CN115032293A - Method for detecting migration behavior of organic phosphate in vertical direction of soil - Google Patents
Method for detecting migration behavior of organic phosphate in vertical direction of soil Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000013508 migration Methods 0.000 title claims abstract description 24
- 230000005012 migration Effects 0.000 title claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 21
- 239000010452 phosphate Substances 0.000 title claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 17
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- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 claims description 12
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 claims description 12
- -1 phosphate ester Chemical class 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
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- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 claims description 2
- KQROHCSYOGBQGJ-UHFFFAOYSA-N 5-Hydroxytryptophol Chemical compound C1=C(O)C=C2C(CCO)=CNC2=C1 KQROHCSYOGBQGJ-UHFFFAOYSA-N 0.000 claims 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
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Abstract
The invention discloses a method for detecting migration behavior of organic phosphate in the vertical direction of soil, which comprises the steps of collecting a plurality of soil samples at different depths and detecting the background concentration of OPEs in the environment; after aging treatment is carried out on a surface soil sample, sequentially filling sample soil into an organic glass column from a bottom layer to a top layer, simulating rainfall according to annual rainfall capacity to carry out a soil column leaching experiment, collecting soil samples in layers and carrying out pretreatment; and then carrying out high performance liquid chromatography-tandem mass spectrometry, and obtaining the concentration levels of the 6 organic phosphate esters in each section layer of the soil by an internal standard method.
Description
Technical Field
The invention relates to the field of environmental monitoring methods, in particular to a method for detecting migration behavior of organic phosphate in a soil vertical direction.
Background
Organic phosphates (ops) are widely used as plasticizers or flame retardants for various materials as a substitute for polybrominated diphenyl ethers, and the demands for ops are increasing. As an additive which is added in a physical mode, the OPEs do not form stable chemical bonds among molecules, so the OPEs can easily enter the surrounding environment in the processes of production, use and abandonment, and at present, OPEs with different concentration levels are detected in environmental media such as surface water, air, dust, soil, sediments and the like and in organisms, and the OPEs are also detected in environmental samples of rare and extremely rare regions. The serious environmental and health hazards of OPEs are increasingly recognized. As a potential persistent organic pollutant, OPEs have the characteristics of high yield, wide application range, persistence, enrichment, biotoxicity and the like, and pose a great threat to the environment and human health.
The presence of OPEs has been detected in a variety of environmental media and organisms, and their migration in the environment is of concern in view of this. Rainfall is an important link of atmospheric water circulation, and under the hydraulic action of runoff rainwater, some substances in soil immediately enter runoff to migrate. Throughout the rainfall process, the pollutants in the soil can migrate in two directions: the pollutants are released into the water body and migrate to a downstream area and an earth surface water body along the horizontal direction, so that the pollutants are diffused and redistributed; secondly, the water migrates to deeper soil along the vertical direction, causing the pollution of the deep soil and further polluting the underground water. The OPEs are widely detected in surface soil as a new organic pollutant at present, however, the migration behavior of the OPEs in the soil is rarely reported, so that the research on the migration behavior of the OPEs in the soil is very important, and a reasonable method for treating the pollution of the OPEs in the soil is established.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for detecting migration behavior of organic phosphate in the vertical direction of soil.
