CN107764918A

CN107764918A - The negative pressure extraction piece-rate system and separation method of organic pollution in sample

Info

Publication number: CN107764918A
Application number: CN201711211555.0A
Authority: CN
Inventors: 谢家理
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-11-28
Filing date: 2017-11-28
Publication date: 2018-03-06

Abstract

The invention discloses the negative pressure extraction piece-rate system and separation method of semi-volatile organic matter in sample and fixedness organic matter.The present invention makes to form lasting negative pressure and heating environment around tested sample by the effect of vavuum pump and heater, the property of semi-volatile organic matter and the similar volatile organic matter of fixedness organic matter generation under this environment, gasification forms steam and is sufficiently separated with sample substrate, organic steam after separation is transmitted to adsorbent adsorption and enrichment by the suction of vavuum pump by sample transfer pipeline, then will enter gas-chromatography after adsorbent direct injection analysis or Thermal desorption, solvent desorption containing target compound or Gc/ms Analyser is analyzed.Present invention extraction, purification and sample concentration are completed simultaneously, greatly reduce analysis cost and time.

Description

The negative pressure extraction piece-rate system and separation method of organic pollution in sample

Technical field

The present invention relates to the Sample Pretreatment Technique field of chromatography, and in particular to the negative pressure of organic pollution in sample Extract and separate system and separation method.

Background technology

According to World Health Organization WHO1989 regulation, (under normal temperature) boiling point is from being effumability less than 0 DEG C to 50 DEG C Organic matter (VVOC), 50 DEG C -250 DEG C of boiling point for volatile organic matter (VOC), saturated vapor pressure exceedes at room temperature for it 133.32Pa, organic compound of the boiling point from 240-260 DEG C to 380-400 DEG C are referred to as semi-volatile organic matter (SVOC), boiling point Organic compound higher than 380-400 DEG C is referred to as fixedness organic matter or particulate organic matter (POM).Organo-chlorine pesticide, have Machine phosphorus insecticide, polycyclic aromatic hydrocarbon, phthalic acid ester, Polychlorinated biphenyls, nitrobenzene, chlorobenzene class (chlorine atom substitution number more than 4) Etc. semi-volatile organic matter and particulate organic matter can be included into.

The pre-treating method for half volatilization of the boiling point higher than 250 DEG C and fixedness organic matter is mainly organic molten at present The method for concentration of agent extract and separate purification method and sample extraction liquid, it specifically includes following several：

The purification method of sample extraction liquid：U.S. EPA 3600C series, such as the purification of EPA3610B alumina columns, 3611B Alumina column purifies and the separation of petroleum-type waste, 3620BFlorisil column purifications, the purification such as 3640A gel chromatography column purifications Method.These purification methods mainly include solid phase extraction and gel permeation chromatography.Solid phase extraction (SPE) uses disposable Solid phase extraction column or chromatographic column, and aging, elution, loading, four steps of elution need to be passed through, each step is required to using many It is also longer in 10ml organic reagents and various consumptive materials, used time.Gel permeation chromatography purification (GPC) method be by with absorption, point With the gel with ion exchange as separation chromatography, organic solvent is allowed continuously by gel chromatography, to work as measured object When solution passes through chromatographic column, volume be more than gel pore macromolecular from gel particles gap by thus outflow speed it is fast, And volume is less than the molecule of gel pore into the aperture of gel particles, the rate of outflow is slow, so that sample is purified.Gel Although chromatogram column purification good purification, need persistently to use organic solvent, consumption of organic solvent is very big.

The extracting process of fluid sample：Such as U.S. EPA 3510- liquid-liquid extraction methods and EPA3535- solid phase extractions.Liquid Liquid-liquid extraction method is to mix sample and organic solvent by a certain percentage in separatory funnel and vibrate a period of time, in water sample Organic matter is just extracted into organic solvent, and the anhydrous sodium sulfate after then being bakeed with high temperature removes organic solvent phase moisture, then Concentrating instrument is blown by Rotary Evaporators or nitrogen and concentrates organic extract liquid to 1mL volume, whole pretreatment process duration, is used A large amount of organic reagents.Solid phase extraction techniques in sample are identical with the solid phase extraction techniques in extract purification method, are it Middle loading step needs the longer time.

The extracting process of solid sample：Such as U.S. EPA 3540C- soxhlet's extractions, the automatic soxhlet's extractions of EPA3541-, EPA3545- Accelerate solvent extractions, EPA3550B- ultrasonic extractions, EPA3546- microwave abstractings, EPA3560- supercritical fluids Extraction etc..EPA-3540C soxhlet's extraction methods are to utilize solvent refluxing and siphon principle, solid matter is continuously had by pure After solvent extraction, the process that the testing compound in solid matter is extracted in organic solvent, whole process needs 12~ 24h or so is, it is necessary to use special soxhlet's extraction equipment.EPA3545 Accelerate solvent extraction methods are that solid matter is put into extraction In tank, in high temperature (Tong Chang≤100 DEG C) and high pressure (Tong Chang≤1000PSI) under the conditions of, using organic solvent by solid matrix The method that extracts of testing compound, it is necessary to using corresponding Accelerate solvent extraction equipment and a large amount of organic solvents. EPA3550B ultrasonic extractions are under the cavitation of ultrasonic wave, the test substance in solid matrix are extracted to organic molten The method of agent is, it is necessary to specific ultrasonic extraction instrument.EPA3546- microwave abstractings are to make solid or half using the effect of electromagnetic field Some organic components in solid matter efficiently separate with matrix, and can keep analyzing the one of the script compound state of object Kind separation method is, it is necessary to specific powerful Microwave Extraction Apparatus.EPA3560- supercritical fluid extractions are at a lower temperature, no During the pressure of disconnected increase gas, gas can change into liquid, more than critical point in the range of, state of matter is in gas and liquid Between body, the fluid within the scope of this turns into supercritical fluid (SF).Supercritical fluid has penetrating more by force for similar gas Power and the greater density and solubility similar to liquid, there are good solvent properties, can be extracted as solvent.It is although super The organic solvent that critical fluids use does not use organic solvent even less, but supercritical fluid needs very harsh environment bar Part, this needs special instrument to form the environmental condition of supercritical fluid so as to complete to extract.

The method for concentration of sample extraction liquid：The method for concentration of extract mainly includes rotary evaporation concentration and nitrogen blows concentration two Kind mode.Rotary evaporation concentration is by the cucurbit containing extract or solvent while heats and rotate, and heating-up temperature is close to molten Agent boiling point, increase disengagement area.In addition, under cooler effect, heat steam is liquefied rapidly, accelerates evaporation rate.Rotation is steamed Concentrating instrument is sent out suitable for reflux operation, the concentration of the rapid evaporation, micro high boiling component of a large amount of solvents, decompression can also be sealed To 400~600 millimetress of mercury, accelerate the speed that solvent evaporation concentrates with component.Nitrogen evaporator is that nitrogen is blowed into heating sample Surface, the solvent in sample is set to evaporate rapidly, separate, so as to realize the concentration of extract.The concentration process of two kinds of condensing modes The plenty of time will be taken, and easily causes the loss of target compound.

In summary, at present for semi-volatile organic matter or the pre-treating method of fixedness organic matter, either The purification method of extract, the extracting process of fluid matrix, the extracting process of solid matrix, the common feature of the above method are to need Will using more organic solvent, reagent and consumptive material, need to use large-scale pre-processing device to reach the extraction efficiency of requirement, and And pre-treatment time length, intermediate steps are more, unit sample processing cost is high, and waste residue and liquid has the possibility of secondary pollution, and Easily introduce and disturb in pilot process, impact analysis result.The concentration process of a large amount of solvents not only grow by the time, and easily causes The loss of target compound causes the failure of an experiment.In addition, these methods also will be big in sample while target compound is extracted Amount impurity extraction comes out, and not only needs extra purification process, and clean-up effect is difficult to ensure that, produce analysis result deviation and The harmful effect that chromatogram service life reduces.

The content of the invention

An object of the present invention is to provide for a kind of negative pressure extraction piece-rate system of organic pollution in sample, this point Combined from system by common apparatus, no large scale equipment facility, and it is simple in construction, reasonable in design, cost is cheap.

