CN102507388A - Improved phosphorus fixing film used in DGT (diffusive gradients in thin films) measurement and preparation method thereof - Google Patents

Improved phosphorus fixing film used in DGT (diffusive gradients in thin films) measurement and preparation method thereof Download PDF

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CN102507388A
CN102507388A CN2011103256158A CN201110325615A CN102507388A CN 102507388 A CN102507388 A CN 102507388A CN 2011103256158 A CN2011103256158 A CN 2011103256158A CN 201110325615 A CN201110325615 A CN 201110325615A CN 102507388 A CN102507388 A CN 102507388A
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孙琴
丁士明
许笛
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Hohai University HHU
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Abstract

一种薄膜扩散梯度测定中的改进型磷固定膜,系包含ZrO2的聚丙烯酰胺凝胶膜,其特征在于:所述的磷固定膜表面均匀分布粒径≤5μm的二氧化锆颗粒。改进型磷固定膜的制备方法是:将含水率45-55%二氧化锆粉末和丙烯酰胺溶液按重量体积比1:3~1:6混匀,研磨后超声破碎,静置除去沉淀物后,加入丙烯酰胺体积1/1600~1/1400的四甲基二乙胺和1/60~1/40的10%过硫酸铵溶液,混合均匀后注入玻璃模具中,室温以下水平放置,待锆粉自由沉降后,升温至40~60℃,至混合液形成凝胶膜,去离子水浸泡12小时以上制得。本发明的磷固定膜保持磷离子高吸附容量的同时,可显著提高DGT在磷分析中的分辨率。

Figure 201110325615

An improved phosphorus immobilized membrane in thin film diffusion gradient measurement is a polyacrylamide gel membrane containing ZrO 2 . The preparation method of the improved phosphorus immobilized film is: mix the zirconium dioxide powder with a moisture content of 45-55% and the acrylamide solution at a weight volume ratio of 1:3 to 1:6, grind, ultrasonically break, and stand to remove the sediment , add tetramethyldiethylamine of 1/1600~1/1400 volume of acrylamide and 10% ammonium persulfate solution of 1/60~1/40, mix evenly and pour into glass mold, place it horizontally below room temperature, wait for zirconium After the powder settles freely, heat up to 40-60°C until the mixture forms a gel film, and soak in deionized water for more than 12 hours. The phosphorus immobilized membrane of the invention can significantly improve the resolution of DGT in phosphorus analysis while maintaining the high adsorption capacity of phosphorus ions.

