CN111855870A - Method for determining polychlorinated biphenyl compounds in water - Google Patents
Method for determining polychlorinated biphenyl compounds in water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 17
- -1 polychlorinated biphenyl compounds Chemical class 0.000 title claims abstract description 15
- 150000003071 polychlorinated biphenyls Chemical group 0.000 claims abstract description 31
- 238000000605 extraction Methods 0.000 claims abstract description 9
- 239000000523 sample Substances 0.000 claims description 92
- 150000002500 ions Chemical class 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 230000014759 maintenance of location Effects 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 238000004458 analytical method Methods 0.000 claims description 15
- 238000011088 calibration curve Methods 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 9
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- OYNXPGGNQMSMTR-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)-phenylphosphane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1P(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=CC=CC=C1 OYNXPGGNQMSMTR-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012496 blank sample Substances 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000010586 diagram Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
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- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004451 qualitative analysis Methods 0.000 claims description 3
- 238000004445 quantitative analysis Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000012086 standard solution 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
- 238000012360 testing method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000010813 internal standard method Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 6
- 238000000622 liquid--liquid extraction Methods 0.000 abstract description 4
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 3
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- MVWHGTYKUMDIHL-UHFFFAOYSA-N 2,2',4,4',5,5'-hexachlorobiphenyl Chemical compound C1=C(Cl)C(Cl)=CC(Cl)=C1C1=CC(Cl)=C(Cl)C=C1Cl MVWHGTYKUMDIHL-UHFFFAOYSA-N 0.000 description 1
- IUTPYMGCWINGEY-UHFFFAOYSA-N 2,3',4,4',5-Pentachlorobiphenyl Chemical compound C1=C(Cl)C(Cl)=CC=C1C1=CC(Cl)=C(Cl)C=C1Cl IUTPYMGCWINGEY-UHFFFAOYSA-N 0.000 description 1
- BZTYNSQSZHARAZ-UHFFFAOYSA-N 2,4-dichloro-1-(4-chlorophenyl)benzene Chemical compound C1=CC(Cl)=CC=C1C1=CC=C(Cl)C=C1Cl BZTYNSQSZHARAZ-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- RPUMZMSNLZHIGZ-UHFFFAOYSA-N PCB138 Chemical compound C1=C(Cl)C(Cl)=CC(Cl)=C1C1=CC=C(Cl)C(Cl)=C1Cl RPUMZMSNLZHIGZ-UHFFFAOYSA-N 0.000 description 1
- WBHQEUPUMONIKF-UHFFFAOYSA-N PCB180 Chemical compound C1=C(Cl)C(Cl)=CC(Cl)=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl WBHQEUPUMONIKF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
- G01N30/8634—Peak quality criteria
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a method for measuring polychlorinated biphenyl compounds in water, which comprises the following steps: s1, sample extraction; s2, analyzing the sample; and S3, calculating and representing the result. The invention has the technical effects and advantages that: (1) the sample extraction is stable, the parallelism is good, and the precision is high. (2) The liquid-liquid extraction is simple to operate, can be realized in most laboratories, and can be used for large-batch detection. (3) The detection limit is low, the types of polychlorinated biphenyl are various, and the evaluation requirements of underground water quality standard (GB14848-2017) can be met. (4) The recovery rate of the sample added with the standard and the substitute can be between 70 and 130 percent.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for measuring polychlorinated biphenyl compounds in water.
Background
Polychlorinated biphenyls (PCBs) are chlorinated aromatic hydrocarbons generated by high-temperature chlorination of aniline serving as a raw material under the action of metal catalysis. PCBs have the advantages of good chemical inertness, heat resistance, incombustibility, low vapor pressure, high dielectric constant and the like, and are widely applied to industries such as electrical equipment, plastic processing, chemical engineering, printing and the like. According to WTO statistics, about 2017 tons of industrial polychlorinated biphenyl is produced globally by the end of 80 years in the 20 th century, and nearly 31 percent of PCBs are discharged into the environment. Even though the production of PCBs has been prohibited by law, leakage or unintended waste discharge of PCBs has caused a large area of contamination since their production.
