Photolysis of bis(2-ethylhexyl) phthalate in aqueous solutions at the presence of natural water photoreactive constituents under simulated sunlight irradiation

  • Qian Yu
  • Xiyao Xiong
  • Jun He
  • Yuegang Zuo
  • Yong Chen
  • Chengjun WangEmail author
Research Article


The photolysis of bis(2-ethylhexyl) phthalate (DEHP) under simulated sunlight in the presence of the natural water photoreactive constituents was investigated. The presence of nitrate or ferric ions facilitated the photodegradation of DEHP via oxidation by generation of •OH. The fulvic acids (FAs), at low concentrations, promoted the photolysis of DEHP via energy transfer from the photoreaction-generated 3FA*. However, the DEHP photolysis was inhibited with high concentrations of FAs since the excess FAs at the surface of solution could act as light screening agents to keep FAs in bulk solution from the light irradiation, further reducing the 3FA* generation. When low concentrations of FAs and chloride ions coexist, the reactive chloride species Cl• and Cl2 could generate via energy transfer from 3FA* to chloride ions and react with DEHP to enhance its degradation. Furthermore, the direct and •OH-initiated DEHP photodegraded intermediates and end products were identified by HPLC-MS2 and its corresponding photolysis pathways were proposed.


Photodegradation Bis(2-ethylhexyl) phthalate Natural photoreactive constituents Aqueous photochemistry 



We thank Mrs. Jialu Lin and Shuihong Pan from Wenzhou University for their operation of LC-MS2 experimental test and analysis of the photodegraded products for this work.

Author contributions

All authors contributed equally.

Funding information

The research project was jointly supported by the National Natural Science Foundation of China (21477088) and the Initiating funding of South-Central University for Nationalities (YZZ18018).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11356_2019_5913_MOESM1_ESM.doc (115 kb)
ESM 1 (DOC 115 kb)


