色谱 ›› 2022, Vol. 40 ›› Issue (12): 1064-1075.DOI: 10.3724/SP.J.1123.2022.07011
收稿日期:
2022-07-22
出版日期:
2022-12-08
发布日期:
2022-11-29
通讯作者:
张岚
基金资助:
CHEN Yongyan, LÜ Jia, ZHANG Lan(), YE Bixiong, JIN Ning
Received:
2022-07-22
Online:
2022-12-08
Published:
2022-11-29
Contact:
ZHANG Lan
Supported by:
摘要:
为进行我国水体中农药风险监测,针对水体中农药种类多、浓度低的特点,建立了在线固相萃取-超高效液相色谱-串联质谱法快速筛查和检测水源水及饮用水中107种典型农药及代谢产物(有机磷类、有机氮类、有机杂环类、氨基甲酸酯类、酰胺类、苯甲酰脲类、新烟碱类等)的方法。样品经0.22 μm孔径亲水性聚四氟乙烯滤膜过滤后,通过自动进样器取5 mL样品注入在线固相萃取系统,经X Bridge C18在线固相萃取柱吸附后用纯水淋洗,以乙腈和0.1%甲酸水溶液为流动相对在线固相萃取柱梯度洗脱后再经ACQUITY HSS T3色谱柱分离,采用电喷雾离子源正离子及负离子模式分析检测,外标法定量。以水源水及饮用水作为基质,对其准确度和精密度进行方法学验证,结果表明:107种农药及代谢产物在不同范围内线性关系良好(r2>0.995),方法检出限(LOD, S/N=3)为0.03~1.5 ng/L,定量限(LOQ, S/N=10)为0.1~5.0 ng/L。将目标分析物在1、20、50 ng/L水平下加标,水源水和饮用水中的加标回收率分别为60.6%~119.8%和61.2%~119.0%,相对标准偏差(RSD, n=6)分别为0.3%~18.6%和0.4%~17.1%。用该方法测定水源水和饮用水中的农药残留,结果显示,酰胺类、三嗪类除草剂、三唑类杀菌剂与烟碱类、氨基甲酸酯类杀虫剂有较高的检出率,其中水源水中检出含量为0.1~97.1 ng/L,饮用水中检出含量为0.1~93.6 ng/L。该方法适用于水源水和饮用水中107种典型农药及代谢产物的痕量分析测定,有效提高了水体中农药类物质的检测效率,实际应用价值较高。
中图分类号:
陈永艳, 吕佳, 张岚, 叶必雄, 金宁. 在线固相萃取-超高效液相色谱-三重四极杆质谱法测定水源水和饮用水中107种典型农药及代谢产物[J]. 色谱, 2022, 40(12): 1064-1075.
CHEN Yongyan, LÜ Jia, ZHANG Lan, YE Bixiong, JIN Ning. Determination of 107 typical pesticides and metabolites in raw water and drinking water by online-solid phase extraction coupled with ultra performance liquid chromatography-triple quadrupole mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(12): 1064-1075.
Time/ min | Flow rate/ (mL/min) | φ(Water)/ % | φ(Acetonitrile)/ % | Curve parameter |
---|---|---|---|---|
0 | 2.00 | 100 | 0 | 11* |
0.5 | 1.00 | 100 | 0 | 11 |
3.5 | 0.01 | 100 | 0 | 11 |
4.5 | 2.00 | 0 | 100 | 11 |
7.5 | 2.00 | 100 | 0 | 11 |
13.0 | 2.00 | 100 | 0 | 11 |
23.0 | 2.00 | 100 | 0 | 11 |
表 1 在线固相萃取梯度洗脱条件
Table 1 Gradient elution conditions of online-solid phase extraction (online-SPE)
Time/ min | Flow rate/ (mL/min) | φ(Water)/ % | φ(Acetonitrile)/ % | Curve parameter |
---|---|---|---|---|
0 | 2.00 | 100 | 0 | 11* |
0.5 | 1.00 | 100 | 0 | 11 |
3.5 | 0.01 | 100 | 0 | 11 |
4.5 | 2.00 | 0 | 100 | 11 |
7.5 | 2.00 | 100 | 0 | 11 |
13.0 | 2.00 | 100 | 0 | 11 |
23.0 | 2.00 | 100 | 0 | 11 |
Time/ min | Flow rate/ (mL/min) | φ(0.1%FA)/ % | φ(Acetonitrile)/ % | Curve parameter |
---|---|---|---|---|
0 | 0.40 | 98 | 2 | 11* |
3.5 | 0.01 | 98 | 2 | 11 |
4.5 | 0.40 | 98 | 2 | 11 |
5.0 | 0.40 | 98 | 2 | 6* |
17.0 | 0.40 | 5 | 95 | 6 |
20.0 | 0.40 | 5 | 95 | 6 |
20.2 | 0.40 | 98 | 2 | 6 |
23.0 | 0.40 | 98 | 2 | 6 |
表2 液相色谱梯度洗脱条件
Table 2 Gradient elution conditions of liquid chromatography
Time/ min | Flow rate/ (mL/min) | φ(0.1%FA)/ % | φ(Acetonitrile)/ % | Curve parameter |
---|---|---|---|---|
0 | 0.40 | 98 | 2 | 11* |
3.5 | 0.01 | 98 | 2 | 11 |
4.5 | 0.40 | 98 | 2 | 11 |
5.0 | 0.40 | 98 | 2 | 6* |
17.0 | 0.40 | 5 | 95 | 6 |
20.0 | 0.40 | 5 | 95 | 6 |
20.2 | 0.40 | 98 | 2 | 6 |
23.0 | 0.40 | 98 | 2 | 6 |
No. | Pesticide | ESI | Retention time/min | Ion pairs (m/z) | CV/V | CEs/eV |
---|---|---|---|---|---|---|
1 | abamectin (阿维菌素) | + | 16.9 | 890.5>305.2, 890.5>567.3 | 82 | 26, 15 |
2 | acetamiprid (啶虫脒) | + | 9.6 | 223.0>125.8, 223.0>98.9 | 24 | 20, 38 |
3 | acetochlor (乙草胺) | + | 13.8 | 270.1>224.0, 270.1>148.1 | 32 | 6, 16 |
4 | acifluorfen (三氟羧草醚) | - | 13.8 | 360.0>316.0, 360.0>195.0 | 15 | 10, 24 |
5 | alachlor (甲草胺) | + | 13.8 | 270.1>238.0, 270.1>162.2 | 30 | 10, 20 |
6 | aldicarb (涕灭威) | + | 10.3 | 213.1>89.0, 213.1>115.9 | 30 | 18, 12 |
7 | aldicarb sulfone (涕灭威砜) | + | 8.1 | 223.0>86.0, 223.0>147.9 | 42 | 12, 8 |
8 | anilofos (莎稗磷) | + | 14.4 | 368.1>198.9, 368.1>124.9 | 28 | 12, 32 |
9 | atrazine (莠去津) | + | 11.6 | 216.1>174.0, 216.1>103.9 | 36 | 15, 28 |
10 | atrazine-2-hydroxy (2-羟基莠去津) | + | 8.1 | 198.1>85.9, 198.1>113.9 | 34 | 24, 22 |
11 | atrazine-desethyl (脱乙基莠去津) | + | 9.4 | 188.0>145.9, 188.0>103.9 | 36 | 18, 24 |
12 | atrazine-desisopropyl (脱异丙基莠去津) | + | 8.5 | 174.0>95.9, 174.0>103.9 | 76 | 16, 20 |
13 | beauvericin (白僵菌素) | + | 17.1 | 784.4>134.0, 784.4>244.1 | 50 | 62, 28 |
14 | benfuracarb (丙硫克百威) | + | 15.7 | 411.2>195.0, 411.2>252.0 | 28 | 24, 14 |
15 | benzovindiflupyr (苯并烯氟菌唑) | + | 14.3 | 398.1>342.1, 398.1>378.1 | 32 | 16, 12 |
16 | buprofezin (噻嗪酮) | + | 14.6 | 306.1>201.1, 306.1>115.9 | 24 | 10, 14 |
17 | butachlor (丁草胺) | + | 15.8 | 312.2>238.0, 312.2>162.1 | 36 | 12, 21 |
18 | cadusafos (硫线磷) | + | 14.6 | 271.0>158.9, 271.0>130.8 | 32 | 14, 24 |
19 | carbaryl (甲萘威) | + | 11.5 | 202.1>145.0, 202.1>126.9 | 24 | 6, 24 |
20 | carbendazim (多菌灵) | + | 7.6 | 192.0>160.0, 192.0>132.0 | 48 | 16, 26 |
21 | carbofuran (克百威) | + | 11.2 | 222.1>122.9, 222.1>165.0 | 32 | 18, 12 |
22 | chlorobenzuron (灭幼脲) | + | 13.8 | 309.0>156.0, 309.0>138.9 | 38 | 14, 29 |
23 | chlorotoluron (绿麦隆) | + | 11.4 | 213.0>71.9, 213.0>45.9 | 46 | 18, 14 |
24 | chlorpyrifos (毒死蜱) | + | 15.9 | 350.0>197.9, 350.0>96.9 | 20 | 16, 28 |
25 | chlorpyrifos-methyl (甲基毒死蜱) | + | 14.9 | 321.9>124.8, 321.9>289.8 | 32 | 20, 10 |
26 | chlorsulfuron (氯磺隆) | + | 11.4 | 358.0>141.0, 358.0>167.0 | 30 | 16, 14 |
27 | clothianidin (噻虫胺) | + | 9.1 | 250.0>168.9, 250.0>132.0 | 22 | 10, 14 |
28 | coumaphos (蝇毒磷) | + | 14.7 | 363.0>226.9, 363.0>307.0 | 40 | 24, 14 |
29 | cyanazine (氰草津) | + | 10.8 | 241.1>214.0, 241.1>103.9 | 40 | 16, 28 |
30 | demeton O & S (内吸磷) | + | 12.2 | 259.0>88.9, 259.0>60.9 | 10 | 10, 35 |
31 | demeton-S-methyl sulfone (内吸磷-S-甲基-砜) | + | 8.6 | 263.0>168.9, 263.0>124.9 | 40 | 14, 23 |
32 | demeton-S-sulfoxide (内吸磷-S-亚砜) | + | 9.1 | 275.0>197.0, 275.0>140.9 | 30 | 12, 22 |
33 | dichlorvos (敌敌畏) | + | 10.8 | 220.9>108.9, 220.9>144.9 | 42 | 14, 10 |
34 | diflubenzuron (除虫脲) | + | 13.5 | 311.0>157.9, 311.0>140.9 | 25 | 12, 32 |
35 | dimethoate (乐果) | + | 9.6 | 230.0>198.9, 230.0>124.8 | 28 | 8, 20 |
36 | dinocap (敌螨普) | - | 16.4 | 295.0>209.0, 295.0>134.0 | 30 | 28, 55 |
37 | dinoseb (地乐酚) | - | 14.3 | 239.0>194.1, 239.0>134.0 | 54 | 20, 46 |
38 | disulfoton-sulfone (乙拌磷砜) | + | 12.5 | 307.0>124.8, 307.0>152.9 | 30 | 16, 10 |
39 | disulfoton-sulfoxide (乙拌磷亚砜) | + | 11.5 | 291.0>184.9, 291.0>212.9 | 32 | 12, 8 |
40 | diuron (敌草隆) | + | 11.8 | 233.0>71.9, 233.0>45.9 | 32 | 18, 14 |
41 | EPN (苯硫磷) | + | 15.1 | 324.0>296.0, 324.0>156.9 | 14 | 12, 22 |
