Automatic online extraction device and method for MNPs in high-salt seawater

Abstract

The invention relates to an automatic online extraction device and method for MNPs in high-salt seawater, and the device comprises an extraction tank which can be placed in a turnover manner and comprises a sealed separation chamber; the supporting partition plate is arranged in the separation chamber and divides the separation chamber into a first chamber and a second chamber, and one end of the supporting partition plate is provided with a filtering opening communicated with the first chamber and the second chamber; the MNPs complex filter membrane is arranged at the filter opening; an analysis liquid inlet and outlet and a complexing agent solution inlet are formed in one end, far away from the MNPs complex filter membrane, of the first chamber; a waste liquid outlet is formed in one end, far away from the MNPs complex filter membrane, of the second chamber, and an extracting solution inlet is formed in one end, close to the MNPs complex filter membrane, of the second chamber. According to the automatic online extraction device and method for the MNPs in the high-salinity seawater, the automatic extraction of the MNPs in the high-salinity seawater is realized through the double-cavity automatic online extraction device, and the separation efficiency of the MNPs is improved.

Description

Technical Field

[0001] This invention relates to the technical field of environmental nanoparticle analysis, and in particular to an automated online extraction device and method for MNPs in high-salinity seawater. Background Technology

[0002] With the rapid development of nanotechnology, nanomaterials have been widely applied in various fields such as industrial production, biomedicine, and environmental governance. Consequently, a large number of metal nanoparticles (MNPs) enter the aquatic environment through all stages of their life cycle, including production emissions, product use, and waste disposal. Due to the unique nano-effects of MNPs (such as high specific surface area and strong reactivity), their migration, transformation, and accumulation in the aquatic environment may pose potential risks to the structure and function of aquatic ecosystems. At the same time, they threaten human health through bioaccumulation in the food chain, and the related environmental risks have attracted widespread attention from the global academic community and regulatory agencies.

[0003] In the field of environmental nanoparticle analysis, the accurate detection of micronutrient nanoparticles (MNPs) in high-salinity seawater systems is a core prerequisite for marine environmental monitoring, ecological risk assessment, and pollution source tracing, possessing significant academic value and practical implications. However, high-salinity seawater matrices contain high concentrations of electrolyte ions (mainly Na+). + Cl - Salt ions, such as those found in high-salinity seawater, can significantly interfere with the instrumental detection of micronutrient nanoparticles (MNPs). In mainstream detection techniques, such as single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS), high concentrations of salt ions can easily lead to problems such as plasma torch instability, signal suppression, increased background noise, and mass spectrometry interference. This directly causes deviations in the particle size and concentration detection results of MNPs, severely affecting the accuracy and sensitivity of the detection. Therefore, efficient enrichment of MNPs in high-salinity seawater and simultaneous deep removal of salt ions before instrumental detection are crucial steps in solving these detection challenges.

[0004] Currently, cloud point extraction (CPE) is the commonly used method in the industry for the enrichment of MNPs and the separation of salt ions in high-salinity seawater. This method involves adding a complexing agent to the sample, causing the MNPs to undergo a specific complexation reaction with the complexing agent to form hydrophobic complexes. The enrichment of MNPs is then achieved through steps such as heating, centrifugation, and phase separation. However, this technology has significant drawbacks: the entire extraction process requires offline, step-by-step operation, is cumbersome, and highly dependent on manual intervention. This not only results in a long operation cycle but also makes it prone to systematic errors introduced by human error, making it difficult to meet the high-throughput processing requirements of large batches of samples.

[0005] In summary, existing enrichment and separation technologies for MNPs in high-salinity seawater suffer from problems such as cumbersome operation, insufficient high-throughput processing capacity, and poor salt ion removal effect. There is an urgent need to develop an efficient, automated, and highly synergistic online extraction and analysis technology and supporting device to overcome the technical bottleneck of accurate detection of MNPs in high-salinity seawater systems. Summary of the Invention

[0006] Based on this, the purpose of the present invention is to provide an automatic online extraction device and method for MNPs in high-salinity seawater, which realizes automatic extraction of MNPs in high-salinity seawater through a dual-chamber online extraction device, thereby improving the separation efficiency of MNPs.

