CN109507316A - A kind of screening method of water pollutant - Google Patents
A kind of screening method of water pollutant Download PDFInfo
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- CN109507316A CN109507316A CN201811375550.6A CN201811375550A CN109507316A CN 109507316 A CN109507316 A CN 109507316A CN 201811375550 A CN201811375550 A CN 201811375550A CN 109507316 A CN109507316 A CN 109507316A
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- 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
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- 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
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Abstract
A kind of water pollutant screening method, comprising: the sample to be tested obtained from water sample to be measured；Two-dimensional gas chromatography analysis is carried out to sample to be tested, obtains intermediate analysis object；A part of intermediate analysis object is generated into the ion of different mass-to-charge ratioes through the bombardment of EI ion source, and is analyzed by mass spectrometry, the first spectrogram arranged by mass-to-charge ratio size order is obtained；Another part carries out ECD and detects to obtain the second spectrogram；The first spectrogram is screened using mass spectrum differential technique, it is compared with the second spectrogram, if there is the useful signal that expression may be organic chloride, organic bromide or nitro substituent in the selection result through mass spectrum differential technique, and second there is also the useful signals in spectrogram, then confirmatory sample contains organic chloride, organic bromide or nitro substituent.This method can quickly and easily realize that chlorine replaces (- Cl) organic pollutant, bromine that (- Br) organic pollutant, nitro is replaced to replace (- NO2) organic pollutant reliable screening.
Description
Technical field
The present invention relates to the screenings of water pollutant, more particularly to a kind of screening method of water pollutant.
Background technique
Currently, frequently detecting that chlorine replaces (- Cl) organic pollutant, bromine that (- Br) is replaced to have in stain disease and surface water
Machine pollutant, nitro replace (- NO2) organic pollutant etc..These water pollutant bring life are caused with health risk
The extensive concern of people.Most of chlorine replace (- Cl) organic pollutants, bromine replace (- Br) organic pollutant, nitro replace (-
NO2) organic pollutant has the characteristics that strong toxicity, difficult to degrade.The screening of Organic Pollutants In Water is outstanding to guarantee water quality safety
It is important.
Existing chlorine replaces (- Cl) organic pollutant, bromine that (- Br) organic pollutant, nitro is replaced to replace (- NO2) organic
Detection (GC-MS/MS) is used in conjunction in the bis- mass spectrums of the detection method of pollutant, mainly gas-chromatography-or the bis- mass spectrums of liquid chromatogram-connect
With detection (LC-MS/MS) method.However, GC-MS/MS scanning speed is inadequate, and instrument price is expensive；LC-MS/MS detection
Mainly for non-volatile organic pollutant, and instrument price is expensive, cumbersome.Therefore still lack rapid screening chlorine at present to take
Generation (- Cl) organic pollutant, bromine replace (- Br) organic pollutant, nitro to replace (- NO2) organic pollutant method.
The disclosure of background above technology contents is only used for auxiliary and understands inventive concept and technical solution of the invention, not
The prior art for necessarily belonging to present patent application shows above content in the applying date of present patent application in no tangible proof
In the case where having disclosed, above-mentioned background technique should not be taken to the novelty and creativeness of evaluation the application.
Summary of the invention
It is a primary object of the present invention to overcome the deficiencies of the prior art and provide a kind of water pollutant screening method.
To achieve the above object, the invention adopts the following technical scheme:
A kind of water pollutant screening method, comprising the following steps:
S1, the sample to be tested obtained from water sample to be measured；
S2, two-dimensional gas chromatography analysis is carried out to the sample to be tested, obtains intermediate analysis object；
S3, the intermediate analysis object are divided into two parts, and a part of the intermediate analysis object is bombarded through EI ion source
The ion of different mass-to-charge ratioes (m/z) is generated, and is analyzed by mass spectrometry (MS), obtains the first spectrum arranged by mass-to-charge ratio size order
Figure；Another part of the intermediate analysis object is carried out ECD to detect to obtain the second spectrogram；
S4, first spectrogram is screened using mass spectrum differential technique, is compared with second spectrogram, if through matter
It composes and there is effective letter that expression may be organic chloride, organic bromide or nitro substituent in the selection result of differential technique
Number, and there is also the useful signals in second spectrogram, it is determined that the sample to be tested correspondingly contain organic chloride,
Organic bromide or nitro substituent.
Further, the water pollutant screening method is further comprising the steps of:
S5, the pollutant filtered out in step S4 is compared with NIST spectrum library, further to identify material composition.
