色谱 ›› 2021, Vol. 39 ›› Issue (5): 541-551.DOI: 10.3724/SP.J.1123.2021.01001
收稿日期:
2021-01-01
出版日期:
2021-05-08
发布日期:
2021-03-31
通讯作者:
于海斌
作者简介:
Tel:(010)84943260,E-mail:yuhb@cnemc.cn.基金资助:
ZHANG Jingxing, ZHENG Xiaoyan, TAN Li, LIU Jinbin, YU Haibin*()
Received:
2021-01-01
Online:
2021-05-08
Published:
2021-03-31
Contact:
YU Haibin
Supported by:
摘要:
建立了测定大气中25种有机氯农药(OCPs)的同位素稀释-高分辨气相色谱/高分辨质谱法(ID-HRGC/HRMS)。样品用正己烷/二氯甲烷(1∶1, v/v)进行加速溶剂萃取(ASE)。通过柱洗脱实验、单柱和组合柱净化实验,最终确定样品的净化方案为弗罗里硅土固相萃取柱和石墨化炭黑固相萃取柱组合净化。样品萃取液净化后进行HRGC/HRMS分析。采用平均相对响应因子(RRF)法对样品中目标物进行定量,6点校准溶液RRF的相对标准偏差(RSD)均≤20%。线性范围为0.4~800 μg/L,相关系数R2均>0.992。对空白样品依次进行100 pg、400 pg和15 ng水平下的加标试验,各添加水平下OCPs测定值的RSD为0.64%~16%,加标回收率为67.2%~135%。穿透试验表明,滤膜+聚氨酯泡沫/聚氨酯泡沫作为吸附介质的大体积主动大气采样器(AAS)在采集环境空气时,五氯苯极易发生穿透,有效采样模式待进一步研究。在上述采样模式下,六氯苯的有效采样体积较小,标准状态(101.325 kPa, 273 K)采样体积应≤30 m3,其他OCPs应≤1200 m3。以上述体积计算,25种目标化合物的检出限为0.002~0.7 pg/m3。对北京环境空气样品分析测定,结果显示除反式-环氧七氯、异狄氏剂、顺式-九氯和4,4'-滴滴滴在部分样品中未检出外,其他OCPs均为100%检出;六氯苯浓度在514~563 pg/m3之间,其他OCPs的浓度在0.01~18.9 pg/m3之间;替代标回收率为33.9%~155%。由于现有相关监测标准的仪器灵敏度较低、方法检出限较高,已无法满足目前空气中痕量OCPs的测定需求,因此亟待修订新的高灵敏度监测方法标准。该方法适用于目前大气中OCPs的超痕量水平分析,为新标准的制订奠定基础,也为国家履行相关国际公约提供有力技术指导。
中图分类号:
张静星, 郑晓燕, 谭丽, 刘进斌, 于海斌. 同位素稀释-高分辨气相色谱/高分辨质谱测定大气中有机氯农药[J]. 色谱, 2021, 39(5): 541-551.
ZHANG Jingxing, ZHENG Xiaoyan, TAN Li, LIU Jinbin, YU Haibin. Determination of atmospheric organochlorine pesticides using isotope dilution high-resolution gas chromatography/high-resolution mass spectrometry[J]. Chinese Journal of Chromatography, 2021, 39(5): 541-551.
No. | Compound | Retention time/min | Characteristic ion m1 (m/z) | Characteristic ion m2 (m/z) | m1/m2 | |
---|---|---|---|---|---|---|
Ratio | Tolerance/% | |||||
Target/surrogate standard | ||||||
1 | hexachlorobenzene (HCB, 六氯苯) | 6.85 | 283.8102 | 285.8073 | 1.24 | ±25 |
13C6-HCB | 6.85 | 289.8303 | 291.8273 | 1.24 | ±25 | |
2 | α-hexachlorocyclohexane (α-HCH, α-六六六) | 7.10 | 180.9379 | 182.9349 | 1.04 | ±25 |
13C6-α-HCH | 7.08 | 186.9580 | 188.9550 | 1.04 | ±25 | |
3 | γ-HCH (γ-六六六) | 7.69 | 180.9379 | 182.9349 | 1.04 | ±25 |
13C6-γ-HCH | 7.69 | 186.9580 | 188.9550 | 1.04 | ±25 | |
4 | β-HCH (β-六六六) | 7.84 | 180.9379 | 182.9347 | 1.04 | ±25 |
13C6-β-HCH | 7.84 | 186.9580 | 188.9550 | 1.04 | ±25 | |
5 | δ-HCH (δ-六六六) | 8.42 | 180.9379 | 182.9349 | 1.04 | ±25 |
13C6-δ-HCH | 8.42 | 186.9580 | 188.9550 | 1.04 | ±25 | |
6 | heptachlor (七氯) | 8.53 | 271.8102 | 273.8072 | 1.24 | ±25 |
13C10-heptachlor | 8.53 | 276.8269 | 278.8240 | 1.24 | ±25 | |
7 | aldrin (艾氏剂) | 9.26 | 262.8570 | 264.8541 | 1.55 | ±25 |
13C12-aldrin | 9.25 | 269.8804 | 271.8775 | 1.55 | ±25 | |
8 | oxychlordane (氧化氯丹) | 10.53 | 386.8053 | 388.8024 | 1.05 | ±25 |
13C10-oxychlordane | 10.51 | 396.8387 | 398.8358 | 1.05 | ±25 | |
9 | cis-heptachlor epoxide (顺式-环氧七氯) | 10.80 | 352.8442 | 354.8413 | 1.24 | ±25 |
13C10-cis-heptachlor epoxide | 10.78 | 362.8777 | 364.8748 | 1.24 | ±25 | |
10 | trans-heptachlor epoxide (反式-环氧七氯) | 10.86 | 352.8442 | 354.8413 | 1.24 | ±25 |
13C10-cis-heptachlor epoxide | 10.78 | 362.8777 | 364.8748 | 1.24 | ±25 | |
11 | trans-chlordane (反式-氯丹) | 11.39 | 372.8260 | 374.8231 | 1.05 | ±25 |
13C10-trans-chlordane | 11.38 | 382.8595 | 384.8565 | 1.05 | ±25 | |
No. | Compound | Retention time/min | Characteristic ion m1 (m/z) | Characteristic ion m2 (m/z) | m1/m2 | |
Ratio | Tolerance/% | |||||
12 | 2,4'-DDE (2,4'-滴滴伊) | 11.46 | 246.0003 | 247.9975 | 1.56 | ±25 |
13C12-2,4'-DDE | 11.46 | 258.0405 | 260.0376 | 1.56 | ±25 | |
13 | trans-nonachlor (反式-九氯) | 11.70 | 406.7870 | 408.7841 | 0.89 | ±25 |
13C10-trans-nonachlor | 11.70 | 416.8205 | 418.8175 | 0.89 | ±25 | |
14 | cis-chlordane (顺式-氯丹) | 11.89 | 372.8260 | 374.8231 | 1.05 | ±25 |
13C10-trans-chlordane | 11.38 | 382.8595 | 384.8565 | 1.05 | ±25 | |
15 | endosulfan-Ⅰ (硫丹-Ⅰ) | 12.06 | 240.9145 | 242.9116 | 0.75 | ±25 |
