CN110320196A - A kind of highly sensitive method for detecting inorganic mercury and organic mercury - Google Patents
A kind of highly sensitive method for detecting inorganic mercury and organic mercury Download PDFInfo
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 184
- 238000000034 method Methods 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001868 water Inorganic materials 0.000 claims abstract description 26
- 239000002086 nanomaterial Substances 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000011896 sensitive detection Methods 0.000 claims abstract description 12
- 239000002028 Biomass Substances 0.000 claims abstract description 9
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 6
- 238000001917 fluorescence detection Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 239000006228 supernatant Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000696 magnetic material Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002242 deionisation method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 244000252132 Pleurotus eryngii Species 0.000 claims description 5
- 235000001681 Pleurotus eryngii Nutrition 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- SIURBWXPWMTEGD-UHFFFAOYSA-N CO.[Si](OCC)(O)(O)O Chemical compound CO.[Si](OCC)(O)(O)O SIURBWXPWMTEGD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- AWGTVRDHKJQFAX-UHFFFAOYSA-M chloro(phenyl)mercury Chemical compound Cl[Hg]C1=CC=CC=C1 AWGTVRDHKJQFAX-UHFFFAOYSA-M 0.000 claims description 2
- BABMCXWQNSQAOC-UHFFFAOYSA-M methylmercury chloride Chemical compound C[Hg]Cl BABMCXWQNSQAOC-UHFFFAOYSA-M 0.000 claims description 2
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 21
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- -1 Hg by reaction2+ Chemical compound 0.000 abstract 1
- 229910002567 K2S2O8 Inorganic materials 0.000 abstract 1
- 239000007850 fluorescent dye Substances 0.000 abstract 1
- 238000012544 monitoring process Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 31
- 238000002360 preparation method Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 244000138502 Chenopodium bonus henricus Species 0.000 description 3
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000002137 ultrasound extraction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PJDVOLYULHZZAG-UHFFFAOYSA-N ethylmercury Chemical compound CC[Hg] PJDVOLYULHZZAG-UHFFFAOYSA-N 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000874 microwave-assisted extraction Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of methods of highly sensitive detection inorganic mercury and organic mercury, according to Hg2+There is highly sensitive specificity fluorescent probe quenching effect to synthesized biomass carbon dots, and be the organic mercury of representative without this effect using methyl mercury, passes through organic mercury and strong oxidizer K2S2O8Or KMnO4Organomercurial transformation is inorganic mercury, i.e. Hg by reaction2+, Fe3O4@SiO2- SH magnetic Nano material is to Hg2+Selective absorption elutes the Hg being adsorbed by adjusting pH2+, detection total mercury, inorganic mercury and organic mercury content establish the new method of highly sensitive fluorescence detection inorganic mercury and organic mercury.The method has detection sensitivity high, and high specificity is easy to operate, is not necessarily to large-scale instrument and equipment, has detection for inorganic mercury in water body and organic mercury, be able to satisfy relevant national standard testing requirements, reach environmental monitoring purpose.
Description
Technical field
The present invention relates to a kind of methods of highly sensitive detection inorganic mercury and organic mercury.Belong to detection technique field.
Background technique
Mercury is universally acknowledged most dangerous one of inorganic pollution, and mercury is in nature with shapes such as inorganic mercury and organic mercuries
Formula exists, and the existing forms of mercury determine its environmental behaviour and environmental pollution effect.Toxicity, the shape of bioavailability and mercury of mercury
State is closely related, and in common compound containing mercury, the toxicity of methyl mercury is most strong.Because methyl mercury has fat-soluble, may pass through cell
Film reaches cell interior, while compared to other forms such as inorganic mercury, Elemental Mercuries, methyl mercury is more stable in human body, is difficult to pass through
Metabolism excretes.Since content is very low in nature for mercury, the methyl mercury in natural water body is 0.02~0.10
NgL-1, in contaminated water body, the mass concentration of methyl mercury is up to several ngL-1, have been cited as international chemicals
6 kinds of most dangerous one of substances in matter security procedures.China's water environment quality standard (GB 3838-2002) regulation I,
II, the limitation of methyl mercury is 1.0 × 10 in III class waters-6MgL-1, there is no Hg(II), the related limit of ethyl mercury (Et Hg)
Amount standard and examination criteria.