To achieve the above object, the technical solution adopted by the present invention is as follows：

The negative pressure extraction piece-rate system of organic pollution in sample, including sample bottle, sample heating device, absorbing mechanism, suction Sample heating device described in receiving mechanism cooling device and pump, which is arranged on, is used for the temperature for adjusting sample bottle, the absorption machine outside sample bottle Structure cooling device, which is arranged on, is used for the temperature for adjusting absorbing mechanism outside absorbing mechanism, the sample bottle passes through the first sample conveying tube Line connects with absorbing mechanism, and the first sample transfer pipeline peripheral hardware put for adjust the first sample transfer pipeline temperature first Heater；The absorbing mechanism is also connected by being evacuated pipeline with the entrance point of pump, and the port of export of the pump is connected with Machine thing steam outlet pipe；The pumping pipeline is provided with pressure controller.

Further, it is equipped with thermometer on the sample bottle, absorbing mechanism and the first sample transfer pipeline.

Specifically, the absorbing mechanism includes absorption bottle and the liquid absorbent being placed in absorption bottle；The sample passes Defeated pipeline one end is stretched into sample bottle at the top of sample bottle, and above sample in sample bottle, the first sample transfer pipeline is another One end is stretched into absorption bottle at the top of absorption bottle, and is submerged in absorption bottle in liquid absorbent；It is described pumping pipeline one end from Stretched at the top of absorption bottle in absorption bottle, and above adsorbent；Absorbing mechanism's cooling device is to be arranged on outside absorption bottle First cooling device of side.

As another embodiment, the absorbing mechanism includes adsorption tube and the solid absorption being filled in adsorption tube Agent；Described first sample transfer pipeline one end is stretched into sample bottle at the top of sample bottle, and above sample in sample bottle, the The one sample transfer line other end is connected with adsorption tube one end, and the adsorption tube other end then connects with pumping pipeline；It is described Absorbing mechanism's cooling device is to be arranged on the second cooling device on the outside of adsorption tube.

As another embodiment, the absorbing mechanism includes adsorption tube, solid absorbent, absorption bottle and liquid adsorption Agent；The solid absorbent is filled in adsorption tube, and the liquid absorbent is placed in absorption bottle；Described adsorption tube one end and the One sample transfer line connects, and the other end is connected with the second sample transfer pipeline；Described second sample transfer pipeline one end is from suction Receive top of bottle to stretch into absorption bottle, and be submerged in absorption bottle in liquid absorbent, while on the second sample transfer pipeline also Provided with the secondary heating mechanism for adjusting its temperature；Described pumping pipeline one end is stretched into absorbing mechanism at the top of absorption bottle, And above adsorbent in absorbing mechanism；Absorbing mechanism's cooling device is wrapped in the second cooling dress outside adsorption tube Put and be wrapped in the first cooling device outside absorption bottle.

Another object of the present invention is then to provide in a kind of separation sample using above-mentioned negative pressure extraction piece-rate system The method of organic pollution, this method collection are extracted, purified, concentrating in one, and simple to operate, separation cycle is short, and is easily achieved Automation.

The separation method is the deficiency for existing abstraction technique, foundation can be by gas-chromatography or Gc-mss The negative pressure extraction separation method of gasifiable semi-volatile organic matter and fixedness organic matter.Its separation principle is：Make sample Under lasting negative pressure and heating condition, the organic matter in sample bottle bottom sample matrix forms steam after being gasified, and Sample substrate with that can not gasify is sufficiently separated, the organic steam after separation by pump suction, by sample bottle The sample transfer pipeline of side is transmitted to adsorbent adsorption and enrichment, is then directly analyzed the adsorbent containing target compound Or analyzed after parsing, elution into gas-chromatography or gas chromatography-mass spectrometry.

The negative pressure extraction separation method of organic pollution, comprises the following steps in a kind of sample：

A, sample is put into sample bottle, and adsorbent is put into absorbing mechanism, then sample bottle is placed in sample heating In device, absorbing mechanism is placed in absorbing mechanism's cooling device；

B, by sample transfer pipeline, absorbing mechanism, pumping pipeline, pressure controller, pump and organic steam outlet according to Secondary connection, and keep closed No leakage；

C, sample heating device is opened, sample bottle keeping temperature is more than or equal to 40 DEG C；Utilize absorbing mechanism's cooling device Absorbing mechanism's temperature is set to be less than or equal to 100 DEG C；

D, the first and second heaters are opened, the first and second sample transfer pipelines is held in a certain temperature, are prevented Only testing compound is condensate in sample transfer line pipe wall.

E, pump and pressure controller are opened, the vacuum of sample bottle and absorbing mechanism is below 3.0kpa, adjusts sample The heating-up temperature of heater, evaporates sample, starts extraction and absorbs, the organic gas for departing from sample substrate passes through sample transfer Pipeline enters absorbing mechanism, and is absorbed by the adsorbent in absorbing mechanism, and into sample bottle, solution evaporates, and extraction is inhaled Harvest into.

Compared with prior art, the invention has the advantages that：

(1) piece-rate system of the invention is simple in construction, and its installations and facilities used is common device facility, without using big Type pre-processing device (such as Accelerate solvent extraction equipment, gel permeation chromatography cleaning equipment etc.), cost is cheap, and simple to operate, Intermediate steps are few, and the used time is few, can automaticity it is also higher, the analysis cost of sample can be greatly reduced.

(2) separation method of the present invention is the negative pressure extraction separation method used, and this method can be analyzed can be by gas chromatograph And the gasifiable semi-volatile organic matter and fixedness organic matter of Gc/ms Analyser measure.

(3) present invention uses on a small quantity or without using organic solvent, unit sample processing cost is lower, in waste residue and liquid also only Containing a small amount of or do not contain organic solvent, i.e., it can effectively reduce secondary pollution.

(4) separation method of the present invention is in negative pressure extraction separation process, the impurity that can not largely gasify (such as macromolecular Protein, sugar, humus, fat, pigment etc.) it can not be gasified by negative pressure extraction mode, thus can be by gasifiable organic matter Separated with the impurity that can not gasify, realize extraction with being carried out while purification, once complete, avoid traditional extraction side The shortcomings that formula also extracts a large amount of impurity while target compound is extracted, significantly reduces the interference during chromatography, makes Qualitative, quantitative is more accurate, extends chromatogram service life.

(5) separation method of the present invention is in negative pressure extraction separation process, and most of solvent is logical in sample bottle, absorbing mechanism The effect for crossing pump is pumped down in air, and remaining a small amount of organic solvent, target compound are then protected in absorption bottle and solid absorbent Stay in absorption bottle and solid absorbent, realize the concentration of sample, greatly reduce analysis cost and time.

(6) it is extraction, purification, dense in piece-rate system of the invention and method using organic matter in system separation sample Contracting is once completed, and step is few, simple to operate, and the cycle is short, easily realizes automation.

Brief description of the drawings

Fig. 1 is the principle schematic of negative pressure extraction separator figure-liquid absorbent absorption process of the present invention.

Fig. 2 is the principle schematic of negative pressure extraction separator figure-solid absorbent absorption process of the present invention.

Fig. 3 is the principle schematic of negative pressure extraction separator figure of the present invention-solid absorption series connection liquid absorption method.

Wherein, it is entitled corresponding to reference：

1- sample heating devices, 2- sample bottles, 3- samples, 4- the first sample transfer pipelines, 5- absorption bottles, 6- liquid adsorptions Agent, the cooling devices of 7- first, 8- pumping pipelines, 9- pressure controllers, 10- pumps, 11- organic steam outlets, 12- second are cold But device, 13- adsorption tubes, 14- the second sample transfer pipelines, 15- first heaters, 16- secondary heating mechanisms.

Embodiment

The invention will be further described with embodiment for explanation below in conjunction with the accompanying drawings, and mode of the invention includes but not only limited In following examples.

