CN109709126B - Automatic detection device and method for heavy metals in water body by algae enrichment-X-ray fluorescence spectrum - Google Patents
Automatic detection device and method for heavy metals in water body by algae enrichment-X-ray fluorescence spectrum Download PDFInfo
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- CN109709126B CN109709126B CN201910129119.1A CN201910129119A CN109709126B CN 109709126 B CN109709126 B CN 109709126B CN 201910129119 A CN201910129119 A CN 201910129119A CN 109709126 B CN109709126 B CN 109709126B
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Abstract
The invention discloses an automatic detection device and method for heavy metals in water body by algae enrichment-X-ray fluorescence spectrum, which take green algae in fresh water microalgae with strong adsorption performance to heavy metals as an adsorption material and take a banded filter membrane as a carrying carrier for algae cells and heavy metals, and realize the simultaneous, rapid, continuous and automatic online detection of various heavy metals in the water body by the adsorption of the algae to the heavy metals, the formation of uniform thin samples by the algae-heavy metal enrichment, the transmission of filter paper bands, the drying of the heavy metal thin samples and XRF spectral measurement and analysis procedures. The method has the characteristics of simple operation, no need of chemical reagents, no secondary pollution, economy, environmental protection, low operation and maintenance cost, high automation degree and the like, and obviously improves the stability and sensitivity of the XRF spectroscopy on the detection of the heavy metals in the water body. The liquid flow accurate control and continuous suction filtration mode can realize multiple continuous repeated sample preparation of the same water sample to be analyzed, and the accuracy of the XRF spectroscopy on the detection of the heavy metals in the water body is improved.
Description
Technical Field
The invention relates to the technical field of detection of environmental heavy metal pollutants, in particular to an automatic detection device and method for heavy metals in water body by algae enrichment-X-ray fluorescence spectrum.
Background
In recent years, with the rapid development of the industry in China, the problem of heavy metal pollution of water bodies is very prominent, and heavy metal pollution events such as 'standard exceeding of blood lead', 'standard exceeding of cadmium', 'bone pain' and the like are frequently developed. Heavy metals are undegradable and bioaccumulation, have significant biotoxicity, can cause cancer, diseases and mutation, once accumulated in organisms, seriously threaten human health and ecological environment, and cause great loss to national economy. Therefore, the rapid, real-time, on-line and automatic detection of the heavy metals in the water body has very important practical significance for preventing and treating the heavy metal pollution of the water body and ensuring the water quality safety of a water source.
Traditional heavy metal detection methods such as Atomic Absorption Spectroscopy (AAS), Atomic Fluorescence Spectroscopy (AFS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), inductively coupled plasma-mass spectroscopy (ICP-MS) and the like have the advantages of high sensitivity, good accuracy and the like, but on-site sampling and laboratory analysis are required, and the requirements of rapid, real-time, online and automatic detection of heavy metals cannot be met. Some heavy metal rapid detection methods emerging in recent years mainly include: biochemical detection methods (e.g., enzyme inhibition assays, immunoassays, microbiological detection methods, chemical chromogenic methods, etc.), electrochemical detection methods (primarily anodic stripping voltammetry), and spectroscopic detection methods (e.g., laser-induced breakdown spectroscopy and X-ray fluorescence spectroscopy). Although the biochemical detection method has higher sensitivity, the selectivity of the method is poorer, and the simultaneous detection of various heavy metals cannot be realized. Although the electrochemical detection method can realize the simultaneous determination of a plurality of heavy metals, the electrode has high manufacturing cost and short service life, and the liquid mercury electrode can precipitate toxic mercury in the using process, so the problems of high detection cost and easy secondary environmental pollution are solved. Although the laser-induced breakdown spectroscopy technology is developed rapidly in recent years and can realize simultaneous determination of multiple heavy metals, the evolution process of plasma generated by laser induction in the spectral measurement is very complex, the process is easily influenced by various factors such as laser energy, sample properties, matrix composition and the surrounding gas environment of the plasma, and the spectral repeatability and stability are poor.
Compared with the method, the X-ray Fluorescence (XRF) spectrometry is an important technology in the heavy metal spectrum rapid detection method, and has the advantages of no destructiveness to a sample to be detected, simultaneous determination of multiple elements, less spectral line interference, high measurement speed, good reproducibility and the like, so that the method is an effective means for rapid, real-time and online analysis of heavy metal elements, and is an important development direction of the heavy metal field rapid detection technology. XRF spectroscopy uses an X-ray tube to generate high-energy X-rays to excite a sample to be measured, causing it to generate characteristic secondary X-rays (also called X-ray fluorescence), and performs qualitative and quantitative analysis on the sample to be measured according to the wavelength or energy of the characteristic X-ray fluorescence and the fluorescence intensity. At present, the XRF spectroscopy has been widely used in the fields of analysis of metal element content in mining industry, geology and oil samples, detection of heavy metal in atmospheric particulates, etc., but the research on direct detection and application of heavy metal in water bodies by the current XRF spectroscopy is very little, because the XRF spectroscopy directly faces the following two main problems to the detection of heavy metal in water bodies:
when high-energy X-rays directly irradiate a water body sample, partial elements of the irradiated area of the sample are subjected to chemical reaction due to local heating, so that the phenomena of air bubbles, precipitation, even precipitation and the like can occur, the fluorescence intensity of the X-rays generated by the sample is extremely unstable and easy to change, the reproducibility and stability of X-ray fluorescence analysis signals are seriously influenced, and the accuracy of heavy metal detection is poor.
