The Nonreversibility of Adsorption-Desorption of Dieldrin and Lindane on Chitin in Seawater

Abstract

Adsorption and desorption of dieldrin and lindane on chitin were investigated in seawater batch tests as a function of chitin concentration, temperature, pH and salinity. For chitin concentrations ranging from 0.5 g l^?1 to 12.5 g l^?1, the pesticide concentrations were varied from 4 μgl^?1 to 65 μg^?1 for dieldrin and from 40 μl^?1 to 680 μg l^?1 for lindane. Both dieldrin and lindane show adsorption-desorption hysteresis at low chitin concentration. At high chitin concentrations (m > 6.25 g l^?1 for dieldrin and m > 10 gl^?1 for lindane) both pesticides exhibit reversible behaviour. However, only lindane adsorption is affected by chitin concentration. These types of behaviour remain fixed in prewashed chitin. However, an increase in the temperature and a decrease in the salinity made the process become reversible. A resistant-reversible two component model has been applied to account for these types of behaviour and provides a way to explain most of the observed effects by defining mass independent distribution coefficients.     

Adsorption-desorption isotherm hysteresis of beta-lactoglobulin A with a weakly hydrophobic surface.

Adsorption-desorption isotherms of bovine beta-lactoglobulin A (beta-lact A) on a weakly hydrophobic stationary phase (C1-ether) were measured by frontal analysis. The adsorption isotherms obtained at different pH were found to be dramatically different in shape, column capacity and desorption reversibility. At pH 4.5, an S-shaped adsorption isotherm was observed whereas at pH 6.0 a Langmuir isotherm was found. In addition, the desorption isotherm at pH 6.0 was found to overlap with the adsorption isotherm, and the adsorption-desorption process of beta-lact A under this condition could be characterized by a fully reversible Langmuir model. The desorption isotherm at pH 4.5, however, did not retrace the adsorption isotherm, resulting in hysteresis loops. A higher aggregate (tetramer) of beta-lact A is shown to be in an equilibrium with the beta-lact A protomer (dimer) at pH 4.5 whereas the dimer alone is predominant at pH 6.0. It is further shown that changes in the absorption coefficient between the adsorption and the desorption cycles for the tetramer at pH 4.5 can account for the hysteresis. The results demonstrate that pH can be a sensitive parameter in protein adsorption isotherm behavior and ultimately the behavior of species in preparative-scale chromatography.     

Electrospun Nanofibers Sorbents for Pre-Concentration of 1,1-dichloro-2,2 bis-(4-chlorophenyl)ethylene with Subsequent Desorption by Pressurized Hot Water Extraction

Electrospun polystyrene (PS) nanofibers (130–500 nm) incorporating a potassium salt of imidazole-1-carbodithioate were evaluated as potential sorbents for the pre-concentration of a model organochlorine pesticide; 1,1-dichloro-2,2bis-(4-chlorophenyl)ethylene (DDE). The efficiencies of DDE (0.25–1.0 μg L^?1) adsorption by the nanofiber sorbent followed by desorption employing pressurized hot water extraction (PHWE) were investigated and monitored using gas chromatography with electron capture detection (GC-ECD). Parameters such as time, temperature and pressure of extraction, sample volume, DDE concentration and sorbent mass were optimized. The maximum adsorption of DDE (0.50 μg L^?1) on electrospun PS and carbodithioate incorporated PS nanofibers was at 43.7 and 94.6%, respectively, in 20 min. Incorporation of carbodithiote doubled the adsorption efficiency of PS and achieved LOD of 0.000234 μg L^?1 for DDE. The optimal DDE desorption on the PHWE system was 93.8% in 10 min. It would seem that the use of electrospun nanofibers as sorbent material with subsequent desorption by PHWE has great potential and thus warrants further investigations. This approach as it uses water as an extraction solvent for an organochlorine pesticide provides an opportunity to eliminate organic solvents, especially for procedures aimed at monitoring organic pollutants in the environment.     

