Application of agricultural fibers in pollution removal from aqueous solution

Discharging different kinds of wastewater and polluted waters such as domestic, industrial and agricultural wastewaters into environment, especially to surface water, can cause heavy pollution of this body sources. With regard to increasing effluent discharge standards to the environment, high considerations should be made when selecting proper treatment processes. Any of chemical, biological and physical treatment processes have its own advantages and disadvantages. It should be kept in mind that economical aspects are important, too. In addition, employing environment-friendly methods for treatment is emphasized much more these days. Application of some waste products that could help in this regard, in addition to reuse of these waste materials, can be an advantage. Agricultural fibers are agricultural wastes and are generated in high amounts. The majority of such materials is generated in developing countries and, since they are very cheap, they can be employed as biosorbents in water and wastewater applications. Polluted surface waters, different wastewaters and partially treated wastewater may be contaminated by heavy metals or some organic matters and these waters should be treated to reduce pollution. The results of investigations show high efficiency of agricultural fibers in heavy metal and phenol removal. In this paper, some studies conducted by the author of this article and other investigators are reviewed.     

Biological nitrate removal from water resources

During the recent decades, the increasing trends in nitrate ion concentration in ground water sources have meant more research to find effective procedures for the prevention of even more water contamination by nitrogen sources. In this study a pilot was designed to examine the application of biological method for eliminating nitrate from the water of well No.903 of Mehrabad Airport, Tehran, Iran. Design, installation and running processes were done from April to November 2003. A fixed biological bed containing five-centimeter trunk pipes 16 mm in diameter were installed in the reactor and the system was operated with upflow current. Instead of Methanol, Acetic acid was used as the carbon source because of its easier acceptance by the public, lower price and availability as well as easier storage. The pilot was run in different hydraulic retention times from 48 h up to one hour. Considering economical, operational and maintenance factors, retention time of 2 h was determined to be optimum, in which 77% nitrate removal was achieved. Considering a ratio of 2 for COD/N, inlet COD of about 140 mg/L and the optimum retention time, COD removal of about 80% is also accomplished in this process. The amount of nitrite concentration, pH values, COD and turbidity is also evaluated versus different hydraulic retention times.     

方解石负载羟基磷灰石复合材料去除水中铀离子的PRB活性介质研究

铀污染地下水分布于世界多国,其危害备受关注。本文基于溶胶-凝胶法制备方解石负载羟基磷灰石复合材料(CLHC),通过静态与动态对比试验,探讨了PRB活性介质对水中铀离子的吸附机理和去除效果。试验结果表明,制备的CLHC表面被羟基磷灰石覆盖,对铀离子具有较强的吸附能力。当U的初浓度为5.0 mg/L、试验周期为2 h、溶液pH值为4、CLHC用量为0.5 g/L时,CLHC可以吸附水中所有的铀离子。CLHC对铀离子的吸附过程可以用Langmuir等温吸附模型、粒子内扩散吸附动力学模型和准二级吸附动力学模型较好地进行描述。石英砂负载羟基磷灰石与CLHC相比,后者具有更强的吸附能力,而且具有更长的使用寿命。CLHC在吸附铀的过程中没有价态变化,其对铀离子的吸附主要为离子交换的化学吸附。本研究的成果可为可渗透反应墙被应用于铀污染地下水修复提供试验依据。     

Lead removal from aqueous solution by basaltic scoria: adsorption equilibrium and kinetics

Pb-contaminated water is a dangerous threat occurring near metallurgic and mining industries. This circumstance produces serious environment concern, due to Pb(II) high toxic effects. Several reactive materials have been reported for Pb(II) adsorption, but not all reached final Pb(II) suitable concentrations, or they are expensive and rejected in massive remediation technologies; hence, natural materials are good options. The adsorption behavior of a volcanic scoria (two sieved fractions 1425 and <425 µm) was studied toward synthetic Pb(II) water solutions in batch experiments (170.4–912.3 mg L^?1) with high removal efficiencies (97%). The Langmuir model fits both fractions with high linear correlation coefficients (0.9988 and 0.9949) with high maximum capacity values (588.23 and 555.55 mg g^?1). Separation factor R _L parameter varies with initial concentration, and the empirical equation predicts the limits of the material usefulness, a criterion proposed in this paper for conditions’ selection. The Lagergren pseudo-second-order analysis demonstrates chemisorption; calculated rate constant (416.66 mg g^?1 min^?1). Weber–Morris intraparticle model proves that the adsorption phenomena occur fast on the material surface (k _inst = 72 g mg^?1 min^?0.5). The characterization of the volcanic material afforded the elemental composition (X-ray fluorescence), and the empirical formula was proposed. X-ray diffraction patterns verify the material structure as basalt, with a plagioclase structure that matches anorthite and albite, mostly composed of quartz. The presence of oxides on the material surface explain the high Pb(II) adsorption capacity, observed on the surface by scanning electronic microscopy. The studied volcanic scoria has potential use as a Pb(II) adsorbent in water remediation technologies.     

