958 resultados para standard molar enthalpy of formation


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We tested the hypothesis that occupational clothing would impair performance during swimming. The sub questions included: (1) Will the standard work wear of a railway worker or laborer impede swimming ability? (2) Will this clothing impact the individual’s ability to tread water? We addressed the research questions with three hypotheses. Analysis showed statistically significant p-values and all three null hypotheses were rejected in favor of the three research hypotheses, showing strong evidence that standard labor wear had adverse effects on 11.43 meter/12.5 yard swim time, water treading time and rate of perceived exertion (RPE) during water treading. The mean swim time more than doubled when the subjects wore standard labor-wear and their average rate of perceived exertion increased from 11.6 in standard swim wear to 17.1 in standard laborwear. It may be beneficial for those workers who work near water to be exposed to educational programs that allow in-water experiences so they develop an understanding of their abilities in, and respect for, the water.

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OBJECTIVE To compare the in vitro effects of hypertonic solutions and colloids to saline on coagulation in dogs. DESIGN In vitro experimental study. SETTING Veterinary teaching hospital. ANIMALS Twenty-one adult dogs. INTERVENTIONS Blood samples were diluted with saline, 7.2% hypertonic saline solution with 6% hydroxyethylstarch with an average molecular weight of 200 kDa and a molar substitution of 0.4 (HH), 7.2% hypertonic saline (HTS), hydroxyethyl starch (HES) 130/0.4 or hydroxyethyl starch 600/0.75 at ratios of 1:22 and 1:9, and with saline and HES at a ratio of 1:3. MEASUREMENTS AND MAIN RESULTS Whole blood coagulation was analyzed using rotational thromboelastometry (extrinsic thromboelastometry-cloting time (ExTEM-CT), maximal clot firmness (MCF) and clot formation time (CFT) and fibrinogen function TEM-CT (FibTEM-CT) and MCF) and platelet function was analyzed using a platelet function analyzer (closure time, CTPFA ). All parameters measured were impaired by saline dilution. The CTPFA was prolonged by 7.2% hypertonic saline solution with 6% hydroxyethylstarch with an average molecular weight of 200 kDa and a molar substitution of 0.4 (HH) and HTS but not by HES solutions. At clinical dilutions equivalent to those generally administered for shock (saline 1:3, HES 1:9, and hypertonic solutions 1:22), CTPFA was more prolonged by HH and HTS than other solutions but more by saline than HES. No difference was found between the HES solutions or the hypertonic solutions. ExTEM-CFT and MCF were impaired by HH and HTS but only mildly by HES solutions. At clinically relevant dilutions, no difference was found in ExTEM-CFT between HTS and saline or in ExTEM-MCF between HH and saline. No consistent difference was found between the 2 HES solutions but HH impaired ExTEM-CFT and MCF more than HTS. At high dilutions, FibTEM-CT and -MCF and ExTEM-CT were impaired by HES. CONCLUSIONS Hypertonic solutions affect platelet function and whole blood coagulation to a greater extent than saline and HES. At clinically relevant dilutions, only CTPFA was markedly more affected by hypertonic solutions than by saline. At high dilutions, HES significantly affects coagulation but to no greater extent than saline at clinically relevant dilutions.

