CN114878615A - Method for carrying out in-situ sampling and detection on effective state metal based on DGT-XRF combined technology - Google Patents

Method for carrying out in-situ sampling and detection on effective state metal based on DGT-XRF combined technology Download PDF

Info

Publication number
CN114878615A
CN114878615A CN202210490946.5A CN202210490946A CN114878615A CN 114878615 A CN114878615 A CN 114878615A CN 202210490946 A CN202210490946 A CN 202210490946A CN 114878615 A CN114878615 A CN 114878615A
Authority
CN
China
Prior art keywords
dgt
xrf
detection
sample
soil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210490946.5A
Other languages
Chinese (zh)
Inventor
王燕
杭小帅
周莉
尤晓慧
张澜
朱冬冬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Institute of Environmental Sciences MEE
Original Assignee
Nanjing Institute of Environmental Sciences MEE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Institute of Environmental Sciences MEE filed Critical Nanjing Institute of Environmental Sciences MEE
Priority to CN202210490946.5A priority Critical patent/CN114878615A/en
Publication of CN114878615A publication Critical patent/CN114878615A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N2013/003—Diffusion; diffusivity between liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Abstract

The invention discloses a method for carrying out in-situ sampling and detection on effective state metals based on a DGT-XRF combined technology, which quantitatively obtains the effective state concentration of metals/metalloids in polluted water and soil by combining the DGT technology and a portable XRF technology. The method comprises the following specific steps: putting the ZrO-ChelexGT device into a polluted water body or soil in situ, standing for 8-48h, synchronously enriching a plurality of metal elements, taking out the DGT, cleaning the residual water and soil on the surface, and directly measuring by using a portable XRF (X-ray fluorescence spectrometer) to obtain the signal intensity values of the plurality of metal elements on the DGT film. And correcting according to a linear curve calibrated in advance by an indoor standard sample to obtain the effective state concentration of the metal in the water body or the soil of the sampling point. The invention relates to the technical field of environmental monitoring. The method for carrying out in-situ sampling and detection on the effective metal based on the DGT-XRF combined technology is simple to operate, high in sensitivity and high in analysis speed, and can realize rapid in-situ monitoring on various metal elements in the polluted water area and soil.

