新尼古丁類農藥為系統性殺蟲劑，由於其使用方式多樣化且對無脊椎動物具高毒性，而被廣泛用於不同的作物上，造成環境中亦可能有新尼古丁農藥存在。因此本研究目的是嘗試開發環境水樣品及底泥樣品中新尼古丁農藥之殘留分析方法，並分析國內所採集之環境樣品，以提供環境中新尼古丁類農藥殘留之相關數據。本研究參考檢測蔬果中農藥殘留的QuEChERS 方法，以減少乙腈(Acetonitrile)萃取液與鹽析之方式結合液相層析-三段四極式質譜儀(LC-MS/MS)開發分析方法，檢測環境水及底泥中新尼古丁類農藥殘留，修改後的QuEChERS方法與以往方法相比較為簡單，能減少前處理時間及分析成本，且方法具有足夠的靈敏度應用於環境水樣及底泥樣品分析，方法定量極限能夠達到各國訂立之標準。本研究取10 mL 水樣品或2 g 底泥樣品(添加10 mL 二次水)，加入含1%醋酸之乙腈、無水硫酸鎂及氯化鈉後，經震盪及離心，取部分上清液乾燥濃縮後回溶於適量50%甲醇中，經濾膜過濾後以LC-MS/MS 進行分析。本方法在環境水樣品中定量極限(S/N ratio ≧ 10)範圍為25 - 200 ng/L，線性最高點為4000 ng/L；底泥樣品中定量極限為125 - 250 ng/kg，線性最高點為10000 ng/kg，在水樣及底泥樣品中均可得到良好的線性(r2 > 0.996)，環境水樣之偵測極限(S/N ratio ≧ 3)
為10 - 100 ng/L；土壤樣品為61.25 - 250 ng/kg。在環境水樣及底泥樣品之精密度(CV%，3 濃度，6 重複)皆小於15 %，而準確度(%Error，3 濃度，6 重複)皆在±15 %範圍內。此外，以本研究之方法分析1. 台灣南部河川樣品(水樣及底泥樣品各32 件)，河川水樣中檢出亞滅培、益達胺及6-氯菸酸，底泥樣品中檢出亞滅培、益達胺及烯啶蟲胺；2. 大學池樣品(水樣及底泥樣品各18 件)與麒麟潭樣品(水樣及底泥樣品各18 件)，大學池環境水樣及底泥樣品皆未檢出殘留，而麒麟潭水樣
品中檢出可尼丁、達特南、益達胺及6-氯菸酸，底泥樣品中檢出可尼丁、益達胺及6-氯菸酸。

Neonicotinoids are one class of the most commonly used insecticides. The increasing applications of the insecticides have raised concerns about its environmental residue and the possible adverse effects. To address the continuing concerns and facilitate the related studies, a simple, sensitive and reliable analytical method is especially needed for monitoring the residues of the neonicotinoid insecticides in the environmental samples. In this study, a simple and low-cost method was developed for the determination of eight neonicotinoids and one major degradation product in environmental water and
soil samples. The modified QuEChERS methods applied obviously less volume of
acetonitrile containing 1% acetic acid to achieve pre-concentration. The extract was analyte by LC-MS/MS. The stable isotope internal standards were also applied. For the water sample analysis, the linear range ranged from 25-200 to 4000 ng/L (r 2>0.996), the estimated detection limits (S/N ratio≧3) were 10-100 ng/L. The method validation by the spiked QC samples (3 spiked levels, 6 replicates), the measured accuracy (%Error) was less than ±15% and the measured precision (CV%) was less than 15%. The developed method applied for surface water samples and sediment samples. Acetamiprid, clothianidin, dinotefuran, imidacloprid and 6-chloronicotinic acid were detected in water samples. In the sediment samples, the residues of acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, and 6-chloronicotinic acid were detected. The results represent the residues of neonicotinoids in the environment are extensively.

