new technique in the field of periglacial geomorphology that allows to distinguish between glacial and non-glacial intrasedimental ice. Collectively, the results indicate that the Chapman Lake massive ground ice formed by firn densification with limited melting-refreezing and underwent deformation near its margin. Given that the massive ground-ice body consists of relict glacier ice, it suggests that permafrost persisted, at least locally, on plateau areas in the central Yukon Territory since the middle Pleistocene. In addition, the d value of Chapman Lake relict glacier ice suggests that the ice covering the area during the Reid glaciation originated from a local alpine glaciation in the Ogilvie Mountains.  相似文献   

2.
Solubility experiments for nitrogen and noble gases (Ar and Ne) in silicate melts were conducted using two experimental configurations: one was conducted at 1 atmospheric pressure, T =1300°C and oxygen fugacity (fO2) of IW + 0.9 (i.e., 0.9 log units higher than the iron-wüstite buffer) and the other at high pressures (Ptotal ∼ 2 × 108 Pa), 1500°C and fO2 ∼ IW + 6. For the former experiment, isotopically labeled-nitrogen (15N15N-enriched) was used to distinguish dissolved nitrogen from contaminating atmospheric or organic nitrogen and to examine dissolution mechanisms of nitrogen in silicate melts. The results obtained for the two series of experiments are consistent with each other, suggesting that Henry's law is satisfied for fN2 of up to ∼250 atm (2.5 × 107 Pa). The results are also consistent with our earlier results (Miyazaki et al., 1995) obtained at highly oxidizing conditions (fO2 ∼ IW + 10). All these results support physical dissolution of nitrogen as N2 molecules in silicate melts for fO2 from ∼IW + 10 down to ∼IW. The observed solubility (Henry's constant) of nitrogen (3-5 × 10−9 mol/g/atm) is comparable to that of Ar (2-4 × 10−9 mol/g/atm), and much lower than that of Ne (11-14 × 10−9 mol/g/atm) at 1300°C. A preliminary experiment was also performed for partitioning of nitrogen and noble gases between clinopyroxene (cpx) and basaltic melt using a piston cylinder-type apparatus at 1.5 GPa and at 1270 to 1350°C. The obtained cpx/melt partition coefficient of nitrogen is 0.06, slightly lower than those of noble gases (∼0.1 for Ne to Xe), suggesting that nitrogen is as incompatible as or even slightly more incompatible than noble gases. The present results imply that a large nitrogen/Ar fractionation would not be produced by magmatic processes. Therefore, the two orders of magnitude difference between the N2/36Ar ratios in the Earth's atmosphere (∼104) and that in the mantle (∼106) must be explained by some other processes, such as incomplete segregation of metal blobs into the core and their later oxidation.  相似文献   

3.
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 (δDH2, δDH2O, δ13CCO2, δ13CCH4, and δ15NN2) 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 Ratm) with low He content (<5 ppm), atmospheric40Ar/36Ar ratio, low N2/Ar ratio (<55) and high δ15NN2 value (∼1 ‰). On the other hand, the latter N2-rich gas shows relatively low3He/4He ratio (0.1–0.4 Ratm) with high He concentration (>300 ppm), slight radiogenic40Ar/36Ar ratio, high N2/Ar ratio (77–97) and low δ15NN2 value (<0‰). Observed δDH2 value of −536‰ in H2-rich gas is distinguished from the literature value of −699‰ in the ophiolite region, giving discrepant isotope formation temperatures.  相似文献   

