CN109212072B - Polycyclic aromatic hydrocarbon soil gas source sink identification method - Google Patents
Polycyclic aromatic hydrocarbon soil gas source sink identification method Download PDFInfo
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Abstract
The invention relates to a polycyclic aromatic hydrocarbon soil gas source convergence identification method which comprises four processes of preparation of a polyethylene film adsorption material containing a marker, in-situ sampling and pretreatment of the polyethylene film adsorption material in soil and air, calculation of equilibrium concentration of polycyclic aromatic hydrocarbon in soil and air and judgment of polycyclic aromatic hydrocarbon migration direction in a soil gas exchange process, and the source convergence pattern of the polycyclic aromatic hydrocarbon in the soil gas exchange process is identified under specific environmental conditions. The method has the advantages of low sampling cost, no limitation of factors such as power supply and noise disturbing residents, simple sample processing process, accurate judgment on the convergence pattern of the 12 kinds of polycyclic aromatic hydrocarbon soil gas exchange sources, and suitability for accurate recognition of the convergence of the polycyclic aromatic hydrocarbon soil gas sources under the environmental conditions of farmlands, polluted sites, residential districts and the like.
Description
Technical Field
The invention belongs to the technical field of source sink identification in the field of environmental monitoring, and particularly relates to a polycyclic aromatic hydrocarbon soil gas source sink identification method for identifying and judging the migration direction of polycyclic aromatic hydrocarbon in a soil gas exchange process.
Background
Polycyclic aromatic hydrocarbons have a triple effect, are difficult to degrade in the environment, and can be cumulatively amplified through the food chain, and thus have received much attention. Polycyclic aromatic hydrocarbons have characteristics such as easy volatility and difficult degradation, can constantly "volatilize-migration-subside" in environmental medium, carry out long distance transmission in global scale, and this kind of "grasshopper effect" leads to in high altitude even polar region etc. less human activity's region can all detect these persistent organic pollutants.
Soil is an important carrier of persistent organic pollutants, and air is an important medium for the transmission of persistent organic pollutants. The polycyclic aromatic hydrocarbon soil gas exchange process is a key process of pollutant transmission and homing, and the soil gas source convergence pattern of the polycyclic aromatic hydrocarbon in the real environment is identified, so that the method is beneficial to judging whether the polluted soil is a secondary pollution source of the polycyclic aromatic hydrocarbon in the air or the air transmission is an important way of the polycyclic aromatic hydrocarbon pollution of the soil. For example, in the Qinghai-Tibet plateau where human activities are weak, the soil is a sink of high-ring polycyclic aromatic hydrocarbons and a potential secondary pollution source of low-ring polycyclic aromatic hydrocarbons in the air, but for hexachloro-cyclohexane and DDTs, the soil is just a sink. Polycyclic aromatic hydrocarbons are also found in Hangzhou agricultural and industrial areas to evaporate from the soil into the air.
In the research of the soil gas exchange process of polycyclic aromatic hydrocarbon, the migration direction of the polycyclic aromatic hydrocarbon in the soil gas exchange process is determined by comparing the fugacity of the polycyclic aromatic hydrocarbon in soil and air at present. When the fugacity of the polycyclic aromatic hydrocarbon in the air is measured, an active sampling method is mostly adopted. Utilize municipal power supply drive air pump to absorb ambient air, the sampling process has certain noise pollution, so, receive the restriction of power supply in farmland and woodland region, receive noise pollution's restriction in residential quarter. When the fugacity of the polycyclic aromatic hydrocarbon in the soil is measured, the completely-extractable concentration of the polycyclic aromatic hydrocarbon in the soil is usually measured, and then the fugacity of the polycyclic aromatic hydrocarbon is calculated based on an organic matter adsorption/absorption model. In the calculation process of the organic matter adsorption/absorption model, the earth gas distribution coefficient (K) needs to be utilizedsoil-air) Fugacity calculations were performed, although K was measured by organic content and black carbon contentsoil-airCorrection is made, but there is still a large uncertainty (>50%), the accuracy of the fugacity of the target object in the soil is influenced, and the judgment of the soil-gas exchange migration direction and the identification of the source and sink are finally influenced.
Based on the background, a polycyclic aromatic hydrocarbon source and sink identification method is developed, which can reduce the limitation of power supply and noise pollution and avoid KSoil-AirThe method has the advantages that the error of the fugacity ratio caused by the estimation deviation is improved, and the accuracy of the identification of the earth-gas exchange source sink is improved, so that the method is a problem which needs to be solved urgently in the environment monitoring work.
