CN105548106B - A kind of method that in-situ synchronization obtains active phosphorus and dissolved oxygen Two dimensional Distribution in water body, soil or deposit - Google Patents
A kind of method that in-situ synchronization obtains active phosphorus and dissolved oxygen Two dimensional Distribution in water body, soil or deposit Download PDFInfo
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N21/64—Fluorescence; Phosphorescence
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Abstract
A kind of in-situ synchronization acquisition water body, the method of active phosphorus and dissolved oxygen Two dimensional Distribution in soil or deposit, DGT devices are assembled into using DGT-PO functional composite membranes, the DGT-PO composite membranes include transparent supporting body, fluorescence sense layer and DGT fixed beds, the first step is based on fluorescence analysis principle, obtain the DO fluorescence intensity images of PO layers of composite membrane in real time using image technique, then second step will carry out film colour developing after the compound film process, and pass through the image of the SRP of DGT layers of Computer-generated images densitometry technical limit spacing colour developings, SRP and DO are measured and detected further according to obtained image.The method uses tri- color ratio rate quantitative technique of a kind of improved film colour developing-computer density imaging technique and RGB, and by DGT, PO binary channels, synchronous realize carries out in-situ monitoring to active phosphorus, dissolved oxygen in matrix.
Description
Technical field
The invention belongs to environmental science and field of earth sciences, it is related to a kind of Simultaneous Monitoring water body, deposit or wetland soil
The method of two kinds of important geochemistry parameter distribution information in the matrix such as earth, and in particular to one kind is balanced based on diffusive gradients in thin-films
The method that technology and plane optoelectronic pole technology in-situ synchronization obtain active phosphorus (SRP) and dissolved oxygen (DO) distributed intelligence.
Background technology
Phosphorus is one of the limiting nutrient of the most of lake eutrophications in China.In recent years, although the external source import of phosphorus
Effectively contained, but lake endogenous phosphorus pollution becoming serious, frequently occur so as to cause lake eutrophication phenomenon.
Deposit oxidation-reduction process control phosphorus is released, i.e., " anaerobic condition promotes the release of phosphorus, aerobic condition to be unfavorable for discharging for phosphorus " obtains
It confirms to many researchs and is generally accepted by everybody.Dissolved oxygen is the electron donor being preferentially utilized in sediment-water system, with
Other materials such as sulfate, nitrate and iron and manganese oxides etc. codetermine deposit redox environment.Therefore research phosphorus-
Oxygen synchronizes distributed intelligence and is conducive to further investigate benthic environment process.
Portability, low cost and performance compatibility are the important trends of enviromental monitoring equipment.Diffusive gradients in thin-films is flat
Weighing apparatus technology (DGT) and plane optoelectronic pole technology (PO) are used as novel in-situ monitoring technology, are developed out a variety of environmental monitorings and set
It is ready for use on a variety of environmental index monitorings.Since the two has complementarity on monitoring index, multifunctional composite and phase are developed
The analytical technology answered will effectively push environmental monitoring and a variety of environmental process Mechanism Studies.For phosphorus yield, DGT is utilized
Technology measures phosphorus by slice-extraction-molybdenum blue colorimetric method flow, can obtain a peacekeeping two dimension point for phosphorus in sediment-water
Cloth information.But this method is cumbersome, and time-consuming length, chemical consumption is big, and is easy to generate error, is unfavorable for high-volume sample
Analyzing processing.And laser ablation and Plasma-Mass Spectroscopy joint technology (LA-ICP-MS) though be widely used in the activity in fixed film
Substance such as phosphorus yield, and the technology is accurate, quick, but it is limited to expensive testing cost, current this method is not suitable for institute
There is laboratory.In the recent period, the colour developing of DGT films is employed successfully in phosphorus in environment with the method that Computer-generated images densitometry technology is combined,
Sulphur, the species analysis such as iron, this method can obtain high-resolution (micron order), the Two dimensional Distribution information of substance in batches.
Based on fluorescence intensity, ratio fluorescent and fluorescence lifetime are quantitatively that substance image letter is obtained in planar light electrode system
Cease most common method.Wherein, fluorescence intensity quantitative approach is that planar light electrode detection is most simple, one of most common method,
But single fluorescence intensity quantitatively exist many such as optical paths, bias light, photobleaching and photostability factor influence and
Interference.Fluorescence lifetime quantitative approach is not influenced by sensing membrane itself and external environmental interference, can provide more accurate and section
Substance distributed intelligence, but this method strongly rely on advanced, accurate hardware and software equipment, therefore testing cost compared with
Height is unfavorable for the universal of the electrode.Compared with fluorescence intensity and fluorescence lifetime quantitative approach, fluorescence intensity ratio rate quantitative approach master
It to utilize commercial digital camera that is simple, being easy to get and can significantly cut down the intrinsic defect of conventional fluorescent quantification of intensities method, it can
With it is accurate, fast implement substance Two dimensional Distribution image acquisition of information.