Application of dried plant biomass as novel low-cost adsorbent for removal of cadmium from aqueous solution

Heavy metals are a threat to human health and ecosystem. These days, great deal of attention is being given to green technologies for purification of water contaminated with heavy metal ions. Biosorption is one among such emerging technologies, which utilizes naturally occurring waste materials to sequester heavy metals from wastewater. Cadmium has hazardous impact on living beings; therefore, its removal through green and economical process is an important task. The aim of the present study was to utilize the locally available Portulaca oleracea plant biomass as an adsorbent for cadmium removal from aqueous solution. The biomass was obtained after drying and grinding the portulaca leaves and stem. No chemical treatment was done on the adsorbent so that it remained green in a true sense. Batch experiments were performed at room temperature. The critical parameters studied were effects of pH, contact time, initial metal ion concentration and adsorbent dose on the adsorption of cadmium. The maximum adsorption was found to be 72 %. The kinetic data were found to best fit the pseudo-second-order equation. High adsorption rates were obtained in the initial 45 min, and adsorption equilibrium was then gradually achieved in about 100 min. Adsorption increased with increase in pH for a range 2 and 6. The equilibrium adsorption results closely followed both the Langmuir and Freundlich isotherms. The values of constants were calculated from isotherms. Results indicated that portulaca plant biomass could be developed as a potential material to be used in green water treatment devices for removal of metal ions.     

Determination of ammonia removal from aqueous solution and volumetric mass transfer coefficient by microwave-assisted air stripping

In this study, the removal of ammonia from synthetically prepared ammonia solution at pH 11 was investigated by using microwave radiation heating. Initially, conventional and microwave radiation heating were compared with respect to ammonia removal efficiency and overall volumetric mass transfer coefficient at five different temperatures. Overall volumetric mass transfer coefficient was calculated from the material balance for ammonia at unsteady-state condition. The effects of temperature, initial ammonia concentration, air flow rate, stirring speed, and microwave radiation power on both ammonia removal efficiency and overall volumetric mass transfer coefficient in liquid phase were also examined. The results of the experiments revealed that microwave-assisted air stripping allowed to the higher ammonia removal efficiency and overall volumetric mass transfer coefficient value compared to the conventional heating air stripping. Additionally, temperature and air flow rate were determined as the most substantial parameters affecting both ammonia removal efficiency and overall volumetric mass transfer coefficient value.     

Equilibrium studies on removal of lead (II) ions from aqueous solution by adsorption using modified red mud

In the present experimental study, solid waste was used as an adsorbent and the effectiveness of the adsorbent was increased by novel treatment methods. Red mud, acid-treated activated red mud and iron oxide-coated acid-treated activated red mud were used for the removal of lead (II). The structural and functional groups were identified to confirm the removal of lead (II) by powder X-ray diffraction and Fourier transform infrared spectroscopy analyses. The enhancement of surface area was confirmed by Brunauer–Emmett–Teller analysis. Batch adsorption experiment was also conducted, and various parameters such as the effect of adsorbent dosage, pH, contact time and initial ion concentration were analyzed and reported. Adsorption equilibrium data were investigated using Langmuir, Freundlich and Dubinin–Radushkevich isotherm models with three parameters, and the rate of reaction was examined through kinetic models. The results indicate that in particular a novel modified form of red mud, namely iron oxide-coated acid-treated activated red mud was well fitted in lead (II) removal compared with reported adsorbents. The Langmuir isotherm shows that the maximum adsorption of adsorbate per gram was greater than other adsorbents (27.02 mg/g). In Freundlich isotherm, the Freundlich constant n values lie between 1 and 10 indicate the favorable adsorption. The calculated n values for normal red mud, acid-treated activated red mud and iron oxide-coated acid-treated activated red mud were found to be 1.9, 2.1 and 2.0 respectively. The correlation coefficient value was higher and the rate of reaction follows the pseudo-second-order kinetic model.     

