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   

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   

On the planing of a flat plate at high Froude numbers in a two-dimensional case     

Y.K. Chung  H.H. Chun   《Ocean Engineering》2008,35(7):646-652

We seek the solution of the planing of a flat plate at high Froude numbers by a perturbation procedure. The angle of attack of the plate is assumed to vary with the speed of the plate in the present study. A harmonic function K is introduced for the solution of the first-order disturbance potential which becomes the Green function in the limiting case when the Froude number tends to infinity. We get the solution of the first-order potential from Green's theorem applied to K and the first-order potential. Then we obtain the asymptotic solutions of the angle of attack α, lift L and drag D as follows: where α1. Here W, L_W, and U are the weight of the plate per unit width, wetted length, and speed of the plate, respectively.  相似文献   

Recent developments in “added-mass” planing theory     

P. R. Payne 《Ocean Engineering》1994,21(3)

The results of several recent isolated investigations in planing theory are consolidated in this paper, together with new insights generated by a recent numerical solution of the vertically impacting wedge problem by Zhao and Faltinsen [(1992), Water entry of two-dimensional bodies. J. Fluid Mech. 246, 593–612]. As a result, in contrast to some earlier studies, it is found that the “wetted width” associated with the added mass is not that of the intersection of the wedge with the undisturbed water surface, but the wetted width of the splashed-up water, as originally proposed by Wagner [(1932), Uber Stoss-und Gleitvorgange an der Oberflache von Flussig-Keiten, Zeitschrift für Angewandte Mathematik und Mechanik, Band 12, Heft 4 (August)]. However, the splash-up ratio is not the value of (π/2–1) which he proposed, but a value which decreases with increasing deadrise, originally proposed in the late-1940s by Pierson (“Pierson's hypothesis” in the paper). For 30° deadrise, for example, Pierson's splash-up ratio is two-thirds that of Wagner's.The new equations are employed to determine the increase in the “added mass” of prismatic hull sections due to chine immersion, using experimental data. If m_o^′ is the added amss of the hull section whose chines are just wetted, Payne [(1988), Design of High-speed Boats. Volume 1: Planing. Fishergate, Inc., Annapolis, Maryland, U.S.A.] postulated that the increase in added mass due to a chine submergence (z_c) would be where b is the chine beam and k is a constant which Payne [(1988), Design of High-speed Boats. Volume 1: Planing. Fishergate, Inc., Annapolis, Maryland, U.S.A.] gave as .The present analysis includes the “one-sided flow” correction introduced in Payne [(1990), Planing and impacting forces at large trim angels. Ocean Engng 17, 201–234]. Partly for that reason and partly because of the more precise analysis of the experimental data, the present paper revises the value to k = 2 for wetted length to beam ratios normally employed. For deadrise angles in excess of 40° and wetted keel to beam ratios in excess of 2.0, there is some evidence that k < 2.0.The revised theoretical formulation is compared with eight different sets of experimental data for flat plate and prismatic hull forms and is found to be in excellent agreement when the speed is high enough for “dynamic suction” (a loss of buoyancy at low speeds and low wetted lenghts) to be unimportant. This is true for “chines-dry” operation with deadrise angles up to 50° and chines-wet operation at length to beam ratios far in excess of the most extreme conventional practice.The research involved in performing this analysis led to the realization that different towing tanks measure different wetted chine lengths for the same hulls and test conditions. Some consistently measure more splash-up than “theory” (based on Pierson's splash-up hypothesis) predicts and others measure somewhat less than the theory. Some examples are given in Appendix B. The reason for this is not understood.  相似文献   

The effect of temperature on carbon dioxide partial pressures in seawater     

L.I. Gordon  L.B. Jones 《Marine Chemistry》1973,1(4):317-322

A correction formula is theoretically derived to evaluate the change in partial pressure of carbon dioxide in seawater upon heating. The constraints on the heating process are constant salinity, total alkalinity, and total carbon dioxide concentration. The result is . This equation fits δP_CO2/δt for open ocean seawater compositions to within approximately 9%. The almost constant 4.4%/°C effect is in agreement with that measured by Kanwisher (1960).  相似文献   

Interference of chlorophyll a in liquid scintillation counting of phytoplankton productivity samples by the C technique     

S. Nayar  B. P. L. Goh  L. M. Chou 《Estuarine, Coastal and Shelf Science》2003,56(5-6):957-960

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Chemical speciation of copper and zinc in surface waters of the western Black Sea     

Franois L. L. Muller  Sergei B. Gulin  shild Kalvy 《Marine Chemistry》2001,76(4):62

