CN104492376A - Preparation method of activated carbon adsorption film and method for measuring bisphenol substances in wetland soil or sediment based on thin-film diffusion gradient technique - Google Patents
Preparation method of activated carbon adsorption film and method for measuring bisphenol substances in wetland soil or sediment based on thin-film diffusion gradient technique Download PDFInfo
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- CN104492376A CN104492376A CN201410800088.5A CN201410800088A CN104492376A CN 104492376 A CN104492376 A CN 104492376A CN 201410800088 A CN201410800088 A CN 201410800088A CN 104492376 A CN104492376 A CN 104492376A
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- bisphenol
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 104
- 239000010408 film Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000002689 soil Substances 0.000 title claims abstract description 64
- 238000009792 diffusion process Methods 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010409 thin film Substances 0.000 title claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 title abstract description 18
- 239000013049 sediment Substances 0.000 title abstract description 6
- 239000000126 substance Substances 0.000 title abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000003480 eluent Substances 0.000 claims abstract description 30
- 229920001817 Agar Polymers 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008272 agar Substances 0.000 claims abstract description 26
- 238000012360 testing method Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000010521 absorption reaction Methods 0.000 claims description 40
- 239000003610 charcoal Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 18
- 230000004888 barrier function Effects 0.000 claims description 16
- 229940058641 actidose Drugs 0.000 claims description 13
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 7
- 239000004809 Teflon Substances 0.000 claims description 6
- 229920006362 Teflon® Polymers 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 8
- 239000003463 adsorbent Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 5
- -1 1-butyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- 239000005446 dissolved organic matter Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000011504 laterite Substances 0.000 description 4
- 229910001710 laterite Inorganic materials 0.000 description 4
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 231100000290 environmental risk assessment Toxicity 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 208000008589 Obesity Diseases 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012502 risk assessment Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of an activated carbon adsorption film and a method for measuring bisphenol substances in wetland soil or sediment based on a thin-film diffusion gradient technique, and belongs to the fields of environmental sciences and earth sciences. According to the preparation method of the activated carbon adsorption film, the activated carbon adsorption film is prepared by mixing activated carbon as an adsorbent with agar, and then is overlapped on an agar diffusion film and a PTFE filter film to form a DGT device; after nitrogen introduction pretreatment, the DGT device is put into the wetland soil or the sediment to be tested for 24 hours, and then the activated carbon adsorption film is taken out and eluted by use of an eluent which is the mixed solution of methanol and sodium hydroxide; next, the adsorbing capacity of the bisphenol compounds in the adsorption film is measured and the concentration of the bisphenol substances in the wetland soil or the sediment is calculated according to the Fick's first law of diffusion. The preparation method of the activated carbon adsorption film is simple in process, the adsorbent is even in distribution, the adsorbing capacity is high and the quality guarantee period is long; the DGT technique based on the adsorption film is simple and easy to operate and the testing result is representative, and therefore, the DGT technique is suitable for in-situ detection of the bisphenol substances in the wetland soil or the sediment.
Description
Technical field
The invention belongs to environmental science and field of earth sciences, more particularly, relate to a kind of preparation method of charcoal absorption film and measure the method for bisphenol in wetland soil or deposit based on diffusion thin film technique.
Background technology
Bisphenol is widely used for the resin-lined layer of polycarbonate synthesis plastics and food service items, has become the incretion interferent that our daily life is common.Therefore, these bisphenols inevitably in entered environment, and extensively exist in the surrounding medium such as wetland soil or deposit.The bisphenol concentration of report is respectively 0.01 ~ 0.15mg/kg (dry weight) and 1.2 ~ 7.3 μ g/kg (dry weight) (Fromme H. for bisphenol-A in deposit and Bisphenol F, et al., Water Res.2002,36,1429-1438).The existence of these bisphenols can cause certain harm to the ecosystem and health.Human body is in the incidence of disease (Jaromir M., Toxicol.Pharmacol., 2014,37,738-758.) that can improve obesity, diabetes and coronary heart disease in BPA environment for a long time.Other bisphenols have slightly to acute toxicity and the estrogen active similar with BPA (Chen M.Y., et al., Environ.Toxicol.2002,17,80-86.) of moderate.Therefore, reliable, stable sampling and determination techniques are not only most important to the environmental behaviour understanding bisphenol, and contribute to assessing its environmental risk.