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A bitopic ligand, 4-(3,5-dimethylpyrazol-4-yl)-1,2,4-triazole (Hpz-tr) (1), containing two different heterocyclic moieties was employed for the design of copper(II)–molybdate solids under hydrothermal conditions. In the multicomponent CuII/Hpz-tr/MoVI system, a diverse set of coordination hybrids, [Cu(Hpz-tr)2SO4]·3H2O (2), [Cu(Hpz-tr)Mo3O10] (3), [Cu4(OH)4(Hpz-tr)4Mo8O26]·6H2O (4), [Cu(Hpz-tr)2Mo4O13] (5), and [Mo2O6(Hpz-tr)]·H2O (6), was prepared and characterized. A systematic investigation of these systems in the form of a ternary crystallization diagram approach was utilized to show the influence of the molar ratios of starting reagents, the metal (CuII and MoVI) sources, the temperature, etc., on the reaction products outcome. Complexes 2–4 dominate throughout a wide crystallization range of the composition triangle, while the other two compounds 5 and 6 crystallize as minor phases in a narrow concentration range. In the crystal structures of 2–6, the organic ligand behaves as a short [N–N]-triazole linker between metal centers Cu···Cu in 2–4, Cu···Mo in 5, and Mo···Mo in 6, while the pyrazolyl function remains uncoordinated. This is the reason for the exceptional formation of low-dimensional coordination motifs: 1D for 2, 4, and 6 and 2D for 3 and 5. In all cases, the pyrazolyl group is involved in H bonding (H-donor/H-acceptor) and is responsible for π–π stacking, thus connecting the chain and layer structures in more complicated H-bonding architectures. These compounds possess moderate thermal stability up to 250–300 °C. The magnetic measurements were performed for 2–4, revealing in all three cases antiferromagnetic exchange interactions between neighboring CuII centers and long-range order with a net moment below Tc of 13 K for compound 4.

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Two active chemoherm build-ups growing freely up into the oceanic water column, the Pinnacle and the South East-Knoll Chemoherms, have been discovered at Hydrate Ridge on the Cascadia continental margin. These microbially-mediated carbonate formations rise above the seafloor by several tens of meters and display a pinnacle-shaped morphology with steep flanks. The recovered rocks are pure carbonates dominated by aragonite. Based on fabric and mineralogic composition different varieties of authigenic aragonite can be distinguished. Detailed visual and petrographic investigations unambiguously reveal the involvement of microbes during the formation of the carbonates. The fabric of the cryptocrystalline and fibrous aragonite can be described as thrombolitic. Fossilized microbial filaments in the microcrystalline aragonite indicate the intimate relationship between microbes and carbonates. The strongly 13C-depleted carbon isotope values of the samples (as low as -48.1 per mill PDB) are characteristic of methane as the major carbon source for the carbonate formation. The methane-rich fluids from which the carbonates are precipitated originate most probably from a gas reservoir below the bottom-simulating reflector (BSR) and rise through fault systems. The d18O values of the aragonitic chemoherm carbonates are substantially higher (as high as 5.0 per mill PDB) than the expected equilibrium value for an aragonite forming from ambient seawater (3.5 per mill PDB). As a first approximation this indicates formation from glacial ocean water but other factors are considered as well. A conceptual model is presented for the precipitation of these chemoherm carbonates based on in situ observations and the detailed petrographic investigation of the carbonates. This model explains the function of the consortium of archaea and sulfate-reducing bacteria that grows on the carbonates performing anaerobic oxidation of methane (AOM) and enabling the precipitation of the chemoherms above the seafloor surrounded by oxic seawater. Beggiatoa mats growing on the surface of the chemoherms oxidize the sulfide provided by sulfate-dependent anaerobic oxidation of methane within an oxic environment. The contact between Beggiatoa and the underlying microbial consortium represents the interface between the overlying oxic water column and an anoxic micro-environment where carbonate formation takes place.

