Browsing by Subject "CHEMISTRY"

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  • Thelin, Eric P.; Raj, Rahul; Bellander, Bo-Michael; Nelson, David; Piippo-Karjalainen, Anna; Siironen, Jari; Tanskanen, Päivi; Hawryluk, Gregory; Hasen, Mohammed; Unger, Bertram; Zeiler, Frederick A. (2020)
    Current accepted cerebrovascular reactivity indices suffer from the need of high frequency data capture and export for post-acquisition processing. The role for minute-by-minute data in cerebrovascular reactivity monitoring remains uncertain. The goal was to explore the statistical time-series relationships between intra-cranial pressure (ICP), mean arterial pressure (MAP) and pressure reactivity index (PRx) using both 10-s and minute data update frequency in TBI. Prospective data from 31 patients from 3 centers with moderate/severe TBI and high-frequency archived physiology were reviewed. Both 10-s by 10-s and minute-by-minute mean values were derived for ICP and MAP for each patient. Similarly, PRx was derived using 30 consecutive 10-s data points, updated every minute. While long-PRx (L-PRx) was derived via similar methodology using minute-by-minute data, with L-PRx derived using various window lengths (5, 10, 20, 30, 40, and 60 min; denoted L-PRx_5, etc.). Time-series autoregressive integrative moving average (ARIMA) and vector autoregressive integrative moving average (VARIMA) models were created to analyze the relationship of these parameters over time. ARIMA modelling, Granger causality testing and VARIMA impulse response function (IRF) plotting demonstrated that similar information is carried in minute mean ICP and MAP data, compared to 10-s mean slow-wave ICP and MAP data. Shorter window L-PRx variants, such as L-PRx_5, appear to have a similar ARIMA structure, have a linear association with PRx and display moderate-to-strong correlations (r ~ 0.700, p 
  • Paasonen, Pauli; Peltola, Maija; Kontkanen, Jenni; Junninen, Heikki; Kerminen, Veli-Matti; Kulmala, Markku (2018)
    Growth of aerosol particles to sizes at which they can act as cloud condensation nuclei (CCN) is a crucial factor in estimating the current and future impacts of aerosol-cloud-climate interactions. Growth rates (GRs) are typically determined for particles with diameters (d(P)) smaller than 40 nm immediately after a regional new particle formation (NPF) event. These growth rates are often taken as representatives for the particle growth to CCN sizes (d(P) > 50-100 nm). In modelling frameworks, the concentration of the condensable vapours causing the growth is typically calculated with steady state assumptions, where the condensation sink (CS) is the only loss term for the vapours. Additionally, the growth to CCN sizes is represented with the condensation of extremely low-volatility vapours and gas-particle partitioning of semi-volatile vapours. Here, we use a novel automatic method to determine growth rates from below 10 nm to hundreds of nanometres from a 20-year-long particle size distribution (PSD) data set in boreal forest. With this method, we are able to detect growth rates also at times other than immediately after a NPF event. We show that the GR increases with an increasing oxidation rate of monoterpenes, which is closely coupled with the ambient temperature. Based on our analysis, the oxidation reactions of monoterpenes with ozone, hydroxyl radical and nitrate radical all are capable of producing vapours that contribute to the particle growth in the studied size ranges. We find that GR increases with particle diameter, resulting in up to 3-fold increases in GRs for particles with d(P) similar to 100 nm in comparison to those with d(P) similar to 10 nm. We use a single particle model to show that this increase in GR can be explained with aerosol-phase reactions, in which semi-volatile vapours form non-volatile dimers. Finally, our analysis reveals that the GR of particles with d(P) <100 nm is not limited by the condensation sink, even though the GR of larger particles is. Our findings suggest that in the boreal continental environment, the formation of CCN from NPF or sub-100 nm emissions is more effective than previously thought and that the formation of CCN is not as strongly self-limiting a process as the previous estimates have suggested.
