Large Volume Injection Gas Chromatography Mass Research Articles

Evaluation of α- and β-Endosulfan Residues in Teas and Yerba Mate Infusions by Bar Adsorptive Microextraction and Large Volume Injection-Gas Chromatography Mass Spectrometry

Tea and yerba mate are traditional beverages prepared through the infusion of leaves of Camellia sinensis and Ilex paraguariensis, respectively. During this process, the leaching of pesticides onto the beverage, such as endosulfan, may occur. In this study, a bar adsorptive microextraction (BAµE) method prior to large gas chromatography mass spectrometry analysis was developed to analyze a- and b-endosulfan in teas and yerba mate infusions. Different sorbent coatings for BAµE were compared and the hydrophilic-lipophilic balanced polymer showed the best selectivity for endosulfan isomers. The method was validated providing good recoveries (varying from 80.4 ± 1.8 to 108 ± 4.9%) and linearities (r2 > 0.99), limits of detection from 8.0 to 4.0 µg kg-1 and limits of quantification from 40 to 20 µg kg-1 for a- and b-endosulfan, respectively. The application of the method in the analysis of real samples showed all free of endosulfan at the limit of detection of the analytical method.

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.

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.

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.

Linear and cyclic methylsiloxanes in air by concurrent solvent recondensation–large volume injection–gas chromatography–mass spectrometry

In the present work, a simple and fast method for the analysis of linear and cyclic methylsiloxanes in ambient air based on active sampling combined with gas chromatography - mass spectrometry (GC-MS) was developed. The retention efficiency of five sampling sorbents (activated coconut charcoal, Carbopack B, Cromosorb 102, Cromosorb 106 and Isolute ENV+) was evaluated and Isolute ENV+ was found to be the most effective. A volume of 2700 L of air can be sampled without significant losses of the most volatile methylsiloxanes. To improve the sensitivity of the GC-MS method, concurrent solvent recondensation - large volume injection (CSR-LVI), using volumes up to 30 µl of sample extract, is proposed and limits of quantification down to 0.03-0.45 ng m(-3), good linearity (r>0.999) and precision (RSD %<9%) were obtained. The developed method was applied to the analysis of ambient air. Concentrations of linear and cyclic methylsiloxanes in indoor air ranging from 3.9 to 319 ng m(-3) and between 48 and 292668 ng m(-3), were obtained, respectively, while levels from 6 to 22 ng m(-3) for linear and between 2.2 and 439 ng m(-3) for cyclic methylsiloxanes in outdoor air from Barcelona (Spain), were found.

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.

Determination of polycyclic aromatic hydrocarbons in water samples using online microextraction by packed sorbent coupled with gas chromatography–mass spectrometry

A fully automated microextraction by packed sorbents (MEPS) coupled with large volume injection gas chromatography–mass spectrometry (GC–MS) has been developed for the determination of eight polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Naphthalene (Nap), pyrene (Pyr), anthracene, acenaphthylene, phenanthrene, fluoranthene (Flr), fluorene and acenaphthene were the PAHs studied. The performance of the microextraction-GC–MS protocol was compared with solid phase extraction (SPE) and GC–MS analysis. Under optimized experimental conditions, the methods were linear for all analytes in the following ranges: 0.05–2.0μgL−1 (MEPS) and 0.25–10.0μgL−1 (SPE). The correlation coefficients (R2) were in the range 0.9965–0.9997 (MEPS) and 0.9978–0.9998 (SPE) for all the analytes. Limits of detection (LODs) for 2mL samples (MEPS) ranged from 0.8ngL−1 to 8.2ngL−1. LODs for 50mL samples (SPE) were between 4.8ngL−1 and 35.9ngL−1. The two methods were successfully applied to the determination of the 8 PAHs in environmental waters, with recoveries in the range of 70–117% (MEPS) and 72–134% (SPE) for a real spiked sample. The two sample preparation processes showed good repeatabilities with intra-day relative standard deviations below 14.0% (MEPS) and 14.6% (SPE). Nap, Flr and Pyr were found in a river water sample.

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.

