Research paperCd(II) adsorption from aqueous solution by raw and modified kaolinite
Introduction
Toxic heavy metals are important pollutants in water and wastewater, and they have become a public health care due to their non-biodegradable and continual nature. The toxicity risk of these metals is increased through accumulation in living organisms and following bioamplification in the food chain (An et al., 2001, Jiang et al., 2010). Among the toxic heavy metals, cadmium is highly toxic and about 80% of global Cd output is discharged to the environment as a byproduct of zinc smelting process. It is used in different industrial areas such as the production of alkaline batteries, pigments, coatings, and stabilizers for plastics (Wilburn, 1999). Cadmium compounds are often found as attached with small particles in air and their breathing with very high levels can seriously give harm to the lungs. USA Environmental Protection Agency has set a limit of only 5 ppb Cd(II) for drinking water (ATSDR, 1999) due to its carcinogenic effect on humans. Therefore, the removal of this ion from wastewaters has become a very important matter. Several methods such as electrodialysis (Mohammadi et al., 2005), ion exchange (Smara et al., 2007), reverse osmosis (Mohsen-Nia et al., 2007), ultrafiltration (Ennigrou et al., 2009), chemical precipitation (Ghosh et al., 2011), biosorption (Du et al., 2011) and adsorption (Luo et al., 2011) have been proposed for the removal of metal ions from wastewaters (Fu and Wang, 2011). Among these methods, adsorption is the most effective and simple method.
Adsorption method has also been employed generally for the elimination of Cd(II) due to its benefits such as easiness, rapidness, suitability, and design costs for the equipment and process (Volesky, 2001). The elimination of Cd(II) ions from aqueous solutions has been carried out by using different kinds of adsorbents such as polymer (Denizli et al., 2005) and modified-polymer (Pan et al., 2001), ion-exchange resin (Dong et al., 2010), modified carbon nanotubes (Gupta et al., 2011), and nano-membrane (Hajdu et al., 2012). However, such type of adsorbents is not ecofriendly and cost-effective for practical wastewater treatments. Thereby, a great attention has been paid to research on different types of low-cost unmodified and modified clay minerals for the removal of Cd(II) ions from aqueous solutions (Erdem and Ozverdi, 2005, Han et al., 2006a, Han et al., 2006b, Sarı et al., 2007a, Sarı et al., 2007b, Sari et al., 2007b, Zhang and Hou, 2008, Gupta and Bhattacharyya, 2008, Salem and Akbari, 2011).
On the other hand, unmodified and modified kaolinite (Kaol) have also been used for the removal of cadmium and other some heavy metal ions from aqueous samples (Jiang et al., 2009, Turan et al., 2007, Unuabonah et al., 2008Unuabonah and Adebowale, 2008). Lately, MnO2-modified adsorbents have attracted more notice because of the following physical and chemical properties of MnO2: (i) ionization ability at low pH, (ii) carrying ability of more negative charge in solution compared to SiO2, TiO2, Al2O3, and FeOOH (Allen et al., 1991), (iii) the loading ability at large amounts to the silica-based surfaces (Khraisheh et al., 2004), and (iv) the noticeably increasing ability of the specific surface areas of silica-based adsorbents (Eren et al., 2009). Therefore, in recent times, the interest in new type MnO2-modified adsorbents is increasing with each passing day (Al-Deges et al., 2000; Han et al., 2006a, Zou et al., 2006 Al-Ghouti et al., 2009). In addition, in previous works (Sarı and Tuzen, 2013, Sarı et al., 2012), two different clay samples (expanded perlite and vermiculite) were also functionalized with MnO2 to increase high adsorptive capacity and selectivity of these adsorbents for antimony and silver ions. In this context, the present study aims to explore the adsorption potential of MnO-Kaol in the removal of Cd(II) from aqueous solution and waste water samples. According to literature survey, there is no study in detail about the adsorption of Cd(II) from aqueous solution and waste water using MnO-Kaol. The effects of batch adsorption parameters were studied systemically. The prepared MnO-Kaol was subjected to the reusability test. The adsorption process was evaluated by examining some thermodynamics parameters, isotherm and kinetic models.
Section snippets
Adsorbents and reagents
Kaol was provided by Eczacıbası mineral industry. The sample was sieved from 200 mesh and dried in an oven at 105 °C for 24 h and maintained in a desiccator until used. The chemical constitution of the adsorbent provided by the manufacturer company was reported in previous study (Sarı et al., 2007a). In the adsorption experiments and modification process, the chemicals with analytical reagent grade were used.
Preparation of MnO-Kaol
Kaol (15 g) was modified by using MnCl2 and NaOH solutions. The Moore and Reid's method (
Characterization of kaol and MnO-Kaol by BET and SEM analyses
The amount of MnO2 fixed to the surface of kaol was determined to be 0.20 g/g-clay. Several different results were reported for the various clays modified by MnO2. For instance; 0.38 g per g-diatomite (Khraisheh, et al., 2004), 5.46 mg Mn per g-sand (Zou et al., 2006), 0.35 g per g-diatomite (Moslehi and Nahid, 2007), 0.18 per g-expanded perlite (Sarı et al., 2012) and 0.25 g per g-vermiculite (Sarı and Tuzen, 2013). These variations between the results are attributed to the deposition ability of MnO
Conclusions
In this study, MnO2 modification of the kaol was confirmed by FTIR spectroscopy, BET surface analysis and SEM technique. The adsorption experiments regarding the removal of Cd(II) from aqueous solution and real sample have been carried out using kaol and MnO-Kaol under different batch conditions. The obtained results can be summarized as follows:
- (1)
By MnO2 modification, the specific surface area of kaol was increased considerably.
- (2)
The initial pH of solution, contact time, adsorbent concentration,
Acknowledgment
The authors thank Güngör Şahinoğlu for his help in some parts of experimental studies. Dr. Mustafa Tuzen wants to thank Turkish Academy of Sciences for financial support.
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