Photochemical studies of atmospherically relevant species in multiple phases

In this thesis, fundamentally and atmospherically relevant species, their heterogeneous chemistry, and photolytic processing in multiple phases are explored both experimentally and computationally, providing important new insights and mechanistic understanding of these complicated systems. HArF is a covalently bonded neutral ground-state molecule of argon that is found to form at very low temperatures. This thesis explores the HArF low temperature formation mechanism and kinetics, and discusses the effect of the environment to the formation. In the next part, a computational study of an atmospherically relevant molecule N2O4 and its isomerization and ionization on model ice and silica surfaces is presented. N2O4 is known to produce HONO, which is a major source of atmospheric OH, an important atmospheric oxidant. The isomerization mechanism is found to be connected to the dangling surface hydrogen atoms at both surfaces, and we suggest that this mechanism could be expanded to other atmospherically relevant surfaces as well. Atmospheric aerosols play a critical role in controlling climate, driving chemical reactions in the atmosphere, acting as surfaces catalyzing heterogeneous reactions, and contributing to air pollution problems and indoor air quality issues. Low-volatility organic compounds that are produced in the oxidation of biogenic and anthropogenic Volatile Organic Compounds (VOC s) are known collectively as Secondary Organic Aerosol (SOA). In this thesis, a comprehensive investigation of aqueous photochemistry of cis-pinonic acid, a common product of ozonolysis of α-pinene (an SOA precursor) is presented. Various experimental techniques are used to study the kinetics, photolysis rates, quantum yields, and photolysis products, and computational methods are used to explore the photolysis mechanisms. Atmospheric implications and importance of aqueous photolysis vs. OH-mediated aging is discussed. The viscosity effects on SOA chemistry are then explored by a novel approach where an environmentally relevant probe molecule 2,4-dinitrophenol is embedded directly inside the SOA matrix, and its photochemistry is studied at different temperatures and compared to reaction efficiency in other reaction media (octanol and water). It is observed that decreasing temperature significantly slows down the photochemical process in the SOA matrix, and this behavior is ascribed to increasing viscosity of the SOA material.Tässä väitöskirjassa on tutkittu ilmakehän sekä kiinteän tilan perustutkimuksen kannalta tärkeiden systeemien heterogeenistä kemiaa sekä valokemiallisia reaktioita eri faaseissa hyödyntäen kokeellisia ja laskennallisia menetelmiä. Saavutetut tutkimustulokset tarjoavat uusia näkemyksiä ja syventävät näiden monimutkaisten mutta tärkeiden prosessien ymmärrystä. HArF-molekyyli on pysyvä, perustilainen argonyhdiste, jonka on havaittu muodostuvan hyvin matalissa lämpötiloissa. Tämän väitöskirjan ensimmäisessä osiossa tutkittiin HArF-molekyylin matalan lämpötilan muodostumismekanismia ja kinetiikkaa, sekä käsiteltiin kiinteän tilan vaikutusta molekyylin ominaisuuksiin. Seuraavassa osiossa ilmakehän kannalta tärkeän N2O4 molekyylin isomeroitumis- ja ionisoitumismekanismeja tutkittiin laskennallisesti jää- ja silikapinnoilla. N2O4 molekyylin tiedetään muodostavan HONO-yhdistettä joka on ilmakehän kannalta tärkeän hapettajan, OH-radikaalin tärkein lähde. Isomeroitumismekanismin havaittiin liittyvän tutkittujen pintojen sitoutumattomiin vetyihin, ja ehdotettiin että havaittua mekanismia voidaan soveltaa myos muihin ilmakehän kannalta oleellisiin pintoihin. Vesifaasissa tapahtuvia reaktioita lähestyttiin cis-pinonihapon vesifaasissa tapahtuvien valokemiallisten prosessien muodossa. cis-Pinonihappo on yksi α-pineenin otsonolyysireaktion yleisimmstä tuotteista. Useita kokeellisia menetelmiä hyödyntäen tutkittiin molekyylin valokemiallisen hajoamisen kinetiikkaa, mekanismeja, kvanttisuhteita, sekä hajoamistuotteita, ja laskennallisten tulosten havaittiin tukevan kokeellisisesti saavutettuja tuloksia. Tutkimustulosten merkittävyyttä ilmakehässä käsiteltiin ja vesifaasissa tapahtuvien reaktioiden tehokkuutta verrattiin OH-radikaalin ajamaan kemiaan. Viskositeetin vaikutusta SOA hiukkasten valokemiaan lähestyttiin tutkimalla kuinka lämpötila muuttaa valokemiallisten reaktioiden nopeutta SOA-matriiseissa. Työssä hyödynettiin täysin uutta lähestymis-tapaa, jossa koetinmolekyyliksi valitun, ympäristön kannalta tärkeän 2,4-dinitrofenolimolekyylin valokemiallisen hajoamisen tehokkuutta tutkittiin SOA-matriisin sisällä. Reaktionopeutta verrattiin mittauksiin vesi- ja oktanoliväliaineissa. Voimakas reaktionopeuden lämpötilariippuvuus SOA-ympäristössä voitiin selittää kasvaneen viskositeetin reaktiota rajoittavalla vaikutuksella