Figure 201110325615

Description

Modified phosphorus fixing film in a kind of diffusive gradients in thin-films measurement and preparation method thereof
Technical field
The present invention relates to be applied to diffusive gradients in thin-films (Diffusive gradients in thin films in the A+E of surrounding mediums such as a kind of soil, sediment; DGT) fixedly film and preparation method thereof of determination techniques, especially a kind of diffusive gradients in thin-films measurement technology that is applicable to is analyzed modified phosphorus fixing film of sediment phosphorus and preparation method thereof.
Background technology
Phosphorus is the important nutrient of hydrobiont growth, also is the major limitation sex factor of lake primary productivity and body eutrophication.After external source phosphorus got into water body in lake, major part accumulated in sediment, and discharges into overlying water again under certain condition, keeps the eutrophic state of water body.The release potentiality of sediment phosphorus and its confidential relation that is distributed with at sediment-water micro-interface.Usually, because the sediment-greatest differences of water micro-interface on physics, chemistry and biological property causes phosphorus possibly exist strong concentration gradient to distribute at this near interface, drive phosphorus thus and between sediment and overlying water, exchange.Obtaining the distributed intelligence of phosphorus between sediment-water micro-interface, is the important evidence of estimating the sediment phosphorus activity and discharging to water body.Routine is obtained the resolution of technology below 1mm, can not satisfy the analysis requirement of micro-interface phosphorus on submillimeter level resolution.
(Diffusive gradients in thin films, DGT) determination techniques is that a kind of non-destructive, original position are obtained pollutant distribution and active new technology in the sediment to diffusive gradients in thin-films.This technique device is mainly formed (Fig. 1) by the stack of fixedly film and diffusion barrier, and both form by the gel configuration, and wherein fixedly film disposes through the fixing agent that adds ability absorb polluted matter ion to gel and forms.When the DGT device is put into sediment; Contaminant ion passes diffusion barrier with diffusion way; The film that is fixed is immediately caught; And the formation linear gradient distributes on diffusion barrier; Diffusion barrier contacts an end with fixing film ion concentration is maintained zero, and the concentration (
Figure 153188DEST_PATH_IMAGE002
) that contacts an end with medium is:
Figure 713482DEST_PATH_IMAGE003
In the following formula MBe the accumulation (μ g) of object ion on the fixing film,
Figure 48911DEST_PATH_IMAGE005
Be thickness of diffusion layer (cm),
Figure 61866DEST_PATH_IMAGE007
Be the rate of diffusion (cm of ion in diffusion barrier 2/ s), Be the fixing area (cm of film 2),
Figure 985271DEST_PATH_IMAGE011
Be diffusion time (s),
Figure 678552DEST_PATH_IMAGE002
Promptly be the content (10 of analyzing the sediment intermediate ion that obtains through DGT 3μ g/L).
High-resolution obtains that the pollutant space distribution information is one of emphasis of DGT technical development in recent years in the sediment.The high resolution analysis that satisfies DGT requires (spatial resolution < 0.5mm), and fixedly the fixing agent size distribution on film surface is one of its influence factor.Current fixing agent commonly used (like Chelex 100) particle diameter can not satisfy the high resolution analysis requirement of DGT all greater than 0.05mm.
" a kind of phosphorus fixing film that is applied to the diffusive gradients in thin-films measurement technology device " (ZL 200910183047.5) have disclosed a kind of phosphorus fixing film that is applied to the diffusive gradients in thin-films technology and preparation method thereof; This phosphorus fixed film has very high adsorption capacity to phosphonium ion; Having overcome in the existing DGT technology fixedly, film has enlarged the application of DGT in phosphorus such as soil, sediment are analyzed to the deficiency of phosphorus fixed capacity.But fixedly film surface fixing agent particle is bigger, and skewness can't satisfy the high resolution analysis requirement of DGT to sediment phosphorus.
Summary of the invention
The object of the invention provides a kind of modified phosphorus fixing film that is applied to diffusive gradients in thin-films (DGT) technology and preparation method thereof; Phosphorus fixing film of the present invention not only keeps the high-adsorption-capacity to phosphonium ion; Can significantly improve simultaneously the resolution of DGT in phosphorus is analyzed, satisfy the requirement of DGT the high resolution analysis of sediment phosphorus.
Above-mentioned purpose of the present invention realizes through following technical scheme:
Modified phosphorus fixing film in a kind of diffusive gradients in thin-films measurement is to comprise ZrO 2The polyacrylamide gel film, it is characterized in that: described phosphorus fixing film surface is the zirconium dioxide particle of distribution particle diameter≤5 μ m evenly.
Described modified phosphorus fixing film adopts following method preparation:
The preparation method of the modified phosphorus fixing film in a kind of diffusive gradients in thin-films measurement is that Zirconium dioxide powder and the acrylamide solution of 45-55% is by 1:3~1:6 (w/v, g/ml) mixing with water percentage; Grind the back ultrasonication, leave standstill remove sediment after, add the tetramethyl diethylamine (TEMED) of acrylamide solution volume 1/1600~1/1400 and 10% (wt) ammonium persulfate solution of 1/60 ~ 1/40; After mixing mixed liquor is injected glass mold, the following horizontal positioned of room temperature, treat zirconium powder free setting after; Be warming up to 40~60 ℃; Form gel mould until mixed liquor, in deionized water, soak more than 12 hours the phosphorus fixing film that is improved.
In theory, when the spatial resolution of analyzing as DGT was confirmed as 0.5mm, the fixing agent particle diameter at least should < 0.05mm can be controlled at the excessive analytical error that causes of fixing agent particle diameter in 10%; < during 0.01mm, analytical error then can be controlled in 2% when the fixing agent particle diameter.But, consider also there are other errors in the DGT analytic process that the actual fixedly peplomer footpath that requires should be much smaller than theoretical value.The inventive method makes the modified phosphorus fixing film (Fig. 2 b) of surperficial zirconium dioxide particle particle diameter≤5 μ m through measures such as grindings, ultrasonication, the high-adsorption-capacity of phosphonium ion not only, and be applied to the analysis of DGT phosphorus, resolution can reach below the 0.2mm.
Described Zirconium dioxide powder is by 1:15~1:30 (w/v by zirconium oxychloride and deionized water; G/ml) mixed dissolution; Use ammoniacal liquor regulator solution pH then between 6.9-7.1, after the precipitate with deionized water that is produced is washed, dry and to control its water percentage be between 45~55%.
The w/v of described Zirconium dioxide powder and acrylamide solution is preferably 1:4~1:6.
The WS of preferred 25~35 wt% acrylic amides of described acrylamide solution wherein comprises 0~5.0 wt % Methacrylamide.
Polyacrylamide gel is the improvement of film properties fixedly, except that fixing agent is carried out the fragmentation, need fixedly be optimized accent on the membrane preparation method simultaneously.The present invention optimizes the addition of Zirconium dioxide powder, acrylamide solution and proportioning thereof and crosslinking chemical TEMED and catalyzer ammonium persulfate; And to preparation method's improvement; Make not only after the film forming that fixedly film surface zirconium dioxide particle is evenly distributed; And zirconium dioxide and third rare acid amides mixed liquor can very successfully inject glass mold, and film formation time also shortened to 1.5 hours by former average 3 hours.ZL 200910183047.5 uses 80% ethanol to zirconium dioxide sediment rinsing 1 ~ 2 time, to impel zirconium dioxide sediment fast dewatering when the preparation phosphorus fixing film; It is thick very easily to become sticky after the zirconium dioxide that this method prepares and third rare acid amides mixed liquor are ultrasonic, makes mixed solution can not inject glass mold smoothly.Therefore when the preparation Zirconium dioxide powder, the present invention does not adopt the ethanol rinsing, only adopts the method for washing.Prepared fixedly film has very excellent physical strength, and retractility is extremely low, can be used for the DGT technical operation more easily.
Advantage of the present invention and beneficial effect comprise:
(1) compares with existing phosphorus fixing film (ZL 200910183047.5); The outstanding advantage of modified phosphorus fixing film of the present invention is through measures such as grinding and ultrasonications the zirconium dioxide particle diameter to be controlled; Reduced the particle diameter of film surface zirconium dioxide fixing agent significantly; Particle diameter is reduced in the 5 μ m from about 30 μ m, makes zirconium dioxide particle at fixing film surface distributed even compact (Fig. 2), has higher phosphorus adsorption capacity; Improved the resolution that DGT phosphorus is analyzed simultaneously, therefore fixedly film can satisfy the high resolution analysis requirement of DGT technology to sediment phosphorus fully.Prepared fixedly film also has very excellent physical strength, and retractility is extremely low, can be used for the DGT technical operation more easily.
(2) compare with the other types phosphorus fixing film of report, modified phosphorus fixing film of the present invention continues the DGT capacity (> that keeping very high; 100 μ g P cm -2) (Fig. 3), be respectively traditional F eO film, modified FeO film and Metsorb film 50 times, more than 14 times and 8 times.Owing to this advantage, can the DGT device of modified phosphorus fixing film assembling be used to analyze the eutrophic lake of high phosphorus background.
(3) modified of the present invention fixedly film have very large development space at DGT high resolution analysis technical elements; Outstanding behaviours exists: combine to process composite membrane with other particulate footpath fixing agents, can realize synchronous, the high-resolution DGT of the different contaminant ions of sediment are analyzed.As add the AgI particle simultaneously, DGT technology capable of using to the phosphorus in the sediment, sulphur plasma carry out synchronously, high resolution analysis; Add SPR-IDA resin fixing agent, can realize synchronous, the high resolution analysis of phosphorus, heavy metal.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with embodiment, but is limited claim.
Description of drawings
Fig. 1 is a DGT device synoptic diagram.
Fig. 2 Fig. 2 a and Fig. 2 b are the phosphorus fixing film (a) of disclosure among the ZL 200910183047.5 and the electron-microscope scanning image of modified phosphorus fixing film of the present invention (b).Can find out through both contrasts, the densification that is evenly distributed of modified phosphorus fixing film of the present invention surface zirconium dioxide particle, particle diameter≤5 μ m, and phosphorus fixing film rough surface before improving, particle diameter is about 30 μ m.
Fig. 3 is the standing time of DGT device in phosphorus solution and the graph of a relation of phosphorus accumulation of modified phosphorus fixing film assembling of the present invention.The figure cathetus is a theoretical value, can find out the DGT Rong Liang > of modified phosphorus fixing film through contrast; 100 μ g P cm -2
 
