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Trace metals associated with nanoparticles are known to possess reactivities that are different from their larger-size counterparts. However, the relative importance of small relative to large particles for the overall distribution and biouptake of these metals is not as well studied in complex environmental systems. Here, we have examined differences in the long term fate and transport of ceria (CeO) nanoparticles of two different sizes (3.8 vs 185 nm), dosed weekly to freshwater wetland mesocosms over 9 months. While the majority of CeO particles were detected in soils and sediments at the end of nine months, there were significant differences observed in fate, distribution, and transport mechanisms between the two materials. Small nanoparticles were removed from the water column primarily through heteroaggregation with suspended solids and plants, while large nanoparticles were removed primarily by sedimentation. A greater fraction of small particles remained in the upper floc layers of sediment relative to the large particles (31% vs 7%). Cerium from the small particles were also significantly more bioavailable to aquatic plants (2% vs 0.5%), snails (44 vs 2.6 ng), and insects (8 vs 0.07 μg). Small CeO particles were also significantly reduced from Ce(IV) to Ce(III), while aquatic sediments were a sink for untransformed large nanoparticles. These results demonstrate that trace metals originating from nanoscale materials have much greater potential than their larger counterparts to distribute throughout multiple compartments of a complex aquatic ecosystem and contribute to the overall bioavailable pool of the metal for biouptake and trophic transfer.

Despite the rapid rise in diversity and quantities of engineered nanomaterials produced, the impacts of these emerging contaminants on the structure and function of ecosystems have received little attention from ecologists. Moreover, little is known about how manufactured nanomaterials may interact with nutrient pollution in altering ecosystem productivity, despite the recognition that eutrophication is the primary water quality issue in freshwater ecosystems worldwide. In this study, we asked two main questions: (1) To what extent do manufactured nanoparticles affect the biomass and productivity of primary producers in wetland ecosystems? (2) How are these impacts mediated by nutrient pollution? To address these questions, we examined the impacts of a citrate-coated gold nanoparticle (AuNPs) and of a commercial pesticide containing Cu(OH) nanoparticles (CuNPs) on aquatic primary producers under both ambient and enriched nutrient conditions. Wetland mesocosms were exposed repeatedly with low concentrations of nanoparticles and nutrients over the course of a 9-month experiment in an effort to replicate realistic field exposure scenarios. In the absence of nutrient enrichment, there were no persistent effects of AuNPs or CuNPs on primary producers or ecosystem productivity. However, when combined with nutrient enrichment, both NPs intensified eutrophication. When either of these NPs were added in combination with nutrients, algal blooms persisted for >50 d longer than in the nutrient-only treatment. In the AuNP treatment, this shift from clear waters to turbid waters led to large declines in both macrophyte growth and rates of ecosystem gross primary productivity (average reduction of 52% ± 6% and 92% ± 5%, respectively) during the summer. Our results suggest that nutrient status greatly influences the ecosystem-scale impact of two emerging contaminants and that synthetic chemicals may be playing an under-appreciated role in the global trends of increasing eutrophication. We provide evidence here that chronic exposure to Au and Cu(OH) nanoparticles at low concentrations can intensify eutrophication of wetlands and promote the occurrence of algal blooms.

Summary Trait‐based approaches offer a way to predict changes in community structure along environmental gradients using measurable properties of individuals. Promoted as being generalizable across systems, trait‐based approaches benefit from information about the environmental drivers of trait variation, how they interact and how they change with scale. However, for most diverse, natural communities, it is largely unknown whether the relationships between leaf‐level traits and interacting environmental drivers (e.g. fire, water availability) are influenced by the scale of trait aggregation. We show that landscape‐level differences in community composition in a diverse, fire‐dependent pine savanna are explained by a small subset of species groups that are strongly correlated with soil moisture and elevation, but are insensitive to the time since the last fire. We used a trait‐based approach to show that significant variation in the community‐weighted mean (CWM) of specific leaf area (SLA) and leaf dry matter content (LDMC), two traits known to drive community structure and function, was explained by a small set of factors including the time since the last fire, soil moisture, precipitation and Shannon diversity. We show that statistical inference about the environmental drivers of community traits is radically altered when using CWMs computed with landscape‐level rather than plot‐level means, even over modest spatial scales. Synthesis: Environmental drivers of community composition across the landscape differed from those explaining trait composition. CWM traits were strongly influenced by interactions between drivers. Fire, in particular, strongly mediated the effect of other environmental variables on LDMC, showing that strong environmental gradients cannot be considered independently when assessing their effects on functional traits. The importance of environmental variables such as fire was lost when using landscape‐level trait means, highlighting the importance of local trait variation. This suggests caution when using traits from distant populations to make inferences about local processes, especially across strong gradients.

