Hickie, Brendan E

The potential release of nanoparticles into aquatic environments is raising global concerns. As antimicrobials, silver nanoparticles (AgNPs) are among the most prominent form in use. Despite this, their fate, long-term toxicity, and ecological relevance have yet to be investigated largely under natural settings with seasonality and environmental complexity. To better understand the environmental significance, we released AgNPs into Lake 222 at the Experimental Lakes Area over two years. AgNPs remained suspended in the water column and were detected throughout the lake and in the lower food web. Total Ag concentrations ranged from below 0.07 to 18.9 μg L-1 in lake water, and were highly dynamic seasonally both in the epilimnion and hypolimnion depending on the physical, chemical and biological conditions of the lake. Approximately 60% of the measured Ag mass in October was present in the sediment in 2014 and 50% in 2015 demonstrating relatively high sedimentation and removal from the water column. During winter months, Ag was largely absent in the water column under the ice. After ice melt and before summer stratification, Ag concentrations increased in the lake suggesting AgNPs may not be tightly bound to the sediment and are able re-enter the water column during spring mixing events. Despite temporal variation, total Ag was highly synchronous across spatial locations for both years, indicating rapid dispersal upon lake entry. When investigating AgNP sizes using spICPMS, size distributions were similar across spatial locations, with the 40-60 nm size class constituting approximately 60% of all particles identified. Large aggregates (>100 nm) and dissolved Ag were infrequently detected within the lake. Ag accumulated in the lower food web ranging from 0.27-16.82 μg Ag mg C-1 in the bacterioplankton and 0.17-6.45 μg Ag mg C-1 in algae (particulate fraction). Partial least squares models revealed the highest predictors of Ag accumulation were dissolved nutrients including DOC, TDN, TDP in bacterioplankton. Major predictors for particulate Ag included temperature, dissolved oxygen, and sampling date. The diversity of predictors among biological compartments emphasizes the importance of understanding the role of environmental complexity within the lower food web. Despite Ag accumulation we did not detect strong negative effects on the lake food web. An increase in particulate and bacterioplankton chlorophyll-a occurred after addition in contrast to reference lakes, which may indicate a hormetic response to low dose AgNP concentrations. Our findings provide the first whole-lake perspective regarding Ag fate and toxicity, suggesting small scale experiments may overestimate environmental

responses.

Author Keywords: Ecotoxicity, Fate, Lower food web, Silver Nanoparticles, Whole-lake addition