Ambient Atmospheric Particles Research Articles

Detecting the pH-dependent liquid-liquid phase separation of single levitated aerosol microdroplets via laser tweezers-Raman spectroscopy

Ambient atmospheric aerosol particles comprised of various inorganic and organic substances ubiquitously undergo phase transition, such as efflorescence, amorphization, and especially liquid-liquid phase separation (LLPS). Resultant changes of physicochemical properties in aerosols then deeply affect the climate system. However, finely detecting these processes occurring in single aerosol particles, especially under the acidic condition of real atmospheric environment, remains a challenge. In this work, we investigated the pH-dependent phase separation in single levitated microdroplets using a self-developed laser tweezers Raman spectroscopy (LTRS) system. The dynamic process of LLPS in laser-trapped droplets over the course of humidity cycles was detected with the time-resolved cavity-enhanced Raman spectra. These measurements provide the first comprehensive account of the pH-dependent LLPS in single levitated aerosol microdroplets and bring possible implications on phase separation in actual atmospheric particles.

Detection of polycyclic aromatic hydrocarbons using a high performance-single particle aerosol mass spectrometer

The real-time detection of the mixing states of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs in ambient particles is of great significance for analyzing the source, aging process, and health effects of PAHs and nitro-PAHs; yet there is still few effective technology to achieve this type of detection. In this study, 11 types of PAH and nitro-PAH standard samples were analyzed using a high performance-single particle aerosol mass spectrometer (HP-SPAMS) in lab studies. The identification principles ‘parent ions’ and ‘mass-to-charge (m/z) = 77’ of each compound were obtained in this study. It was found that different laser energies did not affect the identification of the parent ions. The comparative experiments of ambient atmospheric particles, cooking and biomass burning emitted particles with and without the addition of PAHs were conducted and ruled out the interferences from primary and secondary organics on the identification of PAHs. Besides, the reliability of the characteristic ions extraction method was evaluated through the comparative study of similarity algorithm and deep learning algorithm. In addition, the real PAH-containing particles from vehicle exhaust emissions and ambient particles were also analyzed. This study improves the ability of single particle mass spectrometry technology to detect PAHs and nitro-PAHs, and HP-SPAMS was superior to SPAMS for detecting single particles containing PAHs and nitro-PAHs. This study provides support for subsequent ambient observations to identify the characteristic spectrum of single particles containing PAHs and nitro-PAHs.

The Impact of Ambient Atmospheric Mineral-Dust Particles on the Calcification of Lungs

For the first time, it is shown that inhaled ambient air-dust particles settled in the human lower respiratory tract induce lung calcification. Chemical and mineral compositions of pulmonary calcium precipitates in the lung right lower-lobe (RLL) tissues of 12 individuals who lived in the Upper Silesia conurbation in Poland and who had died from causes not related to a lung disorder were determined by transmission and scanning electron microscopy. Whereas calcium salts in lungs are usually reported as phosphates, calcium salts precipitated in the studied RLL tissue were almost exclusively carbonates, specifically Mg-calcite and calcite. These constituted 37% of the 1652 mineral particles examined. Mg-calcite predominated in the submicrometer size range, with a MgCO3 content up to 50 mol %. Magnesium plays a significant role in lung mineralization, a fact so far overlooked. The calcium phosphate (hydroxyapatite) content in the studied RLL tissue was negligible. The predominance of carbonates is explained by the increased CO2 fugacity in the RLL. Carbonates enveloped inhaled mineral-dust particles, including uranium-bearing oxides, quartz, aluminosilicates, and metal sulfides. Three possible pathways for the carbonates precipitation on the dust particles are postulated: (1) precipitation of amorphous calcium carbonate (ACC), followed by its transformation to calcite; (2) precipitation of Mg-ACC, followed by its transformation to Mg-calcite; (3) precipitation of Mg-free ACC, causing a localized relative enrichment in Mg ions and subsequent heterogeneous nucleation and crystal growth of Mg-calcite. The actual number of inhaled dust particles may be significantly greater than was observed because of the masking effect of the carbonate coatings. There is no simple correlation between smoking habit and lung calcification.

Proton-Catalyzed Decomposition of α-Hydroxyalkyl-Hydroperoxides in Water.