13C9-endosulfan-I | 12.06 | 248.9414 | 250.9384 | 0.75 | ±25 | |
16 | 4,4'-DDE (4,4'-滴滴伊) | 12.63 | 246.0003 | 247.9975 | 1.56 | ±25 |
13C12-4,4'-DDE | 12.61 | 258.0405 | 260.0376 | 1.56 | ±25 | |
17 | dieldrin (狄氏剂) | 13.12 | 262.8570 | 264.8541 | 1.55 | ±25 |
13C12-dieldrin | 13.09 | 269.8804 | 271.8775 | 1.55 | ±25 | |
18 | 2,4'-DDD (2,4'-滴滴滴) | 13.43 | 235.0081 | 237.0053 | 1.56 | ±25 |
13C12-2,4'-DDD | 13.43 | 247.0483 | 249.0454 | 1.56 | ±25 | |
19 | endrin (异狄氏剂) | 14.38 | 262.8570 | 264.8541 | 1.55 | ±25 |
13C12-endrin | 14.36 | 269.8804 | 271.8775 | 1.55 | ±25 | |
20 | 2,4'-DDT (2,4'-滴滴涕) | 14.76 | 235.0081 | 237.0053 | 1.55 | ±25 |
13C12-2,4'-DDT | 14.76 | 247.0483 | 249.0454 | 1.55 | ±25 | |
21 | cis-nonachlor (顺式-九氯) | 14.84 | 406.7870 | 408.7841 | 0.89 | ±25 |
13C10-cis-nonachlor | 14.82 | 416.8205 | 418.8175 | 0.89 | ±25 | |
22 | 4,4'-DDD (4,4'-滴滴滴) | 15.18 | 235.0081 | 237.0053 | 1.56 | ±25 |
13C12-4,4'-DDD | 15.16 | 247.0483 | 249.0454 | 1.56 | ±25 | |
23 | endosulfan-Ⅱ (硫丹-Ⅱ) | 15.37 | 240.9145 | 242.9116 | 0.75 | ±25 |
13C9-endosulfan-Ⅱ | 15.35 | 248.9414 | 250.9384 | 0.75 | ±25 | |
24 | 4,4'-DDT (4,4'-滴滴涕) | 16.72 | 235.0081 | 237.0053 | 1.55 | ±25 |
13C12-4,4'-DDT | 16.70 | 247.0483 | 249.0454 | 1.55 | ±25 | |
25 | mirex (灭蚁灵) | 21.10 | 271.8102 | 273.8072 | 1.24 | ±25 |
13C10-mirex | 21.07 | 276.8269 | 278.8240 | 1.24 | ±25 | |
a | pentachlorobenzene (PeCB, 五氯苯) | 5.61 | 249.8492 | 251.8463 | 1.55 | ±25 |
13C6-PeCB | 5.61 | 255.8693 | 257.8663 | 1.55 | ±25 | |
Injection internal standard | ||||||
b | 13C12-4,4'-DiCB (13C12-4,4'-二氯联苯) | 7.60 | 234.0406 | 236.0376 | 1.56 | ±25 |
c | 13C12-2,3',4',5-TetraCB (13C12-2,3',4',5-四氯联苯) | 10.69 | 301.9626 | 303.9597 | 0.77 | ±25 |
表 1 高分辨气相色谱/高分辨质谱测定OCPs的参数
Table 1 HRGC/HRMS parameters of organochlorine pesticides (OCPs) determination
No. | Compound | Retention time/min | Characteristic ion m1 (m/z) | Characteristic ion m2 (m/z) | m1/m2 | |
---|---|---|---|---|---|---|
Ratio | Tolerance/% | |||||
Target/surrogate standard | ||||||
1 | hexachlorobenzene (HCB, 六氯苯) | 6.85 | 283.8102 | 285.8073 | 1.24 | ±25 |
13C6-HCB | 6.85 | 289.8303 | 291.8273 | 1.24 | ±25 | |
2 | α-hexachlorocyclohexane (α-HCH, α-六六六) | 7.10 | 180.9379 | 182.9349 | 1.04 | ±25 |
13C6-α-HCH | 7.08 | 186.9580 | 188.9550 | 1.04 | ±25 | |
3 | γ-HCH (γ-六六六) | 7.69 | 180.9379 | 182.9349 | 1.04 | ±25 |
13C6-γ-HCH | 7.69 | 186.9580 | 188.9550 | 1.04 | ±25 | |
4 | β-HCH (β-六六六) | 7.84 | 180.9379 | 182.9347 | 1.04 | ±25 |
13C6-β-HCH | 7.84 | 186.9580 | 188.9550 | 1.04 | ±25 | |
5 | δ-HCH (δ-六六六) | 8.42 | 180.9379 | 182.9349 | 1.04 | ±25 |
13C6-δ-HCH | 8.42 | 186.9580 | 188.9550 | 1.04 | ±25 | |
6 | heptachlor (七氯) | 8.53 | 271.8102 | 273.8072 | 1.24 | ±25 |
13C10-heptachlor | 8.53 | 276.8269 | 278.8240 | 1.24 | ±25 | |
7 | aldrin (艾氏剂) | 9.26 | 262.8570 | 264.8541 | 1.55 | ±25 |
13C12-aldrin | 9.25 | 269.8804 | 271.8775 | 1.55 | ±25 | |
8 | oxychlordane (氧化氯丹) | 10.53 | 386.8053 | 388.8024 | 1.05 | ±25 |
13C10-oxychlordane | 10.51 | 396.8387 | 398.8358 | 1.05 | ±25 | |
9 | cis-heptachlor epoxide (顺式-环氧七氯) | 10.80 | 352.8442 | 354.8413 | 1.24 | ±25 |
13C10-cis-heptachlor epoxide | 10.78 | 362.8777 | 364.8748 | 1.24 | ±25 | |
10 | trans-heptachlor epoxide (反式-环氧七氯) | 10.86 | 352.8442 | 354.8413 | 1.24 | ±25 |
13C10-cis-heptachlor epoxide | 10.78 | 362.8777 | 364.8748 | 1.24 | ±25 | |
11 | trans-chlordane (反式-氯丹) | 11.39 | 372.8260 | 374.8231 | 1.05 | ±25 |
13C10-trans-chlordane | 11.38 | 382.8595 | 384.8565 | 1.05 | ±25 | |
No. | Compound | Retention time/min | Characteristic ion m1 (m/z) | Characteristic ion m2 (m/z) | m1/m2 | |
Ratio | Tolerance/% | |||||
12 | 2,4'-DDE (2,4'-滴滴伊) | 11.46 | 246.0003 | 247.9975 | 1.56 | ±25 |
13C12-2,4'-DDE | 11.46 | 258.0405 | 260.0376 | 1.56 | ±25 | |
13 | trans-nonachlor (反式-九氯) | 11.70 | 406.7870 | 408.7841 | 0.89 | ±25 |