Exploring matrix effects on photochemistry of organic aerosols

This work explores the effect of the environment on the rate of photolysis of 2,4-dinitrophenol (24-DNP), an important environmental toxin. In stark contrast to the slow photolysis of 24-DNP in an aqueous solution, the photolysis rate is increased by more than an order of magnitude for 24-DNP dissolved in 1-octanol or embedded in secondary organic material (SOM) produced by ozonolysis of α-pinene. Lowering the temperature decreased the photolysis rate of 24-DNP in SOM much more significantly than that of 24-DNP in octanol, with effective activation energies of 53 kJ/mol and 12 kJ/mol, respectively. We discuss the possibility that the increasing viscosity of the SOM matrix constrains the molecular motion, thereby suppressing the hydrogen atom transfer reaction to the photo-excited 24-DNP. This is, to our knowledge, the first report of a significant effect of the matrix, and possibly viscosity, on the rate of an atmospheric photochemical reaction within SOM. It suggests that rates of photochemical processes in organic aerosols will depend on both relative humidity and temperature and thus altitude. The results further suggest that photochemistry in SOM may play a key role in transformations of atmospheric organics. For example, 24-DNP and other nitro-aromatic compounds should readily photodegrade in organic particulate matter, which has important consequences for predicting their environmental fates and impacts

The Caltech Photooxidation Flow Tube reactor: design, fluid dynamics and characterization

Flow tube reactors are widely employed to study gas-phase atmospheric chemistry and secondary organic aerosol (SOA) formation. The development of a new laminar-flow tube reactor, the Caltech Photooxidation Flow Tube (CPOT), intended for the study of gas-phase atmospheric chemistry and SOA formation, is reported here. The present work addresses the reactor design based on fluid dynamical characterization and the fundamental behavior of vapor molecules and particles in the reactor. The design of the inlet to the reactor, based on computational fluid dynamics (CFD) simulations, comprises a static mixer and a conical diffuser to facilitate development of a characteristic laminar flow profile. To assess the extent to which the actual performance adheres to the theoretical CFD model, residence time distribution (RTD) experiments are reported with vapor molecules (O_3) and submicrometer ammonium sulfate particles. As confirmed by the CFD prediction, the presence of a slight deviation from strictly isothermal conditions leads to secondary flows in the reactor that produce deviations from the ideal parabolic laminar flow. The characterization experiments, in conjunction with theory, provide a basis for interpretation of atmospheric chemistry and SOA studies to follow. A 1-D photochemical model within an axially dispersed plug flow reactor (AD-PFR) framework is formulated to evaluate the oxidation level in the reactor. The simulation indicates that the OH concentration is uniform along the reactor, and an OH exposure (OH_(exp)) ranging from ∼ 10^9 to ∼ 10^(12) molecules cm^(−3) s can be achieved from photolysis of H_2O_2. A method to calculate OH_(exp) with a consideration for the axial dispersion in the present photochemical system is developed

