CN105334284B - It is a kind of to identify and remove the method that carboxylic acids disturbs in perfluorobutyric acid detection - Google Patents

It is a kind of to identify and remove the method that carboxylic acids disturbs in perfluorobutyric acid detection Download PDF

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CN105334284B
CN105334284B CN201510885868.9A CN201510885868A CN105334284B CN 105334284 B CN105334284 B CN 105334284B CN 201510885868 A CN201510885868 A CN 201510885868A CN 105334284 B CN105334284 B CN 105334284B
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extraction column
phase extraction
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CN105334284A (en
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杜兵
杨文龙
郭靖
董亮
黄业茹
张秀蓝
刘金林
朱超飞
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ENVIRONMENTAL ANALYSIS AND TESTING CENTER
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract

The invention belongs to environmental monitoring, discloses the method for carboxylic acids interference and the detection method of perfluorobutyric acid in a kind of identification perfluorobutyric acid detection.The method that carboxylic acids disturbs in identification perfluorobutyric acid detection provided by the invention, using high performance liquid chromatography tandem mass spectrum, analysis process is simple and easy to do, and detection is sensitive, qualitative accurate.The detection method of perfluorobutyric acid provided by the invention, is connected using solid-phase extraction column, is removed carboxylic acids and is disturbed and be enriched with target compound, is greatly improved the detection accuracy of target compound.Carboxylic acids disturbs in identification perfluorobutyric acid detection provided by the invention method, the detection method of perfluorobutyric acid and the pre-treating method for perfluorobutyric acid detection can be used for the analysis of perfluorobutyric acid in surrounding medium.

Description

It is a kind of to identify and remove the method that carboxylic acids disturbs in perfluorobutyric acid detection
Technical field
The present invention relates to environmental monitoring technology field, and in particular to carboxylic acids in one kind identification and removal perfluorobutyric acid analysis The analysis method of interference.
Background technology
Perfluorochemical (PFCs) mainly includes perfluoro capryl carboxylic acid (PFOA), PFOS (PFOS), the perfluor last of the ten Heavenly stems Sour (PFDA) etc., because of its excellent heat endurance, chemical stability, high surface and hydrophobic oleophobic performance, is widely used In the production of many industrial goods such as polymeric additive, lubricant, corrosion inhibiter and many industry fields such as weaving, papermaking, PFOA It is representational PFCs with PFOS.There are some researches show it has organ toxicity, genotoxicity, carcinogenicity and immunotoxicity etc. more Kind poisonous effect, and can be accumulated with food chain in animal and human body, there is serious harm to the mankind.In May, 2009 combines United Nations Environment Programme (UNEP) of state and《Convention of Stockholm on persistence organic pollutant (POPs)》4th conference of contracting party is just Reduce and finally prohibit the use of the toxic chemical substance of 9 kinds of serious harm human healths and natural environment to reach common understanding.This 9 kinds new POPs include PFOS and its derivative.
Perfluorobutyric acid (Perfluorobutyric Acid, PFBA) is perfluori piated carboxylic acids (Perfluorinated Alkyl Acids) one kind in compound, No. CAS is 375-22-4, molecular formula C4HF7O2, molecular weight 214.04, it is that PFOA exists One of catabolite in environment (the degrading perfluorinated octanoic acids of Lei Min .UV-Fenton and its study mechanism Wuhan：Central China science and technology is big Learn, 2011.), Zhang Xianzhong etc. by detect in the sewage disposal plant effluent sample of Tianjin PFCs concentration find PFBA concentration compared with High (the perfluorochemical Environmental Chemistries in the such as Zhang Xianzhong SPEs-high performance liquid chromatography tandem mass spectrum technology measure sewage, 2009(6)：944-945.), occurrence status of the environmental area to perfluorobutyric acid in surrounding medium (water body, soil etc.) are very heavy Depending on.
The international organization of present analysis perfluori piated carboxylic acids compound analysis, national standard method have：The method of ISO tissues ISO 25101:2009《Water quality-Determination of perfluoro octanesulfonate (PFOS)and perfluoroctanoate(PFOA)-Method for unfil tered samples using solid phase extraction and liquid chromatography/mass spectrometry》；U.S. material and experiment The D7979-15 of association (ASTM) issue《Standard Test Method for Determination of Perfluorinated Compounds in Water,Sludge,Influent,Effluent and Wastewater by Liquid Chromatography Tandem Mass Spectrometry(LC/MS/MS)》And D7968-14《Standard Test Method for Determination of Perfluorinated Compounds in Soil by Liquid Chromatography Tandem Mass Spectrometry(LC/MS/MS)》；The EPA method of Environmental Protection Agency's issue 537:2009《Determination of selected perluorinated alkyl acids in drinking water by solid phase extraction and liquid chromatography/tandem mass spectrometry(LC/MS/MS)》With《Draft Procedure for Analysis of Perfluorinated Carboxylic Acids and Sulfonic Acids in Sewage Sludge and Biosolids by HPLC/ MS/MS》；And the JIS K0450-70-10-2011 of Japanese industry association issue《Testing methods for perfluorooctane-sulfonate(PFOS)and perfluorooctanoate(PFOA)in industrial water and wastewater》。
Wherein can be used for PFBA analysis method have American Society Testing and Materials (ASTM) issue D7979-15 and D7968-14, and the EPA draft of Environmental Protection Agency's issue, method are used with the triple level Four bar mass spectrum (LC/ of liquid chromatogram MS/MS the isotopic dilution analysis method based on).PFBA transmission ion pair 213-169 is selected, i.e. perfluorobutyric acid sloughs carboxylic The transmission ion pair of acid group is monitored.Direct-injection technique analysis can be used, EPA draft also use solid phase extraction column (such as WAX etc.) it is enriched with progress Instrumental Analysis analysis after concentration.
