Evaluating the performance of diffusive gradients in thin films for predicting Ni sediment toxicity

Diffusive gradients in thin films (DGTs) rapidly measure labile fractions of metal and are promoted as an assessment tool for bioavailability. Using macroinvertebrate community composition as a response, this study compared the predictive ability of DGT-measured Ni with acid volatile sulfide (AVS) and organic carbon (OC) corrected Ni [(SEM(Ni)-AVS)/f(OC)] and total Ni concentrations. In two experiments, sediments were amended with Ni and placed within either a streamside mesocosm or deployed in situ. DGT-measured Ni concentrations (C(DGT)) increased with increasing total Ni, were greater at depth, and decreased over time. Relationships between Ni C(DGT) and sediment geochemistry indicated a shift in Ni partitioning from AVS-bound to Fe- and Mn-associated Ni. In both experiments, DGT-measured Ni poorly predicted the invertebrate response to metal, whereas models that included total Ni or (SEM(Ni)-AVS)/f(OC) effectively predicted the invertebrate response for the streamside mesocosm and in situ experiments, respectively. C(DGT) overestimated the available Ni fraction, possibly due to sampling either nonbioavailable solid-phase Ni or Ni irrespective of cations competing at the biotic ligand. We suggest that C(DGT) cannot replace (SEM(Ni)-AVS)/f(OC) for predicting invertebrate response to sediment Ni, and greater understanding of metal species lability to DGTs is needed before assuming equivalence between bioavailable and DGT-labile metals in sediments.