[0007] In a first aspect, this application provides an automated online extraction device for MNPs in high-salinity seawater, comprising: An extractor that can be tilted and placed, including a sealed separation chamber; A support partition is disposed in the separation chamber, dividing the separation chamber into a first chamber and a second chamber. One end of the support partition is provided with a filter port that connects the first chamber and the second chamber. MNPs complex filter membrane is disposed at the filter port; The first chamber has an analytical solution inlet / outlet and a complexing agent solution inlet at the end away from the MNPs complex filter membrane; the second chamber has a waste liquid outlet at the end away from the MNPs complex filter membrane and an extractant inlet at the end closer to the MNPs complex filter membrane.

[0008] In some possible implementations, the complexing agent solution inlet faces a first direction, the waste liquid outlet and the extract inlet face a second direction, and the first direction and the second direction are opposite.

[0009] In some possible implementations, the complexing agent solution inlet and the waste liquid outlet are symmetrically arranged with respect to the supporting partition; the analytical liquid inlet and outlet are located on the side of the extraction tank near the complexing agent solution inlet.

[0010] In some possible implementations, the first chamber of the extraction vessel is a sealed chamber made of quartz material, and the supporting partition is a partition made of polytetrafluoroethylene.

[0011] In some embodiments, the pore size of the MNPs complex filter membrane is between 200 nm and 1000 nm.

[0012] In some implementations, a temperature control module is also included, which controls the operating temperature inside the extraction tank.

[0013] In some possible implementations, a plurality of solenoid valves are also included, which independently control the on / off switching of the analytical liquid inlet / outlet, the complexing agent solution inlet, the waste liquid outlet, and the extract inlet.

[0014] In some possible implementations, a drive unit is also included, which includes a connecting pipe network and a multi-channel peristaltic pump connected to the connecting pipe network. The connecting pipe network includes several connecting pipes, each of which is connected to the analytical solution inlet / outlet, the complexing agent solution inlet, and the extract inlet, respectively. The multi-channel peristaltic pump independently controls the delivery of the high-salt seawater sample, the complexing agent solution, and the extract in the connecting pipe network.

[0015] Secondly, this application provides an automated online extraction method for MNPs in high-salinity seawater, applied to the automated online extraction device for MNPs in high-salinity seawater as described in any of the above claims, the method comprising the following steps: S10, complexation enrichment: Seawater sample and complexing agent solution are intermittently introduced into the first chamber in a pulsed manner through the analytical liquid inlet and the complexing agent solution inlet, respectively, and flow along the surface of the support partition to the filter port. This allows the metal nanoparticles in the seawater sample to complex with the complexing agent solution, forming MNPs complexes. The MNPs complexes are then retained by the MNPs complex filter membrane, while the high-salt matrix in the seawater sample, along with the seawater, passes through the MNPs complex filter membrane into the second chamber and is discharged from the waste liquid outlet. S20, elution: The extraction tank is inverted so that the second chamber is on top and the first chamber is on the bottom. The extract inlet and the analytical liquid outlet are opened, while the complexing agent solution inlet and the waste liquid outlet are closed. The extract is introduced into the second chamber through the extract inlet in a pulsed manner, and then through the filter port to irrigate the MNPs complex filter membrane in a pulsed manner, dissolving the MNPs complexes trapped on the MNPs complex filter membrane. The resulting eluent enters the first chamber and flows out through the analytical solution inlet and outlet.

[0016] In some possible implementations, in step S10, during the complexation enrichment, the flow rate of the seawater sample and the complexing agent solution is controlled to be between 1 mL / min and 5 mL / min, the pulse interval is between 5 s and 30 s, the enrichment time is between 3 min and 10 min, and the elution time is between 1 min and 5 min.

