Online molecular characterisation of organic aerosols in an atmospheric chamber using extractive electrospray ionisation mass spectrometry

Abstract. The oxidation of biogenic volatile organic compounds (VOCs) represents a substantial source of secondary organic aerosol (SOA) in the atmosphere. In this study, we present online measurements of the molecular constituents formed in the gas and aerosol phases during α-pinene oxidation in the Cambridge Atmospheric Simulation Chamber (CASC). We focus on characterising the performance of extractive electrospray ionisation (EESI) mass spectrometry (MS) for particle analysis. A number of new aspects of EESI-MS performance are considered here. We show that relative quantification of organic analytes can be achieved in mixed organic–inorganic particles. A comprehensive assignment of mass spectra for α-pinene derived SOA in both positive and negative ion modes is obtained using an ultra-high-resolution mass spectrometer. We compare these online spectra to conventional offline ESI-MS spectra and find good agreement in terms of the compounds identified, without the need for complex sample work-up procedures. Under our experimental conditions, EESI-MS signals arise only from particle-phase analytes. High-time-resolution (7 min) EESI-MS spectra are compared with simulations from the near-explicit Master Chemical Mechanism (MCM) for a range of reaction conditions. We show that MS peak abundances scale with modelled concentrations for condensable products (pinonic acid, pinic acid, OH-pinonic acid). Relative quantification is achieved throughout SOA formation as the composition, size and mass (5–2400 µg m−3) of particles is evolving. This work provides a robust demonstration of the advantages of EESI-MS for chamber studies over offline ESI-MS (time resolution, relative quantification) and over hard online techniques (molecular information). </jats:p

Direct Injection Liquid Chromatography High-Resolution Mass Spectrometry for Determination of Primary and Secondary Terrestrial and Marine Biomarkers in Ice Cores

Many atmospheric organic compounds are long-lived enough to be transported from their sources to polar regions and high mountain environments where they can be trapped in ice archives. While inorganic components in ice archives have been studied extensively to identify past climate changes, organic compounds have rarely been used to assess paleo-environmental changes, mainly due to the lack of suitable analytical methods. This study presents a new method of direct injection HPLC-MS analysis, without the need of pre-concentrating the melted ice, for the determination of a series of novel biomarkers in ice-core samples indicative of primary and secondary terrestrial and marine organic aerosol sources. Eliminating a preconcentration step reduces contamination potential and decreases the required sample volume thus allowing a higher time resolution in the archives. The method is characterised by limits of detections (LODs) in the range of 0.01-15 ppb, depending on the analyte, and accuracy evaluated through an interlaboratory comparison. We find that many components in secondary organic aerosols (SOA) are clearly detectable at concentrations comparable to those previously observed in replicate preconcentrated ice samples from the Belukha glacier, Russian Altai Mountains. Some compounds with low recoveries in preconcentration steps are now detectable in samples with this new direct injection method significantly increasing the range of environmental processes and sources that become accessible for paleo-climate studies

Direct target and non-target analysis of urban aerosol sample extracts using atmospheric pressure photoionisation high-resolution mass spectrometry

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous atmospheric pollutants of high concern for public health. In the atmosphere they undergo oxidation, mainly through reactions with center dot OH and NOx to produce nitro- and oxygenated (oxy-) derivatives. In this study, we developed a new method for the detection of particle-bound PAHs, nitro-PAHs and oxy-PAHs using direct infusion into an atmospheric pressure photoionisation high-resolution mass spectrometer (APPI-HRMS). Method optimisation was done by testing different source temperatures, gas flow rates, mobile phases and dopants. Samples were extracted with methanol, concentrated by evaporation and directly infused in the APPI source after adding toluene as dopant. Acquisition was performed in both polarity modes. The method was applied to target analysis of seasonal PM2.5 samples from an urban background site in Padua (Italy), in the Po Valley, in which a series of PAHs, nitro- and oxy-PAHs were detected. APPI-HRMS was then used for non-target analysis of seasonal PM2.5 samples and results compared with nano-electrospray ionisation (nanoESI) HRMS. The results showed that, when samples were characterised by highly oxidised organic compounds, including S-containing compounds, like in summer samples, APPI did not bring any additional information with respect to nanoESI in negative polarity (nanoESI(-)). Conversely, for winter samples, APPI(-) could detect a series of aromatic and poly-aromatic compounds, mainly oxidised and nitrogenated aromatics, that were not otherwise detected with nanoESI. (C) 2019 Elsevier Ltd. All rights reserved