The exposure of freshwater-dependent coastal ecosystems to saltwater is a present-day impact of climate and land-use changes in many coastal regions, with the potential to harm freshwater and terrestrial biota, alter biogeochemical cycles and reduce agricultural yields. Land-use activities associated with artificial drainage infrastructure (canals, ditches, and drains) could exacerbate saltwater exposure. However, studies assessing the effects of artificial drainage on the vulnerability of coastal landscapes to saltwater exposure are lacking. We examined the extent to which artificial drainage infrastructure has altered the potential for saltwater intrusion in the coastal plain of eastern North Carolina. Regional spatial analyses demonstrate that artificial drainages not only lower the overall elevation in coastal landscapes, but they also alter the routing and concentration of hydrological flows. Together, these factors have the potential to increase the total proportion of the landscape vulnerable to saltwater intrusion, not only in areas adjacent to drainage infrastructure but also in places where no artificial drainages exist due to large scale effects of flow rerouting. Among all land cover types in eastern North Carolina, wetlands are most vulnerable to saltwater exposure. Droughts and coastal storms associated with climate change potentially exacerbate vulnerability to saltwater facilitated by artificial drainage.

The environmental fate and potential impacts of nanopesticides on agroecosystems under realistic agricultural conditions are poorly understood. As a result, the benefits and risks of these novel formulations compared to the conventional products are currently unclear. Here, we examined the effects of repeated realistic exposures of the Cu(OH)2 nanopesticide, Kocide 3000, on simulated agricultural pastureland in an outdoor mesocosm experiment over 1 year. The Kocide applications were performed alongside three different mineral fertilization levels (Ambient, Low, and High) to assess the environmental impacts of this nanopesticide under low-input or conventional farming scenarios. The effects of Kocide over time were monitored on forage biomass, plant mineral nutrient content, plant-associated non-target microorganisms (i.e., N-fixing bacteria or mycorrhizal fungi) and six soil microbial enzyme activities. We observed that three sequential Kocide applications had no negative effects on forage biomass, root mycorrhizal colonization or soil nitrogen fixation rates. In the Low and High fertilization treatments, we observed a significant increase in aboveground plant biomass after the second Kocide exposure (+14% and +27%, respectively). Soil microbial enzyme activities were significantly reduced in the short-term after the first exposure (day 15) in the Ambient (-28% to -82%) and Low fertilization (-25% to -47%) but not in the High fertilization treatment. However, 2 months later, enzyme activities were similar across treatments and were either unresponsive or responded positively to subsequent Kocide additions. There appeared to be some long-term effects of Kocide exposure, as 6 months after the last Kocide exposure (day 365), both beta-glucosidase (-57% in Ambient and -40% in High fertilization) and phosphatase activities (-47% in Ambient fertilization) were significantly reduced in the mesocosms exposed to the nanopesticide. These results suggest that when used in conventional farming with high fertilization rates, Kocide applications did not lead to marked adverse effects on forage biomass production and key plant–microorganism interactions over a growing season. However, in the context of low-input organic farming for which this nanopesticide is approved, Kocide applications may have some unintended detrimental effects on microbially mediated soil processes involved in carbon and phosphorus cycling.

Freshwater ecosystems are exposed to engineered nanoparticles through municipal and industrial wastewater-effluent discharges and agricultural nonpoint source runoff. Because previous work has shown that engineered nanoparticles from these sources can accumulate in freshwater algal assemblages, we hypothesized that nanoparticles may affect the biology of primary consumers by altering the processing of two critical nutrients associated with growth and survivorship, nitrogen and phosphorus. We tested this hypothesis by measuring the excretion rates of nitrogen and phosphorus of Physella acuta, a ubiquitous pulmonate snail that grazes heavily on periphyton, exposed to either copper or gold engineered nanoparticles for 6 months in an outdoor wetland mesocosm experiment. Chronic nanoparticle exposure doubled nutrient excretion when compared to the control. Gold nanoparticles increased nitrogen and phosphorus excretion rates more than copper nanoparticles, but overall, both nanoparticles led to higher consumer excretion, despite contrasting particle stability and physiochemical properties. Snails in mesocosms enriched with nitrogen and phosphorus had overall higher excretion rates than ones in ambient (no nutrients added) mesocosms. Stimulation patterns were different between nitrogen and phosphorus excretion, which could have implications for the resulting nutrient ratio in the water column. These results suggest that low concentrations of engineered nanoparticles could alter the metabolism of consumers and increase consumer-mediated nutrient recycling rates, potentially intensifying eutrophication in aquatic systems, for example, the increased persistence of algal blooms as observed in our mesocosm experiment.

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