超高效液相色谱-串联质谱法同时测定土壤中30种抗生素

doi:10.3724/SP.J.1123.2021.02019

色谱 ›› 2021, Vol. 39 ›› Issue (8): 878-888.DOI: 10.3724/SP.J.1123.2021.02019

超高效液相色谱-串联质谱法同时测定土壤中30种抗生素

胡钰¹^,², 朱青青¹^,², 胡立刚¹^,²^,³, 廖春阳¹^,²^,³^,^*()

1.中国科学院生态环境研究中心, 环境化学与生态毒理学国家重点实验室, 北京 100085
2.中国科学院大学资源与环境学院, 北京 100049
3.国科大杭州高等研究院环境学院, 浙江杭州 310000

收稿日期:2021-02-19 出版日期:2021-08-08 发布日期:2021-06-29
通讯作者: 廖春阳
作者简介:*E-mail: cyliao@rcees.ac.cn.
基金资助:
国家重点研发计划项目(2018YFC1801602);国家重点研发计划项目(2019YFC1604802);国家自然科学基金项目(21806172)

Simultaneous determination of 30 antibiotics in soil by ultra-high performance liquid chromatography-tandem mass spectrometry

HU Yu¹^,², ZHU Qingqing¹^,², HU Ligang¹^,²^,³, LIAO Chunyang¹^,²^,³^,^*()

1. State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
2. College of Resources and Environment, University of Chinese Academy of Sciences (UCAS), Beijing 100049, China
3. Institute of Environment and Health, Hangzhou Institute for Advanced Study, UCAS, Hangzhou 310000, China

Received:2021-02-19 Online:2021-08-08 Published:2021-06-29
Contact: LIAO Chunyang
Supported by:
National Key Research and Development Program of China(2018YFC1801602);National Key Research and Development Program of China(2019YFC1604802);National Natural Science Foundation of China(21806172)

摘要/Abstract

摘要：

土壤基质复杂,土壤中残留的抗生素种类繁多,浓度多为痕量水平,高灵敏度的仪器方法、有效的净化和富集方法、多种类抗生素的同时检测是土壤中抗生素检测的重点和难点。该研究建立了固相萃取-超高效液相色谱-串联质谱法同时测定土壤中7类(磺胺类、氟喹诺酮类、四环素类、大环内酯类、β-内酰胺类、酰胺醇类和林可酰胺类)30种抗生素的方法。首先,通过参数优化确定最佳质谱条件,选择BEH-C18色谱柱,以0.1%(v/v)甲酸甲醇溶液-0.1%(v/v)甲酸水溶液为流动相,10%(v/v)甲醇水溶液为进样溶剂。然后,通过提取条件(萃取剂种类及体积)和固相萃取条件(上样液pH、淋洗液有机溶剂比例、洗脱液种类及体积)的优化,确定使用10 mL乙腈和Na₂EDTA-McIlvaine缓冲液的混合溶液(1∶1, v/v)为萃取剂,萃取液pH调节至8.0后,采用HLB小柱进行固相萃取,并以10 mL超纯水淋洗净化,最后用10 mL甲醇-乙腈(1∶1, v/v)洗脱目标分析物。在优化的分析条件下,该方法的定量限为0.043~4.04 μg/kg,目标化合物的标准曲线线性关系良好,相关系数在0.992~1.00的范围内,在20、100、200 μg/kg的添加浓度下,大多数目标化合物的加标回收率范围为44.8%~164%,相对标准偏差为0.700%~14.8%。将该方法用于6个实际土壤样品的分析,结果显示在30种抗生素中,17种抗生素有检出,其中12种抗生素的检出率为100%。环丙沙星和诺氟沙星是土壤样品中含量最高的两种抗生素,它们的含量范围分别是13.7~32.1和15.6~43.6 μg/kg。本研究建立的方法简单、快速、溶剂使用量少,能用于土壤样品中痕量水平的7类30种抗生素的同时测定。

关键词: 超高效液相色谱-串联质谱, 固相萃取, 抗生素, 土壤

Abstract:

