CN111855373B - Device and method for online measurement of trace polar organic matters in atmospheric concentrated particulate matters - Google Patents

Device and method for online measurement of trace polar organic matters in atmospheric concentrated particulate matters Download PDF

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CN111855373B
CN111855373B CN202010727117.5A CN202010727117A CN111855373B CN 111855373 B CN111855373 B CN 111855373B CN 202010727117 A CN202010727117 A CN 202010727117A CN 111855373 B CN111855373 B CN 111855373B
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CN111855373A (en
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陈建民
尚晓娜
孙剑峰
李凌
隋国栋
李丹
朱超
康慧慧
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Fudan University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40Concentrating samples
    • G01N1/4022Concentrating samples by thermal techniques; Phase changes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40Concentrating samples
    • G01N1/4022Concentrating samples by thermal techniques; Phase changes
    • G01N2001/4033Concentrating samples by thermal techniques; Phase changes sample concentrated on a cold spot, e.g. condensation or distillation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

The invention belongs to the technical field of environmental protection, and particularly relates toA device and a method for on-line measurement of trace polar organic matters by collecting atmospheric fine particles through concentration. The inventive device comprises a PM 2.5 The device comprises a cutting head, a water tank heating system, a virtual cutting system, a condensation circulating system and an online measuring system; the water tank system comprises a water tank, an electric heating rod, a temperature control digital display device and a PM 2.5 The cutting head is communicated with the water tank; the virtual cutting system comprises a virtual cutter, a concentrated airflow vacuum pump and a main airflow vacuum pump; the condensation circulating system comprises a condensing agent circulating pipe and a condensing machine; the condensation circulating system is used for circulating and circulating condensate to condense and grow saturated particles; the on-line measuring system comprises a biological sampling bottle, a computer subdivision constant flow pump and a liquid chromatogram flight time mass spectrum. The device can concentrate actual atmospheric fine particles by 7 to 10 times, and has high concentration efficiency; can be directly collected and used for subsequent on-line analysis; the device is simple and convenient to operate, reliable and stable, and low in maintenance cost.

Description

Device and method for online measurement of trace polar organic matters in atmospheric concentrated particulate matters
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a device and a method for measuring polar organic matters in concentrated atmospheric particulates on line.
Background
PM 2.5 Refers to particles having an aerodynamic equivalent diameter of less than or equal to 2.5 microns in the atmosphere, also known as respirable particles. Albeit PM 2.5 Only the components of the earth's atmosphere with very small contents, but its air qualityAmount and visibility, etc. have important effects. Atmospheric PM 2.5 Small grain size, large specific surface area, containing a large amount of toxic and harmful substances, long suspension time in the atmosphere and long transmission distance, thereby having no negligible negative effects on human health and atmospheric environmental quality.
In recent years, atmosphere PM of China 2.5 Serious pollution causes the rapid increase of the diagnosis rate and the premature death of susceptible people, and causes high attention of the whole society. In recent years, PM to the atmosphere 2.5 The research on medium organic chemical components is quite extensive, and the undetected species are more due to the low content of the organic components in the actual atmospheric particulates.
In order to solve the problem of detection of components of atmospheric particulates, the on-line concentration and collection device for the atmospheric fine particulates can concentrate and enrich aerosol to a level enough for obviously detecting the content of the components on the premise of not changing any physicochemical characteristics except concentration. Meanwhile, the device has an online sampling function, is combined with liquid chromatogram flight time mass spectrum, realizes online monitoring of organic chemical components of atmospheric particulates, and can be widely applied to environmental monitoring and health risk assessment.
Disclosure of Invention
The invention aims to provide a device and a method for measuring trace polar organic matters in atmospheric concentrated particles on line.