中文摘要 ................................................................... i
英文摘要 ................................................................. iii
誌謝 ...................................................................... iv
目錄 ....................................................................... v
表目錄 ................................................................... vii
圖目錄 .................................................................. viii
第一章 緒論................................................................ 1
1.1 前言................................................................ 1
1.2 作用機制及施用方式.................................................... 2
1.3 危害及降解、代謝 ..................................................... 2
1.4 新尼古丁類農藥歷年環境分析方法(縮減).................................... 5
1.4.1 環境水樣分析..................................................... 5
1.4.2 環境土樣分析 .................................................... 6
1.5 液相層析串聯質譜儀(LC-MS/MS) ......................................... 7
1.5.1 電灑游離法(ESI) ................................................. 7
1.6 研究動機 ............................................................ 8
第二章 材料與方法 .......................................................... 9
2.1 藥品及實驗材料 ...................................................... 9
2.1.1 標準品 .......................................................... 9
2.1.2 試劑與材料 ...................................................... 9
2.1.3 環境樣品來源 ................................................... 10
2.2 儀器設備及器材 ..................................................... 10
2.3 標準品與內部標準品儲備溶液配製 ....................................... 11
2.4 樣品前處理方法 ..................................................... 12
2.4.1 樣前處理方法測試 ................................................ 12
2.4.2 環境水樣前處理方法 .............................................. 12
2.4.3 環境土樣(底泥)前處理方法 ........................................ 13
2.5 液相層析串聯質譜方法 ................................................ 13
2.5.1 液相層析條件 ................................................... 13
2.5.2 質譜參數設定 ................................................... 14
2.6 方法性能測試 ....................................................... 14
2.6.1 線性與偵測極限測試 .............................................. 14
2.6.2 基質效應測試.................................................... 15
2.6.3 準確度與精密度測試 .............................................. 15
2.7 環境樣品分析 ....................................................... 16
2.7.1 環境水樣品分析 ................................................. 16
2.7.2 環境底泥樣品分析 ................................................ 16
第三章 結果與討論 ......................................................... 17
3.1 標準品測試 ......................................................... 17
3.1.1 新尼古丁類標準品及內部標準品之質譜分析 ............................ 17
3.1.2 LC-MS/MS 分析農藥標準品......................................... 17
3.2 樣品萃取方法測試..................................................... 18
3.2.1 萃取方法選擇 ................................................... 18
3.2.2 萃取條件測試 ................................................... 20
3.3 方法性能測試 ....................................................... 22
3.3.1 方法線性範圍及方法偵測極限 ....................................... 22
3.3.2 精密度及準確度 ................................................. 23
3.3.3 基質效應測試............... .................................... 23
3.4 環境樣品分析 ....................................................... 24
3.4.1 各國對環境中新尼古丁類農藥(益達胺)殘留標準 ........................ 24
3.4.2 105 及106 年南部8 條河川水樣及底泥樣品分析 ........................ 24
3.4.3 107 年大學池、麒麟潭之湖水樣品及底泥樣品分析 ...................... 25
3.4.4 相關文獻分析結果 ................................................ 26
第四章 結論............................................................... 29
參考文獻 ................................................................. 87
英文論文大綱 ................................................................. 95

1. Tisler, T.; Jemec, A.; Mozetic, B.; Trebse, P., Hazard identification of
imidacloprid to aquatic environment. Chemosphere 2009, 76 (7), 907-14.
2. Kreutzweiser, D.; Good, K.; Chartrand, D.; Scarr, T.; Thompson, D., Nontarget effects on aquatic decomposer organisms of imidacloprid as a systemic
insecticide to control emerald ash borer in riparian trees. Ecotoxicol Environ Saf 2007,68 (3), 315-25.
3. Bienkowski, B. Pesticides are all over the St. Lawrence River — many at levels that hurt fish and invertebrates Scientists tested the river system and found nearly onethird of the samples had neonicotinoid pesticides at levels higher than the threshold to protect aquatic creatures. Glyphosate and atrazine were in more than 80% of samples.
https://www.ehn.org/pesticides-are-all-over-the-st-lawrence-river-many-at-levels-thathurt-fish-and-invertebrates-2635826209.html?rebelltitem=1.
4. Goulson, D.; Kleijn, D., REVIEW: An overview of the environmental risks posed by neonicotinoid insecticides. Journal of Applied Ecology 2013, 50 (4), 977-987.
5. Jeschke, P.; Nauen, R., Neonicotinoids-from zero to hero in insecticide chemistry. Pest Manag Sci 2008, 64 (11), 1084-98.
