Characterization of sargassum accumulated on Dominican beaches in 2021: Analysis of heavy, alkaline and alkaline-earth metals, proteins and fats.

This paper presents the characterization of sargassum that reached the shores of eight Dominican beaches in 2021. The analysis of heavy, alkaline and alkaline-earth metals was performed by ICP-OES. Twelve heavy metals were studied, with the highest concentrations corresponding to Fe, As, and Zn. Regarding the alkaline and alkaline-earth metals, the highest concentrations were detected for Ca, K, Na and Mg. The high values of arsenic and alkali and alkaline-earth metal salts do not suggest using these algae in agriculture. It is recommended to carry out arsenic speciation studies to assess whether the form in which it is found is bioavailable for plants and animals. The heavy metal contamination index was determined, which ranged between 0.318 and 3.279. Finally, for the first time in the country, the organic fraction of sargassum was analyzed.

Theoretical Evaluation of the Molecular Inclusion Process between Chlordecone and Cyclodextrins: A New Method for Mitigating the Basis Set Superposition Error in the Case of an Implicit Solvation Model.

The aim of this work is to describe the molecular inclusion of chlordecone with α-, ß-, and γ-cyclodextrin in aqueous solution using quantum mechanics. The guest-host complexes of chlordecone and cyclodextrins are modeled in aqueous solution using the multiple minima hypersurface methodology with a PM6-D3H4X semiempirical Hamiltonian, and the lowest energy minima obtained are reoptimized using the M06-2X density functional and the intermolecular interactions described using quantum theory of atoms in molecules (QTAIM). The studied complexes are classified according to the degree of inclusion, namely, total occlusion, partial occlusion, and external interaction. More stable complexes are obtained when γ-CD is used as the host molecule. The interactions characterized through QTAIM analysis are all of electrostatic nature, predominantly of dispersive type. In this work, a method based on the counterpoise correction is also discussed to mitigate the basis set superposition error in density functional theory calculations when using an implicit solvation model.

Photo-Fenton reaction at mildly acidic conditions: assessing the effect of bio-organic substances of different origin and characteristics through experimental design.

Urban-waste bio-organic substances (UW-BOS) have been shown to be capable of extending the photo-Fenton reaction to mildly acidic conditions. In this study, the effects of pH (3-7), UW-BOS, H2O2 and iron concentrations on the photo-Fenton process were systematically assessed using a Doehlert experimental design and response surface methodology for two UW-BOS (CVT230 and FORSUD). Solutions of the model antibiotic sulfadiazine (SDZ) were irradiated in a solar simulator equipped with a 550 W Xenon lamp. The results showed that for UW-BOS contents below 30 mg L-1, SDZ removal proceeds at pH 5 with similar rates for both CVT230 and FORSUD, regardless of Fe(III) concentration. For 50 mg L-1 of UW-BOS or higher, CVT230 performs better than FORSUD, even for low Fe(III) content (1-3 mg L-1). In contrast, half-life times of 35-40 min can only be achieved under mildly acidic conditions with FORSUD for iron concentrations higher than 10 mg L-1. The better performance of CVT230 can be associated with its high hydrophilic/hydrophobic ratio, low E2:E3, higher iron content and possibly higher yields of triplet reactive species generation upon solar irradiation. The most appropriate conditions for each UW-BOS studied are discussed for the first time, which are advantageous for possible engineered applications.

Theoretical study on the interactions between chlordecone hydrate and acidic surface groups of activated carbon under basic pH conditions.

A theoretical study of the influence of acidic surface groups (SG) of activated carbon (AC) on chlordecone hydrate (CLDh) adsorption is presented, in order to help understanding the adsorption process under basic pH conditions. A seven rings aromatic system (coronene) with a functional group in the edge was used as a simplified model of AC to evaluate the influence of SG in the course of adsorption from aqueous solution at basic pH conditions. Two SG were modeled in their deprotonated form: carboxyl and hydroxyl (COO- and O-), interacting with CLDh. In order to model the solvation process, all systems under study were calculated with up to three water molecules. Multiple Minima Hypersurface (MMH) methodology was employed to study the interactions of CLDh with SG on AC using PM7 semiempirical Hamiltonian, to explore the potential energy surfaces of the systems and evaluate their thermodynamic association energies. The re-optimization of representative structures obtained from MMH was done using M06-2X Density Functional Theory. The Quantum Theory of Atoms in Molecules (QTAIM) was used to characterize the interaction types. As result, the association of CLDh with acidic SG at basic pH conditions preferentially occurs between the two alcohol groups of CLDh with COO- and O- groups and by dispersive interactions of chlorine atoms of CLDh with the graphitic surface. On the other hand, the presence of covalent interactions between the negatively charged oxygen of SG and one hydrogen atom of CLDh alcohol groups (O-⋯HO interactions) without water molecules, was confirmed by QTAIM study. It can be concluded that the interactions of CLDh with acidic SG of AC under basic pH conditions confirms the physical mechanisms of adsorption process.

