CN109507316B - Method for screening pollutants in water - Google Patents

Method for screening pollutants in water Download PDF

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CN109507316B
CN109507316B CN201811375550.6A CN201811375550A CN109507316B CN 109507316 B CN109507316 B CN 109507316B CN 201811375550 A CN201811375550 A CN 201811375550A CN 109507316 B CN109507316 B CN 109507316B
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CN109507316A (en
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吴乾元
胡洪营
张昕阳
杜烨
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Shenzhen Graduate School Tsinghua University
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Abstract

A method of screening for contaminants in water, comprising: obtaining a sample to be detected from a water sample to be detected; performing two-dimensional gas chromatography on a sample to be detected to obtain an intermediate analyte; bombarding a part of the intermediate analyte by an EI ion source to generate ions with different mass-to-charge ratios, and performing mass spectrometry to obtain a first spectrogram arranged in sequence according to the mass-to-charge ratios; performing ECD detection on the other part of the spectrum to obtain a second spectrogram; and screening the first spectrogram by adopting a mass spectrum difference method, comparing the first spectrogram with the second spectrogram, and if an effective signal which indicates that the first spectrogram is possibly organic chloride, organic bromide or nitro substituent exists in the screening result of the mass spectrum difference method and the effective signal also exists in the second spectrogram, determining that the sample contains the organic chloride, organic bromide or nitro substituent. The method can conveniently and rapidly realize chlorine substitution (-Cl) organic pollutants, bromine substitution (-Br) organic pollutants and nitro substitution (-NO)2) Reliable screening of organic pollutants.

Description

Method for screening pollutants in water
Technical Field
The invention relates to screening of pollutants in water, in particular to a method for screening pollutants in water.
Background
At present, chlorine substituted (-Cl) organic pollutants, bromine substituted (-Br) organic pollutants and nitro substituted (-NO) organic pollutants are frequently detected in sewage, waste water and surface water2) Organic contaminants, and the like. The life and health risks associated with these water pollutants have raised widespread concern. Most of chlorine substituted (-Cl) organic pollutant, bromine substituted (-Br) organic pollutant and nitro substituted (-NO)2) The organic pollutants have strong toxicity and are difficult to degradeIs characterized in that. The screening of organic pollutants in water is particularly important for guaranteeing the water quality safety.
The existing chlorine substituted (-Cl) organic pollutant, bromine substituted (-Br) organic pollutant and nitro substituted (-NO)2) The detection method of the organic pollutants mainly adopts a gas chromatography-dual mass spectrometry combined detection (GC-MS/MS) method or a liquid chromatography-dual mass spectrometry combined detection (LC-MS/MS) method. However, the GC-MS/MS scanning speed is not sufficient and the instrument is expensive; LC-MS/MS detection mainly aims at nonvolatile organic pollutants, and the instrument is expensive and complicated to operate. Therefore, the rapid screening of chlorine substituted (-Cl) organic pollutants, bromine substituted (-Br) organic pollutants and nitro substituted (-NO) organic pollutants is still lacked2) A method for organic contamination.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provide a method for screening pollutants in water.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for screening contaminants in water, comprising the steps of:
s1, obtaining a sample to be detected from a water sample to be detected;
s2, carrying out two-dimensional gas chromatography on the sample to be detected to obtain an intermediate analyte;
s3, dividing the intermediate analyte into two parts, bombarding one part of the intermediate analyte by an EI ion source to generate ions with different mass-to-charge ratios (m/z), and performing Mass Spectrometry (MS) to obtain a first spectrogram arranged in sequence according to the mass-to-charge ratios; performing ECD detection on another part of the intermediate analyte to obtain a second spectrogram;
s4, screening the first spectrogram by adopting a mass spectrum difference method, comparing the first spectrogram with the second spectrogram, and if an effective signal which indicates that the first spectrogram can be organic chloride, organic bromide or nitro substituent exists in the screening result of the mass spectrum difference method and the effective signal also exists in the second spectrogram, determining that the sample to be detected correspondingly contains the organic chloride, organic bromide or nitro substituent.
Further, the method for screening pollutants in water further comprises the following steps:
s5, comparing the contaminants screened in step S4 with the NIST library to further identify the substance components.
