Solar Photo-Fenton Induced Degradation of Combined Chlorpyrifos, Cypermethrin and Chlorothalonil Pesticides in Aqueous Solution
The feasibility of employing solar radiation for
enhanced Fenton process in degradation of combined chlorpyrifos,
cypermethrin and chlorothalonil pesticides was examined. The effect
of various operating conditions of the process on biodegradability
improvement and mineralization of the pesticides were also
evaluated. The optimum operating conditions for treatment of
aqueous solution containing 100, 50 and 250 mg L-1 chlorpyrifos
cypermethrin and chlorothalonil, respectively were observed to be
H2O2/COD molar ratio 2, H2O2/Fe2+ molar ratio 25 and pH 3. Under
the optimum operating conditions, complete degradation of the
pesticides occurred in 1 min. Biodegradability (BOD5/COD)
increased from zero to 0.36 in 60 min, and COD and TOC removal
were 74.19 and 58.32%, respectively in 60 min. Due to
mineralization of organic carbon, decrease in ammonia-nitrogen from
22 to 4.3 mg L-1 and increase in nitrate from 0.7 to 18.1 mg L-1 in
60 min were recorded. The study indicated that solar photo-Fenton
process can be used for pretreatment of chlorpyrifos, cypermethrin
and chlorothalonil pesticides in aqueous solution for further
biological treatment.
[1] S. Kundua, A. Pala, A. K. Dikshitb, ÔÇÿÔÇÿUV induced degradation of
herbicide 2, 4-D: kinetics, mechanism and effect of various conditions
on the degradation," Separation and Purification Technology, Vol. 44,
no. 2, pp. 121-129, 2005.
[2] A. Lagana-, A. Bacaloni, I.D. Leva, A. Faberi, G. Fago, A. Marino,
ÔÇÿÔÇÿOccurrence and determination of herbicides and their major
transformation products in environmental waters," Analytica Chimica
Acta, Vol. 462, no. 2, pp. 187-198, 2000.
[3] E. Chamarro, E. Marco, S. Esplugas, ÔÇÿÔÇÿUse of Fenton reagent to
improve organic chemical biodegradability," Water Research, Vol. 35,
no. 4, pp. 1047-1051, 2001.
[4] J.J. Pignatello, D. Liu, P. Houston, ÔÇÿÔÇÿEvidence for an additional oxidant
in the photo assisted Fenton reaction," Environmental science and
Technology, Vol. 33, no. 11, pp. 1832-1839, 1999.
[5] H. Fallmann, Thomas Krutzler, Rupert Bauer, S. Malato, J. Blanco,
ÔÇÿÔÇÿApplicability of the Photo-Fenton method for treating water containing
pesticides," Catalysis Today, Vol. 54, no.2-3, pp. 309-319,
1999.
[6] J. Fernandez, J. Bandara, A. Lopez, P. Albers, J. Kiwi, ÔÇÿÔÇÿEfficient photoassited
Fenton catalysis mediated by Fe ions on Nafion membranes
active in the abatement of non-biodegradable azo-dye," Chemical
Communications., Vol. 14, pp. 1493-1484, 1998.
[7] R. M. Sherrarda, J.S. Bearrb, C.L. Murray-Guldec, J.H. Rodgers Jr., and
Y.T. Shahd, ÔÇÿÔÇÿFeasibility of constructed wetlands for removing
chlorothalonil and chlorpyrifos from aqueous mixtures," Environmental
Pollution, Vol. 127, no. 3, pp. 385 -394, 2004.
[8] Y. Zhang, J. Lu, L. Wu, A. Chang, and W.T. Frankenberger Jr.,
ÔÇÿÔÇÿSimultaneous removal of chlorothalonil and nitrate by Bacillus cereus
strain NS1", Science of the Total Environment, Vol. 382 no. 2-3, pp.
383 -387, 2007.
[9] Y. Samet, L. Agengui, R. Abdelhédi, ÔÇÿÔÇÿAnodic oxidation of chlorpyrifos
in aqueous solution at lead dioxide electrodes," Journal of
Electroanalytical Chemistry, Vol. 650, no.1, pp. 152-158, 2010.
