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Environ Eng Res > Volume 26(3); 2021 > Article
Sudha, Renu, and Sangeeta: Mineralization and degradation of 4-Nitrophenol using homogeneous Fenton oxidation process

Abstract

The mineralization analysis of wastewater is important for the growth of flora and fauna. The mineralization along with the degradation of 4-NP has been studied using homogeneous Fenton oxidation process. The mineralization of 4-NP has been reported in terms of chemical oxygen demand (COD) removal % and total organic carbon (TOC) removal %. The main parameters that affect the mineralization and degradation of 4-NP i.e. initial pH (1 – 5), reaction time (0 – 60 min), the concentration of hydrogen peroxide (1 – 5 mM) and concentration of ferrous ions (0.05 – 0.5 mM) have been optimized. In the present study, optimum reaction conditions for mineralization and degradation of 4-NP are observed at pH 3, 4 mM of H2O2 concentration, 0.2 mM of Fe2+ concentration and in 40 min of reaction time. At the optimum condition, COD removal and TOC removal were 50% and 60.3%, respectively along with 93.6% of 4-NP degradation. At optimized conditions, intermediate products obtained after homogeneous degradation of 4-NP were identified based on LC-MS spectra analysis. The degradation of 4-NP followed, second order reaction rate. The present study showed the higher degradation and mineralization of 4-NP as compared to available studies on 4-NP.

1. Introduction

4-Nitrophenol (4-NP) is a hazardous, bio-refractory organic compound and is widely used for the production of pesticides, herbicides, insecticides and synthetic dyes [1]. It is highly stable and soluble in water and persists in soil and ground water for a longer period of time [2]. The discharge of 4-NP from various industries to water streams is of main concern due to its toxicity and suspected carcinogenicity. The development of efficient methods for removal of 4-NP, is becoming an important field of study for researchers.
Several treatment methods such as chemical, physical and biological have been employed for the treatment of 4-NP from waste-water [3]. Physical and biological treatment techniques are not very satisfactory as they transfer the pollutants from one phase to another, and the equipment required for these processes is also very costly [4]. Recently advanced oxidation processes (AOPs) showed considerable potential for the removal of 4-NP from industrial effluents [59]. In AOPs, the hydroxyl radicals (OH) are generated in solution and are responsible for the oxidation and mineralization of the organic pollutants to water and carbon dioxide [1013]. Among various AOPs, the Fenton oxidation process has been used extensively, as reagents (ferrous sulphate heptahydrate and hydrogen peroxide) used are easy to handle and environmental friendly [14]. The main advantage of this method is that the reaction takes place at ambient temperature, atmospheric pressure and short reaction period, which makes the process less expensive [15].
Various studies available on degradation of organic pollutants using a homogeneous Fenton oxidation process are presented in Table 1.
It is observed from Table 1, that the homogeneous Fenton oxidation process is still very active for the degradation of various organic pollutants. Further, it is observed that most of the studies are available on the degradation/ decolourization of organic pollutants, however, very few studies are reported on mineralization (TOC and COD removal) of the organic pollutants. The studies of Fathi and Keshmirizadeh [4], Ertugay and Acar [16], Giri and Golder [17] and Barbusinski [18] have analyzed COD removal % for various organic pollutants. Giri and Golder [17] has reported TOC removal (37.9%) for ciprofloxacin. The degradation studies alone do not reveal the conversion of toxic organic pollutants in simpler organic compounds. Thus mineralization of organic pollutants (TOC removal % and COD removal %) is also important along with decolorization/degradation studies and there is a need to study the mineralization of organic pollutants along with the degradation of organic pollutants.
The present study has been focused on mineralization of 4-NP along with its degradation using homogeneous Fenton oxidation process. Various parameters like initial pH, reaction time, concentration of hydrogen peroxide and ferrous ions that affect the degradation and mineralization (COD and TOC removal %) of 4-NP have been optimized. Further the studies have been extended to identify the degradation products of 4-NP using LC-MS spectra technique. The results of mineralization and degradation of 4-NP have also been compared with the available studies.

2. Material and Methods

2.1. Materials

4-NP (w/w, 98% purity), ferrous sulphate heptahydrate (FeSO4.7H2O) (w/w, purity>99%), sulphuric acid (98% purity), mercuric sulphate (purity 99%), silver sulphate (purity > 99%), were obtained from Loba Chemie Pvt. Ltd. (Mumbai, India). Hydrogen peroxide (30% w/w) was purchased from Ranbaxy Fine Chemicals Limited (Gujarat, India). Sodium hydroxide (NaOH, 97% purity), ferrous ammonium sulphate (FAS) (99% purity) was taken from s.d. fine Chemical Limited (Mumbai, India). Potassium dichromate (K2Cr2O7, purity > 99%) was obtained from Qualigens Fine Chemicals (Mumbai, India). All the solutions were prepared using double distilled water.