PCBs are one of the Persistent Organic Pollutants (POPs) of international interest, also known as dioxin analogues. The low solubility, high stability and semi-volatility of PCBs make PCBs not only difficult to degrade in natural environment, but also can migrate remotely, and during the migration and transformation processes, the PCBs are also amplified by biological enrichment, and the concentration can be amplified by several times or hundreds of times, so that residues exist in soil, sediment, water and food. PCBs not only affect the reproductive system, interfere endocrine and reduce memory, but also increase the incidence of cancer, and pose great threat to the ecological environment and human health, thereby having great significance for the determination of PCBs in environmental samples. The underground water quality standard (GB14848-2017) specifies that the total content of polychlorinated biphenyl in class I water is not more than 0.05 mu g/L, wherein the total content of polychlorinated biphenyl is the sum of polychlorinated biphenyl monomers of PCB28, PCB25, PCB101, PCB118, PCB138, PCB153, PCB180, PCB194 and PCB 2069, so that the requirement of the underground water quality standard can be met only by accurately measuring the content of 9 PCBs monomers in water.
At present, the measuring standard of polychlorinated biphenyl in water in China only relates to gas chromatography-mass spectrometry for measuring polychlorinated biphenyl in water (HJ 715-2014) issued by the department of ecological environment, the gas chromatography-mass spectrometry for measuring 18 polychlorinated biphenyls in water is specified in the standard, but the measuring of PCB194 and PCB206 is not contained, and a standard method for measuring PCB194 and PCB206 in water is not available internationally, so that the evaluation requirement of underground water quality standard (GB/T14848-2017) cannot be met. The method can be used for measuring 20 polychlorinated biphenyl compounds in water, wherein 9 monomers in the total amount of polychlorinated biphenyl in the underground water quality standard (GB/T14848-.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for measuring polychlorinated biphenyl compounds in water. The method adopts liquid-liquid extraction/gas chromatography-mass spectrometry to determine 20 polychlorinated biphenyls in water, increases the determination of PCB194 and PCB206 compared with the gas chromatography-mass spectrometry for determining polychlorinated biphenyls in water (HJ 715-2014) of environmental standard, and meets the requirement on polychlorinated biphenyls (total amount) in the underground water quality standard (GB 14848-2017).
In order to achieve the purpose, the invention provides the following technical scheme:
a method for determining polychlorinated biphenyl compounds in water comprises the following steps:
s1, sample extraction
(1) Collecting and preserving
Collecting a sample in a brown glass sample bottle, and filling the sample bottle with a water sample; storing at 4 deg.C in dark place, and extracting within 7 d;
(2) extraction of
Shaking uniformly, accurately measuring 1L-2L of the water sample, putting the water sample into a separating funnel, adjusting the pH value of the water sample to 5-9 by using a hydrochloric acid solution or a sodium hydroxide solution, weighing 30g of sodium chloride, adding the sodium chloride into the water sample, and slightly shaking to dissolve the sodium chloride; adding 50mL of dichloromethane, adding a substitute standard use solution, and shaking for 10 min; standing and layering, collecting an organic phase, and putting into a receiving bottle; extracting for two times, and combining organic phases; adding anhydrous sodium sulfate into the extract to remove water, standing for more than 40min, and concentrating to 1 mL;
(3) purification
Washing the florisil solid-phase extraction column with 10mL of n-hexane, soaking for 5min, and removing the effluent liquid, wherein the flow rate is controlled at 2 mL/min; transferring the concentrated solution into a column, washing a sample concentrated solution bottle twice by using 2mL of normal hexane, transferring the sample concentrated solution bottle onto a solid-phase extraction column together, eluting the solid-phase extraction column by using 10mL of 1+9 acetone/normal hexane mixed eluent, and receiving the eluent;
(4) concentrating
Transferring the extract liquid into a nitrogen blowing pipe, and concentrating the extract liquid by using a nitrogen blowing instrument; setting the temperature of a nitrogen blowing concentrator to be 30 ℃, setting the pressure to be 1, concentrating the extracting solution to be about 1mL by using small-flow nitrogen, using dichloromethane to fix the volume to be 1.0mL, adding the internal standard use solution into the solution with the fixed volume, shaking up, and measuring. The prepared sample is refrigerated and stored below 4 ℃, and the analysis is completed within 30 days;
(5) preparation of a blank
A blank sample was prepared following the same procedure as for sample preparation, with experimental water replacing the sample.
