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J.A. Davis

Publications and source records attributed to J.A. Davis.

44 records · Page 3Linked to original sources

Calorimetry of heterogeneous systems: H+ binding to TiO2 in NaCl

A simultaneous calorimetric and potentiometric technique has been developed for measuring the thermodynamics of proton binding to mineral oxides in the presence of a supporting electrolyte. Modifications made to a commercial titration calorimeter to add a combination pH electrode and maintain an inert atmosphere in the calorimeter reaction vessel are described. A procedure to calibrate potentiometric measurements in heterogeneous systems to correct for the suspension effect on pH is given. The enthalpy change for proton dissociation from TiO 2 in aqueous suspension as a function of pH is reported for 0.01, 0.1, and 0.5 M NaCl. The enthalpy change for proton dissociation is endothermic, ranging from 10.5 ± 3.8 to 45.0 ± 3.8 kJ mol −1 over the pH range from 4 to 10.

Thermochimica Acta

Trace metal associations in the water column of South San Francisco Bay, California

Spatial distributions of copper (Cu), zinc (Zn) and cadmium (Cd) were followed along a longitudinal gradient of dissolved organic carbon (DOC) in South San Francisco Bay (herein referred to as the South Bay). Dissolved Cu, Zn and Cd concentrations ranged from 24 to 66 nM, from 20 to 107 nM and from 1·2 to 4·7 nM, respectively, in samples collected on five dates beginning with the spring phytoplankton bloom and continuing through summer,1985. Dissolved Cu and Zn concentrations varied indirectly with salinity and directly with DOC concentration which ranged from 2·1 to 4·1 mg l −1 . Available thermodynamic data strongly support the hypothesis that Cu speciation may be dominated by association with dissolved organic matter. Analogous control of Zn speciation by organic complexation was, however, not indicated in our computations. Computed free ion activity estimates for Cu, Zn and Cd were of the order of 10 −10 , 10 −8 and 10 −10 M, respectively. The availability of these metals may be among the factors regulating the growth of certain phytoplankton species within this region of the estuary. In contrast to dissolved Cu, dissolved Cd was directly related to the concentration of suspended particulate matter, suggesting a source of dissolved Cd coincident with elevated particle concentrations in the South Bay (e.g. runoff and solute desorption). Consistent with work in other estuaries, partitioning of all three trace metals onto suspended particulates was negatively correlated with salinity and positively correlated with increases in particulate organic carbon associated with the phytoplankton bloom. These results for the South Bay indicate that sorption processes influence dissolved concentrations of these trace metals, the degree of this influence varies among metals, and processes controlling metal distribution in this estuary appear to be more element-specific than spatially- or temporally-specific.

California

Influence of coupling of sorption and photosynthetic processes on trace element cycles in natural waters

Chemical and biological processes have important roles in the transport and cycling of trace elements in natural waters, but their complex interactions are often not well understood. Trace-element concentrations may, for example, be controlled by adsorption-desorption reactions at mineral surfaces, with the equilibrium strongly influenced by pH. Variations in pH due to photosynthetic activity should result in concentration fluctuations as the adsorption-desorption equilibrium shifts with pH. To investigate these interactions, we have studied the effect of diurnal cycling of pH on dissolved arsenate in a perennial stream contaminated with arsenic. As expected, a diurnal cycle in arsenate concentration was observed, but surprisingly, the arsenate cycle lags several hours behind the pH cycle. Laboratory experiments show that the lag results from a slow approach to sorption equilibrium. Our observations demonstrate that the coupling of photosynthesis and sorption processes may have an important influence on the cycling of many trace elements and emphasize the importance of understanding sorption kinetics in modelling these processes.

Nature

Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

The rate of Cd2+ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO3 in CaCO3 formed in recrystallizing material. Desorption of Cd2+ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd2+ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd2+ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation.

Geochimica et Cosmochimica Acta

A study of metal ion adsorption at low suspended-solid concentrations

A procedure for conducting adsorption studies at low suspended solid concentrations in natural waters (<50 mg l −1 ) is described. Methodological complications previously associated with such experiments have been overcome. Adsorption of zinc ion onto synthetic colloidal titania (TiO 2 ) was studied as a function of pH, supporting electrolyte (NaCl) concentration (0·1-0·002 m ) and particle concentration (2–50 mg l −1 ). The lack of success of the Davis Leckie site bonding model in describing Zn(II) adsorption emphasizes the need for further studies of adsorption at low suspended-solid concentrations.

Estuarine, Coastal and Shelf Science

Culturing Selenastrum capricornutum (Chlorophyta) in a synthetic algal nutrient medium with defined mineral particulates

Algal nutrient studies in chemically-defined media typically employ a synthetic chelator to prevent iron hydroxide precipitation. Micronutrient-particulate interactions may, however, significantly affect chemical speciation and hence biovailability of these nutrients in natural waters. A technique is described by which Selenastrum capricornutum Printz (Chlorophyta) may be cultured in a medium where trace metal speciation (except iron) is controlled, not by organic chelation, but by sorption onto titanium dioxide. Application of this culturing protocol in conjunction with results from sorption studies of nutrient ions on mineral particles provides a means of studying biological impacts of sorptive processes in aquatic environments.

Hydrobiologia

Complexation of trace metals by adsorbed natural organic matter

The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu2+ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter.

Geochimica et Cosmochimica Acta