CN115184523B - Method for detecting content of chloromethane in water - Google Patents
Method for detecting content of chloromethane in water Download PDFInfo
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- CN115184523B CN115184523B CN202211006959.7A CN202211006959A CN115184523B CN 115184523 B CN115184523 B CN 115184523B CN 202211006959 A CN202211006959 A CN 202211006959A CN 115184523 B CN115184523 B CN 115184523B
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- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 title claims abstract description 190
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000000523 sample Substances 0.000 claims abstract description 65
- 238000001514 detection method Methods 0.000 claims abstract description 64
- 238000010926 purge Methods 0.000 claims abstract description 45
- 239000012488 sample solution Substances 0.000 claims abstract description 29
- 238000002347 injection Methods 0.000 claims abstract description 21
- 239000007924 injection Substances 0.000 claims abstract description 21
- LTUTVFXOEGMHMP-UHFFFAOYSA-N dibromofluoromethane Chemical compound FC(Br)Br LTUTVFXOEGMHMP-UHFFFAOYSA-N 0.000 claims abstract description 15
- MVPPADPHJFYWMZ-RALIUCGRSA-N 1-chloro-2,3,4,5,6-pentadeuteriobenzene Chemical compound [2H]C1=C([2H])C([2H])=C(Cl)C([2H])=C1[2H] MVPPADPHJFYWMZ-RALIUCGRSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000012224 working solution Substances 0.000 claims abstract description 11
- 238000000642 dynamic headspace extraction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000004817 gas chromatography Methods 0.000 claims description 21
- 238000003795 desorption Methods 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 238000001819 mass spectrum Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 24
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000012086 standard solution Substances 0.000 description 20
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 229940050176 methyl chloride Drugs 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000013582 standard series solution Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- -1 extractants Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 229960005015 local anesthetics Drugs 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Classifications
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides a method for detecting the content of chloromethane in water, which comprises the following steps: mixing a chloromethane standard sample, an internal standard substance and a substitute to prepare a standard working solution; mixing a water sample, an internal standard substance and a substitute to prepare a sample solution; adopting a purging and trapping device to purge and trap a standard working solution or a sample solution, and then adopting a gas chromatograph-mass spectrometer for analysis to obtain the content of chloromethane in water; the internal standard comprises chlorobenzene-D5 and the substitute comprises dibromofluoromethane. According to the invention, chlorobenzene-D5 is used as an internal standard for quantitative detection, a specific heating program is matched, the accuracy is high, the test result is not influenced by sample injection repeatability and experimental condition stability, and the method has the advantages of simplicity in operation, short test period, low loss, high recovery rate, good precision and the like, and can be used for effectively measuring the chloromethane content in water quality and improving the working efficiency.
Description
Technical Field
The invention belongs to the technical field of environmental detection, and particularly relates to a method for detecting the content of chloromethane in water.
Background
Methyl chloride, also known as methyl chloride, is an organic compound of the formula CH 3 Cl is colorless gas at normal temperature and pressure, is slightly soluble in water, and is dissolved in ethanol, chloroform, benzene, carbon tetrachloride, glacial acetic acid and the like, and is mainly used as a raw material of organic silicon, and also used as a solvent, a refrigerant, a spice and the like. Methyl chloride is an important raw material for organic synthesis.
In the organosilicon field, methyl chloride is mainly used for the production of organosilicon compounds, methylchlorosilanes, and methylcellulose. But also widely used as solvents, extractants, propellants, refrigerants, local anesthetics, methylating agents, for the production of pesticides, medicines, fragrances, etc. The chloromethane has the following characteristics: 1. acute toxicity, 2, mutagenicity, 3, teratogenicity, 4, carcinogenicity, 5, reproductive toxicity, etc., and is extremely harmful to human body.
