Spiked River Water Samples Research Articles

Silkworm-derived carbon nano rods (swCNR) for detection of bismuth ions (Bi3+) in aquatic medium and their antiradical properties

The extensive utilization of bismuth and its derivatives in many industries, such as chemical, semiconductor, pharmaceutical, and cosmetics, leads to their accumulation in wastewater, posing a risk to both human health and the environment. Carbon nanorods (CNR) are fluorescent nanoparticles with an ability to detect various analytes as sensing probes. This study focuses on the production, structure, and chemical composition characterization of silkworm-derived CNR (swCNR) and their ability to detect bismuth ions (Bi3+) and inhibit radicals. The optimum wavelength for exciting the fluorescence of swCNR was 370 nm, and the resulting emission peak was observed at 436 nm. The prepared swCNR showed static fluorescence quenching mechanism-based sensing of Bi3+ ions with a limit of detection of 175 nM and two linear ranges from 0.5 to 5 μM (R2 = 0.9997) and 10–50 μM (R2 = 0.9995). The swCNR demonstrated high selectivity in detecting Bi3+ ions in the spiked river water samples, thus establishing the swCNR's role as a nano fluorescence probe designed for the selective detection of Bi3+ ions among other metal ions. Favorable results for the antiradical ability of swCNR were obtained against hydroxyl, 2,2 diphenyl-1 picrylhydrazyl, and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) radicals with scavenging percentages of 15, 32, and 90, respectively. The possible applications of swCNR in the environmental and antioxidant sectors are proposed in this study.

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 0.05-700µg/dm3 for nitrophenols. The obtained limits of detection and quantification under optimized conditions were 0.01-0.02 and 0.04-0.05µg/dm3, respectively. The relative standard deviations (n = 5) were less than 3.8% (at 10µg/dm3). Moreover, the calculated enrichment factors were above 200. In addition, the relative recoveries for a spiked river water sample were satisfactory.

Dispersive liquid-liquid microextraction as a novel enrichment approach for compound-specific carbon isotope analysis of chlorinated phenols.

Compound-specific isotope analysis (CSIA) via gas chromatography-isotope ratio mass spectrometry (GC-IRMS) is a potent tool to elucidate the fate of (semi-)volatile organic contaminants in technical and environmental systems. Yet, due to the comparatively low sensitivity of IRMS, an enrichment step prior to analysis often is inevitable. A promising approach for fast as well as economic analyte extraction and preconcentration prior to CSIA is dispersive liquid-liquid microextraction (DLLME) - a well-established technique in concentration analysis of contaminants from aqueous samples. Here, we present and evaluate the first DLLME method for GC-IRMS exemplified by the analysis of chlorinated phenols (4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol) as model compounds. The analytes were simultaneously acetylated with acetic anhydride and extracted from the aqueous phase using a binary solvent mixture of acetone and tetrachloroethylene. With this method, reproducible δ13C values were achieved with errors ≤ 0.6‰ (n = 3) for aqueous concentrations down to 100 μg L-1. With preconcentration factors between 130 and 220, the method outperformed conventional liquid-liquid extraction in terms of sample preparation time and resource consumption with comparable reproducibility. Furthermore, we have demonstrated the suitability of the method (i) for the extraction of the analytes from a spiked river water sample and (ii) to quantify kinetic carbon isotope effect for 2,4,6-trichlorophenol during reduction with zero-valent zinc in a laboratory batch experiment. The presented work shows for the first time the potential of DLLME for analyte enrichment prior to CSIA and paves the way for further developments, such as the extraction of other compounds or scaling up to larger sample volumes.

Sensitive and selective Cu2+ detection via surface plasmon resonance using ionophore decorated nanocrystalline cellulose-graphene oxide thin film

In this work, highly sensitive and selective surface plasmon resonance (SPR) sensor has been developed using nanocrystalline cellulose-graphene oxide-ionophore (NCC-GO-ionophore) for copper ion (Cu2+) detection. By incorporating SPR with nanocrystalline cellulose-graphene oxide-ionophore (NCC-GO-ionophore) thin film, Cu2+ was able to be detected as low as 0.001 ppm until 0.1 ppm. Moreover, the results show that the NCC-GO-ionophore thin film has good sensitivity towards Cu2+ with sensitivity value of 59.9150° ppm−1 from 0.001 to 0.01 ppm and 2.2261° ppm−1 from 0.01 to 0.1 ppm. Besides that, the developed sensor also shows high affinity towards Cu2+ compared to other metal ions. Using the Langmuir isotherm model, the binding affinity constant, K was calculated i.e., 6.881 × 103 M−1. Furthermore, the ability of the sensor to detect Cu2+ in spiked river water sample was also investigated where Cu2+ as low as 0.5 until 100 ppm can be determined. This result shows that the sensor has high sensitivity and selectivity towards Cu2+ detection.

