Complete holography-based system for the identification of microparticles in water samples.

Here, we present a comprehensive holography-based system designed for detecting microparticles through microscopic holographic projections of water samples. This system is designed for researchers who may be unfamiliar with holographic technology but are engaged in microparticle research, particularly in the field of water analysis. Additionally, our innovative system can be deployed for environmental monitoring as a component of an autonomous sailboat robot. Our system's primary application is for large-scale classification of diverse microplastics that are prevalent in water bodies worldwide. This paper provides a step-by-step guide for constructing our system and outlines its entire processing pipeline, including hologram acquisition for image reconstruction.

Embedding Mixed Sorbents in Binder: Solid-Phase Microextraction Coating with Wide Extraction Coverage and Its Application in Environmental Water Analysis.

Solid-phase microextraction (SPME) is a simple and highly effective sample-preparation technique for water analysis. However, the extraction coverage of a given SPME device with a specific coating can be an issue when analyzing multiple environmental contaminants. Therefore, instead of synthesizing one sorbent material with dual or multiple functions, we investigated a new strategy of preparing SPME blades using a homogeneous slurry made by mixing three different sorbent particles─namely, hydrophobic/lipophilic balanced (HLB), HLB-weak cationic exchange (HLB-WCX), and HLB-weak anionic exchange (HLB-WAX)─with a polyacrylonitrile (PAN) binder. The developed coating is matrix compatible, as the binder functions not only as a glue for immobilizing the sorbent particles but also as a porous filter, which only allows small molecules to enter the pores and interact with the particles, thus avoiding contamination from large elements. The results confirmed that the proposed mixed-coating SPME device provides good extraction performance for polar and nonpolar as well as positively and negatively charged compounds. Based on this device, three comprehensive analytical methodologies─high-throughput SPME-LC-MS/MS (for the quantitative analysis of targeted drugs of abuse and artificial sweeteners), in-bottle SPME-LC-high resolution MS (HRMS) (for the untargeted screening of organic contaminants), and on-site drone sampling SPME-LC-HRMS (for on-site sampling and untargeted screening)─were developed for use in environmental water analysis. The resultant data confirm that the proposed strategies enable comprehensive water quality assessment by using a single SPME device.

Non-target screening in water analysis: recent trends of data evaluation, quality assurance, and their future perspectives.

This trend article provides an overview of recent advancements in Non-Target Screening (NTS) for water quality assessment, focusing on new methods in data evaluation, qualification, quantification, and quality assurance (QA/QC). It highlights the evolution in NTS data processing, where open-source platforms address challenges in result comparability and data complexity. Advanced chemometrics and machine learning (ML) are pivotal for trend identification and correlation analysis, with a growing emphasis on automated workflows and robust classification models. The article also discusses the rigorous QA/QC measures essential in NTS, such as internal standards, batch effect monitoring, and matrix effect assessment. It examines the progress in quantitative NTS (qNTS), noting advancements in ionization efficiency-based quantification and predictive modeling despite challenges in sample variability and analytical standards. Selected studies illustrate NTS's role in water analysis, combining high-resolution mass spectrometry with chromatographic techniques for enhanced chemical exposure assessment. The article addresses chemical identification and prioritization challenges, highlighting the integration of database searches and computational tools for efficiency. Finally, the article outlines the future research needs in NTS, including establishing comprehensive guidelines, improving QA/QC measures, and reporting results. It underscores the potential to integrate multivariate chemometrics, AI/ML tools, and multi-way methods into NTS workflows and combine various data sources to understand ecosystem health and protection comprehensively.

Synthesis and characterization of pH-responsive deep eutectic solvent followed by HPLC for trace determination of bisphenol A in water samples.

