Solid-phase Extraction Recoveries Research Articles

Sustainable bio-based solid phase extraction adsorbent for the determination of various types of organic compounds.

A sustainable, bio-based, mesoporous material, Starbon A800, was explored for use as an adsorbent in solid phase extraction (SPE). A solution containing seven nitrosamines was first used as a standard to optimise conditions for extraction efficiency with Starbon A800. After optimising conditions, 25 compounds of varying polarity (terpenes, phenolics, pesticides, PAHs, amines, and nitrosamines) were extracted with SPE using either Starbon® A800, C18 or Porous Graphitic Carbon (PGC) as the adsorbent, for comparison purposes. At the same time, 3 different elution solvents (heptane, dichloromethane, and ethanol) were used for each type of adsorbent. Hansen solubility parameters can be used to choose an appropriate elution solvent for the selected SPE adsorbent. The best average SPE recoveries found for the 25 various compounds were 83%, 79%, and 65% using Starbon A800, PGC, and C18 adsorbents respectively and these had dichloromethane as the elution solvent. The identification and quantification of components was carried out using UV-visible spectroscopy, two-dimensional gas chromatography (GCxGC) with time of flight/mass spectrometry (TOF/MS) or a nitrogen chemiluminescence detector (NCD). The optimized method was successfully applied to extract volatile organic compounds from red wine and tap water using Starbon A800. Starbon A800 was shown to be a promising, low-cost, green, scalable, alternative adsorbent for the extraction of various types of organic compounds of a wide range of polarities using SPE.

Extraction and analysis by liquid chromatography – tandem mass spectrometry of intra- and extracellular microcystins and nodularin to study the fate of cyanobacteria and cyanotoxins across the freshwater-marine continuum

The presence of microcystins (MCs) is increasingly being reported in coastal areas worldwide. To provide reliable data regarding this emerging concern, reproducible and accurate methods are required to quantify MCs in salt-containing samples. Herein, we characterized methods of extraction and analysis by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) for nine MCs and one nodularin (NOD) variants in both cyanobacteria (intracellular) and dissolved forms (extracellular). Different approaches have been used to cope with salinity for the extraction of dissolved MCs but none assessed solid phase extraction (SPE) so far. It was found that salt had negligible effect on the SPE recovery of dissolved MCs using the C18 cartridge while an overestimation up to 67% was noted for some variants with a polymeric sorbent. The limits of detection (LOD) and quantification (LOQ) were 1.0–22 and 5.5–124 pg on column for the intracellular toxins, while 0.05–0.81 and 0.13–2.4 ng/mL were obtained for dissolved toxins. Extraction recoveries were excellent for intracellular (89–121%) and good to excellent for extracellular cyanotoxins (73–102%) while matrix effects were considered neglectable (<12% for 16/20 toxin-matrix combinations), except for the two MC-RR variants. The strategy based on the application of a corrective factor to compensate for losses proved useful as the accuracy was satisfactory (73–117% for intra- and 81–139% for extracellular cyanotoxins, bias <10% for 46/60 conditions, with a few exceptions), with acceptable precisions (intra- and inter-days variabilities <11%). We then applied this method on natural colonies of Microcystis spp. subjected to a salt shock, mimicking their estuarine transfer, in order to assess their survival and to quantify their toxins. The colonies of Microcystis spp. had both their growth and photosynthetic activity impaired at salinities from 10, while toxins remained mainly intracellular (>76%) even at salinity 20, suggesting a potential health risk and contamination of estuarine organisms.

Compound-Specific Carbon, Hydrogen, and Nitrogen Isotope Analysis of Nitro- and Amino-Substituted Chlorobenzenes in Complex Aqueous Matrices.

