Remediation of petroleum contaminated saline water using value-added adsorbents derived from waste coconut fibres.

Oil spill from petrochemical industries into marine areas has resulted in severe environmental pollution. The use of natural sorbents to clean marine areas affected by petroleum contaminants is a promising approach to alleviate this problem. Therefore, this study aims at developing an technique that uses waste coconut fibres (Cocos nucifera L.) pre-treated with a "green" solvent, viz. protic ionic liquid (PIL) [2-HEA][Ac], for the remediation of oil in saline water. Conventional chemical pre-treatments (mercerisation/acetylation) and the innovative treatment (using PIL), chemical characterisation, Scanning Electron Microscope, Fourier-transform infrared spectroscopy, and oil sorption tests in hydrodynamic simulation on a laboratory scale were conducted. The fibres treated with PIL[2-HEA][Ac] possessed more pores and hydrophobic content than the mercerised/acetylated coconut fibres, indicating the efficiency of sorption. The average sorption of the PIL[2-HEA][Ac] fibre was 1.40 ± 0.06 g/g and that of the mercerised/acetylated fibre was 1.32 ± 0.12 g/g. Although the difference in sorption results is not significant, according to the Tukey test, fibre pre-treatment with PIL[2-HEA][Ac] is more advantageous than conventional treatments because it exhibits better average sorption results; furthermore, the synthesis procedure for PIL[2-HEA][Ac] is simple, reusable and non-toxic. Therefore, the use of these petroleum biosorbents is a technology with environmental benefits, such as the availability of the biosorbent in the form of biodegradable waste and treated with a "green" solvent, both of which can be reused. Thus, it adds value for its use in industries with a circular economy product; that are environment-friendly and economical.

On-Line Preconcentration and Simultaneous Determination of Cu and Mn in Water Samples Using a Minicolumn Packed with Sisal Fiber by MIP OES.

An on-line preconcentration system for the simultaneous determination of Copper (Cu) and manganese (Mn) in water samples was developed and coupled to a microwave-induced plasma optical emission spectrometer (MIP OES). The flow injection system was designed with a minicolumn packed with sisal fiber (Agave sisalana). A multivariate experimental design was performed to evaluate the influence of pH, preconcentration time, and eluent concentration. Optimal conditions for sample preparation were pH 5.5, preconcentration time was 90 s, and HCl 0.5 mol L-1 was the eluent. The main figures of merit were detection limits 3.7 and 9.0 µg L-1 for Cu and Mn, respectively. Precision was expressed as a relative standard deviation better than 10%. Accuracy was evaluated via spiked recovery assays with recoveries between 75-125%. The enrichment factor was 30 for both analytes. These results were adequate for water samples analysis for monitoring purposes. The preconcentration system was coupled and synchronized with the MIP OES nebulizer to allow simultaneous determination of Cu and Mn as a novel sample introduction strategy. The sampling rate was 20 samples/h. Sisal fiber resulted an economical biosorbent for trace element preconcentration without extra derivatization steps and with an awfully time of use without replacement complying with the principles of green analytical methods.

Ability of low contents of biosorbents to bind the food carcinogen aflatoxin B1in vitro.

In vitro experiments were conducted to evaluate the effectiveness of two new biosorbents (lettuce and field horsetail) in removing aflatoxin B1 (AFB1). Formosa firethorn was used as reference material. The adsorption of AFB1 (190 ng/mL) was investigated at two sorbent contents (0.5% and 0.1% w/v) and three pHs (2, 5, and 7). Batch experiments were performed at 40 °C for 2 h. Several methodologies were used to characterize the nature of the biosorbent-AFB1 interaction. In general, when using biosorbents at 0.5% w/v, AFB1 was well adsorbed by the three tested biomaterials (70 to 100%). Furthermore, with the lowest biosorbent content (0.1% w/v), significant AFB1 adsorption efficiencies were attained at pH 5 (33 to 50%). Nevertheless, at pH 7, lettuce showed the highest ability against AFB1 removal (95%). Further characterization of the AFB1-loaded biosorbents demonstrated that chemical and physical mechanisms were involved in the adsorption process.

Treatment of effluent containing thiamethoxam and efficiency evaluation of toxicity reduction.

