CN113390979A - Method for measuring aniline in soil and sediment - Google Patents
Method for measuring aniline in soil and sediment Download PDFInfo
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- CN113390979A CN113390979A CN202110497003.0A CN202110497003A CN113390979A CN 113390979 A CN113390979 A CN 113390979A CN 202110497003 A CN202110497003 A CN 202110497003A CN 113390979 A CN113390979 A CN 113390979A
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000013049 sediment Substances 0.000 title claims abstract description 36
- 239000002689 soil Substances 0.000 title claims abstract description 36
- 238000000605 extraction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 238000000899 pressurised-fluid extraction Methods 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 238000011088 calibration curve Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000005259 measurement Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 10
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002274 desiccant Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- FDSGHYHRLSWSLQ-UHFFFAOYSA-N dichloromethane;propan-2-one Chemical compound ClCCl.CC(C)=O FDSGHYHRLSWSLQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000012086 standard solution Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000005202 decontamination Methods 0.000 claims 1
- 230000003588 decontaminative effect Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 abstract description 2
- 238000004817 gas chromatography Methods 0.000 abstract description 2
- 238000010813 internal standard method Methods 0.000 abstract description 2
- 238000004949 mass spectrometry Methods 0.000 abstract description 2
- 238000005562 fading Methods 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000003804 effect on potassium Effects 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000409 membrane extraction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- 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
- G01N30/8665—Signal analysis for calibrating the measuring apparatus
-
- 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
Landscapes
- 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)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention relates to a method for measuring aniline in soil and sediment, which comprises the following steps: collecting and storing samples: the soil sample is collected and stored according to the related requirements of HJ/T166, the sediment sample is collected and stored according to the related requirements of GB17378.3, the sample is stored in a clean brown glass bottle with a plug and a ground opening, the sample is transported to a laboratory and then analyzed, the determination of the dry matter content of the soil sample by water is performed according to HJ613, and the determination of the water content of the sediment sample is performed according to GB17378.5, so that the invention has the following beneficial effects: extracting aniline in soil or sediment by adopting a proper extraction method (Soxhlet extraction, pressurized fluid extraction and the like), selecting a proper purification method (gel permeation chromatography or column purification) according to the interference condition of a sample matrix to purify, concentrate and fix the volume of an extracting solution, performing gas chromatography separation and mass spectrometry detection, and quantifying by an internal standard method, wherein the consumption time is short, and the determination is more accurate.
Description
Technical Field
The invention discloses a method for measuring aniline in soil and sediments, belonging to the technical field of aniline measurement.
Background
When aniline in soil and sediment is measured, the content of aniline can be accurately measured by a spectrophotometry, some students also propose that aniline has a certain fading effect on potassium permanganate, and the actual fading degree and the content of aniline are closely related, so that a fading photometry is established for measuring aniline substances, and then, some students manufacture a flow injection analysis device for online aniline enrichment liquid membrane extraction, and realize separation and enrichment of aniline through an extraction unit, so as to measure the intensity of fluorescence generated by aniline in an alkaline solution.
In the prior art, the standard photometric method has a plurality of defects in actual aniline determination, and researches of scholars find that the standard photometric method consumes longer time in the process of determining the aniline, the chromaticity of a water sample to be determined also influences the determination result to a certain extent, and under the condition, the determination accuracy of the standard photometric method is difficult to effectively guarantee.
Disclosure of Invention
The invention aims to provide a method for measuring aniline in soil and sediments, and solves the problems that the time consumed in the process of measuring aniline by using the current standard photometric method is long, the chromaticity of a measured water sample can also influence the measurement result to a certain extent, and the measurement accuracy of the standard photometric method is difficult to effectively guarantee.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention relates to a method for measuring aniline in soil and sediment, which comprises the following steps:
(1) collecting and storing samples: the soil sample is collected and stored according to the related requirements of HJ/T166, the sediment sample is collected and stored according to the related requirements of GB17378.3, the sample is stored in a clean brown glass bottle with a plug and a ground opening and is transported to a laboratory for analysis, the determination of the dry matter content of the soil sample by moisture is performed according to HJ613, and the determination of the moisture content of the sediment sample is performed according to GB 17378.5.
