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   

Effect of changes in water salinity on ammonium, calcium, dissolved inorganic carbon and influence on water/sediment dynamics     

P. Lpez 《Estuarine, Coastal and Shelf Science》2003,56(5-6):943-956

The effect of a sudden increase in salinity from 10 to 37 in porewater concentration and the benthic fluxes of ammonium, calcium and dissolved inorganic carbon were studied in sediments of a small coastal lagoon, the Albufera d'Es Grau (Minorca Island, Spain). The temporal effects of the changes in salinity were examined over 17 days using a single diffusion-reaction model and a mass-balance approach. After the salinity change, NH₄⁺-flux to the water and Ca-flux toward sediments increased (NH₄⁺-flux: 5000–3000 μmol m⁻² d⁻¹ in seawater and 600/250 μmol m⁻² d⁻¹ in brackish water; Ca-flux: −40/−76 meq m⁻² d⁻¹ at S=37 and −13/−10 meq m⁻² d⁻¹ at S=10); however, later NH₄⁺-flux decreased in seawater, reaching values lower than in brackish water. In contrast, Ca-flux presented similar values in both conditions. The fluxes of dissolved inorganic carbon, which were constant at S=10 (55/45 mmol m⁻² d⁻¹), increased during the experiment at S=37 (from 30 mmol m⁻² d⁻¹ immediately after salinity increase to 60 mmol m⁻² d⁻¹ after 17 days).In brackish conditions, NH₄⁺ and Ca²⁺ fluxes were consistent with a single diffusion-reaction model that assumes a zero-order reaction for NH₄⁺ production and a first-order reaction for Ca²⁺ production. In seawater, this model explained the Ca-flux observed, but did not account for the high initial flux of NH₄⁺.The mass balance for 17 days indicated a higher retention of NH₄⁺ in porewater in the littoral station in seawater conditions (9.5 mmol m⁻² at S=37 and 1.6 mmol m⁻² at S=10) and a significant reduction in the water consumption at both sites (5 mmol m⁻² at S=37; 35/23 mmol m⁻² at S=10). In contrast, accumulation of dissolved inorganic carbon in porewater was lower in seawater incubations (−10/−1 meq m⁻² at S=37; 50/90 meq m⁻² at S=10) and was linked to a higher efflux of CO₂ to the atmosphere, because of calcium carbonate precipitation in water (675/500 meq m⁻²). These results indicate that increased salinity in shallow coastal waters could play a major role in the global carbon cycle.  相似文献   

Solubility of oxygen in the major sea salts as a function of concentration and temperature     

Frank J. Millero  Fen Huang  Arthur L. Laferiere 《Marine Chemistry》2002,78(4):125

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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   

Formation and stability of mixed Mg/Ca/phytate species in synthetic seawater media: Consequences on ligand speciation     

Pasquale Crea  Concetta De Stefano  Demetrio Milea  Silvio Sammartano   《Marine Chemistry》2008,112(3-4):142-148

The results of a potentiometric investigation (by ISE-H⁺, glass electrode) on the speciation of phytate ion (Phy¹²⁻) in an ionic medium simulating the major components (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻ and SO₄²⁻) of natural seawater, at different salinities and t = 25 °C, are reported. The work was particularly aimed at determining the possible formation of mixed Ca²⁺–Mg²⁺–phytate ion pairs, and to establish how including the formation of these mixed species would affect the speciation modeling in seawater media. After testing various speciation models, that considering the formation of the MgCaH₃Phy⁵⁻, MgCaH₄Phy⁴⁻, Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ species was accepted, and corresponding stability constants were determined at two salinities (S = 5, 10). A discussion is reported both on the choice of the experimental conditions and on the possibility to extend these results to those typical of real seawater. A detailed procedure is also described to demonstrate that the stability of these species is higher than that statistically predicted. As reported in literature, a parameter, namely log X, has been determined in order to quantify this extra stability for the formation of each mixed species at various salinities. For example, at S = 10, log X₁₁₃ = 2.67 and log X₁₁₄ = 1.37 for MgCaH₃Phy⁵⁻ and MgCaH₄Phy⁴⁻ (statistical value is log X_stat = 0.60), and log X₂₁₃ = 6.11 and log X₂₁₄ = 2.15 for Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ (log X_stat = 1.43), respectively. Results obtained also showed that the formation of these species may occur even in conditions of low salinity (i.e. low concentration of alkaline earth cations) and low pH (i.e., more protonated ligand).  相似文献   