42 | fenamiphos (苯线磷) | + | 13.1 | 304.0>216.9, 304.0>201.9 | 50 | 22, 32 |
43 | fenamiphos sulfone (苯线磷砜) | + | 11.1 | 336.1>266.0, 336.1>308.0 | 45 | 18, 18 |
44 | fenamiphos sulfoxide (苯线磷亚砜) | + | 10.3 | 320.1>107.9, 320.1>171.0 | 42 | 40, 25 |
45 | fenobucarb (仲丁威) | + | 12.7 | 208.1>94.9, 208.1>151.8 | 22 | 12, 8 |
46 | fenthion (倍硫磷) | + | 14.4 | 279.0>168.9, 279.0>246.9 | 40 | 16, 10 |
47 | fenthion sulfoxide (倍硫磷亚砜) | + | 11.2 | 295.0>108.9, 295.0>279.9 | 48 | 30, 16 |
48 | fenthion-sulfone (倍硫磷砜) | + | 12.2 | 311.0>124.8, 311.0>109.0 | 44 | 22, 28 |
49 | fipronil (氟虫腈) | - | 14.2 | 435.0>329.9, 435.0>249.9 | 30 | 14, 26 |
50 | fipronil desulfinyl (氟甲腈) | - | 14.5 | 386.9>350.9, 386.9>281.9 | 32 | 10, 30 |
51 | fipronil sulfide (氟虫腈硫化物) | - | 14.8 | 418.9>382.9, 418.9>261.9 | 30 | 10, 28 |
52 | fipronil-sulfone (氟虫腈砜) | - | 14.7 | 450.9>414.9, 450.9>282.0 | 54 | 16, 26 |
53 | fonofos (地虫硫磷) | + | 14.7 | 246.9>108.8, 246.9>136.9 | 8 | 16, 10 |
54 | fosthiazate (噻唑磷) | + | 11.6 | 284.0>103.9, 284.0>228.0 | 20 | 20, 10 |
No. | Pesticide | ESI | Retention time/min | Ion pairs (m/z) | CV/V | CEs/eV |
55 | 3-hydroxycarbofuran (3-羟基克百威) | + | 9.2 | 238.1>181.0, 238.1>163.0 | 38 | 10, 16 |
56 | imidacloprid (吡虫啉) | + | 9.4 | 256.0>209.1, 256.0>175.0 | 40 | 12, 14 |
57 | imidacloprid-urea (吡虫啉尿素) | + | 8.8 | 212.0>127.9, 212.0>98.9 | 54 | 16, 18 |
58 | imidaclothiz (氯噻啉) | + | 9.6 | 262.1>181.0, 262.1>122.3 | 25 | 14, 28 |
59 | iprobenfos (异稻瘟净) | + | 13.6 | 289.1>90.9, 289.1>205.0 | 20 | 18, 8 |
60 | isoprocarb (异丙威) | + | 12 | 194.1>94.9, 194.1>137.0 | 26 | 12, 8 |
61 | isoprothiolane (稻瘟灵) | + | 13.6 | 291.0>230.9, 291.0>188.9 | 30 | 10, 20 |
62 | isoproturon (异丙隆) | + | 11.7 | 207.1>71.9, 207.1>165.0 | 42 | 20, 10 |
63 | malaoxon (马拉氧磷) | + | 11.1 | 315.0>98.9, 315.0>126.9 | 30 | 24, 12 |
64 | malathion (马拉硫磷) | + | 13.6 | 331.0>126.9, 331.0>98.9 | 30 | 12, 20 |
65 | mefenacet (苯噻酰草胺) | + | 13.2 | 299.1>148.0, 299.1>120.0 | 42 | 14, 26 |
66 | mepronil (灭锈胺) | + | 13.6 | 270.1>118.9, 270.1>90.9 | 46 | 20, 42 |
67 | metalaxyl (甲霜灵) | + | 11.8 | 280.1>220.0, 280.1>192.1 | 26 | 12, 18 |
68 | methidathion (杀扑磷) | + | 12.8 | 302.9>144.9, 302.9>85.0 | 2 | 8, 21 |
69 | metolachlor (异丙甲草胺) | + | 13.8 | 284.1>252.1, 284.1>176.1 | 20 | 12, 24 |
70 | metsulfuron-methyl (甲磺隆) | + | 11.1 | 382.0>167.0, 382.0>141.0 | 26 | 14, 12 |
71 | molinate (禾草敌) | + | 13.1 | 188.0>126.0, 188.0>54.9 | 32 | 12, 22 |
72 | monocrotophos (久效磷) | + | 8.2 | 224.0>126.9, 224.0>192.9 | 32 | 14, 6 |
73 | nitenpyram (烯啶虫胺) | + | 8.2 | 271.2>225.1, 271.2>99.0 | 32 | 10, 16 |
74 | oxamyl (杀线威) | + | 8.2 | 237.0>71.9, 237.0>89.9 | 10 | 12, 6 |
75 | parathion (对硫磷) | + | 14.4 | 291.9>235.9, 291.9>93.9 | 32 | 14, 34 |
76 | parathion-methyl (甲基对硫磷) | + | 13.2 | 264.0>124.8, 264.0>108.8 | 42 | 16, 24 |
77 | pencycuron (戊菌隆) | + | 14.8 | 329.1>124.9, 329.1>218.0 | 20 | 22, 16 |
78 | pendimethalin (二甲戊灵) | + | 15.9 | 282.0>212.0, 282.0>194.1 | 28 | 10, 18 |
79 | phenthoate (稻丰散) | + | 14.5 | 320.9>163.0, 320.9>135.0 | 26 | 10, 22 |
80 | phorate (甲拌磷) | + | 14.8 | 261.0>74.9, 261.0>46.9 | 6 | 10, 38 |
81 | phorate sulfone (甲拌磷砜) | + | 12.6 | 293.0>96.9, 293.0>247.0 | 21 | 36, 6 |
82 | phorate sulfoxide (甲拌磷亚砜) | + | 11.5 | 277.0>198.9, 277.0>142.9 | 26 | 8, 18 |
83 | phosfolan-methyl (甲基硫环磷) | + | 8.6 | 228.0>167.9, 228.0>108.8 | 22 | 12, 24 |
84 | phosphamidon (磷胺) | + | 10.4 | 300.0>174.0, 300.0>126.9 | 46 | 12, 20 |
85 | phoxim (辛硫磷) | + | 14.8 | 299.0>128.9, 299.0>152.9 | 8 | 12, 6 |
86 | pretilachlor (丙草胺) | + | 15.2 | 312.1>252.0, 312.1>176.1 | 30 | 16, 28 |
87 | procymidone (腐霉利) | + | 13.7 | 284.0>256.0, 286.0>258.0 | 50 | 16, 16 |
88 | pymetrozin (吡蚜酮) | + | 5.7 | 218.0>104.9, 218.0>78.4 | 32 | 18, 36 |
89 | pyridaben (哒螨灵) | + | 16.7 | 365.1>147.0, 365.1>309.1 | 10 | 24, 12 |
90 | rotenone (鱼藤酮) | + | 13.8 | 395.2>192.1, 395.2>213.1 | 37 | 25, 24 |
91 | simazine (西玛津) | + | 10.6 | 202.0>123.9, 202.0>131.9 | 24 | 16, 18 |
92 | simetryn (西草净) | + | 10.1 | 214.0>124.0, 214.0>96.1 | 22 | 18, 24 |
93 | sulfotep (治螟磷) | + | 14.8 | 323.0>171.0, 323.0>114.8 | 20 | 12, 30 |
94 | tebuconazole (戊唑醇) | + | 13.4 | 308.1>70.0, 308.1>124.9 | 44 | 20, 38 |
95 | terbufos (特丁硫磷) | + | 15.8 | 288.9>102.9, 288.9>232.9 | 18 | 10, 4 |
96 | terbufos sulfone (特丁硫磷砜) | + | 13.4 | 321.0>96.9, 321.0>114.8 | 46 | 42, 26 |
97 | terbufos sulfoxide (特丁磷亚砜) | + | 12.5 | 305.0>186.9, 305.0>130.8 | 16 | 8, 28 |
98 | terbuthylazine (特丁津) | + | 12.7 | 230.1>174.0, 230.1>104.0 | 26 | 14, 32 |
99 | thiabendazole (噻苯哒唑) | + | 7.9 | 202.0>175.0, 202.0>131.0 | 44 | 24, 32 |
100 | thiacloprid (噻虫啉) | + | 10.2 | 253.1>125.9, 253.1>185.9 | 20 | 18, 12 |
101 | thiamethoxam (噻虫嗪) | + | 8.7 | 292.0>211.0, 292.0>181.1 | 20 | 10, 22 |
102 | thiodicarb (硫双威) | + | 11.2 | 355.0>87.9, 355.0>107.8 | 10 | 14, 16 |
103 | triadimefon (三唑酮) | + | 13.2 | 294.0>197.0, 294.0>225.0 | 36 | 14, 12 |
104 | triazophos (三唑磷) | + | 13.7 | 314.0>162.0, 314.0>119.0 | 40 | 18, 34 |
105 | tricyclazole (三环唑) | + | 9.7 | 190.0>136.0, 190.0>163.0 | 44 | 26, 22 |
106 | triflumuron (杀铃脲) | + | 14.3 | 359.1>155.9, 359.1>138.9 | 32 | 16, 30 |
107 | trifluralin (氟乐灵) | + | 11.0 | 336.1>249.0, 336.1>294.1 | 30 | 25, 13 |
表3 目标分析物的保留时间与质谱参数
Table 3 Retention times and MS parameters of the target compounds
No. | Pesticide | ESI | Retention time/min | Ion pairs (m/z) | CV/V | CEs/eV |
---|---|---|---|---|---|---|
1 | abamectin (阿维菌素) | + | 16.9 | 890.5>305.2, 890.5>567.3 | 82 | 26, 15 |
2 | acetamiprid (啶虫脒) | + | 9.6 | 223.0>125.8, 223.0>98.9 | 24 | 20, 38 |
3 | acetochlor (乙草胺) | + | 13.8 | 270.1>224.0, 270.1>148.1 | 32 | 6, 16 |
4 | acifluorfen (三氟羧草醚) | - | 13.8 | 360.0>316.0, 360.0>195.0 | 15 | 10, 24 |
5 | alachlor (甲草胺) | + | 13.8 | 270.1>238.0, 270.1>162.2 | 30 | 10, 20 |
6 | aldicarb (涕灭威) | + | 10.3 | 213.1>89.0, 213.1>115.9 | 30 | 18, 12 |
7 | aldicarb sulfone (涕灭威砜) | + | 8.1 | 223.0>86.0, 223.0>147.9 | 42 | 12, 8 |
8 | anilofos (莎稗磷) | + | 14.4 | 368.1>198.9, 368.1>124.9 | 28 | 12, 32 |
9 | atrazine (莠去津) | + | 11.6 | 216.1>174.0, 216.1>103.9 | 36 | 15, 28 |
10 | atrazine-2-hydroxy (2-羟基莠去津) | + | 8.1 | 198.1>85.9, 198.1>113.9 | 34 | 24, 22 |