Chinese patent CN104237402 discloses perfluorochemical extraction and assay method in a kind of bark, leaf, will set The extract solution of perfluorochemical collects eluent, nitrogen blows over filter, utilizes liquid chromatogram by WAX solid-phase extraction columns in skin, leaf The amount of mass spectrometry analysis method measure wherein perfluorochemical.This method can complete in a short time extraction to PFCs and Detection, there is exclusion that is workable, efficient, but being not directed to detection and the false positive interference of perfluorobutyric acid, to dividing The accuracy of analysis result has a certain impact.
With other perfluori piated carboxylic acids compound analysis can monitor simultaneously two groups of transmission ion pairs (quota ion pair, it is qualitative Ion pair) compare, PFBA due to self structure property, be only capable of produce one group be used for monitor transmission ion pair, i.e., from Son, for producing transmission ion pair 213-169 and retention time identical compound, can produce false positive to 213-169 Interference, by taking dodecane carboxylic acid as an example, its molecular formula is C12H25COOH, molecular weight is consistent with perfluorobutyric acid, and it sloughs carboxylate radical It is also 213-169 to transmit ion pair, and its isomers quantity is very big, is widely present in the environment, and existing analysis method can not arrange Except the false positive issue come from carboxylic acids interference fringe.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of technique is simple, it is qualitative it is accurate, perfluor can be improved The analysis method and remove perfluorobutyric acid analysis that carboxylic acids disturbs during the identification perfluorobutyric acid analysis of butyric acid analytical precision During carboxylic acids disturb analysis method.
Thus, one aspect of the present invention provides a kind of method for identifying that carboxylic acids disturbs in perfluorobutyric acid detection, including as follows Specific steps：
(1) sample detection：By sample filtering film, obtained filtrate carries out high performance liquid chromatography tandem mass spectrum detection, obtained Sample spectrogram；
(2) spectrum analysis：The qualitative ion pair of perfluorobutyric acid is 213-169, interference characterisation ion pair be respectively 213-X, 213-Y and 213-Z, its peak area are respectively T1, T2, T3 and T4；
(3) judgement of carboxylic acids interference：As the peak area T2/T1 that step (2) obtains>A, and/or, T3/T1>B, and/or, T4/T1>During c, carboxylic acids interference be present.
X, Y and Z is the daughter ion that ion pair is transmitted in specific interference, and its span is respectively：200-220,180- 200,130-160；
A, b and c is special ratios coefficient, and its span is respectively：0.2-5.0,0.1-1.0,0.05-1.0.
The condition of high performance liquid chromatography tandem mass spectrum is such as in specific embodiments of the present invention, in described step (1) Under：
Chromatographic condition：
Chromatographic column：Use the liquid-phase chromatographic column of C18 fillers；
Flow velocity：0.1-0.6mL/min；
Column temperature：30-40℃；
Sample size：5-20μL；
Mobile phase and elution time：
Mobile phase A：Acetonitrile；
Mobile phase B：2mM ammonium acetate solutions (pH5.9)；
Elution time 0-3min, mobile phase A concentration：20%-40%, Mobile phase B concentration：60%-80%；
Elution time 3-9min, mobile phase A concentration：55%-75%, Mobile phase B concentration：25%-45%；
Elution time 9-16min, mobile phase A concentration：80%-100%, Mobile phase B concentration：0-20%；
Elution time 16-21min, mobile phase A concentration：20%-40%, Mobile phase B concentration：60%-80%.
Mass Spectrometry Conditions：
Ionization pattern：Negative electrospray ion gun (ESI)；
Detection mode：More reaction detection (MRM) patterns；
Atomization gas flow velocity：2-4L/min；Drier flow velocity：8-12L/min；
Desolventizing pipe (DL) temperature：240-260℃；Heat deblocking temperature (HB)：380-420℃；
Carboxylic acids disturbs during sample can recognize that perfluorobutyric acid analysis using the above method, as testing result shows sample In carboxylic acids be not present disturb, sample can be directly used for the detection and analysis of perfluorobutyric acid；Contain as testing result is shown in sample Carboxylic acids disturbs, and need to remove the analysis that perfluorobutyric acid could be carried out after carboxylic acids disturbs.
Another aspect of the present invention provides a kind of pre-treating method for perfluorobutyric acid detection, including：
(1) rate of recovery indicant adds：Correct amount takes sample, adds rate of recovery indicant after filter membrane, stands；
(2) SPE：Solid-phase extraction column 1 and solid-phase extraction column 2 are taken, connects, the sample that step (1) obtains is led to successively Solid-phase extraction column 1 and solid-phase extraction column 2 are crossed, solid-phase extraction column 1 is nonpolar solid-phase extraction column, and solid-phase extraction column 2 is anion Solid-phase extraction column；
(3) elute：The solid-phase extraction column 1 and solid-phase extraction column 2 that step (2) is obtained are separated, and eluent is carried out respectively Elution, collects eluent 1 and eluent 2 respectively, and eluent 2 is used for the measure of perfluorobutyric acid.
