Publications by authors named "Markus Kalberer"

57 Publications

Ascorbate oxidation by iron, copper and reactive oxygen species: review, model development, and derivation of key rate constants.

Sci Rep 2021 Apr 1;11(1):7417. Epub 2021 Apr 1.

Department of Atmospheric and Oceanic Sciences, University of California At Los Angeles, Los Angeles, CA, 90095-1565, USA.

Ascorbic acid is among the most abundant antioxidants in the lung, where it likely plays a key role in the mechanism by which particulate air pollution initiates a biological response. Because ascorbic acid is a highly redox active species, it engages in a far more complex web of reactions than a typical organic molecule, reacting with oxidants such as the hydroxyl radical as well as redox-active transition metals such as iron and copper. The literature provides a solid outline for this chemistry, but there are large disagreements about mechanisms, stoichiometries and reaction rates, particularly for the transition metal reactions. Here we synthesize the literature, develop a chemical kinetics model, and use seven sets of laboratory measurements to constrain mechanisms for the iron and copper reactions and derive key rate constants. We find that micromolar concentrations of iron(III) and copper(II) are more important sinks for ascorbic acid (both AH and AH) than reactive oxygen species. The iron and copper reactions are catalytic rather than redox reactions, and have unit stoichiometries: Fe(III)/Cu(II) + AH/AH  + O → Fe(III)/Cu(II) + HO + products. Rate constants are 5.7 × 10 and 4.7 × 10 M s for Fe(III) + AH/AH and 7.7 × 10 and 2.8 × 10 M s for Cu(II) + AH/AH, respectively.
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http://dx.doi.org/10.1038/s41598-021-86477-8DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8016884PMC
April 2021

Formation of metal-organic ligand complexes affects solubility of metals in airborne particles at an urban site in the Po valley.

Chemosphere 2020 Feb 1;241:125025. Epub 2019 Oct 1.

Department of Chemical Sciences, University of Padua, via Marzolo 1, 35131, Padova, Italy; Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom. Electronic address:

Metals in atmospheric aerosols play potentially an important role in human health and ocean primary productivity. However, the lack of knowledge about solubility and speciation of metal ions in the particles or after solubilisation in aqueous media (sea or surface waters, cloud or rain droplets, biological fluids) limits our understanding of the underlying physico-chemical processes. In this work, a wide range of metals, their soluble fractions, and inorganic/organic compounds contained in urban particulate matter (PM) from Padua (Italy) were determined. Metal solubility tests have been performed by dissolving the PM in water and in solutions simulating rain droplet composition. The water-soluble fractions of the metal ions and of the organic compounds having ligand properties have been subjected to a multivariate statistical procedure, in order to elucidate associations among the aqueous concentrations of these PM components in simulated rain droplets. In parallel, a multi-dimensional speciation calculation has been performed to identify the stoichiometry and the amount of metal-ligand complexes theoretically expected in aqueous solutions. Both approaches showed that the solubility and the aqueous speciation of metal ions were differently affected by the presence of inorganic and organic ligands in the PM. The solubility of Al, Cr, and Fe was strongly correlated to the concentrations of oxalic acid, as their oxalate complexes represented the expected dominant species in aqueous solutions. Oxalates of Al represented ∼98% of soluble Al, while oxalates of Cu represented 34-75% of the soluble Cu, and oxalates of Fe represented 76% of soluble Fe. The oxidation state of Fe can strongly impact the speciation picture. If Fe is present as Fe(II) rather than Fe(III), the amount of Cr and Cu complexed with diacids can increase from 75% to 94%, and from 32% to 53%, respectively. For other metals, the solubility depended on the formation of soluble aquo-complexes, hence with a scarce effect of the organic ligands. An iron-oxalate complex was also directly detected in aerosol sample extracts.
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http://dx.doi.org/10.1016/j.chemosphere.2019.125025DOI Listing
February 2020

Radical Formation by Fine Particulate Matter Associated with Highly Oxygenated Molecules.

Environ Sci Technol 2019 Nov 7;53(21):12506-12518. Epub 2019 Oct 7.

Institute for Atmospheric and Earth System Research/Physics Faculty of Science , University of Helsinki , FI-00014 Helsinki , Finland.