Further, the mass spectrum differential technique includes:
For the sum of known mass-to-charge ratio x and m, wherein m takes any one of following numerical value:
35/37/46/70/72/74/79/81/105/107/109/111/114/116/118/149/151/153/155/
158/160/162/193/195/197/199/237/239/241/243
If corresponding to the effective signal of x+m subject to confirmation in first spectrogram, if hereinafter referred to as x+m has signal,
In include following scenario described:
If x+35/37 (1Cl35/1Cl37) there is signal, then signal expression may have a chlorine substituent, wherein numerical value 35/
37 correspond to 1Cl35/1Cl37；
If x+70/72/74 (2Cl35/1Cl35+1Cl37/2Cl37) there is signal, then signal expression may have dichloro substitution
Object, wherein numerical value 70/72/74 corresponds to 2Cl35/1Cl35+1Cl37/2Cl37；
If x+105/107/109/111 (3Cl35/2Cl35+1Cl37/1Cl35+2Cl37/3Cl37) there is signal, then the signal table
Trichlorine substituent may be had by showing, wherein numerical value 105/107/109/111 corresponds to 3Cl35/2Cl35+1Cl37/1Cl35+2Cl37/
3Cl37；
If x+79/81 (1Br79/1Br81) there is signal, then signal expression may have monobromo substituent, wherein numerical value 79/
81 correspond to 1Br79/1Br81；
If x+158/160/162 (2Br79/1Br79+1Br81/2Br81) there is signal, then signal expression may have dibromo to take
For object, wherein numerical value 158/160/162 corresponds to 2Br79/1Br79+1Br81/2Br81；
If x+237/239/241/243 (3Br79/2Br79+1Br81/1Br79+2Br81/3Br81) there is signal, then the signal table
Tribromo substituent may be had by showing, wherein numerical value 237/239/241/243 corresponds to 3Br79/2Br79+1Br81/1Br79+2Br81/
3Br81；
If x+114/116/118 (1Cl35+1Br79/1Cl37+1Br79(1Cl35+1Br81)/1Cl37+1Br81) there is signal, then
Signal expression may have a chlorine monobromo substituent, and wherein numerical value 114/116/118 corresponds to 1Cl35+1Br79/1Cl37+1Br79
(1Cl35+1Br81)/1Cl37+1Br81；
If x+149/151/153/155 (2Cl35+1Br79/1Cl35+1Cl37+1Br79(2Cl35+1Br81)/1Cl35+1Cl37+
1Br81(2Cl37+1Br79)/2Cl37+1Br81) there is signal, then signal expression may have Dichloro-monobromo substituent, wherein numerical value
149/151/153/155 corresponds to 2Cl35+1Br79/1Cl35+1Cl37+1Br79(2Cl35+1Br81)/1Cl35+1Cl37+1Br81
(2Cl37+1Br79)/2Cl37+1Br81；
If x+193/195/197/199 (1Cl35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+
1Br81(1Cl35+2Br81)/1Cl37+2Br81) there is signal, then signal expression may have a chlorine dibromo substituent, wherein numerical value
193/195/197/199 corresponds to 1Cl35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+1Br81
(1Cl35+2Br81)/1Cl37+2Br81；
If x+46 (- NO2) there is signal, then signal expression may have nitro substituent, and wherein numerical value 46 corresponds to-NO2；
Wherein, Cl35Indicate that relative atomic mass is 35 chlorine atom, Cl37The chlorine for indicating that relative atomic mass is 37 is former
Son, Br79Indicate that relative atomic mass is 79 bromine atom, Br81Indicate that relative atomic mass is 81 bromine atom, N indicates opposite
The nitrogen-atoms that atomic mass is 14, O indicate that relative atomic mass is 16 nitrogen-atoms.
Further, the total number at peak obtained in first spectrogram, P are indicated with niIt indicates to obtain in first spectrogram
I-th of the peak arrived, PjIndicate j-th of peak obtained in first spectrogram, i, j=1,2 ..., n, and i < j, PxIndicate described
X-th of peak obtained in two spectrograms；
The step S4 is further included steps of
S41, from first peak P in first spectrogram1Start, by i-th of peak PiMass-to-charge ratio and the sum of m with j-th
Peak PjMass-to-charge ratio be compared, if comparison result is equal, enter step S42；
S42, judge Pi、PjSignal-to-noise ratio whether be greater than setting snr threshold and whether relative abundance is greater than setting phase
To abundance threshold value, if Pi、PjSignal-to-noise ratio be greater than setting snr threshold, and relative abundance be greater than setting relative abundance threshold value,
Then judge Pi、PjFor useful signal, S43 is entered step, otherwise return step S41；
S43, judge in second spectrogram with the presence or absence of appearance time and PjThe identical peak P of appearance timexIf depositing
In the identical peak P of appearance timex, S44 is entered step, otherwise return step S41；
S44, judge PxSignal-to-noise ratio whether be greater than setting snr threshold and relative abundance whether to be greater than setting opposite
Abundance threshold value, if PxSignal-to-noise ratio be greater than setting snr threshold, and relative abundance be greater than setting relative abundance threshold value, then sentence
Disconnected PxFor useful signal, S45 is entered step, otherwise return step S41；
S45, basis are judged as the P of useful signali、Pj, the sample to be tested is determined according to the selection result of mass spectrum differential technique
Contained organic chloride, organic bromide or nitro substituent；
Wherein, repeat the above steps S41-S45, until completing to compare between all peaks in first spectrogram.
Further, the snr threshold that sets is 3, and the relative abundance threshold value that sets is 3%.
Further, the step S1 includes: to carry out Solid Phase Extraction with solid-phase extraction column to water sample to be measured；To the solid phase
Extraction column carries out affording eluent；Eluent progress nitrogen is blown to and is completely dried, and the product after drying is dissolved in
In organic solvent, the sample to be tested is obtained.
Further, the solid-phase extraction column includes having the first solid phase of modified polystyrene-divinylbenzene filler
The second solid phase extraction column of extraction column and active carbon filling material, first solid-phase extraction column and the second solid phase extraction column
The series connection when carrying out Solid Phase Extraction, it is in parallel when being eluted.
Further, in the step S1, consolidating for organic matter successively has been adsorbed with methanol, acetone and dichloromethane eluent
Phase extraction column.
Further, the step S1 further include: before carrying out Solid Phase Extraction, successively use methylene chloride, acetone and first
Alcohol elutes the solid-phase extraction column of non-loading.
Further, step S1 further include: before carrying out Solid Phase Extraction, successively washed with methylene chloride, acetone and methanol
The solid-phase extraction column of de- non-loading, again with methanol and ultrapure water activate the solid-phase extraction column.