The complexity of the soil matrix, as well as the wide spectrum and trace levels of antibiotic residues in soil, make highly sensitive instrumental methods, efficient purification and enrichment methods, and simultaneous determination of multiple antibiotics key and challenging aspects in the analysis of antibiotics in soil. In this study, a solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry (SPE-UHPLC-MS/MS) method was developed for the simultaneous determination of 30 antibiotics (grouped into seven categories: sulfonamides, fluoroquinolones, tetracyclines, macrolides, β-lactams, amphenicols, and lincosamides) in soil samples.
In the UHPLC-MS/MS experiment, florfenicol and chloramphenicol were analyzed in the negative ionization multiple-reaction monitoring (MRM) mode, and the other 28 target analytes were analyzed in the positive MRM mode. Sensitive MS conditions were realized by optimizing the instrumental parameters such as collision energy and declustering potential. The effects of the injection solvent (proportion of methanol to water) and mobile phase (types and compositions of the solvents) on the shape and intensity of the chromatographic peaks were studied. The optimized UHPLC conditions were as follows: injection solvent, 10%(v/v) methanol aqueous solution; chromatographic column, BEH-C18 column; mobile phase, methanol and water both containing 0.1%(v/v) formic acid; flow rate, 0.4 mL/min; sample injection volume, 5.0 μL. The effects of the extraction solution (the types and compositions of solvents) and clean-up processes (pH of the loading solution, as well as the types and compositions of the rinse solution and elution solvent) on the method performance were investigated. The acetonitrile/Na₂EDTA-McIlvaine buffer showed better extraction efficiency for fluoroquinolones than did the methanol/Na₂EDTA-McIlvaine buffer. Improved recoveries of sulfonamides, macrolides, tetracyclines, and β-lactams were observed when the pH of the loading solution was set to 8.0. The recoveries of sulfadiazine and amoxicillin increased with a decrease in the proportion of methanol to water for the rinse solution. Compared to individual methanol or acetonitrile, the methanol-acetonitrile (1∶1, v/v) mixture showed better elution efficiency for the target analytes. The optimized pretreatment conditions were determined as follows: the soil sample was spiked with mixed internal standards, and then extracted with 10 mL of acetonitrile/Na₂EDTA-McIlvaine buffer (1∶1, v/v) by shaking for 30 min and ultrasonication for 15 min. The extraction was repeated three times. The sample extract was adjusted to pH 8.0 and loaded onto an Oasis HLB cartridge for purification. The cartridge was rinsed with 10 mL of water to remove impurities and eluted with 10 mL of methanol-acetonitrile (1∶1, v/v). Quantitative analysis was conducted using the isotope internal standard method. The method limits of detection and quantification were in the range of 0.013-1.21 and 0.043-4.04 μg/kg, respectively. The correlation coefficients of the calibration curve were 0.992-1.00, suggesting good linearity of the method. At three spiked levels (20, 100, and 200 μg/kg), the average recoveries of most target antibiotics were 44.8% to 164%, and the relative standard deviations were 0.700% to 14.8%. The method was successfully applied to the analysis of the 30 antibiotics in six soil samples. Seventeen antibiotics were detected in the soil samples, and the total contents of the antibiotics in each sample ranged from 73.4 to 184 μg/kg. Twelve antibiotics with a detection frequency of 100% included roxithromycin, clarithromycin, ciprofloxacin, norfloxacin, enrofloxacin, ofloxacin, fleroxacin, lomefloxacin, oxytetracycline, doxycycline, tetracycline, and penicillin G. Ciprofloxacin and norfloxacin were the predominant antibiotics in the soils, with contents in the range of 13.7-32.1 and 15.6-43.6 μg/kg, respectively.
The developed method is simple, rapid, and solvent-saving, and it shows promise for use in the simultaneous determination of trace levels of the 30 antibiotics in soil.

Key words: ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), solid phase extraction (SPE), antibiotics, soil

中图分类号:

O658

胡钰, 朱青青, 胡立刚, 廖春阳. 超高效液相色谱-串联质谱法同时测定土壤中30种抗生素[J]. 色谱, 2021, 39(8): 878-888.

HU Yu, ZHU Qingqing, HU Ligang, LIAO Chunyang. Simultaneous determination of 30 antibiotics in soil by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2021, 39(8): 878-888.

