Atmospheric Chemistry Research Articles

Valence Electronic Structure of Interfacial Phenol in Water Droplets.

Biochemistry and a large part of atmospheric chemistry occur in aqueous environments or at aqueous interfaces, where (photo)chemical reaction rates can be increased by up to several orders of magnitude. The key to understanding the chemistry and photoresponse of molecules in and "on" water lies in their valence electronic structure, with a sensitive probe being photoelectron spectroscopy. This work reports velocity-map photoelectron imaging of submicrometer-sized aqueous phenol droplets in the valence region after nonresonant (288 nm) and resonance-enhanced (274 nm) two-photon ionization with femtosecond ultraviolet light, complementing previous liquid microjet studies. For nonresonant photoionization, our concentration-dependent study reveals a systematic decrease in the vertical binding energy (VBE) of aqueous phenol from 8.0 ± 0.1 eV at low concentration (0.01 M) to 7.6 ± 0.1 eV at high concentration (0.8 M). We attribute this shift to a systematic lowering of the energy of the lowest cationic state with increasing concentration caused by the phenol dimer and aggregate formation at the droplet surface. Contrary to nonresonant photoionization, no significant concentration dependence of the VBE was observed for resonance-enhanced photoionization. We explain the concentration-independent VBE of ∼8.1 eV observed upon resonant ionization by ultrafast intermediate state relaxation and changes in the accessible Franck-Condon region as a consequence of the lowering of the intermediate state potential energy due to the formation of phenol excimers and excited phenol aggregates. Correcting for the influence of electron transport scattering in the droplets reduced the measured VBEs by 0.1-0.2 eV.

Substantial nitrogen abatement accompanying decarbonization suppresses terrestrial carbon sinks in China

China faces challenges in reaching its carbon neutrality goal by the year 2060 to meet the Paris Agreement and improving air quality simultaneously. Dramatic nitrogen emission reductions will be brought by this ambitious target, yet their impact on the natural ecosystem is not clear. Here, by combining two atmospheric chemistry models and two process-based terrestrial ecosystem models constrained using nationwide measurements, we show that atmospheric nitrogen deposition in China’s terrestrial land will decrease by 44–57% following two emission control scenarios including one aiming at carbon neutrality. They consequently result in a pronounced shrinkage in terrestrial net ecosystem production, by 11–20% depending on models and emission scenarios. Our results indicate that the nitrogen emission reductions accompanying decarbonization would undermine natural carbon sinks and in turn set back progress toward carbon neutrality. This unintended impact calls for great concern about the trade-offs between nitrogen management and carbon neutrality.

Accelerating healing at high altitudes: Oxygen and bFGF delivery through nanoparticle-loaded gel dressings

High altitude environment is mainly characterized by low oxygen. Due to persistent hypoxia, nonhealing wounds are common in high-altitude areas. Moreover, Basic fibroblast growth factor (bFGF) is a versatile biologically active substance that has crucial impact on wound healing. Given the limited availability of atmospheric oxygen and reduced blood oxygen saturation in high-altitude area, and the challenge that arises from direct oxygen and bFGF delivery to wounds through the traumatized vascular structure, it necessitates an innovative solution for local and permeable delivery of oxygen and bFGF. In this study, we present a strategy that involves revamping traditional gel-based wound dressings through the incorporation of nanoparticles encapsulating oxygen and bFGF, engineered to facilitate the localized delivery of dissolved oxygen and bFGF to wound surfaces. The prospective evaluation of this delivery technique's therapeutic impacts on epithelial, endothelial and fibroblasts cells can be materialized. Further experiment corroborated these effects on a high-altitude wounds' murine model. Given its biocompatibility, efficacy, and utility, we posit that NOB-Gel exhibits remarkable translational potential for managing and hastening the healing process of an array of clinical wounds, more so for wounds inflicted at high altitudes.