(2) Preparation of a sample: putting the sample on an enamel disc or a stainless steel disc, uniformly mixing, removing foreign matters such as branches, leaves, stones and the like, roughly dividing by a quartering method according to HJ/T166, using the sample for screening pollutants as a target sample, treating a fresh sample, naturally drying the sample when the natural drying does not influence the analysis purpose, and drying the fresh soil or sediment sample by adopting a freeze drying and drying agent method.
(3) Extraction: the extraction method can select Soxhlet extraction, pressurized fluid extraction and other equivalent extraction methods, and comprises the following steps: transferring all prepared soil or sediment samples into a Soxhlet extraction sleeve, adding substitute intermediate solution with the concentration above the middle point of a calibration curve, carefully placing the mixture into a reflux pipe of a Soxhlet extractor, adding 100ml of dichloromethane-acetone mixed solvent into a round bottom solvent bottle, extracting for 16-18 h, controlling the reflux speed to be 4-6 times per hour, stopping heating and refluxing, taking out the round bottom solvent bottle, and waiting for concentration.
(4) Nitrogen blowing and concentrating; and (3) under the condition of room temperature, starting nitrogen till the surface of the solvent has airflow fluctuation (avoiding forming air vortex), washing the exposed wall of the concentrator tube in the nitrogen blowing process for multiple times by using dichloromethane, concentrating to about 2ml, and stopping concentrating.
(5) And (3) drawing a calibration curve: taking 5ml volumetric flasks, adding 2ml dichloromethane solvent in advance, respectively measuring a proper amount of aniline standard intermediate solution, substitute intermediate solution 4.15 and internal standard intermediate solution, using dichloromethane solvent to perform constant volume, uniformly mixing to prepare a standard series with at least 5 concentration points, wherein the mass concentrations of aniline and substitute are respectively 1.0 mug/ml, 5.0 mug/ml, 10.0 mug/ml, 20.0 mug/ml and 50.0 mug/ml, the internal standard mass concentration is 40.0 mug/ml, or preparing a calibration series with appropriate concentration levels of other gas chromatography-mass spectrometers according to the instrument sensitivity or the target concentration in a sample, sequentially performing sample injection analysis from low concentration to high concentration, taking the target compound concentration as a horizontal coordinate, and taking the product of the ratio of the quantitative ion response value of the target compound and the internal standard compound mass concentration as a vertical coordinate, and drawing a calibration curve.
(6) Measurement of the sample: the sample to be tested is measured according to the same instrumental analysis conditions as the calibration curve.
(7) Calculating the content (mg/kg) of the target object of the soil sample: calculating according to the formula: ω -P [ P ] P/mwdm.
Preferably, the transportation process in the step (1) is sealed and protected from light, the product is refrigerated at the temperature of below 4 ℃, and the product is refrigerated at the temperature of below 4 ℃, protected from light and sealed for storage for no more than 10 days after being transported to an experimental room and cannot be analyzed in time.
Preferably, in the step (2), if the water content in the soil or sediment sample is high (more than 30%), the water phase is separated by centrifugation, and then the drying treatment is carried out, wherein the method comprises the following steps: weighing 20g (accurate to 0.01g) of fresh sample by adopting a drying agent method, adding a certain amount of drying agent, uniformly mixing, dehydrating, grinding into fine particles, fully and uniformly mixing until the particles are dispersed, and completely transferring into an extraction container for later use.
Preferably, step (4) is concentrated to about 1ml when selected for purification by gel permeation chromatography.
A method for measuring aniline in soil and sediment is provided, and the method comprises the following steps after the step (7) on the basis of any one of the measurement methods:
(8) blank experiment: at least one blank test is carried out on every 20 samples, and the concentration of the target object in the measurement result should not exceed the detection limit of the method.
