Abstract. An observationally constrained box model has been constructed in order to investigate the chemistry of the marine boundary layer at Mace Head, a remote location on the west coast of Ireland. The primary aim of the model is to reproduce concentrations of the hydroxyl (OH) and hydroperoxy (HO2) radicals measured by an in situ fluorescence assay by gas expansion (

Comprehensive two-dimensional gas chromatography-time-of-flight-mass-spectrometry can be used to resolve and identify individual petroleum-derived hydrocarbons in unresolved complex mixtures (UCMs), such as those accumulated by mussels (Mytilus edulis). Mussels exhibiting a range of scope for growth values were collected from sites around the UK coast. Tissue extracts from mussels exhibiting impaired health contained large amounts of aromatic hydrocarbon UCMs compared to the extracts from healthy mussels. The UCMs (up to 125 microg g(-1) dry tissue) contained thousands of previously unidentified branched alkyl homologues of known aromatic hydrocarbons such as branched alkylbenzenes (BABs), tetralins (BATs), and indanes and indenes (BINs). The toxicity of few such alkyl branched compounds has been investigated previously, but here we show that a commercial mixture of BABs (C12-C14) is toxic to mussels in laboratory tests (11-57 microg g(-1) dry tissue), reducing feeding rate by up to 40% in 72 h. Thus, some, if not all aromatic UCMs, apparently comprise potent mixtures of persistent, bioaccumulative and toxic compounds which have been overlooked previously.

Abstract. Partially oxidised organic compounds associated with PM2.5 aerosol collected in London, England, have been analysed using direct thermal desorption coupled to comprehensive gas chromatography-time of flight mass spectrometry (GCXGC-TOF/MS). Over 10000 individual organic components were isolated from around 10µg of aerosol material in a single procedure and with no sample pre-treatment. Chemical functionalities observed using this analytical technique ranged from alkanes to poly-oxygenated species. The chemical band structures commonly used in GCXGC for group type identifications overlap for this sample type, and have required mass spectrometry as an additional level of instrument dimensionality. An investigation of oxygenated volatile organic compounds (o-VOC) contained within urban aerosol has been performed and in a typical sample around 130 o-VOCs were identified based on retention behaviour and spectral match. In excess of 100 other oxygenated species were also observed but lack of mass spectral library or pure components prevents positive identification. Many of the carbonyl species observed could be mechanistically linked to gas phase aromatic hydrocarbon oxidation and there is good agreement in terms of speciation between the urban samples analysed here and those degradation products observed in smog chamber experiments of aromatic oxidation. The presence of partially oxidised species such as linear chain aldehydes and ketones and cyclic products such as furanones suggests that species generated early in the oxidative process may undergo gas to particle partitioning despite their relatively high volatility.

Abstract. Measurements of acetone, methanol, acetaldehyde and a range of non-methane hydrocarbons have been made in North Atlantic marine air at the Mace Head observatory. Under maritime conditions the combination of OVOCs (acetone, methanol and acetaldehyde) contributed up to 85% of the total mass of measured non methane organics in air and up to 80% of the OH radical organic sink, when compared with the sum of all other organic compounds including non-methane hydrocarbons, DMS and OH-reactive halocarbons (trichloromethane and tetrachloroethylene). The observations showed anomalies in the variance and abundance of acetaldehyde and acetone over that expected for species with a remote terrestrial emission source and OH controlled chemical lifetime. A detailed model incorporating an explicit chemical degradation mechanism indicated in situ formation during air mass transport was on timescales longer than the atmospheric lifetime of precursor hydrocarbons or primary emission. The period over which this process was significant was similar to that of airmass motion on intercontinental scales, and formation via this route may reproduce that of a widespread diffuse source. The model indicates that continued short chain OVOC formation occurs many days from the point of emission, via longer lived intermediates of oxidation such as organic peroxides and long chain alcohols.