Due to CH in water 3 The Cl concentration is low, and the direct detection is not easy. Yang Guipeng, liu Xiaolan, song Guisheng, wang Xiaomeng, analytical chemistry study bulletin, 2010 (5): 719-222 discloses that purge-trap-gas chromatography is used to determine methyl chloride and methyl bromide in seawater, and external standard method is used to determine the content of methyl chloride in seawater, the accuracy of the method is affected by repeatability of sample injection and stability of experimental conditions, chromatographic conditions (response performance of detector, column temperature, flow rate and composition of mobile phase, sample injection amount, column efficiency, etc.) of each sample analysis are difficult to be identical, and thus large errors are prone to occur. In addition, when the standard working curve is drawn, a standard sample (or a sample with known accurate content) of the component to be measured is generally used, so that the variation of the component to be measured in the pretreatment process of the sample cannot be compensated. And the recovery rate of the chloromethane measured by the method is 89% -97%, and the recovery rate is lower.
CN114487150a discloses a method for detecting chloromethane in surface water by purge and trap/gas chromatography mass spectrometry, wherein the column temperature in gas chromatography analysis is a key factor affecting the separation effect, however, the document does not disclose a corresponding column temperature; and fluorobenzene is adopted as an internal standard, so that the RSD value of multiple measurements is higher.
Therefore, how to provide a method for detecting the content of chloromethane in water quality, which has higher accuracy and precision, and the test result is not influenced by the repeatability of sample injection and the stability of experimental conditions, becomes the problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for detecting the content of chloromethane in water. According to the invention, chlorobenzene-D5 is used as an internal standard for quantitative detection, a specific heating program is matched, the accuracy is high, the test result is not influenced by sample injection repeatability and experimental condition stability, and the method has the advantages of simplicity in operation, short test period, low loss, high recovery rate, good precision and the like, and can be used for effectively measuring the chloromethane content in water quality and improving the working efficiency.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for detecting the content of chloromethane in water, which comprises the following steps:
(1) Mixing a chloromethane standard sample, an internal standard substance, a substitute and water to prepare a standard working solution; mixing a water sample, an internal standard substance and a substitute to prepare a sample solution;
(2) Adopting a purging and trapping device to purge and trap a standard working solution or a sample solution, and then adopting a gas chromatograph-mass spectrometer for analysis to obtain the content of chloromethane in water;
wherein the internal standard in step (1) comprises chlorobenzene-D5 and the substitute comprises dibromofluoromethane;
in the step (2), the temperature increasing program in the detection of the gas chromatograph comprises the following steps: standing at 38-42deg.C for 2.5-3.5min, and heating to 125-135deg.C at 8-12deg.C/min for 2.5-3.5min; then heating to 235-240 ℃ at a heating rate of 15-25 ℃/min, and staying for 1.0-2.0min.
In the invention, in the step (1), before the water sample, the internal standard substance and the substitute are mixed to prepare a sample solution, the water sample needs to be pretreated, and the pretreatment comprises the following steps: adding ascorbic acid into the water sample, and then adjusting the pH value to obtain the pretreated water sample.
Preferably, 40mL of the water sample is added with 0.02-0.03g of ascorbic acid.
Preferably, the pH is adjusted to a pH of 2 or less.
In the present invention, in the step (1), the concentration of the internal standard in the sample solution is 40 to 60. Mu.g/L; the concentration of the surrogate in the sample solution is 40-60 μg/L.
In the invention, the purging flow in the purging and capturing process is set to be 45-55mL/min, the purging temperature is 18-22 ℃, the preheating time is 0.2-0.3min, and the purging time is 10-12min.
In the invention, the dry blowing time in the blowing and capturing process is set to be 0.4-0.6min.
Preferably, the pre-desorption temperature in the purging and capturing process is set to be 246-255 ℃, the desorption temperature is 255-265 ℃, and the desorption time is 2.5-3min.
In the invention, the baking temperature in the purging and capturing process is 255-265 ℃ and the baking time is 7.5-8.5min.
Preferably, the transmission line temperature in the purge catch is set at 195-205 ℃.
In the invention, the temperature of the sample inlet in the detection of the gas chromatograph is 225-235 ℃.
Preferably, the carrier gas in the detection of the gas chromatograph comprises any one or a combination of at least two of nitrogen, helium or argon, preferably helium.
