CN109298024A - A kind of method of field quick detection heavy metal content in soil - Google Patents
A kind of method of field quick detection heavy metal content in soil Download PDFInfo
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- CN109298024A CN109298024A CN201811465345.9A CN201811465345A CN109298024A CN 109298024 A CN109298024 A CN 109298024A CN 201811465345 A CN201811465345 A CN 201811465345A CN 109298024 A CN109298024 A CN 109298024A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/22—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
Abstract
The present invention provides a kind of and entirely different field quick detection heavy metal content in soil of prior art principle method, specific practices are as follows: collection in worksite soil pattern;By soil pattern compacting, drying, it is placed between a pair of of parallel metal sheet, apply the continually changing alternate electrical signal of a frequency to it, real-time detection simultaneously records the electrical parameter that the alternate electrical signal passes through above-mentioned a pair of of parallel metal sheet and soil pattern, make normalized, carries out the identification of curvilinear characteristic degree to by normalized curve, and make curve Auto-matching operation in Standard Curve Database, numerical value in reference standard curve library obtains the content of beary metal of soil pattern collected.
Description
Technical field
The present invention relates to a kind of methods of field quick detection heavy metal content in soil.
Background technique
Heavy metal pollution of soil is a kind of very universal phenomenon, heavy metal pollution of soil refer to due to natural or
Heavy metal is brought into soil by mankind's activity, is caused heavy metal in soil content to be apparently higher than background value and is caused existing
Or the phenomenon that potential assessing index, Environmental deterioration.Heavy metal-polluted soil is from a wealth of sources, mainly includes atmosphere drop
Dirt, sewage irrigation, industrial solid castoff it is improper bank up, mining activities, pesticide and chemical fertilizer etc..It is all with heavy metal and containing weight
The material of metal is the industry of raw materials for production, may discharge heavy metal in process of production, if mishandling, will result in
Environmental pollution.
The place of industrial enterprise is one of most important type in municipal pollution soil.So far the whole nation has super within 2001
Guo10Wan Jia enterprise shuts down operating, produces the place of pollution largely abandon, high risk.These old industrial bases include
The enterprise of danger wastes is largely discharged by metal smelt, plating, machining, steel plant, chemical plant, insecticide factory etc..It is coloured heavy
The exploitation smelting of metalliferous deposit is the discharge most important pollution sources of heavy metal into environment.Weight is discharged into environment by " three wastes "
The industrial and mining enterprises of metal, such as: mining, ore dressing, metallurgy, plating, electrician, dyestuff, weaving, oil refining.Especially with IT product phase
The battery industry and printed circuit board of pass manufacture relevant electroplating industry, and heavy metal pollution problem should more be paid much attention to.Printing
Circuit board relates generally to the pollution such as copper, nickel, nickel compound and chromium, and battery and power supply are then related to lead contamination more, due to largely printing
Board production enterprise is unable to stably reaching standard discharge, and local river, soil and coastal waters has been given to cause pollution.
Heavy metal pollution in soil seriously endangers human health.The heavy metals such as lead, cadmium, mercury, arsenic, due to industrial activity
Development, causes the enrichment in mankind's ambient enviroment, enters human body by big gas and water, food etc., in the certain organ inner products of human body
It is tired, slow poisoning is caused, is detrimental to health.
During prevention, monitoring, administering heavy metal pollution of soil, detection heavy metal content in soil is one extremely important
Link.The quantitative detecting analysis technology of heavy metal usually has: it is ultraviolet can spectrophotometry (UV), atomic absorption method (AAS), former
Sub- fluorescence method (AFS), inductively coupled plasma body method (ICP), X fluorescence spectrum (XRF), Inductively coupled plasma-mass spectrometry
(ICP-MS).In addition to the above methods, there are also spectroscopic methodology detections.Japan and European Union member countries' some use inductive coupling plasma mass spectrometry
Method (ICP-MS) analysis, but for domestic user, instrument cost is high.Also some is analyzed using X fluorescence spectrum (XRF).It is newest
Popular detection method -- Anodic stripping, detection speed is fast, and numerical value is accurate, can use equal environmental emergencies detection on site.
Atomic absorption spectrography (AAS) be the 1950s found a kind of new instrument analysis method, it and be mainly used for nothing
The atomic emission spectrometry of machine qualitative elementary analysis complements each other, it has also become the master of quantitative elementary analysis is carried out to inorganic compound
Want means.
Atomic absorption analysis process is as follows: solution (while doing blank) is made in sample;Prepare a series of known concentrations
The calibration solution (standard specimen) of analytical element;Successively measure the analog value of blank and standard specimen;It is bent that correction is drawn according to above-mentioned analog value
Line;Measure the analog value of unknown sample;Analog value according to calibration curve and unknown sample obtains the concentration value of sample.
