Unusual reactivity of 2,2-diphenyl-1-picrylhydrazyl (DPPH) with Fe3+ controlled by competing reactions.

2,2-Diphenyl-1-picrylhydrazyl (DPPH) is a stable organic free radical widely used in various fields as a model free radical. There is scarce information about the stability of this compound in the chemical environments in which it is used. Side reactions between DPPH and other species can alter the precision of experiments that use DPPH, such as the evaluation of antioxidant properties amongst others. Following recent investigations highlighting reactions between DPPH and metal cations or Lewis acids, a quantitative reaction between DPPH and Fe3+ in acetonitrile was studied in the present work. UV-Vis spectroscopy and electrochemistry were used to monitor the reaction. The results obtained indicate a fast and multistep reaction between Fe3+ and DPPH that can be simplified as a simple redox reaction with the formation of Fe2+ and DPPH+. The reaction mechanism proposed follows complex steps involving two competing phenomena: a disproportionation which accelerates the reaction and an oxidation process that slows it down through DPPH regeneration.

Electrochemical Determination of Epinephrine in Pharmaceutical Preparation Using Laponite Clay-Modified Graphene Inkjet-Printed Electrode.

Epinephrine (EP, also called adrenaline) is a compound belonging to the catecholamine neurotransmitter family. It can cause neurodegenerative diseases, such as Alzheimer's disease, Parkinson's disease, Huntington's disease and amyotrophic lateral sclerosis. This work describes an amperometric sensor for the electroanalytical detection of EP by using an inkjet-printed graphene electrode (IPGE) that has been chemically modified by a thin layer of a laponite (La) clay mineral. The ion exchange properties and permeability of the chemically modified electrode (denoted La/IPGE) were evaluated using multi-sweep cyclic voltammetry, while its charge transfer resistance was determined by electrochemical impedance spectroscopy. The results showed that La/IPGE exhibited higher sensitivity to EP compared to the bare IPGE. The developed sensor was directly applied for the determination of EP in aqueous solution using differential pulse voltammetry. Under optimized conditions, a linear calibration graph was obtained in the concentration range between 0.8 µM and 10 µM. The anodic peak current of EP was directly proportional to its concentration, leading to detection limits of 0.34 µM and 0.26 µM with bare IPGE and La/IPGE, respectively. The sensor was successfully applied for the determination of EP in pharmaceutical preparations. Recovery rates and the effects of interfering species on the detection of EP were evaluated to highlight the selectivity of the elaborated sensor.

An ultra-sensitive uric acid second generation biosensor based on chemical immobilization of uricase on functionalized multiwall carbon nanotube grafted palm oil fiber in the presence of a ferrocene mediator.

In this work, palm oil fiber (POF) grafted functionalized multiwall carbon nanotube (FMWCNT) decorated ferrocene (Fc) has been drop coated on a platinum electrode (Pt), in which uricase (UOx) has been chemically immobilized for sensitive and selective biosensing of uric acid (UA). Through the use of EDC/NHS, a stable bioelectrode (UOx/Fc/FMWCNT-POF/Pt) was obtained and characterized by FTIR/ATRIR, XRD, Raman, EA/EDX, TGA, SEM, TEM, CV, EIS, CA, and DPV. Results from DPV showed the rapid response of the developed bioelectrode towards UA (0.185 V) with high sensitivity (41.14 µA mM-1) and good limit of detection (19 µM) in the linear range 10-1000 µM. The low value of Michaelis-Menten constant (km = 31.364 µM) shows high affinity of the UA towards the enzyme at the electrode surface. The developed biosensor demonstrates good reproducibility, repeatability, and stability with a deviation of less than 2.5%, and was successfully applied for human blood sample analysis. The CA study revealed a fast response time (2 s) of the sensor. The work has pioneered a new addition to the class of tailorable chemical species for biosensor development and proven to be a promising new tool for point of care testing (POCT) applications.

Probing the reactivity of 2,2-diphenyl-1-picrylhydrazyl (DPPH) with metal cations and acids in acetonitrile by electrochemistry and UV-Vis spectroscopy.

