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This study addresses the analysis of emerging contaminants, often using chromatographic techniques coupled to mass spectrometry. However, sample preparation is often required prior to instrumental analysis, and dispersive liquid-liquid microextraction (DLLME) is a viable strategy in this context. DLLME stands out for its ability to reduce sample and solvent volumes. Notably, dispersive liquid-liquid microextraction using magnetic ionic liquids (MILs) has gained relevance due to the incorporation of paramagnetic components in the chemical structure, thereby eliminating the centrifugation step. A pyrolizer was selected in this work to introduce sample onto the GC column, since the MIL is extremely viscous and incompatible with direct introduction through an autosampler. This study is the first to report the use of a DLLME/MIL technique for sample introduction through a pyrolizer in gas chromatography coupled to mass spectrometry (GC-MS). This approach enables the MIL to be compatible with gas chromatography systems, resulting in optimized analytical and instrument performance. The analysis of polybrominated diphenyl ether flame retardants (PBDEs) was focused on the PBDE congeners 28, 47, 99, 100, and 153 in sewage sludge samples. The [P 6,6,6,14 + ] 2 [MnCl 4 2- ] MIL was thoroughly characterized using UV-Vis, Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy, as well as thermal analysis. In the chromatographic method, a pyrolyzer was used in the sample introduction step (Py-GC-MS), and critical injection settings were optimized using multivariate approaches. Optimized conditions were achieved with a temperature of 220 °C, a pyrolysis time of 0.60 min, and an injection volume of 9.00 μL. DLLME optimization was performed through central compound planning (CCD), and optimized training conditions were achieved with 10.0 mg of MIL, 3.00 μL of acetonitrile (ACN) as dispersive solvent, extraction time of 60 s, and volume of a sample of 8.50 mL. Precision was observed to range from 0.11 % to 12.5 %, with limits of detection (LOD) of 44.4 μg L -1 for PBDE 28, 16.9 μg L -1 for PBDE 47 and PBDE 99, 33.0 μg L -1 for PBDE 100 and 375 μg L -1 for PBDE 153. PBDE 28 was identified and analyzed in the sludge sample at a concentration of 800 μg L -1 . The use of MIL in dispersive liquid-liquid microextraction combined with pyrolysis gas chromatography-mass spectrometry enables identification and quantification of PBDEs in sewage sludge samples at concentrations down to the µg L -1 level., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. The author is an Editorial Board Member/Editor-in-Chief/Associate Editor/Guest Editor for Journal of Chromatography A and was not involved in the editorial review or the decision to publish this article., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Omics analyses collectively refer to the possibility of profiling genetic variants, RNA, epigenetic markers, proteins, lipids, and metabolites. The most common analytical approaches used for detecting molecules present within biofluids related to metabolism are vibrational spectroscopy techniques, represented by infrared, Raman, and nuclear magnetic resonance (NMR) spectroscopies and mass spectrometry (MS). Omics-based assessments utilizing MS are rapidly expanding and being applied to various scientific disciplines and clinical settings. Most of the omics instruments are operated by specialists in dedicated laboratories; however, the development of miniature portable omics has made the technology more available to users for field applications. Variations in molecular information gained from omics approaches are useful for evaluating human health following environmental exposure and the development and progression of numerous diseases. As MS technology develops so do statistical and machine learning methods for the detection of molecular deviations from personalized metabolism, which are correlated to altered health conditions, and they are intended to provide a multi-disciplinary overview for researchers interested in adding multiomic analysis to their current efforts. This includes an introduction to mass spectrometry-based omics technologies, current state-of-the-art capabilities and their respective strengths and limitations for surveying molecular information. Furthermore, we describe how knowledge gained from these assessments can be applied to personalized medicine and diagnostic strategies.

Anaerobic bioreactors are an efficient technology for the biodegradation of emerging contaminants in environmental matrices. In this work, a horizontal-flow anaerobic immobilized biomass (HAIB) bioreactor was used to remove caffeine (CAF), which is frequently found in various aqueous matrices. The acrylic bench top bioreactor, with dimensions of 100 × 5.00 cm, was operated with a hydraulic retention time (HRT) of 12 h, during 45 weeks, under mesophilic conditions. The operation was performed in 4 phases: without CAF addition (phase I); CAF spiked at 300 μg L -1 (phase II); CAF at 600 μg L -1 (phase III); and CAF at 900 μg L -1 (phase IV). Samples of bioreactor influent and effluent were analyzed by liquid chromatography/tandem mass spectrometry (LC-MS/MS). The bioreactor removed organic matter (OM) and CAF with efficiencies of 88 and 93%, respectively. The first-order apparent removal constant (K app ) values for OM and CAF were 0.419 and 0.304 h -1 , respectively. Five transformation products (TPs) were identified, with m/z 243, 227, 211, and 181 (two products). The HAIB bioreactor is a suitable system for the removal of CAF present in wastewater, even at a concentration level of µg L -1 ., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The demand for the development of portable and low-cost analytical devices has encouraged studies employing additive manufacturing techniques, such as 3D-printing. This method can be used to produce components such as printed electrodes, photometers, and fluorometers for low-cost systems that provide advantages including low sample volume, reduced chemical waste, and easy coupling with LED-based optics and other instrumental devices. In the present work, a modular 3D-printed fluorometer/photometer was designed and applied for the determination of caffeine (CAF), ciprofloxacin (CIP), and Fe(ii) in pharmaceutical samples. All the plastic parts were printed separately by a 3D printer, using Tritan as the plastic material (black color). The final size of the modular 3D-printed device was 12 × 8 cm. The radiation sources were light-emitting diodes (LEDs), while a light dependent resistor (LDR) was used as a photodetector. The analytical curves obtained for the device were: y = 3.00 × 10 -4 [CAF] + 1.00 and R 2 = 0.987 for caffeine; y = 6.90 × 10 -3 [CIP] - 3.39 × 10 -2 and R 2 = 0.991 for ciprofloxacin; and y = 1.12 × 10 -1 [Fe(ii)] + 1.26 × 10 -2 and R 2 = 0.998 for iron(ii). The results obtained using the developed device were compared with reference methods, with no statistically significant differences observed. The 3D-printed device was composed of moveable parts, providing flexibility for adaptation and application as a photometer or fluorometer, by only switching the photodetector position. The LED could also be easily switched, permitting application of the device for different purposes. The cost of the device, including the printing and electronic components, was lower than US$10. The use of 3D-printing enables the development of portable instruments for use in remote locations with a lack of research resources., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Thousands of chemical compounds produced by industry are dispersed in the human environment widely enough to reach the world population, and the introduction of new chemicals constantly occurs. As new synthetic molecules emerge, rapid analytical workflows for screening possible presence of exogenous compounds in biofluids can be useful as a first pass analysis to detect chemical exposure and guide the development and application of more elaborate LC-MS/MS methods for quantification. In this study, a suspect screening workflow using the multiple reaction monitoring (MRM) profiling method is proposed as a first pass exploratory technique to survey selected exogenous molecules in human urine samples. The workflow was applied to investigate 12 human urine samples using 310 MRMs related to the chemical functionalities of 87 exogenous compounds present in the METLIN database and reported in the literature. A total of 11 MRMs associated with five different compounds were detected in the samples. Product ion scans for the precursor ions of the selected MRMs were acquired as a further identification step for these chemicals. The suspect screening results suggested the presence of five exogenous compounds in the human urine samples analyzed, namely metformin, metoprolol, acetaminophen, paraxanthine and acrylamide. LC-MS/MS was applied as a last step to confirm these results, and the presence of four out of the five targets selected by MRM profiling were corroborated, indicating that this workflow can support the selection of suspect compounds to screen complex samples and guide more time-consuming and specific quantification analyses., (Copyright © 2022 Elsevier B.V. All rights reserved.)