The chemical speciation of Cu and Zn was investigated by voltammetric titration methods in the surface waters (10 m) of the western Black Sea during an Istanbul–Sevastopol cruise conducted in November 1998. Supporting parameters (temperature (T), salinity (S), pH, alkalinity (Alk), suspended particulate matter (SPM) and dissolved and particulate ²³⁴Th) were obtained in order to distinguish hydrographic features against involvement of the metals in biogeochemical processes. In the Turkish continental slope region, the cruise track intersected a narrow vein of colder water originating on the western shelf. The core of this cold water vein was characterised by a relatively low salinity, higher specific alkalinity and higher metal (especially Cu) and metal-binding ligand concentrations.A very large portion of Cu (93–99.8%) and Zn (82–97%) was organically complexed. The degree of complexation was highest in shelf waters and lowest in the central gyre. Titration data for Cu were modelled by two classes of organic binding ligands characterised by (C_L1=3–12 nM, log K₁′=13.1–13.9) and (C_L2=20–70 nM, log K₂′=9.4–11.2). These ligands occurred mainly in the ‘dissolved’ phase, as defined by 0.4-μm filtration. The stronger Cu-binding ligand seemed to be produced in situ in response to Cu concentration, whereas the weaker Cu-binding ligand appeared to be derived from terrestrial sources and/or reducing shelf sediments. Titration results for Zn were generally represented by one class of ligands (C_L1=8–23 nM, log K₁′=9.4–10.2), which were almost uniformly distributed between the ‘dissolved’ (78±8%) and the particulate phase (22±8%). The concentration of these strong Zn-binding ligands showed a very good correlation with SPM (r²=0.64), which improved when the dissolved ligands alone were considered (r²=0.78). It is hypothesised that these ligands were produced in situ by the bacterial breakdown of particulate organic matter.  相似文献   

Solubility of calcite in the ocean     

S. E. Ingle 《Marine Chemistry》1975,3(4):301-319

The apparent solubility product K′_sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′_sp at 25°C was 4.59·10⁻⁷ mole²/(kg seawater)² at 35‰S, 5.34·10⁻⁷ at 43‰S, and 3.24·10⁻⁷ at 27‰S. The apparent partial molal volume was found to be −34.4 cm³ at 25°C and −42.3 cm³ at 2°C from a linear fit of log(K′_sp ^P/K′_sp ¹). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.  相似文献   

Reply     

C. Kuo  Y. Welaya 《Ocean Engineering》1982,9(1):101-102

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Tandem hydrofoil system     

Konstantin I. Matveev  Ivan Ivanovich Matveev 《Ocean Engineering》2001,28(2):963

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Glucuronidation in the polar bear (Ursus maritimus)     

James C. Sacco  Margaret O. James   《Marine environmental research》2004,58(2-5):475

Polar bears bioaccumulate lipophilic pollutants, including polychlorinated biphenyls (PCBs), into their bodies from their exclusive diet of marine organisms. Hydroxylated PCB metabolites (OH-PCBs) have been found in plasma, presumably due to CYP-dependent biotransformation of PCBs in liver. Little is known about the phase 2 metabolism of hydroxylated xenobiotics in polar bears. The objective of this study was to examine UDP-glucuronosyltransferase (UGT) activity with OH-PCBs and a hydroxylated polycyclic aromatic hydrocarbon, 3-hydroxy-benzo(a)pyrene (3-OH-BaP), in polar bear liver. Samples of frozen polar bear liver were used to prepare microsomes. UGT activity with 3-OH-BaP in Brij-treated microsomes, measured by a fluorescence assay, was readily measurable with protein concentrations in assay tubes of up to 10 μg/ml, but dropped off very sharply at higher protein concentrations. The apparent K_m for 3-OH-BaP was 1.71 ± 0.04 μM, and V_max 1.26 ± 0.16 nmol/min/mg protein (mean ± SD, n=3). UGT activities with a model tetrachloro-OH-PCB (4^′-OH-CB72) and a model hexachloro-OH-PCB (4^′-OH-CB159) were assayed with [¹⁴-C]-UDPGA and separation of the [¹⁴-C]-glucuronide by ion-pair extraction and thin-layer chromatography. [¹⁴-C]-glucuronide conjugates were readily formed by polar bear liver microsomes in the absence of added substrate, apparently from contaminants present in liver. This phenomenon was not observed using hepatic microsomes from laboratory-held catfish. Glucuronidation efficiency was much higher with 4^′-OH-CB72 (K_m 7.3 μM; V_max 1.55 nmol/min/mg) than 4^′-OH-CB159 (K_m 16.1 μM; V_max 0.46 nmol/min/mg). The identities of the aglycones present in polar bear liver are not known, but could include OH-PCBs or hydroxylated metabolites of other persistent organic pollutants. This study demonstrates that UGT with high activity for 3-OH-BaP and other substrates is present in polar bear liver.  相似文献   

The solubility of CaCO₃ in seawater at 2°C based upon in-situ sampled pore water composition     

Frederick L. Sayles 《Marine Chemistry》1980,9(4):223-235

Analyses of the concentration product (Ca²⁺) × (CO₃²⁻) in the pore waters of marine sediments have been used to estimate the apparent solubility products of sedimentary calcite (K′_SPc) and aragonite (K′_SPa) in seawater. Regression of the data gives the relation In K′^P_SPc = 1.94 × 10⁻³ δP − 14.59 The 2°C, 1 atm value of K′_SPc is, then, 4.61 × 10⁻⁷ mol² l⁻². The pressure coefficient yields a at 2°C of −43.8 cm³ atm⁻¹. A single station where aragonite is present in the sediments gives a value of K′_SPa = 9.2 × 10⁻⁷ (4°C, 81 atm). The calcite data are very similar to those determined experimentally by Ingle et al. (1973) for K′_SPc at 2°C and 1 atm. The calculated is also indistinguishable from the experimental results of Ingle (1975) if is assumed to be independent of pressure.  相似文献   