4.
Orthopyroxene, clinopyroxene, and olivine from a metasomatized mantle xenolith of garnet lherzolite in alkaline rocks at the Jetty Oasis, East Antarctica, contain numerous carbon dioxide-dominated composite melt-fluid and fluidized sulfide-silicate (±carbonate) inclusions. Although the maximum pressure under which the inclusions were captured by rock-forming minerals was evaluated at 13 kbar, its actual value should have been much higher, judging by the fact that the inclusions have lost part of their material (decrepitated) when the xenolith was brought to the surface. Two major fluid populations are distinguished. The fluids entrapped during the earlier episode have a more complicated composition. Dominated by CO2, these fluids contain much N2 (0.1–0.2 mole fractions), H2S, and perhaps, also H2O and are hosted by sulfide-silicate (±carbonate) inclusions produced by liquid immiscibility. As these inclusions evolved, they enriched in CO2 and depleted in H2S and N2. Although the concentrations of N2, H2S, and H2O were generally relatively low, these components played an important role in mantle metasomatism, as is reflected in the geochemistry of the derived magmas. The fluids of the younger episode (pressures lower than 7 kbar) are notably richer not only in CO2 but also in H2O (up to the appearance of inclusions with a liquid aqueous phase and the formation of CO2 gas hydrate when cooled in a cryometric stage by liquid N2). The effect of fluids on the mantle source in two discrete episodes is also confirmed by isotopic-geochemical data. Isotopic data on gases obtained immediately from fluid inclusions in minerals by the stepwise crushing technique provide evidence of the evolution of elemental and isotopic ratios of the gases in the course of the metasomatic processes. The high-pressure fluid inclusions of the earlier episode have low C/N2, C/Ar, and N2/Ar ratios, isotopically heavy N2, and somewhat elevated (to 530) 40Ar/36Ar ratios. The younger fluids typically have higher (by two to three orders of magnitude) C/N2 and C/Ar ratios, lower δ13C of CO2, and N2/Ar and 40Ar/36Ar ratios close to the atmospheric values. The nitrogen and argon isotopic compositions and elemental ratios suggest that the younger fluids could have been produced by two-component mixing in the mantle-atmosphere system. Comprehensive analysis of the data and in particular the 40Ar/36Ar ratios, which are atypical of the mantle, and an increase in the H2O concentration, suggests a subduction-related nature of the fluids.  相似文献   

5.
《Applied Geochemistry》2000,15(4):455-474
Between 1987 and 1995 more than 100 chemical and isotopic analyses were carried out on the thermal fluids discharged at surface from wells and springs of the Euganean and Berician thermal district. Results for δD and δ18O in waters, δ13C in CO2 and in C1–C4 n-alkanes, δD in CH4, 3He/4He and 40Ar/36Ar ratios in natural gases were coupled with chemical analyses in an attempt to determine the main characteristics and evolutionary trends of thermal fluids emerging in the region. The isotopic and chemical composition of thermal waters has led to the postulation of a meteoric origin of discharged thermal fluids and of a “maturation” trend as water moves from the peripheral manifestations of the Berici Hills towards those of the Battaglia, Montegrotto and Abano springs in the inner part of the geothermal field. Numerical simulation suggested that the observed evolutionary path is consistent with differentiation due to processes of water–rock interaction.The results of bulk analyses have shown that the gases are made up mainly of N2 (65–95 vol%), CO2 (0.5–20.5 vol%) and CH4 (up to 10 vol%), with relatively high Ar and He contents (up to 1.5 vol% and 0.16 vol%, respectively) and detectable amounts of C2–C6 saturated hydrocarbons. The chemical and isotopic composition of the gases suggests that both the meteoric and crustal contributions to the natural discharges are significant, while any significant magmatic contribution, possibly related to vestiges of the volcanic activity that occurred in the Abano area during the Tertiary age, can be ruled out.  相似文献   

6.
To better understand the long-term climate history of Antarctica, we studied Lake Bonney in Taylor Valley, Southern Victoria Land (78°S). Helium isotope ratios and He, Ne, Ar and N2 concentration data, obtained from hydrocasts in the East (ELB) and West (WLB) Lobes of Lake Bonney, provided important constraints on the lakes Holocene evolution. Based on very low concentrations of Ar and N2 in the ELB bottom waters, ELB was free of ice until 200 ± 50 years ago. After which, low salinity water flowing over the sill from WLB to ELB, covered ELB and formed a perennial ice cover, inhibiting the exchange of gases with the atmosphere. In contrast to the ELB, the WLB retained an ice cover through the Holocene. The brine in the WLB bottom waters has meteoric N2 and Ar gas concentrations indicating that it has not been significantly modified by atmospheric exchange or ice formation. The helium concentrations in the deep water of WLB are the highest measured in non-thermal surface water. By fitting a diffusional loss to the 3He/4He, helium, and Cl profiles, we calculate a time of 3000 years for the initiation of flow over the sill separating the East and West Lobes. To supply this flux of helium to the lake, a helium-rich sediment beneath the lake must be providing the helium by diffusion. If at any time during the last million years the ice cover left WLB, there would be insufficient helium available to provide the current flux to WLB. The variations in water levels in Lake Bonney can be related to climatic events that have been documented within the Southern Victoria Land region and indicate that the lakes respond significantly to regional and, perhaps, global climate forcing.  相似文献   

