CN108318613A - The detection method of antibiotic in a kind of environmental sample - Google Patents
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Abstract
The present invention relates to technical field of environmental detection, the measurement of erythromycin, chloramphenicol, sulfamethoxazole, sulphadiazine, roxithromycin, Cefotiam, sulfapryidine, Norfloxacin, Ofloxacin, tetracycline and fortimicin suitable for sewage, surface water and bed mud.After sampling, it is detected using ultra performance liquid chromatography triple quadrupole bar tandem mass spectrum after being pre-processed with mud sample to water sample, passes through target compound characteristic ion pair（m/z）Carry out it is qualitative, with response to respective concentration draw standard curve use quantified by external standard method, to obtain the content of all kinds of antibiotic in sample.This method is accurate, sensitive, simple, the content suitable for measuring 11 kinds of typical antibiotic sewage, surface water, sludge simultaneously.
Description
Technical field
The present invention relates to the detection methods of antibiotic in detection technique field, especially environmental sample.
Background technology
Antibiotic be by animals and plants such as microorganism (including bacterium, fungi, actinomyces) or other height in life process
Generated a kind of secondary metabolite with antipathogen or other active materials is a kind of other living cells to be interfered to send out
The chemical substance for educating function is broadly divided into beta-lactam, aminoglycoside, Tetracyclines, quinolones, macrolide
Deng.Antibiotic is widely used in the protection of human and animal's health, or fast come the growth for improving animal as food additive
Degree.Chinese antibiotic usage amount accounts for about the half of world's dosage up to 16.2 ten thousand tons within 2013, wherein 52% is for animals, 48%
It is used for people, more than 50,000 tons antibiotic are discharged into soil and water resources.2013, the Chinese daily usage amount of thousand people of antibiotic
It is 157 meterings, and the American-European daily usage amount of thousand people is generally between 20~30, the 2011/2012 year U.S. is 28.8,2013
Year Britain be Canada in 27.4,2011 be Europe in 20.4,2003 be 20.1.It can calculate accordingly, China is beautiful
5.5 times of state, 5.7 times of Britain, 7.7 times Canadian, European 7.8 times.
In actual use, only part can be metabolized antibiotic in human body or animal body, 10~90% it is anti-
The raw non-energy metabolism of element, but excreted by urine or excrement in the form of precursor structure.For example, 70% Ofloxacin and
The 30% non-energy metabolism of Norfloxacin and be discharged from urine；65% azithromycin and 55% roxithromycin are with original form
It is discharged by excrement.Therefore, antibiotic is easy to directly or indirectly enter in environment.In addition, in addition to the change of antibiotic itself
It is outer to learn pollution, antibiotic can also accelerate the generation of antibiotics resistance gene and resistance bacterium, and resistant gene and resistance bacterium can be to people
Class and the health of animal generate risk.These bacteriums may be by directly or indirectly contacting from environmental dissemination to the mankind.
Antibiotic into ecological environment easily remains in water body and soil, is chronically exposed in the antibiotic of low dosage,
Microbes are induced to generate drug resistance gene in environment.Although the detectable concentration of antibiotic in the environment be usually nanogram level or
Gamma Magnitude, but these traces of antibiotic have high bioactivity, persistence and bioconcentration, and zoonosis incidence is made to increase
Add, causes slow poisoning and " three cause " effect.Studies have shown that tetracycline can inhibit synthesis and the chloroplaset of microalgae protein
Generation, inhibit the growth of microalgae, can also inhibit the activity of enzyme in chloroplaset, to inhibit the growth of plant, to the root of plant
System generates larger toxicity.
Municipal sewage plant enters the last line of defense of environment as antibiotic in water, to antibiotic removal effect
Quality be then directly becoming control antibiotic and enter the key link of environment.Numerous studies show many countries in sewage disposal
Detect different degrees of antibiotic residue in plant effluent, most of residual antibiotic is in municipal sewage treatment in sanitary sewage
Removal effect is unsatisfactory in factory, and traditional sewage treatment process cannot achieve having for the emerging organic pollution such as residual antibiotic
Effect removal.Sewage treatment plant has been widely regarded as one of the main source of Environmental Trace antibiotic appearance.Realize antibiotic
Etc. emerging organic pollution from sewage treatment plant to environment in decrement discharge, be control antibiotic occur in the environment, drop
The effective ways of low its environmental hazard and risk.
