CN104698119B - Method for detecting amide compounds in environment water sample - Google Patents
Method for detecting amide compounds in environment water sample Download PDFInfo
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Abstract
The invention belongs to the field of chemical analysis, and particularly relates to a method for detecting amide compounds in an environment water sample. The method includes the following steps of firstly, mixing the environment water sample with alkali and sodium chloride to obtain environment water sample liquid to be extracted, wherein the pH value of the environment water sample liquid to be extracted ranges from 10 to 11; secondly, conducting solid phase micro-extraction on the environment water sample liquid to be extracted through an extraction optical fiber to obtain an environment water sample extraction sample, wherein the temperature of solid phase micro-extraction ranges from 70 DEG C to 80 DEG C; thirdly, detecting the environment water sample extraction sample to obtain the types and/or contents of the amide compounds contained in the environment water sample. Through solid phase micro-extraction, the amide compounds in the environment water sample are directly extracted, the stability of the extraction effect is ensured by means of an appropriate extraction temperature and an appropriate pH value of the extraction liquid, and therefore the method has a stable standard recovery rate.
Description
Technical field
The invention belongs to chemical analysis field, the detection method of amides compound in more particularly, to a kind of environmental water sample.
Background technology
Alachlor, Acetochlor, pretilachlor, butachlor, propisochlor are five kinds of the most frequently used and most important amide-type herbicidings
Agent, its drug effect is not limited by region, weather conditions, is mainly used in corn and soybean, cotton, wheat, paddy rice, peanut and other crops
The anti-miscellaneous weeding work in field, applied quite varied in the last few years in China.
Although these acetamide-group herbicides have excellent herbicidal performance, they also have direct toxicity, not volatile,
It is difficult photodissociation, the shortcoming easily remaining.In China with a large amount of uses of acetamide-group herbicides, result in them in lake and pond
Deng a large amount of residuals in waters, cause fish and the death of batrachia group, the mankind and ecological environment are caused potentially huge
Big threat.According to the difference in structure, acetamide-group herbicides wait until higher water solubility and relatively low soil in having
Absorption constant, so be applied to the acetamide-group herbicides in farmland it is easy to transfer to phreatic water or with rainwater by infiltration
Stream enters surface water straight, and mankind drinking water source is polluted.Alachlor, Acetochlor are set to by U.S. environment protection general bureau
B-2 class carcinogenic substance is it is stipulated that within the monitoring phase of 1 month, in underground water, residual concentration must not exceed 0.1mg/l.Some grind recently
Study carefully and show, a certain amount of butachlor can cause the chromatid deformity of the red thin variation of catfish, induction people.Therefore fast and accurately
Measure the residual quantity of acetamide-group herbicides, the pollution level to ambient water for such agricultural chemicals can be visually known.
At present, the detection method with regard to acetamide-group herbicides in environmental water sample mainly has liquid chromatogram (lc-uv) both at home and abroad
Method, the electron capture detector (ECD) detection method (gc-ecd) of gas-chromatography, nitrogen phosphorous detector detection method (gc-npd) and gas-chromatography
With MS (gc-ms).Using these methods before environmental water sample is detected, it is required to environmental water sample is carried out not
With the pre-treatment of degree, required with the sample introduction meeting detecting instrument, but the operation of existing pre-treating method is relatively complicated, pre-treatment
Effect affected by operating condition larger, lead to existing environmental water sample detection method recovery of standard addition fluctuate larger, thus reducing
The accuracy of testing result.
Content of the invention
In view of this, it is an object of the invention to provide in a kind of environmental water sample amides compound detection method, adopt
When environmental water sample being detected with the method that the present invention provides, its recovery of standard addition is relatively stable.
The invention provides in a kind of environmental water sample amides compound detection method, comprise the following steps:
A), environmental water sample is mixed with alkali and sodium chloride, obtains environmental water sample liquid to be extracted；
The ph value of described environmental water sample liquid to be extracted is 9～11；
B), using extraction optical fiber, to described environmental water sample, liquid to be extracted carries out SPME, obtains environmental water sample extraction
Sample；
The temperature of described SPME is 70～80 DEG C；
C), the described environmental water sample of detection extracts sample, obtains in environmental water sample the species of contained amides compound and/or contains
Amount.
Preferably, the mode of described SPME is headspace solid-phase microextraction.
Preferably, the time of described headspace solid-phase microextraction is 30～50min.
Preferably, the coating of described extraction optical fiber is pdms/dvb.
Preferably, the coating layer thickness of described extraction optical fiber is 60～70 μm.
Preferably, in described environmental water sample liquid to be extracted, the concentration of sodium chloride is 0.3～0.36g/ml.