Secondly, after the water body sample is directly irradiated by the X-ray generated by the excitation source, the water body has stronger absorption effect on the X-ray, so that a scattering background with higher intensity is generated, and meanwhile, the intensity of a characteristic X-ray spectral line emitted by an analyzed element is weaker, so that the signal-to-noise ratio of the detection of the heavy metal in the water body is lower, the sensitivity is poorer, and the detection limit of the X-ray fluorescence spectrometry can not meet the detection requirements of the heavy metal elements in the water body in the environment and industrial fields.
Due to the problems, the application of the X-ray fluorescence spectrum technology in the aspect of directly detecting the heavy metal in the water body is limited.
Disclosure of Invention
The invention aims to make up for the defects of the prior art and provides an automatic detection device and method for heavy metals in water by using an algae enrichment-X-ray fluorescence spectrum. The method is characterized in that green algae in freshwater microalgae are used as an adsorption material to simultaneously enrich multiple heavy metal elements in a water body, a banded filter membrane is used as a supporting body of algae cells and heavy metals, a plurality of thin samples with the same heavy metal uniform distribution of the same water body sample are prepared in a liquid flow accurate control and continuous suction filtration mode to carry out XRF spectral measurement and analysis, the heavy metal thin samples are automatically transmitted from an enrichment area to a heating area and from the heating area to the XRF spectral measurement area in a paper tape transmission mode, the multiple heavy metal XRF spectra in the water body are simultaneously rapidly, continuously and automatically detected, and the problems of poor stability and low sensitivity of direct detection of the heavy metal in the water body by an XRF spectrum technology are solved.
The invention is realized by the following technical scheme:
an automatic detection device for heavy metals in water body by algae enrichment-X-ray fluorescence spectrum comprises a heavy metal enrichment system, a paper tape conveying system, a sample drying system, an X-ray fluorescence spectrum measurement system and a data acquisition and control system;
the heavy metal enrichment system comprises a reaction cup, a peristaltic pump, a flow controller, a filter cup, an up-down moving device, a sand core supporting base, a filtrate receiving bottle, a vacuum pump and a filter paper belt, wherein a water outlet at the lower end of the reaction cup is connected with the peristaltic pump through a hose, the other end of the peristaltic pump is connected with an inlet of the flow controller through a hose, an outlet of the flow controller is connected with an inlet at the upper end of the filter cup, the lower end of the cup wall of the filter cup is inwards contracted to form a funnel shape, the bottom of the cup is a circular leak, the filter cup is fixedly connected onto the up-down moving device, the sand core supporting base is a supporting base which is formed by cylindrical glass with a circular sand core embedded at the top center and provided with a through hole at the center of the lower end, the outer diameter of the cylindrical glass at the top of the sand core supporting base is equal to the outer side diameter of the bottom of the filter cup, the diameter of the internal circular sand core is larger than the diameter of the leak at the bottom of the filter cup, the outer diameter of the cylindrical glass at the lower end of the sand core supporting base is smaller than that of the cylindrical glass at the top of the sand core supporting base, the inner diameter of the cylindrical glass is larger than that of the top circular sand core, the lower end of the sand core supporting base is connected with the upper end of the filtrate receiving bottle, the inner wall of the cylindrical glass at the lower end of the sand core supporting base and the outer wall of the glass at the upper end of the filtrate receiving bottle are both frosted glass walls, the calibers of the frosted glass walls are the same, an exhaust port is arranged at the middle upper end of the filtrate receiving bottle, and the exhaust port is connected with a vacuum pump through a rubber pipe;
the paper tape conveying system comprises a filter paper tape, a paper feeding tape reel, a paper feeding motor, a paper rolling tape reel, a paper rolling motor, a motor driver and a paper feeding positioning detection system, wherein the width of the filter paper tape is the same as the inner diameters of the paper feeding tape reel and the paper rolling tape reel, the motor driver respectively drives the paper feeding motor and the paper rolling motor to rotate, the paper feeding motor drives the paper feeding tape reel to rotate to release the filter paper tape, the paper rolling motor drives the paper rolling tape reel to rotate to roll up the filter paper tape, the rotating speeds of the paper feeding tape reel and the paper rolling tape reel are equal, the filter paper tape is arranged between the filter cup and the sand core supporting base, the width of the filter paper tape is larger than the diameter of a circular sand core at the top of the sand core supporting base, and after the up-down moving device drives the filter cup to move downwards, the filter cup, the filter paper tape, the sand core supporting base, a filtrate receiving bottle and a vacuum pump form a suction filtration system; the paper feeding positioning detection system comprises a punching device, a first photoelectric detector and a second photoelectric detector, wherein the punching device comprises a first stepping motor and a needle head, the punching device is positioned on one side of a sand core supporting base, the first photoelectric detector is positioned in a heating area, and the second photoelectric detector is positioned in an X-ray fluorescence spectrum measurement area;
the sample drying system is positioned between the heavy metal enrichment system and the X-ray fluorescence spectrum measurement system, is positioned right below the filter paper tape and is used for heating and drying a heavy metal round thin sample on the filter paper tape, and the sample drying system is composed of a carbon fiber heating pipe and a power supply circuit;
the X-ray fluorescence spectrum measuring system comprises an X-ray tube and an SDD detector which are positioned above a filter paper tape, wherein the X-ray tube is an excitation light source and is used for generating high-energy X-rays for exciting the fluorescence of heavy metal characteristic X-rays in a thin sample;
the data acquisition and control system is respectively and electrically connected with a control end of the peristaltic pump, a control end of the flow controller, a control end of the up-down moving device, a control end of the vacuum pump, a control end of the motor driver, a control end of the first stepping motor, a control end of the sample drying system, a control end of the first photoelectric detector, a control end of the second photoelectric detector, the X-ray tube and a control end of the SDD detector, the data acquisition and control system comprises a power module, a data acquisition module, a single chip microcomputer and a control circuit thereof, the data acquisition module and the power module are respectively connected with the single chip microcomputer, the data acquisition module acquires, stores, analyzes and processes signals converted by photoelectric signals of the SDD detector, and the single chip microcomputer and the control circuit thereof respectively transmit the signals to the peristaltic pump, the flow controller, the up-down moving device, the vacuum pump, the punching device, the sample drying system and the SDD detector, The photoelectric detector I, the photoelectric detector II, the motor driver, the X-ray tube and the SDD detector send control signals to achieve the control function of the whole device, and the power supply module is used for supplying power to the whole device.