Rate of recovery indicant described in step (1) is Isotopic Internal Standard thing13C4-PFBA(M4PFBA) standard liquid, more Preferably, the M4The density of PFBA standard liquids is 40-60 μ g/mL, and solvent is methanol；
Preferably, solid-phase extraction device can be used in the SPE described in step (2), and described solid-phase extraction device is matched somebody with somebody There are independent regulating valve and vent valve, can control flow velocity and pressure；
Preferably, the sample described in step (2) passes sequentially through solid-phase extraction column 1 and solid-phase extraction column 2 and step (3) Described in elution and elution that solid-phase extraction column 1 and solid-phase extraction column 2 are carried out with leacheate and eluent, it is true using taking out The method of empty, pressurization or centrifugation is realized, is more preferably vacuumized using vavuum pump to realize, the max vacuum of described vavuum pump Degree is not less than -50kPa, and capacity is not less than 3m3/h；
Solid-phase extraction column 1 described in step (2) is nonpolar solid-phase extraction column, preferably HLB posts, and its filler is divinyl The macroporous copolymer or other connection of equivalent type fillers that base benzene and NVP are polymerized by a certain percentage；
Solid-phase extraction column 2 described in step (2) is anion solid-phase extraction column, preferably WAX posts, and its filler is N- ethene Base pyrrolidones-divinyl benzene copolymer bonding piperazine group；
Preferably, water-miscible organic solvent 1 and water or water solubility are used before the solid-phase extraction column 1 described in step (2) uses The aqueous solution elution activation of organic solvent 1, described water-miscible organic solvent 1 are selected from：Methanol, ethanol, acetonitrile, formic acid, ammoniacal liquor One or more in methanol solution etc., preferably methanol；
Preferably, water-miscible organic solvent 2 and water or water solubility are used before the solid-phase extraction column 2 described in step (2) uses The aqueous solution elution activation of organic solvent 2, described water-miscible organic solvent 2 are selected from：Methanol, ethanol, acetonitrile, formic acid, ammoniacal liquor One or more in methanol solution etc., preferably ammoniacal liquor methanol solution and/or methanol；Described ammoniacal liquor methanol solution preferred concentration For 0.1%-1.0% ammoniacal liquor methanol solution；
The eluent of solid-phase extraction column 1 described in step (3) is selected from：In methanol, ethanol, acetonitrile, formic acid etc. it is a kind of or It is a variety of, preferred methanol；
The eluent of solid-phase extraction column 2 described in step (3) is selected from：Methanol, ethanol, acetonitrile, formic acid, ammoniacal liquor methanol are molten One or more, preferably ammoniacal liquor methanol solution in liquid etc., more preferably concentration are 0.1%-1.0% ammoniacal liquor methanol solution；
Preferably, the solid-phase extraction column 1 that step (2) obtains can be eluted before elution, and leacheate is selected from：Methanol, second One or more aqueous solution, preferably methanol aqueous solution in alcohol, acetonitrile, formic acid etc.；
Preferably, the solid-phase extraction column 2 that step (2) obtains can be eluted before elution, and leacheate is selected from：Methanol, second In alcohol, acetonitrile, formic acid etc. it is a kind of in one or more aqueous solution or buffer solution and/or methanol, ethanol, acetonitrile, formic acid etc. or A variety of, described buffer solution is selected from：Acetate buffer solution, phosphate buffer, citrate buffer solution etc., preferably acetate buffer solution, more Preferably pH3.0-5.0 acetate buffer solution.
The carboxylic acids chaff interference and other perfluorochemicals that solid-phase extraction column 1 is used in enriched sample, solid-phase extraction column 2 For the perfluorobutyric acid in enriched sample.
Another aspect of the present invention is to provide a kind of detection method of perfluorobutyric acid detection, comprises the following specific steps that：
(1) rate of recovery indicant adds：Correct amount takes sample, adds rate of recovery indicant after filter membrane, stands；
(2) SPE：Solid-phase extraction column 1 and solid-phase extraction column 2 are taken, connects, the sample that step (1) obtains is led to successively Solid-phase extraction column 1 and solid-phase extraction column 2 are crossed, solid-phase extraction column 1 is nonpolar solid-phase extraction column, and solid-phase extraction column 2 is anion Solid-phase extraction column；
(3) elute：The solid-phase extraction column 1 and solid-phase extraction column 2 that step (2) is obtained are separated, and eluent is carried out respectively Elution, collects eluent 1 and eluent 2 respectively, and eluent 2 is used for the measure of perfluorobutyric acid；
Preferably, using distilled water as blank sample, take the distilled water with sample same volume, according to above-mentioned steps (1)- (3) same operation step, the detection of blank sample is carried out；
(4) eluent is handled：The eluent 1 and eluent 2 that step (3) is obtained, which are concentrated into, closely to be done, after solvent constant volume Filter membrane, preserve, the measure for PFBA；Preferably, constant volume solvent for use is methanol, and described is concentrated by 35-45 DEG C Lower nitrogen blows realization, and the aperture of the filter membrane is 0.22 μm；
(5) PFBA is determined：The eluent 2 that step (4) is obtained carries out PFBA measure, it is preferred that uses efficient liquid phase Chromatographic tandem Mass Spectrometer Method, according to the spectrum analysis PFBA rate of recovery.
