CN117686619A - Detection method for volatile organic compounds in soil - Google Patents
Detection method for volatile organic compounds in soil Download PDFInfo
- Publication number
- CN117686619A CN117686619A CN202311791292.0A CN202311791292A CN117686619A CN 117686619 A CN117686619 A CN 117686619A CN 202311791292 A CN202311791292 A CN 202311791292A CN 117686619 A CN117686619 A CN 117686619A
- Authority
- CN
- China
- Prior art keywords
- sample
- target
- volatile organic
- concentration
- retention time
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002689 soil Substances 0.000 title claims abstract description 25
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 23
- 238000001514 detection method Methods 0.000 title abstract description 19
- 230000014759 maintenance of location Effects 0.000 claims abstract description 28
- 150000002500 ions Chemical class 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000011088 calibration curve Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 238000005259 measurement Methods 0.000 claims abstract description 8
- 239000012086 standard solution Substances 0.000 claims abstract description 7
- 238000004451 qualitative analysis Methods 0.000 claims abstract description 4
- 238000004445 quantitative analysis Methods 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims abstract description 4
- 238000010926 purge Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 13
- 238000003795 desorption Methods 0.000 claims description 10
- 238000004364 calculation method Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000012512 characterization method Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000000642 dynamic headspace extraction Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 238000001819 mass spectrum Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000523 sample Substances 0.000 description 81
- 238000005070 sampling Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002279 physical standard Substances 0.000 description 1
- 238000005173 quadrupole mass spectroscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a detection method for volatile organic compounds in soil, which comprises the following steps: s1, collecting a sample; s2, preserving a sample; s3, drawing a calibration curve; respectively transferring quantitative standard use solution and substitute standard solution into blank reagent water by using a microsyringe to prepare standard series with target object concentration and substitute concentration of 5.00, 20.0, 50.0, 100 and 200 mug/L respectively; sequentially measuring from low concentration to high concentration, and recording retention time of standard series target objects and corresponding internal standards and response values of quantitative ions; step S4, sample measurement: if the volatile organic content in the sample is primarily judged to be less than 200 mug/kg, directly measuring by using 5g of sample; when the preliminary judgment concentration is between 200 mug/kg and 1000 mug/kg, directly measuring by using 1g sample; s5, blank test; and S6, qualitative analysis and quantitative analysis. The detection method of the invention has higher accuracy in detecting volatile organic compounds.
Description
Technical Field
The invention relates to the technical field of soil detection methods, in particular to a detection method for volatile organic compounds in soil.
Background
Volatile organic compounds in soil are important indexes for environment detection, and the soil matrix standard substance is used as a physical standard for detection, so that the method has an important effect on ensuring the accuracy and reliability of detection results. Especially, at present, no accurate detection technology is specially aimed at the VOC content in soil, which is mainly due to the lack of the soil matrix standard substances, and the related standard substances have the problems of instability and non-uniformity in view of the complexity of soil components, so that the accuracy and the precision of detection results are poor.
Therefore, the reasonable-design soil matrix standard substance can ensure the stability and accuracy of the detection result of the soil VOC detection technology, and the error control of the detection result is within the precision requirement range, which is the key for ensuring the reliability of the soil VOC detection result.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the problems in the prior art, the invention provides a detection method for volatile organic compounds in soil, which has higher accuracy in detecting semi-volatile organic compounds.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the method for detecting the volatile organic compounds in the soil comprises the following steps:
s1, collecting a sample;
s2, preserving a sample;
s3, drawing a calibration curve;
respectively transferring quantitative standard use solution and substitute standard solution into blank reagent water by using a microsyringe to prepare standard series with target object concentration and substitute concentration of 5.00, 20.0, 50.0, 100 and 200 mug/L respectively; sequentially measuring from low concentration to high concentration, and recording retention time of standard series target objects and corresponding internal standards and response values of quantitative ions;
step S4, sample measurement: if the volatile organic content in the sample is primarily judged to be less than 200 mug/kg, directly measuring by using 5g of sample; when the preliminary judgment concentration is between 200 mug/kg and 1000 mug/kg, directly measuring by using 1g sample;
s5, blank test;
and S6, qualitative analysis and quantitative analysis.
The technical scheme is further improved as follows:
further, in the step S3, a linear calibration curve is drawn by using a least square method, and the response value of the lowest point of the calibration curve is brought into curve calculation, and the calculation result of the target object is between 70% and 130% of the actual value.