Embodiment 1

The negative pressure extraction piece-rate system of organic pollution as shown in figure 1, including connecting successively in the sample that the present embodiment uses Sample bottle 2, the first sample transfer pipeline 4, absorption bottle 5 and the pump 10 connect, the sample bottle 2 be provided with sample to be extracted, it is described Liquid absorbent 6 is provided with absorption bottle 5.Specifically, sample heating device 1 is arranged with outside sample bottle, the is arranged with outside absorption bottle One cooling device 7, the outer wrapping first heater 15 of the first sample transfer pipeline 4；The sample heating device 1 can be electric heater Or the common heater structure (because heater is relatively conventional, therefore not repeating) on the market such as heat exchanger, sample heating Device is arranged on outside sample bottle 2, and for adjusting the temperature of sample bottle, the first heater 15 can be pipe common on the market Shape heater structure, it is arranged on outside the first sample transfer pipeline 4, for adjusting the temperature of sample transfer pipeline.Described first is cold But device 7 selects the existing conventional cooling devices such as the spiral heat exchange tube to match with absorption bottle structure, semiconductor refrigerating equipment, First cooling device 7 is arranged on outside absorption bottle 5, for adjusting the temperature of absorbing mechanism, because sample bottle 2, the first sample pass Defeated pipeline 4 and the temperature of absorption bottle 5 and the effect of separating and extracting have considerable influence, it is therefore desirable to the temperature in it is monitored at any time, Therefore, it is equipped with thermometer on the sample bottle 2, the first sample transfer pipeline 4 and absorption bottle 5.First sample conveying tube The one end of line 4 is stretched into sample bottle from the top of sample bottle 2, and above sample in sample bottle, the first sample transfer pipeline 4 is another End is stretched into absorption bottle from the top of absorption bottle 5, and is submerged in absorption bottle in liquid absorbent.It is described pumping the one end of pipeline 8 from Stretch into absorbing mechanism at the top of absorption bottle, and above adsorbent in absorbing mechanism, and be evacuated the other end of pipeline 8 then with pump 10 Entrance point be connected, the port of export of pump is then connected with organic matter steam outlet pipe 11；In order that in negative when whole system works Pressure condition, the pumping pipeline 8 are provided with pressure controller 9.

The present embodiment additionally provides the method using organic pollution in above-mentioned piece-rate system separation sample, and its principle is logical Crossing the effect of vavuum pump and heater makes to form lasting negative pressure and heating environment around tested sample, the volatilization of this environment lower half Property organic matter and the similar volatile organic matter of fixedness organic matter generation property, gasification form steam and filled with sample substrate Separation, the organic steam after separation are transmitted to adsorbent adsorption and enrichment by the suction of vavuum pump by sample transfer pipeline, Then gas-chromatography or gas will be entered after adsorbent direct injection analysis or Thermal desorption, solvent desorption containing target compound Phase Chromatography/Mass Spectrometry combined instrument is analyzed (the separation method principle of following examples is identical with this).In the present embodiment, its Separation method is that caused gas composition leads in sample to be extracted 3 under pump 10 and the negative pressure state of the offer of pressure controller 9 Cross the first sample transfer pipeline 4 to enter in the liquid absorbent 6 in absorption bottle 5, target compound therein is by liquid absorbent 6 Absorb, remaining gas is then discharged by being evacuated pipeline 8 by organic steam outlet 11, that is, completes separation.Specific operation Step is as follows：

A, sample is put into sample bottle, and adsorbent is put into absorbing mechanism, then sample bottle is placed in sample heating In device, absorbing mechanism is placed in absorbing mechanism's cooling device, the first sample transfer pipeline is placed in first heater；

C, sample heating device is opened, and observes the thermometer registration of sample bottle and absorbing mechanism, makes sample bottle keeping temperature More than or equal to 40 DEG C, sample transfer pipeline temperature is more than or equal to 280 DEG C, and absorbing mechanism's temperature is less than or equal to 100 ℃；

D, pump and pressure controller are opened, sample bottle and absorbing mechanism is in negative pressure state, starts extraction and absorbs, take off Organic gas from sample substrate enters absorbing mechanism by sample transfer pipeline, and is carried out by the adsorbent in absorbing mechanism Absorb, into sample bottle, sample is evaporated, and extraction, which absorbs, to be completed.

In order that its separation method becomes apparent from, separating effect is more directly perceived, below, by taking example 1~7 as an example, carries out more Detailed description.

Example 1

This example is to the organo-chlorine pesticide and chlorobenzene class chemical combination in liquid phase (organic solvent phase, aqueous phase), solid phase (soil) The negative pressure extraction separation method test of thing.

1st, the negative pressure extraction separation method test of concentration is 200 μ g/L in toluene organo-chlorine pesticide and chlorobenzene compound

(1) standard liquid is prepared

By organo-chlorine pesticide and the liquid standard mixture of chlorobenzene, the mixing for the toluene phase that concentration is 100 μ g/mL is configured to Standard, 10mL toluene solvants is then taken into 22mL sample bottles, as whole blank sample；10mL toluene solvants are taken to 22mL samples In product bottle, as sample absorption bottle；10mL toluene solvants are taken into 22mL sample bottles, and add 20 μ L hybrid standards as measure Sample, concentration are 200 μ g/L；20 μ L hybrid standards are taken to be used as bioassay standard into 1mL toluene, concentration is 2 μ g/mL.

(2) gas circuit connects

By sample heating device, the sealed sample bottle equipped with testing sample, the sample absorption bottle equipped with liquid absorbent, first Cooling device, pump, sample transfer pipeline, heater, pumping pipeline, thermometer etc. are sequentially connected and installed as shown in Figure 1.

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 120 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0kpa, sample absorption bottle Temperature be less than 80 DEG C, sample transfer pipeline temperature be 280 DEG C, be evacuated to solution in sample bottle it is closely dry when add 10mL toluene, extremely Solution in sample bottle (to prevent that the absorbing liquid in sample absorption bottle is evaporated, pays attention to supplementing first at any time untill evaporating Benzene).After the completion of extraction, it is to be analyzed that the toluene concentration in absorption bottle is settled to 1mL.

(4) analysis method

Agilent7890A-5975C type gas chromatograph-mass spectrometers, DB-5MS chromatographic columns (30m*0.25mm*250 μm), carrier gas are Helium (purity 99.999%), -20 DEG C/min-150 DEG C of 80 DEG C (4min) (1min) -4 DEG C/min-300 DEG C (5min), sample introduction Mouthful：280 DEG C, do not shunt, 1mL/min, makings interface：300 DEG C, the concentrate in absorption bottle is analyzed.

(5) experimental result

The ratio that the rate of recovery of 33 kinds of organo-chlorine pesticides marks peak area by determination sample and measure is drawn, such as table 1-1 institutes Show.It is 32.9% (being probably because the material decomposes at high temperature) except the recovery of standard addition of endrin is relatively low, remaining is organic The rate of recovery scope of chloro pesticide is between 53.1%~134.4%.

The negative pressure extraction separating resulting of table 1-1 organo-chlorine pesticides

2nd, the negative pressure extraction separation method test of concentration is 100 μ g/L in water organo-chlorine pesticide and chlorobenzene compound

(1) standard liquid is prepared

Organo-chlorine pesticide is configured to the standard for the methanol solvate phase that concentration is 100 μ g/mL, takes 5mL experimental water solvents Into 22mL sample bottles, as whole blank sample；10mL toluene solvants are taken into 22mL sample bottles, as sample absorption bottle； 5mL experimental waters solvent is taken into 22mL sample bottles, and adds 5.0 μ L hybrid standards as determination sample, concentration is 100 μ g/ L；5.0 μ L hybrid standards are taken to be used as bioassay standard into 1mL toluene, concentration is 500 μ g/L.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 280 DEG C (sample transfer pipeline is 1/16 inch of stainless steel column), is evacuated to sample Untill water sample in product bottle evaporates.To prevent that the absorbing liquid in sample absorption bottle is evaporated, pay attention to supplementing toluene at any time.Extraction After the completion of taking, it is to be analyzed that the toluene concentration in absorption bottle is settled to 1mL.

(4) analysis method

Agilent7890A-5975C type gas chromatograph-mass spectrometers, DB-5MS chromatographic columns (30m*0.25mm*250 μm), carrier gas are Helium (purity 99.999%), -8 DEG C/min-80 DEG C of 40 DEG C (4min) (1min) -5 DEG C/min-300 DEG C (5min), injection port： 280 DEG C, do not shunt, 1ml/min, makings interface：280 DEG C, SCAN (45~600), the concentrate in absorption bottle is analyzed.

(5) experimental result

The rate of recovery of 17 kinds of organo-chlorine pesticides is drawn by the ratio of determination sample and measure mark peak area in water sample, such as table Shown in 1-2.The rate of recovery scope of organo-chlorine pesticide is between 70.1%~133.8%.

