Environmental Science and Pollution Research

, Volume 25, Issue 31, pp 31091–31100 | Cite as

Photochemical oxidation of di-n-butyl phthalate in atmospheric hydrometeors by hydroxyl radicals from nitrous acid

  • Yu Lei
  • Chengzhu ZhuEmail author
  • Jun Lu
  • Yongchao Zhu
  • Qiuyue Zhang
  • Tianhu Chen
  • Hongbin XiongEmail author
Research Article


The photochemical oxidation of di-n-butyl phthalate (DBP) by OH radicals from nitrous acid (HONO) in atmospheric hydrometeors was explored by two techniques, steady-state irradiation, and laser flash photolysis (LFP). The effects of atmospheric liquid parameters on DBP transformation were systematically evaluated, showing that DBP does not react with HONO directly and OH-initiated reactions are crucial steps for consumption and transformation of DBP. Two reaction channels are operative: OH addition and hydrogen atom abstraction. The overall rate constant for the reaction of DBP with OH is 5.7 × 109 M−1 s−1, and its specific rate constant for addition is 3.7 × 109 M−1 s−1 determined by using laser flash photolysis technique. Comparing the individual reaction rate constant for aromatic ring addition with the total rate constant, the majority of the OH radicals (about 65%) attack the aromatic ring. The major transformation products were identified by GC-MS, and the trends of their yields derived from both ring addition and H-abstraction with time are discussed. These results provide important insights into the photochemical transformation of DBP in atmospheric hydrometeors and contribute to atmospheric aerosol chemistry.


Di-butyl phthalate Nitrous acid Hydroxyl radicals Kinetics Mechanisms Atmospheric hydrometeors 


Funding information

Financial support was provided by the National Natural Science Foundation of China (NSFC) (21876038) and the Key University Science Research Project of Anhui Provincial Education Department of China (KJ2017ZD46).