Biosynthesis of magnetosome-nanobody complex in Magnetospirillum gryphiswaldense MSR-1 and a magnetosome-nanobody-based enzyme-linked immunosorbent assay for the detection of tetrabromobisphenol A in water.

In this study, two mutant strains, TBC and TBC+, able to biosynthesize anovel functional magnetosome-nanobody (Nb), were derived from the magnetotactic bacteria Magnetospirillum gryphiswaldense MSR-1. The magnetosome-Nbs biosynthesized by TBC+ containing multi-copies of theNb gene had ahigher binding ability to an environmental pollutant, tetrabromobisphenol A (TBBPA), than those biosynthesized by TBC containing only one copy of theNb gene. The magnetosome-Nbs from TBC+ can effectively bind to TBBPA in solutions with high capacity without being affected by a broad range of NaCl and methanol concentrations as well as pH. Therefore, a magnetosome-Nb-based enzyme-linked immunosorbent assay (ELISA) was developed and optimized for the detection of TBBPA, yielding a half-maximum signal inhibition concentration of 0.23 ng/mL and a limit of detection of 0.025 ng/mL. The assay was used to detect TBBPA in spiked river water samples, giving average recoveries between 90 and 120% and coefficients of variation of2.5-6.3%. The magnetosome-Nb complex could be reused 4 times in ELISA without affecting the performance of the assay. Our results demonstrate the potential of magnetosome-Nbs produced by TBC+ as cost-effective and environment-friendly reagents for immunoassays to detect small molecules in environmental waters.

Adsorptive removal of 4-hydroxybenzoic acid via cross-linked polymeric microbeads: analysis of isothermal, kinetic and thermodynamic parameters

In this study, the performance of cross-linked microbeads prepared through suspension polymerization was investigated for removal of 4-hydroxybenzoic acid (4-HBA) from aqueous solution. Adsorption studies were conducted at different pHs (2.0–8.0), temperatures (282–308 K) and initial 4-HBA concentrations (1–500 mg/L). The maximum 4-HBA adsorption was 49.05 ± 2.89 mg/g at pH 2.0 (282 K). The adsorption data obeyed to the Langmuir isotherm model. The modified Ritchie second-order and the pseudo second-order kinetic model fitted the adsorption data. The 4-HBA adsorption capacity did not significantly change after 10 consecutive usages. Gibbs free energy changes of the adsorption were calculated as −24.372, −28.431 and −29.093 kJ/mol for 282, 298 and 308 K, respectively. The microbeads were also used for the removal of 4-HBA from spiked river water samples. The removal efficiencies of 43.2% to 68.8% and RSDs of 0.49% to 4.78% demonstrated the usability of the microbeads in application.

Electroactive molecularly imprinted polymer nanoparticles for selective glyphosate determination

Redox-active molecularly imprinted polymer nanoparticles selective for glyphosate, MIP-Gly NPs, were devised, synthesized, and subsequently integrated onto platinum screen-printed electrodes (Pt-SPEs) to fabricate a chemosensor for selective determination of glyphosate (Gly) without the need for redox probe in the test solution. That was because, ferrocenylmethyl methacrylate was added to the polymerization mixtures during the NPs synthesis so that the resulting MIP-Gly NPs contained covalently immobilized ferrocenyl moieties as the reporting redox ingredient, conferring these NPs with electroactive properties. MIP-Gly NPs of four different compositions were evaluated. The herein described approach represents a simple and effective way to endow MIP NPs with electrochemical reporting capabilities with neither the need to functionalize them post-synthesis nor to use electrochemical mediators present in the tested solution during the analyte determinations. MIP-Gly NPs synthesized using allylamine and squaramide-based monomers appeared most selective to Gly. The Pt-SPEs modified with MIP-Gly NPs were characterized with differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). Changes in the DPV peak originating from the oxidation of the ferrocenyl moieties in these MIP-Gly NPs served as the analytical signal. The DPV limit of detection and the linear dynamic concentration range for Gly were 3.7 pM and 25 pM–500 pM, respectively. Moreover, the selectivity of the fabricated chemosensors was sufficiently high to determine Gly successfully in spiked river water samples.

