Submicron aerosol pollution in Greater Cairo (Egypt): A new type of urban haze?

Greater Cairo, the largest megacity of the Middle East North Africa (MENA) region, is currently suffering from major aerosol pollution, posing a significant threat to public health. However, the main sources of pollution remain insufficiently characterized due to limited atmospheric observations. To bridge this knowledge gap, we conducted a continuous 2-month field study during the winter of 2019-2020 at an urban background site, documenting for the first time the chemical and physical properties of submicron (PM1) aerosols. Crustal material from both desert dust and road traffic dust resuspension contributed as much as 24 % of the total PM1 mass (rising to 66 % during desert dust events), a figure not commonly observed in urban environments. Our observations showed significant decreases in black carbon concentrations and ammonium sulfate compared to data from 15 years ago, indicating an important reduction in both local and regional emissions as a result of effective mitigation measures. The diurnal variability of carbonaceous aerosols was attributed to emissions emanating from local traffic at rush hours and nighttime open biomass burning. Surprisingly, semi-volatile ammonium chloride (NH4Cl) originating from local open biomass and waste burning was found to be the main chemical species in PM1 over Cairo. Its nighttime formation contributed to aerosol water uptake during morning hours, thereby playing a major role in the build-up of urban haze. While our results confirm the persistence of a significant dust reservoir over Cairo, they also unveil an additional source of highly hygroscopic (semi-volatile) inorganic salts, leading to a unique type of urban haze. This haze, with dominant contributors present in both submicron (primarily as NH4Cl) and supermicron (largely as dust) modes, underscores the potential implications of heterogeneous chemical transformation of air pollutants in urban environments.

Investigating the industrial origin of terpenoids in a coastal city in northern France: A source apportionment combining anthropogenic, biogenic, and oxygenated VOC.

Terpenoids have long been known to originate from natural sources. However, there is growing evidence for emissions from anthropogenic activities in cities, in particular from the production, manufacturing, and use of household solvents. Here, as part of the DATAbASE (Do Anthropogenic Terpenoids mAtter in AtmoSpheric chEmistry?) project, we investigate for the first time the potential role of industrial activities on the terpenoid burden in the urban atmosphere. This study is based on continuous VOC observations from an intensive field campaign conducted in July 2014 at an industrial-urban background site located in Dunkirk, Northern France. More than 80 VOCs including oxygenated and terpenoid compounds were measured by on-line Thermal Desorption Gas Chromatography with a Flame Ionization Detection (TD-GC-FID) and Proton Transfer Reaction-Time of Flight Mass Spectrometry (PTR-ToFMS). Isoprene, α-pinene, limonene and the sum of monoterpenes were the terpenoids detected at average mixing ratios of 0.02 ± 0.02 ppbv, 0.02 ± 0.02 ppbv, 0.01 ± 0.01 ppbv and 0.03 ± 0.05 ppbv, respectively. Like other anthropogenic VOCs, the mixing ratios of terpenoids significantly increase downwind the industrial plumes by one order of magnitude. Positive Matrix Factorization (PMF) was performed to identify the different emission sources of VOCs and their contribution. Six factors out of the eight factors extracted (r2 = 0.95) are related to industrial emissions such as solvent use, chemical and agrochemical storage, metallurgy, petrochemical, and coal-fired industrial activities. From the correlations between the industrial-type PMF factors, sulfur dioxide, and terpenoids, we determined their emissions ratios and we quantified for the first time their industrial emissions. The highest emission ratio is related to the alkene-dominated factor and is related to petrochemical, metallurgical and coal-fired industrial activities. The industrial emissions of monoterpenes equal 8.1 ± 4.3 tons/year. Those emissions are as significant as the non-industrialized anthropogenic ones estimated for the Paris megacity.

Light oxygenated volatile organic compound concentrations in an Eastern Mediterranean urban atmosphere rivalling those in megacities.

