Skip to main content
NCBI home page
ACS AuthorChoice logoLink to ACS AuthorChoice
. 2026 Jan 6;60(2):2001–2009. doi: 10.1021/acs.est.5c12041

Direct Organosulfate Production from Terpenoid–SO2 Interactions in the Aqueous Phase

Xiangyu Zhang a,b,c, Junting Qiu a,b,c,*, Xinming Wang a,b,c,*
PMCID: PMC12825166  PMID: 41494739

Abstract

Organosulfates (OSs) are key components of atmospheric secondary organic aerosols (SOAs), yet much of their ambient mass remains unexplained. This study demonstrates that dissolved SO2 reacts directly with major biogenic terpenoids (α-pinene, β-pinene, d-limonene, β-caryophyllene, and α-terpineol) in atmospheric condensed phases to form OSs without the need for traditional oxidants. Electrospray ionization mass spectrometry confirms product molecular formulas consistent with field measurements. Kinetic experiments reveal that α-pinene reacts with SO2 at a second-order rate constant of 4.0 ± 0.9 M–1 s–1 in a 50 vol % acetonitrile/water mixture, with the rate increasing nonlinearly as water content rises, reaching 12 ± 1 M–1 s–1 at 70 vol % water. pH-dependent experiments suggest that this reaction of α-pinene can occur at rates of 60–80 M–1 s–1 at pH 3–5, typical of cloud and aerosol water. This pathway could substantially contribute to OS formation and improve multiphase model predictions. Given that dissolved SO2 concentrations (∼10–3 M) far exceed those of OH, O3, or NO3 in aqueous phase, this pathway may rival or even surpass established oxidant-based sinks for terpenoids, contributing substantially to OS formation. Incorporating terpenoid + SO2 aqueous chemistry into multiphase models could thus enhance predictions of aerosol composition, particle acidity, and climate-relevant properties.

Keywords: organosulfate, terpenoid, SO2 , kinetics, atmospheric aerosol

graphic file with name es5c12041_0008.jpg

graphic file with name es5c12041_0006.jpg

Introduction

Organosulfates (OSs) account for up to 30% of fine-particle organic mass, , and have been detected in rural, urban, marine, forested, and polar environments. − They can lower aerosol surface tension, , enhance hygroscopic growth, , and modulate aerosol acidity, viscosity, and optical properties, ,− with implications for cloud activation and radiative forcing. Deciphering the sources and formation pathways of OSs is therefore critical for constraining secondary organic aerosol (SOA) budgets and evaluating aerosol-climate feedbacks.

Currently, a variety of formation routes of OSs in the atmosphere has been proposed, − among these, terpenoid-derived OSs represent an important fraction of OSs in atmospheric particulate matter. Isoprene-derived OSs are primarily formed through particle-phase reactions of bisulfate anions with isoprene epoxides. − Moreover, ISOPOOH, an organic peroxide derived from isoprene, has also been identified as a key intermediate contributing to OSs formation. , In the case of monoterpenes, it is generally considered that their oxidation products can further react with dissolved SO2 in the particle phase to generate OSs, with functional groups such as hydroperoxides (ROOH) and peroxides (ROOR) playing crucial roles in the reaction pathways. − However, ambient data sets still show that more than half of OSs mass cannot be explained by such pathways. ,−

The aforementioned “indirect” routes for terpenoid-derived OSs formation require prior oxidation of terpenoids. In addition, emerging evidence points to a complementary “direct” route in which the interaction of SO2 with unsaturated species in the presence of O2 leads to OS formation. For instance, Shang et al. and Passananti et al. demonstrated that gas-phase SO2 adds to isolated C = C bonds in oleic acid and long-chain alkenes, producing organosulfur compounds without OH, O3, or NO3. Identical molecular formulas were detected in PM2.5 samples collected in Guangzhou, China, where unsaturated fatty acids are extensively emitted into local atmosphere, suggesting that this “direct” OS formation mechanism is active under ambient conditions. In parallel, field observations have provided compelling evidence for the direct uptake of terpenoids within forest canopies and over grassland, − where extensive aqueous surface areas are present, suggesting that terpenoids can be effectively absorbed onto aqueous interfaces. Additionally, Brüggemann et al. reported higher abundances of monoterpene-derived OSs under conditions of elevated relative humidity, highlighting the significance of aqueous-phase chemistry in OSs formation. Together these observations raise the hypothesis that dissolved SO2 may react directly with unoxidized terpenoids in cloud, fog, or aerosol water to generate OSs in situ.

Quantitative tests of this hypothesis are lacking. Key unknowns include reaction rate coefficients, pH dependencies, product identities, and the relative importance of this pathway compared with canonical “indirect” route for terpenoid-derived OS formation. Addressing these gaps, we systematically investigate the liquid-phase reaction chemistry of five representative terpenoids, α-pinene (α-P), β-pinene (β-P), d-limonene (d-L), β-caryophyllene (β-C) and α-terpineol (α-Tp), with dissolved SO2 under atmospherically relevant conditions. Using electrospray-ionization mass spectrometry coupled to isotope-labeling and time-resolved kinetics, we (i) identify organosulfate products that match ambient signatures, (ii) report second-order rate constants for terpenoids reacting with SO2 as a function of water content and acidity, and (iii) assess the potential of terpenoids + SO2 reactions to compete with OH, O3, and NO3 oxidation in atmospheric condensed phases. Our results reveal a heretofore unrecognized, efficient source of biogenic organosulfates and highlight the need to embed this chemistry in multiphase models of SOA evolution.

Experimental Section

Sodium metabisulfite (NaS2O5) was weighed (Sartorius Quintix224–1CN) and dissolved in ultrapure water to prepare 1 mM HSO3 – stock solution, which was then diluted to the desired concentrations for experiments. The selection of sodium metabisulfite was based on its higher purity in commercial preparations compared to sodium bisulfite, minimizing interference from impurities. Dissolved SO2 was generated via the aqueous equilibrium of HSO3 –. The HSO3 – solution was freshly prepared and used within 1 day to minimize oxidation. α-P, β-P, d-L (C10H16, MW 136), and β-C (C15H24, MW 204) were dissolved in 20 mL of water/acetonitrile (W/AN) mixtures in 30 mL glass vials to examine their reaction products, addressing their low water solubility. Reactions were initiated by mixing terpenes and HSO3 – solutions in a 5 mL glass syringe covered with aluminum foil to prevent photodegradation. After adding the HSO3 – solution (5 μM), the mixtures were immediately injected into an electrospray ionization mass spectrometer (ESI-MS, Agilent G6160A) at a flow rate of 100 μL min–1 using a syringe pump (Longer LSP01–3A) (Figure S1). The moment when the HSO3 – solution was added was considered as the start time of the reactions, and the evolution of HSO3 – as well as other species was followed by ESI-MS as a function of time, recorded with a digital stopwatch. S0 therefore corresponds to the signal recorded at that timestamp. Mass spectra of the reactants and products were recorded and analyzed. Sulfite exhibits a signal at m/z 81 in ESI-MS, enabling time-dependent monitoring of reaction progression.

D2O and H2 18O were used instead of water respectively in isotope labeling experiments to explore detailed characterization of major products in α-P + SO2 reaction. This method was proven to be beneficial for examining the chemical structure of unidentified species in previous studies. − D2O was used to probe exchangeable H atoms, whereas H2 18O helped identify O-containing functional groups, such as carbonyls. Both O atoms in dissolved SO2 can exchange with 18O from H2 18O, as shown in Scheme S1, providing further insight into the origin of the O atoms in the reaction products.