The purpose of the invention is realized by the following technical scheme:
a method for detecting the migration behavior of organic phosphate in the vertical direction of soil comprises the following steps:
collecting a plurality of soil samples from different depths from the soil surface, and obtaining the environmental background concentration of organic phosphate in the soil samples after air drying;
6 organic phosphate ester standard substances are dissolved in acetonitrile to prepare 5 mg/mL -1 Adding the standard stock solution into 100mL of ultra-pure water to prepare an OPEs mixed solution; selecting a surface soil sample closest to the earth surface and mixing the surface soil sample with the OPEs mixed solution uniformly in a beaker, ventilating for 3 hours to fully volatilize acetonitrile, and aging for 15 days at room temperature; placing the aged soil sample in a beaker which is cleaned in advance, freezing, drying, mashing, sieving and storing at the low temperature of-20 ℃;
and (3) performing a soil column leaching experiment: sequentially filling the collected air-dried sample soil into an organic glass column from the bottom layer to the top layer according to the collection concentration, and placing an aged soil sample on the top layer; setting experimental rainfall by programming according to the annual rainfall of the collected soil land, and controlling the flow speed of leachate to spray water to the top of the organic glass column by using a peristaltic pump to simulate rainfall; after each rainfall event is finished, draining water in the column, and carrying out layered sampling on the soil;
placing the sampled soil sample in a beaker which is cleaned in advance, freezing and drying the soil sample, pre-treating the dried soil sample in a solid phase after passing through a 100-mesh screen, and storing the pre-treated soil sample in a refrigerator at the temperature of-20 ℃;
and (3) carrying out quantitative analysis on the pretreated sample by using a high performance liquid chromatography-mass spectrometer (HPLC-MS).
Further, the 6 standards included triethyl phosphate (TEP), tributyl phosphate (TNBP), tris (1-chloro-2-propyl) phosphate (TCIPP), tris (1, 3-dichloro-2-propyl) phosphate (TDCIPP), tris (butoxyethyl) phosphate (TBOEP), and triphenyl phosphate (TPHP).
Further, the device that the earth pillar leaching experiment adopted includes: 3 organic glass columns and peristaltic pumps; wherein, organic glass post length is 36cm, and the internal diameter is 5cm, the setting of soil in the organic glass post is as follows: filling sample soil into the column from the bottom layer to the top layer in sequence, placing the aged soil sample on the surface layer, compacting all the soil of the section layer slightly, and filling the soil with the depth of 30 cm; saturating the soil column with deionized water, and naturally drying for 2 days; the inlet end of a hose of the peristaltic pump is arranged at the bottom of the beaker (used for supplying water), and the outlet end of the hose is fixed above the organic glass column (used for spraying water into the glass column).
Furthermore, plastic products are avoided in the processes of collection, storage and pretreatment of soil samples, so that pollution is reduced; the process water is ultrapure water, all glassware is washed three times by using the ultrapure water and methanol, and is dried for 2 hours at the temperature of 150 ℃ so as to achieve the aim of removing impurities.
Further, the pretreatment method of the soil sample comprises the following steps:
ultrasonic centrifugal extraction: a10 g sample of soil was weighed into a 50mL centrifuge tube, 2ng of internal standard materials (TNBP-d27 and TPHP-d15), 20mL of acetonitrile were added in sequence, and an appropriate amount of copper powder was added to remove sulfur elements. Shaking, performing ultrasonic extraction for 15min, centrifuging at 3000rpm for 10min, standing, and collecting supernatant. Repeating the above processes twice, transferring the supernatant obtained in the two operations to a rotary evaporation bottle, and performing solid phase extraction when the rotary evaporation is carried out to about 1 mL;
solid phase extraction: the solid phase extraction column (HLB) was activated with 5mL of dichloromethane, 5mL of ethyl acetate, and 5mL of methanol in this order, and the sample was then incubated at 4 mL. min -1 Is passed through the solid phase extraction column. After sampling, keeping the solid phase extraction column in a vacuum state, vacuumizing at negative pressure for 30min, and then eluting twice with 6mL ethyl acetate to obtain eluent;
nitrogen blowing: blowing the eluent in a 10mL glass test tube by a nitrogen blowing instrument under the condition of 37 ℃ water bath by using high-purity nitrogen, then rinsing the test tube by using ethyl acetate, transferring the rinsing solution into an automatic sample feeding bottle, and blowing the rinsing solution to be nearly dry under the same nitrogen blowing condition;
and (3) volume fixing: diluting to 200 μ L with methanol, mixing, filtering with 0.22 μm filter membrane, storing the pretreated sample in-20 deg.C refrigerator, and performing HPLC-MS detection.
