Abstract
The Fenton process is used as a tertiary treatment to remove organic pollutants from the effluent of bio-treated pharmaceutical wastewater (EBPW). The optimal and most appropriate Fenton conditions were determined by an orthogonal array test and single-factor experiments. The removal of chemical oxygen demand (COD) was influenced by the following factors in a descending order: H2O2/Fe(II) molar ratio > H2O2 dosage > reaction time. Under the most appropriate Fenton conditions (H2O2/Fe(II) molar ratio of 1:1, H2O2 dosage of 120 mg L−1 and reaction time of 10 min), the COD and dissolved organic carbon (DOC) were removed with efficiencies of 62 and 53%, respectively, which met the national discharge standard (GB 21903-2008) for the Lake Tai Basin, China. However, the Fenton treatment was inadequate for removal of N compounds, and the removal of organic nitrogen led to an increment in N-NH3 from 3.28 to 19.71 mg L−1. Proteins and polysaccharides were completely removed, and humic acids (HAs) were partly removed with an efficiency of 55%. Three-dimensional excitation/emission matrix spectra (3DEEMs) indicated complete removal of fulvic acid-like substances and 90% reduction in the florescence intensity of humic acid-like substances. Organic pollutants with molecular weights (MW) > 10 kDa were completely removed, MW 5–10 kDa were degraded into smaller MW ones, and some low molecular weight acids (MW 0.1–1 kDa) were mineralized during the Fenton process. Some species, including pharmaceutical intermediates and solvents were detected by gas chromatography-mass spectrometry (GC-MS). The operational costs of the Fenton’s treatment were estimated to be 0.58 yuan RMB/m3 EBPW based on reagent usage and iron sludge treatment and disposal.
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Antonopoulou M, Evgenidou E, Lambropoulou D, Konstantinou I (2014) A review on advanced oxidation processes for the removal of taste and odor compounds from aqueous media. Water Res 53(8):215–234. https://doi.org/10.1016/j.watres.2014.01.028
APHA (2005) Standard methods for the examination of water and wastewater, 21th edn. American Public Health Association/American Water Works Association/Water Environmental Federation, Washington DC
Aquino SF, Stuckey DC (2004) Soluble microbial products formation in anaerobic chemostats in the presence of toxic compounds. Water Res 38(2):255–266. https://doi.org/10.1016/j.watres.2003.09.031
Avella AC, Görner T, de Donato P (2010) The pitfalls of protein quantification in wastewater treatment studies. Sci Total Environ 408(20):4906–4909. https://doi.org/10.1016/j.scitotenv.2010.05.039
Babuponnusami A, Muthukumar K (2014) A review on Fenton and improvements to the Fenton process for wastewater treatment. J Environ Chem Eng 2(1):557–572. https://doi.org/10.1016/j.jece.2013.10.011
Badawy MI, Wahaab RA, El-Kalliny AS (2009) Fenton-biological treatment processes for the removal of some pharmaceuticals from industrial wastewater. J Hazard Mater 167(1):567–574. https://doi.org/10.1016/j.jhazmat.2009.01.023
Barker DJ, Stuckey DC (1999) A review of soluble microbial products (SMP) in wastewater treatment systems. Water Res 33(14):3063–3082. https://doi.org/10.1016/S0043-1354(99)00022-6
Barndõk H, Blanco L, Hermosilla D, Blanco Á (2016) Heterogeneous photo-Fenton processes using zero valent iron microspheres for the treatment of wastewaters contaminated with 1,4-dioxane. Chem Eng J 284:112–121. https://doi.org/10.1016/j.cej.2015.08.097
Bautista P, Mohedano AF, Casas JA, Zazo JA, Rodriguez JJ (2008) An overview of the application of Fenton oxidation to industrial wastewaters treatment. J Chem Technol Biotechnol 83(10):1323–1338. https://doi.org/10.1002/jctb.1988
Ben W, Qiang Z, Pan X, Chen M (2009) Removal of veterinary antibiotics from sequencing batch reactor (SBR) pretreated swine wastewater by Fenton’s reagent. Water Res 43(17):4392–4402. https://doi.org/10.1016/j.watres.2009.06.057