Rate of recovery indicant described in step (1) is Isotopic Internal Standard thing13C4-PFBA(M4PFBA) standard liquid, more Preferably, the M4The density of PFBA standard liquids is 40-60 μ g/mL, and solvent is methanol；
Preferably, solid-phase extraction device can be used in the SPE described in step (2), and described solid-phase extraction device is matched somebody with somebody There are independent regulating valve and vent valve, can control flow velocity and pressure；
Preferably, the sample described in step (2) is passed sequentially through in solid-phase extraction column 1 and solid-phase extraction column 2 and step (3) Described elution and elution that solid-phase extraction column 1 and solid-phase extraction column 2 are carried out with leacheate and eluent, using vacuumize, The method of pressurization or centrifugation is realized, is more preferably vacuumized using vavuum pump to realize, the maximum vacuum of described vavuum pump Not less than -50kPa, capacity is not less than 3m3/h；
Solid-phase extraction column 1 described in step (2), its filler are divinylbenzene and NVP by certain The macroporous copolymer or other connection of equivalent type fillers that ratio is polymerized, it is preferred that column volume 4-8mL, amount of filler 100- 1000mg；
Solid-phase extraction column 2 described in step (2), its filler are NVP-divinyl benzene copolymer It is bonded piperazine group or other connection of equivalent type fillers, it is preferred that column volume 1-6mL, amount of filler 30-200mg；
Preferably, water-miscible organic solvent 1 and water or water solubility are used before the solid-phase extraction column 1 described in step (2) uses The aqueous solution elution activation of organic solvent 1, described water-miscible organic solvent 1 are selected from：Methanol, ethanol, acetonitrile, formic acid, ammoniacal liquor One or more in methanol solution etc., preferably methanol；
Preferably, water-miscible organic solvent 2 and water or water solubility are used before the solid-phase extraction column 2 described in step (2) uses The aqueous solution elution activation of organic solvent 2, described water-miscible organic solvent 2 are selected from：Methanol, ethanol, acetonitrile, formic acid, ammoniacal liquor One or more in methanol solution etc., preferably ammoniacal liquor methanol solution and/or methanol；Described ammoniacal liquor methanol solution preferred concentration For 0.1%-1.0% ammoniacal liquor methanol solution；
The eluent of solid-phase extraction column 1 described in step (3) is selected from：In methanol, ethanol, acetonitrile, formic acid etc. it is a kind of or It is a variety of, preferred methanol；
The eluent of solid-phase extraction column 2 described in step (3) is selected from：Methanol, ethanol, acetonitrile, formic acid, ammoniacal liquor methanol are molten One or more, preferably ammoniacal liquor methanol solution in liquid etc., more preferably concentration are 0.1%-1.0% ammoniacal liquor methanol solution；
Preferably, the solid-phase extraction column 1 that step (2) obtains can be eluted before elution, and leacheate is selected from：Methanol, second One or more aqueous solution, preferably methanol aqueous solution in alcohol, acetonitrile, formic acid etc.；
Preferably, the solid-phase extraction column 2 that step (2) obtains can be eluted before elution, and leacheate is selected from：Methanol, second In alcohol, acetonitrile, formic acid etc. it is a kind of in one or more aqueous solution or buffer solution and/or methanol, ethanol, acetonitrile, formic acid etc. or A variety of, described buffer solution is selected from：Acetate buffer solution, phosphate buffer, citrate buffer solution etc., preferably acetate buffer solution, more Preferably pH3.0-5.0 acetate buffer solution；
The instrument condition of high performance liquid chromatography tandem mass spectrum in step (5) is：
Chromatographic condition：
Chromatographic column：Using the liquid-phase chromatographic column of C18 fillers, 3.5 μm, 2.1 × 100mm of particle diameter, or other connection of equivalent type；
Flow velocity：0.1-0.6mL/min；
Column temperature：30-40℃；
Sample size：5-20μL；
Mobile phase and elution time：
Mobile phase A：Acetonitrile；
Mobile phase B：2mM ammonium acetate solutions (pH5.9)；
Elution time 0-3min, mobile phase A concentration：20%-40%, Mobile phase B concentration：60%-80%；
Elution time 3-9min, mobile phase A concentration：55%-75%, Mobile phase B concentration：25%-45%；
Elution time 9-16min, mobile phase A concentration：80%-100%, Mobile phase B concentration：0-20%；
Elution time 16-21min, mobile phase A concentration：20%-40%, Mobile phase B concentration：60%-80%.
