CN118130648A - Detection method of short-chain or medium-chain chlorinated paraffin in aquatic product - Google Patents
Detection method of short-chain or medium-chain chlorinated paraffin in aquatic product Download PDFInfo
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Abstract
The invention discloses a detection method of short-chain or medium-chain chlorinated paraffin in aquatic products, which relates to the technical field of food detection, and comprises the following steps: sequentially carrying out accelerated solvent extraction, gel permeation chromatography purification and organic filter membrane filtration on an aquatic product sample to be detected to obtain a purified solution; obtaining a retention time, characteristic ions and ion fragment mass chromatogram of chlorinated paraffin homologs and a total ion flow mass chromatogram by using a chlorinated paraffin standard solution; establishing a standard curve; and (3) adding a standard to the purifying liquid for detection, carrying out matching analysis, carrying out standard curve calculation, and qualitatively or quantitatively analyzing the short-chain or medium-chain chlorinated paraffin in the aquatic product sample to be detected. The method adopts the combination of accelerated solvent extraction, gel permeation chromatography and gas chromatography mass spectrometry, has the advantages of high automation degree, less reagent consumption, high extraction efficiency, good method reproduction and the like, and is simultaneously suitable for the analysis and detection of short-chain and medium-chain chlorinated paraffin in aquatic products.
Description
Technical Field
The invention relates to the technical field of food detection, in particular to a detection method of short-chain or medium-chain chlorinated paraffin in an aquatic product.
Background
Chlorinated paraffins (Chlorinated paraffins, CPs), also known as polychlorinated normal paraffins (Polychlorinated n-alkanes, PCAs), are a class of synthetic straight-chain alkane chlorinated derivatives, and are widely used in industry for metal working fluids, plasticizers, flame retardants, and the like. Short-chain chlorinated paraffins (C 10-C13, SCCPs), medium-chain chlorinated paraffins (C 14-C17, MCCPs) and long-chain chlorinated paraffins (C 18-C30, LCCPs) are classified according to their carbon chain lengths. Among them, SCCPs were listed in the controlled list of accessory A, about the Stockholm convention of persistent organic pollutants, in month 5 of 2017, due to their environmental persistence, long-range mobility, and bioaccumulation properties. With the limited use of SCCPs, MCCPs was widely used as a substitute for SCCPs because of its similar physicochemical properties and was proposed in the candidate bill of matter under the schde bro convention on persistent organic pollutants, month 1 of 2022.
In recent years, as CPs are successively detected in environmental media such as the atmosphere, water bodies, and sediments, scholars have studied and found that the accumulation of CPs in aquatic animals is not quite small, and different levels of detection are found in aquatic organism groups in north america, western europe, and even in polar regions. However, the detection of CPs in aquatic organisms is relatively few in China, and the research is concentrated on SCCPs. The aquatic products are a mainstream food consumption mode in coastal areas because of rich nutrition, and CPs in the aquatic products are enriched in human bodies through dietary intake, so that the health of human beings is finally affected. Therefore, the establishment of a method capable of simultaneously and rapidly measuring the content of SCCPs and MCCPs in the aquatic products is important to know and master the pollution condition of the CPs in the aquatic products.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a detection method of short-chain or medium-chain chlorinated paraffin in an aquatic product, which adopts the combination of accelerated solvent extraction, gel permeation chromatography and gas chromatography mass spectrometry, has the advantages of high automation degree, less reagent consumption, high extraction efficiency, good method reproduction and the like, and is simultaneously suitable for the analysis and detection of the short-chain or medium-chain chlorinated paraffin in the aquatic product.