Further, the quantitative analysis is to compare the measured value of the sample with a standard curve by selecting an internal standard method to obtain the accurate content of the organic phosphate in the sample; the standard curve of the organophosphate was plotted, with the concentration of the formulation internal standards (TNBP-d27 and TPHP-d15) being 10 ng-ml -1 The concentrations of the 6 organic phosphate esters are 1, 2, 5, 10, 25, 50, 100 and 200 ng/ml -1 The mixed standard solution is tested on a computer to determine the peak area of the quantitative ion integral, and a relation curve of the concentration ratio (the component to be measured and the internal standard substance) and the area ratio (the component to be measured and the internal standard substance) is made, and the curve is a standard curve.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
according to the invention, a soil column leaching experimental device is adopted to simulate the migration behavior of the OPEs in the vertical direction of the soil on the lower layer in the natural state, soil samples at different depths after rainfall simulation are respectively collected and preprocessed, and then high performance liquid chromatography tandem mass spectrometry analysis is performed, so that the concentration value of the OPEs in each soil layer is accurately obtained, and theoretical support is provided for further deep research on the environmental migration behavior of the OPEs.
Drawings
FIG. 1 is a flow chart of the method for detecting the migration of organophosphates in soil according to the present invention;
FIG. 2 is a standard curve of 6 OPEs established at S302 in step three, wherein (a) TEP; (b) TNBP; (c) TCIPP; (d) TDCIPP; (e) TBOEP; (f) TPHP;
FIG. 3 is the composition and concentration levels of organophosphates in the soil surface layers before and after leaching, obtained in step three at S303, where (a) TEP; (b) TNBP; (c) TCIPP; (d) TDCIPP; (e) TBOEP; (f) TPHP.
Detailed Description
In order to make the objects, technical solutions, advantages and significant progress of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described in detail and completely with reference to the drawings provided in the embodiments of the present invention, and it is obvious that all the described embodiments are only some embodiments of the present invention, not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention takes soil in the south of Jinnan, Tianjin city as a research sample to research the migration behavior of organic phosphate (hereinafter abbreviated as OPEs) in the vertical direction in the soil, aims to simulate the actual environment through a soil column leaching experiment, researches the migration behavior of the OPEs with different molecular structures in the soil in the leaching process and the influence of leaching amount on the migration behavior of the OPEs in surface soil, provides theoretical support for further deep research on the environmental behavior of the OPEs, and has very important theoretical significance and practical significance for protecting the environment and human health.
The main instruments selected during the experiment are referred to table 1.
Table 1: instrumentation apparatus
The main chemicals used during the experiment are referred to table 2.
Table 2: chemical reagent
*: the 6 standards were: TEP, TNBP, TBOEP, TPHP, TCIPP and TDCIPP
**: the internal standard substances are: TNBP-d27 and TPHP-d15
According to the composition and concentration level of the OPEs in the soil samples of multiple regions, 6 representative OPEs are selected, wherein the OPEs comprise three alkyl OPEs (TEP, TNBP and TBOEP), one aryl OPE (TPHP) and two chloroalkyl OPEs (TCIPP and TDCIPP).
As shown in figure 1, the specific method for detecting the migration of the organic phosphate in the soil comprises the following steps:
the method comprises the following steps: collecting soil samples
Selecting Tianjin south area (39 degrees 0 '7.66' N and 117 degrees 18 '19.44' E) as a soil sample collection point, collecting samples by a plum blossom distribution method, and taking 6 samples from the depth of 0-5cm, 5-10cm, 10-15cm, 15-20cm, 20-25cm and 25-30 cm away from the soil surface. Wrapping the soil sample with pre-cleaned tinfoil paper, sealing in a self-sealing bag, transporting to a laboratory, air drying at room temperature to remove large particulate matters such as sand, etc., mashing in a bowl, grinding, sieving with a 10-mesh sieve (sieving with a 100-mesh sieve for part of 0-5cm soil sample), and storing at-20 deg.C.