Further, the mass spectrometry difference method comprises:
for a known sum of mass-to-charge ratios x and m, where m takes any of the following values:
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 a signal corresponding to x + m in the first spectrum is to be confirmed, it is abbreviated as if x + m has a signal, which includes the following cases:
if x +35/37(1 Cl)35/1Cl37) With a signal, the signal indicates the possibility of a monochloro substituent, where the value 35/37 corresponds to 1Cl35/1Cl37；
If x +70/72/74(2 Cl)35/1Cl35+1Cl37/2Cl37) With a signal indicating the possibility of a dichloro substituent, where the value 70/72/74 corresponds to 2Cl35/1Cl35+1Cl37/2Cl37；
If x +105/107/109/111(3 Cl)35/2Cl35+1Cl37/1Cl35+2Cl37/3Cl37) With a signal indicating the possibility of a trichloro substituent, where the value 105/107/109/111 corresponds to 3Cl35/2Cl35+1Cl37/1Cl35+2Cl37/3Cl37；
If x +79/81(1 Br)79/1Br81) There is a signal indicating the possibility of a bromine substitution, where the value 79/81 corresponds to 1Br79/1Br81；
If x +158/160/162(2 Br)79/1Br79+1Br81/2Br81) With a signal indicating the possibility of a dibromo substituent, where the number 158/160/162 corresponds to 2Br79/1Br79+1Br81/2Br81；
If x +237/239/241/243(3 Br)79/2Br79+1Br81/1Br79+2Br81/3Br81) With a signal indicating the possibility of tribromo substitution, where the value 237/239/241/243 corresponds to 3Br79/2Br79+1Br81/1Br79+2Br81/3Br81；
If x +114/116/118(1 Cl)35+1Br79/1Cl37+1Br79(1Cl35+1Br81)/1Cl37+1Br81) There is a signal which indicates that a monochloromonobromo substituent is possible, where the value 114/116/118 corresponds to 1Cl35+1Br79/1Cl37+1Br79(1Cl35+1Br81)/1Cl37+1Br81；
If x +149/151/153/155(2 Cl)35+1Br79/1Cl35+1Cl37+1Br79(2Cl35+1Br81)/1Cl35+1Cl37+1Br81(2Cl37+1Br79)/2Cl37+1Br81) With a signal indicating the possibility of a dichloromonobromide substituent, wherein the 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(1 Cl)35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+1Br81(1Cl35+2Br81)/1Cl37+2Br81) If there is a signal, the signal is sentNumbers indicate possible monochlorodibromos, where the number 193/195/197/199 corresponds to 1Cl35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+1Br81(1Cl35+2Br81)/1Cl37+2Br81；
If x +46 (-NO)2) With a signal indicating the possibility of nitro substitution, where the value 46 corresponds to-NO2；
Wherein, Cl35Represents a chlorine atom, Cl, of relative atomic mass 3537Denotes a chlorine atom, Br, of relative atomic mass 3779Represents a bromine atom, Br, having a relative atomic mass of 7981Represents a bromine atom having a relative atomic mass of 81, N represents a nitrogen atom having a relative atomic mass of 14, and O represents a nitrogen atom having a relative atomic mass of 16.
Further, n represents the total number of peaks obtained in the first spectrogram, PiRepresents the ith peak, P, obtained in the first spectrogramjDenotes the j-th peak obtained in the first spectrum, i, j ═ 1, 2, …, n, and i<j，PxRepresents the x-th peak obtained in the second spectrogram;
the step S4 further includes the steps of:
s41, obtaining a first peak P from the first spectrogram1Starting with the ith peak PiThe sum of the mass-to-charge ratio of (A) and (B) and the jth peak PjComparing the mass-to-charge ratios, and if the comparison results are equal, proceeding to step S42;
s42, judgment Pi、PjWhether the signal-to-noise ratio is greater than a set signal-to-noise ratio threshold value and whether the relative abundance is greater than a set relative abundance threshold value, if P isi、PjIs greater than a set signal-to-noise ratio threshold value, and the relative abundance is greater than a set relative abundance threshold value, then P is judgedi、PjIf the signal is a valid signal, the step S43 is entered, otherwise, the step S41 is returned to;
s43, judging whether the second spectrogram has the peak time and PjHave the same peak-off timePeak P of (1)xIf there is a peak P with the same timexStep S44 is entered, otherwise, step S41 is returned to;
s44, judgment PxWhether the signal-to-noise ratio is greater than a set signal-to-noise ratio threshold value and whether the relative abundance is greater than a set relative abundance threshold value, if P isxIs greater than a set signal-to-noise ratio threshold value, and the relative abundance is greater than a set relative abundance threshold value, then P is judgedxIf the signal is a valid signal, the step S45 is entered, otherwise, the step S41 is returned to;
s45, according to P judged as effective signali、PjDetermining organic chloride, organic bromide or nitro substituent contained in the sample to be detected according to the screening result of the mass spectrum difference method;
wherein, the steps S41-S45 are repeated until the comparison between all the peaks in the first spectrogram is completed.
Further, the set signal-to-noise ratio threshold is 3, and the set relative abundance threshold is 3%.
Further, the step S1 includes: performing solid-phase extraction on a water sample to be detected by using a solid-phase extraction column; eluting the solid phase extraction column to obtain an eluent; and blowing nitrogen to the eluent until the eluent is completely dried, and dissolving the dried product in an organic solvent to obtain the sample to be detected.
Further, the solid phase extraction column comprises a first solid phase extraction column with a modified polystyrene-divinylbenzene filler and a second solid phase extraction column with an activated carbon filler, wherein the first solid phase extraction column and the second solid phase extraction column are connected in series when performing solid phase extraction and are connected in parallel when performing elution.
Further, in step S1, the solid phase extraction column, on which the organic substance has been adsorbed, is eluted sequentially with methanol, acetone, and dichloromethane.
Further, the step S1 further includes: before solid phase extraction, the solid phase extraction column without the sample is eluted with dichloromethane, acetone and methanol in sequence.
Further, step S1 further includes: before solid-phase extraction, dichloromethane, acetone and methanol are used for eluting an unloaded solid-phase extraction column in sequence, and then methanol and ultrapure water are used for activating the solid-phase extraction column.
The invention has the following beneficial effects:
the invention provides a method for determining chlorine-substituted (-Cl) organic pollutants, bromine-substituted (-Br) organic pollutants and nitro-substituted (-NO) organic pollutants in water by screening through solid phase extraction-two-dimensional gas chromatography-EI mass spectrometry-mass spectrometry difference method2) A rapid, simple and effective method for organic pollutants. By providing an analysis method of two-dimensional gas chromatography-electron bombardment/mass spectrometry combined with (GC XGC-EI/MS), the method for screening pollutants in water can conveniently and rapidly realize chlorine substitution (-Cl) organic pollutants, bromine substitution (-Br) organic pollutants and nitro substitution (-NO)2) Reliable screening of organic pollutants, better separation effect on the organic pollutants, identification of volatile organic pollutants and lower instrument cost.
Drawings
FIG. 1 is a flow chart of a method for screening contaminants in water according to an embodiment of the present invention;
FIGS. 2(a) to 2(j) are schematic diagrams of a mass spectrometry difference method according to an embodiment of the present invention;
FIG. 3 is a flow chart of a method for determining signals of organic chloride, organic bromide and nitro substituents according to an embodiment of the present invention;
FIG. 4 is a partial mass spectrum obtained in example 1;
FIG. 5 is a partial mass spectrum obtained in example 2;
FIG. 6 is a partial mass spectrum obtained in example 3.
Detailed Description
The present invention will be described in further detail below with reference to examples and the accompanying drawings. The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features which are believed to be characteristic of the invention, both as to its organization and method of operation, together with further objects and advantages will be better understood from the following description when considered in connection with the accompanying figures. It is to be expressly understood, however, that each of the figures is provided for the purpose of illustration and description only and is intended as an illustration only and not as a definition of the limits of the present invention.
In one embodiment, a method for screening contaminants in water includes the steps of:
s1, obtaining a sample to be detected from a water sample to be detected;
s2, carrying out two-dimensional gas chromatography on the sample to be detected to obtain an intermediate analyte;
s3, dividing the intermediate analyte into two parts, bombarding one part of the intermediate analyte by an EI ion source to generate ions with different mass-to-charge ratios (m/z), and performing Mass Spectrometry (MS) to obtain a first spectrogram arranged in sequence according to the mass-to-charge ratios; performing ECD detection on another part of the intermediate analyte to obtain a second spectrogram;
s4, screening the first spectrogram by adopting a mass spectrum difference method, comparing the first spectrogram with the second spectrogram, and if an effective signal which indicates that the first spectrogram can be organic chloride, organic bromide or nitro substituent exists in the screening result of the mass spectrum difference method and the effective signal also exists in the second spectrogram, judging that the sample to be detected contains the organic chloride, organic bromide or nitro substituent which is indicated by the effective signal.
In some preferred embodiments, the method for screening contaminants in water further comprises the following steps:
s5, comparing the contaminants screened in step S4 with the NIST library to further identify the substance components.
In some preferred embodiments, the mass spectrometry difference method comprises:
for a known sum of mass-to-charge ratios x and m, where m takes any of the following values:
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 a signal corresponding to x + m in the first spectrum is to be confirmed, it is abbreviated as if x + m has a signal, which includes the following cases:
if x +35/37(1 Cl)35/1Cl37) With a signal, the signal indicates the possibility of a monochloro substituent, where the value 35/37 corresponds to 1Cl35/1Cl37；
If x +70/72/74(2 Cl)35/1Cl35+1Cl37/2Cl37) With a signal indicating the possibility of a dichloro substituent, where the value 70/72/74 corresponds to 2Cl35/1Cl35+1Cl37/2Cl37；
If x +105/107/109/111(3 Cl)35/2Cl35+1Cl37/1Cl35+2Cl37/3Cl37) With a signal indicating the possibility of a trichloro substituent, where the value 105/107/109/111 corresponds to 3Cl35/2Cl35+1Cl37/1Cl35+2Cl37/3Cl37；
If x +79/81(1 Br)79/1Br81) With a signal indicating the possibility of a monobromide substituent, where the value 79/81 corresponds to 1Br79/1Br81；
