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Main text The CCQM-K10.2018 comparison aimed to evaluate the capabilities of national metrology institutes (NMIs) to prepare and/or value assign primary reference mixtures containing benzene, toluene, ethylbenzene, p-xylene, m-xylene and o-xylene (subsequently referred to as BTEX) in nitrogen. This key comparison was separated into two parallel studies. The first study, deemed the "gravimetric study", evaluated the level of compatibility of BTEX standards provided by NMIs. Seven participating laboratories each submitted one standard at nominal 5 nmol mol-1 BTEX in nitrogen. Comparison measurements were performed by the National Institute of Standards and Technology (NIST) from July to October 2018. The second study, deemed the "comparative study", compared the capabilities of NMIs to measure the amount fractions of BTEX in a mixture provided by NIST. NIST prepared one standard at nominal 5 nmol mol-1 BTEX in nitrogen, which was measured consecutively by three participating laboratories. The participants' measurements took place from August 2018 to March 2019. The comparison protocol adopted for CCQM-K10.2018 was more challenging than for the original comparison, CCQM-K10 in 2001, and the results provide an extended evaluation of the level of compatibility of BTEX in nitrogen standards. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

This work reports the first statistical analysis of multi-annual data on tropospheric aerosols from the German Ultrafine Aerosol Network (GUAN). Compared to other networks worldwide, GUAN with 17 measurement locations has the most sites equipped with particle number size distribution (PNSD) and equivalent black carbon (eBC) instruments and the most site categories in Germany ranging from city street/roadside to High Alpine. As we know, the variations of eBC and particle number concentration (PNC) are influenced by several factors such as source, transformation, transport and deposition. The dominant controlling factor for different pollutant parameters might be varied, leading to the different spatio-temporal variations among the measured parameters. Currently, a study of spatio-temporal variations of PNSD and eBC considering the influences of both site categories and spatial scale is still missing. Based on the multi-site dataset of GUAN, the goal of this study is to investigate how pollutant parameters may interfere with spatial characteristics and site categories.

The environmental impacts of ammonia (NH3) in ambient air have become more evident in the recent decades, leading to intensifying research in this field. A number of novel analytical techniques and monitoring instruments have been developed, and the quality and availability of reference gas mixtures used for the calibration of measuring instruments has also increased significantly. However, recent inter-comparison measurements show significant discrepancies, indicating that the majority of the newly developed devices and reference materials require further thorough validation. There is a clear need for more intensive metrological research focusing on quality assurance, intercomparability and validations. MetNH3 (Metrology for ammonia in ambient air) is a three-year project within the framework of the European Metrology Research Programme (EMRP), which aims to bring metrological traceability to ambient ammonia measurements in the 0.5-500 nmol mol-1 amount fraction range. This is addressed by working in three areas: (1) improving accuracy and stability of static and dynamic reference gas mixtures, (2) developing an optical transfer standard and (3) establishing the link between high-accuracy metrological standards and field measurements. In this article we describe the concept, aims and first results of the project.

The German Ultrafine Aerosol Network (GUAN) is a cooperative atmospheric observation network, which aims at improving the scientific understanding of aerosol-related effects in the troposphere. The network addresses research questions dedicated to both climate- and health-related effects. GUAN's core activity has been the continuous collection of tropospheric particle number size distributions and black carbon mass concentrations at 17 observation sites in Germany. These sites cover various environmental settings including urban traffic, urban background, rural background, and Alpine mountains. In association with partner projects, GUAN has implemented a high degree of harmonisation of instrumentation, operating procedures, and data evaluation procedures. The quality of the measurement data is assured by laboratory intercomparisons as well as on-site comparisons with reference instruments. This paper describes the measurement sites, instrumentation, quality assurance, and data evaluation procedures in the network as well as the EBAS repository, where the data sets can be obtained (doi:10.5072/guan).

The photolysis of o-tolualdehyde by natural sunlight has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The photolysis rate coefficient was measured directly under different solar flux levels, with values in the range j(o-tolualdehyde) = (1.62-2.15) × 10(-4) s(-1) observed, yielding an average value of j(o-tolualdehyde)/j(NO(2)) = (2.53 ± 0.25) × 10(-2). The estimated photolysis lifetime is 1-2 h, confirming that direct photolysis by sunlight is the major atmospheric degradation pathway for o-tolualdehyde. Published UV absorption cross-section data were used to derive an effective quantum yield (290-400 nm) close to unity, within experimental error. Possible reaction pathways for the formation of the major photolysis products, benzocyclobutenol (tentatively identified) and o-phthalaldehyde, are proposed. Appreciable yields (5-13%) of secondary organic aerosol (SOA) were observed at EUPHORE and also during supplementary experiments performed in an indoor chamber using an artificial light source. Off-line analysis by gas chromatography-mass spectrometry allowed identification of o-phthalaldehyde, phthalide, phthalic anhydride, o-toluic acid, and phthalaldehydic acid in the particle phase.