The structure of the device for online measurement of trace polar organic matters in atmospheric concentrated particles is shown in figure 1; the method comprises the following steps: impact PM 2.5 The device comprises a cutting head, a water tank heating system, a virtual cutting system, a condensation circulating system and an online measuring system; wherein:
the collision type PM 2.5 Cutting head comprising PM 10 、PM 5 、PM 2.5 The three-stage impact separation and collection plate is of the same structure, and the number of holes and the aperture of the three-stage impact plate are different due to different impact inertias of particles with different particle diameters;
the water tank heating system comprises a water tank (9) for containing deionized water, and the water tank (9)The inner wall is provided with a heat insulation layer (10) for insulating the deionized water in the water tank (9); one side of the water tank (9) is provided with a visible window (11) for observing the height of the water surface in the tank body; an electric heating rod (12) with a temperature sensor is arranged in the water tank (9) and used for heating the deionized water; a temperature control digital display device (13) is arranged in the water tank (9) and is used for controlling the temperature of the deionized water; impact PM 2.5 The cutting head (7) is communicated with the water tank (9);
the virtual cutting system comprises a virtual cutter (17), a concentrated airflow vacuum pump (2) and a main airflow vacuum pump (3); wherein the virtual cutter (17) comprises a nozzle (19), a nozzle connecting pipe (20) and two air paths: a main gas path and a concentration gas path; the nozzle (19) and the nozzle connecting pipe (20) are coaxially arranged, the nozzle connecting pipe (20) is arranged above the nozzle (19) and is spaced by a certain gap, and the nozzle connecting pipe (20) is used for receiving particles sprayed by the nozzle (19); the main air flow vacuum pump (3) is communicated with a main air path outlet (18) at the upper part of the virtual cutter (17) through a pipeline, a drying pipe (4) and a large-flow mass flow controller (5) are arranged on the communicated pipeline, the drying pipe (4) is used for drying air flow so as to prevent the water vapor of the system from excessively damaging a pump body, and the large-flow mass flow controller (5) is used for accurately controlling the flow of the pipeline; the concentrated airflow vacuum pump (2) is communicated with a concentrated air passage at the upper part of the virtual cutter (17) through a pipeline, and a float flowmeter (1) is arranged on the communicated pipeline and used for metering the flow of the pipeline;
the condensation circulating system comprises a condensing agent circulating pipe (6) and a condenser (8); the condensing agent circulating pipe (6) comprises a condensing inner pipe (14), a soft copper spiral pipe (15) is tightly wound outside the condensing inner pipe (14), and the beginning end and the end of the spiral pipe (15) are respectively connected with an outlet and an inlet of the condensing machine (8); a heat insulation layer (16) is wrapped outside the spiral pipe (15), so that the temperature of the condensation pipe is not influenced by the outside temperature, and the condensation circulating system is used for circulating and circulating condensate to condense and grow saturated particles;
an airflow outlet of the water tank (9) is coaxially arranged with the starting end of a condensation inner pipe (14) in a condensation circulating system and is connected by a quick-connection flange (containing a sealing ring); the terminal of the condensation inner pipe (14) is connected with a nozzle (19) in the virtual cutting system;
the online measurement system comprises a biological sampling bottle (21), a liquid chromatogram flight time mass spectrum (22) and a computer subdivision constant flow pump (23); wherein, the upper port of the biological sampling bottle (21) is communicated with a communication pipeline between the concentrated airflow vacuum pump (2) and the virtual cutter (17) and is used for carrying out on-line collection on the concentrated saturated particles, and the collection solvent is deionized water or other organic solvents (selected according to requirements); the four-channel computer subdivision constant flow pump (23) is provided with two pumps, wherein one pump is used for injecting a solvent into the biological sampling bottle, and the other pump is used for extracting the collected concentrated sample from the biological sampling bottle and realizing on-line concentrated sample collection; because negative high pressure can be produced in the sampling bottle 21, the solvent can still be continuously sucked into the sampling bottle when the computer subdivision constant flow pump is in a dormant state, so that the solution in the sampling bottle (20 ml volume) is full and even flows backwards. In order to solve the problem, an electromagnetic valve and a time relay for controlling the opening and closing of the electromagnetic valve are arranged in front of the two computer subdivision constant-current pumps and are used for controlling the two computer subdivision constant-current pumps to work so as to keep the working and sleeping time of the constant-current pumps synchronous; the concentrated solution extracted by the constant flow pump (23) is injected into a liquid chromatogram flight time mass spectrum (22) on line, and the trace polar molecules in the concentrated solution are detected on line.