Core-shell magnetic molecularly imprinted polymers: nanoparticles targeting selective androgen receptor modulators (sarms) and steroidal models

Super paramagnetic iron oxide nanoparticles (SPIONs) (∼12 nm) were synthesized as the magnetic core for an imprinted polymer (MIP) shell using 4-vinylpyridine as the functional monomer and trimethylolpropane trimethacrylate (TRIM) as the cross-linker, bringing the average size up to ∼45 nm. Five targets were imprinted—the Selective Androgen Receptor Modulators (SARMs) andarine, ligandrol and RAD-140; and the steroids estradiol and gestrinone. All MMIPs produced good selectivity when loaded with a non-target molecule, with all calculated selectivity factors above the 1.2 recommended threshold and also demonstrated good affinity/capacity. The rebinding of the target molecules from a complex matrix was also explored by using spiked river water samples. The SARMs-based MMIPs were able to rebind 99.56, 87.63 and 72.78% of their target molecules (andarine, ligandrol and RAD-140, respectively), while the steroidal-based MMIPs were able to rebind 64.54 and 55.53% of their target molecules (estradiol and gestrinone, respectively) at a nominal loading of 20 ≈μg in 50 mg of NPs. This work highlights the potential of these bi-functional materials for trace material clean-up of complex samples and/or subsequent analysis and opens up possibilities for further simple, rapid-to-synthesise materials for targeted clean-up.

Quantification of 68 elements in river water monitoring samples in single-run measurements

Triple-quadrupole inductively coupled plasma mass spectrometry (ICP-QQQ-MS) is a unique analytical technique which is, next to speciation analyses, applied for the determination of total element concentrations in several matrices. Due to its wide linear range, short analysis times, and the collision-reaction gas technology, it is capable of addressing a high number of analytes in a single run with sufficient low limits of quantification for river water monitoring. Over the last decades, the focus of the environmental monitoring changed from “traditional” and regulated analytes to elements of possibly rising concern from new applications such as the so-called technology-critical elements (TCE). By widening the analytical window of this method for applications in networks of future river water monitoring, a better understanding of natural transport processes and global biogeochemical element cycles will be established and the total number of methods can be reduced. During method development and validation, certified reference materials, calibration check solutions, and spiked river water samples from 12 major German rivers covering different catchment areas were measured and evaluated with the three cell gases He, H2 and O2. The method delivers a best as possible undisturbed simultaneous determination for 68 out of 71 target analytes with recoveries in an accepted range of 80–120% for river water samples (dissolved fraction; <0.45 μm). After comprehensive evaluation, we offer a novel best-practice multi-element method for river water monitoring with the goal of fostering the exchange and discussion between practitioners in long-term river monitoring. It enables the readers to create their own methods based on the scientific needs to monitor elemental “fingerprints” of rivers and their catchments.

A simple fluorescent sensor for highly sensitive detection of UO22+

Extensive application of nuclear energy has caused widespread environmental uranium contamination. New detection approaches without complicated sample pretreatment and precision instruments are in demand for on-site and in-time determination of uranyl ions in environmental monitoring, especially in an emergency situation. In this work, a simple and effective fluorescent sensor (Z)-N'-hydroxy-4-(1,2,2-triphenylvinyl)benzimidamide (TPE-A) with aggregation-induced emission (AIE) character was established and studied. It could realize to detect UO22+via quenching the fluorescence of its aggregation-induced emission, with good selectivity and sensitivity. Such strategy shows a wide linear range from 5.0 × 10−8 mol/L to 4.5 × 10−7 mol/L (R2 = 0.9988) with exceptional sensitivity reaching 4.7 × 10−9 mol/L, which is far below the limit for uranium in drinking water (30 µg/L, ca. 1.1 × 10−7 mol/L) stipulated by the WHO. A response time less than four minutes make it rapid for uranyl ion measurement. It was applied for detection of uranyl ion in spiked river water samples with recoveries in the range of 98.7%-104.0%, comparable to those obtained by ICP-MS. With the advantages of portable apparatus, rapid detection process and high sensitivity, TPE-A can serve as a promising fluorescent sensor for the detection of UO22+ in environmental water samples.

