Authenticating teas using multielement signatures, strontium isotope ratios, and volatile compound profiling.

High value food products are subject to adulterations and frauds. This study aimed to combine, in our knowledge for the first time, inorganic chemical tracers (multi-elements and Sr isotopy) with volatile organic compound (VOCs) to discriminate the geographic origin, the varieties and transformation processes to authenticate 26 tea samples. By measuring Sr isotope ratio using the multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), 6 out of 11 regions were successfully discriminated. The combination with the ICP-MS inorganic pattern allowed to discriminate 4 more regions with a significance level of 0.05. VOCs fingerprints, obtained with selected ion flow tube mass spectrometer (SIFT-MS), were not correlated with origin but with the cultivar and transformation processes. Green, oolong, and dark teas were clearly differentiated, with hexanal and hexanol contributing to the discrimination of oxidation levels. With this multi-instrumental approach, it is possible to certify the geographical origin and the tea conformity.

Volatile fingerprint of food products with untargeted SIFT-MS data coupled with mixOmics methods for profile discrimination: Application case on cheese.

Volatile organic compounds (VOCs) emitted by food products are decisive for the perception of aroma and taste. The analysis of gaseous matrices is traditionally done by detection and quantification of few dozens of characteristic markers. Emerging direct injection mass spectrometry technologies offer rapid analysis based on a soft ionisation of VOCs without previous separation. The recent increase of selectivity offered by the use of several precursor ions coupled with untargeted analysis increases the potential power of these instruments. However, the analysis of complex gaseous matrix results in a large number of ion conflicts, making the quantification of markers difficult, and in a large volume of data. In this work, we present the exploitation of untargeted SIFT-MS volatile fingerprints of ewe PDO cheeses in a real farm model, using mixOmics methods allowing us to illustrate the typicality, the manufacturing processes reproducibility and the impact of the animals' diet on the final product.

Suspension of pheromone microcapsules on vine leaves acting as passive dispensers against pests.

Pheromones are increasingly used as alternatives to pesticides to protect vineyards against L. botrana, a key grape pest. To diffuse (7E,9Z)-7,9-dodecadien-1-ylacetate, the L. botrana pheromone, passive, or aerosol dispensers are commonly applied. This paper deals with another method based on spraying an aqueous formulation, Lobesia Pro Spray, containing the pheromone encapsulated in a resin. The objectives were to assess the ability of vine leaves to act as pheromone dispensers and to check that encapsulation protects the plant from pheromone penetration. Laboratory testing based on an emission cell combined with airborne pheromone measurements by active sampling on sorbent tubes followed by ATD-GC-MS analysis was developed to accurately characterise the release of the pheromone into the air. Release kinetics analysis performed on the vine leaves showed a high pheromone release (about 30% of the sprayed quantity) the first day of the test. The release rate then decreased rapidly to reach about 650 mg/day/ha after 4 days. Kinetic modelling showed that it would be possible to maintain an effective airborne concentration of pheromone for approximately 12 days. Release tests were also carried out on glass, PVC and blotting paper. The results obtained showed that the vine leaves behaved as a non-absorbent material, implying that the pheromone used in the Lobesia Pro Spray formulation did not penetrate the plant. These first results prove the feasibility of using vine leaves as pheromone dispensers for a sprayed formulation and the ability to optimise the treatment conditions (dose and frequency) through laboratory testing.

Assessment of gas-phase concentrations of organophosphate flame retardants at the material surface using a midget emission cell coupled to solid-phase microextraction.

