1. |
- Guo, Y., et al.
(författare)
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Reversible Structural Isomerization of Nature's Water Oxidation Catalyst Prior to O-O Bond Formation
- 2022
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 144:26, s. 11736-11747
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Tidskriftsartikel (refereegranskat)abstract
- Photosynthetic water oxidation is catalyzed by a manganese-calcium oxide cluster, which experiences five "S-states" during a light-driven reaction cycle. The unique "distorted chair"-like geometry of the Mn4CaO5(6)cluster shows structural flexibility that has been frequently proposed to involve "open" and "closed"-cubane forms from the S1 to S3states. The isomers are interconvertible in the S1 and S2states, while in the S3state, the open-cubane structure is observed to dominate inThermosynechococcus elongatus (cyanobacteria) samples. In this work, using density functional theory calculations, we go beyond the S3+Yzstate to the S3nYz•→ S4+Yzstep, and report for the first time that the reversible isomerism, which is suppressed in the S3+Yzstate, is fully recovered in the ensuing S3nYz•state due to the proton release from a manganese-bound water ligand. The altered coordination strength of the manganese-ligand facilitates formation of the closed-cubane form, in a dynamic equilibrium with the open-cubane form. This tautomerism immediately preceding dioxygen formation may constitute the rate limiting step for O2formation, and exert a significant influence on the water oxidation mechanism in photosystem II.
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2. |
- Le Breton, Michael, 1986, et al.
(författare)
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Chlorine oxidation of VOCs at a semi-rural site in Beijing: significant chlorine liberation from ClNO2 and subsequent gas- and particle-phase Cl-VOC production
- 2018
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18:17, s. 13013-13030:18, s. 13013-13030
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Tidskriftsartikel (refereegranskat)abstract
- Nitryl chloride (ClNO2) accumulation at night acts as a significant reservoir for active chlorine and impacts the following day's photochemistry when the chlorine atom is liberated at sunrise. Here, we report simultaneous measurements of N2O5 and a suite of inorganic halogens including ClNO2 and reactions of chloride with volatile organic compounds (Cl-VOCs) in the gas and particle phases utilising the Filter Inlet for Gas and AEROsols time-of-flight chemical ionisation mass spectrometer (FIGAERO-ToF-CIMS) during an intensive measurement campaign 40 km northwest of Beijing in May and June 2016. A maximum mixing ratio of 2900 ppt of ClNO2 was observed with a mean campaign nighttime mixing ratio of 487 ppt, appearing to have an anthropogenic source supported by correlation with SO2, CO and benzene, which often persisted at high levels after sunrise until midday. This was attributed to such high mixing ratios persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3 x 10(5) molecules cm(-3) from ClNO2 alone, peaking at 09:30 LT and up to 8.4 x 10(5) molecules cm(-3) when including the supporting inorganic halogen measurements. Cl-VOCs were observed in the particle and gas phases for the first time at high time resolution and illustrate how the iodide ToF-CIMS can detect unique markers of chlorine atom chemistry in ambient air from both biogenic and anthropogenic sources. Their presence and abundance can be explained via time series of their measured and steady-state calculated precursors, enabling the assessment of competing OH and chlorine atom oxidation via measurements of products from both of these mechanisms and their relative contribution to secondary organic aerosol (SOA) formation.
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3. |
- Li, J. J., et al.
(författare)
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Characterization of Aerosol Aging Potentials at Suburban Sites in Northern and Southern China Utilizing a Potential Aerosol Mass (Go:PAM) Reactor and an Aerosol Mass Spectrometer
- 2019
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Ingår i: Journal of Geophysical Research-Atmospheres. - : American Geophysical Union (AGU). - 2169-897X .- 2169-8996. ; 124:10, s. 5629-5649
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Tidskriftsartikel (refereegranskat)abstract
- Aerosol mass spectrometry was used to characterize submicron aerosols before and after aging in a Gothenburg Potential Aerosol Mass (Go:PAM) reactor at two suburban sites in China, one in northern China at Changping (CP), Beijing, and a second in southern China at Hong Kong (HK). Organic aerosol (OA) dominated in the ambient nonrefractory particulate matter <1m (NR-PM1) for both CP (42-71%) and HK (43-61%), with a large contribution from secondary OA factors that were semivolatile oxygenated (SVOOA) and low-volatility oxygenated (LVOOA). Under constant OH exposure, OA enhancement (78-98%) dominated the NR-PM1 mass increment at both sites, while nitrate was enhanced the most among the inorganic species (7-9%). Overall, the CP site exhibited higher OA oxidation potential and more enhancement of SVOOA than LVOOA (7.5 vs. 2.7g/m(3)), but the reverse was observed in HK (0.8 vs. 2.6g/m(3)). In CP, more enhancement of the less oxygenated SVOOA suggests that aerosol aging was more sensitive to the abundant locally emitted primary OA and volatile organic compound precursors. On the contrary, the more formation of the highly oxidized LVOOA in HK indicates that aerosol aging mainly escalated the degree of oxygenation of OA as ambient aerosol was already quite aged and there was a lack of volatile organic compound precursors. The comparative measurements using the same oxidation system reveal distinct key factors and mechanisms that influence secondary aerosol formation in two suburban locations in China, providing scientific insights to assist formulation of location-specific mitigation measures of secondary pollution. Plain Language Summary Atmospheric submicron particles have significant impacts on the climate and human health. A large part of these particles are formed secondarily through successive aging of primary emissions. To study such aging processes, we used a reactor that can provide highly oxidizing conditions to simulate the oxidation of ambient aerosols at accelerated rates. An online mass spectrometer was connected after the reactor to measure changes in aerosol mass concentration and chemical composition between the ambient samples and the oxidized ones. We presented the first comparative measurements of the aging potentials of ambient aerosols in two suburban sites in northern and southern China (Changping District in Beijing, and Hong Kong). Results showed that generally aerosols at the Changping site had higher aging potentials after passing through the oxidation reactor, probably due to more local emissions of precursors, while air masses in Hong Kong were already in a higher oxidation state with lower aging potentials, mainly because of strong impacts from long-range transported pollution sources. Distinct aerosol aging pathways related to different ambient precursors were observed at the two sites. Understanding of the different characteristics of aerosol aging processes can lead to advances in air quality modeling and pollution management.
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4. |
- Guo, Y. D., et al.
(författare)
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Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical
- 2022
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 22:17, s. 11323-11346
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Tidskriftsartikel (refereegranskat)abstract
- Nighttime NO3-initiated oxidation of biogenic volatile organic compounds (BVOCs) such as monoterpenes is important for the atmospheric formation and growth of secondary organic aerosol (SOA), which has significant impact on climate, air quality, and human health. In such SOA formation and growth, highly oxygenated organic molecules (HOM) may be crucial, but their formation pathways and role in aerosol formation have yet to be clarified. Among monoterpenes, limonene is of particular interest for its high emission globally and high SOA yield. In this work, HOM formation in the reaction of limonene with nitrate radical (NO3) was investigated in the SAPHIR chamber (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). About 280 HOM products were identified, grouped into 19 monomer families, 11 dimer families, and 3 trimer families. Both closed-shell products and open-shell peroxy radicals (RO2 center dot) 2 were observed, and many of them have not been reported previously. Monomers and dimers accounted for 47% and 47% of HOM concentrations, respectively, with trimers making up the remaining 6 %. In the most abundant monomer families, C10H15-17NO6-14, carbonyl products outnumbered hydroxyl products, indicating the importance of RO2 center dot termination by unimolecular dissociation. Both RO2 center dot autoxidation and alkoxy-peroxy pathways were found to be important processes leading to HOM. Time-dependent concentration profiles of monomer products containing nitrogen showed mainly second-generation formation patterns. Dimers were likely formed via the accretion reaction of two monomer RO2 center dot , and HOM-trimers via the accretion reaction between monomer RO2 center dot and dimer RO2 center dot. Trimers are suggested to play an important role in new particle formation (NPF) observed in our experiment. A HOM yield of 1.5%(+1.7%)(-0.7%) was estimated considering only first-generation products. SOA mass growth could be reasonably explained by HOM condensation on particles assuming irreversible uptake of ultra-low volatility organic compounds (ULVOCs), extremely low volatility organic compounds (ELVOCs), and low volatility organic compounds (LVOCs). This work provides evidence for the important role of HOM formed via the limonene +NO3 reaction in NPF and growth of SOA particles.
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5. |
- Le Breton, Michael, 1986, et al.