Preferably, the sample injection mode in the detection of the gas chromatograph is constant-current sample injection, and the split ratio is (8-12): 1.
In the invention, the flow rate of the column in the detection of the gas chromatography is 0.8-1.2mL/min.
Preferably, the chromatographic column used in the detection of the gas chromatography is DB-624, the column length is 30m, the inner diameter is 0.25mm, and the column wall thickness is 1.40 μm.
In the invention, the ion source in the detection of the mass spectrum is an electron bombardment ion source, the temperature of the ion source is 190-210 ℃, and the ionization energy is 65-75eV.
Preferably, the scanning mode in the detection of the mass spectrum is full scanning.
Preferably, the m/z in the detection of the mass spectrum is 25-300amu.
In the invention, the solvent delay in the detection of the mass spectrum is 0.5-1.5min.
Preferably, the electron multiplication voltage in the detection of the mass spectrum coincides with the tuning voltage.
Preferably, the interface temperature in the detection of the mass spectrum is 245-255 ℃.
As a preferable technical scheme of the invention, the method for detecting the content of chloromethane in water quality comprises the following steps:
(I) Mixing a chloromethane standard sample, an internal standard substance, a substitute and water to prepare a standard working solution; adding ascorbic acid into a water sample, then adjusting the pH to be less than or equal to 2 to obtain a pretreated water sample, and mixing the pretreated water sample, an internal standard substance and a substitute to prepare a sample solution;
wherein the internal standard comprises chlorobenzene-D5 and the substitute comprises dibromofluoromethane;
(2) The standard working solution and the sample solution obtained in the step (1) are respectively subjected to purge and trap/gas chromatography-mass spectrometry detection to obtain the content of chloromethane in water;
and setting purge and trap conditions in the purge and trap/gas chromatography-mass spectrometry detection: the purging flow is 45-55mL/min, the purging temperature is 18-22 ℃, the preheating time is 0.2-0.3min, and the purging time is 10-12min; the dry blowing time is 0.4-0.6min; the pre-desorption temperature is 246-255 ℃, the desorption temperature is 255-265 ℃, and the desorption time is 2.5-3min; baking at 255-265 deg.C for 7.5-8.5min; the temperature of the transmission line is 195-205 ℃;
the condition setting of gas chromatography in the purge-trap/gas chromatography-mass spectrometry detection comprises the following steps: the temperature of the sample inlet is 225-235 ℃; the carrier gas comprises any one or a combination of at least two of nitrogen, helium or argon; the sample injection mode is constant-current sample injection, and the split ratio is (8-12): 1; the flow rate of the column is 0.8-1.2mL/min; the chromatographic column is DB-624, the column length is 30m, the inner diameter is 0.25mm, and the column wall thickness is 1.40 mu m; the temperature raising program includes the steps of: standing at 38-42deg.C for 2.5-3.5min, and heating to 125-135deg.C at 8-12deg.C/min for 2.5-3.5min; heating to 235-240 ℃ at a heating rate of 15-25 ℃/min, and staying for 1.0-2.0min;
condition setting of mass spectrum in the purge-trap/gas chromatography-mass spectrometry detection: the ion source is an electron bombardment ion source, the temperature of the ion source is 190-210 ℃, and the ionization energy is 65-75eV; the scanning mode is full scanning; m/z is 25-300amu; the solvent delay is 0.5-1.5min; the electron multiplication voltage is consistent with the tuning voltage; the interface temperature is 245-255 ℃.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, chlorobenzene-D5 is used as an internal standard for quantitative detection, a specific heating program is matched, the accuracy is high, the test result is not influenced by sample injection repeatability and experimental condition stability, and the method has the advantages of simplicity in operation, short test period, low loss, high recovery rate, good precision and the like, and can be used for effectively measuring the chloromethane content in water quality and improving the working efficiency.
