CN109507341A - Half volatile organic mixture scene fast gas chromatograph analysis method in water - Google Patents
Half volatile organic mixture scene fast gas chromatograph analysis method in water Download PDFInfo
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- 238000004458 analytical method Methods 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000012360 testing method Methods 0.000 claims abstract description 64
- 238000001514 detection method Methods 0.000 claims abstract description 43
- 238000000605 extraction Methods 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 41
- 238000004817 gas chromatography Methods 0.000 claims description 25
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 21
- 239000001307 helium Substances 0.000 claims description 15
- 229910052734 helium Inorganic materials 0.000 claims description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 15
- 239000012159 carrier gas Substances 0.000 claims description 14
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 13
- 230000004888 barrier function Effects 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 8
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 7
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical class ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims description 7
- 150000008422 chlorobenzenes Chemical class 0.000 claims description 7
- 238000002470 solid-phase micro-extraction Methods 0.000 claims description 7
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 6
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 6
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 claims description 5
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 claims description 5
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910021642 ultra pure water Chemical group 0.000 claims description 3
- 239000012498 ultrapure water Chemical group 0.000 claims description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 18
- 239000005416 organic matter Substances 0.000 abstract description 13
- 239000000523 sample Substances 0.000 description 34
- 239000000463 material Substances 0.000 description 17
- 230000001473 noxious effect Effects 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000010586 diagram Methods 0.000 description 13
- 239000012086 standard solution Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 4
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000003440 toxic substance Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000000015 trinitrotoluene Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- LXBRSBBYZXLAHW-UHFFFAOYSA-N N=O.C1=CC=CC=C1.Cl Chemical compound N=O.C1=CC=CC=C1.Cl LXBRSBBYZXLAHW-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- -1 Radical siloxane Chemical class 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 208000037805 labour Diseases 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- OSDZHDOKXGSWOD-UHFFFAOYSA-N nitroxyl;hydrochloride Chemical compound Cl.O=N OSDZHDOKXGSWOD-UHFFFAOYSA-N 0.000 description 1
- HVZWVEKIQMJYIK-UHFFFAOYSA-N nitryl chloride Chemical group [O-][N+](Cl)=O HVZWVEKIQMJYIK-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002351 wastewater 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
-
- 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
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Organic contamination in water
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas 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
- G01N2030/062—Preparation extracting sample from raw material
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses half volatile organic mixture scene fast gas chromatograph analysis methods in water, belong to organic matter detection technique field.The analysis method the following steps are included: setting extraction module extraction parameters be 30-50 DEG C of extraction temperature, extraction time 10-15min；Parsing module analytic parameter is 200-250 DEG C of resolution temperature, parses time 5-20s；Column oven temperature programming parameter are as follows: 40 DEG C of initial temperature, keep 2min；160 DEG C are risen to the heating rate of 20 DEG C/min, keeps 0-10min；220 DEG C are risen to the heating rate of 10 DEG C/min, keeps 12-20min；After parameter setting, the sample to be tested of the organic mixture containing half volatile is added in the acquisition cup of Xiang Shangshu analysis instrument；Instrument " beginning " key is clicked, starts to test.The problem of it is complicated that the analysis method overcomes existing test operation, cannot achieve field quick detection has the characteristics that method simplicity, fast and accurately.
Description
Technical field
The invention belongs to half volatile organic mixture scene in organic matter detection technique field more particularly to a kind of water is fast
Fast gas chromatography analysis method.
Background technique
Semi-volatile organic matter is the major class organic matter slower compared with volatile organic matter volatility, they are easier in soil
Transport And Transformation in the media such as earth, air, biology, is detrimental to health by biological concentration；The general character of this type organic is rouge
Dissolubility is soluble in organic solvent, but also polarized is stronger is slightly soluble in water (such as aniline, esters, aldoketones).Due to half volatilization
The molecular weight of property organic matter is big, boiling point is high, therefore the time more difficult to degrade compared with volatile organic matter, existing can be more in the environment
It is long.It sees in the narrow sense, this type organic is thousands of, and environmental hazard is also to be not quite similar because of its physical and chemical, toxicity difference.People
Those are more concerned about with physiological-toxicity, carcinogenicity, half volatilization for causing gene mutagenicity, teratogenesis, persistence and category environmental hormone
Property organic matter.