图/表 8

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Compound	Ion mode	Precursor ion (m/z)	Product ion (m/z)	CE/ eV	DP/ V	Compound	Ion mode	Precursor ion (m/z)	Product ion (m/z)	CE/ eV	DP/ V
Sulfamonomethoxine	ESI⁺	281.2	156.2^*	25	90	Lomefloxacin	ESI⁺	352.1	308.4^*	25	20
(SMM)			92.2	40	90	(LOM)			265.3	30	20
Sulfamethoxazole	ESI⁺	254.2	156.2^*	23	20	Fleroxacin	ESI⁺	370.2	326.3^*	25	80
(SMX)			92.2	35	20	(FLE)			269.1	35	80
Sulfaquinoxaline	ESI⁺	301.2	156.1^*	24	100	Roxithromycin	ESI⁺	837.7	679.5^*	30	20
(SQX)			92.2	38	100	(RTM)			158.3	42	20
Sulfameter	ESI⁺	281.3	156.2^*	25	40	Clarithromycin	ESI⁺	748.7	590.4^*	25	60
(SFM)			92.2	40	40	(CTM)			158.3	35	60
Trimethoprim	ESI⁺	291.3	230.3^*	32	10	Erythromycin-H₂O	ESI⁺	716.6	558.5^*	35	40
(TMP)			123.3	30	10	(ETM-H₂O)			158.3	33	40
Sulfamethazine	ESI⁺	279.2	186.3^*	24	80	Tylosin	ESI⁺	916.7	772.6^*	40	20
(SMZ)			156.2	26	80	(TYL)			174.3	45	20
Sulfadiazine	ESI⁺	251.2	156.2^*	20	20	Oxytetracycline	ESI⁺	461.3	443.2	22	60
(SDZ)			92.2	30	20	(OTC)			426.3^*	27	60
Sulfamethizole	ESI⁺	279.2	156.3^*	20	17	Chlortetracycline	ESI⁺	479.3	462.3	25	40
(SMTZ)			92.3	35	17	(CTC)			444.2^*	30	40
Sulfachlorpyridazine	ESI⁺	285.2	156.2^*	20	20	Doxycycline	ESI⁺	445.3	428.3	25	40
(SCP)			108.2	30	20	(DC)			410.3^*	27	40
Ciprofloxacin	ESI⁺	332.3	314.4^*	30	60	Tetracycline	ESI⁺	445.3	427.2	20	40
(CIP)			288.4	25	60	(TC)			410.2^*	30	35
Norfloxacin	ESI⁺	320.3	302.4^*	30	60	Amoxicillin	ESI⁺	366.2	349.3^*	12	35
(NOR)			276.3	25	60	(AMX)			114.3	30	20
Ofloxacin	ESI⁺	362.3	318.4	37	10	Penicillin-G	ESI⁺	335.2	217.3^*	20	190
(OFL)			261.3^*	27	10	(PCN-G)			202.2	47	130
Enrofloxacin	ESI⁺	360.4	316.4^*	25	20	Lincomycin	ESI⁺	407.2	359.4^*	27	20
(ENR)			245.3	35	20	(LCM)			126.3	35	20
Difloxacin	ESI⁺	400.3	382.4^*	30	40	Florfenicol	ESI^-	355.6	185.1^*	-25	-80
(DIF)			356.4	27	40	(FF)			119.1	-45	-80
Pefloxacin	ESI⁺	334.3	316.3^*	30	40	Chloramphenicol	ESI^-	321.3	257.0^*	-15	-80
(PEF)			290.3	25	40	(CAP)			152.2	-22	-80

Compound	Ion mode	Precursor ion (m/z)	Product ion (m/z)	CE/ eV	DP/ V	Compound	Ion mode	Precursor ion (m/z)	Product ion (m/z)	CE/ eV	DP/ V
Sulfamonomethoxine	ESI⁺	281.2	156.2^*	25	90	Lomefloxacin	ESI⁺	352.1	308.4^*	25	20
(SMM)			92.2	40	90	(LOM)			265.3	30	20
Sulfamethoxazole	ESI⁺	254.2	156.2^*	23	20	Fleroxacin	ESI⁺	370.2	326.3^*	25	80
(SMX)			92.2	35	20	(FLE)			269.1	35	80
Sulfaquinoxaline	ESI⁺	301.2	156.1^*	24	100	Roxithromycin	ESI⁺	837.7	679.5^*	30	20
(SQX)			92.2	38	100	(RTM)			158.3	42	20
Sulfameter	ESI⁺	281.3	156.2^*	25	40	Clarithromycin	ESI⁺	748.7	590.4^*	25	60
(SFM)			92.2	40	40	(CTM)			158.3	35	60
Trimethoprim	ESI⁺	291.3	230.3^*	32	10	Erythromycin-H₂O	ESI⁺	716.6	558.5^*	35	40
(TMP)			123.3	30	10	(ETM-H₂O)			158.3	33	40
Sulfamethazine	ESI⁺	279.2	186.3^*	24	80	Tylosin	ESI⁺	916.7	772.6^*	40	20
(SMZ)			156.2	26	80	(TYL)			174.3	45	20
Sulfadiazine	ESI⁺	251.2	156.2^*	20	20	Oxytetracycline	ESI⁺	461.3	443.2	22	60
(SDZ)			92.2	30	20	(OTC)			426.3^*	27	60
Sulfamethizole	ESI⁺	279.2	156.3^*	20	17	Chlortetracycline	ESI⁺	479.3	462.3	25	40
(SMTZ)			92.3	35	17	(CTC)			444.2^*	30	40
Sulfachlorpyridazine	ESI⁺	285.2	156.2^*	20	20	Doxycycline	ESI⁺	445.3	428.3	25	40
(SCP)			108.2	30	20	(DC)			410.3^*	27	40
Ciprofloxacin	ESI⁺	332.3	314.4^*	30	60	Tetracycline	ESI⁺	445.3	427.2	20	40
(CIP)			288.4	25	60	(TC)			410.2^*	30	35
Norfloxacin	ESI⁺	320.3	302.4^*	30	60	Amoxicillin	ESI⁺	366.2	349.3^*	12	35
(NOR)			276.3	25	60	(AMX)			114.3	30	20
Ofloxacin	ESI⁺	362.3	318.4	37	10	Penicillin-G	ESI⁺	335.2	217.3^*	20	190
(OFL)			261.3^*	27	10	(PCN-G)			202.2	47	130
Enrofloxacin	ESI⁺	360.4	316.4^*	25	20	Lincomycin	ESI⁺	407.2	359.4^*	27	20
(ENR)			245.3	35	20	(LCM)			126.3	35	20
Difloxacin	ESI⁺	400.3	382.4^*	30	40	Florfenicol	ESI^-	355.6	185.1^*	-25	-80
(DIF)			356.4	27	40	(FF)			119.1	-45	-80
Pefloxacin	ESI⁺	334.3	316.3^*	30	40	Chloramphenicol	ESI^-	321.3	257.0^*	-15	-80
(PEF)			290.3	25	40	(CAP)			152.2	-22	-80

Compound	LOD/ (μg/kg)	LOQ/ (μg/kg)	Linear range/ (μg/L)	r	RSDs (intra-day)/%			RSDs (inter-day)/%
Compound	LOD/ (μg/kg)	LOQ/ (μg/kg)	Linear range/ (μg/L)	r	2 μg/L	20 μg/L	100 μg/L	2 μg/L	20 μg/L	100 μg/L
SMM	0.116	0.388	0.01-100	0.997	9.63	2.08	0.619	6.33	5.87	2.08
SMX	0.0459	0.153	0.01-200	0.999	8.81	3.23	1.36	3.26	3.52	2.16
SQX	0.0278	0.0926	0.01-100	0.999	11.3	2.61	1.38	4.52	3.43	1.53
SFM	0.107	0.356	0.01-200	0.999	1.24	1.42	2.59	5.86	4.70	4.49
TMP	0.0388	0.129	0.01-100	0.999	8.68	6.95	1.09	3.95	2.65	2.21
SMZ	0.0284	0.0946	0.01-200	0.999	1.07	1.88	0.613	4.38	1.04	4.06
SDZ	0.0130	0.0433	0.01-200	0.999	5.69	0.730	2.56	2.63	0.507	2.97
SMTZ	0.0325	0.108	0.02-100	1.000	5.48	0.274	3.22	8.68	6.11	12.2
SCP	0.0612	0.204	0.01-100	0.996	11.8	3.11	2.40	6.08	6.00	3.04
RTM	0.0673	0.224	0.01-100	0.999	1.41	6.96	3.83	3.86	10.1	1.19
CTM	0.0492	0.164	0.01-100	0.999	4.76	2.84	3.25	13.1	10.7	1.74
ETM-H₂O	0.0313	0.104	0.02-100	0.999	5.98	2.42	4.44	13.1	4.53	4.97
TYL	0.104	0.347	0.5-200	1.000	3.36	3.58	0.515	14.0	13.8	14.2
CIP	0.623	2.08	2-200	0.998	10.1	3.13	13.7	7.17	13.9	6.54
NOR	0.619	2.06	2-200	0.997	1.36	4.43	12.1	2.86	9.70	12.9
OFL	0.112	0.373	1-200	0.992	9.05	3.38	6.28	9.97	12.8	5.54
ENR	0.104	0.348	1-200	0.999	11.6	3.04	8.07	12.0	8.67	1.15
DIF	0.147	0.492	0.02-200	0.998	10.5	3.11	4.19	9.96	3.37	3.62
PEF	0.197	0.658	0.2-200	0.998	6.00	2.22	12.4	10.0	3.70	4.64
FLE	0.0513	0.171	0.1-100	0.999	9.41	5.31	1.36	3.55	14.0	7.65
LOM	0.129	0.429	0.2-100	0.998	11.9	4.38	3.58	11.4	5.12	13.9
OTC	0.122	0.407	0.5-200	0.995	4.89	4.03	8.99	8.81	3.79	8.31
CTC	1.21	4.04	0.02-200	0.998	11.5	5.23	2.51	13.7	7.91	6.42
DC	0.168	0.560	0.1-200	0.997	14.1	1.82	5.05	13.3	1.60	14.5
TC	0.209	0.698	0.02-200	0.997	11.3	4.66	3.81	7.28	2.85	14.3
AMX	0.119	0.395	0.5-200	0.999	0.964	1.55	8.62	2.96	14.4	13.5
PCN-G	0.134	0.446	0.2-200	1.000	10.4	1.54	4.59	14.3	11.0	11.7
LCM	0.0251	0.0836	0.02-200	0.998	11.4	4.74	0.476	11.4	8.93	6.44
CAP	1.06	3.55	0.01-200	0.998	2.67	2.84	0.238	10.8	12.5	8.81
FF	0.166	0.553	0.01-200	0.998	2.42	1.39	4.90	13.1	9.88	7.60

Compound	LOD/ (μg/kg)	LOQ/ (μg/kg)	Linear range/ (μg/L)	r	RSDs (intra-day)/%			RSDs (inter-day)/%
Compound	LOD/ (μg/kg)	LOQ/ (μg/kg)	Linear range/ (μg/L)	r	2 μg/L	20 μg/L	100 μg/L	2 μg/L	20 μg/L	100 μg/L
SMM	0.116	0.388	0.01-100	0.997	9.63	2.08	0.619	6.33	5.87	2.08
SMX	0.0459	0.153	0.01-200	0.999	8.81	3.23	1.36	3.26	3.52	2.16
SQX	0.0278	0.0926	0.01-100	0.999	11.3	2.61	1.38	4.52	3.43	1.53
SFM	0.107	0.356	0.01-200	0.999	1.24	1.42	2.59	5.86	4.70	4.49
TMP	0.0388	0.129	0.01-100	0.999	8.68	6.95	1.09	3.95	2.65	2.21
SMZ	0.0284	0.0946	0.01-200	0.999	1.07	1.88	0.613	4.38	1.04	4.06
SDZ	0.0130	0.0433	0.01-200	0.999	5.69	0.730	2.56	2.63	0.507	2.97
SMTZ	0.0325	0.108	0.02-100	1.000	5.48	0.274	3.22	8.68	6.11	12.2
SCP	0.0612	0.204	0.01-100	0.996	11.8	3.11	2.40	6.08	6.00	3.04
RTM	0.0673	0.224	0.01-100	0.999	1.41	6.96	3.83	3.86	10.1	1.19
CTM	0.0492	0.164	0.01-100	0.999	4.76	2.84	3.25	13.1	10.7	1.74
ETM-H₂O	0.0313	0.104	0.02-100	0.999	5.98	2.42	4.44	13.1	4.53	4.97
TYL	0.104	0.347	0.5-200	1.000	3.36	3.58	0.515	14.0	13.8	14.2
CIP	0.623	2.08	2-200	0.998	10.1	3.13	13.7	7.17	13.9	6.54
NOR	0.619	2.06	2-200	0.997	1.36	4.43	12.1	2.86	9.70	12.9
OFL	0.112	0.373	1-200	0.992	9.05	3.38	6.28	9.97	12.8	5.54
ENR	0.104	0.348	1-200	0.999	11.6	3.04	8.07	12.0	8.67	1.15
DIF	0.147	0.492	0.02-200	0.998	10.5	3.11	4.19	9.96	3.37	3.62
PEF	0.197	0.658	0.2-200	0.998	6.00	2.22	12.4	10.0	3.70	4.64
FLE	0.0513	0.171	0.1-100	0.999	9.41	5.31	1.36	3.55	14.0	7.65
LOM	0.129	0.429	0.2-100	0.998	11.9	4.38	3.58	11.4	5.12	13.9
OTC	0.122	0.407	0.5-200	0.995	4.89	4.03	8.99	8.81	3.79	8.31
CTC	1.21	4.04	0.02-200	0.998	11.5	5.23	2.51	13.7	7.91	6.42
DC	0.168	0.560	0.1-200	0.997	14.1	1.82	5.05	13.3	1.60	14.5
TC	0.209	0.698	0.02-200	0.997	11.3	4.66	3.81	7.28	2.85	14.3
AMX	0.119	0.395	0.5-200	0.999	0.964	1.55	8.62	2.96	14.4	13.5
PCN-G	0.134	0.446	0.2-200	1.000	10.4	1.54	4.59	14.3	11.0	11.7
LCM	0.0251	0.0836	0.02-200	0.998	11.4	4.74	0.476	11.4	8.93	6.44
CAP	1.06	3.55	0.01-200	0.998	2.67	2.84	0.238	10.8	12.5	8.81
FF	0.166	0.553	0.01-200	0.998	2.42	1.39	4.90	13.1	9.88	7.60