Highly resolved measurements of primary and secondary oxygenated volatile organic compounds (OVOCs) by proton-transfer-reaction mass spectrometry (PTR-MS) and the AMOVOC sampler (Airborne Measurements Of VOC) were performed in Beirut, Lebanon, during the ECOCEM (Emissions and Chemistry of Organic Carbon in the East Mediterranean) experiments. The OVOC concentrations (0.15-7.0 ppb) rival those reported for international megacities like Paris, Tokyo, or São Paulo (0.3-6.5 ppb). This study highlights the seasonal variability of OVOCs, the potential role of background pollution on OVOC concentrations, traffic emissions of OVOCs, and the secondary production of OVOCs during both summer and winter. The primary and secondary OVOC fractions were estimated using two methods based on the night-time emission ratio and photochemical age. Our calculations coupled with a correlation analysis revealed the following: firstly, background concentrations contributed significantly, especially for longer-lived OVOCs, such as methanol and acetone (30%-80%). Secondly, secondary production in summer increased up to 60%, except for methanol and isoprene oxidation products, i.e., for methacrolein and methyl vinyl ketone. Thirdly, the secondary production in the Eastern Mediterranean persisted in winter, and finally, strong primary traffic emissions dominated the primary biogenic emissions. Finally, the emission ratios were used to evaluate the global anthropogenic emission inventories downscaled to Lebanon. Although limited to two individual non-lumped species (formaldehyde and acetone), the emission ratios compared well, within a factor of 2. However, the emissions of aldehydes and ketones from the CAMS, Edgar, and MACCITY inventories showed discrepancies of up to three orders of magnitude. This demonstrates a need for improved OVOC representation in emission inventories, considering the atmospheric relevance and abundance of OVOCs and their use in volatile chemical products.

Temporal trend of diarrhea morbidity rate with climate change: Egypt as a case study.

Many studies have detected a relationship between diarrhea morbidity rates with the changes in precipitation, temperature, floods, droughts, water shortage, etc. But, most of the authors were cautious in their studies, because of the lack of empirical climate-health data and there were large uncertainties in the future projections. The study aimed to refine the link between the morbidity rates of diarrhea in some Egyptian governorates representative of the three Egyptian geographical divisions with the meteorological changes that occurred in the 2006-2016 period for which the medical data are available, as a case study. Medical raw data was collected from the Information Centre Department of the Egyptian Ministry of Health and Population. The meteorological data of temperature and precipitation extremes were defined as data outside the 10th-90th percentile range of values of the period of study, and their analysis was done using a methodology similar to the one recommended by the WMO and integrated in the CLIMDEX software. Relationships between the morbidity rates of diarrhea in seven Egyptian governorates and the meteorological changes that occurred in the period 2006 to 2016 were analyzed using multiple linear regression analysis to identify the most effective meteorological factor that affects the trend of morbidity rate of diarrhea in each governorate. Statistical analysis revealed that some meteorological parameters can be used as predictors for morbidity rates of diarrhea in Cairo, Alexandria, and Gharbia, but not in Aswan, Behaira, and Dakahlia where the temporal evolution cannot be related with meteorology. In Red Sea, there was no temporal trend and no significant relationships between the diarrhea morbidity rate and meteorological parameters. The predictor meteorological parameters for morbidity rates of diarrhea were found to be depending on the geographic locations and infrastructures in these governorates. It was concluded that the meteorological data that can be used as predictors for the morbidity rate of diarrhea is depending on the geographical location and infrastructures of the target location. The socioeconomic levels as well as the infrastructures in the governorate must be considered confounders in future studies.

Evaluation of the Sources, Precursors, and Processing of Aerosols at a High-Altitude Tropical Site.

This work presents the results from a set of aerosol- and gas-phase measurements collected during the BIO-MAÏDO field campaign in Réunion between March 8 and April 5, 2019. Several offline and online sampling devices were installed at the Maïdo Observatory (MO), a remote high-altitude site in the Southern Hemisphere, allowing the physical and chemical characterization of atmospheric aerosols and gases. The evaluation of short-lived gas-phase measurements allows us to conclude that air masses sampled during this period contained little or no anthropogenic influence. The dominance of sulfate and organic species in the submicron fraction of the aerosol is similar to that measured at other coastal sites. Carboxylic acids on PM10 showed a significant contribution of oxalic acid, a typical tracer of aqueous processed air masses, increasing at the end of the campaign. This result agrees with the positive matrix factorization analysis of the submicron organic aerosol, where more oxidized organic aerosols (MOOAs) dominated the organic aerosol with an increasing contribution toward the end of the campaign. Using a combination of air mass trajectories (model predictions), it was possible to assess the impact of aqueous phase processing on the formation of secondary organic aerosols (SOAs). Our results show how specific chemical signatures and physical properties of air masses, possibly affected by cloud processing, can be identified at Réunion. These changes in properties are represented by a shift in aerosol size distribution to large diameters and an increased contribution of secondary sulfate and organic aerosols after cloud processing.

Isoprene in urban Atlantic forests: Variability, origin, and implications on the air quality of a subtropical megacity.

Biosphere-atmosphere interactions play a key role in urban chemistry because of biogenic volatile organic compound (BVOC) emissions. Of the BVOC, isoprene is the most emitted compound; however, it also has anthropogenic origins in urban areas. In this study, we aimed to investigate the spatio-temporal variability and atmospheric impacts of biogenic and anthropogenic isoprene in the subtropical megacity of São Paulo (MASP), Brazil. Several measurement campaigns were conducted in three different urban Atlantic forests (Matão, PEFI, and RMG), and an urban background site (IAG); this equated to a total of 268 samples for the 2018-2019 period. For all sampling points, daytime average concentrations of isoprene were two to three times higher during the rainy season (IAG: 1.75 ± 0.93 ppb; Matão: 0.87 ± 0.35 ppb; PEFI: 0.50 ± 0.30 ppb; RMG: 0.37 ± 0.18 ppb), than those observed during the dry season (IAG: 0.46 ± 0.24 ppb; Matão: 0.31 ± 0.17 ppb; PEFI: 0.17 ± 0.11 ppb; RMG: 0.11 ± 0.07 ppb). Average isoprene concentrations were similar to those observed in other places worldwide, with the exception of the Amazon forest. Our results indicate differences in isoprene concentrations between sites, suggesting that environmental conditions such as the urban heat island and vegetation types, may play a role in spatial variability. Estimates of the isoprene fraction indicated that the biogenic fraction (85%) surpassed the anthropogenic fraction during the rainy season. By contrast, the anthropogenic fraction (52%) exceeded the biogenic fraction during dry periods. These fractions have an impact on potentially forming secondary pollutants gaseous (ozone formation potential: 7.19-33.32 µg m-3), and aerosols (secondary organic aerosols formation potential: 0.41-1.88 µg m-3). These results highlight the role of biogenic isoprene and its potential impact on urban air quality in subtropical megacities; this requires further investigation under future climate change scenarios.

One decade of VOCs measurements in São Paulo megacity: Composition, variability, and emission evaluation in a biofuel usage context.

In South America, the observations of atmospheric pollutants are deficient, and few cities have implemented air quality monitoring programs. In addition, Volatile Organic Compounds (VOCs) observations are still missing, and little is known about their contributions to the atmospheric composition and impacts in a large ethanol usage context like Brazil. Here, we present a wide range of VOCs that have been measured for ten years in São Paulo Megacity (SPM) in different campaigns at traffic, urban and background sites. When compared with other cities worldwide, the average VOCs ambient concentrations in SPM were higher by factors of 2 to 10. However, the ambient VOCs distribution among these cities is homogeneous even for ethanol, aldehydes and alkenes species. Emission ratios (ER) were established related to carbon monoxide and acetylene, which did not depict strong seasonal and interannual variability in SPM. When compared with previous studies, ERs showed an enrichment from road-tunnel to background, suggesting the presence of other sources than traffic. A good agreement in ER was found with Los Angeles and Paris; but limited consistencies with Middle East and Asia cities. Our ethanol measurements show that contrasted ER can be obtained depending on the emission process involved, with a strong impact of evaporation on ethanol concentrations. The multiyear acetaldehyde analysis displayed that ER could be a valuable metric to assess the long-term changes in emissions sources. Finally, VOCs emissions were calculated from ER and compared with those estimated by the global emission inventory (Edgar). The total VOC emissions estimated by the global inventory agree very well with those from our observations up to 75%. Nevertheless, the VOCs speciation is misrepresented in the inventory, mainly for oxygenated and heavier alkanes compounds. These inconsistencies will also have an impact on the quantification of secondary atmospheric pollutants formation associated to road transport emissions.

Is Traffic Still an Important Emitter of Monoaromatic Organic Compounds in European Urban Areas?

Trends of long-term observations and emission inventories suggest that traffic emissions will no longer dominate the concentrations of monoaromatic compounds (i.e., TEX - toluene, xylenes, and ethylbenzene) in European urban areas. But the split limit between traffic and other emission sector contributions such as solvent use remains tenuous. Here long-term observations of an extensive set of hydrocarbons, including TEX, at traffic and urban background sites in London, Paris and Strasbourg were combined to estimate the relative importance of traffic emissions on TEX in every city. When analyzing the urban enhancement emission ratios of TEX-to-benzene on a seasonal basis, two potential source signatures other than traffic could be differentiated in all cities (1) summertime evaporation from fuel and/or solvent and (2) wintertime domestic heating. However, traffic emissions still unambiguously dominate the concentration levels of TEX in every city despite the reduction of their emissions at exhaust pipe over the last two decades. Traffic explains between 60% and 96% (at ±20%) of TEX levels while it is less clear for xylenes at some locations. Our results provide a basis to evaluate regional emission inventories. The method is applicable at any urban area where speciated hydrocarbon monitoring is available.

