PCE Oxidation by Sodium Persulfate in the Presence of Solids

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School of Civil and Environmental Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, Georgia 30332-0512, United States
* Corresponding author phone: (202)564-8526; e-mail: [email protected]
†Present address: U.S. Environmental Protection Agency, Washington, D.C.
‡Present address: DuPont Engineering, Houston, TX.
§Present address: CALMAR Associates LLC, Dorothy, NJ.
∥Present address: Department of Civil and Environmental Engineering, Tufts University, Medford, MA.
Cite this: Environ. Sci. Technol. 2010, 44, 24, 9445–9450
Publication Date (Web):November 11, 2010
Copyright © 2010 American Chemical Society
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Batch reactor experiments were performed to determine the effects of solids on the oxidation of tetracholoroethylene (PCE) by sodium persulfate in aqueous solution. Based on the rates of PCE degradation and chloride formation, PCE oxidation by heat-activated sodium persulfate at 50 °C in the presence of solids ranged from no detectable oxidation of PCE to the levels observed in water-only reactors. Repeated doses of sodium persulfate, undertaken to overcome the inherent solids oxidant demand, improved the rate and extent of PCE oxidation in reactors containing reference solids; however, no improvement was observed in reactors containing field soils. Additionally, no improvements in PCE oxidation were observed after pretreating Great Lakes and Appling soils with ca. 15 g/kg of sodium persulfate or 30% hydrogen peroxide to remove oxidizable fractions, or acetic acid to remove the carbonate fraction. Based on these results, in situ treatment of Great Lakes and Appling soils with heat-activated sodium persulfate is not anticipated to result in substantial PCE oxidation, while in situ treatment of Fort Lewis soils is anticipated to result in PCE oxidation. This work demonstrates the need to perform soil-specific contaminant treatability tests rather than soil oxidant demand tests when determining oxidant dosage requirements.

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Arrhenius rate plot, similarity between degradation kinetics obtained from sacrificial and stirred batch reactors, PCE degradation and persulfate consumption during the initial persulfate treatment, solids oxidant demand, soil fractionation methods and results, and first-order kinetic model plots for each sequential persulfate treatment. This material is available free of charge via the Internet at http://pubs.acs.org.

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  2. Ahmed I. A. Chowdhury, Jason I. Gerhard, David Reynolds, and Denis M. O’Carroll . Low Permeability Zone Remediation via Oxidant Delivered by Electrokinetics and Activated by Electrical Resistance Heating: Proof of Concept. Environmental Science & Technology 2017, 51 (22) , 13295-13303. https://doi.org/10.1021/acs.est.7b02231
  3. Junhe Lu, Wei Dong, Yuefei Ji, Deyang Kong, and Qingguo Huang . Natural Organic Matter Exposed to Sulfate Radicals Increases Its Potential to Form Halogenated Disinfection Byproducts. Environmental Science & Technology 2016, 50 (10) , 5060-5067. https://doi.org/10.1021/acs.est.6b00327
  4. Haizhou Liu, Thomas A. Bruton, Fiona M. Doyle, and David L. Sedlak . In Situ Chemical Oxidation of Contaminated Groundwater by Persulfate: Decomposition by Fe(III)- and Mn(IV)-Containing Oxides and Aquifer Materials. Environmental Science & Technology 2014, 48 (17) , 10330-10336. https://doi.org/10.1021/es502056d
