Acute toxicities of pyraclonil to three aquatic organisms and its primary ecological risk assessment
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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。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.
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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.
changeb/%0 h 48 h/72 h/96 ha 斜生栅藻
S. obliquusCK 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. magnaCK 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. rerioCK 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. 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. obliquus24 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. magna24 y = 7.096x − 9.001 0.999 18.55 17.26 ~ 20.54 48 y = 8.983x − 10.589 0.984 15.09 14.30 ~ 15.97 斑马鱼
B. rerio24* ― ― ― ― 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%. 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 Kow,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 1.9 × 10−7 [20] 水中溶解度 Solubility in water/(mg/L),20 ℃ 50.1 [3] 50.1 a 50.1 [20] 土壤吸附系数 Soil adsorption coefficient,Koc/(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 >365 [21] 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 ℃). 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. obliquus10 1.44 无脊椎动物
Invertebrate大型溞
D. magna100 150.9 脊椎动物
Vertebrate斑马鱼
B. rerio100 230.5 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 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 平均值
Mean第 60 百分位数
60th 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 -
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