A photo-induced fluorescence (PIF) method was developed for the quantification of diclofenac sodium, sodium 2-[2-(2,6-dichloroanilino)phenyl]acetate (NaDCF), in natural waters. Since diclofenac is not naturally fluorescent, its photoconversion under UV irradiation was carried out to produce highly fluorescent photoproduct(s) in various media (water, methanol, isopropanol, acetonitrile, ethyl acetate, dimethyl sulfoxide (DMSO), and a water-isopropanol mixture). The photoproduct responsible for the intense fluorescence of NaDCF in aqueous media was identified as chloro-carbazole by gas chromatography-mass spectrometry (GC-MS). Several PIF parameters were optimized. Using the PIF method, a highly fluorescent diclofenac photoproduct was obtained at λex/λem = 235/360 nm, with optimum fluorescence achieved after 10 min irradiation in a water-isopropanol mixture (90:10 v/v). The limit of detection (LOD) and quantification (LOQ) for diclofenac sodium in this medium were 0.11 ng ml–1 and 0.37 ng ml–1, respectively, with low relative standard deviation (RSD) values. The PIF calibration curves demonstrated good linearity, extending over one to three orders of magnitude, with correlation coefficients (R2) near unity, indicating good reproducibility. Analytical applications of this method to natural water samples yielded satisfactory results, with average recovery rates ranging from 84.77 to 101.72 %.

In this work, we developed an UV-visible (UV-VIS) absorption spectrometric method for the quantification of sodium diclofenac in natural waters. Several UV-VIS absorption method parameters were optimized. The maximum absorption wavelength was comprised between 276 and 292 nm, depending on the solvent, with molar absorption coefficients greater than 104 L mol-1 cm-1. The linearity of the UV-VIS calibration curves extended over one to three orders of magnitude, with correlation coefficients (R2) very close to unity. The low relative standard deviation (RSD) values indicated a good reproducibility of the measurements. Analytical applications to natural waters yielded satisfactory results with average recovery rates between 94.7 and 99.1%.

A spectrofluorimetric method was developed to determine residues of two β-blockers, atenolol (AT) and bisoprolol fumarate (BF), in Senegal's natural waters. The electronic absorption and fluorescence spectral properties of both β-blockers were investigated in several organic solvent mixtures [e.g., MeOH/H2O (60/40 v/v), cyclodextrins (β-cyclodextrin, HP-β-CD], and in the presence of surfactants (SDS, Triton X, Tween 80). After optimization, satisfactory analytical figures of merit were obtained for the determination of both β-blockers: concentration linear dynamic range of over one to two orders of magnitude, limits of detection (LODs) from 1.3 to 5.4 ng/ml for BF and from 1.2 to 3.7 ng/ml for AT, limits of quantification (LOQs) from 4.5 to 18.1 ng/ml for BF and from 4.0 to 12.5 ng/ml for AT. Relative standard deviations (RSDs) were between 2.1 and 5.3 %, according to the β-blockers. The spectrofluorimetric method was applied to the analysis of fortified river water and wastewater (effluent) collected in Senegal and France and spiked with both β-blockers. It yielded good recovery values, from 93.3 to 107.8 % for AT and from 97.4 to 108.9 % for BF. Our results demonstrated the simplicity, rapidity, and sensitivity of the spectrofluorimetric method to quantify residues of β-blockers in environmental waters.

