CN106290785A - A kind of method using DGT technology separation soil heavy metals of different forms - Google Patents
A kind of method using DGT technology separation soil heavy metals of different forms Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 112
- 239000002689 soil Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000005516 engineering process Methods 0.000 title claims abstract description 21
- 238000000926 separation method Methods 0.000 title claims abstract description 17
- 238000009792 diffusion process Methods 0.000 claims abstract description 74
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 33
- 230000005593 dissociations Effects 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 238000002360 preparation method Methods 0.000 claims description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 238000009825 accumulation Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000000020 Nitrocellulose Substances 0.000 claims description 3
- 229920001220 nitrocellulos Polymers 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 238000011156 evaluation Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000005194 fractionation Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 2
- 230000032683 aging Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 4
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002160 Celluloid Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000783 metal toxicity Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/24—Earth materials
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- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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- G01N33/245—Earth materials for agricultural purposes
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
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Abstract
The present invention relates to a kind of method using different-thickness diffusion phase DGT technology that heavy metal-polluted soil is carried out form fractionation, its principle is that DGT spreads the most organic legibility amorph heavy metal and has dissociation capability, and thickness its heavy metal amount dissociated different is different, thus cause DGT to extract the diversity of heavy metal amount, by this diversity, obtain and resolve DGT Dissociation formula, can be with the separation of in-situ accomplishes heavy metal-polluted soil different shape (ionic state, organic legibility amorph and Fei Yi are dynamic).This method is that the contribution of organic legibility amorph heavy metal provides one Forecasting Methodology quickly and easily with in post-evaluation plant absorption heavy metal-polluted soil bio-available Zn concentration.The assessment simultaneously also making the evaluation to heavy metal in soil adsorption/desorption/diffusion process and release risk can more accurately be carried out.
Description
Technical field
The invention belongs to environmental science and field of earth sciences, be specifically related to the environment such as a kind of soil, water body, deposit and be situated between
The method using DGT technology separation heavy metals of different forms in matter.
Background technology
Heavy metal pollution of soil, especially heavy metals in farmland pollution are the complicated difficults that China's environmental improvement aspect faces for a long time
Topic.Heavy metal pollution not only destroys natural environment, and has seriously threatened existence and the health of the mankind.How in environment
Heavy metal is monitored becoming, with pollution control, the topic that people in recent years make earnest efforts.Index of Heavy Metal Toxicity in Soil is played decisive
The heavy metal biological available state form of effect also becomes the emphasis of people's research.Commonly used heavy metal available state extracts
Technology is chemical method, although the method effect, but restricted by a series of extraneous factors, versatility is bad, and
The fractions distribution of heavy metal can be made during mensuration to change.The appearance of DGT technology overcomes this shortcoming, can be to environment
Middle heavy metal available state extracts and reaches preferable effect.But so far, DGT technology is not applied to soil different shape weight
The separation of metal, and separate soil heavy metals of different forms still without other preferable methods.
Although normally used BCR three-step approach and Tessier continuous extraction can be to heavy metal in soil available states
Each component separates, but the method for chemically based extractant still can be affected by chemical reagent, and is extracting
During easily cause the variation of Heavy Metals.
Summary of the invention
The present invention solve be prior art lacks be applicable to the surrounding mediums such as soil, separate soil different shape
The DGT assay method of heavy metal.