Computational Modelling and Sustainable Synthesis of a Highly Selective Electrochemical MIP-Based Sensor for Citalopram Detection.

A novel molecularly imprinted polymer (MIP) has been developed based on a simple and sustainable strategy for the selective determination of citalopram (CTL) using screen-printed carbon electrodes (SPCEs). The MIP layer was prepared by electrochemical in situ polymerization of the 3-amino-4 hydroxybenzoic acid (AHBA) functional monomer and CTL as a template molecule. To simulate the polymerization mixture and predict the most suitable ratio between the template and functional monomer, computational studies, namely molecular dynamics (MD) simulations, were carried out. During the experimental preparation process, essential parameters controlling the performance of the MIP sensor, including CTL:AHBA concentration, number of polymerization cycles, and square wave voltammetry (SWV) frequency were investigated and optimized. The electrochemical characteristics of the prepared MIP sensor were evaluated by both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Based on the optimal conditions, a linear electrochemical response of the sensor was obtained by SWV measurements from 0.1 to 1.25 µmol L−1 with a limit of detection (LOD) of 0.162 µmol L−1 (S/N = 3). Moreover, the MIP sensor revealed excellent CTL selectivity against very close analogues, as well as high imprinting factor of 22. Its applicability in spiked river water samples demonstrated its potential for adequate monitoring of CTL. This sensor offers a facile strategy to achieve portability while expressing a willingness to care for the environment.

Rapid direct cathodic voltammetric determination of insecticide flonicamid by renewable silver-amalgam film electrode

ABSTRACT The voltammetric characterisation and determination of insecticide flonicamid (N-cyanomethyl-4-(trifluoromethyl)nicotinamide) were performed for the first time using a simple electrochemical sensor, renewable silver-amalgam film electrode (Hg(Ag)FE). During the development of the direct cathodic square wave voltammetric method (SWV) for the determination of flonicamid, a voltammetric behaviour of a target analyte in aqueous Britton-Robinson buffer solution from pH 2.0 to pH 11.98 was examined. In the investigated pH range, the peak which appeared in the potential span between −0.86 V and −1.56 V vs. saturated calomel electrode depending on the applied pH value was chosen for analytical purposes. As optimal pH for the determination of flonicamid, pH 2.5 was selected. Cyclic voltammetric measurements at pH 2.5 confirmed that the electrode reaction mechanism is an irreversible reduction controlled by the diffusion of flonicamid at Hg(Ag)FE. The optimised Hg(Ag)FE-SWV method resulted in good linearity in the concentration range of 1.96–41.2 µg mL−1 while the relative standard deviation of the method was 0.30%. Flonicamid was successfully determined in commercial formulation Teppeki 500 WG® and spiked river water sample by the developed method using the standard addition procedure. The average value of flonicamid amount found in a commercial formulation based on three repetitions was 497.8 ± 0.9 g kg−1, which is in good agreement with the manufacturer’s declaration (500 ± 25 g kg−1) and with comparative high-performance liquid chromatographic measurements with diode array detection where a found average value of flonicamid content was 497.5 ± 11.5 g kg−1. The obtained results also indicate that the developed SWV procedure using Hg(Ag)FE was appropriate for the determination of flonicamid in a spiked river water sample with the recovery of 92.86% and RSD of 6.19%.

Electrochemical performance of passivated antimonene nanosheets and of in-situ prepared antimonene oxide-PEDOT:PSS modified screen-printed graphite electrodes

