Monitor For AeRosols And Gases In Ambient Air Research Articles

Sulfate Formation Driven by Wintertime Fog Processing and a Hydroxymethanesulfonate Complex With Iron: Observations From Single‐Particle Measurements in Hong Kong

AbstractFog processing has a significant impact on sulfur chemistry in the atmosphere. This study analyzed three winter fog events in Hong Kong using single‐particle aerosol mass spectrometry (SPAMS) and a Monitor for AeRosols and GAses in ambient air (MARGA). Black carbon (BC)‐related carbonaceous particles with substantial sulfate amounts comprised the largest particle number fraction (56.7%). Sulfate mass concentration decreased during fog due to the cloud's effective scavenging, but fog processing notably promoted sulfate formation at the single‐particle level (average peak area increases of 31.2%). Hydroxymethanesulfonate (HMS), an important S(IV) compound and fog tracer, was identified accounting for up to 12% by particle number fraction. Although pH showed a positive correlation (r = 0.53–0.69) with HMS particles in each fog scenario, a negative overall correlation (r = −0.51) was observed. Further analysis revealed that the higher aerosol acidity (pH 0.65–3.11), promoted Fe dissolution, leading to 49% of HMS particles being mixed with Fe, which potentially facilitated sulfate formation via the Fenton reaction. Additionally, around 40% of HMS‐Fe particles are mixed with oxalate, thereby warranting further attention for their potential to cause more intricate sulfur oxidation processes. This study reveals the initial identification of a high mixed‐state of HMS‐Fe, which could potentially serve as a crucial avenue for the formation of sulfate on individual particulate matter. Considering the persistent augmentation of aerosol acidity in the Asian region, this phenomenon necessitates further investigation and attention.

The observation of atmospheric HONO by wet-rotating-denuder ion chromatograph in a coastal city: Performance and influencing factors

Due to the significance of atmospheric HONO as a reservoir for radicals and the presence of substantial unknown sources of HONO, there is a pressing need for accurate and consistent measurement of its concentration. In this study, we compared the measurements obtained from the monitor for aerosols and gases in ambient air (MARGA) based on wet chemical method with those from the incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) based on optical method to assess the suitability of the MARGA instrument for accurate HONO detection. The diurnal patterns obtained by the two instruments are similar, with peaks at 8 a.m. and lows at 5 p.m. Over the course of the observation period, it was often observed that HONO concentrations recorded by the MARGA instrument consistently exceeded those obtained through the IBBCEAS technique, accounting for approximately 91.33% of the total observation time. Throughout the entire observation period, the R2 value between the two instruments was 0.49, indicating relatively good correlation. However, with a slope of only 0.27, it suggests poor agreement between the two instruments. Furthermore, the R2 and slopes between the two instruments vary with the seasons and day-night. The larger the quartile values of NO2, NH3, and BC, the greater the slopes of both MARGA and IBBCEAS instruments, and the higher the concentrations of NO2, NH3, and BC (indicator of semivolatile oxidizable hydrocarbons), the greater the differences between the two instruments, all indicating that NH3 may promote the reaction of NO2 with semivolatile oxidizable hydrocarbons to produce HONO. The O3 with its strong oxidizing properties may cause underestimation in the MARGA instrument by oxidizing NO2− to NO3− in the absorbing solution. It is challenging to derive a universal correction formula due to the interference of various chemical substances. Hence, MARGA should not be used for HONO research in the future.

