Enhancement Factor for Gas Absorption in a Finite Liquid Layer. Part 1: Instantaneous Reaction in a Liquid in Plug Flow

An approximate analysis of gas absorption with instantaneous reaction in a liquid layer of finite thickness in plug flow is presented. An approximate solution to the enhancement factor for the case of unequal diffusivities between the dissolved gas and the liquid reactant has been derived and validated by numerical simulation. Depending on the diffusivity ratio of the liquid reactant to the dissolved gas (?), the enhancement factor tends to be either lower or higher than the prediction of the classical enhancement factor equation based on the penetration theory (Ei,pen) at Fourier numbers typically larger than 0.1. An empirical correlation valid for all Fourier numbers is proposed to allow a quick estimation of the enhancement factor, which describes the prediction of the approximate solution and the simulation data with a relative error below 5?% under the investigated conditions (? = 0.34, Ei,pen = 21000).

Application of sorbers to mitigate greenhouse gas emissions from land-applied pig litter

Nitrous oxide is the foremost greenhouse gas (GHG)generated by land-applied manures and chemical fertilisers (Australian Government 2013). This research project was part of the National Agricultural Manure Management Program and investigated the potential for sorbers (i.e. specific naturally-occurring minerals) to decrease GHG emissions from spent piggery litter (as well as other manures)applied to soils. The sorbers investigated in this research were vermiculite and bentonite. Both are clays with high cation exchange capacities, of approximately 100–150 cmol/kg Faure 1998). The hypothesis tested in this study was that the sorbers bind ammonium in soil solution thereby suppressing ammonia (NH3)volatilisation and in doing so, slowing the kinetics of nitrate formation and associated nitrous oxide (N2O) emissions. A series of laboratory, glasshouse and field experiments were conducted to assess the sorbers’ effectiveness. The laboratory experiments comprised 64 vessels containing manure and sorber/manure ratios ranging from 1 : 10 to 1 : 1 incorporated into a sandy Sodosol via mixing. The glasshouse trial involved 240 pots comprising manure/sorber incubations placed 5 cm below the soil surface, two soil types (sandy Sodosol and Ferrosol) and two different nitrogen (N) application rates (50 kg N/ha and 150 kg N/ha) with a model plant (kikuyu grass). The field trial consisted of 96, 2 m · 2 m plots on a Ferrosol site with digit grass used as a model plant. Manure/ sorber mixtures were applied in trenches (5 cm below surface) to these plots at increasing sorber levels at anNloading rate of 200 kg/ha. Gas produced in all experiments was plumbed into a purpose-built automated gas analysis (N2O, NH3, CH4, CO2) system. In the laboratory experiments, the sorbers showed strong capacity to decreaseNH3 emissions (up to 80% decrease). Ammonia emissions were close to the detection limit in all treatments in the glasshouse and field trial. In all experiments, considerable N2O decreases (>40%) were achieved by the sorbers. As an example, mean N2O emission decreases from the field trial phase of the project are shown in Fig. 1a. The decrease inGHGemissions brought about by the clays did not negatively impact agronomic performance. Both vermiculite and bentonite resulted in a significant increase in dry matter yields in the field trial (Fig. 1b). Continuing work will optimise the sorber technology for improved environmental and agronomic performance across a range of soils (Vertosol, Dermosol in addition to Ferrosol and Sodosols) and environmental parameters (moisture, temperature, porosity, pH).

Design and fabrication of an automated thermal desorption gas-solid reaction system: Oxidation of ammonia and methanol over YBa2Cu3O7−δ(123) oxide systems

A fully automated, versatile Temperature Programmed Desorption (TDP), Temperature Programmed Reaction (TPR) and Evolved Gas Analysis (EGA) system has been designed and fabricated. The system consists of a micro-reactor which can be evacuated to 10−6 torr and can be heated from 30 to 750°C at a rate of 5 to 30°C per minute. The gas evolved from the reactor is analysed by a quadrupole mass spectrometer (1–300 amu). Data on each of the mass scans and the temperature at a given time are acquired by a PC/AT system to generate thermograms. The functioning of the system is exemplified by the temperature programmed desorption (TPD) of oxygen from YBa2Cu3−xCoxO7 ± δ, catalytic ammonia oxidation to NO over YBa2Cu3O7−δ and anaerobic oxidation of methanol to CO2, CO and H2O over YBa2Cu3O7−δ (Y123) and PrBa2Cu3O7−δ (Pr123) systems.

