CN104155375A - Method for detecting phenylamine compounds in environmental water samples by using synchronous derivation ultrasonic emulsification micro-extraction gas chromatography - Google Patents
Method for detecting phenylamine compounds in environmental water samples by using synchronous derivation ultrasonic emulsification micro-extraction gas chromatography Download PDFInfo
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- CN104155375A CN104155375A CN201410350220.7A CN201410350220A CN104155375A CN 104155375 A CN104155375 A CN 104155375A CN 201410350220 A CN201410350220 A CN 201410350220A CN 104155375 A CN104155375 A CN 104155375A
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Abstract
The invention discloses a method for detecting phenylamine compounds in environmental water samples by using a synchronous derivation ultrasonic emulsification micro-extraction gas chromatography. The method for detecting the phenylamine compounds in the environmental water samples by using the synchronous derivation ultrasonic emulsification micro-extraction gas chromatography comprises the following steps: (1) injecting liquid samples into a sharp-bottom glass centrifugal tube, quickly injecting n-butyl chloroformate which is used as a derivating agent/an extraction phase into the liquid samples by using a micro-syringe, subsequently putting into a high-power numerical control ultrasonic wave washing machine; (2) carrying out the ultrasonic treatment for 7 minutes under the conditions that the frequency is 40kHz, the power is 50W and the temperature is 2 DEG C, preparing the liquid samples in the glass centrifugal tube into an emulsion, centrifuging and fully separating phases of the emulsion in a test tube; (3) sucking a deposition phase at the bottom of the test tube by using a gas chromatography syringe and injecting the deposition phase into a gas chromatograph for analyzing; and (4) analyzing and detecting the phenylamine compounds by using the gas chromatograph. Compared with a conventional detection method, for the method disclosed by the invention, not only the analysis time is shortened, but also organic solvents with toxic action on a human body are reduced.
Description
Technical field
The present invention relates to the detection field of pollutant in environment water, relate in particular to the method for amino benzenes compounds in a kind of synchronous derivative ultrasonic emulsification micro-extraction gas chromatography determination environmental water sample.
Background technology
In the production run of dyestuff, spices, synthetic resin, agricultural chemicals and medicine, amino benzenes compounds is widely used as synthetic intermediate, they are easy to be discharged in river, lake and soil with trade waste, become the organic contaminant that ecologic environment is caused to very big harm, part aromatic amine has high toxicity to the mankind, has been confirmed as carcinogen.Amino benzenes compounds has more polarity than precursor substance, thereby water-soluble stronger, and this has caused their transfer abilities in water environment greatly to strengthen, and the existence of its low dose just may cause serious harm to hydrobionts such as algae, fish.In order can effectively to control and to administer the pollution of amino benzenes compounds to water body environment, the method for setting up aniline compound in a kind of water sample of testing environment is quickly and efficiently very necessary.
Aniline categories content in environment water sample, conventionally in trace level, obtains result more accurately in order to make to analyze, and sample must pass through pre-service.In the To Several Traditional Preconditioning Methods of amino benzenes compounds sample, the cost of solid phase extraction (SPE) is higher, complex steps, Solid-phase Microextraction (SPME) after its improvement, though operate more easy, because its quartz fibre quality used is more crisp and serviceable life is limited, so method price is more expensive, in addition, residual in extracting head of analyte is also a very important problem, liquid-phase extraction method (LLE), transmission based on analyte between fluid sample and water-fast extractant, it is a kind of widely used sample-pretreating method, but there is complex operation, extraction time length and the large shortcoming of consumption of organic solvent, its improved liquid-phase micro-extraction method (LPME) has realized a step extraction, only need the organic solvent of micro-volume to carry out the analyte compound in extraction liquids sample, and coefficient of concentration is high, recently, for the method, developed hanging drop microextraction method (SDME), the new methods such as hollow-fibre membrane microextraction method (HF ?LPME) and headspace liquid-phase microextraction method (HS ?LPME).But in the actual mechanical process of SDME method, the stability of hanging drop is difficult to guarantee, and HF ?LPME method also there is the long problem of pretreatment time.For these problems, Assadi etc. (2006) have proposed a kind of new liquid-phase micro extraction technique---dispersive liquid-liquid microextraction method (DLLME), this method because of easy and simple to handle fast and coefficient of concentration high, and by extensive concern, yet, in the operating process of DLLME method, still need to use a considerable amount of organic solvents, this has certain harmfulness concerning operator.Subsequently, for the use problem of organic solvent, Regueiro etc. (2008) have proposed a kind of novel DLLME method combining with Ultrasonic Radiation, are called ultrasonic auxiliary emulsification microextraction method (USAEME), because this preprocess method is not used spreading agent, thereby environmental protection more.