Mass Spectrometry Conditions：
Ionization pattern：Negative electrospray ion gun (ESI)；
Detection mode：More reaction detection (MRM) patterns；
Atomization gas flow velocity：2-4L/min；Drier flow velocity：8-12L/min；
Desolventizing pipe (DL) temperature：240-260℃；Heat deblocking temperature (HB)：380-420℃；
In the specific embodiment of the present invention, the detection method of described perfluorobutyric acid is also including of the present invention Identification perfluorobutyric acid detection in carboxylic acids disturb method the step of, i.e.,：
(1) sample detection：By sample filtering film, obtained filtrate carries out high performance liquid chromatography tandem mass spectrum detection, obtained Sample spectrogram；
(2) spectrum analysis：The qualitative ion pair of perfluorobutyric acid is 213-169, interference characterisation ion pair be respectively 213-X, 213-Y and 213-Z, its peak area are respectively T1, T2, T3 and T4；
(3) judgement of carboxylic acids interference：As the peak area T2/T1 that step (2) obtains>A, and/or, T3/T1>B, and/or, T4/T1>During c, conditions above sets up its a period of time, carboxylic acids interference be present.
X, Y and Z is the daughter ion that ion pair is transmitted in specific interference, and its span is respectively：200-220,180- 200,130-160；
A, b and c is special ratios coefficient, and its span is respectively：0.2-5.0,0.1-1.0,0.05-1.0.
In the specific embodiment of the present invention, the detection method of described perfluorobutyric acid, comprise the following steps：
(1) collection and preservation of sample：
After sample collection, it is stored in the sampling bottle of polypropylene (PP) material, seals, preserved under the conditions of 4 DEG C of lucifuges；
(2) rate of recovery indicant adds：
The accurate sample for measuring step (1), the Isotopic Internal Standard that concentration is 50 μ g/mL is added after being filtered using quartz filter Thing13C4-PFBA(M4PFBA) standard liquid, stand；
(3) SPE：
Solid-phase extraction device is installed, takes filler to be total to for the macropore that divinylbenzene and NVP are polymerized The solid-phase extraction column 1 and filler of polymers are the solid phase that NVP-divinyl benzene copolymer is bonded piperazine group Extraction column 2, solid phase extraction column 1 use methanol and water wash to activate successively before using, solid phase extraction column 2 is used successively before using 0.5% ammoniacal liquor methanol solution, methanol and water wash activation, are sequentially connected in series the solid phase extraction column 1 activated and SPE are small Post 2, opens vavuum pump, and regulation flow velocity makes the sample that step (2) obtains pass through solid-phase extraction column 1 and 2 to 3-5mL/min；
(4) elute and elute：
After the sample in step (3) is completely by solid-phase extraction column 1 and 2, solid-phase extraction column 1 and solid-phase extraction column are separated 2, wherein solid phase extraction column 1 is eluted using methanol, obtains leacheate 1；Solid-phase extraction column 2 uses high purity water and acetate buffer successively Solution elutes, and discards whole leacheates, dries 1 hour under 65kPa negative pressure, is then eluted with methanol, adds after discarding leacheate Enter the elution of 0.5% ammoniacal liquor methanol solution, obtain eluent 2, collect eluent 2, nitrogen blows the He of concentrate eluant 1 respectively at 40 DEG C Eluent 2 is near dry, after methanol constant volume, with being transferred to sample injection bottle after 0.22 μm of membrane filtration.Wherein eluent 2 is used for PFBA measure, eluent 1 are used for the measure of other perfluorinated compounds；
(5) PFBA is determined：
The eluent 2 that step (4) is obtained carries out high performance liquid chromatography tandem mass spectrum detection, according to spectrum analysis PFBA's The rate of recovery, high performance liquid chromatography tandem mass spectrum experiment condition are as follows：
Chromatographic condition：
Chromatographic column：Using the liquid-phase chromatographic column of C18 fillers, 3.5 μm, 2.1 × 100mm of particle diameter, or other connection of equivalent type；
Flow velocity：0.1-0.6mL/min；
Column temperature：30-40℃；
Sample size：5-20μL；
Mobile phase and elution time：
Mobile phase A：Acetonitrile；
Mobile phase B：2mM ammonium acetate solutions (pH5.9)；
Elution time 0-3min, mobile phase A concentration：20%-40%, Mobile phase B concentration：60%-80%；
Elution time 3-9min, mobile phase A concentration：55%-75%, Mobile phase B concentration：25%-45%；
Elution time 9-16min, mobile phase A concentration：80%-100%, Mobile phase B concentration：0-20%；
Elution time 16-21min, mobile phase A concentration：20%-40%, Mobile phase B concentration：60%-80%.
Mass Spectrometry Conditions：
Ionization pattern：Negative electrospray ion gun (ESI)；
Detection mode：More reaction detection (MRM) patterns；
Atomization gas flow velocity：2-4L/min；Drier flow velocity：8-12L/min；
Desolventizing pipe (DL) temperature：240-260℃；Heat deblocking temperature (HB)：380-420℃.
It is a further object to provide a kind of method, Yi Zhongquan for identifying that carboxylic acids disturbs in perfluorobutyric acid detection The detection method of fluorine butyric acid or a kind of application for the pre-treating method of perfluorobutyric acid detection in environmental monitoring, described answers With the application including analyzing perfluorobutyric acid from surrounding medium.
The method that carboxylic acids disturbs in identification perfluorobutyric acid detection provided by the invention, utilize high performance liquid chromatography series connection matter Spectrum, analysis process is simple and easy to do, and detection is sensitive, qualitative accurate, can improve the accuracy of analysis.Perfluorobutyric acid provided by the invention Detection method, connected using solid-phase extraction column, simple and easy to do, the removal efficiency of carboxylic acids interference is high, the richness of target compound Collect effect and the rate of recovery is high, be greatly improved the detection accuracy of target compound.