(författare)
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Online gas- and particle-phase measurements of organosulfates, organosulfonates and nitrooxy organosulfates in Beijing utilizing a FIGAERO ToF-CIMS
- 2018
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18:14, s. 10355-10371
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Tidskriftsartikel (refereegranskat)abstract
- A time-of-flight chemical ionization mass spectrometer (CIMS) utilizing the Filter Inlet for Gas and Aerosol (FIGAERO) was deployed at a regional site 40 km north-west of Beijing and successfully identified and measured 17 sulfur-containing organics (SCOs are organo/nitrooxy organosulfates and sulfonates) with biogenic and anthropogenic precursors. The SCOs were quantified using laboratory-synthesized standards of lactic acid sulfate and nitrophenol organosulfate (NP OS). The variation in field observations was confirmed by comparison to offline measurement techniques (orbitrap and high-performance liquid chromatography, HPLC) using daily averages. The mean total (of the 17 identified by CIMS) SCO particle mass concentration was 210 +/- 110 ng m(-3) and had a maximum of 540 ng m(-3), although it contributed to only 2 +/- 1% of the organic aerosol (OA). The CIMS identified a persistent gas-phase presence of SCOs in the ambient air, which was further supported by separate vapour-pressure measurements of NP OS by a Knudsen Effusion Mass Spectrometer (KEMS). An increase in relative humidity (RH) promoted partitioning of SCO to the particle phase, whereas higher temperatures favoured higher gas-phase concentrations. Biogenic emissions contributed to only 19% of total SCOs measured in this study. Here, C10H16NSO7, a monoterpene-derived SCO, represented the highest fraction (10 %) followed by an isoprene-derived SCO. The anthropogenic SCOs with polycyclic aromatic hydrocarbon (PAH) and aromatic precursors dominated the SCO mass loading (51 %) with C11H11SO7, derived from methyl naphthalene oxidation, contributing to 40 ng m(-3) and 0.3% of the OA mass. Anthropogenic-related SCOs correlated well with benzene, although their abundance depended highly on the photochemical age of the air mass, tracked using the ratio between pinonic acid and its oxidation product, acting as a qualitative photochemical clock. In addition to typical anthropogenic and biogenic precursors the biomass-burning precursor nitrophenol (NP) provided a significant level of NP OS. It must be noted that the contribution analysis here is only representative of the detected SCOs. There are likely to be many more SCOs present which the CIMS has not identified. Gas- and particle-phase measurements of glycolic acid suggest that partitioning towards the particle phase promotes glycolic acid sulfate production, contrary to the current formation mechanism suggested in the literature. Furthermore, the HSO4 center dot H2SO4- cluster measured by the CIMS was utilized as a qualitative marker for acidity and indicates that the production of total SCOs is efficient in highly acidic aerosols with high SO42- and organic content. This dependency becomes more complex when observing individual SCOs due to variability of specific VOC precursors.
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6. |
- Mohr, Claudia, et al.
(författare)
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Molecular identification of organic vapors driving atmospheric nanoparticle growth
- 2019
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Ingår i: Nature communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- Particles formed in the atmosphere via nucleation provide about half the number of atmospheric cloud condensation nuclei, but in many locations, this process is limited by the growth of the newly formed particles. That growth is often via condensation of organic vapors. Identification of these vapors and their sources is thus fundamental for simulating changes to aerosol-cloud interactions, which are one of the most uncertain aspects of anthropogenic climate forcing. Here we present direct molecular-level observations of a distribution of organic vapors in a forested environment that can explain simultaneously observed atmospheric nanoparticle growth from 3 to 50nm. Furthermore, the volatility distribution of these vapors is sufficient to explain nanoparticle growth without invoking particle-phase processes. The agreement between observed mass growth, and the growth predicted from the observed mass of condensing vapors in a forested environment thus represents an important step forward in the characterization of atmospheric particle growth.
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7. |
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8. |
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9. |
- Wang, Y. J., et al.
(författare)
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The formation of nitro-aromatic compounds under high NOx and anthropogenic VOC conditions in urban Beijing, China
- 2019
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:11, s. 7649-7665
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Tidskriftsartikel (refereegranskat)abstract
- Nitro-aromatic compounds (NACs), as important contributors to the light absorption by brown carbon, have been widely observed in various ambient atmospheres; however, their formation in the urban atmosphere was little studied. In this work, we report an intensive field study of NACs in summer 2016 at an urban Beijing site, characterized by both high-NO(x)and anthropogenic VOC dominated conditions. We investigated the factors that influence NAC formation (e.g., NO2, VOC precursors, RH and photolysis) through quantification of eight NACs, along with major components in fine particulate matter, selected volatile organic compounds, and gases. The average total concentration of the quantified NACs was 6.63 ng m(-3), higher than those reported in other summertime studies (0.14-6.44 ng m(-3)). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC, 28.5 %) were the top two most abundant NACs, followed by methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP), and dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the presence of NOx was found to be a more dominant source of NACs than primary biomass burning emissions. The NO2 concentration level was found to be an important factor influencing the secondary formation of NACs. A transition from low- to high-NOx regimes coincided with a shift from organic- to inorganic-dominated oxidation products. The transition thresholds were NO2 similar to 20 ppb for daytime and NO2 similar to 25 ppb for nighttime conditions. Under low-NOx conditions, NACs increased with NO2, while the NO3 concentrations and (NO3-)/NACs ratios were lower, implying organic-dominated products. Under high-NOx conditions, NAC concentrations did not further increase with NO2, while the NO3- concentrations and (NO3-)/NACs ratios showed increasing trends, signaling a shift from organic- to inorganic-dominated products. Nighttime enhancements were observed for 3M4NC and 4M5NC, while daytime enhancements were noted for 4NP, 2M4NP, and DMNP, indicating different formation pathways for these two groups of NACs. Our analysis suggested that the aqueous-phase oxidation was likely the major formation pathway of 4M5NC and 3M5NC, while photo-oxidation of toluene and benzene in the presence of NO2 could be more important for the formation of nitrophenol and its derivatives. Using the (3M4NC+4M5NC) / 4NP ratios as an indicator of the relative contribution of aqueous-phase and gas-phase oxidation pathways to NAC formation, we observed that the relative contribution of aqueous-phase pathways increased at elevated ambient RH and remained constant at RH > 30 %. We also found that the concentrations of VOC precursors (e.g., toluene and benzene) and aerosol surface area acted as important factors in promoting NAC formation, and photolysis as an important loss pathway for nitrophenols.
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10. |
- Salvador, Christian Mark, 1989, et al.
(författare)
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Indoor ozone/human chemistry and ventilation strategies
- 2019
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Ingår i: Indoor Air. - : Hindawi Limited. - 1600-0668 .- 0905-6947. ; 29:6, s. 913-925
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Tidskriftsartikel (refereegranskat)abstract
- This study aimed to better understand and quantify the influence of ventilation strategies on occupant-related indoor air chemistry. The oxidation of human skin oil constituents was studied in a continuously ventilated climate chamber at two air exchange rates (1 h-1 and 3 h-1 ) and two initial ozone mixing ratios (30 and 60 ppb). Additional measurements were performed to investigate the effect of intermittent ventilation ("off" followed by "on"). Soiled t-shirts were used to simulate the presence of occupants. A time-of-flight-chemical ionization mass spectrometer (ToF-CIMS) in positive mode using protonated water clusters was used to measure the oxygenated reaction products geranyl acetone, 6-methyl-5-hepten-2-one (6-MHO) and 4-oxopentanal (4-OPA). The measurement data were used in a series of mass balance models accounting for formation and removal processes. Reactions of ozone with squalene occurring on the surface of the t-shirts are mass transport limited; ventilation rate has only a small effect on this surface chemistry. Ozone-squalene reactions on the t-shirts produced gas-phase geranyl acetone, which was subsequently removed almost equally by ventilation and further reaction with ozone. About 70% of gas-phase 6-MHO was produced in surface reactions on the t-shirts, the remainder in secondary gas-phase reactions of ozone with geranyl acetone. 6-MHO was primarily removed by ventilation, while further reaction with ozone was responsible for about a third of its removal. 4-OPA was formed primarily on the surfaces of the shirts (~60%); gas-phase reactions of ozone with geranyl acetone and 6-MHO accounted for ~30% and ~10%, respectively. 4-OPA was removed entirely by ventilation. The results from the intermittent ventilation scenarios showed delayed formation of the reaction products and lower product concentrations compared to continuous ventilation.
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11. |
- Voliotis, A., et al.
