CN106526018B - The method that gas chromatography mass spectrometry detects organic solvent residual in soil and water - Google Patents
The method that gas chromatography mass spectrometry detects organic solvent residual in soil and water Download PDFInfo
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Abstract
The present invention relates to the fields such as insecticides adjuvant residue detection, drug test, Environmental security, a kind of method that organic solvent residual in soil and water is detected in particular to gas chromatography mass spectrometry, this method comprises the following steps：1) soil to be detected and water, are distinguished into extracted solvent and anhydrous Na2SO4Centrifuging and taking supernatant and extracting solution is obtained by filtration after pretreatment；2), using gaschromatographic mass spectrometry determination step 1) in extracting solution；Gas chromatographic column used is DB WAX capillary chromatographic columns, and anhydrous MgSO is added in the extracting solution before crossing chromatographic column4；The organic solvent includes toluene, dimethylbenzene, DMF and DMSO；The dimethylbenzene includes ortho-xylene, paraxylene and meta-xylene.This method can it is quick, convenient, accurate, delicately the Determination of Residual Organic Solvents in the environmental samples such as soil and water is detected.
Description
Technical field
The present invention relates to fields such as insecticides adjuvant residue detection, drug test, Environmental securities, in particular to one kind
The method that gas chromatography-mass spectrography detects organic solvent residual in soil and water.
Background technology
Organic solvent is essential chemicals in the productions such as pesticide, chemical industry, medicine and application process, toluene, diformazan
Benzene, DMF and DMSO are the larger organic solvents of wherein great representational dosage.China is the state of pesticide dosage maximum in the world
Family, toluene, dimethylbenzene, dimethylformamide (DMF), dimethyl trident maple (DMSO) are as common solvent, cosolvent, stabilizer
Dosage in pesticidal preparations is very huge, it was reported that China has for preparing toluene used in missible oil, dimethylbenzene etc. every year
About 400,000 tons of solvent.DMF is a kind of industrial organic solvent of function admirable, can be used for extracting acetylene and manufacture polyacrylonitrile
Fiber, be widely used imitation leather manufacture, organic synthesis, dyestuff, pharmacy, Petroleum refining and resin etc. are industrial.Dimethyl sulfoxide (DMSO)
(Dimethyl sulfoxide, DMSO) dimethyl sulfoxide (Dimethylsulfoxide, abbreviation DMSO) is a kind of both containing hydrophilic
Both sexes organic molecule of the sulfoxide radicals again containing two hydrophobic meths, its is existing water-soluble and can dissolve substantial amounts of lipophilicity chemical combination
Thing, suffers from being widely applied in biological medicine and field of textile industry.
But some international organizations such as international chemicals security outline, U.S. environment protection mechanism, World Health Organization
The above-mentioned organic solvent of studies have shown that there is carcinogenic, teratogenesis, have certain harm to environment, human body.Toluene, dimethylbenzene
There is stimulation to skin, mucous membrane, the organs such as lung, liver, kidney and nervous function can be endangered, research shows decis
Missible oil causes the acute poisoning of people, predominantly caused by dimethylbenzene；DMF can be through in skin contact and respiratory tract suction body, causing machine
The symptoms such as body gastrointestinal disorders, liver damage or pathological change and potential remote effect, and using liver damage as very；DMSO
Have an effect with protein hydrophobic group, cause protein denaturation, there is vascular toxicity and liver renal toxicity, have to human skin and ooze
Permeability, has stimulation to eye, can cause Nausea and vomiting, fash.Being excessively used for above-mentioned organic solvent may be damaged directly
Human and livestock health, destroys ecological environment, is negatively affected to Pesticidal products, agricultural product, chemical products, medical product etc..Therefore,
To ensure pesticide drug safety and the developed country such as agricultural product quality and safety, the U.S., Canada according to the toxicity of organic additive
Inventory management is carried out to it with harmfulness, wherein, toluene, dimethylbenzene, DMF, which are clearly classified as, to be limited with insecticides adjuvant, DMSO quilts
It is classified as Group III insecticides adjuvant；DMF was included in the poison of national public health emergency monitoring by China from 1 day January in 2006
Name list.Therefore method that is convenient, fast, accurate, sensitively measuring above-mentioned organic solvent is current environment, food, medicine point
One of research hotspot of analysis worker.