The invention provides a device for measuring trace polar organic matters in atmospheric concentrated particles on line, which comprises the following working procedures:
(1) To collision type PM 2.5 The cutting head (7) is arranged in the actual atmospheric environment, and the original atmospheric sample passes through the collision type PM 2.5 The cutting head (7) discharges PM 2.5 Atmospheric fine particles with the aerodynamic equivalent diameter less than or equal to 2.5 microns are screened out and enter a water tank (9) by means of system suction;
(2) Under a visible window (11), adding deionized water to two thirds of the height of the water tank, heating the deionized water by using an electric heating rod (12) with a temperature sensor, and controlling the temperature to be 35 +/-2 ℃ by using a temperature control digital display device (13) to enable the generated water vapor to enable particles to reach a saturated state;
(3) The particles reaching the saturated state flow through a condensation inner pipe (14) of the condensation circulating system; the external circulation temperature control mode of the condenser controls the temperature to be-12 +/-1 ℃, so that the circulating condensate liquid condenses and grows saturated particles, wherein most PM 2.5 Can grow to 3-4 microns in aerodynamic diameter;
(4) Condensing the growing PM 2.5 The particles enter the virtual cutter (17) and are accelerated at the nozzle (19); the accelerating power of the device comes from two gas paths, namely a main gas path and a concentration gas path; in the main gas path, the main flow is accurately controlled to be 50 +/-1 liter/minute by a large-flow mass flow controller (5); in the concentration gas path, the particles accelerated by the nozzle (19) are received by a nozzle connecting pipe (20) above the coaxially arranged nozzle, and the flow of the concentrated gas flow is controlled to be 5 liters/minute; theoretically, under the condition that the concentration of the particulate matters is the same, the gas flow becomes one tenth of the original gas flow, and the concentration of the particulate matters in the sample becomes ten times of the original concentration, so that the concentration effect is achieved;
(5) Collecting the concentrated saturated particles on line by using a biological sampling bottle (21), wherein the collecting solvent is deionized water or other organic solvents (selected as required); one of the two four-channel computer subdivision constant flow pumps (23) is used for injecting a solvent into the biological sampling bottle, controlling the work for 1 minute, injecting 5 milliliters of the solvent and sleeping for 59 minutes, and the other is used for extracting the collected concentrated sample from the biological sampling bottle, controlling the work for 1 minute, collecting 5 milliliters and sleeping for 59 minutes; in order to keep synchronous with the working and sleeping time of the constant flow pump, the switching time of the electromagnetic valve is set to be 1 minute for switching on and 59 minutes for switching off; and the concentrated solution extracted by the constant flow pump (23) is injected into the liquid chromatography flight time mass spectrum (22) on line, and the trace polar molecules in the concentrated solution are detected on line.
After the collection is finished, finally passing through a concentration factor (PM in the atmosphere after concentration) 2.5 Mass concentration/number concentration/chemical component concentration of (2) and PM in the atmosphere before concentration 2.5 Mass concentration/number concentration/chemical group ofFractional concentration ratio) and concentration efficiency (concentration after actual concentration as a percentage of theoretical concentration). The number concentration and the mass concentration of the particles are measured by a scanning mobility particle size spectrometer connected with the other branch of the stainless steel tee joint (note: when a concentrated sample is collected and the number and the mass concentration of the particles are measured at the same time, the flow of the two branches of the concentrated gas circuit needs to be adjusted, and the sum of the two branches is equal to one tenth of the main gas flow).
