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The diffusion and the recycling of electric and electronic equipment waste (WEEE) are an important issue for industrialised countries. During treatment operations of this equipment, legacy and emerging halogenated flame retardant can be released in the environment, causing great concern for their toxicity. For this purpose, a method to simultaneously determine polybrominated biphenyl ethers, hexabromocyclododecane, 10 emerging brominated flame retardants and in parallel-polychlorinated biphenyls was optimised and applied to particulate matter samples collected within a WEEE facility. In this paper, starting from a previously published method, we drastically simplified the sample preparation, reducing the overall completion time, solvent consumption, costs and achieving adequate selectivity and sensitivity for all the target compounds. The multi–analyte method was evaluated in terms of reproducibility, linearity, recovery, limits of detection, limit of quantification, and matrix effect and compared to the previous method. Quantitative analyses were carried out by gas chromatography-mass spectrometry in negative chemical ionisation, using matrix-matched calibration curves. The reliability and robustness of the method were demonstrated through the analysis of certified and reference compounds in Standard Reference Material 2585. The most abundant compounds in particulate matter samples, collected in an electric and electronic equipment waste treatment plant, were BDE 47 (3.9 ng m−3), CB 138 (2.7 ng m−3), and 1,2-bis(2,4,6-tribromophenoxy) ethane (4.2 ng m−3). [ABSTRACT FROM AUTHOR]

Occupational exposure to airborne particles can increase the development of morbidity, also because of the chemical composition of particulate matter (PM). In workplace, where manual and mechanical disassembly of electric and electronic equipment (EEE) take place, there are evident risks of respiratory exposure to a great number of different toxic organic compounds present in the electrical and plastic materials of which the equipment is made. Airborne particles are numerous, cover a wide range of sizes and are rich in toxic organic compounds. In the present work, a sampling program was conducted and ultrafine, fine and coarse airborne particles were collected in three EEE waste treatment plants. Afterwards, the extraction and analysis of polycyclic aromatic hydrocarbons (PAHs), their nitro and oxygenated derivatives (nitroPAHs, oxyPAHs), organophosphorus compounds (OPEs), Brominated Flame Retardants (BFRs), polychlorinated biphenyls (PCBs), Polybrominated Diphenyl Ethers (PBDEs), and polyfluoralkyl substances (PFASs) was performed. The percentage ratio of the mass of organic compounds and the mass of the ultrafine fraction of PM (PM 0.1) was higher than those of the fine and coarse fractions. Even with low concentrations, the co-occurrence of numerous potentially toxic compounds capable of easily reaching other organs passing by the lung vasculature, through the lymph makes the working environment unhealthy. [Display omitted] • 101 Flame retardants and plasticizers were detected in the air of e-recycling plants. • The most detected FR chemical class is organophosphorus compounds (OPEs). • TPhP predominates among all FRs, with concentrations up to 620 ng/m3. • The size distribution of studied chemicals was higher in the ultrafine fraction of PM. • Organic compound concentrations depend on the amount of waste delivered to the plants. [ABSTRACT FROM AUTHOR]

Potential harmful effects of pesticides include risks to human health of workers involved in the wet spray application in cultivated areas. Inhalation exposure depends on several factors including pesticide concentrations in the respirable fraction of airborne particulate matter (PM4). To ensure a high level of protection, the use of tractors with cabins provides protection against dust, aerosols, and vapors. Since tractors not providing maximum protection are still in use, PM4 was sampled during spreading operations in agricultural fields inside and outside tractor cabins. Sample preparation technique based on accelerated solvent extraction and solid-phase extraction cleanup was optimized before analysis of nine pesticides in PM4. Meptyldinocap, deltamethrin, myclobutanil, fluopyram, methoxyfenozide, dimethomorph, fluopicolide, cyflufenamid, and metrafenone were simultaneously determined by high-performance liquid chromatography–electrospray ionization–tandem mass spectrometry (HPLC–ESI–MS–MS). The results demonstrated the efficacy of the tractor cabs used in the sampling sites. [ABSTRACT FROM AUTHOR]