The electro-Fenton (EF) process was used to assess the electrochemical degradation of the fungicide thiram and its complete removal from water using an undivided electrolytic cell equipped with Pt or BDD anode and carbon felt cathode. Hydroxyl radicals, produced homogeneously in bulk solution from electrochemically generated Fenton's reagent (center dot OH) and heterogeneously on the anode surface (MCOH)) from oxidation of water, reacted with thiram leading to its fast oxidation. Oxidative degradation and mineralization kinetics were monitored by chromatographic analysis (HPLC) and total organic carbon (TOC) measurements. The electrochemical degradation of thiram by hydroxyl radicals followed a pseudo-first-order reaction kinetics with an absolute rate constant k(abs(Thir)) of 5.54 (+0.03) x 10(9) M s(-1), determined by competition kinetics method. The TOC removal rate values were found significantly higher with BDD anode than Pt anode. Thus, almost complete mineralization (92%) of thiram solution was obtained when using BDD anode. These results highlight the major role of heterogeneous BDD(center dot OH) formed in the mineralization of thiram. The contribution of homogeneous center dot OH in mineralization of thiram was found relatively low due to its specific aliphatic structure. The efficiency of the EF process was evaluated by determining mineralization current efficiency and energy consumption per gram of TOC removed. Degradation by-products and inorganic ions, such as nitrate (NO3-), nitrite (NO2-), ammonium (NH4+) and sulfate (SO42-) formed during mineralization process, were identified by GC-MS and ionic chromatography analyses and a plausible mineralization pathway was proposed.

The photolysis of fenvalerate, a pyrethroid insecticide, was studied in acetonitrile by 1H nuclear magnetic resonance (NMR) and 13C NMR to identify the site of bond cleavage and gas chromatography-mass spectrometry (GC-MS) to establish the chemical structure of fenvalerate photoproducts. Ultraviolet (UV) irradiation of fenvalerate solutions was performed for 18 h with a solar light simulator, and the photolysis reaction obeyed first-order kinetics. Photolysis half-life time (t1/2) values ranged between 15.25 and 21.63 h (mean photodegradation percentage = 51.7 %) for 1H NMR and between 4.55 and 8.06 h (mean photodegradation percentage > 80 %) for 13C NMR. We observed five sites of bond cleavage, namely carbonyl-tertiary carbon, tertiary carbon-tertiary carbon, carbonyl-oxygen, carboxyl-tertiary carbon, and aromatic carbon-tertiary carbon, yielding photoproducts formation. GC-MS was associated with 1H NMR and 13C NMR to obtain a complete photodegradation mechanism. Before UV irradiation, two chromatogram peaks were obtained, due to the two fenvalerate isomers. Under irradiation, both peaks decreased, and new peaks appeared, corresponding to photoproduct formation. After a 12- to 13-h irradiation, 99.39 % of fenvalerate was degraded with a mean rate constant of 0.305 h–1. The chemical structure of the formed photoproducts was identified, either by using the National Institute of Standards and Technology (NIST) mass spectral database or by interpreting the mass spectra. Finally, a detailed mechanism was proposed for fenvalerate photodegradation.

A simple, sensitive, and rapid spectrofluorimetric method was developed for the determination of the β-blocker pindolol. The native fluorescence of pindolol was measured in different organic solvents and in cyclodextrin aqueous media. The highest fluorescence signal was obtained in 2-propanol at λem = 303 nm with λex = 260 nm. Analytical figures of merit for the spectrofluorimetric determination of pindolol were satisfactory, with wide linear dynamic range (LDR) values of two orders of magnitude, and rather low limit of detection (LOD) values between 0.2 and 8.7 ng/mL. Moreover, the addition of cyclodextrins (HP-β-CD and β-CD) in aqueous media enhanced the fluorescence of pindolol. In addition, the inclusion complexes of pindolol with cyclodextrins were investigated and the stability constants of complexes were calculated by means of the method of nonlinear regression (NLR). The method was successfully applied to the analysis of tap water and natural water samples, spiked with pindolol.

Highly sensitive multicomponent materials designed for the recognition of hazardous compounds request control over interfacial chemistry. The latter is a key parameter in the construction of the sensing (macro) molecular architectures. In this work, multi-walled carbon nanotubes (CNTs) were deposited on diazonium-modified, flexible indium tin oxide (ITO) electrodes prior to the electropolymerization of pyrrole. This three-step process, including diazonium electroreduction, the deposition of CNTs and electropolymerization, provided adhesively-bonded, polypyrrole-wrapped CNT composite coatings on aminophenyl-modified flexible ITO sheets. The aminophenyl (AP) groups were attached to ITO by electroreduction of the in-situ generated aminobenzenediazonium compound in aqueous, acidic medium. For the first time, polypyrrole (PPy) was electrodeposited in the presence of both benzenesulfonic acid (dopant) and ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA), which acts as a chelator. The flexible electrodes were characterized by XPS, Raman and scanning electron microscopy (SEM), which provided strong supporting evidence for the wrapping of CNTs by the electrodeposited PPy. Indeed, the CNT average diameter increased from 18 ± 2.6 nm to 27 ± 4.8, 35.6 ± 5.9 and 175 ± 20.1 after 1, 5 and 10 of electropolymerization of pyrrole, respectively. The PPy/CNT/NH2-ITO films generated by this strategy exhibit significantly improved stability and higher conductivity compared to a similar PPy coating without any embedded CNTs, as assessed by from electrochemical impedance spectroscopy measurements. The potentiometric response was linear in the 10-8-3 × 10-7 mol L-1 Pb(II) concentration range, and the detection limit was 2.9 × 10-9 mol L-1 at S/N = 3. The EGTA was found to drastically improve selectivity for Pb(II) over Cu(II). To account for this improvement, the density functional theory (DFT) was employed to calculate the EGTA-metal ion interaction energy, which was found to be -374.6 and -116.4 kJ/mol for Pb(II) and Cu(II), respectively, considering solvation effects. This work demonstrates the power of a subtle combination of diazonium coupling agent, CNTs, chelators and conductive polymers to design high-performance electrochemical sensors for environmental applications.

The removal of the phenylurea herbicide monolinuron (MLN) from water was investigated by the electro-Fenton method, based on the electro-catalytic in situ continuous production of large amounts of the strong oxidant hydroxyl radicals. The effect of several parameters, including the Fe2+ initial concentration, applied current and type of anode (Pt and boron-doped diamond - BDD), on the MLN degradation kinetics was evaluated. MLN decay kinetics was monitored by HPLC, fitting a pseudo first-order reaction, leading to a rate constant k(abs) = (3.1 +/- 0.2) x 10(9)M(-1) s(-1). Several oxidation intermediates species were identified and followed by HPLC and GC-MS. A quasi complete mineralization rate (98% TOC removal) of MLN solution was reached after 8 h of treatment on BDD anode with low energy consumption. Identification of carboxylic acids and inorganic ions was carried out by HPLC and ionic chromatography analyses. Based on identification of aromatic and aliphatic intermediates, inorganic end-products and TOC removal value, a complete MLN mineralization pathway was also proposed. (C) 2020 Elsevier B.V. All rights reserved.

Water pollution by heavy metals has many human origins, such as the burning of fossil fuels, exhaust gases of vehicles, mining, agriculture, and incineration of solid and liquid wastes. Heavy metals also occur naturally, due to volcanoes, thermal springs activity, erosion, infiltration, etc. This water contamination is a threat for living beings because most heavy metals are toxic to humans and to aquatic life. Hence, it is important to find effective techniques for removing these contaminants in order to reduce the level of pollution of the natural waters. In this work, we have reviewed the toxicity of several heavy metals (mercury, lead, cadmium, chromium, nickel), their impact on the environment and human health, and the synthesis and characterization methods of conducting organic polymers (COPs) utilized for the removal of heavy metals from the environment. Therefore, this review was essentially aimed to present recent works and methods (2000–2020) on the environmental impact and toxicity of heavy metals and on the removal of toxic heavy metals, using chemically and/or electrochemically synthesized COPs. We have also stressed the great interest of COPs for the removal of toxic heavy metals from waters.