2,2-Diphenyl-1-picrylhydrazyl (DPPH) is certainly one of the most widely used free radicals in several applications, because of its high stability. Unfortunately, there are few works dealing with its stability in the presence of many chemical species that coexist during chemical processes. In this work, the stability of DPPH was investigated by electrochemistry and UV-Vis spectroscopy in the presence of some metal cations (Cu2+ and Zn2+) and acids (HClO4 and HNO3) in acetonitrile. In the presence of Cu2+, DPPH was oxidized to DPPH+ with the formation of an equivalent amount of Cu+. With Zn2+, DPPH undergoes a slow disproportionation with the formation of Zn(DPPH)+ and DPPH+, certainly favored by the acidity of the metal cation. This hypothesis was subsequently confirmed by studying the stability of DPPH in the presence of HClO4. This acid of appreciable strength in acetonitrile (pKa = 1.83) causes a fast disproportionation of DPPH with the formation of DPPH-H and DPPH+. This mechanism was confirmed both by UV-Vis spectroscopy and by electrochemistry, with a stoichiometry corresponding to 2 equivalents of DPPH for about 1 equivalent of HClO4. In the presence of nitric acid, which is about 107 weaker than HClO4 in acetonitrile, the disproportionation was much slower. These preliminary results are proof that many chemical species are likely to react with DPPH and indirectly induce sources of bias during its application, especially when evaluating antioxidant properties.

Fabrication of an Organofunctionalized Talc-like Magnesium Phyllosilicate for the Electrochemical Sensing of Lead Ions in Water Samples.

A talc-like magnesium phyllosilicate functionalized with amine groups (TalcNH2), useful as sensor material in voltammetry stripping analysis, was synthesized by a sol-gel-based processing method. The characterizations of the resulting synthetic organoclay by scanning electron microscopy (SEM), X-ray diffraction, N2 sorption isotherms (BET method), Fourier transform infrared spectroscopy (FTIR), CHN elemental analysis and UV-Vis diffuse reflectance spectroscopy (UV-Vis-DRS) demonstrated the effectiveness of the process used for grafting of amine functionality in the interlamellar clay. The results indicate the presence of organic moieties covalently bonded to the inorganic lattice of talc-like magnesium phyllosilicate silicon sheet, with interlayer distances of 1568.4 pm. In an effort to use a talc-like material as an electrode material without the addition of a dispersing agent and/or molecular glue, the TalcNH2 material was successfully dispersed in distilled water in contrast to natural talc. Then, it was used to modify a glassy carbon electrode (GCE) by drop coating. The characterization of the resulting modified electrode by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed its charge selectivity ability. In addition, EIS results showed low charge transfer resistance (0.32 Ω) during the electro-oxidation of [Fe(CN)6]3-. Kinetics studies were also performed by EIS, which revealed that the standard heterogeneous electron transfer rate constant was (0.019 ± 0.001) cm.s-1, indicating a fast direct electron transfer rate of [Fe(CN)6]3- to the electrode. Using anodic adsorptive stripping differential pulse voltammetry (DPV), fast and highly sensitive determination of Pb(II) ions was achieved. The peak current of Pb2+ ions on TalcNH2/GCE was about three-fold more important than that obtained on bare GCE. The calculated detection and quantification limits were respectively 7.45 × 10-8 M (S/N = 3) and 24.84 × 10-8 M (S/N 10), for the determination of Pb2+ under optimized conditions. The method was successfully used to tap water with satisfactory results. The results highlight the efficient chelation of Pb2+ ions by the grafted NH2 groups and the potential of talc-like amino-functionalized magnesium phyllosilicate for application in electrochemical sensors.

Amino-Functionalized Laponite Clay Material as a Sensor Modifier for the Electrochemical Detection of Quercetin.