Embodiment
The form of presentation such as " perfluorobutyric acid ", " perfluoro butyl carboxylic acid ", " PFBA " has identical implication in the present invention, can be mutual Use is changed, its equal representation compound F3C-CF2-CF2-COOH。
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation Example is only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects Enclose.
Embodiment 1：The collection and preservation of sample
After water sampling need to being detected, it is stored in the sampling bottle of polypropylene (PP) material, is sealed, in 4 DEG C of lucifuge Under the conditions of.The preservation of water sample should meet the general regulation in GB/T 12999 with management, add thiosulfuric acid if necessary Sodium removes chlorine residue.After sample collection, the preceding processing of sample should be completed in 14 days, sample analysis is completed in 30 days.
Embodiment 2：The identification of carboxylic acids interference
Agents useful for same is the guaranteed reagent for meeting national standard or professional standard and the height without target compound detection Pure water.
PFBA standard liquids：The μ g/mL of ρ=50, solvent is methanol, commercially available certified reference material solution；
13C4-PFBA(M4PFBA) standard liquid：The μ g/mL of ρ=50, solvent is methanol, commercially available certified reference material solution.
(1) liquid phase chromatogram condition
Chromatographic column：Using the liquid-phase chromatographic column of C18 fillers, 3.5 μm, 2.1 × 100mm of particle diameter, or other connection of equivalent type；
Mobile phase A：Acetonitrile；
Mobile phase B：2mM ammonium acetate solutions (pH5.9)；
Flow velocity：0.3mL/min；
Column temperature：35℃；
Sample size：5μL；
Gradient elution program：As shown in table 1.
Table 1：Gradient elution program
(2) tandem mass spectrum condition
Mass spectrum tunes：The method program provided using manufacturer is required to carry out instrument tuning and reaches corresponding index requirement. It is used for the optimization of target compound Mass Spectrometry Conditions using initial flow phase configuration 0.5-1.0 μ g/mL PFBA tuning solution.With 0.3mL/min flow velocity will tune solution and import mass spectrum, monitor [M-H]-ion, and regulation mass spectrometry parameters (voltage, dry temperature Degree, flow velocity etc.) target compound response is optimal value；On this basis, MRM transmission ion pairs, regulation MS/MS ginsengs are monitored Number (impact energy, collision voltage etc.) makes target compound response be optimal value.Mass spectrometry parameters after record optimization are simultaneously arranged to The method condition of MRM detections.Mass Spectrometry Conditions of the Mass Spectrometry Conditions of G2, G3 and G4 ion pair with PFBA.
Mass Spectrometry Conditions：
Ion gun：Negative electrospray ion gun (ESI)；
Detection mode：More reaction detections (MRM)；
Atomization gas flow velocity：3L/min；Drier flow velocity：10L/min；
Desolventizing pipe (DL) temperature：250℃；Heat deblocking temperature (HB)：400℃；
Qualitative, quantitative ion see the table below：
Table 2：The MRM selection ions of object
MRM is detected：
The sample that the processing of Example 1 obtains, sample introduction high performance liquid chromatography tandem mass spectrum, according to the instrument bar of above-mentioned optimization Part carries out sample analysis, after completing measure, obtains the chromatogram of each monitoring ion, records peak area, PFBA, G2, G3 and G4's Peak area is designated as T1, T2, T3 and T4 respectively.
The judgement of carboxylic acids interference：
Peak area T2/T1=6>A, and T3/T1=2>B, prompt to disturb with the presence of carboxylic acids.
Embodiment 3：The removal of carboxylic acids interference
Agents useful for same is the guaranteed reagent for meeting national standard or professional standard and the height without target compound detection Pure water.
Ammoniacal liquor (NH3·H2O)：Concentration is 50% (mass ratio), chromatographically pure；
PH4.0 acetic acid buffer solution：1L high purity waters are dissolved in using appropriate acetic acid (pH5.3), adjust pH to 4.0, ultrasound Mix；
0.5% ammoniacal liquor methanol solution：It is dissolved in using 5mL ammoniacal liquor (pH5.5) in 500mL methanol (pH5.2), ultrasound mixes；
PFBA standard liquids：The μ g/mL of ρ=50, solvent is methanol, commercially available certified reference material solution；
13C4-PFBA(M4PFBA) standard liquid：The μ g/mL of ρ=50, solvent is methanol, commercially available certified reference material solution；
Solid phase extraction column 1：HLB posts, filler are two kinds of lipophilicity divinylbenzene and hydrophily NVP The macroporous copolymer that monomer aggregates into by a certain percentage, 1000mg, column volume 6mL；
Solid phase extraction column 2：WAX posts, filler are NVP-divinylbenzene copolymer matrix-CH2- piperazine Piperazine ring, 150mg, column volume 6mL；
Solid-phase extraction device：It is furnished with independent regulating valve per road, flow velocity is can control, equipped with vent valve, pressure adjustable；
Vavuum pump：Maximum vacuum is not less than -50kPa, and capacity is not less than 3m3/h。
(1) rate of recovery indicant adds
Correct amount learn from else's experience embodiment 1 processing sample 0.5L, after being filtered using quartz filter add Isotopic Internal Standard use Liquid (13C4- PFBA standard liquids), stand 30min.
