Comprehensive Analysis of Multiresidue Pesticides from Process Water Obtained from Wastewater Treatment Facilities Using Solid-Phase Microextraction.

A novel magnetic blade spray-tandem mass spectrometry (MBS-MS/MS) assay was developed and optimized, and its performance was characterized for the analysis of 204 pesticides from wastewater treatment facility (WWTF) process water. These results were compared and experimentally validated with an untargeted, high-resolution MS (HRMS) approach that employed liquid chromatography (LC)-amenable thin-film microextraction (TFME) devices to further elucidate the fate of pesticides through the WWTF process. As a result of our optimizations, we report an optimized workflow with an extraction time of 10 min, 150 µg of magnetic HLB particles, and 5 s of desorption. Excellent linearity was obtained for 168 of the 204 pesticides in deionized water, where 90% of the quantifiable pesticides had a determination coefficient (R2) of 0.99 across 3 orders of magnitude and 80% had limits of quantification below 0.5 ng/mL. We subsequently applied our optimized MBS-MS/MS method for the analysis of samples collected during the various stages of wastewater treatment from two WWTFs in Southern Ontario. This article presents a new streamlined methodology with a fast turnaround time for analyzing a large panel of pesticides, ultimately providing us the opportunity to evaluate the performance of two WWTFs for their efficacy in removing these toxic chemicals.

Introducing a mechanically robust SPME sampler for the on-site sampling and extraction of a wide range of untargeted pollutants in environmental waters.

The present study introduces a mechanically robust, sealable SPME sampler for the on-site sampling and extraction of a wide range of untargeted pollutants in environmental waters. Spray-coating and dip coating methodologies were used to coat the surfaces of six stainless steel bolts with a layer of HLB/PAN particles, which served as the extractive substrate in the proposed device. In addition, this sampler was designed to withstand rough handling, long storage times, and various environmental conditions. In order to identify whether the sampler was able to stabilize extracted compounds for long periods of time, the effects of storage time and temperature were evaluated. The results of these tests showed no significant differences in the quantity and quality of the extracted chemicals following 12 days storage at room temperature, thus confirming the device's suitability for use at sampling sites that are far away from the laboratory facilities. The proposed device was also used to perform extraction and untargeted analyses of river waters in five different geographical locations. The constituent chemicals in the samplers were analyzed and determined using high-resolution HPLC-Orbitrap MS. Toxin and Toxin-Target Database was used as a reference database for toxins and environmental contaminants. Ultimately, over 80 tentative chemicals with widely varying hydrophobicities ranging within -2.43 < logP <11.9-including drugs, metabolites, wide ranges of toxins, pesticide, and insecticides-were identified in the samplers used in the different rivers. The log P values for the tentative analytes confirmed that the introduced device is suitable for the extraction and trace analysis of wide ranges of targeted and untargeted pollutants.

An overview of the most common lab-made coating materials in solid phase microextraction.

In the present review, five well-established groups of lab-made SPME coatings materials including metal organic frameworks (MOFs), layered double hydroxides (LDHs), molecular imprinted polymers (MIPs), conductive polymers (CPs), ionic liquids (ILs), and all their derivations have been evaluated comprehensively, and their unique features, well-proven significant extraction performances as well as drawbacks have been also examined. This paper aims to give a comprehensive overview of what these materials are, why they are proper choices for SPME coatings, and what strengths and drawbacks have been associated with their usage as SPME coatings. Moreover, the present review provides information about the perspective developments regarding SPME coating materials.

Development of a Hydrophilic Lipophilic Balanced Thin Film Solid Phase Microextraction Device for Balanced Determination of Volatile Organic Compounds.

A novel hydrophilic-lipophilic balanced (HLB) thin film solid-phase microextraction (TF-SPME) device is proposed for polarity-balanced determinations of volatile organic compounds. The proposed HLB particles used in the preparation of these membranes were prepared using a precipitation polymerization technique and determined to have a specific surface area of 335 m2/g with an average pore diameter of 13 Å. Membranes prepared from these particles were found to extract 1.8, 2.2, 1.9, 1.7, 2.0, and 1.3 times more benzene, 2-pentanone, 1-nitropropane, pyridine, 1-pentanol, and octane, respectively, than the established divinylbenzene/polydimethylsiloxane (DVB/PDMS)-based membranes. Furthermore, membranes prepared from these lab-made particles were shown to extract significantly ( p = 0.00047) larger amounts of these analytes than membranes prepared from comparative commercial HLB particles. The intermembrane extraction efficiency between 3 membranes was determined to be reproducible at 95% confidence for 4 different coating chemistries tested, including the DVB/PDMS membranes, and those prepared with 3 different HLB compositions. Furthermore, method reliability was established by confirming that, once extracted, modified McReynolds standards were stable on the HLB/PDMS membranes stored in thermal desorption tubes on an autosampler rack for at least 120 h, for 5 of the 6 standards, but only for 24 h for pyridine at a 95% level of confidence. Finally, using a TF-SPME enabled, portable GC/MS instrument, an entirely on-site proof of concept application was performed for the determination and quantitation of chlorination byproducts in a private hot tub, successfully identifying chloroform, bromodichloromethane, dichloroacetonitrile, chlorobenzene, benzonitrile, and benzyl chloride, while further quantifying chloroform and dichloroacetonitrile at levels of 270 and 79 ppb with %RSD values of 13% and 5%, respectively.

