Simplification of the IAST for activated carbon adsorption of trace organic compounds from natural water

Recent studies have shown that the ideal adsorbed solution theory (IAST) coupled with the concept of equivalent background compound (EBC) can be simplified for describing trace organic compound adsorption from natural water, provided that the adsorbent surface loading is dominated by competing natural organic matter. The resulting simplified IAST has been used to reduce the complexity of kinetic models for various dynamic adsorption processes. In order to be correctly applied, however, the simplified IAST requires some additional clarification and a quantitative evaluation of the deviation caused by the simplifying assumption. In this study, we derive a simple equation that relates the relative deviation of the simplified IAST directly to the molar ratio of EBC and trace organic compound surface loadings and their Freundlich isotherm exponents. We then verify the simplified IAST using the original IAST and experimental isotherm data from the literature for trace organic compounds at various initial concentrations in natural water. By further assuming that the adsorbed amount of the EBC is substantially greater than what remains in solution, a new pseudo single-solute isotherm equation is derived and a simple relation is subsequently established between the carbon dose and the remaining trace compound concentration. The results show that the adsorption capacity and relative removal of a trace organic compound at any carbon dose can be estimated directly with the simple equations developed here and data from a single isotherm experiment for the target compound conducted in the natural water of interest.     

Adsorption from Brazilian soils of Cu(II) and Cd(II) using cattle manure vermicompost

The potential of cattle manure vermicompost and Brazilian soils (whole soils and soils incubated with vermicompost) was assessed for adsorption of heavy metals such as Cu(II) and Cd(II) from aqueous solutions. Experimental data have been fitted to Langmuir and Freundlich isotherms to obtain the characteristic parameters of each model, with R ² values from 0.89 to 0.99. Based on the maximum adsorption capacity obtained from the Langmuir isotherm the affinity of the studied metals for the vermicompost and soils have been established as Cu(II) > Cd(II). The values of the separation factor, R _L, which has been used to predict affinity between adsorbate and adsorbent were between zero and 1, indicating that sorption was very favourable for Cu(II) and Cd(II) in synthetic solution. Addition of vermicompost to soils resulted in higher distribution coefficient, K _d, as compared with whole soils. The thermodynamic parameter, the Gibbs energy changes, was calculated for each system and the negative values obtained confirm that the adsorption processes are spontaneous. The ΔG° values for the substrates were between ?2.630±1.41 kJ mol^?1 and ?13.700±1.250 kJ mol^?1. Adsorption tests from multimetal systems confirm the affinity order obtained in the individual metal tests. The adsorption capacity for Cu(II) measured in individual tests is not reduced by the presence of Cd(II). There is also desorption of Cu(II) and Cd(II) previously bound to vermicompost, whole soils and soils incubated with vermicompost by DTPA. The experiment indicates the importance of cattle manure vermicompost and oxisol amended with vermicompost in relation to Cu(II) and Cd(II) adsorption from aqueous solution.     

Pb(II)、Cu(II)、Cd(II)在黄土上二元竞争吸附特性研究

铅、铜、镉是3种具有代表性的重金属污染物,可用于模拟多重离子复合污染情况。研究了离子浓度、土水比等因素对3种元素在黄土上二元竞争吸附特性的影响。等温吸附模型Langmuir、Freundlich和D-R模型都能在一定程度上解释Pb(II)-Cu(II)、Pb(II)-Cd(II)、Cu(II)-Cd(II)在黄土上的竞争吸附性能。黄土对Pb(II)、Cu(II)、Cd(II)的选择顺序为Pb(II)>Cu(II)>Cd(II)。相比单一吸附,黄土对每种离子的吸附容量均有不同程度的下降。溶液的初始浓度越大,3种离子在单位黄土上的最大吸附量也随之增大,吸附效率随之降低;适当增大土水比可提高离子的去除效率。试验结果为黄土作为防污屏障和污水处理材料提供了依据。     

Effect of natural organic matter on powdered activated carbon adsorption of trace contaminants: characteristics and mechanism of competitive adsorption