13C10-trans-nonachlor | 11.70 | 416.8205 | 418.8175 | 0.89 | ±25 | |
14 | cis-chlordane (顺式-氯丹) | 11.89 | 372.8260 | 374.8231 | 1.05 | ±25 |
13C10-trans-chlordane | 11.38 | 382.8595 | 384.8565 | 1.05 | ±25 | |
15 | endosulfan-Ⅰ (硫丹-Ⅰ) | 12.06 | 240.9145 | 242.9116 | 0.75 | ±25 |
13C9-endosulfan-I | 12.06 | 248.9414 | 250.9384 | 0.75 | ±25 | |
16 | 4,4'-DDE (4,4'-滴滴伊) | 12.63 | 246.0003 | 247.9975 | 1.56 | ±25 |
13C12-4,4'-DDE | 12.61 | 258.0405 | 260.0376 | 1.56 | ±25 | |
17 | dieldrin (狄氏剂) | 13.12 | 262.8570 | 264.8541 | 1.55 | ±25 |
13C12-dieldrin | 13.09 | 269.8804 | 271.8775 | 1.55 | ±25 | |
18 | 2,4'-DDD (2,4'-滴滴滴) | 13.43 | 235.0081 | 237.0053 | 1.56 | ±25 |
13C12-2,4'-DDD | 13.43 | 247.0483 | 249.0454 | 1.56 | ±25 | |
19 | endrin (异狄氏剂) | 14.38 | 262.8570 | 264.8541 | 1.55 | ±25 |
13C12-endrin | 14.36 | 269.8804 | 271.8775 | 1.55 | ±25 | |
20 | 2,4'-DDT (2,4'-滴滴涕) | 14.76 | 235.0081 | 237.0053 | 1.55 | ±25 |
13C12-2,4'-DDT | 14.76 | 247.0483 | 249.0454 | 1.55 | ±25 | |
21 | cis-nonachlor (顺式-九氯) | 14.84 | 406.7870 | 408.7841 | 0.89 | ±25 |
13C10-cis-nonachlor | 14.82 | 416.8205 | 418.8175 | 0.89 | ±25 | |
22 | 4,4'-DDD (4,4'-滴滴滴) | 15.18 | 235.0081 | 237.0053 | 1.56 | ±25 |
13C12-4,4'-DDD | 15.16 | 247.0483 | 249.0454 | 1.56 | ±25 | |
23 | endosulfan-Ⅱ (硫丹-Ⅱ) | 15.37 | 240.9145 | 242.9116 | 0.75 | ±25 |
13C9-endosulfan-Ⅱ | 15.35 | 248.9414 | 250.9384 | 0.75 | ±25 | |
24 | 4,4'-DDT (4,4'-滴滴涕) | 16.72 | 235.0081 | 237.0053 | 1.55 | ±25 |
13C12-4,4'-DDT | 16.70 | 247.0483 | 249.0454 | 1.55 | ±25 | |
25 | mirex (灭蚁灵) | 21.10 | 271.8102 | 273.8072 | 1.24 | ±25 |
13C10-mirex | 21.07 | 276.8269 | 278.8240 | 1.24 | ±25 | |
a | pentachlorobenzene (PeCB, 五氯苯) | 5.61 | 249.8492 | 251.8463 | 1.55 | ±25 |
13C6-PeCB | 5.61 | 255.8693 | 257.8663 | 1.55 | ±25 | |
Injection internal standard | ||||||
b | 13C12-4,4'-DiCB (13C12-4,4'-二氯联苯) | 7.60 | 234.0406 | 236.0376 | 1.56 | ±25 |
c | 13C12-2,3',4',5-TetraCB (13C12-2,3',4',5-四氯联苯) | 10.69 | 301.9626 | 303.9597 | 0.77 | ±25 |
Compound | Recoveries/% | ||||||||
---|---|---|---|---|---|---|---|---|---|
Acetone/hexane (1∶9, v/v) | Toluene | Dichloromethane/hexane (2∶8, v/v) | |||||||
10 mL | Additional 5 mL | 10 mL | Additional 5 mL | 10 mL | Additional 5 mL | Additional 10 mL dichloromethane/hexane (3∶7, v/v) | |||
13C6-PeCB | 39 | 0 | 75 | 0 | 28 | 0 | 0 | ||
13C6-HCB | 34 | 0 | 61 | 0 | 30 | 0 | 0 | ||
13C6-α-HCH | 53 | 0 | 75 | 0 | 43 | 0 | 0 | ||
13C6-γ-HCH | 57 | 0 | 70 | 0 | 46 | 0 | 0 | ||
13C6-β-HCH | 58 | 0 | 53 | 0 | 52 | 0 | 0 | ||
13C6-δ-HCH | 67 | 0 | 84 | 0 | 68 | 0 | 0 | ||
13C10-Heptachlor | 56 | 0 | 60 | 0 | 45 | 0 | 0 | ||
13C12-Aldrin | 59 | 0 | 84 | 0 | 49 | 0 | 0 | ||
13C10-Oxychlordane | 60 | 0 | 83 | 0 | 55 | 0 | 0 | ||
13C10-cis-Heptachlor epoxide | 65 | 0 | 78 | 0 | 51 | 5 | 1 | ||
13C10-trans-Chlordane | 54 | 0 | 64 | 0 | 50 | 0 | 0 | ||
13C12-2,4'-DDE | 77 | 0 | 98 | 0 | 73 | 0 | 0 | ||
13C10-trans-Nonachlor | 49 | 0 | 47 | 0 | 47 | 0 | 0 | ||
13C9-Endosulfan-Ⅰ | 65 | 0 | 80 | 0 | 5 | 12 | 53 | ||
13C12-4,4'-DDE | 78 | 0 | 92 | 0 | 75 | 0 | 0 | ||
13C12-Dieldrin | 67 | 0 | 100 | 0 | 1 | 8 | 60 | ||
13C12-2,4'-DDD | 89 | 0 | 91 | 0 | 89 | 0 | 0 | ||
13C12-Endrin | 82 | 0 | 83 | 0 | 2 | 5 | 70 | ||
13C12-2,4'-DDT | 91 | 0 | 61 | 0 | 88 | 0 | 0 | ||
13C10-cis-Nonachlor | 56 | 0 | 41 | 0 | 54 | 0 | 0 | ||
13C12-4,4'-DDD | 94 | 0 | 86 | 0 | 95 | 0 | 0 | ||
13C9-Endosulfan-Ⅱ | 70 | 0 | 79 | 0 | 0 | 0 | 7 | ||
13C12-4,4'-DDT | 98 | 0 | 51 | 0 | 93 | 0 | 0 | ||
13C10-Mirex | 80 | 0 | 76 | 0 | 77 | 0 | 0 |
表 2 弗罗里硅土小柱在不同溶剂洗脱下的替代标回收率
Table 2 Surrogate standard recoveries of florisil cartridge with different elution solvents
Compound | Recoveries/% | ||||||||
---|---|---|---|---|---|---|---|---|---|
Acetone/hexane (1∶9, v/v) | Toluene | Dichloromethane/hexane (2∶8, v/v) | |||||||
