A new method for atmospheric detection of the CH3O2 radical

A new method for measurement of the methyl peroxy (CH3O2) radical has been developed using the conversion of CH3O2 into CH3O by excess NO with subsequent detection of CH3O by fluorescence assay by gas expansion (FAGE) with laser excitation at ca. 298 nm. The method can also directly detect CH3O, when no nitric oxide is added. Laboratory calibrations were performed to characterise the FAGE instrument sensitivity using the conventional radical source employed in OH calibration with conversion of a known concentration of OH into CH3O2 via reaction with CH4 in the presence of O2. Detection limits of 3.8 × 108 and 3.0 × 108 molecule cm−3 were determined for CH3O2 and CH3O respectively for a signal-to-noise ratio of 2 and 5 min averaging time. Averaging over 1 h reduces the detection limit for CH3O2 to 1.1 × 108 molecule cm−3, which is comparable to atmospheric concentrations. The kinetics of the second-order decay of CH3O2 via its self-reaction were observed in HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry) at 295 K and 1 bar and used as an alternative method of calibration to obtain a calibration constant with overlapping error limits at the 1σ level with the result of the conventional method of calibration. The overall uncertainties of the two methods of calibrations are similar – 15 % for the kinetic method and 17 % for the conventional method – and are discussed in detail. The capability to quantitatively measure CH3O in chamber experiments is demonstrated via observation in HIRAC of CH3O formed as a product of the CH3O2 self-reaction

Kinetics of CH₂OO reactions with SO₂, NO₂, NO, H₂O and CH₃CHO as a function of pressure

Kinetics of CH₂OO Criegee intermediate reactions with SO₂, NO₂, NO, H₂O and CH₃CHO and CH₂I radical reactions with NO₂ are reported as a function of pressure at 295 K. Measurements were made under pseudo-first-order conditions using flash photolysis of CH₂I₂–O₂–N₂ gas mixtures in the presence of excess co-reagent combined with monitoring of HCHO reaction products by laser-induced fluorescence (LIF) spectroscopy and, for the reaction with SO₂, direct detection of CH₂OO by photoionisation mass spectrometry (PIMS). Rate coefficients for CH₂OO + SO₂ and CH₂OO + NO₂ are independent of pressure in the ranges studied and are (3.42 ± 0.42) × 10‾¹¹ cm³ s‾¹ (measured between 1.5 and 450 Torr) and (1.5 ± 0.5) × 10‾¹² cm³ s‾¹ (measured between 25 and 300 Torr), respectively. The rate coefficient for CH₂OO + CH₃CHO is pressure dependent, with the yield of HCHO decreasing with increasing pressure. Upper limits of 2 × 10−13 cm³ s‾¹ and 9 × 10−17 cm³ s‾¹ are placed on the rate coefficients for CH₂OO + NO and CH₂OO + H₂O, respectively. The upper limit for the rate coefficient for CH₂OO + H₂O is significantly lower than has been reported previously, with consequences for modelling of atmospheric impacts of CH₂OO chemistry

Production of HO₂ and OH radicals from near-UV irradiated airborne TiO₂ nanoparticles

