Indoor air quality at life and work environments in Rome, Italy.

The air quality of three different microenvironments (school, dwelling, and coffee bar) located in the city of Rome, Italy, was assessed. Indoor and outdoor concentrations of polycyclic aromatic hydrocarbons (PAHs) associated with PM2.5 particles were determined during an intensive 3-week sampling campaign conducted in March 2013. In interiors, total particulate PAHs ranged from 1.53 to 4.96 ng/m(3) while outdoor air contained from 2.75 to 3.48 ng/m(3). In addition, gaseous toxicants, i.e., NO2, NOx , SO2, O3, and BTEX (benzene, toluene, ethyl-benzene, and xylene isomers), were determined both in internal and external air. To solve the origin of indoor and outdoor PAHs, several source apportionment methods were applied. Multivariate analysis revealed that emissions from motor vehicles, biomass burning for heating purposes, and soil resuspension were the major sources of PAHs in the city. No linear correlation was established between indoor and outdoor values for PM2.5 and BTEX; the respective indoor/outdoor concentration ratios exceed unity except for PM2.5 in the no smoking home and benzene in all school floors. This suggests that important internal sources such as tobacco smoking, cleaning products, and resuspension dust contributed to indoor pollution. Using the monitoring stations of ARPA Lazio regional network as reference, the percentage within PAH group of benzo[a]pyrene, which is the WHO marker for the carcinogenic risk estimates, was ca. 50% higher in all locations investigated.

Influence of Environmental Factors and Air Composition on the Emission of [alpha]-Pinene from Quercus ilex Leaves.

We studied the emission of [alpha]-pinene from Quercus ilex leaves. Only the abaxial side of the hypostomatous Q. ilex leaf emits [alpha]-pinene. Light induced photosynthesis and [alpha]-pinene emission. However, the response of photosynthesis to dark-to-light transitions was faster than that of [alpha]-pinene, suggesting that ATP controls the emission. The emission was higher at 30 than at 20[deg]C, whereas photosynthesis did not change. Therefore, the relationship between photosynthesis and [alpha]-pinene emission does not always hold. When CO2 was removed from the air, transpiration was stimulated but photosynthesis and [alpha]-pinene emission were inhibited. [alpha]-Pinene inhibition was more rapid under low O2. When CO2 in the air was increased, photosynthesis was stimulated and transpiration was reduced, but [alpha]-pinene emission was unaffected. Therefore, the emission depends on the availability of photosynthetic carbon, is not saturated at ambient CO2, and is not dependent on stomatal opening. The pattern of [alpha]-pinene emission from Q. ilex is different from that of plants having specialized structures for storage and emission of terpenes. We suggest that [alpha]-pinene emitted by Q. ilex leaves is synthesized in the chloroplasts and shares the same biochemical pathway with isoprene emitted by isoprene-emitting oak species.

Evidence of the Photosynthetic Origin of Monoterpenes Emitted by Quercus ilex L. Leaves by 13C Labeling.

The carbon of the four main monoterpenes emitted by Quercus ilex L. leaves was completely labeled with 13C after a 20-min feeding with 99% 13CO2. This labeling time course is comparable with the labeling time course of isoprene, the terpenoid emitted by other Quercus species and synthesized in leaf chloroplasts. It is also comparable with that of phosphoglyceric acid. Our experiment therefore provides evidence that monoterpenes emitted by Q. ilex are formed from photosynthesis intermediates and may share the same synthetic pathway with isoprene. By analyzing the rate and the distribution of labeling in the different fragments, we looked for evidence of differential carbon labeling in the [alpha]-pinene emitted. However, the labeling pattern was quite uniform in the different fragments, suggesting that the carbon skeleton of the emitted monoterpenes comes from a unique carbon source.

Simple laboratory-made system for the determination of C2-C7 hydrocarbons relevant to photochemical smog pollution.

A simple gas chromatographic system suitable for determining volatile organic compounds from C2 to C7 in air is described. It consists of a capillary cold trap filled with graphitic carbon, a thermodesorbing device, a capillary gas chromatograph equipped with an alumina column and a flame ionization detector. Dry, as well as humid, air samples can be analysed with our system. Up to 2-1 samples of air can be enriched on our trapping device by using Nafion membranes for removing water. Direct analysis of air samples is possible by enriching 250 ml on the carbon trap. The recovery, sensitivity and linearity of our system have been checked with standard mixtures and real samples. The performances have been compared with those afforded by a commercially available instrument exploiting a different enrichment procedure. The results obtained show that our analyser can be successfully applied to determinations of C2 to C7 hydrocarbons present in air samples at levels of 0.01 ppb (v/v).