Step two: migration experiment
S201: soil aging treatment
6 organic phosphate ester standard substances are dissolved in acetonitrile to prepare 5 mg/mL -1 Standard stock solutions of (4). During the experiment, 600 g of a soil sample (0-5cm of surface soil) is weighed in a 1000mL beaker, in order to ensure that the OPEs and the soil are uniformly mixed, firstly, the prepared OPEs stock solution is added into 100mL of ultrapure water to prepare an OPEs mixed solution, and then, the OPEs mixed solution and the soil are fully mixed, so that the concentration of the OPEs in the soil reaches a target level. And finally, placing the beaker in a fume hood for ventilation for 3 hours to fully volatilize the acetonitrile, and aging for 15 days at room temperature. During the experiment, ventilation was carried out for 3 hours every day, and the soil surface was kept moist until the experiment was completed. The initial amounts of the 6 standards (i.e., TEP, TNBP, TCIPP, TDCIPP, TBOEP, and TPHP) in the aging experiment were: 500. mu.g, 2.1mg, 400. mu.g and 200. mu.g. After the aging test is finished, placing the aged soil sample in a beaker which is cleaned in advance, freezing and drying the soil sample, mashing and sieving the dried soil sample, and storing the soil sample at the low temperature of-20 ℃.
S202: earth pillar leaching experiment
The soil column leaching experimental apparatus was designed to explore the effect of the amount of leachate on the migration of OPEs in the soil, the details of the design are shown in Table 3.
Table 3: earth pillar leaching simulation experiment design
The soil column leaching experimental device comprises 3 organic glass columns and peristaltic pumps; wherein, organic glass post length is 36cm, and the internal diameter is 5cm, the setting of soil in the organic glass post is as follows: filling sample soil into the column from the bottom layer to the top layer in sequence, placing the aged soil sample on the surface layer, compacting all the soil of the section layer slightly, and filling the soil with the soil part of 30 cm; the column was then saturated with deionized water and air dried naturally for 2 days.
The peristaltic pump is used to control the flow rate of the leachate. The inlet end of a hose of the peristaltic pump is arranged at the bottom of the beaker, and the outlet end of the hose is fixed above the organic glass column and used for spraying water into the glass column. In order to simulate the migration characteristics of OPEs in a soil profile as truly as possible, according to Tianjin City Water resources bulletin issued by Tianjin City Water administration, 2010-2018 annual average rainfall in Tianjin City is 560 mm. Therefore, the average annual rainfall for the leaching experiments was about 1100mL, at 1mL min per day -1 220mL of rainfall. After each rainfall event is finished, collecting the overlying water as a water sample, draining the residual water in the column after the leaching test is finished, and carrying out layered sampling on the soil.
S203: pretreatment
And (3) placing the soil sample sampled in the step (S202) in a beaker which is cleaned in advance, freezing and drying the soil sample, and performing soil sample pretreatment after the dried soil sample passes through a 100-mesh screen.
The pretreatment of the soil sample comprises the following steps:
ultrasonic centrifugal extraction: a10 g sample of soil was weighed into a 50mL centrifuge tube, 2ng of internal standard materials (TNBP-d27 and TPHP-d15), 20mL of acetonitrile were added in sequence, and an appropriate amount of copper powder was added to remove sulfur elements. Shaking, performing ultrasonic extraction for 15min, centrifuging at 3000rpm for 10min, standing, and collecting supernatant. Repeating the above processes twice, transferring the supernatant obtained in the two operations to a rotary evaporation bottle, and performing solid phase extraction when the rotary evaporation is carried out to about 1 mL;
solid phase extraction: the solid phase extraction column (HLB) was activated with 5mL of dichloromethane, 5mL of ethyl acetate, and 5mL of methanol in sequence, and the sample was then run at 4mL min -1 Is passed through the solid phase extraction column. After sampling, keeping the solid phase extraction column in a vacuum state, vacuumizing at negative pressure for 30min, and then eluting twice with 6mL ethyl acetate to obtain eluent;
nitrogen blowing: blowing the eluent in a 10mL glass test tube by a nitrogen blowing instrument under the condition of 37 ℃ water bath by using high-purity nitrogen, then rinsing the test tube by using ethyl acetate, transferring the rinsing solution into an injection bottle, and blowing the rinsing solution to be nearly dry under the same nitrogen blowing condition;
and (3) volume fixing: and (3) diluting to 200 mu L with methanol, uniformly mixing by vortex, filtering with a 0.22 mu m filter membrane by using a needle filter to obtain a sample after solid phase pretreatment, storing the sample after solid phase pretreatment in a refrigerator at the temperature of-20 ℃ and carrying out HPLC-MS detection.
