Please wait a minute...
Journal of Integrative Agriculture  2013, Vol. 12 Issue (11): 2074-2082    DOI: 10.1016/S2095-3119(13)60506-7
Plant Protection Advanced Online Publication | Current Issue | Archive | Adv Search |
Hydrolysis and Photolysis of Herbicide Clomazone in Aqueous Solutions and Natural Water Under Abiotic Conditions
 CAO Jia, DIAO Xiao-ping , HU Ji-ye
1.School of Agriculture, Hainan University, Haikou 570228, P.R.China
2.School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, P.R.China
Download:  PDF in ScienceDirect  
Export:  BibTeX | EndNote (RIS)      
摘要  The hydrolysis and photolysis of clomazone in aqueous solutions and natural water were assessed under natural and controlled conditions. Kinetics of hydrolysis and photolysis of clomazone were determined by HPLC-DAD. Photoproducts were identifi ed by HPLC-MS. No noticeable hydrolysis occurred in aqueous buffer solutions ((25±2)°C, pH (4.5±0.1), pH (7.4±0.1), pH (9.0±0.1); (50±2)°C, pH (4.5±0.1), pH (7.4±0.1)) or in natural water up to 90 d. At pH (9.0±0.1) and (50±2)°C the half-life of clomazone was 50.2 d. Clomazone photodecomposition rate in aqueous solutions under UV radiation and natural sunlight followed fi rst-order kinetics. Degradation rates were faster under UV light (half-life of 51-59 min) compared to sunlight (halflife of 87-136 d). Under UV light, four major photoproducts were detected and tentatively identifi ed according to HPLC-MS spectral information such as 2-chlorobenzamide, N-hydroxy-(2-benzyl)-2-methylpropan-amide, 2-[2-phenol]-4,4-dimethyl- 3-isoxazolidinone and 2-[(4,6-dihydroxyl-2-chlorine phenol)]-4,4-dimethyl-3-isoxazolidinone. These results suggested that clomazone photodegradation proceeds via several reaction pathways: 1) dehalogenation; 2) substitution of chlorine group by hydroxyl; 3) cleavage of the side chain. Photosensitizers, such as H2O2 and ribofl avin, could enhance photolysis of clomazone in natural sunlight. In summary, we found that photoreaction is an important dissipation pathway of clomazone in natural water systems.

Abstract  The hydrolysis and photolysis of clomazone in aqueous solutions and natural water were assessed under natural and controlled conditions. Kinetics of hydrolysis and photolysis of clomazone were determined by HPLC-DAD. Photoproducts were identifi ed by HPLC-MS. No noticeable hydrolysis occurred in aqueous buffer solutions ((25±2)°C, pH (4.5±0.1), pH (7.4±0.1), pH (9.0±0.1); (50±2)°C, pH (4.5±0.1), pH (7.4±0.1)) or in natural water up to 90 d. At pH (9.0±0.1) and (50±2)°C the half-life of clomazone was 50.2 d. Clomazone photodecomposition rate in aqueous solutions under UV radiation and natural sunlight followed fi rst-order kinetics. Degradation rates were faster under UV light (half-life of 51-59 min) compared to sunlight (halflife of 87-136 d). Under UV light, four major photoproducts were detected and tentatively identifi ed according to HPLC-MS spectral information such as 2-chlorobenzamide, N-hydroxy-(2-benzyl)-2-methylpropan-amide, 2-[2-phenol]-4,4-dimethyl- 3-isoxazolidinone and 2-[(4,6-dihydroxyl-2-chlorine phenol)]-4,4-dimethyl-3-isoxazolidinone. These results suggested that clomazone photodegradation proceeds via several reaction pathways: 1) dehalogenation; 2) substitution of chlorine group by hydroxyl; 3) cleavage of the side chain. Photosensitizers, such as H2O2 and ribofl avin, could enhance photolysis of clomazone in natural sunlight. In summary, we found that photoreaction is an important dissipation pathway of clomazone in natural water systems.
Keywords:  clomazone       hydrolysis       photolysis       photoproducts       abiotic  
Received: 10 January 2013   Accepted:
Fund: 

This study was sponsored by Shandong Cynda Chemical Co., Ltd. (Shandong, China) and the Project of Pesticide Registration Residue of Ministry of Agriculture of China (FRF-SD-12-010B).