Distribution of n-alkanes, polynuclear aromatic hydrocarbons and nitrated polynuclear aromatic hydrocarbons between the fine and coarse fractions of inhalable atmospheric particulates.

The distribution ratios of n-alkanes, polynuclear aromatic hydrocarbons (PAHs) and nitrated PAH components between fine and coarse fractions of soot has been investigated in downtown Rome through three field campaigns carried out at different times of the year. The preferential accumulation of almost all species investigated onto fine particles has been observed in all field experiments performed. Moreover, nitrated PAHs had varied distributions, according to the origin of their occurrence in the atmosphere; in fact, congeners of photochemical origin accumulated more in fine particles than those released by primary sources.

Nitroarenes of photochemical origin: a possible source of risk to human health.

Nitrated polynuclear aromatics (NPAH) have been recognized as mutagenic even without enzymatic activation. NPAH have been found in the urban air of the U.S.A. and Western Europe. Their detection in the atmosphere has been related mainly to in situ photochemical production. In this study, the ubiquity of NPAH in the air is presented despite their rare and scarce occurrence in emissions released by mobile and stationary sources. NPAH seem to effectively contribute to both the direct and indirect mutagenicity of air soot (in European countries more than in the U.S.A.). Moreover, they can be taken as a suitable index of the occurrence of reactive nitrogen compounds in the air.

Nitro-PAH in ambient particulate matter in the atmosphere of Athens.

Nitrated polynuclear aromatic hydrocarbons (NPAH) with a molecular mass of 247 Daltons were found in soot collected in downtown Athens during a campaign performed in 1996. In particular, 2-nitrofluoranthene (2-NFa) and 2-nitropyrene (2-NPy), which are mainly related to photo-induced chemical processes occurring in the atmosphere, were more abundant than 1-nitropyrene (1-NPy) usually associated to motor vehicle exhaust.

Chemical characteristics of organic aerosol in Bab-Ezzouar (Algiers). Contribution of bituminous product manufacture.

The organic compositions of atmospheric particulate matter from Bab-Ezzouar (Algiers) have been investigated to assess the air pollution levels suspected to be caused by asphalt product and yeast manufactures. After a medium-volume air sampling, soxhlet extraction, alumina elution and HPLC separation, the extracts were analysed by high-resolution gas chromatography (HRGC) and gas chromatography coupled to mass spectrometry (GC-MS). The composition of n-alkane and polycyclic aromatic hydrocarbons (PAH) fractions reflected the petrogenic origin from the emission of asphalt materials production in addition to vascular plant wax emissions. In contrast, microbial activities seemed to play the main role for the presence of n-alkanoic acids at Bab-Ezzouar. The sole nitrated polycyclic aromatic hydrocarbons (NPAH) observed, i.e., 2-nitrofluoranthene (2NFA), was very likely to arise from gas-phase photochemical reaction of parent PAH in the atmosphere. The total aerial levels ranged from 75 to 206 ng m(-3) for n-alkanes, from 153 to 345 ng m(-3) for n-alkanoic acids and from 44 to 100 ng m(-3) for PAH and NPAH. Although the samples were collected during the hot season, the levels of these pollutants seemed to be important and of environmental concern, especially for PAH species.

Organic content of particulate matter in the atmosphere of Ouargla City, Algeria.

The particle-bound organic compounds comprising n-alkanes, n-alkanoic monocarboxylic acids, polynuclear aromatic hydrocarbons (PAH) and nitrated polynuclear aromatic hydrocarbons (NPAH) were investigated in ambient air of the Ouargla city area (Algeria) during a short campaign performed in November 1999. The distribution profile of n-alkanes was consistent with the petrogenic origin of aerosols, suggesting that they were related to torching processes of crude oil refuses in the petroleum extraction field located not far from Ouargla. Instead, the presence of n-alkanoic acids of low molecular weight was indicative of microbial activity experienced by the site. PAH levels were low when compared to other polluted areas. The presence of 2-nitrofluoranthene and 2-nitropyrene, which can result from in-situ nitration of fluoranthene and pyrene, was concurrent with the substantial depletion of the most reactive among PAH, suggesting that photochemical processes influence the composition of the Saharian atmosphere.

Particle size distribution of n-alkanes and polycyclic aromatic hydrocarbons (PAHS) in urban and industrial aerosol of Algiers, Algeria.

