CN110082447A - Synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument - Google Patents
Synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000012512 characterization method Methods 0.000 title claims abstract description 32
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 25
- 239000005446 dissolved organic matter Substances 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 claims abstract description 69
- 125000001477 organic nitrogen group Chemical group 0.000 claims abstract description 66
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000005416 organic matter Substances 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 102
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 9
- 239000003651 drinking water Substances 0.000 abstract description 9
- 235000020188 drinking water Nutrition 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 6
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- 238000000926 separation method Methods 0.000 description 27
- 230000000694 effects Effects 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 229910021642 ultra pure water Inorganic materials 0.000 description 15
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- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 8
- 239000003864 humus Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
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- 229920001282 polysaccharide Polymers 0.000 description 5
- 239000005017 polysaccharide Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 3
- 238000006213 oxygenation reaction Methods 0.000 description 3
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
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- 229910052724 xenon Inorganic materials 0.000 description 3
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- 239000007800 oxidant agent Substances 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
- 229930182905 microdon Natural products 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
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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
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/64—Electrical detectors
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
- G01N2030/125—Preparation by evaporation pyrolising
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument is characterized the present invention relates to synchronous, belongs to technical field of environmental detection.All appts carry out single-flow-path connection, it is therefore intended that: (1) guarantee the synchronism and stability of multi-detector detection system entirety；(2) influence of the nitrate ion to water sample distribution in water sample to be measured is removed, realizes the accurate detection of different molecular weight distribution.The present invention can the synchronous detection of UV absorption/fluorescent characteristic/organic concentration of carbon to different molecular weight organic matter in water sample/organic nitrogen concentration, realize structure/physics and chemistry/grey density characteristics comprehensive characterization of water sample to be measured.Quantitative/qualitative information is enriched provided by instrument of the present invention and method can be used for research and the applications such as water treatment field water quality quickly scans, accurate identification, fouling membrane mechanism and the water treatment technology of disinfection by-product of drinking water precursor optimize.
Description
Technical field
The present invention relates to technical field of environmental detection, purple more particularly, to a kind of single-flow-path based on size exclusion chromatography
The synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument of outer light/fluorescence/organic carbon/organic nitrogen multi-detector
Device and method.
Background technique
Dissolved Organic Matter (dissolved organic matter, DOM) is widely present in major natural water, it
It is one of the problem of being primarily upon in drinking water treatment.The presence of DOM can make water body that bad color and peculiar smell be presented.In addition,
DOM also will affect the treatment effect of ozone and activated carbon, membrane filtration process, and it is possible to micro- life can be bred in water distributing network
Object.DOM can also reduce the performance of oxidant and disinfectant, generate harmful oxidation and disinfection by-products, seriously threaten drinking water
Water supply security.In view of many hazards of DOM, the removal rate for increasing DOM as far as possible in drinking water treatment technique is optimization water
One of target for the treatment of process, it is therefore necessary to comprehensively characterize DOM structure/physics and chemistry/grey density characteristics and its in single/combination water
Degradation and Transformation rule in treatment process.
Understand that DOM concentration feature has two " Jin Zhibiao ": dissolved organic carbon (DOC) and soluble organic nitrogen (DON).
DOC and biological activity, phytoplankton Primary Production are closely related, and DON can cause water eutrophication, lead to algae, bacterium etc.
Microorganism mass propagation makes drinking water source break out algal tufa, keeps filter tank or film blocking and virulent property in water treatment unit nitrogenous
The risk that disinfection by-products (N-DBPs) occurs greatly increases.Accurate, synchronous detection to micro DON and DOC, to drinking water water
Source algal tufa outburst early warning, fouling membrane and the support work all to the mechanism study of the control of disinfection by-products etc. with key
With, also to improve drinking water quality research be of great significance.
In recent years, more and more with the research of weight distributing characteristic using size exclusion chromatography characterization DOC and DON.
Patent CN201810354795.4 discloses a kind of size exclusion chromatograph combination type Nitrogen detector and application method, although the detection
Device and method can be to the quantitative analyses of sample total nitrogen, organic nitrogen, nitrate nitrogen and ammonia nitrogen, but this method sacrifices DON with molecule
Distributed intelligence is measured, the DON concentration information amount of sample is substantially reduced.It is molten that patent CN201810480719.8 discloses a kind of detection
The instrument and method of solution property organic nitrogen, though this method can accurately detect different molecular weight DON concentration distribution situation, and avoid
The influence of the inorganic nitrogens ion pair testing result such as nitrate anion, but the detecting instrument is more complicated, need to fill is more aobvious
Color medicament reduces the stability of detection system, improves analysis cost.
For size exclusion chromatography and DOC and DON combination detection, mainstream detecting instrument is German DO C-Labor in the world
The LC-OCD-OND system (i.e. size exclusion chromatography-organic carbon detector-organic Nitrogen detector combined system) of development in laboratory,
The system is by detecting DOC the and DON distribution situation of the different molecular weight component of sample after size exclusion chromatography separates come anti-
The water quality characteristic for reflecting water sample has landmark meaning, but its deficiency is in water quality detection: (1) simultaneously using multithread road
Connection mode detects DOC and DON respectively reduces the synchronism and stability of multiple detector system；(2) matching used with instrument
Using Toyopearl HW-50S gel resin filler chromatographic column (and mainstream separation chromatography column at present, due to entire inspection
Examining system matches, and replacement chromatographic column is equal to the entire separation of redesign and detection system) separation limit low (0.1-
10KDa), macro-molecular protein and macromolecular polysaccharide cannot be separated, there is document " Three-dimensional excitation
and emission matrix fluorescence(3DEEM)for quick and pseudo-quantitative
determination of protein and humic-like substances in full-scale membrane
Bioreactor (MBR) " is pointed out, since chromatography post separation limit is too low, by the interference of macromolecular polysaccharide, uses the detection system
The protein-based fluorescence obtained and the protein-based fluorescence correlation for using three-dimensional fluorescence to characterize are bad, further illustrate that it cannot
Meet surface water water sample analysis demand seriously polluted at present；(3) detection system can only reflect that dissolubility is organic in water sample
Structure/concentration information of matter still lacks the characterization of physicochemical characteristics；(4) for the detection of DOC, which has used purple
The CO generated after outer resolution DOC using infrared carbon dioxide detector (NDIR) detection2, and nitrogen has been used to carry out CO2Stripping,
Plant area volume is too big, complicated for operation, very heavy, in addition, the detection limit of NDIR detector is higher；(5) system passes through
It detects DON and passes through the NO that Ultraviolet Oxidation generates3 -To characterize DON concentration, interference of the method vulnerable to inorganic Nitrogen ion, Bu Nengjing
True reflects DON with molecular weight distribution information；(6) due to being in monopoly position, every equipment price is extremely expensive.
Patent CN201811466516.X discloses a kind of organic nitrogen-organic carbon tandem online test method and device,
The device deficiency is: (1) thio product that the oxidant (potassium peroxydisulfate) of preposition addition generates after being activated is such as: sulfate radical from
Son, over cure acid ion etc. have absorption in low ultraviolet wavelength region, can generate larger shadow to the testing result of subsequent DON
It rings；(2) the inorganic Nitrogen ion of the higher nitrate anion of content can be due to going out in advance with the ion exclusion of pillar filler effect in surface water
Peak produces a very large impact the detection of organic nitrogen, it is therefore desirable to it is organic further to eliminate nitrate anion inorganic nitrogen ion pair small molecule
The influence of nitrogen material；(3) since mobile phase needs the flow velocity of 1.0mL/min to be delivered to CO2Selectivity penetrates film, to CO2Selection
Property, cause film damage the problems such as larger through film pressure, propose that carrying out pipeline transformation to organic nitrogen detection system makes organic nitrogen
Design flow path of the detector pipeline back pressure less than 5bar is affected, and may interfere with the synchronism and stability of multi-detector；
(4) with instrument it is matching used using Toyopearl HW-50S gel resin filler chromatographic column (and at present mainstream separate
Chromatographic column) separation limit low (0.1-10KDa), macro-molecular protein and macromolecular polysaccharide cannot be separated, cannot also be met at present
Seriously polluted surface water water sample analysis demand.
