Field measurements of methylglyoxal using proton transfer reaction time-of-flight mass spectrometry and comparison to the DNPH–HPLC–UV method

Methylglyoxal (MGLY) is an important atmospheric α-dicarbonyl species for which photolysis acts as a significant source of peroxy radicals, contributing to the oxidizing capacity of the atmosphere and, as such, the formation of secondary pollutants such as organic aerosols and ozone. However, despite its importance, only a few techniques exhibit time resolutions and detection limits that are suitable for atmospheric measurements.This study presents the first field measurements of MGLY by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) performed during the ChArMEx SOP2 field campaign. This campaign took place at a Mediterranean site characterized by intense biogenic emissions and low levels of anthropogenic trace gases. Concomitant measurements of MGLY were performed using the 2,4-dinitrophenylhydrazine (DNPH) derivatization technique and high performance liquid chromatography (HPLC) with UV detection. PTR-ToF-MS and DNPH–HPLC measurements were compared to determine whether these techniques can perform reliable measurements of MGLY.Ambient time series revealed levels of MGLY ranging from 28 to 365&thinsp;pptv, with a clear diurnal cycle due to elevated concentrations of primary biogenic species during the daytime, and its oxidation led to large production rates of MGLY. A scatter plot of the PTR-ToF-MS and DNPH–HPLC measurements indicates a reasonable correlation (R2 = 0.48) but a slope significantly lower than unity (0.58±0.05) and a significant intercept of 88.3±8.0&thinsp;pptv. A careful investigation of the differences between the two techniques suggests that this disagreement is not due to spectrometric interferences from H3O+(H2O)3 or methyl ethyl ketone (or butanal) detected at m∕z 73.050 and m∕z 73.065, respectively, which are close to the MGLY m∕z of 73.029. The differences are more likely due to uncorrected sampling artifacts such as overestimated collection efficiency or loss of MGLY into the sampling line for the DNPH–HPLC technique or unknown isobaric interfering compounds such as acrylic acid and propanediol for the PTR-ToF-MS.Calculations of MGLY loss rates with respect to OH oxidation and direct photolysis indicate similar contributions for these two loss pathways.</p

Detailed characterizations of the new Mines Douai comparative reactivity method instrument via laboratory experiments and modeling

The hydroxyl (OH) radical is an important oxidant in the troposphere, which controls the lifetime of most air quality- and climate-related trace gases. However, there are still uncertainties concerning its atmospheric budget, and integrated measurements of OH sinks have been valuable to improve this aspect. Among the analytical tools used for measuring total OH reactivity in ambient air, the comparative reactivity method (CRM) is spreading rapidly in the atmospheric community. However, measurement artifacts have been highlighted for this technique, and additional work is needed to fully characterize them. In this study, we present the new Mines Douai CRM instrument, with an emphasis on the corrections that need to be applied to ambient measurements of total OH reactivity. Measurement artifacts identified in the literature have been investigated, including (1) a correction for a change in relative humidity between the measurement steps leading to different OH levels, (2) the formation of spurious OH in the sampling reactor when hydroperoxy radicals (HO2) react with nitrogen monoxide (NO), (3) not operating the CRM under pseudo-first-order kinetics, and (4) the dilution of ambient air inside the reactor. The dependences of these artifacts on various measurable parameters, such as the pyrrole-to-OH ratio and the bimolecular reaction rate constants of ambient trace gases with OH, have also been studied. Based on these observations, parameterizations are proposed to correct ambient OH reactivity measurements. On average, corrections of 5.2 ± 3.2, 9.2 ± 15.7, and 8.5 ± 5.8 s-1 were respectively observed for (1), (2) and (3) during a field campaign performed in Dunkirk, France (summer 2014). Numerical simulations have been performed using a box model to check whether experimental observations mentioned above are consistent with our understanding of the chemistry occurring in the CRM reactor. Two different chemical mechanisms have been shown to reproduce the magnitude of corrections (2) and (3). In addition, these simulations reproduce their dependences on the pyrrole-to-OH ratio and on bimolecular reaction rate constants of gases reacting with OH. The good agreement found between laboratory experiments and model simulations gives us confidence in the proposed parameterizations. However, it is worth noting that the numerical values given in this study are suitable for the Mines Douai instrument and may not be appropriate for other CRM instruments. It is recommended that each group characterize its own instrument following the recommendations given in this study. An assessment of performances for the Mines Douai instrument, including a propagation of errors from the different corrections, indicates a limit of detection of 3.0 s-1 and total uncertainties of 17-25 % for OH reactivity values higher than 15 s-1 and NOx mixing ratios lower than 30 ppbv