2.2. Experimental Procedure

Batch experiments for mineralization and degradation of 4-NP were performed by taking 0.05 mM ferrous sulphate solution into a 250 mL Erlenmeyer glass flask containing 100 mL of 4-NP (100 mg/L) solution. The pH of the solution was adjusted by the addition of a few drops of H2SO4 (0.1 N) and NaOH (0.1 N) and was measured using a pH meter (pH 700 Eutech). After the pH adjustment, 1 mM H2O2 was added quickly to the solution with continuous stirring at 30°C. With the addition of H2O2 solution, the reaction started and the samples were taken out from the flask periodically and the reaction was stopped by adding two drops of 1 M NaOH. Thereafter, the solution was filtered and the filtrate was analyzed for mineralization (TOC and COD removal %) and percentage degradation. The above experiments were repeated to study the effect of various parameters such as: pH (1 – 5), reaction time (0 – 60 min), concentration of ferrous ions (0.05 – 0.5 mM) and concentration of H2O2 (1 – 5 mM). All the experiments were repeated three times to get reproducibility of ± 5%.

2.3. Analytical Methods

The 4-NP degradation (%) after the reaction was analyzed using UV/VIS spectrophotometer at λmax 318 nm (Shimadzu double beam spectrophotometer Model: UV-VIS 2600/2700). The degradation efficiency was calculated as:
(1)
Degradation efficiency (%)=(1-CtC0)×100
Where, C0 is the initial concentration, Ct is the concentration at any time t.
The mineralization studies, chemical oxygen demand (removal %) and total organic carbon (removal %) were also analyzed after reaction. The COD of the samples before and after the reaction, was analyzed with MAC COD digester (Model: COD-439, Karnal, India) using a standard APHA method [28]. The COD efficiency of 4-NP was calculated as:
(2)
COD removal (%)=(1-CODtCOD0)×100
Where, CODt concentration at any time t, and COD0 is initial concentration at time zero.
The TOC analysis of the samples was done using a TOC analyser (Model: ASI-V and TOC-V CPN, Shimadzu, Japan) before and after the degradation of 4-NP. The non-dispersive infrared method was adopted for the detection of TOC. The TOC efficiency was calculated as:
(3)
TOC removal (%)=(1-TOCtTOC0)×100
Where, TOCt concentration at any time t, and TOC0 is initial concentration at time zero.
Liquid chromatography–mass spectroscopy (LC–MS) analysis of the reacted 4-NP samples was made to identify the intermediate products over the mass range of 40–400 amu. (model: Q-TOF micro waters, Waters, USA). The reacted sample was analyzed for determination of intermediate products using negative mode electrospray ionization (ESI) technique.

3. Results and Discussion

3.1. Effect of pH

The pH value of solution influenced the generation of hydroxyl radicals and thus the oxidation efficiency of 4-NP. It is known that the Fenton’s reaction is active in acidic medium. Thus, the effect of pH on the degradation of 4-NP was carried out by varying the pH in the range 1 to 5 at the initial reaction conditions of H2O2 concentration of 2 mM, Fe2+ concentration of 0.2 mM at 30°C and 40 min of reaction time. The effect of pH on oxidation of 4-NP i.e. degradation efficiency, COD removal (%) and TOC removal (%) is presented in Fig. 1.
It is observed that the degradation (%) of 4-NP increased from 28% to 84% with an increase in pH from 1 to 3 and thereafter it decreased to 65% with an increase in pH from 3 to 5. Similarly, the COD and TOC removal (%) of 4-NP has increased from 16% to 42% and 23% to 53%, respectively with increase in pH from 1 to 3 and it decreased to 32% and 40%, respectively with further increase in pH from 3 to 5. The maximum degradation of 84 % was obtained for 4-NP at pH 3. The COD removal (%) and TOC removal (%) for 4-NP, at 3 pH were 42% and 53% respectively. Therefore, the optimum pH for the degradation along with mineralization of 4-NP was 3. Below pH 3, the degradation (%) of 4-NP was low because very less OH radicals were produced as hydrogen peroxide was not decomposed by Fe2+ ions due to the stable oxygen concentration [29]. At very low pH, H+ ion acts as OH radical scavengers according to Eq. (4) [30].
(4)
HO+H++e-H2O
Inhibition of OH radical generation at low pH is due to the formation of complex species [Fe(H2O)6]2+ which reacts very slowly with hydrogen peroxide. In addition, the H2O2 gets solvated in the presence of high concentration of H+ ions at low pH to form stable oxonium ion [H3O2]+. The oxonium ion makes H2O2 electrophilic to enhance its stability, thus reducing the reactivity with Fe2+ ions [31]. At pH 4 and 5, due to the formation of ferrous and ferric oxy-hydroxides complexes, lesser amount of the OH radicals were generated which might have resulted in lower degradation and mineralization of 4-NP [11]. De Luis et al. [32] study has also observed maximum degradation of phenols (ortho, meta and para-cresol) at pH 3 using a homogeneous Fenton oxidation process. Meric et al. [22] achieved COD removal of 78.6% for Reactive Black 5 (RB5) dye at pH 3.

3.2. Effect of Reaction Time

The degradation of 4-NP was analyzed by varying the reaction time from 4 min to 1 h and is shown in Fig. 2. The reaction time needed for the degradation of 4-NP will depend on various parameters like pH, initial concentration of 4-NP, concentrations of ferrous ions and H2O2. For the initial reaction of 100 mg/L of 4-NP, 2 mM of H2O2, 0.2 mM of Fe2+ concentration and at pH 3, it is observed that the degradation of 4-NP increased linearly up to 8 min of reaction time and then followed the non-linear increase up to 40 min. The degradation of 4-NP was increased from 35% to 84% with increase in reaction time from 4 min to 40 min and thereafter no further degradation of 4-NP has been noticed. Therefore, the optimum reaction time for the degradation of 4-NP was observed to be 40 min for further studies.