The distribution of ambient air n-alkanes and polycyclic aromatic hydrocarbons (PAHs) associated to particles with aerodynamic diameters lesser than 10 µm (PM(10)) into six fractions (five stages and a backup filter) was studied for the first time in Algeria. Investigation took place during September of 2007 at an urban and industrial site of Algiers. Size-resolved samples (<0.49, 0.49-0.95, 0.95-1.5, 1.5-3.0, 3.0-7.2, and 7.2-10 µm) were concurrently collected at the two sampling sites using five-stage high-volume cascade impactors. Most of n-alkanes (~72 %) and PAHs (~90 %) were associated with fine particles ≤ 1.5 µm in both urban and industrial atmosphere. In both cases, the n-alkane contents exhibited bimodal or weakly bimodal distribution peaking at the 0.95-1.5-µm size range within the fine mode and at 7.3-10 µm in the coarse mode. Low molecular weight PAHs displayed bimodal patterns peaking at 0.49-0.95 and 7.3-10 µm, while high molecular weight PAHs exhibited mono-modal distribution with maximum in the <0.49-µm fraction. While the mass mean diameter of total n-alkanes in the urban and industrial sites was 0.70 and 0.84 µm, respectively, it did not exceed 0.49 µm for PAHs. Carbon preference index (~1.1), wax% (10.1-12.8), and the diagnostic ratios for PAHs all revealed that vehicular emission was the major source of these organic compounds in PM(10) during the study periods and that the contribution of epicuticular waxes emitted by terrestrial plants was minor. According to benzo[a]pyrene-equivalent carcinogenic power rates, ca. 90 % of overall PAH toxicity across PM(10) was found in particles ≤ 0.95 µm in diameter which could induce adverse health effects to the population living in these areas.

Evaluation of principal cannabinoids in airborne particulates.

The determination of delta(9)-tetrahydrocannabinol (Delta9-THC), cannabidiol (CND) and cannabinol (CNB), primary active components in cannabis preparation, was carried out on airborne particulates by applying a specific procedure consisting of soot extraction by ultrasonic bath, purification by solvent partitioning, derivatization with N-(t-butyldimethylsilyl)-N-methyl-trifluoroacetamide, and separation/detection through gas chromatography coupled with tandem mass spectrometry. The optimized procedure was found suitable for measuring the three psychotropic substances at concentrations ranging from ca. 0.001 to ca. 5.0 ng cm(-3) of air, with recoveries always higher than 82%, accuracy >7.3% and precision >90%. Application of the procedure performed on field in Rome and Bari, Italy, demonstrated that all three compounds contaminate the air in Italian cities whereas in Algiers, Algeria, only cannabinol, the most stable in the atmosphere, exceeded the limit of quantification of the method. The relative percentages of the three cannabinoids in general reproduced those typical of the Cannabis sativa plant and were very different from those found in human blood, urine and sweat.

Organic aerosols in urban and waste landfill of Algiers metropolitan area: occurrence and sources.

In both downtown Algiers and the waste landfill of Oued Smar, the concentrations of particulate organic compounds comprising n-alkanes, n-alkanoic acids, n-alkan-2-ones, polycyclic aromatic hydrocarbons (PAHs), oxygenated (OPAHs), and nitrated polycyclic aromatic hydrocarbons (NPAHs) in ambient air were measured from May 1998 to February 1999. All the components except OPAHs had a tendency to strongly increase in colder weather. Motor vehicles were found to be the main source of airborne particles in downtown Algiers, while the combustion and pyrolysis processes and bacterial activity seemed to concur to the air pollution at the Oued Smar waste landfill. The biogenic emission, which was restricted to the lighter fraction of the n-alkanes and n-alkanoic acids, appeared to contribute at a lesser extent. The in-situ generation of some OPAHs and NPAHs seemed to contribute to air pollution, especially during the summertime. As expected, the ambient concentrations of NPAHs and OPAHs were lower than those of their parent PAHs. The seasonal variations in ambient NPAH and OPAH concentrations are due partly to fluctuations of precursors including NOx, 03, and OH radicals. In general, the wintertime concentrations of the organic pollutants in Algiers were similar to those measured in Europe and especially over the Mediterranean Basin. Further investigations have been planned in order to obtain a thorough knowledge of the air pollution as well as the organic content of materials burning atthe Oued Smarwaste landfill. In particular, our concern will be addressed to sources of toxic components, to formulate strategies suitable for reducing health risk for the populations living in the region of Algiers.

Ozone measurement with silica cartidges and HRGC-MS analysis.

