Epidemiological studies have consistently linked exposure to PM2.5 with adverse health effects. The oxidative potential (OP) of aerosol particles has been widely suggested as a measure of their potential toxicity. Several acellular chemical assays are now readily employed to measure OP; however, uncertainty remains regarding the atmospheric conditions and specific chemical components of PM2.5 that drive OP. A limited number of studies have simultaneously utilised multiple OP assays with a wide range of concurrent measurements and investigated the seasonality of PM2.5 OP. In this work, filter samples were collected in winter 2016 and summer 2017 during the atmospheric pollution and human health in a Chinese megacity campaign (APHH-Beijing), and PM2.5 OP was analysed using four acellular methods: ascorbic acid (AA), dithiothreitol (DTT), 2,7-dichlorofluorescin/hydrogen peroxidase (DCFH) and electron paramagnetic resonance spectroscopy (EPR). Each assay reflects different oxidising properties of PM2.5, including particle-bound reactive oxygen species (DCFH), superoxide radical production (EPR) and catalytic redox chemistry (DTT/AA), and a combination of these four assays provided a detailed overall picture of the oxidising properties of PM2.5 at a central site in Beijing. Positive correlations of OP (normalised per volume of air) of all four assays with overall PM2.5 mass were observed, with stronger correlations in winter compared to summer. In contrast, when OP assay values were normalised for particle mass, days with higher PM2.5 mass concentrations (µg m−3) were found to have lower mass-normalised OP values as measured by AA and DTT. This finding supports that total PM2.5 mass concentrations alone may not always be the best indicator for particle toxicity. Univariate analysis of OP values and an extensive range of additional measurements, 107 in total, including PM2.5 composition, gas-phase composition and meteorological data, provided detailed insight into the chemical components and atmospheric processes that determine PM2.5 OP variability. Multivariate statistical analyses highlighted associations of OP assay responses with varying chemical components in PM2.5 for both mass- and volume-normalised data. AA and DTT assays were well predicted by a small set of measurements in multiple linear regression (MLR) models and indicated fossil fuel combustion, vehicle emissions and biogenic secondary organic aerosol (SOA) as influential particle sources in the assay response. Mass MLR models of OP associated with compositional source profiles predicted OP almost as well as volume MLR models, illustrating the influence of mass composition on both particle-level OP and total volume OP. Univariate and multivariate analysis showed that different assays cover different chemical spaces, and through comparison of mass- and volume-normalised data we demonstrate that mass-normalised OP provides a more nuanced picture of compositional drivers and sources of OP compared to volume-normalised analysis. This study constitutes one of the most extensive and comprehensive composition datasets currently available and provides a unique opportunity to explore chemical variations in PM2.5 and how they affect both PM2.5 OP and the concentrations of particle-bound reactive oxygen species.
Differences in the composition of organic aerosols between winter and summer in Beijing: a study by direct-infusion ultrahigh-resolution mass spectrometry
Steimer, SS; Patton, DJ; Vu, TV; Panagi, M; Monks, PS; Harrison, RM; Fleming, ZL; Shi, Z; Kalberer, M
This study investigates the chemical composition of PM2.5 collected at a central location in Beijing, China, during winter 2016 and summer 2017. The samples were characterised using direct-infusion negative-nano-electrospray-ionisation ultrahigh-resolution mass spectrometry to elucidate the composition and the potential primary and secondary sources of the organic fraction. The samples from the two seasons were compared with those from a road-tunnel site and an urban background site in Birmingham, UK, analysed in the course of an earlier study using the same method. There were strong differences in aerosol particle composition between the seasons, particularly regarding (poly-)aromatic compounds, which were strongly enhanced in winter, likely due to increased fossil fuel and biomass burning for heating. In addition to the seasonal differences, compositional differences between high- and low-pollution conditions were observed, with the contribution of sulfur-containing organic compounds strongly enhanced under high-pollution conditions. There was a correlation of the number of sulfur-containing molecular formulae with the concentration of particulate sulfate, consistent with a particle-phase formation process.