(9) Checking the performance of the instrument: a mixed solution containing 4, 4' -DDT, pentachlorophenol and benzidine each at a concentration of 50. mu.g/ml was prepared, and the standard solution was used to check the inertness of the injection port of a gas chromatograph, and the degradation rate of DDT to DDE and DDD should not exceed 15%.
(10) Checking a calibration curve: the relative standard deviation of the target compound in the initial calibration curve relative to the response factor should be no greater than 30%, or the correlation coefficient should be no greater than 0.990, the concentration of the midpoint of the calibration curve should be analyzed every 24 hours, the relative deviation of the measurement value from the initial measurement value should be less than 30%, at least 1 parallel sample should be analyzed in each 20 samples, the relative deviation of the measurement result of the parallel sample with the concentration level above the lower limit of quantitation should be less than 40%, at least 1 matrix plus standard sample is made for each batch of samples, and the plus standard concentration is 1-5 times the concentration of the original sample or the midpoint of the curve.
(11) Recovery of the surrogate: the laboratory should establish a control chart of the recovery of the substitute with a mark, count according to the same batch of samples (20 to 30 samples), eliminate outliers, calculate the average recovery rate p and the relative standard deviation s of the substitute, and control the average of the substitute within p +/-3 s.
(12) And (3) treatment of waste: all waste liquid and other waste (including residual liquid after detection) generated in the test are stored in a centralized and sealed way, and are attached with warning signs and entrusted to a qualification unit for centralized disposal.
Optionally, in step (9), if the DDT is attenuated too much or a poor chromatographic peak occurs, the sample inlet needs to be cleaned or replaced, and meanwhile, about 5cm of the front end of the capillary column is cut, and the phenomena that polar compounds such as benzidine and pentachlorophenol are prone to decomposition at the sample inlet, and the peak shape has tailing and splitting, etc. are also processed in the same way.
The invention has the following beneficial effects:
according to the method, aniline in soil or sediment is extracted by adopting a proper extraction method (Soxhlet extraction, pressurized fluid extraction and the like), an appropriate purification method (gel permeation chromatography or column purification) is selected according to the interference condition of a sample matrix to purify, concentrate and fix the volume of an extracting solution, gas chromatography separation and mass spectrometry detection are carried out, and the quantity is determined according to retention time, fragment ion mass-to-charge ratio and abundance thereof, the internal standard method is quantitative, the consumed time is short, and the determination is more accurate.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
The invention relates to a method for measuring aniline in soil and sediment, which comprises the following steps:
(1) collecting and storing samples: the soil sample is collected and stored according to the related requirements of HJ/T166, the sediment sample is collected and stored according to the related requirements of GB17378.3, the sample is stored in a clean brown glass bottle with a plug and a ground opening, the sample is transported to a laboratory and then analyzed, the determination of the dry matter content of the soil sample is performed according to HJ613, the determination of the water content of the sediment sample is performed according to GB17378.5, the sediment sample is sealed, protected from light and refrigerated below 4 ℃ in the transportation process, and the sediment sample is stored in a sealed manner at the temperature below 4 ℃ if the sediment sample cannot be analyzed in time after being transported to the laboratory, and the storage time is not more than 10 days.
(2) Preparation of a sample: putting the sample on an enamel plate or a stainless steel plate, uniformly mixing, removing foreign matters such as branches, rods, leaves, stones and the like, roughly dividing by a quartering method according to HJ/T166, using the sample for screening pollutants as a target, processing a fresh sample, naturally drying the sample when the natural drying does not influence the analysis target, drying the fresh soil or sediment sample by adopting a freeze drying and drying agent method, and if the water content in the soil or sediment sample is higher (more than 30 percent), centrifuging to separate out a water phase, and then drying, wherein the method comprises the following steps: weighing 20g (accurate to 0.01g) of fresh sample by adopting a drying agent method, adding a certain amount of drying agent, uniformly mixing, dehydrating, grinding into fine particles, fully and uniformly mixing until the particles are in a granular shape, and completely transferring the particles into an extraction container for later use.