6. Tanner, G.; Czerwenka, C., LC-MS/MS analysis of neonicotinoid insecticides in honey: methodology and residue findings in Austrian honeys. J Agric Food Chem 2011, 59 (23), 12271-7.
7. Sanchez-Bayo, F., Insecticides mode of action in relation to their toxicity to nontarget organisms. Journal of Environmental & Analytical Toxicology 2012.
8. Tomizawa, M.; Casida, J. E., Neonicotinoid insecticide toxicology: mechanisms of selective action. Annu Rev Pharmacol Toxicol 2005, 45, 247-68.
9. Tomizawa, M.; Casida, J. E., Selective toxicity of neonicotinoids attributable to specificity of insect and mammalian nicotinic receptors. Annu Rev Entomol 2003, 48, 339-64.
10. Morita, M.; Ueda, T.; Yoneda, T.; Koyanagi, T.; Haga, T., Flonicamid, a
novel insecticide with a rapid inhibitory effect on aphid feeding. Pest Management Science: formerly Pesticide Science 2007, 63 (10), 969-973.
11. Wang, S.; Jin, F.; Cao, X.; Shao, Y.; Wang, J.; She, Y.; Qi, Y.; Zhang,
C.; Li, H.; Jin, M.; Wang, J.; Shao, H.; Zheng, L., Residue behaviors and risk
assessment of flonicamid and its metabolites in the cabbage field ecosystem. Ecotoxicol Environ Saf 2018, 161, 420-429.
12. Jeschke, P.; Nauen, R.; Schindler, M.; Elbert, A., Overview of the status and global strategy for neonicotinoids. J Agric Food Chem 2011, 59 (7), 2897-908.
13. Leandro, C.; Souza, V.; Dores, E. F.; Ribeiro, M. L. J. J. o. t. B. C. S.,
Determination of pesticides multiresidues in shallow groundwater in a cotton-growing region of Mato Grosso, Brazil. 2008, 19 (6), 1111-1117.
14. Fossen, M. J. C. D. o. P. R., Environmental fate of imidacloprid.2006,1-16.
15. Banerjee, K.; Patil, S. H.; Dasgupta, S.; Oulkar, D. P.; Adsule, P. G., Sorption of thiamethoxam in three Indian soils. J Environ Sci Health B 2008, 43 (2), 151-6.
16. 登記農藥查詢.
https://pesticide.baphiq.gov.tw/web/Insecticides_MenuItem5_3.aspx?fbclid=IwAR3S
_90N4P2vjbSUOqJDBQDT42hYNZbHSmZBci4KegUNLy7cwgFVJ6RsvE.
17. Sanchez-Bayo, F.; Hyne, R. V., Detection and analysis of neonicotinoids in river waters--development of a passive sampler for three commonly used insecticides. Chemosphere 2014, 99, 143-51.
18. Zheng, W.; Liu, W. J. P. s., Kinetics and mechanism of the hydrolysis of
imidacloprid. 1999, 55 (4), 482-485.
19. Baskaran, S.; Kookana, R. S.; Naidu, R. J. P. S., Degradation of bifenthrin, chlorpyrifos and imidacloprid in soil and bedding materials at termiticidal application rates. 1999, 55 (12), 1222-1228.
20. Ford, K. A.; Casida, J. E., Comparative metabolism and pharmacokinetics of seven neonicotinoid insecticides in spinach. Journal of agricultural and food chemistry 2008, 56 (21), 10168-10175.
21. Suchail, S.; Guez, D.; Belzunces, L. P. J. E. t.; chemistry, Discrepancy between acute and chronic toxicity induced by imidacloprid and its metabolites in Apis mellifera. 2001, 20 (11), 2482-2486.
22. Nauen, R.; Ebbinghaus-Kintscher, U.; Salgado, V. L.; Kaussmann, M.,
Thiamethoxam is a neonicotinoid precursor converted to clothianidin in insects and plants. Pesticide Biochemistry and Physiology 2003, 76 (2), 55-69.
23. Pandey, G.; Dorrian, S. J.; Russell, R. J.; Oakeshott, J. G., Biotransformation of the neonicotinoid insecticides imidacloprid and thiamethoxam by Pseudomonas sp. 1G. Biochem Biophys Res Commun 2009, 380 (3), 710-4.
