CN104713955B - Method for detecting 1,4-dioxan in water - Google Patents
Method for detecting 1,4-dioxan in water Download PDFInfo
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- CN104713955B CN104713955B CN201310691254.8A CN201310691254A CN104713955B CN 104713955 B CN104713955 B CN 104713955B CN 201310691254 A CN201310691254 A CN 201310691254A CN 104713955 B CN104713955 B CN 104713955B
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Abstract
The invention discloses a new method for onsite rapid sensitive accurate detection of ppb magnitude of 1,4-dioxan in water. A gas chromatography/differential ion mobility spectrometry (GC/DMS) dimensional separation means is used as a basic detection technology, online membrane extraction sample introduction mode matched ion mobility spectrometry is discussed, and the detection resolution and sensitivity are improved by adjusting a compensation voltage and a radio frequency voltage and optimizing the flow velocity of a carrier gas, the membrane permeation balance time, the GC pre-enrichment time and other parameters in order to determine a concentration calibration curve. The analysis method for GC/DMS analysis of a trace quantity of 1,4-dioxan in underground water and effective separation of halogenated hydrocarbons in the underground water is established in a positive ion mode.
Description
Technical field
The invention discloses a kind of carry out live sensitive, accurate new detecting method to 1,4- dioxanes in water.Extracted with film
Take-gas-chromatography/differential ion mobility spectrum is basic detection technique, using positive ion mode, membrane extraction on-line sampling device, build
The analysis method to underwater trace 1,4- dioxanes is found.
Background technology
1,4- dioxanes（It is often simply called dioxanes）, the monocyclic heterocycles organic compound of clear, colorless is liquid at room temperature
Body, can be miscible with water and common organic solvents, has hygroscopy.There is very strong stability, be mainly used as solvent, emulsifying agent, de-sludging
Agent etc., therefore Jing often adds the material in the detergent class product such as cosmetics, cleaning essence, washing powder.Dioxanes has greatly to health
Harm, if suction, eating, or percutaneous skin is absorbed in vivo, having and anaesthetize and stimulation.It has cumulative effect not in vivo
Easily discharge, it is irritant to skin, eye and respiratory system.Dioxanes may have carcinogenicity, and in IARC, it is divided into 2B classes.Cause
This, realizes in water that dioxanes is online, sensitive, accurate measurement is significant.
At present, the common method of the sample pre-treatments of para-dioxane has liquid-liquid extraction（LLE）, purge and trap (P＆T), directly
Liquid injection sample introduction (DAI), SPE/SPME (SPE/SPME), head space/Headspace-solid phase microextraction (HS/HS-
The method such as SPME).It is gas-chromatography that tradition separates the method for dioxanes（GC）, then respectively with mass spectrum (MS), hydrogen flame ion
Change detector (FID) combination.These traditional analysis processes include the sample pretreating method of complexity, including field sampling, fortune
It is defeated, and Laboratory Instruments analysis.These analysis methods can carry out accurate quantitative analysis, however could not but provide immediately,
The analysis result of line, also analytical cycle is long, bulky, high cost.
Type ion mobility spectrometry（Differential Mobility Spectrometry, hereinafter referred to as DMS）Reach a conclusion after weighing a matter
Since generation, with its high resolution, speed fast, small volume, it is low in energy consumption the features such as be widely used in chemical warfare agent, drugs and explosive
Deng detection.DMS is that the difference using ionic mobility in height off field carries out ion isolation.Sample is entered by carrier gas carrier band
Ionized region, the sample ions being then ionized enter migration area.Migration area is generally two pieces of parallel flat boards or coaxial circle
Barrel structure.The rf electric field of asymmetric waveform is added on one flat plate wherein（Dispersion Voltage, DV）, it is another
Block is grounded.Ion is except outer in airflow direction motion in the migration area, understand also in the presence of high-frequency electric field with carrier gas direction
The motion shaken up and down is done on vertical direction.Due to the mobility difference in height field ion, in each week of high-frequency electric field
Phase, ion all can produce a displacement δ y in vertical direction.After multiple cycles, ion will be got on pole plate and bury in oblivion
Fall.If applying the offset voltage of a matching on high-frequency electric field（CompensationVoltage,CV）, ion is made in y directions
Total displacement s less than its initial position to pole plate distance so that ion can be reached and detect pole by drift region.Pass through
Within the specific limits offset voltage is scanned, it is possible to so that different sample ions pass through to move under specific offset voltage
Area is moved, is then detected by detector.The migration spectrogram standard substance for so obtaining may serve as the identification of sample after characterizing.