Compound	Recoveries (RSDs)/% (n=4)			Matrix effect/%	Compound	Recoveries (RSDs)/% (n=4)			Matrix effect/%
Compound	20 μg/kg	100 μg/kg	200 μg/kg	Matrix effect/%	Compound	20 μg/kg	100 μg/kg	200 μg/kg	Matrix effect/%
SMM	79.0 (3.02)	53.0 (12.0)	51.4 (5.69)	48.0-56.2	OFL	126.0 (2.67)	87.1 (14.8)	75.2 (10.2)	73.9-110
SMX	94.4 (3.71)	72.3 (12.6)	82.1 (11.3)	51.5-65.3	ENR	78.0 (14.4)	77.0 (12.9)	70.7 (6.53)	68.4-110
SQX	45.2 (4.39)	31.5 (13.7)	27.1 (7.26)	27.7-34.2	DIF	109.0 (2.57)	78.8 (12.0)	63.3 (5.48)	61.4-73.7
SFM	111.0 (8.60)	76.3 (8.21)	70.9 (10.1)	67.8-78.1	PEF	128.0 (5.61)	125.0 (12.5)	88.0 (11.3)	94.6-138
TMP	123.0 (2.77)	84.4 (13.1)	70.6 (10.0)	68.0-78.0	FLE	90.2 (6.56)	51.9 (14.5)	44.8 (10.0)	45.5-71.7
SMZ	101.0 (5.05)	66.4 (8.97)	68.5 (7.88)	62.5-75.6	LOM	71.4 (13.5)	69.5 (10.3)	55.8 (12.7)	64.6-78.0
SDZ	94.2 (14.4)	87.6 (14.8)	75.5 (9.10)	71.5-86.7	OTC	164.0 (6.40)	121.0 (11.0)	87.8 (4.86)	73.3-116
SMTZ	101.0 (6.75)	57.4 (11.3)	53.7 (11.7)	63.1-72.9	CTC	136.0 (15.2)	122.0 (17.3)	143.0 (7.58)	48.3-67.3
SCP	90.5 (2.51)	57.9 (10.1)	55.3 (8.06)	56.7-65.5	DC	138.0 (6.29)	74.5 (7.50)	70.7 (5.52)	69.6-115
RTM	89.5 (9.01)	73.7 (8.46)	60.9 (3.43)	68.3-133	TC	146.0 (11.5)	79.2 (12.8)	69.5 (8.45)	73.8-119
CTM	54.5 (10.1)	53.1 (10.3)	45.3 (3.64)	56.8-81.1	AMX	29.6 (6.11)	45.1 (5.39)	43.0 (9.40)	66.5-91.0
ETM-H₂O	57.8 (12.8)	57.6 (13.4)	48.9 (0.700)	53.7-70.9	PCN-G	78.5 (3.31)	29.1 (2.76)	30.6 (8.90)	38.3-40.0
TYL	67.3 (8.16)	75.5 (11.0)	70.8 (3.99)	91.5-115	LCM	70.9 (7.37)	74.9 (4.17)	55.3 (5.69)	74.5-88.4
CIP	45.8 (11.9)	82.9 (10.9)	69.0 (6.11)	91.4-134	FF	96.5 (5.94)	59.9 (11.7)	46.9 (8.50)	44.4-52.4
NOR	64.2 (5.17)	107.0 (11.9)	89.1 (7.73)	137.0-172	CAP	146.0 (8.11)	95.3 (13.5)	80.9 (5.79)	69.4-81.6

