Selective determination of 2-aminobenzothiazole in environmental water and organic extracts from fish and dust samples.

In the present study, a homemade mixed-mode ion-exchange sorbent based on silica with embedded graphene microparticles is applied for the selective extraction of 2-aminobenzothiazole (NH2BT) followed by determination through liquid chromatography coupled to high-resolution mass spectrometry. The sorbent was evaluated for the solid-phase extraction of NH2BT from environmental water samples (river, effluent wastewater, and influent wastewater), and NH2BT was strongly retained through the selective cation-exchange interactions. Therefore, the inclusion of a clean-up step of 7 mL of methanol provided good selectivity for the extraction of NH2BT. The apparent recoveries obtained for environmental water samples ranged from 62 to 69% and the matrix effect from -1 to -14%. The sorbent was also evaluated in the clean-up step of the organic extract for the extraction of NH2BT from organic extracts of indoor dust samples (10 mL of ethyl acetate from pressurized liquid extraction) and fish (10 mL of acetonitrile from QuEChERS extraction). The organic extracts were acidified (adding a 0.1% of formic acid) to promote the cation-exchange interactions between the sorbent and the analyte. The apparent recoveries for fish samples ranged from 22 to 36% depending on the species. In the case of indoor dust samples, the recovery was 41%. It should be highlighted the low matrix effect encountered in such complex samples, with values ranging from -7 to 5% for fish and dust samples. Finally, various samples were analyzed. The concentration in river samples ranged from 31 to 136 ng/L; in effluent wastewater samples, from 55 to 191 ng/L; in influent wastewater samples, from 131 to 549 ng/L; in fish samples, from 14 to 57 ng/g dried weight; and in indoor dust samples, from

Evaluation of ceramic passive samplers using a mixed-mode strong cation-exchange sorbent to monitor polar contaminants in river water.

Although most of the analytical methods developed for the monitoring of contaminants in environmental waters are based on discrete grab sampling, an alternative of increasing interest is the use of passive sampling. Methods based on passive sampling provide the sampling and pre-concentration of the analytes in-situ, which makes the sample treatment less time consuming and costly than using discrete grab sampling. In this study, ceramic passive samplers (CPSs) using mixed-mode strong cation-exchange sorbent (Oasis MCX) as retention phase were evaluated for the determination of a group of 21 therapeutic and illicit drugs and some of their metabolites in river water samples that were determined by liquid chromatography-tandem mass spectrometry. After assessing the stability of the analytes, the CPSs were calibrated for 9 days with bottled water and river water, obtaining, for the 19 stable compounds, sample rates (Rs) ranging between 0.180 and 1.767 mL/day and diffusion coefficients (De) between 2.02E-8 and 2.81E-7 cm2/s. Once calibrated, CPSs were deployed for the determination of contaminants in the Ebre River, with good reproducibility, and some of the analytes were determined, including amongst others, gabapentin at 76 ng/L, caffeine at 203 ng/L or diclofenac amine at 57 ng/L. The passive sampling method herein presented is simple and feasible and allows the time-integrated analysis of pharmaceuticals and drugs at trace levels in river water. This study opens the possibility of using other mixed-mode sorbents or other types of sorbents as retaining phase on CPSs for the determination of very polar contaminants in water.

Ceramic passive samplers for determining pharmaceuticals and drugs of abuse in river and drinking water.

