Development of a sampling protocol for collecting leaf surface material for multiphase chemistry studies.

Plant leaves and water drops residing on them interact with atmospheric oxidants, impacting the deposition and emission of trace gases and mediating leaf damage from air pollution. Characterizing the chemical composition and reactivity of the water-soluble material on leaf surfaces is thus essential for improving our understanding of atmosphere-biosphere interactions. However, the limited knowledge of sources and nature of these chemicals challenges sampling decisions. This work investigates how sampling variables and environmental factors impact the quantity and composition of water-soluble material sampled from wet leaves and proposes a flexible protocol for its collection. The ratio of solvent volume-to-leaf area, the solvent-to-leaf contact time, and environmental parameters - including the occurrence of rain, plant location and its metabolism - drive solute concentration in leaf soaks. Despite minor variations, UV-vis absorption spectra of leaf soaks are comparable to authentic raindrops collected from the same tree and share features with microbial dissolved organic matter - including overall low aromaticity, low chromophore content, and low average molecular weight. In addition to guiding the development of a sampling protocol, our data corroborate recent hypotheses on the amount, origin, nature, and reactivity of water-soluble organics on wet leaves, providing new directions of research into this highly interdisciplinary topic.

Measuring Biosphere-Atmosphere Exchange of Short-Lived Climate Forcers and Their Precursors.

Exchange of reactive trace gases over the biosphere is a key source of reactive organic carbon to the atmosphere and thus influences the formation of both ozone (O3) and secondary organic aerosol (SOA). Both O3 and aerosol particles are short-lived climate forcers and impact the radiative balance of the planet, and their sources and sinks are chemically complex. However, the biosphere also acts as a deposition sink for organic and inorganic compounds, including O3, aerosols, and their precursors. Wet and dry deposition provides a key lever on the lifetime of trace gases and particles in the atmosphere and thus on their potential to influence the radiative balance of the planet. The fluxes of reactive trace gases and particles are part of an atmospheric biogeochemical cycle that includes feedbacks through drought and other climate components.Recent advances in measurement techniques have enabled new field observations of trace gas and particle fluxes. Our method development has focused on the leaf, branch, and forest level, although satellite measurements coupled to modeling also provide promising new approaches to constraining trace gas fluxes. Leaf chamber measurements of volatile organic compound (VOC) emissions highlight leaf-to-leaf and plant-to-plant variability in both photosynthesis and emissions of individual VOCs, in addition to differences in emissions across different isomers of monoterpenes. Isomers obviously have different chemical properties (e.g., reaction rates with OH radicals, SOA yield) and thus hold different potentials as precursors for short-lived climate forcers.The biosphere acts as both sources and sinks of the oxidation products of monoterpenes and other biogenic VOCs. Developments in chemical ionization mass spectrometry have recently enabled measurements of volatile organic acids, which demonstrate a strong temperature-dependent ecosystem source, as well as a source from in-canopy chemistry. In-canopy chemistry also influences particle fluxes, although deposition should dominate their net exchange. Our field observations of chemically resolved particle fluxes demonstrate the simultaneous, competing processes driving forest exchange. To separate out these competing processes, we use black carbon as an inert tracer for particle deposition. Our recent measurements demonstrate the importance of wet deposition in controlling particle lifetime in the atmosphere. Overall, new measurement techniques have enabled both field and laboratory observations to improve our understanding of biosphere-atmosphere interactions and their influence on climate processes.