The morphological analysis method of mercury includes atomic spectroscopy, gas chromatography, inductively coupled plasma mass spectrometry method and liquid
Phase chromatography-atomic fluorescence combination method etc..In the food security standard GB 5009.17-2014 that in March, 2016 implements " in food
The measurement of total mercury and organic mercury " in, it is specified that method is liquid chromatogram-atomic fluorescence combination method.Although being national standard method,
There is also it is complicated for operation, need large-scale instrument and equipment, no matter for testing agency or enterprise, almost without such equipment, side
The application of method is extremely restricted；Operation needs professional technician simultaneously, and different personnel's measurement results are difficult unanimously.
Carbon dots (CDs) be one kind be uniformly dispersed, shape it is subsphaeroidal, partial size is in 10 nm novel fluorescence carbon nanometer below
Material.Because it has, preparation is simple, surface functional group is abundant, low bio-toxicity, resistance to photobleaching, good water-soluble and biofacies
The advantages that capacitive, it is all to be widely used in photocatalysis, biosensor, cell imaging, pharmaceutical carrier, the detection etc. of heavy metal ion
It is multi-field.Hg is detected by fluorescence probe of carbon dots2+There are many reports, is all based on Hg entirely2+To the fluorescent quenching of carbon dots, but
For the detection method of the carbon dots fluorescence probe of methyl mercury, currently without any report；Simultaneously because Hg in current detection method2+
Detection limit is not below 10 ng/L substantially, with existing GB/T 14204-93 compared with GB 5009.17-2014, the inspection of methyl mercury
Survey limit will reach 0.2-10 ng/L, and there are also certain distances.
Therefore, research and develop it is a kind of it is easy to operate, do not need large-scale instrument and equipment and professional operator, can it is simple, quickly,
The new detecting method of Sensitive Detection organic mercury and inorganic mercury just becomes urgent problem to be solved in the prior art.The present invention is main
Organic mercury is oxidized to inorganic mercury using oxidant, detects total mercury and inorganic mercury by fluorescence probe of carbon dots, then calculate organic mercury
Content.Preparing carbon dots disadvantage maximum at present as raw material using biomass is exactly that fluorescent yield is lower, the reason is that not being carbonized largely
Aggregate into the presence of carbon dots hydro-thermal biomass.The present invention prepares raw material by carbon dots of Pleurotus eryngii, and hydro-thermal method prepares sulfur doping fluorescent carbon
Point, then with sodium hydroxide and dioxygen water process unreacted hydro-thermal biomass, the higher carbon dots of fluorescent yield are obtained, for the glimmering of mercury
Light probe, detection are limited up to 0.05 ng/L.
Summary of the invention
The purpose of the present invention is to provide a kind of easy to operate, high sensitivity, detection time short inorganic mercuries and organic mercury
Measuring method.
A kind of highly sensitive method for detecting inorganic mercury and organic mercury, it is characterised in that method includes the following steps:
(1) production of working curve: being separately added into 50~100 μ L (2.0 g/L) fluorescent carbon point solution in 10mL colorimetric cylinder, and 1
~2 mL (0. 2 mol/L, pH=7. 0) NaH2PO4 - Na2HPO4Buffer solution, 400 Hgs of the μ L containing various concentration2+Mark
Quasi- solution, distilled water to 10 mL of total volume, carries out fluorescence detection after shaking up.With Hg2+The fluorescence of the increase of concentration, carbon dots is strong
Angle value constantly reduces, I0/ I and Hg2+Good linear relationship, I is presented in concentration within the scope of 0.1~10 ng/L0For Hg is added2+
Fluorescent carbon point fluorescence intensity at maximum emission wavelength, I are fluorescent carbon point fluorescence intensity at maximum emission wavelength, obtain Hg2+
Regression equation, related coefficient, relative standard deviation, the rate of recovery.
(2) Hg2+ Absorption: containing Hg2+ Aqueous solution in, the Fe of synthesis is added3O4@SiO2- SH magnetic Nano material
Material, 1~2min of vortex mixed after placing 1~2min, separate magnetic material using magnet, after removing supernatant, in magnetic material
0.1 mol L of middle addition-1HCl solution makees eluant, eluent, and magnet separation takes supernatant after 1~2min of ultrasound, and supernatant is with 0.1
mol L-1 NaOH tune pH to 6~7, it is spare.
(3) in the aqueous solution containing inorganic mercury and organic mercury, the hydrochloric acid containing oxidant total mercury and organic mercury determination: is added
Solution, 10~15 min of confined reaction, is oxidized to inorganic mercury for organic mercury, adsorbs inorganic mercury and total mercury respectively according to step (2),
Inorganic mercury and total mercury content are measured respectively according still further to step (1), total mercury content are subtracted into inorganic mercury content, as organic mercury contains
Amount.