Zusammenfassung Die RKI-Empfehlungen aus 1999 sind inzwischen alter als 10 Jahre und auf Grund des Fehlens randomisierter kontrollierter Studien ist die Handehygiene die einzige Evidenz-basierte Methode. Die im MRSA-KISS-Modul uber einen Zeitraum von 3 Jahren (2008 – 2010) ermittelte MRSA-Rate von 37 Krankenhausern nahm kontinuierlich ab und war in 2010 unter dem arithmetischen Mittel der Daten des Nationalen Referenzzentrums fur die Surveillance von Krankenhausinfektionen (NRZ). Die Implementierung intensiver Surveillance, des Screenings von Risikopatienten, der Standardhygienemasnahmen, Handehygiene und individuellen Isolierung ist hinsichtlich der Reduktion nosokomialer MRSA-Kolonisationen und Infektionen eine effektive Masnahme.

Dans le cadre du Programme de Recherche Europeen en Metrologie (EMRP), un projet de trois ans a debute en juin 2014 avec l’objectif d’ameliorer la comprehension et la tracabilite metrologique des mesures d’ammoniac (NH3) ambient, dans le domaine 0.5 - 500 nmol/mol. Les trois tâches principales de ce projet sont 1) d’ameliorer l’exactitude et la stabilite de melanges de gaz de reference statiques et dynamiques, 2) de developper un etalon de transfert optique et 3) d’etablir un lien entre les standards metrologiques de haute precision et les mesures de terrain. Les resultats attendus de ce projet vont ameliorer l’exactitude et la fiabilite des estimations d’emissions et ainsi aider a l’evaluation de l’efficacite des mesures de reduction d’emission prescrites par les reglementations internationales. Dans cette publication nous decrivons le concept, les objectifs et les premiers resultats du projet.

The secondary organic aerosol formed during the photo-oxidation of o-tolualdehyde in a large smog reaction chamber has been studied using comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry. The separation and detection system was coupled directly to an aerosol thermal desorption stage, providing the ability to resolve all gas chromatography amenable species in a single experimental procedure. The organic content of aerosol formed from the photo-oxidation of o-tolualdehyde contained a diverse range of chemical functionalities including mono-aromatic, carboxylic acid and carbonyl which were predicted as photochemical by-products by a comprehensive chemical mechanism. Around 3% of the organic aerosol content resolved was polycyclic-aromatic in nature. This has indicated that the formation of relatively low volatility by-products was possible via the ring-retained channel from a mono-aromatic precursor. Species found included 2,3 naphthalene dicarboxylic acid, and anthraquin...

It is essential to quantify the background reactivity of smog-chambers, since this might be the major limitation of experiments carried out at low pollutant concentrations typical of the polluted atmosphere. Detailed investigation of three chamber experiments at zero-NOx in the European Photoreactor (EUPHORE) were carried out by means of rate-of-production analysis and two uncertainty analysis tools: local uncertainty analysis and Monte Carlo simulations with Latin hypercube sampling. The chemical mechanism employed was that for methane plus the inorganic subset of the Master Chemical Mechanism (MCMv3.1). Newly installed instruments in EUPHORE allowed the measurement of nitrous acid and formaldehyde at sub-ppb concentrations with high sensitivity. The presence of HONO and HCHO during the experiments could be explained only by processes taking place on the FEP Teflon walls. The HONO production rate can be described by the empirical equation W(HONO)EUPHOREdry = a × jNO2× exp (− T0/T) in the low relative humidity region (RH < 2%, a = 7.3×1021 cm−3, T0 = 8945K), and by the equation W(HONO)EUPHOREhumid = W(HONO)EUPHOREdry+ jNO2× b × RHq in the higher relative humidity region (2% < RH < 15%, b = 5.8×108 cm−3 and q = 0.36, and RH is the relative humidity in percentages). For HCHO the expression W(HCHO)EUPHORE = c × jNO2exp (− T′0/T) is applicable (c = 3.1×1017 cm−3 and T′0 = 5686 K). In the 0–15% relative humidity range OH production from HONO generated at the wall is about a factor of two higher than that from the photolysis of 100 ppb ozone. Effect of added NO2 was found to be consistent with the dark HONO formation rate coefficient of MCMv3.1.