Invention content
The purpose of the present invention is to provide a kind of in situ, synchronous, high-resolution to obtain the matrix such as water body, deposit or soil
The method of middle SRP and DO Two dimensional Distributions.The method monitors the DGT-PO of active phosphorus and dissolved oxygen based on a kind of in-situ synchronization
Composite membrane mainly uses tri- color ratio rate quantitative technique of a kind of improved film colour developing-computer density imaging technique and RGB, leads to
DGT, PO binary channels are crossed, synchronous realize carries out in-situ monitoring to active phosphorus, dissolved oxygen in matrix.
To sum up, the present invention is based on a kind of in-situ synchronization monitor active phosphorus and dissolved oxygen DGT-PO functional composite membranes,
A kind of " two stage assay " method of structure realizes that in situ, synchronous, high-resolution obtains the detection of SRP and DO Two dimensional Distributions.This method
It is to be based on two kinds of newest picture imaging techniques, i.e. fluorescent image acquiring technology and film colour developing-Computer-generated images densitometry technology,
The first step is based on fluorescence analysis principle, obtains composite membrane in real time using image technique in the matrix contact interface such as deposit or soil
PO layers of DO fluorescence intensity images, then second step will carry out film colour developing after the compound film process, and pass through Computer-generated images density
Measurement technology obtains the image of DGT layers of SRP colour developings, and SRP and DO are measured and detected further according to obtained image.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of in-situ synchronization obtains active phosphorus (SRP) and dissolved oxygen (DO) Two dimensional Distribution in water body, soil or deposit
Method, which is characterized in that be placed in matrix after DGT-PO composite membranes are assembled into DGT devices, the DGT-PO composite membrane packets
Transparent supporting body, fluorescence sense layer and DGT fixed beds are included, the fluorescence sense layer is by fluorescent dye octaethylporphyrin platinum
(PtOEP) it is uniformly mixed with fluorescein 10-GN, two kinds of fluorescent dyes is fixed on by transparent supporting body surface shape by chemistry embedding
At the DGT fixed beds use sub-micron ZrO particles for fixative, and polyurethane hydrogel is matrix, by coating method glimmering
DGT fixed beds are made on light sensing layer；Fluorescent image acquiring technology is used first, is obtained in real time described under 389nm shooting conditions
The fluorescent image of DGT-PO composite membranes obtains the Two dimensional Distribution information of DO after image software is handled；Then, wait for that DGT is fixed
Active phosphorus carries out pickling, film heat pre-treatment, after pretreatment to balancing after taking out DGT-PO composite membranes in layer fully extraction matrix
DGT-PO composite membranes be added phosphorus color developing agent using molybdenum blue colorimetric method carry out film colour developing, directly DGT fix layer surface coloring, lead to
Cross the Two dimensional Distribution information that deposit SRP is obtained after Computer-generated images densitometry technology calculates.
In the water body, soil or deposit in the Two dimensional Distribution detection method of SRP and DO, the Two dimensional Distribution of DO is obtained
The specific method of information includes the following steps：
(1) nitrogen is used to prepare the dissolved oxygen correcting fluid of one group of difference saturated dissolved oxygen concentration with air, it will be described
DGT-PO composite membranes are placed in buffer solution, using the UV light source activations of 389nm, and are obtained under different saturated dissolved oxygen concentration conditions
The fluorescent image of fluorescence sense layer in the DGT-PO composite membranes；
(2) to obtaining fluorescent image in step (1), gained image is carried out by R-G-B triple channels using image processing software
It splits, obtains corresponding red and blue channel the two kinds of fluorescence intensity figures of two kinds of dyestuff PtOEP and fluorescein 10-GN
Picture calculates two channel fluorescence intensity ratio Rs, and it is carried out curve fitting with corresponding dissolved oxygen concentration (DO values), obtains institute
For the PO layers i.e. fluorescence sense layer for the DGT-PO composite membranes stated to DO value response curves, the PO layer fluorescence release of DGT-PO composite membranes is special
Sign is revised equation (formula 1) according to Stern-Volmer and is described：
R in formula0, R is absolute anaerobic condition (value=0 DO), difference DO values correspond to red channel and green in fluorescent image
Channel fluorescence intensity ratio, α are the dyestuff proportion that quenching reaction does not occur in the film, KsvIt is the DGT-PO composite membranes to DO
Fluorescent quenching constant , [C]For the concentration of DO in matrix.
(3) DO is tested：After being inserted into the compound Membrane cleanings of the DGT-PO in matrix, according to the identical side with step (1)
Method obtains fluorescent image, according still further to the identical method with step (2), by each point on fluorescent image fluorescence intensity ratio R according to
The corresponding DO values of the point are calculated in DO value response curves.
