Advanced risk assessment for aquatic ecology of single-dose of pyraclostrobin registered on four crops
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摘要: 通过对中国目前在水稻、小麦、柑橘和马铃薯4种作物上登记的所有吡唑醚菌酯单剂产品进行统计梳理,利用Top-Rice模型及China-Psem模型预测了其在地表水中的暴露量,评估了吡唑醚菌酯对水生生态的高级风险。结果显示:截至2021年5月,中国在4种作物上登记的吡唑醚菌酯单剂产品共25种,分为5种剂型。其中悬浮剂占比最大,为52%;其次为乳油,占20%;微囊悬浮剂、水分散粒剂及可湿性粉剂分别占16%、8%和4%。基于风险评估保守性原则,归纳出适用模型进行分析的不同剂型吡唑醚菌酯单剂产品的施用模式,对其在4种作物上使用后的暴露风险分组进行了分析。结果显示:不同剂型吡唑醚菌酯单剂在不同场景、不同季节的水稻上施用后,其预测环境浓度 (PEC) 范围为0.07~1.24 μg/L;在小麦上施用后,其PEC值范围为0.45 × 10−3~0.60 μg/L;在柑橘上的PEC值范围为0.03~0.76 μg/L;在马铃薯上的PEC值范围为0.01~0.94 μg/L。风险表征结果显示,在现有登记施用条件下,吡唑醚菌酯单剂按推荐方法、推荐剂量及推荐次数在4种作物上施用,其风险均可接受,但鉴于其对水生生物有较高的毒性,对水生生态系统存在一定风险,因此应谨慎控制吡唑醚菌酯在水田的施用剂量和频率。本研究针对其施药模式的分析偏保守,所得评估结果具有一定的不确定性。
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关键词:
- 吡唑醚菌酯 /
- 水稻 /
- 小麦 /
- 柑橘 /
- 马铃薯 /
- 水生生态系统 /
- 风险 /
- 评估 /
- Top-Rice模型 /
- China-Psem模型
Abstract: The current situation of single-dose pyraclostrobin products registered on rice, wheat, citrus and potato in China were analyzed, and the exposure concentration in surface water was predicted by using Top-Rice and China-Psem models, as well as their advanced risk to aquatic ecosystem were assessed. The results showed that as of May 2021, there were 25 formualtions of pyraclostrobin registered on four crops in China, which were divided into 5 groups. The proportion of suspension concentrate (SC) was the largest, accounting for 52%, followed by emulsifiable concentrate (EC), accounting for 20%, microcapsule suspension (CS), water dispersible granule (WG) and wettable powders (WP) accounted for 16%, 8% and 4%, respectively. The application range of different formulations of pyraclostrobin and the exposure assessment of different groups on the four crops were investigated, according to the conservative principles of risk assessment. The results showed that the predicted environmental concentration (PEC) of pyraclostrobin on rice ranged from 0.07 to 1.24 μg/L in different scenarios and seasons, the predicted environmental concentration of pyraclostrobin used on wheat ranged from 0.45 × 10−3 to 0.60 μg/L, the predicted environmental concentration of pyraclostrobin used on citrus ranged from 0.03 to 0.76 μg/L, and the predicted environmental concentration of pyraclostrobin used on potato ranged from 0.01 to 0.94 μg/L. Under the current registered application conditions, the risk characterization showed that pyraclostrobin was used on four crops for the recommended method, dosage and number of times, the risk was acceptable. However, in view of its high toxicity to aquatic organisms, the dosage and frequency of application on paddy fields should be cautious, as it poses certain risks to aquatic ecosystems. In the present study, the analysis of its application method mode was conservative, which might be underestimeated the evaluation result in some way.-
