Large Volume Injection-gas Chromatography-mass Spectrometry Research Articles

LVI and DI-SPME Combined with GC/MS and GC/MS for Volatile Chemical Profile Investigation and Cytotoxic Power Evaluation of Essential Oil and Hydrolate from Cannabis sativa L. cv. Carmagnola.

Cannabis sativa L. is a plant that has been cultivated since ancient times thanks to its various uses. Even its extraction products, such as essential oil and hydrolate, having a varied chemical composition and rich in bioactive components, find wide use in different sectors, gathering ever-increasing interest over time. In this work, the essential oil of Cannabis sativa L. cv. Carmagnola was characterized by using Gas Chromatography/Mass Spectrometry (GC/MS) and, for the first time, the chemical profile of the hydrolate was also described through different analytical techniques such as Large-Volume Injection Gas Chromatography/Mass Spectrometry (LVI-GC/MS) and Direct Immersion-Solid Phase Microextraction-Gas Chromatography/Mass spectrometry (DI-SPME-GC/MS), in order to provide a more complete compositional profile. The results of the analyses conducted on the hydrolate highlighted a high content of α-terpineol; on the other side, in the essential oil, a prevalence of monoterpenes, with α-pinene and limonene as the characterizing components, was detected. Both matrices were also investigated to evaluate their cytotoxic activity by using a panel of cancer cell lines derived from different histotypes such as melanoma (A375, LOX IMVI), non-small cell lung cancer (H1299, A549), colon (HT29) and pancreatic (L3.6) cancer cell lines. The obtained data demonstrated that essential oil was more effective than hydrolate in terms of reduction in cell viability.

A Fast and Validated High Throughput Bar Adsorptive Microextraction (HT-BAµE) Method for the Determination of Ketamine and Norketamine in Urine Samples.

We developed, optimized and validated a fast analytical cycle using high throughput bar adsorptive microextraction and microliquid desorption (HT-BAμE-μLD) for the extraction and desorption of ketamine and norketamine in up to 100 urine samples simultaneously, resulting in an assay time of only 0.45 min/sample. The identification and quantification were carried out using large volume injection-gas chromatography-mass spectrometry operating in the selected ion monitoring mode (LVI-GC-MS(SIM)). Several parameters that could influencing HT-BAµE were assayed and optimized in order to maximize the recovery yields of ketamine and norketamine from aqueous media. These included sorbent selectivity, desorption solvent and time, as well as shaking rate, microextraction time, matrix pH, ionic strength and polarity. Under optimized experimental conditions, suitable sensitivity (1.0 μg L−1), accuracy (85.5–112.1%), precision (≤15%) and recovery yields (84.9–105.0%) were achieved. Compared to existing methods, the herein described analytical cycle is much faster, environmentally friendly and cost-effective for the quantification of ketamine and norketamine in urine samples. To our knowledge, this is the first work that employs a high throughput based microextraction approach for the simultaneous extraction and subsequent desorption of ketamine and norketamine in up to 100 urine samples simultaneously.

High throughput bar adsorptive microextraction: A simple and effective analytical approach for the determination of nicotine and cotinine in urine samples

A simple, effective, convenient and environmentally friendly methodology using high throughput bar adsorptive microextraction (HT-BAμE) with microliquid desorption in combination with large volume injection-gas chromatography-mass spectrometry operating in the selected-ion monitoring acquisition mode (LVI–GC–MS(SIM)) was applied for the determination of nicotine and cotinine in urine samples. Under optimized experimental conditions, the developed methodology allowed for linear dynamic ranges between 20.0 and 2000.0 μg L-1 with determination coefficients of 0.9991 and 0.9992, as well as average recovery yields of 61.7–67.5% and 53.9–57.8% for nicotine and cotine, respectively. The developed methodology was applied to monitor urine samples from 86 volunteers having different smoking habits, where nicotine and cotinine were quantified in the range from 23.6 to 2612.6 μg L-1.The target compounds were extracted in a HT-BAμE apparatus, which allows for simultaneous microextraction and subsequent back-extraction of up to 100 samples. This is a major improvement over other microextraction techniques.The data from the proposed methodology were satisfactory and in line with current green analytical chemistry guidelines, and proved to be an effective sample preparation alternative with substantial potential for high throughput bioanalysis.