Description

Method for carrying out in-situ sampling and detection on effective state metal based on DGT-XRF combined technology
Technical Field
The invention relates to the technical field of environmental monitoring, in particular to a method for carrying out in-situ sampling and detection on effective-state metal based on a DGT-XRF combined technology.
Background
The technology of film Diffusion Gradient (DGT) is based on the principle of Fick's first-law ion diffusion, and the concentration of ions in an environmental medium with water is obtained through the gradient diffusion of target ions in a defined diffusion layer and the associated process research. The device of DGT measurement technique is composed of a fixed layer and a diffusion layer, ions pass through the diffusion layer in a diffusion mode and are captured by the fixed layer, a linear gradient distribution is formed on the diffusion layer, the ion concentration of one end close to the fixed film is maintained to be zero, and the concentration of one end in contact with a medium (C) DGT ) Comprises the following steps:
Figure BDA0003630913640000011
in the above formula, M is the accumulation amount of ions on the fixed membrane (molcm) -2 ) Δ g is the thickness (cm) of the diffusion layer, and Dg is the diffusion rate (cm) of ions in the diffusion film 2 s -1 ) And t is diffusion time(s). C DGT Is the mean concentration (molL) obtained by DGT analysis of the standing period -1 )。
Compared with the traditional destructive testing technology, the DGT technology can reflect the mobility and bioavailability of the target in the environmental medium more truly in an in-situ state, thereby better reflecting the nutrition or pollution level of the environmental medium. The advantage of DGT techniques over other in-situ passive sampling techniques is: 1) with selectivity, the DGT technique can only measure those soluble forms that can pass through the diffusive phase and can be accumulated by the immobilized membrane; 2) the time average concentration of the effective state of the substance to be detected can be provided, the DGT technology can accurately limit the sampling time, and a plurality of elements can be accumulated at the same time without mutual interference, so that the fluctuation of the ion concentration in the accumulation time can be ignored, and an average concentration value is provided for an analyzer; 3) the effective state of the ultra-trace substance can be measured through enrichment, the concentration of most metals in the deposit in the environment is low, and the DGT technology can enrich the trace substance by prolonging the sampling time, improve the concentration of the trace substance and reduce the analysis error.
The DGT enrichment process can simulate the migration and biological absorption process of target ions in the environment, and the analysis result is more scientific and reliable, which is just the defect of the traditional effective state determination method. The DGT determination process is simple, the operation environment requirement is low, the method has strong popularization and a very wide application prospect.
At present, field portable XRF (FP-XRF) is widely applied to field rapid determination of metal elements. The portable XRF fluorescence spectrometer has the advantages of multi-element simultaneous analysis, high analysis speed, in-situ analysis and the like, and can improve the analysis efficiency and greatly reduce the analysis time and cost. The principle of measurement is that atoms of most elements fluoresce at spectral energy when excited by x-rays. Qualitative and quantitative information of the elements can be obtained by detecting the number of spectral fluorescence photons of the sample. Compared with other methods for analyzing inorganic elements, the field-portable XRF has the following advantages: 1) no field calibration is required; 2) the operation is simple and does not need professional personnel; 3) the measurement is quick and only needs a few minutes; 4) as applicable to any given sample type. Traditional portable XRF is applied to soil and measurement of water system sediment sample mostly, but measurement accuracy can not satisfy microelement's required precision, and the concentrate sample generally has the characteristic of easy absorption, pollutes the XRF probe very easily, causes portable XRF measurement accuracy further to reduce.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method for carrying out in-situ sampling and detection on effective state metal based on a DGT-XRF combined technology, the DGT-XRF combined technology and the DGT-XRF combined technology are combined, metal elements are synchronously enriched by utilizing the DGT sampling technology, and then the portable XRF is used for carrying out on-site measurement, so that the content information of the metal in the polluted water body and the soil can be rapidly obtained in situ.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: the method for carrying out in-situ sampling and detection on the effective metal based on the DGT-XRF combined technology specifically comprises the following steps:
s1, preparing a DGT device;
s2, preparation of indoor standard sample film: establishing a standard curve of various heavy metal elements, putting the DGT device obtained in the step S1 into a mixed solution of various metal solutions with different concentration gradients for enrichment, determining one DGT with the same concentration by XRF to obtain a fluorescence signal value, extracting the other DGT by a solution extraction method, determining by ICP-MS to obtain an accumulated amount, establishing a relation between the XRF signal value and the accumulated amount, and recording the linear relation into portable XRF for calculation during detection of subsequent samples;