10 mL | Additional 5 mL | 10 mL | Additional 5 mL | 10 mL | Additional 5 mL | Additional 10 mL dichloromethane/hexane (3∶7, v/v) | |||
13C6-PeCB | 39 | 0 | 75 | 0 | 28 | 0 | 0 | ||
13C6-HCB | 34 | 0 | 61 | 0 | 30 | 0 | 0 | ||
13C6-α-HCH | 53 | 0 | 75 | 0 | 43 | 0 | 0 | ||
13C6-γ-HCH | 57 | 0 | 70 | 0 | 46 | 0 | 0 | ||
13C6-β-HCH | 58 | 0 | 53 | 0 | 52 | 0 | 0 | ||
13C6-δ-HCH | 67 | 0 | 84 | 0 | 68 | 0 | 0 | ||
13C10-Heptachlor | 56 | 0 | 60 | 0 | 45 | 0 | 0 | ||
13C12-Aldrin | 59 | 0 | 84 | 0 | 49 | 0 | 0 | ||
13C10-Oxychlordane | 60 | 0 | 83 | 0 | 55 | 0 | 0 | ||
13C10-cis-Heptachlor epoxide | 65 | 0 | 78 | 0 | 51 | 5 | 1 | ||
13C10-trans-Chlordane | 54 | 0 | 64 | 0 | 50 | 0 | 0 | ||
13C12-2,4'-DDE | 77 | 0 | 98 | 0 | 73 | 0 | 0 | ||
13C10-trans-Nonachlor | 49 | 0 | 47 | 0 | 47 | 0 | 0 | ||
13C9-Endosulfan-Ⅰ | 65 | 0 | 80 | 0 | 5 | 12 | 53 | ||
13C12-4,4'-DDE | 78 | 0 | 92 | 0 | 75 | 0 | 0 | ||
13C12-Dieldrin | 67 | 0 | 100 | 0 | 1 | 8 | 60 | ||
13C12-2,4'-DDD | 89 | 0 | 91 | 0 | 89 | 0 | 0 | ||
13C12-Endrin | 82 | 0 | 83 | 0 | 2 | 5 | 70 | ||
13C12-2,4'-DDT | 91 | 0 | 61 | 0 | 88 | 0 | 0 | ||
13C10-cis-Nonachlor | 56 | 0 | 41 | 0 | 54 | 0 | 0 | ||
13C12-4,4'-DDD | 94 | 0 | 86 | 0 | 95 | 0 | 0 | ||
13C9-Endosulfan-Ⅱ | 70 | 0 | 79 | 0 | 0 | 0 | 7 | ||
13C12-4,4'-DDT | 98 | 0 | 51 | 0 | 93 | 0 | 0 | ||
13C10-Mirex | 80 | 0 | 76 | 0 | 77 | 0 | 0 |
Compound | Recoveries/% | |||||||
---|---|---|---|---|---|---|---|---|
Toluene | Acetone/hexane (1∶1, v/v) | Dichloromethane/hexane (1∶1, v/v) | ||||||
10 mL | Additional 5 mL | 10 mL | Additional 5 mL | 10 mL | Additional 5 mL | |||
13C6-PeCB | 61 | 1 | 0 | 0 | 13 | 2 | ||
13C6-HCB | 104 | 1 | 0 | 0 | 0 | 0 | ||
13C6-α-HCH | 56 | 1 | 45 | 0 | 47 | 0 | ||
13C6-γ-HCH | 55 | 1 | 54 | 0 | 52 | 1 | ||
13C6-β-HCH | 49 | 1 | 66 | 0 | 61 | 1 | ||
13C6-δ-HCH | 55 | 1 | 80 | 0 | 76 | 1 | ||
13C10-Heptachlor | 83 | 1 | 62 | 0 | 59 | 1 | ||
13C12-Aldrin | 83 | 1 | 63 | 0 | 62 | 0 | ||
13C10-Oxychlordane | 102 | 1 | 75 | 0 | 79 | 1 | ||
13C10-cis-Heptachlorepoxide | 79 | 1 | 79 | 0 | 81 | 1 | ||
13C10-trans-Chlordane | 113 | 1 | 77 | 0 | 79 | 1 | ||
13C12-2,4'-DDE | 87 | 1 | 93 | 0 | 97 | 1 | ||
13C10-trans-Nonachlor | 150 | 1 | 73 | 0 | 72 | 1 | ||
13C9-Endosulfan-Ⅰ | 67 | 1 | 84 | 0 | 91 | 1 | ||
13C12-4,4'-DDE | 74 | 1 | 97 | 0 | 102 | 1 | ||
13C12-Dieldrin | 80 | 1 | 86 | 0 | 94 | 1 | ||
13C12-2,4'-DDD | 87 | 1 | 105 | 0 | 114 | 2 | ||
13C12-Endrin | 79 | 0 | 103 | 0 | 102 | 1 | ||
13C12-2,4'-DDT | 77 | 1 | 99 | 0 | 103 | 1 | ||
13C10-cis-Nonachlor | 133 | 1 | 73 | 0 | 76 | 1 | ||
13C12-4,4'-DDD | 81 | 1 | 110 | 0 | 119 | 2 | ||
13C9-Endosulfan-Ⅱ | 74 | 1 | 96 | 1 | 101 | 1 | ||
13C12-4,4'-DDT | 80 | 1 | 108 | 0 | 110 | 1 | ||
13C10-Mirex | 72 | 1 | 88 | 0 | 94 | 1 |
表 3 石墨化炭黑小柱在不同溶剂洗脱下的替代标回收率
Table 3 Surrogate standard recoveries of graphitized carbon black cartridge with different elution solvents
Compound | Recoveries/% | |||||||
---|---|---|---|---|---|---|---|---|
Toluene | Acetone/hexane (1∶1, v/v) | Dichloromethane/hexane (1∶1, v/v) | ||||||
10 mL | Additional 5 mL | 10 mL | Additional 5 mL | 10 mL | Additional 5 mL | |||
13C6-PeCB | 61 | 1 | 0 | 0 | 13 | 2 | ||
13C6-HCB | 104 | 1 | 0 | 0 | 0 | 0 | ||
13C6-α-HCH | 56 | 1 | 45 | 0 | 47 | 0 | ||
13C6-γ-HCH | 55 | 1 | 54 | 0 | 52 | 1 | ||
13C6-β-HCH | 49 | 1 | 66 | 0 | 61 | 1 | ||
13C6-δ-HCH | 55 | 1 | 80 | 0 | 76 | 1 | ||
13C10-Heptachlor | 83 | 1 | 62 | 0 | 59 | 1 | ||
13C12-Aldrin | 83 | 1 | 63 | 0 | 62 | 0 | ||
13C10-Oxychlordane | 102 | 1 | 75 | 0 | 79 | 1 | ||
13C10-cis-Heptachlorepoxide | 79 | 1 | 79 | 0 | 81 | 1 | ||
13C10-trans-Chlordane | 113 | 1 | 77 | 0 | 79 | 1 | ||
13C12-2,4'-DDE | 87 | 1 | 93 | 0 | 97 | 1 | ||
13C10-trans-Nonachlor | 150 | 1 | 73 | 0 | 72 | 1 | ||
13C9-Endosulfan-Ⅰ | 67 | 1 | 84 | 0 | 91 | 1 | ||
13C12-4,4'-DDE | 74 | 1 | 97 | 0 | 102 | 1 | ||