1,2,3 ,-trichloro-benzenes, 1,2,4- trichloro-benzenes, 1,3,5- trichloro-benzenes, nitrobenzene, m-chloronitrobenzene, paranitrochlorobenzene,
O-nitrochlorobenzene, 1,2,3,4- tetrachlorobenzene, 1,4- dinitrobenzene, 1,3- dinitrobenzene, 1,2- dinitrobenzene, 2,4- dinitro-chlorine
The semi-volatile organic matters such as benzene, 2,4,6-trinitrotoluene are to common are noxious material in water body, the water being induced by it in recent years
Body pollution happens occasionally, China " water environment quality standard)) (GB 3838-2002), " groundwater quality standard "
(GBIT 14,848 1 93), " standards for drinking water quality " (GB 5749-2006), " composite wastewater discharge standard " (GB
8978-1996) etc. the standard in relation to water quality defines the standard limited value of part semi-volatile organic matter.Wherein, " earth's surface water ring
Border quality standard " and " standards for drinking water quality " cover the tens of kinds of half volatiles such as nitrobenzene, chlorobenzene class, nitro-chlorobenzene
Organic matter.
Currently, since workplace may be simultaneously present multiple pollutant, when carrying out sample detection, it usually needs use
Different sample pre-treatments modes handles above-mentioned 13 kinds of noxious materials, is then detected, and therefore, it is necessary to multiple repairing welds, respectively
Detection.It not only makes troubles in this way to spot sampling work, but also there are repeated labors, detect poor in timeliness, are not able to satisfy
The needs of field quick detection.
Summary of the invention
Place in view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to propose a kind of method letter
Just, fast and accurately half volatile organic mixture scene fast gas chromatograph analysis method in water.
To solve the technical problem, the technical solution adopted by the present invention are as follows:
Half volatile organic mixture scene fast gas chromatograph analysis method in water, comprising the following steps:
The analysis instrument test parameter that solid phase microextraction is coupled with gas-chromatography, the analysis instrument test parameter packet are set
Include extraction module extraction parameters, parsing module analytic parameter and gas-chromatography test parameter, the extraction module extraction parameters
Including 30-50 DEG C of extraction temperature, extraction time 10-15min；The parsing module analytic parameter includes resolution temperature 200-250
DEG C, parse time 5-20s；The gas-chromatography test parameter includes column oven temperature programming parameter, the column oven program liter
Warm parameter are as follows: 40 DEG C of initial temperature, keep 2min；160 DEG C are risen to the heating rate of 20 DEG C/min, keeps 0-10min；With 10
DEG C/heating rate of min rises to 220 DEG C, keep 12-20min；
Be added after parameter setting, in the acquisition cup of Xiang Shangshu analysis instrument the organic mixture containing half volatile to test sample
Product；
Instrument " beginning " key is clicked, starts to test.
Preferably, the gas-chromatography test parameter further include:
Carrier gas: helium, carrier gas flux 2-5mL/min；
Make-up gas: helium, make-up gas flow 40-80mL/min；
Split ratio: (2-10): 1.
Preferably, the gas-chromatography uses dielectric barrier discharge detector, the gas-chromatography test parameter further include:
Detecting temperature is 300 DEG C, and discharge gas is helium, discharge gas flow 25-50mL/min.
Preferably, the extraction temperature is 45 DEG C；
The extraction time is 15min；
The resolution temperature is 250 DEG C；
The column oven temperature programming parameter are as follows: 40 DEG C of initial temperature, keep 2min；With the heating rate liter of 20 DEG C/min
To 160 DEG C, 0min is kept；220 DEG C are risen to the heating rate of 10 DEG C/min, keeps 12min；
The carrier gas flux is 2.5mL/min；
The make-up gas flow is 60mL/min；
The discharge gas flow is 30mL/min；
The split ratio is 3:1.
Preferably, the half volatile organic mixture include in nitrobenzene, chlorobenzene class or nitro-chlorobenzene class at least
It is a kind of.