Airborne bacteria are components of the atmospheric aerosol particles and can be responsible of allergic disease, regardless of their viability. In this paper, we report a method for the determination of total (viable and nonviable) bacterial content in airborne particles, using muramic and dipicolinic acids as biomarkers of bacteria and bacterial spores, respectively. The analytical procedure was optimized with bacteria and spores of Bacillus subtilis. After extraction and purification, the two biomarkers were analyzed by HPLC-ESI-MS/MS and their percentage was evaluated to be used as conversion factor. The present method for the determination of the total bacterial content was then applied to environmental samples, after a proper collection in an urban site. Thanks to the use of a low pressure impactor, capable of fractionating particles into the range of 0.03-10 μm, it was also possible to study the bacterial content in ultrafine, fine, and coarse particulate matter. The results from this study showed that muramic and dipicolinic acids can be determined together in one chromatographic run in reversed phase ion pair chromatography. Bacteria were more abundant than bacterial spores in the urban atmosphere, both showing a higher concentration in the coarse fraction of particles, although bacteria and bacterial spore amounts per unit mass of ultrafine particles were higher than in fine and coarse particles. [ABSTRACT FROM AUTHOR]

Oxygenated polycyclic aromatic hydrocarbons are toxicologically relevant pollutants to both humans and environment, identified in urban aerosols, coming from both direct emissions, and heterogeneous reactions in atmosphere. In this paper, 7H-benz[ de ]anthracene-7-one, benz[ a ]anthracene-7,12-dione and benzo[ a ]fluoren-11-one concentrations were studied in size-segregated atmospheric particles collected in Rome, Italy, over one year. The relevant concentration of oxy-PAHs (as sum of three compounds), found in the warmer season (2.1 ng m −3 ), was higher than both polycyclic aromatic hydrocarbon (as sum of fourteen PAHs) and their nitro-derivative (as sum of ten nitro-PAHs) concentrations in the same samples (respectively 1.31 and 0.07 ng m −3 ). The warmer season is also characterized by oxy-PAH higher concentration in the ultrafine fraction of the aerosol (0.74 ng m −3 ) when compared to the same fraction in winter and intermediate seasons (0.22 and 0.09 ng m −3 , respectively). Due to oxy-PAH major distribution in particles capable to reach the human target organs, these results suggest an important role for oxy-PAHs in the air direct-acting mutagenicity, in urban sites, in summer. [ABSTRACT FROM AUTHOR]

Concentrations of free and combined amino acids in an urban atmosphere and their distributions in size-segregated particles were investigated in the cold and warm seasons. In particular this article provides the first investigation of protein bioaerosol concentrations in ultrafine fraction (PM 0.1 ) of particulate matter. In addition the present work provides amino acid and total proteinaceous material concentrations in NIST SRM 1649b, useful as reference values. The reference material was also used to build matrix matched calibration curves. Free amino acid total content in winter and summer PM 0.1 was respectively 48.0 and 94.4 ng m −3 , representing about 0.7 and 7.4% by weight of urban particulate matter in the two seasons. Total airborne protein and peptide concentrations in the same ultrafine fractions were 93.6 and 449.9 ng m −3 respectively in winter and in summer, representing 7.5 and 35.4% w/w of PM 0.1 , and demonstrating an exceptionally high percentage in summer ultrafine fraction. The significant potential adverse health effects of ultrafine particulate matter include allergies mainly caused by protein particles and we assumed that in summer 162 ng h −1 of proteinaceous material, by means of ultrafine particles, can penetrate from the lungs into the bloodstream. [ABSTRACT FROM AUTHOR]

