Permafrost degradation is delivering bioavailable dissolved organic matter (DOM) and inorganic nutrients to surface water networks. While these permafrost subsidies represent a small portion of total fluvial DOM and nutrient fluxes, they could influence food webs and net ecosystem carbon balance via priming or nutrient effects that destabilize background DOM. We investigated how addition of biolabile carbon (acetate) and inorganic nutrients (nitrogen and phosphorus) affected DOM decomposition with 28‐day incubations. We incubated late‐summer stream water from 23 locations nested in seven northern or high‐altitude regions in Asia, Europe, and North America. DOM loss ranged from 3% to 52%, showing a variety of longitudinal patterns within stream networks. DOM optical properties varied widely, but DOM showed compositional similarity based on Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) analysis. Addition of acetate and nutrients decreased bulk DOM mineralization (i.e., negative priming), with more negative effects on biodegradable DOM but neutral or positive effects on stable DOM. Unexpectedly, acetate and nutrients triggered breakdown of colored DOM (CDOM), with median decreases of 1.6% in the control and 22% in the amended treatment. Additionally, the uptake of added acetate was strongly limited by nutrient availability across sites. These findings suggest that biolabile DOM and nutrients released from degrading permafrost may decrease background DOM mineralization but alter stoichiometry and light conditions in receiving waterbodies. We conclude that priming and nutrient effects are coupled in northern aquatic ecosystems and that quantifying two‐way interactions between DOM properties and environmental conditions could resolve conflicting observations about the drivers of DOM in permafrost zone waterways.
The electron ionization and methane chemical ionization mass spectra of some 2,2-disubstituted 1,3-dioxolanes, 1,3-dithiolanes and 1,3-oxathiolanes were studied. Especially, the effect of the length of the side chain in ring position 2 of these compounds and the ease of formation of possible lactone/thiolactone ion as a fragmentation product were examined. In addition, two 2,2-disubstituted 1,3-dioxanes were studied to see the effect of the bigger ring size. The formation of lactone ions was more favorable under methane chemical ionization than under electron ionization conditions. The structures of fragment ions and the ions generated from model compounds were carefully studied using both high-and low-energy collisioninduced dissociation. Also ab initio molecular orbital calculations up to the HF/6-31G** level of theory for protonated 2-methyl-2-propanoic acid ethyl ester of 1,3-dioxolane, 1,3-oxathiolane and 1,3-dithiolane and for two isomeric bicyclic ions were carried out. The theoretical results obtained favor the formation of the lactone ion.
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