CN111060609A - Full-automatic analysis device and analysis method for solid-phase extraction and enrichment - Google Patents
Full-automatic analysis device and analysis method for solid-phase extraction and enrichment Download PDFInfo
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- CN111060609A CN111060609A CN201911241643.4A CN201911241643A CN111060609A CN 111060609 A CN111060609 A CN 111060609A CN 201911241643 A CN201911241643 A CN 201911241643A CN 111060609 A CN111060609 A CN 111060609A
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention discloses an analysis device and an analysis method for full-automatic solid-phase extraction enrichment, which comprise an automatic sample injection module, a multi-position selection module, a reactor module, an extraction module, an automatic collection module and a power supply and control module; the multi-position selection module comprises a multi-position selection valve, the multi-position selection valve comprises a common interface and a plurality of branch interfaces, and the branch interfaces are respectively connected with the reagent bottles, the purging gas source, the automatic sample injector and the extraction module; the reactor module comprises a syringe pump, the syringe pump is provided with a syringe, the cavity of the syringe is used as a solution mixing and reaction container, and the interface of the syringe is connected with the common interface of the multi-position selection valve; the extraction module comprises a six-way switching valve and a solid phase extraction column; the power supply and control module is used for providing working voltage and current, sending a control command and receiving a feedback signal. The invention can realize full-automatic purification, separation, enrichment and detection of water sample analysis.
Description
Technical Field
The invention belongs to the field of analysis of liquid samples such as water samples and the like, and particularly relates to an analysis device and an analysis method for full-automatic solid-phase extraction enrichment.
Background
Pollutants such as heavy metals, residual pesticides and veterinary drugs in the water body endanger the safety of the dampening ecological environment all the time, and nutrients such as nitrogen and phosphorus regulate and control the balance and change of the dampening ecological system. Therefore, it is always an important task to monitor the environment and the ocean to know the concentration distribution and change rule of pollutants such as heavy metals, residual pesticides, veterinary drugs and the like in rivers, lakes, sewage and seawater and nutrient substances such as nitrogen, phosphorus and the like. However, due to the complexity of various water bodies and the limitations of current detection techniques, these pollutants and nutrients are difficult to accurately determine, or complicated pretreatment methods are required, and more toxic and harmful reagents are consumed to determine the concentration of these targets.
For example, the concentration of heavy metals such as lead, copper, chromium, cadmium, etc. in seawater is very low, but the salinity is very high, which seriously affects the application of the conventional measurement techniques such as atomic absorption spectrometry, inductively coupled plasma emission spectrometry, and inductively coupled plasma mass spectrometry in seawater. Although the current national industry standard marine monitoring specification GB 17378.4-2007 lists the atomic absorption spectrometry as an arbitration method, in the method, after organic reagents are added to form chelates with the heavy metals, organic solvents are added, and the chelates of the heavy metals are separated from a seawater substrate through liquid-liquid extraction, the chelates can be detected by the atomic absorption spectrometry. And even if the concentration of organic pollutants such as malachite green, tetracyclines, quinolones and the like in the aquatic product culture water is very low, the organic pollutants still have great harm. The detection of the target objects also needs to be carried out by liquid-liquid extraction or solid-phase extraction enrichment, and then can be detected by a high performance liquid chromatography-tandem mass spectrometer after elution, concentration and constant volume.
At present, the detection of the target objects is performed manually, namely semi-automatic auxiliary equipment is utilized at most, the experimental steps are complicated, the time consumption is long, a large amount of toxic and harmful reagents are consumed, and great harm is caused to operators and the environment. In view of this, there is a need to explore an efficient, simple, reliable automated analytical detection technique.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an analysis device and an analysis method for full-automatic solid-phase extraction enrichment, and solves the problem of automatic analysis and treatment of trace concentration substances in complex water in the technical background.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the full-automatic solid phase extraction enrichment analysis device comprises an automatic sample introduction module, a multi-position selection module, a reactor module, an extraction module, an automatic collection module and a power supply and control module;
the sample injection module comprises an automatic sample injector and a plurality of sample bottles, wherein the automatic sample injector is provided with a sampling needle, and the sampling needle respectively samples in each sample bottle;
the multi-position selection module comprises a multi-position selection valve and a plurality of reagent bottles; the reagent bottles comprise an activating solution reagent bottle, a regulating solution reagent bottle, an eluent reagent bottle and a dissolving solution reagent bottle; the multi-position selection valve comprises a common interface and a plurality of branch interfaces, and the branch interfaces are respectively connected with each reagent bottle, the purging gas source, the automatic sample injector and the extraction module;
the reactor module comprises a syringe pump, the syringe pump is provided with a syringe, the cavity of the syringe is used as a solution mixing and reaction container, and the interface of the syringe is connected with the common interface of the multi-position selection valve;
the extraction module comprises a six-way switching valve and a solid-phase extraction column, the six-way switching valve is provided with six passages, the solid-phase extraction column is arranged in two passages which are centrosymmetric with the six-way switching valve, and the six-way switching valve is also connected with a waste liquid bottle;
the automatic collection module comprises an automatic sample splitter, a collection cup, a thermostat and a waste gas absorption bottle; the automatic sample splitter is provided with sample outlet needles, the sample outlet needles move to the set collection cups, and liquid flowing out of the sample outlet needles enters the set collection cups; the collecting cup is placed in the constant temperature box; the thermostat is provided with an exhaust hole; the waste gas absorption bottle is connected to the exhaust hole;
the power supply and control module is electrically connected with the sample injection module, the multi-position selection module, the reactor module, the extraction module and the automatic collection module and is used for providing working voltage and current, sending a control command and receiving a feedback signal.
In a preferred embodiment of the present invention, a filtering device is disposed between the sampling needle and the sample bottle, and the filtering device includes a needle filter disposed on the sampling needle.
In a preferred embodiment of the present invention, the automatic sample injector and the automatic sample splitter are three-axis mobile or polar-coordinate carousel type automatic sample injectors, or automatic sample multi-position selector valves equipped with a common interface and 4-24 branch interfaces.
In a preferred embodiment of the present invention, the six-way switching valve is connected to a detector, the detector is provided with a sample inlet and a waste liquid discharge port, the sample inlet of the detector is connected to the six-way switching valve through a three-way joint, the waste liquid discharge port is connected to a waste liquid bottle, and the detector includes an ultraviolet-visible spectrophotometer, a molecular fluorescence spectrophotometer, a chemiluminescence spectrophotometer, an atomic absorption photometer, an atomic fluorescence photometer, an inductively coupled plasma emission spectrometer, an inductively coupled plasma mass spectrometer, a gas chromatograph, a liquid chromatograph, a gas chromatograph-tandem mass spectrometer and a liquid chromatograph-tandem mass spectrometer.
In a preferred embodiment of the present invention, the syringe pump is equipped with a 0.5-50 mL syringe, and the flow rate is 1-50 mL/min.
