Vacuum-assisted headspace thin-film microextraction: Theoretical formulation and method optimization for the extraction of polycyclic aromatic hydrocarbons from water samples.

The thin films used in headspace thin-film microextraction (HS-TFME) enable higher sensitivity and superior extraction rates compared to other microextraction approaches, largely due to their greater surface area-to-volume ratio and extraction-phase volume. Nonetheless, analytes exhibiting a low affinity for the headspace and/or large partitioning between the extraction phase and headspace will still require more time to reach equilibrium. In this paper, we detail the development of a new method, termed as vacuum-assisted HS-TFME (Vac-HS-TFME), and we demonstrate how its use of vacuum conditions can accelerate the extraction kinetics of analytes with long equilibration times. The pressure-dependence of the extraction process was formulated and related to improvements in gas-phase diffusivity when lowering the total pressure. Four low-molecular-weight polycyclic aromatic hydrocarbons (PAHs) were used to experimentally verify the improvements in extraction efficiencies enabled by Vac-HS-TFME (vs. HS-TFME). To this end, the effects of temperature and extraction time on Vac-HS-TFME were investigated, with the results being compared to those obtained via regular HS-TFME. Furthermore, the use of a high-capacity sorbent in TFME allowed the positive effects of temperature and vacuum conditions to be combined successfully. Extraction-time profiles constructed at 30 and 50 °C revealed substantial acceleration in the overall extraction kinetics when sampling under vacuum conditions. At 50 °C, all of the analytes extracted via Vac-HS-TFME reached equilibrium within 45 min, whereas only two reached this state under atmospheric pressure. Vac-HS-TFME's analytical performance was evaluated under optimized conditions, and the results were compared to those obtained with regular HS-TFME. The findings revealed that for the two lighter PAHs, the performance of the two methods was similar since they were extracted close or at equilibrium. However, the calibration models for the two heavier PAHs tested here were linear over a wider concentration range (50-10000 ng L-1) when using Vac-HS-TFME, had superior intra-day repeatability (7.4% and 6.7% vs. 11% and 9.3% with regular HS-TFME), and the limits of detection were lower compared to regular HS-TFME (15 and 11 ng L-1 compared to 136 to 100 ng L-1 with regular HS-TFME). Finally, the analysis of spiked wastewater effluent samples showed that the matrix did not affect extraction. The proposed Vac-HS-TFME approach combines the advantages of low-pressure sampling and high-capacity sorbent, and has a great potential for future applications in food, flavour, environmental, and biological analyses.

Plastic pellets, meso- and microplastics on the coastline of Northern Crete: Distribution and organic pollution.

Plastic pollution in the marine environment is one of the foremost environmental problems of our time, as it affects wildlife and human health both directly and indirectly through the effects of contaminants carried by microplastics. This study investigates the temporal and spatial distribution of plastic pellets and fragments in sandy beaches along the coastline of Northern Crete, during 2013. Their densities varied throughout the year in each beach, with highest densities during the summer and towards the upper parts of the beaches. The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) sorbed on microplastics sampled from nine sandy beaches of Northern Crete was quantified using Gas chromatography - Ion Trap Mass Spectrometry (GC-ITMS). PAHs concentrations ranged from non-detectable levels to 1592 ng/g and fluctuated between sampling periods. Based on the observed patterns of meso- and microplastics distribution, practical guidelines are proposed to minimize the entrance of microplastics into the seawater wherefrom they are exceptionally difficult to collect, if mitigation actions are to be applied.

Vacuum-assisted headspace-solid phase microextraction for determining volatile free fatty acids and phenols. Investigations on the effect of pressure on competitive adsorption phenomena in a multicomponent system.