The treatment of seeds using pesticides is a widely employed technique that generates effluents with high contamination potential. In the present study, our objective was to characterize and evaluate the toxicity of washing wastewater from corn seed treaters that contained the pesticide thiamethoxam. Effluents were treated by adsorption using several adsorbent materials, namely activated vegetable carbon, corn straw, and soybean hulls, different pH, and distinct mass concentrations for each material. The activated carbon promoted a greater reduction in the chemical oxygen demand (COD). In the coagulation-flocculation treatment, with ferric chloride (FeCl3) and poly-aluminum chloride (PAC), and using factorial planning with the concentration of FeCl3 and the sedimentation time as independent variables, the best COD removal occurred with 850 mg L-1 FeCl3 and 120 min sedimentation. The treatments C (coagulation), CACA (coagulation followed by adsorption with activated vegetable carbon), and CACS (coagulation followed by adsorption with corn straw) presented the most efficacious physicochemical parameter changes. The CACA treatment showed the best result for removing thiamethoxam. Nevertheless, raw and treated effluents showed high toxicity to the bioindicators Artemia salina L. (immobility/mortality test), Eisenia fetida (avoidance test), and Allium cepa L. (cytotoxicity test). The effluents also produced a mutagenic effect for A. cepa, due to the presence of chromosomal changes. The results demonstrated the risk that this effluent can cause to the environment. These data highlight the need to investigate new technologies to reduce the physicochemical parameters, the agrochemical levels, and, in particular, the final effluent toxicity.

Biosorción de plomo (II) en solución acuosa con biomasa de los cladodios de la tuna (Opuntia ficus indica) / Biosorption of lead (II) in aqueous solution with biomass of prickly pear cladodes (Opuntia ficus indica) / Biossorção de chumbo (II) em solução aquosa com biomassa de cladódios de pera espinhosa (Opuntia ficus indica)

Resumen Se investigó la remoción de plomo de soluciones acuosas por biomasa de los cladodios de la tuna (BCT), una especie abundante en la sierra peruana. Las propiedades físicas y químicas de la BCT se determinaron por técnicas de FTIR y SEM/ EDX. El análisis FTIR confirmó la presencia de grupos -OH, CO-C, C=O y -NH2, los cuales interactuarían con el metal. La micrografía SEM reveló que la morfología superficial de la BCT tiene porosidad adecuada para la biosorción. En un sistema discontinuo se obtuvo la más alta capacidad de biosorción (qe) con una relación masa BCT/volumen de 4 g/L, pH 4,5 y tiempo de contacto de 1 h. La biosorción siguió un modelo cinético de pseudo-segundo orden y el proceso de difusión intraparticular fue el factor principal de control de la velocidad. Los datos en el equilibrio fueron correlacionados con cinco modelos (Langmuir, Freundlich, Temkin, D-R y Redlich-Peterson) y se ajustaron mejor al modelo de Langmuir, lo que indica que el proceso se realiza en centros activos energéticamente homogéneos, el valor de qe máxima fue 50,25 mg/g. Los resultados obtenidos demuestran que la BCT puede ser usada como biosorbente eficiente para el tratamiento de aguas contaminadas con Pb (II).

Abstract The removal of lead from aqueous solutions by the biomass of prickly pear cladodes (BCT), a species found in abundance in the Sierra region in Peru, was investigated. The physical and chemical properties of BCT were determined by FTIR and SEM/EDX techniques. The FTIR analysis confirmed the presence of -OH, C-O-C, C=O and -NH2 groups which would interact with the metal. The SEM micrograph revealed that the surface morphology of the BCT shows adequate porosity for biosorption. In a discontinuous system, the highest biosorption capacity (qe) was obtained with a BCT mass/volume ratio of 4 g/L, pH 4.5 and 1 h of contact time. Biosorption followed a pseudo-second order kinetic model and the intraparticle diffusion process was the main factor controlling speed. Data at equilibrium were correlated using five models (Langmuir, Freundlich, Temkin, DR, and Redlich-Peterson) and were better fitted to the Langmuir model, which would indicate that the process is carried out in energetically homogeneous active centers, the value of qe maximum was 50.25 mg/g. The results obtained demonstrate that BCT can be used as an efficient biosorbent for the treatment of waters contaminated with Pb (II).