Preferably, in step a), before described environmental water sample is mixed with alkali and sodium chloride, first described environmental water sample is carried out
Filter.
Preferably, in step b), using extraction optical fiber before to described environmental water sample, liquid to be extracted carries out SPME,
First described extraction optical fiber is carried out aging.
Preferably, the described aging time is 10～30min.
Preferably, in step c), the mode that the described environmental water sample of detection extracts sample detects for gas chromatography-mass spectrography.
Compared with prior art, the invention provides in a kind of environmental water sample amides compound detection method.This
In the environmental water sample of bright offer, the detection method of amides compound comprises the following steps: a), environmental water sample and alkali and sodium chloride
Mixing, obtains environmental water sample liquid to be extracted；The ph value of described environmental water sample liquid to be extracted is 10～11；B), using extraction optical fiber
To described environmental water sample, liquid to be extracted carries out SPME, obtains environmental water sample extraction sample；The temperature of described SPME
For 70～80 DEG C；C), the described environmental water sample of detection extracts sample, obtain in environmental water sample the species of contained amides compound and/
Or content.The present invention is directly extracted to the amides compound in environmental water sample using the mode of SPME, passes through
To ensure the stability of effect of extracting using suitable extraction temperature and extract ph value, so that the detection side that the present invention provides
Method has stable recovery of standard addition.Test result indicate that, the present invention provide detection method recovery of standard addition be 92～
97%, recovery of standard addition is relatively stable.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this
Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing providing obtains other accompanying drawings.
The sim figure of five kinds of amides compounds that Fig. 1 provides for embodiment 1.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation description is it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of not making creative work
Embodiment, broadly falls into the scope of protection of the invention.
The invention provides in a kind of environmental water sample amides compound detection method, comprise the following steps:
A), environmental water sample is mixed with alkali and sodium chloride, obtains environmental water sample liquid to be extracted；
The ph value of described environmental water sample liquid to be extracted is 10～11；
B), using extraction optical fiber, to described environmental water sample, liquid to be extracted carries out SPME, obtains environmental water sample extraction
Sample；
The temperature of described SPME is 70～80 DEG C；
C), the described environmental water sample of detection extracts sample, obtains in environmental water sample the species of contained amides compound and/or contains
Amount.
The present invention provide detection method in, first water pretreatment is entered to environmental water sample, this process is: environmental water sample with
Alkali and sodium chloride mixing.Wherein, described environmental water sample is preferably the earth's surface water sample extracting from cultivation region and/or sampling of ground water.?
In the embodiment that the present invention provides, in described environmental water sample, contain amides compound.The reality providing in the present invention
Apply in example, described amides compound includes one of Acetochlor, alachlor, propisochlor, butachlor and pretilachlor or many
Kind；In another embodiment that the present invention provides, described amides compound includes Acetochlor, alachlor and butachlor.?
The environmental water sample that the present invention provides includes in the embodiment of Acetochlor, alachlor and butachlor, the concentration of described Acetochlor
For 0.1～105μ g/l, the concentration of described alachlor is 0.1～105μ g/l, the concentration of described butachlor is 0.01～105μg/l；
Another environmental water sample providing in the present invention includes in the embodiment of Acetochlor, alachlor and butachlor, described Acetochlor
Concentration is 0.1～104μ g/l, the concentration of described alachlor is 0.1～104μ g/l, the concentration of described butachlor is 0.01～104μ
g/l；Other environmental water samples providing in the present invention include in the embodiment of Acetochlor, alachlor and butachlor, described Acetochlor
Concentration be 0.3～4000 μ g/l, the concentration of described alachlor is 0.2～4000 μ g/l, the concentration of described butachlor is 0.3～
4000μg/l.Described alkali is preferably one or more of NaOH, potassium hydroxide and lithium hydroxide, more preferably hydroxide
Sodium.After environmental water sample is mixed with alkali and sodium chloride, obtain environmental water sample liquid to be extracted.Described environmental water sample liquid to be extracted
Ph value be 9～11, preferably 9.5～10.5, more preferably 10～10.5.Sodium chloride in described environmental water sample liquid to be extracted
Concentration is preferably 0.3～0.36g/ml, more preferably 0.35～0.36g/ml.
In the present invention, before described environmental water sample is mixed with alkali and sodium chloride, preferably first described environmental water sample is carried out
Filter, the filtrate being filtrated to get is mixed with alkali and sodium chloride again.The mode of described filtration is preferably membrane filtration.In the present invention
In, the purpose of filtration is to remove the suspension in water sample.
In the present invention.Before described environmental water sample is filtered, preferably first described environmental water sample is centrifuged, centrifugation
The supernatant liquor obtaining is filtered again.In the present invention, the purpose of centrifugation is to remove the solid impurity in water sample.
