The rates of thiourea oxidation with Fe(VI) were determined as a function of pH (8.8-11.5) and te... more The rates of thiourea oxidation with Fe(VI) were determined as a function of pH (8.8-11.5) and temperature (10-35°C
Large quantities of African dust are carried across the North Atlantic by Trade Winds every summe... more Large quantities of African dust are carried across the North Atlantic by Trade Winds every summer. The deposition of this dust has an impact on biogeochemical processes in the Tropical and Western Atlantic Ocean and Caribbean and it contributes to the formation of soils on Caribbean islands, the Bahamas, and the southeastern US. Here we report on a study of the temporal and spatial variability of the elemental composition of aerosol samples collected in the Trade Winds at Barbados and Miami over the summers of 2003 and 2004. Our objective is to identify characteristics that might serve as a useful tool to identify natural and anthropogenic sources of specific elements or element classes placing a special focus on dust-linked species. To this end we measured a large suite of elements: Al, Zn. Most elements exhibited a surprising uniformity that is highly correlated with dust concentration as determined by aerosol filter ash residues and by Mn concentration, shown to be an excellent proxy for dust. The concentrations of most elements are very close to average upper crustal abundances. We measured the greatest enrichments and the largest variability for As, Cd, Cu, Cr, Ni, Pb, V, and Zn, elements known to have major anthropogenic sources. For some elements, most notably the Lanthanides, we found statistically significant differences between high-dust-load samples and low-load samples and also between individual dust peaks. However, the absolute differences were generally quite small. Consequently we feel that on a sample-by-sample basis the elemental composition of dust is unlikely to serve as useful indicator of source regions with the possible exception of the Lanthanides. The uniformity of dust composition suggests that a major fraction of the dust is either derived from regions having similar composition or from multiple different sources followed by mixing during transport.
Large quantities of African dust are carried across the North Atlantic by Trade Winds every summe... more Large quantities of African dust are carried across the North Atlantic by Trade Winds every summer. The deposition of this dust has an impact on biogeochemical processes in the Tropical and Western Atlantic Ocean and Caribbean and it contributes to the formation of soils on Caribbean islands, the Bahamas, and the southeastern US. Here we report on a study of the temporal and spatial variability of the elemental composition of aerosol samples collected in the Trade Winds at Barbados and Miami over the summers of 2003 and 2004. Our objective is to identify characteristics that might serve as a useful tool to identify natural and anthropogenic sources of specific elements or element classes placing a special focus on dust-linked species. To this end we measured a large suite of elements: Al, As, and Zn. Most elements exhibited a surprising uniformity that is highly correlated with dust concentration as determined by aerosol filter ash residues and by Mn concentration, shown to be an excellent proxy for dust. The concentrations of most elements are very close to average upper crustal abundances. We measured the greatest enrichments and the largest variability for As, Cd, Cu, Cr, Ni, Pb, V, and Zn, elements known to have major anthropogenic sources. For some elements, most notably the Lanthanides, we found statistically significant differences between high-dust-load samples and low-load samples and also between individual dust peaks. However, the absolute differences were generally quite small. Consequently we feel that on a sample-by-sample basis the elemental composition of dust is unlikely to serve as useful indicator of source regions with the possible exception of the Lanthanides. The uniformity of dust composition suggests that a major fraction of the dust is either derived from regions having similar composition or from multiple different sources followed by mixing during transport.
Deep Sea Research and Oceanographic Abstracts, 1971
ABSTRACT The isothermal compressibility of artificial seawater has been measured by a piezometric... more ABSTRACT The isothermal compressibility of artificial seawater has been measured by a piezometric technique from intervals and from 0 to 40°C in 5° intervals. The measurements were made at 17 bar increments to 34 bars and the data extrapolated to one atmosphere. Compressibility determinations on a Copenhagen seawater sample (∼35‰S) over the same temperature and pressure range yielded results that agreed with the artificial seawater results (within our experimental error of ±0·05 × 10−6 bar−1). The isothermal compressibility results at one atmosphere and 35‰ are in excellent agreement with the values calculated from Wilson's (1960) sound velocity data; however, our results disagree with the P-V-T data of Ekman (1908), Newton and Kennedy (1965) and Wilson and Bradley (1968). The normalized compressibilities of Ekman show excellent agreement with Wilson's and our results. A theoretical equation for the compressibility of seawater as a function of chlorinity has been developed in terms of the apparent equivalent compressibility of the major ionic components of seawater. The theoretically calculated isothermal compressibilities of seawater at 25° agree very well with the experimental results (to within ±0·09 × 10−6 bar−1).