Ultraviolet-visible spectrophotometry (UV) testing principle is: heavy metal is usually organic compound with color developing agent-, can
Complex reaction occurs in heavy metal, generates coloured molecule group, the solution colour depth is directly proportional to concentration.At a particular wavelength, than
Color detection.There are two types of spectrophotometric analyses, and one is be measured using substance itself to ultraviolet and visible light absorption;It is another
Kind is to generate colored compound, i.e., " develops the color ", then measure.
Atomic fluorescence spectrometry (AFS) is by measuring the atomic vapour of element to be measured below specific frequency radiation energy swashs
Generated fluorescent emission intensity, with this come the method that measures constituent content to be measured.Atomic fluorescence spectrometry is a kind of transmitting light
Spectrometry, but it is closely related with atomic absorption spectrography (AAS), the advantages of having two kinds of analysis methods of atomic emissions and Atomic absorption concurrently.
Electrochemical process is to rely on classical direct current polarography, derives oscillographic polarography, anodic stripping voltammetry again on this basis
The methods of.Anodic stripping voltammetry is that potentiostatic deposition is enriched with a kind of electrochemical analysis side combined with voltammetric determination
Method.Anodic Stripping Voltammetry Determination is in two steps.The first step is " electrolysis ", i.e., under a constant potential, by tested ion-conductance
Solution deposition, enrichment generate amalgam with mercury on electrode on the working electrode (s.Second step is " dissolution ", i.e., after enrichment, generally
After static 30s or 60s, applies a backward voltage on the working electrode (s, just scanned by negative sense, metal in amalgam is reoxidized
It is returned in solution for ion, generates oxidation current, recording voltage-current curve, i.e. volt-ampere curve.Curve is in peak shape, peak value electricity
Flow to be tested in solution from concentration it is directly proportional, can be used as the foundation of quantitative analysis, spike potential can be used as qualitative analysis
Foundation.
X ray fluorescence spectrometry (XRF) be using sample to the absorption of X-ray in sample ingredient and its how many variations
And change to qualitatively or quantitatively determine a kind of method of ingredient in sample.When sample is by x-ray, energetic particle beam, ultraviolet light
When Deng irradiating, due to high energy particle or photon and sample atomic collision, atom inner electron being evicted to form hole, is made at atom
In excitation state, this excited state ion service life is very short, and when outer-shell electron inner layer hole transition, extra energy is penetrated with x
The form of line is released, and is generated new hole in religion outer layer and generated new x-ray emission, just generates a series of feature in this way
X-ray.Signature x-ray is that various elements are intrinsic, it is related with the atomic of element.As long as being penetrated so having measured feature x
The wavelength X of line, so that it may find out the element for generating the wavelength.
Inductively coupled plasma mass spectrometry (ICP-MS) is by as ion source ICP torch, interface arrangement and as detection
The mass spectrograph three parts of device form.Ionization source used in ICP-MS is inductively coupled plasma (ICP), and main body is one by three
The torch pipe of layer quartz socket tube composition, torch pipe upper end are wound with loading coil, and three-layer pipe leads to carrier gas respectively from the inside to surface, assist gas and cold
But gas, loading coil are coupled by high frequency electric source and are powered, and generate the magnetic field perpendicular to coil plane.If making argon by high-frequency device
Pneumoelectric from, then argon ion and electronics can collide again with other ar atmos under electromagnetic field effect and generate more ions and electronics,
Form vortex.Powerful electric current generates high temperature, and moment makes argon gas formation temperature up to the plasma torch of 10000k.Analyzed sample
Product are usually introduced into argon gas stream with the aerosol form of aqueous solution, are under atmospheric pressure subsequently into what is excited by RF energy
Argon plasma center, the high temperature of plasma make sample desolvation, vaporization dissociation and ionization.Part plasma passes through
Different pressure areas enter vacuum system, and in vacuum system, cation is drawn out and separates according to its mass-to-charge ratio.
In these above-mentioned detection methods, used instrument and equipment is all more accurate, expensive, and volume is larger, and need to be
It is fixed after the installation and debugging of laboratory to use, it can not go out to carry use, when detecting heavy metal content in soil, require existing
After quarry sampling, pretreatment and dystopy detection and analysis that laboratory carries out later period complexity are delivered, it is not only time-consuming but also inconvenient, it is impossible to be used in
Field quick detection.
Need quickly detection, analysis heavy metal pollution of soil situation when, be badly in need of it is a kind of can be used in on-site test, side
Portable belt, inexpensive detecting instrument and detection method.
Summary of the invention
It is of the existing technology in order to solve the problems, such as, the purpose of the present invention is to provide it is a kind of completely new, be totally different from
The detecting instrument and measurement method of the heavy metal content in soil of the prior art.
