Adsorption of Petroleum Monoaromatics from Aqueous Solutions Using Granulated Surface Modified Natural Nanozeolites: Systematic Study of Equilibrium Isotherms

Petroleum monoaromatics including benzene, toluene, ethylbenzene, and xylenes (BTEX) are among the notorious volatile organic compounds that contaminate water and soil. In this study, a surfactant- modified natural zeolite and its relevant granulated nanozeolites were evaluated as potential adsorbents for removal of petroleum monoaromatics from aqueous solutions. All experiments performed in batch mode at constant temperature of 20°C and pH of 6.8 for 48 h. The results revealed that the amount of BTEX uptake on granulated zeolites nanoparticles were remarkably higher than the parent micron size natural zeolite (in the order of four times). The isotherms data were analyzed using five models namely, Langmuir, Fruendlich, Elovich, Temkin, and Dubinin?CRadushkevich models. It was concluded that the Langmuir model fits the experimental data. The measured adsorption capacities were 3.89 and 4.08 mg of monoaromatics per gram of hexadecyltrimethylammonium-chloride and n-cetylpyridinium bromide (CPB)-modified granulated nanozeolite, respectively. Considering the type of surfactant, adsorbents modified with CPB showed greater tendency for the adsorption of the adsorbates.     

Co(II) Adsorption in Aqueous Media by a Synthetic Fe–Mn Binary Oxide Adsorbent

Co(II) adsorption on high-purity amorphous Fe?CMn binary oxide adsorbent was investigated. The Co(II) adsorption behavior of this synthetic material was studied and discussed as a function of contact time, pH and initial concentration. The Langmuir and Freundlich isotherm models were applied to fit the Co(II) adsorption data on Fe?CMn binary oxide with mesoporous particles of irregular surface morphology and a specific surface area of 201.8?m²?g^?1 with a maximum capacity of 32.25?mg?g^?1. Various kinetic models applied to the adsorption rate data of the Co(II) ion were evaluated. The results show that the pseudo-second order and the intra-particle mass transfer diffusion models correlated best with the experimental rate data. The adsorption activation energy was found to be 9.07?kJ?mol^?1 indicating that it corresponds to a physical adsorption. The evaluated thermodynamics parameters of the adsorption values indicated the endothermic and spontaneous nature of the adsorption. The results obtained confirmed that Fe?CMn binary oxide had the potential to be utilized as a low-cost and relatively effective adsorbent for Co(II) removal from wastewater.     

A Novel Pretreatment Method of Lignocellulosic Material as Adsorbent and Kinetic Study of Dye Waste Adsorption

Sulphuric acid-modified bagasse has been used as low-cost adsorbent for the removal of methylene blue (MB) dye from aqueous solution. In order to remove organic compounds that contribute to chemical oxygen demand (COD), pretreatment with thorough washing of adsorbent using boiling distilled water was performed instead of conventional washing using distilled water at room temperature only. This has resulted in the highest efficiency of color removal of 99.45% and COD reduction of 99.36% for MB dye solution at pH 9. Effects of initial pH, dye concentration, adsorbent dosage, temperature, and contact time have been studied. The adsorption of MB dye was pH dependent. Langmuir and Freundlich isotherm models were tested on the adsorption data. The kinetic experimental data were analyzed using pseudo-first order, pseudo-second order, and the intraparticle diffusion model in order to examine the adsorption mechanisms. The adsorption process followed the Langmuir isotherm as well as the Freundlich isotherm and pseudo-second-order kinetic model. The process was found to be endothermic in nature.     

Adsorption of Congo Red on Various Activated Carbons. A Comparative Study

Studies on the removal of Congo Red (CR) by adsorption on variousactivated carbons [commercial activated carbon (CAC) and indigenously prepared activated carbons(IPACs) from raw materialslike bamboo dust, coconut shell, groundnut shell, rice husk, and straw] have beencarried out with an aim to obtain information on treating effluents from dye/textile industries. The effect of various experimental parameters has been investigated by following batchadsorption technique at 30 ± 1 °C. The percentage removal of dye increased with the decrease in initial concentration, initial pH of the dye solution and particle size of IPACs and increase in contact time and dose of adsorbent. Adsorption data were modelled with the Freundlich and Langmuir adsorption isotherms and first order kinetic equations such asNatarajan and Khalaf, Lagergren, Bhattacharya and Venkbachar equations and intra-particle diffusion model and the models werefound to be applicable. The kinetics of adsorption is observed tobe first order with intra-particle diffusion as one of the rate determining steps. Removal of dye using IPACs is found to be favourable and hence, IPACs could be considered as alternatives to CAC for the treatment of textile effluents, especially for theremoval of dye(s).     

