CN110286163A - The analysis method of 9 kinds or more nitrosamine compounds in water - Google Patents

The analysis method of 9 kinds or more nitrosamine compounds in water Download PDF

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Publication number
CN110286163A
CN110286163A CN201910364387.1A CN201910364387A CN110286163A CN 110286163 A CN110286163 A CN 110286163A CN 201910364387 A CN201910364387 A CN 201910364387A CN 110286163 A CN110286163 A CN 110286163A
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China
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nitroso
analysis method
amine
extraction
nitrosamine
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黄毅
李程
石喆元
饶竹
田芹
刘晨
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STATE GEOLOGY EXPERIMENT AND TEST CENTER
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STATE GEOLOGY EXPERIMENT AND TEST CENTER
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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
    • G01N30/02—Column chromatography
    • 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
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • 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
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material

Abstract

The present invention relates to a kind of analysis methods of 9 kinds or more nitrosamine compounds in detection water, the nitrosamine compound includes N- nitroso dimethyl amine, N- nitroso Methylethyl amine, N- nitroso diethylamide, N- nitroso dipropylamine, N- nitroso dibutylamine, N- nitrosopyrolidine, N-nitroso-piperidine, N-nitrosomorpholine and N- nitrosodiphenylamine int he, and the analysis method includes the following steps: to carry out extraction processing to water sample to be measured using solid phase microextraction；Nitrosamine compound is measured with using gas-chromatography tandem mass spectrometry (GC-MS/MS).The method of the invention realizes with the content of a variety of nitrosamine compounds in quick, convenient, sensitive measurement water sample, analysis efficiency is high, has preferable promotion prospect.

Description

The analysis method of 9 kinds or more nitrosamine compounds in water
Technical field
The invention belongs to environment measurings and analysis field, and in particular to a kind of point of underwater trace nitrosamine compound Analysis method.
Background technique
Nitrosamine compound (Nitrosoamines) is the one kind for having height mutagenicity and carcinogenicity to the mankind Compound, wherein N- nitroso dimethyl amine (NDMA), N- nitroso diethylamide (NDEA), N- nitroso methyl ethyl-amine (NMEA), N- nitrosopyrolidine (NPYR), N-nitrosomorpholine (NMOR), N-nitroso-piperidine (NPIP), N- nitroso two It is possible that n-propylamine (NDPA) and N- nitroso di-n-butylamine (NDBA) by international cancer research general administration (IARC) are included in the mankind Carcinogen, N nitrosodiphenyl amine (NDPhA) can induce mouse bladder cancer, and in recent years, people detect nitrous in water The presence of aminated compounds, which results in people to produce to content of the nitrosamine in water body, distribution, source and to human health Raw concern a series of problems, such as harm.The analysis of N- nitrosamine has become the one of global environment scientific domain in water at present Big research hotspot, existing research detected in river water, underground water, drinking water and sewage N- nitrosamine there are water.
Since nitrosamine compound trace exists in underground water, detection difficulty increases, and is limited by beneficiation technologies and instrument System, establishes a high sensitivity, analysis underground water Central Asia nitramine compound method easily and fast.
Currently, the toxicity of N- nitrosamine and harm have caused the extensive concern of researcher, more and more researchers The sample substrate for developing the detection method of N- nitrosamine, but the being related to mainly inspection based on food, for N- nitrosamine in water It is less to survey technique study.Zhang Qiuju et al. (7 kinds of nitrosamines chemical combination of headspace solid-phase microextraction-Gas Chromatography-Mass Spectrometry Object [J] Chinese Journal of Health Laboratory Technology, 2009,19 (06): 1234-1236.) have studied 7 kinds of nitrosamines in beer sample The analysis method of compound.Since its test sample is beer, the content of nitrosamines in beer is much higher than underground water or tap water In content of nitrosamines, therefore its analysis method for measure water will lead to test result inaccuracy.American documentation literature (US14/155,429) 4 kinds of N- nitrosamine in headspace solid-phase microextraction-gas chromatography-mass spectrography measurement underground water are disclosed Method.The optimum extraction condition of headspace solid-phase microextraction is had studied using Responds Surface Methodology.But its N- for being used for detection Nitrosamine compound only has 4 kinds, when being related to a greater variety of N- nitrosamine compounds, it is difficult to by each of these kind N- nitrosamine compound is all analyzed accurately.
The detection method of middle N- nitrosamine is mostly with gaschromatographic mass spectrometry and high-efficient liquid phase color in currently reported water Spectrum carries out analysis detection, but gaschromatographic mass spectrometry is the result for being easy to generate false positive to nitrosamine in detection water.
Summary of the invention
Technical problem present in currently available technology is, on the one hand, in the prior art cannot be comprehensively in analysis water-like Nitrosamine compound, the nitrosamine compound type that can be measured is less；On the other hand, the detection limit of the prior art Higher, the detection limit for analyzing nitrosamine compound can only achieve about 200-2000ng/L, when the nitrosamines chemical combination in sample Object content is difficult to measure when being about 10-100ng/L.