The photolysis of glyoxal in synthetic air was investigated in a quartz cell at 298 K using three types of UV sources (TL/12 lamps (275–380 nm), TL/03 lamps (390–470 nm) and mercury lamps (254 nm)) and products were identified and quantitatively analyzed using long-path FTIR spectroscopy. For all light sources, the observed products were CO, HCHO and HCOOH. Absolute quantum yields were determined using Cl2 and Br2 as actinometers. Photolysis in the first absorption band of glyoxal, using TL/12 lamps, provided an overall quantum yield of ΦT = 0.97 ± 0.05, independent of total pressure ranging from 100 to 700 Torr air. The absolute quantum yields obtained with the TL/03 lamps, covering the second absorption band of glyoxal, showed dependency on total pressure, ranging from ΦT = 0.12 at 100 Torr to ΦT = 0.042 at 700 Torr, which can be expressed as a Stern–Volmer-type equation 1/ΦT = (6.80 + 251.8) × 10−4 × P (Torr). By combining the product yields with literature data, we deduced the detailed picture of glyoxal photolysis, including the dependency of the quantum yield of each particular channel: CHOCHO + hν → 2HCO (Φ1); CHOCHO + hν → H2 + 2CO (Φ2); CHOCHO + hν → H2CO + CO (Φ3) on the applied wavelength. The product quantum yields indicate that dissociation into two HCO radicals is the most important pathway under atmospheric conditions. The mean photolysis rate was measured under solar radiation in the EUPHORE outdoor chamber to be Jobs = 1.04 ± 0.10 × 10−4 s−1, corresponding to a mean effective quantum yield ϕeff = 0.035 ± 0.007. Although glyoxal has a very low effective quantum yield, photolysis remains an important removal path in the atmosphere.

Monoterpenes are ubiquitous in forested environments and are subject to reactions with OH radicals, NO3 radicals and O3 both within and above forest canopies. While reactions of monoterpenes with OH and O3 have received considerable attention with regard to their reaction kinetics, reaction products and secondary organic aerosol (SOA) formation those with NO3 have received relatively little consideration. To redress this imbalance and to try and assess the possible importance of NO3+monterpene reactions within forest canopies investigations have been performed on selected monterpenes. The products and aerosol formation from the NO3 radical initiated oxidation of limonene and α-pinene have been investigated in the EUPHORE photoreactor facility, and the secondary chemistry of the observed major products was then investigated in a large volume laboratory photoreactor. In addition to large yields of yet unidentified organic nitrates, pinonaldehyde and endolim have been identified as the major reaction products of the NO3 radical initiated oxidation of α-pinene and limonene, respectively. The aerosol formation has been investigated in the presence of different seed aerosols and also water vapour. The reactions lead to the formation of SOA and the results indicate the importance of the chemical character of the seed aerosol in determining the SOA yield in NO3+monoterpene reactions. The possible pathways leading to SOA formation and also their potential importance are discussed based on the laboratory results on the reaction of NO3 with the two major products.

Methods of uncertainty analysis were used for comparison of the Master Chemical Mechanism version 3 (MCMv3) with measurements made in the European Photoreactor (EUPHORE) at Valencia (Spain) to investigate model–measurement discrepancies and to obtain information on the importance of wall effects. Two EUPHORE smog chamber measurements of ethene oxidation, under high and low NOx conditions were analysed by the following methods: (i) local uncertainty analysis, (ii) the global screening method of Morris and (iii) Monte Carlo (MC) analysis with Latin hypercube sampling. For both experiments, ozone (by 25% and 30%, respectively) and formaldehyde (by 34% and 40%, respectively) are significantly over-predicted by the model calculations, while the disagreement for other species is less substantial. According to the local uncertainty analysis and the Morris method, the most important contributor to ozone uncertainty under low NOx conditions is HOCH2CH2O2+NO→HOCH2CH2O+NO2, while under high NOx conditions OH+NO2→HNO3 is the main contributor. The MC simulations give an estimate of the 2σ uncertainty for ozone as ∼20% in both scenarios at the end of the experiment. The results suggest systematic disagreement between measurements and model calculations, although the origin of this is not clear. It seems that chamber effects alone are not responsible for the observed discrepancies.

A high quality dataset on the photo-oxidation of benzene, toluene, p-xylene and 1,3,5-trimethylbenzene has been obtained from experiments in the European Photoreactor (EUPHORE), a large outdoor environmental reaction chamber. The experiments were designed to test sensitive features of detailed aromatic mechanisms, and the dataset has been used to evaluate the performance of the Master Chemical Mechanism Version 3 (MCMv3). An updated version (MCMv3.1) was constructed based on recent experimental data, and details of its development are described in a companion paper. The MCMv3.1 aromatic mechanisms have also been evaluated using the EUPHORE dataset. Significant deficiencies have been identified in the mechanisms, in particular: 1) an over-estimation of the ozone concentration, 2) an under-estimation of the NO oxidation rate, 3) an under-estimation of OH. The use of MCMv3.1 improves the model-measurement agreement in some areas but significant discrepancies remain.