After obtaining environmental water sample liquid to be extracted, using extraction optical fiber, to described environmental water sample, liquid to be extracted carries out the micro- extraction of solid phase
Take.The temperature of described SPME is 70～80 DEG C, preferably 75～80 DEG C.The coating of described extraction optical fiber is preferably
pdms/dvb.The coating layer thickness of described extraction optical fiber is preferably 60～70 μm, more preferably 60～65 μm.Described SPME
Mode be preferably headspace solid-phase microextraction.The time of described headspace solid-phase microextraction preferably 30～50min, more preferably 40
～50min.During SPME, the liquid to be extracted of environmental water sample described in preferred pair is stirred, and the speed of described stirring is excellent
Elect 300～500 revs/min as, more preferably 400～500 revs/min.In the present invention, to environmental water sample, liquid to be extracted is carried out
Stirring is in order that environmental water sample liquid to be extracted composition during SPME keeps uniformly.
In the present invention, using extraction optical fiber before to described environmental water sample, liquid to be extracted carries out SPME, preferably
First described extraction optical fiber is carried out aging.The described aging time is preferably 10～30min, more preferably 20～30min.Described
Aging temperature is preferably 220～270 DEG C, more preferably 250～260 DEG C.
After SPME terminates, obtain environmental water sample extraction sample, the described environmental water sample of detection extracts sample, obtains ambient water
The species of contained amides compound and/or content in sample.
In the present invention, the described environmental water sample of detection extracts the mode preferably gas chromatography-mass spectrography detection of sample.Its
In, the chromatographic column adopting during described gas chromatographic detection is preferably quartzy capillary column, the more preferably db- of middle polarity
35ms elastic quartz capillary column.The length of described chromatographic column is preferably 20～50m, more preferably 30～40m；Described chromatographic column
Internal diameter is preferably 0.1～0.5mm, more preferably 0.25～0.3mm；The thickness of described chromatographic column is preferably 0.1～0.5 μm, more
It is preferably 0.25～0.3 μm.Injector temperature during described gas chromatographic detection is preferably 200～300 DEG C, more preferably
For 240～250 DEG C.The carrier gas using during described gas chromatographic detection is preferably nitrogen.The flow velocity of described carrier gas is preferred
For 0.5～2ml/min, more preferably 1～1.5ml/min.During described gas chromatographic detection, input mode is not preferably
Split sampling.Transmission line temperature during described gas chromatographic detection is preferably 250～300 DEG C, more preferably 280～
300℃.Preferably carry out temperature programming in the following manner during described gas chromatographic detection:
After chromatographic column is with the first temperature very first time, heated up, after being warmed up to second temperature, be incubated for the second time.
The described very first time is preferably arranged to 80～120 DEG C, more preferably 90～100 DEG C；Described first temperature is preferably arranged to 0.5～
5min, is more preferably set to 0.5～1min；Described second temperature is preferably 230～280 DEG C, more preferably 250～260 DEG C；Institute
Second time of stating is preferably 3～10min, more preferably 5～7min；Preferably 10～30 DEG C of the heating rate of described intensification/
Min, more preferably 15～20 DEG C/min.
During described Mass Spectrometer Method, ion source temperature is preferably 200～250 DEG C, more preferably 230～250 DEG C.Described
The mode of Mass Spectrometer Method is preferably level Four bar Mass Spectrometer Method, and during described level Four bar Mass Spectrometer Method, level Four bar temperature is preferably
130～180 DEG C, more preferably 150～160 DEG C.During described Mass Spectrometer Method, mass spectrum ionization mode is preferably ei.Described mass spectrum
In detection process, electron ionization ability is preferably 50～90ev, more preferably 65～70ev.Double during described Mass Spectrometer Method
Voltage is preferably 1000～1300v, more preferably 1100～1200v.During described Mass Spectrometer Method, sample mode is preferably electricity
Ion (sim) and/or full scan (scan), more preferably electron ion (sim) and full scan (scan).Described Mass Spectrometer Method process
Middle mass scan range is preferably 20～400m/z.
The embodiment adopting the described environmental water sample of gas chromatography-mass spectrography detection to extract sample providing in the present invention
In, in the following ways qualitative detection carried out to environmental water sample extraction sample:
Environmental water sample extraction sample carries out gas chromatography-mass spectrography detection, obtains chromatogram and the ambient water of environmental water sample
The mass spectrogram of sample；Standard sample extraction sample carries out gas chromatography-mass spectrography detection, the chromatogram getting standard samples and standard
The mass spectrogram of sample.