An important challenge today is to efficiently monitor the presence of polar pharmaceuticals and drugs in surface and drinking waters to ensure its safeness. Most studies rely on grab sampling techniques, which enable the determination of contaminants at a given point and given time. In this study, we propose the use of ceramic passive samplers (CPSs) to increase the representativeness and efficiency of organic contaminant monitoring in waters. Firstly, we have assayed the stability of 32 pharmaceuticals and drugs and found that five of those compounds were unstable. Moreover, we evaluated the retention capabilities of three sorbents (Sepra ZT, Sepra SBD-L, and PoraPak Rxn RP) in solid-phase extraction (SPE) mode and found no differences in terms of recoveries for all three sorbents. We then calibrated CPSs using the three sorbents for the 27 stable compounds over 13 days, with a suitable uptake for 22 compounds with sampling rates between 0.4 and 17.6 mL/day, which indicates high uptake efficiency. CPSs with the Sepra ZT sorbent were deployed in river water (n = 5) and drinking water (n = 5) for 13 days. Some of the studied compounds occurred with a time-weighted concentration, for instance, of 43 ng/L for caffeine, 223 ng/L for tramadol or 175 ng/L for cotinine in river water.

Extraction of selected benzothiazoles, benzotriazoles and benzenesulfonamides from environmental water samples using a home-made sol-gel silica-based mixed-mode zwitterionic sorbent modified with graphene.

A novel sol-gel silica-based mixed-mode zwitterionic sorbent modified with graphene microparticles was synthesized. Thanks to the inclusion of multiple functional groups and graphene microparticles to exert a wide range of intermolecular/interionic interactions including dipole-dipole interactions, ion-exchange interactions and π-π interactions, the sorbent showed high retention in the solid-phase extraction (SPE) of benzothiazoles, benzotriazoles and benzenesulfonamides. The SPE protocol was optimized in terms of pH, sample loading volume and elution conditions using liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). The method based on SPE followed by LC-HRMS was validated. Apparent recoveries at two levels of concentration were in the range from 48 to 85% (in most cases) in matrices such as influent wastewater, matrix effect was lower than ±30% in most cases, method detection and quantification limits being lower than 20 ng/L and repeatability and reproducibility between days were lower than 18% (n = 4). River, effluent and influent wastewaters samples were analyzed, obtaining concentrations ranging from 3 to 175 ng/L in river samples, from 12 to 499 ng/L in effluent samples and from 15 to 632 ng/L in influent samples, when the compounds were above the method quantification limits.

Development of sol-gel silica-based mixed-mode zwitterionic sorbents for determining drugs in environmental water samples.

Four novel mixed-mode zwitterionic silica-based functionalized with strong moieties sorbents were synthesized and evaluated through solid-phase extraction (SPE) to determine acidic and basic drugs in environmental water samples. All sorbents had the same functionalization: quaternary amine and sulfonic groups and C18 chains so that hydrophobic and strong cationic exchange (SCX) and strong anionic exchange (SAX) interactions could be exploited, in addition, two of them had carbon microparticles embedded. All sorbents retained both acidic and basic compounds in the preliminary assays but only the basic compounds were retained selectively through ionic exchange interactions when a clean-up step was introduced. The SPE method was therefore optimized to promote the selective retention of the basic compounds, initially with the two best-performing sorbents. After optimization of the SPE protocol, these sorbents were evaluated for the analysis of environmental water samples using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method with the best-performing sorbent was then validated with 100 mL of river samples and 50 mL of effluent wastewater samples in terms of apparent recoveries (%Rapp) spiking samples at 50 ng/L (river) and 200 ng/L (river and effluent), matrix effect, linear range, method quantification and detection limits, repeatability, and reproducibility. It should be highlighted that %Rapp ranged from 40 to 85% and matrix effects ranged from -17 to -4% for spiked river samples. When the method was applied to river and effluent wastewater samples, most compounds were found in the range from 24 to 1233 ng/L with detection limits from 1 to 5 ng/L.

Multiresidue analytical method for high production volume chemicals in dust samples, occurrence and human exposure assessment.

