CN109142004A - The detection method of biologically effective state cadmium in a kind of soil - Google Patents
The detection method of biologically effective state cadmium in a kind of soil Download PDFInfo
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- CN109142004A CN109142004A CN201811109615.2A CN201811109615A CN109142004A CN 109142004 A CN109142004 A CN 109142004A CN 201811109615 A CN201811109615 A CN 201811109615A CN 109142004 A CN109142004 A CN 109142004A
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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
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N2001/2866—Grinding or homogeneising
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Abstract
The detection method of biologically effective state cadmium in a kind of soil includes the following steps: the acquisition of S100 sample and pretreatment, and acquisition soil simultaneously air-dries the soil of acquisition at room temperature, and 200 meshes are crossed after grinding, pedotheque is made；1-5g pedotheque is weighed to be placed in 250mL polytetrafluoroethylene (PTFE) Centrifuge Cup, it is separately added into the ethanol solution 25mL of 1mol/L ammonium chloride solution 25mL and 80%, is cleaned using ultrasonic cleaning machine, then be centrifuged through centrifuge, extracting solution is made after taking supernatant liquid filtering film, the HNO for being 1% with concentration3Solution constant volume；S200 measures the concentration of biologically effective state cadmium in extracting solution, and the standard curve for measuring the various concentration of biologically effective state cadmium is established by inductively coupled plasma mass spectrometry using icp ms；The concentration of biologically effective state cadmium in extracting solution is measured by standard curve using icp ms；S300 interpretation of result calculates the content of biologically effective state cadmium in the pedotheque of measurement according to the quality of the pedotheque of measurement and the concentration of the extracting solution of measurement.
Description
Technical field
The present invention relates to soil environment protection detection technique fields, and in particular to biologically effective state cadmium in a kind of soil
Detection method.
Background technique
The environmental behaviour and ecological effect of heavy metal element are not dependent on it in the environmental matrices such as soil or deposit
Total amount, but depend primarily on its existing phase and corresponding quantitative proportion.Metal difference present in environmental matrices
Chemical species determine their mobility and bioavilability；The research of biologically effective state heavy metal can be evaluation environment
Pollute, establish environmental standard and environmental pollution prevention and control and repair the reliable foundation of offer.Cadmium is a kind of widely distributed metal member
Element is located at the IIth B in the periodic table of elements, and the period 5 is mainly used in battery industry, followed by pigment, coating and plating
It is wide Deng, cadmium pollution distribution and there is stronger bio-toxicity, but the complexity of the environmental matrices as where it, it is accurate to extract
And rapid determination of content of cadmium element is detected with larger difficulty, the extraction for the Mobile Forms cadmium for being especially easy to be absorbed by human body, animal or plant
It is even more extremely difficult.The extracting method of biologically effective state cadmium mainly has step by step arithmetic method and single extraction method in soil at present,
Wherein step by step arithmetic mainly includes BCR method and Tessier method, but step by step arithmetic method is there are extraction process complexity, time-consuming, and
Exist between each phase in extraction process and interfere with each other, causes string phase problem；It is more common both at home and abroad in one-step extraction
Extractant have DTPA, EDTA and HCl etc., but these acid solutions due to pH value it is lower, make some non-replacement absorption in soil
The heavy metal of state is also extracted, and causes biggish experimental result deviation.For fields such as environmental protection, geology, ecology and agriculturals
Urgent need, the extracting method for developing rationally reliable biologically effective state cadmium, that is, Mobile Forms cadmium is imperative.
Summary of the invention
Technology of the invention solves the problems, such as: overcome the deficiencies of the prior art and provide it is a kind of be rationally reliable, easy to operation,
The detection method of biologically effective state cadmium in time saving, the accurate and soil that can verify that.
The technical solution of the invention is as follows: the detection method of biologically effective state cadmium, the biology have in a kind of soil
State cadmium is imitated by the summation for the cadmium for being easy to be absorbed by human body and animals and plants in soil, the detection method includes the following steps:
S100), sample acquisition and pretreatment
S110), acquire, grind, sieving
Acquisition soil simultaneously air-dries the soil of acquisition at room temperature, and 200 meshes are crossed after grinding, and pedotheque is made；
S120), extracting solution is prepared
It weighs 1-5g pedotheque to be placed in 250mL polytetrafluoroethylene (PTFE) Centrifuge Cup, is separately added into 1mol/L ammonium chloride solution
The ethanol solution 25mL of 25mL and 80% is cleaned by ultrasonic 30min using ultrasonic cleaning machine under 160W power, then through centrifuge
It is centrifuged 20min under the revolving speed of 4000rpm, extracting solution is made after taking supernatant to cross 0.45 μm of filter membrane, is 1% with concentration
HNO3Solution is settled to 100mL；
S200), the concentration of biologically effective state cadmium in extracting solution is measured
S210), standard curve is formulated
It is established by inductively coupled plasma mass spectrometry for measuring biology using icp ms
The standard curve of the various concentration of available Cd；
S220), the concentration of available Cd in extracting solution is measured
Using icp ms by standard curve measure extracting solution in biologically effective state cadmium it is dense
Degree；
S300), interpretation of result
S310), the content of biologically effective state cadmium in pedotheque is determined
According to the quality of the pedotheque of measurement and the concentration of the extracting solution of measurement, pass through formulaIt calculates
The content of biologically effective state cadmium in the pedotheque measured out, in formula:
W is the content of biologically effective state cadmium in the pedotheque of measurement, and unit is μ g/g, similarly hereinafter；
C be measurement extracting solution in biologically effective state cadmium concentration, unit ng/mL, similarly hereinafter；
V be measurement extracting solution volume, unit mL, similarly hereinafter；
M be measurement pedotheque quality, unit g, similarly hereinafter；
S320), determine ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque
S321), the pedotheque identical in quality with the pedotheque measured in step 310 is weighed, using micro-wave digestion
Method extracts total cadmium in pedotheque；
S322), according to formulaAmmonium chloride and ethyl alcohol are calculated to biologically effective state in pedotheque
The recovery rate of cadmium；
In formula:
W1It is ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque, similarly hereinafter；
WAlwaysFor the content for extracting total cadmium in pedotheque using Microwave Digestion, unit is μ g/g, similarly hereinafter.
