Search Results (20)

Hydroperoxymethyl thioformate (or HPMTF) is a compound relevant to the chemistry of sulfur in the marine atmosphere. The chemical cycling of this molecule in the atmosphere is still uncertain due in part to the lack of accurate knowledge of its photolytic behavior. Only approximations based on the properties of its chromophores are used in previous studies. In this work, we calculated the absorption spectra of the molecule in gas and aqueous phases using the Nuclear Ensemble Approach (NEA) and the CASPT2 method. Furthermore, we used such information to obtain relative photolysis rates. We found that the chromophore approximation overestimates the photolysis rates in the gas phase by twice the value obtained with the NEA-CASPT2 protocol. Furthermore, for the aqueous phase, we predict a lower role of photolysis as compared to the gas phase. Full article

Field studies suggest that NO₃⁻ photolysis may play a more significant role than previously thought. In this study, we concurrently measured HONO, NO₂, and NO₂⁻ in situ to gain a deeper understanding of the photogenerated HONO transfer to air and to better constrain the rate constants of NO₃⁻ photolysis. The presence of fatty acids (e.g., nonanoic acid, NA), which are naturally present in the environment, significantly increases the production of photogenerated HONO and NO₂. With an increase in oxygen percentage, the release rate of photoinduced HONO slowed, while the release rate of NO₂ accelerated. The measured $J_{{{NO}_3}^{-}}$ value averaged 1.65 × 10⁻⁵ s⁻¹, which is two orders of magnitude higher than values reported in similar systems. The HONO transfer rate from the solutions increased from 2.3 × 10⁻⁴ s⁻¹ to 5.6 × 10⁻⁴ s⁻¹ as the NA concentration increased from 0.1 to 20 mM. This can be attributed to the accumulation of NO₂⁻ induced by NA at the interface. Within this interfacial region, NO₂⁻ in the solutions becomes more prone to transfer into gaseous HONO, suggesting that photogenerated NO₂⁻ hosted in atmospheric droplets may serve as a temporary reservoir of atmospheric HONO without illumination, influencing the atmospheric oxidizing capacity in the region for hours. Therefore, simultaneous measurements of both gas and particle phase photoproducts are recommended to better constrain the rate constants of NO₃⁻ photolysis, thereby enhancing the accuracy of predicting the photochemical production of HONO in the atmosphere. Full article

The stable isotope composition of soluble and insoluble organic compounds in carbonaceous chondrites can be used to determine the provenance of organic molecules in space. Deuterium enrichment in meteoritic organics could be a residual signal of synthetic reactions occurring in the cold interstellar medium or an indicator of hydrothermal parent-body reactions. δD values have been measured in grains and bulk samples for a wide range of meteorites; however, these reservoirs are highly variable and may have experienced fractionation during thermal and/or aqueous alteration. Among the plethora of organic compounds in meteorites are polycyclic aromatic hydrocarbons (PAHs), which are stable and abundant in carbonaceous chondrites, and their δD ratio may preserve evidence about their formation environment as well as the influence of parent-body processes. This study tests hypotheses about the potential links between PAHs-deuteration concentrations and their formation conditions by examining the δD ratio of PAHs in three CM carbonaceous chondrites representing an aqueous alteration gradient. We use deuterium enrichments in soluble 2–5-ring PAHs as an indicator of either photon-driven deuteration due to unimolecular photodissociation in warm regions of space, gas-phase ion–molecule reactions in cold interstellar regions of space, or UV photolysis in ices. We also test hypothesized reaction pathways during parent-body processing that differ between partially and fully aromatized PAHs. New methodological approaches were developed to extract small, volatile PAHs without fractionation. Our results suggest that meteoritic PAHs could have formed through reactions in cold regions, with possible overprinting of deuterium enrichment during aqueous parent-body alteration, but the data could not rule out PAH alteration in icy mantles as well. Full article

Monoterpenes are the most essential reactive biogenic volatile organic compounds. Their removal from the atmosphere leads to the formation of oxygenated compounds, such as nopinone (C₉H₁₄O), one of the most important first-generation β-pinene oxidation products that play a pivotal role in environmental and biological applications. In this study, experimental and theoretical rate coefficients were determined for the gas-phase reaction of nopinone with hydroxyl radicals (OH). The absolute rate coefficient was measured for the first time using a cryogenically cooled cell along with the pulsed laser photolysis–laser-induced fluorescence technique at 298 K and 7 Torr. The hydrogen abstraction pathways were found by using electronic structure calculations to determine the most favourable H-abstraction position. Pathway 5 (bridgehead position) was more favourable, with a small barrier height of −1.23 kcal/mol. The rate coefficients were calculated based on the canonical variational transition state theory with the small-curvature tunnelling method (CVT/SCT) as a function of temperature. The average experimental rate coefficient (1.74 × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹) was in good agreement with the theoretical value (2.2 × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹). Conclusively, the results of this study pave the way to understand the atmospheric chemistry of nopinone with OH radicals. Full article