Disclosure of Invention
The purpose of the invention isThe polycyclic aromatic hydrocarbon soil gas source sink identification method is provided for overcoming the defects in the prior art, and not only can the influence on urban power supply limitation and noise disturbance to residents be reduced, but also the soil gas distribution coefficient (K) can be eliminatedsoil-air) The uncertainty brought by the method can accurately identify the soil gas source convergence pattern of the polycyclic aromatic hydrocarbon in the real environment.
The purpose of the invention can be realized by the following technical scheme:
a polycyclic aromatic hydrocarbon soil gas source sink identification method is characterized in that polycyclic aromatic hydrocarbons in soil and air are adsorbed in situ through a polyethylene film, when the polyethylene film reaches adsorption balance, the polycyclic aromatic hydrocarbon adsorption balance concentration difference of the polyethylene film in the soil and the air reflects the source sink pattern of the polycyclic aromatic hydrocarbons in the soil gas exchange process, and the method comprises the following steps:
(1) preparation of polyethylene film adsorbing material containing marker
Dissolving dibromo biphenyl, tetrabromo biphenyl, pentabromo biphenyl, octachloronaphthalene and deuterated pyrene in a methanol aqueous solution to prepare a PRCs solution;
soaking the cut polyethylene film in water, acetone, dichloromethane and n-hexane for 20-40 hours in sequence, then soaking the polyethylene film in a PRCs solution for 20-60 days, taking out the polyethylene film, sealing and storing the polyethylene film, and preparing the polyethylene film adsorbing material containing the marker;
(2) in-situ sampling and pretreatment of polyethylene film adsorption material in soil and air
In-situ sampling of polyethylene film adsorption material in soil: vertically placing a polyethylene film adsorption material containing a marker in surface soil, adsorbing polycyclic aromatic hydrocarbons in the soil by using a polyethylene film to collect an in-situ soil sample, and taking out and storing after adsorbing for 10-60 days;
in-situ sampling of polyethylene film adsorption material in air: suspending a polyethylene film adsorption material containing a marker in the air, adsorbing polycyclic aromatic hydrocarbon in the air to collect an in-situ air sample, and taking back and storing after adsorbing for 10-60 days;
pretreatment: cleaning the sampled polyethylene film adsorption material with water, removing surface impurities, adding deuterated polycyclic aromatic hydrocarbon to the surface of the polyethylene film adsorption material, soaking the sampled polyethylene film adsorption material for 16-48h by using dichloromethane and n-hexane in sequence, then mixing the dichloromethane soaking solution and the n-hexane soaking solution, replacing the solvent with n-hexane, concentrating, adding deuterated fluorene, and finishing sample pretreatment.
(3) Calculation of polycyclic aromatic hydrocarbon adsorption equilibrium concentration in soil and air
Determining the concentration of polycyclic aromatic hydrocarbons and the concentration of PRCs components in the pretreated polyethylene film adsorbing material, calculating the adsorption equilibrium percentage of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorbing material according to the residual concentration of the PRCs components in the sampled polyethylene film adsorbing material, and correcting the adsorption concentration of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorbing material to obtain the adsorption equilibrium concentration of the polycyclic aromatic hydrocarbons in the polyethylene film adsorbing material with single mass in soil and air;
(4) polycyclic aromatic hydrocarbon migration direction judgment in soil gas exchange process
According to the adsorption equilibrium concentration of polycyclic aromatic hydrocarbon in the polyethylene film adsorption material with single mass in the soil and the air, calculating the adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in the soil and the airPE-soil/CPE-air) Judging the migration direction of the polycyclic aromatic hydrocarbon in the soil gas exchange process, wherein CPE-soilAdsorbing equilibrium concentration of polycyclic aromatic hydrocarbon in soil, CPE-airThe adsorption equilibrium concentration of the polycyclic aromatic hydrocarbon in the air.
In the step (1), the mass ratio of the dibromobiphenyl, the tetrabromobiphenyl, the pentabromobiphenyl, the octachloronaphthalene, the deuterated pyrene, the methanol and the water is 1.0-3.0:0.2-1.2:0.1-0.6:0.25-2.5:0.25-2.5:1.0-3.2 × 106:0.8-3.0×106。
The mass ratio of the deuterated polycyclic aromatic hydrocarbon to the deuterated fluorene added in the step (2) is 1:1, and the mass ratio of the deuterated polycyclic aromatic hydrocarbon to the dibromobiphenyl added is 1 multiplied by 10-4:1.0-3.0。
And (3) determining the concentration of the polycyclic aromatic hydrocarbon and the concentration of PRCs components in the pretreated polyethylene film adsorption material by using a gas chromatography-mass spectrometer.