Chloride (HCl ∕ Cl−) dominates inorganic aerosol formation from ammonia in the Indo-Gangetic Plain during winter: modeling and comparison with observations

Abstract. The Winter Fog Experiment (WiFEX) was an intensive field campaign conducted at Indira Gandhi International Airport (IGIA) Delhi, India, in the Indo-Gangetic Plain (IGP) during the winter of 2017–2018. Here, we report the first comparison in South Asia of high-temporal-resolution simulation of ammonia (NH3) along with ammonium (NH4+) and total NHx (i.e., NH3+ NH4+) using the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) and measurements made using the Monitor for AeRosols and Gases in Ambient Air (MARGA) at the WiFEX research site. In the present study, we incorporated the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) aerosol scheme into WRF-Chem. Despite simulated total NHx values and variability often agreeing well with the observations, the model frequently simulated higher NH3 and lower NH4+ concentrations than the observations. Under the winter conditions of high relative humidity (RH) in Delhi, hydrogen chloride (HCl) was found to promote the increase in the particle fraction of NH4+ (which accounted for 49.5 % of the resolved aerosol in equivalent units), with chloride (Cl−) (29.7 %) as the primary anion. By contrast, the absence of chloride (HCl / Cl−) chemistry in the standard WRF-Chem model results in the prediction of sulfate (SO42-) as the dominant inorganic aerosol anion. To understand the mismatch associated with the fraction of NHx in the particulate phase (NH4+ / NHx), we added HCl / Cl− to the model and evaluated the influence of its chemistry by conducting three sensitivity experiments using the model: no HCl, base case HCl (using a published waste burning inventory), and 3 × base HCl run. We found that 3 × base HCl increased the simulated average NH4+ by 13.1 µg m−3 and NHx by 9.8 µg m−3 concentration while reducing the average NH3 by 3.2 µg m−3, which is more in accord with the measurements. Thus HCl / Cl− chemistry in the model increases total NHx concentration, which was further demonstrated by reducing NH3 emissions by a factor of 3 (−3 × NH3_EMI) in the 3 × base HCl simulation. Reducing NH3 emissions in the 3 × base HCl simulation successfully addressed the discrepancy between measured and modeled total NHx. We conclude that modeling the fate of NH3 in Delhi requires a correct chemistry mechanism accounting for chloride dynamics with accurate inventories of both NH3 and HCl emissions.

Practical approach for an easy determination of the limit of detection and uncertainty budget associated with on-line measurements of gas and aerosols by ion chromatography

The Monitor for Aerosols and Gases in Ambient air (MARGA) is an on-line gas and aerosol sampling and analysis system based on ion chromatography (IC) that allows the monitoring at 1-h time resolution of major water-soluble atmospheric species in the gas phase (NH3, HCl, HONO, HNO3, SO2) and the particle phase (NH4+, Na+, K+, Ca2+, Mg2+, Cl−, NO3−, SO42−). The lack of a common procedure among users to determine the LOD and the uncertainty of measurements for each species led to the comparison of four different operational approaches for the LOD determination, one manual and three automatic. This comparison highlighted the high NO3− blank values around 0.6 μg m−3 when using a HNO3-based cation eluent, so the p-TSA-based eluent was proposed instead. A model for an easy estimation of measurement uncertainties is suggested based on main sources of uncertainty (liquid sample volume, air volume, representativeness of the sample, accuracy of the internal standard preparation, chemical background, repeatability), applied to a real dataset acquired in a rural site in the North of France. It gives relative average uncertainties between 5 and 30% for NH3, HONO, HNO3, SO2, NH4+ NO3− and SO42−, while Na+, K+, Ca2+, Mg2+ and Cl− range between 45% and >100%. A comparison between our dataset and other studies confirmed that the variation of the uncertainty budget depends on environmental concentrations of the species and site typology. The practical recommendations drawn in this paper may be helpful to the user community of gas and aerosol online samplers coupled to IC analysis.

