CN111707744B - Instrument and method for synchronously characterizing physicochemical/optical characteristics of organic matters to be tested - Google Patents
Instrument and method for synchronously characterizing physicochemical/optical characteristics of organic matters to be tested Download PDFInfo
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N30/02—Column chromatography
- G01N30/60—Construction of the column
- G01N30/6034—Construction of the column joining multiple columns
- G01N30/6039—Construction of the column joining multiple columns in series
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The utility model relates to an instrument and a method for synchronously representing physical and chemical/optical characteristics of an organic matter to be detected, which comprises a separation system, an online pretreatment system and a detection system, wherein the separation system comprises an automatic sampler, a SEC chromatographic column, a switching valve and an HIC chromatographic column which are sequentially connected, the SEC chromatographic column is used for realizing sequential separation of the sample to be detected according to the molecular weight, and the HIC chromatographic column is used for realizing separation of the sample to be detected according to the hydrophilic and hydrophobic properties; the on-line pretreatment system comprises an injection valve, an inorganic carbon remover and an ultraviolet digestion device, and the detection system comprises an ultraviolet detector, a three-dimensional fluorescence detector, an organic carbon detector and an organic nitrogen detector; according to the flow path direction of the sample to be detected, the HIC chromatographic column is sequentially connected with an ultraviolet detector, a three-dimensional fluorescence detector, an injection valve, an inorganic carbon remover, an ultraviolet digestion device, an organic carbon detector and an organic nitrogen detector. The method can be used for DBPs precursor identification, adsorption competition mechanism research, membrane pollutant prediction, biochemistry organic carbon/nitrogen detection and other aspects.
Description
Technical Field
The utility model belongs to the technical field of environment detection, and relates to an instrument and a method for synchronously characterizing physicochemical/optical characteristics of an organic matter to be detected.
Background
The pollutants in the surface water source are mainly organic matters, wherein the treatment difficulty of the dissolved part (namely, the dissolved organic matters, dissolved organic matter and DOM) is high, and the treatment is also the key for influencing the quality of the factory water. DOM brings a lot of harm to drinking water treatment, for example, can make raw water present colour, smell and even toxic side effect, reduce membrane filtration and carbon filtration effect, cause membrane jam and active carbon adsorption capacity decline, reduce performances of oxidant and disinfectant etc.. Therefore, the removal rate of DOM should be increased as much as possible in the water treatment process, and it is necessary to fully understand the composition characteristics of DOM and the migration and transformation rules of DOM in the water treatment process (single or combination). Since DOM is a complex and heterogeneous mixture, physical and chemical classification (such as classification according to molecular weight and hydrophilicity and hydrophobicity) of DOM is required, and then related characteristic parameters of separated components are detected to comprehensively reflect physical and chemical (concentration/molecular weight/hydrophilicity and hydrophobicity) and optical characteristics (ultraviolet light absorption/fluorescence characteristics) of DOM. In recent years, size exclusion chromatography (size exclusion chromatography, SEC) and hydrophobic interaction chromatography (hydrophobic interaction chromatography, HIC) have been used for mass separation of unknown samples with molecular weight and hydrophobicity, and multiple detector systems to detect the separated components can realize characterization of DOM physicochemical/optical characteristics due to the advantages of convenient operation, almost no loss, and high efficiency and accuracy of separation.
Beginning with the 2011 DOC-Labor laboratory's development of SEC-based separations and co-characterization of DOM different molecular weight component light absorption/organic carbon concentration/organic nitrogen concentration characteristics in conjunction with ultraviolet detector (UVD), organic Carbon Detector (OCD), and Organic Nitrogen Detector (OND) (also known as LC-OCD-OND, paper see: characterisation of aquatic humic and non-humic matter with size-exclusion chromatography-organic carbon detection-organic nitrogen detection (LC-OCD-OND), water Research, 2011), water workers have increasingly recognized that the use of multiple detectors in combination to characterize DOM technology has great promise. Patent CN 201710097221.9 discloses a method for quantitatively detecting DOM by collecting fluorescence multi-emission three-dimensional spectrum data of each component after separating DOM by SEC. According to the method, DOM with different molecular weights is primarily and roughly divided into humus substances, amino acid substances and non-humus substances, but due to the lack of a concentration detector (OCD or OND and the like), the accuracy of the method for quantitatively detecting DOM is insufficient. Patent CN201811466516.X discloses a method and a device for online detection of DOM by organic nitrogen and organic carbon in series, the device is similar to LC-OCD-OND, can realize synchronous detection of organic carbon and organic nitrogen concentration of different molecular weight components, but lacks other key detection parameter information such as fluorescence, and simultaneously does not provide a solution to the problem of background nitrate ion interference in water with great influence on detection of organic nitrogen (dissolved organic nitrogen, DON). The utility model patent CN201910382778.6 and the utility model patent ZL 201920655954.4 recently disclosed/granted by the inventor firstly use a multi-detector synchronous characterization system to perform ultraviolet light absorption, three-dimensional fluorescence, organic carbon and organic nitrogen concentration characteristic synchronous detection (SEC-UVD/3 DEEMD/OCD/OND) on DON components after SEC separation, and use front-rear OND to separate nitrate ions with larger interference on DON detection.