(författare)
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Chamber investigation of the formation and transformation of secondary organic aerosol in mixtures of biogenic and anthropogenic volatile organic compounds
- 2022
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 22:21, s. 14147-14175
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Tidskriftsartikel (refereegranskat)abstract
- A comprehensive chamber investigation of photochemical secondary organic aerosol (SOA) formation and transformation in mixtures of anthropogenic (o-cresol) and biogenic (alpha-pinene and isoprene) volatile organic compound (VOC) precursors in the presence of NOx and inorganic seed particles was conducted. To enable direct comparison across systems, the initial concentration (hence reactivity) of the systems towards the dominant OH oxidant was adjusted. Comparing experiments conducted in single-precursor systems at various initial reactivity levels (referenced to a nominal base case VOC concentration, e.g. halving the initial concentration for a 1/2 initial reactivity experiment) as well as their binary and ternary mixtures, we show that the molecular interactions from the mixing of the precursors can be investigated and discuss challenges in their interpretation. The observed average SOA particle mass yields (the organic particle mass produced for a mass of VOC consumed) in descending order were found for the following systems: alpha-pinene (32 +/- 7 %), alpha-pinene-o-cresol (28 +/- 9 %), alpha-pinene at 1/2 initial reactivity (21 +/- 5 %), alpha-pinene-isoprene (16 +/- 1 %), alpha-pinene at 1/3 initial reactivity (15 +/- 4 %), o-cresol (13 +/- 3 %), alpha-pinene-o-cresol-isoprene (11 +/- 4 %), o-cresol at 1/2 initial reactivity (11 +/- 3 %), o-cresol-isoprene (6 +/- 2 %), and isoprene (0 +/- 0 %). We find a clear suppression of the SOA mass yield from alpha-pinene when it is mixed with isoprene, whilst no suppression or enhancement of SOA particle yield from o-cresol was found when it was similarly mixed with isoprene. The alpha-pinene-o-cresol system yield appeared to be increased compared to that calculated based on the additivity, whilst in the alpha-pinene-o-cresol-isoprene system the measured and predicted yields were comparable. However, in mixtures in which more than one precursor contributes to the SOA particle mass it is unclear whether changes in the SOA formation potential are attributable to physical or chemical interactions, since the reference basis for the comparison is complex. Online and offline chemical composition as well as SOA particle volatility, water uptake, and "phase" behaviour measurements that were used to interpret the SOA formation and behaviour are introduced and detailed elsewhere.
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12. |
- Wu, R. R., et al.
(författare)
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Molecular composition and volatility of multi-generation products formed from isoprene oxidation by nitrate radical
- 2021
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 21:13, s. 10799-10824
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Tidskriftsartikel (refereegranskat)abstract
- Isoprene oxidation by nitrate radical (NO3) is a potentially important source of secondary organic aerosol (SOA). It is suggested that the second or later-generation products are the more substantial contributors to SOA. However, there are few studies investigating the multi-generation chemistry of isoprene-NO3 reaction, and information about the volatility of different isoprene nitrates, which is essential to evaluate their potential to form SOA and determine their atmospheric fate, is rare. In this work, we studied the reaction between isoprene and NO3 in the SAPHIR chamber (Julich) under near-atmospheric conditions. Various oxidation products were measured by a high-resolution time-offlight chemical ionization mass spectrometer using Br as the reagent ion. Most of the products detected are organic nitrates, and they are grouped into monomers (C-4 and C-5 products) and dimers (C-10 products) with 1-3 nitrate groups according to their chemical composition. Most of the observed products match expected termination products observed in previous studies, but some compounds such as monomers and dimers with three nitrogen atoms were rarely reported in the literature as gas-phase products from isoprene oxidation by NO3. Possible formation mechanisms for these compounds are proposed. The multi-generation chemistry of isoprene and NO3 is characterized by taking advantage of the time behavior of different products. In addition, the vapor pressures of diverse isoprene nitrates are calculated by different parametrization methods. An estimation of the vapor pressure is also derived from their condensation behavior. According to our results, isoprene monomers belong to intermediate-volatility or semi-volatile organic compounds and thus have little effect on SOA formation. In contrast, the dimers are expected to have low or extremely low volatility, indicating that they are potentially substantial contributors to SOA. However, the monomers constitute 80% of the total explained signals on average, while the dimers contribute less than 2 %, suggesting that the contribution of isoprene NO3 oxidation to SOA by condensation should be low under atmospheric conditions. We expect a SOA mass yield of about 5% from the wall-loss- and dilution-corrected mass concentrations, assuming that all of the isoprene dimers in the low- or extremely low-volatility organic compound (LVOC or ELVOC) range will condense completely.
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13. |
- Hallquist, Mattias, 1969, et al.
(författare)
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Photochemical smog in China: scientific challenges and implications for air-quality policies
- 2016
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Ingår i: National Science Review. - : Oxford University Press (OUP). - 2095-5138 .- 2053-714X. ; 3:4, s. 401-403
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Tidskriftsartikel (refereegranskat)abstract
- In large areas of China severe air pollution events pose a significant threat to human health, ecosystems and climate. Current reduction of primary emissions will also affect secondary pollutants such as ozone (O3) and particulate matter (PM), but the magnitude of the effects is uncertain. Major scientific challenges are related to the formation of O3 and secondary particulate matter including Secondary Organic Aerosols (SOA). Large uncertainties also remain regarding the interactions of soot, SOA and O3 under the influence of different SO2, NOX and VOC concentrations. To improve the understanding of these secondary atmospheric interactions in China, scientific areas of central importance for photochemically induced air pollutants have been identified. In addition to the scientific challenges, results from research need to be synthesized across several disciplines and communicated to stakeholders affected by air pollution and to policy makers responsible for developing abatement strategies. Development of these science-policy interactions can benefit from experience gained under the UN ECE Convention on Long Range Transboundary Air Pollution (LRTAP)
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14. |
- Wang, Y. J., et al.
(författare)
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The secondary formation of organosulfates under interactions between biogenic emissions and anthropogenic pollutants in summer in Beijing
- 2018
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18:14, s. 10693-10713
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Tidskriftsartikel (refereegranskat)abstract
- Organosulfates (OSs) with ambiguous formation mechanisms are a potential source of "missing secondary organic aerosol (SOA)" in current atmospheric models. In this study, we chemically characterized OSs and nitrooxy-OSs (NOSs) formed under the influence of biogenic emissions and anthropogenic pollutants (e.g., NOx, SO42-) in summer in Beijing. An ultrahigh-resolution mass spectrometer equipped with an electrospray ionization source was applied to examine the overall molecular composition of S-containing organics. The number and intensities of S-containing organics, the majority of which could be assigned as OSs and NOSs, increased significantly during pollution episodes, which indicated their importance for SOA accumulation. To further investigate the distribution and formation of OSs and NOSs, high-performance liquid chromatography coupled with mass spectrometry was employed to quantify 10 OSs and 3 NOS species. The total concentrations of quantified OSs and NOSs were 41.4 and 13.8 ng m(-3), respectively. Glycolic acid sulfate was the most abundant species among all the quantified species, followed by monoterpene NOSs (C10H16NO7S-). The total concentration of three isoprene OSs was 14.8 ng m(-3) and the isoprene OSs formed via the HO2 channel were higher than those formed via the NO/NO2 channel. The OS concentration coincided with the increase in acidic sulfate aerosols, aerosol acidity, and liquid water content (LWC), indicating the acid-catalyzed aqueousphase formation of OSs in the presence of acidic sulfate aerosols. When sulfate dominated the accumulation of secondary inorganic aerosols (SIAs; sulfate, nitrate, and ammonium; SO42-/SIA > 0.5), OS formation would obviously be promoted as the increasing of acidic sulfate aerosols, aerosol LWC, and acidity (pH < 2.8). Otherwise, acid-catalyzed OS formation would be limited by lower aerosol acidity when nitrate dominated the SIA accumulation. The nighttime enhancement of monoterpene NOSs suggested their formation via the nighttime NO3-initiated oxidation of monoterpene under high-NOx conditions. However, isoprene NOSs are presumed to form via acid-catalyzed chemistry or reactive uptake of oxidation products of isoprene. This study provides direct observational evidence and highlights the secondary formation of OSs and NOSs via the interaction between biogenic precursors and anthropogenic pollutants (NOx, SO2, and SO42-). The results imply that future reduction in anthropogenic emissions can help to reduce the biogenic SOA burden in Beijing or other areas impacted by both biogenic emissions and anthropogenic pollutants.
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15. |
- Maurina Morais, Eduardo, 1989, et al.