A new electrosynthesized, fluorescent 4-amino-3-hydroxynaphthalene-1-sulfonic acid-doped polypyrrole (AHNSA-PPy) was used for the detection of Cr(VI), Pb(II) and Cd(II) heavy metallic ions. The optical properties of AHNSA-PPy were studied by UV-VIS absorption and fluorescence spectrometry in diluted DMSO solutions. UV-VIS spectrum showed a main band at 260 nm, a moderate band at 240 nm, and shoulders at 285, 295, 320 and 360 nm, whereas the fluorescence spectrum presented an excitation peak at 330 nm and a main emission peak at 390 nm with a shoulder at 295 nm. The effects of heavy metallic ions, including Cr(VI), Pb(II), and Cd(II), on the AHNSA-PPy UV-VIS absorption and fluorescence spectra were investigated. AHNSA-PPy fluorescence spectra were strongly quenched upon increasing the Cr(VI), Pb(II) and Cd(II) concentrations. Linear Stern-Volmer relationships were established, and polynomial equations for Pb(II) and Cd(II) were obeyed, indicating the existence of a AHNSA-PPy dynamic fluorescence quenching mechanism for Cr(VI) and a combination of dynamic and static fluorescence quenching for Pb(II) and Cd(II). The AHNSA-PPy sensor showed high sensitivity for fluorescence detection of the three heavy metallic ions, with very low limits of detection (3σ) of 1.4 nM for Cr(VI), 2.7 nM for Cd(II) and 2.6 nM for Pb(II). Therefore, this very sensitive quenching fluorimetric sensor is proposed for the detection of trace, toxic heavy metallic ions in the environment.

The last two decades have witnessed attractive, innovative aspects of conductive polymers (CPs) in monitoring environmental pollution. In this regard, CP-based electrode materials were designed for the selective recognition of heavy metal ions in the environment (e.g. waste, river or tap water) or in simulated polluted environmental samples. In this review, the emphasis is on polypyrrole (PPy), an interesting electrosensing electrode material for heavy metals due to its facile preparation, versatile chemistry and physicochemical features. Indeed, health issues raised by metal ion pollutants require an urgent holistic approach for environmental problem solving. In this review, we will summarize the existing knowledge on the use of PPy as electrode material for the detection of heavy metals. We will report strategies of preparation of polypyrrole that exhibit selectivity towards heavy metal ions: (i) choice of dopant, (ii) functionalization of polymer backbone by chelatant groups, and (iii) preparation of ion imprinted polypyrrole. It is clear from this review that dopants could act as chelatant of metal ions and increase the selectivity. Such improvement could also be achieved by copolymerization of pyrrole with pyrrole-bearing chelatant groups (e.g. EDTA-like) or finally by the imprinting technique. The latter imparts artificial receptor sites for the recognition of metal ions combining the shape of the receptor site within the polypyrrole matrix that fit in well with the size of the metal ion, on the one hand, and the receptor site–ion interactions, on the other hand. Regardless, the method employed to design polypyrrole sensing layers for heavy metal nanostructuration seems to definitely improve the sensitivity of polypyrrole-based sensor devices. The review finishes by concluding remarks and indication of possible challenging new directions exploring polypyrrole in tracking occurrence of heavy metal ions in the environment.

To develop conducting organic polymers (COPs) as luminescent sensors for determination of toxic heavy metals, a new benzene sulfonic acid-doped polypyrrole (PPy-BSA) thin film was electrochemically prepared by cyclic voltammetry (CV) on flexible indium tin oxide (ITO) electrode in aqueous solution. PPy-BSA film was characterized by FTIR spectrometry, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The optical properties of PPy-BSA were investigated by ultraviolet (UV)-visible absorption and fluorescence spectrometry in dimethylsulfoxide (DMSO) diluted solutions. PPy-BSA fluorescence spectra were strongly quenched upon increasing copper(II) ion (Cu2+ ) and lead(II) ion (Pb2+ ) concentrations in aqueous medium, and linear Stern-Volmer relationships were obtained, which indicated the existence of a main dynamic fluorescence quenching mechanism. BSA-PPy sensor showed a high sensitivity for detection of both metallic ions, Cu2+ and Pb2+ , with very low limit of detection values of 3.1 and 18.0 nM, respectively. The proposed quenching-fluorimetric sensor might be applied to the determination of traces of toxic heavy metallic ions in water samples.