Highly oxygenated molecules (HOMs) play an important role in the formation and evolution of secondary organic aerosols (SOA). However, the abundance of HOMs in different environments and their relation to the oxidative potential of fine particulate matter (PM) are largely unknown. Here, we investigated the relative HOM abundance and radical yield of laboratory-generated SOA and fine PM in ambient air ranging from remote forest areas to highly polluted megacities. By electron paramagnetic resonance and mass spectrometric investigations, we found that the relative abundance of HOMs, especially the dimeric and low-volatility types, in ambient fine PM was positively correlated with the formation of radicals in aqueous PM extracts. SOA from photooxidation of isoprene, ozonolysis of α- and β-pinene, and fine PM from tropical (central Amazon) and boreal (Hyytiälä, Finland) forests exhibited a higher HOM abundance and radical yield than SOA from photooxidation of naphthalene and fine PM from urban sites (Beijing, Guangzhou, Mainz, Shanghai, and Xi'an), confirming that HOMs are important constituents of biogenic SOA to generate radicals. Our study provides new insights into the chemical relationship of HOM abundance, composition, and sources with the yield of radicals by laboratory and ambient aerosols, enabling better quantification of the component-specific contribution of source- or site-specific fine PM to its climate and health effects.
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http://dx.doi.org/10.1021/acs.est.9b05149DOI Listing
November 2019

Development of a Physiologically Relevant Online Chemical Assay To Quantify Aerosol Oxidative Potential.

Anal Chem 2019 10 27;91(20):13088-13095. Epub 2019 Sep 27.

Department of Chemistry , University of Cambridge , Lensfield Road , Cambridge CB2 1EW , United Kingdom.

Large-scale epidemiological studies have shown a close correlation between adverse human health effects and exposure to ambient particulate matter (PM). The oxidative potential (OP) of ambient PM has been implicated in inducing toxic effects associated with PM exposure. In particular, reactive oxygen species (ROS), either bound to PM or generated by particulate components in vivo, substantially contribute to the OP and therefore toxicity of PM by lowering antioxidant concentrations in the lung, which can subsequently lead to oxidative stress, inflammation, and disease. Traditional methods for measuring aerosol OP are labor intensive and have poor time resolution, with significant delays between aerosol collection and ROS analysis. These methods may underestimate ROS concentrations in PM because of the potentially short lifetime of some ROS species; therefore, continuous online, highly time-resolved measurement of ROS components in PM is highly advantageous. In this work, we develop a novel online method for measuring aerosol OP based on ascorbic acid chemistry, an antioxidant prevalent in the lung, thus combining the advantages of continuous online measurement with a physiologically relevant assay. The method limit of detection is estimated for a range of atmospherically important chemical components such as Cu(II) 0.22 ± 0.03 μg m, Fe(II) 47.8 ± 5.5 μg m, Fe(III) 0.63 ± 0.05 μg m, and secondary organic aerosol 41.2 ± 6.9 μg m, demonstrating that even at this early stage of development, the online method is capable of measuring the OP of PM in polluted urban environments and smog chamber studies.
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http://dx.doi.org/10.1021/acs.analchem.9b03282DOI Listing
October 2019

Direct Depolymerization Coupled to Liquid Extraction Surface Analysis-High-Resolution Mass Spectrometry for the Characterization of the Surface of Plant Tissues.

Anal Chem 2019 07 14;91(13):8326-8333. Epub 2019 Jun 14.

Department of Chemistry , University of Cambridge , Lensfield Road , Cambridge CB2 1EW , United Kingdom.

The cuticle, the outermost layer covering the epidermis of most aerial organs of land plants, can have a heterogeneous composition even on the surface of the same organ. The main cuticle component is the polymer cutin which, depending on its chemical composition and structure, can have different biophysical properties. In this study, we introduce a new on-surface depolymerization method coupled to liquid extraction surface analysis (LESA) high-resolution mass spectrometry (HRMS) for a fast and spatially resolved chemical characterization of the cuticle of plant tissues. The method is composed of an on-surface saponification, followed by extraction with LESA using a chloroform-acetonitrile-water (49:49:2) mixture and direct HRMS detection. The method is also compared with LESA-HRMS without prior depolymerization for the analysis of the surface of the petals of Hibiscus richardsonii flowers, which have a ridged cuticle in the proximal region and a smooth cuticle in the distal region. We found that on-surface saponification is effective enough to depolymerize the cutin into its monomeric constituents thus allowing detection of compounds that were not otherwise accessible without a depolymerization step. The effect of the depolymerization procedure was more pronounced for the ridged/proximal cuticle, which is thicker and richer in epicuticular waxes compared with the cuticle in the smooth/distal region of the petal.
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http://dx.doi.org/10.1021/acs.analchem.9b01094DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6620716PMC
July 2019

Quantification of Particle-Bound Organic Radicals in Secondary Organic Aerosol.