At present, the detection method on organic solvent mainly has direct and headspace sampling gas chromatography-mass spectrography etc.：(1)
Although existing correlative study reports the detection method of DMF and DMSO in textile, medicine, due to DMF and DMSO polarity is big,
Boiling point is high, and existing direct injected pretreatment technology need to pass through extraction and back extraction, complicated and need to use a large amount of organic molten
Agent, environmental friendliness are low；And the sensitivity of head space method often declines 1~2 order of magnitude, existing method, which cannot be fully met, to be worked as
Preceding demand.It is highly sensitive, fast and accurately analysis the two be this area urgent problem to be solved.(2) although both at home and abroad to water
The detection technique of the benzene homologues such as toluene, dimethylbenzene in body, medicine, cosmetics, packaging for foodstuff, weaving, building coating has been done greatly
Quantity research, but headspace sampling is used mostly, equipment tool there are certain requirements, it is higher to promote cost.And in current research method
Calculated more with total xylenes, although adjacent, much like to the chemical constitution of, meta-xylene, due to the space bit of two methyl
Great influence can be had to the electron cloud of phenyl ring by putting, and cause the huge difference of its chemical property, such as paraxylene is in human body
P-methylbenzoic acid can be metabolized to, and then toluric acid is generated with glycine reactant, is discharged from urine, its toxicity is much larger than it
Can produce serious harm to human body when his two kinds of dimethylbenzene, for a long time contact or short-term access high concentration material, realize it is adjacent,
Between, the differentiation of paraxylene is of great significance.(3) due to toluene, dimethylbenzene, the boiling point of DMF, DMSO and polarity spectrum compared with
Greatly, the analysis method for while accurately, sensitively analyzing the organic solvents such as toluene, dimethylbenzene, DMF and DMSO is also rarely reported, pin
Method to soil and water sample is even more to have no report.Quick, sensitive, the above-mentioned organic solvent of Accurate Determining analysis method at the same time
It is the technical barrier of this area.
In view of this, it is special to propose the present invention.
The content of the invention
It is an object of the invention to provide a kind of quick, convenient, accurate, sensitive gas chromatography-mass spectrography detection soil
With the method for the Determination of Residual Organic Solvents such as toluene, dimethylbenzene, DMF, DMSO in the environmental sample such as water, to solve the above problems.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
The method of organic solvent residual, includes the following steps in a kind of gas chromatography-mass spectrography detection soil and water：
1) soil to be detected and water, are distinguished into extracted solvent and anhydrous Na2SO4Centrifuging and taking supernatant is simultaneously after pretreatment
Extracting solution is obtained by filtration；
2), using the extracting solution in Gas Chromatography-Mass Spectrometry step 1)；
Gas chromatographic column used is DB-WAX capillary chromatographic columns, is added excessively before chromatographic column in the extracting solution anhydrous
MgSO4；
The organic solvent includes toluene, dimethylbenzene, DMF and DMSO；
The dimethylbenzene includes ortho-xylene, paraxylene and meta-xylene.
The present invention can accurately, rapidly and sensitively be used for toluene, dimethylbenzene, DMF, DMSO in various agricultural product, soil and water
Deng the monitoring of organic solvent residual.Compared with prior art, although liquid-liquid extraction-makings used in the present invention is not using top
Sky, but due to improving the species of deicer, sensitivity significantly gets a promotion, and pre-treatment step is easily operated, and the technology is grasped
It is convenient to make, and by DB-WAX capillary chromatographic columns combine specific experiment condition can realize to meta-xylene, ortho-xylene with
And the differentiation of paraxylene.
