Recent Developments in Solid Phase Microextraction Techniques

The literature part of this thesis consists of a review of recently introduced forms of solid phase microextraction (SPME): thin film microextraction (TFME), in-tube solid phase microextraction(IT-SPME) and the closely related techniques of capillary in tube adsorption trap/solid phase dynamic extraction (INCAT/SPDE). The experimental part covers the study of reagents for on-fiber derivatization of low molecular weight aliphatic amines in atmospheric concentrations. In TFME a thin film of sorbent is used for extraction instead of a rod-like sorbent as in fiber-SPME. This increases analyte uptake and capacity compared to fiber-SPME, making TFME suitable for non-equilibrium extraction. TFME is used with both gas and liquid chromatography, although the large size of the film presents problems in desorption, especially in gas chromatography. Common applications of TFME are environmental monitoring and in vivo extraction. IT-SPME is a dynamic type of SPME most often coupled with liquid chromatography, in which a liquid sample is pumped through an extraction capillary. It is relatively easily automated with most autosamplers. In the most common form a sorbent is coated on the inside walls of the capillary. Recently, packed types of IT-SPME have been introduced, which can achieve very high extraction efficiencies. In addition, sorbent materials which change their properties according to environmental factors such as temperature, potential and magnetic field seem promising for future development. INCAT/SPDE utilizes internally coated metal needles for extraction. Although similar to IT-SPME, it is used for sampling gaseous compounds by pumping them through the needle. Desorption and analysis is usually performed with a gas chromatograph. INCAT/SPDE has some advantages over fiber-SPME, such as larger sorbent volume and robustness. However, it is currently limited to only polydimethylsiloxane-based sorbents, which limits possible applications. In the experimental part, the possibilities of using allyl isothiocyanate, pentafluorobenzaldehyde(PFBAY) and pentafluorobenzyl chloroformate (PFBCF) in simultaneous extraction and on-fiber derivatization of low molecular weight aliphatic amines were explored. Separation and analysis was performed with gas chromatography-mass spectrometry. Allyl isothiocyanate did not derivatize the analytes. On-fiber derivatization with PFBAY was successful for both ethylamine and methylamine, but the concentrations required to observe signal from the derivatives were too high to use PFBAY for air samples. PFBCF was identified as the most promising reagent, working for both dimethylamine and ethylamine. It was also possible to construct a calibration function for gaseous dimethylamine

Field measurements of biogenic volatile organic compounds in the atmosphere using solid-phase microextraction Arrow

Biogenic volatile organic compounds (BVOCs) emitted by terrestrial vegetation participate in a diversity of natural processes. These compounds impact both on short-range processes, such as on plant protection and communication, and on high-range processes, by e.g. participation on aerosol particle formation and growth. The biodiversity of plant species around the Earth, the vast assortment of emitted BVOCs, and their trace atmospheric concentrations contribute to the high remaining uncertainties about the effects of these compounds on atmospheric chemistry and physics, and call for the development of novel collection devices that can offer portability with improved selectivity and capacity. In this study, a novel solid-phase microextraction (SPME) Arrow sampling system was used for the static and dynamic collection of BVOCs from the boreal forest, and samples were subsequently analysed on-site by gas chromatography-mass spectrometry (GC-MS). This system offers higher sampling capacity and improved robustness than the traditional equilibrium-based SPME techniques, such as SPME fibers. Field measurements were performed in summer 2017 at the Station for Measuring Ecosystem-Atmosphere Relations (SMEAR II) in Hyytiälä, Finland. Complementary laboratory tests were also performed to compare the SPME-based techniques under controlled experimental conditions and to evaluate the effect of temperature and relative humidity on their extraction performance. The most abundant monoterpenes and aldehydes were successfully collected. A significant improvement on sampling capacity was observed with the new SPME Arrow system when compared to SPME fibers, with collected amounts being approximately 2 times higher for monoterpenes and 7-8 times higher for aldehydes. BVOC species exhibited different affinities for the type of sorbent materials used (PDMS/Carbon WR vs. PDMS/DVB). Higher extraction efficiencies were obtained with dynamic collection prior to equilibrium regime, but this benefit during the field measurements was small probably due to the natural agitation provided by the wind. An increase in temperature and relative humidity caused a decrease in the amounts of analytes extracted under controlled experimental conditions, even though the effect was more significant for PDMS/Carbon WR than for PDMS/DVB. Overall, results demonstrated the benefits and challenges of using SPME Arrow for the sampling of BVOCs in the atmosphere.Peer reviewe

