CN111044634B - Method for detecting medium-chain chlorinated paraffin in leather - Google Patents
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Abstract
The invention relates to the technical field of analysis and detection, and provides a method for detecting medium-chain chlorinated paraffin in leather. According to the invention, through extraction and purification, the influence of interference substances in the leather sample on the detection result is removed, and the accuracy of the detection result is improved; the method can effectively separate short-chain chlorinated paraffin and medium-chain chlorinated paraffin, and achieves the purposes of accurate qualitative and quantitative determination. The embodiment result shows that when the concentration is 5-80 mg/L, the linear correlation coefficient of the standard curve is more than or equal to 0.9970, the blank sample standard addition recovery rate is 75-110%, the relative standard deviation is within 8.0%, the detection limit is lower than 50mg/kg, and the test requirement of medium-chain chlorinated paraffin in the leather sample can be met.
Description
Technical Field
The invention relates to the technical field of analysis and detection, and particularly relates to a method for detecting medium-chain chlorinated paraffin in leather.
Background
The chlorinated paraffin is a chlorinated derivative of paraffin, is a complex mixture containing thousands of chlorinated paraffin isomers and diastereomers, has the advantages of low volatility, flame retardance, good electrical insulation, low price and the like, can be used as a flame retardant and a polyvinyl chloride auxiliary plasticizer, is widely used for producing products such as leather, textiles, cables, hoses, rubber and the like, and can also be used as an additive of coating, plastic runways, lubricating oil and the like, and the chlorine content is changed from 30% to 70%. The chlorinated paraffin is divided into short-chain chlorinated paraffin SCCPs (C) according to the length of a carbon chain 10-C13) Medium chain chlorinated paraffin (C)14-C17) MCCPs and long-chain chlorinated paraffins LCCPs (C)18-C38). Wherein the short-chain chlorinated paraffin SCCP (C)10-C13) As plasticizers in rubber, coatings, adhesives, as flame retardants in plastic products such as PVC flooring, carpets and wire and cable insulation sheaths, as leather treatment agents and in the textile industry and as additives to metal working oils; the medium-chain chlorinated paraffin is used as a sealant of metal processing liquid, a flame retardant in a rubber finished product and a textile leather product, and the like; the long-chain chlorinated paraffin is mainly used as a plasticizer of PVC resin, an anticoagulant of lubricating oil and the like.
While chlorinated paraffin is used in large quantities, its hazards are gradually discovered and noticed. Studies have shown that chlorinated paraffins have long-chlorinated, bioaccumulating, and toxic properties, and are added to a class of compounds in persistent organic pollutants by the Stockholm convention on persistent organic pollutants. On 28 th 10 th 2008, the european union chemical administration (ECHA) published on its official website about registration, evaluation, authorization and restriction on chemicals (REACH regulation) the first 15 substances of high interest (SVHC) which were included in the authorization program, short-chain chlorinated paraffin is one of the 15 substances, and the regulation stipulates that the content of short-chain chlorinated paraffin in the related substances entering the market of the european union should not exceed 0.1%. Related regulations have also been recently established for medium chain chlorinated paraffins: resolution of european union 2016/1332 stipulates that medium chain chlorinated paraffin is less than 1000mg/kg in furniture leather textile products; the norwegian PoHS act limits the use of medium-chain chlorinated paraffins for related products; the largest shoe retailer in europe, Deichmann in germany, is constantly updating its limited material list according to the european union and the latest regulations in the united states, and the 2017 year limit material list requires that the MCCP content in shoe raw materials such as natural leather, synthetic textiles, PU leather, PVC, EVA, etc. is not higher than 1000 mg/kg.
At present, the international determination of chlorinated paraffin is mainly focused on short-chain chlorinated paraffin, and a gas chromatography-mass spectrometry (GC-MS) combined method is adopted, wherein the method comprises GC-ECNI-LRMS/HRMS, GC-MAB-HRMS, GC-EI-MS2 and the like. In addition, there is a method of performing quantitative analysis of CPs using ECD, FID or the like as a detector.