Abstract: Organic component of airborne particulate matter originates from both natural and anthropogenic sources whose contributions can be identified through the analysis of chemical markers. The validation of analytical methods for analysis of compounds used as chemical markers is of great importance especially if they must be determined in rather complex matrices. Currently, standard reference materials (SRM) with certified values for all those analytes are not available. In this paper, we report a method for the simultaneous determination of levoglucosan and xylitol as tracers for biomass burning emissions, and arabitol, mannitol and ergosterol as biomarkers for airborne fungi in SRM 1649a, by GC/MS. Their quantitative analysis in SRM 1649a was carried out using both internal standard calibration curves and standard addition method. A matrix effect was observed for all analytes, minor for levoglucosan and major for polyols and ergosterol. The results related to levoglucosan around 160 μg g− 1 agreed with those reported by other authors, while no comparison was possible for xylitol (120 μg g− 1), arabitol (15 μg g− 1), mannitol (18 μg g− 1), and ergosterol (0.5 μg g− 1). The analytical method used for SRM 1649a was also applied to PM10 samples collected in Rome during four seasonal sampling campaigns. The ratios between annual analyte concentrations in PM10 samples and in SRM 1649a were of the same order of magnitude although particulate matter samples analyzed were collected in two different sites and periods. [Copyright &y& Elsevier]

Abstract: Fungal spores are the dominant biological component of air. Although ubiquitous in outdoor air, they are scarcely measured due to the inadequacy of measurement methods. The use of biomarkers as tools for the determination of fungal contribution to bioaerosol has often been suggested, and ergosterol, arabitol and mannitol have been associated to fungal spores as tracers. In the present paper, the fungal component of aerosol was studied at suburban/rural and at urban sites. Ergosterol, arabitol, and mannitol contents in airborne particulate matter, even at different sizes, were determined. Literature conversion factors and calculated conversion factors correlating ergosterol, arabitol, and mannitol masses to fungi mass were applied and compared to each other. The obtained fungal spore concentrations were different depending on the marker utilized both with the conversion factors found in literature and the calculated ones. Size-segregated marker distribution suggested different sources for the three tracers indicating ergosterol as the only reliable biomarker at our latitudes. The fungal spore concentrations were higher at the suburban/rural location and respectively inversely and directly proportional to temperature and relative humidity. [Copyright &y& Elsevier]

Poly- and perfluorinated alkyl substances (PFASs) are widely used in the electrical and electronic appliance industry to the point that waste of electrical and electronic equipment (WEEE), also known as e-waste, creates significant potential for PFAS exposure (by inhalation, ingestion, or dermal exposure) for people handling and recycling e-waste. The aim of this work was the development of an untargeted analytical approach in order to detect the presence of possible unknown PFASs in particulate matter collected in three Italian e-waste facilities through liquid chromatography coupled to high-resolution tandem mass spectrometry (LC-HR-MS/MS) in negative ionization mode. By means of three acquisition experiments, nine compounds were detected as candidate PFASs, and three were definitively confirmed by comparison with their authentic standards. Among these, bistriflimide (bis (trifluoromethylsulfonyl) imide), an ionic liquid with several promising technological applications, was the most abundant compound detected in all three recycling plants. This is the first study associating the presence of fluorinated ionic liquids with e-waste, and as these chemicals are not only toxic and persistent but also highly mobile, our results indicate the need to include them in future PFAS research. Only further data on their actual environmental diffusion will determine whether they are emerging pollutants or not. [ABSTRACT FROM AUTHOR]

Abstract The biomass burning marker levoglucosan is produced via combustion of woody cellulose at temperature over 300 °C, and is hence widely used to trace fires or discriminate urban air pollution sources. In this context, it is very useful the availability of a standard reference material (SRM) with a certified value of levoglucosan, to check the quality, reliability and accuracy of the measurements. To this aim, in this work a simple and rapid method was developed for the detection and quantification of levoglucosan in an urban dust Standard Reference Material 1649a, available from the National Institute of Standards and Technology and the results were compared to those obtained in our previous investigations. 5 mg of SRM particulate material were analyzed, after an ultrasonic extraction with deionized water, using a column, with stationary phase based on hydrophilic interaction, assembled on a liquid chromatography system combined with triple tandem quadrupole mass spectrometry (HPLC-MS/MS) with electrospray ionization. Unlike existing methods, it does not require neither derivatization or extensive clean-up of the sample. For the method validation, the matrix effect, limit of detection (LOD), limit of quantification (LOQ), linearity, accuracy, recovery and precision were evaluated. The concentration determined in the SRM was in good agreement with that determined by gas chromatography-mass spectrometry in our previous study. The precision, tested on SRM, over five replicates and five aliquots were within 15%, whereas accuracy ranged between 85 and 115%. To demonstrate the method is fit for the purpose, particulate matter samples collected in an urban area of the city of Rome Italy were analyzed. The amount of levoglucosan was consistent with the urban emissions typical of the considered season. [ABSTRACT FROM AUTHOR]