Spatiotemporal variation and trends in equivalent black carbon in the Helsinki metropolitan area in Finland

In this study, we present results from 12 years of black carbon (BC) measurements at 14 sites around the Helsinki metropolitan area (HMA) and at one background site outside the HMA. The main local sources of BC in the HMA are traffic and residential wood combustion in fire-places and sauna stoves. All BC measurements were conducted optically, and therefore we refer to the measured BC as equivalent BC (eBC). Measurement stations were located in different environments that represented traffic environment, detached housing area, urban background, and regional background. The measurements of eBC were conducted from 2007 through 2018; however, the times and the lengths of the time series varied at each site. The largest annual mean eBC concentrations were measured at the traffic sites (from 0.67 to 2.64 mu g m(-3)) and the lowest at the regional background sites (from 0.16 to 0.48 mu g m(-3)). The annual mean eBC concentrations at the detached housing and urban background sites varied from 0.64 to 0.80 mu g m(-3) and from 0.42 to 0.68 mu g m(-3), respectively. The clearest seasonal variation was observed at the detached housing sites where residential wood combustion increased the eBC concentrations during the cold season. Diurnal variation in eBC concentration in different urban environments depended clearly on the local sources that were traffic and residential wood combustion. The dependency was not as clear for the typically measured air quality parameters, which were here NOx concentration and mass concentration of particles smaller that 2.5 mu m in diameter (PM2.5). At four sites which had at least a 4-year-long time series available, the eBC concentrations had statistically significant decreasing trends that varied from -10.4 % yr(-1) to -5.9 % yr(-1). Compared to trends determined at urban and regional background sites, the absolute trends decreased fastest at traffic sites, especially during the morning rush hour. Relative long-term trends in eBC and NOx were similar, and their concentrations decreased more rapidly than that of PM2.5. The results indicated that especially emissions from traffic have decreased in the HMA during the last decade. This shows that air pollution control, new emission standards, and a newer fleet of vehicles had an effect on air quality.Peer reviewe

Input-adaptive linear mixed-effects model for estimating alveolar lung-deposited surface area (LDSA) using multipollutant datasets

Lung-deposited surface area (LDSA) has been considered to be a better metric to explain nanoparticle toxicity instead of the commonly used particulate mass concentration. LDSA concentrations can be obtained either by direct measurements or by calculation based on the empirical lung deposition model and measurements of particle size distribution. However, the LDSA or size distribution measurements are neither compulsory nor regulated by the government. As a result, LDSA data are often scarce spatially and temporally. In light of this, we developed a novel statistical model, named the input-adaptive mixed-effects (IAME) model, to estimate LDSA based on other already existing measurements of air pollutant variables and meteorological conditions. During the measurement period in 2017–2018, we retrieved LDSA data measured by Pegasor AQ Urban and other variables at a street canyon (SC, average LDSA = 19.7 ± 11.3 µm2 cm−3) site and an urban background (UB, average LDSA = 11.2 ± 7.1 µm2 cm−3) site in Helsinki, Finland. For the continuous estimation of LDSA, the IAME model was automatised to select the best combination of input variables, including a maximum of three fixed effect variables and three time indictors as random effect variables. Altogether, 696 submodels were generated and ranked by the coefficient of determination (R2), mean absolute error (MAE) and centred root-mean-square difference (cRMSD) in order. At the SC site, the LDSA concentrations were best estimated by mass concentration of particle of diameters smaller than 2.5 µm (PM2.5), total particle number concentration (PNC) and black carbon (BC), all of which are closely connected with the vehicular emissions. At the UB site, the LDSA concentrations were found to be correlated with PM2.5, BC and carbon monoxide (CO). The accuracy of the overall model was better at the SC site (R2=0.80, MAE = 3.7 µm2 cm−3) than at the UB site (R2=0.77, MAE = 2.3 µm2 cm−3), plausibly because the LDSA source was more tightly controlled by the close-by vehicular emission source. The results also demonstrated that the additional adjustment by taking random effects into account improved the sensitivity and the accuracy of the fixed effect model. Due to its adaptive input selection and inclusion of random effects, IAME could fill up missing data or even serve as a network of virtual sensors to complement the measurements at reference stations.Peer reviewe