3.3. Effect of H2O2 Concentration

The dosage of H2O2 is an important parameter as it affects the generation of OH radicals. The H2O2 concentration was varied from 1 mM to 5 mM to study the mineralization and degradation of 4-NP. The effect of H2O2 on the degradation, COD removal and TOC removal of 4-NP is shown in Fig. 3. It is observed that the degradation, COD removal and TOC removal of 4-NP increased with increase in concentration of H2O2 from 1 mM to 4 mM and thereafter decreased. The H2O2 concentration of 4 mM, degradation, COD removal (%) and TOC removal (%) of 4-NP were obtained to be 93.6, 50% and 60.3%, respectively. Increased concentration of H2O2 from 1 mM to 4 mM have resulted in more OH radicals, which might have increased the degradation and mineralization of 4-NP. Further at higher H2O2 dosage, i.e. 5 mM the decrease in degradation, COD removal and TOC removal of 4-NP might be due to the scavenging of generated OH radicals i.e. the OH radicals may react with H2O2 to generate HO2 radicals and which are less reactive than OH radicals [18, 33].
(5)
H2O2+HOHO2+H2O
Also the unused portion of H2O2 during the Fenton process contributed to COD and hence the excess amount was not recommended [34, 35].

3.4. Effect of Fe2+ Ions Concentration

It is utmost important to analyze the optimum loading of Fe2+ ions to mineralize and degrade 4-NP, because at low Fe2+ ion concentrations, the degradation and mineralization of 4-NP are less due to insufficient amount of Fe2+ ions. But higher quantities of Fe2+ ions lead to an unutilized quantity of iron salt, which further contributes to increase the total dissolved solids content in the solution [36, 37]. The range of Fe2+ ion concentration was selected by performing initial experiments. The concentration of Fe2+ ions was varied from 0.05 mM to 0.5 mM and keeping the rest of the parameters constant and the results are shown in Fig. 4. It was found that the degradation and mineralization (TOC and COD removal) rate increased with an increase in the Fe2+ ion concentration up to 0.2 mM of aqueous solution and after that the degradation and mineralization rate decreased (Fig. 4). The maximum degradation of 4-NP (93.6%) was observed at Fe2+ ion concentration of 0.2 mM.
The mineralization i.e. COD removal and TOC removal increased from 30% to 50% and 50.4% to 60.3%, respectively, with increase in Fe2+ ion concentration from 0.05 mM to 0.2 mM. The higher dosage of Fe2+ ions (>0.2mM) may result to scavenging effect with OH radicals present in solution as per the following reaction [22]:
(6)
Fe2++HOFe3++OH-
(7)
H2O2+HO-HO2+H2O+

3.5. Reaction Mechanism Showing the Degradation Pathways of 4-NP

The OH radicals were generated during the reaction between Fe2+ ions and hydrogen peroxide. The OH radicals reacted with 4-NP compound and led to the formation of intermediate products. The reaction products of the degraded 4-NP were identified using LC-MS spectra at a retention time of 3.542 min (Fig. 5). 3,4-dihydroxynitrobenzene, 1,2,4 trihydroxylbenzene, 1,2-dihydroxyaminophenol, 4-aminophenol, Hydroquinone, p-benzoquinone, 3,4,5-tridydroxynitrobenzene, 1,2,6-trihydroxy-4-aminophenol and acetic acid were identified as the some of the intermediate products by the following reactions:
(8)
C6H5NO3+HOC6H5NO4+H+4-Nitrophenenol         3,4-dihydroxynitrobenzene
(9)
C6H5NO4+HOC6H6NO3+NO2         1,2,4-trihydroxylbenzene
(10)
C6H5NO3+2H+C6H7NO+O2+e-         4-aminophenol
(11)
C6H5NO4+H+C6H7NO2+e-         1,2-dihydroxyaminophenol
(12)
C6H7NO+HOC6H8NO+e-         4-aminophenol
(13)
C6H8NO+HOC6H6NO2+NH3         Hydroquinone
(14)
C6H6O2C6HNO2+2H+         1,4-benzoquinone
(15)
C6H5NO4+HOC6H5NO5+H+         (3,4,5-tridydroxynitrobenzene)
(16)
C6H5NO5+2H+C6H7NO3+O2         1,2,6-trihydroxy-4-aminophenol
(17)
C6H4O2+2HOC6H4O4+2H+
(18)
C2H4O2+8HO2CO2+2H2O         Acetic acid
Details of identified intermediate products formed after the degradation of 4-NP are given in Table 2.
3,4-dihydroxynitrobenzene, 1,2,4-trihydroxylbenzene, 3,4,5 trihydroxynitrobenzene, hydroquinone, p-benzoquinone, CO2 and H2O were identified as the intermediate products by Ziang et al. [38]. Daneshvar et al. [39] study has identified 3,4-dihydroxynitrobenzene, 1,2,4 trihydroxylbenzene, hydroquinone as the intermediate products using photo-oxidative degradation of 4-NP. Jiang et al. [40] carried out electrochemical degradation of 4-NP and resulted in the formation of hydroquinone, p-benzoquinone, 4-aminophenol as the intermediate products. Sun and Lemley [41], Zhao et al. [42] and Minz et al. [43] studies have reported the formation of 3,4-dihydroxynitrobenzene, 1,2,4-trihydroxylbenzene, hydroquinone, p-benzoquinone, as the intermediate products after degradation of 4-NP. Some of the residual fragments against molecular weights 76.96, 188.99, 217.0, 225.15, 255.21, 281.22, 283.25, 299.19 and 327.28 remained unidentified may be due to the complexity of their formation in the solution phase.