A new method to assess the acute toxicity toward honeybees of the abrasion particles generated from seeds coated with insecticides

Abstract Background: Large amounts of insecticide-containing dusts produced from abrasion of the seed dressing can be released into the atmosphere during sowing operations. Neonicotinoid pesticides, introduced in the 1990s for several crops, are the leading products for seed-coating treatments in many countries. Neonicotinoid containing dusts can be efectively intercepted by bees in fight over the sowing feld, inducing lethal acute efects, so that restrictions in the use of the main neonicotinoids have been adopted in the European Union. This led to the consequent introduction of replacement insecticides for seed-coating, i.e. methiocarb and thiacloprid, despite the lack of information on both the toxicity and the exposure scenarios for honeybees. Results: In this study, a laboratory apparatus was developed in order to quantify the toxicity of the dusts produced from the abrasion of the seed coating. This quantifcation is based on (i) an airstream transporting coating particles into an exposure chamber; (ii) exposure of bees to reproducible and measurable concentrations of insecticide, and (iii) direct measurement of the exposure dose on single bees. The method allowed us to perform in vivo experiments of honeybee exposure to provide toxicity data in more realistic exposure conditions. In fact, the formulation rather than the active principle alone can be tested, and the exposure is through dusts rather than a solution so that specifc absorption behavior can be studied in representative environmental conditions. The method was used to quantify the acute toxicity (LD50) of dusts obtained from the abrasion of corn seeds coated with clothianidin, thiacloprid and methiocarb. Conclusions: Our results show that, surprisingly, the replacement insecticide methiocarb has a toxicity (LD50=421– 693 ng/bee) in the same order of magnitude as clothianidin (LD50=113–451 ng/bee) through this specifc exposure route, while thiacloprid (LD50=16.9·103 ng/bee) has a signifcantly lower acute toxicity. Moreover, dusts containing methiocarb and clothianidin show a signifcant increase in toxicity when, after exposure, bees are kept under high humidity conditions. This suggests that the method here presented can be used to obtain complementary toxicity data in the risk assessment procedure for the authorization of new seed-coating insecticides or new formulations. Keywords: Systemic insecticides, Neonicotinoids, Methiocarb, Seed coating, Abrasion dusts, Honeybees, Pollinator insects, Acute toxicity, Exposure measuremen

Direct surface analysis coupled to high-resolution mass spectrometry reveals heterogeneous composition of the cuticle of Hibiscus trionum petals.

Plant cuticle, which is the outermost layer covering the aerial parts of all plants including petals and leaves, can present a wide range of patterns that, combined with cell shape, can generate unique physical, mechanical, or optical properties. For example, arrays of regularly spaced nanoridges have been found on the dark (anthocyanin-rich) portion at the base of the petals of Hibiscus trionum. Those ridges act as a diffraction grating, producing an iridescent effect. Because the surface of the distal white region of the petals is smooth and noniridescent, a selective chemical characterization of the surface of the petals on different portions (i.e., ridged vs smooth) is needed to understand whether distinct cuticular patterns correlate with distinct chemical compositions of the cuticle. In the present study, a rapid screening method has been developed for the direct surface analysis of Hibiscus trionum petals using liquid extraction surface analysis (LESA) coupled with high-resolution mass spectrometry. The optimized method was used to characterize a wide range of plant metabolites and cuticle monomers on the upper (adaxial) surface of the petals on both the white/smooth and anthocyanic/ridged regions, and on the lower (abaxial) surface, which is entirely smooth. The main components detected on the surface of the petals are low-molecular-weight organic acids, sugars, and flavonoids. The ridged portion on the upper surface of the petal is enriched in long-chain fatty acids, which are constituents of the wax fraction of the cuticle. These compounds were not detected on the white/smooth region of the upper petal surface or on the smooth lower surface.The authors acknowledge support by the ERC grant 279405.This is the author accepted manuscript. The final version is available at http://dx.doi.org/10.1021/acs.analchem.5b0249