In 1994, fuchs et al used hydrophobic interaction chromatography (hydrophobic interaction chromatography, HIC) for humus separation for the first time and performed simultaneous detection of uv and organic carbon concentration, achieving satisfactory separation characterization and pointed out that the combined use of different chromatographic separation methods (i.e. multidimensional liquid chromatography) holds promise for DOM analysis (see: application of Hydrophobic Interaction Chromatography (HIC) in Water Analysis, clean-oil Air Water, 1994). HIC utilizes the difference of hydrophobic adsorption strength between different hydrophilic and hydrophobic substances and fillers thereof under different ionic strength, and sequentially separates the different hydrophilic and hydrophobic substances by changing the ionic strength of a mobile phase in a gradient way. HIC is mostly used for separating and purifying protein substances in industries such as medicines, foods and the like, but is less applied to the field of environment detection. Multidimensional liquid chromatography (generally referred to as two-dimensional liquid chromatography) refers to serial detection after a sample is subjected to independent separation by a plurality of chromatographic columns in different modes, and can provide column capacity and detection information which are several times that of common one-dimensional liquid chromatography. Both patents cn201711357830.X and CN201510832550.4 disclose a method for purifying kallikrein using HIC, providing a reference example for application of HIC in the technical field of environmental detection. ZL 201310365709.7 discloses a chromatography system with multi-color columns connected in series, which consists of a separation system and a detection system, wherein various chromatographic columns in the separation system can be selected from normal phase chromatographic columns, reverse phase chromatographic columns, gel chromatographic columns, hydrophobic chromatographic columns or ion exchange chromatographic columns; the detection system consists of a UV detector, a pH detector and a conductivity detector. The system forms a prototype of the multidimensional liquid chromatography system, but has the following defects: (1) The system realizes multidimensional separation by using a plurality of four-way valves or three-way valves connected in series with chromatographic columns, has complex structure and influences the stability of the system; (2) The lack of quantitative detectors (OCDs, ONDs, etc.), fluorescence detectors in the subsequent detectors, lack of accuracy in the quantification of the separated components; (3) The above system does not provide any mobile phase related information (indicated by "reservoir" only) related to the type of chromatographic column, the type of detector, and the nature of the separated water sample, which is critical in the specific chromatographic separation process and instrument development; (4) The system is mainly used in chromatographic chromatography, and is not suitable for the high performance liquid chromatography which is currently mainstream. Patent ZL 201010256470.6 discloses a full two-dimensional ultrahigh pressure high performance liquid chromatography separation system, and the patent focuses on the design and operation method of a two-position ten-way valve system in the separation, which shows that the two-dimensional liquid chromatography can be realized by a laboratory device, but the application of the system is not further described. In terms of specific application of two-dimensional liquid chromatography, patents CN202010086190.9, CN201911112232.5, CN201911051738.X and CN201810857019.6 all disclose a method for separating single components (such as target protein, NNK, sucrose ester, etc.) by using two-dimensional liquid chromatography in combination with a single detector (such as an ultraviolet detector, a mass spectrum detector, etc.), which indicates that the two-dimensional liquid chromatography has mature application in industries such as food, medicine and chemical analysis, but has not been reported in patent report in the field of environmental detection technology, especially DOM detection.
In summary, the main problems of the current DOM characterization method are as follows: (1) The detection information provided by the common one-dimensional liquid chromatography is limited, and the analysis requirement of increasingly complex DOM components cannot be met; (2) The multi-detector combined characterization method after SEC or HIC separation cannot synchronously characterize the physicochemical/optical characteristics of DOM components with different molecular weights/hydrophilicity and hydrophobicity, and the problem of detection interference of inorganic nitrogen ions on DON is not solved.
Disclosure of Invention
The utility model aims to provide an instrument and a method for synchronously characterizing physical, chemical and optical characteristics of an organic matter to be tested. In particular, an apparatus and method for simultaneously characterizing the physicochemical/optical properties of soluble organic matter of different molecular weights/hydrophilicity and hydrophobicity is provided.
The utility model discloses an instrument and a method for synchronously characterizing physical and chemical/optical characteristics of an organic matter to be tested, wherein the DOM is subjected to two-dimensional orthogonal separation by utilizing a full-two-dimensional liquid chromatograph, wherein the full-two-dimensional liquid chromatograph refers to Size Exclusion Chromatography (SEC) as a first-dimensional separation and Hydrophobic Interaction Chromatography (HIC) as a second-dimensional separation, and then the DOM is synchronously characterized by utilizing a multi-detection system comprising an ultraviolet detector UVD, a three-dimensional fluorescence detector 3DEEMD, an organic carbon detector OCD and an organic nitrogen detector OND.
Wherein, the physical and chemical properties of DOM include concentration, molecular weight and hydrophilicity and hydrophobicity, and the optical properties of DOM include ultraviolet light absorption property and fluorescence property.
Wherein the first dimension separation may also be referred to as one-dimensional SEC or LC 1 SEC, the second dimension of separation may also be referred to as two-dimensional HIC or LC 2 HIC, also known as SEC x HIC.
The aim of the utility model can be achieved by the following technical scheme:
in a first aspect of the utility model, an apparatus for synchronously characterizing physicochemical/optical characteristics of an organic matter to be tested is provided, comprising a separation system, an on-line pretreatment system and a detection system,
the separation system comprises an automatic sampler, a SEC chromatographic column, a switching valve and an HIC chromatographic column which are sequentially connected according to the flow path direction of the sample to be detected, wherein the automatic sampler is used for receiving the sample to be detected, the SEC chromatographic column is used for realizing the sequential separation of the sample to be detected according to the molecular weight, and the HIC chromatographic column is used for realizing the separation of the sample to be detected according to the hydrophilic-hydrophobic property;
the on-line pretreatment system comprises an injection valve, an inorganic carbon remover and an ultraviolet digestion device,
the detection system comprises an ultraviolet detector, a three-dimensional fluorescence detector, an organic carbon detector and an organic nitrogen detector;
according to the direction of the flow path of the sample to be detected, the HIC chromatographic column is sequentially connected with an ultraviolet detector, a three-dimensional fluorescence detector, an injection valve, an inorganic carbon remover, an ultraviolet digestion device, an organic carbon detector and an organic nitrogen detector.
In one embodiment of the utility model, the separation system further comprises a SEC mobile phase connected to the autosampler by a SEC infusion pump, the SEC mobile phase being transported to the autosampler by the SEC infusion pump.
In one embodiment of the utility model, the separation system further comprises an HIC mobile phase connected to the switching valve by an HIC infusion pump, the HIC mobile phase being delivered to the switching valve by the HIC infusion pump.
In one embodiment of the utility model, the switching valve comprises 5 interfaces and 2 dosing rings, wherein the 5 interfaces are respectively a first interface, a second interface, a third interface, a fourth interface and a fifth interface, the 2 dosing rings are respectively a first dosing ring and a second dosing ring,
the switching valve has two working states,
when the first dosing ring is not fully loaded, the switching valve is in a first operating state, in which,
the SEC chromatographic column, the first interface, the second interface, the first quantitative ring and the fifth interface are sequentially connected,
the HIC infusion pump, the fifth interface, the second quantifying ring, the fourth interface, the third interface and the HIC chromatographic column are sequentially connected,
the components separated from the SEC chromatographic column enter a first interface, then enter a first quantitative ring from a second interface, are mixed with HIC mobile phase conveyed by an HIC infusion pump at a fifth interface, and enter the HIC chromatographic column through the second quantitative ring, a fourth interface and a third interface;
when the first dosing ring is fully loaded, the switching valve is in the second operating state, at which time,
the SEC chromatographic column, the first interface, the fourth interface, the second quantifying ring and the fifth interface are sequentially connected,
the HIC infusion pump, the fifth interface, the first quantitative ring, the second interface, the third interface and the HIC chromatographic column are sequentially connected,
the liquid flow from the HIC infusion pump enters the first quantitative ring, and then the full SEC component is completely sent into the HIC chromatographic column through the second interface and the third interface; at the same time, the first interface is connected with the fourth interface, and the components separated from the SEC chromatographic column enter the second quantifying ring for storage.