If x +158/160/162(2 Br)79/1Br79+1Br81/2Br81) With a signal indicating the possibility of a dibromo substituent, where the number 158/160/162 corresponds to 2Br79/1Br79+1Br81/2Br81；
If x +237/239/241/243(3 Br)79/2Br79+1Br81/1Br79+2Br81/3Br81) With a signal indicating the possibility of tribromo substitution, where the value 237/239/241/243 corresponds to 3Br79/2Br79+1Br81/1Br79+2Br81/3Br81；
If x +114/116/118(1 Cl)35+1Br79/1Cl37+1Br79(1Cl35+1Br81)/1Cl37+1Br81) There is a signal which indicates that a monochloromonobromo substituent is possible, where the value 114/116/118 corresponds to 1Cl35+1Br79/1Cl37+1Br79(1Cl35+1Br81)/1Cl37+1Br81；
If x +149/151/153/155(2 Cl)35+1Br79/1Cl35+1Cl37+1Br79(2Cl35+1Br81)/1Cl35+1Cl37+1Br81(2Cl37+1Br79)/2Cl37+1Br81) With a signal indicating the possibility of a dichloromonobromide substituent, wherein the 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(1 Cl)35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+1Br81(1Cl35+2Br81)/1Cl37+2Br81) With a signal indicating the possibility of a monochlorobrominated substituent, where the value 193/195/197/199 corresponds to 1Cl35+2Br79/1Cl35+1Br79+1Br81(1Cl37+2Br79)/1Cl37+1Br79+1Br81(1Cl35+2Br81)/1Cl37+2Br81；
If x +46 (-NO)2) With a signal indicating the possibility of nitro substitution, where the value 46 corresponds to-NO2；
Wherein, Cl35Represents a chlorine atom, Cl, of relative atomic mass 3537Denotes a chlorine atom, Br, of relative atomic mass 3779Represents a bromine atom, Br, having a relative atomic mass of 7981Represents a bromine atom having a relative atomic mass of 81, and N representsAnd O represents a nitrogen atom having a relative atomic mass of 14 and a nitrogen atom having a relative atomic mass of 16.
In the case of a monochloro substituent, if the substance contains a chlorine atom with a relative atomic mass of 35, then x +35 will have a signal, thus the signal indicates that there may be Cl-containing35A monochloro substituent of (a); if the substance contains a chlorine atom with a relative atomic mass of 37, then there is a signal for x +37, and thus the signal indicates that there may be Cl37A monochloro substituent of (a).
Taking the nitro substituent as an example, if the substance contains a nitro group (relative molecular mass of 46), then x +46 has a signal, and thus the signal indicates that the nitro substituent may be contained. In a further preferred embodiment, the total number of peaks obtained in said first spectrum is represented by n, PiRepresents the ith peak, P, obtained in the first spectrogramjDenotes the j-th peak obtained in the first spectrum, i, j ═ 1, 2, …, n, and i<j，PxRepresents the x-th peak obtained in the second spectrogram;
the step S4 further includes the steps of:
s41, obtaining a first peak P from the first spectrogram1Starting with the ith peak PiThe sum of the mass-to-charge ratio of (A) and (B) and the jth peak PjComparing the mass-to-charge ratios, and if the comparison results are equal, proceeding to step S42;
s42, judgment Pi、PjWhether the signal-to-noise ratio is greater than a set signal-to-noise ratio threshold value and whether the relative abundance is greater than a set relative abundance threshold value, if P isi、PjIs greater than a set signal-to-noise ratio threshold value, and the relative abundance is greater than a set relative abundance threshold value, then P is judgedi、PjIf the signal is a valid signal, the step S43 is entered, otherwise, the step S41 is returned to;
s43, judging whether the second spectrogram has the peak time and PjPeak P with the same peak-off timexIf there is a peak P with the same timexStep S44 is entered, otherwise, step S41 is returned to;
s44, judgment PxWhether the signal-to-noise ratio is greater than a set signal-to-noise ratio threshold valueAnd whether the relative abundance is greater than a set relative abundance threshold, if PxIs greater than a set signal-to-noise ratio threshold value, and the relative abundance is greater than a set relative abundance threshold value, then P is judgedxIf the signal is a valid signal, the step S45 is entered, otherwise, the step S41 is returned to;
s45, according to P judged as effective signali、PjDetermining organic chloride, organic bromide or nitro substituent contained in the sample to be detected according to the screening result of the mass spectrum difference method;
wherein, the steps S41-S45 are repeated until the comparison between all the peaks in the first spectrogram is completed.
In a more preferred embodiment, the set signal-to-noise ratio threshold is 3 and the set relative abundance threshold is 3%.
In some preferred embodiments, the step S1 includes: performing solid-phase extraction on a water sample to be detected by using a solid-phase extraction column; eluting the solid phase extraction column to obtain an eluent; and blowing nitrogen to the eluent until the eluent is completely dried, and dissolving the dried product in an organic solvent to obtain the sample to be detected.
In some preferred embodiments, the solid phase extraction column comprises a first solid phase extraction column having a modified polystyrene-divinylbenzene filler and a second solid phase extraction column having an activated carbon filler, the first solid phase extraction column and the second solid phase extraction column being in series when performing solid phase extraction and in parallel when performing elution.
In some preferred embodiments, in step S1, the solid phase extraction column that has adsorbed the organic substance is eluted sequentially with methanol, acetone, and dichloromethane.
In a more preferred embodiment, the step S1 further includes: before solid phase extraction, the solid phase extraction column without the sample is eluted with dichloromethane, acetone and methanol in sequence.
In a further preferred embodiment, step S1 further includes: before solid-phase extraction, dichloromethane, acetone and methanol are used for eluting an unloaded solid-phase extraction column in sequence, and then methanol and ultrapure water are used for activating the solid-phase extraction column.
The invention provides a method for screening pollutants in water, in particular to a method for screening chlorine substituted (-Cl) organic matters, bromine substituted (-Br) organic matters, nitro substituted (-NO2) organic matters and the like, and screening pollutants with high reliability by using solid phase extraction-two-dimensional gas chromatography-Electron Impact (EI) mass spectrometry-mass spectrometry difference method screening and NIST spectral library identification. In a typical embodiment, the method for screening pollutants in water mainly comprises the following processes: pretreating a water sample to be detected, and respectively carrying out solid-phase extraction, elution and nitrogen blowing. GC X GC-EI/MS analysis is carried out on the sample to be tested. And screening mass spectrograms obtained by EI-MS by adopting a mass spectrometric difference method, and judging the mass spectrograms into potential organic chlorides, organic bromides and nitro substitutes. And comparing the judged potential organic chloride, potential organic bromide and potential nitro substituent with the shunted ECD detection result, judging the potential organic chloride, potential organic bromide and nitro substituent as determined organic chloride, potential organic bromide and nitro substituent, and simultaneously carrying out quantitative analysis on the ECD result. The results obtained were compared with the NIST library to identify the unknown substance components. The screening method for pollutants in water can conveniently and rapidly screen chlorine-substituted (-Cl) organic pollutants, bromine-substituted (-Br) organic pollutants and nitro-substituted (-NO2) organic pollutants, has a better separation effect on the organic pollutants, can identify volatile organic pollutants, and has a lower instrument cost.
The method of the present invention is explained in detail below by specific examples.
A method for screening contaminants in water, comprising the steps of:
step 1: pretreating a water sample to be detected, and respectively carrying out solid-phase extraction, elution and nitrogen blowing.
The solid phase extraction of step 1 may include sequentially eluting the solid phase extraction column without loading with dichloromethane, acetone and methanol solvents to effectively reduce impurities in the packing.
The solid phase extraction in step 1 may include a solid phase extraction column activated with methanol and ultrapure water.
The solid phase extraction in the step 1 can comprise a solid phase extraction column of modified polystyrene-divinylbenzene filler and a solid phase extraction column of activated carbon filler which are connected in series, and the recovery rate of the target compound can be obviously further improved.
The elution for step 1 may comprise eluting the solid phase extraction column having adsorbed the organic material with methanol, acetone and dichloromethane in sequence
The nitrogen blowing in step 1 may include nitrogen blowing the eluate after the solid phase extraction until the eluate is completely dried, dissolving the eluate in an organic solvent such as n-hexane and dichloromethane, and using the eluate in the next step.
Step 2: GC X GC-EI/MS analysis is carried out on the sample to be tested. A sample to be detected is separated by two-dimensional gas chromatography, and ions with different mass-to-charge ratios (m/z) are generated by an EI ion source. A mass spectrum was obtained in a mass analyser. Deriving original data graph data and drawing a mass spectrogram;
the mass spectrogram in the step 2 is a mass spectrogram arranged in the order of mass-to-charge ratio;
and step 3: screening mass spectrograms obtained by EI-MS by adopting a mass spectrometric difference method, and judging the mass spectrograms into potential monochloro substitutes, dichloro substitutes, trichloro substitutes, monobromo substitutes, dibromo substitutes, tribromo substitutes, monochloro-monobromo substitutes, monochloro-dibromo substitutes and dichloro-monobromo substitutes; nitro substituents;
for the mass spectrometry difference method described in step 3, specifically, if m/z is known as x,
if x +35/37 has a signal, then the signal may be a monochloro substituent, see the graph shown in FIG. 2 (a);
if x +70/72/74 has a signal, then the signal may be a dichloro substituent, see the graph shown in FIG. 2 (b);
if x +105/107/109/111 has a signal, then the signal may be a trichloro-substituent, see the spectrum shown in FIG. 2 (c);
if x +79/81 has a signal, then the signal may be a monobromide substituent, see the graph shown in FIG. 2 (d);
if x +158/160/162 has a signal, then the signal may be a dibromo substituent, see the spectrum shown in FIG. 2 (e);
if x +237/239/241/243 has a signal, then the signal is likely to be a tribromo substituent, see the graph shown in FIG. 2 (f);
if x +114/116/118 has a signal, then the signal may be a monochloromonobromo substituent, see the graph shown in FIG. 2 (g);
if x +149/151/153/155 has a signal, then the signal may be a dichloromonobromide substituent, see the graph shown in FIG. 2 (h);
if x +193/195/197/199 has a signal, then the signal may be a monochlorobrominated substituent, see the spectrum shown in FIG. 2 (i);
if x +46 (-NO)2) If there is a signal, then the signal may be a nitro substituent, see the graph shown in FIG. 2 (j).
The method for determining whether the signal is the signal in step 3 preferably includes:
if S/N >3 and the relative abundance > 3%, then it can be counted as a valid signal.
And 4, step 4: in order to avoid the interference of ions with the same mass-to-charge ratio generated by non-organic chloride, non-organic bromide and non-nitro substituent, comparing the potential organic chloride, potential organic bromide and potential nitro substituent determined in the step 3 with the detection result of shunted ECD, determining the potential organic chloride, potential organic bromide and potential nitro substituent as monochloro substituent, dichloro substituent, trichloro substituent, monobromo substituent, dibromo substituent, tribromo substituent, monochloro monobromo substituent, monochloro dibromo substituent, dichloro monobromo substituent and nitro substituent, and simultaneously performing quantitative analysis by using the ECD result;
if the mass spectrum difference method judges that effective signals of the potential organic chloride, the potential organic bromide and the potential nitro substituent exist, and the effective signals also exist in the shunting ECD detector result, the effective signals are determined to be the certain organic chloride, the certain organic bromide or the certain nitro substituent.
The method for determining whether the detection result of the shunted ECD detector is an effective signal in step 4 is preferably as follows:
if S/N >3 and the relative abundance > 3%, then it can be counted as a valid signal.
The comparison of the ECD detector results with the split stream as described in step 4 indicates whether the peak times are consistent
The method for judging the organic chloride, organic bromide or nitro substituent in step 3 and step 4 can be represented by the method shown in FIG. 3, specifically,
Pirepresents the ith peak, P, obtained in the first spectrogramjDenotes the j-th peak obtained in the first spectrum, i, j ═ 1, 2, …, n, and i<j, a total of n peaks, P, in said first spectrumxThe x-th peak obtained in the spectrogram obtained by the result of the divided ECD detector is shown, m/z is the mass-to-charge ratio, S/N is the signal-to-noise ratio, t is the peak-off time, R is the relative abundance, and m is 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, n peaks common to the first spectrogram are determined.
Judging from the first peak, if the first peak is Pi(i ═ 1) mass-to-charge ratio, plus m, is the second peak P2(j-2) mass-to-charge ratio
Further judge Pi、PjWhether it can be counted as a valid signal. The judgment basis is that P is judgedi、PjWhether the signal-to-noise ratio of>3, and relative abundance>3％
If Pi、PjCan be calculated as a valid signal, further determine PjWhether the peak-off time is P with the same peak-off time exists in a spectrogram obtained by an ECD detection result of the shuntingxPeak(s). If there is a peak with the same time of appearance,
further judge Pj、PxWhether it can be counted as a valid signal. The judgment basis is that P is judgedj、PxWhether the signal-to-noise ratio of>3, and relative abundance>3％
If Pj、PxCan be counted as a valid signal, then P is outputi、Pj、PxAnd judging whether i is the last peak in the first spectrogram, if so, ending the operation.
If PiIs not P plus mjMass to charge ratio ofOr P isi、PjIf the j peak is not larger than n, continuing the judgment, if the j peak is larger than n, converting i into i +1 and j into i +1, and further judging PiIs the mass-to-charge ratio of (A) plus whether m is PjThe mass-to-charge ratio of;
if Pi、PjCan be counted as a valid signal, but PjThe peak-off time of the flow divider does not have P with the same peak-off time in a spectrogram obtained by an ECD detection result of the flow dividerxPeak, or Pj、PxIf i is not the last peak, P is carried outj+1And (6) comparing and judging.
And 5: and (4) comparing the organic chloride, the organic bromide and the nitro substituent screened in the step (4) with an NIST spectral library to identify unknown substance components.
Examples of the invention
The general method comprises the following steps: the solid phase extraction column of the modified polystyrene-divinylbenzene filler is connected with the solid phase extraction column of the activated carbon filler in series. Eluting the solid phase extraction column which is not loaded with the sample by using dichloromethane, acetone and methanol solvent in sequence, and activating the solid phase extraction column by using methanol and ultrapure water; after the water sample is extracted, eluting the solid phase extraction column which adsorbs the organic matters by using methanol, acetone and dichloromethane in sequence; and (3) blowing nitrogen to the eluent after solid phase extraction until the eluent is completely dried, and dissolving the eluent in organic solvents such as normal hexane, dichloromethane and the like.
The samples of examples 1-3 were prepared and data collected in the same manner as follows:
preparing a solid phase extraction column: taking a solid phase extraction column empty column tube with the volume of 6mL, and filling a sieve plate at the bottom of the column tube. Soxhlet extraction is carried out for 24h by three solvents of dichloromethane, acetone and methanol for each filler, 400mg of active carbon or 200mg of modified polystyrene-divinylbenzene filler is added into a column tube and is flattened by a sieve plate.