13C12-Dieldrin | 80 | 1 | 86 | 0 | 94 | 1 | ||
13C12-2,4'-DDD | 87 | 1 | 105 | 0 | 114 | 2 | ||
13C12-Endrin | 79 | 0 | 103 | 0 | 102 | 1 | ||
13C12-2,4'-DDT | 77 | 1 | 99 | 0 | 103 | 1 | ||
13C10-cis-Nonachlor | 133 | 1 | 73 | 0 | 76 | 1 | ||
13C12-4,4'-DDD | 81 | 1 | 110 | 0 | 119 | 2 | ||
13C9-Endosulfan-Ⅱ | 74 | 1 | 96 | 1 | 101 | 1 | ||
13C12-4,4'-DDT | 80 | 1 | 108 | 0 | 110 | 1 | ||
13C10-Mirex | 72 | 1 | 88 | 0 | 94 | 1 |
Compound | Recoveries/% | ||||
---|---|---|---|---|---|
Dichloromethane/hexane (1∶9, v/v) | Hexane | ||||
10 mL | Additional 5 mL | 10 mL | Additional 5 mL dichloromethane/hexane (2∶8, v/v) | ||
13C6-PeCB | 25 | 0 | 28 | 0 | |
13C6-HCB | 30 | 0 | 31 | 0 | |
13C6-α-HCH | 40 | 0 | 41 | 0 | |
13C6-γ-HCH | 42 | 0 | 43 | 0 | |
13C6-β-HCH | 50 | 0 | 35 | 12 | |
13C6-δ-HCH | 58 | 3 | 0 | 66 | |
13C10-Heptachlor | 50 | 0 | 48 | 0 | |
13C12-Aldrin | 56 | 0 | 56 | 0 | |
13C10-Oxychlordane | 62 | 0 | 56 | 0 | |
13C10-cis-Heptachlor epoxide | 65 | 0 | 61 | 0 | |
13C10-trans-Chlordane | 55 | 0 | 50 | 0 | |
13C12-2,4'-DDE | 78 | 0 | 71 | 0 | |
13C10-trans-Nonachlor | 51 | 0 | 45 | 0 | |
13C9-Endosulfan-Ⅰ | 65 | 0 | 59 | 1 | |
13C12-4,4'-DDE | 82 | 0 | 73 | 0 | |
13C12-Dieldrin | 74 | 0 | 69 | 0 | |
13C12-2,4'-DDD | 93 | 0 | 84 | 0 | |
13C12-Endrin | 84 | 0 | 68 | 0 | |
13C12-2,4'-DDT | 97 | 0 | 85 | 0 | |
13C10-cis-Nonachlor | 60 | 0 | 53 | 0 | |
13C12-4,4'-DDD | 102 | 0 | 89 | 0 | |
13C9-Endosulfan-Ⅱ | 55 | 14 | 1 | 71 | |
13C12-4,4'-DDT | 104 | 0 | 87 | 0 | |
13C10-Mirex | 83 | 0 | 75 | 0 |
表 4 氧化铝小柱在不同溶剂洗脱下的替代标回收率
Table 4 Surrogate standard recoveries of alumina cartridge with different elution solvents
Compound | Recoveries/% | ||||
---|---|---|---|---|---|
Dichloromethane/hexane (1∶9, v/v) | Hexane | ||||
10 mL | Additional 5 mL | 10 mL | Additional 5 mL dichloromethane/hexane (2∶8, v/v) | ||
13C6-PeCB | 25 | 0 | 28 | 0 | |
13C6-HCB | 30 | 0 | 31 | 0 | |
13C6-α-HCH | 40 | 0 | 41 | 0 | |
13C6-γ-HCH | 42 | 0 | 43 | 0 | |
13C6-β-HCH | 50 | 0 | 35 | 12 | |
13C6-δ-HCH | 58 | 3 | 0 | 66 | |
13C10-Heptachlor | 50 | 0 | 48 | 0 | |
13C12-Aldrin | 56 | 0 | 56 | 0 | |
13C10-Oxychlordane | 62 | 0 | 56 | 0 | |
13C10-cis-Heptachlor epoxide | 65 | 0 | 61 | 0 | |
13C10-trans-Chlordane | 55 | 0 | 50 | 0 | |
13C12-2,4'-DDE | 78 | 0 | 71 | 0 | |
13C10-trans-Nonachlor | 51 | 0 | 45 | 0 | |
13C9-Endosulfan-Ⅰ | 65 | 0 | 59 | 1 | |
13C12-4,4'-DDE | 82 | 0 | 73 | 0 | |
13C12-Dieldrin | 74 | 0 | 69 | 0 | |
13C12-2,4'-DDD | 93 | 0 | 84 | 0 | |
13C12-Endrin | 84 | 0 | 68 | 0 | |
13C12-2,4'-DDT | 97 | 0 | 85 | 0 | |
13C10-cis-Nonachlor | 60 | 0 | 53 | 0 | |
13C12-4,4'-DDD | 102 | 0 | 89 | 0 | |
13C9-Endosulfan-Ⅱ | 55 | 14 | 1 | 71 | |
13C12-4,4'-DDT | 104 | 0 | 87 | 0 | |
13C10-Mirex | 83 | 0 | 75 | 0 |
Compound | Recoveries/% | ||||
---|---|---|---|---|---|
Dichloromethane/hexane (1∶1, v/v) | Hexane | ||||
10 mL | Additional 5 mL | 10 mL | Additional 5 mL dichloromethane | ||
13C6-PeCB | 33 | 0 | 29 | 0 | |
13C6-HCB | 46 | 0 | 38 | 0 | |
13C6-α-HCH | 46 | 0 | 42 | 1 | |
13C6-γ-HCH | 43 | 0 | 47 | 1 | |
13C6-β-HCH | 50 | 1 | 6 | 60 | |
13C6-δ-HCH | 60 | 1 | 0 | 76 | |
13C10-Heptachlor | 62 | 0 | 55 | 0 | |
13C12-Aldrin | 65 | 0 | 60 | 0 | |
13C10-Oxychlordane | 70 | 0 | 74 | 1 | |
13C10-cis-Heptachlor epoxide | 69 | 1 | 49 | 28 | |
13C10-trans-Chlordane | 72 | 0 | 78 | 1 | |
13C12-2,4'-DDE | 79 | 1 | 86 | 1 | |
13C10-trans-Nonachlor | 67 | 1 | 74 | 1 | |
13C9-Endosulfan-Ⅰ | 71 | 1 | 66 | 5 | |
13C12-4,4'-DDE | 80 | 1 | 91 | 0 | |
13C12-Dieldrin | 73 | 1 | 36 | 47 | |
13C12-2,4'-DDD | 84 | 1 | 94 | 1 | |
13C12-Endrin | 67 | 1 | 54 | 28 | |
13C12-2,4'-DDT | 84 | 0 | 90 | 0 | |
13C10-cis-Nonachlor | 67 | 1 | 63 | 14 | |
13C12-4,4'-DDD | 84 | 1 | 97 | 2 | |
13C9-Endosulfan-Ⅱ | 73 | 1 | 0 | 76 | |
13C12-4,4'-DDT | 83 | 0 | 93 | 1 | |
13C10-Mirex | 71 | 0 | 85 | 0 |
表 5 硅胶小柱在不同溶剂洗脱下的替代标回收率
Table 5 Surrogate standard recoveries of silica cartridge with different elution solvents
Compound | Recoveries/% | ||||
---|---|---|---|---|---|
Dichloromethane/hexane (1∶1, v/v) | Hexane | ||||
10 mL | Additional 5 mL | 10 mL | Additional 5 mL dichloromethane | ||
13C6-PeCB | 33 | 0 | 29 | 0 | |
13C6-HCB | 46 | 0 | 38 | 0 | |
13C6-α-HCH | 46 | 0 | 42 | 1 | |
13C6-γ-HCH | 43 | 0 | 47 | 1 | |
13C6-β-HCH | 50 | 1 | 6 | 60 | |
13C6-δ-HCH | 60 | 1 | 0 | 76 | |
13C10-Heptachlor | 62 | 0 | 55 | 0 | |
13C12-Aldrin | 65 | 0 | 60 | 0 | |
13C10-Oxychlordane | 70 | 0 | 74 | 1 | |
13C10-cis-Heptachlor epoxide | 69 | 1 | 49 | 28 | |
13C10-trans-Chlordane | 72 | 0 | 78 | 1 | |
13C12-2,4'-DDE | 79 | 1 | 86 | 1 | |
13C10-trans-Nonachlor | 67 | 1 | 74 | 1 | |
13C9-Endosulfan-Ⅰ | 71 | 1 | 66 | 5 | |
13C12-4,4'-DDE | 80 | 1 | 91 | 0 | |
13C12-Dieldrin | 73 | 1 | 36 | 47 | |
13C12-2,4'-DDD | 84 | 1 | 94 | 1 | |
13C12-Endrin | 67 | 1 | 54 | 28 | |
13C12-2,4'-DDT | 84 | 0 | 90 | 0 | |
13C10-cis-Nonachlor | 67 | 1 | 63 | 14 | |
13C12-4,4'-DDD | 84 | 1 | 97 | 2 | |
13C9-Endosulfan-Ⅱ | 73 | 1 | 0 | 76 | |
13C12-4,4'-DDT | 83 | 0 | 93 | 1 | |
13C10-Mirex | 71 | 0 | 85 | 0 |
Cartridge combination | Elution solvent | Pigments remain |
---|---|---|
Silica→florisil | silica: 10 mL dichloromethane/hexane (1∶1, v/v); florisil: 10 mL toluene | yes |
Silica→graphitized carbon black | silica: 10 mL dichloromethane/hexane (1∶1, v/v); graphitized carbon black: | yes |
10 mL toluene | ||
Silica→alumina | silica: 10 mL dichloromethane/hexane (1∶1, v/v); alumina: 15 mL | yes |
dichloromethane/hexane (1∶9, v/v) | ||
Florisil→alumina | florisil: 10 mL toluene; alumina: 15 mL dichloromethane/hexane (1∶9, v/v) | yes |
Florisil→graphitized carbon black | florisil: 10 mL toluene; graphitized carbon black: 10 mL toluene | no |
Alumina→graphitized carbon black | alumina: 15 mL dichloromethane/hexane (1∶9, v/v); graphitized carbon black: | yes |
10 mL toluene |
表 6 组合固相萃取小柱对空气样品中OCPs的净化效果
Table 6 Cleaning effects of cartridge combination on OCPs in air samples
Cartridge combination | Elution solvent | Pigments remain |
---|---|---|
Silica→florisil | silica: 10 mL dichloromethane/hexane (1∶1, v/v); florisil: 10 mL toluene | yes |
Silica→graphitized carbon black | silica: 10 mL dichloromethane/hexane (1∶1, v/v); graphitized carbon black: | yes |
10 mL toluene | ||
Silica→alumina | silica: 10 mL dichloromethane/hexane (1∶1, v/v); alumina: 15 mL | yes |
dichloromethane/hexane (1∶9, v/v) | ||
Florisil→alumina | florisil: 10 mL toluene; alumina: 15 mL dichloromethane/hexane (1∶9, v/v) | yes |
Florisil→graphitized carbon black | florisil: 10 mL toluene; graphitized carbon black: 10 mL toluene | no |
Alumina→graphitized carbon black | alumina: 15 mL dichloromethane/hexane (1∶9, v/v); graphitized carbon black: | yes |
10 mL toluene |
Compound | Ratios at different sampling volumes/% | |||||||||||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
15 m3 | 30 m3 | 53 m3 | 181 m3 | 271 m3 | 387 m3 | 486 m3 | 607 m3 | 677 m3 | 780 m3 | 892 m3 | 958 m3 | |||||||||||||||
PeCB | 43 | 48 | 53 | 49 | 53 | 51 | 59 | 58 | 50 | 41 | 36 | 35 | ||||||||||||||
HCB | 5 | .0 | 25 | 37 | 45 | 43 | 49 | 24 | 30 | 41 | 55 | 61 | 59 | |||||||||||||
α-HCH | N | .D. | 1 | .0 | 13 | 3 | .0 | 4 | .4 | 13 | 0 | .5 | 0 | .9 | 4 | .3 | 10 | 28 | 20 | |||||||
γ-HCH | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 1 | .1 | 1 | .3 | 6 | .8 | 0 | .8 | 2 | .8 | 3 | .4 | ||
β-HCH | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 1 | .1 | 3 | .5 | ||
δ-HCH | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 0 | .8 | 0 | .9 | ||
Heptachlor | 5 | .0 | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 0 | .6 | 0 | .9 | 7 | .0 | 0 | .4 | 7 | .2 | 1 | .8 | ||
Aldrin | 2 | .2 | 1 | .6 | 1 | .1 | 1 | .0 | 1 | .5 | 2 | .8 | 1 | .6 | 1 | .6 | 3 | .8 | 1 | .3 | 1 | .6 | 1 | .9 | ||