Adsorption kinetics of 17α-ethinyl estradiol and bisphenol A on carbon nanomaterials. I. Several concerns regarding pseudo-first order and pseudo-second order models

Purpose  

Pseudo-first order (PFOM) and pseudo-second order kinetic (PSOM) models are widely used in describing the adsorption kinetics in soils/sediments. This study intends to apply these models to describe the adsorption kinetics of organic contaminants on carbon nanomaterials. However, we noticed several improper applications of these two models.     

Assessment of the Hyperaccumulating Lead Capacity of Salvinia minima Using Bioadsorption and Intracellular Accumulation Factors

Salvinia minima has been reported as a cadmium and lead hyperaccumulator being the adsorption and intracellular accumulation the main uptake mechanisms. However, its physicochemical properties, the effect of metal concentration and the presence of organic and inorganic compounds on its hyperaccumulating capacity are still unknown. Furthermore, the specific adsorption and accumulation mechanisms occurring in the plant are not clear yet. Thus, based on a compartmentalization analysis, a bioadsorption (BAF) and an intracellular accumulation factor (IAF) were calculated in order to differentiate and quantify these two mechanisms. The use of kinetic models allowed predicting the specific type of uptake mechanisms involved. Healthy plants were exposed to five lead concentrations ranging from 0.80?±?0.0 to 28.40?±?0.22 mg Pb²⁺l^?1 in batch systems. A synthetic wastewater, amended with propionic acid and magnesium sulfate, and deionized water were used as media. The BAF and IAF contributed to gain an in-depth insight into the hyperaccumulating lead capacity of S. minima. It is clear that such capacity is mainly due to adsorption (BAF 780–1980) most likely due to its exceptional physico-chemical characteristics such as a very high surface area (264 m² g^?1) and a high content of carboxylic groups (0.95 mmol H⁺g^?1 dw). Chemisorption was predicted as the responsible mechanism according to the pseudo-second order adsorption model. Surprisingly, the ability of S. minima to accumulate the metal into the cells (IAF 57–1007) was not inhibited at concentrations as high as 28.40±0.22 mg Pb²⁺l^?1.     

Comparison of Cadmium Ion Adsorption on Various ACTIVATED CARBONS

Studies on the removal of cadmium(II) ions from aqueous solutions by adsorption on various activated carbons [commercial activated carbon (CAC) and chemically prepared activated carbons (CPACs) from raw materials such as straw, saw dust and datesnut] have been carried out with an aim to obtain information on treating effluents containing Cd(II) ions. Factors influencing the adsorption of Cd(II) ions from aqueous solution by ACs have been investigated by following a batch adsorption technique at 30± 1 ^°C. The percentage removal increased with decrease in initial concentration and particle size of CPACs and an increase in contact time, dose and initial pH of the solution. Adsorption process was inhibited by the added electrolytes. The adsorption data were fitted with the Langmuir, Dubinim–Radushkevich and Freundlich isotherms and first-order kinetic equations viz., first-order, Lagergren and Bhattacharya–Venkobachar equations and intra-particle diffusion model. The kinetics of adsorption is first order with intra-particle diffusion as one of the rate determining steps. Thermodynamic parameters were obtained from equilibrium constants measured at 30, 35 and 40 ^°C (Error = ± 1 ^°C). Results of the studies on adsorption of Cd²⁺ ions from simulated wastewater were compared with that of CAC and Tulsion CXO-9(H), a commercial ion exchange resin/cationic resin (CR). Straw carbon showed the maximum adsorption capacity towards Cd²⁺ ions and a high value of rate constant of adsorption. Straw carbon is an alternative low-cost adsorbent to CAC.     

