CN106290785B - A method of soil heavy metals of different forms is separated using DGT technology - Google Patents
A method of soil heavy metals of different forms is separated using DGT technology Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims abstract description 103
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000005516 engineering process Methods 0.000 title claims abstract description 15
- 238000009792 diffusion process Methods 0.000 claims abstract description 72
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 36
- 230000005593 dissociations Effects 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 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 14
- 239000003480 eluent Substances 0.000 claims description 10
- 238000005259 measurement Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000004364 calculation method Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 239000000020 Nitrocellulose Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229920001220 nitrocellulos Polymers 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000011156 evaluation Methods 0.000 abstract description 3
- 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
- 238000007599 discharging Methods 0.000 abstract 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 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 description 7
- 230000032683 aging Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 235000009566 rice Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 238000011534 incubation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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 methods that heavy metal-polluted soil is carried out form fractionation using different-thickness diffusion phase DGT technology, its principle is that DGT spreads relatively organic legibility amorph heavy metal and has dissociation capability, and the heavy metal amount of its different dissociation of thickness is different, the otherness of heavy metal amount is extracted so as to cause DGT, pass through this otherness, obtain parsing DGT Dissociation formula, it can be with the separation of in-situ accomplishes heavy metal-polluted soil different shape (ionic state, organic legibility amorph and Fei Yi dynamic).This method is to evaluate in plant absorption heavy metal-polluted soil bio-available Zn concentration later, and the contribution of organic legibility amorph heavy metal provides a kind of quickly and easily prediction technique.Simultaneously but also can more accurately be carried out to the evaluation of heavy metal in soil adsorption/desorption/diffusion process and the assessment for discharging risk.
Description
Technical field
The invention belongs to environmental sciences and field of earth sciences, and in particular to the environment such as a kind of soil, water body, deposit are situated between
Using the method for DGT technology separation heavy metals of different forms in matter.
Background technique
The pollution of heavy metal pollution of soil, especially heavy metals in farmland is the complicated difficult that China's environmental improvement aspect faces for a long time
Topic.Heavy metal pollution not only destroys natural environment, and has seriously threatened the existence and health of the mankind.How in environment
Heavy metal, which is monitored, becomes the topic that people in recent years are keen to pollution control.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 this method effect, by a series of restriction of extraneous factors, versatility is bad, and
The fractions distribution of heavy metal can be made to change in continuous mode.The appearance of DGT technology overcomes this disadvantage, can be to environment
Middle heavy metal available state extraction reaches ideal effect.But so far, DGT technology is not applied to soil different shape weight
The separation of metal, and soil heavy metals of different forms is separated still without other preferable methods.
Although usually used BCR three-step approach and Tessier continuous extraction can be to heavy metal in soil available state
Each component is separated, but the method based on chemical extraction agent still will receive the influence of chemical reagent, and extract
The variation of Heavy Metals is easily caused in the process.
Summary of the invention
The invention solves lacking suitable for the surrounding mediums such as soil in the prior art, soil different shape is separated
The DGT measuring method of heavy metal.
The present invention realizes that the technical solution of purpose is:
A method of soil heavy metals of different forms is separated using DGT technology, is included the following steps:
(1) the preparation of pedotheque: use different regions topsoil sample, by collected soil sample with the sampling
It is saved, and is cultivated after sample is ground spare under the conditions of the identical temperature of point；
(2) the preparation of different-thickness diffusion phase DGT: the diffusion phase of different-thickness is made respectively, and calculates film with volumetric method
Precise thickness, it is spare to be assembled into DGT device after cutting, extracts heavy metal-polluted soil and computational rules time using different-thickness DGT
Interior heavy metal-polluted soil activated state content:
(a) the round DGT equipped with different-thickness diffusion phase is inserted into cultured pedotheque, and kept centainly
Operating time, depth of the round DGT with different-thickness diffusion phase in the soil sample was in 1-2cm range for 24 hours
It is interior；
(b) the round DGT equipped with different-thickness diffusion phase is taken out, with ultrapure water device, is equipped with described in taking-up
Combination in the round DGT of different-thickness diffusion phase, which mutually fixes glue and carries out pickling, to be taken off, and eluent is collected；Measure the eluent
The concentration of middle heavy metal, and the heavy metal at the round DGT/ solution interface equipped with different-thickness diffusion phase is calculated
Time mean concentration CDGT；
(3) the organic legibility amorph content of beary metal C of heavy metal Dissociation equation calculation is usedMLAnd dissociation rate constant
K-1；
(4) soil heavy metal ion state content is calculated: the C that fitting is obtainedMLAnd K-1Bring heavy metal Dissociation side into
The complex state content of beary metal C dissociated in heavy metal bio-available Zn concentration in DGT measurement for 24 hours is calculated in journeyM', a free state huge sum of money
Category content is CM=CDGT-CM'。
(5) non-easy dynamic content of beary metal C' is calculated according to heavy metal full dose C result, heavy metal-polluted soil full dose C calculates non-easy
Dynamic content of beary metal C':C'=C-CM-CML。
Moreover, the step (1) in pedotheque the preparation method comprises the following steps: the ground 2mm of pedotheque is sieved, weigh milled
Soil 100g 60% water-holding capacity is added water in plastic casing, be put in after sealing in constant temperature and humidity incubator and cultivated under the conditions of 25 DEG C
48h adds water to 100% water-holding capacity later and continues culture for 24 hours.
