CN114878617A - Enrichment detection method and device for trace heavy metal elements in liquid - Google Patents
Enrichment detection method and device for trace heavy metal elements in liquid Download PDFInfo
- Publication number
- CN114878617A CN114878617A CN202210617981.9A CN202210617981A CN114878617A CN 114878617 A CN114878617 A CN 114878617A CN 202210617981 A CN202210617981 A CN 202210617981A CN 114878617 A CN114878617 A CN 114878617A
- Authority
- CN
- China
- Prior art keywords
- enrichment
- liquid sample
- sample
- liquid
- heavy metal
- 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
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 177
- 238000001514 detection method Methods 0.000 title claims abstract description 70
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 56
- 238000004458 analytical method Methods 0.000 claims abstract description 60
- 239000012086 standard solution Substances 0.000 claims abstract description 56
- 238000004876 x-ray fluorescence Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 17
- 230000003287 optical effect Effects 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 44
- 150000002500 ions Chemical class 0.000 description 18
- 238000005259 measurement Methods 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000012528 membrane Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 239000002352 surface water Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- 238000012864 cross contamination Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 238000011005 laboratory method Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000003968 anodic stripping voltammetry Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000012031 short term test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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 relates to a method and a device for enriching and detecting trace heavy metal elements in liquid, wherein the method comprises the following steps: providing an original liquid sample and an internal standard solution, and preparing a mixed liquid sample according to the original liquid sample and the internal standard solution; extracting a liquid sample to be detected from the mixed liquid sample, and enriching the liquid sample to be detected to obtain a target sample; and carrying out fluorescence spectrum analysis on the target sample by using monochromatic focusing X-ray fluorescence analysis equipment to obtain an element detection result. The method adopts monochromatic focusing XRF analysis equipment to measure the enriched target sample, greatly reduces the scattering background, can reach the required detection precision and detection limit by requiring a very small amount of liquid to be detected to be enriched, realizes the on-site rapid detection of the trace heavy metal elements in the liquid, simultaneously enables the detection limit of the liquid to reach the mu g/L level, has wider application range and high application value.
Description
Technical Field
The invention relates to the technical field of enrichment and detection of heavy metal elements in liquid, in particular to a method and a device for enriching and detecting trace heavy metal elements in liquid.
Background
Some liquids usually have very low content of heavy metal elements, such as surface water, and trace amount, and laboratory method and field detection method are generally adopted for detecting the heavy metal elements. The laboratory methods comprise atomic absorption spectrometry, inductively coupled plasma mass spectrometry, inductively coupled plasma emission spectrometry and the like, and the methods have extremely high sensitivity and can directly detect the heavy metal elements with extremely low content in the surface water. However, the sample pretreatment process of such methods is extremely complex and time-consuming; in addition, the equipment volume and weight are very big, can't carry out on-the-spot quick detection, and application scope and service environment are all limited. Therefore, for the detection of heavy metal elements in a liquid such as surface water, an in-situ detection method, which generally employs anodic stripping voltammetry, is more practical, and the detection sensitivity is high and the analysis speed is fast. However, the electrodes need to be replaced regularly, the calibration is frequent, the maintenance amount of the instrument is large, and the data is unstable; in addition, the method belongs to an electrochemical analysis method, and toxic chemical reagents and heavy metal electrodes are used, so that the method can cause pollution to the environment. Thus, there is still a need to find new breakthroughs in the field detection of heavy metal elements in liquids.
In recent years, X-ray fluorescence (XRF) analysis techniques have been increasingly used for detecting components of solid samples by virtue of advantages of simple sample processing, simultaneous measurement of multiple elements, nondestructive detection, high speed, convenient operation, field use and the like. However, when the XRF analysis technique is directly used for measuring a liquid sample, a relatively high scattering background is caused, so that the XRF analysis technique has a very limited capability of detecting the content of elements in the liquid sample, generally only can achieve the mg/L level, and cannot meet the requirement of detecting the low-content heavy metal elements in the liquid at the μ g/L level. By utilizing a total reflection Type XRF (TXRF) analysis technology, the detection limit of a directly detected liquid sample can reach the level of mu g/L, and the technology can be used for directly detecting heavy metal elements in liquid, but most of equipment of the type is used for scientific research in laboratories, no commercial instruments are sold, and the requirement of rapid field detection of departments at all levels cannot be met.
Therefore, in order to find a breakthrough in the field detection of heavy metal elements in liquid, how to use the XRF analysis technology to realize the field rapid detection and simultaneously make the detection limit of the liquid reach the level of μ g/L becomes a technical difficulty at the present stage.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is how to realize on-site rapid detection by using XRF analysis technology, and simultaneously, the detection limit of the liquid reaches the mu g/L level.
In order to solve the technical problem, the invention provides a method for enriching and detecting trace heavy metal elements in liquid, which comprises the following steps:
providing an original liquid sample and an internal standard solution, and preparing a mixed liquid sample according to the original liquid sample and the internal standard solution;
extracting a liquid sample to be detected from the mixed liquid sample, and enriching the liquid sample to be detected to obtain a target sample;
and carrying out fluorescence spectrum analysis on the target sample by using monochromatic focusing X-ray fluorescence analysis equipment to obtain an element detection result.
