Imidazolate framework material for crude oil removal in aqueus media: Mechanism insight.

Considerable amount of produced water discharged by the oil industry contributes to an environmental imbalance due to the presence of several components potentially harmful to the ecosystem. We investigated the factors influencing the adsorption capacity of Zinc Imidazolate Framework-8 (ZIF-8) in finite bath systems for crude oil removal from petroleum extraction in synthetic produced water. ZIF-8, experimentally obtained by solvothermal method, was characterized by XRD, FTIR, TGA, BET and its point of zero charge (pHpcz) was determined. Synthesized material showed high crystallinity, with surface area equal to 1558 m2 g-1 and thermal stability equivalent to 400 °C. Adsorption tests revealed, based on the Sips model, that the process takes place in a heterogeneous system. Additionally, intraparticle diffusion model exhibited multilinearity characteristics during adsorption process. Thermodynamic investigation demonstrated that adsorption process is spontaneous and exothermic, indicating a physisorption phenomenon. These properties enable the use of ZIF-8 in oil adsorption, which presented an adsorption capacity equal to 452.9 mg g-1. Adsorption mechanism was based on hydrophobic interactions, through apolar groups present on ZIF-8 structure and oil hydrocarbons, and electrostatic interactions, through the difference in charges between positive surface of adsorbent and negatively charged oil droplets.

Application of a novel hybrid MIL-53(Al)@rice husk for the adsorption of glyphosate in water: Characteristics and mechanism of the process.

The development of new materials that have a high capacity to remove pollutants in water-based media is becoming increasingly important because of the serious contamination of water and the negative impact on biodiversity and public health. The presence of glyphosate in water, the most widely used herbicide worldwide, has triggered alerts owing to the collateral effects it may cause on human health. The main objective of the present study was to investigate the potential of the hybrid material MIL-53(Al)@RH for the adsorption of glyphosate in aqueous solution. The material was obtained following the methodology of MIL-53(Al) synthesis in the presence of hydrolyzed rice husk assisted by microwave. Batch adsorption experiments were carried out to evaluate the adsorbent dosage, pH0 solution effect, contact time, adsorbate concentration, and temperature effect. The results demonstrated that a maximum adsorption capacity of 296.95 mg g-1, at pH0 4 with a ratio of 0.04 g MIL-53(Al)@RH/50 mL of solution, was achieved in 30 min. The Avrami and pseudo-second order models appropriately described the adsorption kinetics and the equilibrium by Langmuir and Sips models. The enthalpy changes (ΔH°) determined propose an endothermic reaction governed by chemisorption, corroborating the kinetic and equilibrium settings. Hydrogen bonds, π*-π interactions, and complexation between the metal centers of MIL-53(Al) and the anionic groups of glyphosate were postulated to be involved as adsorption mechanisms. Finally, for practical application, MIL-53(Al)@RH was packed in a column for a fixed-bed test which revealed that the hybrid can remove glyphosate with an adsorption capacity of 76.304 mg L-1, utilizing 90% of the bed.

Microwave-assisted MOF@biomass layered nanomaterials: Characterization and applications in wastewater treatment.

MOF@Biomass layered hybrids were designed through in situ growth from rice husk (RH) and microwave-assisted synthesized MIL-53(Al) particles that enable the reduction of reaction times. The synthesis process included steps to pretreat RH, Al adsorption on RH, and then MIL-53(Al) in-situ growth reaction at 125 °C for 60 min and 200 W irradiation power. The resulting hybrid (MIL-53(Al)@RH) and its parent separate materials were characterized using TGA, SEM, FTIR, XRD, among others. MIL-53(Al)@RH showed high crystallinity in the hybridized MOF particles, thermal decomposition phases, and functional groups (Al-O, O-H, CO, and CC). The hybrid particles allow an easy separation during heterogeneous processing due to their 400 times larger size compared to MIL-53(Al) crystals. The properties of the layered hybrids for removal of Oxytetracycline (OTC), Diclofenac (DCL), and Glyphosate (GLY) in aqueous solutions, were tested by adsorption (ADS) and advanced oxidation processes (AOP). The high ADS capacities (162 mg g-1 GLY, 139 mg g-1 OTC, 93 mg g-1 DCL) and % removal in AOP (97% GLY, 91% OTC, 80% DCL) demonstrated that MIL-53(Al) maintained its properties after hybridization.

Development of an inexpensive and rapidly preparable enzymatic pencil graphite biosensor for monitoring of glyphosate in waters.

Glyphosate (GLY) is the most widely used non-selective broad-spectrum herbicide worldwide under well-reported side effects on the environment and human health. That's why it's necessary to control its presence in the environment. This work describes the development of an affordable, simple, and accurate electrochemical biosensor using a pencil graphite electrode as support, a horseradish peroxidase enzyme immobilized on a polysulfone membrane doped with multi-walled carbon nanotubes. The developed electrochemical sensor was used in the determination of GLY in river and drinking water samples. Cyclic voltammetry and amperometry were used as electrochemical detection techniques for the characterization and analytical application of the developed biosensor. The working mechanism of the biosensor is based on the inhibition of the peroxidase enzyme by GLY. Under optimal experimental conditions, the biosensor showed a linear response in the concentration range of 0.1 to 10 mg L-1. The limits of detection and quantification are 0.025 ± 0.002 and 0.084 ± 0.007 mg L-1, respectively, which covers the maximum residual limit established by the EPA for drinking water (0.7 mg L-1). The proposed biosensor demonstrated high reproducibility, excellent analytical performance, repeatability, and accuracy. The sensor proved to be selective against other pesticides, organic acids, and inorganic salts. Application on real samples showed recovery rates ranging between 98.18 ± 0.11 % and 97.32 ± 0.23 %. The analytical features of the proposed biosensor make it an effective and useful tool for the detection of GLY for environmental analysis.

Challenges in the design of electrochemical sensor for glyphosate-based on new materials and biological recognition.

Glyphosate (GLY) is the main ingredient in the weed killer Roundup and the most widely used pesticide in the world. Studies of the harmful effects of GLY on human health began to become more wide-ranging after 2015. GLY is listed by the International Agency for Research on Cancer (IARC) as a carcinogenic hazard to humans. Moreover, GLY has the property to complex with transition metals and are stable for long periods, being considered a high-risk element for different matrices, such as environmental (soil and water) and food (usually genetically modified crops). Since that, it was noticed an increment in the development of new analytical methods for its determination in different matrices like food, environmental and biological fluids. Noteworthy, the application of electrochemical techniques for downstream detection sparked interest due to the ability to minimize or eliminate the use of polluting chemicals, using simple and affordable equipment. This work aims to review the contribution of the electroanalytical methods for the determination of GLY in different food and environmental matrices. Parameters such as the electrochemical transduction techniques based on the electrical measurement signals, receptor materials for electrodes preparation, and the detection mechanisms are described in this review. The literature review shows that the electrochemical sensors are powerful detection system that can be improved by their design and by their portability to fulfil the needs of the GLY determination in laboratory benches, or even in situ analysis.