In this work, an electrode modified with an amino-functionalized clay mineral was used for the electrochemical analysis and quantification of quercetin (QCT). The resulting amine laponite (LaNH2) was used as modifier for a glassy carbon electrode (GCE). The organic-inorganic hybrid material was structurally characterized using X-ray diffraction, Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and CHN elemental analysis. The covalent grafting of the organosilane to the clay backbone was confirmed. The charge on the aminated laponite, both without and with the protonation of NH2 groups, was evaluated via cyclic voltammetry. On the protonated amine (LaNH3+)-modified GCE, the cyclic voltammograms for QCT showed two oxidation peaks and one reduction peak in the range of -0.2 V to 1.2 V in a phosphate buffer-ethanol mixture at pH 3. By using the differential pulse voltammetry (DPV), the modification showed an increase in the electrode performance and a strong pH dependence. The experimental conditions were optimized, with the results showing that the peak current intensity of the DPV increased linearly with the QCT concentration in the range from 2 × 10-7 M to 2 × 10-6 M, leading to a detection limit of 2.63 × 10-8 M (S/N 3). The sensor selectivity was also evaluated in the presence of interfering species. Finally, the proposed aminated organoclay-modified electrode was successfully applied for the detection of QCT in human urine. The accuracy of the results achieved with the sensor was evaluated by comparing the results obtained using UV-visible spectrometry.

Surface functionalization of natural hydroxyapatite by polymerization of ß-cyclodextrin: application as electrode material for the electrochemical detection of Pb(II).

A composite material prepared by polymerization of ß-cyclodextrin (ß-CD) on the surface of natural hydroxyapatite using citric acid as cross linker, was employed as electrode material for the detection of Pb(II). Hydroxyapatite was obtained from bovine bones, following a three-step procedure including pre-calcination, chemical treatment with (NH4)2HPO4, and calcination. The structure and morphology of the pristine hydroxyapatite (NHAPP0.5) and its functionalized counterpart (NHAPp0.5-CA-ß-CD) were examined using XRD, FTIR, and SEM. Upon deposition as thin film on a glassy carbon electrode (GCE), the ion exchange ability of NHAPp0.5-CA-ß-CD was exploited to elaborate a sensitive sensor for the detection of lead. The electroanalytical procedure was based on the chemical accumulation of Pb(II) ions under open-circuit conditions, followed by the detection of the preconcentrated species using differential pulse anodic stripping voltammetry. The reproducibility of the proposed method, based on a series of 8 measurements in a solution containing 2 µM Pb(II) gave a coefficient of variation of 1.27%. Significant parameters that can affect the stripping response of Pb(II) were optimized, leading to a linear calibration curve for lead in the concentration range of 2 × 10-8 mol L-1 - 20 × 10-8 mol L-1 (R2 = 0.998). The detection limit (3S/m) and the sensitivity of the proposed sensor were 5.06 × 10-10 mol L-1 and 100.80 µA.µM-1, respectively. The interfering effect of several ions expected to affect the determination of lead was evaluated, and the proposed sensor was successfully applied in the determination of Pb(II) ions in spring water, well water, river water and tap water samples.

Electroanalysis of diquat using a glassy carbon electrode modified with natural hydroxyapatite and ß-cyclodextrin composite.

The present work reports the development of a low-cost and reliable differential pulse adsorptive stripping voltammetric procedure for the detection of diquat (DQ) in water, using a glassy carbon electrode (GCE) modified with ß-cyclodextrin (ß-CD)/Natural hydroxyapatite (NHAPP0.5) composite material. The structural characterization of the natural hydroxyapatite and its modified counterpart was achieved using several techniques including X-ray Diffraction, Fourier Transform Infrared Spectroscopy and Thermal Analysis. By comparing the physico-chemical characteristics of hydroxyapatite material before and after reaction with ß-CD, all of these techniques have demonstrated the successful grafting process of ß-CD on the surface hydroxyl groups of hydroxyapatite, using citric acid (CA) as cross linker. The electrochemical features and permeability properties of the obtained materials, coated as thin film onto the GCE surface were characterized using ion exchange multisweep cyclic voltammetry. The ß-cyclodextrin modified hydroxyapatite (NHAPp0.5-CA-ß-CD) was evaluated as electrode modifier for DQ sensing. The electroanalytical procedure followed two steps: the chemical preconcentration of DQ under open-circuit conditions, and the differential pulse voltammetric detection of the preconcentrated pesticide. Various experimental parameters likely to influence the sensibility of electrode were fully investigated and optimized. A linear calibration curve for DQ in the concentration range of 5 × 10-8 - 4.5 × 10-7 mol L-1 was obtained at GCE/NHAPp0.5-CA-ß-CD, with a detection limit of 4.66 × 10-10 mol L-1 (DL = 3S/M). The proposed method was successfully applied to the determination of DQ in spring water.

