Heavy metals contamination in vegetables irrigated with wastewater: a case study of underdeveloping regions of Pakistan.

Irrigation of food crops with untreated wastewater leads to the accumulation of heavy metals in their edible parts. Exposure to toxic elements through consumption of contaminated vegetables even at very low concentration is becoming a serious problem for human health in many countries. This issue of heavy metals contamination needs great attention especially in Pakistan where irrigation by wastewater has become a common practice in urban and periurban areas. The present study was conducted to assess the contamination of different heavy metals including nickel (Ni), cadmium (Cd), lead (Pb) and chromium (Cr) in vegetables irrigated with wastewater in different districts of Punjab (Pakistan) like, Faisalabad, Lahore, Gujranwala, Sargodha, Sahiwal, Multan, Rawalpindi and Bahawalpur during years 2016-2019. The maximum contamination factor (Ni, 1.39; Cd, 5.86; Pb, 3.99; Cr, 2.24), pollution load index (2.92) and degree of contamination (13.48) were observed in wastewater irrigated agricultural soils of district Gujranwala as compared to other districts. Mean metal concentration in vegetables grown with untreated wastewater and transfer factor varied with plant type, frequency of irrigation and soils types/series of different districts of Punjab. The highest metal contamination was observed in Gujranwala where 44% vegetable samples were contaminated with Ni, 87% with Cd, 97% with Pb and 88% with Cr. Radar analysis and hierarchical cluster analysis showed that mustard leaves, spinach and lettuce were more contaminated vegetables compared to other vegetables. This study contributes to the evidence-based conclusion that cultivation of vegetable with untreated wastewater should be prohibited and required treatment of wastewater is needed.

One-Pot Hydrothermal Synthesis of Ternary 1T-MoS2 /Hexa-WO3 /Graphene Composites for High-Performance Supercapacitors.

A new ternary composite of 1T-molybdenum disulfide, hexagonal tungsten trioxide, and reduced graphene oxide (M-W-rGO) is synthesized by using a one-pot hydrothermal process. The synergetic effect of 1T-MoS2 and hexa-WO3 nanoflowers improves the electrochemical performance for supercapacitors by inducing additional active sites and hexagonal tunnels, respectively, which lead to high storage capacity and easy transfer of electrolyte ions. The ternary M-W-rGO composite has a high specific capacitance of 836 F g-1 at 1 A g-1 , which is nearly twice that of binary composites of M-rGO and W-rGO with high capacitance retention of 86.35 % after 3000 cycles at a high current density of 5 A g-1 . This study provides a new ternary composite that can be used as an electrode material for high-performance supercapacitors.

Heterochelates of metals as an effective anti - Urease agents couple with their docking studies.

The current article discusses the activities of several synthesized metal heterochelates in in-vitro as anti-ulcer agents followed by their docking study. For this purpose, two important ligands like 8-hydroxyquinoline and DL-methionine were used in synthesis of heterochelates of metal including Cr (III), Mn (II), Fe (III), Co (II), Ni (II), Cu (II), Zn (II), Cd (II) and Pb (II). It was observed that these complexes showed excellent urease inhibition activities in which thiourea was the standard having IC50 value 21.6 ± 0.12µM. The Cu (II) complex showed potent inhibitory activity (22.6 ± 0.72 µM) when compared with the standard thiourea (21.6±0.12µM) among the nine synthesized complexes while Mn (II), Fe (III), Cd (II) and Pb (II) also showed better inhibitory activities. The urease inhibitory activities of hetercochelates also tested and validated by docking analysis.

Convenient pH-responsive removal of Acid Black 1 by green l-histidine/iron oxide magnetic nanoadsorbent from water: performance and mechanistic studies.

This study was aimed at developing green histidine-modified Fe3O4 nanoparticles (His-MNPs) for the adsorptive removal of Acid Black 1 (AB1) from aqueous solution. The His-MNPs were characterized by atomic force microscopy, scanning electron microscopy-energy dispersive X-ray spectrometry, infra-red spectra and thermogravimetry. These MNPs were spherical (average diameter 11-28 nm) with polydispersity index of 1.40 and about 13% mass coating of histidine. To optimize AB1 adsorption on His-MNPs and understand its mechanism, the influences of different operational variables (pH, adsorbent amount, temperature, initial AB1 concentration, contact time, ionic strength, etc.) on adsorption were examined with adsorption isotherms, kinetics and thermodynamic studies. The AB1 adsorption from water was fast with equilibrium time ≤ 45 min. The adsorption equilibrium was best fitted to the Langmuir isotherm model (q max = 166.7 mg g-1 at the adsorbent dose of 0.2 g L-1, temperature 30 °C and pH 4). The linearity order for other isotherms was as follows: Dubinin-Radushkevich (D-R) < Temkin < Freundlich. The kinetics of the AB1 adsorption demonstrated the best compliance with the pseudo-second-order model, predominantly controlled by film diffusion as compared to intraparticle diffusion. Thermodynamic parameters (ΔH° and ΔG°) reflected the exothermic and spontaneous adsorption process. The values of ΔG°, ΔH°, activation energy and D-R free adsorption energy were all consistent with the physisorptive removal of AB1. The spectral (electronic and IR) and pH studies further corroborated the mechanism of AB1 removal by His-MNPs. The His-MNPs showed efficient adsorption, easy regeneration and excellent reusability, assisted by their pH-responsive properties. The prepared adsorbent can provide a safe, effective and economical alternative strategy for removing azo dyes from wastewater.

