Water heavy metal element enrichment and sample preparation device for XRF (X-Ray Fluorescence) detection and water heavy metal element enrichment and sample preparation method

Abstract

The invention provides a water heavy metal element enrichment and sample preparation device for XRF (X-Ray Fluorescence) detection and a water heavy metal element enrichment and sample preparation method. The enrichment sample preparation device comprises: a cylindrical sample loading member having a first open side and a second open side, the sample loading member comprising a sample collection portion and a sample cup portion, the sample collection portion and the sample cup portion being arranged in sequence from the first open side to the second open side in the axial direction of the sample loading member and being communicated with each other; the membrane sleeve ring is arranged on the periphery of the sample cup part in a sleeving manner; the circular ring limiting cover is located on the second open side, the circular ring limiting cover is detachably connected with the sample collecting part and used for fixing the film sleeve ring, and the circular ring limiting cover is provided with a liquid outlet nozzle corresponding to the position of the sample cup part in the axial direction of the circular ring limiting cover; the sample pressing device comprises a pressing head and a pressing rod which are connected with each other, and the particle enrichment material is pressed into a to-be-detected sample cake located at the sample cup part through the pressing head and the pressing rod. According to the invention, the integration of collection of the granular enrichment material and sample preparation is realized, the sensitivity of the XRF detection method is effectively improved, and the requirements of on-site rapid enrichment and detection are met.

Description

Technical Field

[0001] The present application relates to the technical field of XRF detection, and in particular to a device for enriching and preparing samples of heavy metal elements in water for XRF detection and a method for enriching and preparing samples of heavy metal elements in water. Background Art

[0002] X-ray fluorescence spectrometry (XRF) is a green and environmentally friendly non-destructive multi-element simultaneous analysis and detection method, which is widely used in the analysis of major, minor and trace elements in environmental samples. In recent years, portable X-ray spectrometers (XRF) have been widely used in the analysis of trace elements in geological materials. They have the characteristics of small size, light weight, fast analysis speed and on-site non-destructive detection, and can achieve qualitative and quantitative analysis based on the characteristic X-ray fluorescence energy, wavelength and intensity emitted by heavy metals when they are excited to a high energy state. However, XRF technology is usually used to analyze environmental solid samples. When directly analyzing liquid samples, the high scattering background of X-rays, poor signal-to-noise ratio and high uncertainty of the results obtained have resulted in its application being limited, and the detection limit is generally above mg / L.

[0003] Therefore, in order to make the portable XRF equipment meet the detection requirements of μg / L level trace analytes in liquid samples, a pre-enrichment method is generally used to enrich the target substance in the liquid sample through the enrichment material, so that the target substance content in the liquid sample in the enrichment material is increased to above the detection limit of the XRF equipment, thereby realizing the content detection of the target substance in the liquid sample.

[0004] However, in the current on-site testing process, on the one hand, a small solid phase extraction device is required to enrich the liquid by positive pressure, and a vacuum pump is used to negatively filter and collect the enriched material. The supporting instruments and power supply need to be carried with you. At the same time, due to the limitations of the corresponding equipment, the volume of the enriched liquid is small. If there is a large volume of liquid to be tested, the operation needs to be repeated many times, which cannot meet the needs of rapid on-site enrichment and testing.

[0005] On the other hand, although the existing enrichment device has no external power supply for enrichment, the operation method is complicated and a manual vacuum filtration pump is still required for filtration. The enriched material after the enrichment process is vacuum filtered onto the filter membrane, and then the filter membrane is removed and sampled using a sample box. The sample to be tested after sample preparation is then sent to the XRF detection equipment for detection.

[0006] Therefore, there is an urgent need for a new device and method for enriching and preparing samples of heavy metal elements in water for XRF detection to meet the needs of on-site rapid enrichment detection. Summary of the invention

[0007] The first aspect of the present application provides a device for enriching and preparing samples of heavy metal elements in water for XRF detection, comprising:

[0008] A sample carrier, used for collecting particle enriched materials, is cylindrical and has a first open side and a second open side. The sample carrier includes a sample collecting portion and a sample cup portion. The sample collecting portion and the sample cup portion are arranged in sequence from the first open side to the second open side in the axial direction of the sample carrier and are interconnected.

[0009] A membrane collar is sleeved on the outer periphery of the sample cup and is used to fix the filter screen used to filter the liquid;

[0010] The circular ring limiting cover is located at the second open side, the circular ring limiting cover is detachably connected to the sample collecting part, and is used to fix the membrane sleeve ring. The circular ring limiting cover itself has a liquid outlet corresponding to the position of the sample cup part in the axial direction;

[0011] The sample press comprises a connected pressure head and a pressure rod. When the sample press is inserted into the sample carrier from the first open side, the pressure rod pushes the particle-enriched material to gather toward the sample cup, and the particle-enriched material is pressed into a sample cake to be tested in the sample cup by the pressure head and the pressure rod.

[0012] In some optional embodiments of the first aspect of the present application, a through channel extending axially along the sample carrier is formed in the sample collecting portion, a sample containing cavity is formed in the sample cup portion, the through channel is connected to the sample containing cavity and the diameter of the through channel is larger than the diameter of the sample containing cavity.

[0013] In some optional embodiments of the first aspect of the present application, the diameter of the through channel decreases from the first open side to the second open side.

[0014] In some optional embodiments of the first aspect of the present application, the through channel includes a narrowing section having a conical cross-section in the axial direction of the sample carrier.

[0015] In some optional embodiments of the first aspect of the present application, the pressure head is detachably connected to the first open side of the sample carrier.