Potentiality of open burnt clay as an adsorbent for the removal of Congo red from aqueous solution

Open burnt clay was studied as a potential adsorbent for the adsorption of Congo red (a reactive dye) from aqueous solution. The effect of contact time, pH, adsorbent dosage and temperature were studied. It was observed that the amount of Congo red retained increase with decreasing pH and increasing initial concentration. Removal percentage at pH 2 and 3 are almost same. The adsorption capacity of regenerated burnt clay was showed more than 98 % recovery of the adsorption efficiency of initial virgin adsorbent. The equilibrium data were described well by both Langmuir and Freundlich isotherm model. The adsorption capacity of some natural adsorbents, namely rice husk, wood charcoal, tea waste etc. were also investigated and compared with that of open burnt clay.     

The crystallization of magnesite from aqueous solution

It has been suggested that the highly hydrated character of the Mg²⁺ ion in aqueous solution is responsible for the often encountered difficulty of precipitating stable, anhydrous phases of magnesium carbonate and calcium-magnesium carbonate. In an effort to investigate this, a study of magnesite crystallization kinetics was undertaken, utilizing the reaction of hydromagnesite plus CO₂ to yield magnesite at 126°C. The reactions were characterized by prolonged initial quiescent periods prior to the onset of detectable crystallization. The length of the initial period was found to vary with Mg concentration, pCO₂ and ionic strength. Contrary to classical kinetics, the reaction studied was inhibited by increased Mg concentration. Ionic strength and pCO₂ acted as positive catalysts.     

Adsorptive removal of eight heavy metals from aqueous solution by unmodified and modified agricultural waste: tangerine peel

Analysis was carried out using tangerine peel aiming its use as a potential adsorbent of eight heavy metal ions (Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn) from aqueous solution. This agricultural waste was tested both in its untreated and also chemically modified form. Based on Fourier transformation infrared spectra, a comparison of biosorbent structure before and after chemical treatment was made. Batch adsorption tests were conducted at different pH and mass of sorbent to examine the influence on the effectiveness of simultaneous removal of tested ions. Kinetic studies were conducted at optimum pH 5.0 and sorbent dosage 300 mg. The pseudo-second-order kinetic model best fit the experimental data with high correlation coefficients (r² > 0.9997). By optimizing listed parameters, high removal efficiencies (> 89%) were achieved. According to the results obtained in this study, the remediation of water polluted with heavy metals could be done using modified tangerine peel as an agricultural waste material.     

Adsorption kinetic models for the removal of Cu(II) from aqueous solution by clay liners in landfills

Liners are commonly used in engineered waste disposal landfill to minimize the potential contamination of the aquatic environment. The adsorption behavior of Cu(II) from aqueous solution onto clay admixed with various mix ratios of quarry fines was investigated. The amount of Cu(II) adsorption increases with increase in contact time. The copper removal efficiencies of the composite mixture gradually decrease from 94.53 % (raw clay) to 85.59 % (20 % of quarry fines with clay), and appreciable decrease in percent removal 75.61 % was found with 25 % of quarry fines with clay. The kinetic adsorption data were analyzed by pseudo-first-order, pseudo-second-order, Bhattacharya–Venkobachar and Natarajan–Khalaf kinetic models to classify adsorption process mechanisms. Kinetic experimental data were good agreement with pseudo-second-order kinetic model with the degree of fitness of the data (R ²) 0.9999 for the adsorption of Cu(II). The results revealed that quarry fines can be used with optimum of 20 % replacement of natural clay for removal of Cu(II) as a liner material in landfills.     

Phosphorus sorption from aqueous solution using natural materials

The sorption of phosphorus by using four different natural materials (marble dust, sawdust, soil, and rice husk) was studied by conducting batch tests and kinetic sorption model. The kinetic sorption model based on a pseudo equation was applied to predict the rate constant of sorption. Thorough investigations to understand the mechanism of phosphorus sorption onto the natural materials using kinetic sorption models, pseudo first- and second-order kinetic sorption model showed that the kinetic sorption is consistent with the second-order model, from which it can be inferred that the mechanism of sorption is chemisorption. Batch tests and kinetic sorption model results showed that by using marble dust as sorbent, among other materials, could remove more than 93 % of phosphorus from aqueous solution.     

Removal of chromate from aqueous solution using treated natural zeolite

This paper present the possible alternative removal options for the development of safe drinking water supply in the chromium-affected areas. The Cr (VI) state is of particular concern because of its toxicity. The mordenite has suitable mineralogical properties that enable them to be used for ion-exchange processes. This includes total cation exchange capacity. However, in the present work, the modified-natural zeolite was used as an adsorbent for the removal of Cr (VI) from aqueous solution. The ability of modified natural zeolite (mordenite) to remove inorganic anion was investigated. Laboratory experiments were conducted examining the effect of the sorption of cationic surfactants. On the basis of the results of this study, the HDTMA-HSO₄ modified zeolite appears suitable as a sorbent for hexavalent chromium whereas EHDDMA-modified zeolite were not removed with the same efficiency. The sorption of chromate on HDTMA-zeolite results from a combination of entropic, coulombic, hydrophobic effects, and HDTMA counterion.     