Corresponding Authors:  Correspondence HU Ji-ye, Tel: +86-10-82376002, E-mail: jyhu@ustb.edu.cn; DIAO Xiao-ping, Tel: +86-898-66295028, E-mail: diaoxip@hainu.edu.cn     E-mail:  jyhu@ustb.edu.cn
About author:  CAO Jia, Tel: +86-898-66295028, E-mail: jiabiyang2006@126.com;

Cite this article: 

CAO Jia, DIAO Xiao-ping , HU Ji-ye. 2013. Hydrolysis and Photolysis of Herbicide Clomazone in Aqueous Solutions and Natural Water Under Abiotic Conditions. Journal of Integrative Agriculture, 12(11): 2074-2082.

1.School of Agriculture, Hainan University, Haikou 570228, P.R.China

2.School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Bei[1]Brown D, Masiunas J. 2002. Evaluation of herbicides forpumpkin (Cucurbita spp.). Weed Technology, 16, 282-292

[2]Chamberlain E, Shi H L, Wang T W, Ma Y F, Fulmer A,Adams C. 2012. Comprehensive screening study ofpesticide degradation via oxidation and hydrolysis.Journal of Agriculture and Food Chemistry, 60, 354-363

[3]Chan K H, Chu W. 2009. Riboflavin-sensitizedphotooxidation of phenylurea herbicide monuron inaqueous peroxide solution. Chemical EngineeringJournal, 152, 103-109

[4]Crestani M, Menezes C, Glusczak L, Miron D S, SpanevelloR, Silveira A, Goncalves F F, Zanella R, Loro V L.2007. Effect of clomazone herbicide on biochemical andhistological aspects of silver catfish (Rhamdia quelen)and recovery pattern. Chemosphere, 67, 2305-2311

[5]Da Silva J P, Vieira Ferreira L F, Da Silva A M. 2003.Aqueous photochemistry of pesticides triadimefonand triadimenol. Journal of Photochemistry andPhotobiology (A), 154, 293-298

[6]Evgenidou E, Fytianos K. 2002. Photodegradation oftriazine herbicides in aqueous solutions and naturalwaters. Journal of Agriculture and Food Chemistry, 50,6423-6427

[7]Ferhatoglu Y, Barrett M. 2006. Studies of clomazone mode of action. Pesticide Biochemistry Physiology, 85, 7-14

[8]Hawari J, Demeter A, Samson R. 1992. Sensitizedphotolysis of polychlorobiphenyls in alkaline 2-propanol: dechlorination of Aroclor 1254 in soil samplesby solar radiation. Environmental Science Technology,26, 2022-2027

[9]Hu J Y, Liu C, Yan H. 2008. Degradation of fl umorph insoils, aqueous buffer solutions, and natural waters.Journal of Agricultural and Food Chemistry, 57, 8574-8579

[10]Kiss A, Rapi S, Csutorás C. 2007. GC/MS studieson revealing products and reaction mechanism ofphotodegradation of pesticides. Microchemical Journal,85, 13-20

[11]Konstantinou I K, Albanis T A. 2003. Photocatalytictransformation of pesticides in aqueous titanium dioxidesuspensions using artifi cial and solar light: intermediatesand degradation pathways. Applied Catalysis (B:Environmental), 42, 319-335

[12]Li L F, Li G X, Yang R B, Guo Z Y, Liao X Y. 2004.Clomazone dissipation, adsorption and translocation infour paddy topsoils. Journal of Environmenta Sciences,16, 678-682

[13]Lin B X, Yu Y, Hu X G, Deng D Y, Zhu L C, Wang W J.2011. Degradation mechanisms of phoxim in river water.Journal of Agricultural and Food Chemistry, 59, 312-321