The technical scheme for solving the technical problems is as follows: the method for detecting the short-chain or medium-chain chlorinated paraffin in the aquatic product is characterized by comprising the following steps of:
(1) Crushing an aquatic product sample to be detected, freeze-drying, adding diatomite, uniformly mixing, and then extracting by using an accelerated solvent to obtain an extracting solution;
(2) Adding 40wt% of acidic silica gel into the extract obtained in the step (1), taking supernatant, performing rotary evaporation, dissolving with ethyl acetate and cyclohexane in a volume ratio of 1:1, purifying by gel permeation chromatography, concentrating by nitrogen blowing, dissolving in cyclohexane, and filtering by using an organic filter membrane to obtain a sample purifying liquid to be detected;
(3) Diluting a plurality of chlorinated paraffin standard solutions with cyclohexane with equal volume respectively to obtain standard solution stock solution;
(4) Mixing the standard solution stock solution obtained in the step (3) according to different volume ratios to obtain chlorinated paraffin standard solution series with different chlorine contents;
(5) Carrying out chromatographic separation and mass spectrometry analysis on the standard solution stock solution obtained in the step (3) to obtain a retention time, characteristic ion and ion fragment mass chromatogram and a total ion flow mass chromatogram of the chlorinated paraffin homolog;
(6) Performing chromatographic separation and mass spectrometry analysis on the chlorinated paraffin standard solution series with different chlorine contents obtained in the step (4), and establishing a standard curve between the chlorine content and the total response factor;
(7) And (3) carrying out chromatographic separation and mass spectrometry analysis on the purifying liquid of the to-be-detected sample and the internal standard sample obtained in the step (2) to obtain a chromatogram and a peak area of the to-be-detected aquatic product sample, carrying out matching analysis on the chromatogram, carrying out standard curve calculation, and qualitatively or quantitatively analyzing short-chain or medium-chain chlorinated paraffin in the to-be-detected aquatic product sample by an internal standard method.
Further, in the step (1), the mass ratio of the aquatic product sample to be detected to the diatomite is 1 g:0.8-1.2 g.
Further, in step (1), the solvent extraction is accelerated: the solvent is dichloromethane and n-hexane with the volume ratio of 1:1; the extraction temperature is 100 ℃; the extraction pressure was 1500psi; the static extraction time is 10min; the heating time is 5min; the flush volume was 60%; the purging time is 60s; the number of cycles was 2.
Further, the mass ratio of the aquatic product sample to be detected to 40wt% of acidic silica gel is 1g to 0.8-1.2g.
An appropriate amount of 40wt% acidic silica gel is added into the extract obtained by accelerating solvent extraction to remove the fat and other interfering substances so as to remove the fat and other interfering substances.
Further, in the step (2), when gel permeation chromatography is used for purification: a Bio-beads S-X3 glass gel chromatography column was used; the mobile phase is ethyl acetate and cyclohexane with the volume ratio of 1:1; the flow rate is 5.0mL/min; the effluent collection time is 9-21min.
The beneficial effects of adopting further technical scheme are: the aquatic product matrix is complex, contains a large amount of substances such as moisture, protein, fat and the like, and if the aquatic product matrix is directly injected after extraction, the problems of low recovery rate, poor sensitivity and the like often occur. Therefore, gel permeation chromatography is selected as a purifying means, so that the matrix effect of the detection method is reduced, and the detection accuracy is improved.
Further, in the step (2), the pore size of the organic filter membrane was 0.22. Mu.m.
Further, in the step (3), the various chlorinated paraffin standard solutions are short-chain chlorinated paraffin standard solutions having chlorine contents of 51.5%, 55.5% and 63.O% of 100. Mu.g/mL, respectively.
Then mixing the standard solutions of short-chain chlorinated paraffin with the volume ratio of 51.5% and 55.5% to 1:1, and mixing the standard solutions of short-chain chlorinated paraffin with the volume ratio of 55.5% and 63.0% to 1:1, 4:1 and 1:4 to form a series of standard solutions of chlorinated paraffin with different chlorine contents and chlorine contents of 51.5%, 53.5%, 55.5%, 57.0%, 59.25%, 61.5% and 63.0%.
Further, in the step (3), the various chlorinated paraffin standard solutions are medium-chain chlorinated paraffin standard solutions having chlorine contents of 42%, 52% and 57% respectively, of 100. Mu.g/mL.
Then mixing 42.0% and 52.0% medium chain chlorinated paraffin standard solution according to the volume ratio of 4:1, 1:1 and 1:4, mixing 52.0% and 57.0% short chain chlorinated paraffin standard solution according to the volume ratio of 1:1, and composing chlorinated paraffin standard solution series with different chlorine contents of 42.0%, 44.0%, 47.0%, 50.0%, 52.0%, 54.5% and 57.0%.