S2 analysis sample
(1) Reference conditions of the apparatus
a gas chromatography conditions
Temperature programming:
and (3) sample introduction mode: injecting sample for 1min without shunting; sample introduction amount: 1.0 μ L; sample inlet temperature: 270 ℃; transmission line temperature: 270 ℃; column flow rate: 1.2 mL/min;
b reference conditions for mass spectrometry
Ion source temperature: 250 ℃; ionization energy: 70 eV;
full Scan (Scan) mass range: 45-500 amu;
a Select Ion (SIM) scan;
(2) calibration
a instrument Performance inspection
Before the instrument is used, the perfluorotributylamine is used for tuning a mass spectrometer; before sample analysis and every 12h, injecting 1.0 mu L of Decafluorotriphenylphosphine (DFTPP) use solution into a chromatogram, and checking an instrument system, wherein the abundance of the obtained mass ions is required to be completely in accordance with the requirement;
(3) plotting of calibration curves
Respectively sucking different volumes of standard and substitute standard use solutions to prepare standard series with concentrations of 20.0, 50.0, 100, 200 and 500 mug/L, simultaneously adding the internal standard use solution, and uniformly mixing. And analyzing according to instrument reference conditions to obtain different target compound mass spectrograms. And drawing a calibration curve by taking the ratio of the concentration of the target compound to the concentration of the internal standard compound as a horizontal coordinate and the ratio of the response value of the quantitative ions of the target compound to the response value of the quantitative ions of the internal standard compound as a vertical coordinate.
(4) Sample assay
And (4) taking a sample to be tested and determining according to the same instrument analysis conditions as the calibration curve drawing.
(5) Laboratory blank test
While analyzing the sample, the blank sample was measured under the same instrumental analysis conditions as the calibration curve was drawn.
S3, calculating and representing result
(1) Qualitative analysis
Data were collected in a full Scan mode (Scan) and characterized by the Relative Retention Time (RRT) of the target compound in the sample, the auxiliary qualitative ion and target ion abundance ratio (Q) versus the range of variation in the standard solution. The relative retention time of the compound of interest in the sample should be within ± 0.06 of the average relative retention time of that compound of the calibration curve. The relative deviation of the auxiliary qualitative ion and quantitative ion peak area ratio (Qsample) of the target compound in the sample and the auxiliary qualitative ion and quantitative ion peak area ratio (QStandard) of the target compound in the standard curve is controlled within +/-30%.
Calculating the relative retention time RRT according to equation (1)
In the formula:
RTc-Retention time of target compound, min;
RTisretention time of internal standard, min.
Mean Relative Retention Time (RRT) relative Retention time average of the same target Compound in a Standard series
Calculating the area ratio (Q) of the auxiliary qualitative ion peak to the auxiliary quantitative ion peak according to the formula (2)
In the formula:
at-the area of the quantified ion peak;
aq-area of auxiliary qualitative ion peak.
And drawing a total ion flow diagram of the selected ion scanning of the polychlorinated biphenyl standard substance.
(2) Quantitative analysis
Data were collected in a selective ion scanning mode (SIM) and quantified by internal standard. The mass concentration ρ i (ng/L) of the target in the sample is calculated according to the formula (3).
In the formula:
ρi-concentration of polychlorinated biphenyl compounds or substitutes in the sample, ng/L;
ρis-looking up the concentration of polychlorinated biphenyl compounds or substitutes, ug/L, according to a standard curve;
v is sample volume, mL;
vs — water sample volume, mL.
The invention has the technical effects and advantages that:
(1) the sample extraction is stable, the parallelism is good, and the precision is high.
(2) The liquid-liquid extraction is simple to operate, can be realized in most laboratories, and can be used for large-batch detection.
(3) The detection limit is low, the types of polychlorinated biphenyl are various, and the evaluation requirements of underground water quality standard (GB14848-2017) can be met.
(4) The recovery rate of the sample added with the standard and the substitute can be between 70 and 130 percent.