Patent CN201810480696.0 is the novel organic carbon detector patent that applicant applies early period, and instrument includes logical
Cross end injection valve, chromatographic column, pressure reducing valve, acid adding injection valve, the oxygenation injection valve, sour oxygen reaction spiral of pipeline sequential connection
Pipe, CO2Remover, UV digestion device, the second seperation film, buffer solution injection valve, buffer solution reaction helix tube, cadmium column, colour developing
Agent injection valve, color developing agent react helix tube, UV detector, and the end injection valve is for receiving mobile phase and sample, and described the
Two seperation films connect CO2Electric conductivity detector, the UV detector, CO2Electric conductivity detector connects with the computer for data processing
It connects.The present invention realizes sample to be tested in the synchronous detection of the TOC concentration, DON concentration of different molecular weight distributed area, is water factory
The field of water quality detection such as Inlet and outlet water water analysis, nitrogenous disinfection byproducts Detection & Controling provide reliable easily detection hand
Section.The apparatus is simple, easy to operate, and land occupation is small in size, and detection limit is low, and which is not described herein again.
DOM physicochemical characteristics can be indicated with " light absorption characteristics " and " light excitation feature "." light absorption characteristics " indicate tool
There is the organic matter of particular functional group or structure that there is certain absorption under specific wavelength exciting light, being typically chosen excitation wavelength is
254nm represents the organic matter with carbon-carbon double bond structure." light excitation feature " indicates different organic matters in different wave length exciting light
Under irradiation, the fluorescence for the different wave length that can launch, fluorescent characteristic has very strong representativeness, can distinguish different classes of object
Matter.There are three detection patterns for common fluorescence detector currently on the market: (1) fixed excitation and launch wavelength namely single wave
For length to detection pattern, which is not enough to characterize the physicochemical property of substance comprehensively；(2) fixed excitation or launch wavelength,
A certain range of transmitting and excitation wavelength detection pattern, i.e. half scan mode are scanned, the data under the detection pattern acquire frequency
Rate is generally 1~20HZ, and too high Data Detection frequency necessarily causes scanning speed too fast and too long (the generally 5- of scanning step
10nm), the exciting light scan data accuracy in a wavelength range of acquisition can be made not high in this way；(3) a certain range is scanned
Interior excitation and launch wavelength detection pattern, i.e. full scan mode, the detection pattern are applied to separate in size exclusion chromatography and be characterized
In can generate a large amount of hash, to later data processing bring difficulty.
Patent CN201410502662.9 and CN201510738667.6 are disclosed using LED light emitting diode as the glimmering of light source
Optical signal water monitoring device, this two patent deficiencies are that invented fluorescence signal detection device use is online in water quality
Context of detection, detection is Humus and protein-based fluorescence in practical mixed water body, internal duct thickness, flow cell
Design, the parameters such as matched detection frequency and scanning speed determine that it cannot be combined with liquid phase.
So there is problems at present for the characterization of DOM: (1) detection information is not comprehensive enough, is embodied in chromatography
The selection of spectrum column is not able to satisfy current water sample analysis requirement, and cannot be guaranteed multi-detector combined system stability with it is synchronous
Property, lead to the structure/physics and chemistry/grey density characteristics for being unable to concentrated expression DOM.(2) by measurement after in-line digestion nitrate anion in water
Concentration replaces DON concentration, and inorganic nitrogen ion interference is serious.(3) it is suitble to and fluorescence detector essence associated with size exclusion chromatography
Degree is not high, is embodied in detection pattern, parameter setting, hardware configuration etc. and is not adapted to entire detection system.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind to be based on size exclusion
The synchronous characterization water sample Dissolved Organic Matter structure of chromatographic single-flow-path ultraviolet light/fluorescence/organic carbon/organic nitrogen multi-detector/
Physics and chemistry/grey density characteristics instrument and method.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument, according to liquid flow path stream
To including the size exclusion chromatography system, UV detector, preposition temperature control system, preposition inorganic nitrogen being linked in sequence by pipeline
Detector, fluorescence detector, acid adding injection valve, mixer, CO2Stripping device, ultraviolet digestion device, seperation film, postposition temperature control system
And the organic Nitrogen detector of postposition, the size exclusion chromatography system connect CO for receiving sample, the seperation film2Conductivity detection
Device, the UV detector, preposition inorganic Nitrogen detector, fluorescence detector, the organic Nitrogen detector of postposition with analog-to-digital conversion mould
Block connection, the analog-to-digital conversion module are connect with computer, and the preposition temperature control system and postposition temperature control system and temperature control
Module connection.
In one embodiment of the present invention, the size exclusion chromatography system uses TSK PWXL2500 and TSK
PWXL5000 chromatography in series column systems.
TSK PWXL2500 and TSK PWXL5000 chromatography in series column systems, separation limit is < 8000KDa, much full
The separation demand of sufficient macromolecular polysaccharide and macro-molecular protein, column temperature are set as 40~80 DEG C.
Due to TSK PWXL2500 and TSK PWXL5000 chromatography in series column system diameters and length are smaller, and have higher
Theoretical cam curve, higher separating degree can be kept under low flow rate of mobile phase, therefore flow velocity is preferably 0.5~0.7mL/min
Also it is avoided that higher flow rate of mobile phase to the back of organic carbon detector carbon dioxide separation film while guaranteeing that post separation is spent
Pressure effect, protects carbon dioxide separation membrane stability.
In one embodiment of the present invention, the UV detector is by detection different molecular weight organic matter in 254nm
The absorbance at place, for indicating the aromaticity size of organic matter at the molecular weight.
In one embodiment of the present invention, the preposition inorganic Nitrogen detector passes through detection different molecular weight organic matter
The absorbance of nitrate ion in water sample is calculated as follows in ultraviolet absorptivity at 220nm and 275nm:
Wherein,A220nm, PAnd A275nm, PRespectively indicate nitrate ion in preposition inorganic Nitrogen detector 220nm and
Absorbance at 275nm, coefficient lambda is determined according to the property of actual water sample, is typically in the range of between 1~10.It will be used for postposition
The DON concentration calibration of organic Nitrogen detector.
In one embodiment of the present invention, the preposition temperature control system include the resistive heater with temperature sensor and
Be delayed spiral stainless steel tube, it is described delay spiral stainless steel tube both ends respectively with the outlet of UV detector and preposition inorganic nitrogen
The import of detector connects, and the resistive heater with temperature sensor is close to delay spiral stainless steel tube setting, the temperature
Degree sensor is connect with temperature control modules；
The postposition temperature control system include the resistive heater with temperature sensor and delay spiral stainless steel tube, it is described to prolong
When spiral stainless steel tube both ends connect respectively with the outlet of seperation film and the import of the organic Nitrogen detector of postposition, the band temperature
The resistive heater of sensor is connect close to delay spiral stainless steel tube setting, the temperature sensor with temperature control modules.
Preposition temperature control system is set before preposition inorganic Nitrogen detector, postposition is set before the organic Nitrogen detector of postposition
The purpose of temperature control system is to eliminate ultraviolet light temperature in ultraviolet digestion device and be distributed to inorganic nitrogen in the organic Nitrogen detector of postposition
Influence.
