Degradation of Pentachlorophenol in Aqueous Solution by the UV/ZrO2/H2O2 Photocatalytic Process

Mohammad Reza Samarghandi; Ali Reza Rahmani; Mohammad Taghi Samadi; Majid Kiamanesh; Ghasem Azarian

doi:10.17795/ajehe-4761

Degradation of Pentachlorophenol in Aqueous Solution by the UV/ZrO₂/H₂O₂ Photocatalytic Process

Mohammad Reza Samarghandi ¹ , Ali Reza Rahmani ¹ , Mohammad Taghi Samadi ¹ , Majid Kiamanesh ^{2
, *} and Ghasem Azarian ²

Authors Information

Article Notes and Dates

Abstract

Pentachlorophenol (PCP), which is one of the resistant phenolic compounds, has been classified in the category of EPA’s priority pollutants due to its high toxicity and carcinogenic potential. Therefore, its removal from water and wastewater is very important. Various methods have been studied for removing the compound, among which advanced oxidation processes (AOPs) have attracted much attention because of ease of application and high efficiency. Thus the aim of this study was to investigate the efficiency of the UV/ZrO₂/H₂O₂ process, as an AOP, for PCP removal from aquatic environments. The effects of several parameters such as ultraviolet (UV) exposure time, initial PCP concentration, pH, concentration of zirconium dioxide (ZrO₂) nanoparticles, and H₂O₂ concentration were studied. Kinetics of the reaction was also detected. The concentration of the stated materials in the samples was determined using a spectrophotometer at 500 nm. The results showed that the highest efficiency (approximately 100%) was reached at optimized conditions of pH 6, contact time of 30 minutes, initial PCP concentration of 20 mg/L, the nanoparticles concentration of 0.1 g/L and H₂O₂ concentration of 14.7 mM/L. Also, the process followed the first order kinetics reaction. The obtained results illustrated that the UV/ZrO₂/H₂O₂ process has a high ability in removing PCP.

1. Introduction

Persistent organic pollutants (POPs) generated by various industries can highly contaminate the environment. Pollution of groundwater and surface water with aromatic compounds such as phenolic compounds is one of the most serious environmental problems that humanity faces today (1). Pentachlorophenol (PCP) is a derivative of phenol family that due to 5 chlorine atoms on the benzene ring is used more than other phenolic derivatives (2). Pure PCP exists in colorless crystals with a strong smell as well as white, brown or dark gray. Figure 1 shows the chemical structure of this compound (3).

Figure 1. The Chemical Structure of PCP

Pentachlorophenol is applied in the manufactures of biocides, wood preservatives, making herbicide compounds, and strengthening wooden bridges and fences in large quantities. It can be harmful to kidney, liver, blood, lungs, central nervous system, immune system, digestive system, skin, and eyes. Among the properties of this material is absorption through the gastrointestinal tract (4). Due to the health effects of PCP, various methods have been examined to investigate its removal; among different methods of phenol removal, one can refer to the process of adsorption and advanced oxidation processes (AOPs) such as H₂O₂/microwave, H₂O₂/UV radiation, ozone/H₂O₂, ozone/UV, H₂O₂/UV, ozone process/titanium dioxide/UV and so forth (5). The main mechanism in the AOPs method is based on the production of hydroxyl radical (OH^•) with high oxidation power. As a strong oxidant, it is capable of destroying resistant compounds that cannot simply be oxidized by conventional oxide donors such as, ozone and chlorine dioxide. Compared to conventional oxidation methods, advanced AOPs have significant advantages, because they produce fewer residues and by-products (6). Photo catalytic processes which are based on absorption of light energy are carried out by a solid material (7). In these processes, as catalytic nanoparticles, absorb high-energy photons of UV spectrum and subsequently active chemicals such as OH^•s are formed (8). When photo catalysts are set under ultraviolet (UV) radiation, they stimulate and stir up valence band electrons and cause the electron to move from the valence band to the conduction band. In so doing, some holes are made in the valence band that are very active and they can react either directly with organic contaminants at the catalyst levels or indirectly through the formation of OH^•s. Moreover, active electrons which has excited into the conduction band, such as superoxide and OH^• formation react with organic material (9). In recent years, photocatalytic oxidation processes have received considerable attention by metal oxides in the removal of organic contaminants and microbial agents (10). Among these metal oxides is the nano zirconium dioxide (ZrO₂), which has a catalytic property for many applications (11). Heidari Farsani et al. (12) studied the efficiency of UV/ZrO₂/H₂O₂ on the removal of nickel and found that this process is able to remove 60% of nickel from a real wastewater. This nanoparticle, 20 nm size and a surface area greater than 25 m²/g is regarded as an appropriate catalyst (11).