And (3) calculating the adsorption equilibrium percentage (formula 1) of the polycyclic aromatic hydrocarbon in the sampled polyethylene film adsorption material according to the residual concentration of the PRCs components in the sampled polyethylene film adsorption material, and correcting the adsorption concentration of the polycyclic aromatic hydrocarbon in the sampled polyethylene film adsorption material to obtain the adsorption equilibrium concentration (formula 2) of the polycyclic aromatic hydrocarbon in the polyethylene film adsorption material with single quality in soil and air.
Wherein, equ%: adsorption equilibrium percentage of polycyclic aromatic hydrocarbons;
C0、Ct: the initial concentration of PRCs in the polyethylene film adsorbent and the residual concentration at time t.
Wherein, CPE-air(soil): when the equilibrium state is reached, the polyethylene film adsorption material in the air (or in the soil) adsorbs the concentration of the polycyclic aromatic hydrocarbon;
CPE,t: at time t, the polyethylene film adsorbing material in the air (or in the soil) adsorbs the concentration of the polycyclic aromatic hydrocarbon.
When judging the migration direction of the polycyclic aromatic hydrocarbon in the soil-gas exchange process, detecting to obtain the adsorption equilibrium concentration ratio (C) of the polycyclic aromatic hydrocarbon in the soil and the airPE-soil/CPE-air) More than 1.25, polycyclic aromatic hydrocarbons migrate from the soil to the air; detecting to obtain the polycyclic aromatic hydrocarbon adsorption equilibrium concentration ratio (C) in the soil and the airPE-soil/CPE-air) Less than 0.8, polycyclic aromatic hydrocarbons migrate from the air to the soil; detecting to obtain the polycyclic aromatic hydrocarbon adsorption equilibrium concentration ratio (C) in the soil and the airPE-soil/CPE-air) And in the range of 0.8-1.25, the polycyclic aromatic hydrocarbon reaches dynamic exchange balance in the soil gas exchange process.
More specifically, the equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbons adsorbed in soil and airPE-soil/CPE-air) 1.25-2.1 and not including 1.25, polycyclic aromatic hydrocarbons from earthSoil is migrated to the air; adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in soil and airPE-soil/CPE-air) 0.5-0.8 and not including 0.8, polycyclic aromatic hydrocarbons migrate from the air to the soil.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the polyethylene film is adopted to adsorb polycyclic aromatic hydrocarbons in soil and air in situ, the operation is simple and convenient, the sampling limit of urban power supply and noise disturbing residents is avoided, the sampling cost is low, monitoring points can be distributed in a large range, and the practicability is strong;
2. the invention eliminates the uncertainty caused by the soil gas distribution coefficient (Ksol-air) and improves the accuracy of polycyclic aromatic hydrocarbon soil gas source convergence.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A polycyclic aromatic hydrocarbon soil gas source convergence identification method is disclosed, the process flow is shown in figure 1, polycyclic aromatic hydrocarbon in soil and air is adsorbed in situ by a polyethylene film, when the polyethylene film reaches adsorption balance, the polycyclic aromatic hydrocarbon adsorption balance concentration difference of the polyethylene film in the soil and the air reflects the source convergence pattern of the polycyclic aromatic hydrocarbon in the soil gas exchange process, and the following steps are adopted:
(1) preparation of polyethylene film adsorbing material containing marker
Dissolving 1.0-3.0mg of dibromobiphenyl, 0.2-1.2mg of tetrabromobiphenyl, 0.1-0.6mg of pentabromobiphenyl, 0.25-2.5mg of octachloronaphthalene and 0.25-2.5mg of deuterated pyrene in 1.0-3.2L of methanol, and adding 0.8-3L of water to prepare a PRCs solution.
Cutting a polyethylene film material with the thickness of 30-80 mu m into 20-40cm (length) and 5-10cm (width), and the weight is about 1.0-5.0 g. And (3) soaking the cut polyethylene film for 20-40h by using water, acetone, dichloromethane and normal hexane in sequence, then soaking for 20-60 days by using a PRCs solution, taking out, then placing into a metal sample bag, and sealing and storing to finish the preparation of the polyethylene film adsorbing material containing the marker.
(2) In-situ sampling and pretreatment of polyethylene film adsorption material in soil and air
In-situ sampling of polyethylene film adsorption material in soil: vertically placing the polyethylene film adsorption material containing the marker in surface soil with the depth of 5-15cm, adsorbing polycyclic aromatic hydrocarbon in the soil by the polyethylene film to collect an in-situ soil sample, adsorbing for 10-60 days, taking out the polyethylene film, and placing the polyethylene film into a metal sample bag for storage.
In-situ sampling of polyethylene film adsorption material in air: fixing the polyethylene film adsorption material containing the marker in an inverted stainless steel bowl by using a stainless steel wire, hanging the stainless steel bowl at a position 50-200cm away from the ground, contacting with air, adsorbing polycyclic aromatic hydrocarbon in the air to collect an in-situ air sample, taking out the polyethylene film after adsorbing for 10-60 days, and putting the polyethylene film back into a metal sample bag for storage.
