Application of nanobalance technique and principal component analysis for detection of the soil fumigant Telone residues in the air

Quartz crystal nanobalance (QCN) technique is considered as a powerful mass sensitive sensor for monitoring of materials in the sub-nanogram level. In the current study, a method based on QCN technique developed to determine Telone in air. Various coating materials including methyl phenyl silicon, 75% phenyl (OV25) and molecularly imprinted polymer (MIP) were employed. The frequency shift of OV25-modified quartz crystal was found to be linear against organohalogen compounds [Telone (soil fumigant), Koril (Herbicide), Endosulfan (organochlorine insecticide) and Chloroform (solvent)] concentrations in the range of 2.4 to 48 mg L^?1 for Telone vapor and 4.8–24 mg L^?1 for three other vapors. The correlation coefficients for Telone, Koril, Endosulfan and Chloroform were 0.992, 0.996, 0.989 and 0.991, respectively. The principal component analysis was also utilized to process the frequency response data of the organic vapors. Using principal component analysis, it was found that more than 93.85% of the data variance could still be explained by use of two principal components (PC1 and PC2). Subsequently, the successful discrimination of Telone and other compounds was quite possible through the principal component analysis of the transient responses of the OV25-modified electrode. In the second method, a molecularly imprinted polymer-coated sensor for Telone was developed. Molecularly imprinted polymer coated quartz crystal (MIP-QCN) showed a selective response to Telone and gave a linear relationship between frequency shift and amount of Telone from 1 to 48 mg L^?1. In this investigation, the proficiency of MIP-QCN and OV25-modified QCN sensors were compared.     

Application of nanobalance technique and principal component analysis for detection of the soil fumigant Telone residues in the air

Quartz crystal nanobalance (QCN) technique is considered as a powerful mass sensitive sensor for monitoring of materials in the sub-nanogram level. In the current study, a method based on QCN technique developed to determine Telone in air. Various coating materials including methyl phenyl silicon, 75% phenyl (OV25) and molecularly imprinted polymer (MIP) were employed. The frequency shift of OV25-modified quartz crystal was found to be linear against organohalogen compounds [Telone (soil fumigant), Koril (Herbicide), Endosulfan (organochlorine insecticide) and Chloroform (solvent)] concentrations in the range of 2.4 to 48 mg L(-1) for Telone vapor and 4.8-24 mg L(-1) for three other vapors. The correlation coefficients for Telone, Koril, Endosulfan and Chloroform were 0.992, 0.996, 0.989 and 0.991, respectively. The principal component analysis was also utilized to process the frequency response data of the organic vapors. Using principal component analysis, it was found that more than 93.85% of the data variance could still be explained by use of two principal components (PC1 and PC2). Subsequently, the successful discrimination of Telone and other compounds was quite possible through the principal component analysis of the transient responses of the OV25-modified electrode. In the second method, a molecularly imprinted polymer-coated sensor for Telone was developed. Molecularly imprinted polymer coated quartz crystal (MIP-QCN) showed a selective response to Telone and gave a linear relationship between frequency shift and amount of Telone from 1 to 48 mg L(-1). In this investigation, the proficiency of MIP-QCN and OV25-modified QCN sensors were compared.     

Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics,transformation products,and toxicity evolvement

The aqueous photodegradation of fluopyram was investigated under UV light (λ?≥?200 nm) and simulated sunlight irradiation (λ?≥?290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO₃ ^?), Fe (III) ions, and titanium dioxide (TiO₂) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO₃ ^?, Fe (III), and TiO₂ slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L^?1 Fe (III) and 500 mg L^?1 TiO₂ were about 7-fold and 13-fold faster than that without Fe (III) and TiO₂ under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

An electrochemical nanocomposite modified carbon paste electrode as a sensor for simultaneous determination of hydrazine and phenol in water and wastewater samples