Embodiment
Embodiment 1
Modified phosphorus fixing film in a kind of diffusive gradients in thin-films measurement, its preparation method is following:
The zirconium oxychloride that takes by weighing 25g is dissolved in the 600ml deionized water; Use the ammoniacal liquor of 25% (volume ratio) that pH value of solution is regulated and is stabilized between the 6.9-7.1 then; The precipitate with deionized water that is produced is washed 8-9 time, with hair-dryer its water percentage is dried up between 45~55% at last.By mass volume ratio 1:4 Zirconium dioxide powder and the 7.2ml acrylamide solution (WS of 28.5% acrylic amide and 1.5% Methacrylamide) that 1.8g prepares mixed, ground 10~30 minutes, used clasmatosis appearance 20% frequency more ultrasonic 5~15 minutes with agate mortar; Left standstill 10~30 minutes, remove sediment after, in solution, add the tetramethyl diethylamine (TEMED) of 4.5 μ L and the ammonium persulfate solution (mass ratio 10%) of 180 μ L successively; Then solution is slowly injected the two glass sheets spaces that accompany the U-shaped plastic tab, catch up with bubble to the greatest extent after, glass plate horizontal positioned half an hour under 10 ℃ of low temperature; After treating zirconium powder free setting; Be warming up to 45 ℃, placed 1 hour, make the solution gel film forming; Glass plate after the film forming is put into deionized water to be soaked 24 hours; Pry open glass plate then, take out gel film, be the modified phosphorus fixing film.
The electron-microscope scanning image of prepared modified phosphorus fixing film is seen Fig. 2 b, the densification that is evenly distributed of its surperficial zirconium dioxide particle, particle diameter≤5 μ m.
 
