CN105548106A - Method for in-situ synchronous acquisition of two-dimensional distribution of active phosphor and dissolved oxygen in water, soil or sediment - Google Patents
Method for in-situ synchronous acquisition of two-dimensional distribution of active phosphor and dissolved oxygen in water, soil or sediment Download PDFInfo
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Abstract
The invention discloses a method for in-situ synchronous acquisition of two-dimensional distribution of active phosphor and dissolved oxygen in water, soil or sediment. The method utilizes a DGT device comprising a DGT-PO functional composite membrane. The DGT-PO functional composite membrane comprises a transparent support, a fluorescent sensing layer and a DGT fixed layer. The method comprises 1, based on a fluorescence analysis principle, acquiring a DO fluorescence intensity image of a composite membrane PO layer in real time through an image technology, and 2, treating the composite membrane, carrying out membrane color development, acquiring a SRP developing image of the DGT layer through a computer-generated imagery density measurement technology and carrying out metering and detection on the SRP and DO according to the acquired image. Through use of an improved membrane developing-computer-generated imagery technology and a RGB three-color rate quantification technology, active phosphor and dissolved oxygen in a matrix can be synchronously monitored in real time through DGT-PO double channels.
Description
Technical field
The invention belongs to environmental science and field of earth sciences, to relate in the matrix such as a kind of Simultaneous Monitoring water body, sediment or wetland soil the method for two kinds of importantly Geochemistry parameter distribution information, be specifically related to a kind of method that based thin film diffusion gradient balancing technique and plane optoelectronic pole technology in-situ synchronization obtain active phosphorus (SRP) and dissolved oxygen DO (DO) distributed intelligence.
Background technology
One of limiting nutrient of the most of lake eutrophication of Lin Shi China.In recent years, although the external source import of phosphorus is effectively contained, lake endogenous phosphorus pollution becoming serious, thus cause lake eutrophication phenomenon frequently to occur.Sediment oxidation-reduction process controls phosphorus and releases, and namely " anaerobic condition promotes the release of phosphorus, and aerobic condition is unfavorable for the release of phosphorus " obtains much research confirmation and generally admitted by everybody.Dissolved oxygen DO is the electron donor be preferentially utilized in sediment-water system, and with other material as sulfate, nitrate and iron and manganese oxides etc. determine sediment redox environment jointly.Therefore study the synchronous distributed intelligence of phosphorus-oxygen and be conducive to further investigation benthic environment process.
Portability, low cost and performance compatibility are the important development trend of enviromental monitoring equipment.Diffusive gradients in thin-films balancing technique (DGT) and plane optoelectronic pole technology (PO), as novel in-situ monitoring technology, have been developed out multiple enviromental monitoring equipment and have monitored for multiple environmental index.Because the two has complementarity on monitoring index, development multifunctional composite and corresponding analytical technology effectively will promote environmental monitoring and multiple environmental process Mechanism Study.For phosphorus yield, utilize DGT technology, measure phosphorus by section-extraction-molybdenum blue colorimetric method flow process, a peacekeeping Two dimensional Distribution information of phosphorus in sediment-water can be obtained.But the method complex operation, time-consuming length, chemical consumption is large, and is easy to produce error, is unfavorable for sample analysis process in enormous quantities.And laser ablation and Plasma-Mass Spectroscopy coupling technique (LA-ICP-MS) are though the active substance be widely used in fixing film is as phosphorus yield, and this technology accurately, fast, but be limited to expensive testing cost, current the method is not suitable for all laboratories.In the recent period, the DGT film method combined with Computer-generated images densitometry technology that develops the color is employed successfully in phosphorus in environment, sulphur, the species analysis such as iron, and the method can obtain high resolving power (micron order), the Two dimensional Distribution information of material in batches.
Based on fluorescence intensity, ratio fluorescent and fluorescence lifetime are quantitatively obtain the most frequently used method of material image information in planar light electrode system.Wherein, fluorescence intensity quantivative approach is that planar light electrode detection is the simplest, one of the most general method, but single fluorescence intensity quantitatively exists many impacts as factors such as optical path, bias light, photobleaching and light stability and interference.Fluorescence lifetime quantivative approach does not affect by sensing membrane self and external environmental interference, species distribution information that is more accurate and science can be provided, but the method relies on advanced person, accurate hardware and software equipment strongly, and therefore testing cost is higher, be unfavorable for the universal of this electrode.Compare with fluorescence lifetime quantivative approach with fluorescence intensity, the commercial digital camera that fluorescence intensity ratio rate quantivative approach mainly utilizes simply, be easy to get also significantly can cut down the intrinsic defect of conventional fluorescent quantification of intensities method, can realize material Two dimensional Distribution image acquisition of information accurately, fast.