24. Protection, E.-E. U. S. O. o. P., Pesticides; toxic substances, p., date issued: May, Toxic Substances Agency. Name of Chemical: Clothianidin Reason for Issuance: Conditional Registration. 2003, 30.
25. Armbrust, K. L.; Peeler, H. B., Effects of formulation on the run-off of
imidacloprid from turf. Pest Manag Sci 2002, 58 (7), 702-6.
26. CCME, Canadian Water Quality Guidelines for the Protection of Aquatic
Life:Imidacloprid. Scientific Supporting Document 2007, Canadian Council of
Ministers of the Environment.
27. Gerecke, A. C.; Schärer, M.; Singer, H. P.; Müller, S. R.; Schwarzenbach,
R. P.; Sägesser, M.; Ochsenbein, U.; Popow, G., Sources of pesticides in surface waters in Switzerland: pesticide load through waste water treatment plants––current situation and reduction potential. Chemosphere 2002, 48 (3), 307-315.
28. Elbert, A.; Haas, M.; Springer, B.; Thielert, W.; Nauen, R., Applied aspects of neonicotinoid uses in crop protection. Pest Manag Sci 2008, 64 (11), 1099-105.
29. Thuyet, D. Q.; Jorgenson, B. C.; Wissel-Tyson, C.; Watanabe, H.; Young, T.
M., Wash off of imidacloprid and fipronil from turf and concrete surfaces using
simulated rainfall. Sci Total Environ 2012, 414, 515-24.
30. Agency, U. E. P., Pesticide Ecotoxicity Database (Formerly: Environmental
Effects Database [EEDB]). 2000.
31. Hudson, R. H.; Haegele, M.; Tucker, R. K., Handbook of toxicity of pesticides to wildlife. Resource publication/United States Department of the Interior, Fish and Wildlife Service (USA) 1984.
32. Dzwonkowska, A.; Hübner, H., Induction of chromosmal aberrations in the syrian hamster by insecticides tested in vivo. Archives of toxicology 1986, 58 (3), 152-156.
33. Schafer, E.; Bowles, W., Acute oral toxicity and repellency of 933 chemicals to house and deer mice. Archives of environmental contamination and toxicology 1985, 14 (1), 111-129.
34. Fujimori, K.; Ho, I.; Mehendale, H.; Villeneuve, D., Comparative toxicology
of mirex, photomirex and chlordecone after oral administration to the mouse.
Environmental Toxicology and Chemistry 1983, 2 (1), 49-60.
35. Chugh, Y.; Sankaranarayanan, A.; Sharma, P., Effect of fenvalerate and
endosulfan on behavioral despair and forced locomotor activity on albino mice. Asia pacific journal of pharmacology 1991, 6 (1), 31-35.
36. Gupta, P.; Mujumdar, V.; Rao, P., Studies on the toxicity of some insecticides to a freshwater teleost Lebistes reticulatus (Peters). Acta hydrochimica et hydrobiologica 1984, 12 (6), 629-636.
37. Agugua, S.; Oribhabor, B., The relative toxicity of pesticides, Cypermetrin and Diazol against Clibanarius africanus (Decapoda–Paguridae) and Poecilia reticulata (Teleosti–Poeciliidae). Tropical Freshwater Biology 2008, 17 (2).
38. Mayer, F. L.; Ellersieck, M. R., Manual of acute toxicity: interpretation and data base for 410 chemicals and 66 species of freshwater animals. US Department of the Interior, Fish and Wildlife Service Washington, DC: 1986.
39. Greatti, M.; Sabatini, A. G.; Barbattini, R.; Rossi, S.; Stravisi, A. J. B. o. I., Risk of environmental contamination by the active ingredient imidacloprid used for corn seed dressing. Preliminary results. 2003, 56, 69-72.
40. Leonova, I. N.; Slynko, N. M., Comparative study of insecticide susceptibility and activities of detoxification enzymes in larvae and adults of cotton bollworm, Heliothis armigera. Archives of Insect Biochemistry and Physiology: Published in Collaboration with the Entomological Society of America 1996, 32 (2), 157-172.
41. Kawada, H.; Shono, Y.; Ito, T.; Abe, Y., Laboratory evaluation of insect growth regulators against several species of anopheline mosquitoes. Medical entomology and zoology 1993, 44 (4), 349-353.