The negative pressure extraction separating resulting of table 1-2 organo-chlorine pesticides

3rd, the negative pressure extraction separation method test of concentration is 250ng/g in soil organo-chlorine pesticide and chlorobenzene compound

(1) standard liquid is prepared

Organo-chlorine pesticide is configured to the standard for the methanol solvate phase that concentration is 100 μ g/mL.Weigh 2.0g and be free of targeted The blank soil of compound, is wrapped with filter paper, is put into 22ml sample bottles, then take 10mL toluene solvants soaked into the sample bottle by The pedotheque that filter paper is wrapped, as whole blank sample；

10mL toluene solvants are taken into 22ml sample bottles, as sample absorption bottle；

The blank soil that 2.0g is free of target compound is weighed, is wrapped, is put into filter paper after adding 5.0 μ L hybrid standards In 22ml sample bottles, then 10mL toluene solvants are taken to soak the pedotheque wrapped by filter paper into the sample bottle, as survey Random sample product, mark-on amount are 500ng；

5.0 μ L hybrid standards are taken to be used as bioassay standard into 1mL toluene, mark-on amount is 500ng, and concentration is 500 μ g/L.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 280 DEG C (sample transfer pipeline is 1/16 inch of stainless steel column), is evacuated to sample 10mL toluene is added when solution is closely dry in product bottle, and is evacuated to untill the toluene in sample bottle evaporates, to prevent sample from inhaling The absorbing liquid received in bottle is evaporated, and pays attention to supplementing toluene at any time.After the completion of extraction, the toluene concentration in absorption bottle is settled to 1mL is to be analyzed.

(4) analysis method

(5) experimental result

The rate of recovery of organo-chlorine pesticide is drawn by the ratio of determination sample and bioassay standard peak area in soil mark-on, such as Shown in table 1-3.The rate of recovery scope of organo-chlorine pesticide is between 66.5%~102.2%.

The negative pressure extraction separating resulting of table 1-3 organo-chlorine pesticides

Example 2

The negative pressure extraction separation side of liquid phase (organic solvent phase, aqueous phase), polychlorinated biphenyl in solid phase (soil) Method is tested

1st, the Polychlorinated biphenyls negative pressure extraction separation method that concentration is 100 μ g/L in toluene is tested

(1) standard liquid is prepared

The liquid standard of Polychlorinated biphenyls is configured to the standard liquid for the toluene phase that concentration is 10.0 μ g/mL.

10mL toluene solvants are taken into 22mL sample bottles, as whole blank sample；

10mL toluene solvants are taken into 22mL sample bottles, and adds 100 μ L standard liquids and is as determination sample, concentration 100.0μg/L；

100 μ L standard liquids are taken to be used as bioassay standard into 1mL toluene, concentration is 1 μ g/mL.

(2) gas circuit connects

By sample heating device, the sealed sample bottle equipped with testing sample, the sample absorption bottle equipped with liquid absorbent, first Cooling device, pump, sample transfer pipeline, heater, pumping pipeline, thermometer etc. are sequentially connected and installed as shown in Figure 1.Sample Product transfer line is 1/16 inch of stainless steel column.

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature be less than 80 DEG C, sample transfer pipeline temperature be 350 DEG C, be evacuated to solution in sample bottle it is closely dry when add 10mL toluene, extremely Solution in sample bottle (to prevent that the absorbing liquid in sample absorption bottle is evaporated, pays attention to supplementing first at any time untill evaporating Benzene).Absorbing liquid toluene in absorption bottle is produced, concentration is settled to be analyzed after 1mL.

(4) analysis method

Agilent7890A-5975C type gas chromatograph-mass spectrometers, DB-5MS chromatographic columns (30m*0.25mm*250 μm), carrier gas are Helium (purity 99.999%), -8 DEG C/min-80 DEG C of 40 DEG C (4min) (0min) -5 DEG C/min-320 DEG C (5min), injection port： 280 DEG C, do not shunt, 1ml/min, makings interface：280 DEG C, full scan (45~600), the concentrate in absorption bottle is divided Analysis.

(5) experimental result

The rate of recovery of 19 kinds of Polychlorinated biphenyls is drawn by the ratio of determination sample and measure mark peak area in toluene, such as table 2- Shown in 1, the rate of recovery scope of Polychlorinated biphenyls is between 71.8%~128.8%.

The negative pressure extraction separating resulting of table 2-1 Polychlorinated biphenyls

2nd, the Polychlorinated biphenyls negative pressure extraction separation method that concentration is 50.0 μ g/L in water is tested

(1) standard liquid is prepared

The liquid standard of Polychlorinated biphenyls is configured to the standard liquid for the methanol phase that concentration is 10.0 μ g/mL.

Experimental waters of the 10mL without Polychlorinated biphenyls is taken into 22mL sample bottles, as whole blank sample；

10mL butyl acetate solvents are taken into 22mL sample bottles, as sample absorption bottle；

The experimental water of 10mL Polychlorinated biphenyls is taken into 22mL sample bottles, and adds 50 μ L standard liquids as measure sample Product, concentration are 50.0 μ g/L；

50 μ L standard liquids are taken to be used as bioassay standard into 1mL butyl acetates, concentration is 500 μ g/L.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 100 DEG C, and sample transfer pipeline temperature is 350 DEG C, is evacuated to untill the aqueous solution evaporates in sample bottle.(to prevent Absorbing liquid in sample absorption bottle is evaporated, and pays attention to supplementing butyl acetate at any time).Butyl acetate phase in standing separation absorption bottle And aqueous phase, produce butyl acetate phase and concentrating be settled to it is to be analyzed after 1mL.

(4) analysis method

Agilent7890A-5975C type gas chromatograph-mass spectrometers, DB-5MS chromatographic columns (30m*0.25mm*250 μm), carrier gas are Helium (purity 99.999%), 50 DEG C (1min) -8 DEG C/min-320 DEG C (10min), injection port：330 DEG C, do not shunt, 1mL/ Min, makings interface：300 DEG C, SCAN (45~600).

(5) experimental result

The rate of recovery of 19 kinds of Polychlorinated biphenyls is drawn by the ratio of determination sample and measure mark peak area in water, such as table 2-2 Shown, the rate of recovery scope of Polychlorinated biphenyls is between 68.8%~84.8%.

The negative pressure extraction separating resulting of table 2-2 Polychlorinated biphenyls

3rd, the Polychlorinated biphenyls negative pressure extraction separation method that concentration is 500ng/g in soil is tested

(1) standard liquid is prepared

2g blank soil is taken to be put into after being wrapped up with filter paper in the 22mL sample bottles containing 10mL toluene, as whole blank sample Product.

10mL toluene solvants are taken into 22mL sample bottles, as sample absorption bottle.

2g mark-on blank soil is taken to be put into the 22ml sample bottles containing 10mL toluene the (μ of mark-on amount 100 after being wrapped up with filter paper L), as determination sample, mark-on quality is 1000ng.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 350 DEG C, is evacuated to toluene in sample bottle and evaporates and adds 10mL toluene extremely Evaporate.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, paying attention to supplementing toluene at any time).By the toluene in absorption bottle It is to be analyzed to be settled to 1mL for concentration after solution suctions out.

(4) analysis method

(5) experimental result

The rate of recovery of 19 kinds of Polychlorinated biphenyls is drawn by the ratio of determination sample and measure mark peak area in soil, such as table 2- Shown in 3, the rate of recovery scope of Polychlorinated biphenyls is between 60.5%~83.4%.

The negative pressure extraction separating resulting of table 2-3 Polychlorinated biphenyls

Example 3

The negative pressure extraction separation of phthalate compound in liquid phase (organic solvent phase, aqueous phase), solid phase (soil) Method is tested.

1st, concentration is that the negative pressure extraction separation method of 100.0 μ g/L phthalate compound is surveyed in butyl acetate Examination

(1) standard liquid is prepared

The liquid standard of phthalic acid ester is configured to the standard liquid for the butyl acetate phase that concentration is 10.0 μ g/mL.

10mL butyl acetate solvents are taken into 22mL sample bottles, as whole blank sample；

10mL butyl acetate solvents are taken into 22mL sample bottles, and adds 100 μ L hybrid standards and is used as determination sample, Concentration is 100.0 μ g/L；

100 μ L standard liquids are taken to be used as bioassay standard into 1mL butyl acetates, concentration is 1 μ g/mL.

(2) gas circuit connects

(4) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 2.0L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature be less than 100 DEG C, sample transfer pipeline temperature be 300 DEG C, be evacuated to solution in sample bottle it is closely dry when add 10mL acetic acid fourths Ester, (to prevent that the absorbing liquid in sample absorption bottle is evaporated, pay attention to supplementing at any time untill the solution in sample bottle evaporates Butyl acetate).It is to be analyzed to be settled to 1mL for butyl acetate concentration in absorption bottle.

(4) analysis method

(5) experimental result

The rate of recovery of 15 kinds of phthalic acid esters of butyl acetate solvent phase marks the ratio of peak area by determination sample and measure It is worth, as shown in table 3-1, the rate of recovery scope of phthalic acid ester is between 63.9%~155.1%.