A multiresidue analytical method based on pressurised liquid extraction and gas-chromatography mass spectrometry was developed to determine 22 compounds belonging to different chemical families in indoor dust.: Seven organophosphate esters, six phthalate esters, three benzotriazoles, five benzothiazoles and four benzenesulfonamides were included in the present study, all of them belonging to the category of high production volume chemicals (HPVCs). Apparent recoveries ranged between 45% and 123% and method quantification limits ranged from 0.03 µg/g to 3.8 µg/g. The occurrence of the selected HPVCs was evaluated in indoor dust from different locations in the Tarragona (Catalonia, Spain) region. Two benzenesulfonamides, ortho-toluenesulfonamide and para-toluenesulfonamide, were detected in dust samples for the first time. Phthalate esters and organophosphate esters were the most abundant compounds found, and di-(2-ethylhexyl) phthalate (DEHP) was determined at the highest concentrations. With the data obtained, human exposure was assessed by calculating the estimated daily intakes (EDI) via ingestion and dermal contact. Non-carcinogenic and carcinogenic risk assessments found no risks in any of the scenarios tested, which included two age classes (children and adults) and two possible exposure scenarios (median and worst-case scenario), except for the evaluation of carcinogen risk due to ingestion of DEHP in the worst-case scenario.

Weak anion-exchange mixed-mode materials to selectively extract acidic compounds by stir bar sorptive extraction from environmental waters.

In this study, the first example of a polytetrafluoroethylene (PTFE)-based magnet coated with weak anion exchange (WAX) monolith as novel support for stir bar sorptive extraction (SBSE) is presented. Firstly, the PTFE magnets were properly modified and vinylized in order to immobilize polymer monoliths onto its surface. Then, a glycidyl methacrylate monolith was prepared and modified with ethylenediamine (EDA) to create weak anion exchanger via ring opening reaction of epoxy groups. The prepared covalently immobilized EDA-modified monoliths onto PTFE magnet exhibited good stability and reusability. Application of resulting material as stir bar for SBSE was investigated for a series of acidic compounds that includes acesulfame, saccharin, diclofenac or ibuprofen, among others as target compounds. Firstly, the SBSE conditions were optimized to promote the WAX interactions with the target compounds achieving recoveries from 37 to 75% and enable the selective extraction of these compounds as it provided values of% matrix effect from 17 to -13% when they were determined by SBSE followed by liquid chromatography - tandem mass spectrometry. The analytical methodology, was then validated and applied for the determination of the target solutes in environmental water samples, which were found at concentration up to 2500 ng L-1 in river waters.

Hypercrosslinked polymer microspheres decorated with anion- and cation-exchange groups for the simultaneous solid-phase extraction of acidic and basic analytes from environmental waters.

Mixed-mode ion-exchange sorbents were introduced to improve the selectivity and retention of solid-phase extraction (SPE) sorbents. Mixed-mode ion-exchange sorbents integrate reversed-phase chemistry with ion-exchange groups to promote favourable interactions with ionic species. Nevertheless, a need to extract analytes with acidic and basic properties simultaneously within the same SPE cartridge led to the introduction of novel amphoteric/zwitterionic sorbents, which incorporate cation- and anion-exchange moieties within the same functional group attached to the polymeric network. In the present study, the development, preparation and SPE evaluation of two novel hypercrosslinked zwitterionic polymeric sorbents, functionalised with either strong anion-exchange (SAX) and weak cation-exchange (WCX) or weak anion-exchange (WAX) and strong cation-exchange (SCX) groups (namely HXLPP-SAX/WCX and the HXLPP-WAX/SCX), is presented for the simultaneous retention of acidic and basic compounds. The sorbents were prepared by a precipitation polymerisation route which yielded poly(divinylbenzene-co-vinylbenzylchloride) as a precursor polymer; subsequently, the precursor polymer was hypercrosslinked, to increase the specific surface areas and capacities of the sorbents, and then functionalised to impart the zwitterionic character. The HXLPP-SAX/WCX sorbent was decorated with quaternised sarcosine groups and the HXLPP-WAX/SCX sorbent was decorated with taurine moieties. The SPE parameters were optimised to exploit the ionic interactions between compounds and the functional groups. The optimal conditions involve a washing step to remove the compounds retained by hydrophobic interactions, thus increasing the selectivity. The optimised SPE protocol used the quaternised sarcosine-based sorbent followed by liquid chromatography and tandem mass spectrometry, and was applied to determine compounds with acidic and basic properties from environmental samples, such as river water and effluent wastewater samples, with excellent selectivity and matrix effect values below -30% and apparent recovery results ranging from 52% to 105% for most of the compounds. The analytical method was validated for environmental water samples and used in the analysis of samples in which some of the target compounds were found at ng L-1 concentration levels.