Further, the method, including
S400), verify
S410), 1-5g pedotheque is weighed, seven phase cadmiums is extracted using modified seven footwork of Tessier, determines seven
The content of a phase cadmium passes through formula according to the content of seven phase cadmiums in pedotheque
Calculate benefit
With modified seven footwork of Tessier to the recovery rate of biologically effective state cadmium in pedotheque, in formula:
W2To utilize modified seven footwork of Tessier to the recovery rate of biologically effective state cadmium in pedotheque, similarly hereinafter；
WIt is water-solubleFor the content of water-soluble state cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIon exchangeFor the content of the pedotheque intermediate ion exchange state cadmium of measurement, unit is μ g/g, similarly hereinafter；
WCarbonateFor the content of carbonate combine state cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WFe-Mn oxidationFor the content of Fe-Mn oxide cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIt is weak organicFor the content of weak Organic Cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIt is strong organicFor the content of Organic Cadmium strong in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WResidueFor the content of residual form cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
S420), to the recovery rate of biologically effective state cadmium in pedotheque and utilized modified according to ammonium chloride and ethyl alcohol
Seven footwork of Tessier passes through formula η=W to the recovery rate of biologically effective state cadmium in pedotheque1-W2Calculate ammonium chloride and
Ethyl alcohol is to the recovery rate of biologically effective state cadmium in pedotheque and using modified seven footwork of Tessier to raw in pedotheque
Recovery rate of difference the verifying ammonium chloride and ethyl alcohol of the recovery rate of object available Cd to biologically effective state cadmium in pedotheque, formula
Middle η is ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque and utilizes modified seven footwork pair of Tessier
The difference of the recovery rate of biologically effective state cadmium in pedotheque, similarly hereinafter.
Further, in S210, pass through inductively coupled plasma mass spectrometry using icp ms
The standard curve for measuring the various concentration of biologically effective state cadmium is established, is included the following steps:
S211), the cadmium standard solution 5mL for measuring 100 μ g/mL is placed in 50mL volumetric flask, the HNO for being 1% with concentration3It is molten
Liquid constant volume is made the cadmium standard that cadmium concentration is 10 μ g/mL and uses solution；
S212), measure the cadmium standard that cadmium concentration is 10 μ g/mL and be placed in 100mL volumetric flask using solution 1mL, be with concentration
1% HNO3Solution constant volume is made the cadmium standard that cadmium concentration is 100ng/mL and uses solution；
S213), the cadmium standard that cadmium concentration is 100ng/mL is measured respectively uses solution 0mL, 0.5mL, 1mL, 2mL and 5mL
It is placed in 100mL volumetric flask, the HNO for being 1% with concentration3Solution constant volume, it is 0ng/mL, 0.5ng/mL, 1ng/ that cadmium concentration, which is made,
The cadmium standard of mL, 2ng/mL and 5ng/mL use solution；
S214), successively the cadmium standard that cadmium concentration is 0ng/mL, 0.5ng/mL, 1ng/mL, 2ng/mL and 5ng/mL is made
It is injected in icp ms with solution, using the concentration value of cadmium standard solution as abscissa, available Cd
Intensity value is ordinate, and icp ms draw the standard curve of the various concentration of cadmium automatically, to standard song
Line linear regression acquires the regression equation of cadmium concentration relationship.
Further, step S220 is measured in extracting solution using icp ms by standard curve
The step of concentration of biologically effective state cadmium are as follows: the HNO for being 1% by extracting solution concentration3Injection electricity after solution dilutes 10-100 times
Feel in couple plasma mass spectrometer, with running parameter identical with icp ms in step S214 survey
The intensity value of available Cd is obtained, regression equation is substituted into, the concentration of biologically effective state cadmium in extracting solution is calculated.
Further, while step S120 prepares extracting solution, blank sample is prepared, prepares the method packet of blank sample
It includes following steps: being separately added into the ethanol solution 25mL of 1mol/L ammonium chloride solution 25mL and 80% in 250mL polytetrafluoroethylene (PTFE)
In Centrifuge Cup, it is cleaned by ultrasonic 30min under 160W power using ultrasonic cleaning machine, then through centrifuge under the revolving speed of 4000rpm
It is centrifuged 20min, obtains extracting solution after taking supernatant to cross 0.45 μm of filter membrane, the HNO for being 1% with concentration3Solution is settled to 100mL,
Blank sample is made；
Step S220 measures biologically effective state in extracting solution by standard curve using icp ms
The step of concentration of cadmium are as follows:
S221), the HNO for being 1% by blank sample concentration3Solution injected after diluting 10-100 times inductive coupling etc. from
In daughter mass spectrograph, available Cd is measured with running parameter identical with icp ms in step S214
Intensity value, substitute into regression equation, the concentration of biologically effective state cadmium in blank sample is calculated；
S222), extracting solution is injected in icp ms, with inductive coupling in step S214 etc.