Fluorescent carbon point described in step (1) is prepared by following methods:
(1) 10~15 parts of Pleurotus eryngiis are taken, are smashed with juicer, are added 1~2 part of the concentrated sulfuric acid, are uniformly mixed；It is placed in polytetrafluoroethyl-ne
In alkene liner hydrothermal reaction kettle, 180 DEG C of 20~24 h of heated at constant temperature, cooled to room temperature after the reaction was completed.
(2) acquired solution is crossed into 0.22 μm of filter membrane and obtains hydro-thermal biological particles object, it is each with deionized water and dehydrated alcohol
Washing 3-5 times, dry 24~48 h in 60 DEG C of drying boxes.
(3) sodium hydroxide solution is dispersed by the drying hydro-thermal biomass that step (2) obtains, a small amount of hydrogen peroxide, room is added
Temperature is lower to stir 8~10 h, obtains transparent brown liquid, as fluorescent carbon point.
Fe described in step (2)3O4@SiO2- SH magnetic Nano material is prepared by following methods:
(1) 4.33 g FeCl are taken3∙6H2O and 2.78 g FeSO4 ∙7H2O is dissolved in 70~100 mL water, and nitrogen protection is simultaneously stirred
It mixes down, is warming up to 75~80 DEG C.Then NH3∙H2O tune pH to 11.0, the reaction was continued 1~1.5 h, product deionization are washed 3 times,
And it is dried in vacuo in 40~60 DEG C up to Fe3O4。
(2) step (1) Fe is taken3O4It is scattered in 60~100mL water, 5~10 mLNH is added3 ∙H2O and 50 mL containing 1.5~
3mL ethyl orthosilicate methanol solution after 10~15 min of ultrasonic mixing, stirs 6~8 h.Product deionization is washed 3 times, and in
40~60 DEG C are dried in vacuo up to Fe3O4@SiO2。
(3) step (2) Fe will be taken3O4@SiO2It is scattered in 140~150 mL glycerine, under nitrogen protection and stirring, rises
2.5~3.0 mLNH are added to after 60~80 DEG C in temperature3∙H2O and 80~100 mL contains 2~3 mL mercaptopropyl trimethoxysilanes
Methanol.After reacting 1~2 h, 80 DEG C are continued 5~6 h of stirring.Reaction product deionized water and methanol are during alternately cleaning to pH is in
Property, and up to Fe after 40~60 DEG C of vacuum drying3O4@SiO2- SH magnetic Nano material.
The maximum excitation wavelength of step (1) described carbon dots is 326 nm, and maximum emission wavelength is 411 nm.
Hg described in step (2)2+ Aqueous solution, Fe3O4@SiO2The envelope-bulk to weight ratio of-SH magnetic Nano material and HCl is
1:0.02~0.04:0.02~0.04.
Organic mercury described in step (3) includes methyl-mercuric chloride, ethylmercuric chloride, one or more of in phenylmercuric chloride.
Organic mercury concentration described in step (2) is 0.1~10ng/L, and oxidant is one of potassium peroxydisulfate, potassium permanganate
Kind, percent weight in volume concentration is 4 ~ 6%, and concentration of hydrochloric acid is 0.5~1.0 mol/L, and volume ratio is 1~0.01:0.05
~0.01:0.05.
The w/v of hydro-thermal biomass described in step (3) and sodium hydroxide and hydrogen peroxide be 0.1~30:60~
2:5, naoh concentration are 0.1~0.3 mol/L.
The present invention has the advantages that
1. the present invention prepares the sulfur doping carbon dots of high fluorescent yield by secondary hydro-thermal process for the first time using Pleurotus eryngii as raw material, benefit
With the carbon dots to Hg2+Fluorescence probe establishes Hg2+Highly sensitive detection fluorescent method.
2. organic mercury is oxidized to inorganic Hg using oxidant2+, establish the highly sensitive fluorescence inspection of organic mercury and inorganic mercury
It surveys, this method is easy to operate, does not need high instrument and equipment investment and the professional technician of current art, while can reach existing
The advantages of sensitivity of row technology detection.
3. the technology uses the magnetic Nano material with Specific adsorption to adsorb inorganic mercury, detection sensitivity not only can be improved, but also
Separable Matrix effects substance is limited using the detection of technology detection total mercury up to 0.05 ng/L, has been more than food safety country
The requirement of pollutant limitation GB2762-2017 in standard food.
