双唑草腈对3种水生生物的急性毒性及初级生态风险评估

孔玄庆; 蒋煜; 罗泽伟; 喻快; 成淑芬; 欧阳文森; 李建明; 金晨钟; 欧晓明

doi:10.16801/j.issn.1008-7303.2022.0037

双唑草腈对3种水生生物的急性毒性及初级生态风险评估

doi: 10.16801/j.issn.1008-7303.2022.0037

孔玄庆^{1, 2,},
蒋煜^{1, 2},
罗泽伟³,
喻快^{1, 2},
成淑芬^{1, 2},
欧阳文森^{1, 2},
李建明^{1, 2},
金晨钟³,
欧晓明^{1, 2, 3, ,}

1.
湖南化工研究院国家农药创制工程研究中心/湖南省农用化学品重点实验室，长沙 410014
2.
湖南化研院检测技术有限公司，长沙 410014
3.
湖南人文科技学院/农田杂草防控技术与应用协同创新中心，湖南娄底 417000

详细信息

作者简介:
孔玄庆，731815254@qq.com

通讯作者:
欧晓明，xmouhn@163.com

中图分类号: TQ450.26；S482.4
计量
- 文章访问数: 247
- HTML全文浏览量: 91
- PDF下载量: 36
- 被引次数: 0
出版历程
- 收稿日期: 2021-07-28
- 录用日期: 2022-03-17
- 网络出版日期: 2022-05-11
- 刊出日期: 2022-06-10

Acute toxicities of pyraclonil to three aquatic organisms and its primary ecological risk assessment

KONG Xuanqing^{1, 2
,},
JIANG Yu^{1, 2},
LUO Zewei³,
YU Kuai^{1, 2},
CHENG Shufen^{1, 2},
OUYANG Wensen^{1, 2},
LI Jianming^{1, 2},
JIN Chenzhong³,
OU Xiaoming^{1, 2, 3
, ,}

1.
National Engineering Research Center for Agrochemicals/Hunan Provincial Key Laboratory of Agrochemicals, Hunan Research Institute of Chemical Industry, Changsha 410014, China
2.
Hunan Research Institute of Chemical Industry Testing Technology Co., Ltd., Changsha 410014, China
3.
Collaborative Innovation Center for Field Weeds Control, Hunan University of Humanities, Science and Technology, Loudi 417000, Hunan Province, China

