Isotopically exchangeable cadmium and zinc ('E values') were measured on so
ils historically contaminated by sewage sludge and ones on zinc-rich mine s
poil. The E-value assay involves determining the distribution of an added m
etal isotope, e.g. Cd-109, between the solid and solution phases of a soil
suspension. The E values for both metals were found to be robust to changes
in the position of the metal solid double left right arrow solution equili
brium, even though the concentration of dissolved metal varied substantiall
y with electrolyte composition and soil:solution ratio. Concentration of la
bile metal was also invariant over isotope equilibration times of 2-6 days.
The use of a submicron filtration procedure, in addition to centrifuging a
t 2200 g, proved unnecessary if 0.1 M Ca electrolyte was used to suspend th
e soils.
The proportion of 'fixed' metal, in non-labile forms, apparently increased
with increasing pH, although there was considerable variation in both sets
of contaminated soil. Zinc and cadmium in the sludged soils were similarly
labile. Several possible methods for the measurement of chemically reactive
metal were explored for comparison with E values, including single extract
ion with 1 M CaCl2 and a 'pool depletion' (PD) method. The latter involves
comparing solid double left right arrow solution metal equilibria in two el
ectrolytes with differing degrees of (solution) complex formation, 0.1 M Ca
(NO3)(2) and CaCl2. Both the single extraction and the PD method gave good
estimates of E value for Cd, although the single extraction was more consis
tent. Neither technique was a useful substitute for determining labile Zn,
because of weak chloro-complexation of Zn2+. We therefore suggest that 1 M
CaCl2 extraction of Cd alone be used as an alternative to E values to avoid
the inconvenience of isotopic dilution procedures.