Moreover, (2) middle different-thickness diffusion is accordingly more than or equal to 4 gradients to the step.
Moreover, the step (3) in heavy metal-polluted soil activated state content calculation method in the stipulated time are as follows:
Wherein, CDGTIndicate that the heavy metal available state measured value of soil over a period to come, M are in DGT duration of run t
In conjunction with the amount of metal accumulated in phase, A is DGT window area, and thickness of diffusion layer Δ g is diffusion gel thickness degree and nitrocellulose
The sum of filter membrane thickness, diffusion coefficient of the D for institute's check weighing metal ion in diffusion gel, t are device duration of run.
Moreover, the step (4) described in heavy metal Dissociation equation are as follows:
Wherein Δ g indicates diffusion phase thickness, DMLIndicate the diffusion coefficient of complex state heavy metal in the soil, K-1It is described
The dissociation rate constant of complex state heavy metal, CMLFor legibility amorph content of beary metal organic in soil, CM' it is minute internal disintegration
Content of beary metal.
Moreover, the heavy metal Dissociation equation, and organic legibility amorph weight in soil is obtained using software fitting
Tenor CMLAnd dissociation rate constant K-1；
The C that fitting is obtainedMLAnd K-1It brings heavy metal Dissociation equation into, show there there is heavy metal in DGT measurement for 24 hours
The complex state content of beary metal C dissociated in effect state contentM', free state content of beary metal is CM=CDGT-CM'。
Moreover, combining phase preparation method in step (2) different-thickness diffusion phase DGT, steps are as follows:
(1) DTPA modified material and acrylamide gel solution are mixed, and ultrasound 2-3 minutes, make DTPA modified
Grain sufficiently scatters；The DTPA modified material: weight ratio=3 of acrylamide~1:10；
(2) the ammonium persulfate solution of 10wt% is added, and volume is V (ammonium persulfate): V (acrylamide gel)=3:500；
And tetramethylethylenediamine is added, volume is V (tetramethylethylenediamine): V (acrylamide gel)=3:2000；
(3) suspension is rapidly injected in certain thickness glass guide channel after low temperature ultrasonic 1-3 minutes, with glass cover-plate lid
Constant temperature and humidity incubator is moved to after being transferred to 4-10 DEG C of low temperature incubator culture 20-40 minutes after good to train under the conditions of 42 DEG C
1h is supported, then takes out and is placed in ultrapure water, gel is taken out after 30 minutes, water is changed in 24 hours, DGT combination phase is at least made three times.
The advantages and positive effects of the present invention are:
The present invention uses the DGT equipped with different-thickness diffusion phase, is spread according to complex state heavy metal by different-thickness
The otherness of dissociation amount, application software are fitted when phase, by the structure point that heavy metals of different forms in soil is calculated
Match.This method is to evaluate in plant absorption heavy metal-polluted soil bio-available Zn concentration later, and the contribution of organic legibility amorph heavy metal mentions
A kind of quickly and easily prediction technique is supplied.Simultaneously but also to the evaluation of heavy metal in soil adsorption/desorption/diffusion process and
The assessment of release risk can be carried out more accurately.