11 | atrazine-desethyl (脱乙基莠去津) | + | 9.4 | 188.0>145.9, 188.0>103.9 | 36 | 18, 24 |
12 | atrazine-desisopropyl (脱异丙基莠去津) | + | 8.5 | 174.0>95.9, 174.0>103.9 | 76 | 16, 20 |
13 | beauvericin (白僵菌素) | + | 17.1 | 784.4>134.0, 784.4>244.1 | 50 | 62, 28 |
14 | benfuracarb (丙硫克百威) | + | 15.7 | 411.2>195.0, 411.2>252.0 | 28 | 24, 14 |
15 | benzovindiflupyr (苯并烯氟菌唑) | + | 14.3 | 398.1>342.1, 398.1>378.1 | 32 | 16, 12 |
16 | buprofezin (噻嗪酮) | + | 14.6 | 306.1>201.1, 306.1>115.9 | 24 | 10, 14 |
17 | butachlor (丁草胺) | + | 15.8 | 312.2>238.0, 312.2>162.1 | 36 | 12, 21 |
18 | cadusafos (硫线磷) | + | 14.6 | 271.0>158.9, 271.0>130.8 | 32 | 14, 24 |
19 | carbaryl (甲萘威) | + | 11.5 | 202.1>145.0, 202.1>126.9 | 24 | 6, 24 |
20 | carbendazim (多菌灵) | + | 7.6 | 192.0>160.0, 192.0>132.0 | 48 | 16, 26 |
21 | carbofuran (克百威) | + | 11.2 | 222.1>122.9, 222.1>165.0 | 32 | 18, 12 |
22 | chlorobenzuron (灭幼脲) | + | 13.8 | 309.0>156.0, 309.0>138.9 | 38 | 14, 29 |
23 | chlorotoluron (绿麦隆) | + | 11.4 | 213.0>71.9, 213.0>45.9 | 46 | 18, 14 |
24 | chlorpyrifos (毒死蜱) | + | 15.9 | 350.0>197.9, 350.0>96.9 | 20 | 16, 28 |
25 | chlorpyrifos-methyl (甲基毒死蜱) | + | 14.9 | 321.9>124.8, 321.9>289.8 | 32 | 20, 10 |
26 | chlorsulfuron (氯磺隆) | + | 11.4 | 358.0>141.0, 358.0>167.0 | 30 | 16, 14 |
27 | clothianidin (噻虫胺) | + | 9.1 | 250.0>168.9, 250.0>132.0 | 22 | 10, 14 |
28 | coumaphos (蝇毒磷) | + | 14.7 | 363.0>226.9, 363.0>307.0 | 40 | 24, 14 |
29 | cyanazine (氰草津) | + | 10.8 | 241.1>214.0, 241.1>103.9 | 40 | 16, 28 |
30 | demeton O & S (内吸磷) | + | 12.2 | 259.0>88.9, 259.0>60.9 | 10 | 10, 35 |
31 | demeton-S-methyl sulfone (内吸磷-S-甲基-砜) | + | 8.6 | 263.0>168.9, 263.0>124.9 | 40 | 14, 23 |
32 | demeton-S-sulfoxide (内吸磷-S-亚砜) | + | 9.1 | 275.0>197.0, 275.0>140.9 | 30 | 12, 22 |
33 | dichlorvos (敌敌畏) | + | 10.8 | 220.9>108.9, 220.9>144.9 | 42 | 14, 10 |
34 | diflubenzuron (除虫脲) | + | 13.5 | 311.0>157.9, 311.0>140.9 | 25 | 12, 32 |
35 | dimethoate (乐果) | + | 9.6 | 230.0>198.9, 230.0>124.8 | 28 | 8, 20 |
36 | dinocap (敌螨普) | - | 16.4 | 295.0>209.0, 295.0>134.0 | 30 | 28, 55 |
37 | dinoseb (地乐酚) | - | 14.3 | 239.0>194.1, 239.0>134.0 | 54 | 20, 46 |
38 | disulfoton-sulfone (乙拌磷砜) | + | 12.5 | 307.0>124.8, 307.0>152.9 | 30 | 16, 10 |
39 | disulfoton-sulfoxide (乙拌磷亚砜) | + | 11.5 | 291.0>184.9, 291.0>212.9 | 32 | 12, 8 |
40 | diuron (敌草隆) | + | 11.8 | 233.0>71.9, 233.0>45.9 | 32 | 18, 14 |
41 | EPN (苯硫磷) | + | 15.1 | 324.0>296.0, 324.0>156.9 | 14 | 12, 22 |
42 | fenamiphos (苯线磷) | + | 13.1 | 304.0>216.9, 304.0>201.9 | 50 | 22, 32 |
43 | fenamiphos sulfone (苯线磷砜) | + | 11.1 | 336.1>266.0, 336.1>308.0 | 45 | 18, 18 |
44 | fenamiphos sulfoxide (苯线磷亚砜) | + | 10.3 | 320.1>107.9, 320.1>171.0 | 42 | 40, 25 |
45 | fenobucarb (仲丁威) | + | 12.7 | 208.1>94.9, 208.1>151.8 | 22 | 12, 8 |
46 | fenthion (倍硫磷) | + | 14.4 | 279.0>168.9, 279.0>246.9 | 40 | 16, 10 |
47 | fenthion sulfoxide (倍硫磷亚砜) | + | 11.2 | 295.0>108.9, 295.0>279.9 | 48 | 30, 16 |
48 | fenthion-sulfone (倍硫磷砜) | + | 12.2 | 311.0>124.8, 311.0>109.0 | 44 | 22, 28 |
49 | fipronil (氟虫腈) | - | 14.2 | 435.0>329.9, 435.0>249.9 | 30 | 14, 26 |
50 | fipronil desulfinyl (氟甲腈) | - | 14.5 | 386.9>350.9, 386.9>281.9 | 32 | 10, 30 |
51 | fipronil sulfide (氟虫腈硫化物) | - | 14.8 | 418.9>382.9, 418.9>261.9 | 30 | 10, 28 |
52 | fipronil-sulfone (氟虫腈砜) | - | 14.7 | 450.9>414.9, 450.9>282.0 | 54 | 16, 26 |
53 | fonofos (地虫硫磷) | + | 14.7 | 246.9>108.8, 246.9>136.9 | 8 | 16, 10 |
54 | fosthiazate (噻唑磷) | + | 11.6 | 284.0>103.9, 284.0>228.0 | 20 | 20, 10 |
No. | Pesticide | ESI | Retention time/min | Ion pairs (m/z) | CV/V | CEs/eV |
55 | 3-hydroxycarbofuran (3-羟基克百威) | + | 9.2 | 238.1>181.0, 238.1>163.0 | 38 | 10, 16 |
56 | imidacloprid (吡虫啉) | + | 9.4 | 256.0>209.1, 256.0>175.0 | 40 | 12, 14 |
57 | imidacloprid-urea (吡虫啉尿素) | + | 8.8 | 212.0>127.9, 212.0>98.9 | 54 | 16, 18 |
58 | imidaclothiz (氯噻啉) | + | 9.6 | 262.1>181.0, 262.1>122.3 | 25 | 14, 28 |
59 | iprobenfos (异稻瘟净) | + | 13.6 | 289.1>90.9, 289.1>205.0 | 20 | 18, 8 |
60 | isoprocarb (异丙威) | + | 12 | 194.1>94.9, 194.1>137.0 | 26 | 12, 8 |
61 | isoprothiolane (稻瘟灵) | + | 13.6 | 291.0>230.9, 291.0>188.9 | 30 | 10, 20 |
62 | isoproturon (异丙隆) | + | 11.7 | 207.1>71.9, 207.1>165.0 | 42 | 20, 10 |
63 | malaoxon (马拉氧磷) | + | 11.1 | 315.0>98.9, 315.0>126.9 | 30 | 24, 12 |
64 | malathion (马拉硫磷) | + | 13.6 | 331.0>126.9, 331.0>98.9 | 30 | 12, 20 |
65 | mefenacet (苯噻酰草胺) | + | 13.2 | 299.1>148.0, 299.1>120.0 | 42 | 14, 26 |
66 | mepronil (灭锈胺) | + | 13.6 | 270.1>118.9, 270.1>90.9 | 46 | 20, 42 |
67 | metalaxyl (甲霜灵) | + | 11.8 | 280.1>220.0, 280.1>192.1 | 26 | 12, 18 |
68 | methidathion (杀扑磷) | + | 12.8 | 302.9>144.9, 302.9>85.0 | 2 | 8, 21 |
69 | metolachlor (异丙甲草胺) | + | 13.8 | 284.1>252.1, 284.1>176.1 | 20 | 12, 24 |
70 | metsulfuron-methyl (甲磺隆) | + | 11.1 | 382.0>167.0, 382.0>141.0 | 26 | 14, 12 |
71 | molinate (禾草敌) | + | 13.1 | 188.0>126.0, 188.0>54.9 | 32 | 12, 22 |
72 | monocrotophos (久效磷) | + | 8.2 | 224.0>126.9, 224.0>192.9 | 32 | 14, 6 |
73 | nitenpyram (烯啶虫胺) | + | 8.2 | 271.2>225.1, 271.2>99.0 | 32 | 10, 16 |
74 | oxamyl (杀线威) | + | 8.2 | 237.0>71.9, 237.0>89.9 | 10 | 12, 6 |
75 | parathion (对硫磷) | + | 14.4 | 291.9>235.9, 291.9>93.9 | 32 | 14, 34 |
76 | parathion-methyl (甲基对硫磷) | + | 13.2 | 264.0>124.8, 264.0>108.8 | 42 | 16, 24 |
77 | pencycuron (戊菌隆) | + | 14.8 | 329.1>124.9, 329.1>218.0 | 20 | 22, 16 |
78 | pendimethalin (二甲戊灵) | + | 15.9 | 282.0>212.0, 282.0>194.1 | 28 | 10, 18 |
79 | phenthoate (稻丰散) | + | 14.5 | 320.9>163.0, 320.9>135.0 | 26 | 10, 22 |
80 | phorate (甲拌磷) | + | 14.8 | 261.0>74.9, 261.0>46.9 | 6 | 10, 38 |
81 | phorate sulfone (甲拌磷砜) | + | 12.6 | 293.0>96.9, 293.0>247.0 | 21 | 36, 6 |
82 | phorate sulfoxide (甲拌磷亚砜) | + | 11.5 | 277.0>198.9, 277.0>142.9 | 26 | 8, 18 |
83 | phosfolan-methyl (甲基硫环磷) | + | 8.6 | 228.0>167.9, 228.0>108.8 | 22 | 12, 24 |
84 | phosphamidon (磷胺) | + | 10.4 | 300.0>174.0, 300.0>126.9 | 46 | 12, 20 |
85 | phoxim (辛硫磷) | + | 14.8 | 299.0>128.9, 299.0>152.9 | 8 | 12, 6 |
86 | pretilachlor (丙草胺) | + | 15.2 | 312.1>252.0, 312.1>176.1 | 30 | 16, 28 |
87 | procymidone (腐霉利) | + | 13.7 | 284.0>256.0, 286.0>258.0 | 50 | 16, 16 |