Actual methods for on-site measurement of gaseous concentrations of Semi-Volatile Organic Compounds (SVOCs) at the material surface (y0) are not yet sufficiently developed mainly due to sampling difficulties. These concentrations are the key data to improve knowledge about indoor sources and human exposure to SVOCs. To the end, a specific emission cell coupled to solid-phase microextraction (SPME) was developed. The main challenge with this method is calibration because of very low volatility of SVOCs and static sampling mode. In this study, a generating system of organophosphate flame retardants (OFRs) using polyurethane foam as source combined with an active sampling method with Tenax tubes was proposed as a novel calibration device for SPME-based method. The generating system delivered stable OFR concentrations after 190 h of operation with a variation not exceeding ±5%. It allowed to obtain robust calibrations for tris-(2-chloropropyl)-phosphate (TCPP) and tri-butyl-phosphate (TBP) measured with the emission cell coupled to SPME-based method, define the optimal sampling requirements and achieve reproducible and accurate measurements of y0 at µg.m-3 level. TCPP and TBP gas-phase concentrations at the polyurethane foam surface (y0) were followed up over more 228 days under controlled temperature conditions. A high stability of these concentrations was observed showing that polyurethane foam acts as a stable and continuous source of organophosphate flame retardants indoors. This novel method should be useful for assessing the dynamic of emissions from indoor sources and potential exposure to SVOCs in indoor environments.

Influence of the environmental relative humidity on the inflammatory response of skin model after exposure to various environmental pollutants.

The skin is an essential barrier, protecting the body against the environment and its numerous pollutants. Several environmental pollutants are known to affect the skin, inducing premature aging through mechanisms including oxidative stress, inflammation, and impairment of skin functions. Even climate conditions can impact the skin. Therefore, using a Reconstructed Human Epidermis (RHE), we tested the effect of two samples of fine particulate matters (PM0.3-2.5 - one metals-rich sample and the other organic compounds-rich), two Volatile Organic Compounds mixtures (VOCs - from a solvent-based paint and a water-based paint) and Tobacco Smoke (TS). All pollutants affected cellular functionality, but to a lesser extent for the water-based paint VOC. This effect was enhanced when RHE were preconditioned for 2 h by a semi-dry airflow (45% relative humidity) before pollutants application, compared to preconditioning by a humid airflow (90% relative humidity). In the absence of preconditioning, IL-1α, IL-6, IL-8, and RANTES were almost systematically induced by pollutants. When RHE were preconditioned by a semi-dry or humid airflow before being subjected to pollutants, the increase of IL-1α, IL-8, and RANTES falls into two groups. Similarly to RHE not treated with pollutants, RHE treated with VOCs after preconditioning by a semi-dry airflow showed increased IL-1α, IL-8, and RANTES release. On the contrary, RHE treated with PM or TS after preconditioning by a semi-dry airflow show a lower increase in IL-1α, IL-8, and RANTES compared to preconditioning by a humid airflow. The effect of real environmental relative humidity conditions of the air, combined with acute exposure to various environmental pollutants, seemed to relate mainly to structural changes of the skin, determining the outcome of the inflammatory response depending on the physicochemical characteristics of pollutants.

Comparative analysis of formaldehyde and toluene sorption on indoor floorings and consequence on Indoor Air Quality.

Indoor surfaces may be adsorptive sinks with the potential to change Indoor Air Quality. To estimate this effect, the sorption parameters of formaldehyde and toluene were assessed on five floorings by an experimental method using solid-phase microextraction in an airtight emission cell. Adsorption rate constants ranged from 0.003 to 0.075 m·h-1 , desorption rate constants from 0.019 to 0.51 h-1 , and the partition coefficient from 0.005 to 3.9 m, and these parameters vary greatly from one volatile organic compound/material couple to another indicating contrasted sorption behaviors. A rubber was identified as a sink of formaldehyde characterized by a very low desorption constant close to 0. For these sorbent floorings identified, the adsorption rates of formaldehyde are from 2 to 4 times higher than those of toluene. Two models were used to evaluate the sink effects of floorings on indoor pollutant concentrations in one room from different realistic conditions. The scenarios tested came to the conclusion that the formaldehyde sorption on one rubber (identified as a sink) has a maximum contribution from 15% to 21% for the conditions of low air exchange rate. For other floorings, the sorption has a minor contribution less than or equal to 5%, regardless of the air exchange rate.

Evidence of indoor sinks for formaldehyde through the field measurements using passive flux sampler and mass balance.