In one embodiment of the present invention, the fluorescence detector is three-dimensional fluorescence detector, including power supply system, Xe
Lamp, the first focusing is saturating, the second focusing is saturating, the first narrow band filter, the second narrow band filter, quartzy flow cell, diffraction grating, light
Electric multiplier tube and fluorescence signal acquisition and signal conditioning circuit,
Moved towards by optical path, the Xe lamp, first focus thoroughly, the first narrow band filter, quartzy flow cell, second focus thoroughly,
Second narrow band filter, diffraction grating, photomultiplier tube sequence are arranged,
It is flowed to by liquid flow path, described quartz flow cell one end is used to connect with preposition inorganic Nitrogen detector outlet, another
It holds for being connect with acid adding injection valve,
By communication line, the power supply system is connect with Xe lamp, diffraction grating and photomultiplier tube respectively, for Xe lamp, is spread out
It penetrates grating and photomultiplier tube provides power supply, the photomultiplier tube output end passes sequentially through fluorescence signal acquisition and signal condition
Circuit and analog-to-digital conversion module are communicated with computer.
The power supply system is powered by the way of filtering out electric source disturbance and isolation output, including sequentially connected main function
Rate circuit, APFC rectification circuit, isolation auxiliary power supply circuit and main Topology Driven circuit, the isolation auxiliary power supply circuit difference
It is connect with diffraction grating, fluorescence signal acquisition and signal conditioning circuit and analog-to-digital conversion module, the main power circuit and photoelectricity
Multiplier tube connection, and be the power supply of Xe lamp by main Topology Driven circuit.
The fluorescence signal acquisition and signal conditioning circuit include photomultiplier tube amplification output power supply circuit, linear voltage stabilization
Circuit, amplifying circuit of analog signal, it is photomultiplier transit that the main power circuit, which amplifies output power supply circuit by photomultiplier tube,
Pipe power supply, and constant current feedback controling mode is used, the isolation auxiliary power supply circuit is simulation letter by linear voltage-stabilizing circuit
The power supply of number amplifying circuit, the photomultiplier tube output end is successively after amplifying circuit of analog signal and analog-to-digital conversion module
It is connect with computer.
The amplifying circuit of analog signal handles photosignal using high-precision, high-gain, low noise operational amplifier.
The Xe lamp can produce stable exciting light.
Described first focuses saturating, the second focusing is used for focused light source and electromagnetic radiation light thoroughly；By to a variety of different types
Surface water is investigated, and preferably protein-based fluorescence and Humus Fluorescent Characterization region, selection obtain the centre in two regions out
Value scans model as protein-based and Humus fluorescence best characterization excitation wavelength, preferably 270 ± 10nm, launch wavelength
Enclose preferably 320-520nm.
First narrow band filter is used to screen the exciting light that wavelength is 270 ± 10nm；Second narrow band filter
For screening the transmitting light that wavelength is 320-520nm, which can cover all fluorescence areas and will not occur auspicious
Sharp scattering phenomenon.
The quartz flow cell volume is designed as 100~200uL, and biggish volume is to increase sample in pond and stop
The time is stayed, to reduce the error of fluorescent scanning, 500~1000psi of flow cell maximum back pressure.
The photomultiplier tube is used to detect the fluorescence signal after second narrow band filter optical filtering, fluorescence signal
It is received by fluorescence signal acquisition and signal conditioning circuit.
In the fluorescence signal acquisition and signal conditioning circuit of the fluorescence detector, transmitting light collection step-length is 1nm, time
Axis sample frequency f (HZ) and fluorescent scanning speedWith the volume V (μ L) of the quartzy flow cell and mobile phase
Flow velocity v (μ L/min) matches, and calculates for following formula:
The fluorescence signal acquisition and signal conditioning circuit are conventional structure setting, including photomultiplier tube amplification output supplies
Circuit, artificial circuit part linear voltage-stabilizing circuit, amplifying circuit of analog signal.
The acid adding injection valve is connect with acid solution syringe pump and acid solution bottle.
For filling acid solution, acid solution should select the acid solution bottle according to the difference of sample, but will guarantee IC all acid
Turn to CO2, it is general can be selected as 15%~30% phosphoric acid.Acid solution is injected into flow path by acid adding injection valve, is maintained molten
The pH of liquid is 2 or so；
The acid solution syringe pump and oxygen liquid syringe pump should be able to be injected into acid solution and oxygen into primary flow path according to certain flow velocity
Liquid, and will not flow velocity to primary flow path and pressure have an impact.Preferably: micro-injection pump, pump work pressure should be higher than that
1500psi, less than 0.1%, the conveying of no pulse formula can be distributed accurately from very small to very big injection volume full accuracy,
Acid adding oxygenation pipeline is connected with sample pipe using injection valve.Sour oxygen injection flow rate pump should ensure that sour oxygen solution is excessive, can basis
The concentration selection of sample and sour oxygen solution, it is general to can choose as 1.0~4.0 μ L/min.
The mixer is arranged between ultraviolet digestion device and acid adding injection valve, to guarantee that IC is sufficiently acidified as CO2, preferably
: it is formed using stainless steel tube spiral.One side cost reduces；Another aspect stainless steel tube effectively can prevent medicament from corroding
And guarantee that the component to be measured separated will not mix again wherein.
The CO2Stripping device includes gas-liquid separation membrane, collection gas coil pipe, stripping pump and diaphragm, the gas-liquid separation membrane, gas collection
Coil pipe and diaphragm sequence are connected, and the gas-liquid separation membrane is connect by pipeline with mixer, and the diaphragm passes through outlet ventilation
Pipe and pipeline are connect with ultraviolet digestion device, and the stripping pump is connect with collection gas coil pipe, and the effect of the gas-liquid separation membrane is by IC
It is acidified the CO generated2It is separated with liquid component, and then enters in collection gas coil pipe and collect, the gas-liquid separation membrane is preferably
PDMS membrane belongs to oxygen permeable membrane, to CO2There are good separating effect, and stable structure.The work of the diaphragm
With by the CO in air2It is isolated in outside, prevents from entering in component to be measured.The effect of the stripping pump is to provide stripping power,
The CO collected in gas coil pipe will be collected2Stripping is gone out, and the stripping pump is preferably minitype pneumatic diaphragm pump, and compact can have
The offer stripping power of effect, it is cheap.
The ultraviolet digestion device includes heater strip, suprasil helix tube and UV lamp, and the suprasil helix tube passes through
For piping connection between the diaphragm and seperation film, the UV lamp is located at the top of suprasil helix tube, the heater strip position
In the lower section of suprasil helix tube.
The seperation film connects CO2Electric conductivity detector, the CO for will be generated in ultraviolet digestion device2It separates to CO2Conductance inspection
It surveys in device, remaining sample enters in the organic Nitrogen detector of postposition, and the seperation film is preferably PDMS membrane, belongs to
Oxygen permeable membrane, to CO2There are good separating effect, and stable structure.
The CO2Electric conductivity detector includes ultrapure water tank, ultrapure water pump and the conductance cell being linked in sequence, ultraviolet digestion device oxygen
Sample after change is after seperation film by the CO of generation2It is dissolved in the ultrapure water driven by ultrapure water pump, is passed through conductance cell
In, CO is detected by detecting the variation of conductance cell liquid electric conductivity2Amount, and it is dense by certain conversion relation to characterize TOC
Degree.
Preferably, ultrapure water selects the production of Milli-Q ultrapure water instrument, resistivity is 18.2M Ω, and ultrapure water pump is selected micro-
Type infusion pump, it is 0.01 μ s/cm -300 μ s/cm that conductance cell, which selects measurement range, and resolution ratio is the conductivity electrode of 0.01 μ s/cm
Flow cell.