Embodiment 2
Modified phosphorus fixing film in a kind of diffusive gradients in thin-films measurement, its preparation method is following:
The zirconium oxychloride that takes by weighing 25g is dissolved in the 600ml deionized water; Use the ammoniacal liquor of 25% (volume ratio) that pH value of solution is regulated and is stabilized between the 6.9-7.1 then; The precipitate with deionized water that is produced is washed 8-9 time, with hair-dryer its water percentage is dried up between 45~55% at last.By mass volume ratio 1:5 Zirconium dioxide powder and the 7.2ml acrylamide solution (WS of 28.5% acrylic amide and 1.5% Methacrylamide) that 1.45g prepares mixed, ground 10~30 minutes, used clasmatosis appearance 20% frequency more ultrasonic 5~15 minutes with agate mortar; Left standstill 10~30 minutes, remove sediment after, in solution, add the tetramethyl diethylamine (TEMED) of 5.1 μ L and the ammonium persulfate solution (mass ratio 10%) of 120 μ L successively; Then solution is slowly injected the two glass sheets spaces that accompany the U-shaped plastic tab, catch up with bubble to the greatest extent after, glass plate is 20 ℃ of following horizontal positioned half an hour; After treating zirconium powder free setting; Be warming up to 60 ℃, placed 1 hour, make the solution gel film forming; Glass plate after the film forming is put into deionized water to be soaked 24 hours; Pry open glass plate then, take out gel film, be the modified phosphorus fixing film.
 
Embodiment 3, the modified phosphorus fixing film in a kind of diffusive gradients in thin-films measurement, and its preparation method and embodiment 1 are basic identical,
Be outside the difference that acrylamide solution is 35.0% acrylamide aqueous solution.
 
Embodiment 4, the modified phosphorus fixing film in a kind of diffusive gradients in thin-films measurement, and its preparation method and embodiment 1 are basic identical,
Be outside the difference that acrylamide solution is the WS of 27.5% acrylic amide and 2.5% Methacrylamide.
 