Development of a bar adsorptive micro-extraction–large-volume injection–gas chromatography–mass spectrometric method for pharmaceuticals and personal care products in environmental water matrices

The combination of bar adsorptive micro-extraction using activated carbon (AC) and polystyrene-divinylbenzene copolymer (PS-DVB) sorbent phases, followed by liquid desorption and large-volume injection gas chromatography coupled to mass spectrometry, under selected ion monitoring mode acquisition, was developed for the first time to monitor pharmaceutical and personal care products (PPCPs) in environmental water matrices. Assays performed on 25 mL water samples spiked (100 ng L(-1)) with caffeine, gemfibrozil, triclosan, propranolol, carbamazepine and diazepam, selected as model compounds, yielded recoveries ranging from 74% to 99% under optimised experimental conditions (equilibrium time, 16 h (1,000 rpm); matrix characteristics: pH 5, 5% NaCl for AC phase; LD: methanol/acetonitrile (1:1), 45 min). The analytical performance showed good precision (RSD < 18%), convenient detection limits (5-20 ng L(-1)) and excellent linear dynamic range (20-800 ng L(-1)) with remarkable determination coefficients (r(2) > 0.99), where the PS-DVB sorbent phase showed a much better efficiency. By using the standard addition methodology, the application of the present analytical approach on tap, ground, sea, estuary and wastewater samples allowed very good performance at the trace level. The proposed method proved to be a suitable sorption-based micro-extraction alternative for the analysis of priority pollutants with medium-polar to polar characteristics, showing to be easy to implement, reliable, sensitive and requiring a low sample volume to monitor PPCPs in water matrices.

Micro liquid–liquid extraction combined with large-volume injection gas chromatography–mass spectrometry for the determination of haloacetaldehydes in treated water

Haloacetaldehydes (HAs) are becoming the most widespread disinfection by-products (DBPs) found in drinking water, besides trihalomethanes and haloacetic acids, generated by the interaction of chemical disinfectants with organic matter naturally present in water. Because of their high potential toxicity, HAs have currently received a singular attention, especially trichloroacetaldehyde (chloral hydrate, CH), the most common and abundant compound found in treated water. The aims of this study are focused on the miniaturisation of EPA Method 551.1, including some innovations such as the use of ethyl acetate as the extracting solvent, the enhancement of HAs stability in aqueous solutions by adjusting the pH ∼3.2 and the use of a large-volume sample injection (30 μL) coupled to programmed temperature vaporizer–gas chromatography–mass spectrometry to improve both sensitivity and selectivity. In optimised experimental conditions, the limits of detection for the 7 HAs studied ranged from 6 to 20 ng/L. Swimming pools have recently been recognized as an important source of exposure to DBPs and as a result, in this research for the first time, HAs have been determined in this type of water. Two HAs have been found in the analysed water: CH at concentrations between 1.2–38 and 53–340 μg/L and dichloroacetaldehyde between 0.07–4.0 and 1.8–23 μg/L in tap and swimming pool waters, respectively.

Fully automated determination of parabens, triclosan and methyl triclosan in wastewater by microextraction by packed sorbents and gas chromatography–mass spectrometry

A fully automated method for the determination of triclosan (TCS), its derivative methyl triclosan (MeTCS) and six parabens (esters of 4-hydroxybenzoic acid) including branched and linear isomers of propyl ( i-PrP and n-PrP) and butyl paraben ( i-BuP and n-BuP) in sewage water samples is presented. The procedure includes analytes enrichment by microextraction by packed sorbent (MEPS) coupled at-line to large volume injection-gas chromatography–mass spectrometry (LVI-GC–MS). Under optimised conditions, compounds were extracted from 2 mL samples, adjusted at pH 3, using a C18 MEPS-sorbent. Adsorbed analytes were eluted directly into the Programmable Temperature Vaporizer (PTV) injector of the chromatograph with 2 × 25 μL of ethyl acetate. They were quantified using standard solutions in ultrapure water submitted to the same sample enrichment process as real sewage water samples. After signal normalisation using isotopic labelled species as internal surrogates, no differences were noticed among the extraction efficiency for sewage and ultrapure water; moreover, the proposed method reported lineal calibration curves from 0.1 to 10 ng mL −1, relative standard deviations (%RSD) between 2 and 7.1% and limits of detection (LODs) varying from 0.001 to 0.015 ng mL −1 in ultrapure water and from 0.02 to 0.59 ng mL −1 in the most complex sample (raw wastewater).

