Skip to main content
SpringerLink
Log in

Oxidative degradation of diclofenac by thermally activated persulfate: implication for ISCO

Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Diclofenac (DCF), one of the typically recalcitrant pharmaceuticals, has been frequently detected in groundwater in recent years. This work investigated the performance of DCF degradation by thermally activated persulfate (PS) to further understand its application in in situ chemical oxidation (ISCO) for DCF-contaminated groundwater. The effects of various factors, including activation temperature, solution pH, PS/DCF ratio, and common constitutes, e.g., HCO3 −, Cl− and humic acid, and the toxicity of transformation products were evaluated. The results indicated that the oxidation of DCF was well-fitted with a pseudo-first-order kinetic model, and the rate constants increased with the elevated temperatures. The rate constants from 50–70 °C were further fitted to the Arrhenius equation, yielding an activation energy of 157.63 kJ·mol−1. In addition, the oxidation of DCF was highly pH-dependent, with the rate constants rapidly decreased from pH 5 to 7, then slightly increased at the alkaline pH. The presence of a low dosage of Cl− (0–10 mM) promoted the degradation of DCF, whereas high Cl− addition (>10 mM) inhibited DCF degradation. HCO3 − exhibited a negligible effect on DCF removal, while natural organic matters, e.g., humic acids, lightly inhibited DCF degradation. The rapid degradation of DCF was also confirmed in the real groundwater sample, which might be attributed to the pH drop during the reaction. Moreover, the radical quenching experiments revealed that sulfate radicals (SO4 ·-) was the dominant reactive species for DCF oxidation. Finally, the acute toxicity of the DCF solution, as tested with a bioluminescent assay, was gradually decreased during the reaction, indicating that a thermally activated PS oxidation was a promising alternative approach for DCF-contaminated groundwater remediation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price includes VAT (France)

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

References

  • Anipsitakis GP, Dionysiou DD (2004) Radical generation by the interaction of transition metals with common oxidants. Environ Sci Technol 38:3705–3712

    Article  CAS  Google Scholar 

  • Bennedsen LR, Muff J, Søgaard EG (2012) Influence of chloride and carbonates on the reactivity of activated persulfate. Chemosphere 86:1092–1097

    Article  CAS  Google Scholar 

  • Chawla OP, Fessenden RW (1975) Electron spin resonance and pulse radiolysis studies of some reactions of peroxysulfate. J Phys Chem 79:2693–2700

    Article  CAS  Google Scholar 

  • Chen JB, Zhou XF, Zhang YL, Qian YJ, Gao HP (2012) Interactions of acidic pharmaceuticals with human serum albumin: insights into the molecular toxicity of emerging pollutants. Amino Acids 43:1419–1429

    Article  CAS  Google Scholar 

  • Chen JB, Gao HW, Zhang YL, Zhang Y, Zhou XF, Li CQ, Gao HP (2014) Developmental toxicity of diclofenac and elucidation of gene regulation in zebrafish (Danio rerio). Sci Rep 4:4841

    CAS  Google Scholar 

  • Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107:907–938

    Article  CAS  Google Scholar 

  • Deng J, Shao Y, Gao N, Deng Y, Zhou S, Hu X (2013a) Thermally activated persulfate (TAP) oxidation of antiepileptic drug carbamazepine in water. Chem Eng J 228:765–771

    Article  CAS  Google Scholar 

  • Deng J, Shao Y, Gao N, Tan C, Zhou S, Hu X (2013b) CoFe2O4 magnetic nanoparticles as a highly active heterogeneous catalyst of oxone for the degradation of diclofenac in water. J Hazard Mater 262:836–844

    Article  CAS  Google Scholar 

  • Furman OS, Teel AL, Watts RJ (2010) Mechanism of base activation of persulfate. Environ Sci Technol 44:6423–6428

    Article  CAS  Google Scholar 

  • Ghauch A, Tuqan AM (2012) Oxidation of bisoprolol in heated persulfate/H2O systems: kinetics and products. Chem Eng J 183:162–171

    Article  CAS  Google Scholar 

  • Ghauch A, Tuqan AM, Kibbi N (2012) Ibuprofen removal by heated persulfate in aqueous solution: a kinetics study. Chem Eng J 197:483–492

    Article  CAS  Google Scholar 

  • Grundwasser KIBOU, Heberer T, Schmidt-Bäumler K, Stan H (1998) Occurrence and distribution of organic contaminants in the aquatic system in Berlin. Part I: Drug residues and other polar contaminants in Berlin surface and groundwater. Acta Hydrochim Hydrobiol 26:272–278

    Article  Google Scholar 

  • Gu X, Lu S, Li L, Qiu Z, Sui Q, Lin K, Luo Q (2011) Oxidation of 1,1,1-trichloroethane stimulated by thermally activated persulfate. Ind Eng Chem Res 50:11029–11036