7.
The isotopic composition of atmospheric O2 depends on the rates of oxygen cycling in photosynthesis, respiration, photochemical reactions in the stratosphere and on δ17O and δ18O of ocean and leaf water. While most of the factors affecting δ17O and δ18O of air O2 have been studied extensively in recent years, δ17O of leaf water—the substrate for all terrestrial photosynthesis—remained unknown. In order to understand the isotopic composition of atmospheric O2 at present and in fossil air in ice cores, we studied leaf water in field experiments in Israel and in a European survey. We measured the difference in δ17O and δ18O between stem and leaf water, which is the result of isotope enrichment during transpiration. We calculated the slopes of the lines linking the isotopic compositions of stem and leaf water. The obtained slopes in ln(δ17O + 1) vs. ln(δ18O + 1) plots are characterized by very high precision (∼0.001) despite of relatively large differences between duplicates in both δ17O and δ18O (0.02-0.05‰). This is so because the errors in δ18O and δ17O are mass-dependent. The slope of the leaf transpiration process varied between 0.5111 ± 0.0013 and 0.5204 ± 0.0005, which is considerably smaller than the slope linking liquid water and vapor at equilibrium (0.529). We further found that the slope of the transpiration process decreases with atmospheric relative humidity (h) as 0.522-0.008 × h, for h in the range 0.3-1. This slope is neither influenced by the plant species, nor by the environmental conditions where plants grow nor does it show strong variations along long leaves.  相似文献   

8.
《Applied Geochemistry》1995,10(5):505-516
Stable isotopic ratios of C and H in dissolved CH4 and C in dissolved inorganic C in the ground water of a crude-oil spill near Bemidji, Minnesota, support the concept of CH4 production by acetate fermentation with a contemporaneous increase in HCO3− concentration. Methane concentrations in the saturated zone decrease from 20.6 mg L−1 to less than 0.001 mg L−1 along the investigated flow path. Dissolved N2 and Ar concentrations in the ground water below the oil plume are 25 times lower than background; this suggests that gas exsolution is removing dissolved CH4 (along with other dissolved gases) from the ground water. Oxidation of dissolved CH4 along the flow path seems to be minimal because no measurable change in isotopic composition of CH4 occurs with distance from the oil body. However, CH4 is partly oxidized to CO2 as it diffuses upward from the ground water through a 5- to 7-m thick unsaturated zone; theδ13C of the remaining CH4 increases, theδ13C of the CO2 decreases, and the partial pressure of CO2 increases.Calculations of C fluxes in the saturated and unsaturated zones originating from the degradation of the oil plume lead to a minimum estimated life expectancy of 110 years. This is a minimum estimate because the degradation of the oil body should slow down with time as its more volatile and reactive components are leached out and preferentially oxidized. The calculated life expectancy is an order of magnitude estimate because of the uncertainty in the average linear ground-water velocities and because of the factor of 2 uncertainty in the calculation of the effective CO2 diffusion coefficient.  相似文献   

9.
Stable SO4 isotopes (δ34S-SO4 and δ18O-SO4), and more occasionally δ15N-NO3 were studied in groundwater from seven hard-rock aquifer catchments. The sites are located in Brittany (France) and all are characterized by intensive agricultural activity. The purpose of the study was to investigate the potential use of these isotopes for highlighting the fate of both SO4 and NO3 in the different aquifer compartments. Nitrate-contaminated groundwater occurs in the regolith; δ34S fingerprints the origin of SO4, such as atmospheric deposition and fertilizers, and δ18O-SO4 provides evidence of the cycling of S within soil. The correlation between the δ18O-SO4 of sulfates and the δ15N-NO3 of nitrates suggests that S and N were both cycled in soil before being leached to groundwater. Autotrophic and heterotrophic denitrification was noted in fissured aquifers and in wetlands, respectively, the two processes being distinguished on the basis of stable SO4 isotopes. During autotrophic denitrification, both δ34S-SO4 and δ18O-SO4 decrease due to the oxidation of pyrite and the incorporation of O from the NO3 molecule in the newly formed SO4. Within wetlands, fractionation occurs of O isotopes on SO4 in favour of lighter isotopes, probably through reductive assimilation processes. Fractionation of S isotopes is negligible as the redox conditions are not sufficiently reductive for dissimilatory reduction. δ34S-SO4 and δ18O-SO4 data fingerprint the presence of a NO3-free brackish groundwater in the deepest parts of the aquifer. Through mixing with present-day denitrified groundwater, this brackish groundwater can contribute to significantly increase the salinity of pumped water from the fissured aquifer.  相似文献   