Metal ion release from fine particulate matter sampled in the Po Valley to an aqueous solution mimicking fog water: Kinetics and solubility

Metals are among the key aerosol components exerting adverse health effects. Their toxic properties may vary depending on their chemical form and solubility, which can be affected by aqueous processing during aerosol atmospheric lifetime. In this work, fine particulate matter (PM2.5) was collected in the city centre of Padua in the Po Valley (Italy), during a winter campaign. Part of the sampling filters were used to measure the kinetics by which metal ions and other elements can leach from PM2.5 to an aqueous solution mimicking fog water in the winter in temperate climate regions (pH 4.7, 5\ub0C). The leaching process was interpreted by a first order kinetics, and the fitting of the experimental data allowed to obtain the leaching kinetic constants and the equilibrium concentrations (i.e., at infinite time) for all elements. The remaining filter parts were mineralised, through two subsequent extraction steps, and the extracts were analysed by ICP-MS to gain the total elemental content of PM for a large number of elements. We found that elements can leach from PM with half times generally between 10\u201340 minutes, which is a timescale compatible with atmospheric aqueous processing during fog events. For instance, aluminium(III) in PM2.5 dissolved with an average k = 0.0185 min\u20131, and t1/2 = 37.5 min. Nevertheless, a fraction of each element was immediately solubilised after contact with the extraction solution suggesting that metal ion solubilisation may already had started during particle lifetime in the atmosphere

Secondary organic aerosol formation from isoprene photooxidation during cloud condensation-evaporation cycles

Abstract. The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene ∕ NOx ∕ light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are 2 and 4 times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of 2 or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to the dissolution of water soluble volatile organic compounds (VOCs) in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations. The authors thank Arnaud Allanic, Sylvain Ravier, Pascal Renard and Pascal Zapf for their contributions in the experiments. The authors also acknowledge the institutions that have provided financial support: the French National Institute for Geophysical Research (CNRS-INSU) within the LEFE-CHAT program through the project “Impact de la chimie des nuages sur la formation d’aérosols organiques secondaires dans l’atmosphère” and the French National Agency for Research (ANR) project CUMULUS ANR-2010-BLAN-617-01. This work was also supported by the EC within the I3 project “Integrating of European Simulation Chambers for Investigating Atmospheric Processes” (EUROCHAMP-2, contract no. 228335). The authors thank the MASSALYA instrumental platform (Aix Marseille Université, lce.univ-amu.fr) for the analysis and measurements used in this paper.This is the final version of the article. It first appeared from Copernicus Publications via http://dx.doi.org/10.5194/acp-16-1747-201

Vineyard pruning residues pellets for use in domestic appliances: A quality assessment according to the EN ISO 17225

Nowadays many types of biomass are studied to satisfy the increased demand of renewable energy based on pellet combustion. However, only a few biomasses fulfil the high quality standard required for pellet used in domestic appliances. European and International standards in force define this quality of non-industrial use of pellets in term of the origin of biomass, physical, mechanical and chemical parameters. Vineyard residues are a worldwide potential source of energy but their compliance to be used in domestic pellet stoves has not been yet proven according to the new standards in force. In order to meet this need, this study makes an exhaustive characterisation of vineyard based pellets manufactured from residues of Prosecco (Glera variety) vineyards, assessing both the quality of biofuel and its behaviour during combustion in a domestic pellet stove. The quality of biofuel has been evaluated according to the in force standards for wood and non-woody pellets. The results show that vineyard pellets do not meet the type B quality standards required for non-industrial use of wood pellet mainly because of the high amount of ash content (&gt;2%) and the high amount of copper (&gt;10 ppm) but they fulfil the specifications of the type B non-woody pellets. Furthermore, during combustion test of vineyard-based pellet the high emission of CO indicates incomplete combustion; and vineyard- based pellet NOx emissions are more than double compared to those obtained during the control tests, confirming that the analysed vineyard-based pellets are unsuitable, as they are, for use in traditional pellet stoves.</jats:p