Preferably, the nitrobenzene includes Isosorbide-5-Nitrae-dinitrobenzene, 1,3- dinitrobenzene, 1,2- dinitrobenzene and 2,4,6-
At least one of trinitrotoluene, the chlorobenzene class include 1,2,3 ,-trichloro-benzenes, 1,2,4- trichloro-benzenes, 1,3,5- trichloro-benzenes
And 1, at least one of 2,3,4- tetrachlorobenzenes, the nitro-chlorobenzene class includes m-chloronitrobenzene, paranitrochlorobenzene, adjacent nitro chlorine
At least one of benzene and 1-CHLORO-2,4-DINITROBENZENE.
Preferably, half volatile organic mixture scene fast gas chromatograph analysis method further includes following step in the water
It is rapid:
With diluted high standard sample, standard serial solution is obtained；
The analysis instrument test parameter is set, above-mentioned standard series of samples is analyzed, standard curve is obtained.
Preferably, the dilution is secondary distilled water or ultrapure water without above-mentioned half volatile organic mixture.
Preferably, it if the concentration of the target components is more than 0.5mg/L, is examined again after using the diluted
It surveys.
Compared with prior art, the beneficial effects of the present invention are:
1, half volatile organic mixture scene fast gas chromatograph analysis method can be simultaneously in water provided by the invention
Up to 13 kinds of semi-volatile organic matter mixtures are analyzed, and on-site test is quick, result is accurate, timeliness is high；
2, half volatile organic mixture scene fast gas chromatograph analysis method in water provided by the invention, sample is in color
Compose column in can once completely, quick separating, take around 25min, each group swarming can be kept completely separate, detection limit can reach
0.5μg/L。
Detailed description of the invention
Fig. 1 is 1,3,5- trichloro-benzenes standard curve schematic diagram provided by the embodiment of the present invention；
Fig. 2 is nitrobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Fig. 3 is 1,2,4- trichloro-benzenes standard curve schematic diagram provided by the embodiment of the present invention；
Fig. 4 is 1,2,3- trichloro-benzenes standard curve schematic diagram provided by the embodiment of the present invention；
Fig. 5 is m-chloronitrobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Fig. 6 is paranitrochlorobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Fig. 7 is o-nitrochlorobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Fig. 8 is 1,2,3,4- tetrachlorobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Fig. 9 is 1,4- dinitrobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Figure 10 is 1,3- dinitrobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Figure 11 is 1,2- dinitrobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Figure 12 is 2,4- dinitrobenzene standard curve schematic diagram provided by the embodiment of the present invention；
Figure 13 is 2,4,6- trinitrobenzen standard curve schematic diagram provided by the embodiment of the present invention；
Figure 14 is blank sample spectrogram provided by the embodiment of the present invention；
Figure 15 is sample to be tested spectrogram provided by the embodiment of the present invention；
Figure 16 is that sample to be tested provided by the embodiment of the present invention repeats detection spectrogram.
Specific embodiment
Below the technical solution in the specific embodiment of the invention will in detail, completely describe.Obviously, described
Embodiment is only the part specific embodiment of the total technical solution of the present invention, and not all embodiment.Based on this hair
Bright total design, those of ordinary skill in the art's every other embodiment obtained, all falls within the scope of protection of the invention.
The present invention provides a kind of half volatile organic mixture scene fast gas chromatograph analysis methods in water, including with
Lower step:
S1: the analysis instrument test parameter that setting solid phase microextraction is coupled with gas-chromatography, the analysis instrument test ginseng
Number includes extraction module extraction parameters, parsing module analytic parameter and gas-chromatography test parameter, the extraction module extraction
Parameter includes 30-50 DEG C of extraction temperature, extraction time 10-15min；The parsing module analytic parameter includes resolution temperature 200-
250 DEG C, parse time 5-20s；The gas-chromatography test parameter includes column oven temperature programming parameter, the column oven program
Heat up parameter are as follows: 40 DEG C of initial temperature, keeps 2min；160 DEG C are risen to the heating rate of 20 DEG C/min, keeps 0-10min；With
The heating rate of 10 DEG C/min rises to 220 DEG C, keeps 12-20min；
S2: after parameter setting, the to be measured of the organic mixture containing half volatile is added in the acquisition cup of Xiang Shangshu analysis instrument
Sample；
S3: instrument " beginning " key is clicked, starts to test.