An on-line solid phase extraction using a lab-made restricted access media (RAM) was developed as sample preparation procedure for determination of the pharmaceutical compounds caffeine (CAF), carbamazepine (CBZ), norfloxacin (NOR), ciprofloxacin (CIP), fluoxetine (FLX) and venlafaxine in wastewater treatment plant samples by liquid chromatography-tandem mass spectrometry (LC-MS/MS). This method is suitable for use in routine of analysis, avoiding cross-contamination and requiring only a small sample volume (50 µL), with minimal handling. The method was validated according to international guidelines. The chromatographic efficiency was evaluated using peak resolution and asymmetry parameters. Carryover was also evaluated, in order to ensure reliability of the analysis and the ability to reuse the cartridge. Satisfactory linearity (r 2  > 0.99) was obtained for all the compounds. The intra- and inter-day precision values were lower than 5.79 and 14.1%, respectively. The limits of detection ranged from 0.01 to 3 µg L -1 and the limits of quantification were from 0.1 to 5 µg L -1 . The method was applied to 20 environmental wastewater samples, with caffeine being the most widely detected compound, at the highest concentration of 392 µg L -1 , while other compounds were detected in fewer samples at lower concentrations (up to 9.60 µg L -1 ). The lab-made modification is a cheaper option for on-line sample preparation, compared to commercially available on-line SPE cartridges and RAM columns. Moreover, a high-throughput procedure was achieved, with an analysis time of 16 min including sample preparation and chromatographic separation. The same RAM column was applied over 200 injections including method optimization, validation and application in wastewater samples without loss of analytical response., (Copyright © 2021 Elsevier B.V. All rights reserved.)

An automated method was developed using on-line solid-phase extraction (SPE) as a sample preparation step, coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS), for determination of pharmaceutical compounds in wastewater samples at nanograms per liter to micrograms per liter concentration levels. This method is suitable for use in routine analysis, especially in environmental applications, avoiding cross-contamination and requiring minimal sample handling. Results can be obtained rapidly, with a chromatographic run time of only 24 min (including sample preparation and chromatographic analysis). Using a 50 μL injection volume, the method was validated according to international guidelines, considering parameters included in terms of method detection (MDL) and quantification limit (MQL), linearity, inter-day and intra-day precisions, and matrix effects. Assessment of chromatographic efficiency considered peak resolution and asymmetry, and carryover was evaluated to ensure analytical reliability and the ability to reuse the SPE cartridge. The intra- and inter-day precisions were lower than 10 and 17%, respectively. The MDL values ranged from 1×10 -6 to 1 μg L -1 , while the MQL values were from 0.001 to 3 μg L -1 . Matrix effects were minimized by isotope dilution calibration. Application of the method to 20 wastewater samples showed that caffeine was the most frequently detected compound, with the highest concentration of 715 μg L -1 , while other pharmaceutical compounds were detected in fewer samples and at lower concentrations (up to 8.51 μg L -1 )., (© 2021. Springer-Verlag GmbH Germany, part of Springer Nature.)

Emerging contaminants, including pharmaceutical compounds, are receiving research attention as a result of their widespread presence in effluents and wastewater treatment plants (WWTPs). The antibiotic ciprofloxacin (CIP) is extensively employed to treat infections in animal and human medicine. Both CIP and its metabolites are common contaminants found in WWTPs. In this study, a label-free ultrasensitive U-bent optical fiber-based immunosensor for the determination of CIP in wastewater samples was developed using the properties of the conducting polymer polyaniline (PANI). The anti-CIP immunoglobulin G (IgG) was deposited on a silica optical fiber surface previously functionalized with PANI. Scanning electron microscopy and micro-Raman spectroscopy were used to investigate the surface of the immunosensor. The analysis of CIP in wastewater was performed without the use of an organic solvent or sample preparation steps, with only the sample dilution in saline buffer (pH = 7.4). The linear range for CIP was from 0.01 to 10,000 ng L -1 . The detection limit was 3.30 × 10 -3 ng L -1 and the quantification limit was 0.01 ng L -1 . The immunosensor provided a high average recovery of 91% after spiking wastewater samples with CIP at a concentration of 9,100 ng L -1 . The method was applied in triplicate to wastewater samples from Quebec (Canada), obtaining concentrations of 549 and 267 ng L -1 . A comparison with a reference method showed no significant difference ( t -test at 95% confidence). The new technique developed is selective, allowing a quantitative analysis of CIP in wastewater.

