CN103091435B - Method for detecting chemical residues in organic fertilizer - Google Patents
Method for detecting chemical residues in organic fertilizer Download PDFInfo
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- CN103091435B CN103091435B CN201210428784.9A CN201210428784A CN103091435B CN 103091435 B CN103091435 B CN 103091435B CN 201210428784 A CN201210428784 A CN 201210428784A CN 103091435 B CN103091435 B CN 103091435B
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Abstract
The invention provides a method for detecting chemical residues in an organic fertilizer. The method comprises the following steps of: (1) performing ultrasonic vibration extraction on a sample, and then treating the sample by using a solid-phase extraction column; (2) detecting the chemical residues by using a liquid chromatography-tandem mass spectrometry method; and (3) detecting the content of the chemical residues by using a standard curve method. By adopting the method provided by the invention, various residual antibiotics in the sample can be subjected to qualitative and quantitative detection at the same time, detection steps are greatly simplified, the method detection limit of tetracyclines can be 0.05mg/kg, and the method detection limit of sulfonamides and penicillin drugs can be 0.02mg/kg. Therefore, the detection method provided by the method has the characteristics that the detection limit is low, the result is accurate, and the detection method has an important practical significance in the field of soil improvement and environmental protection.
Description
Technical field
The physicochemical property that the invention belongs to by means of material carry out the field tested, and are specially a kind of method detected medicine residual in organic fertilizer.
Background technology
Along with the development of feed industry, microbiotic is more and more for feed addictive.Conventional antibiosis have: terramycin (oxytetracycline), molecular formula: C
22h
24n
2o
9; Molecular weight: 460.43, belong to broad-spectrum antibiotic, its antimicrobial spectrum, antibacterial mechanisms and tetracycline are substantially identical, all have inhibiting effect to gram positive bacteria and negative bacterium.Tetracycline (tetracycline), molecular formula: C
22h
24n
2o
8; Molecular weight: 444.44 is broad-spectrum antibacterial agent, tool bactericidal action during high concentration.Except common gram positive bacteria, gram-negative bacteria and anaerobion, most rickettsiae, Mycoplasma, chlamydiaceae, anonymous mycobacteria belong to, conveyor screw is also responsive to this product.Aureomycin (chlortetracycline), for TCs, be applicable to the treatment of shallow table ocular infection caused by the responsive gram-negative bacterias such as gram positive bacteria and haemophilus influenzae such as responsive staphylococcus aureus, micrococcus scarlatinae, streptococcus pneumonia, and the treatment that other position sensitive bacterias infect.Fortimicin (doxycycline), molecular formula: C
22h
24n
2o
8; Molecular weight: 444.44, TCs, can treat Chlamydia mycoplasma infection, is mainly used in treating responsive microbial respiratory tract, the urinary tract and infection of biliary tract.Sulphadiazine (sulfadiazine) molecular formula: C
10h
10n
4o
2s; Molecular weight: 250.28, sulfonamides, is used for the treatment of the infection caused by hemolytic streptococcus, pneumococcus, meningococcus, diplococcus, Escherichia coli.Sulfamethazine (sulfadimidine), molecular formula: C
12h
14n
4o
2s, molecular weight: 278.33, is equal to sulphadiazine and imitates, as feed addictive, for preventing and treating the infection of staphylococcus and hemolytic streptococcus etc., i.e. primary treatment cholera fowl, avian typhoid, chicken coccidiasis etc.Sulphathiazole (sulfathiazole), molecular formula: C
9h
9o
2n
3s
2; Molecular weight: 255.32, cures mainly hemolytic streptococcus, meningococcus, pneumococcus etc. and catches.Procaine penicillin (procaine penicillin), molecular formula C
29h
38n
4o
6s; Molecular weight 570.7, mainly acts on the moderate and low-grade infection that cause the GPC of penicillin-susceptible.Benzyl penicillin, (penicillin G), molecular formula: C
16h
18n
2o
4s, molecular weight: 334.39, belongs to beta-lactam antibiotic, the streptococcuses such as hemolytic streptococcus, and streptococcus pneumonia and the staphylococcus not producing penicillase have good antibacterial action.