Oxychlordane | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 4 | .4 | 4 | .3 | 3 | .6 | 3 | .5 | 2 | .0 | 2 | .5 | ||
cis-Heptachlor epoxide | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 2 | .4 | 2 | .3 | 2 | .2 | 2 | .1 | 1 | .2 | 1 | .5 | ||
trans-Heptachlor epoxide | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | ||
trans-Chlordane | N | .D. | 1 | .5 | 1 | .5 | 3 | .4 | 2 | .7 | 2 | .0 | 4 | .2 | 4 | .4 | 5 | .3 | 2 | .5 | 1 | .4 | 2 | .5 | ||
2,4'-DDE | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 2 | .0 | 3 | .2 | 2 | .1 | 1 | .2 | 1 | .0 | 0 | .9 | ||
trans-Nonachlor | 1 | .6 | 0 | .9 | 1 | .7 | 2 | .9 | 1 | .3 | 1 | .2 | 1 | .8 | 2 | .1 | 2 | .8 | 1 | .6 | 0 | .2 | 1 | .2 | ||
cis-Chlordane | N | .D. | N | .D. | N | .D. | 2 | .4 | 2 | .7 | 1 | .5 | 2 | .7 | 1 | .0 | 3 | .5 | 0 | .9 | 0 | .5 | 1 | .5 | ||
Endosulfan-Ⅰ | 1 | .7 | 0 | .6 | N | .D. | 0 | .2 | 0 | .3 | 0 | .2 | 5 | .4 | 5 | .1 | 6 | .7 | 3 | .9 | 0 | .4 | 1 | .5 | ||
4,4'-DDE | N | .D. | N | .D. | N | .D. | 0 | .3 | N | .D. | 0 | .2 | 1 | .6 | 1 | .4 | 1 | .7 | 0 | .3 | 0 | .2 | 0 | .2 | ||
Dieldrin | N | .D. | N | .D. | N | .D. | 3 | .4 | 3 | .7 | 2 | .1 | 2 | .9 | 2 | .4 | 2 | .8 | 5 | .4 | 1 | .2 | 2 | .7 | ||
2,4'-DDD | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 8 | .4 | 3 | .6 | 5 | .0 | ||
Endrin | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 8 | .4 | 7 | .5 | ||
2,4'-DDT | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 2 | .8 | 3 | .3 | 1 | .5 | 0 | .9 | 1 | .0 | ||
cis-Nonachlor | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | ||
4,4'-DDD | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 4 | .7 | 6 | .7 | ||
Endosulfan-Ⅱ | N | .D. | 9 | .5 | N | .D. | 0 | .7 | 2 | .3 | 0 | .9 | 0 | .0 | 5 | .3 | N | .D. | N | .D. | N | .D. | N | .D. | ||
4,4'-DDT | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 2 | .4 | 1 | .0 | 1 | .3 | ||
Mirex | 2 | .9 | 1 | .7 | 1 | .5 | 0 | .4 | 0 | .6 | 0 | .5 | 0 | .8 | 1 | .5 | 2 | .2 | 0 | .6 | 0 | .3 | 0 | .5 |
表 7 穿透实验中下层PUF吸附目标物占总PUF吸附量的比值
Table 7 Ratio of OCPs adsorbed by the bottom polyurethane foam (PUF) to total PUFs during the breakthrough tests
Compound | Ratios at different sampling volumes/% | |||||||||||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
15 m3 | 30 m3 | 53 m3 | 181 m3 | 271 m3 | 387 m3 | 486 m3 | 607 m3 | 677 m3 | 780 m3 | 892 m3 | 958 m3 | |||||||||||||||
PeCB | 43 | 48 | 53 | 49 | 53 | 51 | 59 | 58 | 50 | 41 | 36 | 35 | ||||||||||||||
HCB | 5 | .0 | 25 | 37 | 45 | 43 | 49 | 24 | 30 | 41 | 55 | 61 | 59 | |||||||||||||
α-HCH | N | .D. | 1 | .0 | 13 | 3 | .0 | 4 | .4 | 13 | 0 | .5 | 0 | .9 | 4 | .3 | 10 | 28 | 20 | |||||||
γ-HCH | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 1 | .1 | 1 | .3 | 6 | .8 | 0 | .8 | 2 | .8 | 3 | .4 | ||
β-HCH | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 1 | .1 | 3 | .5 | ||
δ-HCH | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 0 | .8 | 0 | .9 | ||
Heptachlor | 5 | .0 | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 0 | .6 | 0 | .9 | 7 | .0 | 0 | .4 | 7 | .2 | 1 | .8 | ||
Aldrin | 2 | .2 | 1 | .6 | 1 | .1 | 1 | .0 | 1 | .5 | 2 | .8 | 1 | .6 | 1 | .6 | 3 | .8 | 1 | .3 | 1 | .6 | 1 | .9 | ||
Oxychlordane | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 4 | .4 | 4 | .3 | 3 | .6 | 3 | .5 | 2 | .0 | 2 | .5 | ||
cis-Heptachlor epoxide | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 2 | .4 | 2 | .3 | 2 | .2 | 2 | .1 | 1 | .2 | 1 | .5 | ||
trans-Heptachlor epoxide | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | ||
trans-Chlordane | N | .D. | 1 | .5 | 1 | .5 | 3 | .4 | 2 | .7 | 2 | .0 | 4 | .2 | 4 | .4 | 5 | .3 | 2 | .5 | 1 | .4 | 2 | .5 | ||
2,4'-DDE | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 2 | .0 | 3 | .2 | 2 | .1 | 1 | .2 | 1 | .0 | 0 | .9 | ||