Formation of highly oxygenated low-volatility products from cresol oxidation

Hydroxyl radical (OH) oxidation of toluene produces ring-retaining products: cresol and benzaldehyde, and ring-opening products: bicyclic intermediate compounds and epoxides. Here, first- and later-generation OH oxidation products from cresol and benzaldehyde are identified in laboratory chamber experiments. For benzaldehyde, first-generation ring-retaining products are identified, but later-generation products are not detected. For cresol, low-volatility (saturation mass concentration, C* ∼ 3.5  ×  10^4 − 7.7  ×  10^(−3) µg m^(−3)), first- and later-generation ring-retaining products are identified. Subsequent OH addition to the aromatic ring of o-cresol leads to compounds such as hydroxy, dihydroxy, and trihydroxy methyl benzoquinones and dihydroxy, trihydroxy, tetrahydroxy, and pentahydroxy toluenes. These products are detected in the gas phase by chemical ionization mass spectrometry (CIMS) and in the particle phase using offline direct analysis in real-time mass spectrometry (DART-MS). Our data suggest that the yield of trihydroxy toluene from dihydroxy toluene is substantial. While an exact yield cannot be reported as authentic standards are unavailable, we find that a yield for trihydroxy toluene from dihydroxy toluene of ∼ 0.7 (equal to the reported yield of dihydroxy toluene from o-cresol; Olariu et al., 2002) is consistent with experimental results for o-cresol oxidation under low-NO conditions. These results suggest that even though the cresol pathway accounts for only ∼ 20 % of the oxidation products of toluene, it is the source of a significant fraction (∼ 20–40 %) of toluene secondary organic aerosol (SOA) due to the formation of low-volatility products

A note on the effects of inorganic seed aerosol on the oxidation state of secondary organic aerosol-α-Pinene ozonolysis

We compare the oxidation state and molecular composition of α-pinene-derived secondary organic aerosol (SOA) by varying the types and surface areas of inorganic seed aerosol that are used to promote the condensation of SOA-forming vapors. The oxidation state of α-pinene SOA is found to increase with inorganic seed surface area, likely a result of enhanced condensation of low-volatility organic compounds on particles versus deposition on the chamber wall. α-Pinene SOA is more highly oxygenated in the presence of sodium nitrate (SN) seed than ammonium sulfate seed. The relative abundance of semivolatile monomers and low-volatility dimer components that account for more than half of α-pinene SOA mass is not significantly affected by the composition of seed aerosol. Enhanced uptake of highly oxidized small carboxylic acids onto SN seed particles is observed, which could potentially explain the observed higher SOA oxidation state in the presence of SN seed aerosol. Overall, our results demonstrate that a combined effect of seed aerosol composition and surface area leads to an increase in the O:C atomic ratio of α-pinene SOA by as much as a factor of 2

Real-Time Studies of Iron Oxalate-Mediated Oxidation of Glycolaldehyde as a Model for Photochemical Aging of Aqueous Tropospheric Aerosols

The complexation of iron (III) with oxalic acid in aqueous solution yields a strongly absorbing chromophore that undergoes efficient photodissociation to give iron (II) and the carbon dioxide anion radical. Importantly, iron (III) oxalate complexes absorb near-UV radiation (λ > 350 nm), providing a potentially powerful source of oxidants in aqueous tropospheric chemistry. Although this photochemical system has been studied extensively, the mechanistic details associated with its role in the oxidation of dissolved organic matter within aqueous aerosol remain largely unknown. This study utilizes glycolaldehyde as a model organic species to examine the oxidation pathways and evolution of organic aerosol initiated by the photodissociation of aqueous iron (III) oxalate complexes. Hanging droplets (radius 1 mm) containing iron (III), oxalic acid, glycolaldehyde, and ammonium sulfate (pH ~ 3) are exposed to irradiation at 365 nm and sampled at discrete time points utilizing field-induced droplet ionization mass spectrometry (FIDI-MS). Glycolaldehyde is found to undergo rapid oxidation to form glyoxal, glycolic acid, and glyoxylic acid, but the formation of high molecular weight oligomers is not observed. For comparison, particle-phase experiments conducted in a laboratory chamber explore the reactive uptake of gas-phase glycolaldehyde onto aqueous seed aerosol containing iron and oxalic acid. The presence of iron oxalate in seed aerosol is found to inhibit aerosol growth. These results suggest that photodissociation of iron (III) oxalate can lead to the formation of volatile oxidation products in tropospheric aqueous aerosols

