A five year record of high-frequency in situ measurements of non-methane hydrocarbons at Mace Head, Ireland

Continuous high-frequency in situ measurements of a range of non-methane hydrocarbons have been made at Mace Head since January 2005. Mace Head is a background Northern Hemispheric site situated on the eastern edge of the Atlantic. Five year measurements (2005–2009) of six C<sub>2</sub>–C<sub>5</sub> non-methane hydrocarbons have been separated into baseline Northern Hemispheric and European polluted air masses, among other sectors. Seasonal cycles in baseline Northern Hemispheric air masses and European polluted air masses arriving at Mace Head have been studied. Baseline air masses show a broad summer minima between June and September for shorter lived species, longer lived species show summer minima in July/August. All species displayed a winter maxima in February. European air masses showed baseline elevated mole fractions for all non-methane hydrocarbons. Largest elevations (of up to 360 ppt for ethane maxima) from baseline data were observed in winter maxima, with smaller elevations observed during the summer. Analysis of temporal trends using the Mann-Kendall test showed small (<6 % yr<sup>−1</sup>) but statistically significant decreases in the butanes and <i>i</i>-pentane between 2005 and 2009 in European air. No significant trends were found for any species in baseline air

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g. <font face='Symbol' >a</font>- and <font face='Symbol' >b</font>-pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the <font face='Symbol' >a</font>-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in <font face='Symbol' >a</font>-pinene/NO_X photo-oxidation experiments carried out in the European Photoreactor (EUPHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM

Halocarbon ozone depletion and global warming potentials

Concern over the global environmental consequences of fully halogenated chlorofluorocarbons (CFCs) has created a need to determine the potential impacts of other halogenated organic compounds on stratospheric ozone and climate. The CFCs, which do not contain an H atom, are not oxidized or photolyzed in the troposphere. These compounds are transported into the stratosphere where they decompose and can lead to chlorine catalyzed ozone depletion. The hydrochlorofluorocarbons (HCFCs or HFCs), in particular those proposed as substitutes for CFCs, contain at least one hydrogen atom in the molecule, which confers on these compounds a much greater sensitivity toward oxidation by hydroxyl radicals in the troposphere, resulting in much shorter atmospheric lifetimes than CFCs, and consequently lower potential for depleting ozone. The available information is reviewed which relates to the lifetime of these compounds (HCFCs and HFCs) in the troposphere, and up-to-date assessments are reported of the potential relative effects of CFCs, HCFCs, HFCs, and halons on stratospheric ozone and global climate (through 'greenhouse' global warming)

Acid-yield measurements of the gas-phase ozonolysis of ethene as a function of humidity using Chemical Ionisation Mass Spectrometry (CIMS)

Gas-phase ethene ozonolysis experiments were conducted at room temperature to determine formic acid yields as a function of relative humidity (RH) using the integrated EXTreme RAnge chamber-Chemical Ionisation Mass Spectrometry technique, employing a CH&lt;sub&gt;3&lt;/sub&gt;I ionisation scheme. RHs studied were &lt;1, 11, 21, 27, 30 % and formic acid yields of (0.07±0.01) and (0.41±0.07) were determined at &lt;1 % RH and 30 % RH respectively, showing a strong water dependence. It has been possible to estimate the ratio of the rate coefficient for the reaction of the Criegee biradical, CH&lt;sub&gt;2&lt;/sub&gt;OO with water compared with decomposition. This analysis suggests that the rate of reaction with water ranges between 1×10&lt;sup&gt;−12&lt;/sup&gt;–1×10&lt;sup&gt;−15&lt;/sup&gt; cm&lt;sup&gt;3&lt;/sup&gt; molecule&lt;sup&gt;−1&lt;/sup&gt; s&lt;sup&gt;−1&lt;/sup&gt; and will therefore dominate its loss with respect to bimolecular processes in the atmosphere. Global model integrations suggest that this reaction between CH&lt;sub&gt;2&lt;/sub&gt;OO and water may dominate the production of HC(O)OH in the atmosphere