CN102841161A - Gas chromatography-mass spectrometric detection method for octyl phenol and nonyl phenol in aquatic products - Google Patents
Gas chromatography-mass spectrometric detection method for octyl phenol and nonyl phenol in aquatic products Download PDFInfo
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Abstract
The invention relates to a gas chromatography-tandem mass spectrometric detection technology for octyl phenol and nonyl phenol in aquatic products and belongs to the technical field of the detection for the quality safety of the aquatic products. The gas chromatography-tandem mass spectrometric detection technology comprises the following steps of: taking acetone as an extracting agent for ultrasonically extracting the octyl phenol and the nonyl phenol in the aquatic products; removing interferent from the extractive through solid-phase extraction; drying an eluant by blowing nitrogen and then using the acetone and the derivatization reagent N,O-bi(trimethyl silicon alkyl) fluoroacetamide (BSTFA)/trimethylchlorosilane (TMCS) at a volume ratio of 99:1 for deriving; carrying out selected ion scanning detection by utilizing gas chromatography; and fixing the quantity according to an external standard method. The gas chromatography-tandem mass spectrometric detection technology has the advantages of convenience for operation, excellent reproducibility, accuracy in nature determination, higher recovery rate and capability of rapidly analyzing the octyl phenol and the nonyl phenol in the aquatic products.
Description
Technical field
The present invention relates to the gas chromatography-mass spectrography detection technique of octyl phenol and nonylphenol in a kind of aquatic products, belong to aquatic product quality safety detection technology field.
Background technology
Alkylphenol compounds is one type and has the interfering lipophilicity organic compound of endocrine, is widely used in the world in washing agent, pesticide, plastic additive, textile auxiliary and papermaking and the oil field chemical.500,000 tons of APESs of the annual approximately production in the whole world, wherein (nonylphenol ethoxylates NPnEO) accounts for 80% of total production to NPE, and all the other are OPEO (OPnEO) basically.In environment, alkyl phenol mainly comes from the degraded of non-ionic surfactant APES.APES is converted into octyl phenol and nonylphenol in physical environment and sewage disposal process, gets in water body, atmosphere and the soil.In water body environment; These compounds mainly are adsorbed in the suspended particulate substance (mineral, biodetritus, colloidal material and organic matter); Finally be deposited on water bottom through physics, chemistry and biological agent, therefore, sediment is the main home to return to of alkyl phenol; And finally in benthic body, produce accumulation, influence human beings'health thereby can get into human body through food chain simultaneously.In recent years, many scholars have carried out the investigation to alkyl phenol pollution situation in the natural water, find all to have in the water bodys such as most rivers and lake the pollution of the horizontal above-mentioned substance of ng/L.Domestic research to alkyl phenol was since about 2000; Mainly concentrate on induced by alkyl hydroxybenzene in surrounding medium distribution and to aspect the influence of biology, also have on a small quantity alkyl phenol in the research aspect the degraded of the treatment effeciency of sewage treatment plant and nonylphenol.Investigation to alkyl phenol content in the water body aquatic organism is less relatively.The alkyl phenol level of pollution not only receives the influence of water pollution source strength in the aquatic products, and is closely related with factors such as the life habit of aquatic organism, biological natures.Therefore different water contamination of products thing level differs also very big, and aquatic products matrix is complicated.How through sample pre-treatments technology and instrument analysis technology effectively, set up the detection method of alkyl phenol in the high aquatic products of a kind of recovery height, favorable reproducibility, degree of accuracy, become the key of research.
The instrument detecting technology of alkyl phenol have gas chromatography, gas chromatography-mass spectrography,, liquid chromatograph mass spectrography etc., have sensitivity preferably and degree of accuracy.Through SPE, after deriving, realizes derivative reagent that gas chromatography-flame ion detects (GC-FID) and gas chromatography-mass spectrography (GC-MS) analyzing and testing.But because the aquatic products sample substrate is complicated, if Impurity removal is bad in the sample pretreatment process, the directly mensuration result of interference Instrument, even damage instrument.The at present domestic method that does not also detect to alkyl phenol in the aquatic products.Therefore how from aquatic products, extract alkyl phenol efficiently and purify, become the bottleneck that the trace alkyl phenol is analyzed in the aquatic products, this is the object of the invention.