The negative pressure extraction separating resulting of table 3-1 phthalic acid esters

2nd, concentration is the negative pressure extraction separation method test of 200.0 μ g/L phthalate compound in water

(1) standard liquid is prepared

The liquid standard of phthalic acid ester is configured to the standard liquid for the methanol phase that concentration is 10.0 μ g/mL.

5.0mL experimental waters are taken into 22mL sample bottles, as whole blank sample；

5.0mL experimental waters are taken into 22mL sample bottles, and adds 100 μ L hybrid standards and is used as determination sample, it is dense Spend for 200.0 μ g/L；

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 300 DEG C, is evacuated to untill the aqueous solution evaporates in sample bottle.(to prevent sample Absorbing liquid in product absorption bottle is evaporated, and pays attention to supplementing toluene at any time).Toluene in absorption bottle is produced into dehydration concentration to be settled to 1mL is to be analyzed.

(4) analysis method

(5) experimental result

The rate of recovery of 14 kinds of phthalic acid esters is drawn by the ratio of determination sample and measure mark peak area in water sample.Such as Shown in table 3-2, for dibutyl phthalate due to polluting blank, the rate of recovery is excessive (572.1%)；Adjacent benzene dicarboxylic acid two (2- butoxyethyl groups) ester, dicyclohexyl phthalate, di-n-octyl phthalate, the dinonyl phthalate rate of recovery It is relatively low, respectively 28.3%, 31.0%, 39.5%, 30.7%, the rate of recovery scope of remaining 9 kinds of phthalic acid ester is 46.2%~154.2%.

The negative pressure extraction separating resulting of table 3-2 phthalic acid esters

3rd, concentration is the negative pressure extraction separation method test of 500ng/g phthalate compound in soil

(1) standard liquid is prepared

The liquid standard of phthalic acid ester is configured to the standard liquid for the toluene phase that concentration is 10.0 μ g/mL.

2.0g blank soil is taken to be put into after being wrapped with filter paper in the 22mL sample bottles containing 10mL toluene, as whole blank Sample；

2.0g mark-on blank soil is taken to be put into (mark-on amount in the 22mL sample bottles containing 10mL toluene after being wrapped with filter paper 100 μ L), the absolute mass of mark-on is 1000ng；

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 300 DEG C, and 10mL is added after being evacuated to untill toluene evaporates in sample bottle Toluene is to evaporating.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, paying attention to supplementing toluene at any time).By in absorption bottle Toluene produces concentration, and to be settled to 1mL to be analyzed.

(5) analysis method

(5) experimental result

The rate of recovery of 14 kinds of phthalic acid esters is drawn by the ratio of determination sample and measure mark peak area in soil.Such as Shown in table 3-3, dibutyl phthalate and diphenyl phthalate rate of recovery due to being disturbed blank are excessive, respectively For 472.0%, 230.1%；The dinonyl phthalate rate of recovery relatively low 36.4%, the recovery of remaining 11 kinds of phthalic acid ester Rate scope is 44.6%~121.7%.

The negative pressure extraction separating resulting of table 3-3 phthalic acid esters

Example 4

The negative pressure extraction separation method of polycyclic arene compound in liquid phase (organic solvent phase, aqueous phase), solid phase (soil) Test

1st, concentration is the negative pressure extraction separation method test of 20~400 μ g/L polycyclic arene compound in toluene

(1) standard liquid is prepared

The methanol dichloromethane that the liquid standard of polycyclic aromatic hydrocarbon is the μ g/mL of μ g/mL of concentration 100~2000 mutually mixes mark.

10mL toluene solvants are taken into 22mL sample bottles, as whole blank sample.

10mL toluene solvants are taken into 22mL sample bottles, and add 2.0 μ L hybrid standards as determination sample, concentration 20 ~400 μ g/L.

2.0 μ L standard liquids are taken to be used as bioassay standard into 1mL toluene, concentration is 0.2~4 μ g/mL.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature be less than 80 DEG C, sample transfer pipeline temperature be 350 DEG C, be evacuated to solution in sample bottle it is closely dry when add 10mL toluene, extremely Untill solution in sample bottle evaporates.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, pay attention to supplementing first at any time Benzene).It is to be analyzed to be settled to 1mL for toluene concentration in absorption bottle.

(4) analysis method

(5) experimental result

The rate of recovery of 16 kinds of polycyclic aromatic hydrocarbons of toluene solvant phase by determination sample and measure mark peak area ratio draw, such as Shown in table 4-1, the rate of recovery scope of polycyclic aromatic hydrocarbon is between 61.4%~133.9%.

The negative pressure extraction separating resulting of table 4-1 polycyclic aromatic hydrocarbons

2nd, concentration is that the negative pressure extraction separation method of 40~800 μ g/L polycyclic arene compound tests (toluene in water Absorb)

(1) standard liquid is prepared

The methanol dichloromethane that the liquid standard of polycyclic aromatic hydrocarbon is the μ g/mL of concentration 100~2000 mutually mixes mark, is diluted to 10~200 μ g/mL methanol mutually mixes mark.

Experimental waters of the 5.0mL without polycyclic aromatic hydrocarbon is taken into 22ml sample bottles, as whole blank sample.

Experimental waters of the 5.0mL without polycyclic aromatic hydrocarbon is taken into 22ml sample bottles, and adds 20 μ L dilution standards as survey Random sample product, concentration are 40~800 μ g/L.

20 μ L working solutions are taken to be used as bioassay standard into 1mL toluene, concentration is 0.2~4 μ g/mL.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 350 DEG C, is evacuated to after the aqueous solution evaporates in sample bottle and adds 2mL first Benzene, untill treating that toluene evaporates.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, paying attention to supplementing toluene at any time).Inhale It is to be analyzed to be settled to 1mL for toluene concentration in receipts bottle.

(4) analysis method

(5) experimental result

The rate of recovery of 10 kinds of higher boiling polycyclic aromatic hydrocarbons is drawn by the ratio of determination sample and measure mark peak area in water sample, As shown in table 4-2, rate of recovery scope is between 58.7%~119.7%.

The negative pressure extraction separating resulting of table 4-2 polycyclic aromatic hydrocarbons

3rd, concentration is that the negative pressure extraction separation method of 0.1~2ng/g polycyclic arene compound tests (1) mark in soil Quasi- solution is prepared

The methanol dichloromethane that the liquid standard of polycyclic aromatic hydrocarbon is the μ g/mL of concentration 100~2000 mutually mixes mark.

Take 2.0g blank soil to be wrapped with filter paper and be put into the 22mL sample bottles equipped with 10mL toluene solvants, as whole process Blank sample.

Take 2.0g mark-on blank soil to be wrapped with filter paper and be put into (mark-on in the 22mL sample bottles equipped with 10mL toluene solvants Measure 2.0 μ L), as determination sample, the absolute mass of mark-on is 0.2~4 μ g.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 350 DEG C, is evacuated to after toluene evaporates in sample bottle and adds 10mL first Benzene, untill treating that toluene evaporates.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, paying attention to supplementing toluene at any time).Inhale It is to be analyzed to be settled to 1mL for toluene concentration in receipts bottle.

(4) analysis method

(5) experimental result

The rate of recovery of 16 kinds of polycyclic aromatic hydrocarbons is drawn by the ratio of determination sample and bioassay standard peak area in soil-like, such as Shown in table 4-3, rate of recovery scope is between 32.4%~93.8%.

The negative pressure extraction separating resulting of table 4-3 polycyclic aromatic hydrocarbons

Example 5

The negative pressure extraction separation method of nitrobenzene compounds is surveyed in liquid phase (organic solvent phase, aqueous phase), solid phase (soil) Examination

1st, concentration is the negative pressure extraction separation method test of 500~5000 μ g/L nitrobenzene compounds in butyl acetate

(1) standard liquid is prepared

The dichloromethane that the liquid standard of nitrobenzene is the μ g/mL of μ g/mL of concentration 1000~10000 mutually mixes mark.

10mL butyl acetate solvents are taken into 22mL sample bottles, as whole blank sample.

10mL butyl acetate solvents are taken into 22mL sample bottles, as sample absorption bottle.

10mL butyl acetate solvents are taken into 22mL sample bottles, and adds 5.0 μ L standards and is as determination sample, concentration 500~5000 μ g/L.

5.0 μ L standard liquids are taken to be used as bioassay standard into 1mL butyl acetates, concentration is 5~50 μ g/mL.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 80 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle temperature Degree be less than 100 DEG C, sample transfer pipeline temperature be 280 DEG C, be evacuated to solution in sample bottle it is closely dry when add 10mL butyl acetates, Untill the solution in sample bottle evaporates.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, pay attention to supplementing second at any time Acid butyl ester).It is to be analyzed to be settled to 1mL for butyl acetate concentration in absorption bottle.

