Thermal Desorption Gas Chromatography Research Articles

Investigation on air quality of specific indoor environments\u2014spa salons located in Gdynia, Poland

Due to excessive application of essential oils and scented products in spa salons during aromatherapy and massage sessions, the elevated concentration of total volatile organic compounds (TVOCs), particularly terpenes, which are known as secondary organic aerosol (SOA) precursors, is expected there. This study was aimed at determination of VOCs with a particular regard to terpenes in air samples collected in selected spa salons located in Northern Poland. Active air sampling was conducted before and after treatments. Samples were analyzed with the use of thermal desorption gas chromatography coupled with flame-ionization detector (TD-GC-FID) and mass spectrometer (TD-GC-MS). Obtained results allowed to characterize chemical composition of indoor air of spa salons and also to relate the dependence between applied essential oil and indoor air chemical composition. It has been proved that (i) spa salons are characterized by TVOC concentrations exceeding recommended values of 300–400 μg m−3 in most of examined cases, reaching up to several thousand of micrograms per cubic meter, (ii) TVOC concentration is strictly related to salon characteristics and carried out treatments, (iii) terpenes constitute a significant part of TVOCs present in spa indoor air, from 22 up to 86%, (iv) most commonly investigated terpenes in the literature (d-limonene, α-pinene, camphene, and linalool) were also determined at the highest concentration levels in this study and (v) VOC chemical composition is strictly dependent on the type of applied essential oils. On the basis of obtained results, it may be stated that extensive application of essential oils rich in terpenes can significantly alter indoor air chemistry of spa salons, thereby influencing health and well-being of employees working there.Graphical abstract

Determination of recovery rates of adsorbents for sampling very volatile organic compounds (C1C6) in dry and humid air in the sub-ppb range by use of thermal desorption gas chromatography-mass spectrometry.

The reliable measurement of very volatile organic compounds (VVOC) in indoor air by use of thermal desorption gas chromatography (TD-GC) in order to include them into evaluation schemes for building products even nowadays is a great challenge. For capturing these small molecules with carbon numbers ranging from C1C6, strong adsorbents are needed. In the present study, recovery rates of nine suitable adsorbents of the groups of porous polymers, graphitised carbon blacks (GCB) and carbon molecular sieves (CMS) are tested against a complex test gas standard containing 29 VVOC. By consideration of the recovery and the relative humidity (50%RH), combinations of the GCB Carbograph5TD, the two CMS Carboxen1003 and CarbosieveSII as well as the porous polymer Tenax®GR were identified to be potentially suitable for sampling the majority of the VVOC out of the gas mix. The results reveal a better performance of the adsorbents in combination than being used alone, particularly under humid sampling conditions. The recovery rates of the chosen compounds on each adsorbent should be in the range of 80-120%.

Optimisation of a thermal desorption–gas chromatography–mass spectrometry method for the analysis of monoterpenes, sesquiterpenes and diterpenes

Abstract. In this study, a thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) method following sorbent tube sampling was developed for the determination of monoterpenes (MTs), sesquiterpenes (SQTs) and diterpenes (DTs) in gas-phase samples. The analytical figures of merit were determined, and the method performance was tested by conducting experiments related to, for example, sampling recovery, storage stability and ozone reactivity. The limit-of-quantification values were 13–518 pg (0.5–9.3 pptv), intermediate precision was in the range of 3 %–10 % and the expanded measurement uncertainty was in the range of 16 %–55 % for terpenes. The sampling recoveries of terpenes were approximately within 100±20 % with different inlet lines (15 m long Teflon and 1 m long heated stainless steel) and branch enclosure cuvette (6 L Teflon bag) tested. Ozone is an important factor causing losses of the studied compounds during sampling. Therefore, losses of terpenes upon ozone exposure were studied and the reaction rate coefficients were estimated. The ozone reaction rate coefficient (kO3) of ent-kaurene was experimentally estimated to be 2 orders of magnitude greater than the respective literature kO3 value, demonstrating the potential underestimation of DT contribution to atmospheric reactivity. The preliminary comparison between offline- and online-mode TD–GC–MS sampling and analysis revealed that diterpenes and oxygenated sesquiterpenes are lost in excessive amounts in online-mode sampling, hindering the online-mode applicability for the quantitative analysis of these compounds. A few applications to real samples were tested to identify DTs potentially emitted by boreal forest tree species. In dynamic headspace samples of pine needles and spruce twigs heated to 60 ∘C, five DTs and 13 DTs could be detected in emissions, respectively. The semi-quantitatively estimated emission rates of DTs were roughly 1 to 3 orders of magnitude lower than those of MTs and SQTs. Similarly, in spruce branch enclosure emissions from a living tree, six DTs were detected once the enclosure was heated to ca. 60 ∘C. In summary, the developed analytical procedure was demonstrated to be applicable for the analysis of MTs, SQTs and DTs. In addition, DTs could be detected in needles, twigs and branch enclosure emissions; however, high temperatures were required to promote the emissions and for obtaining detectable concentrations.