(2) extract and purify
Solid-phase extraction device is installed, solid phase extraction column 1 uses 4mL methanol, the activation of 4mL water wash successively before using, Gu Activated successively with 4mL 0.5% ammoniacal liquor methanol solution (pH5.8), 4mL methanol and 4mL water wash before mutually extraction pillar 2 uses, The solid phase extraction column 1 and solid phase extraction column 2 that series connection has activated, open vavuum pump, and regulation flow velocity makes sample to 3-5mL/min Product pass sequentially through solid-phase extraction column 1 and 2, after sample is completely by pillar 1 and 2, separate solid-phase extraction column 1 and solid-phase extraction column 2, wherein solid phase extraction column 1 is eluted using 10mL methanol, is obtained eluent 1 and is collected in 10mL test tubes；Solid phase extracts Take post 2 to be eluted successively using 5mL high purity waters and 5mL hac buffers, after discarding whole leacheates, done under 65kPa negative pressure Dry 1 hour, then eluted with 3mL methanol, add the elution of the ammoniacal liquor methanol solutions of 4mL 0.5% after discarding leacheate, eluted Liquid 2 is simultaneously collected in 10mL test tubes, and nitrogen blows concentrate eluant 1 and eluent 2 to closely doing respectively at 40 DEG C, uses respectively Methanol constant volume is to 1.0mL, and solution after constant volume is respectively using after 0.22 μm of membrane filtration and being transferred to sample injection bottle.By above-mentioned place Eluent 1 and eluent 2 after reason are respectively used to the measure of other perfluorinated compounds and PFBA measure.
While sample is analyzed, take the distilled water of same volume, according to sample pre-treatments same operation step, prepare Blank sample.
Embodiment 4：PFBA measure
The eluent 2 that the sample and embodiment 3 that embodiment 1 is collected respectively obtain carries out PFBA analysis, analysis Condition is high performance liquid chromatography tandem mass spectrum, and actual conditions is as follows：
(1) liquid phase chromatogram condition
Chromatographic column：Using the liquid-phase chromatographic column of C18 fillers, 3.5 μm, 2.1 × 100mm of particle diameter, or other connection of equivalent type；
Mobile phase A：Acetonitrile；
Mobile phase B：2mM ammonium acetate solutions (pH5.9)；
Flow velocity：0.3mL/min；
Column temperature：35℃；
Sample size：5μL；
Gradient elution program：As shown in table 1.
Table 1：Gradient elution program
(2) tandem mass spectrum condition
Mass spectrum tunes：The method program provided using manufacturer is required to carry out instrument tuning and reaches corresponding index requirement.
Mass Spectrometry Conditions：
Ion gun：Negative electrospray ion gun (ESI)；
Detection mode：More reaction detections (MRM)；
Atomization gas flow velocity：3L/min；Drier flow velocity：10L/min；
Desolventizing pipe (DL) temperature：250℃；Heat deblocking temperature (HB)：400℃；
Qualitative, quantitative ion see the table below：
Table 2：The MRM selection ions of object
MRM is detected
High performance liquid chromatography tandem mass spectrum, sample introduction, sample analysis is carried out according to the instrument condition of above-mentioned optimization, completes measure Afterwards, the chromatogram of each monitoring ion is obtained, records peak area, analysis calculates PFBA contents.
The PFBA analysis results that embodiment 1 and embodiment 3 handle obtained sample are respectively 11.7ng/L and 7.5ng/L. When carrying out quantitative using isotope-dilution analysis, M4PFBA rate of recovery average out to 85%, relative standard deviation 51%.Illustrate implementing Under conditions of example 2 identifies the carboxylic acids interference in sample, the carboxylic acids that effectively removes in sample is handled by embodiment 3 Interference, substantially increase the accuracy of PFBA analyses.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention Within god and principle, any modification for being made, equivalent substitution etc., it should be included in the scope of the protection.

Claims (12)

1. a kind of method for identifying that carboxylic acids disturbs in perfluorobutyric acid detection, is comprised the following specific steps that：
(1) sample detection：By sample filtering film, obtained filtrate carries out high performance liquid chromatography tandem mass spectrum detection, obtains sample Spectrogram；
(2) spectrum analysis：The qualitative ion pair of perfluorobutyric acid is 213-169, and interference characterisation ion pair is respectively 213-X, 213-Y And 213-Z, its peak area are respectively T1, T2, T3 and T4；
(3) judgement of carboxylic acids interference：As the peak area T2/T1 that step (2) obtains>A, and/or, T3/T1>B, and/or, T4/ T1>During c, carboxylic acids interference be present；
X, Y and Z is the daughter ion that ion pair is transmitted in specific interference, and its span is respectively：200≤X ＜ 213,180- 200,130-160；
A, b and c is special ratios coefficient, and its value is respectively 5.0,1.0,1.0.