Modified zeolitic imidazolate framework-8 as solid-phase microextraction Arrow coating for sampling of amines in wastewater and food samples followed by gas chromatography-mass spectrometry

In this study, a novel solid phase microextration (SPME) Arrow was prepared for the sampling of volatile low molecular weight alkylamines (trimethylamine (TMA) and triethylamine (TEA)) in wastewater, salmon and mushroom samples before gas chromatographic separation with mass spectrometer as detector. Acidified zeolitic imidazolate framework-8 (A-ZIF-8) was utilized as adsorbent and poly(vinyl chloride) (PVC) as the adhesive. The custom SPME Arrow was fabricated via a physical adhesion: (1) ZIF-8 particles were suspended in a mixture of tetrahydrofuran (THF) and PVC to form a homogeneous suspension, (2) a non-coated stainless steel SPME Arrow was dipped in the ZIF-8/PVC suspension for several times to obtain a uniform and thick coating, (3) the pore size of ZIF-8 was modified by headspace exposure to hydrochloric acid in order to increase the extraction efficiency for amines. The effect of ZIF-8 concentration in PVC solution, dipping cycles and aging temperature on extraction efficiency was investigated. In addition, sampling parameters such as NaCI concentration, sample volume, extraction time, potassium hydroxide concentration, desorption temperature and desorption time were optimized. The Arrow-to-Arrow reproducibilities (RSDs) for five ZIF-8 coated Arrows were 15.6% and 13.3% for TMA and TEA, respectively. The extraction with A-ZIF-8/PVC Arrow was highly reproducible for at least 130 cycles without noticeable decrease of performance (RSD < 12.5%). Headspace SPME of 7.5 mL sample solution with the fabricated ZIF-8 coated Arrow achieved linear ranges of 1-200 ngmL(-1) for both TMA and TEA. The limit of quantitation (LOQ) was 1 ng mL(-1) for both TMA and TEA. The method was successfully applied to the determination of TMA and TEA in wastewater, salmon and mushroom samples giving satisfactory selectivity towards the studied amines.Peer reviewe

Metabolic alterations in immune cells associate with progression to type 1 diabetes

Aims/hypothesis Previous metabolomics studies suggest that type 1 diabetes is preceded by specific metabolic disturbances. The aim of this study was to investigate whether distinct metabolic patterns occur in peripheral blood mononuclear cells (PBMCs) of children who later develop pancreatic beta cell autoimmunity or overt type 1 diabetes. Methods In a longitudinal cohort setting, PBMC metabolomic analysis was applied in children who (1) progressed to type 1 diabetes (PT1D, n = 34), (2) seroconverted to >= 1 islet autoantibody without progressing to type 1 diabetes (P1Ab, n = 27) or (3) remained autoantibody negative during follow-up (CTRL, n = 10). Results During the first year of life, levels of most lipids and polar metabolites were lower in the PT1D and P1Ab groups compared with the CTRL group. Pathway over-representation analysis suggested alanine, aspartate, glutamate, glycerophospholipid and sphingolipid metabolism were over-represented in PT1D. Genome-scale metabolic models of PBMCs during type 1 diabetes progression were developed by using publicly available transcriptomics data and constrained with metabolomics data from our study. Metabolic modelling confirmed altered ceramide pathways, known to play an important role in immune regulation, as specifically associated with type 1 diabetes progression. Conclusions/interpretation Our data suggest that systemic dysregulation of lipid metabolism, as observed in plasma, may impact the metabolism and function of immune cells during progression to overt type 1 diabetes. Data availability The GEMs for PBMCs have been submitted to BioModels (), under accession number MODEL1905270001. The metabolomics datasets and the clinical metadata generated in this study were submitted to MetaboLights (), under accession number MTBLS1015.Peer reviewe

