Oxidation capacity changes in the atmosphere of large urban areas in Europe: Modelling and experimental campaigns in atmospheric simulation chambers.

Air pollution is a major concern for human health and the environment. Consequently, environmental standards have become stricter to improve air quality. Thanks to this, the ambient levels of O3 precursors such as VOCs and NOX have decreased. However, O3 levels in Europe, especially during winter, have increased, potentially impacting on atmospheric oxidation capacity and the associated chemistry of tropospheric oxidants. In this work, we focus on recent changes in the oxidation capacity of urban atmospheres. The study is conducted with the results of the CMAQ modelling system with a regional resolution with 12 × 12 km2 across the entire European continent for the winter (January) and summer (July) of 2007 and 2015. The 2015 meteorological data is used for both years to emphasise emission changes during the studied period. We scrutinise the changes in ambient concentration levels of the main tropospheric oxidants (O3 and HOX radicals) in five representative cities, Valencia, Madrid, Milan, Berlin, and The Hague. The enhanced O3 formation in winter seems to be due to the low VOC/NOX ratio, while the opposite trend in summer may be related to a relatively high ratio. Additionally, photooxidation experiments are carried out in the EUPHORE chambers to study the effect of changes in NOX concentration and NO/NO2 ratio on the variation of the given oxidants at constant VOCs concentrations. For the baseline experiments, two scenarios are selected based on the model results of 2015: two representative winter and summer days of low and high pollution in Berlin and Madrid, respectively. The role of VOC/NOX and NO/NO2 ratios on atmospheric reactivity is discussed. As a result, it is first suggested that further decreases in ambient NOX levels are required to reduce ambient O3 levels. Moreover, additional factors should be considered when designing local-specific emission abatement strategies.

Atmospheric Oxidation of a Thiocarbamate Herbicide Used in Winter Cereals.

The gas-phase atmospheric degradation of prosulfocarb (a widely used thiocarbamate herbicide in winter cereals) at different NOx concentrations was investigated at the large outdoor European PHOtoREactor (EUPHORE) in Valencia, Spain. Photolysis under sunlight conditions and reaction with ozone were shown as unimportant. The rate constant for the reaction of prosulfocarb with OH radicals was determined as k = (2.9 ± 0.5) × 10-11 cm3 molecule-1 s-1 at 288 ± 10 K and atmospheric pressure by a conventional relative rate method. Significant ozone and aerosol formation was observed following the reaction of prosulfocarb with OH radicals, and the main detected carbon-containing gas-phase products were benzaldehyde, S-benzyl formyl(propyl)carbamothioate, and S-benzyl propanoyl(propyl)carbamothioate.

Risk assessment of airborne pesticides in a Mediterranean region of Spain.

A risk assessment strategy based on the quantitative target analysis and semi-quantitative retrospective screening determination of pesticides in PM10 has been developed. The proposed methodology was applied to 345 real samples from nine stations of a Mediterranean area in Spain, and the risk was assessed for adult, children and infants. Forty pesticides were detected with average concentrations ranging from 8 to 30,000pgm-3. Each station showed its specific pesticide profile, which is linked to the different types of crops around each station. For adults, children and infants the estimated chronic inhalation risk, expressed as Hazard Quotient (HQ), was <1 for all pesticides. The cumulative exposure for organophosphates, neonicotinoids, benzimidazoles, carbamates, micro-organism and triazoles pesticides (HI, Hazard Index) were <1 for the three groups of populations assessed. For infants, the cancer risk estimated for the detected pesticides classified as possible and potential carcinogens were lower than 1.0 E-06, except for carbendazim and hexythiazox.

Atmospheric degradation of the organothiophosphate insecticide - Pirimiphos-methyl.

