Dissociation constants of protonated cysteine species in seawater media     

Virender K. Sharma  Aurelie Moulin  Frank J. Millero  Concetta De Stefano 《Marine Chemistry》2006,99(1-4):52

The dissociation constants (pK₁, pK₂ and pK₃) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK₃ in the Na–Mg–Cl solutions have been attributed to the formation of Mg²⁺ complexes with Cys²⁻ anionsThe stability constants have been fitted toafter corrections are made for the interaction of Mg²⁺ with H⁺.The pK₁ seawater measurements indicate that H₃Cys⁺ interacts with SO₄²⁻. The Pitzer parameters β⁰(H₃CysSO₄), β¹(H₃CysSO₄) and C(H₃CysSO₄) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK₂ and pK₃ in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK₁, pK₂ and pK₃ that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.  相似文献   

The influence of light on nitrogen cycling and the primary nitrite maximum in a seasonally stratified sea     

Katherine R.M. Mackey  Laura Bristow  David R. Parks  Mark A. Altabet  Anton F. Post  Adina Paytan 《Progress in Oceanography》2011,91(4):545-560

In the seasonally stratified Gulf of Aqaba Red Sea, both release by phytoplankton and oxidation by nitrifying microbes contributed to the formation of a primary nitrite maximum (PNM) over different seasons and depths in the water column. In the winter and during the days immediately following spring stratification, formation was strongly correlated (R² = 0.99) with decreasing irradiance and chlorophyll, suggesting that incomplete reduction by light limited phytoplankton was a major source of . However, as stratification progressed, continued to be generated below the euphotic depth by microbial oxidation, likely due to differential photoinhibition of and oxidizing populations. Natural abundance stable nitrogen isotope analyses revealed a decoupling of the δ¹⁵N and δ¹⁸O in the combined and pool, suggesting that assimilation and nitrification were co-occurring in surface waters. As stratification progressed, the δ¹⁵N of particulate N below the euphotic depth increased from −5‰ to up to +20‰.N uptake rates were also influenced by light; based on ¹⁵N tracer experiments, assimilation of , , and urea was more rapid in the light (434 ± 24, 94 ± 17, and 1194 ± 48 nmol N L⁻¹ day⁻¹ respectively) than in the dark (58 ± 14, 29 ± 14, and 476 ± 31 nmol N L⁻¹ day⁻¹ respectively). Dark assimilation was 314 ± 31 nmol N L⁻¹ day⁻¹, while light assimilation was much faster, resulting in complete consumption of the ¹⁵N spike in less than 7 h from spike addition. The overall rate of coupled urea mineralization and oxidation (14.1 ± 7.6 nmol N L⁻¹ day⁻¹) was similar to that of oxidation alone (16.4 ± 8.1 nmol N L⁻¹ day⁻¹), suggesting that mineralization of labile dissolved organic N compounds like urea was not a rate limiting step for nitrification. Our results suggest that assimilation and nitrification compete for and that N transformation rates throughout the water column are influenced by light over diel and seasonal cycles, allowing phytoplankton and nitrifying microbes to contribute jointly to PNM formation. We identify important factors that influence the N cycle throughout the year, including light intensity, substrate availability, and microbial community structure. These processes could be relevant to other regions worldwide where seasonal variability in mixing depth and stratification influence the contributions of phytoplankton and non-photosynthetic microbes to the N cycle.  相似文献   

Effects of stratification and mesoscale eddies on Kuroshio path variation south of Japan     

Kazunori Akitomo   《Deep Sea Research Part I: Oceanographic Research Papers》2008,55(8):997-1008

Bimodality of the Kuroshio current path south of Japan is investigated, focusing on the effects of stratification and mesoscale eddies. For this purpose, wind-driven numerical experiments are executed in barotropic and two-layered ocean models. Stratification has two effects on the path selection of the Kuroshio south of Japan. First, it makes an alongshore path stable at intermediate wind stress strength τ₀ by arresting an eddy southeast of Kyushu. This enables an alongshore path to appear in the entire experimental range of τ₀. Second, the upper limit of τ₀ which allows a meandering path decreases from ( in the Sverdrup transport at the Tokara Strait) to () as Δρ/ρ₀ increases from 2.0×10^-3 to 4.0×10^-3. While an anticyclonic eddy imposed upstream (southeast of Kyushu) can cause the transition from an alongshore to a meandering path, it occurs most easily when (). The transition from a meandering to an alongshore path requires an eddy imposed downstream (east of the meandering segment) which suppresses redevelopment of the meandering segment and breaks the balance between the advective and beta effects. Applicability of the results to previously observed path variations is discussed.  相似文献   

