Synthesis of fructose bound Fe(iii) integrated carbon dots as a robust turn-off detection sensor for chlortoluron.

A simple, sensitive, and robust fluorescent sensor for chlortoluron detection has been developed. Fluorescent carbon dots were synthesized using ethylene diamine and fructose via a hydrothermal protocol. The molecular interaction between fructose carbon dots and Fe(iii) resulted in a fluorescent metastable state exhibiting remarkable fluorescence quenching at λem of 454 nm and interestingly, further quenching occurred upon the addition of chlortoluron. The quenching in the fluorescence intensity of CDF-Fe(iii) towards chlortoluron occurred in the concentration range of 0.2-5.0 µg mL-1 where the limit of detection was found to be 0.0467 µg mL-1, the limit of quantification was 0.14 µg mL-1, and the relative standard deviation was 0.568%. The selective and specific recognitive nature of the Fe(iii) integrated fructose bound carbon dots towards the chlortoluron make it a suitable sensor for real sample applications. The proposed strategy was applied for the determination of chlortoluron in soil, water, and wheat samples with recoveries in the range of 95% to 104.3%.

Photocatalytic assessed adsorptive removal of tinidazole from aqueous environment using reduced magnetic graphene oxide-bismuth oxychloride and its silver composite.

Antibiotics (tinidazole (TNZ)) in wastewater, exhibit adverse effects on humans and ecosystem. The current study was aimed to synthesize photocatalysts mrGO/BiOCl and mrGO/BiOCl/Ag. mrGO was coupled with BiOCl by hydrothermal method and Ag was deposited over it. The synthesized mrGO/BiOCl and mrGO/BiOCl/Ag were confirmed by Pzc analysis (5.5 and 4.4 for mrGO/BiOCl and mrGO/BiOCl/Ag, respectively), surface area analysis (380 m2 g-1, 227.7 m2 g-1, 220 m2 g-1 for mrGO, mrGO/BiOCl and mrGO/BiOCl/Ag respectively), elemental analysis (Ag, O, Bi, Fe), surface morphology (rough ball like sphere of mrGO/BiOCl and cubic Ag nanoparticles in mrGO/BiOCl/Ag), functional groups and band gap (Eg) determination. The Eg was determined using Kubelka-Munk equation as 3.5 and 2.8 eV for mrGO/BiOCl and mrGO/BiOCl/Ag respectively. During the adsorption study, the best experimental conditions for various operating parameters such as pH (2), contact time (5 min for mrGO/BiOCl and 10 min for mrGO/BiOCl/Ag under UV irradiation), TNZ concentration (18 µgL-1) and catalyst dosage (0.001 g) were achieved. Kinetic study revealed that both composites followed pseudo second order kinetics (R2 = 0.9979 and 0.9986, respectively). Data of rGO/BiOCl was fitted to Freundlich adsorption model (R2 = 0.9687) and rGO/BiOCl/Ag fitted to Langmuir adsorption model (R2 = 0.9994). Moreover, thermodynamic parameters confirmed that a photodegradation phenomenon was spontaneous and exothermic. The results confirmed that rGO/BiOCl and rGO/BiOCl/Ag are appropriate composites for TNZ removal from the aqueous environment with removal efficiency of 97 and 24%, respectively.

Efficient removal of selected fluoroquinolones from the aqueous environment using reduced magnetic graphene oxide/polyaniline composite.

In the present study, reduced magnetic graphene oxide/polyaniline (RmGO/PANI) composite was synthesized via in-situ oxidative polymerization method. The synthesized RmGO/PANI was characterized by fourier transform infrared, scanning electron microscope, X-ray diffraction and energy dispersive X-rays techniques. The synthesized RmGO/PANI was explored as an adsorbent for the removal of moxifloxacin (MOX) and ofloxacin (OFL) from the aqueous samples. To inflate removal efficiency of RmGO/PANI, various adsorption effecting parameters such as effect of pH (2-12), RmGO/PANI dosage (2-14 mg), analyte concentration (150-525 µg mL-1 for MOX and 15-40 µg mL-1 for OFL), contact time (10-120 min) and temperature (293-343 K) were studied. Moreover, kinetic study exhibits that adsorption of MOX/OFL using RmGO/PANI follows pseudo second order kinetic model. The adsorption of MOX/OFL well-fitted to the Langmuir adsorption isotherm which demonstrates mono-layer adsorption of MOX/OFL on the surface of RmGO/PANI with maximum adsorption capacity of 47.7 mg g-1 and 27.33 mg g-1 for OFL and MOX, respectively. Thermodynamic study indicates that the adsorption process was spontaneous and exothermic in nature with the decrease of randomness of the system during the adsorption. On account of its practical applications, RmGO/PANI is considered an excellent adsorbent with 99% and 96% removal efficacy for MOX and OFL, respectively. The synthesized RmGO/PANI was reused for ten consecutive batches as well as applied to the real samples, maintain an excellent removal capacity. The reusable nature of RmGO/PANI declare this solid medium as an innovative adsorbent for real sample applications and wastewater treatment.