The gas phase atmospheric degradation of pirimiphos-methyl (a widely used organophosphate insecticide and acaricide in many European regions) has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. Its photolysis has been studied under sunlight conditions and its reaction rate constant with OH radicals was measured by the relative rate method. The reaction with ozone was also investigated. The tropospheric degradation of pirimiphos-methyl is controlled mainly by the OH radical reaction. The rate coefficient of the OH reaction with pirimiphos-methyl, k, was measured by a conventional relative rate technique, where aniline was taken as a reference. The resulting value of the OH reaction rate constant with pirimiphos-methyl was k=(1.14±0.2)×10-10cm3molecule-1s-1. The tropospheric lifetime of pirimiphos-methyl with respect to the reaction with OH radicals was estimated to be around 1.6h (283±10) K and atmospheric pressure. Significant aerosol formation was observed in the OH reaction with yields that ranged from 25 to 37%, and with particle diameters below 550nm. This therefore reveals a high human risk due to PM<1, without taking into account the chemical composition of the degradation products. SO2, glyoxal and other oxygenated and nitrogenated compounds were the main degradation products detected.

Determination of reduced sulfur compounds in air samples for the monitoring of malodor caused by landfills.

A reliable method for determining malodorous reduced sulfur compounds (RSC) in atmospheric samples has been developed. The method uses an activated coconut solid-phase sorbent for active sampling, hexane as desorption solvent, and gas chromatography-mass spectrometry (GC-MS) technique for specific and sensitive separation-detection. The compounds analyzed were hydrogen sulfide, ethyl mercaptan, dimethyl sulfide, carbon disulfide, butyl mercaptan and dimethyl disulfide. Recovery efficiency varied between 75% and 97% and no detectable losses were observed during storage at -20°C. Satisfactory analytical parameters were reported, such as good linearity (r(2)>0.98), low detection limits (0.6-59 pg m(-3)), adequate repeatability (9%) and reproducibility (17%), and fast GC-MS analysis (<6.5 min). The accurate determination of RSCs, free of interferences from atmospheric components, such as ozone or water was demonstrated. The method has been applied to analyze the composition of environmental air close to three landfills processing urban and industrial solid wastes. The results indicated that hydrogen sulfide and ethyl mercaptan were the main molecules responsible of malodor phenomenon in the study areas.

Insights into the Formation and Evolution of Individual Compounds in the Particulate Phase during Aromatic Photo-Oxidation.

Secondary organic aerosol (SOA) is well-known to have adverse effects on air quality and human health. However, the dynamic mechanisms occurring during SOA formation and evolution are poorly understood. The time-resolved SOA composition formed during the photo-oxidation of three aromatic compounds, methyl chavicol, toluene and 4-methyl catechol, were investigated at the European Photoreactor. SOA was collected using a particle into liquid sampler and analyzed offline using state-of-the-art mass spectrometry to produce temporal profiles of individual photo-oxidation products. In the photo-oxidation of methyl chavicol, 70 individual compounds were characterized and three distinctive temporal profile shapes were observed. The calculated mass fraction (Ci,aer/COA) of the individual SOA compounds showed either a linear trend (increasing/decreasing) or exponential decay with time. Substituted nitrophenols showed an exponential decay, with the nitro-group on the aromatic ring found to control the formation and loss of these species in the aerosol phase. Nitrophenols from both methyl chavicol and toluene photo-oxidation experiments showed a strong relationship with the NO2/NO (ppbv/ppbv) ratio and were observed during initial SOA growth. The location of the nitrophenol aromatic substitutions was found to be critically important, with the nitrophenol in the photo-oxidation of 4-methyl catechol not partitioning into the aerosol phase until irradiation had stopped; highlighting the importance of studying SOA formation and evolution at a molecular level.

Atmospheric degradation of lindane and 1,3-dichloroacetone in the gas phase. Studies at the EUPHORE simulation chamber.