The invention has the following beneficial effects:
Come the invention proposes a kind of with Solid Phase Extraction-two-dimensional gas chromatography-EI mass spectral analysis-mass spectrum differential technique screening
Determine that the chlorine in water replaces (- Cl) organic pollutant, bromine that (- Br) organic pollutant, nitro is replaced to replace (- NO2) organic contamination
Quick, easy, the effective method of object.By proposing that (GC × GC-EI/MS) is used in conjunction in two-dimensional gas chromatography-electron bombardment/mass spectrum
Analysis method, water pollutant screening method of the invention can quickly and easily realize chlorine replace (- Cl) organic pollutant, bromine
(- Br) organic pollutant, nitro is replaced to replace (- NO2) organic pollutant reliable screening, to the separating effect of organic pollutant
More preferably, it can recognize volatile organic contaminant, and instrument cost is lower.
Detailed description of the invention
Fig. 1 is the flow chart according to the water pollutant screening method of the embodiment of the present invention；
Fig. 2 (a) to Fig. 2 (j) is the mass spectrum differential technique schematic diagram according to the embodiment of the present invention；
Fig. 3 is the judgment method according to the organic chloride of the embodiment of the present invention, organic bromide, nitro substituent signal
Flow chart；
Fig. 4 is part mass spectrogram obtained in example 1；
Fig. 5 is part mass spectrogram obtained in example 2；
Fig. 6 is part mass spectrogram obtained in example 3.
Specific embodiment
In conjunction with attached drawing, the present invention is further described in detail by the following examples.Front is quite widely
Feature and technological merit of the invention are outlined, so as to more fully understand following detailed description of the present invention.Below will
Description forms the supplementary features and advantage of the invention of the claims in the present invention theme.It will be appreciated by those skilled in the art that institute
Disclosed concept and specific embodiment can be easily used as a modification or designed for realize the identical purpose of the present invention its
The basis of his structure.It should also be realized by those skilled in the art that this equivalent structure is not departed from appended claims and is explained
The spirit and scope of the present invention stated.When considered in conjunction with the accompanying drawings, feature of present invention will be more fully understood from being described below
Novelty, its organizing and operating method and other objects and advantages.It is expressly understood, however, that each attached drawing be only for
It illustrates and describes and provides, be only exemplary, it is no intended to the limitation as the scope of the present invention.
In one embodiment, a kind of water pollutant screening method, comprising the following steps:
S1, the sample to be tested obtained from water sample to be measured；
S2, two-dimensional gas chromatography analysis is carried out to the sample to be tested, obtains intermediate analysis object；
S3, the intermediate analysis object are divided into two parts, and a part of the intermediate analysis object is bombarded through EI ion source
The ion of different mass-to-charge ratioes (m/z) is generated, and is analyzed by mass spectrometry (MS), obtains the first spectrum arranged by mass-to-charge ratio size order
Figure；Another part of the intermediate analysis object is carried out ECD to detect to obtain the second spectrogram；
S4, first spectrogram is screened using mass spectrum differential technique, is compared with second spectrogram, if through matter
It composes and there is effective letter that expression may be organic chloride, organic bromide or nitro substituent in the selection result of differential technique
Number, and there is also the useful signals in second spectrogram, then judge that the sample to be tested contains having for useful signal expression
Machine chloride, organic bromide or nitro substituent.
In some preferred embodiments, the water pollutant screening method is further comprising the steps of:
S5, the pollutant filtered out in step S4 is compared with NIST spectrum library, further to identify material composition.
In some preferred embodiments, the mass spectrum differential technique includes:
For the sum of known mass-to-charge ratio x and m, wherein m takes any one of following numerical value:
35/37/46/70/72/74/79/81/105/107/109/111/114/116/118/149/151/153/155/
158/160/162/193/195/197/199/237/239/241/243
If corresponding to the effective signal of x+m subject to confirmation in first spectrogram, if hereinafter referred to as x+m has signal,
In include following scenario described:
If x+35/37 (1Cl35/1Cl37) there is signal, then signal expression may have a chlorine substituent, wherein numerical value 35/
37 correspond to 1Cl35/1Cl37；
If x+70/72/74 (2Cl35/1Cl35+1Cl37/2Cl37) there is signal, then signal expression may have dichloro substitution
Object, wherein numerical value 70/72/74 corresponds to 2Cl35/1Cl35+1Cl37/2Cl37；
If x+105/107/109/111 (3Cl35/2Cl35+1Cl37/1Cl35+2Cl37/3Cl37) there is signal, then the signal table
Trichlorine substituent may be had by showing, wherein numerical value 105/107/109/111 corresponds to 3Cl35/2Cl35+1Cl37/1Cl35+2Cl37/
3Cl37；
If x+79/81 (1Br79/1Br81) there is signal, then signal expression may have monobromo substituent, wherein numerical value 79/
81 correspond to 1Br79/1Br81；
If x+158/160/162 (2Br79/1Br79+1Br81/2Br81) there is signal, then signal expression may have dibromo to take
For object, wherein numerical value 158/160/162 corresponds to 2Br79/1Br79+1Br81/2Br81；
If x+237/239/241/243 (3Br79/2Br79+1Br81/1Br79+2Br81/3Br81) there is signal, then the signal table
Tribromo substituent may be had by showing, wherein numerical value 237/239/241/243 corresponds to 3Br79/2Br79+1Br81/1Br79+2Br81/
3Br81；
If x+114/116/118 (1Cl35+1Br79/1Cl37+1Br79(1Cl35+1Br81)/1Cl37+1Br81) there is signal, then
Signal expression may have a chlorine monobromo substituent, and wherein numerical value 114/116/118 corresponds to 1Cl35+1Br79/1Cl37+1Br79
(1Cl35+1Br81)/1Cl37+1Br81；
If x+149/151/153/155 (2Cl35+1Br79/1Cl35+1Cl37+1Br79(2Cl35+1Br81)/1Cl35+1Cl37+
1Br81(2Cl37+1Br79)/2Cl37+1Br81) there is signal, then signal expression may have Dichloro-monobromo substituent, wherein numerical value
149/151/153/155 corresponds to 2Cl35+1Br79/1Cl35+1Cl37+1Br79(2Cl35+1Br81)/1Cl35+1Cl37+1Br81
(2Cl37+1Br79)/2Cl37+1Br81；
If x+193/195/197/199 (1Cl35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+
1Br81(1Cl35+2Br81)/1Cl37+2Br81) there is signal, then signal expression may have a chlorine dibromo substituent, wherein numerical value
193/195/197/199 corresponds to 1Cl35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+1Br81
(1Cl35+2Br81)/1Cl37+2Br81；
If x+46 (- NO2) there is signal, then signal expression may have nitro substituent, and wherein numerical value 46 corresponds to-NO2；
Wherein, Cl35Indicate that relative atomic mass is 35 chlorine atom, Cl37The chlorine for indicating that relative atomic mass is 37 is former
Son, Br79Indicate that relative atomic mass is 79 bromine atom, Br81Indicate that relative atomic mass is 81 bromine atom, N indicates opposite
The nitrogen-atoms that atomic mass is 14, O indicate that relative atomic mass is 16 nitrogen-atoms.
By taking a chlorine substituent as an example, if the chlorine atom for being 35 containing relative atomic mass in the substance, has letter for x+35
Number, therefore, signal expression may have containing Cl35A chlorine substituent；If the chlorine for being 37 containing relative atomic mass in the substance
Atom then has signal for x+37, and therefore, signal expression may have containing Cl37A chlorine substituent.
By taking nitro substituent as an example, if containing nitro (relative molecular mass 46) in the substance, there is signal for x+46,
Therefore, signal expression may have substituent containing nitro.In a further preferred embodiment, first spectrogram is indicated with n
Obtained in peak total number, PiIndicate i-th of peak obtained in first spectrogram, PjIt indicates to obtain in first spectrogram
J-th of peak, i, j=1,2 ..., n, and i < j, PxIndicate x-th of peak obtained in second spectrogram；
The step S4 is further included steps of
S41, from first peak P in first spectrogram1Start, by i-th of peak PiMass-to-charge ratio and the sum of m with j-th
Peak PjMass-to-charge ratio be compared, if comparison result is equal, enter step S42；
S42, judge Pi、PjSignal-to-noise ratio whether be greater than setting snr threshold and whether relative abundance is greater than setting phase
To abundance threshold value, if Pi、PjSignal-to-noise ratio be greater than setting snr threshold, and relative abundance be greater than setting relative abundance threshold value,
Then judge Pi、PjFor useful signal, S43 is entered step, otherwise return step S41；
S43, judge in second spectrogram with the presence or absence of appearance time and PjThe identical peak P of appearance timexIf depositing
In the identical peak P of appearance timex, S44 is entered step, otherwise return step S41；
S44, judge PxSignal-to-noise ratio whether be greater than setting snr threshold and relative abundance whether to be greater than setting opposite
Abundance threshold value, if PxSignal-to-noise ratio be greater than setting snr threshold, and relative abundance be greater than setting relative abundance threshold value, then sentence
Disconnected PxFor useful signal, S45 is entered step, otherwise return step S41；
S45, basis are judged as the P of useful signali、Pj, the sample to be tested is determined according to the selection result of mass spectrum differential technique
Contained organic chloride, organic bromide or nitro substituent；
Wherein, repeat the above steps S41-S45, until completing to compare between all peaks in first spectrogram.
In a more preferred embodiment, the snr threshold that sets is 3, and the relative abundance threshold value that sets is 3%.
In some preferred embodiments, the step S1 includes: to carry out solid phase extraction with solid-phase extraction column to water sample to be measured
It takes；The solid-phase extraction column is carried out to afford eluent；Eluent progress nitrogen is blown to and is completely dried, and will be dried
Product afterwards is dissolved in organic solvent, obtains the sample to be tested.
In some preferred embodiments, the solid-phase extraction column includes that there is modified polystyrene-divinylbenzene to fill out
First solid-phase extraction column of material and the second solid phase extraction column of active carbon filling material, first solid-phase extraction column and described the
The series connection when carrying out Solid Phase Extraction of two solid-phase extraction columns, it is in parallel when being eluted.
In some preferred embodiments, in the step S1, successively inhaled with methanol, acetone and dichloromethane eluent
The solid-phase extraction column of attached organic matter.
In a more preferred embodiment, the step S1 further include: before carrying out Solid Phase Extraction, successively use dichloromethane
Alkane, acetone and methanol elute the solid-phase extraction column of non-loading.
In a further preferred embodiment, step S1 further include: before carrying out Solid Phase Extraction, successively use dichloromethane
Alkane, acetone and methanol elute the solid-phase extraction column of non-loading, and again with methanol and ultrapure water activate the solid-phase extraction column.