The primary goal of the CLIVAR/CO2 Repeat Hydrography Program is to quantify the ocean's role... more The primary goal of the CLIVAR/CO2 Repeat Hydrography Program is to quantify the ocean's role in sequestering anthropogenic CO2 and the effects of natural variability and climate change on marine ecosystems and biogeochemistry. The Pacific Ocean plays a unique role in the ocean carbon cycle because it is the final destination of deep waters containing high levels of preformed nutrients and dissolved inorganic carbon (DIC) and because of the way that Pacific circulation affects the transport and storage of anthropogenic CO2. Discrete high-quality DIC and total alkalinity data were acquired as part of the WOCE/JGOFS global CO2 survey cruises in the early 1990s. Hydrographic survey cruises conducted as part of the CLIVAR/CO2 Repeat Hydrography Program recently reoccupied the east-west P2 line along 30°N in 2004 and the north-south P16 line along 152°W in 2005 and 2006. DIC increases since WOCE/JGOFS were about 10-15 mumol kg-1 in shallow waters along these lines, but not all of the...
Deep Sea Research Part I Oceanographic Research Papers
Measurements of (p,ρ,T) properties of seawater with absolute salinity SA=(31.684, 33.507, 37.372,... more Measurements of (p,ρ,T) properties of seawater with absolute salinity SA=(31.684, 33.507, 37.372, 37.969, 40.164, 41.825, 44.811, 46.119, 48.600, 50.232, 52.449 and 55.529) g kg−1, temperature T=273.15–468.15 K and pressures, p, up to 140 MPa are reported with the reproducibility of the density measurements observed to be in the average percent deviation range Δρ/ρ=±0.01–0.03%. The measurements are made with a new set up vibration-tube densimeter which is calibrated using double-distilled water (Wagner and Pruß, 2002), methanol [(de Reuck and Craven, 1993), (Osada et al., 1999) and (Yokoyama and Uematsu, 2003)] and aqueous NaCl solutions [(Archer, 1992) and (Hilbert, 1979)]. Based on these measurements, an empirical expression for the density of seawater at high salinities has been developed as a function of salinity, pressure and temperature. The results can be used to extend the present equation of state of seawater to higher temperatures for pressure up to 140 MPa.
An important property of aqueous solutions is pH because it affects chemical and biochemical prop... more An important property of aqueous solutions is pH because it affects chemical and biochemical properties such as chemical reactions, equilibrium conditions, and biological toxicity. With the increasing uptake of fossil fuel CO2 into the oceans, a decrease in pH is important to consider at this time. Unfortunately, many different methods for assessing pH have been used by different groups. The objectives of this review were to (1) briefly examine the concept of pH as it was introduced and developed, up to the current scientific developments, assumptions, and recommendations, (2) critically assess the various approaches that different scientific groups have adopted for pH, balancing their preferences and arguments, (3) compare measuring vs. modeling pH, and (4) issue recommendations on an optimized approach or approaches for pH. The main conclusions of this review are: (1) pH definitions and conventions are highly variable, which leads to highly variable estimates of pH. For example, f...