Multiphase composition changes and reactive oxygen species formation during limonene oxidation in the new Cambridge Atmospheric Simulation Chamber (CASC)

The chemical composition of organic aerosols influences their impacts on human health and the climate system. Aerosol formation from gas-to-particle conversion and in-particle reaction was studied for the oxidation of limonene in a new facility, the Cambridge Atmospheric Simulation Chamber (CASC). Health-relevant oxidising organic species produced during secondary organic aerosol (SOA) formation were quantified in real time using an Online Particle-bound Reactive Oxygen Species Instrument (OPROSI). Two categories of reactive oxygen species (ROS) were identified based on time series analysis: a short-lived component produced during precursor ozonolysis with a lifetime of the order of minutes, and a stable component that was long-lived on the experiment timescale (ĝ1/4ĝ€4ĝ€h). Individual organic species were monitored continuously over this time using Extractive Electrospray Ionisation (EESI) Mass Spectrometry (MS) for the particle phase and Proton Transfer Reaction (PTR) MS for the gas phase. Many first-generation oxidation products are unsaturated, and we observed multiphase aging via further ozonolysis reactions. Volatile products such as C9H14O (limonaketone) and C10H16O2 (limonaldehyde) were observed in the gas phase early in the experiment, before reacting again with ozone. Loss of C10H16O4 (7-hydroxy limononic acid) from the particle phase was surprisingly slow. A combination of reduced C Combining double low line C reactivity and viscous particle formation (relative to other SOA systems) may explain this, and both scenarios were tested in the Pretty Good Aerosol Model (PG-AM). A range of characterisation measurements were also carried out to benchmark the chamber against existing facilities. This work demonstrates the utility of CASC, particularly for understanding the reactivity and health-relevant properties of organic aerosols using novel, highly time-resolved techniques.This work was funded by the European Research Council (grant 279405), the UK Natural Environment Research Council (grant NE/H52449X/1), and the Velux foundation (project number 593)

Detection and identification of Criegee intermediates from the ozonolysis of biogenic and anthropogenic VOCs: comparison between experimental measurements and theoretical calculations

Ozonolysis of alkenes is a key reaction in the atmosphere, playing an important role in determining the oxidising capacity of the atmosphere and acting as a source of compounds that can contribute to local photochemical “smog”. The reaction products of the initial step of alkene-ozonolysis are Criegee intermediates (CIs), which have for many decades eluded direct experimental detection because of their very short lifetime. We use an innovative experimental technique, stabilisation of CIs with spin traps and analysis with proton transfer reaction mass spectrometry, to measure the gas phase concentration of a series of CIs formed from ozonolysis of a range of both biogenic and anthropogenic alkenes in flow tube experiments. Density functional theory (DFT) calculations were used to assess the stability of the CI-spin trap adducts and showed that the reaction of the investigated CIs with the spin trap occurs very rapidly except for the large β-pinene CI. Our measurement method was used successfully to measure all the expected CIs, emphasising that this new technique is applicable to a wide range of CIs with different molecular structures previously unidentified experimentally. In addition, for the first time it was possible to study CIs simultaneously in an even more complex reaction system consisting of more than one olefinic precursor. Comparison between our new experimental measurements, calculations of stability of the CI-spin trap adducts and results from numerical modelling, using the master chemical mechanism (MCM), showed that our new method can be used for quantification of CIs produced in situ in laboratory experiments.This work was funded by the European Research Council (ERC starting grant 279405) and NERC (NE/K008218/1). ATA thanks NERC for funding through NCAS