A novel multi-analyte method for the simultaneous determination of 46 compounds of environmental concern, most of them belonging to the category of persistent organic pollutants, was developed using high-performance liquid chromatography and the results were compared to those obtained by gas chromatography. This study was performed in perspective of a cumulative exposure assessment of substances of health concern in environments where high levels, relatively to airborne particulate matter, can be found. The target compounds included polychlorinated biphenyls, brominated flame–retardants and derivatives of polycyclic aromatic hydrocarbons. The multi-analyte method was evaluated in air particulate matter in terms of reproducibility, linearity, recovery, limits of detection and quantification and matrix effect. The recovery was above 70% for all the analytes, whereas limits of quantification ranged between 23 and 390 pg∙m−3in liquid chromatography and less than ten times in gas chromatography–mass spectrometry. Matrix effect was generally negligible for both the techniques, except the case of the detection of oxygenated derivatives of polycyclic aromatic hydrocarbons by gas chromatography. In order to demonstrate the efficacy and to assess the method performances (accuracy and precision), both the techniques were applied to standard reference materials, and the results were compared, discussing their advantages and disadvantages. The method was finally applied to a real sample of indoor airborne particulate matter with aerodynamic diameter ≤4 μm (PM4). We demonstrated that liquid chromatography was the only technique able to analyse the 46 compounds, including thermally degradable ones, with a single chromatographic run without derivatisation steps. On the other hand, gas chromatography still presents higher sensitivity for the detection of some of the investigated compounds. This study can be considered only explorative and further improvements can be expected with new-generation LC-MS instruments (10–100 times more sensitive). [ABSTRACT FROM PUBLISHER]

In Kluyveromyces lactis yeast, OCH1 encodes for the α-1,6-mannosyltrasferase that adds the initial α-1,6-mannose to the outer-chains of N-glycoproteins. Kloch1-1 mutant cells showed altered calcium homeostasis and endoplasmic reticulum (ER) stress. Since ER plays a major role in lipid biosynthesis and lipid droplet (LD) formation, herein the impact of Och1p depletion on lipid homeostasis was investigated. Transcriptional profiles of genes involved in biosynthesis of fatty acids, their amount and composition changed in mutant cells. An increased amount of ergosterol was determined in these cells. Enhanced transcription of genes involved in both synthesis and mobilization of LDs was also found in Kloch1-1 cells, accompanied by a reduced amount of LDs. We provide evidence that ER alterations, determined by protein misfolding as a result of reduced N-glycosylation, induced altered lipid homeostasis in Kloch1-1 cells. Chemical chaperone 4-phenyl butyrate (4-PBA) slightly alleviated the LD phenotype in cells depleted of Och1p. Remarkably, complete suppression of ER stress, via increased expression of plasma membrane calcium channel subunit Mid1, fully restored lipid homeostasis in mutant cells. To further reinforce this finding, low numbers of LDs were observed in wild type cells when ER stress was triggered by DTT treatment. [ABSTRACT FROM AUTHOR]

Abstract: Size-segregated atmospheric particles were collected in Rome, Italy, using a low-pressure impactor. Twelve sampling campaigns were conducted under different meteorological conditions over a whole year covering 155 not consecutive days. The samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) and their nitro- and methyl- derivatives known for their toxicity. An assessment of the carcinogenic potency of the particles known to penetrate into lungs, liver, heart and nervous system was performed. The distribution of the classes of compounds was unimodal and centrated at 0.4 μm size fraction for PAHs and bimodal and centrated at 0.1 and 0.4 μm for methyl- and nitro- derivatives. The 18% of toxic organic compounds we analyzed was distributed into the ultrafine fraction (PM0.1) and 76% in the fine fraction; but substituted PAH distribution in the ultrafine particles shifted toward higher values during warm periods. In July, the 50% of the total nitro-PAHs was found in PM0.1 and an average of 42% of the total methyl-PAHs was found in the same fraction in summer and intermediate seasons. An evaluation of the potential toxicity of the measured compounds was tentatively assessed based on Potency Equivalency Factors (PEF). [Copyright &y& Elsevier]