88 | pymetrozin (吡蚜酮) | + | 5.7 | 218.0>104.9, 218.0>78.4 | 32 | 18, 36 |
89 | pyridaben (哒螨灵) | + | 16.7 | 365.1>147.0, 365.1>309.1 | 10 | 24, 12 |
90 | rotenone (鱼藤酮) | + | 13.8 | 395.2>192.1, 395.2>213.1 | 37 | 25, 24 |
91 | simazine (西玛津) | + | 10.6 | 202.0>123.9, 202.0>131.9 | 24 | 16, 18 |
92 | simetryn (西草净) | + | 10.1 | 214.0>124.0, 214.0>96.1 | 22 | 18, 24 |
93 | sulfotep (治螟磷) | + | 14.8 | 323.0>171.0, 323.0>114.8 | 20 | 12, 30 |
94 | tebuconazole (戊唑醇) | + | 13.4 | 308.1>70.0, 308.1>124.9 | 44 | 20, 38 |
95 | terbufos (特丁硫磷) | + | 15.8 | 288.9>102.9, 288.9>232.9 | 18 | 10, 4 |
96 | terbufos sulfone (特丁硫磷砜) | + | 13.4 | 321.0>96.9, 321.0>114.8 | 46 | 42, 26 |
97 | terbufos sulfoxide (特丁磷亚砜) | + | 12.5 | 305.0>186.9, 305.0>130.8 | 16 | 8, 28 |
98 | terbuthylazine (特丁津) | + | 12.7 | 230.1>174.0, 230.1>104.0 | 26 | 14, 32 |
99 | thiabendazole (噻苯哒唑) | + | 7.9 | 202.0>175.0, 202.0>131.0 | 44 | 24, 32 |
100 | thiacloprid (噻虫啉) | + | 10.2 | 253.1>125.9, 253.1>185.9 | 20 | 18, 12 |
101 | thiamethoxam (噻虫嗪) | + | 8.7 | 292.0>211.0, 292.0>181.1 | 20 | 10, 22 |
102 | thiodicarb (硫双威) | + | 11.2 | 355.0>87.9, 355.0>107.8 | 10 | 14, 16 |
103 | triadimefon (三唑酮) | + | 13.2 | 294.0>197.0, 294.0>225.0 | 36 | 14, 12 |
104 | triazophos (三唑磷) | + | 13.7 | 314.0>162.0, 314.0>119.0 | 40 | 18, 34 |
105 | tricyclazole (三环唑) | + | 9.7 | 190.0>136.0, 190.0>163.0 | 44 | 26, 22 |
106 | triflumuron (杀铃脲) | + | 14.3 | 359.1>155.9, 359.1>138.9 | 32 | 16, 30 |
107 | trifluralin (氟乐灵) | + | 11.0 | 336.1>249.0, 336.1>294.1 | 30 | 25, 13 |
图3 不同在线SPE柱的保留效果
Fig. 3 Efficiencies of different online-SPE columns on the extraction Peak identifications: 1. phosfolan-methyl; 2. imidacloprid; 3. thiacloprid; 4. metsulfuron-methyl; 5. diflubenzuron; 6. EPN.
No. | Pesticide | Linear range/ (ng/L) | LOD/ (ng/L) | LOQ/ (ng/L) | r2 | Raw water | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Content/ (ng/L) | Spiked at 1 ng/L | Spiked at 20 ng/L | Spiked at 50 ng/L | |||||||||||||||
Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | |||||||||||||
1 | abamectin | 5 | -100 | 1.5 | 5.0 | 0.9953 | ND | 64.6* | 6.5 | 61.1 | 9.1 | 61.7 | 9.6 | |||||
2 | acetamiprid | 0.2 | -100 | 0.06 | 0.2 | 0.9999 | 0.2 | 86.3 | 1.7 | 92.6 | 1.4 | 90.5 | 1.0 | |||||
3 | acetochlor | 1 | -100 | 0.3 | 1.0 | 0.9995 | 1.6 | 95.1 | 7.0 | 96.7 | 2.1 | 92.1 | 1.8 | |||||
4 | acifluorfen | 1 | -100 | 0.3 | 1.0 | 0.9993 | ND | 93.4 | 14.6 | 94.4 | 3.1 | 90.6 | 1.0 | |||||
5 | alachlor | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 88.7 | 3.6 | 98.4 | 2.1 | 94.8 | 1.9 | |||||
6 | aldicarb | 5 | -100 | 1.5 | 5.0 | 0.9976 | ND | 61.5* | 7.0 | 95.7 | 9.0 | 82.3 | 8.7 | |||||
7 | aldicarb sulfone | 5 | -100 | 1.5 | 5.0 | 0.9959 | ND | 88.0* | 8.6 | 72.5 | 10.6 | 72.6 | 10.2 | |||||
8 | anilofos | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 90.8 | 2.6 | 105.1 | 4.2 | 99.4 | 0.5 | |||||
9 | atrazine | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | 8.3 | 67.1 | 6.4 | 103.5 | 1.1 | 101.8 | 0.6 | |||||
10 | atrazine-2-hydroxy | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | 7.8 | 79.6 | 9.8 | 104.7 | 1.2 | 102.9 | 0.3 | |||||
11 | atrazine-desethyl | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 66.0 | 10.4 | 94.2 | 1.6 | 92.6 | 0.6 | |||||
12 | atrazine-desisopropyl | 5 | -100 | 1.5 | 5.0 | 0.9976 | 11.5 | 76.6* | 18.6 | 82.2 | 10.6 | 74.7 | 9.5 | |||||
13 | beauvericin | 0.1 | -100 | 0.03 | 0.1 | 0.9968 | ND | 96.3 | 4.1 | 103.3 | 7.6 | 81.1 | 7.0 | |||||
14 | benfuracarb | 0.1 | -100 | 0.03 | 0.1 | 0.9988 | ND | 89.2 | 1.9 | 98.2 | 6.4 | 92.2 | 3.0 | |||||
15 | benzovindiflupyr | 0.1 | -100 | 0.03 | 0.1 | 0.9954 | ND | 69.9 | 14.8 | 109.5 | 11.2 | 89.9 | 7.2 | |||||
16 | buprofezin | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 103.3 | 3.4 | 115.6 | 3.6 | 111.6 | 2.0 | |||||
17 | butachlor | 0.5 | -100 | 0.15 | 0.5 | 0.9999 | ND | 81.6 | 1.9 | 96.5 | 2.2 | 90.3 | 1.1 | |||||
18 | cadusafos | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 78.5 | 2.2 | 115.5 | 2.8 | 100.7 | 3.4 | |||||
19 | carbaryl | 0.5 | -100 | 0.15 | 0.5 | 0.9976 | ND | 68.4 | 7.0 | 96.6 | 2.2 | 90.1 | 0.8 | |||||
20 | carbendazim | 0.1 | -100 | 0.03 | 0.1 | 0.9997 | 0.3 | 88.0 | 2.1 | 93.7 | 0.8 | 91.7 | 0.3 | |||||
21 | carbofuran | 0.1 | -100 | 0.03 | 0.1 | 0.9995 | ND | 83.7 | 1.8 | 94.9 | 1.0 | 92.5 | 0.9 | |||||
22 | chlorobenzuron | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 89.1 | 3.7 | 95.1 | 1.4 | 93.7 | 1.0 | |||||
23 | chlorotoluron | 0.1 | -100 | 0.03 | 0.1 | 0.9997 | ND | 84.9 | 2.1 | 97.0 | 1.1 | 95.8 | 1.3 | |||||
24 | chlorpyrifos | 0.5 | -100 | 0.15 | 0.5 | 0.9993 | ND | 84.9 | 3.2 | 97.6 | 2.0 | 94.5 | 1.2 | |||||
25 | chlorpyrifos-methyl | 1 | -100 | 0.3 | 1.0 | 0.9994 | ND | 80.1 | 9.9 | 90.2 | 2.0 | 87.7 | 1.0 | |||||
26 | chlorsulfuron | 0.2 | -100 | 0.06 | 0.2 | 0.9995 | ND | 61.1 | 8.5 | 67.8 | 5.1 | 62.4 | 3.6 | |||||
27 | clothianidin | 1 | -100 | 0.3 | 1.0 | 0.9989 | ND | 85.6 | 5.6 | 87.7 | 0.7 | 82.6 | 1.5 | |||||
28 | coumaphos | 0.5 | -100 | 0.15 | 0.5 | 0.9996 | ND | 97.0 | 2.7 | 105.3 | 2.3 | 100.5 | 1.2 | |||||
29 | cyanazine | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 95.5 | 2.4 | 98.3 | 1.0 | 96.3 | 0.3 | |||||
30 | demeton O & S | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 92.5 | 5.8 | 95.4 | 2.0 | 95.1 | 1.9 | |||||
31 | demeton-S-methyl sulfone | 1 | -100 | 0.3 | 1.0 | 0.9991 | ND | 79.9 | 5.7 | 97.1 | 1.8 | 92.6 | 1.0 | |||||
32 | demeton-S-sulfoxide | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 99.4 | 2.2 | 108.3 | 1.5 | 103.7 | 0.8 | |||||
33 | dichlorvos | 0.5 | -50 | 0.15 | 0.5 | 0.9993 | ND | 71.2 | 2.1 | 66.1 | 1.3 | 68.3 | 3.0 | |||||
34 | diflubenzuron | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 81.9 | 8.4 | 85.8 | 2.7 | 87.8 | 2.1 | |||||
35 | dimethoate | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 75.4 | 2.9 | 84.4 | 1.0 | 82.5 | 1.3 | |||||
36 | dinocap | 5 | -100 | 1.5 | 5.0 | 0.9976 | ND | 88.2* | 5.5 | 88.5 | 3.3 | 97.3 | 8.2 | |||||
37 | dinoseb | 5 | -100 | 1.5 | 5.0 | 0.9967 | ND | 63.6* | 4.3 | 90.0 | 8.3 | 89.3 | 2.5 | |||||
