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The widespread presence of organic aerosols (OA) in the atmosphere and their dominant role in climate forcing are increasingly recognized. Measurements from the high‐altitude region provide insights into the natural processes and long‐range transport of aerosols. We studied water‐soluble organic compounds in PM1.1 during January‐March 2020 and February‐April 2021 at Ponmudi (8.8°N and 77.1°E), a tropical hill station (960 m a.s.l.) located on the Western Ghats of India. The 5‐day backward trajectories of air masses presented that continental and marine sources impacted the site during the campaign, and thus we classified samples as mixed and marine air masses. Their molecular fingerprints revealed the prevalence of oxalic acid (C2), followed by terephthalic acid in mixed air mass and malonic (C3) or succinic (C4) acid in maritime air mass aerosol samples. This feature and the phthalic to azelaic acid ratio, as well as the C3 to C4 and fumaric to maleic acid ratios, evidenced that water‐soluble OA were of anthropogenic origin and less photochemically aged in mixed air mass samples, whereas they derived from biogenic sources and more photochemical aging in marine air mass samples. However, we found their comparable contributions in water‐soluble organic carbon under mixed and marine air masses. Linear correlations between C2 relative abundance and its ratios with the precursor compounds implied that the oxidation of precursors to oxalic acid occurs during atmospheric transport. The results revealed that the input of anthropogenic and biogenic precursors followed by atmospheric processing controlled the burden of water‐soluble OA across the Western Ghats. Plain Language Summary: Dicarboxylic acids (DCAs), oxocarboxylic acids and dicarbonyls are ubiquitous water‐soluble components of organic aerosol (OA) that can serve as cloud condensation nuclei and affect the climate of the Earth. We reveal for the first time the molecular fingerprints and sources as well as formation processes of water‐soluble OA in PM1.1 at a tropical hill station in Western Ghats of India. Significant differences in the molecular fingerprints and atmospheric processes of water‐soluble OA were found due to the influence of different air masses. DCAs and related compounds in mixed air mass aerosols originated from anthropogenic sources and produced in the atmosphere by photooxidation during long‐range transport whereas they were of biogenic origin followed by intense photochemical aging of biogenic volatile organic compounds such as isoprene and unsaturated fatty acids during atmospheric transport in marine air mass aerosols. The results revealed that DCAs substantially contribute to water‐soluble OA not only in mixed air mass aerosols but also in marine air mass aerosols at the tropical hill station in the Western Ghats. These findings have implications for assessing climate‐forcing feedback of secondary OA over the Western Ghats that is driven by anthropogenic and biogenic sources followed by photochemical processes. Key Points: Mixed and marine air masses drive the molecular fingerprints of atmospheric water‐soluble organic compounds over the Western GhatsAerosols of mixed air masses comprised dicarboxylic acids (DCAs) of anthropogenic origin and less photochemically processedDCAs were produced from biogenic sources followed by intense photochemical aging in marine air mass aerosols [ABSTRACT FROM AUTHOR]

Abstract The widespread presence of organic aerosols (OA) in the atmosphere and their dominant role in climate forcing are increasingly recognized. Measurements from the high‐altitude region provide insights into the natural processes and long‐range transport of aerosols. We studied water‐soluble organic compounds in PM1.1 during January‐March 2020 and February‐April 2021 at Ponmudi (8.8°N and 77.1°E), a tropical hill station (960 m a.s.l.) located on the Western Ghats of India. The 5‐day backward trajectories of air masses presented that continental and marine sources impacted the site during the campaign, and thus we classified samples as mixed and marine air masses. Their molecular fingerprints revealed the prevalence of oxalic acid (C2), followed by terephthalic acid in mixed air mass and malonic (C3) or succinic (C4) acid in maritime air mass aerosol samples. This feature and the phthalic to azelaic acid ratio, as well as the C3 to C4 and fumaric to maleic acid ratios, evidenced that water‐soluble OA were of anthropogenic origin and less photochemically aged in mixed air mass samples, whereas they derived from biogenic sources and more photochemical aging in marine air mass samples. However, we found their comparable contributions in water‐soluble organic carbon under mixed and marine air masses. Linear correlations between C2 relative abundance and its ratios with the precursor compounds implied that the oxidation of precursors to oxalic acid occurs during atmospheric transport. The results revealed that the input of anthropogenic and biogenic precursors followed by atmospheric processing controlled the burden of water‐soluble OA across the Western Ghats.

Complex organic aerosols in the upper atmosphere of Saturn's moon Titan reach the troposphere and surface, where a methane (CH4)‐based hydrological cycle occur. Previous studies have assumed no interactions between organic aerosols and liquid CH4, although the dissolution of low‐molecular‐weight photochemical products in liquid CH4 has been considered. Here we report experimental results of soaking a laboratory analog (so‐called tholin) of Titan's organic aerosols in liquid CH4 at 93–98 K for several hours and then evaporating the liquid, simulating wet–dry cycling on Titan. After wet–dry cycling, residual tholin particles form aggregates through cementation. Solid evaporitic deposits formed by evaporation of interacted liquid contain nitrogen‐bearing aromatics, suggesting selective dissolution of aromatics. Our results suggest that organic aerosols or high‐molecular‐weight compounds adsorbed on them partly dissolve in liquid CH4 on Titan, even during short‐term wetting events, promoting the growth of aerosols to dune particles via aggregation and providing aromatics to evaporites. Plain Language Summary: Saturn's largest moon, Titan has a dense atmosphere composed of nitrogen and methane. Active organic chemistry induced by sunlight occurs in the atmosphere to form complex organic aerosols. These organic aerosols eventually settle on the surface, where rivers, lakes, and seas of liquid methane are present. Upon seasonal changes in precipitation and evaporation, wet–dry cycling of liquid methane is believed to occur on Titan, similar to Earth's water cycles. Can organic aerosols settled on the surface be dissolved into liquid methane? If so, what components of aerosol can be dissolved, and how could this affect Titan's geology? Here we perform laboratory experiments to address these questions. Unlike predictions by previous studies, we find that organic aerosols or aromatics adsorbed on them would partly dissolve into liquid methane efficiently. These processes could play key roles in the formation of unique landforms, such as dunes and evaporites, on Titan. Key Points: We experimentally simulate interactions between laboratory analogs (tholin) of Titan's aerosols and liquid methane at low temperaturesComplex aromatics are dissolved from tholin, forming evaporites after drying; while, residual tholin form aggregatesWet–dry cycling of aerosols on Titan may provide aromatics to evaporites and could explain size growth of aerosols to dune particles [ABSTRACT FROM AUTHOR]

