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GeoloGy, ecoloGy, and landscapes, 2018 Vol . 2, no . 1, 39– 44 https://doi.org/10.1080/24749508.2018.1438746 INWASCON OPEN ACCESS Efficient entrapping of toxic Pb(II) ions from aqueous system on a fixed-bed column of fungal biosorbent Farah Amin, Farah Naz Talpur, Aamna Balouch, Hassan Imran Afridi and Abid Ali Khaskheli national c entre of excellence in analytical chemistry, University of sindh, Jamshoro, p akistan ABSTRACT ARTICLE HISTORY Received 18 a ugust 2017 The present research dealt with the successful viability and practicality of Pleurotus eryngii a ccepted 14 o ctober 2017 packed bed column for Pb(II) ions biosorption. To achieve the aim of the project, the impact of different parameters including flow rate, initial concentration of Pb(II) ions and bed height KEYWORDS were optimized. The column models, i.e.,Thomas and Bed Depth Service Time (BDST) were Fixed-bed column; investigated to assess the column efficiency towards entrapping targeted ion. The adsorption biosorption; pb(II); Thomas capacity, rate constant and correlation coefficient related to each model for column sorption model; bed depth service were also calculated. The adsorption capacity enhanced by increasing the bed height and time (BdsT) model decreasing initial Pb(II) metal ion concentration along with the flow rate. The maximum Thomas −1 model adsorption (entrapping) capacity was obtained 3.30 mg g for initial concentration of −1 −1 20 mg L at a constant flow rate of 1 ml min , bed height of 3 cm and pH 7. The experimental results implied and affirmed the suitability of the P. eryngii fungal biosorbent for Pb(II) ion biosorption with its nature being favourable, efficient and environment friendly. 1. Introduction metal ions in aqueous system has encouraged scientists to seek alternative methods for the removal of this type Heavy metals discharged from untreated industrial and of contamination. municipal effluents are amongst the main sources of To date several techniques such as chemical precip- water pollution in the recent past. The acute toxicity and itation, electrocoagulation, flocculation, membrane carcinogenicity associated with metal ions discharged filtration, adsorption and ion exchange treatment have into the aquatic system pose a serious threat to the envi- been employed for the removal of toxic metal ions from ronment (Vilvanathan & Shanthakumar, 2017). These aqueous system (Gunatilake, 2015); but due to high cost, heavy metals find their way into the micro-environment, dispose off issues, formation of by-products, reliability the aquatic flora and fauna and in turn into the food of the technique and its environmental impacts these chain exhibiting direct health effects on humans. They techniques facing confinements (Barakat, 2011). are classified as toxic materials due to their non-bio- In this scenario, it is important to opt for an econom- degradability and bioaccumulation tendency in liv- ically feasible and effective treatment method which is ing organisms (Klapiszewski, Bartczak, Szatkowski, & free from these limitations and is able to translate the Jesionowski, 2017). need of removal of heavy metals in terms of eco-friendly Special attention needs to be paid to the metal ions, approach. Recently, a state-of-the-art technique ‘biore- particularly Pb(II) ions. The lower concentration of mediation’ is introduced for the removal of heavy metals Pb(II) ion is essential for the promotion of many bio- from wastewater involving the use of natural biomateri- synthesis reactions in the human body and is also play- als (macro and microbial biomass / adsorbents) (Abdel- ing an important role as micronutrients for animal and Raouf & Abdul-Raheim, 2017). plants, yet it is harmful at a higher level of concentration Our previous reported work has demonstrated the (Tchounwou, Yedjou, Patlolla, & Sutton, 2012; Singh, potential use of P. eryngii biomass to enhance bioreme- Gautam, Mishra, & Gupta, 2011). According to the diation of heavy metals by batch experiments (Amin, standards of WHO, the maximum permissible limit of Talpur, Balouch, & Afridi, 2017). However, the results −1 Pb(II) ions in aqueous system is 0.05 mg L (WHO, of batch study may not be directly being applied for the 2008). If this level of concentration exceeds in water, it field applications in wastewater treatments. causes anaemia and stomach intestinal distress (Sravya, In this research work, P. eryngii, a fungal biomass 2015). Therefore, growing problem of the presence of commonly called as ‘white-rot fungus,’, is studied here CONTACT Farah naz Talpur farah.talpur@usindh.edu.pk © 2018 The a uthor(s). published by Informa UK limited, trading as Taylor & Francis Group. This is an open a ccess article distributed under the terms of the creative c ommons a