Such as above-described embodiment, screening, especially chlorine are carried out the invention proposes a kind of pair of water pollutant, (- Cl) is replaced to have
Machine object, bromine replace (- Br) organic matter, nitro to replace the screening of (- NO2) organic matter etc., with Solid Phase Extraction-two dimension gas phase color
The high confidence level screening method of pollutant of spectrum-electron bombardment (EI) mass spectral analysis-mass spectrum differential technique screening and the library identification of NIST spectrum.
In an exemplary embodiment, the screening method of the water pollutant mainly comprises the following processes: water sample to be measured is pre-processed,
Progress Solid Phase Extraction, elution, nitrogen are blown respectively.GC × GC-EI/MS analysis is carried out to sample to be tested.Using mass spectrum differential technique to EI-
The mass spectrogram that MS is obtained is screened, and is judged as potential organic chloride, organic bromide, nitro substituent.By what is judged
Potential organic chloride, potential organic bromide and potential nitro substituent and the ECD testing result of shunting compare, judgement
For determining organic chloride, organic bromide and nitro substituent, while quantitative analysis is done with ECD result.By acquired results
It is compared with NIST spectrum library, Lai Jianding unknown materials component.The screening method of this water pollutant can be realized quickly and easily
Chlorine replaces (- Cl) organic pollutant, bromine that (- Br) organic pollutant, nitro is replaced to replace the screening of (- NO2) organic pollutant, right
The separating effect of organic pollutant is more preferable, can recognize volatile organic contaminant, and instrument cost is lower.
Illustrate method of the invention in detail below by way of specific embodiment.
A kind of water pollutant screening method, comprising the following steps:
Step 1: water sample to be measured being pre-processed, progress Solid Phase Extraction, elution, nitrogen are blown respectively.
It may include successively eluting non-loading with methylene chloride, acetone and methanol solvate for Solid Phase Extraction described in step 1
Solid-phase extraction column, the impurity of filler is effectively reduced.
May include for Solid Phase Extraction described in step 1, with the solid-phase extraction column after methanol and ultrapure water activation.
It may include modified polystyrene-divinylbenzene filler solid-phase extraction column for Solid Phase Extraction described in step 1
It connects with the solid-phase extraction column of active carbon filler, obviously can further improve the rate of recovery of target compound.
It may include successively having adsorbed organic matter with methanol, acetone and dichloromethane eluent for elution described in step 1
Solid-phase extraction column
Nitrogen described in step 1 is blown and may include, nitrogen is carried out to the eluent after Solid Phase Extraction and is blown, until be completely dried, it is molten
In the organic solvents such as n-hexane, methylene chloride, to use in next step.
Step 2: GC × GC-EI/MS analysis is carried out to sample to be tested.Sample to be tested is separated through two-dimensional gas chromatography,
The ion of different mass-to-charge ratioes (m/z) is generated through EI ion source.Mass spectrogram is obtained in the mass analyser.Export raw-data map number
According to drawing mass spectrogram；
It is the mass spectrogram arranged by mass-to-charge ratio size order for mass spectrogram described in step 2；
Step 3: the mass spectrogram that EI-MS is obtained is screened using mass spectrum differential technique, be judged as potential chlorine substituent,
Dichloro substituent, trichlorine substituent, monobromo substituent, dibromo substituent, tribromo substituent, a chlorine monobromo substituent, a chlorine two
Bromine substituent, Dichloro-monobromo substituent；Nitro substituent；
It is specifically for mass spectrum differential technique described in step 3, if known m/z=x,
If x+35/37 has signal, which may be a chlorine substituent, referring to fig. 2 map shown in (a)；
If x+70/72/74 has signal, which may be dichloro substituent, referring to fig. 2 map shown in (b)；
If x+105/107/109/111 has signal, which may be trichlorine substituent, referring to fig. 2 shown in (c)
Map；
If x+79/81 has signal, which may be monobromo substituent, referring to fig. 2 map shown in (d)；
If x+158/160/162 has signal, which may be dibromo substituent, scheme shown in (e) referring to fig. 2
Spectrum；
If x+237/239/241/243 has signal, which may be tribromo substituent, referring to fig. 2 shown in (f)
Map；
If x+114/116/118 has signal, which may be a chlorine monobromo substituent, referring to fig. 2 shown in (g)
Map；
If x+149/151/153/155 has signal, which may be Dichloro-monobromo substituent, referring to fig. 2 institute in (h)
The map shown；
If x+193/195/197/199 has signal, which may be a chlorine dibromo substituent, referring to fig. 2 institute in (i)
The map shown；
If x+46 (- NO2) there is signal, then the signal may be nitro substituent, referring to fig. 2 map shown in (j).
For described in step 3 whether be signal judgment method, preferably are as follows:
If S/N > 3, and relative abundance > 3%, then can be regarded as useful signal.
Step 4: in order to avoid what non-organic chloride, non-organic bromide and non-nitro substituent generated has phase homogeneity
Lotus than ion interference, to the potential organic chloride, potential organic bromide and potential nitro substituent judged in step 3
It is compared with the ECD testing result of shunting, is judged as that a chlorine substituent, dichloro substituent, trichlorine substituent, monobromo replace
Object, dibromo substituent, tribromo substituent, a chlorine monobromo substituent, a chlorine dibromo substituent, Dichloro-monobromo substituent, nitro take
Quantitative analysis is done for object, while with ECD result；
If the potential organic chloride that mass spectrum differential technique is judged, potential organic bromide and potential nitro substituent exist
Useful signal, and shunt ECD detector result in there is also this useful signals, then be certain determine organic chloride,
Organic bromide or nitro substituent.
