CN109668973A - The measuring method of gas station underground water pollutant - Google Patents
The measuring method of gas station underground water pollutant Download PDFInfo
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- CN109668973A CN109668973A CN201710965502.1A CN201710965502A CN109668973A CN 109668973 A CN109668973 A CN 109668973A CN 201710965502 A CN201710965502 A CN 201710965502A CN 109668973 A CN109668973 A CN 109668973A
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
-
- 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
Abstract
The present invention relates to a kind of measuring methods of gas station underground water pollutant, mainly solve the problems, such as that pollutant detection limit is higher in the prior art.The present invention by using a kind of gas station underground water pollutant measuring method, acquire gas station's sampling of ground water, internal standard and substitute solution are added after pretreatment, then by the full-automatic Purge & Trap Concentrator purging of solid-liquid, concentration, into gas-chromatography, enter mass spectrum after chromatographic isolation, by selecting ion scan, obtain quota ion stream peak area, using the ion stream peak area of target compound quota ion ratio corresponding to the peak area of internal standard compound quota ion stream as ordinate, concentration ratio is abscissa, the technical solution for establishing standard curve preferably solves the above problem, it can be used in the measurement of gas station underground water pollutant.
Description
Technical field
The present invention relates to a kind of measuring methods of gas station underground water pollutant.
Background technique
Sunken tankers leakage in gas station's has been the serious problems of environmental pollution prevention and control field face in the world.It is refueling in China
Stand sunken tank system leakage polluted underground water field research it is at the early-stage, the country there is no the pipe of needle gas station underground water pollution
Reason specification and detection technique.Characteristic contamination is mainly derived from methyl tertiary butyl ether(MTBE), benzene series in oil product in gas station's underground water
Object and polycyclic aromatic hydrocarbon.Pollutant monitoring technical research is established, for carrying out investigation work, the palm of gas station's underground water pollution from now on
The Quality situation of gas station's underground water is held, is of great significance to evaluating it to the risk of environmental hazard.It is domestic at present
Outer research mostly uses full scan-mass spectrography, and the detection limit of this method is in (0.2-0.6) μ gL-1Between, it can not measure to lower
The contaminant trace species of concentration are measured.
Currently, the analysis method of methyl tertiary butyl ether(MTBE) has Headspace-Gas Chromatography Analysis, liquid-liquid micro-extraction-GC/FID method in water
[Deng Minjun, Liang Liuling, Yang Anping wait 24 kinds of volatile organic content [J] physics and chemistry inspections in gas chromatography mass spectrometry measurement water
Test-chemistry fascicle, 2012,48 (5): 576-579], solid phase microextraction-GC/MS/SIM method, Puffing and trapping etc., benzene series in water
Object analysis method has gas chromatography, Headspace-Gas Chromatography Analysis, purge and trap-gas chromatography mass spectrometry method and a Solid-phase Microextraction, in water
The common analysis of naphthalene has liquid chromatography and purge and trap-gas chromatography mass spectrometry method.In the above all kinds of methods, purge and trap-
It is gas chromatography mass spectrometry method high sensitivity, qualitative accurate, it is the most advanced effective method of volatile organic matter in present analysis water.
The country rarely has the report for characteristic contamination detection method in gas station's underground water, and inventor was once caught using purging
Collection-gas chromatography mass spectrometry full scan method measure simultaneously methyl tertiary butyl ether(MTBE) in gas station's underground water, benzene, toluene, ethylbenzene, dimethylbenzene and
Naphthalene.There is not yet methyl tertiary butyl ether(MTBE), benzene, first in purge and trap-gas chromatography mass spectrometry-selection ion scan method analysis gas station's underground water
Benzene, ethylbenzene, dimethylbenzene and naphthalene report and patent.
Technical problem to be solved by the present invention lies in establish in a kind of gas station's underground water by selecting ion scan
The measuring method of pollutant load.This method is higher than traditional full scan method sensitivity, anti-interference, is suitable for gas station underground
The monitoring of characteristic contamination in water.
Summary of the invention
The technical problem to be solved by the present invention is to the higher problems of pollutant detection limit in the prior art, provide a kind of new
Gas station underground water pollutant measuring method, have the advantages that pollutant detection limit is lower, high sensitivity.
