Elements with conservative behaviour

Thallium (Tl), which appears to exhibit conservative behaviour in seawater, has two potential oxidation states. As Tl1, thallium is very weakly complexed in solution. In contrast, Tl111 should be strongly hydrolysed in solution ([T13+]/[T13+]t — 10 20 5) with Tl(OH)3 as the dominant species over a very wide range of pH. The calculation of Turner et at. (1981) indicated thatTl111 is the thermodynamically favoured oxidation state at pH 8.2. Lower pH and p()2 would be favourable to Tl1 formation. Within the water column, pH can be considerably less than 8.2 and /)( )2 lower than 0.20 atm. In view of these factors, and the observation that redox disequilibrium in seawater is not uncommon, the oxidation state of Tl in seawater is somewhat uncertain. The existence of Tl in solution as Tl+, a very weakly interactive ion, would reasonably explain the conservative behaviour of Tl in seawater. However, the extremely strong solution complexation of Tl3+ suggests that Tl3+ may be substantially less particle reactive than other Group 13 elements (with the exception of boron). 

The major constituents in seawater are conventionally taken to be those elements present in typical oceanic water of salinity 35 that have a concentration greater than 1 mg kg excluding Si, which is an important nutrient in the marine environment. The concentrations and main species of these elements are presented in Table 1. One of the most significant observations from the Challenger expedition of 1872-1876 was that these major components existed in constant relative amounts. As already explained, this feature was exploited for salinity determinations. Inter-element ratios are generally constant, and often expressed as a ratio to Cl%o as shown in Table 1. This implies conservative behaviour, with concentrations depending solely upon mixing processes, and indeed, salinity itself is a conservative index. 

Not all the major constituents consistently exhibit conservative behaviour in the ocean. The most notable departures occur in deepwaters, where Ca and HCO3 exhibit anomalously high concentrations due to the dissolution of calcite. The concept of relative constant composition does not apply in a number of atypical environments associated with boundary regions. Inter-element ratios for major constituents can be quite different in estuaries and near hydrothermal vents. Obviously, these are not solutions of sea salt with the implication that accuracy of salinity measurements by chemical and conductometric means is limited. 

The distributions of Group 17 elements (Fig. 12.12) are most closely comparable to those of the weakly interactive Group 1 elements. F, Cl and Br are conservative elements. The halides interact strongly with a number of Periods 4 and 5 metals between Groups 8 and 15. However, these metals have seawater concentrations very much lower than H, Br, Cl- and F and, thereby, do not significantly influence the distribution and chemical behaviour of the latter elements. 

The prepreg fibre bed is typically assumed to be an elastic porous medium with incompressible and inextensible fibres and fully saturated with the resin. The resin is assumed to flow in the pores between the fibres, and the fibre mass in the laminate remains constant during cure. The governing equations of the system must describe the behaviour of the composite constituents the fibre bed and the resin. Firstly, the equilibrium of forces on the representative element is considered. Secondly, the mass conservation for the representative element must be satisfied. For a porous medium saturated with a single phase fluid, the total stress tensor a,) is separated into two parts as (tensile stresses are considered positive) ... 

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