In the device, the condensing agent in the condensing machine adopts alcohol, the concentration of which can be adjusted, and the effects of refrigerating and reducing the volatilization amount are only needed to be achieved;
the diameter of the condensation inner pipe (14) is 2.5 cm, and the length is 80 cm;
the control range of the flow controller (5) is 0-200L/min;
the diameter of the nozzle is 0.37 cm, the spacing gap between the nozzle (9) and the nozzle connecting pipe (20) is 0.45 cm, and the diameter of the nozzle connecting pipe is 2.5 cm.
The invention has the beneficial effects that:
(1) The device can concentrate actual atmospheric particulates by 7 to 10 times (the size of the particulates is related), the concentration efficiency is high and can reach 75 to 99 percent (the size of the particulates is related), and the concentration performance is stable;
(2) The device has low requirements on the flow of sampled inlet air, and the actual atmospheric particulate matters can be efficiently concentrated when the medium flow is 50 liters/minute;
(3) The particles concentrated by the device do not need to be dried, and can be directly collected and used for subsequent on-line or off-line analysis;
(4) The device realizes the on-line collection of the concentrated sample, is combined with liquid chromatogram flight time mass spectrum, detects trace organic components in atmospheric particulates on line, and has the advantages of simple and convenient operation, reliability, stability and easy maintenance.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for online measurement of trace polar organic compounds in atmospheric concentrated particulate matters.
FIG. 2 is a comparison of detection signals of organic components before and after concentration of atmospheric fine particles in a real atmospheric environment. In the lower graph, the signal intensity of organic molecules in the concentrated particles is obviously higher than that of the non-concentrated particles in the upper graph, and macromolecular organic matters which are not detected under the actual concentration are detected between the mass-to-charge ratio of 600 to 900.
The reference numbers in the figures: the reference numbers in the figures: 1 is a float flowmeter, 2 is a concentrated airflow vacuum pump, 3 is a main airflow vacuum pump, 4 is a drying pipe, 5 is a mass flow controller, 6 is a condensing agent circulating pipe, and 7 is collision type PM 2.5 The device comprises a cutting head, 8 is a condenser, 9 is a water tank, 10 is a water tank heat insulation layer, 11 is a visible window, 12 is an electric heating rod with a temperature sensor, 13 is a temperature control digital display system, 14 is a condensation inner pipe, 15 is a condensation outer spiral pipe, 16 is a heat insulation layer, 17 is a virtual cutter, 18 is a main air outlet, 19 is a nozzle, 20 is a nozzle connecting pipe, 21 is a biological sampling bottle, 22 is a liquid chromatogram flight time mass spectrum, and 23 is a computer subdivision constant flow pump.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1:
(1) To collision type PM 2.5 The cutting head (7) is arranged outside a 7-storey window of an environment building of the university of Compound Dan in an impact PM 2.5 Under the action of a cutting head (7), PM 2.5 Atmospheric fine particles with the aerodynamic equivalent diameter of less than or equal to 2.5 microns are screened out and enter a water tank (9) by means of pumping force provided by a main gas circuit and a concentration gas circuit;
(2) Under a visible window (11), deionized water is added to two thirds of the height of a water tank, an electric heating rod (12) with a temperature sensor is used for heating the deionized water, the temperature is controlled to be 35 +/-2 ℃ through a temperature control digital display device (13), so that the generated water vapor enables particles to reach a saturated state, an outfield experiment is carried out in summer, the ambient temperature is 25 ℃, the room temperature is 22 ℃, and when the temperature of the water tank (9) is set to be 35 ℃, the supersaturated ambient temperature in the water tank (9) is actually reduced to 25 ℃ after air extraction is started, so that the loss of chemical components of the particles caused by the difference between the system temperature and the ambient temperature is avoided;