The nitrate anion that the organic Nitrogen detector of postposition is converted after ultraviolet digestion by detection organic nitrogen is at 220nm
Absorbance A220nm, R.By the detection to a large amount of earth's surface water samples, the organic nitrogen material of nitrate anion inorganic nitrogen ion pair small molecule
Detection interference is larger, therefore obtained with preposition inorganic Nitrogen detectorTo calibrate A220nm, R, what is obtained is exactly organic nitrogen warp
Cross the nitrate anion absorbance that ultraviolet digestion device obtainsCalibration equation is as follows:
Influence thus eliminating the need nitrate ion to the organic Nitrogen ion of small molecule.It is examined using potassium nitrate calibration organic nitrogen
Device is surveyed, calibration curve is obtained, can be incited somebody to action according to calibration curveNO after being scaled practical DON oxidation3 -Concentration is big
It is small, finally it is scaled DON concentration.
Waste liquid cylinder is connected after the organic Nitrogen detector of postposition, the waste liquid cylinder is used to receive the waste liquid after detection.
The organic Nitrogen detector of postposition uses Potassium Hydrogen Phthalate as organic Nitrogen detector DOC calibration standard
Matter.
It is equipped with to after to reduce the thio object generated after potassium persulfate oxidation agent oxidation such as sulfate radical, over cure acid ion
Machine Nitrogen detector influences, by testing and verification, using the Potassium Hydrogen Phthalate of 5ppm in the case where being added without oxygen liquid and oxygen liquid being added
Peak area is analyzed, obtains being added without oxygen liquid and oxygen liquid being added influencing very little in Potassium Hydrogen Phthalate DOC < 5ppm, it can
To ignore, therefore in order to reduce the interference to the organic Nitrogen detector of postposition, oxygen liquid is added without in entire detection architecture, this
It is the one aspect that the application is different from technology, but in order to guarantee the fully oxidized organic matter of ultraviolet digestion device, sample DOC < 5ppm
When accuracy it is higher.
The temperature control modules can use conventional structure.For guaranteeing preposition temperature control system and postposition temperature control system temperature
It spends identical.
The analog-to-digital conversion module is connect for converting digital signal for the analog signal of each detector by computer 21
It receives, may be implemented using conventional structure.
Using the synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics method of instrument of the present invention:
Sampfe order enters size exclusion chromatography system, UV detector, preposition temperature control system, the detection of preposition inorganic nitrogen
Device, fluorescence detector, acid adding injection valve, mixer, CO2Stripping device, ultraviolet digestion device, seperation film, postposition temperature control system and after
It is equipped with machine Nitrogen detector, absorbance of the UV detector by detection different molecular weight organic matter at 254nm is used to table
Show the aromaticity size of organic matter at the molecular weight；The preposition inorganic Nitrogen detector is for content of inorganic nitrogen in test sample；
The fluorescence detector maintains the steady of entire multi-detector detection system for detecting sample to be tested different molecular weight fluorescence information
Qualitative and synchronism；The acid adding injection valve is used to inject acid solution to the sample flowed to herein, and the mixer is used for nothing
Machine carbonic acid turns to CO2, the CO2Stripping device is used for CO2Stripping；The ultraviolet digestion device is used for Specimen eliminating, the separation
Film will be for that will state the CO generated in ultraviolet digestion device2It separates to CO2It is detected in electric conductivity detector, and then obtains DOC content,
The organic Nitrogen detector of postposition is for organic nitrogen content in test sample；The preposition temperature control system and postposition temperature control system are used
In control system temperature.
In the above method, it is preferable that the size exclusion chromatography system column temperature is set as 40~80 DEG C, and flow velocity is 0.5~
0.7mL/min。
In the above method, it is preferable that the preposition inorganic Nitrogen detector by detection different molecular weight organic matter 220nm and
The absorbance of nitrate ion in water sample is calculated as follows in ultraviolet absorptivity at 275nm:
Wherein,A220nm, PAnd A275nm, PRespectively indicate nitrate ion in preposition inorganic Nitrogen detector 220nm and
Absorbance at 275nm, coefficient lambda is between 1~10；
The nitrate anion that the organic Nitrogen detector of postposition is converted after ultraviolet digestion by detection organic nitrogen is at 220nm
Absorbance A220nm, R, obtained with preposition inorganic Nitrogen detectorTo calibrate A220nm, R, what is obtained is exactly that organic nitrogen passes through
The nitrate anion absorbance that ultraviolet digestion device obtainsCalibration equation is as follows:
Again willNO after being scaled practical DON oxidation3 -Concentration is finally scaled DON concentration；
In the fluorescence signal acquisition and signal conditioning circuit of the fluorescence detector, transmitting light collection step-length is 1nm, time
Axis sample frequency f (HZ) and fluorescent scanning speedWith the volume V (μ L) of the quartzy flow cell and mobile phase
Flow velocity v (μ L/min) matches, and calculates for following formula:
The present invention abandons the gel resin filler chromatographic column of the Toyopearl HW-50S largely used at present, by a large amount of
Experiment, preferably out TSK PWXL2500 and TSK PWXL5000 chromatography in series column systems optimize chromatographic condition, improve point of sample
From limit.By inorganic Nitrogen detector (4) and the organic Nitrogen detector of postposition (12), the higher NO of content in surface water is eliminated3 -It is inorganic
Influence of the Nitrogen ion for DON testing result.The dedicated three-dimensional fluorescence detector of size exclusion chromatography is designed, flow cell is big
The empirical equation of small, data acquiring frequency, fluorescent scanning speed and flow rate of mobile phase setting can guarantee three-dimensional fluorescence of the present invention
Detector accurately detects water sample different molecular weight fluorescence information to be measured, maintains the stability of entire multi-detector detection system and same
Step property.
In the application, all appts carry out single-flow-path connection, it is therefore intended that: (1) guarantee multi-detector detection system whole
Synchronism and stability；(2) preposition inorganic Nitrogen detector and postposition organic nitrogen detector signal are compared to each other, and remove water to be measured
The accurate detection of different molecular weight distribution is realized in influence of the nitrate ion to water sample distribution in sample.
The representative excitation of the dedicated three-dimensional fluorescence detector of size exclusion chromatography provided by the invention and launch wavelength, it is internal
Flow cell size, data acquiring frequency, fluorescent scanning speed and flow rate of mobile phase setting can guarantee that it detects different molecular
Measure fluorescence information.
The present invention can UV absorption/fluorescent characteristic/organic concentration of carbon to different molecular weight organic matter in water sample/organic
The synchronous detection of nitrogen concentration, realizes structure/physics and chemistry/grey density characteristics comprehensive characterization of water sample to be measured.
Quantitative/qualitative information is enriched provided by the instrument and method that the present invention establishes can be used for water treatment field drinking water
The researchs such as accurate identification, fouling membrane mechanism and the optimization of drinking water plant water treatment technology of disinfection by-products formation potential.
Compared with prior art, innovative point major embodiment of the invention is in the following areas:
(1) it is developed based on single-flow-path ultraviolet light/fluorescence/organic carbon/organic nitrogen multi-detector of size exclusion chromatography
The synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/concentration feature of system；
(2) the gel resin filler chromatographic column using Toyopearl HW-50S largely used at present is abandoned, by big
Amount experiment, preferably out TSK PWXL 2500 and TSK PWXL5000 chromatography in series column system, optimize chromatographic condition, improve sample
Separation limit；
(3) it is detected by preposition inorganic nitrogen and the organic Nitrogen detector of postposition, preposition inorganic Nitrogen detector and postposition organic nitrogen
Device signal is compared to each other, and eliminates the higher NO of content in surface water3 -Inorganic nitrogen ion is dense for different molecular weight component organic nitrogen
The influence of testing result is spent, realizes the accurate detection of different molecular weight distribution；
(4) the dedicated three-dimensional fluorescence detector of size exclusion chromatography is designed, it is flow cell size, data acquiring frequency, glimmering
Optical scanning speed, excitation wavelength, scanning wavelength and the empirical equation of flow rate of mobile phase setting can guarantee three-dimensional fluorescence of the present invention
Detector accurately detects water sample different molecular weight fluorescence information to be measured, maintains the stability of entire multi-detector detection system and same
Step property.
