Alumina-Hydroxyapatite Millimetric Spheres for Cadmium(II) Removal in Aqueous Medium.

Heavy metals can act as selective agents in the development and proliferation of antibiotic-resistant bacteria through a process called coselection. In the year 2050, an estimated 10 million deaths will be caused by antibiotic-resistant bacteria; therefore, the presence of heavy metals in bodies of water represents an environmental and sanitary threat that requires efficient treatment processes and/or materials for their removal. In the present study, the effect of the hydroxyapatite coating on the adsorbent capacity of cadmium in alumina spheres was evaluated. The hydroxyapatite coating on the alumina sphere increased the surface area from 0.66 to 0.96 m2/g and the number of acid sites from 0.064 to 0.306 meq/g and displaced the IEP of hydroxyapatite from 5.37 to 4.2, increasing the Cd2+ adsorbing capacity from 59.87 mg/g to 89.37 mg/g and promoting adsorption by surface complexation. Alumina-hydroxyapatite spheres stand out for their improved adsorbent properties and easy handling, which positioned this material as a potential alternative in adsorption processes.

Binary fluoride and As(V) adsorption in water using pleco fish bone chars.

The present work studied individual and binary adsorption of fluorides and As(V) in water on pleco fish bone chars (BC), as well as the effect of BC mass variation on the adsorption capacity of fluoride and As(V) in water for human consumption. The results of individual adsorption indicated that the adsorption of fluoride and As(V) on BC depends on solution pH. The adsorption capacity of fluorides at an initial concentration of 30 mg L-1 increases approximately 3 times, from 5.9 to 15.3 mg g-1, when decreasing the pH of the solution from 9 to 5, however, for the case of As(V) an antagonistic effect is observed, the adsorption capacity increases 7 times when raising the pH from 5 to 9, from 18.4 to 132.1 µg g-1 at an initial As(V) concentration of 300 µg L-1. Besides, in the binary adsorption, BC showed a higher affinity to adsorb fluoride since its adsorption capacity decreased from 16.55 to 12.50 mg g-1 as the As(V) concentration increased from 0 to 800 µg L-1 in solution. In contrast, As(V) adsorption was severely affected, decreasing from 140.2 to 32.7 µg g-1 when the fluoride concentration in the solution increased from 0 to 100 mg L-1. On the other hand, in the adsorption of groundwater contaminated with fluoride and As(V), it was determined that increasing the mass of BC from 0.5 to 20 g increases the removal percentage, reaching 99.3 and 75.7% removal for fluoride and As(V), respectively, due to the fact that increasing the mass of the adsorbent leads to a larger area and a greater number of sites that allow the adsorption of these contaminants. The thermodynamic study revealed the spontaneity of fluoride and As(V) adsorption, better affinity for fluoride but higher adsorption rate of As(V) on BC. Characterization techniques such as XRD and EDS allowed identifying hydroxyapatite as the mineral phase of BC, which is responsible for the adsorption of BC. By studying the effect of solution pH on the adsorption capacities and the characterization of BC such as XRD, EDS and TGA, it was determined that the mechanisms of fluoride adsorption are by electrostatic attractions and ion exchange, and for As(V) it is by coprecipitation and ion exchange. It was concluded that BC from pleco fish could be an alternative for treating water contaminated by fluorides and As(V).

Molecularly imprinted polymers (MIPs) as efficient catalytic tools for the oxidative degradation of 4-nonylphenol and its by-products.

Water pollution is a current global concern caused by emerging pollutants like nonylphenol (NP). This endocrine disruptor cannot be efficiently removed with traditional wastewater treatment plants (WTPs). Therefore, this work aimed to evaluate the adsorption influence of molecularly imprinted polymers (MIPs) on the oxidative degradation (ozone and ultraviolet irradiations) of 4-nonylphenol (4-NP) and its by-products as a coadjuvant in WTPs. MIPs were synthesized and characterized; the effect of the degradation rate under system operating conditions was studied by Box-Behnken response surface design of experiments. The variables evaluated were 4-NP concentration, ozone exposure time, pH, and MIP amount. Results show that the MIPs synthesized by co-precipitation and bulk polymerizations obtained the highest retention rates (> 90%). The maximum adsorption capacities for 4-NP were 201.1 mg L-1 and 500 mg L-1, respectively. The degradation percentages under O3 and UV conditions reached 98-100% at 120 s of exposure at different pHs. The degradation products of 4-NP were compounds with carboxylic and ketonic acids, and the MIP adsorption was between 50 and 60%. Our results present the first application of MIPs in oxidation processes for 4-NP, representing starting points for the use of highly selective materials to identify and remove emerging pollutants and their degradation by-products in environmental matrices.

Design and application of molecularly imprinted polymers for adsorption and environmental assessment of anti-inflammatory drugs in wastewater samples.