Organic fertilizer is natural organic matter through a class fertilizer of microbial decomposition or fermentation.Its raw material mainly animal excretion.The feed ingredient that animal husbandry uses directly affects the composition of the materials such as organic fertilizer, feed, soil.The antibiosis of entered environment have the potential possibility of modificator gene sudden change, and the accumulation of microbiotic in soil environment also can reduce biological activity of soil, weakens the biological function of soil.Animal excretion, as an important sources of microbiotic entered environment, is a major issue that each side must be caused to pay close attention to.Therefore, the detection technique of antibiotics residual in organic fertilizer, soil, feed is very necessary for environmental protection, soil improvement.The method that microbiotic detects has the method such as molecular engram, affine immunity.Comparatively speaking, liquid phase chromatography can analyze Multiple Classes of Antibiotics better.
Feed use microbiotic in, terramycin and tetracycline most widely used general.Prior art also proposes some methods detected, assay method (Wang Lijun etc., modern agriculture science and technology, 2006(11) as TCs medicament residue in pork: 120-121), assay method (the Song Huimin etc. of terramycin in feed, Scientia Agricultura Sinica and technology, 2008,10(S2): 43-47), detection method (the Xiu Lihua etc. of oxytetracycline residues in poultry, poultry, modern food science and technology, 2007,11(23): 88-90) etc.Above document is not mentioned for antibiotics residues quantity measuring method in soil or organic fertilizer.
In actual soil or organic fertilizer sample, often there is Multiple Classes of Antibiotics.There is no the medicament residue that effective method detects Multiple Classes of Antibiotics simultaneously at present, and quantitatively determine its residual content.
Summary of the invention
For the weak point that prior art exists, the object of the invention is the detection method proposing a kind of medicament residue.
The concrete technical scheme realizing the object of the invention is:
A detection method for medicament residue, comprises step:
1) by sample ultrasonic mechanical shaking extraction, then solid phase extraction column process is used;
2) left drug is detected with Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS);
3) with the content that typical curve external standard method detection of drugs is residual.
This detection method can be used for the detection of medicine residual in the samples such as organic fertilizer, soil, feed.
Wherein, described left drug is residual medicine in the sample to which: one or more in terramycin, tetracycline, aureomycin, fortimicin, benzyl penicillin, procaine penicillin, sulphadiazine, sulfamethazine and sulphathiazole.
Wherein, in described step 1), first use buffer solution by described sample blending when sonic oscillation extracts, mechanical shaking extraction again after ultrasonic, centrifuging, then proceeds to solid phase extraction column process by supernatant.
Described solid phase extraction column is with isopyknic methyl alcohol, water and buffer solution counter-balanced solid phase extraction column.
Described buffer solution is Na2EDTA-MclIvaine, and the pH value of this Na2EDTA-MclIvaine buffer solution is 6.8-7.2.
Wherein, described step 2) in the mobile phase of liquid chromatography be A: containing mass ratio 0.05-0.15% first aqueous acid, B: acetonitrile, column equilibration time 7-10min.
Wherein, described step 2) in liquid chromatography use the method for gradient elution, the program of gradient elution is:
Preferably, the program of described gradient elution is:
The % of A and B is volume ratio.
Wherein, described step 2) in Mass Spectrometer Method use many reactive ions (MRM) to detect scanning, the mode of scanning is 0-9.2min is positive ion scanning, and 9.2-13min is negative ion scanning.
Wherein, step 2) middle parent ion and the daughter ion pair detecting each medicine in described sample, if its chromatography of ions peak retention time consistent with standard working solution (variation range is within ± 2.5%); And in sample, the relative abundance of relative abundance (going to determine in the quasi-molecular ions intensity contrast interface) standard solution suitable for concentration of two daughter ions of target compound is no more than in 30% scope consistent in deviation, then judge to there is this kind of medicine in this sample; If above-mentioned two conditions meet time different, then judge not containing this kind of medicine.