The gas-phase degradation of lindane (γ-isomer of hexachlorocyclohexane) towards OH radical was investigated under atmospheric conditions at the large outdoor European simulation chamber (EUPHORE) in Valencia, Spain. The rate coefficient for the reaction of hydroxyl radicals with lindane was measured using a conventional relative rate technique leading to a value of kOH(lindane)=(6.4±1.6)×10(-13) cm(3) molecule(-1) s(-1) at 300±5 K and atmospheric pressure. The results suggest that the tropospheric lifetime of lindane with respect to OH radicals is approximately 20 days. The product distribution studies on the OH-initiated oxidation of lindane provided evidence that the major initial carbon-containing oxidation product is pentachlorocyclohexanone. 1,3-Dichloroacetone was employed as a model compound for pentachlorocyclohexanone, and an investigation of its photolysis and reaction with OH radicals under atmospheric conditions was carried out. The data indicate that the atmospheric degradation of pentachlorocyclohexanone would be relatively rapid, and would not form persistent organic compounds. Theoretical study was also employed to calculate possible degradation pathways. Mechanism for reaction of lindane with OH radicals is proposed, and C-Cl bond cleavage is discussed. OH abstraction is considered to be a reasonable way for Cl to escape during degradation. The atmospheric implications of the use of lindane as an insecticide are discussed.

Gas-phase and particulate products from the atmospheric degradation of the organothiophosphorus insecticide chlorpyrifos-methyl.

The phosphorothioate structure is highly present in several organophosphorus pesticides. However, there is insufficient information about its degradation process after the release to the atmosphere and the secondary pollutants formed. Herein, the atmospheric reaction of chlorpyrifos-methyl (o,o-dimethyl o-(3,5,6-trichloropyridin-2-yl) phosphorothioate), is described for semi-urban or rural locations. The photo-oxidation under low NOx conditions (5-55 ppbV) was reproduced in a large outdoor simulation chamber, observing a rapid degradation (lifetime<3.5 h). The formation of gaseous products and particulate matter (aerosol yield 2-8%) was monitored. The chemical composition of minor products (gaseous and particulate) was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as o,o-dimethyl o-(3,5,6-trichloropyridin-2-yl) phosphorothioate, dimethyl 3,5,6-trichloropyridin-2-yl phosphate, o-methyl o-(3,5,6-trichloropyridin-2-yl) hydrogen phosphorothioate, 3,5,6-trichloropyridin-2-yl dihydrogen phosphate, 3,5,6-trichloropyridin-2-ol, and 3,5,6-trichloropyridine-2,4-diol. An atmospheric degradation mechanism has been proposed based on an oxidation started with OH-nucleophilic attack to P=S bond. The results have been extrapolated to other organothiophosphorus molecules, such as malathion, parathion, diazinon and methidathion, among many others, to estimate their photo-oxidative degradation and the expected products.

The gas-phase degradation of chlorpyrifos and chlorpyrifos-oxon towards OH radical under atmospheric conditions.

The OH initiated oxidation of chlorpyrifos (a widely used insecticide) and its photooxidation product chlorpyrifos-oxon were investigated at the large outdoor European Photoreactor (EUPHORE). The rate constants for reaction of chlorpyrifos and chlorpyrifos oxon with OH radicals were measured using a conventional relative rate method. The value of the OH reaction rate constants with chlorpyrifos and chlorpyrifos-oxon were determined to be k=(9.1±2.1)×10(-11)cm(3)molecule(-1)s(-1) and (1.7±0.9)×10(-11)cm(3)molecule(-1)s(-1) at 303±5K and atmospheric pressure. They gave an atmospheric lifetime in relation to the reaction with OH of approximately 2h and 11h for chlorpyrifos and chlorpyrifos-oxon, respectively. Photolysis was found to be unimportant relative to reaction with OH. The main products detected in the gas phase from the reaction of OH with chlorpyrifos were SO2, chlorpyrifos-oxon, 3,5,6-trichloro-2-pyridinol and diethylphosphate with molar yields of 17±5%, ∼10%, 8±4% and 30±9%, respectively.

Gas-phase degradation of the herbicide ethalfluralin under atmospheric conditions.