Drawings
Fig. 1 is a standard graph of methyl chloride.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for detecting the content of chloromethane in water, which comprises the following steps:
preparation of standard working solution
(1) Respectively preparing a chloromethane standard solution with the concentration of 100 mug/mL, a dibromofluoromethane substitute standard solution with the concentration of 100 mug/mL and a chlorobenzene-D5 internal standard solution with the concentration of 25 mug/mL;
(2) And respectively transferring a certain amount of standard solution of chloromethane and standard solution of dibromofluoromethane substitute into blank reagent water to prepare standard series solutions, wherein the concentrations of the chloromethane and the dibromofluoromethane substitute in the standard series solutions are 5, 10, 20, 50, 100 and 200 mug/L respectively, and then respectively adding 50 mug of internal standard solution into 5mL of standard series solutions to obtain standard working solution.
(II) preparation of sample solution
(1) Using 40mL to purge a bottle, placing 0.025g of ascorbic acid in the bottle before collection, removing residual chlorine interference, fully collecting a water sample, keeping no gap in the bottle, and adding hydrochloric acid to adjust the pH value to 2 to obtain a pretreated water sample;
(2) Adding dibromofluoromethane substitute standard solution and chlorobenzene-D5 internal standard solution into the pretreated water sample to obtain sample solution; the concentration of dibromofluoromethane surrogate and chlorobenzene-D5 internal standard in the sample solution was 50. Mu.g/L.
(III) Instrument Condition and parameter settings
Purge-trap conditions in purge-trap/gas chromatography-mass spectrometry detection were set: the purging flow is 50mL/min, the purging temperature is 20 ℃, the preheating time is 0.25min, and the purging time is 11min; the dry blowing time is 0.5min; the pre-desorption temperature is 250 ℃, the desorption temperature is 260 ℃ and the desorption time is 2.8min; the baking temperature is 260 ℃ and the baking time is 8min; the temperature of the transmission line is 200 ℃;
condition setting of gas chromatography in purge-trap/gas chromatography-mass spectrometry detection: the temperature of the sample inlet is 230 ℃; the carrier gas is helium; the sample injection mode is constant-current sample injection, and the split ratio is 10:1; the flow rate of the column is 1mL/min; the chromatographic column is DB-624, the column length is 30m, the inner diameter is 0.25mm, and the column wall thickness is 1.40 mu m; the temperature raising program includes the steps of: standing at 40deg.C for 3min, and then heating to 130deg.C at 10deg.C/min for 3min; then heating to 238 ℃ at a heating rate of 20 ℃/min, and staying for 1.5min;
condition setting of mass spectrum in purge-trap/gas chromatography-mass spectrometry detection: the ion source is an electron bombardment ion source, the temperature of the ion source is 200 ℃, and the ionization energy is 70eV; the scanning mode is full scanning; m/z is 25-300amu; the solvent delay was 1min; the electron multiplication voltage is consistent with the tuning voltage; the interface temperature was 250 ℃.
(III) drawing of a Standard Curve
Under the instrument conditions and parameter conditions, the standard working solution is subjected to purge and trap/gas chromatography-mass spectrometry detection, the ratio of the response values of the chloromethane and the internal standard is taken as an ordinate, the concentration ratio is taken as an abscissa, and a standard curve of the chloromethane is drawn.
The standard curve of methyl chloride is shown in fig. 1, and is y=0.3976677x+0.25317, r 2 =0.9997, indicating a good linear relationship of the methyl chloride standard curve.
Quantitative analysis of chloromethane in water sample
Under the instrument conditions and parameter conditions, adding a chloromethane standard solution into the sample solution to ensure that the theoretical content of the chloromethane standard solution is 50 mug/L; and detecting the sample solution by adopting a purge trap/gas chromatography-mass spectrometry, and calculating by adopting a standard curve to obtain the concentration of chloromethane in the water sample.