Development, characterization, and application of an improved online reactive oxygen species analyzer based on the Monitor for AeRosols and Gases in ambient Air (MARGA)

Abstract. Excessive reactive oxygen species (ROS) in the human body is an important factor leading to diseases. Therefore, research on the content of reactive oxygen species in atmospheric particles is necessary. In recent years, the online detection technology of ROS has been developed. However, there are few technical studies on online detection of ROS based on the dithiothreitol (DTT) method. Here, to modify the instrument, a DTT experimental module is added that is protected from light and filled with nitrogen at the end based on the Monitor for AeRosols and Gases in ambient Air (MARGA). The experimental study found that the detection limit of the modified instrument is 0.024 nmol min−1. The DTT consumption rate of blank sample (ultrapure water) is reduced by 44 %, which eliminates the influence of outside air and light in the experiment. And the accuracy of the online instrument is determined by comparing the online and offline levels of the samples, which yielded good consistency (slope 0.97, R2=0.95). It shows that the performance of the instrument is indeed optimized, the instrument is stable, and the characterization of ROS is accurate. The instrument not only realizes online detection conveniently and quickly, but also achieves the hour-by-hour detection of ROS based on the DTT method. Meanwhile, reactive oxygen and inorganic ions in atmospheric particles are quantified using the online technique in the northern suburbs of Nanjing. It is found that the content of ROS during the day is higher than that at night, especially after it rains; ROS peaks appear in the two time periods of 08:00–10:00 and 16:00–18:00 (China Standard Time, UTC+8:00; expressed here in local time – LT). In addition, examination of the online ROS, water-soluble ion (SO42-, NO3-, NH4+, Na+, Ca2+, K+), BC, and polluting gas (SO2, CO, O3, NO, NOx) measurements revealed that photo-oxidation and secondary formation processes could be important sources of aerosol ROS. This breakthrough enables the quantitative assessment of atmospheric particulate matter ROS at the diurnal scale, providing an effective tool to study sources and environmental impacts of ROS.

Strong Deviations from Thermodynamically Expected Phase Partitioning of Low-Molecular-Weight Organic Acids during One Year of Rural Measurements

An upgraded monitor for aerosols and gases in ambient air (MARGA) was applied for one year at the Central European TROPOS research site Melpitz investigating the gas- and particle-phase partitionin...

Role of the dew water on the ground surface in HONO distribution: a case measurement in Melpitz

Abstract. To characterize the role of dew water for the ground surface HONO distribution, nitrous acid (HONO) measurements with a Monitor for AeRosols and Gases in ambient Air (MARGA) and a LOng Path Absorption Photometer (LOPAP) instrument were performed at the Leibniz Institute for Tropospheric Research (TROPOS) research site in Melpitz, Germany, from 19 to 29 April 2018. The dew water was also collected and analyzed from 8 to 14 May 2019 using a glass sampler. The high time resolution of HONO measurements showed characteristic diurnal variations that revealed that (i) vehicle emissions are a minor source of HONO at Melpitz station; (ii) the heterogeneous conversion of NO2 to HONO on the ground surface dominates HONO production at night; (iii) there is significant nighttime loss of HONO with a sink strength of 0.16±0.12 ppbv h−1; and (iv) dew water with mean NO2- of 7.91±2.14 µg m−2 could serve as a temporary HONO source in the morning when the dew droplets evaporate. The nocturnal observations of HONO and NO2 allowed the direct evaluation of the ground uptake coefficients for these species at night: γNO2→HONO=2.4×10-7 to 3.5×10-6, γHONO,ground=1.7×10-5 to 2.8×10-4. A chemical model demonstrated that HONO deposition to the ground surface at night was 90 %–100 % of the calculated unknown HONO source in the morning. These results suggest that dew water on the ground surface was controlling the temporal HONO distribution rather than straightforward NO2–HONO conversion. This can strongly enhance the OH reactivity throughout the morning time or in other planted areas that provide a large amount of ground surface based on the OH production rate calculation.

