CN109633068B - Method for analyzing polybrominated diphenyl ether compounds in soil by liquid chromatography tandem mass spectrometry - Google Patents
Method for analyzing polybrominated diphenyl ether compounds in soil by liquid chromatography tandem mass spectrometry Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims abstract description 48
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 11
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 title claims description 8
- 238000012360 testing method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 16
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
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- RZXIRSKYBISPGF-UHFFFAOYSA-N 2,2',4,4',5,5'-Hexabromodiphenyl ether Chemical compound C1=C(Br)C(Br)=CC(Br)=C1OC1=CC(Br)=C(Br)C=C1Br RZXIRSKYBISPGF-UHFFFAOYSA-N 0.000 claims description 4
- VHNPZYZQKWIWOD-UHFFFAOYSA-N 2,2',4,4',5,6'-Hexabromodiphenyl ether Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=CC(Br)=C(Br)C=C1Br VHNPZYZQKWIWOD-UHFFFAOYSA-N 0.000 claims description 4
- XYBSIYMGXVUVGY-UHFFFAOYSA-N 2,2',4,4'-Tetrabromodiphenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1Br XYBSIYMGXVUVGY-UHFFFAOYSA-N 0.000 claims description 4
- WHPVYXDFIXRKLN-UHFFFAOYSA-N 2,4-dibromophenyl 2,4,5-tribromophenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=CC(Br)=C(Br)C=C1Br WHPVYXDFIXRKLN-UHFFFAOYSA-N 0.000 claims description 4
- NSKIRYMHNFTRLR-UHFFFAOYSA-N 2,4-dibromophenyl 2,4,6-tribromophenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=C(Br)C=C(Br)C=C1Br NSKIRYMHNFTRLR-UHFFFAOYSA-N 0.000 claims description 4
- UPNBETHEXPIWQX-UHFFFAOYSA-N 4-bromophenyl 2,4-dibromophenyl ether Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1Br UPNBETHEXPIWQX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 238000004811 liquid chromatography Methods 0.000 claims description 4
- 238000001819 mass spectrum Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
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- YESDYWNWEVPOLZ-UHFFFAOYSA-N 1,2,3,5-tetrabromo-4-(2,4-dibromophenoxy)benzene Chemical compound BrC1=CC(Br)=CC=C1OC1=C(Br)C=C(Br)C(Br)=C1Br YESDYWNWEVPOLZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
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- 239000002904 solvent Substances 0.000 claims description 3
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004885 tandem mass spectrometry Methods 0.000 claims description 3
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- 238000010846 tandem mass spectrometry analysis Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 26
- 238000001228 spectrum Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- NLBLNZDNOSSGPW-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3-dibromophenoxy)benzene Chemical compound BrC1=CC=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2Br)Br)=C1Br NLBLNZDNOSSGPW-UHFFFAOYSA-N 0.000 description 1
- LJDGJCNHVGGOFW-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2-bromophenoxy)benzene Chemical compound BrC1=CC=CC=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br LJDGJCNHVGGOFW-UHFFFAOYSA-N 0.000 description 1
- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 231100000357 carcinogen Toxicity 0.000 description 1
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- 239000003802 soil pollutant Substances 0.000 description 1
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- ARERIMFZYPFJAV-UHFFFAOYSA-N tetrabromodiphenyl ethers Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C(Br)=C1Br ARERIMFZYPFJAV-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
- G01N2030/8845—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving halogenated organic compounds
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Abstract
The invention discloses a liquid chromatogram tandem mass spectrometry analysis of polybrominated diphenyl ether compounds in soil, which relates to the field of soil detection. In the whole operation mode, the peak of the target compound is sharp, the responsiveness is strong, the analysis time of the instrument is short, and the speed is high, so that the accuracy of the test is effectively improved.
Description
Technical Field
The invention relates to the field of soil pollutant content testing, in particular to a method for analyzing polybrominated diphenyl ether compounds in soil by liquid chromatography-tandem mass spectrometry.