In the water body, soil or deposit in the Two dimensional Distribution detection method of SRP and DO, the inspection of SRP Two dimensional Distributions
It surveys based on DGT fixed beds in the composite membrane, being combined method using molybdenum blue method colour developing and Computer-generated images densitometry technology obtains
SRP Two dimensional Distribution information, is as follows：
(1) the DGT-PO composite membranes are fitted into DGT devices, then configure the phosphorous mark of one group of difference known concentration
DGT devices comprising the DGT-PO composite membranes are put into phosphorous standard solution to adsorption equilibrium, each concentration by quasi- solution
Including at least two parallel samples；The DGT-PO composite membranes in DGT devices are taken out, after a parallel sample is extracted with NaOH, are used
Occluded corrosion cell measures DGT fixed beds and adsorbs phosphorus content；
(2) after another parallel sample is rinsed well, pickling, film heat pre-treatment are then carried out, is somebody's turn to do pretreated
Diaphragm, which is put into the anti-developing solution of molybdenum antimony, to develop the color, and with scanner scanning, the film is positive (DGT fixes layer surface), at image
The image obtained is converted to grey value profile image by reason software, by the ash of DGT-PO composite membranes in same phosphorous standard solution
Angle value is fitted to calibration curve or regression equation with absorption phosphorus content；
(3) will be inserted into matrix in extraction active phosphorus to balance after the compound Membrane cleanings of the DGT-PO after, according to step
(2) identical method obtains grey value profile image, and obtaining DGT fixed beds according to obtained calibration curve or regression equation inhales
Attached phosphorus content；
(4) Two dimensional Distribution of SRP on the DGT-PO composite membranes is calculated according to Fick First Laws.
It should be pointed out that it is to adopt to carry out pretreatment to the DGT-PO composite membranes after the Two dimensional Distribution information of acquisition DO
It is synchronized necessary to obtaining SRP and DO Two dimensional Distributions with the method for the present invention.To avoid significantly affecting for DGT layers in DGT-PO composite membranes
Radial diffusions of the DO in composite membrane, and ensure that composite membrane obtains the spatial synchrony of DO and SRP information, the DGT-PO of preparation
Composite membrane is only 150~200 μ m-thicks, wherein DGT layers only about 50 μm, the DGT-PO composite membranes is caused to be easy to when DGT is tested
Film rupture and phosphorus diffusion phenomenon, preprocess method, which occurs, effectively to be solved these problems.Pretreatment is heated using pickling, film
Two-stage process usually carries out pickling in 24 hours with 0.1M dilute nitric acid solutions first, is carried out after then being cleaned up with deionized water
Film heats.
Concrete operations, optimal conditions and the computational methods that SRP Two dimensional Distribution information is obtained in relation to DGT methods, reference can be made to Shen
The application for a patent for invention CN2013100772553 to ask someone.
Heretofore described DGT-PO composite membranes are prepared using following methods, first will be different to oxygen sensitive
Two kinds of fluorescence indicators are selected insensitive to the sensitive octaethylporphyrin platinum of DO concentration-responses (PtOEP), and response respectively
After fluorescein 10-GN dyestuffs are proportionally sufficiently mixed uniformly, mixed liquor is uniformly fixed on by chemical investment transparent
On supporter, the fluorescence sense layer (PO layers) of composite membrane is formed after air drying；Then film preparation technique is fixed by DGT, adopted
Slurries are made with the polyurethane hydrogel and sub-micron ZrO particles of saturating protic and gas permeability, direct film is formed on PO layers
DGT fixed beds；It is final to prepare the ultra-thin composite membrane for becoming like " sandwich " structure.
The transparent supporting body preferred PET (polyethylene terephthalate) film.The thickness of DGT-PO composite membranes
It is 150~200 μm.
In the composite membrane preparation process, in fluorescence sense layer the weight ratio of PtOEP and fluorescein 10-GN be 0.05~
1.5：1, preferably 1：1.PtOEP fluorescent dyes and another fluorescence with reference effect and blast effect are contaminated in the present invention
Material-fluorescein 10-GN mixing is used as fluorescence indicator, by optimizing adding proportion, obtains optimal signal strength to characterize DO
The height of value.It prepared by DGT fixed beds, film base material uses polyurethane hydrogel (HY), by it with alcohol at hydrogel
Mixed liquor (preferably 10:1, V:V), itself and fixative sub-micron ZrO particulate slurries are then sufficiently mixed and are carried out ultrasonic disperse,
W/v is 0.1g~1.0g ZrO/1mL hydrogel mixed liquors, preferred 0.5g ZrO/1mL hydrogels mixed liquor, then
It is stirred overnight, fixed bed slurries is prepared into after mixing well, the DGT fixed beds of film preparation composite membrane are directly applied in PO layer surfaces.
The preparation of the sub-micron ZrO particulate slurries can be found in document Kreuzeder, A.；Santner,J.；
Prohaska,T.；Wenzel,W.W.,Gel for simultaneous chemical imaging of anionic and
cationic solutes using diffusive gradients in thin films.Analytical chemistry
2013,85,(24),12028-36。
Applicant is based on DGT and PO technical principles, and a kind of NEW TYPE OF COMPOSITE work(is successfully prepared by settling film-forming method layer by layer
Energy material, based on the DGT-PO complex function sensor films newly developed, the present invention is close by improving DGT films colour developing-Computer-generated images
Measurement technology and ratio fluorescent quantitative technique are spent, it can be achieved that in-situ synchronization obtains Phosphorus Exchange at Sediment-water Interface-oxygen Two dimensional Distribution letter
Breath, the method is simple and quick, is particularly suited for the processing of batch samples, at low cost.To water/sediment interface and deposit
Phosphorus-oxygen distribution and variation, and it is corresponding with the various reaction type processes in interface further investigate, will be micro-interface process and nutrition
Salt converts quantitative analysis and provides important information.