Batch adsorption experiments using powdered activated carbon (PAC) to remove trace synthetic organic chemicals (SOCs) from water containing natural organic matter (NOM) were conducted. The percentage of SOC removed at any contact time and at any PAC dose was observed to be independent of the initial SOC concentration. Equations derived from the ideal adsorbed solution theory and the pore surface diffusion model validated this observation. For the strongly adsorbing SOCs (simazine and simetryn), the percentage of SOC removed was independent only at low initial SOC concentrations. The NOM fraction competing with the weakly adsorbing SOC (asulam) constituted a larger percentage of the total NOM than that competing with the strongly adsorbing SOCs. Although the adsorptive capacities of the SOCs were greatly reduced in water containing NOM compared with those in pure water, the change in the pore diffusion coefficient was insignificant. Therefore, NOM competed with the SOCs for adsorption sites, reducing the adsorptive capacity, but the amount of NOM loading was not so severe that it blocked or filled the pores, hindering the internal diffusion of the SOCs.     

Comparative and competitive adsorption of Cu(II), Cd(II) and Pb(II) onto Sepia pharaonis endoskeleton biomass from aqueous solutions

In this research, the possibility of simultaneous removal of lead, cadmium and copper divalent ions from water samples through the use of Sepia pharaonis endoskeleton powder (SPEB) as bio‐material, was investigated. The bio‐sorbent was characterised by Fourier transform infrared spectrum (FT‐IR), atomic force microscopy (AFM) and X‐ray fluorescence (XRF). The different factors affecting the bio‐sorption process were studied. Langmuir and Freundlich isotherm models were applied to analyse the experimental data. The kinetic studies showed that the pseudo‐second order model kinetics were compatible with the investigated systems. It was found that under optimal conditions, this bio‐sorbent was efficient in the uptake of these heavy metal ions from both mono and multi‐metal solutions, and high removal percentages were achieved. This study verified the potential ability of SPEB as an efficient natural adsorbent for removal of Pb(II), Cd(II) and Cu(II) ions from river, tap and mineral water samples.     

Activated carbon adsorption of trichloroethylene (TCE) vapor stripped from TCE-contaminated water

Ground water contaminated with trichloroethylene (TCE) used in electronic, electric, dry cleaning and the like industries is often treated by air-stripping. In this treatment process, TCE in its vapor form is stripped from ground water by air stream and sometimes emitted into the atmosphere without any additional treatments. Activated carbon adsorption is one of the practical and useful processes for recovering the TCE vapor from the exhaust air stream. However, adsorption of the TCE vapor from the stripping air stream onto activated carbons is not so simple as that from dry air, since in the exhaust air stream the TCE vapor coexists with water vapor with relatively high concentrations. The understanding of the adsorption characteristics of the TCE vapor to be adsorbed on activated carbon in the water vapor-coexisting system is essential for successfully designing and operating the TCE recovery process. In this work, the adsorption equilibrium relations of the TCE vapor adsorption on activated carbons were elucidated as a function of various relative humidity. Activated carbon fibers (ACFs) were used as model activated carbon. The adsorption equilibrium relations were studied by the column adsorption method. The adsorption isotherms of TCE vapor adsorbed on sample ACFs were successfully correlated by the Dubinin-Radushkevich equation for both cases with and without coexistent water vapor. No effects of coexistent water vapor were found on the limiting adsorption volume. However, the adsorption characteristic energy was significantly reduced by the coexistence of water vapor and its reduction was successfully correlated with the equilibrium amount of water vapor adsorbed under the dynamic condition.     

An overall isotherm for activated carbon adsorption of dissolved natural organic matter in water

Design and analysis of activated carbon processes in water treatment often requires the adsorption isotherm for dissolved natural organic matter (NOM). Of the isotherm models available, the Summers and Roberts (SR) equation, capable of describing the adsorbent dose effect with the fewest parameters, has been successfully used to normalize NOM isotherm data. In this study, we show that the adsorbent dose in the SR equation can be eliminated as an intermediate variable and the initial concentration effect on NOM adsorption is then described explicitly. Comparing with the original SR equation, the derived isotherm equation is in a form more amenable to analysis. To ensure that the prediction is physically attainable, we introduced the limiting adsorption capacity by taking the adsorbent pore volume and size exclusion into consideration. Subsequently, we develop a simple relationship that can be used to determine the minimum adsorbent usage required for any desirable level of treatment. By comparing with extensive isotherm data previously published by Li et al. [2003a. Polydisperse adsorbability composition of several natural and synthetic organic matrices. J. Colloid Interface Sci. 265(2), 265-275], we demonstrated that the isotherm equation derived herein yields predictions that agree with the much more complicated fictive component-ideal adsorbed solution theory (IAST)-based model for NOM from different sources and over a range of initial concentrations.     

