CN105004782A - Method for fast detecting fumigation agent bromomethane residues in foods by headspace sample injection and ion mobility spectrometry - Google Patents
Method for fast detecting fumigation agent bromomethane residues in foods by headspace sample injection and ion mobility spectrometry Download PDFInfo
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Abstract
The invention discloses a method for fast detecting fumigation agent bromomethane residues in foods by headspace sample injection and ion mobility spectrometry. Bromomethane residues in a food sample are extracted by a saturated sodium chloride solution, a full-automatic headspace sample injection process is carried out and an ion mobility spectrometry-based detection process is carried out. A food matrix is pre-separated by rapid gas chromatography (GC), the separated food matrix in a single component form enters into an ion mobility spectrometry (IMS) ionizing zone and then reacts with reagent ions produced by radioactive tritium source ionization to produce product ions, the product ions enter into an IMS migration area under the action of ion pulse and are subjected to two-dimensional separation, and the separated ions are fed to a Faraday plate and are subjected to qualitative and quantitative detection, wherein an external standard method is used for quantification. The method has the characteristics of fastness, simpleness, high sensitivity, good separation effects, reagent saving and accurate and reliable qualitation and quantification and realizes separation of fumigation agent bromomethane residues in foods such as grains and fruits and fast qualitation and quantification.
Description
Technical field
The invention belongs to technical field of food safety, relate to a kind of headspace sampling and ion mobility spectrometry applied and detect the method that in food, fumigant methyl bromide is residual fast.
Background technology
Celfume, also known as bromomethane or methyl bromide, is colourless gas under normal temperature and pressure, usually tasteless, pleasantly sweet when high concentration.Molecular formula CH
3-Br, molecular weight 94.95, relative density 1.730 (0 ~ 4 DEG C); fusing point-93.66 DEG C, boiling point 3.6 DEG C, has strong fumigation action; can efficient, kill various harmful organism wide spectrum, be usually used in plant protection as pesticide, germifuge, soil fumigant and fumigation of grain agent.But, as a kind of pesticide carried all before one to harmful organism, be also apparent to the murder by poisoning of people: it is a kind of strong never poison, can cause direct damage to the skin of people, lung, kidney and liver.Can be there is the symptom such as heart failure, shock in severe poisoning, indivedual poisoner also there will be and loses the sight of both eyes.Further, Celfume is a kind of material of ozone layer depletion.Within 1992, Copenhagen amendment lists Celfume in controlled substance but quarantine and shipment pre-treatment (quarantine and per-shipment treatment, QPS) purposes is exempted, developed country eliminated in 2005, and developing country also eliminated in 2015 the Celfume fumigant using non-QPS purposes.China is food import and export big country, and Celfume is the fumigant that food quarantine suffocating treatment uses the most extensively and use amount is maximum.
Residue limits at present to fumigant methyl bromide, country variant has formulated strict limit standard, if the residue limits of China to the Celfume in grain is 5mg/kg, is 30mg/kg to the residue limits of the Celfume in fruit; The residue limits of European Union to the Celfume in grain is 0.1mg/kg is 0.05mg/kg etc. to the residue limits of the Celfume in fruit.Therefore it is necessary for setting up the method that in food fast and accurately, fumigant methyl bromide remains.
The detection of Celfume in present mensuration food, adopt vapor-phase chromatography more, the domestic examination criteria relating to Celfume in food residual is little at present, the detection method (SN 0649-1997. exports the Celfume residual quantity method of inspection in Cereals) of Celfume in the applicable Cereals that Zhi Jian China promulgates, the method pre-treating method uses sour refluxing extraction device to extract sample, vapor-phase chromatography detects, there is length consuming time in detection method, reagent consumption is large, determinand recovery is unstable, requires the problems such as high to the skill level of experiment operator.