4. using organic mercury and inorganic mercury in sepectrophotofluorometer detection environment food, detection limits low, high sensitivity,
Recovery of standard addition is high.
Detailed description of the invention
From Fig. 1 result: present invention preparation is to water-soluble sulfur doping fluorescent carbon quantum dot to Hg2+There is stronger photoluminescence line
Property quenching effect, Fig. 2 show other metal ions coexisted to Hg2+Measurement do not interfere with, method has preferable specificity.
Specific embodiment
The present invention is described in further detail below by embodiment, but embodiment is not to the technology of the present invention side
The restriction of case, it is all based on present invention teach that made variation or equivalent replacement is within the scope of protection of the invention.
Embodiment 1 utilizes the content of organic mercury and inorganic mercury in present invention detection environmental water sample
1, the preparation of fluorescent carbon point:
(1) 10~15 parts of Pleurotus eryngiis are taken, are smashed with juicer, are added 1~2 part of the concentrated sulfuric acid, are uniformly mixed；It is placed in polytetrafluoroethyl-ne
In alkene liner hydrothermal reaction kettle, 180 DEG C of 20~24 h of heated at constant temperature, cooled to room temperature after the reaction was completed.
(2) acquired solution is crossed into 0.22 μm of filter membrane and obtains hydro-thermal biological particles object, it is each with deionized water and dehydrated alcohol
Washing 3-5 times, dry 24~48 h in 60 DEG C of drying boxes.
(3) sodium hydroxide solution is dispersed by the drying hydro-thermal biomass that step (2) obtains, a small amount of hydrogen peroxide, room is added
Temperature is lower to stir 8~10 h, obtains transparent brown liquid, as fluorescent carbon point.
2、Fe3O4@SiO2The preparation of-SH magnetic Nano material:
(1) 4.33 g FeCl are taken3∙6H2O and 2.78 g FeSO4∙7H2O is dissolved in 70~100 mL water, and nitrogen protection simultaneously stirs
Under, it is warming up to 75~80 DEG C.Then NH3∙H2O tune pH to 11.0, the reaction was continued 1~1.5 h, product deionization are washed 3 times, and
It is dried in vacuo in 40~60 DEG C up to Fe3O4。
(2) step (1) Fe is taken3O4It is scattered in 60~100mL water, 5~10 mLNH is added3 ∙H2O and 50 mL containing 1.5~
3mL ethyl orthosilicate methanol solution after 10~15 min of ultrasonic mixing, stirs 6~8 h.Product deionization is washed 3 times, and in
40~60 DEG C are dried in vacuo up to Fe3O4@SiO2。
(3) step (2) Fe will be taken3O4@SiO2It is scattered in 140~150 mL glycerine, under nitrogen protection and stirring, rises
2.5~3.0 mLNH are added to after 60~80 DEG C in temperature3∙H2O and 80~100 mL contains 2~3 mL mercaptopropyl trimethoxysilanes
Methanol.After reacting 1~2 h, 80 DEG C are continued 5~6 h of stirring.Reaction product deionized water and methanol are during alternately cleaning to pH is in
Property, and up to Fe after 40~60 DEG C of vacuum drying3O4@SiO2- SH magnetic Nano material.
3, the production of working curve: containing 0.1,0.5,1.0,3.0,5.0,8.0,10 .0 ng/L Hg2+In titer,
Sequentially add 50~100 μ L fluorescent carbon point solution of 2.0 g/L, 0.2 NaH of mol/L pH=7. 02PO4 - Na2HPO4
1~2 mL of buffer solution, distilled water to 10 mL of total volume are 326 nm, emission maximum wave in maximum excitation wavelength after shaking up
A length of 411 nm carries out fluorescence detection.With Hg2+Concentration is abscissa, I0/ I is ordinate, I0For Hg is added2+Fluorescent carbon point exists
Fluorescence intensity at maximum emission wavelength, I are fluorescent carbon point fluorescence intensity at maximum emission wavelength, draw standard curve, calculate
Regression equation, related coefficient, relative standard deviation, range of linearity etc. are shown in Table 1, and recovery of standard addition is shown in Table 2 in sample.