    Article  CAS  Google Scholar 

  • Han D, Wan J, Ma Y, Wang Y, Huang M, Chen Y, Li D, Guan Z, Li Y (2014) Enhanced decolorization of Orange G in a Fe(II)-EDDS activated persulfate process by accelerating the regeneration of ferrous iron with hydroxylamine. Chem Eng J 256:316–323

    Article  CAS  Google Scholar 

  • He X, Armah A, Dionysiou DD (2013) Destruction of cyanobacterial toxin cylindrospermopsin by hydroxyl radicals and sulfate radicals using UV-254nm activation of hydrogen peroxide, persulfate and peroxymonosulfate. J Photochem Photobiol A 251:160–166

    Article  CAS  Google Scholar 

  • Heberer T (2002) Tracking persistent pharmaceutical residues from municipal sewage to drinking water. J Hydrol 266:175–189

    Article  CAS  Google Scholar 

  • Hori H, Nagaoka Y, Murayama M, Kutsuna S (2008) Efficient decomposition of perfluorocarboxylic acids and alternative fluorochemical surfactants in hot water. Environ Sci Technol 42:7438–7443

    Article  CAS  Google Scholar 

  • Huang KC, Couttenye RA, Hoag GE (2002) Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE). Chemosphere 49:413–420

    Article  CAS  Google Scholar 

  • Huang KC, Zhao Z, Hoag GE, Dahmani A, Block PA (2005) Degradation of volatile organic compounds with thermally activated persulfate oxidation. Chemosphere 61:551–560

    Article  CAS  Google Scholar 

  • Lee YC, Lo SL, Kuo J, Lin YL (2012) Persulfate oxidation of perfluorooctanoic acid under the temperatures of 20–40°C. Chem Eng J 198–199:27–32

    Article  Google Scholar 

  • Liang C, Su HW (2009) Identification of sulfate and hydroxyl radicals in thermally activated persulfate. Ind Eng Chem Res 48:5558–5562

    Article  CAS  Google Scholar 

  • Liang CJ, Bruell CJ, Marley MC, Sperry KL (2003) Thermally activated persulfate oxidation of trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) in aqueous systems and soil slurries. Soil Sediment Contam 12:207–228

    Article  CAS  Google Scholar 

  • Liang C, Wang ZS, Mohanty N (2006) Influences of carbonate and chloride ions on persulfate oxidation of trichloroethylene at 20 °C. Sci Total Environ 370:271–277

    Article  CAS  Google Scholar 

  • Liang C, Wang ZS, Bruell CJ (2007) Influence of pH on persulfate oxidation of TCE at ambient temperatures. Chemosphere 66:106–113

    Article  CAS  Google Scholar 

  • Liang C, Huang CF, Mohanty N, Kurakalva RM (2008) A rapid spectrophotometric determination of persulfate anion in ISCO. Chemosphere 73:1540–1543

    Article  CAS  Google Scholar 

  • Liu CS, Shih K, Sun CX, Wang F (2012) Oxidative degradation of propachlor by ferrous and copper ion activated persulfate. Sci Total Environ 416:507–512

    Article  CAS  Google Scholar 

  • Liu H, Bruton TA, Doyle FM, Sedlak DL (2014) In situ chemical oxidation of contaminated groundwater by persulfate: decomposition by Fe(III)- and Mn(IV)-containing oxides and aquifer materials. Environ Sci Technol 48:10330–10336

    Article  CAS  Google Scholar 

  • Mahdi Ahmed M, Barbati S, Doumenq P, Chiron S (2012) Sulfate radical anion oxidation of diclofenac and sulfamethoxazole for water decontamination. Chem Eng J 197:440–447

    Article  CAS  Google Scholar 

  • Mora VC, Rosso JA, Mártire DO, Gonzalez MC (2011) Phenol depletion by thermally activated peroxydisulfate at 70 °C. Chemosphere 84:1270–1275

    Article  CAS  Google Scholar 

  • Neta P, Huie RE, Ross AB (1988) Rate constants for reactions of inorganic radicals in aqueous solution. J Phys Chem Ref Data 17:1027–1284

    Article  CAS  Google Scholar 

  • Nie M, Yang Y, Zhang Z, Yan C, Wang X, Li H, Dong W (2014) Degradation of chloramphenicol by thermally activated persulfate in aqueous solution. Chem Eng J 246:373–382

    Article  CAS  Google Scholar 

  • Rabiet M, Togola A, Brissaud F, Seidel JL, Budzinski H, Elbaz-Poulichet F (2006) Consequences of treated water recycling as regards pharmaceuticals and drugs in surface and ground waters of a medium-sized Mediterranean catchment. Environ Sci Technol 40:5282–5288