Pretreatment: and (3) cleaning the sampled polyethylene film adsorbing material with water, removing impurities such as particles attached to the surface, adding 100ng of deuterated polycyclic aromatic hydrocarbon to the surface of the polyethylene film adsorbing material, and soaking the sampled polyethylene film adsorbing material for 16-48h by using 30-60mL of dichloromethane and 30-60mL of n-hexane in sequence. And mixing the dichloromethane soaking solution and the n-hexane soaking solution, converting the solvent into n-hexane, concentrating to 1mL, and finally adding 100ng of deuterated fluorene to complete sample pretreatment.
(3) Calculation of polycyclic aromatic hydrocarbon adsorption equilibrium concentration in soil and air
The method comprises the steps of measuring the concentration of polycyclic aromatic hydrocarbons and the concentration of PRCs components in a pretreated sample by using a gas chromatography-mass spectrometer, calculating the adsorption equilibrium percentage (formula 1) of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorption material according to the residual concentration of the PRCs components in the sampled polyethylene film adsorption material, and correcting the adsorption concentration of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorption material to obtain the adsorption equilibrium concentration (formula 2) of the polycyclic aromatic hydrocarbons in the polyethylene film adsorption material with single mass in soil and air.
Wherein, equ%: adsorption equilibrium percentage of polycyclic aromatic hydrocarbons;
C0、Ct: the initial concentration of PRCs in the polyethylene film adsorbent and the residual concentration at time t.
Wherein, CPE-air(soil): when the equilibrium state is reached, the polyethylene film adsorption material in the air (or in the soil) adsorbs the concentration of the polycyclic aromatic hydrocarbon;
CPE,t: at the time t, the polyethylene film adsorption material in the air (or in the soil) adsorbs the concentration of the polycyclic aromatic hydrocarbon;
(4) polycyclic aromatic hydrocarbon migration direction judgment in soil gas exchange process
According to the adsorption equilibrium concentration of polycyclic aromatic hydrocarbon in the polyethylene film adsorption material with single mass in the soil and the air, calculating the adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in the soil and the airPE-soil/CPE-air) And judging the migration direction of the polycyclic aromatic hydrocarbon in the soil gas exchange process. When the polycyclic aromatic hydrocarbon in the soil and the air adsorbs the equilibrium concentration ratio (C)PE-soil/CPE-air) More than 1.25-2.1, evaporating polycyclic aromatic hydrocarbon from soil to air, wherein the soil is a source and the air is a sink; when the polycyclic aromatic hydrocarbon in the soil and the air adsorbs the equilibrium concentration ratio (C)PE-soil/CPE-air) When the concentration is less than 0.5-0.8, the polycyclic aromatic hydrocarbon is settled from the air to the soil, the air is a source, and the soil is a sink; when the polycyclic aromatic hydrocarbon in the soil and the air adsorbs the equilibrium concentration ratio (C)PE-soil/CPE-air) Between the two, the polycyclic aromatic hydrocarbon approximately moves in the process of soil gas exchangeAnd (4) state exchange balance.
The following are more specific examples.
Example 1
The method is applied to identify the soil gas source sink of the polycyclic aromatic hydrocarbon in the residential community of the Shanghai city;
3.0mg of dibromobiphenyl, 1.2mg of tetrabromobiphenyl, 0.6mg of pentabromobiphenyl, 2.5mg of octachloronaphthalene and 2.5mg of deuterated pyrene were dissolved in 3.2L of methanol, and 0.8L of water was added to prepare a PRCs solution. A polyethylene film material having a thickness of 30 μm was cut into a length of 20cm and a width of 5cm, and weighed about 1.0 g. And (3) soaking the cut polyethylene film for 20 hours by using water, acetone, dichloromethane and normal hexane in sequence, then soaking for 20 days by using a PRCs solution, taking out, then placing into a metal sample bag, sealing and storing, and completing the preparation of the polyethylene film adsorbing material containing the marker.
Vertically placing a polyethylene film adsorption material containing a marker in surface soil with the depth of 10cm, adsorbing polycyclic aromatic hydrocarbons in the soil by the polyethylene film to collect an in-situ soil sample, and taking out the polyethylene film and placing the polyethylene film into a metal sample bag for storage after adsorbing for 15 days. Fixing a polyethylene film adsorption material containing a marker in an inverted stainless steel bowl by using a stainless steel wire, hanging the stainless steel bowl in air 50cm away from the ground, contacting with the air, adsorbing polycyclic aromatic hydrocarbons in the air to collect an in-situ air sample, and taking out the polyethylene film after adsorbing for 15 days and putting the polyethylene film back into a metal sample bag for storage. And (3) cleaning the sampled polyethylene film adsorbing material with water, removing impurities such as particles attached to the surface, adding 100ng of deuterated polycyclic aromatic hydrocarbon to the surface of the polyethylene film adsorbing material, and soaking the sampled polyethylene film adsorbing material for 16 hours by using 30mL of dichloromethane and 30mL of n-hexane in sequence. And mixing the dichloromethane soaking solution and the n-hexane soaking solution, converting the solvent into n-hexane, concentrating to 1mL, and finally adding 100ng of deuterated fluorene to complete sample pretreatment.