Background
Polybrominated diphenyl ether compounds (PBDEs) are taken as typical brominated flame retardants, and mainly comprise three industrial products, namely pentabrominated diphenyl ether, octabrominated diphenyl ether and decabrominated diphenyl ether, and the polybrominated diphenyl ether compounds have been widely applied to industries such as electronic and electric appliances, textiles, traffic and the like due to the advantages of mature production process, outstanding cost advantage, good flame retardant effect and the like. However, PBDEs have both nondegradable property, fat-soluble property and bioaccumulation property, and are gradually controlled by legislation in recent years, hexabromodiphenyl ether and heptabromodiphenyl ether, tetrabromobiphenyl ether and pentabromodiphenyl ether have been listed in the List of controlled supplementary persistent organic pollutants of the St.Golgi convention in 2009, and decabromodiphenyl ether is listed in the List of three carcinogens by the International cancer research organization of the world health organization in 2017.
PBDEs are easy to fall off from products and exist in the environment, and are easy to enrich in environmental media such as soil, sediment and the like due to low water solubility. At present, the most common quantitative detection method for PBDEs in soil is gas chromatography-mass spectrometry (GC-MS), and the national environmental protection agency recommends high-resolution gas chromatography-mass spectrometry for detection. However, the analysis of the high-brominated PBDEs has strict requirements on the conditions of the gas chromatography sample inlet type, the sample inlet temperature, the ion source temperature, the gas chromatography column and the like, and particularly, decabromodiphenyl ether has the advantages that the molecular weight is not easy to gasify, the decabromodiphenyl ether is easy to decompose at the sample inlet of the gas chromatography, and a special high-temperature column is required to be equipped to obtain a satisfactory analysis result.
In addition, because the components of the soil are complex, the recovery rate is only 65-93% when the detection is carried out by using LC alone, and the standard deviation reaches 7-23%, a new testing method is needed to be designed to improve the accuracy.
Disclosure of Invention
The invention aims to provide a method for analyzing polybrominated diphenyl ether compounds in soil by liquid chromatography-tandem mass spectrometry, which has high test precision and wider detection limit range.
The technical purpose of the invention is realized by the following technical scheme:
a method for analyzing polybrominated diphenyl ether compounds in soil by liquid chromatography-tandem mass spectrometry is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
(a) drawing a standard curve:
diluting the standard solution with initial mobile phase by 200 times, 100 times, 50 times, 25 times, 12.5 times and 6.25 times, measuring 1.0mL, adding 16 μ L of the solution with concentration of 5.15mg/L and 4.88mg/L respectively13C12-BDE-139 and13C12two internal standards of BDE-209, tested under certain conditions of liquid chromatography and mass spectrometry, to draw standard curves for 8 compounds of interest, BDE-28: y1 ═ 0.0147x1+0.0002, r1＝0.9988；BDE-47：y2＝0.0123x2+0.000003，r2＝0.9990；BDE-100：y3＝0.9097x3+0.0068，r3＝0.9992；BDE-99：y4＝0.2371x4+0.0015，r4＝0.9994；BDE-154：y5＝1.0784x5+0.0061，r5＝0.9992；BDE-153：y6＝0.4178x6+0.00091，r6＝0.9995；BDE-183：y7＝0.8641x7+0.0059，r7＝0.9995；BDE-209：y8＝0.8223x8+0.0388，r80.9994, wherein y1，y2，y3，y4，y5，y6，y7Quantification of peak area of ion and internal standard for target13C12BDE-139 quantification of the ratio of the ion peak areas, y8Quantification of ion peak area and internal standard for BDE-20913C12-ratio of peak areas of PBDE-209, x1，x2，x3，x4，x5，x6，x7The concentration of the target substance and the internal standard substance13C12The ratio of the concentrations of BDE-139, x8BDE-209 concentration and internal standard substance13C12-ratio of PBDE-209 concentrations, in the course of the analysis13C12PBDE-139 concentration and13C12-PBDE-209 concentration is a fixed value;
(b) sample pretreatment: freeze drying soil, grinding, sieving with 60 mesh sieve to obtain soil sample, weighing about 16g of soil sample, placing in ASE extraction tank, adding 16 μ L of 5.15mg/L and 4.88mg/L solutions13C12-BDE-139 and13C12-BDE-209 two internal standards, extracting with dichloromethane at 1500psi extraction pressure and 100 deg.C for 5min, repeating the extraction twice, collecting the extract, blowing nitrogen to concentrate to 8.0mL, subjecting 5.0mL of the concentrate to GPC purification, using dichloromethane as mobile phase at 5.0mL/min flow rate, pre-washing time 1100s, collecting time 920s, post-washing time 300s, collecting the purified solution, concentrating and converting into methanol solvent to 1.0 mL;
(c) the pretreated sample is put on a computer for testing, then the peak area value of each target compound is taken into a corresponding standard curve, the corresponding concentration Xi of each target compound is obtained by calculation, and then according to the condition that w is XiV3V1/V2And M, calculating the mass fraction of each target compound in the soil. Wherein the unit of w is mu g/kg, V1Is the volume of the first nitrogen blowing concentration constant volume, unit mL, V2Measuring the volume of the concentrated solution in mL and V3The volume of the test was again concentrated in mL, M being the total mass of the soil sample, in g, Xi being X1，X2，X3，X4，X5，X6，X7Or X8According to x1，x2，x3，x4，x5，x6，x7Or x8Multiplied by the concentration of the internal standard.