The second quarter in 2016, Chengdu state pollution control water treatment plant supervisory monitoring was the results show that Chengdu inner city is existing
It is 1,660,000 ton days to have sewage treatment capacity, and the discharge capacity into environment is about 1,400,000 tons daily, so largely after processing
Sewage enter in environment, wherein the antibiotic difficult to degrade of the trace contained constantly will be recycled and be accumulated, so as to environment
Generate larger harm.Therefore, antibiotic detection method in a whole set of complete water body is established, to adapt to in sewage treatment plant
The Survey of contamination status of sea products of typical antibiotic and removal situation research.It is beneficial to control the pollution of antibiotic from source, for
Ensure that resident's health and region environment safety, formulation meet the actual antibiotic contamination control strategy of national conditions and place
And removing measure, there is important directive significance.
Invention content
To solve the above problems, the present invention provides a kind of detection method of middle antibiotic, environment sample can be effectively detected
Antibiotic content in product, to provide reference for the investigation of antibiotic, risk assessment and removal research etc..
To achieve the goals above, the technical solution adopted in the present invention is, the detection of antibiotic in a kind of environmental sample
Method, erythromycin, chloramphenicol, sulfamethoxazole, sulphadiazine, roxithromycin, head suitable for for sewage, surface water and bed mud
Spore is for peace, the measurement of sulfapryidine, Norfloxacin, Ofloxacin, tetracycline and fortimicin.Include the following steps：
(1) sample pretreatment：It takes 1000mL water samples that 1gEDTA disodium salts are added after filtering and removing impurity to protect at 4 DEG C
It deposits；Bed mud sample removes water layer after centrifugation, and then freeze-drying preserves after removing moisture removal at 4 DEG C；
(2) water sample extracts：Take HLB pillar enrichment of the pretreated water samples of 500mL after activation, coutroi velocity 3-5mL/
Min is repeated once, dry to be dried up to HLB pillars progress nitrogen after the ultrapure water wash of 10mL after the completion of enrichment, and 10mL is added after dry
Methanol elutes, and collects eluent at this time, and elution liquid nitrogen, which is blown, to be concentrated within 1mL, methanol constant volume to 1mL, using liquid chromatogram-three
Weight quadrupole rod tandem mass spectrum is detected；
(3) mud sample is extracted：The bed mud sample 2g after drying is taken, 5g diatomite is added, and ASE is extracted after mixing, extract liquor
Using ACN/H2O=7:3, it is diluted after extract liquor filtering and is settled to 500mL, 1gEDTA disodium salts, remaining step and step b is added
It is identical；
(4) result calculates：The peak area of obtained each antibiotic is substituted into standard curve with external standard method, calculates separately sample
In each antibiotic mass concentration, computational methods are：
Water sample：
In formula：ρi--- the mass concentration of component i in water sample, μ g/L；
mi--- the mass concentration of obtained component i, μ g/L are calculated by calibration curve；
Vt--- constant volume, mL；
Vs--- sample volume, mL；
Mud sample：
In formula：ωi--- the content of component i in sample, μ g/kg；
ρi--- the mass concentration of obtained component i, μ g/L are calculated by calibration curve；
V --- constant volume, mL；
M --- sample size (weight in wet base), g；
W --- sample moisture content, %.
Further, the standard curve is accurately to pipette 100 μ L of each antibiotic standard solution, and methanol constant volume to 10mL is held
Measuring bottle, this mixes a concentration of 1mg/L of mark, then the multiple concentration points being diluted in 1000 μ g/L concentration, using using liquid chromatogram-three
Weight quadrupole rod tandem mass spectrum, which is detected, respectively draws respective concentration with response using external standard method each concentration point analysis
Standard curve, related coefficient will reach 0.99 or more.
Further, the liquid chromatogram is handled by gradient elution, and mobile phase is acetonitrile：2.5mmol ammonium acetates ＆
0.1% aqueous formic acid, 40 DEG C of column temperature；Flow velocity 0.4mL/min, elution program such as following table：
Gradient elution program
Further, series connection quadrupole rod Mass Spectrometry Conditions are optimized with each antibiotic list mark standard solution of 0.5mg/L, is selected
ESI is selected as ion source.
Further, the Mass Spectrometry Conditions such as following table of the mass spectrographic Mass Spectrometry Conditions of quadrupole rod:
Mass Spectrometry Conditions
Mass Spectrometry Conditions (Continued)
Further, the sample using Brown Glass Brown glass bottles and jars only collect, Brown Glass Brown glass bottles and jars only first with distilled water clean, after in dichromic acid
Potassium solution impregnates for 24 hours, dries 2h after ultrapure water in 250 DEG C, is rinsed again with DETA disodium salt methanol saturated solutions after cooling
After acquire sample.