A serious of experiments were performed with the pseudo-first-order method (with an excess of terpenoids, at least a factor of 10) to determine the rate coefficients k for the reaction of terpenoids with SO2. The pseudo-first-order rate coefficient k′ can be obtained from the fitted curve of the single-exponential decay, S = S0 exp­(−k′ t), plotted as a function of time (t). The concentrations of terpenoids were varied from 0.3 to 2 mM, and k was then extracted from the slope of the regression line of k′ versus [terpenoid]. To explore the effect of water contents on kinetic measurements, we first investigated the kinetics of the reaction between α-P + SO2 in a 1:1 (v/v) W/AN solution, and subsequently varied the water content to 10%, 30%, and 70% by volume, with the aim of estimating the rate constant for α-P + SO2 in atmospheric condensed phases. To simulate typical pH conditions of atmospheric liquid-phase, α-Tp (C10H16OH, MW 154) was dissolved in neat water due to its relatively higher solubility. The pH of α-Tp solutions was adjusted using hydrogen chloride (HCl) and sodium hydroxide (NaOH) to a range of 4–7, and measured with a calibrated pH meter (Hanna HI200) before each experiment. All the experiments were repeated at least three times.

The mass spectrometer was operated under the following conditions: drying gas (N2) flow rate of 12 L min–1, drying gas temperature of 340 °C, inlet voltage of +3.5 kV relative to ground, and fragmentor voltage of 60 V. Chemicals used were α-pinene (>98%, Sigma-Aldrich), β-pinene (>97%, Sigma-Aldrich), d-limonene (>95%, Sigma-Aldrich), β-caryophyllene (>90%, Tokyo Chemical Industry), α-terpineol (>95%, Tokyo Chemical Industry), sodium metabisulfite (≤100%, Supelco), D2O (>99.9 atom % D, Sigma-Aldrich), H2 18O (≥97%, Cambridge Isotope Laboratories), sodium hydroxide (0.1 N, Anpel), hydrogen chloride (37%, ACS reagent, Sigma-Aldrich), acetonitrile (≥99.9%, Aladdin), and ultrapure water (Meryer), all used as received.

Results and Discussion

Products from α-P and Other Terpenoids Reacting with Dissolved SO2

Figure A presents the mass spectrometric results for 1 mM α-P dissolved AN/W (vol/vol = 1:1) mixture, both in the absence and presence of 5 μM HSO3 –. Upon the addition of HSO3 –, a prominent signal emerged at m/z 81, corresponding to the bisulfite ion. While HSO3 – typically acts as a nucleophile, it has limited reactivity toward the double bond of α-P. In contrast, SO2 is known to interact with double bonds via [2 + 2] cycloaddition or π-complex formation, as reported in previous studies. , These interactions indicate that α-P and SO2 can directly react. As SO2 is consumed, the m/z 81 signal gradually decreases, reflecting a shift in chemical equilibrium (Figure A).

1.

1

Open in a new tab

Results from the reaction of α-P with SO2 in AN/W (vol/vol = 1/1). (A) mass spectra record in the absence of HSO3 –, as well as 5 min, 10 min, 15 min after the addition of HSO3 –; (B) mass spectra for m/z 225–300, showing the major products from the reaction of α-P with SO2 in the presence of O2.

Figure B displays the mass spectra in the m/z 225–300 range, revealing major product ions at m/z 231 (P1) and m/z 265 (P2), with additional signals at m/z 247, 249, and 263. The intensity of these product ions increased as HSO3 – signal decreased, indicating that their formation is linked to SO2 reactions. According to Passananti et al., SO2 can initiate radical chain reactions with unsaturated compounds in the presence of O2, generating sulfur-containing products.

To further assess the generality of this reactivity, α-P was replaced with other terpenoids, including β-pinene (β-P), d-limonene (d-L), β-caryophyllene (β-C), and α-terpinene (α-Tp). Figures S2–S5 demonstrate that these terpenoids also react with SO2 to form a series of sulfur-containing products in the presence of O2 and H2O. Additional experiments confirmed the role of dissolved O2. When O2 was removed by purging the solution with N2, product formation was significantly suppressed (Figure S6).

To our knowledge, this is the first report demonstrating the formation of sulfur-containing compounds from the direct reaction of terpenoids with SO2 under such conditions. We next conducted isotope labeling experiments to explore the chemical structures of the major products.

Chemical Identification of Major Products

The most important products from the α-P + SO2 reaction are P1 (m/z 231) and P2 (m/z 265). We performed isotope labeling experiments using D2O and H2 18O to identify chemical structures. In these experiments, α-P was dissolved in either AN/D2O or AN/H2 18O, and HSO3 – solution was prepared by dissolving sodium metabisulfite in D2O or H2 18O. Figure S7 shows that the HSO3 – ion exhibited a + 1 m/z shift in D2O and a + 6 m/z shift in H2 18O, confirming the proposed oxygen-exchange mechanism in Scheme S1.

P1 is considered to be generated from the reaction of α-P with SO2 in the presence of O2, with a theoretical composition of m/z 231 = 136 (α-P) + 64 (SO2) + 32 (2O) – 1 (H+). As shown in Figure A, P1 exhibited no mass shift in the AN/D2O experiment, and a + 4 m/z shift was observed in AN/H2 18O experiment, indicating that P1 does not contain exchangeable H atoms, and that two 18O atoms from S18O2 were incorporated the exchange mechanism described in Scheme S1. This confirms that P1 originates from the direct reaction of α-P with SO2, rather than with HSO3 –, as the three 18O atoms in HSO3 – would all be exchangeable (Figure S7).

2.

2

Open in a new tab

Mass spectra of (A) m/z 231 and (B) m/z 265 obtained in AN/H2O, AN/D2O and AN/H2 18O solutions. The volume ratio for all the experiments is 1:1.

In contrast, Figure B shows that P2 (m/z 265) underwent a + 1 m/z shift in the AN/D2O experiment, indicating the presence of one exchangeable H atom; and a + 6 m/z shift in AN/H2 18O experiment, suggesting that three 16O atoms in P2 were replaced by 18O. Given that O2 cannot contribute 18O, two of the oxygen atoms likely originate from SO2, with the third from H2 18O. This implies two potential structural features for P2: (1) P2 contains a carbonyl group formed via hydration by H2 18O (e.g., C = 16O → C = 18O), along with another O-containing functional group bearing an exchangeable hydrogen (e.g., – OH or – OOH); or (2) P2 involves the direct incorporation of H2O. Based on the radical chain mechanism for SO2 reactions with unsaturated organics in the presence of O2, as reported by Passananti et al., the first one was deemed unlikely, and we propose that P2 forms through the direct incorporation of H2O. A suggested formation route for P1 and P2, as illustrated in Scheme , is initiated via [2 + 2] cycloaddition or π-interaction of SO2 to C = C bond of α-P, as proposed by Passananti et al., leading to the formation of a biradical compound. O2 and H2O are involved in the subsequent reaction steps, where P1, P2 and other organosulfur compounds generated, including the species appeared at m/z 247, 249, and 263.

1. Suggested Formation Route for m/z 231 and m/z 265.

1

Open in a new tab

Compounds with molecular weights matching P1 and P2 have been reported in previous field studies, ,,− suggesting that the reaction of terpenoids with SO2 in the presence of O2 is an important atmospheric source of OSs. While terpenoid-derived OSs are generally believed to form through the reaction of oxidized terpenoid products with sulfur-containing species, we show that less-oxidized OSs, such as P1 (C10H16O4S), can form directly from the reaction of α-P with SO2.