The present invention provides a kind of sides that heavy metal-polluted soil is carried out to form fractionation using different-thickness diffusion phase DGT technology
Method, principle are that DGT spreads relatively organic legibility amorph heavy metal and has dissociation capability, and a huge sum of money for its different dissociation of thickness
Category amount is different, and the otherness of heavy metal amount is extracted so as to cause DGT, by this otherness, using parsing 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, it is organic
Legibility amorph and Fei Yi dynamic) separation.
Detailed description of the invention
Fig. 1 is that DGT measures different shape Ni in the relation with contents figure in heavy metal difference aging period in the brunisolic soil of Henan；
Fig. 2 is that DGT measures different shape Ni in the relation with contents figure in heavy metal difference aging period in red soil in Guangxi soil；
Fig. 3 is that DGT measures different shape Ni in the relation with contents figure in heavy metal difference aging period in Chongqing purple.
Fig. 4 is that DGT measures different shape Ni in the relation with contents figure in heavy metal difference aging period in rice in Hunan soil；
Fig. 5 is that DGT measures different shape Ni in the relation with contents figure in heavy metal difference aging period in the loessal soil of Xi'an；
Fig. 6 is that DGT measures different shape Ni in the relation with contents figure in heavy metal difference aging period in the yellow soil of Jiangsu；
Fig. 7 and Fig. 8 is parameter fitting process figure in DPS software.
Specific embodiment
The method of the present invention 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.In addition, embodiment is interpreted as illustrative, rather than this hair is limited
Bright range, the spirit and scope of the invention are limited only by the claims that follow.
A method of soil heavy metals of different forms is separated using DGT technology, it will using the DGT of different diffusion phase thickness
The heavy metal of different shape is separated in soil.It is characterized in that: using different-thickness diffusion phase DGT its combine phase on capture
The otherness of heavy metal ion, the method being fitted using software simultaneously passes through calculating, finally by the weight of different shape in soil
Metal is separated.
Using different regions topsoil sample, by collected soil sample under the conditions of temperature identical with the sampled point
It is saved, and is cultivated after sample is ground spare.The diffusion phase (being more than or equal to 4 gradients) of different-thickness is made respectively, and
The precise thickness that film is calculated with volumetric method, it is spare to be assembled into DGT device after cutting, extracts a soil huge sum of money using different-thickness DGT
Belong to heavy metal-polluted soil activated state content in the simultaneously computational rules time: (1) will be inserted into equipped with the round DGT of different-thickness diffusion phase
In cultured pedotheque, and kept for certain operating time for 24 hours, the round DGT with different-thickness diffusion phase exists
Depth in the soil sample is within the scope of 1-2cm；(2) the round DGT equipped with different-thickness diffusion phase is taken out, use is ultrapure
Water flushing device, takes out that glue is mutually fixed in the combination in the round DGT equipped with different-thickness diffusion phase and to carry out pickling de-, receives
Collect eluent；The concentration of heavy metal in the eluent is measured, and the circle equipped with different-thickness diffusion phase is calculated
The time mean concentration C of heavy metal at DGT/ solution interfaceDGT.(3) finally, using heavy metal Dissociation equation and leading to
It crosses software fitting and obtains organic legibility amorph content of beary metal CMLAnd dissociation rate constant K-1, it is computed and obtains heavy metal in soil
Ionic state, organic legibility amorph and non-easy dynamic content of beary metal.
Heavy metals of different forms calculation method in the soil are as follows: the C for obtaining fittingMLAnd K-1Bring heavy metal dissociation into
The complex state content of beary metal C dissociated in heavy metal bio-available Zn concentration in DGT measurement for 24 hours is calculated in kinetics equationM', trip
Amorph content of beary metal is CM=CDGT-CM'.Non- easy dynamic content of beary metal C':C'=C- is calculated according to heavy metal full dose C result
CM-CML。
The material that phase is combined used in the present invention is application number: 201510426767.5 applyings date: 2015-07-20, public
The number of opening is the release DGT combination phase of quick complete solution of CN105148846A, a kind of entitled DTPA modified material and its preparation
Preparation method, the release DGT combination phase material of the quick complete solution of middle preparation.