The present invention is worth the water sample to be detected referred to, can be selected from the water sample at the low-lying place in farmland, or the water sample on farmland periphery, together
When those skilled in the art record according to the present invention, can also apply the present invention to plant chimney stalk, be originally, extra large Organic substance in water
Among detection.
Preferably, the method that gas chromatography-mass spectrography as described above detects organic solvent residual in soil and water, it is described
Anhydrous Na2SO4With anhydrous MgSO4Mass ratio be 3：(0.25~0.5).
Minor amount of water in sample can not only damage chromatographic column, can also influence the sensitivity of DMF and DMSO, the use of deicer
To testing result important.Anhydrous Na2SO4Hydrophobicity preferably, water absorption is very big, cheap, processing is convenient, as de-
It is easier to be eluted when aqua, but its drying capacity is weaker, speed is slow；Anhydrous MgSO4Volatility is smaller, rate of drying
Hurry up, drying capacity it is strong, but its water absorption is relatively small and heat release is more., can be more preferable by the way that both are used with specific proportions
Ground balances water absorption and the relation of drying effect.
Preferably, the method that gas chromatography-mass spectrography as described above detects organic solvent residual in soil and water, in step
It is rapid 1) in, the Extraction solvent is that volume ratio is 1:(0.5~2):The mixing of the acetonitrile-ethyl acetate-acetone of (0.5~2) is molten
Liquid.
Since impurity is many in water in agricultural, food and industrial production environment and soil, the physicochemical property of organic solvent is poor
It is not larger, so sample pre-treatments are very crucial parts.The workload of pre-treatment and error source have accounted for whole detection
More than the 60% of process, emphasis have the selection of Extraction solvent and assisted extraction mode, selection of purification style etc..
Extraction solvent will extract impurity less as far as possible, while require to extract target organic solvent as much as possible.Acetonitrile and third
Ketone is all relatively good to the extraction effect of various organic matters, but matrix interference is larger, using acetonitrile and acetone as extractant often
More highly polar impurity is often had to be mixed into；For ethyl acetate since polarity is smaller, when extraction, can reduce the larger impurity of polarity
Introduce.Consider extraction efficiency and matrix interference, the present invention selects 1:(0.5~2):Acetonitrile-the ethyl acetate of (0.5~2)-
The pre-treatment effect that the mixed solution of acetone carries out sample as organic solvent is preferable；
It is furthermore preferred that it is 1 to select volume ratio:1.2:The mixed solution of the acetonitrile-ethyl acetate-acetone of (1.2~1.5).
Preferably, in gas chromatography-mass spectrography as described above detection soil and water organic solvent residual method, when treating
When sample is soil, in order to improve the extraction effect of DMSO, a certain amount of water need to be added, step 1) specifically includes：
The soil of homogeneous is weighed by 1g：0.25mL:The solid-to-liquid ratio of (0.75~2.25) mL sequentially adds water, acetonitrile-second
Acetoacetic ester-acetone mixed solution simultaneously mixes, and the anhydrous Na with the pedotheque equivalent is added under condition of ice bath2SO4And mix,
Centrifuging and taking supernatant and soil extract is obtained by filtration after standing.
Preferably, the method that gas chromatography-mass spectrography detects organic solvent residual in soil and water, when sample to be tested is water
When, step 1) specifically includes：
By 1mL water：The ratio of (0.5~2.5) mL acetonitriles-ethyl acetate-acetone is by water and acetonitrile-ethyl acetate-acetone
Mixed solution mixes, and the anhydrous Na with 1~2 times of the water quality is added under condition of ice bath2SO4And mix, after standing in centrifuging and taking
Simultaneously aqueous extract is obtained by filtration in clear liquid.
Preferably, the method that gas chromatography-mass spectrography as described above detects organic solvent residual in soil and water, it is described
Filtering was specially 0.2~0.25 μm of organic phase filter membrane.