Solid phase extraction, elution and nitrogen blowing: the extraction column was activated with 5mL of methylene chloride, acetone, methanol, and 10mL of ultrapure water in this order at 1 mL/min. After water sample extraction, separating and respectively eluting solid phase extraction columns containing activated carbon and modified polystyrene-divinylbenzene filler, and merging eluent. The eluent was collected in a glass centrifuge tube and blown to dryness with nitrogen.
And dissolving the dried solid to be detected in a certain amount of organic solvent, and performing two-dimensional gas chromatography-EI mass spectrometry. A sample to be detected is separated by two-dimensional gas chromatography, and then ions with different mass-to-charge ratios (m/z) are generated by an EI ion source. And obtaining mass spectrograms arranged according to the mass-to-charge ratio in a mass analyzer, deriving original data graph data, and drawing the mass spectrograms.
Example 1：
And (3) after the sample to be detected is analyzed by the two-dimensional gas chromatography-EI mass spectrum, obtaining mass spectrograms which are arranged in sequence according to the mass-to-charge ratio, wherein partial mass spectrograms are shown in figure 4. Taking the existing trichloromethane as an example, in the figure, m/z is 14, m/z +105/107/109/111 is 119/121/123/125, mass spectrum peak can be observed at m/z is 119/121/123/125, and S/N is>3，R>3% of the corresponding tapped ECD detector result, and S/N>3，R>3% of the substance to be measured, therefore, contains trichloro (C)35Cl and37cl) contaminants. Further characterization can be performed in conjunction with NIST panel library.
Example 2：
After the sample to be detected is analyzed by the two-dimensional gas chromatography-EI mass spectrometry, mass spectrograms which are arranged in sequence according to the mass-to-charge ratio are obtained, wherein partial mass spectrograms are shown in figure 5. Taking the existing monobromoacetonitrile as an example, in the figure, m/z is 40, m/z +79/81 is 119/121, mass spectrum peak can be observed at m/z is 119/121, and S/N is>3，R>3% of the corresponding tapped ECD detector result, and S/N>3，R>3%, therefore, the substance to be tested contains monobromo (b)79Br and81br) contaminants. Further characterization can be performed in conjunction with NIST panel library.
Example 3：
After the sample to be detected is analyzed by the two-dimensional gas chromatography-EI mass spectrometry, mass spectrograms which are arranged in sequence according to the mass-to-charge ratio are obtained, wherein partial mass spectrograms are shown in figure 6. Taking the conventional nitrobenzene as an example, in the figure, m/z is 77, m/z +46 is 123, mass spectrum peak can be observed at m/z is 123, and S/N is 3, R is 3%, the signal is present in the corresponding divided ECD detector result, and S/N is 3, R is 3%, therefore, the substance to be tested contains nitro-substituted pollutant. Further characterization can be performed in conjunction with NIST panel library.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and these substitutions and modifications should be considered to fall within the scope of the invention. In the description herein, references to the description of the term "one embodiment," "some embodiments," "preferred embodiments," "an example," "a specific example," or "some examples" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. One of ordinary skill in the art will readily appreciate that the above-disclosed, presently existing or later to be developed, processes, machines, manufacture, compositions of matter, means, methods, or steps, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims (2)

1. A method for screening contaminants in water, comprising the steps of:
s1, obtaining a sample to be detected from a water sample to be detected; wherein, the solid phase extraction column of the modified polystyrene-divinylbenzene filler is connected with the solid phase extraction column of the activated carbon filler in series; eluting the solid phase extraction column which is not loaded with the sample by using dichloromethane, acetone and methanol solvent in sequence, and activating the solid phase extraction column by using methanol and ultrapure water; after the water sample is extracted, eluting the solid phase extraction column which adsorbs the organic matters by using methanol, acetone and dichloromethane in sequence; blowing nitrogen to the eluent after solid phase extraction until the eluent is completely dried, and dissolving the eluent in an organic solvent to obtain the sample to be detected;
s2, carrying out two-dimensional gas chromatography on the sample to be detected to obtain an intermediate analyte;
s3, dividing the intermediate analyte into two parts, bombarding one part of the intermediate analyte by an EI ion source to generate ions with different mass-to-charge ratios, and performing mass spectrometry to obtain a first spectrogram arranged in sequence according to the mass-to-charge ratios; performing ECD detection on another part of the intermediate analyte to obtain a second spectrogram;