Resumo Investigou-se a remoção de chumbo de soluções aquosas pela biomassa de cladódios de pera espinhosa (BCT), espécie encontrada em abundância na região da Sierra, no Peru, e as propriedades físicas e químicas do BCT foram determinadas por técnicas de FTIR y SEM/EDX. A análise por FTIR confirma a presença dos grupos -OH, C-O-C, C=O e -NH2 que interagem com o metal; a micrografia SEM revela que a morfologia da superfície do BCT mostra porosidade adequada para biossorção. Em um sistema descontínuo, a maior capacidade de biossorção (qe) foi obtida com uma relação massa/volume de BCT de 4 g/L, pH 4,5 e tempo de contato 1 h. A biossorção seguiu um modelo cinético de pseudo-segunda ordem e o processo de difusão intrapartículas foi o principal fator de controle da velocidade. Os dados em equilíbrio foram correlacionados usando cinco modelos (Langmuir, Freundlich, Temkin, DR e Redlich-Peterson) e foram melhor ajustados ao modelo de Langmuir, o que indicaria que o processo é realizado em centros ativos energeticamente homogêneos, o valor de qe o máximo foi de 50,25 mg/g. Os resultados obtidos demonstram que o BCT pode ser usado como um biossorvente eficiente para o tratamento de águas contaminadas com Pb (II).

Utilization of Pacara Earpod tree (Enterolobium contortisilquum) and Ironwood (Caesalpinia leiostachya) seeds as low-cost biosorbents for removal of basic fuchsin.

Wastes from the Pacara Earpod tree (Enterolobium contortisilquum) and Ironwood (Caesalpinia leiostachya) seeds were studied as biosorbents for the removal of basic fuchsin from waters. Both biosorbents were prepared and characterized by different analytical methods. The characterization data showed that both materials were mainly composed of lignin, cellulose, and hemicellulose. Both biosorbents exhibited roughened surfaces and surface functional groups such as C-H, C=O, C=C, C-O, C-N, and OH bonds. Furthermore, the XRD pattern shows an amorphous phase with a wide peak from 10 to 30° due to the lignin. In terms of dosage and pH, the use of 1 g L-1 and 9.0, respectively, is recommended. The initial concentrations for the biosorption kinetics ranged from 50 to 500 mg L-1, where the Pacara ear and the Ironwood reached an adsorption capacity of 145.62 and 100.743 mg g-1 for the 500 mg L-1. The pseudo-second-order was found to be the proper model for describing biosorption of basic fuchsin onto Pacara Earpod tree and Ironwood, respectively. For the isotherm experiments, the maximum experimental biosorption capacity was found to be 166.858 and 110.317 mg g-1 for the Pacara Earpod and Ironwood for the initial concentration of 500 mg L-1 at 328 K. The Langmuir and the Tóth models were the best for representing the equilibrium curves for the basic fuchsin on the Pacara Earpod and the Ironwood, respectively. Maximum adsorption capacities of 177.084 mg g-1 and 136.526 mg g-1 were achieved for the Pacara Earpod tree and Ironwood, respectively. The biosorption process was spontaneous, endothermic, and favorable for both biosorbents. The biosorbents were also applied for coloration removal of simulated textile effluents, reaching 66% and 54% for the Pacara Earpod and Ironwood, respectively. For the final application, the materials were used in fixed-bed biosorption, with an initial concentration of 200 mg L-1, reaching breakthrough times of 710 and 415 min, leading to biosorption capacities of the column of 124.5 and 76.5 mg g-1, for the Pacara Earpod and Ironwood, respectively.

A Theoretical Study of the Adsorption Process of B-aflatoxins Using Pyracanthakoidzumii (Hayata) Rehder Biomasses.