Formation conditions of the tungsten porous thin film with pulsed laser deposition under various gas atmosphere

Abstract Pulsed laser deposition (PLD) under gas atmospheres has been used to fabricate thin films for various applications. In this study, PLD was performed under various gas atmospheres (helium, oxygen, and argon) using tungsten (W) to investigate the morphology of thin films. Various types of structures were formed, including uniform, nanoparticles, and columnar structures. In particular, the substrate fabricated at an argon pressure of 100 Pa had a high porosity and a low light reflectance in the 200–1400 nm wavelength range. In addition, it was shown that the growth of the thin film thickness was non-linear with respect to time, and the formation of a fuzz-like structure may be influenced by particle diffusion in the gas phase and on the substrate.

Significant chlorine emissions from biomass burning affect the long-term atmospheric chemistry in Asia.

Biomass burning (BB) is a major source of trace gases and particles in the atmosphere, influencing air quality, radiative balance, and climate. Previous studies have mainly focused on the BB emissions of carbon and nitrogen species with less attention on chlorine. Reactive chlorine chemistry has significant effects on atmospheric chemistry and air quality. However, quantitative information on chlorine emissions from BB, particularly the long-term trend and associated atmospheric impacts, is limited both on regional and global scales. Here, we report a long-term (2001-2018) high-resolution BB emission inventory for the major chlorine-containing compounds (HCl, chloride, and CH3Cl) in Asia based on satellite observations. We estimate an average of 730 Gg yr-1 chlorine emitted from BB activity in Asia, with China contributing the largest share at 24.2% (177 Gg yr-1), followed by Myanmar at 18.7% and India at 18.3%. Distinct seasonal patterns and significant spatial and interannual variability are observed, mainly driven by human-mediated changes in agricultural activity. By incorporating the newly developed chlorine emission inventory into a global chemistry-climate model (CAM-Chem), we find that the BB-chlorine emissions lead to elevated levels of HCl and CH3Cl (monthly average up to 2062 and 1421 parts per trillion by volume (pptv), respectively), subsequently resulting in noticeable changes in oxidants (up to 3.1% in O3 and 17% in OH radicals). The results demonstrate that BB is not only a significant source of air pollutants but also of oxidants, suggesting a larger role of BB emissions in the atmospheric chemistry and oxidation process than previously appreciated. In light of the projected increase in BB activity toward the end of the century and the extensive control of anthropogenic emissions worldwide, the contribution of BB emissions may become fundamental to air quality composition in the future.

An investigation into Venusian atmospheric chemistry based on an open-access photochemistry-transport model at 0–112 km

Atmospheric chemistry plays a crucial role in the evolution of climate habitability on Venus. It has been widely explored by chemistry-transport models, but some characteristics are still poorly interpreted. This study is devoted to developing an open-access chemistry-transport model spanning both the middle and lower atmospheres of Venus. It provides a scheme for the structure of the chemistry, especially for the sulfur and oxygen, and investigates the influence of the cloud diffusivity and the SO2 dissolution that are adopted in the clouds. The developed model is based on the VULCAN framework and was updated with the state-of-the-art Venusian atmospheric chemistry. It includes vertical eddy diffusion retrieved recently with the Venus Express observations, and it resolves radiative transfer containing gas absorption and scattering, Mie scattering of the cloud droplets, and absorption of the unknown UV absorber. The obtained abundance profiles of SO, SO2, CO, COS, O, O2, O3, HCl, and NO are in overall agreement with the observations. The results show that the increase in cloud diffusivity has slight effects on the chemical structure. The SO2 mainly dissolves in 50–90 km and evaporates below the clouds. The rapid dissolution-release cycle is responsible for the large upward flux of SO2 at 58 km. At around 70 km, SO has a significant peak that is larger than that of previous studies by an order of magnitude, and S and SO2 also show slight increases. They are attributed to the buffering effects of liquid SO2 in the clouds. O2 is significantly eliminated by SO in this layer. We emphasize the superior regulation of the sulfur cycle on O2 at 70 km and its potential contributions to the long-standing problem of the overestimated O2 abundance.