Summary of the invention
For prior art Problems existing, a kind of application headspace sampling of quick, easy, highly sensitive, good separating effect and ion mobility spectrometry is the object of the present invention is to provide to detect the method that in food, fumigant methyl bromide is residual fast.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of headspace sampling and ion mobility spectrometry applied detects the method that in food, fumigant methyl bromide is residual fast, comprises the following steps:
1) saturated nacl aqueous solution that food samples fumigant methyl bromide is residual extracts;
2) full-automatic headspace sampling;
3) ion mobility spectrometry is used to detect;
4) interpretation of result.
Specifically, comprise the following steps:
1) saturated nacl aqueous solution that food samples fumigant methyl bromide is residual extracts
Accurately take sample 5.00 ± 0.01g in 20mL headspace sampling bottle, add 5mL saturated nacl aqueous solution, gland seals, and puts on the corresponding bottle position of head-space sampler, prepares sample introduction;
2) full-automatic headspace sampling
Head space stove incubation temperature 35 DEG C, ml headspace bottle equilibration time 10min, sample feeding amount 250 μ L, jolting speed 500rpm, sample introduction needle temperature 65 DEG C, filling speed 200 μ L/s, sample introduction speed 150 μ L/s;
3) ion mobility spectrometry is used to detect
C) preparation of standard solution: accurately pipette standard solution respectively, is made into the storing solution of 2mg/mL by water-soluble solution, is diluted to standard working solution during use;
D) ion mobility spectrometry examination criteria and sample is used: draw standard and sample respectively by full-automatic headspace autosampler, inject ion mobility spectrometry, after fast gas chromatography GC pre-separation, enter into ion mobility spectrometry IMS ionisation region with the form of single component, ionize with radioactive tritium source the reagent ion produced and react and form product ion; Product ion enters IMS migration area in ion pulse effect, carries out the separation of two dimension; Ion after separation finally arrives Faraday plate, completes qualitative and quantitative detection, quantified by external standard method;
4) interpretation of result
Software LAV is used for data processing.When sample is in IMS migration area, carry out the separation of two dimension, and after ion after isolation finally arrives Faraday plate, complete qualitative by the response peak position excursion time of this material, complete quantitatively with its signal peak area; With the mass concentration X of standard working solution for horizontal ordinate, the peak response Y of Celfume is ordinate, and drawing standard working curve, carries out quantified by external standard method with standard working curve to sample.
Described step 3) intermediate ion migration spectral condition: ion gun pattern negative ion mode, carrier gas high pure air, injector temperature 60 DEG C, detector temperature 45 DEG C, multidimensional capillary gas chromatographic column MCC, column temperature 40 DEG C, drift airshed 250mL/min, carrier gas flux 2mL/min.
Advantage of the present invention and good effect as follows:
(1) ion mobility spectrometry detection technique is introduced in the detection that in food, fumigant methyl bromide is residual by the present invention first, has novelty.
(2) pre-treatment saturated nacl aqueous solution being applied to Celfume residue detection in food is extracted, this method can complete in 10 minutes, and traditional method is extracted sample as used sour refluxing extraction device, there is length consuming time in detection method, reagent consumption is large, determinand recovery is unstable, requires the problems such as high to the skill level of experiment operator.And the inventive method extraction once only needs 5mL saturated sodium-chloride water solution, Full automatic head-space sample injector is hatched can direct injected after 10 minutes.Therefore the present invention have quick, easy, save reagent, the feature such as expense is low, extraction and cleaning is effective.
(3) qualitative foundation one dimension retention time of gas chromatography, ion mobility spectrometry can according to 2 retention times, the i.e. one dimension retention time of determinand after the pre-separation of one dimension quick MCC post and the two-dimentional retention time in the modulation period be again separated through the migration area of ion mobility spectrometry, mechanism interference can be eliminated, reduce false positive phenomenon, add accuracy qualitatively, therefore the inventive method is very applicable to the analysis that in food complex matrices, Celfume is residual.