[0017] This application provides an automatic online extraction device and method for MNPs in high-salinity seawater, comprising an extraction tank that can be tilted, a supporting partition, and an MNPs complex filter membrane. The extraction tank includes a sealed separation chamber. The supporting partition divides the separation chamber into a first chamber and a second chamber, and has a filter port connecting the two chambers. The MNPs complex filter membrane is disposed at the filter port. The first chamber has an analytical liquid inlet / outlet and a complexing agent solution inlet at the end away from the MNPs complex filter membrane. The second chamber has a waste liquid outlet at the end away from the MNPs complex filter membrane and an extractant inlet at the end closer to the MNPs complex filter membrane. The automated extraction process using the online extraction device provided in this application involves firstly allowing the seawater sample and complexing agent solution to flow intermittently into the first chamber via the analytical solution inlet and the complexing agent solution inlet, respectively, in a pulsed manner. The samples then flow along the surface of the support partition to the filter port, where the metal nanoparticles in the seawater sample complex with the complexing agent solution to form MNPs complexes. These MNPs complexes are then retained by the MNPs complex filter membrane. The high-salt matrix in the seawater sample, along with the seawater, passes through the MNPs complex filter membrane into the second chamber and exits through the waste liquid outlet. Next, the extraction tank is inverted so that the second chamber is on top and the first chamber is below. The extraction solution inlet and the analytical solution inlet are opened, while the complexing agent solution inlet and the waste liquid outlet are closed. The extraction solution then flows intermittently into the second chamber via the extraction solution inlet in a pulsed manner, passing through the filter port and rinsing the MNPs complex filter membrane in a pulsed manner. This dissolves the MNPs complexes retained on the filter membrane, and the resulting eluent enters the first chamber and exits through the analytical solution inlet and outlet. By using this extraction device and the corresponding automatic extraction method, and by controlling the fluid path and timing, the automatic extraction of MNPs from high-salinity seawater is achieved, effectively improving the separation efficiency. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 A schematic diagram of an automatic online extraction device for MNPs in high-salinity seawater provided in this application embodiment; Figure 2 This is a schematic diagram of the automatic online extraction device after it has been flipped. Figure 3 This application provides a flowchart of the steps for an automated online extraction method of MNPs from high-salinity seawater. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the protection scope of this application.

[0021] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to limit the embodiments of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” as used herein refers to and includes any or all possible combinations of one or more of the associated listed items.

[0022] In the following description, when referring to the accompanying drawings, unless otherwise indicated, the same numbers in different drawings represent the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this application. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this application as detailed in the appended claims. In the description of this application, it should be understood that the terms "first," "second," "third," etc., are used only to distinguish similar objects and are not necessarily used to describe a specific order or sequence, nor should they be construed as indicating or implying relative importance. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0023] Furthermore, in the description of this application, unless otherwise stated, "multiple" means two or more. "And / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, or B alone. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0024] Metal nanoparticles (MNPs) in this application specifically refer to nanoscale metallic particles existing in high-salinity seawater environments. MNPs include elemental metal nanoparticles, metal oxide nanoparticles, and other nanoparticles containing metallic elements. MNPs possess the properties of metallic substances as well as the unique morphological characteristics and special properties of nanomaterials, such as size, shape, specific surface area, surface functional groups, and surface charge. Therefore, they play an important role in research across multiple fields. In the field of environmental nanoanalysis, MNPs are important monitoring targets. However, the monitoring of MNPs in high-salinity seawater suffers from inaccuracies. Salt ions (such as Na+ and Cl-) in the high-salinity seawater matrix can interfere with detection, leading to a decrease in analytical sensitivity.

[0025] Based on this, this application aims to provide an automated online extraction device and method for MNPs in high-salinity seawater, which can filter out the high-salinity matrix in high-salinity seawater and extract MNPs, thereby improving analytical accuracy and separation efficiency.

[0026] Example 1 Please see Figures 1 to 2 , Figure 1 This is a schematic diagram of an automatic online extraction device for MNPs in high-salinity seawater provided in an embodiment of this application. Figure 2 This is a schematic diagram of the extraction device after it has been flipped.

