Kinetics of endosulfan sorption on to wood charcoal

Abstract

A part of the research work conducted to evaluate the efficiency of a locally available low cost wood charcoal in removing endosulfan, an organochlorine insecticide, has been presented here in this paper. In the batch experiments conducted at 1 mg/I initial concentration of endosulfan, it was found that wood charcoal could remove endosulfan from water up to 95%. Kinetic profiles were developed for various conditions and they followed second order kinetic reactions. Adsorption equilibrium time was determined by two different approaches namely rough estimate and 2% slope criteria. The equilibrium time was found to be 5 hrs. Forward, reverse, and overall reaction rate constants were determined by approximating the kinetic data to the first order reversible kinetic model. Rate constants increased with increasing initial concentration of endosulfan. Rate limiting process was determined by using kinetics data and further confirmed by the multiple interruption test. Pore and film diffusion coefficients were determined from the half time equations. Film diffusion appeared to be the rate limiting which was further supported by the multiple interruption test.     

Diffusion mechanism of lindane into wood charcoal

Abstract

The wood charcoal treated by 1N HNO₃ (WCT) was used to remove toxic chlorinated pesticide lindane (y‐HCH) residue from water by the sorption process. Using a simple first order reversible kinetics constants and half time equations, the film and pore diffusion coefficients were determined. Film diffusion was found to be rate limiting step in sorbing lindane by WCT. This was further authenticated by kinetics studies at different initial sorbate concentrations, different sorbent sizes, and different agitation speeds besides interruption test. A pore diffusion model was used to fit the data of kinetics in continuously mixed batch reactors (CMBR), and the tortuosity, external resistance, and surface diffusion effects on lindane sorption by WCT were noticed. The tortuosity values of 15 to 28 were obtained for WCT‐lindane system.     

Removal of lignin and tannin colour from aqueous solution by adsorption onto activated charcoal

Sorptive uptake of lignin and tannin from an aqueous phase by activated charcoal was investigated in the laboratory. The sorption reaction was found to be of a first order. The influence on the rate of sorption of various factors, such as amount of sorbent and pH of the system, have been investigated. Sorption data fit well into the Langmuir adsorption isotherm, indicating formation of a monolayer over a homogeneous sorbent surface. Sorption capacity, rate constant, intraparticle diffusion coefficient, etc. were calculated from the sorption data. Desorption studies indicate the irreversible nature of the sorption reaction, whereas interruption studies suggest film diffusion to be rate limiting.     

Removal of perfluorinated surfactants by sorption onto granular activated carbon, zeolite and sludge

Perfluorinated surfactants are emerging pollutants of increasing public health and environmental concern due to recent reports of their world-wide distribution, environmental persistence and bioaccumulation potential. Treatment methods for the removal of anionic perfluorochemical (PFC) surfactants from industrial effluents are needed to minimize the environmental release of these pollutants. Removal of PFC surfactants from aqueous solutions by sorption onto various types of granular activated carbon was investigated. Three anionic PFC surfactants, i.e., perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonate (PFBS), were evaluated for the ability to adsorb onto activated carbon. Additionally, the sorptive capacity of zeolites and sludge for PFOS was compared to that of granular activated carbon. Adsorption isotherms were determined at constant ionic strength in a pH 7.2 phosphate buffer at 30 degrees C. Sorption of PFOS onto activated carbon was stronger than PFOA and PFBS, suggesting that the length of the fluorocarbon chain and the nature of the functional group influenced sorption of the anionic surfactants. Among all adsorbents evaluated in this study, activated carbon (Freundlich K(F) values=36.7-60.9) showed the highest affinity for PFOS at low aqueous equilibrium concentrations, followed by the hydrophobic, high-silica zeolite NaY (Si/Al 80, K(F)=31.8), and anaerobic sludge (K(F)=0.95-1.85). Activated carbon also displayed a superior sorptive capacity at high soluble concentrations of the surfactant (up to 80 mg l(-1)). These findings indicate that activated carbon adsorption is a promising treatment technique for the removal of PFOS from dilute aqueous streams.     