Example 2
The embodiment provides a method for detecting the content of chloromethane in water, which comprises the following steps:
preparation of sample solution
(1) Using 40mL to purge a bottle, placing 0.024g of ascorbic acid in the bottle before collection, removing residual chlorine interference, fully collecting a water sample, keeping no gap in the bottle, and adding hydrochloric acid to adjust the pH value to 1.8 to obtain a pretreated water sample;
(2) Adding dibromofluoromethane substitute standard solution and chlorobenzene-D5 internal standard solution into the pretreated water sample to obtain sample solution; the concentration of dibromofluoromethane surrogate and chlorobenzene-D5 internal standard in the sample solution was 52. Mu.g/L.
(II) Instrument Condition and parameter settings
Purge-trap conditions in purge-trap/gas chromatography-mass spectrometry detection were set: the purging flow is 48mL/min, the purging temperature is 18 ℃, the preheating time is 0.22min, and the purging time is 11.5min; the dry blowing time is 0.55min; the pre-desorption temperature is 246 ℃, the desorption temperature is 263 ℃, and the desorption time is 2.9min; the baking temperature is 263 ℃ and the baking time is 8.2min; the temperature of the transmission line is 203 ℃;
condition setting of gas chromatography in purge-trap/gas chromatography-mass spectrometry detection: the temperature of the sample inlet is 228 ℃; the carrier gas is helium; the sample injection mode is constant-current sample injection, and the split ratio is 11:1; the column flow rate is 1.1mL/min; the chromatographic column is DB-624, the column length is 30m, the inner diameter is 0.25mm, and the column wall thickness is 1.40 mu m; the temperature raising program includes the steps of: the temperature is kept at 41 ℃ for 2.8min, then the temperature is raised to 132 ℃ at a heating rate of 11 ℃/min, and the temperature is kept for 3.2min; then heating to 240 ℃ at a heating rate of 16 ℃/min, and staying for 1.7min;
condition setting of mass spectrum in purge-trap/gas chromatography-mass spectrometry detection: the ion source is an electron bombardment ion source, the temperature of the ion source is 205 ℃, and the ionization energy is 72eV; the scanning mode is full scanning; m/z is 25-300amu; the solvent delay was 1.4min; the electron multiplication voltage is consistent with the tuning voltage; the interface temperature was 253 ℃.
Under the instrument conditions and parameter conditions, adding a chloromethane standard solution into the sample solution to ensure that the theoretical content of the chloromethane standard solution is 50 mug/L; and detecting the sample solution by adopting a purge trap/gas chromatography-mass spectrometry, and calculating by adopting a standard curve to obtain the concentration of chloromethane in the water sample.
Example 3
The embodiment provides a method for detecting the content of chloromethane in water, which comprises the following steps:
preparation of sample solution
(1) Using 40mL to purge a bottle, placing 0.026g of ascorbic acid in the bottle before collection, removing residual chlorine interference, fully collecting a water sample, keeping no gap in the bottle, and adding hydrochloric acid to adjust the pH value to 1.6 to obtain a pretreated water sample;
(2) Adding dibromofluoromethane substitute standard solution and chlorobenzene-D5 internal standard solution into the pretreated water sample to obtain sample solution; the concentration of dibromofluoromethane surrogate and chlorobenzene-D5 internal standard in the sample solution was 48. Mu.g/L.
(II) Instrument Condition and parameter settings
Purge-trap conditions in purge-trap/gas chromatography-mass spectrometry detection were set: the purging flow is 52mL/min, the purging temperature is 22 ℃, the preheating time is 0.24min, and the purging time is 12min; the dry blowing time is 0.6min; the pre-desorption temperature is 248 ℃, the desorption temperature is 258 ℃, and the desorption time is 2.6min; the baking temperature is 258 ℃, and the baking time is 8.2min; the temperature of the transmission line is 203 ℃;
condition setting of gas chromatography in purge-trap/gas chromatography-mass spectrometry detection: the temperature of the sample inlet is 232 ℃; the carrier gas is helium; the sample injection mode is constant-current sample injection, and the split ratio is 9:1; the column flow rate is 0.9mL/min; the chromatographic column is DB-624, the column length is 30m, the inner diameter is 0.25mm, and the column wall thickness is 1.40 mu m; the temperature raising program includes the steps of: the temperature is kept at 38 ℃ for 2.7min, then the temperature is increased to 132 ℃ at the heating rate of 9 ℃/min, and the temperature is kept for 2.7min; then heating to 235 ℃ at a heating rate of 22 ℃/min, and staying for 1.2min;
condition setting of mass spectrum in purge-trap/gas chromatography-mass spectrometry detection: the ion source is an electron bombardment ion source, the temperature of the ion source is 207 ℃, and the ionization energy is 68eV; the scanning mode is full scanning; m/z is 25-300amu; the solvent delay was 1.2min; the electron multiplication voltage is consistent with the tuning voltage; the interface temperature was 252 ℃.