超高效液相色谱-串联质谱法同时测定土壤中30种抗生素

Simultaneous determination of 30 antibiotics in soil by ultra-high performance liquid chromatography-tandem mass spectrometry

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Metrics

Matrix	Category	N ³⁾	Recoveries/%	LOQs/ (μg/kg)	Extraction solvent	Purification and detection method	Reference
Soil	SAs, FQs, TCs, MLs, BLs, LAs¹⁾, APHs	30	27.1-164	0.0430-4.04	ACN/Na₂EDTA-McIlvaine (1∶1, v/v, 10 mL×3)	HLB-UHPLC-MS/MS	this work
Soil	MLs, FQs, LAs	9	65.2-106	0.800-9.67	ACN/Na₂EDTA-H₃PO₄ (1∶1, v/v, 20 mL×2)	SAX-HLB-UHPLC-MS/MS	[10]
Soil	SAs, BLs, APHs	13	78.5-107	1.33-3.33	ACN/Na₂EDTA-McIlvaine (1∶1, v/v, 20 mL×3)	HLB-HPCE	[11]
Soil	SAs, MLs	20	61.4-119	2.00-5.00	QuEChERS	HPLC-MS/MS	[12]
Soil	SAs, TCs	6	40-114	0.600-2.30	Na₂EDTA-McIlvaine (20 mL)	SPE-HPLC-MS/MS	[21]
Soil	SAs, FQs, MLs	22	53.3-112	0.00670-0.017	ACN/Na₂EDTA-McIlvaine (2/1, v/v, 15 mL×3)	HLB-HPLC-MS/MS	[22]
Manure	BLs	5	15.0-87.1⁴⁾	1.13-6.20⁵⁾		SPE-HPLC-MS/MS	[19]
Manure	SAs, FQs, TCs, MLs, LAs, PMs²⁾	25	61.4-106 (SQX: 55.7-56.8)	0.05-5.91	QuEChERS	HPLC-MS/MS	[20]
Waste-water	SAs, FQs, MLs, BLs, LAs, APHs	11	20-180	0.01-0.02⁶⁾		HLB-HPLC-MS/MS	[6]

Compound	GM/ (μg/kg)	Min/ (μg/kg)	Max/ (μg/kg)	DF/%	Compound	GM/ (μg/kg)	Min/ (μg/kg)	Max/ (μg/kg)	DF/%
SMM	0.274	nd	nd	0	OFL	8.07	5.83	16.1	100
SMX	0.108	nd	nd	0	ENR	6.41	4.37	11.1	100
SQX	0.0812	nd	0.238	16.7	DIF	2.02	nd	7.75	83.3
SFM	0.252	nd	nd	0	PEF	0.995	nd	8.51	33.3
TMP	0.125	nd	0.235	50.0	FLE	0.952	0.503	3.49	100
SMZ	0.0669	nd	nd	0	LOM	3.96	2.27	9.80	100
SDZ	0.0306	nd	nd	0	OTC	6.23	3.14	14.0	100
SMTZ	0.0767	nd	nd	0	CTC	2.86	nd	nd	0
SCP	0.144	nd	nd	0	DC	6.14	3.63	14.3	100
RTM	1.00	0.824	1.41	100	TC	5.79	3.45	14.4	100
CTM	0.326	0.255	0.496	100	AMX	0.279	nd	nd	0
ETM-H₂O	0.0738	nd	nd	0	PCN-G	4.57	2.74	11.1	100
TYL	0.658	nd	1.23	83.3	LCM	0.0591	nd	nd	0
CIP	19.5	13.7	32.1	100	FF	0.391	nd	nd	0
NOR	24.2	15.6	43.6	100	CAP	2.51	nd	nd	0

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