Microporous polymer microspheres with amphoteric character for the solid-phase extraction of acidic and basic analytes.

Solid-phase extraction (SPE) is a widely-used and very well-established sample preparation technique for liquid samples. An area of on-going focus for innovation in this field concerns the development of new and improved SPE sorbents that can enhance the sensitivity and/or the selectivity of SPE processes. In this context, mixed-mode ion-exchange sorbents have been developed and commercialised, thereby allowing enhanced capacity and selectivity to be offered by one single material. The ion-selectivity of these materials is such that either anion-exchange or cation-exchange is possible, however one limitation to their use is that more than one sorbent type is required to capture both anions and cations. In this paper, we disclose the design, synthesis and exploitation of a novel SPE sorbent based on microporous polymer microspheres with amphoteric character. We show that it is possible to switch the ion-exchange retention mechanism of the sorbent simply by changing the pH of the loading solution; anion-exchange dominates at low pH, cation-exchange dominates at high pH, and both mechanisms can contribute to retention when the polymer-bound amphoteric species, which are based on the α-amino acid sarcosine (N-methylglycine), are in a zwitterionic state. This is an interesting and useful feature, since it allows distinctly different groups of analytes (acids and bases) to be fractionated using one single amphoteric sorbent with dual-functionality. The sarcosine-based sorbent was applied to the SPE of acidic, basic and amphoteric analytes from ultrapure water, river water and effluent wastewater samples. Under optimised conditions (loading 100 mL of sample at pH 6, washing with 1 mL of MeOH and eluting with an acidic or basic additive in MeOH) the recoveries for most of the compounds were from 57% to 87% for river water and from 61% to 88% for effluent wastewater. We anticipate that these results will lay the basis for the development of a new family of multifunctional sorbents, where two or more separation mechanisms can be embedded within one single, bespoke material optimised for application to challenging chemical separations to give significant selectivity advantages over essentially all other state-of-the-art SPE sorbents.

Enantiomeric determination of cathinones in environmental water samples by liquid chromatography-high resolution mass spectrometry.

The enantiomeric determination of chiral drugs in the environment is of emerging concern since their enantiomers often exhibit stereoselectivity in environmental occurrence, fate and toxicity. In this study a method based on solid-phase extraction followed by chiral liquid chromatography and high-resolution mass spectrometry has been developed for the enantiomeric determination of a group of cathinones in river water and effluent wastewater. The enantioseparation was carried out using a Chiralpak CBH column in reversed-phase mode, and optimised by evaluating the effects of flow rate, buffer concentration and organic modifier. Under optimal conditions, good enantioseparations (Rs ≥1.2) were achieved for all the analytes. Two mixed-mode cation-exchange sorbents (Oasis WCX and Oasis MCX) in solid-phase extraction were evaluated in river water. Oasis MCX sorbent showed better performance with apparent recoveries ranging from 57 to 91% and matrix effect ranging from -10 to 15%. It is worth noting that a shifting of retention times and loss of enantioresolutions in environmental water samples was observed for all the analytes when the Oasis WCX sorbent was used. The method was validated with river water and effluent wastewater samples and its overall performance was satisfactory. The method quantification limits for all the analyte enantiomers ranged from 1.0 to 2.9 ng/L in river water, and from 2.3 to 6.0 ng/L in effluent wastewater. The repeatability and reproducibility values, expressed as% relative standard deviation (n = 5) were less than 15%. The method was then applied to the analysis of river water and effluent wastewater. The racemic methylone and methedrone (EF=0.49 and 0.46, respectively) were detected at low ng/L in some of the river water samples.