The identical running parameter of gas ions mass spectrograph measures the intensity value of available Cd, substitutes into regression equation, is calculated in extracting solution
The concentration of biologically effective state cadmium；
S223), pass through formula c=c1-c0Determine the concentration of biologically effective state cadmium in extracting solution, in formula, c0For blank examination
The concentration of biologically effective state cadmium in sample, unit ng/mL, similarly hereinafter；c1Have for biology in extracting solution is calculated in step S222
The concentration of effect state cadmium, unit ng/mL, similarly hereinafter.
Further, in step S214, step S221 and step S222, the work of icp ms
Parameter are as follows: wriggling pump speed: 48rpm, scanning times: 30 times, duplicate measurements number: 5 times, sample promotes the time: 40s, when cleaning
Between: 45s, nebulizer flow: 0.87L/min, plasma torch power: 1000W.
Further, in step S321, the soil-like identical in quality with the pedotheque measured in step 310 is weighed
Product extract total cadmium in pedotheque using Microwave Digestion, include the following steps:
S3211), weigh and be placed in polytetrafluoroethyl-ne with the pedotheque identical in quality of the pedotheque measured in step 310
In alkene counteracting tank, chloroazotic acid 6mL is added, is put into microwave dissolver, is cleared up, cleared up according to predetermined micro-wave digestion program
It is cooled to room temperature after finishing, digestion solution is transferred in polytetrafluoroethylene (PTFE) crucible, after low temperature catches up with acid on electric hot plate, is transferred to appearance
Measuring bottle, the HNO for being 1% with concentration3Solution is settled to 100mL and prepare liquid is made；
S3212), the HNO for being 1% with concentration3Solution injects inductively coupled plasma after prepare liquid is diluted 10-100 times
In constitution spectrometer, the intensity of total cadmium is measured with running parameter identical with icp ms in step S214
Value substitutes into regression equation, the concentration of total cadmium in prepare liquid is calculated.
Further, in step S3211, resolution is carried out according to predetermined micro-wave digestion program and is included the following steps:
S3211a), 2 minutes are kept the temperature after microwave dissolver is warming up to 120 DEG C with the heating rate of 20 DEG C/min；
S3211b), 5 minutes are kept the temperature after microwave dissolver is warming up to 150 DEG C with the heating rate of 7.5 DEG C/min；
S3211c), wave resolution instrument keeps the temperature 40 minutes after being warming up to 185 DEG C with the heating rate of 7 DEG C/min.
Further, step S410 weighs 1-5g pedotheque, extracts seven phases using modified seven footwork of Tessier
State cadmium determines the content of seven phase cadmiums, includes the following steps:
S411), the extracting solution of seven phase cadmiums is prepared
S4111), water-soluble state cadmium extracting solution is prepared
1-5g pedotheque is weighed in 250mL polytetrafluoroethylene (PTFE) Centrifuge Cup, 25mL ultrapure water is added, at 20-30 DEG C
At a temperature of vibrate 2h, be centrifuged 20min under the revolving speed of 3000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, be made
Water-soluble state cadmium extracting solution；
S4112), ion-exchange state cadmium extracting solution is prepared
The magnesium chloride solution 25mL that concentration is 1mol/L is added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup, at 20-30 DEG C
At a temperature of vibrate 2h, be centrifuged 20min under the revolving speed of 4000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, system
Obtain ion-exchange state cadmium extracting solution；
S4113), carbonate combine state cadmium extracting solution is prepared
The sodium acetate solution 25mL that concentration is 1mol/L is added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup, at 20-30 DEG C
At a temperature of vibrate 5h, be centrifuged 20min under the revolving speed of 4000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, system
Obtain carbonate combine state cadmium extracting solution；
S4114), Fe-Mn oxide cadmium extracting solution is prepared
In the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup be added concentration be 0.25mol/L hydroxylamine hydrochloride 50mL and concentration be
The hydrochloric acid solution 50mL of 0.25mol/L, 20-30 DEG C at a temperature of vibrate 6h, through centrifuge under the revolving speed of 4000rpm from
Heart 20min after taking supernatant to cross 0.45 μm of filter membrane, obtains Fe-Mn oxide cadmium extracting solution；
S4115), weak Organic Cadmium extracting solution is prepared
The sodium pyrophosphate 50mL that concentration is 0.1mol/L is added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup, controls pH value
Within the scope of 9-11,20-30 DEG C at a temperature of vibrate 3h, be centrifuged 20min under the revolving speed of 4000rpm through centrifuge, take
After clear liquid crosses 0.45 μm of filter membrane, weak Organic Cadmium extracting solution is made；
S4116), strong Organic Cadmium extracting solution is prepared
S4116a), hydrogen peroxide 5mL and the concentration that concentration is 30% are added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup
For 70% nitric acid 3mL, 80-86 DEG C at a temperature of keep 1.5h；
S4116b), the hydrogen peroxide 3mL that concentration is 30% is added, keeps 70min；
S4116c), the ammonium acetate 2.5mL that concentration is 3.2mol/L is added and is diluted to 25mL with ultrapure water, at room temperature
10h is stood, is centrifuged 20min under the revolving speed of 4000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, is made strong organic
State cadmium extracting solution；
S4117), residual form cadmium extracting solution is prepared
Residual form cadmium extracting solution is prepared using the method for step S4116；
S412), the content of seven phase cadmiums is determined
Water-soluble state cadmium, ion-exchange state cadmium, carbonate combine state cadmium, ferrimanganic oxygen are determined using step S200-S310 respectively
Change the content of state cadmium, weak Organic Cadmium, strong Organic Cadmium and residual form cadmium.