Compound-specific isotope analysis (CSIA) is an established tool to study the fate of legacy groundwater contaminants but is only emerging for nonconventional contaminants, e.g., nitro- and amino-substituted chlorobenzenes that are widely used as industrial feedstock and the target of this work. To date, CSIA of the target compound groups used special combustion interfaces and the potential matrix interferences in environmental samples has not been assessed. We validated CSIA methods for δ13C, δ2H, and δ15N of four analytes from each chemical group and developed a solid-phase extraction (SPE) method to minimize matrix interferences during preconcentration of complex aqueous samples. The SPE recovery was >80% and the method quantification limits of SPE-CSIA for δ13C, δ2H, and δ15N were 0.03-0.57, 1.3-2.7, and 3.4-10.2 μM aqueous-phase concentrations, respectively, using 2 L of spiked MQ water. The SPE-CSIA procedure showed negligible isotope fractionation for δ13C (≤0.5‰), δ15N (≤0.5‰), and δ2H (≤5‰ for nitroaromatics and ≤10‰ for aminoaromatics). In addition, solvent evaporation, water sample storage up to 7 months, and SPE extract storage for 1.5 years did not change analytes' δ13C signatures beyond ±0.5‰. However, to avoid significant δ2H and δ15N fractionation of aminoaromatics, cartridge breakthrough should be avoided and SPE preconcentration must be conducted at pH > pKa + 2. Application of the method at a contaminated site showed excellent precision, at ≤0.3‰ for C and N, and ≤1.5‰ for H. The methods validated here now allow the use of multielement CSIA to track the environmental fate of nitro- and amino-substituted chlorobenzenes in complex aqueous samples.

Analysis of hydrophilic per- and polyfluorinated sulfonates including trifluoromethanesulfonate using solid phase extraction and mixed-mode liquid chromatography-tandem mass spectrometry

Ultra-hydrophilic per- and polyfluorinated sulfonates (PFSA) are increasingly scrutinized in recent years due to their ubiquitous occurrence, persistence, and aqueous mobility in the environment, yet analysis remains a challenge. This study developed methods for the analysis of trifluoromethanesulfonate, perfluorobutanesulfonate, 10-camphorsulfonate, and a di-fluorinated sulfonate utilizing mixed-mode liquid chromatography, where all analytes were adequately retained and separated. Chromatography and electrospray ionization parameters were optimized; instrumental limits of quantification for the anionic target analytes were in the range of 4.3 - 16.1 ng L−1. Solid phase extraction (SPE) methods were developed using Oasis WAX cartridges; SPE recoveries for the analytes ranged from 86% to 125%. Salinity and total organic carbon both impaired the SPE performance to different extents, depending on the respective analyte. Utilizing widely accessible instrumentation and materials, this is a single method to simultaneously analyze conceivably the most hydrophilic PFAS chemical, i.e., trifluoromethanesulfonate, and moderately hydrophobic PFSAs.

Optimization of Plant Extract Purification Procedure for Rapid Screening Analysis of Sixteen Phenolics by Liquid Chromatography

A solid-phase extraction (SPE) procedure was developed for simultaneous monitoring of sixteen different phenolics of various polarity, quantified by high-performance liquid chromatography (HPLC). The procedure allowed screening the accumulation of intermediates in different metabolic pathways that play a crucial role in plant physiology and/or are beneficial for human health. Metabolites mostly involved in phenylpropanoid, shikimate, and polyketide pathways comprise chlorogenic acid, gentisic acid, vanillic acid, caffeic acid, protocatechuic acid, ferulic acid, rutin, quercetin, epicatechin, gallic acid, sinapic acid, p-coumaric acid, o-coumaric acid, vanillin; two rarely quantified metabolites, 2,5-dimethoxybenzoic acid and 4-methoxycinnamic acid, were included as well. The procedure offered low cost, good overall efficiency, and applicability in laboratories with standard laboratory equipment. SPE recoveries were up to 99.8% at various concentration levels. The method allowed for routine analysis of compounds with a wide range of polarity within a single run, while its applicability was demonstrated for various model plant species (tobacco, wheat, and soybean), as well as different tissue types (shoots and roots).

Mesoporous Silica With Covalently Immobilized Anthracene As Adsorbent For SPE Recovery Of PAHs Pollutants From Highly Lipidic Solutions

Two samples of functionalized mesoporous silica containing anchored anthrylmethylamine groups (SiO2-Ant) have been prepared by surface assembling (1) and one step silane immobilization (2). Both adsorbents can be attributed to bimodal balanced hydrophobic-hydrophilic adsorbents with loading of anthracene groups about 15-33 %. The adsorbents have been used for solid-phase extraction (SPE) of anthracene from organic solvents (acetonitrile, acetone and heptane) and model solutions of lipids (myristic acid and vegetable oil). The obtained results were compared with commercial C18 SPE cartridge. While C18 cartridge recovers anthracene from water-containing media (acetonitrile/water, 1/1), SiO2-Ant cartridges much more efficient in extraction of anthracene from non-polar solvent (heptane). Lipids macrocomponents such as myristic acid and vegetable oil do not decrease the dynamic adsorption capacity and recovery of the model polycyclic aromatic hydrocarbon (PAH) on SiO2-Ant. It was demonstrated that π-π stacking interaction with the analyte determine the selectivity of SiO2-Ant towards of anthracene. This makes SiO2-Ant attractive for selective preconcentration of PAHs from high lipid content objects, such as vegetable oils.