Preferably, the internal standard solution includes any one of an yttrium standard solution and a tungsten standard solution.
Preferably, the preparing a mixed liquid sample from the original liquid sample and the internal standard solution comprises:
filtering the original liquid sample to obtain a filtered liquid sample;
placing the filtered liquid sample into a centrifuge tube;
and adding the internal standard solution with a first preset volume into the filtered liquid sample in the centrifuge tube, and uniformly mixing to obtain the mixed liquid sample.
Preferably, the extracting the liquid sample to be tested from the mixed liquid sample includes:
and extracting the liquid sample to be detected from the mixed liquid sample according to a second preset volume by using an injector.
Preferably, the enriching the liquid sample to be tested to obtain a target sample includes:
connecting an enrichment head to the head of the syringe which extracts the liquid sample to be detected, and putting the syringe connected with the enrichment head into an automatic enrichment device;
and automatically enriching the liquid sample to be detected in the injector by using the automatic enrichment device according to preset enrichment time to obtain the target sample.
Preferably, the centrifuge tube is embodied as a disposable centrifuge tube, and/or the injector is embodied as a disposable syringe, and/or the enrichment head is embodied as a disposable enrichment head.
Preferably, after the enriching of the water sample to be detected is performed to obtain the target sample, the method further includes:
removing the enrichment head with the target sample from the syringe.
Preferably, the performing fluorescence spectrum analysis on the target sample by using a monochromatic focused X-ray fluorescence analysis device to obtain an element detection result includes:
and based on an X-ray fluorescence analysis method, performing fluorescence spectrum analysis on the target sample in the enrichment head by using the monochromatic focusing X-ray fluorescence analysis equipment to obtain the element detection result.
In addition, the invention also provides an enrichment detection device for trace heavy metal elements in liquid, which comprises:
a mixed sample producing device for providing an original liquid sample and an internal standard solution, and producing a mixed liquid sample from the original liquid sample and the internal standard solution;
the enrichment equipment is used for extracting a liquid sample to be detected from the mixed liquid sample and enriching the liquid sample to be detected to obtain a target sample;
and the monochromatic focusing X-ray fluorescence analysis equipment is used for carrying out fluorescence spectrum analysis on the target sample to obtain an element detection result.
Preferably, the monochromatic focused X-ray fluorescence analysis apparatus includes:
an apparatus body;
an X-ray source disposed within the device body;
the hyperbolic crystal optical device is arranged in the equipment body, is positioned on an output optical path of the X-ray source, and is used for receiving the X-rays emitted by the X-ray source, carrying out monochromatization on the X-rays to obtain monochromatic light beams, and exciting the target sample by utilizing the monochromatic light beams;
the detector is arranged in the equipment body and used for detecting an X-ray fluorescence signal generated after the target sample is excited by the monochromatic light beam; and
and the processor is arranged in the equipment body and used for receiving the X-ray fluorescence signal and carrying out fluorescence spectrum analysis on the target sample according to the X-ray fluorescence signal to obtain the element detection result corresponding to the trace heavy metal element in the target sample.
The technical scheme provided by the invention has the following advantages:
the mixed liquid sample is prepared from the original liquid sample and the internal standard solution, so that the trace heavy metal elements in the liquid sample to be measured can be corrected and measured according to the known concentration value of the internal standard solution based on an internal standard method in the follow-up process, and the measurement precision is ensured; the concentration of the element to be detected in the liquid sample to be detected can be improved by extracting the liquid sample to be detected from the mixed liquid sample and enriching the liquid sample to be detected, so that the requirement of directly detecting the low-content heavy metal element in the liquid at the mu g/L level is met; the monochromatic focusing X-ray fluorescence analysis equipment can monochromate and focus the polychromatic and divergent X-rays emitted by a conventional X-ray tube by adopting a hyperbolic crystal optical device, so that the scattering background is reduced, namely, the detection sensitivity of the conventional XRF analysis technology can be greatly improved and the detection limit is reduced based on the monochromatic focusing XRF analysis technology, and the detection limit for directly detecting a liquid sample can reach the level of sub-mg/L; according to the invention, a monochromatic focusing XRF analysis device is adopted to measure the enriched target sample, so that the scattering background is greatly reduced, the extremely low element detection limit is reached, the required detection precision and detection limit can be reached by only needing a very small amount of liquid to be detected to be enriched, the field rapid detection of trace heavy metal elements in the liquid is realized, meanwhile, the detection limit of the liquid reaches the mu g/L level, the application range is wider, and the application value is high.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for detecting enrichment of trace heavy metal elements in a liquid according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart illustrating a process of preparing a mixed liquid sample according to a first embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a model for enrichment detection of trace heavy metal elements in a liquid according to a first embodiment of the present invention;
FIG. 4 is a schematic diagram of the enrichment head according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of a monochromatic focused X-ray fluorescence analyzer according to an embodiment of the present invention;
fig. 6 is a schematic structural diagram of an enrichment detection apparatus for trace heavy metal elements in liquid according to a second embodiment of the present invention.