Step three: analysis of
S301: setting of chromatographic mass spectrometry parameters
The high performance liquid chromatography conditions include: the chromatographic column is Zorbax Eclipse Plus C 18 Columns (2.1 mm. times.150 mm, 3.5 μm); the column temperature was set to 40 ℃; the mobile phase A is 0.1 percent aqueous solution of formic acid, and the mobile phase B is pure methanol; the flow rate was set to 0.4 L.min -1 (ii) a The injection volume was set to 10. mu.L. The gradient elution conditions are shown in Table 4.
Table 4: gradient elution conditions
Mass spectrometry was performed in spot spray ionization mode, and the prime ions were collected using quantitative reaction monitoring (MRM). Other parameters: the ion source temperature is set to 300 ℃; the drying airflow rate was set to 7 L.min -1 (ii) a Atomizer pressure was 45 psi; the desolventizing temperature is 350 ℃; the flow rate of sheath gas is 11L/min -1 (ii) a Impact voltage and nozzle voltageRespectively 3.5kV and 0 kV. The mass spectral parameters of each target compound are shown in table 5.
Table 5: OPES HPLC-MS parameters
S302: quality control and assurance
Plastic products are avoided as much as possible in the processes of collecting, storing and pre-treating soil samples so as to avoid generating blank pollution. The water used in the experiment process is ultrapure water, all glassware is washed once by using the ultrapure water and methanol, and the glassware is dried for 2 hours at the temperature of 150 ℃ so as to achieve the aim of removing impurities. The quality control experiments conducted in this study included: parallel samples, field blanks, transport blanks, procedure blanks, solvent blanks, and spiked samples to ensure accuracy of the experimental process.
In order to correct the systematic error of the whole experimental process, an internal standard method is adopted to establish a standard curve. The concentration of the internal preparation standards (TNBP-d27 and TPHP-d15) is 10 ng/ml -1 The concentrations of the 6 organic phosphate esters are 1, 2, 5, 10, 25, 50, 100 and 200 ng/ml -1 The 6 kinds of organic phosphate mixed standard solutions are tested on a computer to determine the peak area of the quantitative ion integral, and a relation curve of the concentration ratio (the measured component and the internal standard substance) and the area ratio (the measured component and the internal standard substance) is made, and the curve is a standard curve, as shown in fig. 2.
The experimental results show that the correlation coefficient R of the quantitative standard curve of each OPE 2 Greater than 0.99, relative standard error RSD<30 percent. OPEs were not detected in the field blank, transport blank, procedure blank and solvent blank experiments. In addition, the recovery rates of the internal standard substances TPHP-d15 and TNBP-d27 are in the range of 80 +/-30.2% and 110 +/-33%, and the recovery rate of the OPEs in the matrix labeled sample is 75% -118%, which belongs to an acceptable range. Limit of detection (LOD) and quantitation of instrumentsThe Limit (LOQ) is set to 3 times and 10 times S/N, respectively. In the data processing, the concentration lower than LOD was regarded as undetected, and the concentration higher than LOD and lower than LOQ was regarded as 1/2 LOQ. The detection and quantification limits of OPEs in soil samples are shown in Table 6.