Simultaneous screening for chemically diverse micropollutants in public water bodies in Japan by high-performance liquid chromatography–Orbitrap mass spectrometry

An improved assessment of environmental risks to public water bodies requires screening a large number of micropollutants. This study reports the development of a novel target screening method based on solid-phase extraction (SPE), HPLC, and high-resolution Orbitrap MS for the analysis of micropollutants with diverse chemical properties. First, target compounds were screened for their detectability by Orbitrap MS. An optimized SPE cartridge and HPLC column maximized recovery and separated most target compounds. The sensitivity and repeatability of the method was validated by determining the detection limits and relative standard deviation (RSD). Eighty-four compounds with highly diverse properties were simultaneously detected with detection limits of 0.1–100 ng/L. Of these compounds, 52 were quantitated, with R2 ≥ 0.99 by linearity analysis and SPE recovery ratios of ≥50%. The remaining 32 compounds were qualitatively detected, with R2 < 0.99 or SPE recovery ratio of <50%. Satisfactory repeatability was obtained (RSD < 13.5%). This method was applied to the surveillance of the Arakawa River in Japan in 2019. Thirty-two compounds, including pesticides, surfactants, plasticizers, adhesives, and industrial solvents, were detected in the river. The measured concentrations of 13 compounds were compared with their predicted no effect concentrations (PNECs). Decanoic acid showed a higher concentration than the corresponding PNEC value, suggesting that its risk to the Arakawa water environment required further evaluation. The concentrations of dicyclohexylamine, 1,3-diphenylguanidine, and 2,4-dichlorophenoxyacetic acid were higher than their corresponding PNEC/10 values, demonstrating that these compounds were of higher priority than other compounds.

Stable Isotopic Labeling and Nontarget Identification of Nanogram/Liter Amino Contaminants in Water.

We report a new combinatorial approach of stable isotopic labeling (SIL)-solid phase extraction (SPE)-liquid chromatography-tandem high-resolution mass spectrometry (LC-HRMS/MS) for identification of amino-containing contaminants at trace levels in source water. The new SIL method requires small amounts of formaldehyde (CH2O) and deuterated formaldehyde (CD2O) to efficiently label ng/L amino compounds in 1 L of water and improves SPE recovery, enabling environmental analysis of trace amino-compounds. Isotopically methylated components were confirmed using LC-MS/MS based on their retention times, and characteristic isotope patterns of the molecular and product ions. Using the characteristic isotope patterns, we established a data prioritization process to identify the amino compounds in thousands of mass peaks in raw data. Analysis of a labeled authentic source water detected 8952 m/z peaks and tentatively identified 154 amino compounds. Our SIL-methylation prioritization approach effectively reduced the complexity of data. Manual spectrum interpretation identified 77 of the 154 components as amino acids and peptides. We confirmed 8 of the 77 compounds using commercially available standards to demonstrate the feasibility and reliability of our SIL-SPE-LC-HRMS/MS method for environmental analysis of trace amino-containing contaminants. The method can efficiently identify amino-precursors in source water, enabling other studies of nitrogenous disinfection byproduct formation.

The detection of drugs of abuse and pharmaceuticals in drinking water using solid-phase extraction and liquid chromatography-mass spectrometry

Pharmaceuticals and drugs of abuse including novel psychoactive substances (NPS) are emerging as newer contaminants in the aquatic environment. The presence of such pollutants has implications on the environment as well as public health and therefore their identification is important when monitoring water quality. This research presents a new method for the simultaneous detection of 20 drugs of abuse and pharmaceuticals in drinking water, including 15 NPS, three traditional illicit drugs and two antidepressants. The developed method is based on the use of solid-phase extraction (SPE) followed by liquid chromatography-mass spectrometry (LC-MS). The SPE recoveries for the majority of target analytes ranged between 62 and 107%. The method detection and quantification limits ranged between 0.01 and 1.09 ng/L and 0.02–3.64 ng/L respectively. Both instrumental and method precisions resulted in relative standard deviations <15.04%, with an accuracy of < ±8.66%. The results show that LC-MS can be an alternative to the more popular technique of liquid chromatography-tandem mass spectrometry for the analysis of drugs of abuse and pharmaceuticals in drinking water. This newly developed simultaneous detection method has been applied to drinking water collected from the East Anglia region of the UK. Citalopram, cocaine, fluoxetine, ketamine, mephedrone, methamphetamine and methylone were detected at the range of 0.14 and 2.81 ng/L. This is the first time that the two NPS mephedrone and methylone, have been detected in UK drinking water.

