CN109521111A - A kind of method for treating water based on pollutant screening - Google Patents
A kind of method for treating water based on pollutant screening Download PDFInfo
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- G—PHYSICS
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
A kind of method for treating water based on pollutant screening, comprising: the sample to be tested obtained from water sample to be measured；Two-dimensional gas chromatography analysis is carried out, intermediate analysis object is obtained, a part is bombarded through EI ion source generates ion, and is analyzed by mass spectrometry, and obtains the first spectrogram；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 expression in the selection result may be the useful signal that iodine replaces organic pollutant or nitrile organic pollutant, and second there is also the useful signals in spectrogram, then confirmation has iodine to replace organic pollutant or nitrile organic pollutant.This method can quickly and easily realize that iodine replaces the reliable screening of organic pollutant or nitrile organic pollutant, and the pollutant that can go out to screening is effectively treated, and targetedly removes removal organic polluter.
Description
Technical field
The present invention relates to the screenings of water pollutant, more particularly to a kind of method for treating water based on pollutant screening.
Background technique
Currently, frequently detecting that iodine replaces (- I) organic pollutant, the organic dirt of nitrile (- CN) in stain disease and surface water
Contaminate object etc..These water pollutant bring life and health risk cause the extensive concern of people.Most of iodine replace (-
I) organic pollutant, nitrile (- CN) organic pollutant have the characteristics that strong toxicity, difficult to degrade.The sieve of Organic Pollutants In Water
It looks into and targetedly handles particularly important to guarantee water quality safety.
Existing iodine replaces the detection method of (- I) organic pollutant, nitrile (- CN) organic pollutant, mainly gas phase color
Detection (GC-MS/MS) is used in conjunction for bis- mass spectrums or detection (LC-MS/MS) method is used in conjunction in the bis- mass spectrums of liquid chromatogram-for spectrum-.However, GC-
MS/MS scanning speed is inadequate, and instrument price is expensive；LC-MS/MS is detected mainly for non-volatile organic pollutant, and
Instrument price is expensive, cumbersome.Therefore still lacking rapid screening iodine at present replaces (- I) organic pollutant, nitrile (- CN) to have
The method of machine pollutant.
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 process based on pollutant screening
Method.
To achieve the above object, the invention adopts the following technical scheme:
A kind of method for treating water based on pollutant screening, comprising the following steps:
S1, the sample to be tested obtained from water sample to be processed；
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 the useful signal that expression may be iodine substitution organic pollutant or nitrile organic pollutant in the selection result of differential technique,
And there is also the useful signals in second spectrogram, it is determined that the sample to be tested correspondingly contains iodine and replaces organic contamination
Object or nitrile organic pollutant；
S5, according to step S4 determine as a result,
If water to be processed contains iodine and replaces organic pollutant, is disposed as follows: water to be processed is passed through into processing
Facility fills anoxic charcoal and iron filings in treatment facility, replaces organic pollutant to restore and biodegradable iodine；
If water to be processed contains nitrile organic pollutant, disposed as follows: water to be processed is set by processing
It applies, aerobic biological activated carbon is filled in treatment facility, by nitrile Adsorption of Organic and degradation.
Further, the water pollutant screening method is further comprising the steps of between step 4 and step 5:
S4a, 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:
26/127/254/381；
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+26 has signal, signal expression may have nitrile organic pollutant, and wherein numerical value 26 corresponds to-CN；
If x+127 has signal, signal expression may have an iodine substituent, and wherein numerical value 127 corresponds to -1I；
If x+254 has signal, signal expression may have diiodo- substituent, and wherein numerical value 254 corresponds to -2I；
If x+381 has signal, signal expression may have triiodo substituent, and wherein numerical value 381 corresponds to -3I；
Wherein, I indicates that relative atomic mass is 127 iodine atom, and N indicates that relative atomic mass is 14 nitrogen-atoms, C table
Show that relative atomic mass is 12 carbon atom.
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 iodine replaces organic pollutant or nitrile organic pollutant；
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 iodine in water replaces (- I) organic pollutant, nitrile (- CN) organic pollutant and targetedly disposes associated contamination
The method of object.By proposing that the analysis method of (GC × GC-EI/MS), this hair is used in conjunction in two-dimensional gas chromatography-electron bombardment/mass spectrum
Bright water pollutant screening method can quickly and easily realize that iodine replaces (- I) organic pollutant, nitrile (- CN) organic contamination
The reliable screening of object, it is more preferable to the separating effect of organic pollutant, it can recognize volatile organic contaminant, to water pollutant
Removal is more targeted, and removal effect is good, and cost is relatively low.
Detailed description of the invention
Fig. 1 is the flow chart according to the method for treating water based on pollutant screening of the embodiment of the present invention；
Fig. 2 (a) to Fig. 2 (d) is the mass spectrum differential technique schematic diagram according to the embodiment of the present invention；
Fig. 3 is the judgment method for replacing organic pollutant, nitrile organic pollutant signal according to the iodine of the embodiment of the present invention
Flow chart；
Fig. 4 is the treatment facility schematic diagram for replacing organic pollutant to the iodine that screening goes out；
Fig. 5 is the treatment facility schematic diagram of the nitrile organic pollutant gone out to screening；
Fig. 6 is part mass spectrogram obtained in example 1；
Fig. 7 is part mass spectrogram obtained in example 2.