In a preferred embodiment of the present invention, the solid phase extraction column has an inner diameter of 1 to 10mm and a length of 5 to 100 mm. And a tee joint is arranged between the six-way switching valve and the detector or the automatic sample splitter.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the analysis method of the full-automatic solid-phase extraction enrichment analysis device is used for realizing automatic analysis and treatment of trace concentration substances in a complex water body, and comprises the steps of cleaning, activating, enriching, leaching, eluting, detecting or collecting, concentrating and fixing volume.
In a preferred embodiment of the invention, the sampling is carried out sequentially by the sampling needle, the multi-position selection valve or the six-way switching valve is switched to a valve position for sample injection, and the power supply and control module controls the injection pump to suck the sample;
switching to a valve position communicated with a regulating solution reagent bottle through a multi-position selection valve to enable an injection pump to suck regulating solution, standing and mixing in an injector for 5-1000 seconds to realize pH regulation of a sample;
switching to a valve position connected with the six-way switching valve through a multi-position selection valve, pushing out the solution by an injection pump, enabling the solution to flow through the solid-phase extraction column at a flow rate of 0.1-50 mL/min, and enriching the substance to be detected in the solution onto the solid-phase extraction column;
after enrichment is finished, the valve positions connected with an eluent reagent bottle and an eluent reagent bottle are sequentially switched through a multi-position selection valve, the corresponding valve positions are switched through a six-way switching valve, elution and elution of the solid-phase extraction column are realized, and an eluted object to be detected enters a detector for detection or enters a collecting cup through a sample outlet needle of an automatic sample divider to finish collection; through the switching of the six-way switching valve, the direction of eluent flowing through the solid phase extraction column during elution is opposite to the direction of a sample flowing through the solid phase extraction column during enrichment;
and extracting gas from a purging gas source through an injection pump, blowing the gas into the eluent in the collecting cup until the eluent is blown to be nearly dry, extracting the dissolving liquid through the injection pump, injecting the dissolving liquid into the collecting cup, completing the collection and constant volume of the target object in the dissolving cup, and performing subsequent other detections as the pre-treatment liquid.
In a preferred embodiment of the present invention, the auto-sampler needle moves to a first set sample vial; the multi-position selection valve is switched to a valve position connected with the activation liquid, the injection pump sucks 0.1-50 mL of the activation liquid and then switches to the valve position connected with a fourth interface of the six-way switching valve, the injection pump pushes out the activation liquid, and the activation liquid flows through the solid-phase extraction column at the flow rate of 0.1-50 mL/min to activate the solid-phase extraction column; the multi-position selection valve is switched to a valve position connected with the regulating solution, the injection pump sucks 0.1-50 mL of the regulating solution and then switches to the valve position connected with a fourth interface of the six-way switching valve, the injection pump pushes out the regulating solution, the regulating solution flows through the solid-phase extraction column at a flow rate of 0.1-50 mL/min, and the solid-phase extraction column is regulated to the optimal extraction enrichment condition; the multi-position selection valve is switched to a valve position connected with a common interface or a sampling needle of the automatic sampler, and the injection pump sucks 0.1-49.9 mL of sample to the cavity of the injector; the multi-position selection valve is sequentially switched to valve positions connected with different regulating solutions, the injection pump sequentially sucks 0.1-10 mL of various regulating solutions, and the mixture is kept stand and reacts for 5-1000 seconds; the multi-position selection valve is switched to a valve position connected with a fourth interface of the six-way switching valve, the injection pump pushes out a solution obtained after a mixed reaction of the sample and the regulating solution, the solution flows through the solid-phase extraction column at a flow rate of 0.1-50 mL/min, and a substance to be detected in the solution is adsorbed onto the solid-phase extraction column; after enrichment is completed, the multi-position selection valve is switched to a valve position connected with an eluent reagent bottle, and an injection pump sucks 0.1-50 mL of eluent; switching the multi-position selection valve to a valve position connected with a fourth interface of the six-way switching valve, pushing the leacheate out by an injection pump at the flow rate of 0.1-50 mL/min, leaching the solid-phase extraction column, and leaching impurities remained on the column to a waste liquid bottle; the multi-position selection valve is switched to a valve position connected with the eluent reagent bottle, after 0.1-50 mL of eluent is sucked by the injection pump, the multi-position selection valve is switched to the valve position connected with the first interface of the six-way switching valve, the eluent is pushed out by the injection pump at the flow rate of 0.1-50 mL/min, and the object to be detected on the solid phase extraction column is eluted and enters the detector to be detected; the multi-position selection valve is switched to a valve position connected with a purging gas source, 0.1-50 mL of purging gas is sucked in, then the multi-position selection valve is switched to the valve position connected with a first interface of the tee joint, the purging gas in the cavity of the injector is pushed out, and eluent in a pipeline between the solid-phase extraction column and the detector is purged to the waste liquid bottle; the multi-position selection valve is switched to a valve position connected with a purging gas source, 0.1-50 mL of purging gas is sucked in, then the valve position is switched to a valve position connected with a common interface or a sampling needle of the automatic sample injector, the purging gas in the cavity of the injector is pushed out, and a sample remained in the common interface or the sampling needle pipeline of the automatic sample injector is purged into an original sample bottle; and moving the automatic sample injector to a set second sample bottle, and repeating the steps until the detection of all the set samples is completed.
In a preferred embodiment of the present invention, the analyzer of the present invention is connected to an automatic collection module, the temperature of the oven of the automatic collection module is set to be 4 to 90 ℃, and the exhaust port of the oven is connected to the exhaust gas absorption bottle. Through the steps consistent with the first use method, the multi-position selection valve is switched to a valve position connected with an eluent reagent bottle, after 0.1-50 mL of eluent is sucked into the injection pump, the multi-position selection valve is switched to the valve position connected with a first interface of a six-way switching valve, and a sample outlet needle of the automatic sample splitter moves to a set first collection cup; the injection pump pushes the eluent out at the flow rate of 0.1-50 mL/min, the object to be detected on the solid-phase extraction column is eluted, and the eluted object flows into a first collection cup through a sample outlet needle of the automatic sample splitter; the multi-position selection valve is switched to a valve position connected with a purging gas source, 0.1-50 mL of purging gas is sucked in, the multi-position selection valve is switched to the valve position connected with a first interface of the tee joint, the purging gas in the cavity of the injector is pushed out, and all eluent in a pipeline between the solid-phase extraction column and the sample outlet needle of the automatic sample splitter is purged to the first collection cup; the multi-position selection valve is switched to a valve position connected with a purging gas source, 0.1-50 mL of purging gas is sucked in, the multi-position selection valve is switched to the valve position connected with a sampling needle of the automatic sample injector, the purging gas in the cavity of the injector is pushed out, and a sample remained in the sampling needle pipeline of the automatic sample injector is purged into an original sample bottle; and moving the sampling needle of the automatic sampler to a second set sample bottle, repeating the steps until all set samples are processed, and directly using the samples in the collection cup for on-machine detection.