Different chromatographic columns are larger to the retention property difference of compound, six kinds of target compound polarity that this patent is related to and
Boiling point difference is larger, benzene homologues can be realized with preferable separation analysis using the DB-1 chromatographic columns of low pole, but polarity is larger
The hangover of compound DMF and DMSO peaks rows it is more serious；Although the peak shape of 6 kinds of organic matters of DB-624 chromatographic columns using middle polarity
Preferably, but meta-xylene and paraxylene can not be separated；The quick of object can be realized using the DB-WAX chromatographic columns of polarity
Efficiently separate, and peak shape is preferable.It is therefore preferred that gas chromatographic column is DB-WAX chromatographic columns.
Preferably, the method that gas chromatography-mass spectrography as described above detects organic solvent residual in soil and water, in step
It is rapid 2) in, GC conditions are：
Column length is 30m, a diameter of 320 μm, and thickness is 5 μm；Chromatogram column temperature：50~65 DEG C holding 4~6min, then with
5~15 DEG C/min temperature programmings are warming up to 180~200 DEG C to 130~150 DEG C, then with 25~45 DEG C/min, keep 1~3min；
180~230 DEG C of injector temperature；1 μ L of sample size；Input mode is split sampling, split ratio (15~5)：1；Carrier gas is helium；
Constant current mode, 0.8~1.5mL/min of flow.
Temperature programming significantly affects the separating effect and peak shape that detect object, and heating rate is larger, is unfavorable for
The separation of chaff interferent in object and matrix；Conversely, chromatography peak stretching, analysis time are longer.
Preferably, the method that gas chromatography-mass spectrography as described above detects organic solvent residual in soil and water, in step
It is rapid 2) in, Mass Spectrometry Conditions are：
270~290 DEG C of chromatography-mass spectroscopy interface temperature；Electron impact ion source, electron energy 70eV, ion source temperature 220
~240 DEG C, 140~160 DEG C of quadrupole rod temperature；The solvent delay time：5~8.5min；Scanning of the mass spectrum mode is ion monitoring mould
Formula.
Preferably, the method that gas chromatography-mass spectrography as described above detects organic solvent residual in soil and water, with mark
The retention time of quasi- solution chromatographic peak is qualitative, and quantified by external standard method is used in terms of peak area.
Preferably, in gas chromatography-mass spectrography as described above detection soil and water organic solvent residual method, into
During row mass spectrum operation, scan pattern is ion detection mode.
The interference of full scan mode substrates is big, in order to effectively reduce matrix interference, selects ion detection mode.
Preferably, the method that gas chromatography-mass spectrography as described above detects organic solvent residual in soil and water；
When detecting toluene, qualitative ion is used as using mass-to-charge ratio 92,65,39；Quota ion is used as using mass-to-charge ratio 91
When detecting DMF, qualitative ion is used as using mass-to-charge ratio 44；Quota ion is used as using mass-to-charge ratio 73；
When detecting DMSO, qualitative ion is used as using mass-to-charge ratio 78；Quota ion is used as using mass-to-charge ratio 63；
When detecting dimethylbenzene, qualitative ion is used as using mass-to-charge ratio 106,105,77；Quota ion is used as using mass-to-charge ratio 91.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer, is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
S11, instrument and reagent
7890A/5975C gas chromatograph-mass spectrometer (GC-MS)s (Agilent companies of the U.S.)；105 electronic balance (Switzerland of XS
Mettler Toledo companies)；QL-901 vortexs vortex mixer (its woods Bell Instrument Ltd. of Haimen City)；Biofuge
Stratos table-type high-speed refrigerated centrifuges (Thermo companies of the U.S.).