Further, in the verifying of step S400, including measure and calculation recovery of standard addition, the measure and calculation mark-on return
Yield includes the following steps:
The extracting solution with the extracting solution same volume measured in step S220 is measured, the soil-like determined according to step S310
The content of biologically effective state cadmium in product is added cadmium standard solution 0.5-10mL and mixed solution is made, using step S200-
S310 determines the content of cadmium in mixed solution, passes through formula
Calculate the recovery of standard addition of cadmium；In formula:
P is recovery of standard addition, similarly hereinafter；
CMark-onFor the concentration of cadmium in mixed solution, unit ng/mL, similarly hereinafter；
VStandardFor the volume of the cadmium standard solution of addition, unit mL, similarly hereinafter.
The advantages of the present invention over the prior art are that:
1, in soil of the invention biologically effective state cadmium detection method, using the ammonium chloride for being neutral solution and
Ethyl alcohol extracts biologically effective state cadmium, the acid-base property of soil itself is destroyed it is smaller, avoid the prior art using acid solution or
The activation of stable state cadmium and/or the solidification of Mobile Forms cadmium caused by alkaline solution extracts, the accuracy for extracting result substantially mention
It is high.
2, in soil of the invention biologically effective state cadmium detection method, it is creative by neutral solution extraction biology have
Effect state cadmium detects biologically effective state cadmium in soil, experimental method simple possible, analysis in conjunction with Inductively coupled plasma-mass spectrometry
Test speed is fast, stability is high, time-consuming is short, solves prior art operation complexity, time-consuming, and accuracy is low, stability difference etc.
Problem.
3, in soil of the invention biologically effective state cadmium detection method, using the ammonium chloride for being neutral solution and
Ethyl alcohol extracts biologically effective state cadmium, on the basis of the acid-base property to soil itself destroys smaller, Mobile Forms in ammonium chloride and soil
Cadmium occurs complexing and forms stable compound, and the ammonium chloride concentration used is 1mol/L, and the high ionic strength of 1mol/L enhances
Cd2+From the desorption of negatively charged soil surface；The introducing of ethanol solution can make cadmium element by its electronics transfer to its institute
The C that contains and containing on the atomic ion more than C, increases the degree of ionization of cadmium in the plasma, atomization and efficiency of transmission is improved, to rear
Certain effect of enhanced sensitivity is played in the Inductively coupled plasma-mass spectrometry measurement of continuous cadmium, guarantees accuracy when sample measurement and steady
It is qualitative.
4, in soil of the invention biologically effective state cadmium detection method, the main work of icp ms
It is reasonable to make parameter selection, compared with the existing technology, the efficiency and accuracy of detection greatly improved.
Detailed description of the invention
Fig. 1 is the flow chart of the detection method of biologically effective state cadmium in soil of the invention.
In detection method of the Fig. 2 for biologically effective state cadmium in soil of the invention, the various concentration of biologically effective state cadmium
Canonical plotting.
Specific embodiment
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width
Degree ", " thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside",
The orientation or positional relationship of the instructions such as " clockwise ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " is based on the figure
Orientation or positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the device of indication or suggestion meaning or
Element must have a particular orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
In addition, defining " first ", the feature of " second " can explicitly or implicitly include one or more of the features.?
In description of the invention, unless otherwise indicated, the meaning of " plurality " is two or more.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ",
" connected ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integrally connect
It connects；It can be mechanical connection, be also possible to be electrically connected；Can be directly connected, can also indirectly connected through an intermediary,
It can be the connection inside two elements.For the ordinary skill in the art, above-mentioned art can be understood with concrete condition
The concrete meaning of language in the present invention.
As shown in Figs. 1-2, in a kind of soil biologically effective state cadmium detection method, include the following steps:
S100), sample acquisition and pretreatment
S110), acquire, grind, sieving
Somewhere soil is acquired, and the soil of acquisition is air-dried at room temperature to water content at 20-30 DEG C less than 2%, in agate
200 meshes are crossed after grinding in mortar, pedotheque are made, in order to verify the detection of biologically effective state cadmium in soil of the invention
The accuracy of method chooses the GBW07401 national standard reference pedotheque that total cadmium content is 4.3 ± 0.4 μ g/g, and will choosing
The GBW07401 national standard reference pedotheque taken is air-dried at room temperature identical with above-mentioned steps to identical water content,
200 meshes are crossed after grinding, and pedotheque is made.
6 parts, number XN1~XN6 will be divided by pedotheque made from acquisition somewhere soil, while by selection
Pedotheque made from GBW07401 national standard reference pedotheque is divided into 6 parts, number GSS1~GSS6, with verifying
The reliability of the detection method of biologically effective state cadmium in soil of the invention.Preferably, the room temperature is 25 DEG C.
The detection method of biologically effective state cadmium is carried out to the pedotheque of number XN1~XN6 He number GSS1~GSS6,
Include the following steps:
S120), extracting solution is prepared
S121), sample extracting solution is prepared
It weighs 2.5g pedotheque to be placed in 250mL polytetrafluoroethylene (PTFE) Centrifuge Cup, is separately added into 1mol/L ammonium chloride solution
The ethanol solution 25mL of 25mL and 80% is cleaned by ultrasonic 30min using ultrasonic cleaning machine under 160W power, then through centrifuge
It is centrifuged 20min under the revolving speed of 4000rpm, extracting solution is made after taking supernatant to cross 0.45 μm of filter membrane, is 1% with concentration
HNO3Solution is settled to 100mL；The ultrapure water refers to that resistivity reaches the water of 18M Ω * cm (25 DEG C), and pH value is in 6.8-
7.2, preferably pH value is 7.