(författare)
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Solvent-free synthesis of protic ionic liquids. Synthesis, characterization and computational studies of triazolium based ionic liquids
- 2022
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Ingår i: Journal of Molecular Liquids. - : Elsevier BV. - 0167-7322. ; 360
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Tidskriftsartikel (refereegranskat)abstract
- A series of triazolium and imidazolium based protic ionic liquids were synthesized using a solvent-free method designed to address several limitations encountered with other commonly used methods. Using this method, pure (98–99% m/m) and dry (128–553 ppm of water) protic ionic liquids were synthesized (in a laboratory scale) without the need for purification methods that require heating the ionic liquid, hence avoiding the common issue of thermal decomposition. This method was also designed to allow for the accurate measurement of acid and base, and for the controlled mixing of both compounds, which is essential to avoid producing impure protic ionic liquids with excess of either acid or base. The system is constructed of only glass and chemically resistant polymer (PTFE and PVDF) parts, which avoid other contaminants that can result from unwanted reactions involving the reagents with common laboratory tools (metallic objects, paper, plastic, etc.). This process is described in detail in the paper as well as in a video. The resulting ionic liquids were carefully analyzed by spectroscopic and thermal methods designed to avoid water absorption, which is known to affect their properties. To complement this experimental characterization, computational chemistry tools were used to assess the ionic liquids’ properties, as well as to assign vibrational modes.
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16. |
- Sauer, Christopher, 1993
(författare)
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Green Aromatics: Catalytic Valorisation of bio-derived 2,5-dimethylfuran over Zeolites and Zeotypes
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis discusses the use of biomass as a potentially green feedstock for the chemical industry in the urgent shift away from fossil resources. I elaborate on reasons why we cannot afford to burn virgin biomass for energy production, among them a variety of ecosystem services that forests and other lands provide. In addition, the utilisation of biomass should be focused on products that sequester and lock away carbon for more extended periods, e.g. timber, materials and chemicals. In particular, biomass can be used as an alternative "carbon neutral" feedstock for the chemical industry, where we can preserve the already existing chemical complexity in the bio-based molecules. One example is the upgrading of furans to benzene, toluene and xylene (BTX) aromatics with the help of zeolite catalysis. These aromatics are important commodity chemicals, where the shift to a bio-based resource could make use of already existing knowledge, catalyst and production infrastructure. However, research is necessary to understand these new feedstock molecules and their interaction with the catalysts and to enable the design of applicable catalysts. In order to study the interaction of the furans, in particular 2,5-dimethylfuran (2,5-dmf), I describe and discuss the development of an analytical methodology that utilises infrared spectroscopy and mass spectrometry for the on-line identification and quantification of product molecules during catalytic reactions. This on-line analysis method is then applied to the catalytic conversion of 2,5-dmf to aromatics over a range of zeolite and zeotype catalysts. In-depth studies with ammonia as a probe molecule of the catalytic active acid sites, as well as temperature programmed experiments with ammonia and 2,5-dmf give insights into product distribution, selectivity changes and deactivation of the catalyst. For example, olefins and aromatics are initially preferred products, while with increasing time on stream, the isomerisation of 2,5-dmf becomes dominant. The incorporation of Ga into the zeotype framework, resulting in a Ga-Silicate, shows how targeted catalyst design can increase overall aromatics production. This catalyst is also suitable for selective isomerisation of 2,5-dmf to 2,4-dimethylfuran, which has a rare substitution pattern. Finally, itwas found that the most valuable of BTX, p -xylene, can be produced more selectively when 2,5-dmf is pre-adsorbed onto zeolite ZSM-5 and then released during a temperature programmed product desorption.
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17. |
- Bannan, T. J., et al.
(författare)
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A method for extracting calibrated volatility information from the FIGAERO-HR-ToF-CIMS and its experimental application
- 2019
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Ingår i: Atmospheric Measurement Techniques. - : Copernicus GmbH. - 1867-1381 .- 1867-8548. ; 12:3, s. 1429-1439
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Tidskriftsartikel (refereegranskat)abstract
- The Filter Inlet for Gases and AEROsols (FIGAERO) is an inlet specifically designed to be coupled with the Aerodyne High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS). The FIGAERO-HR-ToF-CIMS provides simultaneous molecular information relating to both the gas- and particle-phase samples and has been used to extract vapour pressures (VPs) of the compounds desorbing from the filter whilst giving quantitative concentrations in the particle phase. However, such extraction of vapour pressures of the measured particle-phase components requires use of appropriate, well-defined, reference compounds. Vapour pressures for the homologous series of polyethylene glycols (PEG) ((H-(O-CH 2 CH 2 ) n -OH) for n = 3 to n = 8), covering a range of vapour pressures (VP) (10 -1 to 10 -7 Pa) that are atmospherically relevant, have been shown to be reproduced well by a range of different techniques, including Knudsen Effusion Mass Spectrometry (KEMS). This is the first homologous series of compounds for which a number of vapour pressure measurement techniques have been found to be in agreement, indicating the utility as a calibration standard, providing an ideal set of benchmark compounds for accurate characterization of the FIGAERO for extracting vapour pressure of measured compounds in chambers and the real atmosphere. To demonstrate this, single-component and mixture vapour pressure measurements are made using two FIGAERO-HR-ToF-CIMS instruments based on a new calibration determined from the PEG series. VP values extracted from both instruments agree well with those measured by KEMS and reported values from literature, validating this approach for extracting VP data from the FIGAERO. This method is then applied to chamber measurements, and the vapour pressures of known products are estimated. © 2019 Author(s).
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18. |
- Le Breton, Michael, 1986, et al.
(författare)
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Application of a FIGAERO ToF CIMS for on-line characterization of real-world fresh and aged particle emissions from buses
- 2019
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Ingår i: Aerosol Science and Technology. - : Informa UK Limited. - 0278-6826 .- 1521-7388. ; 53:3, s. 244-259
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Tidskriftsartikel (refereegranskat)abstract
- © 2019, © 2019 The Author(s). Published with license by Taylor & Francis Group, LLC. On-line chemical characterization of real-world particle emissions from 13 transit buses was performed using a chemical ionization mass spectrometer (CIMS) equipped with a filter inlet for gases and aerosols (FIGAERO). In addition to the fresh emissions the emissions were artificially aged using a potential aerosol mass reactor (Go:PAM). The buses studied were running on different fuel types (diesel, compressed natural gas, and rapeseed methyl ester) and exhaust after-treatment systems (selective catalytic reduction (SCR), exhaust gas recirculation (EGR), and a three-way catalyst). When evaluating emissions from passing exhaust plumes using the FIGAERO ToF-CIMS, two technical features were highlighted from this work, the use of high mass calibrants and the factor enhancement method to be able to filter important compounds from mass spectra including hundreds of species. Here, acetate was used as the reagent ion to enable detection of highly oxygenated species in the exhaust particle emissions with potential high toxicity and/or secondary organic aerosol formation (SOA) potential. The acetate ionization scheme accounted for 4% to 46% of the total emitted particulate mass through identification of 61 species in the spectra. For aged emission the various fuel types provided overlapping species that could explain up to 19% of the aged emissions. This is hypothesized to come from the oxidation of engine lubrication oil, thus a common source for various fuels which was further supported by laboratory measurements. Specific markers from the SCR technology, such as urea oxidation products and further byproducts from hydrolysis were identified and attributed to reactions of isocyanic acid.
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19. |
- Salvador, Christian Mark, 1989, et al.
(författare)
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Ambient nitro-aromatic compounds - biomass burning versus secondary formation in rural China
- 2021
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 21:3, s. 1389-1406
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Tidskriftsartikel (refereegranskat)abstract
- Nitro-aromatic compounds (NACs) were measured hourly at a rural site in China during wintertime to monitor the changes due to local and regional impacts of biomass burning (BB). Concurrent and continuous measurements of the concentrations of 16 NACs in the gas and particle phases were performed with a time-of-flight chemical ionization mass spectrometer (CIMS) equipped with a Filter Inlet for Gases and AEROsols (FIGAERO) unit using iodide as the reagent ion. NACs accounted for <2 % of the mass concentration of organic matter (OM) and total particulate matter (PM), but the total particle mass concentrations of these compounds can reach as high as 1000 ng m(-3) (299 ng m(-3) avg), suggesting that they may contribute significantly to the radiative forcing effects of atmospheric particles. Levels of gas-phase NACs were highest during the daytime (15:00-16:00 local time, LT), with a smaller night-time peak around 20:00LT. Box-model simulations showed that this occurred because the rate of NAC production from gas-phase sources exceeded the rate of loss, which occurred mainly via the OH reaction and to a lesser degree via photolysis. Data gathered during extended periods with high contributions from primary BB sources (resulting in 40 %-60 % increases in NAC concentrations) were used to characterize individual NACs with respect to gas-particle partitioning and the contributions of regional secondary processes (i.e. photochemical smog). On days without extensive BB, secondary formation was the dominant source of NACs, and NAC levels correlated strongly with the ambient ozone concentration. Analyses of individual NACs in the regionally aged plumes sampled on these days allowed precursors such as phenol and catechol to be linked to their NAC derivatives (i.e. nitrophenol and nitrocatechol). Correlation analysis using the high time resolution data and box-model simulation results constrained the relationships between these compounds and demonstrated the contribution of secondary formation processes. Furthermore, 13 of 16 NACS were classified according to primary or secondary formation process. Primary emission was the dominant source (accounting for 60 %-70 % of the measured concentrations) of 5 of the 16 studied NACs, but secondary formation was also a significant source. Photochemical smog thus has important effects on brown carbon levels even during wintertime periods dominated by primary air pollution in rural China.