A microextraction based on pH-responsive deep eutectic solvent combined with high-performance liquid chromatography was developed for the separation, preconcentration, and determination of bisphenol A in water samples. Five deep eutectic solvents were prepared using thymol (hydrogen bond acceptor) and 6-, 8-, 9-, 10-, and 12-carbon carboxylic acids (hydrogen bond donor), and were used as extraction solvent. Herein, by alkalinizing the environment, phase transition takes place, and by adding acid, phase separation and extraction of analytes occur simultaneously. Some important parameters on the extraction such as deep eutectic solvent type, molar ratio of deep eutectic solvent components, deep eutectic solvent volume, potassium hydroxide concentration, hydrochloric acid volume, extraction time, and salt addition were optimized. Under the optimum conditions, intra- and interday precisions of the method based on seven replicate measurements of 10 µg L-1 of bisphenol A in water samples were 2.2% and 4.3%, respectively. The analytical performance of the method showed linearity over the concentration of 0.05-50 µg L-1 with the detection limit of 0.02 µg L-1 . The accuracy of the method was confirmed by spiking different concentrations of bisphenol A in real water samples and obtaining relative recoveries in the range of 92.5%-105.2%.

PathoSense: a rapid electroanalytical device platform for screening Salmonella in water samples.

Salmonella contamination is a major global health challenge, causing significant foodborne illness. However, current detection methods face limitations in sensitivity and time, which mostly rely on the culture-based detection techniques. Hence, there is an immediate and critical need to enhance early detection, reduce the incidence and impact of Salmonella contamination resulting in outbreaks. In this work, we demonstrate a portable non-faradaic, electrochemical sensing platform capable of detecting Salmonella in potable water with an assay turnaround time of ~ 9 min. We evaluated the effectiveness of this sensing platform by studying two sensor configurations: one utilizing pure gold (Au) and the other incorporating a semiconductor namely a zinc oxide thin film coated on the surface of the gold (Au/ZnO). The inclusion of zinc oxide was intended to enhance the sensing capabilities of the system. Through comprehensive experimentation and analysis, the LoD (limit of detection) values for the Au sensor and Au/ZnO sensor were 0.9 and 0.6 CFU/mL, respectively. In addition to sensitivity, we examined the sensing platform's precision and reproducibility. Both the Au sensor and Au/ZnO sensor exhibited remarkable consistency, with inter-study percentage coefficient of variation (%CV) and intra-study %CV consistently below 10%. The proposed sensing platform exhibits high sensitivity in detecting low concentrations of Salmonella in potable water. Its successful development demonstrates its potential as a rapid and on-site detection tool, offering portability and ease of use. This research opens new avenues for electrochemical-based sensors in food safety and public health, mitigating Salmonella outbreaks and improving water quality monitoring.

Magnetic Poly(Amidoamine) Dendrimer for the Dispersive Solid Phase Extraction of Nitrophenols from Environmental Water Samples.

A fast and simple dispersive solid phase extraction method is described for nitrophenols determination in water samples by using gas chromatography-nitrogen phosphorous detector. Firstly, the Poly(amidoamine) grafted Fe3O4 magnetic nanoparticles were synthesized in different generations by successive addition of butyl acrylate and ethylenediamine. After characterization, the prepared dendrimer was utilized as an adsorbent for magnetic solid phase extraction of 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol to benefit large number of surface amine interaction sites. The effects of the different parameters influencing the sample preparation efficiency were investigated. The proposed method showed linearity in the ranges of 0.04-700 and 0.05-700 µg/dm3 for nitrophenols. The obtained limits of detection and quantification under optimized conditions were 0.01-0.02 and 0.04-0.05 µg/dm3, respectively. The relative standard deviations (n = 5) were less than 3.8% (at 10 µg/dm3). Moreover, the calculated enrichment factors were above 200. In addition, the relative recoveries for a spiked river water sample were satisfactory.

Electrokinetic motion and viability assessment of algae with a polyethylene glycol-dextran interface.

At present, there is still limited report on the electrokinetic (EK) behavior of bioparticles at the interface of an aqueous two-phase system. In this paper, the EK motion and viability assessment of live algae mixed with the NaClO treated dead algae were carried out at the interface formed by polyethylene glycol (PEG)-rich phase and dextran (DEX)-rich phase in a straight microchannel. The experimental results show that both the live and dead algae at the PEG-DEX interface migrate from the negative electrode to the positive electrode, and the EK velocity of live algae at the interface is slightly larger than that of the dead ones with similar diameters. For either live or dead algae, the EK velocity at the interface decreases with the increase in diameter. A size-velocity curve was used to evaluate the viability of the algae. As most of the microorganisms in ballast water are algae, the method in this paper provides a promising way to detect and evaluate the live microorganism in treated ballast water of a ship.

Synthesis and Applications of Fluorescent Chemosensors: A Review.