Proceedings of the 1998 Science Board Symposium on The Impacts of the 1997/98 El Niño Event on the North Pacific Ocean and Its Marginal Seas

Preface [pdf, 0.01 Mb] James J. O'Brien The big picture - The ENSO of 1997-98 [pdf, 0.01 Mb] James E. Overland, Nicholas A. Bond & Jennifer Miletta Adams Atmospheric anomalies in 1997: Links to ENSO? [pdf, 0.54 Mb] Vladimir I. Ponomarev, Olga Trusenkova, Serge Trousenkov, Dmitry Kaplunenko, Elena Ustinova & Antonina Polyakova The ENSO signal in the northwest Pacific [pdf, 0.47 Mb] Robert L. Smith, A. Huyer, P.M. Kosro & J.A. Barth Observations of El Niño off Oregon: July 1997 to present (October 1998) [pdf, 1.31 Mb] Patrica A. Wheeler & Jon Hill Biological effects of the 1997-1998 El Niño event off Oregon: Nutrient and chlorophyll distributions [pdf, 1.13 Mb] William T. Peterson Hydrography and zooplankton off the central Oregon coast during the 1997-1998 El Niño event [pdf, 0.26 Mb] William Crawford, Josef Cherniawsky, Michael Foreman & Peter Chandler El Niño sea level signal along the west coast of Canada [pdf, 1.25 Mb] Howard J. Freeland & Rick Thomson The El Niño signal along the west coast of Canada - temperature, salinity and velocity [pdf, 0.49 Mb] Frank A. Whitney, David L. Mackas, David W. Welch & Marie Robert Impact of the 1990s El Niños on nutrient supply and productivity of Gulf of Alaska waters [pdf, 0.06 Mb] Craig McNeil, David Farmer & Mark Trevorrow Dissolved gas measurements at Stn. P4 during the 97-98 El Niño [pdf, 0.13 Mb] Kristen L.D. Milligan, Colin D. Levings & Robert E. DeWreede Data compilation and preliminary time series analysis of abundance of a dominant intertidal kelp species in relation to the 1997/1998 El Niño event [pdf, 0.05 Mb] S.M. McKinnell, C.C. Wood, M. Lapointe, J.C. Woodey, K.E. Kostow, J. Nelson & K.D. Hyatt Reviewing the evidence that adult sockeye salmon strayed from the Fraser River and spawned in other rivers in 1997 [pdf,0.03 Mb] G.A. McFarlane & R.J. Beamish Sardines return to British Columbia waters [pdf, 0.34 Mb] Ken H. Morgan Impact of the 1997/98 El Niño on seabirds of the northeast Pacific [pdf, 0.06 Mb] Thomas C. Royer & Thomas Weingartner Coastal hydrographic responses in the northern Gulf of Alaska to the 1997-98 ENSO event [pdf, 0.76 Mb] John F. Piatt, Gary Drew, Thomas Van Pelt, Alisa Abookire, April Nielsen, Mike Shultz & Alexander Kitaysky Biological effects of the 1997/98 ENSO in Cook Inlet, Alaska [pdf, 0.22 Mb] H.J. Niebauer The 1997-98 El Niño in the Bering Sea as compared with previous ENSO events and the "regime shift" of the late 1970s [pdf, 0.10 Mb] A.S. Krovnin, G.P. Nanyushin, M.Yu. Kruzhalov, G.V. Khen, M.A. Bogdanov, E.I. Ustinova, V.V. Maslennikov, A.M. Orlov, B.N. Kotenev, V.V. Bulanov & G.P. Muriy The state of the Far East seas during the 1997/98 El Niño event [pdf, 0.15 Mb] Stacy Smith & Susan Henrichs Phytoplankton collected by a time-series sediment trap deployed in the southeast Bering Sea during 1997 [pdf, 0.21 Mb] Cynthia T. Tynan Redistributions of cetaceans in the southeast Bering Sea relative to anomalous oceanographic conditions during the 1997 El Niño [pdf, 0.02 Mb] Akihiko Yatsu, Junta Mori, Hiroyuki Tanaka, Tomowo Watanabe, Kazuya Nagasawa, Yikimasa Ishida, Toshimi Meguro, Yoshihiko Kamei & Yasunori Sakurai Stock abundance and size compositions of the neon flying squid in the central North Pacific Ocean during 1979-1998 [pdf, 0.11 Mb] O.B. Feschenko A new point of view concerning the El Niño mechanism [pdf, 0.01 Mb] Nathan Mantua 97/98 Ocean climate variability in the northeast Pacific: How much blame does El Niño deserve? [pdf, 0.01 Mb] Vadim P. Pavlychev Sharp changes of hydrometeorological conditions in the northwestern Pacific during the 1997/1998 El Niño event [pdf, 0.01 Mb] Jingyi Wang Predictability and forecast verification of El Niño events [pdf, 0.01 Mb] (Document contains 110 pages)