It is currently assumed that benzene contributes only negligibly to secondary organic aerosol formation in the atmosphere. Our understanding of the capacity of benzene to generate secondary aerosols is based on the work of Izumi and Fukuyama (Atmos. Environ. 1990, 24A, 1433) in which two photosmog experiments with benzene in the presence of NOx were performed and no particle formation was observed. In contrast to the observations of Izumi and Fukuyama, experiments performed in the EUPHORE large outdoor simulation chamber have clearly shown aerosol formation during the photochemical oxidation of benzene in various NOx regimes. The maximum aerosol yields of 8-25% on a mass basis are comparable to yields obtained during the photochemical oxidation of other aromatic compounds under similar conditions. In addition, a density of 1.35+/-0.04 g/cm3 for the secondary organic aerosol from the benzene photochemical oxidation in the presence of NOx has been determined through the simultaneous measurement of aerosol volume and aerosol mass using two independent measurement techniques. Comparing the results in the present work with previous findings underscores the strong influence that the NOx content in the system has on aerosol formation during the photochemical oxidation of aromatic hydrocarbons and the importance of performing experiments with NOx concentrations relevant to the atmosphere.

Using a relative kinetic technique, rate coefficients have been determined at (298 ± 2) K and atmospheric pressure for the gas-phase reactions of the NO3 radical with three vicinal dihydroxy aromatic compounds. The experiments were carried out in a 1080-l quartz glass reactor at the Bergische Universitat Wuppertal and in the European Photoreactor (EUPHORE), Valencia, Spain. The rate coefficients obtained (in units of cm3 molecule−1 s−1) using 2,3-dimethyl-2-butene as the reference hydrocarbon were kNO3(1,2-dihydroxybenzene) = (9.8 ± 5.0) × 10−11, kNO3(1,2-dihydroxy-3-methylbenzene) = (17.2 ± 5.6) × 10−11, and kNO3 (1,2- dihydroxy-4-methylbenzene) = (14.7 ± 6.5) × 10−11. This study represents the first kinetic investigation of the reactions of the NO3 radical with dihydroxybenzenes. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 577–583, 2004

Photo-oxidation products from the reaction of a series of alkyl-benzenes, (benzene, toluene, p-xylene and 1,3,5-trimethyl-benzene) with hydroxyl radicals in the presence of NOx have been investigated using comprehensive gas chromatography (GCxGC). A GCxGC system has been developed which utilises valve modulation and independent separations as a function of both volatility and polarity. A number of carbonyl-type compounds were identified during a series of reactions carried out at the European Photoreactor (EUPHORE), a large volume outdoor reaction chamber in Valencia, Spain. Experiments were carried as part of the EXACT project (Effects of the oXidation of Aromatic Compounds in the Troposphere). Two litre chamber air samples were cryo-focused, with a sampling frequency of 30 minutes, allowing the evolution of species to be followed over oxidation periods of 3-6 hours. To facilitate product identification, several carbonyl compounds, which were possible products of the photo-oxidation, were synthesised and used as reference standards. For toluene reactions, observed oxygenated intermediates found included the co-eluting pair a-angelicalactone/4-oxo-2-pentenal, maleic anhydride, citraconic anhydride, benzaldehyde and p-methyl benzoquinone. In the p-xylene experiment, the products identified were E/Z-hex-3-en-2,5-dione and citraconic anhydride. For 1,3,5-TMB reactions, the products identified were 3,5-dimethylbenzaldehyde, 3,5-dimethyl-3H-furan-2-one and 3-methyl-5-methylene-5H-furan-2-one. Preliminary quantification was carried out on identified compounds using liquid standards. Comparison of FTIR and GCxGC for the measurement of the parent aromatics generally showed good agreement. Comparison of the concentrations observed by GCxGC to concentration-time profiles simulated using the Master Chemical Mechanism, MCMv3, demonstrates that this mechanism significantly over-predicts the concentrations of many product compounds and highlights the uncertainties which exist in our understanding of the atmospheric oxidation of aromatics.

Toluene photooxidation is chosen as an example to examine how simulations of smog-chamber experiments can be used to unravel shortcomings in detailed mechanisms and to provide information on complex reaction systems that will be crucial for the design of future validation experiments. The mechanism used in this study is extracted from the Master Chemical Mechanism Version 3 (MCM v3) and has been updated with new modules for cresol and g-dicarbonyl chemistry. Model simulations are carried out for a toluene-NOx experiment undertaken at the European Photoreactor (EUPHORE). The comparison of the simulation with the experimental data reveals two fundamental shortcomings in the mechanism: OH production is too low by about 80%, and the ozone concentration at the end of the experiment is over-predicted by 55%. The radical budget was analysed to identify the key intermediates governing the radical transformation in the toluene system. Ring-opening products, particularly conjugated g-dicarbonyls, were identified as dominant radical sources in the early stages of the experiment. The analysis of the time evolution of radical production points to a missing OH source that peaks when the system reaches highest reactivity. First generation products are also of major importance for the ozone production in the system. The analysis of the radical budget suggests two options to explain the concurrent under-prediction of OH and over-prediction of ozone in the model: 1) missing oxidation processes that produce or regenerate OH without or with little NO to NO2 conversion or 2) NO3 chemistry that sequesters reactive nitrogen oxides into stable nitrogen compounds and at the same time produces peroxy radicals. Sensitivity analysis was employed to identify significant contributors to ozone production and it is shown how this technique, in combination with ozone isopleth plots, can be used for the design of validation experiments.

