CN109541091A - A kind of analysis method of N- nitrosamine compound in drinking water - Google Patents
A kind of analysis method of N- nitrosamine compound in drinking water Download PDFInfo
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- CN109541091A CN109541091A CN201811187477.XA CN201811187477A CN109541091A CN 109541091 A CN109541091 A CN 109541091A CN 201811187477 A CN201811187477 A CN 201811187477A CN 109541091 A CN109541091 A CN 109541091A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a kind of analysis methods of the N- nitrosamine compound in drinking water, comprising the following steps: a) sample pretreatment: taking 100mL water sample, is filtered with 0.45 μm of nylon membrane, obtain pretreatment sample；B) solid phase extraction column pre-processes: being eluted three times to solid phase extraction column, uses 10mL eluent methylene chloride for the first time, eluted for the second time using 10mL methanol, eluted for the third time using 10mL distilled water, obtains pre-processing solid phase extraction column；C) loading: pretreatment sample is poured into pretreatment solid phase extraction column, and take negative-pressure ward mode, make pretreatment sample by pretreatment solid-phase extraction column, is drained until pre-processing the pretreatment sample in solid-phase extraction column, obtain the solid-phase extraction column for being adsorbed with target analytes；D) collect analyte；E) it analyzes；The application can product processing it is simple, high sensitivity, linear good within the scope of 0.5~100 μ g/L, the 0.5 continuous 5 needle sample introduction of μ g/L standard solution, for peak area RSD less than 2%, reproducibility is good.
Description
[technical field]
The present invention relates to the technical field of water quality detection, point of the N- nitrosamine compound in especially a kind of drinking water
The technical field of analysis method.
[background technique]
N- nitrosamine is a kind of compound with N-N=O structure.At present in more than 130 kinds of N- nitrosamines having found
In compound, 80% or more is all strong carcinogen.In recent years, people start to replace chlorine to disappear drinking water using chloramines
Poison.But studies have shown that chloramines disinfection can generate by-product N- nitrosamine.
Early in 1994, N-Nitrosodimethylamine was detected in Ontario Lake, Canada drinking water for the first time.Then, N- nitrous
Several nitrosamine compounds such as base diethylamine, N nitrosodiphenyl amine are found in drinking water in succession.2005, Environmental Protection in America
6 kinds of N- nitrosamine with genetoxic are classified as the non-limiting pollutant for needing to detect in drinking water, it is specified that in drinking water by administration
The Limited Doses of N-Nitrosodimethylamine, N- nitroso Methylethyl amine and N-Nitrosodiethylamine are respectively 7,20 and 2ng/L.Cause
It is necessary to propose that a kind of sample treatment is simple, the analysis method of N- nitrosamine compound in drinking water of high sensitivity for this.
[summary of the invention]
The object of the invention is to solve the problems of the prior art, propose that a kind of sample treatment is simple, high sensitivity
The analysis method of N- nitrosamine compound in drinking water.
To achieve the above object, the invention proposes a kind of analysis method of the N- nitrosamine compound in drinking water,
The following steps are included:
A) sample pretreatment: taking 100mL water sample, is filtered with 0.45 μm of nylon membrane, obtains pretreatment sample；
B) solid phase extraction column pre-processes: being eluted three times to solid phase extraction column, uses 10mL dichloromethane for the first time
Alkane elution, second is eluted using 10mL methanol, is eluted for the third time using 10mL distilled water, and it is small to obtain pretreatment Solid Phase Extraction
Column；
C) loading: pretreatment sample is poured into pretreatment solid phase extraction column, and takes negative-pressure ward mode, makes pre- place
Sample is managed by pretreatment solid-phase extraction column, drains, is adsorbed with until pre-processing the pretreatment sample in solid-phase extraction column
The solid-phase extraction column of target analytes；
D) target analysis in the solid-phase extraction column of target analytes will collect analyte: be adsorbed with 10mL methylene chloride
Object elutes, and collects the methylene chloride after cleaning；
E) it analyzes: the methylene chloride collected in d) step is settled to 1mL, upper machine analysis.
Preferably, the pretreatment sample in the c) step crosses pretreatment solid-phase extraction column with the speed of 3mL/min.
Preferably, the analysis machine in the e) step is triple quadrupole bar gas chromatograph-mass spectrometer.
Preferably, the analysis condition of the analysis machine in the e) step are as follows: chromatographic column: Stabilwax, 30m ×
0.25mm×0.25μm；Injector temperature: 230 DEG C；Input mode: Splitless injecting samples；Column temperature program: 60 DEG C of initial temperature holdings
2min, then 8 DEG C/min is raised to 140 DEG C of holding 8min, then 40 DEG C/min is raised to 240 DEG C of holding 10min；Constant linear velocity:
36.5cm/sec；Sample volume: 2 μ L；Ionization mode: EI；Ion source temperature: 200 DEG C；Chromatography-mass spectroscopy interface temperature: 240 DEG C；
The solvent delay time: 5.5min；Acquisition mode: the more reaction detection modes of MRM.
Preferably, further including that standard curve is established.
Beneficial effects of the present invention: then the present invention is used by the way that water sample progress Solid Phase Extraction is obtained target analytes
Triple quadrupole bar gas chromatograph-mass spectrometer GCMS is analyzed, and this method sample treatment is simple, high sensitivity.
Feature and advantage of the invention will be described in detail by embodiment combination attached drawing.
[Detailed description of the invention]
Fig. 1 is the appearance spectrogram (100 μ g/L of concentration) of N- nitrosamine compound；
Fig. 2 to Figure 11 is NDMA, NMEA, NDEA, NDPA, NDBA, NPIP, NPYR, NMOR, NDPhA, NDBzA respectively
Chromatogram (0.1 μ g/L of concentration)；
Figure 12 to Figure 14 is NDMA, NMEA and NDEA calibration curve respectively；
Figure 15 is the reproducibility (0.5 μ g/L of concentration) of NMEA, NDPA and NDBA.
[specific embodiment]
The analysis method of N- nitrosamine compound in a kind of drinking water of the present invention, comprising the following steps:
A) sample pretreatment: taking 100mL water sample, is filtered with 0.45 μm of nylon membrane, obtains pretreatment sample；
B) solid phase extraction column pre-processes: being eluted three times to solid phase extraction column, uses 10mL dichloromethane for the first time
Alkane elution, second is eluted using 10mL methanol, is eluted for the third time using 10mL distilled water, and it is small to obtain pretreatment Solid Phase Extraction
Column；
C) loading: pretreatment sample is poured into pretreatment solid phase extraction column, and takes negative-pressure ward mode, makes pre- place
It manages sample and pretreatment solid-phase extraction column is crossed with the speed of 3mL/min, until the pretreatment sample in pretreatment solid-phase extraction column is taken out
It is dry, obtain the solid-phase extraction column for being adsorbed with target analytes；
D) target analysis in the solid-phase extraction column of target analytes will collect analyte: be adsorbed with 10mL methylene chloride
Object elutes, and collects the methylene chloride after cleaning；
E) it analyzes: the methylene chloride collected in d) step is settled to 1mL, upper machine analysis.
The analysis condition of analysis machine are as follows: chromatographic column: Stabilwax, 30m × 0.25mm × 0.25 μm；Injector temperature:
230℃；Input mode: Splitless injecting samples；Column temperature program: 60 DEG C of holding 2min of initial temperature, then 8 DEG C/min is raised to 140 DEG C of holdings
8min, then 40 DEG C/min are raised to 240 DEG C of holding 10min；Constant linear velocity: 36.5cm/sec；Sample volume: 2 μ L；Ionization mode:
EI；Ion source temperature: 200 DEG C；Chromatography-mass spectroscopy interface temperature: 240 DEG C；The solvent delay time: 5.5min；Acquisition mode: MRM
More reaction detection modes.
Characteristic ion is shown in Table 1:
1 each component retention time of table and MRM condition
Chromatogram:
Using methylene chloride as solvent, compound concentration is the N- nitrosamine standard solution of 100 μ g/L, referring to above-mentioned analysis condition
It is acquired, obtained chromatogram is illustrated in fig. 1 shown below.
The N- nitrosamine standard solution that concentration is 100 μ g/L is diluted to 0.1 μ g/L to analyze again, each component chromatogram
As shown in Figures 2 to 11.The result shows that triple quadrupole bar gas chromatograph-mass spectrometer GCMS has very well the standard solution of 0.1 μ g/L
Response.
Standard curve, reproducibility, the rate of recovery and detection limit:
Using methylene chloride as solvent, the N- nitrosamine that compound concentration is 0.5,1,5,10,20,30,100 μ g/L respectively is mixed
Standard solution.It is acquired in a manner of MRM.Each component standard curve (only lists 3 groups as shown in Figure 12 to Figure 14 herein
Point), reproducibility result is as shown in figure 15 (only listing 3 components herein).
Three parts of blank water samples, the N- nitrosamine mixed standard solution that addition concentration is 20 μ g/L are taken, addition concentration is 10pg/
L calculates its rate of recovery.With 3 times of signal-noise ratio computation method detection limits, it the results are shown in Table 2.
2 calibration curve coefficient correlation of table, reproducibility, the rate of recovery and detection limit result
The result shows that GCMS-TQ8030 is linear good within the scope of 0.5~100 μ g/L, 0.5 μ g/L standard solution continuous 5
Needle sample introduction, for peak area RSD less than 2%, reproducibility is good.
Above-described embodiment is the description of the invention, is not limitation of the invention, after any pair of simple transformation of the present invention
Scheme all belong to the scope of protection of the present invention.
