CN104198626A - Method for extracting, enriching and quantifying trace enrofloxacin on suspended particulate matters in water - Google Patents
Method for extracting, enriching and quantifying trace enrofloxacin on suspended particulate matters in water Download PDFInfo
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- CN104198626A CN104198626A CN201410416824.7A CN201410416824A CN104198626A CN 104198626 A CN104198626 A CN 104198626A CN 201410416824 A CN201410416824 A CN 201410416824A CN 104198626 A CN104198626 A CN 104198626A
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Abstract
The invention discloses a method for extracting, enriching and quantifying trace enrofloxacin on suspended particulate matters in water. The method comprises the following steps: filtering a target water sample by using a microporous fiber membrane, collecting the filtered membrane, airing the filtration membrane and then cutting the filtration membrane into pieces, putting the pieces in a triangular flask, adding an extraction agent, sealing, oscillating and carrying out ultrasonic extraction; filtering the extraction solution by using an organic filtration membrane and simultaneously transferring the filtered extraction solution to a K-D concentration bottle; adding a dehydration drying agent to the filtered extract solution, drying water and putting the K-D concentration bottle in a rotary evaporator for concentrating; blowing the concentrated solution until the volume is smaller than 1mL by using nitrogen; extracting the concentrated solution, making the volume of the filtered solution to be 1mL, then transferring the solution to a special Agilent bottle; detecting by using a high-performance liquid chromatography-tandem tertiary mass spectrometry combined instrument by virtue of an internal standard method; and analyzing a chromatography-mass spectrometry analysis diagram to complete detection. By virtue of the method, the content of the enrofloxacin adsorbed by the suspended particulate matters in the water environment is supplemented; and the blank of detection of antibiotics is filled up.
Description
Technical field
The invention belongs to environmental monitoring technology field, relate to the detection method of Enrofloxacin in a kind of water environment, be specifically related in a kind of water the quantivative approach of Enrofloxacin extracting and enriching on particle.
Background technology
Enrofloxacin is the third generation fluoroquinolone antibiotics medicine that is widely used in domestic animal, and it has spectrum antibiotic property, and Gram-negative bacteria and positive bacteria are had to obvious antibacterial action.Therefore, be widely used in livestock culturing and water factory's cultivation.But one of metabolic product of Enrofloxacin Ciprofloxacin, still has powerful antibacterial action, almost all stronger to the antibacterial activity of all pathogens of hydrobiont.
It was reported that, Enrofloxacin does not have complete metabolism in animal body, still has the residual of Enrofloxacin in excreta, by excreta, flows in water environment.In recent years, in water environment, the report of trace enrofloxacin was a lot of both at home and abroad, and concentration is the magnitude to μ g/L by ng/L, and the Enrofloxacin in these water environments, finally enters into potable water system by water intaking, the effectively Technology Need exploitation of Enrofloxacin in degradation water.Therefore,, in order to ensure drinking water safety, accurately detect in water environment, the method for trace enrofloxacin is indispensable prerequisite in water treatment system.
At present, both at home and abroad at extracting and enriching and the quantitative technical also development that detects underwater trace Enrofloxacin, common report has the method for the collaborative using high performance liquid chromatography tandem mass spectrum of Solid-Phase Extraction, before carrying out Solid-Phase Extraction, all water samples need to be through the membrane filtration of 0.45 μ m, the Enrofloxacin of solubilised state, after Solid-Phase Extraction, after enrichment, detects.These methods be confined to solubilised state Enrofloxacin quantitatively on.Studies have reported that, Enrofloxacin belongs to carboxylic acid material, be easy to be adsorbed on particle surface, therefore, the necessary extraction of the Enrofloxacin on particle surface is got off, carry out quantitatively, like this, can omnibearing grasp water in the pollution situation of Enrofloxacin, be to resolve the Transport of Enrofloxacin in water environment, attenuation law in water treatment system, has important supporting role.
Summary of the invention
The object of this invention is to provide in a kind of water trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance.