Dual-hollow fiber microextraction (dual-HFμE) - application for monitoring trace levels of organochlorine pesticides in real matrices

ABSTRACT In this contribution, the features and the advantages of the modified hollow fibre microextraction (HFµE) technique are discussed, by using two membranes (dual-HFµE) per sample, loaded with convenient organic solvents. The new approach proposed combined with micro-liquid desorption followed by large volume injection-gas chromatography-mass spectrometry operating in the selected-ion monitoring acquisition mode, [dual-HFμE-μLD/LVI-GC-MS(SIM)], was applied for trace analysis of 17 organochlorine pesticides (OCPs) in real matrices. By using dual-HFµE devices embedded with n-heptane and toluene (≈ 50 µL), fast kinetics (2 h) and selectivity enhancement were achieved to monitor 17 OCPs, particularly for the benzene hexachlorides, with convenient precision (RSD < 16%). Assays performed on 25 mL aqueous samples spiked with OCPs at the trace level yielded average recoveries between (40.6 ± 6.8) % and (101.7 ± 8.0) %, low detection limits (0.01–0.02 µg L−1), as well as good linear dynamic ranges (0.07–10.00 µg L−1) with suitable determination coefficients (r 2 > 0.9941). Through the standard addition method, the proposed methodology demonstrated good performance to monitor OCPs at the trace level in several types of matrices, including tap water, wastewater, soil, tea, and tomato samples. Besides the performance obtained and the wide applicability demonstrated, the dual-HFμE technique proved to be user-friendly, eco-friendly, cost-effective, and very competitive for routine work, being a remarkable alternative over other well-established microextraction techniques for trace analysis of priority and emerging compounds in real matrices.

Trace detection of explosives with a unique large volume injection gas chromatography-mass spectrometry (LVI-GC-MS) method

Highly sensitive splitless programmed temperature vaporizing (PTV)-large volume injection (LVI)-GC-MS-negative chemical ionization (NCI) method was developed and validated for the trace detection of explosives and related compounds from environmental matrices.

Off-line microextraction by packed sorbent combined with on solid support derivatization and GC-MS: Application for the analysis of five pyrethroid metabolites in urine samples

A novel, fast and eco-friendly analytical method using microextraction by packed sorbent coupled to large volume injection-gas chromatography-mass spectrometry (MEPS-LVI-GC-MS) was developed for the determination of five pyrethroid metabolites (cis-2,2-dimethyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-cyclopropanecarboxylic acid, cis/trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acids, cis-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid and 3-phenoxybenzoic acid) in human urine. MEPS was performed off-line using a manually-operated semiautomatic syringe (eVol), and several parameters including the sample pH, extraction sorbent, washing solvent, volume and type of elution solvent and number of draw-eject cycles were optimized. Analytes were extracted from enzymatically hydrolyzed urine using a C18 solid phase with subsequent simultaneous derivatization and elution with a mixture of 1,1,1,3,3,3-hexafluoroisopropanol and diisopropylcarbodiimide in n-hexane (on-line derivatization). The optimized method was validated, with linearity established from 0.05 to 25ngmL−1 and R values > 0.99. Obtained quantification limits were in the range of 0.06–0.08ngmL−1, and the precision expressed as relative standard deviation (RSD) was below 14% for all of the analytes. The method was cross-validated with a reference approach based on liquid-liquid extraction-gas chromatography-mass spectrometry (LLE-GC-MS) by analyzing 21 urine samples.

Dispersive liquid-liquid microextraction for the determination of nitrophenols in soils by microvial insert large volume injection-gas chromatography–mass spectrometry

A rapid and sensitive procedure for the determination of six NPs in soils by gas chromatography and mass spectrometry (GC–MS) is proposed. Ultrasound assisted extraction (UAE) is used for NP extraction from soil matrices to an organic solvent, while the environmentally friendly technique dispersive liquid-liquid microextraction (DLLME) is used for the preconcentration of the resulting UAE extracts. NPs were derivatized by applying an “in-situ” acetylation procedure, before being injected into the GC–MS system using microvial insert large volume injection (LVI). Several parameters affecting UAE, DLLME, derivatization and injection steps were investigated. The optimized procedure provided recoveries of 86–111% from spiked samples. Precision values of the procedure (expressed as relative standard deviation, RSD) lower than 12%, and limits of quantification ranging from 1.3 to 2.6ngg−1, depending on the compound, were obtained. Twenty soil samples, obtained from military, industrial and agricultural areas, were analyzed by the proposed method. Two of the analytes were quantified in two of the samples obtained from industrial areas, at concentrations in the 4.8–9.6ngg−1 range.

