
职业与健康 ›› 2026, Vol. 42 ›› Issue (17): 2337-2342.
收稿日期:2025-06-25
修回日期:2025-10-14
出版日期:2026-09-01
发布日期:2026-08-14
通信作者:
赵宜静 E-mail:yjzhao@pdcdc.sh.cn
作者简介:张珏,女,主管技师,主要从事理化检验工作。
基金资助:
ZHANG Jue, DAI Jing, MIN Wei, HAN Zhebin, ZHENG Rong, ZHAO Yijing(
)
Received:2025-06-25
Revised:2025-10-14
Online:2026-09-01
Published:2026-08-14
Contact:
ZHAO Yijing E-mail:yjzhao@pdcdc.sh.cn
摘要:
目的 建立生活饮用水中12种三嗪类除草剂的固相萃取-超高液相色谱-串联质谱(ultra-high performance liquid chromatography-tandem mass spectrometry,SPE-UPLC-MS/MS)检测方法。方法 水样添加内标后经Supelclean ENVI-Chrom P SPE小柱萃取后使用超高液相色谱-串联质谱法检测,内标法定量。结果 12种三嗪类除草剂在0.1~50.0 ng/mL范围内线性良好(r≥0.999),以取样量200 mL计,12种三嗪类除草剂的方法检出限为0.05~0.14 ng/L,方法定量限为0.15~0.42 ng/L;3个浓度水平(5、50、200 ng/L)在纯水和自来水中的加标回收率分别为83.6%~101.1%和85.6%~100.4%,相对标准偏差分别为1.1%~4.3%和1.0%~6.0%。结论 所建立的方法灵敏可靠,适用于生活饮用水中12种三嗪类除草剂的检测。
中图分类号:
张珏, 戴菁, 闵巍, 韩哲斌, 郑嵘, 赵宜静. SPE-UPLC-MS/MS测定生活饮用水中12种三嗪类除草剂. [J]职业与健康, 2026, 42(17): 2337-2342.
ZHANG Jue, DAI Jing, MIN Wei, HAN Zhebin, ZHENG Rong, ZHAO Yijing. Determination of 12 triazine herbicides in drinking water by SPE-UPLC-MS/MS. [J]OCCUPATION AND HEALTH, 2026, 42(17): 2337-2342.
| 化合物名称 | CAS号 | 母离子 (m/z) | 子离子 (m/z) | 锥孔 电压 (V) | 碰撞 能量 (eV) | 保留 时间 (min) |
|---|---|---|---|---|---|---|
| 莠去津 | 1912-24-9 | 215.882 | 173.889a/95.859 | 28 | 14/22 | 4.78 |
| 西玛津 | 122-34-9 | 201.862 | 123.875a/131.815 | 26 | 16/16 | 4.01 |
| 氰草津 | 21725-46-2 | 240.892 | 213.890a/103.816 | 22 | 14/28 | 4.08 |
| 扑灭津 | 139-40-2 | 229.848 | 187.878a/145.786 | 4 | 14/20 | 5.50 |
| 特丁津 | 5915-41-3 | 229.848 | 173.828a/95.880 | 2 | 14/24 | 5.66 |
| 西草净 | 1014-70-6 | 213.949 | 123.871a/95.885 | 2 | 16/22 | 3.43 |
| 莠灭净 | 834-12-8 | 227.979 | 185.873a/95.880 | 2 | 16/24 | 4.13 |
| 扑草净 | 7287-19-6 | 241.881 | 157.824a/199.915 | 74 | 20/16 | 4.84 |
| 环嗪酮 | 51235-04-2 | 252.959 | 170.913a/100.833 | 14 | 12/36 | 3.77 |
| 嗪草酮 | 21087-64-9 | 214.875 | 186.889a/130.814 | 36 | 16/18 | 4.20 |
| 莠去通 | 1610-17-9 | 211.973 | 169.862a/99.785 | 2 | 16/22 | 2.98 |
| 扑灭通 | 1610-18-0 | 226.003 | 183.906a/141.878 | 2 | 16/20 | 3.54 |
| 莠去津-d5 | 163165-75-1 | 220.912 | 178.865a/100.836 | 22 | 16/22 | 4.75 |
| 西玛津-d10 | 220621-39-6 | 211.882 | 136.893a/133.960 | 26 | 18/16 | 3.95 |