[0027] This application provides an extraction device for MNPs in high-salinity seawater, comprising: The extractor 1 is tiltable and includes a sealed separation chamber; A support partition 2 is disposed in the separation chamber, dividing the separation chamber into a first chamber 3 and a second chamber 4. One end of the support partition 2 is provided with a filter port that connects the first chamber 3 and the second chamber 4. MNPs complex filter membrane 5 is disposed at the filter port; The first chamber 3 is provided with an analytical liquid inlet / outlet 31 and a complexing agent solution inlet 32 ​​at the end away from the MNPs complex filter membrane 5; the second chamber 4 is provided with a waste liquid outlet 41 at the end away from the MNPs complex filter membrane 5, and an extractant inlet 42 at the end of the second chamber 4 close to the MNPs complex filter membrane 5.

[0028] The automatic online extraction device for MNPs in high-salinity seawater provided in this application includes an extraction tank 1 that can be tilted, a supporting partition 2, and an MNPs complex filter membrane 5. The extraction tank 1 includes a sealed separation chamber. The supporting partition 2 divides the separation chamber into a first chamber 3 and a second chamber 4, and has a filter port connecting the two chambers. The MNPs complex filter membrane 5 is disposed at the filter port. The first chamber 3 has an analytical liquid inlet / outlet 31 and a complexing agent solution inlet 32 ​​at the end away from the MNPs complex filter membrane 5. The second chamber 4 has a waste liquid outlet 41 at the end away from the MNPs complex filter membrane 5, and an extractant inlet 42 at the end of the second chamber 4 close to the MNPs complex filter membrane 5. During the enrichment stage, the high-salinity seawater sample and the complexing agent solution enter the first chamber 3 in a pulsed manner. The MNPs in the high-salinity seawater sample undergo a complexation reaction with the complexing agent solution to form MNPs complexes. The MNPs complexes are retained in the upper first chamber 3 by the supporting partition 2 and the MNPs complex filter membrane 5. The remaining matrix in the high-salinity seawater sample passes through the filter membrane into the second chamber 4 and is discharged through the waste liquid outlet 41 of the second chamber 4. During the elution stage, the extraction tank 1 is flipped so that the relative positions of the first chamber 3 and the second chamber 4 are reversed. At this time, the MNPs complexes are located in the lower chamber. The extractant inlet 42 of the second chamber 4 is pulsedly added to dissolve the MNPs complexes, which are then discharged with the liquid from the analytical liquid outlet 31 of the first chamber 3, thereby achieving effective separation of MNPs.

[0029] The first chamber 3 and the second chamber 4 are sealed chambers. In one embodiment, the first chamber 3 is a sealed chamber made of quartz. Quartz, as a high-performance silicate material, has high hardness, high temperature resistance, and stable chemical properties. Seawater samples contain a high-salt matrix, and the quartz first chamber 3 can effectively resist seawater corrosion, improving the chamber's sealing performance and service life.

[0030] The supporting partition 2 is made of polytetrafluoroethylene (PTFE). PTFE is a polymer material that can reduce fluid flow resistance and prevent MNPs complexes from adhering to the surface of the supporting partition 2, thereby improving the mass transfer efficiency of intermittent flow.

[0031] The MNPs complex filter membrane 5 is a polycarbonate membrane. Polycarbonate (PC) is an engineering plastic with high mechanical strength, chemical stability, and thermal stability, and is resistant to high salt corrosion. The MNPs complex filter membrane 5 separates substances from seawater samples through several filtration pores on its membrane. After the seawater sample is mixed with the complexing agent solution, the MNPs in the sample react chemically with the complexing agent solution to form MNPs complexes. The filtration pore size of the MNPs complex filter membrane 5 is set to allow only the high-salt matrix in the seawater sample to pass through while retaining the MNPs complexes. Even if the filtration pore size of the MNPs complex filter membrane 5 is smaller than the size of the MNPs complexes, in one embodiment, the filtration pore size of the MNPs complex filter membrane 5 is 200nm-1000nm. This allows the MNPs complexes to be retained on the side of the filter membrane facing the first chamber 3 during the enrichment stage, while the high-salt matrix in the seawater sample passes through the filtration pores of the filter membrane into the second chamber 4, thereby separating the MNPs from the high-salt matrix.