Abstract: The present paper highlights the utility of petroleum chemical fingerprinting in investigating known or suspected tank farm releases. A detailed characterization of groundwater was carried out in three tank farms located in north, central and south Italy. Eighteen parent polycyclic aromatic hydrocarbons (naphthalene through coronene), n-alkanes (n-C10 through n-C36), isoprenoids pristane and phytane, vanadium, nickel and lead were determined. Distribution profiles and diagnostic ratios of specific fuel constituents were studied in order to identify contamination sources. Data analysis shows that in the study sites multiple pollutant sources affecting the tank farms and the surrounding industrial areas are present. Both high concentrations of contaminants coming from fuel releases and noticeable concentrations of biogenic compounds were found. A detailed data analysis suggests the origin and the level of pollution of the three sites. The results demonstrate that threshold concentration approach is not always sufficient and it is necessary to carry out studies of contaminant distribution and their diagnostic ratios in order to perform a successful forensic investigation. [Copyright &y& Elsevier]

Abstract: Atmospheric nitrophenols (NPs) were determined both in the gas and particle phases by combining the annular denuder sampling technique with GC–MS analysis. The phase distribution of six mono-NPs identified in air sampled in downtown Rome was assessed. 4-NP, 3-methyl-4-NP and 2,6-dimethyl-4-NP were found for more than 75% in the particle phase, whilst 2-NP, 4-methyl-2-NP and 5-methyl-2-NP predominated in the gas phase. Concentration levels lower than 20ngm−3 were observed for all NPs, among which 4-NP (17.8±5.6ngm−3) and 2-NP (10.4±4.2ngm−3) were the most abundant congeners in the two phases, respectively. [Copyright &y& Elsevier]

• Free/bound sterol ratio was assessed in feed by a smart LC/APCI-MS/MS method. • In addition to phytosterols, non-negligible amount of cholesterol is found in feed. • The seed sterol profile can be predictive of the composition of derived foods. This paper provides a method for the quantification of sterols in different types of calf feedstuffs based on soy, sunflower, hay, calf feed and a mixture of all of them. The free fraction and the total sterolic fraction, after saponification and acidic hydrolysis of the samples, are extracted by solvent and the sterols are identified/quantified by reversed phase HPLC coupled to tandem mass spectrometry by atmospheric pressure chemical ionization. After the recovery evaluation, the method is validated in terms of linearity (coefficient of determination R2), repeatability (coefficient of variation RSD), limit of detection and quantification. In most of the cases, the most representative phytosterol is β-sitosterol, followed by campesterol or stigmasterol and by other minor sterols such as fucosterol, and Δ-5-avenasterol. In addition, also cholesterol and ergosterol, if present, are evaluated in all the samples. As far as we know, very little information is available on the investigated feeds, which are commonly used on farms. The results of this survey were compared to other studies, if present in literature, showing good agreement. The proposed method resulted to be simple, fast and suitable for application to other sterols, feedstuffs and derived foods. The knowledge of the sterolic content and composition is getting more and more important, both in terms of comprehension of the vegetal biochemistry and as basis for sterolomic studies. [ABSTRACT FROM AUTHOR]