Summary of the invention
The object of the invention is exactly the deficiency that overcomes existing analytical approach, can find a kind of fast and accurately to the assay method of octyl phenol, nonylphenol in the aquatic products, with realize octyl phenol, nonylphenol in the aquatic products quantitatively and qualitative determination.
The present invention proposes the gas chromatography-mass spectrum detection method of octyl phenol, nonylphenol in a kind of aquatic products; This method may further comprise the steps successively: the ultrasonic solvent extraction of ⑴, ⑵ solid phase extraction concentration purify, ⑶ derives, the ⑷ gas chromatography-mass spectrum detects, and the method for operating of each step is following:
⑴ ultrasonic solvent extraction: the aquatic products after the weighing 1.0-5.0g homogenate join in the sample bottle, are extractant with acetone; The vibration mixing 1min that jumps a queue, 35 ℃ of-45 ℃ of temperature extract 10 min under the effect of 40KHz ultrasound wave, will extract centrifugal 5 min of sample then, and rotating speed 5000 rpm isolate extract;
⑵ solid phase extraction concentration purifies: Fo Luoli tripoli solid-phase extraction column; 1 g/6 mL specification, upper end are filled high-temperature baking and are crossed anhydrous sodium sulfate 1-2 g, with 5mL acetone rinse activation solid-phase extraction column; Then above-mentioned isolated extract is injected solid-phase extraction column, discard effluent; Add chromatographically pure ethyl acetate at twice to solid-phase extraction column again and carry out wash-out, each 5mL collects eluent;
⑶ derive: eluent is after nitrogen dries up; Add 0.1-1 mL acetone and 0.1mL derivative reagent N; Two (TMS) trifluoroacetamides (BSTFA) of O-/trimethyl chlorosilane (TMCS) volume ratio vibration in 99: 1 mixing; Derivative reagent will guarantee hermetically drying, 60 ℃ of-90 ℃ of 1h that derive after adding; Derive after after nitrogen dried up, normal hexane was settled to 1mL and treats that gaschromatographic mass spectrometry detects; Air inlet phase chromatography-mass spectroscopy will be at indoor placement 1h before detecting;
⑷ gas chromatography-mass spectrum detects, and will derive and has placed the sample of 1h,, in sample flasket, under the gas chromatography-mass spectrum condition of having set, analyzes through organic membrane filtration of 0.22 μ m, selects ion scan to detect the appearance standard measure.Chromatographic condition is: 270 ℃ of injector temperatures, 200 ℃ of ion trap temperature, 150 ℃ of transmission line temperature; The helium flow velocity is 1.0 mL/min, sample size 1 μ L, solvent delay 5min; Heating schedule: 100 ℃ keep 2min, and 10 ℃/min is warming up to 200 ℃, keep 2min; 15 ℃/min is warming up to 290 ℃, keeps 5min, obtains the chromatogram that appearance time is moderate, peak shape is sharp-pointed, degree of separation is good; Appearance time octyl phenol silanization derivant: 11.894min, nonylphenol silanization derivant: 15.950 min, see accompanying drawing 1; The mass spectrum condition is: adopted the ∑ SIM pattern of 4 kinds of characteristic ions, octyl phenol silanization derivant characteristic ion m/z 207 sees accompanying drawing 2; Nonylphenol silanization derivant m/z292,179 sees accompanying drawing 3; The drawing standard working curve is with the external standard standard measure, according to the concentration of calculated by peak area octyl phenol and nonylphenol.