This work proposes a new vacuum headspace solid-phase microextraction (Vac-HSSPME) method combined to gas chromatography-flame ionization detection for the determination of free fatty acids (FFAs) and phenols. All target analytes of the multicomponent solution were volatiles but their low Henry's Law constants rendered them amenable to Vac-HSSPME. The ability of a new and easy to construct Vac-HSSPME sampler to maintain low-pressure conditions for extended sampling times was concurrently demonstrated. Vac-HSSPME and regular HSSPME methods were independently optimized and the results were compared at all times. The performances of four commercial SPME fibers and two polymeric ionic liquid (PIL)-based SPME fibers were evaluated and the best overall results were obtained with the adsorbent-type CAR/PDMS fiber. For the concentrations used here, competitive displacement became more intense for the smaller and more volatile analytes of the multi-component solution when lowering the sampling pressure. The extraction time profiles showed that Vac-HSSPME had a dramatic positive effect on extraction kinetics. The local maxima of adsorbed analytes recorded with Vac-HSSPME occurred faster, but were always lower than that with regular HSSPME due to the faster analyte-loading from the multicomponent solution. Increasing the sampling temperature during Vac-HSSPME reduced the extraction efficiency of smaller analytes due to the enhancement in water molecule collisions with the fiber. This effect was not recorded for the larger phenolic compounds. Based on the optimum values selected, Vac-HSSPME required a shorter extraction time and milder sampling conditions than regular HSSPME: 20 min and 35 °C for Vac-HSSPME versus 40 min and 45 °C for regular HSSPME. The performance of the optimized Vac-HSSPME and regular HSSPME procedures were assessed and Vac-HSSPME method proved to be more sensitive, with lower limits of detection (from 0.14 to 13 µg L-1), and better intra-day precision (relative standard deviations values < 10% at the lowest spiked level) than regular HSSPME for almost all target analytes. The proposed Vac-HSSPME method was successfully applied to quantify FFAs and phenols in milk and milk derivatives samples.

Plastic pellets sorptive extraction: Low-cost, rapid and efficient extraction of polycyclic aromatic hydrocarbons from environmental waters.

For the first time, plastic pellets, a low-cost and easy to reach industrial raw material, are reported as an efficient sorbent material for the laboratory extraction of polycyclic aromatic hydrocarbons (PAHs) from environmental waters. The proposed methodology, termed plastic pellets sorptive extraction (P2SE), consisted of a two-step procedure whereby target analytes were initially adsorbed onto the surface of three low-density polyethylene (LDPE) pellets and then desorbed using microliters of an organic solvent. Interphase mass transfer was greatly accelerated by means of vortex agitation. Organic extracts were analyzed by means of liquid chromatography-fluorescence detection. Different experimental parameters were controlled and the optimum conditions found were: three LDPE pellets (∼80 mg) added to 20 mL aqueous sample (20% w:v NaCl) followed by vortex agitation at 3000 rpm; for desorption, the three LDPE pellets were immersed in 100 µL of acetonitrile and the mixture was shaken at 3000 rpm for 5 min using the vortex agitator. The calculated calibration curves gave high levels of linearity yielding coefficients of determination (r(2)) greater than 0.9913. The precision of the proposed method was found to be good and the limits of the detection were calculated in the low ng L(-1) level. Matrix effects were determined by applying the proposed method to spiked river water, treated municipal wastewater and seawater samples. To compensate for the low recoveries of the more hydrophobic PAHs in spiked effluent wastewater and seawater samples the standard addition methodology was applied. The proposed method was applied to the determination of target pollutants in real seawater samples using the standard addition method. Overall, the performance of the proposed P2SE method suggests that the use of inexpensive and easy to reach sorbent materials for extracting analytes in the laboratory merits more intensive investigation.

Design and testing of a new sampler for simplified vacuum-assisted headspace solid-phase microextraction.

The design and testing of a new and low-cost experimental setup used for vacuum-assisted headspace solid-phase microextraction (Vac-HSSPME) is reported here. The device consists of a specially designed O-ring seal screw cap offering gas-tight seal to commercially available headspace vials. The new polytetrafluoroethylene (PTFE) cap was molded by a local manufacturer and had a hole that could tightly accommodate a septum. All operations were performed through the septum: air evacuation of the sampler, sample introduction and HSSPME sampling. The analytical performance of the new sampler was evaluated using 22 mL headspace vials with 9 mL water samples spiked with polychlorinated biphenyls (PCBs). Several experimental parameters were controlled and the optimized conditions were: 1000 rpm agitation speed; 30 min extraction time; 40 °C sampling temperature; polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber. The lack of accurate Henry's law constant (KH) values and information regarding how they change with temperature was a major limitation in predicting the phase location of evaporation resistance during Vac-HSSPME. Nevertheless, the combined effects of system conditions indicated the increasing importance of gas phase resistance with increasing degree of PCBs chlorination. Stirring enhancements were not recorded for the higher chlorinated PCBs suggesting that the hyperhydrophobic gas/water interface was the preferred location for these compounds. Analytically, the developed method was found to yield linear calibration curves with limits of detection in the sub ng L(-1) level and relative standard deviations ranging between 5.8 and 14%. To compensate for the low recoveries of the higher chlorinated PCB congeners in spiked river water the standard addition methodology was applied. Overall, the compact design of the new and reusable sample container allows efficient HSSPME sampling of organic analytes in water within short extraction times and at low sampling temperatures compared to other published HSSPME methods.

