Wildfires produce large amounts of pyrogenic carbon (PyC), including charcoal, known for its chemical recalcitrance and sorption affinity for organic molecules. Wildfire-derived PyC can be transported to fluvial networks. Here it may alter dissolved organic matter (DOM) concentration and composition as well as microbial biofilm functioning. Effects of PyC on carbon cycling in freshwater ecosystems remain poorly investigated. Employing in-stream flumes with a control vs treatment design (PyC pulse addition), we present evidence that field-aged PyC inputs to rivers can increase dissolved organic carbon (DOC) concentration, and alter DOM composition. DOM fluorescence components were not affected by PyC. In-stream DOM composition was altered due to leaching of pyrogenic DOM from PyC and possibly concurrent sorption of riverine DOM to PyC. Decreased DOM aromaticity indicated by lower SUVA245 (-0.31 units), and higher pH (0.25 units) were associated with changes in enzymatic activities in benthic biofilms, including a lower recalcitrance index (β-glucosidase/phenol oxidase), suggesting preferential usage of recalcitrant over easily available DOM by biofilms. Particulate PyC deposition onto biofilms may further modulate the impacts of PyC due to direct contact with the biofilm matrix. This study highlights the importance of PyC for in-stream biogeochemical organic matter cycling in fire-affected watersheds.
KeywordsCharcoal, black carbon, dissolved organic carbon, dissolved organic matter, biofilm functioning analyze effects of PyC on in-stream biofilm enzymatic activities. We hypothesized that PyC would affect (i) in-stream DOM composition and DOC concentration due to sorption of riverine DOM and leaching of pyrogenic DOM leading to a net increase in DOC concentration, and (ii) microbial functions, measured via enzymatic activities by altering substrate composition and pH.
Methods
Site description and field experimental designThis study was carried out at the Austrian river Kleine Ysper (lat 48.218N, long 15.023E), a tributary of the Ysper with a slope of 3.3 cm/m, an average width of 5.47 m ± 1.44, an upstream catchment area of 68.30 km² at a site situated about 4 km upstream of the confluence with the Danube. This site was selected because the land use in its catchment area is dominated by mixed forest and semi-natural areas which are widespread in the region, and the site has already been characterized in a previous study. 27 To our knowledge there are no recorded wildfire occurrences in the upstream catchment area, making this a pristine site for the experiment. Atmospheric PyC inputs are possible, but we found no evidence thereof. The used PyC was selected as a proxy for forest fire-derived PyC. The PyC was charcoal consisting of fully charred woody material from Pinus sylvestris, collected from the ground as pieces with a radius of 0.5 -2.5 cm one year after an extensive wildfire in a pine forest (Karbole, Sweden). This charcoal was produced at an estimated maximum temperature of 800 °C and a charring duration of...