Fluorescent sensors have emerged as powerful tools in analytical chemistry for the detection and quantification of heavy and transition metal ions in aqueous samples. These metal ions pollute the environment and cause a number of diseases, such as irritability, anaemia, muscle paralysis, neurological damage, and memory loss. Moreover, we explore the wide spectrum of applications in environmental monitoring, where these sensors enable precise detection of contaminants, as well as in biomedical fields, facilitating diagnostic and therapeutic advancements. While highlighting the exceptional progress achieved in this field, I also address the challenges and future prospects for the continued development of fluorescent sensors, emphasizing their potential to shape the future of water quality assessment and analytical chemistry. Heavy and transition metals are of great concern because of their extreme toxicity even at very low concentration and tendency to be accumulated in bodies of living organisms. During the recent years, the design and synthesis of fluorescent chemosensors for sensing environmentally and biologically relevant important metals, particularly for heavy and transition metals, is of great interest. Opon complexation with heavy and transition metals, the fluorescence intensity of these fluorescent chemosensors either quenched or enhanced. The current review paper explains various fluorescent chemosensors for determination of toxic heavy and transition metals in environmental water samples.

Development and validation of a GC × GC-ToFMS method for the quantification of pesticides in environmental waters.

Water is a fundamental resource for living things, which is why its control is necessary. The widespread use of pesticides for agricultural and non-agricultural purposes has resulted in the presence of their residues in surface water and groundwater resources. Their presence in water is regulated through different directives, such as the Groundwater Directive, the Drinking Water Directive, and the Water Framework Directive, modified later several times, setting a maximum concentration of 0.1 µg.L-1 for individual pesticides and their degradation products, and 0.5 µg.L-1 for total pesticide residues present in a sample. There are different kinds of pesticides (e.g., organophosphorus and organochlorine pesticides, triazines, chloroacetamides, triazoles, (thio)carbamates) that have diverse chemical structures. Their determination and monitoring in a single analytical procedure are possible through multiresidue methods. In this study, 53 pesticides belonging to different chemical classes and their metabolites were selected based on their local occurrence and investigated in surface water and groundwater from agricultural areas susceptible to pesticide contamination. The methodology consisted of a classical solid-phase extraction (SPE) for the purification and enrichment of the pesticides, with a subsequent analysis in multidimensional gas chromatography coupled to mass spectrometry (GC×GC-MS). The quantification method was validated according to the Eurachem Guide in terms of linearity, precision, accuracy, limit of detection, and limit of quantification. After validation, the method was applied to 34 real-world water samples, and the results were compared with those obtained by a GC-QMS routine method.

Complementary methods for structural assignment of isomeric candidate structures in non-target liquid chromatography ion mobility high-resolution mass spectrometric analysis.

Non-target screening with LC/IMS/HRMS is increasingly employed for detecting and identifying the structure of potentially hazardous chemicals in the environment and food. Structural assignment relies on a combination of multidimensional instrumental methods and computational methods. The candidate structures are often isomeric, and unfortunately, assigning the correct structure among a number of isomeric candidate structures still is a key challenge both instrumentally and computationally. While practicing non-target screening, it is usually impossible to evaluate separately the limitations arising from (1) the inability of LC/IMS/HRMS to resolve the isomeric candidate structures and (2) the uncertainty of in silico methods in predicting the analytical information of isomeric candidate structures due to the lack of analytical standards for all candidate structures. Here we evaluate the feasibility of structural assignment of isomeric candidate structures based on in silico-predicted retention time and database collision cross-section (CCS) values as well as based on matching the empirical analytical properties of the detected feature with those of the analytical standards. For this, we investigated 14 candidate structures corresponding to five features detected with LC/HRMS in a spiked surface water sample. Considering the predicted retention times and database CCS values with the accompanying uncertainty, only one of the isomeric candidate structures could be deemed as unlikely; therefore, the annotation of the LC/IMS/HRMS features remained ambiguous. To further investigate if unequivocal annotation is possible via analytical standards, the reversed-phase LC retention times and low- and high-resolution ion mobility spectrometry separation, as well as high-resolution MS2 spectra of analytical standards were studied. Reversed-phase LC separated the highest number of candidate structures while low-resolution ion mobility and high-resolution MS2 spectra provided little means for pinpointing the correct structure among the isomeric candidate structures even if analytical standards were available for comparison. Furthermore, the question arises which prediction accuracy is required from the in silico methods to par the analytical separation. Based on the experimental data of the isomeric candidate structures studied here and previously published in the literature (516 retention time and 569 CCS values), we estimate that to reduce the candidate list by 95% of the structures, the confidence interval of the predicted retention times would need to decrease to below 0.05 min for a 15-min gradient while that of CCS values would need to decrease to 0.15%. Hereby, we set a clear goal to the in silico methods for retention time and CCS prediction.