Ozone in ambient air is collected onto silica gel cartridges impregnated with pentafluorophenylhydrazine (PFPH) and 1,2-di(4-pyridyl)ethylene (DPE), so that the pyridine-4 aldehyde formed by DPE oxidation is converted into the corresponding PFPH derivative (PPH). The latter product is determined by HRGC/MS. Since the ozonolysis reaction proceeds stoichiometrically on the cartridge, there is no need for calibration in the gas phase with a standardized ozone source. When compared with UV photometry analyzers, this active chromatographic method (ACM) demonstrates a very good accuracy (ACM/UV photometer = 0.97) and precision (12.0-14.0%) under both laboratory and field sampling conditions at ozone concentrations of 20-200 microg m(-3) and exposure times of 1-3 h. The sampling performance was found to be insensitive to relative humidity (r.h.) variations in the 25-90% range and any interference effects could not be observed from various agents, except light, which can be eliminated by using an aluminium shelter. The detection limit for ozone achievable with the ACM in air samples collected at 0.5 L min(-1) for 1 h was found better than 0.5 microg m(-3).

Polar volatile organic compounds (VOC) of natural origin as precursors of ozone.

HRGC-MS determinations carried out on samples collected in urban, suburban, rural, forest and remote areas suggest that several other classes of non-methane VOC than isoprene and monoterpene hydrocarbons can be emitted by plants. Because of their high photochemical reactivity, they can contribute to tropospheric ozone production which, in turn, can cause climate changes through radiative forcing.

Different sources of reduced carbon contribute to form three classes of terpenoid emitted by Quercus ilex L. leaves.

Quercus ilex L. leaves emit terpenes but do not have specialized structures for terpene storage. We exploited this unique feature to investigate terpene biosynthesis in intact leaves of Q. ilex. Light induction allowed us to distinguish three classes of terpenes: (i) a rapidly induced class including alpha-pinene; (ii) a more slowly induced class, including cis-beta-ocimene; and (iii) the most slowly induced class, including 3-methyl-3-buten-1-ol. Using 13C, we found that alpha-pinene and cis-beta-ocimene were labeled quickly and almost completely while there was a delay before label appeared in linalool and 3-methyl-3-buten-1-ol. The acetyl group of 3-methyl-3-buten-1-yl acetate was labeled quickly but label was limited to 20% of the moiety. It is suggested that the ocimene class of monoterpenes is made from one or more terpenes of the alpha-pinene class and that both classes are made entirely from reduced carbon pools inside the chloroplasts. Linalool and 3-methyl-3-buten-1-ol are made from a different pool of reduced carbon, possibly in nonphotosynthetic plastids. The acetyl group of the 3-methyl-3-buten-1-yl acetate is derived mostly from carbon that does not participate in photosynthetic reactions. Low humidity and prolonged exposure to light favored ocimenes emission and induced linalool emission. This may indicate conversion between terpene classes.

Characterization of oxidative and reductive metabolism in vitro of nitrofluoranthenes by rat liver enzymes.

Nitrofluoranthenes (NFs) are mutagenic and carcinogenic environmental pollutants found in incomplete combustion products and urban air particulate. We have studied both oxidative and reductive metabolism in vitro of different NF isomers mediated by subcellular rat liver fractions. Under aerobic conditions only ring hydroxylation of NFs by rat liver microsomes occurred and the isomeric position of the nitro group affected both the amount and the type of phenolic metabolites formed. Liver microsomes from 3-methylcholanthrene-induced rats were most effective in giving ring hydroxylated 7- and 8-nitrofluoranthene, whereas liver microsomes from phenobarbital-pretreated rats were the most active in metabolizing 1- and 3-nitrofluoranthene. Under anaerobic conditions, only reduction of NFs mediated by both cytosolic and microsomal rat liver enzymes occurred. Cofactor requirements and inhibition experiments indicated that the reductase activity in rat liver cytosolic fractions could be ascribed to DT-diaphorase, aldehyde oxidase and/or other unknown enzymes. The microsomal reductase activity was inhibited by oxygen, carbon monoxide, 2-diethylaminoethyl-2,2-diphenylvalerate hydrochloride and n-octylamine, and slightly by cytochrome c; flavin mononucleotide greatly enhanced this activity. 3-Nitrofluoranthene microsomal nitroreductase activity was increased by phenobarbital rat pretreatment and this increment correlated well with the content of cytochrome P450. These results indicate a participation of cytochrome P450 in the reductive metabolism of NFs by rat liver microsomes.