42. Deo, P.; Hasan, S.; Majumdar, S., Toxicity and suitability of some insecticides for household use. Int Pest Control 1988, 30, 118-129.
43. MELCC Quality criteria for surface water.
http://www.environnement.gouv.qc.ca/eau/criteres_eau/index.asp.
44. Posthuma-Doodeman, C., Environmental risk limits for imidacloprid. RIVM Letter report 601716018 2008.
45. Directive, D. W., Council Directive 80/778. EEC 1980.
46. Council, E., Council directive 98/83 about water quality intended for human
consumption. Official Journal of the European Communities L 1998, 330, 32-54.
47. Stokstad, E. European Union expands ban of three neonicotinoid pesticides.
https://www.sciencemag.org/news/2018/04/european-union-expands-ban-three neonicotinoid-pesticides.
48. Samuel, H. France becomes first country in Europe to ban all five pesticides killing bees https://www.telegraph.co.uk/news/2018/08/31/france-first-ban-five-pesticideskilling-bees/.
49. Zhou, Q.; Ding, Y.; Xiao, J., Sensitive determination of thiamethoxam,
imidacloprid and acetamiprid in environmental water samples with solid-phase
extraction packed with multiwalled carbon nanotubes prior to high-performance liquid chromatography. Anal Bioanal Chem 2006, 385 (8), 1520-5.
50. Dujakovic, N.; Grujic, S.; Radisic, M.; Vasiljevic, T.; Lausevic, M.,
Determination of pesticides in surface and ground waters by liquid chromatography electrospray-tandem mass spectrometry. Anal Chim Acta 2010, 678 (1), 63-72.
51. Hao, C.; Morse, D.; Zhao, X.; Sui, L., Liquid chromatography/tandem mass
spectrometry analysis of neonicotinoids in environmental water. Rapid Commun Mass Spectrom 2015, 29 (23), 2225-32.
52. Struger, J.; Grabuski, J.; Cagampan, S.; Sverko, E.; McGoldrick, D.;
Marvin, C. H., Factors influencing the occurrence and distribution of neonicotinoid insecticides in surface waters of southern Ontario, Canada. Chemosphere 2017, 169, 516-523.
53. Schaafsma, A.; Limay-Rios, V.; Baute, T.; Smith, J.; Xue, Y., Neonicotinoid
insecticide residues in surface water and soil associated with commercial maize (corn) fields in southwestern Ontario. PLoS One 2015, 10 (2), e0118139.
54. Abdel-Ghany, M. F.; Hussein, L. A.; El Azab, N. F.; El-Khatib, A. H.;
Linscheid, M. W., Simultaneous determination of eight neonicotinoid insecticide
residues and two primary metabolites in cucumbers and soil by liquid chromatography tandem mass spectrometry coupled with QuEChERS. J Chromatogr B Analyt Technol Biomed Life Sci 2016, 1031, 15-28.
55. Pook, C.; Gritcan, I., Neonicotinoid insecticide residues in New Zealand maize paddock soil. PeerJ Preprints 5:e2919v1 2017.
56. Vichapong, J.; Burakham, R.; Srijaranai, S., Vortex-assisted surfactantenhanced-emulsification liquid-liquid microextraction with solidification of floating organic droplet combined with HPLC for the determination of neonicotinoid pesticides. Talanta 2013, 117, 221-8.
57. Hao, C.; Noestheden, M. R.; Zhao, X.; Morse, D., Liquid chromatography tandem mass spectrometry analysis of neonicotinoid pesticides and 6-chloronicotinic acid in environmental water with direct aqueous injection. Anal Chim Acta 2016, 925, 43-50.
58. 沈振峰; 藥物食品分析, 何. J., 液相層析質譜術在藥物分析之應用. 1995, 3
(4), 243-258.
59. Banerjee, S.; Mazumdar, S., Electrospray ionization mass spectrometry: a
technique to access the information beyond the molecular weight of the analyte. Int J Anal Chem 2012, 2012, 282574.
60. Jovanov, P.; Guzsvány, V.; Franko, M.; Lazić, S.; Sakač, M.;
Milovanović, I.; Nedeljković, N., Development of multiresidue DLLME and
QuEChERS based LC–MS/MS method for determination of selected neonicotinoid
insecticides in honey liqueur. Food Research International 2014, 55, 11-19.