The release DGT combination phase preparation method of quick complete solution, steps are as follows:
(1) DTPA modified material and acrylamide gel solution are mixed, and ultrasound 2-3 minutes, make DTPA modified
Grain sufficiently scatters；The DTPA modified material: weight ratio=3 of acrylamide~1:10；
(2) the ammonium persulfate solution of 10wt% is added, and volume is V (ammonium persulfate): V (acrylamide gel)=3:500；
And tetramethylethylenediamine is added, volume is V (tetramethylethylenediamine): V (acrylamide gel)=3:2000；
(3) suspension is rapidly injected in certain thickness glass guide channel after low temperature ultrasonic 1-3 minutes, with glass cover-plate lid
Constant temperature and humidity incubator is moved to after being transferred to 4-10 DEG C of low temperature incubator culture 20-40 minutes after good to train under the conditions of 42 DEG C
1h is supported, then takes out and is placed in ultrapure water, gel is taken out after 30 minutes, water is changed in 24 hours, DGT combination phase is at least made three times.
Method provided by the invention using DGT technology separation soil heavy metals of different forms, includes the following steps:
(1) preparation of pedotheque: different regions surface layer (0~20cm) pedotheque is used, collected soil sample is existed
It is saved, and is cultivated after sample is ground spare under the conditions of temperature identical with the sampled point.
(2) preparation of different-thickness diffusion phase DGT: the diffusion phase of different-thickness is made respectively, and with volumetric method to diffusion
Phase thickness carries out strict control.It is spare that DGT device is assembled into after cutting.
(3) heavy metal-polluted soil activated state content in heavy metal-polluted soil and computational rules time is extracted using different-thickness DGT:
(a) the round DGT equipped with different-thickness diffusion phase is inserted into cultured pedotheque, and kept centainly
Operating time (for 24 hours), depth of the round DGT with different-thickness diffusion phase in the soil sample are in 1-2cm range
It is interior；
(b) take out the round DGT equipped with different-thickness diffusion phase, with ultrapure water device it is clean after, take out institute
It states the combination in the round DGT equipped with different-thickness diffusion phase and mutually fixes glue and carry out pickling and take off, collect eluent；Described in measurement
The concentration of heavy metal in eluent, and the weight at the round DGT/ solution interface equipped with different-thickness diffusion phase is calculated
The time mean concentration C of metalDGT。
(4) the organic legibility amorph content of beary metal C of heavy metal Dissociation equation calculation is usedMLAnd dissociation rate constant
K-1。
Calculate soil heavy metal ion state content: the C that fitting is obtainedMLAnd K-1Bring heavy metal Dissociation equation into
Calculate soil heavy metal ion state content.
Non- easy dynamic content of beary metal (C') is calculated according to heavy metal full dose (C) result.
Pedotheque described in step (1) the preparation method comprises the following steps: the ground 2mm of pedotheque is sieved, weigh the soil of milled
Earth 100g adds water to 60% water-holding capacity in plastic casing, is put in constant temperature and humidity incubator after sealing and cultivates 48h under the conditions of 25 DEG C,
100% water-holding capacity is added water to later continues culture for 24 hours.
The diffusion of different-thickness described in step (2) is accordingly more than or equal to 4 gradients, such as 0.53mm, 0.93mm, 1.33mm
And 1.73mm etc..
Heavy metal-polluted soil activated state content calculation method in stipulated time described in step (3) are as follows:
Wherein, CDGTIndicate that the heavy metal available state measured value of soil over a period to come, M are in DGT duration of run t (one
As for for 24 hours) in combine the amount of metal accumulated in phase, A is DGT window area, thickness of diffusion layer Δ g be diffusion gel thickness degree with
The sum of nitrocellulose filter thickness, diffusion coefficient of the D for institute's check weighing metal ion in diffusion gel, when t is that device is unfolded
Between (for 24 hours).
Heavy metal Dissociation equation described in step (4) are as follows:
Wherein CM' be minute internal disintegration content of beary metal, Δ g' indicate diffusion phase thickness, DMLIndicate complex state weight
The diffusion coefficient of metal in the soil, K-1For the dissociation rate constant of the 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) the heavy metal Dissociation equation, using software fitting obtain in soil organic legibility from
State content of beary metal CMLAnd dissociation rate constant K-1。
The C that fitting is obtainedMLAnd K-1It brings heavy metal Dissociation equation into, show there there is heavy metal in DGT measurement for 24 hours
The complex state content of beary metal C dissociated in effect state contentM', free state content of beary metal is CM=CDGT-CM'。
Non- easy dynamic content of beary metal (C'): C'=C-C is calculated according to heavy metal-polluted soil full dose (C)M-CML。
The present invention is carried out actually detected using following sample, the specific steps are as follows:
(1) acquisition and preparation of pedotheque:
Using Henan brunisolic soil, rice in Hunan soil, Xi'an loessal soil, Jiangsu yellow soil, red soil in Guangxi soil and Chongqing purple
Native surface layer (0~20cm) pedotheque.Collected soil sample is saved under the conditions of temperature identical with the sampled point
And the basic physical and chemical parameter of the soil sample is measured.
