Photodegradation of nonylphenol polyethoxylates in aqueous solution
Lei Wang A , Hongwen Sun A C , Yinghong Wu B , Guolan Huang A and Shugui Dai AA Key Laboratory of Pollution Processes and Environmental Criteria (Nankai University), Ministry of Education, Tianjin, 300071, China.
B Tianjin Centers for Disease Control and Prevention, 76 Hualong Road, Tianjin, 300011, China.
C Corresponding author. Email: nkenv@nankai.edu.cn
Environmental Chemistry 6(2) 185-193 https://doi.org/10.1071/EN08101
Submitted: 3 December 2008 Accepted: 3 March 2009 Published: 27 April 2009
Environmental context. Nonylphenol polyethoxylates (NPEOs) are widely used non-ionic surfactants, and they cause environmental concern because some metabolites of NPEOs possess endocrine-disrupting activities. Photodegradation is an important pathway for NPEOs degradation, and different degradation products may lead to different environmental risks. The present paper looks at the kinetics and pathways of NPEO photodegradation in aqueous solutions, focussing on the effects of humic acid, H2O2, and FeIII. We found that the presence of different chemicals led to different degradation pathways, and a new mechanism is proposed.
Abstract. To further elucidate the mechanism of photoinduced degradation of nonylphenol polyethoxylates (NPEOs) in aqueous environments, two different light systems, UVA and simulated sunlight, were used, and the effects of humic acid, H2O2, and FeIII were investigated. The 96-h degradation efficiencies of NPEOs in pure water solution were found to be 36.6 and 22.6% under UVA and SSL irradiation respectively. The presence of humic acid and FeIII in solution increased the photodegradation efficiency of NPEOs to different extents. The proportion of short-chain NPEOs in the NPEOn mixture was found to increase significantly in the solution containing FeIII, whereas this phenomenon was not observed in pure water and solutions containing H2O2 or humic acid. The result of NPEO3 photodegradation experiments indicated that FeIII in solution led to an ethoxylate-reduction pathway. Dicarboxylated formate ethoxylates were proposed as the intermediate products of NPEO photodegradation through an oxidative pathway based on the analytical results of liquid chromatography–electrospray ionisation–mass spectrometry and tandem mass spectrometry. Different mechanisms of NPEO photodegradation were elucidated.
Additional keywords: dicarboxylated formate ethoxylates, ethoxylate-reduction pathway, humic acid, hydrogen peroxide, iron(III).
Acknowledgement
The present study was funded by the National Natural Science Foundation of China (No. 20677031 & No. 50239060).
[1]
N. Jonkers ,
R. W. P. M. Laane ,
C. de Graaf ,
P. de Voogt ,
Fate modeling of nonylphenol ethoxylates and their metabolites in the Dutch Scheldt and Rhine estuaries: validation with new field data.
Estuar. Coast. Shelf. Sci. 2005
, 62, 141.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[2]
G. G. Ying ,
B. Williams ,
R. Kookana ,
Environmental fate of alkylphenols and alkylphenol ethoxylates: a review.
Environ. Int. 2002
, 28, 215.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[3]
J. A. Field ,
R. L. Reed ,
Nonylphenol polyethoxycarboxylate metabolites of non-ionic surfactants in US paper-mill effluents, municipal sewage-treatment plant effluents and river waters.
Environ. Sci. Technol. 1996
, 30, 3544.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[4]
T. L. Potter ,
K. Simmons ,
J. N. Wu ,
P. Kostecki ,
E. Calabress ,
Static die-away of a nonylphenol ethoxylate surfactant in estuarine water samples.
Environ. Sci. Technol. 1999
, 33, 113.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[5]
C. A. Staples ,
J. B. Williams ,
R. L. Blessing ,
P. T. Varineau ,
Measuring the biodegradability of nonylphenol ether carboxylates, octylphenol ether carboxylates and nonylphenol.
Chemosphere 1999
, 38, 2029.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[6]
N. Jonkers ,
T. Knepper ,
P. de Voogt ,
Aerobic biodegradation studies of nonylphenol polyethoxylates in river water using liquid chromatography–electrospray tandem mass spectrometry.
Environ. Sci. Technol. 2001
, 35, 335.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[7]
N. Jonkers ,
R. W. P. M. Laane ,
C. de Graaf ,
P. de Voogt ,
Fate of nonylphenol ethoxylates and their metabolites in two Dutch estuaries: evidence of biodegradation in the field.
Environ. Sci. Technol. 2003
, 37, 321.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[8]
L. Wang ,
Y. Wu ,
H. Sun ,
J. Xu ,
S. Dai ,
Distribution and dissipation pathways of nonylphenol polyethoxylates in the Yellow River: site investigation and lab-scale studies.
Environ. Int. 2006
, 32, 907.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[9]
S. Jobling ,
J. P. Sumpter ,
Detergent components in sewage effluent are weakly oestrogenic to fish: an in vitro study using rainbow trout (Oncorhynchus mykiss) hepatocytes.
Aquat. Toxicol. 1993
, 27, 361.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[10]
S. C. Laws ,
S. A. Carey ,
J. M. Ferrell ,
G. J. Bodman ,
R. L. Cooper ,
Estrogenic activity of octylphenol, nonylphenol, bisphenol A and methoxychlor in rats.