By quantifying the absorption of black carbon (BC), brown carbon (BrC) and the lensing effect, we found that BrC dominates the total absorption at 450 nm, and the largest absorption contribution proportion of BrC could reach 78.3% during heavy pollution. The average absorption enhancement (Eabs) at 530 nm was only 1.38, indicating that BC is not coated well here. The average value of the absorption Ångstrom exponent (AAE) between 450 nm and 530 nm was 5.3, suggesting a high concentration of BrC in Wangdu. CHN+ was the greatest contributor to the light absorption of molecules detected in MSOC with a proportion of 12.2–22.4%, in which the polycyclic aromatic nitrogen heterocycles (PANHs) were the dominant compounds. The C6H5NO3 and its homologous series accounted for 3.0–11.3%, and the C15H9N and its homologous series, including one C16H11N and three C17H13N compounds, accounted for 5.1–12.3%. The absorption of these PANHs is comparable to that of nitro–aromatics, which should attract more attention to the impact of climate radiative forcing. [ABSTRACT FROM AUTHOR]

Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the “real-world” absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds.

Abstract Complex organic aerosols in the upper atmosphere of Saturn's moon Titan reach the troposphere and surface, where a methane (CH4)‐based hydrological cycle occur. Previous studies have assumed no interactions between organic aerosols and liquid CH4, although the dissolution of low‐molecular‐weight photochemical products in liquid CH4 has been considered. Here we report experimental results of soaking a laboratory analog (so‐called tholin) of Titan's organic aerosols in liquid CH4 at 93–98 K for several hours and then evaporating the liquid, simulating wet–dry cycling on Titan. After wet–dry cycling, residual tholin particles form aggregates through cementation. Solid evaporitic deposits formed by evaporation of interacted liquid contain nitrogen‐bearing aromatics, suggesting selective dissolution of aromatics. Our results suggest that organic aerosols or high‐molecular‐weight compounds adsorbed on them partly dissolve in liquid CH4 on Titan, even during short‐term wetting events, promoting the growth of aerosols to dune particles via aggregation and providing aromatics to evaporites.

Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the "real-world" absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds. [ABSTRACT FROM AUTHOR]

Organic aerosols (OAs) are key components of atmospheric PM 2.5, which impose an important influence on citizens' health and atmospheric chemistry. However, the vertical distribution and evolutionary mechanisms of OAs have remained unclear, posing challenges for accurate model simulations. To compare the difference in molecular distribution and sources at different altitudes and explore the impact of vertical transport of mountain-valley breezes on OAs in mountainous regions, PM 2.5 samples were simultaneously collected at both the summit (SM: 1840 m a.s.l) and the foot Mt. Huang (FM: 480 m a.s.l.) in winter. All the 128 detected organic species presented higher concentrations at FM (237 ± 118 ng m−3) than at SM (89.3 ± 40.9 ng m−3), indicating that the influence of anthropogenic emissions on OAs became more significant as elevation decreased. Levoglucosan was the dominant single organic species and displayed robust correlations with most organic components at both sites, suggesting the notable effect of biomass burning on OAs in the alpine atmosphere. Molecular composition, characteristic ratios, and positive matrix factorization analysis suggested that OAs at SM were more aged and mostly derived from secondary oxidation and biomass burning from long-range transport. However, anthropogenic sources (e.g., biomass burning and fossil fuel combustion) contributed more to OAs at FM. Potential source contribution function results revealed that the northeastern part of Jiangxi Province and the nearby regions of the observation point are the potential source regions for OAs at FM, while long-range transport from northwestern Anhui Province and northern Jiangxi Province played a key role in OAs at SM. This study proved that OAs at FM could influence the mountaintop aerosols through the vertical transport of valley breeze in the day at Mt. Huang. These findings enhance our understanding of the vertical distribution of OAs and provide a scientific foundation for cross-regional atmospheric pollution control. [Display omitted] • The concentrations of all the 128 organic species decreased as elevation increased. • The effect of anthropogenic pollutants became more significant as elevation decreased. • The mountaintop organic aerosols (OAs) were more aged than those at the foot. • The mountaintop OAs in the day were strongly impacted by the valley wind in winter. [ABSTRACT FROM AUTHOR]