Investigation of Non-Methane Hydrocarbons at a Central Adriatic Marine Site Mali Lošinj, Croatia

For the first time, volatile hydrocarbons were measured in Croatia, at Mali Lošinj in the period from autumn 2004 to autumn 2005. Mali Lošinj site is conveniently located as a gateway to Croatia for any potential pollution from either Po valley in Italy, or other locations in southern Europe or even Africa. The sampling was performed on multisorbent tubes and then analyzed by thermal desorption gas chromatography with a flame ionization detector. The aim was to determine and estimate the non-methane hydrocarbons in Mali Lošinj, a location with Mediterranean vegetation and species which emit large quantities of volatile organic compounds. Ozone volume fraction and meteorological parameters were also continuously measured, from April to October 2005. Ethane, ethene, ethyne, propane, propene, n-pentane, n-hexane, benzene and toluene were identified in all air samples. Benzene and toluene have been found in ambient air and significant positive correlations between ethyne and ethane, propane and propene indicate emissions from transport.

Photochemical transformation of residential wood combustion emissions: dependence of organic aerosol composition on OH exposure

Abstract. Residential wood combustion (RWC) emits large amounts of gaseous and particulate organic aerosol (OA). In the atmosphere, the emission is transformed via oxidative reactions, which are under daylight conditions driven mainly by hydroxyl radicals (OH). This continuing oxidative ageing produces secondary OA and may change the health- and climate-related properties of the emission. However, it is not well known how the composition of RWC-originated OA changes as the function of OH exposure. In this work, emissions from two modern residential logwood combustion appliances were photochemically aged in an oxidation flow reactor (OFR) with various OH exposure levels, reaching up to 6×1011 s cm−3 (equivalent to 1 week in the atmosphere). Gaseous organic compounds were analysed by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS), while particulate OA was analysed online by a high-resolution soot particle aerosol mass spectrometer (SP-HR-ToF-AMS) and offline by in situ derivatization thermal desorption–gas chromatography–time-of-flight mass spectrometry (IDTD-GC-ToF-MS). Photochemical reactions increased the mass of particulate organic carbon by a factor of 1.3–3.9. The increase in mass took place during the first atmospheric equivalent day of ageing, after which the enhancement was independent of the extent of photochemical exposure. However, ageing increased the oxidation state of the particulate OA linearly throughout the assessed range, with ΔH:C/ΔO:C slopes between −0.17 and −0.49 in van Krevelen space. Ageing led to an increase in acidic fragmentation products in both phases, as measured by the IDTD-GC-ToF-MS for the particulate and PTR-ToF-MS for the gaseous phase. For the gaseous organic compounds, the formation of small carbonylic compounds combined with the rapid degradation of primary volatile organic compounds such as aromatic compounds led to a continuous increase in both the O : C and H : C ratios. Overall, the share of polycyclic aromatic compounds (PACs) in particles degraded rapidly during ageing, although some oxygen-substituted PACs, most notably naphthaldehydic acid, increased, in particular during relatively short exposures. Similarly, the concentrations of particulate nitrophenols rose extensively during the first atmospheric equivalent day. During continuous photochemical ageing, the dominant transformation mechanisms shifted from the initial gas-phase functionalization/condensation to the transformation of the particulate OA by further oxidation reactions and fragmentation. The observed continuous transformation of OA composition throughout a broad range of OH exposures indicates that the entire atmospheric lifetime of the emission needs to be explored to fully assess the potential climate and health effects of RWC emissions.