Kinetics Measurement

Due to the low water solubility of α-P, kinetic measurements were initially performed in in a mixed AN/W (vol/vol = 1:1) solution, and the water content was varied to examine its influence on the reaction rate. The concentration of α-P ranged from 0.3 to 2 mM, while the HSO3 – concentration was fixed at 5 μM, which is at least 60-fold lower than that of α-P, allowing the reaction to be treated under pseudo-first-order conditions. The pseudo-first-order rate constants (k α‑P′ = k α‑P[α-P]) were derived from the decay curves of HSO3 – (Figure A). The second-order rate constant k α‑P for α-P + SO2 reaction was calculated from the linear fit of k α‑P′ versus [α-P], yielding a value of 4.0 ± 0.9 M–1 s–1 (Figure B).

3.

3

Open in a new tab

Kinetics measurement for α-P reacting with SO2. (A) Decay curve fitted from the temporal signals of HSO3 – recorded at different concentrations of α-P. The curve lines for m/z 81 correspond to single-exponential decay S = S0 exp­(−k′ t), which represents the decay of the HSO3 – signal; (B) Second order rate coefficient k α‑P for α-P + SO2 calculated from linear fit of k α‑P′; (C) k α‑P for α-P + SO2 in AN/W mixed solutions as a function of water vol %. Error bars are derived from at least 3 replicate experiments.

The rate coefficients (k α‑P) for the α-P + SO2 reaction were measured to be 0.24 ± 0.02, 0.39 ± 0.02, and 12 ± 1 M–1 s–1 in solutions containing 10%, 30%, and 70% water by volume, respectively (Figure C). The rate coefficient increased nonlinearly with water content, likely due to the formation of microheterogeneous domains in AN/W mixtures, rather than a uniform molecular environment. Similar nonlinear kinetics have been observed in other solvent mixtures. ,

Microheterogeneity is common in water-organic solvent mixtures. − Nagasaka et al. provided direct spectroscopic evidence for the existence of distinct “AN-rich” and “W-rich” domains in AN/W mixtures using soft X-ray absorption spectroscopy combined with ab initio inner-shell calculations. At low water contents (mole fraction of water <0.25), water molecules are isolated within AN chains via dipole–dipole interactions, creating distinct “AN” and “W” phases. Since salts like HSO3 – are only ionized in the “W phase”, SO2 also forms in “W phase”. α-P, which preferentially partitions into the AN phase, has limited contact with SO2, slowing the reaction. As the water content increases, the AN chains become encapsulated within water, forming dynamic ANmWn domains that facilitate greater interactions between α-P and SO2, which enhances the reaction rate.

Rate coefficients for other terpenoids, including β-P, d-L, β-C, were also measured and the results are summarized in Table . Due to their low water solubility, we could not perform kinetic measurements for these compounds in pure water like α-P. However, the high solubility of α-Tp in water allowed us to investigate the pH dependence of the reaction rate. The pH of the α-Tp solution (pH ≈ 6.1 for 1 mM) was adjusted between 4 and 7 using HCl and NaOH. The second-order rate constants for α-Tp with SO2 (k Tp) were determined over this pH range, as presented in Table . Figure shows that k Tp increased 3-fold when pH drops from 7 to 4.

1. Rate Coefficients for Terpenoids Reacting with SO2 in Liquid Phase.

Terpenoids pH water (vol %) k (M–1 s –1)
α-Pinene \ 10 0.24 ± 0.02
\ 30 0.39 ± 0.02
\ 50 4.0 ± 0.9
\ 70 12 ± 1
β-Pinene \ 50 0.55 ± 0.08
d-Limonene \ 50 0.70 ± 0.10
β-Caryophyllene \ 50 0.91 ± 0.04
α-Terpineol 4.2 100 0.93 ± 0.09
4.7 100 0.75 ± 0.06
5.1 100 0.65 ± 0.05
5.7 100 0.47 ± 0.02
6.2 100 0.38 ± 0.04
6.6 100 0.33 ± 0.03
6.9 100 0.30 ± 0.10
Open in a new tab

4.

4

Open in a new tab

Second order rate coefficient k Tp for α-Tp + SO2 in water, as a function of pH. Error bars are derived from at least 3 replicate experiments.

In the atmosphere, once α-P is partitioned into the aqueous phase, the reaction with SO2 is expected to occur under more homogeneous conditions than in AN/W mixtures, likely proceeding at even faster rates than observed in our experiments. Extrapolating the trend in Figure C suggests that the rate constant for α-P + SO2 in pure water could exceed 20 M–1 s–1. A pronounced pH dependence for the reaction of SO2 with unsaturated compounds was observed in the α-Tp experiments. Although the pH dependence of the reactivity of α-P and other terpenoids toward SO2 may differ due to structural variability, we hypothesize that the trend identified for α-Tp is broadly representative of other terpenoids, including α-P, given the experimental challenges associated with directly determining the pH dependence of the α-P + SO2 reaction in pure water. By analogy, the rate constant for α-P + SO2 is expected to fall within 60–80 M–1 s–1 under acidic conditions (pH 3–5) typical of atmospheric aerosols and cloudwater. , This rate is notably faster than other reactions known to produce OSs, highlighting the significance of this aqueous-phase pathway for OS formation under ambient conditions.

Atmospheric Implications

Biogenic volatile organic compounds (BVOCs) are emitted into the atmosphere at ∼1015 g yr–1 globally, with terpenoids contributing over 90% of this total. , Canopy-scale fluxes and laboratory studies demonstrated efficient uptake of terpenoids to wet or acidic surfaces, − where protonation significantly enhances partitioning into the aqueous phase. − Partitioning of SO2 into aerosols and hydrometeors further acidifies the condensed phase, reinforcing this uptake via positive feedback.

Although SO2 reacts rapidly with oxidants like H2O2, O3, and NO2, these reactions primarily produce inorganic sulfate species, not organosulfates. Our study demonstrates a previously unrecognized pathway where SO2 directly reacts with biogenic terpenoids to form OSs. Multiple pathways can transform monoterpenes into OSs, including multiphase, aqueous phase, and heterogeneous reactions with anthropogenic gas-phase SO2 or sulfate seeds. , Field observations consistently show that high nighttime relative humidity favors formation of terpenoid-derived OSs, supporting a significant role for aqueous-phase chemistry. − Proposed mechanisms include the conversion of nitrooxy-organosulfates (NOSs) to OSs and sulfate radical reactions. ,− However, recent forest observational data indicated that CHOS (OS) and CHOSN (NOS) mass fractions do not always covary humidity, implying additional unknown OS sources and, most notably, direct reactions between SO2 and the unsaturated BVOC in the condensed phase.

A simple reactivity comparison highlights the potential importance of this direct route under acidic, water-rich conditions. The rate coefficients for α-P reacting with O3 and NO3 radical in the aqueous phase are estimated to be 6.0 × 104 and 3.9 × 109 M–1 s–1, respectively, derived from the corresponding gas-phase rate constant (k gas(α-P + O3) = 1.0 × 10–16, and k gas(α-P + NO3·) = 6.5 × 10–12 cm3 molecule–1 s–1). Although the α-P + SO2 reaction is significantly slower than those with these oxidants in terms of rate constants, it is offset by the much higher concentration of SO2 (up to 10–3 M) in atmospheric condensed phase, compared to O3 (∼10–9 M) and NO3 radicals (10–16–10–13 M). − Thus, in acidic cloud/fogwater and wet particles, monoterpene + SO2 reaction can rival or exceed oxidant-based sinks despite its lower bimolecular rate constant. Coupled with elevated nighttime monoterpene levels and enhanced solubility in aqueous particles and clouds, this pathway may represent a major sink for terpenes and a consequential source of monoterpene-derived OSs.