  1. Abdel aiem MM, Rivera-Utrilla J, Ocampo-Pérez R, Méndez-Díaz JD, Sánchez-Polo M (2012) Environmental impact of phthalic acid esters and their removal from water and sediments by different technologies - a review. J Environ Manage 109:164–178CrossRefGoogle Scholar
  2. Bajt O, Maihot G, Bolte M (2001) Degradation of dibutyl phthalate by homogeneous photocatalysis with Fe(III) in aqueous solution. Appl Catal B Environ 33:239–248CrossRefGoogle Scholar
  3. Balabanovich AI, Schnabel W (1998) On the photolysis of phthallic acid dimethyl and diethyl ester: a product analysis study. J Photochem Photobiol A Chem 113:145–153CrossRefGoogle Scholar
  4. Balafas D, Shaw KJ, Whitfield FB (1999) Phthalate and adipate esters in Australian packaging materials. Food Chem 65:279–287CrossRefGoogle Scholar
  5. Bamai YA, Araki A, Kawai T, Tsuboi T, Yoshioka E, Kanazawa A, Cong S, Kishi R (2015) Comparisons of urinary phthalate metabolites and daily phthalate intakes among Japanese families. Int J Hyg Environ Health 218:461–470CrossRefGoogle Scholar
  6. Benedict KB, McFall AS, Anastasio C (2017) Quantum yield of nitrite from the photolysis of aqueous nitrate above 300 nm. Environ Sci Technol 51:4387–4395CrossRefGoogle Scholar
  7. Chen CY (2010) The oxidation of di-(2-ethylhexyl) phthalate (DEHP) in aqueous solution by UV/H2O2 photolysis. Water Air Soil Pollut 209:411–417CrossRefGoogle Scholar
  8. Chen C, Wu P, Chung Y (2009) Coupled biological and photo-Fenton pretreatment system for the removal of di-(2-ethylhexyl) phthalate (DEHP) from water. Bioresour Technol 100:4531–4534CrossRefGoogle Scholar
  9. Chen Y, Li H, Wang Z, Li H, Tao T, Zuo Y (2012) Photodegradation of selected β-blockers in aqueous fulvic acid solutions: kinetics mechanism and product analysis. Water Res 46:2965–2972CrossRefGoogle Scholar
  10. Chen Y, Zhang K, Zuo Y (2013) Direct and indirect photodegradation of estriol in the presence of humic acid, nitrate and iron complexes in water solutions. Sci Total Environ 464:802–809CrossRefGoogle Scholar
  11. Cheng L, Pan S, Ding C, He J, Wang C (2017) Dispersive solid-phase microextraction with graphene oxide based molecularly imprinted polymers for determining bis(2-ethylhexyl) phthalate in environmental water. J Chromatogr A 1511:85–91CrossRefGoogle Scholar
  12. Chiou C, Chen Y, Chang C, Chang C, Shie J, Li Y (2006) Photochemical mineralization of di-n-butyl phthalate with H2O2/Fe3+. J Hazard Mater 135:344–349CrossRefGoogle Scholar
  13. Grebel JE, Pignatello JJ, Mitch WA (2012) Impact of halide ions on natural organic matter-sensitized photolysis of 17β-estradiol in saline waters. Environ Sci Technol 46:7128–7134CrossRefGoogle Scholar
  14. Han D, Li J, Cao H, He M, Hu J, Yao S (2014) Theoretical investigation on the mechanisms and kinetics of OH-initiated photooxidation of dimethyl phthalate (DMP) in atmosphere. Chemosphere 95:50–57CrossRefGoogle Scholar
  15. Herrero L, Calvarro S, Fernández MA, Quintanilla-López JE, González MJ, Gómara B (2015) Feasibility of ultra-high performance liquid and gas chromatography coupled to mass spectrometry for accurate determination of primary and secondary phthalate metabolites in urine samples. Anal Chim Acta 853:625–636CrossRefGoogle Scholar
  16. Hizal G, Zhu QQ, Fischer CH, Fritz PM, Schnabel W (1993) On the photolysis of phthalic acid dialkyl esters: a product analysis study. J Photochem Photobiol A Chem 69:33–39CrossRefGoogle Scholar
  17. Jacobs LE, Fimmen RL, Chin Y, Mash HE, Weavers LK (2011) Fulvic acid mediated photolysis of ibuprofen in water. Water Res 45:4449–4458CrossRefGoogle Scholar
  18. Jacobs LE, Weavers LK, Houtz EF, Chin Y (2012) Photosensitized degradation of caffeine: role of fulvic acids and nitrate. Chemosphere 86:124–129CrossRefGoogle Scholar
  19. Kaushal SS, Groffman PM, Likens GE, Belt KT, Stack WP, Kelly VR, Band LE, Fisher GT (2005) Increased salinization of fresh water in the northeastern United States. Proc Natl Acad Sci USA 102:13517–13520CrossRefGoogle Scholar
  20. Kim MK, Zoh KD (2013) Effects of natural water constituents on the photo-decomposition of methylmercury and the role of hydroxyl radical. Sci Total Environ 449:95–101CrossRefGoogle Scholar
  21. Koch HM, Rossbach B, Drexler H, Angerer J (2003) Internal exposure of the general population to DEHP and other phthalates determination of secondary and primary phthalate monoester metabolites in urine. Environ Res 93:177–185CrossRefGoogle Scholar
  22. Kong L, Ferry JL (2003) Effect of salinity on the photolysis of chrysene adsorbed to a smectite clay. Environ Sci Technol 37:4894–4900CrossRefGoogle Scholar
  23. Lau T, Chu W, Graham N (2005) The degradation of endocrine disruptor di-n-butyl phthalate by UV irradiation: a photolysis and product study. Chemosphere 60:1045–1053CrossRefGoogle Scholar
  24. Li S, Sun W (2014) Photocatalytic degradation of 17α-ethinylestradiol in mono- and binary systems of fulvic acid and Fe(III): application of fluorescence excitation/emission matrixes. Chem Eng J 237:101–108Google Scholar