| 氰草津-d5 | 1190003-29-2 | 245.986 | 218.919a/100.891 | 26 | 14/24 | 4.07 |
| 扑灭津-d14 | 1219802-87-5 | 243.938 | 195.931a/147.859 | 68 | 16/22 | 5.42 |
| 特丁津-d5 | 222986-60-9 | 234.878 | 178.916a/136.882 | 54 | 14/22 | 5.63 |
| 扑草净-d14 | 1202864-57-0 | 256.089 | 159.826a/207.960 | 2 | 24/18 | 4.72 |
| 环嗪酮-d6 | 1219804-22-4 | 258.999 | 176.896a/90.938 | 20 | 14/28 | 3.75 |
| 扑灭通-d14 | 1219803-45-8 | 239.965 | 192.022a/143.886 | 76 | 18/22 | 3.47 |
表1 质谱分析条件
| 化合物名称 | CAS号 | 母离子 (m/z) | 子离子 (m/z) | 锥孔 电压 (V) | 碰撞 能量 (eV) | 保留 时间 (min) |
|---|---|---|---|---|---|---|
| 莠去津 | 1912-24-9 | 215.882 | 173.889a/95.859 | 28 | 14/22 | 4.78 |
| 西玛津 | 122-34-9 | 201.862 | 123.875a/131.815 | 26 | 16/16 | 4.01 |
| 氰草津 | 21725-46-2 | 240.892 | 213.890a/103.816 | 22 | 14/28 | 4.08 |
| 扑灭津 | 139-40-2 | 229.848 | 187.878a/145.786 | 4 | 14/20 | 5.50 |
| 特丁津 | 5915-41-3 | 229.848 | 173.828a/95.880 | 2 | 14/24 | 5.66 |
| 西草净 | 1014-70-6 | 213.949 | 123.871a/95.885 | 2 | 16/22 | 3.43 |
| 莠灭净 | 834-12-8 | 227.979 | 185.873a/95.880 | 2 | 16/24 | 4.13 |
| 扑草净 | 7287-19-6 | 241.881 | 157.824a/199.915 | 74 | 20/16 | 4.84 |
| 环嗪酮 | 51235-04-2 | 252.959 | 170.913a/100.833 | 14 | 12/36 | 3.77 |
| 嗪草酮 | 21087-64-9 | 214.875 | 186.889a/130.814 | 36 | 16/18 | 4.20 |
| 莠去通 | 1610-17-9 | 211.973 | 169.862a/99.785 | 2 | 16/22 | 2.98 |
| 扑灭通 | 1610-18-0 | 226.003 | 183.906a/141.878 | 2 | 16/20 | 3.54 |
| 莠去津-d5 | 163165-75-1 | 220.912 | 178.865a/100.836 | 22 | 16/22 | 4.75 |
| 西玛津-d10 | 220621-39-6 | 211.882 | 136.893a/133.960 | 26 | 18/16 | 3.95 |
| 氰草津-d5 | 1190003-29-2 | 245.986 | 218.919a/100.891 | 26 | 14/24 | 4.07 |
| 扑灭津-d14 | 1219802-87-5 | 243.938 | 195.931a/147.859 | 68 | 16/22 | 5.42 |
| 特丁津-d5 | 222986-60-9 | 234.878 | 178.916a/136.882 | 54 | 14/22 | 5.63 |
| 扑草净-d14 | 1202864-57-0 | 256.089 | 159.826a/207.960 | 2 | 24/18 | 4.72 |
| 环嗪酮-d6 | 1219804-22-4 | 258.999 | 176.896a/90.938 | 20 | 14/28 | 3.75 |
| 扑灭通-d14 | 1219803-45-8 | 239.965 | 192.022a/143.886 | 76 | 18/22 | 3.47 |
| 化合物 | 线性方程 | 线性范围(ng/mL) | r值 | 200 mL空白样品加标0.1 ng后测定值(ng/L,n=6) | 方法检出限(ng/L) | 方法定量限(ng/L) |
|---|---|---|---|---|---|---|
| 莠去津 | Y=0.109 5X+0.002 8 | 0.1~50.0 | 0.999 7 | 0.48/0.51/0.51/0.46/0.50/0.48 | 0.11 | 0.33 |