To our best knowledge, no studies have been conducted on PCP destruction by means of the UV/ZrO₂/H₂O₂ process. Thus, since the performance of each treatment system may change with different pollutants. Moreover, in order to study the effects of operating parameters and their impact on the removal efficiency, comprehensive investigations are needed. In this study, the performance of the UV/ZrO₂/H₂O₂ process was studied and the variables of concentration of nanoparticles of ZrO₂, initial pH, initial PCP concentration, H₂O₂ concentration and dioxide were optimized.

2. Materials and Methods

The present study was conducted on laboratory scale discontinuously using a photo reactor (Figure 2) on synthetic solution containing PCP in different concentrations of 10, 20, 30, 40 and 50 mg/L. In this study, a 150 watt low pressure mercury lamp with a quartz envelope within a steel chamber of high reflection was used. The reaction on the samples of contaminated water was done in the space between the UV-C lamp and the steel cover. To perform this experiment, first by dissolving 1 g of PCP in 1000 mL of distilled water of the stock solution of 1000 mg/L was prepared then by making solutions with a concentration of 10 to 100 mg/L and reading the absorbance by a spectrophotometer 500 nm, PCP calibration curve was drawn (13). Next, the impact of the variables pH, reaction time, H₂O₂ concentration, concentration of PCP and nano- ZrO₂ concentration on removal efficiency was examined. All parameters were optimized as one at a time (14). First, pH values of 2, 4, 6, 8 and 10 were adjusted; at this stage, based on the literature review PCP content was set at the real degree (20 mg/L). The pH level was adjusted using NaOH and H₂SO₄ (0.1 N). The pH value was optimized in the presence of 0.5 g of nanoparticles of ZrO₂ and 14.7 mM/L of H₂O₂, and pH = 6 was selected as the optimum amount. Contents of 0.1, 0.25, 0.5, 0.75 and 1 g of nanoparticles of ZrO₂ were used to optimize, which was 0.1 g/L at pH = 6 and H₂O₂ = 14.7 mM/L. Next, in order to optimize the PCP concentration, of which 10, 20, 30, 40 and 50 mg/L were made. So as to investigate all variables and the procedure of pollutant removal, samples were taken from the solution at contact times of 10, 20, 30, 40, 50 and 60 minutes and then were filtered using a 0.2 M syringe filter and finally the concentration of PCP in the samples was measured. The percentage of the removal of PCP was obtained using Equation 1 (14).

Equation 1.

Where C₀ represents the initial concentration of PCP (as mg/L) and C represents the remaining concentration (as mg/L) in the solution after performing all functions. In order to measure PCP concentration and pH value, a spectrophotometer (UV/Vis spectrometer-DR 5000) and portal pH meter (Sensl Hack, Germany), respectively, were used.

Figure 2. A Schematic Diagram of the Photo-Reactor Containing Low-Pressure Mercury Lamp

3. Results and Discussion

pH is one of the most important factors affecting the decomposition of organic compounds. Solution pH plays an important role in photocatalytic reactions and UV/ZrO₂/H₂O₂ has a better function in acidic conditions (15). The effect of pH on the removal efficiency has been shown in Figure 3. In order to evaluate the effect of pH on the process, the pH values of 2, 4, 6, 8 and 10 at the fixed nanoparticle concentration of ZrO₂ (0.5 g/L), the concentrations of H₂O₂ 14.7 mM/L and PCP 20 mg/L were adjusted. The results showed that in acidic conditions, with increasing pH, the removal efficiency enhanced gradually to a maximum 99% until the contact time 30 minutes and pH = 6. However, by increasing pH from acidic to alkaline conditions (from pH of 6 to 10), the removal efficiency was declined from 99% to 75%.