1 Hg of table2+ Linear equation, related coefficient, relative standard deviation, the range of linearity
| Working curve | Related coefficient (r) | Range of linearity ng/L | RSD%(n=5) | LOD ng/L |
| y=3.4196x-10.04 | 0.9990 | 0.1~10.0 | 1.28 | 0.05 |
Hg in 2 sample of table2+Recovery of standard addition
| Scalar quantity (ng/L) | Measured value (ng/L) | The rate of recovery (%) | RSD(%) |
| 0.5 | 0.465 | 93.0 | 6.1 |
| 1.0 | 0.968 | 96.8 | 4.1 |
| 5.0 | 4.86 | 97.2 | 3.5 |
4, organic mercury and Hg in environmental water sample2+Measurement:
(1) oxidation of organic mercury: taking 100 mL water samples, is added 4% potassium peroxydisulfate 1mL, 1.0 mol/L hydrochloric acid solution 1mL, closed
10 min are reacted, organic mercury is oxidized to inorganic mercury；
(2) inorganic mercury and total mercury absorption: take 100 mL water samples and it is above-mentioned aoxidized water sample, each Fe that step 1 is added and synthesizes3O4@
SiO2- SH magnetic Nano material 1mg, 1~2min of vortex mixed after placing 1~2min, separate magnetic material using magnet, remove
After removing supernatant, 0.1 mol L is added in magnetic material-1HCl 1mL solution makees eluant, eluent, after 1~2min of ultrasound, magnet
Separation takes supernatant, 0.1 mol L of supernatant-1 NaOH tune pH to 6~7 obtains inorganic mercury and total mercury sample measurement liquid；
(3) inorganic mercury and Determination of Total Mercury: the sample liquid that step (2) is handled well, according to step 3 Hg2+The identical item of working curve
Inorganic mercury and Determination of Total Mercury are carried out under part, substitutes into regression equation, show that inorganic mercury content is 5.41 ng/L, total mercury content is
5.51 ng/L, organic mercury content are 0.10 ng/L.
Embodiment 2 utilizes the content of organic mercury and inorganic mercury in present invention detection soil, step are as follows:
1, the preparation of fluorescent carbon point: with embodiment 1
2、Fe3O4@SiO2The preparation of-SH magnetic Nano material: with embodiment 1
3, the production of working curve: with embodiment 1
4, organic mercury and Hg in soil2+Measurement:
(1) sample pre-treatments: accurately weighing 1.0g(and be accurate to 0.01g) pedotheque in centrifuge tube, is slowly added to 0.50
Mol/L nitric acid solution 20mL, stirring while adding to bubble is not generated is extremely 1 h of ultrasonic extraction, with 4000 r/min centrifugation
5min, draws upper layer clear solution 10.00mL in 50mL beaker, adjusts pH 7.5 with ammonia spirit (10:90), is transferred to 50mL
In volumetric flask, deionized water is settled to scale.
(2) oxidation of organic mercury: taking step (1) to handle 50 mL solution, and 5% potassium permanganate, 2 mL, 0.5 mol/L salt is added
2 mL of acid solution, 12 min of confined reaction, is oxidized to inorganic mercury for organic mercury；
(3) it inorganic mercury and total mercury absorption: takes step (1) to handle and step (2) was aoxidized each 1 mL of sample, use deionized water
50 mL are diluted to, each Fe that step 1 is added and synthesizes3O4@SiO2- SH magnetic Nano material 1mg, 1~2min of vortex mixed are placed
After 1~2min, magnetic material is separated using magnet, after removing supernatant, 0.1 mol L is added in magnetic material-1 HCl
1mL solution makees eluant, eluent, and after 1~2min of ultrasound, magnet separation takes supernatant, 0.1 mol L of supernatant-1 NaOH tune pH to 6
~7, obtain inorganic mercury and total mercury sample measurement liquid；
(4) inorganic mercury and Determination of Total Mercury: the sample liquid that step (3) is handled well, according to step 3 Hg2+The identical item of working curve
Inorganic mercury and Determination of Total Mercury are carried out under part, substitutes into regression equation, show that inorganic mercury content is 4.85 μ g/kg, total mercury content is
6.08 μ g/kg, organic mercury content are 1.23 μ g/kg.
