Differences in the sorption kinetics of various non-ionisable pesticides in a limited number of agricultural soils from the Mediterranean basin.

Adsorption in soil of organic contaminants, such as pesticides, is a time-dependent process, which can be relevant for understanding and predicting the potential pollution risk of different water sources. The adsorption behavior of six different pesticides with a wide range of physicochemical properties (log KOW 1.26-5.8) was evaluated in up to three different soils with low organic carbon (OC) content (≤1.2%). Pesticide sorbed amounts were fitted to several mathematical models to unravel the mechanisms involved in the adsorption process. The linear distribution constants revealed that pendimethalin and the pyrethroid insecticides were strongly retained in soil, whereas the other three compounds were moderately or weakly adsorbed. In the three soils, the pseudo second order model described more accurately the sorption kinetics of all the contaminants. The more hydrophobic pesticides (log KOW ≥ 4.6) presented lower kinetic rates as compared with the other compounds under study. Both Elovich and intraparticle diffusion models reflected a strong contribution of a rapid initial adsorption on soil surface for thiacloprid, dimethenamid and fenarimol. For the hydrophobic pesticides this contribution was moderate according to the intraparticle diffusion model. Therefore, slower diffusion into the soil micropores was more relevant for the more hydrophobic compounds and for the bigger molecules, and less significant for the more polar pesticides because almost 90% of the total amount adsorbed was achieved in the rapid initial stage.

Application of Natural Clinoptilolite for Ammonium Removal from Sludge Water.

Sludge water (SW) arising from the dewatering of anaerobic digested sludge causes high back loads of ammonium, leading to high stress (inhibition of the activity of microorganisms by an oversupply of nitrogen compounds (substrate inhibition)) for wastewater treatment plants (WWTP). On the other hand, ammonium is a valuable resource to substitute ammonia from the energy intensive Haber-Bosch process for fertilizer production. Within this work, it was investigated to what extent and under which conditions Carpathian clinoptilolite powder (CCP 20) can be used to remove ammonium from SW and to recover it. Two different SW, originating from municipal WWTPs were investigated (SW1: c0 = 967 mg/L NH4-N, municipal wastewater; SW2: c0 = 718-927 mg/L NH4-N, large industrial wastewater share). The highest loading was achieved at 307 K with 16.1 mg/g (SW1) and 15.3 mg/g (SW2) at 295 K. Kinetic studies with different specific dosages (0.05 gCLI/mgNH4-N), temperatures (283-307 K) and pre-loaded CCP 20 (0-11.4 mg/g) were conducted. At a higher temperature a higher load was achieved. Already after 30 min contact time, regardless of the sludge water, a high load up to 7.15 mg/g at 307 K was reached, achieving equilibrium after 120 min. Pre-loaded sorbent could be further loaded with ammonium when it was recontacted with the SW.

Modeling of adsorption flux in nickel-contaminated synthetic simulated wastewater in the batch reactor.

In the present investigation, physico-chemical characterization of composite material revealed the presence of fluffy surface structure with crystalline look and negatively charged surface functional groups. The study of adsorption flux by using dimensionless numbers φ (2.62), Nk (62.68) and λ (1.17 × 10-5) proved that adsorption of nickel ions on the surface of composite material was mostly film diffusion-limited with maximum surface area coverage coupled with weakened surface tension. The results of intraparticle diffusivity and Boyd plot model showed that at the onset of process, film diffusion was the primary mechanism involved and at the later stage intraparticle diffusion played a critical role as rate governing step. The values of film (0.65 × 10-8 cm2 sec-1) and pore diffusivity (1.8 × 10-12 cm2 sec-1) coefficients showed that the adsorption process is dependent upon two different types of diffusion namely film and pore diffusion. Overall, transport and reshuffling mechanism had no substantial role in adsorption dynamics of nickel ions on the surface of composite material. Sorption isotherm and kinetics modeling showed higher values of regression coefficients for Langmuir isotherm (R2 = 0.99) and pseudo-second-order kinetic model (R2 = 0.99) compared to other models. This showed that sorption of nickel followed monolayer coverage with chemisorption at optimized process parameters like pH 6, biosorbent dose 0.1 g/L, temperature 50 °C, agitation rate180 rpm, adsorbate concentration100 mg/L and contact time 60 minutes. The positive value of enthalpy of adsorption (ΔH = + 10.41 kJ/mole) and entropy (ΔS = +58.19 J/mol K) showed that binding of nickel ions on the surface of the composite material was endothermic with improved randomness at solid-liquid interface. The negative value of (ΔG = -6.4 to -8.67 kJ/mol) showed spontaneous nature of nickel adsorption on composite material in the liquid phase.