The production of gas-phase hydroperoxyl radicals, HO2, is observed directly from sub-micron airborne TiO2 nanoparticles (80% anatase and 20% rutile formulation) irradiated by 300 – 400 nm radiation. The rate of HO2 production as a function of O2 pressure follows Langmuir isotherm behaviour suggesting O2 is involved in the production of HO2 following its adsorption onto the surface of the TiO2 aerosol. Reduction of adsorbed O2 by photogenerated electrons is likely to be the initial step followed by reaction with a proton produced via oxidation of adsorbed water with a photogenerated hole. The rate of HO2 production decreased significantly over the range of relative humidities between 8.7 and 36.9 %, suggesting further adsorption of water vapour inhibits HO2 production. The adsorption equilibrium constants were calculated to be: KO2 = 0.27 ± 0.02 Pa-1 and KH2O = 2.16 ± 0.12 Pa-1 for RH = 8.7%, decreasing to KO2 = 0.18 ± 0.01 Pa-1 and KH2O = 1.33 ± 0.04 Pa-1 at RH = 22.1%. The increased coverage of H2O onto the TiO2 aerosol surface may inhibit HO2 production by decreasing the effective surface area of the TiO2 particle and lowering the binding energy of O2 on the aerosol surface, hence shortening its desorption lifetime. The yield of HO2 for atmospheric levels of O2 and normalised for surface area and light intensity was found to be k′prod = (3.64 ± 0.04) × 10-3 HO2 molecule photon-1 at RH = 8.7%. This yield decreased to k′prod = (1.97 ± 0.03) × 10-3 molecule photon-1 as the RH was increased to 22.1%. Using this value, the rate of production of HO2 from TiO2 surfaces under atmospheric conditions was estimated to be in the range 5x104 – 1x106 molecule cm-3 s-1 using observed surface areas of mineral dust at Cape Verde, and assuming a TiO2 fraction of 4.5%. For the largest loadings of dust in the troposphere, the rate of this novel heterogeneous production mechanism begins to approach that of HO2 production from the gas-phase reaction of OH with CO in unpolluted regions.The production of gas-phase OH radicals could only be observed conclusively at high aerosol surface areas, and was attributed to the decomposition of H2O2 at the surface by photogenerated electrons

Direct measurements of OH and other product yields from the HO2 + CH3C(O)O2 reaction

The reaction CH3C(O)O2 + HO2 → CH3C(O)OOH+O2 (Reaction R5a), CH3C(O)OH+O3 (Reaction R5b), CH3+CO2+OH+O2 (Reaction R5c) was studied in a series of experiments conducted at 1000 mbar and (293±2)K in the HIRAC simulation chamber. For the first time, products, (CH3C(O)OOH, CH3C(O)OH, O3 and OH) from all three branching pathways of the reaction have been detected directly and simultaneously. Measurements of radical precursors (CH3OH, CH3CHO), HO2 and some secondary products HCHO and HCOOH further constrained the system. Fitting a comprehensive model to the experimental data, obtained over a range of conditions, determined the branching ratios α(R5a) = 0.37±0.10, α(R5b) =0.12±0.04 and α(R5c) =0.51±0.12 (errors at 2σ level). Improved measurement/model agreement was achieved using k(R5) =(2.4±0.4)×10-11 cm3 molecule-1 s-1, which is within the large uncertainty of the current IUPAC and JPL recommended rate coefficients for the title reaction. The rate coefficient and branching ratios are in good agreement with a recent study performed by Groß et al. (2014b); taken together, these two studies show that the rate of OH regeneration through Reaction (R5) is more rapid than previously thought. GEOS-Chem has been used to assess the implications of the revised rate coefficients and branching ratios; the modelling shows an enhancement of up to 5% in OH concentrations in tropical rainforest areas and increases of up to 10% at altitudes of 6-8 km above the equator, compared to calculations based on the IUPAC recommended rate coefficient and yield. The enhanced rate of acetylperoxy consumption significantly reduces PAN in remote regions (up to 30 %) with commensurate reductions in background NOx

Design of and initial results from a highly instrumented reactor for atmospheric chemistry (HIRAC)

International audienceThe design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO2 radicals with the Fluorescence Assay by Gas Expansion (FAGE) technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC) instrument and a GC instrument for formaldehyde detection; and NO/NO2, CO, O3, and H2O vapour analysers. Ray tracing simulations and measurements of the blacklamp flux have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1) high precision kinetics investigations over a range of atmospheric conditions; (2) detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3) field instrument intercomparison, calibration, development, and investigations of instrument response under a range of atmospheric conditions

On-line solid phase microextraction derivatization for the sensitive determination of multi-oxygenated volatile compounds in air