ttribution license (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 40 F. AMIN ET AL. for its biosorptive potential. Considering its relative material was packed in the column to yield the desired adequacy and abundant availability, this mycelium can bed height of the sorbent. At the top of the column, −1 be a potential resource of natural biosorbent. Hence, the influent (Pb) solution (20, 30 mg L ) was pumped the aim of present work is to investigate the entrapping through the packed column (1, 2 and 3 cm), at flow rates −1 capacity of P. eryngii fungal biomass as a biosorbent for of 1, 3 and 5 ml min , using a peristaltic pump. Samples Pb(II) ions removal from aqueous system in continuous were collected from the exit of the column at regular mode in a fixed-bed column. The biosorption capacity time intervals and analyzed for residual concentration of P. eryngii was investigated under pH controlled con- at room temperature. ditions by varying the flow rate, initial Pb(II) ion con- centration and bed height. The breakthrough data were 2.4. Analytical instrumentation analyzed using Thomas and Bed Depth Service Time e pH m Th etre (InoLab-WTW GmbH; Weilheim, (BDST) models. Germany) with glass electrode and an internal reference electrode were used for pH measurements. 2. Material and methods Quantification of Pb(II) ions before and aer t ft he 2.1. Preparation of fungal biomass (P. eryngii) sorption was carried out by Varian AA 20 spectra atomic absorption spectrometer (Mulgrave, Victoria, Australia) For sorption studies, P. eryngii mycelium using as bio- equipped with cathode lamp of respective elements. The sorbent (biomass) was procured from Edible Fungi process parameters of Flame-AAS are given in Table 1. Institute, Shanghai Academy of Agricultural Sciences, e flo Th w rate for Pb(II) ion solutions during column China. e Th detail of P. eryngii biomass preparation is studies were optimized by Eyela peristaltic pump (Tokyo described in our previously reported work (Amin, Rikakikai Co., Ltd. Japan) and flow system was made of Talpur, Balouch, Surhio, & Bhutto, 2015). PTFE 0.5 mm i.d. 2.2. Preparation of standard solutions for 2.5. Analysis of column data understudy sorbate (Pb-metal) e t Th otal quantity of sorbate (Pb-metal) biosorbed in −1 To acquire 1000 mg L stock solution of pure Pb(II) the column (m ) is calculated from the area above the ad metal, 4.577 g analytical grade salt of Pb(NO ) were dis- 3 2 breakthrough curve multiplied by the flow rate (Foo, −1 solved in ultra-pure water (conductivity 0.05 μS cm ) in a Lee, & Hameed, 2013). volumetric flask. By appropriate dilution of stock solution Dividing the amount of sorbate (m ) by the amount ad with ultra-pure water, working standards of metal were of biosorbent (M) leads to the uptake capacity (Q) of prepared freshly from certified and internal standards. the biomass. e pH o Th f working solutions were adjusted to the e t Th otal amount of Pb(II) ions sent to the column desired values according to subsequent experimental calculated from the following Equation (1): design with 0.1 M NaOH or 0.1 M HCl solutions. C Fte m = (1) total 2.3. Continuous (packed column) biosorption −1 experiment Where C is the inlet Pb(II) ions concentration (mg L ); −1 F is the volumetric flow rate (mL h ); and t locate the Continuous flow sorption experiments were conducted exhaustion time (h). in a mini glass column (5 mm × 120 mm). Total removal (%) with respect to flow volume can be e b Th ottom of the column filled with glass wool calculated from the ratio of Pb(II) ions mass adsorbed followed by a small layer of glass beads at the column (m ) to the total amount of Pb(II) ions sent to the col- ad base in order to provide a uniform inlet flow of the solu - umn (m ) as follows (2): total tion into the column. A known quantity of biosorbent ad Total sorbate removal(%) = × 100 (2) total Table 1. c onditions of F-aas for p b(II) ions determination. Parameter Pb 2.6. Statistical analysis Wavelength (nm) 217.0 Hollow cathode lamp current (ma ) 5.0 All continuous experiments were performed in trip- Type of flame air- c H 2 2 licates and the results are presented as means of the Background correction on slit width (nm) 1.0 triplicates. The linear regression coefficients R were −1 a cetylene flow rate (l min ) 1.5 determined using Microsoft Excel (Microsoft Inc., WA, −1 air flow rate (l min ) 3.0 U.S.A.) to test the adequacy and accuracy of the line- Flame condition o xidizing expansion factor 1 arized forms of the model equations. GEOLOGY, ECOLOGY, AND LANDSCAPES 41 2.7. Column models (Babu, Krishnan, & Singh, 2010). The measurement of sorbent quantity is more precise than the determination In process applications, a packed bed column is an effec - of the respective volume. Therefore, sorbent quantity is tive process for