In the atmosphere, most biogenic terpenes undergo ozonolysis in the presence of water to form reactive α-hydroxyalkyl-hydroperoxides (α-HHs), and the lifetimes of these α-HHs are a key parameter for understanding the processes that occur during the aging of atmospheric particles. We previously reported that α-HHs generated by ozonolysis of terpenes decompose in water to give H2O2 and the corresponding aldehydes, which undergo hydration to form gem-diols. Herein, we report that this decomposition process was dramatically accelerated by acidification of the water with oxalic, acetic, hexanoic, cis-pinonic, or hydrochloric acid. In acidic solution, the temporal profiles of the α-HHs, detected as their chloride adducts by electrospray mass spectrometry, showed single-exponential decays in the pH range from 4.1 to 6.1, and the first-order rate coefficients (k) for the decays increased with decreasing pH. The lifetime of the α-HH derived from α-terpineol was 128 min (k = (1.3 ± 0.4) × 10-4 s-1) at pH 6.1 but only 8 min (k = (2.1 ± 0.1) × 10-3 s-1) at pH 4.1. Because the rate coefficients increased as the pH decreased and the increase depended on pH rather than on the properties of the acid, we propose that the decomposition of the α-HHs in water was specifically catalyzed by H+. Fast H+-catalyzed decomposition of α-HHs could be an important source of H2O2 and multifunctionalized compounds found in ambient atmospheric particles.

Simultaneous Optical Photothermal Infrared (O-PTIR) and Raman Spectroscopy of Submicrometer Atmospheric Particles.

Physicochemical analysis of individual atmospheric aerosols at the most abundant sizes in the atmosphere (<1 μm) is analytically challenging, as hundreds to thousands of species are often present in femtoliter volumes. Vibrational spectroscopies, such as infrared (IR) and Raman, have great potential for probing functional groups in single particles at ambient pressure and temperature. However, the diffraction limit of IR radiation limits traditional IR microscopy to particles > ∼10 μm, which have less relevance to aerosol health and climate impacts. Optical photothermal infrared (O-PTIR) spectroscopy is a contactless method that circumvents diffraction limitations by using changes in the scattering intensity of a continuous wave visible laser (532 nm) to detect the photothermal expansion when a vibrational mode is excited by a tunable IR laser (QCL: 800-1800 cm-1 or OPO: 2600-3600 cm-1). Herein, we simultaneously collect O-PTIR spectra with Raman spectra at a single point for individual particles with aerodynamic diameters <400 nm (prior to impaction and spreading) at ambient temperature and pressure, by also collecting the inelastically scattered visible photons for Raman spectra. O-PTIR and Raman spectra were collected for submicrometer particles with different substrates, particle chemical compositions, and morphologies (i.e., core-shell), as well as IR mapping with submicron spatial resolution. Initial O-PTIR analysis of ambient atmospheric particles identified both inorganic and organic modes in individual sub- and supermicrometer particles. The simultaneous IR and Raman microscopy with submicrometer spatial resolution described herein has considerable potential both in atmospheric chemistry and numerous others fields (e.g., materials and biological research).

Atomic Force Microscopy-Infrared Spectroscopy of Individual Atmospheric Aerosol Particles: Subdiffraction Limit Vibrational Spectroscopy and Morphological Analysis.

Chemical analysis of atmospheric aerosols is an analytical challenge, as aerosol particles are complex chemical mixtures that can contain hundreds to thousands of species in attoliter volumes at the most abundant sizes in the atmosphere (∼100 nm). These particles have global impacts on climate and health, but there are few methods available that combine imaging and the detailed molecular information from vibrational spectroscopy for individual particles <500 nm. Herein, we show the first application of atomic force microscopy with infrared spectroscopy (AFM-IR) to detect trace organic and inorganic species and probe intraparticle chemical variation in individual particles down to 150 nm. By detecting photothermal expansion at frequencies where particle species absorb IR photons from a tunable laser, AFM-IR can study particles smaller than the optical diffraction limit. Combining strengths of AFM (ambient pressure, height, morphology, and phase measurements) with photothermal IR spectroscopy, the potential of AFM-IR is shown for a diverse set of single-component particles, liquid-liquid phase separated particles (core-shell morphology), and ambient atmospheric particles. The spectra from atmospheric model systems (ammonium sulfate, sodium nitrate, succinic acid, and sucrose) had clearly identifiable features that correlate with absorption frequencies for infrared-active modes. Additionally, molecular information was obtained with <100 nm spatial resolution for phase separated particles with a ∼150 nm shell and 300 nm core. The subdiffraction limit capability of AFM-IR has the potential to advance understanding of particle impacts on climate and health by improving analytical capabilities to study water uptake, heterogeneous reactivity, and viscosity.

