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Creators/Authors contains: "Krechmer, Jordan E."

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  1. Abstract

    Drought impacts on microbial activity can alter soil carbon fate and lead to the loss of stored carbon to the atmosphere as CO2and volatile organic compounds (VOCs). Here we examined drought impacts on carbon allocation by soil microbes in the Biosphere 2 artificial tropical rainforest by tracking13C from position-specific13C-pyruvate into CO2and VOCs in parallel with multi-omics. During drought, efflux of13C-enriched acetate, acetone and C4H6O2(diacetyl) increased. These changes represent increased production and buildup of intermediate metabolites driven by decreased carbon cycling efficiency. Simultaneously,13C-CO2efflux decreased, driven by a decrease in microbial activity. However, the microbial carbon allocation to energy gain relative to biosynthesis was unchanged, signifying maintained energy demand for biosynthesis of VOCs and other drought-stress-induced pathways. Overall, while carbon loss to the atmosphere via CO2decreased during drought, carbon loss via efflux of VOCs increased, indicating microbially induced shifts in soil carbon fate.

     
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  2. Volatile chemical products (VCPs) and other non-combustion-related sourceshave become important for urban air quality, and bottom-up calculationsreport emissions of a variety of functionalized compounds that remainunderstudied and uncertain in emissions estimates. Using a new instrumentalconfiguration, we present online measurements of oxygenated organiccompounds in a US megacity over a 10 d wintertime sampling period, whenbiogenic sources and photochemistry were less active. Measurements wereconducted at a rooftop observatory in upper Manhattan, New York City, USAusing a Vocus chemical ionization time-of-flight mass spectrometer, withammonium (NH4+) as the reagent ion operating at 1 Hz. The range ofobservations spanned volatile, intermediate-volatility, and semi-volatileorganic compounds, with targeted analyses of ∼150 ions, whoselikely assignments included a range of functionalized compound classes suchas glycols, glycol ethers, acetates, acids, alcohols, acrylates, esters,ethanolamines, and ketones that are found in various consumer, commercial,and industrial products. Their concentrations varied as a function of winddirection, with enhancements over the highly populated areas of the Bronx,Manhattan, and parts of New Jersey, and included abundant concentrations ofacetates, acrylates, ethylene glycol, and other commonly used oxygenatedcompounds. The results provide top-down constraints on wintertime emissionsof these oxygenated and functionalized compounds, with ratios to commonanthropogenic marker compounds and comparisons of their relative abundancesto two regionally resolved emissions inventories used in urban air qualitymodels.

     
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    Soils harbor complex biological processes intertwined with metabolic inputs from microbes and plants. Measuring the soil metabolome can reveal active metabolic pathways, providing insight into the presence of specific organisms and ecological interactions. A subset of the metabolome is volatile; however, current soil studies rarely consider volatile organic compounds (VOCs), contributing to biases in sample processing and metabolomic analytical techniques. Therefore, we hypothesize that overall, the volatility of detected compounds measured using current metabolomic analytical techniques will be lower than undetected compounds, a reflection of missed VOCs. To illustrate this, we examined a peatland metabolomic dataset collected using three common metabolomic analytical techniques: nuclear magnetic resonance (NMR), gas chromatography-mass spectroscopy (GC-MS), and fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). We mapped the compounds to three metabolic pathways (monoterpenoid biosynthesis, diterpenoid biosynthesis, and polycyclic aromatic hydrocarbon degradation), chosen for their activity in peatland ecosystems and involvement of VOCs. We estimated the volatility of the compounds by calculating relative volatility indices (RVIs), and as hypothesized, the average RVI of undetected compounds within each of our focal pathways was higher than detected compounds ( p < 0.001). Moreover, higher RVI compounds were absent even in sub-pathways where lower RVI compounds were observed. Our findings suggest that typical soil metabolomic analytical techniques may overlook VOCs and leave missing links in metabolic pathways. To more completely represent the volatile fraction of the soil metabolome, we suggest that environmental scientists take into consideration these biases when designing and interpreting their data and/or add direct online measurement methods that capture the integral role of VOCs in soil systems. 
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