Environmental Science and Pollution Research

, Volume 26, Issue 1, pp 684–693 | Cite as

Oxidative removal of recalcitrant organics in shale gas flowback fluid by the microwave-activated persulfate process

  • Weiming Chen
  • Ziyin Luo
  • Chuanwei Wu
  • Peng Wen
  • Qibin LiEmail author
Research Article


Shale gas flowback fluid (SGF) is generated during shale gas extraction and typically contains a variety of toxic and refractory organic compounds. In this work, a microwave-activated persulfate process (MW-PS process) was developed to pretreat SGF. The major factors influencing the treatment efficiency of the MW-PS process (PS dose, initial pH, MW power, and reaction time) were optimized, and the synergetic effect (SE), degradation of recalcitrant matter, and energy consumption were systematically investigated. Results showed that the SE of the process reached a high index (i.e., 9.85), suggesting a significant synergetic effect of MW and PS. In addition, under the optimal MW-PS condition (PS dose of 2.5 g/L, MW power of 900 W, and initial pH of 2), chemical oxygen demand removal reached 66.40% in a short reaction time of 10 min. Other analyses demonstrated that benzene series compounds, organic acids, lipid substances, alkanes, antioxidants, and fluorescent dissolved organic matter in SGF were decomposed to smaller-molecule organic matter, suggesting that refractory and toxic organic matter was removed by the MW-PS treatment process. Overall, the results of this study showed that MW-PS technology is an effective and promising method to treat SGF once the operation parameters are optimized.


Shale gas Flowback fluids Microwave Persulfate Organic 


Funding information

The authors received financial support from the Key Laboratory of Special Waste Water Treatment (SWWT2015-4).