Preferably, the chromatographic conditions are: the column temperature is 35 ℃; the flow rate is 0.4 mL/min; the sample volume is 10 mu L, and the separation time is 13 min; the mobile phase A is water, and the mobile phase B is methanol. Gradient leaching: 0-2 min, 85% B, 2-7 min, 85% -100% B, 7-9.8 min, 100% B, 9.8-10.0 min, 85% B, 10.0-13.0 min, 85% B.
Preferably, A is water plus 0.1% ammonia, and B is methanol plus 0.1% ammonia.
Preferably, the weighed soil sample is mixed with the adsorbent in the step (b).
Preferably, the mass ratio of the adsorbent to the soil sample is (3-4): 8.
preferably, the adsorbent is one or a mixture of more of diatomite, activated carbon and florisil.
Preferably, the mass spectrometry conditions are: monitoring multiple reactions of triple quadrupole rod tandem mass spectrometry; APCI negative ion ionization mode; the pressure of the air curtain is 40psi, the voltage of the spray needle is-4500V, the temperature of the ion source is 300 ℃, and the pressure of the spray air is 55 psi; a collision air pressure medium; target scan time 0.5s, entrance voltage 10V, exit voltage 13V.
Preferably, in the step (b), nitrogen is blown to the collected purifying liquid, when the amount of the solution is reduced to 0.1-0.2 mL in total, 0.5mL of methanol is added, nitrogen blowing is continued, the steps are repeated for three times, and finally the total volume is increased to 1.0mL by using the methanol.
In conclusion, the invention has the following beneficial effects:
1. firstly, the PBDEs with the size of more than pentabromide can obtain higher response value and faster analysis speed by utilizing liquid chromatography and mass spectrum tandem to test the polybrominated diphenyl ether compound;
2. aiming at the target compound, the separation effect of using methanol as a mobile phase is better than that of using acetonitrile as the mobile phase;
3. the ammonia water is added into the mobile phase, so that the peak type of the target object is sharper, and the ionization efficiency of the target object is promoted, thereby enhancing the response signal of each target object and improving the detection sensitivity of PBDEs;
4. the soil sample and the adsorbent are mixed, so that the extraction area can be increased through the adsorbent, and part of impurities can be removed, thereby reducing the interference of the impurities on the test.