These findings motivate inclusion of a pH- and water-dependent SO2 + terpenoids aqueous reaction in multiphase models, alongside NOS formation and sulfate-radical chemistry. Doing so will improve closure on OS budgets, refine predictions of inorganic-to-organosulfur conversion and particle acidity, and better capture impacts on hygroscopicity, CCN activity, and radiative properties in mixed anthropogenic-biogenic environments.

Supplementary Material

es5c12041_si_001.pdf (557.8KB, pdf)

Acknowledgments

This work is financially supported by National Natural Science Foundation (42321003, 42477112, and 42107118) and the Department of Science and Technology of Guangdong (2023B0303000007 and 2023B1212060049).

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.5c12041.

  • Additional experimental data, including the schematic setup and procedure, mass spectra, temporal profile, and mechanism schemes (PDF)

The authors declare no competing financial interest.

References

  1. Surratt J. D., Gómez-González Y., Chan A. W. H., Vermeylen R., Shahgholi M., Kleindienst T. E., Edney E. O., Offenberg J. H., Lewandowski M., Jaoui M., Maenhaut W., Claeys M., Flagan R. C., Seinfeld J. H.. Organosulfate formation in biogenic secondary organic aerosol. J. Phys. Chem. A. 2008;112(36):8345–8378. doi: 10.1021/jp802310p. [DOI] [PubMed] [Google Scholar]
  2. Tolocka M. P., Turpin B.. Contribution of organosulfur compounds to organic aerosol mass. Environ. Sci. Technol. 2012;46(15):7978–7983. doi: 10.1021/es300651v. [DOI] [PubMed] [Google Scholar]
  3. Frossard A. A., Shaw P. M., Russell L. M., Kroll J. H., Canagaratna M. R., Worsnop D. R., Quinn P. K., Bates T. S.. Springtime Arctic haze contributions of submicron organic particles from European and Asian combustion sources. J. Geophys. Res. Atmos. 2011;116:D05205. doi: 10.1029/2010JD015178. [DOI] [Google Scholar]
  4. Hansen A. M. K., Kristensen K., Nguyen Q. T., Zare A., Cozzi F., Nojgaard J. K., Skov H., Brandt J., Christensen J. H., Ström J., Tunved P., Krejci R., Glasius M.. Organosulfates and organic acids in Arctic aerosols: speciation, annual variation and concentration levels. Atmos. Chem. Phys. 2014;14(15):7807–7823. doi: 10.5194/acp-14-7807-2014. [DOI] [Google Scholar]
  5. Iinuma Y., Müller C., Berndt T., Böge O., Claeys M., Herrmann H.. Evidence for the existence of organosulfates from β-pinene ozonolysis in ambient secondary organic aerosol. Environ. Sci. Technol. 2007;41(19):6678–6683. doi: 10.1021/es070938t. [DOI] [PubMed] [Google Scholar]
  6. Kristensen K., Glasius M.. Organosulfates and oxidation products from biogenic hydrocarbons in fine aerosols from a forest in North West Europe during spring. Atmos. Environ. 2011;45(27):4546–4556. doi: 10.1016/j.atmosenv.2011.05.063. [DOI] [Google Scholar]
  7. Maria S. F., Russell L. M., Turpin B. J., Porcja R. J., Campos T. L., Weber R. J., Huebert B. J.. Source signatures of carbon monoxide and organic functional groups in Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) submicron aerosol types. J. Geophys. Res. Atmos. 2003;108(D23):8637. doi: 10.1029/2003JD003703. [DOI] [Google Scholar]
  8. Mazzoleni L. R., Saranjampour P., Dalbec M. M., Samburova V., Hallar A. G., Zielinska B., Lowenthal D. H., Kohl S.. Identification of water-soluble organic carbon in non-urban aerosols using ultrahigh-resolution FT-ICR mass spectrometry: organic anions. Environ. Chem. 2012;9(3):285–297. doi: 10.1071/EN11167. [DOI] [Google Scholar]
  9. Nguyen Q. T., Christensen M. K., Cozzi F., Zare A., Hansen A. M. K., Kristensen K., Tulinius T. E., Madsen H. H., Christensen J. H., Brandt J., Massling A., Nojgaard J. K., Glasius M.. Understanding the anthropogenic influence on formation of biogenic secondary organic aerosols in Denmark via analysis of organosulfates and related oxidation products. Atmos. Chem. Phys. 2014;14(17):8961–8981. doi: 10.5194/acp-14-8961-2014. [DOI] [Google Scholar]
  10. Stone E. A., Yang L. M., Yu L. Y. E., Rupakheti M.. Characterization of organosulfates in atmospheric aerosols at Four Asian locations. Atmos. Environ. 2012;47:323–329. doi: 10.1016/j.atmosenv.2011.10.058. [DOI] [Google Scholar]
  11. Surratt J. D., Kroll J. H., Kleindienst T. E., Edney E. O., Claeys M., Sorooshian A., Ng N. L., Offenberg J. H., Lewandowski M., Jaoui M., Flagan R. C., Seinfeld J. H.. Evidence for organosulfates in secondary organic aerosol. Environ. Sci. Technol. 2007;41(2):517–527. doi: 10.1021/es062081q. [DOI] [PubMed] [Google Scholar]
  12. Huang L. B., Wang Y., Zhao Y., Hu H. L., Yang Y., Wang Y. C., Yu J. Z., Chen T. S., Cheng Z., Li C. X., Li Z. Y., Xiao H. Y.. Biogenic and anthropogenic contributions to atmospheric organosulfates in a typical megacity in Eastern China. J. Geophys. Res. Atmos. 2023;128(17):e2023JD038848. doi: 10.1029/2023JD038848. [DOI] [Google Scholar]
  13. Nozière B., Ekström S., Alsberg T., Holmström S.. Radical-initiated formation of organosulfates and surfactants in atmospheric aerosols. Geophys. Res. Lett. 2010;37:L05806. doi: 10.1029/2009GL041683. [DOI] [Google Scholar]
  14. Riva M., Chen Y. Z., Zhang Y., Lei Z. Y., Olson N. E., Boyer H. C., Narayan S., Yee L. D., Green H. S., Cui T. Q., Zhang Z. F., Baumann K., Fort M., Edgerton E., Budisulistiorini S. H., Rose C. A., Ribeiro I. O., Oliveira R. L. E., dos Santos E. O., Machado C. M. D., Szopa S., Zhao Y., Alves E. G., de Sá S. S., Hu W. W., Knipping E. M., Shaw S. L., Duvoisin S., de Souza R. A. F., Palm B. B., Jimenez J. L., Glasius M., Goldstein A. H., Pye H. O. T., Gold A., Turpin B. J., Vizuete W., Martin S. T., Thornton J. A., Dutcher C. S., Ault A. P., Surratt J. D.. Increasing isoprene epoxydiol-to-inorganic sulfate aerosol ratio results in extensive conversion of inorganic sulfate to organosulfur forms: implications for aerosol physicochemical properties. Environ. Sci. Technol. 2019;53(15):8682–8694. doi: 10.1021/acs.est.9b01019. [DOI] [PMC free article] [PubMed] [Google Scholar]