And (3) measuring the concentration of the polycyclic aromatic hydrocarbons and the concentration of PRCs components in the pretreated sample by adopting a gas chromatography-mass spectrometer, calculating the adsorption equilibrium percentage of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorption material according to the residual concentration of the PRCs components in the sampled polyethylene film adsorption material, and correcting the adsorption concentration of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorption material to obtain the adsorption equilibrium concentration of the polycyclic aromatic hydrocarbons in the polyethylene film adsorption material with single mass in soil and air.
According to the adsorption equilibrium concentration of polycyclic aromatic hydrocarbon in the polyethylene film adsorption material with single mass in the soil and the air, calculating the adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in the soil and the airPE-soil/CPE-airAnd the method is shown in table 1), judging the migration direction of the polycyclic aromatic hydrocarbon in the soil gas exchange process, and identifying the soil gas source convergence pattern.
TABLE 1. recognition of equilibrium concentration ratio of adsorption of polycyclic aromatic hydrocarbons in soil and air in residential quarters of Shanghai City and sink of soil gas
| Serial number | Name of Chinese | Compound | CPE-Soil/CPE-Air | Direction of migration | Source | Sink (C) |
| 1 | Fluorene compounds | Fluorene | 0.24 | Sedimentation | Qi (Qi) | Soil for soil |
| 2 | Phenanthrene | Phenanthrene | 0.04 | Sedimentation | Qi (Qi) | Soil for soil |
| 3 | Anthracene | Anthracene | 0.14 | Sedimentation | Qi (Qi) | Soil for soil |
| 4 | Fluoranthene | Fluoranthene | 0.32 | Sedimentation | Qi (Qi) | Soil for soil |
| 5 | Pyrene | Pyrene | 0.45 | Sedimentation | Qi (Qi) | Soil for soil |
| 6 | Benzo [ a ]]Anthracene | Benz[a]anthracene | 3.85 | Evaporation of | Soil for soil | Qi (Qi) |
| 7 | Flexion type | Chrysene | 2.67 | Evaporation of | Soil for soil | Qi (Qi) |
| 8 | Benzo [ b ]]Fluoranthene | Benzo[b]fluoranthene | 7.24 | Evaporation of | Soil for soil | Qi (Qi) |
| 9 | Benzo [ k ] benzene]Fluoranthene | Benzo[k]fluoranthene | 4.49 | Evaporation of | Soil for soil | Qi (Qi) |
| 10 | Benzo [ a ]]Pyrene | Benzo[a]pyrene | 6.33 | Evaporation of | Soil for soil | Qi (Qi) |
| 11 | Indeno [1,2,3-cd]Pyrene | Indeno[1,2,3-cd]pyrene | 8.97 | Evaporation of | Soil for soil | Qi (Qi) |
| 12 | Dibenzo [ a, h ]]Anthracene | Dibenz[a,h]anthracene | 4.01 | Evaporation of | Soil for soil | Qi (Qi) |
| 13 | Benzo [ g, h, i ]]Pyrene | Benzo[ghi]pyrene | 7.03 | Evaporation of | Soil for soil | Qi (Qi) |
Example 2
The method is applied to identify the gas source sink of the polycyclic aromatic hydrocarbon soil in Shanghai Changxing island farmlands;
1.0mg of dibromobiphenyl, 0.2mg of tetrabromobiphenyl, 0.1mg of pentabromobiphenyl, 0.25mg of octachloronaphthalene and 0.25mg of deuterated pyrene were dissolved in 1.0L of methanol, and 3L of water was added to prepare a PRCs solution. The polyethylene film material having a thickness of 80 μm was cut into pieces of 40cm (length) and 10cm (width) and weighed about 3.0 g. And (3) soaking the cut polyethylene film for 40 hours by using water, acetone, dichloromethane and normal hexane in sequence, then soaking for 60 days by using a PRCs solution, taking out, then placing into a metal sample bag, sealing and storing, and completing the preparation of the polyethylene film adsorbing material containing the marker.