cyclic sorption / desorption, as it makes being preferably used, instead of the bed height. the best use of the concentration difference known to e lin Th ear form of BDST model expressed as Equation be a driving force for pollutant sorption and results in (4): a better quality of the effluent (Negrea, Lupa, Ciopec, & Negrea, 2011). Two frequently used models i.e., Thomas N Z C 0 0 t = − ln − 1 and BDST were used to analyze the compatibility of (4) C K C C 0 a 0 b experimental data of the tested metals. where t is the service time (h), N is the adsorption 2.7.1. Thomas model −3 capacity (mg cm ), Z is the height of column (cm), C e desig Th n of an adsorption packed column requires the −1 is the breakthrough sorbate concentration (mg L ), ϑ determination of column parameters such as adsorption −1 is the linear velocity (cm h ) and K is the rate constant capacity and the kinetic parameters (Al Dwairi, Omar, & −1 −1 (L mg h ) at time t. Al-Harahsheh, 2015). e Th Th omas model can be imple - A plot of t vs. bed depth (Z) should yield a straight line mented to analyze the breakthrough curves and adsorp- and use to evaluate N and K , respectively. Application 0 a tion capacity for each sorbent. The linearized form of of the BDST model requires specification of the break- o Th mas model expressed by Equation (3): through time, which was selected arbitrarily. C k q m 0 Th 0 ln − 1 = − k C t (3) Th 0 C Q 3. Results and discussion 3.1. Column study where C and C are the inlet and the effluent solute con- 3.1.1. Effect of flow rate centrations at any time t (m); k is the Thomas model Th −1 −1 e ad Th sorption columns were operated with different constant (mL m mg ); q is the maximum solid-phase −1 −1 flow rates (1, 3 and 5 mL min ) at a fixed concentration concentration of solute (mg g ); and M is the total mass and bed height until no further Pb removal was observed. of the adsorbent (g). The model constants k and q Th 0 e b Th reakthrough curve for a column were determined can be determined from slope and intercept of a plot of by plotting the ratio of the C /C (C and C are the ln[(C /C) – 1] against t, respectively. e 0 e 0 Pb(II) concentrations of effluent and influent, respec- 2.7.2. BDST model tively) against time, as shown in Figure 1. The column −1 e B Th DST model used to predict the column perfor - performed well at a lower flow rate (1 mL min ). Earlier mance of any bed length, if data for some depths are breakthrough (C /C = 0.05) and exhaustion times were e 0 known. It relates the service time of a fixed bed with the achieved, when the flow rate was increased from 3 to −1 height of adsorbent in the bed, hence with its quantity 5 mL min . This was due to a decrease in the residence −1 Figure 1. Breakthrough curves for different flow rates (initial p b(II) ion concentration: 10 mg l ; bed height: 2 cm). 42 F. AMIN ET AL. −1 Figure 2. Breakthrough curves for different p b(II) ion concentration (flow rate: 1 ml min ; bed height: 2 cm). time, which restricted the contact of Pb(II) solution to explained by Han et al. (2006) for the biosorption of the fungal biomass. At higher flow rates, the Pb(II) ions Cu(II) and Pb(II) ions from aqueous solution by cha ff did not have enough time to diffuse into the pores of in a fixed-bed column. the fungal biomass and they exited the column before 3.1.3. Effect of bed height (BDST model) equilibrium occurred (Mobasherpour, Salahi, & Asjodi, e acc Th umulation of Pb(II) ions in a fixed-bed column 2014). In literature, similar behaviour of breakthrough is dependent on the quantity of biosorbent inside the for Pb(II) by immobilized fungus Phanerochaete chrys- column. To study the effect of bed height on Pb(II) osporium was reported by Pakshirajan and Swaminathan retention, fungal biomass of three different bed heights. (2010). As depicted by Figure 3, the breakthrough time varies 3.1.2. Effect of initial Pb(II) ions concentration with bed height. The breakthrough time decreased with (Thomas model) a decreasing bed depth from 3 to 1 cm, as binding sites e Th adsorption breakthrough curves obtained by chang - were restricted at low bed depths. At low bed depth, the −1 ing initial Pb(II) concentration (20 and 30 mg L ) at Pb(II) ions do not have enough time to diffuse into the −1 1 mL min flow rate as given in Figure 2. As estimated, surface of the biomass, and a reduction in breakthrough a decrease in Pb(II) concentration gave a later break- time occurs. Conversely, with an increase in bed depth, through curve; because the treated volume was greatest the residence time of Pb(II) solution inside the column at the lowest transport due to a decreased diffusion coef - was increased, allowing the Pb(II) ions to diffuse deeper ficient or mass transfer coefficient. into the fungal biomass (Babu et al., 2010). The related Breakthrough