    Article  CAS  Google Scholar 

  • Roshani B, Leitner NKV (2011) Effect of persulfate on the oxidation of benzotriazole and humic acid by e-beam irradiation. J Hazard Mater 190:403–408

    Article  CAS  Google Scholar 

  • Seol Y, Zhang H, Schwartz FW (2003) A review of in situ chemical oxidation and heterogeneity. Environ Eng Geosci 9:37–49

    Article  Google Scholar 

  • Sui Q, Wang B, Zhao W, Huang J, Yu G, Deng S, Qiu Z, Lu S (2012) Identification of priority pharmaceuticals in the water environment of China. Chemosphere 89:280–286

    Article  CAS  Google Scholar 

  • Tan C, Gao N, Deng Y, An N, Deng J (2012) Heat-activated persulfate oxidation of diuron in water. Chem Eng J 203:294–300

    Article  CAS  Google Scholar 

  • Tsitonaki A, Petri B, Crimi M, MosbÆK H, Siegrist RL, Bjerg PL (2010) In situ chemical oxidation of contaminated soil and groundwater using persulfate: a review. Crit Rev Environ Sci Technol 40:55–91

    Article  CAS  Google Scholar 

  • Wang CW, Liang C (2014) Oxidative degradation of TMAH solution with UV persulfate activation. Chem Eng J 254:472–478

    Article  CAS  Google Scholar 

  • Wang H, Yao H, Sun P, Pei J, Li D, Huang CH (2015) Oxidation of tetracycline antibiotics induced by Fe (III) ions without light irradiation. Chemosphere 119:1255–1261

    Article  CAS  Google Scholar 

  • Yan JC, Lei M, Zhu LH, Anjum MN, Zou J, Tang HQ (2011) Degradation of sulfamonomethoxine with Fe3O4 magnetic nanoparticles as heterogeneous activator of persulfate. J Hazard Mater 186:1398–1404

    Article  CAS  Google Scholar 

  • Yang S, Wang P, Yang X, Shan L, Zhang W, Shao X, Niu R (2010) Degradation efficiencies of azo dye Acid Orange 7 by the interaction of heat, UV and anions with common oxidants: persulfate, peroxymonosulfate and hydrogen peroxide. J Hazard Mater 179:552–558

    Article  CAS  Google Scholar 

  • Yukselen-Aksoy Y, Khodadoust A, Reddy K (2010) Destruction of PCB 44 in spiked subsurface soils using activated persulfate oxidation. Water Air Soil Pollut 209:419–427

    Article  CAS  Google Scholar 

  • Zhang Y, Geißen SU, Gal C (2008) Carbamazepine and diclofenac: removal in wastewater treatment plants and occurrence in water bodies. Chemosphere 73:1151–1161

    Article  CAS  Google Scholar 

  • Zhang Q, Chen J, Dai C, Zhang Y, Zhou X (2015) Degradation of carbamazepine and toxicity evaluation using the UV/persulfate process in aqueous solution. J Chem Technol Biotechnol 90:701–708

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We sincerely thank the National Natural Science Foundation of China (51478283) for financially supporting this work.

Author information

Author notes

    Authors and Affiliations

    1. School of Environmental Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215001, People’s Republic of China

      Jiabin Chen & Tianyin Huang

    2. College of Environmental Science and Engineering, Tongji University, Shanghai, 200092, People’s Republic of China

      Yajie Qian & Hongmei Liu

    Authors
    1. Jiabin Chen
      View author publications

      You can also search for this author in PubMed Google Scholar

    2. Yajie Qian
      View author publications

      You can also search for this author in PubMed Google Scholar

    3. Hongmei Liu
      View author publications

      You can also search for this author in PubMed Google Scholar

    4. Tianyin Huang
      View author publications

      You can also search for this author in PubMed Google Scholar

    Corresponding authors

    Correspondence to Jiabin Chen or Tianyin Huang.

    Additional information

    Responsible editor: Santiago V. Luis

    Jiabin Chen and Yajie Qian are contributed equally to this work.

    Electronic supplementary material

    Below is the link to the electronic supplementary material.

    Figure S1

    (DOCX 56 kb)

    Figure S2

    (DOCX 49 kb)

    Rights and permissions

    Reprints and permissions

    About this article

    Check for updates. Verify currency and authenticity via CrossMark

    Cite this article

    Chen, J., Qian, Y., Liu, H. et al. Oxidative degradation of diclofenac by thermally activated persulfate: implication for ISCO. Environ Sci Pollut Res 23, 3824–3833 (2016). https://doi.org/10.1007/s11356-015-5630-0

    Download citation

    • Received:

    • Accepted:

    • Published:

    • Issue Date:

    • DOI: https://doi.org/10.1007/s11356-015-5630-0

    Keywords

    search

    Navigation