Embodiment 3 detects the content of organic mercury and inorganic mercury in wizened bacterium, step using the present invention are as follows:
1, the preparation of fluorescent carbon point: with embodiment 1
2、Fe3O4@SiO2The preparation of-SH magnetic Nano material: with embodiment 1
3, the production of working curve: with embodiment 1
4, organic mercury and Hg in wizened bacterium2+Measurement:
(1) sample pre-treatments: weigh the levigate wizened bacterium sample 2g(of beveller and be accurate to 0.01g) in extraction glass tube,
It is put into magnetic stirrer, is added 100 mL extract liquors (HCl of 0.07 mol/L), with Microwave Extraction Apparatus at 55 DEG C, pressure 15
MPa, 110 W of power keep being extracted under conditions of 15 min.It is put into refrigerator after the completion of extraction and stands 5 min, it will be upper
Clear liquid is transferred in centrifuge tube, 14000 r/min, 4 DEG C, is centrifuged under the conditions of 5 min, is removed supernatant, with ammonia spirit (10:
90) pH 7.5 is adjusted, is transferred in 50mL volumetric flask, deionized water is settled to scale.
(2) oxidation of organic mercury: taking step (1) to handle 50 mL solution, and 6% potassium permanganate, 1.5 mL, 0.5 mol/L is added
1.5 mL of hydrochloric acid solution, 13 min of confined reaction, is oxidized to inorganic mercury for organic mercury；
(3) inorganic mercury and total mercury absorption: taking step (1) to handle and step (2) aoxidized each 50 mL of sample, each that step 1 is added
The Fe of synthesis3O4@SiO2- SH magnetic Nano material 1mg, 1~2min of vortex mixed are separated after placing 1~2min using magnet
0.1 mol L is added after removing supernatant in magnetic material in magnetic material-1HCl 1mL solution makees eluant, eluent, and ultrasound 1~
After 2min, magnet separation takes supernatant, 0.1 mol L of supernatant-1 NaOH tune pH to 6~7 obtains inorganic mercury and total mercury sample
Product measure liquid；
(4) inorganic mercury and Determination of Total Mercury: the sample liquid that step (3) is handled well, according to step 3 Hg2+The identical item of working curve
Inorganic mercury and Determination of Total Mercury are carried out under part, substitutes into regression equation, show that inorganic mercury content is 3.57 ng/kg, total mercury content is
3.86 ng/kg, organic mercury content are 0.29 ng/kg.
Embodiment 4 utilizes the content of organic mercury and inorganic mercury in present invention detection face cleaning cream, step are as follows:
1, the preparation of fluorescent carbon point: with embodiment 1
2、Fe3O4@SiO2The preparation of-SH magnetic Nano material: with embodiment 1
3, the production of working curve: with embodiment 1
4, organic mercury and Hg in face cleaning cream2+Measurement:
(1) sample pre-treatments: accurately weigh 1.0g(and be accurate to 0.01g) in plastic centrifuge tube, 10 mL hydrochloric acid solutions are added
(5 mol/L), vortex mixed 5min, in 15 min of water bath sonicator under room temperature, with 10000 r/ under the conditions of 4 DEG C
Min be centrifuged 15 min, remove supernatant, with ammonia spirit (10:90) adjust pH 7.5, be transferred in 50mL volumetric flask, go from
Sub- water is settled to scale.
(2) oxidation of organic mercury: taking step (1) to handle 50 mL solution, and 6% potassium peroxydisulfate, 0.5 mL, 0.8 mol/L is added
1 mL of hydrochloric acid solution, 15 min of confined reaction, is oxidized to inorganic mercury for organic mercury；
(3) inorganic mercury and total mercury absorption: taking step (1) to handle and step (2) aoxidized each 50 mL of sample, each that step 1 is added
The Fe of synthesis3O4@SiO2- SH magnetic Nano material 1mg, 1~2min of vortex mixed are separated after placing 1~2min using magnet
0.1 mol L is added after removing supernatant in magnetic material in magnetic material-1HCl 1mL solution makees eluant, eluent, and ultrasound 1~
After 2min, magnet separation takes supernatant, 0.1 mol L of supernatant-1 NaOH tune pH to 6~7 obtains inorganic mercury and total mercury sample
Product measure liquid；
(4) inorganic mercury and Determination of Total Mercury: the sample liquid that step (3) is handled well, according to step 3 Hg2+The identical item of working curve
Inorganic mercury and Determination of Total Mercury are carried out under part, substitutes into regression equation, show that inorganic mercury content is 0.45 ng/kg, total mercury content is
0.96 ng/kg, organic mercury content are 0.51 ng/kg.
