CN112540094B - Rapid nanofiber membrane determination method for soil easily-dissociated heavy metals - Google Patents
Rapid nanofiber membrane determination method for soil easily-dissociated heavy metals Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims abstract description 130
- 239000012528 membrane Substances 0.000 title claims abstract description 90
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 73
- 239000002121 nanofiber Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004876 x-ray fluorescence Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000007605 air drying Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000009616 inductively coupled plasma Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000012086 standard solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000002513 implantation Methods 0.000 claims description 3
- 238000012417 linear regression Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 18
- 238000000227 grinding Methods 0.000 abstract description 8
- 238000007873 sieving Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000003891 environmental analysis Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
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Abstract
The invention relates to the technical field of environmental analysis, and discloses a rapid nanofiber membrane measuring method for soil easily-dissociated heavy metals, which comprises the following steps: measuring the humidity of soil to be measured, and after the humidity requirement is met, dispersedly implanting a plurality of nanofiber membranes into the soil, wherein the membranes are kept flat and completely buried by the soil in the implanting process; after the membrane is implanted, keeping 100% of the maximum field water capacity for at least 10 hours; carefully taking out all the nanofiber membranes buried in the soil from the soil by using plastic tweezers, cleaning, air-drying, and measuring the air-dried nanofiber membranes by using a calibrated X-ray fluorescence spectrometer to obtain the content of the heavy metal indicating the soil in the easily-dissociated state; the measuring method has small disturbance to the soil, and the film is directly buried in the soil without any grinding to the soil; in addition, in the analysis process, the soil does not need to be collected back to a laboratory for grinding, sieving and other pretreatment, and only certain soil humidity needs to be controlled, so that the on-site in-situ non-disturbance analysis can be really realized.
Description
Technical Field
The invention relates to the technical field of environmental analysis, relates to a rapid nanofiber membrane determination method for soil easily-dissociated heavy metals, and mainly relates to a method for rapidly detecting the forms of heavy metals in polluted soil by adopting a nanofiber membrane and an X-ray fluorescence device.
Background
The forms of heavy metals in soil include an ionic state in a soil solution, an exchange state in a soil solid phase, a soil iron manganese oxide and organic matter combined state, and a residue state combined in a soil mineral lattice, wherein the ionic state in the soil solution and the exchange state in the solid phase are generally regarded as forms with the highest effectiveness as easily-dissociated states, and are easily absorbed and utilized by crops and organisms in soil.
In the past, the analysis of soil heavy metal easily-dissociated state mainly adopts static extraction of various chemical reagents. For example, 0.01mol/L calcium chloride, 1.0mol/L ammonium acetate (pH 7), 0.1mol/L sodium nitrate, and the like. The extraction method comprises the steps of taking a soil sample back to a laboratory, carrying out air drying, grinding, sieving by a 100-mesh sieve, carrying out long-time oscillation extraction on the obtained supernatant under the condition that an extraction reagent and soil are 40:1, centrifuging, filtering, and measuring the concentration of heavy metal in the supernatant by using an inductively coupled plasma emission spectrometer (ICP) to obtain the content of the easily-dissociated heavy metal. However, the heavy metal balance in the soil-solution of the soil after the treatment is destroyed, and the content of the extracted and measured heavy metal cannot represent the content of the real easily-dissociated heavy metal in the soil. And the extraction process of the methods is complex and long, a large amount of chemical reagents and labor are consumed, the analysis cost is high, and the potential environmental pollution problem is also brought.
For example, the DGT technology has been widely used since the establishment of the DGT technology in 1994, and for example, the invention of Chinese patent with the grant of CN106290785B discloses a method for separating heavy metals in different forms in soil by using the DGT technology; DGT devices consist of a well-defined diffusion phase gel (diffusion membrane and filter) and a binding phase gel with strong complexation. According to the first Fick's diffusion law, when the DGT device is in an ambient medium, the analyte to be detected passes through the filter membrane and the diffusion membrane gel, and is captured by the binding phase, so that a stable linear concentration gradient is formed in the diffusion layer. The main steps of the technology include taking the soil to be tested back to the laboratory, air drying, grinding and sieving with a 60-mesh sieve, pre-culturing the soil for 48 hours under the condition of 60% field water capacity, and then placing the DGT device into the soil for stabilization for 24 hours. The DGT apparatus was then removed, the heavy metals in the bound phase were eluted with nitric acid into a collector and the heavy metal concentration in the eluate was determined by ICP.