In a preferred embodiment of the present invention, the analyzer of the present invention is connected to a syringe filter and an autosampler, the temperature of the incubator is set to 4 to 90 ℃, and the exhaust port of the incubator is connected to the exhaust gas absorption bottle. Through the steps consistent with the second use method, until the multi-position selection valve is switched to the valve position connected with the purging gas source, 0.1-50 mL of purging gas is sucked in, and then the multi-position selection valve is switched to the valve position connected with the first interface of the tee joint, the purging gas in the cavity of the injector is pushed out, and all eluent in a pipeline between the solid-phase extraction column and the sample outlet needle of the automatic sample splitter is purged to the first collection cup; the sample outlet needle of the automatic sample splitter is inserted into the collection cup until the sample outlet needle is close to the bottom of the cup, the multi-position selection valve is switched to a valve position connected with a purging gas source, 0.1-50 mL of purging gas is sucked in, then the valve position is switched to a valve position connected with a first interface of the tee joint, the purging gas in the cavity of the injector is pushed out, the gas is used for purging eluent in the collection cup through the sample outlet needle of the automatic sample splitter, and the purging step is repeated for 2-10 times until the eluent in the collection cup is purged to be nearly dry; the multi-position selection valve is switched to a valve position connected with a solution reagent bottle, the injection pump sucks 0.1-50 mL of solution, the multi-position selection valve is switched to the valve position connected with a first connector of the tee joint, the injection pump pushes out the solution in the cavity of the injector, the solution enters a first collection cup, and residues in the solution cup are dissolved; the multi-position selection valve is switched to a valve position connected with a purging gas source, 0.1-50 mL of purging gas is sucked in, then the multi-position selection valve is switched to the valve position connected with a first interface of the tee joint, the purging gas in the cavity of the injector is pushed out, and all dissolved liquid in a pipeline between the solid-phase extraction column and the sample outlet needle of the automatic sample splitter is purged to a first collection cup; the multi-position selection valve is switched to a valve position connected with a purging gas source, 0.1-50 mL of purging gas is sucked in, the multi-position selection valve is switched to the valve position connected with a sampling needle of the automatic sample injector, the purging gas in the cavity of the injector is pushed out, and a sample remained in the sampling needle pipeline of the automatic sample injector is purged into an original sample bottle; and moving the sampling needle of the automatic sampler to a second set sample bottle, repeating the steps until all set samples are processed, and directly using the samples in the collection cup for on-machine detection.
Compared with the background technology, the technical scheme has the following advantages:
the analysis device and the analysis method can fully automatically purify, separate, enrich and detect the target object to be detected in the water sample so as to make up the defects of complexity and low efficiency of a manual method, and the existing automatic analysis device has single function and low automation degree, reduce manual intervention in sample analysis, avoid pollution or errors caused by manual introduction in the sample pretreatment process, improve analysis efficiency and provide on-line analysis technical support.
Drawings
FIG. 1 is a schematic view of the structure of an analysis apparatus according to the present invention;
FIG. 2 is a schematic view of the structure of an analysis apparatus according to embodiment 2;
FIG. 3 is a base-scaled curve of example 2;
FIG. 4 is a schematic view of the structure of an analysis apparatus according to embodiment 3;
FIG. 5 is a base-scaled curve of example 3;
FIG. 6 is a schematic view of the structure of an analysis apparatus according to embodiment 4;
wherein the content of the first and second substances,
an automatic sampler 1, a sampling needle 1a, a needle filter 17;
a multi-position selection valve 2, a common interface 2a of the multi-position selection valve and 12 branch interfaces 2 b-2 m of the multi-position selection valve;
a six-way switching valve 3 and six-way switching valve ports 3a to 3 f;
a waste liquid bottle 4;
an injection pump 5;
a sample bottle 6;
a purge gas source 7;
a solid phase extraction column 8;
a tee joint (valve) 9;
an activating solution reagent bottle 10a, regulating solution reagent bottles 10 b-10 d, an eluent reagent bottle 10e, an eluent reagent bottle 10f and a dissolving solution reagent bottle 10 g;
a power and control module 11;
a detector 12;
an automatic sample splitter 13 and a sample outlet needle 13 a;
a collection cup 14;
a thermostat 15;
an exhaust gas absorption bottle 16.
Detailed Description
Example 1
The analysis device for full-automatic solid-phase extraction and enrichment comprises a sample introduction module, a multi-position selection module, a reactor module, an extraction module, an automatic collection module and a power supply and control module;
the sample injection module comprises an automatic sample injector 1, a plurality of sample bottles 6, an automatic sample splitter 13 and a plurality of collection cups 14, wherein the automatic sample injector 1 is provided with a sampling needle 1a, the sampling needle samples the sample in each sample bottle 6 respectively, the automatic sample splitter 13 is provided with a sample outlet needle 13a, and the sample outlet needles inject solutions into the collection cups 14 respectively;
the automatic collection module further comprises a thermostat 15, the automatic sample divider 13 and the collection cup 14 are arranged in the thermostat 15, the thermostat 15 is provided with exhaust holes, and the exhaust holes are externally connected with a waste gas absorption bottle 16. The temperature control range of the constant temperature box 15 is-4 ℃ to 90 ℃.
In this embodiment, a filtering device is disposed between the sampling needle and the sample bottle 6, and the filtering device includes a needle filter 17 disposed on the sampling needle 1 a.
The automatic sample injector 1 and the automatic sample splitter 13 are both provided with a sampling needle 1a and a sampling needle 13a which can move in three directions, or an automatic multi-position selection valve provided with a common interface 1a and 4-24 branch interfaces is adopted.
The multi-position selection module comprises a multi-position selection valve 2 and a plurality of reagent bottles; the reagent bottles comprise an activating solution reagent bottle 10a (the variety of the activating solution is 1-5), a regulating solution reagent bottle 10 b-10 d (the variety of the regulating solution is 1-15), an eluent reagent bottle 10e, an eluent reagent bottle 10f and/or a dissolving solution reagent bottle 10 g; the multi-position selection valve 2 comprises a common interface 2a and 12 branch interfaces 2 b-2 m, and the branch interfaces 2 b-2 m are respectively connected with each reagent bottle, the purging gas source 7, the automatic sample injector 1 and the extraction module;
the multi-position switching valve is connected with a detector 12, the detector 12 is provided with a sample inlet and a waste liquid discharge port, the sample inlet of the detector 12 is connected with one interface of the tee joint 9, and the waste liquid discharge port is connected with the waste liquid bottle 4; the detector 12 includes an ultraviolet-visible spectrophotometer, a molecular fluorescence spectrophotometer, a chemiluminescence spectrophotometer, an atomic absorption photometer, an atomic fluorescence photometer, an inductively coupled plasma emission spectrometer, an inductively coupled plasma mass spectrometer, a gas chromatograph, a liquid chromatograph, a gas chromatograph-tandem mass spectrometer, and a liquid chromatograph-tandem mass spectrometer.