In this study, we report preparation of a high sensitive electrochemical sensor for determination of hydrazine in the presence of phenol in water and wastewater samples. In the first step, we describe synthesis and characterization of ZnO/CNTs nanocomposite with different methods such as transmission electron microscopy (TEM) and X-ray diffraction (XRD). In the second step, application of the synthesis nanocomposite describes the preparation of carbon paste electrode modified with n-(4-hydroxyphenyl)-3,5-dinitrobenzamide as a high sensitive and selective voltammetric sensor for determination of hydrazine and phenol in water and wastewater samples. The mediated oxidation of hydrazine at the modified electrode was investigated by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy (EIS). Also, the values of catalytic rate constant (k) and diffusion coefficient (D) for hydrazine were calculated. Square wave voltammetry (SWV) of hydrazine at the modified electrode exhibited two linear dynamic ranges with a detection limit (3σ) of 8.0 nmol L^?1. SWV was used for simultaneous determination of hydrazine and phenol at the modified electrode and quantitation of hydrazine and phenol in some real samples by the standard addition method.     

Evaluation of growth and biochemical indicators of Salvinia natans exposed to zinc oxide nanoparticles and zinc accumulation in plants

The adverse effects of zinc oxide nanoparticles (ZnO NPs) with an average diameter of 25 nm on the aquatic plant Salvinia natans (L.) All. were determined. Growth, superoxide dismutase (SOD) activity, catalase (CAT) activity, peroxidase activity, and chlorophyll content of the plants were measured after 7 days of exposure to different concentrations of ZnO NPs (1 to 50 mg L^?1). The particle distribution in the culture medium (without plants) during the first 24 h was determined using a Nanotrac 250 particle analyzer. We also investigated the zinc accumulation in leaves and roots of the plant after 7 days of exposure. Exposure to 50 mg L^?1 ZnO NPs significantly increased SOD and CAT activities (P?<?0.05) and significantly depressed photosynthetic pigments (P?<?0.05). However, plant growth was not significantly affected (P?>?0.05). NPs completely precipitated at the bottom of the container at 8 h except for the portions of dissolution and aggregation on the roots. ZnO NPs at a concentration of 50 mg L^?1 can adversely affect S. natans, and their stress is affected by their aggregation and dissolution.     

Facile, effective, and environment-friendly degradation of sulfamonomethoxine in aqueous solution with the aid of a UV/Oxone oxidative process

The degradation of sulfamonomethoxine (SMM) in the aqueous environment by the combination of UV illumination and Oxone has been studied. Experimental results indicated that the UV illumination can effectively activate Oxone to produce sulfate-free radicals (SO₄ ^??). When 10 mmol L^?1 Oxone was added, 96.78 % removal of SMM (5 mg L^?1) was achieved within 90 min. Mineralization of SMM was investigated by measuring the total organic carbon, which decreased by 89.01 % after 90 min reaction. Six intermediate compounds generated during the SMM degradation were identified with the aid of liquid chromatography and mass spectroscopy, combined with proton nuclear magnetic resonance spectroscopy. A general reaction pathway for the degradation of SMM was proposed, where the presence of SO₄ ^?? remained crucial during the degradation process.     

Online microchannel preconcentrator for carbofuran detection

A simple and rapid online microchannel preconcentrator coupled with an amperometric detection for the analysis of carbofuran using polyethylene glycol coated onto magnetic particle (PEG-magnetic particles) sorbents was developed. This simple-to-prepare microchannel preconcentrator used an external magnet to retain the PEG-magnetic particle sorbents inside the microchannel. Under optimum conditions, the system provided two linear ranges, from 0.01 to 10.0 mg L^?1 and from 10.0 to 130.0 mg L^?1 with a limit of detection of 8.7 ± 0.1 μg L^?1. The microchannel preconcentrator provided very good stability; it can be used for up to 326 consecutive injections of 5.0 mg L^?1 carbofuran with a relative standard deviation of less than 3%. The developed system provided a good microchannel-to-microchannel and a good electrode-to-electrode reproducibility (n = 6, %RSD < 1). It also provided an excellent selectivity when it was tested with two other carbamate pesticides, carbaryl and methomyl, with a 43 and 256 times higher detection sensitivity for carbofuran, respectively. The developed system was successfully applied to detect carbofuran in surface water samples obtained near vegetable plantation areas. The concentrations of carbofuran in these samples were found to be in the range of non-detectable to 0.047 ± 0.001 mg L^?1. The developed system is easy to operate and easy to couple with other analytical instruments and it could be easily adapted for the analysis of other polar organic contaminants.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