Figure 3. Effect of pH Variations on PCP Removal Using the UV/ZrO₂/H₂O₂ Process (ZrO₂ = 0.5 g/L, PCP = 20 mg/L, H₂O₂ = 14.7 mM/L)

The reason of increasing the removal efficiency in acidic pH is that the surface of nano-ZrO₂ is positively charged and attracts more PCP. As a result of more adsorption of PCP, generation of OH^•s as well as the decomposition rate in acidic environment are increased resulting in the removal efficiency heightening. The efficiency decline in the alkaline condition is because of the fact that the nano-particle surface gets a negative charge, which reduces the adsorption of PCP reducing the production of OH^•s and that also leads to the reduction of the rate of decomposition in the alkaline environment; thus, it decreases removal efficiency (16). Another reason for the decline of the removal efficiency of UV/ZrO₂/H₂O₂ in alkaline conditions is that H₂O₂ is converted to water and oxygen (7). On the other hand, in acidic environments it acts as the dominant oxidant and will have more oxidation power (17). The results of this study are perfectly constant with the obtained results of a study done by Quan et al. (18) In order to remove PCP, they used titanium dioxide nanotubes and found that the removal efficiency decreased with increasing pH value. Also, in a study conducted by Asadi et al. (19) titled using the photocatalytic process UV/NiO in eliminating direct poliazo dyes, the pH optimum of 4 was achieved. Dependence of PCP elimination on the concentration of nanoparticle at concentrations of 0.1 to 1 g/L of nanoparticles was studied. The results presented in Figure 4 indicates that the process, which is examined in this study, with an increase in the concentration of nanoparticles, PCP removal rate decreased and the highest removal efficiency for this compound related to the concentration was 0.1 g/L nanoparticle. With concentrations above this, the removal efficiency reduced. The reason behind this efficiency decline lies in the fact that increasing the initial amount of nanoparticles, due to their accumulation, causes turbidity and thereby reduces the intensity light of UV as well as decreasing the production of OH^•s (20). This result is consistent with the results of Samarghandi et al. (7) in the field of the efficiency of the photocatalytic process of titanium dioxide in removing reactive black 5 and cyanide from aqueous solutions.

Figure 4. Effect of ZrO₂ Variations on Pentachlorophenol Removal Using the UV/ZrO₂/H₂O₂ Process (pH = 6, PCP = 20 mg/L, H₂O₂ = 14.7 mM/L)

In AOPs, the type and concentration of an oxidizing agent is one of the effective factors in the removal of organic compounds. To determine the effect of the concentration changes of hydrogen peroxide on the process of UV/ZrO₂/H₂O₂, the experiments were performed at the concentration of pollutants in fixed conditions: 20 mg/L of PCP, pH 6 and the concentration nanoparticles of 0.1 g/L. The results of hydrogen peroxide concentration changes (Figure 5) showed that different concentrations of 2.9, 7.3, 14.7, 22.0 and 29.4 mM/L of hydrogen peroxide for 30 minutes could remove 78%, 95%, 100%, 80% and 77% of organic matter. These results indicated that the removal efficiency of organic matter is under the influence of the ionic conditions and polarity of the system. Also, as expected, with the increase of the concentration of hydrogen peroxide removal efficiency of organic matter, the removal efficiency rose and then decreased gradually. It has been determined that in the existence of a high dose of hydrogen peroxide, OH^• reacts with hydrogen peroxide and this leads to the production of peroxide radical (HO2^•) which is weaker than peroxide radical (21, 22). Also, in excessive amounts of hydrogen peroxide, hydroperoxyl radicals, which are less active, are produced (reaction 1) and exceeded amounts of hydroxyl are converted to hydrogen peroxide through dimerization (reaction 2). According to reactions 2 to 4, hydroperoxil radicals do not participate in oxidation reactions and contribute to the chain reactions and hydrogen peroxide is decomposed to O₂ and HO₂ anions (21).