  5. Hans F. Stroo, Andrea Leeson, Jeffrey A. Marqusee, Paul C. Johnson, C. Herb Ward, Michael C. Kavanaugh, Tom C. Sale, Charles J. Newell, Kurt D. Pennell, Carmen A. Lebrón, and Marvin Unger . Chlorinated Ethene Source Remediation: Lessons Learned. Environmental Science & Technology 2012, 46 (12) , 6438-6447. https://doi.org/10.1021/es204714w
  6. Xiaogang Gu, Shuguang Lu, Lin Li, Zhaofu Qiu, Qian Sui, Kuangfei Lin, and Qishi Luo . Oxidation of 1,1,1-Trichloroethane Stimulated by Thermally Activated Persulfate. Industrial & Engineering Chemistry Research 2011, 50 (19) , 11029-11036. https://doi.org/10.1021/ie201059x
  7. Liping He, Jianhao Tong, Yuanqiang Yang, Jianxun Wu, Linqian Li, Zhonghua Wei, Wei Long, Jingli Pang, Jiyan Shi. Overestimate of remediation efficiency due to residual sodium persulfate in PAHs contaminated soil and a solution. Journal of Environmental Sciences 2022, 113 , 242-250. https://doi.org/10.1016/j.jes.2021.06.004
  8. Sarah Sühnholz, Alina Gawel, Frank-Dieter Kopinke, Katrin Mackenzie. Evidence of heterogeneous degradation of PFOA by activated persulfate – FeS as adsorber and activator. Chemical Engineering Journal 2021, 423 , 130102. https://doi.org/10.1016/j.cej.2021.130102
  9. Haechan Kim, Jungsoo Kim, Donghyun Kim. Enhancement of Gel Strength of Itaconic Acid-Based Superabsorbent Polymer Composites Using Oxidized Starch. Polymers 2021, 13 (17) , 2859. https://doi.org/10.3390/polym13172859
  10. Samia Gul Niazi, Chanda Javed, Taiba Suleman, Samra Sadiq, Imtiaz Mahmood Tahir. Perfluoroalkyl Chemicals and Neurological Disorders: From Exposure to Preventive Interventions. 2021,,, 309-334. https://doi.org/10.1007/978-3-030-66376-6_14
  11. Uthirakrishnan Ushani, Xueqin Lu, Jianhui Wang, Zhongyi Zhang, Jinjin Dai, Yujie Tan, Shasha Wang, Wanjiang Li, Chengxin Niu, Teng Cai, Na Wang, Guangyin Zhen. Sulfate radicals-based advanced oxidation technology in various environmental remediation: A state-of-the–art review. Chemical Engineering Journal 2020, 402 , 126232. https://doi.org/10.1016/j.cej.2020.126232
  12. Nicholas A. Head, Jason I. Gerhard, Ainsley M. Inglis, Ariel Nunez Garcia, Ahmed I.A. Chowdhury, David A. Reynolds, Cjestmir V. de Boer, Audrey Sidebottom, Leanne M. Austrins, Jake Eimers, Denis M. O’Carroll. Field test of electrokinetically-delivered thermally activated persulfate for remediation of chlorinated solvents in clay. Water Research 2020, 183 , 116061. https://doi.org/10.1016/j.watres.2020.116061
  13. Nur Dalila Mohamad, Zuhaida Mohd Zaki, Amnorzahira Amir. Mechanisms of enhanced oxidative degradation of tetrachloroethene by nano-magnetite catalysed with glutathione. Chemical Engineering Journal 2020, 393 , 124760. https://doi.org/10.1016/j.cej.2020.124760
  14. Haoran Wei, Stephanie K. Loeb, Naomi J. Halas, Jae-Hong Kim. Plasmon-enabled degradation of organic micropollutants in water by visible-light illumination of Janus gold nanorods. Proceedings of the National Academy of Sciences 2020, 117 (27) , 15473-15481. https://doi.org/10.1073/pnas.2003362117
  15. Runlong Hao, Chu Li, Zheng Wang, Yaping Gong, Bo Yuan, Yi Zhao, Lidong Wang, John Crittenden. Removal of gaseous elemental mercury using thermally catalytic chlorite-persulfate complex. Chemical Engineering Journal 2020, 391 , 123508. https://doi.org/10.1016/j.cej.2019.123508
  16. Zhou Zhou, Xitao Liu, Ke Sun, Chunye Lin, Jun Ma, Mengchang He, Wei Ouyang. Persulfate-based advanced oxidation processes (AOPs) for organic-contaminated soil remediation: A review. Chemical Engineering Journal 2019, 372 , 836-851. https://doi.org/10.1016/j.cej.2019.04.213