  • Iyer, Siddharth; He, Xucheng; Hyttinen, Noora; Kurten, Theo; Rissanen, Matti P. (2017)
    The HO2 radical is an important atmospheric molecule that can potentially influence the termination of autoxidation processes of volatile organic compounds (VOCs) that lead to the formation of highly oxygenated multifunctional compounds (HOMs). In this work, we demonstrate the direct detection of the HO2 radical using an iodide-based chemical ionization mass spectrometer (iodide-CIMS). Expanding on the previously established correlation between molecule-iodide binding enthalpy and iodide-CIMS instrument sensitivity, the experimental detection of the HO2 radical was preceded by the quantum chemical calculation of the HO2*I- cluster (PBE/aug-cc-pVTZ-PP level), which showed a reasonably strong binding enthalpy of 21.60 kcal/mol. Cyclohexene ozonolysis intermediates and closed-shell products were next detected by the iodide-CIMS. The ozone-initiated cyclohexene oxidation mechanism was perturbed by the introduction of the HO2 radical, leading to the formation of closed-shell hydroperoxides. The experimental investigation once again followed the initial computational molecule-iodide binding enthalpy calculations. The quantum chemical calculations were performed at the PBE/aug-cc-pVTZ-PP level for radicals and DLPNO-CCSD(T)/def2-QZVPP//PBE/aug-cc-pVTZ-PP level for the closed-shell products. A comparison between the iodide-CIMS and nitrate-CIMS spectra with identical measurement steps revealed that the iodide-CIMS was able to detect the low-oxidized (O/C ratio 0.5 and 0.66) cyclohexene ozonolysis monomer products more efficiently than nitrate-CIMS. Higher-oxidized monomers (O/C ratio 1 to 1.5) were detected equally well by both methods. An investigation of dimers showed that both iodide- and nitrate-CIMS were able to detect the dimer compositions possibly formed from reactions between the peroxy radical monomers considered in this study. Additionally, iodide-CIMS detected organic ions that were formed by a previously suggested mechanism of dehydroxylation of peroxy acids (and deoxygenation of acyl peroxy radicals) by H2O*I- clusters. These mechanisms were computationally verified.
  • Kurten, Theo; Rissanen, Matti P.; Mackeprang, Kasper; Thornton, Joel A.; Hyttinen, Noora; Jorgensen, Solvejg; Ehn, Mikael; Kjaergaard, Henrik G. (2015)
    Autoxidation by: sequential peroxy radical hydrogen shifts (H-shifts) and O-2 additions has recently emerged as a promising mechanism for the rapid formation of highly oxidized, low-Volatility organic Compounds in the. atmosphere: A kg prerequisite for auto)ddation is that the H-shifts of the initial peroxy radicals formed by, e.g., OH or O-3 oxidation are fast enough to compete with bimolecular sink reactions. In most atmospheric conditions, these restrict the lifetime Of peroxy.radicals to be on the order of seconds. We have systematically investigated all potentially important (nonmethyl, sterically unhindered) H-shifts of all four peroxy radicals formed in the ozonolysis of alpha-pinene using density functional (omega B97XD) and coupled cluster [CCSD(T)-F12] theory. In contrast to the related but chemically simpler tyclohexene ozonolysis system, none of the calculated li-shifts have rate constants above 1 s(-1) at 298 K, and most are below 0.01 s(-1). The law rate constants are connected to the presence of the' strained tyclobutyi sing in the alpha-pinene-derived peroxy radicals, which hinders H-shifts both from and across the ring. For autoxidation to yield the experimentally observed highly oxidized products in the alpha-pinene ozonolysis system, additional ring-opening reaction mechanisms breaking the cyclobutyl ring are therefore needed. We further investigate possible uni- and bimolecular pathways for,opening the cydobutyl ring in, the alpha-pinene ozonolysis system.