Environ Sci Technol 2019 06 24;53(12):6729-6737. Epub 2019 May 24.

Centre for Atmospheric Science, Department of Chemistry , University of Cambridge , Cambridge CB2 1EW , United Kingdom.

The chemical composition and evolution of secondary organic aerosol (SOA) in the atmosphere represents one of the largest uncertainties in our current understanding of air quality. Despite vast research, the toxicological mechanisms relating to adverse human health effects upon exposure to particulate matter are still poorly understood. Particle-bound reactive oxygen species (ROS) may substantially contribute to observed health effects by influencing aerosol oxidative potential (OP). The role of radicals in both the formation and aging of aerosol, as well as their contribution to aerosol OP, remains highly uncertain. The profluorescent spin trap BPEAnit (9,10-bis(phenylethynyl)anthracenenitroxide), previously utilized to study combustion-generated aerosol, has been applied to provide the first estimate of particle-bound radical concentrations in SOA. We demonstrate that SOA from different atmospherically important VOC precursors have different particle-bound radical concentrations, estimated for the ozonolysis of α-pinene (0.020 ± 0.0050 nmol/μg), limonene (0.0059 ± 0.0010 nmol/μg), and β-caryophyllene (0.0025 ± 0.00080 nmol/μg), highlighting the potential importance of OH-initiated formation of particle-bound organic radicals. Additionally, the lifetime of particle-bound radical species in α-pinene SOA was estimated, and a pseudo-first-order rate constant of k = 7.3 ± 1.7 × 10 s was derived, implying a radical lifetime on the order of minutes.
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http://dx.doi.org/10.1021/acs.est.9b00825DOI Listing
June 2019

A light-driven burst of hydroxyl radicals dominates oxidation chemistry in newly activated cloud droplets.

Sci Adv 2019 May 1;5(5):eaav7689. Epub 2019 May 1.

Department of Atmospheric and Oceanic Sciences, University of California at Los Angeles, Los Angeles, CA 90095-1565, USA.

Aerosol particles and their interactions with clouds are one of the most uncertain aspects of the climate system. Aerosol processing by clouds contributes to this uncertainty, altering size distributions, chemical composition, and radiative properties. Many changes are limited by the availability of hydroxyl radicals in the droplets. We suggest an unrecognized potentially substantial source of OH formation in cloud droplets. During the first few minutes following cloud droplet formation, the material in aerosols produces a near-UV light-dependent burst of hydroxyl radicals, resulting in concentrations of 0.1 to 3.5 micromolar aqueous OH ([OH]). The source of this burst is previously unrecognized chemistry between iron(II) and peracids. The contribution of the "OH burst" to total OH in droplets varies widely, but it ranges up to a factor of 5 larger than previously known sources. Thus, this new process will substantially enhance the impact of clouds on aerosol properties.
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http://dx.doi.org/10.1126/sciadv.aav7689DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6494489PMC
May 2019

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

Anal Chem 2019 04 29;91(8):5051-5057. Epub 2019 Mar 29.

Department of Chemistry , University of Cambridge , Lensfield Road , Cambridge CB2 1EW , United Kingdom.

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 high performance liquid chromatography-mass spectrometry (HPLC-MS) analysis, without the need of preconcentrating 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 characterized by limits of detection (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 (SOAs) 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 the 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.
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http://dx.doi.org/10.1021/acs.analchem.8b05224DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6536135PMC
April 2019

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

Chemosphere 2019 Jun 27;224:786-795. Epub 2019 Feb 27.