The presence of organic compounds on the particulate matter (PM) or aerosols can arise from the condensation of gaseous organic compounds on the existing aerosols, or from organic precursors to form secondary organic aerosols (SOA) through photochemistry. The objective of this study is to characterize organic constituents on aerosols relevant to their emission sources and the key compounds revealing the evolution of aerosols with the use of a novel analytical technique. A time-of-flight mass spectrometry (TOFMS) coupled with comprehensive two-dimensional gas chromatography (GC×GC) was developed using a flow type of modulator instead of a thermal type as a prelude to field applications without the need for cryogen. The methodology of GC×GC-TOFMS is discussed in this study in detail. Since the coarse PM (PM 10-2.5) may exhibit with a relatively high OC content compared to PM 2.5 , the GC×GC results have been obtained by analyzing PM 10 samples collected in parallel with OC/EC analysis of PM 2.5 samples at the Lulin Atmospheric Background Station (LABS, 23.47°N, 120.87°E, 2862 m ASL) as the high-mountain background site in East Asia. We found that the organic analytes were in a majority in the range of 12–30 carbon numbers falling in the category of semi-volatile organic compounds (SVOCs) with 43 compounds of alcohol, aldehyde, ketone, and ester varieties if excluding alkanes. Intriguingly, trace amounts of plasticizers and phosphorus flame retardants such as phthalates (PAEs) and triphenyl phosphate (TPP) were also found, likely originating from regions involved in open burning of household solid waste in Southeast Asia or e-waste recycling in southern China and along the long-range transport route. Compounds such as these are unique to the specific sources, demonstrating the wide spread of these hazardous compounds in the environment. [Display omitted] • A GC×GC-TOFMS method is developed for aerosols using flow type modulation. • The PM organic constituents at a high-mountain site in March 2015 were analyzed. • PAEs and TPP were detected presumably from transboundary sources. [ABSTRACT FROM AUTHOR]

Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing.

Air quality simulations were performed for the Greater Athens Area in very high spatial resolution using the modeling system WRF-CAMx. Sensitivity runs were performed using the SOAP and VBS schemes for organic gas–aerosol partitioning and oxidation. In January 2019, OA-VBS decreased compared to OA-SOAP because of POA reduction. In July 2019, the OA-VBS increased with respect to OA-SOAP as a result of the increase in SOA levels exceeding the decrease in POA ones. The comparison of the WRF-CAMx results against PM10, PM2.5, and OC surface measurements provides the first indications for improved CAMx performance with the VBS scheme.

Air pollution is an important environmental risk factor associated with increased morbidity and excess mortality. Fine particulate matter (PM2.5) is a complex mixture of both organic and inorganic compounds, depending on emissions sources and atmospheric chemistry. According to toxicological studies, there is strong evidence that anthropogenic carbonaceous aerosols, especially those emitted from combustion sources, are more hazardous to human health than other types of fine particles. In this study, we use WRF-Chem to simulate PM2.5 and the carbonaceous sub-components (black carbon and organics from anthropogenic sources) over Europe. The excess mortality attributed to long-term exposure to these particles is quantified using the MR-BRT (meta-Regression–Bayesian, regularized, trimmed) and the Global Exposure Mortality Model (GEMM) exposure–response functions to assess the public health outcomes. Differential toxicity of carbonaceous aerosols is assumed to account for their potentially more pronounced effect on excess mortality.

As a part of the Integrated Campaign for Aerosols, gases and Radiation Budget (ICARB-2018), shipborne measurements of aerosol properties were carried out to study the influence of South Asian outflow on cloud condensation nuclei (CCN) characteristics over the South East Arabian Sea (SEAS) and equatorial Indian Ocean (EIO) during winter, 2018. The poor association between CCN concentration and mass concentrations of the major aerosol species (organic matter, sulfate, and elemental carbon) is observed over SEAS, where airmass is mostly continental. In comparison, the CCN is well-correlated with aerosol mass concentrations over remote EIO. The dependence of CCN activation (at lower supersaturations) on the ultrafine particle fraction differs between SEAS and EIO depending on the mass concentration of organic aerosols. The coexistence of small and hydrophobic aerosols (organics) decreased the CCN activation ratio during ultrafine particle events. The hygroscopicity estimated using the chemical composition of aerosols is comparable to that estimated from CCN measurements over the Indian Ocean, except for the SEAS, where organic aerosols dominate. The effect of outflow aerosols on cloud droplet number concentration (CDNC) is simulated using a parcel model, which showed a good association (R ∼0.96) with CCN measurements over the EIO; however, the estimated CDNC did not follow the CCN variation over the SEAS region. This study highlights the importance of aerosol chemical composition, especially organics, in CCN activation and cloud droplet formation in the South Asian outflow over the Indian Ocean. • Hygroscopicity (κ) of continental aerosols over the Indian Ocean is examined. • Ultrafine particles and organics decrease the CCN activation of South Asian outflow. • CCN at 0.2% SS estimated from measured κ has positive bias over the Arabian Sea. • Estimated CDNC over near-coastal regions is mostly invariant with CCN concentration. [ABSTRACT FROM AUTHOR]

Organic aerosols (OA) represent a significant fraction of total submicron particulate matter (PM1) concentrations globally, including densely populated megacities such as Seoul. However, scientific understanding of the atmospheric formation and removal processes of OA, especially for secondary organic aerosols (SOA), is still highly uncertain. In this study, we examine the characteristics of SOA formation in Seoul during spring‐summer 2016 and fall‐winter 2017/2018, using airborne and ground observations along with a 3‐D global chemical transport model, GEOS‐Chem. We use four different SOA schemes in the model, including simplified and complex volatility‐based frameworks, and evaluate them by comparing the simulations with the observations to examine how our scientific understanding embedded in each SOA scheme affects the observed biases. Our analysis of the model performance of each scheme also provides the most suitable approach in simulating SOA in a typical urban environment. Comparisons of the simulated versus observed OA concentrations show that model biases range from −72% to +118%, with considerable variability among different schemes and seasons. We find that the inclusion of semi/intermediate volatile precursors, in addition to the traditional precursors, and chemical aging (functionalization) are important factors to simulate surface SOA concentrations in Seoul. However, a comparison of observed and simulated SOA/∆CO enhancement ratios suggests that most schemes underpredict SOA aging in upper levels in the boundary layer. We also find that the simplified SOA scheme can reproduce observed OA but often shows overestimation in surface air, indicating that uncertainties exist in bottom‐up emissions and precursor parameterization in Seoul. Plain Language Summary: We compare four different modeling approaches for simulating secondary organic aerosol (SOA) formation, accounting for a significant fraction of total fine particulate matter concentrations in Seoul, Korea. Using GEOS‐Chem, a chemical transport model, we find that current SOA schemes show large variabilities. Including an additional precursor species and further oxidation (i.e., chemical aging) of simulated SOA improves model performance. We also find that a simplified scheme with less computational cost can reproduce observed values but generally shows an overestimation in Seoul, indicating uncertainties in parameterization. Key Points: Model evaluation of simulated organic aerosols (OA) using different secondary organic aerosols (SOA) schemes in Seoul shows large variabilityThe inclusion of semi/intermediate volatile precursors and chemical aging are important factors in reducing model biasesThe simplified SOA scheme can reproduce observed OA, but uncertainties exist in precursor parameterization in Seoul [ABSTRACT FROM AUTHOR]

Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing. [ABSTRACT FROM AUTHOR]

Abstract Organic aerosols (OA) represent a significant fraction of total submicron particulate matter (PM1) concentrations globally, including densely populated megacities such as Seoul. However, scientific understanding of the atmospheric formation and removal processes of OA, especially for secondary organic aerosols (SOA), is still highly uncertain. In this study, we examine the characteristics of SOA formation in Seoul during spring‐summer 2016 and fall‐winter 2017/2018, using airborne and ground observations along with a 3‐D global chemical transport model, GEOS‐Chem. We use four different SOA schemes in the model, including simplified and complex volatility‐based frameworks, and evaluate them by comparing the simulations with the observations to examine how our scientific understanding embedded in each SOA scheme affects the observed biases. Our analysis of the model performance of each scheme also provides the most suitable approach in simulating SOA in a typical urban environment. Comparisons of the simulated versus observed OA concentrations show that model biases range from −72% to +118%, with considerable variability among different schemes and seasons. We find that the inclusion of semi/intermediate volatile precursors, in addition to the traditional precursors, and chemical aging (functionalization) are important factors to simulate surface SOA concentrations in Seoul. However, a comparison of observed and simulated SOA/∆CO enhancement ratios suggests that most schemes underpredict SOA aging in upper levels in the boundary layer. We also find that the simplified SOA scheme can reproduce observed OA but often shows overestimation in surface air, indicating that uncertainties exist in bottom‐up emissions and precursor parameterization in Seoul.

Abstract The Community Earth System Model version 2 (CESM2) includes three main atmospheric configurations: the Community Atmosphere Model version 6 (CAM6) with simplified chemistry and a simplified organic aerosol (OA) scheme, CAM6 with comprehensive tropospheric and stratospheric chemistry representation (CAM6‐chem), and the Whole Atmosphere Community Climate Model version 6 (WACCM6). Both, CAM6‐chem and WACCM6 include a more comprehensive secondary organic aerosols (SOA) approach using the Volatility Basis Set (VBS) scheme and prognostic stratospheric aerosols. This paper describes the different OA schemes available in the different atmospheric configurations of CESM2 and discusses differences in aerosol burden and resulting climate forcings. Derived OA burden and trends differ due to differences in OA formation using the different approaches. Regional differences in Aerosol Optical Depth with larger values using the comprehensive approach occur over SOA source regions. Stronger increasing SOA trends between 1960 and 2015 in WACCM6 compared to CAM6 are due to increasing biogenic emissions aligned with increasing surface temperatures. Using the comprehensive SOA approach further leads to improved comparisons to aircraft observations and SOA formation of ≈143 Tg/yr. We further use WACCM6 to identify source contributions of OA from biogenic, fossil fuel, and biomass burning emissions, to quantify SOA amounts and trends from these sources. Increasing SOA trends between 1960 and 2015 are the result of increasing biogenic emissions aligned with increasing surface temperatures. Biogenic emissions are at least two thirds of the total SOA burden. In addition, SOA source contributions from fossil fuel emissions become more important, with largest values over Southeast Asia. The estimated total anthropogenic forcing of OA in WACCM6 for 1995–2010 conditions is −0.43 W/m2, mostly from the aerosol direct effect.

The current understanding of water-soluble organic aerosol (OA) composition, sources, transformations, and effects is still limited to outdoor scenarios. However, the OA is also an important component of particulate matter indoors, whose complexity impairs a full structural and molecular identification. The current limited knowledge on indoor OA, and particularly on its water-soluble organic matter (WSOM) fraction is the basis of this feature paper. Inspired by studies on outdoor OA, this paper discusses and prioritizes issues related to indoor water-soluble OA and their effects on human health, providing a basis for future research in the field. The following three main topics are addressed: (1) what is known about the origin, mass contribution, and health effects of WSOM in outdoor air particles; (2) the current state-of-the-art on the WSOM in indoor air particles, the main challenges and opportunities for its chemical characterization and cytotoxicity evaluation; and (3) why the aerosol WSOM should be considered in future indoor air quality studies. While challenging, studies on the WSOM fraction in air particles are highly necessary to fully understand its origin, fate, toxicity, and long-term risks indoors. [ABSTRACT FROM AUTHOR]

In the troposphere, the heterogeneous lifetime of an organic molecule in an aerosol exposed to hydroxyl radicals (OH) is thought to be weeks, which is orders of magnitude slower than the analogous gas phase reactions (hours). Here, we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10-50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. A kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.

The air quality in the outflow from Fort Worth, TX was studied in June 2011 at a location surrounded by oil and gas development in the Barnett Shale. The objectives of this study were to understand the major sources of volatile organic compounds (VOCs) and organic aerosols and explore the potential influence each VOC source had on ozone and secondary organic aerosol formation. Measurements of VOCs were apportioned between six factors using Positive Matrix Factorization (PMF): Natural Gas (25 ± 2%; ±99% CL); Fugitive Emissions (15 ± 2%); Internal Combustion Engines (15 ± 2%); Biogenic Emissions (7 ± 1%); Industrial Emissions/Oxidation 1(8 ± 1%); and Oxidation 2 (18 ± 2%). Reactivity calculations suggest the Biogenic and Oxidation 2 factors were the most likely VOC sources to influence local ozone. However, enough OH reactivity was calculated for factors related to the oil and gas development that they could incrementally increase O3. Three organic aerosol (OA) types were identified with PMF applied to high-resolution time-of-flight aerosol mass spectrometry measurements: hydrocarbon-like OA (HOA; 11% of mass) and two classes of oxidized OA (semi- and less-volatile OOA, SV and LV; 45% and 44%, respectively). The HOA correlated with the Internal Combustion Engine VOC factor indicating that a large fraction of the HOA was emitted by gasoline and diesel motors. The SV-OOA correlated with the oxidized VOC factors during most of the study, whereas a correlation between LV-OOA and the oxidized VOC factors was only observed during part of the study. It is hypothesized that SV-OOA and the oxidized VOC factors correlated reasonably well because these factors likely were separated by at most only a few oxidation generations on the oxidation pathway of organic compounds.

The North China Plain (NCP) is a region that experiences serious aerosol pollution. A number of studies have focused on aerosol pollution in urban areas in the NCP region; however, research on characterizing aerosols in rural NCP areas is comparatively limited. In this study, we deployed a TD-HR-AMS (thermodenuder high-resolution aerosol mass spectrometer) system at a rural site in the NCP region in summer 2013 to characterize the chemical compositions and volatility of submicron aerosols (PM1). The average PM1 mass concentration was 51.2 ± 48.0 µg m−3 and organic aerosol (OA) contributed most (35.4%) to PM1. Positive matrix factorization (PMF) analysis of OA measurements identified four OA factors, including hydrocarbon-like OA (HOA, accounting for 18.4%), biomass burning OA (BBOA, 29.4%), less-oxidized oxygenated OA (LO-OOA, 30.8%) and more-oxidized oxygenated OA (MO-OOA, 21.4%). The volatility sequence of the OA factors was HOA > BBOA > LO-OOA > MO-OOA, consistent with their oxygen-to-carbon (O:C) ratios. Additionally, the mean concentration of organonitrates (ON) was 1.48–3.39 µg m−3, contributing 8.1%–19% of OA based on cross validation of two estimation methods with the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurement. Correlation analysis shows that ON were more correlated with BBOA and black carbon emitted from biomass burning but poorly correlated with LO-OOA. Also, volatility analysis for ON further confirmed that particulate ON formation might be closely associated with primary emissions in rural NCP areas. [ABSTRACT FROM AUTHOR]

Biomass burning (BB) significantly influences the chemical composition of organic aerosols (OA) in the East Asian outflow. Source apportionment of BB-derived OA is an influential factor for understanding their regional emissions, which is crucial for reducing uncertainties in their projected climate and health-effects. We analyzed here three different classes of atmospheric sugar compounds (anhydrosugars, primary sugars, and sugar alcohols) and two types of biogenic secondary organic aerosol (BSOA) tracers (isoprene- and monoterpene derived SOA products) in a year-long collected total suspended particulate matter (TSP) from an island-based receptor site in South Korea, the Gosan. We investigate seasonal variations in the source-emissions of BB-derived OA using mass concentrations of anhydrosugars and radiocarbon (14C-) isotopic composition of organic carbon (OC) and elemental carbon (EC) in ambient aerosols. Levoglucosan (Lev) is the most abundant anhydrosugar, followed by galactosan (Gal) and/or mannosan (Man). Strong correlations of Lev with Gal and Man as well as their high mass ratios such as Lev/Gal (6.7±2.2) and Lev/Man (15.0±6.7), indicate the contribution from hardwood burning emissions. The seasonal trends revealed that the biomass-burning impact is more pronounced in winter and fall, as evidenced from the high concentrations of anhydrosugars. Likewise, significant correlations were observed among three primary sugars (i.e., glucose, fructose, and sucrose), emphasizing the contribution from airborne pollen. The primary sugars showed higher concentrations in spring/summer than winter/fall. The fungal spore tracer compounds (i.e., arabitol, mannitol, and erythritol) correlated well with trehalose (i.e., a proxy for soil organic carbon), suggesting the origin from airborne fungal spores and soil microbes in the East Asian outflow. These sugar alcohols peaked in summer, followed by spring/fall and winter. Monoterpene-derived SOA tracers were most abundant compared to isoprene-SOA tracers. Both BSOA tracers were dominant in summer, followed by fall, spring, and winter. The source apportionment based on multiple linear regressions, diagnostic mass ratios, and positive matrix factorization analysis altogether revealed that biomass burning (41.9%) and biogenic SOA (21.1%) mostly dictates the OA loading in the ambient aerosols from East Asian outflow. We also found significant positive linear relationships of 14C-based nonfossil- and fossil-derived organic carbon fractions with Lev-C along with the comparable regression slopes, suggesting the importance of BB and coal combustion sources in the East Asian outflow. [ABSTRACT FROM AUTHOR]

Two approaches were applied for characterization of organic compounds in the atmospheric aerosols. These were chemical and statistical grouping analysis. We applied chemical group analysis as a new approach using the GC×GC data. Based on the principle of GC×GC, analytes in two dimensional data were divided into 6 chemical group depending on their volatility and polarity. Using this classification standards, all analytes were classified as one of 6 chemical groups, HP-VOC, LP-VOC, HP-SVOC, LP-SVOC, HP-NVOC and LP-NVOC. The relationship between the sum of the peak areas of each chemical group with other variables such as the concentrations of OC, EC, OCPOC, OC/EC and OCSOC were studied. However, no apparent relationship was observed. The principle component analysis (PCA) was carried out to find out the relationship among the analytes based on their sources. The OVOCs were dominant compounds in 3 out of 4 factors in summer. In winter, factor 1 was related to secondary organic aerosol and factor 3 was related to primary emission sources. The proposed approach looks promising in characterization of chemical groups but have limitations at current stage which are discussed.