The present invention realizes the technical scheme of purpose:
A kind of method using DGT technology separation soil heavy metals of different forms, comprises the steps:
(1) the preparation of pedotheque: use different regions topsoil samples, by the soil sample that collects with described sampling
Preserve under the temperature conditions that point is identical, and standby by cultivating after sample grinding；
(2) the preparation of different-thickness diffusion phase DGT: make the diffusion phase of different-thickness respectively, and calculate film by volumetric method
Precise thickness, is assembled into DGT device standby after cutting, use different-thickness DGT to extract heavy metal-polluted soil computational rules time
Interior heavy metal-polluted soil activated state content:
A () will be equipped with the circular DGT of different-thickness diffusion phase and insert in the most cultured pedotheque, and keep certain
Operating time 24h, the described circular DGT with the different-thickness diffusion phase degree of depth in described soil sample is in 1-2cm scope
In；
B () takes out the described circular DGT equipped with different-thickness diffusion phase, use ultrapure water device, take out described equipped with
Different-thickness diffusion phase circular DGT in combination fix glue and carry out pickling take off, collect eluent；Measure described eluent
The concentration of middle heavy metal, and it is calculated the described heavy metal spread at the circular DGT/ solution interface of phase equipped with different-thickness
Time average concentration CDGT；
(3) use heavy metal Dissociation Equation for Calculating organic legibility amorph content of beary metal CMLAnd dissociation rate constant
K-1；
(4) calculating soil heavy metal ion state content: the C that matching is drawnMLAnd K-1Bring heavy metal Dissociation side into
Journey calculates DGT and measures the complex state content of beary metal C dissociated in heavy metal bio-available Zn concentration in 24hM', a free state huge sum of money
Genus content is CM=CDGT-CM'。
(5) calculating non-the most dynamically content of beary metal C' according to heavy metal full dose C result, the calculating of heavy metal-polluted soil full dose C is non-easily
Dynamically content of beary metal C':C'=C-CM-CML。
And, the preparation method of described step (1) middle pedotheque is: is sieved by ground for pedotheque 2mm, weighs milled
Soil 100g in plastic casing, add water to 60% water-holding capacity, be put in after sealing in constant temperature and humidity incubator under the conditions of 25 DEG C and cultivate
48h, adds water to 100% water-holding capacity afterwards and continues to cultivate 24h.
And, the (2) middle different-thickness diffusion of described step is corresponding more than or equal to 4 gradients.
And, in the described step (3) middle stipulated time, heavy metal-polluted soil activated state cubage method is:
Wherein, CDGTRepresenting soil heavy metal available state measured value over a period to come, M is in DGT duration of run t
In conjunction with the amount of metal of upper accumulation mutually, A is DGT window area, and thickness of diffusion layer Δ g is diffusion gel layer thickness and celluloid
Filter membrane thickness sum, D is institute's check weighing metal ion diffusion coefficient in diffusion gel, and t is device duration of run.
And, described step (4) described in heavy metal Dissociation equation be:
Wherein Δ g represents diffusion phase thickness, DMLRepresent complex state heavy metal diffusion coefficient in soil, K-1For described
The dissociation rate constant of complex state heavy metal, CMLFor legibility amorph content of beary metal organic in soil, CM' for minute internal disintegration
Content of beary metal.
And, described heavy metal Dissociation equation, and use software matching to draw organic legibility amorph weight in soil
Tenor CMLAnd dissociation rate constant K-1；
The C that matching is drawnMLAnd K-1Bringing heavy metal Dissociation equation into, in drawing DGT mensuration 24h, heavy metal has
The complex state content of beary metal C dissociated in effect state contentM', free state content of beary metal is CM=CDGT-CM'。
And, step (2) different-thickness diffusion phase DGT combines phase preparation method, step is as follows:
(1) by material modified for DTPA and acrylamide gel solution mix and blend, and ultrasonic 2-3 minute, make modified of DTPA
Grain fully scatters；Described DTPA is material modified: weight ratio=3 of acrylamide～1:10；
(2) adding the ammonium persulfate solution of 10wt%, volume is V (Ammonium persulfate .): V (acrylamide gel)=3:500；
And adding tetramethylethylenediamine, volume is V (tetramethylethylenediamine): V (acrylamide gel)=3:2000；
(3) suspension is rapidly injected in certain thickness glass guide channel after 1-3 minute at low temperature ultrasonic, uses glass cover-plate lid
Proceed to be moved to constant temperature and humidity incubator after 4-10 DEG C of low temperature incubator is cultivated 20-40 minute after Hao train under the conditions of 42 DEG C
Support 1h, then take out and be placed in ultra-pure water, take out gel after 30 minutes, change at least three prepared DGT of water in 24 hours and combine phase.