38 | disulfoton-sulfone | 0.5 | -100 | 0.15 | 0.5 | 0.9990 | ND | 66.3 | 3.7 | 88.7 | 1.6 | 84.4 | 0.7 | |||||
39 | disulfoton-sulfoxide | 0.2 | -100 | 0.06 | 0.2 | 0.9992 | ND | 94.0 | 4.1 | 110.7 | 2.5 | 107.1 | 0.8 | |||||
40 | diuron | 0.5 | -100 | 0.15 | 0.5 | 0.9996 | ND | 83.8 | 3.2 | 93.8 | 1.6 | 91.0 | 1.4 | |||||
No. | Pesticide | Linear range/ (ng/L) | LOD/ (ng/L) | LOQ/ (ng/L) | r2 | Raw water | ||||||||||||
Content/ (ng/L) | Spiked at 1 ng/L | Spiked at 20 ng/L | Spiked at 50 ng/L | |||||||||||||||
Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | |||||||||||||
41 | EPN | 0.5 | -100 | 0.15 | 0.5 | 0.9994 | ND | 61.0 | 6.9 | 66.3 | 2.8 | 61.1 | 4.5 | |||||
42 | fenamiphos | 0.1 | -100 | 0.03 | 0.1 | 0.9974 | ND | 81.0 | 6.6 | 118.1 | 2.1 | 109.8 | 2.3 | |||||
43 | fenamiphos sulfone | 0.5 | -100 | 0.15 | 0.5 | 0.9997 | ND | 90.5 | 3.8 | 93.4 | 1.3 | 92.2 | 1.8 | |||||
44 | fenamiphos sulfoxide | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 92.9 | 2.2 | 98.1 | 1.2 | 95.3 | 0.8 | |||||
45 | fenobucarb | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 93.2 | 2.8 | 99.8 | 0.9 | 97.4 | 1.6 | |||||
46 | fenthion | 1 | -100 | 0.3 | 1.0 | 0.9995 | ND | 95.6 | 7.6 | 95.4 | 1.5 | 92.8 | 2.0 | |||||
47 | fenthion sulfoxide | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 95.5 | 3.1 | 98.5 | 1.5 | 95.1 | 1.1 | |||||
48 | fenthion-sulfone | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 75.8* | 8.8 | 79.0 | 2.8 | 76.6 | 1.4 | |||||
49 | fipronil | 1 | -100 | 0.3 | 1.0 | 0.9995 | ND | 83.3 | 14.4 | 96.3 | 3.3 | 85.8 | 2.9 | |||||
50 | fipronil desulfinyl | 0.5 | -100 | 0.15 | 0.5 | 0.9999 | ND | 94.6 | 8.0 | 95.5 | 2.2 | 90.2 | 2.3 | |||||
51 | fipronil sulfide | 1 | -100 | 0.3 | 1.0 | 0.9993 | ND | 71.7 | 10.6 | 95.5 | 2.8 | 85.5 | 1.9 | |||||
52 | fipronil-sulfone | 0.5 | -100 | 0.15 | 0.5 | 0.9992 | ND | 84.8 | 5.1 | 96.5 | 4.2 | 86.7 | 2.5 | |||||
53 | fonofos | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 91.1 | 2.4 | 97.4 | 1.2 | 96.3 | 0.7 | |||||
54 | fosthiazate | 0.1 | -100 | 0.03 | 0.1 | 0.9991 | ND | 84.8 | 1.7 | 105.4 | 2.2 | 101.3 | 1.3 | |||||
55 | 3-hydroxycarbofuran | 0.5 | -100 | 0.15 | 0.5 | 0.9960 | ND | 94.2 | 2.4 | 100.4 | 3.5 | 93.2 | 1.9 | |||||
56 | imidacloprid | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | 4.1 | 74.0 | 2.8 | 76.5 | 1.4 | 74.2 | 1.3 | |||||
57 | imidacloprid-urea | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 73.1 | 13.3 | 63.3 | 13.2 | 70.3 | 16.2 | |||||
58 | imidaclothiz | 1 | -100 | 0.3 | 1.0 | 0.9998 | ND | 73.4 | 3.9 | 77.5 | 2.3 | 74.6 | 0.7 | |||||
59 | iprobenfos | 0.1 | -50 | 0.03 | 0.1 | 0.9996 | ND | 78.5 | 1.3 | 111.8 | 2.3 | 100.3 | 2.1 | |||||
60 | isoprocarb | 0.1 | -100 | 0.03 | 0.1 | 0.9997 | ND | 78.0 | 4.4 | 84.7 | 1.1 | 81.6 | 2.8 | |||||
61 | isoprothiolane | 0.1 | -100 | 0.03 | 0.1 | 0.9993 | ND | 77.6 | 2.4 | 103.3 | 2.1 | 95.3 | 1.0 | |||||
62 | isoproturon | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 88.8 | 1.8 | 100.0 | 1.3 | 97.8 | 0.6 | |||||
63 | malaoxon | 0.1 | -100 | 0.03 | 0.1 | 0.9988 | ND | 94.3 | 2.7 | 119.8 | 1.0 | 114.6 | 0.7 | |||||
64 | malathion | 0.1 | -100 | 0.03 | 0.1 | 0.9990 | ND | 73.1 | 4.9 | 102.4 | 2.1 | 93.7 | 0.9 | |||||
65 | mefenacet | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 79.5 | 1.7 | 96.8 | 1.3 | 93.3 | 0.8 | |||||
66 | mepronil | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 65.1 | 1.6 | 78.8 | 1.1 | 78.3 | 0.7 | |||||
67 | metalaxyl | 0.1 | -100 | 0.03 | 0.1 | 0.9992 | ND | 96.7 | 4.2 | 102.7 | 2.2 | 99.7 | 0.9 | |||||
68 | methidathion | 0.5 | -100 | 0.15 | 0.5 | 0.9995 | ND | 75.2 | 2.4 | 86.2 | 2.1 | 82.2 | 2.6 | |||||
69 | metolachlor | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 84.7 | 1.4 | 98.5 | 1.0 | 96.5 | 0.9 | |||||
70 | metsulfuron-methyl | 0.1 | -100 | 0.03 | 0.1 | 0.9993 | ND | 80.2 | 2.4 | 97.6 | 1.3 | 89.2 | 1.5 | |||||
71 | molinate | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 91.2 | 2.7 | 99.2 | 1.5 | 98.4 | 0.8 | |||||
72 | monocrotophos | 0.2 | -100 | 0.06 | 0.2 | 0.9999 | ND | 86.9 | 4.0 | 96.0 | 1.0 | 93.3 | 1.0 | |||||
73 | nitenpyram | 5 | -100 | 1.5 | 5.0 | 0.9967 | ND | 103.2* | 6.3 | 82.6 | 4.0 | 76.0 | 6.0 | |||||
74 | oxamyl | 1 | -100 | 0.3 | 1.0 | 0.9978 | ND | 67.7 | 13.2 | 74.2 | 13.7 | 72.3 | 8.7 | |||||
75 | parathion | 1 | -100 | 0.3 | 1.0 | 0.9995 | ND | 62.1 | 7.3 | 88.8 | 3.8 | 89.9 | 3.1 | |||||
76 | parathion-methyl | 5 | -100 | 1.5 | 5.0 | 0.9987 | ND | 61.6* | 2.5 | 75.0 | 6.3 | 73.3 | 6.1 | |||||
77 | pencycuron | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 81.1 | 2.3 | 95.4 | 1.2 | 91.4 | 1.1 | |||||
78 | pendimethalin | 0.2 | -100 | 0.06 | 0.2 | 0.9991 | ND | 87.0 | 2.1 | 94.8 | 2.1 | 92.8 | 1.1 | |||||
79 | phenthoate | 0.5 | -100 | 0.15 | 0.5 | 0.9977 | ND | 90.9 | 7.4 | 95.3 | 2.5 | 90.9 | 1.0 | |||||
80 | phorate | 0.1 | -100 | 0.03 | 0.1 | 0.9996 | ND | 85.5 | 1.5 | 94.6 | 2.0 | 90.4 | 1.0 | |||||
81 | phorate sulfone | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 82.9 | 3.8 | 84.9 | 1.3 | 82.6 | 2.6 | |||||
82 | phorate sulfoxide | 0.5 | -100 | 0.15 | 0.5 | 0.9994 | ND | 86.3 | 3.4 | 104.9 | 1.1 | 101.1 | 0.4 | |||||
83 | phosfolan-methyl | 0.5 | -100 | 0.15 | 0.5 | 0.9996 | ND | 81.4 | 4.5 | 86.6 | 2.8 | 83.9 | 1.2 | |||||
84 | phosphamidon | 0.1 | -100 | 0.03 | 0.1 | 0.9995 | ND | 89.7 | 0.9 | 100 | 1.3 | 97.8 | 0.9 | |||||
85 | phoxim | 0.5 | -100 | 0.15 | 0.5 | 0.9993 | ND | 82.3 | 3.0 | 89.6 | 2.3 | 82.5 | 2.2 | |||||
86 | pretilachlor | 0.1 | -100 | 0.03 | 0.1 | 0.9997 | ND | 63.2 | 3.1 | 82.7 | 2.4 | 70.9 | 1.6 | |||||
87 | procymidone | 1 | -100 | 0.3 | 1.0 | 0.9956 | ND | 99.9 | 7.1 | 103.3 | 3.1 | 98.8 | 2.4 | |||||
88 | pymetrozin | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 114.2 | 2.7 | 107.2 | 3.7 | 106.6 | 3.7 | |||||
89 | pyridaben | 0.1 | -50 | 0.03 | 0.1 | 0.9990 | ND | 89.6 | 1.4 | 71.2 | 3.6 | 78.9 | 5.5 | |||||
No. | Pesticide | Linear range/ (ng/L) | LOD/ (ng/L) | LOQ/ (ng/L) | r2 | Raw water | ||||||||||||
Content/ (ng/L) | Spiked at 1 ng/L | Spiked at 20 ng/L | Spiked at 50 ng/L | |||||||||||||||
Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | |||||||||||||
90 | rotenone | 0.5 | -100 | 0.15 | 0.5 | 0.9982 | ND | 83.5 | 5.3 | 109.3 | 1.0 | 95.9 | 1.2 | |||||
91 | simazine | 0.2 | -100 | 0.06 | 0.2 | 0.9999 | ND | 98.6 | 1.9 | 100.1 | 1.7 | 99.1 | 0.9 | |||||
92 | simetryn | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 99.3 | 1.1 | 102.7 | 0.9 | 100.2 | 0.6 | |||||
93 | sulfotep | 0.5 | -100 | 0.15 | 0.5 | 0.9994 | ND | 73.3 | 3.9 | 90.6 | 2.7 | 82.2 | 2.4 | |||||
94 | tebuconazole | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | 0.7 | 84.3 | 2.8 | 95.3 | 1.7 | 93.5 | 0.6 | |||||
95 | terbufos | 1 | -100 | 0.3 | 1.0 | 0.9980 | ND | 60.6 | 6.4 | 95.8 | 4.3 | 86.7 | 2.6 | |||||
96 | terbufos sulfone | 1 | -100 | 0.3 | 1.0 | 0.9995 | ND | 69.4 | 11.3 | 101.3 | 1.9 | 98.8 | 1.6 | |||||
97 | terbufos sulfoxide | 0.1 | -100 | 0.03 | 0.1 | 0.9993 | ND | 81.1 | 2.6 | 99.5 | 1.5 | 96.9 | 0.7 | |||||
98 | terbuthylazine | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 101.5 | 0.7 | 104.4 | 0.9 | 102.6 | 0.6 | |||||
99 | thiabendazole | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 73.3 | 5.0 | 75.4 | 2.2 | 90.8 | 2.7 | |||||
100 | thiacloprid | 0.2 | -100 | 0.06 | 0.2 | 0.9998 | ND | 81.9 | 2.6 | 86.1 | 0.7 | 84.3 | 1.5 | |||||
101 | thiamethoxam | 1 | -100 | 0.3 | 1.0 | 0.9992 | ND | 76.7 | 5.6 | 80.5 | 2.0 | 80.3 | 3.3 | |||||
102 | thiodicarb | 0.1 | -100 | 0.03 | 0.1 | 0.9991 | ND | 93.6 | 2.6 | 118.9 | 2.9 | 115.0 | 1.2 | |||||
103 | triadimefon | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 88.5 | 2.2 | 94.7 | 2.8 | 91.2 | 1.8 | |||||
104 | triazophos | 0.2 | -100 | 0.06 | 0.2 | 0.9998 | ND | 85.7 | 2.1 | 99.1 | 2.6 | 96.3 | 1.0 | |||||
105 | tricyclazole | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 84.2 | 1.8 | 90.8 | 1.5 | 88.8 | 1.3 | |||||
106 | triflumuron | 0.2 | -100 | 0.06 | 0.2 | 0.9999 | ND | 93.5 | 3.3 | 101.9 | 3.3 | 98.7 | 0.5 | |||||
107 | trifluralin | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 96.6 | 5.9 | 92.5 | 2.9 | 91.6 | 1.7 |
表4 107种目标分析物的线性范围、相关系数、检出限、定量限、加标回收率及RSD(n=6)
Table 4 Linear ranges, correlation coefficients (r2), LODs, LOQs, spiked recoveries, and RSDs of the 107 compounds (n=6)
No. | Pesticide | Linear range/ (ng/L) | LOD/ (ng/L) | LOQ/ (ng/L) | r2 | Raw water | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Content/ (ng/L) | Spiked at 1 ng/L | Spiked at 20 ng/L | Spiked at 50 ng/L | |||||||||||||||
Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | |||||||||||||
1 | abamectin | 5 | -100 | 1.5 | 5.0 | 0.9953 | ND | 64.6* | 6.5 | 61.1 | 9.1 | 61.7 | 9.6 | |||||
2 | acetamiprid | 0.2 | -100 | 0.06 | 0.2 | 0.9999 | 0.2 | 86.3 | 1.7 | 92.6 | 1.4 | 90.5 | 1.0 | |||||
3 | acetochlor | 1 | -100 | 0.3 | 1.0 | 0.9995 | 1.6 | 95.1 | 7.0 | 96.7 | 2.1 | 92.1 | 1.8 | |||||
4 | acifluorfen | 1 | -100 | 0.3 | 1.0 | 0.9993 | ND | 93.4 | 14.6 | 94.4 | 3.1 | 90.6 | 1.0 | |||||
5 | alachlor | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 88.7 | 3.6 | 98.4 | 2.1 | 94.8 | 1.9 | |||||
6 | aldicarb | 5 | -100 | 1.5 | 5.0 | 0.9976 | ND | 61.5* | 7.0 | 95.7 | 9.0 | 82.3 | 8.7 | |||||
7 | aldicarb sulfone | 5 | -100 | 1.5 | 5.0 | 0.9959 | ND | 88.0* | 8.6 | 72.5 | 10.6 | 72.6 | 10.2 | |||||
8 | anilofos | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 90.8 | 2.6 | 105.1 | 4.2 | 99.4 | 0.5 | |||||
9 | atrazine | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | 8.3 | 67.1 | 6.4 | 103.5 | 1.1 | 101.8 | 0.6 | |||||
10 | atrazine-2-hydroxy | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | 7.8 | 79.6 | 9.8 | 104.7 | 1.2 | 102.9 | 0.3 | |||||
11 | atrazine-desethyl | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 66.0 | 10.4 | 94.2 | 1.6 | 92.6 | 0.6 | |||||
12 | atrazine-desisopropyl | 5 | -100 | 1.5 | 5.0 | 0.9976 | 11.5 | 76.6* | 18.6 | 82.2 | 10.6 | 74.7 | 9.5 | |||||
13 | beauvericin | 0.1 | -100 | 0.03 | 0.1 | 0.9968 | ND | 96.3 | 4.1 | 103.3 | 7.6 | 81.1 | 7.0 | |||||
14 | benfuracarb | 0.1 | -100 | 0.03 | 0.1 | 0.9988 | ND | 89.2 | 1.9 | 98.2 | 6.4 | 92.2 | 3.0 | |||||
15 | benzovindiflupyr | 0.1 | -100 | 0.03 | 0.1 | 0.9954 | ND | 69.9 | 14.8 | 109.5 | 11.2 | 89.9 | 7.2 | |||||
16 | buprofezin | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 103.3 | 3.4 | 115.6 | 3.6 | 111.6 | 2.0 | |||||
17 | butachlor | 0.5 | -100 | 0.15 | 0.5 | 0.9999 | ND | 81.6 | 1.9 | 96.5 | 2.2 | 90.3 | 1.1 | |||||
18 | cadusafos | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 78.5 | 2.2 | 115.5 | 2.8 | 100.7 | 3.4 | |||||
19 | carbaryl | 0.5 | -100 | 0.15 | 0.5 | 0.9976 | ND | 68.4 | 7.0 | 96.6 | 2.2 | 90.1 | 0.8 | |||||
20 | carbendazim | 0.1 | -100 | 0.03 | 0.1 | 0.9997 | 0.3 | 88.0 | 2.1 | 93.7 | 0.8 | 91.7 | 0.3 | |||||
21 | carbofuran | 0.1 | -100 | 0.03 | 0.1 | 0.9995 | ND | 83.7 | 1.8 | 94.9 | 1.0 | 92.5 | 0.9 | |||||
22 | chlorobenzuron | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 89.1 | 3.7 | 95.1 | 1.4 | 93.7 | 1.0 | |||||
23 | chlorotoluron | 0.1 | -100 | 0.03 | 0.1 | 0.9997 | ND | 84.9 | 2.1 | 97.0 | 1.1 | 95.8 | 1.3 | |||||
24 | chlorpyrifos | 0.5 | -100 | 0.15 | 0.5 | 0.9993 | ND | 84.9 | 3.2 | 97.6 | 2.0 | 94.5 | 1.2 | |||||
25 | chlorpyrifos-methyl | 1 | -100 | 0.3 | 1.0 | 0.9994 | ND | 80.1 | 9.9 | 90.2 | 2.0 | 87.7 | 1.0 | |||||
26 | chlorsulfuron | 0.2 | -100 | 0.06 | 0.2 | 0.9995 | ND | 61.1 | 8.5 | 67.8 | 5.1 | 62.4 | 3.6 | |||||
27 | clothianidin | 1 | -100 | 0.3 | 1.0 | 0.9989 | ND | 85.6 | 5.6 | 87.7 | 0.7 | 82.6 | 1.5 | |||||
28 | coumaphos | 0.5 | -100 | 0.15 | 0.5 | 0.9996 | ND | 97.0 | 2.7 | 105.3 | 2.3 | 100.5 | 1.2 | |||||
29 | cyanazine | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 95.5 | 2.4 | 98.3 | 1.0 | 96.3 | 0.3 | |||||
30 | demeton O & S | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 92.5 | 5.8 | 95.4 | 2.0 | 95.1 | 1.9 | |||||
31 | demeton-S-methyl sulfone | 1 | -100 | 0.3 | 1.0 | 0.9991 | ND | 79.9 | 5.7 | 97.1 | 1.8 | 92.6 | 1.0 | |||||
32 | demeton-S-sulfoxide | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 99.4 | 2.2 | 108.3 | 1.5 | 103.7 | 0.8 | |||||
33 | dichlorvos | 0.5 | -50 | 0.15 | 0.5 | 0.9993 | ND | 71.2 | 2.1 | 66.1 | 1.3 | 68.3 | 3.0 | |||||
34 | diflubenzuron | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 81.9 | 8.4 | 85.8 | 2.7 | 87.8 | 2.1 | |||||