Further, in the step S4, the purge-and-trap device references the condition: purge flow rate: 40ml/min; purge temperature: 40 ℃; preheating time: 2min; purge time: 11min; dry blowing time: 2min; pre-desorption temperature: 245 ℃; desorption temperature: 250 ℃; desorption time: 2min; baking temperature: 280 ℃; baking time: 5min; transmission line temperature: 250 ℃;
gas chromatography reference conditions: sample inlet temperature: 200 ℃; carrier gas: helium gas; split ratio: 26:1, a step of; column flow (constant flow mode): 1.0ml/min; heating program: 38 ℃ (2.0 min) →10 ℃/min→120 ℃ →15 ℃/min→240 ℃ (0.5 min);
mass spectrometry reference conditions: scanning mode: full scanning; scanning range: 35-270 amu; ionization energy: 70eV; electron multiplier voltage: consistent with the tuning voltage; interface temperature: 280 ℃.
Further, in the step S6, the target object is characterized by the relative retention time and the mass spectrum comparison with the standard substance;
when using relative retention time characterization, the difference between the relative retention time of the target in the sample and the relative retention time of the target in the calibration curve should be within 0.06, the relative retention time of the target being calculated according to the following equation:
wherein: RRT is the relative retention time of the target; RTx is the retention time of the target; RTIS is the retention time of the internal standard corresponding to the target.
Further, in the step S6, for the low-content sample, the content of the target in the sample is calculated according to formula (1):
ω＝ρ ex ×10×100/m/(100-w) (1)
wherein: omega is the content of the target in the sample; 10 is the sample volume; ρ ex The mass concentration of the target in the sample; w is the water content of the sample; m is the sample size;
for high content samples, the content of the target in the sample is calculated according to formula (2):
ω＝ρ ex ×V c ×10×K×100/m/(100-w)/V s (2)
wherein: omega is the content of the target in the sample; 10 is the sample volume; ρ ex The mass concentration of the target in the sample; v (V) c Is the volume of the extracting solution; m is the sample size; v (V) s Is the volume of extract used for purging; w is the water content of the sample; k is dilution multiple of the extract.
Compared with the prior art, the detection method for the volatile organic compounds in the soil has the following advantages:
the invention is used for detecting volatile organic compounds in soil, the volatile organic compounds in a sample are purged and enriched in a trapping tube by high-purity helium (or nitrogen), the trapping tube is heated and back-blown by the high-purity helium, and the components subjected to thermal desorption enter a gas chromatograph and are separated, and then are detected by a mass spectrometer. And the quality is improved by comparing the standard mass spectrogram of the target object to be detected with the standard mass spectrogram of the target object to be detected and the retention time, and the internal standard method is used for quantification, so that the detection precision is high.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Examples
The invention relates to a detection method for volatile organic compounds in soil, which comprises the following steps:
step S1, collecting a sample
Sample collection was divided into the following 3 cases:
(1) Soil and sediment samples can be collected on a sampling site by using a portable instrument for measuring volatile organic compounds to perform primary screening on the samples for the content of target substances. All samples should be taken in at least 3 parallel samples and another sample is taken in a 60ml sample bottle (or a sample bottle of other specifications greater than 60 ml) for determining volatile organic compounds and sample water content in the high-content samples.
(2) Sampling method of manual sample feeding mode
The sampling method is suitable for a purging and trapping device without an automatic sampler. Samples were collected into 60ml sample bottles (or sample bottles of other specifications greater than 60 ml) as soon as possible with a spatula or spatula and filled as much as possible. And (3) rapidly removing the threads of the sample bottle and the samples adhered to the outer surface of the sample bottle, and sealing the sample bottle.
(3) Sampling method of automatic sampling mode
If a purge-and-trap device with an autosampler is provided, a clean magnetic stirrer bar is placed in each 40ml brown sample bottle, sealed, labeled and weighed (to the nearest 0.01 g), the weight recorded and noted on the label prior to sampling. When sampling, a proper amount of sample is collected into the sample bottle by the sampler, the screw thread of the sample bottle and the sample adhered on the outer surface of the sample bottle are rapidly removed, and the sample bottle is sealed.
Wherein, if a disposable plastic syringe is used to collect the sample, the diameter of the syringe portion should be such that it can extend into the neck of a 40ml sample bottle. The injector portion at the end of the syringe should be shut off prior to sampling. One syringe can only be used to collect one sample. If a special stainless steel sampler is used, the sampler needs to be provided with a booster, so that soil can be pushed into the sample bottle.
If the content of the target substances in the sample is primarily judged to be less than 200 mug/kg, about 5g of sample is collected; if the content of the target in the sample is larger than or equal to 200 mug/kg, about 1g of the sample and about 5g of the sample are respectively collected.