Synthesis and characterization of phenothiazine sensor for spectrophotometric and fluorescence detection of cyanide.

A sensitive and selective phenothiazine-based sensor (PTZ) has been successfully synthesized. The sensor PTZ displayed specific identification of CN- 'turn-off' fluorescence responses with a quick reaction and strong reversibility in an acetonitrile:water (90:10, V/V) solution. The sensor PTZ for detecting CN- exhibits the marked advantages of quenching the fluorescence intensity, fast response time (60 s), and low value of the detection limit. The concentration that is authorized for drinking water by the WHO (1.9 µM) is far higher than the detection limit, which was found to be 9.11 × 10-9 . The sensor displays distinct colorimetric and spectrofluorometric detection for CN- anion due to the addition of CN- anion to the electron-deficient vinyl group of PTZ, which reduces intramolecular charge transfer efficiencies. The 1:2 binding mechanism of PTZ with CN- was validated by fluorescence titration, Job's plot, HRMS, 1 H NMR, FTIR analysis, and density functional theory (DFT) investigations, among other methods. Additionally, the PTZ sensor was successfully used to precisely and accurately detect cyanide anions in actual water samples.

Flower-like molybdenum disulfide/cobalt ferrite composite for the extraction of benzotriazole UV stabilizers in environmental samples.

Benzotriazole UV stabilizers (BUVSs) are a class of emerging contaminants of concern; the development of rapid and convenient monitoring method for these trace-level pollutants in waters is of crucial significance in environmental science. Here, a novel magnetic flower-like molybdenum disulfide/cobalt ferrite nanocomposite (MoS2/CoFe2O4) was synthesized by hydrothermal reaction. Compared with the conventional Fe3O4-based magnetic composites, the proposed material just required a minimum consumption of Co/Fe towards the equivalent of MoS2 while providing superior magnetization performance. Taking advantages of high adsorption capacity, extraordinary stability, and repeatability in construction, MoS2/CoFe2O4 was applied to the extraction to BUVSs. The enrichment factors of three BUVSs were in the range 164-193 when 20 mL of environmental water sample was loaded on 40 mg of the adsorbent. MoS2/CoFe2O4 could be regenerated and recycled at least 10 cycles of adsorption/desorption with recoveries of 80.1-111%. The method of MoS2/CoFe2O4-based extraction coupled with high-performance liquid chromatography-variable wavelength detector was applied to the monitoring of BUVSs in seawater, lake water, and wastewater, which gave detection limits (S/N = 3) of 0.023-0.030 ng·mL-1 and recoveries of 80.1-110%. The intra-day and inter-day precisions (relative standard deviation, RSDs, n = 3) were in the range 1.6-7.5% and 3.2-11.5%, respectively. The approach is an alternative for efficient and sensitive extraction and determination of trace-level environmental pollutants in waters.

Preparation of molecularly imprinted ratiometric fluorescence sensor for visual detection of tetrabromobisphenol A in water samples.

A sensitive molecularly imprinted ratiometric fluorescence sensor was constructed for the first time to visually detect tetrabromobisphenol A (TBBPA). The blue fluorescent carbon quantum dots (CQDs) were coated with SiO2 through the reverse microemulsion method to obtain a stable internal reference signal CQDs@SiO2. The ratiometric fluorescence sensor was finally prepared using red fluorescent CdTe QDs as the response signal in the presence of CQDs@SiO2. When the molecularly imprinted polymers were combined with TBBPA, the fluorescence of CdTe QDs (Ex = 365 nm, Em = 665 nm) was rapidly quenched, while that of CQDs (Ex = 365 nm, Em = 441 nm) remained stable, resulting in a noticeable fluorescence color change. Moreover, the fluorescence intensity ratio (I665/I441)0/(I665/I441) of the sensor showed a linear response to TBBPA in the concentration range 0.1 to 10 µM with a low detection limit of 3.8 nM. The prepared sensor was successfully applied to detect TBBPA in water samples. The recoveries were in the range 98.2-103%, with relative standard deviations lower than 2.5%. Furthermore, a fluorescent test strip for visual monitoring of TBBPA was constructed to streamline the procedure. The excellent results demonstrate that the prepared test strip has a broad prospect for the offline detection of pollutants.

Dispersive solid phase extraction based on cross-linked hydroxypropyl ß-cyclodextrin polymers for simultaneous enantiomeric determination of three chiral triazole fungicides in water.

An efficient method is presented for simultaneous enantioselective determination of three chiral triazole fungicides (namely paclobutrazol, hexaconazole, and diniconazole) in water samples by DSPE-HPLC-UV. The perfect chiral separation of the enantiomers was achieved on a Chiralpak IH column within 15 min. In order to adsorb and enrich the analytes from water matrices, a cross-linked hydroxypropyl ß-cyclodextrin polymer was synthesized. The prepared material exhibited good adsorption capacity, which was assessed by adsorption kinetic and adsorption thermodynamic experiments. One-variable-at-a-time and the response surface methodology were used to optimize the extraction parameters. Under the optimum sample preparation conditions, good linearity (2.0 ~ 800 µg L-1, R2 ≥ 0.9978), detection limits (0.6 to 1.0 µg L-1), quantitation limits (2.0 to 3.2 µg L-1), recoveries (86.7 ~ 105.8%), and the relative standard deviation (intra-day RSD ≤ 3.7%, inter-day RSD ≤ 5.1%) were obtained, satisfying the requirements of pesticides residues determination. These results demonstrated that the proposed method was applicable for routine determination of chiral triazole fungicide residues in water samples.

Dispersive magnetic solid phase extraction of triazole fungicides based on polybenzidine/magnetic nanoparticles in environmental samples.

A polybenzidine-modified Fe3O4@SiO2 nanocomposite was successfully synthesized through a chemical oxidation method and employed as a novel sorbent in dispersive magnetic solid phase extraction (DMSPE) for the preconcentration and determination of three triazole fungicides (TFs), namely diniconazole, tebuconazole, and triticonazole in river water, rice paddy soil, and grape samples. The synthesis method involved a polybenzidine self-assembly coating on Fe3O4@SiO2 magnetic composite. Characterization techniques such as FT-IR, XRD, FESEM, EDX, and VSM were used to confirm the correctness of the synthesized nano-sorbent. The target TFs were determined in actual samples using the synthesized nanocomposite sorbent in combination with gas chromatography-flame ionization detection (FID). Several variables were carefully optimized , including the sample pH, sorbent dosage, extraction time, ionic strength, and desorption condition (solvent type, volume, and time). Under the optimized experimental conditions, the method exhibited linearity in the concentration range 5-1000 ng mL-1 for triticonazole and 2-1000 ng mL-1 for diniconazole and tebuconazole. The limits of detection (LOD) for the three TFs were in the range 0.6-1.5 ng mL-1. The method demonstrated acceptable precision with intra-day and inter-day relative standard deviation (RSD) values of less than 6.5%. The enrichment factors ranged from 248 to 254. Finally, the method applicability was evaluated by determining TFs in river water, rice paddy soil, and grape samples with recoveries in the range 90.5-106, indicating that the matrix effect was negligible in the proposed DMSPE procedure.

Sensitive Silver-Enhanced Microplate Apta-Enzyme Assay of Sb3+ Ions in Drinking and Natural Waters.

