CN107522238A - Nano ferriferrous oxide liquid combines phase and the ion measurement method based on DGT - Google Patents
Nano ferriferrous oxide liquid combines phase and the ion measurement method based on DGT Download PDFInfo
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- CN107522238A CN107522238A CN201710561272.2A CN201710561272A CN107522238A CN 107522238 A CN107522238 A CN 107522238A CN 201710561272 A CN201710561272 A CN 201710561272A CN 107522238 A CN107522238 A CN 107522238A
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- 239000007788 liquid Substances 0.000 title claims abstract description 141
- 238000000691 measurement method Methods 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 114
- 150000002500 ions Chemical class 0.000 claims abstract description 98
- 239000008367 deionised water Substances 0.000 claims abstract description 46
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 46
- -1 phosphate anion Chemical class 0.000 claims abstract description 44
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 39
- 239000010452 phosphate Substances 0.000 claims abstract description 39
- 239000008187 granular material Substances 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 46
- 229910052698 phosphorus Inorganic materials 0.000 claims description 46
- 239000011574 phosphorus Substances 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 34
- 239000003480 eluent Substances 0.000 claims description 34
- 238000000502 dialysis Methods 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 18
- 238000009792 diffusion process Methods 0.000 claims description 17
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910001447 ferric ion Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 11
- 229920002678 cellulose Polymers 0.000 claims description 11
- 238000010828 elution Methods 0.000 claims description 11
- 230000001172 regenerating effect Effects 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000004627 regenerated cellulose Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000011017 operating method Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 19
- 238000005259 measurement Methods 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 238000002386 leaching Methods 0.000 description 7
- 239000001117 sulphuric acid Substances 0.000 description 7
- 235000011149 sulphuric acid Nutrition 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000011684 sodium molybdate Substances 0.000 description 6
- 235000015393 sodium molybdate Nutrition 0.000 description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 6
- 235000010344 sodium nitrate Nutrition 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 150000005837 radical ions Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229940077449 dichromate ion Drugs 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012428 routine sampling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
- G01N2013/003—Diffusion; diffusivity between liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Combined mutually the invention discloses a kind of nano ferriferrous oxide liquid and the ion measurement method based on DGT, the preparation method of the nano ferriferrous oxide liquid combination phase include：According to 2~12mg nano ferriferrous oxide granule ratios are used in every ml deionized water, nano ferriferrous oxide granule is added in deionized water, and ultrasonic disperse is uniform.The mutually liquid combination phase as DGT is combined using the nano ferriferrous oxide liquid, is measured available for the phosphate anion in water body to be measured.Not only adsorption capacity is big, application is wide, can preserve for a long time by the present invention, and easily prepare, be enriched with after do not need rinsing step, simplify operating procedure, save production cost and time cost.
Description
Technical field
The present invention relates to diffusion thin film technique (Diffusive gradients in thin-films
Technique, DGT) field, more particularly to a kind of nano ferriferrous oxide liquid combination phase and the ion measurement side based on DGT
Method.
Background technology
Diffusion thin film technique has simple to operate, low cost and other advantages, and can measure in water-outlet body metal or
The nonmetallic mean concentration within a period of time, therefore diffusion thin film technique has become a kind of effective application point on the spot
Analysis instrument, and be widely used in terms of long-term, large-scale waters detections and assessment.
One DGT device includes diffusion mutually and with reference to phase.In addition to dialysis membrane, hydrogel is to apply most diffusions
Phase, especially PAHG.In addition to sub-fraction polymer solution is used as and combines phase, hydrogel combines different
Material be used as DGT combination phase (combination based on hydrogel mutually be commonly referred to as solid-state bond phase).Although this solid-state junction
Close mutually has had very successful application case in DGT devices, but this solid-state bond mutually has the characteristics of frangible, is unsuitable for
Produce in enormous quantities and store for a long time, and can only be assembled using the DGT devices of this solid-state bond phase before use, can not product
Metaplasia is produced and extensive use.
2003, Zhao Huijun et al. took the lead in proposing to substitute traditional gel as diffusion phase using commercial dialysis membrane, and
Using 0.02mol/L polystyrene sulfonate (PSS) solution as with reference to phase (solution be used as combine mutually be commonly referred to as liquid knot
Close phase), in-situ enrichment measurement is carried out to the Cd (II) in water body and Cu (II), and achieve good effect.Then, poly- third
Olefin(e) acid sodium, POLYPROPYLENE GLYCOL, polyethyleneimine, sodium carboxymethylcellulose and quaternary ammonium salt Polymer material are used as liquid in succession
In-situ enrichment measurement is carried out with reference to some heavy metal ion in relative water body and free state phosphorus.The hair of these liquid combination phases
Exhibition, is avoided rinsing step when being detected using solid-state bond relative target material, reduces cumbersome operating process, greatly
The big accuracy and precision for improving DGT technology for detection.But in the prior art, the species of liquid combination phase is still less,
And adsorption capacity is smaller, application is narrower.
The content of the invention
For solid-state bond in the prior art it is mutually frangible, be difficult to ensure and deposit, and liquid combination phase species is few, adsorbance is relatively low, should
With the technical problem such as scope is narrower, the invention provides a kind of nano ferriferrous oxide liquid to combine mutually and the ion based on DGT
Assay method, not only adsorption capacity is big, application is wide, can preserve for a long time, and easily prepare, be enriched with after need not elute step
Suddenly operating procedure, is simplified, saves production cost and time cost.
The purpose of the present invention is achieved through the following technical solutions：
A kind of nano ferriferrous oxide liquid combination phase, its preparation method include：According in every ml deionized water use 2
~12mg nano ferriferrous oxide granule ratios, nano ferriferrous oxide granule is added in deionized water, and ultrasonic disperse
Uniformly, so as to obtained nano ferriferrous oxide liquid combination phase.
Preferably, particle diameter≤10nm of the nano ferriferrous oxide granule.