Further, in step (7), the internal standard sample is ε -HCH.
Further, in steps (5), (6) and (7), upon chromatographic separation: the chromatographic column is DB-5MS with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m; the temperature of the sample inlet is 280 ℃; the sample injection amount is 1 mu L; the sample injection mode is non-split sample injection; the carrier gas is high-purity helium; the flow rate of carrier gas is 1mL/min; the temperature of the transmission line is 280 ℃; the temperature program is 100 ℃ and kept for 1min, 15 ℃/min is used for heating to 160 ℃ and kept for 2min, and 30 ℃/min is used for heating to 310 ℃ and kept for 15min.
Further, in steps (5), (6) and (7), mass spectrometry analysis: an electron capture anion source; the temperature of the ion source is 150 ℃; the reaction gas is methane; the scanning mode is selected ion monitoring; the solvent delay time was 3min.
The qualitative and quantitative ions of the short-and medium-chain chlorinated paraffins are shown in Table 1.
Tables 1 SCCPs and MCCPs qualitative and quantitative ion tables
The invention has the following beneficial effects:
1. The invention establishes a detection method for measuring short-chain or medium-chain chlorinated paraffin in aquatic products by combining accelerated solvent extraction, gel permeation chromatography purification, gas chromatography mass spectrometry, and the method adopts equipment such as an accelerated solvent extractor, a gel permeation chromatograph and the like, has the advantages of high degree of automation, less reagent consumption, high extraction efficiency, good method reproduction and the like, and is simultaneously suitable for the analysis and detection of SCCPs and MCCPs in the aquatic products.
2. The detection method of the short-chain or medium-chain chlorinated paraffin in the aquatic product has the advantages of weak matrix effect, good repeatability, high precision and low detection limit. The detection limits of SCCPs and MCCPs in the method of the invention are 16.2ng/g and 17.9ng/g respectively. CPs are used as novel organic pollutants, food detection standards related to CPs are not established at home and abroad at present, and the establishment of the method can provide technical support for establishing related food standard methods.
Drawings
FIG. 1 is a graph of recovery of SCCPS and MCCPS in different extraction solvents;
FIG. 2 is a graph of recovery of SCCPS and MCCPS at different extraction temperatures;
FIG. 3 is a graph of recovery at SCCPS and MCCPS for different static extraction times;
FIG. 4 is a graph of recovery of SCCPS and MCCPS for various accelerated solvent extraction cycles;
FIG. 5 is a GPC outflow diagram of SCCPS and MCCPS;
FIG. 6 is a SCCPS total ion current mass chromatogram;
FIG. 7 is a MCCPS total ion current mass chromatogram.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
A detection method of short-chain or medium-chain chlorinated paraffin in aquatic products comprises the following steps:
(1) Crushing 1g of bream sample, freeze-drying, adding 0.8g of diatomite, uniformly mixing, and extracting by using an accelerated solvent to obtain an extracting solution; accelerating solvent extraction: the solvent is dichloromethane and n-hexane with the volume ratio of 1:1; the extraction temperature is 100 ℃; the extraction pressure was 1500psi; the static extraction time is 10min; the heating time is 5min; the flush volume was 60%; the purging time is 60s; the cycle number is 2;
(2) Adding 0.8g of 40wt% acidic silica gel into the extract obtained in the step (1), taking supernatant, rotationally evaporating, dissolving with 10mL of ethyl acetate and cyclohexane with the volume ratio of 1:1, purifying by gel permeation chromatography, concentrating by nitrogen blowing, dissolving in 200 mu L of cyclohexane, and finally filtering by using a 0.22 mu m organic filter membrane to obtain a sample purifying liquid to be detected; gel permeation chromatography purification: a Bio-beads S-X3 glass gel chromatography column was used; the mobile phase is ethyl acetate and cyclohexane with the volume ratio of 1:1; the flow rate is 5.0mL/min; the effluent liquid collecting time is 9-21min;
(3) Respectively diluting 100 mug/ml short-chain chlorinated paraffin standard solutions with chlorine content of 51.5%, 55.5% and 63.0% by using cyclohexane with equal volumes to obtain standard solution stock solution;
(4) Mixing the standard solution stock solutions obtained in the step (3) according to different volume ratios to obtain chlorinated paraffin standard solution series with different chlorine contents, wherein the chlorine contents are respectively 51.5%, 53.5%, 55.5%, 57.0%, 59.25%, 61.5% and 63.0%;