Embodiment 5 utilizes the content of organic mercury and inorganic mercury in present invention detection fish, step are as follows:
1, the preparation of fluorescent carbon point: with embodiment 1
2、Fe3O4@SiO2The preparation of-SH magnetic Nano material: with embodiment 1
3, the production of working curve: with embodiment 1
4, organic mercury and Hg in fish2+Measurement:
(1) sample pre-treatments: accurately weighing 1.0g(and be accurate to 0.01g) fish sample is placed in centrifuge tube, it is slowly added to 10 mL
5 mol/L HCl extract reagent, closed to stand overnight.During which 60 min of ultrasonic extraction at room temperature shakes number with oscillator
It is secondary.15 min are centrifuged with 4000 rpm revolving speeds at 4 DEG C, upper layer clear solution 10.00mL is drawn in 50mL beaker, uses ammonium hydroxide
Solution (10:90) adjusts pH 7.5, is transferred in 50mL volumetric flask, deionized water is settled to scale.
(2) oxidation of organic mercury: taking step (1) to handle 50 mL solution, and 4% potassium permanganate, 2 mL, 0.7 mol/L salt is added
2 mL of acid solution, 14 min of confined reaction, is oxidized to inorganic mercury for organic mercury；
(3) inorganic mercury and total mercury absorption: taking step (1) to handle and step (2) aoxidized each 1 mL of sample, dilute with deionized water
It releases to 50 mL, each Fe that step 1 is added and synthesizes3O4@SiO2- SH magnetic Nano material 1mg, 1~2min of vortex mixed place 1
After~2min, magnetic material is separated using magnet, after removing supernatant, 0.1 mol L is added in magnetic material-1 HCl 1mL
Solution makees eluant, eluent, and after 1~2min of ultrasound, magnet separation takes supernatant, 0.1 mol L of supernatant-1 NaOH tune pH to 6~
7, obtain inorganic mercury and total mercury sample measurement liquid；
(4) inorganic mercury and Determination of Total Mercury: the sample liquid that step (3) is handled well, according to step 3 Hg2+The identical item of working curve
Inorganic mercury and Determination of Total Mercury are carried out under part, substitutes into regression equation, show that inorganic mercury content is 0.15 μ g/kg, total mercury content is
0.72 μ g/kg, organic mercury content are 0.12 μ g/kg.
Above embodiments carry out recovery of standard addition test, the results are shown in Table 3.
3 recovery of standard addition test result of table (μ g/kg)
Inorganic mercury addition is in table with Hg2+For standard, organic mercury is added using methyl mercury as standard.
As seen from the results in Table 3: detecting Hg with carbon dots fluorescence probe of the present invention2+And nothing will be changed into for organic mercury by oxidation
Machine mercury summarize mercury and organic mercury detection, have comparable accuracy and reliability.
Claims (9)
1. a kind of method of highly sensitive detection inorganic mercury and organic mercury, it is characterised in that method includes the following steps:
(1) production of working curve: being separately added into 50~100 μ L (2.0 g/L) fluorescent carbon point solution in 10mL colorimetric cylinder, and 1
~2 mL (0.2 mol/L, pH=7. 0) NaH2PO4 - Na2HPO4Buffer solution, 400 Hgs of the μ L containing various concentration2+Mark
Quasi- solution, distilled water to 10 mL of total volume, carries out fluorescence detection after shaking up；With Hg2+The fluorescence of the increase of concentration, carbon dots is strong
Angle value constantly reduces, I0/ I and Hg2+Good linear relationship, I is presented in concentration within the scope of 0.01~10 ng/L0For Hg is added2 +Fluorescent carbon point fluorescence intensity at maximum emission wavelength, I are fluorescent carbon point fluorescence intensity at maximum emission wavelength, obtain Hg2+
Regression equation, related coefficient, relative standard deviation, the rate of recovery；
(2) Hg2+ Absorption: containing Hg2+ Aqueous solution in, the Fe of synthesis is added3O4@SiO2- SH magnetic Nano material, whirlpool
1~2min of mixing is revolved, after placing 1~2min, magnetic material is separated using magnet, after removing supernatant, adds in magnetic material
Enter 0.1 mol L-1HCl solution makees eluant, eluent, and magnet separation takes supernatant, 0.1 mol L of supernatant after 1~2min of ultrasound-1 NaOH tune pH to 6~7, it is spare；
(3) in the aqueous solution containing inorganic mercury and organic mercury, it is molten that the hydrochloric acid containing oxidant total mercury and organic mercury determination: is added
Liquid, 10~15 min of confined reaction, is oxidized to inorganic mercury for organic mercury, adsorbs inorganic mercury and total mercury respectively according to step (2), then
Inorganic mercury and total mercury content are measured respectively according to step (1), total mercury content are subtracted into inorganic mercury content, as organic mercury content.