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20. |
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21. |
- Zhao, D. F., et al.
(författare)
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Size-dependent hygroscopicity parameter (κ) and chemical composition of secondary organic cloud condensation nuclei
- 2015
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Ingår i: Geophysical Research Letters. - 1944-8007. ; 42:24
-
Tidskriftsartikel (refereegranskat)abstract
- Secondary organic aerosol components (SOA) contribute significantly to the activation of cloud condensation nuclei (CCN) in the atmosphere. The CCN activity of internally mixed submicron SOA particles is often parameterized assuming a size-independent single-hygroscopicity parameter κ. In the experiments done in a large atmospheric reactor (SAPHIR, Simulation of Atmospheric PHotochemistry In a large Reaction chamber, Jülich), we consistently observed size-dependent κ and particle composition for SOA from different precursors in the size range of 50nm–200nm. Smaller particles had higher κ and a higher degree of oxidation, although all particles were formed from the same reaction mixture. Since decreasing volatility and increasing hygroscopicity often covary with the degree of oxidation, the size dependence of composition and hence of CCN activity can be understood by enrichment of higher oxygenated, low-volatility hygroscopic compounds in smaller particles. Neglecting the size dependence of κ can lead to significant bias in the prediction of the activated fraction of particles during cloud formation.
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22. |
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23. |
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24. |
- Tsiligiannis, Epameinondas, et al.
(författare)
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Effect of NOx on 1,3,5-trimethylbenzene (TMB) oxidation product distribution and particle formation
- 2019
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Ingår i: Atmospheric Chemistry And Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:23, s. 15073-15086
-
Tidskriftsartikel (refereegranskat)abstract
- Secondary organic aerosol (SOA) represents a significant fraction of the tropospheric aerosol and its precursors are volatile organic compounds (VOCs). Anthropogenic VOCs (AVOC) dominate the VOC budget in many urban areas with 1,3,5-trimethylbenzene (TMB) being among the most reactive aromatic AVOCs. TMB formed highly oxygenated organic molecules (HOMs) in an NOx-free environment, which could contribute to new particle formation (NPF) depending on oxidation conditions where elevated OH oxidation enhanced particle formation. The experiments were performed in an oxidation flow reactor, the Go:PAM unit, under controlled OH oxidation conditions. By addition of NOx to the system we investigated the effect of NOx on particle formation and on the product distribution. We show that the formation of HOMs, and especially HOM accretion products, strongly varies with NOx conditions. We observe a suppression of HOM and particle formation with increasing NOx/ΔTMB ratio and an increase in the formation of organonitrates (ONs) mostly at the expense of HOM accretion products. We propose reaction mechanisms and pathways that explain the formation and observed product distributions with respect to oxidation conditions. We hypothesise that, based on our findings from TMB oxidation studies, aromatic AVOCs may not contribute significantly to NPF under typical NOx/AVOC conditions found in urban atmospheres.
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25. |
- Sun, Bing, et al.
(författare)
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Ion transport in polycarbonate based solid polymer electrolytes : experimental and computational investigations
- 2016
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 18:14, s. 9504-9513
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Tidskriftsartikel (refereegranskat)abstract
- Among the alternative host materials for solid polymer electrolytes (SPEs), polycarbonates have recently shown promising functionality in all-solid-state lithium batteries from ambient to elevated temperatures. While the computational and experimental investigations of ion conduction in conventional polyethers have been extensive, the ion transport in polycarbonates has been much less studied. The present work investigates the ionic transport behavior in SPEs based on poly(trimethylene carbonate) (PTMC) and its co-polymer with epsilon-caprolactone (CL) via both experimental and computational approaches. FTIR spectra indicated a preferential local coordination between Li+ and ester carbonyl oxygen atoms in the P(TMC20CL80) co-polymer SPE. Diffusion NMR revealed that the co-polymer SPE also displays higher ion mobilities than PTMC. For both systems, locally oriented polymer domains, a few hundred nanometers in size and with limited connections between them, were inferred from the NMR spin relaxation and diffusion data. Potentiostatic polarization experiments revealed notably higher cationic transference numbers in the polycarbonate based SPEs as compared to conventional polyether based SPEs. In addition, MD simulations provided atomic-scale insight into the structure-dynamics properties, including confirmation of a preferential Li+-carbonyl oxygen atom coordination, with a preference in coordination to the ester based monomers. A coupling of the Li-ion dynamics to the polymer chain dynamics was indicated by both simulations and experiments.
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26. |
- Shwan, Soran, 1984
(författare)
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Metal-exchanged zeolites for NH3-SCR applications - Activity and Deactivation studies
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Emissions of nitrogen oxides (NOX) formed during the burning process in internal combustion engines is a major contributor to global air pollutions. One effective way to reduce NOX in lean environments, i.e. oxygen excess is selective catalytic reduction with ammonia (NH3-SCR). Metal-exchanged zeolites have proven to be active as SCR catalysts, where copper and iron are the most common metals. When using metal-exchanged zeolites in exhaust aftertreatment systems, several challenges arise. Resistance towards hydrothermal deactivation and chemisorption of impurities on the active sites of the catalyst are two of the more important challenges. Temperatures between 600-700oC can be seen during regeneration of the particulate filter, which usually is placed upstream close to the SCR catalyst in the exhaust aftertreatment system, and therefore hydrothermal stability of the metal-exchanged zeolite is crucial. Furthermore, high tolerance against catalyst poisons which originate from (bio-) fuels and lubricating oils is desired, where phosphorous and potassium are among the more important poisons. In this thesis thermal and chemical deactivation of iron-exchanged zeolite BEA as SCR catalyst is experimentally studied with special focus paid on the active iron species. Based on the experimental results a kinetic model is developed to predict the decreased activity of the catalyst after deactivation. Several characterization techniques are used to evaluate and correlate structural changes in the catalyst with the decreased activity. Catalysts are prepared and characterized using BET, XPS, XRD, TPD, in-situ FTIR and UV-Vis. The catalytic performance of the samples is measured using a flow-reactor system.It is concluded that the hydrothermal deactivation of Fe-BEA is a result of migration of isolated iron species forming iron cluster inside the zeolite pores and iron particles located on the external surface of the zeolite crystals. Further, it is shown that the growth of iron clusters and particles can be partially reversed by high temperature hydrogen treatment. The chemical deactivation due to phosphorous exposure is the result of formation of metaphosphates replacing hydroxyl groups on the active isolated iron species. Furthermore, the chemical deactivation of Fe-BEA by potassium is concluded to be due to exchange and loss of active isolated iron species in the zeolite forming smaller iron clusters inside the zeolite pores.A kinetic model where different iron species are included was developed based on the hydrothermal deactivation experiments and validated using phosphorous and potassium exposed samples. By fitting and fix the kinetic parameters towards a fresh sample, the decreased SCR activity can be predicted by just decreasing the number of active iron sites, representing loss of active iron species due to hydrothermal treatment and poisoning.The effect of gas atmosphere during solid-state ion-exchange of copper-zeolites was studied as well. It is concluded that copper becomes highly mobile due to formation of copper-ammine complexes in presence of NH3 after reduction of CuII to CuI by adding NO in the exposing gas during the solid-state ion-exchange. Copper-exchanged zeolites could be prepared by exposing physical mixtures of copper-oxides with zeolites to NO and NH3 at as low temperature as 250oC.Finally, the ammonia formation during the rich period of NOX storage and reduction (NSR) cycles was studied using kinetic modeling for the possibility of combining NSR and SCR catalysts in the exhaust aftertreatment system. It is concluded that the formation of ammonia is due to stored NOX and hydrogen from the gas in the first half of the catalyst. However, it was further concluded that the formation of ammonia is delayed due to formation of N2O from stored NOX and formed NH3.