Carbamazepine removal from water by carbon dot-modified magnetic carbon nanotubes.

Carbon dot- and magnetite-modified magnetic carbon nanotubes (CMNTs) were synthesized and evaluated for carbamazepine removal from water. The adsorbent was characterized by multiple modern surface and microstructure analyzing techniques. CMNTs were composed of three components including carbon dots (CDs), carbon nanotubes (CNTs) and magnetite. CDs and CNTs introduce abundant carboxyl groups onto CMNTs and magnetite allows rapid magnetic separation of the adsorbent realizable after batch adsorption. This adsorbent has a moderately high adsorption capacity of 65 mg-carbamazepine/g-adsorbent at pH 7.0 ±â€¯0.2, which is superior to many reported adsorbents. Carbamazepine was uptaken well in a wide pH range, regardless of the surface charging of CMNTs. Its adsorption on CMNTs was quite fast and reached 80% of removal during the initial 3 h. The mass transfer within CMNTs and the time-dependent utilization, exhaustion and depletion of the adsorption capacity were successfully described using a simplified homogeneous surface diffusion model (HSDM). The surface diffusion coefficients (Ds) rose with increasing initial carbamazepine concentrations. After six regeneration and recycle experiments, the capacity loss of CMNTs was less than 2.2% at the conditions tested. FTIR spectra showed the characteristics of the components. Raman spectra implied a π-π electron donor-acceptor (EDA) interaction during adsorption. This work proposed a method of combining π-bond-rich materials (CNTs and CDs) and magnetite to make separable composite adsorbents with high affinity interactions between carbamazepine and carbon materials. The prepared adsorbent is attractive for carbamazepine removal due to its good performance, moderate cost, ease of separation, and ability to regenerate.

Sorption kinetics, isotherms and mechanisms of PFOS on soils with different physicochemical properties.

Perfluorooctane sulfonate (PFOS), an emerging contaminant, is environmentally persistent, bioaccumulative and toxic to human health and ecosystems. It has been widely detected in groundwater, surface water, soil and sediment. So far, very few research has reported on the PFOS sorption behaviors onto soils, one of the primary processes that influence its fate and transport in the subsurface. In this study, the sorption and desorption of PFOS onto six soils with different physicochemical properties were investigated. Kinetic and equilibrium studies of PFOS sorption onto six soils were carried out in batch experiment. The sorption kinetics of PFOS on the six soils demonstrated that PFOS sorption reached equilibrium within 48h, and the well-fitted pseudo-second-order kinetic model to experimental data suggested that chemisorption was involved in PFOS sorption on soils. The intraparticle diffusion model results indicated that both film diffusion and intraparticle diffusion were the rate-limiting steps for five of the six soil samples, while the intraparticle diffusion was the only limiting step in the PFOS sorption on the sixth soil. PFOS sorption isotherms can be described by the Freundlich model well for all six soils (R2=0.979-0.999). The correlation analysis between KF of PFOS and the physicochemical properties of the soils showed that a positive correlation between KF and Al2O3, SOC and Fe2O3. The FTIR data demonstrated hydrophobic interaction, ion exchange, surface complexing and hydrogen bonding might all play a role in the PFOS sorption onto soil samples. PFOS sorption onto soil minerals, especially iron oxide minerals, needs to be further explored in future.

Kinetic analysis of mass transfer of Eu(III) in extractant-impregnated polymer-layered silica particle in multiple-ion distribution system.

The Eu(III) distribution mechanism in single extractant-impregnated polymer-layered silica particle in a complex solution containing multiple lanthanide ions was investigated using fluorescence microspectroscopy, which was compared with the single-ion distribution system. The rate-determining step of the Eu(III) distribution was the reaction of Eu(III) with the two extractant molecules in the particle. The distribution mechanism and rate constants obtained in the multiple lanthanide ions-distribution system agreed with those of the single-ion distribution system.