The present inventor is in order to solve the above technical problems, by adjusting detection method, using solid phase microextraction to the sample in water Product are enriched with, then use the analysis method of gas-chromatography tandem mass spectrum (GC-MS/MS), pass through scanning secondary ion fragment drop Low impurity interference, can analyze in water with nitrosamine compound existing for trace rank, including N- nitroso dimethyl amine (NDMA), N- nitroso Methylethyl amine (NMEA), N- nitroso diethylamide (NDEA), N- nitroso dipropylamine (NDPA), N- nitroso dibutylamine (NDBA), N- nitrosopyrolidine (NPYR), N-nitroso-piperidine (NPIP), N- are sub- The nitrosamine compound of 9 kinds or more of nitro morpholine (NMOR), N- nitrosodiphenylamine int he (NDPhA) etc..
Detection method disclosed in conventional art document is only to 4 kinds relatively easily detected or 7 kinds of nitrosamine compounds It is tested and analyzed, when there are the nitrosamine compounds of more difficult detections, especially when nitrosamine compound It is difficult to realize comprehensively to detect nitrosamine compound therein when content reaches trace rank.It is shorter in same chromatographic column Accomplish that 9 kinds of nitrosamine compound baseline separation difficulty are bigger in analysis time.Both chemical combination of especially NPYR and NMOR Object is the higher compound of recall rate in water, but since enrichment is not easy, analysis difficulty is further increased.
Specifically, the invention proposes following technical solutions:
The present invention provides a kind of analysis method of 9 kinds or more nitrosamine compounds in detection water, the nitrosamines Compound includes N- nitroso dimethyl amine, N- nitroso Methylethyl amine, N- nitroso diethylamide, N- nitroso dipropyl Base amine, N- nitroso dibutylamine, N- nitrosopyrolidine, N-nitroso-piperidine, N-nitrosomorpholine and N- nitroso hexichol Base amine, the analysis method include the following steps:
(1) extraction processing is carried out to water sample to be measured using solid phase microextraction；With
(2) nitrosamine compound is measured using gas-chromatography tandem mass spectrometry (GC-MS/MS).
Preferably, above-mentioned analysis method, wherein step (2) gas-chromatography uses highly polar or middle polarity Stationary phase chromatographic column；
Preferably, the Strong-polar stationary is selected from polyethylene glycol or (100% cyanogen propyl phenyl of degree of substitution)-methyl Polysiloxanes, it is further preferred that use AC20, PEG20M, HP-Wax, DB-Wax, Carbowax-10, HP-INNOWax, DB-WAXetr, Carbowax-20M, HP-FFAP, DB FFAP or OV-351 chromatographic column；
It may further be preferable that the middle polarity stationary phase is selected from 50% diphenyl of degree of substitution-degree of substitution, 50% diformazan Based polysiloxane, (14% cyanogen propyl phenyl of degree of substitution)-methyl polysiloxane or (50% cyanogen propyl phenyl of degree of substitution)-methyl Polysiloxanes, it is further preferred that use AC10, OV-1701, DB-1701, RTX-1701, AC225, OV-225, BP- 225, DB-225, HP-225 or RTX-225 chromatographic column.
Preferably, above-mentioned analysis method, wherein step (2) described GC conditions include:
Temperature program: 30~50 DEG C of initial temperature, 1~5min is kept, rises to 100~120 DEG C with 10~30 DEG C/min Afterwards, 170~190 DEG C are risen to 5~20 DEG C/min, 230~250 DEG C of holding 6min is risen to 10~30 DEG C/min；Preferably It is 35~45 DEG C of initial temperature, 1~5min is kept, after rising to 105~115 DEG C with 15~25 DEG C/min, with 5~15 DEG C/min 175~185 DEG C are risen to, 235~245 DEG C of 3~9min of holding are risen to 15~25 DEG C/min；It may further be preferable that initial temperature 40 DEG C of degree keeps 2min, after rising to 110 DEG C with 20 DEG C/min, rises to 180 DEG C with 10 DEG C/min, rise to 240 with 20 DEG C/min DEG C keep 6min；
And/or carrier gas and flow: the helium of purity 99.9990V%~99.9999V%, flow 1.0-1.5mL/min, It is preferred that 1.3mL/min；
And/or injector temperature: 160~240 DEG C, preferably 160~200 DEG C, further preferred 170~190 DEG C, Further preferred 180 DEG C；
And/or Sampling liner pipe internal diameter is 0.75-2mm, preferably 0.75-1mm, further preferred 0.75mm.
Preferably, above-mentioned analysis method, wherein step (2) described Mass Spectrometry Conditions include:
Ion source temperature: 160~240 DEG C, preferably 170~220 DEG C, further preferred 180~210 DEG C, further It is preferred that 200 DEG C；
And/or interface temperature: 160~240 DEG C, preferably 190~240 DEG C, it is further preferred that, 200~230 DEG C, further preferred 220 DEG C；
And/or scanning mode: SIM ion monitoring mode or MRM multiple-reaction monitoring pattern, it is preferred to use MRM reacts more Monitoring pattern；It may further be preferable that analyte is divided into 4 periods: 5~8min using MRM multiple-reaction monitoring pattern: N- nitroso dimethyl amine, N- nitroso Methylethyl amine, N- nitroso diethylamide；8~9.5min:N- nitroso dipropyl Base amine；9.5~15min:N- nitroso dibutylamine, N-nitroso-piperidine, N- nitrosopyrolidine, N-nitrosomorpholine；15 ~20min:N- nitrosodiphenylamine int he.
