Steady-state concentration profile, trace

The quantity and quality of experimental information determined by the new techniques call for the use of comprehensive data treatment and evaluation methods. In earlier literature, quite often kinetic studies were simplified by using pseudo-first-order conditions, the steady-state approach or initial rate methods. In some cases, these simplifications were fully justified but sometimes the approximations led to distorted results. Autoxidation reactions are particularly vulnerable to this problem because of strong kinetic coupling between the individual steps and feed-back reactions. It was demonstrated in many cases, that these reactions are very sensitive to the conditions applied and their kinetic profiles and stoichiometries may be significantly altered by changing the pH, the absolute concentrations and concentration ratios of the reactants, and also by the presence of trace amounts of impurities which may act either as catalysts and/or inhibitors. 

Simple steady-state models can only predict mean concentrations. Seasonal variations and concentration depth profiles in the water column of lakes give further insight into the mechanisms governing the removal of metal ions. Data on depth concentration profiles of trace metals in lakes are however still scarce (Sigg, 1985 Sigg et al., 1983 Murray, 1987). In a similar way as in the oceans, it might be expected to observe in lakes different types of profiles for different elements, depending on the predominant removal mechanism (Murray, 1987 Whitfield and Turner, 1987). 

The relationships between particle flux, trace element flux and trace element concentration in sediment are more complicated in deep lakes. In a deep lake, there may be a significant proportion of dissolved element held in the water column. If the water column dissolved element inventory approaches the magnitude of the annual flux for that element, then a steady state model is invalid. Instead, the dynamic model outlined in Figure 7 must be used to allow for the time delay in the response of the sediment to changes in trace element supply rate. The disadvantage of this, compared with the steady state sitnation, is that an observed trace element concentration profile does not lead back to a nniqne trace element supply history. However, a trace element snpply history does lead to a definite trace element concentration profile, so it is possible to see if any particular supply history is compatible with the observed concentration data. A practical example of this from Lake Baikal is shown in Boyle et al. (1998), where the exceptional water depth makes this effect particularly strong. 

The use of SECM to probe homogeneous reaction kinetics can be traced to the earliest applications of UMEs to profile concentration gradients at macroscopic (millimeter-sized) electrodes. There has been considerable progress subsequently, such that short-lived intermediates, in electrode reactions, can readily be identified by SECM under steady-state conditions, that would be difficult to characterize by alternative transient UME methods, such as fast scan cyclic voltammetry (FSCV). 2... 

---