Wherein, described step 3) standard curve is formulated as standard solution respectively with the described medicine of variable concentrations, detects its chromatographic peak area with described Liquid Chromatography-Tandem Mass Spectrometry, the typical curve obtained relative to concentration drafting.Namely, the Standard pharmaceutical formulation of residual drug target to be detected is used to become standard solution, measure by same scan method, take concentration as horizontal ordinate, chromatographic peak area is ordinate, draw the typical curve of each medicine respectively, adopt this typical curve to calculate the content of 9 kinds of medicines in testing sample respectively with external standard method.For terramycin, its typical curve has 0.05,0.1,0.2,0.5,1.0, the chromatographic peak area of 5.0mg/L six some correspondences, with concentration, curve map is done to peak area, obtain linearity curve equation, bring the chromatographic peak area of sample into equation, the concentration of this medicine in machine solution can be can be regarded as, namely can be regarded as to obtain the content of terramycin in sample in conjunction with the extension rate in sample handling processes and sample weighting amount.
Beneficial effect of the present invention is:
Method of the present invention can carry out the mensuration of quantitative and qualitative analysis simultaneously to Multiple Classes of Antibiotics medicine residual in sample, enormously simplify the step of detection; The method detection limit of tetracycline medication all can reach 0.05mg/kg, and the method detection limit of sulfamido and penicillin medicine can reach 0.02mg/kg.Detection limit is low, and result is accurate, has important practical significance in soil improvement and field of environment protection.
Accompanying drawing explanation
Fig. 1 is the total ion chromatogram of 9 kinds of antibiotic medicines of negative ions fractional scanning.
Fig. 2 is 8 kinds of antibiotic medicine chromatography of ions figure of first paragraph positive ion scanning.
Fig. 3 is terramycin chromatography of ions figure.
Fig. 4 is tetracycline chromatography of ions figure.
Fig. 5 is aureomycin chromatography of ions figure.
Fig. 6 is fortimicin chromatography of ions figure.
Fig. 7 is procaine penicillin chromatography of ions figure.
Fig. 8 is sulphadiazine chromatography of ions figure.
Fig. 9 is sulfamethazine chromatography of ions figure.
Figure 10 is sulphathiazole chromatography of ions figure.
Figure 11 is microbiotic negative ion scanning chromatogram.
Figure 12 is the ion flow graph of negative ion scanning benzyl penicillin.
Embodiment
Now with following most preferred embodiment, the present invention is described, but is not used for limiting the scope of the invention.
The ultrasound processing equipment used in embodiment is Kunshan KQ-200KDE type ultrasonoscope;
Solid phase extraction column purchased from American Féraud door company;
0.22 μm of filter membrane is purchased from Tianjin Jin Teng experimental facilities company limited.
Embodiment 1: the detection of left drug in organic fertilizer sample
1. sample pretreatment: by organic fertilizer sample blending, takes 1.0g sample in 50mL centrifuge tube, with the Na of 2 × 15mL pH 7.0
2the mixing of EDTA-MclIvaine buffer solution (repeats for twice to extract, each 15mL), mechanical shaking extraction 10min again after ultrasonic 10min, 10000rpm high speed centrifugation 10min, supernatant water layer directly proceeds to silica matrix solid phase extraction column (the Strata SDB-L activated, quantity of sorbent/volume is 500mg/6mL, uses 5mL methyl alcohol, 5mL water and 5mL Na in advance
2eDTA-MclIvaine damping fluid balances).Collect all effluxes simultaneously, shift extract in 100mL centrifuge tube with after 20mL ethyl acetate mechanical shaking extraction 10min.Solid phase extraction column drains rear 10mL methyl alcohol, 5mL acetonitrile and 5mL eluent ethyl acetate, merge all eluents in aforementioned 100mL centrifuge tube, supernatant is proceeded to glass heart bottle after the centrifugal 5min of 4500rpm, in 40 DEG C of water-baths, vacuum rotary steam dries up to nearly dry rear nitrogen in 50 DEG C, cross 0.22 μm of filter membrane with after formic acid water (volume ratio 50/50) the solution constant volume of 1.0mL acetonitrile/0.1%, upper LC-MS/MS measures.
2.LC-MS/MS measures
Instrument: Agilent 1200 high performance liquid chromatography (U.S., Agilent)-API2000 three grades of quadrupole rod tandem mass spectrum combined instruments (U.S., AB SCIEX), are equipped with electron spray (ESI) ion gun;
Chromatographic column: Agilent XDB C18,4.6 × 150mm, particle diameter 5 μm;
Mobile phase: (A) water (containing 0.1% formic acid); (B) acetonitrile;
Flow velocity: 0.3mL/min;
Sample size: 10 μ L;
Column temperature: room temperature (about 26 DEG C);
The column equilibration time (before next sample feeding): 8min;
Gradient elution program is as table 1.