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom; Department of Environmental Sciences, University of Basel, Klingelbergstrasse 27, 4056, Basel, Switzerland.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous atmospheric pollutants of high concern for public health. In the atmosphere they undergo oxidation, mainly through reactions with ·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 PM 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 PM 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.
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http://dx.doi.org/10.1016/j.chemosphere.2019.02.151DOI Listing
June 2019

A new method for the determination of primary and secondary terrestrial and marine biomarkers in ice cores using liquid chromatography high-resolution mass spectrometry.

Talanta 2019 Mar 16;194:233-242. Epub 2018 Oct 16.

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom. Electronic address:

The majority of atmospheric compounds measured in ice cores are inorganic, while analysis of their organic counterparts is a less well developed field. In recent years, understanding of formation, transport pathways and preservation of these compounds in ice and snow has improved, showing great potential for their use as biomarkers in ice cores. This study presents an optimised analytical technique for quantification of terrestrial and marine biosphere emissions of secondary organic aerosol (SOA) components and fatty acids in ice using HPLC-MS analysis. Concentrations of organic compounds in snow and ice are extremely low (typically ppb or ppt levels) and thus pre-concentration is required prior to analysis. Stir bar sorptive extraction (SBSE) showed potential for fatty acid compounds, but failed to recover SOA compounds. Solid phase extraction (SPE) recovered compounds across both organic groups but methods improving some recoveries came at the expense of others, and background contamination of fatty acids was high. Rotary evaporation was by far the best performing method across both SOA and fatty acid compounds, with average recoveries of 80%. The optimised preconcentration - HPLC-MS method achieved repeatability of 9% averaged for all compounds. In environmental samples, both concentrations and seasonal trends were observed to be reproducible when analysed in two different laboratories using the same method.
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http://dx.doi.org/10.1016/j.talanta.2018.10.042DOI Listing
March 2019

Observations of sesquiterpenes and their oxidation products in central Amazonia during the wet and dry seasons.

Atmos Chem Phys 2018 Jul;18(14):10433-10457

Instituto Nacional de Pesquisas da Amazonia, Manaus, AM, Brazil.

Biogenic volatile organic compounds (BVOCs) from the Amazon forest region represent the largest source of organic carbon emissions to the atmosphere globally. These BVOC emissions dominantly consist of volatile and intermediate-volatility terpenoid compounds that undergo chemical transformations in the atmosphere to form oxygenated condensable gases and secondary organic aerosol (SOA). We collected quartz filter samples with 12 h time resolution and performed hourly in situ measurements with a semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) at a rural site ("T3") located to the west of the urban center of Manaus, Brazil as part of the Green Ocean Amazon (GoAmazon2014/5) field campaign to measure intermediate-volatility and semi-volatile BVOCs and their oxidation products during the wet and dry seasons. We speciated and quantified 30 sesquiterpenes and 4 diterpenes with mean concentrations in the range 0.01-6.04 ngm (1-670ppq). We estimate that sesquiterpenes contribute approximately 14 and 12% to the total reactive loss of O via reaction with isoprene or terpenes during the wet and dry seasons, respectively. This is reduced from ~ 50-70 % for within-canopy reactive O3 loss attributed to the ozonolysis of highly reactive sesquiterpenes (e.g., -caryophyllene) that are reacted away before reaching our measurement site. We further identify a suite of their oxidation products in the gas and particle phases and explore their role in biogenic SOA formation in the central Amazon region. Synthesized authentic standards were also used to quantify gas- and particle-phase oxidation products derived from -caryophyllene. Using tracer-based scaling methods for these products, we roughly estimate that sesquiterpene oxidation contributes at least 0.4-5 % (median 1 %) of total submicron OA mass. However, this is likely a low-end estimate, as evidence for additional unaccounted sesquiterpenes and their oxidation products clearly exists. By comparing our field data to laboratory-based sesquiterpene oxidation experiments we confirm that more than 40 additional observed compounds produced through sesquiterpene oxidation are present in Amazonian SOA, warranting further efforts towards more complete quantification.
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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7751628PMC
July 2018

Measuring Aerosol Phase Changes and Hygroscopicity with a Microresonator Mass Sensor.

Anal Chem 2018 08 31;90(16):9716-9724. Epub 2018 Jul 31.

Centre for Atmospheric Science, Department of Chemistry , University of Cambridge , Cambridge CB2 1EW , United Kingdom.

