Organic Matter Accumulation and Hydrology as Drivers of Greenhouse Gas Dynamics in Newly Developed Artificial Channels.

Artificial channels, common features of inland waters, have been suggested as significant contributors to methane (CH4) and carbon dioxide (CO2) dynamics and emissions; however, the magnitude and drivers of their CH4 and CO2 emissions (diffusive and ebullitive) remain unclear. They are characterized by reduced flow compared to the donor river, which results in suspended organic matter (OM) accumulation. We propose that in such systems hydrological controls will be reduced and OM accumulation will control emissions by promoting methane production and outgassing. Here, we monitored summertime CH4 and CO2 concentrations and emissions on six newly constructed river-fed artificial channels, from bare riparian mineral soil to lotic channels, under two distinct flow regimes. Chamber-based fluxes were complemented with hydrology, total fluxes (diffusion + ebullition), and suspended OM accumulation assessments. During the first 6 weeks after the flooding, inflowing riverine water dominated the emissions over in-channel contributions. Afterwards, a substantial accumulation of riverine suspended OM (≥50% of the channel's volume) boosted in-channel methane production and led to widespread ebullition 10× higher than diffusive fluxes, regardless of the flow regime. Our finding suggests ebullition as a dominant pathway in these anthropogenic systems, and thus, their impact on regional methane emissions might have been largely underestimated.

Emerging Midges Transport Pesticides from Aquatic to Terrestrial Ecosystems: Importance of Compound- and Organism-Specific Parameters.

Emerging aquatic insects have the potential to retain aquatic contaminants after metamorphosis, potentially transporting them into adjacent terrestrial food webs. It is unknown whether this transfer is also relevant for current-use pesticides. We exposed larvae of the nonbiting midge, Chironomus riparius, to a sublethal pulse of a mixture of nine moderately polar fungicides and herbicides (logKow 2.5-4.7) at three field relevant treatment levels (1.2-2.5, 17.5-35.0, or 50.0-100.0 µg/L). We then assessed the pesticide bioaccumulation and bioamplification over the full aquatic-terrestrial life cycle of both sexes including the egg laying of adult females. By applying sensitive LC-MS/MS analysis to small sample volumes (∼5 mg, dry weight), we detected all pesticides in larvae from all treatment levels (2.8-1019 ng/g), five of the pesticides in the adults from the lowest treatment level and eight in the higher treatment levels (1.5-3615 ng/g). Retention of the pesticides through metamorphosis was not predictable based solely on pesticide lipophilicity. Sex-specific differences in adult insect pesticide concentrations were significant for five of the pesticides, with greater concentrations in females for four of them. Over the duration of the adults' lifespan, pesticide concentrations generally decreased in females while persisting in males. Our results suggest that a low to moderate daily dietary exposure to these pesticides may be possible for tree swallow nestlings and insectivorous bats.

Singlet Oxygen Photooxidation of Peptidic Oxazoles and Thiazoles.

Oxazoles and thiazoles are commonly found moieties in nonribosomal peptides (NRPs) and ribosomally synthesized post-translationally modified peptides (RiPPs), which are important biomolecules present in the environment and in natural waters. From previous studies, they seem susceptible to oxidation by singlet oxygen (1O2); therefore, we designed and synthesized model oxazole- and thiazole-peptides and measured their 1O2 bimolecular reaction rate constants, showing slow photooxidation under environmental conditions. We reasoned their stability through the electron-withdrawing effect of the carboxamide substituent. Reaction products were elucidated and support a reaction mechanism involving cycloaddition followed by a series of rearrangements. The first 1O2 bimolecular reaction rate constant for a RiPP, the thiazole-containing peptide Aerucyclamide A, was measured and found in good agreement with the model peptide's rate constant, highlighting the potential of using model peptides to study the transformations of other environmentally relevant NRPs and RiPPs.