By repeating this, the components separated by the SEC chromatographic column can be transferred to the HIC chromatographic column for further separation.
In one embodiment of the utility model, the volume of the first dosing ring is preferably 5-15 mL.
In one embodiment of the utility model, the fifth interface is further provided with a waste stream outlet, which is provided for preventing the first dosing ring from overflowing in case of accident.
In one embodiment of the utility model, the SEC column packing is preferably a TOYOPEARL company HW-50S packing.
In one embodiment of the utility model, the HIC column is preferably a TSKgel Butyl-NPR column from TOYOPEARL.
In one embodiment of the utility model, the in-line pretreatment system further comprises an acidulant and an oxidizing agent, both of which are connected to the injection valve.
In one embodiment of the utility model, the ultraviolet absorber comprises a metal shell, a low-pressure mercury lamp and a spiral quartz tube, wherein the low-pressure mercury lamp and the spiral quartz tube are both positioned in the metal shell, and the spiral quartz tube is sleeved outside the low-pressure mercury lamp.
In one embodiment of the present utility model, the metal housing is preferably made of stainless steel, and is corrosion resistant; the low-pressure mercury lamp is designed to be arranged in an oxidizing way by double low-pressure mercury lamps, so that the oxidizing efficiency is ensured to the greatest extent; the inner diameter of the spiral quartz tube is preferably 0.5-1.5 mm, the outer diameter of the spiral is preferably 1.5-2.0 cm, and the length is preferably 10-20 m.
In one embodiment of the utility model, the injection valve is preferably a dead volume free, short mixing time, corrosion resistant, high pressure resistant, round injection valve that allows for adequate mixing of the sample stream and oxidant into the ultraviolet digester.
In one embodiment of the utility model, the inorganic carbon remover is preferably a commercial degassing gas module.
In one embodiment of the utility model, the ultraviolet detector, the three-dimensional fluorescence detector, the organic carbon detector and the organic nitrogen detector are all connected with a data acquisition computer.
In the utility model, the ultraviolet detector is used for detecting ultraviolet light absorption characteristics of the separation component.
The three-dimensional fluorescence detector is used for detecting fluorescence characteristics of the separated components.
The organic carbon detector is used for detecting the concentration of organic carbon of the separation component.
The organic nitrogen detector is used for detecting the concentration of organic nitrogen of the separation component.
In one embodiment of the utility model, the data acquisition computer is used for acquiring data of an ultraviolet detector, a three-dimensional fluorescence detector, an organic carbon detector and an organic nitrogen detector.
The utility model also provides an instrument for synchronously characterizing the physicochemical/optical characteristics of the organic matter to be tested, and a method for synchronously characterizing the physicochemical/optical characteristics of the organic matter to be tested, comprising the following steps:
s1, in a SEC flow path: the SEC mobile phase is conveyed to an automatic sampler by a SEC infusion pump, a sample is injected into a flow path by the automatic sampler, the sample flow is sequentially separated in a SEC chromatographic column according to the molecular weight, and then components with different molecular weights enter a switching valve;
s2, in the HIC flow path: the HIC mobile phase is conveyed to the switching valve through an HIC infusion pump;
s3, in the switching valve: the flow paths of the switching valves are switched, all DOM components with different molecular weights are conveyed into an HIC chromatographic column from HIC mobile phases, and are further separated according to the hydrophilic-hydrophobic property;
s4, the sample flow further enters an ultraviolet detector to detect ultraviolet light absorption characteristics, then enters a three-dimensional fluorescence detector to detect/fluorescence characteristics, then is injected with an acidulant and an oxidant and is fully mixed in an injection valve, the sample flow then enters an inorganic carbon remover to remove background carbon dioxide in water, the sample enters an ultraviolet digestion device to be fully oxidized, and DOC and DON are respectively converted into CO 2 And nitrate ions, and detected by a subsequent organic carbon detector and organic nitrogenThe content of the substances is detected by a detector respectively, and finally the substances pass through CO 2 And nitrate ion content is reflected in DOC and DON content.
In one embodiment of the utility model, the SEC mobile phase is preferably a phosphate buffer solution configured using ultrapure water. Further, the concentration of the phosphate buffer solution is preferably 4mm, ph=6.8. The SEC mobile phase ionic strength is critical for SEC to separate DOM accurately according to molecular weight, and is generally related to the type of SEC column packing, the type of sample separated, and the subsequent ability of OCD detector to withstand high salt concentrations, and the applicant has demonstrated through a number of experiments that when HW-50S packing from TOYOPEARL is used as the packing for SEC columns, the SEC mobile phase ionic strength is preferably 0.05 to 0.5mol/L.
In one embodiment of the utility model, the ionic strength of the SEC mobile phase may be adjusted using sodium sulfate.
In one embodiment of the utility model, the flow rate of the SEC infusion pump needs to be adapted to the whole system, so that the full separation of DOM in SEC is ensured, meanwhile, the complete transfer of SEC sample flow into HIC flow path is ensured, and the flow rate of the SEC infusion pump is preferably 1.0-5.0 mL/min and the elution time is 100-150 min as proved by a large amount of experiments.
In one embodiment of the present utility model, the sample injection amount of the autoinjector is preferably 1.0-10.0 mL to ensure the detection accuracy.
In one embodiment of the present utility model, the SEC column is used as a pretreatment column for HIC columns, preferably a preparative column, which can withstand large volumes of sample to ensure accuracy in subsequent HIC separations. The applicant has proved through a large number of experiments that the SEC chromatographic column packing is preferably a TOYOPEARL HW-50S packing, has excellent separation effect on DOM and is suitable for the instrument.
In one embodiment of the utility model, the HIC mobile phase acts as a carrier for the different SEC components, requiring compatibility with the SEC sample stream; meanwhile, the requirements of HIC gradient elution are also met. Applicants have demonstrated through extensive experimentation that the preferred HIC mobile phase is phase A: phosphate buffer solution with high ionic strength, phase B: pure phosphate buffer (4 mm concentration, ph=6.8). Further preferably, the A phase is adjusted to have an ionic strength of 0.5 to 5mol/L using sodium sulfate.
In one embodiment of the utility model, the HIC infusion pump has a flow rate such that: first, transfer SEC components all into HIC; and secondly, shortening the HIC analysis time as much as possible. It is related to SEC infusion pump flow rate, sample loading, and type of sample separated. The applicant has proved through a large number of experiments that on the premise of meeting the parameter settings of other instruments of the system, the flow rate of the HIC infusion pump is preferably 1-3 mL/min; the elution gradient is: 0 to 1min: 100-0% of phase A and 0-100% of phase B; 1 to 1.5min: phase A0%, phase B100%; 1.5 to 2 minutes: 100% of phase A and 0% of phase B.