The filter paper tape is a banded glass fiber microporous filter film, and the aperture size is 0.22 mu m.
The up-down moving device comprises a support frame, a vertical rail is installed on the support frame, a filter cup holder is installed on the vertical rail in a sliding mode, the filter cup holder is connected with a second stepping motor, the second stepping motor drives the filter cup holder to move up and down on the vertical rail of the support frame, and the second stepping motor is connected with a data acquisition and control system.
An algae enrichment-X-ray fluorescence spectrum water heavy metal automatic detection device, each part function is: the reaction cup is a reaction vessel for adsorbing heavy metals in a water body by algae; the peristaltic pump is used for driving the liquid sample in the reaction cup to flow into the filter cup; the flow controller is used for accurately metering the flow rate and the volume of liquid flow; the filter paper belt is used for carrying carriers of algae cells and heavy metals; the vacuum pump is used for pumping a closed system formed by the filter cup, the filter paper tape, the sand core supporting base and the filtrate receiving bottle so as to ensure that algae cells which are uniformly dispersed in the filter cup and adsorbed with heavy metals are uniformly settled under the action of pressure and form a round thin sample with uniformly distributed heavy metals on the filter paper tape at the bottom of the filter cup; the sample drying system is used for drying heavy metal round thin samples so as to avoid the influence of the sample humidity on the subsequent XRF spectrum measurement, a power supply circuit in the sample drying system is connected with the data acquisition and control system, the data acquisition and control system sends a control signal to the power supply circuit, when the power supply circuit receives the control signal and then powers on the carbon fiber heating pipe, the carbon fiber heating pipe transmits the electric energy to the surroundings in an infrared radiation mode, the round thin heavy metal sample on the upper part is subjected to open heating and drying treatment, and meanwhile, the data acquisition and control system controls the electrifying time and the current of the power supply circuit, the heating temperature of the sample drying system is controlled to be 45 ℃ so as to realize the control of the heating time and the temperature and effectively shorten the sample cooling time before XRF spectrum measurement in order to avoid the deformation of the sample and the filter paper belt caused by overhigh temperature; the data acquisition and control system is used for acquiring, storing, analyzing and processing signals converted from the photoelectric signals of the SDD detector and controlling the execution of working instructions of the whole device, and comprises a peristaltic pump, a flow controller, an up-and-down moving device, a vacuum pump, a perforating device, a sample drying system, a photoelectric detector, a motor driver, an X-ray tube and the SDD detector, and liquid samples in the reaction cup flow into the filter cup by controlling the peristaltic pump; the flow and the volume of the flowing liquid are accurately judged by controlling the flow controller; the filter cup is lifted by controlling the up-and-down moving device, so that a gap is formed between the filter cup and the filter paper belt, and the filter paper belt is convenient to convey; the filter cup is put down by controlling the up-and-down moving device, so that the filter cup, the filter paper tape, the sand core supporting base, the filtrate receiving bottle and the vacuum pump form a suction filtration system; the algae cell suspension liquid absorbed with heavy metals in the filter cup is filtered by controlling the vacuum pump; the paper tape feeding motor and the paper roll motor are controlled to drive the paper tape feeding disc and the paper roll disc to rotate by controlling the motor driver, so that the function of paper tape conveying is realized; the function of accurately punching a small hole at the edge of the heavy metal enrichment area is realized by controlling the punching device; the specific conveying position of the round thin sample on the filter paper belt is accurately judged by controlling the photoelectric detector, so that the function of accurately positioning the thin sample from an enrichment position to a heating position and from the heating position to an X-ray fluorescence spectrum measuring position is realized; the function of quickly drying the thin test sample enriched with heavy metals is realized by controlling the sample drying system; the function that the X-ray tube excitation source generates high-energy X-rays to excite a sample to be tested is realized by controlling the X-ray tube; the SDD detector is controlled to receive X-ray fluorescence signals emitted by a sample and perform photoelectric conversion.
The heavy metal enrichment system can realize repeated sample preparation for the same water sample to be analyzed for multiple times under the combined action of the peristaltic pump and the flow controller and the control of the data acquisition and control system, and the volume of the liquid sample flowing into the filter cup during sample preparation for each time is the same under the accurate control of the flow controller, so that multiple XRF spectrum measurement and analysis of the same water sample to be analyzed are realized, and the accuracy of the XRF spectrum technology for detecting the heavy metal in the water is improved.