Fiber-in-tube solid-phase microextraction of caffeine as a molecular tracer in wastewater by electrochemically deposited layered double hydroxide.

Modified stainless-steel wires with a layer of polyaniline conductive polymer were coated by electrochemical deposition with Zn/Al layered double hydroxide to make solid-phase microextraction fibers. The coating layer was also electrochemically deposited on the inner surface of a stainless-steel tube. Then, ten prepared fibers were put inside the inner coated tube to make a fiber-in-tube solid phase microextraction device. The device was applied for the extraction of caffeine (1,3,7-trimethylxanthine) from domestic wastewater samples. Extraction conditions including extraction and desorption times, pH and ionic strength of the sample solution, and content of the organic desorption solvent were investigated and optimized. Under the optimized conditions, the fiber-in-tube solid phase microextraction exhibited excellent extraction efficiency toward caffeine. The precision of the method was evaluated. Average relative standard deviation of 5.7% (n = 6) for intraday analysis and 8.3% (n = 5) for interday analysis was obtained. The limits of detection and limits of quantification of the method (at signal to noise ratio of 3 and 10) were obtained as 0.14 and 0.37 ng/mL, respectively. The current study can provide new prospective applications of layered double hydroxide conductive polymer fiber coatings.

Ordered mesoporous carbon as sorbent for the extraction of N-nitrosamines in wastewater and swimming pool water.

The analysis and determination of N-nitrosamines (NAs) in water samples are challenging and demanding. In this study, a simple, reliable, and practical methodology is reported for the quantitative determination by gas chromatography-tandem mass spectrometry with electron impact ionization (EI) and triple quadrupole analyzer (GC-EI-MS/MS) of eight NAs after micro-solid-phase extraction (µ-SPE) from wastewater and swimming pool water. Thirty milligram of an ordered mesoporous carbonaceous material, oxidative surface-modified CMK-3, enclosed within a porous polypropylene membrane bag, were used as sorbent for µ-SPE. A central composite design approach was applied to optimize the µ-SPE parameters. An isotopically-labeled NA was used as internal standard. Under the optimized conditions, µ-SPE-GC-EI-MS/MS was validated for an NA concentration range of between 0.1-100ng/mL. The precision of the method was evaluated and an average relative standard deviation of 4.8% (n=8) for a standard solution spiked at 50ng/mL of each NA was obtained. The limits of detection were measured to be in the range of 0.005-0.283ng/mL. Domestic wastewater and swimming pool water samples were used to evaluate the applicability of the method. NAs were detected in swimming pool water and wastewater at concentrations of <2ng/mL and 11ng/mL, respectively.

Introducing surface-modified ordered mesoporous carbon as a promising sorbent for extraction of N-nitrosamines.

The extraction and pre-concentration of N-nitrosamines (NAs) before their determination are mainly achieved by carbonaceous sorbents. However, the non-polar or relatively less polar NAs are strongly absorbed on the carbonaceous surface of the sorbent, leading to low extraction recoveries. In the present study, for the first time, CMK-3 and surfacemodified CMK-3 (O-CMK-3) were used to extract NAs from water. The CMK-3 surface was modified by oxidative treatment and different carboxylic groups were attached to create a hydrophilic/hydrophobic balance on the inert surface of the carbonaceous sorbent. The proposed sorbents were compared with 10 different kinds of commercial carbonaceous sorbents for the micro-solid phase extraction of eight NAs possessing a wide range of polarities. The best extraction results for both polar and non-polar NAs were obtained using O-CMK-3. Specifically, significant enhancements in the extraction of the nonpolar NAs were observed. For instance, extraction of up to 27.67 and 2.32 times greater were observed for N-nitrosodiphenylamine, and N-nitrosodimethylamine respectively, when O-CMK-3 was used instead of coconut charcoal sorbent.

Micro-solid phase extraction of perfluorinated carboxylic acids from human plasma.