In-situ synchronization obtains the rapid assay methods of the Two dimensional Distribution information of SRP and DO, tool in the environmental matrices of the present invention
It has the advantage that：
(1) two kinds of image capture technologies, rapid batch are relied on to obtain system SRP and DO Two dimensional Distribution information, compared to tradition
Expensive laser ablation-inductive coupling plasma mass spectrometry combination measures or the micro colour developing skill of cumbersome film two dimension slicing-extraction-
The SRP image acquiring method costs of art monitoring technology, the composite membrane are lower, and are simple and efficient；In addition, composite membrane PO inductive layers
Dye formulation not only rely on a kind of indicator dye, but coordinate the use of fluorescein 10-GN dyestuffs, swash in 389nm
It shines under excitation, fluorescein 10-GN has very high fluorescent brightness, can not only enhance the brightness of sensing membrane, but also can be with
As the reference dye of DO, various external interferences, more accurate acquisition DO Two dimensional Distributions letter are eliminated based on ratio fluorescent quantitative technique
Breath.
(2) DGT layers of the composite membrane uses ultra-fine ZrO sorbing materials, about 12.3 μ g/cm of adsorption capacity2, it is higher than traditional Fe
Film (about 1.36 μ g/cm2), higher adsorption capacity has widened the scope of application of DGT technologies；In addition, the PO inductions of the composite membrane
Layer is very wide to the response range of DO：0~100% air saturation.
(3) high spatial resolution can obtain micron order spatial resolution SRP and DO distribution letter using image capture technology
Breath.
Description of the drawings
The structural schematic diagram of Fig. 1 .DGT-PO composite membranes.
Fig. 2 .DGT-PO composite membranes DGT fixes the SEM image of the ultra-fine ZrO particles of layer surface.
Fig. 3 .DGT-PO composite membrane DGT fixed bed adsorption capacity curves.
Fig. 4 pickling-washing fixes phosphorous recovery to DGT-PO composite membranes to be influenced.
Calibration curve under Fig. 5 .DGT-PO composite membrane difference developing times between Phosphate Sorption and gray value.
Fig. 6 .DGT-PO composite membrane PO inductive layers respond effect and DO standard curves.
Fig. 7 .DGT-PO composite membranes response time of (0% and 100%) and reproducibility under different dissolved oxygen conditions.
The Two dimensional Distribution variation characteristic of Fig. 8 DO and SRP under aerobic and anaerobic conditions；Wherein A, B respectively represent aerobic item
DO and SRP distributions under part, C, D respectively represent DO and SRP distributions under anaerobic condition, and dimension of picture is 50mm × 70mm.
Specific implementation mode
Embodiment 1
The DGT-PO composite membranes of in-situ synchronization monitoring active phosphorus and dissolved oxygen that the present invention uses, preparation are used with lower section
Method：
(1) 10mg, the PtOEP dyestuffs of 10mg, 500mg, fluorescein 10-GN dyestuffs and polyethylene particle are taken respectively, are dissolved
In the toluene of 10mL, after ultrasonic dissolution, 200 μ L mixed liquors is taken, are uniformly coated the mixed liquor using the method for 100 μm of knifing
On transparent PET film base material, after drying at room temperature 30min, the fluorescence sense layer (PO) of composite membrane is formed；Dark place is placed on to be protected from light
It is sealed for use.
(2) Kreuzeder is pressed, the method for the descriptions such as A prepares sub-micron ZrO ultra-fine grain slurries；It includes 8.0g to weigh
The ultra-fine grain slurries of ZrO, then (polyurethane hydrogel, type D4 are purchased from U.S. with polyurethane hydrogel HYD4
AdvanSource Biomaterials companies of state) with the mixed liquor (10 of alcohol:1, V:V) 16mL is mixed, using ultrasonication
After instrument handles 20min, it is sufficiently stirred on magnetic stirring apparatus overnight, is prepared into fixed bed slurries；It is placed on magnetic stirring apparatus and holds
Continuous stirring is spare.
(3) on the fluorescence sense layer (PO) prepared in step (1), the filling pad of 500 μ m thicks is pasted, takes 5mL above-mentioned
Fixed bed slurries obtained in step (2) carry out painting film preparation DGT fixed beds in the U-type groove using glass bar.It is stored at room temperature
Compound film preparation is completed after 1 day, is placed on dark place and is protected from light and is sealed.
There is obtained DGT-PO composite membranes " sandwich " structure (Fig. 1), DGT to fix the SEM image of layer surface as schemed
2, the ultra-fine ZrO particles in surface are uniform, Li Jing <0.5 μm, (5 μm) significant decreases of peplomer diameter are fixed than traditional ZrO.