Preferably, the preparation method of the nano ferriferrous oxide granule includes：Prepare ferrous ion and ferric iron from
The mixed solution of son, the concentration of wherein ferrous ion is 0.025~0.125moL/L, the concentration of ferric ion be 0.05~
0.25moL/L；Ammoniacal liquor or saturation sodium hydroxide are added into the mixed solution of ferrous ion and ferric ion, until producing
Black precipitate, and continue stirring 30 minutes；Described black precipitate is separated and collected with magnet, and is cleaned to remove residual examination
Agent, then product addition deionized water is freezed, place into freeze drier and dry 18 hours, so as to which black powder be made
The nano ferriferrous oxide granule of shape.
Preferably, the nano ferriferrous oxide liquid preserves with reference to phase in 4 DEG C of environment.
A kind of ion measurement method based on DGT, using the nano ferriferrous oxide liquid described in above-mentioned technical proposal
With reference to the mutually liquid combination phase as DGT.
Preferably, the mutually liquid as DGT is combined using the nano ferriferrous oxide liquid described in above-mentioned technical proposal
With reference to phase, for being measured to the phosphate anion in water body to be measured.
Preferably, including：The assembling and placement of DGT devices：Using the oxidation of nanometer four three described in above-mentioned technical proposal
Iron liquid state combines the mutually liquid combination phase as DGT devices, and is filled using the activating and regenerating cellulose dialysis film of cleaning as DGT
The diffusion phase put, then completes the assembling of DGT devices, and the DGT devices assembled are positioned in water body to be measured, and record is placed
Time；
The recovery of DGT devices and liquid combination phase intermediate ion concentration mensuration：DGT devices are taken out from water body to be measured, and
DGT apparatus surfaces are cleaned with deionized water, then take out the liquid combination phase in DGT devices, then the liquid is combined and is mutually placed in
The sodium hydroxide that concentration is 0.25moL/L elutes to be eluted 12 hours in agent, and eluent determines phosphoric acid in eluent after diluting 10 times
Ion concentration；
The concentration of DGT devices calculates：Phosphorus acid ion concentration in eluent is converted into the adsorbance in liquid combination phase：
M=Ce×(Ve+VLBP)/fe (1)
In formula (1), M be absorption in liquid combination phase phosphate anion quality, CeIt is phosphate anion in eluent
Concentration, VeIt is the volume of eluent, VLBPIt is the volume of liquid combination phase, feIt is elution efficiency；
The adsorbance in liquid combination phase is converted into the phosphorus acid ion concentration that DGT devices determine again：
CDGT=M × Δ g/ (D × A × T) (2)
In formula (2), CDGTIt is the phosphorus acid ion concentration that DGT devices determine, M is absorption phosphoric acid in liquid combination phase
The quality of radical ion, Δ g are that diffusion barrier adds the total thickness of filter membrane, and D is the diffusion coefficient of phosphate anion, and A is DGT devices
Window area, T are standing times.
Preferably, the preparation method of the activating and regenerating cellulose dialysis film of the cleaning includes：By maximum molecular cut off
For 3500 regenerated cellulose dialysis membrane be placed in sodium acid carbonate mass concentration be 2%, disodium ethylene diamine tetraacetate concentration be
In 1mmol/L mixed solution, and 100 DEG C are heated to, 10min is boiled under fluidized state, then cleaned with deionized water, so as to obtain
The activating and regenerating cellulose dialysis film of cleaning.
Preferably, the dosage that the sodium hydroxide elutes agent is 20~40 times of liquid combination phase volume.
Preferably, the NO of water body to be measured3-Concentration is 0~0.5mol/L, and the pH value of the water body to be measured is 3~9.
As seen from the above technical solution provided by the invention, nano ferriferrous oxide liquid provided by the invention combines
It is mutually to aoxidize three using 2~12mg nanometers four according to every ml deionized water by particle diameter≤10nm nano ferriferrous oxide granule
The ratio uniform of iron particle is scattered to be formed in deionized water, not only can be to be provided in water body by the ion of in-situ enrichment
Substantial amounts of adsorption space and site, the adsorption capacity of liquid combination phase is greatly improved, and can ensure that absorption property is stable
In the case of store for a long time.The nano ferriferrous oxide liquid is employed to combine mutually as the DGT ion measurement methods with reference to phase
Can be in NO3-Applied in the water body that concentration is 0~0.5mol/L and pH value is 3~9, and to concentration in the range of 0.5~7mg/L
Phosphate anion, dichromate ion, arsenic acid radical ion, cadmium ion, copper ion and lead ion plasma carry out measurement of concetration,
Therefore application is wide.It can be seen that nano ferriferrous oxide liquid provided by the present invention combines mutually, not only adsorption capacity is big, applies
Scope is wide, can preserve for a long time, and easily prepare, be enriched with after do not need rinsing step, simplify operating procedure, save production
Cost and time cost.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the transmission electron microscope picture of the nano ferriferrous oxide liquid combination phase obtained by the embodiment of the present invention 1.
Fig. 2 is phosphate anion amount standing time change in water body with it that DGT devices are enriched with the embodiment of the present invention 1
Schematic diagram.
Fig. 3 is that the phosphate anion amount that DGT devices are enriched with the embodiment of the present invention 6 becomes with phosphorus acid ion concentration in solution
The schematic diagram of change.
Fig. 4 is NO in the embodiment of the present invention 33-PH value is in water body and the embodiment of the present invention 2 that concentration is 0~0.5mol/L
The influence schematic diagram for the phosphate anion amount that 3~9 water body is enriched with to DGT devices.
Fig. 5 is the phosphate anion amount of DGT devices enrichment in the embodiment of the present invention 7 with the oxygen of nanometer four in liquid combination phase
Change the schematic diagram of three-iron change in concentration.
Fig. 6 is the phosphate anion amount that water body existing for a variety of anion is enriched with to DGT devices in the embodiment of the present invention 4
Influence schematic diagram.
Fig. 7 is that the liquid of nano ferriferrous oxide in the embodiment of the present invention 5 is combined mutually in 0.01mol/L sodium nitrate solutions
The influence schematic diagram for the phosphate anion amount that storage time is enriched with to DGT devices.
Embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on this
The embodiment of invention, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to protection scope of the present invention.
The nano ferriferrous oxide liquid that the present invention is described below in detail combines phase and the ion measurement method based on DGT.
A kind of nano ferriferrous oxide liquid combination phase, its preparation method include：According in every ml deionized water use 2
~12mg nano ferriferrous oxide granule ratios, particle diameter≤10nm nano ferriferrous oxide granule is added to deionized water
In, and ultrasonic disperse is uniform, so as to which nano ferriferrous oxide liquid combination phase be made.
Wherein, the preparation method of the nano ferriferrous oxide granule can include：Prepare ferrous ion and ferric iron
The mixed solution of ion, wherein ferrous ion (ferrous ion can come from ferrous sulfate, ferrous nitrate or frerrous chloride)
Concentration for 0.025~0.125moL/L, ferric ion (ferric ion can come from ferric sulfate, ferric nitrate or iron chloride)
Concentration be 0.05~0.25moL/L；Ammoniacal liquor or saturation hydrogen are added into the mixed solution of ferrous ion and ferric ion
Sodium oxide molybdena, until producing black precipitate, and it is continuously stirred at room temperature 30 minutes；Described black is separated and collected with magnet to sink
Form sediment, and cleaned (such as：Ethanol and deionized water can be used clean repeatedly) to remove remaining reagent, then will production
Thing adds deionized water and freezed, and places into freeze drier and dries 18 hours, so as to which the nanometer four of black powder be made
Fe 3 O particle.
Specifically, the ion measurement method based on DGT can use above-mentioned nano ferriferrous oxide liquid to combine mutually conduct
DGT liquid combination phase, and for the phosphate anion in water body, dichromate ion, arsenic acid radical ion, cadmium ion, copper
Ion and lead ion plasma carry out measurement of concetration；Surveyed with carrying out the ion based on DGT to the phosphate anion in water body to be measured
It is set to example, there is assay method can include herein below for it：
(1) select suitable dialysis membrane and activated：Preferably with maximum molecular cut off it is 3500 in the present invention
The dialysis membrane in diffusion phase of the regenerated cellulose dialysis membrane as DGT devices, this material and aperture can not only make target analysis
Thing is combined by diffusing into DGT devices and mutually captured, and can effectively be prevented as the nano ferriferrous oxide with reference to phase
Particle oozes out.The activation process of dialysis membrane can be included：By the regenerated cellulose dialysis membrane that maximum molecular cut off is 3500
It is placed in the mixed solution that sodium acid carbonate mass concentration is 2%, disodium ethylene diamine tetraacetate concentration is 1mmol/L, and is heated to
100 DEG C, 10min is boiled under fluidized state, to remove the glycerine and heavy metal ion on dialysis membrane, then is cleaned with deionized water, from
And the activating and regenerating cellulose dialysis film cleaned.The activating and regenerating cellulose dialysis film of the cleaning can be placed in 4 DEG C
Preserved in environment, only need to be cleaned with deionized water before use.
(2) assembling and placement of DGT devices：Combined using above-mentioned nano ferriferrous oxide liquid mutually as DGT devices
Liquid combination phase, and using diffusion phase of the activating and regenerating cellulose dialysis film cleaned as DGT devices, then complete DGT dresses
The assembling put, and the DGT devices assembled are positioned in water body to be measured, record standing time.
(3) recovery of DGT devices and liquid combination phase intermediate ion concentration mensuration：DGT devices are taken out from water body to be measured,
And DGT apparatus surfaces are cleaned with deionized water, the liquid combination phase in DGT devices is then taken out, then the liquid is combined and mutually put
Eluting 12 hours in the sodium hydroxide elution agent that concentration is 0.25moL/L, (dosage that the sodium hydroxide elutes agent is liquid
With reference to 20~40 times of phase volume), eluent determines phosphorus acid ion concentration in eluent after diluting 10 times.In practical application
In, phosphorus acid ion concentration can be measured using molybdenum blue colorimetric method, the reaction time is 1 hour, and reaction temperature is 35 DEG C.
(4) DGT devices concentration calculates：The adsorbance that phosphorus acid ion concentration in eluent is changed into liquid combination phase：
M=Ce×(Ve+VLBP)/fe (1)
In formula (1), M be absorption in liquid combination phase phosphate anion quality, CeIt is phosphate anion in eluent
Concentration, VeIt is the volume of eluent, VLBPIt is the volume of liquid combination phase, feIt is elution efficiency；
The adsorbance in liquid combination phase is converted into the phosphorus acid ion concentration that DGT devices determine again：
CDGT=M × Δ g/ (D × A × T) (2)
In formula (2), CDGTIt is the phosphorus acid ion concentration that DGT devices determine, M is absorption phosphoric acid in liquid combination phase
The quality of radical ion, Δ g are that diffusion barrier adds the total thickness of filter membrane, and D is the diffusion coefficient of phosphate anion, and A is DGT devices
Window area, T are standing times.
Further, compared with prior art, it is provided by the present invention to be combined using above-mentioned nano ferriferrous oxide liquid
Mutually the DGT ion measurements method as DGT liquid combination phase at least has advantages below：
(1) nano ferriferrous oxide liquid provided by the present invention combine mutually can with efficient absorption phosphate anion, and
Nano ferriferrous oxide granule particle diameter≤10nm in liquid combination phase, this provides huge adsorption space for phosphate anion
And site, the adsorption capacity of liquid combination phase in each DGT devices can be made to reach 105 μ g, therefore aoxidized using the nanometer four
The DGT devices of three-iron liquid combination phase can be used in the monitoring of phosphate anion in high pollution water body.
(2) nano ferriferrous oxide liquid provided by the present invention is with reference to the mixing that can be mutually put into deionized water and ethanol
Solution is placed in 4 DEG C of environment and preserved, and can also be placed in 0.01mol/L sodium nitrate solution and store.Through examining, the nanometer
Ferroso-ferric oxide liquid still has good characterization of adsorption after being stored 2 years in 0.01mol/L sodium nitrate solution with reference to phase,
Therefore nano ferriferrous oxide liquid provided by the present invention, which combines, mutually has good stability, is adapted to long-term storage.