Immobilization of Hg(II) in water with polysulfide-rubber (PSR) polymer-coated activated carbon

An effective mercury removal method using polymer-coated activated carbon was studied for possible use in water treatment. In order to increase the affinity of activated carbon for mercury, a sulfur-rich compound, polysulfide-rubber (PSR) polymer, was effectively coated onto the activated carbon. The polymer was synthesized by condensation polymerization between sodium tetrasulfide and 1,2-dichloroethane in water. PSR-mercury interactions and Hg-S bonding were elucidated from x-ray photoelectron spectroscopy, and Fourier transform infra-red spectroscopy analyses. The sulfur loading levels were controlled by the polymer dose during the coating process and the total surface area of the activated carbon was maintained for the sulfur loading less than 2 wt%. Sorption kinetic studies showed that PSR-coated activated carbon facilitates fast reaction by providing a greater reactive surface area than PSR alone. High sulfur loading on activated carbon enhanced mercury adsorption contributing to a three orders of magnitude reduction in mercury concentration. μ-X-ray absorption near edge spectroscopic analyses of the mercury bound to activated carbon and to PSR on activated carbon suggests the chemical bond with mercury on the surface is a combination of Hg-Cl and Hg-S interaction. The pH effect on mercury removal and adsorption isotherm results indicate competition between protons and mercury for binding to sulfur at low pH.     

The effects of dissolved natural organic matter on the adsorption of synthetic organic chemicals by activated carbons and carbon nanotubes

Understanding the influence of natural organic matter (NOM) on synthetic organic contaminant (SOC) adsorption by carbon nanotubes (CNTs) is important for assessing the environmental implications of accidental CNT release and spill to natural waters, and their potential use as adsorbents in engineered systems. In this study, adsorption of two SOCs by three single-walled carbon nanotubes (SWNTs), one multi-walled carbon nanotube (MWNT), a microporous activated carbon fiber (ACF) [i.e., ACF10] and a bimodal porous granular activated carbon (GAC) [i.e., HD4000] was compared in the presence and absence of NOM. The NOM effect was found to depend strongly on the pore size distribution of carbons. Minimal NOM effect occurred on the macroporous MWNT, whereas severe NOM effects were observed on the microporous HD4000 and ACF10. Although the single-solute adsorption capacities of the SWNTs were much lower than those of HD4000, in the presence of NOM the SWNTs exhibited adsorption capacities similar to those of HD4000. Therefore, if released into natural waters, SWNTs can behave like an activated carbon, and will be able to adsorb, carry, and transfer SOCs to other systems. However, from an engineering application perspective, CNTs did not exhibit a major advantage, in terms of adsorption capacities, over the GAC and ACF. The NOM effect was also found to depend on molecular properties of SOCs. NOM competition was more severe on the adsorption of 2-phenylphenol, a nonplanar and hydrophilic SOC, than phenanthrene, a planar and hydrophobic SOC, tested in this study. In terms of surface chemistry, both adsorption affinity to SOCs and NOM effect on SOC adsorption were enhanced with increasing hydrophobicity of the SWNTs.     

Sorption of Zn(II), Pb(II), and Co(II) using natural sorbents: equilibrium and kinetic studies