Influence of the drying step within disk-based solid-phase extraction both on the recovery and the limit of quantification of organochlorine pesticides in surface waters including suspended particulate matter

In this study, 21 organochlorine pesticides (OCPs) were determined based on sample preparation using solid-phase extraction disks (SPE disks) coupled with programmable temperature vaporizer (PTV)—large-volume injection gas–chromatography mass spectrometry (LVI-GC–MS). The work includes a comprehensive testing scheme on the suitability of the method for routine analysis of surface and drinking water including suspended particulate matter (SPM) with regard to requirements derived from the European Water Framework Directive (WFD, Directive 2000/60/EC). SPM is an important reservoir for OCPs, which contributes to the transport of these compounds in the aquatic environment. To achieve the detection limits required by the WFD, a high pre-concentration factor during sample preparation is necessary, which was achieved by disk SPE in this study. The performance of disk SPE is strongly influenced by the drying step, which could be significantly improved by effective elimination of the residual water by combination of a high vacuum pump and a low humidity atmosphere. Detection limits of the WFD in the ng/L range were achieved by large volume injection of 100μL sample extract. The recoveries ranged from 82% to 117% with an RSD smaller than 13%. The applicability of this method to natural samples was tested for instrumental qualification and system suitability evaluation. Successful participation in an interlaboratory comparison proved the suitability of the method for routine analysis.

Analysis of polycyclic aromatic hydrocarbons in aqueous samples by large volume injection gas chromatography–mass spectrometry using the through oven transfer adsorption desorption interface

A new procedure for the determination of 17 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples by large volume injection–gas chromatography–mass spectrometry (LVI–GC–MS) using the Through Oven Transfer Adsorption Desorption (TOTAD) interface with nitrogen for solvent elimination is developed and validated. Up to 75mL of aqueous samples were injected to be sure that good solvent elimination were achieved, although 500µL were sufficient to achieve the required sensitivity.The performance of the developed method can be considered good: the relative standard deviation (RSD), (n=3) was lower than 13.8% for all the target analytes, the concentration of each PAH being 0.25μgL−1, the limit of detection and limit of quantitation ranged from 21.5 to 211.0 ng L−1 and from 71.7 to 703.3ngL−1 respectively, and the correlation coefficients (R2) were all higher than 0.9764 in the 1–16μgL−1 range.

Application of SPE followed by large-volume injection GC/MS for the analysis of geosmin and 2-methylisoborneol in water

A new method comprising solid phase extraction (SPE) and subsequent large volume injection-gas chromatography/mass spectrometry (LVI-GC/MS) was developed to analyze 2-methylisoborneol (2-MIB) and geosmin in water.

Dispersive Micro Solid‐phase Extraction Coupled with Ultrasound‐assisted Solvent Desorption for Determination of Synthetic Polycyclic and Nitro‐aromatic Musks in Aqueous Samples

AbstractAn optimized method for the determination of five synthetic polycyclic: celestolide (ADBI), phantolide (AHMI), traseolide (ATII), galaxolide (HHCB), tonalide (AHTN), and two nitro‐aromatic musks: musk xylene (MX) and musk ketone (MK), in water samples is described. The method involves a dispersive micro solid‐phase extraction (D‐μ‐SPE) plus ultrasound‐assisted solvent desorption (UASD) prior to their determination by gas chromatography‐mass spectrometry (GC‐MS) using the selected ion storage (SIS) mode. Factors affecting the extraction efficiency of the target analytes from water samples and ultrasound‐assisted solvent desorption were optimized by a Box‐Behnken design method. The optimal extraction conditions involved immersing 10.1 mg of a typical octadecyl (C18) bonded silica adsorbent (i.e., ENVI‐18) in a 50 mL water sample. After 10.4 min of extraction by vigorously shaking, the adsorbent was collected and dried on a filter, and the target musks were desorbed by ultrasound‐assisted for 38 sec with n‐hexane (200 μL) as the desorption solvent. A 10 μL aliquot was then directly determined by large‐volume injection GC‐MS. The limits of quantitation (LOQs) were 1.2 to 5 ng/L. The precision for these analytes, as indicated by relative standard deviations (RSDs), were less than 11% for both intra‐ and inter‐day analysis. Accuracy, expressed as the mean extraction recovery, was between 74% and 92%. A preliminary analysis of the effluents from municipal wastewater treatment plants (MWTP) and river water samples revealed that HHCB and AHTN were the two most commonly detected synthetic musks; their concentration were determined to range from 88 to 690 ng/L for effluent samples, and 5 to 320 ng/L for river water samples. This is a simple, low cost, effective, and eco‐friendly analytical method.