In one embodiment of the utility model, the HIC column should be able to withstand extremely high column pressures and flow rates, and the analysis time should be as short as possible. The applicant has proved through a large number of experiments that the HIC chromatographic column is preferably a TSKgel Butyl-NPR chromatographic column of TOYOPEARL company, which has the greatest advantage of loading Butyl as a filler, so that the chromatographic column is suitable for organic matter analysis of general natural surface water bodies. Meanwhile, the filler can withstand higher pressure and flow rate and adapt to the analysis conditions of the instrument.
In one embodiment of the utility model, the acidulant is preferably a 6M phosphoric acid solution.
In one embodiment of the utility model, the oxidizing agent is preferably a1 to 5mM potassium persulfate solution.
Preferably, in the above method, each detector signal is acquired by a data acquisition computer.
The instrument and the method provided by the utility model can be used for identifying the disinfection by-product (DBPs) precursor in the field of environmental detection, researching adsorption competition mechanism, predicting membrane pollutants, detecting biochemically-applicable organic carbon/nitrogen and the like.
Compared with the prior art, the instrument and the method can realize synchronous/nondestructive detection of DOM physicochemical (concentration/molecular weight/hydrophilicity) and optical (ultraviolet light absorption/fluorescence) characteristics of different molecular weights/hydrophilicity.
On the other hand, in the utility model, HIC has excellent separation effect on inorganic ions in water, so that micromolecule DON and DIN can be effectively separated, interference of background DIN in water on DON detection can be avoided, and accurate DON detection can be realized.
Drawings
FIG. 1 is a flow chart of a system of an instrument for synchronously characterizing physicochemical/optical characteristics of an organic matter to be tested in an embodiment of the utility model;
FIG. 2 is a schematic diagram of a first operating state of the switching valve;
FIG. 3 is a schematic diagram of a second operating state of the switching valve;
FIG. 4 is a schematic view of the internal structure of the ultraviolet detector;
FIG. 5 is a schematic diagram of raw water detection chromatography of a Taihu lake, suzhou, in example 1;
fig. 6 is a schematic diagram of the quantitative matrix of DON content for creating DOM of different molecular weight/hydrophilicity and hydrophobicity after extracting the color data of the raw water detection chromatogram of a certain water source in the tai lake in su in example 1.
The reference numerals in the figures indicate:
1 a separation system; 1-1SEC mobile phase; 1-2SEC infusion pump; 1-3 an autosampler; 1-4SEC chromatography column; 1-5 switching valves; 1-6HIC mobile phase; 1-7HIC infusion pump; 1-8HIC chromatographic column
2 an online pretreatment system; 2-1 acidulant; 2-2 an oxidizing agent; 2-3 injection valves; 2-4 inorganic carbon remover; 2-5 ultraviolet counteractors;
3, a detection system; 3-1 ultraviolet detector; 3-2 three-dimensional fluorescence detector; 3-3 organic carbon detector; 3-4 organic nitrogen detector; 3-5 data acquisition computers;
1-5-1 to 1-5-5 are respectively different interfaces; 1-5-6 first quantitative loop, 1-5-7 second quantitative loop;
2-5-1 metal housing; 2-5-2 low pressure mercury lamps; 2-5-3 quartz spiral tube.
Detailed Description
Referring to fig. 1, the utility model provides an instrument for synchronously characterizing physicochemical/optical characteristics of an organic matter to be tested, which comprises a separation system 1, an online pretreatment system 2 and a detection system 3, wherein the separation system 1 comprises an automatic sampler 1-3, a SEC chromatographic column 1-4, a switching valve 1-5 and an HIC chromatographic column 1-8 which are sequentially connected according to the flow path direction of the sample to be tested, the automatic sampler 1-3 is used for receiving the sample to be tested, the SEC chromatographic column 1-4 is used for realizing sequential separation of the sample to be tested according to the molecular weight, and the HIC chromatographic column 1-8 is used for realizing separation of the sample to be tested according to the hydrophilic-hydrophobic property; the online pretreatment system 2 comprises an injection valve 2-3, an inorganic carbon remover 2-4 and an ultraviolet digestion device 2-5, and the detection system 3 comprises an ultraviolet detector 3-1, a three-dimensional fluorescence detector 3-2, an organic carbon detector 3-3 and an organic nitrogen detector 3-4; according to the flow path direction of the sample to be detected, the HIC chromatographic column 1-8 is sequentially connected with an ultraviolet detector 3-1, a three-dimensional fluorescence detector 3-2, an injection valve 2-3, an inorganic carbon remover 2-4, an ultraviolet digestion device 2-5, an organic carbon detector 3-3 and an organic nitrogen detector 3-4.
With further reference to FIG. 1, in one embodiment of the present utility model, the separation system 1 further comprises a SEC mobile phase 1-1 and a SEC infusion pump 1-2, the SEC mobile phase 1-1 being connected to the autosampler 1-3 by the SEC infusion pump 1-2, the SEC mobile phase 1-1 being delivered to the autosampler 1-3 by the SEC infusion pump 1-2.
With further reference to FIG. 1, in one embodiment of the utility model, the separation system 1 further comprises an HIC mobile phase 1-6 and an HIC infusion pump 1-7, the HIC mobile phase 1-6 being connected to the switching valve 1-5 by the HIC infusion pump 1-7, the HIC mobile phase 1-6 being transported by the HIC infusion pump 1-7 to the switching valve 1-5.