Biphasic effect of extracellular ATP on human and rat airways is due to multiple P2 purinoceptor activation

BACKGROUND: Extracellular ATP may modulate airway responsiveness. Studies on ATP-induced contraction and [Ca(2+)](i )signalling in airway smooth muscle are rather controversial and discrepancies exist regarding both ATP effects and signalling pathways. We compared the effect of extracellular ATP on rat trachea and extrapulmonary bronchi (EPB) and both human and rat intrapulmonary bronchi (IPB), and investigated the implicated signalling pathways. METHODS: Isometric contraction was measured on rat trachea, EPB and IPB isolated rings and human IPB isolated rings. [Ca(2+)](i )was monitored fluorimetrically using indo 1 in freshly isolated and cultured tracheal myocytes. Statistical comparisons were done with ANOVA or Student's t tests for quantitative variables and χ(2 )tests for qualitative variables. Results were considered significant at P < 0.05. RESULTS: In rat airways, extracellular ATP (10(-6)–10(-3 )M) induced an epithelium-independent and concentration-dependent contraction, which amplitude increased from trachea to IPB. The response was transient and returned to baseline within minutes. Similar responses were obtained with the non-hydrolysable ATP analogous ATP-γ-S. Successive stimulations at 15 min-intervals decreased the contractile response. In human IPB, the contraction was similar to that of rat IPB but the time needed for the return to baseline was longer. In isolated myocytes, ATP induced a concentration-dependent [Ca(2+)](i )response. The contractile response was not reduced by thapsigargin and RB2, a P2Y receptor inhibitor, except in rat and human IPB. By contrast, removal of external Ca(2+), external Na(+ )and treatment with D600 decreased the ATP-induced response. The contraction induced by α-β-methylene ATP, a P2X agonist, was similar to that induced by ATP, except in IPB where it was lower. Indomethacin and H-89, a PKA inhibitor, delayed the return to baseline in extrapulmonary airways. CONCLUSION: Extracellular ATP induces a transient contractile response in human and rat airways, mainly due to P2X receptors and extracellular Ca(2+ )influx in addition with, in IPB, P2Y receptors stimulation and Ca(2+ )release from intracellular Ca(2+ )stores. Extracellular Ca(2+ )influx occurs through L-type voltage-dependent channels activated by external Na(+ )entrance through P2X receptors. The transience of the response cannot be attributed to ATP degradation but to purinoceptor desensitization and, in extrapulmonary airways, prostaglandin-dependent PKA activation

Giving birth: Expectations of first time mothers in Switzerland at the mid point of pregnancy

Problem and background: Despite a generally affluent society, the caesarean section rate in Switzerland has steadily climbed in recent years from 22.9% in 1998 to 33.7% in 2014. Speculation by the media has prompted political questions as to the reasons. However, there is no clear evidence as to why the Swiss rate should be so high especially in comparison with neighbouring countries. Aim: To describe the emerging expectations of giving birth of healthy primigravid women in the early second semester of pregnancy in four Swiss cantons. Methods: Qualitative individual interviews with 58 healthy primigravid women, were audio recorded, transcribed and subjected to thematic analysis. Recruitment took place through public and private hospitals, birth centres, obstetricians and independent midwives. The main ethical issues were informed consent, autonomy, confidentiality and anonymity. Findings: The three main themes identified were taking or avoiding decisions, experiencing a continuum of emotions and planning the care. Discussion: Being pregnant was part of a project women had mapped out for their lives. Only three women in our sample expressed a wish for a caesarean section. One of the strongest emotions was that of fear but in contrast some participants expressed faith that their bodies would cope with the experience. Conclusion: Bringing together the three languages and cultures produced a truly “Swiss” study showing contrasts between a matter of fact approach to pregnancy and the concept of fear. Such a contrast is worthy of further and deeper exploration by a multi-disciplinary research team

Secondary organic aerosol formation from isoprene photooxidation during cloud condensation-evaporation cycles

Abstract. The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene ∕ NOx ∕ light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are 2 and 4 times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of 2 or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to the dissolution of water soluble volatile organic compounds (VOCs) in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations. The authors thank Arnaud Allanic, Sylvain Ravier, Pascal Renard and Pascal Zapf for their contributions in the experiments. The authors also acknowledge the institutions that have provided financial support: the French National Institute for Geophysical Research (CNRS-INSU) within the LEFE-CHAT program through the project “Impact de la chimie des nuages sur la formation d’aérosols organiques secondaires dans l’atmosphère” and the French National Agency for Research (ANR) project CUMULUS ANR-2010-BLAN-617-01. This work was also supported by the EC within the I3 project “Integrating of European Simulation Chambers for Investigating Atmospheric Processes” (EUROCHAMP-2, contract no. 228335). The authors thank the MASSALYA instrumental platform (Aix Marseille Université, lce.univ-amu.fr) for the analysis and measurements used in this paper.This is the final version of the article. It first appeared from Copernicus Publications via http://dx.doi.org/10.5194/acp-16-1747-201

Characterizing the impact of urban emissions on regional aerosol particles: airborne measurements during the MEGAPOLI experiment

The MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) experiment took place in July 2009. The aim of this campaign was to study the aging and reactions of aerosol and gas-phase emissions in the city of Paris. Three ground-based measurement sites and several mobile platforms including instrument equipped vehicles and the ATR-42 aircraft were involved. We present here the variations in particle- and gas-phase species over the city of Paris, using a combination of high-time resolution measurements aboard the ATR-42 aircraft. Particle chemical composition was measured using a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), giving detailed information on the non-refractory submicron aerosol species. The mass concentration of black carbon (BC), measured by a particle absorption soot photometer (PSAP), was used as a marker to identify the urban pollution plume boundaries. Aerosol mass concentrations and composition were affected by air-mass history, with air masses that spent longest time over land having highest fractions of organic aerosol and higher total mass concentrations. The Paris plume is mainly composed of organic aerosol (OA), BC, and nitrate aerosol, as well as high concentrations of anthropogenic gas-phase species such as toluene, benzene, and NO_x. Using BC and CO as tracers for air-mass dilution, we observe the ratio of ΔOA / ΔBC and ΔOA / ΔCO increase with increasing photochemical age (−log(NO_x / NO_y)). Plotting the equivalent ratios of different organic aerosol species (LV-OOA, SV-OOA, and HOA) illustrate that the increase in OA is a result of secondary organic aerosol (SOA) formation. Within Paris the changes in the ΔOA / &Delta;CO are similar to those observed during other studies in London, Mexico City, and in New England, USA. Using the measured SOA volatile organic compounds (VOCs) species together with organic aerosol formation yields, we were able to predict ~50% of the measured organics. These airborne measurements during the MEGAPOLI experiment show that urban emissions contribute to the formation of OA and have an impact on aerosol composition on a regional scale

HAMAP: a database of completely sequenced microbial proteome sets and manually curated microbial protein families in UniProtKB/Swiss-Prot

The growth in the number of completely sequenced microbial genomes (bacterial and archaeal) has generated a need for a procedure that provides UniProtKB/Swiss-Prot-quality annotation to as many protein sequences as possible. We have devised a semi-automated system, HAMAP (High-quality Automated and Manual Annotation of microbial Proteomes), that uses manually built annotation templates for protein families to propagate annotation to all members of manually defined protein families, using very strict criteria. The HAMAP system is composed of two databases, the proteome database and the family database, and of an automatic annotation pipeline. The proteome database comprises biological and sequence information for each completely sequenced microbial proteome, and it offers several tools for CDS searches, BLAST options and retrieval of specific sets of proteins. The family database currently comprises more than 1500 manually curated protein families and their annotation templates that are used to annotate proteins that belong to one of the HAMAP families. On the HAMAP website, individual sequences as well as whole genomes can be scanned against all HAMAP families. The system provides warnings for the absence of conserved amino acid residues, unusual sequence length, etc. Thanks to the implementation of HAMAP, more than 200 000 microbial proteins have been fully annotated in UniProtKB/Swiss-Prot (HAMAP website: http://www.expasy.org/sprot/hamap)

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

In situ, satellite measurement and model evidence on the dominant regional contribution to fine particulate matter levels in the Paris megacity

International audiencePublished by Copernicus Publications on behalf of the European Geosciences Union. 9578 M. Beekmann et al.: Evidence for a dominant regional contribution to fine particulate matter levels Abstract. A detailed characterization of air quality in the megacity of Paris (France) during two 1-month intensive campaigns and from additional 1-year observations revealed that about 70 % of the urban background fine particulate matter (PM) is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in situ measurements during short intensive and longer-term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE chemistry transport models. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by comprehensive analysis of aerosol mass spectrometer (AMS), radio-carbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions constituted less than 20 % in winter and 40 % in summer of carbonaceous fine PM, unexpectedly small for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin , i.e., from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant , flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only being partially responsible for its own average and peak PM levels has important implications for air pollution regulation policies