A review of the geochemistry of methane in natural gas hydrate

The largest accumulations on Earth of natural gas are in the form of gas hydrate, found mainly offshore in outer continental margin sediment and, to a lesser extent, in polar regions commonly associated with permafrost. Measurements of hydrocarbon gas compositions and of carbon-isotopic compositions of methane from natural gas hydrate samples, collected in subaquatic settings from around the world, suggest that methane guest molecules in the water clathrate structures are mainly derived by the microbial reduction of CO₂ from sedimentary organic matter. Typically, these hydrocarbon gases are composed of > 99% methane, with carbon-isotopic compositions (δ¹³C_PDB) ranging from − 57 to − 73‰. In only two regions, the Gulf of Mexico and the Caspian Sea, has mainly thermogenic methane been found in gas hydrate. There, hydrocarbon gases have methane contents ranging from 21 to 97%, with δ¹³C values ranging from − 29 to − 57‰. At a few locations, where the gas hydrate contains a mixture of microbial and thermal methane, microbial methane is always dominant. Continental gas hydrate, identified in Alaska and Russia, also has hydrocarbon gases composed of > 99% methane, with carbon-isotopic compositions ranging from − 41 to − 49‰. These gas hydrate deposits also contain a mixture of microbial and thermal methane, with thermal methane likely to be dominant. Published by Elsevier Science Ltd     

A new method for estimating rate constants for trace gas reactions within stratospheric sulphuric acid aerosol droplets

Uptake of trace gases by (stratospheric aerosol can be significant particularly after large injections of volcanic sulphur. A theoretical scheme is presented to quantify the rate at which trace gases diffuse into these aerosol droplets. Rate constants for 19 trace gases are calculated and it is found that the rates vary from a value of 2.85 × 10^-7s^-1 for CC14 to 8.08 × 10^-7s^-1 for NO. The calculations are characterised by their ease of application and can be incorporated into stratospheric chemical models.     

Geochemistry of the volcano-hydrothermal system of El Chichón Volcano, Chiapas, Mexico

 The 1982 eruption of El Chichón volcano ejected more than 1 km³ of anhydrite-bearing trachyandesite pyroclastic material to form a new 1-km-wide and 300-m-deep crater and uncovered the upper 500 m of an active volcano-hydrothermal system. Instead of the weak boiling-point temperature fumaroles of the former lava dome, a vigorously boiling crater spring now discharges  / 20 kg/s of Cl-rich (∼15 000 mg/kg) and sulphur-poor ( / 200 mg/kg of SO₄), almost neutral (pH up to 6.7) water with an isotopic composition close to that of subduction-type magmatic water (δD=–15‰, δ¹⁸O=+6.5‰). This spring, as well as numerous Cl-free boiling springs discharging a mixture of meteoric water with fumarolic condensates, feed the crater lake, which, compared with values in 1983, is now much more diluted (∼3000 mg/kg of Cl vs 24 030 mg/kg), less acidic (pH=2.6 vs 0.56) and contains much lower amounts of S ( / 200 mg/kg of SO₄, vs 3550 mg/kg) with δ³⁴S=0.5–4.2‰ (+17‰ in 1983). Agua Caliente thermal waters, on the southeast slope of the volcano, have an outflow rate of approximately 100 kg/s of 71  °C Na–Ca–Cl water and are five times more concentrated than before the eruption (B. R. Molina, unpublished data). Relative N₂, Ar and He gas concentrations suggest extensional tectonics for the El Chichón volcanic centre. The ³He/⁴He and ⁴He/²⁰Ne ratios in gases from the crater fumaroles (7.3R_a, 2560) and Agua Caliente hot springs (5.3R_a, 44) indicate a strong magmatic contribution. However, relative concentrations of reactive species are typical of equilibrium in a two-phase boiling aquifer. Sulphur and C isotopic data indicate highly reducing conditions within the system, probably associated with the presence of buried vegetation resulting from the 1982 eruption. All Cl-rich waters at El Chichón have a common source. This water has the appearence of a "partially matured" magmatic fluid: condensed magmatic vapour neutralized by interaction with fresh volcaniclastic deposits and depleted in S due to anhydrite precipitation. Shallow ground waters emerging around the volcano from the thick cover of fresh pumice deposits (Red waters) are Ca–SO₄–rich and have a negative oxygen isotopic shift, probably due to ongoing formation of clay at low temperatures. Received: 21 July 1997 / Accepted: 4 December 1997     

Solar cycle length hypothesis appears to support the ipcc on global warming

Since the discovery of a striking correlation between 1-2-2-2-1 filtered solar cycle lengths and the 11-year running average of northern hemisphere land air temperatures, there have been widespread speculations as to whether these findings would rule out any significant contributions to global warming from the enhanced concentrations of greenhouse gases. The solar hypothesis (as we shall term this assumption) claims that solar activity causes a significant component of the global mean temperature to vary in phase opposite to the filtered solar cycle lengths. In an earlier article we have demonstrated that for data covering the period 1860–1980 the solar hypothesis does not rule out any significant contribution from man-made greenhouse gases and sulphate aerosols. The present analysis goes a step further. We analyse the period 1579–1987 and find that the solar hypothesis—instead of contradicting—appears to support the assumption of a significant warming due to human activities. We have tentatively corrected the historical northern hemisphere land air temperature anomalies by removing the assumed effects of human activities. These are represented by northern hemisphere land air temperature anomalies calculated as the contributions from man-made greenhouse gases and sulphate aerosols by using an upwelling diffusion-energy balance model similar to the model of Wigley and Raper, 1993 employed in the Second Assessment Report of The Intergovernmental Panel on Climate Change (IPCC). It turns out that the agreement of the filtered solar cycle lengths with the corrected temperature anomalies is substantially better than with the historical anomalies, with the mean square deviation reduced by 36% for a climate sensitivity of 2.5°C, the central value of the IPCC assessment, and by 43% for the best-fit value of 1.7°C. Therefore our findings support a total reversal of the common assumption that a verification of the solar hypothesis would challenge the IPCC assessment of man-made global warming.     

Noble gas components in planetary atmospheres and interiors in relation to solar wind and meteorites

We discuss observed xenon isotopic signatures in solar system reservoirs and possible relationships. The predominant trapped xenon component in ordinary chondrites (OC) is OC-Xe and its isotopic signature differs from Xe in ureilites, in carbonaceous chondrites, in the atmospheres of Earth and Mars, and in the solar wind. Additional minor Xe components were identified in type 3 chondrites and in the metal phase of chondrites. The OC-Xe and ureilite signatures are both consistent with varying mixtures of HL-Xe and slightly mass fractionated solar-type Xe. Xenon in the Martian atmosphere is found to be strongly mass fractionated by 37.7‰ per amu, relative to solar Xe, favoring the heavy isotopes. Xenon in SNC’s from the Martian mantle show admixture of solar-type Xe, which belongs to an elementally strongly fractionated component. The origin of the isotopic signatures of Ne and Xe in the terrestrial atmosphere are discussed in the light of evidence that the Xe isotopic fractionations in the Martian and terrestrial atmospheres are consistent. However, in the terrestrial atmospheric Xe component excesses are observed for¹³²Xe and also for^129,131Xe, relative to fractionated solar Xe. The suggested chemically fractionated fission Xe component (CFF-Xe) seems to closely match the above excesses. We discuss models of origin for planetary volatiles and possible processes driving their evolution to present day compositions.     

原煤尾气和煤渣中多环芳烃相关性测定

对原煤、尾气和煤渣中多环芳烃进行了相关性测试。在模拟工业锅炉代表性燃烧条件下将烟煤和无烟煤样品在管式炉中燃烧，分别采用ＧＣＭＳ和ＨＰＬＣ法对原煤、尾气和煤渣中的多环芳烃种类和含量进行了定性和定量测定。通过在特定条件下某一煤种中多环芳烃种类、含量在燃前、燃后变化的相关性，探索煤中多环芳烃在燃烧过程中的衍变规律     

CO2气肥固体发生剂在温棚室蔬菜栽培中的应用

温棚室内Ｃ炒足是影响温棚蔬菜生产的重要因素之一。温棚人工增施ＣＯ２的方法很多，但都有一定的局限性，作者根据现在温棚室的实际情况研制出一种新型高效的ＣＯ２发生剂－－固体气肥发生剂，对比试验表明，该发生剂能使蔬菜增产２５％以上，投入产比在１：６以上，并且具有无公害的特点。     

Seasonal and latitudinal distribution of trace gases in the stratosphere: Results from a 2D residual circulation model

Results for minor stratospheric constituents using a 2D model with self-consistent transport parameters are reported. The meridional circulation is obtained from the output of the MIT-GIT 3D stratospheric model (Cunnold et al., 1975). Consistent data from the same model are used to evaluate the diffusive tensors following the formalism of Holton (1981) and Tung (1982). Chemical damping is consequently taken into account, so that the entire model is built in a selfconsistent manner at the least with the 3D model and no ad hoc assumptions are made with respect of transport parameters. This version of the model represents a major improvement on previous work (Pitari and Visconti, 1984), which used to much too simple chemistry. Results are compared whenever possible with available experimental data, with particular emphasis on chemical reacting species. This comparison shows in general an agreement which is qualitatively similar to the one obtained from classical Eulerian models where transport parameters are often tuned to long-lived tracers without any sound physical basis.     

Wet removal of highly soluble gases

Partition, not kinetics, ultimately determines the concentration of highly soluble gases in cloud droplets. Partition equations are formulated and applied to idealized air-mass thunderclouds and precipitating stratus. Contribution to aqueous concentrations from sub-cloud scavenging of highly soluble gases is estimated at between 10 and 20% under relatively unpolluted conditions. Data indicate that evaporation can produce enhancements in concentration of as much as a factor of 3. The calculations give large-scale mean coefficients of wet removal of highly soluble gases of about 2.8×10^-6 s^-1 (4-day residence time) for air-mass thunderclouds and precipitating stratus. Removal is so effective that the mean scale heights of these gases should be decreased to 2 km or less. The criterion of high solubility in this paper is that K ^H (Henry's Law coefficient) > 10⁵ mol l^-1 atm^-1. Gases that are effectively highly soluble include HCl, HNO₃, H₂SO₄, H₂O₂, NH₃ in acid droplets, SO₂ in oxidizing droplets (and probably some light amines and sulfonic acids), but not SO₂ in the absence of oxidants, nor HCHO. A variation of removal coefficient and scale height with solubility is presented. A comparison of atmospheric NH₃ concentrations deduced from rain NH₄ ⁺ and measured directly gives reasonable agreement.