| 西玛津 | Y=0.091 1X+0.002 7 | 0.1~50.0 | 0.999 7 | 0.48/0.47/0.46/0.49/0.48/0.48 | 0.07 | 0.21 |
| 氰草津 | Y=0.087 7X+0.001 1 | 0.1~50.0 | 0.999 6 | 0.49/0.46/0.49/0.48/0.48/0.47 | 0.08 | 0.24 |
| 扑灭津 | Y=0.174 2X+0.004 1 | 0.1~50.0 | 0.999 6 | 0.47/0.42/0.43/0.42/0.41/0.43 | 0.11 | 0.33 |
| 特丁津 | Y=0.175 2X+0.004 7 | 0.1~50.0 | 0.999 8 | 0.48/0.51/0.49/0.48/0.50/0.46 | 0.10 | 0.30 |
| 西草净 | Y=0.382 9X+0.007 0 | 0.1~50.0 | 0.999 9 | 0.49/0.50/0.52/0.50/0.50/0.50 | 0.05 | 0.15 |
| 莠灭净 | Y=0.885 6X+0.014 0 | 0.1~50.0 | 0.999 0 | 0.48/0.49/0.47/0.49/0.48/0.48 | 0.05 | 0.15 |
| 扑草净 | Y=0.047 1X+0.001 1 | 0.1~50.0 | 0.999 7 | 0.41/0.44/0.42/0.46/0.42/0.43 | 0.10 | 0.30 |
| 环嗪酮 | Y=0.098 7X+0.002 3 | 0.1~50.0 | 0.999 4 | 0.44/0.41/0.45/0.44/0.45/0.43 | 0.10 | 0.30 |
| 嗪草酮 | Y=0.130 5X+0.001 5 | 0.1~50.0 | 0.999 5 | 0.46/0.49/0.43/0.44/0.48/0.48 | 0.13 | 0.39 |
| 莠去通 | Y=0.611 2X+0.016 1 | 0.1~50.0 | 0.999 1 | 0.46/0.45/0.51/0.44/0.46/0.48 | 0.14 | 0.42 |
| 扑灭通 | Y=0.461 2X+0.011 3 | 0.1~50.0 | 0.999 4 | 0.49/0.48/0.50/0.51/0.47/0.49 | 0.08 | 0.24 |
表2 12种三嗪类除草剂的线性、方法检出限和方法定量限
| 化合物 | 线性方程 | 线性范围(ng/mL) | r值 | 200 mL空白样品加标0.1 ng后测定值(ng/L,n=6) | 方法检出限(ng/L) | 方法定量限(ng/L) |
|---|---|---|---|---|---|---|
| 莠去津 | Y=0.109 5X+0.002 8 | 0.1~50.0 | 0.999 7 | 0.48/0.51/0.51/0.46/0.50/0.48 | 0.11 | 0.33 |
| 西玛津 | Y=0.091 1X+0.002 7 | 0.1~50.0 | 0.999 7 | 0.48/0.47/0.46/0.49/0.48/0.48 | 0.07 | 0.21 |
| 氰草津 | Y=0.087 7X+0.001 1 | 0.1~50.0 | 0.999 6 | 0.49/0.46/0.49/0.48/0.48/0.47 | 0.08 | 0.24 |
| 扑灭津 | Y=0.174 2X+0.004 1 | 0.1~50.0 | 0.999 6 | 0.47/0.42/0.43/0.42/0.41/0.43 | 0.11 | 0.33 |
| 特丁津 | Y=0.175 2X+0.004 7 | 0.1~50.0 | 0.999 8 | 0.48/0.51/0.49/0.48/0.50/0.46 | 0.10 | 0.30 |
| 西草净 | Y=0.382 9X+0.007 0 | 0.1~50.0 | 0.999 9 | 0.49/0.50/0.52/0.50/0.50/0.50 | 0.05 | 0.15 |
| 莠灭净 | Y=0.885 6X+0.014 0 | 0.1~50.0 | 0.999 0 | 0.48/0.49/0.47/0.49/0.48/0.48 | 0.05 | 0.15 |
| 扑草净 | Y=0.047 1X+0.001 1 | 0.1~50.0 | 0.999 7 | 0.41/0.44/0.42/0.46/0.42/0.43 | 0.10 | 0.30 |
| 环嗪酮 | Y=0.098 7X+0.002 3 | 0.1~50.0 | 0.999 4 | 0.44/0.41/0.45/0.44/0.45/0.43 | 0.10 | 0.30 |
| 嗪草酮 | Y=0.130 5X+0.001 5 | 0.1~50.0 | 0.999 5 | 0.46/0.49/0.43/0.44/0.48/0.48 | 0.13 | 0.39 |