Oxidative Conversion of the Key Vegetable Carotenoids β‐Carotene, Lutein and Lycopene under Atmospheric Oxygen and Light

Oxidative Conversion of the Key Vegetable Carotenoids β‐Carotene, Lutein and Lycopene under Atmospheric Oxygen and Light

The Palaeo-Productivity Signals Chronicled from the Buxa Formation, North-East Lesser Himalaya, India

ABSTRACT The Mesoproterozoic era is known for its relatively stable ecological conditions and limited atmospheric oxygen. Despite this understanding, uncertainties remain about how ocean chemistry evolved during this time and its potential impact on the development of complex eukaryotic life forms. In response to these uncertainties; we have undertaken a study to investigate indicators of ancient productivity within the Buxa Formation of the Lesser Himalaya in Sikkim. By analyzing the isotopic values ( δ13 C and δ 18Ο values) as well as Rare Earth Element (REE) composition, a total n = 151 carbonate samples were investigated across three sections of the Buxa Formation: Jorethang to Mangalbare, Legship to Naya Bazar, and Reshi to Mangalbare, Sikkim. The study’s findings show that there was minimal variation in δ13C values, consistently ranging between –0.5 and +2.5 ‰ VPDB. This pattern suggests a relatively steady and moderately high level of productivity during that time. This productivity might have been influenced by a temporary increase in atmospheric oxygen levels. Additionally, we have also reviewed and examined stromatolites as part of the investigation.

The Yadovitaya fumarole, Tolbachik volcano: A comprehensive mineralogical and geochemical study and driving factors for mineral diversity

Active volcanic fumaroles are one of the most spectacular natural objects in terms of mineral diversity. The Great Tolbachik Fissure Eruption (GTFE) (Kamchatka) fumaroles are renowned for its exceptional number of mineral species. The total number of minerals that have been reliably identified from this particular locality exceeds 400, which is approximately 6.5 % of all known minerals to date. In this study, we employ a comprehensive approach (bulk chemistry, microprobe analysis, powder X-ray diffraction, HR X-ray computed tomography, and 34S, 18O, and 65Cu isotope measurements) to study the distribution of primary exhalation and secondary mineral assemblages and to reveal the driving factors responsible for the unique mineral diversity in the Yadovitaya fumarole. High oxygen fugacity, the interaction of minerals with atmospheric oxygen and water from seasonal precipitation (leading to abundant hydrated mineral associations), temperature conditions controlling the spatial distribution of mineral-forming components, gas-rock interactions, and basaltic scoria morphology perfect for the crystallization of various minerals are some of the factors revealed. The combination of these factors caused a stepwise mineralization resulting in 12 zones of the Yadovitaya fumarole with characteristic mineral assemblages. The described mineralogy of the Yadovitaya fumarole demonstrates a consistent spatial evolution of fumarolic mineral assemblages that vary in complexity, chemistry, and interaction patterns with the surrounding environment. The examination of mineralogical and geochemical data yields novel insights into the active volcanic systems that are associated with the formation of distinct oxidation-type fumaroles.

Study of the influence of carbon nanotubes on the superconducting properties of YBCO composite

Abstract This article describes a method for producing a superconducting composite based on YBCO doped with carbon nanotubes by solid-phase combustion in an atmosphere of pure oxygen. It has been determined that the initial connection of the components, the ignition temperature and holding time, as well as the degree of doping with CNT nanoparticles affect the qualitative and quantitative provision of the superconducting Y123 phase, including its superconducting properties.

Physiology, Not Nutrient Availability, May Have Limited Primary Productivity After the Emergence of Oxygenic Photosynthesis.