Description of reference numerals:
1. the device comprises a mixed sample manufacturing device, 2, an enrichment device, 3, a monochromatic focusing X-ray fluorescence analysis device, 4, a filtered liquid sample, 5, an internal standard solution, 6, a target sample, 11, a centrifuge tube, 21, an injector, 22, an enrichment head, 23, an automatic enrichment device, 24, an enrichment cup holder, 31, a device body, 32, an X-ray source, 33, a hyperbolic crystal optical device, 34, a detector, 35, a processor, 221, a powder enrichment cup, 222, a powder enrichment cover, 223, a micropore sieve plate, 224, enrichment ion powder, 225, a micropore filter membrane, 226, a membrane collar, 227 and a rubber gasket.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. The invention will be described in detail hereinafter with reference to the accompanying drawings in conjunction with embodiments. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
In the present invention, unless specified to the contrary, use of the terms of orientation such as "upper, lower, top, bottom" or the like, generally refer to the orientation as shown in the drawings, or to the component itself in a vertical, perpendicular, or gravitational orientation; likewise, for ease of understanding and description, "inner and outer" refer to the inner and outer relative to the profile of the components themselves, but the above directional words are not intended to limit the invention.
Trace elements refer to any element present in an amount below one part per million (i.e., ppm). Elements other than ten elements of O, H, Si, Al, Fe, Ca, Mg, Na, K and Ti (the total abundance of the elements accounts for about 99 percent) in the crust are generally called trace elements or trace elements.
The method and the device for enriching and detecting the trace heavy metal elements in the liquid can be applied to any liquid containing the trace heavy metal elements, such as surface water and underground water, and the following embodiment takes the measurement of the trace heavy metal elements applied to the surface water as an example for illustration.
Example one
As shown in fig. 1, this embodiment provides a method for enriching and detecting a trace heavy metal element in a liquid, including:
s1, providing an original liquid sample and an internal standard solution, and preparing a mixed liquid sample according to the original liquid sample and the internal standard solution.
Preferably, the internal standard solution includes any one of an yttrium standard solution and a tungsten standard solution.
Through different internal standard solutions, enrichment of a liquid sample to be detected can be realized subsequently aiming at different enrichment materials, and finally, targeted analysis and determination of heavy metal elements are carried out.
Before S1, the present embodiment further includes:
the internal standard solution was prepared.
Specifically, in the present embodiment, the original liquid sample is a surface water sample.
Before S1, the present embodiment further includes:
obtaining a third predetermined volume of the raw liquid sample from the surface water.
Specifically, the third preset volume in this embodiment is 20 ml.
Preferably, as shown in fig. 2, in S1, preparing a mixed liquid sample from the original liquid sample and the internal standard solution includes:
s11: filtering the original liquid sample to obtain a filtered liquid sample;
s12: placing the filtered liquid sample into a centrifuge tube;
s13: and adding the internal standard solution with a first preset volume into the filtered liquid sample in the centrifuge tube, and uniformly mixing to obtain the mixed liquid sample.
Impurities in the original liquid sample can be filtered out through filtering the original liquid sample, so that the measurement accuracy of the trace heavy metal elements can be improved to a certain extent; according to the steps, the filtered liquid sample and the internal standard solution are uniformly mixed, so that the subsequent enrichment effect can be improved, the trace heavy metal elements in the liquid sample to be measured can be corrected and measured according to the known concentration value of the internal standard solution on the basis of an internal standard method, and the measurement precision is ensured.
Specifically, as shown in fig. 3, in this example S13, the first preset volume is 1ml, the capacity of the centrifuge tube 11 is 50ml, and when 20ml of the filtered liquid sample 4 is put into the 50ml centrifuge tube 11, 1ml of the internal standard solution 5 is added into the filtered liquid sample 4 in the centrifuge tube 11, and then the mixture is shaken by 3 to 5 to achieve the uniform mixing effect, so as to obtain 21ml of the mixed liquid sample.
As shown in fig. 1, S2, extracting a liquid sample to be tested from the mixed liquid sample, and enriching the liquid sample to be tested to obtain a target sample.
Preferably, in S2, extracting a liquid sample to be tested from the mixed liquid sample includes:
s21: and extracting the liquid sample to be detected from the mixed liquid sample according to a second preset volume by using an injector.
The liquid sample to be detected with the second preset volume is extracted from the mixed liquid sample through the injector, so that the mixed liquid sample can be used for field repeated detection on one hand, and the pollution to the mixed liquid sample is avoided on the other hand.
Specifically, the syringe in this embodiment has a volume of 30ml, and the second preset volume is set according to actual conditions.
Preferably, in S2, enriching the liquid sample to be tested to obtain a target sample, including:
s22: connecting an enrichment head to the head of the syringe which extracts the liquid sample to be detected, and putting the syringe connected with the enrichment head into an automatic enrichment device;
s23: and according to the preset enrichment time, automatically enriching the liquid sample to be detected in the injector by using the automatic enrichment device to obtain the target sample.
Through the enrichment step, the enrichment process of the liquid sample to be measured can be completed with less liquid and shorter enrichment time, the required measurement precision and detection limit are reached, and the saturation phenomenon of the enrichment material is avoided.
Preferably, as shown in fig. 3, the centrifuge tube 11 is embodied as a disposable centrifuge tube, and/or the syringe 21 is embodied as a disposable syringe, and/or the enrichment head 22 is embodied as a disposable enrichment head.