Acetonitrile, ethyl acetate, toluene, acetone, DMF, DMSO (chromatographically pure, German Merck companies)；Ortho-xylene, two
Toluene, paraxylene (chromatography standard items, Chinese medicines group chemical reagent Beijing Co., Ltd)；Heartily drinking pure water (is breathed out
Breathe out group)；Other reagents are that analysis is pure, are purchased from the good Co., Ltds that make the science and technology prosperous of Beijing Bai Hui.
Pedotheque and water sample are gathered from Yanjiao periphery farmland.
S12, standard solution are prepared
Acetonitrile, ethyl acetate, acetone are made into volume ratio as 1:1.2:1.2 extracting solution；
Toluene, ortho-xylene, paraxylene, meta-xylene, DMF and DMSO with extracting solution be made into concentration for 2.0 ×
1046 kinds of standard reserving solutions of mg/L.Benzene homologues are made into extracting solution, DMF, DMSO concentration are respectively 2.0 × 10 again2mg/L、1.0
×103mg/L、2.0×103The hybrid standard working solution of mg/L.
S13, sample pre-treatments
S13.1, pedotheque pre-treatment
The soil of homogeneous is weighed by 1g：0.25mL:The solid-to-liquid ratio of 1.5mL sequentially adds water, extracting solution mixed solution simultaneously
Mix, the anhydrous Na with the pedotheque equivalent is added under condition of ice bath2SO4And mix, centrifuging and taking supernatant and mistake after standing
Filter obtains soil extract.
2mL soil extracts are taken to add anhydrous MgSO4, upper machine testing after 0.22 μm of membrane filtration.
S13.2, water sample pre-treatment
By 1mL water：The ratio of 1.5mL extracting solutions mixes water and extracting solution mixed solution, adds and accounts under condition of ice bath
The anhydrous Na of 1.5 times of the water quality2SO4And mix, centrifuging and taking supernatant and aqueous extract is obtained by filtration after standing.
2mL aqueous extracts are taken to add anhydrous MgSO4, upper machine testing after 0.22 μm of membrane filtration.
S14, chromatography and Mass Spectrometry Conditions
GC conditions：Agilent DB-WAX capillary chromatographic columns；Column length is 30m, a diameter of 320 μm, thickness 5
μm；Chromatogram column temperature：60 DEG C of holding 5min, then with 10 DEG C/min temperature programmings to 140 DEG C, then are warming up to 40 DEG C/min
190 DEG C, keep 2min；220 DEG C of injector temperature；1 μ L of sample size；Input mode is split sampling, split ratio 15：1；Carrier gas is
Helium；Constant current mode, flow 1.0mL/min.Anhydrous MgSO is added in chromatography before machine4；The anhydrous Na2SO4With anhydrous MgSO4
Mass ratio be 3:0.35.
Mass Spectrometry Conditions：280 DEG C of chromatography-mass spectroscopy interface temperature；Electron impact ion source, electron energy 70eV, ion gun temperature
230 DEG C of degree, 150 DEG C of quadrupole rod temperature；The solvent delay time：6min；Scanning of the mass spectrum mode is ion monitoring mode.
The retention time of each organic matter, qualitatively and quantitatively ion is shown in Table 1.
The GC-MS detection parameters of 1 dimethylbenzene of table
| Component | Retention time | Quota ion (m/z) | Qualitative ion (m/z) |
| Toluene | 9.06 | 91 | 92,65,39 |
| Ortho-xylene | 12.39 | 91 | 106,105,77 |
| Paraxylene | 11.30 | 91 | 106,105,77 |
| Meta-xylene | 11.44 | 91 | 106,105,77 |
| DMF | 15.25 | 73 | 44 |
| DMSO | 19.21 | 63 | 78 |
Embodiment 2
S21, instrument and reagent
Same S11.