Water-soluble organic aerosols (OA) are an important component of air particles and one of the key drivers that impact both climate and human health. Understanding the processes involving water-soluble OA depends on how well the chemical composition of this aerosol component is decoded. Yet, obtaining detailed information faces several challenges, including water-soluble OA collection, extraction, and chemical complexity. This review highlights the multidimensional non-targeted analytical strategies that have been developed and employed for providing new insights into the structural and molecular features of water-soluble organic components present in air particles. First, the most prominent high-resolution mass spectrometric methods for near real-time measurements of water-soluble OA and their limitations are discussed. Afterward, a special emphasis is given to the degree of compositional information provided by offline multidimensional analytical techniques, namely excitation–emission (EEM) fluorescence spectroscopy, high-resolution mass spectrometry and two-dimensional nuclear magnetic resonance (NMR) spectroscopy and their hyphenation with chromatographic systems. The major challenges ahead on the application of these multidimensional analytical strategies for OA research are also addressed so that they can be used advantageously in future studies. [ABSTRACT FROM AUTHOR]

The Community Earth System Model version 2 (CESM2) includes three main atmospheric configurations: the Community Atmosphere Model version 6 (CAM6) with simplified chemistry and a simplified organic aerosol (OA) scheme, CAM6 with comprehensive tropospheric and stratospheric chemistry representation (CAM6‐chem), and the Whole Atmosphere Community Climate Model version 6 (WACCM6). Both, CAM6‐chem and WACCM6 include a more comprehensive secondary organic aerosols (SOA) approach using the Volatility Basis Set (VBS) scheme and prognostic stratospheric aerosols. This paper describes the different OA schemes available in the different atmospheric configurations of CESM2 and discusses differences in aerosol burden and resulting climate forcings. Derived OA burden and trends differ due to differences in OA formation using the different approaches. Regional differences in Aerosol Optical Depth with larger values using the comprehensive approach occur over SOA source regions. Stronger increasing SOA trends between 1960 and 2015 in WACCM6 compared to CAM6 are due to increasing biogenic emissions aligned with increasing surface temperatures. Using the comprehensive SOA approach further leads to improved comparisons to aircraft observations and SOA formation of ≈143 Tg/yr. We further use WACCM6 to identify source contributions of OA from biogenic, fossil fuel, and biomass burning emissions, to quantify SOA amounts and trends from these sources. Increasing SOA trends between 1960 and 2015 are the result of increasing biogenic emissions aligned with increasing surface temperatures. Biogenic emissions are at least two thirds of the total SOA burden. In addition, SOA source contributions from fossil fuel emissions become more important, with largest values over Southeast Asia. The estimated total anthropogenic forcing of OA in WACCM6 for 1995–2010 conditions is −0.43 W/m2, mostly from the aerosol direct effect. Key Points: CESM2 (WACCM6) includes an updated secondary aerosol scheme using the volatility basis set approachThe new SOA parameterization results in regional changes in radiative forcings and aerosol optical depthPositive SOA trends between 1960 and 2015 are caused by both increasing biogenic and anthropogenic sources [ABSTRACT FROM AUTHOR]

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow.

Here we report a new method for measuring the heterogeneous chemistry of submicron organic aerosol particles using a continuous flow stirred tank reactor. This approach is designed to quantify the real time heterogeneous kinetics, using a relative rate method, under conditions of low oxidant concentration and long reaction times that more closely mimic the real atmosphere. A general analytical expression, which couples the aerosol chemistry with the flow dynamics in the chamber is developed and applied to the heterogeneous oxidation of squalane particles by hydroxyl radicals (OH) in the presence of O2. The particle phase reaction is monitored via photoionization aerosol mass spectrometry and yields a reactive uptake coefficient of 0.51+-0.10, using OH concentrations of 1-7x108 molec cdot cm-3 and reaction times of 1.5+-3 hours. This uptake coefficient is larger than that found for the reaction carried out under high OH concentrations (~;;1x1010 molec cdot cm-3) and short reaction times in a flow tube reactor. This difference suggests that oxidant concentration and reaction time are not interchangeable quantities in reactions of organic aerosols with radicals. In general, this approach provides a new way to examine how the chemical aging of organic particles measured at short reaction times and high oxidant concentrations in flow tubes might differ from the long reaction times and low oxidant levels found in the real atmosphere.

The current understanding of water-soluble organic aerosol (OA) composition, sources, transformations, and effects is still limited to outdoor scenarios. However, the OA is also an important component of particulate matter indoors, whose complexity impairs a full structural and molecular identification. The current limited knowledge on indoor OA, and particularly on its water-soluble organic matter (WSOM) fraction is the basis of this feature paper. Inspired by studies on outdoor OA, this paper discusses and prioritizes issues related to indoor water-soluble OA and their effects on human health, providing a basis for future research in the field. The following three main topics are addressed: (1) what is known about the origin, mass contribution, and health effects of WSOM in outdoor air particles; (2) the current state-of-the-art on the WSOM in indoor air particles, the main challenges and opportunities for its chemical characterization and cytotoxicity evaluation; and (3) why the aerosol WSOM should be considered in future indoor air quality studies. While challenging, studies on the WSOM fraction in air particles are highly necessary to fully understand its origin, fate, toxicity, and long-term risks indoors.

Atmospheric aerosol deposition (wet and dry) is an important source of macro and micronutrients (N, P, C, Si, and Fe) to the oceans. Most of the mass flux of air particles is made of fine mineral particles emitted from arid or semi-arid areas (e.g., deserts) and transported over long distances until deposition to the oceans. However, this atmospheric deposition is affected by anthropogenic activities, which heavily impacts the content and composition of aerosol constituents, contributing to the presence of potentially toxic elements (e.g., Cu). Under this scenario, the deposition of natural and anthropogenic aerosols will impact the biogeochemical cycles of nutrients and toxic elements in the ocean, also affecting (positively or negatively) primary productivity and, ultimately, the marine biota. Given the importance of atmospheric aerosol deposition to the oceans, this paper reviews the existing knowledge on the impacts of aerosol deposition on the biogeochemistry of the upper ocean, and the different responses of marine biota to natural and anthropogenic aerosol input.