The SCOR/IAPSO Working Group 127 on the “Equation of State and Thermodynamics of Seawater” is cha... more The SCOR/IAPSO Working Group 127 on the “Equation of State and Thermodynamics of Seawater” is charged with providing improved algorithms and descriptions of the thermodynamic properties of seawater. The working group has made significant progress on many of its goals, and it is now time to seek the advice of the oceanographic community regarding the best practical ways of adopting these developments into oceanographic practice. The Working Group has met twice to date, once in Warnemünde in 2006, then in Reggio Calabria in 2007. Our next meeting is in Berlin in September 2008. The working group will soon provide the most accurate algorithms to date for the thermodynamic properties of seawater (such as density, entropy, enthalpy, specific heat capacity, etc). In order to achieve such accuracy it became evident that a salinity variable is required that more accurately represents absolute salinity than does the conductivity-based Practical Salinity. Spatial variations in the composition...
Deep Sea Research Part I Oceanographic Research Papers
The practical (Sp) and reference (SR) salinities do not account for variations in physical proper... more The practical (Sp) and reference (SR) salinities do not account for variations in physical properties such as density and enthalpy. Trace and minor components of seawater, such as nutrients or inorganic carbon affect these properties. This limitation has been recognized and several studies have been made to estimate the effect of these compositional changes on the conductivity-density relationship. These studies have been limited in number and geographic scope. Here, we combine the measurements of previous studies with new measurements for a total of 2,857 conductivity-density measurements, covering all of the world’s major oceans, to derive empirical equations for the effect of silica and total alkalinity on the density and absolute salinity of the global oceans and to recommend an equation applicable to most of the World’s oceans. The potential impact on salinity as a result of uptake of anthropogenic CO2 is also discussed.
... Hlgher Order Electrostatic Terms Rabindra N. Roy,* Susan A. Rice, Kathleen M. Vogel, Lakshmi ... more ... Hlgher Order Electrostatic Terms Rabindra N. Roy,* Susan A. Rice, Kathleen M. Vogel, Lakshmi N. Roy, Department of Chemistry, Drury College, Springfield. Missouri 65802 and Frank J. Millero ... SOC. 1961,83, 2636. (2) Rush, RM; Johnson, J. S. J. Phys. Chem. 1968, 72, 767. ...
The rates of thiourea oxidation with Fe(VI) were determined as a function of pH (8.8-11.5) and te... more The rates of thiourea oxidation with Fe(VI) were determined as a function of pH (8.8-11.5) and temperature (10-35°C
Large quantities of African dust are carried across the North Atlantic by Trade Winds every summe... more Large quantities of African dust are carried across the North Atlantic by Trade Winds every summer. The deposition of this dust has an impact on biogeochemical processes in the Tropical and Western Atlantic Ocean and Caribbean and it contributes to the formation of soils on Caribbean islands, the Bahamas, and the southeastern US. Here we report on a study of the temporal and spatial variability of the elemental composition of aerosol samples collected in the Trade Winds at Barbados and Miami over the summers of 2003 and 2004. Our objective is to identify characteristics that might serve as a useful tool to identify natural and anthropogenic sources of specific elements or element classes placing a special focus on dust-linked species. To this end we measured a large suite of elements: Al, Zn. Most elements exhibited a surprising uniformity that is highly correlated with dust concentration as determined by aerosol filter ash residues and by Mn concentration, shown to be an excellent proxy for dust. The concentrations of most elements are very close to average upper crustal abundances. We measured the greatest enrichments and the largest variability for As, Cd, Cu, Cr, Ni, Pb, V, and Zn, elements known to have major anthropogenic sources. For some elements, most notably the Lanthanides, we found statistically significant differences between high-dust-load samples and low-load samples and also between individual dust peaks. However, the absolute differences were generally quite small. Consequently we feel that on a sample-by-sample basis the elemental composition of dust is unlikely to serve as useful indicator of source regions with the possible exception of the Lanthanides. The uniformity of dust composition suggests that a major fraction of the dust is either derived from regions having similar composition or from multiple different sources followed by mixing during transport.