  15. Estillore A. D., Hettiyadura A. P. S., Qin Z., Leckrone E., Wombacher B., Humphry T., Stone E. A., Grassian V. H.. Water uptake and hygroscopic growth of organosulfate aerosol. Environ. Sci. Technol. 2016;50(8):4259–4268. doi: 10.1021/acs.est.5b05014. [DOI] [PubMed] [Google Scholar]
  16. Hansen A. M. K., Hong J., Raatikainen T., Kristensen K., Ylisirniö A., Virtanen A., Petäjä T., Glasius M., Prisle N. L.. Hygroscopic properties and cloud condensation nuclei activation of limonene-derived organosulfates and their mixtures with ammonium sulfate. Atmos. Chem. Phys. 2015;15(24):14071–14089. doi: 10.5194/acp-15-14071-2015. [DOI] [Google Scholar]
  17. Fleming L. T., Ali N. N., Blair S. L., Royeretto M., George C., Nizkorodov S. A.. Formation of light-absorbing organosulfates during evaporation of secondary organic material extracts in the presence of sulfuric acid. ACS Earth Space Chem. 2019;3(6):947–957. doi: 10.1021/acsearthspacechem.9b00036. [DOI] [Google Scholar]
  18. Zhang Y., Chen Y., Lei Z., Olson N. E., Riva M., Koss A. R., Zhang Z., Gold A., Jayne J. T., Worsnop D. R., Onasch T. B., Kroll J. H., Turpin B. J., Ault A. P., Surratt J. D.. Joint impacts of acidity and viscosity on the formation of secondary organic aerosol from isoprene epoxydiols (IEPOX) in phase separated particles. ACS Earth Space Chem. 2019;3(12):2646–2658. doi: 10.1021/acsearthspacechem.9b00209. [DOI] [Google Scholar]
  19. Brüggemann M., Xu R., Tilgner A., Kwong K. C., Mutzel A., Poon H. Y., Otto T., Schaefer T., Poulain L., Chan M. N., Herrmann H.. Organosulfates in ambient aerosol: state of knowledge and future research directions on formation, abundance, fate, and importance. Environ. Sci. Technol. 2020;54(7):3767–3782. doi: 10.1021/acs.est.9b0675. [DOI] [PubMed] [Google Scholar]
  20. Deng H., Lakey P. S. J., Wang Y., Li P., Xu J., Pang H., Liu J., Xu X., Li X., Wang X., Zhang Y., Shiraiwa M., Gligorovski S.. Daytime SO2 chemistry on ubiquitous urban surfaces as a source of organic sulfur compounds in ambient air. Sci. Adv. 2022;8(39):eabq6830. doi: 10.1126/sciadv.abq6830. [DOI] [PMC free article] [PubMed] [Google Scholar]
  21. Jiang H., He Y., Wang Y., Li S., Jiang B., Carena L., Li X., Yang L., Luan T., Vione D., Gligorovski S.. Formation of organic sulfur compounds through SO2-initiated photochemistry of PAHs and dimethylsulfoxide at the air-water interface. Atmos. Chem. Phys. 2022;22(6):4237–4252. doi: 10.5194/acp-22-4237-2022. [DOI] [Google Scholar]
  22. Eddingsaas N. C., VanderVelde D. G., Wennberg P. O.. Kinetics and products of the acid-catalyzed ring-opening of atmospherically relevant butyl epoxy alcohols. J. Phys. Chem. A. 2010;114(31):8106–8113. doi: 10.1021/jp103907c. [DOI] [PubMed] [Google Scholar]
  23. Minerath E. C., Elrod M. J.. Assessing the potential for diol and hydroxy sulfate ester formation from the reaction of epoxides in tropospheric aerosols. Environ. Sci. Technol. 2009;43(5):1386–1392. doi: 10.1021/es8029076. [DOI] [PubMed] [Google Scholar]
  24. Piletic I. R., Edney E. O., Bartolotti L. J.. A computational study of acid catalyzed aerosol reactions of atmospherically relevant epoxides. Phys. Chem. Chem. Phys. 2013;15(41):18065–18076. doi: 10.1039/c3cp52851k. [DOI] [PubMed] [Google Scholar]
  25. Dovrou E., Bates K. H., Rivera-Rios J. C., Cox J. L., Shutter J. D., Keutsch F. N.. Towards a chemical mechanism of the oxidation of aqueous sulfur dioxide via isoprene hydroxyl hydroperoxides (ISOPOOH) Atmos. Chem. Phys. 2021;21(11):8999–9008. doi: 10.5194/acp-21-8999-2021. [DOI] [Google Scholar]
  26. Dovrou E., Rivera-Rios J. C., Bates K. H., Keutsch F. N.. Sulfate formation via cloud processing from isoprene hydroxyl hydroperoxides (ISOPOOH) Environ. Sci. Technol. 2019;53(21):12476–12484. doi: 10.1021/acs.est.9b04645. [DOI] [PubMed] [Google Scholar]
  27. Ehn M., Thornton J. A., Kleist E., Sipila M., Junninen H., Pullinen I., Springer M., Rubach F., Tillmann R., Lee B., Lopez-Hilfiker F., Andres S., Acir I. H., Rissanen M., Jokinen T., Schobesberger S., Kangasluoma J., Kontkanen J., Nieminen T., Kurten T., Nielsen L. B., Jorgensen S., Kjaergaard H. G., Canagaratna M., Dal Maso M., Berndt T., Petaja T., Wahner A., Kerminen V. M., Kulmala M., Worsnop D. R., Wildt J., Mentel T. F.. A large source of low-volatility secondary organic aerosol. Nature. 2014;506(7489):476. doi: 10.1038/nature13032. [DOI] [PubMed] [Google Scholar]
  28. Wang S., Liu T., Jang J., Abbatt J. P. D., Chan A. W. H.. Heterogeneous interactions between SO2 and organic peroxides in submicron aerosol. Atmos. Chem. Phys. 2021;21(9):6647–6661. doi: 10.5194/acp-21-6647-2021. [DOI] [Google Scholar]
  29. Wang S., Zhou S., Tao Y., Tsui W. G., Ye J., Yu J. Z., Murphy J. G., McNeill V. F., Abbatt J. P. D., Chan A. W. H.. Organic peroxides and sulfur dioxide in aerosol: source of particulate sulfate. Environ. Sci. Technol. 2019;53(18):10695–10704. doi: 10.1021/acs.est.9b02591. [DOI] [PubMed] [Google Scholar]
  30. Yao M., Zhao Y., Chang C. X., Wang S. Y., Li Z. Y., Li C. X., Chan A. W. H., Xiao H. Y.. Multiphase reactions between organic peroxides and sulfur dioxide in internally mixed inorganic and organic particles: key roles of particle phase separation and acidity. Environ. Sci. Technol. 2023;57(41):15558–15570. doi: 10.1021/acs.est.3c04975. [DOI] [PubMed] [Google Scholar]
  31. Yao M., Zhao Y., Hu M., Huang D., Wang Y., Yu J. Z., Yan N.. Multiphase reactions between secondary organic aerosol and sulfur dioxide: kinetics and contributions to sulfate formation and aerosol aging. Environ. Sci. Technol. Lett. 2019;6(12):768–774. doi: 10.1021/acs.estlett.9b00657. [DOI] [Google Scholar]
  32. Ye J. H., Abbatt J. P. D., Chan A. W. H.. Novel pathway of SO2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol. Atmos. Chem. Phys. 2018;18(8):5549–5565. doi: 10.5194/acp-18-5549-2018. [DOI] [Google Scholar]
  33. Xu L., Tsona N. T., Du L.. Relative humidity changes the role of SO2 in biogenic secondary organic aerosol formation. J. Phys. Chem. Lett. 2021;12(30):7365–7372. doi: 10.1021/acs.jpclett.1c01550. [DOI] [PubMed] [Google Scholar]