Toxicol. Sci. 2000
, 54, 154.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[11]
D. Vione ,
G. Falletti ,
V. Maurino ,
C. Minero ,
E. Pelizzetti ,
M. Malandrino ,
R. Ajassa ,
R. I. Olariu ,
C. Arsene ,
Sources and sinks of hydroxyl radicals upon irradiation of natural water samples.
Environ. Sci. Technol. 2006
, 40, 3775.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[12]
C. D. Clark ,
W. J. De Bruyn ,
J. Ting ,
W. Scholle ,
Solution medium effects on the photochemical degradation of pyrene in water.
J. Photochem. Photobiol. A 2007
, 186, 342.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[13]
R. Goto ,
T. Kubota ,
Y. Ibuki ,
K. Kaji ,
A. Goto ,
Degradation of nonylphenol polyethoxylates by ultraviolet B irradiation and effects of their products on mammalian cultured cells.
Toxicology 2004
, 202, 237.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[14]
K. B. Sherrard ,
P. J. Marriott ,
R. G. Amiet ,
M. J. McCormick ,
R. Colton ,
K. Millington ,
Spectroscopic analysis of heterogeneous photocatalysis products of nonylphenol and primary alcohol ethoxylate non-ionic surfactants.
Chemosphere 1996
, 33, 1921.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[15]
K. B. Sherrard ,
P. J. Marriott ,
R. G. Amiet ,
R. Colton ,
M. J. McCormick ,
G. C. Smith ,
Photocatalytic degradation of secondary alcohol ethoxylate: spectroscopic, chromatographic and mass spectrometric studies.
Environ. Sci. Technol. 1995
, 29, 2235.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[16]
N. Brand ,
G. Mailhot ,
M. Bolte ,
The interaction ‘light, Fe(III)’ as a tool for pollutant removal in aqueous solution: degradation of alcohol ethoxylates.
Chemosphere 2000
, 40, 395.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[17]
N. Brand ,
G. Mailhot ,
M. Bolte ,
Degradation photoinduced by Fe(III): method of alkylphenol ethoxylates removal in water.
Environ. Sci. Technol. 1998
, 32, 2715.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[18]
L. Chen ,
H. Zhou ,
Q. Deng ,
Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products.
Chemosphere 2007
, 68, 354.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[19]
R. G. Zepp ,
P. F. Schlotzhauer ,
R. M. Sink ,
Photosensitized transformations involving electronic energy transfer in natural waters: role of humic substances.
Environ. Sci. Technol. 1985
, 19, 74.
| Crossref | GoogleScholarGoogle Scholar |
[20]
S. Canonica ,
U. Jans ,
K. Stemmler ,
J. Hoigné ,
Transformation kinetics of phenols in water: photosensitization by dissolved natural organic material and aromatic ketones.
Environ. Sci. Technol. 1995
, 29, 1822.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[21]
[22]
J. R. Garbin ,
D. M. B. P. Milori ,
M. L. Simões ,
W. T. L. da Silva ,
L. M. Neto ,
Influence of humic substances on the photolysis of aqueous pesticide residues.
Chemosphere 2007
, 66, 1692.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[23]
E. Rodríguez ,
M. Mimbrero ,
F. J. Masa ,
F. J. Beltrán ,
Homogeneous iron-catalyzed photochemical degradation of muconic acid in water.
Water Res. 2007
, 41, 1325.
| Crossref | GoogleScholarGoogle Scholar | PubMed |
[24]
B. C. Faust ,
J. Hoigne ,
Photolysis of Fe(III)–hydroxy complexes as sources of OH radicals in cloud, fog and rain.
Atmos. Environ. 1990
, 24, 79.
[25]
O. Bajt ,
G. Mailhot ,
M. Bolte ,
Degradation of dibutyl phthalate by homogeneous photocatalysis with Fe(III) in aqueous solution.
Appl. Catal. B 2001
, 33, 239.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[26]
S. Lunák ,
P. J. Sedlák ,
Photoinitiated reactions of hydrogen peroxide in the liquid phase.
Photochem. Photobiol. A 1992
, 68, 1.
| Crossref | GoogleScholarGoogle Scholar |
[27]
[28]
S. Hayashi ,
S. Saito ,
J. H. Kim ,
O. Nishimura ,
R. Sudo ,
Aerobic biodegradation behavior of nonylphenol polyethoxylates and their metabolites in the presence of organic matter.
Environ. Sci. Technol. 2005
, 39, 5626.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
[29]
A. Di Corcia ,
A. Costantino ,
C. Crescenzi ,
E. Marinoni ,
R. Sampero ,
Characterization of recalcitrant intermediates from biotransformation of the branched alkyl side chain of nonylphenol ethoxylate surfactants.
Environ. Sci. Technol. 1998
, 32, 2401.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
[30]
J. A. Howitt ,
D. S. Baldwin ,
G. N. Rees ,
B. T. Hart ,
Facilitated heterogeneous photodegradation of dissolved organic matter by particulate iron.
Environ. Chem. 2004
, 1, 197.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