Realizing the specific technical solution of the object of the invention is:
A kind of method of field quick detection heavy metal content in soil, its step are as follows:
1, collection in worksite soil pattern;
2, the soil pattern collected is smashed, then applies pressure and is compacted, thin discs shape or thin square piece is made
Shape;
3, the soil pattern of compacting is placed between a pair of of parallel metal sheet and is compressed;
4, heating, drying is carried out in the state of compression to the soil pattern of compacting to constant weight;
5, sweep check: at a constant temperature, apply one on above-mentioned a pair of of parallel metal sheet using an alternating signal source
The continually changing alternate electrical signal v of frequencytIt acts on the soil pattern of drying, the output alternating electrical in the alternating signal source
Number vtFrequency f at any time t and change, signal amplitude then remains unchanged;
6, it real-time detection and records the alternate electrical signal and passes through the electricity ginseng of above-mentioned a pair of of parallel metal sheet and soil pattern
Number, the electrical parameter includes the apparent capacity real part Cp of alternate electrical signal, apparent capacity imaginary part Cp ', loss tangent Tan
(Delta), frequency f;Wherein, loss tangent Tan (Delta) is equal to apparent capacity imaginary part Cp ' and apparent capacity real part Cp
Ratio;
7, will obtained data of detection record in step 6, respectively export obtain apparent capacity real part Cp-frequency f curve,
Loss tangent Tan (Delta)-frequency f curve;In all apparent capacity real parts-frequency curve, loss tangent-
In frequency curve, frequency takes logarithm, i.e. logf or lgf;
8, the real part of apparent capacity obtained in step 7-frequency curve is made into normalized;
Loss tangent Tan (Delta)-frequency f curve itself has been substantially nondimensional, normalized song
Line, without remaking normalized;
9, curve is carried out to by normalized apparent capacity real part-frequency curve, loss tangent-frequency curve
The identification of feature degree, does Auto-matching operation with the curve in Standard Curve Database, the numerical value in reference standard curve library obtains being adopted
The content of beary metal of the soil pattern of collection, the Standard Curve Database record have multiple pre- first pass through to measure a huge sum of moneys obtain, different
Belong to apparent capacity real part-frequency curve, the loss tangent-frequency by normalized of the standard soil sample of content
Rate curve;In all apparent capacity real part-frequency curves, loss tangent-frequency curve, frequency takes logarithm,
That is logf or lgf.
Above-mentioned steps 5-9 is automatically completed by microprocessor or computer control, calculating.
Actual test temperature value is identical as the measurement temperature in Standard Curve Database.
Preferably, the size of the thin discs shape or thin square piece shape is Centimeter Level, with a thickness of grade;
Preferably, soil pattern is thin discs shape;
Preferably, a pair of of parallel metal sheet is thin discs shape;
Preferably, the sampling quantity of soil pattern is several grams to ten grams, in this way, in measurement, it both will not be because of sample size too
Cause measurement error big less, will not lead to overlong time spent by heating, drying because sample size is too big, expend
Electric energy is excessive.Normally, for several grams to ten grams of soil pattern amount, heating, drying is carried out in the state of compression to perseverance
Weight, generally requires 3-5 minutes;
By soil pattern, drying to constant weight, be moisture in order to avoid containing in sample to subsequent electrical measurement bring compared with
Big error.
Further, when acquiring soil pattern at the scene, dead twigs and withered leaves, macroscopic gravel particle are removed.
Preferably, step 2-3 merges are as follows: the soil pattern collected is pulverized, the soil pattern pulverized is direct
It is placed between a pair of of parallel metal sheet and applies pressure compaction, scrape off the redundance leaked out outside parallel metal sheet, system with scraping blade
At identical as parallel metal plate shape, equal-sized laminar sample;
Preferably, the temperature of heating, drying is carried out in the state of compression to the soil pattern of compacting between 100 DEG C -120
℃;
Preferably, the output alternate electrical signal v in the alternating signal sourcetFrequency f down to hundred Hz magnitudes, up to million Hz amounts
Grade;
Preferably, the output alternate electrical signal v in the alternating signal sourcetFrequency f t makees logarithmic parabola variation at any time;
According to our practical experience, in low-frequency range, apparent capacity real part Cp-frequency f curve of sample, loss angle are just
Value Tan (Delta)-frequency f curve is cut usually to change more slowly, if t makees linear rule variation to frequency f at any time, from hundred Hz
Magnitude will lead to time-consuming too long to million Hz magnitudes, be up to a few hours, and obtained data volume is too many, does not see in low-frequency range bright
Aobvious variation;And select frequency f t makees logarithmic parabola variation at any time, then it takes only about 1 minute, can be shown in each frequency band
Changing rule.