Wastewater-based monitoring of illicit drug consumption in Istanbul: Preliminary results from two districts

Wastewater-based epidemiology is a well-established and complementary approach for monitoring illicit drug use in the general population. In this study, amphetamine (AMP), methamphetamine (METH), 3,4-methylenedioxymethamphetamine (MDMA), cocaine (COC) (from benzoylecgonine), and cannabis (from THC-COOH) consumption levels were investigated for the first time in Turkey (Istanbul). A solid-phase extraction method was applied to influent wastewater samples collected from two districts, Beyoglu and Catalca. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis was conducted with electrospray ionization in positive mode. Calibration curves were acquired in linear form with >0.999 correlation coefficients. Limit of detection levels were measured as 0.91–151 ng/L, and limit of quantitation levels were in the range of 3 to 500 ng/L. Solid-phase extraction recovery and repeatability experiments were achieved by spiking the mix solution to different concentrations (50, 250, 750 ng/L) in 50 mL tap water and wastewater (500, 1000 ng/L) samples in six replicates. The method was optimized, and recoveries were found to be over 80% for all six substances with up to 11.9% relative standard deviation. According to the real sample results, cannabis was found to be the most abused illicit substance among the analytes. The mean consumptions of the two districts, including seven consecutive days for AMP, METH, MDMA, COC, and cannabis, were found to be 27.2, 322, 331, 385, and 1224 mg/day/1000 inhabitants, respectively. In this presented study, all targeted compounds were analyzed simultaneously with the same analytical conditions. To the best of our knowledge, this report is the first to present illicit drug consumption data from Istanbul.

A new analytical framework for multi-residue analysis of chemically diverse endocrine disruptors in complex environmental matrices utilising ultra-performance liquid chromatography coupled with high-resolution tandem quadrupole time-of-flight mass spectrometry

This manuscript presents a comprehensive analytical framework for identification and quantification of chemically diverse endocrine disrupting chemicals (EDCs) used in personal care and consumer products in diverse solid and liquid environmental matrices with an ultimate goal of evaluating public exposure to EDCs via water fingerprinting. Liquid chromatography coupled with tandem quadrupole time-of-flight mass spectrometry (UHPLC-ESI-MS/MS) was used for targeted analysis of selected EDCs as well as to identify and quantify a few metabolites using post-acquisition data mining. Solid-phase extraction (SPE) was applied to liquid matrices in order to reduce matrix effects and provide required sample concentration and ultimately, high sensitivity and selectivity of measurements. SPE recoveries in liquid samples ranged from 49 to 140% with method quantification limits not exceeding 1 ng L−1 for the majority of EDCs. Microwave-assisted extraction (MAE) was applied to solid samples and when followed by SPE, it permitted the analysis of EDCs in digested sludge. MAE/SPE recoveries varied from 11 to 186% and MQLs between 0.03 and 8.1 ng g−1 with the majority of compounds showing MQLs below 2 ng g−1. Mass error for quantifier and qualifier ions was below 5 ppm when analysing river water and effluent wastewater and below 10 ppm when analysing influent wastewater and solid samples. The method was successfully applied to environmental samples, with 33 EDCs identified and quantified in wastewater and receiving waters. In addition, several EDCs were found in digested sludge, which confirms that for a more comprehensive understanding of exposure patterns and environmental impact, analysis of solids cannot be neglected. Finally, post-acquisition data mining permitted the identification and quantification of a metabolite of BPA and the identification of a metabolite of 4-Cl-3-methylphenol.Graphical abstractᅟ

Determination of fluoroquinolones in cattle manure-based biogas residue by ultrasonic-enhanced microwave-assisted extraction followed by online solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry

The present work describes the development and application of an ultrasonic-enhanced microwave-assisted extraction (UEMAE) followed by online solid phase extraction (SPE)–ultra–high performance liquid chromatography–tandem mass spectrometry method for the analysis of 14 fluoroquinolones in cattle manure-based biogas residue (CMBBR). The UEMAE was performed using the mixed solution of sodium dihydrogen phosphate and disodium ethylenediamine tetraacetic acid, avoiding use of any organic solvent. The online SPE system employed two solid phase extraction columns in a parallel manner, and the extraction was performed by passing 1 mL of the extract through the column. Quantification was performed using standard spiked samples and structural analogue internal standard, which were indispensable to reduce the matrix effects. Validation parameters were performed and good linearity (R2 > 0.99 in all cases) and precision (inter- and intra-day relative standard deviations were lower than 12.8%) were obtained. Limits of detection were as low as 0.021 ng ∙ g−1 and lower limits of quantification were 0.5 ng ∙ g−1 for all fluoroquinolones. The overall extraction recovery, which was the product of the UEMAE recovery and the online SPE recovery, was assessed for three concentration levels (0.8, 40 and 400 ng ∙ g−1) and acceptable values (74.3–99.3%) were found. As a part of the method validation, the developed method has been used to analyze real CMBBR samples. Nine fluoroquinolones were found in the concentration range of 0.9–74.6 ng ∙ g−1, while five were not detected in the samples. The results showed the method could be adapted for screening the presence or the final fate of fluoroquinolones during fermentation of animal waste.

Solid-phase extraction as sample preparation of water samples for cell-based and other in vitro bioassays.

In vitro bioassays are increasingly used for water quality monitoring. Surface water samples often need to be enriched to observe an effect and solid-phase extraction (SPE) is commonly applied for this purpose. The applied methods are typically optimised for the recovery of target chemicals and not for effect recovery for bioassays. A review of the few studies that have evaluated SPE recovery for bioassays showed a lack of experimentally determined recoveries. Therefore, we systematically measured effect recovery of a mixture of 579 organic chemicals covering a wide range of physicochemical properties that were spiked into a pristine water sample and extracted using large volume solid-phase extraction (LVSPE). Assays indicative of activation of xenobiotic metabolism, hormone receptor-mediated effects and adaptive stress responses were applied, with non-specific effects determined through cytotoxicity measurements. Overall, effect recovery was found to be similar to chemical recovery for the majority of bioassays and LVSPE blanks had no effect. Multi-layer SPE exhibited greater recovery of spiked chemicals compared to LVSPE, but the blanks triggered cytotoxicity at high enrichment. Chemical recovery data together with single chemical effect data were used to retrospectively estimate with reverse recovery modelling that there was typically less than 30% effect loss expected due to reduced SPE recovery in published surface water monitoring studies. The combination of targeted experiments and mixture modelling clearly shows the utility of SPE as a sample preparation method for surface water samples, but also emphasizes the need for adequate controls when extraction methods are adapted from chemical analysis workflows.

A new method for macrolide antibiotics determination in wastewater from three different wastewater treatment plants

Abstract An effective and practical method for the determination of macrolide antibiotics azithromycin, clarithromycin, erythromycin and roxithromycin in wastewater samples has been developed. The analytical method combines solid phase extraction followed by a chromatographic separation by hydrophilic interaction liquid chromatography (HILIC) coupled with an ion trap mass spectrometer utilizing the electrospray ionization technique. Detection of positively charged ions was performed in full scan mode from 500 to 900 m/z. The method detection limits and method quantification limits obtained were in the range of 2.03-7.59 ng L-1 and 6.08-23.84 ng L-1, respectively. Recoveries of solid phase extraction were obtained using SupelTM-Select HLB cartridges ranging from 85.76 % to 92.54 %. All target antibiotics were detected in 100 % of the collected raw influent samples with concentrations varying from 15 ng L-1 to 1849 ng L-1. Azithromycin, clarithromycin and erythromycin were also detected in 100 % of the treated water samples and roxithromycin was present in 96 % of the samples. The highest determined concentration in the treated water samples was 1404 ng L-1 of azithromycin. Based on the determined macrolide concentrations, removal efficiencies of individual wastewater treatment plants were calculated to range from 13 % to 100 %.

Deep eutectic solvents for the purification of chloromycetin and thiamphenicol from milk.