time (C /C = 0.05) came up aer ft affinity was also reported in the literature (Biswas & e 0 −1 9.0 min at 20 mg L initial Pb concentration while the Mishra, 2015). −1 breakthrough time was 3.0 min at 30 mg L . The break - A plot of service time vs. bed depth, at a flow rate of −1 through time decreased with increasing Pb concentra- 1 mL min (Figure 4–60b) was linear. The correlation 2= tion as the binding sites became more quickly saturated coefficient value (R 0.964) indicated the validity of the in the column. BDST model for the present system. The values of BDST e Th o Th mas model kinetic parameters calculated Table 2. The Thomas and BdsT model parameters for the from equation 3 reveals a good fit of the experimen- biosorption of pb(II) on P. eryngii fungal biomass. tal data at all concentration examined (Table 2). The Thomas model parameters correlation coefficients greater than 0.905 showed that Pb(II) concentra- the external and internal diffusions were not the rate −1 −1 −1 −1 2 tion (mg L ) q (mg g ) k (mL m mg ) R o Th limiting step. The rate constant (k ) decreased with Th −3 20 2.78 1.42 × 10 0.983 increasing Pb(II) concentration which indicates that the −3 30 3.30 1.39 × 10 0.905 mass transport resistance increases due to the driving The BDST model parameters −3 2 force between Pb(II) concentration and fungal biomass No (mg cm ) Ka (L R −1 −1 −3 mg h ) × 10 (Negrea et al., 2011). Comparable outcomes were also 0.767 5.385 0.964 GEOLOGY, ECOLOGY, AND LANDSCAPES 43 −1 −1 Figure 3. (a) Breakthrough curves for different bed height (flow rate: 1 ml min ; initial pb(II) ion concentration: 20 mg l ) and (b) Bed depth service time plot for the adsorption of pb(II) ions by fungal biomass in column. Table 3. c omparison of pb(II) ions sorption capacity. 3.3. Application of column on real contaminated water samples Sorption capacity Batch mode Column mode −1 mg g 2.971 3.30 e r Th emoval of toxic ions from real water samples is a link between laboratory and commercial application of column. In this study, all the laboratory adsorption Table 4. Removal of pb(II) ions from real water samples via column method. column conditions developed (flow rate, bed height) are transferred to the normal level. The results obtained are Influent Pb(II) Effluent Pb(II) Total Pb(II) −1 −1 Samples* (mg L ) (mg L ) removal (%) given in Table 4 suggest that Pb(II) ions removed suc- Industrial area, 0.146 ± 0.005 0.018 ± 0.0026 87.67 ± 1.79 cessfully below the permissible limits of WHO drinking Kotri water standards. phuleli c anal, 0.063 ± 0.0026 0.0049 ± 0.0015 92.22 ± 1.97 Hyderabad number of replicates *n = 3 4. Conclusion In this work, continuous biosorption operation in a model parameters are presented in Table 2 calculated fixed-bed column was performed for Pb(II) ions bio- Equation (4). sorption by P. eryngii fungal biomass. Thomas and BDST e va Th lue of Ka characterizes the rate of transfer from models were used to successfully evaluate the column the fluid phase to the solid phase. If Ka is large, even a performance. The breakthrough curves of the continu- short bed will avoid breakthrough, but as Ka decreases ous flow systems (columns) were adequately fitted with a progressively deeper bed is required to avoid break- the Thomas model, which provided an estimation of the through. From this model and its obtained constants, −1 dynamic adsorption capacities of 3.30 mg g for the feasibility of column structure and its performance were −1 3 cm bed height at a constant flow rate of 1 ml min evaluated using sufficient concentration and flow rate and pH 7. In the fluidized bed system, increase in the for sorption of Pb(II) ions onto fungal biomass without solution flow rate decreased the breakthrough time due further experimental analysis and data. to the decrease in the contact time between the adsorb- ate (Pb) and the adsorbent (biomass); besides, at low 3.2. Comparison of Pb(II) ions sorption capacity flow rates the metal ions had a sufficient contact time during batch and column mode to occupy the spaces within the particles. An increase in concentration of Pb(II) ions caused a decrease in the Table 3 represents a good sorption capacity by column, operating time due to the driving force between Pb(II) then previously conducted batch mode (Amin et al., concentration and fungal biomass. Likewise, it was 2017). It is generally attributed to the more time inter- found that increase in the bed depth of fungal biomass action between the biosorbent and the sorbate surface increased the breakthrough time. 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Geology Ecology and Landscapes – Taylor & Francis
Published: Jan 2, 2018
Keywords: Fixed-bed column; biosorption; Pb(II); Thomas model; bed depth service time (BDST) model
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