However, the form of heavy metals in soil is a dynamic balance under the condition of soil-soil solution, and can be changed by soil disturbance, so that a detection technology which is as close to in-situ undisturbed as possible is required to truly reflect the content of easily-dissociated heavy metals in soil. However, the static extraction method of the traditional chemical reagent takes the soil back to the laboratory, and the morphological characteristics of the heavy metal in the soil are seriously damaged through the processes of grinding, adding a large amount of chemical reagent and the like. Therefore, the heavy metal morphology detected by the method is not the morphology in real soil. While the DGT technique reduces this disturbance, the following problems exist in use:
(1) the soil needs to be sieved by a 60-mesh sieve, and the original heavy metal form in the soil can be changed in the process;
(2) after the DGT device is taken out of the soil, the heavy metal in the binding phase needs to be eluted by nitric acid, and more nitric acid solution is used in the step, so that potential pollution is caused to the environment;
(3) compared with a nano-fiber membrane material, the DGT device is complex in composition and needs to be composed of a shell, diffusion gel and binding phase gel.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a rapid nanofiber membrane measuring method for soil easily-dissociable heavy metals, which has small soil disturbance and can be directly buried in soil without any grinding; in addition, in the analysis process, the soil does not need to be collected back to a laboratory for grinding, sieving and other pretreatment, and only certain soil humidity needs to be controlled, so that the on-site in-situ non-disturbance analysis can be really realized.
In order to achieve the above purpose, the invention provides the following technical scheme:
a rapid nanofiber membrane measuring method for soil easily-dissociated heavy metals comprises the following steps:
step 1: measuring the humidity of the soil to be measured, and if the humidity reaches or exceeds 60% of the maximum water holding capacity in the field, directly performing the step 3, otherwise, performing the step 2;
step 2: adding deionized water into the soil to be detected until the humidity of the soil reaches 60% of the maximum field water capacity and the humidity of the soil stably reaches 60% of the maximum field water capacity within 24 hours, and then performing the step 3; if the soil humidity is reduced in a 24-hour stabilization period, the water needs to be supplemented to the maximum field water capacity of 60%;
and step 3: continuously adding deionized water into the soil to be tested until the humidity of the soil reaches 100% of the maximum field water capacity, and at the moment, dispersedly implanting a plurality of nanofiber membranes into the soil, wherein the membranes are kept flat and completely buried by the soil in the implantation process;
after the membrane is implanted, keeping 100% of the maximum field water capacity for at least 10 hours;
and 4, step 4: after 10 hours, carefully taking all the nanofiber membranes buried in the soil out of the soil with plastic tweezers, washing the membrane surface with deionized water to remove soil particles adhered to the surface, after three times of washing, naturally drying at room temperature (25 ℃), and storing the membranes in sample boxes respectively;
and 5: and (3) measuring the air-dried nanofiber membrane by using a calibrated X-ray fluorescence spectrometer to obtain the content of the easily-dissociated heavy metal in the indicated soil.
Preferably, the heavy metals measured include lead, zinc, copper, nickel, chromium.
Preferably, the calibration method of the X-ray fluorescence spectrometer in the step 5 comprises the following steps:
s1: preparing a series of heavy metal standard solutions with concentration gradients by using a dilute nitric acid solution, respectively immersing the nanofiber membrane into the heavy metal standard solutions with different concentrations, after stabilizing for 10 hours at room temperature, cleaning the surface by using deionized water, then air-drying at room temperature, and measuring the nanofiber membrane by using an X-ray fluorescence spectrometer to obtain an XRF (X-ray fluorescence) reading A;
s2: putting the nanofiber membrane into a centrifuge tube, eluting with ultrapure nitric acid, placing the centrifuge tube on a shaking table for shaking, filtering with a supernatant filter membrane, and measuring the concentration of heavy metal in the filtrate by using an inductively coupled plasma mass spectrometer;
s3: dividing the concentration of the heavy metal in the filtrate by the mass (dry weight) of the nanofiber membrane to obtain the content Cn of the heavy metal in the nanofiber membrane;
s4: and (3) calibrating the X-ray fluorescence spectrometer by establishing a linear regression model of the XRF reading A and the heavy metal content Cn.