S121), blank sample is prepared
Be separately added into the ethanol solution 25mL of 1mol/L ammonium chloride solution 25mL and 80% in 250mL polytetrafluoroethylene (PTFE) from
In heart cup, be cleaned by ultrasonic 30min under 160W power using ultrasonic cleaning machine, then through centrifuge under the revolving speed of 4000rpm from
Heart 20min obtains extracting solution after taking supernatant to cross 0.45 μm of filter membrane, the HNO for being 1% with concentration3Solution is settled to 100mL, system
Obtain blank sample.Blank test is carried out by preparing blank sample, it can be with the method detection limit of measuring and calculation test and correction
The error due to caused by reagent, specific method are to be measured in parallel 5 times with Inductively coupled plasma mass spectrometry to blank solution, are obtained
To standard deviation, 3 times of standard deviation values are the detection limit of method.
S200), the concentration of biologically effective state cadmium in extracting solution is measured
S210), standard curve is formulated
It is established by inductively coupled plasma mass spectrometry for measuring biology using icp ms
The standard curve of the various concentration of available Cd.
S211), standard solution (Chinese measuring science is marked by the 080119 cadmium single element country of GBW (E) for measuring 100 μ g/mL
Research institute) cadmium standard solution 5mL be placed in 50mL volumetric flask, with concentration be 1% HNO3Constant volume, it is 10 μ g/ that cadmium concentration, which is made,
The cadmium standard of mL uses solution.
S212), measure the cadmium standard that cadmium concentration is 10 μ g/mL and be placed in 100mL volumetric flask using solution 1mL, be with concentration
1% HNO3Solution constant volume is made the cadmium standard that cadmium concentration is 100ng/mL and uses solution.
S213), the cadmium standard that cadmium concentration is 100ng/mL is measured respectively uses solution 0mL, 0.5mL, 1mL, 2mL and 5mL
It is placed in 100mL volumetric flask, the HNO for being 1% with concentration3Solution constant volume, it is 0ng/mL, 0.5ng/mL, 1ng/ that cadmium concentration, which is made,
The cadmium standard of mL, 2ng/mL and 5ng/mL use solution.
S214), successively the cadmium standard that cadmium concentration is 0ng/mL, 0.5ng/mL, 1ng/mL, 2ng/mL and 5ng/mL is made
It is injected in icp ms with solution, using the concentration value of cadmium standard solution as abscissa, available Cd
Intensity value is ordinate, and icp ms draw the standard curve of the various concentration of cadmium automatically, to standard song
Line linear regression acquires the regression equation of cadmium concentration relationship, wherein the intensity of available Cd is signal strength, i.e. different ions
The count value per second of detector under concentration.Wherein, inspection apparatus before measurement, it is ensured that it is in normal operating conditions, passes through instrument
The tuning of device dedicated tune liquid, the icp ms running parameter after being optimized are as follows: wriggling pump speed:
48rpm, scanning times: 30 times, duplicate measurements number: 5 times, sample promotes the time: 40s, scavenging period: 45s, atomizer stream
Amount: 0.87L/min, plasma torch power: 1000W.
S220), the concentration of available Cd in extracting solution is measured
S221), the HNO for measuring 50mL blank sample and being 1% with concentration3After solution dilutes 10 times, inductive coupling is injected
In plasma mass spectrograph, measured effectively with running parameter identical with icp ms in step S214
The intensity value of state cadmium substitutes into regression equation, the concentration of biologically effective state cadmium in blank sample is calculated.
S222), the HNO for measuring 50mL extracting solution and being 1% with concentration3After solution dilutes 10 times, injection inductive coupling etc.
In gas ions mass spectrograph, available state is measured with running parameter identical with icp ms in step S214
The intensity value of cadmium substitutes into regression equation, the concentration of biologically effective state cadmium in extracting solution is calculated.
S223), pass through formula c=c1-c0Determine the concentration of biologically effective state cadmium in extracting solution, in formula, c0For blank examination
The concentration of biologically effective state cadmium in sample, unit ng/mL, similarly hereinafter；c1Have for biology in extracting solution is calculated in step S222
The concentration of effect state cadmium, unit ng/mL, similarly hereinafter.
S300), interpretation of result
S310), the content of biologically effective state cadmium in pedotheque is determined
According to the quality of the pedotheque of measurement and the concentration of the extracting solution of measurement, pass through formulaIt calculates
The content of biologically effective state cadmium in the pedotheque measured out, in formula:
W is the content of biologically effective state cadmium in the pedotheque of measurement, and unit is μ g/g, similarly hereinafter；
C be measurement extracting solution in biologically effective state cadmium concentration, unit ng/mL, similarly hereinafter；
V be measurement extracting solution volume, unit mL, similarly hereinafter, in the present embodiment, the volume of the extracting solution of measurement
For 50mL；
M be measurement pedotheque quality, unit g, similarly hereinafter, in the present embodiment, the matter of the pedotheque of measurement
Amount is 1.25g.
