Evidence for bioavailable copper-dissolved organic matter complexes and transiently increased copper bioavailability in manure-amended soils as determined by bioluminescent bacterial biosensors

The short-term (3 months) dynamics of bioavailable copper (Cu) species was determined in soils amended with various amounts of manure and Cu. Bioavailable Cu species were operationally defined as those species that were able to induce gene expression in a Cu-specific Pseudomonas fluorescens biosensor. Biosensor measurements were backed by analysis of total Cu in soil and of total Cu and free CU2+ ion activity in solution. Cu bioavailability relative to the total Cu concentration increased dramatically with increasing Cu loading of manure and with increasing manure amendment to soil. In both cases, the immediate increase in bioavailability could be explained in part by increased Cu concentration in solution and in part by an increased bioavailability of dissolved Cu species. In contrast to Cu bioavailability, Cu2+ ion activity decreased progressively with increasing manure loading. Cu bioavailability declined rapidly during the weeks after manure amendment concomitant with a marked slow-down of C mineralization indicating a shift from initially bioavailable Cu-dissolved organic matter (Cu-DOM) complexes to nonavailable Cu-DOM complexes over time. Our data do not support the conventional view of metal bioavailability being primarily related to the free metal ion activity and strongly suggest differential bioavailability of Cu-DOM complexes in manure-amended soils.