The evolution of oxygenic photosynthesis in Cyanobacteria was a transformative event in Earth's history. However, the scientific community disagrees over the duration of the delay between the origin of oxygenic photosynthesis and oxygenation of Earth's atmosphere, with estimates ranging from less than a hundred thousand to more than a billion years, depending on assumptions about rates of oxygen production and fluxes of reductants. Here, we propose a novel ecological hypothesis that a geologically significant delay could have been caused by biomolecular inefficiencies within proto-Cyanobacteria-ancestors of modern Cyanobacteria-that limited their maximum rates of oxygen production. Consideration of evolutionary processes and genomic data suggest to us that proto-cyanobacterial primary productivity was initially limited by photosystem instability, oxidative damage, and photoinhibition rather than nutrients or ecological competition. We propose that during the Archean era, cyanobacterial photosystems experienced protracted evolution, with biomolecular inefficiencies initially limiting primary productivity and oxygen production. Natural selection led to increases in efficiency and thus primary productivity through time. Eventually, evolutionary advances produced sufficient biomolecular efficiency that environmental factors, such as nutrient availability, limited primary productivity and shifted controls on oxygen production from physiological to environmental limitations. If correct, our novel hypothesis predicts a geologically significant interval of time between the first local oxygen production and sufficient production for oxygenation of environments. It also predicts that evolutionary rates were likely highly variable due to strong environmental selection pressures and potentially high mutation rates but low competitive interactions.

Study on the cracking process of epoxy resin under oxygen and water atmosphere based on ReaxFF force field

Amino-cured epoxy resins are widely used in the electrical and electronic industry for their excellent properties. To investigate the mechanism of the effect of O2 and H2O on the pyrolysis behavior of epoxy resin, in this paper, the cross-linked structure of bisphenol A type epoxy resin cured by adducts of diethylenetriamine and butyl glycidyl ether is modeled based on the ReaxFF force field, and the thermal decomposition processes at different temperatures and gas atmospheres were simulated and the pathways of the small molecule products were clarified. The results show that epoxy resin will produce small molecule gas products, such as H2, CO, H2O, OH, CH2O, and free radicals, in the process of pyrolysis; the presence of amino groups also generates nitrogen-containing radicals, such as CN, CH2N, and C2H4N; as the reaction temperature increases, the rate of pyrolysis reaction will be accelerated. The same temperature in oxygen and water atmospheres can accelerate the breakage of epoxy resin main chain by promoting the breakage of carbon and oxygen bonds and, at the same time, promote the generation of small molecule gases, such as H2 and CO.

Chromatic acclimation in cyanobacteria renders robust photosynthesis and fitness in dynamic light environment: Recent advances and future perspectives.

Cyanobacteria are photoautotrophic organisms that use light and water as a source of energy and electrons, respectively, to fix atmospheric carbon dioxide and release oxygen as a by-product during photosynthesis. However, photosynthesis and fitness of organisms are challenged by seasonal and diurnal fluctuations in light environments. Also, the distribution of cyanobacteria in a water column is subject to changes in the light regime. The quality and quantity of light change significantly in low and bright light environments that either limit photochemistry or result in photoinhibition due to an excess amount of light reaching reaction centers. Therefore, cyanobacteria have to adjust their light-harvesting machinery and cell morphology for the optimal harvesting of light. This adjustment of light-harvesting involves remodeling of the light-harvesting complex called phycobilisome or incorporation of chlorophyll molecules such as chlorophyll d and f into their light-harvesting machinery. Thus, photoacclimation responses of cyanobacteria at the level of pigment composition and cell morphology maximize their photosynthetic ability and fitness under a dynamic light environment. Cyanobacteria exhibit different types of photoacclimation responses that are commonly known as chromatic acclimation (CA). In this work, we discuss different types of CA reported in cyanobacteria and present a molecular mechanism of well-known type 3 CA where phycoerythrin and phycocyanin of phycobilisome changes according to light signals. We also include other aspects of type 3 CA that have been recently studied at a molecular level and highlight the importance of morphogenes, cytoskeleton, and carboxysome proteins. In summary, CA gives a unique competitive benefit to cyanobacteria by increasing their resource utilization ability and fitness.

