The effects of aquatic contaminants are propagated across ecosystem boundaries by aquatic insects that export resources and contaminants to terrestrial food webs; however, the mechanisms driving these effects are poorly understood. We examined how emergence, contaminant concentration, and total contaminant flux by adult aquatic insects changed over a gradient of bioavailable metals in streams and how these changes affected riparian web-building spiders. Insect emergence decreased 97% over the metal gradient, whereas metal concentrations in adult insects changed relatively little. As a result, total metal exported by insects (flux) was lowest at the most contaminated streams, declining 96% among sites. Spiders were affected by the decrease in prey biomass, but not by metal exposure or metal flux to land in aquatic prey. Aquatic insects are increasingly thought to increase exposure of terrestrial consumers to aquatic contaminants, but stream metals reduce contaminant flux to riparian consumers by strongly impacting the resource linkage. Our results demonstrate the importance of understanding the contaminant-specific effects of aquatic pollutants on adult insect emergence and contaminant accumulation in adults to predict impacts on terrestrial food webs.

Insects are integral to most freshwater and terrestrial food webs, but due to their accumulation of environmental pollutants they are also contaminant vectors that threaten reproduction, development, and survival of consumers. Metamorphosis from larvae to adult can cause large chemical changes in insects, altering contaminant concentrations and fractionation of chemical tracers used to establish contaminant biomagnification in food webs, but no framework exists for predicting and managing these effects. We analyzed data from 39 studies of 68 analytes (stable isotopes and contaminants), and found that metamorphosis effects varied greatly. δ(15)N, widely used to estimate relative trophic position in biomagnification studies, was enriched by ∼ 1‰ during metamorphosis, while δ(13)C used to estimate diet, was similar in larvae and adults. Metals and polycyclic aromatic hydrocarbons (PAHs) were predominantly lost during metamorphosis leading to ∼ 2 to 125-fold higher larval concentrations and higher exposure risks for predators of larvae compared to predators of adults. In contrast, manufactured organic contaminants (such as polychlorinated biphenyls) were retained and concentrated in adults, causing up to ∼ 3-fold higher adult concentrations and higher exposure risks to predators of adult insects. Both food web studies and contaminant management and mitigation strategies need to consider how metamorphosis affects the movement of materials between habitats and ecosystems, with special regard for aquatic-terrestrial linkages.

Mountain terrestrial and aquatic ecosystems are responsive to external drivers of change, especially climate change and atmospheric deposition of nitrogen (N). We explored the consequences of a temperature-warming trend on stream nitrate in an alpine and subalpine watershed in the Colorado Front Range that has long been the recipient of elevated atmospheric N deposition. Mean annual stream nitrate concentrations since 2000 are higher by 50% than an earlier monitoring period of 1991-1999. Mean annual N export increased by 28% from 2.03 kg N ha À1 yr À1 before 2000 to 2.84 kg N ha À1 yr À1 in Loch Vale watershed since 2000. The substantial increase in N export comes as a surprise, since mean wet atmospheric N deposition from 1991 to 2006 (3.06 kg N ha À1 yr À1 ) did not increase. There has been a period of below average precipitation from 2000 to 2006 and a steady increase in summer and fall temperatures of 0.12 1C yr À1 in both seasons since 1991. Nitrate concentrations, as well as the weathering products calcium and sulfate, were higher for the period 2000-2006 in rock glacier meltwater at the top of the watershed above the influence of alpine and subalpine vegetation and soils. We conclude the observed recent N increases in Loch Vale are the result of warmer summer and fall mean temperatures that are melting ice in glaciers and rock glaciers. This, in turn, has exposed sediments from which N produced by nitrification can be flushed. We suggest a water quality threshold may have been crossed around 2000. The phenomenon observed in Loch Vale may be indicative of N release from ice features such as rock glaciers worldwide as mountain glaciers retreat.