| 莠去通 | Y=0.611 2X+0.016 1 | 0.1~50.0 | 0.999 1 | 0.46/0.45/0.51/0.44/0.46/0.48 | 0.14 | 0.42 |
| 扑灭通 | Y=0.461 2X+0.011 3 | 0.1~50.0 | 0.999 4 | 0.49/0.48/0.50/0.51/0.47/0.49 | 0.08 | 0.24 |
| 化合物 | 加标 浓度 (ng/L) | 纯水(n=6) | 自来水(n=6) | ||||
|---|---|---|---|---|---|---|---|
| 实测浓度 (ng/L) | RSD (%) | 回收率 (%) | 实测浓度 (ng/L) | RSD(%) | 回收率 (%) | ||
| 莠去津 | 5 | 4.94 | 4.3 | 98.8 | 4.87 | 2.8 | 97.4 |
| 50 | 47.39 | 1.5 | 94.8 | 48.38 | 4.2 | 96.8 | |
| 200 | 190.94 | 1.8 | 95.5 | 198.17 | 1.0 | 99.1 | |
| 西玛津 | 5 | 5.03 | 2.6 | 100.6 | 4.94 | 1.7 | 98.8 |
| 50 | 47.51 | 2.4 | 95.0 | 49.21 | 2.5 | 98.4 | |
| 200 | 191.52 | 3.2 | 95.8 | 197.77 | 2.3 | 98.9 | |
| 氰草津 | 5 | 4.98 | 2.2 | 99.6 | 4.79 | 3.6 | 95.8 |
| 50 | 46.93 | 3.0 | 93.9 | 47.00 | 2.9 | 94.0 | |
| 200 | 187.11 | 1.4 | 93.6 | 193.73 | 1.8 | 96.9 | |
| 扑灭津 | 5 | 4.91 | 3.5 | 98.2 | 5.00 | 2.3 | 100.1 |
| 50 | 48.02 | 2.5 | 96.0 | 49.46 | 3.7 | 98.9 | |
| 200 | 192.72 | 2.8 | 96.4 | 200.77 | 1.8 | 100.4 | |
| 特丁津 | 5 | 5.03 | 2.7 | 100.6 | 4.95 | 5.2 | 99.0 |
| 50 | 48.05 | 2.0 | 96.1 | 49.14 | 1.3 | 98.3 | |
| 200 | 193.69 | 1.2 | 96.8 | 198.04 | 1.3 | 99.0 | |
| 西草净 | 5 | 4.71 | 2.7 | 94.2 | 4.52 | 5.6 | 90.3 |
| 50 | 47.05 | 1.8 | 94.1 | 44.13 | 3.5 | 88.3 | |
| 200 | 188.41 | 2.3 | 94.2 | 183.15 | 3.6 | 91.6 | |
| 莠灭净 | 5 | 4.89 | 3.9 | 97.8 | 4.45 | 6.0 | 89.0 |
| 50 | 48.33 | 1.6 | 96.7 | 42.82 | 3.3 | 85.6 | |
| 200 | 196.72 | 1.1 | 98.4 | 181.33 | 4.0 | 90.7 | |
| 扑草净 | 5 | 4.53 | 2.2 | 90.5 | 4.30 | 3.1 | 86.0 |
| 50 | 41.80 | 2.0 | 83.6 | 43.69 | 4.6 | 87.4 | |
| 200 | 182.85 | 4.2 | 91.4 | 181.77 | 3.0 | 90.9 | |
| 环嗪酮 | 5 | 4.98 | 1.8 | 99.6 | 4.85 | 2.6 | 97.0 |
| 50 | 48.87 | 1.7 | 97.7 | 47.82 | 1.6 | 95.6 | |
| 200 | 190.12 | 1.5 | 95.1 | 193.98 | 2.0 | 97.0 | |
| 嗪草酮 | 5 | 5.05 | 2.1 | 101.1 | 4.77 | 3.1 | 95.3 |
| 50 | 48.00 | 2.3 | 96.0 | 47.08 | 3.4 | 94.2 | |
| 200 | 194.01 | 2.1 | 97.0 | 191.75 | 2.0 | 95.9 | |
| 莠去通 | 5 | 4.99 | 2.0 | 99.9 | 4.81 | 2.1 | 96.2 |
| 50 | 48.34 | 1.4 | 96.7 | 48.67 | 1.1 | 97.3 | |
| 200 | 190.26 | 2.7 | 95.1 | 195.34 | 2.6 | 97.7 | |
| 扑灭通 | 5 | 4.82 | 1.7 | 96.4 | 4.80 | 2.7 | 96.0 |
| 50 | 46.63 | 2.1 | 93.3 | 48.51 | 2.3 | 97.0 | |