Multi-oxygenated volatile organic compounds are important markers of air pollution and precursors of ozone and secondary aerosols in both polluted and remote environments. Herein, their accurate determination was enhanced. The approach was based on an automated system for active sampling and on-fibre derivatization coupled with the gas chromatography–mass spectrometry (GC–MS) technique. The method capability was determined for different compound families, such as aldehydes, ketones, α-dicarbonyls, hydroxy-aldehydes, hydroxy-ketones, and carboxylic acids. A good accuracy (<7 %) was demonstrated from the results compared to Fourier-transform infrared spectroscopy (FTIR). Limits of detection (LODs) of 6–100 pptV were achieved with a time resolution lower than 20 min. The developed method was successfully applied to the determination of multi-oxygenated compounds in air samples collected during an intercomparison campaign (EUROCHAMP-2020 project). Also, its capability and accuracy for atmospheric monitoring was demonstrated in an isoprene ozonolysis experiment. Both were carried out in the high-volume outdoor atmospheric simulation chambers (EUPHORE, 200 m3). In summary, our developed technique offers near-real-time monitoring with direct sampling, which is an advantage in terms of handling and labour time for a proper quantification of trace levels of atmospheric multi-oxygenated compounds

Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR

Hydroxyl (OH) radical reactivity (kOH) has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection  < 1 s−1 at a time resolution of 30 s to a few minutes) is higher for instruments directly detecting hydroxyl radicals, whereas the indirect comparative reactivity method (CRM) has a higher limit of detection of 2 s−1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapour or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds (mixing ratio of OH reactants were up to 10 ppbv). In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM measurements is most likely limited by the corrections that need to be applied to account for known effects of, for example, deviations from pseudo first-order conditions, nitrogen oxides or water vapour on the measurement. Methods used to derive these corrections vary among the different CRM instruments. Measurements taken with a flow-tube instrument combined with the direct detection of OH by chemical ionisation mass spectrometry (CIMS) show limitations in cases of high reactivity and high NO concentrations but were accurate for low reactivity (< 15 s−1) and low NO (< 5 ppbv) conditions

A newly developed tool for intra-tracheal temperature and humidity assessment in laryngectomized individuals: the Airway Climate Explorer (ACE)

The aim of this study is to develop a postlaryngectomy airway climate explorer (ACE) for assessment of intratracheal temperature and humidity and of influence of heat and moisture exchangers (HMEs). Engineering goals were within-device condensation prevention and fast response time characteristics. The ACE consists of a small diameter, heated air-sampling catheter connected to a heated sensor house, containing a humidity sensor. Air is sucked through the catheter by a controlled-flow pump. Validation was performed in a climate chamber using a calibrated reference sensor and in a two-flow system. Additionally, the analyser was tested in vivo. Over the clinically relevant range of humidity values (5–42 mg H2O/l air) the sensor output highly correlates with the reference sensor readings (R2 > 0.99). The 1–1/e response times are all <0.5 s. A first in vivo pilot measurement was successful. The newly developed, verified, fast-responding ACE is suitable for postlaryngectomy airway climate assessment

Disorientating, fun or meaningful? Disadvantaged families' experiences of a science museum visit

It is widely agreed that there is a need to increase and widen science partici- pation. Informal science learning environments (ISLEs), such as science museums, may provide valuable spaces within which to engage visitors—yet the visitor profile of science museums remains narrow. This paper seeks to understand the experiences of socially disadvantaged families within such spaces. Using a Bourdieusian analytic lens, we analyse qualitative data from a small study conducted with ten parents and ten children from an urban school who visited a large science museum. Data includes pre- and post-interviews, audio recordings and visit fieldnotes. We characterised families’ experiences as falling into three discourses, as ‘disorientating’, ‘fun’ or ‘meaningful’ visits. Analysis identifies how the families’ experiences, and the likelihood of deriving science learning from the visit, were shaped through interactions of habitus and capital. Implications for improving equity and inclusion within ISLEs are discussed