35 | dimethoate | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 75.4 | 2.9 | 84.4 | 1.0 | 82.5 | 1.3 | |||||
36 | dinocap | 5 | -100 | 1.5 | 5.0 | 0.9976 | ND | 88.2* | 5.5 | 88.5 | 3.3 | 97.3 | 8.2 | |||||
37 | dinoseb | 5 | -100 | 1.5 | 5.0 | 0.9967 | ND | 63.6* | 4.3 | 90.0 | 8.3 | 89.3 | 2.5 | |||||
38 | disulfoton-sulfone | 0.5 | -100 | 0.15 | 0.5 | 0.9990 | ND | 66.3 | 3.7 | 88.7 | 1.6 | 84.4 | 0.7 | |||||
39 | disulfoton-sulfoxide | 0.2 | -100 | 0.06 | 0.2 | 0.9992 | ND | 94.0 | 4.1 | 110.7 | 2.5 | 107.1 | 0.8 | |||||
40 | diuron | 0.5 | -100 | 0.15 | 0.5 | 0.9996 | ND | 83.8 | 3.2 | 93.8 | 1.6 | 91.0 | 1.4 | |||||
No. | Pesticide | Linear range/ (ng/L) | LOD/ (ng/L) | LOQ/ (ng/L) | r2 | Raw water | ||||||||||||
Content/ (ng/L) | Spiked at 1 ng/L | Spiked at 20 ng/L | Spiked at 50 ng/L | |||||||||||||||
Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | |||||||||||||
41 | EPN | 0.5 | -100 | 0.15 | 0.5 | 0.9994 | ND | 61.0 | 6.9 | 66.3 | 2.8 | 61.1 | 4.5 | |||||
42 | fenamiphos | 0.1 | -100 | 0.03 | 0.1 | 0.9974 | ND | 81.0 | 6.6 | 118.1 | 2.1 | 109.8 | 2.3 | |||||
43 | fenamiphos sulfone | 0.5 | -100 | 0.15 | 0.5 | 0.9997 | ND | 90.5 | 3.8 | 93.4 | 1.3 | 92.2 | 1.8 | |||||
44 | fenamiphos sulfoxide | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 92.9 | 2.2 | 98.1 | 1.2 | 95.3 | 0.8 | |||||
45 | fenobucarb | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 93.2 | 2.8 | 99.8 | 0.9 | 97.4 | 1.6 | |||||
46 | fenthion | 1 | -100 | 0.3 | 1.0 | 0.9995 | ND | 95.6 | 7.6 | 95.4 | 1.5 | 92.8 | 2.0 | |||||
47 | fenthion sulfoxide | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | ND | 95.5 | 3.1 | 98.5 | 1.5 | 95.1 | 1.1 | |||||
48 | fenthion-sulfone | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 75.8* | 8.8 | 79.0 | 2.8 | 76.6 | 1.4 | |||||
49 | fipronil | 1 | -100 | 0.3 | 1.0 | 0.9995 | ND | 83.3 | 14.4 | 96.3 | 3.3 | 85.8 | 2.9 | |||||
50 | fipronil desulfinyl | 0.5 | -100 | 0.15 | 0.5 | 0.9999 | ND | 94.6 | 8.0 | 95.5 | 2.2 | 90.2 | 2.3 | |||||
51 | fipronil sulfide | 1 | -100 | 0.3 | 1.0 | 0.9993 | ND | 71.7 | 10.6 | 95.5 | 2.8 | 85.5 | 1.9 | |||||
52 | fipronil-sulfone | 0.5 | -100 | 0.15 | 0.5 | 0.9992 | ND | 84.8 | 5.1 | 96.5 | 4.2 | 86.7 | 2.5 | |||||
53 | fonofos | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 91.1 | 2.4 | 97.4 | 1.2 | 96.3 | 0.7 | |||||
54 | fosthiazate | 0.1 | -100 | 0.03 | 0.1 | 0.9991 | ND | 84.8 | 1.7 | 105.4 | 2.2 | 101.3 | 1.3 | |||||
55 | 3-hydroxycarbofuran | 0.5 | -100 | 0.15 | 0.5 | 0.9960 | ND | 94.2 | 2.4 | 100.4 | 3.5 | 93.2 | 1.9 | |||||
56 | imidacloprid | 0.5 | -100 | 0.15 | 0.5 | 0.9998 | 4.1 | 74.0 | 2.8 | 76.5 | 1.4 | 74.2 | 1.3 | |||||
57 | imidacloprid-urea | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 73.1 | 13.3 | 63.3 | 13.2 | 70.3 | 16.2 | |||||
58 | imidaclothiz | 1 | -100 | 0.3 | 1.0 | 0.9998 | ND | 73.4 | 3.9 | 77.5 | 2.3 | 74.6 | 0.7 | |||||
59 | iprobenfos | 0.1 | -50 | 0.03 | 0.1 | 0.9996 | ND | 78.5 | 1.3 | 111.8 | 2.3 | 100.3 | 2.1 | |||||
60 | isoprocarb | 0.1 | -100 | 0.03 | 0.1 | 0.9997 | ND | 78.0 | 4.4 | 84.7 | 1.1 | 81.6 | 2.8 | |||||
61 | isoprothiolane | 0.1 | -100 | 0.03 | 0.1 | 0.9993 | ND | 77.6 | 2.4 | 103.3 | 2.1 | 95.3 | 1.0 | |||||
62 | isoproturon | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 88.8 | 1.8 | 100.0 | 1.3 | 97.8 | 0.6 | |||||
63 | malaoxon | 0.1 | -100 | 0.03 | 0.1 | 0.9988 | ND | 94.3 | 2.7 | 119.8 | 1.0 | 114.6 | 0.7 | |||||
64 | malathion | 0.1 | -100 | 0.03 | 0.1 | 0.9990 | ND | 73.1 | 4.9 | 102.4 | 2.1 | 93.7 | 0.9 | |||||
65 | mefenacet | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 79.5 | 1.7 | 96.8 | 1.3 | 93.3 | 0.8 | |||||
66 | mepronil | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 65.1 | 1.6 | 78.8 | 1.1 | 78.3 | 0.7 | |||||
67 | metalaxyl | 0.1 | -100 | 0.03 | 0.1 | 0.9992 | ND | 96.7 | 4.2 | 102.7 | 2.2 | 99.7 | 0.9 | |||||
68 | methidathion | 0.5 | -100 | 0.15 | 0.5 | 0.9995 | ND | 75.2 | 2.4 | 86.2 | 2.1 | 82.2 | 2.6 | |||||
69 | metolachlor | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 84.7 | 1.4 | 98.5 | 1.0 | 96.5 | 0.9 | |||||
70 | metsulfuron-methyl | 0.1 | -100 | 0.03 | 0.1 | 0.9993 | ND | 80.2 | 2.4 | 97.6 | 1.3 | 89.2 | 1.5 | |||||
71 | molinate | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 91.2 | 2.7 | 99.2 | 1.5 | 98.4 | 0.8 | |||||
72 | monocrotophos | 0.2 | -100 | 0.06 | 0.2 | 0.9999 | ND | 86.9 | 4.0 | 96.0 | 1.0 | 93.3 | 1.0 | |||||
73 | nitenpyram | 5 | -100 | 1.5 | 5.0 | 0.9967 | ND | 103.2* | 6.3 | 82.6 | 4.0 | 76.0 | 6.0 | |||||
74 | oxamyl | 1 | -100 | 0.3 | 1.0 | 0.9978 | ND | 67.7 | 13.2 | 74.2 | 13.7 | 72.3 | 8.7 | |||||
75 | parathion | 1 | -100 | 0.3 | 1.0 | 0.9995 | ND | 62.1 | 7.3 | 88.8 | 3.8 | 89.9 | 3.1 | |||||
76 | parathion-methyl | 5 | -100 | 1.5 | 5.0 | 0.9987 | ND | 61.6* | 2.5 | 75.0 | 6.3 | 73.3 | 6.1 | |||||
77 | pencycuron | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | ND | 81.1 | 2.3 | 95.4 | 1.2 | 91.4 | 1.1 | |||||
78 | pendimethalin | 0.2 | -100 | 0.06 | 0.2 | 0.9991 | ND | 87.0 | 2.1 | 94.8 | 2.1 | 92.8 | 1.1 | |||||
79 | phenthoate | 0.5 | -100 | 0.15 | 0.5 | 0.9977 | ND | 90.9 | 7.4 | 95.3 | 2.5 | 90.9 | 1.0 | |||||
80 | phorate | 0.1 | -100 | 0.03 | 0.1 | 0.9996 | ND | 85.5 | 1.5 | 94.6 | 2.0 | 90.4 | 1.0 | |||||
81 | phorate sulfone | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 82.9 | 3.8 | 84.9 | 1.3 | 82.6 | 2.6 | |||||
82 | phorate sulfoxide | 0.5 | -100 | 0.15 | 0.5 | 0.9994 | ND | 86.3 | 3.4 | 104.9 | 1.1 | 101.1 | 0.4 | |||||
83 | phosfolan-methyl | 0.5 | -100 | 0.15 | 0.5 | 0.9996 | ND | 81.4 | 4.5 | 86.6 | 2.8 | 83.9 | 1.2 | |||||
84 | phosphamidon | 0.1 | -100 | 0.03 | 0.1 | 0.9995 | ND | 89.7 | 0.9 | 100 | 1.3 | 97.8 | 0.9 | |||||
85 | phoxim | 0.5 | -100 | 0.15 | 0.5 | 0.9993 | ND | 82.3 | 3.0 | 89.6 | 2.3 | 82.5 | 2.2 | |||||
86 | pretilachlor | 0.1 | -100 | 0.03 | 0.1 | 0.9997 | ND | 63.2 | 3.1 | 82.7 | 2.4 | 70.9 | 1.6 | |||||
87 | procymidone | 1 | -100 | 0.3 | 1.0 | 0.9956 | ND | 99.9 | 7.1 | 103.3 | 3.1 | 98.8 | 2.4 | |||||
88 | pymetrozin | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 114.2 | 2.7 | 107.2 | 3.7 | 106.6 | 3.7 | |||||