s3, carrying out DGT enrichment on a water body or soil sample on site: putting the DGT device into a polluted water body or soil in situ, standing for 8-48h, and synchronously enriching metal elements of Mn, Co, Ni, Cu, Zn, Pb, Cd, As or Cr;
and S4, detecting the DGT sample by using the portable XRF, and obtaining the content of the heavy metal effective state of the sample to be detected according to internal calculation.
Preferably, the DGT is used as a passive sampling method of the metal elements in the water body or the soil, the water body or the soil does not need to be collected to a laboratory, and a plurality of metal elements can be synchronously enriched in situ;
preferably, portable XRF is used as a detection method for rapid determination of elements on a DGT film;
preferably, the metal elements to be measured simultaneously include Mn, Co, Ni, Cu, Zn, Pb, Cd, As and Cr;
preferably, the metal form measured by DGT is the available state concentration, and the bioavailable part of the dissolved state concentration is not the total amount of the metal element;
preferably, the DGT device in step S1, which does not include a diffusion membrane and is composed of two membranes, i.e., a ZrO-Chelex immobilized membrane and a PVDF filter membrane, has an improved structure compared to a standard DGT device, shortens the absorption path of the target element by the immobilized membrane, and enhances the XRF-analyzed fluorescence signal without affecting the DGT measurement;
preferably, in step S2, multiple parallel standard sample films are prepared, multiple repeated measurements are performed, multiple random positions are selected at the same time, and an arithmetic mean is obtained;
preferably, in step S2, the DGT standard sample is measured by XRF, the sample is placed on a clean table, the XRF is precisely positioned, the XRF start button is turned on, the trigger is triggered, the instrument starts to measure, the XRF spot size is kept at 8mm, and the subsequent sample measurement is consistent with the standard curve parameter setting.
Preferably, in the step S3, the standing time is determined according to the concentration of the polluted water and soil, the enrichment time of a heavily polluted site is shortened, the enrichment time of a lightly polluted site is lengthened, the membrane is recovered after DGT enrichment is completed, the surface of the filter membrane is cleaned after recovery, and the membrane is kept dry and is measured as soon as possible;
preferably, in step S4, the DGT sample is measured by XRF to obtain the fluorescence signal value of each element, and the data is input to the Niton software to obtain the accumulated amount or concentration of the metal element in the sample according to the standard curve and calibration coefficient of different elements.
(III) advantageous effects
The invention provides a method for carrying out in-situ sampling and detection on effective-state metal based on a DGT-XRF combined technology. Compared with the prior art, the method has the following beneficial effects:
(1) the method for carrying out in-situ sampling and detection on the effective metal based on the DGT-XRF combined technology is simple to operate, does not need to sample to a laboratory for pretreatment and extraction, is low in labor and material consumption cost, rapid in determination, short in time consumption and low in cost, and does not need to use large instruments such as atomic absorption and ICP-MS.
(2) According to the method for carrying out in-situ sampling and detection on the effective metal based on the DGT-XRF combined technology, a standard calibration curve can be obtained only by once preparation of a laboratory standard sample and analysis of the corresponding XRF and a laboratory method, and the method can be applied to water and soil samples with any unknown content.
(3) According to the method for carrying out in-situ sampling and detection on the effective metal based on the DGT-XRF combined technology, the defects existing in single use are overcome by utilizing the technical advantages of DGT and XRF, multiple target metal elements can be synchronously enriched, the content of the target metal elements can be simultaneously detected, and errors of respective sampling and detection of single elements are avoided.
(4) The method for carrying out in-situ sampling and detection on the effective metal based on the DGT-XRF combined technology has important popularization significance, and firstly, the application environment range is wide, and the method comprises water, soil and sediments; secondly, the concentration range of the pollutants measured simultaneously is wide, and the pollutants comprise macroelements, microelements and trace elements; and thirdly, the types of the measured target objects are multiple, and the method not only can be used for metal elements related to the patent, but also can be applied to the fields of nutrient elements such as nitrogen and phosphorus, mercury, organic pollutants, pesticides and the like.
Drawings
FIG. 1 is a schematic diagram of a DGT-XRF device according to the present invention;
FIG. 2 is a standard plot of multiple elements built indoors for the DGT-XRF method of the present invention;
FIG. 3 is a schematic diagram illustrating the concentration of metal elements in a polluted water body according to an embodiment of the present invention;