(4) analysis method

(5) experimental result

The ratio that the rate of recovery of 16 kinds of nitrobenzenes of butyl acetate solvent phase marks peak area by determination sample and measure is worth Go out, as shown in Table 5-1, the rate of recovery scope of nitrobenzene is between 72.8%~135.8%.

The negative pressure extraction separating resulting of table 5-1 nitrobenzene

2nd, concentration is that the negative pressure extraction separation method of 1~10 μ g/mL nitrobenzene compounds tests (butyl acetate in water Absorb)

(1) standard liquid is prepared

The experimental water of 5.0mL not nitrobenzene-containings is taken into 22mL sample bottles, as whole blank sample.

The experimental water of 5.0mL not nitrobenzene-containings is taken into 22mL sample bottles, and adds 5.0 μ L standards as measure sample Product, concentration are 1~10 μ g/mL.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 80 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle temperature Degree is less than 100 DEG C, and sample transfer pipeline temperature is 280 DEG C, is evacuated to untill the aqueous solution evaporates in sample bottle.(to prevent sample Absorbing liquid in product absorption bottle is evaporated, and pays attention to supplementing butyl acetate at any time).Butyl acetate dehydration concentration is settled in absorption bottle 1mL is to be analyzed.

(4) analysis method

(5) experimental result

The ratio that the rate of recovery of 16 kinds of nitrobenzenes of aqueous phase marks peak area by determination sample and measure is drawn, such as table 5-2 Shown, the rate of recovery scope of nitrobenzene is between 58.8%~102.2%.

The negative pressure extraction separating resulting of table 5-2 nitrobenzene

3rd, concentration is that the negative pressure extraction separation method of 500~5000 μ g/L nitrobenzene compounds tests (toluene in water Absorb)

(1) standard liquid is prepared

The experimental water of 5.0mL not nitrobenzene-containings is taken into 22ml sample bottles, and adds 2.5 μ L standards as measure sample Product, concentration are 500~5000 μ g/L.

2.5 μ L standard liquids are taken to be used as bioassay standard into 1mL toluene, concentration is 2.5~25 μ g/mL.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 80 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle temperature Degree is less than 80 DEG C, and sample transfer pipeline temperature is 280 DEG C, is evacuated to untill the aqueous solution evaporates in sample bottle.(to prevent sample Absorbing liquid in absorption bottle is evaporated, and pays attention to supplementing toluene at any time).It is to be analyzed to be settled to 1mL for toluene dehydration concentration in absorption bottle.

(4) analysis method

(5) experimental result

The ratio that the rate of recovery of 15 kinds of nitrobenzenes of aqueous phase marks peak area by determination sample and measure is drawn, such as table 5-3 Shown, the rate of recovery scope of nitrobenzene is between 69.3%~103.7%.

The negative pressure extraction separating resulting of table 5-3 nitrobenzene

4th, concentration is that the negative pressure extraction separation method of 1.25~12.5 μ g/g nitrobenzene compounds tests (1) in soil Standard liquid is prepared

Take 2.0g blank soil and be put into after being wrapped with filter paper in the 22ml sample bottles containing 10mL toluene, as whole empty White sample.

Take 2.0g mark-on blank soil and (mark-on is put into containing 10mL toluene into 22ml sample bottles after being wrapped with filter paper Measure 2.5 μ L), mark-on absolute magnitude is 2.5~25 μ g.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 80 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle temperature Degree is less than 80 DEG C, and sample transfer pipeline temperature is 280 DEG C, is evacuated to after toluene evaporates in sample bottle and adds 10mL toluene extremely Untill evaporating.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, paying attention to supplementing toluene at any time).Toluene in absorption bottle It is to be analyzed that concentration is settled to 1mL.

(4) analysis method

(5) experimental result

The rate of recovery of 15 kinds of nitrobenzenes is drawn by the ratio of determination sample and measure mark peak area in soil, such as table 5- Shown in 4, the rate of recovery scope of nitrobenzene is between 56.6%~104.3%.

The negative pressure extraction separating resulting of table 5-4 nitrobenzene

Example 6

The negative pressure extraction separation method of organophosphorus compound is surveyed in liquid phase (organic solvent phase, aqueous phase), solid phase (soil) Examination

1st, concentration is the negative pressure extraction separation method test of 100.0 μ g/L organophosphorus compound in butyl acetate

(1) standard liquid is prepared

The liquid standard of organophosphor is configured to the standard liquid for the butyl acetate phase that concentration is 10.0 μ g/mL.

10mL butyl acetates are taken into 22mL sample bottles, as whole blank sample.

10mL butyl acetates are taken into 22mL sample bottles, and adds 100 μ L hybrid standards and is as determination sample, concentration 100.0μg/L。

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 100 DEG C, and the pump speed of exhaust is 2.0L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 100 DEG C, and sample transfer pipeline temperature is 280 DEG C, is evacuated to after butyl acetate evaporates in sample bottle and adds 10mL butyl acetates (to prevent that the absorbing liquid in sample absorption bottle is evaporated, pay attention to supplementing acetic acid fourth at any time to evaporating Ester).It is to be analyzed to be settled to 1mL for butyl acetate concentration in absorption bottle.

(4) analysis method

(5) experimental result

The rate of recovery of 6 kinds of organophosphorus pesticides is worth by the ratio of determination sample and measure mark peak area in butyl acetate phase Go out.As shown in Table 6-1, the rate of recovery scope of 6 kinds of organophosphorus pesticides is between 87.4%~100%.

The negative pressure extraction separating resulting of table 6-1 organophosphors

2nd, concentration is that the negative pressure extraction separation method of 200.0 μ g/L organophosphorus compound tests (toluene absorption) in water

(1) standard liquid is prepared

The liquid standard of organophosphor is configured to the standard liquid for the methanol phase that concentration is 10.0 μ g/mL.

Experimental waters of the 5.0mL without organophosphor is taken into 22ml sample bottles, as whole blank sample.

Experimental waters of the 5.0mL without organophosphor is taken into 22ml sample bottles, and adds 100 μ L hybrid standards as measure Sample, concentration are 200.0 μ g/L.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 100 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 280 DEG C, is evacuated to after toluene evaporates in sample bottle and adds 10mL toluene To evaporating.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, paying attention to supplementing toluene at any time).Toluene takes off in absorption bottle It is to be analyzed that water concentration is settled to 1mL.

(4) analysis method

(5) experimental result

The rate of recovery of 6 kinds of organophosphorus pesticides is drawn by the ratio of determination sample and measure mark peak area in aqueous phase.Such as table Shown in 6-2, wherein demeton, malathion, the rate of recovery of Rogor are undesirable, respectively 16.7%, 28.5%, 24.2%, but the rate of recovery of DDVP, parathion-methyl, parathion can meet that analysis requires, the rate of recovery is respectively 75.2%, 128.9%th, 114.2%.

The negative pressure extraction separating resulting of table 6-2 organophosphors

3rd, concentration is the negative pressure extraction separation method test of 500ng/g organophosphorus compound in soil

(1) standard liquid is prepared

The liquid standard of organophosphor is configured to the standard liquid for the toluene phase that concentration is 10.0 μ g/mL.

2.0g blank soil is taken to be put into after being wrapped with filter paper in the 22ml sample bottles containing 10mL toluene, as whole blank Sample.

The blank soil of 2.0g mark-ons is taken to be put into containing 10mL toluene into 22ml sample bottles (mark-on after being wrapped with filter paper Measure 100 μ L), the absolute magnitude of mark-on is 1000ng.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 100 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 280 DEG C, is evacuated to after toluene evaporates in sample bottle and adds 10mL toluene To evaporating and (to prevent that the absorbing liquid in sample absorption bottle is evaporated, pay attention to supplementing toluene at any time).Toluene takes off in absorption bottle It is to be analyzed that water concentration is settled to 1mL.

(4) analysis method

(5) experimental result

The rate of recovery of 6 kinds of organophosphorus pesticides is drawn by the ratio of determination sample and measure mark peak area in soil.Such as table Shown in 6-3, wherein demeton, the rate of recovery of Rogor are relatively low, respectively 35.8%, 27.5% but DDVP, parathion-methyl, Malathion, the rate of recovery of parathion are respectively 48.5%, 60.4%, 61.9%, 57.3%.