S320), determine ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque
S321), the pedotheque identical in quality with the pedotheque measured in step 310 is weighed, in the present embodiment
In, the quality of the pedotheque of measurement is 1.25g, extracts total cadmium in pedotheque using Microwave Digestion；
S3211), the pedotheque identical in quality with the pedotheque measured in step 310 is weighed, in the present embodiment
In, the quality of the pedotheque of measurement is 1.25g, is placed in polytetrafluoroethylene (PTFE) counteracting tank, after 6mL chloroazotic acid is added, is put into microwave
It clears up in instrument, is cleared up according to predetermined micro-wave digestion program, be cooled to room temperature after resolution, digestion solution is transferred to poly-
In tetrafluoroethene crucible, after low temperature catches up with acid on electric hot plate, preferably catching up with sour temperature is 100 DEG C, is transferred to volumetric flask, uses concentration
For 1% HNO3Solution is settled to 100mL, shakes up, and it is to be measured that prepare liquid is made.Wherein, the chloroazotic acid is concentrated hydrochloric acid and concentrated nitric acid
It is by volume the mixture of 3:1 composition,
Preferably, the predetermined micro-wave digestion program is
S3211a), 2 minutes are kept the temperature after microwave dissolver is warming up to 120 DEG C with the heating rate of 20 DEG C/min；
S3211b), 5 minutes are kept the temperature after microwave dissolver is warming up to 150 DEG C with the heating rate of 7.5 DEG C/min；
S3211c), wave resolution instrument keeps the temperature 40 minutes after being warming up to 185 DEG C with the heating rate of 7 DEG C/min.
S3212), the HNO for being 1% with concentration3Solution injects inductively coupled plasma constitution after prepare liquid is diluted 10 times
In spectrometer, the intensity value of total cadmium, generation are measured with running parameter identical with icp ms in step S214
Enter regression equation, the concentration of total cadmium in prepare liquid is calculated.
S322), according to formulaAmmonium chloride and ethyl alcohol are calculated to biologically effective state in pedotheque
The recovery rate of cadmium；
In formula:
W1It is ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque, similarly hereinafter；
WAlwaysFor the content for extracting total cadmium in pedotheque using Microwave Digestion, unit is μ g/g, similarly hereinafter.
S400), verify
S410), 1-5g pedotheque is weighed, seven phase cadmiums is extracted using modified seven footwork of Tessier, determines seven
The content of a phase cadmium,
S411), the extracting solution of seven phase cadmiums is prepared
S4111), water-soluble state cadmium extracting solution is prepared
2.5g pedotheque is accurately weighed in 250mL polytetrafluoroethylene (PTFE) Centrifuge Cup, 25mL is added after boiling cooling
PH value be 7 ultrapure water, 25 DEG C at a temperature of vibrate 2h, be centrifuged 20min under the revolving speed of 3000rpm through centrifuge, take
After clear liquid crosses 0.45 μm of filter membrane, water-soluble state cadmium extracting solution is made；
S4112), ion-exchange state cadmium extracting solution is prepared
In the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup be added concentration be 1mol/L, pH value be 7 magnesium chloride solution 25mL,
25 DEG C at a temperature of vibrate 2h, be centrifuged 20min under the revolving speed of 4000rpm through centrifuge, supernatant taken to cross 0.45 μm of filter membrane
Afterwards, ion-exchange state cadmium extracting solution is made；
S4113), carbonate combine state cadmium extracting solution is prepared
The sodium acetate solution 25mL that concentration is 1mol/L is added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup, at 25 DEG C
At a temperature of vibrate 5h, be centrifuged 20min under the revolving speed of 4000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, be made
Carbonate combine state cadmium extracting solution；
S4114), Fe-Mn oxide cadmium extracting solution is prepared
In the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup be added concentration be 0.25mol/L hydroxylamine hydrochloride 50mL and concentration be
The hydrochloric acid solution 50mL of 0.25mol/L, 25 DEG C at a temperature of vibrate 6h, be centrifuged under the revolving speed of 4000rpm through centrifuge
20min after taking supernatant to cross 0.45 μm of filter membrane, obtains Fe-Mn oxide cadmium extracting solution；
S4115), weak Organic Cadmium extracting solution is prepared
The sodium pyrophosphate 50mL that concentration is 0.1mol/L is added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup, controls pH value
Be 10,25 DEG C at a temperature of vibrate 3h, be centrifuged 20min under the revolving speed of 4000rpm through centrifuge, supernatant taken to cross 0.45 μ
After m filter membrane, weak Organic Cadmium extracting solution is made；
S4116), strong Organic Cadmium extracting solution is prepared
S4116a), hydrogen peroxide 5mL and the concentration that concentration is 30% are added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup
For 70% nitric acid 3mL, shake up, 83 DEG C at a temperature of keep 1.5h；
S4116b), the hydrogen peroxide 3mL that concentration is 30% is added, shakes up, keep 70min and stirs frequently, it is preferred that
Agitation in every 10 minutes is primary；
S4116c), the ammonium acetate 2.5mL that concentration is 3.2mol/L is added and is diluted to 25mL with ultrapure water, at room temperature
10h is stood, is centrifuged 20min under the revolving speed of 4000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, is made strong organic
State cadmium extracting solution；
S4117), residual form cadmium extracting solution is prepared
Residual form cadmium extracting solution is prepared using the method for step S4116；
S412), the content of seven phase cadmiums is determined
Water-soluble state cadmium, ion-exchange state cadmium, carbonate combine state cadmium, ferrimanganic oxygen are determined using step S200-S310 respectively
Change the content of state cadmium, weak Organic Cadmium, strong Organic Cadmium and residual form cadmium.