  • Keshavarz, Fatemeh; Shcherbacheva, Anna; Kubecka, Jakub; Vehkamäki, Hanna; Kurten, Theo (2019)
    The effect of dust aerosols on accretion reactions of water, formaldehyde, and formic acid was studied in the conditions of earth's troposphere at the DLPNO-CCSD(T)/aug-cc-pVTZ//omega B97X-D/6-31++G** level of theory. A detailed analysis of the reaction mechanisms in the gas phase and on the surface of mineral dust, represented by mono- and trisilicic acid, revealed that mineral dust has the potential of decreasing reaction barrier heights. Specifically, at 0 K, mineral dust can lower the apparent energy barrier of the reaction of formaldehyde with formic acid to zero. However, when the entropic contributions to the reaction free energies were accounted for, mineral dust was found to selectively enhance the reaction of water with formaldehyde, while inhibiting the reaction of formaldehyde and formic acid, in the lower parts of the troposphere (with temperatures around 298 K). In the upper troposphere (with temperatures closer to 198 K), mineral dust catalyzes both reactions and also the reaction of methanol with formic acid. Despite the intrinsic potential of mineral dust, calculation of the catalytic enhancement parameter for a likely range of dust aerosol concentrations suggested that dust aerosols will not contribute to secondary organic aerosol formation via dimerization of closed-shell organic compounds. The main reason for this is the relatively low absolute concentratign of tropospheric dust aerosol and its inefficiency in increasing the effective reaction rate coefficients.
  • Blum, Markus; Gebhardt, Jacqueline; Papendick, Marius; Schlindwein, Simon H.; Nieger, Martin; Gudat, Dietrich (2018)
    Two N-heterocyclic phosphines with exocyclic SCN substituents were synthesised via metathesis of chlorophosphine precursors with KSCN and fully characterised. The crystallographic studies reveal that the products exhibit pronounced structural differences. The thiocyanato unit binds in one case via the nitrogen atom to yield a molecular structure with a slightly elongated P-N single bond and, in the other case, via the sulfur atom to form a structure that is best described as an ion pair and forms a one-dimensional coordination polymer in the crystal. DFT calculations suggest that the P-N and P center dot center dot center dot S interactions can be described as covalent and dative bonds, respectively, and that the structural differences correlate with the different cation stabilities of the individual phosphenium cation fragments.
  • Dugan, Hilary A.; Summers, Jamie C.; Skaff, Nicholas K.; Krivak-Tetley, Flora E.; Doubek, Jonathan P.; Burke, Samantha M.; Bartlett, Sarah L.; Arvola, Lauri; Jarjanazi, Hamdi; Korponai, Jnos; Kleeberg, Andreas; Monet, Ghislaine; Monteith, Don; Moore, Karen; Rogora, Michela; Hanson, Paul C.; Weathers, Kathleen C. (2017)
    Anthropogenic sources of chloride in a lake catchment, including road salt, fertilizer, and wastewater, can elevate the chloride concentration in freshwater lakes above background levels. Rising chloride concentrations can impact lake ecology and ecosystem services such as fisheries and the use of lakes as drinking water sources. To analyze the spatial extent and magnitude of increasing chloride concentrations in freshwater lakes, we amassed a database of 529 lakes in Europe and North America that had greater than or equal to ten years of chloride data. For each lake, we calculated climate statistics of mean annual total precipitation and mean monthly air temperatures from gridded global datasets. We also quantified land cover metrics, including road density and impervious surface, in buffer zones of 100 to 1,500m surrounding the perimeter of each lake. This database represents the largest global collection of lake chloride data. We hope that long-term water quality measurements in areas outside Europe and North America can be added to the database as they become available in the future.