A measurement campaign was conducted in 24 student rooms where formaldehyde emissions from all the indoor surfaces were measured using a passive flux sampler (PFS) parallel to monitoring of indoor and outdoor concentrations as well as the assessment of air exchange rate. Two mass balance models were used to predict indoor concentrations basing on input data recorded during this measurement campaign. The first model only takes into account the total emission from the indoor sources and the incoming and outgoing flows of compound brought by the air exchange rate. The second model added to these terms a further component related to the overall rate of removal processes (or "indoor sinks") which was assessed in these same rooms during a previous field test campaign. A good agreement was found between the concentrations calculated by the model with the component relative to indoor removal processes and the measured concentrations. On the other hand, the predicted concentrations with a first model tend to highly overestimate the measured concentrations by a factor 1.9 on average. Apportionment of formaldehyde inputs and losses in the rooms was estimated and discussed. The results highlighted that indoor removal processes are a component to consider for formaldehyde budget indoors.

Fireproofing of domestic upholstered furniture: Migration of flame retardants and potential risks.

Flame retardants (FRs) are widely incorporated in polyurethane foams to decrease their fire reaction. Currently, the risks associated with the use of FRs in domestic upholstered furniture (UF) are evaluated according to FRs volatility and potency to be emitted into the atmosphere. However, exposure via contact and dermal penetration, mediated by sweat, has not been considered so far. Our study provides an identification of the latest-generation of FRs most commonly used in UF, and an evaluation of their potency to migrate into artificial sweat. First of all, an extensive literature search, along with surveys with professionals, led to the identification of twenty-two FRs and synergists commonly used in France and Europe. Then, migration into artificial sweat of various FRs embedded into synthetic or commercially available polymer matrix was studied and evidenced. These results were analysed in the light of their potential effects on human health and the environment. Based on the migration's data, it is not possible to clearly rule out potential effects of FRs on human and environment health. Therefore, the authors consider that the use of FRs in domestic upholstery does not seem to be justified due to potential risks and a lack of clear benefits.

Oxidative damage and impairment of protein quality control systems in keratinocytes exposed to a volatile organic compounds cocktail.

Compelling evidence suggests that volatile organic compounds (VOCs) have potentially harmful effects to the skin. However, knowledge about cellular signaling events and toxicity subsequent to VOC exposure to human skin cells is still poorly documented. The aim of this study was to focus on the interaction between 5 different VOCs (hexane, toluene, acetaldehyde, formaldehyde and acetone) at doses mimicking chronic low level environmental exposure and the effect on human keratinocytes to get better insight into VOC-cell interactions. We provide evidence that the proteasome, a major intracellular proteolytic system which is involved in a broad array of processes such as cell cycle, apoptosis, transcription, DNA repair, protein quality control and antigen presentation, is a VOC target. Proteasome inactivation after VOC exposure is accompanied by apoptosis, DNA damage and protein oxidation. Lon protease, which degrades oxidized, dysfunctional, and misfolded proteins in the mitochondria is also a VOC target. Using human skin explants we found that VOCs prevent cell proliferation and also inhibit proteasome activity in vivo. Taken together, our findings provide insight into potential mechanisms of VOC-induced proteasome inactivation and the cellular consequences of these events.

Using the chemical mass balance model to estimate VOC source contributions in newly built timber frame houses: a case study.

Basing on the material emission data obtained in a test chamber, chemical mass balance (CMB) was used to assess the source apportionment of volatile organic compound (VOC) concentrations in three newly built timber frame houses. CMB has been proven to be able to discriminate the source contributions for two contrasted environmental conditions (with and without ventilation). The shutdown of the ventilation system caused an increase in the VOC concentrations due to the increased contribution of indoor surface materials like the door material and furniture explaining together over 65% of total VOCs. While the increase in formaldehyde concentration is mainly due to furniture (contribution of 70%), the increase in α-pinene concentration is almost exclusively attributable to the emission of door material (up to 84%). The apportionment of VOC source contributions appears as highly dependent on the position of source materials in the building (surface materials or internal materials) and the ventilation conditions explaining that the concentrations of compounds after the shutdown of ventilation system do not increase in equivalent proportion. Knowledge of indoor sources and its contributions in real conditions may help in the selection of materials and in the improvement of construction operations to reduce the indoor air pollution.