3.6. Kinetic Study

The kinetics of the reaction helps to study the factors which influence the rate of reaction like reactant concentration, oxidant concentration and composition of the reaction mixture [44] and provides useful information about the mechanism and rate of chemical reaction. Kinetic study for the degradation of 4-NP was done as a function of time at optimum reaction conditions, i.e. initial 4-NP concentration 100 mg/L, [H2O2]: 4 mM, [Fe2+]: 0.2 mM and pH 3. The degradation data of 4-NP was analyzed for 1st order and 2nd order rate expressions as:
First order kinetics
(17)
lnC0Ct=kt
Second order kinetics
(18)
1Ct=1Co+kt
Where, C0 is the initial concentration of 4-NP and Ct is the concentration of 4-NP at any time t, k and k′ represents the rate constants of first and second order reactions respectively.
Kinetic rate constant for the degradation of 4-NP for 1st order and 2nd order rate expression are 0.0829 min−1 and 0.0037 L mg−1 min−1. The higher value of the regression coefficient (0.974) for 2nd order reaction as compared to 1st order reaction (0.853) shows that the degradation of 4-NP obeys 2nd order reaction rate with rate constant of 0.0037 L mg−1 min−1. Ghosh et al. [26] also observed second order rate for the degradation of 4-chlorophenol (4-CP) and nitrobenzene using Fenton reagent. The degradation of 2,6-dimethyl aniline using OH radicals also showed that the data was well fitted to second order kinetic model [45].

3.7. Comparison with Earlier Studies

A comparison of homogeneous Fenton process for the degradation of 4-NP for the present and available reported studies has been made and is shown in Table 3. Ma et al. [21] achieved 99% degradation of 4-NP using 5 mM of H2O2 concentration, 5 mg/L of Fe2+ at pH 3 in 2 h. Also, the dissolved organic carbon (DOC) removal efficiency was 30.6%, i.e. only one-third of 4-NP was mineralized. Another study on the degradation of nitrophenols: 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2,4-dinitrophenol (DNP) and 2,4,6-trinitrophenol (TNP), the maximum mineralization (DOC) for mono-nitrophenols was 32% [23]. However, in the present study, 93.6% degradation of 4-NP was achieved with 50% COD removal and 60.3% TOC removal efficiency in the short reaction period of 40 min. The mineralization efficiency achieved is higher than the previous studies.

4. Conclusions

The mineralization studies on 4-NP along with degradation have been made using homogeneous Fenton’s oxidation.
The present study revealed that homogeneous Fenton’s oxidation process can be used for the mineralization and degradation of 4-NP. The optimum reaction conditions for 4-NP degradation and mineralization are observed at pH 3, H2O2 concentration of 4 mM, Fe2+ concentration of 0.2 mM in 40 min of reaction time. At optimal condition, 93.6% of 4-NP were degraded within 40 min with COD removal (%) and TOC removal (%) of 50% and 60.3%, respectively. The kinetic study revealed the degradation of 4-NP by second order kinetics with rate constant of 0.0037 L mg−1 min−1 and correlation coefficient 0.974. The higher mineralization efficiency of 4-NP (50% COD removal and 60.3% TOC removal) has been observed in the present study as compared to the previous reported studies. Based upon the LC-MS spectra analysis 3,4-dihydroxynitrobenzene, 1,2-dihydroxyaminophenol, 1,2,6-trihydroxy-4-aminophenol, 3,4,5-trihydroxynitrobenze, 4-aminophenol, hydroquinone, p-benzoquinone, acetic acid etc. have been identified as the intermediate products. The present study indicated that the Fenton process was a feasible method to treat acidic wastewaters. This method could also be used in combination with other AOPs for better results.

Acknowledgment

The authors thankfully acknowledge the facilities extended by sophisticated analytical instrumentation facility of Panjab University, Chandigarh, India and Dr. B. R. Ambedkar National Institute of Technology, Jalandhar, India.

Notes

Author Contributions

S.M. (Ph.D student) conducted all the experimental work under the joint supervision of Dr. R.G. (Associate Professor) and Dr. S.G. (Associate Professor).

References

1. Zhao B, Mele G, Pio I, Li J, Palmisano L, Vasapoll G. Degradation of 4-nitrophenol (4-NP) using Fe-TiO2 as a heterogeneous photo-Fenton catalyst. J Hazard Mater. 2010;176:569–574.
crossref

2. Sun S-P, Lemley T. p-Nitrophenol degradation by a heterogeneous Fenton-like reaction on nano-magnetite: Process optimization, kinetics, and degradation pathways. J Mol Catal A Chem. 2011;349:71–79.
crossref

3. Liotta LF, Gruttadauria M, Carlo GD, Perrini G, Librando V. Heterogeneous catalytic degradation of phenolic substrates: Catalysts activity. J Hazard Mater. 2009;162:588–606.
crossref

4. Fathi Z, Keshmirizadeh E. Use of Fenton Reagent as Advanced Oxidative Process for Removal of Basic and Acid Red Dyes from Aqueous Solutions. J Appl Chem Res. 2015;9:7–19.