Domestic research aiming at chlorinated paraffin is mainly focused on short-chain chlorinated paraffin, and related research contents are mainly focused on environmental samples, soil samples, coastal sediments and the like; in addition, studies on paints, metal cutting fluids, leather, textiles, and the like have been reported. The short-chain chlorinated paraffin and the medium-chain chlorinated paraffin are simultaneously analyzed in the paint products, such as Chenman English (Chenman English, Chen Weixin, etc.), the detection research on the chlorinated paraffin and the DDT in the paint [ J ]. modern chemical industry, 2014, 34 (9): 169-172.), and the like, and no relevant test method for detecting the medium-chain chlorinated paraffin is found for the leather material.
Because the positions of chlorine atoms and the chlorination proportion are changed into various types, the mass of MCCPs and SCCPs are overlapped in a cross mode, so that the analysis of the short-chain chlorinated paraffin and the medium-chain chlorinated paraffin is interfered, and the MCCPs are difficult to separate, identify and measure.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for detecting medium-chain chlorinated paraffin in leather. The detection method provided by the invention is accurate in qualitative and quantitative determination and low in detection limit, and can meet the detection requirement of medium-chain chlorinated paraffin in leather.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for detecting medium-chain chlorinated paraffin in leather comprises the following steps:
mixing a leather sample and an extraction solvent for extraction to obtain an extracting solution;
mixing the extracting solution and concentrated sulfuric acid, standing and separating liquid, removing a concentrated sulfuric acid layer, and filtering the residual solution to obtain a solution to be detected;
performing GC-ECNI-MSD test on the liquid to be tested to obtain a spectrogram, and calculating the content of the medium-chain chlorinated paraffin in the leather according to the spectrogram and a standard working curve; the standard working curve is a relation curve of the concentration and the peak area of the medium-chain chlorinated paraffin in the leather;
the column temperature program of the gas chromatograph in the GC-ECNI-MSD test is as follows: initial temperature 100 deg.C, maintaining for 1min, heating to 190 deg.C at 30 deg.C/min, maintaining for 3min, heating to 310 deg.C at 30 deg.C/min, and maintaining for 7 min; the GC-ECNI-MSD test has medium-chain chlorinated paraffin with qualitative ions of 326, 340, 361, 377, 395, 411, 423, 443 and 459 and quantitative ions of 368, 382, 396, 402, 416, 430, 437, 451 and 473.
Preferably, the extraction solvent comprises one or more of dichloromethane, acetone and n-hexane.
Preferably, the leather sample and the extraction solvent are used in a ratio of 1g to 25 mL.
Preferably, the extraction mode is ultrasonic extraction or Soxhlet extraction.
Preferably, the temperature of the ultrasonic extraction is 30-50 ℃, the time is 10-60 min, and the ultrasonic power is 80-200W; the soxhlet extraction time is 4 hours, and the temperature is 65-90 ℃.
Preferably, the volume ratio of the extracting solution to the concentrated sulfuric acid is 2-3: 1.
Preferably, the GC-ECNI-MSD test has the following gas chromatographic conditions: the chromatographic column is a weak-polarity chromatographic column, the sample injection amount is 1-2 mu L, and the temperature of a sample injection port is 280 +/-2 ℃.
Preferably, the mass spectrum conditions of the GC-ECNI-MSD test are as follows: solvent time delay: 6 + -0.5 min, scan range: 50-550, ion source temperature: 150 ℃, quadrupole temperature: at 150 ℃.
The invention provides a method for detecting medium-chain chlorinated paraffin in leather, which comprises the steps of firstly extracting a leather sample by using an extraction solvent, then purifying an extracting solution by using concentrated sulfuric acid, testing GC-ECNI-MSD (gas chromatography-electron capture negative ion source mass spectrometry) of an obtained liquid to be tested, and then calculating the content of the medium-chain chlorinated paraffin in the leather according to a spectrogram and a standard working curve. According to the invention, through extraction and purification, the influence of interference substances in the leather sample on the detection result is removed, so that the accuracy of the detection result is improved; furthermore, the GC-ECNI-MSD chromatographic condition provided by the invention can effectively separate short-chain chlorinated paraffin (SCCPs) and medium-chain chlorinated paraffin (MCCPs) to achieve the purposes of accurate qualitative and quantitative determination. The embodiment result shows that when the concentration is 5-80 mg/L, the linear correlation coefficient of the standard curve is more than or equal to 0.9970, the blank sample standard addition recovery rate is 75-110%, the relative standard deviation is within 8.0%, the detection limit is lower than 50mg/kg, and the test requirement of medium-chain chlorinated paraffin in the leather sample can be met.