Background: Caffeine, theophylline, and theobromine are methylxanthines commonly found in coffee, tea, cola, and cocoa. Other sources may be soft drinks or energy drinks. All of them are stimulants of the nervous system and can be used for the treatment of some diseases. The three xanthines produce addiction with typical abstinence symptoms. Among young people, the consumption of energy beverages is increasing, and the growing market causes concern about the caffeine intake. To evaluate intake of methylxanthines, their accurate determination can be helpful. Methods: A simple method for their determination without sample pretreatment was applied to beverages, including coffee, tea, cola, and energy drinks. The separation was achieved by LC with UV detection. The method was validated in terms of linearity, LOD and LOQ, accuracy, and reproducibility. Results: The drinks were directly injected after a filtration, and no matrix effect was demonstrated. The procedure proved to be simple, time saving, accurate, and reproducible and may be recommended for reliable assays in routine work. The investigated samples showed a range of caffeine concentration from 100 to 3050 mg/L. Possible intake of methylxanthines from miscellaneous types of drinks was assessed considering the European Food Safety Authority Opinion on the safety of caffeine consumption. Our results were in good agreement with other authors. Conclusions: A fast and accurate method for the simultaneous determination of three xanthynes in beverages was validated. The selected strategy has proved to be fit-for-purpose by applying it to different nervous system stimulant drinks. Highlights: A simple and time saving procedure was proposed for the separation, detection, and quantitation of three methylxantynes in nervous system stimulant drinks. No sample preparation was needed, and speculation could be made about the possible intake of them from beverages. [ABSTRACT FROM AUTHOR]

• The migration of OPEs and PFASs from FMCs was assessed. • Baking paper and aluminium foil were chosen among the most widely used FMCs. • Two simulants were used to mime the migration into different kind of food. • Comparison between different samples was made by a quantitative LC-MS/MS analysis. • Through the method developed in this work, a non-negligible concentration of OPE was detected in FMC. The present work focused on the development of an analytical method suitable to study the presence and the release of organophosphate esters (OPEs) and perfluoroalkylated substances (PFASs) from food contact materials (FCMs), from baking paper and aluminium foil. Although these classes of compounds are attracting increasing attention due to their toxicity the knowledge is still insufficient. The extent of their migration from FCMs to food was estimated using different liquid simulants. Ethanol 95 % was used to simulate the contact with fatty food, whilst acetic acid 3 % to mime contact with acidic aqueous-based food and the contact mode involved the use of the ultrasound-assisted technique. Preliminary results showed the higher migration for baking paper samples in contact with aqueous simulant with contaminations in the ranges 78.30–413.21 ng/dm2 and 1.43–13.87 ng/dm2 for OPEs and PFASs respectively. These findings highlighting the need to monitor particularly OPEs in FCMs. [ABSTRACT FROM AUTHOR]

This work aimed to study the fate and effect of β-hexachlorocyclohexane (β-HCH) during several steps of PHA production and purification, by using an artificially contaminated cheese whey (CW) as the feedstock. Most of β-HCH (around 90%) was adsorbed on CW solids and it was removed after the acidogenic fermentation step, when residual CW solids are separated along with anaerobic biomass from the liquid-phase. Purification steps also contributed strongly to the removal of residual β-HCH; overall, the PHA production process removed about 99.9% of initial β-HCH content. Moreover, it has been shown that β-HCH has neither detrimental effect on acidogenic fermentation nor on PHA accumulation, that were performed by using unacclimated mixed microbial cultures. [ABSTRACT FROM AUTHOR]

An effective analytical method for the screening of mycotoxins, in indoor/outdoor airborne particulate matter, was developed and method performance data are presented. Mycotoxins are natural compounds produced, in particular conditions, as secondary metabolites by filamentous fungi and moulds, and, after their production, they can be transported far from their source. To simulate real samples, an urban dust (reference material 1649a) free from mycotoxins was used as matrix and spiked by the most common mycotoxins, chosen on the basis of studies carried out previously in other real matrices: deoxynivalenol, aflatoxin B1, ochratoxin A, T-2 toxin, zearalenone and sterigmatocystin. The analytical method was optimised and structured in four successive steps: (1) accelerated solvent extraction of the (spiked) analytes from matrix, (2) solid-phase purification (SPE) of the previous extract, (3) pre-concentration of the eluates from SPE and (4) analysis of the concentrated eluates by high performance liquid chromatography tandem mass spectrometry in multiple reaction monitoring mode. After a proper sampling campaign, the method was applied to real indoor and outdoor particulate matter samples, where the clean-up step showed to be very effective and fundamental to avoid misleading analytical results. [ABSTRACT FROM AUTHOR]

• The content of quercetin and its derivatives were determined by HPLC-MS/MS in several Italian wines. • The proposed method resulted smart, fast, economic and fit for the purpose. • Sangiovese and Nero d'Avola showed the highest level of the investigated compounds. Quercetin and its structural derivatives are natural compounds belonging to the flavonoid class, widely distributed in plants. Beneficial physiological activities have been attributed to them, but some require deeper investigation. In this paper the content of quercetin and five analogues (quercetin-3-glucoside, quercetin-3-rutinoside, quercetin-3-ramnoside, quercetin-3-arabinoglucoside, 4′-O-methylquercetin) were determined by HPLC-ESI-MS/MS in wines made of different varieties of red and white vines. The aim was a comparative study focusing on quercetin and on the contribution of related compounds in twenty wines coming from different part of Italy. Wines produced from Sangiovese and Nero d'Avola, monovarietal grapes, were richest in quercetin compounds and our results were compared to our previous study and to other investigations. The proposed method resulted simple, fast, economical, and suitable for the analysis of quercetin analogues without the need of hydrolysis and falls in the optic of a 360° characterization of active wine compounds, with nutraceutical properties. [ABSTRACT FROM AUTHOR]

Abstract: A liquid chromatography–tandem mass spectrometry analytical procedure has been developed for the detection and quantitative determination of underivatized amino acids at low concentrations in a Standard Reference Material—urban dust. In order to minimize interferences of other compounds, an accelerated solvent extraction followed by a solid phase extraction on two different cartridges was applied prior to LC–MS–MS. Fourteen amino acids were separated by high resolution liquid chromatography, detected and quantified by multiple reaction monitoring on a triple quadrupole. The proposed methodology has been applied for the first time on Standard Reference Material 1649a (urban dust) from the National Institute of Standards and Technology, that does not report certification values for these compounds. This methodology avoids the derivatization step and allows the amino acid quantification in a complex matrix, such as that of atmospheric particulate matter, and represent a good method suitable to analyze this class of compounds in atmospheric aerosol. The selected strategy demonstrated to be fit-for-purpose, by applying it to a real atmospheric sample with the aim to verify the efficacy of the study and to provide information about the organic matter content. [Copyright &y& Elsevier]

Abstract: Airborne microorganisms, as bacteria and fungi, are ubiquitous components of the atmospheric aerosol particles. In this paper, we report a method for the simultaneous extraction, purification, separation, identification and quantification of ergosterol, mannitol and arabitol as biomarkers of fungal spores in bioaerosol particles. After sampling by a low volume sampler, filters were spiked with mannitol-13C and dehydrocholesterol as internal standards. Samples were then extracted by accelerated solvent extraction using pure ethanol. The extract was then passed through an amino cartridge and divided in two parts: the apolar fraction, released from the cartridge, was subjected to liquid liquid extraction (by n-hexane), while polar compounds, retained by the cartridge, were eluted by a mixture of methanol–water. The two fractions were joined and analyzed by HPLC equipped with two different columns in series, and coupled to a triple-quadrupole mass spectrometer with Atmospheric Pressure Chemical Ionization source. In addition, the same fractions were analyzed, after derivatization, by GC–MS. The results obtained by the two techniques were finally compared, showing good agreement between them. Last, the contents of the three biomarkers have been estimated in three atmospheric samples collected in a suburban/rural site and, using literature conversion factors, correlated to fungal biomass. [Copyright &y& Elsevier]

