We investigated environmental, landscape, and microbial factors that could structure the spatiotemporal variability in the nontarget chemical composition of four riverine systems in the Oregon Coast Range, USA. We hypothesized that the nontarget chemical composition in river water would be structured by broad-scale landscape gradients in each watershed. Instead, only a weak relationship existed between the nontarget chemical composition and land cover gradients. Overall, the effects of microbial communities and environmental variables on chemical composition were nearly twice as large as those of the landscape, and much of the influence of environmental variables on the chemical composition was mediated through the microbial community (i.e., environment affects microbes, which affect chemicals). Therefore, we found little evidence to support our hypothesis that chemical spatiotemporal variability was related to broad-scale landscape gradients. Instead, we found qualitative and quantitative evidence to suggest that chemical spatiotemporal variability of these rivers is controlled by changes in microbial and seasonal hydrologic processes. While the contributions of discrete chemical sources are undeniable, water chemistry is undoubtedly impacted by broad-scale continuous sources. Our results suggest that diagnostic chemical signatures can be developed to monitor ecosystem processes, which are otherwise challenging or impossible to study with existing off-the-shelf sensors.
Keywords: chemical forensics; environmental gradient; freshwater microbial communities; multivariate analysis; nontarget chemical analysis; source attribution; spatiotemporal trend analysis; watershed analysis.