A key component of the marine sulfur cycle is the climate-active gas dimethylsulfide (DMS), which is synthesized by a range of organisms from phytoplankton to corals, and accounts for up to 80% of global biogenic sulfur emissions. The DMS cycle starts with the intracellular synthesis of the non-gaseous precursor dimethylsulfoniopropionate (DMSP), which is released to the water column by various food web processes such as zooplankton grazing. This dissolved DMSP pool is rapidly turned over by microbially mediated conversion using two known pathways: demethylation (releasing methanethiol) and cleavage (producing DMS). Some of the formed DMS is ventilated to the atmosphere, where it undergoes rapid oxidation and contributes to the formation of sulfate aerosols, with the potential to affect cloud microphysics, and thus the regional climate. The marine phase cycling of DMS is complex, however, as heterotrophs also contribute to the consumption of the newly formed dissolved DMS. Interestingly, due to microbial consumption and other water column sinks such as photolysis, the amount of DMS that enters the atmosphere is currently thought to be a relatively minor fraction of the total amount cycled through the marine food web—less than 10%. These microbial processes are mediated by water column temperature, but the response of marine microbial assemblages to ocean warming is poorly characterized, although bacterial degradation appears to increase with an increase in temperature. This review will focus on the potential impact of climate change on the key microbially mediated processes in the marine cycling of DMS. It is likely that the impact will vary across different biogeographical regions from polar to tropical. For example, in the rapidly warming polar oceans, microbial communities associated with the DMS cycle will likely change dramatically during the 21st century with the decline in sea ice. At lower latitudes, where corals form an important source of DMS (P), shifts in the microbiome composition have been observed during thermal stress with the potential to alter the DMS cycle. Full article

In this study, a TiO₂–alumina photocatalyst was manufactured by coating a surface-treated alumina substrate with TiO₂ sol using the sol–gel method, and the photolysis and conversion of acetaldehyde in the gas phase were evaluated. The effects of acetaldehyde flow rate (i.e., retention time), ultraviolet wavelength, moisture, and catalyst heat-treatment temperature on the conversion of acetaldehyde were investigated. The experiments confirmed that a decrease in flow rate (i.e., increase in retention time), increase in moisture level, and decrease in the ultraviolet wavelength of the light source increased the conversion rate of the gaseous acetaldehyde. Among the three heat-treatment temperatures (450, 650, and 850 °C) used in the catalyst manufacturing process, the catalyst treated at 650 °C had the highest acetaldehyde conversion rate. As a result of its increased acetaldehyde decomposition and photoefficiency, the newly manufactured TiO₂–alumina photocatalyst is expected to be used alongside a photoreactor as an air-purifying filter. Furthermore, the photocatalyst surface treatment demonstrated herein can be adopted to fabricate various environmentally friendly materials in the future. Full article

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. Full article

The degradation mechanism of NH₄⁺/NH₃ in aqueous solutions by heterogeneous photocatalysis (TiO₂/SiO₂) and photolysis in UV-C pilot photoreactor has been studied. Under the conditions used, NH₄⁺/NH₃ can be decomposed both by photolytically and photocatalytically, without disregarding stripping processes. The greatest degradation is achieved at the highest pH studied (pH 11.0) and at higher lamp irradiation power used (25 W) with degradation performances of 44.1% (photolysis) and 59.7% (photocatalysis). The experimental kinetic data fit well with a two parallel reactions mechanism. A low affinity of ammonia for adsorption and surface reaction on the photocatalytic fiber was observed (coverage not higher than 10%), indicating a low influence of surface phenomena on the reaction rate, the homogeneous phase being predominant over the heterogeneous phase. The proposed reaction mechanism was validated, confirming that it is consistent with the photocatalytic and photolytic formation of nitrogen gas, on the one hand, and the formation of nitrate, on the other hand. At the optimal conditions, the rate constants were k₃ = 0.154 h⁻¹ for the disappearance of ammonia and k₁ = 3.3 ± 0.2 10⁻⁵ h⁻¹ and k₂ = 1.54 ± 0.07 10⁻¹ h⁻¹ for the appearance of nitrate and nitrogen gas, respectively. Full article