  1. Baeza C, Knappe DR (2011) Transformation kinetics of biochemically active compounds in low-pressure UV photolysis and UV/H2O2 advanced oxidation processes. Water Res 45:4531–4543CrossRefGoogle Scholar
  2. Butkovskyi A, Faber AH, Wang Y, Grolle K, Hofmancaris R, Bruning H, Van AW, Rijnaarts H (2018) Removal of organic compounds from shale gas flowback water. Water Res 100(76)Google Scholar
  3. Cortez S, Teixeira P, Oliveira R, Mota M (2011) Evaluation of Fenton and ozone-based advanced oxidation processes as mature landfill leachate pre-treatments. J Environ Manag 92:749–755CrossRefGoogle Scholar
  4. Deng Y, Ezyske CM (2011) Sulfate radical-advanced oxidation process (SR-AOP) for simultaneous removal of refractory organic contaminants and ammonia in landfill leachate. Water Res 45:6189–6194CrossRefGoogle Scholar
  5. Domeizel M, Khalil A, Prudent P (2004) UV spectroscopy: a tool for monitoring humification and for proposing an index of the maturity of compost. Bioresour Technol 94:177–184CrossRefGoogle Scholar
  6. Fida H, Zhang G, Guo S, Naeem A (2016) Heterogeneous Fenton degradation of organic dyes in batch and fixed bed using La-Fe montmorillonite as catalyst. J Colloid Interface Sci 490:859–868CrossRefGoogle Scholar
  7. Fuentes M, González-Gaitano G, García-Mina JMa (2006) The usefulness of UV–visible and fluorescence spectroscopies to study the chemical nature of humic substances from soils and composts. Org Geochem 37:1949–1959CrossRefGoogle Scholar
  8. Furman OS, Teel AL, Watts RJ (2010) Mechanism of base activation of persulfate. Environ Sci Technol 44:6423–6428CrossRefGoogle Scholar
  9. Guo XJ, Xi BD, Yu HB, Ma WC, He XS (2011) The structure and origin of dissolved organic matter studied by UV-vis spectroscopy and fluorescence spectroscopy in lake in arid and semi-arid region. Water Sci Technol 63:1010–1017CrossRefGoogle Scholar
  10. He C, Zhang T, Vidic RD (2016) Co-treatment of abandoned mine drainage and Marcellus shale flowback water for use in hydraulic fracturing. Water Res 104:425–431CrossRefGoogle Scholar
  11. Homem V, Alves A, Santos L (2013) Microwave-assisted Fenton's oxidation of amoxicillin. Chem Eng J 220:35–44CrossRefGoogle Scholar
  12. Horikoshi S, Saitou A, Hidaka H, Serpone N (2003) Environmental remediation by an integrated microwave/UV illumination method. V. Thermal and nonthermal effects of microwave radiation on the photocatalyst and on the photodegradation of rhodamine-B under UV/Vis radiation. Environ Sci Technol 37:5813–5822CrossRefGoogle Scholar
  13. Jiang J, Yu H, Xi B, Meng F, Zhou Y, Liu H (2011) UV–visible spectroscopic properties of dissolved fulvic acids extracted from salined fluvo-aquic soils in the Hetao Irrigation District, China. Soil Res 49:670–679CrossRefGoogle Scholar
  14. 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 108:260–270CrossRefGoogle Scholar
  15. Kausley SB, Malhotra CP, Pandit AB (2017) Treatment and reuse of shale gas wastewater: electrocoagulation system for enhanced removal of organic contamination and scale causing divalent cations. J Water Process Eng 16:149–162CrossRefGoogle Scholar
  16. Kavurmaci SS, Bekbolet M (2014) Specific UV–vis absorbance changes of humic acid in the presence of clay particles during photocatalytic oxidation. Desalin Water Treat 52:1903–1910CrossRefGoogle Scholar
  17. Koh DY, Kang H, Lee JW, Park Y, Kim SJ, Lee J, Lee JY, Lee H (2016) Energy-efficient natural gas hydrate production using gas exchange. Appl Energy 162:114–130CrossRefGoogle Scholar
  18. Korshin GV, Li CW, Benjamin MM (1997) Monitoring the properties of natural organic matter through UV spectroscopy: a consistent theory. Water Res 31:1787–1795CrossRefGoogle Scholar
  19. Lai B, Zhou Y, Wang J, Yang Z, Chen Z (2013) Application of excitation and emission matrix fluorescence (EEM) and UV–vis absorption to monitor the characteristics of Alizarin Red S (ARS) during electro-Fenton degradation process. Chemosphere 93:2805–2813CrossRefGoogle Scholar
  20. Li S, Zhang G, Wang P, Zheng H, Zheng Y (2016) Microwave-enhanced Mn-Fenton process for the removal of BPA in water. Chem Eng J 294:371–379CrossRefGoogle Scholar
  21. Li X, Zhou M, Pan Y, Xu L, Tang Z (2017) Highly efficient advanced oxidation processes (AOPs) based on pre-magnetization Fe0 for wastewater treatment. Sep Purif Technol 178:49–55CrossRefGoogle Scholar
  22. Liang C, Huang CF, Mohanty N, Kurakalva RM (2008) A rapid spectrophotometric determination of persulfate anion in ISCO. Chemosphere 73:1540-1543Google Scholar