Colorimetric techniques have been developed and used in routine analyses for over a century and apparently all their potentialities have been exhaustively explored. However, colorimetric techniques have gained high visibility in the last two decades mainly because of the development of the miniaturization concept, for example, paper-based analytical devices that mostly employ colorimetric reactions, and by the advances and popularity of image capture instruments. The impressive increase in the use of these devices was followed by the development and enhancement of different modes of color detection to meet the demands of making qualitative, semi-quantitative, and fully quantitative analyses of multiple analytes. Cameras, scanners, and smartphones are now being used for this purpose and have become suitable alternatives for different approaches to colorimetric analysis; this, in addition to advancements in miniaturized devices. On the other hand, recent developments in optoelectronics technologies have launched more powerful, more stable and cheaper light-emitting diodes (LEDs), which once again have become an interesting tool for the design of portable and miniaturized devices based on colored reactions. Here, we present a critical review of recent developments and challenges of colorimetric detection in modern analytical chemistry in the last five years, and present thoughts and insights towards future perspectives in the area to improve the use of colorimetric detection in different application approaches., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this study an impedimetric immunosensor was developed in order to determine ciprofloxacin (CIP) in wastewater samples, an emergent contaminant widely found in wastewater. To achieve this, an anti-ciprofloxacin antibody was immobilized on the surface of a printed carbon electrode. Then, the developed immunosensor was applied in wastewater samples from Université Laval residences (Québec, Canada) through the load transfer resistance ( R ct ) using [Fe(CN) 6 ] 3-/4- as a redox probe, and the average CIP concentration was found to be 2.90 × 10 -4 μg mL -1 . The observed R ct changes presented a linear relationship from CIP concentrations of 10 -5 to 1.0 μg mL -1 , with detection and quantification limits of 2.50 × 10 -6 and 7.90 × 10 -6 μg mL -1 , respectively. The immunosensor presented high selectivity and repeatability, as well as a good recovery rate in wastewater samples (97%). Significant interference with other compounds was not observed. The proposed method requires only 30 μL of sample without the use of organic solvents or preceding sample preparation and/or extraction techniques. Moreover, the method is fast: only 20 min of incubation followed by 2 min of analysis time was sufficient to obtain the CIP concentration. The method's estimated cost is U$ 2.00 per sample., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Caffeine is an element that is consumed worldwide. It is present in many products such as beverages, chocolate, coffee, tea, energy drinks and medicines. Portable 3D devices working together with colorimetric and fluorimetric reactions have been able to determine the presence of caffeine in different kinds of samples. Also, digital image-based methods using smartphones have conferred portability and accessibility to miniaturized devices that are innovative and promising options for quick and low cost analyses. This study proposes a miniaturized fluorimetric device to determine caffeine by digital image using a smartphone. The OpenCamera app was used to capture images that were processed using ImageJ software to obtain RGB channels values. The red (R) channel signal intensity was selected as the analytical response. The device developed was applied to determine caffeine in an energy drink and medicines. The method developed presented a linear range from 100 to 600 mg L -1 of caffeine, and quantification (LOQ) and detection (LOD) limits of 100 mg L -1 and 30.0 mg L -1 , respectively. The caffeine concentration found in the products analyzed was 328 mg L -1 (±2.5%) for the energy drink, 345 mg L -1 (±15%) for medicine A and 322 mg L- 1 (±7.3%) for medicine B. The proposed device presented important characteristics such as low cost, required small volumes of reagents and samples, quick analysis, portability and suitable to be applied in complex