Application of time-of-flight aerosol mass spectrometry for the online measurement of gaseous molecular iodine.

Here we present a new application of a time-of-flight aerosol mass spectrometer (TOF-AMS) for the measurement of atmospheric trace gases in real-time. Usually, TOF-AMS instruments are not sensitive to gas-phase species due to the aerodynamic particle focusing inlet system which reduces the gas phase species by a factor of about 10(7) relative to the particle phase. This efficient removal of the gas phase and the resulting high relative enrichment of particles is one reason for the very high sensitivity of TOF-AMS instruments for particle phase compounds (detection limits in the sub-μg/m(3)-range for online measurements with 1 min integration time), which allows application of the instrument…

Development of a coupled diffusion denuder system combined with gas chromatography/mass spectrometry for the separation and quantification of molecular iodine and the activated iodine compounds iodine monochloride and hypoiodous acid in the marine atmosphere.

This study concerns the development of a coupled diffusion denuder system capable of separating and quantifying gaseous molecular iodine (I(2)) and two other highly reactive iodine species, ICl and HOI, which are collectively named activated iodine compounds (AIC). Both I(2) and AIC are key species in the atmospheric chemistry of iodine. 1,3,5-Trimethoxybenzene (1,3,5-TMB)- and alpha-cyclodextrin/(129)I(-) (alpha-CD/(129)I(-))-coated denuders proved to be suitable for the collection of gaseous AIC and I(2), respectively. The experimental collection efficiencies for AIC (tested as ICl) and I(2) agreed well with the theoretical values for gas flow rates in the range between 300 and 1800 mL mi…

Urban organic aerosol composition in Eastern China differs from North to South: Molecular insight from a liquid chromatography-Orbitrap mass spectrometry study

Particulate air pollution in China is influencing human health, ecosystem and climate. However, the chemical composition of particulate aerosol, especially of the organic fraction, is still not well understood. In this study, particulate aerosol samples with a diameter ≤ 2.5 μm (PM2.5) were collected in January 2014 in three cities located in Northeast, East and Southeast China, i.e., Changchun, Shanghai and Guangzhou, respectively. Organic aerosol (OA) in the PM2.5 samples was analyzed by ultrahigh performance liquid chromatography (UHPLC) coupled to high-resolution Orbitrap mass spectrometry in both negative mode (ESI−) and positive mode electrospray ioni…

PM2.5-bound oxygenated PAHs, nitro-PAHs and parent-PAHs from the atmosphere of a Chinese megacity: Seasonal variation, sources and cancer risk assessment

Polycyclic aromatic compounds (PACs) in air particulate matter contribute considerably to the health risk of air pollution. The objectives of this study were to assess the occurrence and variation in concentrations and sources of PM2.5 bound PACs [Oxygenated PAHs (OPAHs) nitro PAHs and parent PAHs] sampled from the atmosphere of a typical Chinese megacity (Xi'an) to study the influence of meteorological conditions on PACs and to estimate the lifetime excess cancer risk to the residents of Xi'an (from inhalation of PM2.5 bound PACs). To achieve these objectives we sampled 24 h PM2.5 aerosols (once in every 6days from 5 July 2008 to 8 August 2009) from the atmosphere of Xi'an and measured the…

In situ measurements of molecular iodine in the marine boundary layer: the link to macroalgae and the implications for O<sub>3</sub>, IO, OIO and NO<sub>x</sub>

Abstract. Discrete in situ atmospheric measurements of molecular iodine (I2) were carried out at Mace Head and Mweenish Bay on the west coast of Ireland using diffusion denuders in combination with a gas chromatography-mass spectrometry (GC-MS) method. I2, IO and OIO were also measured by long-path differential optical absorption spectroscopy (LP-DOAS). The simultaneous denuder and LP-DOAS I2 measurements were well correlated (R2=0.80) but the denuder method recorded much higher concentrations. This can be attributed to the fact that the in situ measurements were made near to macroalgal sources of I2 in the intertidal zone, whereas the LP-DOAS technique provides distance-averaged mixing rat…

Measurement report: PM<sub>2.5</sub>-bound nitrated aromatic compounds in Xi'an, Northwest China – seasonal variations and contributions to optical properties of brown carbon