Described standard sample extraction sample is obtained by standard sample.In the present invention, described standard sample prepares standard sample
The operating procedure of extraction sample and Parameter Conditions prepare, with above-mentioned environmental water sample, operating procedure and the parameter bar that environmental water sample extracts sample
Part is consistent.The species of described standard sample includes but is not limited to Acetochlor, alachlor, propisochlor, fourth draft and pretilachlor
One or more of.The concentration of described standard sample is preferably 1～1000mg/l, more preferably 2～100mg/l.
By comparing the appearance time of each component and environment in the chromatogram of environmental water sample and the chromatogram of standard sample
The m/z of each component in the mass spectrogram of the mass spectrogram of water sample and standard sample, it is fixed that the amides compound in environmental water sample is carried out
Property detection, obtain the species of contained amides compound in environmental water sample.
The embodiment adopting the described environmental water sample of gas chromatography-mass spectrography detection to extract sample providing in the present invention
In, in the following ways quantitative determination carried out to environmental water sample extraction sample:
Environmental water sample extraction sample carries out gas chromatography-mass spectrography detection, obtains the chromatogram of environmental water sample, and calculates color
The chromatographic peak area of each material in spectrogram；A series of standard sample extraction sample of variable concentrations carries out gas chromatography-mass spectrum respectively
Combination detection, the chromatogram getting standard samples, and the chromatographic peak area of computer chromatography in figure standard sample, according to standard sample
Concentration and the corresponding relation of chromatographic peak area, Criterion curve.
A series of standard sample extraction sample of described variable concentrations is obtained by a series of standard sample of variable concentrations.At this
In invention, a series of standard sample of described variable concentrations prepares a series of operation of the extraction sample of the standard sample of variable concentrations
Step and Parameter Conditions and above-mentioned environmental water sample prepare that environmental water sample extracts the operating procedure of sample and Parameter Conditions are consistent.Described
The species of standard sample includes but is not limited to one of Acetochlor, alachlor, propisochlor, butachlor and pretilachlor or many
Kind.In the embodiment that the present invention provides, a series of standard sample of described variable concentrations is a series of variable concentrations
Acetochlor standard sample, a series of alachlor standard sample of variable concentrations, a series of propisochlor standard sample of variable concentrations
Product, a series of butachlor standard sample of variable concentrations, a series of pretilachlor standard sample of variable concentrations.There is provided in the present invention
An embodiment in, a series of Acetochlor standard sample of described variable concentrations is by the Acetochlor standard sample of 5 variable concentrations
Product form, and its concentration is followed successively by 2mg/l, 10mg/l, 20mg/l, 50mg/l, 100mg/l.The enforcement providing in the present invention
In example, a series of alachlor standard sample of described variable concentrations is made up of the alachlor standard sample of 5 variable concentrations, and it is dense
Degree is followed successively by 2mg/l, 10mg/l, 20mg/l, 50mg/l, 100mg/l.In the embodiment that the present invention provides, described one
The propisochlor standard sample of serial variable concentrations is made up of the propisochlor standard sample of 5 variable concentrations, and its concentration is successively
For 2mg/l, 10mg/l, 20mg/l, 50mg/l, 100mg/l.The present invention provide an embodiment in, described a series of not
Butachlor standard sample with concentration is made up of the butachlor standard sample of 5 variable concentrations, its concentration be followed successively by 2mg/l,
10mg/l、20mg/l、50mg/l、100mg/l.In the embodiment that the present invention provides, a series of described variable concentrations
Pretilachlor standard sample is made up of the pretilachlor standard sample of 5 variable concentrations, its concentration be followed successively by 2mg/l, 10mg/l,
20mg/l、50mg/l、100mg/l.
The chromatographic peak area of the environmental water sample being obtained according to gas chromatography-mass spectrography detection and the calibration curve meter set up
Calculate the content obtaining contained amides compound in environmental water sample.
The present invention is directly extracted to the amides compound in environmental water sample using the mode of SPME, passes through
To improve the stability of effect of extracting using suitable extraction temperature and extract ph value, so that the detection side that the present invention provides
Method has stable recovery of standard addition.Test result indicate that, the present invention provide detection method recovery of standard addition be 92～
97%, recovery of standard addition is relatively stable.
For the sake of becoming apparent from, it is described in detail below by following examples.
Embodiment 1
The gas chromatography mass spectrometry detection of standard sample
Acetochlor, alachlor, propisochlor, butachlor and the pretilachlor standard liquid being 1mg/ml by 5ml concentration respectively
Add in different 20ml ml headspace bottle, adjusting solution ph is 10.5, adds stirrer, adds the chlorination of saturation capacity in solution
Sodium, after gland sealing, will extract the injection port in ml headspace bottle for the optical fiber (coating layer thickness is 65 μm, and coating material is pdms/dvb)
Aging 20min at 250 DEG C, then will extract optical fiber insertion ml headspace bottle, and be placed in ml headspace bottle afterwards and be furnished with magnetic stirring apparatus
Extract in water bath with thermostatic control.Setting mixing speed is 400 revs/min, adjusts bath temperature to 75 DEG C, controls extraction time 40min.