Embodiment 5
Modified phosphorus fixing film and existing phosphorus fixing film (ZL 200910183047.5) film that embodiment 1 is made are cut into the disk of diameter 2.5cm; Be assembled into the DGT device; Put into the phosphorus solution that concentration is 21mg/L, place behind the different time withdrawing device and fixing film.
At first fixedly film is cut into 10 * 10mm square; Be cut into 0.2 * 10mm rectangular (being spatial resolution 0.2mm) then, select 20 arbitrarily, put into 1 ml centrifuge tube every; Adding 0.2 ml 1M NaOH solution extracts; Vibrated 16 hours, and analyzed the phosphorus concentration in the extract, be converted into each rectangular unit area phosphorus fixed amount that goes up with the molybdenum blue colorimetric method.Measure the result and see table 1.
Can find out from table 1; With non-modified fixedly film compare, modified fixedly film assembling DGT measure the unit area phosphorus fixed amount that obtains and theoretical value coincide better, simultaneously after placement 4 hours; Error at measurment promptly can be controlled in 10%, but not modified fixedly the error of film surpass 20%.Comparing result can find out, the modified fixedly film DGT that can be used for resolution 0.2mm is measured, and non-modified fixedly film then can't be used for the mensuration under this resolution condition.
Phosphorus fixing film recorded at different time before and after table 1 improved unit area phosphorus fixed amount and analytical error (one dimension resolution is 0.2mm) thereof
Figure 241120DEST_PATH_IMAGE012

Claims (6)