Determination of organic priority pollutants and emerging compounds in wastewater and snow samples using multiresidue protocols on the basis of microextraction by packed sorbents coupled to large volume injection gas chromatography–mass spectrometry analysis

This paper describes the development and validation of a new procedure for the simultaneous determination of 41 multi-class priority and emerging organic pollutants in water samples using microextraction by packed sorbent (MEPS) followed by large volume injection–gas chromatography–mass spectrometry (LVI–GC–MS). Apart from method parameter optimization the influence of humic acids as matrix components on the extraction efficiency of MEPS procedure was also evaluated. The list of target compounds includes polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalate esters (PEs), nonylphenols (NPs), bisphenol A (BPA) and selected steroid hormones. The performance of the new at-line microextraction-LVI–GC–MS protocol was compared to standard solid-phase extraction (SPE) and LVI–GC–MS analysis. LODs for 100 mL samples (SPE) ranged from 0.2 to 736 ng L −1 were obtained. LODs for 800 μL of sample (MEPS) were between 0.2 and 266 ng L −1. In the case of MEPS methodology even a sample volume of only 800 μL allowed to detect the target compounds. These results demonstrate the high sensitivity of both procedures which permitted to obtain good recoveries (>75%) for all cases. The precision of the methods, calculated as relative standard deviation (RSD) was below 21% for all compounds and both methodologies. Finally, the developed methods were applied to the determination of target analytes in various samples, including snow and wastewater.

At-line microextraction by packed sorbent-gas chromatography–mass spectrometry for the determination of UV filter and polycyclic musk compounds in water samples

An at-line analysis protocol is presented that allows the determination of four UV filters, two polycyclic musk compounds and caffeine in water at concentration level of ng L −1. The fully automated method includes analytes enrichment by Microextraction by packed sorbent (MEPS) coupled directly to large volume injection-gas chromatography–mass spectrometry. Two common SPE phases, C8 and C18, were examined for their suitability to extract the target substances by MEPS. The analytes were extracted from small sample volumes of 800 μL with recoveries ranging from 46 to 114% for the C8-sorbent and 65–109% for the C18-sorbent. Limits of detection between 34 and 96 ng L −1 enable the determination of the analytes at common environmental concentration levels. Both sorbents showed linear calibration curves for most of the analytes up to a concentration level of 20 ng mL −1. Carryover was minimized by washing the sorbents 10 times with 100 μL methanol. After this thorough cleaning, the MEPS are re-used and up to 70 analyses can be performed with the same sorbent. The fully automated microextraction GC–MS protocol was evaluated for the influence of matrix substances typical for wastewater. Dilution of samples prior to MEPS is recommended when the polar caffeine is present at high concentration. Real water samples were analyzed by the MEPS-GC–MS method and compared to standard SPE.

Stir-bar-sorptive extraction and liquid desorption combined with large-volume injection gas chromatography–mass spectrometry for ultra-trace analysis of musk compounds in environmental water matrices

Stir-bar-sorptive extraction with liquid desorption followed by large-volume injection and capillary gas chromatography coupled to mass spectrometry in selected ion monitoring acquisition mode (SBSE-LD/LVI-GC-MS(SIM)) has been developed to monitor ultra-traces of four musks (celestolide (ADBI), galaxolide (HHCB), tonalide (AHTN) and musk ketone (MK)) in environmental water matrices. Instrumental calibration (LVI-GC-MS(SIM)) and experimental conditions that could affect the SBSE-LD efficiency are discussed. Assays performed on 30-mL water samples spiked at 200 ng L(-1) under optimized experimental conditions yielded recoveries ranging from 83.7 ± 8.1% (MK) to 107.6 ± 10.8% (HHCB). Furthermore, the experimental data were in very good agreement with predicted theoretical equilibria described by octanol-water partition coefficients (K (PDMS/W) ≈ K (O/W)). The methodology also showed excellent linear dynamic ranges for the four musks studied, with correlation coefficients higher than 0.9961, limits of detection and quantification between 12 and 19 ng L(-1) and between 41 and 62 ng L(-1), respectively, and suitable precision (< 20%). Application of this method for analysis of the musks in real water matrices such as tap, river, sea, and urban wastewater samples resulted in convenient selectivity, high sensitivity and accuracy using the standard addition methodology. The proposed method (SBSE-LD/LVI-GC-MS(SIM)) was shown to be feasible and sensitive, with a low-sample volume requirement, for determination of musk compounds in environmental water matrices at the ultra-trace level, overcoming several disadvantages presented by other sample-preparation techniques.