Explanatory Parameter Research Articles

A Comparison of Gas−Hexadecane and Gas−Apolane Partition Coefficients

Gas-apolane partition coefficients (L(87)) of 157 nonpolar and polar organic solutes, spanning a wide range of functional groups, dipolarities, and hydrogen-bonding capabilities, are measured by open tubular capillary gas chromatography at 40 °C. The experimental values compare well (R(2) = 0.999) with literature values of log L(87) from packed-column gas chromatography. The log L(87) values are also compared with gas-hexadecane partition coefficients (log L(16)) at 25 °C. A strong linear relationship exists between log L(87) and log L(16) for all solutes (R(2) = 0.994), as well as for chemically relevant subsets of the data. Therefore, unknown L(16) values at 25 °C can be predicted from the corresponding L(87) values, which can be measured on open-tubular or packed columns at higher temperatures, due to the low volatility of apolane. Predicted values of L(16) would be extremely useful, since log L(16) is often the major explanatory parameter in many linear solvation energy relationships.

Electrochemical studies of Tl(I) crown-ether complexes in nonaqueous media

Complexation equilibria of the Tl(I) ion with 18-crown-6 and dibenzo-18-crown-6 were studied polarographically in 10 nonaqueous solvents. The stability of the complexes is strongly influenced by the nature of solvents and varies with their Lewis basicities. It has been found that the logKs value (Ks is the stability constant of the complex) can be well described by empirical relation logKs=a DN+b, whereDN stands for the Gutmann donor number anda andb mark the regression coefficient. Addition of the second explanatory parameter, the acceptor number, is not statistically significant. This result is in agreement with the predominant role of Tl(I) ion solvation.

Metaux lourds dans les sediments de l'estuaire de la loire

Estuaries, being interfaces between fluviatile and marine environments, are the scene of considerable physico-chemical and biological gradients which can have an effect on the distribution of metallic elements between the solid and dissolved phases. The purpose of the present study was to determine the relative influence of each parameter in this distribution. The study included two series of samples (ICOLO 26 and ICOLO 32) taken by means of the Schipeck grab at 19 selected points of the estuary as indicated in Fig. 1. Within the framework of this study we first investigated and were able to determine the origin and evolution of the metallic elements in the Loire estuary. Pollution level Table 1 and Fig. 2 summarize the results: firstly, the metallic element contents are relatively low, indicating that pollution is not very strong. Secondly, the contents measured in the different samples vary considerably due to the great heterogeneity of sample composition and particle-size distribution. Upstream-downstream evolution Figure 2 shows that the longitudinal profiles for metals are very similar to those obtained for the different characteristics of the sediments. Such an observation has already been made by various authors. Owing to the existence of these relationships, we believe, as do Boust et al. (1981), that it is preferable to interpret the results relative to metals obtained on a given site in terms of the various characteristics of the sediment. In Fig. 3, the metallic element contents (ICOLO 26 samples) is thus plotted against organic carbon. As shown in the figure, there is a very good relationship between the two parameters. Figures 2 and 3 indicate that the contents are uniform throughout the estuary with no evidence of further significant sedimentation this uniformity being due to tidal action. Owing to this uniformity, the impact of significant discharges is highly localized except for the wastewater from the city of Nantes as a whole, whose impact which is felt along the entire estuary. The relationship between copper and volatile matter for the ICOLO 32 samples, as represented in Fig. 4, shows that the points fall into two groups, which are the same whatever the explanatory parameter involved. Though the results are more uniform for the ICOLO 26 than for the ICOLO 32 samples, Fig. 6 clearly shows that the “marine” points stand out in both series of samples. This is indicative of a reduction in contents in the downstream direction, especially noticeable beyond point B (Zn, Cr, Ni) or even M (Cd, Cu, Pb). The seasonal evolution is clearly shown on the “metal-characteristic of sediment” graphs by the comparison of the slopes of the lines linking the same point sampled during the two sampling campaigns. The example of copper is shown in Fig. 7. On the whole, analysis of the results derived from the study of one characteristics of the sediment, indicates that only limited enrichment or depletion occurs at a point over a period of time. This probably reflects a good constancy over time of the metallic flux in the estuary. There is little doubt that changes in the composition of the sediment, will cause changes in the trapping of the metallic flux. In this case, variations in contents do not reflect alterations in the metallic flux over the sediment, but the varying capacity of the sediment under investigation to trap the same polluting flux according to is own composition. This study was also productive in the investigation of the various phenomena responsible for the reduction in metal contents during estuarial transit, which phenomenon can be expected to occur in a large number of estuaries. The impact depends on the chemical properties of the element under investigation. Solubilization of metallic elements due to to increased salinity occurs but plays only a secondary role in the upstream-downstream reductions. This is presumably because of the low percentages of metal absorbed in relation to the total amount of metals associated with the sediments. The reduction in metal contents related to the degradation of organic matter also occurs but it is of little significance compared with the overall phenomenon. The disappearance of metals associated with organic matter could well be related to salinity. The considerable reduction of contents in the lower estuary markedly occurs downstream of the salinity front and precisely where the first sediments characteristic of the marine environment are encountered. Consequently, the most obvious parameter responsible for the reduction in the metallic element contents is the mixing of relatively laden fluviatile sediment with “clean” marine sediments.