[0016] In some optional embodiments of the first aspect of the present application, the pressure head is connected to the sample carrier, and the tail end of the pressure rod is located in the sample cup and there is a gap between the tail end of the pressure rod and the end of the sample cup on the second open side.

[0017] In some optional embodiments of the first aspect of the present application, the sample carrier is formed with a circular cap head on the first open side, the circular cap head is connected to the pressure head and the connection between the two is sealed by a sealing ring, and the circular cap head is connected to the sample collecting part near the first open side.

[0018] In some optional embodiments of the first aspect of the present application, the annular cap head is threadedly connected to the pressure head.

[0019] In some optional embodiments of the first aspect of the present application, a first internal thread is formed on the inner periphery of the annular cap head, and a first external thread matching the first internal thread is formed on the outer periphery of the pressure head.

[0020] In some optional embodiments of the first aspect of the present application, the pressure head and the pressure rod are integrally formed, and the pressure head has a screwing and pressing portion protruding from the circular cap head in the axial direction of the sample carrier.

[0021] In some optional embodiments of the first aspect of the present application, the pressure head includes a round cover and a screw-pressing piece which are separately arranged, the round cover and the pressure rod are integrally formed, the pressure rod and the round cover are coaxially arranged, a first external thread is formed on the outer circumference of the round cover, and the screw-pressing piece and the side of the round cover opposite to the pressure rod are matched with each other in a male and female manner so that the round cover and the ring cap head are threadedly connected by screwing the screw-pressing piece and the pressure rod is pressed downward toward the second open side.

[0022] In some optional embodiments of the first aspect of the present application, a cross groove is formed on the side of the round cover opposite to the pressure rod, and the screw-pressing piece has a handle and a cross boss arranged on the handle, and the cross groove and the cross boss are male-female fit.

[0023] In some optional embodiments of the first aspect of the present application, the sample collecting portion is threadedly connected to the circular limiting cover.

[0024] In some optional embodiments of the first aspect of the present application, a second external thread is formed on the outer circumference of the sample collecting portion, and a second internal thread matching the second external thread is formed on the inner circumference of the annular limiting cover.

[0025] In some optional embodiments of the first aspect of the present application, in the axial direction of the sample carrier, the second external thread is fully distributed on the outer circumference of the sample collecting part, and when the annular limit cover is threadedly connected to the sample collecting part, the cover body of the annular limit cover covers the entire outer circumference of the sample collecting part.

[0026] In some optional embodiments of the first aspect of the present application, in the axial direction of the sample carrier, the sample collecting portion includes an extension section and an end section close to the second open side, a second external thread is formed on the end section, and when the annular limit cover is threadedly connected to the sample collecting portion, the cover body of the annular limit cover covers the outer circumference of the end section.

[0027] The second aspect of the present application provides a method for preparing a sample for enriching heavy metal elements in water for XRF detection, which uses the device for preparing a sample for enriching heavy metal elements in water for XRF detection according to the first aspect of the present application, comprising:

[0028] An enrichment step, wherein a first volume of granular enrichment material is put into an open enrichment bottle containing a liquid to be tested to form a solid-liquid enrichment system, and the solid-liquid enrichment system is shaken to allow the granular enrichment material to enrich the target analyte in the liquid to be tested, wherein the first volume is the same as the volume of the sample chamber;

[0029] The enriched test liquid is discharged, and the collecting part of the water heavy metal element enrichment sample preparation device for XRF detection is installed on the bottle mouth of the enrichment bottle, the collecting part includes a sample loading piece, a membrane sleeve ring and a circular ring limit cover, the first open side of the sample loading piece corresponds to the position of the bottle mouth and is sealed, the filter screen is sealed on the opening of the sample cup part close to the second open side, and the edge of the filter screen is constrained by the membrane sleeve ring, and the circular ring limit cover fixes the membrane sleeve ring, and the enriched test liquid in the solid-liquid enrichment system is discharged from the enrichment bottle from the filter screen and the liquid outlet in turn, and the granular enriched material is collected in the sample cavity of the sample cup part;

[0030] To form a sample cake to be tested, the collection part is removed from the enrichment bottle, and the sample press is inserted into the sample carrier from the first open side. The tail end of the pressing rod enters the sample cup through the sample collecting part, and the granular enriched material in the sample cup is squeezed through the pressing rod by the pressure head to form a sample cake to be tested.

[0031] In some optional embodiments of the second aspect of the present application, the granular enrichment material is granular resin powder.

[0032] In some optional embodiments of the second aspect of the present application, the present invention further includes:

[0033] Dry the sample cake to be tested, disassemble the circular limiting cover and the sample collecting part, expose the sample cake to be tested in the sample cup part, and use a water-absorbing material to absorb excess water of the sample cake to be tested to obtain a dry sample cake to be tested.

[0034] In some optional embodiments of the second aspect of the present application, the water-absorbing material includes dry filter paper.

[0035] In some optional embodiments of the second aspect of the present application, the enrichment bottle is made of an extrudable material, and in the step of discharging the enriched liquid to be tested:

[0036] The enrichment bottle is squeezed so that the enriched liquid to be tested in the enrichment bottle is squeezed out to the bottle mouth of the enrichment bottle and discharged from the enrichment bottle through the filter screen.

[0037] In some optional embodiments of the second aspect of the present application, the extrudable material is selected from at least one of polyethylene plastic, polyethylene aliphatic polymer plastic, polyethylene terephthalate plastic or polycarbonate plastic.

