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2.
To determine if Cu mediated reactions on atmospheric particles are important to HO2 chemistry in the ambient atmosphere, Cu molalities were calculated from measured Cu aerosol particle concentrations, mass and number size distribution data from a site in central Sweden. A comparison of characteristic times indicates that at low relative humidities the reaction is limited by the mass transport of gas phase HO2 to the particle surface and not by the chemical kinetics of the aqueous reaction. Comparison of half-lives for particle reactions and the gas phase destruction of HO2 to form H2O2 indicate that heterogeneous reactions on aerosol particles may have important consequences on the chemistry of HO2 and H2O2 in the troposphere.  相似文献   
3.
Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si4+ by Al3+ and Fe3+. The induced charge imbalance is compensated chiefly by Ca2+, Mg2+, Mn2+, Ba2+, K+, and Na+. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.  相似文献   
4.
In 2001 a partial skeleton of an Iguanodon was discovered in the Upper Weald Clay (Barremian, Early Cretaceous) at Smokejacks Brickworks near Ockley, Surrey, UK. When the dinosaur was excavated, a detailed stratigraphic section was logged and 25 samples taken for palynological and micropalaeontological (ostracod and megaspore) analysis, including a detailed sample set of the dinosaur bed itself. Qualitative and quantitative analysis of the palynoflora revealed rich and well-preserved non-marine assemblages of pollen and spores, including early angiosperms, and freshwater green algae. Four types of angiosperm pollen are described and assigned to the genus Retimonocolpites Pierce, 1961, but left in open nomenclature. Some marine elements such as dinoflagellate cysts are identified as the result of reworking of Middle and Upper Jurassic sediments. The pollen/spore assemblages depict a vegetational change from principally gymnosperm-dominated assemblages at the base to principally pteridophyte-dominated assemblages at the top of the section. The dinosaur bed shows a pteridophyte-dominated assemblage, with a significantly high amount of the freshwater green alga Scenedesmus novilunaris He Cheng-quan et al., 1992. Samples close to the dinosaur bed yielded the first useful ostracod finds from Smokejacks Brickworks: well-preserved assemblages containing Cypridea clavata (Anderson, 1939), Damonella cf. pygmaea (Anderson, 1941), Stenestroemia cf. cressida Anderson, 1971 and Stenestroemia sp. A, and fragments and damaged valves of a thin-shelled ostracod, possibly belonging to Mantelliana Anderson, 1966. Those identified as Cypridea clavata show a wide range of morphological variety and in opposition to Anderson's (1967, 1985) taxonomic scheme, which would assign them to up to five different taxa, they are considered to be intraspecific variants of a single species. The possibilities and limitations of age determination of the Wealden sediments using palynomorphs and ostracods are discussed; distinct forms of early angiosperm pollen, together with the ostracod fauna, are consistent with an early Barremian age. Pollen and spores are discussed in terms of their parent plants and the reconstruction of vegetation and palaeoclimate. Palynology and ostracods give evidence for temporary freshwater conditions at the time when the Iguanodon died and the carcase was buried.  相似文献   
5.
Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca5(PO4)3.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO4·H2O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce3+ ions oxidizing to CeO2. Reaction product analysis shows the formation of CO2, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M4,5 and C-K absorption edges on reacted CePO4·H2O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO4·H2O and O2 but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O2 (aq) causes both the oxidation of structural Ce3+ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO2, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O2, CeO2 can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO2 particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.  相似文献   
6.
Dissolved tetrafluoromethane (CF4) and sulfur hexafluoride (SF6) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF4 and SF6 are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF4 from the lithosphere. A gradual basin-wide enhancement in dissolved CF4 and SF6 concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF4 and SF6 concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF4, but not of SF6, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF4 and SF6 into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF4 and SF6.  相似文献   
7.
Most previous studies and applications of electrochemical stabilization of soils through electroosmosis have been made on clayey soils. The object of this investigation was to find out if relatively small amounts of clay (1.5%–3.5%, by weight) present in a sandy soil would be enough for stabilization and strengthening to be possible. The results indicate increases of cohesion of the order of 100–200 lb./sq.ft. X-ray analyses of treated soils indicate that sheet structures of clays are reduced and silicates destroyed upon treatment by electroosmosis. Newly-formed minerals also cement the soil. These neoformations include gibbsite, limonite, calcite, hydrohematite, hydrogoethite (hydrolepidocrocite), hisingerite, allophane, allophanoid, gypsum, hematite, magnetite, nontronite, trona and natron (Na2 CO3, 10H2O). The process seems to be irreversible.  相似文献   
8.