1.一种薄膜扩散梯度测定中的改进型磷固定膜,系包含ZrO2的聚丙烯酰胺凝胶膜,其特征在于:所述的磷固定膜表面均匀分布粒径≤5μm的二氧化锆颗粒。 1. An improved phosphorus immobilized membrane in the thin film diffusion gradient measurement is composed of ZrO Polyacrylamide gel membrane, characterized in that: the surface of the phosphorus immobilized membrane is uniformly distributed with zirconium dioxide particles with a particle diameter≤5 μm . 2.根据权利要求1所述的的薄膜扩散梯度测定中的改进型磷固定膜,其特征在于,所述的改进型磷固定膜采用以下方法制备:将含水率为45-55%的二氧化锆粉末和丙烯酰胺溶液按重量体积比1:3~1:6混匀,研磨后超声破碎,静置除去沉淀物后,加入丙烯酰胺溶液体积1/1600~1/1400的四甲基二乙胺和1/60~1/40的10 wt %过硫酸铵溶液,混合均匀后将混合液注入玻璃模具中,室温以下水平放置,待锆粉自由沉降后,升温至40~60℃,直至混合液形成凝胶膜,在去离子水中浸泡12小时以上,得到改进的磷固定膜。 2. The improved phosphorus fixed membrane in the thin film diffusion gradient measurement according to claim 1 is characterized in that, the described improved phosphorus fixed membrane is prepared by the following method: Dioxide with a moisture content of 45-55% Zirconium powder and acrylamide solution are mixed at a weight-volume ratio of 1:3 to 1:6, ground and ultrasonically crushed, and left standing to remove the precipitate, then adding tetramethyldiethyl ether with a volume of 1/1600 to 1/1400 of the acrylamide solution Amine and 1/60~1/40 10 wt % ammonium persulfate solution, mix evenly, pour the mixture into a glass mold, place it horizontally below room temperature, and after the zirconium powder settles freely, raise the temperature to 40~60°C until mixed The solution forms a gel film, soaked in deionized water for more than 12 hours, and an improved phosphorus immobilization film is obtained. 3.一种薄膜扩散梯度测定中的改进型磷固定膜的制备方法,其特征在于,将含水率为45-55%的二氧化锆粉末和丙烯酰胺溶液按重量体积比1:3~1:6混匀,研磨后超声破碎,静置除去沉淀物后,加入丙烯酰胺溶液体积1/1600~1/1400的四甲基二乙胺和1/60~1/40的10% wt 过硫酸铵溶液,混合均匀后将混合液注入玻璃模具中,室温以下水平放置,待锆粉自由沉降后,升温至40~60℃,直至混合液形成凝胶膜,在去离子水中浸泡12小时以上,得到改进的磷固定膜。 3. a kind of preparation method of the improved phosphorus immobilized film in the thin film diffusion gradient measurement, it is characterized in that, the zirconium dioxide powder and the acrylamide solution that moisture content is 45-55% are by weight volume ratio 1:3~1: 6. Mix well, after grinding, ultrasonically crush, and after standing to remove the precipitate, add tetramethyldiethylamine of 1/1600~1/1400 volume of acrylamide solution and 10% wt ammonium persulfate of 1/60~1/40 Solution, after mixing evenly, pour the mixed solution into a glass mold, place it horizontally below room temperature, and after the zirconium powder settles freely, raise the temperature to 40-60°C until the mixed solution forms a gel film, soak it in deionized water for more than 12 hours, and obtain Improved Phosphorus Fixation Membranes. 4.根据权利要求3所述的薄膜扩散梯度测定中的改进型磷固定膜的制备方法的应用于薄膜扩散梯度测定技术的改进型磷固定膜,其特征在于,所述的二氧化锆粉末是由氧氯化锆和去离子水按重量体积比1:15~1:30混合溶解,然后用氨水将调节溶液pH在6.9-7.1之间,所产生的沉淀用去离子水后,干燥并控制其含水率为45~55%之间。 4. according to the preparation method of the improved phosphorus fixed membrane in the thin film diffusion gradient measurement according to claim 3, the improved phosphorus fixed membrane applied to the thin film diffusion gradient measurement technology, is characterized in that, described zirconium dioxide powder is Zirconium oxychloride and deionized water are mixed and dissolved in a weight-to-volume ratio of 1:15 to 1:30, and then the pH of the solution is adjusted between 6.9 and 7.1 with ammonia water, and the resulting precipitate is dried and controlled with deionized water. Its moisture content is between 45% and 55%. 5.根据权利要求3所述的薄膜扩散梯度测定中的改进型磷固定膜的制备方法,其特征在于,所述的二氧化锆粉末和丙烯酰胺溶液的重量体积比为1:4~1:6。 5. the preparation method of the improved phosphorus immobilized membrane in the film diffusion gradient measurement according to claim 3, is characterized in that, the weight-to-volume ratio of described zirconium dioxide powder and acrylamide solution is 1:4~1: 6. 6.根据权利要求3所述的薄膜扩散梯度测定中的改进型磷固定膜的制备方法,其特征在于,所述的丙烯酰胺溶液为25~35 wt%丙烯酰胺的水溶液,其中包含0~5.0 wt%甲基丙烯酰胺。 6. The preparation method of the improved phosphorus immobilized membrane in the film diffusion gradient measurement according to claim 3, is characterized in that, described acrylamide solution is the aqueous solution of 25~35 wt% acrylamide, wherein contains 0~5.0 wt% methacrylamide.
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CN104048930A (en) * 2013-03-12 2014-09-17 中国科学院南京地理与湖泊研究所 Synchronization acquisition method of active phosphorus and iron in deposit
CN104043409B (en) * 2013-03-12 2016-08-17 中国科学院南京地理与湖泊研究所 A kind of fixing film synchronizing enriched phosphorus and ferrum and preparation method thereof
CN103657618A (en) * 2013-12-16 2014-03-26 南京大学 Adsorption film for synchronously fixing various oxygen-containing negative ions and preparation method thereof
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CN104568673A (en) * 2014-12-25 2015-04-29 安徽建筑大学 A kind of Mg(OH)2-based phosphorus binding film and its preparation and application
CN104568675A (en) * 2015-01-08 2015-04-29 中国环境科学研究院 DGT testing analysis method for phosphorus absorption characteristics of lake aquatic plant root zone
CN106198319A (en) * 2016-06-23 2016-12-07 中国科学院南京地理与湖泊研究所 A kind of method based on 8 kinds of oxidized form aniones of DGT Simultaneous Determination
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CN106568689B (en) * 2016-10-17 2019-06-18 农业部环境保护科研监测所 Totally dissociated DGT binding membrane for measuring soil available phosphorus and preparation method thereof
CN108680726A (en) * 2018-05-08 2018-10-19 中国科学院地球化学研究所 Measure the DGT enrichment films and preparation method thereof of Paddy Soil Solutions biological effectiveness Hg (II)
CN108680726B (en) * 2018-05-08 2020-06-26 中国科学院地球化学研究所 DGT enrichment membrane for measuring bioavailability of Hg(II) in paddy soil solution and preparation method thereof
CN108993373A (en) * 2018-07-10 2018-12-14 广州大学 A kind of adsorbed film and preparation method thereof of fixed thallium ion
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
CN111470533A (en) * 2019-06-14 2020-07-31 南京赛诺特斯材料科技有限公司 Nano zirconium oxide powder for optical fiber ferrule and optical fiber sleeve and production process thereof
CN111504988A (en) * 2020-04-07 2020-08-07 天津大学 Method for measuring two-dimensional distribution of available phosphorus content
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