  25. Makunina MP, Pozdnyakow IP, Chen Y, Grivin VP, Bazhin NM, Plyusnin VF (2015) Mechanistic study of fulvic acid assisted propranolol photodegradation in aqueous solution. Chemosphere 119:1406–1410CrossRefGoogle Scholar
  26. Murray K, Linder PW (1983) Fulvic acids: structure and metal binding. I. A random molecular model. J Soil Sci 34:511–523CrossRefGoogle Scholar
  27. Net S, Delmont A, Sempéré R, Paluselli A, Ouddane B (2015) Reliable quantification of phthalates in environmental matrices (air, water, sludge, sediment and soil): a review. Sci Total Environ 515:162–180CrossRefGoogle Scholar
  28. Pan S, Feng C, Lin J, Cheng L, Wang C, Zuo Y (2017) Occurrence and photodegradation of methylmercury in surface water of Wen-Rui-Tang River network, Wenzhou, China. Environ. Sci Pollut Res 24:11289–11298CrossRefGoogle Scholar
  29. Parker KM, Mitch WA (2016) Halogen radicals contribute to photooxidation in coastal and esturine waters. Proc Natl Acad Sci 113:5868–5873CrossRefGoogle Scholar
  30. Peng X, Feng L, Li X (2013) Pathway of diethyl phthalate photolysis in sea-water determined by gas chromatography–mass spectrometry and compound-specific isotope analysis. Chemosphere 90:220–226CrossRefGoogle Scholar
  31. Rajca M, Bodzek M (2013) Kinetics of fulvic and humic acids photodegradation in water solutions. Sep Purif Technol 120:35–42CrossRefGoogle Scholar
  32. Reemtsma T, These A, Springer A, Linscheid M (2008) Differences in the molecular composition of fulvic acid size fractions detected by size-exclusion chromatography–on line Fourier transform ion cyclotron resonance mass spectrometry. Water Res 42:63–72CrossRefGoogle Scholar
  33. Staples CA, Peterson DR, Parkerton TF, Adams WJ (1997) The environmental fate of phthalate esters: a literature review. Chemosphere 35:667–749CrossRefGoogle Scholar
  34. Sun R, Wang D, Zhang Y, Mao W, Zhang T, Ma M, Zhang C (2013) Photo-degradation of monomethylmercury in the presence of chloride ion. Chemosphere 91:1471–1476CrossRefGoogle Scholar
  35. Ukpebor JE, Halsall CJ (2012) Effects of dissolved water constituents on the photodegradation of fenitrothion and diazinon. Water Air Soil Pollut 223:655–666CrossRefGoogle Scholar
  36. Vione D, Maurino V, Minero C, Calza P, Pelizzetti E (2005) Phenol chlorination and photochlorination in the presence of chloride ions in homogeneous aqueous solution. Environ Sci Technol 39:5066–5075CrossRefGoogle Scholar
  37. Wang C, Cheng L, Zhang L, Zuo Y (2019) Graphene oxide-based molecularly imprinted polymers modified with β-cyclodextrin for selective extraction of di(2-ethylhexyl)phthalate in environmental waters. J Sep Sci 42:1248–1256CrossRefGoogle Scholar
  38. Wen G, Ma J, Liu Z, Zhao L (2011) Ozonation kinetics for the degradation of phthalate esters in water and the reduction of toxicity in the process of O3/H2O2. J Hazard Mater 195:371–377CrossRefGoogle Scholar
  39. Xia X, Li G, Yang Z, Chen Y, Huang G (2009) Effects of fulvic acid concentration and origin on photodegradation of polycyclic aromatic hydrocarbons in aqueous solution: importance of active oxygen. Environ Pollut 157:1352–1359CrossRefGoogle Scholar
  40. Yang G, Zhao X, Sun X, Lu X (2005) Oxidative degradation of diethyl phthalate by photochemically-enhanced Fenton reaction. J Hazard Mater 26:112–118CrossRefGoogle Scholar
  41. Zeng F, Wen J, Gui K, Wu L, Liu M, Li Y, Lin Y, Zhu F, Ma Z, Zeng Z (2009) Seasonal distribution of phthalate esters in surface water of the urban lakes in the subtropical city, Guangzhou, China. J Hazard Mater 169:719–725CrossRefGoogle Scholar
  42. Zhang Y, Lee H (2013) Low-density solvent-based vortex-assisted surfactant-enhanced-emulsification liquid–liquid microextraction combined with gas chromatography–mass spectrometry for the fast determination of phthalate esters in bottled water. J Chromatogr A 1274:28–35CrossRefGoogle Scholar
  43. Zhao X, Yang G, Wang Y, Gao X (2004) Photochemical degradation of dimethyl phthalate by Fenton reagent. J Photochem Photobiol A 161:215–220CrossRefGoogle Scholar
  44. Zuo Y, Deng Y (1998) The near-UV absorption constants for nitrite ion in aqueous solution. Chemosphere 36:181–188CrossRefGoogle Scholar
  45. Zuo Y, Hoigné J (1992) Formation of hydrogen peroxide and depletion of oxalic acid in atmospheric water by photolysis of iron(III)-oxalato complexes. Environ Sci Technol 26:1014–1022Google Scholar
  46. Zuo Y, Hoigné J (1993) Evidence for photochemical formation of H2O2 and oxidation of SO2 in authentic fog water. Science 260:71–73Google Scholar
  47. Zuo Y, Zhang K, Wu J, Men B, He M (2011) Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection. Chemosphere 83:1014–1019CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Resources and Environmental ScienceSouth-Central University for NationalitiesWuhanChina
  2. 2.Department of Chemical and Environmental EngineeringThe University of Nottingham Ningbo ChinaNingboChina
  3. 3.Department of Chemistry and BiochemistryUniversity of Massachusetts DartmouthNorth DartmouthUSA
  4. 4.School of Environmental Science and EngineeringHuazhong University of Science and TechnologyWuhanChina

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