Tea bag filter paper as a novel protective membrane for micro-solid phase extraction of butachlor in aqueous samples

An innovative, cost-effective, simple, and environmental friendly tea bag filter paper protected micro-solid phase extraction (μ-SPE) technique was developed for the first time with the aim to miniaturize and minimize the use of organic solvents for the extraction and determination of butachlor in aqueous samples. The μ-SPE device was produced by packing 3.0 mg of an easily synthesized new sorbent, hydroxyl-functionalized polypyrrole (OH-PPY), inside a small tea bag filter paper sachet (1.0 cm × 0.5 cm) that served as a protective envelope. Both the extraction and desorption procedures were facilitated by sonication. Due to the high porosity and the fast water absorption of the tea bag filter paper, the analyte could easily diffuse through and enhance the interaction with the sorbent. Under the optimized conditions for the GC-ECD and the μ-SPE, the limit of detection (S/N ≥ 3) was 2.0 μg L^?1 while the limit of quantitation (S/N ≥ 10) was 10.0 μg L^?1. The recoveries of the butachlor spiked at 0.050, 0.10, and 0.50 μg mL^?1 ranged from 77.9 ± 3.0 to 112.5 ± 2.9%. The proposed method was successfully applied for the determination of butachlor in water samples from paddy cultivation sites. The levels found were from non-detectable to 24.71 ± 0.37 μg L^?1.     

A new strategy for determination of hydroxylamine and phenol in water and waste water samples using modified nanosensor

A carbon paste electrode modified with p-chloranil and carbon nanotubes was used for the sensitive and selective voltammetric determination of hydroxylamine (HX) and phenol (PL). The oxidation of HX at the modified electrode was investigated by cyclic voltammetry (CV), chronoamperommetry, and electrochemical impedance spectroscopy. The values of the catalytic rate constant (k), and diffusion coefficient (D) for HX were calculated. Square wave voltammetric peaks current of HX and PL increased linearly with their concentrations at the ranges of 0.1–172.0 and 5.0–512.0 μmol L^?1, respectively. The detection limits for HX and PL were 0.08 and 2.0 μmol L^?1, respectively. The separation of the anodic peak potentials of HX and PL reached to 0.65 V, using square wave voltammetry. The proposed sensor was successfully applied for the determination of HX and PL in water and wastewater samples.     

Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation

The objective of this work was to evaluate the efficiency of a solar TiO₂-assisted photocatalytic process on amoxicillin (AMX) degradation, an antibiotic widely used in human and veterinary medicine. Firstly, solar photolysis of AMX was compared with solar photocatalysis in a compound parabolic collectors pilot scale photoreactor to assess the amount of accumulated UV energy in the system (Q _UV) necessary to remove 20 mg L^?1 AMX from aqueous solution and mineralize the intermediary by-products. Another experiment was also carried out to accurately follow the antibacterial activity against Escherichia coli DSM 1103 and Staphylococcus aureus DSM 1104 and mineralization of AMX by tracing the contents of dissolved organic carbon (DOC), low molecular weight carboxylate anions, and inorganic anions. Finally, the influence of individual inorganic ions on AMX photocatalytic degradation efficiency and the involvement of some reactive oxygen species were also assessed. Photolysis was shown to be completely ineffective, while only 3.1 kJ_UV?L^?1 was sufficient to fully degrade 20 mg L^?1 AMX and remove 61 % of initial DOC content in the presence of the photocatalyst and sunlight. In the experiment with an initial AMX concentration of 40 mg L^?1, antibacterial activity of the solution was considerably reduced after elimination of AMX to levels below the respective detection limit. After 11.7 kJ_UV?L^?1, DOC decreased by 71 %; 30 % of the AMX nitrogen was converted into ammonium and all sulfur compounds were converted into sulfate. A large percentage of the remaining DOC was in the form of low molecular weight carboxylic acids. Presence of phosphate ions promoted the removal of AMX from solution, while no sizeable effects on the kinetics were found for other inorganic ions. Although the AMX degradation was mainly attributed to hydroxyl radicals, singlet oxygen also plays an important role in AMX self-photosensitization under UV/visible solar light.     

