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.

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.

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.

Comprehensive chemical characterization of PM2.5 in the large East Mediterranean-Middle East city of Beirut, Lebanon.

The chemical composition of PM2.5 at two sites in Lebanon, a country in the East Mediterranean - Middle East region, is investigated in the spring and summer seasons. The average PM2.5 concentrations were of (29 ± 16) µg/m3 for Beirut urban site and (32 ± 14) µg/m3 for Beirut suburban site. This study showed that the geographic location of the East Mediterranean region, such as its proximity to the Mediterranean Sea and the dust storm intrusion are a significant contributor to the high PM levels from natural sources, which cannot be mitigated, rendering the PM2.5 WHO annual Air Quality guideline unattainable due to high natural background, which also applies to the entire Middle East region. Turkey and Eastern Europe are the dominant origin of air masses throughout our sampling days, suggesting the long-range transport as an important potential contributor to the high observed concentrations of V, Ni, and sulfate in this region most probably in other East Mediterranean countries than Lebanon too. Main local sources determined through the chemical speciation including organics are road transport, resuspension of dust and diesel private generators. A health risk assessment of airborne metals was performed and the carcinogenic risk for all the metals exceeded by 42 (adults) and 14 (children) times the acceptable risk level (10-6) at both sites. Vanadium was the predominant carcinogenic metal, emphasizing the need to replace energy production with cleaner energy on a regional level and highlighting the severe impact of air pollution on the health of inhabitants in this region's main cities.

Source apportionment of PM2.5 oxidative potential in an East Mediterranean site.

This study aimed to evaluate the oxidative potential (OP) of PM2.5 collected for almost a year in an urban area of the East Mediterranean. Two acellular assays, based on ascorbic acid (AA) and dithiothreitol (DTT) depletion, were used to measure the OP. The results showed that the mean volume normalized OP-AAv value was 0.64 ± 0.29 nmol·min-1·m-3 and the mean OP-DTTv was 0.49 ± 0.26 nmol·min-1·m-3. Several approaches were adopted in this work to study the relationship between the species in PM2.5 (carbonaceous matter, water-soluble ions, major and trace elements, and organic compounds) or their sources and OP values. Spearman correlations revealed strong correlations of OP-AAv with carbonaceous subfractions as well as organic compounds while OP-DTTv seemed to be more correlated with elements emitted from different anthropogenic activities. Furthermore, a multiple linear regression method was used to estimate the contribution of PM2.5 sources, determined by a source-receptor model (Positive Matrix Factorization), to the OP values. The results showed that the sources that highly contribute to the PM2.5 mass (crustal dust and ammonium sulfate) were not the major sources contributing to the values of OP. Instead, 69 % of OP-AAv and 62 % of OP-DTTv values were explained by three local anthropogenic sources: Heavy Fuel Oil (HFO) combustion from a power plant, biomass burning, and road traffic emissions. As for the seasonal variations, higher OP-AAv values were observed during winter compared to summer, while OP-DTTv did not show any significant differences between the two seasons. The contribution of biomass burning during winter was 33 and 34 times higher compared to summer for OP-AAv and OP-DTTv, respectively. On the other hand, higher contributions were observed for HFO combustion during summer.

Source apportionment of PM2.5 using organic/inorganic markers and emission inventory evaluation in the East Mediterranean-Middle East city of Beirut.

Source contributions to PM2.5 concentrations were evaluated in Greater Beirut (Lebanon), a typical East Mediterranean-Middle East (EMME) city, using Positive Matrix Factorization with two approaches. The first approach included only inorganic species (PMF-trad) and the other approach added organic markers (PMF-org). PMF-org identified 4 additional sources, and large discrepancies in contributions were observed for some major sources found in both approaches, highlighting the importance of including organic markers. The traffic factor was underestimated in PMF-trad by 2 to 7 folds. Moreover, results showed that this city is prone to high desert dust concentrations originating from uncontrollable dust storm events, like all cities in the Middle East. A PM2.5 mitigation plan taking into account the potency of the identified sources was developed. Sources like diesel generators or traffic presented smaller contributions in term of mass compared to desert dust, however the health impact of the latter is relatively small and actions should target sources with the highest potency. Local emission inventories in the EMME region are scarce and studies typically rely on global emission inventories for local air quality management plans, but these inventories significantly underestimate Beirut's road transport emissions by more than an order of magnitude.

Chemical profiles of PM2.5 emitted from various anthropogenic sources of the Eastern Mediterranean: Cooking, wood burning, and diesel generators.

The chemical profiles of PM2.5 emitted from a non-road diesel generator, wood burning and cooking activities including chicken and beef charcoal grilling and general cooking activities were determined. The characterization included the carbonaceous fraction (OC/EC), water-soluble ions, elements, and organic species comprising n-alkanes, polycyclic aromatic hydrocarbons, carboxylic acids, levoglucosan, dioxins, furans, and dioxin-like polychlorinated biphenyls. The main component in the PM2.5 from the different sources was carbonaceous matter with a mass contribution to PM2.5 of 49% for cooking activities, 53% for wood burning, 66% for beef grilling, 72% for chicken grilling, and 74% for diesel generator with different OC/EC concentration ratios. The analysis of organic compounds contents using diagnostic ratios and indexes showed differences between the sources and revealed specific source markers. The water-soluble ions had the highest contribution in the cooking activities profile with 17% of PM2.5 and the least in the chicken grilling profile (1.1%). Additionally, 29 analyzed elements were identified, and their contribution varied with the sources (ranging from 1% to 11% of PM2.5). These findings could be used to differentiate these sources and could assist in the use of source apportionment methods.

Prenatal exposure to criteria air pollutants and associations with congenital anomalies: A Lebanese national study.

Maternal exposure to air pollution has been associated with a higher birth defect (BD) risk. Previous studies suffer from inaccurate exposure assessment methods, confounding individual-level variations, and classical analytical modelling. This study aimed to examine the association between maternal exposure to criteria air pollutants and BD risk. A total of 553 cases and 10,214 controls were identified from private and public databases. Two subgroups were then formed: one for a matched case-control design, and another for Feature Selection (FS) analysis. Exposure assessment was based on the mean air pollutant-specific levels in the mother's residential area during the specific BD gestational time window of risk (GTWR) and other time intervals. Multivariate regression models outcomes consistently showed a significant protective effect for folic acid intake and highlighted parental consanguinity as a strong BD risk factor. After adjusting for these putative risk factors and other covariates, results show that maternal exposure to PM2.5 during the first trimester is significantly associated with a higher overall BD risk (OR:1.05, 95%CI:1.01-1.09), and with a higher risk of genitourinary defects (GUD) (OR:1.06, 95%CI:1.01-1.11) and neural tube defects (NTD) (OR:1.10, 95%CI:1.03-1.17) during specific GTWRs. Maternal exposure to NO2 during GTWR exhibited a significant protective effect for NTD (OR:0.94, 95%CI:0.90-0.99), while all other examined associations were not statistically significant. Additionally, maternal exposure to SO2 during GTWR showed a significant association with a higher GUD risk (OR:1.17, 95%CI:1.08-1.26). When limiting selection to designated monitor coverage radiuses, PM2.5 maintained significance with BD risk and showed a significant gene-environment interaction for GUD (p = 0.018), while NO2 protective effect expanded to other subtypes. On the other hand, FS analysis confirmed maternal exposure to PM2.5 and NO2 as important features for GUD, CHD, and NTD. Our findings, set the basis for building a novel BD risk prediction model.

Impact of a novel partial defatting technology on oxidative stability and sensory properties of peanut kernels.

A novel process, 'mechanical expression preserving shape integrity', was conceived to prepare low-fat peanuts in response to health-conscious consumer demands. The main purpose of this study was to preserve the taste, aroma, and oxidative stability of the defatted product. Results generated from a central composite rotatable design showed that highest consumer sensory scores were reached at low pressures (4-6 MPa). Free fatty acid, peroxide, p-anisidine, and total oxidation values were mostly affected by water content [W] and pressure [P] with high correlation coefficients (82% < R2 < 87%). Overall, lipid oxidation and flavor fade were associated with higher defatting ratios and greater physical damage. The latter plays a major role in increasing the surface area and facilitating the access of oxygen to the remaining oil, thus rendering the defatted product more prone to oxidation. However, oxidation was reduced significantly using a Response Surface Methodology to optimize conditions ([W] 12.2 ± 0.6%d.b., [P] 6 ± 0.3 MPa and time [t] 18.2 ± 0.6 min).