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To reconstruct Recent and past sedimentary environments, marine sediments of Upper Pleistocene and Holocene ages from the eastern Arctic Ocean and especially from the Nansen-Gakkel Ridge (NGR) were investigated by means of radioisotopic, geochemical and sedimentological methods. In combination with mass physical property data and lithological analysis these investigations allow clearly to characterize the depositional environments. Age dating by using the radioisotope 230Th gives evidence that the investigated sediments from the NGR are younger than 250,000 years. Identical lithological sediment sequences within and between sediment cores from the NGR can be related to sedimentary processes which are clearly controlled by palaeoclimate. The sediments consist predominantly of siliciclastic, terrigenous ice-rafted detritus (IRD) deriving from assorted and redeposited sediments from the Siberian shelfs. By their geochemical composition the sediments are similar to mudstone, graywacke and arcose. Sea-ice as well as icebergs play a major roll in marine arctic sedimentation. In the NGR area rapid change in sedimentary conditions can be detected 128,000 years ago. This was due to drastic change in the kind of ice cover, resulting from rapid climatic change within only hundreds of years. So icebergs, deriving mostly from Siberian shelfs, vanished and sea-ice became dominant in the eastern Arctic Ocean. At least three short-period retreats of the shelf ice between 186,000 and 128,000 years are responsible for the change of coarse to fine-grained sediments in the NGR area. These warmer stages lasted between 1,000 and 3,000 years. By monitoring and comparing the distribution patterns of sedimentologic, mass physical and geochemical properties with 230Th ex activity distribution patterns in the sediment cores from the NGR, there is clear evidence that sediment dilution is responsible for high 230Th ex activity variations. Thus sedimentation rate is the controlling factor of 230Th ex activity variations. The 230Th flux density in sediments from the NGR seems to be highly dependent On topographic Position. The distribution patterns of chemical elements in sediment cores are in general governed by lithology. The derivation of a method for dry bulk density determination gave the opportunity to establish a high resolution stratigraphy on sediment cores from the eastern Arctic Ocean, based on 230Thex activity analyses. For the first time sedimentation and accumulation rates were determined for recent sediments in the eastern Arctic Ocean by 230Th ex analyses. Bulk accumulation rates are highly variable in space and time, ranging between 0.2 and 30 g/cm**2/ka. In the sediments from the NGR highly variable accumulation rates are related to the kind of ice cover. There is evidence for hydrothermal input into the sediments of the NGR. Hydrothermal activity probably also influences surficial sediments in the Sofia Basin. High contents of As are typical for surficial sediments from the NGR. In particular SL 370-20 from the bottom of the rift valley has As contents exceeding in parts 300 ppm. Hydrothermal activity can be traced back to at least 130,000 years. Recent to subrecent tectonic activity is documented by the rock debris in KAL 370 from the NGR. In four other sediment cores from the NGR rift valley area tectonically induced movements can be dated to about 130,000 years ago, related most probably to the rapid climate change. Processes of early diagenesis in sediments from the NGR caused the aobilization and redeposition of Fe, Mn and Mo. These diagenetic processes probably took place during the last 130,000 years. In sediment cores from the NGR high amounts of kaolinite are related to coarse grained siliciclastic material, probably indicating reworking and redeposition of siberian sandstones with kaolinitic binding material. In contrast to kaolinite, illite is correlated to total clay and 232Th contents. Aragonite, associated with serpentinites in the rift valley area of the NGR, was precipitated under cold bottom-water conditions. Preliminary data result in a time of formation about 60 - 80 ka ago. Manganese precipitates with high Ni contents, which can be related to the ultrabasic rocks, are of similar age.