Further, the HLB pillars add 10mL water and are activated using 10mL methanol is first added.
Further, multiple concentration points are 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ
g/L、200μg/L、500μg/L、1000μg/L。
Further, the sample will be located when progress liquid chromatogram-triple quadrupole bar tandem mass spectrum is detected analysis
The 5 μ L of sample and blank direct injected managed, peak area quantification qualitative according to retention time and characteristic ion.
Using detection method of the present invention, while being effectively enriched with antibiotic, removal interference as much as possible
Component, while realizing the detection of Multiple Classes of Antibiotics, and accuracy of detection higher.
Specific implementation mode
The present invention is described in further detail below by specific embodiment.
Embodiment 1：The detection method of antibiotic in a kind of environmental sample.
1, Method And Principle
Bed mud sample concentrates constant volume through drying, ASE extractions, the enrichment elution of SPE pillars；Water sample is washed through the enrichment of SPE pillars
It is de-, concentrate constant volume.It is detected using liquid chromatogram-triple quadrupole bar tandem mass spectrum, it is qualitative with retention time and qualitative ion,
Peak area quantification calculates the content of each antibiotic in sample.
2, the scope of application
This method is suitably for erythromycin, chloramphenicol, sulfamethoxazole, sulphadiazine, Luo Hong in sewage, surface water and bed mud
The measurement of mycin, Cefotiam, sulfapryidine, Norfloxacin, Ofloxacin, tetracycline and fortimicin.
3, reagent and material
Each antibiotic standard items 100mg/L (Ministry of Agriculture), ultra-pure water (resistivity 18.2M Ω cm, U.S. millipore
Company), acetonitrile (HPLC grades, Honeywell), ammonium acetate (German Merck), formic acid (CNW), methanol (HPLC grades,
Honeywell), Waters Oasis HLB pillars (6CC, 500mg), diatomite.
4, instrument and equipment
High performance liquid chromatography-series connection quadrupole rod mass spectrometer (liquid phase：Thermo UltiMate 3000, mass spectrum：
ABSCIEXAPI 4000), Accelerate solvent extraction (Thermo ASE150), 0.22 μm of filter membrane syringe filter and 0.22 μm of water phase
Filter membrane, Merck Millipore ultrapure water machines, micro syringe (1000 μ L, 100 μ L, 10 μ L), pH meter, a ten thousandth analyze day
Flat, solid-phase extraction device, quick nitrogen evaporator.
5, sample collection
Sample Brown Glass Brown glass bottles and jars only is acquired first to be cleaned with distilled water, after impregnated for 24 hours, after ultrapure water in potassium bichromate solution
2h are dried in 250 DEG C, acquire sample after being rinsed again with DETA disodium salt methanol saturated solutions after cooling, in 4 DEG C after sample collection
Lower preservation, takes back laboratory as early as possible.
1gEDTA disodium salts are added after filtering and removing impurity and are preserved at 4 DEG C for water sample, analyze as early as possible.Bed mud sample passes through
Water layer is removed after centrifugation, then freeze-drying preserves after removing moisture removal at 4 DEG C, analyzes as early as possible.
6, analytic process
6.1 sample pre-treatments
6.1.1HLB pillar activates
10mL methanol is first added, adding 10mL water can activate.
6.1.2 water sample is handled
HLB pillar enrichment of the 500mL samples after activation, coutroi velocity 3-5mL/min is taken to be repeated once, enrichment is completed
To be carried out to HLB pillars after the ultrapure water wash of 10mL, nitrogen drying is dry, and the elution of addition 10mL methanol, collects elution at this time after drying afterwards
Liquid.Elution liquid nitrogen, which is blown, to be concentrated within 1mL, methanol constant volume to 1mL, upper machine analysis.
6.1.3 mud sample is handled
The sample 2g after drying is taken, 5g diatomite is added, and ASE is extracted after mixing, and extract liquor uses ACN/H2O=7:
3, it is diluted after extract liquor filtering and is settled to 500mL, 1gEDTA disodium salts are added, remaining step is the same as 6.1.2 water sample processing procedures.
6.2 chromatographic condition
Mobile phase is acetonitrile：2.5mmol Yi Suanan ＆0.1% aqueous formic acids；Chromatographic column is Aglient Poroshell
120EC-C18 columns (100mm × 2.1mm × 2.7 μm)；40 DEG C of column temperature；Flow velocity 0.4mL/min.Type of elution uses gradient elution,
Elution program following table.
Gradient elution program
6.3 liquid chromatography tandem quadrupole rod Mass Spectrometry Conditions
HPLC-MS/MS conditions are optimized with each antibiotic list mark standard solution of 0.5mg/L, select ESI as from
Component, actual conditions are as shown in the table.