s4, screening the first spectrogram by adopting a mass spectrum difference method, comparing the first spectrogram with the second spectrogram, and if an effective signal which indicates that the first spectrogram is possibly organic chloride, organic bromide or nitro substituent exists in a screening result of the mass spectrum difference method and the effective signal also exists in the second spectrogram, determining that the sample to be detected correspondingly contains the organic chloride, the organic bromide or the nitro substituent;
s5, comparing the pollutants determined in the step S4 with a NIST spectrum library to further identify substance components;
the mass spectrum difference method comprises the following steps:
for a known sum of mass-to-charge ratios x and m, where m takes any of the following values:
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 a signal corresponding to x + m is to be validated in the first spectrum, it is abbreviated as if x + m has a signal, which includes the following cases:
if x +35/37 has a signal, this signal indicates the possibility of a chlorine substituent, where the value 35/37 corresponds to 1Cl35/1 Cl37；
If x +70/72/74 has a signal, then the signal indicates that a dichloro substituent is possible, where the value 70/72/74 corresponds to 2Cl35/ 1Cl35+1 Cl37/2 Cl37；
If x +105/107/109/111 has a signal, the signal indicates the possibility of a trichloro substituent, where the value 105/107/109/111 corresponds to 3Cl35/ 2Cl35+1 Cl37/ 1Cl35+2Cl37/3Cl37；
If x +79/81 has a signal, the signal indicates the possibility of a bromine substitution, where the value 79/81 corresponds to 1Br79/1 Br81；
If x +158/160/162 has a signal, this signal indicates the possibility of a dibromo substituent, where the number 158/160/162 corresponds to 2Br79/ 1 Br79+1 Br81/2 Br81；
If x +237/239/241/243 has a signal, the signal indicates that tribromide substitution is possible, where the value 237/239/241/243 corresponds to 3Br79/ 2 Br79+1 Br81/ 1 Br79+2 Br81/3 Br81；
If x +114/116/118 has a signal, this signal indicates the possibility of a monochloro-monobromo substituent, where the value 114/116/118 corresponds to 1Cl35+1 Br79/ 1 Cl37+1 Br79(1 Cl35+1 Br81)/ 1 Cl37+1 Br81；
If x +149/151/153/155 has a signal, the signal indicates that dichloromonobromide substituents are possible, where the number 149/151/153/155 pairsTo 2Cl35+1 Br79/ 1 Cl35+1 Cl37+1 Br79（2Cl35+1 Br81）/ 1 Cl35+1 Cl37+1 Br81（2 Cl37+1 Br79）/2 Cl37+1 Br81；
If x +193/195/197/199 has a signal, this signal indicates the possibility of monochlorobrominated substituents, where the number 193/195/197/199 corresponds to 1Cl35+2 Br79/ 1 Cl35+1 Br79+1 Br81（1Cl37+2Br79）/ 1 Cl37+1 Br79+1 Br81（1Cl35+2 Br81）/1 Cl37+2 Br81；
If x +46 has a signal, this signal indicates the possibility of nitro substitution, where the value 46 corresponds to-NO2；
Wherein, Cl35Represents a chlorine atom, Cl, of relative atomic mass 3537Denotes a chlorine atom, Br, of relative atomic mass 3779Represents a bromine atom, Br, having a relative atomic mass of 7981Represents a bromine atom having a relative atomic mass of 81, N represents a nitrogen atom having a relative atomic mass of 14, and O represents a nitrogen atom having a relative atomic mass of 16;
n represents the total number of peaks obtained in the first spectrogram, PiRepresents the ith peak, P, obtained in the first spectrogramjDenotes the jth peak obtained in the first spectrum, i, j =1, 2, …, n, and i<j，PxRepresents the x-th peak obtained in the second spectrogram;
the step S4 further includes the steps of:
s41, obtaining a first peak P from the first spectrogram1Starting with the ith peak PiThe sum of the mass-to-charge ratio of (A) and (B) and the jth peak PjComparing the mass-to-charge ratios, and if the comparison results are equal, proceeding to step S42;
s42, judgment Pi、PjWhether the signal-to-noise ratio is greater than a set signal-to-noise ratio threshold value and whether the relative abundance is greater than a set relative abundance threshold value, if P isi、PjIs greater than a set signal-to-noise ratio threshold value, and the relative abundance is greater than a set relative abundance threshold value, then P is judgedi、PjIf the signal is a valid signal, the step S43 is entered, otherwise, the step S41 is returned to;
s43, judging whether the second spectrogram has the peak time and PjPeak P with the same peak-off timexIf there is a peak P with the same timexStep S44 is entered, otherwise, step S41 is returned to;
s44, judgment PxWhether the signal-to-noise ratio is greater than a set signal-to-noise ratio threshold value and whether the relative abundance is greater than a set relative abundance threshold value, if P isxIs greater than a set signal-to-noise ratio threshold value, and the relative abundance is greater than a set relative abundance threshold value, then P is judgedxIf the signal is a valid signal, the step S45 is entered, otherwise, the step S41 is returned to;
s45, according to P judged as effective signali、PjDetermining organic chloride, organic bromide or nitro substituent contained in the sample to be detected according to the screening result of the mass spectrum difference method;
wherein, the steps S41-S45 are repeated until the comparison between all the peaks in the first spectrogram is completed.
2. The method of screening for contaminants in water of claim 1, wherein the set threshold signal to noise ratio is 3 and the set threshold relative abundance is 3%.
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