Trace analysis of Pt (IV) metal ions in roadside soil and water samples by Fe3O4/graphene/polypyrrole nanocomposite as a solid-phase extraction sorbent followed by atomic absorption spectrometry

A novel Fe₃O₄/graphene/polypyrrole nanocomposite has been successfully synthesised via a simple chemical method and applied as a new magnetic solid-phase extraction (MSPE) sorbent for the separation and pre-concentration of trace amounts of Pt (IV) in environmental samples followed by flame atomic absorption spectrometric (FAAS) detection. The nanocomposite has been characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy. Seven important parameters, affecting the extraction efficiency of Pt (IV), including pH, adsorption time, desorption solvent type and concentration, desorption time, elution volume and sample volume, were investigated. Under the optimised conditions, the calibration graph was linear in the range of 50–1500 μg L^?1 (R = 0.993). The detection limit and pre-concentration factor (PF) for Pt (IV) were found to be 16 μg L^?1 and 112.5, respectively. Under the optimised solid-phase extraction (SPE) conditions, the adsorption isotherm and the adsorption capacity of the nanocomposite for Pt (IV) were studied. Pt (IV) adsorption equilibrium data were fitted well to the Langmuir isotherm and the maximum adsorption capacity of the magnetic sorbent was calculated from the Langmuir isotherm model as 416.7 mg g^?1. The precision of the method was studied as intraday and interday variations. A relative standard deviation percentage (RSD%) value less than 3.0 indicates that the method is precise. Also, the accuracy of the method was tested by the analysis of the standard reference material (NIST SRM 2556) and by recovery measurements on spiked real samples. It was also shown that the optimised method was suitable for the analysis of trace amounts of Pt (IV) in roadside soil, tap water and wastewater samples.     

Chitin-based magnetic composite for the removal of contaminating substances from aqueous media

A method of obtaining multipurpose magnetic chitin, which combines the magnetic properties of magnetite and the adsorption properties of polysaccharide, was proposed. The possibility of using chitin-(CT) and chitosan (CS)-containing magnetic composites for the adsorption of inorganic ions Co^II and Cr^VI and organic substances (2- and 4-nitrophenols) from aqueous media was analyzed. It was shown that the adsorption capacity of magnetic chitin with respect to Co^II and Cr^VI ions reached 41 mg g^?1 and 15 mg g^?1, respectively. The maximum adsorption capacity for 4-nitrophenol (19 mg g^?1 per CT-containing magnetic composite or 56 mg g^?1 per chitin component) was about three times higher than for 2-nitrophenol. The obtained adsorbent Fe₃O₄/CT is environmentally friendly and reusable.

     

A facile fabrication of MOF for selective removal of chromium (III) from aqueous solution

A simple method for fabricating a metal organic framework (MOF: HKUST-1) as sorbent for selective removal of chromium (III) from aqueous solution is discussed. The structure and morphology of HKUST-1 was identified by fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), the powder X-ray diffraction (XRD) and N₂ adsorption-desorption (BET) analysis. Its removal process of chromium (III) and chromium (VI) on HKUST-1 was assessed systematically under various conditions such as pH value, shaking time and initial concentration of chromium (III). At pH 6.0–8.0, HKUST-1 were selective towards chromium (III) but hardly chromium (VI). Kinetic parameters fitted well with pseudo-second-order model and adsorption progress was described by Langmuir isotherm equations and spontaneous and endothermic according to the results of thermodynamics studies (?G?<?0, ?H?>?0, ?S?>?0).     

Study of Sorption Processes of Selected Pesticides on Soils and Ceramic Porous Cups used For Soil Solution Sampling

Abstract

Soil sorption constants of four organochlorine (lindane, dicofol, chlorfenson and tetradifon) and three organophos-phorus pesticides (dimethoate, fenitrothion and methidathion) were measured using two different soils at six concentrations.

Soil samples were collected at depths of 0-20 cm and around 100 cm from an experimental citrus crop field. Effects of soil properties (organic matter, moisture content, pH and texture) on the sorption processes were also investigated.

Partitioning of pesticides between soil and solution was investigated after batch equilibration, using pesticide concentrations ranging from 10 to 200 μg1^?1. The equilibration time was estimated in 2 h for organochlorine, and 72 h for organophosphorus pesticides. Data fitted to Freundlich types adsorption isotherms.

Analytical determinations were carried out by gas chromatography with ECD and NPD detectors, after liquid-liquid extraction with dichloromethane of the water supernatant.

Moreover, a validation of the use of suction samplers used to collect soil solution samples from the vadose zone, based on a short term study in the laboratory was determined.     