Vacuum-assisted headspace solid phase microextraction of polycyclic aromatic hydrocarbons in solid samples.

For the first time, Vacuum Assisted Headspace Solid Phase Microextraction (Vac-HSSPME) is used for the recovery of polycyclic aromatic hydrocarbons (PAHs) from solid matrices. The procedure was investigated both theoretically and experimentally. According to the theory, reducing the total pressure increases the vapor flux of chemicals at the soil surface, and hence improves HSSPME extraction kinetics. Vac-HSSPME sampling could be further enhanced by adding water as a modifier and creating a slurry mixture. For these soil-water mixtures, reduced pressure conditions may increase the volatilization rates of compounds with a low K(H) present in the aqueous phase of the slurry mixture and result in a faster HSSPME extraction process. Nevertheless, analyte desorption from soil to water may become a rate-limiting step when significant depletion of the aqueous analyte concentration takes place during Vac-HSSPME. Sand samples spiked with PAHs were used as simple solid matrices and the effect of different experimental parameters was investigated (extraction temperature, modifiers and extraction time). Vac-HSSPME sampling of dry spiked sand samples provided the first experimental evidence of the positive combined effect of reduced pressure and temperature on HSSPME. Although adding 2 mL of water as a modifier improved Vac-HSSPME, humidity decreased the amount of naphthalene extracted at equilibrium as well as impaired extraction of all analytes at elevated sampling temperatures. Within short HSSPME sampling times and under mild sampling temperatures, Vac-HSSPME yielded linear calibration curves in the range of 1-400 ng g(-1) and, with the exception of fluorene, regression coefficients were found higher than 0.99. The limits of detection for spiked sand samples ranged from 0.003 to 0.233 ng g(-1) and repeatability from 4.3 to 10 %. Finally, the amount of PAHs extracted from spiked soil samples was smaller compared to spiked sand samples, confirming that soil could bind target analytes more strongly and thus decrease the readily available fraction of target analytes.

Downsizing vacuum-assisted headspace solid phase microextraction.

Recently, we proposed a new headspace solid-phase microextraction (HSSPME) procedure, termed vacuum-assisted HSSPME (Vac-HSSPME), where headspace sampling of 10mL aqueous sample volumes took place in 500 or 1000mL sample containers under vacuum conditions. In the present study, we downsized the extraction device to a 22mL modified sample vial and concluded that changes in the final total pressure of the pre-evacuated vial following sample introduction were sufficiently low to allow efficient Vac-HSSPME sampling. The downsized extraction device was used to extract five low molecular weight polycyclic aromatic hydrocarbons and several experimental parameters were controlled and optimized. For those compounds whose mass transfer resistance in the thin gas-film adjacent to the gas/sample interface controls evaporation rates, reducing the total pressure during HSSPME sampling dramatically enhanced extraction kinetics in the 22mL modified vial. Humidity was found to affect the amount of naphthalene (intermediate KH compound) extracted by the fiber at equilibrium as well as impair extraction of all analytes at elevated sampling temperatures. All the same, the high extraction efficiency and very good sensitivity achieved at room temperature and within short sampling times comprised the most important features of Vac-HSSPME in this downsized extraction device. Analytically, the developed method was found to yield linear calibration curves with limits of detection in the low ngL(-1) level and relative standard deviations ranging between 1.3 and 5.8%. Matrix was found not to affect extraction.

Vacuum-assisted headspace solid phase microextraction: improved extraction of semivolatiles by non-equilibrium headspace sampling under reduced pressure conditions.