Table 6: detection limit and quantification limit of OPEs in soil sample
S303: performing high performance liquid chromatography tandem mass spectrometry on the pretreated actual soil sample
This example measured the concentration levels of 6 OPEs in soil samples at each section level of the sample site, including 3 alkyl OPEs (TEP, TNBP and TBOEP), 2 chloro OPEs (TCIPP and TDCIPP) and one aryl OPEs (TPHP), the concentration levels of which are shown in Table 7. In all profile layer soil samples, TEP, TCIPP and TNBP are the most abundant OPEs, the contribution rate of the OPEs reaches 95.24%, and the contribution rate of the OPEs is as follows from large to small: TEP>TCIPP> TNBP>TPHP>TBOEP>TDCIPP with average concentrations of 31.43, 8.92, 6.09, 1.29, 0.60 and 0.42 ng g -1 dw. TCIPP is the most predominant ops in soil samples.
Table 7: concentration and composition of soil organophosphate
n.d.: not detected out
S304: performing high performance liquid chromatography tandem mass spectrometry on soil sample after rainfall simulation
OPEs in the cross-sectional layers of the leached A, B and C experimental column groups exhibited similar distribution characteristics, as shown in FIG. 3, with most OPEs accumulating at depths of 0-10 cm. The concentration at a particular depth is higher than the adjacent depth, which is referred to as the accumulated depth. For example, the cumulative depth of TEP and TCIPP was 10-15cm and 5-10cm, respectively, at 20 days of leaching. It can be clearly seen that the cumulative depth of TEP at the end of the leaching experiment > the cumulative depth of TCIPP > the cumulative depth of TNBP, TDCIPP, TBOEP and TPHP. As the amount of leaching increased, the concentrations of TNBP, TDCIPP, TBOEP and TPHP increased gradually for the 5-10cm profile layer, but the profile layer failed to be cumulative depth during the leaching experiment, while TEP and TCIPP exhibited variations in cumulative depth. The results show that the physicochemical properties of OPEs play a role in the leaching process. In the leaching process, OPEs in surface soil are desorbed and leached, and gradually migrate to a deep soil section and accumulate. Thus, there is a risk that OPEs in the soil will be diverted to groundwater under prolonged leaching.
Although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that various changes, modifications and substitutions may be made without departing from the spirit and scope of the invention, and it is intended that all changes, modifications and substitutions that are not essential to the skilled in the art are to be construed as being limited by the scope of the present invention.
Claims (6)
1. A method for detecting migration behavior of organic phosphate in a vertical direction of soil comprises the following steps:
collecting a plurality of soil samples from different depths from the soil surface, and obtaining the environmental background concentration of 6 organic phosphate esters in the soil samples after air drying;
6 organic phosphate ester standard substances are dissolved in acetonitrile to prepare 5 mg/mL -1 Adding the standard stock solution into 100mL of ultrapure water to prepare an OPES mixed solution; selecting a surface soil sample closest to the earth surface and mixing the surface soil sample with the OPEs mixed solution uniformly in a beaker, ventilating for 3 hours to fully volatilize acetonitrile, and aging for 15 days at room temperature; then will bePlacing the aged soil sample in a beaker which is cleaned in advance, freezing, drying, crushing, sieving, and storing at a low temperature of-20 ℃;
and (3) performing a soil column leaching experiment: sequentially filling the collected air-dried sample soil into an organic glass column from the bottom layer to the top layer according to the collection concentration, and placing an aged soil sample on the top layer; setting experimental rainfall according to the annual rainfall of the collected soil land by programming, and controlling the flow speed of leachate to spray water to the top of the organic glass column by using a peristaltic pump to simulate rainfall; after each rainfall event is finished, draining water in the column, and carrying out layered sampling on the soil;
placing the sampled soil sample in a beaker which is cleaned in advance, freezing and drying the soil sample, performing solid phase pretreatment on the dried soil sample after the dried soil sample passes through a 100-mesh screen, and storing the pretreated soil sample in a refrigerator at the temperature of-20 ℃;
and carrying out quantitative analysis on the pretreated sample by using a high performance liquid chromatography-mass spectrometer.