Calcium lignosulfonate adsorption and desorption on Berea sandstone

This paper describes adsorption and desorption studies carried out with calcium lignosulfonate (CLS) on Berea sandstone. Circulation experiments were performed to determine CLS adsorption isotherms and the effects of CLS concentration, temperature, salinity, brine hardness, and injection rate on adsorption density. Flow-through experiments were performed to assess the reversibility of CLS adsorption and the influence of postflush rate, brine concentration, brine hardness, brine pH, and temperature on the desorption process. Results indicate that CLS adsorption isotherms on Berea sandstone follow the Freundlich isotherm law. The results presented in this paper on the effects of CLS adsorption and desorption on Berea sandstone show that: (1) increasing CLS concentration and salinity increases CLS adsorption density; (2) increasing temperature will decrease adsorption density; (3) increasing injection rate of CLS solution will slightly decrease CLS adsorption density; (4) postflush rate and salinity of brine have a large impact on the CLS desorption process; (5) the adsorption and desorption process are not completely reversible; and (5) temperature and pH of the postflush brine have little effect on desorption.     

Removal of Th4+ ions from aqueous solutions by graphene oxide

The removal of Th⁴⁺ ions from aqueous solutions was investigated using single-layer graphene oxide (GO) as a sorbent which was prepared by the modified Hummers’ method through batch adsorption experiments at room temperature. Structural characterizations of the sorbent were also investigated. The influences of the pH value of solution, contact time, sorbent dose, ionic strength, the initial metal ion concentration and temperature on the adsorption of Th⁴⁺ were also investigated. These results indicated that the adsorption of Th⁴⁺ was dependent on the pH and independent on the ionic strength. The sorbent provided significant Th⁴⁺ removal (>98.7 %) at pH 3.0 and the adsorption equilibrium was achieved after only 10 min. The Langmuir adsorption isotherm fit the absorption profile very closely, and indicated that a maximum adsorption capacity of 1.77 mmol g^?1 of GO (411 mg g^?1) after 2 h. The thermodynamic parameters showed that this adsorption process was endothermic and spontaneous. Moreover, the desorption level of Th⁴⁺ from GO, by using 0.1 mol L^?1 H₂SO₄ as a stripping agent, was 84.2 ± 1.2 %, and that of 0.5 mol L^?1 HNO₃ as a stripping agent, was 79.8 ± 3.0 %.     

Highly efficient removal of uranium(VI) from aqueous solutions by poly(acrylic acid-co-acrylamide) hydrogels

In this study, poly(acrylic acid-co-acrylamide) (PAAAM) hydrogels were used to remove uranium (VI) ions in wastewater and characterized by FTIR, SEM, EDX. The effects of pH value, coexistence of ionic strength, contact time, initial U (VI) ion concentration and adsorption temperature were also studied. Adsorption data fitted well with pseudo-second-order, intra-particle diffusion model and Langmuir isotherm mode, the maximum adsorption capacity of U(VI) was 713.24 mg g^?1. Thermodynamic analysis shows that the adsorption of U(VI) is spontaneous endothermic. PAAAM hydrogel has excellent regeneration performance, after five time adsorption–desorption cycles, the adsorbent still maintained 99.24% adsorption capacity.     

Determination of chlorite at very low levels by using differential pulse polarography

A method is reported for the determination of μgl^?1 levels of chlorite by using differential pulse polarography. The electrochemical reduction of chlorite was studied between pH 3.7 and 14 and in an ionic strength range of 0.05–3.0 M. The optimum conditions are pH 4.1–4.4 and an ionic strength of 0.45 M. The current under these conditions is diffusion-controlled and is a linear function of chlorite concentration ranging from 2.77×10^?7 to 2.80×10^?4 M (19 μgl^?1 to 19 mg l^?1). The imprecision is better than ±1.0% and ±3.4% at concentrations of 2.87×10^?5 M and 1.74×10^?6M, respectively, with a detection limit of 1×10^?7 M (7μgl^?1). An interference study and the application of this method for determining chlorite in drinking water are reported.     

Highly efficient elimination of thorium(IV) from aqueous solution using poly(cyclotriphosphazene-co-melamine) microspheres

Highly crosslinked organic–inorganic hybrid polymer poly(cyclotriphosphazene-co-melamine) microspheres (PZM) were synthesized by a simple method. The microspheres was characterized by FTIR, SEM and EDX. It was applied to eliminate thorium(IV) from aqueous solution under various conditions, i.e., pH, initial concentration, dosage and contact time. The experimental data were well-imitated via the pseudo-second-order kinetic model and its adsorption processes comply with the Langmuir isotherm model. Adsorption thermodynamic studies demonstrated that the adsorption process, in essence, was spontaneous and endothermic. Furthermore, the maximum experimental adsorption capacity was 98.6 mg g^?1 for initial thorium(IV) concentration 50 mg L^?1. When pH?=?0.0, the thorium(IV) removal efficiency reached at 76.9%, which indicates that the adsorbent can also was used in a peracid environment. Adsorption behavior of thorium(IV) onto the microspheres were weakly affected via temperature, implying that adsorption would be done at room temperature.

     

Adsorption of Cl<Superscript>−</Superscript> ions on γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> oxide from nitrate solutions

The adsorption of chloride ions on γ-Fe₂O₃ oxide (maggemite) from nitrate solution is studied using the method of potentiometric titration and an ion-selective electrode. The specific character of adsorption is determined. It is shown that the maggemite surface coverage with Cl^? ions increases with increasing concentration of ions in the solution, decreasing pH value, and increasing potential. The adsorbability of ions changes drastically in the pH range about pH₀ (γ-Fe₂O₃)6.2. It is found that the adsorption of chloride ions from neutral nitrate solution exponentially increases in the potential range from 0.1 to 1.0 V. The type of adsorption isotherm and the adsorption parameters are determined. It is found that, in the absence of external polarization, the concentration dependences of adsorption of Cl^? ions are complex-shaped, and their initial portions are described by the Langmuir isotherm. Further increase of adsorption is explained by the penetration of Cl^? ions inwards the oxide.     

Controlled adsorption of cellulase onto pretreated corncob by pH adjustment

The effective recycling of cellulase requires an in-depth understanding of cellulase adsorption and desorption. In the present study, we examined the adsorption behaviors and stabilities of cellulase at different pH values. Acidic pH (<4.8) was found to favor adsorption, whereas neutral and alkaline pH (especially pH 7 and 10) favored desorption. The influence of pH on cellulase activity was temperature dependent. Under mild conditions (e.g., pH 7 and 25 °C), the effect of pH on cellulase activity was reversible, and the cellulase activity can return to almost 100% by adjusting the pH value to 4.8. However, under severe conditions (e.g. pH 10 and 50 °C), irreversible inactivation may take place. We also explored the roles of pH and temperature in cellulase adsorption kinetics and isotherms. At pH 4.8, temperature had no remarkable effect on the adsorption capacity of the cellulases onto substrate. However, at pH 7 and 10, high temperatures lead to more cellulase desorption. Only at pH 4.8 does cellulase adsorption well fit (R ² > 0.96) the pseudo-first-order kinetic and Langmuir adsorption isotherm (R ² > 0.99) models.     

Adsorption on Quartz of Co(II), Ni(II), and Cu(II) in the Form of Hydroxide Nanoparticles or Metal Ionic Species from Solutions with pH Close to That of the Onset of Hydroxide Formation

The kinetics of adsorption and desorption of Co(II), Ni(II), and Cu(II) from aqueous solutions were studied at such pH values when the prevailing metal species in the continuous phase is either hydroxide or Me^{2 +} (at pH only slightly lower than that at which the hydroxide starts to precipitate). The desorption was performed by methods producing different effects on the adsorbed layer. The time of the preceding adsorption was also varied. A significant difference in the adsorption-desorption behavior of the metals was revealed. This difference cannot be explained without considering the effects related to the detailed electronic structure of metal species and of the adsorbent active centers. The observed trends are attributed to the difference in the properties of the metals as electron pair acceptors and of the surface coordination compounds formed.     

The adsorption of the HgEDTA complex at mercury electrodes

While free EDTA has no tendency to adsorption on mercury surfaces, its complex with Hg(II) is adsorbed strongly. The coverage is very small in alkaline solutions where HgYOH^3? is present, reaches 60% at moderate pH, and is high at pH = 2, where the predominant species in solution is HgYH^?. Dependence of peak potential on pH for cathodic stripping voltammetry indicated that for pH > 3, HgY^2? is adsorbed at the surface, while at pH 2 the adsorbed complex is protonated. Cyclic chronopotentiometric experiments suggest formation of a coherent film of adsorbed material at pH 2. At pH = 2 adsorption of HgEDTA can be described by a Frumkin isotherm, and at pH = 4.8 by either a virial or HFL isotherm.     