中国大中型气田天然气成藏物理化学模拟研究

Natural gas pays more important role in the society as clean fuel. Natural gas exploration has been enhanced in recent years in many countries. It also has prospective future in our country through "85" and "95" national research. Many big size gas fields have been discovered in different formations in different basins such as lower and upper Paleozoic in Erdos basin, Tertiary system in Kuche depression in Tarim basin, Triassic system in east of Sichuan basin. Because gas bearing basins had been experienced multiple tectogenesis. The characteristics of natural gases usually in one gas field are that they have multiple source rocks and are multiple maturities and formed in different ages. There has most difficult to research on the gas-rock correlation and mechanism of gas formation. Develop advanced techniques and methods and apply them to solve above problems is necessary. The research is focused on the critical techniques of geochemistry and physical simulation of gas-rock correlation and gas formation. The lists in the following are conclusions through research and lots of experiments. I 8 advanced techniques have been developed or improved about gas-rock correlation and gas migration, accumulation and formation. A series of geochemistry techniques has been developed about analyzing inclusion enclave. They are analyzing gas and liquid composition and biomarker and on-line individual carbon isotope composition in inclusion enclave. These techniques combing the inclusion homogeneous temperature can be applied to study on gas-rock correlation directly and gas migration, filling and formation ages. Technique of on-line determination individual gas carbon isotope composition in kerogen and bitumen thermal pyrolysis is developed. It is applied to determine the source of natural is kerogen thermal degradation or oil pyrolysis. Method of on-line determination individual gas carbon isotope composition in rock thermal simulation has being improved. Based on the "95"former research, on-line determination individual gas carbon isotope composition in different type of maceral and rocks thermal pyrolys is has been determined. The conclusion is that carbon isotope composition of benzene and toluene in homogenous texture kerogen thermal degradation is almost same at different maturity. By comparison, that in mixture type kerogen thermal pyrolysis jumps from step to step with the changes of maturity. This conclusion is a good proof of gas-rock dynamic correlation. 3. Biomarker of rock can be determined directly through research. It solves the problems such as long period preparing sample, light composition losing and sample contamination etc. It can be applied to research the character of source rock and mechanism of source rock expulsion and the path of hydrocarbon migration etc. 4. The process of hydrocarbon dynamic generation in source rock can be seen at every stage applying locating observation and thermal simulation of ESEM. The mechanism of hydrocarbon generation and expulsion in source rock is discussed according to the experiments. This technique is advanced in the world. 5. A sample injection system whose character is higher vacuum, lower leaks and lower blank has been built up to analyze inert gas. He,Ar,Kr and Xe can be determined continuously on one instrument and one injection. This is advanced in domestic. 7. Quality and quantity analysis of benzene ring compounds and phenolic compounds and determination of organic acid and aqueous gas analysis are applied to research the relationship between compounds in formation water and gas formation. This is another new idea to study the gas-rock correlation and gas formation. 8. Inclusion analysis data can be used to calculate the Paleo-fluid density, Paleo-geothermal gradient and Paleo-geopressure gradient and then to calculate the Paleo-fluid potential. It's also a new method to research the direction of hydrocarbon migration and accumulation. 9. Equipment of natural gas formation simulation is produced during the research to probe how the physical properties of rock affect the gas migration and accumulation and what efficiency of gas migrate and factors of gas formation and the models of different type of migration are. II study is focused on that if the source rocks of lower Paleozoic generated hydrocarbon and what the source rocks of weathered formation gas pool and the mechanism of gas formation are though many advanced techniques application. There are four conclusions. 1.The maturity of Majiagou formation source rocks is higher in south than that in north. There also have parts of the higher maturity in middle and east. Anomalous thermal pays important role in big size field formation in middle of basin. 2. The amount of gas generation in high-over maturity source rocks in lower Paleozoic is lager than that of most absorption of source rocks. Lower Paleozoic source rocks are effective source rocks. Universal bitumen exists in Ordovician source rocks to prove that Ordovician source rocks had generated hydrocarbon. Bitumen has some attribution to the middle gas pool formation. 3. Comprehensive gas-rock correlation says that natural gases of north, west, south of middle gas field of basin mainly come from lower Paleozoic source rocks. The attribution ratio of lower Paleozoic source rocks is 60%-70%. Natural gases of other areas mainly come from upper Paleozoic. The attribution ratio of upper Paleozoic source rocks is 70%. 4. Paleozoic gases migration phase of Erdos basin are also interesting. The relative abundance of gasoline aromatic is quite low especially toluene that of which is divided by that of methyl-cyclohexane is less than 0.2 in upper Paleozoic gas pool. The migration phase of upper Paleozoic gas may be aqueous phase. By comparison, the relative abundance of gasoline aromatic is higher in lower Paleozoic gas. The distribution character of gasoline gas is similar with that in source rock thermal simulation. The migration phase of it may be free phase. IH Comprehensive gas-rock correlation is also processed in Kuche depression Tarim basin. The mechanism of gas formation is probed and the gas formation model has been built up. Four conclusions list below. 1. Gases in Kuche depression come from Triassic-Jurassic coal-measure source rocks. They are high-over maturity. Comparatively, the highest maturity area is Kelasu, next is Dabei area, Yinan area. 2. Kerogen thermal degradation is main reason of the dry gas in Kuche depression. Small part of dry gas comes from oil pyrolysis. VI 3.The K12 natural gas lays out some of hydro-gas character. Oil dissolved in the gas. Hydro-gas is also a factor making the gas drier and carbon isotope composition heavier. 4. The mechanism and genesis of KL2 gas pool list as below. Overpressure has being existed in Triassic-Jurassic source rocks since Keche period. Natural gases were expulsed by episode style from overpressure source rocks. Hetero-face was main migration style of gas, oil and water at that time. The fluids transferred the pressure of source rocks when they migrated and then separated when they got in reservoir. After that, natural gas migrated up and accumulated and formed with the techno-genesis. Tectonic extrusion made the natural gas overpressure continuously. When the pressure was up to the critical pressure, the C6-C7 composition in natural gas changed. The results were that relative abundance of alkane and aromatic decreased while cycloalkane and isoparaffin increased. There was lots of natural gas filling during every tectonic. The main factors of overpressure of natural gas were tectonic extrusion and fluid transferring pressure of source rocks. Well preservation was also important in the KL2 gas pool formation. The reserves of gas can satisfy the need of pipeline where is from west to east. IV A good idea of natural gas migration and accumulation modeling whose apparent character is real core and formation condition is suggested to model the physical process of gas formation. Following is the modeling results. 1. Modeling results prove that the gas accumulation rule under cap layer and gas fraction on migration path. 2. Natural gas migration as free phase is difficult in dense rock. 3. Natural gases accumulated easily in good physical properties reservoirs where are under the plugging layer. Under the condition of that permeability of rock is more than 1 * 10~(-3)μm~(-1), the more better the physical properties and the more bigger pore of rock, the more easier the gas accumulation in there. On the contrary, natural gas canonly migrate further to accumulate in good physical properties of rock. 4. Natural gas migrate up is different from that down. Under the same situation, the amount of gas migration up is lager than that of gas migration down and the distance of migration up is 3 times as that of migration down. 5. After gas leaks from dense confining layer, the ability of its dynamic plug-back decreased apparently. Gas lost from these arils easily. These confining layer can confine again only after geology condition changes. 6. Water-wetted and capillary-blocking rocks can't block water but gases generally. The result is that water can migrate continuously through blocking rocks but the gases stay under the blocking rocks then form in there. The experiments have proved the formation model of deep basin gas.