  34. Le Breton M., Wang Y., Hallquist A. M., Pathak R. K., Zheng J., Yang Y., Shang D., Glasius M., Bannan T. J., Liu Q., Chan C. K., Percival C. J., Zhu W., Lou S., Topping D., Wang Y., Yu J., Lu K., Guo S., Hu M., Hallquist M.. Online gas- and particle-phase measurements of organosulfates, organosulfonates and nitrooxy organosulfates in Beijing utilizing a FIGAERO ToF-CIMS. Atmos. Chem. Phys. 2018;18(14):10355–10371. doi: 10.5194/acp-18-10355-2018. [DOI] [Google Scholar]
  35. Chen Y., Dombek T., Hand J., Zhang Z., Gold A., Ault A. P., Levine K. E., Surratt J. D.. Seasonal contribution of isoprene-derived organosulfates to total water-soluble fine particulate organic sulfur in the United States. Acs Earth Space Chem. 2021;5(9):2419–2432. doi: 10.1021/acsearthspacechem.1c00102. [DOI] [Google Scholar]
  36. Ye Y., Zhan H., Yu X., Li J., Wang X., Xie Z.. Detection of organosulfates and nitrooxy-organosulfates in Arctic and Antarctic atmospheric aerosols, using ultra-high resolution FT-ICR mass spectrometry. Sci. Total Environ. 2021;767:144339. doi: 10.1016/j.scitotenv.2020.144339. [DOI] [PubMed] [Google Scholar]
  37. Glasius M., Thomsen D., Wang K., Iversen L. S., Duan J., Huang R.-J.. Chemical characteristics and sources of organosulfates, organosulfonates, and carboxylic acids in aerosols in urban Xi’an, Northwest China. Sci. Total Environ. 2022;810:151187. doi: 10.1016/j.scitotenv.2021.151187. [DOI] [PubMed] [Google Scholar]
  38. Shang J., Passananti M., Dupart Y., Ciuraru R., Tinel L., Rossignol S., Perrie S., Zhu T., George C.. SO2 uptake on oleic acid: a new formation pathway of organosulfur compounds in the atmosphere. Environ. Sci. Technol. Lett. 2016;3(2):67–72. doi: 10.1021/acs.estlett.6b00006. [DOI] [Google Scholar]
  39. Passananti M., Kong L. D., Shang J., Dupart Y., Perrier S., Chen J. M., Donaldson D. J., George C.. Organosulfate formation through the heterogeneous reaction of sulfur dioxide with unsaturated fatty acids and long-chain alkenes. Angew. Chem., Int. Ed. 2016;55(35):10336–10339. doi: 10.1002/anie.201605266. [DOI] [PubMed] [Google Scholar]
  40. Zhu M., Jiang B., Li S., Yu Q. Q., Yu X., Zhang Y. L., Bi X. H., Yu J. Z., George C., Yu Z. Q., Wang X. M.. Organosulfur compounds formed from heterogeneous reaction between SO2 and particulate-bound unsaturated fatty acids in ambient ai. Environ. Sci. Technol. Lett. 2019;6(6):318–322. doi: 10.1021/acs.estlett.9b00218. [DOI] [Google Scholar]
  41. Bamberger I., Hörtnagl L., Ruuskanen T. M., Schnitzhofer R., Müller M., Graus M., Karl T., Wohlfahrt G., Hansel A.. Deposition fluxes of terpenes over grassland. J. Geophys. Res. Atmos. 2011;116:D14305. doi: 10.1029/2010JD015457. [DOI] [PMC free article] [PubMed] [Google Scholar]
  42. Karl T., Harley P., Emmons L., Thornton B., Guenther A., Basu C., Turnipseed A., Jardine K.. Efficient atmospheric cleansing of oxidized organic trace gases by vegetation. Science. 2010;330(6005):816–819. doi: 10.1126/science.1192534. [DOI] [PubMed] [Google Scholar]
  43. Zhou P., Ganzeveld L., Taipale D., Rannik Ü., Rantala P., Rissanen M. P., Chen D., Boy M.. Boreal forest BVOC exchange: emissions versus in-canopy sinks. Atmos. Chem. Phys. 2017;17(23):14309–14332. doi: 10.5194/acp-17-14309-2017. [DOI] [Google Scholar]
  44. Brüggemann M., Poulain L., Held A., Stelzer T., Zuth C., Richters S., Mutzel A., van Pinxteren D., Iinuma Y., Katkevica S., Rabe R., Herrmann H., Hoffmann T.. Real-time detection of highly oxidized organosulfates and BSOA marker compounds during the F-BEACh 2014 field study. Atmos. Chem. Phys. 2017;17(2):1453–1469. doi: 10.5194/acp-17-1453-2017. [DOI] [Google Scholar]
  45. Qiu J., Shen X., Chen J., Li G., An T.. A possible unaccounted source of nitrogen-containing compound formation in aerosols: amines reacting with secondary ozonides. Atmos. Chem. Phys. 2024;24(1):155–166. doi: 10.5194/acp-24-155-2024. [DOI] [Google Scholar]
  46. Qiu J., Liang Z., Tonokura K., Colussi A. J., Enami S.. Stability of monoterpene-derived alpha-hydroxyalkyl-hydroperoxides in aqueous organic media: relevance to the fate of hydroperoxides in aerosol particle phases. Environ. Sci. Technol. 2020;54(7):3890–3899. doi: 10.1021/acs.est.9b07497. [DOI] [PubMed] [Google Scholar]
  47. Qiu J., Tonokura K., Enami S.. Proton-catalyzed decomposition of alpha-hydroxyalkyl-hydroperoxides in water. Environ. Sci. Technol. 2020;54(17):10561–10569. doi: 10.1021/acs.est.0c03438. [DOI] [PubMed] [Google Scholar]
  48. Qiu J., Ishizuka S., Tonokura K., Colussi A. J., Enami S.. Water dramatically accelerates the decomposition of alpha-hydroxyalkyl-hydroperoxides in aerosol particles. J. Phys. Chem. Lett. 2019;10(19):5748–5755. doi: 10.1021/acs.jpclett.9b01953. [DOI] [PMC free article] [PubMed] [Google Scholar]
  49. Booth D., Dainton F. S., Ivin K. J.. Thermodynamics of formation and absorption spectra of 1:1 complexes between sulphur dioxide and olefines. Trans. Faraday Soc. 1959;55(0):1293–1309. doi: 10.1039/tf9595501293. [DOI] [Google Scholar]
  50. Wang Y. C., Ma Y. G., Kuang B. Y., Lin P., Liang Y. M., Huang C., Yu J. Z.. Abundance of organosulfates derived from biogenic volatile organic compounds: Seasonal and spatial contrasts at four sites in China. Sci. Total Environ. 2022;806:151275. doi: 10.1016/j.scitotenv.2021.151275. [DOI] [PubMed] [Google Scholar]
  51. Surratt J. D., Murphy S. M., Kroll J. H., Ng N. L., Hildebrandt L., Sorooshian A., Szmigielski R., Vermeylen R., Maenhaut W., Claeys M., Flagan R. C., Seinfeld J. H.. Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene. J. Phys. Chem. A. 2006;110(31):9665–9690. doi: 10.1021/jp061734m. [DOI] [PubMed] [Google Scholar]
  52. Nguyen T. B., Lee P. B., Updyke K. M., Bones D. L., Laskin J., Laskin A., Nizkorodov S. A.. Formation of nitrogen- and sulfur-containing light-absorbing compounds accelerated by evaporation of water from secondary organic aerosols. J. Geophys. Res. Atmos. 2012;117(D1):2011JD016944. doi: 10.1029/2011JD016944. [DOI] [Google Scholar]