Determination of tributyltin in environmental water matrices using stir bar sorptive extraction with in-situ derivatisation and large volume injection-gas chromatography–mass spectrometry

Stir bar sorptive extraction with in-situ derivatization using sodium tetrahydridoborate (NaBH4) followed by liquid desorption and large volume injection-gas chromatography–mass spectrometry detection under the selected ion monitoring mode (SBSE(NaBH4)in-situ–LD/LVI-GC–MS(SIM)) was successfully developed for the determination of tributyltin (TBT) in environmental water matrices. NaBH4 proved to be an effective and easy in-situ speciation agent for TBT in aqueous media, allowing the formation of adducts with enough stability and suitable polarity for SBSE analysis. Assays performed on water samples spiked at the 10.0μg/L, yielded convenient recoveries (68.2±3.0%), showed good accuracy, suitable precision (RSD<9.0%), low detection limits (23ng/L) and excellent linear dynamic range (r2=0.9999) from 0.1 to 170.0µg/L, under optimized experimental conditions. By using the standard addition method, the application of the present methodology to real surface water samples allowed very good performance at the trace level. The proposed methodology proved to be a feasible alternative for routine quality control analysis, easy to implement, reliable and sensitive to monitor TBT in environmental water matrices.

Improvements on bar adsorptive microextraction (BAμE) technique–Application for the determination of insecticide repellents in environmental water matrices

Bar adsorptive microextraction combined with micro-liquid desorption followed by large volume injection-gas chromatography-mass spectrometry operating in the selected-ion monitoring acquisition mode (BAµE-µLD/LVI-GC-MS(SIM)), is proposed for the determination of trace levels of three insecticide repellents (N,N-diethyl-meta-toluamide (DEET), cis and trans permethrin (PERM)) in environmental water matrices. By comparing different sorbent coatings (five activated carbons and six polymers) through BAµE, an activated carbon (AC2) proved to be the best compromise between selectivity and efficiency, even against polydimethylsiloxane through stir bar sorptive extraction. The novel improvement proposed on the back-extraction stage performed in a single step, by reducing the desorption solvent volume at the microliter level, demonstrated remarkable performance turning possible to save time, making easier the practical manipulation and more environmentally friendly. Assays performed by BAµE(AC2)-µLD/LVI-GC-MS(SIM) on 25 mL of ultrapure water samples spiked at the 1.0 μg/L level, yielded recoveries ranging from 73.8±8.8% (trans-PERM) to 96.4±9.9% (DEET), under optimised experimental conditions. The analytical performance showed convenient detection limits (8-20 ng/L) and good linear dynamic ranges (0.04-4.0 µg/L) with suitable determination coefficients (r(2)>0.9963, DEET). Excellent repeatability were also achieved through intraday (RSD<14.9%) and interday (RSD<11.9%) experiments. The novel improvement on downsizing the BAµE device to half-size proved to be either a promising option in forthcoming to reduce still more the desorption solvent volume without losing microextraction efficiency. By using the standard addition methodology, the application of the present analytical approach on tap, ground, river, swimming-pool and estuary water samples revealed good sensitivity at trace level and absence of matrix effects.

Determination of organic priority pollutants in the low nanogram-per-litre range in water by solid-phase extraction disk combined with large-volume injection/gas chromatography–mass spectrometry

Polybrominated diphenyl ethers, polychlorinated biphenyls, polycyclic aromatic hydrocarbons and organochlorine pesticides in the low nanogram-per-litre range in water were enriched by solid-phase extraction (SPE) disks and their concentration determined by large-volume injection/gas chromatography-mass spectrometry (LVI/GC-MS). One advantage of using SPE disks in comparison with SPE cartridges is that suspended particulate matter (SPM) does not have to be separated prior to the enrichment step, which saves time and effort. To increase the sensitivity of the method, the SPE disk procedure was combined with LVI/GC-MS, which has not been reported so far for water analysis. The method was calibrated in ranges from 0.25 to 2.5 ng/L and from 2.5 to 25 ng/L. The average recovery was 76% at an analyte concentration of 2.5 ng/L. The limits of quantification, defined at a signal-to-noise ratio of 6:1, reach from 0.1 to 24.0 ng/L and are up to 400 times lower than previously reported in water analysis. By the developed SPE/LVI/GC-MS method, it is possible to investigate the whole water sample without prior separation of the SPM within 2 h including GC-MS analysis.