Determination of Isoproturon in Environmental Samples using the QuEChERS Extraction-Spectrofluorimetric Method.

An accurate and sensitive method has been developed for determination of the herbicide isoproturon using the Quick Easy Cheap Effective Rugged Safe (QuEChERS) extraction-spectrofluorimetric technique. The method involves the reaction of 2-cyanoacetamide with isoproturon in basic medium (NH3 ; 15 mol/L). The resulting fluorescent product was found to show maximum emission at 378 nm and maximum excitation at 333 nm. Fluorescence intensity under the influence of different parameters was investigated. The linear range of analyte concentrations was found to be 0.5 to 15 µg/mL, with a limit of detection of 0.144 µg/mL, a limit of quantification of 0.437 µg/mL (signal to noise ratio = 3), and a regression coefficient of 0.9991, under optimized conditions. The proposed method was effectively applied for determination of isoproturon in different matrices; the percentage of recovery varied from 85.00 ± 1.2% to 96.00 ± 0.5%. The method was also applied for residue analysis of isoproturon in real soil samples collected from a pilot field. For extraction of isoproturon, the QuEChERS extraction approach was used, and the average residue in the soil samples was found to be 0.81 ± 0.07 µg/g. To show the potential of this approach, our results were compared with those of other methods reported in the literature. Environ Toxicol Chem 2019;38:2614-2620. © 2019 SETAC.

Kinetic and equilibrium profile of the adsorptive removal of Acid Red 17 dye by surfactant-modified fuller's earth.

In the present study, fuller's earth (FE) was modified with sodium dodecyl sulfate for removal of Acid Red 17 (AR 17) dye from aqueous solutions. The surfactant-modified FE and FE were characterized by a Fourier transform infrared spectrometer, thermogravimetric analyzer and scanning electron microscope. Batch adsorption experiments were carried out as a function of contact time, pH, initial concentration of AR 17 and adsorbent dosage. About 99.1% adsorption efficiency was achieved within 60 min at adsorbent dose of 0.1 g for initial dye concentration of 1,000 mg L-1 at pH 10. The adsorption data were well fitted with the Dubinin-Radushkevich isotherm model implying physisorption as the major phenomenon for adsorption. The kinetic data were analyzed using four kinetic equations: pseudo-first-order, pseudo-second-order, intraparticle diffusion and Elovich equations. The rates of adsorption confirmed the pseudo-second-order kinetics with good correlation value (R2 = 0.999). The results indicate that the modified adsorbent can effectively be used for the removal of AR 17 from wastewater with high absorption capacity of 2164.61 mg g-1.

Spectrofluorimetric Method for Quantification of Triazine Herbicides in Agricultural Matrices.

A spectrofluorimetric method for determination of triazine herbicides was developed. The method involves reaction of ammonical 2-cyanoacetamide with the herbicide. The net fluorescent intensity (FI) of the product was measured at 376 nm using 330 nm as excitation wavelength. A linear relationship between concentration and FI was found in the range of 0.3 - 10 µg mL(-1) for atrazine and 0.2 - 10 µg mL(-1) for terbutryn. The LOD and LOQ were found to be 0.07 ± 0.023 µg mL(-1) and 0.23 ± 0.023 µg mL(-1), respectively, with %RSD <12.1% for atrazine and 0.027 ± 0.009 µg mL(-1) and 0.091 ± 0.009 µg mL(-1), respectively, with %RSD <5% for terbutryn. The %recoveries of the subject triazines from soil and wheat grains were found in the range of 90.0 ± 0.14 to 96.0 ± 0.15% for atrazine and 95.0 ± 0.05 to 98 ± 0.02% for terbutryn.

Determination of ametryn in sugarcane and ametryn-atrazine herbicide formulations using spectrophotometric method.

A sensitive spectrophotometric method has been developed for determination of ametryn in agricultural samples. The proposed method was based on reaction with pyridine and further coupling with sulfanilic acid to form a colored product. The absorbance was measured at 400 nm with a molar absorptivity of 2.1 x 10(5) L mol(-1) cm(-1). The method shows a linear range from 0.2-20 µg mL(-1) with limit of detection and limit of quantification 0.16 and 0.54 µg mL(-1), respectively. The method has been successfully applied to the determination of ametryn in sugarcane juice and commercial formulations after separation of ametryn from triazine herbicides based on solvent extraction. Recovery values were found to be in the range of 96.0 ± 0.2% to 98.4 ± 0.1%.