Methane-dominated thermochemical sulphate reduction in the Triassic Feixianguan Formation East Sichuan Basin, China: towards prediction of fatal H₂S concentrations   总被引：2，自引：0，他引：2  

Chunfang Cai  Zengye Xie  Richard H. Worden  Guoyi Hu  Lansheng Wang  Hong He 《Marine and Petroleum Geology》2004,21(10):1265-1279

New sour pools have recently found in the Lower Triassic Feixianguan Fm carbonate reservoirs in the East Sichuan Basin in China with H₂S up to 17.4% by volume. A recent blowout from a well drilled into this formation killed hundreds of people as a result of the percentage concentrations of H₂S. In order to assess the origin of fatal H₂S as well as the cause of petroleum alteration, H₂S concentrations and the isotopes, δ³⁴S and δ¹³C have been collected and measured in gas samples from reservoirs. Anhydrite, pyrite and elemental sulphur δ³⁴S values have been measured for comparison. The high concentrations of H₂S gas are found to occur at depths >3000 m (temperature now at 100 °C) in evaporated platform facies oolitic dolomite or limestone that contains anhydrite nodule occurrence within the reservoirs. Where H₂S concentrations are greater than 10% its δ³⁴S values lie between +12.0 and +13.2‰ CDT. This is within the range of anhydrite δ³⁴S values found within the Feixianguan Fm (+11.0 to +21.7‰; average 15.5±3.5‰ CDT). Thus H₂S must have been generated by thermochemical sulphate reduction (TSR) locally within the reservoirs. Burial history analysis and fluid inclusion data reveal that the temperature at which TSR occurred was greater than about 130–140 °C, suggesting that the present depth-temperature minimum is an artifact of post-TSR uplift. Both methane and ethane were actively involved in TSR since the petroleum became almost totally dry (no alkanes except methane) and methane δ¹³C values become significantly heavier as TSR proceeded. Methane δ¹³C difference thus reflects the extent of TSR. While it is tempting to use a present-day depth control (>3000 m) to predict the distribution of H₂S in the Feixianguan Fm, this is an invalid approach since TSR occurred when the formation was buried some 1000–2000 m deeper than it is at present. The likelihood of differential uplift across the basin means that it is important to develop a basinal understanding of the thermal history of the Feixianguan Fm so that it is possible to determine which parts of the basin have been hotter than 130–140 °C.  相似文献   

Simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation: conditions for precise shipboard measurements   总被引：1，自引：0，他引：1  

Xos A. lvarez-Salgado  Axel E. J. Miller 《Marine Chemistry》1998,62(3-4)

Appropriate conditions have been achieved for the accurate, rapid, and highly precise shipboard simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation. A nitrogen-specific Antek 705D chemiluminescence detector and a CO₂-specific LiCor Li6252 IRGA have been coupled in-series with a Shimadzu TOC-5000 organic carbon analyser. Precision of both simultaneous measurements is ≤1.5%, i.e. ±1 μmol C l⁻¹ and ±0.3 μmol N l⁻¹, respectively. Quality of analysis is not compromised by vibrations associated with ocean going research vessels.  相似文献   

Aggregation of riverine colloidal iron in estuaries: A new kinetic study using stopped-flow mixing     

Urszula Nowostawska  Jonathan P. Kim  Keith A. Hunter   《Marine Chemistry》2008,110(3-4):205-210