Drawings
Fig. 1 is a total ion flow diagram of selective ion scanning of polychlorinated biphenyl standard substances.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A method for determining polychlorinated biphenyl compounds in water comprises the following steps:
s1, sample extraction
(1) Collecting and preserving
Collecting a sample in a brown glass sample bottle, and filling the sample bottle with a water sample; storing at 4 deg.C in dark place, and extracting within 7 d;
(2) extraction of
Shaking uniformly, accurately measuring 1L-2L of the water sample, putting the water sample into a separating funnel, adjusting the pH value of the water sample to 5-9 by using a hydrochloric acid solution or a sodium hydroxide solution, weighing 30g of sodium chloride, adding the sodium chloride into the water sample, and slightly shaking to dissolve the sodium chloride; adding 50mL of dichloromethane, adding a substitute standard use solution, and shaking for 10 min; standing and layering, collecting an organic phase, and putting into a receiving bottle; extracting for two times, and combining organic phases; adding anhydrous sodium sulfate into the extract to remove water, standing for more than 40min, and concentrating to 1 mL;
(3) purification
Washing the florisil solid-phase extraction column with 10mL of n-hexane, soaking for 5min, and removing the effluent liquid, wherein the flow rate is controlled at 2 mL/min; transferring the concentrated solution into the column, washing the sample concentrated solution bottle twice with 2mL of n-hexane, transferring to the solid phase extraction column together, eluting the solid phase extraction column with 10mL of 1+9 acetone/n-hexane mixed eluent, and receiving the eluent.
(4) Concentrating
Transferring the extract liquid into a nitrogen blowing pipe, and concentrating the extract liquid by using a nitrogen blowing instrument; setting the temperature of a nitrogen blowing concentrator to be 30 ℃, setting the pressure to be 1, concentrating the extracting solution to be about 1mL by using small-flow nitrogen, using dichloromethane to fix the volume to be 1.0mL, adding the internal standard use solution into the solution with the fixed volume, shaking up, and measuring. The prepared samples were stored under refrigeration at below 4 ℃ and the analysis was completed within 30 days.
(5) Preparation of a blank
A blank sample was prepared following the same procedure as for sample preparation, with experimental water replacing the sample.
S2 analysis sample
(1) Reference conditions of the apparatus
a gas chromatography conditions
Temperature programming:
and (3) sample introduction mode: injecting sample for 1min without shunting; sample introduction amount: 1.0 μ L; sample inlet temperature: 270 ℃; transmission line temperature: 270 ℃; column flow rate: 1.2 mL/min;
b reference conditions for mass spectrometry
Ion source temperature: 250 ℃; ionization energy: 70 eV;
full Scan (Scan) mass range: 45-500 amu;
select Ion (SIM) scan, target compound scan ion see table 1;
TABLE 1 corresponding Scan ions for target Compounds
(2) Calibration
a instrument Performance inspection
Before the instrument is used, the perfluorotributylamine is used for tuning a mass spectrometer; before sample analysis and every 12h, injecting 1.0 mu L of Decafluorotriphenylphosphine (DFTPP) use solution into a chromatogram, and checking an instrument system, wherein the abundance of the obtained mass ions all meets the requirements in the table 2;
TABLE 2 Critical Ionic and abundance criteria for Decafluorotriphenylphosphine (DFTPP)
| Mass to charge ratio | Abundance standard | Mass ion (m/z) | Abundance standard |
| 51 | 30 to 60 percent of the basic peak | 199 | 5 to 9 percent of base peak |
| 68 | Less than 2% of the 69 peak | 275 | |
| 70 | Less than 2% of the 69 peak | 365 | More than 1 percent of the basic peak |
| 127 | 40 to 60 percent of the basic peak | 441 | Is present and is less than 443 |
| 197 | Less than% of the base peak | 442 | More than 40 percent of the basic peak |
| 198 | Basic peak with abundance of 100% | 443 | 442 peak 17% > E |
(3) Plotting of calibration curves
Respectively sucking different volumes of standard and substitute standard use solutions to prepare standard series with concentrations of 20.0, 50.0, 100, 200 and 500 mug/L, simultaneously adding the internal standard use solution, and uniformly mixing. And analyzing according to instrument reference conditions to obtain different target compound mass spectrograms. And drawing a calibration curve by taking the ratio of the concentration of the target compound to the concentration of the internal standard compound as a horizontal coordinate and the ratio of the response value of the quantitative ions of the target compound to the response value of the quantitative ions of the internal standard compound as a vertical coordinate.
(4) Sample assay
And (4) taking a sample to be tested and determining according to the same instrument analysis conditions as the calibration curve drawing.
(5) Laboratory blank test
While analyzing the sample, the blank sample was measured under the same instrumental analysis conditions as the calibration curve was drawn.