Preferably, above-mentioned analysis method, wherein step (1) described extraction processing is selected from extracting head fiber coat One or more of PDMS, PA, PDMS/DVB, CAR/PDMS；Preferably, the extracting head is PDMS/DVB；
It may further be preferable that the fiber coat is with a thickness of 50 μm or more, further preferred 65-100 μm.
Preferably, above-mentioned analysis method, wherein step (1) extraction processing is extracted using immersion or head space Formula extraction；Preferably, the extraction processing is extracted using head space formula.
Preferably, above-mentioned analysis method, wherein the extraction temperature of step (1) described extraction processing is 30~50 DEG C, preferably 35~45 DEG C, further preferred 40 DEG C；
And/or extraction time is 20min or more, preferably 30min or more, it is further preferred that 30-60min, Further preferred 30min.
Preferably, above-mentioned analysis method, wherein Isotopic Internal Standard is added into step (1) water sample to be measured； Preferably, N- nitroso dimethyl amine-d is added6, N- nitroso Methylethyl amine-d3, N- nitroso diethylamide-d4, N- Nitroso dipropylamine-d14, nitroso dibutylamine-d9, N-nitrosomorpholine-d4With N nitrosodiphenyl amine-d1Isotope One or more of internal standard；It may further be preferable that N- nitroso dimethyl amine-d is added6And/or N- nitroso two Propyl amine-d14Isotopic Internal Standard.
Preferably, above-mentioned analysis method, wherein step (1) volume of water sample to be measured is less than 50ml, preferably 20- 50ml, further preferred 20-30ml.
Preferably, above-mentioned analysis method, wherein include the following steps:
It prepares and contains N- nitroso dimethyl amine, N- nitroso Methylethyl amine, N- nitroso diethylamide, N- nitrous Base dipropylamine, N- nitroso dibutylamine, N- nitrosopyrolidine, N-nitroso-piperidine, N-nitrosomorpholine and N- nitrous The mixed standard solution of base diphenylamine is tested as the water sample to be measured in step (1).
Preferably, above-mentioned analysis method, it is bent including standard of the production chromatography response intensity to concentration of standard solution Line.
On the other hand, the present invention provides a kind of detection methods of disinfection by-products in water, using analysis method of the present invention It is tested and analyzed.
The beneficial effect comprise that
1. the present invention can more fully detect nitrosamine compound present in water sample, detection compound 9 Kind or more.
2. the detection limit of nitrosamine compound present in present invention detection water sample can reach trace rank.
3. the present invention pre-processes water sample using solid phase microextraction, original water sample can be concentrated hundreds times, be reached The minimum detection limit of GC-MS/MS.When the nitrosamine compound content in water sample is trace rank, detection side of the invention Method greatly reduces required volume of water sample, and only detection can be realized in 20ml water sample.
With reference to the accompanying drawing with each specific embodiment, the present invention and its advantageous effects are described in detail, Wherein:
Detailed description of the invention
Fig. 1 is that different extraction needle effect of extracting compare figure.
Fig. 2 is that different extraction mode effect of extracting compare figure.
Fig. 3 is that different extraction temperature effect of extracting compare figure.
Fig. 4-1 and Fig. 4-2 is that different extraction time effect of extracting compare figure, and wherein Fig. 4-1 is 9 kinds of nitrosamine compounds Chromatographic peak peak area and extraction time figure, Fig. 4-2 is NMEA in Fig. 4-1, NDEA, NPIP, NPYR, NMOR5 kind compound Chromatographic peak peak area and extraction time figure.
Fig. 5-1 is capillary column RTX5SiL separation compound effect picture, and (a) is partially 9 kinds of nitrosamine chromatograms in figure, The part b is NMOR, NPYR chromatography enlarged drawing, 1.NDMA in figure；2.NMEA；3.NDEA；4.NDPA；5.NDBA；6.NPIP； 7.NPYR；8.NMOR；9. NDPhA.
Fig. 5-2 is capillary column MEGA-WAX separation compound effect picture, 1.NDMA in figure；2.NMEA；3.NDEA； 4.NDPA；5.NDBA；6.NPIP；7.NPYR；8.NMOR；9. NDPhA.
Fig. 6 is that injection port different temperatures chromatographic peak area compares figure.
Fig. 7-1 is to carry out test chromatogram using 0.75mm internal diameter bushing pipe.
Fig. 7-2 is to carry out test chromatogram using 2mm internal diameter bushing pipe.
Fig. 8 is that distinct interface temperature compares figure to object respective strengths.
Fig. 9 is that different ions source temperature compares figure to object respective strengths.
Figure 10-1 is SIM ion scan mode sample chromatogram figure.
Figure 10-2 is MRM ion scan mode sample chromatogram figure.