The reactor module comprises an injection pump 5, the injection pump 5 is provided with a 0.5-50 mL injector, the flow rate ranges from 1 mL/min to 50mL/min, a cavity of the injector is used as a solution mixing and reaction container, and an interface of the injector is connected with a common interface of the multi-position selector valve 2;
the extraction module comprises a six-way switching valve 3 and a solid-phase extraction column 8, the solid-phase extraction column 8 is arranged in two centrosymmetric passages of the six-way switching valve, and the multi-position switching valve is also connected with a waste liquid bottle 4;
the automatic collection module comprises an automatic sample splitter 13, a collection cup 14, a thermostat 15 and an exhaust gas absorption bottle 16; the automatic sample splitter is provided with sample outlet needles 13a, the sample outlet needles 13a move to the set collection cups 14, and the liquid flowing out of the sample outlet needles 13a enters the set collection cups 14; the collecting cup 14 is placed in the constant temperature box 15; the thermostat 15 is provided with an exhaust hole; the waste gas absorption bottle 16 is connected to the exhaust hole;
the power supply and control module 11 is electrically connected with the sample injection module, the multi-position selection module, the reactor module, the extraction module and the automatic collection module, and is used for providing working voltage and current, sending a control command and receiving a feedback signal.
In this embodiment, the six-way switching valve 3 includes a first port 3a, a second port 3b, a third port 3c, a fourth port 3d, a fifth port 3e, and a sixth port 3 f; the solid phase extraction column 8 is arranged between two branch connectors (a third connector 3c and a sixth connector 3f) which are centrosymmetric, the solid phase extraction column 8 comprises a first connector and a second connector, and the inner diameter and the length of the solid phase extraction column 8 are 1-10 mm and 5-100 mm respectively. A tee joint 9 is arranged between the six-way switching valve 3 and the detector 12 or the automatic sample splitter 13.
In this embodiment, a common interface 2a of the multi-position selector valve 2 is connected to an injector interface of the injection pump 5, and 12 branch interfaces 2b to 2m of the multi-position selector valve 2 are respectively connected to the activating solution reagent bottle 10a, the regulating solution reagent bottles 10b, 10c and 10d, the eluent reagent bottle 10e, the sampling needle 1a, the purge gas source 7, the eluent reagent bottle 10f, the solution reagent bottle 10g, the fourth interface 3d of the six-way switching valve 3, the first interface 3a of the six-way switching valve 3, and the first interface of the three-way valve 9; the second port 3b of the six-way switching valve 3 is connected to the second port, the third port 3c and the sixth port 3f of the three-way valve 9, and the first port and the second port of the solid-phase extraction column 8 and the fifth port 3e are respectively connected to the waste liquid collecting bottle 4; the third interface of the tee 9 is connected to the sample outlet 13a or the sample inlet of the detector 12.
The collecting cup 14 is placed inside the incubator 15, and an exhaust port of the incubator 15 is connected to the exhaust gas absorption bottle 16.
The power supply and control module 11 is connected with the automatic sampler 1, the automatic sampler 13, the multi-position selector valve 2, the six-way switching valve 3, the injection pump 5, the thermostat 15 and the detector 12, and is used for providing stable voltage for the components, sending control commands and receiving feedback signals.
When the sampling device is used, samples are sequentially sampled through the sampling needle 1a, the multi-position selection valve 2 or the six-way switching valve 3 is switched to a sample injection valve position, and the power supply and control module controls the injection pump 5 to suck the samples;
switching to a valve position communicated with a regulating solution reagent bottle through a multi-position selection valve 2 to enable an injection pump 5 to suck regulating solution, standing and mixing in an injector for 5-1000 seconds to realize pH regulation of a sample;
the multi-position selection valve 2 is switched to a valve position connected with the six-way switching valve 3, the injection pump 5 pushes out the solution, the solution flows through the solid phase extraction column 8 at the flow rate of 0.1-50 mL/min, and the substances to be detected in the solution are enriched on the solid phase extraction column 8;
after enrichment is finished, the valve positions connected with an eluent reagent bottle and an eluent reagent bottle are sequentially switched through a multi-position selection valve 2, the corresponding valve positions are switched through a six-way switching valve 3, elution and elution of a solid-phase extraction column 8 are realized, and an eluted object to be detected enters a detector 12 for detection or enters a collection cup 14 through an automatic sample splitter 13 to finish collection;
and extracting gas from a purging gas source 7 by using an injection pump 5, blowing the gas into the eluent in the collection cup 14 until the eluent is dried, extracting the dissolving liquid by using the injection pump 5, injecting the dissolving liquid into the collection cup 14, and collecting the target object in the dissolving cup to be used as the pretreatment liquid for subsequent other detections.
According to further requirements of application, the temperature of the constant temperature box 15 is set, the injection pump 5 pumps gas from the purging gas source 7 to blow the eluent into the collection cup 14 until the eluent is nearly dry, then a certain amount of solution is pumped by the injection pump 5 to be injected into the collection cup 14, and the target in the cup is dissolved and the volume is fixed. The purge gas source 7 comprises air purified by filtration or inert gases such as nitrogen and argon provided by a compressed gas cylinder.
Example 2
Example 2 the analysis device of example 1 was used to detect heavy metals in seawater samples:
as shown in fig. 2, the autosampler 13 is not connected in this embodiment, the solution reagent bottle 10g is not required, and the detector 12 is provided as an inductively coupled plasma mass spectrometer.
In this embodiment, the third interface of the tee 9 is connected to the sample inlet of the inductively coupled plasma mass spectrometer of the detector 12, and the waste liquid outlet thereof is connected to the waste liquid bottle 4. The multi-position selector valve 2 is an eight-position selector valve; the injection pump 5 is provided with a 5mL syringe; the automatic sample injector 1 is a fourteen-position selector valve; the common port 1a of the automatic sample injector 1 is connected with the 2k interface of the multi-position selection valve 2; the sample bottle 6 is filled with a seawater sample to be detected; the activating solution reagent bottle 10a and the leacheate reagent bottle 10e are both filled with ammonium acetate buffer solutions with the concentration of 0.05mol/L, pH value of 6.4 +/-0.2 and are respectively connected to the valve positions 2b and 2d of the multi-position selection valve 2; the regulating solution reagent bottle 10d is filled with an ammonium acetate buffer solution with the concentration of 5mol/L, pH and the value of 8.95 +/-0.2 and is connected to the valve position 2c of the multi-position selection valve 2; the eluent reagent bottle 10f is filled with a nitric acid solution with the concentration of 1mol/L and is connected to a valve position 2i of the multi-position selection valve 2; the purge gas source 7 is air and is connected to a valve position 2j of the multi-position selection valve 2; the solid phase extraction column 8 is a solid phase extraction column 8 which has an inner diameter of 2mm and a length of 2cm and is filled with ion chelating resin with iminodiacetic acid functional groups.