5. Song Y, Xiao L. Comparison treatment of various chlorophenols by electro-Fenton method: relationship between chlorine content and degradation. J Hazard Mater. 2005;118:85–92.
crossref

6. Kang N, Lee DS, Yoon J. Kinetic modeling of Fenton oxidation of phenol and monochlorophenols. Chemosphere. 2002;47:915–924.
crossref

7. Hong APK, Zeng Y. Degradation of pentachlorophenol by ozonation and biodegradability of intermediates. Water Res. 2002;36:4243–4254.
crossref

8. Sauleda R, Brillas E. Mineralization of aniline and 4-chlorophenol in acid solution by ozonation catalyzed with Fe2+ and UVA light. Appl Catal. 2001;29:135–145.
crossref

9. Ho TFL, Bolton JR. Toxicity changes during the UV treatment of pentachlorophenol in dilute aqueous solution. Water Res. 1998;32:489–497.
crossref

10. Chang MW, Chen TS, Chern JM. Initial degradation rate of p-nitrophenol in aqueous solution by Fenton reaction. Ind Eng Chem Res. 2008;47:8533–8541.
crossref

11. Ghaly MY, Härtel G, Mayer R, Haseneder R. Photochemical oxidation of p-chlorophenol by UV/H2O2 and photo-Fenton process. A comparative study. Waste Manag. 2001;21:41–47.
crossref

12. Subramonian W, Wu TY, Chai S-P. Photocatalytic degradation of industrial pulp and paper mill effluent using synthesized magnetic Fe2O3-TiO2: Treatment efficiency and characterizations of reused photocatalyst. J Environ Manag. 2017;187:298–310.
crossref

13. Teh CY, Wu TY, Juan JC. An application of ultrasound technology in synthesis of titania-based photocatalyst for degrading pollutant. Chem Eng J. 2017;317:586–612.
crossref

14. Duan F, Yang Y, Li Y, Cao H, Wang Y, Zhang Y. Heterogeneous Fenton-like degradation of 4-chlorophenol using iron/ordered mesoporous carbon catalyst. J Environ Sci. 2014;26:1171–1179.
crossref

15. Palaniandy P; AHBA SF. A review on the Fenton process for wastewater treatment. J Innov Eng. 2014;2:34


16. Ertugay N, Acar FN. Removal of COD and color from Direct Blue 71 azo dye wastewater by Fenton’s oxidation: Kinetic study. Arab J Chem. 2017;10:S1158–S1163.
crossref

17. Giri AS, Golder AK. Ciprofloxacin degradation from aqueous solution by Fenton oxidation: reaction kinetics and degradation mechanisms. RSC Advances. 2014;4:6738–6745.
crossref

18. Barbusinski K. Toxicity of industrial wastewater treated by Fenton’s reagent”. Pol J Environ Stud. 2005;14:11–16.


19. Barbeni M, Minero C, Pelizzetti E, Borgarello E, Serpone N. Chemical degradation of chlorophenols with Fenton’s reagent (Fe2++ H2O2). Chemosphere. 1987;16:2225–2237.
crossref

20. Kwon BG, Lee DS, Kang N, Yoon J. Characteristics of p-chlorophenol oxidation by Fenton’s reagent. Water Res. 1999;33:2110–2118.
crossref

21. Ma YS, Huang ST, Lin JG. Degradation of 4-nitrophenol using the Fenton process. Water Sci Technol. 2000;42:155–160.
crossref pdf

22. Meriç S, Kaptan D, Ölmez T. Color and COD removal from wastewater containing Reactive Black 5 using Fenton’s oxidation process. Chemosphere. 2004;54:435–441.
crossref

23. Kavitha V, Palanivelu K. Degradation of nitrophenols by Fenton and photo-Fenton processes. J Photochem Photobiol A. 2005;170:83–95.
crossref

24. La Nafie N. Application of Fenton’s reagent on remediation of Polycyclic Aromatic Hydrocarbons (PAHs) in spiked soil. Indones J Chem. 2010;7:208–213.
crossref

25. Khamaruddin PF, Bustam MA, Omar AA. Using Fenton’s reagents for the degradation of diisopropanolamine: effect of temperature and pH”. In International Conference on Environment and Industrial Innovation. 2011;12:12–17.


26. Ghosh P, Kelapure P, Samanta AN, Ray S. Determination of reaction rate constant for p-chlorophenol and nitrobenzene reacting with •OH during oxidation by Fe(II)/ H2O2 system. Int J Chem Tech Res. 2012;4:116–123.


27. El Haddad M, Regti A, Laamari MR, Mamouni R, Saffaj N. Use of Fenton reagent as advanced oxidative process for removing textile dyes from aqueous solutions. J Mater Environ Sci. 2014;5:667–674.