Specific embodiment
As described above, being able to detect in water 9 kinds or more nitrosamine compounds the purpose of the present invention is to provide a kind of Method, detection limit are reduced to trace rank.
In the preferred embodiments of the disclosure, detection method includes the following steps for underwater trace N- nitrosamine:
(1) water sample and sodium chloride, NDMA-d will be surveyed6With NDPA-d14Isotopic Internal Standard mixing；
(2) stirring balance, is extracted using head space mode；
(3) gas chromatography-mass spectrum detection is carried out to the sample that extraction is completed；
(4) according to testing result and the standard curve that pre-establishes calculate in water sample to be measured the type of N- nitrosamine and Content.
In the preferred embodiments of the disclosure, while detecting the analysis side of 9 kinds of trace nitrosamine compounds in water Method sequentially includes the following steps:
A, water sample carries out solid phase microextraction processing, and wherein extraction conditions is as follows:
It takes water sample 20mL to be measured in 40mL brown glass sample bottle, sodium chloride is added into water sample respectively to saturation, magnetic Rotor, NDMA-d6(its concentration can by adjusting to sample to be tested response intensity close to determining, preferably 1 μ g/L) with NDPA-d14(its concentration can by adjusting to sample to be tested response intensity close to determining, preferably 1 μ g/L) in isotope Mark；Sample bottle is put into water-bath, balances 10min under conditions of 40 DEG C, revolving speed 1000r/min；65 μm of PDMS/DVB are consolidated Phase extraction head is inserted into sample bottle, extracts 30min using headspace extraction mode；
By combining Isotopic Internal Standard precisely quantitative, effectively excludes instrument wave zone and carry out error, it both can be to a variety of in water sample Trace N- nitrosamine is quantitative determined, but can visual evaluation detection method stability.
B, the sample for obtaining extracting and enriching carries out gas-chromatography tandem mass spectrum test analysis, and wherein gas-chromatography is connected Triple level four bars mass spectrometer parameters；
Chromatographic column: MEGA-WAX (0.25 μ m 0.25mm × 30m)；
Temperature program: 40 DEG C of initial temperature, 2min is kept, after rising to 110 DEG C with 20 DEG C/min, is risen to 10 DEG C/min 180 DEG C, 240 DEG C of holding 6min are risen to 20 DEG C/min；
Carrier gas and flow velocity: high-purity helium, flow velocity 1.3mL/min.
Injector temperature: 180 DEG C；Input mode: Splitless injecting samples；
Ionization mode: the source EI, ionizing energy: 70eV；
Ion source temperature: 200 DEG C, interface temperature: 220 DEG C；
Multiple-reaction monitoring pattern (MRM), the optimization of MRM ion parameters are as shown in table 1.
1 nitrosamine quota ion of table and collision voltage
C, hybrid standard stock solution and standard curve sample are made:
It is accurate according to demand to measure 9 kinds of N- nitrosamine compound mixed standard solutions (concentration of every kind of compound is 1000ug/L), 200 μ g/L, 100 μ g/L, 50 μ g/L, 20 μ g/L, 5 μ g/L are diluted to step by step with methylene chloride, are obtained corresponding dense The hybrid standard stock solution of degree；It is respectively with methylene chloride compound concentration by 9 kinds of nitrosamine compound hybrid standard stock solutions 100ng/L, 200ng/L, 500ng/L, 1000ng/L, 5000ng/L, then it is separately added into Isotopic Internal Standard (preferably 100ng/ L standard curve sample) is obtained, is put in -20 DEG C of refrigerators and saves.
D, standard curve is made
Using gas-chromatography string mass spectrograph, by standard curve sample according to the pretreated method of solid phase microextraction in step a In the sample insertion gas-chromatography tandem mass spectrometer that enrichment is obtained, gas-chromatography series connection is carried out according to the parameter that step b is determined Mass spectrograph measurement, obtains being enriched with to obtain the chromatogram of sample through solid phase microextraction, utilizes chromatographic peak response intensity and addition concentration Respectively transverse and longitudinal coordinate makes standard curve.
E, qualitative analyses and quantitative analysis are carried out to 9 kinds of nitrosamine in water sample, has obtained in water sample containing for 9 kinds of nitrosamine Amount.
In the preferred embodiments of the disclosure, middle polarity or highly polar stationary phase chromatography is can be selected in chromatographic column Column, wherein middle polarity stationary phase is solid relative to non-polar stationary phase (such as 100% dimethyl silicone polymer) or low pole Determine the stronger stationary phase of polarity for phase (such as 100% dimethyl silicone polymer)；The polarity of Strong-polar stationary is than medium Polar stationary phase is stronger.Middle polarity stationary phase can use -50% dimethyl polysiloxane of 50% diphenyl, (14% cyanogen third Base phenyl)-methyl polysiloxane or (50% cyanogen propyl phenyl)-methyl polysiloxane, wherein percentage is the quantity of substituent group Percentage.The corresponding pillar trade mark of middle polarity stationary phase has: AC10, OV-1701, DB-1701, RTX-1701, AC225, OV-225, BP-225, DB-225, HP-225 or RTX-225.Polyethylene glycol is typical Strong-polar stationary, to polar substances There is special separation efficiency, the corresponding pillar trade mark has: HP-Wax, DB-Wax, Carbowax-10, HP-INNOWax, DB- WAXetr, Carbowax-20M, HP-FFAP, DBFFAP, OV-351 etc..