A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations

A pre-concentration system has been validated for use with a gas chromatography/mass spectrometry/isotope ratio mass spectrometer (GC/MS/IRMS) to determine ambient air 13C/12C ratios for methyl halides (MeCl and MeBr) and chlorofluorocarbons (CFCs). The isotopic composition of specific compounds can provide useful information on their atmospheric budgets and biogeochemistry that cannot be ascertained from abundance measurements alone. Although pre-concentration systems have been previously used with a GC/MS/IRMS for atmospheric trace gas analysis, this is the first study also to report system validation tests. Validation results indicate that the pre-concentration system and subsequent separation technologies do not significantly alter the stable isotopic ratios of the target methyl halides, CFC-12 (CCl2F2) and CFC-113 (C2Cl3F3). Significant, but consistent, isotopic shifts of -27.5 to -25.6 do occur within the system for CFC-11 (CCl3F), although the shift is correctible. The method presented has the capacity to separate these target halocarbons from more than 50 other compounds in ambient air samples. Separation allows for the determination of stable carbon isotope ratios of five of these six target trace atmospheric constituents within ambient air for large volume samples (10 L). Representative urban air analyses from Belfast City are also presented which give carbon isotope results similar to published values for 13C/12C analysis of MeCl (-39.1) and CFC-113 (-28.1). However, this is the first paper reporting stable carbon isotope signatures for CFC-11 (-29.4) and CFC-12 (-37.0).