(3) Extraction: the extraction method can select Soxhlet extraction, pressurized fluid extraction and other equivalent extraction methods, and comprises the following steps: transferring all prepared soil or sediment samples into a Soxhlet extraction sleeve, adding substitute intermediate solution with the concentration above the middle point of a calibration curve, carefully placing the mixture into a reflux pipe of a Soxhlet extractor, adding 100ml of dichloromethane-acetone mixed solvent into a round bottom solvent bottle, extracting for 16-18 h, controlling the reflux speed to be 4-6 times per hour, stopping heating and refluxing, taking out the round bottom solvent bottle, and waiting for concentration.
(4) Nitrogen blowing and concentrating; at room temperature, starting nitrogen gas till the surface of the solvent has gas flow fluctuation (avoiding gas vortex formation), washing the exposed wall of the concentrator tube in the nitrogen blowing process with dichloromethane for multiple times, concentrating to about 2ml, stopping concentrating, and concentrating to about 1ml when purifying by gel permeation chromatography.
(5) And (3) drawing a calibration curve: taking 5ml volumetric flasks, adding 2ml dichloromethane solvent in advance, respectively measuring a proper amount of aniline standard intermediate solution, substitute intermediate solution 4.15 and internal standard intermediate solution, using dichloromethane solvent to perform constant volume, uniformly mixing to prepare a standard series with at least 5 concentration points, wherein the mass concentrations of aniline and substitute are respectively 1.0 mug/ml, 5.0 mug/ml, 10.0 mug/ml, 20.0 mug/ml and 50.0 mug/ml, the internal standard mass concentration is 40.0 mug/ml, or preparing a calibration series with appropriate concentration levels of other gas chromatography-mass spectrometers according to the instrument sensitivity or the target concentration in a sample, sequentially performing sample injection analysis from low concentration to high concentration, taking the target compound concentration as a horizontal coordinate, and taking the product of the ratio of the quantitative ion response value of the target compound and the internal standard compound mass concentration as a vertical coordinate, and drawing a calibration curve.
(6) Measurement of the sample: the sample to be tested is measured according to the same instrumental analysis conditions as the calibration curve.
(7) Calculating the content (mg/kg) of the target object of the soil sample: calculating according to the formula: omega is the content of the target object in the sample, mg/kg; v is the constant volume of the sample, and is ml; m is the weighed amount of the sample, g; the content of target is μ g/ml, and the content of sample is Wdm.
In the course of carrying out the experiment, quality assurance and quality control should be achieved, including:
blank experiment: at least one blank test is carried out on every 20 samples, and the concentration of the target object in the measurement result should not exceed the detection limit of the method;
checking the performance of the instrument: preparing a mixed solution containing 4, 4' -DDT, pentachlorophenol and benzidine with the concentration of 50 mu g/ml, using the standard solution to check the inertia of an injection inlet of a gas chromatograph, wherein the degradation rate from DDT to DDE and DDD is not more than 15%, if too much DDT is attenuated or a poor chromatographic peak is generated, a sample inlet needs to be cleaned or replaced, meanwhile, about 5cm of the front end of a capillary column is cut, polar compounds such as benzidine and pentachlorophenol are easy to decompose at the sample inlet, the phenomenon of tailing and splitting of the peak shape is generated, and the like treatment is also performed.
Checking a calibration curve: the relative standard deviation of the target compound in the initial calibration curve relative to the response factor should be no more than 30%, or the correlation coefficient should be no less than 0.990, the concentration of the middle point of the calibration curve should be analyzed every 24 hours, the relative deviation of the measured value and the initial measured value should be less than 30%, at least 1 parallel sample should be analyzed in each 20 samples, the relative deviation of the measured result of the parallel sample with the concentration level above the lower limit of quantitation should be less than 40%, at least 1 matrix plus standard sample is made for each batch of samples, and the plus standard concentration is 1-5 times of the concentration of the original sample or the middle concentration point of the curve.