Bar adsorptive microextraction device coated with polyimide microsphere assembled by nanosheets combined with thermal desorption-gas chromatography for trace analysis of nitroaromatic explosives in environmental waters

Polyimide (PI) microspheres assembled by nanosheets were used for bar adsorptive microextraction (BAμE) for the first time. The PI microsphere possessed self-organized hierarchical nanostructure, large specific surface area (170 m2/g) and good thermostability (up to 400 °C). The BAμE device was prepared by adhering the PI microspheres on a quartz bar with Kapton double sided tape. Trace nitroaromatic explosives in environmental waters were extracted by the BAμE device, desorbed by thermal desorption (TD), and analyzed by gas chromatography-mass spectrometry (GC–MS). The reproducibility of five BAμE devices prepared in parallel was less than 13.0% (expressed as relative standard deviation, RSD). The BAμE device could stand up to 30 extraction/desorption cycles without decrease of extraction efficiency. The results of method validation showed that the BAμE-TD/GC–MS method possessed wide linearity (0.05–50 μg/L or 0.05–20 μg/L), high correlation coefficients (> 0.9987), good precision (RSDs < 11.8%), low detection limits (0.005–0.013 μg/L) and high enrichment factors (528–1410). Relative recoveries were in the range of 72.2–122.6% with RSDs between 0.1% and 10.5% for real water samples. These results proved that the proposed method was a good choice for determination of organic pollutants in water samples.

Spatiotemporal variation of odor-active VOCs in Thessaloniki, Greece: implications for impacts from industrial activities.

A yearlong study of odor-active VOCs was carried out in the northwestern district of the city of Thessaloniki, Greece, which is in close vicinity to a large-scale petroleum refining and petrochemical process complex, as well as other activities such as power generation from natural gas burning and liquefied petroleum gas (LPG) shipping. Odor nuisance has been a major concern in the district often rising complaints from local residents. A total of 312 samples of VOCs were collected at three sites during a 12-month period (May 2018-May 2019) on thermal desorption cartridges and analyzed by thermal desorption gas chromatography interfaced with mass selective detector (TD-CG/MS). Fifty-five odorous compounds including 8 mercaptans, 5 thiophenes, 7 sulfides, 22 aromatics, and 13 aldehydes were measured, and their spatial and temporal variations were assessed. Concentrations found were compared with those measured at other sites within the urban agglomeration Thessaloniki. Correlations with meteorological conditions (ambient temperature, relative humidity, wind direction/speed, and frequency/depth of temperature inversions) were investigated. Bivariate polar plots of the concentrations of Σ8Mercaptans, Σ5Thiophenes, Σ7Sulfides, Σ22Aromatics, and Σ13Aldehydes as a function of wind speed and wind direction were constructed for source localization.

Organic molecular markers and source contributions in a polluted municipality of north-east Italy: Extended PCA-PMF statistical approach

Exceeding the maximum levels for environmental pollutants creates public and scientific interest for the environmental and human health impact it may have. In Northern Italy, the Po Valley, and in particular the Veneto region, is still a hotspot for air quality improvement. Several monitoring campaigns were carried out in this area to acquire information about sources of pollutants which are considered critical. For the first time, a deep study of the aerosol organic fraction was performed in the town Sernaglia della Battaglia, nearby Treviso. During three seasons of 2017, PM1 and PM2.5 samples were collected simultaneously. Organic molecular markers have been analyzed by in-situ derivatization thermal desorption gas chromatography time-of-flight mass spectrometry (IDTD-GC-TOFMS). Alkanes, polycyclic aromatic hydrocarbons, oxi-polycyclic aromatic hydrocarbons, anhydrous sugars, resins acids, triterpenoids, and acids were considered. The organic chemical composition has been analyzed based on seasonal variation and source contributions. Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF) have been combined to deeply investigate the main sources of particulate organic matter. On the one hand, PCA evaluates the correlations between the organic markers and their seasonal distribution. On the other hand, the source contributions to aerosol composition are estimated by PMF. Four main emission sources were found by PMF: solid fuel combustion (coal, wood), combustion of petroleum distillates (gas and fuel oil) and exhaust gases of vehicles, industrial combustion processes, home heating, and forest fires are evaluated as the most important sources for the air quality and pollution in this municipality of Northern Italy.