Summary of the invention
The object of the present invention is to provide a kind of original position, the method that synchronous, high resolving power obtains SRP and DO Two dimensional Distribution in the matrix such as water body, sediment or soil.Described method monitors the DGT-PO composite membrane of active phosphorus and dissolved oxygen DO based on a kind of in-situ synchronization, film colour developing-computer density the imaging technique of a kind of improvement of main employing and RGB tri-color ratio rate quantitative technique, by DGT, PO binary channels, synchronous realization carries out in-situ monitoring to active phosphorus, dissolved oxygen DO in matrix.
Put it briefly, the present invention is based on a kind of in-situ synchronization monitoring active phosphorus and the DGT-PO functional composite membrane of dissolved oxygen DO, build a kind of " two stage assay " method and realize original position, the detection that synchronous, high resolving power obtains SRP and DO Two dimensional Distribution.The method is based on two kinds of up-to-date picture imaging techniques, i.e. fluoroscopic image acquiring technology and film colour developing-Computer-generated images densitometry technology, the first step is based on fluorescence analysis principle, adopt image technique Real-time Obtaining composite membrane at the DO fluorescence intensity image of the base contact such as sediment or soil interface PO layer, then second step carries out film colour developing by after this composite membrane process, and by the image that the SRP of Computer-generated images densitometry technical limit spacing DGT layer develops the color, then according to obtained image SRP and DO measured and detect.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of in-situ synchronization obtains water body, the method of active phosphorus (SRP) and dissolved oxygen DO (DO) Two dimensional Distribution in soil or sediment, it is characterized in that, insert in matrix after DGT-PO composite membrane is assembled into DGT device, described DGT-PO composite membrane comprises transparent supporting body, fluorescence sense layer and DGT fixed bed, described fluorescence sense layer is by fluorescent dye octaethylporphyrin platinum (PtOEP) and fluorescein 10-GN Homogeneous phase mixing, by chemistry embedding, two kinds of fluorescent dyes are fixed on transparent support surface to be formed, described DGT fixed bed adopts sub-micron ZrO particle to be fixing agent, polyurethane hydrogel is matrix, by coating method obtained DGT fixed bed on fluorescence sense layer, first adopt fluoroscopic image acquiring technology, under real-time acquisition 389nm shooting conditions, the fluoroscopic image of described DGT-PO composite membrane, after image software process, obtains the Two dimensional Distribution information of DO, then, treat that DGT fixed bed fully extracts active phosphorus extremely balance in matrix, pickling, film heating pretreatment is carried out after taking out DGT-PO composite membrane, pretreated DGT-PO composite membrane adds phosphorus developer and adopts molybdenum blue colorimetric method to carry out film colour developing, directly in the surface colour of DGT fixed bed, by obtaining the Two dimensional Distribution information of sediment SRP after Computer-generated images densitometry technique computes.
In described water body, soil or sediment SRP and DO Two dimensional Distribution detection method in, the concrete grammar of Two dimensional Distribution information obtaining DO comprises the steps:
(1) nitrogen and air is adopted to prepare the dissolved oxygen DO correcting fluid of one group of different saturated dissolved oxygen concentration, described DGT-PO composite membrane is placed in damping fluid, adopt the UV light source activation of 389nm, and the fluoroscopic image of fluorescence sense layer in this DGT-PO composite membrane under obtaining different saturated dissolved oxygen concentration conditions;
(2) fluoroscopic image is obtained in step (1), adopt image processing software that gained image is carried out the fractionation of R-G-B triple channel, obtain two kinds of fluorescence intensity images of two kinds of dyestuff PtOEP and fluorescein 10-GN redness corresponding respectively and blue channel, calculate two channel fluorescence intensity ratio R, and it is carried out curve fitting with corresponding dissolved oxygen concentration (DO value), obtain the PO layer of described DGT-PO composite membrane and fluorescence sense layer to DO value response curve, the PO layer fluorescence release characteristic of DGT-PO composite membrane is revised equation (formula 1) according to Stern-Volmer and is described:
R in formula
0, R is red channel and green channel fluorescence intensity ratio in absolute anaerobic condition (DO value=0), the corresponding fluoroscopic image of different DO values, and α is the dyestuff proportion that quencher reaction does not occur in this film, K
svfor this DGT-PO composite membrane is to the fluorescent quenching constant of DO, [C] is the concentration of DO in matrix.
(3) DO test: after the described DGT-PO composite membrane inserted in matrix is cleaned, fluoroscopic image is obtained according to the method identical with step (1), again according to the method identical with step (2), calculated the DO value of this some correspondence according to DO value response curve by the fluorescence intensity ratio R of each point on fluoroscopic image.
