CN104730168A - Synchronous detection method of tetracyclines, fluoroquinolones and sulfonamide antibiotics remained in water body - Google Patents
Synchronous detection method of tetracyclines, fluoroquinolones and sulfonamide antibiotics remained in water body Download PDFInfo
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Abstract
The invention belongs to the technical field of detection of enrichment of remained antibiotics in a water body environment, and particularly relates to a synchronous detection method of tetracyclines, fluoroquinolones and sulfonamide antibiotics remained in the water body. The detection method comprises the following steps: (1) performing water sample pretreatment; (2) performing small-column enrichment of target antibiotics by using solid-phase extraction; (3) detecting on a machine by using high performance liquid chromatography and tandem mass spectrum. According to the method, once the sample feeding is carried out at one time, multiple antibiotics in the water body can be detected at the same time, the time consumption of a detection process is reduced, the detection accuracy and sensitivity are increased, the detection limit is low, and the condition of the trace amount of remained antibiotics in the water body environment can be detected; meanwhile, the detection method is convenient to operate and low in environment toxicity and is low in using amount of organic reagents.
Description
Technical field
The invention belongs to the enrichment detection technique field of residual antibiotic in water body environment, be specifically related to a kind of method that residue in water Tetracyclines, fluoroquinolones and sulfa antibiotics synchronously detect.
Background technology
Microbiotic causes a large amount of concern in recent years as pollutant emerging in environment, and because its long duration is input in environment, academia calls it as false persistent organism.In China, abuse of antibiotics situation was serious in the last few years, was widely used in animal husbandry and pharmacy industry.Microbiotic wide material sources in environment, comprise the untreated discharge of production waste of pharmaceutical factory and the mishandling of expired medicament all can cause in environment antibiotic residual.In addition, research shows, the microbiotic used in the mankind and animal feeding process, wherein 30%-90% gets rid of external without effective utilization of biosome by excretas such as ight soil, the microbiotic in sanitary sewage effectively cannot be removed by sewage treatment plant, and then makes a large amount of microbiotic enter into environment.Microbiotic and metabolic product thereof enter into environment water by number of ways, cause the pollution of environment water.Because microbiotic generally has sterilizing function, microbiotic residual is in the environment conducive to promoting that the gene evolution of occurring in nature bacterium produces drug tolerant bacteria, and this will cause serious threat to the ecologic equilibrium in the health of the mankind and biosphere.
The means of antibiotic residue in testing environment sample, mainly concentrate at present and use Solid-Phase Extraction-using high performance liquid chromatography tandem mass spectrum method.The advantage of the method is shorter, high sensitivity, low detectability easy and simple to handle, consuming time.But in current existing research, to be mostly for a few microbiotic and the microbiotic belonging to same type detects more, although reach the object detected simultaneously, method still has limitation.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, object is a kind of method providing residue in water Tetracyclines, fluoroquinolones and sulfa antibiotics synchronously to detect.
For achieving the above object, the technical solution adopted in the present invention is:
The method that residue in water Tetracyclines, fluoroquinolones and sulfa antibiotics synchronously detect, comprises the steps:
(1) water sample pre-treatment: water sample regulates pH to 3 ~ 4 after membrane filtration, then add sequestrant Na
2-EDTA, obtains treating enrichment water sample;
(2) solid phase extraction column enrich target microbiotic is used: successively with methyl alcohol and ultrapure water activated solid extraction pillar, then pass into and treat enrichment water sample, control water sample flow velocity, make target microbiotic in water sample by adsorption and enrichment on solid phase extraction column, after sample all imports, with ultrapure water drip washing solid phase extraction column, and drain solid phase extraction column under vacuum, re-use methanol-eluted fractions, collect eluent and concentrate under nitrogen purge, obtaining concentrating sample;
(3) upper machine testing: by concentrating sample methyl alcohol: the solution of 0.1% formic acid water=1:1 is settled to 1mL, adds internal standard compound, the content of Tetracyclines, fluoroquinolones and sulfa antibiotics in upper machine testing sample.
By such scheme, the filtering membrane of step (1) described membrane filtration is 0.45 μm of glass fiber filter.The solution of described adjustment pH is hydrochloric acid solution.
By such scheme, step (2) described solid phase extraction column is the Oasis HLB pillar of 60mg/3mL specification.
By such scheme, the water sample flow velocity described in step (2) is: 0.5 ~ 5mL/min.