Drawings
FIG. 1 is a spectrum of a standard solution test;
FIG. 2 is a spectrum of a standard solution test obtained without adding ammonia water;
FIG. 3 is a test spectrum for sample set 4-A;
FIG. 4 is a test spectrum of a sample plus a standard.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
A method for analyzing polybrominated diphenyl ether compounds in soil by liquid chromatography-tandem mass spectrometry comprises the following steps,
(a) drawing a standard curve:
diluting the standard solution with initial mobile phase by 200 times, 100 times, 50 times, 25 times, 12.5 times and 6.25 times, measuring 1.0ml, adding 16 μ L of the solution with concentration of 5.15mg/L and 4.88mg/L respectively13C12-BDE-139 and13C12-BDE-209 two internal standards, tested under certain conditions of liquid chromatography and mass spectrometry, to obtain a spectrum as shown in fig. 1, and plotting standard curves for 8 target compounds, as shown in table one below:
TABLE I, Standard curves for 8 PBDEs
| Target object | Linear equation of equations | Correlation coefficient | MDL(μg/kg) |
| BDE-28 | y1＝0.0147x1+0.0002 | r1＝0.9988 | 0.44 |
| BDE-47 | y2＝0.0123x2+0.000003 | r2＝0.9990 | 0.59 |
| BDE-100 | y3＝0.9097x3+0.0068 | r3＝0.9992 | 0.33 |
| BDE-99 | y4＝0.2371x4+0.0015 | r4＝0.9994 | 0.46 |
| BDE-154 | y5＝1.0784x5+0.0061 | r5＝0.9992 | 0.48 |
| BDE-153 | y6＝0.4178x6+0.00091 | r6＝0.9995 | 0.45 |
| BDE-183 | y7＝0.8641x7+0.0059 | r7＝0.9995 | 0.42 |
| BDE-209 | y8＝0.8223x8+0.0388 | r8＝0.9994 | 0.22 |
Wherein, y1，y2，y3，y4，y5，y6And y7Quantification of peak area of ion and internal standard for target13C12BDE-139 quantification of the ratio of the ion peak areas, y8Quantification of ion peak area and internal standard for BDE-20913C12-ratio of peak areas of PBDE-209, x1，x2，x3，x4，x5，x6，x7The concentration of the target substance and the internal standard substance13C12The ratio of the concentrations of BDE-139, x8BDE-209 concentration and internal standard substance13C12-ratio of the concentrations of PBDE-209, wherein13C12PBDE-139 concentration and13C12the PBDE-209 concentration is a fixed value. Meanwhile, standard solutions of 8 polybrominated diphenyl ether compounds were purchased from Accustandard, USA, and the concentrations of BDE-28, BDE-47, BDE-100, BDE-99, BDE-154, BDE-153 and BDE-183 were all 20mg/L, and the concentration of BDE-209 was 200 mg/L. The 8 PBDEs show good linear relation in a certain range, the correlation coefficient range is 0.9988-0.9995, and the requirement of quantitative analysis is met; according to EPA SW-846 method, calculating detection limit, and 7 times of blank and mapping according to sample pretreatmentThe detection limit was calculated by the standard deviation (SD, n is 7) of the measurement of the blank spiked solution with the detection limit being 3 to 5 times, and the detection limit was obtained at 0.22 to 0.59 μ g/kg.
The linear range of the seven polybrominated diphenyl ethers except decabromodiphenyl ether is 4-200 mug/L, and the other seven polybrominated diphenyl ethers are selected13C12PBDE-139 as an internal standard for quantification, and decabromodiphenyl ether has a linear range of 10-1000. mu.g/L, where it is selected13C12PBDE-209 as an internal standard for quantification.
And, here the chromatographic conditions: the column temperature is 35 ℃; the flow rate is 0.4 mL/min; the sample volume is 10 mu L, and the separation time is 13 min; the mobile phase A is water and 0.1% ammonia water, and the mobile phase B is methanol and 0.1% ammonia water. Gradient leaching: 0-2 min, 85% B, 2-7 min, 85% -100% B, 7-9.8 min, 100% B, 9.8-10.0 min, 85% B, 10.0-13.0 min, 85% B.
It should be noted here that, as can be seen from a comparison between fig. 2 and fig. 1, the addition of ammonia water to the mobile phases a and B can make the peak shape of the target object sharper and promote the ionization efficiency of the target object, thereby enhancing the response signal of each target object and improving the detection sensitivity of PBDEs.
Mass spectrum conditions: monitoring multiple reactions of triple quadrupole rod tandem mass spectrometry; APCI negative ion ionization mode; the pressure of the air curtain is 40psi, the voltage of the spray needle is-4500V, the temperature of the ion source is 300 ℃, and the pressure of the spray air is 55 psi; a collision air pressure medium; target scan time 0.5s, entrance voltage 10V, exit voltage 13V.