[10] Y. Samet, L. Agengui, R. Abdelhédi, ÔÇÿÔÇÿElectrochemical degradation of
chlorpyrifos pesticide in aqueous solutions by anodic oxidation at borondoped
diamond electrodes," Chemical Engineering Journal, Vol. 161,
no. 1-2, pp. 167-172, 2010.
[11] A. Ghauch, A. Tuqan, ÔÇÿÔÇÿCatalytic degradation of chlorothalonil in water
using bimetallic iron-based systems", Chemosphere, Vol. 73 no. 5, pp.
751-759, 2008.
[12] F. Chen, L. Zeng, Y. Zhang, X. Liao, Y. Ge, X. Hua, L. Jiang,
ÔÇÿÔÇÿDegradation behaviour of methamidophos and chlorpyrifos in apple
juice treated with pulsed electric fields," Food Chemistry,Vol. 112, no.
4, pp. 956-961, 2009.
[13] J.G. Wu, T.G. Luan, C.Y. Lan, W.H. Lo, G.Y.S. Chan, ÔÇÿÔÇÿEfficacy
evaluation of low-concentration of ozonated water in removal of residual
diazinon, parathion, methyl-parathion and cypermethrin on vegetable,"
Journal of Food Engineering, Vol. 79, no. 3, pp. 803-809,
2007.
[14] C.F. Gromboni, M.Y. Kamogawa, A.G. Ferreira, J.A. N'Obrega, and
A.R.A. Nogueira, ÔÇÿÔÇÿMicrowave-assisted photo-Fenton decomposition of
chlorfenvinphos and cypermethrin in residual water," Journal of
Photochemistry and Photobiology A: Chemistry, Vol. 185, no.1, pp.
32-37, 2007.
[15] APHA, AWWA, WPCF, ÔÇÿÔÇÿStandard Methods for the Examination of
Water and Wastewater," 21st edition, American Public Health
Association, Washington, DC, 2005.
[16] I. Talinli, G.K. Anderson, ÔÇÿÔÇÿInterference of hydrogen peroxide on the
standard COD test," Water Research, Vol. 26, no. 1, pp. 107-110, 1992.
[17] Y.W. Kang, M.J. Cho, K.Y. Hwang, ÔÇÿÔÇÿCorrection of hydrogen peroxide
interference on standard chemical oxygen demand test," Water
Research, Vol. 33, no. 5, pp. 1247-1251, 1999.
[18] V. A. Sakkas, T. A. Albanis, ÔÇÿÔÇÿPhotocatalyzed degradation of the
biocides chlorothalonil and dichlofluanid over aqueous TiO2
suspensions,-- Applied Catalysis B: Environmental, Vol. 46, no. 1, pp.
175-188, 2003.
[19] L. Tong, P. Eichhorn, S. Pérez, Y. Wang, D. Barcel├│,
ÔÇÿÔÇÿPhotodegradation of azithromycin in various aqueous systems under
simulated and natural solar radiation: Kinetics and identification of
photoproducts,-- Chemosphere, Vol. 83, no.3, pp.340-348, 2011.
[20] R.G. Zepp, G.L. Baughman, P.F. Schlotzhauer, ÔÇÿÔÇÿComparison of
photochemical behavior of various humic substances in water: I.
Sunlight induced reactions of aquatic pollutants photosensitized by
humic substances,-- Chemosphere, Vol. 10, no.1, pp.109-117, 1981a
[21] ] R.G. Zepp, G.L. Baughman, P.F. Schlotzhauer, 1981b. ÔÇÿÔÇÿComparison
of photochemical behavior of various humic substances in water: II.
Photosensitized oxygenations,-- Chemosphere, Vol. 10, no.1, pp.119-
126, 1981b.
[22] M.I. Badawy, M. Y. Ghaly, T. A. Gad-Allah, ÔÇÿÔÇÿAdvanced oxidation
processes for the removal of organophosphorus pesticides from
wastewater," Desalination Vol. 194, no. 1-3, pp. 166-175, 2006.