Vertically placing the polyethylene film adsorption material containing the marker in surface soil with the depth of 15cm, adsorbing polycyclic aromatic hydrocarbon in the soil by the polyethylene film to collect an in-situ soil sample, and taking out the polyethylene film and placing the polyethylene film into a metal sample bag for storage after 60 days of adsorption. Fixing a polyethylene film adsorption material containing a marker in an inverted stainless steel bowl by using a stainless steel wire, hanging the stainless steel bowl in air 200cm away from the ground, contacting with the air, adsorbing polycyclic aromatic hydrocarbons in the air to collect an in-situ air sample, and taking out the polyethylene film and putting the polyethylene film into a metal sample bag for storage after 60 days of adsorption. And (3) cleaning the sampled polyethylene film adsorbing material with water, removing impurities such as particles attached to the surface, adding 100ng of deuterated polycyclic aromatic hydrocarbon to the surface of the polyethylene film adsorbing material, and soaking the sampled polyethylene film adsorbing material for 48 hours by sequentially using 60mL of dichloromethane and 60mL of n-hexane. And mixing the dichloromethane soaking solution and the n-hexane soaking solution, converting the solvent into n-hexane, concentrating to 1mL, and finally adding 100ng of deuterated fluorene to complete sample pretreatment.
And (3) measuring the concentration of the polycyclic aromatic hydrocarbons and the concentration of PRCs components in the pretreated sample by adopting a gas chromatography-mass spectrometer, calculating the adsorption equilibrium percentage of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorption material according to the residual concentration of the PRCs components in the sampled polyethylene film adsorption material, and correcting the adsorption concentration of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorption material to obtain the adsorption equilibrium concentration of the polycyclic aromatic hydrocarbons in the polyethylene film adsorption material with single mass in soil and air.
According to the adsorption equilibrium concentration of polycyclic aromatic hydrocarbon in the polyethylene film adsorption material with single mass in the soil and the air, calculating the adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in the soil and the airPE-soil/CPE-airAnd see table 2), judging the migration direction of the polycyclic aromatic hydrocarbon in the soil gas exchange process, and identifying the soil gas source convergence pattern.
Table 2. recognition of equilibrium concentration ratio of polycyclic aromatic hydrocarbons adsorbed in soil and air in Changxing island farmland environment in Shanghai city and soil gas source sink
Example 3
The method is applied to identify the polycyclic aromatic hydrocarbon soil gas source sink in the environment of the air pollution source area of the marine port;
1.0mg of dibromobiphenyl, 0.2mg of tetrabromobiphenyl, 0.1mg of pentabromobiphenyl, 0.25mg of octachloronaphthalene and 0.25mg of deuterated pyrene were dissolved in 1.0L of methanol, and 3L of water was added to prepare a PRCs solution. A polyethylene film material having a thickness of 50 μm was cut into a length of 20cm and a width of 5cm, and weighed about 2.0 g. And (3) soaking the cut polyethylene film for 20 hours by using water, acetone, dichloromethane and normal hexane in sequence, then soaking for 30 days by using a PRCs solution, taking out, then placing into a metal sample bag, sealing and storing, and completing the preparation of the polyethylene film adsorbing material containing the marker.
Vertically placing the polyethylene film adsorption material containing the marker in surface soil with the depth of 10cm, adsorbing polycyclic aromatic hydrocarbon in the soil by the polyethylene film to collect an in-situ soil sample, and taking out the polyethylene film and placing the polyethylene film into a metal sample bag for storage after adsorbing for 45 days. Fixing a polyethylene film adsorption material containing a marker in an inverted stainless steel bowl by using a stainless steel wire, hanging the stainless steel bowl in the air 100cm away from the ground, contacting with the air, adsorbing polycyclic aromatic hydrocarbons in the air to collect an in-situ air sample, and taking out the polyethylene film after adsorbing for 45 days and putting the polyethylene film back into a metal sample bag for storage. And (3) cleaning the sampled polyethylene film adsorbing material with water, removing impurities such as particles attached to the surface, adding 100ng of deuterated polycyclic aromatic hydrocarbon to the surface of the polyethylene film adsorbing material, and soaking the sampled polyethylene film adsorbing material for 36 hours by using 40mL of dichloromethane and 40mL of n-hexane in sequence. And mixing the dichloromethane soaking solution and the n-hexane soaking solution, converting the solvent into n-hexane, concentrating to 1mL, and finally adding 100ng of deuterated fluorene to complete sample pretreatment.
And (3) measuring the concentration of the polycyclic aromatic hydrocarbons and the concentration of PRCs components in the pretreated sample by adopting a gas chromatography-mass spectrometer, calculating the adsorption equilibrium percentage of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorption material according to the residual concentration of the PRCs components in the sampled polyethylene film adsorption material, and correcting the adsorption concentration of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorption material to obtain the adsorption equilibrium concentration of the polycyclic aromatic hydrocarbons in the polyethylene film adsorption material with single mass in soil and air.