No abstract

Abstract. In March 2020, non-pharmaceutical intervention measures in the form of lockdowns were applied across Europe to urgently reduce the transmission of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the virus which causes the COVID-19 disease. The aggressive curtailing of the European economy had widespread impacts on the atmospheric composition, particularly for nitrogen dioxide (NO2) and ozone (O3). To investigate these changes, we analyse data from 246 ambient air pollution monitoring sites in 102 urban areas and 34 countries in Europe between February and July 2020. Counterfactual, business-as-usual air quality time series are created using machine-learning models to account for natural weather variability. Across Europe, we estimate that NO2 concentrations were 34 % and 32 % lower than expected for respective traffic and urban background locations, whereas O3 was 30 % and 21 % higher (in the same respective environments) at the point of maximum restriction on mobility. To put the 2020 changes into context, average NO2 trends since 2010 were calculated, and the changes experienced across European urban areas in 2020 was equivalent to 7.6 years of average NO2 reduction (or concentrations which might be anticipated in 2028). Despite NO2 concentrations decreasing by approximately a third, total oxidant (Ox) changed little, suggesting that the reductions in NO2 were substituted by increases in O3. The lockdown period demonstrated that the expected future reductions in NO2 in European urban areas are likely to lead to widespread increases in urban O3 pollution unless additional mitigation measures are introduced.

Abstract. Wintertime in situ measurements of OH, HO2 and RO2 radicals and OH reactivity were made in central Beijing during November and December 2016. Exceptionally elevated NO was observed on occasions, up to ∼250 ppbv. The daily maximum mixing ratios for radical species varied significantly day-to-day over the ranges 1–8×106 cm−3 (OH), 0.2–1.5×108 cm−3 (HO2) and 0.3–2.5×108 cm−3 (RO2). Averaged over the full observation period, the mean daytime peak in radicals was 2.7×106, 0.39×108 and 0.88×108 cm−3 for OH, HO2 and total RO2, respectively. The main daytime source of new radicals via initiation processes (primary production) was the photolysis of HONO (∼83 %), and the dominant termination pathways were the reactions of OH with NO and NO2, particularly under polluted haze conditions. The Master Chemical Mechanism (MCM) v3.3.1 operating within a box model was used to simulate the concentrations of OH, HO2 and RO2. The model underpredicted OH, HO2 and RO2, especially when NO mixing ratios were high (above 6 ppbv). The observation-to-model ratio of OH, HO2 and RO2 increased from ∼1 (for all radicals) at 3 ppbv of NO to a factor of ∼3, ∼20 and ∼91 for OH, HO2 and RO2, respectively, at ∼200 ppbv of NO. The significant underprediction of radical concentrations by the MCM suggests a deficiency in the representation of gas-phase chemistry at high NOx. The OH concentrations were surprisingly similar (within 20 % during the day) in and outside of haze events, despite j(O1D) decreasing by 50 % during haze periods. These observations provide strong evidence that gas-phase oxidation by OH can continue to generate secondary pollutants even under high-pollution episodes, despite the reduction in photolysis rates within haze.

Abstract. A fast growing area of research is the development of low-cost sensors for measuring air pollutants. The affordability and size of low-cost particle sensors makes them an attractive option for use in experiments requiring a number of instruments such as high density spatial mapping. However, for these low-cost sensors to be useful for these types of studies their accuracy and precision needs to be quantified. We evaluated the Alphasense OPC-N2, a promising low-cost miniature optical particle counter, for monitoring ambient airborne particles at typical urban background sites in the UK. The precision of the OPC-N2 was assessed by co-locating 14 instruments at a site to investigate the variation in measured concentrations. Comparison to two different reference optical particle counters as well as a TEOM-FDMS enabled the accuracy of the OPC-N2 to be evaluated. Comparison of the OPC-N2 to the reference optical instruments demonstrated reasonable agreement for the measured mass concentrations of PM1, PM2.5 and PM10. However, the OPC-N2 demonstrated a significant positive artefact in measured particle mass during times of high ambient RH (> 85 %) and a calibration factor was developed based upon κ-Kohler theory, using average bulk particle aerosol hygroscopicity. Application of this RH correction factor resulted in the OPC-N2 measurements being within 33 % of the TEOM-FDMS, comparable to the agreement between a reference optical particle counter and the TEOM-FDMS (20 %). Reasonable inter-unit precision for the 14 OPC-N2 sensors was observed. Overall, the OPC-N2 was found to accurately measure ambient airborne particle mass concentration provided they are i) correctly calibrated and ii) corrected for ambient RH. The reasonable level of precision demonstrated between multiple OPC-N2 suggests that they would be suitable device for applications where the spatial variability in particle concentration was to be determined.