  23. Liu P, Ren Y, Ma W, Ma J, Du Y (2018) Degradation of shale gas produced water by magnetic porous MFe2O4 (M = Cu, Ni, Co and Zn) heterogeneous catalyzed ozone. Chem Eng JGoogle Scholar
  24. Mackenzie AS, Leythaeuser D, Schaefer RG, Bjorøy M (1983) Expulsion of petroleum hydrocarbons from shale source rocks. Nature 301:506–509CrossRefGoogle Scholar
  25. Oulego P, Collado S, Laca A, Díaz M (2016) Impact of leachate composition on the advanced oxidation treatment. Water Res 88:389–402CrossRefGoogle Scholar
  26. Qi C, Liu X, Zhao W, Lin C, Ma J, Shi W, Sun Q, Xiao H (2015) Degradation and dechlorination of pentachlorophenol by microwave-activated persulfate. Environ Sci Pollut Res Int 22:4670–4679CrossRefGoogle Scholar
  27. Qi C, Liu X, Lin C, Zhang H, Li X, Ma J (2017) Activation of peroxymonosulfate by microwave irradiation for degradation of organic contaminants. Chem Eng J 315:201–209CrossRefGoogle Scholar
  28. Ravera M, Buico A, Gosetti F, Cassino C, Musso D, Osella D (2009) Oxidative degradation of 1,5-naphthalenedisulfonic acid in aqueous solutions by microwave irradiation in the presence of H2O2. Chemosphere 74:1309–1314CrossRefGoogle Scholar
  29. Rodríguez FJ, Schlenger P, Garcíavalverde M (2016) Monitoring changes in the structure and properties of humic substances following ozonation using UV-Vis, FTIR and (1) H NMR techniques. Sci Total Environ 541:623–637CrossRefGoogle Scholar
  30. Saleem M, Spagni A, Alibardi L, Bertucco A, Lavagnolo MC (2018) Assessment of dynamic membrane filtration for biological treatment of old landfill leachate. J Environ Manag 213:27–35CrossRefGoogle Scholar
  31. Shukla P, Sun H, Wang S, Ang HM, Tadé MO (2011) Co-SBA-15 for heterogeneous oxidation of phenol with sulfate radical for wastewater treatment. Catal Today 175:380–385CrossRefGoogle Scholar
  32. Song F, Wu F, Guo F, Wang H, Feng W, Zhou M, Deng Y, Bai Y, Xing B, Giesy JP (2017) Interactions between stepwise-eluted sub-fractions of fulvic acids and protons revealed by fluorescence titration combined with EEM-PARAFAC. Sci Total Environ 605-606:58–65CrossRefGoogle Scholar
  33. Tan C, Dong Y, Fu D, Gao N, Ma J, Liu X (2017) Chloramphenicol removal by zero valent iron activated peroxymonosulfate system: kinetics and mechanism of radical generation. Chem Eng J 334Google Scholar
  34. Warner NR, Christie CA, Jackson RB, Vengosh A (2013) Impacts of shale gas wastewater disposal on water quality in Western Pennsylvania. Environ Sci Technol 47:11849–11857CrossRefGoogle Scholar
  35. Weng CH, Huang V (2015) Application of Fe0 aggregate in ultrasound enhanced advanced Fenton process for decolorization of methylene blue. J Ind Eng Chem 28:153–160CrossRefGoogle Scholar
  36. Wu J, Zhang H, He PJ, Shao LM (2011) Insight into the heavy metal binding potential of dissolved organic matter in MSW leachate using EEM quenching combined with PARAFAC analysis. Water Res 45:1711–1719CrossRefGoogle Scholar
  37. Xiong Z, Lai B, Yuan Y, Cao J, Yang P, Zhou Y (2016) Degradation of p -nitrophenol (PNP) in aqueous solution by a micro-size Fe0/O3 process (mFe0/O3): optimization, kinetic, performance and mechanism. Chem Eng J 302:137–145CrossRefGoogle Scholar
  38. Xu XR, Li XZ (2010) Degradation of azo dye Orange G in aqueous solutions by persulfate with ferrous ion. Sep Purif Technol 72:105–111CrossRefGoogle Scholar
  39. Yang Y, Pignatello JJ, Ma J, Mitch WA (2014) Comparison of halide impacts on the efficiency of contaminant degradation by sulfate and hydroxyl radical-based advanced oxidation processes (AOPs). Environ Sci Technol 48:2344–2351CrossRefGoogle Scholar
  40. Zhang X, Wang Y, Li G, Qu J (2006) Oxidative decomposition of azo dye C.I. Acid Orange 7 (AO7) under microwave electrodeless lamp irradiation in the presence of H2O2. J Hazard Mater 134:183–189CrossRefGoogle Scholar
  41. Zhang T, Lu J, Ma J, Qiang Z (2008) Comparative study of ozonation and synthetic goethite-catalyzed ozonation of individual NOM fractions isolated and fractionated from a filtered river water. Water Res 42:1563–1570CrossRefGoogle Scholar
  42. Zhang H, Xiong Z, Ji F, Lai B, Yang P (2017) Pretreatment of shale gas flowback fluid (SGF) by the microscale Fe0/persulfate/O3 process (mFe0/PS/O3). Chemosphere 176:192–201CrossRefGoogle Scholar
  43. Zou J, Rezaee R, Liu K (2017) The effect of temperature on methane adsorption in shale gas reservoirs. Energy Fuel 31:12081–12092CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Weiming Chen
    • 1
  • Ziyin Luo
    • 1
  • Chuanwei Wu
    • 1
  • Peng Wen
    • 1
  • Qibin Li
    • 1
    Email author
  1. 1.Faculty of Geosciences and Environmental EngineeringSouthwest Jiaotong UniversityChengduChina

Personalised recommendations