The gas-phase degradation of ethalfluralin, N-ethyl-α,α,α-trifluoro-N-(2-methylallyl)-2,6-dinitro-p-toluidine, a widely used herbicide, was investigated under atmospheric conditions at the large outdoor European simulation chamber (EUPHORE) in Valencia, Spain. The photolysis of ethalfluralin was investigated under solar radiation and the mean photolysis rate coefficient was determined: J(ethalfluralin)=(1.3±0.2)×10(-3) s(-1) (JNO2=8×10(-3) s(-1)). The rate coefficients for the reactions of hydroxyl radicals and ozone with ethalfluralin in the dark were also measured under atmospheric conditions using the relative rate and the absolute rate technique, respectively. The rate coefficients values for the reactions of kOH(ethalfluralin)=(3.5±0.9)×10(-11)cm(3)molecule(-1)s(-1), and kO3(ethalfluralin)=(1.6±0.4)×10(-17) cm(3) molecule(-1) s(-1) were determined at 300±5 K and atmospheric pressure. The results show that removal of ethalfluralin from the atmosphere by reactions with OH radicals (τ ~ 4 h) or ozone (τ ~ 25 h) is slow compared to loss by photolysis. The available kinetic data suggest that the gas-phase tropospheric degradation of ethalfluralin will be controlled mainly by photolysis and provide an estimate for the tropospheric lifetime of approximately 12 min. The atmospheric implications of using ethalfluralin as a herbicide are discussed.

Gas-phase and particulate products from the atmospheric degradation of an isoxazole fungicide.

The isoxazole structure is present in several pesticides. However, there is a lack of information about its degradation products after the release to the atmosphere. The main atmospheric reactions of hymexazol (5-methylisoxazol-3-ol), selected as representative model, were investigated at a large outdoor simulation chamber. The predominant products of atmospheric degradations were gaseous nitrogen derivates (nitric acid, nitrogen dioxide, nitrogen oxide, nitrous acid, and peroxyacetylnitrate), ozone, and small oxygenated compounds (formic acid, formaldehyde, and methylglyoxal). The aerosol yields were lower than 5%, and an OH rate-dependence was observed in the nucleation, particle growth, and size distribution. Also, the chemical composition of minor multi-oxygenated products was studied for OH-photo-oxidations. More than 20 products were detected in the gas or particulate phase. The most abundant were heterocyclic cleavage products with C4-chain and oxygenated moieties at positions 1 and 3, such as 3,4-dioxobutanoic acid, 3-oxobutanoic acid, and 3-oxobutanal. The suggested reaction pathway is the opening of heterocycle ring by the cleavage of N-O bond and C-N bond, releasing nitrogen oxides.

Online and offline mass spectrometric study of the impact of oxidation and ageing on glyoxal chemistry and uptake onto ammonium sulfate aerosols.

Recent laboratory and modelling studies have shown that reactive uptake of low molecular weight alpha-dicarbonyls such as glyoxal (GLY) by aerosols is a potentially significant source of secondary organic aerosol (SOA). However, previous studies disagree in the magnitude of the uptake of GLY, the mechanism involved and the physicochemical factors affecting particle formation. In this study, the chemistry of GLY with ammonium sulfate (AS) in both bulk laboratory solutions and in aerosol particles is investigated. For the first time, Aerosol Time of Flight Mass Spectrometry (ATOFMS), a single particle technique, is used together with offline (ESI-MS and LC-MS2) mass spectrometric techniques to investigate the change in composition of bulk solutions of GLY and AS resulting from aqueous photooxidation by OH and from ageing of the solutions in the dark. The mass spectral ions obtained in these laboratory studies were used as tracers of GLY uptake and chemistry in AS seed particles in a series of experiments carried out under dark and natural irradiated conditions at the outdoor European Photo-reactor (EUPHORE). Glyoxal oligomers formed were not detected by the ATOFMS, perhaps due to inefficient absorption at the laser wavelength. However, the presence of organic nitrogen compounds, formed by reaction of GLY with ammonia was confirmed, resulting in an increase in the absorption efficiency of the aerosol, and this increased the number of particles successfully ionised by the ATOFMS. A number of light absorbing organic nitrogen species, including 1H-imidazole, 1H-imidazole-2-carboxaldehyde, 2,2'-bis-imidazole and a glyoxal substituted 2,2'-bisimidazole, previously identified in aqueous laboratory solutions, were also identified in chamber aerosol and formed on atmospherically relevant timescales. An additional compound, predicted to be 1,2,5-oxadiazole, had an enhanced formation rate when the chamber was open and is predicted to be formed via a light activated pathway involving radical oxidation of ammonia to hydroxylamine, followed by subsequent reaction with glyoxal to form an intermediate glyoxime.