The application of electrospray ionisation mass spectrometry (ESI-MS) as a direct method for detecting reactive intermediates is a technique of developing importance in the routine monitoring of solution-phase reaction pathways. Here, we utilise a novel on-line photolysis ESI-MS approach to detect the photoproducts of riboflavin in aqueous solution under mildly alkaline conditions. Riboflavin is a constituent of many food products, so its breakdown processes are of wide interest. Our on-line photolysis setup allows for solution-phase photolysis to occur within a syringe using UVA LEDs, immediately prior to being introduced into the mass spectrometer via ESI. Gas-phase photofragmentation studies via laser-interfaced mass spectrometry of deprotonated riboflavin, [RF − H]⁻, the dominant solution-phase species under the conditions of our study, are presented alongside the solution-phase photolysis. The results obtained illustrate the extent to which gas-phase photolysis methods can inform our understanding of the corresponding solution-phase photochemistry. We determine that the solution-phase photofragmentation observed for [RF − H]⁻ closely mirrors the gas-phase photochemistry, with the dominant m/z 241 condensed-phase photoproduct also being observed in gas-phase photodissociation. Further gas-phase photoproducts are observed at m/z 255, 212, and 145. The value of exploring both the gas- and solution-phase photochemistry to characterise photochemical reactions is discussed. Full article

Nitrophenols are important products of the aromatic compounds photooxidation and play a considerable role in urban chemistry. Nitrophenols are important components of agricultural biomass burning that could influence the climate. The formation of secondary organic aerosol from the direct photolysis of nitrophenols was investigated for the first time in a quartz glass simulation chamber under simulated solar radiation. The results from these experiments indicate rapid SOA formation. The proposed mechanism for the gas-phase degradation of nitrophenols through photolysis shows the formation of biradicals that could react further in the presence of oxygen to form low volatile highly oxygenated compounds responsible for secondary organic aerosol formation. The inhibiting effect of NOx and the presence of an OH radical scavenger on the aerosol formation were also studied. For 2-nitrophenol, significant aerosol formation yields were observed in the absence of an OH radical scavenger and NOx, varying in the range of 18%–24%. A gas-phase/aerosol partitioning model was applied assuming the presence of only one compound in both phases. A degradation mechanism is proposed to explain the aerosol formation observed in the photolysis of nitrophenols. The atmospheric impact of nitrophenol photolysis is discussed and the importance for atmospheric chemical models is assessed. Full article

Verteporfin, a free base benzoporphyrin derivative monoacid ring A, is a photosensitizing drug for photodynamic therapy (PDT) used in the treatment of the wet form of macular degeneration and activated by red light of 689 nm. Here, we present the first direct study of its photofragmentation channels in the gas phase, conducted using a laser interfaced mass spectrometer across a broad photoexcitation range from 250 to 790 nm. The photofragmentation channels are compared with the collision-induced dissociation (CID) products revealing similar dissociation pathways characterized by the loss of the carboxyl and ester groups. Complementary solution-phase photolysis experiments indicate that photobleaching occurs in verteporfin in acetonitrile; a notable conclusion, as photoinduced activity in Verteporfin was not thought to occur in homogenous solvent conditions. These results provide unique new information on the thermal break-down products and photoproducts of this light-triggered drug. Full article

Chlorine atoms play a key role in the oxidative potential of the atmosphere and biogeochemical cycling of selected elements. This study provides a decadal analysis (2010−2019) of chloride ions in PM_2.5 particles in the city of Montreal, where these are most concentrated systematically in the winter (up to 1.6 µg/m³). We also herein present the measurement of photolabile chlorine, which includes chlorine-containing compounds (e.g., Cl₂, HOCl, ClNO₂, ClNO₃, and BrCl) that release chlorine atoms upon interaction with radiation, in urban Montreal, Canada using Cl2-RPGE (Cl2 Reactive Phase Gas Extraction) tubes and quantifying the chlorinated product by GC-MS. Photolabile chlorine in urban Montreal was measured during a discontinuous period primarily in summer 2018 and winter 2019 with a time resolution of 30 min, with concentrations ranging from 3 to 545 ng/m³ expressed as Cl₂. The reported values are considered lower limits, as compounds such as HOCl and ClNO₂ can only be partially converted in the current setup. The largest peak of gaseous photolabile chlorine occurred in the winter, when significant sources of anthropogenic salt are used in snow removal in the city. This coincides with observed chloride ion measurements in airborne particles, implying that anthropogenic salt addition produces photoactive chlorine. The maximum chlorine signal was consistently obtained during the daytime, which is in accordance with the tropospheric radiation profile. Complementary photochemistry laboratory experiments indicated that upon tropospheric radiation (340 ≤ λ ≤ 400 nm; UVA), an increase (20–100%) was observed, confirming the formation of Cl atoms from photolabile chlorine compounds. Thus, this portable technique is adequate for Cl atoms and photolabile chlorine-containing compounds upon photolysis using UVA lamps. High-resolution S/TEM and energy-dispersive X-ray spectroscopy (EDS) were used to evaluate collected particle morphology and composition. The behavior of complementary pollutants (O₃, CO, PM_2.5, and NO_x) was also briefly discussed. We herein discuss the measurement of photolabile halogens within a northern urban metropolitan environment and the impact of anthropogenic sources on chlorine concentrations. Full article

The reactions of five structurally similar unsaturated alcohols, i.e., (Z)-2-penten-1-ol, (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, (Z)-3-hexen-1-ol, and 1-octen-3-ol, with Cl atoms in the gas phase, were investigated at 296 ± 2 K and 1 atm by the relative-rate kinetic technique using a 600-L Teflon reaction chamber. Selected ion flow tube mass spectrometry (SIFT-MS) was used simultaneously to monitor the decay of the alcohols of interest and selected reference compounds. Tetrahydrofuran (THF), propan-1-ol, and octane were used as reference compounds. Chlorine atoms were produced by the photolysis of molecular chlorine (Cl₂) using broadband actinic lamps near 365 nm. The estimated rate constant values (in 10⁻¹⁰ cm³∙molecule⁻¹∙s⁻¹) followed the order 2.99 ± 0.53 ((Z)-2-penten-1-ol) < 3.05 ± 0.59 ((E)-3-hexen-1-ol) < 3.15 ± 0.58 ((Z)-3-hexen-1-ol) < 3.41 ± 0.65 ((E)-2-hexen-1-ol) < 4.03 ± 0.77 (1-octen-3-ol). The present work provides the first value of the rate constant for the reaction of 1-octen-3-ol with Cl atoms. The results are discussed and interpreted in relation to other studies where literature data are available. The structure–activity relationship and the atmospheric implications are discussed as well. Full article

Western Australia is a semi-/arid region known for saline lakes with a wide range of geochemical parameters (pH 2.5–7.1, Cl⁻ 10–200 g L⁻¹). This study reports on the haloacetones chloro- and bromoacetone in air over 6 salt lake shorelines. Significant emissions of chloroacetone (up to 0.2 µmol m⁻² h⁻¹) and bromoacetone (up to 1. 5 µmol m⁻² h⁻¹) were detected, and a photochemical box model was employed to evaluate the contribution of their atmospheric formation from the olefinic hydrocarbons propene and methacrolein in the gas phase. The measured concentrations could not explain the photochemical halogenation reaction, indicating a strong hitherto unknown source of haloacetones. Aqueous-phase reactions of haloacetones, investigated in the laboratory using humic acid in concentrated salt solutions, were identified as alternative formation pathway by liquid-phase reactions, acid catalyzed enolization of ketones, and subsequent halogenation. In order to verify this mechanism, we made measurements of the Henry’s law constants, rate constants for hydrolysis and nucleophilic exchange with chloride, UV-spectra and quantum yields for the photolysis of bromoacetone and 1,1-dibromoacetone in the aqueous phase. We suggest that heterogeneous processes induced by humic substances in the quasi-liquid layer of the salt crust, particle surfaces and the lake water are the predominating pathways for the formation of the observed haloacetones. Full article

A new device and methodology for vertically coupling confocal Raman microscopy with optical tweezers for the in situ physico- and photochemical studies of individual microdroplets (Ø ≤ 10 µm) levitated in air is presented. The coupling expands the spectrum of studies performed with individual particles using laser tweezers Raman spectroscopy (LTRS) to photochemical processes and spatially resolved Raman microspectroscopy on airborne aerosols. This is the first study to demonstrate photochemical studies and Raman mapping on optically levitated droplets. By using this configuration, photochemical reactions in aerosols of atmospheric interest can be studied on a laboratory scale under realistic conditions of gas-phase composition and relative humidity. Likewise, the distribution of photoproducts within the drop can also be observed with this setup. The applicability of the coupling system was tested by studying the photochemical behavior of microdroplets (5 µm < Ø < 8 µm) containing an aqueous solution of sodium nitrate levitated in air and exposed to narrowed UV radiation (254 ± 25 nm). Photolysis of the levitated NaNO₃ microdroplets presented photochemical kinetic differences in comparison with larger NaNO₃ droplets (40 µm < Ø < 80 µm), previously photolyzed using acoustic traps, and heterogeneity in the distribution of the photoproducts within the drop. Full article