Herein, we present the production of antimonene nanosheets and the in-situ preparation of antimonene oxide/PEDOT:PSS nanocomposite via tip sonication of bulk β-phase antimony in water and aqueous PEDOT:PSS, respectively. Nanomaterials were characterized via SEM, EDX, XRD, FT-IR, electrochemical impedance spectroscopy and cyclic voltammetry, while the resulting modified graphite screen-printed electrodes (Sbene/SPE and Sbene oxide/PEDOT:PSS/SPE, respectively) were evaluated in the cathodic determination of 4-nitrotoluene (4-NT), which was used as a model compound, in the presence of dissolved oxygen and in deoxygenated environments. Data document the electrochemical passivation of Sbene/SPE, which, on the one hand, demonstrate a beneficial poor activity towards the oxygen reduction reaction, and on the other hand, enhanced detection capabilities, thus allowing the determination of 4-NT at the micromolar concentration level at non-deoxygenated solutions. As a result, passivated Sbene/SPE show great promise in sensing applications outside of the laboratory where the deoxygenation of the samples is a big obstacle. Moreover, data demonstrate enhanced detection capabilities for Nafion membrane protected Sbene oxide/PEDOT:PSS/SPE, in deoxygenated solutions, which exhibit a detection range from 50 to 5000 nM 4-NT, while achieving an LOD of 16.7 nM (S/N 3). Nafion membrane is essential for the reusability of the electrodes. Sbene oxide/PEDOT:PSS/SPE was also used to the analysis of a spiked river water sample. Recovery was 97.9%.

Performance of free-flow field-step electrophoresis as cleanup step for the non-target analysis of environmental water samples

For the analysis of low concentrations of micropollutants in environmental water samples, efficient sample enrichment and cleanup are necessary to reduce matrix effects and to reach low detection limits. For analytes of low and medium polarity, solid-phase extraction is used, but robust methods for the preconcentration of highly polar or ionizable analytes are scarce. In this work, field-step electrophoresis (FSE) was developed as an environmental sample cleanup technique for ionizable micropollutants and ionic transformation products. The FSE electrolyte system preconcentrated 15 acidic model analytes (pKa from −2.2 to 9.1) present in aqueous samples in two fractions by factors of 5–10. Simultaneously, highly mobile matrix compounds were removed including inorganic ions such as sulfate and chloride. The fractions were either directly injected for downstream analysis by reversed-phase liquid chromatography (RPLC) or further processed by evaporative preconcentration with subsequent reconstitution in an organic solvent suitable for separation methods like hydrophilic interaction chromatography. The FSE/RPLC-MS method exhibited high quantitative precision with RSDs of 3–6%. The method was successfully applied to a spiked river water sample and its performance compared with common solid-phase extraction and evaporative concentration, demonstrating a high analyte coverage. FSE combined with non-target screening by RPLC-MS revealed a strong reduction in matrix load especially at low retention times. Seventeen compounds were identified in the FSE fractions sampled at the field step boundary by retention time, accurate mass, and mass fragments. Suspect screening by FSE/RPLC-MS was facilitated by FSE’s selectivity for anionic compounds.

Multifunctional 3D-printed platform integrated with a smartphone ambient light sensor for halocarbon contaminants monitoring

3D-printed platforms integrated with smartphone light sensors have become a powerful tool for the development of frugal and facile biosensing systems. Herein, we report a 3D-printed platform for multimodal analysis (3D-PMA) based on a smartphone ambient light sensor (ALS). The proposed approach was first validated using a microtiter plate reader, and then its application potential was demonstrated by measuring halohydrin dehalogenase activities employing three different sample modes, viz . using enzyme-linked immunosorbent assay (ELISA) plate strips, cuvettes, and the glass fiber membrane as sample containers. For real-sample analysis, 1,3-dichloro-2-propanol (1,3-DCP), a toxic halogenated compound, was successfully detected in spiked river water samples with recoveries in the range of 101.95–109.70%. After demonstrating the suitability for liquid-phase assays, the 3D-PMA was also optimized for 1,3-DCP detection using a glass fiber membrane. The detection could be done using a 10 μ L reaction system with an assay time of 2 min. The assay showed two linear ranges. The calibration equation of Y = 81.687x + 140.060 was obtained from the lower part of the calibration curve and was used to calculate the detection limit of the system. Under optimized conditions, a detection limit of 80 μ M was achieved for 1,3-DCP. The small size of the device endows it with great promise for use as a benchtop and an on-demand detection system. The proposed low-cost and portable system has great potential for the (bio) sensing of different biological and environmental samples where biocomponent-analyte interaction leads to a color change of the reaction system, indicating its applicability in resource-constrained settings. • A smartphone assisted portable system was developed for environmental contaminants monitoring. • 3D-printed platform demonstrated potential utility for multimodal analysis. • Smartphone Ambient Light Sensor as a potential transducer for halocarbon detection.