Deep eutectic solvents were used in both dispersive liquid-liquid microextraction and solid-phase extraction for the purification of chloromycetin and thiamphenicol from milk. In the dispersive liquid-liquid microextraction procedure, deep eutectic solvents mixed with chloroform at different ratios (0:1-5:1, v/v) were used as the extraction agent to optimize the procedure, and the ratio of 2:1 v/v was found to be the best extraction agent with 87.23 and 83.17% recoveries of chloromycetin and thiamphenicol, respectively. Furthermore, deep eutectic solvents were also used to modify molecular imprinted polymers in solid-phase extraction procedure, and the polymers were used to purify chloromycetin and thiamphenicol from milk. Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy were used to characterize the polymers. The solid-phase extraction recoveries with deep eutectic solvents with molecularly imprinted polymers (chloromycetin and thiamphenicol, two templates), molecularly imprinted polymers (without deep eutectic solvents), and nonimprinted polymers (without a template) for chloromycetin were 91.23, 82.64, and 57.3%, respectively, and recoveries for thiamphenicol were 87.02, 79.03, and 52.27%, respectively. The recoveries of chloromycetin and thiamphenicol from milk in the solid-phase extraction procedure were higher than using deep eutectic solvents mixed with chloroform as the extraction agent in the dispersive liquid-liquid microextraction procedure.

On-line solid-phase extraction method for determination of triazine herbicides and degradation products in seawater by ultra-pressure liquid chromatography–tandem mass spectrometry

A fast, simple, selective and sensitive method has been developed for the determination of nine triazine herbicides (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) and eight degradation products (desethyl atrazine, desethyl-desisopropyl atrazine, desethyl 2-hydroxyatrazine, desethyl terbuthylazine, desisopropyl atrazine, desisopropyl 2-hydroxyatrazine, 2-hydroxyatrazine and 2-hidroxyterbuthylazine) in seawater samples. On-line solid-phase extraction coupled with ultra-pressure liquid chromatography-tandem mass spectrometry was employed for simultaneous analysis of all compounds in 11min. Validation parameters were studied through the estimation of the limits of detection and quantification, calibration curves and precision. Limits of quantification ranged from 0.023 to 0.657μgL−1. Good linearity was obtained for all compounds with R2>0.99 in all cases. Furthermore, inter-day precision (0–2.1%) and intra-day precision (0–3.9%) were shown to be satisfactory. On-line solid-phase extraction recoveries in spiked unpolluted seawater sample were evaluated and acceptable values (80.3–99.8%) with adequate RSD (0.1–3.1%) were found.Finally, the proposed method was applied to the analysis of the target compounds in seawater samples collected from seawater nearby a zone of intensive horticulture of Matosinhos (Portugal). The concentrations of the herbicides were below the limit of detection in all cases.

Development of an LC-MS/MS Method for the Assessment of Selected Active Pharmaceuticals and Metabolites in Wastewaters of a Swiss University Hospital.

A multi-residue analytical method was developed and validated for the quantification of 11 selected active pharmaceutical ingredients (API) and 2 human metabolites in hospital effluents using solid-phase extraction followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Targeted analytes belong to different therapeutic classes: non steroidal anti-inflammatory drugs (NSAID), analgesics, antibiotics and psychiatric drugs. Solid-phase extraction recoveries ranged between 21 and 101% for the selected API. Calibration curves were built with 6 standard samples prepared in ultrapure water ranging from 0.05 to 10 μg/L and showed regression coefficients above 0.994. The instrumental detection limits (IDL) varied between 0.05 and 5 μg/L, and the method detection limits (MDL) between 0.1 and 100 ng/L. Precision of the method, evaluated with spiked water samples at four different concentrations, varied between 84 and 117% for all compounds and an overall variability below 20%, with the exception of carbamazepine (71-123%). Except for two compounds, recoveries of spiked hospital wastewaters at four different concentrations (0.1, 1, 10 and 100 μg/L) varied between 44 and 133%, with relative standard deviation (RSD) between 0.6 and 28.5%. The evaluation of the matrix effects showed that diluted samples exhibit lower signal suppression. Analysis of effluent samples from a Swiss university hospital resulted in a mean detection frequency of 92% for the selected compounds, with concentrations up to 1535 μg/L for the analgesic paracetamol.