Advantages of the present invention and good effect be:
The present invention uses the DGT equipped with different-thickness diffusion phase, is being spread by different-thickness according to complex state heavy metal
The diversity of the phase time amount of dissociating, application software is fitted, and divides by calculating the structure of heavy metals of different forms in soil
Join.This method is that the contribution of organic legibility amorph heavy metal carries with in post-evaluation plant absorption heavy metal-polluted soil bio-available Zn concentration
Supply one Forecasting Methodology quickly and easily.Also make simultaneously the evaluation to heavy metal in soil adsorption/desorption/diffusion process and
The assessment of release risk can more accurately be carried out.
The invention provides a kind of side using different-thickness diffusion phase DGT technology that heavy metal-polluted soil carries out form fractionation
Method, its principle is that DGT spreads the most organic legibility amorph heavy metal and has dissociation capability, and thickness its huge sum of money dissociated different
Genus amount is different, thus causes DGT to extract the diversity of heavy metal amount, by this diversity, uses and resolves DGT Dissociation
Formula CM'=CML(1-exp[-k-1(Δg')2/2DML]), can with in-situ accomplishes heavy metal-polluted soil different shape (ionic state, organic
Legibility amorph and Fei Yi are dynamic) separation.
Accompanying drawing explanation
Fig. 1 is that in the brunisolic soil of Henan, DGT measures the different shape Ni relation with contents figure in heavy metal different aging period；
Fig. 2 is that in red soil in Guangxi soil, DGT measures the different shape Ni relation with contents figure in heavy metal different aging period；
Fig. 3 is that in Chongqing purple, DGT measures the different shape Ni relation with contents figure in heavy metal different aging period.
Fig. 4 is that in rice in Hunan soil, DGT measures the different shape Ni relation with contents figure in heavy metal different aging period；
Fig. 5 is that in the loessal soil of Xi'an, DGT measures the different shape Ni relation with contents figure in heavy metal different aging period；
Fig. 6 is that in the yellow soil of Jiangsu, DGT measures the different shape Ni relation with contents figure in heavy metal different aging period；
Fig. 7 and Fig. 8 is parameter fitting process figure in DPS software.
Detailed description of the invention
The inventive method is described below by specific embodiment.Unless stated otherwise, technology used in the present invention
Means are method known in those skilled in the art.It addition, embodiment is interpreted as illustrative, and unrestricted is sent out
Bright scope, the spirit and scope of the invention are limited only by the claims that follow.
A kind of method using DGT technology separation soil heavy metals of different forms, uses the DGT of different diffusion phase thickness to incite somebody to action
In soil, the heavy metal of different shape separates.It is characterized by: utilize its combination of DGT upper capture mutually of different-thickness diffusion phase
The diversity of heavy metal ion, uses the method that is fitted of software and by calculating, the weight of different shape in soil the most at last
Metal separates.
Use different regions topsoil samples, by the soil sample that collects under the temperature conditions identical with described sampled point
Preserve, and standby by cultivating after sample grinding.Make the diffusion phase (more than or equal to 4 gradients) of different-thickness respectively, and
Calculate the precise thickness of film by volumetric method, be assembled into DGT device after cutting standby, use different-thickness DGT to extract a soil huge sum of money
Belong to and heavy metal-polluted soil activated state content in the computational rules time: (1) will be equipped with the circular DGT of different-thickness diffusion phase and inserted
In cultured pedotheque, and certain operating time 24h, the described circular DGT with different-thickness diffusion phase is kept to exist
In the range of the degree of depth in described soil sample is in 1-2cm；(2) the described circular DGT equipped with different-thickness diffusion phase is taken out, with ultrapure
Water flushing device, takes out and described fix glue equipped with the combination in the circular DGT of different-thickness diffusion phase and carry out pickling and take off, receive
Collection eluent；Measure the concentration of heavy metal in described eluent, and be calculated the described circle equipped with different-thickness diffusion phase
The time average concentration C of the heavy metal at DGT/ solution interfaceDGT.(3) last, use heavy metal Dissociation equation and lead to
Cross software matching and draw organic legibility amorph content of beary metal CMLAnd dissociation rate constant K-1, it is computed drawing heavy metal in soil
Ionic state, organic legibility amorph and non-the most dynamically content of beary metal.