(5) Carrying out chromatographic separation and mass spectrometry analysis on the standard solution stock solution obtained in the step (3) to obtain a retention time, characteristic ion and ion fragment mass chromatogram and a total ion flow mass chromatogram of the chlorinated paraffin homolog; the mass chromatogram of the short-chain chlorinated paraffin total ion flow is shown in figure 6;
(6) Performing chromatographic separation and mass spectrometry analysis on the chlorinated paraffin standard solution series with different chlorine contents obtained in the step (4), and establishing a standard curve between the chlorine content and the total response factor;
(7) And (3) carrying out chromatographic separation and mass spectrometry analysis on the sample purifying liquid to be detected obtained in the step (2) and 10ng/g epsilon-HCH of an internal standard sample to obtain a chromatogram and a peak area of the bream sample, carrying out matching analysis on the chromatogram, carrying out standard curve calculation, and qualitatively or quantitatively analyzing short-chain chlorinated paraffin in the bream sample by an internal standard method.
Wherein, during chromatographic separation: the chromatographic column is DB-5MS with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m; the temperature of the sample inlet is 280 ℃; the sample injection amount is 1 mu L; the sample injection mode is non-split sample injection; the carrier gas is high-purity helium; the flow rate of carrier gas is 1mL/min; the temperature of the transmission line is 280 ℃; the temperature program is 100 ℃ and kept for 1min, 15 ℃/min is used for heating to 160 ℃ and kept for 2min, and 30 ℃/min is used for heating to 310 ℃ and kept for 15min.
Wherein, during mass spectrometry analysis: an electron capture anion source; the temperature of the ion source is 150 ℃; the reaction gas is methane; the scanning mode is selected ion monitoring; the solvent delay time was 3min.
Example 2
A detection method of short-chain or medium-chain chlorinated paraffin in aquatic products comprises the following steps:
(1) Crushing 1g of crab sample, freeze-drying, adding 1.2g of diatomite, uniformly mixing, and extracting by using an accelerated solvent to obtain an extracting solution; accelerating solvent extraction: the solvent is dichloromethane and n-hexane with the volume ratio of 1:1; the extraction temperature is 100 ℃; the extraction pressure was 1500psi; the static extraction time is 10min; the heating time is 5min; the flush volume was 60%; the purging time is 60s; the cycle number is 2;
(2) Adding 1.2g of 40wt% acidic silica gel into the extract obtained in the step (1), taking supernatant, rotationally evaporating, dissolving with 10mL of ethyl acetate and cyclohexane with the volume ratio of 1:1, purifying by gel permeation chromatography, concentrating by nitrogen blowing, dissolving in 200 mu L of cyclohexane, and finally filtering by using a 0.22 mu m organic filter membrane to obtain a sample purifying liquid to be detected; gel permeation chromatography purification: a Bio-beads S-X3 glass gel chromatography column was used; the mobile phase is ethyl acetate and cyclohexane with the volume ratio of 1:1; the flow rate is 5.0mL/min; the effluent liquid collecting time is 9-21min;
(3) Respectively diluting 100 mug/mL medium-chain chlorinated paraffin standard solutions with chlorine content of 42%, 52% and 57% by using cyclohexane with equal volume to obtain standard solution stock solution;
(4) Mixing the standard solution stock solutions obtained in the step (3) according to different volume ratios to obtain chlorinated paraffin standard solution series with different chlorine contents, wherein the chlorine contents are 42.0%, 44.0%, 47.0%, 50.0%, 52.0%, 54.5% and 57.0% respectively;
(5) Carrying out chromatographic separation and mass spectrometry analysis on the standard solution stock solution obtained in the step (3) to obtain a retention time, characteristic ion and ion fragment mass chromatogram and a total ion flow mass chromatogram of the chlorinated paraffin homolog; the mass chromatogram of the medium-chain chlorinated paraffin total ion flow is shown in figure 7;
(6) Performing chromatographic separation and mass spectrometry analysis on the chlorinated paraffin standard solution series with different chlorine contents obtained in the step (4), and establishing a standard curve between the chlorine content and the total response factor;
(7) And (3) carrying out chromatographic separation and mass spectrometry analysis on the sample purifying liquid to be detected and the internal standard sample 10ng/g epsilon-HCH obtained in the step (2) to obtain a chromatogram and a peak area of the crab sample, carrying out matching analysis on the chromatogram, carrying out standard curve calculation, and qualitatively or quantitatively analyzing medium-chain chlorinated paraffin in the crab sample by an internal standard method.