According to the adsorption equilibrium concentration of polycyclic aromatic hydrocarbon in the polyethylene film adsorption material with single mass in the soil and the air, calculating the adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in the soil and the airPE-soil/CPE-airAnd see table 3), judging the migration direction of the polycyclic aromatic hydrocarbon in the soil gas exchange process, and identifying the soil gas source convergence pattern.
TABLE 3 recognition of equilibrium concentration ratio of polycyclic aromatic hydrocarbons in soil and air in air pollution source area environment and soil gas source sink
| Serial number | Name of Chinese | Compound | CPE-Soil/CPE-Air | Direction of migration | Source | Sink (C) |
| 1 | Fluorene compounds | Fluorene | 0.0001 | Sedimentation | Qi (Qi) | Soil for soil |
| 2 | Phenanthrene | Phenanthrene | 0.130 | Sedimentation | Qi (Qi) | Soil for soil |
| 3 | Anthracene | Anthracene | 0.021 | Sedimentation | Qi (Qi) | Soil for soil |
| 4 | Fluoranthene | Fluoranthene | 0.188 | Sedimentation | Qi (Qi) | Soil for soil |
| 5 | Pyrene | Pyrene | 0.214 | Sedimentation | Qi (Qi) | Soil for soil |
| 6 | Benzo [ a ]]Anthracene | Benz[a]anthracene | 0.063 | Sedimentation | Qi (Qi) | Soil for soil |
| 7 | Flexion type | Chrysene | 0.229 | Sedimentation | Qi (Qi) | Soil for soil |
| 8 | Benzo [ b ]]Fluoranthene | Benzo[b]fluoranthene | 0.145 | Sedimentation | Qi (Qi) | Soil for soil |
| 9 | Benzo [ k ] benzene]Fluoranthene | Benzo[k]fluoranthene | 0.111 | Sedimentation | Qi (Qi) | Soil for soil |
| 10 | Benzo [ a ]]Pyrene | Benzo[a]pyrene | 0.010 | Sedimentation | Qi (Qi) | Soil for soil |
| 11 | Indeno [1,2,3-cd]Pyrene | Indeno[1,2,3-cd]pyrene | 0.010 | Sedimentation | Qi (Qi) | Soil for soil |
| 12 | Dibenzo [ a, h ]]Anthracene | Dibenz[a,h]anthracene | 0.002 | Sedimentation | Qi (Qi) | Soil for soil |
| 13 | Benzo [ g, h, i ]]Pyrene | Benzo[ghi]pyrene | 0.005 | Sedimentation | Qi (Qi) | Soil for soil |
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (6)
1. A polycyclic aromatic hydrocarbon soil gas source sink identification method is characterized by comprising the following steps:
(1) preparation of polyethylene film adsorbing material containing marker
Dissolving dibromo biphenyl, tetrabromo biphenyl, pentabromo biphenyl, octachloronaphthalene and deuterated pyrene in a methanol aqueous solution to prepare a PRCs solution;
soaking the cut polyethylene film in water, acetone, dichloromethane and n-hexane for 20-40 hours in sequence, then soaking the polyethylene film in a PRCs solution for 20-60 days, taking out the polyethylene film, sealing and storing the polyethylene film, and preparing the polyethylene film adsorbing material containing the marker;
(2) in-situ sampling and pretreatment of polyethylene film adsorption material in soil and air
In-situ sampling of polyethylene film adsorption material in soil: vertically placing a polyethylene film adsorption material containing a marker in surface soil, adsorbing polycyclic aromatic hydrocarbons in the soil by using a polyethylene film to collect an in-situ soil sample, and taking out and storing after adsorbing for 10-60 days;
in-situ sampling of polyethylene film adsorption material in air: suspending a polyethylene film adsorption material containing a marker in the air, adsorbing polycyclic aromatic hydrocarbon in the air to collect an in-situ air sample, and taking back and storing after adsorbing for 10-60 days;
pretreatment: cleaning the sampled polyethylene film adsorption material with water, removing surface impurities, adding deuterated polycyclic aromatic hydrocarbon to the surface of the polyethylene film adsorption material, sequentially soaking the sampled polyethylene film adsorption material with dichloromethane and n-hexane for 16-48h, then mixing the dichloromethane soaking solution and the n-hexane soaking solution, replacing a solvent with n-hexane, concentrating, and adding deuterated fluorene to complete sample pretreatment;
(3) calculation of polycyclic aromatic hydrocarbon adsorption equilibrium concentration in soil and air
Determining the concentration of polycyclic aromatic hydrocarbons and the concentration of PRCs components in the pretreated polyethylene film adsorbing material, calculating the adsorption equilibrium percentage of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorbing material according to the residual concentration of the PRCs components in the sampled polyethylene film adsorbing material, and correcting the adsorption concentration of the polycyclic aromatic hydrocarbons in the sampled polyethylene film adsorbing material to obtain the adsorption equilibrium concentration of the polycyclic aromatic hydrocarbons in the polyethylene film adsorbing material with single mass in soil and air;