The reliability of the thermodynamic constants for the dissociation of carbonic acid in seawater     

Kitack Lee  Frank J. Millero  Douglas M. Campbell 《Marine Chemistry》1996,55(3-4)

Laboratory measurements of all four CO₂ parameters [f_CO2 ( = fugacity of CO₂), pH, TCO₂ ( = total dissolved inorganic carbon), and TA ( = total alkalinity)] were made on the same sample of Gulf Stream seawater (S = 35) as a function of temperature (5–35 °C) and the ratio of TA/TCO₂ (X) (1.0–1.2). Overall the measurements were consistent to ±8 μ atm in f_CO2, ± 0.004 in pH, ± 3 μ mol kg⁻¹ in TCO₂, and ± 3 μ mol kg⁻¹ in TA with the thermodynamic constants of Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995). Deviations between the measured pH, TCO₂, TA and those calculated from various input combinations increase with increasing X when the same constants are used. This trend in the deviations indicates that the uncertainties in pK₂ become important with increasing X (surface waters), but are negligible for samples with the lower X (deep waters). This trend is < 5 μ mol kg⁻¹ when the pK₂ values of Lee and Millero (1995) are used.The overall probable error of the calculated f_CO2 due to uncertainties in the accuracy of the parameters (pH, TCO₂, TA, pK₀, pk₁, and pK₂) is ± 1.2%, which is similar to the differences between the measured values and those calculated using the thermodynamic constants of Millero (1995).The calculated values of pK₁, (from f_CO2-TCO₂-TA) agree to within ± 0.004 compared to the results of Dickson and Millero (1987), Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995) over the same experimental conditions. The calculated values of pK₂ (from pH-TCO₂-TA) are in good agreement (± 0.004) with the results of Lee and Millero (1995) and also in reasonable agreement (± 0.008) with the results of Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995). The salinity dependence of our derived values of pK₁ and pK₂, (S = 35) can be estimated using the equations determined by Millero (1995).  相似文献   

Anomalously low alkenone temperatures caused by lateral particle and sediment transport in the Malvinas Current region, western Argentine Basin     

Albert Benthien  Peter J. Müller 《Deep Sea Research Part I: Oceanographic Research Papers》2000,47(12):373

We analysed the alkenone unsaturation ratio (U^K′₃₇) in 87 surface sediment samples from the western South Atlantic (5°N–50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured U^K′₃₇ ratios were converted into temperature using the global core-top calibration of Müller et al. (1998) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by −2° to −6°C are found in the regions of the Brazil–Malvinas Confluence (35–39°S) and the Malvinas Current (41–48°S). From the oceanographic evidence these low U^K′₃₇ values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating U^K′₃₇ temperatures. In this way, particles and sediments carrying a cold water U^K′₃₇ signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.  相似文献   

Time-series sediment trap record of alkenones from the western Sea of Okhotsk     

Osamu Seki  Takeshi Nakatsuka  Kimitaka Kawamura  Sei-Ichi Saitoh  Masaaki Wakatsuchi 《Marine Chemistry》2007,104(3-4):253-265

C₃₇–C₃₉ alkenones were measured in time-series sediment trap samples collected from August 1998 to June 2000 at two depths in the seasonal sea ice region of the western Sea of Okhotsk, off Sakhalin, in order to investigate alkenone production and water-column processes in the region. Measurable export fluxes of alkenones are ranged from < 0.1 to 5.8 μg/m²/day and clearly showed that the alkenone production was restricted to autumn. In 1998, maximum export flux of alkenones occurred in September when surface water column was well stratified with low nutrients in the surface mixing layer. In the next year, the maximum flux is observed in October. Comparison between alkenone temperature and satellite based sea surface temperature (SST) shows that the estimated alkenone temperatures in August 1998 were found to be  10 °C lower than the temporal satellite SST, suggesting that alkenones are produced in surface to subsurface thermocline layers during the period. Annual mean flux of alkenones is lower in the lower traps than that of the upper traps, suggesting rapid degradation of alkenones in water column, but the U^K₃₇′ value is not significantly altered. This study indicates that U^K₃₇′ values preserved in the surface sediments off Sakhalin reflect the seasonal temperature signal of near surface water, rather than annual mean surface temperature.  相似文献   

Earthquake response of submerged circular cylinder     

Anthony N. Williams 《Ocean Engineering》1986,13(6)

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Seasonal variations of alkenones and U₃₇ in the Chesapeake Bay water column     

Jennifer L. Mercer  Meixun Zhao  Steven M. Colman   《Estuarine, Coastal and Shelf Science》2005,63(4):675-682

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.  相似文献