[0038] Beneficial effects:

[0039] The present application provides a sample preparation device for enriching heavy metal elements in water for XRF detection. During the enrichment process of the liquid to be tested, it is connected to the enrichment bottle to facilitate in-situ collection after enrichment. After the enrichment is completed, the enriched material is collected into the sample carrier through the enrichment sample preparation device, and the water after enrichment flows out from the filter screen fixed by the membrane ring to the circular limit cover, and finally the water is discharged through the liquid outlet. The sample cake to be tested is then prepared by the mutual compression and cooperation between the sample press and the sample carrier. The present application provides a sample preparation device for enriching heavy metal elements in water for XRF detection, which realizes the integration of enrichment of target analytes in the liquid to be tested, collection of granular enrichment materials and preparation of sample cakes to be tested, simplifies the experimental process, shortens the experimental time, and effectively improves the sensitivity of the XRF detection method. There is no need to carry additional supporting instruments and power supplies and vacuum filtration pumps for filtration, which simplifies the equipment requirements for XRF detection in outdoor scenes, meets the needs of rapid on-site enrichment and detection, and simplifies the detection steps.

[0040] The second aspect of the present application provides an enrichment and sample preparation method for XRF detection, which uses granular enrichment materials to oscillate in liquid samples to effectively improve the adsorption efficiency of the target to be detected in the liquid. At the same time, a volumetric flask with a volume commensurate with the volume of the liquid to be detected can be selected according to actual detection needs. Select a granular enrichment material of corresponding volume according to the volume of the liquid to be detected. The step of discharging the enriched liquid to be tested intercepts and collects the granular enrichment material through a filter screen, and the enriched liquid to be tested is discharged, and manual operation can be performed without the need to add other equipment. The limitation of the volume of the liquid to be tested by the traditional solid phase extraction method is lifted, and the need to carry solid phase extraction devices or centrifuges and other equipment during outdoor operations on site is avoided, and no power supply is required. The traditional method selects the corresponding enrichment and sample preparation device for XRF detection according to the volume of the actual granular enrichment material used, and the corresponding refers to the volume of the sample cavity in the sample cup being equal to the volume of the actual granular enrichment material used. Further, the first open side of the sample carrier is set to correspond to the size of the bottle mouth of the enrichment bottle, which is convenient for the operation when discharging the enriched liquid to be tested, and simplifies the sample preparation process and the equipment required for sample preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0042] Figure 1 This is an overall assembly structure diagram of a heavy metal element enrichment and sample preparation device for water used for XRF detection in Example 1 of the first aspect of the present application;

[0043] Figure 2It is an exploded view from one perspective of the heavy metal element enrichment and sample preparation device for XRF detection in Example 1 of the first aspect of the present application;

[0044] Figure 3 It is an exploded view of the sample preparation device for enriching heavy metal elements in water for XRF detection in Example 1 of the first aspect of the present application from another perspective;

[0045] Figure 4 yes Figure 1 Schematic diagram of the cross-section structure along the AA direction;

[0046] Figure 5 This is an overall assembly structure diagram of a heavy metal element enrichment and sample preparation device for water used for XRF detection in Example 2 of the first aspect of the present application;

[0047] Figure 6 It is an exploded view from one perspective of the sample preparation device for enriching heavy metal elements in water for XRF detection in Example 2 of the first aspect of the present application;

[0048] Figure 7 It is an exploded view from another perspective of the device for enriching and preparing samples of heavy metal elements in water for XRF detection in Example 2 of the first aspect of the present application;

[0049] Figure 8 yes Figure 4 Schematic diagram of the cross-sectional structure along direction BB.

[0050] Description of reference numerals:

[0051] Sample carrier-1; first open side-a; second open side-b; sample collecting part-11; through channel-111; narrowing section-1111; second external thread-112; extension section-113; end section-114; sample cup part-12; sample holding cavity-121; second open side-b; annular cap head-13; first internal thread-131; sealing ring-14;

[0052] Membrane collar-2;

[0053] Circular limiting cover-3; liquid outlet nozzle-31; second internal thread-32;

[0054] Sample press-4; pressure head-41; first external thread-411; screwing and pressing part-412; round cover-413; cross groove-4131; screwing and pressing piece-414; hand-held part-4141; cross protrusion-4142; pressure rod-42; spacing-c. DETAILED DESCRIPTION

[0055] The technical solution of the present application will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0056] In the description of the present application, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicating the orientation or positional relationship, are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present application. In addition, the terms "first", "second", and "third" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance.

[0057] In the description of this application, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0058] In addition, the technical features involved in the different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0059] [Example 1]

[0060] like Figures 1 to 4 As shown, the first aspect of the present application provides a device for enriching and preparing samples of heavy metal elements in water for XRF detection, comprising:

[0061] The sample carrier 1 is used to collect the particle enrichment material, is cylindrical and has a first open side a and a second open side bb. The sample carrier 1 includes a sample collecting portion 11 and a sample cup portion 12. The sample collecting portion 11 and the sample cup portion 12 are sequentially arranged from the first open side a to the second open side bb in the axial direction of the sample carrier 1 and are connected to each other.

[0062] The membrane ring 2 is sleeved on the outer periphery of the sample cup 12 and is used to fix the filter screen used for filtering the liquid;

[0063] The annular limiting cover 3 is located at the second open side bb. The annular limiting cover 3 is detachably connected to the sample collecting portion 11 and is used to fix the membrane sleeve ring 2. The annular limiting cover 3 itself has a liquid outlet 31 in the axial direction corresponding to the position of the sample cup portion 12.