  1. Acker K, Möller D, Wieprecht W, Auel R, Kalass D, Tscherwenka W (2001) Nitrous and nitric acid measurements inside and outside of clouds at Mt. Brocken. Water Air Soil Pollut 130:331–336. CrossRefGoogle Scholar
  2. Ahmad R, Gautam AK, Verma Y, Sedha S, Kumar S (2014) Effects of in utero di-butyl phthalate and butyl benzyl phthalate exposure on offspring development and male reproduction of rat. Environ Sci Pollut Res 21:3156–3165. CrossRefGoogle Scholar
  3. An T, Gao Y, Li G, Kamat PV, Peller J, Joyce MV (2014) Kinetics and mechanism of OH mediated degradation of dimethyl phthalate in aqueous solution: experimental and theoretical studies. Environ Sci Technol 48:641–648. CrossRefGoogle Scholar
  4. Anastasio C, Chu L (2009) Photochemistry of nitrous acid (HONO) and nitrous acidium ion (H2ONO+) in aqueous solution and ice. Environ Sci Technol 43:1108–1114. CrossRefGoogle Scholar
  5. Anastasio C, Mcgregor KG (2001) Chemistry of fog waters in California’s central valley: 1. In situ photoformation of hydroxyl radical and singlet molecular oxygen. Atmos Environ 35:1079–1089. CrossRefGoogle Scholar
  6. Arakaki T, Faust BC (1998) Sources, sinks, and mechanisms of hydroxyl radical (OH) photoproduction and consumption in authentic acidic continental cloud waters from Whiteface Mountain, New York: the role of the Fe(r) (r=II, III) photochemical cycle. J Geophys Res 103:3487–3504. CrossRefGoogle Scholar
  7. Arakaki T, Miyake T, Hirakawa T, Sakugawa H (1999) pH dependent photoformation of hydroxyl radical and absorbance of aqueous-phase N(III) (HNO2 and NO2 ). Environ Sci Technol 33:2561–2565. CrossRefGoogle Scholar
  8. Atlas E, Giam CS (1981) Global transport of organic pollutants: ambient concentrations in the remote marine atmosphere. Science 211:163–165. CrossRefGoogle Scholar
  9. Bajt O, Mailhot G, Bolte M (2001) Degradation of dibutyl phthalate by homogeneous photocatalysis with Fe(III) in aqueous solution. Appl Catal B Environ 33:239–248. CrossRefGoogle Scholar
  10. Bartolomei V, Sörgel M, Gligorovski S, Alvarez EG, Gandolfo A, Strekowski R, Quivet E, Held A, Zetzsch C, Wortham H (2014) Formation of indoor nitrous acid (HONO) by light-induced NO2 heterogeneous reactions with white wall paint. Environ Sci Pollut Res 21:9259–9269. CrossRefGoogle Scholar
  11. Behnke W, Nolting F, Zetzsch C (1987) The atmospheric fate of DI(2-ethylhexyl-)phthalate, adsorbed on various metal oxide model aerosols and on coal fly ash. J Aerosol Sci 18:849–852. CrossRefGoogle Scholar
  12. Benjamin S, Masai E, Kamimura N, Takahashi K, Anderson RC, Faisal PA (2017) Phthalates impact human health: epidemiological evidences and plausible mechanism of action. J Hazard Mater 340:360–383. CrossRefGoogle Scholar
  13. Bernard F, Cazaunau M, Grosselin B, Zhou B, Zheng J, Liang P, Zhang Y, Ye X, Daele V, Mu Y, Zhang R, Chen J, Mellouki A (2016) Measurements of nitrous acid (HONO) in urban area of Shanghai, China. Environ Sci Pollut Res 23:5818–5829. CrossRefGoogle Scholar
  14. Chen J, Ehrenhauser FS, Valsaraj KT, Wornat MJ (2006) Uptake and UV-photooxidation of gas-phase PAHs on the surface of atmospheric water films. 1. Naphthalene. J Phys Chem A 110:9161–9168. CrossRefGoogle Scholar
  15. Dematteo MP, Poole JS, Shi X, Sachdeva R, Hatcher PG, Hadad CM, Platz MS (2005) On the electrophilicity of hydroxyl radical: a laser flash photolysis and computational study. J Am Chem Soc 127:7094–7109. CrossRefGoogle Scholar
  16. Fang J, Fu Y, Shang C (2014) The roles of reactive species in micropollutant degradation in the UV/free chlorine system. Environ Sci Technol 48:1859–1868. CrossRefGoogle Scholar
  17. Gao Y, An T, Ji Y, Li G, Zhao C (2015) Eco-toxicity and human estrogenic exposure risks from OH-initiated photochemical transformation of four phthalates in water: a computational study. Environ Pollut 206:510–517. CrossRefGoogle Scholar
  18. George C, Ammann M, D’Anna B, Donaldson DJ, Nizkorodov S (2015) Heterogeneous photochemistry in the atmosphere. Chem Rev 115:4218–4258. CrossRefGoogle Scholar
  19. Gligorovski S, Strekowski R, Barbati S, Vione D (2015) Environmental implications of hydroxyl radicals (OH). Chem Rev 115:13051–13092. CrossRefGoogle Scholar