Passive sampling technology can overcome conventional active Sampling techniques and only survey moment concentration and the shortcoming wasted time and energy, and is widely used in recent years in the field such as environmental monitoring, risk assessment.As the outstanding person in passive sampling technology, diffusion thin film technique (Diffusive gradients in thin films, DGT) since the nineties in last century is invented by Lancaster University of Britain DavidWilliams and a sky, be widely used in the metal ion measuring available state in water body, soils and sediments.In recent years, (the Chen C.E. such as Chen, et al., J.Environ.Monit., 2012,14,1523-1530.) by XAD18 resin for the preparation of adsorbed film, by DGT technological expansion to measuring Environmental Trace organic pollution antibiotic, this provides thinking for application DGT technology measures bisphenol.
Through retrieval, Chinese patent application publication number CN 103743655A, the applying date is a kind of method that the patent application document on February 13rd, 2014 discloses that based thin film diffusion gradient technology measures inorganic arsenic in soil or water body, based thin film diffusion gradient principle, adopting zirconium dioxide to be the gel film (Zr-oxide film) that adsorbent is made is fixing film, DGT device is assembled into diffusion barrier etc., it is contacted with soil or water body (comprising deposit), place after 1 ~ 6 day, Zr-oxide film in withdrawing device, extract and measure the accumulation of inorganic arsenic in Zr-oxide film, the concentration of inorganic arsenic is calculated according to Fick's 1st law of diffusion, but this invention is not suitable for the bisphenol measured in wetland soil or deposit.Chinese patent application publication number CN102692474A, the applying date is the method for quick that the patent application document on June 6th, 2012 discloses bisphenol-A and bisphenol AF in a kind of food, this invention with ionic liquid (1-butyl-3-methylimidazole hexafluorophosphate) for extractant, with TritonX-100 or acetone for dispersant, by shaking ultrasonic formation emulsion, directly take off layer extraction drop after centrifugation and carry out HPLC quantitative analysis, the method narrow application range of this invention, and unfriendly to environment.
Current research has shown that the carbon based material comprising active carbon has good absorption property to bisphenol, is widely used (Yoon Y., et al. in the bisphenol in removal sewage, Water.Res., 2003,37,3530-3537.; Bautista-Toledo A., et al., Environ.Sci.Technol., 2005,39,6246-6250.).Although charcoal absorption film has been succeeded in developing and for measuring gold (Au) ion (the Lucas A. in water environment, et al., Anal.Chem., 2012,84,6994-7000.), but this DGT device can not be used for measuring bisphenol, wherein main cause has two aspects: one is that the polyether sulfone material filter membrane that its device adopts can adsorb bisphenol in a large number, cause this material can not be formed in filter membrane and diffusion barrier diffusion gradient and and then caught by adsorbed film; Two is that adopted pickling takes off or the bisphenol that charcoal absorption film adsorbs can not elute by digestion procedure, therefore cannot carry out follow-up concentration determination.The application such as Zheng measures bisphenol based on the DGT device of charcoal absorption film, to some extent solves the problems referred to above, but is only applied to distribution uniform and flow velocity faster in river water.And wetland soil or deposit poor fluidity (semimobile, to there is certain moisture content, the requirement of DGT test to moisture content in medium can be met), be the environment of anaerobism or anoxic.Be compared to river water, wetland soil or sedimental component completely different, interfering material is also more, so light water processing method cannot be used for the mensuration of bisphenol in wetland soil or deposit, this is because different handling objects is different with parameter requests such as antijamming capabilities to the adsorption capacity of adsorbed film.Therefore, the bisphenol how measured in wetland soil or deposit is the study hotspot of association area always.
