Criegee intermediates and their impacts on the troposphere.

Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. The decomposition of CIs can be a significant source of OH to the tropospheric oxidation cycle especially during nighttime and winter months. A variety of model-measurement studies have estimated surface-level stabilized Criegee intermediate (sCI) concentrations on the order of 1 × 104 cm-3 to 1 × 105 cm-3, which makes a non-negligible contribution to the oxidising capacity in the terrestrial boundary layer. The reactions of sCI with the water monomer and the water dimer have been found to be the most important bimolecular reactions to the tropospheric sCI loss rate, at least for the smallest carbonyl oxides; the products from these reactions (e.g. hydroxymethyl hydroperoxide, HMHP) are also of importance to the atmospheric oxidation cycle. The sCI can oxidise SO2 to form SO3, which can go on to form a significant amount of H2SO4 which is a key atmospheric nucleation species and therefore vital to the formation of clouds. The sCI can also react with carboxylic acids, carbonyl compounds, alcohols, peroxy radicals and hydroperoxides, and the products of these reactions are likely to be highly oxygenated species, with low vapour pressures, that can lead to nucleation and SOA formation over terrestrial regions.

Constraints on oceanic methane emissions west of Svalbard from atmospheric in situ measurements and Lagrangian transport modeling.

Methane stored in seabed reservoirs such as methane hydrates can reach the atmosphere in the form of bubbles or dissolved in water. Hydrates could destabilize with rising temperature further increasing greenhouse gas emissions in a warming climate. To assess the impact of oceanic emissions from the area west of Svalbard, where methane hydrates are abundant, we used measurements collected with a research aircraft (Facility for Airborne Atmospheric Measurements) and a ship (Helmer Hansen) during the Summer 2014 and for Zeppelin Observatory for the full year. We present a model-supported analysis of the atmospheric CH4 mixing ratios measured by the different platforms. To address uncertainty about where CH4 emissions actually occur, we explored three scenarios: areas with known seeps, a hydrate stability model, and an ocean depth criterion. We then used a budget analysis and a Lagrangian particle dispersion model to compare measurements taken upwind and downwind of the potential CH4 emission areas. We found small differences between the CH4 mixing ratios measured upwind and downwind of the potential emission areas during the campaign. By taking into account measurement and sampling uncertainties and by determining the sensitivity of the measured mixing ratios to potential oceanic emissions, we provide upper limits for the CH4 fluxes. The CH4 flux during the campaign was small, with an upper limit of 2.5 nmol m-2 s-1 in the stability model scenario. The Zeppelin Observatory data for 2014 suggest CH4 fluxes from the Svalbard continental platform below 0.2 Tg yr-1. All estimates are in the lower range of values previously reported.

Physical and chemical processes of air masses in the Aegean Sea during Etesians: Aegean-GAME airborne campaign.

High-resolution measurements of gas and aerosols' chemical composition along with meteorological and turbulence parameters were performed over the Aegean Sea (AS) during an Etesian outbreak in the framework of the Aegean-GAME airborne campaign. This study focuses on two distinct Etesian patterns, with similarities inside the Marine Atmospheric Boundary Layer (MABL) and differences at higher levels. Under long-range transport and subsidence the pollution load is enhanced (by 17% for CO, 11% for O3, 28% for sulfate, 62% for organic mass, 47% for elemental carbon), compared to the pattern with a weaker synoptic system. Sea surface temperature (SST) was a critical parameter for the MABL structure, turbulent fluxes and pollutants' distribution at lower levels. The MABL height was below 500 m asl over the eastern AS (favoring higher accumulation), and deeper over the western AS. The most abundant components of total PM1 were sulfate (40-50%) and organics (30-45%). Higher average concentrations measured over the eastern AS (131 ± 76 ppbv for CO, 62.5 ± 4.1 ppbv for O3, 5.0 ± 1.1 µg m(-3) for sulfate, 4.7 ± 0.9 µg m(-3) for organic mass and 0.5 ± 0.2 µg m(-3) for elemental carbon). Under the weaker synoptic system, cleaner but more acidic air masses prevailed over the eastern part, while distinct aerosol layers of different signature were observed over the western part. The Aitken and accumulation modes contributed equally during the long-range transport, while the Aitken modes dominated during local or medium range transport.

Criegee intermediates in the indoor environment: new insights.

Criegee intermediates are formed in the ozonolysis of alkenes and play an important role in indoor chemistry, notably as a source of OH radicals. Recent studies have shown that these Criegee intermediates react very quickly with NO2 , SO2 , and carbonyls, and in this study, steady-state calculations are used to inspect the potential impact of these data on indoor chemistry. It is shown that these reactions could accelerate NO3 formation and SO2 removal in the indoor environment significantly. In addition, reaction between Criegee intermediates and halogenated carbonyls could provide a significant loss process indoors, where currently one does not exist.

Layer guided-acoustic plate mode biosensors for monitoring MHC-peptide interactions.

The transduction signals from the immobilisation of a class I heavy chain, HLA-A2, on a layer guided acoustic plate mode device, followed by binding of beta(2)-microglobulin and subsequent selective binding of a target peptide are reported.

Detection of polycyclic aromatic hydrocarbons using quartz crystal microbalances.

A chemically coated piezoelectric sensor has been developed for the determination of PAHs in the liquid phase. An organic monolayer attached to the surface of a gold electrode of a quartz crystal microbalance (QCM) via a covalent thiol-gold link complete with an ionically bound recognition element has been produced. This study has employed the PAH derivative 9-anthracene carboxylic acid which, once bound to the alkane thiol, functions as the recognition element. Binding of anthracene via pi-pi interaction has been observed as a frequency shift in the QCM with a detectability of the target analyte of 2 ppb and a response range of 0-50 ppb. The relative response of the sensor altered for different PAHs despite pi-pi interaction being the sole communication between recognition element and analyte. It is envisaged that such a sensor could be employed in the identification of key marker compounds and, as such, give an indication of total PAH flux in the environment.

Molecular imprinted polymer coated QCM for the detection of nandrolone.

An acoustic wave sensor coated with an artificial biomimetic recognition element has been developed to selectively screen for nandrolone in the liquid phase. A highly specific covalently imprinted polymer (MIP) was spin coated onto one electrode of a quartz crystal microbalance (QCM) as a thin permeable film. Selective rebinding of the nandrolone was observed as a frequency shift in the QCM for concentrations up to 0.2 ppm with the sensor binding shown to favour nandrolone over analogous compounds.

Molecular-imprinted, polymer-coated quartz crystal microbalances for the detection of terpenes.

A piezoelectric sensor coated with an artificial biomimetic recognition element has been developed for the determination of L-menthol in the liquid phase. A highly specific noncovalently imprinted polymer (MIP) was cast in situ on to the surface of a gold-coated quartz crystal microbalance (QCM) electrode as a thin permeable film. Selective rebinding of the target analyte was observed as a frequency shift quantified by piezoelectric microgravimetry with the QCM. The detectability of L-menthol was 200 ppb with a response range of 0-1.0 ppm. The response of the MIP-QCM to a range of monoterpenes was investigated with the sensor binding menthol in favor of analogous compounds. The sensor was able to distinguish between the D- and L-enantiomers of menthol owing to the enantioselectivity of the imprinted sites. To our knowledge, this is the first report describing enantiomeric resolution within an MIP utilizing a single monomer-functional moiety interaction. It is envisaged that this technique could be employed to determine the concentration of terpenes in the atmosphere.

Arterial-alveolar oxygen partial pressure ratio: a theoretical reappraisal.

The relationship between the arterial-alveolar oxygen partial pressure ratio (PaO2/PAO2) and different fractions of inspired oxygen (FIO2) was studied using a bicompartmental computer model. PaO2/PAO2 was found to be less stable than in previous clinical works probably because the venous admixture varied with changes in the FIO2.