(3) Particles reaching saturation stateThe particles flow through a condensation inner pipe (14) of the condensation circulating system; the external circulation temperature control mode of the condenser controls the temperature to be-12 +/-1 ℃, so that the circulating condensate liquid condenses and grows saturated particles, wherein most PM 2.5 Can grow to 3-4 microns in aerodynamic diameter;
(4) Condensing the growing PM 2.5 The particles enter the virtual cutter (17) and are accelerated at the nozzle (19); the accelerating power of the device comes from two gas paths, namely a main gas path and a concentration gas path; in the main gas path, the main flow is accurately controlled to be 50 liters/minute by a large-flow mass flow controller (5); in the concentration gas path, the particles accelerated by the nozzle (19) are received by a nozzle connecting pipe (20) above the coaxially arranged nozzle, and the flow of the concentrated gas flow is controlled to be 5 liters/minute; theoretically, under the condition that the concentration of the particulate matters is the same, the gas flow becomes one tenth of the original gas flow, and the concentration of the particulate matters in the sample becomes ten times of the original concentration, so that the concentration effect is achieved;
(5) Collecting the concentrated saturated particles on line by using a biological sampling bottle (21), wherein the collecting solvent is deionized water or other organic solvents (selected as required); one of the two four-channel computer subdivision constant flow pumps (23) is used for injecting a solvent into the biological sampling bottle, controlling the work for 1 minute, injecting 5 milliliters of the solvent and sleeping for 59 minutes, and the other is used for extracting the collected concentrated sample from the biological sampling bottle, controlling the work for 1 minute, collecting 5 milliliters and sleeping for 59 minutes; in order to keep synchronous with the working and sleeping time of the constant flow pump, the switching time of the electromagnetic valve is set to be 1 minute for switching on and 59 minutes for switching off; and the concentrated solution extracted by the constant flow pump (23) is injected into the liquid chromatography flight time mass spectrum (22) on line, and the trace polar molecules in the concentrated solution are detected on line.
In the concentration process, the sample inlets of the two scanning electric mobility particle size spectrometers are respectively connected with a concentration gas circuit of the enrichment system and the actual atmosphere, and the number concentration and the mass concentration of particles (10 to 1000 nanometers) in each particle size range in the system and the actual atmosphere are continuously monitored, so that concentration factors (PM in the atmosphere after concentration) are calculated 2.5 Mass concentration/number concentration ofDegree and PM in the atmosphere before concentration 2.5 Mass concentration/number concentration ratio) and concentration efficiency (concentration after actual concentration as a percentage of the theoretical concentration). The flow rates of the two scanning electric mobility particle size spectrometers were set at 0.3 liters/minute, so that, when connected to the enrichment system, 0.3 liters/minute of air flow in the concentration gas line entered the scanning electric mobility particle size spectrometers, and the remaining 4.7 liters/minute of air flow was used for subsequent concentrated sample collection. In addition, because system steam is too big, be difficult for direct access to scan mobility particle size spectrometer, need add the drying tube in the front end and get rid of steam and reduce the particle size. (note: when collecting the concentrated sample and determining the number and mass concentration of the particulate matter, the flow of two branches of the concentrated gas path needs to be adjusted to make the sum of the two branches equal to one tenth of the main gas flow).