[0064] The sample press 4 includes a connected pressure head 41 and a pressure rod 42. When the sample press 4 is inserted into the sample carrier 1 from the first open side a, the pressure rod 42 pushes the particle-enriched material to gather toward the sample cup 12, and the particle-enriched material is pressed into a sample cake to be tested in the sample cup 12 by the pressure head 41 and the pressure rod 42.

[0065] The present application provides a sample preparation device for enriching heavy metal elements in water for XRF detection. During the enrichment process of the liquid to be tested, it is connected to the enrichment bottle to facilitate in-situ collection after enrichment. After the enrichment is completed, the enriched material is collected into the sample carrier 1 through the enrichment sample preparation device, and the water after enrichment flows out from the filter screen fixed by the membrane ring 2 to the circular limit cover 3, and finally the water is discharged through the liquid outlet 31. The sample cake to be tested is then prepared by the mutual pressing and cooperation of the sample press 4 and the sample carrier 1. The present application provides a sample preparation device for enriching heavy metal elements in water for XRF detection, which realizes the integration of enrichment of target analytes in the liquid to be tested, collection of granular enrichment materials and preparation of sample cakes to be tested, simplifies the experimental process, shortens the experimental time, and effectively improves the sensitivity of the XRF detection method. There is no need to carry additional supporting instruments and power supplies and vacuum filtration pumps for filtration, which simplifies the equipment requirements for XRF detection in outdoor scenes, meets the needs of rapid on-site enrichment and detection, and simplifies the detection steps.

[0066] In some optional embodiments of the present application, a through channel 111 extending axially along the sample carrier 1 is formed in the sample collecting portion 11, and a sample containing cavity 121 is formed in the sample cup portion 12. The through channel 111 is connected to the sample containing cavity 121 and the diameter of the through channel 111 is greater than the diameter of the sample containing cavity 121.

[0067] In some optional embodiments of the first aspect of the present application, the diameter of the through channel 111 is larger than the diameter of the sample cavity 121. The diameter of each part of the through channel 111 is larger than the diameter of the sample cavity 121, or the diameter of the through channel 111 (average value) is larger than the diameter of the sample cavity 121. It is convenient for the particle enrichment material to be collected into the sample cavity 121 through the through channel 111. The sample cup portion 12 is annular, similar to the shape of a general sample cup for XRF detection.

[0068] In some optional embodiments of the first aspect of the present application, the diameter of the through channel 111 decreases from the first open side a to the second open side bb. In these embodiments, in the process of collecting the particle enrichment material, the particle enrichment material quickly moves and slides along the wall of the through channel 111 toward the sample chamber 121, thereby improving the collection efficiency.

[0069] In some optional embodiments of the first aspect of the present application, the through channel 111 includes a narrowing section 1111 having a conical cross-section in the axial direction of the sample carrier 1 .

[0070] In some optional embodiments of the present application, the pressure head 41 is detachably connected to the first open side a of the sample carrier 1. In these embodiments, when the pressure head 41 is connected to the first open side a of the sample carrier 1, pressure is applied to the particle enrichment material in the sample cup 12 of the sample carrier 1. After the pressure head 41 is detached from the sample carrier 1, it is convenient for the sample carrier 1 to collect the particle enrichment material enriched with heavy metal elements in water from the enrichment bottle.

[0071] In some optional embodiments of the present application, the pressure head 41 is connected to the sample carrier 1, and the tail end of the pressure rod 42 is located in the sample cup 12 and there is a spacing c between the tail end of the pressure rod 42 and the end of the sample cup 12 at the second open side bb. In these embodiments, the spacing c is reserved for forming a sample cake to be tested, and the length of the spacing c is approximately equal to the thickness of the sample cake to be tested.

[0072] In some optional embodiments of the present application, the length of the sample cavity 121 of the sample cup portion 12 is greater than the length of the spacing c, which facilitates the sample press 4 to compress the particle-enriched material in the sample cavity 121 for sample preparation.

[0073] In some optional embodiments of the present application, the sample carrier 1 is formed with a circular cap head 13 on the first open side a, and the circular cap head 13 is connected to the pressure head 41, and the connection between the two is sealed by a sealing ring 14. The sealing ring 14 can prevent the enriched test liquid and the particle enriched material from flowing out from the first open side a, so that the enriched test liquid flows out of the sample carrier 1 from the second open side bb, and then flows out from the liquid outlet 31 of the circular limit cover 3. The particle enriched material is collected in the sample cavity 121 of the sample cup portion 12 near the second open side bb.

[0074] In some optional embodiments of the first aspect of the present application, the sample carrier 1 is formed with a circular cap head 13 on the first open side a, and the circular cap head 13 is connected to the pressure head 41 and the connection between the two is sealed by a sealing ring 14. The sealing ring 14 can prevent the enriched test liquid and the particle enriched material from flowing out from the first open side a, so that the enriched test liquid flows out of the sample carrier 1 from the second open side bb, and then flows out from the liquid outlet 31 of the circular limit cover 3. The particle enriched material is collected in the sample cavity 121 of the sample cup portion 12 near the second open side bb.

[0075] In some optional embodiments of the first aspect of the present application, the annular cap head 13 is threadedly connected to the pressure head 41. The pressure head 41 can apply pressure to the particle enrichment material in the sample chamber 121 through the pressure rod 42 by screwing with the annular cap head 13. The threaded connection can realize quick and convenient disassembly and assembly between the annular cap head 13 and the pressure head 41, which is beneficial to the enrichment operation and tableting operation.