Selective monitoring of acidic and basic compounds in environmental water by capsule phase microextraction using sol-gel mixed-mode sorbents followed by liquid chromatography-mass spectrometry in tandem.

In addition to the diverse extraction techniques available, capsule phase microextraction (CPME), which uses a microextraction capsule (MEC), has recently been introduced as a sorptive-based sample preparation technique. In this study, two different MECs (MEC-C18/SAX and MEC-C18/SCX) based on mixed-mode ion-exchange technology were synthesized and evaluated for the selective extraction of a group of ionizable compounds, including acidic and basic analytes. A sulfonic acid was used as the cation-exchange group in MEC-C18/SCX, and a quaternary amine as the anion-exchange group in MEC-C18/SAX. The extraction parameters optimized were sample pH, elution solvent, sample/elution volume and extraction/elution time. The optimized CPME method followed by LC-MS/MS was used to determine the ionizable compounds in environmental water samples, including river water and effluent wastewater, with excellent selectivity and matrix effect values below -30% (except -33% for mephedrone) and apparent recovery results ranging from 40% to 69%, except for ibuprofen (< 35%) and atenolol (< 25%). The analytical method was validated for environmental water samples, and used in the analysis of several samples in which some of the target compounds were found at ng L-1 concentration levels.

Overview of mixed-mode ion-exchange materials in the extraction of organic compounds.

Mixed-mode ion-exchange materials, including silica-based, polymer-based and other supports, have been applied in sample treatment with different techniques, mainly solid-phase extraction, but also other microextraction techniques such as solid-phase microextraction, stir bar sorptive extraction and microextraction by packed sorbent. These materials are widespread because they conveniently combine capacity (through the reversed-phase interactions in the material backbone) and selectivity (through the specific ion-exchange interactions). This review provides an overview of the advances and applications of mixed-mode ion-exchange materials for the extraction of organic compounds from complex matrices in environmental, food and biological samples. We summarise the different approaches used to prepare these materials and discuss the extraction protocols applied and the types of compounds and samples analysed based on different selected examples.

Comparison of polysaccharide-based and protein-based chiral liquid chromatography columns for enantioseparation of drugs.

Two different columns-Lux Cellulose-1 and Chiralpak CBH-were evaluated for their chiral recognition abilities for eight drugs comprising three ß-blockers, one antacid, and four cathinones in polar-organic elution mode and reversed-phase elution mode, respectively. The factors that affected the enantioseparation were tested and optimized to develop a suitable chiral separation method whose LC conditions are compatible with MS detection. In polar-organic elution mode with the Lux Cellulose-1 column, methanol and acetonitrile were tested as the main components of the mobile phase. In addition, the effects of adding isopropanol as organic modifier, acidic additives (formic acid), and basic additives (diethylamine) were evaluated. In reversed-phase elution mode with the Chiralpak CBH column, the effect of type and concentration of organic modifier (isopropanol, acetonitrile, and methanol), the mobile phase pH (6.4 and 5.0), and buffer concentration (1mM-20mM ammonium acetate) were evaluated. The best enantioseparation was achieved with the Chiralpak CBH column with a mobile phase composed of 5mM ammonium acetate aqueous (pH = 6.4)/methanol (95/5, v/v) at a flow rate of 0.1 mL/min and a temperature of 30°C. Under these conditions, six of eight chiral drugs were baseline separated.

Mixed-mode ion-exchange polymeric sorbents in environmental analysis.