Determination of polycyclic and nitro musks in environmental water samples by means of microextraction by packed sorbents coupled to large volume injection-gas chromatography–mass spectrometry analysis

In this work the development and validation of a new procedure for the simultaneous determination of 9 nitro and polycyclic musk compounds: musk ambrette (MA), musk ketone (MK), musk mosken (MM), celestolide (ADBI), phantolide (AHMI), tonalide (AHTN), traseolide (ATII), cashmeran (DPMI) and galaxolide (HHCB) in environmental water samples (estuarine and wastewater) using microextraction by packed sorbent (MEPS) followed by large volume injection-gas chromatography–mass spectrometry (LVI-GC–MS) was carried out. Apart from the optimization of the different variables affecting MEPS (i.e., nature of the sorbent, nature of the solvent elution, sample load, and elution/injection volume) extraction recovery was also evaluated, not only for water samples but also for environmental water matrices such as estuarine and waste water. The use of two deuterated analogs ([2H3]-AHTN and [2H15]-MX) was successfully evaluated in order to correct matrix effect in complex environmental matrices such as influent samples from wastewater treatment plants. Method detection limits (MDLs) ranged from 5 to 25ngL−1, 7 to 39ngL−1 and 8 to 84ngL−1 for influent, effluent and estuarine samples, respectively. Apparent recoveries were higher than 75% for all target compounds in all the matrices studied (estuarine water and wastewater) and the precision of the method, calculated as relative standard deviation (RSD), was below 13.2% at 200ngL−1 concentration level and below 14.9% at low level (20ngL−1 for all the target analytes, except for AHTN which was set at 40ngL−1 and HHCB at 90ngL−1, due to the higher MDL values presented by those target compounds). Finally, this MEPS procedure was applied to the determination of the target analytes in water samples, including estuarine and wastewater, from two estuaries, Urdaibai (Spain) and Adour (France) and an established stir-bar sorptive extraction-liquid desorption/large volume injection-gas chromatography–mass spectrometry (SBSE-LD/LVI-GC–MS) method was performed in parallel for comparison. Results were in good agreement for all the analytes determined, except for DPMI.

Determination of cyclic volatile methylsiloxanes in water, sediment, soil, biota, and biosolid using large-volume injection–gas chromatography–mass spectrometry

Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid–solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection–gas chromatography−mass spectrometry (LVI−GC−MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI–GC–MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS’s associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4°C were stable within 29d; however, significant depletion of D6 (60–70%) occurred only after 3d. Whereas cVMS in sewage influent and effluent were stable at 4°C within 21d. cVMS in sediment sealed in amber glass jars at −20°C and in pentane extracts in vials at −15°C were stable during 1month under both storage conditions.

Fully automated determination of macrocyclic musk fragrances in wastewater by microextraction by packed sorbents and large volume injection gas chromatography–mass spectrometry

A fully automated method has been developed for the determination of eight macrocyclic musk fragrances in urban wastewater. The procedure includes the enrichment of the analytes by microextraction by packed sorbent (MEPS) followed by large volume injection–gas chromatography–mass spectrometry (LVI–GC–MS). The main factors in the MEPS technique were optimized. For all of the analytes, the highest enrichment factors were achieved when 4mL samples were extracted by using C18 MEPS-sorbent and 50μL of ethyl acetate were used for desorption. The eluate was directly analysed by GC–MS. Detection limits were found to be between 5ngL−1 and 10ngL−1, depending on the target analytes. In addition, under optimized conditions, the method gave good levels of intra-day and inter-day repeatability in wastewater samples with relative standard deviation (RSD) (n=3, 1000ngL−1) less than 5% and 9%, respectively. The applicability of the method was tested with wastewater samples from two influent and effluent urban wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed the presence of most of the macrocylic musks at concentrations higher than the method quantification limits (MQLs), being the most abundant analyte ambrettolide at 9.29μgL−1. In addition, the analyses of effluent urban wastewater showed a decrease in the concentrations with macrocyclic musk concentrations of between not detected (n.d.) and 2.26μgL−1 being detected.