Surface-Enhanced Raman Spectroscopy: A Facile and Rapid Method for the Chemical Component Study of Individual Atmospheric Aerosol.

A simple and rapid method for detecting chemical components of individual aerosol particles on Klarite substrate with surface-enhanced Raman spectroscopy (SERS) is described. For both single simulated aerosol particles and ambient atmospheric particles, this new analytical method promotes the enhancement factor of the Raman signal. The spectra of ammonium sulfate and naphthalene particles at the microscopic level are enhanced by a factor of 6 and therefore greatly improve the detection of the chemical composition of an individual aerosol particle. When aerosol particles are found over a microscopic domain, a set of Raman spectra with chemical information can be obtained via SERS mapping. The maps illustrate the distribution of organic or inorganic species on the SERS substrate. This constitutes a facile and rapid method to study aerosol particles. This new method allows the analysis of chemical composition in single aerosol particles, demonstrating the power of SERS to probe the ambient atmospheric particles and to study the formation of aerosol particles.

Water-soluble Inorganic Ions in the Road Ambient Atmospheric Particles of Tianjin

Atmospheric particles, especially water-soluble inorganic ions are hazardous to human body. Motor vehicle exhaust is the greatest contributor to atmosphere pollution in Tianjin. In order to explore the emission characteristics of different road types, PM2.5 and PM10 from four types of roads were sampled and analyzed by water-soluble ions component analysis and Pearson correlation analysis during the period of April to May, 2015 to discover the ratio of PM2.5 to PM10 and the major pollutants. The results showed that water-soluble inorganic ions mainly existed in fine particles varying with different road types, which mainly came from secondary pollution. The quantities of secondary ions in PM2.5 were twice as high as that in PM10, which were the key components of the water-soluble inorganic ions. This was probably due to the increase of automobiles and their emissions, as well as the transmission and spreading of pollutants in the surroundings. Furthermore, water-soluble inorganic ions might exist in the forms of NaNO3, NH4Cl, NH4NO3, (NH4)2SO4, KCl, KNO3, K2SO4, MgCl2, CaCl2, etc. K+, Mg2+, Na+and Ca2+ showed high homology and the contributors of PM2.5 and PM10 were mainly the mixture of combustion and secondary pollutants, then followed by the mixture of re-suspended dust and traffic source.

Chemical Characteristics of Fine Particles Emitted from Different Chinese Cooking Styles

Cooking process was regarded as one of the most significant contributor to fine particles (PM2.5) in ambient atmosphere and its chemical characteristics would be great different among various cooking styles. In this study, PM2.5 emitted from four different Chinese cooking styles, including Home cooking, Shandong cuisine, Hunan cuisine, and Barbecue, were collected using a dilution sampling system. Then, PM2.5 mass concentrations were weighted, and its chemical composition were analyzed. It was found that Barbecue emitted PM2.5 concentrations with the highest level, followed by Home cooking, Shandong cuisine and Hunan cuisine. PM2.5 emission amounts and emission factors were also estimated according to the measured data. Home cooking notably had the highest levels. The difference between Barbecue and other cuisines of PM2.5 chemical profiles were the largest by using the coefficient of divergence (CD) method. The predominant chemical composition was organic carbon (OC) in PM2.5. The main water-soluble ions were Na+, SO42–, NO3–, Cl–, and Ca2+, and Fe, S, and Ca had made up a big proportion of element. Little difference had been found between the mass fractions of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) from different cooking cuisines. However, Barbecue displayed the highest mass fractions of organic acids in cooking fume.

Seasonal variation of aerosol water uptake and its impact on the direct radiative effect at Ny-Ålesund, Svalbard

Abstract. In this study we investigated the impact of water uptake by aerosol particles in ambient atmosphere on their optical properties and their direct radiative effect (ADRE, W m−2) in the Arctic at Ny-Ålesund, Svalbard, during 2008. To achieve this, we combined three models, a hygroscopic growth model, a Mie model and a radiative transfer model, with an extensive set of observational data. We found that the seasonal variation of dry aerosol scattering coefficients showed minimum values during the summer season and the beginning of fall (July-August-September), when small particles (&lt; 100 nm in diameter) dominate the aerosol number size distribution. The maximum scattering by dry particles was observed during the Arctic haze period (March-April-May) when the average size of the particles was larger. Considering the hygroscopic growth of aerosol particles in the ambient atmosphere had a significant impact on the aerosol scattering coefficients: the aerosol scattering coefficients were enhanced by on average a factor of 4.30 ± 2.26 (mean ± standard deviation), with lower values during the haze period (March-April-May) as compared to summer and fall. Hygroscopic growth of aerosol particles was found to cause 1.6 to 3.7 times more negative ADRE at the surface, with the smallest effect during the haze period (March-April-May) and the highest during late summer and beginning of fall (July-August-September).

