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We characterized the dissolved organic matter (DOM) under baseflow conditions from a set of rivers in the Mohawk and Hudson River watersheds. The rivers in this study drain a range of bedrock geologies and land cover. We identify how those factors influence riverine DOM reactivity and the source, age, and composition of the biolabile DOM. We performed laboratory incubation experiments to characterize each river's reactive and non‐reactive DOM pools. Measurements of dissolved organic carbon concentration, radiocarbon, Ultraviolet‐visible spectroscopy absorbance, and Fourier‐transform ion cyclotron resonance mass spectrometry (FTICR‐MS) analysis were performed at each incubation start and end, allowing us to determine the quantity, age, and composition of the reactive and nonreactive DOM pools. We find that lithology controls bulk DOM ages, with watersheds underlain by shale/limestone having the most aged DOM and crystalline/metasedimentary watersheds having the youngest DOM. We observe that for a given lithology, bulk DOM age increases with the proportion of agricultural land in the watershed–suggesting agricultural practices mobilize aged DOM. FTICR‐MS analysis reveals that both lithology and land cover influence DOM composition. Shale/limestone watersheds showed DOM compositions distinct from other watershed lithologies, and the percentage of nitrogen‐containing DOM correlated with agricultural influence. In two of the studied rivers we find that the biolabile DOM fraction is older than the bulk DOM (upwards of 7 kyr) revealing that aged DOM may be preferentially consumed in these rivers. Our findings provide insight into how riverine carbon cycles may respond to watershed disturbances that influence DOM inputs to rivers. Plain Language Summary: As rivers drain land areas around the globe they pick up organic matter (OM) which is then transported and transformed as water flows downstream. Through the degradation of some of this OM to carbon dioxide (CO2), rivers play a critical role in the global carbon cycle, with CO2 emissions from rivers estimated to be equivalent to >20% of the CO2 emissions from the burning of fossil fuels. Despite the importance of rivers in the global carbon cycle, many questions remain as to what controls the composition and reactivity of OM within rivers. We investigated how watershed geology and land cover (e.g., forested vs. agricultural land) influence the chemical composition, age, and reactivity of the OM in rivers. We found that rivers draining shale/limestone watersheds had chemically distinct OM that is much older and more reactive than OM from other types of watersheds. We also found that across all watersheds the age of OM increased with the proportion of the watershed that is devoted to agricultural activity and that in some watersheds the older OM was preferentially consumed. Our findings suggest that disturbances to land (e.g., agriculture) may release aged, previously buried OM that can then be transformed to CO2. Key Points: Watershed geology and land cover influence river dissolved organic matter composition and biolability under baseflow conditionsDissolved organic carbon (DOC) bulk ages are strongly influenced by watershed geology and the proportion of agricultural land coverUnder baseflow, high molecular weight compounds are preferentially consumed and aged DOC is preferentially consumed in smaller streams [ABSTRACT FROM AUTHOR]

Most soil carbon (C) is in the form of soil organic matter (SOM), the composition of which is controlled by the plant–microbe–soil continuum. The extent to which plant and microbial inputs contribute to persistent SOM has been linked to edaphic properties such as mineralogy and aggregation. However, it is unknown how variation in plant inputs, microbial community structure, and soil physical and chemical attributes interact to influence the chemical classes that comprise SOM pools. We used two long‐term biofuel feedstock field experiments to test the influence of cropping systems (corn and switchgrass) and soil characteristics (sandy and silty loams) on microbial selection and SOM chemistry. Cropping system had a strong influence on water‐extractable organic C chemistry with perennial switchgrass generally having a higher chemical richness than the annual corn cropping system. Nonetheless, cropping system was a less influential driver of soil microbial community structure and overall C chemistry than soil type. Soil type was especially influential on fungal community structure and the chemical composition of the chloroform‐extractable C. Although plant inputs strongly influence the substrates available for decomposition and SOM formation, total C and nitrogen (N) did not differ between cropping systems within either site. We conclude this is likely due to enhanced microbial activity under the perennial cropping system. Silty soils also had a higher activity of phosphate and C liberating enzymes. After 8 years, silty loams still contained twice the total C and N as sandy loams, with no significant response to biofuel cropping system inputs. Together, these results demonstrate that initial site selection is critical to plant–microbe interactions and substantially impacts the potential for long‐term C accrual in soils under biofuel feedstock production. [ABSTRACT FROM AUTHOR]

