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The density of North Atlantic and North Pacific deep waters
286
Oceanographic Abstracts
MERCERET F . J . , 1976. The turbulent microstructure of Hurricane Caroline (1975). Mon. Neath. Rev., 104 (10): 1297-1307. Microscale horizontal velocity fluctuation measurements in Hurricane Caroline (1975) show that except in the eye, turbulent energy dissipation does not vary systematically with wind speed or altitude. Inertial subrange-shaped spectra are found below cloud base and slightly above it. At higher altitudes, some deviation from that shape may occur. The amount of energy dissipated within the body of the storm is slightly larger than that dissipated at the surface in accord with earlier estimates by residuals. The dissipation is highly intermittent with a log-normal cumulative probability distribution. MILLER R. L., 1976. Role of vortices in surf zone prediction: sedimentation and wave forces. Spec. Pub& Soc. econ. Palaeont. Miner., Tulsa, 24: 92-114. There are difficulties in the crealion of numerical prediction models in the surf zone. Specific examination of fundamental breaker mechanics is necessary, if successful prediction is to be achieved. Investigation of the internal velocity field indicates the importance of "breaker vortices" whose size and strength are a function of breaker shape. Numerous experiments have provided data for a detailed analysis of the vortices. As a result, a first approximation model is discussed, although further work is necessary. The effect of breaker shape and brea~:er vortices is indicated in three applications; (1) bedforms in the surf zone, (2) impact pressures due to breaking waves, (3) the interaction of post-breaking bore and foreshore. In each case the reliability of prediction is considered. MILLERO F . J . , 1 9 7 4 / 7 5 The state of metal ions in seawater. Thalassia Jugosl., II (1/2): 53-84. The methods of determining the state or structure of metal ions in seawater are examined in terms of ion-water and ion-ion interactions. The ion-water interactions are related to the changes that occur when an ion is transferred from the gas to the infinite dilution solution state. The experimental thermodynamic properties at infinite dilution are compared to the values determined using the continuum model and a structural hydration model. The hydration model considers the ion-water interactions in terms of ion-dipole, ion-quadrupole interactions and water structure effects. By combining partial molal volume and compressibility data a method is developed to determine hydration numbers for the major sea salts and some trace metal ions. The ion-ion interactions that occur as the concentration is increased are examined by using three methods: (1) the ion pairing model, (2) the specific interaction model, and (3) the cluster (or non-specific interaction) model. For the major sea salts all the methods yield reasonable estimates for total or stoichiometric activity coefficients. The use of the ion pairing model for determining the speciation of heavy metats in seawater are examined and briefly discussed. Methods of studying the structure of ion paired species are developed and applied to the MgSO4° ion pair. MILLERO F . J . , AUGUSTIN GONZALEZ, P. G. BREWER and ALVIN BRADSHAW, 1976. The density of North Atlantic and North Pacific deep waters. GEOSECSPubI., 75. Also in: Earth planet. Sci. Letts, 32 (2): 468-472. The densities of seventeen samples of seawater from GEOSECS stations 27 (North Atlantic) and 217 (North Pacific) have been measured with a vibrating flow densimeter at 25°C. The densities of the deep samples were found to be 5 -+ 1.5 and 16 +- 3.6 ppm greater, for the North Atlantic and North Pacific, respectively, than predicted by the equation of state of Millero, Gonzalez and Ward (1976) derived for seawaters of constant relative composition. The results are in good agreement with the density anomalies predicted by Brewer and Bradshaw (1975) on the basis of the observed increase of dissolved silica, alkalinity, and total carbon dioxide in oceanic deep waters. The application of these corrections results in an agreement with the Millero, Gonzalez and Ward (1976) equation of state to -+4 ppm. MILLERO F. J. and W. H. LEUNG, 1976. The thermodynamics of seawater at one atmosphere. Am. ,L ScL, 276 (9): 1035-1077. The solution thermodynamic properties of seawater at l atm have been examined over the range of 0 ° to 40°C and 0 to 40 °/o0 salinity. By combining the osmotic coefficients [ ¢ = - - ( 5 5 . 5 1 / 2 m ) In a~, where m is the molality and a l is the activity of water] determined from the freezing point measurements of Doherty and Kester (1974), with the heat capacity data of Millero, Perron, and Desnoyers (1973), and the enthalpy data of Millero, Hansen, and Hoff (1973), we have determined the osmotic coefficients over the range of 0 ° to 40°C at I atm using the extended Debye-Hiickel equation: I - - ¢ = 2.303 8 7 1 1 / ~ ( o / 3 ) + By1 + C 7 1 3 / 2 + D 7 1 2 , where S 7, BT, C 7, and D 7 are t,~'mperature dependent parameters. The results at 25°C were found to be in excellent agreement with the results of Robinson (1954). From the osmotic coefficient data, the vapor pressure and osmotic pressure have been determined. The osmotic coefficient data at 0°C has been used to calculate the mean activity coefficient ( 7 +) and activity (a~) of "sea salt". By using the thermodynamic equation blna2/aT = - - L 2 / R T , activities have been determined at other temperatures (0 ° to 40°C). The relative free energies of seawater, G - - G o _ 55.51 RT In a~ + m RT In a2, have been calculated from the osmotic and activity data. The relative entropy of seawater (S -- S o) was determined from the relative free energies by using the