S22, standard solution are prepared
Acetonitrile, ethyl acetate, acetone are made into volume ratio as 1:1.2:2 extracting solution；
Toluene, ortho-xylene, paraxylene, meta-xylene, DMF and DMSO with extracting solution be made into concentration for 2.0 ×
1046 kinds of standard reserving solutions of mg/L.Benzene homologues are made into extracting solution, DMF, DMSO concentration are respectively 2.0 × 10 again2mg/L、1.0
×103mg/L、2.0×103The hybrid standard working solution of mg/L.
S23, sample pre-treatments
S23.1, pedotheque pre-treatment
The soil of homogeneous is weighed by 1g：0.25mL:The solid-to-liquid ratio of 2.25mL sequentially adds water, extracting solution mixed solution simultaneously
Mix, the anhydrous Na with the pedotheque equivalent is added under condition of ice bath2SO4And mix, centrifuging and taking supernatant and mistake after standing
Filter obtains soil extract.
2mL soil extracts are taken to add anhydrous MgSO4, upper machine testing after 0.2 μm of membrane filtration.
S23.2, water sample pre-treatment
By 1mL water：The ratio of 0.5mL extracting solutions mixes water and extracting solution mixed solution, adds and accounts under condition of ice bath
The anhydrous Na of 1 times of the water quality2SO4And mix, centrifuging and taking supernatant and aqueous extract is obtained by filtration after standing.
2mL aqueous extracts are taken to add anhydrous MgSO4, upper machine testing after 0.2 μm of membrane filtration.
S24, chromatography and Mass Spectrometry Conditions
GC conditions：Agilent DB-WAX capillary chromatographic columns；Column length is 30m, a diameter of 320 μm, thickness 5
μm；Chromatogram column temperature：50 DEG C of holding 6min, then with 5 DEG C/min temperature programmings to 130 DEG C, then with 45 DEG C/min are warming up to 200
DEG C, keep 1min；180 DEG C of injector temperature；1 μ L of sample size；Input mode is split sampling, split ratio 15：1；Carrier gas is helium
Gas；Constant current mode, flow 0.8mL/min.Anhydrous MgSO is added in chromatography before machine4；The anhydrous Na2SO4With anhydrous MgSO4's
Mass ratio is 3:0.25.
Mass Spectrometry Conditions：270 DEG C of chromatography-mass spectroscopy interface temperature；Electron impact ion source, electron energy 70eV, ion gun temperature
240 DEG C of degree, 160 DEG C of quadrupole rod temperature；The solvent delay time：5min；Scanning of the mass spectrum mode is ion monitoring mode.
The retention time of each organic matter, qualitatively and quantitatively ion is shown in Table 1.
Embodiment 3
S31, instrument and reagent
Same S11.
S32, standard solution are prepared
Acetonitrile, ethyl acetate, acetone are made into volume ratio as 1:1.2:0.5 extracting solution；
Toluene, ortho-xylene, paraxylene, meta-xylene, DMF and DMSO with extracting solution be made into concentration for 2.0 ×
1046 kinds of standard reserving solutions of mg/L.Benzene homologues are made into extracting solution, DMF, DMSO concentration are respectively 2.0 × 10 again2mg/L、1.0
×103mg/L、2.0×103The hybrid standard working solution of mg/L.
S33, sample pre-treatments
S33.1, pedotheque pre-treatment
The soil of homogeneous is weighed by 1g：0.25mL:The solid-to-liquid ratio of 0.75mL sequentially adds water, extracting solution mixed solution simultaneously
Mix, the anhydrous Na with the pedotheque quality equivalent is added under condition of ice bath2SO4And mix, centrifuging and taking supernatant after standing
And soil extract is obtained by filtration.
2mL soil extracts are taken to add anhydrous MgSO4, upper machine testing after 0.25 μm of membrane filtration.
S33.2, water sample pre-treatment
By 1mL water：The ratio of 2.5mL extracting solutions mixes water and extracting solution mixed solution, adds and accounts under condition of ice bath
The anhydrous Na of 2 times of the water quality2SO4And mix, centrifuging and taking supernatant and aqueous extract is obtained by filtration after standing.