trans-Nonachlor | 1 | .6 | 0 | .9 | 1 | .7 | 2 | .9 | 1 | .3 | 1 | .2 | 1 | .8 | 2 | .1 | 2 | .8 | 1 | .6 | 0 | .2 | 1 | .2 | ||
cis-Chlordane | N | .D. | N | .D. | N | .D. | 2 | .4 | 2 | .7 | 1 | .5 | 2 | .7 | 1 | .0 | 3 | .5 | 0 | .9 | 0 | .5 | 1 | .5 | ||
Endosulfan-Ⅰ | 1 | .7 | 0 | .6 | N | .D. | 0 | .2 | 0 | .3 | 0 | .2 | 5 | .4 | 5 | .1 | 6 | .7 | 3 | .9 | 0 | .4 | 1 | .5 | ||
4,4'-DDE | N | .D. | N | .D. | N | .D. | 0 | .3 | N | .D. | 0 | .2 | 1 | .6 | 1 | .4 | 1 | .7 | 0 | .3 | 0 | .2 | 0 | .2 | ||
Dieldrin | N | .D. | N | .D. | N | .D. | 3 | .4 | 3 | .7 | 2 | .1 | 2 | .9 | 2 | .4 | 2 | .8 | 5 | .4 | 1 | .2 | 2 | .7 | ||
2,4'-DDD | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 8 | .4 | 3 | .6 | 5 | .0 | ||
Endrin | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 8 | .4 | 7 | .5 | ||
2,4'-DDT | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 2 | .8 | 3 | .3 | 1 | .5 | 0 | .9 | 1 | .0 | ||
cis-Nonachlor | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | ||
4,4'-DDD | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 4 | .7 | 6 | .7 | ||
Endosulfan-Ⅱ | N | .D. | 9 | .5 | N | .D. | 0 | .7 | 2 | .3 | 0 | .9 | 0 | .0 | 5 | .3 | N | .D. | N | .D. | N | .D. | N | .D. | ||
4,4'-DDT | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | N | .D. | 2 | .4 | 1 | .0 | 1 | .3 | ||
Mirex | 2 | .9 | 1 | .7 | 1 | .5 | 0 | .4 | 0 | .6 | 0 | .5 | 0 | .8 | 1 | .5 | 2 | .2 | 0 | .6 | 0 | .3 | 0 | .5 |
Compound | MDL/ (pg/m3) | R2 | Recovery/ % |
---|---|---|---|
HCB | 0.7 | 0.9986 | 90.2-125 |
α-HCH | 0.006 | 0.9997 | 88.6-135 |
γ-HCH | 0.007 | 0.9998 | 92.9-121 |
β-HCH | 0.004 | 0.9999 | 97.8-117 |
δ-HCH | 0.004 | 0.9999 | 92.0-110 |
Heptachlor | 0.003 | 0.9994 | 77.6-102 |
Aldrin | 0.006 | 1.0000 | 82.1-98.6 |
Oxychlordane | 0.003 | 0.9996 | 81.4-124 |
cis-Heptachlor epoxide | 0.002 | 0.9999 | 83.3-103 |
trans-Heptachlor epoxide | 0.002 | 0.9969 | 70.9-104 |
trans-Chlordane | 0.006 | 0.9994 | 76.8-120 |
2,4'-DDE | 0.003 | 0.9999 | 76.0-102 |
trans-Nonachlor | 0.003 | 0.9998 | 76.5-130 |
cis-Chlordane | 0.004 | 0.9987 | 76.2-118 |
Endosulfan-Ⅰ | 0.004 | 0.9929 | 67.2-120 |
4,4'-DDE | 0.004 | 0.9999 | 80.0-102 |
Dieldrin | 0.003 | 0.9997 | 82.4-104 |
2,4'-DDD | 0.003 | 0.9999 | 74.9-98.4 |
Endrin | 0.003 | 0.9990 | 75.7-107 |
2,4'-DDT | 0.003 | 0.9995 | 82.6-108 |
cis-Nonachlor | 0.002 | 0.9993 | 75.9-130 |
4,4'-DDD | 0.003 | 0.9998 | 84.8-98.2 |
Endosulfan-Ⅱ | 0.005 | 0.9973 | 81.5-115 |
4,4'-DDT | 0.003 | 0.9990 | 82.2-99.3 |
Mirex | 0.003 | 0.9999 | 85.6-101 |
表 8 25种OCPs的方法检出限、线性相关系数和加标回收率
Table 8 Method detection limits (MDL), liner correlation coefficients (R2) and recoveries of the 25 OCPs
Compound | MDL/ (pg/m3) | R2 | Recovery/ % |
---|---|---|---|
HCB | 0.7 | 0.9986 | 90.2-125 |
α-HCH | 0.006 | 0.9997 | 88.6-135 |
γ-HCH | 0.007 | 0.9998 | 92.9-121 |
β-HCH | 0.004 | 0.9999 | 97.8-117 |
δ-HCH | 0.004 | 0.9999 | 92.0-110 |
Heptachlor | 0.003 | 0.9994 | 77.6-102 |
Aldrin | 0.006 | 1.0000 | 82.1-98.6 |
Oxychlordane | 0.003 | 0.9996 | 81.4-124 |
cis-Heptachlor epoxide | 0.002 | 0.9999 | 83.3-103 |
trans-Heptachlor epoxide | 0.002 | 0.9969 | 70.9-104 |
trans-Chlordane | 0.006 | 0.9994 | 76.8-120 |
2,4'-DDE | 0.003 | 0.9999 | 76.0-102 |
trans-Nonachlor | 0.003 | 0.9998 | 76.5-130 |
cis-Chlordane | 0.004 | 0.9987 | 76.2-118 |
Endosulfan-Ⅰ | 0.004 | 0.9929 | 67.2-120 |
4,4'-DDE | 0.004 | 0.9999 | 80.0-102 |
Dieldrin | 0.003 | 0.9997 | 82.4-104 |
2,4'-DDD | 0.003 | 0.9999 | 74.9-98.4 |
Endrin | 0.003 | 0.9990 | 75.7-107 |
2,4'-DDT | 0.003 | 0.9995 | 82.6-108 |
cis-Nonachlor | 0.002 | 0.9993 | 75.9-130 |
4,4'-DDD | 0.003 | 0.9998 | 84.8-98.2 |
Endosulfan-Ⅱ | 0.005 | 0.9973 | 81.5-115 |
4,4'-DDT | 0.003 | 0.9990 | 82.2-99.3 |
Mirex | 0.003 | 0.9999 | 85.6-101 |
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