In described soil, heavy metals of different forms computational methods are: C matching drawnMLAnd K-1Bring heavy metal into dissociate
Kinetics equation calculates DGT and measures the complex state content of beary metal C dissociated in heavy metal bio-available Zn concentration in 24hM', trip
Amorph content of beary metal is CM=CDGT-CM'.Non-the most dynamically content of beary metal C':C'=C-is calculated according to heavy metal full dose C result
CM-CML。
The material of the combination phase used in the present invention is application number: 201510426767.5 applyings date: 2015-07-20, public
The number of opening is CN105148846A, and material modified and preparation the release DGT of quick complete solution of invention entitled a kind of DTPA combines phase
Preparation method, the release DGT of quick complete solution of middle preparation combines phase material.
The described release DGT of quick complete solution combines phase preparation method, and step is as follows:
(1) by material modified for DTPA and acrylamide gel solution mix and blend, and ultrasonic 2-3 minute, make modified of DTPA
Grain fully scatters；Described DTPA is material modified: weight ratio=3 of acrylamide～1:10；
(2) adding the ammonium persulfate solution of 10wt%, volume is V (Ammonium persulfate .): V (acrylamide gel)=3:500；
And adding tetramethylethylenediamine, volume is V (tetramethylethylenediamine): V (acrylamide gel)=3:2000；
(3) suspension is rapidly injected in certain thickness glass guide channel after 1-3 minute at low temperature ultrasonic, uses glass cover-plate lid
Proceed to be moved to constant temperature and humidity incubator after 4-10 DEG C of low temperature incubator is cultivated 20-40 minute after Hao train under the conditions of 42 DEG C
Support 1h, then take out and be placed in ultra-pure water, take out gel after 30 minutes, change at least three prepared DGT of water in 24 hours and combine phase.
The method of the employing DGT technology separation soil heavy metals of different forms that the present invention provides, comprises the steps:
(1) preparation of pedotheque: use top layer, different regions (0～20cm) pedotheque, the soil sample collected is existed
Preserve under the temperature conditions identical with described sampled point, and standby by cultivating after sample grinding.
(2) preparation of different-thickness diffusion phase DGT: make the diffusion phase of different-thickness respectively, and by volumetric method to diffusion
Phase thickness strictly controls.DGT device it is assembled into standby after cutting.
(3) different-thickness DGT is used to extract heavy metal-polluted soil heavy metal-polluted soil activated state content in the computational rules time:
A () will be equipped with the circular DGT of different-thickness diffusion phase and insert in the most cultured pedotheque, and keep certain
Operating time (24h), the described circular DGT with the different-thickness diffusion phase degree of depth in described soil sample is in 1-2cm scope
In；
B () takes out the described circular DGT equipped with different-thickness diffusion phase, with ultrapure water device clean after, take out institute
State equipped with different-thickness diffusion phase circular DGT in combination fix glue and carry out pickling take off, collect eluent；Measure described
The concentration of heavy metal in eluent, and it is calculated described equipped with the weight at the circular DGT/ solution interface of different-thickness diffusion phase
The time average concentration C of metalDGT。
(4) heavy metal Dissociation Equation for Calculating organic legibility amorph content of beary metal C is usedMLAnd dissociation rate constant
K-1。
Calculating soil heavy metal ion state content: the C that matching is drawnMLAnd K-1Bring heavy metal Dissociation equation into
Calculate soil heavy metal ion state content.
Non-the most dynamically content of beary metal (C') is calculated according to heavy metal full dose (C) result.