A Low-Cost Layered Double Hydroxide (LDH) Based Amperometric Sensor for the Detection of Isoproturon in Water Using Carbon Paste Modified Electrode.

In this work, a Layered Double Hydroxide (NiAl-LDH) was obtained by coprecipitation method and used to elaborate an electrochemical sensor for the determination of isoproturon, which is a hazardous pollutant, widely used in agriculture, and its residue is distributed into aqueous environment through run-off and leaching from the soil. Various physicochemical techniques such as FT-IR spectroscopy, X-ray diffraction, and thermal analysis were used to characterize this material. The anionic exchange capacity of NiAl-LDH on carbon paste modified electrode was investigated toward [Fe(CN)6]3- using cyclic voltammetry. Used as electrode modifier of carbon paste electrode for isoproturon detection, a remarkable increase in isoproturon signal on modified carbon paste electrode by LDH was observed. The peak current obtained after 3 min of preconcentration in 25 µM ISO on NiAl-LDH/CPE was 2.6 times higher than that exhibited by the same analyte on the unmodified CPE, thereby opening the way to the development of a sensitive method for the detection of ISO. Other parameters that can affect the stripping response (preconcentration time, pH of detection medium, and LDH loading within the paste) were investigated to optimize the proposed sensor. After optimization, a linear calibration curve was obtained in the concentration range from 2 × 10-8 to 1.8 × 10-7 M, leading to a detection limit of 1 × 10-9 M (S/N = 3). The relative standard deviation for 5 identical measurements was 2.7%. The interfering effect of some compounds and ions was examined on the stripping response of ISO. The applicability of the method was verified by the determination of ISO in spiked water sample.

Performances of Alkaloid Extract from Rauvolfia macrophylla Stapf toward Corrosion Inhibition of C38 Steel in Acidic Media.

Alkaloid extract from Rauvolfia macrophylla Stapf (AERMS) was studied as the corrosion inhibitor for C38 steel in 1 M HCl and 0.5 M H2SO4 using electrochemistry and surface analysis. The corrosion inhibition was efficient and proceeds via adsorption of AERMS on the steel surface due to the active functional groups present in the molecules. AERMS acts as a mixed inhibitor in HCl and as a cathodic inhibitor in H2SO4. In H2SO4 corrosive medium, the presence of iodides improves the adsorption of the alkaloid molecules by reducing the surface charge of the electrode and thus substantially decreases the corrosion rate. Two pure alkaloids (tetrahydroalastonine (THA) and perakine (PER)) were quantitatively isolated from AERMS, and their anticorrosive properties for C38 steel in 1 M HCl and 0.5 M H2SO4 were evaluated. THA showed the highest efficiency while the performance of PER was less important compared to the extract. This confirms that the efficiency of AERMS was the result of the complementary action of the chemical compounds present in the extract.

Preparation of Methyl Viologen-Kaolinite Intercalation Compound: Controlled Release and Electrochemical Applications.

This work reports the preparation of novel kaolinite nanohybrid material obtained by intercalation of methyl viologen (MV) in the interlayer space of kaolinite, using methoxykaolinite (K-M) as starting material. Characterization of the resulting material (K-MV) confirmed the presence of MV units in the interlayer space of K-M with lateral orientation, associated with a high amount of water molecules due to the hydrophilic nature of MV. The resulting structural formula of this organoclay based on thermogravimetric analysis was Si2Al2O5(OH)3.72(OCH3)0.28(MV)0.17(H2O)0.82. The release of MV from the K-MV composite was studied in order to evaluate the advantages of using this material for pesticide formulation with MV as active ingredient. The localization of MV in the interlayer space of K-M significantly slows its release in water. However, the interactions that retain MV in the interlayer space remain sufficiently less intense to ensure a complete release of MV in a relatively short time (2 h). On the basis of the interactions that ensure MV intercalation in methoxykaolinite, K-M was used as electrode modifier and applied for the electrochemical determination of MV. The electrochemical signal of MV on the K-M modified electrode was 2 times more intense compared to the pristine kaolinite modified electrode. After optimization of experimental parameters, a sensitivity of 3.91 µA M-1 and a detection limit of 0.14 nM were obtained at the K-M modified electrode. This performance represents one of the most important reported so far in the literature during the electrochemical determination of MV. The sensor was also found very efficient for MV determination in real water systems (well, spring, and tap water) despite the decrease of sensitivity due to the presence of interfering species.

Voltammetric behavior of Mammeisin (MA) at a glassy carbon electrode and its interaction with Bovine Serum Albumin (BSA).

The electrochemical oxidation of Mammeisin (MA) was studied in a solution containing acetone and 0.1M phosphate buffer +0.1M KCl (pH=5.3) at a glassy carbon electrode (GCE), using cyclic (CV) and square wave voltammetry (SWV). MA showed a quasi-reversible process, which is pH dependent and that involves the exchange of two electrons and two protons. The oxidation product was adsorbed by the electrode surface to form a film that blocks active sites over repetitive cyclic. Moreover, the interaction of MA and bovine serum albumin (BSA) was studied by CV and SWV at different pHs (5.4, 7.2, 9.5). As a result of the affinity binding with BSA, electrochemically inactive complex was formed. In addition, the oxidation potential of MA in the presence of BSA depends on the pH. The diffusion coefficients of both free and bound MA were estimated from the cyclic voltammetry data using the method developed by Randles-Sevich (Df=9.85×10-5cm2s-1 and Db=1.27×10-9cm2s-1) and the binding constant of MA-BSA complex, K=3.47×102Lmol-1, was obtained.

Square wave voltammetric detection by direct electroreduction of paranitrophenol (PNP) using an organosmectite film-modified glassy carbon electrode.

This work describes the development of a low-cost and reliable adsorptive stripping voltammetric method for the detection of PNP in water. Organoclays were prepared by intercalation in various loading amounts of cetyltrimethylammonium ions (CTA(+)) in the interlayer space of a smectite-type clay mineral. Their structural characterization was achieved using several techniques including X-ray diffraction (XRD), N2 adsorption-desorption (BET method) and Fourier Transform Infrared spectroscopy (FTIR) that confirmed the intercalation process and the presence of the surfactant ions within the clay mineral layers. Using [Fe(CN)6](3-) and [Ru(NH3)6](3+) as redox probes, the surface charge and the permeability of the starting clay mineral and its modified counterparts were assessed by multisweep cyclic voltammetry, when these materials were coated on the surface of a glassy carbon electrode (GCE). In comparison with the bare GCE, the organoclay modified electrodes exhibited more sensitive response towards the reduction of paranitrophenol (PNP). Under optimized conditions, a calibration curve was obtained in the concentration range from 0.2 to 5.2µmolL(-1); leading to a detection limit of 3.75×10(-8)molL(-1) (S/N=3). After the study of some interfering species on the electrochemical response of PNP, the developed sensor was successfully applied to the electroanalytical quantification of the same pollutant in spring water.

Removal of Cd (II) from synthetic wastewater by alginate-Ayous wood sawdust (Triplochiton scleroxylon) composite material.

The biosorption characteristics of Cd (II) ions from synthetic wastewater using raw Ayous wood sawdust (Triplochiton scleroxylon), r-AS, immobilized by sodium alginate were investigated with respect to pH, biomass quantity, contact time, initial concentration of heavy metal, temperature and stirring rate. The experimental data fitted well with the Langmuir isotherm, suggesting that monolayer adsorption of the cadmium ions onto alginate-Ayous sawdust composite (a-ASC). The obtained monolayer adsorption capacity of a-ASC for Cd (II) was 6.21 mg/g. From the Dubinin-Radushkevich isotherm model, a 5.39 kJ/mol value for the mean free energy was calculated, indicating that Cd (II) biosorption could include an important physisorption stage. Thermodynamic calculations showed that the Cd (II) biosorption process was feasible, endothermic and spontaneous in nature under examined conditions. The results indicated that a-ASC could be an alternative material replacing more costly adsorbents used for the removal of heavy metals.