The detection operation steps are as follows:
first, washing and activation. The autosampler 1 switches to the first sample stage. The multi-position selection valve 2 is switched to a valve position 2i, and the injection pump 5 is started to suck 3mL of 1mol/L nitric acid solution from the eluent reagent bottle 10 f; the multi-position selection valve 2 is switched to the position of 2g, meanwhile, the six-way switching valve 3 is switched to the solid line state of communication between 3d and 3c, the injection pump 5 is started to push out the nitric acid solution, so that the nitric acid solution flows through the solid phase extraction column 8, and after the solid phase extraction column 8 is cleaned, the nitric acid solution is discharged to the waste liquid bottle 4; the multi-position selection valve 2 is switched to a valve position 2b of an activation solution reagent bottle 10a, and a syringe pump 5 is started to suck 3mL of 1mol/L activation solution of the solid phase extraction column 8, namely ammonium acetate buffer solution with the concentration of 0.05mol/L, pH and the value of 6.4 +/-0.2; the multi-position selection valve 2 is switched to the position of 2g, the six-way switching valve 3 keeps the solid line state of the communication between the 3d and the 3c, the injection pump 5 is started to push the activation liquid out, so that the activation liquid flows through the solid phase extraction column 8, and after the activation of the solid phase extraction column 8, the activation liquid is discharged to the waste liquid bottle 4.
And step two, enriching and leaching. The multi-position selection valve 2 is switched to a valve position 2k, and the injection pump 5 is started to suck 2mL of the first seawater sample; switching the multi-position selection valve 2 to a valve position 2c, starting the injection pump 5 to suck 0.25mL of regulating solution 10d, and standing for 30s to enable the regulating solution to regulate the pH value of the seawater sample to 6.4 +/-0.2; the multi-position selection valve 2 is switched to a valve position 2g, the six-way switching valve 3 is switched to a state of a dotted line communicated with the 3d and the 3e, and the injection pump 5 is started to push out the seawater sample mixed with the regulating solution so as to rinse a pipeline in front of the solid-phase extraction column 8. The multi-position selection valve 2 is switched to a valve position 2k, and the injection pump 5 is started to suck a first seawater sample of 4.5 mL; switching the multi-position selection valve 2 to a valve position 2c, starting the injection pump 5 to suck 0.5mL of regulating solution for 10d, and standing for 30s to enable the regulating solution to regulate the pH value of the seawater sample to 6.4 +/-0.2; the multi-position selection valve 2 is switched to a valve position 2g, meanwhile, the six-way switching valve 3 is switched to a solid line state of communication between 3d and 3c, the injection pump 5 is started to push out the seawater sample at a flow rate of 2mL/min, the seawater flows through the solid phase extraction column 8, heavy metals in the seawater are chelated and adsorbed to the solid phase extraction column 8, and a solution flowing out of the solid phase extraction column 8 enters the waste liquid bottle 4; the multi-position selection valve 2 is switched to a valve position 2d of an eluent reagent bottle 10e, and an injection pump 5 is started to suck 3mL of eluent, namely ammonium acetate buffer solution with the concentration of 0.05mol/L, pH and the value of 6.4 +/-0.2; the multi-position selection valve 2 is switched to the position of 2g, the six-way switching valve 3 keeps the solid line state of communication between the 3d and the 3c, the injection pump 5 is started to push out the leacheate to enable the leacheate to flow through the solid phase extraction column 8, and the seawater substrate remained on the solid phase extraction column 8 is leached to the waste liquid bottle 4.
And thirdly, eluting and detecting. The multi-position selection valve 2 is switched to a valve position 2i of the eluent reagent bottle 10f, and an injection pump 5 is started to suck 2mL of 1mol/L nitric acid solution; the multi-position selection valve 2 is switched to a valve position 2f, meanwhile, the six-way switching valve 3 is switched to a state of a dotted line communicated with the 3b and the 3c, the injection pump 5 is started to push out the nitric acid solution, the nitric acid solution flows through the solid phase extraction column 8, heavy metals on the solid phase extraction column 8 are eluted and sent to the detector 12 for detection, the signal response value of the target object is recorded, and redundant solution enters the waste liquid bottle 4. The multi-position selection valve 2 is switched to a valve position 2j of a purging air source 7, the injection pump 5 is started, and 2mL of air is sucked; the multi-position selection valve 2 is switched to a valve position 2e, the six-way switching valve 3 is switched to a solid line state where the 3d and the 3c are communicated, the injection pump 5 is started, air in the injector is pushed out, and then liquid remained in a pipeline between the three-way valve 9 and the detector 12 is blown to the waste liquid bottle 4.
And fourthly, cleaning. The multi-position selection valve 2 is switched to a valve position 2i of the eluent reagent bottle 10f, and the injection pump 5 is started to suck 1mL of 1mol/L nitric acid solution; the multi-position selection valve 2 is switched to a valve position 2k, the injection pump 5 is started to push out the nitric acid solution, so that the nitric acid solution enters a first seawater sample bottle 6 through a common port of the automatic sample injector 1, and a seawater sample tube at the position is cleaned; the multi-position selection valve 2 is switched to a valve position 2j of a purging air source 7, the injection pump 5 is started, and 2mL of air is sucked; the multi-position selection valve 2 is switched to a valve position 2k, the injection pump 5 is started to push out air, and the solution remained in the pipeline between the valve position 2k and the first seawater sample bottle 6 is swept into the first seawater sample bottle 6, so that the influence of the remained solution on the next sample is avoided.
The detection of one seawater sample is completed through the steps, the automatic sample injector 1 is switched to the next sample grade, and the detection of the next sample is started by repeating the steps.
Through the above steps, the seawater substrate calibration curves of chromium, iron, nickel, copper, zinc, cadmium and lead in seawater were simultaneously determined in the present example, and the calibration concentrations were 0, 2.5, 5.0, 7.5, 10.0 and 12.5nmol/L, and the obtained results are shown in table 1 and fig. 3.