Described in step (1), the preparation method of pedotheque is: is sieved by ground for pedotheque 2mm, weighs the soil of milled
Earth 100g adds water to 60% water-holding capacity in plastic casing, is put in constant temperature and humidity incubator and cultivates 48h under the conditions of 25 DEG C after sealing,
Add water to 100% water-holding capacity afterwards continue to cultivate 24h.
The diffusion of different-thickness described in step (2) is corresponding more than or equal to 4 gradients, such as 0.53mm, 0.93mm, 1.33mm
And 1.73mm etc..
Described in step (3), in the stipulated time, heavy metal-polluted soil activated state cubage method is:
Wherein, CDGTRepresenting soil heavy metal available state measured value over a period to come, M is in DGT duration of run t (
As be 24h) in combine the amount of metal of upper accumulation mutually, A is DGT window area, thickness of diffusion layer Δ g be diffusion gel layer thickness with
Nitrocellulose filter thickness sum, D is institute's check weighing metal ion diffusion coefficient in diffusion gel, when t is device expansion
Between (24h).
Described in step (4), heavy metal Dissociation equation is:
Wherein CM' for the content of beary metal of minute internal disintegration, Δ g' represents diffusion phase thickness, DMLRepresent complex state weight
Metal diffusion coefficient in soil, K-1For the dissociation rate constant of described complex state heavy metal, CMLFor legibility organic in soil from
State content of beary metal.
The calculating process of heavy metals of different forms in soil:
According to step (4) described heavy metal Dissociation equation, use software matching draw in soil organic legibility from
State content of beary metal CMLAnd dissociation rate constant K-1。
The C that matching is drawnMLAnd K-1Bringing heavy metal Dissociation equation into, in drawing DGT mensuration 24h, heavy metal has
The complex state content of beary metal C dissociated in effect state contentM', free state content of beary metal is CM=CDGT-CM'。
Non-the most dynamically content of beary metal (C'): C'=C-C is calculated according to heavy metal-polluted soil full dose (C)M-CML。
It is actually detected that the present invention uses following sample to carry out, and specifically comprises the following steps that
(1) collection of pedotheque and preparation:
Use Henan brunisolic soil, rice in Hunan soil, Xi'an loessal soil, Jiangsu yellow soil, red soil in Guangxi soil and Chongqing purple
Soil top layer (0～20cm) pedotheque.The soil sample collected is preserved under the temperature conditions identical with described sampled point
And the basic physical and chemical parameter of described soil sample is measured.
In the case of measuring different heavy metal Ni content in same soil, DGT measures the distribution of Ni different shape,
Carry out heavy metal degradation.In the soil of milled, add the heavy metal Ni of 100mg/kg, parallel weigh 4 parts and add heavy metal
Soil 800g is in plastic casing, and the ultra-pure water adding 60% is put in after stirring and sealing in constant temperature and humidity incubator, 25 DEG C of bars
48h is cultivated under part.The moisture content adding 100% afterwards stirs, and cultivates 90 days under the conditions of 25 DEG C.
(2) making of DGT different-thickness diffusion phase:
Make respectively 0.53mm, 0.93mm, 1.33mm and 1.73mm (actual measurement 0.53mm, 0.91mm, 1.13mm and
1.73mm) the diffusion phase of thickness, and by volumetric method, diffusion phase thickness is strictly controlled.DGT device it is assembled into standby after cutting
With.