Preferably, in Standard Curve Database, each curve also has additional information, and the additional information includes: each
Apparent capacity real part-frequency curve, all extreme points of loss tangent-frequency curve, one by normalized
Zero point, the zero point of Second derivative curves of order derivative curve;
Further, curve Auto-matching mathematical algorithm is as follows:
A) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
Value-frequency curve first derivative, line segment of i-th point of the first derivative of each curve between the i-th, i+l point are oblique
Rate;
B) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
The zero point of value-frequency curve first derivative curve;
C) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
All extreme points of value-frequency curve;
D) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
Value-frequency curve second dervative, i-th point of second dervative of each curve are the i-th of its first derivative curve, i+l point
Between line segment slope;
E) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
The zero point of value-frequency curve Second derivative curves;
F) the normalized apparent capacity real part-frequency curve of all processes, loss angle are filtered out in Standard Curve Database just
Cut the corresponding extreme point of value-frequency curve, the zero point of first derivative curve, the quantity of the zero point of Second derivative curves with
Apparent capacity real part-frequency curve, loss tangent-of each of soil pattern Jing Guo normalized is calculated
The corresponding extreme point of frequency curve, the zero point of first derivative curve, the quantity of the zero point of Second derivative curves are distinguished equal
Curve, these curves filtered out remain to use in next step g;
G) the apparent capacity real part by normalized of the step b-e soil pattern being calculated-frequency is bent
Line, all extreme points of loss tangent-frequency curve, the zero point of first derivative curve, the zero point of Second derivative curves,
Apparent capacity real part-frequency of each in Standard Curve Database screened respectively with step f Jing Guo normalized is bent
Line, all extreme points of loss tangent-frequency curve, the zero point of first derivative curve, the zero point of Second derivative curves point
It does not compare, filters out the curve that all relative errors are less than pre-set tolerance value, these curves filtered out remain in next step
It is used in rapid h;
H) curve filtered out in step g is screened again, method are as follows: the soil pattern that step b-e is calculated
Apparent capacity real part-frequency curve by normalized, all numerical points of loss tangent-frequency curve,
Apparent capacity real part-frequency of each in Standard Curve Database screened respectively with step h Jing Guo normalized is bent
Line, all numerical points of loss tangent-frequency curve are respectively calculated meansquaredeviationσ, filter out wherein that meansquaredeviationσ is most
Small corresponding apparent capacity real part-frequency curve, loss tangent-frequency curve, by the apparent capacity filtered out reality
Portion-frequency curve, loss tangent-frequency curve corresponding content of beary metal in Standard Curve Database are tried as soil
The content of beary metal of sample.
Optionally, step f can ignore and skip, and in this case, the operand of step g will rise, but not be
Difference on the order of magnitude.
Optionally, step g can ignore and skip, in this case, although the arithmetic operation of step g is omitted, step
The operand of rapid h will rise, and from the point of view of our practice, great probability is the difference on the order of magnitude.Therefore, synthesis is examined
Worry is got off, and is considered from data-handling efficiency, speed, and step g, which had better not ignore, to be skipped.
Optionally, step f and g can ignore and skip, and in this case, the operand of step h will rise, and
The necessarily difference on the order of magnitude.
Therefore, preferably, step f, g does not ignore and skips, can lower significantly in this way operand, improve curve from
The efficiency of dynamic matching operation.
Further, the continually changing alternate electrical signal of frequency is generated by signal generator, and signal generator receives micro- place
Manage the control instruction that device or computer issue.
When the result of detection be reported out heavy metal in soil content it is significantly exceeded when, mark the soil of the sampling section by weight
Metallic pollution, and using it is ultraviolet can spectrophotometry (UV), atomic absorption method (AAS), atomic fluorescence method (AFS), inductive coupling
Plasma method (ICP), X fluorescence spectrum (XRF), any method in Inductively coupled plasma-mass spectrometry (ICP-MS) carry out
Further heavy metal type identifies, content accurately measures.
Measuring principle of the invention is described below:
Solid dielectric is in the effect by external electrical field, it may occur that electric polarization effect is not overlapped with positive and negative charge centroid
Electric polarization mode show electricity role and influence;Wherein play a major role be bound charge (in solid matter just
Anion, the electron outside nucleus fettered by atomic nucleus).Electrode law of bound charge under the action of electric field inside solid dielectric
There are substantial connections with medium microstructure.
There are three electropolarized basic processes: the 1. distortion polarization of extranuclear electron cloud;2. positive and negative ion in molecule
(opposite) displacement polarization;3. the steering of the intrinsic electric moment of molecule polarizes.Under extraneous electric field action, the permittivity ε of medium is comprehensive
Close the macroscopic physical quantity that ground reflects these three microprocess;It is the function of ε (f) of frequency f.