(3) nano ferriferrous oxide liquid provided by the present invention can avoid Cl in water body with reference to phase-、SO4 2-、
CrO4 2-、HAsO4 2-Deng the interference of Common Anions, when carrying out Concentration Testing to phosphate anion in water body so as to effectively prevent
The ion interference problem often occurred.
(4) nano ferriferrous oxide liquid provided by the present invention combines mutually combines what is mutually used in preparation with as DGT
During be to use deionized water (i.e. volume resistance >=15.0M Ω cm water), this is it is possible to prevente effectively to phosphorus in water body
Acid ion carries out ion interference problem occur during Concentration Testing.
(5) the ion measurement method provided by the present invention based on DGT, as a result of above-mentioned nano ferriferrous oxide liquid
State combines the mutually liquid combination phase as DGT, therefore can be in NO3-The water body that concentration is 0~0.5mol/L and pH value is 3~9
Middle application, thus the ion measurement method provided by the present invention based on DGT be adapted to various water bodies in phosphate anion it is effective
Monitoring.
(6) the ion measurement method provided by the present invention based on DGT, as a result of above-mentioned nano ferriferrous oxide liquid
State combines the mutually liquid combination phase as DGT, therefore can be applied in 0.5~7mg/L of phosphorus acid ion concentration water body, makes
It is wide with scope.
(7) the ion measurement method provided by the present invention based on DGT is a kind of in situ, nondestructive passive sampling skill
Art, so as to solve in the prior art actively sampling can not in-situ enrichment and the technologies such as the routine sampling technology degree of accuracy is low ask
Topic, test result is more credible.
(8) concentration value obtained by the ion measurement method provided by the present invention based on DGT is certain standing time model
The average value obtained in enclosing, phosphorus acid ion concentration change in certain time in water body can be preferably reacted, compared to actively
Obtained instantaneous value is sampled, with more the meaning of environmental monitoring.
(9) do not need rinsing step after the ion measurement method enrichment provided by the present invention based on DGT, simplify operation
Step, save production cost and time cost.
As fully visible, not only adsorption capacity is big, application is wide, can preserve for a long time for the embodiment of the present invention, and easily makes
Rinsing step is not needed after standby, enrichment, simplifies operating procedure, saves production cost and time cost.
In order to more clearly from show technical scheme provided by the invention and caused technique effect, below with specific
Embodiment the nano ferriferrous oxide liquid of the present invention is combined mutually and the ion measurement method based on DGT is described in detail.
Embodiment 1
A kind of nano ferriferrous oxide liquid combination phase, its preparation method comprise the following steps：
Step a1,2.70g iron chloride and 0.99g frerrous chlorides are dissolved in 40mL deionized waters, and continue to stir, obtained
The ferrous ion of clarification and the mixed solution of ferric ion, the wherein concentration of ferrous ion are 0.125moL/L, trivalent
The concentration of iron ion is 0.25moL/L.
Step b1,5mL ammoniacal liquor is added into the mixed solution of ferrous ion and ferric ion, adjusts mixed solution
PH value, until producing black precipitate, and it is continuously stirred at room temperature 30 minutes.
Step c1, the black precipitate is separated and collected with magnet, and is cleaned repeatedly using ethanol and deionized water, with
Remaining reagent is removed, is then freezed product addition deionized water, freeze drier is placed into and dries 18 hours, so as to make
Obtain the nano ferriferrous oxide granule of black powder.
Step d1, according to 2mg nano ferriferrous oxide granule ratios are used in every ml deionized water, by particle diameter≤10nm
Nano ferriferrous oxide granule be added in deionized water, and ultrasonic disperse is uniform, so as to which transmission electron microscope picture such as Fig. 1 institutes be made
The nano ferriferrous oxide liquid combination phase shown.
Specifically, using the river of certain phosphorus-containing acid ion as water body to be measured, and according to the ion measurement method based on DGT
The combination combined using the nano ferriferrous oxide liquid obtained by the embodiment of the present invention 1 mutually as DGT mutually carries out ion measurement,
The water quality of the water body to be measured is as shown in table 1 below,
Table 1：
Ion measurement method based on DGT may comprise steps of：
Step A1, select suitable dialysis membrane and activated：By the regenerated cellulose that maximum molecular cut off is 3500
Dialysis membrane is placed in the mixed solution that sodium acid carbonate mass concentration is 2%, disodium ethylene diamine tetraacetate concentration is 1mmol/L, and
100 DEG C are heated to, 10min is boiled under fluidized state, to remove the glycerine and heavy metal ion on dialysis membrane, then it is clear with deionized water
Wash, so as to the activating and regenerating cellulose dialysis film cleaned.
Step B1, the assembling and placement of DGT devices：Using the nano ferriferrous oxide liquid obtained by the embodiment of the present invention 1
State combines the mutually liquid combination phase as DGT devices, and using the activating and regenerating cellulose dialysis film cleaned as DGT devices
Phase is spread, then completes the assembling of DGT devices, and the DGT devices assembled are positioned in water body to be measured, when record is placed
Between.
Step C1, the recovery of DGT devices and liquid combination phase intermediate ion concentration mensuration：DGT devices are placed on respectively and treated
3h, 6h, 9h, 12h and 24h in water body are surveyed, then takes out DGT devices from water body to be measured, and DGT dresses are cleaned with deionized water
Surface is put, then takes out the liquid combination phase in DGT devices, then the liquid is combined to the hydrogen for being mutually placed in that concentration is 0.25moL/L
Eluted 12 hours in sodium oxide molybdena eluant, eluent；Take 1mL eluents be diluted to 10mL and add 0.015% sulphuric acid leaching 8.0mL with
And after sodium molybdate dilution heat of sulfuric acid 2.0mL, the 1h that develops the color, at spectrophotometer (UV-2700, Shimadzu, Japan) 650nm
Measure absorption values simultaneously calculate phosphorus acid ion concentration in eluent.