(1) H₂O₂ + OH^¯ → HO^•₂ + H₂O

(2) OH^• + OH^• → H₂O₂

(3) HO₂^• + OH^• → H₂O + O₂

(4) OH^• + H₂O₂ → O₂ + H⁺ + H₂O

(5) HO^•₂ + H₂O₂ → O^•₂ + OH^• + H₂O

The results of Jamshidi et al. (23) study, in which the removal of phenol from aqueous solutions using advanced photochemical oxidation technologies was investigated, verifies the results of the present study.

Figure 5. Effect of H₂O₂ Concentration Changes on Pentachlorophenol Removal Using UV/ZrO₂/H₂O₂ (ZrO₂ = 0.1 g/L, PCP = 20 mg/L, pH = 6)

The effect of the concentration of PCP figure (Figure 6) showed that the efficiency of the UV/ZrO₂/H₂O₂ process had an inverse relation with PCP concentrations and with increasing concentrations of PCP, its removal rate gradually reduced. It should be noted that the process under the investigation at high concentrations also enjoys a good ability to remove PCP. As can be seen in the results, PCP at the concentration of 30 mg/L UV/ZrO₂/H₂O₂ had a removal efficiency of 92%. The reason is that by increasing the initial concentration, more PCP molecules are adsorbed on the surface of the nanoparticle; thus, it prevents the reaction of PCP molecules with the photonic cavities and OH^•s produced, due to the lack of a direct contact between them (7). In addition to this, the high concentration of organic matter in the environment leads to greater consumption of antioxidants and increase the duration of complete decontamination. So, by increasing the concentration of organic matter, process efficiency reduces. On the other hand, the low concentration of organic matter in the environment also reduces the efficiency of the process (24). In this case, the existence of much more oxidizing agents in the environment has a negative impact on the process efficiency. That is, when the concentration of hydrogen peroxide ions in the environment increases in the ratio of PCP concentrations, with it forms a stable complex with the hydroxyl radicals; therefore, reducing the amount of free radicals in the environment resulting in reduced efficiency of the process or in other words, increasing the concentration of pollutants in intact stationary conditions of operation, because of two main reasons, it reduces efficiency; in constant quantities of OH^•, with increase in the concentration of pollutants, the extent of contact and encountering increases (25-27). Also, increasing the concentration of the pollutant can cause producing more byproducts arising from the oxidation of these compounds. These compounds will consume more OH^•. The results of this study indicated that increasing the concentration of PCP causes reducing the rate of reaction thereby lessening the efficiency. The results of other studies also have put an emphasis on this fact and they have recognized the solutions in increasing the reaction time (28). It is worth mentioning that the process under this study in high concentrations is of a good ability in removing PCP. As can be seen in the results, in PCP at a concentration of 30 mg/L, the process of UV/ZrO₂/H₂O₂ had a removal efficiency of 92%.The results obtained from Malakootian et al. (24) study on removal of phenol from aqueous solutions using advanced oxidation technologies also verify the present results. Also, because of the impact of advanced oxidation reaction, kinetics curves were determined (Figure 7). It showed that this process follows the optimized kinetic model, which indicates that the rate of decrease in the concentration of PCP is a function of reaction time.

Figure 6. Effect of Initial Concentration of Pentachlorophenol on the Removal Efficiency Using UV/ZrO₂/H₂O₂ (ZrO₂ = 0.1 g/L, H₂O₂ = 14.7 mM/L, pH = 6)

Figure 7. A, The Zero-Order Kinetic Model; B, First-Order Kinetic Model

The findings showed that each process of AOPs could not remove PCP well separately. For example, the processes of H₂O₂ and UV irradiation are applied separately because of high resistance of PCP against destruction. However, when they are combined together the efficiency increased dramatically because of the rapid generation of OH^•s and an increase in a reaction rate. It should be noted that the UV/ZrO₂/H₂O₂ photocatalytic process can enhance the efficiency and meet economical aspects.