(3) mensuration of heavy metal in soil available state:
A will be equipped with during () soil incubation spreading phase thickness is the circle of 0.53mm, 0.91mm, 1.13mm, 1.73mm
DGT is respectively in aging 1d, 45d and the 90d of heavy metal inserts pedotheque, and keeps certain operating time (24h), described
In the range of being in 1-2cm with the circular DGT degree of depth in described soil sample of different-thickness diffusion phase；
B () takes out the described circular DGT equipped with different-thickness diffusion phase, after being rinsed well by device with ultra-pure water, take out
The described circular DGT equipped with different-thickness diffusion phase combines and fixes glue and use the HNO of 1mol/L3Solution carries out pickling
De-, collect eluent；Measure the concentration of heavy metal in described eluent, and be calculated described equipped with different-thickness diffusion phase
The time average concentration C of the heavy metal at circular DGT/ solution interfaceDGT。
Wherein, CDGTRepresenting soil heavy metal available state measured value over a period to come, M is in DGT duration of run t
(24h) combining the amount of metal of upper accumulation mutually in, A is that (this experimental provision is 4.64cm to DGT window area2), thickness of diffusion layer Δ g
For diffusion gel layer thickness and nitrocellulose filter thickness (0.013cm) sum, D is that institute's check weighing metal ion is in diffusion gel
In diffusion coefficient (6.09 × 10-6Cm/s), t is device duration of run (24h).
(4) use following equation, and use DPS software general nonlinearity Regression Model Simulator to draw organic legibility in soil
Amorph content of beary metal CMLAnd dissociation rate constant K-1。
Wherein Δ g' represents diffusion phase thickness, DMLRepresent complex state heavy metal diffusion coefficient in soil (1.218 ×
10-6Cm/s), K-1For the dissociation rate constant of described complex state heavy metal, CMLFor legibility amorph content of beary metal organic in soil,
CM' it is the content of beary metal dissociated.
Equation in input DPS software is: x2=c1* (1-exp (-c2x1)).
Equation is the deformation of heavy metal Dissociation equation in step (4).Wherein x2 and CM' corresponding, represent with not
Bio-available Zn concentration (the C that the DGT of stack pile diffusion phase recordsDGT) difference, CM'-CM；C1 is the complex state that can dissociate in described soil
Content of beary metal CML；C2 is described dissociation rate constant K-1；X1 is (Δ g)2/2DML, Δ g' is and CM'-CMCorresponding diffusion is mutually thick
The difference of degree.
(5) C that matching is drawnMLAnd K-1Bring in above-mentioned formula, show that DGT measures the heavy metal bio-available Zn concentration of 24h
In the combined state content of beary metal C that dissociatesM'。
The free state content of beary metal measured in DGT duration of run 24h is CM=CDGT-CM'。
Heavy metal available state concentration total in soil is CMLWith CMSum.
Non-the most dynamically content of beary metal (C'): C'=C-C is calculated according to heavy metal-polluted soil full dose (C)M-CML。
During using DGT to measure heavy metal in soil available state concentration, it is generally recognized that diffusion phase gel thicknesses is
The available state concentration recorded during 0.8mm can represent the available state concentration that heavy metal in soil is real.It is as shown in Figures 1 to 6
Use six kinds of heavy metal in soil Cd free states, organic legibility amorph and non-movability that the DGT of 0.91mm thickness diffusion phase records
State content of beary metal.As can be seen here, employing DGT technology separation soil heavy metals of different forms of the present invention is with post-evaluation
Heavy metal-polluted soil different shape content has supplied one detection method quickly and easily.
By Fig. 7, as a example by 8, the acquisition process of parameter fitting process and result is illustrated,
Table 1 heavy metal-polluted soil full dose and matching obtain parameter
Note: C in tableMLFor parameter C1 obtained in fit procedure, K-1For parameter C2 obtained in fit procedure.