Reactive uptake of N&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O&amp;lt;sub&amp;gt;5&amp;lt;/sub&amp;gt; to internally mixed inorganic and organic particles: the role of organic carbon oxidation state and inferred organic phase separations

Abstract. We measured N2O5 reactive uptake onto mixed organic/inorganic submicron particles using organic compounds with a variety of oxidation states (using mainly atomic O : C ratios as a proxy) and molecular weights. The organic mass fraction, organic molecular composition, and relative humidity (RH) were varied to assess their effects separately on the N2O5 uptake coefficient, γ(N2O5). At a constant RH, mixtures of organic components having an O : C &lt; 0.5 with ammonium bisulfate significantly suppressed the uptake of N2O5(g) compared to pure ammonium bisulfate, even at small organic mass fractions (e.g., ≤ 15%). The effect of the organic component became less pronounced at higher RH. In general, highly oxygenated organic components (O : C &gt; 0.8) had a smaller or even negligible impact on N2O5(g) uptake at all RHs probed; however, a few exceptions were observed. Notably, γ(N2O5) for mixtures of ammonium bisulfate with polyethylene glycol (PEG), PEG-300 (O : C = 0.56), decreased nearly linearly as the PEG mass fraction increased at constant RH until leveling off at the value measured for pure PEG. The response of γ(N2O5) to increasing PEG mass fraction was similar to that measured on ambient atmospheric particles as a function of organic mass fraction. The effects of the organic mass fraction on γ(N2O5), for mixtures having an O : C &lt; ~0.8, were best described using a standard resistor model of reactive uptake assuming the particles had an RH-dependent inorganic core–organic shell morphology. This model suggests that the N2O5 diffusivity and/or solubility in the organic layer is up to a factor of 20 lower compared to aqueous solution particles, and that the diffusivity, solubility, and reactivity of N2O5 within organic coatings and particles depend upon both RH and the molecular composition of the organic medium. We use these dependencies and ambient measurements of organic aerosol from the global aerosol mass spectrometry (AMS) database to show that the typical impact of organic aerosol components is to both uniformly decrease γ(N2O5), by up to an order of magnitude depending on the RH, organic mass fraction, and O : C ratio, and to induce a stronger dependence of γ(N2O5) upon RH compared to purely inorganic aqueous solutions.

Observations of linear dependence between sulfate and nitrate in atmospheric particles

AbstractHourly measurements of water‐soluble inorganic ionic species in ambient atmospheric particles were conducted at Shanghai, Hangzhou, and Guangzhou sampling sites in China during the period of 2009–2011. The relation between sulfate and nitrate in particulate matter (PM10 and PM2.5) was examined based on these measurements. Results showed that the mass fraction of sulfate was strongly negatively correlated with that of nitrate in atmospheric particles on most of the sampling days, especially when sulfate and nitrate made up the vast majority of the total soluble anions and cations (Na+, K+, Ca2+, and Mg2+) made a small contribution to the total water‐soluble ions, revealing that the formation mechanisms of sulfate and nitrate in the atmosphere are highly correlated, and there exists a significant negative correlation trend between sulfate and nitrate mass fractions in the atmospheric particles. We found that local meteorological conditions presented opposite influences on the mass fractions of sulfate and nitrate. Further analysis indicated that the two mass fractions were modulated by the neutralizing level of atmospheric aerosols, and the negative correlation could be found in acidic atmospheric particles. Strong negative correlation was usually observed on clear days, hazy days, foggy days, and respirable particulate air pollution days, whereas poor negative correlation was often observed during cloud, rain, snow, dust storm, and suspended dust events. The results can help to better understand the formation mechanisms of atmospheric sulfate and nitrate during air pollution episodes and to better explain field results of atmospheric chemistry concerning sulfate and nitrate.