61. Jovanov, P.; Guzsvany, V.; Franko, M.; Lazic, S.; Sakac, M.; Saric, B.;
Banjac, V., Multi-residue method for determination of selected neonicotinoid
insecticides in honey using optimized dispersive liquid-liquid microextraction
combined with liquid chromatography-tandem mass spectrometry. Talanta 2013, 111, 125-33.
62. Anastassiades, M.; Lehotay, S. J.; Štajnbaher, D.; Schenck, F. J., Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. Journal of AOAC international 2003, 86 (2), 412-431.
63. Dankyi, E.; Gordon, C.; Carboo, D.; Fomsgaard, I. S., Quantification of
neonicotinoid insecticide residues in soils from cocoa plantations using a QuEChERS extraction procedure and LC-MS/MS. Sci Total Environ 2014, 499, 276-83.
64. Main, A. R.; Headley, J. V.; Peru, K. M.; Michel, N. L.; Cessna, A. J.;
Morrissey, C. A., Widespread use and frequent detection of neonicotinoid insecticides in wetlands of Canada's Prairie Pothole Region. PLoS One 2014, 9 (3), e92821.
65. 6-Chloronicotinic acid(5326-23-8).
https://www.chemicalbook.com/ProductMSDSDetailCB4707499_EN.htm.
66. THE PPDB Pesticide Properties Database. https://sitem.herts.ac.uk/aeru/iupac/.
67. Leandro, C.; Souza, V.; Dores, E. F.; Ribeiro, M. L., Determination of
pesticides multiresidues in shallow groundwater in a cotton-growing region of Mato Grosso, Brazil. Journal of the Brazilian Chemical Society 2008, 19 (6), 1111-1117.
68. Starner, K.; Goh, K. S., Detections of the neonicotinoid insecticide imidacloprid in surface waters of three agricultural regions of California, USA, 2010-2011. Bull Environ Contam Toxicol 2012, 88 (3), 316-21.
69. Masia, A.; Campo, J.; Vazquez-Roig, P.; Blasco, C.; Pico, Y., Screening of
currently used pesticides in water, sediments and biota of the Guadalquivir River Basin (Spain). J Hazard Mater 2013, 263 Pt 1, 95-104.
70. Phillips, P. J.; Bode, R. W., Concentrations of pesticides and pesticide degradates in the Croton River watershed in southeastern New York, July-September 2000. US
Department of the Interior, US Geological Survey Reston, Va.: 2002.
71. Bonmatin, J.; Moineau, I.; Charvet, R.; Fleche, C.; Colin, M.; Bengsch, E.,
A LC/APCI-MS/MS method for analysis of imidacloprid in soils, in plants, and in
pollens. Analytical Chemistry 2003, 75 (9), 2027-2033.
72. Phillips, P. J.; Bode, R. W., Pesticides in surface water runoff in south-eastern New York State, USA: seasonal and stormflow effects on concentrations. Pest Manag Sci 2004, 60 (6), 531-43.
73. Kreuger, J.; Graaf, S.; Patring, J.; Adielsson, S. Pesticides in surface water in areas with open ground and greenhouse horticultural crops in Sweden 2008; 0347-9307; 2010.
74. Environment; Canada, Presence and levels of priority pesticides in selected
Canadian aquatic ecosystems. Water Science and Technology Directorate. 2011.
75. Giroux, I.; Sarrasin, B., Pesticides et nitrates dans l'eau souterraine près de cultures de pommes de terre: échantillonnage dans quelques régions du Québec en 2008 et 2009. Développement durable, environnement et parcs Québec: 2011.
76. Lamers, M.; Anyusheva, M.; La, N.; Nguyen, V. V.; Streck, T., Pesticide
Pollution in Surface- and Groundwater by Paddy Rice Cultivation: A Case Study from Northern Vietnam. CLEAN - Soil, Air, Water 2011, 39 (4), 356-361.
77. Yamamoto, A.; Terao, T.; Hisatomi, H.; Kawasaki, H.; Arakawa, R.,
Evaluation of river pollution of neonicotinoids in Osaka City (Japan) by LC/MS with dopant-assisted photoionisation. J Environ Monit 2012, 14 (8), 2189-94.
78. Anderson, J. C.; Dubetz, C.; Palace, V. P., Neonicotinoids in the Canadian
aquatic environment: a literature review on current use products with a focus on fate, exposure, and biological effects. Sci Total Environ 2015, 505, 409-22.
79. Sarkar, M.; Biswas, P.; Roy, S.; Kole, R.; Chowdhury, A. J. B. o. e. c.;
toxicology, Effect of pH and type of formulation on the persistence of imidacloprid in water. 1999, 63 (5), 604-609.
80. MacBean, C., Flonicamid (158062-67-0). The Pesticide Manual 2010, 15th
Version 5.0.1. (Surrey UK, British Crop Protection Council.).
81. Gupta, S.; Gajbhiye, V. T., Persistence of acetamiprid in soil. Bull Environ Contam Toxicol 2007, 78 (5), 349-52.
82. Haith, D. A. J. E. s.; technology, Ecological risk assessment of pesticide runoff from grass surfaces. 2010, 44 (16), 6496-6502.
83. Rexrode, M.; Barrett, M.; Ellis, J.; Gabe, P.; Vaughan, A.; Felkel, J.;
Melendez, J., EFED risk assessment for the seed treatment of clothianidin 600FS on corn and canola. United States Environmental Protection Agency 2003, 20.
84. Li, L.; Jiang, G.; Liu, C.; Liang, H.; Sun, D.; Li, W., Clothianidin
dissipation in tomato and soil, and distribution in tomato peel and flesh. Food Control 2012, 25 (1), 265-269.
85. Morrissey, C. A.; Mineau, P.; Devries, J. H.; Sanchez-Bayo, F.; Liess, M.;
Cavallaro, M. C.; Liber, K., Neonicotinoid contamination of global surface waters and associated risk to aquatic invertebrates: a review. Environment international 2015, 74, 291-303.
86. Chawla, S.; Gor, H. N.; Patel, H. K.; Parmar, K. D.; Patel, A. R.; Shukla,
V.; Ilyas, M.; Parsai, S. K.; Somashekar; Meena, R. S.; Shah, P. G., Validation, residue analysis, and risk assessment of fipronil and flonicamid in cotton (Gossypiumsp.) samples and soil. Environ Sci Pollut Res Int 2018, 25 (19), 19167-19178.
87. Anon, Draft assessment Report (DAR) – public version – Initial risk assessment provided by the rapporteur Member State Germany for the existing active substance imidacloprid. 2006, 3, Annex B, B.8, 2006.
88. PPDB, University of Hertfordshire, funded by UK national sources and the EUfunded FOOTPRINT project (FP6-SSP-022704). The Pesticide Properties Database
(PPDB) developed by the Agriculture & Environment Research Unit (AERU). 2013.
89. Wang, C.; Guan, W. B.; Zhang, H. Y., Dissipation and residue of thiacloprid in cabbage and soil. Bull Environ Contam Toxicol 2011, 87 (4), 440-3.
90. Rodrigues, A. M.; Ferreira, V.; Cardoso, V. V.; Ferreira, E.; Benoliel, M. J., Determination of several pesticides in water by solid-phase extraction, liquid chromatography and electrospray tandem mass spectrometry. J Chromatogr A 2007, 1150 (1-2), 267-78.
91. Lazartigues, A.; Fratta, C.; Baudot, R.; Wiest, L.; Feidt, C.; Thomas, M.;
Cren-Olive, C., Multiresidue method for the determination of 13 pesticides in three environmental matrices: water, sediments and fish muscle. Talanta 2011, 85 (3), 1500-7.
92. Fernandes, V. C.; Domingues, V. F.; Mateus, N.; Delerue-Matos, C.,
Multiresidue pesticides analysis in soils using modified QuEChERS with disposable pipette extraction and dispersive solid-phase extraction. J Sep Sci 2013, 36 (2), 376-82.
93. Berlioz-Barbier, A.; Vauchez, A.; Wiest, L.; Baudot, R.; Vulliet, E.; Cren-
Olive, C., Multi-residue analysis of emerging pollutants in sediment using QuEChERS based extraction followed by LC-MS/MS analysis. Anal Bioanal Chem 2014, 406 (4), 1259-66.