By such scheme, step (3) described internal standard compound is 100ng Gesadrual.
By such scheme, the checkout equipment that the described upper machine testing of step (3) uses is using high performance liquid chromatography tandem mass spectrum.
By such scheme, the optimum configurations of described high performance liquid chromatography is: mobile phase A is acetonitrile, and Mobile phase B is the ultrapure water containing 0.1% formic acid and 5mmol/L ammonium acetate, and flow velocity is 0.25mL/min; Gradient is mobile phase A initial concentration is 15%, keep 2min, after in 3min, be increased to 90%, keep 2min, be then reduced to 15% at 3min and keep 5min, the total used time 15min of wash-out; Sampling volume is 5 μ L; Use chromatographic column is Extend-C18column (1.8 μm, 2.1mm i.d. × 100mm, Agilent, USA), and temperature keeps 40 DEG C; Described mass spectrographic optimum configurations is: cation mode; Dry gas temperature is 325 DEG C; Dry gas flow velocity is 6L/min; Capillary voltage is 3500V; Electron spray pressure is 40psi.
Beneficial effect of the present invention is as follows: (1) the present invention once goes up machine sample introduction can detect Multiple Classes of Antibiotics (21 kinds of microbiotic) in water body simultaneously, testing process few (15min consuming time) consuming time, the degree of accuracy and highly sensitive detected, detection limit is low, can detect the residual condition of traces of antibiotic in environment water; Meanwhile, the inventive method also has high-recovery, and relative standard deviation is less, and this illustrates the pre-treating method of the application and detection method is reliable and repeating effect is good; (2) detection method is easy and simple to handle, and organic reagent use amount is few, and environmental toxicity is low.
Accompanying drawing explanation
Fig. 1 is that in varying environment water sample (underground water, river, waste water), the microbiotic recovery compares.
Fig. 2 is 100 μ gL
-1the total ion current figure of 21 kinds of microbiotic hybrid standard product solution of concentration, horizontal ordinate is retention time, and ordinate is signal intensity.
Fig. 3 is the concentration-peak area typical curve of the main residual antibiotic (aureomycin, Doxycycline, Sparfloxacin, Nuo Fosha star, sulfamethazine, Sulfamethoxazole) in environmental water sample, wherein horizontal ordinate is antibiotic concentration and interior mark concentration proportion, and ordinate is microbiotic peak area and interior mark peak area ratio.
Fig. 4 is main residual antibiotic (aureomycin, Doxycycline, Sparfloxacin, Nuo Fosha star, sulfamethazine, Sulfamethoxazole) the Selective ion mode spectrogram under 100 μ g/L concentration in environmental water sample.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
The pre-service of embodiment 1 water sample
The all glasswares used in experiment all clean through organic washing lotion, leave standstill and use tap water, milli-Q water eight times successively after 4 hours.In experimentation, light source direct projection avoided by sample, and glassware counter used is divided into brown, and but part needs the step of observing sample phenomenon then to use flint glass vessel need be overlying on surface with lucifuge with aluminium foil.
The sample that can measure different volumes for dissimilar water sample carries out concentrated and can reach can detectable concentration, obtains, underground water 1L, river 0.5L, waste water 0.1L through series of experiments.The water sample of certain volume is weighed with graduated cylinder, this water sample through the glass filter of the glass fiber filter being furnished with 0.45 μm, collecting the water sample through filtering, regulating water sample to be after filtration 3 ~ 4 to pH with hydrochloric acid solution, then adding the sequestrant Na that 10mL concentration is 5% (v/v)
2-EDTA, to prevent the metal cation complexing in TCs and water body and then to affect the antibiotic detection of target.
Embodiment 2 solid phase extraction method
(1) activated solid extraction column
The solid-phase extraction column of Waters Oasis HLB 60mg/3mL specification is used to extract.Solid-phase extraction column first adds the chromatographically pure methanol solution of 6mL before using wherein, and make under gravity methanol solution slowly by solid matter to activate.For avoiding residual methanol solvent in solid phase to have an impact to the enrichment of wherein target compound when passing into water sample, then add 6mL ultrapure water wherein, equally under gravity by solid matter, to complete activation.