Simultaneous analysis of free and sulfo-conjugated steroid estrogens in artificial urine solution and agricultural soils by high-performance liquid chromatography

A simple and robust analytical method was developed to simultaneously detect and quantify 17β-estradiol (E2), estrone (E1), 17β-estradiol-3-sulphate (E2-3S), and estrone-3-sulphate (E1-3S) in aqueous solutions (calcium chloride and artificial urine solutions) and agricultural soils using high performance liquid chromatography and UV detection. The standards for all four compounds were linear in the range of 0.01 to 1.0 μg mL^?1 (n = 6) and 1.0 to 20 μg mL^?1 (n = 6), respectively, with correlation coefficients > 0.999. The on-column limits of detection at an injection volume of 50 μL and S/N (signal: noise) ratio of 3 were: 9.0 ng mL^?1, 10 ng mL^?1, 5.0 ng mL^?1, and 7.0 ng mL^?1 for E2-3S, E1-3S, E2 and E1, respectively. The limit of detection and quantification in artificial urine solution and CaCl₂ solution was 1.0 ng mL^?1 for all four compounds. Method detection limits for the compounds in the 3 soils ranged from 2 to 2.4 ng g^?1 (E2-3S and E1-3S), and 1.0 to 2.9 ng g^?1 (E2 and E1), respectively.     

Determination of phenols and pharmaceuticals in municipal wastewaters from Polish treatment plants by ultrasound-assisted emulsification–microextraction followed by GC–MS

A method combining ultrasound-assisted emulsification–microextraction (USAEME) with gas chromatography–mass spectrometry (GC–MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002–0.121/(0.005–0.403) μg L^?1 and 0.002–0.828/(0.006–2.758) μg L^?1, respectively. Quantitative recoveries (≥94 %) and satisfactory precision (average RSD 8.2 %) were obtained. The optimized USAEME/GC–MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06–551.96 μg L^?1 and 0.01–22.61 μg L^?1, respectively, while for phenols were in the range of 0.03–102.54 μg L^?1 and 0.02–10.84 μg L^?1, respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99 %.     

Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Continuous flow photo-Fenton treatment of ciprofloxacin in aqueous solutions using homogeneous and magnetically recoverable catalysts

The degradation of ciprofloxacin was studied in aqueous solutions by using a continuous flow homogeneous photo-Fenton process under simulated solar light. The effect of different operating conditions on the degradation of ciprofloxacin was investigated by changing the hydrogen peroxide (0–2.50 mM) and iron(II) sulphate (0–10 mg Fe L^?1) concentrations, as well as the pH (2.8–10), irradiance (0–750 W m^?2) and residence time (0.13–3.4 min) of the process. As expected, the highest catalytic activity in steady state conditions was achieved at acidic pH (2.8), namely 85 % of ciprofloxacin conversion, when maintaining the other variables constant (i.e. 2.0 mg L^?1 of iron(II), 2.50 mM of hydrogen peroxide, 1.8 min of residence time and 500 W m^?2 of irradiance). Additionally, magnetite magnetic nanoparticles (ca. 20 nm of average particle size) were synthesized, characterized and tested as a possible catalyst for this reaction. In this case, the highest catalytic activity was achieved at natural pH, namely a 55 % average conversion of ciprofloxacin in 1.8 min of residence time and under 500 W m^?2. Some of the photocatalytic activity was attributed to Fe²⁺ leaching from the magnetic nanoparticles to the solution.     