Used each reagent and instrument source are as follows in following example, the reagent or instrument do not recorded herein or operation Step is the content that those of ordinary skill in the art can routinely determine:
2 embodiment agents useful for same of table and instrument
Embodiment sample and method
In following embodiment, not specified test sample, sample uses following sample:
It is certain density obtained from being diluted containing 9 kinds of nitrosamine compound mixed standard solutions through methylene chloride Solution takes the certain volume solution that the water sample to be measured that ultrapure water obtains is added；
In the examples below, detection method and testing conditions unless stated otherwise, are following head space formula extracting process Method and test condition:
Step a, water sample carries out solid phase microextraction processing, and wherein extraction conditions is as follows:
It takes water sample 20mL to be measured in 40mL brown glass sample bottle, sodium chloride is added into water sample respectively to saturation, magnetic Rotor, NDMA-d6(1 μ g/L) and NDPA-d1(41 μ g/L) Isotopic Internal Standard；Sample bottle is put into water-bath, at 40 DEG C, revolving speed 10min is balanced under conditions of 1000r/min；By in 65 μm of PDMS/DVB solid phase micro-extracting head insertion sample bottles, extracted using head space Mode is taken to extract 30min；
Step b, the extraction needle that extracting and enriching is completed is manually inserted into the injection port of gas-chromatography tandem mass spectrum, Thermal desorption After 30 seconds, start to carry out test analysis, wherein the triple level four bars mass spectrometer parameters of gas-chromatography series connection are as follows:
Chromatographic column: MEGA-WAX (0.25 μ m 0.25mm × 30m)；
Temperature program: 40 DEG C of initial temperature, 2min is kept, after rising to 110 DEG C with 20 DEG C/min, is risen to 10 DEG C/min 180 DEG C, 240 DEG C of holding 6min are risen to 20 DEG C/min；
Carrier gas and flow velocity: high-purity helium, flow velocity 1.3mL/min.
Injector temperature: 180 DEG C；Input mode: Splitless injecting samples；
Ionization mode: the source EI, ionizing energy: 70eV；
Ion source temperature: 200 DEG C, interface temperature: 220 DEG C；
Multiple-reaction monitoring pattern (MRM).
Methodology validation
Determination method above has carried out methodology validation by following steps:
Due to using deionized water not ensure that without containing nitrosamine compound in water, because of nitrosamine compound It is also disinfection by-products, background can interference experiment result.18 megaohms of ultrapure waters and the Evian Water without background can be used Complete the method research.
To determine that experimentation is polluted with the presence or absence of object, to the ultrapure water for not adding object, determined according to experiment Solid phase micro-extraction method and gas phase chromatographic tandem mass spectrometric analysis method carry out analysis detection, 9 kinds of mesh are not detected as the result is shown Object is marked, it is thus determined that this experimentation is polluted without blank.
It is respectively the object aqueous solution of 100ng/L, 1000ng/L and 5000ng/L with ultrapure water compound concentration, measurement Each object rate of recovery, the rate of recovery are 62.4%~104.2%, and relative standard deviation is not more than 10%.By 9 kinds of nitrosamines Compound hybrid standard stock solution with ultrapure water compound concentration be respectively 5000ng/L, 1000ng/L, 500ng/L, 200ng/L, 100ng/L, using inner mark method ration.The analysis method linear relationship established is good, linearly dependent coefficient be 0.9970~ 0.9996。
At measuring method detection limit (MDL), 7 duplicate concentration of METHOD FOR CONTINUOUS DETERMINATION are 100ng/L mark-on sample, are utilized Formula (1) calculates gained
MDL=S × t (n-1,1-a=0.99) (1)
In formula: the mark-on sample number of n=replication, the standard deviation of S=n mark-on measurement concentration, t=freedom degree T test value when for n-1,1-a is confidence level.
3 regression equation of table, the range of linearity and 20mL sample size method detection limit (n=7)
The comparison of the extraction needle of embodiment 1
The present embodiment has chosen different types of fiber coat extraction needle, according to above-mentioned " embodiment sample and method " It is tested.In the present embodiment water sample to be measured containing NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and The concentration of NDPhA compound standard sample is all 1 μ g/L.
5 kinds of different types of fiber coatings are chosen, 7 μm of PDMS (dimethyl silicone polymer) are chosen in selection, 100 μm of PDMS (gather Dimethyl siloxane), 85 μm of PA (polyacrylate), 65 μm of PDMS/DVB (dimethyl silicone polymer/divinylbenzene), 75 μ MCAR/PDMS (carbon molecular sieve/dimethyl silicone polymer) different types of fiber coating, compares the extraction efficiency to nitrosamine.