For the shunting described in step 4 ECD detector testing result whether be useful signal judgment method, preferably
Are as follows:
If S/N > 3, and relative abundance > 3%, then can be regarded as useful signal.
For the ECD detector Comparative result with shunting described in step 4, refer to whether appearance time is consistent
For using the organic chloride of step 3 and step 4, the judgment method of organic bromide, nitro substituent,
It can be indicated with method shown in Fig. 3, be specifically expressed as,
PiIndicate i-th of peak obtained in first spectrogram, PjIndicate j-th of peak obtained in first spectrogram, i,
J=1,2 ..., n, and i < j share n peak, P in first spectrogramxIndicate the spectrogram that the ECD detector result shunted obtains
Obtained in x-th of peak, m/z is mass-to-charge ratio, and S/N is signal-to-noise ratio, and t is appearance time, and R is relative abundance, m=35/37/46/
70/72/74/79/81/105/107/109/111/114/116/118/149/151/153/155/158/160/162/193/
195/197/199/237/239/241/243。
First, it is determined that the n peak shared in first spectrogram out.
Judged from first peak, if first peak Pi(i=1) mass-to-charge ratio adds m to be second peak P2(j=2) matter
Lotus ratio
Then further judge Pi、PjWhether useful signal can be can be regarded as.Judgment basis is to judge Pi、PjSignal-to-noise ratio whether >
3, and relative abundance > 3%
If Pi、PjUseful signal can be can be regarded as, then further judge PjAppearance time whether shunting ECD testing result
There is the P with same appearance time in the spectrogram obtainedxPeak.The identical peak of appearance time if it exists,
Then further judge Pj、PxWhether useful signal can be can be regarded as.Judgment basis is to judge Pj、PxSignal-to-noise ratio whether >
3, and relative abundance > 3%
If Pj、PxUseful signal can be can be regarded as, then export Pi、Pj、Px, and judge whether i is last in first spectrogram
One peak, if the last one peak, then end of run.
If PiMass-to-charge ratio add m not to be PjMass-to-charge ratio or Pi、PjUseful signal cannot be can be regarded as, or the i judged is differed
In n, then+1 peak of jth being judged, if j-th of peak is not more than n, continuing to judge, if j-th of peak is greater than n, converting i is i+1, j
For i+1, P is further judgediMass-to-charge ratio add whether m is PjMass-to-charge ratio；
If Pi、PjUseful signal, but P can be can be regarded asjAppearance time in the spectrogram that the ECD testing result of shunting obtains not
In the presence of the P with same appearance timexPeak or Pj、PxUseful signal can not be can be regarded as, then i is judged, if i is not last
A peak then carries out Pj+1Multilevel iudge.
Step 5: in conjunction with the organic chloride, organic bromide, nitro substituent filtered out in step 4, composing library with NIST
It is compared, Lai Jianding unknown materials component.
Example
Universal method: the solid phase of modified polystyrene-divinylbenzene filler solid-phase extraction column and active carbon filler extraction
Column is taken to connect.The solid-phase extraction column that non-loading is successively eluted with methylene chloride, acetone and methanol solvate, it is living with methanol and ultrapure water
Change solid-phase extraction column；After water sample extraction, the Solid Phase Extraction of organic matter has successively been adsorbed with methanol, acetone and dichloromethane eluent
Column；Nitrogen is carried out to the eluent after Solid Phase Extraction to blow, until being completely dried, is dissolved in the organic solvents such as n-hexane, methylene chloride.
The preparation of sample and data acquisition are identical in example 1-3, and detailed process is as follows:
The preparation of solid-phase extraction column: taking volume is the solid-phase extraction column void column pipe of 6mL, and sieve plate is padded on column tube bottom.According to
It is secondary to use methylene chloride, acetone, each pair of solvent of three kinds of methanol filler Soxhlet extraction for 24 hours, by active carbon 400mg or modified polyphenyl second
Alkene-divinylbenzene filler 200mg is added in column tube, and is flattened with sieve plate.
Solid Phase Extraction, elution, nitrogen are blown: successively living with 1mL/min with 5mL methylene chloride, acetone, methanol and 10mL ultrapure water
Change extraction column.After water sample extraction, it will be separated containing active carbon and modified polystyrene-divinylbenzene filler solid-phase extraction column
And elute respectively, merge eluent.Glass centrifuge tube collects eluent, and nitrogen, which is blown to, to be completely dried.
Solid to be measured after drying is dissolved in a certain amount of organic solvent, two-dimensional gas chromatography-EI mass spectral analysis is carried out.
Sample to be tested is separated through two-dimensional gas chromatography, and the ion of different mass-to-charge ratioes (m/z) is generated by EI ion source.In quality point
The mass spectrogram arranged by mass-to-charge ratio size order is obtained in parser, is exported initial data diagram data, is drawn mass spectrogram.
Example 1:
Sample to be tested obtains the mass spectrogram arranged by mass-to-charge ratio size order after two-dimensional gas chromatography-EI mass spectral analysis,
Part of mass spectrogram is as shown in Figure 4.By taking existing chloroform as an example, in the figure, m/z=14, m/z+105/107/
109/111=119/121/123/125, it can be observed that mass spectra peak at m/z=119/121/123/125, and S/N > 3, R >
3%, there are this signals in the ECD detector result of corresponding shunting, and therefore S/N > 3, R > 3% wrap in the test substance
Containing three chloros (35Cl and37Cl) pollutant.Further identification is done in conjunction with library being composed with NIST.