After extraction finishes, the injection port that extraction optical fiber is inserted directly into gc-ms detector (agilent 5975-6890n) carries out 3min
Thermal desorption, detected in gc-ms detector after sample thermal desorption, the gas chromatographic detection result getting standard samples and
Mass Spectrometer Method result.In experimentation, keep extraction pin every time consistent with the insertion depth of injection port in ml headspace bottle.
Gas chromatographic detection condition: adopt the db-35ms elastic quartz capillary column of middle polarity, its The concrete specification in experiment
For 30m × 0.25mm × 0.25 μm；Temperature programming: 100 DEG C of post initial temperature, keep 1min, be warming up to 260 with 15 DEG C/min
DEG C, keep 5min；Injector temperature is 250 DEG C；Carrier gas is high-purity helium (> 99.999%)；Flow rate of carrier gas: 1.0ml/min；Adopt
With Splitless injecting samples, after 1min, drive blow down valve；280 DEG C of transmission line temperature.
Mass Spectrometer Method condition: ion source temperature: 230 DEG C；Level Four bar temperature: 150；Mass spectrum ionization mode is ei；Electronics electricity
It is 70ev from energy；Multiplier electrode: 1100v；Acquisition mode is single ion (sim) and full scan (scan) combines；Quality is swept
Retouch scope: 20～400m/z.
The testing result of chromatography of gases is as shown in figure 1, the sim of five kinds of amides compounds that provides for embodiment 1 of Fig. 1
Figure, wherein, when 1 expression the first appearance time, 2 expression the second appearance times, 3 expression the 3rd appearance times, 4 expression four appearance
Between, 5 expression the 5th appearance times.
Mass Spectrometer Method result is: the corresponding m/z of the first appearance time is 146, and the corresponding m/z of the second appearance time is 160,
The corresponding m/z of 3rd appearance time is 238, and the corresponding m/z of the 4th appearance time is 176, and the corresponding m/z of the 5th appearance time is
162.
In conjunction with gas-chromatography and Mass Spectrometer Method result and nist 2008 standard mass spectrometric data (referring to table 1) it is known that:
The corresponding material of first appearance time is Acetochlor, and the corresponding material of the second appearance time is alachlor, and the 3rd goes out
The corresponding material of peak time is propisochlor, and the corresponding material of the 4th appearance time is butachlor, and the 5th appearance time is corresponding
Material is pretilachlor.
Table 1nist 2008 standard mass spectrometric data
Embodiment 2
The foundation of calibration curve
First, prepare series of standards solution according to table 2 concentration；
Table 2 series of standards solution concentration table
Above-mentioned each standard liquid 5ml is taken to be separately added in different 20ml ml headspace bottle, adjusting solution ph is 10.5, adds
Stirrer, adds the sodium chloride of saturation capacity in solution, and after gland sealing, (coating layer thickness is 65 μm, coating will to extract optical fiber
Material be pdms/dvb) ml headspace bottle injection port at 250 DEG C aging 20min, then will extract optical fiber insert ml headspace bottle, it
Afterwards ml headspace bottle is placed in extraction in the water bath with thermostatic control be furnished with magnetic stirring apparatus.Setting mixing speed is 400 revs/min, adjusts water
Bath temperature to 75 DEG C, control extraction time 40min.After extraction finishes, extraction optical fiber is inserted directly into gc-ms detector
The injection port of (agilent 5975-6890n) carries out the thermal desorption of 3min, carries out after sample thermal desorption in gc-ms detector
Detection, obtains gas chromatographic detection result and Mass Spectrometer Method result.In experimentation, extraction pin every time is kept in ml headspace bottle and to enter
The insertion depth of sample mouth is consistent.
Gas chromatographic detection condition: adopt the db-35ms elastic quartz capillary column of middle polarity, its The concrete specification in experiment
For 30m × 0.25mm × 0.25 μm；Temperature programming: 100 DEG C of post initial temperature, keep 1min, be warming up to 260 with 15 DEG C/min
DEG C, keep 5min；Injector temperature is 250 DEG C；Carrier gas is high-purity helium (> 99.999%)；Flow rate of carrier gas: 1.0ml/min；Adopt
With Splitless injecting samples, after 1min, drive blow down valve；280 DEG C of transmission line temperature.
Mass Spectrometer Method condition: ion source temperature: 230 DEG C；Level Four bar temperature: 150；Mass spectrum ionization mode is ei；Electronics electricity
It is 70ev from energy；Multiplier electrode: 1100v；Acquisition mode is single ion (sim) and full scan (scan) combines；Quality is swept
Retouch scope: 20～400m/z.