Mass Spectrometry Conditions
Mass Spectrometry Conditions (Continued)
6.4 draw standard curve
Accurately pipette each single mark 100 μ L of standard solution, methanol constant volume to 10mL volumetric flasks, this mixed a concentration of 1mg/L (this of mark
Standard liquid storage life it is shorter about one week), refrigerate when refrigerator, use diluted on site at multiple concentration points in 1000 μ g/L concentration
Each concentration point is measured respectively under the conditions of the chromatographic mass spectrometry of optimization, using external standard method, respective concentration is drawn with response and is marked
Directrix curve, related coefficient will reach 0.99 or more.
6.5 samples measure
By 5 μ L of the sample handled well and blank direct injected, qualitative according to retention time and characteristic ion, peak area is fixed
Amount.
7. calculating and interpretation of result
7.1 results calculate
The peak area of obtained each antibiotic is substituted into standard curve with external standard method and calculates separately each antibiotic in sample
Mass concentration.
Water sample：
In formula：ρi--- the mass concentration of component i in water sample, μ g/L；
mi--- the mass concentration of obtained component i, μ g/L are calculated by calibration curve；
Vt--- constant volume, mL；
Vs--- sample volume, mL；
In formula：ωi--- the content of component i in sample, μ g/kg；
ρi--- the mass concentration of obtained component i, μ g/L are calculated by calibration curve；
V --- constant volume, mL；
M --- sample size (weight in wet base), g；
W --- sample moisture content, %.
By standard sample detection and recovery testu, following table is obtained：
Compound Retention time and the range of linearity
It takes 7 groups of sewage to be detected, obtains result such as following table：
Method detection limit, Determination Limit tables of data
Method detection limit, Determination Limit tables of data (Continued)
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, there can be various modifications and variations in the spirit and principles in the present invention, these equivalent modifications or replacement etc.,
It is all included in the scope of protection of the present invention.
Claims (9)
1. the detection method of antibiotic in a kind of environmental sample, it is characterised in that：It is red mould suitable for sewage, surface water and bed mud
Element, chloramphenicol, sulfamethoxazole, sulphadiazine, roxithromycin, Cefotiam, sulfapryidine, Norfloxacin, Ofloxacin, four
The measurement of ring element and fortimicin, includes the following steps：
(1) sample pretreatment：It takes 1000mL water samples that 1gEDTA disodium salts are added after filtering and removing impurity to preserve at 4 DEG C；Bottom
Mud sample product remove water layer after centrifugation, and then freeze-drying preserves after removing moisture removal at 4 DEG C；
(2) water sample extracts：HLB pillar of the pretreated water samples of 500mL after activation is taken to be enriched with, coutroi velocity 3-5mL/min,
It is repeated once, dry, addition 10mL methanol after drying is dried up to carry out nitrogen to HLB pillars after the ultrapure water wash of 10mL after the completion of enrichment
Eluent is collected in elution at this time, and elution liquid nitrogen, which is blown, to be concentrated within 1mL, methanol constant volume to 1mL, using liquid chromatogram-triple four
Pole bar tandem mass spectrum is detected；
(3) mud sample is extracted：The bed mud sample 2g after drying is taken, 5g diatomite is added, and ASE is extracted after mixing, and extract liquor uses
ACN/H2O=7:3, it is diluted after extract liquor filtering and is settled to 500mL, 1gEDTA disodium salts, remaining step and step b phases is added
Together；
(4) result calculates：The peak area of obtained each antibiotic is substituted into standard curve with external standard method, is calculated separately each in sample
The mass concentration of antibiotic, computational methods are：
Water sample：
In formula：ρi--- the mass concentration of component i in water sample, μ g/L；
mi--- the mass concentration of obtained component i, μ g/L are calculated by calibration curve；
Vt--- constant volume, mL；
Vs--- sample volume, mL；
Mud sample：
In formula：ωi--- the content of component i in sample, μ g/kg；
ρi--- the mass concentration of obtained component i, μ g/L are calculated by calibration curve；
V --- constant volume, mL；
M --- sample size (weight in wet base), g；
W --- sample moisture content, %.
2. the detection method of antibiotic in a kind of environmental sample according to claim 1, it is characterised in that：The standard
Curve is accurately to pipette 100 μ L of each antibiotic standard solution, methanol constant volume to 10mL volumetric flasks, this mixed a concentration of 1mg/L of mark, then
The multiple concentration points being diluted in 1000 μ g/L concentration are detected difference using liquid chromatogram-triple quadrupole bar tandem mass spectrum
To each concentration point analysis, using quantified by external standard method, standard curve is drawn to respective concentration with response, related coefficient will reach
0.99 or more.