Lime and Gypsum as Source Measures to Decrease Phosphorus Loss from Soils to Water

The adsorption of pentachlorophenol (PCP) from aqueous solutions using pristine multi-walled carbon nanotubes (MWCNTs) was studied kinetically and thermodynamically. The results showed that MWCNTs are good adsorbents for the elimination of PCP from aqueous solutions in a very short time compared with activated charcoal. The kinetics study showed that the adsorption of PCP is mainly due to the diffusion of PCP from the aqueous phase to the solid phase beside intra-particle diffusion. This intra-particle diffusion was more significant for activated charcoal compared with MWCNTs. The equilibrium adsorption of PCP at different temperatures was studied, and the adsorption isotherms were well described using different adsorption models. Thermodynamics study showed that the adsorption process was product-favored (enhanced) as the temperature decreased.     

Removal of Ammonia from Aqueous Solutions,Ground Water,and Wastewater Using Mechanically Activated Clinoptilolite and Synthetic Zeolite-A: Kinetic and Equilibrium Studies

Natural zeolite clinoptilolite and synthetic zeolite Na-A were characterized using XRD and SEM to be used as adsorbents for ammonia from aqueous solutions, ground water, and sewage water. Clinoptilolite was mechanically activated for 2, 4, 6, and 8 h to study the effect of activation in enhancing the adsorption capacity. The adsorption by activated natural zeolite and synthetic zeolite is high pH dependent and achieve the best values at pH?=?7. The adsorption capacity of activated natural zeolite increases with increasing the activation from 2 to 8 h achieving removal percentage close to that obtained using synthetic zeolite. The equilibrium was obtained after 60 min for synthetic zeolite and all the activated natural zeolite (except 2-h-activated product, the equilibrium was achieved after 30 min). The kinetic studies reflected the high fitness of the adsorption results of activated natural zeolite products and synthetic zeolite with pseudo-second-order model rather than the other kinetic models. The obtained isotherms reflected the formation of S-type isotherm curve for the adsorption using mechanically activated clinoptilolite and L-type curve for the uptake using synthetic zeolite. The results represented well with Langmuir model followed by Temkin and Freundlich model for adsorption using synthetic zeolite. The uptake using mechanically activated clinoptilolite can be represented by Temkin model rather than both Langmuir and Freundlich models. Thermodynamic parameters indicate spontaneous endothermic adsorption of ammonia using all the zeolitic products under investigation. Finally, the mechanically activated natural zeolite and synthetic zeolite exhibit high efficiency in the removal of ammonia and other water pollutants from ground water and sewage water.     

Removal of Pb2+ Ions from Water by Poly(Acrylamide-co-Sodium Methacrylate) Hydrogels

The application of poly(acrylamide-co-sodium methacrylate) (AAm/SMA) hydrogel for the removal of Pb²⁺ ions from aqueous solutions has been investigated using batch adsorption technique. The extent of adsorption was investigated as a function of pH, adsorbent dose, and temperature. The Fourier transform infrared (FTIR) spectra showed that ?CNH₂ and ?CCOOH groups are involved in Pb²⁺ ion adsorption. The obtained results were analyzed by pseudo-first-order, pseudo-second?Corder, and intraparticle diffusion models using both linear and nonlinear methods. It was found that the Pb²⁺ ion adsorption followed pseudo-first-order kinetics. Nonlinear regression analysis of six isotherms, Langmuir, Freundlich, Redlich-Peterson, Toth, Dubinin-Radushkevich, and Sips, have been applied to the sorption data, while the best interpretation was given by Redlich-Peterson. Based on the separation factor, R _L, the Pb²⁺ ion adsorption is favorable, while the negative values of ?G indicates that the Pb²⁺ ion adsorption on the investigated hydrogel is spontaneous.     