Comparison of the extraction efficiency of ice concentration linked with extractive stirrer, stir bar sorptive extraction, and solid-phase microextraction for pesticides from drinking water

With the advent of highly selective analysis techniques (e.g., liquid chromatography-tandem mass spectrometry), and lower limits of detection requirements, extraction efficiency is arguably the most important property of modern sample preparation techniques. In this study, the extraction efficiency of Ice Concentration Linked with Extractive Stirrer (ICECLES) was compared to Stir Bar Sorptive Extraction (SBSE) and Solid-Phase Microextraction (SPME). A direct comparison of these sample preparation techniques was carried out with analysis via both Liquid Chromatography – Tandem Mass Spectrometry (LC–MS/MS) and Thermal Desorption Gas Chromatography – Mass Spectrometry (TD-GC–MS). ICECLES produced 2x and 7x greater TD-GC–MS signals than SBSE and SPME, respectively. When comparing extraction techniques for a suite of 60 pesticides in drinking water, 32, 25, and 13 pesticides were detected via LC–MS/MS at 0.1 ng/mL by ICECLES, SBSE, and SPME, respectively. Overall, ICECLES consistently produced better extraction efficiencies than the other extraction techniques evaluated.

Extraction-Free, Direct Determination of Caffeine in Microliter Volumes of Beverages by Thermal Desorption-Gas Chromatography Mass Spectrometry.

An extraction-free method requiring microliter (μL) volumes has been developed for the determination of caffeine in beverages. Using a pyrolysis-gas chromatography mass spectrometry system, the conditions required for the direct thermal desorption-gas chromatography mass spectrometry (TD-GC/MS) determination of caffeine were optimised. A 5 μL aliquot was introduced to the thermal desorption unit, dried, and thermally desorbed to the GC/MS. The response was linear over the range 10 to 500 μg/mL (R2 = 0.996). The theoretical limit of detection (3 σ) was 0.456 μg/mL. No interferences were recorded from endogenous beverage components or from commonly occurring drugs, such as nicotine, ibuprofen, and paracetamol. Replicate caffeine determinations on fortified latte style white coffee and Pepsi Max® gave mean recoveries of 93.4% (%CV = 4.1%) and 95.0% (%CV = 0.98%), respectively. Good agreement was also obtained with the stated values of caffeine for an energy drink and for Coca-Cola®. These data suggest that the method holds promise for the determination of caffeine in such samples.

Identification of Anoplophora glabripennis (Moschulsky) by its emitted specific volatile organic compounds

Explorative experiments were done to figure out differences in the emission of volatile organic compounds (VOCs) of not infested trees and trees infested by Anoplophora glabripennis (Asian longhorn beetle, ALB), a quarantine pest. Therefore, VOCs from some native insect species, Anoplophora glabripennis infested Acer, stressed Acer, healthy Acer, Populus and Salix were obtained by enrichment on adsorbents. Qualitative analysis was done by thermal desorption gas chromatography coupled with a mass selective detector (TD-GC/MS). Altogether 169 substances were identified. 11 substances occur from ALB infested or mechanically damaged trees i.e. stressed trees, but not from healthy trees. (+)-Cyclosativene, (+)-α-longipinene, copaene and caryophyllene are detectable only from ALB-infested Acer not from mechanically damaged or healthy Acer. However, these substances are also emitted by healthy Salix. 2,4-Dimethyl-1-heptene is among all tree samples exclusively present in the ambience of ALB-infested trees. It´s rarely detectable from native insect species’ samples.

Aerosol-associated non-polar organic compounds (NPOCs) at Jammu, India, in the North-Western Himalayan Region: seasonal variations in sources and processes.