Step S2, preserving the sample
The sample should be refrigerated and transported after collection, the sample storage area should not be interfered by organic matters, and the storage time is 7d below 4 ℃.
Step S3, drawing a calibration curve
(1) Instrument performance inspection
The 1-2 mu LBFB solution is removed by a micro-injector and directly injected into a gas chromatograph for analysis or added into 10ml blank reagent water and injected into the gas chromatograph for analysis by a purging and trapping device. The BFB key ion abundance obtained with the quadrupole mass spectrometry should meet the criteria specified in table 1, otherwise parameters of the mass spectrometer should be adjusted or the source of cleaning ions considered. If the instrument software can not automatically judge whether the abundance of the BFB key ions meets the standard of the table 1, the abundance of the key ions can be obtained by subtracting the background value from the average value of the abundance of the ions at the scanning point at the peak top and the front and rear scanning points of the scanning point, and the abundance of the key ions meets the standard of the table 1. The background value can be chosen to be any point in the 20 scan points before the BFB peaks, which should be column loss or instrument background ion generation.
TABLE 1 Critical ion abundance
| Quality of | Ion abundance criterion | Quality of | Ion abundance criterion |
| 50 | 95% to 40% of the weight | 174 | Greater than 50% of the mass 95 |
| 75 | 30 to 80 percent of the mass of 95 | 175 | 5 to 9 percent of mass 174 |
| 95 | Basal peak, 100% relative abundance | 176 | 93 to 101 percent of mass 174 |
| 96 | 95 to 9 percent of the mass | 177 | 5 to 9 percent of the mass 176 |
| 173 | Less than 2% of the mass 174 | － | － |
(2) Drawing of calibration curves
Quantitative standard use solution and substitute standard solution are respectively removed into blank reagent water by a microsyringe, and standard series with target object concentration and substitute concentration of 5.00, 20.0, 50.0, 100 and 200 mug/L are respectively prepared.
10.00ml of the standard series to 40ml of sample bottles (directly into the purge tube if no autosampler is present) were measured separately using an airtight syringe, and 10.0. Mu.l of the internal standard solution was added separately to give an internal standard concentration of 20.0. Mu.g/L at each point.
And (3) sequentially measuring from low concentration to high concentration, and recording the retention time of the standard series target objects and corresponding internal standards and the response value of quantitative ions (first or second characteristic ions).
If the Relative Standard Deviation (RSD) of a target object Relative Response Factor (RRF) in the standard series is greater than 20%, the target object is calibrated by using a least square calibration curve. And drawing a calibration curve by taking the response value ratio of the target object and the corresponding internal standard as an ordinate and the concentration ratio as an abscissa.
When a linear calibration curve is drawn by adopting a least square method, the response value of the lowest point of the calibration curve is brought into curve calculation, and the calculation result of the target object is 70-130% of the actual value.
Step S4, sample measurement
If the volatile organic content in the sample is primarily judged to be less than 200 mug/kg, directly measuring by using 5g of sample; when the preliminary determination concentration is between 200. Mu.g/kg and 1000. Mu.g/kg, the sample is directly measured by 1 g.
(1) If the purging and trapping device does not have an automatic sampler, the purging pipe is weighed first, a proper amount of sample is added, then the purging pipe is weighed again (accurate to 0.01 g), and the purging pipe is filled into the purging and trapping device. 10.0 μl of the internal standard and the total were added separately using a microinjector
10.0. Mu.l of the substitute was put into a purge tube as a sample in 10.0ml of reagent blank water measured by an airtight syringe, and the measurement was performed.
(2) If the purge-trap device was equipped with an autosampler, the vial was gently shaken to confirm that the sample in the vial was free to move, and the vial weight (to the nearest 0.01 g) was weighed and recorded. Measurement was performed by measuring 10.0ml of blank reagent water with an airtight syringe and 10.0. Mu.l of an internal standard and 10.0. Mu.l of a substitute with a microinjector, respectively, into a sample bottle.
Wherein, purge trap device reference condition: purge flow rate: 40ml/min; purge temperature: 40 ℃; preheating time: 2min; purge time: 11min; dry blowing time: 2min; pre-desorption temperature: 245 ℃; desorption temperature: 250 ℃; desorption time: 2min; baking temperature: 280 ℃; baking time: 5min; transmission line temperature: 250 ℃.
Gas chromatography reference conditions: sample inlet temperature: 200 ℃; carrier gas: helium gas; split ratio: 26:1, a step of; column flow (constant flow mode): 1.0ml/min; heating program: 38 ℃ (2.0 min) →10 ℃/min→120 ℃ →15 ℃/min→240 ℃ (0.5 min).