PM2.5 characterization of primary and secondary organic aerosols in two urban-industrial areas in the East Mediterranean.

Primary and secondary organic aerosols in PM2.5 were investigated over a one-year campaign at Zouk Mikael and Fiaa, Lebanon. The n-alkanes concentrations were quite similar at both sites (26-29 ng/m3) and mainly explained by anthropogenic emissions rather than natural ones. The concentrations of total Polycyclic Aromatic Hydrocarbons (PAHs) were nearly three times higher at Zouk Mikael (2.56 ng/m3) compared to Fiaa (0.95 ng/m3), especially for indeno[1,2,3-c,d]pyrene linked to the presence of the power plant. A characteristic indeno[1,2,3-c,d]pyrene/(indeno[1,2,3-c,d]pyrene + benzo[g,h,i]perylene) ratio in the range 0.8-1.0 was determined for heavy fuel oil combustion from the power plant. Fatty acids and hopanes were also investigated and were assigned to cooking activities and vehicular emissions respectively. Phthalates were identified for the first time in Lebanon with high concentrations at Zouk and Fiaa (106.88 and 97.68 ng/m3 respectively). Moreover, the biogenic secondary aerosols revealed higher concentrations in summer. The total terpene concentration varied between 131 ng/m3 at Zouk Mikael in winter to 469 ng/m3 at Fiaa in summer. Additionnally, the concentrations of the dicarboxylic acids especially for adipic and phthalic acids were more influenced by anthropogenic sources.The analysis of molecular markers and diagnostic ratios indicated that the sites were strongly affected by anthropogenic sources such as waste open burning, diesel private generators, cooking activities, road transport, power plant, and industrial emissions. Moreover, results showed different pattern during winter and summer seasons. Whereas, higher concentrations of biogenic markers were clearly encountered during the summer period.

Ability of Soil Isolated Actinobacterial Strains to Prevent, Bind and Biodegrade Ochratoxin A.

Ochratoxin A (OTA) is one of the most important mycotoxins, and contaminates several agricultural products, particularly cereals, grapes, maize, barley, spices and coffee. The aim of this project was to reduce the levels of OTA by supplementing the artificially contaminated solutions with seven strains of actinobacteria (AT10, AT8, SN7, MS1, ML5, G10 and PT1) in order to evaluate their capacity for binding and metabolizing the OTA, as well as their ability to reduce the expression of the genes responsible for its production in A. carbonarius. In the first part of this study, we evaluated the capacity of Streptomyces strains for binding OTA on their surfaces after 0, 30 and 60 min of incubation with PBS solution supplemented with OTA. In the second part, we tested the ability of these strains, as well as their supernatants, to detoxify the ISP2 medium. Finally, we studied the effect of the Streptomyces cocultured with Aspergillus carbonarius on the expression of OTA biosynthesis genes. Results showed that, among the strains co-cultured with A. carbonarius, the strain G10 was able to reduce the expression of acpks, acOTApks, acOTAnrps and vea genes, thus reducing OTA from solid PDA medium to 13.50% of reduction. This strain was remarkably able to detoxify and bind OTA up to 47.07%. Strain AT8 was stronger in detoxifying OTA (52.61%), but had no significant effect on the studied gene expression.

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.

Color and texture of low-calorie peanuts as affected by a new oil extraction process named "Mechanical Expression Preserving Shape Integrity" (MEPSI).

The current healthy life style pushed to develop and implement a novel efficient defatting process of high quality called "Mechanical Expression Preserving Shape Integrity" that conserved the sensory, color, textural, morphological and acceptability of partially defatted roasted peanuts. In this study, Response Surface Methodology was used to investigate the best extraction parameters (initial water content, pressure and pressing duration) based on the highest Color Consumer Evaluation scores, the best colorimetric parameters (L*, a*, b*, ΔE*) and the most appealing textural attributes (Fracturability, First Fracture Work Done, First Fracture Percentage of Deformation, Rupture Force, Percentage of Deformation at Rupture). Experimental results showed that defatting promotes a lighter and neutral grain color, higher fracturability and rupture force as well as higher deformation strength. Aiming to retain most of the colorimetric and textural properties after defatting and roasting, it was found that peanuts should be hydrated to 7 % d.b. and treated at 4.74 MPa for 14.22 min.

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.

A novel process for preparing low-fat peanuts: Optimization of the oil extraction yield with limited structural and organoleptic damage.

The main purpose of this study was to extract the maximum amount of oil from peanuts without causing major damage and preserving their organoleptic quality after defatting. Accordingly, a successful, healthy, eco-friendly and economic defatting process for peanuts was implemented using mechanical oil expression, which was optimized by means of Response Surface Methodology. The results demonstrated that maximum extraction yields were obtained at a low initial moisture content (5-7% d.b.). Defatting and deformation ratios were mostly affected by the pressure and water content with high correlation coefficients (98.4% and 97.5%, respectively), and overall acceptability decreased following higher oil extraction yields. It was concluded that the optimum values for the product moisture content, pressure, and pressing duration were 5% d.b., 9.7 MPa and 4 min, respectively, with a defatting ratio of 70.6%. This resulted in an insignificant irreversible deformation ratio (<1%) and an overall acceptability of 7.6 over 10.

ß-Cyclodextrin-assisted extraction of polyphenols from vine shoot cultivars.

This work optimized the ß-cyclodextrin (ß-CD)-assisted extraction process of polyphenols from vine shoots. The efficiency of ß-CD was compared to that of ethanol in terms of the quantity and antioxidant capacity (AC) of the extracted polyphenols. Response surface methodology permitted the optimization of the ß-CD concentration, time, and temperature. The optimal polyphenol content (PC) [5.8 mg of gallic acid equivalent (GAE)/g of dry matter (DM)] and AC [3146 micromolar trolox equivalent per milliliter (µMTE)] were initially obtained with Syrah cultivar after an extraction of 48 h at 66.6 °C with a 37.7 mg/mL aqueous ß-CD solvent. The same PC (5.8 mg of GAE/g of DM) was reached with 50% ethanol/water solvent after 1.65 h. However, a lower AC was found with ethanol (2000 µMTE) compared to ß-CD. A comparison of the PC and AC of four different vine shoot cultivars was realized. Our results clearly show the capacity of ß-CD to amplify polyphenol extraction from vine shoots.

Detection of Golden apples' climacteric peak by laser biospeckle measurements.

In this paper, we report a study in which a laser biospeckle technique is used to detect the climacteric peak indicating the optimal ripeness of fruits. We monitor two batches of harvested Golden apples going through the ripening phase in low- and room-temperature environments, determine speckle parameters, and measure the emitted ethylene concentration using gas chromatography as reference method. Speckle results are then correlated to the emitted ethylene concentration by a principal component analysis. From a practical point of view, this approach allows us to validate biospeckle as a noninvasive and alternative method to respiration rate and ethylene production for climacteric peak detection as a ripening index.

Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid.

The hydroxyl (OH) radical is the most important oxidant in the atmosphere since it controls its self-oxidizing capacity. The main sources of OH radicals are the photolysis of ozone and the photolysis of nitrous acid (HONO). Due to the attenuation of solar radiation in the indoor environment, the possibility of OH formation through photolytic pathways indoors has been ignored up to now. In the indoor air, the ozonolysis of alkenes has been suggested as an alternative route of OH formation. Models and indirect measurements performed up to now according to this hypothesis suggest concentrations of OH radicals on the order of 10(4)-10(5) molecules per cubic centimeter. Here, we present direct measurements of significant amounts of OH radicals of up to 1.8⋅10(6) molecules per cubic centimeter during an experimental campaign carried out in a school classroom in Marseille. This concentration is on the same order of magnitude of outdoor OH levels in the urban scenario. We also show that photolysis of HONO is an important source of OH radicals indoors under certain conditions (i.e., direct solar irradiation inside the room). Additionally, the OH concentrations were found to follow a linear dependence with the product J(HONO)⋅[HONO]. This was also supported by using a simple quasiphotostationary state model on the OH radical budget. These findings force a change in our understanding of indoor air quality because the reactivity linked to OH would involve formation of secondary species through chemical reactions that are potentially more hazardous than the primary pollutants in the indoor air.