28. Clesceri LS, Greenburg AE, Eaton AD. Standard methods for the examination of water and wastewater. 20th edWashington, DC: American Public Health Association (APHA); 1999. Part 5220


29. Nidheesh PV, Gandhimathi R. Trends in electro-Fenton process for water and wastewater treatment: an overview. Desalination. 2012;299:1–15.
crossref

30. Lucas MS, Peres JA. Decolorization of the azo dye Reactive Black 5 by Fenton and photo-Fenton oxidation. Dyes Pigm. 2006;71:236–244.
crossref

31. Dhahir SA, Al-Saade KA, Al-Jobouri IS. Degradation studies of Rhodamine B in the presence of UV/H2O2/Fe2+ . Int J Tech Res Appl. 2014;2:123–127.


32. De Luis A, Lombraña JI, Varona F, Menéndez A. Kinetic study and hydrogen peroxide consumption of phenolic compounds oxidation by Fenton’s reagent. Korean J Chem Eng. 2009;26:48–56.
crossref pdf

33. Loow YL, Wu TY, Lim YS, Tan KA, Siow LF, Jahim JM, Mohammad AW. (2017)Improvement of xylose recovery from the stalks of oil palm fronds using inorganic salt and oxidative agent. Energy Convers Manag. 2017;138:248–260.
crossref

34. Babuponnusami A, Muthukumar K. A review on Fenton and improvements to the Fenton process for wastewater treatment. J Environ Chem Eng. 2014;2:557–572.
crossref

35. Lin SH, Lo CC. Fenton process for treatment of desizing wastewater. Water Res. 1997;31:2050–2056.
crossref

36. De AK, Dutta BK, Bhattacharjee S. Reaction kinetics for the degradation of phenol and chlorinated phenols using Fenton’s reagent. Environ Prog Sustain Energy. 2005;25:64–71.


37. Zhou L, Hu J, Zhong H, Li X. Study of phenol removal using fluidized-bed Fenton process. Chem Eng Res Des. 2012;90:377–382.
crossref

38. Zhang W, Xiao X, An T. , et alKinetics, degradation pathway and reaction mechanism of advanced oxidation of 4-nitrophenol in water by a UV/H2O2 process. J Chem Technol Biot. 2003;78:788–794.
crossref

39. Daneshvar N, Behnajady MA, Asghar YZ. Photo-oxidative degradation of 4-nitrophenol (4-NP) in UV/H2O2 process: Influence of operational parameters and reaction mechanism. J Hazard Mater. 2007;139:275–279.
crossref

40. Jiang P, Zhou J, Zhang A, Zhong Y. Electrochemical degradation of p-nitrophenol with different processes. J Environ Sci. 2010;22:500–506.
crossref

41. Sun SP, Lemley AT. p-Nitrophenol degradation by a heterogeneous Fenton-like reaction on nano-magnetite: process optimization, kinetics, and degradation pathways. J Mol Catal - A Chem. 2011;349:71–79.
crossref

42. Zhao S, Ma H, Wang M, Cao C, Yao S. Study on the role of hydroperoxyl radical in degradation of p-nitrophenol attacked by hydroxyl radical using photolytical technique. J Photoch Photobio - A Chem. 2013;259:17–24.
crossref

43. Minz S, Garg S, Gupta R. Catalytic wet peroxide oxidation of 4-nitrophenol over Al–Fe, Al–Cu and Al–Cu–Fe pillared clays. Indian Chem Eng. 2018;60:16–36.
crossref

44. Sun JH, Sun SP, Fan MH, Guo HQ, Qiao LP, Sun RX. A kinetic study on the degradation of p-nitroaniline by Fenton oxidation process. J Hazard Mater. 2007;148:172–177.
crossref

45. Boonrattanakij N, Lu MC, Anotai J. Kinetics and mechanism of 2, 6-dimethyl-aniline degradation by hydroxyl radicals. J Hazard Mater. 2009;172:952–957.
crossref

Fig. 1
Effect of pH on the degradation of 100 mg/L of 4-NP at reaction conditions: [H2O2] = 2 mM, [Fe2+] = 0.2 mM and time = 40 min.
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Fig. 2
Effect of reaction time on the degradation of 4-NP; Conditions: [4-NP] = 100 mg/L, [H2O2] = 2 mM, [Fe2+] = 0.2 mM, pH = 3 and time 60 min.
/upload/thumbnails/eer-2019-145f2.gif
Fig. 3
Effect of H2O2 concentration on the degradation of 4-NP, COD removal and TOC removal; Conditions: [4-NP] = 100 mg/L, [Fe2+] = 0.2 mM, pH = 3, time = 40 min.
/upload/thumbnails/eer-2019-145f3.gif
Fig. 4
Effect of ferrous ions concentration on the degradation of 4-NP, COD removal and TOC removal; Conditions: [4-NP] = 100 mg/L, [H2O2] = 4 mM, pH = 3, time 40 min.
/upload/thumbnails/eer-2019-145f4.gif
Fig. 5
LC-MS spectra analysis after degradation of 4-NP at optimized reaction conditions: 4 mM of H2O2 concentration, 0.2 mM of Fe2+ concentration, 40 min reaction time.
/upload/thumbnails/eer-2019-145f5.gif
Table 1
Degradation of Organic Pollutants Using Homogeneous Fenton Oxidation Process
Reference Organic pollutants Operating parameters/conditions Observations
Barbeni et al., 1987 [19] 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 3,4-dichlorophenol and 2,4,5-trichlorophenol. C0 = 3×10−4 M, T = 25°C
  • - Increase in concentration of Fe2+ ions enhanced decomposition rate of chlorophenols.

  • - Chlorinated aliphatic species were formed as intermediates.

Kwon et al., 1999 [20] p-chlorophenol C0 = 2.0 mM, [H2O2] = 3 – 12 mM, [Fe2+] = 0.1 – 1.0 mM, pH = 1–5
  • - The optimum reaction conditions were: 6 mM H2O2, 0.3 mM Fe2+ and pH 3.

  • - The decomposition of p-chlorophenol was high in pH range 2 – 4.

  • - The initial reaction rate was high and followed first order reaction rate with initial concentration of Fe2+ and H2O2.

Ma et al., 2000 [21] 4-Nitrophenol C0 = 1 mM, [H2O2] = 1 – 10 mM, [Fe2+] = 1 – 10 mg/L, pH = 3
  • - 99% decomposition of 4-NP was achieved at 5 mM H2O2 and 5 mg/L Fe2+ in 2 h.

  • - The dissolved organic carbon removal efficiency was 30.6%.

  • - 4-NP degradation obeyed pseudo first order reaction rate.

Meriç et al., 2004 [22] Reactive Black 5 C0 = 100 and 200 mg/L, [FeSO4]/H2O2 = 0.5 to 0.2, pH = 2.5 – 4, T = 30 – 60 °C
  • - For 100 mg/L of reactive black 5 dye, the color removal and COD removal were 99% and 71% with 100 mg/L of FeSO4, 400 mg/L of H2O2, pH 3 and 40°C.

  • - For 200 mg/L of reactive black 5, the color removal and COD removal were 99% and 84% with 200 mg/L of FeSO4, 1000 mg/L of H2O2, pH 3 and 40°C.

Barbusinski, 2005 [18] Industrial wastewater having maleic acid anhydride (MAA), 2-ethylhexyl alcohol (2-EHA) n-butanal, urea-formaldehyde resin adhesive (UFRA), pesticide-containing wastewater (PCW) [H2O2] = 2 – 10 g/dm3, [Fe2+/H2O2] = 0.2 – 0.75, pH = 2 – 5, t = 2 – 24 h
  • - At optimized conditions of 5 g/dm3 H2O2, molar ratio of Fe2+/H2O2: 0.33 and pH 3, the toxicity removal% for MAA, 2-EHA, UFRA and PCW were 47%, 51%, 12% and 100%, respectively.

  • - COD removal for MAA, 2-EHA, UFRA and PCW were 87.8%, 86.3%, 88.6% and 71.7%, respectively.

  • - Only for MAA, 2-EHA and UFRA, the toxicity was reduced to non-toxic level.

Kavitha and Palanivelu, 2005 [23] 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2,4-dinitrophenol (DNP), 2,4,6-trinitrophenol (TNP) C0 for [2-NP/4-NP] = 1.43, [DNP] = 1.08 mM and [TNP] = 0.87 mM, pH 3
  • - For mono-NP, at the optimum conditions of 17.3 mM H2O2 and 0.45 mM Fe2+, the mineralization efficiency was 32%.

  • - For DNP, at the optimum conditions of 12.9 mM H2O2 and 0.36 mM Fe2+, the mineralization efficiency was 25%.

  • - Whereas for TNP at 10.4 mM of H2O2 and 0.36 mM of Fe2+, it was 21%.

  • - Degradation of NPs followed pseudo-first-order reaction.

Chang et al., 2008 [10] p-nitrophenol (PNP) C0 = 0.1 – 0.4 mM, [H2O2] = 2 – 20 mM, [Fe2+] = 0.1 – 0.8 mM, pH = 3
  • - The optimum conditions obtained for the degradation of PNP were 0.1 mM Fe2+, 4 mM H2O2 and pH 3.

  • - For low concentration of PNP, the reaction rate was first order whereas at higher concentrations of PNP, it was zeroth order.

La Nafie, 2010 [24] Spiked soil having polycyclic aromatic hydrocarbons C0 = 200 each PAHs, pH = 3, H2O2/Fe2+ = 10:1
  • - Polycyclic aromatic hydrocarbons containing naphthalene, anthracene, fluoranthene, pyrene and benzo(a)pyrene in spiked soil were degraded to 96%.

Khamaruddin et al., 2011 [25] Diisopropanolamine C0 = 3 g/L, T = 30°C – 60°C, pH = 2 – 4, [H2O2/Fe2+] = 95
  • - Degradation efficiency of diisopropanolamine increased with increase in temperature and at 60°C, it was 85%.

  • - The optimum pH for diisopropanolamine degradation was 2.5.

  • - The degradation of diisopropanolamine followed pseudo first-order reaction rate.

Ghosh et al., 2012 [26] p-Chlorophenol (pCP) and Nitrobenzene (NB) C0-pCP = [3.889 – 7.778] × 10−3 gmol/l, [H2O2]/[pCP] = 5.65 – 7.55, [H2O2]/[Fe2+] = 8.2
C0-NB = [3.25 – 4.87] × 10−3 gmol/l, [H2O2]/[NB] = 3.6 – 10.8, [H2O2]/[Fez+] = 8.2
  • - The degradation of p-chlorophenol was 99.29% at [H2O2]/[pCP] of 7.55 whereas for nitrobenzene, it was 96.32% at [H2O2]/[pCP] of 3.60.

  • - The degradation of p-chlorophenol and nitrobenzene followed second order reaction rate with constants 2.144 × 106/M-s and 1.102 × 106/M-s, respectively.

El Haddad et al., 2014 [27] Reactive Yellow 84 dye C0 = 60 mg/L, H2O2 = 50 – 500 mg/L, Fe2+ = 10 – 100 mg/L, pH = 2 – 10, T = 20°C – 50°C
  • - 85% decolorization efficiency for reactive yellow 84 was obtained at the optimum conditions of 25 mg/L Fe2+, 250 mg/L H2O2, pH 3, 20°C in 20 min.

  • - Decolorization of reactive yellow 84 followed pseudo second order reaction rate.

  • - The activation energy for the Fenton reaction was 16.78 kJ/mol.

Giri and Golder, 2014 [17] Ciprofloxacin C0 = 15 mg/L, [Fe2+/H2O2] = 0.125, time = 45 min, T = 25°C and pH 3.5
  • - The degradation, COD and TOC removal for ciprofloxacin were 74%, 47.1% and 37.9%, respectively.

  • - Thirteen intermediate products have been reported by mass spectra analysis.

  • - The degradation of ciprofloxacin followed 2nd order reaction rate with rate constant of 3.13 × 103 M−1 s−1.

Fathi and Keshmirizadeh, 2015 [4] Acid Red 52 dye, Basic Red 18 dye C0-AR52 and C0-BR18 = 100 – 500 mg/L, [H2O2] = 1 – 3.5 g/L, [Fe2+] = 4 – 8 mg/L, pH = 3 – 9.
  • - The optimum conditions were: pH 3, 8 mg/L of Fe2+, 1.5 g/L of H2O2, 25°C and 18 min in reaction time.

  • - The color and COD removal for acid red 52 dye were 99.5% and 92%, whereas for basic red 18 dye, it were 98.5% and 85%, respectively.

Ertugay and Acar, 2017 [16] Direct Blue 71 azo dye C0 = 25 – 150 mg/L, pH = 2.0 – 6.0, [Fe2+] = 0 – 5 mg/L, [H2O2] = 25 – 150 mg/L, T = 20°C – 60°C
  • - At optimum conditions: pH 3.0, 3 mg/L Fe2+, 125 mg/L H2O2 and 20°C, the decolorization and COD removal of direct blue 71 were 100% and 49%, respectively.

Table 2
The Various Intermediate Products Formed After The Degradation of 4-NP
Intermediate name Chemical formula Structure Molecular weight
4-nitrobenzene-1,2-diol (3,4-dihydroxynitrobenzene) C6H5NO4 /upload/thumbnails/eer-2019-145f6.gif 155
Benzene-1,2,4-triol (1,2,4 trihydroxylbenzene) C6H6O3 /upload/thumbnails/eer-2019-145f7.gif 126
4-aminobenzene-1,2-diol (1,2-dihydroxyaminophenol) C6H7NO2 /upload/thumbnails/eer-2019-145f8.gif 126
4-aminophenol C6H7NO /upload/thumbnails/eer-2019-145f9.gif 109
Hydroquinone C6H6O2 /upload/thumbnails/eer-2019-145f10.gif 110
p-benzoquinone 1,4-benzoquinone C6H4O2 /upload/thumbnails/eer-2019-145f11.gif 108
5-nitrobenzene-1,2,3-triol (3,4,5-tridydroxynitrobenzene) C6H5NO5 /upload/thumbnails/eer-2019-145f12.gif 171
5-aminobenzene-1,2,3-triol (1,2,6-trihydroxy-4-aminophenol) C6H7NO3 /upload/thumbnails/eer-2019-145f13.gif 141
Acetic acid C2H4O2 /upload/thumbnails/eer-2019-145f14.gif 60
Table 3
Comparison of Present Study for The Degradation of 4-NP with Previous Studies
Reference Pollutant Initial operating conditions Degradation (%) COD removal (%) TOC removal (%) DOC removal (%) Kinetic study
Ma et al., 2000 [18] 4-Nitrophenol [4-NP]0 = 1 mM, [H2O2] = 1 – 10 mM, [Fe2+] = 1 – 10 mg/L, pH = 3 99 - - 30.6 4-NP degradation profiles fitted well into a pseudo first-order kinetic equation.
Kavitha and Palanivelu, 2005 [20] 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2,4-dinitrophenol (DNP), 2,4,6-trinitrophenol (TNP) [2-NP/4-NP]0 = 1.43 mM, [H2O2] = 17.3 mM, [Fe2+] = 0.45 mM, [DNP] = 1.08 mM, [TNP] = 0.87 mM, pH = 3 - - - 32 Degradation of NPs obeys a pseudo-first-order kinetics. Treatment efficiency for the NPs followed the sequence: NP > DNP > TNP.
Present Study 4-NP [4-NP]0 = 0.72 mM, [H2O2] = 1 – 5 mM, [Fe2+] = 0.05 – 0.5 mM, pH = 3 93.6 50 60.3 - The degradation of 4-NP followed second order kinetics.
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