Surface water samples were collected from 43 streams distributed throughout watersheds of mixed land use in southern Ontario, Canada. Absorbance and fluorescence spectroscopy with parallel factor analysis (PARAFAC) was used to characterize dissolved organic matter (DOM). DOM characteristics were related to environmental variables, microbial activity indicators (bacterial production and extracellular leucine aminopeptidase activity), and riparian land use to understand better how these factors influence DOM in streams. PARAFAC produced a six-component model (C1 to C6). Temperature correlated with each PARAFAC component, suggesting that water source, drainage area, and light penetration broadly affected DOM characteristics. C1 and C2 represented terrestrial, humic-like DOM fluorophore groups and comprised 41-65% of stream DOM fluorescence. C5, a tryptophan-like component, related negatively to a humification index but positively to leucine-aminopeptidase activity and recently produced DOM, suggesting that C5 consisted of autochthonous, microbially produced DOM. C3, C4, and C6 showed signs of quinone-like, humic-like, and microbial transformable fluorophores. The distribution of these potentially redox-active PARAFAC components indicated that DOM was in a more reduced state in streams with higher bacterial production and agricultural land use than in streams with increased wetlands area, which had greater relative abundance of the oxidized quinone-like component. Anthropogenic land use and microbial activity altered the quantity and quality of DOM exported from human-affected streams from that observed in forest-and wetland-dominated streams. DOM in agriculturally affected streams was likely more labile and accessible to the microbial community than DOM in wetland streams, which supported low rates of microbial activity.

Dissolved organic matter (DOM) composition in freshwater ecosystems is influenced by the interactions among physical, chemical, and biological processes that are controlled, at one level, by watershed landscape, hydrology, and their connections. Against this environmental template, humans may strongly influence DOM composition. Yet, we lack a comprehensive understanding of DOM composition variation across freshwater ecosystems differentially affected by human activity. Using optical properties, we described DOM variation across five ecosystem groups of the Laurentian Great Lakes region: large lakes, Kawartha Lakes, Experimental Lakes Area, urban stormwater ponds, and rivers (n = 184 sites). We determined how between ecosystem variation in DOM composition related to watershed size, land use and cover, water quality measures (conductivity, dissolved organic carbon (DOC), nutrient concentration, chlorophyll a), and human population density. The five freshwater ecosystem groups had distinctive DOM composition from each other. These significant differences were not explained completely through differences in watershed size nor spatial autocorrelation. Instead, multivariate partial least squares regression showed that DOM composition was related to differences in human impact across freshwater ecosystems. In particular, urban/developed watersheds with higher human population densities had a unique DOM composition with a clear anthropogenic influence that was distinct from DOM composition in natural land cover and/or agricultural watersheds. This nonagricultural, human developed impact on aquatic DOM was most evident through increased levels of a microbial, humic-like parallel factor analysis component (C6). Lotic and lentic ecosystems with low human population densities had DOM compositions more typical of clear water to humic-rich freshwater ecosystems but C6 was only present at trace to background levels. Consequently, humans are strongly altering the quality of DOM in waters nearby or flowing through highly populated areas, which may alter carbon cycles in anthropogenically disturbed ecosystems at broad scales.

