ALBERT

Notizen: Abstract A very precise and accurate new method is described for determination of the Henry coefficient k and the isotopic fractionation of gases dissolved in liquids. It yields fully corrected values for k at essentially infinite dilution. For oxygen the random error for k is less than 0.02%, which is an order of magnitude better than the best previous measurements on that or any other gas. Extensive tests and comparison with other work indicate that systematic errors probably are negligible and that the accuracy is determined by the precision of the measurements. In the virial correction factor (1+λPt), where Pt is the total pressure of the vapor phase, the coefficient λ for oxygen empirically is a linear decreasing function of the temperature over the range 0–60°C. The simple three-term power series in 1/T proposed by Benson and Krause, $$\ln k = a_0 + a_1 /T + a_2 /T^2 $$ provides a much better form for the variation of k with temperature than any previous expression. With a0=3.71814, a1=5596.17, and a2=−1049668, the precision of fit to it of 37 data points for oxygen from 0–60°C is 0.018% (one standard deviation). The three-term series in 1/T also yields the best fit for the most accurate data on equilibrium constants for other types of systems, which suggests that the function may have broader applications. The oxygen results support the idea that when the function is rewritten as $$\ln k = - (A_1 + A_2 ) + A_1 \left( {\frac{{T_1 }}{T}} \right) + A_2 \left( {\frac{{T_1 }}{T}} \right)^2 $$ it becomes a universal solubility equation in the sense that A2 is common to all gases, with T1 and A1 characteristic of the specific gas. Accurate values are presented for the partial molal thermodynamic function changes for the solution of oxygen in water between the usual standard states for the liquid and vapor phases. These include the change in heat capacity, which varies inversely with the square of the absolute temperature and for which the random error is 0.15%. Analysis of the high-temperature data of Stephan et al., in combination with our values from 0–60°C, shows that for oxygen the fourterm series in 1/T, $$\ln k = - 4.1741 + 1.3104 \times 10^4 /T - 3.4170 \times 10^6 /T^2 + 2.4749 \times 10^8 /T^3 $$ where p=kx and p is the partial pressure in atmospheres of the gas, probably provides the best and easiest way presently available to calculate values for k in the range 100–288°C, but more precise measurements at elevated temperatures are needed. The new method permits direct mass spectrometric comparison of the isotopic ratio34O2/32O2 in the dissolved gas to that in the gas above the solution. The fractionation factor α=32k/34k varies from approximately 1.00085 (±0.00002) at 0°C to 1.00055 (±0.00002) at 60°C. Although the results provide the first quantitative determination of α vs. temperature for oxygen, it is not possible from these data to choose among several functions for the variation ofInα with temperature. If the isotopic fractionation is assumed to be due to a difference in the zero-point energy of the two species of oxygen molecules, the size of the solvent cage is calculated to be approximately 2.5 Å. The isotopic measurements indicate that substitution of a34O2 molecule for a32O2 molecule in solution involves a change in enthalpy with a relatively small change in entropy.

Notizen: Synopsis Juvenile bluegill,Lepomis macrochirus, collected from Mississippi coastal drainages were held at 0, 5, and 10% S and fed diets containing 0, 2, and 4% dietary NaCl. Over a 58 day period, fish from each of the nine treatments (salinity x diet) were fed ad libitum twice daily for 5 min. Mean treatment growth rates did not differ when adjusted for initial wet weights. Hematocrit and intestinal Na+/K+-ATPase activity also did not differ. All fish maintained in 0% S had a marginally lower plasma osmolality compared to fish held in 5 and 10% S. Plasma Cl concentration of fish held in 0% S receiving the 0% NaCl diet was lower than that of the other eight treatments. Results indicate that coastal juvenile bluegill can exploit waters up to 10% S while consuming prey items containing up to 4% NaCl with no influence on growth or certain osmoregulatory characteristics.

Notizen: Synopsis Female Gambusia affinis were collected from low salinity/near-neutral pH and tidal freshwater/low pH localities to document life history variation between these two habitats. Mosquito fish were 2.7 times more abundant in low salinity/near-neutral pH (2.37 ± 0.72 ppt; pH = 5.73 ± 0.11) than in tidal freshwater/low pH (0.27 ± 0.19 ppt; pH = 4.46 ± 0.18) habitats in Old Fort Bayou, a black-water tidal river of the Biloxi Bay estuary, Mississippi. Fish were common in both areas from June 1985 through February 1986. There were no significant differences between habitats in the length-weight relationships during the reproductive season with the exception of February. However, there were significant differences in life histories, although the areas were only 4 km apart. Ovarian recrudescence was observed in fish from both areas in February, but ovaries of low salinity fish were more developed than ovaries of freshwater fish. All fish from both areas had regressed ovaries by late September. The monthly slopes of the brood size vs. standard length regressions were significantly different between areas throughout the reproductive season with the exception of June. Although freshwater fish produced heavier tail-free embryos, fish from low salinity had significantly higher GSI values and brood size throughout the reproductive season. These observations suggest that Gambusia affonis may have a greater reproductive effort in low salinity/near-neutral pH environments than in freshwater/low pH habitats.