Beneficial effect of the present invention: the present invention adopts nonylphenol and the Xinji phenol in the ultrasonic auxiliary acetone extract aquatic products at a certain temperature, and effect of extracting is good, and is simple to operate; Adopt the enrichment of Fo Luoli tripoli solid-phase extraction column to purify, good purification has reduced impurity in the extract is measured process to gas chromatography-mass spectrum interference effectively; Adopt gas chromatography-mass spectrography to select ion monitoring, have higher sensitivity and degree of accuracy; Compare with existing measuring technology; The present invention does not need expensive liquid chromatography-mass spectrography or miscellaneous equipment in detecting the alkyl phenol process, method can be carried out qualitative and quantitative measurement simultaneously, and operation is simple; Consuming cost is low, octyl phenol and nonylphenol in can the express-analysis aquatic products.
The present invention adopts the CP-3800 Saturn of VARIAN Oncology Systems 2000 gas chromatograph-mass spectrometer (GCMS)s; Configuration Varian CP-8410 automatic sampler uses VF1701 capillary gas chromatography mass spectrum post (30 m * 0.25 mm * 0.25 μ m) to realize the component separation.
Description of drawings
The chromatogram of accompanying drawing 1:0.5 μ g/mL standard solution;
Accompanying drawing: 2: the mass spectrogram of octyl phenol;
Accompanying drawing 3: the mass spectrogram of nonylphenol.
Embodiment
Through embodiment technical scheme of the present invention is done further to describe below.
The gas chromatography-mass spectrum of octyl phenol and nonylphenol detects in embodiment 1 grass carp
⑴ solvent supersonic extraction: accurately weighing 1.0g blends the grass carp sample of mixing with high-speed tissue mashing machine, joins in the tool plug test tube, accurately adds 10 mL chromatographically pure acetone; Back concussion 1min jumps a queue; Under 35 ℃ of temperature, carry out ultrasonic extraction 10 min of 40KHz; To extract sample then and carry out centrifugal 5 min, rotating speed 5000 rpm; Centrifugal back is collected upper layer of extraction liquid with suction pipe and is steamed in the bottle in revolving;
⑵ solid phase extraction concentration purifies: Florisil solid-phase extraction column (model is 1 g/6 mL) upper end is filled the 1g anhydrous sodium sulfate and is dewatered; Earlier with 5 mL acetone rinse activation solid-phase extraction columns; The solid-phase extraction column that then extract is injected, liquid flows out naturally, discards effluent; In solid-phase extraction column, add chromatographically pure ethyl acetate more at twice and carry out wash-out, each 5mL collects eluent in 15 mL test tubes;
⑶ derive: eluent is after nitrogen dries up; Add 0.1 mL acetone and 0.1mL derivative reagent N; Two (TMS) trifluoroacetamides (BSTFA) of O-/trimethyl chlorosilane (TMCS) volume ratio vibration in 99: 1 mixing with 60 ℃ of derivatization reaction 1h in constant temperature gas bath oscillator, are derived liquid after nitrogen dries up; Normal hexane is settled to 1.0mL, and air inlet phase chromatography-mass spectroscopy will be at indoor placement 1h before detecting;
⑷ gas chromatography-mass spectrum detects: get constant volume and placed the 1h liquid of deriving, be injected in the 1mL needle set, organic membrane filtration of via hole diameter 0.22 μ m carries out the gas chromatography-mass spectrum condition and detects in sample flasket.Chromatographic condition is: 270 ℃ of injector temperatures, 200 ℃ of ion trap temperature, 150 ℃ of transmission line temperature; The helium flow velocity is 1.0 mL/min, sample size 1 μ L, solvent delay 5min; Heating schedule: 100 ℃ keep 2min, and 10 ℃/min is warming up to 200 ℃, keep 2min; 15 ℃/min is warming up to 290 ℃, keeps 5min; Gas chromatography-mass spectrum detects to adopt in the step selects the ion monitoring mode monitoring, has adopted the ∑ SIM pattern of 4 kinds of characteristic ions, octyl phenol silanization derivant characteristic ion m/z 207; Nonylphenol silanization derivant m/z292,179; The drawing standard working curve is with the external standard standard measure, according to the concentration of calculated by peak area octyl phenol and nonylphenol;
⑸ typical curve is drawn
Using chromatographically pure acetone compound concentration is octyl phenol and the nonylphenol mixed standard solution of 0.5 μ g/mL, 1.0 μ g/mL, 2.0 μ g/mL, 5.0 μ g/mL, 10 μ g/mL; Get respectively in above-mentioned each solution 0.1 mL and the test tube with transfer pipet; Operate according to the requirement of above-mentioned ⑶, ⑷ step then, according to the alkyl phenol concentration that adds and the corresponding relation drawing standard curve of peak area;
⑹ the mensuration of the method recovery
In the grass carp sample, add the mixed standard solution of octyl phenol and nonylphenol by the concentration of 0.05 μ g/g, 0.1 μ g/g, 0.2 μ g/g, 0.5 μ g/g, 1.0 μ g/g respectively, each interpolation level is done six parallel appearance respectively; ⑴-⑷ carries out gas chromatography-mass spectrum and detects set by step, and with the above-mentioned typical curve that obtains relatively, finally obtain the concentration of octyl phenol and nonylphenol in the grass carp sample to be measured through converting.The method recovery is at 75-96%, RSD≤15%.
The gas chromatography-mass spectrum of octyl phenol and nonylphenol detects in embodiment 2 grass carps
⑴ solvent supersonic extraction: accurately weighing 3.0 g blend the grass carp sample of mixing with high-speed tissue mashing machine, join in the tool plug test tube, accurately add 10 mL chromatographically pure acetone; Back concussion 1min jumps a queue; Under 40 ℃ of temperature, carry out ultrasonic extraction 10 min of 40KHz; To extract sample then and carry out centrifugal 5 min, rotating speed 5000 rpm; Centrifugal back is collected upper layer of extraction liquid with suction pipe and is steamed in the bottle in revolving;
⑵ solid phase extraction concentration purifies: Florisil solid-phase extraction column, model are 1 g/6 mL, and the upper end is filled the 1.5g anhydrous sodium sulfate and dewatered; Earlier with 5 mL acetone rinse activation solid-phase extraction columns; Then extract is injected solid-phase extraction column, liquid flows out naturally, discards effluent; In solid-phase extraction column, add chromatographically pure ethyl acetate more at twice and carry out wash-out, each 5mL collects eluent in 15 mL test tubes;
⑶ derive: eluent is after nitrogen dries up; Add 0.5 mL acetone and 0.1mL derivative reagent N; Two (TMS) trifluoroacetamides (BSTFA) of O-/trimethyl chlorosilane (TMCS) volume ratio vibration in 99: 1 mixing, derivatization reaction 1h in 75 ℃ of baking ovens derives liquid after nitrogen dries up; Normal hexane is settled to 1.0 mL, and air inlet phase chromatography-mass spectroscopy will be at indoor placement 1h before detecting;
⑷ gas chromatography-mass spectrum detects: get the liquid of deriving that constant volume has also been placed 1h, be injected in the 1mL needle set, organic membrane filtration of via hole diameter 0.22 μ m carries out the gas chromatography-mass spectrum condition and detects in sample flasket.Chromatographic condition is: 270 ℃ of injector temperatures, 200 ℃ of ion trap temperature, 150 ℃ of transmission line temperature; The helium flow velocity is 1.0 mL/min, sample size 1 μ L, solvent delay 5min; Heating schedule: 100 ℃ keep 2min, and 10 ℃/min is warming up to 200 ℃, keep 2min; 15 ℃/min is warming up to 290 ℃, keeps 5min; Gas chromatography-mass spectrum detects to adopt in the step selects the ion monitoring mode monitoring, has adopted the ∑ SIM pattern of 4 kinds of characteristic ions, octyl phenol silanization derivant characteristic ion m/z 207; Nonylphenol silanization derivant m/z292,179; The drawing standard working curve is with the external standard standard measure, according to the concentration of calculated by peak area octyl phenol and nonylphenol;
⑸ typical curve is drawn
Using chromatographically pure acetone compound concentration is octyl phenol and the nonylphenol mixed standard solution of 0.5 μ g/mL, 1.0 μ g/mL, 2.0 μ g/mL, 5.0 μ g/mL, 10 μ g/mL; Get respectively in above-mentioned each solution 0.1 mL and the test tube with transfer pipet; Operate according to the requirement of above-mentioned ⑶, ⑷ step then, according to the alkyl phenol concentration that adds and the corresponding relation drawing standard curve of peak area;
⑹ the mensuration of the method recovery
In the grass carp sample, add the mixed standard solution of octyl phenol and nonylphenol by the concentration of 0.05 μ g/g, 0.1 μ g/g, 0.2 μ g/g, 0.5 μ g/g, 1.0 μ g/g respectively, each interpolation level is done six parallel appearance respectively; ⑴-⑷ carries out gas chromatography-mass spectrum and detects set by step, and with the above-mentioned typical curve that obtains relatively, finally obtain the concentration of octyl phenol and nonylphenol in the grass carp sample to be measured through converting.The method recovery is at 80-105%, RSD≤15%.
The gas chromatography-mass spectrum of octyl phenol and nonylphenol detects in embodiment 3 grass carps
⑴ solvent supersonic extraction: accurately weighing 5.0 g blend the grass carp sample of mixing with high-speed tissue mashing machine, join in the tool plug test tube, accurately add 10 mL chromatographically pure acetone; Back concussion 1min jumps a queue; Under 45 ℃ of temperature, carry out ultrasonic extraction 10 min of 40KHz; To extract sample then and carry out centrifugal 5 min, rotating speed 5000 rpm; Centrifugal back is collected upper layer of extraction liquid with suction pipe and is steamed in the bottle in revolving;
⑵ solid phase extraction concentration purifies: Florisil solid-phase extraction column upper end is filled the 2g anhydrous sodium sulfate and is dewatered; Earlier with 5 mL acetone rinse activation solid-phase extraction columns; Then extract is injected the solid-phase extraction column of 1 g/6 mL, liquid flows out naturally, discards effluent; In solid-phase extraction column, add chromatographically pure ethyl acetate more at twice and carry out wash-out, each 5mL collects eluent in 15 mL test tubes;
⑶ derive: eluent is after nitrogen dries up; Add 1.0 mL acetone and 0.1mL derivative reagent N; Two (TMS) trifluoroacetamides (BSTFA) of O-/trimethyl chlorosilane (TMCS) volume ratio vibration in 99: 1 mixing with 90 ℃ of derivatization reaction 1h, are derived liquid after nitrogen dries up; Normal hexane is settled to 1mL, and air inlet phase chromatography-mass spectroscopy will be at indoor placement 1h before detecting;
⑷ gas chromatography-mass spectrum detects: get the liquid of deriving that constant volume has also been placed 1h, be injected in the 1mL needle set, organic membrane filtration of via hole diameter 0.22 μ m carries out the gas chromatography-mass spectrum condition and detects in sample flasket.Chromatographic condition is: 270 ℃ of injector temperatures, 200 ℃ of ion trap temperature, 150 ℃ of transmission line temperature; The helium flow velocity is 1.0 mL/min, sample size 1 μ L, solvent delay 5min; Heating schedule: 100 ℃ keep 2min, and 10 ℃/min is warming up to 200 ℃, keep 2min; 15 ℃/min is warming up to 290 ℃, keeps 5min;
Gas chromatography-mass spectrum detects to adopt in the step selects the ion monitoring mode monitoring, has adopted the ∑ SIM pattern of 4 kinds of characteristic ions, octyl phenol silanization derivant characteristic ion m/z 207; Nonylphenol silanization derivant m/z292,179; The drawing standard working curve is with the external standard standard measure, according to the concentration of calculated by peak area octyl phenol and nonylphenol;
⑸ typical curve is drawn
Using chromatographically pure acetone compound concentration is octyl phenol and the nonylphenol mixed standard solution of 0.5 μ g/mL, 1.0 μ g/mL, 2.0 μ g/mL, 5.0 μ g/mL, 10 μ g/mL; Get respectively in above-mentioned each solution 0.1 mL and the test tube with transfer pipet; Operate according to the requirement of above-mentioned ⑶, ⑷ step then, according to the alkyl phenol concentration that adds and the corresponding relation drawing standard curve of peak area;
⑹ the mensuration of the method recovery
In the grass carp sample, add the mixed standard solution of octyl phenol and nonylphenol by the concentration of 0.05 μ g/g, 0.1 μ g/g, 0.2 μ g/g, 0.5 μ g/g, 1.0 μ g/g respectively, each interpolation level is done six parallel appearance respectively; ⑴-⑷ carries out gas chromatography-mass spectrum and detects set by step, and with the above-mentioned typical curve that obtains relatively, finally obtain the concentration of octyl phenol and nonylphenol in the grass carp sample to be measured through converting.The method recovery is at 75-110%, RSD≤15%.