Bu L, Wang K, Zhao QL, Wei LL, Zhang J, Yang JC (2010) Characterization of dissolved organic matter during landfill leachate treatment by sequencing batch reactor, aeration corrosive cell-Fenton, and granular activated carbon in series. J Hazard Mater 179(1):1096–1105. https://doi.org/10.1016/j.jhazmat.2010.03.118
Buresh RJ, Moraghan JT (1976) Chemical reduction of nitrate by ferrous iron. J Environ Qual 5(3):320–325. https://doi.org/10.2134/jeq1976.00472425000500030021x
Burgin AJ, Hamilton SK (2007) Have we overemphasized the role of denitrification in aquatic ecosystems? A review of nitrate removal pathways. Front Ecol Environ 5(2):89–96. https://doi.org/10.1890/1540-9295(2007)5[89:HWOTRO]2.0.CO;2
Canizares P, Paz R, Sáez C, Rodrigo MA (2009) Costs of the electrochemical oxidation of wastewaters: a comparison with ozonation and Fenton oxidation processes. J Environ Manag 90(1):410–420. https://doi.org/10.1016/j.jenvman.2007.10.010
Cao GM, Sheng M, Niu WF, Fei YL, Li D (2009) Regeneration and reuse of iron catalyst for Fenton-like reactions. J Hazard Mater 172(2):1446–1449. https://doi.org/10.1016/j.jhazmat.2009.08.010
Chelliapan S, Wilby T, Yuzir A, Sallis PJ (2011) Influence of organic loading on the performance and microbial community structure of an anaerobic stage reactor treating pharmaceutical wastewater. Desalination 271(1):257–264. https://doi.org/10.1016/j.desal.2010.12.045
Chen W, Westerhoff P, Leenheer JA, Booksh K (2003) Fluorescence excitation–emission matrix regional integration to quantify spectra for dissolved organic matter. Environ Sci Technol 37(24):5701–5710. https://doi.org/10.1021/es034354c
Chu L, Wang J, Dong J, Liu H, Sun X (2012) Treatment of coking wastewater by an advanced Fenton oxidation process using iron powder and hydrogen peroxide. Chemosphere 86(4):409–414. https://doi.org/10.1016/j.chemosphere.2011.09.007
Elmolla ES, Chaudhuri M (2009) Degradation of the antibiotics amoxicillin, ampicillin and cloxacillin in aqueous solution by the photo-Fenton process. J Hazard Mater 172(2–3):1476–1481. https://doi.org/10.1016/j.jhazmat.2009.08.015
Feng F, Xu ZL, Li XH, You WT, Zhen Y (2010) Advanced treatment of dyeing wastewater towards reuse by the combined Fenton oxidation and membrane bioreactor process. J Environ Sci 22(11):1657–1665. https://doi.org/10.1016/S1001-0742(09)60303-X
Frølund B, Palmgren R, Keding K, Nielsen PH (1996) Extraction of extracellular polymers from activated sludge using a cation exchange resin. Water Res 30(8):1749–1758. https://doi.org/10.1016/0043-1354(95)00323-1
González O, Sans C, Esplugas S (2007) Sulfamethoxazole abatement by photo-Fenton: toxicity, inhibition and biodegradability assessment of intermediates. J Hazard Mater 146(3):459–464. https://doi.org/10.1016/j.jhazmat.2007.04.055
Haber F, Weiss J (1934) The catalytic decomposition of hydrogen peroxide by iron salts. Proc R Soc A Math Phys Eng Sci 147(147):332–351. https://doi.org/10.1098/rspa.1934.0221
Hu H, Jiang C, Ma H, Ding L, Geng J, Xu K, Ren H (2017) Removal characteristics of DON in pharmaceutical wastewater and its influence on the N-nitrosodimethylamine formation potential and acute toxicity of DOM. Water Res 109:114–121. https://doi.org/10.1016/j.watres.2016.10.010
Huang LJ, Song LY, Wan HY, and Zeng K (2013) Study on the advanced treatment of pulp and paper wastewater by Fenton oxidation and its comparison with ozone oxidation. In Advanced materials research, 726. Trans Tech Publications pp 1744–1750
ISO (2007) ISO 11348-3. Water quality—determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (luminescent bacteria test)—Part 3: method using freeze-dried bacteria. International Organization for Standardization, Geneve