2mL aqueous extracts are taken to add anhydrous MgSO4, upper machine testing after 0.25 μm of membrane filtration.
S34, chromatography and Mass Spectrometry Conditions
GC conditions：Agilent DB-WAX capillary chromatographic columns；Column length is 30m, a diameter of 320 μm, thickness 5
μm；Chromatogram column temperature：65 DEG C of holding 4min, then with 15 DEG C/min temperature programmings to 150 DEG C, then are warming up to 25 DEG C/min
180 DEG C, keep 3min；230 DEG C of injector temperature；1 μ L of sample size；Input mode is split sampling, split ratio 10：1；Carrier gas is
Helium；Constant current mode, flow 1.5mL/min.Anhydrous MgSO is added in chromatography before machine4；The anhydrous Na2SO4With anhydrous MgSO4
Mass ratio be 3:0.5.
Mass Spectrometry Conditions：290 DEG C of chromatography-mass spectroscopy interface temperature；Electron impact ion source, electron energy 70eV, ion gun temperature
220 DEG C of degree, 140 DEG C of quadrupole rod temperature；The solvent delay time：8.5min；Scanning of the mass spectrum mode is ion monitoring mode.
The retention time of dimethylbenzene, qualitatively and quantitatively ion is shown in Table 1.
Experimental example 1
For the accuracy of evaluation method, recovery of standard addition and Precision Experiment are carried out using blank sample.In different substrates
6 kinds of organic solvent mixed standard solutions of 3 concentration (basic, normal, high) are added in (water or soil) blank sample respectively, by implementation
The method parallel determination of example 1~3 5 times.The range of linearity, related coefficient, detected level and the quantitative limit of each embodiment are counted, as a result
As shown in table 2.
Each embodiment effect of table 2
Further, comparative example is set as follows：
Comparative example：Article (Wang Shanshan etc., the 6 kinds of organic solvent residuals in agricultural product delivered with applicant in May, 2015
Gas chromatography-mass spectrum detection method,《Analysis test journal》Vol.34；No.5；588~594) method described in is to identical
Sample be detected, as a comparison case.
Recovery of standard addition in technical solution described in comparative example and preferred embodiment (embodiment 1) is carried out
Compare, the results are shown in Table 3.The results show that the rate of recovery of present invention toluene in the range of varying level for 75.1%~
95.5%, RSD are 1.3%~3.4%；The rate of recovery of meta-xylene is that 79.1%~94.3%, RSD is 1.2%~4.5%；
The rate of recovery of paraxylene is that 78.9%~97.2%, RSD is 0.9%~3.4%；The rate of recovery of ortho-xylene for 80.1%~
93.2%, RSD are 1.6%~4.7%；The rate of recovery of DMF is that 95.4%~102.1%, RSD is 0.8%~2.6%；DMSO
The rate of recovery be that 94.8%~105.6%, RSD is 0.7%~4.6% (being shown in Table 3).
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, but it will be understood by those of ordinary skill in the art that：Its
It can still modify to the technical solution described in foregoing embodiments, either to which part or all technical characteristic
Carry out equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention skill
The scope of art scheme.
The recovery of standard addition (n=6) of 6 kinds of organic solvents in 3 different substrates vegetables vegetables and fruits of table
Claims (9)
1. a kind of method of organic solvent residual in gas chromatography-mass spectrography detection soil and water, it is characterised in that including as follows
Step：
1) soil to be detected and water, are distinguished into extracted solvent and anhydrous Na2SO4Centrifuging and taking supernatant and filtered after pretreatment
Obtain extracting solution；The Extraction solvent is that volume ratio is 1:(0.5~2):Acetonitrile-the ethyl acetate-acetone of (0.5~2) mixes
Close solution；
2), using the extracting solution in Gas Chromatography-Mass Spectrometry step 1)；
Gas chromatographic column used is DB-WAX capillary chromatographic columns, and anhydrous MgSO is added in the extracting solution before crossing chromatographic column4；
The organic solvent includes toluene, dimethylbenzene, DMF and DMSO；
The dimethylbenzene includes ortho-xylene, paraxylene and meta-xylene.