  17. Hongxia Liu, Jiayi Yao, Lianhong Wang, Xinghao Wang, Ruijuan Qu, Zunyao Wang. Effective degradation of fenitrothion by zero-valent iron powder (Fe0) activated persulfate in aqueous solution: Kinetic study and product identification. Chemical Engineering Journal 2019, 358 , 1479-1488. https://doi.org/10.1016/j.cej.2018.10.153
  18. Dan Wu, Xukai Li, Jingxian Zhang, Weirui Chen, Ping Lu, Yiming Tang, Laisheng Li. Efficient PFOA degradation by persulfate-assisted photocatalytic ozonation. Separation and Purification Technology 2018, 207 , 255-261. https://doi.org/10.1016/j.seppur.2018.06.059
  19. Jingju Cai, Minghua Zhou, Ye Liu, André Savall, Karine Groenen Serrano. Indirect electrochemical oxidation of 2,4-dichlorophenoxyacetic acid using electrochemically-generated persulfate. Chemosphere 2018, 204 , 163-169. https://doi.org/10.1016/j.chemosphere.2018.04.004
  20. Rui Zhang, Xiaoxiang Wang, Lei Zhou, Zhu Liu, Doug Crump. The impact of dissolved oxygen on sulfate radical-induced oxidation of organic micro-pollutants: A theoretical study. Water Research 2018, 135 , 144-154. https://doi.org/10.1016/j.watres.2018.02.028
  21. Jie Ma, Haiyan Li, Liping Chi, Hongkun Chen, Changzhao Chen. Changes in activation energy and kinetics of heat-activated persulfate oxidation of phenol in response to changes in pH and temperature. Chemosphere 2017, 189 , 86-93. https://doi.org/10.1016/j.chemosphere.2017.09.051
  22. Jed Costanza, Tyler Marcet, Natalie L. Cápiro, Kurt D. Pennell. Tetrachloroethene Release and Degradation During Combined ERH and Sodium Persulfate Oxidation. Groundwater Monitoring & Remediation 2017, 37 (4) , 43-50. https://doi.org/10.1111/gwmr.12251
  23. Nick Zrinyi, Anh Le-Tuan Pham. Oxidation of benzoic acid by heat-activated persulfate: Effect of temperature on transformation pathway and product distribution. Water Research 2017, 120 , 43-51. https://doi.org/10.1016/j.watres.2017.04.066
  24. Runlong Hao, Shuo Yang, Bo Yuan, Yi Zhao. Simultaneous desulfurization and denitrification through an integrative process utilizing NaClO 2 /Na 2 S 2 O 8. Fuel Processing Technology 2017, 159 , 145-152. https://doi.org/10.1016/j.fuproc.2017.01.018
  25. Weiping Xie, Wei Dong, Deyang Kong, Yuefei Ji, Junhe Lu, Xiaoming Yin. Formation of halogenated disinfection by-products in cobalt-catalyzed peroxymonosulfate oxidation processes in the presence of halides. Chemosphere 2016, 154 , 613-619. https://doi.org/10.1016/j.chemosphere.2016.04.025
  26. Laura W. Matzek, Kimberly E. Carter. Activated persulfate for organic chemical degradation: A review. Chemosphere 2016, 151 , 178-188. https://doi.org/10.1016/j.chemosphere.2016.02.055
  27. Xiaoqing Chen, Muthu Murugananthan, Yanrong Zhang. Degradation of p-Nitrophenol by thermally activated persulfate in soil system. Chemical Engineering Journal 2016, 283 , 1357-1365. https://doi.org/10.1016/j.cej.2015.08.107
  28. Ku-Fan Chen, Yu-Chen Chang, Kuan-Yu Liu. A kinetic and mechanistic study of the degradation of 1,2-dichloroethane and methyl tert-butyl ether using alkaline-activated persulfate oxidation. RSC Advances 2016, 6 (79) , 75578-75587. https://doi.org/10.1039/C6RA16050F
  29. Kuo Liu, Junhe Lu, Yuefei Ji. Formation of brominated disinfection by-products and bromate in cobalt catalyzed peroxymonosulfate oxidation of phenol. Water Research 2015, 84 , 1-7. https://doi.org/10.1016/j.watres.2015.07.015