Comparison of the selectivity of different sorbent phases for bar adsorptive microextraction—Application to trace level analysis of fungicides in real matrices

Bar adsorptive micro-extraction combined with liquid desorption followed by large volume injection–gas chromatography–mass spectrometry operating in the selected-ion monitoring acquisition mode (BAμE–LD/LVI–GC–MS(SIM)) was developed for the determination of trace levels of ten fungicides (azoxystrobin, difenoconazole, metalaxyl-M, myclobutanil, penconazole, tebuconazole, flusilazole, cyprodinil, procymidone and benalaxyl) in aqueous matrices. By comparing different sorbent coatings (two activated carbons, two styrene–divinylbenzene and one modified pyrrolidone polymers) through BAμE, the latter phase showed much higher selectivity and capacity offering multiple mechanisms of interaction, even against polydimethylsiloxane by stir bar sorptive extraction. Assays performed on 25mL of water samples spiked at the 0.8μg/L level, yielded recoveries ranging from 100.0 to 107.8%, under optimized experimental conditions; BAμE(modified pyrrolidone) – equilibrium time: 4h (1000rpm), pH 5.5; LD – solvent:methanol/acetonitrile (1/1), 15min with sonification. The analytical performance showed convenient detection limits (4.0–30.0ng/L) and excellent linear dynamic ranges (0.04–1.60μg/L) with remarkable correlation coefficients (r2>0.9980). Excellent repeatability was also achieved through intraday (RSD<13.7%) and interday (RSD<9.9%) assays. By using the standard addition methodology, the application of the present analytical approach on tap and ground water, as well as, wine samples revealed good sensitivity and absence of matrix effects. The proposed method operating under floating sampling technology proved to be a suitable sorption-based static microextraction alternative to monitor fungicides in real matrices, showing to be easy to implement, reliable, sensitive, requiring low sample volume and the possibility to choose the most selective sorbent coating according to the targets of interest.

Membrane-assisted solvent extraction coupled to large volume injection–gas chromatography–mass spectrometry for the determination of a variety of endocrine disrupting compounds in environmental water samples

Membrane-assisted solvent extraction coupled to large volume injection in a programmable temperature vaporisation injector using gas chromatography–mass spectrometry analysis was optimised for the simultaneous determination of a variety of endocrine disrupting compounds in environmental water samples (estuarine, river and wastewater). Among the analytes studied, certain hormones, alkylphenols and bisphenol A were included. The nature of membranes, extraction solvent, extraction temperature, solvent volume, extraction time, ionic strength and methanol addition were evaluated during the optimisation of the extraction. Matrix effects during the extraction step were studied in different environmental water samples: estuarine water, river water and wastewater (influent and effluent). Strong matrix effects were observed for most of the compounds in influent and effluent samples. Different approaches were studied in order to correct or minimise matrix effects, which included the use of deuterated analogues, matrix-matched calibration, standard addition calibration, dilution of the sample and clean-up of the extract using solid-phase extraction (SPE). The use of deuterated analogues corrected satisfactorily matrix effect for estuarine and effluent samples for most of the compounds. However, in the case of influent samples, standard addition calibration and dilution of the sample were the best approaches. The SPE clean-up provided similar recoveries to those obtained after correction with the corresponding deuterated analogue but better chromatographic signal was obtained in the case of effluent samples. Method detection limits in the 5-54 ng L(-1) range and precision, calculated as relative standard deviation, in the 2-25% range were obtained.

Membrane assisted solvent extraction coupled to large volume injection-gas chromatography–mass spectrometry for trace analysis of synthetic musks in environmental water samples

This work describes the optimisation, validation and application of membrane assisted solvent extraction (MASE) together with a large volume injection (LVI) in a programmable temperature vaporisation (PTV) injector coupled to gas chromatography–mass spectrometry (GC–MS) for the quantification of ten synthetic musk fragrances (musks) in surface and wastewater samples. Regarding the MASE, musks were extracted from 150mL of aqueous samples to 200μL of n-hexane hold in home-made low density polyethylene (LDPE) bags. The extraction took 240min and the performance of the method made possible the direct analysis of the extracts by LVI-PTV-GC–MS without needing any further treatment and avoiding losses of analytes. During the optimisation of LVI-PTV set-up, the response surfaces of every analyte signal against the cryo-focussing temperature, injection speed and vent time were built. Finally, the figures of merit of the whole procedure allowed the analysis of most of the musks owing to the low method detection limits (between 4 and 25ngL−1) and good precisions (<20%). In fact, this method was successfully applied to the analysis of musks in surface and wastewater samples. Galaxolide and tonalide are the main two synthetic musks observed in most of the analysed environmental water samples.