  • Kust, Andreja; Mares, Jan; Jokela, Jouni; Urajova, Petra; Hajek, Jan; Saurav, Kumar; Voracova, Katerina; Fewer, David P.; Haapaniemi, Esa; Permi, Perttu; Rehakova, Klara; Sivonen, Kaarina; Hrouzek, Pavel (2018)
    The pederin family includes a number of bioactive compounds isolated from symbiotic organisms of diverse evolutionary origin. Pederin is linked to beetle-induced dermatitis in humans, and pederin family members possess potent antitumor activity caused by selective inhibition of the eukaryotic ribosome. Their biosynthesis is accomplished by a polyketide/nonribosomal peptide synthetase machinery employing an unusual trans-acyltransferase mechanism. Here, we report a novel pederin type compound, cusperin, from the free-living cyanobacterium Cuspidothrix issatschenkoi (earlier Aphanizomenon). The chemical structure of cusperin is similar to that of nosperin recently isolated from the lichen cyanobiont Nostoc sharing the tehrahydropyran moiety and major part of the linear backbone. However, the cusperin molecule is extended by a glycine residue and lacks one hydroxyl substituent. Pederins were previously thought to be exclusive to symbiotic relationships. However, C. issatschenkoi is a nonsymbiotic planktonic organism and a frequent component of toxic water blooms. Cusperin is devoid of the cytotoxic activity reported for other pederin family members. Hence, our findings raise questions about the role of pederin analogues in cyanobacteria and broaden the knowledge of ecological distribution of this group of polyketides.
  • Harju, Jorma; Pineda, Jaime E.; Vasyunin, Anton; Caselli, Paola; Offner, Stella S. R.; Goodman, Alyssa A.; Juvela, Mika; Sipilä, Olli; Faure, Alexandre; Le Gal, Romane; Hily-Blant, Pierre; Alves, Joao; Bizzocchi, Luca; Burkert, Andreas; Chen, Hope; Friesen, Rachel K.; Guesten, Rolf; Myers, Philip C.; Punanova, Anna; Rist, Claire; Rosolowsky, Erik; Schlemmer, Stephan; Shirley, Yancy; Spezzano, Silvia; Vastel, Charlotte; Wiesenfeld, Laurent (2020)
    We present Atacama Large Millimeter/submillimeter Array maps of the starless molecular cloud core Ophiuchus/H-MM1 in the lines of deuterated ammonia (ortho-NH2D), methanol (CH3OH), and sulfur monoxide (SO). The dense core is seen in NH2D emission, whereas the CH3OH and SO distributions form a halo surrounding the core. Because methanol is formed on grain surfaces, its emission highlights regions where desorption from grains is particularly efficient. Methanol and sulfur monoxide are most abundant in a narrow zone that follows the eastern side of the core. This side is sheltered from the stronger external radiation field coming from the west. We show that photodissociation on the illuminated side can give rise to an asymmetric methanol distribution but that the stark contrast observed in H-MM1 is hard to explain without assuming enhanced desorption on the shaded side. The region of the brightest emission has a wavy structure that rolls up at one end. This is the signature of Kelvin-Helmholtz instability occurring in sheared flows. We suggest that in this zone, methanol and sulfur are released as a result of grain-grain collisions induced by shear vorticity.
  • Heikkinen, Liine; Äijälä, Mikko; Dällenbach, Kaspar; Chen, Gang; Garmash, Olga; Aliaga, Diego; Graeffe, Frans; Räty, Meri; Luoma, Krista; Aalto, Pasi; Kulmala, Markku; Petäjä, Tuukka; Worsnop, Douglas; Ehn, Mikael (2021)
    The Station for Measuring Ecosystem-Atmosphere Relations (SMEAR) II, located within the boreal forest of Finland, is a unique station in the world due to the wide range of long-term measurements tracking the Earth-atmosphere interface. In this study, we characterize the composition of organic aerosol (OA) at SMEAR II by quantifying its driving constituents. We utilize a multi-year data set of OA mass spectra measured in situ with an Aerosol Chemical Speciation Monitor (ACSM) at the station. To our knowledge, this mass spectral time series is the longest of its kind published to date. Similarly to other previously reported efforts in OA source apportionment from multi-seasonal or multi-annual data sets, we approached the OA characterization challenge through positive matrix factorization (PMF) using a rolling window approach. However, the existing methods for extracting minor OA components were found to be insufficient for our rather remote site. To overcome this issue, we tested a new statistical analysis framework. This included unsupervised feature extraction and classification stages to explore a large number of unconstrained PMF runs conducted on the measured OA mass spectra. Anchored by these results, we finally constructed a relaxed chemical mass balance (CMB) run that resolved different OA components from our observations. The presented combination of statistical tools provided a data-driven analysis methodology, which in our case achieved robust solutions with minimal subjectivity. Following the extensive statistical analyses, we were able to divide the 2012-2019 SMEAR II OA data (mass concentration interquartile range (IQR): 0.7, 1.3, and 2.6 mu gm(-3)) into three sub-categories - low-volatility oxygenated OA (LV-OOA), semi-volatile oxygenated OA (SV-OOA), and primary OA (POA) - proving that the tested methodology was able to provide results consistent with literature. LV-OOA was the most dominant OA type (organic mass fraction IQR: 49 %, 62 %, and 73 %). The seasonal cycle of LV-OOA was bimodal, with peaks both in summer and in February. We associated the wintertime LV-OOA with anthropogenic sources and assumed biogenic influence in LV-OOA formation in summer. Through a brief trajectory analysis, we estimated summertime natural LV-OOA formation of tens of ngm 3 h 1 over the boreal forest. SV-OOA was the second highest contributor to OA mass (organic mass fraction IQR: 19 %, 31 %, and 43 %). Due to SV-OOA's clear peak in summer, we estimate biogenic processes as the main drivers in its formation. Unlike for LV-OOA, the highest SV-OOA concentrations were detected in stable summertime nocturnal surface layers. Two nearby sawmills also played a significant role in SV-OOA production as also exemplified by previous studies at SMEAR II. POA, taken as a mix of two different OA types reported previously, hydrocarbon-like OA (HOA) and biomass burning OA (BBOA), made up a minimal OA mass fraction (IQR: 2 %, 6 %, and 13 %). Notably, the quantification of POA at SMEAR II using ACSM data was not possible following existing rolling PMF methodologies. Both POA organic mass fraction and mass concentration peaked in winter. Its appearance at SMEAR II was linked to strong southerly winds. Similar wind direction and speed dependence was not observed among other OA types. The high wind speeds probably enabled the POA transport to SMEAR II from faraway sources in a relatively fresh state. In the event of slower wind speeds, POA likely evaporated and/or aged into oxidized organic aerosol before detection. The POA organic mass fraction was significantly lower than reported by aerosol mass spectrometer (AMS) measurements 2 to 4 years prior to the ACSM measurements. While the co-located long-term measurements of black carbon supported the hypothesis of higher POA loadings prior to year 2012, it is also possible that short-term (POA) pollution plumes were averaged out due to the slow time resolution of the ACSM combined with the further 3 h data averaging needed to ensure good signal-to-noise ratios (SNRs). Despite the length of the ACSM data set, we did not focus on quantifying long-term trends of POA (nor other components) due to the high sensitivity of OA composition to meteorological anomalies, the occurrence of which is likely not normally distributed over the 8-year measurement period. Due to the unique and realistic seasonal cycles and meteorology dependences of the independent OA subtypes complemented by the reasonably low degree of unexplained OA variability, we believe that the presented data analysis approach performs well. Therefore, we hope that these results encourage also other researchers possessing several-yearlong time series of similar data to tackle the data analysis via similar semi- or unsupervised machine-learning approaches. This way the presented method could be further optimized and its usability explored and evaluated also in other environments.