Tackling the mortality from long-term exposure to outdoor air pollution in megacities: Lessons from the Greater Cairo case study.

OBJECTIVE: The poor outdoor air quality in megacities of the developing world and its impact on health is a matter of concern for both the local populations and the decision-makers. The objective of this work is to quantify the mortality attributable to long-term exposure to PM2.5, NO2, and O3 in Greater Cairo (Egypt). METHODS: We analyze the temporal and spatial variability of the three pollutants concentrations measured at 18 stations of the area. Then, we apply the method recommended by the WHO to estimate the excess mortality. In this assessment, three different shapes (log-linear, linear, and log-log) of the concentration-response functions (CRF) are used. RESULTS: With PM2.5 concentrations varying from 50 to more than 100µg/m3 in the different sectors of the megacity, the spatial variability of this pollutant is found to be one important cause of uncertainty on the excess mortality associated with it. Also important is the choice of the CRF. With the average (75µg/m3) PM2.5 concentration and the most favorable log-log shape of the CRF, 11% (CI, 9-14%) of the non-accidental mortality in the population older than 30 years can still be attributed to PM2.5, which corresponds to 12520 (CI, 10240-15930) yearly premature deaths. Should the Egyptian legal 70µg/m3 PM10 limit (corresponding to approximately 37.5µg/m3 for PM2.5) be met, this number would be reduced to 7970, meaning that 4550 premature deaths could be avoided each year. Except around some industrial or traffic hot spots, NO2 concentration is found to be below the 40µg/m3 air quality guideline of the WHO. However, the average concentration (34µg/m3) of this gas exceeds the stricter 10µg/m3 recommendation of the HRAPIE project and it is thus estimated that from 7850 to 10470 yearly deaths can be attributed to NO2. Finally, with the ozone concentration measured at one station only, it is found that, depending on the choice of the CRF, between 2.4% and 8.8% of the mortality due to respiratory diseases can be attributed to this gas. CONCLUSION: In Greater Cairo, PM2.5 and NO2 constitute major health risks. The best estimate is that in the population older than 30 years, 11% and 8% of the non-accidental mortality can be attributed to these two pollutants, respectively.

Quantitative cancer risk assessment and local mortality burden for ambient air pollution in an eastern Mediterranean City.

Health risks posed by ambient air pollutants to the urban Lebanese population have not been well characterized. The aim of this study is to assess cancer risk and mortality burden of non-methane hydrocarbons (NMHCs) and particulates (PM) based on two field-sampling campaigns conducted during summer and winter seasons in Beirut. Seventy NMHCs were analyzed by TD-GC-FID. PM2.5 elemental carbon (EC) components were examined using a Lab OC-EC aerosol Analyzer, and polycyclic aromatic hydrocarbons were analyzed by GC-MS. The US EPA fraction-based approach was used to assess non-cancer hazard and cancer risk for the hydrocarbon mixture, and the UK Committee on Medical Effects of Air Pollutants (COMEAP) guidelines were followed to determine the PM2.5 attributable mortality burden. The average cumulative cancer risk exceeded the US EPA acceptable level (10-6) by 40-fold in the summer and 30-fold in the winter. Benzene was found to be the highest contributor to cancer risk (39-43%), followed by 1,3-butadiene (25-29%), both originating from traffic gasoline evaporation and combustion. The EC attributable average mortality fraction was 7.8-10%, while the average attributable number of deaths (AD) and years of life lost (YLL) were found to be 257-327 and 3086-3923, respectively. Our findings provide a baseline for future air monitoring programs, and for interventions aiming at reducing cancer risk in this population.

NitroMAC: An instrument for the measurement of HONO and intercomparison with a long-path absorption photometer.

NitroMAC (French acronym for continuous atmospheric measurements of nitrogenous compounds) is an instrument which has been developed for the semi-continuous measurement of atmospheric nitrous acid (HONO). This instrument relies on wet chemical sampling and detection using high performance liquid chromatography (HPLC)-visible absorption at 540 nm. Sampling proceeds by dissolution of gaseous HONO in a phosphate buffer solution followed by derivatization with sulfanilamide/N-(1-naphthyl)-ethylenediamine. The performance of this instrument was found to be as follows: a detection limit of around 3 ppt with measurement uncertainty of 10% over an analysis time of 10 min. Intercomparison was made between the instrument and a long-path absorption photometer (LOPAP) during two experiments in different environments. First, air was sampled in a smog chamber with concentrations up to 18 ppb of nitrous acid. NitroMAC and LOPAP measurements showed very good agreement. Then, in a second experiment, ambient air with HONO concentrations below 250 ppt was sampled. While NitroMAC showed its capability of measuring HONO in moderate and highly polluted environments, the intercomparison results in ambient air highlighted that corrections must be made for minor interferences when low concentrations are measured.

Intermediate-volatility organic compounds: a large source of secondary organic aerosol.

Secondary organic aerosol (SOA) is a major component of atmospheric fine particle mass. Intermediate-volatility organic compounds (IVOCs) have been proposed to be an important source of SOA. We present a comprehensive analysis of atmospheric IVOC concentrations and their SOA production using measurements made in Pasadena, California during the California at the Nexus of Air Quality and Climate Change (CalNex) study. The campaign-average concentration of primary IVOCs was 6.3 ± 1.9 µg m(-3) (average ± standard deviation), which is comparable to the concentration of organic aerosol but only 7.4 ± 1.2% of the concentration of speciated volatile organic compounds. Only 8.6 ± 2.2% of the mass of the primary IVOCs was speciated. Almost no weekend/weekday variation in the ambient concentration of both speciated and total primary IVOCs was observed, suggesting that petroleum-related sources other than on-road diesel vehicles contribute substantially to the IVOC emissions. Primary IVOCs are estimated to produce about 30% of newly formed SOA in the afternoon during CalNex, about 5 times that from single-ring aromatics. The importance of IVOCs in SOA formation is expected to be similar in many urban environments.

New off-line aircraft instrumentation for non-methane hydrocarbon measurements.

New off-line instrumentation was developed to implement measurements of non-methane hydrocarbons (NMHC) on (French) research aircraft. NMHC are collected on multisorbent tubes by AMOVOC (Airborne Measurements Of Volatile Organic Compounds), a new automatic sampler. AMOVOC is a versatile and portable sampler targeting a wide range of NMHC at high frequency (sampling time of 10 min). Multisorbent tubes are analyzed on the ground by short-path thermal desorption coupled with gas chromatography and mass spectrometry. The development and optimization of both NMHC sampling and analysis are reported here. On the one hand, the paper points out technical choices that were made according to aircraft constraints and avoiding sample loss or contamination. On the other hand, it describes analytical optimization, tube storage stability, and moisture removal. The method shows high selectivity, sensitivity (limit of detection less than 10 ppt) and precision (less than 24%). Finally, NMHC data collected on French aircraft during the African Monsoon Multidisciplinary Analysis campaign are reported for the first time. The results highlight instrumentation validity and protocol efficiency for NMHC measurements in the lower and upper troposphere.

Characterising sources and sinks of rural VOC in eastern France.

Fifty non-methane hydrocarbons (NMHC) and seventeen carbonyl compounds were measured at a French rural site from 1997 to 2001, as part of the EMEP programme. Data handling was based on an original source-receptor approach. First, the examination of the levels and trends was completed by the comparison of the seasonal distribution of rural and urban VOC/acetylene ambient ratios. This analysis has shown that most of the compounds derived from mixing and photochemical transformation of mid-range transported urban pollutants from the downwind urban area. Then, identified sources and sinks were temporally apportioned. Urban air masses mixing explains, at least, 80% of the wintertime levels of anthropogenic NMHC and isoprene. In summer, photochemistry dominates the day-to-day distribution of anthropogenic NMHC whilst summertime isoprene is also controlled by in-situ biogenic emissions. Then, the results of C(1)-C(3) carbonyls were discussed with respect to their direct biogenic and anthropogenic emissions and photochemical production through the [carbonyl/auto-exhaust tracers] emission ratio. Diluted vehicle exhaust emissions mainly contribute to the total content of lower aldehydes in winter while other processes control lower ketones. Secondary production is predominant in summer with at least a 50% high intensity. Its dependence upon temperature and radiation is also demonstrated. Finally, the importance of the primary and secondary biogenic production of acetone and formaldehyde is assessed. In particular, biogenic contribution would explain 37 +/- 25% of acetone levels in summer.