Concentration according to above-mentioned each standard liquid and the corresponding relation of chromatographic peak area, set up Acetochlor, alachlor, isopropyl
Careless amine, butachlor, the calibration curve of pretilachlor, concrete outcome is shown in Table 3.
The calibration curve of the different amides compound of table 3
In table 3, x is the concentration of amides compound, and y is chromatographic peak area, and detection limit to be inferred by signal to noise ratio s/n=3
Embodiment 3
The quantitative determination of environmental water sample
Take environmental water sample 10ml to be measured in centrifuge tube, centrifuge is centrifuged 5min with 4000 turns/min, and upper liquid is through water
Phase filter membrane oil removal.5ml filtrate is taken to add in 20ml ml headspace bottle, adjusting solution ph is 10.5, adds stirrer, to solution
The middle sodium chloride adding saturation capacity, after gland sealing, (coating layer thickness is 65 μm, and coating material is pdms/ will to extract optical fiber
Dvb) ml headspace bottle injection port at 250 DEG C aging 20min, then will extract optical fiber insertion ml headspace bottle, afterwards by ml headspace bottle
It is placed in extraction in the water bath with thermostatic control be furnished with magnetic stirring apparatus.Setting mixing speed is 400 revs/min, adjusts bath temperature to 75
DEG C, control extraction time 40min.After extraction finishes, extraction optical fiber is inserted directly into gc-ms detector (agilent 5975-
Injection port 6890n) carries out the thermal desorption of 3min, carries out qualitative and quantitative determination after sample thermal desorption in gc-ms detector.
Wherein, during qualitative detection, the standard sample Mass Spectrometer Method result of reference and standard sample gas chromatographic detection result are to implement
Acetochlor, alachlor, the Mass Spectrometer Method result of propisochlor, butachlor and pretilachlor standard liquid and the gas phase obtaining in example 1
Chromatogram testing result, during quantitative determination, the calibration curve of reference is the calibration curve that embodiment 2 is set up.In experimentation,
Keep extraction pin consistent with embodiment 2 with the insertion depth of injection port in ml headspace bottle.
Gas chromatographic detection condition: adopt the db-35ms elastic quartz capillary column of middle polarity, its The concrete specification in experiment
For 30m × 0.25mm × 0.25 μm；Temperature programming: 100 DEG C of post initial temperature, keep 1min, be warming up to 260 with 15 DEG C/min
DEG C, keep 5min；Injector temperature is 250 DEG C；Carrier gas is high-purity helium (> 99.999%)；Flow rate of carrier gas: 1.0ml/min；Adopt
With Splitless injecting samples, after 1min, drive blow down valve；280 DEG C of transmission line temperature.
Mass Spectrometer Method condition: ion source temperature: 230 DEG C；Level Four bar temperature: 150；Mass spectrum ionization mode is ei；Electronics electricity
It is 70ev from energy；Multiplier electrode: 1100v；Acquisition mode is single ion (sim) and full scan (scan) combines；Quality is swept
Retouch scope: 20～400m/z.
Gc-ms testing result is: in environmental water sample to be measured Acetochlor concentration be 0.45 μ g/l, alachlor concentration be 0.27 μ
G/l, butachlor concentration are 0.82 μ g/l, do not contain propisochlor and pretilachlor.
Embodiment 4
The quantitative determination of environmental water sample
Take environmental water sample 10ml to be measured in centrifuge tube, centrifuge is centrifuged 5min with 4000 turns/min, and upper liquid is through water
Phase filter membrane oil removal.5ml filtrate is taken to add in 20ml ml headspace bottle, adjusting solution ph is 10.5, adds stirrer, to solution
The middle sodium chloride adding saturation capacity, after gland sealing, (coating layer thickness is 65 μm, and coating material is pdms/ will to extract optical fiber
Dvb) ml headspace bottle injection port at 250 DEG C aging 20min, then will extract optical fiber insertion ml headspace bottle, afterwards by ml headspace bottle
It is placed in extraction in the water bath with thermostatic control be furnished with magnetic stirring apparatus.Setting mixing speed is 400 revs/min, adjusts bath temperature to 75
DEG C, control extraction time 40min.After extraction finishes, extraction optical fiber is inserted directly into gc-ms detector (agilent 5975-
Injection port 6890n) carries out the thermal desorption of 3min, carries out qualitative and quantitative determination after sample thermal desorption in gc-ms detector.