[0032] In this embodiment, the first chamber 3, the supporting partition 2, and the MNPs complex filter membrane 5 of the extraction tank 1 are respectively composed of quartz, polytetrafluoroethylene, and polycarbonate, which enables the device to resist high salt corrosion, thereby improving the stability and service life of the device.

[0033] In one embodiment, the seawater sample and the complexing agent solution are introduced into the first chamber 3 by pulses with preset flow parameters. For example, the flow rate during the enrichment stage can be set to 1~5 mL / min, and the pulse interval can be set to 5~30 s.

[0034] In one embodiment, the device further includes a flipping drive mechanism, which is connected to the extraction tank 1 and is used to drive the extraction tank 1 to flip.

[0035] The complexing agent solution inlet 32 ​​faces a first direction, while the waste liquid outlet 41 and the extract inlet 42 face a second direction, with the first and second directions being opposite. The complexing agent inlet is located on the side of the first chamber 3 away from the second chamber 4, and the waste liquid outlet 41 and the extract inlet 42 are located on the side of the second chamber 4 away from the first chamber 3. Therefore, the first direction facing the complexing agent solution inlet 32 ​​is opposite to the second direction facing the waste liquid outlet 41 and the extract inlet 42. For example, in the enrichment stage, the first chamber 3 and the second chamber 4 are respectively located at the upper and lower positions of the extraction tank 1. With the complexing agent solution inlet 32 ​​facing upwards, the first direction is vertically upwards; with the waste liquid outlet 41 and the extract inlet 42 facing downwards, the second direction is vertically downwards. Correspondingly, when the extraction tank 1 is tilted, the first direction is vertically downwards, and the second direction is vertically upwards, with the first and second directions being opposite.

[0036] In one embodiment, the complexing agent solution inlet 32 ​​and the waste liquid outlet 41 are symmetrically arranged with respect to the supporting partition 2. The supporting partition 2 divides the separation chamber into a first chamber 3 and a second chamber 4. The complexing agent solution inlet 32 ​​and the waste liquid outlet 41 are symmetrical about the central axis of the supporting partition 2 and are both located at the end away from the filter port. This facilitates the flow of seawater sample and complexing agent solution within the chamber through an inlet-filter port-outlet pathway, allowing for more uniform flow to the surface of the MNPs complex filter membrane 5 during the flow process. Simultaneously, it maintains fluid balance during waste liquid discharge, avoiding pressure unevenness.

[0037] In one embodiment, the analytical solution inlet / outlet 31 is located on the side of the extraction tank 1 near the complexing agent solution inlet 32. Specifically, the analytical solution inlet / outlet 31 is located on the side of the first chamber 3 near the complexing agent solution inlet 32. During the enrichment stage, the seawater sample and the complexing agent solution enter the first chamber 3 from the analytical solution inlet / outlet 31 and the complexing agent solution inlet 32, respectively, and rapidly fuse, thereby allowing the mixed solution to flow uniformly onto the surface of the MNPs complex filter membrane 5.

[0038] In one embodiment, the device further includes a temperature control module that controls the operating temperature inside the extraction tank 1. The temperature control module can be a temperature control system installed inside or outside the extraction tank 1, which adjusts the temperature inside the chamber by heating or cooling, allowing the device to perform separation at a preset operating temperature. This operating temperature is the temperature that achieves optimal efficiency in the enrichment and elution stages; for example, the operating temperature is set between 15 and 25°C. The operating temperatures for the enrichment and elution stages can be the same or different.

[0039] In this embodiment, the temperature of the separation environment in the chamber is controlled by a temperature control module. This not only avoids the impact of temperature fluctuations on the filter membrane efficiency, but also maintains the optimal temperature for the complexing reaction between the complexing agent solution and MNPs in the seawater sample, thereby improving the recovery rate of MNPs. By dynamically adjusting the operating temperature of the device, the separation efficiency of MNPs is effectively improved.