(2) pretreatment sample is imported
In the solid-phase extraction column after overactivation, pass into pretreated water sample, through flow control contrast experiment, the present invention selects flow velocity to be underground water 5mL/min, river 2.5mL/min, waste water 0.5mL/min.Concrete operations are connection 12 pipe solid-phase extraction device, waste liquid bottle and vacuum pump, open vacuum pump, regulate the flow control valve coutroi velocity on the extraction equipment of each solid-phase extraction column lower end, by Large Copacity injector, water sample is imported in solid-phase extraction column, water sample by target compound in solid matter process by adsorption and enrichment on solid matter, aqueous sample stream is to waste liquid bottle afterwards.
(3) drip washing solid-phase extraction column
In the process of water sample by solid-phase extraction column, not only target compound is by solid matter adsorption and enrichment, and in water sample, some non-checked for impurities also can partly remain in solid-phase extraction column, as the sequestrant Na added in water sample pre-treatment step
2-EDTA etc.Therefore under equal conditions impurity is removed by solid-phase extraction column with drip washing solid matter with 12mL ultrapure water.After drip washing, under vacuumized conditions, after dry solid-phase extraction column 10min, wait for wash-out.
(4) wash-out solid-phase extraction column
The present invention found through experiments, and methyl alcohol is best for the elute effect of three major types target compound.Therefore in the solid-phase extraction column drained, 6mL methanol solution is added, under gravity by the microbiotic wash-out that adsorbs in solid matter out, collect in glass test tube, finally open vacuum pump applying negative pressure again and make the methyl alcohol in solid-phase extraction column all flow out and collect.
(5) eluent nitrogen flushing constant volume
Carrying out purging under the eluent collected in glass test tube being placed on gentle stream of nitrogen gas makes methyl alcohol volatilize, nitrogen flushing is stopped when eluent is concentrated into about 0.5mL, transfer them in the brown sample injection bottle of 2mL, continuing nitrogen flushing after adding 100ng interior mark compound Gesadrual is concentrated near dry, use methyl alcohol again: the solution of 0.1% formic acid water=1:1 is settled to 1mL, be placed in 4 DEG C of refrigerators and wait for upper machine testing.
Embodiment 3:HPLC-MS/MS detection method is set up
For traces of antibiotic in sample, use using high performance liquid chromatography tandem mass spectrum to detect, be equipped with high-performance automatic sampler, binary pump, constant temperature chromatogram column compartment and variable-wavelenght detector, concrete detected parameters sees the following form 1.
Table 1 using high performance liquid chromatography tandem mass spectrum (HPLC-MS/MS) detected parameters
Embodiment 4: data processing
Target microbiotic adopts internal standard method matching standard curve to carry out quantitatively.Prepare 21 kinds of antibiotic mixed standard solutions of 6 groups of concentration, 6 groups of concentration are respectively 5 μ g/L, 25 μ g/L, 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, wherein often organize often kind of antibiotic concentration in the mixed standard solution of concentration identical, in 6 groups of mixed standard solutions, often kind of antibiotic concentration is respectively: 5 μ g/L, 25 μ g/L, 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, mark Gesadrual in 100ng is all injected in the standard solution of each concentration, concentration detects with the instrumental method in embodiment 3 from low to high successively, obtain the standard correction curve of 6 matchings, transverse axis X is the ratio of target microbiotic peak area and interior mark peak area, longitudinal axis Y is the ratio of target antibiotic concentration and interior mark concentration, the R of standard correction curve
2value is between 0.9-0.9999, and the concentration-peak area typical curve of the main residual antibiotic (aureomycin, Doxycycline, Sparfloxacin, Nuo Fosha star, sulfamethazine, Sulfamethoxazole) wherein in environmental water sample is shown in Fig. 3.
Embodiment 5: recovery experiment
Adopt the standard addition method detection method recovery, prepare 21 kinds of microbiotic mixed standard solutions.For water body of different nature, after having weighed the water sample of certain volume, first inject certain density mixed standard solution wherein, carry out water sample pre-treatment according to step described in embodiment 1 afterwards, ensuing disposal route and detection method are as previous embodiment 2,3,4.Each group recovery experiment comprises injects 3, mixed standard solution sample, and do not inject mixed standard solution sample and blank sample 3, the computing formula of ult rec is as follows:
R: the recovery, %;
C
0: the concentration of hybrid standard liquid, ng/mL;
C
1: the detectable concentration not adding the sample of hybrid standard liquid, ng/mL;
C
2: the detectable concentration adding the sample of mixed standard solution, ng/mL;
V
0: the volume of hybrid standard liquid, mL;
V
1: constant volume before machine on the sample not adding hybrid standard liquid, mL;
V
2: constant volume before machine on the sample adding mixed standard solution, mL;
Herein, V
1=V
2=1mL.
Embodiment 6: acquisition test field actual water sample mark-on reclaims measurement result
Gather Jianghan Plain underground water, river and Pig raising wastewater water sample, according to previous embodiment progressively enrichment detect, obtain in three kinds of environmental water samples that 21 kinds of antibiotic concentration residual condition are in table 2, the mark-on of three kinds of water bodys reclaims and the results are shown in Figure 1.As shown in Figure 1, make to use the same method and Treatment Analysis is carried out to different aqueous samples, in underground water, river and Pig raising wastewater, antibiotic recovery scope is respectively 63-123%, 64-123% and 57-116%, the recovery there are differences, there is matrix interference in explanation, use standard addition method calculate the recovery and correct testing result with it, the impact that matrix interference is brought can be reduced to a certain extent; As shown in Table 2, use the method that the present invention relates to, all detect antibiotic residue in three kinds of water bodys, and residual level in Pig raising wastewater is the highest, the residual level in underground water is minimum.The result of table 2 also demonstrates detection method can detect Multiple Classes of Antibiotics (21 kinds of microbiotic) in water body, testing process few (15min consuming time) consuming time simultaneously, the degree of accuracy of detection and highly sensitive.
Compared with prior art, detection method of the present invention is lower to detection limit antibiotic in underground water, river and Pig raising wastewater, and in three kinds of water bodys, 21 kinds of antibiotic detection limit scopes are respectively 0.03-2.16ngL
-1, 0.08-4.91ngL
-1and 1.39-21.73ngL
-1the antibiotic residue situation of low concentration in environment water can be detected, in addition, detection method of the present invention is less to the relative standard deviation of antibiotic residue Concentration Testing in underground water, river and Pig raising wastewater, the standard deviation variation range of three kinds of water samples is respectively 0.1-7.1%, 0.1-3.3% and 0.1-9.5%, illustrates the pre-treating method of the application and detection method is reliable and repeating effect is good.
21 kinds of antibiotic residual concentrations in table 2 three kinds of environmental samples
Obviously, above-described embodiment is only for the example done clearly is described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And therefore amplified apparent change or variation are still within the protection domain of the invention.
Claims (7)
1. the method that synchronously detects of residue in water Tetracyclines, fluoroquinolones and sulfa antibiotics, is characterized in that, comprise the steps:
(1) water sample pre-treatment: water sample regulates pH to 3 ~ 4 after membrane filtration, then add sequestrant Na
2-EDTA, obtains treating enrichment water sample;
(2) solid phase extraction column enrich target microbiotic is used: successively with methyl alcohol and ultrapure water activated solid extraction pillar, then pass into and treat enrichment water sample, control water sample flow velocity, make target microbiotic in water sample by adsorption and enrichment on solid phase extraction column, after sample all imports, with ultrapure water drip washing solid phase extraction column, and drain solid phase extraction column under vacuum, re-use methanol-eluted fractions, collect eluent and concentrate under nitrogen purge, obtaining concentrating sample;
(3) upper machine testing: by concentrating sample methyl alcohol: the solution of 0.1% formic acid water=1:1 is settled to 1mL, adds internal standard compound, the content of Tetracyclines, fluoroquinolones and sulfa antibiotics in upper machine testing sample.
2. detection method according to claim 1, is characterized in that, the filtering membrane of step (1) described membrane filtration is 0.45 μm of glass fiber filter.
3. detection method according to claim 1, is characterized in that, step (2) described solid phase extraction column is the Oasis HLB pillar of 60mg/3mL specification.
4. detection method according to claim 1, is characterized in that, the water sample flow velocity described in step (2) is: 0.5 ~ 5mL/min.
5. detection method according to claim 1, is characterized in that, step (3) described internal standard compound is 100ng Gesadrual.
6. detection method according to claim 1, is characterized in that, the checkout equipment that the described upper machine testing of step (3) uses is using high performance liquid chromatography tandem mass spectrum.
7. detection method according to claim 6, is characterized in that, the optimum configurations of described high performance liquid chromatography is: mobile phase A is acetonitrile, and Mobile phase B is the ultrapure water containing 0.1% formic acid and 5mmol/L ammonium acetate; Flow velocity is 0.25mL/min; Gradient is mobile phase A initial concentration is 15%, keep 2min, after in 3min, be increased to 90%, keep 2min, be then reduced to 15% at 3min and keep 5min, the total used time 15min of wash-out; Sampling volume is 5 μ L; Use chromatographic column is Extend-C18column, and temperature keeps 40 DEG C; Described mass spectrographic optimum configurations is: cation mode; Dry gas temperature is 325 DEG C; Dry gas flow velocity is 6L/min; Capillary voltage is 3500V; Electron spray pressure is 40psi.
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| CN105004831A (en) * | 2015-07-21 | 2015-10-28 | 金河生物科技股份有限公司 | Method for determining aureomycin premix content and related substances through high-performance liquid chromatography method |
| CN105699537A (en) * | 2016-04-07 | 2016-06-22 | 大连理工大学 | Synchronous detection method for plurality of types of drug residues in water body |
| CN105929047A (en) * | 2016-04-19 | 2016-09-07 | 山东省科学院新材料研究所 | Method for determining antibiotics in livestock and poultry breeding wastewater |
| CN107024548A (en) * | 2016-07-10 | 2017-08-08 | 华中农业大学 | The method for detecting 92 kinds of antibacterial medicine residues in water environment simultaneously |
| CN107490649A (en) * | 2017-09-15 | 2017-12-19 | 河南省兽药饲料监察所 | The screening method of 62 kinds of antibacterials in a kind of farm animal excrement |
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| CN113063864A (en) * | 2021-03-17 | 2021-07-02 | 湖北省地质实验测试中心(国土资源部武汉矿产资源监督检测中心) | Method for extracting and measuring sulfonamide antibiotics in solid-state environment sample by using aqueous solvent |
| CN113109481A (en) * | 2021-04-29 | 2021-07-13 | 厦门理工学院 | Method for simultaneously detecting four types of 13 antibiotics in drinking water source water body by solid phase extraction-liquid chromatography tandem mass spectrometry |
| CN113945658A (en) * | 2021-10-13 | 2022-01-18 | 深圳技师学院（深圳高级技工学校） | Method for simultaneously determining content of 7 antibiotics in water sample |
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| CN105929047A (en) * | 2016-04-19 | 2016-09-07 | 山东省科学院新材料研究所 | Method for determining antibiotics in livestock and poultry breeding wastewater |
| CN106018636B (en) * | 2016-06-30 | 2018-08-24 | 中国水产科学研究院长江水产研究所 | A kind of kit, sample-pretreating method and dithiocyano-methane detection method |
| CN107024548A (en) * | 2016-07-10 | 2017-08-08 | 华中农业大学 | The method for detecting 92 kinds of antibacterial medicine residues in water environment simultaneously |
| CN107490649A (en) * | 2017-09-15 | 2017-12-19 | 河南省兽药饲料监察所 | The screening method of 62 kinds of antibacterials in a kind of farm animal excrement |
| CN110501203A (en) * | 2019-08-05 | 2019-11-26 | 未名环境分子诊断(广东)有限公司 | The Preconcentration in-situ purification device and method of psychoactive drug substance in a kind of water environment |
| CN110501203B (en) * | 2019-08-05 | 2024-04-02 | 未名环境分子诊断(广东)有限公司 | On-site rapid enrichment and purification device and method for mental active substances in water environment |
| CN113063864A (en) * | 2021-03-17 | 2021-07-02 | 湖北省地质实验测试中心(国土资源部武汉矿产资源监督检测中心) | Method for extracting and measuring sulfonamide antibiotics in solid-state environment sample by using aqueous solvent |
| CN113109481A (en) * | 2021-04-29 | 2021-07-13 | 厦门理工学院 | Method for simultaneously detecting four types of 13 antibiotics in drinking water source water body by solid phase extraction-liquid chromatography tandem mass spectrometry |
| CN113945658A (en) * | 2021-10-13 | 2022-01-18 | 深圳技师学院（深圳高级技工学校） | Method for simultaneously determining content of 7 antibiotics in water sample |
| CN113945658B (en) * | 2021-10-13 | 2023-10-31 | 深圳技师学院（深圳高级技工学校） | Method for simultaneously measuring contents of 7 antibiotics in water sample |
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