When just thinking that frequency is zero or frequency very low (such as 200Hz), three kinds of microprocess are involved in effect, dielectric at this moment
Constant ε (0) is constant for certain dielectric, is commonly referred to as dielectric constant, this namely static permittivity ε s or
Low-frequency dielectric constant.With the increase of frequency, the steering polarization of the intrinsic electric moment of molecule gradually lags behind the variation in outfield, at this moment,
Dielectric constant takes plural form ε (ω)=ε ' (f)-j ε " (f), and wherein imaginary part ε " (ω) represents dielectric loss;Although (dielectric
Capacitor changing with frequency, " dielectric constant " be not be a constant, but usually still use that " dielectric is normal in this field
Count " this term);It is since electric polarization course is not followed caused by the variation in outfield.Real part with frequency increase
And be remarkably decreased, there is peak value in imaginary part.Frequency is further added by, and real part ε ' (f) is down to new value, and imaginary part ε " (ω) becomes zero, this expression
The steering polarization of the intrinsic electric moment of molecule cannot respond.When frequency enters infrared region, the vibration of positive and negative ion electric moment in molecule
When dynamic frequency and outfield are resonated, real part ε ' (f) first increase suddenly suddenly declines, ε that " (f) peak value occurs again immediately;Cross this
After, the displacement polarization of positive and negative ion no longer works.
It is always defective in solid state medium for hard-packed solid state medium, under the action of an external electric field, charged defects
As soon as jumping to another equilbrium position or ion in certain local from equilbrium position to vibrate back and forth, effect phase
When in the steering of electric moment.Some solids with strong ionic (key), their static permittivity ε s are always bigger than the numerical value of n2
Much, outside the contribution of deionization displacement polarization, difference is exactly caused by the jump of charged defects under the action of an external electric field.
Study dielectric constant with frequency variation i.e. research dielectric constant frequency dispersion (dispersion) relationship, research dielectric loss,
Absorption of Medium and dielectric relaxation, rotation, ion for the structure of analyzing molecules and solid, the property of chemical bond and molecule
Vibration etc. it is clearly highly important.
For the solid dielectric of existing defects (especially foreign ion), under the action of an external electric field, not only exist
Electric polarization course, there is also conductance processes, show macroscopic view conduction current effect.
For the soil pattern by heavy metal pollution, since the quality of heavy metal ion is greater than other elements significantly
Ions/atoms, frequency response process of the ion of different quality in alternating electric field is there is apparent difference, in alternation electricity
During the frequency of field gradually rises, heavy metal ion becomes increasingly difficult to keep up with first the steering of applied alternating field, matter
It is such to measure bigger ion;And since heavy metal ion exists in the form of foreign ion in soil pattern, so that native
Earth sample, there is also being lost as caused by conduction electric current, shows electricresistance effect, soil pattern institute when by extra electric field
Impure ion is more, and leakage current is bigger, in test, shows as apparent capacity imaginary part Cp ', loss tangent Tan
(Delta) increase.
In the soil pattern by heavy metal pollution, type, the content of heavy metal significantly affect apparent capacity reality
Portion Cp-frequency f curve, loss tangent Tan (Delta)-frequency f curve shape, the distortion degree of curve shape, body
Reveal the weight of the substance of heterogeneity in soil.
By the apparent capacity real part Cp-frequency f curve, loss tangent Tan for the soil pattern that experiment measurement obtains
(Delta)-frequency f curve shape, can be finally inversed by heavy metal content in soil.In inverting, the standard of heavy metal content in soil
True degree depends on the sample-rich degree of established Standard Curve Database.
The content that this specification is not described in detail belongs to the prior art well known to professional and technical personnel in the field.
Beneficial effects of the present invention:
Using technical solution of the present invention, compared with the existing technology, have the advantages that following significant:
Since signal generator can be made Portable belt small in size, and test device there is no it is such as ultraviolet can spectrophotometric
Method (UV), atomic absorption method (AAS), atomic fluorescence method (AFS), inductively coupled plasma body method (ICP), X fluorescence spectrum
(XRF), accurate, the enervated component in Inductively coupled plasma-mass spectrometry (ICP-MS), is quite suitable for field condition and quickly examines
It surveys.
Due to being taken in step 8 to the normalized processing of test data, so that in front in step, it is flat without substituting into
The area of row metal plate, spacing are come the dielectric constant that converts, also, even if when soil sample compresses between parallel metal sheet, no matter
Really whether the completely dense space filled up between parallel metal sheet can be brought soil sample even if there are some perforations, lacking
The measured deviation of apparent capacity real part Cp, apparent capacity imaginary part Cp ', but after normalized, these influence all disappear,
Subsequent Data processing without considering the absolute size of these measured values, but need to only consider the shape for the curve that measurement obtains
Shape.This point brings the convenience of measurement.
And it is ultraviolet can spectrophotometry (UV), atomic absorption method (AAS), atomic fluorescence method (AFS), inductive coupling etc. from
Daughter method (ICP), X fluorescence spectrum (XRF), in Inductively coupled plasma-mass spectrometry (ICP-MS) measuring technique, none is not needed
Accurate, careful pre-treatment work is carried out to sample, is also had in measurement work meticulous.
It quickly being detected in addition, being suitable for field condition just because of technical solution of the present invention, operation very simple is convenient,
So that monitoring efficiency greatly improves in efforts at environmental protection.
Specific embodiment
It is of the invention for ease of understanding, come specifically to introduce technical solution of the present invention below with reference to example.