Key words:
- pyraclostrobin /
- rice /
- wheat /
- citrus /
- potato /
- aquatic ecosystem /
- risk /
- assessment /
- Top-Rice model /
- China-Psem model
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表 1 不同剂型吡唑醚菌酯在水稻田的模拟施用量及分组
Table 1. Simulation dosage and grouping of different formulations of pyraclostrobin used on rice
剂型
Formulation施用量范围
Applied range, a.i./
(kg/hm2)分组 I
Group I, a.i./
(kg/hm2)分组 II
Group II, a.i./
(kg/hm2)分组 III
Group III, a.i./
(kg/hm2)分组 IV
Group IV, a.i./
(kg/hm2)微囊悬浮剂
Microcapsule suspension, CS0.0756~0.0986 0.0986,施 2 次
Applied twice0.0986,施 1 次
Applied once0.0756,施 2 次
Applied twice0.0756,施 1 次
Applied once表 4 不同剂型吡唑醚菌酯在马铃薯田的模拟施用量及分组
Table 4. Simulation dosage and grouping of different formulations of pyraclostrobin used on potato
剂型
Formulation施用量范围
Applied range, a.i./(kg/hm2)分组 I
Group I, a.i./(kg/hm2)分组 II
Group II, a.i./(kg/hm2))分组 III
Group III, a.i./(kg/hm2)分组 IV
Group IV, a.i./(kg/hm2)悬浮剂
Suspension concentrate, SC0.075~0.15 0.15,施 3 次
Applied three times0.15,施 1 次
Applied once0.075,施 3 次
Applied three times0.075,施 1 次
Applied once微囊悬浮剂
Microcapsule suspension, CS0.09~0.15 0.15,施 2 次
Applied twice0.15,施 1 次
Applied once0.09,施 2 次
Applied twice0.09,施 1 次
Applied once乳油
Emulsifiable concentrate, EC0.075~0.18 0.18,施 3 次
Applied three times0.18,施 1 次
Applied once0.075,施 3 次
Applied three times0.075,施 1 次
Applied once表 2 不同剂型吡唑醚菌酯在小麦田的模拟施用量及分组
Table 2. Simulation dosage and grouping of different formulations of pyraclostrobin used on wheat
剂型
Formulation施用量范围
Applied range, a.i./(kg/hm2)分组 I
Group I, a.i./(kg/hm2)分组 II
Group II, a.i./(kg/hm2)分组 III
Group III, a.i./(kg/hm2)分组 IV
Group IV, a.i./(kg/hm2)悬浮剂
Suspension concentrate, SC0.0765~0.15 0.15,施 2 次
Applied twice0.15,施 1 次
Applied once0.0765,施 2 次
Applied twice0.0765,施 1 次
Applied once水分散粒剂
Water dispersible granule, WG0.094~0.1125 0.1125,施 2 次
Applied twice0.1125,施 1 次
Applied once0.094,施 2 次
Applied twice0.094,施 1 次
Applied once乳油
Emulsifiable concentrate, EC0.1125~0.15 0.15,施 2 次
Applied twice0.15,施 1 次
Applied once0.1125,施 2 次
Applied twice0.1125,施 1 次
Applied once表 3 不同剂型吡唑醚菌酯在柑橘园的模拟施用量及分组
Table 3. Simulation dosage and grouping of different formulations of pyraclostrobinl used on citrus
剂型
Formulation施用量范围
Applied range, a.i./(kg/hm2)分组 I
Group I, a.i./(kg/hm2)分组 II
Group II, a.i./(kg/hm2)分组 III
Group III, a.i./(kg/hm2)分组 IV
Group IV, a.i./(kg/hm2)悬浮剂
Suspension concentrate, SC0.18~0.36 0.36,施 3 次
Applied three times0.36,施 1 次
Applied once0.18,施 3 次
Applied three times0.18,施 1 次
Applied once乳油
Emulsifiable concentrate, EC0.15~0.225 0.225,施 3 次
Applied three times0.225,施 1 次
Applied once0.15,施 3 次
Applied three times0.15,施 1 次
Applied once可湿性粉剂
Wettable powders, WP0.225~0.45 0.45,施 4 次