With further reference to fig. 2 and 3, in one embodiment of the present utility model, the switching valve 1-5 includes 5 ports and 2 dosing rings, the 5 ports are respectively a first port 1-5-1, a second port 1-5-2, a third port 1-5-3, a fourth port 1-5-4, and a fifth port 1-5, the 2 dosing rings are respectively a first dosing ring 1-5-6 and a second dosing ring 1-5-7,
the switching valve 1-5 has two operating states,
when the first quantitative ring 1-5-6 is not fully loaded, the switching valve 1-5 is in a first working state, at this time, the SEC chromatographic column 1-4, the first interface 1-5-1, the second interface 1-5-2, the first quantitative ring 1-5-6 and the fifth interface 1-5-5 are sequentially connected, the HIC infusion pump 1-7, the fifth interface 1-5-5, the second quantitative ring 1-5-7, the fourth interface 1-5-4, the third interface 1-5-3 and the HIC chromatographic column 1-8 are sequentially connected, the components separated from the SEC chromatographic column 1-4 enter the first interface 1-5-1, the components then enter the first quantitative ring 1-5-6 through the second interface 1-5-2, and then enter the HIC chromatographic column 1-8 through the second quantitative ring 1-5-7, the fourth interface 1-5-4 and the third interface 1-3 after being mixed with HIC mobile phase conveyed by the HIC infusion pump 1-7 at the fifth interface 1-5-5;
when the first quantitative ring 1-5-6 is fully loaded, the switching valve 1-5 is in a second working state, at the moment, the SEC chromatographic column 1-4, the first interface 1-5-1, the fourth interface 1-5-4, the second quantitative ring 1-5-7 and the fifth interface 1-5-5 are sequentially connected, the HIC infusion pump 1-7, the fifth interface 1-5-5, the first quantitative ring 1-5-6, the second interface 1-5-2, the third interface 1-5-3 and the HIC chromatographic column 1-8 are sequentially connected, liquid flow from the HIC infusion pump 1-7 enters the first quantitative ring 1-5-6, and full SEC components are all fed into the HIC chromatographic column 1-8 through the second interface 1-5-2 and the third interface 1-5-3; at the same time, the first port 1-5-1 is in communication with the fourth port 1-5-4 and the separated components from the SEC column 1-4 enter the second dosing ring 1-5-7 for storage.
By repeating this, all the components separated by SEC columns 1-4 can be transferred to HIC columns 1-8 for further separation.
In one embodiment of the utility model, the volume of the first dosing ring 1-5-6 is preferably 5-15 mL.
In one embodiment of the utility model, the fifth connection 1-5-5 is further provided with a waste stream outlet, which is provided for the purpose of preventing the first dosing ring 1-5-6 from overflowing in case of accident.
In one embodiment of the utility model, the SEC column 1-4 packing is preferably a TOYOPEARL company HW-50S packing.
In one embodiment of the present utility model, the HIC column 1-8 is preferably a TSKgel Butyl-NPR column from TOYOPEARL.
With further reference to FIG. 1, in one embodiment of the present utility model, the in-line pretreatment system further comprises an acidulant 2-1 and an oxidizing agent 2-2, both of which acidulant 2-1 and oxidizing agent 2-2 are connected to injection valves 2-3.
With further reference to FIG. 4, in one embodiment of the present utility model, the ultraviolet digestion vessel 2-5 comprises a metal shell 2-5-1, a low pressure mercury lamp 2-5-2, and a spiral quartz tube 2-5-3, wherein the low pressure mercury lamp 2-5-2 and the spiral quartz tube 2-5-3 are both positioned in the metal shell 2-5-1, and the spiral quartz tube 2-5-3 is sleeved outside the low pressure mercury lamp 2-5-2.
With further reference to fig. 4, the metal casing 2-5-1 is preferably made of stainless steel, and is corrosion resistant; the low-pressure mercury lamps 2-5-2 are designed to be arranged in an oxidizing way by double low-pressure mercury lamps, so that the oxidizing efficiency is ensured to the greatest extent; the inner diameter of the spiral quartz tube 2-5-3 is preferably 0.5-1.5 mm, the outer diameter of the spiral is preferably 1.5-2.0 cm, and the length is preferably 10-20 m.
In one embodiment of the present utility model, the injection valve 2-3 is preferably a dead volume free, short mixing time, corrosion resistant, high pressure resistant circular injection valve that allows for adequate mixing of the sample stream and oxidant into the uv digestion vessel.
In one embodiment of the present utility model, the inorganic carbon remover 2-4 is preferably a commercial gas removal module.
In one embodiment of the utility model, the ultraviolet detector 3-1, the three-dimensional fluorescence detector 3-2, the organic carbon detector 3-3 and the organic nitrogen detector 3-4 are all connected with the data acquisition computer 3-5.
In the present utility model, the ultraviolet detector 3-1 is used to detect the ultraviolet light absorption characteristics of the separated components.
The three-dimensional fluorescence detector 3-2 is used for detecting fluorescence characteristics of the separated components.
The organic carbon detector 3-3 is used for detecting the concentration of organic carbon of the separation component.
The organic nitrogen detector 3-4 is used for detecting the concentration of organic nitrogen of the separation component.
In one embodiment of the present utility model, the data acquisition computer 3-5 is used for acquiring data of the ultraviolet detector 3-1, the three-dimensional fluorescence detector 3-2, the organic carbon detector 3-3 and the organic nitrogen detector 3-4.
Referring to fig. 1, the utility model also provides an instrument for synchronously characterizing physical and chemical/optical characteristics of an organic matter to be tested, and a method for synchronously characterizing physical and chemical/optical characteristics of the organic matter to be tested, comprising the following steps:
s1, in a SEC flow path: the SEC mobile phase 1-1 is conveyed to the autosampler 1-3 by the SEC infusion pump 1-2, a sample is injected into a flow path by the autosampler 1-3, the sample flow is sequentially separated according to the molecular weight in the SEC chromatographic column 1-4, and then components with different molecular weights enter the switching valve 1-5;
s2, in the HIC flow path: the HIC mobile phase 1-6 is conveyed to the switching valve 1-5 through the HIC infusion pump 1-7;
s3, in the switching valve 1-5: the flow paths of the switching valves 1-5 are switched, all DOM components with different molecular weights are conveyed into HIC chromatographic columns 1-8 from HIC mobile phases, and are further separated according to the hydrophilic-hydrophobic property;
s4, then the sample flow further enters an ultraviolet detector 3-1 to detect ultraviolet light absorption characteristics, then enters a three-dimensional fluorescence detector 3-2 to detect/fluorescence characteristics, then is injected into an acidulant 2-1 and an oxidant 2-2 and is fully mixed in an injection valve 2-3, the sample flow then enters an inorganic carbon remover 2-4 to remove background carbon dioxide in water, then the sample enters an ultraviolet digestion device 2-5 to be fully oxidized, DOC and DON are respectively converted into CO 2 And nitrate ions, and the contents thereof are detected by the subsequent organic carbon detector 3-3 and organic nitrogen detector 3-4, respectively, and finally by CO 2 And nitrate ion content is reflected in DOC and DON content.
In one embodiment of the utility model, the SEC mobile phase 1-1 is preferably a phosphate buffer solution configured using ultrapure water. Further, the concentration of the phosphate buffer solution is preferably 4mm, ph=6.8. The SEC mobile phase 1-1 ionic strength is critical for SEC to separate DOM accurately according to molecular weight, and is generally related to the type of SEC column packing, the type of sample separated, and the ability of the subsequent OCD detector to withstand high salt concentrations, applicants have demonstrated through a number of experiments that when HW-50S packing from TOYOPEARL is used as the packing for SEC column 1-4, the SEC mobile phase 1-1 ionic strength is preferably 0.05 to 0.5mol/L.
