Biogeochemical interfaces play a key role for retardation and elimination of organic pesticides: (i) as sorption medium for retention; (ii) by harbouring microorganisms that facilitate degradation. Tracing these processes under natural conditions in the absence of mass balances is difficult. Of particular concern are polar and anionic pesticides because they are highly mobile. This proposal aims to provide two important, new contributions towards a better process understanding, each focussed in one Ph.D. project:(1) Measurements of compound-specific 13C and 15N isotope fractionation to investigate pesticide sorption and degradation. We will for the first time (a) measure degradation-associated isotope fractionation for bentazone and MCPA, as a new approach to detecting their transformation in natural systems; (b) use the isotope effect between the neutral and anionic form of bentazone to characterize directly which form (neutral versus ionic) is preferentially retained at geochemical surfaces (pure minerals, artificial and natural soils).(2) Column studies in conjunction with cutting-edge mathematical modelling to assess the role of immobile water on sorption and degradation. We aim to test the hypotheses that (a) surface interactions of pesticides are more pronounced when more of the substances are present in immobile (= stagnant, near-surface) water, and (b) that this proportion is greater under unsaturated conditions. To this end, (i) tracer tests (3H, bromide) at different degrees of water content will quantify the proportions of mobile versus immobile water at different degrees of saturation; (ii) an advanced mathematical model including slow, irreversible sorption, and rapid sorption equilibrium in the immobile water zone will be developed to describe for the first time the influence of immobile water on pesticide sorption and degradation.
DFG Programme
Priority Programmes