Multivariate optimization of a two-way technique for extraction of pharmaceuticals in surface water using a combination of membrane assisted solvent extraction and a molecularly imprinted polymer

This work demonstrates development and evaluation of a two-way technique based on the combination of membrane assisted solvent extraction and a molecularly imprinted polymer (MASE-MIP) for selective and efficient extraction of five selected pharmaceuticals belonging to five different therapeutic classes. The pharmaceuticals were extracted from surface water samples followed by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-qTOF/MS) determination. A central composite design was applied to optimize the influence of the sample salt content, the stirring rate, the stirring time and the amount of MIP on the extraction of an anticonvulsant (carbamazepine), a cardiac stimulant (etilefrine), a muscle relaxant (methocarbamol), an antiretroviral (nevirapine) and an antidepressant (venlafaxine) from surface water. Optimization of the analytical method was performed by spiking water with a mixture of all five pharmaceuticals at 500 ng mL−1. Optimum extraction conditions for a sample volume of 18 mL were found to be 5 g of salt content, a stirring rate of 400 rpm, an extraction time of 60 min and 50 mg of MIP. The MASE-MIP-LC-qTOF/MS method gave detection and quantification limits ranging from 0.09 to 0.20 ng mL−1 and 0.31–0.69 ng mL−1, respectively. The spiked river water samples yielded recoveries ranging from 38 to 91% for the selected model compounds belonging to the five classes of pharmaceuticals. Upon the application of the developed analytical method in water analysis, all selected pharmaceuticals were detected in South African river water with nevirapine and venlafaxine being more prominent attaining the maximum concentrations of 1.64 and 2.48 ng mL−1, respectively.

Electrochemical Characterization and Detection of Lead in Water Using SPCE Modified with BiONPs/PANI.

The need for constant assessment of river water qualities for both aquatic and other biological survival has emerged a top priority, due to increasing exposure to industrial pollutants. A disposable screen print carbon electrode was modified with a conductive polymer (PANI) and Zn and/or Cu oxides NPs, obtained through bioreduction in citrus peel extracts (lemon and orange), for ultra-sensitive detection of PB2+, in the Crocodile River water sample. The synthesized materials were characterized with Fourier-transform infra-red spectroscopy (FTIR), ultra-violet visible spectroscopy (UV-Vis), and scanning electron microscopy (SEM). The SPC-modified electrodes designated as SPCE/LPE/BiONPs/PANI and SPCE/OPE/BiONPs/PANI were characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) and eventually deployed in the electrochemical detection of PB2+ in water using square wave voltammetry (SWV) technique. The electrochemical responses of the modified electrodes for both CV and EIS in 0.1 M HCl demonstrated enhanced performance relative to the bare SPCE. A detection and quantification limit of 0.494 ppb and 1.647 were obtained at SPCE/LPE/BiONPs/PANI, respectively, while a detection and quantification limit of 2.79 ppb and 8.91 ppb, respectively, were derived from SPCE/OPE/BiONPs/PANI. The relative standard deviations (RSD) for SPC electrode at a 6.04 µM PB2+ analyte concentration was 4.76% and 0.98% at SPCE/LPE/BiONPs/PANI and SPCE/LPE/BiONPs/PANI, respectively. The effect of copper, zinc, iron, cobalt, nickel, and magnesium on the stripping peaks of PB2+ at SPCE/OPE/BiONPs/PANI, showed no significant change except for cobalt, with about 17.67% peak current drop. The sensors were assessed for possible determination of PB2+ in spiked river water samples. The average percentage recovery and RSD calculated were 94.25% and 3.74% (n = 3) at SPCE/LPE/BiONPs/PANI and, 96.70% and 3.71% (n = 3) at SPCE/OPE/BiONPs/PANI, respectively. Therefore, the fabricated sensor material could be used for environmental assessment of this highly toxic heavy metal in the aquatic system

Magnetic Solid Phase Extraction Based on Nanostructured Magnetic Porous Porphyrin Organic Polymer for Simultaneous Extraction and Preconcentration of Neonicotinoid Insecticides From Surface Water.