The present work represents a continuation of part I of this series of papers, in which we investigated the phenol yields in the OH-initiated oxidation of benzene under conditions of low to moderate concentrations of NOx, to elevated NOx levels. The products of the OH-initiated oxidation of benzene in 700–760 Torr of N2/O2 diluent at 297 ± 4 K were investigated in 3 different photochemical reaction chambers. In situ spectroscopic techniques were employed for the detection of products, and the initial concentrations of benzene, NOx, and O2 were widely varied (by factors of 6300, 1500, and 13, respectively). In contrast to results from previous studies, a pronounced dependence of the product distribution on the NOx concentration was observed. The phenol yield decreases from approximately 50–60% in the presence of low concentrations ( 10 000 ppb) NOx concentrations. In the presence of high concentrations of NOx, the phenol yield increases with increasing O2 partial pressure. The rate constant of the reaction of hydroxycyclohexadienyl peroxyl radicals with NO was determined to be (1.7 ± 0.6) × 10−11 cm3 molecule−1 s−1. This reaction leads to the formation of E,E-2,4-hexadienedial as the main identifiable product (29 ± 16%). The reaction of the hydroxycyclohexadienyl radical with NO2 gave phenol (5.9 ± 3.4%) and E,E-2,4-hexadienedial (3.4 ± 1.9%), no other products could be identified. The residual FTIR product spectra indicate the formation of unknown nitrates or other nitrogen-containing species in high yield. The results from the present work also show that experimental studies aimed at establishing/verifying chemical mechanisms for aromatic hydrocarbons must be performed using NOx levels which are representative of those found in the atmosphere.

The evaluation results of the metrological performance of a dilution and a permeation standard for generating SI-traceable calibration gas mixtures of NO, SO2 and NO2 for ambient air measurements are presented. The composition of the in situ produced reference gas mixtures is calculated from the instantaneous values of the input quantities of the generating standards. In a measurement comparison, the calibration and measurement capabilities of five laboratories were evaluated for the three analytes at limiting amount of substance fractions in ambient air between 20 and 150 nmol mol−1. For the upper generated reference values the target relative uncertainties of ≤2% (for NO and SO2) and ≤3% (for NO2) for evaluating the laboratory results were fulfilled in 12 out of 13 cases. For the analytical results seven out of nine laboratories met the criteria for the upper values for NO and NO2, for SO2 it was one out of four. From the negative degrees of equivalence of all NO2 comparison results it was supposed that the permeation rate of NO2 through the FEP polymer membrane of the permeator was different in air and N2. Subsequent precision permeation measurements with various carrier gases revealed that the permeation rate of NO2 was ≈0.8% lower in synthetic air compared to N2. With the corrected NO2 reference values for air the degrees of equivalence of the laboratory results were improved and closer to be symmetrically distributed.

A new approach is presented to study the ring-cleavage process of benzene, toluene, and p-xylene (BTX). DOAS (differential optical absorption spectroscopy) was used for the simultaneous measurement of the respective ring-retaining products as well as glyoxal (a ring-cleavage product) in a series of experiments at the EUPHORE outdoor simulation chamber, Valencia/Spain. The good time resolution of the DOAS measurements (1-2 min) allowed the primary formation of glyoxal to be separated from any further contributions through additional pathways via reactions of stable intermediate compounds (secondary glyoxal formation). The ring-retaining products and glyoxal were identified as primary products. The primary glyoxal yield was found to be essentially identical to the overall yield of glyoxal formed over the time scale of the experiments. The negligible contribution from secondary glyoxal formation pathways was quantitatively understood for the experimental conditions of this study and was found to be representative for the troposphere. The yield of glyoxal was determined to be 35% ( 10% for benzene and about 5% higher for toluene and p-xylene. For benzene, the yield of hexadienedial was estimated to be e 8%. It is concluded that ringcleavage pathways involving the bicycloalkyl radical are major pathways in the oxidation of monocyclic aromatic hydrocarbons, i.e., BTX. The branching ratio for the bicycloalkyl radical intermediate, proposed to form from the reaction of the aromatic-OH adduct with atmospheric oxygen, could be directly identified with the primary glyoxal yield for the benzene system and as a lower limit in the case of toluene and p-xylene. Implications for the chemical behavior of aromatic hydrocarbons in the atmosphere are discussed.