Wherein, during chromatographic separation: the chromatographic column is DB-5MS with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m; the temperature of the sample inlet is 280 ℃; the sample injection amount is 1 mu L; the sample injection mode is non-split sample injection; the carrier gas is high-purity helium; the flow rate of carrier gas is 1mL/min; the temperature of the transmission line is 280 ℃; the temperature program is 100 ℃ and kept for 1min, 15 ℃/min is used for heating to 160 ℃ and kept for 2min, and 30 ℃/min is used for heating to 310 ℃ and kept for 15min.
Wherein, during mass spectrometry analysis: an electron capture anion source; the temperature of the ion source is 150 ℃; the reaction gas is methane; the scanning mode is selected ion monitoring; the solvent delay time was 3min.
Example 3
A detection method of short-chain or medium-chain chlorinated paraffin in aquatic products comprises the following steps:
(1) Crushing 1g of clam sample, freeze-drying, adding 1g of diatomite, uniformly mixing, and then extracting by using an accelerated solvent to obtain an extracting solution; accelerating solvent extraction: the solvent is dichloromethane and n-hexane with the volume ratio of 1:1; the extraction temperature is 100 ℃; the extraction pressure was 1500psi; the static extraction time is 10min; the heating time is 5min; the flush volume was 60%; the purging time is 60s; the cycle number is 2;
(2) Adding 1g of 40wt% acidic silica gel into the extract obtained in the step (1), taking supernatant, rotationally evaporating, dissolving with 10mL of ethyl acetate and cyclohexane with the volume ratio of 1:1, purifying by gel permeation chromatography, concentrating by nitrogen blowing, dissolving in 200 mu L of cyclohexane, and finally filtering by using a 0.22 mu m organic filter membrane to obtain a sample purifying liquid to be detected; gel permeation chromatography purification: a Bio-beads S-X3 glass gel chromatography column was used; the mobile phase is ethyl acetate and cyclohexane with the volume ratio of 1:1; the flow rate is 5.0mL/min; the effluent liquid collecting time is 9-21min;
(3) Diluting 100 mug/ml of short-chain chlorinated paraffin with chlorine content of 51.5%, 55.5% and 63.0% and medium-chain chlorinated paraffin standard solution with chlorine content of 42%, 52% and 57% respectively by using cyclohexane with equal volume to obtain standard solution stock solution;
(4) Mixing the standard solution stock solutions obtained in the step (3) according to different volume ratios to obtain chlorinated paraffin standard solution series with different chlorine contents, wherein the chlorine content of the short-chain chlorinated paraffin is respectively 51.5%, 53.5%, 55.5%, 57.0%, 59.25%, 61.5% and 63.0%, and the chlorine content of the medium-chain chlorinated paraffin is respectively 42.0%, 44.0%, 47.0%, 50.0%, 52.0%, 54.5% and 57.0%;
(5) Carrying out chromatographic separation and mass spectrometry analysis on the standard solution stock solution obtained in the step (3) to obtain a retention time, characteristic ion and ion fragment mass chromatogram and a total ion flow mass chromatogram of the chlorinated paraffin homolog;
(6) Performing chromatographic separation and mass spectrometry analysis on the chlorinated paraffin standard solution series with different chlorine contents obtained in the step (4), and establishing a standard curve between the chlorine content and the total response factor;
(7) And (3) carrying out chromatographic separation and mass spectrometry analysis on the sample purifying liquid to be detected and the internal standard sample 10ng/g epsilon-HCH obtained in the step (2) to obtain a chromatogram and a peak area of the clam sample, carrying out matching analysis on the chromatogram, carrying out standard curve calculation, and qualitatively or quantitatively analyzing short-chain chlorinated paraffin and medium-chain chlorinated paraffin in the clam sample by an internal standard method.