Embodiment one
A kind of method of field quick detection heavy metal content in soil, step are:
1, collection in worksite soil pattern about 5g;In acquisition, dead twigs and withered leaves, macroscopic gravel particle are removed;
2, the soil pattern collected is smashed, then applies pressure and is compacted, thin discs shape is made, thickness is about
1mm;
3, the soil pattern of compacting is placed between a pair of of parallel metal sheet and is compressed;
4, heating, drying is carried out in the state of compression to the soil pattern of compacting, heating temperature is 110 DEG C, drying time
3 minutes;
5, at a constant temperature, apply a frequency on above-mentioned a pair of of parallel metal sheet using an alternating signal source constantly to become
The alternate electrical signal v of changetIt acts on the soil pattern of drying, signal amplitude remains unchanged, the output alternation in alternating signal source
Electric signal vtFrequency f it is primary every 100ms variation, frequency increases from 100Hz, until increasing to 1MHz or so;
6, it real-time detection and records the alternate electrical signal and passes through the electricity ginseng of above-mentioned a pair of of parallel metal sheet and soil pattern
Number, the electrical parameter includes the apparent capacity real part Cp of alternate electrical signal, apparent capacity imaginary part Cp ', loss tangent Tan
(Delta), frequency f;Wherein, loss tangent Tan (Delta) is equal to apparent capacity imaginary part Cp ' and apparent capacity real part Cp
Ratio;
7, will obtained data of detection record in step 6, respectively export obtain apparent capacity real part Cp-frequency f curve,
Loss tangent Tan (Delta)-frequency f curve;In all apparent capacity real parts-frequency curve, loss tangent-
In frequency curve, frequency takes logarithm, i.e. logf or lgf;
8, the real part of apparent capacity obtained in step 7-frequency curve is made into normalized;
Loss tangent Tan (Delta)-frequency f curve itself has been substantially nondimensional, normalized song
Line, without remaking normalized;
9, curve is carried out to by normalized apparent capacity real part-frequency curve, loss tangent-frequency curve
The identification of feature degree, and makees curve Auto-matching operation, the numerical value in reference standard curve library obtains being acquired in Standard Curve Database
Soil pattern content of beary metal, Standard Curve Database record, which has, multiple pre- first passes through heavy metals that measurement obtains, different
Apparent capacity real part-frequency curve, the loss tangent-frequency by normalized of the standard soil sample of content
Curve;In all apparent capacity real part-frequency curves, loss tangent-frequency curve, frequency takes logarithm, i.e.,
Logf or lgf.
Above-mentioned steps 5-9 is automatically completed by microprocessor or computer control, calculating.
Embodiment two
In above-mentioned steps 5, the output alternate electrical signal v in alternating signal sourcetFrequency f it is primary every 200ms variation, frequency
Rate increases from 100Hz, and 1.1 times are differed between every two frequency, until increasing to 1MHz or so, specific list of frequency is as follows:
100Hz, 110Hz, 121Hz, 133.1Hz ..., 777.88KHz, 855.67KHz, 941.23KHz, 1.035MHz,
98 Frequency points in total,
Remaining is the same as example 1.
98 Frequency point tests are completed, and need time 49s in total.
Embodiment three
Step 2-3 is adjusted are as follows: the soil pattern collected is pulverized, the soil pattern pulverized is placed directly in
Apply pressure compaction between a pair of of parallel metal sheet, scrapes off the redundance leaked out outside parallel metal sheet with scraping blade, be made and put down
Row metal plate shape is identical, equal-sized laminar sample;
Remaining is identical as embodiment two.
Example IV
Step 9 concrete operations are as follows, remaining is identical as embodiment two:
A) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
Value-frequency curve first derivative, line segment of i-th point of the first derivative of each curve between the i-th, i+l point are oblique
Rate;
B) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
The zero point of value-frequency curve first derivative curve;
C) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
All extreme points of value-frequency curve;
D) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
Value-frequency curve second dervative, i-th point of second dervative of each curve are the i-th of its first derivative curve, i+l point
Between line segment slope;
E) apparent capacity real part-frequency curve, loss angle tangent by normalized of soil pattern is calculated
The zero point of value-frequency curve Second derivative curves;
F) the normalized apparent capacity real part-frequency curve of all processes, loss angle are filtered out in Standard Curve Database just
Cut the corresponding extreme point of value-frequency curve, the zero point of first derivative curve, the quantity of the zero point of Second derivative curves with
Apparent capacity real part-frequency curve, loss tangent-of each of soil pattern Jing Guo normalized is calculated
The corresponding extreme point of frequency curve, the zero point of first derivative curve, the quantity of the zero point of Second derivative curves are distinguished equal
Curve, these curves filtered out remain to use in next step g;
G) the apparent capacity real part by normalized of the step b-e soil pattern being calculated-frequency is bent
Line, all extreme points of loss tangent-frequency curve, the zero point of first derivative curve, the zero point of Second derivative curves,
Apparent capacity real part-frequency of each in Standard Curve Database screened respectively with step f Jing Guo normalized is bent
Line, all extreme points of loss tangent-frequency curve, the zero point of first derivative curve, the zero point of Second derivative curves point
It does not compare, filters out the curve that all relative errors are less than pre-set tolerance value, these curves filtered out remain in next step
It is used in rapid h;
H) curve filtered out in step g is screened again, method are as follows: the soil pattern that step b-e is calculated
Apparent capacity real part-frequency curve by normalized, all numerical points of loss tangent-frequency curve,
Apparent capacity real part-frequency of each in Standard Curve Database screened respectively with step h Jing Guo normalized is bent
Line, all numerical points of loss tangent-frequency curve are respectively calculated meansquaredeviationσ, filter out wherein that meansquaredeviationσ is most
Small corresponding apparent capacity real part-frequency curve, loss tangent-frequency curve, by the apparent capacity filtered out reality
Portion-frequency curve, loss tangent-frequency curve corresponding content of beary metal in Standard Curve Database are tried as soil
The content of beary metal of sample.