Drawings
FIG. 1 is a TIC spectrum corresponding to the group 10 temperature program;
FIG. 2 is S3mixMass spectrogram of (1);
FIG. 3 is M2mixMass spectrogram of (1);
FIG. 4 is S3mix、M2mixAnd S-M5mixWherein m/z is 368, 382, 396, 402, 416, 430, 437, 451, 473;
FIG. 5 is S3mix、M2mixAnd S-M5mixWherein m/z is 326, 340, 361, 377, 395, 411, 423, 443, 459;
FIG. 6 is a chromatogram of cleaned and unpurified leather samples;
fig. 7 is a standard operating curve.
Detailed Description
The invention provides a method for detecting medium-chain chlorinated paraffin in leather, which comprises the following steps:
mixing a leather sample and an extraction solvent for extraction to obtain an extracting solution;
mixing the extracting solution and concentrated sulfuric acid, standing, separating, removing a concentrated sulfuric acid layer, and filtering the residual solution to obtain a solution to be detected;
performing GC-ECNI-MSD test on the liquid to be tested to obtain a spectrogram, and calculating the content of the medium-chain chlorinated paraffin in the leather according to the spectrogram and a standard working curve; the standard working curve is a relation curve of the concentration and the peak area of the medium-chain chlorinated paraffin in the leather.
The leather sample and the extraction solvent are mixed and extracted to obtain the extracting solution. In the present invention, the extraction solvent preferably includes one or more of dichloromethane, acetone and n-hexane, more preferably dichloromethane; the leather sample and extraction solvent are preferably used in a ratio of 1g to 25 mL.
In the invention, the extraction mode is preferably ultrasonic extraction or soxhlet extraction; the temperature of the ultrasonic extraction is preferably 30-50 ℃, more preferably 35 ℃, the time of the ultrasonic extraction is preferably 10-60 min, more preferably 40min, and the ultrasonic power of the ultrasonic extraction is preferably 80-200W, more preferably 120W; in the present invention, the ultrasonic extraction is specifically preferably: the leather sample and the extraction solvent are mixed and then subjected to ultrasonic treatment. In the invention, the soxhlet extraction time is preferably 4 hours, the temperature is preferably 65-90 ℃, and more preferably 80 ℃; the soxhlet extraction is preferably carried out under reflux conditions; in the present invention, the soxhlet extraction is preferably performed in a soxhlet extraction flask.
After the extracting solution is obtained, the extracting solution and concentrated sulfuric acid are mixed and then are subjected to standing and liquid separation, a concentrated sulfuric acid layer is removed, and the residual solution is filtered to obtain the solution to be detected. In the invention, the volume ratio of the extracting solution to the concentrated sulfuric acid is preferably 2-3: 1, and more preferably 2.5: 1; the filter membrane for filtration is preferably a polytetrafluoroethylene organic filter membrane, and the pore diameter of the filter membrane is preferably 0.45 mu m; the invention uses concentrated sulfuric acid to purify the extracting solution, and the leather sample contains various chemical substances such as grease and pigment, and the interference substances can seriously influence the detection result; the concentrated sulfuric acid can perform addition, sulfonation and oxidation reactions with interference substances, the obtained product has high polarity, and can be condensed in a nonpolar solvent to achieve the purpose of purification, the medium-chain chlorinated paraffin has stable chemical properties, and the concentrated sulfuric acid does not influence the medium-chain chlorinated paraffin.
After the liquid to be detected is obtained, the GC-ECNI-MSD test is carried out on the liquid to be detected to obtain a spectrogram. In the invention, the column temperature-rising program of the gas chromatograph in the GC-ECNI-MSD test is as follows: initial temperature 100 deg.C, maintaining for 1min, raising temperature to 190 deg.C at 30 deg.C/min, maintaining for 3min, raising temperature to 310 deg.C at 30 deg.C/min, and maintaining for 7 min; other gas chromatography conditions are preferably: the chromatographic column is a weak-polarity chromatographic column, preferably an HP-5MS chromatographic column, the sample injection amount is 1-2 mu L, and the sample injection port temperature is 280 +/-2 ℃; the GC-ECNI-MSD test has the qualitative ions of 326, 340, 361, 377, 395, 411, 423, 443 and 459 and the quantitative ions of 368, 382, 396, 402, 416, 430, 437, 451 and 473; other mass spectrometric conditions are preferably: solvent time delay: 6 + -0.5 min, scan range: 50-550, ion source temperature: 150 ℃, quadrupole temperature: at 150 ℃. Under the chromatographic condition of the invention, short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) can be effectively separated, thereby realizing the accurate qualitative and quantitative determination of medium-chain chlorinated paraffins.