Claims (7)
1. the method using DGT technology separation soil heavy metals of different forms, it is characterised in that: comprise the steps:
(1) the preparation of pedotheque: use different regions topsoil samples, by the soil sample that collects with described sampled point phase
Preserve under same temperature conditions, and standby by cultivating after sample grinding；
(2) the preparation of different-thickness diffusion phase DGT: make the diffusion phase of different-thickness respectively, and calculate the accurate of film by volumetric method
Thickness, is assembled into DGT device standby after cutting, employing different-thickness DGT extraction heavy metal-polluted soil soil in the computational rules time
Earth heavy metal activity state content:
A () will be equipped with the circular DGT of different-thickness diffusion phase and insert in the most cultured pedotheque, and keep certain operation
In the range of time 24h, the described circular DGT with the different-thickness diffusion phase degree of depth in described soil sample is in 1-2cm；
B () takes out the described circular DGT equipped with different-thickness diffusion phase, use ultrapure water device, takes out described equipped with difference
Thickness diffusion phase circular DGT in combination fix glue and carry out pickling take off, collect eluent；Measure weight in described eluent
The concentration of metal, and it is calculated the described time equipped with the heavy metal at the circular DGT/ solution interface of different-thickness diffusion phase
Mean concentration CDGT；
(3) use heavy metal Dissociation Equation for Calculating organic legibility amorph content of beary metal CMLAnd dissociation rate constant K-1；
(4) calculating soil heavy metal ion state content: the C that matching is drawnMLAnd K-1Bring heavy metal Dissociation Equation for Calculating into
Show that DGT measures the complex state content of beary metal C dissociated in heavy metal bio-available Zn concentration in 24hM', free state content of beary metal
For CM=CDGT-CM'。
(5) calculating non-the most dynamically content of beary metal C' according to heavy metal full dose C result, the calculating of heavy metal-polluted soil full dose C is non-the most dynamically
Content of beary metal C':C'=C-CM-CML。
The method of employing DGT technology separation soil heavy metals of different forms the most according to claim 1, it is characterised in that:
The preparation method of described step (1) middle pedotheque is: is sieved by ground for pedotheque 2mm, weighs the soil 100g of milled in moulding
Magazine adds water to 60% water-holding capacity, is put in after sealing in constant temperature and humidity incubator and under the conditions of 25 DEG C, cultivates 48h, add water to afterwards
100% water-holding capacity continues to cultivate 24h.
The method of employing DGT technology separation soil heavy metals of different forms the most according to claim 1, it is characterised in that:
The (2) middle different-thickness diffusion of described step is corresponding more than or equal to 4 gradients.
The method of employing DGT technology separation soil heavy metals of different forms the most according to claim 1, it is characterised in that:
In the described step (3) middle stipulated time, heavy metal-polluted soil activated state cubage method is:
Wherein, CDGTRepresenting soil heavy metal available state measured value over a period to come, M is to combine in DGT duration of run t
The amount of metal of upper accumulation mutually, A is DGT window area, and thickness of diffusion layer Δ g is diffusion gel layer thickness and nitrocellulose filter
Thickness sum, D is institute's check weighing metal ion diffusion coefficient in diffusion gel, and t is device duration of run.
The method of employing DGT technology separation soil heavy metals of different forms the most according to claim 1, it is characterised in that:
Described step (4) described in heavy metal Dissociation equation be:
Wherein Δ g represents diffusion phase thickness, DMLRepresent complex state heavy metal diffusion coefficient in soil, K-1For described complex state
The dissociation rate constant of heavy metal, CMLFor legibility amorph content of beary metal organic in soil, CM' for the huge sum of money of minute internal disintegration
Belong to content.