The object of the invention is by below data-selected scheme being realized:
(1) get target water sample 2000-4000ml, use microporous fibre membrane filtration, collect filter membrane and the surperficial suspended particulate substance of holding back after filtering, after filter membrane is dried, be cut into fragment and be placed in triangular flask, with graduated cylinder, measure appropriate extractant and pour in triangular flask; With sealed membrane good seal, be placed in shaken cultivation case, Temperature Setting is 4-10 ℃, closes illumination and makes its dark, speed setting is 100-200 time/min, after vibration 8-12h, triangular flask is taken out, carry out ultrasonic extraction, extraction time 20-35min, is extracted liquid.
(2) extract obtaining by organic membrane filtration step 1 is transferred to the extract after filtering in the concentrated bottle of K-D simultaneously.
(3) add and dehydrate agent to the extraction filtered fluid in the concentrated bottle of step 2 K-D, after wipe dry, the concentrated bottle of K-D is put into rotary evaporator and concentrate, thickening temperature 30-45 ℃, the time is 10-20min, concentrated after volume be that 1-2ml is advisable.
(4) liquid after step 3 is concentrated is, below 1ml, to stop nitrogen blowing with nitrogen blowing to volume.
(5) concentrate extraction filtered fluid step 4 being obtained is settled to 1mL, and the liquid rotating after constant volume is moved on in Agilent special-purpose bottle.
(6) internal standard compound that adds 0.5ml in the liquid to be measured obtaining in step 5 then detects in three grades of mass spectrometry instruments of ultrahigh pressure liquid phase chromatogram series connection, and detected parameters is as follows:
Liquid-phase condition: a) mobile phase composition: formic acid A.0.2vol.%, B. methyl alcohol; B) sample size: 10 μ L; C) flow velocity: 0.2 mL/min; D) column temperature: 30 ℃; E) working time: 8min; F) chromatographic column: Acquity UPLC BEH; G) gradient: as shown in table 1.
Mass spectrum condition: a) desolventizing temperature degree: 350 ℃; B) source temperature: 150 ℃; C) capillary voltage: 3000V; D) desolventizing gas velocity: 650L/h; E) cone gas velocity: 50L/h.Quantitative and qualitative analysis ion is set in Table 2.
(7) chromatograph mass spectrum analysis figure is analyzed, complete detection.
In said method, the aperture of the microporous fiber membranes that step (1) is described is 0.45 μ m.
In said method, the described quality of suspended particulate substance and the volume ratio of extractant of step (1) is 1g:15-20ml.
In said method, the described extractant of step (1) is methyl alcohol.
In said method, the HZQ-F160 type shaken cultivation case of the oscillator WeiHDL company that step (1) is described, rotating speed is 100-200 time/min; Ultrasonic extracting machine is KQ-100DE type ultrasonic extracting machine, and ultrasonic frequency is 23-40kHz.
In said method, the aperture of organic filter membrane that step (2) is described is 0.22 μ m.
In said method, the described agent that dehydrates of step (3) is anhydrous sodium sulfate.
In said method, the described constant volume organic solvent of step (5) is methyl alcohol.
In said method, the described internal standard compound of step (6) is selected according to actual residue in water situation, and this method adopts sarafloxacin or Lomefloxacin, and structure and Enrofloxacin are similar, at the NF fluoroquinolones material of target water body.Internal standard compound is not only confined to these two kinds, so long as allied substances, its structural similarity, and do not detect and all can in detected water sample.
In said method, the described three grades of mass spectrometry instruments of ultrahigh pressure liquid phase chromatogram series connection of step (6) are Waters Xevo TQ MS Acquity UPLC System, the ultrahigh pressure liquid phase chromatographic column that instrument carries (Acquity UPLC BEH).
Table 1 eluent gradient elution program
Qualitative and the quota ion of table 2 Enrofloxacin
Note: MRM
1for quota ion, MRM
2for qualitative ion.
Tool of the present invention has the following advantages:
1, adopt method provided by the invention, can detect the content of the Enrofloxacin adsorbing on suspended particulate substance in water environment, reflect more really the content of Enrofloxacin in water, thus the pollution situation of Enrofloxacin in omnibearing grasp water.
2, this method is for resolving the Transport of Enrofloxacin in water environment, and the attenuation law in water treatment system, has important supporting role.
3, this method has been supplemented the content of the Enrofloxacin adsorbing on suspended particulate substance in water environment, has supplemented the blank that microbiotic detects.
Accompanying drawing explanation
Fig. 1 is particle extracting and enriching overhaul flow chart.
Embodiment
Below technical scheme of the present invention is further described, but does not limit to so, every technical solution of the present invention is modified or is equal to replacement, and do not depart from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
As shown in Figure 1, trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water provided by the invention, its concrete implementation step is as follows:
(1) get target water sample 2000ml, with 0.45 μ m microporous fibre membrane filtration, collect the filter membrane after filtering, after filter membrane is dried, be cut into fragment and be placed in triangular flask, with graduated cylinder, measure appropriate methyl alcohol and pour in triangular flask, the quality of described suspended particulate substance and the volume ratio of methyl alcohol are 1g:20ml; With sealed membrane good seal, be placed in shaken cultivation case, Temperature Setting is 4 ℃, closes illumination and makes its dark, and speed setting is 100 times/min, after vibration 8h, triangular flask is taken out, and carries out ultrasonic extraction, and extraction time 35min, is extracted liquid.
(2) extract obtaining by the organic membrane filtration step 1 of 0.22 μ m is transferred to the extract after filtering in the concentrated bottle of K-D simultaneously.
(3) add anhydrous sodium sulfate to concentrate the extraction filtered fluid in bottle to step 2 K-D, after wipe dry, the concentrated bottle of K-D is put into rotary evaporator and concentrate, 30 ℃ of thickening temperatures, the time is 20min, concentrated rear volume is 1ml.
(4) liquid after step 3 is concentrated is, below 1ml, to stop nitrogen blowing with nitrogen blowing to volume.
(5) the concentrate extraction filtered fluid with methyl alcohol, step 4 being obtained is settled to 1mL, and the liquid rotating after constant volume is moved on in Agilent special-purpose bottle.
(6) in the liquid to be measured obtaining in step 5, add 0.5ml internal standard compound Lomefloxacin (concentration 10 μ g/L), then in three grades of mass spectrometry instruments of ultrahigh pressure liquid phase chromatogram series connection, detect, detected parameters is as follows:
Liquid-phase condition: a) mobile phase composition: formic acid A.0.2%, B. methyl alcohol; B) sample size: 10 μ L; C) flow velocity: 0.2 mL/min; D) column temperature: 30 ℃; E) working time: 8min; F) chromatographic column: Acquity UPLC BEH; G) gradient: as shown in table 1.
Mass spectrum condition: a) desolventizing temperature degree: 350 ℃; B) source temperature: 150 ℃; C) capillary voltage: 3000V; D) desolventizing gas velocity: 650L/h; E) cone gas velocity: 50L/h.Quantitative and qualitative analysis ion is set in Table 3.
(7) chromatograph mass spectrum analysis figure is analyzed, complete detection.
Table 4 is the inventive method analysis results to 3 sub-samplings of the Enrofloxacin on solubilised state and suspended particulate substance in the Yuan Shui of Song Hua River.Visible, on particle, adhere to a certain amount of Enrofloxacin, the highest ratio is more than 8%.Illustrate, the detection of Enrofloxacin in water environment, can not ignore the part of adsorbing on suspended particulate substance.
Qualitative and the quota ion of table 3 Enrofloxacin
Table 4 testing result
| Project | The content (ng/L) of solubilised state Enrofloxacin in 0.45 μ m membrane filtration water | The content (ng/L) of suspended particle Enrofloxacin on 0.45 μ m membrane filtration film | On particle, Enrofloxacin accounts for the ratio % of solubilised state Enrofloxacin |
| Water sample 1 | 114.12±19.71 | 9.90±0.83 | 8.68 |
| Water sample 2 | 81.22±2.84 | 4.86±0.65 | 5.98 |
| Water sample 3 | 77.14±3.56 | 2.77±0.78 | 3.59 |
Claims (10)
1. trace enrofloxacin extracting and enriching and a quantitative method on suspended particulate substance in water, is characterized in that described method step is as follows:
(1) get target water sample 2000-4000ml, use microporous fibre membrane filtration, collect filter membrane and the surperficial suspended particulate substance of holding back after filtering, after filter membrane is dried, be cut into fragment and be placed in triangular flask, with graduated cylinder, measure appropriate extractant and pour in triangular flask, controlling the quality of suspended particulate substance and the volume ratio of extractant is 1g:15-20ml; With sealed membrane good seal, be placed in shaken cultivation case, Temperature Setting is 4-10 ℃, closes illumination and makes its dark, speed setting is 100-200 time/min, after vibration 8-12h, triangular flask is taken out, carry out ultrasonic extraction, extraction time 20-35min, is extracted liquid;
(2) extract obtaining by organic membrane filtration step 1 is transferred to the extract after filtering in the concentrated bottle of K-D simultaneously;
(3) add and dehydrate agent to the extraction filtered fluid in the concentrated bottle of step 2 K-D, after wipe dry, the concentrated bottle of K-D is put into rotary evaporator and concentrate, thickening temperature 30-45 ℃, the time is 10-20min;
(4) liquid after step 3 is concentrated is, below 1ml, to stop nitrogen blowing with nitrogen blowing to volume;
(5) add organic solvent, the concentrate extraction filtered fluid that step 4 is obtained is settled to 1mL, and the liquid rotating after constant volume is moved on in Agilent special-purpose bottle;
(6) internal standard compound that adds 0.5ml in the liquid to be measured obtaining in step 5 then detects in three grades of mass spectrometry instruments of ultrahigh pressure liquid phase chromatogram series connection;
(7) chromatograph mass spectrum analysis figure is analyzed, complete detection.
2. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the aperture of the microporous fiber membranes that step (1) is described is 0.45 μ m.
3. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the described extractant of step (1) is methyl alcohol.
4. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the described ultrasonic frequency of step (1) is 23-40kHz.
5. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the aperture of organic filter membrane that step (2) is described is 0.22 μ m.
6. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the described agent that dehydrates of step (3) is anhydrous sodium sulfate.
7. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the liquid volume after described concentrated of step (3) is 1-2ml.
8. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the described constant volume organic solvent of step (5) is methyl alcohol.
9. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the described internal standard compound of step (6) is sarafloxacin or Lomefloxacin.
10. trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, it is characterized in that the described three grades of mass spectrometry instruments of ultrahigh pressure liquid phase chromatogram string series connection of step (6) are Waters Xevo TQ MS Acquity UPLC System, detected parameters is as follows:
Liquid-phase condition: a) mobile phase composition: formic acid A.0.2vol.%, B. methyl alcohol; B) sample size: 10 μ L; C) flow velocity: 0.2 mL/min; D) column temperature: 30 ℃; E) working time: 8min; F) chromatographic column: Acquity UPLC BEH; G) gradient: 0min:V (A) %-80, V (B) %-20,5min:V (A) %-30, V (B) %-70,5.1min:V (A) %-0, V (B) %-100,6.5min:V (A) %-0, V (B) %-100,6.6min:V (A) %-80, V (B) %-20,8min:V (A) %-80, V (B) %-20;
Mass spectrum condition: a) desolventizing temperature degree: 350 ℃; B) source temperature: 150 ℃; C) capillary voltage: 3000V; D) desolventizing gas velocity: 650L/h; E) cone gas velocity: 50L/h.
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| CN114428137A (en) * | 2022-01-28 | 2022-05-03 | 中国科学院东北地理与农业生态研究所 | Trace detection method for suspended particulate matters in water body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101493443A (en) * | 2009-02-25 | 2009-07-29 | 哈尔滨工业大学 | Method for detecting organics attached to granule |
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| CN101493443A (en) * | 2009-02-25 | 2009-07-29 | 哈尔滨工业大学 | Method for detecting organics attached to granule |
Non-Patent Citations (3)
| Title |
|---|
| FATIMA TAMTAM ETAL.: "Occurrence and the fate of antibiotics in the seine river in various hydrological conditions", 《SCIENCE OF THE ENVIROMENT》 * |
| N. DORIVAL‐GARCIA ETAL: "（Simultaneous determination of 13 quinolone antibiotic derivatives in wastewater samples using solid‐phase extraction and ultra performance liquid chromatography–tandem mass spectrometry", 《MICROCHEMICAL JOURNAL》 * |
| N. DORIVAL-GARCIA ETAL: "Analysis of quinolone antibiotic derivatives in sewage sludge samples by liquid chromatography–tandem mass spectrometry: Comparison of the efficiency of three extraction techniques", 《TALANTA》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114428137A (en) * | 2022-01-28 | 2022-05-03 | 中国科学院东北地理与农业生态研究所 | Trace detection method for suspended particulate matters in water body |
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