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81.
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A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment. Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as [Fe(H2O)6]2+ or free H2S as H2S/HS- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H2S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe2SH3+ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom waters are similar to the pKsp of mackinawite. Soluble iron-sulfide species are stable in the absence of O2 (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes can react with O2 to oxidize sulfide and can also dissociate releasing volatile H2S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/grdry wt) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich sulfide complexes.  相似文献   
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Given the difficulty of separating the three Picea species—P. glauca, P. mariana, and P. rubens (white, black, and red spruce)—in the pollen record, little is known about their unique histories in eastern North America following deglaciation. Here we report the first use of a classification tree analysis (CART) to distinguish pollen grains of these species. It was successfully applied to fossil pollen from eight sites in Maine and one in Massachusetts. We focused on the late glacial/early Holocene (14,000 to 8000 cal yr B.P.) and the late Holocene (1400 cal yr B.P. to present)—the two key periods since deglaciation when Picea has been abundant in the region. The result shows a shift from a Picea forest of P. glauca and P. mariana in the late glacial to a forest of P. rubens and P. mariana in the late Holocene. The small number of P. rubens grains identified from the late glacial/early Holocene samples (<5%) suggests that that species was either absent or rare at most of the sites. The occurrence and distribution of the three species do not reveal any geographic or temporal trend during late glacial time, but the data suggest that they were distributed in local patches on the landscape. The results of this study indicate that the recent population expansion of Picea (1000 to 500 cal yr B.P.) was likely the first time since deglaciation that P. rubens was abundant in the region.  相似文献   
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The oxidation kinetics of trithionate (S3O62- ) and tetrathionate (S4O 6 2- ) with hydroxyl radicals (OH*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S4O 6 2- with OH* goes through an unknown intermediate, tentatively assigned as S3O 4 n- . An outer-sphere electron transfer mechanism for the reaction of S4O 6 2- with OH* to form S3O 4 n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH* is in excess of 108 M-1 sec-1.  相似文献   
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Dynamic stochastic estimation of physical variables   总被引:1,自引:0,他引:1  
A fundamental problem facing the physical sciences today is analysis of natural variations and mapping of spatiotemporal processes. Detailed maps describing the space/time distribution of groundwater contaminants, atmospheric pollutant deposition processes, rainfall intensity variables, external intermittency functions, etc. are tools whose importance in practical applications cannot be overestimated. Such maps are valuable inputs for numerous applications including, for example, solute transport, storm modeling, turbulent-nonturbulent flow characterization, weather prediction, and human exposure to hazardous substances. The approach considered here uses the spatiotemporal random field theory to study natural space/time variations and derive dynamic stochastic estimates of physical variables. The random field model is constructed in a space/time continuum that explicitly involves both spatial and temporal aspects and provides a rigorous representation of spatiotemporal variabilities and uncertainties. This has considerable advantages as regards analytical investigations of natural processes. The model is used to study natural space/time variations of springwater calcium ion data from the Dyle River catchment area, Belgium. This dataset is characterized by a spatially nonhomogeneous and temporally nonstationary variability that is quantified by random field parameters, such as orders of space/time continuity and random field increments. A rich class of covariance models is determined from the properties of the random field increments. The analysis leads to maps of continuity orders and covariances reflecting space/time calcium ion correlations and trends. Calcium ion estimates and the associated statistical errors are calculated at unmeasured locations/instants over the Dyle region using a space/time kriging algorithm. In practice, the interpretation of the results of the dynamic stochastic analysis should take into consideration the scale effects.  相似文献   
90.
A review and analysis of chemical and nuclear explosive-induced porewater pressure increases and induced rise in groundwater table elevations (groundwater mounding) is presented. Our analysis indicates that residual pore pressure increases and groundwater mounding can be induced by underground chemical and nuclear explosions to scaled distances of 879 m/(kt)1/3. This relationship is linear over seven orders of magnitude of explosive energy ranging from a 0.01 kg chemical explosion to a 100 kt nuclear explosion and is valid for a wide variety of saturated geological profiles. Underground chemical explosions, and probably underground nuclear explosions have the potential to induce liquefaction of water-saturated soils to scaled distances of about 260 m/(kt)1/3.  相似文献   
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