Chemical characterization of fine particles (PM2.5) at a coastal site in the South Western Mediterranean during the ChArMex experiment.

As part of the ChArMEx project (Chemistry-Aerosol Mediterranean Experiment, http://charmex.lsce.ipsl.fr), one year of continuous filter sampling was conducted from August 2012 to August 2013 at a rural (coastal) site in Algeria aiming to better document fine aerosol seasonal variability and chemical composition in the Southern part of the Mediterranean. Over 350 filters have been collected, weighted, and analyzed for the main ions and organic and elemental carbon. The obtained mass concentrations varied between 2.5 and 50.6 µg/m3 for PM2.5. The annual modulations of PM2.5 showed higher concentrations in the end summer 2012 and the early summer 2013 (28.50 µg/m3 in August 2012, 20.23 µg/m3 in September 2012, 20.19 µg/m3 in July 2013, and 17.88 µg/m3in August 2013). The particulate organic matter (POM) presented the greatest contribution (50%), followed by the secondary inorganic aerosols (SIA, 27%). The average organic carbon OC concentrations ranged from 1.66 to 6.05 µgC/m3. The average elemental carbon EC concentrations ranged from 0.92 to 3.49 µgC/m3 and contributed 7% of the PM2.5 mass to Bou-Ismail. The average value of the OC /EC ratio was close to 5.1 in Bou-Ismail, and was close to that found in Finokalia 4 (Greece 2004, 2006) but was lower than that of Montseny 11 (Spain 2002-2007) Western Mediterranean Basin (WMB). The concentrations of water-soluble organic carbon WSOC in the PM2.5 ranging from 0.66 to 3.70 µg/m3 recorded the minimum level in March 2013, and the maximum level in August 2012, with an average of 2.02 µg/m3.

Polycyclic aromatic hydrocarbons, phthalates, parabens and other environmental contaminants in dust and suspended particulates of Algiers, Algeria.

Chemicals such as polycyclic aromatic hydrocarbons (PAHs), phthalateesters, parabens, siloxanes and squalene, all of them classified as endocrine-disrupting chemicals (EDCs), have been reported to occur in all environmental compartments. The effects of EDCs on development, reproduction, growth, metabolism and obesity constitute a real public health issue. A list of EDCs (> 40 compounds) were characterised in total suspended particulates (outdoor soot: 92 samples) collected in July-September 2016 in an Algiers urban area; besides, settled indoor dusts (36 samples) were collected between November and December 2016 in schools, homes, manufacture and hospital of the same province. The analytical procedure consisted of ultrasonic bath extraction, column chromatography separation into fractions of different polarity and gas chromatographic-mass spectrometric processing. The total loads of phthalates ranging from 6.0 to 347 ng/m2 (median, 26 ng/m2) were determined in indoor dust and 4.6 to 11.6 ng/m3 (median, 7.9 ng/m3) in outdoor soot; meanwhile, PAHs ranged from 12.1 to 108 ng/m2 (median, 36 ng/m2) in indoor dust and ranged from 5.6 to 7.7 ng/m3 (median 5.7 ng/m3) in outdoor soot. Finally, illicit substances such as cocaine, cannabinol and Δ9-tetrahydrocannabinol were found to range from 0.5 to 11 pg/m3, 4.6 to 9.2 pg/m3 and 11 to 81 pg/m3, respectively, in outdoor soot.

Assessment of dioxin-like activity in PM10 air samples from an industrial location in Algeria, using the DRE-CALUX bioassay.

When compared to the European guidelines, PM10 (particulate matter up to 10-µm size) concentrations in Algeria are often exceeding the maximum limits, and in general, no information exists on the compounds bound on its surface. The objective of this study was to measure the dioxin-like activity of polychlorinated dibenzodioxines and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (PCBs) in the PM10 fraction at the Sour El Ghozlane cement plant in Algeria. PM10 samples (n = 23) were taken between 24 March and 15 April 2013, using a medium volume sampler and 47-mm PTFE filters. The 24-h samples were dried to determine the PM10 content and afterward extracted, cleaned up, and analyzed with the dioxin-responsive element-chemical-activated luciferase gene expression (DRE-CALUX) bioassay. Our results showed that the measured bioanalytical equivalents (BEQs) were similar to those in other international industrial sites worldwide. The PCDD/Fs and dioxin-like PCBs (dl-PCBs) were positively correlated (rho = 0.6, p = 0.002), indicating that they have similar sources. Furthermore, samples from March showed higher PCDD/F and dl-PCB BEQs and humidity but lower temperatures compared to samples from April, while there was no difference in the PM10 concentrations between the two months. These results reveal that PM10 alone is not a good proxy and that meteorological conditions are an important factor in assessing dioxin-like pollution in the atmosphere. It seems that, at present, there is no health hazard through direct airborne human exposure to dioxin-like pollutants in PM10 from this site. However, it is important to monitor these POPs for a longer period of time and also to gain more insight in their distribution between the particulate and gas phase in relation to meteorological conditions.