Table 1 example 2 determination of seawater base spiking fitting curves for 7 heavy metals
| Metallic element | Sea water base standard-adding fitting curve | Linear dependence R2 |
| Chromium (III) | y＝5659.2x+1133.8 | 0.9997 |
| Iron | y＝3310.3x+3986.8 | 0.9984 |
| Nickel (II) | y＝3347.9x+1561.7 | 0.9991 |
| Copper (Cu) | y＝9866x+8696.8 | 0.9994 |
| Zinc | y＝982.97x+733.99 | 0.9979 |
| Cadmium (Cd) | y＝2380.6x+150.15 | 0.9997 |
| Lead (II) | y＝41650x+7434.6 | 0.9995 |
Example 3
Example 3 the analysis apparatus of example 1 was used to enrich heavy metals in seawater samples:
as shown in FIG. 4, in this example, the autosampler 13 and the incubator 15 are connected, but the detector 12 is not provided, and the solution reagent bottle 10g is not provided;
in this embodiment, the third port of the tee 9 is connected to the common port 13a of the autosampler 13, the other ports of the autosampler 13 are connected to the collection cups 14, respectively, and the temperature of the incubator 15 is set to 4 ℃. The multi-position selector valve 2 is an eight-position selector valve; the injection pump 5 is provided with a 5mL syringe; the automatic sample injector 1 and the automatic sample splitter 13 are fourteen-bit selection valves; the common port 1a of the automatic sample injector 1 is connected with the 2k interface of the multi-position selection valve 2; the positions, specifications and reagent concentrations of the sample bottle 6, the activating solution reagent bottle 10a, the leacheate reagent bottle 10e, the regulating solution reagent bottle 10d, the eluent reagent bottle 10f, the purging gas source 7 and the solid-phase extraction column 8 are the same as those in the embodiment 2.
The detection operation steps of this example, the first step and the second step, were the same as in example 2.
And thirdly, eluting and collecting. The autosampler 13 switches to the first collection cup 14 position. The multi-position selection valve 2 is switched to a valve position 2i of the eluent reagent bottle 10f, and an injection pump 5 is started to suck 2mL of 1mol/L nitric acid solution; the multi-position selection valve 2 is switched to a valve position 2f, meanwhile, the six-way switching valve 3 is switched to a state of a dotted line communicated with the 3b and the 3c, the injection pump 5 is started to push out the nitric acid solution, so that the nitric acid solution flows through the solid phase extraction column 8, heavy metals on the solid phase extraction column 8 are eluted, and the nitric acid solution flows through a common port 13a of the automatic sample splitter 13 and then enters the first collection cup 14. The multi-position selection valve 2 is switched to a valve position 2j of a purging air source 7, the injection pump 5 is started, and 2mL of air is sucked; the multi-position selection valve 2 is switched to a valve position 2e, the six-way switching valve 3 is switched to a solid line state where the 3d and the 3c are communicated, the injection pump 5 is started, air in the injector is pushed out, and then eluent remained in a pipeline between the three-way valve 9 and the common port 13a of the automatic sample splitter 13 and subsequent pipelines is blown into the collection cup 14.
And fourthly, cleaning. The multi-position selection valve 2 is switched to a valve position 2i of the eluent reagent bottle 10f, and the injection pump 5 is started to suck 1mL of 1mol/L nitric acid solution; the multi-position selection valve 2 is switched to a valve position 2k, the injection pump 5 is started to push out the nitric acid solution, so that the nitric acid solution enters a first seawater sample bottle 6 through a common port of the automatic sample injector 1, and a seawater sample tube at the position is cleaned; the multi-position selection valve 2 is switched to a valve position 2j of a purging air source 7, the injection pump 5 is started, and 2mL of air is sucked; the multi-position selection valve 2 is switched to a valve position 2k, the injection pump 5 is started to push out air, and the solution remained in the pipeline between the valve position 2k and the first seawater sample bottle 6 is swept into the first seawater sample bottle 6, so that the influence of the remained solution on the next sample is avoided.
The enrichment and separation treatment of heavy metals in a seawater sample is completed through the steps, the automatic sample injector 1 is switched to the next sample grade, the automatic sample injector 13 is switched to the next collection cup 14, and the pretreatment of the next sample is started after the steps are repeated.
Through the above steps, the seawater substrate spiked samples of chromium, iron, nickel, copper, zinc, cadmium and lead in seawater were treated in the present example with spiked concentrations of 0, 2.5, 5.0, 7.5, 10.0 and 12.5nmol/L, and the eluate in the collection cup 14 was measured by an inductively coupled plasma mass spectrometer, and the results are shown in table 2 and fig. 5.
Table 2 example 3 determination of seawater base spiking fitting curves for 7 heavy metals
Example 4
Example 4 the analytical device of example 1 was used to enrich water samples for tetracycline and quinolone antibiotics:
as shown in FIG. 6, the present embodiment is connected to an autosampler 13 and an incubator 15, and provided with a solution reagent bottle 10 g;
in this embodiment, a needle filter 17 is connected to each sample inlet of the autosampler 1, the third port of the tee 9 is connected to the common port 13a of the autosampler 13, and the other ports of the autosampler 13 are connected to one collection cup 14. The multi-position selector valve 2 is a twelve-position selector valve; the injection pump 5 is provided with a 50mL syringe; the automatic sample injector 1 is a fourteen-position selector valve; the common port 1a of the automatic sample injector 1 is connected with the 2k interface of the multi-position selection valve 2; the sample bottle 6 is filled with a water sample to be detected; the activating solution reagent bottle 10a is filled with methanol, and the leacheate reagent bottle 10e is filled with pure water and is respectively connected to the valve positions 2b and 2d of the multi-position selection valve 2; the regulating solution reagent bottles 10c and 10d are respectively filled with hydrochloric acid solution and Na2EDTA-Mclvaine buffer solution which is respectively connected to the valve positions 2l and 2c of the multi-position selection valve 2; the eluent reagent bottle 10f is filled with 20% methanol/acetone solution and is connected to a valve position 2i of the multi-position selection valve 2; the purge gas source 7 is high-purity nitrogen and is connected to a valve position 2j of the multi-position selection valve 2; the solid phase extraction column 8 is an HLB solid phase extraction column 8 with the inner diameter of 9mm and the length of 5 mm; and 10g of the solution reagent bottle is filled with 80% methanol aqueous solution and is connected to the valve position 2h of the multi-position selection valve 2.
The operation steps of this example are as follows:
first, washing and activation. The autosampler 1 was switched to the first sample stage and the temperature of the oven 15 was set to 40 ℃. The multi-position selection valve 2 is switched to a valve position 2i, and the injection pump 5 is started to suck 5mL of 20% methanol/acetone solution from the eluent reagent bottle 10 f; the multi-position selection valve 2 is switched to the position of 2g, meanwhile, the six-way switching valve 3 is switched to the solid line state of communication between 3d and 3c, the injection pump 5 is started to push the eluent out, so that the eluent flows through the enrichment column 8, and the eluent is discharged to the waste liquid bottle 4 after the solid phase extraction column 8 is cleaned; the multi-position selection valve 2 is switched to a valve position 2b, and the injection pump 5 is started to suck 3mL of methanol from the activating solution reagent bottle 10 a; the multi-position selection valve 2 is switched to the position of 2g, meanwhile, the six-way switching valve 3 is switched to the solid line state of communication between 3d and 3c, the injection pump 5 is started to push out the methanol, so that the methanol flows through the solid phase extraction column 8, and the methanol is discharged to the waste liquid bottle 4 after the solid phase extraction column 8 is activated; the multi-position selection valve 2 is switched to a valve position 2d, and the injection pump 5 is started to suck 3mL of leacheate, namely pure water, from the leacheate reagent bottle 10 e; the multi-position selection valve 2 is switched to the position of 2g again, meanwhile, the six-way switching valve 3 keeps the solid line state of communication between the 3d and the 3c, the injection pump 5 is started to push out the leacheate, so that the leacheate flows through the solid phase extraction column 8, and after the solid phase extraction column 8 is leached, the leacheate is discharged to the waste liquid bottle 4.