Summary of the invention
1. the problem that will solve
Immature for the determination techniques of bisphenol in wetland soil in prior art or deposit, elute effect is poor, the problems such as narrow application range, the invention provides a kind of preparation method of charcoal absorption film and measure the method for bisphenol in wetland soil or deposit based on diffusion thin film technique, choose the active carbon that particle is less than 50 μm be adsorbent and obtain charcoal absorption film with agar gel film forming, DGT device is assembled into AGP test film and teflon membrane filter, after filling nitrogen pretreatment, be positioned in wetland soil to be measured or deposit, achieve the mensuration of DGT technology to bisphenol in wetland soil or deposit.2. technical scheme
In order to solve the problem, the technical solution adopted in the present invention is as follows:
A preparation method for charcoal absorption film, the steps include:
A agar powder mixes with pure water and more than heated solution to 80 DEG C makes its transparentization obtain agar solution by (), wherein the mass ratio of agar powder and pure water is 1.5:100;
B active carbon powder mixes with pure water and stirs and obtains Actidose by (), wherein the mass ratio of active carbon powder and pure water is (5 ~ 10): 100;
C Actidose that step (b) prepares by () adds in the agar solution that step (a) prepares and mixes, obtained mixed solution, wherein, the Actidose added and the volume ratio of agar solution are (1 ~ 1.5): 4;
D mixed solution that step (c) prepares by () injects two glass sheets spaces, extrudes bubble between glass plate, is placed horizontally at by glass plate in room temperature and cools 30 ~ 120min, and in glass plate, solution solidifies and forms charcoal absorption film.
Preferably, the particle diameter <50 μm of active carbon powder in described step (b).
Measure a method for bisphenol in wetland soil or deposit based on diffusion thin film technique, the steps include:
(1) assembling of DGT device: above-mentioned charcoal absorption film, AGP test film and the teflon membrane filter prepared is superimposed between DGT base and the lid with window successively, is assembled into DGT device;
(2) pretreatment of DGT device: DGT device is put into the glass container that pure water is housed, in water, inflated with nitrogen is to remove the oxygen in DGT device;
(3) placement of DGT device: DGT device pretreated in step (2) is put into the absorption that wetland soil to be measured or deposit carry out bisphenol;
(4) recovery of adsorbed film and wash-out: after being taken out from wetland soil to be measured or deposit by DGT device, with pure water rinsing apparatus surface dirt, then takes out charcoal absorption film, is positioned in vial, obtains eluent after adding eluant, eluent;
(5) mensuration of bisphenol: the concentration of bisphenol in the eluent obtained in determination step (4);
(6) calculating of bisphenol adsorbance: according to the adsorbance of bisphenol on following formula (I) calculated activity charcoal adsorbed film
M＝C
e(V
g+V
e)/f
e(I)
In formula, M is bisphenol adsorbance on adsorbed film, and unit is ng; C
ebe the concentration of bisphenol in eluent, unit is ng/mL; V
gbe the volume of adsorbed film, unit is mL; V
ebe the volume of eluent, unit is mL; f
ebe the elution efficiency of bisphenol, obtained by the adsorbed film of the known bisphenol adsorbance of wash-out;
(7) DGT concentration conversion: the concentration calculating bisphenol in wetland soil or deposit according to Fick's 1st law of diffusion with following formula (II),
C
DGT＝M*Δg/(D*A*t) (II)
In formula, C
dGTbe the concentration of bisphenol in wetland soil or deposit, unit is ng/mL; Δ g is the thickness sum of diffusion barrier and filter membrane, and unit is cm; D is the diffusion coefficient of bisphenol in diffusion barrier, and unit is cm
2/ s; A is the window area of DGT device, and unit is cm
2; T is the standing time of DGT device, and unit is s.
Preferably, the base of described DGT device and the material of lid are acrylonitrile-butadiene-styrene copolymer.
Preferably, in described wetland soil to be measured or deposit, the concentration of bisphenol is less than 40mg/L.
Preferably, in described step (2) inflated with nitrogen time >=6h, described nitrogen is High Purity Nitrogen.
Preferably, in described step (3) DGT device in wetland soil to be measured or deposit standing time >=24h.
Preferably, the eluant, eluent in described step (4) is the mixed liquor of methyl alcohol and sodium hydroxide solution, and wherein the concentration of sodium hydroxide solution is 0.1 ~ 1.0mol/L, and the volume ratio of methyl alcohol and sodium hydroxide solution is 6:4 ~ 10:0.
Preferably, the concentration measuring bisphenol in eluent with the high performance liquid chromatography of fluorescence detector or liquid chromatogram-second order ms method for combined use is adopted in described step (5).