Fluorine-Free Synthesis of High-Purity Ti3 C2 Tx (T=OH, O) via Alkali Treatment.

MXenes, 2D compounds generated from layered bulk materials, have attracted significant attention in energy-related fields. However, most syntheses involve HF, which is highly corrosive and harmful to lithium-ion battery and supercapacitor performance. Here an alkali-assisted hydrothermal method is used to prepare a MXene Ti3 C2 Tx (T=OH, O). This route is inspired from a Bayer process used in bauxite refining. The process is free of fluorine and yields multilayer Ti3 C2 Tx with ca. 92 wt % in purity (using 27.5 m NaOH, 270 °C). Without the F terminations, the resulting Ti3 C2 Tx film electrode (ca. 52 µm in thickness, ca. 1.63 g cm-3 in density) is 314 F g-1 via gravimetric capacitance at 2 mV s-1 in 1 m H2 SO4 . This surpasses (by ca. 214 %) that of the multilayer Ti3 C2 Tx prepared via HF treatments. This fluorine-free method also provides an alkali-etching strategy for exploring new MXenes for which the interlayer amphoteric/acidic atoms from the pristine MAX phase must be removed.

Advanced oxidation of acridine orange by aqueous alkaline iodine.

The advanced oxidation process is certainly used for the dye waste water treatment. In this continuation a new advanced oxidation via aqueous alkaline iodine was developed for the oxidation of acridine orange (AO) {3, 6 -bis (dimethylamino) acridine zinc chloride double salt}. Oxidation Kinetics of AO by alkaline solution of iodine was investigated spectrophotometrically at λmax 491 nm. The reaction was monitored at various operational parameters like several concentrations of dye and iodine, pH, salt electrolyte and temperature. The initial steps of oxidation kinetics followed fractional order reaction with respect to the dye while depend upon the incremental amount of iodine to certain extent whereas maximum oxidation of AO was achieved at high pH. Decline in the reaction rate in the presence of salt electrolyte suggested the presence of oppositely charged species in the rate determining step. Kinetic data revealed that the de-colorization mechanism involves triodate (I3-) species, instead of hypoidate (OI-) and hypiodous acid (HOI), in alkaline medium during the photo-excitation of hydrolyzed AO. Alleviated concentration of alkali result in decreasing of rate of reaction, clearly indicate that the iodine species are active oxidizing species instead of OH radical. Activation parameters at elevated temperatures were determined which revealed that highly solvated state of dye complex existed into solution. Reaction mixture was subjected to UV/Visible and GC mass spectrum analysis that proves the secondary consecutive reaction was operative in rate determining step and finally dye complex end into smaller fragments.

Reduction of methylene green by EDTA: a relation between dielectric constant of medium and activated state.

Kinetics of an alkaline reduction of the methylene green with ethylenediaminetetraaceticacid (EDTA) as a role of dielectric constant of the medium with anecdotal ionic strength in a diverse solvent system (aqueous mixtures of methanol) (10-30%) was studied by measuring the specific rate constant of the reaction spectrophotometrically at λ (max) = 660nm. An effort has been made to give an elucidation of vital role of dielectric constant of the medium captivating into reflection of single sphere and double sphere complex in reaction assortment. This investigation leads to disclose that single sphere complex of the dye and reductant was found to be the most suitable complex existed in a varied organic solvent. The deviation of the theoretical values from experimental results for single sphere and double sphere complex model in the presence of an alkali and nitrate ions were justified through HPLC analysis. HPLC analysis recommended that a considerable amount of the dye degrades in the existence of nitrate ion and alkali and additional peaks which may be of by-product were obtained. This leads to confirm the non identical values of single sphere and double sphere model in the occurrence of nitrate and an alkali. Rate of deletion of color showed a linear liaison with respect to water content below 30% and temperature between 20-40(o)C whereas an increase in the concentration of organic solvent showed the inhibition of dye decoloration at given optimum condition. Therefore study was restricted up to 30% of methanol binary mixtures. A mechanism of reduction of dye has been proposed based on verdict.