When determining contaminants from environmental samples, sample treatment plays an important role. Among the different extraction techniques available, solid-phase extraction (SPE) has been commonly used for liquid samples, as well as for solid samples after an extraction technique amenable for solids. The broad applicability of SPE is attributed to the availability of different sorbents. Among these sorbents, the mixed-mode ion-exchange polymeric ones have been widely exploited since they suitably combine both capacity (to concentrate the compounds) and selectivity (to clean-up the interferences from complex matrices). This review overviews the application of mixed-mode ion-exchange polymeric sorbents in environmental field when water and solid samples are analyzed. The sample analyzed, the compounds determined, the type of mixed-mode sorbent selected, the approach used and the SPE protocol applied are comprehensively discussed through different examples. This review intends to summarize the role of mixed-mode ion-exchange polymeric sorbents in the environmental field.

Optimised extraction methods for the determination of trichothecenes in rat faeces followed by liquid chromatography-tandem mass spectrometry.

The mycotoxin deoxynivalenol (DON) and some of its derivatives, such as 3­acetyl­deoxynivalenol (3AcDON), 15­acetyl­deoxynivalenol (15AcDON), deoxynivalenol­3­glucoside (DON3G) and de-epoxy deoxynivalenol (DOM-1), are commonly found in food and/or biological samples. However, literature does not present suitable methodologies for detecting and quantifying these mycotoxins at very low levels, which would be especially useful when they are present in biological samples. The main goal of the present paper was to evaluate different extraction techniques for the determination of these mycotoxins in rat faecal samples, in order to reduce the interferences present in the matrix and be able to quantify the mycotoxins at low concentration levels. Using diverse extraction methodologies such as QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and pressurised liquid extraction (PLE), the clean-up strategy was optimised. QuEChERS extraction followed by a dispersive solid-phase extraction (dSPE) clean-up step with activated carbon was the method with the best extraction recovery results, ranging between 78% and 83% (except for DON3G). The matrix effect values were from -2% to -20% which supposed a reduction in comparison with the other tested strategies. These results enabled low quantification limits to be achieved, from 0.2 µg kg-1 to 3.4 µg kg-1. In view of the results, it was possible to quantify the natural presence of DON and DOM-1 in the tested faecal samples at low concentration levels.

Monitoring and evaluation of the interaction between deoxynivalenol and gut microbiota in Wistar rats by mass spectrometry-based metabolomics and next-generation sequencing.

Published evidence has demonstrated the several toxic characteristics of mycotoxins and their considerable risk to human and animal health. One of the most common uncertainties regards whether if very low concentrations of the mycotoxin deoxynivalenol (DON), easily consumed within the Mediterranean Diet, can cause metabolic alterations; some of them produced by the interaction between DON and gut microbiota. Accordingly, faecal samples were collected from Wistar rats that had consumed the mycotoxin DON at low levels (60 and 120 µg kg-1 body weight of DON per day), and were analysed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry detection, in order to monitor the mycotoxin DON and its metabolite de-epoxy deoxynivalenol (DOM-1). The obtained results showed an evolution in DON excretion and the metabolite DOM-1 which has less toxic properties, over the course of the days of the study. To elucidate whether intestinal microbiota had a role in the observed detoxification process, the changes in microbial gut biodiversity were explored through 16s rRNA high throughput sequencing. No main changes were detected but significant increase in Coprococcus genus relative abundance was found. Further studies are needed to confirm if intestinal microbiota composition and function are affected by low mycotoxin concentrations.

Novel capsule phase microextraction in combination with liquid chromatography-tandem mass spectrometry for determining personal care products in environmental water.

