CN104155400A - Method for extraction enrichment and quantification of trace ciprofloxacin on suspended particles in water - Google Patents
Method for extraction enrichment and quantification of trace ciprofloxacin on suspended particles in water Download PDFInfo
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- CN104155400A CN104155400A CN201410416934.3A CN201410416934A CN104155400A CN 104155400 A CN104155400 A CN 104155400A CN 201410416934 A CN201410416934 A CN 201410416934A CN 104155400 A CN104155400 A CN 104155400A
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Abstract
The invention discloses a method for extraction enrichment and quantification of trace ciprofloxacin on suspended particles in water. The method comprises the steps: filtering a target water sample by a microporous fiber membrane, collecting the filter membrane after filtration, air-drying the filter membrane, then cutting into pieces, placing in a triangular flask, adding an extracting agent, sealing, oscillating, and carrying out ultrasonic extraction; filtering the extracted liquid by an organic filter membrane, and at the same time, transferring the filtered extracted liquid to an K-D concentration bottle; adding a dehydrating drying agent into the extracted filtrate, after absorbing up water, putting the K-D concentration bottle into a rotary evaporator, and concentrating; blowing the concentrated liquid with nitrogen gas until the volume is below 1 mL; making the concentrated extracted filtered liquid to a constant volume of 1 mL, and then transferring to an Agilent special flask; adopting an internal standard method, and detecting by a high performance liquid chromatography-tandem three-grade mass spectrometry instrument; and analyzing a chromatographic mass spectrometric analysis diagram, and thus completing the detection. The method supplements the content of ciprofloxacin adsorbed on the suspended particles in the water environment, and supplements a blank of antibiotic detection.
Description
Technical field
The invention belongs to environmental monitoring technology field, relate to the detection method of Ciprofloxacin in a kind of water environment, be specifically related in a kind of water the quantivative approach of Ciprofloxacin extracting and enriching on particle.
Background technology
Ciprofloxacin belongs to third generation fluoroquinolone antibiotic drug, its antibacterial activity is the strongest in the fluoroquinolones of current widespread use, it has height antibacterial activity to gram negative bacilli, staphylococcus is had to good antibacterial action, the effect of pneumococcus, streptococcus is slightly worse than to staphylococcus, can kill as the bacterium of anthrax one class, cause the enzyme of reverse transcription after DNA replication dna by interference, stop the synthetic of DNA and protein.
Ciprofloxacin uses extensively in clinical treatment, due to not exclusively metabolism in vivo, still can keep higher drug concentration in excreta, and conventional water treatment and wastewater treatment can not thoroughly reduce its concentration, finally flow in water environment.In recent years, in water environment, the report of trace Ciprofloxacin was a lot of both at home and abroad, and concentration is the magnitude to μ g/L by ng/L, and the Ciprofloxacin in these water environments, finally enters into potable water system by water intaking, the effectively Technology Need exploitation of Ciprofloxacin in degradation water.Therefore,, in order to ensure drinking water safety, accurately detect in water environment, the method for trace Ciprofloxacin 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 Ciprofloxacin, 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 Ciprofloxacin of solubilised state, after Solid-Phase Extraction, after enrichment, detects.These methods be confined to solubilised state Ciprofloxacin quantitatively on.Studies have reported that, Ciprofloxacin belongs to carboxylic acid material, be easy to be adsorbed on particle surface, therefore, the necessary extraction of the Ciprofloxacin on particle surface is got off, carry out quantitatively, like this, can omnibearing grasp water in the pollution situation of Ciprofloxacin, be to resolve the Transport of Ciprofloxacin 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 Ciprofloxacin 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, measure appropriate extractant with graduated cylinder and pour in triangular flask; Be placed in shaken cultivation case with sealed membrane good seal, Temperature Setting is 4-10 DEG C, 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, concentrated K-D bottle is put into rotary evaporator and concentrate, thickening temperature 30-45 DEG C, the time is 10-20min, concentrated after volume be that 1-2ml is advisable.
(4) liquid after step 3 is concentrated, with nitrogen blowing to volume be, below 1ml, to stop nitrogen blowing.
(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) in the liquid to be measured obtaining in step 5, add the internal standard compound of 0.5ml, 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: A.0.2vol.% formic acid, B. methyl alcohol; B) sample size: 10 μ L; C) flow velocity: 0.2 mL/min; D) column temperature: 30 DEG C; 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 DEG C; B) source temperature: 150 DEG C; 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 described microporous fiber membranes of step (1) 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 described oscillator of step (1) is the HZQ-F160 type shaken cultivation case of HDL company, and 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 the described organic filter membrane of step (2) 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 Ciprofloxacin are similar, at the NF fluoroquinolones material of target water body.Internal standard compound is not only confined to these two kinds, as long as allied substances, and 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 (Acquity UPLC BEH) that instrument carries.