Jordá LSJ, Martín MB, Gómez EO, Reina AC, Sánchez IR, López JC, Pérez JS (2011) Economic evaluation of the photo-Fenton process. Mineralization level and reaction time: the keys for increasing plant efficiency. J Hazard Mater 186(2):1924–1929. https://doi.org/10.1016/j.jhazmat.2010.12.100
Jung C, Deng Y, Zhao R, Torrens K (2016) Chemical oxidation for mitigation of UV-quenching substances (UVQS) from municipal landfill leachate: Fenton process versus ozonation. Water Res 108:260–270
Kang YW, Cho MJ, Hwang KY (1999) Correction of hydrogen peroxide interference on standard chemical oxygen demand test. Water Res 33(5):1247–1251. https://doi.org/10.1016/S0043-1354(98)00315-7
Kiril MB (2010) Pre-treatment studies on olive oil mill effluent using physicochemical, Fenton and Fenton-like oxidations processes. J Hazard Mater 174(1–3):122–128. https://doi.org/10.1016/j.jhazmat.2009.09.025
Kulik N, Trapido M, Goi A, Veressinina Y, Munter R (2008) Combined chemical treatment of pharmaceutical effluents from medical ointment production. Chemosphere 70(8):1525–1531. https://doi.org/10.1016/j.chemosphere.2007.08.026
Laera G, Cassano D, Lopez A, Pinto A, Pollice A, Ricco G, Mascolo G (2012) Removal of organics and degradation products from industrial wastewater by a membrane bioreactor integrated with ozone or UV/H2O2 treatment. Environ Sci Technol 46(2):1010–1018. https://doi.org/10.1021/es202707w
LaPara TM, Nakatsu CH, Pantea LM, Alleman JE (2002) Stability of the bacterial communities supported by a seven-stage biological process treating pharmaceutical wastewater as revealed by PCR-DGGE. Water Res 36(3):638–646. https://doi.org/10.1016/S0043-1354(01)00277-9
Lester Y, Mamane H, Zucker I, Avisar D (2013) Treating wastewater from a pharmaceutical formulation facility by biological process and ozone. Water Res 47(13):4349–4356. https://doi.org/10.1016/j.watres.2013.04.059
Li Y, Zhang A (2014) Removal of steroid estrogens from waste activated sludge using Fenton oxidation: influencing factors and degradation intermediates. Chemosphere 105:24–30. https://doi.org/10.1016/j.chemosphere.2013.10.043
Li W, Nanaboina V, Zhou Q, Korshin GV (2012) Effects of Fenton treatment on the properties of effluent organic matter and their relationships with the degradation of pharmaceuticals and personal care products. Water Res 46(2):403–412. https://doi.org/10.1016/j.watres.2011.11.002
Lian L, Yan S, Yao B, Chan SA, Song W (2017) Photochemical transformation of nicotine in wastewater effluent. Environ Sci Technol 2017(51):11718–11730
Liu H, Sun P, Liu H, Yang S, Wang L, Wang Z (2015a) Acute toxicity of benzophenone-type UV filters for Photobacterium phosphoreum and Daphnia magna: QSAR analysis, interspecies relationship and integrated assessment. Chemosphere 135:182–188. https://doi.org/10.1016/j.chemosphere.2015.04.036
Liu Z, Wu W, Shi P, Guo J, Cheng J (2015b) Characterization of dissolved organic matter in landfill leachate during the combined treatment process of air stripping, Fenton, SBR and coagulation. Waste Manag 41:111–118. https://doi.org/10.1016/j.wasman.2015.03.044
Liu ZW, Li WX, Ma WH, Yin ZL, Wu GB (2015c) Comparison of deep desulfurization methods in alumina production process. J Cent South Univ 22(10):3745–3750. https://doi.org/10.1007/s11771-015-2918-7
Loures CC, Izário Filho HJ, Samanamud GRL, Souza AL, Salazar RF, Peixoto AL, Guimarães OL (2013) Performance evaluation of photoFenton and Fenton processes for dairy effluent treatment. Int Rev Chem Eng 5(4):280–288. https://doi.org/10.15866/ireche.v5i4.6930
Lowry OH, Rosebrough NJ, Farr AL, Randall RJ (1951) Protein measurement with the Folin phenol reagent. J Biol Chem 193(1):265–275
Maletzky P, Bauer R (1998) The photo-Fenton method—degradation of nitrogen containing organic compounds. Chemosphere Kidlington 37(5):899–909. https://doi.org/10.1016/S0045-6535(98)00093-9
Mohapatra DP, Brar SK, Tyagi RD, Picard P, Surampalli RY (2014) Analysis and advanced oxidation treatment of a persistent pharmaceutical compound in wastewater and wastewater sludge-carbamazepine. Sci Total Environ 471(2):58–75