Observation of Aerosol Optical Properties and New Particle Formation in the Yangtze River Delta

In a recent field campaign focused on air quality study, aerosol optical properties, particle number concentration, and PM2.5 components were monitored in Changzhou, Jiangsu Province, from May 27 to June 27, 2019. An array of instruments were deployed that included scanning mobility particle size spectrometer (SMPS), aethalometer (AE33), cavity attenuation phase shift single albedo monitor (CAPS-ALB), monitor for aerosols and gases in ambient air (MARGA) and RT-4 organic carbon/elemental carbon (OC/EC) carbon analyzer to study the ① changes in chemical composition and optical parameters of the new particles generated during the campaign period. ② comparison of the aerosol extinction coefficient recorded by these instruments and measured value in the reconstruction of IMPROVE (interagency monitoring of protected visual environment) and the calculated coefficient using MIE theory model were carried out. During the entire campaign, two new particle generation events were observed and also found that the particle size continued to increase from 4 nm to 64 nm. It was monitored that in the initial stage of new particle generation, sulfate contributed greatly. The measured average aerosol extinction coefficient during the period of particle generation, using these instruments was 95.40 Mm-1, while the average aerosol extinction reconstruction using the IMPROVE model was observed to be 140.20 Mm-1. The theoretical calculations based on Mie theory model yielded an average extinction coefficient of 93.54 Mm-1. It was found that the average aerosol extinction in Changzhou is lower than the average value of the urban aerosol extinction coefficient, which is measured to be 300 Mm-1 in China, during this period. The deployment of multiple instruments in a single campaign is more desirable because the combination of all observations helped in better characterization of the physicochemical properties of ambient aerosols from various aspects, including particle size spectrum and chemical composition.

Influence of Chinese New Year overlapping COVID-19 lockdown on HONO sources in Shijiazhuang

Nitrous acid (HONO) is an important precursor of hydroxyl radical (OH) in the atmosphere. It is also toxic to human health. In this work, HONO concentrations were measured in Shijiazhuang using a Monitor for AeRosols and Gases in ambient Air (MARGA) from December 15, 2019 to March 15, 2020, which covered the heavy air pollution season, the Chinese New Year (CNY) vocation and the Corona Virus Disease-19 (COVID-19) lockdown period. During & after CNY overlapping COVID-19 lockdown, the air quality was significantly improved because of both the emission reduction and the increase in diffusion ability of air masses. The mean HONO concentration was 2.43 ± 1.08 ppbv before CNY, while it decreased to 1.53 ± 1.16 ppbv during CNY and 0.97 ± 0.76 ppbv after CNY. The lockdown during & after CNY reduced ~31% of ambient HONO along with ~62% of NO and ~36% of NO2 compared with those before CNY after the improvement of diffusion ability had been taken into consideration. Heterogeneous reaction of NO2 on ground surface dominated the nocturnal HONO sources, followed by heterogeneous reaction on aerosol surface, vehicle emission, reaction between NO and OH and emission from soil on pollution days throughout the observation. Except for elevated soil emission, other nighttime HONO sources and sinks decreased significantly during & after CNY. The relative importance of heterogeneous reaction of NO2 on surfaces further increased because of both the decrease in vehicle emission and the increase in the heterogeneous conversion kinetics from NO2 to HONO during & after CNY.

Field Evidence of Fe-Mediated Photochemical Degradation of Oxalate and Subsequent Sulfate Formation Observed by Single Particle Mass Spectrometry.