Each corresponding test of extraction needle extracts 20mL water sample to be measured, and Mass Spectrometer Method is used in conjunction by gas-chromatography:
Extraction results are as shown in Figure 1, peak area refers to that chromatogram corresponds to compound chromatographic peak peak area in figure.Experiment The result shows that 7 μm of PDMS (dimethyl silicone polymer) are because coating is relatively thin, extraction efficiency is poor, and NMEA, NDEA are substantially without response. Two kinds of coatings of 100 μm of PDMS (dimethyl silicone polymer) and 65 μm of PDMS/DVB (dimethyl silicone polymer/divinylbenzene), Efficiency is taken to be apparently higher than the single coating of absorption mechanism in same extraction time in extraction time；75μm CAR/PDMS (carbon molecular sieve/dimethyl silicone polymer) is high to low molecular weight compound extraction efficiency, but is not so good as 65 μm of PDMS/DVB.
The comparison of the extraction mode of embodiment 2
The present embodiment is tested according to above-mentioned " embodiment with sample and method " part head space formula extraction, and will Head space formula extraction replaces with immersion extraction as a comparison, and immersion extraction is that extraction needle is directly immersed in sample to be tested In extracted, head space formula extraction is will to extract needle to be suspended on above sample to be tested, is not extracted with sample to be tested direct contact type It takes.NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and NDPhA compound mark in the present embodiment water sample to be measured The concentration of quasi- sample is all 5 μ g/L.
The organic matter in immersion extraction and head space formula extraction extracting and enriching water, experimental result such as Fig. 2 is respectively adopted Shown, peak area refers to that chromatogram corresponds to compound chromatographic peak peak area in figure.From the experimental results, using different extractions Mode is affected to nitrosamine compound, and wherein low molecular weight compound is preferable using head space formula, for volatile Asia Nitramine compound especially NDMA, 10 times higher than immersion or so of response of the detection of head space formula.The diffusion of analyte in gas phase Coefficient is higher than in liquid phase, and headspace extraction mode can effectively shorten equilibration time, reduces sample matrices interference.
The comparison of 3 extraction temperature of embodiment
The present embodiment uses different bath temperatures, is tested according to above-mentioned " embodiment with sample and method ".This NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and NDPhA compound standard sample in embodiment water sample to be measured Concentration be all 1 μ g/L.
Under the conditions of 0-100 DEG C of temperature, using the organic matter in head space formula extraction extracting and enriching water, experimental result is such as Shown in Fig. 3, peak area refers to that chromatogram corresponds to compound chromatographic peak peak area in figure.Although it can be seen from the figure that 0 DEG C Analyte distribution coefficient between head space is larger when extraction, but compound entirety concentration is also low between the low head space of temperature.When temperature increases When to 40 DEG C, target concentration reaches highest between head space, and extraction efficiency also accordingly reaches highest, as temperature continues to increase, heat Mechanics factor accounts for leading, and all compound extraction efficiencies have different degrees of decline.
4 extraction time of embodiment compares
The present embodiment uses different extraction times, is tested according to above-mentioned " embodiment with sample and method ".This NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and NDPhA compound standard sample in embodiment water sample to be measured Concentration be all 1 μ g/L.
Extraction time is parameter important in entire Solid Phase Extraction, and extraction time is related to the sensitivity, again of entire method Renaturation and analytical effect.Compare 0min, 5min, 10min, 20min, 30min, 40min, 60min difference extraction time nitrous Aminated compounds effect of extracting, experimental result is as shown in Fig. 4-1 and 4-2, and peak area refers to that chromatogram corresponds to compound in figure Chromatographic peak peak area.
From the experimental results, the lower nitrosamine of boiling point just has reached extraction equilibrium (such as NDEA) in 20min, Object basically reaches extraction equilibrium when 30min.
The comparison of 5 chromatographic column of embodiment
The present embodiment uses above-mentioned " embodiment with sample and method " and is tested, and select different chromatographic columns into Row compares.NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and NDPhA chemical combination in the present embodiment water sample to be measured The concentration of object standard sample is all 100 μ g/L.
Polarity capillary column MEGA-WAX (0.25 μ m 0.25mm × 30m) and weak polarity capillary column is respectively adopted Comparison of the RTX5SiL (1.0 μ m 0.25mm × 30m) to nitrosamine separating effect, it is horizontal in figure as shown in Fig. 5-1 and Fig. 5-2 Coordinate is that chromatography acquires retention time, and ordinate is chromatography response intensity.WAX capillary chromatographic column stationary phase is polyethylene glycol, Polarity is stronger, and RTX5SiL capillary chromatographic column stationary phase is -95% dimethyl polysiloxane of 5% phenyl, and polarity is weaker.Such as Figure, RTX5SiL chromatographic column cannot separate N- nitrosopyrolidine (NPYR), N-nitrosomorpholine (NMOR).By using pole Property capillary column (WAX) realizes the optimal separation and richer peak and improved peak shape of 9 kinds of nitrosamine compounds (ebb is wide and trails).This discovery shows the stronger chromatographic column of polarity more suitable for measuring nitrosamine compound.
