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A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn2+ and Fe2+ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn2+ and Fe2+. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn2+ and Fe2+ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.  相似文献   
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Thermodynamic stability constants have been estimated for the complexation of iron(III) with catecholate-type siderophores isolated from the marine bacterium Alteromonas luteoviolacea and from the marine cyanobacterium Synechococcus sp. PCC 7002. Stability constants were determined utilizing the “chelate scale” of Taylor et al. (1994). The scale is based upon a linear relationship between the reduction potentials and the pH-independent thermodynamic stability constants for known iron(III) complexes. Log K values for the alterobactin B ferric iron complex are 43.6 ± 1.5 at pH 8.2 and 37.6 ± 1.2 at pH 6, consistent with a shift from bis-catecholate to monosalicylate/monocatecholate iron coordination with decreasing pH. Synechococcus isolates PCC 7002 Nos. 1 and 3 formed iron(III) complexes with stability constants of approximately 38.1 ± 1.2 and 42.3 ± 1.5, respectively. The binding strengths of the iron(III) complexes examined in this study are quite high, suggesting that catecholate siderophores may play a role in the solubilization and biological uptake of iron in the marine environment.  相似文献   
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An in situ method of estimating the effective diffusion coefficient for a chemical constituent that diffuses into the primary porosity of a rock is developed by abruptly changing the concentration of the dissolved constituent in a borehole in contact with the rock matrix and monitoring the time-varying concentration. The experiment was conducted in a borehole completed in mudstone on the campus of the University of the Free State in Bloemfontein, South Africa. Numerous tracer tests were conducted at this site, which left a residual concentration of sodium chloride in boreholes that diffused into the rock matrix over a period of years. Fresh water was introduced into a borehole in contact with the mudstone, and the time-varying increase of chloride was observed by monitoring the electrical conductivity (EC) at various depths in the borehole. Estimates of the effective diffusion coefficient were obtained by interpreting measurements of EC over 34 d. The effective diffusion coefficient at a depth of 36 m was approximately 7.8×10?6 m2/d, but was sensitive to the assumed matrix porosity. The formation factor and mass flux for the mudstone were also estimated from the experiment.  相似文献   
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A dense bloom of the ichthyotoxic dinoflagellate Karlodinium veneficum was discovered in the Neuse River Estuary, North Carolina, on 19 October 2006 and was associated with four subsequent fish kills. Microscopic, photopigment, DNA, and toxicological techniques confirmed bloom identity and toxicity. High-resolution spatio-temporal data from ship-board and fixed automated sampling stations provided a unique opportunity to investigate the environmental conditions that initiated, maintained, and terminated the K. veneficum bloom. Bloom initiation and growth were favored by high nutrient availability and reduced dispersal during the period of declining riverine discharge after Tropical Storm Ernesto. K. veneficum out-competed other co-occurring dinoflagellates, perhaps because of the production of karlotoxins that are known to act as grazing deterrents and to facilitate mixotrophic feeding. Once the bloom was established, small-scale hydrodynamic processes, coupled with vertical migration, concentrated cells along a frontal convergence to high densities (>200,000 cells per milliliter). By 26 October 2006, wind mixing and possible nutrient stress disrupted the bloom. Release of cell-bound toxins during the bloom collapse likely accounted for the associated fish kill events where fish were reported as exhibiting typical symptoms of karlotoxin poisoning. The dynamics of this bloom underscore the tight control of harmful algal blooms by meteorological forcing, hydrology, and sediment nutrient input in this shallow lagoonal estuary.  相似文献   
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Two different goals in fitting straight lines to data are to estimate a true linear relation (physical law) and to predict values of the dependent variable with the smallest possible error. Regarding the first goal, a Monte Carlo study indicated that the structural-analysis (SA) method of fitting straight lines to data is superior to the ordinary least-squares (OLS) method for estimating true straight-line relations. Number of data points, slope and intercept of the true relation, and variances of the errors associated with the independent (X) and dependent (Y) variables influence the degree of agreement. For example, differences between the two line-fitting methods decrease as error in X becomes small relative to error in Y. Regarding the second goal—predicting the dependent variable—OLS is better than SA. Again, the difference diminishes as X takes on less error relative to Y. With respect to estimation of slope and intercept and prediction of Y, agreement between Monte Carlo results and large-sample theory was very good for sample sizes of 100, and fair to good for sample sizes of 20. The procedures and error measures are illustrated with two geologic examples.  相似文献   
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The peraluminous tonalite–monzogranite Port Mouton Pluton is a petrological, geochemical, structural, and geochronological anomaly among the many Late Devonian granitoid intrusions of the Meguma Lithotectonic Zone of southern Nova Scotia. The most remarkable structural feature of this pluton is a 4-km-wide zone of strongly foliated (040/subvertical) monzogranites culminating in a narrow (10–30 m), straight, zone of compositionally banded rocks that extends for at least 3 km along strike. The banded monzogranites consist of alternating melanocratic and leucocratic compositions that are complementary to the overall composition of that part of the pluton, suggesting an origin by mineral–melt and mineral–mineral sorting. Biotite and feldspar are strongly foliated in the plane of the compositional bands. These compositional variations and foliations originated by a process of segregation flow during shearing of the main magma with a crystallinity of 55–75%. Subsequent minor brittle fracturing of feldspars, twinning of microcline, development of blocky sub-grains in quartz, and kinking of micas demonstrate overprinting by a high-temperature deformation straddling the monzogranite solidus. Small folds and late sigmoidal dykes indicate dextral movement on the shear zone. This Port Mouton Shear Zone (PMSZ) is approximately co-linear with the only outcrops of Late Devonian mafic intrusions in the area, two of which are syn-plutonic with well-developed mingling textures in the marginal tonalite of the Port Mouton Pluton. Also closely co-linear with the mafic intrusions are a granitoid dyke that extends well beyond the outer contact of the Port Mouton Pluton, a swarm of large aligned angular xenolithic slabs, a zone of thin wispy schlieren banding, a large Be-bearing pegmatite, and a breccia pipe with abundant garnetiferous metapelitic xenoliths. In various ways, the shear zone may control all of these features. The Port Mouton Shear Zone is parallel to many other NE-trending faults and shear zones in the northern Appalachians, probably related to the docking of the Meguma Zone along the Cobequid–Chedabucto Fault system.  相似文献   
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Drying estuarine sandbanks experience only that part of the tidal cycle around high water. In a partially progressive tidal wave, this means that the duration of the flood over the sandbank will be greater than that of the ebb: a process of tidal rectification. In this paper, we propose the hypothesis that this leads to flood-directed tidal residual currents over drying sandbanks. The hypothesis is tested by observation and a 2-D hydrodynamical model in the Conwy estuary, a vertically well-mixed macrotidal estuary in North Wales. The observations include tide gauge data, tidal cycle boat surveys, and fixed current meter data. The data show weak flood-directed residual currents over a drying sandbank and much stronger ebb-directed residuals in the channels along the sides of the sandbank. The model reproduces the observations in the vicinity of the sandbank and shows that the tidal rectification mechanism produces a general pattern of residual circulation in the estuary, with flood-directed flow in the drying areas and ebb-directed flow in the channels. The flood residuals are most marked near the estuary mouth where the tidal wave is most progressive in nature. The main application of this mechanism is believed to be in the transport of bedload sediment. The flood-directed residuals will tend to move the tops of the sandbanks upstream.  相似文献   
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