In this work, we deployed a single particle aerosol mass spectrometer (SPAMS) at a suburban coastal site in Hong Kong from February 04 to April 17, 2013 to study individual oxalate particles and a monitor for aerosols and gases in ambient air (MARGA) to track the bulk oxalate concentrations in particle matter smaller than 2.5 μm in diameter (PM2.5). A shallow dip in the bulk oxalate concentration was consistently observed before 10:00 am in the morning throughout the observation campaign, corresponding to a 20% decrease in the oxalate concentration on average during the decay process. Such a decrease in PM oxalate was found to be coincident with a decrease in Fe-containing oxalate particles, providing persuasive evidence of Fe-mediated photochemical degradation of oxalate. Oxalate mixed with Fe and Fe_NaK particles, from industry sources, were identified as the dominant factors for oxalate decay in the early morning. We further found an increase of sulfate intensity by a factor of 1.6 on these individual Fe-containing particles during the oxalate decomposition process, suggesting a facilitation of sulfur oxidation. This is the first report on the oxalate-Fe decomposition process with individual particle level information and provides unique evidence to advance our current understanding of oxalate and Fe cycling. The present work also indicates the importance of anthropogenic sourced iron in oxalate-Fe photochemical processing. In addition, V-containing oxalate particles, from ship emissions, also showed evidence of morning photodegradation and need further attention since current models rarely consider photochemical processing of oxalate_V particles.

Change in Characteristics of Pollution Gas and Water-soluble Ions at Different Development Stages of Haze

To explore the variation in characteristics of atmospheric pollutants at different stages of haze, the monitor for aerosols and gases in ambient air (MARGA) was used to observe the concentrations of precursor pollutants (NH3, HNO3, and SO2) and eight water-soluble ions in a regional haze in the Yangtze River Delta region from November 18 to December 07, 2018. Combined with environmental data (PM2.5, NO2, CO, and O3) and meteorological data, the causes of regional haze formation, diurnal variation characteristics of air pollutants, and distribution characteristics of air pollutants in different stages of haze were analyzed. The results showed that the Yangtze River Delta region was mainly controlled by a ridge of high pressure during the haze process and the weather situation was stable, which was conducive to the accumulation of air pollutants. On hazy days, the concentrations of PM2.5, NO2, NO3-, SO42-, NH4+, Cl-, and Na+ were (118.91±39.23), (61.62±26.34), (45.64±16.01), (18.80±8.02), (20.82±7.16), (3.02±2.25), and (0.23±0.22) μg·m-3, respectively, and these were 2.73, 1.63, 2.64, 1.94, 2.50, 2.05, and 2.56 times the levels found on clean days, respectively. The concentration of CO was (1.34±0.39) mg·m-3 on hazy days, which was 1.86 times that found on clean days. Diurnal variation characteristics of different air pollutants were different, as were the distribution characteristics of air pollutants at different haze stages. The concentrations of SO2 was the highest in the haze occurrence stage. The concentrations of PM2.5, NO2, NH3, CO, and SNA were highest in the haze development stage, and the concentrations of O3, Cl-, Na+, and K+ were highest in the haze dissipation stage. The relative contributions of SNA to PM2.5 in different stages of haze could reach 94%-96%, and their growth rate was largest in the development stage. The order of growth rate was NO3- > NH4+ > SO42-. SNA mainly existed in the form of NH4NO3 on clean days and in the occurrence and development stages, and (NH4)2SO4 in the dissipation stage. This haze process was mainly caused by the growth of NO3-, which was mainly generated by gas-phase homogeneous phase reaction, and NO3-contributes 51.06%, 51.85%, and 48.22%, respectively, to PM2.5 in the occurrence, development, and dissipation stages of haze.

Development of an online-coupled MARGA upgrade for the 2 h interval quantification of low-molecular-weight organic acids in the gas and particle phases

Abstract. A method is presented to quantify the low-molecular-weight organic acids such as formic, acetic, propionic, butyric, pyruvic, glycolic, oxalic, malonic, succinic, malic, glutaric, and methanesulfonic acid in the atmospheric gas and particle phases, based on a combination of the Monitor for AeRosols and Gases in ambient Air (MARGA) and an additional ion chromatography (Compact IC) instrument. Therefore, every second hourly integrated MARGA gas and particle samples were collected and analyzed by the Compact IC, resulting in 12 values per day for each phase. A proper separation of the organic target acids was initially tackled by a laboratory IC optimization study, testing different separation columns, eluent compositions and eluent flow rates for both isocratic and gradient elution. Satisfactory resolution of all compounds was achieved using a gradient system with two coupled anion-exchange separation columns. Online pre-concentration with an enrichment factor of approximately 400 was achieved by solid-phase extraction consisting of a methacrylate-polymer-based sorbent with quaternary ammonium groups. The limits of detection of the method range between 0.5 ng m−3 for malonate and 17.4 ng m−3 for glutarate. Precisions are below 1.0 %, except for glycolate (2.9 %) and succinate (1.0 %). Comparisons of inorganic anions measured at the TROPOS research site in Melpitz, Germany, by the original MARGA and the additional Compact IC are in agreement with each other (R2 = 0.95–0.99). Organic acid concentrations from May 2017 as an example period are presented. Monocarboxylic acids were dominant in the gas phase with mean concentrations of 306 ng m−3 for acetic acid, followed by formic (199 ng m−3), propionic (83 ng m−3), pyruvic (76 ng m−3), butyric (34 ng m−3) and glycolic acid (32 ng m−3). Particulate glycolate, oxalate and methanesulfonate were quantified with mean concentrations of 26, 31 and 30 ng m−3, respectively. Elevated concentrations of gas-phase formic acid and particulate oxalate in the late afternoon indicate photochemical formation as a source.

Two years of online measurement of fine particulate nitrate in the western Yangtze River Delta: influences of thermodynamics and N<sub>2</sub>O<sub>5</sub> hydrolysis

Abstract. Particulate nitrate contributes a large fraction of secondary aerosols. Despite understanding of its important role in regional air quality and global climate, long-term continuous measurements are rather limited in China. In this study, we conducted online measurement of PM2.5 (particulate matter with diameters less than 2.5 µm) nitrate for 2 years from March 2014 to February 2016 using the Monitor for AeRosols and Gases in ambient Air (MARGA) in the western Yangtze River Delta (YRD), eastern China, and investigate the main factors that influenced its temporal variations and formation pathways. Compared to other sites in China, an overall high concentration of particulate nitrate was observed, with a mean value of 15.8 µg m−3 (0.5 to 92.6 µg m−3). Nitrate on average accounted for 32 % of the total mass of water-soluble ions and the proportion increased with PM loading, indicating that nitrate is a major driver of haze pollution episodes in this region. Sufficient ammonia drove most nitrate into the particle phase in the form of ammonium nitrate. A typical seasonal cycle of nitrate was observed, with the concentrations in winter on average 2 times higher than those in summer mainly due to different meteorological conditions. In summer, the diurnal variation of particulate nitrate was determined by thermodynamic equilibrium, resulting in a much lower concentration during daytime despite a considerable photochemical production. Air masses from the polluted YRD and biomass burning region contributed to the high nitrate concentration during summer. In winter, particulate nitrate did not reveal an evident diurnal variation. Regional transport from northern China played an important role in enhancing nitrate concentration. A total of 18 nitrate episodes were selected to understand the processes that drive the formation of high concentration of nitrate. Rapid nitrate formation was observed during the pre-episode (the day before nitrate episode day) nights, and dominated the increase of total water-soluble ions. Calculated nitrate from N2O5 hydrolysis was highly correlated to and accounted for 80 % of the observed nitrate, suggesting that N2O5 hydrolysis was a major contributor to the nitrate episodes. Our results suggested that rapid formation of nitrate could be a main cause for extreme aerosol pollution events in the YRD during winter, and illustrated the urgent need to control NOx emission.

Coupling of organic and inorganic aerosol systems and the effect on gas-particle partitioning in the southeastern US.

Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2× sulfate, RN/2S ≈ 0.8 to 0.9) with approximately 70% of total ammonia and ammonium (NHx) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H+]air (H+ in μgm−3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid–liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic–organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C≥0.6) compounds including several isoprene-derived tracers as well as levoglu-cosan but decrease particle-phase partitioning for low O: C, monoterpene-derived species.

Chromatography related performance of the Monitor for AeRosols and GAses in ambient air (MARGA): laboratory and field-based evaluation.

Evaluation of the semi-continuous Monitor for AeRosols and GAses in ambient air (MARGA, Metrohm Ap-plikon B.V.) was conducted with an emphasis on examination of accuracy and precision associated with processing of chromatograms. Using laboratory standards and atmospheric measurements, analytical accuracy, precision and method detection limits derived using the commercial MARGA software were compared to an alternative chromatography procedure consisting of a custom Java script to reformat raw MARGA conductivity data and Chromeleon (Thermo Scientific Dionex) software for peak integration. Our analysis revealed issues with accuracy and precision resulting from misidentification and misintegration of chromatograph peaks by the MARGA automated software as well as a systematic bias at low concentrations for anions. Reprocessing and calibration of raw MARGA data using the alternative chromatography method lowered method detection limits and re-duced variability (precision) between parallel sampler boxes. Instrument performance was further evaluated during a 1-month intensive field campaign in the fall of 2014, including analysis of diurnal patterns of gaseous and particulate water-soluble species (NH3, SO2, HNO3, , and , gas-to-particle partitioning and particle neutralization state. At ambient concentrations below ~ 1 µg m–3, concentrations determined using the MARGA software are biased +30 and +10 % for and , respectively, compared to concentrations determined using the alternative chromatography procedure. Differences between the two methods increase at lower concentrations. We demonstrate that positively biased and measurements result in overestimation of aerosol acidity and introduce nontrivial errors to ion balances of inorganic aerosol. Though the source of the bias is uncertain, it is not corrected by the MARGA online single-point internal LiBr standard. Our results show that calibra-tion and verification of instrument accuracy by multilevel external standards is required to adequately control analytical accuracy. During the field intensive, the MARGA was able to capture rapid compositional changes in PM2.5 due to changes in meteorology and air mass history relative to known source regions of PM precursors, including a fine aerosol event associated with intrusion of Arctic air into the southeastern US.

Measurements of PM10 ions and trace gases with the online system MARGA at the research station Melpitz in Germany \u2013 A five-year study

An hourly quantification of inorganic water-soluble PM10 ions and corresponding trace gases was performed using the Monitor for AeRosols and Gases in ambient Air (MARGA) at the TROPOS research site in Melpitz, Germany. The data availability amounts to over 80% for the five-year measurement period from 2010 to 2014. Comparisons were performed for the evaluation of the MARGA, resulting in coefficients of determinations (slopes) of 0.91 (0.90) for the measurements against the SO2 gas monitor, 0.84 (0.88), 0.79 (1.39), 0.85 (1.20) for the ACSM NO3−, SO42− and NH4+ measurements, respectively, and 0.85 (0.65), 0.88 (0.68), 0.91 (0.83), 0.86 (0.82) for the filter measurements of Cl−, NO3−, SO42− and NH4+, respectively. A HONO comparison with a batch denuder shows large scatter (R2 = 0.41). The MARGA HNO3 is underestimated compared to a batch and coated denuder with shorter inlets (slopes of 0.16 and 0.08, respectively). Less NH3 was observed in coated denuders for high ambient concentrations. Long-time measurements show clear daily and seasonal variabilities. Potential Source Contribution Function (PSCF) analysis indicates the emission area of particulate ions Cl−, NO3−, SO42−, NH4+, K+ and gaseous SO2 to lie in eastern European countries, predominantly in wintertime. Coarse mode sea salt particles are transported from the North Sea to Melpitz. The particles at Melpitz are nearly neutralised with a mean molar ratio of 0.90 for the five-year study. A slight increase of the neutralization ratio over the last three years indicates a stronger decrease of the anthropogenically emitted NO3− and SO42− compared to NH4+.

An assessment of the performance of the Monitor for AeRosols and GAses in ambient air (MARGA): a semi-continuous method for soluble compounds

Abstract. Ambient air monitoring as part of the US Environmental Protection Agency's (US EPA's) Clean Air Status and Trends Network (CASTNet) currently uses filter packs to measure weekly integrated concentrations. The US EPA is interested in supplementing CASTNet with semi-continuous monitoring systems at select sites to characterize atmospheric chemistry and deposition of nitrogen and sulfur compounds at higher time resolution than the filter pack. The Monitor for AeRosols and GAses in ambient air (MARGA) measures water-soluble gases and aerosols at an hourly temporal resolution. The performance of the MARGA was assessed under the US EPA Environmental Technology Verification (ETV) program. The assessment was conducted in Research Triangle Park, North Carolina, from 8 September to 8 October 2010 and focused on gaseous SO2, HNO3, and NH3 and aerosol SO42-, NO3-, and NH4+. Precision of the MARGA was evaluated by calculating the median absolute relative percent difference (MARPD) between paired hourly results from duplicate MARGA units (MUs), with a performance goal of ≤ 25%. The accuracy of the MARGA was evaluated by calculating the MARPD for each MU relative to the average of the duplicate denuder/filter pack concentrations, with a performance goal of ≤ 40%. Accuracy was also evaluated by using linear regression, where MU concentrations were plotted against the average of the duplicate denuder/filter pack concentrations. From this, a linear least squares line of best fit was applied. The goal was for the slope of the line of best fit to be between 0.8 and 1.2. The MARGA performed well in comparison to the denuder/filter pack for SO2, SO42−, and NH4+, with all three compounds passing the accuracy and precision goals by a significant margin. The performance of the MARGA in measuring NO3- could not be evaluated due to the different sampling efficiency of coarse NO3- by the MUs and the filter pack. Estimates of "fine" NO3- were calculated for the MUs and the filter pack. Using this and results from a previous study, it is concluded that if the MUs and the filter pack were sampling the same particle size, the MUs would have good agreement in terms of precision and accuracy. The MARGA performed moderately well in measuring HNO3 and NH3, though neither met the linear regression slope goals. However, recommendations for improving the measurement of HNO3 and NH3 are discussed. It is concluded that SO42-, SO2, NO3-, HNO3, NH4+, and NH3 concentrations can be measured with acceptable accuracy and precision when the MARGA is operated in conjunction with the recommendations outlined in the manuscript.

Simultaneous online monitoring of inorganic compounds in aerosols and gases in an industrialized area

The automatic MARGA (monitor for aerosols and gases in ambient air) sampling system was used to measure the inorganic ions Cl–, NO3–, SO42–, Na+, NH4+, K+, Mg2+ and Ca2+ in the PM2.5 aerosol phase and the corresponding inorganic gases HCl, HNO2, SO2, HNO3 and NH3 present in the gas phase. Samples were collected and analyzed hourly for 3 months between April and June, 2011, from a sampling site in Singapore close to a heavy industrial area containing extensive petrochemical refineries. The data (hourly and daily average) were analyzed, compared and discussed based on the ratios of HNO2/HNO3 and NH3/NH4+, the levels of nitrate and sulfate, the total nitrogen, the distribution of particulate matter and gaseous compounds, and the acidity of the aerosols. SO2 was the most abundant gas that appeared in an order of magnitude higher concentration than the other trace gases, and correspondingly SO42– was found to be at least 3–10 times higher than other anionic aerosol species. The concentration of major ions in aerosol samples and the related gaseous compounds followed the order of: SO42– > NH4+ > NO3– > K+ > Na+ > Cl– > Ca2+ > Mg2+ and SO2 > NH3 > HNO2 > HNO3, respectively. The maximum values for many of the target analytes occurred during the hazy period in May when there was significant contamination from regional fires. The elevated levels of HNO2 compared to HNO3 and high levels of HNO3 were rationalized based on artifacts in the denuder sampling methodology.