A new headspace solid-phase microextraction (HSSPME) procedure carried out under vacuum conditions is proposed here where sample volumes commonly used in HSSPME (9 mL) were introduced into pre-evacuated commercially available large sampling chambers (1000 mL) prior to HSSPME sampling. The proposed procedure ensured reproducible conditions for HSSPME and excluded the possibility of analyte losses. A theoretical model was formulated demonstrating for the first time the pressure dependence of HSSPME sampling procedure under non equilibrium conditions. Although reduced pressure conditions during HSSPME sampling are not expected to increase the amount of analytes extracted at equilibrium, they greatly increase extraction rates compared to HSSPME under atmospheric pressure due to the enhancement of evaporation rates in the presence of an air-evacuated headspace. The effect is larger for semivolatiles whose evaporation rates are controlled by mass transfer resistance in the thin gas film adjacent to the sample/headspace interface. Parameters that affect HSSPME extraction were investigated under both vacuum and atmospheric conditions and the experimental data obtained were used to discuss and verify the theory. The use of an excessively large headspace volume was also considered. The applicability of Vac-HSSPME was assessed using chlorophenols as model compounds yielding linearities better than 0.9915 and detection limits in the low-ppt level. The repeatability was found to vary from 3.1 to 8.6%.

Effect of Henry's law constant and operating parameters on vacuum-assisted headspace solid phase microextraction.

Nonequilibrium headspace solid-phase microextraction (HSSPME) sampling under vacuum conditions may dramatically improve extraction kinetics compared to regular HSSPME at room temperature. This paper investigates the effects of organic analyte properties and sampling parameters (headspace volume and sample agitation) on vacuum-assisted HSSPME (Vac-HSSPME). It was found that at room temperature, acceleration effects on extraction rates induced by reducing the total pressure of the sample container are important for those compounds where the Henry's law constant, K(H), is close or below the reported threshold values for low K(H) solutes. For these compounds evaporation rate is controlled by mass transfer resistance in the thin gas-film adjacent to the gas/sample interface and reducing the total pressure will increase evaporation rates and result in a faster overall extraction process. Conversely, for analytes with an intermediate K(H) value, Vac-HSSPME is not expected to improve extraction rates compared to regular HSSPME given that mass transfer resistance in the liquid-film becomes important. In accordance with the theory, at equilibrium, the amount of analyte extracted by the SPME fiber is not affected by the pressure conditions inside the sample container. Furthermore, Vac-HSSPME extraction kinetics for low K(H) analytes were marginally affected by the tested change in headspace volume as evaporation rates dramatically increase under reduced pressure conditions and the sample responds much faster to the concentration drops in the headspace when compared to regular HSSPME. At equilibrium however, increasing the headspace volume may result in a loss of sensitivity for Vac-HSSPME similar to that observed for regular HSSPME. As expected, stirring the liquid sample was found to improve Vac-HSSPME. Finally, the method yielded a linearity of 0.998 and detection limits in the ppt level. The precision varied between 1.8% and 8.4%.

Vortex-assisted liquid-liquid microextraction of octylphenol, nonylphenol and bisphenol-A.

A new and fast equilibrium-based solvent microextraction technique termed vortex-assisted liquid-liquid microextraction (VALLME) has been developed and used for the trace analysis of octylphenol, nonylphenol and bisphenol-A in water and wastewater samples. According to VALLME, dispersion of microvolumes of a low density extractant organic solvent into the aqueous sample is achieved by using for the first time vortex mixing, a mild emulsification procedure. The fine droplets formed could extract target analytes towards equilibrium faster because of the shorter diffusion distance and larger specific surface area. Upon centrifugation the floating extractant acceptor phase restored its initial single microdrop shape and was used for high-performance liquid chromatographic analysis. Different experimental parameters were controlled and the optimum conditions found were: 50 microl of octanol as the extractant phase; 20 ml aqueous donor samples; a 2 min vortex extraction time with the vortex agitator set at a 2500 rpm rotational speed; centrifugation for 2 min at 3500 rpm; no ionic strength or pH adjustment. The calculated calibration curves gave high levels of linearity yielding correlation coefficients (r(2)) greater than 0.9935. The repeatability and reproducibility of the proposed method were found to be good and the limits of the detection were calculated in the low microg l(-1) level ranging between 0.01 and 0.07 microg l(-1). Matrix effects were determined by applying the proposed method to spiked tap, river water and treated municipal wastewater samples. The proposed method was finally applied to the determination of target pollutants in real wastewater effluent samples using the standard addition method.