Under the instrument conditions and parameter conditions, adding a chloromethane standard solution into the sample solution to ensure that the theoretical content of the chloromethane standard solution is 50 mug/L; and detecting the sample solution by adopting a purge trap/gas chromatography-mass spectrometry, and calculating by adopting a standard curve to obtain the concentration of chloromethane in the water sample.
Example 4
The embodiment provides a method for detecting the content of chloromethane in water, which is different from embodiment 1 only in that the purging flow in the purging and capturing process is set to be 40mL/min, the purging time is 15min, and other steps are the same as embodiment 1.
Example 5
The embodiment provides a method for detecting the content of chloromethane in water, which is different from embodiment 1 only in that the purging flow in the purging and capturing process is set to be 60mL/min, the purging time is 8min, and other steps are the same as embodiment 1.
Example 6
The present embodiment provides a method for detecting chloromethane content in water, which is different from embodiment 1 only in that the chromatographic column is replaced with R in the detection of gas chromatography tx -624 elastic quartz capillary column, 60m length, 0.32mm inner diameter, 1.80 μm column wall thickness, otherwise the same procedure as in example 1.
Example 7
The present example provides a method for detecting the content of chloromethane in water, which is different from example 1 only in that the chromatographic column is replaced by Agilent HP-VOC in the detection of gas chromatography, the column length is 30m, the inner diameter is 0.2mm, the column wall thickness is 1.12 μm, and other steps are the same as example 1.
Example 8
The present embodiment provides a method for detecting the content of chloromethane in water, which is different from embodiment 1 only in that the sample injection mode in the detection of gas chromatography is split sample injection, and other steps are the same as embodiment 1.
Comparative example 1
The comparative example provides a method for detecting the content of chloromethane in water, which is different from the embodiment 1 only in that the temperature raising program in the detection of gas chromatography comprises the following steps: stay at 45 ℃ for 10min, then heat up to 200 ℃ at a heating rate of 15 ℃/min, stay for 5min; the other steps are the same as in example 1.
Comparative example 2
The comparative example provides a method for detecting the content of chloromethane in water, which is different from the embodiment 1 only in that the temperature raising program in the detection of gas chromatography comprises the following steps: standing at 40deg.C for 3min, and then heating to 238 deg.C at 10deg.C/min for 1.5min; the other steps are the same as in example 1.
Comparative example 3
The comparative example provides a method for detecting the content of chloromethane in water, which is different from the embodiment 1 only in that the temperature raising program in the detection of gas chromatography comprises the following steps: standing at 40deg.C for 3min, and then heating to 130deg.C at 20deg.C/min for 3min; then the temperature is raised to 238 ℃ at a heating rate of 10 ℃/min, and the rest time is 1.5min, and other steps are the same as in example 1.
Comparative example 4
The comparative example provides a method for detecting the content of chloromethane in water, which is different from the embodiment 1 only in that the temperature raising program in the detection of gas chromatography comprises the following steps: standing at 40deg.C for 3min, and then heating to 130deg.C at a heating rate of 5deg.C/min for 3min; then the temperature is raised to 238 ℃ at a heating rate of 30 ℃/min, and other steps are performed for 1.5min in the same way as in example 1.
Comparative example 5
The comparative example provides a method for detecting the content of chloromethane in water, which is different from example 1 only in that the internal standard is replaced by fluorobenzene, and other steps are the same as in example 1.