3. the detection method of antibiotic in a kind of environmental sample according to claim 1 or 2, it is characterised in that：Described
Liquid chromatogram is handled by gradient elution, and mobile phase is acetonitrile：2.5mmol Yi Suanan ＆0.1% aqueous formic acids, 40 DEG C of column temperature；
Flow velocity 0.4mL/min, elution program such as following table：
Gradient elution program
4. the detection method of antibiotic in a kind of environmental sample according to claim 1, it is characterised in that：Use 0.5mg/L
Each antibiotic list mark standard solution to series connection quadrupole rod Mass Spectrometry Conditions optimize, select ESI as ion source.
5. the detection method of antibiotic in a kind of environmental sample according to claim 1,2, one of 4, it is characterised in that：Four
The mass spectrographic Mass Spectrometry Conditions of pole bar such as following table：
Mass Spectrometry Conditions
Mass Spectrometry Conditions (Continued)
6. the detection method of antibiotic in a kind of environmental sample according to claim 1, it is characterised in that：The sample is adopted
Collected with Brown Glass Brown glass bottles and jars only, Brown Glass Brown glass bottles and jars only first with distilled water clean, after in potassium bichromate solution impregnate for 24 hours, ultrapure water
2h is dried in 250 DEG C afterwards, sample is acquired after being rinsed again with DETA disodium salt methanol saturated solutions after cooling.
7. the detection method of antibiotic in a kind of environmental sample according to claim 1, it is characterised in that：The HLB
Pillar adds 10mL water and is activated using 10mL methanol is first added.
8. the detection method of antibiotic in a kind of environmental sample according to claim 2, it is characterised in that：Described is multiple
Concentration point is 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 500 μ g/L.
9. the detection method of antibiotic in a kind of environmental sample according to claim 1, it is characterised in that：The sample
When progress liquid chromatogram-triple quadrupole bar tandem mass spectrum is detected analysis, by the sample handled well and blank direct injected 5
μ L, peak area quantification qualitative according to retention time and characteristic ion.
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| CN109142572A (en) * | 2018-08-23 | 2019-01-04 | 中南大学 | A variety of drugs are synchronous in a kind of environment multimedium extracts and determination method |
| CN109342624A (en) * | 2018-12-07 | 2019-02-15 | 上海市环境科学研究院 | The method that Solid Phase Extraction pre-treatment combination LC-MS technology detects 15 kinds of antibiotic in aquaculture system simultaneously |
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| CN112505195A (en) * | 2020-11-13 | 2021-03-16 | 山西省环境科学研究院 | Method for accurately and sensitively detecting antibiotics in environmental sample |
| 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 |
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| CN109142572B (en) * | 2018-08-23 | 2021-06-04 | 中南大学 | Synchronous extraction and detection analysis method for multiple drugs in environmental multi-media |
| CN109142576A (en) * | 2018-09-03 | 2019-01-04 | 江西省农业科学院农产品质量安全与标准研究所 | The detection method of roxithromycin residual quantity in a kind of animal hair |
| CN109342624A (en) * | 2018-12-07 | 2019-02-15 | 上海市环境科学研究院 | The method that Solid Phase Extraction pre-treatment combination LC-MS technology detects 15 kinds of antibiotic in aquaculture system simultaneously |
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| CN111707772A (en) * | 2020-06-05 | 2020-09-25 | 哈尔滨工业大学 | Method for synchronously and efficiently detecting residual quantity of various antibiotics in sludge |
| CN111751482A (en) * | 2020-06-05 | 2020-10-09 | 哈尔滨工业大学 | Method for synchronously detecting residual quantity of various antibiotics in pig-raising wastewater |
| CN111707772B (en) * | 2020-06-05 | 2022-12-23 | 哈尔滨工业大学 | Method for synchronously and efficiently detecting residual quantity of various antibiotics in sludge |
| CN111751482B (en) * | 2020-06-05 | 2022-12-23 | 哈尔滨工业大学 | Method for synchronously detecting residual quantity of various antibiotics in pig-raising wastewater |
| CN111707763A (en) * | 2020-06-23 | 2020-09-25 | 南宁学院 | Method for rapidly detecting chloramphenicol in food |
| CN112505195A (en) * | 2020-11-13 | 2021-03-16 | 山西省环境科学研究院 | Method for accurately and sensitively detecting antibiotics in environmental sample |
| 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 |
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