Urban stormwater ponds are considered to be a best management practice for flood control and the protection of downstream aquatic ecosystems from excess suspended solids and other contaminants. Following this, urban ponds are assumed to operate as unreactive settling basins, whereby their overall effectiveness in water treatment is strictly controlled by physical processes. However, pelagic microbial biogeochemical dynamics could be significant contributors to nutrient and carbon cycling in these small, constructed aquatic systems. In the present study, we examined pelagic biogeochemical dynamics in 26 stormwater ponds located in southern Ontario, Canada, during late summer. Initially, we tested to see if total suspended solids (TSS) concentration, which provides a measure of catchment disturbance, landscape stability, and pond performance, could be used as an indirect predictor of plankton stocks in stormwater ponds. Structural equation modeling (SEM) using TSS as a surrogate for external loading suggested that TSS was an imperfect predictor. TSS masked plankton-nutrient relationships and appeared to reflect autochthonous production moreso than external forces. When TSS was excluded, the SEM model explained a large amount of the variation in dissolved organic matter (DOM) characteristics (55-75%) but a small amount of the variation in plankton stocks (3-38%). Plankton stocks were correlated positively with particulate nutrients and extracellular enzyme activities, suggesting rapid recycling of the fixed nutrient and carbon pool with consequential effects on DOM. DOM characteristics across the ponds were mainly of autochthonous origin. Humic matter from the watershed formed a larger part of the DOM pool only in ponds with low productivity and low dissolved organic carbon concentrations. Our results suggest that in these small, high nutrient systems internal processes might outweigh the impact of the landscape on carbon cycles. Hence, the overall benefit that constructed ponds serve to protect downstream environments must be weighed with the biogeochemical processes that take place within the water body, which could offset pond water quality gains by supporting intense microbial metabolism. Finally, TSS did not provide a useful indication of stormwater pond biogeochemistry and was biased by autochthonous production, which could lead to erroneous TSS-based management conclusions regarding pond performance.

Silver nanoparticles (AgNPs) may be introduced into aquatic ecosystems because of their widespread use as antimicrobial agents. However, few studies have investigated the impacts of AgNPs on natural aquatic microbial activity in an environmentally relevant context. In this study, bacterioplankton were collected from nine aquatic habitats and exposed to six concentrations of carboxy-functionalized AgNP (ViveNano, 10-nm particle size, 20% Ag w/w) over 48 h. After 1 h of exposure, bacterial production and extracellular alkaline phosphatase affinity were significantly reduced in all AgNP-exposed samples. However, across a 48-h exposure, extracellular aminopeptidase affinity was not consistently impacted by AgNPs. After 48 h, bacterial production recovered by 40 to 250% at low AgNP nominal concentrations (0.05 and 0.1 mg/L) but remained inhibited at the two highest AgNP nominal concentrations (1 and 10 mg/L). In contrast, AgNO(3) additions between 0.01 to 2 mg Ag/L fully inhibited bacterial production over the 48-h exposure. At 48-h exposure, the lowest observed effective concentrations and average median effective concentration for bacterial production ranged from 8 to 66 and 15 to 276 µg Ag/L, respectively. Thus, in natural aquatic systems, AgNP concentrations in the nanogram per liter range are unlikely to negatively impact aquatic biogeochemical cycles. Instead, exposures in the low microgram per liter range would likely be required to negatively impact natural aquatic bacterioplankton processes.

Dissolved organic matter (DOM) is recognized for its importance in freshwater ecosystems, but historical reliance on DOM quantity rather than indicators of DOM composition has led to an incomplete understanding of DOM and an underestimation of its role and importance in biogeochemical processes. A single sample of DOM can be composed of tens of thousands of distinct molecules. Each of these unique DOM molecules has their own chemical properties and reactivity or role in the environment. Human activities can modify DOM composition and recent research has uncovered distinct DOM pools laced with human markers and footprints. Here we review how land use change, climate change, nutrient pollution, browning, wildfires, and dams can change DOM composition which in turn will affect internal processing of freshwater DOM. We then describe how human-modified DOM can affect biogeochemical processes. Drought, wildfires, cultivated land use, eutrophication, climate change driven permafrost thaw, and other human stressors can shift the composition of DOM in freshwater ecosystems increasing the relative contribution of microbial-like and aliphatic components. In contrast, increases in precipitation may shift DOM towards more relatively humic-rich, allochthonous forms of DOM. These shifts in DOM pools will likely have highly contrasting effects on carbon outgassing and burial, nutrient cycles, ecosystem metabolism, metal toxicity, and the treatments needed to produce clean drinking water. A deeper understanding of the links between the chemical properties of DOM and biogeochemical dynamics can help to address important future environmental issues, such as the transfer of organic contaminants through food webs, alterations to nitrogen cycling, impacts on drinking water quality, and biogeochemical effects of global climate change.