Detailed description of the invention
Fig. 1 is synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics apparatus structure schematic diagram.
Fig. 2 is that size exclusion chromatography system uses polyethylene glycol and polystyrene sodium sulfonate as molecular weight standard substance,
Obtained molecular mass standard curve figure.
Fig. 3 is preposition temperature control system structure and connection schematic diagram.
Fig. 4 is postposition temperature control system structure and connection schematic diagram.
Fig. 5 is three-dimensional fluorescence detector structural schematic diagram.
Fig. 6 is alternating current 220V exchange access and rectification circuit figure.
Fig. 7 is that auxiliary power supply circuit diagram is isolated in low-voltage equipment.
Fig. 8 is main Topology Driven circuit diagram.
Fig. 9 is the main power circuit of Xe lamp work.
Figure 10 is protein-based fluorescence and Humus Fluorescent Characterization administrative division map.
Figure 11 is photomultiplier tube amplification output power supply circuit.
Figure 12 is the linear voltage-stabilizing circuit figure of artificial circuit part.
Figure 13 is amplifying circuit of analog signal figure.
Figure 14 is CO2Stripping device structural schematic diagram.
Figure 15 is ultraviolet digestion device structural schematic diagram.
Figure 16 is to calibrate the calibration curve that organic Nitrogen detector obtains using potassium nitrate.
Figure 17 is the testing result deducted before and after nitrate anion.
Figure 18 is to use Potassium Hydrogen Phthalate as organic Nitrogen detector DOC calibration standard matter, obtains calibration curve
Figure.
Figure 19 is to analyze peak area in the case where being added without oxygen liquid and oxygen liquid being added using the Potassium Hydrogen Phthalate of 5ppm to show
It is intended to.
Figure 20 is to examine detection system of the present invention using bovine serum albumin(BSA), sodium alginate and Suez river natural organic matter
Characterization effectiveness results.
Figure 21 is to take by the filtered Wujiang East Taihu Lake raw water of 0.45 μm of film, is tied after being detected using instrument of the present invention
Fruit.
Figure 22 is to obtain reproducibility result by detecting same water sample 7 times in embodiment 2.
Figure label: 1- size exclusion chromatography system；2- UV detector；The preposition temperature control system of 3-；The preposition inorganic nitrogen of 4-
Detector；5- fluorescence detector；6- acid adding injection valve；7- mixer；8-CO2Stripping device；9- ultraviolet digestion device；10- seperation film；
11- postposition temperature control system；The organic Nitrogen detector of 12- postposition；13- waste liquid cylinder；14- acid solution bottle；15- acid solution syringe pump；16- is ultrapure
Water tank；The ultrapure water pump of 17-；18- conductance cell；19- analog-to-digital conversion module；20- temperature control modules；21- computer.
Specific embodiment
A kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument, with reference to Fig. 1, according to liquid
Flow path flow direction, including the size exclusion chromatography system 1, UV detector 2, preposition temperature control system 3, preceding being linked in sequence by pipeline
Set inorganic Nitrogen detector 4, fluorescence detector 5, acid adding injection valve 6, mixer 7, CO2Stripping device 8, ultraviolet digestion device 9, seperation film
10, postposition temperature control system 11 and the organic Nitrogen detector 12 of postposition, the size exclusion chromatography system 1 are described for receiving sample
Seperation film 10 connects CO2Electric conductivity detector, the acid adding injection valve 6 are connect with acid solution syringe pump 14 and acid solution bottle 15.The purple
External detector 2, preposition inorganic Nitrogen detector 4, fluorescence detector 5, the organic Nitrogen detector 12 of postposition with analog-to-digital conversion module 19
Connection, the analog-to-digital conversion module 19 are connect with computer 21, the preposition temperature control system 3 and postposition temperature control system 11 and temperature
Control module 20 connects.Waste liquid cylinder 13 is connected after the organic Nitrogen detector 12 of postposition, the waste liquid cylinder 13 is for receiving detection
Waste liquid afterwards.
Wherein, the size exclusion chromatography system 1 uses TSK PWXL2500 and TSK PWXL5000 chromatography in series column systems
System.
TSK PWXL2500 and TSK PWXLThe chromatography in series column system of 5000I.D.7.8mm × 30mm × 2 separates limit
For < 8000KDa, much meet the separation demand of macromolecular polysaccharide and macro-molecular protein, column temperature is set as 40~80 DEG C.
Due to TSK PWXL2500 and TSK PWXL5000 chromatography in series column system diameters and length are smaller, and have higher
Theoretical cam curve, higher separating degree can be kept under low flow rate of mobile phase, therefore flow velocity is preferably 0.5~0.7mL/min
Also it is avoided that higher flow rate of mobile phase to the back of organic carbon detector carbon dioxide separation film while guaranteeing that post separation is spent
Pressure acts on back pressure < 150psi, protects carbon dioxide separation membrane stability.
The size exclusion chromatography system 1 uses polyethylene glycol and polystyrene sodium sulfonate as molecular weight standard substance,
Obtained molecular mass standard curve is as shown in Figure 2.
Absorbance of the UV detector 2 by detection different molecular weight organic matter at 254nm, for indicating this point
The aromaticity size of organic matter at sub- amount.
The preposition inorganic Nitrogen detector 4 passes through the ultraviolet light absorption at detection different molecular weight organic matter 220nm and 275nm
Degree, is calculated as follows the absorbance of nitrate ion in water sample:
Wherein,A220nm, PAnd A275nm, PRespectively indicate nitrate ion, preposition inorganic Nitrogen detector 220nm and
Absorbance at 275nm.Coefficient lambda is determined according to the property of actual water sample, is typically in the range of between 1~10.It will be used for postposition
The DON concentration calibration of organic Nitrogen detector.
With reference to Fig. 3, the preposition temperature control system 3 includes the resistive heater 3-1 with temperature sensor and is delayed spiral not
Become rusty steel pipe 3-2, and the both ends of the delay spiral stainless steel tube 3-2 are examined with the outlet of UV detector 2 and preposition inorganic nitrogen respectively
The import connection of device 4 is surveyed, the resistive heater 3-1 with temperature sensor is close to delay spiral stainless steel tube 3-2 setting, institute
Temperature sensor is stated to connect with temperature control modules 20；
With reference to Fig. 4, the postposition temperature control system 11 includes the resistive heater 11-1 with temperature sensor and delay spiral
Stainless steel tube 11-2, the both ends of the delay spiral stainless steel tube 11-2 are examined with the outlet of seperation film 10 and postposition organic nitrogen respectively
The import connection of device 12 is surveyed, the resistive heater 11-1 with temperature sensor is set close to delay spiral stainless steel tube 11-2
It sets, the temperature sensor is connect with temperature control modules 20.
Preposition temperature control system 3 is set before preposition inorganic Nitrogen detector 4, is arranged before the organic Nitrogen detector 12 of postposition
The purpose of postposition temperature control system 11 is to eliminate in ultraviolet digestion device 9 ultraviolet light temperature to nothing in the organic Nitrogen detector of postposition 12
The influence of machine nitrogen distribution.
With reference to Fig. 5,
The fluorescence detector 5 is three-dimensional fluorescence detector, including power supply system 5-1, Xe lamp 5-2, the first saturating 5- of focusing
3, second saturating 5-6, the first narrow band filter 5-4, the second narrow band filter 5-7, quartzy flow cell 5-5, diffraction grating 5- are focused
8, photomultiplier tube 5-9 and fluorescence signal acquisition and signal conditioning circuit 5-10,
Moved towards by optical path, the Xe lamp 5-2, first focus saturating 5-3, the first narrow band filter 5-4, quartzy flow cell 5-5,
Second, which focuses saturating 5-6, the second narrow band filter 5-7, diffraction grating 5-8, photomultiplier tube 5-9 sequence, is arranged,
It being flowed to by liquid flow path, described quartz one end flow cell 5-5 is used to connect with the preposition inorganic outlet of Nitrogen detector 4,
The other end is used to connect with acid adding injection valve 6,
By communication line, the power supply system 5-1 connects with Xe lamp 5-2, diffraction grating 5-8 and photomultiplier tube 5-9 respectively
It connects, provides power supply for Xe lamp 5-2, diffraction grating 5-8 and photomultiplier tube 5-9, the photomultiplier tube 5-9 output end successively leads to
It crosses fluorescence signal acquisition and signal conditioning circuit 5-10 and analog-to-digital conversion module 19 is communicated with computer 21.
The power supply system 5-1 is powered by the way of filtering out electric source disturbance and isolation output, including sequentially connected
Main power circuit, APFC rectification circuit, isolation auxiliary power supply circuit and main Topology Driven circuit, the isolation auxiliary power supply circuit
It is connect respectively with diffraction grating 5-8, fluorescence signal acquisition and signal conditioning circuit 5-10 and analog-to-digital conversion module 19, the main function
Rate circuit is connect with photomultiplier tube 5-9, and is Xe lamp 5-1 power supply by main Topology Driven circuit.
Wherein, the power supply system 5-1 can use power supply mode below.
It is alternating current 220V exchange access and rectification circuit with reference to Fig. 6, Fig. 6, power network fluctuation is eliminated using common mode, differential mode filtering
Influence to rear class, while APFC rectification circuit lifting means inlet wire output power factor is used, the active efficiency of optimization power supply, together
When also meet IEC standard, finally export stable DC voltage.
It is that auxiliary power supply circuit is isolated in low-voltage equipment with reference to Fig. 7, Fig. 7, the voltage of 6 commercial power rectification circuit output of map interlinking is adopted
With three winding and opto-coupled feedback, export three road boost voltages: wherein+8V, -8V supply rear class linear voltage-stabilizing circuit, i.e. Figure 12
It uses；The servo motor that+12V supplies rear class light path part diffraction grating 5-8 motion parts uses.
With reference to Fig. 8, Fig. 8 is main Topology Driven circuit, provides the driving of strong switch pipe to the main power circuit for Fig. 9,
Because xenon lamp 40~80Vac of 5-2 need of work power, on startup the outlet of Fig. 9 be connected to ballast provide moment 20kV~
40kV high pressure moment ionized gas point bright light source maintains stable exchange to export supply xenon lamp work later.
The Xe lamp 5-2 can produce stable exciting light.Fig. 9 is the main power circuit of Xe lamp work, uses resonance
Converter with optimization efficiency, and can largely reduce power supply system volume and weight.In conjunction with the main Topology Driven of Fig. 8
Circuit is capable of providing the excellent power output of dynamic, stability, guarantees that instantaneous pressure output can seamlessly transit when starting,
Output accuracy, stability are high when steady operation, and ripple fluctuates smaller guarantee xenon lamp intensity of illumination and stability not by power supply
The influence of power supply, this is also that rear class sampled signal completely guarantees.
Described first focuses saturating 5-3, the second saturating 5-6 of focusing is used for focused light source and electromagnetic radiation light；By to it is a variety of not
Same type surface water is investigated, and preferably protein-based fluorescence and Humus Fluorescent Characterization region, selection obtain two regions out
Median as protein-based and Humus fluorescence best characterization excitation wavelength, preferably 270 ± 10nm, launch wavelength
Scanning range is preferably 320-520nm, with reference to Figure 10.
The first narrow band filter 5-4 is used to screen the exciting light that wavelength is 270 ± 10nm；Second narrow-band-filter
Piece 5-7 is used to screen the transmitting light that wavelength is 320-520nm, which can cover all fluorescence areas and will not send out
Raw Rayleigh scattering phenomenon.
The quartz flow cell 5-5 volume is designed as 100~200uL, and biggish volume is to increase sample in pond
Residence time, to reduce the error of fluorescent scanning, 500~1000psi of flow cell maximum back pressure.
The photomultiplier tube 5-9 is used to detect the fluorescence signal after the second narrow band filter 5-7 optical filtering, glimmering
Optical signals fluorescence signal acquisition and signal conditioning circuit 5-10 are received.
The fluorescence signal acquisition and signal conditioning circuit 5-10 include photomultiplier tube amplification output power supply circuit, linear
Voltage regulator circuit, amplifying circuit of analog signal, it is photoelectricity that the main power circuit, which amplifies output power supply circuit by photomultiplier tube,
Multiplier tube 5-9 power supply, and constant current feedback controling mode is used, the isolation auxiliary power supply circuit is by linear voltage-stabilizing circuit
Amplifying circuit of analog signal power supply, the photomultiplier tube 5-9 output end successively pass through amplifying circuit of analog signal and modulus
It is connect after conversion module 19 with computer 21.
In the fluorescence signal acquisition and signal conditioning circuit 5-10 of the fluorescence detector 5, transmitting light collection step-length is
1nm, time shaft sample frequency f (HZ) and fluorescent scanning speedWith the volume V (μ L) of the quartzy flow cell 5-5
And the flow velocity v (μ L/min) of mobile phase matches, and calculates for following formula:
The fluorescence signal acquisition and signal conditioning circuit 5-10 include photomultiplier tube amplification output power supply circuit, simulation
Circuit part linear voltage-stabilizing circuit, amplifying circuit of analog signal.
Figure 11 is photomultiplier tube amplification output power supply circuit, wherein P1 is photomultiplier tube power supply interface, and use is high-precision
Degree feedback current constant control, maximum can provide the photoelectric current amplification ability close to 200,000 times.Since using constant current-supplying, Ke Yiyou
Effect avoids dark current from being switched to photoelectric current glitch, and multiplier tube works into non-after strong illumination and long-time receive illumination
The problem of linear operating region, can guarantee that the linearity of sampling guarantees the validity of subsequent processing data.
Figure 12 is the linear voltage-stabilizing circuit of artificial circuit part, because the low-voltage equipment isolation auxiliary that prime accesses Fig. 7 supplies
Circuit has accessed 78 and 79 serial low pressure difference linear voltage regulators for the power supply environment stable to sampled operational amplifier
The voltage feedback circuit of LDO and high-precision TL431 composition, guarantees the stability of analog circuit power supply.
Figure 13 is amplifying circuit of analog signal, wherein U8 is photomultiplier tube output signal interface, passes through initial discharge tune
Amplifier Q2 biasing and balance are saved, guarantees the influence for eliminating photomultiplier tube 5-9 dark current overlapping portion, output photoelectric stream passes through
After the same phase of operational amplifier, inverting input terminal, the low-pass filter of cutoff frequency very little is added in amplification output end, is obtained smooth
Linear analogue voltage output, supply the microcontroller ADC Sampling Interface of rear class, and by amplitude limiter circuit D4 to protect output
It is unlikely to damage microcontroller.Operational amplifier U9 is high-gain, low noise, high-precision junction type pipe amplifier, is had excellent performance,
It is able to satisfy the demand of current signal fast dynamic response and high-amplification-factor completely.
For filling acid solution, acid solution should select the acid solution bottle according to the difference of sample, but will guarantee IC all acid
Turn to CO2, it is general can be selected as 15%~30% phosphoric acid.Acid solution is injected into flow path by acid adding injection valve 6, is maintained molten
The pH of liquid is 2 or so.
The acid solution syringe pump and oxygen liquid syringe pump should be able to be injected into acid solution and oxygen into primary flow path according to certain flow velocity
Liquid, and will not flow velocity to primary flow path and pressure have an impact.Preferably: micro-injection pump, pump work pressure should be higher than that
1500psi, less than 0.1%, the conveying of no pulse formula can be distributed accurately from very small to very big injection volume full accuracy,
Acid adding oxygenation pipeline is connected with sample pipe using injection valve.Sour oxygen injection flow rate pump should ensure that sour oxygen solution is excessive, can basis
The concentration selection of sample and sour oxygen solution, it is general to can choose as 1.0~4.0 μ L/min.
The mixer 7 is arranged between ultraviolet digestion device 9 and acid adding injection valve 6, to guarantee that IC is sufficiently acidified as CO2,
Preferably: being formed using stainless steel tube spiral.One side cost reduces；Another aspect stainless steel tube can effectively prevent medicament
The component to be measured that corrosion and guarantee are separated will not mix again wherein.
The CO28 structure of stripping device is as shown in figure 14, including gas-liquid separation membrane 8-1, collection gas coil pipe 8-2, stripping pump 8-3
And diaphragm 8-4, the gas-liquid separation membrane, collection gas coil pipe and diaphragm sequence are connected, and the gas-liquid separation membrane passes through pipeline and mixed
Clutch 7 connects, and the diaphragm is connect by outlet snorkel 8-5 and pipeline with ultraviolet digestion device 9, the stripping pump and gas collection disk
Pipe connection, the effect of the gas-liquid separation membrane are the CO for generating IC acidification2It is separated with liquid component, and then enters collection gas coil pipe
In collect, the gas-liquid separation membrane is preferably PDMS membrane, belongs to oxygen permeable membrane, to CO2Have well
Separating effect, and stable structure.The effect of the diaphragm is by the CO in air2It is isolated in outside, prevents from entering component to be measured
In.The effect of the stripping pump is to provide stripping power, will collect the CO collected in gas coil pipe2Stripping is gone out, and the stripping pump is excellent
Choosing is minitype pneumatic diaphragm pump, and compact can effectively provide stripping power, cheap.
With reference to Figure 15, the ultraviolet digestion device 9 includes heater strip 9-1, suprasil helix tube 9-2 and UV lamp 9-3, described
Through piping connection between the diaphragm 8-4 and seperation film 10, the UV lamp 9-3 is located at transparent suprasil helix tube 9-2
The top of quartzy helix tube 9-2, the heater strip 9-1 are located at the lower section of suprasil helix tube 9-2.
Referring again to Fig. 1, the seperation film 10 connects CO2Electric conductivity detector, the CO for will be generated in ultraviolet digestion device 92Point
From to CO2In electric conductivity detector, remaining sample enters in the organic Nitrogen detector 12 of postposition, and the seperation film 10 is preferably poly- two
Methylsiloxane film, belongs to oxygen permeable membrane, to CO2There are good separating effect, and stable structure.The CO2Electric conductivity detector packet
The ultrapure water tank 16, ultrapure water pump 17 and conductance cell 18 of sequential connection are included, the sample after ultraviolet digestion device 9 aoxidizes passes through seperation film
By the CO of generation after 102It is dissolved in the ultrapure water driven by ultrapure water pump 17, is passed through in conductance cell 18, by detecting conductance
The variation of pond liquid electric conductivity detects CO2Amount, and pass through certain conversion relation and characterize TOC concentration.Preferably, ultrapure
Wet concentration makes of Milli-Q ultrapure water instrument, and resistivity is 18.2M Ω, and ultrapure water pump selects micro-infusion pump, and conductance cell, which is selected, to be surveyed
Amount range is 0.01 μ s/cm -300 μ s/cm, and resolution ratio is the conductivity electrode flow cell of 0.01 μ s/cm.
The nitrate anion that the organic Nitrogen detector 12 of postposition is converted after ultraviolet digestion by detection organic nitrogen is in 220nm
The absorbance A at place220nm, R.Pass through the detection to a large amount of earth's surface water samples, the organic nitrogen material of nitrate anion inorganic nitrogen ion pair small molecule
Detection interference it is larger, therefore obtained with preposition inorganic Nitrogen detectorTo calibrate A220nm, R, what is obtained is exactly organic nitrogen
The nitrate anion absorbance obtained by ultraviolet digestion deviceCalibration equation is as follows:
Influence thus eliminating the need nitrate ion to the organic Nitrogen ion of small molecule.
Organic Nitrogen detector is calibrated using potassium nitrate, obtains calibration curve as shown in Figure 16,17, it can be with according to calibration curve
It willNO3- concentration after being scaled practical DON oxidation, is finally scaled DON concentration.
The organic Nitrogen detector 12 of postposition uses Potassium Hydrogen Phthalate as organic Nitrogen detector DOC calibration standard
Matter.It is as shown in figure 18 to obtain calibration curve, can be incited somebody to action according to calibration curveNO after being scaled practical DON oxidation3 -
Concentration is finally scaled DON concentration.Influence thus eliminating the need nitrate ion to the organic Nitrogen ion of small molecule.
It is equipped with to after to reduce the thio object generated after potassium persulfate oxidation agent oxidation such as sulfate radical, over cure acid ion
Machine Nitrogen detector 12 influences, and by testing and verification, the Potassium Hydrogen Phthalate using 5ppm is being added without oxygen liquid and oxygen liquid is added
Under analyze peak area, as shown in figure 19, obtain being added without oxygen liquid and oxygen liquid be added in Potassium Hydrogen Phthalate DOC < 5ppm
Waiting influences very little, can be ignored, therefore in order to reduce the interference to the organic Nitrogen detector of postposition, in entire detection architecture
It is added without oxygen liquid, this is the one aspect that the application is different from the prior art, but is had to guarantee that ultraviolet digestion device 5 is fully oxidized
Machine object, accuracy is higher when sample DOC < 5ppm.
The temperature control modules 20 can use conventional structure.For guaranteeing preposition temperature control system 3 and postposition temperature control system
11 temperature of uniting are identical.
The analog-to-digital conversion module 19 is used to convert digital signal by computer 21 for the analog signal of each detector
It receives, may be implemented using conventional structure.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Using the single-flow-path ultraviolet light based on size exclusion chromatography as shown in Figure 1 disclosed in embodiment of the present invention/
Fluorescence/organic carbon/organic nitrogen multi-detector.Using bovine serum albumin(BSA) (BSA), sodium alginate (SA) and Suez river naturally have
Machine matter (SRNOM) examines the characterization effect of detection system of the present invention, and every kind of substance DOC is 2.0ppm, as a result as shown in figure 20.
The result shows that: instrument provided by the invention and method can be to polysaccharose substance (sodium alginates), and (ox blood is pure for protein substance
Albumen) and humus material (Suez river natural organic matter) have well separation and characterization effect.
Embodiment 2
Using the single-flow-path ultraviolet light based on size exclusion chromatography as shown in Figure 1 disclosed in embodiment of the present invention/
Fluorescence/organic carbon/organic nitrogen multi-detector.It takes by the filtered Wujiang East Taihu Lake raw water of 0.45 μm of film, uses the present invention
Instrument detection, is as a result illustrated in fig. 21 shown below.The result shows that instrument provided by the invention and method can have actual water sample well
Characterize effect.By detecting same water sample 7 times, obtains reproducibility and be illustrated in fig. 22 shown below, it is seen that the reproducibility of instrument of the present invention
Well.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument, which is characterized in that according to liquid
Body flow path flow direction, including the size exclusion chromatography system (1), UV detector (2), preposition temperature control system being linked in sequence by pipeline
System (3), preposition inorganic Nitrogen detector (4), fluorescence detector (5), acid adding injection valve (6), mixer (7), CO2Stripping device (8),
Ultraviolet digestion device (9), seperation film (10), postposition temperature control system (11) and the organic Nitrogen detector of postposition (12),
The size exclusion chromatography system (1) connects CO for receiving sample, the seperation film (10)2Electric conductivity detector,
The UV detector (2), preposition inorganic Nitrogen detector (4), fluorescence detector (5), the organic Nitrogen detector of postposition (12)
It is connect with analog-to-digital conversion module (19), the analog-to-digital conversion module (19) connect with computer (21), the preposition temperature control system
System (3) is connect with postposition temperature control system (11) with temperature control modules (20).
2. a kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument according to claim 1
Device, which is characterized in that the size exclusion chromatography system (1) uses TSK PWXL2500 and TSK PWXL5000 chromatography in series columns
System.
3. a kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument according to claim 1
Device, which is characterized in that the preposition temperature control system (3) includes the resistive heater (3-1) with temperature sensor and delay spiral
Stainless steel tube (3-2), the both ends of delay spiral stainless steel tube (3-2) respectively with the outlet of UV detector (2) and preposition
The import of inorganic Nitrogen detector (4) connects, and the resistive heater (3-1) with temperature sensor is close to delay spiral stainless steel
(3-2) setting is managed, the temperature sensor is connect with temperature control modules (20)；
The postposition temperature control system (11) includes the resistive heater (11-1) with temperature sensor and delay spiral stainless steel tube
It is detected respectively with the outlet of seperation film (10) and postposition organic nitrogen at the both ends of (11-2), delay spiral stainless steel tube (11-2)
The import of device (12) connects, and the resistive heater (11-1) with temperature sensor is close to delay spiral stainless steel tube (11-2)
Setting, the temperature sensor are connect with temperature control modules (20).
4. a kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument according to claim 1
Device, which is characterized in that the fluorescence detector (5) be three-dimensional fluorescence detector, including power supply system (5-1), Xe lamp (5-2),
First, which focuses (5-3), second thoroughly, focuses (5-6), the first narrow band filter (5-4), the second narrow band filter (5-7), quartz thoroughly
Flow cell (5-5), diffraction grating (5-8), photomultiplier tube (5-9) and fluorescence signal acquisition and signal conditioning circuit (5-
10),
It is moved towards by optical path, the Xe lamp (5-2), first focus (5-3), the first narrow band filter (5-4), quartzy flow cell thoroughly
(5-5), second focus (5-6), the second narrow band filter (5-7), diffraction grating (5-8), photomultiplier tube (5-9) thoroughly and sequentially set
It sets,
It being flowed to by liquid flow path, described quartz flow cell one end (5-5) is used to connect with preposition inorganic Nitrogen detector (4) outlet,
The other end is used to connect with acid adding injection valve (6),
By communication line, the power supply system (5-1) respectively with Xe lamp (5-2), diffraction grating (5-8) and photomultiplier tube (5-
9) it connects, is Xe lamp (5-2), diffraction grating (5-8) and photomultiplier tube (5-9) provide power supply, the photomultiplier tube (5-9)
Output end passes sequentially through fluorescence signal acquisition and signal conditioning circuit (5-10) and analog-to-digital conversion module (19) and computer (21)
Communication.
5. a kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument according to claim 4
Device, which is characterized in that the power supply system (5-1) is powered by the way of filtering out electric source disturbance and isolation output, including according to
Main power circuit, APFC rectification circuit, isolation auxiliary power supply circuit and the main Topology Driven circuit of secondary connection, the isolation auxiliary
Power supply circuit respectively with diffraction grating (5-8), fluorescence signal acquisition and signal conditioning circuit (5-10) and analog-to-digital conversion module
(19) it connects, the main power circuit is connect with photomultiplier tube (5-9), and is Xe lamp (5- by main Topology Driven circuit
1) it powers.
6. a kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument according to claim 4
Device, which is characterized in that the fluorescence signal acquisition and signal conditioning circuit (5-10) include photomultiplier tube amplification output power supply
Circuit, linear voltage-stabilizing circuit, amplifying circuit of analog signal, the main power circuit amplify output power supply electricity by photomultiplier tube
Road is photomultiplier tube (5-9) power supply, and uses constant current feedback controling mode, and the isolation auxiliary power supply circuit passes through linear
Voltage regulator circuit is amplifying circuit of analog signal power supply, and the photomultiplier tube (5-9) output end is successively put by analog signal
Big circuit and analog-to-digital conversion module (19) are connect with computer (21) afterwards.
7. a kind of synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument according to claim 4
Device, which is characterized in that first narrow band filter (5-4) is used to screen the exciting light that wavelength is 270 ± 10nm；Described second
Narrow band filter (5-7) is used to screen the transmitting light that wavelength is 320-520nm.
8. using the synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics method of instrument described in claim 1,
It is characterized in that,
Sampfe order enters size exclusion chromatography system (1), UV detector (2), preposition temperature control system (3), preposition inorganic nitrogen
Detector (4), fluorescence detector (5), acid adding injection valve (6), mixer (7), CO2Stripping device (8), divides ultraviolet digestion device (9)
From film (10), postposition temperature control system (11) and the organic Nitrogen detector of postposition (12),
Absorbance of the UV detector (2) by detection different molecular weight organic matter at 254nm, for indicating the molecule
The aromaticity size of organic matter at amount；
The preposition inorganic Nitrogen detector (4) is for content of inorganic nitrogen in test sample；
The fluorescence detector (5) maintains entire multi-detector to detect for detecting sample to be tested different molecular weight fluorescence information
The stability and synchronism of system；
The acid adding injection valve (6) is used to inject acid solution to the sample flowed to herein,
The mixer (7) is used to inorganic carbonate turning to CO2,
The CO2Stripping device (8) is used for CO2Stripping；
The ultraviolet digestion device (9) is used for Specimen eliminating,
The seperation film (10) is used to that the CO generated in ultraviolet digestion device (9) will to be stated2It separates to CO2It is examined in electric conductivity detector
It surveys, and then obtains DOC content,
The organic Nitrogen detector of postposition (12) is for organic nitrogen content in test sample；
The preposition temperature control system (3) and postposition temperature control system (11) are used for control system temperature.
9. synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics method according to claim 8, special
Sign is that size exclusion chromatography system (1) column temperature is set as 40~80 DEG C, and flow velocity is 0.5~0.7mL/min.
10. synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics method according to claim 8, special
Sign is that the preposition inorganic Nitrogen detector (4) passes through the ultraviolet suction at detection different molecular weight organic matter 220nm and 275nm
The absorbance of nitrate ion in water sample is calculated as follows in luminosity:
Wherein,A220nm, RAnd A275nm, PNitrate ion is respectively indicated in preposition inorganic Nitrogen detector 220nm and 275nm
The absorbance at place, coefficient lambda is between 1~10；
The nitrate anion that the organic Nitrogen detector of postposition (12) is converted after ultraviolet digestion by detection organic nitrogen is at 220nm
Absorbance A220nm, R, obtained with preposition inorganic Nitrogen detectorTo calibrate A220nm, R, what is obtained is exactly that organic nitrogen passes through
The nitrate anion absorbance that ultraviolet digestion device obtainsCalibration equation is as follows:
Again willNO after being scaled practical DON oxidation3 -Concentration is finally scaled DON concentration；
In the fluorescence signal acquisition and signal conditioning circuit (5-10) of the fluorescence detector (5), transmitting light collection step-length is
1nm, time shaft sample frequency f (HZ) and fluorescent scanning speedWith the volume V (μ of the quartzy flow cell (5-5)
L) and the flow velocity v of mobile phase (μ L/min) matches, and calculates for following formula:
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