Mass spectrometry reference conditions: scanning mode: full scanning; scanning range: 35-270 amu; ionization energy: 70eV; electron multiplier voltage: consistent with the tuning voltage; interface temperature: 280 ℃.
Step S5, blank test
10.0. Mu.l of an internal standard solution and 10.0. Mu.l of a substitute standard solution were each measured by a microinjector into 10.0ml of blank reagent water measured by an airtight syringe, and used as blank samples. The blank was then placed in a 40ml sample bottle (directly in a purge tube if no autosampler was present) and the measurement was performed.
Step S6, qualitative analysis and quantitative analysis
(1) The target is characterized in terms of relative retention time (or retention time) and comparison with a standard mass spectrum.
When using relative retention time characterization, the difference between the Relative Retention Time (RRT) of the target in the sample and the Relative Retention Time (RRT) of the target in the calibration curve should be within 0.06. The Relative Retention Time (RRT) of the target is calculated according to the following formula.
Wherein:
rrt—relative retention time of target;
rtx—retention time of target;
rtis—retention time of internal standard corresponding to target.
(2) And calculating according to the response values of the target object and the internal standard first characteristic ions. The second characteristic ion may be used for quantification when the first characteristic ion of the target in the sample is interfering. The peak order of the target, the quantitative internal standard, the first characteristic ion, the second characteristic ion and other measurement parameters are shown in table 1.
TABLE 1 quantitative parameters of targets
For low content samples, the content of the target in the sample (μg/kg) is calculated according to formula (1):
ω＝ρ ex ×10×100/m/(100-w) (1)
wherein:
omega-the content of target in the sample;
10-sample volume;
ρ ex -the mass concentration of the target in the sample;
w-the water content of the sample;
m-sample amount.
For high content samples, the target content in the sample (μg/kg) was calculated according to equation (2).
ω＝ρ ex ×V c ×10×K×100/m/(100-w)/V s (2)
Wherein:
omega-the content of target in the sample;
10-sample volume;
ρ ex -the mass concentration of the target in the sample;
V c -extract volume;
m-sample amount;
V s -volume of extract for purging;
w-the water content of the sample;
k is the dilution factor of the extracting solution.
Wherein, if the water content of the sample is more than 10%, the volume V of the extracting solution c The sum of the volumes of methanol and water in the sample; if the water content of the sample is less than or equal to 10%, the volume V of the extracting solution c 10ml.
Claims (5)
1. The method for detecting the volatile organic compounds in the soil is characterized by comprising the following steps of:
s1, collecting a sample;
s2, preserving a sample;
s3, drawing a calibration curve;
respectively transferring quantitative standard use solution and substitute standard solution into blank reagent water by using a microsyringe to prepare standard series with target object concentration and substitute concentration of 5.00, 20.0, 50.0, 100 and 200 mug/L respectively; sequentially measuring from low concentration to high concentration, and recording retention time of standard series target objects and corresponding internal standards and response values of quantitative ions;
step S4, sample measurement: if the volatile organic content in the sample is primarily judged to be less than 200 mug/kg, directly measuring by using 5g of sample; when the preliminary judgment concentration is between 200 mug/kg and 1000 mug/kg, directly measuring by using 1g sample;
s5, blank test;
and S6, qualitative analysis and quantitative analysis.
2. The method for detecting volatile organic compounds in soil according to claim 1, wherein in the step S3, a linear calibration curve is drawn by a least square method, the response value of the lowest point of the calibration curve is brought into curve calculation, and the calculation result of the target object is between 70% and 130% of the actual value.
3. The method for detecting volatile organic compounds in soil according to claim 1, wherein in the step S4, the purge-and-trap device references the conditions: purge flow rate: 40ml/min; purge temperature: 40 ℃; preheating time: 2min; purge time: 11min; dry blowing time: 2min; pre-desorption temperature: 245 ℃; desorption temperature: 250 ℃; desorption time: 2min; baking temperature: 280 ℃; baking time: 5min; transmission line temperature: 250 ℃;
gas chromatography reference conditions: sample inlet temperature: 200 ℃; carrier gas: helium gas; split ratio: 26:1, a step of; column flow (constant flow mode): 1.0ml/min; heating program: 38 ℃ (2.0 min) →10 ℃/min→120 ℃ →15 ℃/min→240 ℃ (0.5 min);
mass spectrometry reference conditions: scanning mode: full scanning; scanning range: 35-270 amu; ionization energy: 70eV; electron multiplier voltage: consistent with the tuning voltage; interface temperature: 280 ℃.
4. The method for detecting volatile organic compounds in soil according to claim 1, wherein in the step S6, the target is characterized by a relative retention time and a mass spectrum comparison with a standard substance;
when using relative retention time characterization, the difference between the relative retention time of the target in the sample and the relative retention time of the target in the calibration curve should be within 0.06, the relative retention time of the target being calculated according to the following equation:
wherein: RRT is the relative retention time of the target; RTx is the retention time of the target; RTIS is the retention time of the internal standard corresponding to the target.
5. The method for detecting volatile organic compounds in soil according to claim 1, wherein in the step S6, for the low-content sample, the content of the target compound in the sample is calculated according to formula (1):
ω＝ρ ex ×10×100/m/(100-w) (1)
wherein: omega is the content of the target in the sample; 10 is the sample volume; ρ ex The mass concentration of the target in the sample; w is the water content of the sample; m is the sample size;
for high content samples, the content of the target in the sample is calculated according to formula (2):
ω＝ρ ex ×V c ×10×K×100/m/(100-w)/V s (2)
wherein: omega is the content of the target in the sample; 10 is the sample volume; ρ ex The mass concentration of the target in the sample; v (V) c Is the volume of the extracting solution; m is the sample size; v (V) s Is the volume of extract used for purging; w is the water content of the sample; k is dilution multiple of the extract.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311791292.0A CN117686619A (en) | 2023-12-25 | 2023-12-25 | Detection method for volatile organic compounds in soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311791292.0A CN117686619A (en) | 2023-12-25 | 2023-12-25 | Detection method for volatile organic compounds in soil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117686619A true CN117686619A (en) | 2024-03-12 |
Family
ID=90133448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311791292.0A Pending CN117686619A (en) | 2023-12-25 | 2023-12-25 | Detection method for volatile organic compounds in soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117686619A (en) |
-
2023
- 2023-12-25 CN CN202311791292.0A patent/CN117686619A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107884493B (en) | Method for analyzing short-chain chlorinated paraffin in environmental sample by using full-two-dimensional gas chromatography-time-of-flight mass spectrometry | |
| CN112014485A (en) | Method for measuring geosmin and 2-methylisoborneol in sediment | |
| US11828739B2 (en) | Large volume gas chromatography injection port | |
| CN110808203A (en) | Device and method for quickly and accurately detecting impurities in high-purity hydrogen for hydrogen fuel cell | |
| CN112114072A (en) | Detection method for simultaneously analyzing multiple organic gases | |
| CN110082469B (en) | Method for measuring content of trace alcohols and ketones in transformer insulating oil | |
| CN111398487A (en) | Application method of retention index in gas chromatography-tandem mass spectrometry analysis of tobacco flavor components | |
| CN106950303B (en) | Method for measuring benzene series in biological sample blood | |
| CN114487150A (en) | Sweeping and trapping/gas chromatography-mass spectrometry detection method for chloromethane in surface water | |
| CN111707774B (en) | Method for detecting volatile compounds in tobacco | |
| CN113834884A (en) | Ozone layer consumables on-line monitoring system | |
| CN117686619A (en) | Detection method for volatile organic compounds in soil | |
| CN110082468B (en) | Method for measuring trace aldehyde and ketone substance content in transformer insulating oil | |
| CN113341018B (en) | Method for measuring migration quantity of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO | |
| CN106680405B (en) | A kind of gas chromatography mass spectrometry of full-automatic gas pocket type sample introduction thermal desorption | |
| CN111307992B (en) | Pre-column derivative liquid chromatography-mass spectrometry analysis method for quantitatively detecting organic acid in PM2.5 | |
| CN110658265A (en) | Method for simultaneously measuring contents of benzene, toluene, xylene and naphthalene in coal gas | |
| CN113866314B (en) | Method for measuring content of nonafluorobutyl ethyl ether in soil and sediment | |
| CN113820421A (en) | Method for measuring 6 phenolic compounds in water | |
| CN109490455B (en) | Method for detecting formamide release amount and release rate in yoga mat | |
| CN111398486A (en) | Method for rapidly determining acquisition time window in gas chromatography-tandem mass spectrometry dynamic multi-reaction monitoring mode analysis method | |
| CN111024872A (en) | Method for rapidly detecting 3-methylthio propanol in sesame-flavor liquor | |
| CN111060632A (en) | Method for detecting tetraethyl lead in water | |
| CN1900711A (en) | Method and device for detecting micro oxygen containing compound in low boiling point hydrocarbon | |
| CN111579666A (en) | Method for detecting levoglucosan in water sample by using ultra-high performance liquid chromatography-triple quadrupole mass spectrometer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |