Amalia Muñoz

Centro de Estudios Ambientales del Mediterráneo | CEAM

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 atmospheric o...

The detailed chemical characterization of gas and particle phase species is essential for interpreting the results of atmospheric simulation chamber experiments. Although the application of online techniques has advanced significantly over the last two decades, offline analytical methods such as GC–MS and LC–MS are still frequently used. In this ch...

Preparation of the air mixture used in chamber experiments requires typically the injection of trace gases into a bath gas. In this chapter, recommendations and standard protocols are given to achieve quantitative injections of gaseous, liquid or solid species. Various methods to produce ozone, nitrate radicals and hydroxyl radicals are discussed....

In this chapter, we focus on aspects of analysis of typical simulation chamber experiments and recommend best practices in term of data analysis of simulation chamber results relevant for both gas phase and particulate phase atmospheric chemistry. The first two sections look at common gas-phase measurements of relative rates and product yields. The...

A field campaign has been performed in the Madrid region to study the VOC influence in the growth of new particles in ambient air. A number of instruments have been deployed to characterize the main pollutant gases and particle properties and composition. The measurements were performed simultaneously at three sites (rural, urban background and urb...

Once pesticides are released into the environment, their active ingredient and other formulation compounds, such as coadjuvants or solvents, may undergo biological and chemical degradation, and form a range of products that could be even more hazardous than their precursors. These degradation products may also interact with the natural biogenic com...

In early 2020, the COVID-19 pandemic spread globally, and severe measures to control it were implemented. This study investigates the impact of the lockdown on the air quality of three provinces in the Valencia region, eastern Spain, in the years 2015-2020, focusing on particulate matter (PM). A thorough statistical analysis using different approac...

Multi-oxygenated volatile organic compounds are important markers of air pollution and precursors of ozone and secondary aerosols in both polluted and remote environments. Herein, their accurate determination was enhanced. The approach was based on an automated system for active sampling and on-fibre derivatization coupled with the gas chromatograp...

This paper provides scientific results from a European LIFE project carried out in the Valencian region of Spain during the 2017 to 2018 time frame. In 2018, more than 60,000 tons of pesticides were commercialized in Spain, with approximately 15% destined for Valencian crops. In order to improve the air quality in the agricultural areas of this reg...

Photolysis is one the main drivers in atmospheric chemistry. Volatile organic compounds that bear one or more carbonyl functions can absorb UV light between 295 nm and 450 nm, enabling them to possibly photolyze in the atmosphere. Yet, very few data are available regarding the impact of such photolysis processes on the fate of multifunctional carbo...

Multi-oxygenated volatile organic compounds are important markers of air pollution and precursors of ozone and secondary aerosols in both polluted and remote environments. Herein, their accurate determination was enhanced. The approach was based on an automated system for active sampling and on-fiber derivatization coupled with GC-MS technique. The...

The chemical characterization of aerosols, especially fine organic fraction, is a relevant atmospheric challenge because their composition highly depends on localization. Herein, we studied the concentration of multi-oxygenated organic compounds in the western Mediterranean area, focusing on sources and the effect of air patterns. The organic aeros...

Nitrogen oxides (NOx=NO+NO2) are critical intermediates in atmospheric chemistry and air pollution. NOx levels control the cycling and hence abundance of the primary atmospheric oxidants OH and NO3 and regulate the ozone production which results from the degradation of volatile organic compounds (VOCs) in the presence of sunlight. They are also atm...

Nitrogen oxides (NOx=NO + NO2) are critical intermediates in atmospheric chemistry and air pollution. NOx levels control the cycling and hence abundance of the primary atmospheric oxidants OH and NO3 and regulate the ozone production which results from the degradation of volatile organic compounds (VOCs) in the presence of sunlight. They are also a...

Nitrogen oxides (NOx = NO + NO2) are critical intermediates in atmospheric chemistry. NOx levels control the cycling and hence abundance of the primary atmospheric oxidants OH and NO3, and regulate the ozone production which results from the degradation of volatile organic compounds (VOCs) in the presence of sunlight. They are also atmospheric poll...

Criegee Intermediates (CI), formed in the ozonolysis of alkenes, play a central role in tropospheric chemistry as an important source of radicals, with stabilised CI (SCI) able to participate in bimolecular reactions, affecting climate through the formation of inorganic and organic aerosol. However, total SCI yields have only been determined for a...

