Warmer climates have been associated with reduced bioreactivity of soil organic matter (SOM) typically attributed to increased diagenesis; the combined biological and physiochemical transformation of SOM. In addition, cross-site studies have indicated that ecosystem regime shifts, associated with long-term climate warming, can affect SOM properties through changes in vegetation and plant litter production thereby altering the composition of soil inputs. The relative importance of these two controls, diagenesis and inputs, on SOM properties as ecosystems experience climate warming, however, remains poorly understood. To address this issue we characterized the elemental, chemical (nuclear magnetic resonance spectroscopy and total hydrolysable amino acids analysis), and isotopic composition of plant litter and SOM across a well-constrained mesic boreal forest latitudinal transect in Atlantic Canada. Results across forest sites within each of three climate regions indicated that (1) climate history and diagenesis affect distinct parameters of SOM chemistry, (2) increases in SOM bioreactivity with latitude were associated with elevated proportions of carbohydrates relative to plant waxes and lignin, and (3) despite the common forest type across regions, differences in SOM chemistry by climate region were associated with chemically distinct litter inputs and not different degrees of diagenesis. The observed climate effects on vascular plant litter chemistry, however, explained only part of the regional differences in SOM chemistry, most notably the higher protein content of SOM from warmer regions. Greater proportions of lignin and aliphatic compounds and smaller proportions of carbohydrates in warmer sites' soils were explained by the higher proportion of vascular plant relative to moss litter in the warmer relative to cooler forests. These results indicate that climate change induced decreases in the proportion of moss inputs not only impacts SOM chemistry but also increases the resistance of SOM to decomposition, thus significantly altering SOM cycling in these boreal forest soils.

Soil microbial biomass is a key source of soil organic carbon (SOC), and the increasing proportion of microbially derived SOC is thought to drive the enrichment of 13 C during SOC decomposition. Yet, little is known about how the d 13

Ultra-basic reducing springs at continental sites of serpentinization act as portals into the biogeochemistry of a subsurface environment with H2 and CH4 present. Very little, however, is known about the carbon substrate utilization, energy sources, and metabolic pathways of the microorganisms that live in this ultra-basic environment. The potential for microbial methanogenesis with bicarbonate, formate, acetate, and propionate precursors and carbon monoxide (CO) utilization pathways were tested in laboratory experiments by adding substrates to water and sediment from the Tablelands, NL, CAD, a site of present-day continental serpentinization. Microbial methanogenesis was not observed after bicarbonate, formate, acetate, or propionate addition. CO was consumed in the live experiments but not in the killed controls and the residual CO in the live experiments became enriched in 13C. The average isotopic enrichment factor resulting from this microbial utilization of CO was estimated to be 11.2 ± 0.2‰. Phospholipid fatty acid concentrations and δ13C values suggest limited incorporation of carbon from CO into microbial lipids. This indicates that in our experiments, CO was used primarily as an energy source, but not for biomass growth. Environmental DNA sequencing of spring fluids collected at the same time as the addition experiments yielded a large proportion of Hydrogenophaga-related sequences, which is consistent with previous metagenomic data indicating the potential for these taxa to utilize CO.

Present-day serpentinization generates groundwaters with conditions (pH > 11, Eh < À550 mV) favorable for the microbial and abiotic production of organic compounds from inorganic precursors. Elevated concentrations of methane, C 2 -C 6 alkanes, acetate, and formate have been detected at these sites, but the microbial or abiotic origin of these compounds remains unclear. While geochemical data indicate that methane at most sites of present-day serpentinization is abiogenic, the stable carbon, hydrogen, and clumped isotope data as well as the hydrocarbon gas composition from The Cedars, CA, USA, are consistent with a microbial origin for methane. However, there is no direct evidence of methanogenesis at this site of serpentinization. We report on laboratory experiments in which the microbial communities in fluids and sediments from The Cedars were incubated with 13 C labeled substrates. Increasing methane concentrations and the incorporation of 13 C into methane in live experiments, but not in killed controls, demonstrated that methanogens converted methanol, formate, acetate (methyl group), and bicarbonate to methane. The apparent fractionation between methane and potential substrates (α 13 C CH4-CO2(g) = 1.059 to 1.105, α 13 C CH4-acetate = 1.042 to 1.119) indicated that methanogenesis was dominated by the carbonate reduction pathway. Increasing concentrations of volatile organic acid anions indicated microbial acetogenesis. α 13 C CO2(g)-acetate values (0.999 to 1.000), however, were inconsistent with autotrophic acetogenesis, thus suggesting that acetate was produced through fermentation. This is the first study to show direct evidence of microbial methanogenesis and acetogenesis by the native microbial community at a site of present-day serpentinization.