Molinos-Senante M, Hernández-Sancho F, Sala-Garrido R (2010) Economic feasibility study for wastewater treatment: a cost–benefit analysis. Sci Total Environ 408(20):4396–4402. https://doi.org/10.1016/j.scitotenv.2010.07.014
Mowla A, Mehrvar M, Dhib R (2014) Combination of sonophotolysis and aerobic activated sludge processes for treatment of synthetic pharmaceutical wastewater. Chem Eng J 255:411–423. https://doi.org/10.1016/j.cej.2014.06.064
Nam SN, Krasner SW, Amy GL (2008) Differentiating effluent organic matter (EfOM) from natural organic matter (NOM): impact of EfOM on drinking water sources. Adv Environ Monit 259–270. https://doi.org/10.1007/978-1-4020-6364-0_20
Oturan MA, Aaron JJ (2014) Advanced oxidation processes in water/wastewater treatment: principles and applications. A review. Crit Rev Environ Sci Technol 44(23):2577–2641. https://doi.org/10.1080/10643389.2013.829765
Qian F, Sun X, Liu Y (2013) Removal characteristics of organics in bio-treated textile wastewater reclamation by a stepwise coagulation and intermediate GAC/O3 oxidation process. Chem Eng J 214:112–118. https://doi.org/10.1016/j.cej.2012.09.130
Rodrigues CS, Boaventura RA, Madeira LM (2014) Technical and economic feasibility of polyester dyeing wastewater treatment by coagulation/flocculation and Fenton’s oxidation. Environ Technol 35(10):1307–1319. https://doi.org/10.1080/09593330.2013.866983
San Sebastian N, Figuls J, Font X, Sanchez A (2003) Pre-oxidation of an extremely polluted industrial wastewater by the Fenton’s reagent. J Hazard Mater 101(3):315–322
Segura Y, Martínez F, Melero JA (2013) Effective pharmaceutical wastewater degradation by Fenton oxidation with zero-valent iron. Appl Catal B Environ 136–137(8):64–69
Sellers RM (1980) Spectrophotometric determination of hydrogen peroxide using potassium titanium (IV) oxalate. Analyst 105(1255):950–954. https://doi.org/10.1039/an9800500950
Shon HK, Vigneswaran S, Snyder SA (2006) Effluent organic matter (EfOM) in wastewater: constituents, effects, and treatment. Crit Rev Environ Sci Technol 36(4):327–374.
Sirtori C, Zapata A, Oller I, Gernjak W, Agüera A, Malato S (2009a) Decontamination industrial pharmaceutical wastewater by combining solar photo-Fenton and biological treatment. Water Res 43(3):661–668. https://doi.org/10.1016/j.watres.2008.11.013
Sirtori C, Zapata A, Oller I, Gernjak W, Aguera A, Malato S (2009b) Solar photo-Fenton as finishing step for biological treatment of a pharmaceutical wastewater. Environ Sci Technol 43(4):1185–1191. https://doi.org/10.1021/es802550y
Straub KL, Benz M, Schink B, Widdel F (1996) Anaerobic, nitrate-dependent microbial oxidation of ferrous iron. Appl Environ Microbiol 62(4):1458–1460
Sun Q, Deng S, Huang J, Shen G, Yu G (2008) Contributors to estrogenic activity in wastewater from a large wastewater treatment plant in Beijing, China. Environ Toxicol Pharmacol 25(1):20–26. https://doi.org/10.1016/j.etap.2007.08.003
Tekin H, Bilkay O, Ataberk SS, Balta TH, Ceribasi IH, Sanin FD et al (2006) Use of Fenton oxidation to improve the biodegradability of a pharmaceutical wastewater. J Hazard Mater 136(2):258–265. https://doi.org/10.1016/j.jhazmat.2005.12.012
USEPA (2005) Method 625-base/neutrals and acids, PART 136 guidelines establishing test procedures for the analysis of pollutants; appendix A: methods for organic chemical analysis of municipal and industrial wastewater. U.S. Environmental Protection Agency, Washington DC
Walling C (1975) Fenton’s reagent revisited. Acc Chem Res 8(4):125–131. https://doi.org/10.1021/ar50088a003
Wang X, Han J, Chen Z, Jian L, Gu X, Lin CJ (2012) Combined processes of two-stage Fenton-biological anaerobic filter–biological aerated filter for advanced treatment of landfill leachate. Waste Manag 32(12):2401–2405. https://doi.org/10.1016/j.wasman.2012.06.022
Wei X, Li B, Zhao S, Wang L, Zhang H, Li C, Wang S (2012) Mixed pharmaceutical wastewater treatment by integrated membrane-aerated biofilm reactor (MABR) system—a pilot-scale study. Bioresour Technol 122:189–195. https://doi.org/10.1016/j.biortech.2012.06.041
Westgate PJ, Park C (2010) Evaluation of proteins and organic nitrogen in wastewater treatment effluents. Environ Sci Technol 44(14):5352–5357. https://doi.org/10.1021/es100244s
Wu Y, Zhou S, Ye X, Zhao R, Chen D (2011) Oxidation and coagulation removal of humic acid using Fenton process. Colloids Surf A Physicochem Eng Asp 379(1–3):151–156. https://doi.org/10.1016/j.colsurfa.2010.11.057
Wu DL, Wang W, Guo QW, Shen YH (2013) Combined Fenton–SBR process for bamboo industry wastewater treatment. Chem Eng J 214:278–284. https://doi.org/10.1016/j.cej.2012.10.049
Wu J, Ma L, Chen Y, Cheng Y, Liu Y, Zha X (2016) Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst: removal and pathways. Water Res 92:140–148. https://doi.org/10.1016/j.watres.2016.01.053
Xie B, Lv Z, Lv BY, Gu YX (2010) Treatment of mature landfill leachate by biofilters and Fenton oxidation. Waste Manag 30(11):2108–2112. https://doi.org/10.1016/j.wasman.2010.06.018
Xie Y, Chen L, Rui L (2016) Oxidation of AOX and organic compounds in pharmaceutical wastewater in RSM-optimized-Fenton system. Chemosphere 155:217–224. https://doi.org/10.1016/j.chemosphere.2016.04.057
Xing ZP, Sun DZ (2009) Treatment of antibiotic fermentation wastewater by combined polyferric sulfate coagulation, Fenton and sedimentation process. J Hazard Mater 168(2):1264–1268. https://doi.org/10.1016/j.jhazmat.2009.03.008
Xu X, Cheng Y, Zhang T, Ji F, Xu X (2016) Treatment of pharmaceutical wastewater using interior micro-electrolysis/Fenton oxidation-coagulation and biological degradation. Chemosphere 152:23–30. https://doi.org/10.1016/j.chemosphere.2016.02.100
Yan M, Korshin G, Wang D, Cai Z (2012) Characterization of dissolved organic matter using high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) with a multiple wavelength absorbance detector. Chemosphere 87(8):879–885. https://doi.org/10.1016/j.chemosphere.2012.01.029
Yang J, Hong L, Liu YH, Guo JW, Lin LF (2014) Treatment of oilfield fracturing wastewater by a sequential combination of flocculation, Fenton oxidation and SBR process. Environ Technol 35(22):2878–2884. https://doi.org/10.1080/09593330.2014.924570
Zhao X, Wei X, Xia P, Liu H, Qu J (2013) Removal and transformation characterization of refractory components from biologically treated landfill leachate by Fe2+/NaClO and Fenton oxidation. Sep Purif Technol 116:107–113. https://doi.org/10.1016/j.seppur.2013.05.030
Zhao S, Li JL, Ma TN, Li JZ (2014) Advanced treatment of Secondary Effluent of a Pharmaceutical Factory in Northern. Adv Mater Res 955:2444–2448 Trans Tech Publications
Zhou R, Zhang W (2017) Treatment of the high concentration nonylphenol ethoxylates (NPEOs) wastewater by Fenton oxidation process. Am J Anal Chem 8(01):72–80. https://doi.org/10.4236/ajac.2017.81006
Zhou P, Su C, Li B, Qian Y (2006) Treatment of high-strength pharmaceutical wastewater and removal of antibiotics in anaerobic and aerobic biological treatment processes. J Environ Eng 132(1):129–136. https://doi.org/10.1061/(ASCE)0733-9372(2006)132:1(129)
Zhuang H, Han H, Hou B, Jia S, Zhao Q (2014) Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts. Bioresour Technol 166:178–186. https://doi.org/10.1016/j.biortech.2014.05.056
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Cheng, Y., Chen, Y., Lu, J. et al. Fenton treatment of bio-treated fermentation-based pharmaceutical wastewater: removal and conversion of organic pollutants as well as estimation of operational costs. Environ Sci Pollut Res 25, 12083–12095 (2018). https://doi.org/10.1007/s11356-018-1400-0
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DOI: https://doi.org/10.1007/s11356-018-1400-0