And step two, enriching and leaching. The multi-position selection valve 2 is switched to a valve position 2k, and the injection pump 5 is started to suck 2mL of the first water sample; the multi-position selection valve 2 is switched to the valve position 2c, and the injection pump 5 is started to suck 0.45mL of Na2EDTA-Mclvaine buffer solution 10d, standing for 30 s; switching the multi-position selection valve 2 to a valve position of 2l, starting the injection pump 5 to suck 0.05mL of hydrochloric acid solution, and standing for 30 s; the multi-position selection valve 2 is switched to a valve position 2g, the six-way switching valve 3 is switched to a dotted line state of communication between 3d and 3e, and the injection pump 5 is started to push out the water sample mixed with the regulating solution so as to rinse a pipeline in front of the HLB solid-phase extraction column 8.
The multi-position selection valve 2 is switched to a valve position 2k, and the injection pump 5 is started to suck 10mL of the first water sample; the multi-position selection valve 2 is switched to the valve position 2c, and the injection pump 5 is started to suck 2.25mL of Na2EDTA-Mclvaine buffer solution 10 d; the multi-position selection valve 2 is switched to the valve position 2l, and the injection pump 5 is started to suck 0.25mL of hydrochloric acid solution. This was repeated 4 times, and a total of 40mL of the water sample, 9mL of Na, was aspirated into syringe pump 52EDTA-Mclvaine buffer solution and 1mL hydrochloric acid solution, and adjusting the pH value of the water sample to be about 4.0. After standing for 30s, the multi-position selection valve 2 is switched to a valve position 2g, meanwhile, the six-way switching valve 3 is switched to a solid line state communicated with 3d and 3c, the injection pump 5 is started to push out the water sample at a flow rate of 3mL/min, the water sample flows through the HLB solid-phase extraction column 8, a target object in the water sample is enriched to the HLB column 8, and a solution flowing out of the HLB column 8 enters the waste liquid bottle 4; the multi-position selection valve 2 is switched to a valve position 2d, and the injection pump 5 is started to suck 3mL of leacheate 10 e; the multi-position selection valve 2 is switched to the position of 2g, and the six-way switching valve 3 is protectedAnd (5) keeping the solid line state of the communication between the 3d and the 3c, starting the injection pump 5 to push out the leacheate to enable the leacheate to flow through the solid phase extraction column 8, and leaching impurities remained on the column to the waste liquid bottle 4. The multi-position selection valve 2 is switched to a valve position 2j of a purge gas source 7, the injection pump 5 is started, and 50mL of nitrogen is sucked; the multi-position selection valve 2 is switched to a valve position 2g, the six-way switching valve 3 keeps the solid line state of communication between the 3d and the 3c, the injection pump 5 is started to push out nitrogen at the speed of 10mL/min, and the solid phase extraction column 8 is dried.
And thirdly, eluting and cleaning. The autosampler 13 switches to the first collection cup 14 position. The multi-position selection valve 2 is switched to a valve position 2i, and the injection pump 5 is started to suck 6mL of 20% methanol/acetone solution from the eluent reagent bottle 10 f; the multi-position selection valve 2 is switched to a valve position 2f, meanwhile, the six-way switching valve 3 is switched to a dotted line state of communication between the 3b and the 3c, the injection pump 5 is started to push the eluent out, the target object on the solid phase extraction column 8 is eluted, and the eluent enters the first collection cup 14 through the common port 13a of the automatic sample splitter 13. The multi-position selection valve 2 is switched to a valve position 2j of a purge gas source 7, the injection pump 5 is started, and 10mL of nitrogen is sucked; the multi-position selection valve 2 is switched to a valve position 2e, the six-way switching valve 3 is switched to a solid line state where the 3d and the 3c are communicated, the injection pump 5 is started, 5mL of nitrogen is pushed out, and eluent remained in a pipeline between the three-way valve 9 and the public port 13a of the automatic sample splitter 13 and subsequent pipelines is purged into the collection cup 14.
The multi-position selection valve 2 is switched to a valve position 2b, and the injection pump 5 is started to suck 3mL of methanol solution from the activating solution reagent bottle 10 a; the multi-position selection valve 2 is switched to a valve position 2k, the injection pump 5 is started to push out the methanol solution, so that the methanol solution enters a first sample bottle 6 through a common port of the automatic sample injector 1, and a sample pipeline at the position is cleaned; the multi-position selection valve 2 is switched to a valve position 2j of a purge gas source 7, the injection pump 5 is started, and 3mL of nitrogen is sucked; the multi-position selection valve 2 is switched to a valve position 2k, the injection pump 5 is started to push out nitrogen, and residual solution in a pipeline between the valve position 2k and the first sample bottle 6 is purged out, so that the influence of the residual solution on the next sample is avoided.
And (3) switching the automatic sample injector 1 and the automatic sample splitter 13 to the next sample grade and the position of the collecting cup 14, and repeating the three steps circularly until all the water samples on the automatic sample injector 1 are processed.
And fourthly, nitrogen is blown to concentrate. The autosampler 13 switches to the first collection cup 14. The multi-position selection valve 2 is switched to a valve position 2j of a purge gas source 7, the injection pump 5 is started, and 50mL of nitrogen is sucked; the multi-position selector valve 2 was switched to the valve position 2e, the six-way selector valve 3 was switched to the solid line state where 3d and 3c communicate, and the syringe pump 5 was started to push out 50mL of nitrogen gas and blow it into the collection cup 14. This step is repeated 50 times, and the eluate in the first collection cup 14 is concentrated to near dryness. The autosampler 13 switches to the second collection cup 14 again, and the above steps are repeated to concentrate the eluent in the second collection cup 14 to near dryness. The above steps are repeated until all the eluents in the collection cups 14 on the autosampler 13 are concentrated to near dryness.