4. Conclusions

The use of nanotechnology in the removal of environmental pollutants is among the methods, which has attracted much attention in recent years. In this study, the PCP removal through using the process of UV/ZrO₂/H₂O₂ was examined and it was found that the highest removal efficiency (100%) was attained at pH = 6, contact time of 30 minutes, nanoparticle concentration of 0.1 g/L and the H₂O₂ concentration of 14.7 mM/L. Furthermore, pertaining to the correlation coefficients obtained for the data in the kinetic models, it is inferred that this process follows the first-order kinetic model. Generally, it can be concluded that the UV/ZrO₂/H₂O₂ process with a high efficiency is capable of removing PCP from aquatic environments.

Acknowledgements

Footnote

References

1. Busca G, Berardinelli S, Resini C, Arrighi L. Technologies for the removal of phenol from fluid streams: a short review of recent developments. J Hazard Mater. 2008; 160(2-3): 265-88[DOI][PubMed]
2. Nadavala SK, Swayampakula K, Boddu VM, Abburi K. Biosorption of phenol and o-chlorophenol from aqueous solutions on to chitosan-calcium alginate blended beads. J Hazard Mater. 2009; 162(1): 482-9[DOI][PubMed]
3. Agency for Toxic Substances and Disease Registry (ATSDR) . Toxicological Profile for Pentachlorophenol . 2015;
4. Scheck CK, Frimmel FH. Degradation of phenol and salicylic acid by ultraviolet radiation/hydrogen peroxide/oxygen. Water Res. 1995; 29(10): 2346-52[DOI]
5. Bi X, Wang P, Jiang H. Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater. J Hazard Mater. 2008; 154(1-3): 543-9[DOI][PubMed]
6. Wong WT, Chan WI, Liao PH, Lo KV, Mavinic DS. Exploring the role of hydrogen peroxide in the microwave advanced oxidation process: solubilization of ammonia and phosphates. J Environ Eng Sci. 2006; 5(6): 459-65[DOI]
7. Samarghandi M, Shirzad Siboni M, Maleki A, Jafari SJ, Nazemi F. Kinetic Determination and Efficiency of Titanium Dioxide Photocatalytic Process in Removal of Reactive Black 5 (RB5) Dye and Cyanide from Aquatic Solution [in Persian]. J Mazandaran Univ Med Sci. 2011; 21(81): 44-52
8. Parga JR, Shukla SS, Carrillo-Pedroza FR. Destruction of cyanide waste solutions using chlorine dioxide, ozone and titania sol. Waste Manag. 2003; 23(2): 183-91[DOI][PubMed]
9. Daneshvar N, Aber S, Dorraji SMS, Khataee AR, Rasoulifard MH. Photocatalytic degradation of the insecticide diazinon in the presence of prepared nanocrystalline ZnO powders under irradiation of UV-C light. Sep Purif Technol. 2007; 58(1): 91-8[DOI]
10. Kamat PS, Huehn R, Nicolaescu R. Semiconductor nanostructures for simultaneous detection and degradation of organic contaminants in water. J Photochem Photobiol Chem. 2008; (42): 573-7
11. Sharma SC, Gokhale NM, Dayal R, Lal R. Synthesis, microstructure and mechanical properties of ceria stabilized tetragonal zirconia prepared by spray drying technique. Bull Mater Sci. 2002; 25(1): 15-20[DOI]
12. Heidari Farsani M, Ahmadi Moghaddam M, Shirmardi M, Mengelizadeh N, Heidari Farsani A, Naeimabadi A. The effectiveness of the UV/H2O2/UV/H2O2 and ZrO2/SiO2 processes in removal of the nickel from the aqueous environments. J North Khorasan Uni Med Sci. 2013; 5(4): 741-50
13. Yang S, Wang P, Yang X, Wei G, Zhang W, Shan L. A novel advanced oxidation process to degrade organic pollutants in wastewater: microwave-activated persulfate oxidation. J Environ Sci (China). 2009; 21(9): 1175-80[PubMed]
14. Curteanu S, Godini K, Piuleac CG, Azarian G, Rahmani AR, Butnariu C. Electro-Oxidation Method Applied for Activated Sludge Treatment: Experiment and Simulation Based on Supervised Machine Learning Methods. Ind Eng Chem Res. 2014; 53(12): 4902-12[DOI]
15. Lipczynska-Kochany E, Sprah G, Harms S. Influence of some groundwater and surface waters constituents on the degradation of 4-chlorophenol by the fenton reaction. Chemosphere. 1995; 30(1): 9-20[PubMed]
16. Muruganandham M, Swaminathan M. Decolourisation of Reactive Orange 4 by Fenton and photo-Fenton oxidation technology. Dyes and Pigments. 2004; 63(3): 315-21[DOI]
17. Zhang H, Duan L, Zhang Y, Wu F. The use of ultrasound to enhance the decolorization of the CI Acid Orange 7 by zero-valent iron. Dyes and Pigments. 2005; 65(1): 39-43[DOI]
18. Quan X, Ruan X, Zhao H, Chen S, Zhao Y. Photoelectrocatalytic degradation of pentachlorophenol in aqueous solution using a TiO2 nanotube film electrode. Environ Pollut. 2007; 147(2): 409-14[DOI][PubMed]
19. Asadi A, Nateghi R, Naseri S, Mohammadian M, Mohammadi H, Bonyadinejad GR. Direct poly azo dye decolorization using nanophotocatalytic uv/nio process. Water Wastewater . 2012; 23(8): 78-84
20. Kusvuran E, Gulnaz O, Irmak S, Atanur OM, Yavuz HI, Erbatur O. Comparison of several advanced oxidation processes for the decolorization of Reactive Red 120 azo dye in aqueous solution. J Hazard Mater. 2004; 109(1-3): 85-93[DOI][PubMed]
21. Chu W, Wong CC. The photocatalytic degradation of dicamba in TiO2 suspensions with the help of hydrogen peroxide by different near UV irradiations. Water Res. 2004; 38(4): 1037-43[DOI][PubMed]
22. Rahmani AR, Nematollahi D, Azarian G, Godini K, Berizi Z. Activated sludge treatment by electro-Fenton process: Parameter optimization and degradation mechanism. Korean J Chem Eng. 2015; 23(8): 1570-7[DOI]
23. Jamshidi N, Torabian A, Azimi AA, Nabi Bidhendi GH, Jafarzadeh MT. Investigation of phenol removal in aqueous solutions using advanced photochemical oxidation (APO). Water Wastewater. 2009; (4): 24-9
24. Malakootian M, Asadi M. Efficiency of fenton oxidation process in removal of phenol in aqueous solutions. Water Wastewater . 2011; 22(3): 46-52
25. Zhou M, Yu Q, Lei L, Barton G. Electro-Fenton method for the removal of methyl red in an efficient electrochemical system. Sep Purif Technol. 2007; 57(2): 380-7[DOI]
26. Godini K, Azarian G, Rahmani AR, Zolghadrnasab H. Treatment of waste sludge: a comparison between anodic oxidation and electro-Fenton processes. J Res Health Sci. 2013; 13(2): 188-93[PubMed]
27. Rahmani AR, Godini K, Nematollahi D, Azarian G. Electrochemical oxidation of activated sludge by using direct and indirect anodic oxidation. Desalination Water Treat. 2015; 56(8): 2234-45[DOI]
28. Peyton GR. The free-radical chemistry of persulfate-based total organic carbon analyzers. Mar Chem. 1993; 41(1–3): 91-103[DOI]

Except where otherwise noted, this work is licensed under Creative Commons Attribution Non Commercial 4.0 International License .

Download Fulltext :

PDF(size: 995.93 KB) | HTML Full Text

Table of Contents:

Share This Article on:

Search Relations:

Author(s):

Mohammad Reza Samarghandi: [PubMed] [Scholar]
Ali Reza Rahmani: [PubMed] [Scholar]
Mohammad Taghi Samadi: [PubMed] [Scholar]
Majid Kiamanesh: [PubMed] [Scholar]
Ghasem Azarian: [PubMed] [Scholar]

Article(s):

Related Article in PubMed
Related Article in Google Scholar

Create Citiaion Alert via Google Reader

Cited By: