Cell wall ester modifications and volatile emission signatures of plant response to abiotic stress.

Growth suppression and defence signalling are simultaneous strategies that plants invoke to respond to abiotic stress. Here, we show that the drought stress response of poplar trees (Populus trichocarpa) is initiated by a suppression in cell wall derived methanol (MeOH) emissions and activation of acetic acid (AA) fermentation defences. Temperature sensitive emissions dominated by MeOH (AA/MeOH <30%) were observed from physiologically active leaves, branches, detached stems, leaf cell wall isolations and whole ecosystems. In contrast, drought treatment resulted in a suppression of MeOH emissions and strong enhancement in AA emissions together with volatiles acetaldehyde, ethanol, and acetone. These drought-induced changes coincided with a reduction in stomatal conductance, photosynthesis, transpiration, and leaf water potential. The strong enhancement in AA/MeOH emission ratios during drought (400%-3500%) was associated with an increase in acetate content of whole leaf cell walls, which became significantly 13 C2 -labelled following the delivery of 13 C2 -acetate via the transpiration stream. The results are consistent with both enzymatic and nonenzymatic MeOH and AA production at high temperature in hydrated tissues associated with accelerated primary cell wall growth processes, which are downregulated during drought. While the metabolic source(s) require further investigation, the observations are consistent with drought-induced activation of aerobic fermentation driving high rates of foliar AA emissions and enhancements in leaf cell wall O-acetylation. We suggest that atmospheric AA/MeOH emission ratios could be useful as a highly sensitive signal in studies investigating environmental and biological factors influencing growth-defence trade-offs in plants and ecosystems.

The role of a suburban forest in controlling vertical trace gas and OH reactivity distributions - a case study for the Seoul metropolitan area.

We present trace gas vertical profiles observed by instruments on the NASA DC-8 and at a ground site during the Korea-US air quality study (KORUS) field campaign in May to June 2016. We focus on the region near the Seoul metropolitan area and its surroundings where both anthropogenic and natural emission sources play an important role in local photochemistry. Integrating ground and airborne observations is the major research goal of many atmospheric chemistry field campaigns. Although airborne platforms typically aim to sample from near surface to the free troposphere, it is difficult to fly very close to the surface especially in environments with complex terrain or a populated area. A detailed analysis integrating ground and airborne observations associated with specific concentration footprints indicates that reactive trace gases are quickly oxidized below an altitude of 700 m. The total OH reactivity profile has a rapid decay in the lower part of troposphere from surface to the lowest altitude (700 m) sampled by the NASA DC-8. The decay rate is close to that of very reactive biogenic volatile organic compounds such as monoterpenes. Therefore, we argue that photochemical processes in the bottom of the boundary layer, below the typical altitude of aircraft sampling, should be thoroughly investigated to properly assess ozone and secondary aerosol formation.

Chemical evolution of atmospheric organic carbon over multiple generations of oxidation.

The evolution of atmospheric organic carbon as it undergoes oxidation has a controlling influence on concentrations of key atmospheric species, including particulate matter, ozone and oxidants. However, full characterization of organic carbon over hours to days of atmospheric processing has been stymied by its extreme chemical complexity. Here we study the multigenerational oxidation of α-pinene in the laboratory, characterizing products with several state-of-the-art analytical techniques. Although quantification of some early generation products remains elusive, full carbon closure is achieved (within measurement uncertainty) by the end of the experiments. These results provide new insights into the effects of oxidation on organic carbon properties (volatility, oxidation state and reactivity) and the atmospheric lifecycle of organic carbon. Following an initial period characterized by functionalization reactions and particle growth, fragmentation reactions dominate, forming smaller species. After approximately one day of atmospheric aging, most carbon is sequestered in two long-lived reservoirs-volatile oxidized gases and low-volatility particulate matter.

Alkoxy Radical Bond Scissions Explain the Anomalously Low Secondary Organic Aerosol and Organonitrate Yields From α-Pinene + NO3.

Oxidation of monoterpenes (C10H16) by nitrate radicals (NO3) constitutes an important source of atmospheric secondary organic aerosol (SOA) and organonitrates. However, knowledge of the mechanisms of their formation is incomplete and differences in yields between similar monoterpenes are poorly understood. In particular, yields of SOA and organonitrates from α-pinene + NO3 are low, while those from Δ3-carene + NO3 are high. Using computational methods, we suggest that bond scission of the nitrooxy alkoxy radicals from Δ3-carene lead to the formation of reactive keto-nitrooxy-alkyl radicals, which retain the nitrooxy moiety and can undergo further reactions to form SOA. By contrast, bond scissions of the nitrooxy alkoxy radicals from α-pinene lead almost exclusively to the formation of the relatively unreactive and volatile product pinonaldehyde (C10H16O2), thereby limiting organonitrate and SOA formation. This hypothesis is supported by laboratory experiments that quantify products of the reaction of α-pinene + NO3 under atmospherically relevant conditions.