The atmospheric photolysis of o-tolualdehyde.

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.

Studies on atmospheric degradation of diazinon in the EUPHORE simulation chamber.

The gas phase atmospheric degradation of diazinon has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The rate constant for reaction of diazinon with OH radicals was measured using a conventional relative rate method with di-n-buthylether as reference compound being k = (3.5 ± 1.2) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ at 302 ± 10 K and atmospheric pressure. The available evidence indicates that tropospheric degradation of diazinon is mainly controlled by reaction with OH radicals, and that the tropospheric lifetime with respect to the OH reaction is estimated to be around 4h whereas its lifetime with respect to the photolysis is higher than 1d under our conditions. Significant aerosol formation was observed following the reaction of diazinon with OH radicals, and the main carbon-containing products detected in the particle phase were hydroxydiazinon, hydroxydiazoxon and 2-isopropyl-6-methyl-pyrimidinyl-4-ol.

Studies on the atmospheric degradation of chlorpyrifos-methyl.

The gas-phase atmospheric degradation of chlorpyrifos-methyl (a widely used organophosphate insecticide in Southern European regions) has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. Photolysis under sunlight conditions and reaction with ozone were shown to be unimportant. The rate constant for reaction of chlorpyrifos-methyl with OH radicals was measured using a conventional relative rate method with cyclohexane and n-octane employed as reference compounds with k = (4.1 ± 0.4) × 10(-11) cm(3) molecule(-1) s(-1) at 300 ± 5 K and atmospheric pressure. The available evidence indicates that tropospheric degradation of chlorpyrifos-methyl is mainly controlled by reaction with OH radicals and that the tropospheric lifetime is estimated to be around 3.5 h. Significant aerosol formation was observed following the reaction of chlorpyrifos-methyl with OH radicals, and the main carbon-containing products detected in the gas phase were chlorpyrifos-methyl oxone and 3,5,6-trichloro-2-pyridinol.

Temperature effect of tapered element oscillating microbalance (TEOM) system measuring semi-volatile organic particulate matter.

The tapered element oscillating microbalance (TEOM) system is widely used to measure continuous particle mass concentrations in air quality networks. However, the semi-volatile aerosol material is lost under normal operation conditions (50 °C). This study has evaluated the error in the organic fraction of the TEOM-measured secondary organic aerosols formed from the degradation of biogenic pollutants. Experiments were carried out under controlled, water-free conditions in a fully equipped, high volume atmospheric simulator--the European PhotoReactor (EUPHORE). The ozonolysis of α-pinene, ß-pinene and limonene provided a reproducible source of organic aerosol. Particulate matter concentration profiles were registered for different TEOM operating temperatures. When these values were compared with values from a filter-based gravimetric method and a scanning mobility particle sizer (SMPS), they showed that the differences between monitoring systems increased with increasing TEOM temperature. According to our results, when the TEOM is operated at 50 °C, it fails to measure 32-46% of the organic particulate material, depending on the aerosol precursor. This study has also identified and quantified the multi-oxygenated organic compounds lost in the TEOM monitoring by using a method based on the gas chromatography-mass spectrometry technique. Important losses have been calculated for relevant ambient aerosol compounds such as pinonic acid, pinonaldehyde, norpinone and limonalic acid. In conclusion, the present study has demonstrated that a high operating temperature of the TEOM monitor reduces the humidity interference but underestimates the semi-volatile organic fraction.