Example 2:
Sample to be tested obtains the mass spectrogram arranged by mass-to-charge ratio size order after two-dimensional gas chromatography-EI mass spectral analysis,
Part of mass spectrogram is as shown in Figure 5.By taking an existing bromoacetonitrile as an example, in the figure, m/z=40, m/z+79/81=119/
121, mass spectra peak, and S/N > 3, R > 3%, the ECD detector knot of corresponding shunting are observed that at m/z=119/121
There are this signal in fruit, and S/N > 3, R > 3%, therefore, in the test substance comprising a bromo (79Br and81Br) pollutant.It can
Further identification is done in conjunction with NIST spectrum library.
Example 3:
Sample to be tested obtains the mass spectrogram arranged by mass-to-charge ratio size order after two-dimensional gas chromatography-EI mass spectral analysis,
Part of mass spectrogram is as shown in Figure 6.By taking existing nitrobenzene as an example, in the figure, m/z=77, m/z+46=123, in m/z
It is observed that mass spectra peak, and S/N > 3 at=123, R > 3%, there are this letters in the ECD detector result of corresponding shunting
Number, and therefore S/N > 3, R > 3% replace pollutant comprising nitro in the test substance.It is done further in conjunction with library being composed with NIST
Identification.
The above content is combine it is specific/further detailed description of the invention for preferred embodiment, cannot recognize
Fixed specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs,
Without departing from the inventive concept of the premise, some replacements or modifications can also be made to the embodiment that these have been described,
And these substitutions or variant all shall be regarded as belonging to protection scope of the present invention.In the description of this specification, with reference to art
Language " a kind of embodiment ", " some embodiments ", " preferred embodiment ", " example ", " specific example " or " some examples " etc. is retouched
It states and means that particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained in of the invention at least one
In a embodiment or example.In the present specification, schematic expression of the above terms are necessarily directed to identical implementation
Example or example.Moreover, particular features, structures, materials, or characteristics described can be in any one or more embodiment or examples
In can be combined in any suitable manner.In addition, without conflicting with each other, those skilled in the art can will be in this specification
The different embodiments or examples of description and the feature of different embodiments or examples are combined.Although retouching in detail
The embodiment of the present invention and its advantage have been stated, it is to be understood that, do not departing from the embodiment spirit being defined by the following claims
In the case where range, various changes, replacement and change can be carried out herein.In addition, the scope of the present invention is not intended to limit
In process described in the specification, machine, manufacture, material composition, means, method and steps specific embodiment.This field is general
Logical technical staff is it will be readily understood that can use execution and the essentially identical function of corresponding embodiment described herein or obtain and this paper
The essentially identical result of embodiment presently, there are or above-mentioned disclosure, process, machine, the manufacture, substance to be developed later
Composition, means, method or step.Therefore, appended claims be intended to by these processes, machine, manufacture, material composition, means,
Method or step is embraced within their scope.
Claims (10)
1. a kind of water pollutant screening method, which comprises the following steps:
S1, the sample to be tested obtained from water sample to be measured；
S2, two-dimensional gas chromatography analysis is carried out to the sample to be tested, obtains intermediate analysis object；
S3, the intermediate analysis object is divided into two parts, a part of the intermediate analysis object is bombarded through EI ion source and is produced
The ion of raw different mass-to-charge ratioes, and be analyzed by mass spectrometry, obtain the first spectrogram arranged by mass-to-charge ratio size order；In described
Between analyte another part carry out ECD detect to obtain the second spectrogram；
S4, first spectrogram is screened using mass spectrum differential technique, is compared with second spectrogram, if poor through mass spectrum
There is the useful signal that expression may be organic chloride, organic bromide or nitro substituent in the selection result of value method, and
And there is also the useful signals in second spectrogram, it is determined that the sample to be tested correspondingly contains organic chloride, organic
Bromide or nitro substituent.
2. water pollutant screening method as described in claim 1, which is characterized in that further comprising the steps of:
S5, the pollutant determined in step S4 is compared with NIST spectrum library, further to identify material composition.
3. water pollutant screening method as claimed in claim 1 or 2, which is characterized in that the mass spectrum differential technique includes:
For the sum of known mass-to-charge ratio x and m, wherein m takes any one of following numerical value:
35/37/46/70/72/74/79/81/105/107/109/111/114/116/118/149/151/153/155/158/
160/162/193/195/197/199/237/239/241/243
If corresponding to the effective signal of x+m subject to confirmation in first spectrogram, if hereinafter referred to as x+m has signal, wherein
Including following scenario described:
If x+35/37 has signal, signal expression may have a chlorine substituent, and wherein numerical value 35/37 corresponds to 1Cl35/
1Cl37；
If x+70/72/74 has signal, signal expression may have dichloro substituent, and wherein numerical value 70/72/74 corresponds to
2Cl35/1Cl35+1Cl37/2Cl37；
If x+105/107/109/111 has signal, signal expression may have trichlorine substituent, wherein numerical value 105/107/
109/111 corresponds to 3Cl35/2Cl35+1Cl37/1Cl35+2Cl37/3Cl37；
If x+79/81 has signal, signal expression may have monobromo substituent, and wherein numerical value 79/81 corresponds to 1Br79/
1Br81；
If x+158/160/162 has signal, signal expression may have dibromo substituent, and wherein numerical value 158/160/162 is right
It should be in 2Br79/1Br79+1Br81/2Br81；
If x+237/239/241/243 has signal, signal expression may have tribromo substituent, wherein numerical value 237/239/
241/243 corresponds to 3Br79/2Br79+1Br81/1Br79+2Br81/3Br81；
If x+114/116/118 has signal, signal expression may have a chlorine monobromo substituent, wherein numerical value 114/116/
118 correspond to 1Cl35+1Br79/1Cl37+1Br79(1Cl35+1Br81)/1Cl37+1Br81；
If x+149/151/153/155 has signal, signal expression may have Dichloro-monobromo substituent, wherein numerical value 149/
151/153/155 corresponds to 2Cl35+1Br79/1Cl35+1Cl37+1Br79(2Cl35+1Br81)/1Cl35+1Cl37+1Br81(2Cl37+
1Br79)/2Cl37+1Br81；
If x+193/195/197/199 has signal, signal expression may have a chlorine dibromo substituent, wherein numerical value 193/
195/197/199 corresponds to 1Cl35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+1Br81(1Cl35+
2Br81)/1Cl37+2Br81；
If x+46 has signal, signal expression may have nitro substituent, and wherein numerical value 46 corresponds to-NO2；
Wherein, Cl35Indicate that relative atomic mass is 35 chlorine atom, Cl37Indicate that relative atomic mass is 37 chlorine atom, Br79
Indicate that relative atomic mass is 79 bromine atom, Br81Indicate that relative atomic mass is 81 bromine atom, N indicates relative atom matter
The nitrogen-atoms that amount is 14, O indicate that relative atomic mass is 16 nitrogen-atoms.