Optimization of ciprofloxacin degradation in wastewater by homogeneous sono-Fenton process at high frequency.

Emerging pollutants such as pharmaceuticals have been focusing international attention for a few decades. Ciprofloxacin (CIP) is a common drug that is widely found in hospital and wastewater treatment plants effluents, as well as in rivers. In this work, the feasibility of CIP degradation by ultrasound process at high frequency is discussed and sonolysis, sonolysis with hydrogen peroxide and sono-Fenton are evaluated. The amounts of hydrogen peroxide and ferrous ions (Fe2+) needed were optimized using response surface methodology. Best results were obtained with the sono-Fenton process resulting in a total pharmaceutical degradation within 15 min and a mineralization greater than 60% after 1 h. Optimal conditions were tested on a real matrix from a municipal wastewater treatment plant. Even if the degradation of the pollutants by sono-Fenton was hampered, the removal efficiency of both CIP and total organic carbon (TOC) is interesting as an increase in the biodegradability of the wastewater is found. These results show that sono-Fenton oxidation can be a promising pretreatment process for pharmaceutical-containing wastewaters.

Sonolysis and sono-Fenton oxidation for removal of ibuprofen in (waste)water.

Two sonochemical processes were compared for the removal of ibuprofen in different water matrixes (distilled water and effluent from wastewater treatment plant). The effect of various operating parameters, such as pH (2.6-8.0), ultrasound power density (25-100W/L), sonication frequency (12-862kHz), addition of radical promoters (H2O2 and Fenton's reagent) or scavengers (n-butanol and acetic acid), was evaluated. Sono-degradation of ibuprofen followed a first-order kinetic trend, whose rate constant increased with ultrasound density and frequency. For this hydrophobic and low volatile molecule, a free-radical mechanism at the bubble interface was established. Coupling ultrasound with Fenton reaction showed a positive synergy, especially in terms of mineralization yield, while adding H2O2 alone had no significant beneficial effect. Dedicated experiments proved this synergy to be due to the enhanced regeneration of ferrous ions by ultrasound. Efficacy of the sonolysis process was hampered in wastewater matrix, mainly as the consequence of higher pH increasing the molecule solubility. However, after convenient acidification, sono-Fenton oxidation results remained almost unchanged, indicating no significant radical scavenging effects from the effluent compounds.

Interacción de la 1-yodoclordecona como radiotrazador, con el grupo carboxilato en carbón activado / Interaction of 1-iodochlordecone, as radioactive tracer, with the carboxylate group on activated carbon

La clordecona es un compuesto organoclorado sintético, empleado como insecticida agrícola y clasificado como contaminante orgánico persistente de aguas y suelos por la Convención de Estocolmo. El uso de carbones activados es una metodología muy popular para la purificación de aguas contaminadas con contaminantes orgánicos persistentes. La clordecona marcada con yodo radiactivo (1-yodoclordecona) puede ser un radiotrazador adecuado para estudios de adsorción, de disponibilidad medioambiental y biodistribución de la clordecona. La selección del carbón activado más adecuado para la adsorción de clordecona requiere evaluar la eficiencia de una gran cantidad de los mismos, de manera empírica, lo que aumenta los costos de investigación. En el presente trabajo, un modelo simplificado de carbón activado con siete anillos aromáticos (coroneno) y un grupo funcional en el borde (carboxilato) se utilizó para evaluar in silico la influencia de este grupo superficial en la adsorción de la clordecona y la 1-yodoclordecona, bajo condiciones neutras de pH. Para ello se empleó la metodología de Hipersuperficie de Múltiples Mínimos con el hamiltoniano semiempírico PM7. Los resultados obtenidos muestran que para el carboxilato en medio neutro existen asociaciones significativas que sugieren quimisorción de la clordecona en el carbón activado. La 1-yodoclordecona se comporta de manera similar a la clordecona en su interacción con el carboxilato, por lo que constituye un buen candidato a radiotrazador para estudios experimentales.