10.
Fluid inclusions found trapped in speleothems (cave deposited travertine) are interpreted as samples of seepage water from which enclosing calcium carbonate was deposited. The inclusions are assumed to have preserved their D/H ratios since the time of deposition. Initial 18O/16O ratios can be inferred from δD because rain- and snow-derived seepage waters fall on the meteoric water line (δD = 8δ18O + 10). Estimates of temperature of deposition of the carbonate can be calculated from inclusion D/H ratios and δ18O of enclosing calcite in Pleistocene speleothems. For most speleothems investigated (0–200,000 yr old) δ18O of calcite appears to have decreased with increasing temperature of deposition indicating that the dominant cause of climate-dependent change in δ18O of calcite was the change in Kcw, the isotope fractionation equilibrium constant, with temperature; δ18O of meteoric precipitation generally increased with increasing temperature, but not sufficiently to compensate for the decrease in Kcw.  相似文献   

11.
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 (δl3C PDB) of carbon dioxide ranges from -20‰ to -2‰. δl5N(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.  相似文献   

12.
Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ34SΣs of 0.7 ± 0.1 ‰. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is +7.5 ± 1.5‰. On the other hand, the concentration and δ34SΣs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and ?0.8 ± 0.2‰, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the ?o2 and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO2 from basalt thereby depleting sulfate and 34S in basalt.The volcanic sulfur gases, predominantly SO2, from the 1971 and 1974 fissures in Kilauea Crater have δ34S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ34S value of sulfur gases (largely SO2) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ34S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ34S values (+5 to +6%.o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.  相似文献   

13.
Chemical and isotopic compositions have been measured for N2-He-rich bubbling gases discharging from hot springs in the Hainan Island, Southern China. Observed 3He/4He ratios (0.1–1.3 RA) indicate the occurrence of a mantle component throughout the island, which has been highly diluted by a crustal radiogenic 4He component. The occurrence of mantle-derived helium is high in the northern island (12%–16% of total He) and gradually decreases towards southern coast (1%–3% of total He). Such a distribution pattern is most likely controlled by the Pleocene-Quaternary volcanic activities in the northern island and groundwater circulation along the deep major faults. The 40Ar/36Ar and N2/Ar ratios suggest that N2 and Ar of the hot spring gases are mostly meteoric. Although δ13C values of CO2 (–20‰ to –27‰) with low concentrations are consistent with the biogenic origin, the combination of 3He/4He and d13CCO2 suggests a two end-member mixing of mantle and crustal components with CO2/3He ratios of 2×109 and 8×1011, respectively. However, the low CO2/3He ratios (1–22×106) can not be ascribed in terms of the simple mixing but has to be explained by the addition of radiogenic 4He and loss of CO2 by calcite precipitation in the hydrothermal system, which is most likely controlled by the degree of gas-water-rock interaction.  相似文献   

14.
This paper reports the first rare earth element (REE) concentrations in accreted ice refrozen from sub-glacial Lake Vostok (East Antarctica). REE were determined in various sections of the Vostok ice core in order to geochemically characterize its impurities. Samples were obtained from accreted ice and, for comparison, from the upper glacier ice of atmospheric origin (undisturbed, disturbed and glacial flour ice). REE concentrations ranged between 0.8-56 pg g−1 for Ce and 0.0035-0.24 pg g−1 for Lu in glacier ice, and between <0.1-24 pg g−1 for Ce and <0.0004-0.02 pg g−1 for Lu in accreted ice. Interestingly, the REE concentrations in the upper accreted ice (AC1; characterized by visible aggregates containing a mixture of very fine terrigenous particles) and in the deeper accreted ice (AC2; characterized by transparent ice) are lower than those in fresh water and seawater, respectively. We suggest that such ultra-low concentrations are unlikely to be representative of the real REE content in Lake Vostok, but instead may reflect phase exclusion processes occurring at the ice/water interface during refreezing. In particular, the uneven spatial distribution (on the order of a few cm) and the large range of REE concentrations observed in AC1 are consistent with the occurrence/absence of the aggregates in adjacent ice, and point to the presence of solid-phase concentration/exclusion processes occurring within separate pockets of frazil ice during AC1 formation. Interestingly, if the LREE enrichment found in AC1 was not produced by chemical fractionation occurring in Lake Vostok water, this may reflect a contribution of bedrock material, possibly in combination with aeolian dust released into the lake by melting of the glacier ice. Collectively, this valuable information provides new insight into the accreted ice formation processes, the bedrock geology of East Antarctica as well as the water chemistry and circulation of Lake Vostok.  相似文献   