An EC50 database was established to assess the acute toxicity of 16 PESTANAL pesticide standards and of seven pesticide commercial formulations using a Vibrio fischeri bioluminescence method. Half maximal effective concentration (EC50 ) is defined as the concentration of pollutant (in this case, pesticide) destroying 50% of the bacteria population and causing 50% bioluminescence inhibition, after a specified exposure time. Linear curves of bioluminescence inhibition versus pesticide concentration and EC50 values were obtained for exposure times (t) of 5 or 15 min for these pesticides. The EC50 values ranged from 6.90 × 10-4 to 0.83 mg/ml (t = 5 min), and from 9.00 × 10-4 to 0.37 mg/ml (t = 15 min) for pesticide standards, plus from 0.0077 to 0.74 mg/ml (t = 5 min), and from 0.0076 and 0.57 mg/ml (t = 15 min) for pesticide commercial formulations. The EC50 database allowed classification of the pesticides under study into three categories according to their toxicity: very toxic, toxic and moderately toxic. These results demonstrated that the establishment of an EC50 database and of linear curves of bioluminescence inhibition versus the pesticide concentration resulted in very important and irreplaceable tools to estimate the global and individual toxicity of pesticides present in environmental samples.

Because of their important fluorescence properties, coumarins are widely applied in sensing devices. In this paper, the electronic inductive, mesomeric, and electromeric substituent effects on the electronic absorption and fluorescence spectra of 11 substituted coumarins, including NH2, NMe2, NEt2, OH, CF3, CH3, COOH, Cl, and Br substituents, have been quantitatively studied by means of structure‐reactivity relationships. We have applied the Hammett, Brown‐Okamoto, and Yukawa‐Tsuno correlations to the coumarins electronic absorption and fluorescence spectra wavenumbers and Stokes shifts. The Stokes shift of coumarins decreased when the electron‐donor inductive/mesomeric power of the substituent increased. This Stokes shift decrease was more pronounced when the solvent polarity increased, which might be explained by the electromeric effect increase.

A new method was developed for determining trace amounts of pesticides, using an ultraviolet (UV) lamp to obtain photo-induced fluorescent (PIF) compounds, and then using laser excitation (LE) by a tunable source to excite and simultaneously characterize their fluorescence over a short acquisition time using an intensified charge-coupled device camera. This new UV-PIF-LE method was applied to determine isoproturon, oxadiazon, and fipronil in natural waters. This approach represents an improvement on the previously published direct laser photo-induced fluorescent (DL-PIF) approach that utilized the inclusion of a supplementary UV irradiation device in the experimental setup, permitting the separation of the formation and detection steps for the PIF analytes. This evolution improves the selectivity and increases the sensitivity while maintaining a short analysis time. The UV-PIF-LE method gave very good results with satisfactory analytical performance for the determination of the selected pesticides. This approach also demonstrated good reproducibility, with relative square deviation values between 3.3% and 6.3%, for spiked river water and seawater samples with detection limits in the ng mL(-1) range.

Diflubenzuron (DFB) and fenuron (FEN) are benzoylurea and phenylurea pesticides, widely used in Senegal, that do not exhibit any natural fluorescence, but can be determined by means of photoinduced fluorescence (PIF) methods. Photodegradation of DFB and FEN yielded a number of fluorescent and non-fluorescent photoproducts. For both pesticides, at least 10 photoproducts were detected and identified by gas chromatography-mass spectrometry (GC/MS). To identify the formed fluorescent DFB and FEN photoproducts, their fluorescence spectra were compared with those of standard compounds, including phenol and p-hydroxyaniline.