Competitive Adsorption of Methylene Blue and Rhodamine B on Natural Zeolite: Thermodynamic and Kinetic Studies

A batch system was applied to study the adsorption behavior of methylene blue (MB) and rhodamine B (RB) in single and binary component systems on natural zeolite. In the single component systems, the zeolite presents higher adsorption capacity for MB than RB with the maximal adsorption capacity of 7.95×10^?5 and 1.26×10^?5 mol/g at 55°C for MB and RB, respectively. Kinetic studies indicated that the adsorption followed pseudo‐second‐ order kinetics and could be described by a two‐step diffusion process. For the single component systems, the adsorption isotherm could be fitted by the Langmuir model. In the binary component system, MB and RB exhibit competitive adsorption on the zeolite. The adsorption is approximately reduced to 50% and 60% of single component adsorption systems of MB and RB, respectively at an initial concentration of 6×10^?6 mol·L^?1 at 25°C. In the binary component system, kinetic and adsorption isotherm studies demonstrate that the experimental data are following pseudo‐second‐order kinetics and Langmuir isotherm and kinetic data are fairly described by a two‐step diffusion model. Effect of solution pH on adsorption of MB and RB in both single and binary component systems was studied and the results were described by electrostatic interactions.     

Efficient removal of methyl violet from aqueous solution by a low-cost adsorbent—C. camphora fallen leaves powder

The adsorption property of C. camphora fallen leaves powder (CFLP) to methyl violet (MV) from aqueous solution was studied in this work. The results showed that the CFLP has considerable adsorption property to MV. The percentage adsorption reached 91% in 50?mg?L^?1 of MV solution at dosage 0.6?mg?g^?1. The adsorption kinetics for MV on the CFLP follow a pseudo-second-order pathway, and the adsorption equilibrium data can be described well by the Langmuir isotherm model compared to Freundlich isotherm model. Intra-particle diffusion is not the only rate-controlling step and combination of mechanisms was involved in the entire adsorption process for MV on the CFLP; the adsorption process is endothermic, spontaneous and random. Therefore, the CFLP can be used as low-cost adsorbent for refractory cationic organic dye in wastewater.     

Bio-adsorption of dyes from aqueous solution by powdered excess sludge (PES): Kinetic,isotherm, and thermodynamic study

Over 30 million tons of excess sludge is discharged from rural municipal sewage plants annually in China and it is predicted that this figure will keep increasing. However, most of the excess sludge is dumped in landfills except for minor applications. In this study, based on low-cost and recycling waste, the excess sludge was used to adsorb organic dyes from aqueous solution after being directly dewatered. The powdered excess sludge (PES) presents selective adsorption property to cationic dyes. Statics batch adsorption experiments of malachite green (MG) on PES were performed to evaluate the effects of pH, adsorbent dosage, and initial MG concentration. Results revealed that the bio-adsorption equilibrium of MG on the PES can be quickly achieved at 30 min with maximum percentage adsorption of 84% at pH 7, initial dye concentration of 20 mg L^?1, and adsorbent dosage of 1.5 g L^?1. Moreover, the adsorption kinetics follows a pseudo-second-order pathway, and the equilibrium adsorption data could be described well by the Langmuir isotherm equation. Intra-particle diffusion is not the only rate-controlling step in the entire adsorption process. The adsorption process is endothermic, spontaneous, and random. PES can be used as a low-cost adsorbent for refractory cationic organic dye in effluent.     

Preparation of Thermo-Sensitive Magnetic Cationic Hydrogel for the Adsorption of Reactive Red Dye

In this study, thermo-sensitive magnetic cationic hydrogel (TSMCH) based on (3-acrylamidopropyl) trimethyl ammonium chloride (APTMACl) and N-isopropylacrylamide (NIPAm) was synthesized by free radical copolymerization. The TSMCH was characterized with Fourier transform infrared spectroscopy, thermal gravimetric analysis, x-ray diffraction, scanning electron microscope with energy dispersive x-ray, vibrating sample magnetometer, and zeta potential, and employed as adsorbent for adsorbing reactive red (RR) dye. Effects of molar ratios of APTMACl to NIPAm on the adsorption capacity of TSMCH were studied, and the results showed that a maximum adsorption capacity (1428.57 mg RR g^?1 TSMCH) had been achieved when the molar ratio of APTMACl to NIPAm was 1:1. The adsorption isotherm of RR was well fitted by the Langmuir isotherm equation. TSMCH had good selectivity for adsorbing RR. Solution pH hardly affected the adsorption of RR on the TSMCH. The adsorption amount of RR increased with the increase of temperature. The adsorption–desorption of TSMCH was evaluated in three circles and a high regeneration rate was demonstrated.