The rate constant for the reaction of OH radicals with pinonaldehyde has been measured at 293 6 6 K using the relative rate method in the laboratory in Wuppertal (Germany) using photolytic sources for the production of OH radicals and in the EUPHORE smog chamber facility in Valencia (Spain) using the in situ ozonolysis of 2,3-dimethyl-2-butene as a dark source of OH radicals. In all the experiments pinonaldehyde and the reference compounds were monitored by FTIR spectroscopy, and in addition in the EUPHORE smog chamber the decay of pinonaldehyde was monitored by the HPLC/DNPH method and the reference com- pound by GC/FID. The results from all the different series of experiments were in good agree- ment and lead to an average value of k(pinonaldehyde 1 OH) 5 (4.0 6 1.0) 3 10 211 cm 3 molecule 21 s 21 . This result lead to steady-state estimates of atmospheric pinonaldehyde con- centrations in the ppbV range (1 ppbV < 2.5 3 10 10 molecule cm 23 at 298 K and 1 atm) in regions with substantial a-pinene emission. It also implies that atmospheric sinks of pinon- aldehyde by reaction with OH radicals could be half as important as its photolysis. The rate constant of the reaction of pinonaldehyde with Cl atoms has been measured for the first time. Relative rate measurements lead to a value of k(pinonaldehyde 1 Cl) 5 (2.4 6 1.4) 3 10210 cm3 molecule21 s21. In contrast to previous studies which suggested enhanced kinetic reactivity for pinonaldehyde compared to other aldehydes, the results from both the OH- and Cl-initiated oxidation of pinonaldehyde in the present work are in line with predic- tions using structure-activity relationships. q 1999 John Wiley & Sons, Inc., Int J Chem Kinet 31: 291- 301, 1999

Experiments on the photooxidation of toluene/NOx/air mixtures were performed in the European Photoreactor (EUPHORE), a large-scale outdoor reaction chamber located in Valencia/Spain. The objective of the study was the in situ determination of the yields of ring-retaining products by differential optical absorption spectroscopy (DOAS) and the elucidation of their formation pathways. The experiments were performed with toluene concentrations between 0.68 and 3.85 ppm and initial NOx concentrations ranging from 3 to 300 ppb, i.e., down to the range actually observed in the lower atmosphere. The ring-retaining product yields were found to be 5.8 ± 0.8%, 12.0 ± 1.4%, 2.7 ± 0.7%, and 3.2 ± 0.6% for benzaldehyde, o-cresol, m-cresol, and p-cresol, respectively. Under the experimental conditions, no dependency of the yields on the NOx concentration or the toluene/NOx ratio could be found. The formation kinetics of the cresols are in line with a “prompt” formation mechanism, i.e., abstraction of a hydrogen atom fro...

A method for the analysis of carboxylic acids in aerosols was developed, based on the collection of particles on Teflon filters (2.5 cm diameter with a 0.4 μm pore size), extraction with dichloromethane, and derivatization with BF3-methanol followed by analysis of the formed methylesters by large-volume injection GC/MS. In aerosol samples from smog chamber experiments with α-pinene and ozone, this method was applied and resulted in the identification for the first time of cis-pinic acid. Yields were in the range of 1-3% for 1000 pbbv α-pinene reacted with 750 pbbv ozone, and in in the range of 0.3-0.5% for 100 pbbv α-pinene reacted with 75 pbbv ozone. Being a dicarboxylic acid this product is estimated to possess an extremely low vapour pressure and may thus be an important element in gas-to-particle conversion of α-pinene.

The European Directive (2008/50/EC) sets up, among other things, the limit values i.e. the maximum allowed concentrations at given time average in the air, for specified pollutants. Calibration of the measurement instruments needs to be performed at regular time intervals. In the framework of an European Joint Research Programme (JRP) named Metrology for Chemical Pollutants in Air (MACPoll) one task aims to provide harmonized dilution methods for air pollutant gases at low concentration for calibration and quality control purposes. The study focuses on the reactive gases nitrogen dioxide and sulphur dioxide at concentration levels corresponding to the limit values given in the European Directive (2008/50/EC). Nitrogen oxide (NO) is studied as well as NO2 because both of them are measured simultaneously for NOx. This work consists in improving the dilution methods for generating calibration standards for SO2 , NO, NO2 at limit values and to validate them by an interlaboratory comparison.

The methodology of solid phase microextraction (SPME) with O-(2,3,4,5,6)-pentafluorobenzylhydroxylamine hydrochloride (PFBHA) on-fiber derivatization for the determination of carbonyls has been applied to the photo-oxidation of benzene and toluene carried out in the EUPHORE chambers. This work focuses on the results obtained for a number of highly reactive carbonyls, crucial in the determination of branching ratios and confirmation of the carbonylic route. The observed yields and kinetic behavior were compared to simulations with the Master Chemical Mechanism model, version 3.1 (MCMv3.1). The following yields were measured in the toluene system: glyoxal, (37 +/- 2)%; methylglyoxal, (37 +/- 2)%; 4-oxo-2-pentenal,(13.8 +/- 1.5)%; and total butenedial, (13 +/- 7)% (cis-butenedial, (6 +/- 3)%; trans-butenedial, (7 +/- 4)%]. For benzene, the experimental glyoxal yields were (42 +/- 3) and (36 +/- 2)% for the two successive experiments (September 24 and 25, 2003), (17 +/- 9)% for total butenedial [(8 +/- 4)% cis-butenedial and (9 +/- 5)% trans-butenedial (September 24, 2003)] and (15 +/- 6)% total butenedial (September 25, 2003) [(7 +/- 3) and (7 +/- 3)% for the cis and trans isomers, respectively]. PTR-MS estimations for butenedial also allowed the two isomers of butenedial to be distinguished, but the measurements showed signs of interference from other products. The results presented confirm the fast ring cleavage and provide further experimental confirmation of the dicarbonylic route.