Applied four times0.45,施 1 次
Applied once0.225,施 4 次
Applied four times0.225,施 1 次
Applied once表 5 吡唑醚菌酯在Top-Rice模型中的输入值
Table 5. Pyraclostrobin input values into the Top-Rice model
参数
Parameter查询参数值
Query parameter模型输入值
Inputs values of model摩尔质量
Molar mass/(g/mol)387.82 387.82 水中溶解度
Solubility in water/(mg/L)1.9, 20 ℃ 1.9, 20 ℃ 饱和蒸气压
Saturated vapor pressure/Pa2.6 × 10−8, 20 ℃ 2.6 × 10−8, 20 ℃ 土壤有机质吸附常数
Adsorption constant of soil organic matter, Kom/(L/kg)5396.75 5395.59c 5396.75a 5394.43b 土壤好氧降解半衰期
Aerobic degradation half-life in soil/d, ℃40.9 (DT50 lab), 20 ℃ 41.40c, 20 ℃ 41.9 (DT50 lab)a, 20 ℃ 土壤厌氧降解半衰期
Anaerobic degradation half-life in soil/d2, 20 ℃
2.4, 20 ℃
3b, 20 ℃2.43c, 20 ℃ 池塘水层半衰期
Half-life in the water layer of water body/d1) 水-沉积物系统中水层降解, 2.13, 20 ℃
Degradation of the water layer in the water-sediment system, 2.13, 20 ℃2.21d, 20 ℃ 2) 水-沉积物系统中水层降解, 2.3, 20 ℃
Degradation of the water layer in the water-sediment system, 2.3, 20 ℃稻田水层半衰期
Half-life in the water layer of paddy field/d1) 水-沉积物系统中水层降解, 2.13, 20 ℃
Degradation of the water layer in the water-sediment system, 2.13, 20 ℃2.21d, 20 ℃ 2) 水-沉积物系统中水层降解, 2.3, 20 ℃
Degradation of the water layer in the water-sediment system, 2.3, 20 ℃施药时期
Applied dateBBCH 20~60 BBCH 20~60e 施药剂量
Applied dosage, a.i./(kg/hm2)0.0756~0.0986 0.0756~0.0986f 施药次数
Applied times2 2f 施药间隔
Applied interval/d7 7f 施药方式
Applied mode喷雾 Spray 喷雾 Spray 施药漂移率
Applied spraydrift/%1.16 1.16g 注:非另外标注,表中数据均来源于EFSA报告[24]。a数据来源于PPDB数据库[22];b数据来源于PAN数据库[21];c取几何平均值,其中Kom=Koc/1.724;d根据相关准则[25],池塘水层半衰期取水-沉积物降解试验中农药在水层的消解半衰期,稻田水层半衰期取水-沉积物降解试验中农药在水层的消解半衰期;eBBCH 代表植物生长期标准分级,用于描述植物生长阶段;f取值可根据分组评估情况进行选择,计算时优先计算风险最大的情况 (最大推荐施药剂量、最多推荐使用次数、最短推荐施药间隔);g根据准则[25],当有资料表明施药时水稻株高≥50 cm时,漂移率可取1.16或实测值。Note: Unless otherwise noted, the data in the table were all from the EFSA report[24]. aThe data come from the PPDB database[22]. bThe data come from the PAN database[21]. cThe geometric mean, Kom =Koc/1.724. dAccording to the guidelines[25], pond water layer half-life takes the half-life of the water layer in the water-sediment system and paddy field water layer half-life takes the half-life of the water layer in the water-sediment system). eBBCH represents the standard grading of plant growth period, used to describe the plant growth stage. fThe value can be selected according to the group evaluation situation, and the calculation will give priority to the most risky situation (the maximum recommended dosage, the maximum recommended frequency of application, and the shortest recommended application interval). gAccording to the guidelines[25] when there is data showing that the rice plant height is more than 50 cm when applying the pesticide, the drift rate can be 1.16 or the actual value. 表 6 吡唑醚菌酯在China-Psem模型中的输入值