[23] E. Elmolla and M. Chaudhuri, ÔÇÿÔÇÿOptimization of Fenton process for
treatment of amoxicillin, ampicillin and cloxacillin antibiotics in
aqueous solution," Journal of Hazardous Materials, Vol. 170, no. 2-
3, pp. 666-672, 2009.
[24] M.V. Shankar, S. Anandan, N. Venkatachalam, B. Arabindoo, V.
Murugesan, ÔÇÿÔÇÿNovel thin-film reactor for photocatalytic degradation of
pesticides in aqueous Solutions," Journal of Chemical Technology and
Biotechnology., Vol. 79, no. 11, pp. 1279 - 1285, 2004.
[25] E. Neyens, J. Baeyens, ÔÇÿÔÇÿA review of classic Fenton-s peroxidation as an
advanced oxidation technique," Journal of Hazardous Materials. Vol.
98, no. 1-3, pp. 33-50, 2003.
[26] N. Modirshahla, M.A. Behnajady, F. Ghanbary, ÔÇÿÔÇÿDecolorization and
mineralization of C.I. acid yellow 23 by Fenton and photo-Fenton
processes," Dyes Pigments, Vol. 73, no.3, pp. 305-310, 2007.
[27] D.A. Dhas, I. H. Joea, S.D.D. Roy, T.H. Freed, ÔÇÿÔÇÿDFT computations and
spectroscopic analysis of a pesticide: Chlorothalonil," Spectrochimica
Acta Part A: Molecular and Biomolecular Spectroscopy Spectrochimica
Acta Part A, Vol. 77, no. 1, pp. 36-44, 2010.
[28] S. Armenta, G. Quint├ís, S. Garrigues, M. de la Guardi , ÔÇÿÔÇÿA validated
and fast procedure for FTIR determination of cypermethrin and
chlorpyrifos," Talanta, Vol. 67, no. 3, pp. 634-639, 2005.
[29] V. Pareek, S. Chong, M. Tade, A. Adesina, Light intensity distribution
in heterogeneous photocatalytic reactors," Asia-Pacific Journal of
Chemical Engineering, Vol. 3, no. 2, pp. 171-201, 2008.
[30] A.E. Cassano, O.M. Alfano, ÔÇÿÔÇÿReaction engineering of suspended solid
heterogenous photocatalytic reactors," Catalysis Today, Vol. 58 no. 2-3,
pp. 167-197, 2000.
[31] M. Mahalakshmi, Banumathi Arabindoo, M. Palanichamy, V.
Murugesan, ÔÇÿÔÇÿPhotocatalytic degradation of carbofuran using
semiconductor oxides," Journal of Hazardous Materials, Vol. 143 no. 1-
2, pp. 240-245, 2007.
[32] D. F. Ollis, E. Pelizzetti, N. Serpone, ÔÇÿÔÇÿPhotocatalyzed destruction of
water contaminants," Environmental Science and Technology, Vol. 25,
no. 9, pp. 1522-1529, 1991.
[33] R. Terzian, N. Serpone, ÔÇÿÔÇÿHeterogeneous photocatalysed oxidation of
creosote components; mineralization of xylenols by illuminated TiO2 in
oxygenated aqueous media," Journal of Photochemistry and
Photobiology A: Chemistry Vol. 89, no. 2, pp. 163-175, 1991.
[34] F. Al-Momani, J.R. Touraud, J. R. Degorce-Dumas, J. Roussy, O.
Thomas, ÔÇÿÔÇÿBiodegradility enhancement of textile dyes and textile
wastewater by UV photocatalysis," Journal of Photochemistry and
Photobiology, A: Chemistry, Biodegradility enhancement of textile dyes
and textile wastewater by UV photocatalysis, Vol. 153, no. 1-3, pp.
191-197, 2002.