The enrichment membrane in the existing enrichment device adopts an imported finished product heavy metal ion enrichment membrane, so that the cost is higher; when the device is used on site, most of consumables are reused, cross contamination among samples is possible, and the reproducibility and accuracy of a measurement result are difficult to ensure; and before each new enrichment operation, parts of consumable materials such as pipelines and the like must be cleaned, the field operation is complex and time-consuming, the cleaning is not thorough, and the effect is difficult to guarantee. The disposable consumable can be used on site, so that pollution to a liquid sample to be detected can be avoided to the maximum extent, good reproducibility is realized, and the result is accurate and reliable; the disposable consumable cleaning device is basically free from cleaning and maintenance on site, and can be used for cleaning disposable consumables in a centralized manner in idle time so as to be repeatedly used for many times.
Specifically, in S22, the connection between the enrichment head 22 and the head of the syringe 21 is in the form of a luer fitting.
Specifically, in S22, the enrichment head 22 is packaged in a disposable sealed package, as shown in fig. 4, the enrichment head 22 includes a powder enrichment cup 221, a powder enrichment lid 222, a microporous sieve plate 223, an ion-enriched powder 224, a microporous filter membrane 225, a membrane collar 226, and a rubber gasket 227; the powder enrichment cup 221 is provided with a through channel, a bayonet is arranged on the channel, a micropore sieve plate 223 is arranged on the bayonet, the micropore sieve plate 223 is matched with the powder enrichment cup 221, the enriched ion powder 224 is compacted in the powder enrichment cover 222, and the powder enrichment cover 222 is connected to the powder enrichment cup 51 in a threaded connection mode. The specific structure of the enrichment head 22 in this embodiment is conventional, and other details are not described herein.
In the existing enrichment technology, imported finished heavy metal ion enrichment membranes are adopted, and in the embodiment, the ion resin powder is adopted as an enrichment material, so that compared with the enrichment membranes, the single enrichment cost is low, and the solid phase extraction mode is simpler, more convenient and faster than other pre-enrichment modes.
Wherein, the ion-enriched powder 224 comprises cation-enriched resin powder and anion-enriched resin powder, and for the cation-enriched resin powder, the internal standard solution added in the S1 is yttrium (Y) standard solution, and the concentration is 2 mg/L; for the anion-enriched resin powder, the internal standard solution added in S1 was a tungsten (W) standard solution at a concentration of 1 mg/L. In the conventional enrichment technology using enrichment membranes, because the performance of the enrichment membranes is different, and the PH value of the liquid used for enrichment is also different, these factors can bring obvious influence on the enrichment process, thereby influencing the final measurement result. In this embodiment, a targeted internal standard solution is added to different ion-enriched resin powders, a liquid sample to be measured is obtained after uniform mixing and extraction by an injector, the internal standard solution and a liquid to be subjected to element measurement undergo a pre-enrichment process together, and the internal standard solution and heavy metal elements in the liquid are adsorbed by the ion-enriched resin powders together to form a viscous target sample. In the enrichment process, the influence mechanism of elements in liquid needing element determination and elements in an internal standard solution is consistent due to the difference of the quantity and the efficiency of the enriched ion resin powder, the influence of the PH value on the elements in the liquid and the elements in the internal standard solution is also the same, and in a spectrogram obtained through fluorescence spectrum analysis finally, the net counting values of the elements in the liquid needing element determination and the elements in the internal standard solution are uniformly higher or lower, so that the final measurement result can be corrected through the known concentration value of the internal standard solution in a quantitative algorithm, the influence possibly caused by the factors such as the quantity of the enriched ion resin powder and the PH value of the liquid to be measured is reduced to the minimum, and the measurement precision is ensured.
Specifically, as shown in fig. 3, in the present embodiment, the syringe 21 connected with the enrichment head 22 is placed in the automatic enrichment device 23, the enrichment speed is kept at the default setting, and the "start" button on the automatic enrichment device 23 is clicked to start the automatic enrichment process. The preset enrichment time can be set according to actual conditions, and is set to 3 minutes in the embodiment, that is, the whole automatic enrichment process lasts for 3 minutes, and after the automatic enrichment is completed, the target sample is obtained. The automatic enrichment device 23 in this embodiment is an enrichment device in the prior art, and details thereof are not described herein.
Preferably, after S23, the method further includes:
removing the enrichment head with the target sample from the syringe.
By taking down the enrichment head, the target sample is conveniently sent into monochromatic focusing X-ray fluorescence analysis equipment for fluorescence spectrum analysis, and the determination of heavy metal elements in the target sample is realized.
Specifically, in the present embodiment, as shown in fig. 3, after the enrichment head 22 is removed from the syringe 21, the powder enrichment cap 222 above the enrichment head 22 is unscrewed to expose the powder enrichment cup 221, and then the powder enrichment cup 221 is mounted on the enrichment cup holder 24 that matches the powder enrichment cup 221.
As shown in fig. 1, S3, performing fluorescence spectrum analysis on the target sample by using a monochromatic focused X-ray fluorescence analysis device to obtain an element detection result.
Preferably, S3 includes:
and based on an X-ray fluorescence analysis method, performing fluorescence spectrum analysis on the target sample in the enrichment head by using the monochromatic focusing X-ray fluorescence analysis equipment to obtain the element detection result.