| 200 | 184.97 | 1.8 | 92.5 | 197.37 | 1.0 | 98.7 | |
表3 12种三嗪类除草剂的加标回收率和精密度
| 化合物 | 加标 浓度 (ng/L) | 纯水(n=6) | 自来水(n=6) | ||||
|---|---|---|---|---|---|---|---|
| 实测浓度 (ng/L) | RSD (%) | 回收率 (%) | 实测浓度 (ng/L) | RSD(%) | 回收率 (%) | ||
| 莠去津 | 5 | 4.94 | 4.3 | 98.8 | 4.87 | 2.8 | 97.4 |
| 50 | 47.39 | 1.5 | 94.8 | 48.38 | 4.2 | 96.8 | |
| 200 | 190.94 | 1.8 | 95.5 | 198.17 | 1.0 | 99.1 | |
| 西玛津 | 5 | 5.03 | 2.6 | 100.6 | 4.94 | 1.7 | 98.8 |
| 50 | 47.51 | 2.4 | 95.0 | 49.21 | 2.5 | 98.4 | |
| 200 | 191.52 | 3.2 | 95.8 | 197.77 | 2.3 | 98.9 | |
| 氰草津 | 5 | 4.98 | 2.2 | 99.6 | 4.79 | 3.6 | 95.8 |
| 50 | 46.93 | 3.0 | 93.9 | 47.00 | 2.9 | 94.0 | |
| 200 | 187.11 | 1.4 | 93.6 | 193.73 | 1.8 | 96.9 | |
| 扑灭津 | 5 | 4.91 | 3.5 | 98.2 | 5.00 | 2.3 | 100.1 |
| 50 | 48.02 | 2.5 | 96.0 | 49.46 | 3.7 | 98.9 | |
| 200 | 192.72 | 2.8 | 96.4 | 200.77 | 1.8 | 100.4 | |
| 特丁津 | 5 | 5.03 | 2.7 | 100.6 | 4.95 | 5.2 | 99.0 |
| 50 | 48.05 | 2.0 | 96.1 | 49.14 | 1.3 | 98.3 | |
| 200 | 193.69 | 1.2 | 96.8 | 198.04 | 1.3 | 99.0 | |
| 西草净 | 5 | 4.71 | 2.7 | 94.2 | 4.52 | 5.6 | 90.3 |
| 50 | 47.05 | 1.8 | 94.1 | 44.13 | 3.5 | 88.3 | |
| 200 | 188.41 | 2.3 | 94.2 | 183.15 | 3.6 | 91.6 | |
| 莠灭净 | 5 | 4.89 | 3.9 | 97.8 | 4.45 | 6.0 | 89.0 |
| 50 | 48.33 | 1.6 | 96.7 | 42.82 | 3.3 | 85.6 | |
| 200 | 196.72 | 1.1 | 98.4 | 181.33 | 4.0 | 90.7 | |
| 扑草净 | 5 | 4.53 | 2.2 | 90.5 | 4.30 | 3.1 | 86.0 |
| 50 | 41.80 | 2.0 | 83.6 | 43.69 | 4.6 | 87.4 | |
| 200 | 182.85 | 4.2 | 91.4 | 181.77 | 3.0 | 90.9 | |
| 环嗪酮 | 5 | 4.98 | 1.8 | 99.6 | 4.85 | 2.6 | 97.0 |
| 50 | 48.87 | 1.7 | 97.7 | 47.82 | 1.6 | 95.6 | |
| 200 | 190.12 | 1.5 | 95.1 | 193.98 | 2.0 | 97.0 | |
| 嗪草酮 | 5 | 5.05 | 2.1 | 101.1 | 4.77 | 3.1 | 95.3 |
| 50 | 48.00 | 2.3 | 96.0 | 47.08 | 3.4 | 94.2 | |
| 200 | 194.01 | 2.1 | 97.0 | 191.75 | 2.0 | 95.9 | |
| 莠去通 | 5 | 4.99 | 2.0 | 99.9 | 4.81 | 2.1 | 96.2 |
| 50 | 48.34 | 1.4 | 96.7 | 48.67 | 1.1 | 97.3 | |
| 200 | 190.26 | 2.7 | 95.1 | 195.34 | 2.6 | 97.7 | |
| 扑灭通 | 5 | 4.82 | 1.7 | 96.4 | 4.80 | 2.7 | 96.0 |
| 50 | 46.63 | 2.1 | 93.3 | 48.51 | 2.3 | 97.0 | |
| 200 | 184.97 | 1.8 | 92.5 | 197.37 | 1.0 | 98.7 | |
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