Organosulfates (OSs), also referred to as organic sulfate esters, are well-known and ubiquitous constituents of atmospheric aerosol particles. Commonly, they are assumed to form upon mixing of air ...masses of biogenic and anthropogenic origin, that is, through multiphase reactions between organic compounds and acidic sulfate particles. However, in contrast to this simplified picture, recent studies suggest that OSs may also originate from purely anthropogenic precursors or even directly from biomass and fossil fuel burning. Moreover, besides classical OS formation pathways, several alternative routes have been discovered, suggesting that OS formation possibly occurs through a wider variety of formation mechanisms in the atmosphere than initially expected. During the past decade, OSs have reached a constantly growing attention within the atmospheric science community with evermore studies reporting on large numbers of OS species in ambient aerosol. Nonetheless, estimates on OS concentrations and implications on atmospheric physicochemical processes are still connected to large uncertainties, calling for combined field, laboratory, and modeling studies. In this Critical Review, we summarize the current state of knowledge in atmospheric OS research, discuss unresolved questions, and outline future research needs, also in view of reductions of anthropogenic sulfur dioxide (SO2) emissions. Particularly, we focus on (1) field measurements of OSs and measurement techniques, (2) formation pathways of OSs and their atmospheric relevance, (3) transformation, reactivity, and fate of OSs in atmospheric particles, and (4) modeling efforts of OS formation and their global abundance.
Investigation of the consecutive reactions of first-generation terpene oxidation products provides insight into the formation of secondary organic aerosol (SOA). To this end, OH radical reactions ...with α-pinene, β-pinene, and limonene were examined along with the OH-oxidation of nopinone as a β-pinene oxidation product and pinonaldehyde and myrtenal as α-pinene oxidation products. The SOA yield of β-pinene (0.50) was much higher than that of α-pinene (0.35) and the limonene/OH system (0.30). This is opposite to the ozonolysis SOA yields described in the literature. The growth curve of SOA from β-pinene shows the contribution of secondary reactions, such as further reaction of nopinone. This contribution (17%) and the high SOA yield of nopinone (0.24) might lead to the high SOA formation potential observed for β-pinene. The majority of the C9 oxidation products observed from β-pinene can be attributed to the consecutive reaction of nopinone, whereas in the case of pinonaldehyde, only a few α-pinene oxidation products were identified. Nopinone contributes significantly to the formation of pinic acid (51%), homoterpenylic acid (74%), and 3-methyl-1,2,3-butane-tricarboxylic acid (MBTCA, 88%) during β-pinene oxidation. The oxidation of pinonaldehyde was expected to produce important SOA markers, but only negligible amounts were identified. This indicates that their formation by oxidation of α-pinene must proceed via different pathways from the further oxidation of pinonaldehyde. Only pinonic acid and MBTCA were found in considerable amounts and were formed in α-pinene oxidation with 57% yield, while that for the pinonaldehyde/OH reaction was 33%. The lack of important SOA marker compounds might cause the low SOA yield (0.07) observed for pinonaldehyde. Based on the low SOA yield, pinonaldehyde contributes only 4.5% to α-pinene SOA. Myrtenal was identified among the gas-phase products of α-pinene oxidation. A majority of α-pinene SOA marker compounds was indeed formed by myrtenal oxidation, especially terebic acid (84%), pinic acid (76%), and diaterpenylic acid acetate (DTAA; 40%). In general, the contribution of myrtenal to α-pinene SOA is estimated to be as high as 23%. Among the detected compounds, homoterpenylic acid was positively identified as a new SOA marker compound, which was formed from β-pinene/OH and nopinone/OH but not from α-pinene/OH. A new reaction pathway yielding MBTCA was also identified in the β-pinene/OH system formed by the oxidation of nopinone, while in the case of α-pinene, the oxidation of pinonaldehyde yielded MBTCA.
•SOA formation potential of β-pinene/OH > α-pinene/OH > limonene/OH.•Oxidation of first-generation oxidation products enables insights into the formation of secondary organic aerosol (SOA).•New reaction channels yielding SOA marker compounds.•First analytical evidence for homoterpenylic acid – a SOA marker compound.