Determination of Holocene cave temperatures from Kr and Xe concentrations in stalagmite fluid inclusions

From the concentrations of dissolved atmospheric noble gases in water, a so-called “noble gas temperature” (NGT) can be determined that corresponds to the temperature of the water when it was last in contact with the atmosphere. Here we demonstrate that the NGT concept is applicable to water inclusions in cave stalagmites, and yields NGTs that are in good agreement with the ambient air temperatures in the caves. We analysed samples from two Holocene and one undated stalagmite. The three stalagmites originate from three caves located in different climatic regions having modern mean annual air temperatures of 27 °C, 12 °C and 8 °C, respectively. In about half of the samples analysed Kr and Xe concentrations originated entirely from the two well-defined noble gas components air-saturated water and atmospheric air, which allowed NGTs to be determined successfully from Kr and Xe concentrations. One stalagmite seems to be particularly suitable for NGT determination, as almost all of its samples yielded the modern cave temperature. Notably, this stalagmite contains a high proportion of primary water inclusions, which seem to preserve the temperature-dependent signature well in their Kr and Xe concentrations. In future work on stalagmites detailed microscopic inspection of the fluid inclusions prior to noble gas analysis is therefore likely to be crucial in increasing the number of successful NGT determinations.

Geochemical synthesis for the Effingen Member in boreholes at Oftringen, Gösgen and Küttigen