A wintertime study of polycyclic aromatic hydrocarbons (PAHs) in indoor and outdoor air in a big student residence in Algiers, Algeria.

The wintertime concentrations and diel cycles of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) associated to atmospheric particulate matter with aerodynamic diameter lesser than 10 µm were determined at the biggest student residence in Algeria located in Bab-Ezzouar, 15 km southeast from Algiers city area. Samplings were carried out from December 2009 to March 2010, and organic compounds were characterized using gas chromatography coupled with mass spectrometric detection. Volatile PAHs were also monitored inside some student residence rooms in order to evaluate the impact of indoor air pollution to student health. For the sake of comparison, aerial concentrations of n-alkanes and PAHs were determined in parallel in the Oued Smar industrial zone and two suburban areas, all located in Algiers. Total concentrations recorded in CUB1 student residence ranged from 101 to 204 ng m(-3) for n-alkanes and from 8 to 87 ng m(-3) for PAHs. Diel cycles have shown that, while concentrations of n-alkanes peaked at morning and afternoon-evening and dropped at night, those of PAHs exhibited higher levels at morning and night and lower levels at afternoon-evening, likely due to the reactivity of some PAHs. As expected, the indoor levels of PAHs were larger than in the outdoor of the student residence and were of serious health concern. Overall, the concentrations of n-alkanes and PAHs were as high as those observed in the industrial zone and higher than the two suburban sites.

Enantiomeric and non-enantiomeric monoterpenes of Juniperus communis L. and Juniperus oxycedrus needles and berries determined by HS-SPME and enantioselective GC/MS.

For the first time, enantiomeric and non-enantiomeric distribution of monoterpenes in the headspace of Juniperus communis L. and Juniperus oxycedrus needles and berries has been determined using HS-SPME combined with enantioselective GC/MS. The essential oils from needles and berries of both Juniperus species obtained by hydrodistillation were also performed. HS-SPME has shown good potential to reproduce the same results as the commonly used hydrodistillation extraction technique. While needles and berries of J. communis showed high contents of sabinene, α-pinene and ß-myrcene with 19-30%, 12-24% and 9-20%, respectively, J. oxycedrus was strongly dominated by α-pinene with 85-92% in both needles and berries. Large variations in chiral distribution of monoterpenes within the same plant species and between the two junipers were observed. Interestingly, similar enantiomeric preferences of monoterpenes were obtained between needles and berries of the two junipers.

Organic components of Algerian desert dusts.

The organic fraction associated to sands of five localities of Algerian Sahara Desert was characterized with regards to n-alkanes, polynuclear aromatic hydrocarbons (PAH) and mono/dicarboxylic acids. Huge differences were observed among total contents of the three groups in the sands and, within each group, with regard to percent distribution patterns of congeners. Mutagenic nitro-PAH were virtually absent. Organic acids were identified as the most abundant compounds in all samples (up to 4800 ng g(-1) vs. less than 700 of n-alkanes and 22 ng g(-1) of PAH); their presence was overall related to biogenic sources except for the Hassi Messaoud petroleum area, where an important contribution of anthropogenic emission was present. The sand composition at Hassi Messaoud (and, at lesser extent, Tougguort) seemed to indicate that environmental conditions promote there the oxidative decomposition of organics; by contrast, at Laghouat, Hassi Bahbah and Gardaïa oases the deposition involved fresh (non-reacted) air pollutants. The sand composition at the Hassi Messaoud was compared to that of airborne particulates of the industrial district and city. Airborne n-alkanes (≈500 ng m(-3)) and fatty acids (≈15000 ng m(-3)) were very high compared to Algiers city, whilst PAH contents (10-60 ng m(-3)) were typical of polluted areas in winter; similarly, the sands were reach of the two aliphatic groups and relatively poor of PAH.

Distribution of the solvent-extractable organic compounds in fine (PM1) and coarse (PM1-10) particles in urban, industrial and forest atmospheres of Northern Algeria.

The distribution of the solvent-extractable organic components in the fine (PM(1)) and coarse (PM(1-10)) fractions of airborne particulate was studied for the first time in Algeria. That was done during October 2006 concurrently in a big industrial district, a busy urban area, and a forest national park located in Algiers, Boumerdes, Blida, respectively, which are the three biggest provinces of Northern Algeria. Most of the organic matter identified in both particle size ranges consisted of n-alkanes and n-alkanoic acids, with minor contributions coming from polycyclic aromatic hydrocarbons (PAHs), nitrated polycyclic aromatic hydrocarbons (NPAHs), oxygenated PAHs, and other polar compounds (e.g., caffeine and nicotine). The potential emission sources of airborne contaminants were reconciled by combining the values of n-alkane carbon preference index (CPI) and selected diagnostic ratios of PAHs, calculated in both size ranges. The mean cumulative concentrations of PAHs reached 3.032 ng m(-3) at the Boumerdes site, urban, 80% of which (i.e. 2.246 ng m(-3)) in the PM(1) fraction, 6.462 ng m(-3) at Rouiba-Réghaia, industrial district, (5.135 ng m(-3) or 80% in PM(1)), and 0.512 ng m(-3) at Chréa, forested mountains (0.370 ng m(-3) or 72% in PM(1)). Similar patterns were shown by all organic groups, which resulted overall enriched in the fine particles at the three sites. Carcinogenic and mutagenic potencies associated to PAHs were evaluated by multiplying the concentrations of "toxic" compounds times the corresponding potency factors normalized vs. benzo(a)pyrene (BaP), and were found to be both acceptable.

Screening volatile organic compounds (VOCs) emissions from five marine phytoplankton species by head space gas chromatography/mass spectrometry (HS-GC/MS).

Five marine cosmopolitan phytoplankton species namely; Calcidiscus leptoporus, Emiliania huxleyi, Phaeodactylum tricornutum, Chaetoceros neogracilis and Dunaliella tertiolecta were screened for emissions of selected VOCs using head space gas chromatography/mass spectrometry (HS-GC/MS) in single ion mode. The VOCs investigated included isoprene and various halogenated compounds. Among the different algae groups, the two diatoms Ch. neogracilis and P. tricornutum were the strongest emitters of methyl bromide (CH3Br), and Ch. neogracilis was the strongest emitter of isoprene. Furthermore, we present evidence that several chlorinated organic compounds, normally considered as anthropogenic, can be produced from marine phytoplankton (namely chloroform, dichloromethane, trichloroethylene, tetrachloroethylene, chlorobenzene and dichlorobenzene).

Enantiomeric monoterpene emissions from natural and damaged Scots pine in a boreal coniferous forest measured using solid-phase microextraction and gas chromatography/mass spectrometry.

In order to develop a valuable method for accurate screening of biogenic emissions from undisturbed living plants or for plant-insect interactions, solid-phase microextraction (SPME) has been combined with dynamic branch enclosure cuvettes and enantioselective GC/MS. The study was conducted at Hyytiälä forest station, Finland within a boreal coniferous forest dominated by Scots pine (Pinus sylvestris). The SPME method was optimized for monoterpenes by testing three fibre coatings: polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB) and carbowax/divinylbenzene (CW/DVB) and determining the optimum exposure time. The PDMS/DVB fibre was found to be most suitable and was used to characterize emissions of P. sylvestris enclosed in dynamic branch enclosure cuvettes by exposure for 1 min followed by desorption and separation on a beta-cyclodextrin column installed in the GC/MS oven. Dynamic cuvette measurements have been compared to static headspace SPME samples of the emission of detached needles from the same tree species and a portable dynamic air sampler (PDAS)-SPME for sampling the ambient air around the same trees. The method developed has allowed an accurate characterization of the gaseous emission of P. sylvestris and the identification of 17 isoprenoids comprising chiral and achiral monoterpenes. Two chemotypes of Scots pine can be differentiated through their emission of (+)-delta-3-carene. While SPME-dynamic cuvette, portable dynamic sampler and absorbent results agreed well, significant differences in enantiomeric ratios were observed in natural emissions and those of damaged leaves. Therefore, in enantioselective studies of plant-insect and/or plant-plant interactions, the two enantiomers of a given monoterpene should be treated as two separate substances.

Isomeric analysis of BTEXs in the atmosphere using beta-cyclodextrin capillary chromatography coupled with thermal desorption and mass spectrometry.

An analytical method capable of determining trace levels of BTEX-aromatics (benzene, toluene, ethylbenzene, m-, p- and o-xylenes) in the atmosphere with as high resolution as possible has been developed. The method is based on the preconcentration of air samples using a multibed tube (Carbopack C, Carbograph 1) at ambient temperature, followed by thermal desorption, and analysis of aromatic species by a beta-cyclodextrin capillary chromatography coupled with mass spectrometry. The resolution achieved was sufficient for individual separation of BTEXs as well as m- and p-xylenes. The BTEX-ratios have been determined in an air tunnel and in on-road, suburban and rural forest atmosphere. The ethylbenzene/m-xylene ratios could provide a deep insight into anthropogenic related NMHC patterns at different locations and under different meteorological conditions and may reflect photochemical processes in the best way.

Composition of torched crude oil organic particulate emitted by refinery and its similarity to atmospheric aerosol in the surrounding area.

The absolute contents and relative distributions of organic aerosols [n-alkanes, n-alkanoic and n-alkenoic acids, n-alkan-2-ones and polycyclic aromatic hydrocarbons (PAH)] were determined in torched gases emitted during the crude oil extraction and in the free atmosphere of the Hassi-Messaoud city (Algeria). Monocarboxylic acids, both saturated and monounsaturated (from 9802 to 20,057 ng m(-3)), accounted for the major fraction of the total particulate organic matter identified both in torch exhaust and atmospheric particulate. n-Alkanes were also abundant both in the direct emission (from 460 to 632 ng m(-3)) and city atmosphere (462 ng m(-3)) and displayed a peculiar fingerprint characterised by the presence of a set of branched congeners around even carbon-numbered homologues and a strong even-to-odd predominance along the whole carbon number range (C16-C34). Whilst n-alkan-2-ones were absent in the city and poor in smokes emitted from the torches (from 31 to 42 ng m(-3)), PAH were present at low extents in all sites (from 18 to 65 ng m(-3)). The incomplete thermal combustion of torched crude oil was very likely the main source of these particle-bound organic constituents in the city and its surrounding region.

Observation of volatile and semi-volatile carbonyls in an Algerian urban environment using dinitrophenylhydrazine/silica-HPLC and pentafluorophenylhydrazine/silica-GC-MS.

Lower carbonyls and n-alkanals from C5 to C10 were measured from late autumn 2000 to summer 2001 in two urban areas in the Algerian territory: Algiers and Ouargla. They were collected on silica cartridges coated with dinitrophenylhydrazine (DNPH) and pentafluorophenylhydrazine (PFPH), which were analysed by HPLC-UV and high-resolution GC-MS. respectively. The two methods were used in parallel samplings in a suburban Algiers site and provided consistent results for semi-volatile congeners, as differences in the concentration data did not exceed 21% on average for individual carbonyl levels ranging from 0.0 to 0.5-2.6 microg m(-3). Concentrations of formaldehyde up to 27 and 5 microg m(-3) were monitored during 10 h samplings in the daytime in Algiers and Ouargla, respectively; acetaldehyde reached values of 13 and 5 microg m(-3), whilst acetone was the most abundant ketone with peak levels of 14 and 4 microg m(-3), respectively. High night-time levels of lower carbonyls were also measured at both locations. Among the semi-volatile alkanals, the highest levels were observed in suburban Algiers for hexanal and nonanal (2.2 microg m(-3)) and in downtown Algiers for valeraldehyde (2.6 microg m(-3)), whilst in Ouargla only hexanal and nonanal levels within the C5-C10 fraction exceeded 1 microg m(-3). Moreover, benzaldehyde concentrations as high as 5 microg m(-3) were measured in the centre of Algiers. Algiers data are comparable with those found in photochemically polluted urban areas of Europe and the USA. Strong correlations between formaldehyde and acetaldehyde and between formaldehyde and benzaldehyde were observed; by contrast, acetone did not show any correlation with the lower aldehydes, suggesting the existence of carbonyl sources other than vehicular traffic. Diurnal variations of almost all carbonyls suggested that motor vehicles were the most important source in the winter, whereas photochemical production appeared to predominate during the summer.