Formic acid (HCOOH), one of the most important and ubiquitous organic acids in the Earth’s atmosphere, contributes substantially to atmospheric acidity and affects pH-dependent reactions in the aqueous phase. However, based on the current mechanistic understanding, even the most advanced chemical models significantly underestimate the HCOOH concent...

Control of pests and diseases in commercial crops is a permanent concern for farmers due the important yield and economic losses. Pesticides play an important role in agricultural production, preventing disease and infestation of crops. In Europe, every year around 400.000 tones of pesticide active ingredients are sold (Eurostat, 2018). As expected...

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 re...

The gas-phase reaction of alkenes with ozone is known to produce stabilised Criegee intermediates (SCIs). These biradical/zwitterionic species have the potential to act as atmospheric oxidants for trace pollutants such as SO2, enhancing the formation of sulfate aerosol with impacts on air quality and health, radiative transfer and climate. However,...

Indoor pollution poses a serious threat to human health. Plants represent a sustainable but underexploited solution to enhance indoor air quality. However, the current selection of plants suitable for indoors fails to consider the physiological processes and mechanisms involved in phytoremediation. Therefore, the capacity of plants to remove indoor...

The gas-phase reaction of alkenes with ozone is known to produce stabilised Criegee intermediates (SCIs). These biradical/zwitterionic species have the potential to act as atmospheric oxidants for trace pollutants such as SO2, enhancing the formation of sulfate aerosol with impacts on air quality and health, radiative transfer and climate. However,...

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 mea...

Several experiments were performed in the European Photo-reactor - EUPHORE - for studying aerosol formation from organophosphorus pesticides such as diazinon, chlorpyrifos, chlorpyrifos-methyl and pirimiphos-methyl. The mass concentration yields obtained (Y) were in the range 5 - 44% for the photo-oxidation reactions in the presence and the absence...

The atmospheric particulate matter has a large impact on climate, biosphere behaviour and human health. Its study is complex because of large number of species are present at low concentrations and the continuous time evolution, being not easily separable from meteorology, and transport processes. Closed systems have been proposed by isolating spec...

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 a...

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, we...

The phosphorothioate structure is highly present in several pesticides. However, there is a lack of information about its degradation process in air and the secondary pollutants formed. Herein, the atmospheric reactions of chlorpyrifos, one of the most world-used insecticide, and its main degradation product - chlorpyrifos-oxon - are described. The...

Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting...

The α-dicarbonyl compounds glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO) are produced in the atmosphere by the oxidation of hydrocarbons and emitted directly from pyrogenic sources. Measurements of ambient concentrations inform about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation. We present...

Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting...

The removal of SO2 in the presence of alkene-ozone systems has been studied for ethene, cis-but-2-ene, trans-but-2-ene and 2,3-dimethyl-but-2-ene, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity for all four alkene-ozone systems confirming a significant reactio...

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) phosphorothio...

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 oxonwith OH radicals weremeasured using a conventional relative rate method. The value of th...

The α-dicarbonyl compounds glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO) are produced in the atmosphere by the oxidation of hydrocarbons, and emitted directly from pyrogenic sources. Measurements of ambient concentrations inform about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation. We present...

The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound (VOC) that was recently identified as the main floral emission from an oil palm plantation in Malay...

The Tropics provide a reactive atmospheric environment with high levels of biogenic emissions, rapidly growing anthropogenic influence, high solar radiation and temperature levels. The major reactive biogenic emission is isoprene which reacts rapidly with the primary daytime oxidant OH, the hydroxyl radical. This key photooxidation process has rece...

With the aim of characterizing the main air pollutants (anthropogenic, biogenic and secondary reaction products) present in the Mediterranean coast of the Iberian Peninsula under different meteorological conditions (summer and winter) two field campaigns (February and June 2011) were performed in the context of the MODELISMOS project (Modelling and...

Within the MODELISMOS project (Modelling and analysis of mesometeorological processes on transport and accumulation of pollutants in the Western Mediterranean and their influence on chemical degradation mechanisms) two different campaigns, the first one in winter-(February 2012) and the second one in summer (September 2012), were carried out at the...

A microfluidic lab-on-a-chip derivatisation technique has been developed to measure part per billion (ppbV) mixing ratios of gaseous glyoxal (GLY) and methylglyoxal (MGLY), and the method is compared with other techniques in a smog chamber experiment. The method uses o-(2, 3, 4, 5, 6-pentafluorobenzyl) hydroxylamine (PFBHA) as a derivatisation reag...