Photocatalytic degradation of microcystin-LR in aqueous solutions

In this work, the photocatalytic degradation of aqueous microcystin-LR was studied using TiO₂ and ZnO as photocatalysts. The process was optimised and characterised at the bench scale (200 mL); both semiconductors exhibited a high degradation capacity at reaction times of 1 min (degradation greater than 95%). The transient species that were observed indicate that the degradation occurs via the multiple hydroxylation and elimination of the labile peptide residues of the molecule. When photocatalysis was applied in a continuous treatment system (20–50 L), the photocatalytic process exhibited a high degradation efficiency, which resulted in residual microcystin-LR concentrations that were less than 1 μg L^?1 (C₀ = 5 μg L^?1).     

Degradation of chlordecone and beta-hexachlorocyclohexane by photolysis, (photo-)fenton oxidation and ozonation

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlorocyclohexane (β-HCH) in 1 mg L^?1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of β-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for β-HCH the major product peak exhibited C₃H₃Cl₂ as most abundant fragment.     

Environmentally friendly system for the degradation of multipesticide residues in aqueous media by the Fenton’s reaction

A Fenton oxidation system employing zero-valent iron (whose source was swarf, a residue of metallurgical industries, in powder form) and hydrogen peroxide for the treatment of an aqueous solution with six pesticides was developed, and the effect of the iron metal content, pH, and hydrogen peroxide concentration was evaluated. The characterization of the aqueous solution resulted in: pH 5.6, 105 mg L^?1 of dissolved organic carbon, and 44.6 NTU turbidity. In addition, the characterization of the swarf by FAAS and ICP-MS showed 98.43?±?7.40 % of zero-valent iron. The removal was strongly affected by the content of iron metal, pH, and hydrogen peroxide concentration. The best degradation conditions were 2.0 g swarf, pH 2.0, and 5 mmol L^?1 H₂O₂. At the end of the treatment, the pesticide degradation ranged from 60 to 100 %, leading to 55 % mineralization. Besides, all hydrogen peroxide was consumed and the determination of total dissolved iron resulted in 2 mg L^?1. Thus, the advantages of this system are rapid degradation (up to 20 min), high-degradation rates, simple handling, and low cost.

Photocatalytic degradation of the herbicide pendimethalin using nanoparticles of BaTiO3/TiO2 prepared by gel to crystalline conversion method: A kinetic approach

Photocatalytic degradation of the herbicide, pendimethalin (PM) was investigated with BaTiO₃/TiO₂ UV light system in the presence of peroxide and persulphate species in aqueous medium. The nanoparticles of BaTiO₃ and TiO₂ were obtained by gel to crystallite conversion method. These photo catalysts are characterized by energy dispersive x-ray analysis (EDX), scanning electron microscope (SEM), x-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) adsorption isotherm and reflectance spectral studies. The quantum yields for TiO₂ and BaTiO₃ for the degradation reactions are 3.166 Einstein m^?2 s^?1 and 2.729 Einstein m^?2 s^?1 and catalytic efficiencies are 6.0444 × 10^?7 mg^?2h^?1L² and 5.403 × 10^?7 mg^?2h^?1L², respectively as calculated from experimental results. BaTiO₃ exhibited comparable photocatalytic efficiency in the degradation of pendimethalin as the most widely used TiO₂ photocatalyst. The persulphate played an important role in enhancing the rate of degradation of pendimethalin when compared to hydrogen peroxide. The degradation process of pendimethalin followed the first-order kinetics and it is in agreement with Langmuir-Hinshelwood model of surface mechanism. The reason for high stability of pendimethalin for UV-degradation even in the presence of catalyst and oxidizing agents were explored. The higher rate of degradation was observed in alkaline medium at pH 11. The degradation process was monitored by spectroscopic techniques such as ultra violet-visible (UV-Vis), infrared (IR) and gas chromatography mass spectroscopy (GC-MS). The major intermediate products identified were: N-propyl-2-nitro-6-amino-3, 4-xylidine, (2, 3-dimethyl-5-nitro-6-hydroxy amine) phenol and N-Propyl-3, 4-dimethyl-2, 6-dinitroaniline by GC-MS analysis and the probable reaction mechanism has been proposed based on these products.