Wherein, during qualitative detection, the standard sample Mass Spectrometer Method result of reference and standard sample gas chromatographic detection result are to implement
Acetochlor, alachlor, the Mass Spectrometer Method result of propisochlor, butachlor and pretilachlor standard liquid and the gas phase obtaining in example 1
Chromatogram testing result, during quantitative determination, the calibration curve of reference is the calibration curve that embodiment 2 is set up.In experimentation,
Keep extraction pin consistent with embodiment 2 with the insertion depth of injection port in ml headspace bottle.
Gas chromatographic detection condition: adopt the db-35ms elastic quartz capillary column of middle polarity, its The concrete specification in experiment
For 30m × 0.25mm × 0.25 μm；Temperature programming: 100 DEG C of post initial temperature, keep 1min, be warming up to 260 with 15 DEG C/min
DEG C, keep 5min；Injector temperature is 250 DEG C；Carrier gas is high-purity helium (> 99.999%)；Flow rate of carrier gas: 1.0ml/min；Adopt
With Splitless injecting samples, after 1min, drive blow down valve；280 DEG C of transmission line temperature.
Mass Spectrometer Method condition: ion source temperature: 230 DEG C；Level Four bar temperature: 150；Mass spectrum ionization mode is ei；Electronics electricity
It is 70ev from energy；Multiplier electrode: 1100v；Acquisition mode is single ion (sim) and full scan (scan) combines；Quality is swept
Retouch scope: 20～400m/z.
Gc-ms testing result is: in environmental water sample to be measured Acetochlor concentration be 0.53 μ g/l, alachlor concentration be 1.1 μ g/
L, butachlor concentration are 0.45 μ g/l, do not contain propisochlor and pretilachlor.
Embodiment 5
The quantitative determination of environmental water sample
Take environmental water sample 10ml to be measured in centrifuge tube, centrifuge is centrifuged 5min with 4000 turns/min, and upper liquid is through water
Phase filter membrane oil removal.5ml filtrate is taken to add in 20ml ml headspace bottle, adjusting solution ph is 10.5, adds stirrer, to solution
The middle sodium chloride adding saturation capacity, after gland sealing, (coating layer thickness is 65 μm, and coating material is pdms/ will to extract optical fiber
Dvb) ml headspace bottle injection port at 250 DEG C aging 20min, then will extract optical fiber insertion ml headspace bottle, afterwards by ml headspace bottle
It is placed in extraction in the water bath with thermostatic control be furnished with magnetic stirring apparatus.Setting mixing speed is 400 revs/min, adjusts bath temperature to 75
DEG C, control extraction time 40min.After extraction finishes, extraction optical fiber is inserted directly into gc-ms detector (agilent 5975-
Injection port 6890n) carries out the thermal desorption of 3min, carries out qualitative and quantitative determination after sample thermal desorption in gc-ms detector.
Wherein, during qualitative detection, the standard sample Mass Spectrometer Method result of reference and standard sample gas chromatographic detection result are to implement
Acetochlor, alachlor, the Mass Spectrometer Method result of propisochlor, butachlor and pretilachlor standard liquid and the gas phase obtaining in example 1
Chromatogram testing result, during quantitative determination, the calibration curve of reference is the calibration curve that embodiment 2 is set up.In experimentation,
Keep extraction pin consistent with embodiment 2 with the insertion depth of injection port in ml headspace bottle.
Gas chromatographic detection condition: adopt the db-35ms elastic quartz capillary column of middle polarity, its The concrete specification in experiment
For 30m × 0.25mm × 0.25 μm；Temperature programming: 100 DEG C of post initial temperature, keep 1min, be warming up to 260 with 15 DEG C/min
DEG C, keep 5min；Injector temperature is 250 DEG C；Carrier gas is high-purity helium (> 99.999%)；Flow rate of carrier gas: 1.0ml/min；Adopt
With Splitless injecting samples, after 1min, drive blow down valve；280 DEG C of transmission line temperature.
Mass Spectrometer Method condition: ion source temperature: 230 DEG C；Level Four bar temperature: 150；Mass spectrum ionization mode is ei；Electronics electricity
It is 70ev from energy；Multiplier electrode: 1100v；Acquisition mode is single ion (sim) and full scan (scan) combines；Quality is swept
Retouch scope: 20～400m/z.
Gc-ms testing result is: in environmental water sample to be measured Acetochlor concentration be 0.34 μ g/l, alachlor concentration be 1.8 μ g/
L, butachlor concentration are 0.33 μ g/l, do not contain propisochlor and pretilachlor.
Embodiment 6
Recovery of standard addition
Carry out the test of recovery of standard addition by the way of blank sample mark-on.From not containing Acetochlor, alachlor, different
The secondary deionized water of pretilachlor, butachlor and pretilachlor, adds a certain amount of amides compound, obtains mark-on prepare liquid.