Table 1: the gradient elution program of embodiment 1
| Sequence number | Time (min) | A（%） | B（%） |
| 1 | 0 | 70 | 30 |
| 2 | 4.0 | 10 | 90 |
| 3 | 9.0 | 10 | 90 |
| 4 | 9.1 | 70 | 30 |
| 5 | 13.0 | 70 | 30 |
3. mass spectroscopy
Scan mode: many reactive ion monitoring (MRM) scanning;
Ion source temperature TEM:450.00 DEG C;
Electron spray voltage IS:+5500V;-4500V;
Gas curtain gas CUR:25.00psi;
Atomization gas GS1:45.00psi;
Dry gas GS2:65.00psi;
Collision gas CAD:7.00psi;
Scan mode: 0-9.2min is positive ion scanning, and 9.2-13min is negative ion scanning;
The ion pair parameter of the drug target that MRM detects is in table 2.Wherein Q1 is three grades of quadrupole rod first order, and Q3 is three grades of quadrupole rod third level, detects parent ion and the daughter ion of drug target respectively.Time, DP, CE are ion residence time (ms), separate bunch voltage (V) and impact energy (V).
Table 2MRM detects ion pair parameter
* be quota ion pair.
4, Qualitative Identification
For parent ion and the daughter ion pair of each medicine, at identical conditions, if the chromatography of ions peak retention time consistent with standard working solution (variation range is within ± 2.5%) in sample; In sample, the relative abundance of the relative abundance of two daughter ions of target compound standard solution suitable for concentration is consistent, and relative abundance deviation is no more than 30%, then can there is this kind of medicine in judgement sample.
5, quantitatively calculate
With vehicle solution prepare concentration be 0.05,0.1,0.2,0.5,1.0, each medicine mixed-matrix standard solution of 5.0mg/L, the chromatogram of each drug standard solution is shown in Fig. 1-12.Fig. 1 cathetus is the cut-off rule of two sections of scannings, and first paragraph is positive ion scanning, and second segment is negative ion scanning.The linearity curve equation of various medicine is respectively terramycin y=31.7x+2340, tetracycline y=110x+7490, aureomycin y=19.4x+5660, fortimicin y=20.1x+3270, procaine penicillin y=747x+97600, sulphadiazine y=104x+8930, sulfamethazine y=215x+13900, sulphathiazole y=11.8x+120, benzyl penicillin y=8.42x-1380.Measure by above-mentioned ion scan method sample introduction, take concentration as horizontal ordinate, the chromatographic peak area of quota ion is the typical curve that ordinate draws each medicine respectively, adopts this curve to calculate the content of various medicine in organic fertilizer sample to be measured respectively with external standard method.In the present embodiment, survey sample preparation two Duplicate Samples of organic fertilizer, represent the content of this sample Chinese traditional medicine after upper machine measures with mean value, two Duplicate Samples and mean value deviation be all less than 10%.Detecting sample, there is chromatographic peak at retention time 4.49min, 5.48min, 9.72min in it.By the chromatographic peak area obtained, according to the linear standard curve equation of each medicine, try to achieve the content of each medicine in machine solution, the content being scaled organic fertilizer Gold Samples mycin with the extension rate in sample handling processes and sample weighting amount is 0.41mg/kg, terramycin 0.23mg/kg, fortimicin 0.07mg/kg, sulphadiazine 0.02mg/kg, sulfamethazine 0.18mg/kg, tetracycline, procaine penicillin, sulphathiazole and benzyl penicillin do not detect.