In the water provided in above-described embodiment half volatile organic mixture scene fast gas chromatograph analysis method be can
With on site quickly or vehicle-mounted instrument on detection method, avoid the prior art organic mixing of half volatile in water
When object is detected, multiple repairing weld is needed, carries out pre-treatment respectively, the complex operations step detected respectively.Using sample preparation-
Thermal desorption-chromatography automatic on-line analyzer tests the target components, realizes sampling, extracting and enriching, Thermal desorption to GC
Separation detection full process automatization operation, avoids artificial bring error.Meanwhile overcoming traditional liquid-liquid extraction organic solvent
Dosage big (200-1000mL) is also easy to produce secondary pollution, analytical cycle long (sampling and sample presentation time, at least 150min is not added) etc.
Drawback.The present embodiment realizes while analyzing the purpose of up to 13 kinds half volatile organic mixtures, and sampling amount only needs 10mL,
Detection time only needs 20-25min, and method is easy, quick, accurate, is more suitable for the quick detection at scene, and testing result has more
Timeliness.The method realizes field quick detection, for overall monitor Water quality, effectively supervises all kinds of emission sources, answers in time
Environmental pollution accident provides effective data and supports.
The present embodiment specifically defines that extraction temperature is 30-50 DEG C, extraction time 10-15min, in the extraction temperature and
Under extraction time, effect of extracting is preferable, and extraction quantity can reach the detection limit of instrument, while being conducive to shorten detection time, mentions
High detection efficiency.It should be noted that extraction temperature can also be any point value in 35 DEG C, 40 DEG C, 45 DEG C and its range, extraction
Taking the time can also be any point value in 11min, 12min, 13min, 14min and its range.The present embodiment also specifically limits
Resolution temperature is 200-250 DEG C, within the scope of the resolution temperature, can be realized the abundant parsing of target components, extends simultaneously
The service life of fiber material.It should be noted that resolution temperature can also be 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C and its model
Enclose interior any point value.The embodiment of the present invention also specifically defines gas-chromatography column oven temperature programming parameter, using program liter
Temperature have many advantages, such as improve separation, so that peak is narrowed, detect limit decline and it is time saving, the setting of actual temp then needs to be produced according to target
The boiling point composition of object is selected.It should be noted that with 20 DEG C/min's in the chromatographic column temperature program that the present embodiment limits
Heating rate rises to 160 DEG C, keeps 0-10min, or the arbitrary point in 2min, 4min, 6min, 8min and its range
Value.
In a preferred embodiment, the gas-chromatography test parameter further include:
Carrier gas: helium, carrier gas flux 2-5mL/min；
Make-up gas: helium, make-up gas flow 40-80mL/min；
Split ratio: (2-10): 1.
In the above-described embodiments, the size of gas-chromatography test parameter carrier gas flux will affect out the appearance speed of chromatography,
The too small appearance of flow is slower, and low efficiency, flow is excessive, will affect the accuracy of analysis；The setting of make-up gas can guarantee chromatography
It works under highly sensitive state, while its dead volume extra column effect that can eliminate detector；Split ratio influences the spirit of detection
Sensitivity, while also having a certain impact to detection limit.Gas-chromatography test parameter employed in the present embodiment can be realized more
Kind component preferably separates, and improves the accuracy of analysis.It should be noted that carrier gas flux may be 2.5mL/min, 3mL/
Any point value in min, 3.5mL/min, 4mL/min, 4.5mL/min and its range, make-up gas flow may be 50mL/
Any point value in min, 60mL/min, 70mL/min and its range, split ratio may be 3:1,4:1,5:1,6:1,7:1,
Any point value ratio in 8:1,9:1 and its range.