To solve the above problems, The technical solution adopted by the invention is as follows: a kind of survey of gas station underground water pollutant
Determine method, acquire gas station's sampling of ground water, internal standard and substitute solution are added after pretreatment, then passes through solid-liquid full-automatic blowing
It sweeps trapping concentrating instrument purging, concentration and enters mass spectrum after chromatographic isolation into gas-chromatography, by selecting ion scan, obtain
Quota ion stream peak area, with the peak area of the ion stream peak area of target compound quota ion and internal standard compound quota ion stream
Corresponding ratio is ordinate, and concentration ratio is abscissa, establishes standard curve.
In above-mentioned technical proposal, it is preferable that acquire water sample with sample bottle, make water sample overflow not spacing, the sample after having adopted
Product carry out cryo-conservation.
In above-mentioned technical proposal, it is preferable that take 5-25mL standard sample and water sample to be tested by autosampler.
In above-mentioned technical proposal, it is preferable that when sample concentration exceeds the standard curve range of linearity, be diluted to water sample
After redeterminate.
In above-mentioned technical proposal, it is preferable that internal standard compound is fluorobenzene, 1,2- dichloro-benzenes-d4.
In above-mentioned technical proposal, it is preferable that substitute solution is 4- bromofluoro benzene.
In above-mentioned technical proposal, it is preferable that the full-automatic Purge & Trap Concentrator condition of solid-liquid are as follows: purging pipe volume (5-25)
mL；Purge temperature: room temperature；Purge flow velocity: (20-60) ml/min；Purge time: (6-15) min；Dry purge time: (0.5-3)
min；Purge flow velocity: (100-300) mL/min；Pre- desorption temperature: 150-200 DEG C；Desorption temperature: 160-210 DEG C；When desorption
Between: (1-3) min；Baking temperature: (150-230) DEG C；Baking time: (4-8) min；Transmission line temperature: (120-180) DEG C.
In above-mentioned technical proposal, it is preferable that GC conditions: (5%)-diphenyl (95%)-dimethyl polysiloxane
Capillary chromatographic column or other equivalent chromatographic columns；Injector temperature (180-210) DEG C；Detector (220-250) DEG C, carrier gas are
High-purity helium；Split ratio 30:1-60:1；Column and programmed temperature: initial column temperature (40-60) DEG C keeps (3-5) min, with (5-10)
℃·min-1Rate rise to (140-180) DEG C.
In above-mentioned technical proposal, it is preferable that Mass Spectrometry Conditions: the source EI, electron energy 70eV, ion source temperature (210-230)
℃；Quadrupole rod (140-160) DEG C；Transmission line temperature: (260-280) DEG C；Acquisition mode: selection ion scan mode；Selection is special
Sign ion grouping setting: according to compound appearance time, the maximum ion of compound ions abundance is grouped, every group selection
3-4 ion, while resolution ratio and residence time are carried out, every group of 2-4 characteristic ion, residence time (60-120) ms, point
Resolution is set as high or low by the degree of closeness of ion mass-to-charge ratio.
For the present invention compared with traditional full scan mode, detection limit (3S/N) is 0.02 μ gL-1~0.06 μ gL-1, spirit
Sensitivity is higher, and strong interference immunity, is suitable for the detection of underground underwater trace gasoline, contaminated by diesel oil object, achieves preferable skill
Art effect.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
The measurement of characteristic contamination in certain gas station's underground water.
1 instrument and accessory
(1) Agilent 7890A/5975C type gas chromatograph-mass spectrometer (source EI)；Tekmar ATOMX solid-liquid automatically purges
Trap concentrating instrument.
(2) chromatographic column: HP-5MS type capillary chromatographic column (30m × 0.25mm × 0.25 μm).
(3) 40mL sample bottle, band teflon seal silicone rubber pad.
2 materials and reagent
(1) high-purity helium: purity >=99.9995%.
(2) methyl tertiary butyl ether(MTBE), benzene, toluene, paraxylene, meta-xylene, ortho-xylene, ethylbenzene, naphthalene are chromatography
It is pure；Methanol, liquid chromatogram is pure, noiseless by examining；Naphthalene/methanol standard solution is 20.1mg/L chromatography standard solution；Test
It is commercially available pure water with water, it is noiseless by blank check.Hydrochloric acid, excellent pure grade.
(3) internal standard: fluorobenzene, 1,2- dichloro-benzenes-d4；Substitute: 4- bromofluoro benzene (BFB), 2.0mg mL-1 use first before use
Alcohol is diluted to 25 μ gmL-1。
3 sampling operations
Water sample is acquired with 40mL sample bottle, makes water sample overflow not spacing, and be fixed to pH < 2 with hydrochloric acid.Sample after having adopted
Product put people immediately to be had in the incubator of ice cube, is transported back to be immediately placed in refrigerator behind laboratory and is saved at a temperature of 4 DEG C, is surveyed as early as possible
It is fixed.
4 sample treatments
Autosampler takes 5mL standard sample and water sample, and 25 μ gmL are added-12.0 μ L of internal standard and substitute solution.
If sample concentration exceeds the standard curve range of linearity, then redeterminated after diluting.
5 experimental procedures
(1) experiment condition:
A. the full-automatic Purge & Trap Concentrator condition of solid-liquid: purging pipe volume 5mL；Purge temperature: room temperature；Purge flow velocity:
40ml/min；Purge time: 11min；Dry purge time: 1min；Purge flow velocity: 200mL/min；Pre- desorption temperature: 180 DEG C；
Desorption temperature: 190 DEG C；Desorption time: 2min；Baking temperature: 200 DEG C；Baking time: 6min；Transmission line temperature: 150 DEG C.
B. GC conditions: HP-5MS type capillary chromatographic column (30m × 0.25mm × 0.25 μm)；Injector temperature
210℃；250 DEG C of detector, carrier gas is high-purity helium；Split ratio 30:1；Column and programmed temperature:, keeping 5min by 50 DEG C of initial column temperature,
With 5 DEG C of min-1Rate rise to 140 DEG C.
C. Mass Spectrometry Conditions: the source EI, electron energy 70eV, 230 DEG C of ion source temperature；Quadrupole rod 150C；Transmission line temperature:
280℃；Acquisition mode: selection ion scan；Scanning ion and grouping are shown in Table 1.
Table 1 selects ion scan acquisition parameter
With this condition, in addition to paraxylene, meta-xylene, other are separated completely each target compound, response and peak
Shape reaches best.
(2) standard solution is prepared:
Take 10.0 μ L MTBE, benzene, toluene, paraxylene, meta-xylene, ortho-xylene, ethylbenzene respectively with micro syringe
It is added in 10mL volumetric flask, is configured to Standard Reserving Solution with methanol constant volume, takes 250 μ L standard reserving solutions, extremely with methanol dilution
10mL obtains MTBE18.5mgL-1, benzene 22.0mgL-1, toluene 21.7mgL-1, ethylbenzene 21.7mgL-1To meta-xylene
43.1mg·L-1, ortho-xylene 22.0mgL-1Mixed standard solution.Naphthalene/methanol standard solution is 20.1mg/L colour code.Point
10 μ L, 40 μ L, 100 μ L, 200 μ L and 400 μ L mixed standard solutions and naphthalene standard solution are not taken, after being settled to 250mL with water
To standard liquid series with the ion stream peak area of standard series target compound quota ion and internal standard compound quota ion stream
The corresponding ratio of peak area is ordinate, and concentration ratio is that abscissa establishes standard curve.
Monitor the selection of ion: by taking benzene as an example, the main fragment ion of benzene is 77 and 78, the ion that wherein mass-to-charge ratio is 78
Fragment abundance is maximum, therefore the mass-to-charge ratio of choice ion pattern monitoring ion is set as 78 and 78.When according to compound appearance
Between, the maximum ion of compound ions abundance is grouped, 2-4 ion of every group selection, while to resolution ratio and it is resident when
Between optimize setting.Due to there is 4 ions in group 2, and 77 and 78 is close, therefore high-resolution is set as in acquisition mode,
Residence time is accordingly shortened.After packet-optimized, the ion stream response of each target compound reaches best.
2 equation of linear regression of table, related coefficient, detection limit, quota ion
(3) analytic process
Sample is derived from certain gas station tank field inspection well, is measured by test method to water sample.In traditional full scan mould
Under formula, chaff interferent is more, near the MTBE mass spectra peak of especially 3.7min.And in the case where selecting ion scan mode, it is entire to analyze
Substantially noiseless peak in the process.When test result shows that select ion scan mode to not only eliminate retains with target compound
Between close other organic matters influence, while decreasing the interference of chromatographic column bleed, the sample more complex for ingredient
Available optimal analysis result.
The measurement result of MTBE and benzene is respectively 4.41 and 4.94 μ gL in the sample-1, toluene, ethylbenzene, diformazan is not detected
Benzene and naphthalene.
(4) method precision and mark-on reclaims test
Appropriate standard solution is taken to be added to progress mark-on reclaims test (n=6) in blank water, recovery of standard addition exists
Between 94.6%-103%, relative standard deviation is between 2.4%-4.7%.