Amino benzenes compounds belongs to polar compound, in gas chromatographic analysis process, can cause hangover and irreversible adsorption, in order to obtain better chromatogram effect, conventionally need to carry out derivatization, in addition, derivatization can also help pre-treating method to obtain wider analyst coverage.Derivatization can be divided into before post, in post and post column derivatization, and wherein more welcome pre-column derivatization, can be further divided into again the front derivatization of extraction, the rear derivatization of extraction and synchronous derivatization.In synchronous derivatization process, extraction and derivatization synchronously carry out, thus more simple, facilitate and save time.Farajzadeh and Nouri (2012) are used butyl chlorocarbonate (Butylchloroformate) as derivating agent/extraction phase, have introduced a kind of aniline fluid sample analysis new technology based on synchronous derivatization and DLLME technology.
For the analysis that makes amino benzenes compounds in environmental water sample more rapidly and efficiently and environmental protection, the present invention combines the two technological merit of synchronous derivatization and USAEME method, by experimental study and technical optimization to derivative/extraction efficiency influence factor, set up a kind of Novel liquid-phase extractant technology, synchronously derive ultrasonic emulsification microextraction method (Simultaneous derivatization and ultrasound assisted emulsification microextraction, SD ?USAEME), and it is combined with gas chromatography flame ionization ditector (GC ?FID), in actual environment water sample, the testing result of amino benzenes compounds shows, the detection of this method to amino benzenes compounds in environmental water sample, have easy and simple to handle, highly sensitive, the feature of environmental protection.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the method for amino benzenes compounds in a kind of synchronous derivative ultrasonic emulsification micro-extraction gas chromatography determination environmental water sample is provided.
In synchronous derivative ultrasonic emulsification micro-extraction gas chromatography determination environmental water sample, the method for amino benzenes compounds comprises the steps:
(1) 10mL fluid sample is injected to 15mL point end glass centrifuge tube, in the quick filling liquid sample of butyl chlorocarbonate with 50 μ L micro-sampling pins using 20 μ L as derivating agent/extraction phase, then moved in high power numerical control supersonic cleaning machine;
(2) ultrasonic 7min under the condition of 2 ℃ of frequency 40kHz, power 50W, temperature, in glass centrifuge tube, fluid sample becomes after emulsion, with hydro-extractor centrifugal 6min under 4000rpm condition, emulsion in test tube is completed and be separated, sedimentary facies cumulative volume is 10 μ L;
(3) with the gas chromatographic sample introduction pin of 5 μ L, draw the sedimentary facies 2 μ L of test tube bottom, inject gas chromatograph is analyzed, and gas chromatographic sample introduction pin dead volume is 0;
(4) with gas chromatograph, analyze and detect amino benzenes compounds, gas chromatograph is equipped with shunting/Splitless injecting samples system and flame ionization ditector, gas chromatographic column be HT ?5 capillary gas chromatographic columns, 30m * 0.25mm * 0.25 μ m, fill mutually 5% ?diphenyl ?95% ?dimethyl polysiloxane, temperature programme: initial 80 ℃ retain 4min, then with 8 ℃/min, be warmed up to 160 ℃, in 160 ℃, keep 2min, with 5 ℃/min, be warmed up to 230 ℃ of end afterwards, gas chromatograph sampling device and detector temperature are 270 ℃, the nitrogen of 99.999% purity is carrier gas and make-up gas, flow rate of carrier gas is 1.20mL/min, make-up gas flow velocity is 25mL/min, air velocity 300mL/min, hydrogen flow rate 30mL/min,
(5), according to the analysis result of gas chromatography, obtain the content data of amino benzenes compounds in environmental water sample.