S413), according to the content of seven phase cadmiums in pedotheque, pass through formula
Calculate benefit
With modified seven footwork of Tessier to the recovery rate of biologically effective state cadmium in pedotheque, in formula:
W2To utilize modified seven footwork of Tessier to the recovery rate of biologically effective state cadmium in pedotheque, similarly hereinafter；
WIt is water-solubleFor the content of water-soluble state cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIon exchangeFor the content of the pedotheque intermediate ion exchange state cadmium of measurement, unit is μ g/g, similarly hereinafter；
WCarbonateFor the content of carbonate combine state cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WFe-Mn oxidationFor the content of Fe-Mn oxide cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIt is weak organicFor the content of weak Organic Cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIt is strong organicFor the content of Organic Cadmium strong in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WResidueFor the content of residual form cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
S420), to the recovery rate of biologically effective state cadmium in pedotheque and utilized modified according to ammonium chloride and ethyl alcohol
Seven footwork of Tessier passes through formula η=W to the recovery rate of biologically effective state cadmium in pedotheque1-W2Calculate ammonium chloride and
Ethyl alcohol is to the recovery rate of biologically effective state cadmium in pedotheque and using modified seven footwork of Tessier to raw in pedotheque
Recovery rate of difference the verifying ammonium chloride and ethyl alcohol of the recovery rate of object available Cd to biologically effective state cadmium in pedotheque, formula
Middle η is ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque and utilizes modified seven footwork pair of Tessier
The difference of the recovery rate of biologically effective state cadmium in pedotheque, similarly hereinafter.
S430), measure and calculation recovery of standard addition
50mL extracting solution is measured, the content of biologically effective state cadmium in the pedotheque determined according to step S310 is added
Mixed solution is made in 100ng/mL cadmium standard solution 5mL, and the content of cadmium in mixed solution is determined using step S200-S310,
Pass through formula
Calculate the recovery of standard addition of cadmium.In formula:
P is recovery of standard addition, similarly hereinafter；
CMark-onFor the concentration of cadmium in mixed solution, unit ng/mL, similarly hereinafter；
VStandardFor the volume of the cadmium standard solution of addition, unit mL, similarly hereinafter, and in the present embodiment, the cadmium mark of addition
Standard is 5mL using the volume of liquid.
The data such as the measurement result of pedotheque of above-mentioned number XN1~XN6 and GSS1~GSS6 are referring to table 1.
The measurement result of 1 pedotheque of table
Wherein, the calculation formula of relative standard deviation is(in formula, n is
The pendulous frequency of sample；WiFor the i-th measured value of sample,For the average value of n times measurement).Pass through the survey to pedotheque
Determine the analysis of result it follows that
1, the requirement in experimental analysis to the microcomponent rate of recovery is (100 ± 10) %, recovery of standard addition shown in table 1
It between 94.32-107.33%, meets the requirements, illustrates that measurement result is accurate.
2, the recovery rate W of ammonium chloride and ethanol solution to biologically effective state cadmium1With international amendment Tessier seven
Recovery rate W obtained by footwork2Difference between -0.26-1.65%, it was demonstrated that the method for the present invention it is accurate and reliable.
3, according to the requirement of People's Republic of China (PRC) geological and mineral professional standard DZ/T0011-2015, relative standard deviation
It should be less than 7%, the relative standard deviation value in table 1 illustrates that the precision of the method for the present invention is high, instrument between 0.58-4.29%
Device measurement result is stablized.
The standard working curve of cadmium and detection limit are shown in Table 2. in the method for the present invention measurement soil
Table 2: the standard working curve and detection limit table of cadmium in measurement soil
| Linearly | Detection limit |
| The range of linearity (ng/mL) | 0-5.0 |
| Instrument detection limit (ng/mL) | 0.08×10-3 |
| Working curve fitting coefficient | 0.99996 |
In the method for the present invention, the range of linearity of standard working curve is 0-5.0ng/mL, and fitting coefficient 0.99996 is high
In 0.999, illustrate that its linear relationship is good；The detection of instrument is limited to 0.08 × 10-3Ng/mL is measured by blank assay
The detection of the method for ammonium chloride and ethanol extraction method is limited to 0.32 × 10-3Ng/mL, detection limit are lower；The total cadmium of GSS1~GSS6 contains
The measurement result of amount is respectively 4.78,4.58,4.63,4.33,3.97 and 4.59 μ g/g, and average value is 4.48 μ g/g, with country
4.3 ± 0.4 μ g/g of standard value is compared, and the analysis result for meeting standard substance should control the requirement within the scope of (100 ± 5) %,
These all further demonstrate the experiment of the method for the present invention and testing conditions are reliable.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " illustrative examples ",
The description of " example ", " specific example " or " some examples " etc. mean specific features described in conjunction with this embodiment or example,
Structure, material or feature are included at least one embodiment or example of the invention.In the present specification, to above-mentioned art
The schematic representation of language may not refer to the same embodiment or example.Moreover, description specific features, structure, material or
Person's feature can be combined in any suitable manner in any one or more of the embodiments or examples.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective,
The scope of the present invention is defined by the claims and their equivalents.