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27. |
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28. |
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29. |
- Qiao, K., et al.
(författare)
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Size-resolved effective density of submicron particles during summertime in the rural atmosphere of Beijing, China
- 2018
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Ingår i: Journal of Environmental Sciences. - : Elsevier BV. - 1001-0742. ; 73, s. 69-77
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Tidskriftsartikel (refereegranskat)abstract
- Particle density is an important physical property of atmospheric particles. The information on high time-resolution size-resolved particle density is essential for understanding the atmospheric physical and chemical aging processes of aerosols particles. In the present study, a centrifugal particle mass analyzer (CPMA) combined with a differential mobility analyzer (DMA) was deployed to determine the size-resolved effective density of 50 to 350 nm particles at a rural site of Beijing during summer 2016. The measured particle effective densities decreased with increasing particle sizes and ranged from 1.43 to 1.55 g/cm(3), on average. The effective particle density distributions were dominated by a mode peaked at around 1.5 g/cm(3) for 50 to 350 nm particles. Extra modes with peaks at 1.0, 0.8, and 0.6 g/cm(3) for 150, 240, and 350 nm particles, which might be freshly emitted soot particles, were observed during intensive primary emissions episodes. The particle effective densities showed a diurnal variation pattern, with higher values during daytime. A case study showed that the effective density of Aitken mode particles during the new particle formation (NPF) event decreased considerably, indicating the significant contribution of organics to new particle growth. (C) 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
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30. |
- Hassellöv, Martin, 1970, et al.
(författare)
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REACH missar nano!
- 2009
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Ingår i: Miljöforskning. ; 2009:3-4
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)
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31. |
- Sznitko, L., et al.
(författare)
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Low-threshold stimulated emission from lysozyme amyloid fibrils doped with a blue laser dye
- 2015
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Ingår i: Applied Physics Letters. - : AIP Publishing. - 0003-6951 .- 1077-3118. ; 106:2
-
Tidskriftsartikel (refereegranskat)abstract
- © 2015 AIP Publishing LLC. Amyloid fibrils are excellent self-assembling nanotemplates for organic molecules such as dyes. Here, we demonstrate that laser dye-doped lysozyme type fibrils exhibit significantly reduced threshold for stimulated emission compared to that observed in usual matrices. Laser action was studied in slab planar waveguides of the amyloids doped with Stilbene 420 laser dye prepared using a film casting technique. The lowering of the threshold of stimulated emission is analyzed in the context of intrinsic structure of the amyloid nanotemplates, electrostatic interaction of different microstructures with dye molecules, as well as material properties of the cast layers. All these factors are considered to be of importance for introducing gain for random laser operation.
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32. |
- Antonsen, Simen, et al.
(författare)
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Atmospheric Chemistry of tert-butylamine and AMP
- 2017
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Ingår i: Energy Procedia. Volume 114, 2017, Pages 1026-103213th International Conference on Greenhouse Gas Control Technologies, GHGT 2016; Lausanne; Switzerland; 14 November 2016 through 18 November 2016. - : Elsevier BV. - 1876-6102.
-
Konferensbidrag (refereegranskat)abstract
- © 2017 The Authors. The atmospheric chemistry of (CH 3 ) 3 CNH 2 (tert-butylamine, tBA) and (CH 3 ) 2 (CH 2 OH)CNH 2 (2-amino-2-methyl-1-propanol, AMP) has been studied by quantum chemistry methods and in photo-oxidation experiments in the EUPHORE chamber in Valencia (Spain). Aerosol formation and composition has been quantified. Yields of nitramines and other products in the photo-oxidations have been determined and complete photo-oxidation schemes including branching between the major reaction routes have been obtained. Published by Elsevier Ltd.
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33. |
- Hammes, Julia, et al.
(författare)
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Carboxylic acids from limonene oxidation by ozone and hydroxyl radicals: insights into mechanisms derived using a FIGAERO-CIMS
- 2019
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:20, s. 13037-13052
-
Tidskriftsartikel (refereegranskat)abstract
- This work presents the results from a flow reactor study on the formation of carboxylic acids from limonene oxidation in the presence of ozone under NOx-free conditions in the dark. A High-Resolution Time-of-Flight acetate Chemical Ionisation Mass Spectrometer (HR-ToF-CIMS) was used in combination with a Filter Inlet for Gases and AEROsols (FIGAERO) to measure the carboxylic acids in the gas and particle phases. The results revealed that limonene oxidation produced large amounts of carboxylic acids which are important contributors to secondary organic aerosol (SOA) formation. The highest 10 acids contributed 56 %-91 % to the total gas-phase signal, and the dominant gas-phase species in most experiments were C8H12O4, C9H14O4, C7H10O4 and C10H16O3. The particle-phase composition was generally more complex than the gas-phase composition, and the highest 10 acids contributed 47 %-92 % to the total signal. The dominant species in the particle phase were C8H12O5, C9H14O5, C9H12O5 and C10H16O4. The measured concentration of dimers bearing at least one carboxylic acid function in the particle phase was very low, indicating that acidic dimers play a minor role in SOA formation via ozone (O-3)/hydroxyl (OH) oxidation of limonene. Based on the various experimental conditions, the acidic compositions for all experiments were modelled using descriptions from the Master Chemical Mechanism (MCM). The experiment and model provided a yield of large (C-7-C-10) carboxylic acid of the order of 10 % (2 %-23 % and 10 %-15 %, respectively). Significant concentrations of 11 acids, from a total of 16 acids, included in the MCM were measured with the CIMS. However, the model predictions were, in some cases, inconsistent with the measurement results, especially regarding the OH dependence. Reaction mechanisms are suggested to fill-in the knowledge gaps. Using the additional mechanisms proposed in this work, nearly 75 % of the observed gas-phase signal in our lowest concentration experiment (8.4 ppb converted, ca. 23 % acid yield) carried out under humid conditions can be understood.
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34. |
- Lutz, Anna, 1986, et al.
(författare)
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Gas to Particle Partitioning of Organic Acids in the Boreal Atmosphere
- 2019
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Ingår i: Acs Earth and Space Chemistry. - : American Chemical Society (ACS). - 2472-3452. ; 3:7, s. 1279-1287
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Tidskriftsartikel (refereegranskat)abstract
- Gas to particle partitioning of carboxylic acids was investigated using a high-resolution chemical ionization time-of-flight mass spectrometer (HR-CI-ToF-MS) with the filter inlet for gases and aerosol (FIGAERO). Specifically, the partitioning coefficients of 640 components with unique molecular composition were calculated from an assumed linear relationship between [particle]/[gas] versus the mass of the organic fraction (M-org) according to Raoult's law, i.e., equilibrium phase partitioning. We demonstrate that, using the full data set, most of the compounds do not follow a linear relationship. This is especially the case for low- and high-molecular-weight species. Using a subset of the data, with concurrent low sulfate ambient observations ([SO42- < 0.4 mu g m(-3)), the relationship improved significantly and K-i could be derived from the slope of a linear regression to the data. The 100 species with the highest R-2 (>= 0.7) of this regression are presented. The restrictions during high sulfate conditions can be explained by changes in either the equilibrium conditions (e.g., the activity coeffient, gamma(i)) or uptake kinetics (mass transfer limitation). This study demonstrates that partitioning of compounds in the complex ambient atmosphere follows ideal Raoult's law for some limited conditions and stresses the need for studies also in more polluted environments.
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35. |
- Maurina Morais, Eduardo, 1989
(författare)
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Synthesis of protic ionic liquids. Challenges and solutions for the synthesis of pure compounds.
- 2022
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The urgent need to diversify our energy matrix is responsible for a renewed interest in fuel cell technology, which can use hydrogen gas, a renewable green fuel, as an energy source. This technology is currently a commercially available option, however, it still requires technological improvements before it can be widely used for different applications. One way this technology could potentially be improved is by increasing its temperature range of operation by developing new, anhydrous proton conducting materials. Protic ionic liquids, which are organic salts with low melting temperatures, are interesting candidates for this application, since they can conduct protons in the operational conditions of fuel cells and without the need of water. These compounds can be synthesized by a simple acid-base neutralization reaction, but certain considerations must be taken in order to obtain high quality (dry and pure) protic ionic liquids. In this thesis, a series of triazolium and imidazolium based protic ionic liquids were synthesized using a solvent-free method designed to address several limitations encountered with other commonly used methods. Using this method, pure (98-99% m/m) and dry (128-553 ppm of water) protic ionic liquids were synthesized (in a laboratory scale) without the need for purification methods that require heating the ionic liquid, hence avoiding the common issue of thermal decomposition. This method was also designed to allow for the accurate measurement of acid and base, and for the controlled mixing of both compounds, which is essential to avoid producing impure protic ionic liquids with excess of either acid or base. The system is consists of only glass and chemically resistant polymer(PTFE and PVDF) parts, which avoids other contaminants that can result from unwanted reactions involving the reagents with common laboratory tools (metallic objects, paper, plastic, etc.). The resulting ionic liquids were carefully analyzed by spectroscopic and thermal analysis methods designed to avoid water absorption, which is known to affect their properties. To complement this experimental characterization, computational chemistry tools were used to assess the ionic liquids’ properties, as well as to assign vibrational modes.