Natural Jordanian sorbent (consisting of primary minerals, i.e., quartz and aluminosilicates and secondary minerals, i.e., calcite and dolomite) was shown to be effective for removing Zn(II), Pb(II) and Co(II) from aqueous solution. The major mineral constitutions of the sorbent are calcite and quartz. Dolomite was present as minor mineral and palygorskite was present as trace mineral. The sorbent has microporous structure with a modest surface area of 14.4 m(2)g(-1). pH(zpc) (pH of zero point charge) of the sorbent was estimated by alkaline-titration methods and a value of 9.5 was obtained. The sorption capacities of the metals were: 2.860, 0.320, 0.076 mmol cation g(-1) for Zn(II), Pb(II) and Co(II) at pH 6.5, 4.5 and 7.0, respectively. The shape of the experimental isotherm of Zn(II) was of a "L2" type, while that of Pb(II) and Co(II) was of a "L1" type according to Giles classification for isotherms. Sorption data of metals were described by Langmuir and Freundlich models over the entire concentration range. It was found that the mechanism of metal sorption was mainly due to precipitation of metal carbonate complexes. The overall sorption capacity decreased after acid treatment, as this decreased the extent of precipitation on calcite and dolomite. The effect of Zn(II) ions concentration on sorption kinetics was investigated. Kinetic data were accurately fitted to pseudo-first order and external diffusion models which indicated that sorption of Zn(II) occurred on the exterior surface of the sorbent and the contribution of internal diffusion mechanism was insignificant. Furthermore, the sorption rate of Zn(II) was found to be slow, where only 10-20% of the maximum capacity was utilized in the first 30 min of interaction.     

Removal of Cu(II) from aqueous solutions by adsorption process with anatase-type titanium dioxide

The experiment was performed in the reactor with suspended anatase-type titanium dioxide particles. The adsorption amount increased rapidly with an increasing pH value from pH 2 to 5 and remained constant over pH 5. The adsorption amount of Cu(2+) increased with temperature from 15 degrees C to 40 degrees C. The adsorption equilibrium constant (K(ads)) was 0.854 and adsorption isotherm of Cu(2+) adsorption on titanium dioxide was more suitable in Langmuir adsorption isotherm than in Freundlich isotherm. The adsorption rate was rapid with an increasing number of UV lamps of 254 nm.     

Elucidating competitive adsorption mechanisms of atrazine and NOM using model compounds

Based on the relative adsorbability of natural organic matter (NOM) fractions with different molecular weights (MWs), two model compounds, poly(styrene sulfonate) (PSS) (nominal MW=1800 Dalton) and p-dichlorobenzene (DCB), were chosen to study the competitive effect of large and small NOM molecules on atrazine adsorption by two powdered activated carbons (PACs) with different pore size distributions. Both isotherm and kinetic tests of atrazine adsorption were conducted using fresh PAC and PAC preloaded with the model compounds. The model compounds were found to affect atrazine adsorption through two different mechanisms due to their size difference: direct competition for sites by p-DCB and pore constriction/blockage by PSS-1.8k. p-DCB was found to significantly reduce atrazine adsorption capacity but to have no effect on atrazine adsorption kinetics. In contrast, the effect of PSS-1.8k on atrazine adsorption capacity was very small. Furthermore, during simultaneous adsorption, PSS-1.8k had no effect on atrazine surface diffusion. However, preloading PAC with PSS-1.8k lowered the atrazine surface diffusion coefficient, D(s), by more than three orders of magnitude; D(s) decreased with increasing solid phase PSS-1.8k concentration. The pore size distribution of the PAC was found to play an important role in competitive adsorption. A high mesopore surface area could alleviate pore blockage significantly.     

Removal of zinc, copper and lead by natural zeolite-a comparison of adsorption isotherms

An uptake of zinc (Zn), copper (Cu), and lead (Pb) from aqueous solutions by ion exchange on natural zeolitic tuff has been studied. The Croatian zeolite clinoptilolite from the Donje Jesenje deposit has been used as a natural ion exchanger. The efficiency of removal is higher for Pb and Cu than for Zn ions. Measured concentrations of Si in the liquid phase identify the detachment of the aluminosilicate structure during ion exchange in the presence of H(+) and OH(-) ions. The adsorption isotherm equations; Langmuir-Freundlich, Redlich-Petersen, Toth, Dubinin-Radushkevich, modified Dubinin-Radushkevich, and Lineweawer-Burk were derived from the basic empirical equations, and used for calculation of ion exchange parameters. The best fitting of experimental results to the proposed isotherms was observed in models that assume that ionic species bind first at energetically most favorable sites, with multi-layer adsorption taking place subsequently.     