2. The method of claim 1, wherein the 6 organophosphate standards comprise triethyl phosphate, tributyl phosphate, tris (1-chloro-2-propyl) phosphate, tris (1, 3-dichloro-2-propyl) phosphate, tris (butoxyethyl) phosphate, and triphenyl phosphate.
3. The method for detecting the migration of organic phosphate in soil according to claim 1, wherein the soil column leaching experiment uses an apparatus comprising: 3 organic glass columns and peristaltic pumps; wherein, organic glass post length is 36cm, and the internal diameter is 5cm, the setting of soil in the organic glass post is as follows: filling sample soil into the column from the bottom layer to the top layer in sequence, placing the aged soil sample on the surface layer, compacting all the soil of the section layer slightly, and filling the soil with the soil part of 30 cm; saturating the soil column with deionized water, and naturally drying for 2 days; the inlet end of a hose of the peristaltic pump is arranged at the bottom of the beaker and used for supplying water, and the outlet end of the hose is fixed above the organic glass column and used for spraying water into the glass column.
4. The method for detecting the migration of organic phosphate in soil according to claim 1, wherein plastic products are avoided during the collection, storage and pretreatment of soil samples to reduce pollution; the process water is ultrapure water, all glassware is washed three times by using the ultrapure water and methanol, and is dried for 2 hours at the temperature of 150 ℃ so as to achieve the aim of removing impurities.
5. The method for detecting the migration of an organic phosphate in soil according to claim 1, wherein the pretreatment of the solid phase comprises:
ultrasonic centrifugal extraction: weighing 10g of soil sample, placing the soil sample in a 50mL centrifuge tube, sequentially adding 2ng of internal standard substances (TNBP-d27 and TPHP-d15) and 20mL of acetonitrile, and adding a proper amount of copper powder to remove sulfur elements; shaking, performing ultrasonic extraction for 15min, centrifuging at 3000rpm for 10min, standing, and pouring out supernatant; repeating the above processes twice, transferring the supernatants obtained by the two operations to a rotary evaporation bottle, and performing solid phase extraction when the rotary evaporation is about 1 mL;
solid phase extraction: the solid phase extraction column (HLB) was activated with 5mL of dichloromethane, 5mL of ethyl acetate, and 5mL of methanol in sequence, and the sample was then run at 4mL min -1 Through the solid phase extraction column; after sampling, keeping the solid phase extraction column in a vacuum state, vacuumizing for 30min under negative pressure, and then eluting twice with 6mL ethyl acetate to obtain eluent;
nitrogen blowing: blowing the eluent in a 10mL glass test tube by a nitrogen blowing instrument under the condition of 37 ℃ water bath by using high-purity nitrogen, then rinsing the test tube by using ethyl acetate, transferring the rinsing solution into an injection bottle, and blowing the rinsing solution to be nearly dry under the same nitrogen blowing condition;
volume fixing: and (3) diluting to 200 mu L with methanol, uniformly mixing by vortex, filtering with a 0.22 mu m filter membrane by using a needle filter to obtain a sample subjected to solid phase pretreatment, storing the sample subjected to solid phase pretreatment in a refrigerator at the temperature of-20 ℃, and performing HPLC-MS detection.
6. According to claim 1, there areThe method for detecting the migration of the organic phosphate in the soil is characterized in that the quantitative analysis is to compare a sample measured value with a standard curve by selecting an internal standard method to obtain the accurate content of the organic phosphate in the sample; drawing an organic phosphate standard curve, namely preparing an internal standard with the concentration of 10 ng/ml -1 The concentrations of the 6 organic phosphate esters are 1, 2, 5, 10, 25, 50, 100 and 200 ng/ml -1 The peak area of the quantitative ion integral is tested on a computer, and a relation curve of the concentration ratio and the area ratio is made, wherein the curve is a standard curve; the internal standards refer to TNBP-d27 and TPHP-d 15.
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