Opinion: Insights into updating Ambient Air Quality Directive 2008/50/EC

As evidence of adverse health effects due to air pollution continues to increase, the World Health Organization (WHO) recently published its latest edition of the global air quality guidelines (World Health Organization, 2021). Although not legally binding, the guidelines aim to provide a framework in which policymakers can combat air pollution by formulating evidence-based air quality management strategies. In the light of this, the European Union has stated its intent to revise the current ambient air quality directive (2008/50/EC) to more closely resemble the newly published WHO guidelines (European Commission, 2020). This article provides an informed opinion on selected features of the air quality directive that we believe would benefit from a reassessment. The selected features include discussion about (1) air quality sensors as a part of a hierarchical observation network, (2) the number of minimum sampling points and their siting criteria, and (3) new target air pollution parameters for future consideration.Peer reviewe

Measurement report : The influence of traffic and new particle formation on the size distribution of 1–800 nm particles in Helsinki – a street canyon and an urban background station comparison

Peer reviewe

Metabolic alterations in immune cells associate with progression to type 1 diabetes

Aims/hypothesisPrevious metabolomics studies suggest that type 1 diabetes is preceded by specific metabolic disturbances. The aim of this study was to investigate whether distinct metabolic patterns occur in peripheral blood mononuclear cells (PBMCs) of children who later develop pancreatic beta cell autoimmunity or overt type 1 diabetes.MethodsIn a longitudinal cohort setting, PBMC metabolomic analysis was applied in children who (1) progressed to type 1 diabetes (PT1D, n = 34), (2) seroconverted to ≥1 islet autoantibody without progressing to type 1 diabetes (P1Ab, n = 27) or (3) remained autoantibody negative during follow-up (CTRL, n = 10).ResultsDuring the first year of life, levels of most lipids and polar metabolites were lower in the PT1D and P1Ab groups compared with the CTRL group. Pathway over-representation analysis suggested alanine, aspartate, glutamate, glycerophospholipid and sphingolipid metabolism were over-represented in PT1D. Genome-scale metabolic models of PBMCs during type 1 diabetes progression were developed by using publicly available transcriptomics data and constrained with metabolomics data from our study. Metabolic modelling confirmed altered ceramide pathways, known to play an important role in immune regulation, as specifically associated with type 1 diabetes progression.Conclusions/interpretationOur data suggest that systemic dysregulation of lipid metabolism, as observed in plasma, may impact the metabolism and function of immune cells during progression to overt type 1 diabetes.</p

Integrated atomic layer deposition and chemical vapor reaction for the preparation of metal organic framework coatings for solid-phase microextraction Arrow

New chemical vapor reaction (CVR) and atomic layer deposition (ALD)-conversion methods were utilized for preparation of metal organic frameworks (MOFs) coatings of solid phase microextraction (SPME) Arrow for the first time. With simple, easy and convenient one-step reaction or conversion, four MOF coatings were made by suspend ALD iron oxide (Fe2O3) film or aluminum oxide (Al2O3) film above terephthalic acid (H2BDC) or trimesic acid (H3BTC) vapor. UIO-66 coating was made by zirconium (Zr)-BDC film in acetic acid vapor. As the first documented instance of all-gas phase synthesis of SPME Arrow coatings, preparation parameters including CVR/conversion time and temperature, acetic acid volume, and metal oxide film/metal-ligand films thickness were investigated. The optimal coatings exhibited crystalline structures, excellent uniformity, satisfactory thickness (2-7.5 μm), and high robustness (>80 times usage). To study the practical usefulness of the coatings for the extraction, several analytes with different chemical properties were tested. The Fe-BDC coating was found to be the most selective and sensitive for the determination of benzene ring contained compounds due to its highly hydrophobic surface and unsaturated metal site. UIO-66 coating was best for small polar, aromatic, and long chain polar compounds owing to its high porosity. The usefulness of new coatings were evaluated for gas chromatography-mass spectrometer (GC-MS) determination of several analytes, present in wastewater samples at three levels of concentration, and satisfactory results were achieved.Peer reviewe