Fine particulate (PM2.5) bound non-polar organic compounds (NPOCs) and associated diagnostic parameters were studied at Jammu, an urban location in the foothills of North-Western Himalayan Region. PM2.5 was collected daily (24h, once a week) over a year to assess monthly and seasonal variations in NPOC concentration and their source(s) activity. Samples were analyzed on thermal desorption-gas chromatography mass spectrometry to identify and quantify source-specific organic markers. Homologous series of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), isoprenoid hydrocarbons and nicotine were investigated to understand the sources of aerosols in the region. The annual mean concentration of PM2.5 during the sampling period was found higher than the permissible limit of India's National Ambient Air Quality Standards (NAAQS) and World Health Organisation (WHO) guidelines. The rise of concentration for PM2.5 and associated NPOCs in summer season was attributed to enhanced emission. The n-alkane-based diagnostic parameters indicated mixed contributions of NPOCs from anthropogenic sources like fossil fuel-related combustion with significant inputs from biogenic emission. Moreover, high influence of petrogenic contributionwas observed in summer (monsoon) months. The quantifiable amounts of isoprenoid hydrocarbons further confirmed this observation. Total PAH concentration also followed an increasing trend from March to June, and June onwards a sharp decrease was observed. The higher concentration of environmental tobacco smoke marker nicotine in winter months was plausibly due to lower air temperature and conditions unfavourable to photo-degradation. A clear dominance of low molecular weight PAHs was noticed with rare presence of toxic PAHs in the ambient atmosphere of Jammu. PAH-based diagnostic parameters suggested substantial contribution from low temperature pyrolysis processes like biomass/crop-residue burning, wood and coal fire in the region. Specific wood burning markers further confirmed this observation.

Optimization of a Method for the Detection of Biomass-Burning Relevant VOCs in Urban Areas Using Thermal Desorption Gas Chromatography Mass Spectrometry

Forest fire smoke influence in urban areas is relatively easy to detect at high concentrations but more challenging to detect at low concentrations. In this study, we present a simplified method that can reliably quantify smoke tracers in an urban environment at relatively low cost and complexity. For this purpose, we used dual-bed thermal desorption tubes with an auto-sampler to collect continuous samples of volatile organic compounds (VOCs). We present the validation and evaluation of this approach using thermal desorption gas chromatography mass spectrometry (TD-GC-MS) to detect VOCs at ppt to ppb concentrations. To evaluate the method, we tested stability during storage, interferences (e.g., water and O3), and reproducibility for reactive and short-lived VOCs such as acetonitrile (a specific chemical tracer for biomass burning), acetone, n-pentane, isopentane, benzene, toluene, furan, acrolein, 2-butanone, 2,3-butanedione, methacrolein, 2,5- dimethylfuran, and furfural. The results demonstrate that these VOCs can be quantified reproducibly with a total uncertainty of ≤30% between the collection and analysis, and with storage times of up to 15 days. Calibration experiments performed over a dynamic range of 10–150 ng loaded on to each thermal desorption tube at different relative humidity showed excellent linearity (r2 ≥ 0.90). We utilized this method during the summer 2019 National Oceanic and Atmospheric Administration (NOAA) Fire Influence on Regional to Global Environments Experiment–Air Quality (FIREX-AQ) intensive experiment at the Boise ground site. The results of this field study demonstrate the method’s applicability for ambient VOC speciation to identify forest fire smoke in urban areas.

Change in hydrocarbon composition in rock samples as a function of time: A thermodynamic evaporation model

Recent pyrolysis analytical methods such as Shale Play (Romero-Sarmiento et al. 2016), HAWK-PAM (Maende et al., 2017) and Incremental S1 (Beti et al., 2018) enable improved understanding of the quantity and quality of free petroleum present in rock samples. However, it is well established that the evaporation losses restrict the ability of an experiment to accurately quantify and qualify free petroleum in rock sample (Michael et al., 2013; Jiang et al., 2016; Li et al. 2020). This article presents a thermodynamic model to explain the change in hydrocarbons composition of rock samples residing in a laboratory as a function of time. The model involves multicomponent residue curves and vapor-liquid equilibrium calculations. The changes in hydrocarbon composition predicted using models were compared with experimental data obtained from thermal desorption-gas chromatography (TD-GC) analysis of rock samples. High correlation coefficients are observed between predicted compositions and the experimental data inferring a good model fidelity. Relatively higher deviations were also observed between experimental data and predicted composition with time. The proposed model is useful in complementing the experimental results and enhancing the fundamental understanding of hydrocarbon loss from rock samples. This model also has the potential to eliminate multiple experiments to estimate the compositions after hours of sample collections.

Hydrocarbon distributions of incremental S1 peaks corresponding to different boiling point ranges of petroleum in rock samples

This correspondence presents an extension to the article “A New Method of Source and Reservoir Rock Pyrolysis to Determine the Boiling Point Distribution of Petroleum in Rock Samples” by Beti et al. (2018). Thermal desorption-gas chromatography (TD-GC) analysis of S1 peak and the sequential split of S1 into three peaks were performed on a Gothic shale sample from the Paradox Basin, Utah. The results indicate that the total area and composition of the S1 peak that includes all of the hydrocarbon molecules detected are equivalent to the sum of the three sequential peaks. The hydrocarbon distribution of the three sequential peaks was used to predict the range of hydrocarbons detected at “Incremental S1” temperatures.