In a preferred embodiment, the gas-chromatography uses dielectric barrier discharge detector, the gas-chromatography test
Parameter further include: detection temperature is 300 DEG C, and discharge gas is helium, discharge gas flow 25-50mL/min.In this implementation
It in example, specifically defines using dielectric barrier discharge detector, reason is that dielectric barrier discharge detector volatilizees to all half
Property organic matter realize general and highly sensitive detection, avoid selective detector from being combined (FID, ECD, NPD), the device is complicated for reduction
Degree, dielectric barrier discharge detector only use a kind of inert gas, and the separation of detector high voltage discharge field and reaction zone, improve
Fast inspection screening equipment anti-interference ability and safe and practical property.
Will test temperature measuring in the present embodiment is 300 DEG C, and specifically defines that discharge gas is helium and discharge gas
Flow is conducive to the accuracy for improving testing result, specifically, dielectric barrier discharge detector detects temperature setting as high temperature baking
Roasting 300 DEG C of temperature effectively prevent semi-volatile organic matter to remain in addition itself is designed from blowback, and raising continuously measures reliable
Property, stability.Dielectric barrier discharge detector ionization detector excitation generate helium plasma energy be up to 13.5eV~
The ionization of majority of compounds and permanent gases may be implemented in 17.7eV, improves the versatility of detector.It is selected by experiment
Select suitable gas flow, be beneficial to prevent air-flow it is too low when plasma unstable either flow it is excessively high when noise increase etc.
Problem.Meanwhile in trace analysis, the purity for guaranteeing discharge gas is generally required, the present invention is using helium as discharge gas, energy
Enough effectively improve detector sensitivity.It should be noted that discharge gas flow can also for 30mL/min, 35mL/min,
Any point value in 40mL/min, 45mL/min and its range.
In a preferred embodiment, the extraction temperature is 45 DEG C；
The extraction time is 15min；
The resolution temperature is 250 DEG C；
The column oven temperature programming parameter are as follows: 40 DEG C of initial temperature, keep 2min；With the heating rate liter of 20 DEG C/min
To 160 DEG C, 0min is kept；220 DEG C are risen to the heating rate of 10 DEG C/min, keeps 12min；
The carrier gas flux is 2.5mL/min；
The make-up gas flow is 60mL/min；
The discharge gas flow is 30mL/min；
The split ratio is 3:1.
In the present embodiment, extraction parameters, analytic parameter and gas-chromatography test parameter are specifically defined, realize a variety of half
The preferable separation of volatile organic compounds and the accuracy of testing result, realize and once can be detected out all target components
The purpose of composition and content, method is easy, high-efficient, timeliness is good.
In a preferred embodiment, the half volatile organic mixture includes nitrobenzene, chlorobenzene class or nitro-chlorobenzene
At least one of class.
In a preferred embodiment, the nitrobenzene includes Isosorbide-5-Nitrae-dinitrobenzene, 1,3- dinitrobenzene, 1,2- dinitro
At least one of benzene and 2,4,6-trinitrotoluene, the chlorobenzene class include 1,2,3 ,-trichloro-benzenes, 1,2,4- trichloro-benzenes, 1,
3,5- trichloro-benzenes and 1, at least one of 2,3,4- tetrachlorobenzenes, the nitro-chlorobenzene class includes m-chloronitrobenzene, to nitroxyl chloride
At least one of benzene, o-nitrochlorobenzene and 1-CHLORO-2,4-DINITROBENZENE.
In a preferred embodiment, half volatile organic mixture scene fast gas chromatograph analysis method is also wrapped in the water
Include following steps:
With diluted high standard sample, standard serial solution is obtained；
The analysis instrument test parameter is set, above-mentioned standard series of samples is analyzed, standard curve is obtained.
In the above-described embodiments, by the detection to standard solution, standard curve is drawn, is conducive to the fast of target components
Speed detection, obtains rapidly the content of target components.
In a preferred embodiment, the dilution be secondary distilled water without above-mentioned half volatile organic mixture or
Person's ultrapure water.
In a preferred embodiment, if the concentration of the target components is more than 0.5mg/L, the diluted is used
It detects again afterwards.If the concentration of target components is more than 0.5mg/L, it be easy to cause chromatographic peak separation not exclusively, mesh on fiber material
It is big to mark object residual quantity, activation time lengthens, influence the accuracy and timeliness of testing result, therefore, it is necessary to after diluting again again
Measurement, improves the accuracy of testing result.