Intraparticle sorption and desorption of antibiotics.

Intraparticle domains are the critical locations for storing contaminants and retarding contaminant transport in subsurface environments. While the kinetics and extent of antibiotics sorption and desorption in subsurface materials have been extensively studied, their behaviors in intraparticle domains have not been well understood. This study investigated the sorption and desorption of antibiotics (ATs) in the intraparticle domains using quartz grains and clay, and antibiotic tetracycline (TC) and levofloxacin (LEV) as examples that are commonly present in groundwater systems. Batch experiments coupled with the analyses using various microscopic and spectroscopic techniques were performed to investigate the sorption and desorption kinetics, and to provide insights into the intraparticle sorption and desorption of TC and LEV. Results indicated that both TC and LEV with different physiochemical properties can migrate into intraparticle domains that were consistent with sorptive diffusion. The rate and extent of the sorption are a function of intraparticle surface area and properties, pore volume and connectivity, and ionic properties of the ATs. The sorptive diffusion led to the slow desorption of both TC and LEV after their sorption, apparently showing an irreversible desorption behavior (with desorption percentage about 1.86-20.51%). These results implied that intraparticle domains can be important locations for storing ATs, retarding ATs transport, and may serve as a long-term secondary source for groundwater contamination.

Adsorptive removal of oxytetracycline hydrochloride using bagasse-based biochar powder and beads.

Oxytetracycline Hydrochloride (OTC), a common antibiotic used to treat specific illnesses in humans and animals, is characterized by poor absorption into cells, low volatility, and high hydrophilicity. It is a potent contaminant that poses a serious threat to the ecosystem, particularly the aquatic sources. Adsorption onto natural adsorbents is one of the most successful, economical, and ecologically friendly ways to remove antibiotics from waste water. The present work focuses on the adsorption of OTC utilizing alginate biochar beads (AlBCB) and biochar powder (BC) derived from bagasse. The influence of several factors were studies and optimized through batch studies employing BC and AlBCB. After 50 min BC displayed a removal of 97%, at an initial concentration of 10 ppm. The experimental data was discovered to follow PFO kinetics and fit with the Freundlich isotherm adsorption model. AlBCB, after a contact time of 40 min, indicated a maximum percentage removal of 86% for initial concentration of 10 ppm OTC. Al-biochar beads showed the maximum percentage removal at pH 10. 0.5 g of adsorbent was used to carry out all batch experiments at room temperature. The adsorption fitted Freundlich adsorption isotherm and intraparticle diffusion kinetics.

Causative mechanisms limiting the removal efficiency of short-chain per- and polyfluoroalkyl substances (PFAS) by activated carbon.

Short-chain per and polyfluoroalkyl substances (PFAS) have been found to be relatively high in water treatment systems compared to long-chain PFAS because of the unsatisfactory adsorption efficiency of short-chain PFAS. Knowledge about why short-chain PFAS are less removed by porous carbon is very limited. The study focused on providing causal mechanisms that link the low adsorption of short-chain PFAS and proposing an improved method for removing both short- and long-chain PFAS. The long-chain PFAS with higher hydrophobicity diffused more quickly than the short-chain PFAS due to stronger partitioning driving forces. In the initial adsorption stage, therefore, pores of activated carbon were blocked by long-chain PFAS, which makes it difficult for the short-chain PFAS to enter the internal pores. Although several short-chain PFAS diffuse into the pores, the relatively more hydrophilic short-chain congeners cannot be fully adsorbed on activated carbon due to limited positively charged sites. Moreover, compared to larger particle sizes, smaller activated carbon particles have shorter pore channels near the surface, reducing the risk of pore-blocking and ensuring the pores remain accessible for more efficient adsorption. Additionally, these smaller particles offer a greater external surface area and more functional groups, which enhance the adsorption capacity. It indicates that the smaller particle size of activated carbon would have a positive effect on the short-chain PFAS removal.

Rethinking of the intraparticle diffusion adsorption kinetics model: Interpretation, solving methods and applications.