A novel sample preparation technique named capsule phase microextraction (CPME) is presented here. The technique utilizes a miniaturized microextraction capsule (MEC) as the extraction medium. The MEC consists of two conjoined porous tubular polypropylene membranes, one of which encapsulates the sorbent through sol-gel technology, while the other encapsulates a magnetic metal rod. As such, MEC integrates both the extraction and stirring mechanisms into a single device. The aim of this article is to demonstrate the application potential of CPME as sample preparation technique for the extraction of a group of personal care products (PCPs) from water matrices. Among the different sol-gel sorbent materials (UCON®, poly(caprolactone-dimethylsiloxane-caprolactone) (PCAP-DMS-CAP) and Carbowax 20M (CW-20M)) evaluated, CW-20M MEC demonstrated the best extraction performance for the selected PCPs. The extraction conditions for sol-gel CW-20M MEC were optimized, including sample pH, stirring speed, addition of salt, extraction time, sample volume, liquid desorption solvent, and time. Under the optimal conditions, sol-gel CW-20M MEC provided recoveries, ranging between 47 and 90% for all analytes, except for ethylparaben, which showed a recovery of 26%. The method based on CPME with sol-gel CW-20M followed by liquid chromatography-tandem mass spectrometry was developed and validated for the extraction of PCPs from river water and effluent wastewater samples. When analyzing different environmental samples, some analytes such as 2,4-dihydroxybenzophenone, 2,2-dihydroxy-4-4 methoxybenzophenone and 3-benzophenone were found at low ng L-1.

Hypercrosslinked particles for the extraction of sweeteners using dispersive solid-phase extraction from environmental samples.

This work presents a new extraction material, namely, Q-100, based on hypercrosslinked magnetic particles, which was tested in dispersive solid-phase extraction for a group of sweeteners from environmental samples. The hypercrosslinked Q-100 magnetic particles had the advantage of suitable pore size distribution and high surface area, and showed good retention behavior toward sweeteners. Different dispersive solid-phase extraction parameters such as amount of magnetic particles or extraction time were optimized. Under optimum conditions, Q-100 showed suitable apparent recovery, ranging in the case of river water sample from 21 to 88% for all the sweeteners, except for alitame (12%). The validated method based on dispersive solid-phase extraction using Q-100 followed by liquid chromatography with tandem mass spectrometry provided good linearity and limits of quantification between 0.01 and 0.1 µg/L. The method was applied to analyze samples from river water and effluent wastewater, and four sweeteners (acesulfame, saccharin, cyclamate, and sucralose) were found in both types of sample.

Combining cationic and anionic mixed-mode sorbents in a single cartridge to extract basic and acidic pharmaceuticals simultaneously from environmental waters.

The aim of the present study is to broaden the applications of mixed-mode ion-exchange solid-phase extraction sorbents to extract both basic and acidic compounds simultaneously by combining the sorbents in a single cartridge and developing a simplified extraction procedure. Four different cartridges containing negative and positive charges in the same configuration were evaluated and compared to extract a group of basic, neutral, and acidic pharmaceuticals selected as model compounds. After a thorough optimization of the extraction conditions, the four different cartridges showed to be capable of retaining basic and acidic pharmaceuticals simultaneously through ionic interactions, allowing the introduction of a washing step with 15 mL methanol to eliminate interferences retained by hydrophobic interactions. Using the best combined cartridge, a method was developed, validated, and further applied to environmental waters to demonstrate that the method is promising for the extraction of basic and acidic compounds from very complex samples.

Determination of seven drugs of abuse and their metabolites in surface and wastewater using solid-phase extraction coupled to liquid chromatography with high-resolution mass spectrometry.

A method based on liquid chromatography with electrospray ionization high-resolution mass spectrometry (Exactive Orbitrap) combined with solid-phase extraction using a strong cationic exchange mixed-mode sorbent has been developed for the determination of seven drugs of abuse, including two synthetic cathinones, as well as some of their metabolites in environmental water samples. The method provides low detection limits and a high confirmation power thanks to the diagnostic and two fragment ions monitored for each compound in high-resolution mass spectrometry, providing six identification points for each analyte. The clean-up step based on methanol in the extraction step adequately decreased the matrix effect, mainly for river and effluent water, and provided suitable process efficiency. Method detection and quantitation limits for environmental waters were at low nanogram per liter. The method was applied to analyze the samples of influent and effluent wastewater, as well as surface water. Codeine, methadone, and its metabolite were determined in all samples of wastewater and the metabolite of cocaine, benzoylecgonine, was found at the highest concentration.