Table 6. Pyraclostrobin input values into the China-Psem model
参数
Parameter查询参数值
Query parameter模型输入值
Inputs values of model摩尔质量
Molar mass/(g/mol)387.82 387.82 水中溶解度
Solubility in water/(mg/L)1.9, 20 ℃ 1.9, 20 ℃ 饱和蒸气压
Saturated vapor pressure/torr1.95 × 10−10, 20 ℃ 1.95 × 10−10, 20 ℃ 吸附系数
Sorption coefficient, Koc/(mL/g)9304 9302c 9304a 9300b 土壤好氧降解半衰期
Aerobic degradation half-life in soil/d40.9(DT50 lab), 20 ℃ 41.40c, 20 ℃ 41.9(DT50 lab)a, 20 ℃ 水中光解半衰期
Aqueous photolysis half-life/d1) 水-沉积物系统中水层降解, 2.13, 20 ℃
Degradation of the water layer in the water-sediment system, 2.13, 20 ℃2.21c 2) 水-沉积物系统中水层降解, 2.3, 20 ℃
Degradation of the water layer in the water-sediment system, 2.3, 20 ℃水体代谢半衰期
Water column metabolism
half-life/d1) 水-沉积物系统中水层降解, 2.13, 20 ℃
Degradation of the water layer in the water-sediment system, 2.13, 20 ℃
2.14c, 20 ℃2) 水-沉积物系统中水层降解, 2.3, 20 ℃
Degradation of the water layer in the water-sediment system, 2.3, 20 ℃3) 水体代谢, 2a, 20 ℃
Water column metabolism half-life, 2a, 20 ℃底泥代谢半衰期
Benthic metabolism half-life/d1) 水-沉积物降解试验, 28, 20 ℃
Water-sediment degradation test, 28, 20 ℃25.54c, 20 ℃ 2) 水-沉积物降解试验, 23.3, 20 ℃
Water-sediment degradation test, 23.3, 20 ℃3) 28a, 20 ℃ 水解半衰期
Hydrolysis half-life/d30b 30 叶面降解半衰期
Foliar degradation half-life/d5a 5 施药时期
Applied date小麦 Wheat BBCH 31~59 BBCH 31~59d 柑橘 Citrus BBCH 31~39 BBCH 31~39d 马铃薯 Potato BBCH 40~49 BBCH 40~49d 施药剂量
Applied dosage, a.i./(kg/hm2)小麦 Wheat 0.0765~0.15 0.0765~0.15e 柑橘 Citrus 0.15~0.45 0.15~0.45e 马铃薯 Potato 0.075~0.18 0.075~0.18e 施药次数
Applied times小麦 Wheat 2 2e 柑橘 Citrus 3~4 3~4e 马铃薯 Potato 2~3 2~3e 施药间隔 Applied interval/d 7~10 7~10e 施药方式 Applied mode 喷雾 Spray 喷雾 Spray 注:非另外标注,表中数据均来源于EFSA报告[24]。a数据来源于PPDB数据库[22];b数据来源于PAN数据库[21];c取几何平均值;dBBCH 表示植物生长期标准分级,用于描述植物生长阶段;e取值可以根据分组评估情况进行选择,计算时优先计算风险最大的情况 (最大推荐施药剂量、最多推荐使用次数、最短推荐施药间隔)。Note: Unless otherwise noted, the data in the table are all from the EFSA report[24]. aThe data comes from the PPDB database[22]. bThe data comes from the PAN database[21]. cThe geometric mean. dBBCH represents the standard grading of plant growth period, used to describe the growth stage of the plant. eThe value can be selected according to the group evaluation situation, and the calculation will give priority to the most risky situation (the maximum recommended dosage, the maximum recommended frequency of application, and the shortest recommended application interval). 表 7 吡唑醚菌酯对水生生态系统的效应分析
Table 7. Analysis of the effects of pyraclostrobin on aquatic ecosystem
毒性试验类型
Toxicity test
type生物分类
Biological
classification生物物种
Biological
species毒性终点
Toxicity
endpoint毒性效应
终点值
EnP/(μg/L)评估终点值
Assessment
endpoint/(μg/L)不确定性因子
UF预测无效应浓度
PNEC/(μg/L)中宇宙
Mesocosm无脊椎动物、
脊椎动物、
初级生产者
Invertebrates,
vert-ebrates,
primary
producer浮游动物、
大型无脊椎动物、
浮游植物、锦鲤
Zooplankton,
macroinvertebrates,