[1] S. Kundua, A. Pala, A. K. Dikshitb, ÔÇÿÔÇÿUV induced degradation of
herbicide 2, 4-D: kinetics, mechanism and effect of various conditions
on the degradation," Separation and Purification Technology, Vol. 44,
no. 2, pp. 121-129, 2005.
[2] A. Lagana-, A. Bacaloni, I.D. Leva, A. Faberi, G. Fago, A. Marino,
ÔÇÿÔÇÿOccurrence and determination of herbicides and their major
transformation products in environmental waters," Analytica Chimica
Acta, Vol. 462, no. 2, pp. 187-198, 2000.
[3] E. Chamarro, E. Marco, S. Esplugas, ÔÇÿÔÇÿUse of Fenton reagent to
improve organic chemical biodegradability," Water Research, Vol. 35,
no. 4, pp. 1047-1051, 2001.
[4] J.J. Pignatello, D. Liu, P. Houston, ÔÇÿÔÇÿEvidence for an additional oxidant
in the photo assisted Fenton reaction," Environmental science and
Technology, Vol. 33, no. 11, pp. 1832-1839, 1999.
[5] H. Fallmann, Thomas Krutzler, Rupert Bauer, S. Malato, J. Blanco,
ÔÇÿÔÇÿApplicability of the Photo-Fenton method for treating water containing
pesticides," Catalysis Today, Vol. 54, no.2-3, pp. 309-319,
1999.
[6] J. Fernandez, J. Bandara, A. Lopez, P. Albers, J. Kiwi, ÔÇÿÔÇÿEfficient photoassited
Fenton catalysis mediated by Fe ions on Nafion membranes
active in the abatement of non-biodegradable azo-dye," Chemical
Communications., Vol. 14, pp. 1493-1484, 1998.
[7] R. M. Sherrarda, J.S. Bearrb, C.L. Murray-Guldec, J.H. Rodgers Jr., and
Y.T. Shahd, ÔÇÿÔÇÿFeasibility of constructed wetlands for removing
chlorothalonil and chlorpyrifos from aqueous mixtures," Environmental
Pollution, Vol. 127, no. 3, pp. 385 -394, 2004.
[8] Y. Zhang, J. Lu, L. Wu, A. Chang, and W.T. Frankenberger Jr.,
ÔÇÿÔÇÿSimultaneous removal of chlorothalonil and nitrate by Bacillus cereus
strain NS1", Science of the Total Environment, Vol. 382 no. 2-3, pp.
383 -387, 2007.
[9] Y. Samet, L. Agengui, R. Abdelhédi, ÔÇÿÔÇÿAnodic oxidation of chlorpyrifos
in aqueous solution at lead dioxide electrodes," Journal of
Electroanalytical Chemistry, Vol. 650, no.1, pp. 152-158, 2010.
[10] Y. Samet, L. Agengui, R. Abdelhédi, ÔÇÿÔÇÿElectrochemical degradation of
chlorpyrifos pesticide in aqueous solutions by anodic oxidation at borondoped
diamond electrodes," Chemical Engineering Journal, Vol. 161,
no. 1-2, pp. 167-172, 2010.
[11] A. Ghauch, A. Tuqan, ÔÇÿÔÇÿCatalytic degradation of chlorothalonil in water
using bimetallic iron-based systems", Chemosphere, Vol. 73 no. 5, pp.
751-759, 2008.
[12] F. Chen, L. Zeng, Y. Zhang, X. Liao, Y. Ge, X. Hua, L. Jiang,
ÔÇÿÔÇÿDegradation behaviour of methamidophos and chlorpyrifos in apple
juice treated with pulsed electric fields," Food Chemistry,Vol. 112, no.
4, pp. 956-961, 2009.
[13] J.G. Wu, T.G. Luan, C.Y. Lan, W.H. Lo, G.Y.S. Chan, ÔÇÿÔÇÿEfficacy
evaluation of low-concentration of ozonated water in removal of residual
diazinon, parathion, methyl-parathion and cypermethrin on vegetable,"
Journal of Food Engineering, Vol. 79, no. 3, pp. 803-809,
2007.
[14] C.F. Gromboni, M.Y. Kamogawa, A.G. Ferreira, J.A. N'Obrega, and
A.R.A. Nogueira, ÔÇÿÔÇÿMicrowave-assisted photo-Fenton decomposition of
chlorfenvinphos and cypermethrin in residual water," Journal of
Photochemistry and Photobiology A: Chemistry, Vol. 185, no.1, pp.
32-37, 2007.
[15] APHA, AWWA, WPCF, ÔÇÿÔÇÿStandard Methods for the Examination of
Water and Wastewater," 21st edition, American Public Health
Association, Washington, DC, 2005.
[16] I. Talinli, G.K. Anderson, ÔÇÿÔÇÿInterference of hydrogen peroxide on the
standard COD test," Water Research, Vol. 26, no. 1, pp. 107-110, 1992.
[17] Y.W. Kang, M.J. Cho, K.Y. Hwang, ÔÇÿÔÇÿCorrection of hydrogen peroxide
interference on standard chemical oxygen demand test," Water
Research, Vol. 33, no. 5, pp. 1247-1251, 1999.
[18] V. A. Sakkas, T. A. Albanis, ÔÇÿÔÇÿPhotocatalyzed degradation of the
biocides chlorothalonil and dichlofluanid over aqueous TiO2
suspensions,-- Applied Catalysis B: Environmental, Vol. 46, no. 1, pp.
175-188, 2003.
[19] L. Tong, P. Eichhorn, S. Pérez, Y. Wang, D. Barcel├│,
ÔÇÿÔÇÿPhotodegradation of azithromycin in various aqueous systems under
simulated and natural solar radiation: Kinetics and identification of
photoproducts,-- Chemosphere, Vol. 83, no.3, pp.340-348, 2011.
[20] R.G. Zepp, G.L. Baughman, P.F. Schlotzhauer, ÔÇÿÔÇÿComparison of
photochemical behavior of various humic substances in water: I.
Sunlight induced reactions of aquatic pollutants photosensitized by
humic substances,-- Chemosphere, Vol. 10, no.1, pp.109-117, 1981a
[21] ] R.G. Zepp, G.L. Baughman, P.F. Schlotzhauer, 1981b. ÔÇÿÔÇÿComparison
of photochemical behavior of various humic substances in water: II.
Photosensitized oxygenations,-- Chemosphere, Vol. 10, no.1, pp.119-
126, 1981b.
[22] M.I. Badawy, M. Y. Ghaly, T. A. Gad-Allah, ÔÇÿÔÇÿAdvanced oxidation
processes for the removal of organophosphorus pesticides from
wastewater," Desalination Vol. 194, no. 1-3, pp. 166-175, 2006.
[23] E. Elmolla and M. Chaudhuri, ÔÇÿÔÇÿOptimization of Fenton process for
treatment of amoxicillin, ampicillin and cloxacillin antibiotics in
aqueous solution," Journal of Hazardous Materials, Vol. 170, no. 2-
3, pp. 666-672, 2009.
[24] M.V. Shankar, S. Anandan, N. Venkatachalam, B. Arabindoo, V.
Murugesan, ÔÇÿÔÇÿNovel thin-film reactor for photocatalytic degradation of
pesticides in aqueous Solutions," Journal of Chemical Technology and
Biotechnology., Vol. 79, no. 11, pp. 1279 - 1285, 2004.
[25] E. Neyens, J. Baeyens, ÔÇÿÔÇÿA review of classic Fenton-s peroxidation as an
advanced oxidation technique," Journal of Hazardous Materials. Vol.
98, no. 1-3, pp. 33-50, 2003.
[26] N. Modirshahla, M.A. Behnajady, F. Ghanbary, ÔÇÿÔÇÿDecolorization and
mineralization of C.I. acid yellow 23 by Fenton and photo-Fenton
processes," Dyes Pigments, Vol. 73, no.3, pp. 305-310, 2007.
[27] D.A. Dhas, I. H. Joea, S.D.D. Roy, T.H. Freed, ÔÇÿÔÇÿDFT computations and
spectroscopic analysis of a pesticide: Chlorothalonil," Spectrochimica
Acta Part A: Molecular and Biomolecular Spectroscopy Spectrochimica
Acta Part A, Vol. 77, no. 1, pp. 36-44, 2010.
[28] S. Armenta, G. Quint├ís, S. Garrigues, M. de la Guardi , ÔÇÿÔÇÿA validated
and fast procedure for FTIR determination of cypermethrin and
chlorpyrifos," Talanta, Vol. 67, no. 3, pp. 634-639, 2005.
[29] V. Pareek, S. Chong, M. Tade, A. Adesina, Light intensity distribution
in heterogeneous photocatalytic reactors," Asia-Pacific Journal of
Chemical Engineering, Vol. 3, no. 2, pp. 171-201, 2008.
[30] A.E. Cassano, O.M. Alfano, ÔÇÿÔÇÿReaction engineering of suspended solid
heterogenous photocatalytic reactors," Catalysis Today, Vol. 58 no. 2-3,
pp. 167-197, 2000.
[31] M. Mahalakshmi, Banumathi Arabindoo, M. Palanichamy, V.
Murugesan, ÔÇÿÔÇÿPhotocatalytic degradation of carbofuran using
semiconductor oxides," Journal of Hazardous Materials, Vol. 143 no. 1-
2, pp. 240-245, 2007.
[32] D. F. Ollis, E. Pelizzetti, N. Serpone, ÔÇÿÔÇÿPhotocatalyzed destruction of
water contaminants," Environmental Science and Technology, Vol. 25,
no. 9, pp. 1522-1529, 1991.
[33] R. Terzian, N. Serpone, ÔÇÿÔÇÿHeterogeneous photocatalysed oxidation of
creosote components; mineralization of xylenols by illuminated TiO2 in
oxygenated aqueous media," Journal of Photochemistry and
Photobiology A: Chemistry Vol. 89, no. 2, pp. 163-175, 1991.
[34] F. Al-Momani, J.R. Touraud, J. R. Degorce-Dumas, J. Roussy, O.
Thomas, ÔÇÿÔÇÿBiodegradility enhancement of textile dyes and textile
wastewater by UV photocatalysis," Journal of Photochemistry and
Photobiology, A: Chemistry, Biodegradility enhancement of textile dyes
and textile wastewater by UV photocatalysis, Vol. 153, no. 1-3, pp.
191-197, 2002.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:58836", author = "Augustine Chioma Affam and Shamsul Rahman M. Kutty and Malay Chaudhuri", title = "Solar Photo-Fenton Induced Degradation of Combined Chlorpyrifos, Cypermethrin and Chlorothalonil Pesticides in Aqueous Solution", abstract = "The feasibility of employing solar radiation for
enhanced Fenton process in degradation of combined chlorpyrifos,
cypermethrin and chlorothalonil pesticides was examined. The effect
of various operating conditions of the process on biodegradability
improvement and mineralization of the pesticides were also
evaluated. The optimum operating conditions for treatment of
aqueous solution containing 100, 50 and 250 mg L-1 chlorpyrifos
cypermethrin and chlorothalonil, respectively were observed to be
H2O2/COD molar ratio 2, H2O2/Fe2+ molar ratio 25 and pH 3. Under
the optimum operating conditions, complete degradation of the
pesticides occurred in 1 min. Biodegradability (BOD5/COD)
increased from zero to 0.36 in 60 min, and COD and TOC removal
were 74.19 and 58.32%, respectively in 60 min. Due to
mineralization of organic carbon, decrease in ammonia-nitrogen from
22 to 4.3 mg L-1 and increase in nitrate from 0.7 to 18.1 mg L-1 in
60 min were recorded. The study indicated that solar photo-Fenton
process can be used for pretreatment of chlorpyrifos, cypermethrin
and chlorothalonil pesticides in aqueous solution for further
biological treatment.", keywords = "Chlorpyrifos, Cypermethrin, Chlorothalonil, Solar
photo-Fenton", volume = "6", number = "2", pages = "167-7", }