Recovery of the surrogate: the laboratory should establish a control chart of the recovery of the substitute with the standard, count according to the same batch of samples (20 to 30 samples), eliminate outliers, calculate the average recovery rate p and the relative standard deviation s of the substitute, and control the average of the substitute within p +/-3 s.
And (3) treatment of waste: all waste liquid and other wastes (including residual liquid after detection) generated in the test are stored in a centralized and sealed way, and are attached with warning signs to entrust a qualified unit to dispose in a centralized way.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method for determining aniline in soils and sediments, comprising the steps of:
(1) collecting and storing samples: the soil sample is collected and stored according to the related requirements of HJ/T166, the sediment sample is collected and stored according to the related requirements of GB17378.3, the sample is stored in a clean brown glass bottle with a plug and a ground opening, the sample is transported to a laboratory and then analyzed, the determination of the dry matter content of the soil sample by water is performed according to HJ613, and the determination of the water content of the sediment sample is performed according to GB 17378.5.
(2) Preparation of a sample: putting the sample on an enamel disc or a stainless steel disc, uniformly mixing, removing foreign matters such as branches, leaves, stones and the like, roughly dividing by a quartering method according to HJ/T166, using the sample for screening pollutants as a target sample, treating a fresh sample, naturally drying the sample when the natural drying does not influence the analysis purpose, and drying the fresh soil or sediment sample by adopting a freeze drying and drying agent method.
(3) Extraction: the extraction method can select Soxhlet extraction, pressurized fluid extraction and other equivalent extraction methods, and comprises the following steps: transferring all prepared soil or sediment samples into a Soxhlet extraction sleeve, adding substitute intermediate solution with the concentration above the middle point of a calibration curve, carefully placing the mixture into a reflux pipe of a Soxhlet extractor, adding 100ml of dichloromethane-acetone mixed solvent into a round bottom solvent bottle, extracting for 16-18 h, controlling the reflux speed to be 4-6 times per hour, stopping heating and refluxing, taking out the round bottom solvent bottle, and waiting for concentration.
(4) Nitrogen blowing and concentrating; and (3) under the condition of room temperature, starting nitrogen till the surface of the solvent has airflow fluctuation (avoiding forming air vortex), washing the exposed wall of the concentrator tube in the nitrogen blowing process for multiple times by using dichloromethane, concentrating to about 2ml, and stopping concentrating.
(5) And (3) drawing a calibration curve: taking 5ml volumetric flasks, adding 2ml dichloromethane solvent in advance, respectively measuring a proper amount of aniline standard intermediate solution, substitute intermediate solution 4.15 and internal standard intermediate solution, using dichloromethane solvent to perform constant volume, uniformly mixing to prepare a standard series with at least 5 concentration points, wherein the mass concentrations of aniline and substitute are respectively 1.0 mug/ml, 5.0 mug/ml, 10.0 mug/ml, 20.0 mug/ml and 50.0 mug/ml, the mass concentration of internal standard is 40.0 mug/ml, or preparing a calibration series with appropriate concentration levels of other gas chromatography-mass spectrometers according to the instrument sensitivity or the target concentration in a sample, sequentially performing sample injection analysis from low concentration to high concentration, taking the target compound concentration as a horizontal coordinate, and taking the product of the ratio of the quantitative ion response value of the target compound and the internal standard compound and the mass concentration of the internal standard compound as a vertical coordinate, and (6) drawing a calibration curve.
(6) Measurement of the sample: the sample to be tested is measured according to the same instrumental analysis conditions as the calibration curve.
(7) Calculating the content (mg/kg) of the target object of the soil sample: calculating according to the formula: ω -P [ P ] P/mwdm.