phyt-oplankton,
Cyprinus carpioNOEC-EROa
NOEC-ETOa13.8b
0.9b3.52 3 1.17 注:aNOEC-ERO 表示基于生态恢复选项的最大无效应浓度;NOEC-ETO 表示基于生态阈值选项的最大无效应浓度。b毒性资料来源于 EFSA 报告[24]。 Note: aNOEC-ERO represent the maximum no effect concentration based on ecological restoration options. NOEC-ETO represent the maximum no effect concentration based on the ecological threshold option. bToxicity information comes from EFSA report[24]. -
[1] BALBA H. Review of strobilurin fungicide chemicals[J]. J Environ Sci Health B, 2007, 42(4): 441-451. doi: 10.1080/03601230701316465 [2] 王丽, 石延霞, 李宝聚, 等. 甲氧基丙烯酸酯类杀菌剂研究进展[J]. 农药科学与管理, 2008, 29(9): 24-27. doi: 10.3969/j.issn.1002-5480.2008.09.008WANG L, SHI Y X, LI B J, et al. The progresses of research on strobilurin fungicides[J]. Pestic Sci Adm, 2008, 29(9): 24-27. doi: 10.3969/j.issn.1002-5480.2008.09.008 [3] 马超, 赵宜君, 张力卜, 等. 吡唑醚菌酯悬浮剂的研制及配方中表面活性剂的复配性能分析[J]. 农药, 2021, 60(1): 18-22.MA C, ZHAO Y J, ZHANG L B, et al. The preparation of pyraclostrobin SC and the combination of surfactant in the formulation[J]. Agrochemicals, 2021, 60(1): 18-22. [4] WIGHTWICK A M, BUI A D, ZHANG P, et al. Envirornmental fate of fungicides in surface waters of a horticultural-production catchment in southeastern Australia[J]. Arch Environ Contam Toxicol, 2012, 62(3): 380-390. doi: 10.1007/s00244-011-9710-y [5] MIMBS W H, CUSAAC J P W, SMITH L M, et al. Occurrence of current-use fungicides and bifenthrin in rainwater basin wetlands[J]. Chemosphere, 2016, 159: 275-281. doi: 10.1016/j.chemosphere.2016.06.012 [6] GUO X Y, WU W Z, SONG N H, et al. Residue dynamics and risk assessment of pyraclostrobin in rice, plants, hulls, field soil, and paddy water[J]. Hum Ecol Risk Assess Int J, 2017, 23(1): 67-81. doi: 10.1080/10807039.2016.1222579 [7] SMALLING K L, KUIVILA K M, ORLANDO J L, et al. Environmental fate of fungicides and other current-use pesticides in a central California estuary[J]. Mar Pollut Bull, 2013, 73(1): 144-153. doi: 10.1016/j.marpolbul.2013.05.028 [8] OLIVEIRA F A, REIS L P G, SOTO-BLANCO B, et al. Pesticides residues in the Prochilodus costatus (Valenciennes, 1850) fish caught in the São Francisco River, Brazil[J]. J Environ Sci Health B, 2015, 50(6): 398-405. doi: 10.1080/03601234.2015.1011946 [9] BARTLETT D W, CLOUGH J M, GODWIN J R, et al. The strobilurin fungicides[J]. Pest Manag Sci, 2002, 58(7): 649-662. doi: 10.1002/ps.520 [10] 李慧, 曹芳杰, 邱立红. 甲氧基丙烯酸酯类杀菌剂对水生生物的生态毒理学研究进展[J]. 