Step D1, the concentration of DGT devices calculates：Phosphorus acid ion concentration in eluent is converted into liquid combination phase
Adsorbance：M=Ce×(Ve+VLBP)/fe (1)
In formula (1), M be absorption in liquid combination phase phosphate anion quality, CeIt is phosphate anion in eluent
Concentration, VeIt is the volume of eluent, VLBPIt is the volume of liquid combination phase, feIt is elution efficiency；
The adsorbance in liquid combination phase is converted into the phosphorus acid ion concentration that DGT devices determine again：
CDGT=M × Δ g/ (D × A × T) (2)
In formula (2), CDGTIt is the phosphorus acid ion concentration that DGT devices determine, M is absorption phosphoric acid in liquid combination phase
The quality of radical ion, Δ g are that diffusion barrier adds the total thickness of filter membrane, and D is the diffusion coefficient of phosphate anion, and A is DGT devices
Window area, T are standing times.
After calculating by step D1, can obtain the phosphate anion amount of DGT devices enrichment as shown in Figure 2 with its
The schematic diagram that standing time changes in water body.As seen from Figure 2：The phosphate anion amount of DGT devices enrichment is with it in water body
The extension of middle standing time is in the trend that rises appreciably；Importantly, the phosphate anion amount of DGT devices enrichment is counted with step D1
The Molded Line (solid black lines) calculated coincide substantially, this further demonstrates the DGT devices of the invention planted in natural water
Applicability and good Detection results.
Embodiment 2
A kind of nano ferriferrous oxide liquid combination phase, its preparation method and the embodiment of the present invention 1 are essentially identical, and it is distinguished
Part is as follows：
(1) it is dissolved in 40mL deionized waters in step a1, by 0.20g ferric sulfate and 5.56g ferrous sulfate, and persistently stirs
Mix, the ferrous ion and the mixed solution of ferric ion clarified, the wherein concentration of ferrous ion are 0.05moL/
L, the concentration of ferric ion is 0.025moL/L.
(2) in step d1, according to 4mg nano ferriferrous oxide granule ratios are used in every ml deionized water, by grain
Footpath≤10nm nano ferriferrous oxide granule is added in deionized water, and ultrasonic disperse is uniform, so as to which the oxygen of nanometer four be made
Change three-iron liquid combination phase.
Specifically, the phosphorus solution that 12L concentration is about 0.5mg/L is prepared, and by adding NaNO3Make the ion of phosphorus solution strong
Spend for 0.01mol/L, magnetic agitation 24 hours at 25 DEG C, the ion in solution is reached balance, then pass through addition
0.01mol/L HNO3Solution and 0.05mol/L NaOH solution adjust the pH value of solution, be respectively 3.0 so as to obtain pH value,
4.0th, 5.0,6.0,7.0,8.0,9.0 simulated wastewater.Using the simulated wastewater of these different pH value as water body to be measured, and according to
Ion measurement method based on DGT is combined using the nano ferriferrous oxide liquid obtained by the embodiment of the present invention 2 and is mutually used as DGT
Combination mutually carry out ion measurement (3 Duplicate Samples of every group of placement), its specific ion measurement method with the embodiment of the present invention 1
The ion measurement method based on DGT it is essentially identical, its distinguish part it is as follows：It is placed in step C1, by DGT devices to be measured
5h in water body, then DGT devices are taken out from water body to be measured, and DGT apparatus surfaces are cleaned with deionized water, further take out DGT
Liquid combination phase in device, and the liquid is combined mutually to be placed in the sodium hydroxide elution agent that concentration is 0.25moL/L and eluted
12 hours；Take 1mL eluents to be diluted to 10mL and add 0.015% sulphuric acid leaching 8.0mL and sodium molybdate dilution heat of sulfuric acid
After 2.0mL, the 1h that develops the color, with measure absorption values at spectrophotometer (UV-2700, Shimadzu, Japan) 650nm and count
Phosphorus acid ion concentration in eluent is calculated, the water body that the pH value so as to obtain as shown in Figure 4 b is 3~9 is to DGT devices
The influence schematic diagram of the phosphate anion amount of enrichment.It can be seen that by Fig. 4 b：DGT devices in the embodiment of the present invention 2 can answer
In the water body for being 3~9 for pH value.
Embodiment 3
A kind of nano ferriferrous oxide liquid combination phase, its preparation method and the embodiment of the present invention 1 are essentially identical, and it is distinguished
Part is as follows：
(1) it is dissolved in 40mL deionized waters in step a1, by 1.01g ferric nitrates and 0.90g ferrous nitrates, and persistently stirs
Mix, the ferrous ion and the mixed solution of ferric ion clarified, the wherein concentration of ferrous ion are 0.125moL/
L, the concentration of ferric ion is 0.0625moL/L.
(2) in step d1, according to 6mg nano ferriferrous oxide granule ratios are used in every ml deionized water, by grain
Footpath≤10nm nano ferriferrous oxide granule is added in deionized water, and ultrasonic disperse is uniform, so as to which the oxygen of nanometer four be made
Change three-iron liquid combination phase.