Embodiment 2
DGT-PO composite membranes are as follows phosphorus fixation volume test：
(1) the DGT-PO composite membranes prepared are sliced (diameter 2.0cm) using ring stainless steel knife, are justified
Piece is put into deionized water, and purity nitrogen is inflated 12 hours, excludes the oxygen in film, spare.
(2) the DGT-PO composite membranes prepared are assembled into piston type DGT devices, are then put into assembled device
Aquation at least four hour, spare in denitrification, ultra-pure water.
(3) assembled DGT devices in step (2) are put into 8 kinds of different phosphate-containing concentration mother liquors of 0.5~10mg/L
In (0.001mg P/L~20mg P/L, pH=7.0 ± 0.2；0.03M NaCl), carry out 6h absorption, every group of 3 Duplicate Samples.
(4) after the completion of to be adsorbed, DGT devices are taken out, recycle composite membrane, then with being put into 5mL 1.0M after ultrapure water
It is fully extracted for 24 hours in NaOH solution, then microcolorimetry is used to measure the phosphorus concentration in extracting solution.
(5) composite membrane disk effective unit area is calculated according to concentration measured in (4) and fixes phosphorus content, then basis
DGT principles seek the theoretical fixed phosphorus average content of calculating, draw theoretical value and actual value curve, obtain that the results are shown in Figure 3, as a result
Show that the capacity that the film fixes phosphorus is 12.34 μ g P/cm2, consolidate phosphorus content (1.8~9.0 times) far above used iron film.
Embodiment 3
The organic efficiency that DGT-PO composite membranes pickling-heat pre-treatment fixes composite membrane in phosphorus influences, according to the following steps
It carries out：
(1) the DGT-PO composite membranes for preparing embodiment 1, after abundant aquation 4h, using radius 1cm stainless steel circular shear blades
It is sliced, then carries out the assembling of piston type DGT devices.
(2) assembled DGT devices in (1) are put into (pH=7.0 ± 0.2 in different phosphate-containing mother liquors；0.03M
NaCl)), after the completion of absorption, the DGT-PO composite membranes in the device of recycling are subjected to pickling (0.1M dust technologies) for 24 hours and water respectively
4h is washed, 1.0M NaOH extractions are carried out after heating, another set directly uses 1.0M NaOH extractions, two groups of processing to measure the knot of phosphorus
Fruit sees Fig. 4.The result shows that pickling, washing and heating to the phosphorous recovery in composite membrane about in (96.50 ± 0.26) % and
Between (103.92 ± 1.91) %, illustrate that pickling and heat pre-treatment will not cause active phosphorus to be lost in above composite membrane.
Embodiment 4
Calibration curve between DGT-PO composite membranes DGT fixed beds Phosphate Sorption and gray value, is established according to the following steps：
(1) the DGT-PO composite membranes that will be prepared are put into aquation at least four hour in denitrification, ultra-pure water, spare.
(2) step (1) treated DGT-PO composite membranes, carry out cutting film, obtain using the stainless steel round cutter of radius 1cm
To the composite membrane disk of radius 1cm, by gained composite membrane disk, 0.45 μm of filter membrane is assembled into DGT devices after being sequentially overlapped.
(3) gained DGT devices in step (2) are put into deionized water and carry out 12h nitrogen charging removal oxygen and (exclude DO pairs
PO layers of influence).
(4) difference of configuration 0.05,0.1,0.2,0.25,0.3,0.5,1.0,2.0,3.0,4.0,6.0,10.0mg/L is dense
The phosphorous mother liquor (each 2mL) of degree, DGT devices of placing in 6 steps (3) that treated in each mother liquor respectively adsorb one respectively
After fixing time (4~12 hours), the compound film sheet in withdrawing device, wherein 3 composite membrane disks is taken to be carried with the NaOH of 1M
It takes, measures absorption phosphorus content, the other three is spare.
(5) spare composite membrane is rinsed well, according to pickling (0.1M dust technologies), electric hot plate heats two steps and located in advance
Reason.It is to be heated finish after, diaphragm to be developed the color is put into the anti-developing solution of molybdenum antimony and is developed the color respectively according to 45min developing times, so
Afterwards with cold water flush it is clean after, gently blot surface moisture with filter paper, it is soft by image procossing with scanner scanning film front
Part is converted to grey value profile image, by the gray value of DGT-PO composite membranes in same phosphorous mother liquor and absorption phosphorus content fitting
At calibration curve or regression equation.
(6) it according to step (4) 2 groups of experiments of progress are repeated, obtains diaphragm to be developed the color and develops the color respectively according to step (5),
Developing time is respectively 60min and 90min, and fitting respectively obtains obtaining composite membrane gray scale-absorption under the conditions of different developing times
Capacity relationship curve, as shown in Figure 5.