In one embodiment of the utility model, the ionic strength of the SEC mobile phase 1-1 may be adjusted using sodium sulfate.
In one embodiment of the utility model, the flow rate of the SEC infusion pump 1-2 needs to be adapted to the whole system, so that the DOM is fully separated in SEC, meanwhile, the SEC sample flow is fully transferred into the HIC flow path, and the applicant has proved through a large amount of experiments that the flow rate of the SEC infusion pump 1-2 is preferably 1.0-5.0 mL/min, and the elution time is 100-150 min.
In one embodiment of the present utility model, the sample injection amount of the autoinjector 1-3 is preferably 1.0-10.0 mL to ensure the detection accuracy.
In one embodiment of the present utility model, the SEC columns 1-4 are used as pretreatment columns of HIC columns, preferably preparative columns, which can withstand large volumes of sample injection to ensure accuracy of subsequent HIC separation. The applicant has proved through a large number of experiments that the packing of the SEC chromatographic column 1-4 is preferably HW-50S packing of TOYOPEARL company, and the packing has excellent separation effect on DOM and is suitable for the instrument.
In one embodiment of the utility model, the HIC mobile phases 1-6 are used as carriers for different SEC components, and are required to be compatible with SEC sample streams; meanwhile, the requirements of HIC gradient elution are also met. Applicants have demonstrated through extensive experimentation that the preferred HIC mobile phase is phase A: phosphate buffer solution with high ionic strength, phase B: the pure phosphate buffer solution had a concentration of 4mm, ph=6.8. Further preferably, the A phase is adjusted to have an ionic strength of 0.5 to 5mol/L using sodium sulfate.
In one embodiment of the utility model, the HIC infusion pumps 1-7 have a flow rate such that: first, transfer SEC components all into HIC; and secondly, shortening the HIC analysis time as much as possible. It is related to SEC infusion pump flow rate, sample loading, and type of sample separated. The applicant has proved through a large number of experiments that under the premise of meeting the parameter settings of other instruments of the system, the flow rate of the HIC infusion pump 1-7 is preferably 1-3 mL/min; the elution gradient is: 0 to 1min: 100-0% of phase A and 0-100% of phase B; 1 to 1.5min: phase A0%, phase B100%; 1.5 to 2 minutes: 100% of phase A and 0% of phase B.
In one embodiment of the utility model, the HIC column 1-8 is tolerant of very high column pressures and flow rates, and the analysis time should be as short as possible. The applicant has shown through a number of experiments that the HIC columns 1-8 are preferably TSKgel Butyl-NPR columns from TOYOPEARL corporation, which have the greatest advantage of being loaded with Butyl as a packing, making them suitable for organic analysis of general natural surface water bodies. Meanwhile, the filler can withstand higher pressure and flow rate and adapt to the analysis conditions of the instrument.
In one embodiment of the utility model, the acidulant 2-1 is preferably a 6M phosphoric acid solution.
In one embodiment of the utility model, the oxidizing agent 2-2 is preferably a1 to 5mM potassium persulfate solution.
Preferably, in the above method, each detector signal is acquired by the data acquisition computer 3-5.
The utility model will now be described in detail with reference to the drawings and specific examples.
Examples
The raw water in a certain place of Taihu lake in Suzhou is taken as a detection object.
The sample analysis results as the detection object were: doc=3.41 ppm; tn=1.17 ppm; before sample injection, 0.45 μm regenerated cellulose membrane was used for filtration, and the filtered sample water was stored at 4℃in a refrigerator and injected within 3 days.
The sample as the object of the test was tested using the apparatus shown in FIG. 1, which provides OCD, OND, UVD as well as 3DEEMD maps of DOM components of different molecular weights/hydrophilicity and hydrophobicity, and the method described above.
When the method for synchronously characterizing the physical and chemical/optical characteristics of the organic matter to be tested is carried out on the basis of the instrument for synchronously characterizing the physical and chemical/optical characteristics of the organic matter to be tested, all mobile phases are configured by newly prepared ultrapure water (the resistivity is 18.2MΩ & ltcm & gt) so as to prevent the interference of mobile phase impurities on the detection result.
SEC mobile phase: phosphate buffer at a concentration of 4mM, ph=6.8, and the ionic strength was adjusted to 0.5mM using sodium sulfate; the flow rate of the pump is 1mL/min; the sample injection amount is 1mL; the pump running time is 70min; sample injection time is 70min; the data acquisition time was 70min.
HIC mobile phase: phase A: phosphate buffer solution at a concentration of 4mm, ph=6.8, and the ionic strength was adjusted to 2M using sodium sulfate; and B phase: phosphate buffer at a concentration of 4mm, ph=6.8. The elution gradient is: 0 to 1min: 100-0% of phase A and 0-100% of phase B; 1 to 1.5min: phase A0%, phase B100%; 1.5 to 2 minutes: 100% of phase A and 0% of phase B. The pump flow rate was 2mL/min.
As shown in fig. 5, LC 1 -SEC represents a first dimension SEC separation; LC (liquid Crystal) device 2 HIC represents a second dimension of HIC separation. LC (liquid Crystal) device 1 -SEC chromatogram with progressively decreasing molecular weight from left to right, LC 2 The HIC chromatogram shows a gradual increase in hydrophobicity from top to bottom, and therefore the DIN component is immobilized in the upper right corner and effectively separated from the DON component. The remainder were different molecular weight/hydrophilic-hydrophobic DON content (represented by shades of color, raw data have been normalized for ease of comparison). The color data in fig. 5 were extracted to create quantitative matrices of DON content for DOM of different molecular weight/hydrophilicity and hydrophobicity, as shown in fig. 6, each letter and number combination represents the content size. For example: a1 to A7 represent the hydrophilic-hydrophobic size arrangements (1 to 7) of the components having a molecular weight range A, and the other positions can be sequentially compared. Specifically, OND quantitative matrix data are shown in table 1, OCD quantitative matrix data are shown in table 2, UVD quantitative matrix data are shown in table 3, protein species (em=340 nm) quantitative matrix data in 3 deimd are shown in table 4, and humus species (em=440 nm) quantitative matrix data in 3 deimd are shown in table 5.