Claims (5)
1. a kind of analysis method of the N- nitrosamine compound in drinking water, it is characterised in that: the following steps are included:
A) sample pretreatment: taking 100mL water sample, is filtered with 0.45 μm of nylon membrane, obtains pretreatment sample；
B) solid phase extraction column pre-processes: being eluted to solid phase extraction column, is drenched for the first time using 10mL methylene chloride three times
It washes, is eluted for the second time using 10mL methanol, eluted for the third time using 10mL distilled water, obtain pre-processing solid phase extraction column；
C) loading: pretreatment sample being poured into pretreatment solid phase extraction column, and takes negative-pressure ward mode, makes to pre-process sample
Product are drained until pre-processing the pretreatment sample in solid-phase extraction column by pretreatment solid-phase extraction column, obtain being adsorbed with target
The solid-phase extraction column of analyte；
D) collect analyte: the target analytes being adsorbed in the solid-phase extraction column of target analytes are drenched with 10mL methylene chloride
It washes, and collects the methylene chloride after cleaning；
E) it analyzes: the methylene chloride collected in d) step is settled to 1mL, upper machine analysis.
2. the analysis method of the N- nitrosamine compound in a kind of drinking water as described in claim 1, it is characterised in that: institute
It states the pretreatment sample in c) step and pretreatment solid-phase extraction column is crossed with the speed of 3mL/min.
3. the analysis method of the N- nitrosamine compound in a kind of drinking water as described in claim 1, it is characterised in that: institute
Stating the analysis machine in e) step is triple quadrupole bar gas chromatograph-mass spectrometer.
4. the analysis method of the N- nitrosamine compound in a kind of drinking water as described in claim 1, it is characterised in that: institute
State the analysis condition of the analysis machine in e) step are as follows: chromatographic column: Stabilwax, 30m × 0.25mm × 0.25 μm；Injection port temperature
Degree: 230 DEG C；Input mode: Splitless injecting samples；Column temperature program: 60 DEG C of holding 2min of initial temperature, then 8 DEG C/min is raised to 140 DEG C of guarantors
8min is held, then 40 DEG C/min is raised to 240 DEG C of holding 10min；Constant linear velocity: 36.5cm/sec；Sample volume: 2 μ L；Ionization side
Formula: EI；Ion source temperature: 200 DEG C；Chromatography-mass spectroscopy interface temperature: 240 DEG C；The solvent delay time: 5.5min；Acquisition mode:
The more reaction detection modes of MRM.
5. the analysis method of the N- nitrosamine compound in a kind of drinking water as described in claim 1, it is characterised in that: also
It is established including standard curve.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022186796A1 (en) * | 2021-03-01 | 2022-09-09 | Cukurova Universitesi Rektorlugu | Method to remove off-odour compounds in food by molecular imprinted polymer |
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| CN102580351A (en) * | 2012-01-12 | 2012-07-18 | 浙江大学 | Series solid-phase extraction (SPE) method for nitrosamine compounds in drinking water |
| CN104062377A (en) * | 2014-07-04 | 2014-09-24 | 湖南科技大学 | Total-detection method of volatile N-nitrosamine compounds in foods |
| CN104568562A (en) * | 2014-12-31 | 2015-04-29 | 中国地质大学（武汉） | Water sample and pretreatment method of nitrosoamine compound in suspended matter of water sample |
| CN108008040A (en) * | 2017-12-01 | 2018-05-08 | 暨南大学 | A kind of detection method of underwater trace N- nitrosamine |
| CN108508111A (en) * | 2018-04-08 | 2018-09-07 | 哈尔滨工业大学 | Analysis method that is a kind of while detecting 9 kinds of trace nitrosamines disinfection by-products in water |
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2018
- 2018-10-12 CN CN201811187477.XA patent/CN109541091A/en active Pending
Patent Citations (5)
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| CN102580351A (en) * | 2012-01-12 | 2012-07-18 | 浙江大学 | Series solid-phase extraction (SPE) method for nitrosamine compounds in drinking water |
| CN104062377A (en) * | 2014-07-04 | 2014-09-24 | 湖南科技大学 | Total-detection method of volatile N-nitrosamine compounds in foods |
| CN104568562A (en) * | 2014-12-31 | 2015-04-29 | 中国地质大学（武汉） | Water sample and pretreatment method of nitrosoamine compound in suspended matter of water sample |
| CN108008040A (en) * | 2017-12-01 | 2018-05-08 | 暨南大学 | A kind of detection method of underwater trace N- nitrosamine |
| CN108508111A (en) * | 2018-04-08 | 2018-09-07 | 哈尔滨工业大学 | Analysis method that is a kind of while detecting 9 kinds of trace nitrosamines disinfection by-products in water |
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Cited By (1)
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| WO2022186796A1 (en) * | 2021-03-01 | 2022-09-09 | Cukurova Universitesi Rektorlugu | Method to remove off-odour compounds in food by molecular imprinted polymer |
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Application publication date: 20190329 |