Adsorption is a widely used unit process in various fields, such as chemical, environmental and pharmaceutical, etc. The intraparticle diffusion adsorption kinetics model is one of the most widely used adsorption kinetics models. However, the application and solving method of this model have yet to be discussed. This model has two forms (qt = kt1/2 and qt = kt1/2 + constant, where qt is the adsorption capacity at time t, k and constant are the model parameters), which have not been unified yet. Moreover, the interpretation of this kinetics model lacks a theoretical basis (if the line passes through the origin point (0, 0), the adsorption is dominated by the intraparticle diffusion; if not, it is a multiple adsorption process). In this study, we analyzed the proper equations of the intraparticle diffusion model and their applications, discussed the interpretation of the mass transfer steps revealed by this model, and provided the solving methods. The result indicated that the piecewise function qt = k1t1/2 (0 ≤ t ≤ t1); qt - qt = t1 = k2(t - t1)1/2 (t1 < t ≤ t2) is the proper form of this model. The adsorbate diffusion in the pores inside the adsorbent is the mass transfer step revealed by this model. The statistical parameters should be used to evaluate the fitting results instead of judging whether the model lines pass through the origin point (0, 0). We provide the solving methods to use the Origin and Microsoft EXCEL software to solve the model. Our study established the method for application of the intraparticle diffusion model.

Cost-effective phosphorus removal from aqueous solution by a chitosan/lanthanum hydrogel bead: Material development, characterization of uptake process and investigation of mechanisms.

Excessive phosphorus is one of the main reasons leading to eutrophication that causes severe ecosystem imbalance and negative human health impacts. In this study, several chitosan (CS)/lanthanum (La) hydrogel beads were first synthesized and tested for phosphorus removal. The stable cross-linked CS/La hydrogel bead prepared with the optimized conditions of 10 wt% La/CS and 1.5 mL of 5% glutaraldehyde demonstrated exceptional performance in the removal. It removed phosphate effectively from an aqueous solution in the pH range from 2 to 7. The complete phosphate uptake was achieved at contact time of 6 h under the completely mixing batch condition. The experimental maximum adsorption capacity of 107.7 mg g-1 was observed at solution pH 4. The phosphate adsorption was well described by the Freundlich isotherm and the intraparticle surface diffusion model. Furthermore, the adsorbent was effectively regenerated and reused in a five-cycle adsorption-desorption operation. The removal of phosphate can be attributed to electrostatic attraction and ion exchange. Moreover, the bead was capable of removing heavy metals: copper, zinc and lead. This adsorbent may be served as a cost-effective material for the treatment of phosphorus-contaminated water so as to minimize the occurrence of eutrophication.

Enrofloxacin and Sulfamethoxazole Sorption on Carbonized Leonardite: Kinetics, Isotherms, Influential Effects, and Antibacterial Activity toward S. aureus ATCC 25923.

Excessive antibiotic use in veterinary applications has resulted in water contamination and potentially poses a serious threat to aquatic environments and human health. The objective of the current study was to quantify carbonized leonardite (cLND) adsorption capabilities to remove sulfamethoxazole (SMX)- and enrofloxacin (ENR)-contaminated water and to determine the microbial activity of ENR residuals on cLND following adsorption. The cLND samples prepared at 450 °C and 850 °C (cLND450 and cLND550, respectively) were evaluated for structural and physical characteristics and adsorption capabilities based on adsorption kinetics and isotherm studies. The low pyrolysis temperature of cLND resulted in a heterogeneous surface that was abundant in both hydrophobic and hydrophilic functional groups. SMX and ENR adsorption were best described using a pseudo-second-order rate expression. The SMX and ENR adsorption equilibrium data on cLND450 and cLND550 revealed their better compliance with a Langmuir isotherm than with four other models based on 2.3-fold higher values of qmENR than qmSMX. Under the presence of the environmental interference, the electrostatic interaction was the main contributing factor to the adsorption capability. Microbial activity experiments based on the growth of Staphylococcus aureus ATCC 25923 revealed that cLND could successfully adsorb and subsequently retain the adsorbed antibiotic on the cLND surface. This study demonstrated the potential of cLND550 as a suitable low-cost adsorbent for the highly efficient removal of antibiotics from water.