[0076] In some optional embodiments of the first aspect of the present application, a first internal thread 131 is formed on the inner periphery of the annular cap head 13, and a first external thread 411 matching the first internal thread 131 is formed on the outer periphery of the pressure head 41. In some examples, the sealing ring 14 is disposed in the annular cap head 13 and is located on the side of the first internal thread 131 facing the second open side bb, so as to achieve a threaded sealing connection between the pressure head 41 and the annular cap head 13.

[0077] In some optional embodiments of the first aspect of the present application, the pressure head 41 is integrally formed with the pressure rod 42, and the pressure head 41 has a screwing and pressing portion 412 protruding from the annular cap head 13 in the axial direction of the sample carrier 1. The pressure head 41 is tightly suspended with the first open side a of the sample carrier 1, so that the pressure rod 42 plays a supporting role for the sample round cake. In some examples, the inspection personnel hold the screwing and pressing portion 412 to rotate the sample press 4, so that the first external thread 411 of the pressure head 41 is screwed with the internal thread in the annular cap head 13, and the sample press 4 and the annular cap head 13 of the sample carrier 1 are threadedly connected, so that the pressure head 41 is connected with the first open side a of the sample carrier 1.

[0078] In some optional embodiments of the first aspect of the present application, the sample collecting portion 11 is threadedly connected to the annular limiting cover 3. In these embodiments, the sample collecting portion 11 is threadedly connected to the annular limiting cover 3, so as to quickly and conveniently fix the membrane ring 2 outside the sample cup portion 12.

[0079] In some optional embodiments of the first aspect of the present application, a second external thread 112 is formed on the outer periphery of the sample collecting portion 11 , and a second internal thread 32 matching the second external thread 112 is formed on the inner periphery of the annular limiting cover 3 .

[0080] In some optional embodiments of the first aspect of the present application, in the axial direction of the sample carrier 1, the second external thread 112 is fully distributed on the outer circumference of the sample collecting part 11, and when the annular limit cover 3 is threadedly connected to the sample collecting part 11, the cover body of the annular limit cover 3 covers the entire outer circumference of the sample collecting part 11.

[0081] [Example 2]

[0082] like Figure 2 As shown, the first aspect of the present application provides a device for enriching and preparing samples of heavy metal elements in water for XRF detection, comprising:

[0083] The sample carrier 1 is used to collect the particle enrichment material, is cylindrical and has a first open side a and a second open side bb. The sample carrier 1 includes a sample collecting portion 11 and a sample cup portion 12. The sample collecting portion 11 and the sample cup portion 12 are sequentially arranged from the first open side a to the second open side bb in the axial direction of the sample carrier 1 and are connected to each other.

[0084] The membrane ring 2 is sleeved on the outer periphery of the sample cup 12 and is used to fix the filter screen used for filtering the liquid;

[0085] The annular limiting cover 3 is located at the second open side bb. The annular limiting cover 3 is detachably connected to the sample collecting portion 11 and is used to fix the membrane sleeve ring 2. The annular limiting cover 3 itself has a liquid outlet 31 in the axial direction corresponding to the position of the sample cup portion 12.

[0086] The sample press 4 includes a connected pressure head 41 and a pressure rod 42. When the sample press 4 is inserted into the sample carrier 1 from the first open side a, the pressure rod 42 pushes the particle-enriched material to gather toward the sample cup 12, and the particle-enriched material is pressed into a sample cake to be tested in the sample cup 12 by the pressure head 41 and the pressure rod 42.

[0087] The diameter of the through channel 111 is larger than the diameter of the sample cavity 121. This means that the diameter of each part of the through channel 111 is larger than the diameter of the sample cavity 121, or the diameter of the through channel 111 (average value) is larger than the diameter of the sample cavity 121. This facilitates the particle enrichment material to be collected into the sample cavity 121 through the through channel 111. The sample cup 12 is annular, similar to the shape of a general sample cup for XRF detection.

[0088] The diameter of the through channel 111 decreases from the first open side a to the second open side bb. In these embodiments, during the process of collecting the particle-enriched material, the particle-enriched material quickly moves and slides along the wall of the through channel 111 toward the sample chamber 121, thereby improving the collection efficiency.

[0089] The through channel 111 includes a narrowing section 1111 having a conical cross section in the axial direction of the sample carrier 1 .

[0090] In some optional embodiments of the present application, the pressure head 41 is detachably connected to the first open side a of the sample carrier 1. In these embodiments, when the pressure head 41 is connected to the first open side a of the sample carrier 1, pressure is applied to the particle enrichment material in the sample cup 12 of the sample carrier 1. After the pressure head 41 is detached from the sample carrier 1, it is convenient for the sample carrier 1 to collect the particle enrichment material enriched with heavy metal elements in water from the enrichment bottle.

[0091] In some optional embodiments of the present application, the pressure head 41 is connected to the sample carrier 1, and the tail end of the pressure rod 42 is located in the sample cup 12 and there is a spacing c between the tail end of the pressure rod 42 and the end of the sample cup 12 at the second open side bb. In these embodiments, the spacing c is reserved for forming a sample cake to be tested, and the length of the spacing c is approximately equal to the thickness of the sample cake to be tested.

[0092] In some optional embodiments of the present application, the length of the sample cavity 121 of the sample cup portion 12 is greater than the length of the spacing c, which facilitates the sample press 4 to compress the particle-enriched material in the sample cavity 121 for sample preparation.

[0093] The sample carrier 1 is formed with a circular cap head 13 on the first open side a, and the circular cap head 13 is connected to the pressure head 41 and the connection between the two is sealed by a sealing ring 14. The sealing ring 14 can prevent the enriched test liquid and the particle enriched material from flowing out from the first open side a, so that the enriched test liquid flows out of the sample carrier 1 from the second open side bb, and then flows out of the enriched sample preparation device for XRF detection from the liquid outlet 31 of the circular limit cover 3. The particle enriched material is collected in the sample cavity 121 of the sample cup part 12 near the second open side bb.