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36. |
- Wang, Y. J., et al.
(författare)
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Comparative Study of Particulate Organosulfates in Contrasting Atmospheric Environments: Field Evidence for the Significant Influence of Anthropogenic Sulfate and NOx
- 2020
-
Ingår i: Environmental Science & Technology Letters. - : American Chemical Society (ACS). - 2328-8930. ; 7:11, s. 787-794
-
Tidskriftsartikel (refereegranskat)abstract
- Organosulfates (OSs) are an important group of secondary organic aerosols, but the key influential factors of their formation in polluted atmospheres are not well understood. In this study, we monitored particulate OSs (carboxy OSs, hydroxyacetone sulfate, and isoprene- and monoterpene-derived OSs) at an urban site and a regional site in Beijing and examined their compositions and formation pathways under contrasting atmospheric conditions. The quantified OSs were most abundant in the summer at the regional site due to higher biogenic emissions and favorable formation conditions (higher aerosol acidity and humidity), followed by urban summer and winter conditions. Larger fractions of inorganic sulfate were converted to organosulfur when sulfate was less abundant. This implies that OSs would play more important roles in aerosol properties as the decline of sulfate. Monoterpene-derived nitrooxy-OSs were enhanced via NO3 oxidation in the summer under high-NOx conditions at night, while the day-night variations in the winter were not as obvious. Among isoprene-OSs, IEPOX (isoprene epoxydiols)-OS formation was clearly suppressed under high-NOx conditions, while other isoprene-OSs that are favored under high-NOx conditions showed increasing formation with NOx. The results highlight that isoprene-OS formation pathways in polluted atmospheres could be different from the IEPOX-dominated regions reported for the low-NOx environments in the literature.
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37. |
- Zhou, L. Y., et al.
(författare)
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Emissions and Secondary Formation of Air Pollutants from Modern Heavy-Duty Trucks in Real-World Traffic-Chemical Characteristics Using On-Line Mass Spectrometry
- 2021
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 55:21, s. 14515-14525
-
Tidskriftsartikel (refereegranskat)abstract
- Complying with stricter emissions standards, a new generation of heavy-duty trucks (HDTs) has gradually increased its market share and now accounts for a large percentage of on-road mileage. The potential to improve air quality depends on an actual reduction in both emissions and subsequent formation of secondary pollutants. In this study, the emissions in real-world traffic from Euro VI-compliant HDTs were compared to those from older classes, represented by Euro V, using high-resolution time-of-flight chemical ionization mass spectrometry. Gas-phase primary emissions of several hundred species were observed for 70 HDTs. Furthermore, the particle phase and secondary pollutant formation (gas and particle phase) were evaluated for a number of HDTs. The reduction in primary emission factors (EFs) was evident (similar to 90%) and in line with a reduction of 28-97% for the typical regulated pollutants. Secondary production of most gas- and particle-phase compounds, for example, nitric acid, organic acids, and carbonyls, after photochemical aging in an oxidation flow reactor exceeded the primary emissions (EFAged/EFFresh ratio >= 2). Byproducts from urea-selective catalytic reduction systems had both primary and secondary sources. A non-negative matrix factorization analysis highlighted the issue of vehicle maintenance as a remaining concern. However, the adoption of Euro VI has a significant positive effect on emissions in real-world traffic and should be considered in, for example, urban air quality assessments.
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38. |
- McFiggans, Gordon, et al.
(författare)
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Secondary organic aerosol reduced by mixture of atmospheric vapours
- 2019
-
Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 565:7741, s. 587-593
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Tidskriftsartikel (refereegranskat)abstract
- Secondary organic aerosol contributes to the atmospheric particle burden with implications for air quality and climate. Biogenic volatile organic compounds such as terpenoids emitted from plants are important secondary organic aerosol precursors with isoprene dominating the emissions of biogenic volatile organic compounds globally. However, the particle mass from isoprene oxidation is generally modest compared to that of other terpenoids. Here we show that isoprene, carbon monoxide and methane can each suppress the instantaneous mass and the overall mass yield derived from monoterpenes in mixtures of atmospheric vapours. We find that isoprene 'scavenges' hydroxyl radicals, preventing their reaction with monoterpenes, and the resulting isoprene peroxy radicals scavenge highly oxygenated monoterpene products. These effects reduce the yield of low-volatility products that would otherwise form secondary organic aerosol. Global model calculations indicate that oxidant and product scavenging can operate effectively in the real atmosphere. Thus highly reactive compounds (such as isoprene) that produce a modest amount of aerosol are not necessarily net producers of secondary organic particle mass and their oxidation in mixtures of atmospheric vapours can suppress both particle number and mass of secondary organic aerosol. We suggest that formation mechanisms of secondary organic aerosol in the atmosphere need to be considered more realistically, accounting for mechanistic interactions between the products of oxidizing precursor molecules (as is recognized to be necessary when modelling ozone production).
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39. |
- Wang, Xuan, et al.
(författare)
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Effects of Anthropogenic Chlorine on PM2.5 and Ozone Air Quality in China
- 2020
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 54:16, s. 9908-9916
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Tidskriftsartikel (refereegranskat)abstract
- China has large anthropogenic chlorine emissions from agricultural fires, residential biofuel, waste incineration, coal combustion, and industrial processes. Here we quantify the effects of chlorine on fine particulate matter (PM2.5) and ozone air quality across China by using the GEOS-Chem chemical transport model with comprehensive anthropogenic emissions and detailed representation of gas-phase and heterogeneous chlorine chemistry. Comparison of the model to observed ClNO2, HCl, and particulate Cl- concentrations shows that reactive chlorine in China is mainly anthropogenic, unlike in other continental regions where it is mostly of marine origin. The model is successful in reproducing observed concentrations and their distributions, lending confidence in the anthropogenic chlorine emission estimates and the resulting chemistry. We find that anthropogenic chlorine emissions increase total inorganic PM2.5 by as much as 3.2 μg m-3 on an annual mean basis through the formation of ammonium chloride, partly compensated by a decrease of nitrate because ClNO2 formation competes with N2O5 hydrolysis. Annual mean MDA8 surface ozone increases by up to 1.9 ppb, mainly from ClNO2 chemistry, while reactivities of volatile organic compounds increase (by up to 48% for ethane). We find that a sufficient representation of chlorine chemistry in air quality models can be obtained from consideration of HCl/Cl- thermodynamics and ClNO2 chemistry, because other more complicated aspects of chlorine chemistry have a relatively minor effect.
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40. |
- Halldin Stenlid, Joakim, 1987-
(författare)
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Computational Studies of Chemical Interactions: Molecules, Surfaces and Copper Corrosion
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The chemical bond – a corner stone in science and a prerequisite for life – is the focus of this thesis. Fundamental and applied aspects of chemical bonding are covered including the development of new computational methods for the characterization and rationalization of chemical interactions. The thesis also covers the study of corrosion of copper-based materials. The latter is motivated by the proposed use of copper as encapsulating material for spent nuclear fuel in Sweden.In close collaboration with experimental groups, state-of-the-art computational methods were employed for the study of chemistry at the atomic scale. First, oxidation of nanoparticulate copper was examined in anoxic aqueous media in order to better understand the copper-water thermodynamics in relation to the corrosion of copper material under oxygen free conditions. With a similar ambition, the water-cuprite interface was investigated with regards to its chemical composition and reactivity. This was compared to the behavior of methanol and hydrogen sulfide at the cuprite surface.An overall ambition during the development of computational methods for the analysis of chemical bonding was to bridge the gap between molecular and materials chemistry. Theory and results are thus presented and applied in both a molecular and a solid-state framework. A new property, the local electron attachment energy, for the characterization of a compound’s local electrophilicity was introduced. Together with the surface electrostatic potential, the new property predicts and rationalizes regioselectivity and trends of molecular reactions, and interactions on metal and oxide nanoparticles and extended surfaces.Detailed atomistic understanding of chemical processes is a prerequisite for the efficient development of chemistry. We therefore envisage that the results of this thesis will find widespread use in areas such as heterogeneous catalysis, drug discovery, and nanotechnology.