An automatic detection method for heavy metals in water by algae enrichment-X-ray fluorescence spectrum comprises a heavy metal adsorption process, a uniform thin sample formation process by algae-heavy metal enrichment, a filter paper belt conveying process, a heavy metal thin sample drying process and an XRF spectrum measurement and analysis process;
the process of heavy metal adsorption by algae is as follows: the reaction cup is used for a reaction container for adsorbing heavy metals in water by algae, and when algae cells and heavy metals in the reaction cup reach adsorption balance, the process of enriching algae and heavy metals to form a uniform thin sample is started;
the process of forming the uniform thin sample by enriching the algae and the heavy metal comprises the following steps: when the algae cells and the heavy metals in the reaction cup reach adsorption balance, the up-down moving device controls the filter cup to descend and tightly press on a filter paper belt on the sand core supporting base, then the peristaltic pump and the flow controller are started, a liquid sample with a certain volume flows into the filter cup, then the peristaltic pump and the flow controller are closed, then the vacuum pump is started, the filtration of the algae cell suspension liquid with the heavy metals adsorbed in the filter cup is started, the algae cells with the heavy metals adsorbed are enabled to be uniformly settled on the filter paper belt under the action of pressure, and a round thin sample with the heavy metals uniformly distributed is formed;
the filter paper belt conveying process comprises the following steps: after the liquid sample in the filter cup is completely filtered, the vacuum pump is closed, the perforating device punches a small hole in the edge of the round thin sample on the filter paper tape, then the filter cup is controlled by the up-and-down moving device to lift upwards, the motor driver and the photoelectric detector are respectively started, the paper feeding motor and the paper rolling motor drive the paper feeding tape reel and the paper rolling tape reel to rotate clockwise under the control of the motor driver so as to convey the filter paper tape, the heavy metal thin sample on the filter paper tape is conveyed to the heating area under the judgment of the photoelectric detector I, and at the moment, the motor driver and the photoelectric detector stop working;
the drying process of the heavy metal thin sample comprises the following steps: starting a sample drying system, and heating and drying the heavy metal thin sample arranged above the sample drying system;
the XRF spectroscopy measurement and analysis process was: after heating and drying, the sample drying system stops working, after the thin sample is cooled to room temperature, the motor driver and the photoelectric detector are started, the paper feeding motor and the paper winding motor drive the paper feeding belt disc and the paper winding belt disc to rotate clockwise to convey the filter paper belt under the control of the motor driver, the heavy metal thin sample on the filter paper belt is accurately conveyed to the X-ray fluorescence spectrum measurement area under the judgment of the photoelectric detector, at the moment, the motor driver and the photoelectric detector stop working, the X-ray tube and the SDD detector start to work, the X-ray tube generates high-energy X rays to excite the heavy metal thin sample, the SDD detector carries out photoelectric conversion on the detected X-ray fluorescence signals, and the signals are conveyed to the data acquisition and control system to carry out data acquisition and processing.
The algae are green algae in freshwater microalgae, particularly chlorella or chlorella pyrenoidosa or aschersonia, are unicellular algae, have the characteristics of small cell volume, large specific surface area, difficult agglomeration and difficult agglomeration of cells, uniform dispersion in a water sample and the like, and have good adsorption performance on lead (Pb), cadmium (Cd), chromium (Cr), nickel (Ni), copper (Cu), cobalt (Co), silver (Ag) and the like, and can adsorb various heavy metals in a water body simultaneously.
The heavy metal is two or more of lead (Pb), cadmium (Cd), chromium (Cr), nickel (Ni), copper (Cu), cobalt (Co) and silver (Ag).
The invention has the advantages that: the method is based on the strong adsorption characteristic of algae on heavy metals, combines an algae enrichment technology, a filter paper belt transmission technology and an X-ray fluorescence spectrum measurement technology, uses a filter paper belt as a receiving carrier of algae cells and heavy metals, forms a uniform thin sample through the adsorption of algae on the heavy metals, the enrichment of algae and the heavy metals, realizes the quick, continuous and automatic online detection of various heavy metals in the water body through the filter paper belt transmission, the drying of the heavy metal thin sample, the XRF spectrum measurement and analysis program, has the characteristics of simple operation, no need of chemical reagents, no secondary pollution, economy, environmental protection, low operation and maintenance cost, high automation degree and the like, is favorable for improving the stability, sensitivity and accuracy of the XRF spectrum detection of the heavy metals in the water body, and is suitable for the quick, continuous and automatic online detection of various heavy metals in natural water body at the same time.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
FIG. 2 is a flow chart of the method of the present invention.
Detailed Description
As shown in FIG. 1, this example is a laboratory-formulated Pb2+And Cr3+The aqueous solution being the sample to be analyzed, Pb2+Has a concentration of 20 mg.L-1，Cd3+Has a concentration of 20 mg.L-1Chlorella is used as adsorbent, inoculated with BG-11 culture medium in laboratory, and irradiated at 20 deg.C and light intensity of 200 μmol · m-2·s-1Culturing for 30 days under the condition of light-dark ratio of 12h:12h, wherein chlorophyll concentration reaches 24000 mu g.L-1。
As shown in fig. 1, the algae enrichment-X-ray fluorescence spectrum water heavy metal automatic detection device comprises a heavy metal enrichment system, a paper tape conveying system, a sample drying system 12, an X-ray fluorescence spectrum measurement system and a data acquisition and control system 21;