The kinetics of aggregation of riverine colloidal iron have been examined using a stopped-flow technique which probes the first few seconds of mixing between river and sea water end members. A significant fraction, up to 80%, of the colloidal iron is aggregated during the first 1–2 s of mixing, indicating that the aggregation process is much faster than previously thought. Most of the aggregation induced by seawater results from the divalent cations Mg²⁺ and Ca²⁺, with the overall ionic strength having little influence. At equal concentrations of 27 mM, the rate of aggregation by alkaline earth cations increased with ionic size Mg²⁺ < Ca²⁺ < Sr²⁺ < Ba²⁺. The aggregation rates were indifferent to the anion (Cl⁻ or SO₄²⁻) present. Very high aggregation rates were also induced by the common water treatment coagulant Al₂(SO₄)₃ at concentrations in the range 20–30 µM Al(III), several orders of magnitude lower that those used for the seawater cations. Our results support the view that specific chemical interactions between the cations and the colloid particle surface, rather than simple electrical effects, control the colloid stability.  相似文献   

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)₃ and SiO₂(OH)₂. A precision study at 25°C in a simplified seawater medium     

Staffan Sjberg  Agneta Nordin  Nils Ingri 《Marine Chemistry》1981,10(6)

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH⁻ was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 B 0.008 M and 2.5 -log[H⁺] 11.7, respectively. Within these ranges the formation of SiO(OH)₃⁻ and SiO₂(OH)₂²⁻ with formation constants log β₋₁₁(Si(OH)₄ SiO(OH)₃⁻ + H⁺) = −9.472 ±0.002 and log β₋₂₁(Si(OH)₄ SiO₂(OH)₂²⁻ + 2H⁺) = −22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with -log[H⁺] 10.7 their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.  相似文献   

Temporal and spatial variability in phytoplankton ammonium and nitrate uptake in the Delaware Estuary     

Jonathan R. Pennock 《Estuarine, Coastal and Shelf Science》1987,24(6)

Phytoplankton NH₄⁺ and NO₃⁻ uptake was examined along the longitudinal salinity gradient of the Delaware Estuary over several seasonal cycles using ¹⁵N-tracer techniques. Saturated nitrogen uptake rates increased directly with water temperature and reached a maximum of 380 nmol Nl⁻¹h⁻¹ during summer. This temperature dependence was related primarily to changes in the rate of maximum chlorophyll specific uptake, which varied exponentially between 2 and 70 nmol N [μg Chl h]⁻¹ over a temperature range of 2–28°C. Despite these high uptake rates, balanced growth (C:N7:1) could be maintained over the diel light cycle only by highly efficient nitrogen uptake at low light intensities and dark uptake below the photic zone and at night (dark UPTAKE=25% maximum uptake).Ammonium fulfilled 82% of the annual phytoplankton nitrogen demand in the estuary despite dominance of NO₃⁻ in the ambient dissolved inorganic nitrogen pool. The predominance of NH₄⁺ uptake occurred because of the general suppression of NO₃⁻ assimilation at NH₄⁺ concentrations in excess of 2 μ . This suppression, however, was not as universal as has been reported for other systems, and it is suggested that the extremely high NO₃⁻ concentrations found in the estuary contribute to this pattern. Nitrate was a significant source of nitrogen only during periods of high phytoplankton production in summer, and when NH₄⁺ concentrations were low towards the end of the spring bloom.  相似文献   

Factors influencing the magnitude of phytoplankton primary production in a high-energy surf zone     

Eileen E. Campbell  G. C. Bate 《Estuarine, Coastal and Shelf Science》1987,24(6)

The main factors influencing phytoplankton primary production in the surf zone of the Sundays River Beach, Algoa Bay have been characterized. These factors include cell concentration, chlorophyll concentration, irradiance, temperature and salinity. Good relationships have been obtained between cell concentration, chlorophyll concentration and primary production. The P-I curves showed dependence on temperature with a linear regression between temperature and I_k values. Light saturation was shown to occur between 300 and 510 μmol m⁻² s⁻¹ at normal field temperatures. T_max and T_min were found to be 34°C and 0°C, respectively; P_max was 25°C. Salinity had a marked effect on primary production with S_max occurring at 60 ppt and an extrapolated S_min at 0 ppt. P_max was found to occur at 30 ppt.  相似文献