The result shows that the gray value that developing time 45min and 60min are obtained is low compared to 90min developing time discretenesses,
And the developing time of 60min gray value corresponding compared to 45min colour developing curves is sensitiveer to phosphorus content, therefore the method for the present invention
Preferred developing time is set as 60min, and the correction between Phosphate Sorption and gray value that correspondingly 60min developing times obtain is bent
Line is as standard curve.
Embodiment 5
Influence of DGT layers of the DGT-PO composite membranes to PO layers of response curve is tested, and is carried out by step in detail below：
(1) it presses step (1) in embodiment 1 to obtain without DGT layers of PO films, and the DGT-PO composite membranes prepared, be put into
In deionized water, purity nitrogen is inflated 12 hours, excludes the oxygen in film.
(2) by one side on the inside of step (1) treated two kinds of diaphragms are attached to quartz glass box, supporter one side and quartz
Face is in direct contact, and a ultra-thin filter membrane of strata carbonic ester is then covered on diaphragm, and fix filter membrane using adhesive waterproof tape, in box
Simulation lake water solution (pH=7.0 ± 0.2 is added；0.03M NaCl).
(3) it is passed through the ultrapure nitrogen and air of different proportion, adjusting aqueous solution is saturated dissolved oxygen concentration (0%~100%
Saturated dissolved oxygen), using the UV light source activations of 389nm, and obtain under different saturated dissolved oxygen concentration conditions two kinds of PO films and
The fluorescent image of sense film in DGT-PO composite membranes.
(4) to obtaining fluorescence picture in step (3), using image processing software ImageJ 1.46, R-G-B threeways are carried out
Road is split, and obtains the corresponding red and blue channels of two kinds of dyestuff PtOEP and fluorescein 10-GN, it is glimmering to calculate two channels
Intensity ratio R, and it is carried out curve fitting with corresponding dissolved oxygen concentration (DO values), it obtains the PO films and DGT-PO is multiple
DO value response curves, fluorescence sense film fluorescence release characteristic can be revised according to Stern-Volmer by closing PO fluorescence senses film in film
Equation (formula 1) describes：
R in formula0, it is strong that R is absolute anaerobic condition, difference DO values correspond to red channel and green channel fluorescence in fluorescent image
Ratio is spent, α is the dyestuff proportion that quenching reaction does not occur in the film, KsvIt is the sense film to the fluorescent quenching constant of DO,
[C]For the concentration of DO in matrix.
Eligible result is as shown in Figure 6.The result shows that index variation is presented to DO responses in two kinds of fluorescence sense films, calculate
The two kinds of films obtained are distributed as 1.95 and 2.12 to DO response sensitivities, it was demonstrated that in composite membrane DGT layers there are minor impact,
This influence can be eliminated by three point calibrations.
It is further fitted the response curve of DGT-PO composite membranes, equation (2) can be obtained, for calculating DO values.
Embodiment 6
PO layers of response time of DGT-PO composite membranes and reproduction performance, follow the steps below test：
(1) by after the abundant aquation 4h of the DGT-PO composite membranes prepared, 50mm × 50mm films is cut into using Stupalox, are pressed
The diaphragm is pasted onto quartz glass box inner wall (50mm × 50mm × 10mm) according to step (2) in embodiment 5.
(2) by adjusting pure nitrogen gas and air mixture ratio, the saturation of solution is molten in quartz glass box in rate-determining steps (1)
Oxygen amount is converted between 100% and 0%, and at 20 DEG C, ionic strength is 0.03M NaCl for temperature control, and pH is 7.0 ± 0.2.
(3) it takes pictures at interval of 2s, data processing, knot is carried out according to step (4) in embodiment 5 after acquisition fluorescent image
Fruit is as shown in Figure 7.The result shows that the DGT-PO composite membranes have good repeatability to DO inductions, when DO is from 100% to 0%
When conversion, which reaches 95% highest signal time (t95) it is 24s, and when DO is converted from 0% to 100%, the film
Response signal reaches minimum stable signal time;3s.
Embodiment 7
Active phosphorus (SRP) and the two dimension of dissolved oxygen (DO) point in deposit are obtained based on DGT-PO composite membrane in-situ synchronizations
Cloth, steps are as follows：
(1) the DGT-PO composite membranes that will be prepared are put into aquation at least four hour in denitrification, ultra-pure water, spare.
(2) Taihu Lake Sediment sample and water sample are acquired, takes back that laboratory is spare, it is mixed that the deposit being collected is carried out sieving
It is even, it is put into respectively in two incubators after water sample filtering, sediment depth 15cm, overlying water depth 25cm is kept then to adjust
Air and nitrogen ratios blast mixed gas to two groups of devices, carry out continuing aeration 2 weeks, build aerobic and anaerobic conditions respectively.
(3) composite membrane in step (1) is dropped into (50mm in the quartz glass case for be tightly pasted onto both ends open using waterproof
×100mm×150mm).Then the ultra-thin polycarbonate leaching film of 10 μ m thicks (ventilative, saturating ion) is attached on composite membrane
Face, as protective film.