Electrochemical determination of mesotrione at organoclay modified glassy carbon electrodes.

A natural Cameroonian smectite-type clay (SaNa) was exchanged with cationic surfactants, namely cetyltrimethylammonium (CTA) and didodecyldimethyl ammonium (DDA) modifying its physico-chemical properties. The resulting organoclays that have higher adsorption capacity for mesotrione than the pristine SaNa clay, have been used as modifiers of glassy carbon electrode for the electrochemical detection of this herbicide by square wave voltammetry. The stripping performances of SaNa, SaCTA and SaDDA modified electrodes were therefore evaluated and the experimental parameters were optimized. SaDDA gives the best results in deoxygenated acetate buffer solution (pH 6.0) after 2 min accumulation under open circuit conditions. Under optimal conditions, the reduction current is proportional to mesotrione concentration in the range from 0.25 to 2.5 µM with a detection limit of 0.26 µM. The fabricated electrode was also applied for the commercial formulation CALLISTO, used in European maize market.

Amperometric sensors based on sawdust film modified electrodes: application to the electroanalysis of paraquat.

Natural or sodium hydroxide treated Ayous sawdusts were used to prepare thin film electrodes (denoted respectively as PSTFE and SSTFE). The sensors obtained exhibit good mechanical stability and a wide electrochemical potential range. Their electrochemical characterization revealed that they present a good capacity to accumulate cations, but are not useful for the electroanalysis of anions. In all cases, the signals were more intense and well defined on SSTFE compared to PSTFE. When applied to the electroanalysis of paraquat, a significant improvement of the current intensities was obtained on these electrodes compared to the bare glassy carbon electrode. The diffusion of this compound through the film which is the main process governing the electrochemical reaction at the electrode surface, is 2.2 times more important with SSTFE compared to PSTFE. After the optimization of the detection parameters, calibration curves were obtained in the concentration range 0.1-0.725 µmol L(-1) for PSTFE and 0.05-0.6 µmol L(-1) for SSTFE. The detection limits determined for a signal/noise ratio=3 are 5.49×10(-9) mol L(-1) for PSTFE and 3.02×10(-9) mol L(-1) for SSTFE.

Electrochemical response of ascorbic and uric acids at organoclay film modified glassy carbon electrodes and sensing applications.

A naturally occurring Cameroonian smectite clay has been grafted with trimethylpropylammonium groups and the resulting organoclay deposited as thin film onto a glassy carbon electrode (GCE) surface. It was then exploited as a suitable matrix for the accumulation and the electrochemical detection of ascorbic acid (AA) and uric acid (UA). Cyclic voltammetry revealed an increase in oxidation peak responses along with a negative shift of the corresponding anodic peak potential for both AA and UA species when using the organoclay coated GCE in comparison with the bare electrode. The electroanalytical response was improved by coating the electrode surface with a first layer of sublimed ferrocene (FC(s)), and then overcoating with the organoclay film to avoid the mediator leaching. The resulting bilayer film exhibited good characteristics such as extended linear range and high sensitivities for AA and UA, in cyclic voltammetry and amperometry. Interestingly, the redox mediator FC(s) was likely to lower overpotentials for AA oxidation (but not for UA), making possible the selective detection of these species in a mixture. The developed method could be used for the determination of AA in a pharmaceutical preparation and for UA in urine.

Electrochemical analysis of methylparathion pesticide by a gemini surfactant-intercalated clay-modified electrode.