The foregoing description is to explanation of the present invention, is not to qualification of the present invention, any scheme after the simple transformation of the present invention is all belonged to protection scope of the present invention.
Claims (1)
1. the gas chromatography-mass spectrum detection method of octyl phenol, nonylphenol in the aquatic products, it is characterized in that: this method comprises: 1. ultrasonic solvent extraction, 2. solid phase extraction concentration purifies, 3. derives, 4. gas chromatography-mass spectrum detects, wherein:
1. described ultrasonic solvent extraction, by following procedure: the aquatic products after the weighing 1.0-5.0g homogenate join in the sample bottle, are extractant with acetone; The vibration mixing 1min that jumps a queue, 35 ℃ of-45 ℃ of temperature extract 10 min under the effect of 40KHz ultrasound wave, will extract centrifugal 5 min of sample then, and rotating speed 5000 rpm isolate extract;
2. described solid phase extraction concentration purifies; Press following procedure: Fo Luoli tripoli solid-phase extraction column; 1 g/6 mL specification, upper end are filled high-temperature baking and are crossed anhydrous sodium sulfate 1-2 g, with acetone rinse activation solid-phase extraction column; Then above-mentioned isolated extract is injected solid-phase extraction column, discard effluent; Add chromatographically pure ethyl acetate at twice to solid-phase extraction column again and carry out wash-out, each 5mL collects eluent;
3. described deriving; By following procedure: eluent is after nitrogen dries up; Add 0.1-1 mL acetone and 0.1mL derivative reagent N; Two (TMS) trifluoroacetamides (BSTFA) of O-/trimethyl chlorosilane (TMCS) volume ratio vibration in 99: 1 mixing are derived for 60 ℃-90 ℃, and the derivatization reaction process will guarantee hermetically drying; Derive liquid after nitrogen dries up, and normal hexane is settled to 1mL; Air inlet phase chromatography-mass spectroscopy will be at indoor placement 1h before detecting;
4. described gas chromatography-mass spectrum detects, by following procedure: get constant volume and placed the liquid of deriving of 1h, in sample flasket, carry out the gas chromatography-mass spectrum detection through organic membrane filtration of 0.22 μ m.Chromatographic condition is: 270 ℃ of injector temperatures, 200 ℃ of ion trap temperature, 150 ℃ of transmission line temperature; The helium flow velocity is 1.0 mL/min, sample size 1 μ L, solvent delay 5min; Heating schedule: 100 ℃ keep 2min, and 10 ℃/min is warming up to 200 ℃, keep 2min; 15 ℃/min is warming up to 290 ℃, keeps 5min.Mass spectrum condition: adopted the ∑ SIM pattern of 4 kinds of characteristic ions, octyl phenol silanization derivant characteristic ion m/z207; Nonylphenol silanization derivant m/z292,179; The drawing standard working curve is with the external standard standard measure, according to the concentration of calculated by peak area octyl phenol and nonylphenol.
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| CN114813992A (en) * | 2022-03-09 | 2022-07-29 | 上海交通大学医学院 | Method for detecting phenols, esters and pesticide intermediates in urine |
| CN114994194A (en) * | 2022-05-09 | 2022-09-02 | 广东安纳检测技术有限公司 | Method and device for measuring malonic acid in water |
| CN114994194B (en) * | 2022-05-09 | 2024-04-09 | 广东安纳检测技术有限公司 | Method and device for measuring malonic acid in water |
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