Sorption Behavior of 4-Chlorophenol from Aqueous Solutions By a Surfactant-modified Mexican Zeolitic Rock in Batch and Fixed Bed Systems

The removal of 4-chlorophenol from aqueous solutions by both a Mexican clinoptilolite-heulandite zeolitic rock and the modified zeolitic material with the surfactant hexadecyltrimethylammonium bromide (HDTMABr), using batch and packed-bed (column) configurations, was investigated. The unmodified zeolitic rock did not show any adsorption of 4-chlorophenol. The effects of pH, contact time and concentration of 4-chlorophenol on the adsorption process by the surfactant modified material were examined. The sorption of 4-chlorophenol was not affected by the pH range from 4 to 9.5. 4-chlorophenol retention reached equilibrium in about 18 h and the rate of 4-chorophenol adsorption by the modified material was faster in the first 10 h than later. The experimental data were treated with the models: pseudo-first order, pseudo-second order, fractional power and Elovich models. Although, the last three gave correlation coefficients higher than 0.96, the pseudo-second order model was the best to describe the reaction rate. The experimental data follow a linear isotherm which is characteristic for sorption of organic solutes by the partition mechanism. The Bed Depth-Service Time Model was applied to the sorption results in order to model the column operation. The results showed that the surfactant modified zeolitic rock could be considered as a potential adsorbent for 4-chlorophenol removal from aqueous solutions.     

Copper Ions Adsorption from Aqueous Medium Using the Biosorbent Sugarcane Bagasse In Natura and Chemically Modified

This study evaluated the copper ion adsorption capacity of sugarcane bagasse in natura and chemically modified with citric acid and sodium hydroxide. Adsorption analyses in batch system were carried out in function of contact time with the adsorbent and adsorbate concentration. Flame atomic absorption spectrometry was used to determine the copper concentrations. Adsorption experimental data were fitted to Langmuir and Freundlich linear models, and the maximum adsorption capacity was estimated for copper ions in function of modifications. The chemical modifications were confirmed at 1,730 cm^?1 peak in infrared spectra, referring to the carboxylate groups. The required time for the adsorption to reach equilibrium was 24 h and the kinetics follows the behavior described by the pseudo-second order equation. Besides, a significant improvement of the copper adsorption has been observed after the bagasse treatment, where the maximum adsorption capacity was 31.53 mg g^?1 for copper using modified bagasse with nitric acid according to Langmuir isotherm linear model. The high uptake of copper ions from aqueous medium verified by chemically modified sugarcane bagasse makes this material an attractive alternative for effluent treatment and avoids environmental contamination.     

Environmental fate of petroleum hydrocarbons in soil: Review of multiphase transport, mass transfer, and natural attenuation processes

The increasing use of petroleum-derived fuels over the last few decades has subsequently augmented the risk of spills in the environment. Soil pollution with petroleum hydrocarbons (principally caused by leaks in pipelines and underground storage tanks) is one of the major sources of soil degradation. Once in soil, fuel hydrocarbons suffer from a wide variety of multiphase processes including transport (advection, diffusion, and dispersion) among and within phases (aqueous and non-aqueous liquid, gas, and soil solids), mass transfer among phases (volatilization, sorption, and solution), and other natural attenuation processes, such as biodegradation and plant uptake and metabolism. This review identifies and describes the major processes occurring in soil that have a significant influence on the environmental fate of petroleum hydrocarbons. The definition of the processes involved in pollutant migration and distribution in soil and the formulation of adequate equations using accurate parameters (e.g., diffusion coefficients, velocity of advective flows, and mass transfer coefficients) will allow prediction of the final fate of soil pollutants. In addition to transport and mass transfer processes, which are more widely studied, the incorporation of attenuation mechanisms driven by microorganisms and plants is essential to predict the final concentration of the pollutants in the whole multiphase scenario. This work underlines the importance of the determination of accurate parameters through the performance of laboratory and/or field-scale experiments to develop precise pollutant migration models.     

Use of Biopolymeric Membranes for Adsorption of Paraquat Herbicide from Water

The use of membranes prepared with alginate and chitosan to adsorb paraquat aqueous solution was evaluated as a potential alternative technique for remediation of contaminated water. Production of bilayer membranes was based on the electrostatic interaction between alginate (a polyanion) and chitosan (a polycation). Herbicide adsorption experiments were performed using three different membranes, consisting of pure alginate, pure chitosan, and a chitosan/alginate bilayer. Adsorption was characterized using the Langmuir and Freundlich isotherm models, as well as by applying pseudo-first order and pseudo-second order kinetic models. The potential use of the membranes in environmental applications was evaluated using water collected from the Sorocabinha River in S?o Paulo State, Brazil. The results indicated that interactions between the membranes and the herbicide were strongly related to the type of biopolymer and the physical?Cchemical characteristics of the herbicide.     