In described water body, soil or sediment SRP and DO Two dimensional Distribution detection method in, the detection of SRP Two dimensional Distribution is based on DGT fixed bed in this composite membrane, adopt molybdenum blue method colour developing and the Computer-generated images densitometry technology method that combines to obtain SRP Two dimensional Distribution information, concrete steps are as follows:
(1) described DGT-PO composite membrane is loaded in DGT device, then the phosphorous standard solution of one group of different concentration known is configured, the DGT device comprising described DGT-PO composite membrane is put into phosphorous standard solution to adsorption equilibrium, and each concentration at least comprises two parallel sample; Take out the DGT-PO composite membrane in DGT device, after a parallel sample is extracted with NaOH, measure DGT fixed bed Phosphate Sorption content with occluded corrosion cell;
(2) after another parallel sample is rinsed well, then pickling, film heating pretreatment is carried out, this diaphragm pretreated is put into the anti-nitrite ion of molybdenum antimony develop the color, with this film front of scanner scanning (DGT fixed bed surface), by image processing software, obtained image is changed into grey value profile image, the gray-scale value of DGT-PO composite membrane in same phosphorous standard solution and Phosphate Sorption content are fitted to calibration curve or regression equation;
(3) by after inserting in matrix the described DGT-PO composite membrane cleaning after extracting active phosphorus to balance, obtain grey value profile image according to the method identical with step (2), obtain DGT fixed bed Phosphate Sorption content according to obtained calibration curve or regression equation;
(4) Two dimensional Distribution of SRP on described DGT-PO composite membrane is calculated according to Fick First Law.
Carrying out pre-service to described DGT-PO composite membrane after it is pointed out that the Two dimensional Distribution information obtaining DO is adopt the inventive method synchronously to obtain SRP and DO Two dimensional Distribution necessary.For avoiding the radial diffusion of DGT layer appreciable impact DO in composite membrane in DGT-PO composite membrane, and ensure that composite membrane obtains the spatial synchrony of DO and SRP information, preparation DGT-PO composite membrane be only 150 ~ 200 μm thick, wherein only about 50 μm, DGT layer, cause this DGT-PO composite membrane to be easy to when DGT tests film rupture and phosphorus diffusion phenomena occur, preprocess method can effectively address these problems.Pre-service adopts pickling, film heating two-stage process, usually first carries out pickling in 24 hours with 0.1M dilute nitric acid solution, then with washed with de-ionized water totally after carry out film heating.
About DGT method obtains the concrete operations of SRP Two dimensional Distribution information, optimal conditions and computing method, can see the application for a patent for invention CN2013100772553 of applicant.
DGT-PO composite membrane described in the present invention adopts following methods preparation, first be by two kinds of fluorescence indicators different to oxygen sensitive, select the octaethylporphyrin platinum (PtOEP) sensitive to DO concentration-response respectively, and respond after insensitive fluorescein 10-GN dyestuff proportionally fully mixes, by chemical investment, mixed liquor is fixed on transparent supporting body uniformly, after air drying, forms the fluorescence sense layer (PO layer) of composite membrane; Then fix film preparation technique by DGT, adopt the polyurethane hydrogel of protic and gas penetration potential and sub-micron ZrO particle to make slurries, on PO layer, direct film forms DGT fixed bed; Final preparation becomes the ultra-thin composite membrane being similar to " sandwich " structure.
The preferred PET of described transparent supporting body (polyethylene terephthalate) film.The thickness of DGT-PO composite membrane is 150 ~ 200 μm.
In described composite membrane preparation process, in fluorescence sense layer, the weight ratio of PtOEP and fluorescein 10-GN is 0.05 ~ 1.5:1, preferred 1:1.In the present invention, PtOEP fluorescent dye being mixed as fluorescence indicator with the another kind of fluorescent dye-fluorescein 10-GN with reference effect and blast effect, by optimizing adding proportion, obtaining optimum signal intensity to characterize the height of DO value.Prepared by DGT fixed bed, film base material adopts polyurethane hydrogel (HY), it is become hydrogel mixed liquor (preferred 10:1 with alcohol, V:V), then it fully mixed with fixing agent sub-micron ZrO particulate slurry and carry out ultrasonic disperse, w/v is 0.1g ~ 1.0gZrO/1mL hydrogel mixed liquor, preferred 0.5gZrO/1mL hydrogel mixed liquor, then stir and spend the night, be prepared into fixed bed slurries after abundant mixing, be directly coated with the DGT fixed bed of film preparation composite membrane on PO layer surface.
The preparation of described sub-micron ZrO particulate slurry can see document Kreuzeder, A.; Santner, J.; Prohaska, T.; Wenzel, W.W., Gelforsimultaneouschemicalimagingofanionicandcationicsol utesusingdiffusivegradientsinthinfilms.Analyticalchemist ry2013,85, (24), 12028-36.
Applicant is based on DGT and PO know-why, a kind of NEW TYPE OF COMPOSITE functional material is successfully prepared by sedimentation film-forming method layer by layer, based on the DGT-PO complex function sensor film newly developed, the present invention is by improving DGT film colour developing-Computer-generated images densitometry technology and ratio fluorescent quantitative technique, in-situ synchronization can be realized and obtain Phosphorus Exchange at Sediment-water Interface-oxygen Two dimensional Distribution information, described method is simple and quick, and be particularly suited for the process of batch samples, cost is low.To water/sediment interface and sediment phosphorus-oxygen distribution and change, and the further investigation corresponding to interface various reaction type process, important information will be provided for micro-interface process and nutritive salt transform quantitative test.