Employing theoretical calculations with density functional theory (DFT) using the B3LYP/6-311++G(d,p) functional and basis set, the interaction of the aflatoxin B1 (AFB1) molecule and the functional groups present in the Pyracantha koidzumii biosorbent was investigated. Dissociation free energy and acidity equilibrium constant values were obtained theoretically both in solution (water) and gas phases. Additionally, the molecular electrostatic potential for the protonated molecules was calculated to verify the reactivity. Thus, methanol (hydroxyl group), methylammonium ion (amino group), acetate ion (carboxyl group), and acetone (carbonyl group), were used as representatives of the substrates present in the biomass; these references were considered using the corresponding protonated or unprotonated forms at a pH value of 5. The experimental infrared spectrophotometric data suggested the participation of these functional groups in the AFB1 biosorption process, indicating that the mechanism was dominated by electrostatic interactions between the charged functional groups and the positively charged AFB1 molecule. The theoretical determination indicated that the carboxylate ion provided the highest interaction energy with the AFB1 molecule. Consequently, an enriched biosorbent with compounds containing carboxyl groups could improve the yield of the AFB1 adsorption when using in vitro and in vivo trials.

Use of Salvinia sp on the adsorption of hexavalent chromium.

The remotion of hexavalent chromium in the form of chromate in aqueous solution was done using the aquatic plant Salvinia sp as biosorbent. The chemical modification of the Salvinia surface was performed by organosolv adapted method. The untreated Salvinia and the modified were characterized by infrared spectroscopy, Boehm titration, scanning electron microscopy, energy dispersive system, point of zero charge, surface area analysis, and porosity. Batch adsorption experiments were performed to observe the effects of pH, contact time, initial concentration, and temperature on the metal removal process. The characterization results show the chemistry modifically changed the modified Salvinia structure compared with untreated Salvinia. The adsorption test results showed the maximum adsorption capacity of 26.03 mg g-1. The kinetic equilibrium was reached in about 3 h, and the better temperature and pH were 298 K and 7, respectively. The adsorption and kinetic models were Freundlich and pseud-second order, respectively. This study showed the Salvinia sp after the chemical treatment can be used with biosorbent for hexavalent chromate in the form of chromate, being a natural material with low cost and plentiful in the environment.

Biosorption of Methylene Blue Dye Using Natural Biosorbents Made from Weeds.

The purpose of this work is to make use of vegetables that, although widely found in nature, there are few applications. The weeds used here, Cyanthilium cinereum (L.) H. Rob (CCLHR) and Paspalum maritimum (PMT) found in the Amazon region of Belém state of Pará-Brazil, contribute to the problem of water contamination by the removal of the methylene blue dye through the biosorption process, taking advantage of other materials for economic viability and processing. The influences of parameters such as, biosorbent dose, contact time, and initial concentration of dye were examined. The characterizations were realized using SEM to verify the morphology of the material and spectroscopy in the FTIR region. As for the adsorption mechanism, the physical adsorption mechanism prevailed. The time required for the system to reach equilibrium for both biosorbents was from 50 min, following a kinetics described by the pseudo-second order model. The adsorption isotherm data for PMT were better adjusted to the Langmuir model and the biosorption capacity (qmax) value was (56.1798 mg/g). CCLHR was better adjusted to the Freundlich model and its maximum biosorption capacity was 76.3359 mg/g. Thus, these weed species are promising for the biosorption of methylene blue dye in effluents.

Assessing the Aflatoxin B1 Adsorption Capacity between Biosorbents Using an In Vitro Multicompartmental Model Simulating the Dynamic Conditions in the Gastrointestinal Tract of Poultry.

Experiments were carried out to evaluate the effectiveness of three different biosorbents (banana peel, Pyracantha leaves, and Aloe powder) in removing aflatoxin B1 (AFB1). A noncommercial mycotoxin binder (zeolite) was used as a reference material. A laboratory model that simulated the in vivo conditions of the poultry gastrointestinal tract was utilized to prove the removal efficiency of the biosorbents when added to AFB1-contaminated diet (100 µg/kg). The concentration of AFB1 was determined using antibody-based immunoaffinity column and spectrofluorometry methodologies. Z potential (ζ), point of zero charge (pHpzc), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR), and UV-Vis diffuse reflectance spectroscopy (DRS) techniques were used to further characterize the biosorbents. The addition of the biosorbents (1.5%, w/w) to the diet significantly reduced the bioavailability of AFB1 in the intestinal section. The highest aflatoxin adsorption values were 69% and 70% using Aloe powder and zeolite, respectively. A moderate biosorption uptake of 46% was achieved using Pyracantha leaves. The biomaterial with the lowest removal capacity was banana peel (28%). In conclusion, Aloe powder could be used as an alternative to conventional systems for AFB1 removal.