Multi-walled carbon nanotubes as solid-phase extraction sorbents for simultaneous determination of type A trichothecenes in maize, wheat and rice by ultra-high performance liquid chromatography-tandem mass spectrometry

A solid-phase extraction (SPE) procedure using multi-walled carbon nanotubes (MWCNTs) as sorbents coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for simultaneous determination of four type A trichothecenes in maize, wheat and rice for the first time. Several key parameters including the composition of sample loading solutions, washing and elution solvents were thoroughly investigated to achieve optimal SPE recoveries and efficiency. Performance of the MWCNTs materials was significantly affected by pH, and after optimization, n-hexane and 5% methanol aqueous solution as the washing solutions and methanol containing 1% formic acid as the elution solvent presented an excellent purification efficiency for the four targets in the different matrices. The method was validated by determining the linearity (R2≥0.992), recovery (73.4–113.7%), precision (1.2–17.1%) and sensitivity (limit of quantification in the range of 0.02–0.10μg/kg), and was further applied for simultaneous determination of type A trichothecenes in 30 samples. Although low contamination levels of type A trichothecenes in wheat, maize and rice were observed revealing mitigated risks to consumers in Shanghai, China, the developed method has proven to be a valuable tool for type A trichothecenes monitoring in complex crop matrices.

Deep Eutectic Solvents Modified Molecular Imprinted Polymers for Optimized Purification of Chlorogenic Acid from Honeysuckle

Deep eutectic solvents (DES) were synthesized with choline chloride (ChCl), and DES modified molecular imprinted polymers (DES-MIPs), DES modified non-imprinted polymers (DES-NIPs, without template), MIPs and NIPs were prepared in an identical procedure. Fourier transform infrared spectrometer (FT-IR) and field emission scanning electron microscopy (FE-SEM) were used to characterize the obtained polymers. Rebinding experiment and solid-phase extraction (SPE) were used to prove the high selectivity adsorption properties of the polymers. Box-Behnken design (BBD) with three factors was used to optimize the extraction condition of chlorogenic acid (CA) from honeysuckles. The optimum extraction conditions were found to be ultrasonic time optimized (20 min), the volume fraction of ethanol (60%) and ratio of liquid to material (15 mL g(-1)). Under these conditions, the mean extraction yield of CA was 12.57 mg g(-1), which was in good agreement with the predicted BBD model value. Purification of hawthorn extract was achieved by SPE process, and SPE recoveries of CA were 72.56, 64.79, 69.34 and 60.08% by DES-MIPs, DES-NIPs, MIPs and NIPs, respectively. The results showed DES-MIPs had potential for promising functional adsorption material for the purification of bioactive compounds.

Determination of BMAA and three alkaloid cyanotoxins in lake water using dansyl chloride derivatization and high-resolution mass spectrometry.

A new analytical method was developed for the detection of alkaloid cyanotoxins in harmful algal blooms. The detection of the nonproteinogenic amino acid β-N-methylamino-L-alanine (BMAA) and two of its conformation isomers, 2,4-diaminobutyric acid (DAB) and N-(2-aminoethyl) glycine (AEG), as well as three alkaloid cyanotoxins, anatoxin-a (ANA-a), cylindrospermopsin (CYN), and saxitoxin (STX), is presented. The use of a chemical derivatization with dansyl chloride (DNS) allows easier separation with reversed phase liquid chromatography. Detection with high-resolution mass spectrometry (HRMS) with the Q-Exactive enables high selectivity with specific fragmentation as well as exact mass detection, reducing considerably the possibilities of isobaric interferences. Previous to analysis, a solid phase extraction (SPE) step is used for purification and preconcentration. After DNS derivatization, samples are submitted to ultra high-performance liquid chromatography coupled with heated electrospray ionisation and the Q-Exactive mass spectrometer (UHPLC-HESI-HRMS). With an internal calibration using isotopically-labeled DAB-D3, the method was validated with good linearity (R (2) > 0.998), and method limits of detection and quantification (MLD and MLQ) for target compounds ranged from 0.007 to 0.01 μg L(-1) and from 0.02 to 0.04 μg L(-1), respectively. Accuracy and within-day/between-days variation coefficients were below 15%. SPE recovery values ranged between 86 and 103%, and matrix effects recovery values ranged between 75 and 96%. The developed analytical method was successfully validated with 12 different lakes samples, and concentrations were found ranging between 0.009 and 0.3 μg L(-1) except for STX which was not found in any sample.