Because conventional XRF analytical equipment's sensitivity is low, and the detection limit is higher, in order to reach the detection limit requirement of heavy metal element in liquid such as surface water, must use a large amount of liquid to carry out the preconcentration, and it is long consuming time, and cause the saturation phenomenon of enrichment diaphragm very easily. The embodiment utilizes monochromatic focusing X-ray fluorescence analysis equipment to measure the sample after enrichment, greatly reduces the scattering background, reaches extremely low element detection limit, needs a very small amount of liquid to be detected to be enriched to reach the required detection precision and detection limit, effectively avoids the saturation phenomenon of the enrichment material, and greatly shortens the enrichment time.
Specifically, as shown in fig. 5, the monochromatic focused X-ray fluorescence analysis apparatus 3 of the present embodiment includes:
an apparatus body 31;
an X-ray source 32 provided in the apparatus body 31;
the hyperbolic crystal optical device 33 is arranged in the equipment body 31, is positioned on an output light path of the X-ray source, and is used for receiving the X-rays emitted by the X-ray source, carrying out monochromatization on the X-rays to obtain monochromatic light beams, and exciting the target sample 6 by using the monochromatic light beams;
the detector 34 is arranged in the equipment body 31 and is used for detecting an X-ray fluorescence signal generated after the target sample 6 is excited by the monochromatic light beam; and
and the processor 35 is arranged in the equipment body 31 and is used for receiving the X-ray fluorescence signal and performing fluorescence spectrum analysis on the target sample 6 according to the X-ray fluorescence signal to obtain the element detection result corresponding to the trace heavy metal element in the target sample 6.
The monochromatic focusing X-ray fluorescence analysis equipment with the structure adopts the high-efficiency hyperbolic crystal optical device to carry out monochromatization and focusing on the multicolor and divergent X-rays emitted by the X-ray source, so that on one hand, the scattering background is greatly reduced due to monochromatization, the sensitivity is improved, and on the other hand, the useful X-ray intensity of a sample area is greatly improved due to focusing, and the signal intensity is improved; the monochromatic focused X-ray is set to irradiate the surface of the target sample at a small angle, so that the distance between the sample and the detector can be small, the collection solid angle of the detector is remarkably increased, the system sensitivity is further improved, and the detection limit is reduced.
Specifically, the monochromatic focused X-ray fluorescence analysis device 3 is further provided with a sample chamber and a safety door, the powder enrichment cup 221 of the embodiment is placed into the sample chamber of the monochromatic focused X-ray fluorescence analysis device 3 in a lateral sample introduction manner by using the enrichment cup holder 24 on the powder enrichment cup, the safety door is closed, and a corresponding measurement curve is selected for analysis and test, so as to obtain the content information of the heavy metal elements in the surface water. Selecting a cation enrichment curve for measurement, wherein the cation enrichment curve is an analysis curve after calibration of a standard sample when the cation enrichment resin powder leaves a factory, the adopted standard sample is prepared from GSB04-1767-2004 multi-element standard solution and pure water, and the gradient concentration is 0 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L and 100 mu g/L; for the anion-enriched resin powder, an anion enrichment curve is selected for measurement, the anion enrichment curve is also an analysis curve after calibration of a standard sample, the adopted standard sample is prepared from a single element standard solution of hexavalent chromium, arsenic, selenium and the like and pure water, and the gradient concentration is 0 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L and 100 mu g/L.
The components of the monochromatic focused X-ray fluorescence analysis device 3 are all prior art, and the details thereof are not described herein.
The results of measuring the heavy metal elements in the surface water by the method in this example are shown in the following table. According to the following table, the detection limit of the method for measuring the heavy metal elements in the surface water is far lower than the standard detection limit of the surface water, so that the detection limit is greatly reduced.
Comparison result of surface water heavy metal element determination
Based on the complete enrichment detection method for trace heavy metal elements in liquid, the following beneficial effects can be realized:
(1) the enrichment head adopts the enrichment ion resin powder, and compared with an imported enrichment membrane, the cost is greatly reduced. The cost for single enrichment is about 20 yuan after the import enrichment membrane is cut into the required size by a special cutting die, while the cost for single enrichment is less than 2 yuan when the enrichment ion resin powder is used.
(2) Because the quantity and the efficiency of the ion-enriched resin powder filled in the enrichment heads of different enrichment materials are different, in addition, the factors such as the pH value of a liquid sample to be detected and the like can also influence the enrichment process; therefore, in the embodiment, the internal standard solution is added into the original liquid sample, the liquid sample to be measured is obtained after uniform mixing and extraction, the enrichment process is carried out, and the internal standard solution and the heavy metal elements in the liquid to be measured are adsorbed by the ionic resin. In the enrichment process, the influence mechanisms of the quantity and the efficiency of the enriched ion resin powder on elements in the liquid to be measured and elements in the internal standard solution are consistent, the influence of the pH value on the elements in the liquid to be measured and the elements in the internal standard solution is also the same, and in the finally obtained fluorescence spectrogram, the net counting values of the elements in the liquid to be measured and the elements in the internal standard solution are uniformly higher or lower, so that the final measurement result can be corrected through the known concentration value of the internal standard solution in a quantitative algorithm, the influence of the difference of the enriched ion resin powder, the pH value difference of the liquid to be measured and the like is reduced to the minimum, and the measurement precision is ensured.