[14]Liu S Y, Shocken M, John P, Rosazza N. 1996. Microbialtransformations of clomazone. Journal of Agriculturaland Food Chemistry, 44, 313-319

[15]Mandal S, Joardar S, Das S, Bhattacharyya A. 2011.Photodegradation of hexythiazox in different solventsystems under the influence of ultraviolet light andsunlight in the presence of TiO2, H2O2, and KNO3and identification of the photometabolites. Journal ofAgricultural and Food Chemistry, 59, 11727-11734

[16]Mervosh T L, Sims G K, Stollert E W. 1995. Clomazonefate in soil as affected by microbial activity, temperature,and soil-moisture. Journal of Agricultural and FoodChemistry, 43, 537-543

[17]Patrick L T, Dirk M H, Zou W, Tjeerdema R. 2010.Microbial degradation of clomazone under simulatedcalifornia rice fi eld conditions. Journal of Agriculturaland Food Chemistry, 58, 3674-3680

[18]Prevot A B, Vincenti M, Bianciotto A, Pramauro E.1999. Photocatalytic and photolytic transformation ofchloramben in aqueous solutions. Applied Catalysis (B:Environmental), 22, 149-158

[19]Quayle W C, Oliver D P, Zrna S. 2006. Field dissipationand environmental hazard assessment of clomazone,molinate, and thiobencarb in Australian rice culture.Journal of Agricultural and Food Chemistry, 54, 7213-7220

[20]Sevilla-Moran B, Sandin-Espana P, Vicente-Aranab M J,Alonso-Prados J L, Garcia-Baudin J M. 2008. Study ofalloxydim photodegradation in the presence of naturalsubstances: elucidation of transformation products.Journal of Photochemistry and Photobiology (A:Chemistry), 198, 162-168