The interaction between atmospheric aerosol particles and water vapor influences aerosol size, phase, and composition, parameters which critically influence their impacts in the atmosphere. Methods to accurately measure aerosol water uptake for a wide range of particle types are therefore merited. We present here a new method for characterizing aerosol hygroscopicity, an impaction stage containing a microelectromechanical systems (MEMS) microresonator. We find that deliquescence and efflorescence relative humidities (RHs) of sodium chloride and ammonium sulfate are easily diagnosed via changes in resonant frequency and peak sharpness. These agree well with literature values and thermodynamic models. Furthermore, we demonstrate that, unlike other resonator-based techniques, full hygroscopic growth curves can be derived, including for an inorganic-organic mixture (sodium chloride and malonic acid) which remains liquid at all RHs. The response of the microresonator frequency to temperature and particle mechanical properties and the resulting limitations when measuring hygroscopicity are discussed. MEMS resonators show great potential as miniaturized ambient aerosol mass monitors, and future work will consider the applicability of our approach to complex ambient samples. The technique also offers an alternative to established methods for accurate thermodynamic measurements in the laboratory.
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http://dx.doi.org/10.1021/acs.analchem.8b00114DOI Listing
August 2018

1064 nm Dispersive Raman Microspectroscopy and Optical Trapping of Pharmaceutical Aerosols.

Anal Chem 2018 08 13;90(15):8838-8844. Epub 2018 Jul 13.

Central Laser Facility, Research Complex at Harwell , Rutherford Appleton Laboratory , Didcot , OX11 0FA , United Kingdom.

Raman spectroscopy is a powerful tool for investigating chemical composition. Coupling Raman spectroscopy with optical microscopy (Raman microspectroscopy) and optical trapping (Raman tweezers) allows microscopic length scales and, hence, femtolitre volumes to be probed. Raman microspectroscopy typically uses UV/visible excitation lasers, but many samples, including organic molecules and complex tissue samples, fluoresce strongly at these wavelengths. Here we report the development and application of dispersive Raman microspectroscopy designed around a near-infrared continuous wave 1064 nm excitation light source. We analyze microparticles (1-5 μm diameter) composed of polystyrene latex and from three real-world pressurized metered dose inhalers (pMDIs) used in the treatment of asthma: salmeterol xinafoate (Serevent), salbutamol sulfate (Salamol), and ciclesonide (Alvesco). For the first time, single particles are captured, optically levitated, and analyzed using the same 1064 nm laser, which permits a convenient nondestructive chemical analysis of the true aerosol phase. We show that particles exhibiting overwhelming fluorescence using a visible laser (514.5 nm) can be successfully analyzed with 1064 nm excitation, irrespective of sample composition and irradiation time. Spectra are acquired rapidly (1-5 min) with a wavelength resolution of 2 nm over a wide wavenumber range (500-3100 cm). This is despite the microscopic sample size and low Raman scattering efficiency at 1064 nm. Spectra of individual pMDI particles compare well to bulk samples, and the Serevent pMDI delivers the thermodynamically preferred crystal form of salmeterol xinafoate. 1064 nm dispersive Raman microspectroscopy is a promising technique that could see diverse applications for samples where fluorescence-free characterization is required with high spatial resolution.
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http://dx.doi.org/10.1021/acs.analchem.8b00817DOI Listing
August 2018

Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation.

J Phys Chem A 2017 Oct 27;121(40):7641-7654. Epub 2017 Sep 27.

Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR7583, CNRS, Université Paris-Est-Créteil et Université Paris Diderot, Institut Pierre Simon Laplace , Créteil, France.

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth's changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25-32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of-flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15-20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.
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http://dx.doi.org/10.1021/acs.jpca.7b05933DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5642272PMC
October 2017

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

Faraday Discuss 2017 08;200:559-578

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.

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 the 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 show 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 that were 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), shows that our new method can be used for the quantification of CIs produced in situ in laboratory experiments.
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http://dx.doi.org/10.1039/c7fd00025aDOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5708353PMC
August 2017

Online Quantification of Criegee Intermediates of α-Pinene Ozonolysis by Stabilization with Spin Traps and Proton-Transfer Reaction Mass Spectrometry Detection.

J Am Chem Soc 2017 03 7;139(11):3999-4008. Epub 2017 Mar 7.

Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge, CB2 1EW, United Kingdom.

Biogenic alkenes, which are among the most abundant volatile organic compounds in the atmosphere, are readily oxidized by ozone. Characterizing the reactivity and kinetics of the first-generation products of these reactions, carbonyl oxides (often named Criegee intermediates), is essential in defining the oxidation pathways of organic compounds in the atmosphere but is highly challenging due to the short lifetime of these zwitterions. Here, we report the development of a novel online method to quantify atmospherically relevant Criegee intermediates (CIs) in the gas phase by stabilization with spin traps and analysis with proton-transfer reaction mass spectrometry. Ozonolysis of α-pinene has been chosen as a proof-of-principle model system. To determine unambiguously the structure of the spin trap adducts with α-pinene CIs, the reaction was tested in solution, and reaction products were characterized with high-resolution mass spectrometry, electron paramagnetic resonance, and nuclear magnetic resonance spectroscopy. DFT calculations show that addition of the Criegee intermediate to the DMPO spin trap, leading to the formation of a six-membered ring adduct, occurs through a very favorable pathway and that the product is significantly more stable than the reactants, supporting the experimental characterization. A flow tube set up has been used to generate spin trap adducts with α-pinene CIs in the gas phase. We demonstrate that spin trap adducts with α-pinene CIs also form in the gas phase and that they are stable enough to be detected with online mass spectrometry. This new technique offers for the first time a method to characterize highly reactive and atmospherically relevant radical intermediates in situ.
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http://dx.doi.org/10.1021/jacs.6b10981DOI Listing
March 2017

Mass Spectrometry Characterization of Peroxycarboxylic Acids as Proxies for Reactive Oxygen Species and Highly Oxygenated Molecules in Atmospheric Aerosols.

Anal Chem 2017 03 10;89(5):2873-2879. Epub 2017 Feb 10.

Department of Chemistry, University of Cambridge , Cambridge, CB2 1EW, United Kingdom.

A significant fraction of atmospheric aerosol particles is composed of organic material with a highly complex but poorly characterized composition. For a better understanding of aerosol effects and processes in the atmosphere, a more detailed knowledge of aerosol components at a molecular level is needed. Peroxy acids might play a significant role in particle toxicity, due to their oxidizing properties, and they were recently found to be involved in particle formation. Because of the lack of appropriate standards, the identification and quantification of peroxy acids is often highly uncertain. Mass spectrometry (MS) is a powerful tool to characterize unidentified compounds in complex mixtures. However, so far there is only little information regarding the ionization and fragmentation behavior of peroxy acids in mass spectrometers. To study their fragmentation patterns, we synthesized 12 peroxy acids with C to C carbon backbones and mono- or diperoxy acid functionality. The peroxy acids were separated using liquid chromatography, detected via negative mode electrospray ionization high-resolution MS, and their fragmentation patterns (MS/MS spectra) were identified. The MS/MS spectra of the peroxy acids showed fragmentation patterns clearly different from the corresponding acid, with a strong similarity between compounds of different chain length but analogous functional groups. Neutral loss of CHO was observed for all investigated linear peroxy acids but not for carboxylic acids and could therefore serve as a diagnostic ion for peroxy acids. The obtained results are a large step toward unambiguous characterization of peroxy acids in the atmosphere.
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http://dx.doi.org/10.1021/acs.analchem.6b04127DOI Listing
March 2017

Dynamic viscosity mapping of the oxidation of squalene aerosol particles.

Phys Chem Chem Phys 2016 Nov;18(44):30385-30393

Department of Chemistry, Imperial College London, London, SW7 2AZ, UK.

Organic aerosols (OAs) play important roles in multiple atmospheric processes, including climate change, and can impact human health. The physico-chemical properties of OAs are important for all these processes and can evolve through reactions with various atmospheric components, including oxidants. The dynamic nature of these reactions makes it challenging to obtain a true representation of their composition and surface chemistry. Here we investigate the microscopic viscosity of the model OA composed of squalene, undergoing chemical aging. We employ Fluorescent Lifetime Imaging Microscopy (FLIM) in conjunction with viscosity sensitive probes termed molecular rotors, in order to image the changes in microviscosity in real time during oxidation with ozone and hydroxyl radicals, which are two key oxidising species in the troposphere. We also recorded the Raman spectra of the levitated particles to follow the reactivity during particle ozonolysis. The levitation of droplets was achieved via optical trapping that enabled simultaneous levitation and measurement via FLIM or Raman spectroscopy and allowed the true aerosol phase to be probed. Our data revealed a very significant increase in viscosity of the levitated squalene droplets upon ozonolysis, following their transformation from the liquid to solid phase that was not observable when the oxidation was carried out on coverslip mounted droplets. FLIM imaging with sub-micron spatial resolution also revealed spatial heterogeneity in the viscosity distribution of oxidised droplets. Overall, a combination of molecular rotors, FLIM and optical trapping is able to provide powerful insights into OA chemistry and the microscopic structure that enables the dynamic monitoring of microscopic viscosity in aerosol particles in their true phase.
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http://dx.doi.org/10.1039/c6cp05674aDOI Listing
November 2016

Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols.

Sci Rep 2016 10 13;6:35038. Epub 2016 Oct 13.

Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UK.

Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.
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http://dx.doi.org/10.1038/srep35038DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5062071PMC
October 2016

Molecular composition of organic aerosols at urban background and road tunnel sites using ultra-high resolution mass spectrometry.

Faraday Discuss 2016 07;189:51-68

Centre for Atmospheric Science, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.

Organic aerosol composition in the urban atmosphere is highly complex and strongly influenced by vehicular emissions which vary according to the make-up of the vehicle fleet. Normalized test measurements do not necessarily reflect real-world emission profiles and road tunnels are therefore ideal locations to characterise realistic traffic particle emissions with minimal interference from other particle sources and from atmospheric aging processes affecting their composition. In the current study, the composition of fine particles (diameter ≤2.5 μm) at an urban background site (Elms Road Observatory Site) and a road tunnel (Queensway) in Birmingham, UK, were analysed with direct infusion, nano-electrospray ionisation ultrahigh resolution mass spectrometry (UHRMS). The overall particle composition at these two sites is compared with an industrial harbour site in Cork, Ireland, with special emphasis on oxidised mono-aromatics, polycyclic aromatic hydrocarbons (PAHs) and nitro-aromatics. Different classification criteria, such as double bond equivalents, aromaticity index and aromaticity equivalent are used and compared to assess the fraction of aromatic components in the approximately one thousand oxidized organic compounds at the different sampling locations.
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http://dx.doi.org/10.1039/c5fd00206kDOI Listing
July 2016

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

Anal Chem 2015 Oct 30;87(19):9900-7. Epub 2015 Sep 30.

Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge, CB2 1EW, United Kingdom.

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.
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http://dx.doi.org/10.1021/acs.analchem.5b02498DOI Listing
October 2015

Toxicity of aged gasoline exhaust particles to normal and diseased airway epithelia.

Sci Rep 2015 Jun 29;5:11801. Epub 2015 Jun 29.

Institute of Anatomy, University of Bern, 3012 Bern, Switzerland.

Particulate matter (PM) pollution is a leading cause of premature death, particularly in those with pre-existing lung disease. A causative link between particle properties and adverse health effects remains unestablished mainly due to complex and variable physico-chemical PM parameters. Controlled laboratory experiments are required. Generating atmospherically realistic aerosols and performing cell-exposure studies at relevant particle-doses are challenging. Here we examine gasoline-exhaust particle toxicity from a Euro-5 passenger car in a uniquely realistic exposure scenario, combining a smog chamber simulating atmospheric ageing, an aerosol enrichment system varying particle number concentration independent of particle chemistry, and an aerosol deposition chamber physiologically delivering particles on air-liquid interface (ALI) cultures reproducing normal and susceptible health status. Gasoline-exhaust is an important PM source with largely unknown health effects. We investigated acute responses of fully-differentiated normal, distressed (antibiotics-treated) normal, and cystic fibrosis human bronchial epithelia (HBE), and a proliferating, single-cell type bronchial epithelial cell-line (BEAS-2B). We show that a single, short-term exposure to realistic doses of atmospherically-aged gasoline-exhaust particles impairs epithelial key-defence mechanisms, rendering it more vulnerable to subsequent hazards. We establish dose-response curves at realistic particle-concentration levels. Significant differences between cell models suggest the use of fully-differentiated HBE is most appropriate in future toxicity studies.
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http://dx.doi.org/10.1038/srep11801DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4484354PMC
June 2015