Removal of Remazol Brilliant Blue Dye from Dye-Contaminated Water by Adsorption Using Red Mud: Equilibrium, Kinetic, and Thermodynamic Studies

Utilization of industrial solid wastes for the treatment of wastewater from another industry could help environmental pollution abatement, in solving both solid waste disposal as well as liquid waste problems. Red mud (RM) is a waste product in the production of alumina and it poses serious pollution hazard. The present paper focuses on the possibility of utilization of RM as an adsorbent for removal of Remazol Brilliant Blue dye (RBB), a reactive dye from dye-contaminated water. Adsorption of RBB, from dye-contaminated water was studied by adsorption on powdered sulfuric acid-treated RM. The effect of initial dye concentration, contact time, initial pH, and adsorbent dosage were studied. Langmuir isotherm model has been found to represent the equilibrium data for RBB?CRM adsorption system better than Freundlich model. The adsorption capacity of RM was found to be 27.8?mg dye/g of adsorbent at 40?°C. Thermodynamic analysis showed that adsorption of RBB on acid-treated RM is an endothermic reaction with ?H ⁰ of 28.38?kJ/mol. The adsorption kinetics is represented by second-order kinetic model and the kinetic constant was estimated to be 0.0105?±?0.005?g/mg?min. Validity of intra-particle diffusion kinetic model suggested that among the mass transfer processes during the dye adsorption process, pore diffusion is the controlling step and not the film diffusion. The process can serve dual purposes of utilization of an industrial solid waste and the treatment of liquid waste.     

Effect of reduced iron on the degradation of chlorinated hydrocarbons in contaminated soil and ground water: A review of publications

Chlorinated hydrocarbons are among the most hazardous organic pollutants. The traditional remediation technologies, i.e., pumping of contaminated soil- and groundwater and its purification appear to be costly and not very efficient as applied to these pollutants. In the last years, a cheaper method of destroying chlorine-replaced hydrocarbons has been used based on the construction of an artificial permeable barrier, where the process develops with the participation of in situ bacteria activated by zerovalent iron. The forced significant decrease in the redox potential (Eh) down to ?750 mV provides the concentration of electrons necessary for the reduction of chlorinated hydrocarbons. A rise in the pH drastically accelerates the dechlorination process. In addition to chlorine-organic compounds, ground water is often contaminated with heavy metals. The influence of the latter on the effect of zerovalent iron may be different: both accelerating its degradation (Cu) and inhibiting it (Cr). Most of the products of zerovalent iron corrosion, i.e., green rust, magnetite, ferrihydrite, hematite, and goethite, weaken the efficiency of the Fe⁰ barrier by mitigating the dechlorination and complicating the water filtration. However, pyrrhotite FeS, on the contrary, accelerates the dechlorination of chlorine hydrocarbons.     

The impact of extraction methodologies on the toxicity of sediments in the zebrafish (Danio rerio) embryo test

Purpose

Traditionally, methods for sediment extractions are characterised using chemical analyses. However, in order to evaluate sediment extracts with regard to biological effects and, thus, bioaccessibility, extraction methods have to be compared to effect data obtained from experiments with in situ exposure scenarios, i.e., sediment contact tests. This study compares four extraction methods and sediment contact test data from a previous project with respect to predictive power in the fish embryo test with zebrafish (Danio rerio).

Materials and methods

A natural and an artificial sediment spiked with a mixture of six organic pollutants (2,4-dinitrophenol, diuron, fluoranthene, nonylphenol, parathion and pentachlorophenol) were extracted using (a) membrane dialysis extraction (MDE), (b) a Soxhlet procedure, (c) hydroxypropyl-??-cyclodextrin (HPCD) or (d) Tenax^®-TA. Whereas the former two are regarded being exhaustive with respect to non-covalently bound contaminants, the latter two are considered to predict bioaccessibility. Resulting extracts were tested in the fish embryo assay with D. rerio for embryotoxic and teratogenic potential.

Results and discussion

Mortalities caused by organic extracts from Soxhlet extraction and MDE were high. However, HPCD extracts turned out to be at least as effective as extracts obtained with these two methods. One possible reason might be short ageing time of the spiked sediments. Only Tenax^®-TA extracts gave results comparable to the sediment contact assay for natural sediment, but revealed low reproducibility. Significant differences between natural and artificial sediment were found for extracts obtained with techniques using native (i.e., non-freeze-dried) sediments, i.e., HPCD and Tenax^®-TA. In contrast, MDE and Soxhlet extracts used freeze-dried sediment and did not differentiate between natural and artificial sediment. Therefore, freeze-drying has likely altered and equalised sediment properties that influence accessibility, such as composition of bacterial communities and organic matter quality.

Conclusions

Four extraction methods were successfully characterised with respect to their stringency and predictiveness for bioaccessibility. MDE was confirmed as an alternative to Soxhlet extraction. High mortalities induced by HPCD extracts underline the need to include ageing into consideration when assessing sediments. Although Tenax^®-TA may basically be used to predict bioaccessibility in the fish embryo test, the high variability observed warrants further investigation of the relation between effect and extractability. Apparently, freeze-drying can severely affect sediment properties, potentially eliminating individual properties of natural sediments.     

Kinetic and Removal Mechanisms of Ethylbenzene from Contaminated Solutions by Chitin and Chitosan

In this study, the efficiency of chitin and chitosan toward the removal of ethylbenzene from aqueous solutions was investigated. Batch adsorption experiments of ethylbenzene-contaminated waters (5?C200 mg/L) were carried out to evaluate the removal performance. Ethylbenzene uptake was determined from the changes in concentration, as the residual concentration was measured by gas chromatography with mass spectroscopy. The results indicated that the adsorption of ethylbenzene by chitin and chitosan were in agreement with the Langmuir isotherm, for two parameters model, and Redlich?CPeterson isotherm, for three parameters model. A maximum removal percentage of 65% of ethylbenzene can be achieved using chitosan as adsorbent material. The adsorption capacity of ethylbenzene followed the order chitosan?>?chitin. The pseudo-second order rate model described best the adsorption kinetics of ethylbenzene for the two selected adsorbents. The kinetic studies also revealed that the pore diffusion is not the only rate controlling step in the removal of ethylbenzene. Overall, the study demonstrated that chitosan is a potential adsorbent for the removal of ethylbenzene at concentrations as high as 200 mg/L.     

Pollutant transfer into water bodies

Although considerable effort has been devoted to the development of air pollution models, little has been done to incorporate natural mechanisms capable of removing pollutants from the atmosphere. One important process is the uptake of atmospheric pollutants by water bodies. In this paper, a calculational scheme to quantify this transport process is presented. In particular, two models characterizing wind induced turbulence in a water body are invoked to estimate the liquid phase mass transfer coefficient. A priori specification of parameters yielded predictions well within an order of magnitude of experimental evidence in both the laboratory and the field.     

Removal of Zn2+ from Aqueous Solution using Castor Seed Hull

The effects of various experimental parameters on adsorption of Zn²⁺ metal ion from its aqueous solution by castor seed hull and also by activated carbon have been investigated using batch adsorption experiments. It has been found that the amount of zinc adsorbed per unit mass of the hull increases with the initial metal ion concentration, contact time, solution pH and with the amount of the adsorbent. Kinetic experiments clearly indicate that adsorption of zinc on both castor hull and activated carbon is a three-step process??a rapid adsorption of the metal ion, a transition phase, and an almost flat plateau. This has also been confirmed by the intraparticle diffusion model. It has also been found that the zinc adsorption process followed pseudo-second order kinetics. The kinetic parameters including rate constants have been determined at different initial metal ion concentration, pH, amount, and type of adsorbent, respectively. The Langmuir and Freundlich adsorption isotherm models have been used to interpret the equilibrium adsorption data. The Langmuir model yields better correlation coefficients. The monolayer adsorption capacities (q _m ) of castor hull and activated carbon have been compared with those for others reported in the literature. The value of separation factor (R _L ) derived from the Langmuir model gives an indication of favorable adsorption. Finally, from comparative studies, it has been found that castor hull is a potentially attractive adsorbent as compared to commercial activated carbon for the removal of zinc from aqueus effluents.