Certainly, described above is only that presently preferred embodiments of the present invention is answered the present invention is not limited to enumerate above-described embodiment
When explanation, anyone skilled in the art is all equivalent substitutes for being made, bright under the introduction of this specification
Aobvious variant, all falls within the essential scope of this specification, ought to be by protection of the invention.
The content that this specification is not described in detail belongs to the prior art well known to professional and technical personnel in the field.
Claims (10)
1. a kind of method of field quick detection heavy metal content in soil, which comprises the steps of: collection in worksite soil
Earth sample;Soil pattern is put into measuring instrument;Measurement obtains the physical parameter curve of soil, is compared with Standard Curve Database
It is right, obtain heavy metal in soil content.
2. a kind of method of field quick detection heavy metal content in soil as described in claim 1, which is characterized in that specific step
It is rapid as follows:
(1) collection in worksite soil pattern;
(2) soil pattern collected is smashed, then applies pressure and is compacted, thin discs shape or thin square piece shape is made;
(3) soil pattern of compacting is placed between a pair of of parallel metal sheet and is compressed;
(4) heating, drying is carried out in the state of compression to the soil pattern of compacting to constant weight;
(5) sweep check: at a constant temperature, apply a frequency on above-mentioned a pair of of parallel metal sheet using an alternating signal source
Continually changing alternate electrical signalv t It acts on the soil pattern of drying;
The output alternate electrical signal in the alternating signal sourcev t Frequency f at any time t and change, signal amplitude then remains unchanged;
(6) real-time detection and the alternate electrical signal is recorded by above-mentioned a pair of of parallel metal sheet and the electrical parameter of soil pattern,
The electrical parameter includes the apparent capacity real part Cp of alternate electrical signal, loss tangent Tan (Delta), frequency f;Wherein, it damages
Consume the ratio that angle tangent value Tan (Delta) is equal to apparent capacity imaginary part Cp ' and apparent capacity real part Cp;
(7) by the data that detection record obtains in step 6, export obtains apparent capacity real part Cp-frequency f curve, loss respectively
Angle tangent value Tan (Delta)-frequency f curve;In all apparent capacity real part-frequency curves, loss tangent-frequency
In curve, frequency takes logarithm, i.e. logf or lgf;
(8) real part of apparent capacity obtained in step 7-frequency curve is made into normalized;
(9) curve spy is carried out to by normalized apparent capacity real part-frequency curve, loss tangent-frequency curve
The identification of sign degree, does Auto-matching operation with the curve in Standard Curve Database, the numerical value in reference standard curve library obtains being acquired
Soil pattern content of beary metal;
The Standard Curve Database record has multiple pre- standard soil samples for first passing through content of beary metal that measurement obtains, different
Apparent capacity real part-frequency curve, loss tangent-frequency curve by normalized;In Standard Curve Database,
Each curve also has additional information, and the additional information includes: that apparent capacity of each Jing Guo normalized is real
Portion-frequency curve, all extreme points of loss tangent-frequency curve, the zero point of first derivative curve, second dervative are bent
The zero point of line;
In all apparent capacity real part-frequency curves, loss tangent-frequency curve, frequency takes logarithm, i.e.,
Logf or lgf;
Above-mentioned steps 5-9 is automatically completed by microprocessor or computer control, calculating.
3. a kind of method of field quick detection heavy metal content in soil as claimed in claim 2, it is characterised in that: the step
Suddenly (2)-(3) merge adjustment are as follows: pulverize the soil pattern collected, the soil pattern pulverized is placed directly in a pair
Apply pressure compaction between parallel metal sheet, scrape off the redundance leaked out outside parallel metal sheet with scraping blade, is made and parallel gold
Belong to that plate shape is identical, equal-sized laminar sample;Remaining step is constant.