The negative pressure extraction separating resulting of table 6-3 organophosphors

Example 7

The negative pressure extraction separation method of betacyfluthrin is surveyed in liquid phase (organic solvent phase, aqueous phase), solid phase (soil) Examination

1st, concentration is the negative pressure extraction separation method test of 100 μ g/L betacyfluthrin in toluene

(1) standard liquid is prepared

Compound concentration is 100 μ g/mL methanol phase betacyfluthrin liquid standard.

10mL toluene solvants are taken into 22mL sample bottles, and add 10 μ L standards as determination sample, concentration is 100 μ g/ L。

10 μ L standard liquids are taken to be used as bioassay standard into 1mL toluene, concentration is 1 μ g/mL.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature be less than 80 DEG C, sample transfer pipeline temperature be 350 DEG C, be evacuated to solution in sample bottle it is closely dry when add 10mL toluene, extremely Solution in sample bottle (to prevent that the absorbing liquid in sample absorption bottle is evaporated, pays attention to supplementing first at any time untill evaporating Benzene).It is to be analyzed to be settled to 1mL for toluene concentration in absorption bottle.

(4) analysis method

(5) experimental result

The rate of recovery of betacyfluthrin is drawn by the ratio of determination sample and measure mark peak area in toluene solvant, As shown in table 7-1, the rate of recovery of betacyfluthrin is 123.4%.

The negative pressure extraction separating resulting of table 7-1 betacyfluthrins

2nd, concentration is the negative pressure extraction separation method test of 100 μ g/L betacyfluthrin in water

(1) standard liquid is prepared

Experimental waters of the 5.0mL without betacyfluthrin is taken into 22mL sample bottles, as whole blank sample.

Experimental waters of the 5.0mL without betacyfluthrin is taken into 22mL sample bottles, and adds 10 μ L standard conducts Determination sample, concentration are 100 μ g/L.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 350 DEG C, is evacuated to the aqueous solution in sample bottle and evaporates and adds 2mL toluene Untill toluene evaporates.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, paying attention to supplementing toluene at any time).Absorption bottle It is to be analyzed that middle toluene dehydration concentration is settled to 1mL.

(4) analysis method

(5) experimental result

The rate of recovery of betacyfluthrin is drawn by the ratio of determination sample and measure mark peak area in water, such as table 7- Shown in 2, the rate of recovery of betacyfluthrin is 89.1%.

The negative pressure extraction separating resulting of table 7-2 betacyfluthrins

3rd, concentration is the negative pressure extraction separation method test of 500ng/g betacyfluthrin in soil

(1) standard liquid is prepared

2.0g blank soil is taken to be put into after being wrapped with filter paper in the 22mL sample bottles equipped with 10mL toluene, as whole blank Sample.

2.0g mark-on blank soil is taken to be put into (mark-on amount 10 in the 22mL sample bottles equipped with 10mL toluene after being wrapped with filter paper μ L), the absolute mass of mark-on is 1 μ g, is concentrated into identical with bioassay standard concentration after 1mL.

(2) gas circuit connects

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and the pump speed of exhaust is 1.5L/S, and vacuum is less than 3.0KPA, sample absorption bottle Temperature is less than 80 DEG C, and sample transfer pipeline temperature is 350 DEG C, is evacuated to the aqueous solution in sample bottle and evaporates and adds 2mL toluene Untill toluene evaporates.(to prevent that the absorbing liquid in sample absorption bottle is evaporated, paying attention to supplementing toluene at any time).Absorption bottle It is to be analyzed that middle toluene concentration is settled to 1mL.

(4) analysis method

(5) experimental result

The rate of recovery of betacyfluthrin is drawn by the ratio of determination sample and measure mark peak area in soil, such as table Shown in 7-3, the rate of recovery of betacyfluthrin is 44.8%.

The negative pressure extraction separating resulting of table 7-3 betacyfluthrins

Embodiment 2

The piece-rate system of the present embodiment the difference is that only that its absorbing mechanism is by liquid adsorption device with embodiment 1 Solid absorption device is changed to, i.e., absorption bottle 5 and liquid absorbent 6 are replaced by adsorption tube 13 and solid absorbent, it is specific next Say, as shown in Fig. 2 first solid absorbent 6 is packed into adsorption tube 13, then by one end of adsorption tube and the first sample conveying tube Line 4 is connected, and the other end connects with pumping pipeline 8；In addition, with adsorption tube 13 corresponding to cooling device be then replaced by corresponding (the second cooling device is the conventional semiconductor cooling device or water circulation refrigeration dress to match with adsorption tube to two cooling devices Put), the structure of remaining structure then uniform embodiment 1 is identical.

The present embodiment is carried out to the negative pressure extraction separation method of phthalate organic pollution in organic solvent phase Test, concentration is that the negative pressure extraction separation method of 500.0 μ g/L phthalate compound is surveyed specially in toluene Examination, comprises the following steps：

(1) standard liquid is prepared

Concentration is the liquid standard of 1000.0 μ g/mL phthalic acid ester.

0.5g Fo Luoli tripoli florisil (60~80 mesh) is taken, is loaded to long 10cm, the stainless steel that 1/4 inch of internal diameter is inhaled Solid absorbent is used as in attached pipe, adsorbent both ends are stoppered with the mineral wool of silanization, and adsorption tube is used as after good seal.

10mL toluene solvants are taken into 22mL sample bottles, and add 5.0 μ L phthalic acid esters standard liquids as measure Sample, concentration are 500.0 μ g/L.

5.0 μ L standard liquids are taken to be used as bioassay standard into 1mL toluene, concentration is 5000 μ g/L.

(2) gas circuit connects

By sample heating device, the sealed sample bottle equipped with testing sample, the adsorption tube equipped with Fo Luoli tripoli, the first cooling Device, pump, sample transfer pipeline, heater, pumping pipeline are sequentially connected as shown in Figure 2.Sample transfer pipeline is 1/16 English Very little stainless steel tube.

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and pump uses Varian DS102, and the pump speed of exhaust is 114L/min, and the limit is true Empty 10-4mbar, adsorption tube temperature are less than 50 DEG C, and sample transfer pipeline temperature is 300 DEG C, when being evacuated to that solution is closely dry in sample bottle 10mL toluene is added, untill the solution in sample bottle evaporates.By the Fo Luoli tripoli toluene acetones in adsorption tube Mixed solvent (v/v, 1/1) desorbs 5h, separates Fo Luoli tripoli and desorption solvent, and desorption solvent concentration is settled into 1mL treats point Analysis.

(4) analysis method

(5) experimental result

The rate of recovery of 14 kinds of phthalic acid esters is drawn by the ratio of determination sample and measure mark peak area in toluene, such as Shown in table 8-1, phthalic acid diethylhexyl ester its rate of recovery due to polluting blank is 230.5%, O-phthalic Dimethyl phthalate and adjacent benzene dicarboxylic acid two (2- butoxyethyl groups) ester may be incomplete due to desorbing, and its rate of recovery is respectively 34.3% With 24.1%, the rate of recovery scope of remaining phthalic acid ester is between 50.3%~97.1%.

The negative pressure extraction separating resulting of table 8-1 phthalic acid esters

Embodiment 3

The present embodiment and the difference of above-described embodiment piece-rate system have both used liquid absorbent for it, have used solid again Adsorbent, i.e. its absorbing mechanism are the combining structure of liquid adsorption device and solid absorption device, specifically, as shown in figure 3, Its absorbing mechanism both includes adsorption tube and solid absorbent, includes absorption bottle and liquid absorbent again.In particular, institute State solid absorbent to be filled in adsorption tube, the liquid absorbent is placed in absorption bottle；Described adsorption tube one end and the first sample Product transfer line 4 is connected, and the other end is connected by the second sample transfer pipeline 14 with absorption bottle, and the second sample transfer pipeline from Stretch into absorption bottle, and be submerged in absorption bottle in liquid absorbent at the top of absorption bottle；Meanwhile the second sample transfer pipeline 14 Secondary heating mechanism 16 is additionally provided with outside, for adjusting the temperature of the second sample transfer pipeline 14.The pumping pipeline 8 and absorption bottle Connected one end is stretched into absorbing mechanism at the top of absorption bottle, and above adsorbent in absorbing mechanism；The absorbing mechanism Cooling device then includes first cooling device corresponding with absorption bottle and the second cooling device corresponding with adsorption tube.

The present embodiment is to organo-chlorine pesticide class, chlorobenzene class, polychlorinated biphenyl, multiring aromatic hydrocarbon, adjacent benzene in organic solvent phase The negative pressure extraction separation method test of diformic ester, nitrobenzene organic pollution, specifically, comprises the following steps：

(1) standard liquid is prepared

Concentration is the liquid standard of 100.0 μ g/mL polychlorinated biphenyl.