2. the method for highly sensitive detection inorganic mercury according to claim 1 and organic mercury, it is characterised in that: step (1) institute
The fluorescent carbon point stated is prepared by following methods:
(1) 10~15 parts of Pleurotus eryngiis are taken, are smashed with juicer, are added 1~2 part of the concentrated sulfuric acid, are uniformly mixed；It is placed in polytetrafluoroethyl-ne
In alkene liner hydrothermal reaction kettle, 180 DEG C of 20~24 h of heated at constant temperature, cooled to room temperature after the reaction was completed；
(2) acquired solution is crossed into 0.22 μm of filter membrane and obtains hydro-thermal biological particles object, respectively washed with deionized water and dehydrated alcohol
3-5 times, dry 24~48 h in 60 DEG C of drying boxes；
(3) sodium hydroxide solution is dispersed by the drying hydro-thermal biomass that step (2) obtains, a small amount of hydrogen peroxide is added, at room temperature
8~10 h are stirred, transparent brown liquid, as fluorescent carbon point are obtained.
3. the method for highly sensitive detection inorganic mercury according to claim 1 and organic mercury, it is characterised in that: step (2) institute
The Fe stated3O4@SiO2- SH magnetic Nano material is prepared by following methods:
(1) 4.33 g FeCl are taken3∙ 6H2O and 2.78 g FeSO4∙7H2O is dissolved in 70~100 mL water, and nitrogen protection simultaneously stirs
Under, 75~80 DEG C are warming up to, then NH3∙H2O tune pH to 11.0, the reaction was continued 1~1.5 h, product deionization are washed 3 times, and
It is dried in vacuo in 40~60 DEG C up to Fe3O4。
4.(2) take step (1) Fe3O4It is scattered in 60~100mL water, 5~10 mLNH is added3 ∙ H2O and 50 mL containing 1.5~
3mL ethyl orthosilicate methanol solution after 10~15 min of ultrasonic mixing, stirs 6~8 h, and product deionization is washed 3 times, and in
40~60 DEG C are dried in vacuo up to Fe3O4@SiO2；
(3) step (2) Fe will be taken3O4@SiO2It is scattered in 140~150 mL glycerine, under nitrogen protection and stirring, is warming up to
After 60~80 DEG C, 2.5~3.0 mLNH are added3∙H2O and 80~100 mL contains 2~3 mL mercaptopropyl trimethoxysilane first
Alcohol, after reacting 1~2 h, 80 DEG C are continued 5~6 h of stirring, and reaction product deionized water and methanol are during alternately cleaning to pH is in
Property, and up to Fe after 40~60 DEG C of vacuum drying3O4@SiO2- SH magnetic Nano material.
5. the method for highly sensitive detection inorganic mercury according to claim 1 and organic mercury, it is characterised in that: step (1) institute
The maximum excitation wavelength for stating carbon dots is 326 nm, and maximum emission wavelength is 411 nm.
6. the method for highly sensitive detection inorganic mercury according to claim 1 and organic mercury, it is characterised in that: step (2) institute
The Hg stated2+ Aqueous solution, Fe3O4@SiO2The envelope-bulk to weight ratio of-SH magnetic Nano material and HCl are 1:0.02~0.04:0.02
~0.04.
7. the method for highly sensitive detection inorganic mercury according to claim 1 and organic mercury, it is characterised in that: step (3) institute
The organic mercury stated includes methyl-mercuric chloride, ethylmercuric chloride, one or more of in phenylmercuric chloride.
8. the method for highly sensitive detection inorganic mercury according to claim 1 and organic mercury, it is characterised in that: step (2) institute
The organic mercury concentration stated is 0.5~10ng/L, and oxidant is one of potassium peroxydisulfate, potassium permanganate kind, bulking value percentage
Specific concentration is 4 ~ 6%, and concentration of hydrochloric acid is 0.5~1.0 mol/L, and volume ratio is 0.1~1:0.1~0.3:1.
9. the method for highly sensitive detection inorganic mercury according to claim 2 and organic mercury, it is characterised in that: step (3) institute
The w/v of the hydro-thermal biomass and sodium hydroxide and hydrogen peroxide stated is 0.1~30:60~2:5, and naoh concentration is
0.1~0.3 mol/L.
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