The calibration of the X-ray fluorescence spectrometer is not necessary every time, theoretically, the same membrane material and the same elements can be calibrated only once; in actual analysis, the same membrane material and the same elements can be calibrated at intervals of 5000 samples or half a year.
Preferably, the heavy metal standard solution is formulated for at least 3 groups, preferably 3-5 groups.
Preferably, the nanofiber membrane is circular and has a diameter of 1 cm.
Preferably, 6-8 membranes of the same type size are placed per square of soil.
Preferably, the sample box is made of plastic or glass.
The principle of the method is as follows: referring to the attached figure 1, the easily-dissociated heavy metals in the soil are mainly in the form of heavy metals which are weakly adsorbed and easily exchanged on the surfaces of some soil particles, and the heavy metals and the heavy metal content in the soil solution keep dynamic balance; after the nanofiber membrane with strong adsorption capacity is embedded in the system, ions and complex heavy metals can be continuously adsorbed from a soil solution, so that easily-dissociated heavy metals are continuously released into the soil solution until dynamic adsorption-desorption balance is achieved between the soil solution and the nanofiber membrane; and then, directly measuring the content of the heavy metal on the nanofiber membrane by using a calibrated x-ray fluorescence spectrometer.
This content is indicative of the easily dissociable form of the heavy metal in the soil and is also the form of the heavy metal most likely to be taken up by soil organisms.
The method comprises the steps of burying a nano-fiber membrane material in heavy metal polluted soil containing 100% of maximum field water holding capacity for about 10 hours, taking out the nano-fiber membrane material, washing with deionized water to remove surface soil particles, naturally drying the nano-fiber membrane material at room temperature, and analyzing the content of heavy metals in the nano-fiber membrane material by using calibrated x-ray fluorescence equipment, wherein the content is the content of easily-dissociated heavy metals in the soil.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method has small disturbance to the soil, does not need to grind the soil, and can be used for directly burying the membrane in the soil; in the analysis process, the soil is not required to be collected back to a laboratory for grinding, sieving and other pretreatment, and only certain soil humidity is required to be controlled, so that the on-site in-situ non-disturbance analysis can be really realized;
(2) the method has simple using device, only one nanofiber membrane material with the diameter of 1cm is used, and no other additional device is used;
(3) no chemical reagent is needed, only a small amount of deionized water is needed to clean soil particles on the surface of the membrane in the whole detection process, no other chemical reagent is needed, no secondary pollution is caused, and the method is a green detection technology;
(4) the analysis process flow is simple, controllable and repeatable; the detection speed is high, the XRF is combined to determine the content of the heavy metal in the nitrocellulose membrane material to realize the rapid analysis of the soil easily-dissociated heavy metal, the method is obviously improved compared with the conventional method for determining the total amount of the soil heavy metal by XRF, and the detection time can be shortened to be within 10 seconds.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
FIG. 2 is a schematic diagram of the method of the present invention.
FIG. 3 is a diagram of the determination of the content of easily dissociable lead in the actual contaminated soil by using a rapid nanofiber membrane method, and FIG. 3(1) an XRF (X-ray fluorescence) determination instrument is calibrated by using 3 nanofiber membranes with different lead contents; fig. 3(2) comparison of the XRF and ICP measurements of nanofiber membranes taken from contaminated soils.