Very recent studies have reported the existence of highly oxidized multifunctional organic compounds (HOMs) with O/C ratios greater than 0.7. Because of their low vapor pressure, these compounds are ...often referred as extremely low-volatile organic compounds (ELVOCs), and thus, they are able to contribute significantly to organic mass in tropospheric particles. While HOMs have been successfully detected in the gas phase, their fate after uptake into particles remains unclear to date. Hence, the present study was designed to detect HOMs and related oxidation products in the particle phase and, thus, to shed light on their fate after phase transfer. To this end, aerosol chamber investigations of α-pinene ozonolysis were conducted under near environmental precursor concentrations (2.4 ppb) in a continuous flow reactor. The chemical characterization shows three classes of particle constituents: (1) intact HOMs that contain a carbonyl group, (2) particle-phase decomposition products, and (3) highly oxidized organosulfates (suggested to be addressed as HOOS). Besides chamber studies, HOM formation was also investigated during a measurement campaign conducted in summer 2013 at the TROPOS research station Melpitz. During this field campaign, gas-phase HOM formation was found to be correlated with an increase in the oxidation state of the organic aerosol.
During haze periods in the North China Plain, extremely high NO concentrations have been observed, commonly exceeding 1 ppbv, preventing the classical gas-phase H2O2 formation through HO2 ...recombination. Surprisingly, H2O2 mixing ratios of about 1 ppbv were observed repeatedly in winter 2017. Combined field observations and chamber experiments reveal a photochemical in-particle formation of H2O2, driven by transition metal ions (TMIs) and humic-like substances (HULIS). In chamber experiments, steady-state H2O2 mixing ratios of 116 ± 83 pptv were observed upon the irradiation of TMI- and HULIS-containing particles. Correspondingly, H2O2 formation rates of about 0.2 ppbv h–1 during the initial irradiation periods are consistent with the H2O2 rates observed in the field. A novel chemical mechanism was developed explaining the in-particle H2O2 formation through a sequence of elementary photochemical reactions involving HULIS and TMIs. Dedicated box model studies of measurement periods with relative humidity >50% and PM2.5 ≥ 75 μg m–3 agree with the observed H2O2 concentrations and time courses. The modeling results suggest about 90% of the particulate sulfate to be produced from the SO2 reaction with OH and HSO3 – oxidation by H2O2. Overall, under high pollution, the H2O2-caused sulfate formation rate is above 250 ng m–3 h–1, contributing to the sulfate formation by more than 70%.
Hydroxy hydroperoxides are formed upon OH oxidation of volatile organic compounds in the atmosphere and may contribute to secondary organic aerosol growth and aqueous phase chemistry after phase ...transfer to particles. Although the detection methods for oxidized volatile organic compounds improved much over the past decades, the limited availability of synthetic standards for atmospherically relevant hydroxy hydroperoxides prevented comprehensive investigations for the most part. Here, we present a straightforward improved synthetic access to isoprene-derived hydroxy hydroperoxides, i.e., 1,2-ISOPOOH and 4,3-ISOPOOH. Furthermore, we present the first successful synthesis of an α-pinene derived hydroxy hydroperoxide. All products were identified by 1H, 13C NMR spectroscopy for structure elucidation, additional 2D NMR experiments were performed. Furthermore, gas-phase FTIR- and UV/VIS spectra are presented for the first time. Using the measured absorption cross section, the atmospheric photolysis rate of up to 2.1 × 10−3 s−1 was calculated for 1,2-ISOPOOH. Moreover, we present the investigation of synthesized hydroxy hydroperoxides in an aerosol chamber study by online MS techniques, namely PTR-ToFMS and (NO3−)-CI-APi-ToFMS. Fragmentation patterns recorded during these investigations are presented as well. For the (NO3−)-CI-APi-ToFMS, a calibration factor for 1,2-ISOPOOH was calculated as 4.44 × 10−5 ncps·ppbv−1 and a LOD (3σ, 1 min average) = 0.70 ppbv.
The chemical composition of ambient organic aerosols was analyzed using complementary mass spectrometric techniques during a field study in central Europe in July 2014 (Fichtelgebirge – Biogenic ...Emission and Aerosol Chemistry, F-BEACh 2014). Among several common biogenic secondary organic aerosol (BSOA) marker compounds, 93 acidic oxygenated hydrocarbons were detected with elevated abundances and were thus attributed to be characteristic for the organic aerosol mass at the site. Monoterpene measurements exhibited median mixing ratios of 1.6 and 0.8 ppbV for in and above canopy levels respectively. Nonetheless, concentrations for early-generation oxidation products were rather low, e.g., pinic acid (c = 4.7 (±2.5) ng m−3). In contrast, high concentrations were found for later-generation photooxidation products such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA, c = 13.8 (±9.0) ng m−3) and 3-carboxyheptanedioic acid (c = 10.2 (±6.6) ng m−3), suggesting that aged aerosol masses were present during the campaign period. In agreement, HYSPLIT trajectory calculations indicate that most of the arriving air masses traveled long distances (> 1500 km) over land with high solar radiation. In addition, around 47 % of the detected compounds from filter sample analysis contained sulfur, confirming a rather high anthropogenic impact on biogenic emissions and their oxidation processes. Among the sulfur-containing compounds, several organosulfates, nitrooxy organosulfates, and highly oxidized organosulfates (HOOS) were tentatively identified by high-resolution mass spectrometry. Correlations among HOOS, sulfate, and highly oxidized multifunctional organic compounds (HOMs) support the hypothesis of previous studies that HOOS are formed by reactions of gas-phase HOMs with particulate sulfate. Moreover, periods with high relative humidity indicate that aqueous-phase chemistry might play a major role in HOOS production. However, for dryer periods, coinciding signals for HOOS and gas-phase peroxyradicals (RO2 ) were observed, suggesting RO2 to be involved in HOOS formation.