the heavy metal enriching system comprisesReaction cup 1, peristaltic pump 2, flow controller 3, filter cup 4, up-down moving device 5, sand core support base 6, filtrate receiving bottle 7, vacuum pump 8 and filter paper tape 18, reaction cup 1 is used as chlorella to adsorb heavy metal Pb in water2+And Cr3+The reaction vessel, the water outlet of the lower end of the reaction vessel is connected with the peristaltic pump 2 through a hose, the other end of the peristaltic pump 2 is connected with the inlet of a flow controller 3 through a hose, the outlet of the flow controller 3 is connected with the inlet of the upper end of a filter cup 4, the lower end of the cup wall of the filter cup 4 is inwards contracted into a funnel shape, the bottom of the cup is a circular leak, the filter cup 4 is fixedly connected on an up-down moving device 5, a sand core support base 6 is a support base which is composed of cylindrical glass with the same thickness embedded in the center of the top and cylindrical glass with a through hole in the center of the lower end, the outer diameter of the cylindrical glass at the top of the sand core support base 6 is equal to the outer diameter of the bottom of the filter cup 4, the diameter of the internal circular sand core is larger than the diameter of the leak at the bottom of the filter cup 4, and the outer diameter of the cylindrical glass at the lower end of the sand core support base 6 is smaller than the outer diameter of the cylindrical glass at the top of the sand core support base 6, the inner diameter of the sand core is larger than the diameter of the top round sand core, the lower end of the sand core supporting base 6 is connected with the upper end of the filtrate receiving bottle 7, the cylindrical glass inner wall at the lower end of the sand core supporting base 6 and the glass outer wall at the upper end of the filtrate receiving bottle 7 are both designed into frosted glass walls, the calibers are the same, an exhaust port is arranged at the middle upper end of the filtrate receiving bottle 7, and the exhaust port is connected with a vacuum pump 8 through a rubber pipe;
the paper tape conveying system is composed of a filter paper tape 18, a paper feeding tape disc 9, a paper feeding motor 10, a paper rolling tape disc 15, a paper rolling motor 16, a motor driver 17 and a paper feeding positioning detection system, wherein the width of the filter paper tape 18 is the same as the inner diameters of the paper feeding tape disc 9 and the paper rolling tape disc 15, the motor driver 17 drives the paper feeding motor 10 and the paper rolling motor 16 to rotate respectively, the paper feeding motor 10 drives the paper feeding disc 9 to rotate to release a filter paper tape 18, the paper rolling motor 16 drives the paper rolling tape disc 15 to rotate to roll up the filter paper tape 18, the rotating speeds of the paper feeding tape disc 9 and the paper rolling tape disc 15 are equal, the filter paper tape 18 is arranged between the filter cup 4 and the sand core supporting base 6, the width of the filter paper tape 18 is larger than the diameter of a circular sand core at the top of the sand core supporting base 6, and after the filter cup 4 is driven by the up-down moving device to move downwards, the filter cup 4, the filter cup 18, the sand core supporting base 6, the filter paper core supporting base 6, the filter cup 4, the sand core 18, the sand core supporting base 6, the filter paper tape 4 and the filter paper coreThe liquid receiving bottle 7 and the vacuum pump 8 form a suction filtration system; the paper feeding positioning detection system comprises a punching device 11, a first photoelectric detector 13 and a second photoelectric detector 14, wherein the punching device 11 comprises a first stepping motor and a needle head, the punching device is positioned on one side of a sand core supporting base, the diameter of the needle head is 1mm, and the punching device is used for enriching heavy metal Pb on a filter paper belt 182+And Cr3+When the heavy metal thin sample is conveyed to the heating area or the X-ray fluorescence spectrum measurement area, the small hole at the edge of the thin sample is just positioned between the emitting diode and the receiving diode of the photoelectric detector, and the receiving diode accurately judges the specific conveying position of the thin sample according to the change of the received light intensity signal;
the sample drying system 12 is arranged between the heavy metal enrichment system and the X-ray fluorescence spectrum measurement system and is arranged right below the filter paper belt 18 and used for supplying heavy metal Pb on the filter paper belt 182+And Cr3+The round thin test sample is heated and dried, and the sample drying system 12 is composed of a carbon fiber heating pipe and a power supply circuit;
the X-ray fluorescence spectrum measuring system comprises an X-ray tube 19 and an SDD detector 20 which are positioned above a filter paper tape, wherein the X-ray tube 19 is an excitation light source and is used for generating high-energy X-rays for exciting the fluorescence of heavy metal characteristic X-rays in a thin sample, when the heavy metal is excited by the high-energy X-rays and generates energy level transition, the emitted characteristic X-ray fluorescence signals are received by the SDD detector 20, and the SDD detector 20 performs photoelectric signal conversion;
the data acquisition and control system 21 is respectively connected with the control end of the peristaltic pump 2, the control end of the flow controller 3, the control end of the up-and-down moving device 5, the control end of the vacuum pump 8, the control end of the motor driver 17, the control end of the first stepping motor, the control end of the sample drying system 12, the control end 13 of the first photoelectric detector, the control end of the second photoelectric detector 14, the X-ray tube 19 and the control end of the SDD detector 20, the data acquisition and control system 21 comprises a power module, a data acquisition module, a single chip microcomputer and a control circuit, wherein the data acquisition module is used for acquiring, storing, analyzing and processing signals converted from photoelectric signals of the SDD detector 20, and the single chip microcomputer and the control circuit thereof respectively transmit the signals to the peristaltic pump 2, the flow controller 3, the up-and-down moving device 5, the vacuum pump 8, the perforating device 11, the sample drying system 12 and the first photoelectric detector 13, The second photo detector 14, the motor driver 17, the X-ray tube 19 and the SDD detector 20 send control signals to realize the control function of the whole device, and the power module is used for supplying power to the whole device.
The filter paper tape is a banded glass fiber microporous filter film with the aperture of 0.22 mu m, and is used as chlorella cells and heavy metal Pb2+And Cr3+To receive the carrier.