  53. Ma Y., Xu X., Song W., Geng F., Wang L.. Seasonal and diurnal variations of particulate organosulfates in urban Shanghai, China. Atmos. Environ. 2014;85:152–160. doi: 10.1016/j.atmosenv.2013.12.017. [DOI] [Google Scholar]
  54. Tao S., Lu X., Levac N., Bateman A. P., Nguyen T. B., Bones D. L., Nizkorodov S. A., Laskin J., Laskin A., Yang X.. Molecular characterization of organosulfates in organic aerosols from Shanghai and Los Angeles urban areas by nanospray-desorption electrospray ionization high-resolution mass spectrometry. Environ. Sci. Technol. 2014;48(18):10993–11001. doi: 10.1021/es502467. [DOI] [PubMed] [Google Scholar]
  55. Riva M., Da Silva Barbosa T., Lin Y.-H., Stone E. A., Gold A., Surratt J. D.. Chemical characterization of organosulfates in secondary organic aerosolderived from the photooxidation of alkanes. Atmos. Chem. Phys. 2016;16(17):11001–11018. doi: 10.5194/acp-16-11001-2016. [DOI] [Google Scholar]
  56. Wang Y. C., Ren J. Y., Huang X. H. H., Tong R. B., Yu J. Z.. Synthesis of four monoterpene-derived organosulfates and their quantification in atmospheric aerosol samples. Environ. Sci. Technol. 2017;51(12):6791–6801. doi: 10.1021/acs.est.7b01179. [DOI] [PubMed] [Google Scholar]
  57. Subramanian D., Boughter C. T., Klauda J. B., Hammouda B., Anisimov M. A.. Mesoscale inhomogeneities in aqueous solutions of small amphiphilic molecules. Faraday. Discuss. 2014;167:217–238. doi: 10.1039/c3fd00070b. [DOI] [PubMed] [Google Scholar]
  58. Rak D., Sedlák M.. On the mesoscale solubility in liquid solutions and mixtures. J. Phys. Chem. B. 2019;123(6):1365–1374. doi: 10.1021/acs.jpcb.8b10638. [DOI] [PubMed] [Google Scholar]
  59. Kononov L. O.. Chemical reactivity and solution structure: on the way to a paradigm shift? RSC Adv. 2015;5(58):46718–46734. doi: 10.1039/C4RA17257D. [DOI] [Google Scholar]
  60. Nagasaka M., Yuzawa H., Kosugi N.. Microheterogeneity in aqueous acetonitrile solution probed by soft x-ray absorption spectroscopy. J. Phys. Chem. B. 2020;124(7):1259–1265. doi: 10.1021/acs.jpcb.0c00551. [DOI] [PubMed] [Google Scholar]
  61. Pye H. O. T., Nenes A., Alexander B., Ault A. P., Barth M. C., Clegg S. L., Collett J. L., Fahey K. M., Hennigan C. J., Herrmann H., Kanakidou M., Kelly J. T., Ku I. T., McNeill V. F., Riemer N., Schaefer T., Shi G. L., Tilgner A., Walker J. T., Wang T., Weber R., Xing J., Zaveri R. A., Zuend A.. The acidity of atmospheric particles and clouds. Atmos. Chem. Phys. 2020;20(8):4809–4888. doi: 10.5194/acp-20-4809-2020. [DOI] [PMC free article] [PubMed] [Google Scholar]
  62. Collett J. L., Bator A., Rao X., Demoz B. B.. Acidity variations across the cloud drop size spectrum and their influence on rates of atmospheric sulfate production. Geophys. Res. Lett. 1994;21(22):2393–2396. doi: 10.1029/94GL02480. [DOI] [Google Scholar]
  63. Guenther A. B., Jiang X., Heald C. L., Sakulyanontvittaya T., Duhl T., Emmons L. K., Wang X.. The model of emissions of gases and aerosols from nature version 2.1 (MEGAN 2.1): An extended and updated framework for modeling biogenic emissions. Geosci. Model. Dev. 2012;5(6):1471–1492. doi: 10.5194/gmd-5-1471-2012. [DOI] [Google Scholar]
  64. Guenther A., Hewitt C. N., Erickson D., Fall R., Geron C., Graedel T., Harley P., Klinger L., Lerdau M., McKay W. A., Pierce T., Scholes B., Steinbrecher R., Tallamraju R., Taylor J., Zimmerman P.. A global model of natural volatile organic compound emissions. J. Geophys. Res. Atmos. 1995;100(D5):8873–8892. doi: 10.1029/94JD02950. [DOI] [Google Scholar]
  65. Liggio J., Li S. M., Brook J. R., Mihele C.. Direct polymerization of isoprene and α-pinene on acidic aerosols. Geophys. Res. Lett. 2007;34(5):1. doi: 10.1029/2006GL028468. [DOI] [Google Scholar]
  66. Enami S., Hoffmann M. R., Colussi A. J.. Dry deposition of biogenic terpenes via cationic oligomerization on environmental aqueous surfaces. J. Phys. Chem. Lett. 2012;3(21):3102–3108. doi: 10.1021/jz301294q. [DOI] [PubMed] [Google Scholar]
  67. Enami S., Mishra H., Hoffmann M. R., Colussi A. J.. Protonation and oligomerization of gaseous isoprene on mildly acidic surfaces: Implications for atmospheric chemistry. J. Phys. Chem. A. 2012;116(24):6027–6032. doi: 10.1021/jp2110133. [DOI] [PubMed] [Google Scholar]
  68. Donaldson D. J., Valsaraj K. T.. Adsorption and reaction of trace gas-phase organic compounds on atmospheric water film surfaces: A critical review. Environ. Sci. Technol. 2010;44(3):865–873. doi: 10.1021/es902720s. [DOI] [PubMed] [Google Scholar]
  69. Ishizuka S., Fujii T., Matsugi A., Sakamoto Y., Hama T., Enami S.. Controlling factors of oligomerization at the water surface: why is isoprene such a unique VOC? Phys. Chem. Chem. Phys. 2018;20(22):15400–15410. doi: 10.1039/C8CP01551A. [DOI] [PubMed] [Google Scholar]
  70. Ishizuka S., Matsugi A., Hama T., Enami S.. Interfacial water mediates oligomerization pathways of monoterpene carbocations. J. Phys. Chem. Lett. 2020;11(1):67–74. doi: 10.1021/acs.jpclett.9b03110. [DOI] [PubMed] [Google Scholar]
  71. Connelly B. M., Tolbert M. A.. Reaction of isoprene on thin sulfuric acid films: Kinetics, uptake, and product analysis. Environ. Sci. Technol. 2010;44(12):4603–4608. doi: 10.1021/es100708b. [DOI] [PubMed] [Google Scholar]
  72. Mahilang M., Deb M. K., Pervez S.. Biogenic secondary organic aerosols: A review on formation mechanism, analytical challenges and environmental impacts. Chemosphere. 2021;262:127771. doi: 10.1016/j.chemosphere.2020.127771. [DOI] [PubMed] [Google Scholar]
  73. Liu L., Hohaus T., Franke P., Lange A. C., Tillmann R., Fuchs H., Tan Z., Rohrer F., Karydis V., He Q., Vardhan V., Andres S., Bohn B., Holland F., Winter B., Wedel S., Novelli A., Hofzumahaus A., Wahner A., Kiendler-Scharr A.. Observational evidence reveals the significance of nocturnal chemistry in seasonal secondary organic aerosol formation. npj Clim Atmos Sci. 2024;7(1):207. doi: 10.1038/s41612-024-00747-6. [DOI] [PMC free article] [PubMed] [Google Scholar]