Environmental matrices situ of the present invention synchronously obtains the rapid assay methods of the Two dimensional Distribution information of SRP and DO, has the following advantages:
(1) two kinds of image capture technology are relied on, rapid batch obtains system SRP and DO Two dimensional Distribution information, laser ablation-inductive coupling plasma mass spectrometry the coupling comparing traditional costliness measures or loaded down with trivial details film two dimension slicing-extraction-micro-developing technology monitoring technology, the SRP image acquiring method cost of this composite membrane is lower, and simply efficient; In addition, the dye formulation of this composite membrane PO inductive layer not only relies on a kind of indicator dye, but coordinate the use of fluorescein 10-GN dyestuff, under 389nm excitation, fluorescein 10-GN has very high fluorescent brightness, not only can strengthen the brightness of sensing membrane, but also can as the reference dye of DO, various external interference is eliminated, more accurate acquisition DO Two dimensional Distribution information based on ratio fluorescent quantitative technique.
(2) this composite membrane DGT layer adopts ultra-fine ZrO sorbing material, adsorption capacity about 12.3 μ g/cm
2, higher than traditional Fe film (about 1.36 μ g/cm
2), higher adsorption capacity, has widened the scope of application of DGT technology; In addition, the PO inductive layer of this composite membrane is very wide to the responding range of DO: 0 ~ 100% air saturation.
(3) high spatial resolution, utilizes image capture technology can obtain micron order spatial resolution SRP and DO distributed intelligence.
Accompanying drawing explanation
The structural representation of Fig. 1 .DGT-PO composite membrane.
The SEM image of the ultra-fine ZrO particle in Fig. 2 .DGT-PO composite membrane DGT fixed bed surface.
Fig. 3 .DGT-PO composite membrane DGT fixed bed adsorption capacity curve.
Fig. 4. pickling-wash and phosphorous recovery impact is fixed on DGT-PO composite membrane.
Calibration curve under the different developing time of Fig. 5 .DGT-PO composite membrane between Phosphate Sorption and gray-scale value.
Fig. 6 .DGT-PO composite membrane PO inductive layer response effect and DO typical curve.
Fig. 7 .DGT-PO composite membrane is response time of (0% and 100%) and reproducibility under different dissolved oxygen condition.
Fig. 8. the Two dimensional Distribution variation characteristic of DO and SRP under aerobic and anaerobic conditions; Under wherein A, B represent aerobic condition respectively, DO and SRP distributes, and under C, D represent anaerobic condition respectively, DO and SRP distributes, and dimension of picture is 50mm × 70mm.
Embodiment
Embodiment 1
The in-situ synchronization monitoring active phosphorus that the present invention adopts and the DGT-PO composite membrane of dissolved oxygen DO, its preparation adopts following methods:
(1) 10mg is got respectively, 10mg, the PtOEP dyestuff of 500mg, fluorescein 10-GN dyestuff and polyethylene particle, be dissolved in the toluene of 10mL, after ultrasonic dissolution, get 200 μ L mixed liquors, adopt the method for 100 μm of knifing to be evenly coated in by this mixed liquor on transparent PET film base material, after drying at room temperature 30min, form the fluorescence sense layer (PO) of composite membrane; Being placed on dark place lucifuge sealing preserves stand-by.
(2) method described by Kreuzeder, A etc. prepares sub-micron ZrO ultra-fine grain slurries; Take the ultra-fine grain slurries comprising 8.0gZrO, then with polyurethane hydrogel HYD4 (polyurethanehydrogel, typeD4, purchased from American AdvanSourceBiomaterials company) with the mixed liquor (10:1 of alcohol, V:V) 16mL mixing, after adopting Ultrasonic Cell Disruptor process 20min, magnetic stirring apparatus fully stirs and spends the night, be prepared into fixed bed slurries; Be placed in Keep agitation on magnetic stirring apparatus for subsequent use.
(3) on the fluorescence sense layer (PO) prepared in step (1), paste the filling pad of 500 μm of thickness, get fixed bed slurries obtained in 5mL above-mentioned steps (2), in this U-type groove, adopt glass bar to carry out painting film preparation DGT fixed bed.Room temperature leaves standstill composite membrane after 1 day and has prepared, and is placed on dark place lucifuge sealing and preserves.
Obtained DGT-PO composite membrane has " sandwich " structure (Fig. 1), the SEM image on DGT fixed bed surface is as Fig. 2, its surperficial ultra-fine ZrO uniform particles, particle diameter <0.5 μm, fixes peplomer footpath (5 μm) than traditional ZrO and significantly reduces.