matrices., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Sulfamethazine (SMZ) is an antibiotic from sulfonamides class widely used in veterinary medicine and reported in wastewater and sewage. Thus, it is essential to study technologies to reduce SMZ present in the aquatic environment. Anaerobic bioreactors are a low-cost technology applied for wastewater treatment. The objective of this paper is to study kinetics parameters related to SMZ removal using a horizontal flow-anaerobic immobilized biomass reactor (HAIB) and to evaluate its transformation products formed during this treatment. The bioreactor was operated at mesophilic condition with a hydraulic retention time of 12 h. The removal of SMZ was evaluated at three different concentrations: 200 ng L -1 (phase I), 400 ng l -1 (phase II) and 600 ng L -1 (phase III). The apparent first-order removal constant obtained for chemical oxygen demand was 0.885 ± 0.094 h -1 while SMZ showed a removal constant of 0.356 h -1 . SMZ was removed with an efficiency of 56.0 ± 13.0 % (phase I); 62.0 ± 12.0 % (phase II) and 62.0 ± 6.00 % (phase III). Seven transformation products were detected and one of these with m/z 233 is reported for the first-time. The HAIB bioreactor has a potential to assist in wastewater treatment to remove contaminants at ng L -1 concentration level., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The use of anaerobic biomass attached to a support has been recently presented as a good prospect in the treatment of wastewater containing recalcitrant compounds, such as sulfamethazine (SMZ). SMZ has been found in swine wastewater and sewage treatment plants, which motivates assessing their degradation by new wastewater treatment technologies. Thus, this paper describes the use of a continuous fixed structured bed bioreactor for the purpose of evaluating SMZ removal kinetics present in lab-made wastewater. The analysis of SMZ used online solid-phase extraction coupled to liquid chromatography/tandem mass spectrometry (SPE online-LC-MS/MS). Chemical oxygen demand (COD) was also monitored to evaluate the organic matter removal. The bioreactor was operated under mesophilic conditions (30 ∘ C), with a hydraulic retention time of 24 h. In order to evaluate SMZ removal, four different concentration levels were studied: 200, 400, 600, and 800 ng L -1 . COD removal efficiency obtained for filtered effluent kept at 91.01% and there was no interference due to the increase of SMZ concentration. For SMZ, the removal efficiencies were of 52.8 ± 12.1 % for 200 ng L -1 concentration level; 55.0 ± 8.15 % for 400 ng L -1 ; 53.0 ± 6.14 % for 600 ng L -1 , and 48.8 ± 5.44 % for 800 ng L -1 . COD removal kinetics presented a first-order apparent removal rate constant ( k app ) of 0.281 ± 0.0295  h -1 . SMZ also showed a first-order apparent removal rate constant of 0.158 ± 0.0093  h -1 for the following concentrations levels: 200, 400, 600, and 800 ng L -1 .

This study presents a new method developed for the simultaneous determination of anionic surfactant (linear alkylbenzene sulfonate - LAS, 4 homologs) and nonionic surfactant (linear alcohol ethoxylate - LAE) in commercial laundry wastewater. The surfactants were identified and quantified using online column-switching solid-phase extraction (SPE) coupled with liquid chromatography/tandem mass spectrometry (LC-MS/MS). Ten and three transitions (m/z) were identified for LAS and LAE, respectively. The detection and quantification limits were 75 and 200μg/L for LAS, respectively, and 75μg/L for LAE. This method was applied to the determination of the surfactants in the influent and effluent of an anaerobic fluidized bed reactor that was used for the treatment of commercial laundry wastewater. After 480days of operation with a hydraulic retention time (HRT) of 18h, the removal of 45.9±5.6% LAS and 99.2±4.3% LAE from an influent with surfactant concentrations of 26.1±12.9mg/L and 23.8±6.8mg/L, respectively, was obtained. Under these conditions, the breakage of longer-chain LAS homologs with the release of carbon units was observed with an increase in the number of shorter homolog chains. This SPE online sample treatment method is simple, fast and effective for the analysis of both surfactants. This technique is pioneering in its simultaneous measurement of two surfactant categories in anaerobic fluidized bed reactors., (Copyright © 2016 Elsevier B.V. All rights reserved.)