89 | pyridaben | 0.1 | -50 | 0.03 | 0.1 | 0.9990 | ND | 89.6 | 1.4 | 71.2 | 3.6 | 78.9 | 5.5 | |||||
No. | Pesticide | Linear range/ (ng/L) | LOD/ (ng/L) | LOQ/ (ng/L) | r2 | Raw water | ||||||||||||
Content/ (ng/L) | Spiked at 1 ng/L | Spiked at 20 ng/L | Spiked at 50 ng/L | |||||||||||||||
Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | |||||||||||||
90 | rotenone | 0.5 | -100 | 0.15 | 0.5 | 0.9982 | ND | 83.5 | 5.3 | 109.3 | 1.0 | 95.9 | 1.2 | |||||
91 | simazine | 0.2 | -100 | 0.06 | 0.2 | 0.9999 | ND | 98.6 | 1.9 | 100.1 | 1.7 | 99.1 | 0.9 | |||||
92 | simetryn | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 99.3 | 1.1 | 102.7 | 0.9 | 100.2 | 0.6 | |||||
93 | sulfotep | 0.5 | -100 | 0.15 | 0.5 | 0.9994 | ND | 73.3 | 3.9 | 90.6 | 2.7 | 82.2 | 2.4 | |||||
94 | tebuconazole | 0.1 | -100 | 0.03 | 0.1 | 0.9998 | 0.7 | 84.3 | 2.8 | 95.3 | 1.7 | 93.5 | 0.6 | |||||
95 | terbufos | 1 | -100 | 0.3 | 1.0 | 0.9980 | ND | 60.6 | 6.4 | 95.8 | 4.3 | 86.7 | 2.6 | |||||
96 | terbufos sulfone | 1 | -100 | 0.3 | 1.0 | 0.9995 | ND | 69.4 | 11.3 | 101.3 | 1.9 | 98.8 | 1.6 | |||||
97 | terbufos sulfoxide | 0.1 | -100 | 0.03 | 0.1 | 0.9993 | ND | 81.1 | 2.6 | 99.5 | 1.5 | 96.9 | 0.7 | |||||
98 | terbuthylazine | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 101.5 | 0.7 | 104.4 | 0.9 | 102.6 | 0.6 | |||||
99 | thiabendazole | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 73.3 | 5.0 | 75.4 | 2.2 | 90.8 | 2.7 | |||||
100 | thiacloprid | 0.2 | -100 | 0.06 | 0.2 | 0.9998 | ND | 81.9 | 2.6 | 86.1 | 0.7 | 84.3 | 1.5 | |||||
101 | thiamethoxam | 1 | -100 | 0.3 | 1.0 | 0.9992 | ND | 76.7 | 5.6 | 80.5 | 2.0 | 80.3 | 3.3 | |||||
102 | thiodicarb | 0.1 | -100 | 0.03 | 0.1 | 0.9991 | ND | 93.6 | 2.6 | 118.9 | 2.9 | 115.0 | 1.2 | |||||
103 | triadimefon | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 88.5 | 2.2 | 94.7 | 2.8 | 91.2 | 1.8 | |||||
104 | triazophos | 0.2 | -100 | 0.06 | 0.2 | 0.9998 | ND | 85.7 | 2.1 | 99.1 | 2.6 | 96.3 | 1.0 | |||||
105 | tricyclazole | 0.1 | -100 | 0.03 | 0.1 | 0.9999 | ND | 84.2 | 1.8 | 90.8 | 1.5 | 88.8 | 1.3 | |||||
106 | triflumuron | 0.2 | -100 | 0.06 | 0.2 | 0.9999 | ND | 93.5 | 3.3 | 101.9 | 3.3 | 98.7 | 0.5 | |||||
107 | trifluralin | 1 | -100 | 0.3 | 1.0 | 0.9996 | ND | 96.6 | 5.9 | 92.5 | 2.9 | 91.6 | 1.7 |
Class | Pesticides | Raw water (n=20) | Drinking water (n=20) | |||||||
---|---|---|---|---|---|---|---|---|---|---|
Detection rate/% | Content range/(ng/L) | Detection rate/% | Content range/(ng/L) | |||||||
Carbamate insecticides | benfuracarb, carbofuran, aldicarb sulfone, isoprocarb | 5 | -90 | 0.1 | -5.5 | 10 | -55 | 0.1 | -10.2 | |
Sulfonylurea herbicides | chlorsulfuron, metsulfuron-methyl | 25 | -50 | 0.1 | -1.4 | 0 | -35 | ND | -0.5 | |
Triazine herbicides | atrazine, atrazine-2-hydroxy, atrazine-desethyl, atrazine-desisopropyl, cyanazine, simazine, simetryn, terbuthylazine | 50 | -100 | 0.1 | -97.1 | 0 | -100 | ND | -93.6 | |
Triazole insecticides/ fungicides | triazophos, tebuconazole, triadimefon, tricyclazole, | 40 | -100 | 0.1 | -65.2 | 0 | -95 | ND | -64.6 | |
Amide herbicides | acetochlor, butachlor, metolachlor, pretilachlor | 75 | -100 | 0.1 | -37.6 | 50 | -85 | 0.1 | -26.8 | |
Neonicotinoid insecticides | acetamiprid, clothianidin, imidacloprid, imidacloprid- urea, thiacloprid, thiamethoxam | 35 | -100 | 0.1 | -95.8 | 15 | -85 | 0.1 | -78.4 |
表5 水源水和饮用水中农药的主要检出情况
Table 5 Primary detection of pesticides in raw water and drinking water samples
Class | Pesticides | Raw water (n=20) | Drinking water (n=20) | |||||||
---|---|---|---|---|---|---|---|---|---|---|
Detection rate/% | Content range/(ng/L) | Detection rate/% | Content range/(ng/L) | |||||||
Carbamate insecticides | benfuracarb, carbofuran, aldicarb sulfone, isoprocarb | 5 | -90 | 0.1 | -5.5 | 10 | -55 | 0.1 | -10.2 | |
Sulfonylurea herbicides | chlorsulfuron, metsulfuron-methyl | 25 | -50 | 0.1 | -1.4 | 0 | -35 | ND | -0.5 | |
Triazine herbicides | atrazine, atrazine-2-hydroxy, atrazine-desethyl, atrazine-desisopropyl, cyanazine, simazine, simetryn, terbuthylazine | 50 | -100 | 0.1 | -97.1 | 0 | -100 | ND | -93.6 | |
Triazole insecticides/ fungicides | triazophos, tebuconazole, triadimefon, tricyclazole, | 40 | -100 | 0.1 | -65.2 | 0 | -95 | ND | -64.6 | |
Amide herbicides | acetochlor, butachlor, metolachlor, pretilachlor | 75 | -100 | 0.1 | -37.6 | 50 | -85 | 0.1 | -26.8 | |
Neonicotinoid insecticides | acetamiprid, clothianidin, imidacloprid, imidacloprid- urea, thiacloprid, thiamethoxam | 35 | -100 | 0.1 | -95.8 | 15 | -85 | 0.1 | -78.4 |
Detection method | Samples | Number of detected pesticides | LODs | Sample volume/ mL | Reagents | Ref. |
---|---|---|---|---|---|---|
Online-SPE-LC-MS/MS | raw water, drinking water | 107 | 0.03-1.5 ng/L | 5 | acetonitrile | this study |
SPE-LC-MS/MS | drinking water | 450 (including 7 groups) | 0.01-65 mg/L | 25 | acetonitrile, methylbenzene, sodium acetate, anhydrous sodium sulfate, anhydrous magnesium sulfate | [ |
SPE-LC-MS/MS | surface water, groundwater, domestic sewage, industrial waste water | 15 | 0.002-0.031 μg/L | 100 | methanol | [ |
Liquid-liquid extraction- LC-MS/MS | surface water, groundwater | 40 | 0.1-5 μg/L (LOQ) | 20 | acetone, dichloromethane, hexane, acetonitrile, anhy- drous sodium sulfate | [ |
表6 本方法与其他方法的比较
Table 6 Comparison of the proposed method with other methods
Detection method | Samples | Number of detected pesticides | LODs | Sample volume/ mL | Reagents | Ref. |
---|---|---|---|---|---|---|
Online-SPE-LC-MS/MS | raw water, drinking water | 107 | 0.03-1.5 ng/L | 5 | acetonitrile | this study |
SPE-LC-MS/MS | drinking water | 450 (including 7 groups) | 0.01-65 mg/L | 25 | acetonitrile, methylbenzene, sodium acetate, anhydrous sodium sulfate, anhydrous magnesium sulfate | [ |
SPE-LC-MS/MS | surface water, groundwater, domestic sewage, industrial waste water | 15 | 0.002-0.031 μg/L | 100 | methanol | [ |
Liquid-liquid extraction- LC-MS/MS | surface water, groundwater | 40 | 0.1-5 μg/L (LOQ) | 20 | acetone, dichloromethane, hexane, acetonitrile, anhy- drous sodium sulfate | [ |
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