An improvement is made to a method for the quantification of SOA-bound peroxides. The procedure is based on an iodometric-spectrophotometric method that has been commonly used for the determination ...of peroxides in a wide range of biological and environmental samples. The improved method was applied to determine the peroxide content of laboratory-generated SOA from α-pinene ozonolysis. Besides main improvements for the detection conditions, the use of more environmentally sound solvents is considered instead of carcinogenic solvents. In addition to the improved method for peroxide determination, the present study provides evidence for artefact formation caused by ultrasonic agitation for the extraction of organic compounds in SOA filter samples. The concentration of SOA-bound peroxides in the extracts from ultrasonic agitation were up to three times higher than those from a laboratory orbital shaker under the same extraction conditions, indicating peroxide formation caused by acoustic cavitation during extraction. In contrast, pinic acid, terebic acid and terpenylic acid showed significantly lower concentrations in the sample extract prepared using ultrasonic agitation, indicating that these compounds react with OH radicals that are formed from acoustic cavitation. Great care should be taken when extracting SOA samples and the use of ultrasound should be avoided.
There has been increasing interest in ice nucleation research in the last decade. To identify important gaps in our knowledge of ice nucleation processes and their impacts, two international ...workshops on ice nucleation were held in Vienna, Austria in 2015 and 2016. Experts from these workshops identified the following research needs: (1) uncovering the molecular identity of active sites for ice nucleation; (2) the importance of modeling for the understanding of heterogeneous ice nucleation; (3) identifying and quantifying contributions of biological ice nuclei from natural and managed environments; (4) examining the role of aging in ice nuclei; (5) conducting targeted sampling campaigns in clouds; and (6) designing lab and field experiments to increase our understanding of the role of ice-nucleating particles in the atmosphere. Interdisciplinary teams of scientists should work together to establish and maintain a common, unified language for ice nucleation research. A number of commercial applications benefit from ice nucleation research, including the production of artificial snow, the freezing and preservation of water-containing food products, and the potential modulation of weather. Additional work is needed to increase our understanding of ice nucleation processes and potential impacts on precipitation, water availability, climate change, crop health, and feedback cycles.
Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO
) represents one of the important interactions between anthropogenic emissions related to combustion and natural ...emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO
-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO
-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO
radical, the difficulty of characterizing the spatial distributions of BVOC and NO
within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO
-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO
-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.
The oxidation of biogenic and anthropogenic compounds leads to the formation of secondary organic aerosol mass (SOA). The present study aims to investigate α-pinene, limonene, and m-cresol with ...regards to their SOA formation potential dependent on relative humidity (RH) under night- (NO.sub.3 radicals) and daytime conditions (OH radicals) and the resulting chemical composition. It was found that SOA formation potential of limonene with NO.sub.3 under dry conditions significantly exceeds that of the OH-radical reaction, with SOA yields of 15-30 % and 10-21 %, respectively. Additionally, the nocturnal SOA yield was found to be very sensitive towards RH, yielding more SOA under dry conditions. In contrast, the SOA formation potential of α-pinene with NO.sub.3 slightly exceeds that of the OH-radical reaction, independent from RH. On average, α-pinene yielded SOA with about 6-7 % from NO.sub.3 radicals and 3-4 % from OH-radical reaction. Surprisingly, unexpectedly high SOA yields were found for m-cresol oxidation with OH radicals (3-9 %), with the highest yield under elevated RH (9 %), which is most likely attributable to a higher fraction of 3-methyl-6-nitro-catechol (MNC). While α-pinene and m-cresol SOA was found to be mainly composed of water-soluble compounds, 50-68 % of nocturnal SOA and 22-39 % of daytime limonene SOA are water-insoluble. The fraction of SOA-bound peroxides which originated from α-pinene varied between 2 and 80 % as a function of RH.
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