Specifically, the phosphorus solution that 12L concentration is about 0.5mg/L is prepared, and by adding 0.01mol/L HNO3Solution and
The pH value of 0.05mol/L NaOH solution regulation phosphorus solution is 6.5, then adds different amounts of NaNO3Make mixed solution from
Sub- intensity is respectively 0.001mol/L, 0.01mol/L, 0.1mol/L, 0.5mol/L, and magnetic agitation 24 hours at 25 DEG C,
So as to obtain the simulated wastewater that ionic strength is respectively 0.001mol/L, 0.01mol/L, 0.1mol/L, 0.5mol/L.With these
The simulated wastewater of different ionic strength is implemented as water body to be measured, and according to the ion measurement method based on DGT using the present invention
The combination that nano ferriferrous oxide liquid obtained by example 3 combines mutually as DGT mutually carries out ion measurement (every group of placement 3 is put down
Row sample), its specific ion measurement method and the ion measurement method based on DGT in the embodiment of the present invention 1 are essentially identical, its
Difference part is as follows：5h in water body to be measured is placed in step C1, by DGT devices, then by DGT devices from water body to be measured
Take out, and clean DGT apparatus surfaces with deionized water, further take out the liquid combination phase in DGT devices, and by the liquid combination phase
It is placed in the sodium hydroxide elution agent that concentration is 0.25moL/L and elutes 12 hours；Take 1mL eluents to be diluted to 10mL and add
After 0.015% sulphuric acid leaching 8.0mL and sodium molybdate dilution heat of sulfuric acid 2.0mL, the 1h that develops the color, with spectrophotometer (UV-
2700, Shimadzu, Japan) absorption values are determined at 650nm and calculate phosphorus acid ion concentration in eluent, so as to
NO as shown in fig. 4 a can be obtained3-Concentration is the shadow for the phosphate anion amount that 0~0.5mol/L water body is enriched with to DGT devices
Ring schematic diagram.It can be seen that by Fig. 4 a：DGT devices in the embodiment of the present invention 3 can apply to NO3-Concentration is 0~0.5mol/
In L water body.
Embodiment 4
A kind of nano ferriferrous oxide liquid combination phase, its preparation method and the embodiment of the present invention 1 are essentially identical, and it is distinguished
Part is as follows：In step d1, according to 8mg nano ferriferrous oxide granule ratios are used in every ml deionized water, by particle diameter
≤ 10nm nano ferriferrous oxide granule is added in deionized water, and ultrasonic disperse is uniform, is aoxidized so as to which nanometer four be made
Three-iron liquid combination phase.
Specifically, the phosphorus solution that 12L concentration is about 0.5mg/L is prepared, and add 0.188g KCl, 0.997g
MgSO4, 1.731g CaCl2, 6.753g NaNO3, adding As (V) solution and Cr (VI) solution makes As in mixed solution (V)
Ion concentration with Cr (VI) is about 100 μ g/L, and the pH value for then adjusting mixed solution is 6.3, and the magnetic agitation at 25 DEG C
24 hours, the ion in solution is set to reach balance, so as to obtain the simulated wastewater containing a variety of interference anion.With containing a variety of
The simulated wastewater of interference anion uses the embodiment of the present invention 4 as water body to be measured, and according to the ion measurement method based on DGT
The combination that obtained nano ferriferrous oxide liquid combines mutually as DGT mutually carries out ion measurement (every group of placement 3 is parallel
Sample), its specific ion measurement method and the ion measurement method based on DGT in the embodiment of the present invention 1 are essentially identical, its area
Part is not as follows：5h in water body to be measured is placed in step C1, by DGT devices, then takes DGT devices from water body to be measured
Go out, and DGT apparatus surfaces are cleaned with deionized water, further take out the liquid combination phase in DGT devices, and the liquid is combined and mutually put
Elute in agent and elute 12 hours in the sodium hydroxide that concentration is 0.25moL/L；Take 1mL eluents to be diluted to 10mL and add
After 0.015% sulphuric acid leaching 8.0mL and sodium molybdate dilution heat of sulfuric acid 2.0mL, the 1h that develops the color, with spectrophotometer (UV-
2700, Shimadzu, Japan) absorption values are determined at 650nm and calculate phosphorus acid ion concentration in eluent, so as to
The influence signal for the phosphate anion amount that water body existing for a variety of anion as shown in Figure 6 is enriched with to DGT devices can be obtained
Figure.As seen from Figure 6：DGT devices in the embodiment of the present invention 4 are to the adsorption effect of phosphate anion not Cl in by water body-、
SO4 2-、CrO4 2-、HAsO4 2-Deng the interference of Common Anions.
Embodiment 5
A kind of nano ferriferrous oxide liquid combination phase, its preparation method and the embodiment of the present invention 1 are essentially identical, and it is distinguished
Part is as follows：In step d1, according to 10mg nano ferriferrous oxide granule ratios are used in every ml deionized water, by particle diameter
≤ 10nm nano ferriferrous oxide granule is added in deionized water, and ultrasonic disperse is uniform, is aoxidized so as to which nanometer four be made
Three-iron liquid combination phase.
Specifically, the phosphorus solution that 12L concentration is about 0.5mg/L is prepared, and the pH value for adjusting phosphorus solution is 6.5, Ran Houjia
Enter NaNO3The ionic strength for making mixed solution is 0.01mol/L, and magnetic agitation 24 hours at 25 DEG C, make in solution from
Son reaches balance, so as to obtain simulated wastewater.By the nano ferriferrous oxide liquid combination phase point obtained by the embodiment of the present invention 5
It Zhuan not stored 0 year, 1 year and 2 years in 0.01mol/L sodium nitrate solutions, then using the simulated wastewater as water body to be measured,
And mutually conduct is combined using the nano ferriferrous oxide liquid of these storage different times according to the ion measurement method based on DGT
DGT combination mutually carries out ion measurement (3 Duplicate Samples of every group of placement) respectively, and its specific ion measurement method is real with the present invention
The ion measurement method based on DGT applied in example 1 is essentially identical, and it is as follows that it distinguishes part：Put in step C1, by DGT devices
The 5h in water body to be measured is put, then takes out DGT devices from water body to be measured, and DGT apparatus surfaces are cleaned with deionized water, then
The liquid combination phase in DGT devices is taken out, and the liquid is combined to the sodium hydroxide elution agent for being mutually placed in that concentration is 0.25moL/L
Middle elution 12 hours；Take 1mL eluents to be diluted to 10mL and add 0.015% sulphuric acid leaching 8.0mL and the dilute sulphur of sodium molybdate
After acid solution 2.0mL, the 1h that develops the color, with the measure extinction number of degrees at spectrophotometer (UV-2700, Shimadzu, Japan) 650nm
It is worth and calculates phosphorus acid ion concentration in eluent, it is as shown in Figure 7 in 0.01mol/L sodium nitrate solutions so as to obtain
The influence schematic diagram for the phosphate anion amount that middle storage time is enriched with to DGT devices.As seen from Figure 7：The embodiment of the present invention 5
Obtained nano ferriferrous oxide liquid still has good after being stored 2 years in 0.01mol/L sodium nitrate solution with reference to phase
Good characterization of adsorption, therefore nano ferriferrous oxide liquid provided by the present invention combination mutually has good stability, is adapted to length
Phase stores.