A Tale of Two Molecules: The Underprediction of CO2 and Overprediction of PH3 in Late T and Y Dwarf Atmospheric Models

The sensitivity and spectral coverage of JWST are enabling us to test our assumptions of ultracool dwarf atmospheric chemistry, especially with regards to the abundances of phosphine (PH3) and carbon dioxide (CO2). In this paper, we use Near Infrared Spectrograph PRISM spectra (∼0.8−5.5 μm, R ∼ 100) of four late T and Y dwarfs to show that standard substellar atmosphere models have difficulty replicating the 4.1−4.4 μm wavelength range, as they predict an overabundance of phosphine and an underabundance of carbon dioxide. To help quantify this discrepancy, we generate a grid of models using PICASO, based on the Elf Owl chemical and temperature profiles, where we include the abundances of these two molecules as parameters. The fits to these PICASO models show a consistent preference for orders-of-magnitude higher CO2 abundances and a reduction in PH3 abundance as compared to the nominal models. This tendency means that the claimed phosphine detection in UNCOVER−BD−3 could instead be explained by a CO2 abundance in excess of standard atmospheric model predictions; however, the signal-to-noise ratio of the spectrum is not high enough to discriminate between these cases. We discuss atmospheric mechanisms that could explain the observed underabundance of PH3 and overabundance of CO2, including a vertical eddy diffusion coefficient (K zz) that varies with altitude, incorrect chemical pathways, or elements condensing out in forms such as NH4H2PO4. However, our favored explanation for the required CO2 enhancement is that the quench approximation does not accurately predict the CO2 abundance, as CO2 remains in chemical equilibrium with CO after CO quenches.

Neoarchaean oxygen-based nitrogen cycle en route to the Great Oxidation Event.

The nitrogen isotopic composition of sedimentary rocks (δ15N) can trace redox-dependent biological pathways and early Earth oxygenation1,2. However, there is no substantial change in the sedimentary δ15N record across the Great Oxidation Event about 2.45 billion years ago (Ga)3, a prominent redox change. This argues for a temporal decoupling between the emergence of the first oxygen-based oxidative pathways of the nitrogen cycle and the accumulation of atmospheric oxygen after 2.45 Ga (ref. 3). The transition between both states shows strongly positive δ15N values (10-50‰) in rocks deposited between 2.8 Gaand 2.6 Ga, but their origin and spatial extent remain uncertain4,5. Here we report strongly positive δ15N values (>30‰) in the 2.68-Gyr-old shallow to deep marine sedimentary deposit of the Serra Sul Formation6, Amazonian Craton, Brazil. Our findings are best explained by regionally variable extents of ammonium oxidation to N2 or N2O tied to a cryptic oxygen cycle, implying that oxygenic photosynthesis was operating at 2.7 Ga. Molecular oxygen production probably shifted the redox potential so that an intermediate N cycle based on ammonium oxidation developed before nitrate accumulation in surface waters. We propose to name this period, when strongly positive nitrogen isotopic compositions are superimposed on the usual range of Precambrian δ15N values, the Nitrogen Isotope Event. We suggest that it marks the earliest steps of the biogeochemical reorganizations that led to the Great Oxidation Event.

Phosphorus flux during the Ediacaran: Rooted in continental weathering or pelagic upwelling?