The UV-vis and infrared absorption cross sections of perfluoro-2-methyl-3-pentanone (CF3CF2C(O)CF(CF3)2, 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-penta none), has been obtained, and a photolysis study was carried out under natural sunlight conditions in the European simulation chamber, Valencia, Spain (EUPHORE). The photolysis loss rate, J(photol), equaled (6.4 +/- 0.3) x 10(-6) s(-1) in the period of 10-14 GMT, July 14, 2003 in Valencia (0.5 W, 39.5 N) and corresponded to an effective quantum yield of photolysis of 0.043 +/- 0.011 over the wavelength range of 290-400 nm; the error limits correspond to 2sigma from the statistical analyses. The atmospheric lifetime of CF3CF2C(O)CF(CF3)2 is estimated to be around 1 week, and the global warming potential of the compound is negligible.

The photolysis of chloral under atmospheric conditions was studied at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The photodissociation rate coefficient, J(chloral), was measured directly under different sunlight conditions during April 1999. Values in the range of J(chloral) = (4.61-6.11) x 10(-5) s(-1) were obtained, yielding an average value of J(chloral)/J(NO2) = (6.15 +/- 0.62) x 10(-3). This corresponds to a photolysis lifetime of 4.5-6 h under conditions appropriate to the solar flux during summer months and confirms that atmospheric photolysis is the major degradation pathway for chloral. The overall quantum efficiency of photolysis under atmospheric conditions was determined to be 1.00 +/- 0.05. The atmospheric photolysis of chloral produced phosgene, CO, and Cl atoms with molar yields of 0.83 +/- 0.04, 1.01 +/- 0.05, and 1.18 +/- 0.06, respectively. The product yield data are consistent with a mechanism in which the primary photolysis channel produces a Cl atom and a CCl2CHO radical. The latter species is converted to the oxy radical OCCl2CHO,which decomposes by both C-C and C-Cl bond fission. A chemical mechanism for the photolysis of chloral by sunlight is proposed, and the atmospheric implications are discussed.

Reactions of ozone with alkenes can be a significant source of hydroxyl radicals in the atmosphere. In the present paper, the formation of OH radicals in the ozonolysis of selected alkenes under atmospheric conditions was directly observed. The experiments were carried out in the European photoreactor EUPHORE (Valencia, Spain). OH radicals were quantitatively detected by means of laser-induced fluorescence (LIF) using a new analytical instrument, which has been constructed on the basis of an existing setup already established in field studies. The OH radicals observed resulted directly from the reaction of ozone with the corresponding alkene. There was no indication that OH radicals were produced in the system by secondary processes. The experimentally observed concentration-time profiles of OH and ozone were excellently described by chemical modeling using explicit reaction mechanisms. The following OH yields were derived: 2,3-dimethyl-2-butene: (1.00 +/- 0.25); 2-methyl-2-butene: (0.89 +/- 0.22); trans-2-butene: (0.75 +/- 0.19); alpha-pinene: (0.91 +/- 0.23). In addition, the experiments carried out were modeled using the Regional Atmospheric Chemistry Mechanism (RACM), an established condensed chemical model applied in tropospheric chemistry. For 2,3-dimethyl-2-butene, 2-methyl-2-butene, and trans-2-butene the calculated concentration-time profiles of OH and ozone are in quite good agreement with the experimental data. However, in the case of alpha-pinene, the model fails for the simulation of OH due to the high grade of mechanism condensation, which results in a poor characterization of the primary reaction products.

Benzene and the alkyl-substituted benzenes, toluene and xylenes, are the most abundant aromatics observed in urban atmospheres (see Table 1). The aromatic fraction reaches 20 to 40% of the total non-methane hydrocarbons with the traffic emission being the major source. Their contribution to the photochemical smog and the formation of photooxidants, especially ozone, have been studied in smog chamber experiments and by simulations using atmospheric chemical models (Atkinson et al., 1980; Killus and Whitten, 1982; Leone et al., 1985). As a result of these studies, the aromatic hydrocarbons are considered to contribute significantly to the tropospheric ozone formation (Carter and Atkinson, 1987). However, the oxidation mechanisms of aromatic hydrocarbons in the atmosphere are up to now not well understood. Recent product studies from the OH-radical initiated oxidation of toluene under NOx-free conditions and in the presence of NOx (Atkinson and Aschmann, 1994; Bierbach et al., 1994) gave a poor carbon balance. Therefore, a detailed oxidation mechanism for the aromatic hydrocarbons is at present not possible.

Environmental Context. Atmospheric particulate material can affect the radiative balance of the atmosphere and is believed to be detrimental to human health. Secondary organic aerosols (SOA), which make a significant contribution to the total atmospheric burden of fine particulate material, are formed in situ following the photochemical transformation of organic pollutants into relatively less-volatile, oxygenated compounds which can subsequently transfer from the gas phase to a particle phase. SOA formation from the atmospheric photooxidation of aromatic hydrocarbons—present, for example, as a result of automobile use—is believed to be important in the urban environment and yet the mechanisms are not well understood. For example, even the reasons for observed variations in the relative propensity for SOA formation, from the photooxidation of various simple aromatic hydrocarbons, are not clear. Abstract. The formation and composition of secondary organic aerosol (SOA) from the photooxidation of benzene, p-xylene, and 1,3,5-trimethylbenzene has been simulated using the Master Chemical Mechanism version 3.1 (MCM v3.1) coupled to a representation of the transfer of organic material from the gas to particle phase. The combined mechanism was tested against data obtained from a series of experiments conducted at the European Photoreactor (EUPHORE) outdoor smog chamber in Valencia, Spain. Simulated aerosol mass concentrations compared reasonably well with the measured SOA data only after absorptive partitioning coefficients were increased by a factor of between 5 and 30. The requirement of such scaling was interpreted in terms of the occurrence of unaccounted-for association reactions in the condensed organic phase leading to the production of relatively more nonvolatile species. Comparisons were made between the relative aerosol forming efficiencies of benzene, toluene, p-xylene, and 1,3,5-trimethylbenzene, and differences in the OH-initiated degradation mechanisms of these aromatic hydrocarbons. A strong, nonlinear relationship was observed between measured (reference) yields of SOA and (proportional) yields of unsaturated dicarbonyl aldehyde species resulting from ring-fragmenting pathways. This observation, and the results of the simulations, is strongly suggestive of the involvement of reactive aldehyde species in association reactions occurring in the aerosol phase, thus promoting SOA formation and growth. The effect of NOx concentrations on SOA formation efficiencies (and formation mechanisms) is discussed.

Environmental Context. Atmospheric particulate material can affect climate by absorbing and scattering solar radiation and by altering the properties of clouds. They are also implicated as a health risk. Secondary organic aerosol (SOA) material makes an important contribution to this particulate burden. SOA material results from the transfer of gas-phase species into a particle state after the formation of products from the reaction of atmospheric volatile organic compounds (VOCs) with oxygen. SOA from the oxidation of aromatic hydrocarbons, such as toluene, a gasoline fuel component, is important in the polluted urban environment and yet formation mechanisms are not well understood. Abstract. The formation and composition of secondary organic aerosol (SOA) from the gas-phase photooxidation of toluene has been simulated using the Master Chemical Mechanism version 3.1 (MCM v3.1) coupled to a representation of the transfer of organic material from the gas phase to a particle phase. The mechanism was tested against data from a series of toluene photooxidation experiments performed at the European Photoreactor (EUPHORE) outdoor smog chamber in Valencia, Spain. Simulated aerosol mass concentrations compared reasonably well with the measured SOA data after absorptive partitioning coefficients were increased by a factor of between 20 and 80, although the simulated onset of SOA growth was delayed with respect to the experiments. A simplified representation of peroxyhemiacetal adduct formation, from the reaction of organic hydroperoxides with aldehydes in the condensed organic phase, was included in the mechanism and this reduced the required scaling of partitioning coefficients and reduced the time-lag in simulated SOA growth. These observations, and the dependence of SOA formation efficiency upon the initial NO concentration, strongly imply the significant occurrence of association reactions in the condensed organic phase and the important role of organic hydroperoxides in SOA formation. Aerosol data from photooxidation experiments of intermediate degradation products (butenedial, 4-oxo-pentenal, and ortho-cresol) were also simulated using the developed mechanism.

An assessment of the accuracy of OH concentrations measured in a smog chamber by a calibrated laser-induced fluorescence (LIF) instrument has been made, in the course of 9 experiments performed to study the photo-oxidation of benzene, toluene, 1,3,5-trimethylbenzene, para-xylene, ortho-cresol and ethene at the European Photoreactor facility (EUPHORE). The LIF system was calibrated via the water photolysis / ozone actinometry approach. OH concentrations were inferred from the instantaneous rate of removal of each hydrocarbon species (measured by FTIR or HPLC) via the appropriate rate coefficient for their reaction with OH, and compared with those obtained from the LIF system. Good agreement between the two approaches was found for all species with the exception of 1,3,5-trimethylbenzene, for which OH concentrations inferred from hydrocarbon removal were a factor of 3 lower than those measured by the LIF system. From the remaining 8 experiments, an overall value of 1.15±0.13 (±1σ) was obtained for [OH]LIF / [OH]Hydrocarbon Decay, compared with the estimated uncertainty in the accuracy of the water photolysis / ozone actinometry OH calibration technique of 26% (1σ).