(4) when being tested, the glass box for posting composite membrane is directly inserted perpendicularly into cultured deposit, clear water is used
The deposit on glass box periphery is washed, the side's of being used in combination plug pedestal fixes deposit and moves to darkroom, is obtained using fluorescent image
System is tested.
(5) DO distributed intelligences by obtaining observation section fluorescent image in real time in deposit, according to 5 step of embodiment (4)
Calculate or can be obtained after drawing the DO two dimension DYNAMIC DISTRIBUTIONs of water/sediment interface.
(6) after having obtained DO fluorescent images, composite membrane is taken out, after carrying out fully cleaning with deionized water, is located in advance
Reason, pickling (0.1M dust technologies) are washed afterwards for 24 hours, and 80 DEG C of heater plates are fixed, and film, which is then put into phosphorus developing solution, carries out molybdenum blue
Colour developing and scanning, the gray scale established according to 4 step of embodiment (6)-adsorbance standard curve carry out concentration calculating.
The measurement result of the Two dimensional Distribution of SRP and DO is as shown in Figure 8 in deposit.
Claims (7)
1. the method for active phosphorus SRP and dissolved oxygen DO Two dimensional Distributions in a kind of in-situ synchronization acquisition water body, soil or deposit,
It is characterized in that, is placed in matrix after DGT-PO composite membranes are assembled into DGT devices, the DGT-PO composite membranes include transparent branch
Support body, fluorescence sense layer and DGT fixed beds, the fluorescence sense layer are by fluorescent dye octaethylporphyrin platinum and fluorescein
10-GN is uniformly mixed, and two kinds of fluorescent dyes, which are fixed on transparent supporting body surface, by chemistry embedding forms, and the DGT is solid
Given layer uses sub-micron ZrO particles for fixative, and polyurethane hydrogel is matrix, is made on fluorescence sense layer by coating method
DGT fixed beds；Fluorescent image acquiring technology is used first, obtains the DGT-PO composite membranes under 389nm shooting conditions in real time
Fluorescent image obtains the Two dimensional Distribution information of DO after image software is handled；Then, wait for that DGT fixed beds fully extract matrix
Middle active phosphorus carries out pickling, film heat pre-treatment, pretreated DGT-PO composite membranes to balancing after taking out DGT-PO composite membranes
Phosphorus color developing agent is added, film colour developing is carried out using molybdenum blue colorimetric method, directly fixes layer surface coloring in DGT, pass through Computer-generated images density
Measurement technology obtains the Two dimensional Distribution information of deposit SRP after calculating.
2. active phosphorus SRP and dissolved oxygen DO bis- in in-situ synchronization acquisition water body according to claim 1, soil or deposit
The method for tieing up distribution, which is characterized in that the method for obtaining the Two dimensional Distribution information of DO includes the following steps：
(1) nitrogen is used to prepare the dissolved oxygen correcting fluid of one group of difference saturated dissolved oxygen concentration with air, by the DGT-PO
Composite membrane is placed in buffer solution, using the UV light source activations of 389nm, and obtains the DGT- under different saturated dissolved oxygen concentration conditions
The fluorescent image of fluorescence sense layer in PO composite membranes；
(2) to obtaining fluorescent image in step (1), gained image is carried out by R-G-B triple channel fractionations using image processing software,
Corresponding red and blue channel the two kinds of fluorescence intensity images of two kinds of dyestuff PtOEP and fluorescein 10-GN are obtained, are calculated
Two channel fluorescence intensity ratio Rs, and it is carried out curve fitting with corresponding DO values, obtain the PO of the DGT-PO composite membranes
Layer revises equation description to DO value response curves, the PO layer fluorescence release characteristics of DGT-PO composite membranes according to Stern-Volmer：
R in formula0, R is absolute anaerobic condition, difference DO values correspond to red channel and green channel fluorescence intensity ratio in fluorescent image
Value, α are the dyestuff proportion that quenching reaction does not occur in the film, KsvIt is normal to the fluorescent quenching of DO for the DGT-PO composite membranes
Number, C are the concentration of DO in matrix；
(3) DO is tested：After being inserted into the compound Membrane cleanings of the DGT-PO in matrix, obtained according to the identical method with step (1)
Fluorescent image is taken, according still further to the identical method with step (2), by the fluorescence intensity ratio R of each point on fluorescent image according to DO values
The corresponding DO values of each point are calculated in response curve.
3. active phosphorus SRP and dissolved oxygen DO bis- in in-situ synchronization acquisition water body according to claim 1, soil or deposit
The method for tieing up distribution, which is characterized in that the method for obtaining the Two dimensional Distribution information of SRP includes the following steps：
(1) the DGT-PO composite membranes are fitted into DGT devices, the phosphorous standard for then configuring one group of difference known concentration is molten
DGT devices comprising the DGT-PO composite membranes are put into phosphorous standard solution to adsorption equilibrium by liquid, and each concentration is at least
Including two parallel samples；The DGT-PO composite membranes in DGT devices are taken out, after a parallel sample is extracted with NaOH, with phosphorus molybdenum
Blue colorimetric method for determining DGT fixed beds adsorb phosphorus content；
(2) after another parallel sample is rinsed well, pickling, film heat pre-treatment is then carried out, pretreated diaphragm is put
Enter and develop the color in the anti-developing solution of molybdenum antimony, layer surface is fixed with scanner scanning DGT, will be obtained by image processing software
Image is converted to grey value profile image, by the gray value of DGT-PO composite membranes in same phosphorous standard solution and absorption phosphorus content
It is fitted to calibration curve or regression equation；
(3) will be inserted into matrix in extraction active phosphorus to balance after the compound Membrane cleanings of the DGT-PO after, according to step (2) phase
Same method obtains grey value profile image, and DGT fixed bed Phosphate Sorptions are obtained according to obtained calibration curve or regression equation
Content；
(4) Two dimensional Distribution of SRP on the DGT-PO composite membranes is calculated according to Fick First Laws.
4. active phosphorus SRP and dissolving in in-situ synchronization acquisition water body according to claim 1,2 or 3, soil or deposit
The method of oxygen DO Two dimensional Distributions, which is characterized in that the DGT-PO composite membranes are prepared using following methods, select eight second first
It is by chemical investment that mixed liquor is uniform after base porphyrin platinum and fluorescent yellow dye 10-GN are proportionally sufficiently mixed uniformly
It is fixed on transparent supporting body, forms the fluorescence sense layer of composite membrane after air drying；Then film preparation work is fixed by DGT
Slurries are made using polyurethane hydrogel and sub-micron ZrO particles in skill, and direct film forms DGT and fixes on fluorescence sense layer
The DGT-PO composite membranes are made in layer.
5. active phosphorus SRP and dissolved oxygen DO bis- in in-situ synchronization acquisition water body according to claim 4, soil or deposit
The method for tieing up distribution, which is characterized in that the thickness of the DGT-PO composite membranes is 150~200 μm, and transparent supporting body is poly- pair
Ethylene terephthalate film.
6. active phosphorus SRP and dissolved oxygen DO bis- in in-situ synchronization acquisition water body according to claim 4, soil or deposit
The method for tieing up distribution, which is characterized in that the weight ratio of PtOEP and fluorescein 10-GN are 0.05~1.5 in fluorescence sense layer：1.
7. active phosphorus SRP and dissolved oxygen DO bis- in in-situ synchronization acquisition water body according to claim 4, soil or deposit
The method for tieing up distribution, which is characterized in that slurries volume ratio by weight is sub-micron ZrO：Polyurethane hydrogel alcohol is mixed
Liquid 0.1g~1.0g/1mL is closed to be obtained by mixing.
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| CN105973886B (en) * | 2016-05-30 | 2019-03-29 | 田发益 | A kind of method and device determining concentration value based on visible light |
| CN106092992B (en) * | 2016-07-13 | 2019-04-19 | 王亮 | A kind of oxygen in soil Two dimensional Distribution measuring device |
| CN108344723B (en) * | 2018-02-24 | 2021-05-04 | 南京智感环境科技有限公司 | In-situ synchronous monitoring method for wetland soil |
| CN108344724B (en) * | 2018-02-24 | 2021-05-04 | 南京智感环境科技有限公司 | Portable wetland soil monitoring devices |
| CN109507177A (en) * | 2018-11-28 | 2019-03-22 | 南京维申环保科技有限公司 | A method of colour developing monitoring available phosphorus in situ is carried out based on DGT technology |
| CN110987726B (en) * | 2019-09-20 | 2022-07-15 | 农业农村部环境保护科研监测所 | Method for in-situ monitoring two-dimensional plane migration of soil trace elements |
| CN113030031A (en) * | 2019-12-24 | 2021-06-25 | 杭州柔谷科技有限公司 | Oxygen concentration test method, oxygen concentration test device and fluorescent oxygen sensor |
| CN111060511B (en) * | 2020-01-10 | 2022-07-19 | 南京国兴环保产业研究院有限公司 | PO-DGT combined detection device and acquisition detection method for sediment nutrients |
| CN111781198A (en) * | 2020-07-15 | 2020-10-16 | 南通大学 | Two-dimensional determination method for ammonia nitrogen content in water body, soil or sediment |
| CN112730358A (en) * | 2020-12-17 | 2021-04-30 | 中国科学院南京地理与湖泊研究所 | Optical sensing film for monitoring pH two-dimensional dynamic distribution in sediment |
| CN112730359A (en) * | 2020-12-17 | 2021-04-30 | 中国科学院南京地理与湖泊研究所 | Composite optical sensing film for synchronously monitoring dissolved oxygen and pH of sediment |
| CN112730357A (en) * | 2020-12-17 | 2021-04-30 | 中国科学院南京地理与湖泊研究所 | Optical sensing film for detecting two-dimensional distribution of carbon dioxide in sediment |
| CN112747950B (en) * | 2021-01-14 | 2022-08-05 | 自然资源部第一海洋研究所 | Columnar sediment sampling system with in-situ data acquisition function |
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