TABLE 1 OND quantitative matrix data
TABLE 2 OCD quantitative matrix data
| A | B | C | D | E | F | G | H | I | |
| 1 | 0.01 | 0.01 | 0.02 | 0.02 | 0.02 | 0.00 | 0.01 | 0.01 | 0.03 |
| 2 | 0.73 | 0.59 | 0.56 | 1.00 | 0.60 | 0.57 | 0.00 | 0.08 | 0.00 |
| 3 | 0.00 | 0.02 | 0.57 | 0.65 | 0.78 | 0.55 | 0.00 | 0.09 | 0.03 |
| 4 | 0.00 | 0.04 | 0.02 | 0.50 | 0.53 | 0.59 | 0.00 | 0.05 | 0.00 |
| 5 | 0.04 | 0.04 | 0.01 | 0.01 | 0.56 | 0.54 | 0.00 | 0.15 | 0.18 |
| 6 | 0.56 | 0.52 | 0.58 | 0.00 | 0.48 | 0.45 | 0.05 | 0.05 | 0.24 |
| 7 | 0.51 | 0.53 | 0.58 | 0.01 | 0.45 | 0.47 | 0.05 | 0.04 | 0.02 |
Table 3 UVD quantitative matrix data
| A | B | C | D | E | F | G | H | I | |
| 1 | 0.00 | 0.00 | 0.00 | 0.05 | 0.01 | 0.04 | 0.01 | 0.00 | 0.00 |
| 2 | 0.03 | 0.15 | 0.52 | 1.00 | 0.56 | 0.53 | 0.00 | 0.10 | 0.03 |
| 3 | 0.03 | 0.02 | 0.53 | 0.24 | 0.74 | 0.56 | 0.03 | 0.10 | 0.03 |
| 4 | 0.00 | 0.08 | 0.00 | 0.50 | 0.51 | 0.57 | 0.00 | 0.02 | 0.00 |
| 5 | 0.03 | 0.07 | 0.06 | 0.52 | 0.59 | 0.56 | 0.00 | 0.16 | 0.03 |
| 6 | 0.02 | 0.05 | 0.54 | 0.54 | 0.46 | 0.50 | 0.01 | 0.05 | 0.53 |
| 7 | 0.00 | 0.00 | 0.00 | 0.03 | 0.00 | 0.02 | 0.00 | 0.00 | 0.00 |
Table 4 quantitative matrix data for proteinaceous substances (Em=340 nm) in 3DEEMD
| A | B | C | D | E | F | G | H | I | |
| 1 | 0.01 | 0.01 | 0.02 | 0.02 | 0.02 | 0.00 | 0.01 | 0.01 | 0.03 |
| 2 | 1.00 | 0.59 | 0.16 | 0.00 | 0.00 | 0.17 | 0.00 | 0.08 | 0.00 |
| 3 | 0.00 | 0.02 | 0.17 | 0.65 | 0.18 | 0.15 | 0.00 | 0.09 | 0.03 |
| 4 | 0.00 | 0.04 | 0.02 | 0.50 | 0.03 | 0.09 | 0.00 | 0.05 | 0.00 |
| 5 | 0.04 | 0.04 | 0.01 | 0.01 | 0.06 | 0.04 | 0.00 | 0.15 | 0.58 |
| 6 | 0.56 | 0.52 | 0.08 | 0.00 | 0.08 | 0.05 | 0.05 | 0.05 | 0.24 |
| 7 | 0.51 | 0.53 | 0.08 | 0.01 | 0.05 | 0.07 | 0.05 | 0.04 | 0.02 |
Table 5 quantitative matrix data for humus species (Em=440 nm) in 3DEEMD
| A | B | C | D | E | F | G | H | I | |
| 1 | 0.01 | 0.01 | 0.02 | 0.02 | 0.02 | 0.00 | 0.01 | 0.01 | 0.03 |
| 2 | 0.02 | 0.08 | 0.50 | 1.00 | 0.53 | 0.50 | 0.00 | 0.10 | 0.03 |
| 3 | 0.00 | 0.02 | 0.50 | 0.22 | 0.72 | 0.57 | 0.00 | 0.07 | 0.02 |
| 4 | 0.00 | 0.00 | 0.00 | 0.51 | 0.49 | 0.59 | 0.00 | 0.01 | 0.05 |
| 5 | 0.04 | 0.02 | 0.06 | 0.54 | 0.58 | 0.60 | 0.00 | 0.16 | 0.08 |
| 6 | 0.03 | 0.02 | 0.52 | 0.55 | 0.41 | 0.52 | 0.00 | 0.07 | 0.50 |
| 7 | 0.02 | 0.01 | 0.05 | 0.00 | 0.01 | 0.04 | 0.01 | 0.04 | 0.00 |
For comparison, the values in all the quantitative matrices are normalized.
The 5-class quantitative matrix can provide abundant quantitative and qualitative detection information of DOM, and comprehensively/systematically characterizes the physicochemical and optical characteristics of DOM.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present utility model. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present utility model is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present utility model.
Claims (4)
1. An instrument for synchronously characterizing physical and chemical/optical characteristics of an organic matter to be tested is characterized by comprising a separation system (1), an online pretreatment system (2) and a detection system (3),
the separation system (1) comprises an automatic sampler (1-3), a SEC chromatographic column (1-4), a switching valve (1-5) and an HIC chromatographic column (1-8) which are sequentially connected according to the flow path direction of a sample to be detected, wherein the automatic sampler (1-3) is used for receiving the sample to be detected, the SEC chromatographic column (1-4) is used for realizing sequential separation of the sample to be detected according to the molecular weight, and the HIC chromatographic column (1-8) is used for realizing separation of the sample to be detected according to the hydrophilic and hydrophobic properties;
the online pretreatment system (2) comprises an injection valve (2-3), an inorganic carbon remover (2-4) and an ultraviolet digestion device (2-5),
the detection system (3) comprises an ultraviolet detector (3-1), a three-dimensional fluorescence detector (3-2), an organic carbon detector (3-3) and an organic nitrogen detector (3-4);
according to the flow path direction of a sample to be detected, the HIC chromatographic column (1-8) is sequentially connected with an ultraviolet detector (3-1), a three-dimensional fluorescence detector (3-2), an injection valve (2-3), an inorganic carbon remover (2-4), an ultraviolet digestion device (2-5), an organic carbon detector (3-3) and an organic nitrogen detector (3-4);
the separation system (1) further comprises an HIC mobile phase (1-6) and an HIC infusion pump (1-7), wherein the HIC mobile phase (1-6) is connected with the switching valve (1-5) through the HIC infusion pump (1-7);
the switching valve (1-5) comprises 5 interfaces and 2 quantitative rings, the 5 interfaces are respectively a first interface (1-5-1), a second interface (1-5-2), a third interface (1-5-3), a fourth interface (1-5-4) and a fifth interface (1-5-5), the 2 quantitative rings are respectively a first quantitative ring (1-5-6) and a second quantitative ring (1-5-7),
the switching valve (1-5) has two working states,
when the first dosing ring (1-5-6) is not fully loaded, the switching valve (1-5) is in a first operating state, in which,
the SEC chromatographic column (1-4), the first interface (1-5-1), the second interface (1-5-2), the first quantitative ring (1-5-6) and the fifth interface (1-5-5) are sequentially connected,
the HIC infusion pump (1-7), the fifth interface (1-5-5), the second quantitative ring (1-5-7), the fourth interface (1-5-4), the third interface (1-5-3) and the HIC chromatographic column (1-8) are sequentially connected,
the components separated from the SEC chromatographic column (1-4) enter a first interface (1-5-1), then enter a first quantitative ring (1-5-6) from a second interface (1-5-2), then enter the HIC chromatographic column (1-8) from a second quantitative ring (1-5-7), a fourth interface (1-5-4) and a third interface (1-5-3) after being mixed with HIC mobile phase conveyed by an HIC infusion pump (1-7) at a fifth interface (1-5-5);