S3, calculating and representing result
(1) Qualitative analysis
Data were collected in a full Scan mode (Scan) and characterized by the Relative Retention Time (RRT) of the target compound in the sample, the auxiliary qualitative ion and target ion abundance ratio (Q) versus the range of variation in the standard solution. The relative retention time of the compound of interest in the sample should be within ± 0.06 of the average relative retention time of that compound of the calibration curve. The relative deviation of the auxiliary qualitative ion and quantitative ion peak area ratio (Qsample) of the target compound in the sample and the auxiliary qualitative ion and quantitative ion peak area ratio (QStandard) of the target compound in the standard curve is controlled within +/-30%.
Calculating the relative retention time RRT according to equation (1)
In the formula:
RTc-Retention time of target compound, min;
RTisretention time of internal standard, min.
Mean Relative Retention Time (RRT) relative Retention time average of the same target Compound in a Standard series
Calculating the area ratio (Q) of the auxiliary qualitative ion peak to the auxiliary quantitative ion peak according to the formula (2)
In the formula:
at-the area of the quantified ion peak;
aq-area of auxiliary qualitative ion peak.
The total ion flow diagram of the selective ion scanning of the polychlorinated biphenyl standard substance is shown in figure 1.
The compounds in the figure are, in order of retention time: 1-PCB28-2 ', 3', 5 ', 6' -d4；2-PCB28；3-PCB52；4-PCB101；5-PCB81；6-PCB77；7-PCB77-d6；8-PCB123；9-PCB118；10-PCB114；11-PCB114-2′,3′,5′,6′-d4；12-PCB138；13-PCB105；14-PCB153；15-PCB126；16-PCB167；17-PCB156；18-PCB156-2′,6,6′-d3；19-PCB157；20-PCB180；21-PCB169；22-PCB189；23-PCB194；24-PCB206
(2) Quantitative analysis
Data were collected in a selective ion scanning mode (SIM) and quantified by internal standard. The mass concentration ρ i (ng/L) of the target in the sample is calculated according to the formula (3).
In the formula:
ρi-concentration of polychlorinated biphenyl compounds or substitutes in the sample, ng/L;
ρis-looking up the concentration of polychlorinated biphenyl compounds or substitutes, ug/L, according to a standard curve;
v is sample volume, mL;
vs — water sample volume, mL.
The polychlorinated biphenyl in the sample is extracted by adopting a liquid-liquid extraction method, and the extract liquid is separated and determined by a gas chromatography-mass spectrometry method after dehydration, concentration, purification and constant volume. And (4) according to retention time, fragment ion mass-to-charge ratio and different ion abundance ratios, determining the nature and quantifying by an internal standard method.
When the sample size was 1L, the detection limits of the method are specified in Table 3.
TABLE 3 name of target Compound and detection and lower determination limits
The points to be finally explained are: first, in the description of the present application, it should be noted that, unless otherwise specified and limited, the terms "mounted," "connected," and "connected" should be understood broadly, and may be a mechanical connection or an electrical connection, or a communication between two elements, and may be a direct connection, and "upper," "lower," "left," and "right" are only used to indicate a relative positional relationship, and when the absolute position of the object to be described is changed, the relative positional relationship may be changed;
secondly, the method comprises the following steps: in the drawings of the disclosed embodiments of the invention, only the structures related to the disclosed embodiments are referred to, other structures can refer to common designs, and the same embodiment and different embodiments of the invention can be combined with each other without conflict;
and finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (1)
1. A method for measuring polychlorinated biphenyl compounds in water is characterized by comprising the following steps:
s1, sample extraction
(1) Collecting and preserving
Collecting a sample in a brown glass sample bottle, and filling the sample bottle with a water sample; storing at 4 deg.C in dark place, and extracting within 7 d;
(2) extraction of
Shaking uniformly, accurately measuring 1L-2L of the water sample, putting the water sample into a separating funnel, adjusting the pH value of the water sample to 5-9 by using a hydrochloric acid solution or a sodium hydroxide solution, weighing 30g of sodium chloride, adding the sodium chloride into the water sample, and slightly shaking to dissolve the sodium chloride; adding 50mL of dichloromethane, adding a substitute standard use solution, and shaking for 10 min; standing and layering, collecting an organic phase, and putting into a receiving bottle; extracting for two times, and combining organic phases; adding anhydrous sodium sulfate into the extract to remove water, standing for more than 40min, and concentrating to 1 mL;
(3) purification