Removal of fluoride from aqueous solution by modified fly ash

Removal of fluoride from aqueous solution by modified fly ash was studied in batch model. The influences of the contact time, the initial F^- concentration, the dosage of fly ash, and the temperature on removal of F have been studied, respectively. It was found that fly ash modified with dilute HCl has the maximum adsorption of fluoride from aqueous solutions, and that the retention of fluoride ions by material was 85% or higher with initial 10 mg F^-/L. First-order kinetics was observed for the adsorption process, which follows the Langrnuir and Freundlich isotherms. The thermodynamic parameters such as ΔG0, ΔH0, ΔS0 were calculated from Langmuir constants. The positive value of ΔH0 （1.273 J/mol） confirms the endothermic nature of adsorption.     

Cd2+在甘肃靖远坡缕石粘土上的吸附作用研究

以提纯后的甘肃靖远坡缕石粘土作吸附剂,常温下对水中Cd2 进行吸附实验,考察了吸附时间、吸附剂用量、振荡速率及pH值对吸附效果的影响,并对吸附动力学过程和吸附平衡进行了探讨.XRD和红外光谱分析结果显示,原矿在提纯后杂质石英被有效分离,得到了坡缕石含量较高的提纯样品.吸附实验结果显示,约60 min吸附反应可达平衡;pH值对吸附效果有显著影响,吸附率随pH值的升高而增加,当平衡溶液pH>8时吸附率超过99%;吸附过程与pseudo-second-order Lagergren动力学模型方程有较好的一致性,吸附平衡同时符合Langmuir和Freundlich等温吸附模型,由Langmuir方程得到饱和吸附量为31.65 mg/g.     

Use of Tunisian raw clay to remove dye from aqueous solution

This paper presents the first attempt to investigate the potential of Tunisian palygorskite-rich clay (Pal-clay) on the effectiveness of a textile dye “Direct orange 34” (DO34) removal. Important parameters which affect adsorption, such as initial solution pH, contact time, adsorbent mass, initial dye concentration, and temperature, were investigated. The raw Pal-clay was characterized using X-ray diffractometer (XRD), X-ray fluorescence (XRF), Fourier transform infrared spectroscopy (FTIR), cation exchange capacity (CEC), specific surface area (SSA) analysis, and point of zero charge (PZC) determination. The results showed that the Pal-clay has a high selectivity for DO34 and had maximum removal efficiency reaching up to about 91 %. The highest adsorption capacity was obtained at 25 °C and pH of 2. The dye uptake process fitted well to the pseudo-second-order kinetic expression and was best described by the Langmuir and Freundlich isotherms. Intra-particle diffusion studies showed that the adsorption mechanism was not exclusively controlled by the diffusion step and was more likely to be governed by external mass transfer. Thermodynamic parameters such as change in free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also calculated. The parameters revealed that the adsorption of dye by the raw clay is spontaneous and exothermic. The results indicate that the Pal-clay has a moderate adsorption capacity towards anionic dye.     

Adsorption of copper(II) from aqueous solution by Beidellite

Dry lakes, degraded sandy grasslands, abandoned farmland and mobile dunes which are widely distributed throughout the arid areas of northern China have been investigated in this work. Gain-size distribution of the surface sediments of Manas lake in Junggar basin, Juyan lake in the Alxa plateau, Zhuye lake in Minqin basin and most deserts (such as Mu Us desert, Otindag desert, Horqin desert and Hulun Buir desert) in China have been analyzed. The results show clay with particle sized <10 μm on the surface sediments of dry lakebed and sandy grassland developed from dry lakebed, respectively, account for >60% and ∼50% of the total mass. Since the tiny particles on the surface of abandoned farmland are blown away easily and rapidly, the content of clay particles in Minqin basin is <14%. The grain-size distribution of mobile dunes in northern China mainly consists of particles >63 μm and few particles <10 μm. Consequently, although sand/dust storms originate primarily in the western deserts, the gobi areas of the Alxa plateau, the north and east of Hexi Corridor and in central Mongolia, the widely distributed dry lakebeds, sandy grasslands and abandoned farmland adjacent to the deserts also contribute to aeolian dusts. Hence, the material sources for sand dust storm in East Asia include inland deserts, but also dry lakes, sandy grasslands and abandoned farmland, which are widely distributed throughout the arid inlands of northern China.