  30. Junhe Lu, Jinwei Wu, Yuefei Ji, Deyang Kong. Transformation of bromide in thermo activated persulfate oxidation processes. Water Research 2015, 78 , 1-8. https://doi.org/10.1016/j.watres.2015.03.028
  31. Yafei Shi, Jiakuan Yang, Wei Mao, Yalin Li, Xin Xu, Hao Zhang, Wenbo Yu, Ye Li, Changzhu Yang. Influence of Fe 2+ -sodium persulfate on extracellular polymeric substances and dewaterability of sewage sludge. Desalination and Water Treatment 2015, 53 (10) , 2655-2663. https://doi.org/10.1080/19443994.2013.868833
  32. Chengdu Qi, Xitao Liu, Wei Zhao, Chunye Lin, Jun Ma, Wenxiao Shi, Qu Sun, Hao Xiao. Degradation and dechlorination of pentachlorophenol by microwave-activated persulfate. Environmental Science and Pollution Research 2015, 22 (6) , 4670-4679. https://doi.org/10.1007/s11356-014-3718-6
  33. Yi Zhao, Runlong Hao, Peng Zhang, Sihan Zhou. An integrative process for Hg0 removal using vaporized H2O2/Na2S2O8. Fuel 2014, 136 , 113-121. https://doi.org/10.1016/j.fuel.2014.07.046
  34. Yi Zhao, Runlong Hao, Peng Zhang, Sihan Zhou. Integrative Process for Simultaneous Removal of SO 2 and NO Utilizing a Vaporized H 2 O 2 /Na 2 S 2 O 8. Energy & Fuels 2014, 28 (10) , 6502-6510. https://doi.org/10.1021/ef501686j
  35. Chengdu Qi, Xitao Liu, Chunye Lin, Xiaohui Zhang, Jun Ma, Haobo Tan, Wan Ye. Degradation of sulfamethoxazole by microwave-activated persulfate: Kinetics, mechanism and acute toxicity. Chemical Engineering Journal 2014, 249 , 6-14. https://doi.org/10.1016/j.cej.2014.03.086
  36. Dean F. Williamson. Combined Remedies. 2014,,, 559-598. https://doi.org/10.1007/978-1-4614-6922-3_15
  37. Zhun Zhao, Yu-Lun Fang, Pedro J.J. Alvarez, Michael S. Wong. Degrading perchloroethene at ambient conditions using Pd and Pd-on-Au reduction catalysts. Applied Catalysis B: Environmental 2013, 140-141 , 468-477. https://doi.org/10.1016/j.apcatb.2013.04.032
  38. Si-Hyun Do, Yong-Jae Kwon, Su-Jin Bang, Sung-Ho Kong. Persulfate reactivity enhanced by Fe2O3–MnO and CaO–Fe2O3–MnO composite: Identification of composite and degradation of CCl4 at various levels of pH. Chemical Engineering Journal 2013, 221 , 72-80. https://doi.org/10.1016/j.cej.2013.01.097
  39. Gokulakrishnan Subramanian, Priyadarshini Parakh, Halan Prakash. Photodegradation of methyl orange and photoinactivation of bacteria by visible light activation of persulphate using a tris(2,2′-bipyridyl)ruthenium( ii ) complex. Photochem. Photobiol. Sci. 2013, 12 (3) , 456-466. https://doi.org/10.1039/C2PP25316J
  40. Antoine Ghauch, Al Muthanna Tuqan, Nadine Kibbi, Sally Geryes. Methylene blue discoloration by heated persulfate in aqueous solution. Chemical Engineering Journal 2012, 213 , 259-271. https://doi.org/10.1016/j.cej.2012.09.122
  41. Antoine Ghauch, Al Muthanna Tuqan, Nadine Kibbi. Ibuprofen removal by heated persulfate in aqueous solution: A kinetics study. Chemical Engineering Journal 2012, 197 , 483-492. https://doi.org/10.1016/j.cej.2012.05.051
  42. C.S. Liu, K. Shih, C.X. Sun, F. Wang. Oxidative degradation of propachlor by ferrous and copper ion activated persulfate. Science of The Total Environment 2012, 416 , 507-512. https://doi.org/10.1016/j.scitotenv.2011.12.004
  43. Kelly E. Fletcher, Jed Costanza, Kurt D. Pennell, Frank E. Löffler. Electron donor availability for microbial reductive processes following thermal treatment. Water Research 2011, 45 (20) , 6625-6636. https://doi.org/10.1016/j.watres.2011.09.033
  44. Amy L. Teel, Mushtaque Ahmad, Richard J. Watts. Persulfate activation by naturally occurring trace minerals. Journal of Hazardous Materials 2011, 196 , 153-159. https://doi.org/10.1016/j.jhazmat.2011.09.011