Domestic biomass heating and wildfires strongly affect particulate matter (PM) concentration in the atmosphere. The individuation of alternative chemical tracers may provide a valuable tool to apportion different possible contributions to biomass burning. In this study, we used a new experimental procedure, based on high spatial resolution analyses of PM 10 , to assess the spatial distribution of levoglucosan (LVG) and evaluate the possible use of alternative biomass burning tracers in the Terni basin, a wide urban and industrial hot-spot of Central Italy, which includes several spatially disaggregated sources. Spatially-resolved chemical characterization of PM 10 was obtained through the use of innovative samplers working in parallel in a dense monitoring network (20 sampling sites, about 1 km between each other), during wintertime. PM 10 samples were analyzed for LVG, water-soluble organic carbon (WSOC) and water-soluble and insoluble fraction of 33 elements. Principal component analysis (PCA) on the obtained spatially-resolved data allowed us to identify biomass burning tracers across the polluted study area. Analyses of size-segregated PM samples showed the presence of LVG, and water-soluble Cd, Cs, K, Rb and Tl in particles with size fraction smaller than 1 μm, confirming them as tracers of combustion processes (mainly related to biomass burning). Pearson correlation coefficients demonstrated that concentrations of WSOC and water-soluble Cd, Cs, K, Rb and Tl were well correlated with the spatial variability of LVG concentration. The combined use of spatially and dimensionally resolved data was found to be particularly advantageous for the identification of alternative source tracers, which were used to reliably trace the main local biomass burning sources in the study area. Unlabelled Image • Innovative PM 10 samplers worked for two winter months at twenty monitoring sites in Terni. • PM 10 samples were analyzed for LVG, WSOC and water-soluble and insoluble fractions of 33 elements. • LVG was confirmed to be a highly selective tracer for biomass burning. • Water-soluble Cd, Cs, K, Rb and Tl were identified as alternative biomass burning tracers. • Size distribution analyses confirmed the target analytes as tracers of combustion processes. [ABSTRACT FROM AUTHOR]

The microbial synthesis of polyhydroxyalkanoates (PHA) from organic wastes is a valuable process to valorize available renewable resources, such as food wastes and biological sludge. Bioplastics find many applications in various sectors, from medical field to food industry. However, persistent organic pollutants could be transferred from wastes to the final product. The present paper demonstrates that the use of municipal wastes in PHA production is safe for the environment and human health and provides a polychlorinated biphenyl (PCB) profile in both commercial and waste-based PHA samples. PCB analysis in several PHA samples showed very low concentrations of the target analytes. Commercial PHA samples showed a similar PCB level with respect to PHA samples from municipal waste/sludge and higher than PHA samples from fruit waste. For all analyzed PCBs, detected concentrations were consistently lower than the ones reported in regulatory framework or guidelines. [ABSTRACT FROM AUTHOR]

This work is part of an extensive research project aimed at the determination and characterization of bioaerosol with a multidisciplinary approach. In this context, one of the main objectives of the project has been the development of a comprehensive analytical method for the determination of different chemical biomarkers of the bioaerosol, by liquid chromatography coupled with tandem mass spectrometry. The following biomarkers have been considered, and correlated to specific components of bioaerosol as unambiguous indicators: • ergosterol → fungal components • chlorophylls, phytosterols (stigmasterol and b-sitosterol), α-tocoferol → vegetable cells and algae • cholesterol → animal cells, vegetable cells and algae. • dipicolinic acid → bacterial spores • muramic and meso-2,6-diaminopimelic acid → bacterial cells To verify the method, to find diagnostic ratios and to calculate the appropriate conversion factors, fungal spores, bacterial cells and spores, and algae of known species, commonly airborne, were analysed. The material was subjected to freezing and de-freezing cycles, followed by extraction, hydrolysis and purification of the biomarkers. The chromatographic separation of the bacterial biomarkers was achieved by using a polymeric column, based on Hydrophilic Liquid Interaction with the electrospray ionization mass spectrometric detection, whereas sterols and chlorophylls were separated by a reversed phase column, coupled to atmospheric pressure chemical ionization – tandem mass spectrometer. The optimized method was applied to environmental particulate matter sampled in an outdoor site. Bacterial and fungal content was compared to the results obtained from the classical direct viable counting method in the sampled particulate matter. • A methodology for the investigation of bioaerosol components, based on a parallel determination of biomarkers, was proposed. • meso-2,6-diaminopimelic acid (mDAPA) acid, as marker for bacterial cell, correlates well to muramic acid • Sterols are typical of vegetable cells, algae and fungi • Comparison between the proposed method and the classical microbiological one, showed the inaccuracy of the biological method. [ABSTRACT FROM AUTHOR]