Prototypes of on-site automatic photo induced fluorescence detectors of pesticide in natural waters are set up and applied for the determination of the benzoyl-and phenylurea pesticides, namely fluometuron, monolinuron and diflubenzuron. As these pesticides present no native fluorescence the set up systemuse the photo conversion under UV irradiation of these pesticides into highly fluorescent photoproducts. A first system, called AUTOPIF, (evolution the commercial AQUAPOD system) is develop using a detection via a diode array spectrometer. To improve the sensitivity of the method, a second system, called AUTOPIF+, is developed with a more resolute spectrometer and an intensified CCD camera detection. Analytical applicationswere carried out in aqueous solution and detected on linewith the AUTOPIF and AUTOPIF+ system. The calibration curves are linear over one order of magnitude, and the limits of detection are in the mu g mL(-1) range. The analytical performances of these methods for the determination of the three pesticides are satisfactory in comparison to other classical PIF methods published for the determination of phenylurea pesticides in aqueous solutions. Our results show that the AUTOPIF and AUTOPIF+ methods are versatile, sensible and can be easily applied as an alert system to detect pollutant residues in naturals waters over a threshold value. (C) 2019 Elsevier B.V. All rights reserved.

Adhesively bonded polypyrrole thin films doped with benzene sulfonic acid (BSA) were electrodeposited on aminobenzenediazonium-modified flexible ITO electrodes and further employed for the detection of Pb2+, Cu2+, and Cd2+ metal ions in aqueous medium. The aminophenyl (AP) adhesive layer was grafted to ITO by electroreduction of the in situ generated parent diazonium compound. Polypyrrole (PPy) thin films exhibited remarkable adhesion to aminophenyl (ITO-AP). The strongly adherent polypyrrole films exhibited excellent electroactivity in the doped state with BSA which itself served to chelate the metal ions in aqueous medium. The surface of the resulting, modified flexible electrode was characterized by XPS, SEM, and electrochemical methods. The ITO-AP-PPy electrodes were then used for the simultaneous detection of Cu2+, Cd2+, and Pb2+ by differential pulse voltammetry (DPV). The detection limits were 11.1, 8.95, and 0.99 nM for Cu2+, Cd2+, and Pb2+, respectively. In addition, the modified electrodes displayed a good reproducibility, making them suitable for the determination of heavy metals in real wastewater samples.

Adhesion of polymers to surfaces is of the upmost importance in timely applications such as protective coatings, biomaterials, sensors, new power sources and soft electronics. In this context, this work examines the role of molecular interactions in the adhesion of polypyrrole thin films to flexible Indium Tin Oxide (ITO) electrodes grafted with aryl layers from various diazonium salts, namely 4-carboxybenzenediazonium (ITO-CO2H), 4-sulfonicbenzenediazonium (ITO-SO3H), 4-N,N-dimethylbenzenediazonium (ITO-N(CH3)(2)), 4-aminobenzenediazonium (ITO-NH2), 4-cyanobenzenediazonium (ITO-CN) and 4-N-phenylbenzenediazonium (ITO-NHPh). It was demonstrated that PPy thin layers were adherent to all aryl-modified surfaces, whereas adhesive failure was noted for bare ITO following simple solvent washing or sonication. Adhesion of polypyrrole was investigated in terms of hydrophilic/hydrophobic character of the underlying aryl layer as probed by contact angle measurements. It was found that sulfonic acid-doped polypyrrole (PPy-BSA) thin films were preferably deposited on the most hydrophobic surfaces. More importantly, the redox properties and electrochemical impedance of PPy were closely related to the hydrophobic character of the aryl layers. This work demonstrates that diazonium compounds are unique molecular glues for conductive polymers and permit to tune their interfacial properties. With robust, diazonium-based architectured interfaces, one can design high performance materials for e.g., sensors, printed soft electronics and flexible thermoelectrics.