Wherein, during chromatographic separation: the chromatographic column is DB-5MS with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m; the temperature of the sample inlet is 280 ℃; the sample injection amount is 1 mu L; the sample injection mode is non-split sample injection; the carrier gas is high-purity helium; the flow rate of carrier gas is 1mL/min; the temperature of the transmission line is 280 ℃; the temperature program is 100 ℃ and kept for 1min, 15 ℃/min is used for heating to 160 ℃ and kept for 2min, and 30 ℃/min is used for heating to 310 ℃ and kept for 15min.
Wherein, during mass spectrometry analysis: an electron capture anion source; the temperature of the ion source is 150 ℃; the reaction gas is methane; the scanning mode is selected ion monitoring; the solvent delay time was 3min.
Test example 1
Accelerated Solvent Extraction (ASE) is an automated process for extracting solid or semi-solid samples with solvents at a temperature (40-200 ℃) and pressure (1000-3000 psi). The main factors affecting the ASE extraction efficiency are the kind of extraction solvent, extraction temperature, static extraction time, the number of cycles, etc. The test example adopts the recovery rate of negative samples (adding the standard quantity of 50 ng/g) to reflect the extraction efficiency, and respectively examines the influence of the four factors, and in order to ensure the accuracy and the precision, each optimization condition carries out the measurement of 1 blank sample and 3 parallel samples.
(1) Optimization of extraction solvent
CPs are weak polar compounds with good solubility in nonpolar or weak polar solvents. The effect on the extraction efficiency of the target was verified using methylene chloride, n-hexane, and 3 common extraction solvents of methylene chloride and n-hexane in a volume ratio of 1:1, respectively, and the results are shown in FIG. 1.
As can be seen from FIG. 1, the extraction effect of dichloromethane and n-hexane in a volume ratio of 1:1 is better than that of other 2 extraction solvents used independently, so that the extraction solvent is finally selected to be dichloromethane and n-hexane in a volume ratio of 1:1.
(2) Optimization of extraction temperature
Accelerated solvent extraction was performed at three extraction temperatures, 80 ℃,100 ℃ and 120 ℃, respectively, and the effect on extraction efficiency was verified, and the results are shown in fig. 2.
As can be seen from fig. 2, the extraction efficiency is improved with the increase of the extraction temperature. The average recovery of SCCPs and MCCPs was 80.9% and 87.4% when the extraction temperature was 80 ℃; when the extraction temperature is raised to 100 ℃, the average recovery rate of the target substances is respectively increased to 96.3 percent and 103.5 percent; when the extraction temperature is 120 ℃, the recovery rate is not obviously changed. However, the higher the temperature, the more likely it is that part of the co-extract will be extracted from the matrix, thus interfering with the GC-MS determination, so that in one embodiment of the invention the ASE extraction temperature is chosen to be 100 ℃.
(3) Optimization of static extraction time
Accelerated solvent extraction was performed at three different static extraction time periods of 5min, 10min, and 15min, respectively, and the effect on extraction efficiency was examined, and the results are shown in fig. 3.
As can be seen from fig. 3, the recovery rate was lower when the static extraction time was 5min (average recovery rates of SCCPs and MCCPs were 78.1% and 82.7%); however, when the static extraction time is from 10min, the extraction efficiency of the sample is not changed obviously, and the average recovery rate is between 96.8 and 103.8 percent. Considering the increase of the extraction time, on the one hand, the extraction of interfering substances in the sample matrix may result in influencing the detection result, and on the other hand, the experimental time may also be increased. Thus, in one embodiment of the invention, ASE static extraction time is selected to be 10min.
(4) Optimization of cycle times
The effect of different cycle times (1, 2, 3) on extraction efficiency was examined and the results are shown in figure 4.
As can be seen from FIG. 4, the recovery rate of the target was poor (average recovery rates of SCCPs and MCCPs were 75.2% and 86.8%) at 1 cycle, and the samples were not sufficiently extracted; when the cycle is carried out for 2 times, the average recovery rate of the target object is respectively improved to 96.3 percent and 105.4 percent; the recovery rate is not obviously changed when the cycle is carried out for 3 times, but the extraction time is increased by 15 minutes, and the extraction solvent consumes 20mL more. The number of ASE cycles selected in one embodiment of the invention is 2.
Test example 2
The aquatic product matrix is complex, contains a large amount of substances such as moisture, protein, fat and the like, and if the aquatic product matrix is directly injected after extraction, the problems of low recovery rate, poor sensitivity and the like often occur. Therefore, it is necessary to select an appropriate purification means to reduce the matrix effect. Gel Permeation Chromatography (GPC) techniques are based on the principle of size exclusion, with separation at different retention times depending on molecular weight. The test selects a Bio-beads S-X3 gel chromatographic column (470 mm multiplied by 40mm,200-400 meshes) as a purifying column, and takes ethyl acetate and cyclohexane with the volume ratio of 1:1 as mobile phases to examine the outflow time of SCCPS and MCCPS in GPC. GPC effluent was discarded 5 minutes before, and then collected every 2 minutes, and GPC effluent was collected for a total of 20 minutes, concentrated and then examined by GC/MS, and GPC effluent curves of SCCPS and MCCPS are shown in FIG. 5.
As can be seen from FIG. 5, SCCPS flows out for 13-21min and MCCPS flows out for 9-19min, so the collection time is 9-21min in one embodiment of the invention.
Test example 3
The linear range, limit of detection, matrix effect, recovery, precision and reproducibility of the method of the invention were evaluated by methodological validation.
(1) Linear range and detection limit
The prepared SCCPs (51.5%, 53.5%, 55.5%, 59.25%, 63.0%) with five different chlorine contents and MCCPs (42%, 47%, 52%, 54.5%, 57%) with five different chlorine contents are respectively sampled, and analyzed according to the quantitative method proposed by Teth and the like, namely, the actual chlorine content (D') is taken as an abscissa, the total response factor (Fa) is taken as an ordinate, a standard working curve is drawn, and linear regression equations of the SCCPs and MCCPs are respectively F a1＝2.90×109D'1-1.65×109 and F a2＝3.04×109D'2-1.58×109, and the correlation coefficient (R 2) is respectively 0.9541 and 0.9614.
The detection limit was calculated by 3 Standard Deviations (SD) of the blank samples by referring to the USEPA specification, i.e., measuring SCCPs and MCCPs contents in 7 blank samples. The results showed that the detection limits of the SCCPs and MCCPs method were 16.2ng/g and 17.9ng/g, respectively.
(2) Matrix effect
The Matrix Effect (ME) is one of the indicators for evaluating the accuracy of the method. The stronger the matrix effect, the lower the accuracy of the method. In order to examine the influence of matrix effect, a pomfret negative sample is selected, a matrix standard solution and a solvent standard solution are respectively prepared, and a standard curve is drawn by sample injection detection. The calculation formula of the matrix effect is as follows: me= (matrix standard curve slope/solvent standard curve slope-1) ×100%.
Weak matrix effects when |me| < 20%; when the ME is more than or equal to 20% and less than or equal to 50%, the effect is medium matrix; when |ME| > 50%, a strong matrix effect is obtained. The results showed that SCCPs and MCCPs matrix effect ME were 10.12% and 11.64%, respectively, as weak matrix effects. The samples treated by the pretreatment method of the experiment are shown to have little matrix effect.
(3) Recovery rate and precision
Mixed standard solutions of SCCPs and MCCPs at low (50 ng/g), medium (100 ng/g) and high (500 ng/g) 3 different levels were added to the pomfret negative samples as samples of the aquatic products to be tested, and then the samples were tested according to the method of the present invention, and each level was repeatedly measured 6 times, and the recovery rate and Relative Standard Deviation (RSD) were calculated, and the results are shown in Table 2.
TABLE 2 precision and recovery results Table
As shown in Table 2, the average recovery rate of SCCPs and MCCPs is 80.8-91.7%, and RSD is 4.53% -8.48%, which shows that the accuracy and repeatability of the method are good.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The detection method of the short-chain or medium-chain chlorinated paraffin in the aquatic product is characterized by comprising the following steps of:
(1) Crushing an aquatic product sample to be detected, freeze-drying, adding diatomite, uniformly mixing, and then extracting by using an accelerated solvent to obtain an extracting solution;
(2) Adding 40wt% of acidic silica gel into the extract obtained in the step (1), taking supernatant, performing rotary evaporation, dissolving with ethyl acetate and cyclohexane in a volume ratio of 1:1, purifying by gel permeation chromatography, concentrating by nitrogen blowing, dissolving in cyclohexane, and filtering by using an organic filter membrane to obtain a sample purifying liquid to be detected;
(3) Diluting a plurality of chlorinated paraffin standard solutions with cyclohexane with equal volume respectively to obtain standard solution stock solution;
(4) Mixing the standard solution stock solution obtained in the step (3) according to different volume ratios to obtain chlorinated paraffin standard solution series with different chlorine contents;
(5) Carrying out chromatographic separation and mass spectrometry analysis on the standard solution stock solution obtained in the step (3) to obtain a retention time, characteristic ion and ion fragment mass chromatogram and a total ion flow mass chromatogram of the chlorinated paraffin homolog;
(6) Performing chromatographic separation and mass spectrometry analysis on the chlorinated paraffin standard solution series with different chlorine contents obtained in the step (4), and establishing a standard curve between the chlorine content and the total response factor;
(7) And (3) carrying out chromatographic separation and mass spectrometry analysis on the purifying liquid of the to-be-detected sample and the internal standard sample obtained in the step (2) to obtain a chromatogram and a peak area of the to-be-detected aquatic product sample, carrying out matching analysis on the chromatogram, carrying out standard curve calculation, and qualitatively or quantitatively analyzing short-chain or medium-chain chlorinated paraffin in the to-be-detected aquatic product sample by an internal standard method.
2. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in the step (1), the mass ratio of the aquatic product sample to be detected to diatomite is 1 g:0.8-1.2 g.
3. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in step (1), the solvent extraction is accelerated: the solvent is dichloromethane and n-hexane with the volume ratio of 1:1; the extraction temperature is 100 ℃; the extraction pressure was 1500psi; the static extraction time is 10min; the heating time is 5min; the flush volume was 60%; the purging time is 60s; the number of cycles was 2.
4. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in step (2), the gel permeation chromatography is performed during purification: a Bio-beads S-X3 glass gel chromatography column was used; the mobile phase is ethyl acetate and cyclohexane with the volume ratio of 1:1; the flow rate is 5.0mL/min; the effluent collection time is 9-21min.
5. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in the step (2), the pore size of the organic filter membrane is 0.22 μm.
6. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in the step (3), the plurality of chlorinated paraffin standard solutions are short-chain chlorinated paraffin standard solutions with 100 μg/mL chlorine content of 51.5%, 55.5% and 63.0%, respectively.
7. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in the step (3), the plurality of chlorinated paraffin standard solutions are medium-chain chlorinated paraffin standard solutions with chlorine contents of 42%, 52% and 57% respectively, which are 100 μg/mL.
8. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in step (7), the internal standard sample is epsilon-HCH.
9. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in steps (5), (6) and (7), the chromatographic separation is performed: the chromatographic column is DB-5MS with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m; the temperature of the sample inlet is 280 ℃; the sample injection amount is 1 mu L; the sample injection mode is non-split sample injection; the carrier gas is high-purity helium; the flow rate of carrier gas is 1mL/min; the temperature of the transmission line is 280 ℃; the temperature program is 100 ℃ and kept for 1min, 15 ℃/min is used for heating to 160 ℃ and kept for 2min, and 30 ℃/min is used for heating to 310 ℃ and kept for 15min.
10. The method for detecting short-chain or medium-chain chlorinated paraffin in aquatic products according to claim 1, wherein in steps (5), (6) and (7), mass spectrometry is performed: an electron capture anion source; the temperature of the ion source is 150 ℃; the reaction gas is methane; the scanning mode is selected ion monitoring; the solvent delay time was 3min.
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