摘要

摘要: 为研究双唑草腈对水生生物的毒性和水体环境风险，在实验室条件下，以斜生栅藻、大型溞和斑马鱼为研究对象，分别采用OECD推荐的生长抑制法、活动抑制法、静态法和TOP-RICE模型，开展了双唑草腈的急性毒性试验和初级生态风险评估。结果表明：双唑草腈对斜生栅藻细胞增殖的72 h半数抑制效应浓度 (72 h-EC₅₀) 为1.44 × 10⁻² mg/L，对大型溞活动的48 h半数抑制效应浓度 (48 h-EC₅₀) 为15.09 mg/L，对斑马鱼的96 h半数致死效应浓度 (96 h-LC₅₀) 为23.05 mg/L，根据我国《化学农药环境安全评价实验准则》中的毒性等级划分标准，相应毒性等级分别为高毒、低毒和低毒；在水生生态系统中，双唑草腈对脊椎动物和无脊椎动物的急性毒性风险商(RQ) 值小于1的分组占所有模拟场景的60%以上，超过60% 的分组对初级生产者的RQ值大于1，说明双唑草腈对大型溞和斑马鱼较为安全，对水生生态系统中脊椎动物和无脊椎动物的风险在可接受范围，但其对斜生栅藻毒性高，且对初级生产者的风险为不可接受。因此，生产中在施用双唑草腈时应避免药剂进入稻田周边水体，可通过减少农药使用量、合理调整施药时期等方法来减少双唑草腈对水生生态环境的风险，建议在早稻分蘖前期和晚稻分蘖后期使用。
- 双唑草腈 /
- 水生生物 /
- 急性毒性 /
- TOP-RICE模型 /
- 生态风险评估 /
- 斜生栅藻 /
- 大型溞 /
- 斑马鱼
Abstract: In order to study the toxicity of herbicide pyraclonil to aquatic organisms and its risk to water environment, the acute toxicity of pyracllonil against three aquatic organisms such as Scenedesmus obliquus, Daphnia magna, and Brachydonio rerio were investigated under laboratory conditions using the alga growth inhibition, immobilization test and static test recommended by OECD, and its primary ecological risk was assessed based on TOP-RICE model. The results showed that the 72-hour median inhibitory concentration (72 h-EC₅₀) of pyraclonil on the proliferation of S. obliquus cells was 1.44 × 10⁻² mg/L, and the 48-hour median inhibitory concentration (48 h-EC₅₀) on the activity of D. magna was 15.09 mg/L, and the 96-h medium lethal concentration (96 h-LC₅₀) on B. rerio was 23.05 mg/L. According to the classification standard of toxicity grades in "Chemical Pesticide Environmental Safety Evaluation Experiment Guidelines", the corresponding toxicity grades were high toxicity, low toxicity, and low toxicity respectively. In aquatic ecosystems, groups with an acute toxicity risk quotient (RQ) value less than 1 for pyraclonil to vertebrates and invertebrates accounted for more than 60% of all simulated scenarios, and more than 60% of groups had an RQ value greater than 1 for primary producers. The results indicated that pyraclonil is relatively safe for D. magna and B. rerio, and the risk to the vertebrates and the invertebrates in the aquatic ecosystem is acceptable, but its toxicity to S. obliquus is high, and the risk to primary producers is unacceptable. Therefore, the pyraclonil should be avoided from entering the water body around the paddy fields in the production process. The risk of pyraclonil to the aquatic ecosystem can be reduced by decreasing the amount of herbicide used and adjusting the application period reasonably. It is recommended to use pyraclonil at the early tillering stage of early rice or the late tillering stage of late rice.
- pyraclonil /
- aquatic organisms /
- acute toxicity /
- TOP-RICE model /
- ecological risk assessment /
- Scenedesmus obliquus /
- Daphnia magna /
- Brachydanio rerio

HTML全文

图 1 大型溞试验中双唑草腈为20.7 mg/L 时的色谱图 (48 h)

Figure 1. Liquid chromatogram of pyraclonil with 20.7 mg/L in the acute toxicity test of D. magna (48 h)

下载: 全尺寸图片幻灯片

图 2 不同场景点双唑草腈的预测环境浓度

注：TWA 表示时间加权平均值。

Figure 2. PEC of pyraclonil under different scenarios

Note: TWA means time weighted average.

下载: 全尺寸图片幻灯片

图 3 不同预测环境浓度下双唑草腈对3种水生生物的风险商

Figure 3. RQs of pyraclonil to D. magna, B. rerio and S. obliquus under different PECs

下载: 全尺寸图片幻灯片

表 1 各试验体系中双唑草腈的实测浓度

Table 1. Measured concentrations of pyraclonil in each test system

供试生物Test organism	暴露浓度Exposure conc./ (mg/L)	实测浓度 Measured conc./(mg/L)		浓度变化率^bRate of conc. change^b/%
供试生物Test organism	暴露浓度Exposure conc./ (mg/L)	0 h	48 h/72 h/96 h^a	浓度变化率^bRate of conc. change^b/%
斜生栅藻 S. obliquus	CK	0	0	0
	1.00 × 10⁻²	9.00 × 10⁻³	9.40 × 10⁻³	−4.44
	1.20 × 10⁻²	1.02 × 10⁻²	1.01 × 10⁻²	0.98
	1.44 × 10⁻²	1.49 × 10⁻²	1.45 × 10⁻²	2.55
	1.73 × 10⁻²	1.74 × 10⁻²	1.61 × 10⁻²	7.47
	2.07 × 10⁻²	1.97 × 10⁻²	1.71 × 10⁻²	13.20
	2.49 × 10⁻²	2.41 × 10⁻²	2.47 × 10⁻²	−2.49
大型溞 D. magna	CK	0	0	0
	10	9.89	9.31	5.86
	12	11.77	11.78	−0.08
	14.4	14.53	14.02	3.51
	17.3	17.20	17.01	1.10
	20.7	20.81	20.16	3.12
斑马鱼 B. rerio	CK	0	0	0
	15	14.98	14.01	3.14
	18	17.72	17.44	1.58
	21.6	21.75	20.13	7.45
	25.9	25.68	25.97	−1.13
	31.1	30.01	29.17	2.80
注：^a48 h为大型溞毒性试验结束时的实测浓度，72 h为斜生栅藻毒性试验结束时的实测浓度，96 h为斑马鱼毒性试验结束时的实测浓度；^b浓度变化率 (%)：[(试验结束时的实测浓度–0 h实测浓度)/0 h实测浓度] × 100。Note: ^a48 h indicates the measured concentration at the end of D. magna toxicity test, 72 h indicates the measured concentration at the end of the toxicity test of S. obliquus, 96 h indicates the measured concentration at the end of B. rerio toxicity test; ^bRate of concentration change (%): [(measured concentration at the end of toxicity test – 0 h-measured concentration)/0 h-measured concentration] × 100.