Embodiment 2
DGT-PO composite membrane is to phosphorus fixation volume test, and concrete steps are as follows:
(1) adopt ring stainless steel cutter to carry out cut into slices (diameter 2.0cm) the DGT-PO composite membrane prepared, obtain disk, be put in deionized water, purity nitrogen inflates 12 hours, gets rid of the oxygen in film, for subsequent use.
(2) the DGT-PO composite membrane prepared is assembled in piston type DGT device, then the device assembled is put in denitrification, ultrapure water aquation at least 4 hours, for subsequent use.
(3) the DGT device assembled in step (2) is put into 8 kinds of different phosphate-containing concentration mother liquor (0.001mgP/L ~ 20mgP/L, pH=7.0 ± 0.2 of 0.5 ~ 10mg/L; 0.03MNaCl), carry out 6h absorption, often organize 3 Duplicate Samples.
(4) upon adsorption complete after, take out DGT device, reclaim composite membrane, then carry out 24h fully extract with putting into 5mL1.0MNaOH solution after ultrapure water, then adopt microcolorimetry to measure phosphorus concentration in extract.
(5) calculate composite membrane disk effective unit area according to concentration measured in (4) and fix phosphorus content, then ask according to DGT principle and calculate theoretical fixing phosphorus average content, draw theoretical value and actual value curve, obtain result as shown in Figure 3, result shows that the capacity that this film fixes phosphorus is 12.34 μ gP/cm
2, far above the solid phosphorus content (1.8 ~ 9.0 times) of used iron film.
Embodiment 3
DGT-PO composite membrane pickling-heating pretreatment fixes the organic efficiency impact of phosphorus to composite membrane, carries out according to following steps:
(1) DGT-PO composite membrane embodiment 1 prepared, after abundant aquation 4h, adopts radius 1cm stainless steel circular shear blade to cut into slices, then carries out the assembling of piston type DGT device.
(2) the DGT device assembled in (1) is put into different phosphate-containing mother liquor (pH=7.0 ± 0.2; 0.03MNaCl)), after having adsorbed, DGT-PO composite membrane in the device of recovery is carried out respectively pickling (0.1M dust technology) 24h and washing 4h, 1.0MNaOH extraction is carried out after heating, other one group directly adopts 1.0MNaOH to extract, and what two groups of process recorded phosphorus the results are shown in Figure 4.Result shows pickling, washing and heating to the phosphorous recovery in composite membrane between (96.50 ± 0.26) % and (103.92 ± 1.91) %, illustrates that pickling and heating pretreatment can not cause active phosphorus to run off above composite membrane.
Embodiment 4
Calibration curve between DGT-PO composite membrane DGT fixed bed Phosphate Sorption and gray-scale value, set up according to following steps:
(1) the DGT-PO composite membrane will prepared, to be put in denitrification, ultrapure water aquation at least 4 hours, for subsequent use.
(2) the DGT-PO composite membrane after step (1) process, adopts the stainless steel round cutter of radius 1cm to carry out cutting film, obtains the composite membrane disk of radius 1cm, by gained composite membrane disk, be assembled into DGT device after 0.45 μm of filter membrane superposes successively.
(3) gained DGT device in step (2) put into deionized water and carry out 12h and fill nitrogen and remove oxygen (getting rid of DO to the impact of PO layer).
(4) 0.05,0.1,0.2 is configured, 0.25,0.3,0.5,1.0,2.0,3.0, the phosphorous mother liquor (each 2mL) of the variable concentrations of 4.0,6.0,10.0mg/L, the DGT device after process in 6 steps (3) is placed respectively in each mother liquor, respectively after absorption certain hour (4 ~ 12 hours), the compound film sheet in withdrawing device, the NaOH wherein getting 3 composite membrane disk 1M extracts, and measures Phosphate Sorption content, other three for subsequent use.
(5) rinsed well by composite membrane for subsequent use, according to pickling (0.1M dust technology), electric hot plate heats two steps and carries out pre-service.To be heated finish after, to treat that colour developing diaphragm is put into the anti-nitrite ion of molybdenum antimony and developed the color according to 45min developing time respectively, then after clean by cold water flush, surface moisture is blotted gently with filter paper, with this film front of scanner scanning, by image processing software, change into grey value profile image, the gray-scale value of DGT-PO composite membrane in same phosphorous mother liquor and Phosphate Sorption content are fitted to calibration curve or regression equation.
(6) 2 groups of experiments are carried out according to repetition step (4), obtain and treat that colour developing diaphragm develops the color according to step (5) respectively, developing time is respectively 60min and 90min, matching obtains composite membrane gray scale-adsorption capacity relation curve under obtaining different developing time condition respectively, as shown in Figure 5.
Result shows, the gray-scale value that developing time 45min and 60min obtains is low compared to 90min developing time discreteness, and the gray-scale value that the developing time of 60min compares 45min colour developing curve corresponding is sensitiveer to phosphorus content, therefore the preferred developing time of the inventive method is set as 60min, and the calibration curve correspondingly between the Phosphate Sorption that obtains of 60min developing time and gray-scale value is as typical curve.
