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1.
Chemosphere ; 281: 130706, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34020190

RESUMO

Chitosan was fabricated via gelation method using CaBr2.xH2O/methanol solution and was studied as a potential adsorbent (MCh) in adsorbing anionic synthetic dyes like Bromophenol blue (BB), Direct blue 6 (DB) and Congo red (CR) from single (one dye species at a time) and multi (having two dyes; binary and all three dyes; tertiary) adsorptive systems. Physico-chemical modifications of MCh surface prior and post modification and dye adsorption were evaluated using scanning electron microscopy, Energy-dispersive X-ray spectroscopy, powder X-ray diffraction analysis, surface area analysis and Fourier-transformed infrared spectroscopy. Influential parameters influencing the adsorption process viz. initial pH of dye solution, MCh dosage, adsorption temperature and initial concentration of dye species were optimised. Adsorptive studies involving single adsorptive setups verified formation of sorbate's (dye species) monolayer over the sorbent's (MCh) surface via chemisorption; as established by Langmuir isotherm and pseudo-second order kinetics model analysis. Theoretical maximum adsorption capacities of MCh for BB, DB and CR was found to be 81.301 mg/g, 163.934 mg/g and 75.758 mg/g, respectively. Meanwhile, for all multi-adsorptive systems, competitive Langmuir isotherm model verified antagonistic behaviour of an individual dye over other dye adsorption over MCh surface in their respective adsorptive systems. Thermodynamics of the sorbate-sorbent interaction was exothermic, spontaneous, with elevated degree of disorderedness; concluding the interaction as thermodynamically favourable. Co-existing metal cations and anionic salts had minimal effect on MCh's adsorption efficiency. Phytotoxicity assay via germination of Vigna mungo seeds verified the efficacy of the adsorbent in eliminating the dye species from single and multi-adsorptive systems.


Assuntos
Quitosana , Poluentes Químicos da Água , Adsorção , Corantes , Concentração de Íons de Hidrogênio , Cinética , Porosidade , Espectroscopia de Infravermelho com Transformada de Fourier , Termodinâmica , Poluentes Químicos da Água/análise
2.
J Environ Manage ; 278(Pt 2): 111523, 2021 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-33161298

RESUMO

A commercial activated carbon (AC), obtained from peanut shells, was characterized and tested as adsorbent for the removal of the pharmaceutical products caffeine (CF) and diclofenac (DIC), which were used as model emerging contaminants. Nitrogen adsorption, XRD, SEM, FT-IR spectroscopy, and chemical analyses were typical of ACs, and Boehm titrations, calculations of surface sites distributions and zeta potential measurements indicated that reactions of deprotonable oxygenated groups at the AC surface lead to an isoelectric point of 3.2. A theoretical equation derived from the Langmuir isotherm is proposed to explain the adsorption percentage or adsorbed fraction (fads) as a function of the adsorbent dose (D, adsorbent "concentration"). Good fittings of the fads vs. D curves and the normal adsorption isotherms were obtained with the same Langmuir parameters. An important and practical application of this new equation is to permit a straightforward calculation of the solid dose needed to achieve a required adsorption percentage. With the aim of describing the adsorption processes of CF and DIC and their competition for surface sites under an ample range of concentrations, the adsorption of the emerging contaminants was investigated in single adsorbate experiments and with binary mixtures, and the competitive Langmuir model was applied. CF adsorption was high and independent of pH, whereas DIC adsorption was high between pH 4 and 6 and showed a continuous decrease from pH 6 to 10.5. The use of the competitive Langmuir isotherm for binary mixtures indicated that there was no pure competition between CF and DIC for surface sites. Instead, there was influenced competition, meaning that the presence of one substance at the surface modified the adsorption parameters of the other, either through lateral interaction forces or by changing the molecular orientation at the surface. In both cases, one substance favored the adsorption of the other, compared to pure competition.


Assuntos
Carvão Vegetal , Poluentes Químicos da Água , Adsorção , Cafeína , Diclofenaco , Concentração de Íons de Hidrogênio , Cinética , Soluções , Espectroscopia de Infravermelho com Transformada de Fourier , Poluentes Químicos da Água/análise
3.
Environ Res ; 188: 109825, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32798946