(b) Sample pretreatment: collecting 8 soil samples collected near a Taizhou city road, bridge peak, river and old dismantling park, freeze-drying the soil, grinding the soil uniformly, sieving the soil samples through a 60-mesh pore size sieve to obtain soil samples, mixing the soil samples with an adsorbent, weighing about 16g of the soil samples, placing the soil samples in an ASE (accelerated extraction) extraction pool, adding 16 mu L of the soil samples with the concentrations of 5.15mg/L and 4.88mg/L respectively13C12-BDE-139 and13C12extracting two internal standards of-BDE-209 by dichloromethane at the extraction pressure of 1500psi and the extraction temperature of 100 ℃ for 5min, repeating the extraction twice, collecting the extract, blowing nitrogen to concentrate to 8.0mL, taking 5.0mL of concentrated solution for GPC purification, taking dichloromethane as mobile phase, and making the flow rate 5.0 mL/ionAnd min, wherein the pre-leaching time is 1100s, the collecting time is 920s, the post-washing time is 300s, the purifying solution is finally collected, concentrated and converted into a methanol solvent to be 1.0mL, the adsorbent can be one or a mixture of more of kieselguhr, activated carbon and Florisil, the preferred adsorbent is kieselguhr, and the mass ratio of the kieselguhr to the soil sample is (3-4): 8;
(c) loading the pretreated sample on a computer for testing to obtain figure 2, wherein other test spectrograms are similar to figure 2 and only differ in peak number and peak area, finding out the peak position of each target compound by combining a standard spectrogram, then substituting the measured peak area value of each target compound into a corresponding standard curve, calculating to obtain the corresponding concentration Xi of each target compound, and then obtaining the corresponding concentration Xi of each target compound according to the w-XiV3V1/V2And M, calculating the mass fraction of each target compound in the soil. Wherein the unit of w is mu g/kg, V1Is the volume of the first nitrogen blowing concentration constant volume, unit mL, V2Measuring the volume of the concentrated solution in mL and V3The volume of the test was again concentrated in mL, M being the total mass of the soil sample, in g, Xi being X1，X2，X3，X4，X5，X6，X7Or X8Unit is μ g/L, according to x1，x2，x3，x4，x5，x6，x7Or x8Multiplied by the concentration of the internal standard. The results of the specific sample testing are shown in table two.
TABLE II, polybrominated diphenyl ether content of soil sample
Wherein N.D represents no detected (not detected), sample A represents surface soil, i.e., soil with a depth of 0-20cm, and B represents lower soil, i.e., soil with a depth of 20-60 cm.
In addition, soil samples of the surface layer and the lower layer are respectively taken in the same dismantling park, mixed standard substance solutions with two concentration levels of high and low in respective standard curves are added, and the standard addition recovery rate of each target compound is calculated according to a sample pretreatment method. Preparing a standard solution with the concentration of the middle point, wherein the concentration of BDE from tribromide to nonabromide is 100 mug/L, the concentration of BDE-209 is 400 mug/L, adding the standard solution into the sample analysis process, and generally adding the standard solution into the middle concentration point every 10 soil samples to be analyzed, and calculating the precision of the measured value of the middle concentration point. And (3) taking the SQC-072 soil polybrominated diphenyl ether quality control sample, determining according to sample pretreatment to obtain an attached figure 4, and meanwhile, calculating the accuracy by comparing a test value with a theoretical value. The specific measurement results are shown in table three.