Claims (9)
1. a kind of measuring method of gas station underground water pollutant acquires gas station's sampling of ground water, after pretreatment in addition
Mark and substitute solution, then by the full-automatic Purge & Trap Concentrator purging of solid-liquid, concentration, into gas-chromatography, through chromatography
Enter mass spectrum after separation, by selecting ion scan, obtain quota ion stream peak area, with target compound quota ion from
Subflow peak area ratio corresponding to the peak area of internal standard compound quota ion stream is ordinate, and concentration ratio is abscissa, establishes standard
Curve.
2. the measuring method of gas station underground water pollutant according to claim 1, it is characterised in that acquired with sample bottle
Water sample makes water sample overflow not spacing, and the sample after having adopted carries out cryo-conservation.
3. the measuring method of gas station underground water pollutant according to claim 1, it is characterised in that pass through automatic sampling
Device takes 5-25mL standard sample and water sample to be tested.
4. the measuring method of gas station underground water pollutant according to claim 1, it is characterised in that when sample concentration is super
Out when the standard curve range of linearity, redeterminated after being diluted to water sample.
5. the measuring method of gas station underground water pollutant according to claim 1, it is characterised in that internal standard compound be fluorobenzene,
1,2- dichloro-benzenes-d4.
6. the measuring method of gas station underground water pollutant according to claim 1, it is characterised in that substitute solution 4-
Bromofluoro benzene.
7. the measuring method of gas station underground water pollutant according to claim 1, it is characterised in that solid-liquid full-automatic blowing
Sweep trapping concentrating instrument condition are as follows: purging pipe volume 5-25mL；Purge temperature: room temperature；Purge flow velocity: 20-60ml/min；When purging
Between: 6-15min；Dry purge time: 0.5-3min；Purge flow velocity: 100-300mL/min；Pre- desorption temperature: 150-200 DEG C；It is de-
Enclosure temperature: 160-210 DEG C；Desorption time: 1-3min；Baking temperature: 150-230 DEG C；Baking time: 4-8min；Transmission line temperature
Degree: 120-180 DEG C.
8. the measuring method of gas station underground water pollutant according to claim 1, it is characterised in that GC conditions:
Diphenyl-dimethyl polysiloxane capillary chromatographic column, 180-210 DEG C of injector temperature；220-250 DEG C of detector, carrier gas is
High-purity helium；Split ratio 30:1-60:1；Temperature programming: 40-60 DEG C of initial column temperature, 3-5min is kept, with 5-10 DEG C of min-1's
Rate rises to 140-180 DEG C.
9. the measuring method of gas station underground water pollutant according to claim 1, it is characterised in that Mass Spectrometry Conditions: EI
Source, electron energy 70eV, 210-230 DEG C of ion source temperature；140-160 DEG C of quadrupole rod；Transmission line temperature: 260-280 DEG C；Acquisition
Mode: selection ion scan mode；Select characteristic ion grouping setting: rich to compound ions according to compound appearance time
It spends maximum ion to be grouped, 3-4 ion of every group selection, while resolution ratio and residence time is carried out, every group 2-4 special
Ion, residence time 60-120ms are levied, resolution ratio is set as high or low by the degree of closeness of ion mass-to-charge ratio.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110221013A (en) * | 2019-07-04 | 2019-09-10 | 河北省地质环境监测院 | Simple, Practical Determination Method of VOCs in underground water |
| CN112114049A (en) * | 2019-06-19 | 2020-12-22 | 天津科技大学 | Quantitative detection method for main aroma component 2-acetyl-1-pyrroline in fragrant rice |
| CN114354786A (en) * | 2021-12-25 | 2022-04-15 | 生态环境部南京环境科学研究所 | Method for analyzing benzene series spatial distribution of underground water in polluted site based on pollution plume |
| CN115343403A (en) * | 2022-08-16 | 2022-11-15 | 生态环境部南京环境科学研究所 | Detection device for benzene series in underground water of typical pesticide pollution site |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112114049A (en) * | 2019-06-19 | 2020-12-22 | 天津科技大学 | Quantitative detection method for main aroma component 2-acetyl-1-pyrroline in fragrant rice |
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| CN114354786A (en) * | 2021-12-25 | 2022-04-15 | 生态环境部南京环境科学研究所 | Method for analyzing benzene series spatial distribution of underground water in polluted site based on pollution plume |
| CN115343403A (en) * | 2022-08-16 | 2022-11-15 | 生态环境部南京环境科学研究所 | Detection device for benzene series in underground water of typical pesticide pollution site |
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