下载: 导出CSV

表 2 双唑草腈对斜生栅藻、大型溞和斑马鱼和的急性毒性

Table 2. The acute toxicity of pyraclonil to S. obliquus, D. magna and B. rerio

供试生物 Test organism	暴露时间 Exposure time/h	回归方程Regression equation	R²	LC₅₀ or EC₅₀/ (mg/L)	95% 置信区间 95% CL/(mg/L)
斜生栅藻 S. obliquus	24	y = 2.806x + 4.660	0.832	2.18 × 10⁻²	1.78 × 10⁻² ~ 3.81 × 10⁻²
	48	y = 4.011x + 7.234	0.975	1.57 × 10⁻²	1.48 × 10⁻² ~ 1.67 × 10⁻²
	72	y = 5.225x + 9.625	0.981	1.44 × 10⁻²	1.37 × 10⁻² ~ 1.51 × 10⁻²
大型溞 D. magna	24	y = 7.096x − 9.001	0.999	18.55	17.26 ~ 20.54
大型溞 D. magna	48	y = 8.983x − 10.589	0.984	15.09	14.30 ~ 15.97
斑马鱼 B. rerio	24^*	―	―	―	―
	48	y = 6.873x − 9.497	0.978	24.09	21.04 ~ 29.34
	72	y = 7.197x − 9.783	0.986	23.05	20.13 ~ 27.17
	96	y = 7.197x − 9.783	0.986	23.05	20.13 ~ 27.17
注：^因死亡率远低于50%而未进行数据分析。Note: ^Data analysis was not performed because the mortality rate was much lower than 50%.

下载: 导出CSV

表 3 双唑草腈的理化性质及环境归趋数据

Table 3. Physicochemical properties and environmental fate data of pyraclonil

参数名称　　　　　　　　　　　　　 Parameter name	数据 Data	数据来源 Data source	模型最终输入值 Final input value
辛醇/水分配系数 log K_ow，pH = 7，20 ℃	1.61	[19]	1.61
摩尔分子量 Molar mass/(g/mol)，20 ℃	314.77	[19]	314.77
饱和蒸气压 Saturated vapor pressure/Pa，25 ℃	1.9 × 10⁻⁷	[3]	1.9 × 10^{−7 a}
饱和蒸气压 Saturated vapor pressure/Pa，25 ℃	1.9 × 10⁻⁷	[20]	1.9 × 10^{−7 a}
水中溶解度 Solubility in water/(mg/L)，20 ℃	50.1	[3]	50.1 ^a
水中溶解度 Solubility in water/(mg/L)，20 ℃	50.1	[20]	50.1 ^a
土壤吸附系数 Soil adsorption coefficient，K_oc/(L/kg)，20 ℃	243	[21]	243
Freundlich 吸附指数 Freundlich sorption exponent，1/n	0.852	[21]	0.852
土壤降解半衰期 (好氧) Soil degradation half-life (aerobic)/d，25 ℃	6.8~8.2	[22]	8.2 ^b
土壤降解半衰期(厌氧) Soil degradation half-life (anaerobic)/d，25 ℃	131~139	[22]	139 ^b
水解半衰期 Hydrolysis half-life/d，25℃	>365	[20]	1000 ^c
水解半衰期 Hydrolysis half-life/d，25℃	>365	[21]	1000 ^c
每日允许摄入量 ADI/(mg/kg bw)	0.0044	[22]	0.0044
注：^a有2 个及以上数据相同时，选出现最多的数据作为模型输入值；^b遵循风险最大化原则，取半衰期最大值；^c取默认值，温度默认为20 ℃。Note: ^a If two or more data are the same, the most frequent data was selected as the final input value；^b Following the principle of risk maximization, the longest degradation half-life was chosen; ^c The default value and default temperature (20 ℃).

下载: 导出CSV

表 4 双唑草腈的急性毒性数据

Table 4. Acute toxicity data of pyraclonil

生物类型　　　　　　 Biological type	物种 Specie	不确定性因子 UF	预测无效应浓度 PNEC/(μg/L)
初级生产者 Primary producer	斜生栅藻 S. obliquus	10	1.44
无脊椎动物 Invertebrate	大型溞 D. magna	100	150.9
脊椎动物 Vertebrate	斑马鱼 B. rerio	100	230.5

下载: 导出CSV

表 5 不同预测环境浓度下双唑草腈RQ < 1的占比分布

Table 5. Proportion of RQ < 1 of pyraclonil to organisms under different PECs %

物种 Specie	场景 Scenario	预测环境浓度 PEC
物种 Specie	场景 Scenario	地表径流 Runoff	池塘水 Pond	时间加权 TWA
斜生栅藻 S. obliquus	连平-早稻 Lianping- early rice	0.00	0.00	0.00
	连平-晚稻 Lianping-late rice	26.09	21.74	26.09
	南昌-早稻 Nanchang-early rice	5.00	5.00	5.00
	南昌-晚稻 Nanchang-late rice	43.48	43.48	43.48
大型溞 D. magna	连平-早稻 Lianping-early rice	33.33	100.00	100.00
	连平-晚稻 Lianping-late rice	69.57	100.00	100.00
	南昌-早稻 Nanchang-early rice	60.00	100.00	100.00
	南昌-晚稻 Nanchang-late rice	86.96	100.00	100.00
斑马鱼 B. rerio	连平-早稻 Lianping-early rice	42.86	100.00	100.00
	连平-晚稻 Lianping-late rice	78.26	100.00	100.00
	南昌-早稻 Nanchang-early rice	75.00	100.00	100.00
	南昌-晚稻 Nanchang-late rice	95.65	100.00	100.00

下载: 导出CSV

表 6 不同预测环境浓度下双唑草腈的风险商值分析

Table 6. Analysis of RQs under different PECs

物种 Specie	类别 Different category	风险商 RQ
物种 Specie	类别 Different category	平均值 Mean	第 60 百分位数 60^th Quantile	最大值 Maximum	最小值 Minimum
斜生栅藻 S. obliquus	地表径流 Runoff	143.09	97.24	618.52	0
	池塘水 Pond	28.22	35.72	84.39	1.39 × 10⁻⁶
	时间加权 TWA	26.29	35.02	82.85	0
大型溞 D. magna	地表径流 Runoff	1.37	0.9280	5.90	0
	池塘水 Pond	0.27	0.3409	0.81	1.33 × 10⁻⁸
	时间加权 TWA	0.25	0.3345	0.80	0
斑马鱼 B. rerio	地表径流 Runoff	0.89	0.6075	3.86	0
	池塘水 Pond	0.18	0.2232	0.53	8.68 × 10⁻⁹
	时间加权 TWA	0.16	0.2186	0.51	0

下载: 导出CSV

参考文献(25)

[1]	牛立志, 桂文君, 朱国念. 草铵膦在水中的降解特性及对水生生物的毒性[J]. 浙江农业学报, 2010, 22(4): 485-490. NIU L Z, GUI W J, ZHU G N. The degradation of glufosinate in water and toxicity to aquatic organism[J] Acta Agric Zhejiangensis, 2010, 22(4): 485-490.
[2]	单正军, 陈祖义. 农药对水生生物的污染影响及污染控制技术[J]. 农药科学与管理, 2007, 28(10): 18-20. doi: 10.3969/j.issn.1002-5480.2007.10.006 SHAN Z J, CHEN Z Y. Pollution effects of pesticides on aquatic organisms and pollution control technology[J]. Pestic Sci Adm, 2007, 28(10): 18-20. doi: 10.3969/j.issn.1002-5480.2007.10.006
[3]	张一宾. 水稻田用除草剂双唑草腈 (pyraclonil) 的研发及其应用普及[J]. 世界农药, 2014, 36(6): 1-3. ZHANG Y B. Development and application of pyraclonil in paddy field[J]. World Pestic, 2014, 36(6): 1-3.
[4]	徐蓬, 吴佳文, 王红春, 等. 双唑草腈的除草活性及对水稻的安全性[J]. 植物保护, 2017, 43(5): 198-204. doi: 10.3969/j.issn.0529-1542.2017.05.033 XU P, WU J W, WANG H C, et al. Herbicidal activity of pyraclonil to the weeds in rice fields and its safety to rice[J]. Plant Prot, 2017, 43(5): 198-204. doi: 10.3969/j.issn.0529-1542.2017.05.033
[5]	田志慧, 袁国徽, 沈国辉. 双唑草腈防除直播稻田杂草效果及其对水稻安全性研究[J]. 上海农业学报, 2021, 37(1): 76-81. TIAN Z H, YUAN G H, SHEN G H. Control effects and safety of pyraclonil on weeds in direct seeding rice fields[J]. Acta Agric Shanghai, 2021, 37(1): 76-81.
[6]	张月, 李卫, 周雯雯, 等. 双唑草腈在 3 种典型土壤中的降解[J]. 农药学学报, 2020, 22(5): 897-902. ZHANG Y, LI W, ZHOU W W, et al. Degradation of pyraclonil in three typical soils[J]. Chin J Pestic Sci, 2020, 22(5): 897-902.
[7]	张月, 周雯雯, 贾浩然, 等. 双唑草腈在 7 种土壤中的淋溶特性[J]. 农药, 2019, 58(12): 893-897. ZHANG Y, ZHOU W W, JIA H R, et al. Leaching characteristics of pyraclonil in seven soils[J]. Agrochemicals, 2019, 58(12): 893-897.
[8]	孔玄庆, 欧晓明, 金晨钟, 等. 双唑草腈对非洲爪蟾蝌蚪和胚胎的影响[J]. 农药, 2018, 57(7): 503-505. KONG X Q, OU X M, JIN C Z, et al. Effects of pyraclonil on Xenopus leavis tadpoles and embryos[J]. Agrochemicals, 2018, 57(7): 503-505.
[9]	TAKASHI N, KIYOSHI T, IKUKO Y. Comparative toxicity of 20 herbicides to 5 periphytic algae and the relationship with mode of action[J]. Environ Toxicol Chem, 2016, 35(2): 368-375. doi: 10.1002/etc.3150
[10]	OECD. Method 201 guidelines for testing of chemicals: freshwater alga and cyanobacteria, growth inhibition test [S]. Paris: Environment Health and Safety Publication, 2011.
[11]	OECD. Method 202 guidelines for testing of chemicals: Daphnia sp. , acute immobilization test [S]. Paris: Environment Health and Safety Publication, 2004.
[12]	OECD. Method 203 guidelines for testing of chemicals: fish, acute toxicity test [S]. Paris: Environment Health and Safety Publication, 1992.
[13]	中国农业农村部农药检定所. TOP-RICE模型操作手册[Z]. 北京: 中国农业农村部农药检定所, 2014. Top-rice model operation manual[Z]. Beijing: ICAMA, 2014.
[14]	毛连纲, 周艳明, 张兰, 等. 基于 TOP-RICE 模型嘧菌酯·噻呋酰胺 4% 展膜油剂稻田水溢出对水生生态系统风险评估研究[J]. 生态毒理学报, 2017, 12(4): 153-163. MAO L G, ZHOU Y M, ZHANG L, et al. Risk assessment of azoxystrobin·thifluzamide 4% spreading oil water overflow in rice paddies on aquatic ecosystem based on TOP-RICE model[J]. Asian J Ecotoxicol, 2017, 12(4): 153-163.