After obtaining the spectrogram, calculating the content of the medium-chain chlorinated paraffin in the leather according to the spectrogram and a standard working curve; the standard working curve is a relation curve of the concentration and the peak area of the medium-chain chlorinated paraffin in the leather. The method for drawing the standard curve has no special requirement, and the standard curve can be drawn according to a method well known by the technical personnel in the field.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Instrument
Agilent 7890A-5975C gas chromatography mass spectrometer (GC-ECNI-MSD); KQ-500E model digital control ultrasonic cleaner, kunshan ultrasonic instruments; polytetrafluoroethylene organic filter membrane with aperture of 0.45 μm, and is available in Shanghai industry clean materials factories; tubular hard glass extractor, 60mL, with screw cap (with Teflon gasket).
(2) Reagent
Concentrated sulfuric acid is analytically pure; methylene chloride, acetone, n-hexane, methanol were chromatographically pure and purchased from M-TEDIA, USA; the water is ultrapure water.
Medium-chain chlorinated paraffin standard solutions (chlorine content 52% and 57%, respectively), 100mg/L, 10mL, cyclohexane as solvent, dr. ehrenstorfer, germany; short-chain chlorinated paraffin standard solutions (chlorine content 51.5%, 55.5% and 63%, respectively), 100mg/L, 10mL, cyclohexane as solvent, Dr. Ehrenstontorfer, Germany.
Two-component mixed stock solutions of MCCPs (M)2mix): accurately transferring 10mL of 2 MCCPs standard solutions with chlorine content of 52% and 57%, and mixing the solutions in an equal volume in a 40mL brown liquid storage bottle at the concentration of 100 mg/L.
MCCPs two-component mixed working solution: respectively transferring 2 MCCPs standard solutions with chlorine content of 52% and 57% in certain volume, fixing the volume, and preparing standard working solutions with concentration of 5mg/L, 10mg/L, 20mg/L, 40mg/L, 60mg/L and 80 mg/L.
Three-component mixed stock solution (S) of SCCPs3mix): accurately transferring 10mL of each of the three SCCPs standard solutions, and mixing the solutions in a 40mL brown liquid storage bottle in equal volume, wherein the concentration is 100 mg/L.
SCCPs-MCCPs five-component mixed stock solution (S-M)5mix): accurately removing 200 μ L of each of 3 SCCPs and 2 MCCPs standard solutions, and mixing in an equal volume in a 2mL sample bottle at a concentration of 10 mg/L.
(3) Analytical procedure
(3.1) sample treatment
Placing the sample in a 60mL tubular hard glass extractor, adding 25mL dichloromethane, performing ultrasonic extraction at 40 ℃ for 40min, pouring the obtained extract into a separating funnel, adding concentrated sulfuric acid (the volume ratio of the extract to the concentrated sulfuric acid is 2:1), oscillating, standing, layering, removing a concentrated sulfuric acid layer, filtering the residual solution with an organic filter membrane, and testing the filtrate for GC-ECNI-MSD.
(3.2) column oven temperature program
10 sets of temperature rising programs are set, and standard solution S-M is analyzed5mixAn instrumental measurement method capable of separating peaks of SCCPs and MCCPs was investigated. The temperature-raising program is as follows:
(1)100℃(1min)30℃/min 160℃(2min)20℃/min 310℃(7min)；
(2)100℃(1min)30℃/min 160℃(1min)10℃/min 310℃(7min)；
(3)100℃(1min)30℃/min 160℃(1min)5℃/min 310℃(7min)；
(4)100℃(1min)7℃/min 260℃(8min)；
(5)100℃(1min)30℃/min 280℃(2min)30℃/min 310℃(7min)；
(6)100℃(1min)40℃/min 300℃(10min)；
(7)100℃(1min)15℃/min 280℃(2.5min)20℃/min 300℃(12.5min)；
(8)100℃(1min)5℃/min 310℃(10min)；
(9)250℃(30min)；
(10)100℃(1min)30℃/min 190℃(3min)30℃/min 310℃(7min)。
taking group 10 as an example, the specific meaning of the temperature raising program is: initial temperature of 100 deg.C, holding for 1min, raising to 190 deg.C at 30 deg.C/min, holding for 3min, raising to 310 deg.C at 30 deg.C/min, and holding for 7min
Analytical Standard solution S-M5mixMass spectrum conditions of (2): solvent time delay: 6 + -0.5 min, scan range: 50-550; (ii) ion source temperature; 150 ℃, quadrupole temperature: at 150 ℃. Gas chromatography conditions: the chromatographic column is HP-5 MS; sample introduction amount: 1 μ L, injection port temperature: 280 plus or minus 2 ℃.
The results show that cluster peaks all appear in the total ion current chromatogram, and 10 groups of temperature-raising programs can not effectively separate SCCPs and MCCPs. And (3) comprehensively considering factors such as the shape of a cluster peak, the peak width, the response value, the peak-off time and the like, and finally selecting the 10 th group as the optimal column incubator temperature-rising program. The total ion chromatogram is shown in FIG. 1.
(3.3) qualitative and quantitative ion determination
Through the TIC spectrogram, SCCPs and MCCPs cannot be effectively separated, and the purpose of qualitative and quantitative determination of the MCCPs cannot be achieved. FIGS. 2 and 3 are S3mixAnd M2mixAs can be seen from fig. 2 and 3, the ions with high relative abundance of MCCPs are: 368. 382, 396, 402, 416, 430, 437, 451, 473, 326, 340, 361, 377, 395, 411, 423, 443, 459 are characteristic ions with high relative abundance of SCCPs. Through the selection of the characteristic ions, the separation, the qualitative and the quantitative of the target substance can be achieved to the maximum extent. In this example, ions with high relative abundance of MCCPs (m/ z 368, 382, 396, 402, 416, 430, 437, 451, 473) and characteristic ions with high relative abundance of SCCPs (m/ z 326, 340, 361, 377, 395, 411, 423, 443, 459) were selected, and the corresponding ions were selected for S 3mix、M2mixAnd S-M5mixThe results of the selective ion monitoring of GC-ECNI-MSD are shown in FIGS. 4 and 5.
As can be seen from fig. 4, when selecting the ion monitoring (SIM) with high relative abundance of MCCPs (m/ z 368, 382, 396, 402, 416, 430, 437, 451, 473), the SCCPs and MCCPs peaks, although partially overlapping, have different initial peak-out times and end times, different peak shapes, and are separated by the selectionSub-monitoring, SCCPs (S)3mix) The response is relatively small in 12.8-15.5 min (namely MCCPs peak-off time), the monitoring of the MCCPs is basically not influenced, and the purpose of quantifying the MCCPs can be achieved.
As can be seen from fig. 5, when the ion monitoring (SIM) with high relative abundance of SCCPs is selected (m/ z 326, 340, 361, 377, 395, 411, 423, 443, 459), S3mixAnd M2mixThe retention times of the two peaks overlap and cannot be separated, but under this selective ion monitoring, MCCPs (M)2mix) The initial peak-off time and the end time of the SCCPs are different in 10.5-12.5 min (namely the peak-off time of the SCCPs), and the peak shapes are different, so that the purpose of determining the MCCPs can be achieved.
Therefore, the MCCPs were characterized by selecting ions with high relative abundance of SCCPs (m/ z 326, 340, 361, 377, 395, 411, 423, 443, 459) and performing selective ion monitoring of GC-ECNI-MSD on the samples. The MCCPs are quantified by selecting ions with high relative abundance of MCCPs (m/ z 368, 382, 396, 402, 416, 430, 437, 451, 473) and performing selective ion monitoring of GC-ECNI-MSD on the sample.
(3.4) sample clarification
The other conditions are the same as those in (3.1), only the concentrated sulfuric acid purification step is omitted, and the obtained extract is directly subjected to GC-ECNI-MSD detection. Detection conditions are as follows: gas chromatography conditions: the chromatographic column is an HP-5MS chromatographic column, the sample injection amount is 1 mu L, the temperature of a sample injection port is 280 +/-2 ℃, and the column temperature-rising program: initial temperature 100 deg.C, maintaining for 1min, heating to 190 deg.C at 30 deg.C/min, maintaining for 3min, heating to 310 deg.C at 30 deg.C/min, and maintaining for 7 min; the mass spectrometry conditions are preferably: solvent time delay: 6 + -0.5 min, scan range: 50-550, ion source temperature: 150 ℃, quadrupole temperature: the qualitative ions of the mid-chain chlorinated paraffin at 150 ℃ are 326, 340, 361, 377, 395, 411, 423, 443 and 459, and the quantitative ions are 368, 382, 396, 402, 416, 430, 437, 451 and 473;
FIG. 6 is a chromatogram of a solution under test purified with concentrated sulfuric acid and without concentrated sulfuric acid, respectively. As can be seen from FIG. 6, the sample contains a large amount of interfering substances without being purified by concentrated sulfuric acid, which interferes the detection of the MCCPs and causes great interference to the detection result. The concentrated sulfuric acid is used for purification, interference substances are removed, the chromatogram of the chlorinated paraffin is clearly displayed, and the qualitative and quantitative analysis can be accurately carried out.
(3.5) extraction method and extraction solvent
Dichloromethane, normal hexane and acetone are used as solvents, two pre-treatments of ultrasonic extraction and Soxhlet extraction are respectively adopted for extraction, and methanol is used as an extraction solvent for a comparison experiment. Wherein the ultrasonic extraction test process comprises the following steps: adding 25mL of extraction solvent into 1.00g of sample, and performing ultrasonic treatment for 40 minutes, wherein the extraction temperatures of dichloromethane, n-hexane, acetone and methanol are 35 ℃, 40 ℃, 50 ℃ and 50 ℃ respectively; soxhlet extraction test procedure: adding 1.00g of sample into 25mL of extraction solvent, distilling and refluxing for 4h in a Soxhlet extraction bottle, wherein the extraction temperatures of dichloromethane, n-hexane, acetone and methanol are 65 ℃, 80 ℃, 90 ℃ and 90 ℃ respectively.
After extraction, concentrated sulfuric acid purification is carried out to obtain a liquid to be detected, and the purification method is the same as that in the step (3.1); and (3) carrying out GC-ECNI-MSD detection on the liquid to be detected, wherein the detection conditions are consistent with those in (3.4), carrying out parallel test for 3 times, and taking an average value. The test results are shown in Table 1, and the data in Table 1 is the medium chain chlorinated paraffin content (mg/kg) in the leather sample.
TABLE 1 Effect of extraction solvent and extraction mode on results
As can be seen from the results in Table 1, the results of ultrasonic extraction and Soxhlet extraction with the same solvent are relatively close to each other, which indicates that the two extraction methods can achieve better effects; the extraction result of the methanol is obviously lower than that of the other three types, the extraction efficiency of the acetone and the normal hexane is similar, and the extraction efficiency of the dichloromethane is the best. Considering that the Soxhlet extraction time is long, the ultrasonic extraction is finally selected for subsequent experiments.
(3.6) ultrasonic extraction time and ultrasonic Power
And (3) carrying out ultrasonic extraction by using dichloromethane as a solvent, and testing the influence of the ultrasonic extraction time and the ultrasonic power on the test result, wherein the specific test conditions are consistent with those in (3.5). The ultrasonic time is respectively set to 10min, 20min, 40min and 60 min; the ultrasonic power was set at 80W, 120W, 160W, 200W, respectively. The result shows that the ultrasonic time is 10-60 minn, the ultrasonic power is 80-200W, and the optimal extraction effect can be achieved under the ultrasonic time of 120W for 40 min.
(3.7) drawing of Standard working Curve
According to the GC-ECNI-MSD instrument condition analysis (2) in (3.4), the MCCPs mixed standard working solution with the concentration of 5.0,10.0,20.0,40.0,60.0 and 80.0mg/L is prepared, the MCCPs concentration is used as an abscissa, the peak area is used as an ordinate, a standard working curve is drawn, the obtained result is shown in figure 7, and according to figure 7, the correlation coefficient of the standard working curve is 0.9974 within the concentration range of 5.0-80.0 mg/L.