The Ediacaran Period was punctuated by major environmental and evolutionary milestones, including large-scale phosphogenesis during intervals of elevated phosphorous (P) flux. Although increased P flux could be an important driver of animal evolution and associated ocean oxygenation, the processes responsible for triggering the remarkable Ediacaran phosphogenesis episodes remain unclear. In this study, we present new δ138Ba, 87Sr/86Sr, and major and trace element data from Ediacaran phosphorites of the Doushantou Formation (Nanhua Basin, China). Low-to-negative δ138Ba (−0.31 to 0.06 ‰, analogous to δ138Ba of modern and ancient restricted depositional settings) and elevated 87Sr/86Sr values (0.7100 ± 0.0002, greater than the global average) from lower Doushantuo phosphorites indicate intense local continental weathering enhanced P delivery to the restricted Nanhua Basin at ∼630–600 Ma. During this early phosphogenesis stage, macroeukaryote blooms stimulated atmospheric oxygenation and eutrophication of deep seawater in the Nanhua Basin. In contrast to the lower phosphorites, the elevated and open-marine-like δ138Ba of 0.17 to 0.35 ‰, as well as lower 87Sr/86Sr values (mostly lower than 0.7096, comparable to the global average), from overlying ∼587–574 Ma phosphorites indicate that this later phosphogenesis interval was characterized by upwelling of pelagic deep ocean waters rich in re-mineralized P. Global-scale P burial (as phosphorite) could not lead to decreased eutrophic conditions in the global ocean, but, together with increasing oxygen levels in deep seawater and/or the atmosphere, this process may have finally facilitated the evolution of Ediacaran fauna.

Over 100-fold improvement in the accuracy of relaxed eddy accumulation flux estimates through error diffusion

Measurements of atmosphere-surface exchange are largely limited by the availability of fast-response gas analyzers; this limitation hampers our understanding of the role of terrestrial ecosystems in atmospheric chemistry and global change. Current micrometeorological methods, compatible with slow-response gas analyzers, are difficult to implement, or rely on empirical parameters that introduce large systematic errors.Here, we develop a new micrometeorological method, optimized for slow-response gas analyzers, that directly measures exchange rates of different atmospheric constituents, with minimal requirements. The new method requires only the sampling of air at a constant rate and directing it into one of two reservoirs, depending on the direction of the vertical wind velocity. An integral component of the new technique is an error diffusion algorithm that minimizes the biases in the measured fluxes and achieves direct flux estimates.We demonstrate that the new method provides an unbiased estimate of the flux, with accuracy within 0.1% of the reference eddy covariance flux, and importantly, allows for significant enhancements in the signal-to-noise ratio of measured scalars without compromising accuracy. Our new method provides a simple and reliable way to address complex environmental questions and offers a promising avenue for advancing our understanding of ecological systems and atmospheric chemistry.

Intense intrusion of low-oxygen waters into mid-Cambrian surface ocean carbonate factories

The Phanerozoic surface ocean is characterized by its high dissolved oxygen content owing to mixing with the atmosphere. However, atmospheric oxygen levels varied in the early Paleozoic and it remains unclear whether the surface ocean was susceptible to significant redox fluctuations in response to extreme environmental events. In this study, we probed the redox structures of shallow middle Cambrian marine depositional environments across the North China Platform, ranging from open tidal flats to relatively deep subtidal environments. We utilized a combination of least diagenetically altered carbonate materials (such as ooid cortices, calcimicrobes, and their fringing cements), as well as in situ element measurement and imaging techniques. By analyzing a set of redox-related elements (e.g., Ce anomaly, Zn/Fe molar ratio, Mn and Cr) and mineralogical proxies (hydrogenetic Fe oxides), we revealed a stratified redox structure in the Drumian surface oceans. Compared to earlier Drumian conditions, late Drumian surface oceans experienced significant intrusions of ferruginous waters, probably reaching into shallow subtidal environments with water depths less than 10 m. Furthermore, we identified shallow subtidal microbial O2-producing factories, characterized by dendritic Epiphyton thalli. These calcimicrobes exhibited more oxygenated signatures (negative Ce anomalies and enrichment of hydrogenetic Fe oxides) relative to contemporaneous less oxic shallower and deeper environments. This finding indicates that they produced oxygen oases or refuges during periods of both normal and poor dissolved O2 conditions. This study has the potential to broaden our understanding of redox conditions and microbial oxygen-producing mechanisms in the surface ocean, particularly during intervals characterized by low atmospheric oxygen levels or episodic anoxic events.