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.
Referring to Fig. 1, in one embodiment, a kind of method for treating water based on pollutant screening, comprising the following steps:
S1, the sample to be tested obtained from water sample to be processed；
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 the useful signal that expression may be iodine substitution organic pollutant or nitrile organic pollutant in the selection result of differential technique,
And there is also the useful signals in second spectrogram, then the iodine for judging that the sample to be tested contains useful signal expression replaces
Organic pollutant or nitrile organic pollutant.
S5, according to step S4 determine as a result,
If water to be processed contains iodine and replaces organic pollutant, is disposed as follows: water to be processed is passed through into processing
Facility fills anoxic charcoal and iron filings in treatment facility, replaces organic pollutant to restore and biodegradable iodine；
If water to be processed contains nitrile organic pollutant, disposed as follows: water to be processed is set by processing
It applies, aerobic biological activated carbon is filled in treatment facility, by nitrile Adsorption of Organic and degradation.
In some preferred embodiments, the water pollutant screening method also wraps between step S4 and step S5
Include following steps:
S4a, 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:
26/127/254/381；
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+26 has signal, signal expression may have nitrile organic pollutant, and wherein numerical value 26 corresponds to-CN；
If x+127 has signal, signal expression may have an iodine substituent, and wherein numerical value 127 corresponds to -1I；
If x+254 has signal, signal expression may have diiodo- substituent, and wherein numerical value 254 corresponds to -2I；
If x+381 has signal, signal expression may have triiodo substituent, and wherein numerical value 381 corresponds to -3I；
Wherein, I indicates that relative atomic mass is 127 iodine atom, and N indicates that relative atomic mass is 14 nitrogen-atoms, C table
Show that relative atomic mass is 12 carbon atom.
By taking an iodine substituent as an example, if the iodine atom for being 127 containing relative atomic mass in the substance, has for x+127
Signal, therefore, signal expression may be an iodine substituent.
By taking nitrile organic pollutant as an example, if containing-CN (relative molecular mass 26) in the substance, there is letter for x+26
Number, therefore, signal expression may have organic pollutant containing nitrile.In a further preferred embodiment, described is indicated with n
The total number at peak obtained in one spectrogram, PiIndicate i-th of peak obtained in first spectrogram, PjIndicate first spectrogram
Obtained in 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 iodine replaces organic pollutant or nitrile organic pollutant；
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 iodine are carried out the invention proposes a kind of pair of water pollutant, (- I) is replaced to have
The screening of machine object, nitrile (- CN) organic matter etc., with Solid Phase Extraction-two-dimensional gas chromatography-electron bombardment (EI) mass spectral analysis-
The high confidence level screening of pollutant of the screening of mass spectrum differential technique and the library identification of NIST spectrum, and the method for carrying out targetedly water process.
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 that potential iodine replaces organic pollutant, nitrile organic pollutant.It is latent by what is judged
Replace organic pollutant and potential nitrile organic pollutant and the ECD testing result of shunting to compare in iodine, is judged as determining
Iodine replace organic pollutant and nitrile organic pollutant, while doing quantitative analysis with ECD result.Acquired results and NIST are composed
Library is compared, Lai Jianding unknown materials component.The screening method of this water pollutant, can quickly and easily realize iodine replace (-
I) the screening of organic pollutant, nitrile (- CN) organic pollutant, it is more preferable to the separating effect of organic pollutant, it can recognize volatilization
Property organic pollutant, and iodine in water removal can targetedly be gone to replace organic pollutant, nitrile organic pollutant, and instrument
Cost is relatively low.
Referring to fig. 4 and Fig. 5, Fig. 4 are the treatment facility schematic diagram for replacing organic pollutant to the iodine that screening goes out, for containing
Iodine replaces the pending water of organic pollutant, and by filling the treatment facility of anoxic charcoal and iron filings, iodine is replaced organic dirt
Contaminate object reduction and biodegrade；Fig. 5 is the treatment facility schematic diagram of the nitrile organic pollutant gone out to screening, for containing nitrile
The pending water of class organic pollutant, by filling the treatment facility of aerobic biological activated carbon, by nitrile Adsorption of Organic
And degradation.
Illustrate method of the invention in detail below by way of specific embodiment.
A kind of method for treating water based on pollutant screening, comprising the following steps:
Step 1: water sample to be processed 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 iodine substituent,
Diiodo- substituent, triiodo substituent；Nitrile organic pollutant；
It is specifically for mass spectrum differential technique described in step 3, if known m/z=x,
If x+127 has signal, which may be an iodine substituent, referring to fig. 2 map shown in (a)；
If x+254 has signal, which may be diiodo- substituent, referring to fig. 2 map shown in (b)；
If x+381 has signal, which may be triiodo substituent, referring to fig. 2 map shown in (c)；
If x+26 (- CN) has signal, which may be nitrile organic pollutant, scheme shown in (d) referring to fig. 2
Spectrum.
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-iodine substitution organic pollutant and nonnitriles organic pollutant generated has phase homogeneity lotus
Than the interference of ion, organic pollutant and potential nitrile organic pollutant are replaced to the potential iodine judged in step 3 and shunted
ECD testing result compare, be judged as an iodine substituent, diiodo- substituent, triiodo substituent, nitrile organic pollutant,
Quantitative analysis is done with ECD result simultaneously；
If the potential iodine that mass spectrum differential technique is judged replaces to be had existing for organic pollutant and potential nitrile organic pollutant
Signal is imitated, and there is also this useful signals in the ECD detector result shunted, then replaces organic pollutant for certain iodine determined
Or nitrile organic pollutant.
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
It, can for using the iodine of step 3 and step 4 to replace the judgment method of organic pollutant nitrile organic pollutant
It is indicated with method shown in Fig. 3, is 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=26/127/
254/381。
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: replace organic pollutant, nitrile organic pollutant in conjunction with the iodine that filters out in step 4, with NIST compose library into
Row compares, Lai Jianding unknown materials component.
Step 6: according to step 5 determine as a result,
If water to be processed contains iodine and replaces organic pollutant, is disposed as follows: water sample to be processed is passed through into place
Manage facility, anoxic charcoal and iron filings filled in treatment facility, by iodine replaces organic pollutant i.e. iodo pollutant restore and
Biodegrade；
If water to be processed contains nitrile organic pollutant, disposed as follows: water sample to be processed is passed through into processing
Facility fills aerobic biological activated carbon in treatment facility, by nitrile Adsorption of Organic and degradation；
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 1-2, 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 6.With C7H3I3O2For, in the figure, m/z=119, m/z+381=500, in m/z=
It is observed that mass spectra peak, and S/N > 3 at 500, R > 3%, there are this signal in the ECD detector result of corresponding shunting,
And therefore S/N > 3, R > 3% include three iodo pollutants in the test substance.Further identification is done in conjunction with library being composed with NIST.
It is that iodine replaces organic pollutant since screening comes out, water sample to be processed can be passed through treatment facility, place
It manages and fills anoxic charcoal and iron filings in facility, haloginated polluants reduction and biodegrade are disposed, at water sample used
It is as shown in Figure 4 to manage device.
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 7.By taking existing diphenatril as an example, in the figure, m/z=167, m/z+26=193,
It can be observed that mass spectra peak at m/z=193, and S/N > 3, R > 3%, there are this in the ECD detector result of corresponding shunting
Therefore signal, and S/N > 3, R > 3% include nitrile organic pollutant in the test substance.It does in conjunction with library being composed with NIST into one
Step identification.
It is nitrile organic pollutant since screening comes out, water sample to be processed can be passed through treatment facility, processing
Aerobic biological activated carbon is filled in facility, by nitrile Adsorption of Organic and degradation, to dispose, water sample processing dress used
It sets as shown in Figure 5.
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 method for treating water based on pollutant screening, which comprises the following steps:
S1, the sample to be tested obtained from water to be processed；
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 expression in the selection result of value method may be the useful signal that iodine replaces organic pollutant or nitrile organic pollutant, and
There is also the useful signals in second spectrogram, it is determined that the sample to be tested correspondingly contain iodine replace organic pollutant or
Nitrile organic pollutant；
S5, according to step S4 determine as a result,
If water to be processed contains iodine and replaces organic pollutant, disposed as follows: water to be processed passed through into treatment facility,
Anoxic charcoal and iron filings are filled in treatment facility, and halogen is replaced into organic pollutant reduction and biodegrade；
If water to be processed contains nitrile organic pollutant, disposed as follows: water to be processed is passed through into treatment facility, place
Aerobic biological activated carbon is filled in reason facility, by nitrile Adsorption of Organic and degradation.
2. water pollutant screening method as described in claim 1, which is characterized in that further include between step 4 and step 5
Following steps:
S4a, 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:
26/127/254/381；
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+26 has signal, signal expression may have nitrile organic pollutant, and wherein numerical value 26 corresponds to-CN；
If x+127 has signal, signal expression may have an iodine substituent, and wherein numerical value 127 corresponds to -1I；
If x+254 has signal, signal expression may have diiodo- substituent, and wherein numerical value 254 corresponds to -2I；
If x+381 has signal, signal expression may have triiodo substituent, and wherein numerical value 381 corresponds to -3I；
Wherein, I indicates that relative atomic mass is 127 iodine atom, and N indicates that relative atomic mass is 14 nitrogen-atoms, and C indicates phase
The carbon atom for being 12 to atomic mass.
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 iodine replaces organic pollutant or nitrile organic pollutant；
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 |
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