Therefore, this patent is used in online membrane extraction sampling apparatus on GC/DMS, sets up-two evil of Isosorbide-5-Nitrae of underwater trace
The online, accurate of alkane, the new method of Sensitive Detection.
The content of the invention
In order to improve separating degree and the sensitivity of detection simultaneously, the highly sensitive detection to the Isosorbide-5-Nitrae-dioxanes in water is realized.
The technical solution used in the present invention is：
By online membrane extraction sampling device, Isosorbide-5-Nitrae-dioxanes is carried out point passing through in gas-chromatography by carrier gas transport
Online membrane extraction sampling device, the Isosorbide-5-Nitrae-dioxanes in water is separated in gas-chromatography by carrier gas transport, Ran Houfen
From sample component be used for quickly detecting with type ion mobility spectrometry.Described online membrane extraction sampling device：It is by hollow
Tubular film is fastened in the container of a constant volume, and in container, filling water sample to be measured, is passed through carrier gas, carrier gas in tubular film one end
With certain flow rate by tubular film, in being analysed to organic matter from liquid-phase extraction to gas phase, and it is thermal agitation device using magnetic force
Accelerate this mass transport process, organic matter to be analyzed is exported into gas-chromatography from the other end of tubular film with carrier gas.
Dimethyl silicone polymer of the described hollow tubular film for commercialization（PDMS）Film（Co.）, its internal diameter is
1.47mm, wall thickness 0.23mm.The container sample bottle of a described constant volume is 250mL quartz glass bottles, and bottle cap is PTFE material（Co.）.The described hollow tubular film tubular film that mode is 50cm length of being fastened in container is fixed on spiral gold
On category support, the support is fixed on the lid of sample bottle；The two ends of tubular film are respectively fitted over two external diameter 2mm internal diameter 0.5mm
Tetrafluoro connecting tube on, it is and logical by the two of 1/4 turn of 1/8inch（）Respectively with film carrier gas inlet gas circuit and outlet
Gas circuit mutually closely connects.
The described carrier gas with certain flow rate is through being dried trap（Trap）With molecular sieve filtration
Air passes through program flow controller（Alicat0.2%）To realize accurate flow control.Described biography
Matter process is a kind of process of pervaporation.Due to material difference in the liquid phase with concentration in film phase, material leads to from liquid phase
Cross the dissolving of concentration difference effect of mass transmitting and enter into film phase, and diffusive migration wherein, eventually arrive at the opposite side of film and made by evaporating
With desorption in gas phase；This process for entering into gas phase via dissolving diffusive evaporation from liquid phase is referred to as oozing
Evaporate thoroughly.
The standard liquid of the Isosorbide-5-Nitrae-dioxanes of variable concentrations is prepared using the standard items of Isosorbide-5-Nitrae-dioxanes, and carrier gas is respectively adopted
Bring in gas-chromatography and separated, the sample component being then peeled off is used for quickly detecting with type ion mobility spectrometry, obtain
The retention time of the standard items of gas chromatographic detection and the corresponding peak intensity of variable concentrations standard liquid, and differential type ion moves
Offset voltage and the corresponding peak intensity of variable concentrations standard liquid of the standard items of spectrum detection is moved, as the qualitative of sample to be analysed
Or quantitative reference, to complete the analysis process to sample to be analysed.
Advantages of the present invention is as follows：
1. with gas-chromatography/differential ion mobility spectrum（GC/DMS）For basic detection technique, the retention time of GC and DMS
Offset voltage enhances its specificity to target compound as two dimensional separation means.Both separating degree had been ensure that, had been improve again
Detection sensitivity.
2. in combination with the membrane extraction device being made up of tubular film, dioxanes in a step Aulomatizeted Detect water is realized, saved
The sampling and transport of sample is gone, it is time-consuming.
3. the detection method of this patent is applicable not only to monitor the dioxanes in water on-line, while it is applied to halogenated hydrocarbons, inspection
Survey sensitivity and reach ppb magnitudes.
Description of the drawings
Device flow charts of the Fig. 1 for ME-GC/DMS；
Fig. 2 is that the response signal on 100ppb dioxane different in flow rate of sampling carrier gas affects. built-in figure:Adopting respectively
GC chromatogram of the sample flow velocity for 50,150and300sccm；
Fig. 3 is GC/DMS to 100ppb1, and the response intensity of 4-dioxane is sampled with the Changing Pattern of film time of penetration
Gas velocity is respectively the spectrogram of 50sccm and 150sccm；
Fig. 4 is effect of signals figure of the enrichment time of GC preenrichment devices (Trap) to 1,4-dioxane；
Concentration-response curve figures of the Fig. 5 for 1,4-dioxane (2-500ppb).Insertion:To 1,4-dioxane (2-
Linearity correction figure 20ppb)；
Fig. 6 be water in 1,4-dioxane and five kinds of halogenated hydrocarbons ME-GC/DMS two dimensional separation collection of illustrative plates.