(3) In the process of on-site detection, the automatic enrichment device does not contact with a liquid sample to be detected, so that the phenomenon of cross contamination does not exist, and the accuracy of enrichment and measurement at each time is ensured.
(4) In the process of on-site detection, the used consumables and containers (such as syringes, enrichment heads and the like) are all disposable, cleaning operation is not needed on site, the enrichment operation steps and time are saved, and the residual phenomenon is not worried about. In addition, disposable consumptive material after using can collect in special accomodate the bag, treat to get back to the laboratory after, concentrate and adopt special technology to unify the washing, can guarantee abluent effect to used repeatedly.
(5) In the utilized monochromatic focusing X-ray fluorescence analysis equipment, a high-efficiency hyperbolic crystal optical device is adopted to carry out monochromatization and focusing on multicolor and divergent X-rays emitted by an X-ray source, so that on one hand, the scattering background is greatly reduced due to monochromatization, the sensitivity is improved, and on the other hand, the useful X-ray intensity of a sample area is greatly improved due to focusing, and the signal intensity is improved; the monochromatic focused X-ray is set to irradiate the surface of the target sample at a small angle, so that the distance between the sample and the detector can be small, the collection solid angle of the detector is remarkably increased, the system sensitivity is further improved, and the detection limit is reduced.
Example two
As shown in fig. 6, this embodiment provides an enrichment detection apparatus for trace heavy metal elements in a liquid, including:
a mixed sample producing device 1 for providing an original liquid sample and an internal standard solution, and producing a mixed liquid sample from the original liquid sample and the internal standard solution;
the enrichment equipment 2 is used for extracting a liquid sample to be detected from the mixed liquid sample, and enriching the liquid sample to be detected to obtain a target sample;
and the monochromatic focusing X-ray fluorescence analysis equipment 3 is used for carrying out fluorescence spectrum analysis on the target sample to obtain an element detection result.
The enrichment detection device of this embodiment adopts monochromatic focus XRF analytical equipment to measure the target sample after the enrichment, has greatly reduced the scattering background, reaches extremely low element detection limit, and the liquid that needs the fewest to be measured carries out the enrichment and can reach required detection precision and detection limit, has realized the on-the-spot short-term test of trace heavy metal element in the liquid, makes the detection limit of liquid reach the mu g/L level simultaneously, has more extensive application scope, and use value is high.
Specifically, as shown in fig. 3, the mixed sample preparation apparatus 1 in the present embodiment specifically includes a centrifuge tube 11; as shown in fig. 3, the enrichment apparatus 2 includes a syringe 21, an enrichment head 22, an automatic enrichment device 23, and an enrichment cup holder 24; as shown in fig. 5, the monochromatic focused X-ray fluorescence analysis apparatus 3 includes an apparatus body 31, an X-ray source 32, hyperbolic crystal optics 33, a detector 34, and a processor 35.
In particular, the centrifuge tube 11 is embodied as a disposable centrifuge tube, and/or the syringe 21 is embodied as a disposable syringe, and/or the enrichment head 22 is embodied as a disposable enrichment head.
Specifically, in the present embodiment, as shown in fig. 4, the enrichment head 22 includes a powder enrichment cup 221, a powder enrichment cover 222, a microporous sieve plate 223, an ion-enriched powder 224, a microporous filter membrane 225, a membrane collar 226, and a rubber gasket 227; the powder enrichment cup 221 is provided with a through channel, a bayonet is arranged on the channel, a micropore sieve plate 223 is arranged on the bayonet, the micropore sieve plate 223 is matched with the powder enrichment cup 221, the enriched ion powder 224 is compacted in the powder enrichment cover 222, and the powder enrichment cover 222 is connected to the powder enrichment cup 51 in a threaded connection mode.
Details of the embodiment are not described in detail in the first embodiment and the specific descriptions in fig. 1 to 5, which are not repeated herein.
It is to be understood that the above-described embodiments are only a few, but not all, embodiments of the present invention. Based on the embodiments of the present invention, those skilled in the art may make other variations or modifications without creative efforts, and shall fall within the protection scope of the present invention.
Claims (10)
1. An enrichment detection method of trace heavy metal elements in liquid is characterized by comprising the following steps:
providing an original liquid sample and an internal standard solution, and preparing a mixed liquid sample according to the original liquid sample and the internal standard solution;
extracting a liquid sample to be detected from the mixed liquid sample, and enriching the liquid sample to be detected to obtain a target sample;
and carrying out fluorescence spectrum analysis on the target sample by using monochromatic focusing X-ray fluorescence analysis equipment to obtain an element detection result.
2. The method for detecting the enrichment of the trace heavy metal elements in the liquid according to claim 1, wherein the internal standard solution comprises any one of a yttrium standard solution and a tungsten standard solution.
3. The method for detecting the enrichment of the trace heavy metal elements in the liquid according to claim 1 or 2, wherein the step of preparing a mixed liquid sample according to the original liquid sample and the internal standard solution comprises the following steps:
filtering the original liquid sample to obtain a filtered liquid sample;
placing the filtered liquid sample into a centrifuge tube;
and adding the internal standard solution with a first preset volume into the filtered liquid sample in the centrifuge tube, and uniformly mixing to obtain the mixed liquid sample.