fig. 4 is a schematic diagram comparing the concentration of metal elements in the contaminated soil measured in example two of the present invention with conventional detection.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Referring to fig. 1-4, the embodiment of the present invention provides two technical solutions: the method for carrying out in-situ sampling and detection on the effective metal based on the DGT-XRF combined technology specifically comprises the following embodiments:
example one
The method for carrying out in-situ sampling and detection on effective state metals based on the DGT-XRF combined technology is used for on-site monitoring of river polluted water bodies with black and odorous substances, and specifically comprises the following steps:
s1, preparation of DGT device: compared with standard DGT equipment, the device has an improved structure, does not assemble a diffusion membrane, consists of two layers of membranes, namely a ZrO-Chelex fixed membrane and a PVDF filter membrane, shortens the path of a target element absorbed by the fixed membrane, and enhances the fluorescence signal of XRF analysis under the condition of not influencing DGT measurement;
s2, preparation of indoor standard sample film: and establishing a standard curve of various heavy metal elements. And (4) putting the DGT device obtained in the step S1 into a mixed solution of a plurality of metal solutions with different concentration gradients for enrichment, determining one DGT with the same concentration by XRF to obtain a fluorescence signal value, extracting the other DGT by a solution extraction method, determining the accumulation amount by ICP-MS, and establishing a relation between the XRF signal value and the accumulation amount. The linear relation is recorded into a portable XRF for calculation during subsequent sample detection;
s3, field in-situ sampling: the ZrO-ChelexGT device is put into the river polluted water body with black and odor in situ, and is placed for 5 days to synchronously enrich multiple metal elements (Mn, Co, Ni, Cu, Zn, Pb, Cd, As and Cr). Taking out DGT every day, measuring the DGT once by XRF, and then putting back to continue enrichment;
and S4, detecting the DGT sample by using the portable XRF, and obtaining the content of the heavy metal effective state of the sample to be detected according to internal calculation.
In the embodiment of the invention, DGT is used As a passive sampling method of metal elements in a water body, various metal elements can be synchronously enriched in situ, portable XRF is used As a detection method for rapidly determining the elements on a DGT film, the synchronously determined metal elements comprise Mn, Co, Ni, Cu, Zn, Pb, Cd, As and Cr, the metal form determined by DGT is effective state concentration, and the bioavailable part of dissolved state concentration is not the total amount of the metal elements;
in the embodiment of the invention, the DGT device in the step S1 does not comprise a diffusion membrane and consists of two layers of membranes, namely a ZrO-Chelex fixed membrane and a PVDF filter membrane, so that the fluorescence signal of XRF analysis can be enhanced under the condition of not influencing DGT measurement;
in the embodiment of the invention, in step S2, multiple parallel standard sample films are prepared, multiple repeated measurements are performed, multiple random positions are selected, an arithmetic mean value is obtained, the DGT standard sample is determined by XRF, the sample needs to be placed on a clean desktop, the sample is accurately positioned with XRF, an XRF start key is turned on, a trigger is triggered, the instrument starts to measure, and the size of an XRF spot is kept at 8 mm. Subsequent sample measurements were consistent with the standard curve parameter settings.
In the embodiment of the invention, in the step S3, the standing time is determined according to the concentration of the polluted water and soil, the enrichment time of a heavily polluted site is shortened, the enrichment time of a lightly polluted site is prolonged, DGT is recovered after enrichment is finished, the surface of the filter membrane is cleaned after recovery, and is kept dry and is measured as soon as possible;
in the embodiment of the invention, in step S4, the DGT sample is measured by XRF to obtain the fluorescence signal value of each element, and the accumulated amount or concentration of the metal element in the sample is obtained by inputting the data into the Niton software according to the standard curve and calibration coefficient of different elements.
In the embodiment of the invention, fig. 3 is the concentration of metal elements in the polluted water body measured in the embodiment 1 of the invention, and fig. 3 shows that the enrichment amount is insufficient when the polluted water body is placed in water for 1-2 days, the measured concentration of the polluted water body is low, and the measured concentration is basically stable in 3-5 days, which shows that the concentration of the polluted water body can be accurately and quantitatively monitored when the polluted water body is placed for 3 days in the embodiment. Therefore, the putting time of the DGT with different water body concentrations needs to be determined according to the concentrations.
Example two
The method for carrying out in-situ sampling and detection on effective state metals based on the DGT-XRF combined technology is used for in-situ monitoring of contaminated site soil, and specifically comprises the following steps:
s1, preparation of DGT device: compared with standard DGT equipment, the device has an improved structure, does not assemble a diffusion membrane, consists of two layers of membranes, namely a ZrO-Chelex fixed membrane and a PVDF filter membrane, shortens the path of a target element absorbed by the fixed membrane, and enhances the fluorescence signal of XRF analysis under the condition of not influencing DGT measurement;
s2, preparation of indoor standard sample film: and establishing a standard curve of various heavy metal elements. And (4) putting the DGT device obtained in the step S1 into a mixed solution of a plurality of metal solutions with different concentration gradients for enrichment, determining one DGT with the same concentration by XRF to obtain a fluorescence signal value, extracting the other DGT by a solution extraction method, determining the accumulation amount by ICP-MS, and establishing a relation between the XRF signal value and the accumulation amount. The linear relation is recorded into a portable XRF for calculation during subsequent sample detection;
s3, sampling in situ on site, and putting the ZrO-ChelexDGT device into the polluted site soil in situ. It should be noted here that, because the DGT must be in a water environment to allow ion diffusion and enrichment, if the field soil is dry, water should be added at selected sampling points in advance to control the water content between 70-100%. After the soil is completely wet, the side of the membrane is placed against the soil in an inverted manner for 1-2 days, the soil is kept wet in the standing period, and a proper amount of water can be added after the soil is dry. Can synchronously enrich a plurality of metal elements (Mn, Co, Ni, Cu, Zn, Pb, Cd, As and Cr). Meanwhile, collecting a soil sample and bringing back to an experiment, extracting the concentration of the effective metal by using sodium bicarbonate, carrying out acid digestion according to a standard method, diluting digestion liquid, and monitoring by using ICP-MS;
and S4, detecting the DGT sample by using the portable XRF, and obtaining the content of the heavy metal effective state of the sample to be detected according to internal calculation.
In the embodiment of the invention, DGT is used As a passive sampling method of metal elements in soil, various metal elements can be synchronously enriched in situ, portable XRF is used As a detection method for rapidly determining the elements on a DGT film, the synchronously determined metal elements comprise Mn, Co, Ni, Cu, Zn, Pb, Cd, As and Cr, the metal form determined by DGT is effective concentration, and the bioavailable part of dissolved concentration is not the total amount of the metal elements;
in the embodiment of the invention, the DGT device in the step S1 does not comprise a diffusion membrane and consists of two layers of membranes, namely a ZrO-Chelex fixed membrane and a PVDF filter membrane, so that the fluorescence signal of XRF analysis can be enhanced under the condition of not influencing DGT measurement;
in the embodiment of the invention, in step S2, multiple parallel standard sample films are prepared, multiple repeated measurements are performed, multiple random positions are selected, an arithmetic mean value is obtained, the DGT standard sample is determined by XRF, the sample needs to be placed on a clean desktop, the sample is accurately positioned with XRF, an XRF start key is turned on, a trigger is triggered, the instrument starts to measure, and the size of an XRF spot is kept at 8 mm. Subsequent sample measurements were consistent with the standard curve parameter settings.
In the embodiment of the invention, in the step S3, the standing time is determined according to the concentration of the polluted water and soil, the enrichment time of a heavily polluted site is shortened, the enrichment time of a lightly polluted site is prolonged, DGT is recovered after enrichment is finished, the surface of the filter membrane is cleaned after recovery, and is kept dry and is measured as soon as possible;
in the embodiment of the invention, in step S4, the DGT sample is measured by XRF to obtain the fluorescence signal value of each element, and the accumulated amount or concentration of the metal element in the sample is obtained by inputting the data into the Niton software according to the standard curve and calibration coefficient of different elements.
In one embodiment of the present invention, FIG. 1 is a schematic diagram of a DGT-XRF device of the present invention, which is mainly composed of two parts, wherein the first part XRF device comprises a housing and a light source emitter; the second part is a DGT device comprising a housing, a fixed membrane and a filter membrane. When the device is used, the DGT device is horizontally placed on a table top and cannot move, light spots are formed after XRF and DGT need to be accurately positioned, and 3-5 points are respectively measured at different positions to obtain an average value.
In the embodiment of the invention, FIG. 2 is a multi-element standard curve graph established indoors by using a DGT-XRF method, and it can be seen that the standard curve of each element has a good linear relation, R 2 More than 0.9, the linear relation between Mn and Cr is best, R 2 Up to over 0.99.