The method of employing DGT technology separation soil heavy metals of different forms the most according to claim 5, it is characterised in that:
Described heavy metal Dissociation equation, and use software matching to draw organic legibility amorph content of beary metal C in soilMLAnd solve
From rate constant K-1；
The C that matching is drawnMLAnd K-1Bringing heavy metal Dissociation equation into, in drawing DGT mensuration 24h, heavy metal available state contains
The complex state content of beary metal C dissociated in amountM', free state content of beary metal is CM=CDGT-CM'。
The method of employing DGT technology separation soil heavy metals of different forms the most according to claim 1, it is characterised in that:
Combining phase preparation method in step (2) different-thickness diffusion phase DGT, step is as follows:
(1) by material modified for DTPA and acrylamide gel solution mix and blend, and ultrasonic 2-3 minute, make DTPA modified particles fill
It scatter；Described DTPA is material modified: weight ratio=3 of acrylamide～1:10；
(2) adding the ammonium persulfate solution of 10wt%, volume is V (Ammonium persulfate .): V (acrylamide gel)=3:500；And add
Entering tetramethylethylenediamine, volume is V (tetramethylethylenediamine): V (acrylamide gel)=3:2000；
(3) suspension is rapidly injected in certain thickness glass guide channel, after building with glass cover-plate after 1-3 minute at low temperature ultrasonic
Proceed to be moved to constant temperature and humidity incubator after 4-10 DEG C of low temperature incubator is cultivated 20-40 minute cultivate under the conditions of 42 DEG C
1h, then takes out and is placed in ultra-pure water, takes out gel, change at least three prepared DGT of water and combine phase in 24 hours after 30 minutes.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108325508A (en) * | 2018-03-09 | 2018-07-27 | 北京交通大学 | Heavy metal available state adsorbed film and heavy metal available state detection method |
| CN108680726A (en) * | 2018-05-08 | 2018-10-19 | 中国科学院地球化学研究所 | Measure the DGT enrichment films and preparation method thereof of Paddy Soil Solutions biological effectiveness Hg (II) |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103743655A (en) * | 2014-02-13 | 2014-04-23 | 中国科学院南京地理与湖泊研究所 | Method for determining inorganic arsenic in soil or water body based on diffusive gradients in thin-films technique |
| CN104048924A (en) * | 2013-03-12 | 2014-09-17 | 中国科学院南京地理与湖泊研究所 | Two-dimensional high-resolution method for determination of distribution of active phosphorus in wetland soil and deposit |
| CN104198405A (en) * | 2014-08-11 | 2014-12-10 | 渤海大学 | Method for determining bio-available phosphorus in soil |
| CN104492376A (en) * | 2014-12-19 | 2015-04-08 | 南京大学 | 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 |
| CN105148846A (en) * | 2015-07-20 | 2015-12-16 | 农业部环境保护科研监测所 | DTPA modified material and preparation method for rapid-full-dissociation type DGT (Diffusive gradients in thin films) coupling phase prepared therefrom |
| CN105148847A (en) * | 2015-07-20 | 2015-12-16 | 农业部环境保护科研监测所 | Bond phase gel film easy for dynamic heavy metal adsorption and preparation method for bond phase gel film |
-
2016
- 2016-07-29 CN CN201610627442.8A patent/CN106290785B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104048924A (en) * | 2013-03-12 | 2014-09-17 | 中国科学院南京地理与湖泊研究所 | Two-dimensional high-resolution method for determination of distribution of active phosphorus in wetland soil and deposit |
| CN103743655A (en) * | 2014-02-13 | 2014-04-23 | 中国科学院南京地理与湖泊研究所 | Method for determining inorganic arsenic in soil or water body based on diffusive gradients in thin-films technique |
| CN104198405A (en) * | 2014-08-11 | 2014-12-10 | 渤海大学 | Method for determining bio-available phosphorus in soil |
| CN104492376A (en) * | 2014-12-19 | 2015-04-08 | 南京大学 | 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 |
| CN105148846A (en) * | 2015-07-20 | 2015-12-16 | 农业部环境保护科研监测所 | DTPA modified material and preparation method for rapid-full-dissociation type DGT (Diffusive gradients in thin films) coupling phase prepared therefrom |
| CN105148847A (en) * | 2015-07-20 | 2015-12-16 | 农业部环境保护科研监测所 | Bond phase gel film easy for dynamic heavy metal adsorption and preparation method for bond phase gel film |
Non-Patent Citations (2)
| Title |
|---|
| AMIR HOUSHANG SHIVA ETAL: "In situ evaluation of DGT techniques for measurement of trace metals in estuarine waters:a comparison of four binding layers with open and restricted diffusive layers", 《ENVIRONMENTAL SCIENCE PROCESSES & IMPACTS》 * |
| PEIFANG WANG ETAL: "A Diffusive Gradient-in-Thin-Film Technique for Evaluation of the Bioavailability of Cd in Soil Contaminated with Cd and Pb", 《INTERNATIONAL JOURNAL OF ENVIRONMENTAL RESEARCH AND PUBLIC HEALTH》 * |
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