[0040] In one embodiment, the system also presets the working duration of the enrichment stage and the elution stage, and uses a temperature control module to synchronously adjust the working temperature in the chamber according to the time sequence changes of the enrichment stage and the elution stage. For example, the duration of the enrichment stage is set to 3~10min, and the duration of the elution stage is set to 1~5min.

[0041] In one embodiment, the device further includes a plurality of solenoid valves, which independently control the on / off switching of the analytical liquid inlet / outlet 31, the complexing agent solution inlet 32, the waste liquid outlet 41, and the extract inlet 42. Each of the analytical liquid inlet / outlet 31, the complexing agent solution inlet 32, the waste liquid outlet 41, and the extract inlet 42 is equipped with a solenoid valve with an on / off switch, and the solenoid valves are controlled to open and / or close by a programmable logic controller (PLC). During the enrichment stage, the solenoid valves of the analytical solution inlet / outlet 31 and the complexing agent solution inlet 32 ​​of the first chamber 3 are opened, the solenoid valve of the waste liquid outlet 41 of the second chamber 4 is opened, and the solenoid valve of the extract inlet 42 is closed, allowing the seawater sample and the complexing agent solution to enter the first chamber 3. The resulting waste liquid containing a high-salt matrix passes through the MNPs complex filter membrane 5 into the second chamber 4 and is discharged from the waste liquid outlet 41. During the elution stage, the extraction tank 1 is inverted, the solenoid valves of the complexing agent solution and the waste liquid outlet 41 are closed, and the solenoid valves of the extract inlet 42 and the analytical solution inlet / outlet 31 are opened, allowing the extract to enter the chamber and dissolve the MNPs complexes on the MNPs complex filter membrane 5, so that the solution is discharged from the analytical solution inlet / outlet 31.

[0042] In this embodiment, the flow path is switched by opening and / or closing the solenoid valves at each solution port in the control device, thereby switching the working state of the device.

[0043] The device further includes a drive unit, which includes a connecting pipe network and a multi-channel peristaltic pump connected to the pipe network. The connecting pipe network includes several connecting pipes, each of which is connected to the analytical solution inlet / outlet 31, the complexing agent solution inlet 32, and the extraction solution inlet 42, respectively. The multi-channel peristaltic pump independently controls the delivery of the high-salt seawater sample, complexing agent solution, and extraction solution in the connecting pipe network.

[0044] The connecting tube can be a flexible connecting tube made of corrosion-resistant material (such as fluororubber or silicone). The multi-channel peristaltic pump is a pump body that uses rollers to squeeze the hose to generate negative pressure to transport liquid, and can control the fluid in the connecting tubes that are connected to each solution port.

[0045] The inner diameter of the connecting pipe is matched with the size of the solenoid valve. The multi-channel peristaltic pump works in conjunction with the solenoid valve and operates through a preset program control device to achieve automatic separation of MNPs in high-salinity seawater.

[0046] In one embodiment, the apparatus further includes an MNPs analysis device connected to the analytical solution inlet / outlet 31. The analytical solution inlet / outlet 31 is connected to a container holding a seawater sample and the MNPs analysis device, respectively, and the flow state is controlled by a solenoid valve and a drive unit. During the elution stage, the MNPs analysis device and the analytical solution inlet / outlet 31 are in a flow state. After the extract dissolves the MNPs complex, the solution enters the MNPs analysis device through the analytical solution inlet / outlet 31, thereby realizing MNPs analysis.

[0047] In one embodiment, the MNPs analysis device is an SP-ICP-MS device.

[0048] Example 2 Secondly, please refer to Figure 3 , Figure 3 This application provides a flowchart of the steps for an automated online extraction method of MNPs from high-salinity seawater.