Formaldehyde passive sampler using an optical chemical sensor: how to limit the humidity interference.

The behaviour of a new formaldehyde diffusive sampler using an optical chemical sensor with respect to high humidity conditions is examined in controlled atmospheres. Five prototypes of the radial diffusion sampler having the same chemical sensor and different designs were tested. In addition, a set of experiments were performed on the chemical sensor to characterise its efficiency of trapping water vapour in the absence and in the presence of the reactants, Fluoral-P and formaldehyde. Differences in humidity interference between the five diffusive sampler prototypes were studied and discussed. From all the results obtained, it was shown that the prototype LDE1.4 combining a small diffusion slot, a reduced internal volume and a sensor shifted upwards from the diffusion slot provided formaldehyde measurements least affected by humidity up to 80% RH at 20 °C. This new type of diffusive sampler with on-site direct reading is intended to ultimately replace conventional passive samplers with DNPH requiring offset laboratory analyses.

New sampling device for on-site measurement of SVOC gas-phase concentration at the emitting material surface.

The gas-phase concentration at the material surface (y 0 ) is pointed out in the literature as a key parameter to describe semivolatile organic compound (SVOC) emissions from materials. This is an important input data in predictive models of SVOC behavior indoors and risk exposure assessment. However, most of the existing measurement methods consist of determining emission rates and not y 0 and none allow on-site sampling. Hence, a new passive sampler was developed. It consists of a glass cell that is simply placed on the material surface until reaching equilibrium between material and air; y 0 is then determined by solid-phase microextraction (SPME) sampling and GC-MS analysis. The limits of detection are at the µg/m3 level and relative standard deviations (RSD) below 10%. A variation of 11% between two sets of experiments involving different cell volumes confirmed the y 0 measurement. In addition, due to the ability of SVOCs to be sorbed on surfaces, the cell wall/air partition was assessed by determining the inner cell surface concentration of SVOCs, which is the concentration of SVOCs adsorbed on the glass, and the cell surface/air partition coefficient (K glass ). The recovery yields of the SVOCs sorbed on the cell walls are strongly compound-dependent and comprise between 2 and 93%. The K glass coefficients are found to be lower than the stainless steel/air partition coefficient (K ss ), showing that glass is suitable for the SVOC sampling. This innovative tool opens up promising perspectives in terms of identification of SVOC sources and quantification of their emissions indoors, and would significantly contribute to human exposure assessment. Graphical Abstract Passive sampling for the determination of SVOCs concentration at the material/air interface.

Determination of the volatile fraction of phosphorus flame retardants in cushioning foam of upholstered furniture: towards respiratory exposure assessment.

The purpose of this paper was to highlight potential exposure in indoor air to phosphorus flame retardants (PFRs) due to their use in upholstered furniture. For that, an analytical method of PFRs by headspace coupled to solid-phase micro-extraction (HS-SPME) was developed on cushioning foams in order to determine the PFRs' volatile fraction in the material. Tests on model foams proved the feasibility of the method. The average repeatability (RSD) is 6.3 % and the limits of detection range from 0.33 to 1.29 µg g(-1) of foam, depending on the PFRs. Results showed that some PFRs can actually be emitted in air, leading to a potential risk of exposure by inhalation. The volatile fraction can be high (up to 98 % of the total PFRs amount) and depends on the physicochemical properties of flame retardants, on the textural characteristics of the materials and on the temperature. The methodology developed for cushioning foams could be further applied to other types of materials and can be used to rate them according to their potential releases of phosphorus flame retardants.

Assessment of diffusion parameters of new passive samplers using optical chemical sensor for on-site measuring formaldehyde in indoor air: experimental and numerical studies.