The present invention compared with prior art has obvious advantage:
1. adopt this method to measure amino benzenes compounds in environmental water sample, not only highly sensitive, detect and be limited to 1.1～4.1 μ g/L, and there is the wider range of linearity (6～60000 μ g/L).
2. this method will synchronously derive the micro-extraction process of being combined with ultrasonic auxiliary Emulsion Phase, makes operation more easy, and the consumption of organic solvent only needs 20 μ L.Than traditional detection method, not only shortened analysis time, and reduced the organic solvent to the toxic effect of human body.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that synchronously derives amino benzenes compounds in ultrasonic emulsification micro-extraction gas chromatography determination environmental water sample.In figure: (a) 15mL point end glass centrifuge tube is equipped with 10mL fluid sample, (b) in fluid sample, inject 20 μ L butyl chlorocarbonates as derivating agent/extraction phase, (c) under 2 ℃ of conditions, ultrasonic 7min forms emulsion, (d) under 4000rpm condition, centrifugal 6min realization is separated, (e) with 5 μ L gas chromatographic sample introduction pins (dead volume is 0), pipette the sedimentary facies 2 μ L of glass centrifuge tube bottom, inject gas chromatograph is analyzed.
Fig. 2 is actual environment water sample gas chromatogram.(A) mark-on deionized water (600 μ g/L); (B) deionized water blank; 1, aniline; 2,2,6 ?xylidin; 3, para-totuidine; 4, o-aminoanisole; 5,4 ?Lv ?2 ?methylaniline; S1, sludge drying condensed fluid; S2, city garbage percolate; S2, municipal effluent; S4, the Changjiang river saliva; S5, Qiantang River water; S6, Xi Hushui; S7, tap water.
Embodiment
In synchronous derivative ultrasonic emulsification micro-extraction gas chromatography determination environmental water sample, the method for amino benzenes compounds comprises the steps:
(1) 10mL fluid sample is injected to 15mL point end glass centrifuge tube, in the quick filling liquid sample of butyl chlorocarbonate with 50 μ L micro-sampling pins using 20 μ L as derivating agent/extraction phase, then moved in high power numerical control supersonic cleaning machine;
(2) ultrasonic 7min under the condition of 2 ℃ of frequency 40kHz, power 50W, temperature, in glass centrifuge tube, fluid sample becomes after emulsion, with hydro-extractor centrifugal 6min under 4000rpm condition, emulsion in test tube is completed and be separated, sedimentary facies cumulative volume is 10 μ L;
(3) with the gas chromatographic sample introduction pin of 5 μ L, draw the sedimentary facies 2 μ L of test tube bottom, inject gas chromatograph is analyzed, and gas chromatographic sample introduction pin dead volume is 0;
(4) with gas chromatograph, analyze and detect amino benzenes compounds, gas chromatograph is equipped with shunting/Splitless injecting samples system and flame ionization ditector, gas chromatographic column be HT ?5 capillary gas chromatographic columns, 30m * 0.25mm * 0.25 μ m, fill mutually 5% ?diphenyl ?95% ?dimethyl polysiloxane, temperature programme: initial 80 ℃ retain 4min, then with 8 ℃/min, be warmed up to 160 ℃, in 160 ℃, keep 2min, with 5 ℃/min, be warmed up to 230 ℃ of end afterwards, gas chromatograph sampling device and detector temperature are 270 ℃, the nitrogen of 99.999% purity is carrier gas and make-up gas, flow rate of carrier gas is 1.20mL/min, make-up gas flow velocity is 25mL/min, air velocity 300mL/min, hydrogen flow rate 30mL/min,
(5), according to the analysis result of gas chromatography, obtain the content data of amino benzenes compounds in environmental water sample.