We report a ten-year study of the abundance and activity of megabenthos on the Porcupine Abyssal Plain, northeast Atlantic, together with observations on the occurrence of phytodetritus at the deep-sea floor (4850 m). Using the Southampton Oceanography Centre time-lapse camera system, ‘Bathysnap’, we have recorded a radical change in the abundance and activity of megabenthos between the two periods of study (1991–1994 and 1997–2000). In 1991–1994, the larger megabenthos occurred at an abundance of c. 71.6/ha and were dominated by large holothurians. In addition, there were very substantial populations of smaller megabenthic ophiuroids (c. 4979/ha). Together, the total megabenthos are estimated to track over some 17 cm2/m2/d (exploiting 100% of the surface of the seabed in c. 2.5 years). In 1997–2000, the larger megabenthos increased to an abundance of c. 204/ha and were joined by exceptional numbers of a small holothurian species (Amperima rosea, 6457/ha) and ophiuroids (principally Ophiocten hastatum, 53,539/ha). The total megabenthos population was tracking at an estimnated rate of c. 247 cm2/m2/d (exploiting 100% of seabed in just 6 weeks). Coincident with these increases in the abundance and activity of the megabenthos, there were apparently no mass depositions of aggregated phytodetritus to the seabed in the summers of 1997–1999. Mass occurrences of phytodetritus had been noted during the summer months of the three years previously studied (1991, 1993 and 1994), with covering between 50 and 96% of the sediment surface. There is a statistically significant (p<0.02) negative correlation between maximum extent of this seabed cover of phytodetritus and seabed tracking by megabenthos. Additional studies [Lampitt et al., Progr. Ocean. 50 (2001)], indicate that there were no substantial changes in surface ocean primary productivity, in export flux, or in the composition of the flux that might otherwise account for the apparent absence of observable concentrations of phytodetritus during the summers of 1997–1999. We postulate that the marked increase in megabenthic tracking activity resulted in the removal (via consumption, disaggregation, burial etc.) of the bulk of the incoming phytodetrital flux during these years. A simple conceptual model, based on the apparent phytodetrital fluxes observed in 1991 and 1993, suggests that the megabenthos tracking rates estimated for 1997–1999 are sufficient to account for near-total removal of this flux. However, we are not able to estimate other processes removing phytodetritus (i.e. other elements of the benthos) that may also have increased between 1991–1994 and 1997–1999. Other independent studies [e.g. Ginger et al., Progr. Ocean. 50 (2001)] of flux constituents support the possibility that just a few species of megabenthos (e.g. A. rosea, and O. hastatum) could well have consumed a major proportion of the incoming flux and so substantially modified the composition of the organic matter available to other components of the benthos.  相似文献   
9.
A theoretical and an experimental investigation was carried out, where a carbon fibre corrugated circular cylinder was tested to destuction under external hydrostatic pressure. The theoretical investigation was via the finite element method, where the structure was modelled with several orthotropic axisymmetric thin-walled shell elements. The experimental observations were aided with strategically placed strain gauges. Comparison between theory and experiment showed that the experimentally observed buckling pressure was a little lower than the theoretical prediction. This may have been due to the fact that the model had slight initial geometrical imperfections in the circumferenential direction.  相似文献   
10.
The northern Pacific seastar, Asterias amurensis, was first collected in southeast Tasmania in 1986. Mistaken for the endemic asteroid Uniophora granifera, its true identity was not realised until 1992. It is now a conspicuous predator in soft sediment habitats in this region, and is considered a major threat to native assemblages and commercial species. We examined the structure of soft sediment assemblages at different spatial scales in southeast Tasmania, and correlated spatial variation in community composition with seastar abundances. We found that the structure of soft sediment assemblages is highly variable at a range of spatial scales from metres to tens of kilometres. Clear differences in the composition of assemblages and abundances of major taxa were detected between areas with and without seastars and between areas with low and high seastar densities. However, the nature of these patterns suggests that they are more likely due to differences in sediment characteristics than due to impacts of the seastar. Thus, spatial differences in soft sediment assemblages might have been erroneously attributed to seastars without detailed information on important physical factors such as sediment characteristics. A second survey, using larger sampling units (1 m2) but across a more limited spatial extent, targeted bivalves and heart urchins that were identified as important prey of the seastar in observations of feeding and in experimental studies. Large-scale patterns of abundance and size structure were consistent with seastar effects anticipated from small-scale experimental and feeding studies for some, but not all, species. While the field survey ultimately provided evidence about the presence or absence of seastar impacts at large-scales, the identification of key ecological variables in experimental and feeding studies proved crucial to both the design and interpretation of patterns observed in the large-scale surveys. Overall, this work highlighted the necessity to consider multiple lines of evidence rather than relying on a single ‘inferential’ test, in the absence of pre-impact data.  相似文献   
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