In order to measure different heavy metal Ni contents in same soil, DGT measures the distribution of Ni different shape,
Carry out heavy metal degradation.The heavy metal Ni that 100mg/kg is added into the soil of milled weighs 4 parts of exacerbation metals in parallel
Soil 800g adds 60% ultrapure water to stir evenly and be put in constant temperature and humidity incubator after sealing in plastic casing, 25 DEG C of items
48h is cultivated under part.Later plus 100% moisture content stirs evenly, and cultivates 90 days under the conditions of 25 DEG C.
(2) production of DGT different-thickness diffusion phase:
Respectively make 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 strict control is carried out to diffusion phase thickness with volumetric method.It is standby that DGT device is assembled into after cutting
With.
(3) measurement of heavy metal in soil available state:
(a) by the circle equipped with diffusion phase thickness for 0.53mm, 0.91mm, 1.13mm, 1.73mm during soil incubation
DGT is inserted into pedotheque in 1d, 45d and 90d of heavy metal aging respectively, and is kept for certain operating time (for 24 hours), described
Round DGT with different-thickness diffusion phase is within the scope of 1-2cm in the depth in the soil sample；
(b) the round DGT equipped with different-thickness diffusion phase is taken out, after being rinsed well device with ultrapure water, is taken out
It is combined in the round DGT equipped with different-thickness diffusion phase and mutually fixes glue and using the HNO of 1mol/L3Solution carries out pickling
It is de-, collect eluent；The concentration of heavy metal in the eluent is measured, and the different-thickness that is equipped with is calculated and spreads phase
The time mean concentration C of heavy metal at round DGT/ solution interfaceDGT。
Wherein, CDGTIndicate that the heavy metal available state measured value of soil over a period to come, M are in DGT duration of run t
(for 24 hours) amount of metal accumulated in phase is combined in, A is that (this experimental provision is 4.64cm to DGT window area2), thickness of diffusion layer Δ g
For the sum of diffusion gel thickness degree and nitrocellulose filter thickness (0.013cm), D is institute's check weighing metal ion in diffusion gel
In diffusion coefficient (6.09 × 10-6Cm/s), t is device duration of run (for 24 hours).
(4) following equation is used, and organic legibility in soil is obtained using DPS software general nonlinearity Regression Model Simulator
Amorph content of beary metal CMLAnd dissociation rate constant K-1。
Wherein Δ g' indicates diffusion phase thickness, DMLIndicate complex state heavy metal in the soil diffusion coefficient (1.218 ×
10-6Cm/s), K-1For the dissociation rate constant of the complex state heavy metal, CMLFor legibility amorph content of beary metal organic in soil,
CM' it is the content of beary metal dissociated.
Input the equation in DPS software are as follows: x2=c1* (1-exp (- c2x1)).
Equation is the deformation of heavy metal Dissociation equation in step (4).Wherein x2 and CM' corresponding, it indicates with not
Bio-available Zn concentration (the C that the DGT of stack pile diffusion phase is measuredDGT) difference, CM'-CM；C1 is the complex state that can be dissociated in the soil
Content of beary metal CML；C2 is the 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 for obtaining fittingMLAnd K-1It brings into above-mentioned formula, obtains the heavy metal bio-available Zn concentration of DGT measurement for 24 hours
The reference state content of beary metal C of middle dissociationM'。
It is C in the free state content of beary metal that DGT duration of run measures in for 24 hoursM=CDGT-CM'。
Total heavy metal available state concentration is C in soilMLWith CMThe sum of.