In described mark-on prepare liquid, the content of Acetochlor is 3.9 μ g/ml, and the content of alachlor is 4.01 μ g/ml, the content of propisochlor
For 4.20 μ g/ml, the content of butachlor is 3.92 μ g/ml, and the content of pretilachlor is 3.87 μ g/ml.
Take in the 20ml ml headspace bottle that 5ml above-mentioned mark-on prepare liquid adds, adjusting solution ph is 10.5, adds stirrer,
Add the sodium chloride of saturation capacity in solution, after gland sealing, (coating layer thickness is 65 μm, and coating material is will to extract optical fiber
Pdms/dvb) ml headspace bottle injection port at 250 DEG C aging 20min, then will extract optical fiber insertion ml headspace bottle, will push up afterwards
Empty bottle is placed in extraction in the water bath with thermostatic control be furnished with magnetic stirring apparatus.Setting mixing speed is 400 revs/min, adjusts bath temperature
To 75 DEG C, control extraction time 40min.After extraction finishes, extraction optical fiber is inserted directly into gc-ms detector
(agilent5975-6890n) injection port carries out the thermal desorption of 3min, and it is fixed to carry out in gc-ms detector after sample thermal desorption
Property and quantitative determination.Wherein, the standard sample Mass Spectrometer Method result of reference and standard sample gas-chromatography during qualitative detection
Testing result is the Acetochlor of acquisition, alachlor, the mass spectrum of propisochlor, butachlor and pretilachlor standard liquid in embodiment 1
Testing result and gas-chromatography testing result, during quantitative determination, the calibration curve of reference is that the standard that embodiment 2 is set up is bent
Line.In experimentation, keep extraction pin consistent with embodiment 2 with the insertion depth of injection port in ml headspace bottle.
Gas chromatographic detection condition: adopt the db-35ms elastic quartz capillary column of middle polarity, its The concrete specification in experiment
For 30m × 0.25mm × 0.25 μm；Temperature programming: 100 DEG C of post initial temperature, keep 1min, be warming up to 260 with 15 DEG C/min
DEG C, keep 5min；Injector temperature is 250 DEG C；Carrier gas is high-purity helium (> 99.999%)；Flow rate of carrier gas: 1.0ml/min；Adopt
With Splitless injecting samples, after 1min, drive blow down valve；280 DEG C of transmission line temperature.
Mass Spectrometer Method condition: ion source temperature: 230 DEG C；Level Four bar temperature: 150；Mass spectrum ionization mode is ei；Electronics electricity
It is 70ev from energy；Multiplier electrode: 1100v；Acquisition mode is single ion (sim) and full scan (scan) combines；Quality is swept
Retouch scope: 20～400m/z.
Gc-ms testing result and recovery of standard addition result are as shown in table 4.Data in table 4 is contained in mark-on prepare liquid
Contained amides compound in the mark-on prepare liquid that the theoretical value of amides compound, mark-on prepare liquid obtain after tested
Measured value and calculated recovery of standard addition.
The theoretical value of amides compound content, measured value and corresponding recovery of standard addition in table 4 mark-on prepare liquid
It can be seen from Table 4 that, the detection method that the present invention provides has stable recovery of standard addition.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. in a kind of environmental water sample amides compound detection method, comprise the following steps:
A), environmental water sample is mixed with alkali and sodium chloride, obtains environmental water sample liquid to be extracted；
The ph value of described environmental water sample liquid to be extracted is 9～11；In described environmental water sample liquid to be extracted, the concentration of sodium chloride is 0.3
～0.36g/ml；
B), using the extraction optical fiber for pdms/dvb for the coating, to described environmental water sample, liquid to be extracted carries out headspace solid-phase microextraction,
Obtain environmental water sample extraction sample；
The temperature of described SPME is 70～80 DEG C；
C), the described environmental water sample of detection extracts sample, obtains the species of contained amides compound and/or content in environmental water sample；
Described amides compound includes Acetochlor, alachlor and butachlor.
2. detection method according to claim 1 it is characterised in that described headspace solid-phase microextraction time be 30～
50min.
3. detection method according to claim 1 is it is characterised in that the coating layer thickness of described extraction optical fiber is 60～70 μ
m.
4. detection method according to claim 1 is it is characterised in that in step a), described environmental water sample and alkali and chlorination
Before sodium mixing, first described environmental water sample is filtered.
5. detection method according to claim 1 is it is characterised in that in step b), using extraction optical fiber to described environment
Before water sample liquid to be extracted carries out SPME, first described extraction optical fiber is carried out aging.
6. detection method according to claim 5 is it is characterised in that the described aging time is 10～30min.
7. the detection method according to any one of claim 1～6 is it is characterised in that in step c), detect described ambient water
The mode that sample extracts sample detects for gas chromatography-mass spectrography.
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