(4) in conventional gas-phase stratographic analysis food, Celfume remains, and instrument may provide false-positive judgement.And Ion mobility spectrometry is a kind of trace level chemical substance analytical technology based on the migration velocity difference in the electric field of different ions in gas phase, there is high sensitivity, high selectivity detects the feature of volatile compound, be specially adapted to the compound to high electronegativity or high proton affinities, as the trace analysis of Celfume, compare with traditional sensing techniques, it is short that Ion mobility spectrometry has sense cycle, highly sensitive, to environment and the advantage such as sample requirement is low.
Accompanying drawing explanation
Fig. 1 is two-dimensional ionic migration spectrogram spectrum (part-time section spectrogram) of Celfume standard solution;
Fig. 2 is the single width ion mobility spectrometry feature spectrogram (part-time section spectrogram) of Celfume standard solution;
Fig. 3 is the standard working curve of this method;
Fig. 4 is two-dimensional ionic migration spectrogram spectrum (part-time section spectrogram) adding Celfume in embodiment 1 rice matrix
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
Application headspace sampling of the present invention and ion mobility spectrometry detect the method that in food, fumigant methyl bromide is residual fast, comprise the following steps:
1) saturated nacl aqueous solution that food samples fumigant methyl bromide is residual extracts;
2) full-automatic headspace sampling;
3) ion mobility spectrometry is used to detect;
4) interpretation of result.
Specifically, comprise the following steps:
1) saturated nacl aqueous solution that food samples fumigant methyl bromide is residual extracts
Accurately take sample 5.0O ± 0.01g in 20mL headspace sampling bottle, add 5mL saturated nacl aqueous solution, gland seals, and puts on the corresponding bottle position of head-space sampler, prepares sample introduction;
2) full-automatic headspace sampling
Head space stove incubation temperature 35 DEG C, ml headspace bottle equilibration time 10min, sample feeding amount 250 μ L, jolting speed 500rpm, sample introduction needle temperature 65 DEG C, filling speed 200 μ L/s, sample introduction speed 150 μ L/s;
3) ion mobility spectrometry is used to detect
E) preparation of standard solution: accurately pipette standard solution respectively, is made into the storing solution of 2mg/mL by water-soluble solution, is diluted to standard working solution during use;
F) ion mobility spectrometry examination criteria and sample is used: draw standard and sample respectively by full-automatic headspace autosampler, inject ion mobility spectrometry, after fast gas chromatography GC pre-separation, enter into ion mobility spectrometry IMS ionisation region with the form of single component, ionize with radioactive tritium source the reagent ion produced and react and form product ion; Product ion enters IMS migration area in ion pulse effect, carries out the separation of two dimension; Ion after separation finally arrives Faraday plate, completes qualitative and quantitative detection, quantified by external standard method;
4) interpretation of result
Software LAV is used for data processing.When sample is in IMS migration area, carry out the separation of two dimension, and after ion after isolation finally arrives Faraday plate, complete qualitative by the response peak position excursion time of this material, complete quantitatively with its signal peak area; The two-dimensional ionic migration spectrogram spectrum of Celfume standard solution, is shown in Fig. 1; The single width ion mobility spectrometry feature spectrogram of Celfume standard solution, is shown in Fig. 2; With the mass concentration X of standard working solution for horizontal ordinate, the peak response Y of Celfume is ordinate, and drawing standard working curve, carries out quantified by external standard method with standard working curve to sample.
Described step 3) intermediate ion migration spectral condition: ion gun pattern negative ion mode, carrier gas high pure air, injector temperature 60 DEG C, detector temperature 45 DEG C, multidimensional capillary gas chromatographic column MCC, column temperature 40 DEG C, drift airshed 250mL/min, carrier gas flux 2mL/min.
Embodiment 1
Celfume is detected in rice matrix
1. instrument and reagent
Instrument: Flavour
ion mobility spectrometry (German G.A.S company), is equipped with Full automatic head-space sample injector; Sample passes through head-space sampler sample introduction, negative ion mode.