Non- easy dynamic content of beary metal (C'): C'=C-C is calculated according to heavy metal-polluted soil full dose (C)M-CML。
During using DGT measurement heavy metal in soil available state concentration, it is generally recognized that spreading phase gel thicknesses is
The available state concentration measured when 0.8mm can represent the real available state concentration of heavy metal in soil.It is as shown in Figures 1 to 6
Six kinds of heavy metal in soil Cd free states, organic legibility amorph and the non-movability measured using the DGT of 0.91mm thickness diffusion phase
State content of beary metal.It can be seen that of the present invention use DGT technology separation soil heavy metals of different forms for evaluation later
Heavy metal-polluted soil different shape content has supplied a kind of quickly and easily detection method.
By taking Fig. 7,8 as an example, the acquisition process of parameter fitting process and result is illustrated,
1 heavy metal-polluted soil full dose of table and fitting obtain parameter
Note: C in tableMLFor the parameter C1, K obtained in fit procedure-1For the parameter C2 obtained in fit procedure.
Claims (2)
1. a kind of method using DGT technology separation soil heavy metals of different forms, characterized by the following steps:
(1) the preparation of pedotheque: topsoil sample in different regions is used, by collected soil sample identical with sampled point
It is saved, and is cultivated after sample is ground spare under the conditions of temperature；
(2) the preparation of different-thickness diffusion phase DGT: the diffusion phase of different-thickness is made respectively, and calculates the accurate of film with volumetric method
Thickness, it is spare to be assembled into DGT device after cutting, when extracting heavy metal-polluted soil and computational rules using different-thickness diffusion phase DGT
Interior heavy metal-polluted soil bio-available Zn concentration:
(a) the round DGT equipped with different-thickness diffusion phase is inserted into cultured pedotheque, and keeps certain operation
Time, the round DGT with different-thickness diffusion phase was within the scope of 1-2cm in the depth in the soil sample for 24 hours；
(b) the round DGT equipped with different-thickness diffusion phase is taken out, with ultrapure water, taking-up is described to be equipped with different-thickness
It spreads the combination in the round DGT of phase and mutually fixes glue and carry out pickling and take off, collect eluent；Measure heavy metal in the eluent
Concentration, and the heavy metal-polluted soil available state at the round DGT/ solution interface equipped with different-thickness diffusion phase is calculated
Content CDGT；
(3) heavy metal Dissociation equation is used, obtains in soil have using DPS software general nonlinearity Regression Model Simulator
Machine legibility amorph content of beary metal CMLAnd the dissociation rate constant K of complex state heavy metal-1；
(4) soil free state content of beary metal is calculated: the C that fitting is obtainedMLAnd K-1Bring heavy metal Dissociation equation calculation into
Obtain the complex state content of beary metal C dissociated in heavy metal bio-available Zn concentration in DGT measurement for 24 hoursM', free state content of beary metal
For CM=CDGT-CM'；
(5) non-easy dynamic content of beary metal C' is calculated according to heavy metal full dose C result, heavy metal-polluted soil full dose C calculates non-easy dynamic
Content of beary metal C':C'=C-CM-CML；
The step (3) with step (4) described in heavy metal Dissociation equation are as follows:
Wherein phase thickness, D are spread in Δ g ' expressionMLIndicate the diffusion coefficient of complex state heavy metal in the soil, K-1For complex state weight
The dissociation rate constant of metal, CMLFor legibility amorph content of beary metal organic in soil, CM' be minute internal disintegration complex state
Content of beary metal；
The step (2) in heavy metal-polluted soil bio-available Zn concentration calculation method in the stipulated time are as follows:
Wherein, CDGTFor heavy metal-polluted soil bio-available Zn concentration, M is that the amount of metal accumulated in phase, A are combined in DGT duration of run t
For DGT window area, thickness of diffusion layer Δ g is the sum of diffusion gel thickness degree and nitrocellulose filter thickness, and D is institute's check weighing
Diffusion coefficient of the metal ion in diffusion gel, t are device duration of run.
2. the method according to claim 1 using DGT technology separation soil heavy metals of different forms, it is characterised in that:
(2) middle different-thickness diffusion is accordingly more than or equal to 4 gradients to the step.
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| CN110849776A (en) * | 2019-11-26 | 2020-02-28 | 中国科学院城市环境研究所 | Method for measuring content of effective silicon in water body and soil |
| CN111103215A (en) * | 2019-12-16 | 2020-05-05 | 天津大学 | Method for evaluating desorption rate of heavy metals and metalloids in polluted or overproof soil |
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