2. the method that carboxylic acids disturbs in the detection of identification perfluorobutyric acid as claimed in claim 1, it is characterised in that step (1) The experiment condition of middle high performance liquid chromatography tandem mass spectrum is as follows：
Chromatographic condition：
Chromatographic column：Use the liquid-phase chromatographic column of C18 fillers；
Flow velocity：0.1-0.6mL/min；
Column temperature：30-40℃；
Sample size：5-20μL；
Mobile phase and elution time：
Mobile phase A：Acetonitrile；
Mobile phase B：2mM ammonium acetate solutions；
Elution time 0-3min, mobile phase A concentration：20%-40%, Mobile phase B concentration：60%-80%；
Elution time 3-9min, mobile phase A concentration：55%-75%, Mobile phase B concentration：25%-45%；
Elution time 9-16min, mobile phase A concentration：80%-100%, Mobile phase B concentration：0-20%；
Elution time 16-21min, mobile phase A concentration：20%-40%, Mobile phase B concentration：60%-80%；
Mass Spectrometry Conditions：
Ionization pattern：Negative electrospray ion gun；
Detection mode：More reaction detection patterns；
Atomization gas flow velocity：2-4L/min；Drier flow velocity：8-12L/min；
Desolventizing pipe (DL) temperature：240-260℃；Heat deblocking temperature (HB)：380-420℃.
3. a kind of detection method of perfluorobutyric acid, is comprised the following specific steps that：
(1) rate of recovery indicant adds：Correct amount takes sample, adds rate of recovery indicant after filter membrane, stands；
(2) SPE：Solid-phase extraction column 1 and solid-phase extraction column 2 are taken, is connected, the sample for obtaining step (1) passes sequentially through solid Phase extraction column 1 and solid-phase extraction column 2, solid-phase extraction column 1 are nonpolar solid-phase extraction column, and solid-phase extraction column 2 is anion solid phase Extraction column；
(3) elute：The solid-phase extraction column 1 and solid-phase extraction column 2 that step (2) is obtained are separated, and eluent is eluted respectively, Eluent 1 and eluent 2 are collected respectively, and eluent 2 is used for the measure of perfluorobutyric acid；
(4) eluent is handled：The eluent 1 and eluent 2 that step (3) is obtained concentrate, and with filter membrane after solvent constant volume, protect Deposit, the measure for PFBA；
(5) PFBA is determined：The eluent 2 that step (4) is obtained carries out PFBA measure；
The detection method of described perfluorobutyric acid also includes carboxylic acids in identification perfluorobutyric acid detection as claimed in claim 1 and done Step in the method disturbed.
A kind of 4. detection method of perfluorobutyric acid as claimed in claim 3, it is characterised in that constant volume institute described in step (4) It is methanol with solvent, the described nitrogen at 35-45 DEG C that is concentrated by blows realization, and the aperture of the filter membrane is 0.22 μm.
A kind of 5. detection method of perfluorobutyric acid as claimed in claim 3, it is characterised in that PFBA measure in step (5) Detected using high performance liquid chromatography tandem mass spectrum.
A kind of 6. detection method of perfluorobutyric acid as claimed in claim 3, it is characterised in that the solid phase described in step (2) Extraction column 1 is HLB posts, and/or, the solid-phase extraction column 2 described in step (2) is WAX posts.
A kind of 7. detection method of perfluorobutyric acid as claimed in claim 3, it is characterised in that the solid phase described in step (2) Extraction column 1 and solid-phase extraction column 2 are activated before use with water-miscible organic solvent and water wash, described water-miscible organic solvent 1 is selected from：One or more in methanol, ethanol, acetonitrile, formic acid, ammoniacal liquor methanol solution.
A kind of 8. detection method of perfluorobutyric acid as claimed in claim 3, it is characterised in that the solid phase described in step (2) Extraction column 1 uses preceding methanol and water wash to activate, or, elutes activation with the aqueous solution of methanol；And/or described in step (2) Solid-phase extraction column 2 use before with ammoniacal liquor methanol solution, first alcohol and water elute activation successively.
A kind of 9. detection method of perfluorobutyric acid as claimed in claim 3, it is characterised in that the solid phase described in step (3) The eluent of extraction column 1 is selected from：It is one or more in methanol, ethanol, acetonitrile, formic acid；
And/or the eluent of the solid-phase extraction column 2 described in step (3) is selected from：Methanol, ethanol, acetonitrile, formic acid, ammoniacal liquor methanol It is one or more in solution.
A kind of 10. detection method of perfluorobutyric acid as claimed in claim 3, it is characterised in that the solid phase extraction that step (2) obtains Post 1 is taken to be eluted before elution, leacheate is selected from：One or more aqueous solution in methanol, ethanol, acetonitrile, formic acid；
And/or the solid-phase extraction column 2 that step (2) obtains is eluted before elution, leacheate is selected from：Methanol, ethanol, acetonitrile, One or more in one or more aqueous solution or buffer solution and/or methanol, ethanol, acetonitrile, formic acid in formic acid, described is slow Fliud flushing is selected from：Acetate buffer solution, phosphate buffer, citrate buffer solution.
11. a kind of detection method of perfluorobutyric acid as claimed in claim 10, it is characterised in that what the step (2) obtained The leacheate that solid-phase extraction column 1 is eluted before elution is methanol aqueous solution.
12. a kind of detection method of perfluorobutyric acid as claimed in claim 10, it is characterised in that described buffer solution is acetic acid Buffer solution.
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