  20. Han C, Liu Y, He H (2017) Heterogeneous reaction of NO2 with soot at different relative humidity. Environ Sci Pollut Res 24:21248–21255. CrossRefGoogle Scholar
  21. Harris CA, Henttu P, Parker MG, Sumpter JP (1997) The estrogenic activity of phthalate esters in vitro. Environ Health Persp 105:802–811. CrossRefGoogle Scholar
  22. He Y, Zhou X, Hou J, Gao H, Bertman SB (2006) Importance of dew in controlling the air-surface exchange of HONO in rural forested environments. Geophys Res Lett 33:87–94. CrossRefGoogle Scholar
  23. Herrmann H, Schaefer T, Tilgner A, Styler SA, Weller C, Teich M, Otto T (2015) Tropospheric aqueous phase chemistry: kinetics, mechanisms, and its coupling to a changing gas phase. Chem Rev 115:4259–4334. CrossRefGoogle Scholar
  24. Huang L, Dong W, Hou H (2013) Photochemical reaction of 2-chlorobiphenyl with N(III) (H2ONO+/HONO/NO2 ) in acidic environment studied by using co-linear laser flash photolysis. J Photochem Photobiol A Chem 268:44–49. CrossRefGoogle Scholar
  25. Kong S, Ji Y, Liu L, Chen L, Zhao X (2013) Spatial and temporal variation of phthalic acid esters(PAEs) in atmospheric PM10 and PM2.5 and the influence of ambient temperature in Tianjin, China. Atmos Environ 74:199–208. CrossRefGoogle Scholar
  26. Lammel G, Cape JN (1996) Nitrous acid and nitrite in the atmosphere. Chem Soc Rev 25:361–369. CrossRefGoogle Scholar
  27. Laurentiis DE, Buoso S, Maurino V, Minero C, Vione D (2013) Optical and photochemical characterization of chromophoric dissolved organic matter from lakes in Terra Nova bay, Antarctica. Evidence of considerable photoreactivity in an extreme environment. Environ Sci Technol 47:14089–14098. CrossRefGoogle Scholar
  28. Lebedev AT, Polyakova OV, Mazur DM, Artaev VB, Canet I, Lallement A, Vaïtilingom M, Deguillaume L, Delort AM (2018) Detection of semi-volatile compounds in cloud waters by GC×GC-TOFMS. Evidence of phenols and phthalates as priority pollutants. Environ Pollut 241:616–625. CrossRefGoogle Scholar
  29. Lei Y, Zhu C, Lu J, Zhu Y, Zhu M, Chen T, Peng S (2018) Photochemical reaction kinetics and mechanisms of diethyl phthalate with N (III) in the atmospheric aqueous environment. J Photochem Photobiol A Chem 362:21–30. CrossRefGoogle Scholar
  30. Lottrup G, Andersson AM, Leffers H, Mortensen GK, Toppari J, Skakkebaeek NE, Main KM (2006) Possible impact of phthalates on infant reproductive health. Int J Androl 29:172–180. CrossRefGoogle Scholar
  31. Lovato ME, Gilliard MB, Cassano AE, Martín CA (2015) Kinetics of the degradation of n-butyl benzyl phthalate using O3/UV, direct photolysis, direct ozonation and UV effects. Environ Sci Pollut Res 22:909–917. CrossRefGoogle Scholar
  32. Ma J, Zhu C, Lu J, Wang T, Hu S, Chen T (2017a) Photochemical reaction between biphenyl and N(III) in the atmospheric aqueous phase. Chemosphere 167:462–468. CrossRefGoogle Scholar
  33. Ma J, Zhu C, Lu J, Lei Y, Wang J, Chen T (2017b) Photochemical reaction between triclosan and nitrous acid in the atmospheric aqueous environment. Atmos Environ 157:38–48. CrossRefGoogle Scholar
  34. Mabey W, Mill T (1978) Critical review of hydrolysis of organic compounds in water under environmental conditions. J Phys Chem Ref Data 7:383–415. CrossRefGoogle Scholar
  35. Mailhot G, Sarakha M, Lavedrine B, Caceres J, Malato S (2002) Fe(III)-solar light induced degradation of diethyl phthalate (DEP) in aqueous solutions. Chemosphere 49:525–532. CrossRefGoogle Scholar
  36. Mcneill VF (2015) Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols. Environ Sci Technol 49:1237–1244. CrossRefGoogle Scholar
  37. Mohnen VA, Vong RJ (1993) A climatology of cloud chemistry for the eastern United States derived from the mountain cloud chemistry project. Environ Rev 1:38–54. CrossRefGoogle Scholar
  38. Ouyang B, Dong W, Hou H (2005) A laser flash photolysis study of nitrous acid in the aqueous phase. Chem Phys Lett 402:306–311. CrossRefGoogle Scholar
  39. Poole JS, Shi X, Hadad CM, Platz MS (2005) Reaction of hydroxyl radical with aromatic hydrocarbons in nonaqueous solutions: a laser flash photolysis study in acetonitrile. J Phys Chem A 109:2547–2551. CrossRefGoogle Scholar
  40. Rubio MA, Lissi E, Villena G (2002) Nitrite in rain and dew in Santiago city, Chile. Its possible impact on the early morning start of the photochemical smog. Atmos Environ 36:293–297. CrossRefGoogle Scholar