The comparison of 6 injection port of chromatograph temperature of embodiment
The present embodiment uses different injection port of chromatograph temperature, carries out according to above-mentioned " embodiment with sample and method " Test.NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and NDPhA chemical combination in the present embodiment water sample to be measured The concentration of object standard sample is all 100 μ g/L.
This experiment optimizes injector temperature from 160 DEG C~240 DEG C, obtained chromatogram such as Fig. 6, schemes the face Zhong Feng Product refers to that chromatogram corresponds to compound chromatographic peak peak area.Injector temperature gradually rises in 160 DEG C~180 DEG C response intensities Height, then as temperature increases, response intensity dies down.
The comparison of 7 chromatograph Sampling liner pipe pipe diameter size of embodiment
The present embodiment uses the bushing pipe of different tube diameters size, is tried according to above-mentioned " embodiment with sample and method " It tests.NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and NDPhA compound mark in the present embodiment water sample to be measured The concentration of quasi- sample is all 1 μ g/L.
It is tested respectively with the bushing pipe of 0.75mm internal diameter and 2mm internal diameter, result is as shown in Fig. 7-1 and Fig. 7-2, figure Middle abscissa is that chromatography acquires retention time, and ordinate is chromatography response intensity.By experiment as can be seen that 0.75mm bushing pipe Than common 2mm internal diameter Sampling liner pipe carrier gas linear velocity faster, analyte is transferred to analytical column, forms relatively narrow diffusion Band, and more sharp peak is obtained, hangover can also be reduced and sample loss peak type is obviously sharper, the low Asia of script detection intensity Nitramine response intensity also increases, and baseline is also more steady.
The comparison of 8 spectrometer interface temperature of embodiment
The present embodiment adjusts spectrometer interface temperature, is tested according to above-mentioned " embodiment with sample and method ".This NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and NDPhA compound standard sample in embodiment water sample to be measured Concentration be all 100 μ g/L.
In order to investigate influence of the interface temperature to object respective strengths, interface temperature is carried out from 160 DEG C~240 DEG C Optimization, experimental result is shown in Fig. 8, peak area refers to that chromatogram corresponds to compound chromatographic peak peak area in figure.Interface temperature exists 220 DEG C reach best response intensity, continue to increase with temperature, and response intensity variation is unobvious.
The comparison of 9 mass spectrometer ion source temperature of embodiment
The present embodiment adjusts mass spectrometer ion source temperature, is tested according to above-mentioned " embodiment with sample and method ". NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and NDPhA compound standard sample in the present embodiment water sample to be measured The concentration of product is all 100 μ g/L.
Ion source temperature is investigated in this experiment from 160 DEG C~240 DEG C, experimental result such as Fig. 9, peak area in figure Refer to that chromatogram corresponds to compound chromatographic peak peak area.When ion source temperature is between 160 DEG C~200 DEG C, object is rung Should be worth can increase accordingly with the raising of ion source temperature, response highest at 200 DEG C.When temperature further increases, change The cracking of object object ion fragment is closed, so that monitoring response intensity reduces.
The comparison of 10 mass spectrograph scanning mode of embodiment
The present embodiment is tested according to above-mentioned " embodiment with sample and method ", and is swept using different mass spectrographs The mode of retouching is compared.In the present embodiment water sample to be measured NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR and The concentration of NDPhA compound standard sample is all 200 μ g/L.
After selection ion scan (SIM) and multiple-reaction monitoring (MRM) scanning mode is scanned, result such as Figure 10-1 With Figure 10-2, abscissa is the retention time of chromatography in figure, and ordinate is the response intensity of chromatography.The experimental results showed that SIM It is high that method detects response intensity ratio MRM mode, but background interference is also relatively large simultaneously, in actual sample detection, by Yu Shuizhong sample substrate is complicated, and the movement of SIM method baseline is very big, and background interference is serious, influences normal detection, and MRM method can effectively reduce background interference on the basis of response is preferable again.

Claims (12)

1. the analysis method of 9 kinds or more nitrosamine compounds in a kind of detection water, which is characterized in that the nitrosamines chemical combination Object include N- nitroso dimethyl amine, N- nitroso Methylethyl amine, N- nitroso diethylamide, N- nitroso dipropylamine, N- nitroso dibutylamine, N- nitrosopyrolidine, N-nitroso-piperidine, N-nitrosomorpholine and N- nitrosodiphenylamine int he, The analysis method includes the following steps:
(1) extraction processing is carried out to water sample to be measured using solid phase microextraction；With
(2) nitrosamine compound is measured using gas-chromatography tandem mass spectrometry (GC-MS/MS).
2. analysis method according to claim 1, wherein step (2) gas-chromatography is using highly polar or medium pole Property stationary phase chromatographic column；
Preferably, the Strong-polar stationary is selected from polyethylene glycol or (100% cyanogen propyl phenyl of degree of substitution)-methyl polysilicon oxygen Alkane, it is further preferred that use AC20, PEG20M, HP-Wax, DB-Wax, Carbowax-10, HP-INNOWax, DB- WAXetr, Carbowax-20M, HP-FFAP, DBFFAP or OV-351 chromatographic column；
It may further be preferable that the middle polarity stationary phase is poly- selected from 50% diphenyl of degree of substitution-degree of substitution, 50% dimethyl Siloxanes, (14% cyanogen propyl phenyl of degree of substitution)-methyl polysiloxane or (50% cyanogen propyl phenyl of degree of substitution)-methyl polysilicon oxygen Alkane, it is further preferred that use AC10, OV-1701, DB-1701, RTX-1701, AC225, OV-225, BP-225, DB- 225, HP-225 or RTX-225 chromatographic column.