Above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineering technical personnel in this area make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (1)
1. a detection method for organic fertilizer drug residue, comprises step:
1) sample pretreatment: by organic fertilizer sample blending, takes 1.0g sample in 50mL centrifuge tube, with the Na of 2 × 15mL pH 7.0
2eDTA-MclIvaine buffer solution mixes, repeat for twice to extract, each 15mL, mechanical shaking extraction 10min again after ultrasonic 10min, 10000rpm high speed centrifugation 10min, supernatant water layer directly proceeds to the silica matrix solid phase extraction column Strata SDB-L activated, and quantity of sorbent/volume is 500mg/6mL, uses 5mL methyl alcohol, 5mL water and 5mL Na in advance
2eDTA-MclIvaine damping fluid balances; Collect all effluxes simultaneously, shift extract in 100mL centrifuge tube with after 20mL ethyl acetate mechanical shaking extraction 10min; Solid phase extraction column drains rear 10mL methyl alcohol, 5mL acetonitrile and 5mL eluent ethyl acetate, merge all eluents in aforementioned 100mL centrifuge tube, supernatant is proceeded to glass heart bottle after the centrifugal 5min of 4500rpm, in 40 DEG C of water-baths, vacuum rotary steam dries up to nearly dry rear nitrogen in 50 DEG C, cross 0.22 μm of filter membrane with after the acetonitrile/0.1% aqueous formic acid constant volume of 1.0ml volume ratio 50/50, upper LC-MS/MS measures;
2) LC-MS/MS measures
Instrument: Agilent 1200 high performance liquid chromatography-API2000 three grades of quadrupole rod tandem mass spectrum combined instruments, are equipped with electron spray ESI ion gun;
Chromatographic column: Agilent XDB C18,4.6 × 150mm, particle diameter 5 μm;
Mobile phase: A water, containing 0.1% formic acid; B acetonitrile;
Flow velocity: 0.3mL/min;
Sample size: 10 μ L;
Column temperature: room temperature, 26 DEG C;
The column equilibration time, namely before next sample feeding: 8min;
Gradient elution program is as follows
3) mass spectroscopy
Scan mode: many reactive ion monitoring scanning;
Ion source temperature TEM:450.00 DEG C;
Electron spray voltage IS:+5500V;-4500V;
Gas curtain gas CUR:25.00psi;
Atomization gas GS1:45.00psi;
Dry gas GS2:65.00psi;
Collision gas CAD:7.00psi;
Scan mode: 0-9.2min is positive ion scanning, and 9.2-13min is negative ion scanning;
The ion pair parameter of the drug target that MRM detects is as follows, wherein Q1 is three grades of quadrupole rod first order, Q3 is three grades of quadrupole rod third level, detects parent ion and the daughter ion of drug target respectively, and Time, DP, CE are ion residence time ms, separate bunch voltage V and impact energy V;
* be quota ion pair;
4) Qualitative Identification
For parent ion and the daughter ion pair of each medicine, at identical conditions, if the chromatography of ions peak retention time in sample is consistent with standard working solution, variation range is within ± 2.5%; In sample, the relative abundance of the relative abundance of two daughter ions of target compound standard solution suitable for concentration is consistent, and relative abundance deviation is no more than 30%, then there is this kind of medicine in judgement sample;
5) quantitatively calculate
With vehicle solution prepare concentration be 0.05,0.1,0.2,0.5,1.0, each medicine mixed-matrix standard solution of 5.0mg/L, the linearity curve equation of various medicine is respectively terramycin y=31.7x+2340, tetracycline y=110x+7490, aureomycin y=19.4x+5660, fortimicin y=20.1x+3270, procaine penicillin y=747x+97600, sulphadiazine y=104x+8930, sulfamethazine y=215x+13900, sulphathiazole y=11.8x+120, benzyl penicillin y=8.42x-1380; Measure by above-mentioned ion scan method sample introduction, take concentration as horizontal ordinate, the chromatographic peak area of quota ion is the typical curve that ordinate draws each medicine respectively, adopts this curve to calculate the content of various medicine in organic fertilizer sample to be measured respectively with external standard method; Survey sample preparation two Duplicate Samples of organic fertilizer, represent the content of this sample Chinese traditional medicine after upper machine measures with mean value, two Duplicate Samples and mean value deviation be all less than 10%; Detecting sample, there is chromatographic peak at retention time 4.49min, 5.48min, 9.72min in it; By the chromatographic peak area obtained, according to the linear standard curve equation of each medicine, try to achieve the content of each medicine in machine solution, with the content in the extension rate in sample handling processes and sample weighting amount conversion organic fertilizer sample.
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| CN103439419B (en) * | 2013-07-12 | 2014-10-15 | 南开大学 | Experimental method of determining extracting agent for oxytetracycline residue in earthworm |
| CN106872628A (en) * | 2016-11-07 | 2017-06-20 | 上海德诺产品检测有限公司 | A kind of method for determining neoproc content |
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