[15]	农药登记环境风险评估指南第 2 部分: 水生生态系统: NY/T 2882.2—2016[S]. 北京: 中国农业出版社, 2016. Guidance on environmental risk assessment for pesticide registration, part 2: aquatic ecosystem: NY/T 2882.2—2016[S]. Beijing: Chinese Agriculture Press, 2016.
[16]	钱传范. 农药残留分析原理与方法[M]. 北京: 化学工业出版社, 2011. QIAN C F. Principle and method of pesticide residue analysis[M]. Beijing: Chemical Industry Press, 2011.
[17]	化学农药环境安全评价试验准则: GB/T 31270[S]. 北京: 中国标准出版社, 2014. Experimental guideline for environmental safety evaluation of chemical pesticid: GB/T 31270[S]. Beijing: Standards Press of China, 2014.
[18]	中国农药信息网[EB/OL]. [2021-04-23]. http://www.icama.org.cn/hysj/index.jhtml. China Pesticide Information Network[EB/OL]. [2021-04-23]. http://www.icama.org.cn/hysj/index.jhtml.
[19]	University of Hertfordshire. The PPDB (Pesticide Properties Database): IUPAC, global availability of information on agrochemicals [DB/OL]. [2021-03-03]. http://sitem.herts.ac.uk/aeru/ppdb/en/Reports/1166.htm
[20]	日本环境省. 水産動植物の被害防止に係る農薬登録保留基準の設定に関する資料 (ピラクロニル)[DB/OL]. [2006-06-29]. https://www.env.go.jp/water/sui-kaitei/kijun/rv/h02_pyraclonil.pdf Ministry of the Environment Government of Japan. Data on the establishment of standards for retention of agricultural chemicals for prevention of damage to aquatic animals and plants (pyraconil)[DB/OL]. [2006-06-29]. https://www.env.go.jp/water/sui-kaitei/kijun/rv/h02_pyraclonil.pdf
[21]	農林水産消費安全技術センター(FAMIC). ピラクロニル農薬抄録[DB/OL]. [2012-09-15]. http://www.acis.famic.go.jp/syouroku/ pyraclonil/index.htm Food and Agricultural Materials Inspection Center (FAMIC). Pyraconil pesticides abstract[DB/OL]. [2012-09-15]. http://www. acis.famic.go.jp/syouroku/pyraclonil/index.htm
[22]	日本食品安全委员会. 第 71 回農薬専門調査会幹事会ピラクロニル評価書, 第 2 版 [DB/OL]. [2011-04-15]. http://www.fsc.go.jp/ fsciis/evaluationDocument/show/kya20100618447. Food Safety Commission of Japan. The 71^st report to the secretary's meeting pyraconil of the agricultural door investigation committee, version 2 [DB/OL ]. [2011-04-15]. http://www.fsc.go.jp/fsciis/evaluationDocument/show/kya20100618447.
[23]	瞿晶菁, 刘春霞, 付少华, 等. 双唑草腈原药大鼠亚慢性毒性试验[J]. 毒理学杂志, 2015, 29(2): 158-160. QU J J, LIU C X, FU S H, et al. Subchronic toxicity test of pyraconil in rats[J]. J Toxicol, 2015, 29(2): 158-160.
[24]	农业农村部农药检定所. 农药登记环境风险评估指南[M]. 北京: 中国农业出版社, 2018. Institute for the Control of Agrochemicals, Ministry of Agriculture and Rural Affairs. Guidance on environmental risk assessment for pesticide registration[M]. Beijing: Chinese Agriculture Press, 2018.
[25]	林绿, 覃志豪, 李文娟. 我国农药地下水环境风险评估场景体系的建立[J]. 农业环境科学学报, 2014, 33(11): 2194-2203. doi: 10.11654/jaes.2014.11.018 LIN L, QIN Z H, LI W J. Development of a GIS-based scenario analysis system for pesticide groundwater risk assessment in China[J]. J Agro Environ Sci, 2014, 33(11): 2194-2203. doi: 10.11654/jaes.2014.11.018