Chlordecone is a synthetic organo chlorinated compound that has been used as pesticide. It has been identified and listed as persistent organic pollutant by the Stockholm Convention. The use of activated carbon filters is one of the most widely popular solutions for water decontamination. The chlordecone labeled with radioactive iodine (1-iodochordecone) is a potential radioactive tracer for studying adsorption, environmental availability and bio-distribution of chlordecone. The selection of the best suited activation carbon for this type of contaminants is mainly an empiric process, increasing the costs of research. A simplified activation carbon model, consisting of a seven ring graphene sheet with a functional group (carboxylate) was used to assess the interaction of chlordecone and 1-iodochlordecone with this surface group under neutral pH conditions over the adsorption process. The Multiple Minima Hypersurface methodology with the semiempirical Hamiltonian PM7 was used. The results indicate that for carboxylate, in neutral conditions, significant associations appear which suggest chemisorption in activated carbon. No significant differences were observed for the interactions of chlordecone and 1-iodochlordecone with carboxylate, making 1-iodochlordecone a good candidate as a radioactive tracer in medical research.

Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions.

Activated carbons (ACs) are widely used in the purification of drinking water without almost any knowledge about the adsorption mechanisms of the persistent organic pollutants. Chlordecone (CLD, Kepone) is an organochlorinated synthetic compound that has been used mainly as agricultural insecticide. CLD has been identified and listed as a persistent organic pollutant by the Stockholm Convention. The selection of the best suited AC for this type of contaminants is mainly an empirical and costly process. A theoretical study of the influence of AC surface groups (SGs) on CLD adsorption is done in order to help understanding the process. This may provide a first selection criteria for the preparation of AC with suitable surface properties. A model of AC consisting of a seven membered ring graphene sheet (coronene) with a functional group on the edge was used to evaluate the influence of the SGs over the adsorption. Multiple Minima Hypersurface methodology (MMH) coupled with PM7 semiempirical Hamiltonian was employed in order to study the interactions of the chlordecone with SGs (hydroxyl and carboxyl) at acidic and neutral pH and different hydration conditions. Selected structures were re-optimized using CAM-B3LYP to achieve a well-defined electron density to characterize the interactions by the Quantum Theory of Atoms in Molecules approach. The deprotonated form of surface carboxyl and hydroxyl groups of AC models show the strongest interactions, suggesting a chemical adsorption. An increase in carboxylic SGs content is proposed to enhance CLD adsorption onto AC at neutral pH conditions.

Ultrasonic degradation of sulfadiazine in aqueous solutions.

Advanced oxidation methods, like ultrasound (US), are a promising technology for the degradation of emerging pollutants in water matrices, such as sulfonamide antibiotics. Nevertheless, few authors report the degradation of sulfonamides by high-frequency US (>100 kHz), and limited information exist concerning the use of ultrasonic-driven processes in the case of sulfadiazine (SDZ). In this study, SDZ degradation was investigated with the aim to evaluate the influence of initial concentration, pH and US frequency, and power. Ultrasonic frequencies of 580, 862, and 1,142 kHz at different power values and SDZ initial concentrations of 25, 50, and 70 mg L(-1) were used. The results show that SDZ degradation followed pseudo first-order reaction kinetics with k values and percent removals decreasing for increasing solute initial concentration. Higher SDZ percent removals and removal rates were observed for the lowest operating frequency (580 kHz), higher dissipated power, and in slightly acidic solution (pH 5.5). Addition of the radical scavenger n-butanol confirmed that hydroxyl radical-mediated reactions at the interface of the cavitation bubbles are the prevailing degradation mechanism, which is directly related to the pKa-dependent speciation of SDZ molecules. Finally, addition of H2O2 had a detrimental effect on SDZ degradation, whereas the addition of the Fenton reagent showed a positive effect, revealing to be a promising alternative for the removal of sulfadiazine.