Specific embodiment
As shown in figure 1, described membrane extraction-gas-chromatography/differential ion mobility spectrometer, including membrane extraction device, pre- richness
Acquisition means and GC/DMS analyzers.Differential expression ion mobility spectrometry is a relatively new technology, depends on ion in High-Field（It is logical
Often greater than 40*10-17V.cm2）Separated and detected with the difference of low field mobility.Carrier gas is through being dried trap（Trap）Pass through program flow controller with the air of molecular sieve filtration（Alicat0.2%）After divide
Into two-way road.All the way 100sccm as auxiliary gas for the gas circuit of film sampling system and instrument extraneous air are kept apart；One
The adjustable carrier gas as tubulose film device of road flow velocity（Carrier Gas）, for dividing of extracting film from the aqueous solution
Analysis thing steam is sent in preenrichment device.Due to material difference in the liquid phase with concentration in film phase, material leads to from liquid phase
Cross the dissolving of concentration difference effect of mass transmitting and enter into film phase, and diffusive migration wherein, eventually arrive at the opposite side of film and made by evaporating
With desorption in gas phase.This process for entering into gas phase via dissolving diffusive evaporation from liquid phase is referred to as oozing
Evaporate thoroughly.It is exactly a kind of process of pervaporation that in this chapter, PDMS films from water are extracted into halogenated hydrocarbons in gas phase.
Fig. 2-6 provides some experiment spectrograms and gives explanation to the present invention.The experiment condition of these spectrograms is：During experiment
Radio-frequency voltage RF of DMS is 1000V, and offset voltage is -3.3V.Migration tube temperature is maintained at 120 DEG C, membrane extraction unit temp 25
DEG C, the GC chromatogram Preconcentration times are the 20-200 seconds.
Embodiment 1
Fig. 2 is the different in flow rate of carrier gas of sampling（50-300sccm）Response signal shadow to the 1,4-dioxane of 100ppb
Ring. inside it is set to respectively in the GC chromatograms that sampling flow velocity is 50,150and300sccm.The increasing with flow rate of carrier gas can be seen
Plus, the response intensity of Isosorbide-5-Nitrae-dioxane is to reduce successively, therefore 50sccm is the membrane extraction sample carrier gas speed of optimization.
Fig. 3 is GC/DMS to 100ppb1, and the response intensity of 4-dioxane is sampled with the Changing Pattern of film time of penetration
Gas velocity is respectively the spectrogram of 50sccm and 150sccm.It can be seen that no matter sample gas flow velocity is much, it is flat that membrane extraction reaches infiltration
The time of weighing apparatus is 30 minutes, and rear response intensity tends to saturation.
Fig. 4 is effect of signals figure of the enrichment time of GC preenrichment devices (Trap) to 1,4-dioxane.As can be seen that
With the increase of trap times, loudness increase is responded, tend to saturation when more than 150 seconds, therefore during the preenrichment of optimization
Between be 150 seconds.
Embodiment 2
With GC/DMS as detecting instrument under positive and negative double ion pattern, all the way 100sccm as auxiliary gas for film is entered
The gas circuit of sample system and instrument extraneous air are kept apart；Carrier gas of the flow velocity 50sccm as tubulose film device all the way, for inciting somebody to action
The analyte vapor that film is extracted from the aqueous solution is sent in preenrichment device.During experiment, radio-frequency voltage RF of DMS is
1000V, offset voltage are -3.3V.Migration tube temperature is maintained at 120 DEG C, 25 DEG C of membrane extraction unit temp, GC chromatogram Preconcentrations
Time is 150 seconds.
What Fig. 5 was given is the concentration-response curve figure of the 1,4-dioxane (2-500ppb) in water.Insertion:To 1,4-
The linearity correction figure of dioxane (2-20ppb).The response of the method para-dioxane is sensitive, 2-20ppb concentration ranges linear correlations
Coefficients R2=0.992, minimum detectability is calculated as 0.67 μ g/L.
Fig. 6 be water in 1,4-dioxane and five kinds of halogenated hydrocarbons mixture ME-GC/DMS two dimensional separation collection of illustrative plates.