15.
The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as −23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δDEPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from −60 to −78‰, and δ18OEPIDOTE in these wells are between −3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ18O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δDFLUID of ∼ −79‰ and −89‰, respectively, show δDEPIDOTE values of −115‰ and −125‰. In contrast, δDEPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is −68‰; comparable to δDEPIDOTE from well RN-10 at Reykjanes.Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ18O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δDFLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ18OFLUID values are within range of the observed fluid isotope composition. We propose that modern δDEPIDOTE and δDFLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δDROCK value is −125‰ and the water to rock mass ratio is 0.25, predicts a δDFLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.  相似文献   

16.
张体强  胡树国  韩桥 《岩矿测试》2014,33(6):775-781
超高纯气体在工业生产中有非常重要的地位,如半导体工业中电子气的质量直接影响半导体器件的性能,百万分之几的微量杂质气体便可导致集成电路中元件存储信息量的减少。越来越高的气体纯度要求对分析方法及仪器的灵敏度提出了很大的挑战。大气压电离质谱(APIMS)由于可以在大气压条件下对杂质进行电离,并伴随高效的电离方式,因此具有极高的灵敏度,成为超高纯气体杂质分析中极为有效的技术手段,特别适合检测10-9 mol/mol甚至10-12 mol/mol浓度量级的气体杂质。APIMS采用电晕放电及63Ni两种电离源,通常以电晕放电电离源为主,质量分析器常采用四极杆,同时为适应超高纯气体分析,APIMS配备了气体进样系统及可将标准气体稀释产生校正气体的稀释系统。APIMS对杂质检测的灵敏度与杂质的电离方式密切相关,电荷传递是杂质电离最主要的一种方式,适用于电离能相差较大的底气与杂质,常见的N2、Ar由于电离能较高,其中的大部分杂质均可依靠该方式测定;质子转移反应的应用通常与H2有关,常用于H2中杂质的测定,也可以通过添加H2的方法促进对Ar中N2杂质的检测;运用形成团簇离子的反应尽管较少,但亦有报道,通过监测团簇离子O2+·H2O,可提高O2中杂质H2O的检测灵敏度。依据不同的电离反应,可以设计对不同杂质的测定方式,实现对痕量、超痕量杂质的检测。APIMS检测灵敏度通常比电子轰击电离质谱(EI/MS)高104~106倍,因此目前依然是超高纯气体分析中不可替代的仪器方法,但在某些方面如对有腐蚀性电子特气的分析,方法灵敏度有待提高。  相似文献   

17.
《Applied Geochemistry》2001,16(3):323-338
Chemical and isotopic compositions are reported for water, and CO2 and noble gases in groundwater and soda springs from Bioko, Principé, São Tomé and Annobon, all islands located in the off-shore part of the Cameroon Volcanic Line in West Africa. The soda spring waters are of Ca–Mg–HCO3 type, with δD and δ18O values that range from −20 to −8‰ and −5.4 to −2.7‰ respectively, indicative of a meteoric origin. CO2 is the main gas species in the springs. δ13C–CO2 values vary from −2.8 to −5.0‰, overlapping the observed mantle C range (−3 to −8‰). CO2/3He ratios (3–9×109) suggest that most C (∼90%) in the samples is derived from the mantle. Neon has atmospheric isotopic compositions, while Ar is slightly enriched in radiogenic 40Ar. 3He/4He ratios (3.0 to 10.1×10−6 or 2.1 to 7.2Ra, where Ra is the atmospheric ratio of 1.4×10−6) are much higher than those for typical crustal fluids (∼10−8) but lower than those expected for fluids derived from ‘high-3He/4He’ hotspots like Loihi and Iceland. This precludes significant contributions of such fluids in the source regions of the gases, and by inference, in the magmatism of these oceanic islands. Alternatively, approximately 90% of the He in São Tomé gases is inferred to be derived from a source similar to the MORB source. The 3He/4He ratio for the Bioko gas (6.6×10−6) may be derived from a source with a higher time integrated (U+Th)/3He ratio than the MORB source.  相似文献   