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41. |
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42. |
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43. |
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44. |
- Farewell, Anne, 1961
(författare)
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Rising to the Top: Promoting Deeper Learning in the Laboratory
- 2018
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Ingår i: National Center for Case Study Teaching in Science.
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Bokkapitel (refereegranskat)abstract
- Inquiry-based labs differ from cookbook labs in that inquiry-based labs contain an element of experimentation. A cookbook lab can be performed by a student without understanding any of the theory connected with the exercise whereas inquiry-based labs require a degree of conceptual knowledge for a student to perform the lab. Inquiry-based labs also strengthen and deepen students understanding of topics discussed in lectures or reading assignments. There are many variations and degrees of inquiry in these labs ranging from a lab that is entirely designed by the students to those that include small questions requiring that the students predict the outcomes of a lab or fill in missing information (guided inquiry). A simple specific example of a cookbook lab would be instructing students to measure volume changes between ice and liquid water. The students would be given step by step instructions to follow and would not need to apply any conceptual knowledge. An inquiry based lab on the same topic would allow the students to design their own experiment to discover how the volume of liquid water differs from that of ice. One goal of this activity is to introduce inquiry-based lab design. Beyond lab design, lab supervision is crucial to encouraging students to use their conceptual knowledge when doing a practical lab. Lab assistants or teachers who are involved in the lab can use student questions to encourage deeper understanding. This case study includes a role-play exercise for this skill. This case study has been designed to be used in science education courses for both graduate student laboratory assistants and lecturers or professors in natural sciences at the university or college level. It includes discussion and role-play of a hypothetical laboratory. No specific knowledge of biology or chemistry is needed beyond high school level to complete this task, though knowledge of the existence of microorganisms (yeast) and proteins is assumed. In addition, this activity is suitable for participants with little or no pedagogics training.
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45. |
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46. |
- Kolavali, Reddysuresh, 1983, et al.
(författare)
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The sorption of monovalent cations onto wood flour and holocelluloses of Norway spruce: molecular interactions during LiCl impregnation
- 2017
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Ingår i: Holzforschung. - : Walter de Gruyter GmbH. - 1437-434X .- 0018-3830. ; 71:5, s. 373-381
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Tidskriftsartikel (refereegranskat)abstract
- Active functional groups and interactions involved in the sorption of Li+ ions from an aqueous LiCl solution onto the Norway spruce sapwood (sW) flour have been investigated. To this purpose, sW was delignified by peracetic acid (PAA) treatments and the resulting holocelluloses (HC6 h, HC24 h, HC51 h, HC72 h, where the lower case data indicate the PAA treatment time) with various lignin contents were immersed in aqueous solution of LiCl and the sorption effects were studied by flame atomic emission spectroscopy (FAES), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). The Brunauer- Emmett-Teller (BET) specific surface area increased from 1.5±0.0 m2g−1 to 2.4±0.1 m2g−1 for HC6 h, and from 1.6±0.03 m2g−1 to 2.7±0.6 m2g−1 for HC72 h upon LiCl treatment. It was found that Li+/Cl− retention occurs predominantly via O-containing functionalities and the carbohydrate-rich samples sorbed more Li+. Upon LiCl treatment, the mobility and accessibility of the wood matrix was enhanced, possibly by interference of the introduced ions with the existing intermolecular bonds.
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47. |
- Emanuelsson, Eva U., et al.
(författare)
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Formation of anthropogenic secondary organic aerosol (SOA) and its influence on biogenic SOA properties
- 2013
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Ingår i: Atmos. Chem. Phys.. - : Copernicus Publications. - 1680-7324. ; 13:5, s. 2837-2855
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Tidskriftsartikel (refereegranskat)abstract
- Secondary organic aerosol (SOA) formation from mixed anthropogenic and biogenic precursors has been studied exposing reaction mixtures to natural sunlight in the SAPHIR chamber in Jülich, Germany. In this study aromatic compounds served as examples of anthropogenic volatile organic compound (VOC) and a mixture of α-pinene and limonene as an example for biogenic VOC. Several experiments with exclusively aromatic precursors were performed to establish a relationship between yield and organic aerosol mass loading for the atmospheric relevant range of aerosol loads of 0.01 to 10 μg m−3. The yields (0.5 to 9%) were comparable to previous data and further used for the detailed evaluation of the mixed biogenic and anthropogenic experiments. For the mixed experiments a number of different oxidation schemes were addressed. The reactivity, the sequence of addition, and the amount of the precursors influenced the SOA properties. Monoterpene oxidation products, including carboxylic acids and dimer esters were identified in the aged aerosol at levels comparable to ambient air. OH radicals were measured by Laser Induced Fluorescence, which allowed for establishing relations of aerosol properties and composition to the experimental OH dose. Furthermore, the OH measurements in combination with the derived yields for aromatic SOA enabled application of a simplified model to calculate the chemical turnover of the aromatic precursor and corresponding anthropogenic contribution to the mixed aerosol. The estimated anthropogenic contributions were ranging from small (≈8%) up to significant fraction (>50%) providing a suitable range to study the effect of aerosol composition on the aerosol volatility (volume fraction remaining (VFR) at 343 K: 0.86–0.94). The aromatic aerosol had higher oxygen to carbon ratio O/C and was less volatile than the biogenic fraction. However, in order to produce significant amount of aromatic SOA the reaction mixtures needed a higher OH dose that also increased O/C and provided a less volatile aerosol. The SOA yields, O/C, and f44 (the mass fraction of CO2+ ions in the mass spectra which can be considered as a measure of carboxylic groups) in the mixed photo-chemical experiments could be described as linear combinations of the corresponding properties of the pure systems. For VFR there was in addition an enhancement effect, making the mixed aerosol significantly less volatile than what could be predicted from the pure systems. A strong positive correlation was found between changes in volatility and O/C with the exception during dark hours where the SOA volatility decreased while O/C did not change significantly. Thus, this change in volatility under dark conditions as well as the anthropogenic enhancement is due to chemical or morphological changes not affecting O/C.
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48. |
- Faxon, Cameron, et al.
(författare)
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Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry
- 2018
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Ingår i: Atmospheric Chemistry And Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18, s. 5467-5481
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Tidskriftsartikel (refereegranskat)abstract
- The gas-phase nitrate radical (NO 3 • ) initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA) formation and organic nitrates may serve as a NO x reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO 3 • with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO). Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM) limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C 10 H 15 NO 6 , C 10 H 17 NO 6 , C 8 H 11 NO 6 , C 10 H 17 NO 7 , and C 9 H 13 NO 7 ) that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO 3 • produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.
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49. |
- Kourtchev, Ivan, et al.
(författare)
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Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols
- 2016
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 6
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Tidskriftsartikel (refereegranskat)abstract
- Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.
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50. |
- Lopez-Hilfiker, F. D., et al.
(författare)
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A novel method for on-line analysis of gas and particle composition: description and evaluation of a Filter Inlet for Gases and AEROsols (FIGAERO)
- 2013
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Ingår i: Atmospheric Measurement Techniques Discussions. - : Copernicus Publications. - 1867-8610. ; 6:5, s. 9347-9395
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Tidskriftsartikel (refereegranskat)abstract
- We describe a novel inlet that allows measurement of both gas and particle molecular composition when coupled to mass spectrometric, chromatographic, or optical sensors: the Filter Inlet for Gas and AEROsol (FIGAERO). The design goals for the FIGAERO are to allow unperturbed observation of ambient air while simultaneously analyzing gases and collecting particulate matter on a Teflon filter via an entirely separate sampling port. The filter is analyzed periodically by the same sensor on hourly or faster timescales using temperature-programmed thermal desorption. We assess the performance of the FIGAERO by coupling it to a high-resolution time-of-flight chemical-ionization mass spectrometer (HRToF-CIMS) in laboratory chamber studies of α-pinene oxidation and field measurements at a boreal forest location. Low instrument backgrounds give detection limits of ppt or lower for compounds in the gas-phase and in the pg m−3 range for particle phase compounds. The FIGAERO-HRToF-CIMS provides molecular information about both gases and particle composition on the 1 Hz and hourly timescales, respectively for hundreds of compounds. The FIGAERO thermal desorptions are highly reproducible (better than 10%), allowing a calibrated assessment of the effective volatility of desorbing compounds and the role of thermal decomposition during the desorption process. We show that the often multi-modal desorption thermograms arising from secondary organic aerosol (SOA) provide additional insights into molecular composition and/or particle morphology, and exhibit changes with changes in SOA formation or aging pathways.
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