Abstract. Nitrated aromatic compounds (NACs) are a group of key chromophores for brown carbon (light-absorbing organic carbon, i.e., BrC) aerosol, which affects radiative forcing. The chemical composition and sources of NACs and their contributions to BrC absorption, however, are still not well understood. In this study, PM 2.5 -bound NACs in Xi'an, Northwest China, were investigated for 112 daily PM 2.5 filter samples from 2015 to 2016. Both the total concentrations and contributions from individual species of NACs show distinct seasonal variations. The seasonally averaged concentrations of NACs are 2.1 (spring), 1.1 (summer), 12.9 (fall), and 56 ng m −3 (winter). Thereinto, 4-nitrophenol …

Supplementary material to "Measurement report: PM<sub>2.5</sub>-bound nitrated aromatic compounds in Xi'an, Northwest China: Seasonal variations and contributions to optical properties of brown carbon"

Concentrations, optical properties and sources of humic-like substances (HULIS) in fine particulate matter in Xi'an, Northwest China

Humic-like substances (HULIS) are ubiquitous in the atmospheric environment, which affects both human health and climate. We present here the mass concentration and optical characteristics of HULIS isolated from aerosol samples collected in Xi'an, China. Both mass concentration and absorption coefficient (Abs365) of HULIS show clear seasonal differences, with the highest average in winter (3.91 μgC m-3 and 4.78 M m-1, respectively) and the lowest in summer (0.65 μgC m-3 and 0.55 M m-1, respectively). The sources of HULIS_C and light absorption of HULIS were analyzed by positive matrix factorization (PMF) and four major sources were resolved, including secondary formation, biomass burning, c…

Determination of alkylamines in atmospheric aerosol particles: a comparison of gas chromatography–mass spectrometry and ion chromatography approaches

Abstract. In recent years low molecular weight alkylamines have been recognized to play an important role in particle formation and growth in the lower atmosphere. However, major uncertainties are associated with their atmospheric processes, sources and sinks, mostly due to the lack of ambient measurements and the difficulties in accurate quantification of alkylamines at trace level. In this study, we present the evaluation and optimization of two analytical approaches, i.e., gas chromatography–mass spectrometry (GC-MS) and ion chromatography (IC), for the determination of alkylamines in aerosol particles. Alkylamines were converted to carbamates through derivatization with isobutyl chlorof…

Supplementary material to "Measurement report: Large contribution of biomass burning and aqueous-phase processes to the wintertime secondary organic aerosol formation in Xi’an, Northwest China"

Radical Formation by Fine Particulate Matter Associated with Highly Oxygenated Molecules

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 formatio…

Molecular Characterization and Source Identification of Atmospheric Particulate Organosulfates Using Ultrahigh Resolution Mass Spectrometry.

Organosulfates (OSs) have been observed as substantial constituents of atmospheric organic aerosol (OA) in a wide range of environments; however, the chemical composition, sources, and formation mechanism of OSs are still not well understood. In this study, we first created an "OS precursor map" based on the elemental composition of previous OS chamber experiments. Then, according to this "OS precursor map", we estimated the possible sources and molecular structures of OSs in atmospheric PM2.5 (particles with aerodynamic diameter ≤ 2.5 μm) samples, which were collected in urban areas of Beijing (China) and Mainz (Germany) and analyzed by ultrahigh-performance liquid chromatography (UHPLC) c…

The seaweeds <i>Fucus vesiculosus</i> and <i>Ascophyllum nodosum</i> are significant contributors to coastal iodine emissions

Abstract. Based on the results of a pilot study in 2007, which found high mixing ratios of molecular iodine (I2) above the intertidal macroalgae (seaweed) beds at Mweenish Bay (Ireland), we extended the study to nine different locations in the vicinity of Mace Head Atmospheric Research Station on the west coast of Ireland during a field campaign in 2009. The mean values of I2 mixing ratio found above the macroalgae beds at nine different locations ranged from 104 to 393 ppt, implying a high source strength of I2. Such mixing ratios are sufficient to result in photochemically driven coastal new-particle formation events. Mixing ratios above the Ascophyllum nodosum and Fucus vesiculosus beds …

UHPLC-Orbitrap mass spectrometric characterization of organic aerosol from a central European city (Mainz, Germany) and a Chinese megacity (Beijing)

Abstract Fine urban aerosol particles with aerodynamic equivalent dimeter ≤2.5 μm (PM2.5) were collected in Mainz (a city within the Rhine-Main area, the third largest metropolitan region in Germany) and Beijing (Chinese megacity). A solvent mixture of acetonitrile-water was used to extract the organic aerosol fraction (OA) from the particle samples. The extracts were analyzed by an ultrahigh resolution mass spectrometer (UHRMS) Orbitrap coupled with ultra-high-performance liquid chromatography (UHPLC) both in the negative and positive ion mode. The number of compounds observed in Beijing is a factor of 2–10 higher compared to Mainz. The clear differences on chemical composition of OA in th…