Algae enrichment-X ray fluorescence spectrum water heavy metal automatic checkout device, each part function is: the reaction cup 1 is used for adsorbing water heavy metal Pb by chlorella2+And Cr3+The reaction vessel of (1); the peristaltic pump 2 is used for driving the liquid sample in the reaction cup 1 to flow into the filter cup 4; the flow controller 3 is used for accurately metering the flow rate and the volume of liquid flow; the vacuum pump 8 is used for pumping a closed system consisting of the filter cup 4, the filter paper belt 18, the sand core supporting base 6 and the filtrate receiving bottle 7 so as to ensure that the filter cup 4 is uniformly dispersed and adsorbed with heavy metal Pb2+And Cr3+The chlorella cells are uniformly settled under the pressure, and heavy metal Pb is formed on the filter paper belt 18 at the bottom of the filter cup 42+And Cr3+Uniformly distributed round thin samples; the sample drying system 12 is used for heavy metal Pb2+And Cr3+The circular thin sample is dried to avoid sample humidity to influence follow-up XRF spectral measurement, power supply circuit in sample drying system 12 is connected with data acquisition and control system 21, control signal is sent to power supply circuit by data acquisition and control system 21, carbon fiber heating pipe circular telegram to carbon fiber heating pipe after power supply circuit receives control signal, carbon fiber heating pipe is with the electric energy with infrared radiation mode to transmission all around, to being in the heavy metal Pb of top2+And Cr3+Open type heating and drying position for round thin sampleMeanwhile, the data acquisition and control system 21 controls the power-on time and the current of the power supply circuit to control the heating time and the heating temperature, and in order to avoid the deformation of the sample and the filter paper belt 18 caused by overhigh temperature and effectively shorten the sample cooling time before XRF spectrum measurement, the heating temperature of the sample drying system 12 is controlled to be 45 ℃; the data acquisition and control system 21 is used for acquiring, storing, analyzing and processing signals converted by photoelectric signals of the SDD detector 20 and controlling the execution of working instructions of the whole device, and comprises a peristaltic pump 2, a flow controller 3, an up-down moving device 5, a vacuum pump 8, a perforating device 11, a sample drying system 12, a first photoelectric detector 13, a second photoelectric detector 14, a motor driver 17, an X-ray tube 19 and the SDD detector 20, and the liquid sample in the reaction cup 1 flows into the filter cup 4 by controlling the peristaltic pump 2; the flow and the volume of the liquid flow are accurately judged by controlling the flow controller 3; the up-and-down moving device 5 is controlled to lift the filter cup 4, so that a gap is formed between the filter cup 4 and the filter paper belt 18, and the filter paper belt 18 is convenient to convey; the filter cup 4 is put down by controlling the up-and-down moving device 5, so that the filter cup 4, the filter paper tape 18, the sand core supporting base 6, the filtrate receiving bottle 7 and the vacuum pump 8 form a suction filtration system; the heavy metal Pb absorbed in the filter cup 4 is realized by controlling the vacuum pump 82+And Cr3+Carrying out suction filtration on the chlorella cell suspension; the paper tape conveying function is realized by controlling the motor driver 17 to control the paper feeding motor 10 and the paper rolling motor 16 to drive the paper feeding tape reel 9 and the paper rolling tape reel 15 to rotate; through the control of the perforating device 11, the heavy metal Pb is realized2+And Cr3+Accurately punching a small hole with the aperture size of 1mm on the edge of the enrichment area; the specific conveying position of the round thin sample on the filter paper tape 18 is accurately judged by controlling the first photoelectric detector 13 and the second photoelectric detector 14, so that the function of accurately positioning the thin sample from an enrichment position to a heating position and from the heating position to an X-ray fluorescence spectrum measuring position is realized; the control of the sample drying system 12 realizes the enrichment of heavy metal Pb2+And Cr3+The thin sample is dried and processed fast; by pairsThe X-ray tube 19 is controlled to realize the function that the X-ray tube 19 excitation source generates high-energy X-rays to excite the sample to be tested; the SDD detector 20 is controlled to receive the X-ray fluorescence signal emitted from the sample and perform photoelectric conversion.
The heavy metal enrichment system can realize the Pb-containing under the combined action of the peristaltic pump 2 and the flow controller 3 and the control of the data acquisition and control system 212+And Cr3+The same water body sample to be analyzed is repeatedly prepared for a plurality of times, and the volume of the liquid sample flowing into the filter cup 4 is the same under the accurate control of the flow controller 3, so as to realize the purpose of preparing the Pb-containing water body sample2+And Cr3+The multiple XRF spectrum measurement and analysis of the same water sample to be analyzed are favorable for improving the XRF spectrum technology to the heavy metal Pb in the water body2+And Cr3+And (4) the detection accuracy.
As shown in fig. 2, the method for automatically detecting heavy metals in water body by algae enrichment-X-ray fluorescence spectroscopy comprises a process of adsorbing heavy metals by algae, a process of forming a uniform thin sample by algae-heavy metal enrichment, a process of conveying a filter paper belt, a process of drying the thin heavy metal sample, and an XRF spectroscopy measurement and analysis process;
the process of heavy metal adsorption by algae is as follows: reaction cup 1 for chlorella to adsorb water heavy metal Pb2+And Cr3+When chlorella cells in the reaction cup 1 are mixed with heavy metal Pb2+And Cr3+After the adsorption balance is achieved, the process of forming a uniform thin sample by algae-heavy metal enrichment is started;
the process of forming the uniform thin sample by enriching the algae and the heavy metal comprises the following steps: when the chlorella cells in the reaction cup 1 are mixed with heavy metal Pb2+And Cr3+After the adsorption balance is achieved, the up-and-down moving device 5 controls the filter cup 4 to descend and tightly press the filter paper tape 18 on the sand core support base 6, the peristaltic pump 2 and the flow controller 3 are started again, the liquid sample with a certain volume is controlled to flow into the filter cup 4, then the peristaltic pump 2 and the flow controller 3 are closed again, the vacuum pump 8 is started again, and the heavy metal Pb is adsorbed in the filter cup 42+And Cr3+The chlorella cell suspension is filtered to absorb heavy metal Pb2+And Cr3+The chlorella algae cells are uniformly settled on the filter paper tape 18 under the pressure action to form heavy metal Pb2+And Cr3+Uniformly distributed round thin samples;
the filter paper belt conveying process comprises the following steps: after the liquid sample in the filter cup 4 is completely filtered, the vacuum pump 8 is closed, and the perforating device 11 is used for perforating Pb on the filter paper belt 182+And Cr3+Punching a small hole with the aperture size of 1mm on the edge of the round thin sample, then controlling the filter cup 4 to lift upwards by the up-down moving device 5, respectively starting the motor driver 17 and the photoelectric detector one 13, driving the paper feeding reel 9 and the paper rolling reel 15 to rotate clockwise by the paper feeding motor 10 and the paper rolling motor 16 under the control of the motor driver 17 so as to convey the filter paper tape 18, and judging Pb on the filter paper tape 18 by the photoelectric detector one 132+And Cr3+The heavy metal thin sample is conveyed to a heating area, and at the moment, the motor driver 17 and the first photoelectric detector 13 stop working;
the drying process of the heavy metal thin sample comprises the following steps: the sample drying system 12 is started to place Pb thereon2+And Cr3+Heating and drying the heavy metal thin sample;
the XRF spectroscopy measurement and analysis process was: after heating and drying, the sample drying system 12 stops working, after the thin sample is cooled to room temperature, the motor driver 17 and the second photoelectric detector 14 are started, the paper feeding motor 10 and the paper winding motor 16 drive the paper feeding reel 9 and the paper winding reel 15 to rotate clockwise under the control of the motor driver 17 so as to convey the filter paper tape 18, and Pb on the filter paper tape 18 is judged by the second photoelectric detector 142+And Cr3+The heavy metal thin sample is accurately transmitted to an X-ray fluorescence spectrum measuring area, at the moment, the motor driver 17 and the second photoelectric detector 14 stop working, the X-ray tube 19 and the SDD detector 20 start working, and the X-ray tube 19 generates high-energy X-rays to excite the heavy metal Pb2+And Cr3+For thin samples, the SDD detector 20 performs photoelectric conversion on the detected X-ray fluorescence signal, and transmits the signal to the data acquisition and control system 21 for data acquisition and processing.
Claims (7)
1. The utility model provides an algae enrichment-X ray fluorescence spectrum water heavy metal automatic checkout device which characterized in that: the device comprises a heavy metal enrichment system, a paper tape conveying system, a sample drying system, an X-ray fluorescence spectrum measuring system and a data acquisition and control system; the heavy metal enrichment system comprises a reaction cup, a peristaltic pump, a flow controller, a filter cup, an up-down moving device, a sand core supporting base, a filtrate receiving bottle, a vacuum pump and a filter paper belt, wherein a water outlet at the lower end of the reaction cup is connected with the peristaltic pump through a hose, the other end of the peristaltic pump is connected with an inlet of the flow controller through a hose, an outlet of the flow controller is connected with an inlet at the upper end of the filter cup, the lower end of the wall of the filter cup is inwards contracted to form a funnel shape, the bottom of the cup is a circular leak, the filter cup is fixedly connected to the up-down moving device, the sand core supporting base is composed of an upper part and a lower part, the upper part is cylindrical glass with a circular sand core embedded in the center, the thicknesses of the circular sand core and the cylindrical glass are the same, the lower part is cylindrical glass with a through hole in the center, and the outer diameter of the cylindrical glass at the upper part of the sand core supporting base is equal to the outer diameter of the bottom of the filter cup, the diameter of the internal circular sand core is larger than that of a bottom leakage opening of the filter cup, the outer diameter of cylindrical glass at the lower part of the sand core support base is smaller than that of cylindrical glass at the upper part of the sand core support base, the inner diameter of the cylindrical glass at the lower part of the sand core support base is larger than that of the upper circular sand core, the lower part of the sand core support base is connected with the upper end of the filtrate receiving bottle, the inner wall of the cylindrical glass at the lower part of the sand core support base and the outer wall of the glass at the upper end of the filtrate receiving bottle are both frosted glass walls, the calibers are the same, an exhaust opening is arranged at the middle upper end of the filtrate receiving bottle, and the exhaust opening is connected with a vacuum pump through a rubber pipe; the paper tape conveying system comprises a filter paper tape, a paper feeding tape reel, a paper feeding motor, a paper rolling tape reel, a paper rolling motor, a motor driver and a paper feeding positioning detection system, wherein the width of the filter paper tape is the same as the inner diameters of the paper feeding tape reel and the paper rolling tape reel, the motor driver respectively drives the paper feeding motor and the paper rolling motor to rotate, the paper feeding motor drives the paper feeding tape reel to rotate to release the filter paper tape, the paper rolling motor drives the paper rolling tape reel to rotate to roll up the filter paper tape, the rotating speeds of the paper feeding tape reel and the paper rolling tape reel are equal, the filter paper tape is arranged between the filter cup and the sand core supporting base, the width of the filter paper tape is larger than the diameter of a circular sand core on the upper portion of the sand core supporting base, and after the up-down moving device drives the filter cup to move downwards, the filter cup, the filter paper tape, the sand core supporting base, a filtrate receiving bottle and a vacuum pump form a suction filtration system; the paper feeding positioning detection system comprises a punching device, a first photoelectric detector and a second photoelectric detector, wherein the punching device comprises a first stepping motor and a needle head, the punching device is positioned on one side of a sand core supporting base, the first photoelectric detector is positioned in a heating area, and the second photoelectric detector is positioned in an X-ray fluorescence spectrum measurement area; the sample drying system is positioned between the heavy metal enrichment system and the X-ray fluorescence spectrum measurement system, is positioned right below the filter paper tape and is used for heating and drying a heavy metal round thin sample on the filter paper tape, and the sample drying system is composed of a carbon fiber heating pipe and a power supply circuit; the X-ray fluorescence spectrum measuring system comprises an X-ray tube and an SDD detector which are positioned above a filter paper tape, wherein the X-ray tube is an excitation light source and is used for generating high-energy X-rays for exciting the fluorescence of heavy metal characteristic X-rays in a thin sample; the data acquisition and control system is respectively and electrically connected with a control end of the peristaltic pump, a control end of the flow controller, a control end of the up-down moving device, a control end of the vacuum pump, a control end of the motor driver, a control end of the stepping motor I, a control end of the sample drying system, a control end of the photoelectric detector I, a control end of the photoelectric detector II, the X-ray tube and a control end of the SDD detector.