Source apportionment of atmospheric volatile aromatic compounds (BTEX) by stable carbon isotope analysis: A case study during heating period in Taiyuan, northern China

Due to the high negative effects on health and environment, volatile aromatic compounds (benzene, toluene, ethylbenzene and xylene, BTEX) have drawn more and more attention recently. BTEX samples of four emission sources (coal combustion, vehicle exhaust, gasoline volatilization and solvent evaporation) and ambient air from three sampling sites (rural, urban and suburban) were collected during winter in Taiyuan, northern China. Gas chromatography–mass spectrometry and thermal desorption–gas chromatography–isotope ratio mass spectrometry were employed to investigate the composition characteristics and stable carbon isotopic (δ13C) analysis of BTEX, respectively. The results revealed that the δ13C value of BTEX for coal combustion, with the range of −23.8‰ to −25.2‰, was higher than that for vehicle exhaust, gasoline volatilization and solvent evaporation, ranging from −25.5‰ to −27.6‰, −28.0‰ to −30.9‰ and −27.7‰ to −32.1‰, respectively. Atmospheric BTEX concentrations were the highest at the suburban site (41.5 μg/m3) and the lowest at the rural site (27.0 μg/m3). The δ13C values of atmospheric BTEX at rural, urban and suburban sites ranged from −24.8‰ to −26.2‰ (average −25.3‰), −24.8‰ to −26.9‰ (average −26.0‰) and −23.9‰ to −25.4‰ (average −24.8‰), respectively, indicating that the suburban site was enriched in 13C relative to rural and urban sites. The B/T ratio results indicated that coal combustion was the primary source of atmospheric pollution in Taiyuan. The mean contribution of emission sources in all three sampling site were determined by adopting Isosource-based quantitative calculation. For rural, urban and suburban sites, coal combustion, as the major source, made mean contributions of 62.3%, 46.0% and 74.1%, while vehicle exhaust was responsible for 22.0%, 30.6% and 15.3%, respectively. Coal combustion and vehicle exhaust were the top two primary sources of BTEX in Taiyuan, especially coal combustion provided a half contribution to atmospheric BTEX. Therefore, implementing controls on coal combustion is crucial to reduce ambient volatile aromatic compound pollution, especially in areas with high coal consumption.

Trapping and preconcentration of volatile organic sulfur compounds in water samples by portable and battery-powered trapping device prior to gas chromatography-sulfur chemiluminescence determination

A simple, portable and battery-powered trapping device (iTrap) consisting of a purification tube, a trapping unit and a miniature air pump was developed for the pre-concentration of volatile organic sulfur compounds (VOSCs). The tested VOSCs, including methanthiol (MT), ethanethiol (ET), dimethyl sulfide (DMS), diethyl sulfide (DES) and dimethyl disulfide (DMDS), were firstly purged from water samples and then in situ pre-concentrated with the iTrap prior to their analysis by thermal desorption gas chromatography coupling with a sulfur chemiluminescence detector (TD-GC-SCD). Twenty-six adsorbents were studied to find the most suitable adsorbent for the efficient pre-concentration of VOSCs. Under optimal conditions, limits of detection of 6, 8, 6, 2 and 3 ng L−1 were obtained for MT, ET, DMS, DES and DMDS, respectively. The precisions were better than 5.3% (relative standard deviations, RSDs). The iTrap was successfully applied for the analysis of VOSCs in Certified Reference Materials, several surface water, underground water and wastewater samples collected from Pengzhou city, Sichuan, China. Moreover, the VOSCs trapped in the iTrap were much more stable than those directly stored in water samples and the recoveries for all samples could be maintained at acceptable levels (>73%), even their preservation time as long as 8 h.