Application of a three-component competitive adsorption model to evaluate and optimize granular activated carbon systems

A recently developed kinetic model for granular activated carbon (GAC) adsorbers (COMPSORB-GAC) that quantitatively describes the adsorption of trace organic contaminant in the presence of competing natural organic matter (NOM) was applied to evaluate the performance of different GAC system configurations: conventional fixed-bed adsorbers, layered upflow carbon adsorbers (LUCA), and moving-bed adsorbers (with few or many bed sections). COMPSORB-GAC separately tracks the adsorption of three components: a trace compound, a strongly competing NOM fraction that reduces trace compound equilibrium capacity, and a pore-blocking NOM fraction that reduces kinetics. Performance was simulated for various design criteria and with model parameters derived for two natural waters with significantly different NOM concentrations. For the range of simulated conditions and with baseline performance defined by a fixed-bed adsorber, LUCA generally reduced carbon usage rates (CURs) by 15-35%. A 2-section and a 16-section moving-bed reactor reduced baseline CURs by 20-30% and 45-55%, respectively. Projected CURs for the water source with a relatively high NOM concentration were 2-3 times higher for all reactor configurations and indicated that NOM preloading would cause performance deterioration in deep GAC beds, which highlights the importance of source water quality. These results show how COMPSORB-GAC can be used in a comprehensive, site-specific optimization of GAC systems to ensure robust system performance and to balance capital and operating costs.     

Chromate (CrO(4)(2-)) and copper (Cu2+) adsorption by dual-functional ion exchange resins made from agricultural by-products

Ion exchange resins commonly have a single functionality for either cations or anions. Resins that have a dual functionality for both cations and anions are uncommon. The objective of this study was to create dual-functional ion exchange resins derived from soybean hulls, sugarcane bagasse and corn stover. Dual-functional resins were prepared by two separate two-step processes. In the first two-step process, by-products were reacted with a solution of citric acid in order to impart additional negative charge, and then reacted with the cross-linking reagent dimethyloldihydroxyethylene urea (DMDHEU) and a quaternary amine (choline chloride) to add positive charge to the lignocellulosic material. In the second two-step process, the order of reaction was reversed, with positive charge added first, followed by the addition of negative charge. These combined reactions added both cationic and anionic character to the by-products as evidenced by the increased removal from solution of copper (Cu(2+)) cation and the chromate (CrO(4)(2-)) anion compared to unmodified by-products. The order of reaction appeared to slightly favor the functionality that was added last. That is, if negative charge was added last, the resulting resin sequestered more copper ion than a comparable resin where the negative charge was added first and vice-versa. Cu(2+) and CrO(4)(2-) were used as marker ions in a solution that contained both competing cations and anions. The dual-functional resins adsorbed as much as or more of the marker ions compared to commercial cation or anion exchange resins used for comparison. None of the commercial resins exhibited dual-functional properties to the same extent as the by-product-based resins.     

Enhanced adsorption of Cd (II) on a hydrous Al (III) floc in the presence of a modified form of polyethylenimine

A polymer modified with succinic anhydride has been investigated for the adsorption of cadmium (II) on a freshly precipitated aluminium (III) hydroxide floc. The proportion of chelate attached to the polymer is varied to determine the relationship between carboxyl and amino groups on the polyelectrolyte, in terms of enhanced adsorption of cadmium (II) on a hydrous aluminium floc. The presence of polyelectrolyte enhanced the adsorption of 3.3 ppm Cd (II) on a 333 ppm Al (III) floc at every concentration of polyelectrolyte investigated. The proportion of succinic anhydride attached to the polymer had an impact on the increased adsorption of Cd (II) on an Al (III) floc observed. A decreasing proportion of succinic anhydride to polymer resulted in a decrease in the amount of cadmium adsorbed on the floc. Above pH 8, a decrease in the % Cd (II) adsorbed on the floc and % Al (III) retained within the floc decreases with the presence of polyelectrolyte as a result of the formation of soluble Cd-Polyethylenimine-succinic acid (PEISA) complexes. When the Al-PEISA combination was applied to a complex matrix where Cd (II), Cu (II) and Ni (II) ions competed for adsorption, enhanced adsorption was observed for Cd (II) and Ni (II). At pH 7, dissolution of the floc observed with the addition of discrete chelates was not observed with the addition of polyelectrolytes.     