Embodiment 5
DGT-PO composite membrane DGT layer is tested the impact of PO layer response curve, is undertaken by following concrete steps:
(1) the PO film without DGT layer is obtained by step (1) in embodiment 1, and the DGT-PO composite membrane prepared, be put in deionized water, purity nitrogen inflates 12 hours, gets rid of the oxygen in film.
(2) two kinds of diaphragms after step (1) being processed to be attached to inside quartz glass box in one side, supporter one side directly contacts with quartzy face, then on diaphragm, cover the ultra-thin filter membrane of one deck polycarbonate, and adopt adhesive waterproof tape to be fixed by filter membrane, add simulation lake water solution (pH=7.0 ± 0.2 in box; 0.03MNaCl).
(3) ultrapure nitrogen and the air of different proportion is passed into, aqueous solution is regulated to be saturated dissolved oxygen concentration (0% ~ 100% saturated dissolved oxygen), adopt the UV light source activation of 389nm, and the fluoroscopic image of sense film in these two kinds of PO films and DGT-PO composite membrane under obtaining different saturated dissolved oxygen concentration conditions.
(4) fluorescence picture is obtained in step (3), adopt image processing software ImageJ1.46, carry out the fractionation of R-G-B triple channel, obtain two kinds of dyestuff PtOEP and fluorescein 10-GN redness corresponding respectively and blue channel, calculate two channel fluorescence intensity ratio R, and it is carried out curve fitting with corresponding dissolved oxygen concentration (DO value), to obtain in described PO film and DGT-PO composite membrane PO fluorescence sense film to DO value response curve, fluorescence sense film fluorescence release characteristic can be revised equation (formula 1) according to Stern-Volmer and describe:
R in formula
0, R is red channel and green channel fluorescence intensity ratio in absolute anaerobic condition, the corresponding fluoroscopic image of different DO values, and α is the dyestuff proportion that quencher reaction does not occur in this film, K
svfor this sense film is to the fluorescent quenching constant of DO, [C] is the concentration of DO in matrix.
Institute's result that obtains as shown in Figure 6.Result shows, two kinds of fluorescence sense films all present index variation to DO response, calculate the two kinds of films obtained and be distributed as 1.95 and 2.12 to DO response sensitivity, confirm the impact that the existence of DGT layer in composite membrane is less, this impact can be eliminated by three point calibrations.
The response curve of further matching DGT-PO composite membrane, can obtain equation (2), is used for calculating DO value.
Embodiment 6
DGT-PO composite membrane PO layer response time and reproduction performance, test according to following steps:
(1) by after the abundant aquation 4h of DGT-PO composite membrane for preparing, adopt Stupalox to be cut into 50mm × 50mm film, according to step (2) in embodiment 5, this diaphragm is pasted onto quartz glass box inwall (50mm × 50mm × 10mm).
(2) by regulating pure nitrogen gas and air mixture ratio, in rate-determining steps (1), in quartz glass box, the saturated dissolved oxygen amount of solution is changed between 100% and 0%, and temperature controls at 20 DEG C, and ionic strength is 0.03MNaCl, pH is 7.0 ± 0.2.
(3) take pictures at interval of 2s, carry out data processing according to step (4) in embodiment 5 after obtaining fluoroscopic image, result as shown in Figure 7.Result shows, this DGT-PO composite membrane has good repeatability to DO induction, and when DO is from 100% to 0% conversion, this film response signal arrives 95% highest signal time (t
95) be 24s, and when DO changes from 0% to 100%, this film response signal arrives minimum stable signal time <3s.
Embodiment 7
Obtain the Two dimensional Distribution of active phosphorus (SRP) and dissolved oxygen DO (DO) in sediment based on DGT-PO composite membrane in-situ synchronization, step is as follows:
(1) the DGT-PO composite membrane will prepared, to be put in denitrification, ultrapure water aquation at least 4 hours, for subsequent use.
(2) Taihu Lake Sediment sample and water sample is gathered, take back laboratory for subsequent use, the sediment be collected is carried out mixing of sieving, water sample is put in two incubators after filtering respectively, keep sediment depth 15cm, overlying water degree of depth 25cm, then regulate air and nitrogen ratios to blast mixed gas to two groups of devices, carry out lasting aeration 2 weeks, build aerobic and anaerobic conditions respectively.
(3) adopt waterproof to drop to composite membrane in step (1) and be tightly pasted onto (50mm × 100mm × 150mm) in the quartz glass case of both ends open.Then the ultra-thin polycarbonate leaching film (ventilative, saturating ion) of 10 μm of thickness is attached to above composite membrane, as diaphragm.
(4) when testing, the glass box posting composite membrane is directly vertically inserted in cultured sediment, wash with the sediment of clear water by glass box periphery, and fix sediment move to darkroom with side's plug base, adopt fluoroscopic image to obtain system and test.
