Quantification of Chlorpyrifos Residues in Water under Thermodynamically Favorable Electrodics Using the f-MWCNT/N-(2-C2H5O) ED(CH3COONa)3 Composite of Superior Selectivity.

Researchers are continually seeking potential alternatives to develop water quality sensors with higher selectivity to obtain the desired performance during real-time deployment. Quantification technologies involving interface materials of distinguishing capacity at elevated matrix complexity are desirable. However, there remains a challenge in designing suitable techniques, methodologies, and appropriate validations to support the grounds for the selection of interface materials of enhanced selectivity. The ability to monitor chlorpyrifos in analytical and commercial grade compounds and in the water matrix using an interface material of suitable states is the focus of this work. Herein, N-(2-hydroxyethyl) ethylenediamine triacetic acid trisodium (N-(2-C2H5O) ED(CH3COONa)3) incorporated with functionalized multiwalled carbon nanotube (f-MWCNT) is reported to provide thermodynamically favorable charge transfer for the quantification of chlorpyrifos residues under varying internal and external conditions with appropriate validations using density functional theory (DFT) and high-performance liquid chromatography (HPLC). The sensor exhibited excellent figures of merit such as limit of detection (LOD) and limit of quantitation (LOQ) of 9.7 pM and 29.4 pM, respectively.

Photocatalytic degradation of Reactive Black dye using ZnO-CeO2 nanocomposites.

This study presents the photocatalytic efficiency of ZnO-CeO2 nanocomposites for the degradation of a model Reactive Black (RB) dye. Nano-CeO2 was synthesized using cerium nitrate precursor solution via chemical precipitation. Synthesized nano-CeO2 was mixed with ZnO nanoparticles in different mass ratios to obtain ZnO-CeO2 heterojunction photocatalyst. The morphology of the nanocomposites was examined using transmission electron microscope (TEM). X-ray diffraction patterns of the CeO2 corresponded well with (1 1 1) plane of cubic-phase CeO2. The band gap of the ZnO-CeO2 nanocatalyst synthesized was determined to be 3.08 eV, which was lower than that of the pristine CeO2 and ZnO powders, respectively. The results indicate that 1:1 wt. ratio ZnO-CeO2 nanocomposite provides about 85% RB degradation within 90 min under UV light under alkaline pH conditions. Degradation rate of RB dye achieved with ZnO-CeO2 nanocomposite was almost 1.5 times greater than that obtained with pristine ZnO. Increasing CeO2 ratio beyond 1:1 wt. ratio did not significantly increase RB degradation. The results demonstrate that addition of CeO2 to ZnO results in lowering its band gap energy and aids charge carrier separation resulting in enhanced oxidation of RB dye under UV light.

Real-time detection of imidacloprid residues in water using f-MWCNT/EDTA as energetically suitable electrode interface.

Real-time assessment of an active ingredient imidacloprid in the water matrix is critically momentous in monitoring the levels of pesticide contaminants in water bodies. Conventional approaches predominantly deal with the detection of imidacloprid, relying on the purified analytical grade compound. Herein, we report an organic/inorganic composite (f-MWCNT/EDTA) integrated electrochemical sensor for the real-time analysis of analytical grade imidacloprid and extended the performance evaluation in agriculture-purpose imidacloprid compound used commercially by farmers. The choice of the electrode interface significantly supports the electrocatalytic activity towards imidacloprid due to the presence of appropriate energy levels, which are favourable for charge transfer processes validated with Density Functional Theory (DFT) calculations. Further, the performance of the sensor was evaluated in the aquatic environment using river water samples procured from seven different sampling sites and in tap water. The organic/inorganic composite-based electrochemical sensor shows a detection limit of 3.1 × 10-3 pM and three significant wide linear concentration ranges of 0.001-0.05 nM, 0.001-0.04 µM, and 0.001-0.004 mM with apparent interferent resistance. This work paves the way for the real-time environmental monitoring and quantification of imidacloprid by utilizing the highly effective f-MWCNT/EDTA composite catalytic layer.

Biosorption study of amaranth dye removal using Terminalia chebula shell, Peltophorum pterocarpum leaf and Psidium guajava bark.

Amaranth dye (AD) is trisodium (4E)-3-oxo-4-[(4-sulfonato-1- naphthyl) hydrazono] naphthalene-2, 7-disulfonate and anionic in nature. In the present investigation, waste biomasses such as Terminalia chebula shell (TCS), Peltophorum pterocarpum leaf (PPL) and Psidium guajava bark (PGB) are explored as biosorbents for the first time toward the removal of AD from aqueous solution in a batch method. Influence of biosorption parameters such as pH, initial concentration of AD, biosorbents (TCS, PPL, PGB) dosage, temperature and contact time was studied. Biosorption equilibrium data was analyzed using two parameter isotherms. The kinetics of the biosorption process was analyzed using different models to understand the rate-determining step. The results of the biosorption experiment and modeling investigation illustrated that the pseudo-second-order rate equation fits the experimental data and further the experimental results showed Langmuir isotherm fitted well the biosorption equilibrium data. TCS showed more efficiency toward the removal of AD than PPL and PGB. The value of enthalpy for TCS is 1.527 kJ/mol suggests that the AD removal process is endothermic. The positive value of entropy is 6.429 J/mol K indicates that the particle is randomly disordered and negative values of standard Gibbs free energy (ΔG°) suggested that the biosorption process is spontaneous.Novelty statementBiomasses of Terminalia chebula shell (TCS), Peltophorum pterocarpum leaf (PPL) and Psidium guajava bark (PGB) reported as first time explored biosorbent for amaranth dye (AD) removal from aqueous solution.Optimal biosorption parameter for AD removal determined.Experimental data examined using isotherm, kinetic and thermodynamic analysis.

Arsenic sorption on TiO2 nanoparticles: size and crystallinity effects.

Single solute As (III) and As (V) sorption on nano-sized amorphous and crystalline TiO(2) was investigated to determine: size and crystallinity effects on arsenic sorption capacities, possible As (III) oxidation, and the nature of surface complexes. Amorphous and crystalline nanoparticles were prepared using sol-gel synthesis techniques. For amorphous TiO(2), solute pH in the range of 4-9 had a profound impact on only As (V) sorption. As (III) and As (V) sorption isotherms indicated that sorption capacities of the different TiO(2) polymorphs were dependent on the sorption site density, surface area (particle size) and crystalline structure. When normalized to surface area, As (III) surface coverage on the TiO(2) surface remained almost constant for particles between 5 and 20 nm. However, As (V) surface coverage increased with the degree of crystallinity. X-ray absorption spectroscopic analysis provided evidence of partial As (III) oxidation on amorphous TiO(2) rather than crystalline TiO(2). The data also indicated that As (III) and As (V) form binuclear bidentate inner-sphere complexes with amorphous TiO(2) at neutral pH.

Investigation of a mercury speciation technique for flue gas desulfurization materials.

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method. Potential candidates of pure mercury standards including mercuric chloride (HgCl2), mercurous chloride (Hg2Cl2), mercury oxide (HgO), mercury sulfide (HgS), and mercuric sulfate (HgSO4) were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg2Cl2 and HgCl2 could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury.

Speciation, characterization, and mobility of As, Se, and Hg in flue gas desulphurization residues.

Flue gas from coal combustion contains significant amounts of volatile toxic trace elements such as arsenic (As), selenium (Se), and mercury (Hg). The capture of these elements in the flue gas desulphurization (FGD) scrubber unit has resulted in generation of a metal-laden residue. With increasing reuse of the FGD residues in beneficial applications, it is important to determine metal speciation and mobilityto understand the environmental impact of its reuse. In this paper, we report the solid phase speciation of As, Se, and Hg in FGD residues using X-ray absorption spectroscopy (XAS), X-ray fluorescence spectroscopy (XRF), and sequential chemical extraction (SCE) techniques. The SCE results combined with XRF data indicated a strong possibility of As association with iron oxides, whereas Se was distributed among all geochemical phases. Hg appeared to be mainly distributed in the strong-complexed phase. XRF images also suggested a strong association of Hg with Fe oxide materials within FGD residues. XAS analysis indicated that As existed in its oxidized state (As(V)), whereas Se and Hg was observed in primarily reduced states as selenite (Se(IV)) and Hg(I), respectively. The results from the SCE and variable pH leaching tests indicated that the labile fractions of As, Se, and Hg were fairly low and thus suggestive of their stability in the FGD residues. However, the presence of a fine fraction enriched in metal content in the FGD residue suggested that size fractionation is important in assessing the environmental risks associated with their reuse.