Table 1 eluent gradient elution program
Qualitative and the quota ion of table 2 Ciprofloxacin
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 Ciprofloxacin adsorbing on suspended particulate substance in water environment, reflect more really the content of Ciprofloxacin in water, thus the pollution situation of Ciprofloxacin in omnibearing grasp water.
2, this method is to resolve the Transport of Ciprofloxacin 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 Ciprofloxacin adsorbing on suspended particulate substance in water environment, has supplemented the blank that microbiotic detects.
Brief description of the drawings
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 Ciprofloxacin 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, measure appropriate methyl alcohol with graduated cylinder and pour in triangular flask, the quality of described suspended particulate substance and the volume ratio of methyl alcohol are 1g:20ml; Be placed in shaken cultivation case with sealed membrane good seal, Temperature Setting is 4 DEG C, 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, concentrated K-D bottle is put into rotary evaporator and concentrate, 30 DEG C of thickening temperatures, the time is 20min, concentrated rear volume is 1ml.
(4) liquid after step 3 is concentrated, with nitrogen blowing to volume be, below 1ml, to stop nitrogen blowing.
(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: A.0.2% formic acid, B. methyl alcohol; B) sample size: 10 μ L; C) flow velocity: 0.2 mL/min; D) column temperature: 30 DEG C; 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 DEG C; B) source temperature: 150 DEG C; 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 analysis results of 3 sub-samplings of the inventive method to the Ciprofloxacin on solubilised state and suspended particulate substance in the Yuan Shui of Song Hua River.Visible, on particle, adhere to a certain amount of Ciprofloxacin, the highest ratio is more than 145%.Illustrate, the detection of Ciprofloxacin in water environment, can not ignore the part of adsorbing on suspended particulate substance.
Qualitative and the quota ion of table 3 Ciprofloxacin
Table 4 testing result
| Project | The content (ng/L) of solubilised state Ciprofloxacin in 0.45 μ m membrane filtration water | The content (ng/L) of suspended particle Ciprofloxacin on 0.45 μ m membrane filtration film | The divine by astrology ratio % of solubilised state Ciprofloxacin of particle pressed on ring the third sand |
| Water sample 1 | 3.54±0.35 | 5.16±1.36 | 145.76 |
| Water sample 2 | 3.13±0.18 | 3.45±1.56 | 110.22 |
| Water sample 3 | 3.08±0.26 | 2.21±1.70 | 71.75 |
Claims (10)
1. trace Ciprofloxacin 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, measure appropriate extractant with graduated cylinder and pour in triangular flask, controlling the quality of suspended particulate substance and the volume ratio of extractant is 1g:15-20ml; Be placed in shaken cultivation case with sealed membrane good seal, Temperature Setting is 4-10 DEG C, 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, concentrated K-D bottle is put into rotary evaporator and concentrate, thickening temperature 30-45 DEG C, the time is 10-20min;
(4) liquid after step 3 is concentrated, with nitrogen blowing to volume be, below 1ml, to stop nitrogen blowing;
(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) in the liquid to be measured obtaining in step 5, add the internal standard compound of 0.5ml, then in three grades of mass spectrometry instruments of ultrahigh pressure liquid phase chromatogram series connection, detect;
(7) chromatograph mass spectrum analysis figure is analyzed, complete detection.
2. trace Ciprofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the aperture of the described microporous fiber membranes of step (1) is 0.45 μ m.
3. trace Ciprofloxacin 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 Ciprofloxacin 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 Ciprofloxacin extracting and enriching and quantitative method on suspended particulate substance in water according to claim 1, is characterized in that the aperture of the described organic filter membrane of step (2) is 0.22 μ m.
6. trace Ciprofloxacin 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 Ciprofloxacin 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 Ciprofloxacin 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 Ciprofloxacin 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 Ciprofloxacin 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: A.0.2vol.% formic acid, B. methyl alcohol; B) sample size: 10 μ L; C) flow velocity: 0.2 mL/min; D) column temperature: 30 DEG C; 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 DEG C; B) source temperature: 150 DEG C; C) capillary voltage: 3000V; D) desolventizing gas velocity: 650L/h; E) cone gas velocity: 50L/h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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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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2014
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| JPH01305091A (en) * | 1988-06-01 | 1989-12-08 | Daicel Chem Ind Ltd | Optical resolution of esters of ofloxacin |
| CN101493443A (en) * | 2009-02-25 | 2009-07-29 | 哈尔滨工业大学 | Method for detecting organics attached to granule |
| CN102798689A (en) * | 2012-08-15 | 2012-11-28 | 哈尔滨工业大学 | Method for separation enrichment and detection of trace fluoroquinolone antibiotic in water environment |
| CN103344732A (en) * | 2013-06-20 | 2013-10-09 | 中国环境科学研究院 | Method for simultaneous detection of ofloxacin and sarafloxacin in water body |
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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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