(5) in sediment, DO distributed intelligence, by Real-time Obtaining observation section fluoroscopic image, calculates or can obtain after drawing the DO two dimension DYNAMIC DISTRIBUTION of water/sediment interface according to embodiment 5 step (4).
(6) after having obtained DO fluoroscopic image, composite membrane is taken out, after fully cleaning with deionized water, carry out pre-service, pickling (0.1M dust technology) 24h after washing, 80 DEG C of heater plate are fixed, and then film are put into phosphorus nitrite ion and carry out molybdenum blue colour developing and scanning, carry out concentration calculating according to gray scale-adsorbance typical curve that embodiment 4 step (6) is set up.
In sediment, the measurement result of the Two dimensional Distribution of SRP and DO as shown in Figure 8.
Claims (7)
1. an in-situ synchronization obtains water body, the method of active phosphorus SRP and dissolved oxygen DO DO Two dimensional Distribution in soil or sediment, it is characterized in that, insert in matrix after DGT-PO composite membrane is assembled into DGT device, described DGT-PO composite membrane comprises transparent supporting body, fluorescence sense layer and DGT fixed bed, described fluorescence sense layer is by fluorescent dye octaethylporphyrin platinum and fluorescein 10-GN Homogeneous phase mixing, by chemistry embedding, two kinds of fluorescent dyes are fixed on transparent support surface to be formed, described DGT fixed bed adopts sub-micron ZrO particle to be fixing agent, polyurethane hydrogel is matrix, by coating method obtained DGT fixed bed on fluorescence sense layer, first adopt fluoroscopic image acquiring technology, under real-time acquisition 389nm shooting conditions, the fluoroscopic image of described DGT-PO composite membrane, after image software process, obtains the Two dimensional Distribution information of DO, then, treat that DGT fixed bed fully extracts active phosphorus extremely balance in matrix, pickling, film heating pretreatment is carried out after taking out DGT-PO composite membrane, pretreated DGT-PO composite membrane adds phosphorus developer and adopts molybdenum blue colorimetric method to carry out film colour developing, directly in the surface colour of DGT fixed bed, by obtaining the Two dimensional Distribution information of sediment SRP after Computer-generated images densitometry technique computes.
2. in-situ synchronization according to claim 1 obtains the method for active phosphorus SRP and dissolved oxygen DO DO Two dimensional Distribution in water body, soil or sediment, it is characterized in that, the method obtaining the Two dimensional Distribution information of DO comprises the steps:
(1) nitrogen and air is adopted to prepare the dissolved oxygen DO correcting fluid of one group of different saturated dissolved oxygen concentration, described DGT-PO composite membrane is placed in damping fluid, adopt the UV light source activation of 389nm, and the fluoroscopic image of fluorescence sense layer in this DGT-PO composite membrane under obtaining different saturated dissolved oxygen concentration conditions;
(2) fluoroscopic image is obtained in step (1), adopt image processing software that gained image is carried out the fractionation of R-G-B triple channel, obtain two kinds of fluorescence intensity images of two kinds of dyestuff PtOEP and fluorescein 10-GN redness corresponding respectively and blue channel, calculate two channel fluorescence intensity ratio R, and it is carried out curve fitting with corresponding DO value, obtain the PO layer of described DGT-PO composite membrane to DO value response curve, the PO layer fluorescence release characteristic of DGT-PO composite membrane is revised equation (formula 1) according to Stern-Volmer and is described:
R in formula
0, R is red channel and green channel fluorescence intensity ratio in absolute anaerobic condition, the corresponding fluoroscopic image of different DO values, and α is the dyestuff proportion that quencher reaction does not occur in this film, K
svfor this DGT-PO composite membrane is to the fluorescent quenching constant of DO, [C] is the concentration of DO in matrix;
(3) DO test: after the described DGT-PO composite membrane inserted in matrix is cleaned, fluoroscopic image is obtained according to the method identical with step (1), again according to the method identical with step (2), calculated the DO value of this some correspondence according to DO value response curve by the fluorescence intensity ratio R of each point on fluoroscopic image.
3. in-situ synchronization according to claim 1 obtains the method for active phosphorus SRP and dissolved oxygen DO DO Two dimensional Distribution in water body, soil or sediment, it is characterized in that, the method obtaining the Two dimensional Distribution information of SRP comprises the steps:
(1) described DGT-PO composite membrane is loaded in DGT device, then the phosphorous standard solution of one group of different concentration known is configured, the DGT device comprising described DGT-PO composite membrane is put into phosphorous standard solution to adsorption equilibrium, and each concentration at least comprises two parallel sample; Take out the DGT-PO composite membrane in DGT device, after a parallel sample is extracted with NaOH, measure DGT fixed bed Phosphate Sorption content with occluded corrosion cell;
(2) after another parallel sample is rinsed well, then pickling, film heating pretreatment is carried out, this diaphragm pretreated is put into the anti-nitrite ion of molybdenum antimony develop the color, with scanner scanning DGT fixed bed surface, by image processing software, obtained image is changed into grey value profile image, the gray-scale value of DGT-PO composite membrane in same phosphorous standard solution and Phosphate Sorption content are fitted to calibration curve or regression equation;
(3) by after inserting in matrix the described DGT-PO composite membrane cleaning after extracting active phosphorus to balance, obtain grey value profile image according to the method identical with step (2), obtain DGT fixed bed Phosphate Sorption content according to obtained calibration curve or regression equation;
(4) Two dimensional Distribution of SRP on described DGT-PO composite membrane is calculated according to Fick First Law.