Embodiment 6
A kind of nano ferriferrous oxide liquid combination phase, its preparation method and the embodiment of the present invention 1 are essentially identical, and it is distinguished
Part is as follows：In step d1, according to 12mg nano ferriferrous oxide granule ratios are used in every ml deionized water, by particle diameter
≤ 10nm nano ferriferrous oxide granule is added in deionized water, and ultrasonic disperse is uniform, is aoxidized so as to which nanometer four be made
Three-iron liquid combination phase.
Specifically, prepare 12L concentration be respectively 2.0mg/L, 4.0mg/L, 6.0mg/L, 7.0mg/L, 8.0mg/L,
9.0mg/L, 10.0mg/L phosphorus solution, and the pH value for adjusting phosphorus solution is 6.5, then adds NaNO3Make mixed solution from
Sub- intensity is 0.01mol/L, and magnetic agitation 24 hours at 25 DEG C, the ion in solution is reached balance, so as to obtain not
With the simulated wastewater of phosphorus acid ion concentration.Using the simulated wastewater of different phosphorus acid ion concentrations as water body to be measured, and according to
Ion measurement method based on DGT is combined using the nano ferriferrous oxide liquid obtained by the embodiment of the present invention 6 and is mutually used as DGT
Combination mutually respectively carry out ion measurement (3 Duplicate Samples of every group of placement), its specific ion measurement method with the present invention implement
The ion measurement method based on DGT in example 1 is essentially identical, and it is as follows that it distinguishes part：Placed in step C1, by DGT devices
The 5h in water body to be measured, then DGT devices are taken out from water body to be measured, and DGT apparatus surfaces are cleaned with deionized water, then taken
The liquid combination phase gone out in DGT devices, and the liquid is combined and is mutually placed in the sodium hydroxide elution agent that concentration is 0.25moL/L
Elution 12 hours；Take 1mL eluents to be diluted to 10mL and add 0.015% sulphuric acid leaching 8.0mL and sodium molybdate dilute sulfuric acid
After solution 2.0mL, the 1h that develops the color, with measure absorption values at spectrophotometer (UV-2700, Shimadzu, Japan) 650nm
And phosphorus acid ion concentration in eluent is calculated, so as to obtain the phosphate anion of DGT devices enrichment as shown in Figure 3
The signal that amount changes with phosphorus acid ion concentration in solution.As seen from Figure 3：DGT devices in the embodiment of the present invention 6 can be with
Applied in 0.5~7mg/L of phosphorus acid ion concentration water body, use range is wide.
Embodiment 7
A kind of nano ferriferrous oxide liquid combination phase, its preparation method and the embodiment of the present invention 1 are essentially identical, and it is distinguished
Part is as follows：In step d1, respectively according to using 2mg, 4mg, 6mg, 8mg, 10mg, 12mg nanometer in every ml deionized water
Ferriferrous oxide particles ratio, particle diameter≤10nm nano ferriferrous oxide granule is added in deionized water, and ultrasound point
Dissipate uniformly, so as to which the nano ferriferrous oxide liquid combination phase of different nano ferriferrous oxide concentration be made.
Specifically, prepare 12L concentration and be 0.5mg/L phosphorus solution, and the pH value for adjusting phosphorus solution is 6.5, is then added
NaNO3The ionic strength for making mixed solution is 0.01mol/L, and magnetic agitation 24 hours at 25 DEG C, makes the ion in solution
Reach balance, so as to obtain simulated wastewater.Using the simulated wastewater as water body to be measured, and according to the ion measurement side based on DGT
Method is combined using the nano ferriferrous oxide liquid of the different nano ferriferrous oxide concentration obtained by the embodiment of the present invention 7 mutually to be made
Ion measurement (3 Duplicate Samples of every group of placement), its specific ion measurement method and the present invention are mutually carried out respectively for DGT combination
The ion measurement method based on DGT in embodiment 1 is essentially identical, and it is as follows that it distinguishes part：In step C1, by DGT devices
24h in water body to be measured is placed on, then takes out DGT devices from water body to be measured, and DGT device tables are cleaned with deionized water
Face, the liquid combination phase in DGT devices is further taken out, and the liquid is combined to the sodium hydroxide for being mutually placed in that concentration is 0.25moL/L
Eluted 12 hours in eluant, eluent；Take 1mL eluents to be diluted to 10mL and add 0.015% sulphuric acid leaching 8.0mL and molybdic acid
After sodium dilution heat of sulfuric acid 2.0mL, the 1h that develops the color, inhaled with being determined at spectrophotometer (UV-2700, Shimadzu, Japan) 650nm
Luminosity numerical value simultaneously calculates phosphorus acid ion concentration in eluent, so as to obtain the phosphorus of DGT devices enrichment as shown in Figure 5
Acid ion amount is with the schematic diagram of nano ferriferrous oxide change in concentration in liquid combination phase.As seen from Figure 5：In this hair
DGT devices in bright embodiment 7 are placed in water body to be measured after 24h, nano ferriferrous oxide concentration be 2mg/L, 4mg/L,
6mg/L, 8mg/L, 10mg/L, 12mg/L nano ferriferrous oxide liquid have progressivelyed reach full with reference to the enriching quantity of relative phosphorus
With, therefore enriching quantity can increase with the increase of nano ferriferrous oxide concentration, and nano ferriferrous oxide concentration is
Nano ferriferrous oxide liquid during 10mg/L and 12mg/L combines relative phosphorus and also has very high enriching quantity and simultaneously unsaturation.Due to
The concentration of nano ferriferrous oxide will be a greater impact to its dispersiveness in deionized water, therefore preferably from the oxidation of nanometer four three
The nano ferriferrous oxide liquid that concentration of iron is 10mg/L combines the mutually combination phase as DGT.