Removal of endosulfan using aerobic mixed bacterial culture

With the increasing use of pesticides in modern agriculture, increased evidence of their disastrous effects on the environment has been noticed. Pesticides applied in various modes and places contaminate various parts of the environment, including groundwater sources. As pesticide problems are greater in the rural areas, the authors have developed a successful low-cost technology for rural areas with wood charcoal treated with nitric acid. As pesticides are classified as hazardous waste, the sludge resulting from their treatment has to be disposed off safely. This paper describes the removal of pesticides at a higher concentration of 24 mg/l, using a mixed culture of aerobic bacteria, and also a study of the inhibiting action of endosulfan on bacterial cells. It was found that bacteria without acclimatisation could remove 89.7% of endosulfan, and with prior acclimatisation the efficiency was 96%. It was found that removal in the initial phase is because of the hydrophobic nature of endosulfan and its affinity to sediments. The adsorbed endosulfan subsequently undergoes biotransformation, which has been confirmed by monitoring endosulfan concentrations in the bacterial sludge. Transformation was found to be significant in the acclimatised culture system. The fluctuation in bacterial performance was greater at lower concentrations of endosulfan, and overall inhibition was greater at higher concentrations.     

Impacts of charcoal characteristics on sorption of polycyclic aromatic hydrocarbons

Sorption of three polycyclic aromatic hydrocarbons (PAHs, phenanthrene, anthracene and pyrene) on three charcoals and their precursor substance (sawdust) was studied. The charcoals obtained by heating at 400 °C for different periods were different in chemical composition and structure. Sorption characteristics were described by a Polanyi–Dubinin–Manes model combined with poly-parameter linear free energy relationships. The results revealed that though partition could not be neglected for sawdust and charcoal containing large sawdust residue, adsorption controlled the sorption of PAHs on matured charcoals, where π–π electron donor–acceptor (EDA) exerted as the main molecular-scale interactions. Charring elevated partition coefficients (K_oc) of the three PAHs more than one order of magnitude, which ranged from 10^5.74 to 10^6.58 on charcoals (for PAHs at equilibrium concentration C_e = 0.005S_w). Adsorption increased with the aromaticity of the charcoals, however, polar aromatic structure may stimulate sorption of PAHs due to the presence of π–π EDA interactions.     

Multi-component sorption isotherms of basic dyes onto peat

The adsorption of basic dyes onto peat from single component and multi-component solution is reported. The adsorption is presented in the form of the equilibrium isotherms. The Freundlich, Langmuir and Redlich-Peterson isotherm equations are fitted to the results and the isotherm constants obtained.     

pH dependence of ferrous sorption onto two smectite clays

This work examines the abilities of two smectite minerals (SWa-1 and Wyoming montmorillonite) to adsorb ferrous iron at concentrations from 0.037 mM (2 ppm) to 2.5 mM (240 ppm) over a range of pHs from 4.0 to 8.0. Both sorption isotherm and sorption edge data are presented. Ferrous sorption (Fe(aq)2+ = 0.1 mM) to both SWa-1 and Wyoming montmorillonite over the pH range 4.0-6.75 is relatively constant at approximately 1000 l kg(-1) for both minerals. Sorption in this pH range is attributed to the cation exchange capacity of the clay along the basal surfaces. At pH values above 6.75 the amount of ferrous iron sorbed increases dramatically. At pH 8, sorption (Fe(aq)+ = 0.1 mM) reaches 6600 l kg(-1) and 8000 l kg(-1) for Swa-1 and Wyoming montmorillonite respectively. This is attributed to the specific interaction between ferrous ions and surface sites along mineral edges. The overriding geochemical implication is that in reduced sediments containing more than a few percent clay, the pool of sorbed ferrous iron is vast. This pool of reduced iron is both redox labile and bio-available and is not readily indicated by simple measurement of dissolved Fe2+.     

Fe/Mg负载改性竹炭去除水中的氨氮

用MgCl2溶液、FeCl3溶液浸渍对竹炭进行改性,以BET比表面积和SEM-EDS对其进行表征。通过静态吸附实验,研究改性竹炭对氨氮的吸附特性以及吸附时间、初始氨氮浓度、pH值和磷存在等因素对改性竹炭吸附氨氮能力的影响。实验表明,用氯化镁和氯化铁对竹炭进行改性,可使竹炭表面化学性质和物理结构特性同时发生变化;未改性竹炭与改性竹炭对氨氮的吸附量大小依次为:BC< MBC< FBC< FMBC;竹炭在吸附时间为24 h时基本达到吸附平衡,吸附过程符合准二级动力学方程;改性竹炭对氨氮的吸附等温方程与Freundlich模型拟合较好;改性竹炭对氨氮吸附的最佳pH为5;磷存在可使改性竹炭对氨氮的吸附量显著增加。     

Cadmium ion sorption onto lignocellulosic biosorbent modified by sulfonation: the origin of sorption capacity improvement

Juniper (Juniperus monosperma), a small-diameter underutilized material, has been studied as a lignocellulosic biosorbent for removing heavy metals from water. In this study, juniper wood was modified by sulfonation to enhance sorption capacity for cadmium in water. The origin of the enhancement was investigated by observing the sorption behaviors and the change in surface functional group concentrations. Cadmium sorption by all juniper wood biosorbents studied was fast and the sorption capacity decreased with decreasing pH, similar to results found for other biosorbents. Sulfonated juniper was found to have at least twice the sorption capacity for cadmium removal from water compared to that of untreated juniper, though the sorption capacity increased with increasing pH. A slight increase in carboxylate content after sulfonation was likely responsible for a small portion of the enhancement. Elemental analysis showed an increase in sulfur content after sulfonation. Diffuse reflectance infrared Fourier transform (DRIFT) spectra showed a decrease in the band at 1660 cm(-1) in the range of carbonyl groups as a result of sulfonation. This indicates that coniferaldehyde groups in the lignin of juniper wood corresponding to this band were substituted into sulfonic acid groups after sulfonation. This interpretation was supported by both the color forming reaction with phloroglucinol-hydrochloric acid and the reaction mechanisms from the acid sulfite pulping process. Consequently, the enhancement of cadmium sorption capacity of juniper wood by sulfonation mainly originated from the production of sulfonic acid groups, which are binding sites for heavy metals.     

Characteristics of sorption losses of polychlorinated biphenyl congeners onto glass surfaces

Sorption losses to glass surfaces of five polychlorinated biphenyl (PCB) congeners in aqueous solutions were investigated. Adsorption/desorption experiments were conducted under conditions that simulated actual sample handling procedures for environmental samples. It was found that the adsorption loss is related to the degree of chlorination. PCB congener 180 lost the most onto glass surfaces, followed by congeners 138, 101/28, and 52, in decreasing order. More PCB adsorption occurred onto glass under conditions of agitation and higher temperature (22°C) during the five-day experimental period. The salinity effect (“salting out effect”) was also observed in this work. The efficiency of desorption (rinsing three times with solvent) was found to be ineffective in extracting adsorbed PCBs. It was necessary to use mechanical shaking for extraction. Storage of samples up to five days resulted in sorption losses as much as 30%, 17%, 30%, 40%, and 55% of PCB 28, 52, 101, 138, and 180, respectively. Sorption losses need to be considered when conducting water sampling or toxicological studies to avoid underestimation of the actual PCB concentrations and their toxic effects.     

Landfill leachate effects on sorption of organic micropollutants onto aquifer materials

The effect of dissolved organic carbon as present in landfill leachate, on the sorption of organic micropollutants in aquifer materials was studied by laboratory batch and column experiments involving 15 non-polar organic chemicals, 5 landfill leachates and 4 aquifer materials of low organic carbon content. The experiments showed that hydrophobic organic micropollutants do partition into dissolved organic carbon found in landfill leachate potentially increasing their mobility. However, landfill leachate interacted with aquifer materials apparently increases the sorbent affinity for the hydrophobic micropollutants. The combination of these two mechanisms affected the observed distribution coefficients within a factor of two, in some cases increasing and in other cases decreasing the sorption of the chemicals. No means for prediction of the effect is currently available, but from a practical point of view, the effect of landfill leachate on retardation of organic micropollutants in aquifer material seems limited.     

The sorption of PAH onto dissolved organic matter in Lake Michigan waters

The polynuclear aromatic hydrocarbons are hydrophobic organic contaminants (HOC) that associate with dissolved organic matter (DOM) in natural water systems. The DOM-HOC complex is sufficiently stable to allow measurement of an association constant, K_B. For individual HOC in different natural waters, K_B ranges over two orders of magnitude. Our results show that the K_B is more dependent on the source of the DOM than the water solubility of the HOC but that for a specific water sample, correlation of K_B with solubility does exist.     

Chemical and biological characterization of emissions from small residential stoves burning wood and charcoal

Emissions from a small residential wood stove and a newly developed residential stove burning charcoal have been characterized by chemical analysis and mutagenicity testing (Ames Salmonella test). For wood burning the samples were taken under normal and starved air conditions burning birch and spruce separately. The burning conditions in the stove seemed to influence the emissions to a larger extent than the type of wood.The emissions of aldehydes, benzene and polycyclic aromatic hydrocarbons from the charcoal-burning stove are lower by a factor of 25–1000 as compared to the wood stove. The mutagenicity of the emissions showed a similar trend.     

Removal of aqueous-phase polynuclear aromatic hydrocarbons using aspen wood fibers

Roadway runoff derived polynuclear aromatic hydrocarbons (PAHs) impact the quality of surface and ground water. Inexpensive aspen wood fibers have been investigated as a means to remove dissolved PAH under laboratory conditions. Our isotherm experiments demonstrated that the uptake of naphthalene, fluorene, anthracene, and pyrene required up to 12.5 days to reach equilibrium. Aspen wood-water sorption coefficients, Kww, were linearly correlated to octanol-water partition coefficients and the molecular weight of the studied PAH compounds. The correlation between Kww and molecular weight was the most significant. Column experiments were carried out to study the sorption and desorption of fluorene, anthracene, and pyrene under dynamic conditions. The results indicate linear sorption, but non-linear desorption behavior. The degree of desorption was inversely correlated to a compound's hydrophobicity. Flow interruption experiments showed that sorption and desorption was rate limited. A mass balance of the sorption and desorption tests indicated that sorptive uptake exceeded desorptive release over a given number of pore volumes. Further, absolute mass-removal efficiency increased with the molecular weight and hydrophobicity of the PAH compound. Batch and column studies demonstrated that aspen wood has the potential to become an effective remedial agent for PAH in stormwater runoff or other PAH contaminated waters.     

Single-solute and bi-solute sorption of phenanthrene and pyrene onto pine needle cuticular fractions

To better understand interaction mechanisms of pine needles with persistent organic pollutants, single-solute and bi-solute sorption of phenanthrene and pyrene onto isolated cuticular fractions of pine needle were investigated. The structures of cuticular fractions were characterized by elemental analysis, Fourier transform infrared spectroscopy and solid-state ¹³C NMR. Polymeric lipids (cutin and cutan) exhibited notably higher sorption capabilities than the soluble lipids (waxes), while cellulose showed little affinity with sorbates. With the coexistence of the amorphous cellulose, the sorption of cutan (aromatic core) was completely inhibited, so the cutin components (nonpolar aliphatic moieties) dominated the sorption of bulk needle cuticle. By the consumption of the amorphous cellulose under acid hydrolysis, sorption capacities of the de-sugared fractions were dramatically enhanced, which controlled by the exposed aromatic cores and the aliphatic moieties. Furthermore, the de-sugared fractions demonstrated nonlinear and competitive sorption due to the specific interaction between aromatic cores and polycyclic aromatic hydrocarbon.     

竹炭吸附对硝基苯胺的过程与机理研究

研究了竹炭吸附对硝基苯胺的过程影响因子以及吸附过程的动力学、等温线和热力学。结果表明,粒径80~100目的竹炭即可实现对对硝基苯胺的高效吸附,吸附效率为95.65%。竹炭对硝基苯胺的吸附效率随溶液pH值的升高而逐渐下降,当溶液pH值超过7.0以后,下降趋势明显加快,实验条件下,溶液pH=2.0可以获得最佳吸附效果,吸附效率为95.85%,静电作用力和氢键作用力在不同溶液pH值下变化的联合作用是造成吸附效率变化的主要原因。吸附动力学研究结果表明：准二级吸附动力学模型可以很好的拟合3种不同温度下的吸附速率数据;吸附等温线研究结果表明,Redlich-Peterson吸附等温线模型可以很好的拟合3种不同温度下的吸附等温线数据,说明吸附过程兼有单分子层吸附和吸附表面异质性的特点;吸附热力学计算结果表明,吉布斯自由能ΔG0小于零,说明竹炭吸附对硝基苯胺的过程可以自发进行,吸附焓变ΔH0小于零,说明吸附反应为放热过程,并且吸附焓变数值大于单纯由范德华力引起的吸附放热范围,说明吸附过程中存在多种作用力;吸附熵变ΔS0大于零,说明吸附过程中体系的混乱度显著增大。     

pH和温度对2,2’,4,4’-四溴联苯醚在土壤中吸附和解吸行为的影响研究

研究了pH和温度对2,2’,4,4’-四溴联苯醚(BDE-47)在土壤中的吸附和解吸行为的影响。结果表明,pH和温度都可以影响BDE-47在受试土壤中的吸附和解吸行为。pH升高或降低均会使土壤对BDE-47的吸附能力提高,且在碱性环境中提高的程度更大;酸性或碱性条件下BDE-47在土壤中的解吸滞后性显著增强。温度降低后,土壤对BDE-47的吸附能力提高,5℃时的单点分配系数(Kd,表征土壤对BDE-47的吸附能力)是25℃时的1.03~1.67倍;温度由25℃降低到5℃后,BDE-47在土壤中的解吸滞后性增强。     

Nonequilibrium sorption of phenols onto geosorbents: the impact of pH on intraparticle mass transfer

While the pH effect on sorption equilibrium of weak acids on natural sorbents was investigated in a number of studies, less is known about the pH dependence of sorption kinetics. This paper investigates the impact of pH on sorption kinetics during the transport of some selected phenols through a sandy aquifer material. Breakthrough curves measured in column experiments were analyzed using a mass transfer based nonequilibrium model designated as dispersed flow, film and particle diffusion model (DF-FPDM). In this model, the rate limiting intraparticle diffusion is characterized by the mass transfer coefficient, kSaV, which can be determined from breakthrough curves by curve fitting. The experimental results indicate that the kSaV is pH-dependent and inversely correlated with the pH-dependent distribution coefficient, K(d,app). Regression equations are presented that may be used to estimate approximate values of intraparticle mass transfer coefficients on the basis of experimentally determined or LFER predicted distribution coefficients.     

The mechanism of chromate sorption by three variable charge soils

Adsorption of chromate and desorption of the pre-adsorbed chromate were studied using three representative variable charge soils from the south of China. The mechanisms of the adsorption were discussed based on the hydroxyl release and the change of zeta potential during the chromate adsorption. The adsorption and desorption of chromate followed the same order: the Hyper-Rhodic Ferralsol>the Rhodic Ferralsol>the Haplic Acrisol. The adsorption and the desorption both increased with elevation of the equilibrium chromate concentration and decreased with increasing of the soil solution pH. The percentage of the specific adsorption of chromate was 54.0-59.4%, 54.3-60.3%, and 43.9-46.2% for the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol, and the Haplic Acrisol, respectively; the percentage of the electrostatic adsorption was 40.0-46.6%, 39.7-45.8%, and 50.8-56.5% for the three soils, respectively. These findings suggest that both the specific adsorption and the electrostatic adsorption contributed to the chromate adsorption by the variable charge soils. The hydroxyl release during the chromate adsorption shared the same trend with the adsorption envelopes, and decreased with increasing of pH. This is attributed to the exchange of chromate with the hydroxyl on the soil particle surfaces and the formation of a chemical bond between chromate and the surface. Our results indicate that the adsorption of chromate resulted in a shift of zeta potential-pH curves of the soil colloids to negative values, which suggests that the adsorption increased the negative surface charge and decreased the surface potential of the soil colloids.