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Dynamics of the Pacific Plate is recorded in the systematic variation of location and the 40Ar-39Ar age of seamounts in the Western Pacific from 120 to 65 Ma ago. The seamounts are grouped into three linear zones as long as 5000 km. The seamounts become younger in the southeastern direction along the strike of these zones. Correlation between age and location of seamounts allows to divide the history of their formation into three stages. Rate of seamount growth was relatively low (2-4 cm/yr) during the first and the third stages within intervals of 120-90 and 85-65 Ma, whereas during the second stage (90-85 Ma), the seamounts were growing very fast (80-100 cm/yr). In the midst of this stage, at ~87 Ma ago, magmatic activity increased abruptly. Dynamics of seamount building is in good agreement with (1) pulses in development of the Ontong Java, Manihiki, and Caribbean-Colombian oceanic plateaus; (2) age of spreading acceleration in the mid-Cretaceous; and (3) a short period when the Izanagi Plate ceased to exist and the Kula Plate was formed. Variation in seamounts' age and location are in consistence with the hypothesis of diffuse extension of the Pacific Plate in course of its motion with formation of impaired zones of decompression melting. Direction of extension (325°-340° NW) calculated from the strike of seamount zones is consistent with the path of the Pacific Plate (330° NW) in the Late Cretaceous. Immense perioceanic volcanic belts were formed at that time along the margin of the Asian continent. The Okhotsk-Chukchi Peninsula Belt extends at a right angle to the compression vector. Three stages of this belt's evolution are synchronous with the stages of seamount formation in the Pacific Plate. Delay in origination of the East Sikhote-Alin Volcanic Belt and its different orientation were caused by counterclockwise rotation of the vector of convergence of oceanic and continental plates in the mid-Cretaceous. At the same time, i.e. 95-85 Ma ago, volcanic activity embraced the entire continental margin and tin granites were emplaced everywhere in the Eastern Asia. This short episode (90+/-5 Ma) corresponds to the mid-Cretaceous maximum of compression of the continental margin, and its age fits well a culmination in extension of the Pacific Plate.

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Two genetically different types of authigenic carbonate mounds are studied: (1) from an active hydrothermal field related to serpentinite protrusions in a zone of intersection of a transform fracture zone with the Mid-Atlantic Ridge, (2) from an active field of methane seepings in the Dnieper canyon of the Black sea. General geochemical conditions, under which authigenic carbonate formation occurs within these two fields, were found. They include: presence of reduced H2S, H2, and CH4 gases at absence of free oxygen; high alkalinity of waters participating in carbonate formation; similarity of textural and structural features of authigenic aragonite, which represents the initial carbonate mineral of the mounds; paragenesis of aragonite with sulfide minerals; close relation of carbonate mounds with communities of sulfate-reducing and methane-oxidizing microorganisms. A new mechanism of formation of hydrothermal authigenic carbonates is suggested. It implies their microbial sulfate reduction over hydrogen from fluid in the subsurface mixing zone of hydrothermal solution and adjacent seawater.

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Barremian through uppermost Aptian strata from ODP Hole 641C, located upslope of a tilted fault block on the Galicia margin (northwest Spain), are syn-rift sediments deposited in the bathyal realm and are characterized by rapid sedimentation from turbidity currents and debris flows. Calcarenite and calcirudite turbidites contain shallow-water carbonate, terrigenous, and pelagic debris, in complete or partial Bouma sequences. These deposits contain abraded micritized bioclasts of reefal debris, including rudist fragments. The youngest turbidite containing shallow-water carbonate debris at Site 641 defines the boundary between syn-rift and post-rift sediments; this is also the boundary between Aptian and Albian sediments. Some Aptian turbidites are partially silicified, with pore-filling chalcedony and megaquartz. Adjacent layers of length-fast and -slow chalcedony are succeeded by megaquartz as the final pore-filling stage within carbonate reef debris. Temperatures of formation, calculated from the oxygen isotopic composition of the authigenic quartz, are relatively low for formation of quartz but are relatively warm for shallow burial depths. This quartz cement may be interpreted as a rift-associated precipitate from seawater-derived epithermal fluids that migrated along a fault associated with the tilted block and were injected into the porous turbidite beds. These warm fluids may have cooled rapidly and precipitated silica at the boundaries of the turbidite beds as a result of contact with cooler pore waters. The color pattern in the quartz cement, observed by cathodoluminescence and fluorescence techniques, and changes in the trace lement geochemistry mimic the textural change of the different quartz layers and indicates growth synchronism of the different quartz phases. Fluorescence petrography of neomorphosed low-Mg-calcite bioclasts in the silicified turbidites shows extensive zonation and details of replacive crystal growth in the bioclasts that are not observed by cathodoluminescence. Fluorescence microscopy also reveals a competitive growth history during neomorphism of the adjacent crystals in an altered carbonate bioclast. Barremian-Aptian background pelagic sediments from Hole 641C have characteristics similar to pelagic sediments from the Blake-Bahama Formation described by Jansa et al. (1979) from the western North Atlantic. Sediments at this site differ from the Blake-Bahama Formation type locality in that the Barremian-Aptian pelagic sediments have a higher percentage of dark calcareous claystone and some turbidites are silicified at Site 641. The stable isotopic composition of the pelagic marlstones from Site 641 is similar to those of other Berriasian-Aptian pelagic sediments from the Atlantic.