4. a kind of method of field quick detection heavy metal content in soil as claimed in claim 2 or claim 3, it is characterised in that: hand over
The output alternate electrical signal in varying signal sourcev t Frequency f down to hundred Hz magnitudes, up to million Hz magnitudes;The output in alternating signal source is handed over
Varying electrical signalsv t Frequency f t makees logarithmic parabola variation at any time.
5. a kind of method of such as described in any item field quick detection heavy metal content in soil of claim 2-4, feature exist
In:
The curve Auto-matching operation, algorithm are as follows:
A) apparent capacity real part-frequency curve, loss tangent-by normalized of soil pattern is calculated
The first derivative of frequency curve, line segment slope of i-th point of the first derivative of each curve between the i-th, i+l point;
B) apparent capacity real part-frequency curve, loss tangent-by normalized of soil pattern is calculated
The zero point of the first derivative curve of frequency curve;
C) apparent capacity real part-frequency curve, loss tangent-by normalized of soil pattern is calculated
All extreme points of frequency curve;
D) apparent capacity real part-frequency curve, loss tangent-by normalized of soil pattern is calculated
The second dervative of frequency curve, i-th point of second dervative of each curve are between the i-th of its first derivative curve, i+l point
Line segment slope;
E) apparent capacity real part-frequency curve, loss tangent-by normalized of soil pattern is calculated
The zero point of the Second derivative curves of frequency curve;
F) it is filtered out in Standard Curve Database all by normalized apparent capacity real part-frequency curve, loss angle tangent
The corresponding extreme point of value-frequency curve, the zero point of first derivative curve, the quantity of the zero point of Second derivative curves with meter
Calculate apparent capacity real part-frequency curve, loss tangent-frequency of each for obtaining soil pattern Jing Guo normalized
The corresponding extreme point of rate curve, the zero point of first derivative curve, the quantity of the zero point of Second derivative curves distinguish equal song
Line, these curves filtered out remain to use in next step g;
G) by apparent capacity real part-frequency curve, damage by normalized of the step b-e soil pattern being calculated
Consume angle tangent value-all extreme points of frequency curve, the zero point of first derivative curve, the zero point of Second derivative curves, respectively with
Apparent capacity real part-frequency curve, damage of each in Standard Curve Database that step f is screened Jing Guo normalized
Consume angle tangent value-all extreme points of frequency curve, the zero point of first derivative curve, the zero point of Second derivative curves respectively into
Row comparison, filters out the curve that all relative errors are less than pre-set tolerance value, these curves filtered out remain in next step h
It uses;
H) curve filtered out in step g is screened again, method are as follows: by the warp of the step b-e soil pattern being calculated
Apparent capacity real part-frequency curve, all numerical points of loss tangent-frequency curve of normalized are crossed, respectively
Apparent capacity real part-frequency curve of each in Standard Curve Database screened with step h Jing Guo normalized,
All numerical points of loss tangent-frequency curve are respectively calculated meansquaredeviationσ, and it is the smallest to filter out wherein meansquaredeviationσ
Corresponding apparent capacity real part-frequency curve, loss tangent-frequency curve, the apparent capacity real part-that will be filtered out
Frequency curve, loss tangent-frequency curve corresponding content of beary metal in Standard Curve Database, as soil pattern
Content of beary metal.
6. a kind of method of such as described in any item field quick detection heavy metal content in soil of claim 2-5, feature exist
In: the continually changing alternate electrical signal of frequency is generated by signal generator, and signal generator receives microprocessor or computer hair
Control instruction out.
7. a kind of method of such as described in any item field quick detection heavy metal content in soil of claim 2-4, feature exist
In: actual test temperature value is identical as the measurement temperature in Standard Curve Database.
8. a kind of method of such as described in any item field quick detection heavy metal content in soil of claim 2-4, feature exist
In: step f and/or g, which ignore, to be skipped.
9. a kind of method of such as described in any item field quick detection heavy metal content in soil of claim 2-8, feature exist
In: the temperature of heating, drying is carried out in the state of compression between 100 DEG C -120 DEG C to the soil pattern of compacting;A pair of parallel gold
Belonging to plate is disc-shaped.
10. a kind of application of such as method of the described in any item field quick detection heavy metal content in soil of claim 2-9,
Be characterized in that: after step 9 further include: when the result of detection be reported out heavy metal in soil content it is significantly exceeded when, label should
Sample the The Heavy Metal Contaminated Soil of section, and using it is ultraviolet can spectrophotometry (UV), atomic absorption method (AAS), atom it is glimmering
Light method (AFS), inductively coupled plasma body method (ICP), X fluorescence spectrum (XRF), Inductively coupled plasma-mass spectrometry (ICP-MS)
In any method, further progress heavy metal type identifies, content accurately measures.
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CN117609686A (en) * | 2024-01-23 | 2024-02-27 | 云南农业大学 | Soil moisture content evaluation method based on frequency domain dielectric spectrum |
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