[0094] The annular cap head 13 is threadedly connected to the pressure head 41. The pressure head 41 can apply pressure to the particle enrichment material in the sample chamber 121 through the pressure rod 42 by screwing with the annular cap head 13. The threaded connection can realize quick and convenient disassembly and assembly between the annular cap head 13 and the pressure head 41, which is beneficial to the enrichment operation and tableting operation.

[0095] A first internal thread 131 is formed on the inner periphery of the annular cap head 13, and a first external thread 411 matching the first internal thread 131 is formed on the outer periphery of the pressure head 41. In some examples, the sealing ring 14 is disposed in the annular cap head 13 and is located on the side of the first internal thread 131 facing the second open side bb, so as to achieve a threaded sealing connection between the pressure head 41 and the annular cap head 13.

[0096] The difference from the first embodiment is that the pressure head 41 includes a circular cover 413 and a screwing and pressing member 414 which are separately arranged, the circular cover 413 and the pressure rod 42 are integrally formed, the pressure rod 42 and the circular cover 413 are coaxially arranged, a first external thread 411 is formed on the outer periphery of the circular cover 413, the screwing and pressing member 414 and the circular cover 413 and the side of the pressure rod 42 opposite to each other are male and female matched, so that the circular cover 413 is threadedly connected with the annular cap head 13 by screwing the screwing and pressing member 414, and the pressure rod 42 is pressed downward toward the second open side bb. A cross groove 4131 is formed on the side of the circular cover 413 opposite to the pressure rod 42, the screwing and pressing member 414 has a hand-held portion 4141 and a cross convex head 4142 arranged on the hand-held portion 4141, and the cross groove 4131 and the cross convex head 4142 are male and female matched. When forming the sample cake to be tested, the granular enriched material in the sample chamber 121 needs to be pressed into tablets. The round cover 413 is held by hand to insert the pressing rod 42 into the through channel 111, and then the hand-held portion 4141 in the screw-pressing member 414 is held by hand, and the cross protrusion 4142 is aligned with the cross groove 4131 on the round cover 413 and then inserted into the cross groove 4131 to complete the male-female fit. The hand-held portion 4141 is rotated to drive the round cover 413 and the pressing rod 42 to rotate together, and the first external thread 411 on the outer periphery of the round cover 413 and the first internal thread 131 formed on the inner periphery of the annular cap head 13 are screwed together to complete the threaded connection.

[0097] In some optional embodiments of the first aspect of the present application, the sample collecting portion 11 is threadedly connected to the annular limiting cover 3. In these embodiments, the sample collecting portion 11 is threadedly connected to the annular limiting cover 3, so as to quickly and conveniently fix the membrane ring 2 outside the sample cup portion 12.

[0098] The difference from Example 1 is that: in the axial direction of the sample carrier 1, the sample collecting portion 11 includes an extension section 113 and an end section 114 close to the second open side bb, the second external thread 112 is formed on the end section 114, and when the circular ring limiting cover 3 is threadedly connected to the sample collecting portion 11, the cover body of the circular ring limiting cover 3 covers the outer periphery of the end section 114.

[0099] The second aspect of the present application provides a method for preparing a sample for enriching heavy metal elements in water for XRF detection, which uses the device for preparing a sample for enriching heavy metal elements in water for XRF detection according to the first aspect of the present application, comprising:

[0100] S10: Enrichment step, putting a first volume of granular enrichment material into an open enrichment bottle containing a test liquid to form a solid-liquid enrichment system, and shaking the solid-liquid enrichment system to allow the granular enrichment material to enrich the target analyte in the test liquid. The first volume is the same as the volume of the sample chamber 121.

[0101] S20: discharge the enriched test liquid, install the collecting part of the enrichment sample preparation device for XRF detection to the bottle mouth of the enrichment bottle, the collecting part includes a sample carrier 1, a membrane ring 2 and a circular limit cover 3, the first open side a of the sample carrier 1 corresponds to the position of the bottle mouth and is sealed, the filter screen is sealed on the opening of the sample cup part 12 close to the second open side bb, and the membrane ring 2 is used to constrain the edge of the filter screen, the circular limit cover 3 fixes the membrane ring 2, and the enriched test liquid in the solid-liquid enrichment system is discharged from the enrichment bottle from the filter screen and the liquid outlet 31 in turn, and the granular enriched material is collected in the sample cavity 121 of the sample cup part 12.

[0102] S30: forming a sample cake to be tested, removing the collected part from the enrichment bottle, inserting the sample press 4 into the sample carrier 1 from the first open side a, and the tail end of the pressing rod 42 enters the sample cup 12 through the sample collecting part 11, and the granular enriched material in the sample cup 12 is squeezed through the pressing rod 42 by the pressure head 41 to form a sample cake to be tested.

[0103] In some optional embodiments of the second aspect of the present application, the granular enrichment material is granular resin powder.

[0104] In some optional embodiments of the second aspect of the present application, the first open side a of the sample carrier 1 corresponds to the position of the bottle mouth and is sealed and connected specifically as follows: the bottle mouth of the enrichment bottle is selected to have a first external thread 411 and the size of the bottle mouth matches the size of the circular cap head 13. The bottle mouth of the enrichment bottle can be threadedly connected to the circular cap head 13 to facilitate the drainage operation after enrichment.