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In an attempt to establish criteria for obtaining reliable K-Ar dates, conventional K-Ar studies of several Deep Sea Drilling Project sites were undertaken. K-Ar dates of these rocks may be subject to inaccuracies as the result of sea-water alteration. Inaccuracies may also result from the presence of excess radiogenic 40Ar trapped in rapidly cooled rocks at the time of their formation. The results obtained for DSDP Leg 34 basalts indicate that lowering of K-Ar dates, which is related to potassium addition by weathering, is a major cause of uncertainty in obtaining reliable K-Ar dates for deep-sea rocks. It could not be determined if the potassium addition to the basalts occurred at the time of formation, t_o, or continuously from t_o to the present. Calculations show that sediment cover is not a significant barrier to the diffusion of potassium into the basalt. 40Ar loss contributes, at least in part, to the lowering of the K-Ar date in rocks that have added potassium. The meaning of the K-Ar results obtained for DSDP Legs 35 and 2 basalts could not be unambiguously established. Because of the problems involved, caution must be used in interpreting the meaning of conventional K-Ar dates for deep-sea rocks.

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Iron speciation was determined in hemiplegic sediments from a high productivity area to investigate systematically the early diagenetic reactivity of Fe. A combination of various leaching agents (1 M HCI, dithionite buffered in citrate/acetic acid, HF/H2SO4, acetic Cr(II)) was applied to sediment and extracted more than 80% of total Fe. Subsequent Fe species determination defined specific mineral fractions that are available for Fe reduction and fractions formed as products of Fe diagenesis. To determine the Fe speciation of (sheet) silicates we explored an extraction procedure (HF/H2SO4) and verified the procedure by application to standard rocks. Variations of Fe speciation of (sheet) silicates reflect the possible formation of Fe-bearing silicates in near surface sediments. The same fraction indicates a change in the primary input at greater depth, which is supported by other parameters. The Fe(II)/ Fe(III) -ratio of total sediment determined by extractions was compared with Mössbauer-spectroscopy ] at room temperature and showed agreement within 10%. M6ssbauer-spectroscopy indicates the occurrence of siderite in the presence of free sulfide and pyrite, supporting the importance of microenvironments during mineral formation. The occurrence of other Fe(II) bearing minerals such as ankerite (Ca-, Fe-, Mg-carbonate) can be presumed but remains speculative.

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Grain-size, mineral and chemical compositions of suspended particulate matter (SPM) from waters of the Severnaya (North) Dvina River mouth area during the spring flood in May 2004 is studied. Data published on composition of riverine SPM in the White Sea basin are very poor. The spring flood period when more than half of annual runoff is supplied from the river to the sea in during short time is understood more poorly. The paper considers comparison results of the grain size compositions of SPM and bottom sediments. Data of laser and hydraulic techniques of grain size analysis are compared. Short-period variations of SPM concentration and composition representing two diurnal peaks of the tide level are studied. It is found that SPM is mainly transferred during the spring flood as mineral aggregates up to 40 µm diameter. Sandy-silty fraction of riverine SPM settles in delta branches and channels, and bulk of clay-size material is supplied to the sea. Mineral and chemical compositions of SPM from the North Dvina River are determined by supply of material from the drainage basin. This material is subjected to intense mechanic separation during transfer to the sea. Key regularities of formation of mineral composition of SPM during the flood time are revealed. Effect of SPM grain size composition on distribution of minerals and chemical elements in study in the dynamic system of the river mouth area are characterized.