Claims (6)

1. The utility model provides an on-line measuring device of polarity organic matter in concentrated atmospheric particulates which characterized in that includes: impact PM 2.5 The device comprises a cutting head, a water tank heating system, a virtual cutting system, a condensation circulating system and an online measuring system; wherein:
the collision type PM 2.5 Cutting head comprising PM 10 、PM 5 、PM 2.5 Three stages, each stage consists of an impact pore plate and an impact separation and collection plate, wherein the three stages of impact separation and collection plates have the same structure, and the pore numbers and the pore diameters of the three stages of impact plates are different due to different impact inertias of particles with different particle diameters;
the water tank heating system comprises a water tank (9) for containing deionized water, and a heat insulation layer (10) is arranged on the inner wall of the water tank (9) and used for preserving the heat of the deionized water in the water tank (9); a visible window (11) is arranged on one side of the water tank (9) and used for observing the height of the water surface in the tank body; an electric heating rod (12) with a temperature sensor is arranged in the water tank (9) and used for heating the deionized water; a temperature control digital display device (13) is arranged in the water tank (9) and is used for controlling the temperature of the deionized water; impact PM 2.5 The cutting head (7) is communicated with the water tank (9);
the virtual cutting system comprises a virtual cutter (17), a concentrated airflow vacuum pump (2) and a main airflow vacuum pump (3); wherein the virtual cutter (17) comprises a nozzle (19), a nozzle connecting pipe (20) and two air paths: a main gas path and a concentration gas path; the nozzle (19) and the nozzle connecting pipe (20) are coaxially arranged, the nozzle connecting pipe (20) is arranged above the nozzle (19) and is spaced by a certain gap, and the nozzle connecting pipe (20) is used for receiving particles sprayed by the nozzle (19); the main air flow vacuum pump (3) is communicated with a main air path outlet (18) at the upper part of the virtual cutter (17) through a pipeline, a drying pipe (4) and a large-flow mass flow controller (5) are arranged on the communicated pipeline, the drying pipe (4) is used for drying air flow so as to prevent the water vapor of the system from excessively damaging a pump body, and the large-flow mass flow controller (5) is used for accurately controlling the flow of the pipeline; the concentrated airflow vacuum pump (2) is communicated with a concentrated air passage at the upper part of the virtual cutter (17) through a pipeline, and a float flowmeter (1) is arranged on the communicated pipeline and used for metering the flow of the pipeline;
the condensation circulating system comprises a condensing agent circulating pipe (6) and a condenser (8); the condensing agent circulating pipe (6) comprises a condensing inner pipe (14), a soft copper spiral pipe (15) is tightly wound outside the condensing inner pipe (14), and the beginning end and the end of the spiral pipe (15) are respectively connected with an outlet and an inlet of the condensing machine (8); a heat insulation layer (16) is wrapped outside the spiral pipe (15), so that the temperature of the condensation pipe is not influenced by the outside temperature, and the condensation circulating system is used for circulating and circulating condensate to condense and grow saturated particles;
an airflow outlet of the water tank (9) is coaxially arranged with the beginning end of a condensation inner pipe (14) in a condensation circulating system and is connected by a quick-connection flange (containing a sealing ring); the terminal of the condensation inner pipe (14) is connected with a nozzle (19) in the virtual cutting system;
the online measurement system comprises a biological sampling bottle (21), a liquid chromatogram flight time mass spectrum (22) and a computer subdivision constant flow pump (23); wherein, the upper port of the biological sampling bottle (21) is communicated with a communication pipeline between the concentrated airflow vacuum pump (2) and the virtual cutter (17) and is used for carrying out on-line collection on the concentrated saturated particles, and the collection solvent is deionized water; the four-channel computer subdivision constant flow pump (23) is provided with two pumps, wherein one pump is used for injecting a solvent into the biological sampling bottle, and the other pump is used for extracting the collected concentrated sample from the biological sampling bottle and realizing on-line concentrated sample collection; an electromagnetic valve and a time relay for controlling the opening and closing of the electromagnetic valve are arranged in front of the two computer subdivision constant-current pumps and are used for controlling the two computers to subdivide the constant-current pumps to work so that the working and sleeping time of the constant-current pumps can be kept synchronous; the concentrated solution extracted by the constant flow pump (23) is injected into a liquid chromatogram flight time mass spectrum (22) on line, and the trace polar molecules in the concentrated solution are detected on line.
2. The apparatus of claim 1, wherein the condensing agent in the condenser is alcohol, and the concentration of the alcohol is adjustable, so as to achieve the effects of refrigerating and reducing the volatilization amount of saturated particulate matters.