Abstract: The path of carbon (C) from plant litter to soil organic matter (SOM) is key to understanding how soil C stocks and microbial decomposition will respond to climate change and whether soil C sinks can be enhanced. Long‐term ecosystem‐scale litter manipulations and molecular characterization of SOM provide a unique opportunity to explore these issues. We incubated soils from a 20‐year litter input experiment for 525 days and asked how litter quantity and source (i.e., roots versus aboveground litter) affected C cycling, microbial function, and the size and molecular composition of C pools. Input exclusion led to a 30% loss of soil C, attributable largely to the nonmineral‐associated C fraction, and to declines in soil C decomposition. The absence of roots caused a shift in the microbial catabolic profile, though there was little evidence that root litter was preferentially stabilized. Although C pool size did not change with litter additions, Fourier transform ion cyclotron resonance mass spectrometry analysis of the finest mineral fraction revealed dramatic changes to the chemical composition of carbon. Lipid content increased proportionally with input addition and was subsequently mineralized during incubation, indicating that this fraction was metabolically active. Moreover, nonmetric dimensional scaling showed that both litter treatments and incubation caused the molecular composition of SOM to change. We conclude that the path of C from litter to soil may involve labile pools and root‐driven microbial activity associated directly with SOM in the soil mineral matrix otherwise previously hypothesized to be stable. [ABSTRACT FROM AUTHOR]

Abstract: In light of increasing terrestrial carbon (C) transport across aquatic boundaries, the mechanisms governing organic carbon (OC) oxidation along terrestrial‐aquatic interfaces are crucial to future climate predictions. Here we investigate the biochemistry, metabolic pathways, and thermodynamics corresponding to OC oxidation in the Columbia River corridor using ultrahigh‐resolution C characterization. We leverage natural vegetative differences to encompass variation in terrestrial C inputs. Our results suggest that decreases in terrestrial C deposition associated with diminished riparian vegetation induce oxidation of physically bound OC. We also find that contrasting metabolic pathways oxidize OC in the presence and absence of vegetation and—in direct conflict with the “priming” concept—that inputs of water‐soluble and thermodynamically favorable terrestrial OC protect bound‐OC from oxidation. In both environments, the most thermodynamically favorable compounds appear to be preferentially oxidized regardless of which OC pool microbiomes metabolize. In turn, we suggest that the extent of riparian vegetation causes sediment microbiomes to locally adapt to oxidize a particular pool of OC but that common thermodynamic principles govern the oxidation of each pool (i.e., water‐soluble or physically bound). Finally, we propose a mechanistic conceptualization of OC oxidation along terrestrial‐aquatic interfaces that can be used to model heterogeneous patterns of OC loss under changing land cover distributions. [ABSTRACT FROM AUTHOR]

Tandem mass spectrometry (MS/MS) provides detailed information for structural characterization of biomolecules. The combination of electron capture dissociation (ECD) techniques with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) often provides unique ion-electron reactions and fragmentation channels in MS/MS. ECD is often a complimentary, sometimes even a superior tool to conventional MS/MS techniques. This article is aimed at providing a short overview of ECD-based fragmentation techniques (ExD) and optimization of ECD experiments for FTICR mass analyzers. Most importantly, it is meant to pique the interest of potential users for this exciting research field. © 2015 Wiley Periodicals, Inc. Mass Spec Rev 36:4-15, 2017. [ABSTRACT FROM AUTHOR]

A letter to the editor is presented in response to the article which discusses a study on the use of electron-capture dissociation (ECD) to investigate host/guest complexes of 18-crown-6-ether and peptides.