Embodiment
Adopt synchronous derivative ultrasonic emulsification micro-extraction vapor-phase chromatography, 5 kinds of amino benzenes compounds (aniline, Aniline in testing environment water sample; 2,6 ?xylidin, 2,6 ?Dimethylaniline; Para-totuidine, p ?Touidine; O-aminoanisole, o ?Anisidine; 4 ?Lv ?xylidin, 4 ?Chloro ?2 ?methylaniline) content, concrete implementation step is as follows:
(1) get respectively: sludge drying condensed fluid, city garbage percolate, municipal effluent, the Changjiang river saliva, Qiantang River water, West Lake water and 7 kinds of each 10mL of environmental water sample of tap water, inject 15mL point end glass centrifuge tube, with 50 μ L micro-sampling pins, 20 μ L butyl chlorocarbonates (as derivating agent/extraction phase) are injected respectively to environmental water sample fast, then moved in KQ ?400KDE type high power numerical control supersonic cleaning machine.
(2) ultrasonic 7min under the condition of 2 ℃ of frequency 40kHz, power 50W, temperature, in glass centrifuge tube, fluid sample becomes after emulsion, with D ?78532 type hydro-extractors centrifugal 6min under 4000rpm condition, make the emulsion in test tube complete be separated (sedimentary facies cumulative volume is 10 μ L).
(3) with the gas chromatographic sample introduction pin (dead volume is 0) of 5 μ L, draw the sedimentary facies 2 μ L of test tube bottom, inject gas chromatograph is analyzed.
(4) adopt the content of the amino benzenes compounds in gas chromatograph (FULI9790) analysis water-like that is equipped with shunting/Splitless injecting samples system and flame ionization ditector (FID), gas chromatographic column be HT ?5 capillary gas chromatographic columns (30m * 0.25mm * 0.25 μ m, fill mutually 5% ?diphenyl ?95% ?dimethyl polysiloxane), temperature programme: initial 80 ℃ retain 4min, then with 8 ℃/min, be warmed up to 160 ℃, in 160 ℃ of maintenance 2min, with 5 ℃/min, be warmed up to 230 ℃ of end afterwards.Injector and detector temperature are all made as 270 ℃.Nitrogen (99.999%) is carrier gas and make-up gas, and flow velocity is respectively 1.20mL/min and 25mL/min, air velocity 300mL/min, hydrogen flow rate 30mL/min.
Table 1 has provided the content characteristics of 5 kinds of amino benzenes compounds in 7 kinds of environmental water samples.From table 1 and Fig. 2, can find out, in sludge drying condensed fluid (S1), detected aniline, 2,6 ?xylidin, para-totuidine and 4 ?Lv ?2 ?methylaniline, concentration is respectively 47.1,23.2,9.7 and 163.8 μ g/L; In city garbage percolate (S2), detected aniline, o-aminoanisole and 4 ?Lv ?2 ?methylaniline, concentration is respectively 6.1,19.7 and 38.6 μ g/L; In municipal effluent (S3), detected aniline and 4 ?Lv ?2 ?methylaniline, concentration is respectively 12.9 and 11.7 μ g/L; In other environmental water samples, do not detect amino benzenes compounds.Seven kinds of environmental water samples have been carried out respectively to three groups of parallel mark-ons and reclaimed analysis (mark-on concentration is 60 μ g/L), result shows, the relative recovery of tested amino benzenes compounds (RR) is between 86.8%～105.5%, and standard deviation RSD (n=3) is between 2.6%～5.5%.