2. The device for automatically detecting the heavy metals in the water body by the algae enrichment-X-ray fluorescence spectrum according to claim 1, which is characterized in that: the filter paper tape is a banded glass fiber microporous filter film, and the aperture size is 0.22 mu m.
3. The device for automatically detecting the heavy metals in the water body by the algae enrichment-X-ray fluorescence spectrum according to claim 1, which is characterized in that: the up-down moving device comprises a support frame, a vertical rail is installed on the support frame, a filter cup holder is installed on the vertical rail in a sliding mode, the filter cup holder is connected with a second stepping motor, the second stepping motor drives the filter cup holder to move up and down on the vertical rail of the support frame, and the second stepping motor is connected with a data acquisition and control system.
4. The device for automatically detecting the heavy metals in the water body by the algae enrichment-X-ray fluorescence spectrum according to claim 3, characterized in that: the data acquisition and control system comprises a power supply module, a data acquisition module, a single chip microcomputer and a control circuit of the single chip microcomputer, wherein the data acquisition module and the power supply module are connected with the single chip microcomputer, the data acquisition module acquires, stores, analyzes and processes signals converted by photoelectric signals of the SDD detector, the single chip microcomputer and the control circuit of the single chip microcomputer respectively send control signals to the peristaltic pump, the flow controller, the up-and-down moving device, the vacuum pump, the punching device, the sample drying system, the first photoelectric detector, the second photoelectric detector, the motor driver, the X-ray tube and the SDD detector, and the power supply module is used for supplying power to the whole device.
5. The detection method of the algae enrichment-X-ray fluorescence spectrum water body heavy metal automatic detection device based on claim 1 is characterized in that: the method comprises a heavy metal adsorption process of algae, a uniform thin sample formation process of algae-heavy metal enrichment, a filter paper belt conveying process, a heavy metal thin sample drying process and an XRF spectrum measurement and analysis process; the process of heavy metal adsorption by algae is as follows: the reaction cup is used for a reaction container for adsorbing heavy metals in water by algae, and when algae cells and heavy metals in the reaction cup reach adsorption balance, the process of enriching algae and heavy metals to form a uniform thin sample is started; the process of forming the uniform thin sample by enriching the algae and the heavy metal comprises the following steps: when the algae cells and the heavy metals in the reaction cup reach adsorption balance, the up-down moving device controls the filter cup to descend and tightly press on a filter paper belt on the sand core supporting base, then the peristaltic pump and the flow controller are started, a liquid sample with a certain volume flows into the filter cup, then the peristaltic pump and the flow controller are closed, then the vacuum pump is started, the filtration of the algae cell suspension liquid with the heavy metals adsorbed in the filter cup is started, the algae cells with the heavy metals adsorbed are enabled to be uniformly settled on the filter paper belt under the action of pressure, and a round thin sample with the heavy metals uniformly distributed is formed; the filter paper belt conveying process comprises the following steps: after the liquid sample in the filter cup is completely filtered, the vacuum pump is closed, the perforating device punches a small hole in the edge of the round thin sample on the filter paper tape, then the filter cup is controlled by the up-and-down moving device to lift upwards, the motor driver and the photoelectric detector are respectively started, the paper feeding motor and the paper rolling motor drive the paper feeding tape reel and the paper rolling tape reel to rotate clockwise under the control of the motor driver so as to convey the filter paper tape, the heavy metal thin sample on the filter paper tape is conveyed to the heating area under the judgment of the photoelectric detector I, and at the moment, the motor driver and the photoelectric detector stop working; the drying process of the heavy metal thin sample comprises the following steps: starting a sample drying system, and heating and drying the heavy metal thin sample arranged above the sample drying system; the XRF spectroscopy measurement and analysis process was: after heating and drying, the sample drying system stops working, after the thin sample is cooled to room temperature, the motor driver and the photoelectric detector are started, the paper feeding motor and the paper winding motor drive the paper feeding belt disc and the paper winding belt disc to rotate clockwise to convey the filter paper belt under the control of the motor driver, the heavy metal thin sample on the filter paper belt is accurately conveyed to the X-ray fluorescence spectrum measurement area under the judgment of the photoelectric detector, at the moment, the motor driver and the photoelectric detector stop working, the X-ray tube and the SDD detector start to work, the X-ray tube generates high-energy X rays to excite the heavy metal thin sample, the SDD detector carries out photoelectric conversion on the detected X-ray fluorescence signals, and the signals are conveyed to the data acquisition and control system to carry out data acquisition and processing.
6. The detection method according to claim 5, characterized in that: the algae is green algae in fresh water microalgae, specifically Chlorella or Scenedesmus obliquus.
7. The detection method according to claim 5, characterized in that: the heavy metal is two or more of lead, cadmium, chromium, nickel, copper, cobalt and silver.
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| CN117907072B (en) * | 2024-03-19 | 2024-05-28 | 上海利元环保检测技术有限公司 | Heavy metal chelating pre-enrichment treatment device in seawater |
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