[0049] This application provides an automated online extraction method for MNPs in high-salinity seawater, applied to the automated online extraction device for MNPs in high-salinity seawater as described in the above embodiments. The method includes: S10, complexation enrichment: Seawater sample and complexing agent solution are intermittently introduced into the first chamber in a pulsed manner through the analytical liquid inlet and the complexing agent solution inlet, respectively, and flow along the surface of the support partition to the filter port. This allows the metal nanoparticles in the seawater sample to complex with the complexing agent solution, forming MNPs complexes. The MNPs complexes are then retained by the MNPs complex filter membrane, while the high-salt matrix in the seawater sample, along with the seawater, passes through the MNPs complex filter membrane into the second chamber and is discharged from the waste liquid outlet. S20, elution: The extraction vessel is inverted so that the second chamber is on top and the first chamber is on the bottom. The extract inlet and the analytical solution outlet are opened, while the complexing agent solution inlet and the waste liquid outlet are closed. The extract is introduced into the second chamber through the extract inlet in a pulsed manner, and then through the filter port to irrigate the MNPs complex filter membrane in a pulsed manner, dissolving the MNPs complexes trapped on the MNPs complex filter membrane. The resulting eluent enters the first chamber and flows out through the analytical solution inlet and outlet.

[0050] In step S10, during the complexation enrichment, the flow rate of the seawater sample and the complexing agent solution is controlled to be between 1 mL / min and 5 mL / min, the pulse interval is between 5 s and 30 s, the enrichment time is between 3 min and 10 min, and the elution time is between 1 min and 5 min.

[0051] In one embodiment, the method further includes step S30, MNP analysis: The eluent flows out through the analytical solution inlet and outlet to the MNPs analysis device, where MNPs analysis is performed using single-particle inductively coupled plasma mass spectrometry.

[0052] Among them, single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) is a mass spectrometry technique for high-sensitivity, high-resolution analysis of nanoparticles (such as MNPs). It uses inductively coupled plasma (ICP) to ionize individual nanoparticles into gaseous ions, and uses a mass spectrometer to separate and detect ion signals according to mass-to-charge ratio (m / z), thereby obtaining information such as the size distribution, concentration, elemental composition and surface modification of nanoparticles.

[0053] This application provides an automated extraction method for MNPs in high-salinity seawater. First, a seawater sample and a complexing agent solution are intermittently introduced into a first chamber via the analytical solution inlet and the complexing agent solution inlet, respectively, in a pulsed manner. The mixture flows along the surface of a support partition to a filter port, where the metal nanoparticles in the seawater sample complex with the complexing agent solution to form MNPs complexes. These MNPs complexes are then retained by an MNPs complex filter membrane. The high-salinity matrix in the seawater sample, along with the seawater, passes through the MNPs complex filter membrane into a second chamber and is discharged from a waste outlet. Next, the extraction vessel is inverted so that the second chamber is on top and the first chamber is below. The extraction solution inlet and the analytical solution inlet are opened, while the complexing agent solution inlet and the waste outlet are closed. The extraction solution is then introduced into the second chamber via the extraction solution inlet in a pulsed manner, passing through the filter port and pulse-washing the MNPs complex filter membrane, dissolving the MNPs complexes retained on the membrane. The resulting eluent enters the first chamber and flows out via the analytical solution inlet and the outlet.

[0054] The automated online extraction method provided in this embodiment achieves automated extraction of MNPs from high-salinity seawater by controlling the fluid path and timing, effectively improving the separation efficiency.

[0055] Those skilled in the art will understand that embodiments of this application can be provided as methods, systems, or computer program products. Therefore, this application can take the form of a completely hardware embodiment, a completely software embodiment, or an embodiment combining software and hardware aspects. Furthermore, this application can take the form of a computer program product embodied on one or more computer-usable storage media (including but not limited to disk storage, CD-ROM, optical storage, etc.) containing computer-usable program code.