18.
Past global mean ocean temperature may be reconstructed from measurements of atmospheric noble gas concentrations in ice core bubbles. Assuming conservation of noble gases in the atmosphere-ocean system, the total concentration within the ocean mostly depends on solubility which itself is temperature dependent. Therefore, the colder the ocean, the more gas can be dissolved and the less remains in the atmosphere. Here, the characteristics of this novel paleoclimatic proxy are explored by implementing krypton, xenon, argon, and N2 into a reduced-complexity climate model. The relationship between noble gas concentrations and global mean ocean temperature is investigated and their sensitivities to changes in ocean volume, ocean salinity, sea-level pressure and geothermal heat flux are quantified. We conclude that atmospheric noble gas concentrations are suitable proxies of global mean ocean temperature. Changes in ocean volume need to be considered when reconstructing ocean temperatures from noble gases. Calibration curves are provided to translate ice-core measurements of krypton, xenon, and argon into a global mean ocean temperature change. Simulated noble gas-to-nitrogen ratios for the last glacial maximum are δKratm = ?1.10‰, δXeatm = ?3.25‰, and δAratm = ?0.29‰. The uncertainty of the krypton calibration curve due to uncertainties of the ocean saturation concentrations is estimated to be ±0.3 °C. An additional ±0.3 °C uncertainty must be added for the last deglaciation and up to ±0.4 °C for earlier transitions due to age-scale uncertainties in the sea-level reconstructions. Finally, the fingerprint of idealized Dansgaard-Oeschger events in the atmospheric krypton-to-nitrogen ratio is presented. A δKratm change of up to 0.34‰ is simulated for a 2 kyr Dansgaard-Oeschger event, and a change of up to 0.48‰ is simulated for a 4 kyr event.  相似文献   

19.
Results of the chemical and isotopic analysis of the water and gases discharged from volcanic crater lakes and soda springs located along the Cameroon Volcanic Line were used to characterize and infer their genetic relationships. Variations in the solute compositions of the waters indicate the dominant influence of silicate hydrolysis. Na+ (40–95%) constitutes the major cation in the springs while Fe2+ + Mg2+ (70%) dominate in the CO2-rich lakes. The principal anion is HCO3 (>90%), except in the coastal springs where Cl-predominates. Lakes Nyos and Monoun have FeMgCaHCO3− type signatures; the soda springs are essentially NaHCO3− type, while all other lakes show similar ionic compositions to dilute surface waters. Dissolved gases show essentially CO2 (>90%), with small amounts of Ar and N2, while CH4 constitutes the principal component in the non-gassy lakes. Active volcanic gases are generally absent, except in the Lobe spring with detectable H2S. Stable isotope ratio evidence indicates that the bicarbonate waters are essentially of meteoric origin. CO2 (δ13C = −2 to −8%0 and He (3He/4He = 1 to 5.6Ra) infer a mantle contribution to the total CO2. CH4 has a biogenic source, while Ar and N2 are essentially atmospheric in origin, but mixing is quite common.  相似文献   

20.
Polar ice cores are unique climate archives. Indeed, most of them have a continuous stratigraphy and present high temporal resolution of many climate variables in a single archive. While water isotopic records (δD or δ18O) in ice cores are often taken as references for past atmospheric temperature variations, their relationship to temperature is associated with a large uncertainty. Several reasons are invoked to explain the limitation of such an approach; in particular, post-deposition effects are important in East Antarctica because of the low accumulation rates. The strong influence of post-deposition processes highlights the need for surface polar research programs in addition to deep drilling programs. We present here new results on water isotopes from several recent surface programs, mostly over East Antarctica. Together with previously published data, the new data presented in this study have several implications for the climatic reconstructions based on ice core isotopic data: (1) The spatial relationship between surface mean temperature and mean snow isotopic composition over the first meters in depth can be explained quite straightforwardly using simple isotopic models tuned to d-excess vs. δ18O evolution in transects on the East Antarctic sector. The observed spatial slopes are significantly higher (～ 0.7–0.8‰·°C?1 for δ18O vs. temperature) than seasonal slopes inferred from precipitation data at Vostok and Dome C (0.35 to 0.46‰·°C?1). We explain these differences by changes in condensation versus surface temperature between summer and winter in the central East Antarctic plateau, where the inversion layer vanishes in summer. (2) Post-deposition effects linked to exchanges between the snow surface and the atmospheric water vapor lead to an evolution of δ18O in the surface snow, even in the absence of any precipitation event. This evolution preserves the positive correlation between the δ18O of snow and surface temperature, but is associated with a much slower δ18O-vs-temperature slope than the slope observed in the seasonal precipitation. (3) Post-deposition effects clearly limit the archiving of high-resolution (seasonal) climatic variability in the polar snow, but we suggest that sites with an accumulation rate of the order of 40 kg.m?2.yr?1 may record a seasonal cycle at shallow depths.  相似文献   

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