Laboratory-scale Experiment and Model Calculation on the Washout Mechanism of Asian Dust Particles

In this study, an investigation was conducted to assess the washout mechanism of Asian dust particles through both laboratory-scale experiment and model calculation. To artificially simulate Asian dust particle, CaCO₃ particles were generated inside an experimental chamber. They were then scavenged by the artificial rain drops. The abundant CaCO₃ particles scavenged on a rain drop were successively identified by SEM observation. The concentrations of Ca in residual CaCO₃ particles on individual droplet were quantified by PIXE analysis. There was a tendency toward a high accumulation of Ca on a relatively small drop (e.g., .1.0 mm diameter). It is thus suggested that smaller rain drops can effectively scavenge a significant amount of Asian dust particles in ambient atmosphere. The numerical estimation can account for 92.1% and 83.2% of Ca that were measured in small (.1.0 mm diameter) and large (.2.0 mm diameter) size drops, respectively.

Responses of lung cells to realistic exposure of primary and aged carbonaceous aerosols

Diesel exhaust and wood burning are important sources of ambient atmospheric particles due to increasing numbers of diesel cars and the importance of wood as a source of renewable energy. Inhalation is the predominant route of entry and uptake for fine and ultrafine particles into the body. Health effects of atmospheric particles are still not completely understood. There is consistent evidence from epidemiology that particle exposure contributes to respiratory and cardiovascular diseases.This study aimed at examining acute responses of airway epithelial cells and luminal macrophages after exposure to freshly emitted and photochemically aged carbonaceous aerosols under realistic atmospheric conditions. In addition to a bronchial epithelial cell line advanced cell cultures namely fully differentiated respiratory epithelia and primary surface macrophages were used.Our results demonstrate that a single exposure of the cells to realistic particle doses of 0.3–3 ng diesel or 3–9 ng wood aerosol per cm2 cell surface induces small, particle-specific responses. The release of interleukin-6 and -8 was found to be decreased in differentiated airway epithelia but not in the other cell models studied. Aerosol exposure decreased macrophage phagocytic activity by 45–90%. Cell and tissue integrity remained unaffected. Overall, primary and aged particles from the same combustion induced similar responses in the cell models tested, whereby particles from diesel exhaust affected the cells more than those from wood combustion.

Numerical investigation of Rayleigh nanoparticlesensing using a whispering-gallery-mode resonator

We present a rigorous numerical study of a Rayleigh nanoparticle sensing scheme using a whispering-gallery-mode resonator and compare the results to a recent theoretical analysis. Our calculations confirm that the number of adsorbed nanoparticles is accurately proportional to the central spectral shift of the transmission spectrum. Moreover, our results show that when two particles are in proximity, so that each particle experiences the polarization field from the other, the induced secondary spectral shift remains small. Our calculations provide a basis for extending the sensing scheme to large particle influx regimes for real-world applications, such as the determination of the concentration of ultra-fine particles in arc welding, ambient atmosphere, combustion, or on-road aerosol due to traffic exhaust emissions.

Is hydrodynamic escape from Titan possible?

When examining thermal atmospheric escape, usually either Jeans escape or hydrodynamic escape is considered. Jeans escape, where particles with velocities higher than the escape velocity can escape a planetary atmosphere, is usually considered, when particles in a collision-free region are examined. Hydrodynamic escape, on the other hand, presumes that the outflowing gas can be considered as a continuous, homogeneous medium where neither light, nor heavy particles can be discriminated from each other. Recently, Strobel (2009) applied a so-called ‘slow hydrodynamic escape model’, which describes cases intermediate between Jeans escape and hydrodynamic escape, for the nitrogen and methane molecules in Titan's upper atmosphere. This model requires an extended quasi-collisional region above the exobase where efficient energy transfer can presumably occur. In this study, we examine the collision probability of nitrogen and methane molecules with ambient atmospheric particles within Titan's exosphere using a modified Monte Carlo code introduced by Wurz and Lammer (2003), to analyze if the ‘slow hydrodynamic escape model’ is applicable to Titan's exosphere or not. Our results show that the collision probability of nitrogen and methane within Titan's exosphere decreases quickly with height above the exobase. Also, the probability of a nitrogen or a methane molecule to collide with another heavy molecule is far larger than the probability of a collision with a light particle, since in the region where nitrogen and methane are mainly present, the heavy molecules dominate the light molecules by a factor of 10–100. The results of our particle simulation do not confirm the existence of an extended quasi-collisional region above the exobase, where heavy, slow molecules can gain the escape velocity through collisions with light, fast particles.