Large quantities of African dust are carried across the North Atlantic by Trade Winds every summe... more Large quantities of African dust are carried across the North Atlantic by Trade Winds every summer. The deposition of this dust has an impact on biogeochemical processes in the Tropical and Western Atlantic Ocean and Caribbean and it contributes to the formation of soils on Caribbean islands, the Bahamas, and the southeastern US. Here we report on a study of the temporal and spatial variability of the elemental composition of aerosol samples collected in the Trade Winds at Barbados and Miami over the summers of 2003 and 2004. Our objective is to identify characteristics that might serve as a useful tool to identify natural and anthropogenic sources of specific elements or element classes placing a special focus on dust-linked species. To this end we measured a large suite of elements: Al, As, and Zn. Most elements exhibited a surprising uniformity that is highly correlated with dust concentration as determined by aerosol filter ash residues and by Mn concentration, shown to be an excellent proxy for dust. The concentrations of most elements are very close to average upper crustal abundances. We measured the greatest enrichments and the largest variability for As, Cd, Cu, Cr, Ni, Pb, V, and Zn, elements known to have major anthropogenic sources. For some elements, most notably the Lanthanides, we found statistically significant differences between high-dust-load samples and low-load samples and also between individual dust peaks. However, the absolute differences were generally quite small. Consequently we feel that on a sample-by-sample basis the elemental composition of dust is unlikely to serve as useful indicator of source regions with the possible exception of the Lanthanides. The uniformity of dust composition suggests that a major fraction of the dust is either derived from regions having similar composition or from multiple different sources followed by mixing during transport.
Deep Sea Research and Oceanographic Abstracts, 1971
ABSTRACT The isothermal compressibility of artificial seawater has been measured by a piezometric... more ABSTRACT The isothermal compressibility of artificial seawater has been measured by a piezometric technique from intervals and from 0 to 40°C in 5° intervals. The measurements were made at 17 bar increments to 34 bars and the data extrapolated to one atmosphere. Compressibility determinations on a Copenhagen seawater sample (∼35‰S) over the same temperature and pressure range yielded results that agreed with the artificial seawater results (within our experimental error of ±0·05 × 10−6 bar−1). The isothermal compressibility results at one atmosphere and 35‰ are in excellent agreement with the values calculated from Wilson's (1960) sound velocity data; however, our results disagree with the P-V-T data of Ekman (1908), Newton and Kennedy (1965) and Wilson and Bradley (1968). The normalized compressibilities of Ekman show excellent agreement with Wilson's and our results. A theoretical equation for the compressibility of seawater as a function of chlorinity has been developed in terms of the apparent equivalent compressibility of the major ionic components of seawater. The theoretically calculated isothermal compressibilities of seawater at 25° agree very well with the experimental results (to within ±0·09 × 10−6 bar−1).
The primary goal of the CLIVAR/CO2 Repeat Hydrography Program is to quantify the ocean's role... more The primary goal of the CLIVAR/CO2 Repeat Hydrography Program is to quantify the ocean's role in sequestering anthropogenic CO2 and the effects of natural variability and climate change on marine ecosystems and biogeochemistry. The Pacific Ocean plays a unique role in the ocean carbon cycle because it is the final destination of deep waters containing high levels of preformed nutrients and dissolved inorganic carbon (DIC) and because of the way that Pacific circulation affects the transport and storage of anthropogenic CO2. Discrete high-quality DIC and total alkalinity data were acquired as part of the WOCE/JGOFS global CO2 survey cruises in the early 1990s. Hydrographic survey cruises conducted as part of the CLIVAR/CO2 Repeat Hydrography Program recently reoccupied the east-west P2 line along 30°N in 2004 and the north-south P16 line along 152°W in 2005 and 2006. DIC increases since WOCE/JGOFS were about 10-15 mumol kg-1 in shallow waters along these lines, but not all of the...
Deep Sea Research Part I Oceanographic Research Papers
Measurements of (p,ρ,T) properties of seawater with absolute salinity SA=(31.684, 33.507, 37.372,... more Measurements of (p,ρ,T) properties of seawater with absolute salinity SA=(31.684, 33.507, 37.372, 37.969, 40.164, 41.825, 44.811, 46.119, 48.600, 50.232, 52.449 and 55.529) g kg−1, temperature T=273.15–468.15 K and pressures, p, up to 140 MPa are reported with the reproducibility of the density measurements observed to be in the average percent deviation range Δρ/ρ=±0.01–0.03%. The measurements are made with a new set up vibration-tube densimeter which is calibrated using double-distilled water (Wagner and Pruß, 2002), methanol [(de Reuck and Craven, 1993), (Osada et al., 1999) and (Yokoyama and Uematsu, 2003)] and aqueous NaCl solutions [(Archer, 1992) and (Hilbert, 1979)]. Based on these measurements, an empirical expression for the density of seawater at high salinities has been developed as a function of salinity, pressure and temperature. The results can be used to extend the present equation of state of seawater to higher temperatures for pressure up to 140 MPa.
An important property of aqueous solutions is pH because it affects chemical and biochemical prop... more An important property of aqueous solutions is pH because it affects chemical and biochemical properties such as chemical reactions, equilibrium conditions, and biological toxicity. With the increasing uptake of fossil fuel CO2 into the oceans, a decrease in pH is important to consider at this time. Unfortunately, many different methods for assessing pH have been used by different groups. The objectives of this review were to (1) briefly examine the concept of pH as it was introduced and developed, up to the current scientific developments, assumptions, and recommendations, (2) critically assess the various approaches that different scientific groups have adopted for pH, balancing their preferences and arguments, (3) compare measuring vs. modeling pH, and (4) issue recommendations on an optimized approach or approaches for pH. The main conclusions of this review are: (1) pH definitions and conventions are highly variable, which leads to highly variable estimates of pH. For example, f...
The SCOR/IAPSO Working Group 127 on the “Equation of State and Thermodynamics of Seawater” is cha... more The SCOR/IAPSO Working Group 127 on the “Equation of State and Thermodynamics of Seawater” is charged with providing improved algorithms and descriptions of the thermodynamic properties of seawater. The working group has made significant progress on many of its goals, and it is now time to seek the advice of the oceanographic community regarding the best practical ways of adopting these developments into oceanographic practice. The Working Group has met twice to date, once in Warnemünde in 2006, then in Reggio Calabria in 2007. Our next meeting is in Berlin in September 2008. The working group will soon provide the most accurate algorithms to date for the thermodynamic properties of seawater (such as density, entropy, enthalpy, specific heat capacity, etc). In order to achieve such accuracy it became evident that a salinity variable is required that more accurately represents absolute salinity than does the conductivity-based Practical Salinity. Spatial variations in the composition...
Deep Sea Research Part I Oceanographic Research Papers
The practical (Sp) and reference (SR) salinities do not account for variations in physical proper... more The practical (Sp) and reference (SR) salinities do not account for variations in physical properties such as density and enthalpy. Trace and minor components of seawater, such as nutrients or inorganic carbon affect these properties. This limitation has been recognized and several studies have been made to estimate the effect of these compositional changes on the conductivity-density relationship. These studies have been limited in number and geographic scope. Here, we combine the measurements of previous studies with new measurements for a total of 2,857 conductivity-density measurements, covering all of the world’s major oceans, to derive empirical equations for the effect of silica and total alkalinity on the density and absolute salinity of the global oceans and to recommend an equation applicable to most of the World’s oceans. The potential impact on salinity as a result of uptake of anthropogenic CO2 is also discussed.
... Hlgher Order Electrostatic Terms Rabindra N. Roy,* Susan A. Rice, Kathleen M. Vogel, Lakshmi ... more ... Hlgher Order Electrostatic Terms Rabindra N. Roy,* Susan A. Rice, Kathleen M. Vogel, Lakshmi N. Roy, Department of Chemistry, Drury College, Springfield. Missouri 65802 and Frank J. Millero ... SOC. 1961,83, 2636. (2) Rush, RM; Johnson, J. S. J. Phys. Chem. 1968, 72, 767. ...
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Papers by Frank Millero