3. analysis method according to claim 1 or 2, wherein step (2) described GC conditions include:
Temperature program: 30~50 DEG C of initial temperature, 1~5min is kept, after rising to 100~120 DEG C with 10~30 DEG C/min, with 5 ~20 DEG C/min rises to 170~190 DEG C, rises to 230~250 DEG C of 3~9min of holding with 10~30 DEG C/min；Preferably, just 35~45 DEG C of beginning temperature, 1~5min is kept, after rising to 105~115 DEG C with 15~25 DEG C/min, is risen to 5~15 DEG C/min 175~185 DEG C, 235~245 DEG C of 3~9min of holding are risen to 15~25 DEG C/min；It may further be preferable that initial temperature 40 DEG C, 2min is kept, after rising to 110 DEG C with 20 DEG C/min, 180 DEG C is risen to 10 DEG C/min, 240 DEG C of holdings is risen to 20 DEG C/min 6min；
And/or carrier gas and flow: the helium of purity 99.9990V%~99.9999V%, flow 1.0-1.5mL/min, preferably 1.3mL/min；
And/or injector temperature: 160~240 DEG C, preferably 160~200 DEG C, further preferred 170~190 DEG C, into one Preferably 180 DEG C of step；
And/or Sampling liner pipe internal diameter is 0.75-2mm, preferably 0.75-1mm, further preferred 0.75mm.
4. analysis method according to claim 1-3, wherein step (2) described Mass Spectrometry Conditions include:
Ion source temperature: 160~240 DEG C, preferably 170~220 DEG C, further preferred 180~210 DEG C, further preferably 200℃；
And/or interface temperature: 160~240 DEG C, preferably 190~240 DEG C, it is further preferred that, 200~230 DEG C, into Preferably 220 DEG C of one step；
And/or scanning mode: SIM ion monitoring mode or MRM multiple-reaction monitoring pattern, it is preferred to use MRM multiple-reaction monitoring mould Formula；It may further be preferable that analyte is divided into 4 periods: 5~8min:N- nitrous using MRM multiple-reaction monitoring pattern Base dimethyl amine, N- nitroso Methylethyl amine, N- nitroso diethylamide；8~9.5min:N- nitroso dipropylamine；9.5 ~15min:N- nitroso dibutylamine, N-nitroso-piperidine, N- nitrosopyrolidine, N-nitrosomorpholine；15~20min: N- nitrosodiphenylamine int he.
5. analysis method according to claim 1-4, wherein step (1) extraction processing extracting head fibre It ties up coating and is selected from one or more of PDMS, PA, PDMS/DVB, CAR/PDMS；Preferably, the extracting head is PDMS/DVB；
It may further be preferable that the fiber coat is with a thickness of 50 μm or more, further preferred 65-100 μm.
6. analysis method according to claim 1-5, wherein step (1) extraction processing uses immersion Extraction or the extraction of head space formula；Preferably, the extraction processing is extracted using head space formula.
7. analysis method according to claim 1-6, wherein the extraction temperature of step (1) described extraction processing It is 30~50 DEG C, preferably 35~45 DEG C, further preferred 40 DEG C；
And/or extraction time is 20min or more, preferably 30min or more, it is further preferred that 30-60min, further It is preferred that 30min.
8. analysis method according to claim 1-7, wherein be added into step (1) water sample to be measured same The plain internal standard in position；Preferably, N- nitroso dimethyl amine-d is added6, N- nitroso Methylethyl amine-d3, N- nitroso diethyl Amine-d4, N- nitroso dipropylamine-d14, nitroso dibutylamine-d9, N-nitrosomorpholine-d4With N nitrosodiphenyl amine-d1 One or more of Isotopic Internal Standard；It may further be preferable that N- nitroso dimethyl amine-d is added6And/or N- is sub- Nitro dipropylamine-d14Isotopic Internal Standard.
9. analysis method according to claim 1-8, wherein step (1) volume of water sample to be measured is less than 50ml, preferably 20-50ml, further preferred 20-30ml.
10. -9 described in any item analysis methods according to claim 1, wherein include the following steps:
It prepares and contains N- nitroso dimethyl amine, N- nitroso Methylethyl amine, N- nitroso diethylamide, N- nitroso dipropyl Base amine, N- nitroso dibutylamine, N- nitrosopyrolidine, N-nitroso-piperidine, N-nitrosomorpholine and N- nitroso hexichol The mixed standard solution of base amine is tested as the water sample to be measured in step (1).
11. analysis method according to claim 10, including production chromatography response intensity to the standard of concentration of standard solution Curve.
12. the detection method of disinfection by-products in a kind of water, which is characterized in that use described in any item points of claim 1-9 Analysis method.
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