Application of the Steric Mass Action formalism for modeling under high loading conditions: Part 2. Investigation of high loading and column overloading effects.

The application of a model-based approach for industrial chromatography development requires the capability of the model to describe protein elution under high loading and overloading conditions. In a previous work, an extensive dataset was created to model the elution behavior of a bispecific antibody (bsAb) on the strong cation exchange resin POROS™ XS. Thereby, the pH-dependence of the model parameters in the Steric Mass Action (SMA) model could be examined and described over a pH range of 4.5 to 8.9. However, discrepancies between simulated and experimental data were observed under high loading and overloading conditions, particularly in the lower pH range (pH 4.5 to 5.3) and in the higher pH range (pH 6.0 to 9.0). In this work, these discrepancies are studied by performing new experiments which show that these differences were primarily not caused by limitations of the SMA model. At lower pH values, overloading phenomena such as protein breakthrough during the loading phase, additional peaks, and peak shoulders occurred. The application of various experiments performed with different Na+ concentrations and different loading times during sample loading revealed that intraparticle diffusion effects and conformational changes of the bsAb are responsible for these overloading phenomena at low pH. The applied lumped rate mass transfer model is not adequate and should be extended to consider these effects. At higher pH, the assumption of describing the bsAb's elution behavior with only one simulated species was insufficient to predict complex peak shapes that arise because of multi-component elution of the bsAb's charge variants. The extension of the model to a simple multi-component system consisting of two variants allowed the prediction of a majority of the complex elution profiles.

A systematic study of cellulose-reactive anionic dye removal using a sustainable bioadsorbent.

Cellulose-reactive anionic dyes are one of the dominant colorants used in textile finishing. Unfortunately, they also produce large quantities of wastewater that must be treated before discharge, demanding low-cost and sustainable adsorbents that can easily be implemented, especially for developing countries with thriving cotton-based textile sectors. In this study, a high specific surface area (670 m2/g) water hyacinth root powder (WHRP) bioadsorbent that is neither carbonized nor activated was prepared to remove cellulose-reactive anionic blue dye from an aqueous solution. The effect of adsorption pH (pH = 2-8), adsorbent dose (1 g/L-6 g/L), dye concentration (50 mg/L-500 mg/L), adsorbent particle size (50 µm-1000 µm), mixing speed (100 rpm -200 rpm), and adsorption temperatures (22 °C-60 °C) were systematically studied. It was found that the protonation of lignin polyphenols in WHRP at pH = 2 was responsible for the observed high (∼99%) adsorptive removal of reactive blue dye. The maximum equilibrium adsorption capacity was 128.8 mg/g when 1 g/L WHRP and 500 mg/L dye concentration were used. In addition, adsorption isotherms, kinetic models, and adsorption thermodynamics were investigated. Increasing adsorbent dose, decreasing adsorbent particle size, increasing mixing speed, and lowering temperature favored the adsorption of reactive dye to WHRP adsorbent. The batch adsorption data were best fitted with both Langmuir and Temkin models, especially at 22 °C, while the adsorption kinetic behavior was described best using pseudo-second-order kinetics. Adsorption of cellulose-reactive blue dye to WHRP was spontaneous as characterized by the negative Gibbs energy (-11 kJ/mol to -24 kJ/mol) and exothermic with negative enthalpy (-13 kJ/mol to -23 kJ/mol). The overall adsorption process was controlled by more than one mechanism since the intraparticle diffusion was not the only rate-limiting step under our experimental conditions. Taken together, the abundantly available and sustainable WHRP is an efficient adsorbent that could be scaled up for treating cellulose-reactive dye-contaminated water.

Biochar heavy metal removal in aqueous solution depends on feedstock type and pyrolysis purging gas.