In the embodiment of the invention, fig. 4 is a comparison between the concentration of metal elements in the contaminated soil measured in the embodiment 2 of the invention and the conventional detection, and it can be found from the figure that the concentration of the effective state of the metal measured by using the DGT-XRF combination is close to the concentration of the effective state of the metal extracted by the conventional solution, and the comparison proves that the method of the invention is accurate and feasible.
And those not described in detail in this specification are well within the skill of those in the art.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The method for carrying out in-situ sampling and detection on the effective metal based on the DGT-XRF combined technology is characterized in that: the method specifically comprises the following steps:
s1, preparing a DGT device;
s2, preparation of indoor standard sample film: establishing standard curves of various heavy metal elements, putting the DGT device obtained in the step S1 into a mixed solution of various metal solutions with different concentration gradients for enrichment, determining one DGT with the same concentration by XRF to obtain a fluorescence signal value, extracting the other DGT by a solution extraction method, then determining by ICP-MS to obtain an accumulated amount, and establishing a relation between the XRF signal value and the accumulated amount, wherein the linear relation is recorded in portable XRF for calculation during detection of subsequent samples;
s3, carrying out DGT enrichment on a water body or soil sample on site: putting the DGT device into a polluted water body or soil in situ, standing for 8-48h, and synchronously enriching metal elements of Mn, Co, Ni, Cu, Zn, Pb, Cd, As or Cr;
and S4, detecting the DGT sample by using the portable XRF, and obtaining the content of the heavy metal effective state of the sample to be detected according to internal calculation.
2. The method of claim 1 for in situ sampling and detection of available state metals based on DGT-XRF combination technology, wherein: the DGT is used as a passive sampling method of the metal elements in the water body or the soil, the water body or the soil does not need to be collected to a laboratory, and a plurality of metal elements can be synchronously enriched in situ.
3. The method of claim 1 for in situ sampling and detection of available state metals based on DGT-XRF combination technology, wherein: portable XRF as a detection method for rapid determination of elements on DGT films.
4. The method of claim 1 for in situ sampling and detection of available state metals based on DGT-XRF combination technology, wherein: the metal elements synchronously measured comprise Mn, Co, Ni, Cu, Zn, Pb, Cd, As and Cr.
5. The method of claim 1 for in situ sampling and detection of available state metals based on DGT-XRF combination technology, wherein: the metal form measured by DGT is the concentration of the available state, and the concentration of the bioavailable part of the dissolved state is not the total amount of the metal elements.
6. The method of claim 1 for in situ sampling and detection of available state metals based on DGT-XRF combination technology, wherein: in the step S1, the DGT device does not comprise a diffusion membrane and consists of two layers of membranes, namely a ZrO-Chelex fixed membrane and a PVDF filter membrane.
7. The method for in-situ sampling and detection of metal in an active state based on DGT-XRF combined technology as claimed in claim 1, wherein: in step S2, multiple parallel standard sample films are prepared, multiple repeated measurements are performed, multiple random positions are selected, and an arithmetic mean is obtained.
8. The method of claim 1 for in situ sampling and detection of available state metals based on DGT-XRF combination technology, wherein: in the step S2, the DGT standard sample is measured by the XRF, the sample needs to be horizontally placed on a clean desktop, the sample is accurately positioned with the XRF, an XRF starting key is opened, a trigger is buckled, the instrument starts to measure, the size of an XRF light spot is kept at 8mm, and the subsequent measurement of the sample is kept consistent with the standard curve parameter setting.
9. The method of claim 1 for in situ sampling and detection of available state metals based on DGT-XRF combination technology, wherein: and in the step S3, the standing time is determined according to the concentration of the polluted water and the soil, the enrichment time of a heavily polluted site is shortened, the enrichment time of a lightly polluted site is prolonged, the membrane is recovered after DGT (denaturing gradient transistor) enrichment is finished, the surface of the filter membrane is cleaned after the membrane is recovered, the membrane is kept dry, and the measurement is carried out as soon as possible.
10. The method of claim 1 for in situ sampling and detection of available state metals based on DGT-XRF combination technology, wherein: in the step S4, the DGT sample is measured by XRF to obtain a fluorescence signal value of each element, and the data is input to the Niton software to obtain the accumulated amount or concentration of the metal element in the sample according to the standard curve and calibration coefficient of different elements.
CN202210490946.5A 2022-05-07 2022-05-07 Method for carrying out in-situ sampling and detection on effective state metal based on DGT-XRF combined technology Pending CN114878615A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210490946.5A CN114878615A (en) 2022-05-07 2022-05-07 Method for carrying out in-situ sampling and detection on effective state metal based on DGT-XRF combined technology