3. The apparatus for on-line measurement of polar organic compounds in concentrated atmospheric particulates according to claim 1, wherein the condensation inner tube (14) has a diameter of 2.5 cm and a length of 80 cm.
4. The apparatus for on-line measurement of polar organic compounds in concentrated atmospheric particulates according to claim 1, wherein the nozzle diameter is 0.37 cm, the gap between the nozzle (9) and the nozzle adapter (20) is 0.45 cm, and the nozzle adapter diameter is 2.5 cm.
5. A method for measuring polar organic matters in concentrated atmospheric particulates on line based on the device in any one of claims 1 to 4 is characterized by comprising the following specific steps:
(1) To collision type PM 2.5 The cutting head (7) is arranged in the actual atmospheric environment, and the original atmospheric sample passes through the collision type PM 2.5 The cutting head (7) discharges PM 2.5 Atmospheric fine particles with the aerodynamic equivalent diameter of less than or equal to 2.5 micrometers are screened out and enter a water tank (9) by means of system suction;
(2) Under a visible window (11), adding deionized water to two thirds of the height of the water tank, heating the deionized water by using an electric heating rod (12) with a temperature sensor, and controlling the temperature to be 35 +/-2 ℃ by using a temperature control digital display device (13) to enable the generated water vapor to enable particles to reach a saturated state;
(3) The particles reaching the saturated state flow through a condensation inner pipe (14) of the condensation circulating system; the external circulation temperature control mode of the condenser controls the temperature to be-12 +/-1 ℃, so that the circulating condensate liquid condenses and grows saturated particles, wherein most PM 2.5 Can grow to 3-4 microns in aerodynamic diameter;
(4) Condensing the elongated PM 2.5 The particles enter the virtual cutter (17) and are accelerated at the nozzle (19); the accelerating power of the gas-liquid separator comes from two gas paths, namely a main gas path and a concentration gas path; in the main gas path, the main flow is accurately controlled to be 50 +/-1 liter/minute by a large-flow mass flow controller (5); in the concentration gas path, the particles accelerated by the nozzle (19) are received by a nozzle connecting pipe (20) above the coaxially arranged nozzle, and the flow of the concentrated gas flow is controlled to be 5 liters per minute; theoretically, under the condition that the concentration of the particulate matters is the same, the gas flow becomes one tenth of the original gas flow, and the concentration of the particulate matters in the sample becomes ten times of the original concentration, so that the concentration effect is achieved;
(5) Carrying out on-line collection on the concentrated saturated particles by using a biological sampling bottle (21), wherein a collection solvent is deionized water; one of the two four-channel computer subdivision constant flow pumps (23) is used for injecting a solvent into the biological sampling bottle, controlling the work for 1 minute, injecting 5 to 10 milliliters of the solvent and sleeping for 59 minutes, and the other is used for extracting the collected concentrated sample from the biological sampling bottle, controlling the work for 1 minute, collecting 5 to 10 milliliters of the solvent and sleeping for 59 minutes; in order to keep synchronous with the working and sleeping time of the constant flow pump, the switching time of the electromagnetic valve is set to be 1 minute for switching on and 59 minutes for switching off; and the concentrated solution extracted by the constant flow pump (23) is injected into a liquid chromatogram flight time mass spectrum (22) on line, and the trace polar molecules in the concentrated solution are detected on line.
6. The method for on-line measurement of trace water-soluble ions according to claim 5, wherein after the concentration is completed, the final evaluation is performed by a concentration factor and a concentration efficiency; wherein, the concentration factor refers to: PM in atmosphere after concentration 2.5 Mass concentration/number concentration/chemical component concentration of (1) and PM in the atmosphere before concentration 2.5 The ratio of mass concentration/number concentration/chemical component concentration of (a); the concentration efficiency is as follows: the actual post-concentration is a percentage of the theoretical concentration.
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