In this study, an hybrid material obtained by the intercalation of a gemini surfactant between the layers of smectite-type clay, was fully characterized by X-ray diffraction (XRD), infrared spectroscopy (FTIR) and N(2) adsorption-desorption experiments (BET method). To ascertain the intercalation process of the starting clay by the dimeric surfactant, the permselectivity and ion exchange properties of the organoclay were investigated by ion exchange voltammetry using [Fe(CN)(6)](3-) and [Ru(NH(3))(6)](3+) as redox probes, by the means of a clay film-modified electrode. Due to its organophilic character, the surfactant-intercalated complex was evaluated as electrode modifier for the accumulation of methylparathion (MP) pesticide. The electroanalytical procedure involves two steps: preconcentration under open-circuit followed by voltammetric detection by square wave voltammetry: the peak current obtained (after 5min preconcentration in 4x10(-5)molL(-1)MP) on a glassy carbon electrode coated by a thin film of the modified clay was more than five times higher than that exhibited by the same substrate covered by a film of the pristine clay. This opens the way to the development of a sensitive method for the detection of the pesticide. Many parameters that can affect the stripping response (surfactant loading of the hybrid material, film composition, pH of the detection medium, preconcentration time, electrolysis potential and duration as well as some other instrumental parameters) were systematically investigated to optimize the sensitivity of the organoclay-modified electrode. After optimization, a linear calibration curve for MP was obtained in the concentration range from 4x10(-7) to 8.5x10(-6)molL(-1) in acetate buffer (pH 5), with a detection limit of 7x10(-8)molL(-1) (signal-to-noise ratio equal to 3). The interference effect of various inorganic ions likely to influence the stripping determination of the pesticide was also examined, and the described method was applied to spring water analysis.

Study of the removal of paraquat from aqueous solution by biosorption onto Ayous (Triplochiton schleroxylon) sawdust.

This study concerns the batch biosorption of paraquat on Ayous (Triplochiton schleroxylon) sawdust; the study centers on the evolution of biosorption parameters during the process. It appears that paraquat forms a monolayer on the sawdust surface as evidenced by the good correlation between the experimental data and the Langmuir model. The biosorption which is rather fast (the equilibrium was reached after ten minutes) follows a pseudo-second-order kinetic model and does not obey to the intra-particle diffusion model. According to the mathematical kinetic modeling, pore and surface mass transfer well describe the phenomenon. NaCl reduces the adsorption capacity of the material but has no significant effect on the kinetics. Alkaline solutions enhance the accumulation of the pollutant, the reverse being observed for acidic media. According to the thermodynamic data, this biosorption is a spontaneous and exothermic process. From these results we concluded that the adsorption of the pollutant is mainly due to cation exchange as indicated by the adsorption energy determined by the Dubinin-Radushkevich model (E=12.0736 kJ mol(-1)); some other interactions resulting from the affinity through organophilic interactions between paraquat and sawdust have also been pointed out. Desorption experiments conducted in HCl and HNO(3) solutions confirmed the proposed mechanism.

Treatment of dairy effluents by electrocoagulation using aluminium electrodes.

This work sets out to examine the efficiency of an electrolytic treatment: electrocoagulation, applied to dairy effluents. The experiments were carried out using a soluble aluminium anode on artificial wastewater derived from solutions of milk powder. The flocks generated during this treatment were separated by filtration. The analysis of the filtrates showed that the chemical oxygen demand (COD) was reduced by up to 61% while the removal of phosphorus, nitrogen contents, and turbidity were 89, 81 and 100%, respectively. An analogous treatment applied to phosphate and lactose solutions revealed that lactose was not eliminated, a fact that could account for the rather poor lowering of the COD. Compared to the chemical coagulation treatment with aluminium sulphate, the efficiency of the electrocoagulation technique was almost identical. However the wastewaters treated by electrocoagulation differed by the fact that they exhibited a lower conductivity and a neutral pH value (by contrast to the acid nature of the solution treated by the chemical coagulation). This result (low conductivity, neutral pH) tends to show that it may be possible to recycle the treated water for some industrial uses. Moreover, the electrocoagulation process uses fewer reagents: the mass of the aluminium anode dissolved during the treatment is lower compared to the quantity of the aluminium salt used in chemical coagulation. These two observations clearly show that the electrocoagulation technique is more performing.