2. The method for determining aniline in soil and sediment according to claim 1, wherein the transportation process in step (1) is performed in a sealed and light-proof manner, and is refrigerated below 4 ℃, and after the test sample is transported to a laboratory, if the test sample cannot be analyzed in time, the test sample is refrigerated below 4 ℃, and is stored in a light-proof and sealed manner, and the storage time is not more than 10 days.
3. The method for determining aniline in soil and sediment as claimed in claim 1, wherein in step (2), if the water content in the soil or sediment sample is high (more than 30%), the water phase is separated by centrifugation and then dried, and the method comprises the following steps: weighing 20g (accurate to 0.01g) of fresh sample by adopting a drying agent method, adding a certain amount of drying agent, uniformly mixing, dehydrating, grinding into fine particles, fully and uniformly mixing until the particles are dispersed, and completely transferring into an extraction container for later use.
4. The method of claim 1, wherein step (4) is concentrated to about 1ml when gel permeation chromatography is selected for decontamination.
5. A method for determining aniline in soil and sediments, which is characterized by comprising the following steps: the method according to any one of claims 1 to 4, further comprising the following step after step (7):
(8) blank experiment: at least one blank test is carried out on every 20 samples, and the concentration of the target object in the measurement result should not exceed the detection limit of the method.
(9) Checking the performance of the instrument: a mixed solution containing 4, 4' -DDT, pentachlorophenol and benzidine each at a concentration of 50. mu.g/ml was prepared, and the standard solution was used to check the inertness of the injection port of a gas chromatograph, and the degradation rate of DDT to DDE and DDD should not exceed 15%.
(10) Checking a calibration curve: the relative standard deviation of the target compound in the initial calibration curve relative to the response factor should be no greater than 30%, or the correlation coefficient should be no greater than 0.990, the concentration at the midpoint of the calibration curve should be analyzed every 24 hours, the relative deviation between the measurement value and the initial measurement value should be less than 30%, at least 1 replicate should be analyzed per 20 samples, the relative deviation of the measurement result of a replicate with a concentration level above the lower limit of quantitation should be less than 40%, at least 1 matrix plus standard sample per batch of samples should be made, and the plus standard concentration is 1-5 times the concentration of the original sample or the midpoint of the curve.
(11) Recovery of the surrogate: the laboratory should establish a control chart of the recovery of the substitute with the standard, count according to the same batch of samples (20 to 30 samples), eliminate outliers, calculate the average recovery rate p and the relative standard deviation s of the substitute, and control the average of the substitute within p +/-3 s.
(12) And (3) treatment of waste: all waste liquid and other wastes (including residual liquid after detection) generated in the test are stored in a centralized and sealed way, and are attached with warning signs to entrust a qualified unit to dispose in a centralized way.
6. The method for detecting aniline in soil and sediment as claimed in claim 5, wherein in step (9), if too much DDT attenuation or poor chromatographic peak occurs, the sample inlet needs to be cleaned or replaced, and the front end of the capillary column is cut by about 5cm, so that polar compounds such as benzidine and pentachlorophenol are liable to decompose at the sample inlet, and the peak shape shows tailing and splitting, and the like, and the same treatment is carried out.
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| CN114324660A (en) * | 2021-12-29 | 2022-04-12 | 广电计量检测（湖南）有限公司 | Method for detecting methomyl oxime in soil and/or sediment by gas chromatography-mass spectrometry |
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| CN110441436A (en) * | 2019-09-03 | 2019-11-12 | 江苏环科检测有限公司 | The analysis method of aniline in a kind of measurement soil |
| CN111474261A (en) * | 2020-04-24 | 2020-07-31 | 山东省济南生态环境监测中心 | Method for measuring aniline in soil and sediment |
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| CN110441436A (en) * | 2019-09-03 | 2019-11-12 | 江苏环科检测有限公司 | The analysis method of aniline in a kind of measurement soil |
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