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210490946.5A CN114878615A (en) 2022-05-07 2022-05-07 Method for carrying out in-situ sampling and detection on effective state metal based on DGT-XRF combined technology

Publications (1)

Publication Number Publication Date
CN114878615A true CN114878615A (en) 2022-08-09

Family

ID=82674023

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210490946.5A Pending CN114878615A (en) 2022-05-07 2022-05-07 Method for carrying out in-situ sampling and detection on effective state metal based on DGT-XRF combined technology

Country Status (1)

Country Link
CN (1) CN114878615A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115758690A (en) * 2022-11-07 2023-03-07 中国科学院烟台海岸带研究所 Site soil arsenic bioavailability prediction model and construction method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115758690A (en) * 2022-11-07 2023-03-07 中国科学院烟台海岸带研究所 Site soil arsenic bioavailability prediction model and construction method and application thereof
CN115758690B (en) * 2022-11-07 2023-11-24 中国科学院烟台海岸带研究所 Site soil arsenic bioavailability prediction model, construction method and application thereof

Similar Documents

Publication Publication Date Title
Greenwood et al. Passive sampling techniques in environmental monitoring
Searle et al. Determination of lead in blood and urine by anodic stripping voltammetry
Dočekalová et al. Use of constrained DET probe for a high-resolution determination of metals and anions distribution in the sediment pore water
Válega et al. Determination of organic mercury in biota, plants and contaminated sediments using a thermal atomic absorption spectrometry technique
US20050191757A1 (en) Method and apparatus for detecting humans and human remains
CN114878615A (en) Method for carrying out in-situ sampling and detection on effective state metal based on DGT-XRF combined technology
CN114594077A (en) High-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox condition change
CN104697980B (en) A kind of method that quantitative determination is carried out to mercury ion based on the change of raman characteristic peak peak position
US11971375B2 (en) Method for detecting adsorption performance of microplastics for heavy metals using low-field NMR relaxation method
Sowlat et al. Development and field evaluation of an online monitor for near-continuous measurement of iron, manganese, and chromium in coarse airborne particulate matter (PM)
Martin et al. Elemental analysis of environmental and biological samples using laser‐induced breakdown spectroscopy and pulsed Raman spectroscopy
CN111521577B (en) Infrared spectrum quantitative analysis method taking carbon dioxide peak area as reference
CN113237938A (en) Method for detecting heavy metals in surface water based on second-order differential peak finding method
Ma et al. Using optimized particle imaging of micro-Raman to characterize microplastics in water samples
CN204405548U (en) A kind of portable SERS detects dull and stereotyped
CN110261346A (en) A method of quickly detecting PVC content in soil based near infrared spectrum
CN110873727A (en) XRF-based analysis method for in-situ determination of water body metals
Ridošková et al. Prediction of cadmium, lead and mercury availability to plants: comparison between diffusive gradient in thin films technique measurement and soil grown plants
Mirmohseni et al. Application of quartz crystal nanobalance and principal component analysis for detection and determination of nickel in solution
West The identification and determination of airborne particulates by means of the ring oven technique
Kim et al. Evaluation of ion-selective membranes for real-time soil nutrient sensing
US11933777B1 (en) Model for predicting bioavailability of arsenic in site soil and construction method and application thereof
Emons et al. Perspective. Electroanalysis for the purpose of environmental monitoring and specimen banking: is there a future?
CN104132931B (en) The detection method of lemon chrome concentration in one heavy metal species concentrated acid liquid
CN117907158A (en) DGT device and application and use method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination