Local formation of HArF in solid argon: Low-temperature limit and thermal activation

The H + Ar + F reaction leading to HArF formation in an argon matrix is studied at temperatures down to 8 K. The effects of the precursor concentration, deuteration, IR light, and deposition temperature as well as thermal activation of this reaction are studied. It is found that HArF molecules are formed slowly but efficiently at 8 K in a photolyzed HF/Ar matrix, supporting the previously reported results. The formation rate of HArF (and DArF) exhibits a low-temperature limit and enhances at elevated temperatures with activation energy of ca. 40 meV. All the data show that HArF is formed as a result of a local reaction of hydrogen atoms with the parent Ar−F centers and the tunneling mechanism is very probable here. The locality of the precursor photolysis required for this tunneling reaction is consistent with the partial HArF formation observed during photolysis of HF in an argon matrix. The decay mechanism of (ArHAr)⁺ cations is also studied. The present results confirm the previous conclusions that the decay of the cations is not essentially connected to the HArF formation

Laboratory Determination of the Infrared Band Strengths of Pyrene Frozen in Water Ice: Implications for the Composition of Interstellar Ices

Broad infrared emission features (e.g., at 3.3, 6.2, 7.7, 8.6, and 11.3 microns) from the gas phase interstellar medium have long been attributed to polycyclic aromatic hydrocarbons (PAHs). A significant portion (10%-20%) of the Milky Way's carbon reservoir is locked in PAH molecules, which makes their characterization integral to our understanding of astrochemistry. In molecular clouds and the dense envelopes and disks of young stellar objects (YSOs), PAHs are expected to be frozen in the icy mantles of dust grains where they should reveal themselves through infrared absorption. To facilitate the search for frozen interstellar PAHs, laboratory experiments were conducted to determine the positions and strengths of the bands of pyrene mixed with H2O and D2O ices. The D2O mixtures are used to measure pyrene bands that are masked by the strong bands of H2O, leading to the first laboratory determination of the band strength for the CH stretching mode of pyrene in water ice near 3.25 microns. Our infrared band strengths were normalized to experimentally determined ultraviolet band strengths, and we find that they are generally ~50% larger than those reported by Bouwman et al. based on theoretical strengths. These improved band strengths were used to reexamine YSO spectra published by Boogert et al. to estimate the contribution of frozen PAHs to absorption in the 5-8 micron spectral region, taking into account the strength of the 3.25 micron CH stretching mode. It is found that frozen neutral PAHs contain 5%-9% of the cosmic carbon budget, and account for 2%-9% of the unidentified absorption in the 5-8 micron region.Comment: Accepted for publication in ApJ on 14 Feb 201

Vapor wall deposition in Teflon chambers

Teflon chambers are ubiquitous in studies of atmospheric chemistry. Secondary organic aerosol (SOA) formation can be underestimated, owing to deposition of SOA-forming vapors to the chamber wall. We present here an experimental protocol and a model framework to constrain the vapor–wall interactions in Teflon chambers. We measured the wall deposition rates of 25 oxidized organic compounds generated from the photooxidation of isoprene, toluene, α-pinene, and dodecane in two chambers that had been extensively used and in two new unused chambers. We found that the extent of prior use of the chamber did not significantly affect the sorption behavior of the Teflon films. Among the 25 compounds studied, the maximum wall deposition rate is exhibited by the most highly oxygenated and least volatile compounds. By optimizing the model output to the observed vapor decay profiles, we identified that the dominant parameter governing the extent of wall deposition of a compound is its wall accommodation coefficient (α_(wi)), which can be correlated through its volatility with the number of carbons and oxygens in the molecule. By doing so, the wall-induced deposition rate of intermediate/semi-volatile organic vapors can be reasonably predicted based on their molecular constituency. The extent to which vapor wall deposition impacts measured SOA yields depends on the competition between uptake of organic vapors by suspended particles and the chamber wall. The timescale associated with vapor wall deposition can vary from minutes to hours depending on the value of α_(w,i). For volatile and intermediate volatility organic compounds (small α_(w,i)), gas-particle partitioning will dominate wall deposition for typical particle number concentrations in chamber experiments. For compounds characterized by relatively large α_(w,i), vapor transport to particles is suppressed by competition with the chamber wall even with perfect particle accommodation