In this study, a magnetic porphyrin-based porous organic polymer (MP-POP) nanocomposite was successfully synthesized according previous studies and applied as an adsorbent for simultaneous extraction and preconcentration of four neonicotinoid insecticides from surface river water. The MP-POP was characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy/energy dispersive x-ray spectroscopy (SEM/EDS), N2-adsorption/desorption analysis, Fourier Transform infrared spectroscopy (FTIR). The neonicotinoid insecticides were quantified using high performance chromatography coupled with diode array detector (HPLC-DAD). The MP-POP shown to have a high surface area, highly porous structure and strong affinity toward the investigated analytes. The adsorption capacities were 99.0, 85.5, 90.0, and 79.4 mg g−1 for acetamiprid, clothiandin, thiacloprid and imidacloprid, respectively. The influential parameters affecting the magmatic μ-solid phase extraction (M-μ-SPE) procedure were investigated using fractional factorial design and surface response methodology (RSM). Under optimum conditions, the method exhibited relatively low limit of detection in the range of 1.3–3.2 ng L−1, limit of quantification in the range of 4.3–11 ng L−1 and wide linearity (up to 600 μg L−1). The intraday and interday precision, expressed as the relative standard deviation (RSD) were <5%. The percentage recoveries for the four target analytes ranged from 91 to 99.3% for the spiked river water samples. The method was applied for determination of neonicotinoids in river water samples and concentrations ranged from 0 to 190 ng L−1.

A Sensitive Impedimetric Aptasensor Based on Carbon Nanodots Modified Electrode for Detection of 17ß-Estradiol.

A simple and sensitive aptasensor based on conductive carbon nanodots (CDs) was fabricated for the detection of 17ß-Estradiol (E2). In the present study, the hydrothermal synthesis of carbon nanodots was successfully electrodeposited on a screen-printed electrode (SPE) as a platform for immobilization of 76-mer aptamer probe. The morphology and structure of the nanomaterial were characterized by UV-visible absorption spectra, Fluorescence spectra, Transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). Moreover, cyclic voltammetry and electrochemical impedance spectroscopy were used to investigate the electrochemical performance of the prepared electrodes. Subsequently, impedimetric (EIS) measurements were employed to investigate the relative impedances changes before and after E2 binding, which results in a linear relationship of E2 concentration in the range of 1.0 × 10−7 to 1.0 × 10 −12 M, with a detection limit of 0.5 × 10−12 M. Moreover, the developed biosensor showed high selectivity toward E2 and exhibited excellent discrimination against progesterone (PRG), estriol (E3) and bisphenol A (BPA), respectively. Moreover, the average recovery rate of spiked river water samples with E2 ranged from 98.2% to 103.8%, with relative standard deviations between 1.1% and 3.8%, revealing the potential application of the present biosensor for E2 detection in water samples.

Development and evaluation of the iron oxide-hydroxide based resin gel for the diffusive gradient in thin films technique

An ion-exchange resin Lewatit FO 36 was used for the preparation of a new resin gel for the diffusive gradient in thin films technique (DGT). The DGT method was optimized for the accumulation of four bioavailable arsenic species (AsIII, AsV, monomethylarsonic acid, dimethylarsinic acid) in the aquatic environment. The total sorption capacity of Lewatit FO 36 resin gel was 535 μg As disc−1. The microwave-assisted extraction in the presence of NaCl (10 g L−1) and NaOH (10 g L−1) was used for the isolation of arsenic species from the Lewatit FO 36 resin gel. The elution efficiency of arsenic was 98.4 ± 2.0%. Arsenic was determined by the optimized electrothermal atomic absorption spectrometry (ET-AAS) method using palladium modifier, pre-atomization cool-down step and tungsten carbides coating of graphite tube. The Lewatit FO 36 resin gel provides accurate results (cDGT/cSOL ratio 0.86–1.00) in the pH range 4–8. No significant influence of experimental conditions was observed in the presence of chlorides (0–0.5 mol L−1) and humic acid (0–100 mg L−1). Only a very high concentration of phosphates (10 mg L−1) caused a slight decrease in the diffusion coefficients of MMA and AsV species (8.4% and 12.4%, respectively). The presence of iron (0–1 mg L−1) caused a decrease in the diffusion coefficients, but with regard to the common concentrations of iron (less than 0.3 mg L−1), the negative effect was considered not significant for AsIII and DMA in natural water. The DGT-ET-AAS method was applied for the determination of bioavailable arsenic species in the spiked river water samples and also in-situ in the water reservoir. The new resin gel was characterized by a homogeneous gel structure with excellent reproducibility (< 5% variation of results between batches) and high sorption capacity which suggests its possible long-term application (up to 286 days in the environment with the arsenic concentration of 100 μg L−1).