农药学学报, 2019, 21(5-6): 831-840.LI H, CAO F J, QIU L H. Research progress of the ecotoxicology of strobilurins on aquatic organisms[J]. Chin J Pestic Sci, 2019, 21(5-6): 831-840. [11] WANG K, SUN Z H, YANG L D, et al. Respiratory toxicity of azoxystrobin, pyraclostrobin and coumoxystrobin on Chlorella vulgaris[J]. Bull Environ Contam Toxicol, 2020, 104(6): 799-803. doi: 10.1007/s00128-020-02869-y [12] FENG C, CHAI T T, LIU X X, et al. Toxicity of three strobilurins (kresoxim-methyl, pyraclostrobin, and trifloxystrobin) on Daphnia magna[J]. Environ Toxicol Chem, 2017, 36(1): 182-189. doi: 10.1002/etc.3520 [13] LI D, LIU M Y, YANG Y S, et al. Strong lethality and teratogenicity of strobilurins on Xenopus tropicalis embryos: basing on ten agricultural fungicides[J]. Environ Pollut, 2016, 208(Pt B): 868-874. [14] 贾伟, 蒋红云, 张兰, 等. 4种甲氧基丙烯酸酯类杀菌剂不同剂型对斑马鱼急性毒性效应[J]. 生态毒理学报, 2016, 11(6): 242-251.JIA W, JIANG H Y, ZHANG L, et al. Acute toxicity of different formulation of four strobilurin fungicides to the zebrafish (Brachydonio rerio)[J]. Asian J Ecotoxicol, 2016, 11(6): 242-251. [15] YANG L, HUANG T, LI R, et al. Evaluation and comparison of the mitochondrial and developmental toxicity of three strobilurins in zebrafish embryo/larvae[J]. Environ Pollut, 2021, 270: 116277. doi: 10.1016/j.envpol.2020.116277 [16] LI H, CAO F J, ZHAO F, et al. Developmental toxicity, oxidative stress and immunotoxicity induced by three strobilurins (pyraclostrobin, trifloxystrobin and picoxystrobin) in zebrafish embryos[J]. Chemosphere, 2018, 207: 781-790. doi: 10.1016/j.chemosphere.2018.05.146 [17] LI H, ZHAO F, CAO F J, et al. Mitochondrial dysfunction-based cardiotoxicity and neurotoxicity induced by pyraclostrobin in zebrafish larvae[J]. Environ Pollut, 2019, 251: 203-211. doi: 10.1016/j.envpol.2019.04.122 [18] 中国农药信息网 [Z/OL]. [2021-06-01]. http://www.icama.org.cn/.China Pesticide Information Network[Z/OL]. [2021-06-01]. http://www.icama.org.cn/. [19] TOP-RICE 模型操作手册[R]. 北京: 农业农村部农药检定所, 2014: 2-6.TOP-RICE user manual [R]. Beijing: Institute for the Control of Agrochemicals, Ministry of Agriculture and Rural Affairs, 2014: 2-6. [20] 农药地表水暴露模型[R]. 北京: 农业农村部农药检定所, 2020: 1-11.China pesticide surface exposure model[R]. Beijing: Institute for the Control of Agrochemicals, Ministry of Agriculture and Rural Affairs, 2020: 1-11. [21] PAN pesticide database[DB/OL]. [2021-06-01]. https://www.pesticideinfo. org/chemical/PRI5461. [22] Pesticide properties database[DB/OL]. [2021-04-27]. http://sitem.herts.ac.uk/aeru/ppdb/en/Reports/564.htm. [23] Ecotox knowledgebase[DB/OL]. [2021-06-15]. https://cfpub.epa.gov/ecotox/search.cfm. [24] EFSA. Public consultation on the active substance pyraclostrobin[DB/OL]. [2018-09-10]. http://www.efsa.europa.eu/sites/default/files/consultation/consultation/Pyraclostrobin.zip. [25] 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. [26] 那晓磊, Haytham SHBAITA, 朱春雨, 等. 巴斯夫9%吡唑醚菌酯微囊悬浮剂技术特点分析[J]. 农药科学与管理, 2018, 39(7): 28-34. doi: 10.3969/j.issn.1002-5480.2018.07.009NA X L, SHBAITA H, ZHU C Y, et al. Analysis of technical characteristics of BASF pyraclostrobin 9% CS[J]. Pestic Sci Adm, 2018, 39(7): 28-34. doi: 10.3969/j.issn.1002-5480.2018.07.009 -