MIMiX: a Multipurpose In situ Microreactor system for X-ray microspectroscopy to mimic atmospheric aerosol processing
Forster, JD; Gurk, C; Lamneck, M; Tong, HJ; Ditas, F; Steimer, SS; Alpert, PA; Ammann, M; Raabe, J; Weigand, M; Watts, B; Poschl, U; Andreae, MO; Pohlker, C
| Atmos. Meas. Tech.
hygroscopic growth measurements
particle critical supersaturation
The dynamic processing of aerosols in the atmosphere is difficult to mimic under laboratory conditions, particularly on a single-particle level with high spatial and chemical resolution. Our new microreactor system for X-ray microscopy facilitates observations under in situ conditions and extends the accessible parameter ranges of existing setups to very high humidities and low temperatures. With the parameter margins for pressure (180-1000 hPa), temperature (similar to 250 K to room temperature), and relative humidity (similar to 0% to above 98 %), a wide range of tropospheric conditions is covered. Unique features are the mobile design and compact size that make the instrument applicable to different synchrotron facilities. Successful first experiments were conducted at two X-ray microscopes, MAXYMUS, located at beamline UE46 of the synchrotron BESSY II, and PolLux, located at beamline X07DA of the Swiss Light Source in the Paul Scherrer Institute. Here we present the design and analytical scope of the system, along with first results from hydration-dehydration experiments on ammonium sulfate and potassium sulfate particles and the tentative observation of water ice at low temperature and high relative humidity in a secondary organic aerosol particle from isoprene oxidation.
Visualizing reaction and diffusion in xanthan gum aerosol particles exposed to ozone
Atmospheric aerosol particles with a high viscosity may become inhomogeneously mixed during chemical processing. Models have predicted gradients in condensed phase reactant concentration throughout particles as the result of diffusion and chemical reaction limitations, termed chemical gradients. However, these have never been directly observed for atmospherically relevant particle diameters. We investigated the reaction between ozone and aerosol particles composed of xanthan gum and FeCl2 and observed the in situ chemical reaction that oxidized Fe2+ to Fe3+ using X-ray spectromicroscopy. Iron oxidation state of particles as small as 0.2 µm in diameter were imaged over time with a spatial resolution of tens of nanometers. We found that the loss off Fe2+ accelerated with increasing ozone concentration and relative humidity, RH. Concentric 2-D column integrated profiles of the Fe2+ fraction, ɑ, out of the total iron were derived and demonstrated that particle surfaces became oxidized while particle cores remained unreacted at RH = 0-20%. At higher RH, chemical gradients evolved over time, extended deeper from the particle surface, and Fe2+ became more homogeneously distributed. We used the kinetic multi-layer model for aerosol surface and bulk chemistry (KM-SUB) to simulate ozone reaction constrained with our observations and inferred key parameters as a function of RH including Henry's Law constant for ozone, HO3, and diffusion coefficients for ozone and iron, DO3 and DFe, respectively. We found that HO3 is higher in our xanthan gum/FeCl2 particles than for water and increases when RH decreased from about 80% to dry conditions. This coincided with a decrease in both DO3 and DFe. In order to reproduce observed chemical gradients, our model predicted that ozone could not be present further than a few nanometers from a particle surface indicating near surface reactions were driving changes in iron oxidation state. However, the observed chemical gradients in ɑ observed over hundreds of nanometers must have been the result of iron transport from the particle interior to the surface where ozone oxidation occurred. In the context of our results, we examine the applicability of the reacto-diffusive framework and discuss diffusion limitations for other reactive gas-aerosol systems of atmospheric importance.
Synthesis and characterisation of peroxypinic acids as proxies for highly oxygenated molecules (HOMs) in secondary organic aerosol
Steimer, SS; Delvaux, A; Campbell, SJ; Gallimore, PJ; Grice, P; Howe, DJ; Pitton, D; Claeys, M; Hoffmann, T; Kalberer, M
Peroxy acids were recently found to be involved in new particle formation in the atmosphere and could also substantially contribute towards particle toxicity. However, a lack of suitable analytical methods for the detection and characterisation of peroxy acids in the particle phase is currently hindering the quantitative investigation of their contribution to these important atmospheric processes. Further development of appropriate techniques and relevant standards is therefore urgently needed. In this study, we synthesised three peroxypinic acids, developed a liquid chromatography separation method and characterised them with tandem mass spectrometry. The observed fragmentation patterns clearly distinguish the different peroxypinic acids from both the acid and each other, showing several neutral losses previously already observed for other peroxy acids. Both monoperoxypinic acids were found to be present in secondary organic aerosol generated from ozonolysis of alpha-pinene in laboratory experiments. The yield of monoperoxypinic acid formation was not influenced by humidity. Monoperoxypinic acid quickly degrades on the filter, with about 60% lost within the first 5 h. This fast degradation shows that time delays in traditional off-line analysis will likely lead to severe underestimates of peroxy compound concentrations in ambient particles.
Fatty Acid Surfactant Photochemistry Results in New Particle Formation
Alpert, PA; Ciuraru, R; Rossignol, S; Passananti, M; Tinel, L; Perrier, S; Dupart, Y; Steimer, SS; Ammann, M; Donaldson, DJ; George, C
Organic interfaces that exist at the sea surface microlayer or as surfactant coatings on cloud droplets are highly concentrated and chemically distinct from the underlying bulk or overlying gas phase. Therefore, they may be potentially unique locations for chemical or photochemical reactions. Recently, photochemical production of volatile organic compounds (VOCs) was reported at a nonanoic acid interface however, subsequent secondary organic aerosol (SOA) particle production was incapable of being observed. We investigated SOA particle formation due to photochemical reactions occurring at an air-water interface in presence of model saturated long chain fatty acid and alcohol surfactants, nonanoic acid and nonanol, respectively. Ozonolysis of the gas phase photochemical products in the dark or under continued UV irradiation both resulted in nucleation and growth of SOA particles. Irradiation of nonanol did not yield detectable VOC or SOA production. Organic carbon functionalities of the SOA were probed using X-ray microspectroscopy and compared with other laboratory generated and field collected particles. Carbon-carbon double bonds were identified in the condensed phase which survived ozonolysis during new particle formation and growth. The implications of photochemical processes occurring at organic coated surfaces are discussed in the context of marine SOA particle atmospheric fluxes.
Mass Spectrometry Characterization of Peroxycarboxylic Acids as Proxies for Reactive Oxygen Species and Highly Oxygenated Molecules in Atmospheric Aerosols
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 C8 to C10 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 CH2O2, 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.
The effect of viscosity and diffusion on the HO2 uptake by sucrose and secondary organic aerosol particles
Lakey, PSJ; Berkemeier, T; Krapf, M; Dommen, J; Steimer, SS; Whalley, LK; Ingham, T; Baeza-Romero, MT; Poschl, U; Shiraiwa, M; Ammann, M; Heard, DE
We report the first measurements of HO2 uptake coefficients, ɣ, for secondary organic aerosol (SOA) particles and for the well-studied model compound sucrose which we doped with copper(II). Above 65% relative humidity (RH), ɣ for copper(II)-doped sucrose aerosol particles equalled the surface mass accommodation coefficient ɑ = 0.22 +/- 0.06, but it decreased to ɣ = 0.012 +/- 0.007 upon decreasing the RH to 17 %. The trend of ɣ with RH can be explained by an increase in aerosol viscosity and the contribution of a surface reaction, as demonstrated using the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). At high RH the total uptake was driven by reaction in the near-surface bulk and limited by mass accommodation, whilst at low RH it was limited by surface reaction. SOA from two different precursors, ɑ-pinene and 1,3,5-trimethylbenzene (TMB), was investigated, yielding low uptake coefficients of ɣ < 0.001 and ɣ = 0.004 +/- 0.002, respectively. It is postulated that the larger values measured for TMB-derived SOA compared to ɑ-pinene-derived SOA are either due to differing viscosity, a different liquid water content of the aerosol particles, or an HO2 + RO2 reaction occurring within the aerosol particles.
Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO2 radical formation and aerosol growth
Palacios, LG; Arroyo, PC; Aregahegn, KZ; Steimer, SS; Bartels-Rausch, T; Noziere, B; George, C; Ammann, M; Volkamer, R
The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its light-absorbing product imidazole-2-carboxaldehyde (IC). IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake) via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT) experiments using films of IC and citric acid (CA), an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO2 radicals (PHO2) was measured indirectly by converting gas-phase NO into NO2. We report on experiments that relied on measurements of NO2 formation, NO loss and HONO formation. P-HO2 was found to be a linear function of (1) the [IC] x [CA] concentration product and (2) the photon actinic flux. Additionally, (3) a more complex function of relative humidity (25% < RH < 63 %) and of (4) the O2/N2 ratio (15% < O-2/N-2 < 56 %) was observed, most likely indicating competing effects of dilution, HO2 mobility and losses in the film. The maximum PHO2 was observed at 25-55% RH and at ambient O2/N2. The HO2 radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O2 to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO2 in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NOx in aerosol flow tube experiments, confirming significant PHO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO2 production, aerosol growth and ageing in the atmosphere.
Ozone uptake on glassy, semi-solid and liquid organic matter and the role of reactive oxygen intermediates in atmospheric aerosol chemistry
Berkemeier, T; Steimer, SS; Krieger, UK; Peter, T; Poschl, U; Ammann, M; Shiraiwa, M
Heterogeneous and multiphase reactions of ozone are important pathways for chemical ageing of atmospheric organic aerosols. To demonstrate and quantify how moisture-induced phase changes can affect the gas uptake and chemical transformation of organic matter, we apply a kinetic multi-layer model to a comprehensive experimental data set of ozone uptake by shikimic acid. The bulk diffusion coefficients were determined to be 10-12 cm2 s-1 for ozone and 10-20 cm2 s-1 for shikimic acid under dry conditions, increasing by several orders of magnitude with increasing relative humidity (RH) due to phase changes from amorphous solid over semisolid to liquid. Consequently, the reactive uptake of ozone progresses through different kinetic regimes characterised by specific limiting processes and parameters. At high RH, ozone uptake is driven by reaction throughout the particle bulk; at low RH it is restricted to reaction near the particle surface and kinetically limited by slow diffusion and replenishment of unreacted organic molecules. Our results suggest that the chemical reaction mechanism involves long-lived reactive oxygen intermediates, likely primary ozonides or O atoms, which may provide a pathway for self-reaction and catalytic destruction of ozone at the surface. Slow diffusion and ozone destruction can effectively shield reactive organic molecules in the particle bulk from degradation. We discuss the potential non-orthogonality of kinetic parameters, and show how this problem can be solved by using comprehensive experimental data sets to constrain the kinetic model, providing mechanistic insights into the coupling of transport, phase changes, and chemical reactions of multiple species in complex systems.
Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?
New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of alpha-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH4HSO4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous ice nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.
Electrodynamic balance measurements of thermodynamic, kinetic, and optical aerosol properties inaccessible to bulk methods
Steimer, SS; Krieger, UK; Te, YF; Lienhard, DM; Huisman, AJ; Luo, BP; Ammann, M; Peter, T
Measurements of a single, levitated particle in an electrodynamic balance are an established tool for deriving thermodynamic and material data such as density, refractive index and activities of components of an aqueous solution under supersaturated conditions, where bulk measurements are not possible. The retrieval relies on combining mass-to-charge data and size data from light scattering. Here, we use a combination of low- and high-resolution Mie resonance spectroscopy to obtain radius data, enabling an accurate size determination not only when the particle is in equilibrium, but also when it is out of equilibrium due to kinetic limitation of mass transport. With the data measured under non-equilibrium conditions, it is possible to retrieve the water diffusivity. A challenge is that the radius retrieval by comparing measured light scattering with Mie theory requires the knowledge of refractive index as a function of concentration. Here, we show an iterative retrieval of refractive index and size for compounds for which data cannot be obtained in the bulk either due to lack of sufficient amounts of sample or limited solubility. We demonstrate the measurement strategy and the retrieval of water activity, density, refractive index and water diffusivity for aqueous shikimic acid. Water diffusivity in concentrated shikimic acid decreases by 6 orders of magnitude at 250 K compared to that at room temperature.