  • Leverentz, Hannah R.; Siepmann, J. Ilja; Truhlar, Donald G.; Loukonen, Ville; Vehkamäki, Hanna (2013)
  • Sahyoun, Maher; Freney, Evelyn; Brito, Joel; Duplissy, Jonathan; Gouhier, Mathieu; Colomb, Aurélie; Dupuy, Regis; Bourianne, Thierry; Nowak, John B.; Yan, Chao; Petäjä, Tuukka; Kulmala, Markku; Schwarzenboeck, Alfons; Planche, Céline; Sellegri, Karine (2019)
    Abstract Volcanic emissions can significantly affect the Earth's radiation budget by emitting aerosol particles and gas-phase species that can result in the new particle formation (NPF). These particles can scatter solar radiation or modify cloud properties, with consequences on health, weather, and climate. To our knowledge, this is the first dedicated study detailing how gas-phase precursors emitted from volcanic plumes can influence the NPF. A series of airborne measurements were performed around the Etna and Stromboli volcanoes within the framework of the CLerVolc and STRAP projects. The ATR-42 aircraft was equipped with a range of instrumentation allowing the measurement of particle number concentration in diameter range above 2.5 nm, and gaseous species to investigate the aerosol dynamics and the processes governing the NPF and their growth within the volcanic plumes. We demonstrate that NPF occurs within the volcanic plumes in the Free Troposphere (FT) and Boundary Layer (BL). Typically, the NPF events were more pronounced in the FT, where the condensational sink was up to two orders of magnitude smaller and the temperature was ~20°C lower than in the BL. Within the passive volcanic plume, the concentration of sulfur dioxide, sulfuric acid, and N2.5 were as high as 92 ppbV, 5.65?108 and 2.4?105 cm?3, respectively. Using these measurements, we propose a new parameterization for NPF rate (J2.5) within the passive volcanic plume in the FT. These results can be incorporated into mesoscale models to better assess the impact of the particle formed by natural processes, i.e. volcanic plumes, on climate.
  • Talvenmäki, Harri; Lallukka, Niina; Survo, Suvi; Romantschuk, Martin (2019)
    Fenton's reaction-based chemical oxidation is in principle a method that can be utilized for all organic fuel residues thus making it a potential all-purpose, multi-contaminant, in situ application for cases in which storage and distribution of different types of fuels have resulted in contamination of soil or groundwater. Since peroxide breakdown reactions are also expected to lead to a physical transport of the target compound, this secondary physical removal, or rebound concentrations related to it, is prone to be affected by the chemical properties of the target compound. Also, since soil conditions are seldom optimal for Fenton's reaction, the balance between chemical oxidation and transport may vary. In this study, it was found that, with a high enough hydrogen peroxide concentration (5 M), methyl tert-butyl ether-spiked groundwater could be treated even under suboptimal conditions for chemical mineralization. In these cases, volatilization was not only contributing to the total removal but also leading to rebound effects similar to those associated with air sparging techniques. Likewise for diesel, temporal transport from soil to the aqueous phase was found to lead to false positives that outweighed the actual remediation effect through chemical mineralization.
  • Draper, Danielle C.; Myllys, Nanna; Hyttinen, Noora; Moller, Kristian H.; Kjaergaard, Henrik G.; Fry, Juliane L.; Smith, James N.; Kurten, Theo (2019)
    NO3 radical oxidation of most monoterpenes is a significant source of secondary organic aerosol (SOA) in many regions influenced by both biogenic and anthropogenic emissions, but there are very few published mechanistic studies of NO3 chemistry beyond simple first generation products. Here, we present a computationally derived mechanism detailing the unimolecular pathways available to the second generation of peroxy radicals following NO3 oxidation of Delta-3-carene, defining generations based on the sequence of peroxy radicals formed rather than number of oxidant attacks. We assess five different types of unimolecular reactions, including peroxy and alkoxy radical (RO2 and RO) hydrogen shifts, RO2 and RO ring closing (e.g., endoperoxide formation), and RO decomposition. Rate constants calculated using quantum chemical methods indicate that this chemical system has significant contribution from both bimolecular and unimolecular pathways. The dominant unimolecular reactions are endoperoxide formation, RO H-shifts, and RO decomposition. However, the complexity of the overall reaction is tempered as only 1 or 2 radical propagation pathways dominate the fate of each radical intermediate. Chemical ionization mass spectrometry (CIMS) measurements using the NO3- reagent ion during Delta-3-carene + NO3 chamber experiments show products consistent with each of the three types of unimolecular reactions predicted to be important from the computational mechanism. Moreover, the SIMPOL group contribution method for predicting vapor pressures suggests that a majority of the closed-shell products inferred from these unimolecular reactions are likely to have low enough vapor pressure to be able to contribute to SOA formation.
  • Navarro-Almaida, D.; Le Gal, R.; Fuente, A.; Riviere-Marichalar, P.; Wakelam,; Cazaux, S.; Caselli, P.; Laas, J. C.; Alonso-Albi, T.; Loison, J. C.; Gerin, M.; Kramer, C.; Roueff, E.; Bachillerl, R.; Commercon, B.; Friesen, R.; Garcia-Burillo, S.; Goicoechea, J. R.; Giuliano, B. M.; Jimenez-Serram,; Kirk, J. M.; Lattanzi, M.; Malinen, J.; Marcelino, N.; Martin-Domenech, R.; Caro, G. M. Munoz; Pineda, J.; Tercero, B.; Trevino-Morales, S. P.; Roncero, O.; Hacar, A.; Tafalla, M.; Ward-Thompson, D. (2020)
    Context. Sulphur is one of the most abundant elements in the Universe. Surprisingly, sulphuretted molecules are not as abundant as expected in the interstellar medium and the identity of the main sulphur reservoir is still an open question.Aims. Our goal is to investigate the H2S chemistry in dark clouds, as this stable molecule is a potential sulphur reservoir.Methods. Using millimeter observations of CS, SO, H2S, and their isotopologues, we determine the physical conditions and H2S abundances along the cores TMC 1-C, TMC 1-CP, and Barnard 1b. The gas-grain model NAUTILUS is used to model the sulphur chemistry and explore the impact of photo-desorption and chemical desorption on the H2S abundance.Results. Our modeling shows that chemical desorption is the main source of gas-phase H2S in dark cores. The measured H2S abundance can only be fitted if we assume that the chemical desorption rate decreases by more than a factor of 10 when n(H) > 2 x 10(4). This change in the desorption rate is consistent with the formation of thick H2O and CO ice mantles on grain surfaces. The observed SO and H2S abundances are in good agreement with our predictions adopting an undepleted value of the sulphur abundance. However, the CS abundance is overestimated by a factor of 5-10. Along the three cores, atomic S is predicted to be the main sulphur reservoir.Conclusions. The gaseous H2S abundance is well reproduced, assuming undepleted sulphur abundance and chemical desorption as the main source of H2S. The behavior of the observed H2S abundance suggests a changing desorption efficiency, which would probe the snowline in these cold cores. Our model, however, highly overestimates the observed gas-phase CS abundance. Given the uncertainty in the sulphur chemistry, we can only conclude that our data are consistent with a cosmic elemental S abundance with an uncertainty of a factor of 10.
  • Hyttinen, Noora; Wolf, Matthieu; Rissanen, Matti; Ehn, Mikael; Peräkylä, Otso; Kurten, Theo; Prisle, Nønne L. (2021)
    Oxidized organic compounds are expected to contribute to secondary organic aerosol (SOA) if they have sufficiently low volatilities. We estimated saturation vapor pressures and activity coefficients (at infinite dilution in water and a model water-insoluble organic phase) of cyclohexene- and alpha-pinene-derived accretion products, "dimers", using the COSMOtherm19 program. We found that these two property estimates correlate with the number of hydrogen bond-donating functional groups and oxygen atoms in the compound. In contrast, when the number of H-bond donors is fixed, no clear differences are seen either between functional group types (e.g., OH or OOH as H-bond donors) or the formation mechanisms (e.g., gas-phase radical recombination vs liquid-phase closed-shell esterification). For the cyclohexene-derived dimers studied here, COSMOtherm19 predicts lower vapor pressures than the SIMPOL.1 group-contribution method in contrast to previous COSMOtherm estimates using older parameterizations and nonsystematic conformer sampling. The studied dimers can be classified as low, extremely low, or ultra-low-volatility organic compounds based on their estimated saturation mass concentrations. In the presence of aqueous and organic aerosol particles, all of the studied dimers are likely to partition into the particle phase and thereby contribute to SOA formation.