Adsorption of Cu(II), Cd(II) and Pb(II) from aqueous single metal solutions by succinylated twice-mercerized sugarcane bagasse functionalized with triethylenetetramine

This study describes the preparation of two new chelating materials, MMSCB 3 and 5, derived from succinylated twice-mercerized sugarcane bagasse (MMSCB 1). MMSCB 3 and 5 were synthesized from MMSCB 1 using two different methods as described by Gurgel and Gil (2009). In the first method MMSCB 1 was activated with 1,3-diisopropylcarbodiimide and in the second with acetic anhydride (to form an internal anhydride) and later both were reacted with triethylenetetramine in order to obtain MMSCB 3 and 5. New obtained materials were characterized by mass percent gain, concentration of amine groups, FTIR, and elemental analysis. MMSCB 3 and 5 showed mass percent gain of 19.9 and 57.1%, concentration of amine groups of 2.0 and 2.1 mmol/g, and nitrogen content of 5.8 and 4.4%. The capacity of MMSCB 3 and 5 to adsorb Cu²⁺, Cd²⁺, and Pb²⁺ from aqueous single metal ion solutions was evaluated at different contact times, pHs, and initial metal ion concentrations. Adsorption isotherms were well fitted by Langmuir model. Maximum adsorption capacities of MMSCB 3 and 5 for Cu²⁺, Cd²⁺, and Pb²⁺ were found to be 59.5 and 69.4, 86.2 and 106.4, 158.7 and 222.2 mg/g, respectively.     

Sorption kinetics of Fe(II), Zn(II), Co(II), Ni(II), Cd(II), and Fe(II)/Me(II) onto hematite

The reactions of Fe(II) and other divalent metal ions including Zn, Co, Ni, and Cd on hematite were studied in single and competitive binary systems with high sorbate/sorbent ratios in 10 mM PIPES (pH 6.8) solution under strict anoxic conditions. Adsorbed Me(II) was defined as extractable by 0.5 N HCl within 20 h, and fixed Me(II) was defined as the additional amount that was extracted by 3.0 N HCl within 7 days. Binary systems contained Fe(II) plus a second metal ion. The extent of uptake of divalent metal ions by hematite was in order of Fe> or =Zn>Co> or =Ni>Cd. For all metals tested, there was an instantaneous adsorption followed by a relatively slow stage that continued for the next 1-5 days. This sequence occurred in both single and binary systems, and could have been due to a variety of sorption site types or due to slow conversion from outer- to inner-sphere surface complexes due to increasing surface charge. Sorption competition was observed between Fe(II) and the other metal ions. The displacement of Fe(II) by Me(II) was in order of Ni approximately Zn>Cd, and the displacement of Me(II) by Fe(II) was in order of Cd>Zn approximately Ni>Co. Fixed Fe(II) was in order of Fe+Co (20%)>Fe+Cd (6%)>Fe approximately Zn (4%)>Fe approximately Ni (4%) after 30 days. There was no fixation for the other metals in single or binary systems.     

Removal of Co(II), Ni(II) and Cd(II) from Aqueous Solutions by Magnetic Sorbents

The possibility of using magnetic sorbents for the removal of Co(II), Ni(II) and Cd(II) from water media is shown. It was established that magnetite is more effective compared with magnetic potassium–zinc hexacyanoferrate(II). The pH (> 4) and the dose of sorbents were defined for obtaining maximum possible degree of removing ions of specified metals from water media.     

Removal of Cu(II) and Cd(II) from aqueous solution by seafood processing waste sludge

Dried waste slurry generated in seafood processing factories has been shown to be an effective adsorbent for the removal of heavy metals from dilute solutions. Characterization of the sludge surface with scanning electron microscope and X-ray microanalyzer were carried out to evaluate the components on the sludge surface that are related to the adsorption of metal ions. Aluminum and calcium, as well as organic carbon are distributed on the surface of sludge. Alkalimetric titration was used to characterize the surface acidity of the sludge sample. The surface acidity constants, pKa1s and pKa2s, were 5.80 and 9.55, respectively. Batch as well as dynamic adsorption studies were conducted with 10(-5) to 5 x 10(-3) M Cu(II) and Cd(II). A surface complexation model with the diffuse layer model successfully predicted Cu(II) and Cd(II) removals in single metal solutions. Predictions of sorption in binary-adsorbate systems based on single-adsorbate data fits represented competitive sorption data reasonably well over a wide range of conditions. The breakthrough capacity found from column studies was different for each metal ion and the data reflect the order of metal affinity for the adsorbent material very well.