In this study, a series of molecularly imprinted polymers (MIPs) have been synthesized using separately diclofenac, naproxen, and ibuprofen as templates with three different polymerization approaches. Two functional monomers, methacrylic acid (MAA) and 2-vinylpyridine (2-VP), were tested and ethylene glycol dimethacrylate (EGDMA) was used as crosslinker; also, template-free polymers (NIPs) were synthesized. It was found that the MIP with the highest retention percentage for diclofenac was the one prepared by the emulsion approach and with MAA (98.3%); for naproxen, the one prepared by the bulk polymerization with MAA (99%); and for ibuprofen, the one synthesized by bulk with 2-VP (97.7%). These three MIPs were characterized by scanning electron microscopy, thermogravimetric test, Fourier transform infrared, specific area measurements, and surface charge. It was found that the emulsion method allowed particle size control, while the bulk method gave heterogeneous particles. The three evaluated MIPs exhibited thermal stability up to 300 °C, and it was observed that 2-VP confers greater stability to the material. From the BET analysis, it was demonstrated that the MIPs and NIPs evaluated are mesoporous materials with a pore size between 10 and 20 nm. In addition, the monomer influenced the surface charge of the material, since the MAA conferred an acidic point of zero charge (PZC), while the 2-VP conferred a PZC of basic character. Through adsorption isotherms, it was determined  that there is a higher adsorption capacity of the MIPs at acidic pH following a pseudo-second-order kinetic model. Finally, the MIPs were used to determine the non-steroidal anti-inflammatory drugs (NSAIDs) understudy in San Luis Potosí, México, wastewater, finding concentrations of 0.642, 0.985, and 0.403 mg L-1 for DCF, NPX, and IBP, respectively.

Synthesis and characterization of hydrochar from industrial Capsicum annuum seeds and its application for the adsorptive removal of methylene blue from water.

Chili seeds (CS) represent one of the most abundant residues in Mexico due to the high production and consumption. In this work, CS were used as raw material for the production of low-cost adsorbents for the removal of methylene blue from water. The adsorbents were synthesized from a hydrothermal treatment (based on a surface response experiment design) and characterized texturally by assessing changes in their properties. The mass yield (%R), carbon content (%C), and the second order adsorption rate constant (k2) were derived in relation to a list of input variables (e.g., the reaction temperature, residence time, and water/biomass ratio). Accordingly, those output variables were affected most sensitively by temperature and/or residence time, while changes of the water/biomass ratio were insignificant. Besides, an increase in the reaction temperature favored the degradation of the lignocellulosic material with increases in the carbon fixation. The adsorption capacity of methylene blue (MB) by the hydrochars depended drastically on the oxygen/carbon ratio. As such, the maximum adsorption capacity value of 145 mg g-1 was attained at the initial MB concentration of ~3000 µM (optimal oxygen/carbon value of 0.43). On the other hand, the maximum partition coefficient (KD) was estimated as 2.96 µM-1 mg g-1 with the initial/equilibrium concentrations of 20.5/6.93 µM. The performance evaluation between different studies, when made in terms of KD, suggests that the tested hydrochar should be one of the best adsorbents to treat methylene blue, especially at near-real environmental conditions (e.g., below micromolar levels).

Removal of diethyl phthalate from water solution by adsorption, photo-oxidation, ozonation and advanced oxidation process (UV/H2O2, O3/H2O2 and O3/activated carbon).

The objective of this work was to compare the effectiveness of conventional technologies (adsorption on activated carbon, AC, and ozonation) and technologies based on advanced oxidation processes, AOPs, (UV/H(2)O(2), O(3)/AC, O(3)/H(2)O(2)) to remove phthalates from aqueous solution (ultrapure water, surface water and wastewater). Diethyl phthalate (DEP) was chosen as a model pollutant because of its high water solubility (1,080 mg/L at 293 K) and toxicity. The activated carbons showed a high adsorption capacity to adsorb DEP in aqueous solution (up to 858 mg/g), besides the adsorption mechanism of DEP on activated carbon is governed by dispersive interactions between π electrons of its aromatic ring with π electrons of the carbon graphene planes. The photodegration process showed that the pH solution does not significantly affect the degradation kinetics of DEP and the first-order kinetic model satisfactorily fitted the experimental data. It was observed that the rate of decomposition of DEP with the O(3)/H(2)O(2) and O(3)/AC systems is faster than that with only O(3). The technologies based on AOPs (UV/H(2)O(2), O(3)/H(2)O(2), O(3)/AC) significantly improve the degradation of DEP compared to conventional technologies (O(3), UV). AC adsorption, UV/H(2)O(2), O(3)/H(2)O(2), and O(3)/AC showed a high yield to remove DEP; however, the disadvantage of AC adsorption is its much longer time to reach maximum removal. The best system to treat water (ultrapure and natural) polluted with DEP is the O(3)/AC one since it achieved the highest DEP degradation and TOC removal, as well as the lower water toxicity.