when the first dosing ring (1-5-6) is fully loaded, the switching valve (1-5) is in the second operating state, in which case,
the SEC chromatographic column (1-4), the first interface (1-5-1), the fourth interface (1-5-4), the second quantitative ring (1-5-7) and the fifth interface (1-5-5) are sequentially connected,
the HIC infusion pump (1-7), the fifth interface (1-5-5), the first quantitative ring (1-5-6), the second interface (1-5-2), the third interface (1-5-3) and the HIC chromatographic column (1-8) are sequentially connected,
the liquid flow from the HIC infusion pump (1-7) enters the first quantitative ring (1-5-6), and then the fully loaded SEC component is completely sent into the HIC chromatographic column (1-8) through the second interface (1-5-2) and the third interface (1-5-3); at the same time, the first interface (1-5-1) is communicated with the fourth interface (1-5-4), and the separated components from the SEC chromatographic column (1-4) enter the second quantitative ring (1-5-7) for storage;
the SEC chromatographic column (1-4) packing is selected as HW-50S packing of TOYOPEARL company;
the HIC column (1-8) was selected as TSKgel Butyl-NPR column from TOYOPEARL.
2. The apparatus for synchronously characterizing physicochemical/optical characteristics of organic matters to be tested according to claim 1, wherein the separation system (1) further comprises a SEC mobile phase (1-1) and a SEC infusion pump (1-2), and the SEC mobile phase (1-1) is connected with the autosampler (1-3) through the SEC infusion pump (1-2).
3. The instrument for synchronously characterizing physical and chemical/optical characteristics of an organic matter to be tested according to claim 1, wherein the ultraviolet detector (3-1), the three-dimensional fluorescence detector (3-2), the organic carbon detector (3-3) and the organic nitrogen detector (3-4) are all connected with a data acquisition computer (3-5).
4. An instrument for synchronously characterizing physicochemical/optical characteristics of an organic matter to be tested based on any one of claims 1-3, a method for synchronously characterizing physicochemical/optical characteristics of an organic matter to be tested, comprising the steps of:
s1, in a SEC flow path: the SEC mobile phase (1-1) is conveyed to the automatic sampler (1-3) by the SEC infusion pump (1-2), a sample is injected into a flow path by the automatic sampler (1-3), the sample flow is sequentially separated according to the molecular weight in the SEC chromatographic column (1-4), and then different molecular weight components enter the switching valve (1-5);
s2, in the HIC flow path: the HIC mobile phase (1-6) is conveyed to the switching valve (1-5) through the HIC infusion pump (1-7);
s3, in the switching valve (1-5): the flow paths of the switching valves (1-5) are switched, all DOM components with different molecular weights are conveyed into the HIC chromatographic column (1-8) from HIC mobile phases, and are further separated according to the size of the hydrophilicity and the hydrophobicity;
s4, subsequent sampleThe product flow further enters an ultraviolet detector (3-1) to detect ultraviolet absorption characteristics, then enters a three-dimensional fluorescence detector (3-2) to detect/fluorescence characteristics, then is injected into an acidulant (2-1) and an oxidant (2-2) and is fully mixed in an injection valve (2-3), the sample flow then enters an inorganic carbon remover (2-4) to remove background carbon dioxide in water, then the sample enters an ultraviolet digestion device (2-5) to be fully oxidized, DOC and DON are respectively converted into CO 2 And nitrate ions, and the contents thereof are detected by a subsequent organic carbon detector (3-3) and an organic nitrogen detector (3-4), respectively, and finally by CO 2 And nitrate ion content is reflected in DOC and DON content;
the SEC mobile phase (1-1) is phosphate buffer solution prepared by using ultrapure water, and the ionic strength of the SEC mobile phase (1-1) is 0.05-0.5 mol/L;
the flow rate of the SEC infusion pump (1-2) is selected to be 1.0-5.0 mL/min, and the elution time is 100-150 min;
the HIC mobile phase (1-6) is selected as follows:
phase A: phosphate buffer solution with high ionic strength, wherein the ionic strength of A phase is 0.5-5 mol/L,
and B phase: pure phosphate buffer solution;
the flow rate of the HIC infusion pump (1-7) is 1-3 mL/min; the elution gradient is: 0 to 1min: 100-0% of phase A and 0-100% of phase B; 1 to 1.5min: phase A0%, phase B100%; 1.5 to 2 minutes: 100% of phase A and 0% of phase B.
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| CN108872420A (en) * | 2018-05-18 | 2018-11-23 | 同济大学 | A kind of instrument and method detecting soluble organic nitrogen |
| CN108918746A (en) * | 2018-05-18 | 2018-11-30 | 同济大学 | A kind of synchronous instrument and method for detecting water sample molecular weight distribution and organic nitrogen |
| CN109358128A (en) * | 2018-12-03 | 2019-02-19 | 南京大学 | A kind of organic nitrogen-organic carbon tandem online test method and device |
| CN210294179U (en) * | 2019-05-09 | 2020-04-10 | 同济大学 | Instrument for synchronously representing structure/physicochemical/concentration characteristics of soluble organic matters in water sample |
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| CN108872420A (en) * | 2018-05-18 | 2018-11-23 | 同济大学 | A kind of instrument and method detecting soluble organic nitrogen |
| CN108918746A (en) * | 2018-05-18 | 2018-11-30 | 同济大学 | A kind of synchronous instrument and method for detecting water sample molecular weight distribution and organic nitrogen |
| CN109358128A (en) * | 2018-12-03 | 2019-02-19 | 南京大学 | A kind of organic nitrogen-organic carbon tandem online test method and device |
| CN210294179U (en) * | 2019-05-09 | 2020-04-10 | 同济大学 | Instrument for synchronously representing structure/physicochemical/concentration characteristics of soluble organic matters in water sample |
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