Application of aerosol electrometer for ambient particle charge measurements

The charge on ambient atmospheric particles is an important parameter in the investigation of particle dynamics. Yet, there is only limited knowledge available on it, mainly due to the lack of instrumentation for its direct measurement. The aim of this study was to explore the application and suitability of the Aerosol Electrometer (AE) TSI Model 3068 as a direct instrument for measuring ambient particle charge concentration, thereby extending its use beyond the current applications. Through a set of experimental investigations the AE was applied to measure net concentration of charged particles in different environments. Results of the study showed the instrument is mostly suitable for outdoor field measurement, when particle charge concentrations are elevated, such as in the vicinity of strong ion emitting sources (high voltage powerlines, electricity substations, etc); and under conditions of air relative humidity of below 60%. Operating the instrument above this humidity value would require the use of a dehumidifier. 74% ( R 2) statistical correlation ( P < 0.05) was obtained between the readings of the AE and the Air Ion Counter, when both instruments were used to simultaneously sample ambient air.

A microscopic study of the effects of particle size and composition of atmospheric aerosols on the corrosion of mild steel

A novel approach to measure the corrosion effects of aerosols as a function of their aerodynamic size and chemical composition was used to study the effects of atmospheric aerosols on mild steel at a rural coastal site. The technique uses collocated micro-orifice uniform deposition impactor samplers to deposit ambient atmospheric particles on exposure steel coupons and collect aerosol samples for ionic analyses. Rusts were found on the coupons with aerosols but none on the blank coupons even the blanks were incubated at the same conditions. FTIR analysis shows that the composition of rusts changes gradually with the aerosol particle size.

Distributions and health risks of polycyclic aromatic hydrocarbons (PAHs) in atmospheric aerosols of Kuala Lumpur, Malaysia

The concentrations and distributions of particle bound polycyclic aromatic hydrocarbons (PAHs) collected over a 10 month period in ambient environment, at street levels as well as during a hazy episode are reported. Ambient and street level distributions of PAHs were similar and their occurrence was attributed to vehicular emissions. However, in haze particles, a different pattern of PAHs was observed, characterized by relatively low levels of benzo[a]pyrene (BaP) and high levels of benzofluoranthenes (BFs). The BaP equivalency results showed that the potential health risk associated with haze smoke particles was 4 times higher than that of street level particles whereas the lowest health risk was associated with ambient atmospheric particles.

The regional influence of volcanic emissions from Popocatéptl, Mexico: Discussion of “Measurement of aerosol particles, gases and flux radiation in the Pico de Orizaba Nacional Park, and its relationship to air pollution transport”, Márquez et al., 2005, Atmospheric Environment, 39, 3877–3890

An understanding of the influence of anthropogenic and natural point sources of pollution on the compositions of distant airmasses requires the careful collection of atmospheric composition data over extended periods of time. Equally, a proper understanding of the influence of megacities, biomass burning plumes and persistent volcanic emissions on the oxidising capacity of the atmosphere requires analysis of the downstream fate of their associated gas and aerosol plumes. Marquez et al. (2005) recently presented some interesting data on the compositions of ambient atmospheric gases and particles at a sampling site in Mexico (Pico de Orizaba National Park, elevation 3300 m; Fig. 1) in late February and early March 2001. Two notable features of their data were the high concentrations of SO2 (mean value 14 ppb) and particulate sulphate (mean 5 μg m−3). The authors ascribed these features to the arrival of air from urban sources nearby, either Mexico City (200 km to the west, elevation 2240 m) or Puebla City (70 km to the west, elevation 2160 m). However, airmass parcels which arrive at the sampling location from either Mexico City, or Puebla, are likely to have passed close to the active volcano of Popocatepetl, 160 km from the sampling endpoint (Fig. 1). In their original paper, Marquez et al. (2005) dismissed any possible volcanic influence on their sampling on the basis of the absence of any volcanic (ash) plume visible in AVHRR weather satellite data. However, Popocatepetl, like many volcanoes, is a prodigious source of reactive gas and aerosol even in the absence of any visible ash plumes. ‘Passively’ degassing volcanoes are becoming increasingly well known as major contributors to the tropospheric gas and aerosol burden, and in particular that of SO2, sulphate and other particles