[0056] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. An automated online extraction device for MNPs in high-salinity seawater, characterized in that, include: An extractor that can be tilted and placed, including a sealed separation chamber; A support partition is disposed in the separation chamber, dividing the separation chamber into a first chamber and a second chamber. One end of the support partition is provided with a filter port that connects the first chamber and the second chamber. MNPs complex filter membrane is disposed at the filter port; The first chamber has an analytical solution inlet / outlet and a complexing agent solution inlet at the end away from the MNPs complex filter membrane; the second chamber has a waste liquid outlet at the end away from the MNPs complex filter membrane and an extractant inlet at the end closer to the MNPs complex filter membrane.

2. The automatic online extraction device for MNPs in high-salinity seawater according to claim 1, characterized in that, The complexing agent solution inlet faces a first direction, the waste liquid outlet and the extract inlet face a second direction, and the first direction and the second direction are opposite.

3. The automatic online extraction device for MNPs in high-salinity seawater according to claim 2, characterized in that, The complexing agent solution inlet and the waste liquid outlet are symmetrically arranged with respect to the supporting partition; the analytical liquid inlet and outlet are located on the side of the extraction tank near the complexing agent solution inlet.

4. The automatic online extraction device for MNPs in high-salinity seawater according to claim 1, characterized in that, The first chamber of the extraction tank is a sealed chamber made of quartz, and the supporting partition is a partition made of polytetrafluoroethylene.

5. The automatic online extraction device for MNPs in high-salinity seawater according to claim 1, characterized in that, The filtration pore size of the MNPs complex filter membrane is 200 nm to 1000 nm.

6. The automatic online extraction device for MNPs in high-salinity seawater according to any one of claims 1 to 5, characterized in that, It also includes a temperature control module, which controls the working temperature inside the extraction tank.

7. The automatic online extraction device for MNPs in high-salinity seawater according to any one of claims 1 to 5, characterized in that, It also includes several solenoid valves, which independently control the on / off switching of the analytical liquid inlet / outlet, the complexing agent solution inlet, the waste liquid outlet, and the extract inlet.

8. The automatic online extraction device for MNPs in high-salinity seawater according to claim 7, characterized in that, It also includes a drive unit, which includes a connecting pipe network and a multi-channel peristaltic pump connected to the connecting pipe network. The connecting pipe network includes several connecting pipes, each of which is connected to the analytical solution inlet / outlet, the complexing agent solution inlet, and the extract inlet, respectively. The multi-channel peristaltic pump independently controls the delivery of the high-salt seawater sample, the complexing agent solution, and the extract in the connecting pipe network.

9. An automated online extraction method for MNPs in high-salinity seawater, applied to the automated online extraction device for MNPs in high-salinity seawater as described in claims 1-8, characterized in that, Includes the following steps: S10, complexation enrichment: Seawater sample and complexing agent solution are intermittently introduced into the first chamber in a pulsed manner through the analytical liquid inlet and the complexing agent solution inlet, respectively, and flow along the surface of the support partition to the filter port. This allows the metal nanoparticles in the seawater sample to complex with the complexing agent solution, forming MNPs complexes. The MNPs complexes are then retained by the MNPs complex filter membrane, while the high-salt matrix in the seawater sample, along with the seawater, passes through the MNPs complex filter membrane into the second chamber and is discharged from the waste liquid outlet. S20, elution: The extraction vessel is inverted so that the second chamber is on top and the first chamber is on the bottom. The extract inlet and the analytical solution outlet are opened, while the complexing agent solution inlet and the waste liquid outlet are closed. The extract is introduced into the second chamber through the extract inlet in a pulsed manner, and then through the filter port to irrigate the MNPs complex filter membrane in a pulsed manner, dissolving the MNPs complexes trapped on the MNPs complex filter membrane. The resulting eluent enters the first chamber and flows out through the analytical solution inlet and outlet.

10. The automated extraction method for MNPs in high-salinity seawater according to claim 9, characterized in that, In step S10, during the complexation enrichment, the flow rate of the seawater sample and the complexing agent solution is controlled between 1 mL / min and 5 mL / min, the pulse interval is between 5 s and 30 s, the enrichment time is between 3 min and 10 min, and the elution time is between 1 min and 5 min.

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