The Effingen Member is a low-permeability rock unit of Oxfordian age (ca. 160 Ma) that occurs across northern Switzerland. It comprises sandy calcareous marls and (argillaceous) limestones. This report describes the hydrogeochemistry, mineralogy and supporting physical properties of the Effingen Member in three boreholes in the Jura-Südfuss area: Oftringen, Gösgen and Küttigen, where it is 220–240 m thick. The top of the Effingen Member is at 420, 66 and 32 m depths at the three sites. Core materials are available from Oftringen and Gösgen, whereas information from Küttigen is limited to cuttings, in-situ hydrogeological testing and geophysical logging. Hydrogeological boundaries of the Effingen Member vary between locations. Ground-water flows were identified during drilling at the top (Geissberg Member), but not at the base, of the Effingen Member at Oftringen, at the base (Hauptrogenstein Formation) of the Effingen Member at Gösgen, and in a limestone layer (Gerstenhübel unit) within the Effingen Member at Küttigen. The marls and limestones of the Effingen Member have carbonate contents of 46–91 wt.-% and clay-mineral contents of 5–37 wt.-%. Pyrite contents are up to 1.6 wt.-%, but no sulphate minerals were detected by routine analyses. Clay minerals are predominantly mixed-layer illite-smectite, illite and kaolinite, with sporadic traces of chlorite and smectite. Veins filled with calcite ± celestite occur through the Effingen Member at Oftringen but not at Gösgen or Küttigen. They formed at 50–70 ºC from externally derived fluids, probably of Miocene age. Water contents are 0.7–4.2 wt.-%, corresponding to a water-loss porosity range of 1.9–10.8 vol.-%. Specific surface areas, measured by the BET method, are 2–30 m2/g, correlating with clay-mineral contents. Water activity has been measured and yielded surprisingly low values down to 0.8. These cannot be explained by pore-water salinity alone and include other effects, such as changes in the fabric due to stress release or partial saturation. Observed variations in measurements are not fully understood. Cation exchange capacity (CEC) and exchangeable cation populations have been studied by the Ni-en method. CEC, derived from the consumption of the index cation Ni, is 9–99 meq/kgrock at a solid:liquid ratio of 1, correlating with the clay-mineral content. Cation concentrations in Ni-en extract solutions are in the order Na+≥Ca2+>Mg2+>K+>Sr2+. However, the analytical results from the Ni-en extractions have additional contributions from cations originating from pore water and from mineral dissolution reactions that occurred during extraction, and it was not possible to reliably quantify these contributions. Therefore, in-situ cation populations and selectivity coefficients could not be derived. A suite of methods have been used for characterising the chemical compositions of pore waters in the Effingen Member. Advective displacement was used on one sample from each Oftringen and Gösgen and is the only method that produces results that approach complete hydrochemical compositions. Aqueous extraction was used on core samples from these two boreholes and gives data only for Cl- and, in some cases, Br-. Out-diffusion was used on core samples from Oftringen and similarly gives data for Cl- and Br- only. For both aqueous extraction and out-diffusion, reaction of the experimental water with rock affected concentrations of cations, SO42 and alkalinity in experimental solutions. Another method, centrifugation, failed to extract pore water. Stable isotope ratios (δ18O and δ2H) of pore waters in core samples from Oftringen were analysed by the diffusive exchange method and helium contents of pore water in Oftringen samples were extracted for mass spectrometric analysis by quantitative outgassing of preserved core samples. Several lines of evidence indicate that drillcore samples might not have been fully saturated when opened and subsampled in the laboratory. These include comparisons of water-loss porosities with physical porosities, water-activity measurements, and high contents of dissolved gas as inferred from ground-water samples. There is no clear proof of partial saturation and it is unclear whether this might represent in-situ conditions or is due to exsolution of gas due to the pressure release since drilling. Partial saturation would have no impact on the recalculation of pore-water compositions from aqueous extraction experiments using water-loss porosity data. The largest uncertainty in the pore-water Cl- concentrations recalculated from aqueous extraction and out-diffusion experiments is the magnitude of the anion-accessible fraction of water-loss porosity. General experience of clay-mineral rich formations suggests that the anion-accessible porosity fraction is very often about 0.5 and generally in a range of 0.3 to 0.6 and tends to be inversely correlated with clay-mineral contents. Comparisons of the Cl- concentration in pore water obtained by advective displacement with that recalculated from aqueous extraction of an adjacent core sample suggests a fraction of 0.27 for an Oftringen sample, whereas the same procedure for a Gösgen sample suggests a value of 0.64. The former value for anion-accessible porosity fraction is presumed to be unrepresentative given the local mineralogical heterogeneity at that depth. Through-diffusion experiments with HTO and 36Cl- suggest that the anion-accessible porosity fraction in the Effingen Member at Oftringen and Gösgen is around 0.5. This value is proposed as a typical average for rocks of the Effingen Member, bearing in mind that it varies on a local scale in response to the heterogeneity of lithology and pore-space architecture. The substantial uncertainties associated with the approaches to estimating anion-accessible porosity propagate into the calculated values of in-situ pore-water Cl- concentrations. On the basis of aqueous extraction experiments, and using an anion-accessible porosity fraction of 0.5, Cl- concentrations in the Effingen Member at Oftringen reach a maximum of about 14 g/L in the centre. Cl- decreases upwards and downwards from that, forming a curved depth profile. Cl- contents in the Effingen Member at Gösgen increase with depth from about 3.5 g/L to about 14 g/L at the base of the cored profile (which corresponds to the centre of the formation). Out-diffusion experiments were carried out on four samples from Oftringen, distributed through the Effingen Member. Recalculated Cl- concentrations are similar to those from aqueous extraction for 3 out of the 4 samples, and somewhat lower for one sample. Concentrations of other components, i.e. Na+, K+, Ca2+, Mg2+, Sr2+, SO42- and HCO3- cannot be obtained from the aqueous extraction and out-diffusion experimental data because of mineral dissolution and cation exchange reactions during the experiments. Pore-water pH also is not constrained by those extraction experiments. The only experimental approach to obtain complete pore-water compositions for samples from Oftringen and Gösgen is advective displacement of pore water. The sample from Oftringen used for this experiment is from 445 m depth in the upper part of the Effingen Member and gave eluate with 16.5 g/L Cl- whereas aqueous extraction from a nearby sample indicated about 9 g/L Cl-. The sample from Gösgen used for advective displacement is from 123 m depth in the centre of the Effingen Member sequence and gave eluate with about 9 g/L Cl- whereas aqueous extraction gave 11.5 g/L Cl-. In both cases the pore waters have Na-(Ca)-Cl compositions and SO42- concentrations of about 1.1 g/L. The Gösgen sample has a Br/Cl ratio similar to that of sea water, whereas this ratio is lower for the Oftringen sample. Taking account of uncertainties in the applied experimental approaches, it is reasonable to place an upper limit of ca. 20 g/L on Cl- concentration for pore water in the Effingen Member in this area. There are major discrepancies between pore-water SO42- concentrations inferred from aqueous extraction or out-diffusion experiments and those obtained from advective displacement in both the Oftringen and Gösgen cases. A general conclusion is that all or at least part of the discrepancies are attributable to perturbation of the sulphur system and enhancement of SO42- by sulphate mineral dissolution and possibly minor pyrite oxidation during aqueous extraction and out-diffusion. Therefore, data for SO42- calculated from those pore-water sampling methods are considered not to be representative of in-situ conditions. A reference pore-water composition was defined for the Effingen Member in the Jura Südfuss area. It represents the probable upper limits of Cl- contents and corresponding anion and cation concentrations that are reasonably constrained by experimental data. Except for Cl- and possibly Na+ concentrations, this composition is poorly constrained especially with respect to SO42- and Ca2+ concentrations, and pH and alkalinity. Stable isotope compositions, δ18O and δ2H, of pore waters in the Effingen Member at Oftringen plot to the right of the meteoric water line, suggesting that 18O has been enriched by water-rock exchange, which indicates that the pore waters have a long residence time. A long residence time of pore water is supported by the level of dissolved 4He that has accumulated in pore water of the Effingen Member at Oftringen. This is comparable with, or slightly higher than, the amounts of 4He in the Opalinus Clay at Benken. Ground waters were sampled from flowing zones intersected by boreholes at the three locations. The general interpretation is that pore waters and ground-water solutes may have similar origins in Mesozoic and Cenozoic brackish-marine formations waters, but ground-water solutes have been diluted rather more than pore waters by ingress of Tertiary and Quaternary meteoric waters. The available hydrochemical data for pore waters from the Effingen Member at these three locations in the Jura-Südfuss area suggest that the geochemical system evolved slowly over geological periods of time, in which diffusion was an important mechanism of solute transport. The irregularity of Cl- and δ18O profiles and spatial variability of advective ground-water flows in the Malm-Dogger system suggests that palaeohydrogeological and hydrochemical responses to changing tectonic and surface environmental conditions were complex.

Pressure core barrel characteristics and composition of gases at DSDP Site 76-533

A pressure core barrel (PCB), developed by the Deep Sea Drilling Project, was used successfully to recover, at in situ pressure, sediments of the Blake Outer Ridge, offshore the southeastern United States. The PCB is a unique, wire-line tool, 10.4 m long, capable of recovering 5.8 m of core (5.8 cm in diameter), maintained at or below in situ pressures of 34.4 million Pascals (MPa), and 1.8 m of unpressurized core (5.8 cm in diameter). All excess internal pressure above the operating pressure of 34.4 MPa is automatically vented off as the barrel is retrieved. The PCB was deployed five times at DSDP Site 533 where geophysical evidence suggests the presence of gas hydrates in the upper 600 m of sediment. Three cores were obtained holding average in situ pressures of 30 MPa. Two other cores did not maintain in situ pressures. Three of the five cores were intermittently degassed at varying intervals of time, and portions of the vented gas were collected for analysis. Pressure decline followed paths indicative of gas hydrates and/or dissolved gas. The released gas was dominantly methane (usually greater than 90%), along with higher molecular-weight hydrocarbon gases and carbon dioxide. During degassing the ratio of methane to ethane did not vary significantly. On the other hand, concentrations of higher molecular-weight hydrocarbon gases increased, as did carbon dioxide concentrations. The results from the PCB experiments provide tentative but equivocal evidence for the presence of .gas hydrates at Site 533. The amount of gas hydrate indicated is small. Nevertheless, this work represents the first successful study of marine gas hydrates utilizing the PCB.

Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.

Identificación de los riesgos ambientales y sanitarios de la producción de gas mediante fracturación hidráulica y bases para una propuesta metodológica de vulnerabilidad de las aguas subterráneas