Micro-solid phase extraction (µ-SPE), with liquid chromatography-tandem mass spectrometry has been developed for the determination of trace levels of perfluorinated carboxylic acids (PFCAs) in human plasma. The µ-SPE sorbent was surfactant-templated mesoporous silica. Extraction time, desorption time and salt concentration were chosen as the most effective parameters and were optimized simultaneously by use of central composite design. Under the optimized extraction conditions, good linearity in the range of 100 and 5000ngL(-1) was obtained with coefficients of determination of between 0.986 and 0.995. The limits of detection (at a signal to noise ratio of 3) were measured to be in the range of between 21.23 and 65.07ngL(-1), and limits of quantification (at a signal to noise ratio of 10) were in the range of between 70.77 and 216.92ngL(-1). The relative recoveries of spiked PFCAs in different samples were in the range of between 87.58 and 102.45%. As expected from the global distribution of PFCs, contaminations at low levels (less than 200ngL(-1)) were detected (with the highest concentration recorded for perfluorooctanoic acid (PFOA)). Considering the complex nature of biological samples and the issue of matrix effects in the analysis of PFCAs, µ-SPE as an extraction method was shown to be advantageous; it combined extraction and concentration in one single step with no additional sample clean-up, and was able to remove significant matrix interferences.

Application of surfactant-templated ordered mesoporous material as sorbent in micro-solid phase extraction followed by liquid chromatography-triple quadrupole mass spectrometry for determination of perfluorinated carboxylic acids in aqueous media.

In the present study, micro-solid phase extraction (µ-SPE) followed by liquid chromatography-triple tandem mass spectrometery (LC-MS/MS) was developed for the determination of perfluorocarboxylic acids (PFCAs) at trace levels in water samples. The µ-SPE device comprised of a porous polypropylene membrane bag containing 5mg sorbent. The membrane bag acted as a clean-up filter and prevented matrix compounds from interfering with the extraction process. Analysis was carried out by LC-MS/MS in negative electrospray ionization mode. MS/MS parameters were optimized for multiple reaction monitoring. Calcined and non-calcined MCM-41, as silica-ordered mesoporous materials, were used as sorbents in µ-SPE for the extraction of five PFCAs-perfluoropentanoic acid (PFPA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorodecanoic acid (PFDA)-from aqueous media. The performances of these two sorbents were compared with other sorbents such as octadecylsilane (C18) modified silica, HayeSep-A, HayeSep-B, and Porapak-R. It was found that non-calcined MCM-41 showed better extraction performance for the analytes considered. Parameters influencing extraction efficiency, such as desorption time, extraction time, desorption solvent, and salt concentration, were investigated. The effect of the matrix on MS signals (suppression or enhancement) was also evaluated. Only minor effects on ionization efficiencies were observed. The developed method proved to be convenient and offered good sensitivity and reproducibility. The limits of detection ranged from 0.02 to 0.08ng L(-1), with a relative standard deviations between 1.9 and 10.5. It was successfully applied to the extraction of PFCAs in river and rain water samples. As expected from the ubiquitous nature of PFCAs, contamination at low levels was detected for some analytes in the samples (with the highest concentration recorded for PFOA). Satisfactory relative recoveries ranging between 64% and 127% at spiking levels of 10ng L(-1) of each analyte were obtained.

Determination of perfluorinated carboxylic acids in fish fillet by micro-solid phase extraction, followed by liquid chromatography-triple quadrupole mass spectrometry.

In the current study, a simple, fast and efficient combination of protein precipitation and micro-solid phase extraction (µ-SPE) followed by liquid chromatography-triple quadrupole tandem mass spectrometry (LC-MS/MS) was developed for the determination of perfluorinated carboxylic acids (PFCAs) in fish fillet. Ten PFCAs with different hydrocarbon chain lengths (C5-C14) were analysed simultaneously using this method. Protein precipitation by acetonitrile and µ-SPE by surfactant-incorporated ordered mesoporous silica were applied to the extraction and concentration of the PFCAs as well as for removal of interferences. Determination of the PFCAs was carried out by LC-MS/MS in negative electrospray ionization mode. MS/MS parameters were optimized for multiple reaction monitoring of the analytes. (13)C mass labelled PFOA as a stable-isotopic internal standard, was used for calibration. The detection limits of the method ranged from 0.97 ng/g to 2.7 ng/g, with a relative standard deviation of between 5.4 and 13.5. The recoveries were evaluated for each analyte and were ranged from 77% to 120%. The t-test at 95% confidence level showed that for all the analytes, the relative recoveries did not depend on their concentrations in the explored concentration range. The effect of the matrix on MS signals (suppression or enhancement) was also evaluated. Contamination at low levels was detected for some analytes in the fish samples. The protective role of the polypropylene membrane used in µ-SPE in the elimination of matrix effects was evaluated by parallel experiments in classical dispersive solid phase extraction. The results evidently showed that the polypropylene membrane was significantly effective in reducing matrix effects.