Anthropogenic and biogenic hydrophobic VOCs detected in clouds at the puy de Dôme station using Stir Bar Sorptive Extraction: Deviation from the Henry's law prediction

Abstract Cloud droplets are able to trap many gaseous compounds and represent a very reactive media in the atmosphere. However, phase-partitioning of Volatile Organic Compounds (VOCs) between gaseous phase (interstitial air) and atmospheric liquid phase (cloud droplets) is still poorly characterized. In the present work, air samples and cloud water were collected simultaneously and hydrophobic organic compounds from anthropogenic and biogenic origins were quantified in order to evaluate their air/water partitioning. For this, cloud events were sampled at the puy de Dome station (PUY). A new analytical approach was optimized to explore dissolved VOCs in the aqueous phase by Stir Bar Sorptive Extraction (SBSE) and gaseous samples were collected using sorbent tubes. All samples were analyzed by Thermal Desorption (TD) Gas Chromatography (GC) coupled with Mass Spectrometry (MS). Extraction efficiencies by SBSE vary between 22% and 97% and the detection limit of VOCs in aqueous cloud samples lies between 1.0 and 8.7 ng L−1. Experimental partitioning is evaluated towards the theoretical one described by the Henry's Law constants. Our results show that observed concentrations of hydrophobic VOCs are supersaturated by a factor of 10–103 in comparison with Henry's law equilibrium. Calculations have been performed to evaluate the potential role of adsorption at the air/water interface and of sorption with non-dissolved organic carbon. However, the supersaturation in the cloud droplets requires more laboratory experiments to understand processes at the air/water interface and constrain cloud chemistry models.

Polybenzimidazole Solid-Phase Microextraction Bar Combined with Thermal Desorption–Gas Chromatography for Determination of Triazine Herbicides in Environmental Waters

In this work, polybenzimidazole (PBI) was used as extraction phase for solid-phase microextraction (SPME) combined with thermal desorption and gas chromatography–mass spectrometry (SPME/TD–GC–MS) to detect triazine herbicides in environmental waters. PBI with high thermostability (up to 370 °C) was coated on the quartz bar by the immersion–precipitation phase transformation method. Key parameters including extraction temperature, stirring rate, pH value, ionic strength, extraction time, desorption temperature and desorption time were optimized. The SPME/TD–GC–MS method showed the advantages of wide linearity (0.05–20 μg L−1) with good correlation coefficients (> 0.99), good precision (RSDs < 8.7%), low detection limits (0.0013–0.010 μg L−1), good reproducibility among SPME bars (< 8.8%), and long lifetime of more than 30 extraction/desorption cycles. Finally, the method was applied to determine triazines in real water samples including tap water, pond water, and river water. The relative recoveries were between 70.5 and 103.5% with RSDs ranging from 0.1 to 8.7%. These results indicate that PBI is a promising candidate for SPME extraction phase, especially for the determination of polar analytes combined with TD–GC–MS.

Determination of booster biocides in sediments by focused ultrasound-assisted extraction and stir bar sorptive extraction–thermal desorption–gas chromatography–mass spectrometry

Booster biocides present in natural waters may be captured by the sediments. Highly sensitive, robust, selective and reliable analytical methods are required to evaluate their presence in the sediments. A focused ultrasound assisted extraction method for the simultaneous determination of five organic booster biocides (Chlorothalonil, Dichlofluanid, Sea-Nine 211, Irgarol 1051 and TCMTB) in marine sediments is proposed. The isolation of the target compounds from 0.5 g of sediment was efficient using 2.5 mL of methanol as solvent, an output amplitude of 50 W, 100% duty cycle and an extraction time of 300 s. The extraction procedure was followed by solid-phase clean-up on non-polar sorbents (Oasis HLB). The compounds were sampled using stir bars (20 mm length, 0.5 mm film thickness) coated with polydimethylsiloxane (PDMS). The stir bars were stirred at 900 rpm for 3 h at room temperature. Desorption was carried out by thermal desorption (TD), and the analytes were separated in the gas chromatography (GC). They were detected by triple quadrupole mass spectrometry (MS/MS) using the multiple reaction monitor (MRM) mode. The detection limits (DLs) of booster biocides were in the range of 0.02 to 2.2 ng g − 1 dry weight. The regression coefficients were higher than 0.999. The average recovery was higher than 86% (R.S.D.: 7–11%). The analytical procedure was applied to determination of the booster biocides in port sediment samples from the southwestern Spain. Sea-Nine 211 was found in one sediment at a level of 2.1 ng g−1. Irgarol was present in all the sediments at concentrations between 2 and 9 ng g−1.