Abstract. Studies that quantify plant methane (CH4) emission rely on the accurate measurement of small changes in the mixing ratio of CH4 that coincide with much larger changes in the mixing ratio of volatile organic compounds (VOCs). Here, we assessed whether 11 commonly occurring VOCs (e.g. methanol, α- and β-pinene, Δ3-carene) interfered with the quantitation of CH4 by five laser-absorption spectroscopy and Fourier-transformed infrared spectroscopy (FTIR) based CH4 analysers, and quantified the interference of seven compounds on three instruments. Our results showed minimal interference with laser-based analysers and underlined the importance of identifying and compensating for interferences with FTIR instruments. When VOCs were not included in the spectral library, they exerted a strong bias on FTIR-based instruments (64–1800 ppbv apparent CH4 ppmv−1 VOC). Minor (0.7–126 ppbv ppmv−1) interference with FTIR-based measurements were also detected when the spectrum of the interfering VOC was included in the library. In contrast, we detected only minor (<20 ppbv ppmv−1) and transient (< 1 min) VOC interferences on laser-absorption spectroscopy-based analysers. Overall, our results demonstrate that VOC interferences have only minor effects on CH4 flux measurements in soil chambers, but may severely impact stem and shoot flux measurements. Laser-absorption-based instruments are better suited for quantifying CH4 fluxes from plant leaves and stems than FTIR-based instruments; however, significant interferences in shoot chamber measurements could not be excluded for any of the tested instruments. Our results furthermore showed that FTIR can precisely quantify VOC mixing ratios and could therefore provide a method complementary to proton-transfer-reaction mass spectrometry (PTR-MS).

Summary Aerenchymatic transport is an important mechanism through which plants affect methane (CH4) emissions from peatlands. Controlling environmental factors and the effects of plant phenology remain, however, uncertain. We identified factors controlling seasonal CH4 flux rate and investigated transport efficiency (flux rate per unit of rhizospheric porewater CH4 concentration). We measured CH4 fluxes through individual shoots of Carex rostrata, Menyanthes trifoliata, Betula nana and Salix lapponum throughout growing seasons in 2020 and 2021 and Equisetum fluviatile and Comarum palustre in high summer 2021 along with water‐table level, peat temperature and porewater CH4 concentration. CH4 flux rate of C. rostrata was related to plant phenology and peat temperature. Flux rates of M. trifoliata and shrubs B. nana and S. lapponum were insensitive to the investigated environmental variables. In high summer, flux rate and efficiency were highest for C. rostrata (6.86 mg m−2 h−1 and 0.36 mg m−2 h−1 (μmol l−1)−1, respectively). Menyanthes trifoliata showed a high flux rate, but limited efficiency. Low flux rates and efficiency were detected for the remaining species. Knowledge of the species‐specific CH4 flux rate and their different responses to plant phenology and environmental factors can significantly improve the estimation of ecosystem‐scale CH4 dynamics in boreal peatlands.

Glucans like cellulose and starch are a major source of carbon for decomposer food webs, especially during early- and intermediate-stages of decomposition. Litter quality has previously been suggested to notably influence decomposition processes as it determines the decomposability of organic material and the nutrient availability to the decomposer community. To study the impact of chemical and elemental composition of resources on glucan decomposition, a laboratory experiment was carried out using beech (Fagus sylvatica, L.) litter from four different locations in Austria, differing in composition (concentration of starch, cellulose and acid unhydrolyzable residue or AUR fraction) and elemental stoichiometry (C:N:P ratio). Leaf litter was incubated in mesocosms for six months in the laboratory under controlled conditions. To investigate the process of glucan decomposition and its controls, we developed an isotope pool dilution (IPD) assay using 13C-glucose to label the pool of free glucose in the litter, and subsequently measured the dilution of label over time. This enabled us to calculate gross rates of glucose production through glucan depolymerization, and glucose consumption by the microbial community. In addition, potential activities of extracellular cellulases and ligninases (peroxidases and phenoloxidases) were measured to identify effects of resource chemistry and stoichiometry on microbial enzyme production. Gross rates of glucan depolymerization and glucose consumption were highly correlated, indicating that both processes are co-regulated and intrinsically linked by the microbial demand for C and energy and thereby to resource allocation to enzymes that depolymerize glucans. At early stages of decomposition, glucan depolymerization rates were correlated with starch content, indicating that starch was the primary source for glucose. With progressing litter decomposition, the correlation with starch diminished and glucan depolymerization rates were highly correlated to cellulase activities, suggesting that cellulose was the primary substrate for glucan depolymerization at this stage of decomposition. Litter stoichiometry did not affect glucan depolymerization or glucose consumption rates early in decomposition. At later stages, however, we found significant negative relationships between glucan depolymerization and litter C:N and AUR:N ratio and a positive relationship between glucan depolymerization and litter N concentration. Litter C:N and C:P ratios were negatively related to cellulase, peroxidase and phenoloxidase activities three and six months after incubation, further corroborating the importance of resource stoichiometry for glucan depolymerization after the initial pulse of starch degradation.

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