4. water pollutant screening method as claimed in claim 3, which is characterized in that
The total number at peak obtained in first spectrogram, P are indicated with niIndicate i-th of peak obtained in first spectrogram, Pj
Indicate j-th of peak obtained in first spectrogram, i, j=1,2 ..., n, and i < j, PxIt indicates to obtain in second spectrogram
X-th of peak；
The step S4 is further included steps of
S41, from first peak P in first spectrogram1Start, by i-th of peak PiMass-to-charge ratio and the sum of m and j-th of peak Pj
Mass-to-charge ratio be compared, if comparison result is equal, enter step S42；
S42, judge Pi、PjSignal-to-noise ratio whether be greater than setting snr threshold and relative abundance whether to be greater than setting relatively rich
Threshold value is spent, if Pi、PjSignal-to-noise ratio be greater than setting snr threshold, and relative abundance be greater than setting relative abundance threshold value, then sentence
Disconnected Pi、PjFor useful signal, S43 is entered step, otherwise return step S41；
S43, judge in second spectrogram with the presence or absence of appearance time and PjThe identical peak P of appearance timex, go out if it exists
The identical peak P of peak timex, S44 is entered step, otherwise return step S41；
S44, judge PxSignal-to-noise ratio whether be greater than setting snr threshold and whether relative abundance is greater than setting relative abundance
Threshold value, if PxSignal-to-noise ratio be greater than setting snr threshold, and relative abundance be greater than setting relative abundance threshold value, then judge Px
For useful signal, S45 is entered step, otherwise return step S41；
S45, basis are judged as the P of useful signali、Pj, determined contained by the sample to be tested according to the selection result of mass spectrum differential technique
Some organic chlorides, organic bromide or nitro substituent；
Wherein, repeat the above steps S41-S45, until completing to compare between all peaks in first spectrogram.
5. water pollutant screening method as claimed in claim 4, which is characterized in that the snr threshold that sets as 3, and
The relative abundance threshold value that sets is 3%.
6. such as water pollutant screening method described in any one of claim 1 to 5, which is characterized in that the step S1 includes:
Solid Phase Extraction is carried out with solid-phase extraction column to water sample to be measured；The solid-phase extraction column is carried out to afford eluent；To described
Eluent progress nitrogen, which is blown to, to be completely dried, and the product after drying is dissolved in organic solvent, obtains the sample to be tested.
7. water pollutant screening method as claimed in claim 6, which is characterized in that in the step S1, the solid phase extraction
Taking column includes second with the first solid-phase extraction column of modified polystyrene-divinylbenzene filler and active carbon filling material
Solid-phase extraction column, first solid-phase extraction column are connected when carrying out Solid Phase Extraction with the second solid phase extraction column, are being carried out
It is in parallel when elution.
8. water pollutant screening method as claimed in claim 6, which is characterized in that in the step S1, successively with methanol,
Acetone and dichloromethane eluent have adsorbed the solid-phase extraction column of organic matter.
9. water pollutant screening method as claimed in claim 6, which is characterized in that the step S1 further include: carrying out
Before Solid Phase Extraction, the solid-phase extraction column of non-loading is successively eluted with methylene chloride, acetone and methanol.
10. water pollutant screening method as claimed in claim 6, which is characterized in that the step S1 further include: carrying out
Before Solid Phase Extraction, the solid-phase extraction column of non-loading, again with methanol and ultrapure water are successively eluted with methylene chloride, acetone and methanol
Activate the solid-phase extraction column.
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| CN111650299A (en) * | 2020-06-16 | 2020-09-11 | 山东大学 | High-sensitivity determination method for trace volatile organic compounds in ambient air |
| CN114577966A (en) * | 2020-11-18 | 2022-06-03 | 湘潭大学 | GC x GC fingerprint fast comparison method for classification of MSCC combined with modulation peak |
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| CN111650299A (en) * | 2020-06-16 | 2020-09-11 | 山东大学 | High-sensitivity determination method for trace volatile organic compounds in ambient air |
| CN114577966A (en) * | 2020-11-18 | 2022-06-03 | 湘潭大学 | GC x GC fingerprint fast comparison method for classification of MSCC combined with modulation peak |
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