  41. Sedha S, Gautam AK, Verma Y, Ahmad R, Kumar S (2015) Determination of in vivo estrogenic potential of Di-isobutyl phthalate (DIBP) and Di-isononyl phthalate (DINP) in rats. Environ Sci Pollut Res 22:18197–18202. CrossRefGoogle Scholar
  42. Song W, Yan S, Cooper WJ, Dionysiou DD, O’Shea KE (2012) Hydroxyl radical oxidation of cylindrospermopsin (cyanobacterial toxin) andits role in the photochemical transformation. Environ Sci Technol 46:12608–12615. CrossRefGoogle Scholar
  43. Staples CA, Peterson DR, Parkerton TF, Adams WJ (1997) The environmental fate of phthalate esters: a literature review. Chemosphere 35:667–749. CrossRefGoogle Scholar
  44. Teil MJ, Blanchard M, Chevreuil M (2006) Atmospheric fate of phthalate esters in an urban area (Paris-France). Sci Total Environ 354:212–223. CrossRefGoogle Scholar
  45. Thanassi JW, Bruice TC (1966) Neighboring carboxyl group participation in the hydrolysis of monoesters of phthalic acid. The dependence of mechanisms on leaving group tendencies. J Am Chem Soc 88:747–752. CrossRefGoogle Scholar
  46. Thuren A, Larsson P (1990) Phthalate esters in the Swedish atmosphere. Environ Sci Technol 24:554–559. CrossRefGoogle Scholar
  47. Tomaz S, Jaffrezo JL, Favez O, Perraudin E, Villenave E, Albinet A (2017) Sources and atmospheric chemistry of oxy- and nitro-PAHs in the ambient air of Grenoble (France). Atmos Environ 161:144–154. CrossRefGoogle Scholar
  48. Torre A, Lain L, Bochicchio R (2003) Bond orders and their relationships with cumulant and unpaired electron densities. J Phys Chem A 107:127–130. CrossRefGoogle Scholar
  49. Treinin A, Hayon E (1970) Absorption spectra and reaction kinetics of NO2, N2O3, and N2O4 in aqueous solution. J Am Chem Soc 92:5821–5828. CrossRefGoogle Scholar
  50. Valsaraj KT (2009) Trace gas adsorption thermodynamics at the air-water interface: implications in atmospheric chemistry. Pure Appl Chem 81:1889–1901. CrossRefGoogle Scholar
  51. Vione D, Maurino V, Minero C, Pelizzetti E, Harrison MA, Olariu RI, Arsene C (2006) Photochemical reactions in the tropospheric aqueous phase and on particulate matter. Chem Soc Rev 35:441–453. CrossRefGoogle Scholar
  52. Vitali M, Guidotti M, Macilenti G, Cremisini C (1997) Phthalate esters in freshwaters as markers of c-ontamination sources—a site study in Italy. Environ Int 23:337–347. CrossRefGoogle Scholar
  53. Wang B, Wang H, Zhou W, Chen Y, Zhou Y, Jiang Q (2015) Urinary excretion of phthalate metabolites in school children of China: implication for cumulative risk assessment of phthalate exposure. Environ Sci Technol 49:1120–1129. CrossRefGoogle Scholar
  54. Wen G, Ma J, Liu ZQ, 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 195:371–377. CrossRefGoogle Scholar
  55. Wolfe NL, Steen WC, Burns LA (1980) Phthalate ester hydrolysis: linear free energy relationships. Chemosphere 9:403–408. CrossRefGoogle Scholar
  56. Xie Z, Ebinghaus R, Temme C, Caba A, Ruck W (2005) Atmospheric concentrations and air-sea exchanges of phthalates in the North Sea (German bight). Atmos Environ 39:3209–3219. CrossRefGoogle Scholar
  57. Xu B, Gao NY, Sun XF, Xia SJ, Rui M (2007) Photochemical degradation of diethyl phthalate with UV/H2O2. J Hazard Mater B 139:132–139. CrossRefGoogle Scholar
  58. Yuan B, Li X, Graham N (2008) Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe (VI) systems. Chemosphere 72:197–204. CrossRefGoogle Scholar
  59. Zhan M, Yang X, Xian Q, Kong L (2006) Photosensitized degradation of bisphenol A involving reactive oxygen species in the presence of humic substances. Chemosphere 63:378–386. CrossRefGoogle Scholar
  60. Zhu CZ, Ouyang B, Wang JQ, Huang L, Dong WB, Hou HQ (2007) Photochemistry in the mixed aqueous solution of nitrobenzene and nitrous acid as initiated by the 355 nm UV light. Chemosphere 67:855–861. CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Institute of Atmospheric Environment and Pollution Control, School of Resource and Environmental EngineeringHefei University of TechnologyHefeiPeople’s Republic of China
  2. 2.Center of Analysis and MeasurementHefei University of TechnologyHefeiPeople’s Republic of China

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