In order to become apparent from, to introduce in water provided by the embodiment of the present invention half volatile organic mixture scene in detail fast
Fast gas chromatography analysis method, is described below in conjunction with specific embodiment.
Embodiment 1
(1) standard serial solution configures
A, take standard sample, concentration parameter is shown in Table 1, with hplc grade methanol by big concentration standards be diluted to 10mg/L or
Person is 13 kinds of intermediate stock solutions of 20mg/L, is stored in spare in 4 DEG C of environment；
B, intermediate stock solution is diluted to standard series shown in table 2 with dilution.
1 standard items information of table
2 standard series of table
The standard solution for pipetting 10mL respectively according to standard series shown in table 2 measures each standard series into specimen cup.
(2) drafting of standard series sample detection and standard curve
The analysis instrument test parameter that solid phase microextraction is coupled with gas-chromatography is arranged: solid-phase micro-extraction coating is poly- diformazan
Radical siloxane, extraction temperature are 45 DEG C, extraction time 15min；Resolution temperature is 250 DEG C；It 40 DEG C of chromatographic column initial temperature, protects
2min is held, 160 DEG C of holding 0min are risen to 20 DEG C/min heating rate, 220 DEG C of holdings are risen to 10 DEG C/min heating rate
12min；Detector is dielectric barrier discharge detector (DBD detector), and temperature is 300 DEG C, and discharge gas is helium, and discharge gas
Flow is 30mL/min；Carrier gas is helium, carrier gas flux 2.5mL/min；Make-up gas is helium, and make-up gas flow is 60mL/
min；Split ratio is 3:1.
After parameter setting, standard series sample is added in the acquisition cup of Xiang Shangshu analysis instrument；
Instrument " beginning " key is clicked, starts to test.
Standard series sample parses in parsing module after solid phase microextraction, the mesh being adsorbed on solid phase microextraction needle
Mark component is resolved, and brings chromatographic column by carrier gas, after each group lease making chromatographic column separation in sample, examines into detector
It surveys, detector responds the target components flowed out from chromatographic column, and the data processing function through process-scale chromatography software will test
The signal of device is converted to chromatogram and carries out the qualitative, quantitative of target components.
P-nitrophenyl, 1,4- dinitrobenzene, 1,3- dinitrobenzene, 1,2- dinitrobenzene, 2,4 are distinguished with the peak area of survey,
6- trinitrotoluene, 1,2,3 ,-trichloro-benzenes, 1,2,4- trichloro-benzenes, 1,3,5- trichloro-benzenes, 1,2,3,4- tetrachlorobenzene, nitroxyl chloride
Benzene, paranitrochlorobenzene, o-nitrochlorobenzene, 2,4-dinitrochlorobenzene concentration (μ g/L) draw standard curve, as shown in figures 1-13.
Embodiment 2
Sample and blank sample (dilution) detection, detection method and parameter are with embodiment 1, the difference is that if sample
The concentration of target components is more than 0.5mg/L, then detects again after using diluted.
After the peak area measured, by the nitrobenzene of standard curve, Isosorbide-5-Nitrae-dinitrobenzene, 1,3- dinitrobenzene, 1,2- dinitro
Base benzene, 2,4,6- trinitrotoluene, 1,2,3 ,-trichloro-benzenes, 1,2,4- trichloro-benzenes, 1,3,5- trichloro-benzenes, 1,2,3,4- tetrachlorobenzene,
M-chloronitrobenzene, paranitrochlorobenzene, o-nitrochlorobenzene, 1-CHLORO-2,4-DINITROBENZENE concentration (μ g/L).Figure 14 is the dilute of sample blank
The chromatogram of liquid is released, Figure 15 is sample chromatogram figure.
Embodiment 3
Sample in embodiment 2 is carried out repeating to detect test, with embodiment 1, difference exists for detection method and parameter
If being more than 0.5mg/L in the concentration of sample object component, using detecting again after diluted, obtained testing result is such as
Shown in Figure 16.
Analysis of test results
Above-mentioned testing result is analyzed, analyzes result as shown in table 3 to table 6.
(1) 13 kind of noxious material precision test
The standard sample that concentration in standard series sample is 20.00 μ g/L is carried out 6 times according to the detection method of embodiment 1
Retest experiment, measurement concentration value are the standard solution of detection range upper limit value 50% or so, and continuous measurement 6 times calculates 6 times
The relative standard deviation of measured value, using the relative standard deviation as the decision content of precision.Calculation method are as follows:
Sr: precision measured value；
The average value of standard solution measured value；
N: pendulous frequency
Xi: i-th measured value
It the results are shown in Table 3.
3 13 kinds of noxious material Precision test results (n=6) of table
As shown in Table 3, the standard deviation that this method detects that each object obtains is respectively less than 0.35, shows this method to 13 kinds
Toxic target object assay has good precision.
(2) test is added in standard specimen
Any sample in sample Determination is taken to carry out standard specimen addition test, the detection method provided according to implementation 1 is continuous
Measurement sample 6 times, and measured value average value is calculated, it (is herein 13 with the standard solution of 1.0mL is added in 1000mL same sample
The mixed standard solution of kind of noxious material), the sample that is added after standard solution of continuous measurement 6 times simultaneously calculates being averaged for measured value
Value.Test rate of recovery R, calculation formula is added according to the standard specimen that formula calculates actual sample are as follows:
R: the test rate of recovery is added in standard specimen；
The average value of 6 measured values of sample after standard solution is added；
The average value of 6 measured values of sample；
C: standard liquid concentration (10ppm)
It the results are shown in Table 4.
Test test result is added in 4 13 kinds of noxious material standard specimens of table
The rate of recovery of 13 kinds of levels of toxic substances known to 4 data of table in this method is in 96.2%-103.70%.
(3) 13 kinds of noxious material quantitative repeatabilities and detection limit test
Repetitive test:
Instrument is switched on and recalls operation method, and instrument is made to be in optimal operational condition, the detection side provided according to embodiment 1
Method tests the mixed standard solution of 13 kinds of noxious materials, measurement 7 times at least continuous after stable reading, and records measurement concentration
Xi, wherein i is pendulous frequency (i=1,2..., n), and quantitative repeatability is calculated as follows.
RSD: quantitative repeatability；
Xi: i-th sample introduction measures concentration, μ g/L；
N times sample introduction measures mean concentration, μ g/L；
I: the serial number (i=1~7) of data is recorded；
N: the total number (n=7) of data is recorded.
Detection limit test:
Instrument is switched on and recalls operation method, and instrument is made to be in optimal operational condition, the detection side provided according to embodiment 1
Method tests the mixed standard solution of 13 kinds of noxious materials, continuously measures after stable reading 7 times.Each Toxic is calculated according to formula
The detection limit of matter.
D=t(n-1,0.99)×s
D: detection limit, μ g/L；
S: the concentration standard deviation of continuous measurement n times；
T: freedom degree n-1, t when confidence level is 99% is distributed (unilateral side), as n=7, t=3.143；
N: pendulous frequency, n=7.
It the results are shown in Table 5.
5 13 kinds of noxious material quantitative repeatabilities of table and detection limit test result
The quantitative repeatability of 13 kinds of levels of toxic substances known to 5 data of table in this method is respectively less than 6%, and detection limit is equal
Less than 1ppb, the detection of the emission limit of each target in national standard GB 3838-2002 " water environment quality standard " can be met.
(4) 13 kinds of noxious material qualitative tests
Instrument is switched on and recalls operation method, and instrument is made to be in optimal operational condition, the detection side provided according to embodiment 1
Method tests the mixed standard solution of 13 kinds of noxious materials, measurement 7 times at least continuous after stable reading, and records retention time
Xi, wherein i is pendulous frequency (i=1,2..., n), and qualitative repeatablity is calculated as follows.
RSD: qualitative repeatablity；
Xi: the chromatographic peak retention time of i-th measurement, min；
N times measure the average value of chromatographic peak retention time, min.
I: the serial number (i=1~7) of data is recorded；
N: the total number (n=7) of data is recorded.
It the results are shown in Table 6.
6 13 kinds of noxious material qualitative test results of table
The qualitative repeatablity of 13 kinds of levels of toxic substances known to 6 data of table in this method is respectively less than 0.05%, explanation
The retention time of each noxious material is highly stable.