3. beneficial effect
Compared to prior art, beneficial effect of the present invention is:
(1) the invention provides a kind of preparation method of charcoal absorption film, the activated carbon being less than 50 μm with particle diameter obtains charcoal absorption film for adsorbent and agar gel film forming, the small particle diameter sorbing material of adsorbed film surface uniform distribution can provide more adsorption site for bisphenol, high adsorption capacity, adsorbed film of the present invention has stronger toughness and larger adsorption capacity, is wherein all greater than 30 μ g/cm to the adsorption capacity of bisphenol-A, bisphenol b and Bisphenol F
2, compared with prior art, adsorption capacity at least increases 1/3rd;
(2) the charcoal absorption film that the present invention prepares store in 4 DEG C of pure water medium after more than 12 months to the adsorption capacity of bisphenol and performance constant, long shelf-life, be applicable to absorption before long-time preservation and absorption after long-distance transportation;
(3) the invention provides a kind of method measuring bisphenol in wetland soil or deposit based on diffusion film (DGT) technology, choose the charcoal absorption film and AGP test film with high-adsorption-capacity and polytetrafluoroethylene (PTFE) (PTFE) filter membrane is assembled into DGT device, be positioned over after filling the oxygen in nitrogen pretreatment removal device in wetland soil to be measured or deposit, what decrease DGT device puts into script anaerobism or the wetland soil of anaerobic environment or the impact of deposit oxygen, and then eliminate the degraded of the bisphenol caused by change or the conversion of original biological community structure, achieve the in-site detecting of DGT technology to bisphenol in wetland soil or deposit,
(4) in DGT device of the present invention, charcoal absorption film and AGP test film not only make raw material active carbon and agar and easily to obtain and cheap, and preparation technology is simple consuming time short, in addition, teflon membrane filter is more cheap than polyethersulfone membranes conventional in existing DGT technology;
(5) method of bisphenol in the mensuration wetland soil provided in the present invention or deposit, compared with the active Sampling techniques of routine, it is simple to operate laborsaving that DGT technology measures bisphenol, without the need to concentrated, it is convenient to analyze, test result has the representativeness of time span and Spatial Dimension, is applicable to the in situ detection of bisphenol in wetland soil or deposit, and can be used for the environmental risk assessment of bisphenol;
(6) method of bisphenol in mensuration wetland soil provided by the invention or deposit, compared with conventional polar organic matter integrated sampling technology (POCIS), DGT technology measures bisphenol without the need to laboratory investment, and not being subject to the impact of surrounding medium physicochemical property, test result is more credible.
Accompanying drawing explanation
Fig. 1 is the structural representation of DGT device in the present invention;
Fig. 2 be adopt under two kinds of chromatographic conditions respectively in the present invention high performance liquid chromatography (HPLC) method measure bisphenol-A (left side) in eluent, bisphenol b (in) and the spectrogram of Bisphenol F (right side), wherein (a) standard spectrogram obtaining for employing condition I, a b standard spectrogram that () obtains for employing condition II, in (a) and (b), three peaks are followed successively by BPF, BPA and BPB from left to right;
In figure: 1, base; 2, charcoal absorption film; 3, AGP test film; 4, polytetrafluoroethylene (PTFE) (PTFE) filter membrane; 5, lid.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
By reference to the accompanying drawings 1 and Fig. 2, the preparation method of a kind of charcoal absorption film of the present embodiment and the method based on bisphenol in diffusion thin film technique mensuration wetland soil or deposit, adsorbed film is that surface distributed has the short grained agar film of active carbon, the wherein particle diameter <50 μm of activated carbon granule, the adsorbable bisphenol of charcoal absorption film of the present embodiment, is particularly useful for absorption and the analysis of bisphenol in wetland soil or deposit.
Inventor through Specialized Theory analysis and repeatedly repetition test draw: measure bisphenol in wetland soil or deposit utilizing DGT technology effective, not only need to select suitable adsorbent, also need to select suitable diffusion barrier and filter membrane and eluant, eluent.Existing research shows that carbon based material has excellent absorption property to bisphenol, although succeed in developing based on the agar adsorbed film of active carbon, but its corresponding DGT device can not be used for measuring bisphenol, wherein main cause has two aspects: one is that the polyether sulfone material filter membrane that its device adopts can adsorb bisphenol in a large number, cause this material can not be formed in filter membrane and diffusion barrier diffusion gradient and and then caught by adsorbed film; Two is that adopted pickling takes off or the bisphenol that charcoal absorption film adsorbs can not elute by digestion procedure, therefore cannot carry out follow-up concentration determination.Because different handling objects is different with parameter requests such as antijamming capabilities to the adsorption capacity of adsorbed film, wetland soil or deposit do not have mobility substantially, and there is special heterogeneity and the temporal heterogeneity of height, this has higher requirement, so light water processing method cannot be used for the mensuration of bisphenol in wetland soil or deposit to the scene placement of the preparation of adsorbed film and DGT device.Inventor is through theory analysis for many years with repeatedly after repetition test, propose new adsorbed film preparation condition, choose the acticarbon of specific dimensions, in the ratio of specific active carbon and pure water and agar, the adsorbed film prepared increases significantly in performance, the good toughness of the adsorbed film prepared after improving preparation method, adsorbent on adsorbed film distributes very evenly, and can process the mensuration of bisphenol in the wetland soil with height space and temporal heterogeneity or deposit that commonsense method cannot process.The shelf-life of adsorbed film involved in the present invention reaches 12 months, based on the DGT technology (see Fig. 1) of this adsorbed film, AGP test film and PTFE filter membrane, be suitable for placing for a long time in wetland soil or deposit, and it is simple to operate laborsaving, it is convenient to analyze, the concentration measured has the representativeness of time span and Spatial Dimension, and serviceability is excellent, and can be used for the environmental risk assessment of bisphenol.
Based on above-mentioned result of study, the present embodiment adopts the DGT device of charcoal absorption film, AGP test film and teflon membrane filter composition to measure bisphenol in wetland soil or deposit, and wherein the concrete steps of the preparation method of diffusion barrier and adsorbed film are:
A () prepares agar solution: mixed with pure water by agar powder and more than heated solution to 80 DEG C make its transparentization, described agar powder and the mass ratio of pure water are 1.5:100;
B agar solution that step (a) prepares by () injects the two glass sheets spaces accompanying sheet between 0.75mm thick U-shaped plastic partition, extrude bubble between glass plate, be placed horizontally in room temperature by glass plate and cool 1h, in glass plate, solution solidifies and forms AGP test film;
C () prepares Actidose: mixed with pure water by active carbon powder (particle diameter <50 μm) and stir, described active carbon powder and the mass ratio of pure water are 10:100;
D Actidose that step (c) prepares by () adds in the agar solution that step (a) prepares and mixes, obtained mixed solution; Wherein, the Actidose added and the volume ratio of agar solution are 1.5:4;
E mixed solution that step (d) prepares by () injects the two glass sheets spaces accompanying sheet between 0.5mm thick U-shaped plastic partition, extrude bubble between glass plate, be placed horizontally in room temperature by glass plate and cool 1h, in glass plate, solution solidifies and forms charcoal absorption film;
F () is taken out in step (b) and (e) and is cut into the thin rounded flakes that diameter is 2.51cm after film between two glass plates, namely obtain described diffusion barrier and adsorbed film respectively.
The method of charcoal absorption film is prepared in the present embodiment, agar solution and Actidose are mixed to get described charcoal absorption film, preparation process is easily controlled, preparation technology is simple, the diffusion barrier that different batches is obtained and adsorbed film stable performance, and adsorption capacity is large, ageing resistace is good, under acid or alkaline conditions stable performance.
Measure a method for bisphenol in wetland soil or deposit based on diffusion thin film technique, the steps include:
(1) assembling of DGT device: by above-mentioned the charcoal absorption film, AGP test film and the teflon membrane filter (hydrophily that prepare, diameter 25mm, 0.45 μm, aperture, Shanghai ANPEL Scientific Instrument Co., Ltd.) be superimposed between DGT base and the lid with window successively, be assembled into DGT device (as shown in Figure 1), wherein the base of DGT device and the material of lid are acrylonitrile-butadiene-styrene copolymer;
(2) pretreatment of DGT device: DGT device is put into the glass container that pure water is housed, Xiang Shuizhong fills High Purity Nitrogen 6h to remove the oxygen in DGT device.