4. The method for detecting the enrichment of the trace heavy metal elements in the liquid according to claim 3, wherein the extracting of the liquid sample to be detected from the mixed liquid sample comprises:
and extracting the liquid sample to be detected from the mixed liquid sample according to a second preset volume by using an injector.
5. The method for enriching and detecting the trace heavy metal elements in the liquid according to claim 4, wherein the enriching the liquid sample to be detected to obtain a target sample comprises:
connecting an enrichment head to the head of the syringe which extracts the liquid sample to be detected, and putting the syringe connected with the enrichment head into an automatic enrichment device;
and automatically enriching the liquid sample to be detected in the injector by using the automatic enrichment device according to preset enrichment time to obtain the target sample.
6. The method for enriching and detecting the trace heavy metal elements in the liquid according to claim 5, wherein the centrifugal tube is a disposable centrifugal tube, and/or the injector is a disposable syringe, and/or the enriching head is a disposable enriching head.
7. The method for enriching and detecting the trace heavy metal elements in the liquid according to claim 5, wherein after the enriching of the water sample to be detected to obtain the target sample, the method further comprises:
removing the enrichment head with the target sample from the syringe.
8. The method for detecting the enrichment of the trace heavy metal elements in the liquid according to claim 7, wherein the performing fluorescence spectrum analysis on the target sample by using a monochromatic focused X-ray fluorescence analysis device to obtain an element detection result comprises:
and based on an X-ray fluorescence analysis method, performing fluorescence spectrum analysis on the target sample in the enrichment head by using the monochromatic focusing X-ray fluorescence analysis equipment to obtain the element detection result.
9. The utility model provides an enrichment detection device of trace heavy metal element in liquid which characterized in that includes:
a mixed sample producing device for providing an original liquid sample and an internal standard solution, and producing a mixed liquid sample from the original liquid sample and the internal standard solution;
the enrichment equipment is used for extracting a liquid sample to be detected from the mixed liquid sample and enriching the liquid sample to be detected to obtain a target sample;
and the monochromatic focusing X-ray fluorescence analysis equipment is used for carrying out fluorescence spectrum analysis on the target sample to obtain an element detection result.
10. The apparatus for detecting the enrichment of trace heavy metal elements in liquid according to claim 9, wherein the monochromatic focused X-ray fluorescence analysis device comprises:
an apparatus body;
an X-ray source disposed within the device body;
the hyperbolic crystal optical device is arranged in the equipment body, is positioned on an output optical path of the X-ray source, and is used for receiving the X-rays emitted by the X-ray source, carrying out monochromatization on the X-rays to obtain monochromatic light beams, and exciting the target sample by utilizing the monochromatic light beams;
the detector is arranged in the equipment body and used for detecting an X-ray fluorescence signal generated after the target sample is excited by the monochromatic light beam; and
and the processor is arranged in the equipment body and used for receiving the X-ray fluorescence signal and carrying out fluorescence spectrum analysis on the target sample according to the X-ray fluorescence signal to obtain the element detection result corresponding to the trace heavy metal element in the target sample.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210617981.9A CN114878617A (en) | 2022-06-01 | 2022-06-01 | Enrichment detection method and device for trace heavy metal elements in liquid |
| PCT/CN2022/140851 WO2023231385A1 (en) | 2022-06-01 | 2022-12-22 | Enrichment detection method and apparatus for trace heavy metal elements in liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210617981.9A CN114878617A (en) | 2022-06-01 | 2022-06-01 | Enrichment detection method and device for trace heavy metal elements in liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114878617A true CN114878617A (en) | 2022-08-09 |
Family
ID=82679710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210617981.9A Pending CN114878617A (en) | 2022-06-01 | 2022-06-01 | Enrichment detection method and device for trace heavy metal elements in liquid |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114878617A (en) |
| WO (1) | WO2023231385A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023231385A1 (en) * | 2022-06-01 | 2023-12-07 | 苏州佳谱科技有限公司 | Enrichment detection method and apparatus for trace heavy metal elements in liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106248710A (en) * | 2016-09-09 | 2016-12-21 | 广州市怡文环境科技股份有限公司 | Method for detecting element based on total reflection X-ray fluorescence analysis |
| CN113176286A (en) * | 2021-06-16 | 2021-07-27 | 浙江萤火虫环境科技有限公司 | High-sensitivity X-ray fluorescence detection method for elements such as cadmium in water |
| CN214585015U (en) * | 2020-12-25 | 2021-11-02 | 西安佳谱电子科技有限公司 | Disposable heavy metal element pre-enrichment head in surface water |