(3.8) detection and quantitation limits
A low concentration standard solution was added to the leather blank matrix corresponding to a MCCPs content of 25mg/Kg in the sample for 8 independent tests, and the data analysis is shown in Table 2. The standard deviation was calculated from the test results, and the detection limit and the quantification limit (assay lower limit) were calculated as 3-fold and 10-fold standard deviations, respectively. As can be seen from Table 2, the method has a quantitative limit of 41mg/Kg and a detection limit of 12mg/Kg, and can fully meet the quantitative requirements of detection.
TABLE 2 detection Limit (IDL) and quantitation Limit (IQL) test results for methods (mg/kg)
(3.9) recovery and precision
A blank leather sample is selected as a substrate, and 250 mu L, 1.250mL and 5.000mL M are added2mixThe stock solutions correspond to MCCPs in the sample at 25mg/Kg, 125mg/Kg and 500 mg/Kg. The pretreatment is carried out according to the method described in the standard, the parallel measurement is carried out for 5 times, the recovery rate and the precision are measured, the obtained results are shown in the table 3, and the recovery rate of the method is 75-110 percent and the Relative Standard Deviation (RSD) is within 8.0 percent according to the table 3.
TABLE 3 leather sample Standard recovery test results (mg/kg)
(4) Analysis of test samples
8 leather samples were treated as in (3.1) and then subjected to GC-ECNI-MSD test, the test conditions being identical to those in (3.4).
And (3) testing results: the medium-chain chlorinated paraffin was detected in 2 out of 8 samples, which were 1258mg/Kg and 546mg/Kg, respectively, and the other samples were not detected.
The embodiment shows that the method provided by the invention has accurate detection result, can effectively separate short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs), and can meet the test requirement of medium-chain chlorinated paraffins in leather samples.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (6)
1. The method for detecting the medium-chain chlorinated paraffin in the leather is characterized by comprising the following steps of:
mixing a leather sample and an extraction solvent for extraction to obtain an extracting solution; the extraction solvent is dichloromethane;
mixing the extracting solution and concentrated sulfuric acid, standing, separating, removing a concentrated sulfuric acid layer, and filtering the residual solution to obtain a solution to be detected;
performing GC-ECNI-MSD test on the liquid to be tested to obtain a spectrogram, and calculating the content of the medium-chain chlorinated paraffin in the leather according to the spectrogram and a standard working curve; the standard working curve is a relation curve of the concentration and the peak area of the medium-chain chlorinated paraffin in the leather;
the column temperature program of the gas chromatograph in the GC-ECNI-MSD test is as follows: initial temperature 100 deg.C, maintaining for 1min, heating to 190 deg.C at 30 deg.C/min, maintaining for 3min, heating to 310 deg.C at 30 deg.C/min, and maintaining for 7 min; the GC-ECNI-MSD test has the qualitative ions of 326, 340, 361, 377, 395, 411, 423, 443 and 459 and the quantitative ions of 368, 382, 396, 402, 416, 430, 437, 451 and 473;
the mass spectrum conditions of the GC-ECNI-MSD test are as follows: solvent time delay: 6 + -0.5 min, scan range: 50-550, ion source temperature: 150 ℃, quadrupole temperature: at 150 ℃.
2. The detection method according to claim 1, wherein the leather sample and the extraction solvent are used in a ratio of 1g to 25 mL.
3. The method according to claim 1, wherein the extraction is ultrasonic extraction or soxhlet extraction.
4. The detection method according to claim 3, wherein the temperature of the ultrasonic extraction is 30-50 ℃, the time is 10-60 min, and the ultrasonic power is 80-200W; the soxhlet extraction time is 4 hours, and the temperature is 65-90 ℃.
5. The detection method according to claim 1, wherein the volume ratio of the extraction solution to the concentrated sulfuric acid is 2-3: 1.
6. The detection method according to claim 1, wherein the GC-ECNI-MSD test has gas chromatography conditions: the chromatographic column is a weak-polarity chromatographic column, the sample injection amount is 1-2 mu L, and the temperature of a sample injection port is 280 +/-2 ℃.
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