calculating the adsorption equilibrium percentage of the polycyclic aromatic hydrocarbon in the sampled polyethylene film adsorption material (formula 1) according to the residual concentration of PRCs components in the sampled polyethylene film adsorption material, correcting the adsorption concentration of the polycyclic aromatic hydrocarbon in the sampled polyethylene film adsorption material to obtain the adsorption equilibrium concentration of the polycyclic aromatic hydrocarbon in the polyethylene film adsorption material with single quality in soil and air (formula 2),
equ%: adsorption equilibrium percentage of polycyclic aromatic hydrocarbons;
C0、Ct: the initial concentration of PRCs in the polyethylene film adsorbing material and the residual concentration at the time t,
CPE-air(soil): when the balance state is reached, the polyethylene film adsorption material in the air or the soil adsorbs the concentration of the polycyclic aromatic hydrocarbon;
CPE,t: at the time t, the polyethylene film adsorption material in the air or the soil adsorbs the concentration of the polycyclic aromatic hydrocarbon;
(4) polycyclic aromatic hydrocarbon migration direction judgment in soil gas exchange process
According to the adsorption equilibrium concentration of polycyclic aromatic hydrocarbon in the polyethylene film adsorption material with single mass in the soil and the air, calculating the adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in the soil and the airPE-soil/CPE-air) Judging the migration direction of the polycyclic aromatic hydrocarbon in the soil gas exchange process, wherein CPE-soilIn the soilEquilibrium concentration of adsorption of polycyclic aromatic hydrocarbons, CPE-airThe adsorption equilibrium concentration of the polycyclic aromatic hydrocarbon in the air is shown;
when the migration direction of the polycyclic aromatic hydrocarbon in the soil-gas exchange process is judged, the adsorption equilibrium concentration ratio (C) of the polycyclic aromatic hydrocarbon in the soil and the air is detectedPE-soil/CPE-air) More than 1.25, polycyclic aromatic hydrocarbons migrate from the soil to the air; detecting to obtain the polycyclic aromatic hydrocarbon adsorption equilibrium concentration ratio (C) in the soil and the airPE-soil/CPE-air) Less than 0.8, polycyclic aromatic hydrocarbons migrate from the air to the soil; detecting to obtain the polycyclic aromatic hydrocarbon adsorption equilibrium concentration ratio (C) in the soil and the airPE-soil/CPE-air) And in the range of 0.8-1.25, the polycyclic aromatic hydrocarbon reaches dynamic exchange balance in the soil gas exchange process.
2. The polycyclic aromatic hydrocarbon soil gas source sink identification method as claimed in claim 1, wherein the mass ratio of dibromobiphenyl, tetrabromobiphenyl, pentabromobiphenyl, octachloronaphthalene, deuterated pyrene, methanol and water in step (1) is 1.0-3.0:0.2-1.2:0.1-0.6:0.25-2.5:0.25-2.5:1.0-3.2 x 106:0.8-3.0×106。
3. The method for identifying the soil gas source sink of polycyclic aromatic hydrocarbon as claimed in claim 1, wherein the mass ratio of the deuterated polycyclic aromatic hydrocarbon to the deuterated fluorene added in step (2) is 1: 1.
4. The method for identifying the soil gas source sink of polycyclic aromatic hydrocarbon as claimed in claim 1, wherein the mass ratio of the deuterated polycyclic aromatic hydrocarbon to the dibromobiphenyl added in the step (2) is 1 x 10-4:1.0-3.0。
5. The polycyclic aromatic hydrocarbon soil gas source sink identification method according to claim 1, wherein in the step (3), a gas chromatography-mass spectrometer is adopted to measure the concentration of polycyclic aromatic hydrocarbons and the concentration of PRCs components in the pretreated polyethylene film adsorbing material.
6. A polypeptide according to claim 1A method for identifying the gas source sink of cyclic aromatic hydrocarbon soil is characterized by that the adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in soil and airPE-soil/CPE-air) 1.25-2.1 and not including 1.25, polycyclic aromatic hydrocarbons migrate from the soil to the air; adsorption equilibrium concentration ratio (C) of polycyclic aromatic hydrocarbon in soil and airPE-soil/CPE-air) 0.5-0.8 and not including 0.8, polycyclic aromatic hydrocarbons migrate from the air to the soil.
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