A note on the effects of inorganic seed aerosol on the oxidation state of secondary organic aerosol-α-Pinene ozonolysis

We compare the oxidation state and molecular composition of α-pinene-derived secondary organic aerosol (SOA) by varying the types and surface areas of inorganic seed aerosol that are used to promote the condensation of SOA-forming vapors. The oxidation state of α-pinene SOA is found to increase with inorganic seed surface area, likely a result of enhanced condensation of low-volatility organic compounds on particles versus deposition on the chamber wall. α-Pinene SOA is more highly oxygenated in the presence of sodium nitrate (SN) seed than ammonium sulfate seed. The relative abundance of semivolatile monomers and low-volatility dimer components that account for more than half of α-pinene SOA mass is not significantly affected by the composition of seed aerosol. Enhanced uptake of highly oxidized small carboxylic acids onto SN seed particles is observed, which could potentially explain the observed higher SOA oxidation state in the presence of SN seed aerosol. Overall, our results demonstrate that a combined effect of seed aerosol composition and surface area leads to an increase in the O:C atomic ratio of α-pinene SOA by as much as a factor of 2

Harmonized human biomonitoring in European children, teenagers and adults: EU-wide exposure data of 11 chemical substance groups from the HBM4EU Aligned Studies (2014–2021)

HBM4EU is co-financed under Horizon 2020 (grant agreement No 733032).As one of the core elements of the European Human Biomonitoring Initiative (HBM4EU) a human biomonitoring (HBM) survey was conducted in 23 countries to generate EU-wide comparable HBM data. This survey has built on existing HBM capacity in Europe by aligning national or regional HBM studies, referred to as the HBM4EU Aligned Studies. The HBM4EU Aligned Studies included a total of 10,795 participants from three age groups: (i) 3,576 children aged 6-12 years, (ii) 3,117 teenagers aged 12-18 years, and (iii) 4,102 young adults aged 20-39 years. The participants were recruited between 2014 and 2021 in 11-12 countries per age group, geographically distributed across Europe. Depending on the age group, internal exposure to phthalates and the substitute DINCH, halogenated and organophosphorus flame retardants, per- and polyfluoroalkyl substances (PFASs), cadmium, bisphenols, polycyclic aromatic hydrocarbons (PAHs), arsenic species, acrylamide, mycotoxins (deoxynivalenol (total DON)), benzophenones and selected pesticides was assessed by measuring substance specific biomarkers subjected to stringent quality control programs for chemical analysis. For substance groups analyzed in different age groups higher average exposure levels were observed in the youngest age group, i.e., phthalates/DINCH in children versus teenagers, acrylamide and pesticides in children versus adults, and benzophenones in teenagers versus adults. Many biomarkers in teenagers and adults varied significantly according to educational attainment, with higher exposure levels of bisphenols, phthalates, benzophenones, PAHs, and acrylamide in participants (from households) with lower educational attainment, while teenagers from households with higher educational attainment have higher exposure levels for PFASs and arsenic. In children, a social gradient was only observed for the non-specific pyrethroid metabolite 3-PBA and di-isodecyl phthalate (DiDP), with higher levels in children from households with higher educational attainment. Geographical variations were seen for all exposure biomarkers. For 15 biomarkers, the available health-based HBM guidance values were exceeded with the highest exceedance rates for toxicologically relevant arsenic in teenagers (40%), 3-PBA in children (36%), and between 11 and 14% for total DON, Σ (PFOA + PFNA + PFHxS + PFOS), bisphenol S and cadmium. The infrastructure and harmonized approach succeeded in obtaining comparable European-wide internal exposure data for a prioritized set of 11 chemical groups. These data serve as a reference for comparison at the global level, provide a baseline to compare the efficacy of the European Commission's chemical strategy for sustainability, and will give leverage to national policymakers for the implementation of targeted measures.info:eu-repo/semantics/publishedVersio