In conclusion detection method provided by technical solution detects 13 kinds of noxious materials through the invention, respectively
Noxious material retention time is stable, peak shape is good and separating effect is fine, and accuracy is high, reproducible, and detection limit is low, meets state
Mark the detection demand of each noxious material of GB3838-2002 " water environment quality standard " standard.In addition, this technology of the present invention side
Detection method provided by case can carry out spot sampling, on-site test, and working efficiency significantly improves, test data timeliness
It is good, it can satisfy the demand quickly detected.
Claims (9)
1. half volatile organic mixture scene fast gas chromatograph analysis method in water, which comprises the following steps:
The analysis instrument test parameter that solid phase microextraction is coupled with gas-chromatography is set, and the analysis instrument test parameter includes extraction
Modulus block extraction parameters, parsing module analytic parameter and gas-chromatography test parameter, the extraction module extraction parameters include
30-50 DEG C of extraction temperature, extraction time 10-15min；The parsing module analytic parameter includes 200-250 DEG C of resolution temperature, solution
Analyse time 5-20s；The gas-chromatography test parameter includes column oven temperature programming parameter, the column oven temperature programming parameter
Are as follows: 40 DEG C of initial temperature, keep 2min；160 DEG C are risen to the heating rate of 20 DEG C/min, keeps 0-10min；With 10 DEG C/min
Heating rate rise to 220 DEG C, keep 12-20min；
After parameter setting, the sample to be tested of the organic mixture containing half volatile is added in the acquisition cup of Xiang Shangshu analysis instrument；
Instrument " beginning " key is clicked, starts to test.
2. analysis method according to claim 1, it is characterised in that: the gas-chromatography test parameter further include:
Carrier gas: helium, carrier gas flux 2-5mL/min；
Make-up gas: helium, make-up gas flow 40-80mL/min；
Split ratio: (2-10): 1.
3. analysis method according to claim 2, it is characterised in that: the gas-chromatography is detected using dielectric barrier discharge
Device, the gas-chromatography test parameter further include: detection temperature is 300 DEG C, and discharge gas is helium, and discharge gas flow is
25-50mL/min。
4. analysis method according to claim 3, it is characterised in that:
The extraction temperature is 45 DEG C；
The extraction time is 15min；
The resolution temperature is 250 DEG C；
The column oven temperature programming parameter are as follows: 40 DEG C of initial temperature, keep 2min；It is risen to the heating rate of 20 DEG C/min
160 DEG C, keep 0min；220 DEG C are risen to the heating rate of 10 DEG C/min, keeps 12min；
The carrier gas flux is 2.5mL/min；
The make-up gas flow is 60mL/min；
The discharge gas flow is 30mL/min；
The split ratio is 3:1.
5. analysis method according to claim 1-4, it is characterised in that: the half volatile organic mixture packet
Include at least one of nitrobenzene, chlorobenzene class or nitro-chlorobenzene class.
6. analysis method according to claim 5, it is characterised in that: the nitrobenzene includes Isosorbide-5-Nitrae-dinitrobenzene, 1,
At least one of 3- dinitrobenzene, 1,2- dinitrobenzene and 2,4,6-trinitrotoluene, the chlorobenzene class include 1,2,3 ,-three
Chlorobenzene, 1,2,4- trichloro-benzenes, 1,3,5- trichloro-benzenes and 1, at least one of 2,3,4- tetrachlorobenzenes, the nitro-chlorobenzene class include
At least one of m-chloronitrobenzene, paranitrochlorobenzene, o-nitrochlorobenzene and 1-CHLORO-2,4-DINITROBENZENE.
7. analysis method according to claim 6, it is characterised in that: further comprising the steps of:
With diluted high standard sample, standard serial solution is obtained；
The analysis instrument test parameter is set, above-mentioned standard series of samples is analyzed, standard curve is obtained.
8. analysis method according to claim 7, it is characterised in that: the dilution is organic without above-mentioned half volatile
The secondary distilled water or ultrapure water of mixture.
9. analysis method according to claim 8, it is characterised in that: if the concentration of the target components is more than 0.5mg/L,
It is detected again after then using the diluted.
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