Water-soluble organic aerosols (OA) are an important component of air particles and one of the key drivers that impact both climate and human health. Understanding the processes involving water-soluble OA depends on how well the chemical composition of this aerosol component is decoded. Yet, obtaining detailed information faces several challenges, including water-soluble OA collection, extraction, and chemical complexity. This review highlights the multidimensional non-targeted analytical strategies that have been developed and employed for providing new insights into the structural and molecular features of water-soluble organic components present in air particles. First, the most prominent high-resolution mass spectrometric methods for near real-time measurements of water-soluble OA and their limitations are discussed. Afterward, a special emphasis is given to the degree of compositional information provided by offline multidimensional analytical techniques, namely excitation–emission (EEM) fluorescence spectroscopy, high-resolution mass spectrometry and two-dimensional nuclear magnetic resonance (NMR) spectroscopy and their hyphenation with chromatographic systems. The major challenges ahead on the application of these multidimensional analytical strategies for OA research are also addressed so that they can be used advantageously in future studies.

The cell-free dithiothreitol (DTT) assay is widely used and the DTT consumption rate is interpreted to assess the oxidative potential (OP). Most researchers use an experimental procedure developed by Cho et al. (2005) while some adopt a procedure by Li et al. (2009). The key difference between the two procedures is the initial DTT concentration, 100 μM used in the former and 20 μM in the latter, raising an unaddressed issue of comparability. We examine in this work this issue using metal-free humic-like substance (HULIS) samples isolated from ambient aerosol and two metals (i.e. copper and manganese). We found that higher initial DTT concentrations led to higher DTT consumption rates for both HULIS and metals. For HULIS, the increase in DTT consumption rate was proportional to the initial DTT concentration (i.e., roughly by 5-fold), allowing correction of the concentration effect and direct comparison of results from the two protocols. However, the proportionality did not hold for the metals or metal-organic mixtures. The increase was much lower than the proportionality of 5 and metal concentration-dependent, specifically, 1.2–1.3 for Cu and from negligible to 2.0 for Mn. For six water extracts of ambient aerosol samples, in which HULIS and metals co-exist, the proportionality ranged from 1.3 to 2.2. This deviation from a linear dependence on initial DTT concentration, plausibly due to metal-DTT binding, impedes assessing and comparing OP of metals and metal-organic mixtures using different implementations of the DTT assay. Considering the different antioxidants concentrations in real human lung fluid, this work raises caution about using the DTT assay to assess metal-containing mixtures, such as ambient aerosol samples. Image 1 • Oxidative potential of redox active organics is proportional to initial DTT concentration. • The proportionality does not hold for Cu and Mn with the DTT assay. • A 5-fold increase in DTT produced <2-fold rise in measured OP for Cu and Mn. • Deviation from linear dependence impedes the utility of the DTT assay for metals. • Caution is needed in quantifying OP of metal-organics mixtures by the DTT assay. Oxidative potential by metals measured with the dithiothreitol (DTT) assay significantly deviates from being proportional to the DTT concentration, raising concerns for the suitability of the DTT assay for aerosol samples. [ABSTRACT FROM AUTHOR]

Abstract A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed during wintertime (5 February to 15 March 2016) at a suburban site in Douai, northern France, in order to investigate the characteristics and sources of the organic matter (OM). The campaign average concentration of non-refractory submicron particulate matter (NR-PM 1) was 11.1 ± 9.3 μg m−3, and composed of 38% OM, 36% nitrate, 16% ammonium and 9% sulfate. The average values for the OM:OC, O:C and H:C ratios were 1.60 ± 0.15, 0.32 ± 0.11 and 1.55 ± 0.14, respectively, indicating a moderate level of aerosol oxidation. The positive matrix factorization (PMF) source apportionment method was applied to the high-resolution organic aerosol (OA) mass spectra, resulting in four factors: a hydrocarbon-like (HOA) factor; one associated with oxidized biomass burning (oBBOA); and two oxygenated factors (OOA) denoted as less oxidized (LO-OOA) and more oxidized (MO-OOA), with average contributions to OA of 20%, 28%, 17% and 35%, respectively. The oBBOA factor was found to be mainly local as shown by non-parametric wind regression (NWR) analysis, and to correlate well with relative humidity (RH), suggesting fast aqueous processing of locally emitted primary biomass burning emissions. During most part of the campaign, the sampling site was affected by different air masses. However, during the last period of the campaign (5–16 March 2016) the site was heavily impacted by air masses from Eastern Europe which were rich in secondary inorganic and organic aerosols. The H:C versus O:C (Van Krevelen, VK) diagram highlighted that the aerosol followed an oxidation process throughout the whole campaign, with an average slope of −1.05. The impact of continental air masses towards the end of the campaign confined the aerosol towards a narrower space in the VK diagram, suggesting a homogenization of the different aerosol sources due to OA ageing during transport. Several nocturnal NPF (new particle formation)-like events were observed and associated to the fast processing of BBOA emissions and the formation of ammonium nitrate. Graphical abstract Image 1 Highlights • Organic matter at a suburban site in winter investigated at high time resolution. • Aerosols were moderately oxidized with four sources of organic aerosol identified. • Oxidized biomass burning organic aerosols (BBOA) mostly local represented 28% of OA. • Several nocturnal NPF (new particle formation)-like events were observed. • It suggests a fast processing of BBOA and the possible role of ammonium nitrate. [ABSTRACT FROM AUTHOR]