  74. Li L., Li J., Zhang X., Lin Y., Wang R., Cao J., Han Y.. Effects of relative humidity on atmospheric organosulfur species derived from photooxidation and nocturnal chemistry in a forest environment. Environ. Pollut. 2024;363:125253. doi: 10.1016/j.envpol.2024.125253. [DOI] [PubMed] [Google Scholar]
  75. Zhong S., Chen S., Deng J., Fan Y., Zhang Q., Xie Q., Qi Y., Hu W., Wu L., Li X., Pavuluri C. M., Zhu J., Wang X., Liu D., Pan X., Sun Y., Wang Z., Xu Y., Tong H., Su H., Cheng Y., Kawamura K., Fu P.. Impact of biogenic secondary organic aerosol (SOA) loading on the molecular composition of wintertime PM2.5 in urban Tianjin: an insight from Fourier transform ion cyclotron resonance mass spectrometry. Atmos. Chem. Phys. 2023;23(3):2061–2077. doi: 10.5194/acp-23-2061-2023. [DOI] [Google Scholar]
  76. Zhang H., Yee L. D., Lee B. H., Curtis M. P., Worton D. R., Isaacman-VanWertz G., Offenberg J. H., Lewandowski M., Kleindienst T. E., Beaver M. R., Holder A. L., Lonneman W. A., Docherty K. S., Jaoui M., Pye H. O. T., Hu W., Day D. A., Campuzano-Jost P., Jimenez J. L., Guo H., Weber R. J., De Gouw J., Koss A. R., Edgerton E. S., Brune W., Mohr C., Lopez-Hilfiker F. D., Lutz A., Kreisberg N. M., Spielman S. R., Hering S. V., Wilson K. R., Thornton J. A., Goldstein A. H.. Monoterpenes are the largest source of summertime organic aerosol in the southeastern United States. Proc. Natl. Acad. Sci. U.S.A. 2018;115(9):2038–2043. doi: 10.1073/pnas.1717513115. [DOI] [PMC free article] [PubMed] [Google Scholar]
  77. Huang R.-J., Cao J., Chen Y., Yang L., Shen J., You Q., Wang K., Lin C., Xu W., Gao B., Li Y., Chen Q., Hoffmann T., O’Dowd C. D., Bilde M., Glasius M.. Organosulfates in atmospheric aerosol: synthesis and quantitative analysis of PM2.5 from Xi’an, northwestern China. Atmos. Meas. Technol. 2018;11(6):3447–3456. doi: 10.5194/amt-11-3447-2018. [DOI] [Google Scholar]
  78. Hatch L. E., Creamean J. M., Ault A. P., Surratt J. D., Chan M. N., Seinfeld J. H., Edgerton E. S., Su Y., Prather K. A.. Measurements of Isoprene-Derived Organosulfates in Ambient Aerosols by Aerosol Time-of-Flight Mass SpectrometryPart 2: Temporal Variability and Formation Mechanisms. Environ. Sci. Technol. 2011;45(20):8648–8655. doi: 10.1021/es2011836. [DOI] [PubMed] [Google Scholar]
  79. Marais E. A., Jacob D. J., Jimenez J. L., Campuzano-Jost P., Day D. A., Hu W., Krechmer J., Zhu L., Kim P. S., Miller C. C., Fisher J. A., Travis K., Yu K., Hanisco T. F., Wolfe G. M., Arkinson H. L., Pye H. O. T., Froyd K. D., Liao J., McNeill V. F.. Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls. Atmos. Chem. Phys. 2016;16(3):1603–1618. doi: 10.5194/acp-16-1603-2016. [DOI] [PMC free article] [PubMed] [Google Scholar]
  80. Darer A. I., Cole-Filipiak N. C., O’Connor A. E., Elrod M. J.. Formation and Stability of Atmospherically Relevant Isoprene-Derived Organosulfates and Organonitrates. Environ. Sci. Technol. 2011;45(5):1895–1902. doi: 10.1021/es103797z. [DOI] [PubMed] [Google Scholar]
  81. Nozière B., Ekström S., Alsberg T., Holmström S.. Radical-initiated formation of organosulfates and surfactants in atmospheric aerosols. Geophys. Res. Lett. 2010;37(5):2009GL041683. doi: 10.1029/2009GL041683. [DOI] [Google Scholar]
  82. Seinfeld, J. H. ; Pandis, S. N. . Atmospheric chemistry and physics: From Air Pollution to Climate Change; John Wiley & Sons, 2016. [Google Scholar]
  83. Ma L., Worland R., Jiang W. Q., Niedek C., Guzman C., Bein K. J., Zhang Q., Anastasio C.. Predicting photooxidant concentrations in aerosol liquid water based on laboratory extracts of ambient particles. Atmos. Chem. Phys. 2023;23(15):8805–8821. doi: 10.5194/acp-23-8805-2023. [DOI] [Google Scholar]
  84. Ng N. L., Brown S. S., Archibald A. T., Atlas E., Cohen R. C., Crowley J. N., Day D. A., Donahue N. M., Fry J. L., Fuchs H., Griffin R. J., Guzman M. I., Herrmann H., Hodzic A., Iinuma Y., Jimenez J. L., Kiendler-Scharr A., Lee B. H., Luecken D. J., Mao J., McLaren R., Mutzel A., Osthoff H. D., Ouyang B., Picquet-Varrault B., Platt U., Pye H. O. T., Rudich Y., Schwantes R. H., Shiraiwa M., Stutz J., Thornton J. A., Tilgner A., Williams B. J., Zaveri R. A.. Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol. Atmos. Chem. Phys. 2017;17(3):2103–2162. doi: 10.5194/acp-17-2103-2017. [DOI] [PMC free article] [PubMed] [Google Scholar]
  85. Herrmann H., Schaefer T., Tilgner A., Styler S. A., Weller C., Teich M., Otto T.. Tropospheric aqueous-phase chemistry: kinetics, mechanisms, and its coupling to a changing gas phase. Chem. Rev. 2015;115(10):4259–4334. doi: 10.1021/cr500447k. [DOI] [PubMed] [Google Scholar]
  86. Jones C. E., Hopkins J. R., Lewis A. C.. In situ measurements of isoprene and monoterpenes within a south-east Asian tropical rainforest. Atmos. Chem. Phys. 2011;11(14):6971–6984. doi: 10.5194/acp-11-6971-2011. [DOI] [Google Scholar]
  87. Surdu M., Lamkaddam H., Wang D. S., Bell D. M., Xiao M., Lee C. P., Li D., Caudillo L., Marie G., Scholz W., Wang M., Lopez B., Piedehierro A. A., Ataei F., Baalbaki R., Bertozzi B., Bogert P., Brasseur Z., Dada L., Duplissy J., Finkenzeller H., He X.-C., Höhler K., Korhonen K., Krechmer J. E., Lehtipalo K., Mahfouz N. G. A., Manninen H. E., Marten R., Massabò D., Mauldin R., Petäjä T., Pfeifer J., Philippov M., Rörup B., Simon M., Shen J., Umo N. S., Vogel F., Weber S. K., Zauner-Wieczorek M., Volkamer R., Saathoff H., Möhler O., Kirkby J., Worsnop D. R., Kulmala M., Stratmann F., Hansel A., Curtius J., Welti A., Riva M., Donahue N. M., Baltensperger U., El Haddad I.. Molecular Understanding of the Enhancement in Organic Aerosol Mass at High Relative Humidity. Environ. Sci. Technol. 2023;57(6):2297–2309. doi: 10.1021/acs.est.2c04587. [DOI] [PMC free article] [PubMed] [Google Scholar]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

es5c12041_si_001.pdf (557.8KB, pdf)

Articles from Environmental Science & Technology are provided here courtesy of American Chemical Society

RESOURCES