Test example 1
The results of the tests of examples 1 to 8 and comparative examples 1 to 5 are shown in Table 1 below:
TABLE 1
As can be seen from the data in Table 1, the RSD range of the chloromethane in the water quality measured by adopting the detection method provided by the preferred technical scheme (examples 1-3) of the invention is 2.4-3.3%, and the detection method of the chloromethane content in the water quality provided by the invention has the advantages of small variation coefficient, high robustness and good repeatability.
As can be seen from a comparison of examples 1 and examples 4-5, the purge flow rate affects the test results, and the magnitude of the purge flow rate affects not only the trapping effect of the gas, but also the sample analysis time: too small a flow rate can result in too long a measurement time; too high a flow rate is detrimental to the adsorption of methyl chloride on the collection tubes.
As can be seen from a comparison of example 1 and examples 6-7, the selection of the chromatographic column affects the detection of methyl chloride.
As can be seen from a comparison of example 1 and example 8, split injection is detrimental to the detection of methyl chloride.
As is evident from the comparison of example 1 and comparative examples 1 to 4, the temperature elevation program affects the detection of methyl chloride.
From a comparison of example 1 and comparative example 5, it is evident that the selection of the internal standard influences the detection of the methyl chloride content.
Test example 2
Calculation of chloromethane standard recovery rate
The testing method comprises the following steps: the standard recovery rate test was performed on samples with known chloromethane content, 3 concentration levels of chloromethane standard solutions were added, and the test was performed according to the conditions of purge-trap/gas chromatograph-mass spectrometer detection in example 1, and the test results were shown in table 2 below, in parallel for 5 times:
TABLE 2
Recovery (%) = (average measured content/theoretical content after addition of standard) ×100%.
As can be seen from the data in Table 2, the standard recovery rate of the chloromethane is 95-105% in different concentration levels, which shows that the method for detecting the content of the chloromethane in the water quality provided by the invention has good precision and high accuracy.
Test example 3
Substitute labeling recovery calculation
The testing method comprises the following steps: the standard solutions of dibromofluoromethane substitutes were added at 3 concentration levels, and the test was performed under the conditions of purge-trap/gas chromatograph-mass spectrometer detection in example 1, and the test results were shown in table 3 below, in parallel for 5 times.
TABLE 3 Table 3
Recovery (%) = (average measured content/theoretical content after addition of standard) ×100%.
As can be seen from the data in Table 3, the standard recovery rate of dibromofluoromethane substitutes in different concentration levels is 95-105%, which shows that the method for detecting the content of chloromethane in water quality has good precision and high accuracy.
Test example 4
Detection limit and quantification limit test
The testing method comprises the following steps: referring to the annex A.1-B of HJ 168-2020, taking a water sample without chloromethane as a blank test solution, adding a standard mark to the chloromethane concentration of 5.0 mug/L, testing according to the condition of purge-trap/gas chromatography-mass spectrometry detection in the example 1, repeating the test for 7 times, calculating the detection limit of the method according to 3.143 times of standard deviation of the standard mark adding result, and calculating the quantitative limit according to 4 times of the detection limit.
The detection limit of methyl chloride in the water is 1.0 mug/L, and the quantitative limit is 4.0 mug/L.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (22)
1. The method for detecting the content of chloromethane in water is characterized by comprising the following steps of:
(1) Mixing a chloromethane standard sample, an internal standard substance, a substitute and water to prepare a standard working solution; mixing a water sample, an internal standard substance and a substitute to prepare a sample solution;
(2) Adopting a purging and trapping device to purge and trap a standard working solution or a sample solution, and then adopting a gas chromatograph-mass spectrometer for analysis to obtain the content of chloromethane in water;
wherein the internal standard in step (1) comprises chlorobenzene-D5 and the substitute comprises dibromofluoromethane;
in the step (2), the purging flow rate in the purging and capturing process is 45-55mL/min;
in the step (2), the temperature increasing program in the detection of the gas chromatograph comprises the following steps: standing at 38-42deg.C for 2.5-3.5min, and heating to 125-135deg.C at 8-12deg.C/min for 2.5-3.5min; then heating to 235-240 ℃ at a heating rate of 15-25 ℃/min, and staying for 1.0-2.0min.