Quantification of triazine herbicides in soil by microwave-assisted extraction and high-performance liquid chromatography.

A method for the determination of herbicides residues, triazine (atrazine, metribuzin, ametryn, and terbutryn), in soil samples with high-performance liquid chromatography (HPLC)-UV detection is described. The proposed method is based on microwave-assisted extraction (MAE) of soil samples for 4 min at 80% of 850-W magnetron outputs in the presence of mixture of solvents (methanol/acetonitrile/ethylacetate). Related important factors influencing the MAE efficiency, such as the solvent type and volume, irradiation energy, and time, were optimized in detail. Calibration curve ranges established using HPLC for metribuzin, atrazine, ametryn, and terbutryn are 1.0-19.0, 0.9-18.0, 0.6-11.0, and 0.7-11.0 µg mL( -1), respectively. The limits of detection of metribuzin, atrazine, ametryn, and terbutryn are 0.30, 0.24, 0.16, and 0.20 µg mL( -1) while limits of quantification are 1.0, 0.80, 0.50, and 0.60 µg mL( -1), respectively. A Plackett-Burman factorial design was used as a screening method in order to select the variables that influence MAE extraction. The recoveries of the method at three different spiked levels were assessed by analyzing real soil samples and were found to be in the range of 83.33 ± 0.12-96.33 ± 0.23 with good precision (<8%).

Quantification of pendimethalin in soil and garlic samples by microwave-assisted solvent extraction and HPLC method.

A method for the residual pendimethalin in soil and vegetable samples was developed. The method is based on extraction of pendimethalin from samples using microwave-assisted solvent extraction (MASE) with acetone, ethanol, and water as extraction solvent. Extracted pendimethalin samples were analyzed by high-performance liquid chromatography with ultraviolet detector at 240 nm. The MASE parameters, temperature, heating time, and solvent types were optimized with the feasibility of MASE application in the determination of pendimethalin extraction efficiency of pendimethalin from soil and vegetable samples. The maximum temperature that can be used during the heating for MASE is 60°C, where the recovery percentages reached 97%. Linearity for pendimethalin was found in the range of 2-20 µg mL(-1) with limits of detection and limits of quantification of 0.059 and 0.17 µg mL(-1), respectively.

Glyphosate herbicide residue determination in samples of environmental importance using spectrophotometric method.

A simple selective spectrophotometric method has been developed for the determination of glyphosate herbicide in environmental and biological samples. Glyphosate was reacted with carbon disulphide to form dithiocarbamic acid which was further followed for complex formation with copper in the presence of ammonia. The absorbance of the resulting yellow coloured copper dithiocarbamate complex was measured at 435 nm with molar absorptivity of 1.864 x 10(3) L mol(-1)cm(-1).The analytical parameters were optimized and Beer's law was obeyed in the range of 1.0-70 microg mL(-1). The composition ratio of the complex was glyphosate: copper (2:1) as established by Job's method with a formation constant of 1.06 x 10(5). Glyphosate was satisfactorily determined with limit of detection and quantification of 1.1 and 3.7 microg mL(-1), respectively. The investigated method was applied successfully to the environmental samples. Recovery values in soil, wheat grains and water samples were found to be 80.0+/-0.46 to 87.0+/-0.28%, 95.0+/-0.88 to 102.0+/-0.98% and 85.0+/-0.68 to 92.0+/-0.37%, respectively.

Extractive spectrophotometric method for determination of metribuzin herbicide and application of factorial design in optimization of various factors.

A simple extractive spectrophotometric method has been described for the determination of metribuzin herbicide. Metribuzin was reacted with copper and a stable complex in the presence of ammonia (0.2M) at pH 10.5 was formed. The resulting yellow coloured complex was extracted in chloroform and showed absorption maxima at 340 nm. Beer's law was obeyed in the range of 0.8-25 microg mL(-1) with molar absorptivity of 5.67 x 10(3)L mol(-1)cm(-1). The composition of the complex was studied by Job's method of continuous variation and the results indicated that the mole ratio of metribuzin:Cu(2+) is 2:1. The optimum reaction conditions for complexation and other analytical parameters were evaluated. A two-level factorial design was also used to determine the effect of different parameters and their interaction on metribuzin:Cu(2+) complex formed. The method was successfully applied for the determination of metribuzin in commercial formulations and real samples.