The effectiveness of biochar as a sorptive material to remove contaminants, particularly heavy metals, from water is dependent on biomass type and pyrolysis condition. Biochars were produced from pulp mill sludge (PMS) and rice straw (RS) with nitrogen (N2) or carbon dioxide (CO2) as the purging gas. The sorptive capacity of the biochars for cadmium(II), copper(II), nickel(II) and lead(II) was studied. The heavy metal adsorption capacity was mainly affected by biomass type, with biochars adsorption capacities higher for lead(II) (109.9-256.4 mg g-1) than for nickel(II) (40.2-64.1 mg g-1), cadmium(II) (29.5-42.7 mg g-1) and copper(II) (18.5-39.4 mg g-1) based on the Langmuir adsorption model. The highest lead(II) adsorption capacities for PMS and RS biochars were 256.4 and 133.3 mg g-1, respectively, when generated using N2 as the purging gas. The corresponding lead(II) adsorption capacities were 250.0 and 109.9 mg g-1, respectively, when generated using CO2 as the purging gas. According to the intraparticle diffusion model, 30-62% of heavy metal adsorption was achieved in 1 h; film diffusion was the rate-dominating step, whereas pore diffusion was a rate-limiting step. Ion exchange and complexation between heavy metals and biochar surface functional groups such as carbonyl and hydroxyl groups were effective mechanisms for heavy metal sorption from the aqueous solution. We conclude that proper selection of both the feedstock type and the purging gas is important in designing biochars for the effective removal of potentially toxic metals from wastewater.

Synthesis of low-cost bentonite/Duranta erecta's fruit powder imbedded alginate beads and its application in surfactant removal.

High industrialization and improved medical facilities are deteriorating aquatic bodies through untreated effluents. This study is aimed to design and characterize the bentonite, Duranta erecta, and their hybrid-alginate beads for the removal of cetyltrimethylammonium bromide (CTAB) from its aqueous solution. D. erecta's seed powder was treated by using a sonochemical method and embedded into alginate beads. All designed beads were characterized by using physicochemical methods, Fourier-transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) technique. Hybrid beads were found to form an appropriate hydrogel structure with maximum surface area per unit gram (544 cm2 g-1), 0.42 mg dry weight, and 2.70 mm diameter. Kinetics and intraparticle diffusion models were fitted where involvement of both chemisorption and intraparticle diffusion was observed during the initial 30 and post-30-min phase, respectively. Thermodynamic studies corroborated the spontaneity of the CTAB adsorption process. Bentonite alginate beads showed the highest adsorption capacity of 97.06 mg g-1 in 100 mg L-1 CTAB solution at optimized conditions, while hybrid-alginate beads showed excellent efficiency with a wide range of physicochemical conditions frame. Conclusively, designed beads can be used to remove the surfactant, i.e., CTAB, from industrial waste effluents for the betterment of water reservoirs.

Dataset on adsorption of phenol onto activated carbons: Equilibrium, kinetics and mechanism of adsorption.

Two activated carbons (AC) prepared from onion leaves (OL) (Allium fistulosum) and palm kernel shell (PS) (Elaeis guineesis) were used to adsorb phenol from aqueous solution. Adsorption kinetics was studied by Pseudo-first order (PFO) and Pseudo-second order (PSO) models, while equilibrium was modelled using Langmuir, Freundlich, Toth and Redlich Peterson isotherms. Adsorption mechanism was analyzed applying Boyd and intraparticle diffusion models. The parameters of each one of the models were calculated using Minitab17® by non-linear regression. Piecewise linear regression was applied to calculate the parameters of Boyd and intraparticle diffusion models. Phenol adsorption onto activated carbons is describe better by Langmuir isotherm and PSO kinetic model. Maximum adsorption capacity was between 30 and 40 mg.g-1.

Linearized form effect on estimation adsorption parameters of three industrial dyes by lignocellulosic sorbent.