Washing the florisil solid-phase extraction column with 10mL of n-hexane, soaking for 5min, and removing the effluent liquid, wherein the flow rate is controlled at 2 mL/min; transferring the concentrated solution into a column, washing a sample concentrated solution bottle twice by using 2mL of normal hexane, transferring the sample concentrated solution bottle onto a solid-phase extraction column together, eluting the solid-phase extraction column by using 10mL of 1+9 acetone/normal hexane mixed eluent, and receiving the eluent;
(4) concentrating
Transferring the extract liquid into a nitrogen blowing pipe, and concentrating the extract liquid by using a nitrogen blowing instrument; setting the temperature of a nitrogen blowing concentrator to be 30 ℃ and the pressure to be 1, concentrating the extracting solution to about 1mL by using small-flow nitrogen, fixing the volume to 1.0mL by using dichloromethane, adding an internal standard use solution into the solution with the fixed volume, shaking up and measuring; the prepared sample is refrigerated and stored below 4 ℃, and the analysis is completed within 30 days;
(5) preparation of a blank
Replacing a sample with experimental water, and preparing a blank sample according to the same operation steps of sample preparation;
s2 analysis sample
(1) Reference conditions of the apparatus
a gas chromatography conditions
Temperature programming:
and (3) sample introduction mode: injecting sample for 1min without shunting; sample introduction amount: 1.0 μ L; sample inlet temperature: 270 ℃; transmission line temperature: 270 ℃; column flow rate: 1.2 mL/min;
b reference conditions for mass spectrometry
Ion source temperature: 250 ℃; ionization energy: 70 eV;
full Scan (Scan) mass range: 45-500 amu;
a Select Ion (SIM) scan;
(2) calibration
a instrument Performance inspection
Before the instrument is used, the perfluorotributylamine is used for tuning a mass spectrometer; before sample analysis and every 12h, injecting 1.0 mu L of Decafluorotriphenylphosphine (DFTPP) use solution into a chromatogram, and checking an instrument system, wherein the abundance of the obtained mass ions is required to be completely in accordance with the requirement;
(3) plotting of calibration curves
Respectively sucking standard and substitute standard use solutions with different volumes to prepare standard series with the concentrations of 20.0, 50.0, 100, 200 and 500 mug/L, simultaneously adding the internal standard use solution, and uniformly mixing; analyzing according to instrument reference conditions to obtain mass spectrograms of different target compounds; drawing a calibration curve by taking the ratio of the concentration of the target compound to the concentration of the internal standard compound as a horizontal coordinate and the ratio of the response value of the quantitative ions of the target compound to the response value of the quantitative ions of the internal standard compound as a vertical coordinate;
(4) sample assay
Taking a sample to be tested and determining according to the same instrument analysis conditions as the calibration curve;
(5) laboratory blank test
While analyzing the sample, measuring the blank sample according to the same instrument analysis conditions as the calibration curve;
s3, calculating and representing result
(1) Qualitative analysis
Collecting data in a full Scan mode (Scan), and characterizing the Relative Retention Time (RRT) of a target compound in a sample, the abundance ratio (Q) of auxiliary qualitative ions and target ions and the variation range in a standard solution; the difference between the relative retention time of the compound of interest in the sample and the average relative retention time of that compound of the calibration curve should be within ± 0.06; controlling the relative deviation of the area ratio of the auxiliary qualitative ion peak to the quantitative ion peak (Qsample) of the target compound in the sample and the area ratio of the auxiliary qualitative ion peak to the quantitative ion peak (Qstandard) of the target compound in the standard curve within +/-30%;
calculating the relative retention time RRT according to equation (1)
In the formula:
RTc-Retention time of target compound, min;
RTisretention time of internal standard, min.
Mean Relative Retention Time (RRT) relative Retention time average of the same target Compound in a Standard series
Calculating the area ratio (Q) of the auxiliary qualitative ion peak to the auxiliary quantitative ion peak according to the formula (2)
In the formula:
at-the area of the quantified ion peak;
aq-area of auxiliary qualitative ion peak.
Drawing a total ion flow diagram of selective ion scanning of polychlorinated biphenyl standard substances;
(2) quantitative analysis
Collecting data in a selective ion scanning mode (SIM), and quantifying by an internal standard method; calculating the mass concentration rho i (ng/L) of the target object in the sample according to the formula (3);
in the formula:
ρi-concentration of polychlorinated biphenyl compounds or substitutes in the sample, ng/L;
ρis-looking up the concentration of polychlorinated biphenyl compounds or substitutes, ug/L, according to a standard curve;
v is sample volume, mL;
vs — water sample volume, mL.
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