Oxidation of copper(I) in seawater at nanomolar levels     

M. Gonzlez-Dvila  J.M. Santana-Casiano  A.G. Gonzlez  N. Prez  F.J. Millero 《Marine Chemistry》2009,115(1-2):118-124

The oxidation and reduction of nanomolar levels of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17–8.49), temperature (5–35 °C) and ionic strength (0.1–0.7 M). The oxidation rates were fitted to an equation valid at different pH and ionic strength conditions in sodium chloride and seawater solutions:The reduction of Cu(II) was studied in both media for different initial concentrations of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) productions were 20% and 9% for NaCl and seawater, respectively. The effect of speciation of copper(I) reduced from Cu(II) on the rates was studied. The Cu(I) speciation is dominated by the CuCl₂⁻ species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range of 0.1 M to 0.7 M chloride concentrations.  相似文献   

Reynolds number dependence of mixing in a lock-exchange system from direct numerical and large eddy simulations     

Tamay M. zgkmen  Traian Iliescu  Paul F. Fischer 《Ocean Modelling》2009,30(2-3):190-206

Turbulent mixing of water masses of different temperatures and salinities is an important process for both coastal and large-scale ocean circulation. It is, however, difficult to capture computationally. One of the reasons is that mixing in the ocean occurs at a wide range of complexity, with the Reynolds number reaching , or even higher.In this study, we continue to investigate whether large eddy simulation (LES) can be a reliable computational tool for stratified mixing in turbulent oceanic flows. LES is attractive because it can be times faster than a direct numerical simulation (DNS) of stratified mixing in turbulent flows. Before using the LES methodology to compute mixing in realistic oceanic flows, however, a careful assessment of the LES sensitivity with respect to Re needs to be performed first. The main objectives of this study are: (i) to investigate the performance of different LES models at high Re, such as those encountered in oceanic flows; and (ii) to study how mixing varies as a function of Re. To this end, as a benchmark we use the lock-exchange problem, which is described by unambigous and simple initial and boundary conditions. The background potential energy, which accurately quantifies irreversible mixing in an enclosed system, is used as the main criterion in a posteriori testing of LES.This study has two main achievements. The first is that we investigate the accuracy of six combinations of two different classes of LES models, namely eddy-viscosity and approximate deconvolution types, for 3×10³Re3×10⁴, for which DNS data is computed. We find that all LES models almost always provide significantly more accurate results than cases without LES models. Nevertheless, no single LES model that is persistently superior to others over this Re range could be identified. Then, an ensemble of the four best performing LES models is selected in order to estimate mixing taking place in this system at Re=10⁵ and 10⁶, for which DNS is presently not feasible. Thus the second achievement of this study is to quantify mixing taking place in this system over an Re range that changes by three orders of magnitude. We find that the background potential energy increases by about 67% when Re is increased from Re=10³ to Re=10⁶, within the computation period, with the most significant increase taking place from Re=3×10³ to Re=10⁵.  相似文献   

Steepness and spectrum of nonlinear deformed shallow water wave     

Narcisse Zahibo  Irina Didenkulova  Andrey Kurkin  Efim Pelinovsky   《Ocean Engineering》2008,35(1):47-52

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Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy   总被引：74，自引：0，他引：74  

Paula G. Coble 《Marine Chemistry》1996,51(4):325-346

High-resolution fluorescence spectroscopy was used to characterize dissolved organic matter (DOM) in concentrated and unconcentrated water samples from a wide variety of freshwater, coastal and marine environments. Several types of fluorescent signals were observed, including humic-like, tyrosine-like, and tryptophan-like. Humic-like fluorescence consisted of two peaks, one stimulated by UV excitation (peak A) and one by visible excitation (peak C). For all samples, the positions of both excitation and emission maxima for peak C were dependent upon wavelength of observation, with a shift towards longer wavelength emission maximum at longer excitation wavelength and longer wavelength excitation maximum at longer emission wavelength. A trend was observed in the position of wavelength-independent maximum fluorescence () for peak C, with maximum at shorter excitation and emission wavelengths for marine samples than for freshwater samples. Mean positions of these maxima were: rivers = nm; coastal water = nm; marine shallow transitional = nm; marine shallow eutrophic = nm; and marine deep = nm. Differences suggest that the humic material in marine surface waters is chemically different from humic material in the other environments sampled. These results explain previous conflicting reports regarding fluorescence properties of DOM from natural waters and also provide a means of distinguishing between water mass sources in the ocean.  相似文献   

The effect of pressure on transition metals in seawater     

Frank J. Millero  Fen Huang 《Deep Sea Research Part I: Oceanographic Research Papers》2011,58(3):298-305

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A general theory of three-dimensional wave groups Part I: The formal derivation     

Paolo Boccotti 《Ocean Engineering》1997,24(3):265-280

If we know that a wave of given exceptionally large crest-to-trough height occurs at a fixed point at an instant t_o in a random wind-generated sea state, we can predict what happens with a very high probability before and after t_o in an area surrounding . The expressions of the surface displacement and velocity potential in this area are obtained in closed form. They are exact to the first order in a Stokes expansion and hold for nearly arbitrary bandwidth and solid boundary. It will be shown in Part II that these expressions represent either the evolution of a single three-dimensional wave group or the collision of two wave groups, according to the configuration of the solid boundary. The theory was developed in a series of papers starting on 1981. This paper presents the whole theory in a compact form thanks to a radical simplification of the mathematical proof.  相似文献