The analysis result of amino benzenes compounds in table 1 environmental water sample
Note: S1, sludge drying condensed fluid; S2, city garbage percolate; S3, municipal effluent; S4, the Changjiang river saliva; S5, Qiantang River water; S6, Xi Hushui; S7, tap water.
ND does not detect amino benzenes compounds.
Claims (1)
1. a method for amino benzenes compounds in synchronous derivative ultrasonic emulsification micro-extraction gas chromatography determination environmental water sample, is characterized in that it comprises the steps:
(1) 10mL fluid sample is injected to 15mL point end glass centrifuge tube, in the quick filling liquid sample of butyl chlorocarbonate with 50 μ L micro-sampling pins using 20 μ L as derivating agent/extraction phase, then moved in high power numerical control supersonic cleaning machine;
(2) ultrasonic 7min under the condition of 2 ℃ of frequency 40kHz, power 50W, temperature, in glass centrifuge tube, fluid sample becomes after emulsion, with hydro-extractor centrifugal 6min under 4000rpm condition, emulsion in test tube is completed and be separated, sedimentary facies cumulative volume is 10 μ L;
(3) with the gas chromatographic sample introduction pin of 5 μ L, draw the sedimentary facies 2 μ L of test tube bottom, inject gas chromatograph is analyzed, and gas chromatographic sample introduction pin dead volume is 0;
(4) with gas chromatograph, analyze and detect amino benzenes compounds, gas chromatograph is equipped with shunting/Splitless injecting samples system and flame ionization ditector, gas chromatographic column is HT-5 capillary gas chromatographic column, 30m * 0.25mm * 0.25 μ m, fill phase 5%-diphenyl-95%-dimethyl polysiloxane, temperature programme: initial 80 ℃ retain 4min, then with 8 ℃/min, be warmed up to 160 ℃, in 160 ℃, keep 2min, with 5 ℃/min, be warmed up to 230 ℃ of end afterwards, gas chromatograph sampling device and detector temperature are 270 ℃, the nitrogen of 99.999% purity is carrier gas and make-up gas, flow rate of carrier gas is 1.20mL/min, make-up gas flow velocity is 25mL/min, air velocity 300mL/min, hydrogen flow rate 30mL/min,
(5), according to the analysis result of gas chromatography, obtain the content data of amino benzenes compounds in environmental water sample.
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Cited By (5)
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| CN104655779A (en) * | 2015-03-03 | 2015-05-27 | 浙江中一检测研究院股份有限公司 | Simple and convenient testing method for phenylamine in soil |
| CN105548383A (en) * | 2015-12-10 | 2016-05-04 | 苏州国环环境检测有限公司 | Method for detecting aniline in seawater |
| CN105548430A (en) * | 2015-12-10 | 2016-05-04 | 苏州国环环境检测有限公司 | Method for detecting aniline in soil |
| CN105675771A (en) * | 2016-03-22 | 2016-06-15 | 河北工业大学 | Method for gathering aromatic amine compounds from water |
| CN111077259A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Solid-phase extraction, derivatization, separation and determination method of aniline compounds in gasoline |
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| JP2005134274A (en) * | 2003-10-31 | 2005-05-26 | Jfe Steel Kk | Quantitative analytical method for aldehyde in solid sample |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104655779A (en) * | 2015-03-03 | 2015-05-27 | 浙江中一检测研究院股份有限公司 | Simple and convenient testing method for phenylamine in soil |
| CN105548383A (en) * | 2015-12-10 | 2016-05-04 | 苏州国环环境检测有限公司 | Method for detecting aniline in seawater |
| CN105548430A (en) * | 2015-12-10 | 2016-05-04 | 苏州国环环境检测有限公司 | Method for detecting aniline in soil |
| CN105675771A (en) * | 2016-03-22 | 2016-06-15 | 河北工业大学 | Method for gathering aromatic amine compounds from water |
| CN111077259A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Solid-phase extraction, derivatization, separation and determination method of aniline compounds in gasoline |
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