Reagent: saturated nacl aqueous solution, Celfume standard solution 2000mg/L (purity is not less than 95%, purchased from O2Si company), uses the standard solution of front water (secondary water) required for solvent preparation.
2. sample preparation
(1) sample extraction: accurately take sample 5.00 ± 0.01g in 20mL headspace sampling bottle, add 5mL saturated nacl aqueous solution, gland seals, and puts on the corresponding bottle position of head-space sampler, prepares sample introduction to be measured.
(2) standard working solution: add corresponding standard solution respectively in the sample injection bottle that 5ml bare substrate saturated nacl aqueous solution is housed, be made into 0,0.02,0.05,0,10,0.20,0.30,0.40,0.50,0.60,0.70,0.80,0.90,1.00,1.20,1.40,1.60,1.80,2.00ug/g series standard, drawing standard working curve, is shown in Fig. 3.
(3) sample determination method: standard and sample be difference sample introduction on ion mobility spectrometry.
Head-space sampler condition: head space stove incubation temperature 35 DEG C, ml headspace bottle equilibration time 10min, sample feeding amount 250 μ L, jolting speed 500rpm, sample introduction needle temperature 65 DEG C, filling speed 200 μ L/s, sample introduction speed 150 μ L/s.
Ion mobility spectrometry testing conditions: multi capalliry column (MCC) chromatographic column (OV-5); Ion gun pattern is negative ion mode, carrier gas high pure air, injector temperature 60 DEG C, detector temperature 45 DEG C, column temperature 40 DEG C, drift airshed 250mL/min, carrier gas flux 2mL/min.
(4) interpretation of result: software LAV2.1.1 is used for data processing, first standard spectrogram is obtained, (the method can comprise determinand title to set up qualitative-and-quantitative method, GC and IMS retention time, GC and IMS retention time permissible variation, sample type, concentration unit, the information such as signal to noise ratio (S/N ratio), table of corrections, correction equation, normal concentration), sample spectrogram qualitative or quantitative Treatment method carry out spectrogram process, obtain quantitative and qualitative analysis result.In this rice sample, detect Celfume 0.80mg/kg, spectrogram is shown in Fig. 4.
Embodiment 2
Wheat samples utilizes gas chromatography electron capture detector (ECD) to check, and detects Celfume, utilizes ion mobility spectrometry to confirm this sample, and result shows not detect Celfume in sample, and what gas chromatographic detection arrived is chaff interference.
Instrument and reagent
Instrument condition and pre-treating method are with embodiment 1
Result: do not detect Celfume in wheat samples.
Embodiment 3
Strawberry sample after methyl bromide fumigation process utilizes the inventive method to detect Celfume.
Instrument condition and pre-treating method are with embodiment 1, and result utilizes the inventive method to detect Celfume 1.40mg/kg at strawberry sample.
The mark-on recovery test of three kinds of different substrates is carried out according to 0.05mg/kg, 0.1mg/kg, 0.2mg/kg tri-mark-on levels, result is the average recovery rate 76%-110% (n=10) of Celfume, relative standard deviation is less than 8.0%, and having good stability of this method, the results are shown in Table 1.Quantitative limit (LOQ) value of this method is 0.05mg/kg, meets the limitation requirement that relevant Celfume is residual both at home and abroad.
Table 1 recovery of standard addition measurement result (n=10)
Table 1 The result of recoveriestest(n＝10)
Remain with the fumigant methyl bromide in methods analyst food of the present invention and there is higher sensitivity, method accurately and reliably, simple fast, save reagent, the fumigant methyl bromide residue detection analysis be applied to by ion mobility spectrometry in food has novelty, this inventive method can meet limitation requirement as residual to Celfume in food in European Union, the U.S., Japan and Korea S etc. both at home and abroad, is conducive to the edible safety of guarantee consumer and promotes the smooth outlet of China's food.