And fifthly, dissolving to fix the volume. The temperature of the oven 15 was set to 4 ℃ and the six-way switching valve 3 was maintained in the solid line state with the communication between 3d and 3 c. The automatic sample splitter 13 is switched to a first collecting cup 14, the multi-position selector valve 2 is switched to a valve position for 2h, and the injection pump 5 is started to suck a dissolving solution, namely 80% methanol-water solution, in a 1mL dissolving solution reagent bottle 10 g; the multi-position selection valve 2 is switched to a valve position 2e, the injection pump 5 is started, 1mL of solution is pushed out to the first collection cup 14, and then the injection pump 5 is stopped; the multi-position selection valve 2 is switched to a valve position 2j, the injection pump 5 is started, and 2mL of nitrogen is sucked; and (3) switching the multi-position selection valve 2 to a valve position 2e, starting the injection pump 5, pushing out 2mL of nitrogen, and purging residual solution in a pipeline between the multi-position selection valve 2 and the common port 13a of the automatic sample splitter 13 and a subsequent pipeline thereof into the collection cup 14 to finish constant volume. The autosampler 13 continues to switch to the second collection cup 14, the multi-position selector valve 2 is switched to the valve position 2h, the syringe pump 5 is started, and the above steps are repeated until all the collection cups 14 on the autosampler 13 are filled with 1mL of the dissolution solution.
After all the steps are completed, the solution in the collecting cup 14 is filtered by a filter membrane with the diameter of 0.22 μm, and then the solution can be measured by an ultra-high performance liquid chromatography-tandem mass spectrometer.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (8)
1. The utility model provides an analytical equipment of full-automatic solid phase extraction enrichment which characterized in that: the device comprises an automatic sample introduction module, a multi-position selection module, a reactor module, an extraction module, an automatic collection module and a power supply and control module;
the sample injection module comprises an automatic sample injector and a plurality of sample bottles, wherein the automatic sample injector is provided with a sampling needle, and the sampling needle respectively samples in each sample bottle;
the multi-position selection module comprises a multi-position selection valve and a plurality of reagent bottles; the reagent bottles comprise an activating solution reagent bottle, a regulating solution reagent bottle, an eluent reagent bottle and a dissolving solution reagent bottle; the multi-position selection valve comprises a common interface and a plurality of branch interfaces, and the branch interfaces are respectively connected with each reagent bottle, the purging gas source, the automatic sample injector and the extraction module;
the reactor module comprises a syringe pump, the syringe pump is provided with a syringe, the cavity of the syringe is used as a solution mixing and reaction container, and the interface of the syringe is connected with the common interface of the multi-position selection valve;
the extraction module comprises a six-way switching valve and a solid-phase extraction column, the six-way switching valve is provided with six passages, the solid-phase extraction column is arranged in two passages which are centrosymmetric with the six-way switching valve, and the six-way switching valve is also connected with a waste liquid bottle;
the automatic collection module comprises an automatic sample splitter, a collection cup, a thermostat and a waste gas absorption bottle; the automatic sample splitter is provided with sample outlet needles, the sample outlet needles move to the set collection cups, and liquid flowing out of the sample outlet needles enters the set collection cups; the collecting cup is placed in the constant temperature box; the thermostat is provided with an exhaust hole; the waste gas absorption bottle is connected to the exhaust hole;
the power supply and control module is electrically connected with the sample injection module, the multi-position selection module, the reactor module, the extraction module and the automatic collection module and is used for providing working voltage and current, sending a control command and receiving a feedback signal.
2. The analysis device for full-automatic solid-phase extraction enrichment according to claim 1, characterized in that: and a filtering device is arranged between the sampling needle and the sample bottle, and the filtering device comprises a needle head type filter arranged on the sampling needle.
3. The analysis device for full-automatic solid-phase extraction enrichment according to claim 1, characterized in that: the automatic sample injector and the automatic sample splitter are three-axis movable or polar coordinate rotating disc type automatic distributors or automatic sample injection multi-position selection valves provided with public interfaces and 4-24 branch interfaces.
4. The analysis device for full-automatic solid-phase extraction enrichment according to claim 1, characterized in that: the six-way switching valve is connected with a detector, the detector is provided with a sample inlet and a waste liquid discharge port, the sample inlet of the detector is connected with the six-way switching valve through a tee joint, the waste liquid discharge port is connected with a waste liquid bottle, and the detector comprises an ultraviolet visible spectrophotometer, a molecular fluorescence photometer, a chemiluminescence photometer, an atomic absorption photometer, an atomic fluorescence photometer, an inductively coupled plasma emission spectrometer, an inductively coupled plasma mass spectrometer, a gas chromatograph, a liquid chromatograph, a gas chromatograph-tandem mass spectrometer and a liquid chromatograph-tandem mass spectrometer.
5. The analysis device for full-automatic solid-phase extraction enrichment according to claim 1, characterized in that: the injection pump is provided with a 0.5-50 mL injector, and the flow rate ranges from 1-50 mL/min.
6. The analysis device for full-automatic solid-phase extraction enrichment according to claim 1, characterized in that: the solid phase extraction column has an inner diameter of 1-10 mm and a length of 5-100 mm.
7. An analysis method for full-automatic solid phase extraction enrichment is characterized in that: the full-automatic solid-phase extraction and enrichment analysis device as claimed in any one of claims 2 to 6 is used for realizing automatic analysis and treatment of trace concentration substances in a complex water body, and comprises the steps of filtering, cleaning, activating, enriching, leaching, eluting, detecting or collecting, concentrating and fixing volume.
8. The analysis method of the full-automatic solid phase extraction enrichment according to claim 7, characterized in that:
sampling is carried out in sequence through the sampling needle, the multi-position selection valve is switched to a valve position of sample injection, and the power supply and control module controls the injection pump to suck the sample;
switching to a valve position communicated with a regulating solution reagent bottle through a multi-position selection valve to enable an injection pump to suck regulating solution, standing and mixing in an injector for 5-1000 seconds to realize pH regulation of a sample;
switching to a valve position connected with the six-way switching valve through a multi-position selection valve, pushing out the solution by an injection pump, enabling the solution to flow through the solid-phase extraction column at a flow rate of 0.1-50 mL/min, and enriching the substance to be detected in the solution onto the solid-phase extraction column;
after enrichment is finished, the valve positions connected with an eluent reagent bottle and an eluent reagent bottle are sequentially switched through a multi-position selection valve, the corresponding valve positions are switched through a six-way switching valve, elution and elution of the solid-phase extraction column are realized, and an eluted object to be detected enters a detector for detection or enters a collecting cup through a sample outlet needle of an automatic sample divider to finish collection; through the switching of the six-way switching valve, the direction of eluent flowing through the solid phase extraction column during elution is opposite to the direction of a sample flowing through the solid phase extraction column during enrichment;
and extracting gas from a purging gas source by using an injection pump, blowing the gas into the eluent in the collecting cup until the eluent is dried, extracting a dissolving solution by using the injection pump, injecting the dissolving solution into the collecting cup, and collecting the target object in the dissolving cup to be used as a pretreatment solution for subsequent detection.
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| CN113358767A (en) * | 2021-04-30 | 2021-09-07 | 上海睿康生物科技有限公司 | Full-automatic ultra-high performance liquid chromatography tandem mass spectrometry detection system and working method |
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