TABLE III, recovery rate, precision and accuracy of each compound
The result shows that the method has the advantages that the standard recovery rate is 71-126%, the standard deviation is 3-18%, the testing precision of the intermediate point standard solution is less than 10%, the quality control sample testing results are within the allowable range, and the precision is better.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (2)
1. A method for analyzing polybrominated diphenyl ether compounds in soil by liquid chromatography-tandem mass spectrometry is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
(a) drawing a standard curve:
respectively diluting the standard solution by 200 times, 100 times, 50 times, 25 times, 12.5 times and 6.25 times with the initial mobile phase, measuring 1.0mL, and adding 16 muL of the solution with the concentration of 5.15mg/L and 4.88mg/L13C12-BDE-139 and13C12two BDE-209 internal standard substances are tested under certain conditions of liquid chromatography and mass spectrum, and standard curves of 8 target compounds are drawn,BDE-28：y1=0.0147x1+0.0002，r1=0.9988；BDE-47：y2=0.0123x2+0.000003，r2=0.9990；BDE-100：y3=0.9097x3+0.0068，r3=0.9992；BDE-99：y4=0.2371x4+0.0015，r4=0.9994；BDE-154：y5=1.0784x5+0.0061，r5=0.9992；BDE-153：y6=0.4178x6+0.00091，r6=0.9995；BDE-183：y7=0.8641x7+0.0059，r7=0.9995；BDE-209：y8=0.8223x8+0.0388，r8=0.9994, wherein y1，y2，y3，y4，y5，y6，y7Quantification of peak area of ion and internal standard for target13C12BDE-139 quantification of the ratio of the ion peak areas, y8Quantification of ion peak area and internal standard for BDE-20913C12-ratio of peak areas of PBDE-209, x1，x2，x3，x4，x5，x6，x7The concentration of the target substance and the internal standard substance13C12The ratio of the concentrations of BDE-139, x8BDE-209 concentration and internal standard substance13C12-ratio of PBDE-209 concentrations, in the course of the analysis13C12PBDE-139 concentration and13C12-PBDE-209 concentration is a fixed value;
(b) sample pretreatment: freeze-drying soil, grinding uniformly, sieving with a 60-mesh pore size sieve to obtain a soil sample, weighing about 16g of the soil sample, and mixing with an adsorbent, wherein the mass ratio of the adsorbent to the soil sample is (3-4): 8; mixing a soil sample with an adsorbent, placing the mixture in an ASE extraction pool, and adding the mixture with the concentration of 5.15mg/L and 4.88mg/L in 16 muL13C12-BDE-139 and13C12extracting two internal standard substances BDE-209 by using dichloromethane, wherein the extraction pressure is 1500psi, the extraction temperature is 100 ℃, the extraction time is 5min, repeatedly extracting for two times, collecting extract liquor, carrying out nitrogen blowing concentration to fix the volume to 8.0mL, taking 5.0mL of concentrated solution for GPC purification, using dichloromethane as a mobile phase, carrying out flow rate of 5.0mL/min, pre-leachingWashing for 1100s, collecting for 920s, and washing for 300s, collecting the purified solution, concentrating, and converting into methanol solvent to 1.0 mL;
the adsorbent is one or a mixture of more of diatomite, activated carbon and Florisil;
(c) the pretreated sample is put on a computer for testing, then the peak area value of each target compound is taken into a corresponding standard curve, the corresponding concentration Xi of each target compound is obtained by calculation, and then the concentration Xi is calculated according to w = XiV3V1/V2M, calculating the mass fraction of each target compound in the soil, wherein the unit of w is microgram/kg, V1Is the volume of the first nitrogen blowing concentration constant volume, unit mL, V2Measuring the volume of the concentrated solution, unit mL, V3For the volume tested in reconcentration, the units mL, M are the total mass of the soil sample, the units g, Xi are X1，X2，X3，X4，X5，X6，X7Or X8Unit is microgram/L according to x1，x2，x3，x4，x5，x6，x7Or x8Multiplying the concentration of the internal standard substance;
chromatographic conditions are as follows: the column temperature is 35 ℃; the flow rate is 0.4 mL/min; sampling amount is 10 muL, and separation time is 13 min; the mobile phase A is water added with 0.1 percent of ammonia water, and the mobile phase B is methanol added with 0.1 percent of ammonia water; gradient leaching: 0-2 min, 85% B, 2-7 min, 85% -100% B, 7-9.8 min, 100% B, 9.8-10.0 min, 85% B, 10.0-13.0 min, 85% B;
mass spectrum conditions: monitoring multiple reactions of triple quadrupole rod tandem mass spectrometry; APCI negative ion ionization mode; the pressure of the air curtain is 40psi, the voltage of the spray needle is-4500V, the temperature of the ion source is 300 ℃, and the pressure of the spray air is 55 psi; a collision air pressure medium; target scan time 0.5s, entrance voltage 10V, exit voltage 13V.
2. The method for analyzing polybrominated diphenyl ether compounds in soil by liquid chromatography-tandem mass spectrometry according to claim 1, characterized in that: (b) and blowing nitrogen to the collected purification liquid, adding 0.5mL of methanol when the amount of the solution is reduced to 0.1-0.2 mL of the total volume, continuing nitrogen blowing, repeating the previous steps for three times, and finally fixing the volume to 1.0mL by using methanol.
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