4. the in-situ synchronization according to claim 1,2 or 3 obtains the method for active phosphorus SRP and dissolved oxygen DO DO Two dimensional Distribution in water body, soil or sediment, it is characterized in that, described DGT-PO composite membrane adopts following methods preparation, first after selecting octaethylporphyrin platinum and fluorescent yellow dye 10-GN proportionally fully to mix, by chemical investment, mixed liquor is fixed on transparent supporting body uniformly, after air drying, forms the fluorescence sense layer of composite membrane; Then fix film preparation technique by DGT, adopt polyurethane hydrogel and sub-micron ZrO particle to make slurries, on fluorescence sense layer, direct film forms DGT fixed bed, obtained described DGT-PO composite membrane.
5. in-situ synchronization according to claim 4 obtains the method for active phosphorus SRP and dissolved oxygen DO DO Two dimensional Distribution in water body, soil or sediment, it is characterized in that, the thickness of described DGT-PO composite membrane is 150 ~ 200 μm, and transparent supporting body is pet film.
6. in-situ synchronization according to claim 4 obtains the method for active phosphorus SRP and dissolved oxygen DO DO Two dimensional Distribution in water body, soil or sediment, and it is characterized in that, in fluorescence sense layer, the weight ratio of PtOEP and fluorescein 10-GN is 0.05 ~ 1.5:1.
7. in-situ synchronization according to claim 4 obtains the method for active phosphorus SRP and dissolved oxygen DO DO Two dimensional Distribution in water body, soil or sediment, it is characterized in that, described slurries by weight volume ratio are sub-micron ZrO: polyurethane hydrogel alcohol blend 0.1g ~ 1.0g/1mL is obtained by mixing.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105973886A (en) * | 2016-05-30 | 2016-09-28 | 田发益 | Method and device for determining concentration value based on visible light spectrum |
| CN106092992A (en) * | 2016-07-13 | 2016-11-09 | 苏州普兰塔环境科技有限公司 | A kind of oxygen in soil Two dimensional Distribution measurement apparatus |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995008107A1 (en) * | 1993-09-13 | 1995-03-23 | Optical Sensors Incorporated | A ratiometric fluorescence method to measure oxygen |
| US20100279428A1 (en) * | 2009-04-29 | 2010-11-04 | Industry Foundation Of Chonnam National University | OPTICAL SENSING MEMBRANES, DEVICES AND METHODS FOR SIMULTANEOUS DETECTION OF TWO OR MORE PARAMETERS OF DISSOLVED OXYGEN CONCENTRATION, pH AND TEMPERATURE |
| CN104048924A (en) * | 2013-03-12 | 2014-09-17 | 中国科学院南京地理与湖泊研究所 | Two-dimensional high-resolution method for determination of distribution of active phosphorus in wetland soil and deposit |
-
2015
- 2015-12-15 CN CN201510940840.0A patent/CN105548106B/en active Active
- 2015-12-15 CN CN201510940485.7A patent/CN105466899B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995008107A1 (en) * | 1993-09-13 | 1995-03-23 | Optical Sensors Incorporated | A ratiometric fluorescence method to measure oxygen |
| US20100279428A1 (en) * | 2009-04-29 | 2010-11-04 | Industry Foundation Of Chonnam National University | OPTICAL SENSING MEMBRANES, DEVICES AND METHODS FOR SIMULTANEOUS DETECTION OF TWO OR MORE PARAMETERS OF DISSOLVED OXYGEN CONCENTRATION, pH AND TEMPERATURE |
| CN104048924A (en) * | 2013-03-12 | 2014-09-17 | 中国科学院南京地理与湖泊研究所 | Two-dimensional high-resolution method for determination of distribution of active phosphorus in wetland soil and deposit |
Non-Patent Citations (2)
| Title |
|---|
| CHAOSHENG ZHANG ET AL.: "Bioavailability assessment of phosphorous and metals in soils and sediments:A review of diffusive gradients in thin films（DGT）", 《ENVIRON MOINT ASSESS》 * |
| 李栋 等: "生物扰动下海底沉积物-水界面溶解氧二维观测方法", 《海洋科学》 * |
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| CN106092992B (en) * | 2016-07-13 | 2019-04-19 | 王亮 | A kind of oxygen in soil Two dimensional Distribution measuring device |
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