2. The method for detecting the content of chloromethane in water according to claim 1, wherein in the step (1), pretreatment is required for the water sample before the water sample, the internal standard substance and the substitute are mixed and prepared into a sample solution, and the pretreatment comprises the following steps: adding ascorbic acid into the water sample, and then adjusting the pH value to obtain the pretreated water sample.
3. The method for detecting the content of chloromethane in water according to claim 2, wherein 40mL of the water sample is added with 0.02-0.03g of ascorbic acid.
4. The method for detecting the content of chloromethane in water according to claim 2, wherein the pH is adjusted to be less than or equal to 2.
5. The method for detecting the content of chloromethane in water according to claim 1, wherein in the step (1), the concentration of the internal standard substance in the sample solution is 40-60 μg/L; the concentration of the surrogate in the sample solution is 40-60 μg/L.
6. The method for detecting the content of chloromethane in water according to claim 1, wherein the purging temperature in the purging and capturing process is set to be 18-22 ℃, the preheating time is 0.2-0.3min, and the purging time is 10-12min.
7. The method for detecting the content of chloromethane in water according to claim 1, wherein the dry blowing time in the purging and capturing process is set to be 0.4-0.6min.
8. The method for detecting the content of chloromethane in water according to claim 1, wherein the pre-desorption temperature in the purging and capturing process is set to be 246-255 ℃, the desorption temperature is 255-265 ℃, and the desorption time is 2.5-3min.
9. The method for detecting the content of chloromethane in water according to claim 1, wherein the baking temperature in the purging and capturing process is 255-265 ℃ and the baking time is 7.5-8.5min.
10. The method for detecting the content of chloromethane in water according to claim 1, wherein the temperature of a transmission line in the purging and capturing is set to be 195-205 ℃.
11. The method for detecting the content of chloromethane in water according to claim 1, wherein the temperature of a sample inlet in the detection of gas chromatography is 225-235 ℃.
12. The method for detecting the content of chloromethane in water according to claim 1, wherein the carrier gas in the detection of gas chromatography comprises any one or a combination of at least two of nitrogen, helium and argon.
13. The method for detecting the content of chloromethane in water according to claim 1, wherein the carrier gas in the detection of gas chromatography is helium.
14. The method for detecting the content of chloromethane in water according to claim 1, wherein the sample injection mode in the detection of gas chromatography is constant-flow sample injection, and the split ratio is (8-12): 1.
15. The method for detecting the content of chloromethane in water according to claim 1, wherein the flow rate of the column in the detection of the gas chromatography is 0.8-1.2mL/min.
16. The method for detecting the content of chloromethane in water according to claim 1, wherein a chromatographic column used in the detection of the gas chromatography is DB-624, the column length is 30m, the inner diameter is 0.25mm, and the column wall thickness is 1.40 μm.
17. The method for detecting the content of chloromethane in water according to claim 1, wherein the ion source in the detection of the mass spectrum is an electron bombardment ion source, the temperature of the ion source is 190-210 ℃, and the ionization energy is 65-75eV.
18. The method for detecting the content of chloromethane in water according to claim 1, wherein the scanning mode in the detection of mass spectrum is full scanning.
19. The method for detecting the content of chloromethane in water according to claim 1, wherein m/z in the detection of mass spectrum is 25-300amu.
20. The method for detecting the content of chloromethane in water according to claim 1, wherein the solvent delay in the detection of the mass spectrum is 0.5-1.5min.
21. The method for detecting the content of chloromethane in water according to claim 1, wherein the electron multiplication voltage is consistent with the tuning voltage in the detection of the mass spectrum.
22. The method for detecting the content of chloromethane in water according to claim 1, wherein the interface temperature in the detection of the mass spectrum is 245-255 ℃.
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