Hasta ahora, la gran mayoría de los recursos explotados de gas natural procedían de acumulaciones convencionales de gas aislado y de gas asociado y disuelto en el petróleo. Sin embargo, el gas natural se encuentra también en yacimientos que, debido a su baja porosidad y permeabilidad, tienen unas características que hacen que hasta muy recientemente no hayan sido económicamente rentables y que sólo puedan ser explotados mediante técnicas no convencionales, dando lugar al denominado gas no convencional. Las técnicas utilizadas para su extracción son la fracturación hidráulica o “fracking” y la perforación horizontal. Entre los diversos tipos de gas no convencional, es de prever que el gas de pizarra sea el que sufra mayor desarrollo a medio plazo en nuestro país, por lo que se están generando grandes debates, debido al riesgo de contaminación de las aguas superficiales y subterráneas del entorno, provocados por la elevada cantidad de agua utilizada, los aditivos empleados, los fluidos de retorno, por la alteración del medio físico, así como por la dificultad de monitorización de estos procesos. En este proyecto se identifican los riesgos ambientales y sanitarios asociados a la extracción de gas no convencional. El trabajo se basa principalmente en experiencias ocurridas en países donde el fracking se ha convertido en una práctica habitual. Se trata además de establecer las bases necesarias para la estimación de la vulnerabilidad de los acuíferos frente a la contaminación inducida por la fracturación hidráulica. Abstract Until now, most of the natural gas resources exploited were from isolated conventional gas accumulations and associated and dissolved gas in oil. However, the natural gas is also in reservoirs that, due to their low porosity and permeability, have characteristics that make until recently not been economically profitable and can be exploited only by unconventional techniques, leading to the so called unconventional gas. The techniques used for extraction are hydraulic fracturing or "fracking" and horizontal drilling. Among the various types of unconventional gas, it is expected that shale gas is the suffering greater medium-term development in our country, so it is generating much debate, due to the risks of contamination in surface waters and subterranean environment, caused by the high amount of water used, the additives used, the return fluid, by altering the physical environment, and the difficulty of monitoring these processes. In this project identifies the environmental and health risks associated with unconventional gas extraction. The work is mainly based on experiences that occurred in countries where fracking has become a common practice. This is for establish the necessary basis for estimating the vulnerability of aquifers from contamination induced by hydraulic fracturing.

The North Pacific biological pump: Rates, efficiency and influence on ocean carbon uptake

Thesis (Ph.D.)--University of Washington, 2016-05

A novel wastewater treatment process: Simultaneous nitrification, denitrification and phosphorus removal

Simultaneous nitrification and denitrification (SND) via the nitrite pathway and anaerobic-anoxic enhanced biological phosphorus removal (EBPR) are two processes that can significantly reduce the COD demand for nitrogen and phosphorus removal. The combination of these two processes has the potential of achieving simultaneous nitrogen and phosphorus removal with a minimal requirement for COD. A lab-scale sequencing batch reactor (SBR) was operated in alternating anaerobic-aerobic mode with a low dissolved oxygen concentration (DO, 0.5 mg/L) during the aerobic period, and was demonstrated to accomplish nitrification, denitrification and phosphorus removal. Under anaerobic conditions, COD was taken up and converted to polyhydroxyalkanoates (PHA), accompanied with phosphorus release. In the subsequent aerobic stage, PHA was oxidized and phosphorus was taken up to less than 0.5 mg/L at the end of the cycle. Ammonia was also oxidised during the aerobic period, but without accumulation of nitrite or nitrate in the system, indicating the occurrence of simultaneous nitrification and denitrification. However, off-gas analysis found that the final denitrification product was mainly nitrous oxide (N2O) not N-2. Further experimental results demonstrated that nitrogen removal was via nitrite, not nitrate. These experiments also showed that denitrifying glycogen.-accumulating organisms rather than denitrifying polyphosphate-accumulating organisms were responsible for the denitrification activity.

Determination of external and internal mass transfer limitation in nitrifying microbial aggregates

In this article we present a study of the effects of external and internal mass transfer limitation of oxygen in a nitrifying system. The oxygen uptake rates (OUR) were measured on both a macro-scale with a respirometric reactor using off-gas analysis (Titrimetric and Off-Gas Analysis (TOGA) sensor) and on a micro-scale with microsensors. These two methods provide independent, accurate measurements of the reaction rates and concentration profiles around and in the granules. The TOGA sensor and micro-sensor measurements showed a significant external mass transfer effect at low dissolved oxygen (DO) concentrations in the bulk liquid while it was insignificant at higher DO concentrations. The oxygen distribution with anaerobic or anoxic conditions in the center clearly shows major mass transfer limitation in the aggregate interior. The large drop in DO concentration of 22 - 80% between the bulk liquid and aggregate surface demonstrates that the external mass transfer resistance is also highly important. The maximum OUR even for floccular biomass was only attained at much higher DO concentrations ( approximate to 8 mg/L) than typically used in such systems. For granules, the DO required for maximal activity was estimated to be > 20mg/L, clearly indicating the effects of the major external and internal mass transfer limitations on the overall biomass activity. Smaller aggregates had a larger volumetric OUR indicating that the granules may have a lower activity in the interior part of the aggregate. (C) 2004 Wiley Periodicals, Inc.