| CN113820342A (en) * | 2021-09-09 | 2021-12-21 | 台州高视通智能科技有限公司 | Trace element X-ray fluorescence measuring method and device and electronic equipment |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2513566C (en) * | 2003-01-21 | 2012-04-24 | X-Ray Flux Pty Ltd | X-ray fluorescence flux composition |
| JP2005083827A (en) * | 2003-09-05 | 2005-03-31 | Horiba Ltd | Method and instrument for fluorescent x-ray analysis |
| CN103604823A (en) * | 2013-11-13 | 2014-02-26 | 宣化钢铁集团有限责任公司 | Method for measuring contents of potassium, sodium, lead and zinc in iron ore |
| CN107064510A (en) * | 2017-04-24 | 2017-08-18 | 武汉大学 | A kind of method of circulating tumor cell in utilization ICP MS and fluorescence imaging detection whole blood |
| CN107764799A (en) * | 2017-11-21 | 2018-03-06 | 江西农业大学 | Device based on resonant excitation LIBS quick detection tealeaves heavy metal |
| CN110095433A (en) * | 2019-06-17 | 2019-08-06 | 广西师范大学 | A method of silicate is measured with Resonance Rayleigh Scattering Spectra |
| CN113740194A (en) * | 2021-09-06 | 2021-12-03 | 安徽工业大学 | Method for detecting palladium in palladium-carbon catalyst by bismuth-gold-testing gravimetric method |
| CN114136726B (en) * | 2021-11-08 | 2024-03-26 | 南京农业大学 | Method for simultaneously detecting lead, cadmium and arsenic in shellfish |
| CN114878617A (en) * | 2022-06-01 | 2022-08-09 | 苏州佳谱科技有限公司 | Enrichment detection method and device for trace heavy metal elements in liquid |
-
2022
- 2022-06-01 CN CN202210617981.9A patent/CN114878617A/en active Pending
- 2022-12-22 WO PCT/CN2022/140851 patent/WO2023231385A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106248710A (en) * | 2016-09-09 | 2016-12-21 | 广州市怡文环境科技股份有限公司 | Method for detecting element based on total reflection X-ray fluorescence analysis |
| CN214585015U (en) * | 2020-12-25 | 2021-11-02 | 西安佳谱电子科技有限公司 | Disposable heavy metal element pre-enrichment head in surface water |
| CN113176286A (en) * | 2021-06-16 | 2021-07-27 | 浙江萤火虫环境科技有限公司 | High-sensitivity X-ray fluorescence detection method for elements such as cadmium in water |
| CN113820342A (en) * | 2021-09-09 | 2021-12-21 | 台州高视通智能科技有限公司 | Trace element X-ray fluorescence measuring method and device and electronic equipment |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023231385A1 (en) * | 2022-06-01 | 2023-12-07 | 苏州佳谱科技有限公司 | Enrichment detection method and apparatus for trace heavy metal elements in liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023231385A1 (en) | 2023-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7016462B1 (en) | Ionic pre-concentration XRF identification and analysis device, system and method | |
| CN102301219A (en) | Device for pretreating biological sample and mass spectrometer equipped with same | |
| CN108872075A (en) | The detection system and method for heavy metal in a kind of water | |
| JP5583362B2 (en) | Simultaneous analysis method for multi-element components in soil | |
| CN114878617A (en) | Enrichment detection method and device for trace heavy metal elements in liquid | |
| CN105891245A (en) | Solid-phase extraction and XFR combined method and device for detecting heavy metal in water | |
| CN107907617A (en) | It is a kind of to trap the method for phenolic compound and ammonia in cigarette mainstream flue gas at the same time using liquid feeding filter disc is in situ | |
| US20240085358A1 (en) | Method for detecting adsorption performance of microplastics for heavy metals using low-field nmr relaxation method | |
| RU2585369C1 (en) | Method of determining content of cadmium, lead, arsenic, chromium, nickel, copper, zinc, manganese, vanadium, strontium, selenium, thallium in blood by mass spectrometry with inductively coupled plasma | |
| US20200395201A1 (en) | Composition analysis technology of ultramicro volume liquid by laser ablation plasma mass spectrometry | |
| US11692954B1 (en) | Trace detection method of heavy metals and application thereof | |
| CN210775527U (en) | Device for pretreatment of multiple samples | |
| CN202256162U (en) | Portable atomic fluorescence spectrograph | |
| CN103995046A (en) | Application and method for detecting forchlorfenuron residues in crops by using ionic migration spectrometer | |
| JP2012073264A (en) | Simple test method for content of harmful substance in soil | |
| CN108508223A (en) | A kind of high-throughput Continuous Flow Analysis method for chlorinity in tobacco gene editor's material | |
| JP4174567B2 (en) | Simple quantitative analysis method for heavy metals and chemical substances in the environment | |
| CN113984871B (en) | Method for determining shale soluble organic carbon isotope by using EA-IRMS | |
| RU2760002C2 (en) | Method for determining mass concentration of total iron in associated waters and waters of oil and gas condensate fields by x-ray fluorescence method | |
| Olukoga et al. | Laboratory instrumentation in clinical biochemistry: an historical perspective | |
| Blazewicz | Selected problems on ion chromatography determinations of trace elements in clinical samples | |
| CN218726954U (en) | Low-concentration organic amine detection device containing concentration device | |
| CN107192756A (en) | The detection means of a variety of mycotoxins in a kind of on-line checking corn | |
| CN108489789A (en) | A kind of high-throughput Continuous Flow Analysis method for sulfate in tobacco gene editor's material | |
| JP2005114700A (en) | Analysis pretreatment method and device for atmospheric aerosol particle used for pixe analysis |
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 |