[21]Zanella R, Primel E G, Goncalves F F, Martins M L,Adaime M B, Marchesan E, Machado S L. 2008. Studyof the degradation of t he herbicide clomazone in distilledand in irrigated rice fi eld waters using HPLC-DAD andGC-MS. Journal of the Brazilian Chemical Society, 19,987-995
[1] CHI Qing, DU Lin-ying, MA Wen, NIU Ruo-yu, WU Bao-wei, GUO Li-jian, MA Meng, LIU Xiang-li, ZHAO Hui-xian. The miR164-TaNAC14 module regulates root development and abiotic-stress tolerance in wheat seedlings[J]. >Journal of Integrative Agriculture, 2023, 22(4): 981-998.
[2] LI Zhi-qi, Xie Qian, YAN Jia-hui, CHEN Jian-qing, CHEN Qing-xi. Genome-wide identification and characterization of the abiotic-stress-responsive lipoxygenase gene family in diploid woodland strawberry (Fragaria vesca)[J]. >Journal of Integrative Agriculture, 2022, 21(7): 1982-1996.
[3] DU Qiao-li, FANG Yuan-peng, JIANG Jun-mei, CHEN Mei-qing, LI Xiang-yang, XIE Xin. Genome-wide identification and characterization of the JAZ gene family and its expression patterns under various abiotic stresses in Sorghum bicolor[J]. >Journal of Integrative Agriculture, 2022, 21(12): 3540-3555.
[4] LI Sheng-lan, TAN Ting-ting, FAN Yuan-fang, Muhammad Ali RAZA, WANG Zhong-lin, WANG Bei-bei, ZHANG Jia-wei, TAN Xian-ming, CHEN Ping, Iram SHAFIQ, YANG Wen-yu, YANG Feng. Response of leaf stomatal and mesophyll conductance to abiotic stress factors[J]. >Journal of Integrative Agriculture, 2022, 21(10): 2787-2804.
[5] SHI Bei-bei, WANG Juan, GAO Hai-feng, ZHANG Xiao-juan, WANG Yang, MA Qing. The TaFIM1 gene mediates wheat resistance against Puccinia striiformis f. sp. tritici and responds to abiotic stress[J]. >Journal of Integrative Agriculture, 2021, 20(7): 1849-1857.
[6] WANG Xi-cheng, WU Wei-min, ZHOU Bei-bei, WANG Zhuang-wei, QIAN Ya-ming, WANG Bo, YAN Li-chun. Genome-wide analysis of the SCPL gene family in grape (Vitis vinifera L.)[J]. >Journal of Integrative Agriculture, 2021, 20(10): 2666-2679.
[7] MIAO Li-li, LI Yu-ying, ZHANG Hong-juan, ZHANG Hong-ji, LIU Xiu-lin, WANG Jing-yi, CHANG Xiao-ping, MAO Xin-guo, JING Rui-lian. TaSnRK2.4 is a vital regulator in control of thousand-kernel weight and response to abiotic stress in wheat[J]. >Journal of Integrative Agriculture, 2021, 20(1): 46-54.
[8] QIN Jin-xia, JIANG Yu-jie, LU Yun-ze, ZHAO Peng, WU Bing-jin, LI Hong-xia, WANG Yu, XU Sheng-bao, SUN Qi-xin, LIU Zhen-shan. Genome-wide identification and transcriptome profiling reveal great expansion of SWEET gene family and their wide-spread responses to abiotic stress in wheat (Triticum aestivum L.)[J]. >Journal of Integrative Agriculture, 2020, 19(7): 1704-1720.
[9] FANG Zheng-wu, HE Yi-qin, LIU Yi-ke, JIANG Wen-qiang, SONG Jing-han, WANG Shu-ping, MA Dong-fang, YIN Jun-liang. Bioinformatic identification and analyses of the non-specific lipid transfer proteins in wheat[J]. >Journal of Integrative Agriculture, 2020, 19(5): 1170-1185.
[10] ZHANG Ya-bin, TANG Wei, WANG Li-huan, HU Ya-wen, LIU Xian-wen, LIU Yong-sheng. Kiwifruit (Actinidia chinensis) R1R2R3-MYB transcription factor AcMYB3R enhances drought and salinity tolerance in Arabidopsis thaliana[J]. >Journal of Integrative Agriculture, 2019, 18(2): 417-427.
[11] GUO Yuan, XU Chang-bing, SUN Xian-jun, HU Zheng, FAN Shou-jin, JIANG Qi-yan, ZHANG Hui. TaSAUR78 enhances multiple plant abiotic stress responses by regulating the interacting gene TaVDAC1[J]. >Journal of Integrative Agriculture, 2019, 18(12): 2682-2690.
[12] WANG Ling-shuang, CHEN Qing-shan, XIN Da-wei, QI Zhao-ming, ZHANG Chao, LI Si-nan, JIN Yang-mei, LI Mo, MEI Hong-yao, SU An-yu, WU Xiao-xia. Overexpression of GmBIN2, a soybean glycogen synthase kinase 3 gene, enhances tolerance to salt and drought in transgenic Arabidopsis and soybean hairy roots[J]. >Journal of Integrative Agriculture, 2018, 17(09): 1959-1971.
[13] ZHANG Yong-hua, CHEN Chao, SHI Zi-han, CHENG Hui-mei, BING Jie, MA Xiao-feng, ZHENG Chao-xing, LI Hong-jie, ZHANG Gen-fa. Identification of salinity-related genes in ENO2 mutant (eno2) of Arabidopsis thaliana[J]. >Journal of Integrative Agriculture, 2018, 17(01): 94-110.
[14] ZHANG Jia, HU Yong, XU Li-he, HE Qin, FAN Xiao-wei, XING Yong-zhong. The CCT domain-containing gene family has large impacts on heading date, regional adaptation, and grain yield in rice[J]. >Journal of Integrative Agriculture, 2017, 16(12): 2686-2697.
[15] LI Wen-lan, SUN Qi, LI Wen-cai, YU Yan-li, ZHAO Meng, MENG Zhao-dong. Characterization and expression analysis of a novel RING-HC gene, ZmRHCP1, involved in brace root development and abiotic stress responses in maize[J]. >Journal of Integrative Agriculture, 2017, 16(09): 1892-1899.
No Suggested Reading articles found!