The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound that was recently identified as the main floral emission from an oil palm plantation in Malaysian B...

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 a...

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 photo...

A microfluidic lab-on-a-chip derivatization technique has been developed to measure part per billion volume (ppbV) mixing ratios of gaseous glyoxal (GLY) and methylglyoxal (MGLY), and the method compared with other techniques in a smog chamber experiment. The method uses o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) as a derivatization reag...

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...

The oxidation of volatile organic compounds (VOCs) leads to formation of ozone and SOA, with consequences for air quality, health, crop yields, atmospheric chemistry and radiative transfer. Recent observations have identified Methyl Chavicol ("MC": Estragole; 1-allyl-4-methoxybenzene, C10H12O) as a major BVOC above pine forests in the USA, and oil...

Field measurements give on-site information about the state of the atmosphere under certain meteorological conditions on a specific time and location. But the atmosphere is a highly complicated reactive system on which many processes (transport, accumulation of pollutants, deposition, chemical reaction, etc) affected by weather conditions happen at...

Los aerosoles orgánicos secundarios (AOS) constituyen una fracción de las partículas atmosféricas. Este tipo de partículas se forman como consecuencia de la reacción de oxidación de ciertos gases orgánicos, lo que conduce a la formación de compuestos de baja volatilidad. Del mismo modo que para otros contaminantes atmosféricos, los modelos de calid...

HONO is an important source of OH-radicals, the major oxidant in the atmosphere during daytime that participates in ozone formation and can lead to photo-smog. Nevertheless, there are still many open questions about its formation and role as a source of OH-radicals. A better knowledge of HONO processes is highly desirable for the improvement of air...

The α-dicarbonyl compounds glyoxal (GLY, CH(O)CHO) and methylglyoxal (MGLY, CH3C(O)CHO)) are ubiquitous intermediates formed in the photooxidation of a wide range of anthropogenic and biogenic volatile organic compounds (VOCs). Recent measurements demonstrate that large uncertainties exist in the amount of glyoxal formed from isoprene photooxidatio...

Nitrogen oxides (NO and NO2, collectively NOx) are critical intermediates in atmospheric chemistry. NOx abundance controls the levels of the primary atmospheric oxidants OH, NO3 and O3, and regulates the ozone production which results from the degradation of volatile organic compounds. NOx are also atmospheric pollutants in their own right, and NO2...

The gas-phase degradation of propachlor (2-chloro-N-isopropylacetanilide), a widely used herbicide, 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 propachlor was measured using a conventional relative rate te...

The degradation of 2-aminoethanol (MEA) by the hydroxyl radical (OH) was studied in the European Photoreactor (EUPHORE), a large outdoor environmental chamber. High-Temperature Proton-Transfer-Reaction Mass Spectrometry (HT-PTR-MS) and Fast Fourier Transform Infrared (FT-IR) were used to follow concentrations of reactants in the gas phase. Aerosol...

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(...

A reliable multi-residue method for determining gaseous and particulate phase pesticides in atmospheric samples has been developed. This method, based on full scan gas chromatography-mass spectrometry (GC-MS), allowed the proper determination of sixteen relevant pesticides, in a wide range of concentrations and without the influence of interference...

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...

The gas-phase degradation of hymexazol (5-methylisoxazol-3-ol), a widely used fungicide, was investigated under atmospheric conditions at the European Photoreactor (EUPHORE) in Valencia, Spain, a large outdoor simulation chamber. The rate coefficient for the reaction of hydroxyl radicals with hymexazol was measured using a conventional relative rat...

Nitrous acid (HONO) is an important source of the OH radical, the primary oxidant in the atmosphere. The chemistry of HONO and its possible sources in the atmosphere are not well understood. The aims of the FIONA (Formal Intercomparisons of Observations of Nitrous Acid) campaign are to establish a better understanding of HONO chemistry and to inte...

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...

The degradation of 2-aminoethanol (MEA) by the hydroxyl radical (OH) was studied in the European Photoreactor (EUPHORE), a large outdoor environmental chamber. High-Temperature Proton-Transfer-Reaction Mass Spectrometry (HT-PTR-MS) and Fast Fourier Transform Infrared (FT-IR) were used to follow concentrations of reactants in the gas phase. Aerosol...