Oceanographic Abstracts
MERCERET F . J . , 1976. The turbulent microstructure of Hurricane Caroline (1975). Mon. Neath. Rev., 104 (10): 1297-1307. Microscale horizontal velocity fluctuation measurements in Hurricane Caroline (1975) show that except in the eye, turbulent energy dissipation does not vary systematically with wind speed or altitude. Inertial subrange-shaped spectra are found below cloud base and slightly above it. At higher altitudes, some deviation from that shape may occur. The amount of energy dissipated within the body of the storm is slightly larger than that dissipated at the surface in accord with earlier estimates by residuals. The dissipation is highly intermittent with a log-normal cumulative probability distribution. MILLER R. L., 1976. Role of vortices in surf zone prediction: sedimentation and wave forces. Spec. Pub& Soc. econ. Palaeont. Miner., Tulsa, 24: 92-114. There are difficulties in the crealion of numerical prediction models in the surf zone. Specific examination of fundamental breaker mechanics is necessary, if successful prediction is to be achieved. Investigation of the internal velocity field indicates the importance of "breaker vortices" whose size and strength are a function of breaker shape. Numerous experiments have provided data for a detailed analysis of the vortices. As a result, a first approximation model is discussed, although further work is necessary. The effect of breaker shape and brea~:er vortices is indicated in three applications; (1) bedforms in the surf zone, (2) impact pressures due to breaking waves, (3) the interaction of post-breaking bore and foreshore. In each case the reliability of prediction is considered. MILLERO F . J . , 1 9 7 4 / 7 5 The state of metal ions in seawater. Thalassia Jugosl., II (1/2): 53-84. The methods of determining the state or structure of metal ions in seawater are examined in terms of ion-water and ion-ion interactions. The ion-water interactions are related to the changes that occur when an ion is transferred from the gas to the infinite dilution solution state. The experimental thermodynamic properties at infinite dilution are compared to the values determined using the continuum model and a structural hydration model. The hydration model considers the ion-water interactions in terms of ion-dipole, ion-quadrupole interactions and water structure effects. By combining partial molal volume and compressibility data a method is developed to determine hydration numbers for the major sea salts and some trace metal ions. The ion-ion interactions that occur as the concentration is increased are examined by using three methods: (1) the ion pairing model, (2) the specific interaction model, and (3) the cluster (or non-specific interaction) model. For the major sea salts all the methods yield reasonable estimates for total or stoichiometric activity coefficients. The use of the ion pairing model for determining the speciation of heavy metats in seawater are examined and briefly discussed. Methods of studying the structure of ion paired species are developed and applied to the MgSO4° ion pair. MILLERO F . J . , AUGUSTIN GONZALEZ, P. G. BREWER and ALVIN BRADSHAW, 1976. The density of North Atlantic and North Pacific deep waters. GEOSECSPubI., 75. Also in: Earth planet. Sci. Letts, 32 (2): 468-472. The densities of seventeen samples of seawater from GEOSECS stations 27 (North Atlantic) and 217 (North Pacific) have been measured with a vibrating flow densimeter at 25°C. The densities of the deep samples were found to be 5 -+ 1.5 and 16 +- 3.6 ppm greater, for the North Atlantic and North Pacific, respectively, than predicted by the equation of state of Millero, Gonzalez and Ward (1976) derived for seawaters of constant relative composition. The results are in good agreement with the density anomalies predicted by Brewer and Bradshaw (1975) on the basis of the observed increase of dissolved silica, alkalinity, and total carbon dioxide in oceanic deep waters. The application of these corrections results in an agreement with the Millero, Gonzalez and Ward (1976) equation of state to -+4 ppm. MILLERO F. J. and W. H. LEUNG, 1976. The thermodynamics of seawater at one atmosphere. Am. ,L ScL, 276 (9): 1035-1077. The solution thermodynamic properties of seawater at l atm have been examined over the range of 0 ° to 40°C and 0 to 40 °/o0 salinity. By combining the osmotic coefficients [ ¢ = - - ( 5 5 . 5 1 / 2 m ) In a~, where m is the molality and a l is the activity of water] determined from the freezing point measurements of Doherty and Kester (1974), with the heat capacity data of Millero, Perron, and Desnoyers (1973), and the enthalpy data of Millero, Hansen, and Hoff (1973), we have determined the osmotic coefficients over the range of 0 ° to 40°C at I atm using the extended Debye-Hiickel equation: I - - ¢ = 2.303 8 7 1 1 / ~ ( o / 3 ) + By1 + C 7 1 3 / 2 + D 7 1 2 , where S 7, BT, C 7, and D 7 are t,~'mperature dependent parameters. The results at 25°C were found to be in excellent agreement with the results of Robinson (1954). From the osmotic coefficient data, the vapor pressure and osmotic pressure have been determined. The osmotic coefficient data at 0°C has been used to calculate the mean activity coefficient ( 7 +) and activity (a~) of "sea salt". By using the thermodynamic equation blna2/aT = - - L 2 / R T , activities have been determined at other temperatures (0 ° to 40°C). The relative free energies of seawater, G - - G o _ 55.51 RT In a~ + m RT In a2, have been calculated from the osmotic and activity data. The relative entropy of seawater (S -- S o) was determined from the relative free energies by using the