New passive samplers using a sensor consisting of a sol-gel matrix entrapping Fluoral-P as sampling media were developed for the determination of formaldehyde in indoor air. The reaction between Fluoral-P and formaldehyde produces a colored compound which is quantified on-site by means of a simple optical reading module. The advantages of this sensor are selectivity, low cost, ppb level limit of detection, and on-site direct measurement. In the development process, it is necessary to determine the sampling rate, a key parameter that cannot be directly assessed in the case of diffusive samplers using optical chemical sensor. In this study, a methodology combining experimental tests and numerical modeling is proposed and applied at five different radial diffusive samplers equipped with the same optical chemical sensor to assess the sampled material flows and sampling rates. These radial diffusive samplers differ in the internal volume of the sampler (18.97 and 6.14 cm(3)), the position of sensor inside the sampler (in front and offset of 1.2 cm above the membrane) and the width of the diffusion slot (1.4 and 5.9 mm). The influences of these three parameters (internal volume, position of sensor inside the sampler, and width of the diffusion slot) were assessed and discussed with regard to the formaldehyde sampling rate and water uptake by sensor (potential interference of measure). Numerical simulations based on Fick's laws are in agreement with the experimental results and provide to estimate the effective diffusion coefficient of formaldehyde through the membrane (3.50 × 10(-6) m(2) s(-1)). Conversion factors between the sensor response, sampled formaldehyde mass and sampling rate were also assessed.

Formaldehyde emission behavior of building materials: on-site measurements and modeling approach to predict indoor air pollution.

The purpose of this paper was to investigate formaldehyde emission behavior of building materials from on-site measurements of air phase concentration at material surface used as input data of a box model to estimate the indoor air pollution of a newly built classroom. The relevance of this approach was explored using CFD modeling. In this box model, the contribution of building materials to indoor air pollution was estimated with two parameters: the convective mass transfer coefficient in the material/air boundary layer and the on-site measurements of gas phase concentration at material surfaces. An experimental method based on an emission test chamber was developed to quantify this convective mass transfer coefficient. The on-site measurement of gas phase concentration at material surface was measured by coupling a home-made sampler to SPME. First results had shown an accurate estimation of indoor formaldehyde concentration in this classroom by using a simple box model.

A model of human nasal epithelial cells adapted for direct and repeated exposure to airborne pollutants.

Airway epithelium lining the nasal cavity plays a pivotal role in respiratory tract defense and protection mechanisms. Air pollution induces alterations linked to airway diseases such as asthma. Only very few in vitro studies to date have succeeded in reproducing physiological conditions relevant to cellular type and chronic atmospheric pollution exposure. We therefore, set up an in vitro model of human Airway Epithelial Cells of Nasal origin (hAECN) close to real human cell functionality, specifically adapted to study the biological effects of exposure to indoor gaseous pollution at the environmental level. hAECN were exposed under air-liquid interface, one, two, or three-times at 24 h intervals for 1 h, to air or formaldehyde (200 µg/m(3)), an indoor air gaseous pollutant. All experiments were ended at day 4, when both cellular viability and cytokine production were assessed. Optimal adherence and confluence of cells were obtained 96 h after cell seeding onto collagen IV-precoated insert. Direct and repeated exposure to formaldehyde did not produce any cellular damage or IL-6 production change, although weak lower IL-8 production was observed only after the third exposure. Our model is significantly better than previous ones due to cell type and the repeated exposure protocol.

Development of SPME on-fiber derivatization for the sampling of formaldehyde and other carbonyl compounds in indoor air.