[0105] The pore size of the filter screen is smaller than the particle size of the granular enrichment material, and the membrane sleeve ring 2 fixes the filter screen to form a flat surface.

[0106] In some optional embodiments of the second aspect of the present application, the present invention further includes:

[0107] S40: Drying the sample cake to be tested, disassembling the annular limiting cover 3 and the sample collecting portion 11, exposing the sample cake to be tested in the sample cup portion 12, and using a water absorbing material to absorb excess water from the sample cake to be tested to obtain a dry sample cake to be tested.

[0108] In some optional embodiments of the second aspect of the present application, the water-absorbing material includes dry filter paper.

[0109] In some optional embodiments of the second aspect of the present application, in step S20, the enrichment bottle is made of an extrudable material, and in the step of discharging the enriched liquid to be tested:

[0110] The enrichment bottle is squeezed so that the enriched liquid to be tested in the enrichment bottle is squeezed out to the bottle mouth of the enrichment bottle and discharged from the enrichment bottle through the filter screen.

[0111] In some optional embodiments of the second aspect of the present application, the extrudable material is selected from at least one of polyethylene plastic, polyethylene aliphatic polymer plastic, polyethylene terephthalate plastic or polycarbonate plastic.

[0112] In some optional embodiments of the second aspect of the present application, the enrichment bottle is a plastic bottle, such as a polyethylene (PE) plastic bottle, a polyethylene aliphatic polymer (PP) plastic bottle, a polyethylene terephthalate (PET) plastic bottle or a polycarbonate (PC) plastic bottle.

[0113] The use of extrusion operation and filter screen eliminates the trouble of carrying a vacuum pump or vacuum adsorption device, and is suitable for rapid on-site testing.

[0114] The enrichment and sample preparation method for XRF detection provided in the second aspect of the present application adopts the granular enrichment material to enrich in the liquid sample in an oscillating manner, which effectively improves the adsorption efficiency of the target to be detected in the liquid. At the same time, a volumetric flask with a volumetric flask volume commensurate with the volume of the liquid to be detected can be selected according to the actual detection needs. The granular enrichment material of the corresponding volume is selected according to the volume of the liquid to be detected. The step of discharging the enriched liquid to be tested intercepts and collects the granular enrichment material through a filter screen, and the enriched liquid to be tested is discharged, and manual operation can be performed without the need to add other equipment. The limitation of the volume of the liquid to be tested by the traditional solid phase extraction method is lifted, and the need to carry solid phase extraction devices or centrifuges and other equipment during outdoor operations on site is avoided, and no power supply is required. The traditional enrichment and sample preparation device for XRF detection is selected according to the volume of the actual granular enrichment material used, and the corresponding refers to the volume of the sample chamber 121 in the sample cup 12 is equal to the volume of the actual granular enrichment material used. Further, the first open side a of the sample carrier 1 is set to correspond to the bottle mouth size of the enrichment bottle, which is convenient for discharging the enriched liquid to be tested, simplifying the sample preparation process and the equipment required for sample preparation.

[0115] The traditional solid phase extraction method eliminates the limitation of the volume of the liquid to be tested, avoids the need to carry solid phase extraction devices or centrifuges and other equipment during outdoor work, and does not require power supply. The liquid processed in step S10 can be from tens of milliliters to several liters, and enrichment can be achieved in about 10 minutes. The mass of the particle enrichment material used is determined by the volume of the liquid to be tested, and the volume of the sample cup is further determined, and enrichment sample preparation devices of different specifications for XRF detection can be prepared.

[0116] In step S30 and step S40: the steps of shaping the particle-enriched material into an XRF sample cake by tableting and drying the XRF sample cake avoid the influence of residual liquid on the measurement to a great extent, and at the same time improve the stability of instrument detection and the detection limit of the method.

[0117] During the process of squeezing out the liquid in step S20, the use of the filter and the oscillating enrichment method greatly reduces the high pressure caused by the accumulation of particle powder, and manual operation can be performed. At the same time, the collection step operation time period can be completed in about 1 minute (when the water sample is 100 mL).

[0118] The above is only a specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application shall be based on the protection scope of the claims.

Claims

1. A device for enriching and preparing samples of heavy metal elements in water for XRF detection, characterized in that: include: A sample carrier, used for collecting particle enrichment materials, is cylindrical and has a first open side and a second open side, the sample carrier comprises a sample collecting portion and a sample cup portion, the sample collecting portion and the sample cup portion are sequentially arranged from the first open side to the second open side in the axial direction of the sample carrier and are interconnected; A membrane collar, sleeved on the outer periphery of the sample cup, for fixing the filter screen used for filtering the liquid; A circular stop cover is located at the second open side, the circular stop cover is detachably connected to the sample collecting portion and is used to fix the membrane sleeve ring, and the circular stop cover itself has a liquid outlet corresponding to the position of the sample cup portion in the axial direction; The sample press comprises a connected pressure head and a pressure rod. When the sample press is inserted into the sample carrier from the first open side, the pressure rod pushes the particle-enriched material to gather toward the sample cup portion, and the particle-enriched material is pressed into a sample cake to be tested in the sample cup portion by the pressure head and the pressure rod.

2. The device for enriching and preparing samples of heavy metal elements in water for XRF detection according to claim 1, characterized in that: A through channel extending along the axial direction of the sample carrier is formed in the sample collecting portion, a sample containing cavity is formed in the sample cup portion, the through channel is communicated with the sample containing cavity and the diameter of the through channel is greater than the diameter of the sample containing cavity; Preferably, the diameter of the through passage decreases from the first open side to the second open side.