  • Liu, Licheng; Zhuang, Qianlai; Zhu, Qing; Liu, Shaoqing; van Asperen, Hella; Pihlatie, Mari (2018)
    Carbon monoxide (CO) plays an important role in controlling the oxidizing capacity of the atmosphere by reacting with OH radicals that affect atmospheric methane (CH4) dynamics. We develop a process-based biogeochemistry model to quantify the CO exchange between soils and the atmosphere with a 5 min internal time step at the global scale. The model is parameterized using the CO flux data from the field and laboratory experiments for 11 representative ecosystem types. The model is then extrapolated to global terrestrial ecosystems using monthly climate forcing data. Global soil gross consumption, gross production, and net flux of the atmospheric CO are estimated to be from -197 to -180, 34 to 36, and -163 to -145 TgCOyr(-1) (1 Tg = 10(12) g), respectively, when the model is driven with satellite-based atmospheric CO concentration data during 2000-2013. Tropical evergreen forest, savanna and deciduous forest areas are the largest sinks at 123 TgCOyr(-1). The soil CO gross consumption is sensitive to air temperature and atmospheric CO concentration, while the gross production is sensitive to soil organic carbon (SOC) stock and air temperature. By assuming that the spatially distributed atmospheric CO concentrations (similar to 128 ppbv) are not changing over time, the global mean CO net deposition velocity is estimated to be 0.16-0.19mms 1 during the 20th century. Under the future climate scenarios, the CO deposition velocity will increase at a rate of 0.0002-0.0013 mms 1 r(-1) during 2014-2100, reaching 0.20-0.30 mm s(-1) by the end of the 21st century, primarily due to the increasing temperature. Areas near the Equator, the eastern US, Europe and eastern Asia will be the largest sinks due to optimum soil moisture and high temperature. The annual global soil net flux of atmospheric CO is primarily controlled by air temperature, soil temperature, SOC and atmospheric CO concentrations, while its monthly variation is mainly determined by air temperature, precipitation, soil temperature and soil moisture.
  • Wannarit, Nanthawat; Pakawatchai, Chaveng; Mutikainen, Ilpo; Costa, Ramon; Moreira, Iberio de P. R.; Youngme, Sujittra; Illas, Francesc (2013)
  • Freese, Tyll; Luecke, Ana-Luiza; Namyslo, Jan C.; Nieger, Martin; Schmidt, Andreas (2018)
    Sydnone imines were deprotonated at the C4 position to give lithium-stabilized anions, which proved to be stable for several months in solution. These anions are elements of the intersection of the substance classes of N-heterocyclic carbenes and mesomeric betaines. They can be formulated as anionic N-heterocyclic carbenes. The negative charge translates into high-field shifts of the C-13 NMR resonance frequencies of C4 in comparison to other NHCs. Similar to the chemistry of N-heterocyclic carbenes, reactions with isocyanates and isothiocyanates gave 4-(N-carbamoyl)-benzoylsydnone imines in trapping reactions. As a result of ring transformations involving the characteristic p-architecture of the mesoionic framework, imidazolidine-2,4-dithiones, imidazolin-2,4-diones and 1,2,4-triazol-5-ones were formed depending on the substitution pattern of the starting materials and the reaction conditions.
  • Lee, Ben H.; Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurten, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A. (2016)
    Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene-and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (similar to 2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.