Characterization of the light absorbing properties, chromophores composition and sources of brown carbon aerosol in Xi'an, Northwest China

Abstract. The impact of brown carbon aerosol (BrC) on the Earth's radiative forcing balance has been widely recognized but remains uncertain, mainly because the relationships among BrC sources, chromophores, and optical properties of aerosol are poorly understood. In this work, the light absorption properties and chromophore composition of BrC were investigated for samples collected in Xi'an, Northwest China from 2015 to 2016. Both absorption Ångström exponent and mass absorption efficiency show distinct seasonal differences, which could be attributed to the differences in sources and chromophore composition of BrC. Three groups of light-absorbing organics were found to be important BrC ch…

Water-Insoluble Organics Dominate Brown Carbon in Wintertime Urban Aerosol of China: Chemical Characteristics and Optical Properties.

The chromophores responsible for light absorption in atmospheric brown carbon (BrC) are not well characterized, which hinders our understanding of BrC chemistry, the links with optical properties, and accurate model representations of BrC to global climate and atmospheric oxidative capacity. In this study, the light absorption properties and chromophore composition of three BrC fractions of different polarities were characterized for urban aerosol collected in Xi'an and Beijing in winter 2013-2014. These three BrC fractions show large differences in light absorption and chromophore composition, but the chromophores responsible for light absorption are similar in Xi'an and Beijing. Water-ins…

A denuder-impinger system with in situ derivatization followed by gas chromatography-mass spectrometry for the determination of gaseous iodine-containing halogen species.

Reactive iodine species have been suggested to play an important role in the atmosphere (e.g. tropospheric ozone depletion, coastal new particle formation). However, there still exist major uncertainties about their atmospheric chemistry, mostly due to the lack of analytical approaches for the accurate speciation of certain key compounds. In this study, 1,3,5-trimethoxybenzene (1,3,5-TMB)-coated denuder proved to be suitable for the differentiation between gaseous interhalogens (iodine monochloride (ICl), iodine monobromide (IBr)) and molecular iodine (I2) based on a selective collection/derivatization method. The results of the denuder sampling were compared with the results of impinger sa…

Measurement report of the change of PM2.5 composition during the COVID-19 lockdown in urban Xi'an: Enhanced secondary formation and oxidation

Enhanced secondary aerosol formation was observed during the COVID-19 lockdown in Xi'an, especially for polluted episodes. More oxidized‑oxygenated organic aerosol (MO-OOA) and sulfate showed the dominant enhancements, especially in large particle-mode. Meanwhile, relative humidity (RH) showed a positive promotion on the formation of sulfate and MO-OOA during the lockdown, but had no obvious correlation with less oxidized‑oxygenated organic aerosol (LO-OOA) or nitrate. Organosulfurs (OS) displayed a higher contribution (~58%) than inorganic sulfate to total sulfate enhancement in the polluted episode during the lockdown. Although the total nitrate (TN) decreased during the lockdown ascribin…

Severe Pollution in China Amplified by Atmospheric Moisture

AbstractIn recent years, severe haze events often occurred in China, causing serious environmental problems. The mechanisms responsible for the haze formation, however, are still not well understood, hindering the forecast and mitigation of haze pollution. Our study of the 2012–13 winter haze events in Beijing shows that atmospheric water vapour plays a critical role in enhancing the heavy haze events. Under weak solar radiation and stagnant moist meteorological conditions in winter, air pollutants and water vapour accumulate in a shallow planetary boundary layer (PBL). A positive feedback cycle is triggered resulting in the formation of heavy haze: (1) the dispersal of water vapour is cons…

Atmospheric analytical chemistry.

Emission of iodine-containing volatiles by selected microalgae species

In this study we present the results of an emission study of different phytoplankton samples in aqueous media treated with elevated ozone levels. Halocarbon measurements show that the samples tested released bromoform and different iodocarbons, including iodomethane, iodochloromethane and diiodomethane. Iodide and iodate levels in the liquid phase were representative of concentrations of surface water in a natural environment. Measurement of volatile iodine (I2) emissions from two diatom samples (Mediopyxis helysia and Porosira glacialis) and the background sample (F/2 medium from filtered natural seawater) showed that the quantity of evolved I2 depends on the ozone concentration in the air…

Brown Carbon Aerosol in Urban Xi'an, Northwest China: The Composition and Light Absorption Properties.

Light-absorbing organic carbon (i.e., brown carbon or BrC) in the atmospheric aerosol has significant contribution to light absorption and radiative forcing. However, the link between BrC optical properties and chemical composition remains poorly constrained. In this study, we combine spectrophotometric measurements and chemical analyses of BrC samples collected from July 2008 to June 2009 in urban Xi'an, Northwest China. Elevated BrC was observed in winter (5 times higher than in summer), largely due to increased emissions from wintertime domestic biomass burning. The light absorption coefficient of methanol-soluble BrC at 365 nm (on average approximately twice that of water-soluble BrC) w…

Terpenoid composition and chemotaxonomic aspects of Miocene amber from the Koroglu Mountains, Turkey

Abstract A recently discovered fossil resin from Koroglu Mountain in Turkey has been analyzed by gas chromatography–mass spectrometry and pyrolysis gas chromatography–mass spectrometry to determine its structural class and botanical origin. The sesqui- and diterpenoids contained in the amber extract were used as chemosystematic markers when compared with terpenoids in extant conifers. The pyrolysis products were dominated by labdanoid derived bicyclic products together with succinic acid indicating Class Ia type amber. The biomarker compositions of the resin comprise mainly sesqui- and diterpenoids, and lack triterpenoids. This distribution suggests a gymnosperm, and more specifically a con…

The maximum carbonyl ratio (MCR) as a new index for the structural classification of secondary organic aerosol components

RATIONALE Organic aerosols (OA) account for a large fraction of atmospheric fine particulate matter and thus are affecting climate and public health. Elucidation of the chemical composition of OA is the key for addressing the role of ambient fine particles at the atmosphere-biosphere interface and mass spectrometry is the main method to achieve this goal. METHODS High-resolution mass spectrometry (HRMS) is on its way to becoming one of the most prominent analytical techniques, also for the analysis of atmospheric aerosols. The combination of high mass resolution and accurate mass determination allows the elemental compositions of numerous compounds to be easily elucidated. Here a new parame…

Maintenance of iodine intake

Dietary iodine status is routinely assessed by measuring urinary iodine excretion (UI). In most European countries iodine intake is maintained at WHO recommended levels by iodisation of table salt [1]. Exceptions to this practice include Ireland and the UK where only 5% (approximately) of table salt sold is iodine supplemented. However despite the finding of relatively low median UI values in study populations in both Ireland and the UK [2-4] there is little evidence of an increased prevalence of hypothyroidism, overt or subclinical, of non autoimmune pathogenesis [5-8]. In this communication studies on iodine status in the Irish population over the years 1988-2007 are reviewed, as are inve…

Iodine emissions from the sea ice of the Weddell Sea

Iodine compounds were measured above, below and within the sea ice of the Weddell Sea during a cruise in 2009, to make progress in elucidating the mechanism of local enhancement and volatilisation of iodine. I<sub>2</sub> mixing ratios of up to 12.4 pptv were measured 10 m above the sea ice, and up to 31 pptv was observed above surface snow on the nearby Brunt Ice Shelf – large amounts. Atmospheric IO of up to 7 pptv was measured from the ship, and the average sum of HOI and ICl was 1.9 pptv. These measurements confirm the Weddell Sea as an iodine hotspot. Average atmospheric concentrations of CH<sub>3</sub>I, C<sub>2</sub>H<sub>5</sub>I, CH&l…

Effects of NH3 and alkaline metals on the formation of particulate sulfate and nitrate in wintertime Beijing

Sulfate and nitrate from secondary reactions remain as the most abundant inorganic species in atmospheric particle matter (PM). Their formation is initiated by oxidation (either in gas phase or particle phase), followed by neutralization reaction primarily by NH3, or by other alkaline species such as alkaline metal ions if available. The different roles of NH3 and metal ions in neutralizing H2SO4 or HNO3, however, are seldom investigated. Here we conducted semi-continuous measurements of SO4 2−, NO3 −, NH4 +, and their gaseous precursors, as well as alkaline metal ions (Na+, K+, Ca2+, and Mg2+) in wintertime Beijing. Analysis of aerosol acidity (estimated from a thermodynamic model) indicat…

One-year characterization of organic aerosol markers in urban Beijing: Seasonal variation and spatiotemporal comparison

Abstract Organic aerosol (OA) is a major component of fine particulate matter (PM); however, only 10%–30% of OA have been identified as individual compounds, and some are used as markers to trace the sources and formation mechanisms of OA. The temporal and spatial coverage of these OA markers nonetheless remain inadequately characterized. This study presents a year-long measurement of 92 organic markers in PM2.5 samples collected at an urban site in Beijing from 2014 to 2015. Saccharides were the most abundant (340.1 ng m−3) species detected, followed by phthalic acids (283.4 ng m−3). In summer, high proportions (8%–24%) of phthalic acids, n-alkanes, fatty acids, and n-alcohols indicate dom…

Determination of n-alkanes, PAHs and hopanes in atmospheric aerosol: evaluation and comparison of thermal desorption GC-MS and solvent extraction GC-MS approaches

Organic aerosol (OA) constitutes a large fraction of fine particulate matter (PM) in the urban air. However, the chemical nature and sources of OA are not well constrained. Quantitative analysis of OA is essential for understanding the sources and atmospheric evolution of fine PM, which requires accurate quantification of some organic compounds (e.g., markers). In this study, two analytical approaches, i.e., thermal desorption (TD) gas chromatography-mass spectrometry (GC-MS) and solvent extract (SE) GC-MS were evaluated for the determination of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and hopanes in ambient aerosol. For the SE approach, the recovery obtained is 89.3–101.5&…

Contrasting sources and processes of particulate species in haze days with low and high relative humidity in winter time Beijing

Abstract. Although there are many studies of particulate matter (PM) pollution in Beijing, the sources and processes of secondary PM species during haze periods remain unclear. Limited studies have investigated the PM formation in highly-polluted environments under low and high relative humidity (RH) conditions. Herein, we present a systematic comparison of species in submicron particles (PM1) in wintertime Beijing (29 December 2014 to 28 February 2015) for clean periods and pollution periods under low and high RH conditions. PM1 species were measured with an aerosol chemical species monitor (ACSM) and an aethalometer. Sources and processes for organic aerosol (OA) were resolved by positive…

Diffusion technique for the generation of gaseous halogen standards

Abstract Halogens are known to play an important role in the tropospheric ozone-depletion chemistry and are of special interest because of their influence on the atmospheric oxidation capacity. In this paper, we investigate the application of a capillary diffusion technique for the generation of gaseous halogen standards like Br 2 , IBr, ICl and I 2 . The influence of capillary dimension (i.e. length and inner diameter), ambient pressure and headspace volume of the diffusion vessel on the test gas output has been evaluated. The experimental output rates are determined from the mass loss of the analyte vessel on a regular schedule and compared with their respective theoretical predictions. W…

Extensive Evaluation of a Diffusion Denuder Technique for the Quantification of Atmospheric Stable and Radioactive Molecular Iodine

In this paper we present the evaluation and optimization of a new approach for the quantification of gaseous molecular iodine (I(2)) for laboratory- and field-based studies and its novel application for the measurement of radioactive molecular iodine. alpha-Cyclodextrin (alpha-CD) in combination with (129)I(-) is shown to be an effective denuder coating for the sampling of gaseous I(2) by the formation of an inclusion complex. The entrapped (127)I(2) together with the (129)I(-) spike in the coating is then released and derivatized to 4-iodo-N,N-dimethylaniline (4-I-DMA) for gas chromatography-mass spectrometry (GC-MS) analysis. The (127)I(2) collected can be differentiated from the (129)I(-…

Observations of high concentrations of I2and IO in coastal air supporting iodine-oxide driven coastal new particle formation

[1] Theoretical studies have predicted that concentrations of gaseous I2 and IO of the order of 80–100 ppt and 40–50 ppt, respectively, are required in coastal air to account for photochemically-driven coastal new-particle formation events to occur. However, measurements reported to date (i.e., ∼20 ppt I2, ≤ 10 ppt IO) have not supported the required model predictions. Here, we present measurements of high concentrations of I2 and IO in N.E. Atlantic marine air on the west coast of Ireland. The maximum mixing ratios of daytime I2 and IO over the seaweed beds during low tide were 302 ppt and 35 ppt, respectively. The I2 distribution was rather inhomogeneous, even at the inter-tidal zone, but…

Organosulfates in atmospheric aerosol: synthesis and quantitative analysis of pm<sub>2.5</sub> from xi'an, northwestern china

Abstract. The sources, formation mechanism and amount of organosulfates (OS) in atmospheric aerosol are not yet well understood, partly due to the lack of authentic standards for quantification. In this study, we report an improved robust procedure for the synthesis of organosulfates with different functional groups. Nine authentic organosulfate standards were synthesized and four standards (benzyl sulfate, phenyl sulfate, glycolic acid sulfate, and hydroxyacetone sulfate) were used to quantify their ambient concentrations. The authentic standards and ambient aerosol samples were analyzed using an optimized ultra performance liquid chromatography–electrospray ionization-tandem mass spectrom…