3. The device for enriching and preparing samples of heavy metal elements in water for XRF detection according to claim 2, characterized in that: The through channel includes a narrowing section with a conical cross section in the axial direction of the sample carrier.

4. The device for enriching and preparing samples of heavy metal elements in water for XRF detection according to claim 1, characterized in that: The pressure applying head is detachably connected to the first open side of the sample carrier; Preferably, the pressure head is connected to the sample carrier, and the tail end of the pressure rod is located in the sample cup portion and there is a gap between the tail end of the pressure rod and the end of the sample cup portion located at the second open side; Preferably, the sample carrier is formed with a circular cap head on the first open side, the circular cap head is connected to the pressure head and the connection between the two is sealed by a sealing ring, and the circular cap head is connected to the sample collecting part close to the first open side.

5. The device for enriching and preparing samples of heavy metal elements in water for XRF detection according to claim 4, characterized in that: The annular cap head is threadedly connected with the pressure applying head.

6. The device for enriching and preparing samples of heavy metal elements in water for XRF detection according to claim 5, characterized in that: The inner circumference of the annular cap head is formed with a first internal thread, and the outer circumference of the pressure applying head is formed with a first external thread matching the first internal thread; Preferably, the pressure head is integrally formed with the pressure rod, and the pressure head has a screwing and pressing portion protruding from the annular cap head in the axial direction of the sample carrier; Preferably, the pressure head comprises a circular cover and a screw-pressing piece which are separately arranged, the circular cover and the pressure rod are integrally formed, the pressure rod and the circular cover are coaxially arranged, the circular cover is formed with the first external thread on its outer circumference, the screw-pressing piece and the circular cover on the side opposite to the pressure rod are male and female matched, so that the circular cover is threadedly connected with the circular cap head by screwing the screw-pressing piece and the pressure rod is pressed downward toward the second open side; Preferably, a cross groove is formed on the side of the round cover opposite to the pressure rod, and the screwing and pressing member has a hand-held portion and a cross protrusion arranged on the hand-held portion, and the cross groove and the cross protrusion are male-female fit.

7. The device for enriching and preparing samples of heavy metal elements in water for XRF detection according to claim 1, characterized in that: The sample collecting portion is threadedly connected to the annular limiting cover; Preferably, the outer circumference of the sample collecting portion is formed with a second external thread, and the inner circumference of the annular limiting cover is formed with a second internal thread matching the second external thread; Preferably, in the axial direction of the sample carrier, the second external thread is fully distributed on the outer circumference of the sample collecting portion, and when the annular limiting cover is threadedly connected to the sample collecting portion, the cover body of the annular limiting cover covers the entire outer circumference of the sample collecting portion; Preferably, in the axial direction of the sample carrier, the sample collecting portion includes an extension section and an end section close to the second open side, the second external thread is formed on the end section, and when the annular limit cover is threadedly connected to the sample collecting portion, the cover body of the annular limit cover covers the outer circumference of the end section.

8. A method for enriching and preparing samples of heavy metal elements in water for XRF detection, characterized in that: The sample preparation device for enriching heavy metal elements in water for XRF detection according to any one of claims 1 to 7 is used to prepare the sample, comprising: an enrichment step, putting a first volume of granular enrichment material into an open enrichment bottle containing a liquid to be tested to form a solid-liquid enrichment system, and shaking the solid-liquid enrichment system to allow the granular enrichment material to enrich the target analyte in the liquid to be tested, wherein the first volume is the same as the volume of the sample chamber; The enriched liquid to be tested is discharged, and the collecting part of the sample preparation device for enriching heavy metal elements in water for XRF detection is installed on the bottle mouth of the enrichment bottle, the collecting part includes the sample loading part, the membrane ring and the circular ring limit cover, the first open side of the sample loading part corresponds to the position of the bottle mouth and is sealed, the filter screen is sealed on the opening of the sample cup part close to the second open side, and the edge of the filter screen is constrained by the membrane ring, and the circular ring limit cover fixes the membrane ring, the enriched liquid to be tested in the solid-liquid enrichment system is discharged from the enrichment bottle from the filter screen and the liquid outlet in turn, and the granular enrichment material is collected in the sample holding cavity of the sample cup part; To form a sample cake to be tested, the collecting part is removed from the enrichment bottle, the sample press is inserted into the sample carrier from the first open side, the tail end of the pressing rod enters the sample cup through the sample collecting part, and the granular enriched material in the sample cup is squeezed through the pressing rod by the pressing head to form a sample cake to be tested; Preferably, the granular enrichment material is a granular resin powder.

9. The method for enriching and preparing samples of heavy metal elements in water for XRF detection according to claim 8, characterized in that: Also includes: Drying the sample cake to be tested, disassembling the annular limiting cover and the sample collecting part to expose the sample cake to be tested in the sample cup part, and using a water absorbing material to absorb excess water from the sample cake to be tested to obtain a dry sample cake to be tested; Preferably, the water-absorbing material comprises dry filter paper.

10. The method for enriching and preparing samples of heavy metal elements in water for XRF detection according to claim 8, characterized in that: The enrichment bottle is made of an extrudable material, and in the step of discharging the enriched liquid to be tested: Squeezing the enrichment bottle so that the enriched liquid to be tested in the enrichment bottle is squeezed out to the bottle mouth of the enrichment bottle and discharged from the enrichment bottle through the filter screen; Preferably, the extrudable material is selected from at least one of polyethylene plastic, polyethylene aliphatic polymer plastic, polyethylene terephthalate plastic or polycarbonate plastic.

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