CONTEXT: Textile industries discharge large amounts of untreated colored wastewater into ecosystems which have adverse effects on the human, living and aquatic environment. The aims of this study were: upgrading and testing the brewery waste adsorption affinity towards BEMACID red (B-R), BEMACID yellow (B-Y) and BEZAKTIV black (B-B), verified the effect of linear form modeling on adsorption parameters values and to find the limiting kinetic step in adsorption process. METHODS: The adsorption efficiency of brewery waste towards three textile dyes: B-Y, B-R and B-B is tested. The evolution between the adsorption capacity and the operating conditions such as: pH solution, adsorbent mass, contact time and initial dye concentration is determined by kinetics measurements. Effect of a form of pseudo-first order, six forms of pseudo-second order, a form of intra-particle diffusion and a form of external mass transfer diffusion are tested to the prediction of kinetic parameters and to find the limiting kinetic step. In order to modeling the equilibrium data, a form of Freundlich and five forms of Langmuir isotherms are tested. The residual concentration of dye in solution was measured by spectrophotometer. Scanning Electron Microscope (SEM) was using to investigate the structure of raw adsorbent. RESULTS: The results of kinetics measurements show that the perfect adsorption operating conditions are: acidic medium for all dyes (pH = 2 and pH = 3), low mass adsorbent (m = 40 mg), equilibrium time t = 40 min and for initial concentration of 250 mg/L. Also the results prove that the adsorption mechanism is controlled by both steps of diffusions (interne and extern diffusion) and fitted well by the first and the second linearized form of pseudo-second order model with correlation coefficient R2 = 0.99. The results of isotherms modeling show that the second and the third linearized forms of Langmuir giving the best removed amount for B-Y equal 200 and 219.4 mg/g respectively compared to others linearized forms. CONCLUSION: In summary, the effect of linear forms used either in the medellization of isotherms or kinetic data is significant in the prediction of adsorption parameters, also brewery waste has a significant B-Y dye adsorption affinity compared to others dyes, the descending order of maximum adsorption capacity finding is: qe = 209 mg/g for B-Y, qe = 152 mg/g for B-R and finally qe = 108 mg/g for B-B.

Extended Rate Constants Distribution (RCD) Model for Sorption in Heterogeneous Systems: 2. Importance of Diffusion Limitations for Sorption Kinetics on Cryogels in Batch.

Here we address the problem of what we can expect from investigations of sorption kinetics on cryogel beads in batch. Does macroporosity of beads indeed help eliminate diffusion limitations under static sorption conditions? Are sorption rate constants calculated using phenomenological kinetic models helpful for predicting sorption properties under dynamic conditions? Applying the rate constants distribution (RCD) model to kinetic curves of Cu(II) ions sorption on polyethyleneimine (PEI) cryogel and gel beads and fines, we have shown that diffusion limitations in highly swollen beads are very important and result in at least ten-fold underestimation of the sorption rate constants. To account for intraparticle diffusion, we have developed the RCD-diffusion model, which yields "intrinsic" kinetic parameters for the sorbents, even if diffusion limitations were important in kinetic experiments. We have shown that introduction of a new variable-characteristic diffusion time-to the RCD model significantly improved the reliability of sorption kinetic parameters and allowed prediction of the minimal residence time in column required for efficient uptake of the adsorbate under dynamic conditions. The minimal residence time determined from kinetic curves simulated using the RCD-diffusion model was in good agreement with experimental data on breakthrough curves of Cu(II) ion sorption on monolith PEI cryogel at different flow rates.

Phosphorus removal from secondary wastewater effluent using copper smelter slag.

This study investigated the use of copper smelter slag for the removal of phosphorus from secondary wastewater effluent through batch tests. The media was physically and chemically characterized and showed presence of Fe2O3 (45.22%), SiO2 (14.98%), Al2O3 (3.21%), CaO (1.99%), SO3 (1.77%) and MgO (1.33%). Scanning electron microscopy monographs revealed smooth and flat surface and no heterogeneity on the surface of the slag with visible micro pores before the experiment and less visible after the experiment. The point of zero charge of the media was 5.0. Equilibrium was reached after 4 h at 29.5 ± 0.71% phosphorus removal efficiency and media dosage of 0.4/100 mL. The kinetic data was best described by Pseudo second order equation. More than one mechanisms were involved in the adsorption of phosphorus onto copper smelter slag as suggested by multi-linearity of intra particle diffusion model. Ninety seven percent (97.5 ± 0.0%) removal efficiency was achieved at an equilibrium dosage of 160 gL-1. The equilibrium isotherm was described better by Langmuir equation with observed maximum adsorption capacity of 0.16 mg P g-1 media and the experimental maximum adsorption capacity was 0.26 mg P g-1 media. Regeneration studies showed low performance with maximum efficiency of 11.7% revealed during the first regeneration trial therefore low practical benefits. Copper smelter slag is a poor adsorbent for phosphorus and further studies on the media should be conducted.