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

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

Determinants of serum concentrations of perfluoroalkyl acids (PFAAs) in school children and the contribution of low-level PFAA-contaminated drinking water

Little is known about the demographic/life-style/physiological determinants explaining the variation of serum perfluoroalkyl acid (PFAA) concentrations in children. We identified significant determinants in children and investigated the influence of low-level PFAA-contaminated drinking water (DW) (<10 ng L−1 of single PFAAs) on serum concentrations. Four perfluorosulfonic acids (PFSAs) and 11 perfluorocarboxylic acids (PFCAs) were analyzed in serum from 5th grade children from 11 Swedish schools (N = 200; average age: 12 years) using liquid chromatography-tandem-mass-spectrometry. Data on demography and life-style/physiological factors were obtained by questionnaires. PFAA concentrations in raw and drinking water (DW) were obtained from the water works supplying DW to the schools. In multiple regression analyses school was the determinant contributing most to the variation in PFAA concentrations, with the lowest contribution for PFHpA (10%) and the highest for PFHxS (81%). Girls had lower adjusted mean concentrations of PFHxS, PFOS, PFNA and PFDA than boys, but a higher concentration of PFHxA. Girls reporting onset of menstruation had lower PFHxS and PFOA concentrations than other girls, suggesting menstrual bleeding elimination. Children born by mothers from less industrialized countries had lower mean concentrations of both PFSAs and PFCAs than children with mothers from highly industrialized countries, suggesting differences in early-life exposure. Life-style factors associated with paternal education levels appeared to influence PFAA concentrations differently than maternal education level. Already at an average DW PFHxS concentration of 2 ng L−1, children had a significantly higher adjusted mean serum PFHxS concentration than at an average DW concentration of <1.6 ng PFHxS L−1. Similar results were observed for PFOS and PFOA. The DW variable explained 16% (PFOA) to 78% (PFHxS) of the variation in serum PFAA concentrations, suggesting that low-level-contaminated DW is a significant source of exposure for children in Sweden. Although some of the associations, especially those with menstruation and maternal birth country, should be interpreted with extra caution due to the small size of the study, the results contribute to future work on identifying populations of children at risk of elevated PFAA exposures

Formation of highly oxygenated low-volatility products from cresol oxidation

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

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

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

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

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

Aktinomykeettien ja homeiden esiintyminen verkostovedessä

Valtaosa Suomen talousvesistä täyttää kaikki asetetut normit ja kuluttajat pitävät talousveden laatua hyvänä, mutta myös suomalaisissa talousvesissä esiintyy mikrobiologisia ongelmia. Yksi tällainen ilmiö on verkostovesien haju- ja makuongelmat, jotka aiheutuvat verkostoissa tapahtuvasta mikrobikasvusta. Tässä oleelliset tekijät ovat putkistojen pinnoilla biofilmeillä kasvavat aktinomykeetit ja mikrosienet (homeet ja hiivat). Aiempaa tutkimustietoa asiasta ei juuri ole, joten Kansanterveyslaitos aloitti vuonna 2004 Vesihuoltolaitosten kehittämisrahaston tukemana tutkimuksen, jossa selvitettiin homeiden ja aktinomykeettien esiintymisestä Suomen talousvesiverkostoissa. Tutkimus käynnistettiin valtakunnallisella kyselyllä, johon vastasi 405: vedenottamoa. Näistä n. 10%:lla oli homeisiin/aktinomykeetteihinmahdollisesti liittyviä haju- tai makuongelmia verkostovesissä