Concentration range is the liquid standard of 1000.0~10000.0 μ g/mL nitrobenzene.

Concentration is the liquid standard of 1000.0 μ g/mL phthalate.

Concentration is the liquid standard of 100~2000 μ g/mL multiring aromatic hydrocarbon.

Concentration is the liquid standard of 2000.0 μ g/mL organo-chlorine pesticide class.

Take 0.5g Carboxen 1000 (specific surface area 1200m2/g), load to long 10cm, 1/4 inch of internal diameter it is stainless Solid absorbent is used as in steel adsorption tube, adsorbent both ends are stoppered with the mineral wool of silanization, and adsorption tube is used as after good seal.

10mL toluene solvants are taken into 22mL sample bottles, and add the liquid standard of 10.0 μ L Polychlorinated biphenyls, 5.0 μ L nitros The liquid standard of benzene, the liquid standard of 5.0 μ L phthalic acid esters, the liquid standard of 10.0 μ L polycyclic aromatic hydrocarbons, 4 μ L organochlorine agricultures The liquid standard of medicine as determination sample, wherein polychlorinated biphenyl, nitrobenzene, phthalate, multiring aromatic hydrocarbon, have The concentration of machine chloro pesticide class is respectively 100 μ g/L, 500~5000 μ g/L, 500.0 μ g/L, 100~2000 μ g/L, 800 μ g/L.

The above-mentioned five classes organic pollution of same volume is taken to being used as bioassay standard, wherein Polychlorinated biphenyls into 1mL toluene Class, nitrobenzene, phthalate, multiring aromatic hydrocarbon, the concentration of organo-chlorine pesticide class be respectively 1000 μ g/L, 5000~ 50000 μ g/L, 5000.0 μ g/L, 1000~20000 μ g/L, 8000 μ g/L.

(2) gas circuit connects

By sample heating device, the sealed sample bottle equipped with testing sample, the adsorption tube equipped with Carboxen 1000, second Cooling device, the absorption bottle equipped with absorption liquid, the first cooling device, pump, sample transfer pipeline, heater, pumping pipeline It is sequentially connected as shown in Figure 3, whether measure Carboxen 1000 is pierced.Sample transfer pipeline is 1/16 inch of stainless steel Pipe.

(3) negative pressure extraction separation method

Sample bottle heating-up temperature is 125 DEG C, and pump uses Varian DS102, and the pump speed of exhaust is 114L/min, and the limit is true Empty 10-4mbar, adsorption tube temperature are less than 40 DEG C, and sample transfer pipeline temperature is 350 DEG C, when being evacuated to that solution is closely dry in sample bottle 10mL toluene is added, untill the solution in sample bottle evaporates, while keeps volume of toluene in liquid absorption bottle not Less than 5mL.1.0mL progress gaschromatographic mass spectrometric analysises will be settled to after toluene rinse will be added in sample bottle.By liquid absorption bottle In residual toluene be concentrated into 1mL carry out gaschromatographic mass spectrometric analysis.

Pass through the compounds content absorbed in the content and sample absorption bottle of remaining compound in determination sample bottle.Use standard The total amount of compound that solution adds when preparing subtracts what is absorbed in sample bottle in the content of remaining compound and sample absorption bottle Compounds content is the content for the target compound that Carboxen 100 is adsorbed.

(4) analysis method

(5) experimental result

It is each in the polychlorinated biphenyl of measure, nitrobenzene, phthalate, multiring aromatic hydrocarbon, organo-chlorine pesticide class Shown in objectives compound as example 1~7.Measurement result shows remaining target compound and sample absorption bottle in sample bottle The content of the target compound of middle absorption is zero, illustrates that Carboxen 1000 can effectively adsorb above-mentioned organic pollution.

Above-described embodiment is only the preferred embodiment of the present invention, should not be taken to limit protection scope of the present invention, but All body design thought in the present invention and that mentally makes have no the change of essential meaning or polishing, its technology solved Problem is still consistent with the present invention, should be included within protection scope of the present invention.

Claims

1. the negative pressure extraction piece-rate system of organic pollution in sample, it is characterised in that including sample bottle (2), sample heating device (1), absorbing mechanism, absorbing mechanism's cooling device and pump (10) sample heating device (1), which are arranged on outside sample bottle, is used to adjust The temperature of sample bottle, absorbing mechanism's cooling device, which is arranged on, is used for the temperature for adjusting absorbing mechanism outside absorbing mechanism, described Sample bottle (2) is connected by the first sample transfer pipeline (4) with absorbing mechanism, and the first sample transfer pipeline (4) is set outside For adjusting the first heater (15) of the first sample transfer pipeline temperature；The absorbing mechanism is also by being evacuated pipeline (8) It is connected with the entrance point of pump (10), the port of export of the pump is connected with organic matter steam outlet pipe (11)；The pumping pipeline (8) it is provided with pressure controller (9).

2. the negative pressure extraction piece-rate system of organic pollution in sample according to claim 1, it is characterised in that the sample Thermometer is equipped with product bottle (2), absorbing mechanism and the first sample transfer pipeline (4).

3. the negative pressure extraction piece-rate system of organic pollution in sample according to claim 2, it is characterised in that the suction Receiving mechanism includes absorption bottle (5) and the liquid absorbent (6) being placed in absorption bottle；Described sample transfer pipeline (4) one end is from sample Stretch into sample bottle at the top of product bottle (2), and above sample in sample bottle, first sample transfer pipeline (4) other end is from suction Receive and stretched at the top of bottle (5) in absorption bottle, and be submerged in absorption bottle in liquid absorbent；Described pipeline (8) one end that is evacuated is from suction Top of bottle is received to stretch into absorption bottle, and above adsorbent；Absorbing mechanism's cooling device is to be arranged on the outside of absorption bottle The first cooling device (7).

4. the negative pressure extraction piece-rate system of organic pollution in sample according to claim 2, it is characterised in that the suction Receiving mechanism includes adsorption tube (13) and the solid absorbent being filled in adsorption tube；Described first sample transfer pipeline (4) one end Stretched at the top of from sample bottle (2) in sample bottle, and above sample in sample bottle, first sample transfer pipeline (4) other end It is connected with adsorption tube one end, the adsorption tube other end then connects with pumping pipeline (8)；Absorbing mechanism's cooling device is The second cooling device (12) being arranged on the outside of adsorption tube.

5. the negative pressure extraction piece-rate system of organic pollution in sample according to claim 2, it is characterised in that the suction Receiving mechanism includes adsorption tube, solid absorbent, absorption bottle and liquid absorbent；The solid absorbent is filled in adsorption tube, The liquid absorbent is placed in absorption bottle；Described adsorption tube one end is connected with the first sample transfer pipeline, and the other end is connected with Second sample transfer pipeline (14)；Described second sample transfer pipeline (14) one end is stretched into absorption bottle at the top of absorption bottle, and It is submerged in absorption bottle in liquid absorbent, while is additionally provided with the second sample transfer pipeline (14) for adjusting its temperature Secondary heating mechanism (16)；Described pumping pipeline (8) one end is stretched into absorbing mechanism at the top of absorption bottle, and is located at absorbing mechanism Above middle adsorbent；The second cooling device and be wrapped in absorption that absorbing mechanism's cooling device is wrapped in outside adsorption tube The first cooling device outside bottle.

6. the negative pressure extraction separation method of organic pollution in the sample described in claim 2, it is characterised in that including following step Suddenly：

A, sample is put into sample bottle, and adsorbent is put into absorbing mechanism, then sample bottle is placed in sample heating device, Absorbing mechanism is placed in absorbing mechanism's cooling device；

B, sample transfer pipeline, absorbing mechanism, pumping pipeline, pressure controller, pump and organic steam outlet are connected successively Connect, and keep closed No leakage；

C, sample heating device is opened, sample bottle keeping temperature is more than or equal to 40 DEG C；Make suction using absorbing mechanism's cooling device Receive mechanism temperature and be less than or equal to 100 DEG C；

D, the first and second heaters are opened, the first and second sample transfer pipelines is held in a certain temperature, prevents from treating Survey compound and be condensate in sample transfer line pipe wall.

E, pump and pressure controller are opened, the vacuum of sample bottle and absorbing mechanism is below 3.0kpa, adjustment sample heating The heating-up temperature of device, evaporates sample, starts extraction and absorbs, the organic gas for departing from sample substrate passes through sample transfer pipeline Absorbed into absorbing mechanism, and by the adsorbent in absorbing mechanism, into sample bottle, solution evaporates, and extraction has absorbed Into.