Solid-phase microextraction on-fiber derivatization applied to carbonyl compounds is known, but application to indoor air is poorly developed and the methods deserve to be complemented and optimized. In this work, two derivatization reagents, pentafluorophenylhydrazine and o-2,3,4,5,6-(pentaflurobenzyl)hydroxylamine (PFBHA), and three fiber coatings were tested in order to select the best combination. As Carboxen-based coatings were proven to induce the formation of by-products during the thermal desorption step, a polydimethylsiloxane-divinylbenzene fiber in association with PFBHA was finally chosen. The study of the derivatization kinetics showed that the reaction of PFBHA with carbonyl compounds was instantaneous, except for acetone. Analyses were performed by gas chromatography coupled with flame ionization detection and mass spectrometry. For 5 min fiber exposure, the limits of detection are below 0.5 µg m(-3) in selected ion monitoring mode, the reproducibility was 15% on average, and the linearity of the calibration curves was satisfactory. For on-site application, the influence of air humidity and the conditions in which the impregnated fibers were stored were studied. It is possible to store the fibers for 3 days before and for at least 2 days after sampling. The relative humidity of air was shown to have no influence on solid-phase microextraction sampling in the range from 0 to 70%. For formaldehyde, the method was compared with sampling on 2,4-dinitrophenylhydrazine cartridges, and the first results showed good agreement. Finally, the method was applied to three different indoor environments to check its feasibility.

Static SPME sampling of VOCs emitted from indoor building materials: prediction of calibration curves of single compounds for two different emission cells.

Solid-phase microextraction (SPME) is a powerful technique, easy to implement for on-site static sampling of indoor VOCs emitted by building materials. However, a major constraint lies in the establishment of calibration curves which requires complex generation of standard atmospheres. Thus, the purpose of this paper is to propose a model to predict adsorption kinetics (i.e., calibration curves) of four model VOCs. The model is based on Fick's laws for the gas phase and on the equilibrium or the solid diffusion model for the adsorptive phase. Two samplers (the FLEC® and a home-made cylindrical emission cell), coupled to SPME for static sampling of material emissions, were studied. A good agreement between modeling and experimental data is observed and results show the influence of sampling rate on mass transfer mode in function of sample volume. The equilibrium model is adapted to quite large volume sampler (cylindrical cell) while the solid diffusion model is dedicated to small volume sampler (FLEC®). The limiting steps of mass transfer are the diffusion in gas phase for the cylindrical cell and the pore surface diffusion for the FLEC®. In the future, this modeling approach could be a useful tool for time-saving development of SPME to study building material emission in static mode sampling.

Optimization of FLEC-SPME for field passive sampling of VOCs emitted from solid building materials.

The FLEC-SPME sampler, described in a previous paper, consists of an emission cell coupled with solid phase microextraction (SPME) for passive sampling of VOCs emitted from building materials. It represents an interesting alternative to standard dynamic sampling protocol as it is easier to implement. If standard dynamic sampling determines emission rates, passive FLEC-SPME aims to the determination of the concentration in air at the material surface. That could be assumed provided that material/air equilibrium is reached. Thus, VOCs emission kinetics were studied for 3 different materials (pine wood panel, carpet and PVC floor) to determine equilibrium times. Then, the relevance of the method has been assessed using new materials through a 3-day emission test. Qualitative results were compared to those obtained from the standard method to check the ability of FLEC-SPME to detect the most toxic compounds, named "VOCs of interest" and listed in the French regulation. Minor differences were observed, so this methodology seems promising, especially for field studies aiming in the identification of VOCs sources in buildings. Moreover, the concentration at the material surface combined to emission modeling could be used to predict indoor VOCs concentrations helping in indoor air quality diagnostic.

Solid phase microextraction sampling for a rapid and simple on-site evaluation of volatile organic compounds emitted from building materials.

A new sampling method was developed for a simple and fast evaluation of volatile organic compounds (VOCs) emitted at trace levels from building materials. The device involves an emission cell coupled with solid phase microextraction (SPME) for diffusive sampling. Owing to possible competitive adsorption of VOCs onto the PDMS-Carboxen fiber used, the co-adsorption conditions were determined through kinetics study of isolated and in mixture compounds. Hence, the linear concentration ranges which ensure reliable quantification were determined from 4.8 to 10mgm(-3)min according to the VOC studied. Thus, the analyst can select the extraction time that fits for his best analytical objectives. For example, sub microgm(-3) limits of detection can be achieved for GC-MS analysis for 20min extraction. On the other hand, 5min sampling is sufficient for a rapid screening of the major emitted VOCs, since the average limit of quantification reaches 20microgm(-3) for GC-FID analysis.