Wherein five kinds halogenated hydrocarbons include TCE, PCE, Trans-1,2-DCE, CHCl3And CCl4.It can be seen that the inventive method
Above-mentioned six kinds of mixtures can be separated well.
Claims (4)
1. it is a kind of detection water in Isosorbide-5-Nitrae-dioxanes method, it is characterised in that：By online membrane extraction sampling device, by water
Isosorbide-5-Nitrae-dioxanes by carrier gas transport separated in gas-chromatography, the sample component differential type ion being then peeled off is moved
Move spectrum to be used for quickly detecting；
Described online membrane extraction sampling device：It is to be fastened in the container of a constant volume, in container by hollow tubular film
Water sample to be measured being filled, carrier gas being passed through in tubular film one end, carrier gas, is analysed to by tubular film with 50～500ml/min flow velocitys
During organic matter is from liquid-phase extraction to gas phase, and this mass transport process is accelerated using magnetic force heating and stirring device, made to be analyzed organic
Thing is exported into gas-chromatography from the other end of tubular film with carrier gas；
Described hollow tubular film for commercialization dimethyl silicone polymer (PDMS) film, its internal diameter be 1.47mm, wall thickness
0.23mm；Its purpose is primarily to reduce permeation flux of the water in film；
The standard liquid of Isosorbide-5-Nitrae-dioxanes is prepared using the standard items of Isosorbide-5-Nitrae-dioxanes, carrier gas is respectively adopted and is brought in gas-chromatography
Separated, the sample component being then peeled off is used for quickly detecting with type ion mobility spectrometry, obtained gas chromatographic detection
The retention time of standard items and the corresponding peak intensity of variable concentrations standard liquid, and the standard of type ion mobility spectrometry detection
The offset voltage of product and the corresponding peak intensity of variable concentrations standard liquid, as the qualitative or quantitative reference of sample to be analysed, with
Complete the analysis process to sample to be analysed；Radio-frequency voltage RF of described DMS is 1000V, and offset voltage is -3.3V；Migration
Pipe temperature is maintained at 120 DEG C, 25 DEG C of membrane extraction unit temp, and the GC chromatogram Preconcentration times are the 20-200 seconds；Membrane extraction sample
Carrier gas speed is 50sccm, and membrane extraction reaches the time of osmotic equilibrium and is 30 minutes；The preenrichment time is the 150-200 seconds.
2. method according to claim 1, it is characterised in that：
The container sample bottle of a described constant volume is 250mL quartz glass bottles, and bottle cap is PTFE material.
3. method according to claim 1, it is characterised in that：
The described hollow tubular film tubular film that mode is 50cm length of being fastened in container is fixed on spiral metal support
On, the support is fixed on the lid of sample bottle；The two ends of tubular film are respectively fitted over the tetrafluoro of two external diameter 2mm internal diameter 0.5mm
In connecting tube, and mutually closely it is not connected with film carrier gas inlet gas circuit and outlet gas circuit by two reduction of fractions to a common denominators of 1/4 turn of 1/8inch.
4. method according to claim 1, it is characterised in that：
The carrier gas is realizing precise control stream through being dried the air of trap and molecular sieve filtration by program flow controller
Amount.
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| CN109883803B (en) * | 2017-12-06 | 2021-06-04 | 中国科学院大连化学物理研究所 | Secondary enrichment and analysis device and method |
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Non-Patent Citations (5)
| Title |
|---|
| Method Development for the Analysis of 1,4-Dioxane in Drinking Water Using Solid-Phase Extraction and Gas Chromatography-Mass Spectrometry;Paul E. Grimmett 等;《Journal of Chromatographic Science》;20090131;第47卷;31-39 * |
| The Extraction and Analysis of 1,4-Dioxane from Water Using Solid-Phase Microextraction Coupled with Gas Chromatography and Gas Chromatography—Mass Spectrometry;Robert E. Shirey 等;《Journal of Chromatographic Science》;20060831;第44卷;444-450 * |
| 顶空/气相色谱_串联质谱法测定合成洗涤剂及化妆品中二噁烷残留;崔进 等;《分析测试学报》;20121130;第31卷(第11期);1446-1450 * |
| 顶空固相微萃取-气相色谱法测定洗涤制品中二噁烷;任海林;《齐齐哈尔大学学报》;20060731;第22卷(第4期);13-15 * |
| 顶空固相微萃取-气相色谱联用技术检测水相中的1,4-二噁烷;奚星林 等;《中国卫生检验杂志》;20030831;第13卷(第4期);452-453 * |
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