Ionic migration spectrometer technology is a kind of trace level chemical substance analytical technology based on the migration velocity difference in the electric field of different ions in gas phase, has high sensitivity, and high selectivity detects the feature of volatile compound.Complex mixture, after fast GC pre-separation, enters into IMS ionisation region with the form of single component, ionizes the reagent ion produced react and form product ion with radioactive tritium source; Product ion enters IMS migration area in ion pulse effect, carries out the separation of two dimension; Ion after separation finally arrives Faraday plate and is detected.Be specially adapted to the trace analysis of the compound to high electronegativity or high proton affinities, compare with traditional sensing techniques, it is short that IMS technology has sense cycle, highly sensitive, and there is the outstanding advantages such as sample size is few, fast and convenient, to environment and the advantage such as sample requirement is low.
Utilize headspace sampling and ion mobility spectrometry to carry out detection and to complete in food that fumigant methyl bromide is residual to be detected this method fast there is not been reported at present both at home and abroad.
Above-described embodiment is only for illustration of technological thought of the present invention and feature, its object is to enable those skilled in the art understand content of the present invention and implement according to this, only can not limit the scope of the claims of the present invention with the present embodiment, namely the equal change done of all disclosed spirit or modification, still drop in the scope of the claims of the present invention.
Claims (3)
1. apply headspace sampling and ion mobility spectrometry and detect the method that in food, fumigant methyl bromide is residual fast, it is characterized in that, comprise the following steps:
1) saturated nacl aqueous solution that food samples fumigant methyl bromide is residual extracts;
2) full-automatic headspace sampling;
3) ion mobility spectrometry is used to detect;
4) interpretation of result.
2. application headspace sampling according to claim 1 and ion mobility spectrometry detect the method that in food, fumigant methyl bromide is residual fast, it is characterized in that, comprise the following steps:
1) saturated nacl aqueous solution that food samples fumigant methyl bromide is residual extracts
Accurately take sample 5.00 ± 0.01g in 20mL headspace sampling bottle, add 5mL saturated nacl aqueous solution, gland seals, and puts on the corresponding bottle position of head-space sampler, prepares sample introduction;
2) full-automatic headspace sampling
Head space stove incubation temperature 35 DEG C, ml headspace bottle equilibration time 10min, sample feeding amount 250 μ L, jolting speed 500rpm, sample introduction needle temperature 65 DEG C, filling speed 200 μ L/s, sample introduction speed 150 μ L/s;
3) ion mobility spectrometry is used to detect
A) preparation of standard solution: accurately pipette standard solution respectively, is made into the storing solution of 2mg/mL by water-soluble solution, is diluted to standard working solution during use;
B) ion mobility spectrometry examination criteria and sample is used: draw standard and sample respectively by full-automatic headspace autosampler, inject ion mobility spectrometry, after fast gas chromatography GC pre-separation, enter into ion mobility spectrometry IMS ionisation region with the form of single component, ionize with radioactive tritium source the reagent ion produced and react and form product ion; Product ion enters IMS migration area in ion pulse effect, carries out the separation of two dimension; Ion after separation finally arrives Faraday plate, completes qualitative and quantitative detection, quantified by external standard method;
4) interpretation of result
Software LAV is used for data processing.When sample is in IMS migration area, carry out the separation of two dimension, and after ion after isolation finally arrives Faraday plate, complete qualitative by the response peak position excursion time of this material, complete quantitatively with its signal peak area; With the mass concentration X of standard working solution for horizontal ordinate, the peak response Y of Celfume is ordinate, and drawing standard working curve, carries out quantified by external standard method with standard working curve to sample.
3. application headspace sampling according to claim 2 and ion mobility spectrometry detect the method that in food, fumigant methyl bromide is residual fast, it is characterized in that, described step 3) intermediate ion migration spectral condition: ion gun pattern negative ion mode, carrier gas high pure air, injector temperature 60 DEG C, detector temperature 45 DEG C, multidimensional capillary gas chromatographic column MCC, column temperature 40 DEG C, drift airshed 250mL/min, carrier gas flux 2mL/min.
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Application publication date: 20151028 |