This study reports for the first-time the ambient concentrations of HULIS mass (HULIS-OM, Humic-like substances) and HULIS-C (carbon) in PM10 (particulate matter with aerodynamic diameter ≤ 10 μm) from the Indo-Gangetic Plain (IGP at Kanpur, wintertime). HULIS extraction followed by purification and isolation protocol with methanol: acetonitrile (1:1 v/v) on HLB (Hydrophilic-Lipophilic Balanced) cartridge has been established. Quantification of HULIS-C was achieved on a total organic carbon (TOC) analyser whereas HULIS-OM was determined gravimetrically. Consistently high recovery (> 90%) of HULIS-C based on analysis of Humic standard (sodium salt of Humic acid) suggested suitability of our established analytical protocol involving solvent extraction, purification and accurate quantification of HULIS. HULIS-OM varied from 17.3-38 μg m−3 during daytime and from 19.8-40.6 μg m−3 during night in this study. During daytime the HULIS-OM constituted 20-30% mass fraction of OMTotal and 10-15% of PM10 mass. However, a relatively low contribution of HULIS-OM has been observed during the night. This observation has been attributed to higher concentrations of OM and PM10 in night owing to nighttime chemical reactivity and condensation of organics in conjunction with shallower planetary boundary layer height. Strong correlation of HULIS-C with K+BB (R2 > 0.80) and significant day-night variability of HULIS-C/WSOC ratio in conjunction with air-mass back trajectories (showing transport of pollutants from upwind IGP) suggest biomass burning emission and secondary transformations as important sources of HULIS over IGP. High-loading of atmospheric PM10 (as high as 440 μg m−3) with significant contribution of water-soluble organic aerosols (WSOC/OC: ~ 0.40-0.80) during wintertime highlights their plausible potential role in fog and haze formation and their impact on regional-scale atmospheric radiative forcing over the IGP. [ABSTRACT FROM AUTHOR]

The characteristics of non-refractory submicron aerosols (NR-PM 1), focusing on organic aerosols, are examined over a tropical coastal location, Thumba, in southern peninsular India. The measurements were carried out using an aerosol chemical speciation monitor during 2017–2021. The results indicated organic aerosols as the major component (67–85%) in the NR-PM 1 mass loading during all seasons. Positive matrix factorization (PMF) analysis on the OA mass spectra yielded two factors resolving Hydrocarbon-like organic aerosols (HOA) and Oxygenated organic aerosols (OOA), with the major contribution to OA coming from OOA (mass fraction >50%) during all the seasons. Examination of the diurnal variations revealed the daytime enhancement in OOA and sulfate mass fractions, indicating photochemical production overwhelming the dilution at the surface due to local atmospheric boundary layer expansion. The OOA mass concentration showed a good correlation (R > 0.5) with odd oxygen (O 3 +NO 2) and with an increase in oxygen-to-carbon ratio (ΔO:C = 0.11 to 0.35 with Δodd oxygen = 60 μg m−3 for different seasons) (i.e., increased oxidation degree of OA) signifying the dominance of photochemistry and subsequent enhanced atmospheric oxidative capacity in OOA formation. Interestingly, the aerosol liquid water content (ALWC) doubled during the nighttime (>40 μg m−3) compared to the daytime (<20 μg m−3) in different seasons, indicating the combined impact of varying submicron aerosol composition and ambient relative humidity. Since highly humid (relative humidity >85%) conditions prevail over this tropical coastal station, especially during the nighttime, the role of aqueous-phase formation of OA is also examined. It was found that less oxidized/less-hygroscopic OA were prevalent during the nighttime, resulting in lower aqueous-phase OA processing. During all the seasons, the hygroscopicity of organics (к organics) reached as high as > 0.22 and was mainly driven by photochemical processing rather than aqueous-phase chemistry. These results highlight the importance of the OA formation pathways in affecting their hygroscopic properties over the tropical atmosphere. • Organics are the dominant NR-PM 1 species in all seasons. • Oxygenated species dominated (>50%) the overall OA. • Photochemical reactions dominated OOA production. • The hygroscopicity of organics is mainly driven by photochemical processing. [ABSTRACT FROM AUTHOR]

Matrix-induced signal suppression or enhancements are known phenomena in electrospray ionization mass spectrometry. Very few studies report on method development for organic aerosols analyses with the evaluation of the matrix effects. The matrix effects lead to errors in the quantification of the analytes and affect the detection capability, precision, and accuracy of an analysis method. The present study reports on the matrix effects in the analysis of organic chemical compounds present in atmospheric aerosol particles collected on quartz filters. A total number of 19 analytes, including different classes of organic compounds, such as monoaromatic phenols and derivatives (e.g., catechol, 4-methylcatechol, 3-methoxycatechol, 4-nitrocatechol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dimethyl-4-nitrophenol), carboxylic acids (terebic acid, adipic acid, pimelic acid, phthalic acid, vanillic acid), and sulfonic acids (e.g., camphor-10-sulfonic acid), was investigated by high-performance liquid chromatography coupled to electrospray ionization time-of-flight mass spectrometry (HPLC/ESI-ToF-MS). The HPLC and ESI set-up parameters used in this study were previously optimized for the investigated compounds. Different volumes of a standard mixture were added to sample extracts, with final solutions concentrations in the 50–1500 μg L−1 range. For the investigated concentration range, the observed matrix effect was independent of the standard concentration level. For quartz filter extracts, the average matrix effect determined on a concentration-based method was 109.5 ± 6.1%. Both signal suppression and enhancement effects were observed for different compounds. For other analytes, the influence of the matrix effect is variable, suggesting that the use of an internal standard is not sufficient for the matrix effects correction. Competition between analyte ions and matrix components in the gas-phase ionization processes occurring in electrospray might explain signal suppression while generated coeluted isobaric compounds might induce signal enhancement.