The toxic effects of antimony pose risks to human health. Therefore, simple analytical techniques for its widescale monitoring in water sources are in demand. In this study, a sensitive microplate apta-enzyme assay for Sb3+ detection was developed. The biotinylated aptamer A10 was hybridized with its complementary biotinylated oligonucleotide T10 and then immobilized on the surface of polysterene microplate wells. Streptavidin labeled with horseradish peroxidase (HRP) bound to the biotin of a complementary complex and transformed the 3,3',5,5'-tetramethylbenzidine substrate, generating an optical signal. Sb3+ presenting in the sample bounded to an A10 aptamer, thus releasing T10, preventing streptavidin-HRP binding and, as a result, reducing the optical signal. This effect allowed for the detection of Sb3+ with a working range from 0.09 to 2.3 µg/mL and detection limit of 42 ng/mL. It was established that the presence of Ag+ at the stage of A10/T10 complex formation promoted dehybridization of the aptamer A10 and the formation of the A10/Sb3+ complex. The working range of the Ag+-enhanced microplate apta-enzyme assay for Sb3+ was determined to be 8-135 ng/mL, with a detection limit of 1.9 ng/mL. The proposed enhanced approach demonstrated excellent selectivity against other cations/anions, and its practical applicability was confirmed through an analysis of drinking and spring water samples with recoveries of Sb3+ in the range of 109.0-126.2% and 99.6-106.1%, respectively.

Recent Trends in Graphene-Based Sorbents for LC Analysis of Food and Environmental Water Samples.

This review provides an overview of recent advancements in applying graphene-based materials as sorbents for liquid chromatography (LC) analysis. Graphene-based materials are promising for analytical chemistry, including applications as sorbents in liquid chromatography. These sorbents can be functionalized to produce unique extraction or stationary phases. Additionally, graphene-based sorbents can be supported in various materials and have consequently been applied to produce various devices for sample preparation. Graphene-based sorbents are employed in diverse applications, including food and environmental LC analysis. This review summarizes the application of graphene-based materials in food and environmental water analysis in the last five years (2019 to 2023). Offline and online sample preparation methods, such as dispersive solid phase microextraction, stir bar sorptive extraction, pipette tip solid phase extraction, in-tube solid-phase microextraction, and others, are reviewed. The review also summarizes the application of the columns produced with graphene-based materials in separating food and water components and contaminants. Graphene-based materials have been reported as stationary phases for LC columns. Graphene-based stationary phases have been reported in packed, monolithic, and open tubular columns and have been used in LC and capillary electrochromatography modes.

Evaluating the impact of a cemetery on groundwater by multivariate analysis.

Water analyses in conjunction with hydrological and geotechnical investigations were carried out to assess the potential for groundwater contamination from the decomposition of buried human bodies. Water samples were collected from 2007 to 2018 in three monitoring wells built within the cemetery area. Water quality was evaluated based on the determination of 25 analytical parameters (20 physical-chemical and 5 microbiological). Laboratory data reported by the local sewage water company for water collected in household cisterns located outside the cemetery area were also evaluated. Multivariate analysis showed a similar pattern between iron content, turbidity, and rainfall data collected at the rainfall station closest to the study area. This behavior is a direct consequence of soil leaching (oxisol). The physical characterization of the soil of the unsaturated area above the aquifer indicates that the absorption of body waste by the soil is favored, preventing surface contaminants from reaching the aquifer. This work also found that the water samples collected outside the cemetery area do not comply with the Brazilian limits for drinking water. In conclusion, water samples collected from monitoring wells located within the cemetery area have little to none impact on both subsurface and underground contamination.

Selective Detection of Mg2+ for Sensing Applications in Drinking Water.

A new series of ligands containing the 2-(2-hydroxy-3- naphthyl)-4-methylbenzoxazole (HNBO) fluorophore showed selectivity for Mg2+ ions, without the interference of Ca2+ . The most promising representative L3 resulted the best performing sensor for Mg2+ both in solution and embedded in an all-solid-state optode, especially towards real samples of drinkable water.

Recent advances in aptamer applications for analytical biochemistry.

Aptamers are typically defined as relatively short (20-60 nucleotides) single-stranded DNA or RNA molecules that bind with high affinity and specificity to various types of targets. Aptamers are frequently referred to as "synthetic antibodies" but are easier to obtain, less expensive to produce, and in several ways more versatile than antibodies. The beginnings of aptamers date back to 1990, and since then there has been a continual increase in aptamer publications. The intent of the present account was to focus on recent original research publications, i.e., those appearing in 2019 through April 2020, when this account was written. A Google Scholar search of this recent literature was performed for relevance-ranking of articles. New methods for selection of aptamers were not included. Nine categories of applications were organized and representative examples of each are given. Finally, an outlook is offered focusing on "faster, better, cheaper" application performance factors as key drivers for future innovations in aptamer applications.