(3) placement of DGT device: wetland black earth DGT device pretreated in step (2) being put into organic contamination to be measured, standing time is 24h, wherein, the fundamental property of soil is as follows: pH is 6.1, the content of iron oxide is 4985mg/kg (dry weight), Dissolved Organic Matter is 450mg/kg (dry weight), and maximum field capacity is 55%;
(4) recovery of adsorbed film and wash-out: by DGT device after taking out until black earth hygrometrically, with pure water rinsing apparatus surface dirt, then charcoal absorption film is taken out, be positioned in vial, add after 24h placed by eluant, eluent and obtain eluent, eluant, eluent is the mixed liquor of the NaOH of 8mL methyl alcohol and 2mL 0.1mol/L;
(5) mensuration of bisphenol: utilize BPA, BPB and BPF concentration in the eluent obtained in high performance liquid chromatography (HPLC) method determination step (4) to be respectively 38.3 μ g/L, 26.4 μ g/L and 12.1 μ g/L, the method of HPLC is as follows: adopt with fluorescence detector (Waters 2475, Ireland) and XBridge
tMthe liquid chromatograph (HPLC, Waters e2695, Ireland) of C18 post (5 μm, 4.6mm × 250mm), column temperature is set as 35 DEG C, and mobile phase is the mixture of methyl alcohol and pure water, and flow velocity is 1.0mL/min; For reaching best Detection results, when surveying BPA, in mobile phase, the volume ratio of methyl alcohol and pure water is 70:30, and transmitting and excitation wavelength are respectively 315nm and 278nm, this condition called after condition I; When surveying BPB and BPF, in mobile phase, the volume ratio of methyl alcohol and pure water is 60:40, and transmitting and excitation wavelength are respectively 300nm and 273nm, this condition called after condition II.Certainly, three kinds of bisphenols adopt identical conditions also can realize detecting simultaneously.Fig. 2 (a) is the standard spectrogram that employing condition I obtains, the standard spectrogram that Fig. 2 (b) obtains for employing condition II, both differences are the difference of appearance time, and three peaks in figure are followed successively by BPF, BPA and BPB from left to right;
(6) calculating of bisphenol adsorbance: the adsorbance calculating bisphenol on adsorbed film according to following formula (I),
M＝C
e(V
g+V
e)/f
e(I)
In formula, M is bisphenol adsorbance on adsorbed film, C
ethe concentration of bisphenol in eluent, V
gthe volume 0.26mL of adsorbed film, V
ethe volume 10mL of eluent, f
eit is the elution efficiency of bisphenol, when eluant, eluent is the mixed liquor of the NaOH of 8mL methyl alcohol and 2mL 0.1mol/L, the elution efficiency of BPA, BPB and BPF is respectively 45%, 62% and 54%, therefore, BPA, BPB and BPF adsorbance M on adsorbed film can be calculated and be respectively 873ng, 436ng and 230ng;
(7) DGT concentration conversion: the concentration calculating bisphenol in water environment according to Fick's 1st law of diffusion with following formula (II),
C
DGT＝M*Δg/(D*A*t) (II)
In formula, C
dGTbe the concentration of bisphenol in water environment, Δ g is the thickness sum 0.086cm of diffusion barrier and filter membrane, D is the diffusion coefficient of bisphenol in diffusion barrier, and wherein bisphenol-A, bisphenol b and the Bisphenol F diffusion coefficient 25 DEG C time is respectively 5.03 × 10
-6, 5.64 × 10
-6with 4.44 × 10
-6cm
2/ s, A are the window area 2.51cm that DGT device exposes
2, t is 24h and 86400s standing time of DGT device.
DGT according to above-mentioned formulae discovery bisphenol BPA, BPB and BPF measures concentration (C
dGT) be respectively 69 μ g/L, 31 μ g/L and 21 μ g/L.
Embodiment 2
In the present embodiment, the preparation process of diffusion barrier and adsorbed film is with embodiment 1, and difference is: in step (b), the mass ratio of active carbon powder and pure water is 8:100; In step (c), the volume ratio of Actidose and agar solution is 1:4; Step (d) cool time is 30min.
A kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique in the present embodiment, its step is with embodiment 1, difference is: the determination object in step (3) is the wetland laterite of organic contamination, the fundamental property of soil is as follows: pH is 4.0, the content of iron oxide is 18520mg/kg (dry weight), Dissolved Organic Matter is 75mg/kg (dry weight), and maximum field capacity is 52%; The standing time of DGT device in wetland laterite is 30h; Eluant, eluent in step (4) is 10mL methyl alcohol, and the elution efficiency of BPA, BPB and BPF is respectively 56%, 96% and 35%; Utilize BPA and the BPF concentration in liquid chromatogram-second order ms coupling (LC-MS/MS) method mensuration eluent in step (5), LC-MS/MS method is as follows: adopt with Waters XBridge
tMthe HPLC (1260, Agilent) of C18 post (3.5 μm, 2.1mm × 100mm) and the mass spectrum (AB science, the U.S.) of triple level Four bar are connected; The mobile phase of HPLC is the mixture of methyl alcohol and pure water, and volume ratio is 60:40, and flow velocity is 0.2mL/min, and the sampling volume of each sample is 5 μ L; Mass spectrographic all parameters are all optimized, quota ion and the confirmation same bibliography of ion (Gallart-Ayala H., et al., Anal.Chim.Acta 2011,683,227-233).In the wetland laterite finally measured, BPA, BPB and BPF concentration is respectively 92 μ g/L, 5.6 μ g/L and 2.1 μ g/L.
Embodiment 3
In the present embodiment, the preparation process of diffusion barrier and adsorbed film is with embodiment 1, and difference is: in step (b), the mass ratio of active carbon powder and pure water is 5:100; In step (c), the volume ratio of Actidose and agar solution is 1.5:4; Step (d) cool time is 120min.
A kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique in the present embodiment, its step is with embodiment 3, and difference is: the time of filling High Purity Nitrogen in step (2) is 8h; Determination object in step (3) is wetland sand, and the pH of soil is 7.5, and the content of iron oxide is 5080mg/kg (dry weight), and Dissolved Organic Matter is 45mg/kg (dry weight), and maximum field capacity is 37%; The standing time of DGT device in wetland laterite is 36h; Eluant, eluent in step (4) is the mixed liquor of the NaOH of 9mL methyl alcohol and 1mL 0.5mol/L, and the elution efficiency of BPA, BPB and BPF is respectively 43%, 62% and 57%; Utilize BPA, BPB and BPF content in liquid chromatogram-second order ms coupling (LC-MS/MS) method mensuration eluent in step (5), result is respectively 39 μ g/L, does not detect and 6.1 μ g/L.
Embodiment 4
In the present embodiment, the preparation process of diffusion barrier and adsorbed film is with embodiment 1, and difference is: in step (b), the mass ratio of active carbon powder and pure water is 6:100; In step (c), the volume ratio of Actidose and agar solution is 1.2:4; Step (d) cool time is 80min.
A kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique in the present embodiment, its step is with embodiment 3, and difference is: the time of filling High Purity Nitrogen in step (2) is 10h; Determination object in step (3) is freshwater lake deposit, and sedimental fundamental property is as follows: pH is 7.85, and the content of iron oxide is 650mg/kg (dry weight), and Dissolved Organic Matter is 184mg/kg (dry weight); Eluant, eluent in step (4) is the mixed liquor of the NaOH of 6mL methyl alcohol and 4mL 0.2mol/L, and the elution efficiency of BPA, BPB and BPF is respectively 53%, 65% and 57%; Utilize BPA, BPB and BPF content in liquid chromatogram-second order ms coupling (LC-MS/MS) method mensuration eluent in step (5), result is respectively 78 μ g/L, 6.7 μ g/L and 10.2 μ g/L.
A kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique described in embodiment 1 ~ 4, the charcoal absorption film preparation technique related to is simple, toughness is strong, even particle distribution on adsorbed film, adsorption capacity are high, long shelf-life, and serviceability is excellent.The DGT device that charcoal absorption film of the present invention is housed is utilized to measure the concentration of bisphenol in wetland soil or deposit, simple operation, time saving and energy saving, reliable results.
Claims (9)
1. a preparation method for charcoal absorption film, the steps include:
A agar powder mixes with pure water and more than heated solution to 80 DEG C makes its transparentization obtain agar solution by (), wherein the mass ratio of agar powder and pure water is 1.5:100;
B active carbon powder mixes with pure water and stirs and obtains Actidose by (), wherein the mass ratio of active carbon powder and pure water is (5 ~ 10): 100;
C Actidose that step (b) prepares by () adds in the agar solution that step (a) prepares and mixes, obtained mixed solution, wherein, the Actidose added and the volume ratio of agar solution are (1 ~ 1.5): 4;
D mixed solution that step (c) prepares by () injects two glass sheets spaces, extrudes bubble between glass plate, is placed horizontally at by glass plate in room temperature and cools 30 ~ 120min, and in glass plate, solution solidifies and forms charcoal absorption film.
2. the preparation method of a kind of charcoal absorption film according to claim 1, is characterized in that: the particle diameter <50 μm of active carbon powder in described step (b).
3. measure a method for bisphenol in wetland soil or deposit based on diffusion thin film technique, the steps include:
(1) assembling of DGT device: the charcoal absorption film prepared in claim 1, AGP test film and teflon membrane filter are superimposed between DGT base and the lid with window successively, are assembled into DGT device;
(2) pretreatment of DGT device: DGT device is put into the glass container that pure water is housed, in water, inflated with nitrogen is to remove the oxygen in DGT device;
(3) placement of DGT device: DGT device pretreated in step (2) is put into the absorption that wetland soil to be measured or deposit carry out bisphenol;
(4) recovery of adsorbed film and wash-out: after being taken out from wetland soil to be measured or deposit by DGT device, with pure water rinsing apparatus surface dirt, then takes out charcoal absorption film, is positioned in vial, obtains eluent after adding eluant, eluent;
(5) mensuration of bisphenol: the concentration of bisphenol in the eluent obtained in determination step (4);
(6) calculating of bisphenol adsorbance: according to the adsorbance of bisphenol on following formula (I) calculated activity charcoal adsorbed film
M＝C
e(V
g+V
e)/f
e(I)
In formula, M is bisphenol adsorbance on adsorbed film, and unit is ng; C
ebe the concentration of bisphenol in eluent, unit is ng/mL; V
gbe the volume of adsorbed film, unit is mL; V
ebe the volume of eluent, unit is mL; f
ebe the elution efficiency of bisphenol, obtained by the adsorbed film of the known bisphenol adsorbance of wash-out;
(7) DGT concentration conversion: the concentration calculating bisphenol in wetland soil or deposit according to Fick's 1st law of diffusion with following formula (II),
C
DGT＝M*Δg/(D*A*t) (II)
In formula, C
dGTbe the concentration of bisphenol in wetland soil or deposit, unit is ng/mL; Δ g is the thickness sum of diffusion barrier and filter membrane, and unit is cm; D is the diffusion coefficient of bisphenol in diffusion barrier, and unit is cm
2/ s; A is the window area of DGT device, and unit is cm
2; T is the standing time of DGT device, and unit is s.
4. a kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique according to claim 3, is characterized in that: the base of described DGT device and the material of lid are acrylonitrile-butadiene-styrene copolymer.
5. a kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique according to claim 4, is characterized in that: in described wetland soil to be measured or deposit, the concentration of bisphenol is less than 40mg/L.
6. a kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique according to claim 4, is characterized in that: in described step (2) inflated with nitrogen time >=6h, described nitrogen is High Purity Nitrogen.
7. a kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique according to claim 6, is characterized in that: in described step (3) DGT device in wetland soil to be measured or deposit standing time >=24h.
8. a kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique according to claim 3, it is characterized in that: the eluant, eluent in described step (4) is the mixed liquor of methyl alcohol and sodium hydroxide solution, wherein the concentration of sodium hydroxide solution is 0.1 ~ 1.0mol/L, and the volume ratio of methyl alcohol and sodium hydroxide solution is 6:4 ~ 10:0.
9. a kind of method measuring bisphenol in wetland soil or deposit based on diffusion thin film technique according to claim 3-8 any one, is characterized in that: adopt the concentration measuring bisphenol in eluent with the high performance liquid chromatography of fluorescence detector or liquid chromatogram-second order ms method for combined use in described step (5).
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