Detailed Description
A rapid nanofiber membrane measuring method for soil easily-dissociated heavy metals comprises the following steps:
step 1: measuring the humidity of the soil to be measured, and if the humidity reaches or exceeds 60% of the maximum water holding capacity in the field, directly performing the step 3, otherwise, performing the step 2;
step 2: adding deionized water into the soil to be detected until the humidity of the soil reaches 60% of the maximum field water capacity and the humidity of the soil stably reaches 60% of the maximum field water capacity within 24 hours, and then performing the step 3; if the soil humidity is reduced in a 24-hour stabilization period, the water needs to be supplemented to the maximum field water capacity of 60%;
and step 3: continuously adding deionized water into the soil to be tested until the humidity of the soil reaches 100% of the maximum field water capacity, and at the moment, dispersedly implanting 6-8 circular nanofiber membranes with the diameter of 1cm into each square of the soil, wherein the membranes are kept flat and completely buried by the soil in the implantation process;
after the membrane is implanted, keeping 100% of the maximum field water capacity for at least 10 hours;
and 4, step 4: after 10 hours, carefully taking all the nanofiber membranes buried in the soil out of the soil with plastic tweezers, washing the membrane surface with deionized water to remove soil particles adhered to the surface, after three times of washing, naturally drying at room temperature (25 ℃), and storing the membranes in plastic or glass sample boxes respectively;
and 5: and (3) measuring the air-dried nanofiber membrane by using a calibrated X-ray fluorescence spectrometer to obtain the content of the easily-dissociated heavy metal in the indicated soil.
The calibration method of the X-ray fluorescence spectrometer in the step 5 comprises the following steps:
s1: preparing 3-5 groups of heavy metal standard solutions with concentration gradients by using a dilute nitric acid solution, respectively immersing the nanofiber membrane into the heavy metal standard solutions with different concentrations, stabilizing at room temperature for 10 hours, cleaning the surface by using deionized water, then air-drying at room temperature, and measuring the nanofiber membrane by using an X-ray fluorescence spectrometer to obtain an XRF (X-ray fluorescence) reading A;
s2: placing the nanofiber membrane in a 15mL centrifuge tube, eluting with 3mL ultrapure nitric acid, placing the centrifuge tube on a shaking table, shaking for at least 2 hours, and filtering the supernatant with a 0.45-micrometer filter membrane; measuring the concentration of heavy metal in the filtrate by using an inductively coupled plasma mass spectrometer;
s3: dividing the concentration of the heavy metal in the filtrate by the mass (dry weight) of the nanofiber membrane to obtain the content Cn of the heavy metal in the nanofiber membrane;
s4: and (3) calibrating the X-ray fluorescence spectrometer by establishing a linear regression model of the XRF reading A and the heavy metal content Cn.
In this embodiment, lead is taken as an example, the easily-dissociated state of lead is relatively low, and if the analysis result of lead is good, elements such as zinc, copper, nickel, chromium and the like can be well analyzed.
Selecting three actual lead-polluted soils with different degrees, and respectively adopting a nanofiber membrane and an XRF instrument to rapidly determine the content of easily-dissociated heavy metals in the soil.
Example 1: selecting the test soil 1 polluted by lead, taking out the nanofiber membrane implanted in the test soil 1 according to the steps with the total lead content of 1256mg/kg and the soil pH of 8.79, and detecting by adopting two analysis methods of calibrated XRF and ICP.
Example 2: selecting the test soil 2 polluted by lead, wherein the total lead content is 6524mg/kg, the soil pH is 7.78, taking out the nanofiber membrane implanted in the test soil 2 according to the analysis steps, and detecting by adopting two analysis methods of calibrated XRF and ICP.
Example 3: selecting the test soil 3 polluted by lead, wherein the total lead content of the test soil 3 is 9486mg/kg, the pH value of the soil is 8.13, taking out the nanofiber membrane implanted in the test soil 3 according to the analysis steps, and detecting by adopting two analysis methods of calibrated XRF (X-ray fluorescence) and ICP (inductively coupled plasma).
The data from examples 1-3 were compared and the results are shown in FIG. 3.
The analysis shows that: the two measuring instruments have good correspondence when the measuring instrument is less than 200mg/kg, and both data are on the line of x-y; at high concentrations (around 1800 mg/kg), the XRF measurement will be slightly higher than the ICP measurement. But in general terms, rapid measurement of easily dissociable heavy metal content using nanofiber membrane materials in combination with XRF can be used to assess contaminated soil.
XRF calibration results As shown in FIG. 3(1), the XRF readings (A) and ICP measurements achieved a very significant linear correlation (R)2＝0.99588,p<0.01)。
Claims (6)
1. A rapid nanofiber membrane measuring method for soil easily-dissociated heavy metals is characterized by comprising the following steps:
step 1: measuring the humidity of the soil to be measured, and if the humidity reaches or exceeds 60% of the maximum water holding capacity in the field, directly performing the step 3, otherwise, performing the step 2;
step 2: adding deionized water into the soil to be detected until the humidity of the soil reaches 60% of the maximum field water capacity and the humidity of the soil stably reaches 60% of the maximum field water capacity within 24 hours, and then performing the step 3; if the soil humidity is reduced in a 24-hour stabilization period, the water needs to be supplemented to the maximum field water capacity of 60%;
and step 3: continuously adding deionized water into the soil to be tested until the humidity of the soil reaches 100% of the maximum field water capacity, and at the moment, dispersedly implanting a plurality of nanofiber membranes into the soil, wherein the membranes are kept flat and completely buried by the soil in the implantation process;
after the membrane is implanted, keeping 100% of the maximum field water capacity for at least 10 hours;
and 4, step 4: carefully taking all the nanofiber membranes buried in the soil out of the soil by using plastic tweezers, washing the surfaces of the membranes by using deionized water to remove soil particles adhered to the surfaces, naturally drying the membranes at room temperature after three times of washing, and respectively storing the membranes in sample boxes;
and 5: the air-dried nanofiber membrane is measured by a calibrated X-ray fluorescence spectrometer,
the calibration method of the X-ray fluorescence spectrometer comprises the following steps:
s1: preparing a series of heavy metal standard solutions with concentration gradients by using a dilute nitric acid solution, respectively immersing the nanofiber membrane into the heavy metal standard solutions with different concentrations, after stabilizing for 10 hours at room temperature, cleaning the surface by using deionized water, then air-drying at room temperature, and measuring the nanofiber membrane by using an X-ray fluorescence spectrometer to obtain an XRF (X-ray fluorescence) reading A;
s2: putting the nanofiber membrane into a centrifuge tube, eluting with ultrapure nitric acid, placing the centrifuge tube on a shaking table for shaking, filtering with a supernatant filter membrane, and measuring the concentration of heavy metal in the filtrate by using an inductively coupled plasma mass spectrometer;
s3: dividing the concentration of the heavy metal in the filtrate by the mass of the nanofiber membrane to obtain the content Cn of the heavy metal in the nanofiber membrane, wherein the mass of the nanofiber membrane is the mass of the nanofiber membrane in a dry weight state;
s4: and (3) calibrating the X-ray fluorescence spectrometer by establishing a linear regression model of the XRF reading A and the heavy metal content Cn, so as to obtain the content of the heavy metal indicating the soil in the easily-dissociated state.
2. The method for rapidly measuring the nanofiber membrane of the soil easily-dissociable heavy metal according to claim 1, wherein at least 3 groups of heavy metal standard solutions are prepared.
3. The method for rapidly measuring the nanofiber membrane of the heavy metal in the soil easily-dissociable state according to claim 1 or 2, wherein the measured heavy metal comprises lead, zinc, copper, nickel and chromium.
4. The method for rapidly measuring the nanofiber membrane of the soil easily-dissociable heavy metal according to claim 1, wherein the nanofiber membrane is circular and has a diameter of 1 cm.
5. The method for rapidly measuring the nanofiber membranes of the soil easily-dissociable heavy metals according to claim 4, wherein 6-8 membranes with the same type size are placed in each square of soil.
6. The method for rapidly measuring the nanofiber membrane of the soil easily-dissociable heavy metal according to claim 1, wherein the sample box is made of plastic or glass.
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| CN113941384B (en) * | 2021-11-21 | 2022-11-01 | 洛阳职业技术学院 | Capsule type secondary centrifuge tube capable of being applied to rapid nondestructive analysis |
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