Marine Fe cycling linked to dynamic redox variability, biological activity and post-depositional mineralization in the 1.1 Ga Mesoproterozoic Taoudeni Basin, Mauritania

The concentration of redox sensitive trace metals (RSTEs) and their isotopic composition preserved in Precambrian marine sediments, are critical for the reconstruction of ocean–atmosphere oxygenation history. Particularly, the concentration of Fe, its redox speciation, and isotopic distribution, have gained widespread use for inferring the biogeochemical processes that controlled Fe cycling in Precambrian oceans linked to the reconstruction of Earth surface redox budget. However, questions remain about the biotic and abiotic processes involved in Fe cycling in these ancient oceans, including the impact of post-depositional alterative processes on the reliability of the Fe redox proxy. Here we present a multi-proxy mineralogical and geochemical study of the ∼1.1 Ga Atar and El Mreiti strata of the Taoudeni Basin in Mauritania, to better constrain pathways involved in Fe cycling, linked to Fe mineralogy, redox speciation, isotopic ratios during this time and metamorphism. We compare unmetamorphosed sedimentary deposits with facies metamorphosed by dolerite sill intrusion. The results reveal the occurrence of diagenetic Fe minerals in the basal unmetamorphosed samples associated with light δ56Fe signatures, reflecting dominant anoxic conditions that promoted microbial dissimilatory Fe reduction. Notably, δ56Fe composition of these rocks reveal several fluctuations in evolving seawater redox state from oxic to anoxic/sulfidic conditions associated with changes in sea level stand and periods of full bottom water oxygenation and redox stratification. Overall, Ce anomalies suggest a general up sequence increase in seawater oxygen content. Metamorphosed rocks display heterogeneous δ56Fe distribution, consisting of light and heavy signatures associated with secondary Fe-bearing minerals produced by metamorphic and metasomatic overprinting of carbonated rocks by hot circulating fluids. The results thus indicate metamorphic overprinting of primary seawater δ56Fe promoted by increased mobility of reactive Fe during post-depositional metamorphic transformation. They show that post-depositional metamorphic/metasomatic overprinting complicates direct reconstruction of seawater biogeochemical Fe cycling and redox state using δ56Fe systematics.

Responses of plant volatile emissions to increasing nitrogen deposition: A pilot study on Eucalyptus urophylla

Biogenic volatile organic compounds (BVOCs) significantly impact atmospheric chemistry, with emissions potentially influenced by nitrogen (N) deposition. The response of BVOC emissions to increasing N deposition remains debated. In this study, we examined Eucalyptus urophylla (E. urophylla) using three N treatments: N0, N50, and N100 (0, 50, and 100 kg N hm−2 yr−1 N addition). These treatments were applied to mature E. urophylla trees in a plantation subjected to over 10 years of soil N addition in southern China, a region with severe N deposition. Seventeen BVOCs were measured, with isoprene (36.99 %), α-pinene (38.80 %), and d-limonene (14.27 %) being the predominant compounds under natural conditions. Total BVOC emissions under N50 were nearly double those under N0 and N100, with leaf net CO2 assimilation identified as the most critical photosynthetic parameter. Isoprene and α-pinene emissions significantly increased under N50 compared to N0, while d-limonene emission decreased under N100. Stronger correlations for individual BVOCs under N50 and N100 compared to N0 might be due to differences in BVOC biosynthetic pathways and storage structures. The localized canopy-scale emission factors (EFs) under N50 were significantly higher than the default values in the Model of Emissions of Gases and Aerosols from Nature (MEGAN), suggesting the model might underestimate BVOC emissions from Eucalyptus in southern China under increased N deposition. Additionally, the secondary pollutant formation potentials of BVOCs were evaluated, identifying isoprene and monoterpenes as primary precursors of ozone and secondary organic aerosols. This study provides insights into the impacts of increased N deposition on BVOC emissions and their contribution to secondary atmospheric pollution. Updating localized BVOC EFs for subtropical tree species in southern China is crucial to reduce uncertainties in BVOC estimations under current and future N deposition scenarios.