RESUMO

Adsorptive removal of emerging contaminants like antibiotics from aqueous systems having one or more antibiotics using acid activated carbon have rarely been studied and reported. Current study deals with the adsorptive removal of individual antibiotic species i.e. Ciprofloxacin (CIP) and Amoxicillin (AMX) from single (CIP and AMX) and binary (CIP + AMX) adsorption systems using acid activated carbon prepared from Prosopis juliflora wood (PPJ). Binary adsorption system involved the synergistic and antagonistic influence of one antibiotic over the adsorption of other antibiotic. Physico-chemical alterations of PPJ surface due to acid activation and after adsorption were characterized for any surface modification. Parameters influencing the efficient adsorption of CIP and AMX viz. Initial pH of antibiotic solution, dosage of PPJ, sorbent-sorbate incubation temperature and initial concentration of antibiotic species were optimized. Sorbate-sorbent interaction studies for single system revealed sorbate's monolayer formation over adsorbent's surface and the involvement of chemisorption as verified by Langmuir isotherm model and pseudo-second order model respectively. For single system, Langmuir maximum adsorption capacity of PPJ was 250 mg/g for CIP and 714.29 mg/g for AMX. Meanwhile, competitive Langmuir model was used to investigate adsorption capacity of individual antibiotics in binary system i.e. 370.37 mg/g for CIP and 482.14 mg/g for AMX thus verifying CIP has antagonistic effect on AMX adsorption and AMX has synergistic effect on CIP adsorption on PPJ surface. Recyclability studies verified the PPJ can be used up to 4 cycles and co-existing cationic and anionic salts had minimal effect on the adsorption of antibiotics over PPJ surface. Conclusively PPJ proved efficient in eliminating emerging contaminants like that of antibiotics and thus it can be exploited for other grades of pollutants.


Assuntos
Prosopis , Poluentes Químicos da Água , Adsorção , Amoxicilina , Carvão Vegetal , Ciprofloxacina , Concentração de Íons de Hidrogênio , Cinética , Poluentes Químicos da Água/análise
4.
Environ Pollut ; 266(Pt 2): 115102, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32650200

RESUMO

Current study deals with the surface modification of acid activated carbon (prepared from Pongamia pinnata shells) with Cetyltrimethylammonium bromide (CTAB) and its role as an adsorbent in eliminating anionic azo dyes viz. Congo red (CR) and Direct blue 6 (DB) from single and binary adsorptive systems. Binary adsorptive system involved the synergistic and antagonistic influence of one dye over the adsorption of other dye. Physico-chemical alterations due to surfactant modification and post adsorption were studied using atomic force microscopy (AFM), Zeta Potential, scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), surface area analysis and Fourier-transformed infrared spectroscopy (FTIR). Process parameters influencing efficient adsorption of CR and DB species viz. initial pH of dye solution, adsorbent dosage, incubation temperature and initial concentration of dye species were optimised. Sorbate-sorbent interaction studies for single adsorptive system revealed sorbate's monolayer formation over adsorbent's surface and the involvement of chemisorption, as verified by Langmuir isotherm model and pseudo-second order model, respectively. Langmuir maximum adsorption capacity of the adsorbent was 555.56 mg/g for CR and 625.00 mg/g for DB. Meanwhile, for binary adsorptive system, competitive Langmuir model verified both CR and DB had antagonistic/competitive effect over each other's adsorption. Thermodynamic analysis revealed the adsorptive process as exothermic, spontaneous and thermodynamically favourable with an elevated degree of dis-orderedness. Co-existing cations and anions has nominal effect on the adsorption capacity of dyes. Recyclability studies verified a modest efficiency of 62.52% for CR and 50.47% for DB species after the end of 4th adsorption-desorption cycle; thus affirming its recyclability potential. Phytotoxic assay affirmed the effectivity of the adsorbent in adsorbing dye species from aqueous solutions using Vigna mungo seeds as the model.


Assuntos
Carvão Vegetal , Poluentes Químicos da Água/análise , Adsorção , Ânions , Compostos Azo , Corantes , Concentração de Íons de Hidrogênio , Cinética , Termodinâmica
5.
Plants (Basel) ; 8(7)2019 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-31269757

RESUMO

The global agricultural industry requires improved efficacy of sprays being applied to weeds and crops to increase financial returns and reduce environmental impact. Enhancing foliar penetration is one way to improve efficacy. Within the plant leaf, the cuticle is the most significant barrier to agrochemical diffusion. It has been noted that a comprehensive set of mechanisms for ionic active ingredient (AI) penetration through plant leaves with surfactants is not well defined, and oils that enhance penetration have been given little attention. The importance of a mechanistic mathematical model has been noted previously in the literature. Two mechanistic mathematical models have been previously developed by the authors, focusing on plant cuticle penetration of calcium chloride through tomato fruit cuticles. The models included ion binding and evaporation with hygroscopic water absorption, along with the ability to vary the AI concentration and type, relative humidity, and plant species. Here, we further develop these models to include lipophilic adjuvant effects, as well as the adsorption and desorption, of compounds on the cuticle surface with a novel Adaptive Competitive Langmuir model. These modifications to a penetration model provide a novel addition to the literature. We validate our theoretical model results against appropriate experimental data, discuss key sensitivities, and relate theoretical predictions to physical mechanisms. The results indicate the addition of the desorption mechanism may be one way to predict increased penetration at late times, and the sensitivity of model parameters compares well to those present in the literature.

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