2. the method for organic solvent residual in gas chromatography-mass spectrography detection soil according to claim 1 and water, it is special
Sign is, the anhydrous Na2SO4With anhydrous MgSO4Mass ratio be 3:(0.25~0.5).
3. the method for organic solvent residual in gas chromatography-mass spectrography detection soil according to claim 1 and water, it is special
Sign is that, when sample to be tested is soil, step 1) specifically includes：
The soil of homogeneous is weighed by 1g：0.25mL:The solid-to-liquid ratio of (0.75~2.25) mL sequentially adds water, acetonitrile-acetic acid second
Ester-acetone mixed solution simultaneously mixes, and the anhydrous Na with the pedotheque equivalent is added under condition of ice bath2SO4And mix, stand
Centrifuging and taking supernatant and soil extract is obtained by filtration afterwards.
4. the method for organic solvent residual in gas chromatography-mass spectrography detection soil according to claim 1 and water, it is special
Sign is that, when sample to be tested is water, step 1) specifically includes：
By 1mL water：The ratio of (0.5~2.5) mL acetonitriles-ethyl acetate-acetone mixes water with acetonitrile-ethyl acetate-acetone
Solution mixes, and the anhydrous Na with 1~2 times of the water quality is added under condition of ice bath2SO4And mix, centrifuging and taking supernatant after standing
And aqueous extract is obtained by filtration.
5. the method for organic solvent residual in the gas chromatography-mass spectrography detection soil and water according to claim 3 or 4,
It is characterized in that, the filtering was specially 0.2~0.25 μm of organic phase filter membrane.
6. the method for organic solvent residual in gas chromatography-mass spectrography detection soil according to claim 1 and water, it is special
Sign is, in step 2), GC conditions are：
Column length is 30m, a diameter of 320 μm, and thickness is 5 μm；Chromatogram column temperature：50~65 DEG C of 4~6min of holding, then with 5~
15 DEG C/min temperature programmings are warming up to 180~200 DEG C to 130~150 DEG C, then with 25~45 DEG C/min, keep 1~3min；Into
180~230 DEG C of sample mouth temperature；1 μ L of sample size；Input mode is split sampling, split ratio (15~5)：1；Carrier gas is helium；It is permanent
Stream mode, 0.8~1.5mL/min of flow.
7. the method for organic solvent residual in gas chromatography-mass spectrography detection soil according to claim 1 and water, it is special
Sign is, in step 2), Mass Spectrometry Conditions are：
270~290 DEG C of chromatography-mass spectroscopy interface temperature；Electron impact ion source, electron energy 70eV, ion source temperature 220~
240 DEG C, 140~160 DEG C of quadrupole rod temperature；The solvent delay time：5~8.5min；Scanning of the mass spectrum mode is ion monitoring mode.
8. the method for organic solvent residual in gas chromatography-mass spectrography detection soil according to claim 7 and water, it is special
Sign is that, when carrying out mass spectrum operation, scan pattern is ion detection mode.
9. the method for organic solvent residual in gas chromatography-mass spectrography detection soil according to claim 8 and water, it is special
Sign is：
When detecting toluene, qualitative ion is used as using mass-to-charge ratio 92,65,39；Quota ion is used as using mass-to-charge ratio 91；
When detecting DMF, qualitative ion is used as using mass-to-charge ratio 44；Quota ion is used as using mass-to-charge ratio 73；
When detecting DMSO, qualitative ion is used as using mass-to-charge ratio 78；Quota ion is used as using mass-to-charge ratio 63；
When detecting dimethylbenzene, qualitative ion is used as using mass-to-charge ratio 106,105,77；Quota ion is used as using mass-to-charge ratio 91.
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