As fully visible, not only adsorption capacity is big, application is wide, can preserve for a long time for the embodiment of the present invention, and easily makes
Rinsing step is not needed after standby, enrichment, simplifies operating procedure, saves production cost and time cost.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can readily occur in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (10)
1. a kind of nano ferriferrous oxide liquid combination phase, it is characterised in that its preparation method includes：According to every milliliter of deionization
2~12mg nano ferriferrous oxide granule ratios are used in water, nano ferriferrous oxide granule is added in deionized water, and
Ultrasonic disperse is uniform, so as to which nano ferriferrous oxide liquid combination phase be made.
2. nano ferriferrous oxide liquid combination phase according to claim 1, it is characterised in that the oxidation of nanometer four three
Particle diameter≤10nm of iron particle.
3. nano ferriferrous oxide liquid combination phase according to claim 1 or 2, it is characterised in that the oxygen of nanometer four
Changing the preparation method of three iron particles includes：Prepare the mixed solution of ferrous ion and ferric ion, wherein ferrous ion
Concentration be 0.025~0.125moL/L, the concentration of ferric ion be 0.05~0.25moL/L；To ferrous ion and three
Ammoniacal liquor or saturation sodium hydroxide are added in the mixed solution of valency iron ion, until producing black precipitate, and continues stirring 30 minutes；
Described black precipitate is separated and collected with magnet, and is cleaned to remove remaining reagent, product is then added into deionized water
Freezed, place into freeze drier and dry 18 hours, so as to which the nano ferriferrous oxide granule of black powder be made.
4. nano ferriferrous oxide liquid combination phase according to claim 1 or 2, it is characterised in that the oxygen of nanometer four
Change three-iron liquid to preserve in 4 DEG C of environment with reference to phase.
A kind of 5. ion measurement method based on DGT, it is characterised in that using any one of the claims 1 to 4
Nano ferriferrous oxide liquid combines the mutually liquid combination phase as DGT.
6. the ion measurement method according to claim 5 based on DGT, it is characterised in that using the claims 1 to
Nano ferriferrous oxide liquid any one of 4 combines the mutually liquid combination phase as DGT, in water body to be measured
Phosphate anion is measured.
7. the ion measurement method according to claim 6 based on DGT, it is characterised in that including：
The assembling and placement of DGT devices：Using the nano ferriferrous oxide liquid any one of the claims 1 to 4
With reference to the mutually liquid combination phase as DGT devices, and using expansion of the activating and regenerating cellulose dialysis film cleaned as DGT devices
Dephasing, then completes the assembling of DGT devices, and the DGT devices assembled are positioned in water body to be measured, records standing time；
The recovery of DGT devices and liquid combination phase intermediate ion concentration mensuration：DGT devices are taken out from water body to be measured, and spent
Ionized water cleans DGT apparatus surfaces, then takes out the liquid combination phase in DGT devices, then the liquid is combined and is mutually placed in concentration
For 0.25moL/L sodium hydroxide elute agent in elute 12 hours, eluent dilute 10 times after measure eluent in phosphate radical from
Sub- concentration；
The concentration of DGT devices calculates：Phosphorus acid ion concentration in eluent is converted into the adsorbance in liquid combination phase：
M=Ce×(Ve+VLBP)/fe (1)
In formula (1), M be absorption in liquid combination phase phosphate anion quality, CeIt is phosphorus acid ion concentration in eluent,
VeIt is the volume of eluent, VLBPIt is the volume of liquid combination phase, feIt is elution efficiency；
The adsorbance in liquid combination phase is converted into the phosphorus acid ion concentration that DGT devices determine again：
CDGT=M × Δ g/ (D × A × T) (2)
In formula (2), CDGTThe phosphorus acid ion concentration that DGT devices determine, M be absorption in liquid combination phase phosphate radical from
The quality of son, Δ g are that diffusion barrier adds the total thickness of filter membrane, and D is the diffusion coefficient of phosphate anion, and A is the window of DGT devices
Area, T are standing times.
8. the ion measurement method according to claim 7 based on DGT, it is characterised in that the activating and regenerating of the cleaning
The preparation method of cellulose dialysis film includes：The regenerated cellulose dialysis membrane that maximum molecular cut off is 3500 is placed in bicarbonate
In the mixed solution that sodium mass concentration is 2%, disodium ethylene diamine tetraacetate concentration is 1mmol/L, and 100 DEG C are heated to, seethed with excitement
10min is boiled under state, then is cleaned with deionized water, so as to the activating and regenerating cellulose dialysis film cleaned.
9. the ion measurement method according to claim 7 based on DGT, it is characterised in that the sodium hydroxide elutes agent
Dosage be 20~40 times of liquid combination phase volume.
10. the ion measurement method based on DGT according to any one of claim 6 to 9, it is characterised in that described to treat
Survey the NO of water body3-Concentration is 0~0.5mol/L, and the pH value of the water body to be measured is 3~9.
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| CN105148846A (en) * | 2015-07-20 | 2015-12-16 | 农业部环境保护科研监测所 | DTPA modified material and preparation method for rapid-full-dissociation type DGT (Diffusive gradients in thin films) coupling phase prepared therefrom |
| CN105271430A (en) * | 2015-09-28 | 2016-01-27 | 江苏振宇环保科技有限公司 | Preparation method of modified super-dispersed ferriferrous oxide |
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| CN105148846A (en) * | 2015-07-20 | 2015-12-16 | 农业部环境保护科研监测所 | DTPA modified material and preparation method for rapid-full-dissociation type DGT (Diffusive gradients in thin films) coupling phase prepared therefrom |
| CN105271430A (en) * | 2015-09-28 | 2016-01-27 | 江苏振宇环保科技有限公司 | Preparation method of modified super-dispersed ferriferrous oxide |
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