Claims (10)
1. the detection method of biologically effective state cadmium in a kind of soil, which comprises the steps of:
S100), sample acquisition and pretreatment
S110), acquire, grind, sieving
Acquisition soil simultaneously air-dries the soil of acquisition at room temperature, and 200 meshes are crossed after grinding, and pedotheque is made；
S120), extracting solution is prepared
It weighs 1-5g pedotheque to be placed in 250mL polytetrafluoroethylene (PTFE) Centrifuge Cup, is separately added into 1mol/L ammonium chloride solution 25mL
Ethanol solution 25mL with 80%, is cleaned by ultrasonic 30min using ultrasonic cleaning machine, then exist through centrifuge under 160W power
It is centrifuged 20min under the revolving speed of 4000rpm, extracting solution is made after taking supernatant to cross 0.45 μm of filter membrane, the HNO for being 1% with concentration3It is molten
Liquid is settled to 100mL；
S200), the concentration of biologically effective state cadmium in extracting solution is measured
S210), standard curve is formulated
It is established by inductively coupled plasma mass spectrometry for measuring biologically effective using icp ms
The standard curve of the various concentration of state cadmium；
S220), the concentration of available Cd in extracting solution is measured
The concentration of biologically effective state cadmium in extracting solution is measured by standard curve using icp ms；
S300), interpretation of result
S310), the content of biologically effective state cadmium in pedotheque is determined
According to the quality of the pedotheque of measurement and the concentration of the extracting solution of measurement, pass through formulaCalculate measurement
Pedotheque in biologically effective state cadmium content, in formula:
W is the content of biologically effective state cadmium in the pedotheque of measurement, and unit is μ g/g, similarly hereinafter；
C be measurement extracting solution in biologically effective state cadmium concentration, unit ng/mL, similarly hereinafter；
V be measurement extracting solution volume, unit mL, similarly hereinafter；
M be measurement pedotheque quality, unit g, similarly hereinafter；
S320), determine ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque
S321), the pedotheque identical in quality with the pedotheque measured in step 310 is weighed, is mentioned using Microwave Digestion
Take total cadmium in pedotheque；
S322), according to formulaAmmonium chloride and ethyl alcohol are calculated to biologically effective state cadmium in pedotheque
Recovery rate；
In formula:
W1It is ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque, similarly hereinafter；
WAlwaysFor the content for extracting total cadmium in pedotheque using Microwave Digestion, unit is μ g/g, similarly hereinafter.
2. according to the method described in claim 1, it is characterized by comprising
S400), verify
S410), 1-5g pedotheque is weighed, seven phase cadmiums is extracted using modified seven footwork of Tessier, determines seven phases
The content of cadmium passes through formula according to the content of seven phase cadmiums in pedotheque
It calculates to utilize and repair
Positive seven footwork of Tessier is to the recovery rate of biologically effective state cadmium in pedotheque, in formula:
W2To utilize modified seven footwork of Tessier to the recovery rate of biologically effective state cadmium in pedotheque, similarly hereinafter；
WIt is water-solubleFor the content of water-soluble state cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIon exchangeFor the content of the pedotheque intermediate ion exchange state cadmium of measurement, unit is μ g/g, similarly hereinafter；
WCarbonateFor the content of carbonate combine state cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WFe-Mn oxidationFor the content of Fe-Mn oxide cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIt is weak organicFor the content of weak Organic Cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WIt is strong organicFor the content of Organic Cadmium strong in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
WResidueFor the content of residual form cadmium in the pedotheque of measurement, unit is μ g/g, similarly hereinafter；
S420), modified Tessier to the recovery rate of biologically effective state cadmium in pedotheque and is utilized according to ammonium chloride and ethyl alcohol
Seven footworks pass through formula η=W to the recovery rate of biologically effective state cadmium in pedotheque1-W2Ammonium chloride and ethyl alcohol are calculated to soil
The recovery rate of biologically effective state cadmium and modified seven footwork of Tessier of utilization are to biologically effective state cadmium in pedotheque in earth sample
Recovery rate difference verifying ammonium chloride and ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque, η is ammonium chloride in formula
With ethyl alcohol to the recovery rate of biologically effective state cadmium in pedotheque and using modified seven footwork of Tessier to raw in pedotheque
The difference of the recovery rate of object available Cd, similarly hereinafter.
3. according to the method described in claim 1, it is characterized by:
In S210, established by inductively coupled plasma mass spectrometry for measuring life using icp ms
The standard curve of the various concentration of object available Cd, includes the following steps:
S211), the cadmium standard solution 5mL for measuring 100 μ g/mL is placed in 50mL volumetric flask, the HNO for being 1% with concentration3Solution constant volume,
The cadmium standard that cadmium concentration is 10 μ g/mL is made and uses solution；
S212), measure the cadmium standard that cadmium concentration is 10 μ g/mL and be placed in 100mL volumetric flask using solution 1mL, be 1% with concentration
HNO3Solution constant volume is made the cadmium standard that cadmium concentration is 100ng/mL and uses solution；
S213), the cadmium standard that cadmium concentration is 100ng/mL is measured respectively to be placed in using solution 0mL, 0.5mL, 1mL, 2mL and 5mL
100mL volumetric flask, the HNO for being 1% with concentration3Solution constant volume, it is 0ng/mL, 0.5ng/mL, 1ng/mL, 2ng/ that cadmium concentration, which is made,
The cadmium standard of mL and 5ng/mL uses solution；
S214), the cadmium standard that cadmium concentration is 0ng/mL, 0.5ng/mL, 1ng/mL, 2ng/mL and 5ng/mL is successively used into solution
It injects in icp ms, using the concentration value of cadmium standard solution as abscissa, the intensity value of available Cd
For ordinate, icp ms draw the standard curve of the various concentration of cadmium automatically, linear to standard curve
It returns, acquires the regression equation of cadmium concentration relationship.
4. according to the method described in claim 3, it is characterized by:
Step S220 measures biologically effective state cadmium in extracting solution by standard curve using icp ms
The step of concentration are as follows: the HNO for being 1% by extracting solution concentration3Solution injects inductively coupled plasma body after diluting 10-100 times
In mass spectrograph, the intensity of available Cd is measured with running parameter identical with icp ms in step S214
Value substitutes into regression equation, the concentration of biologically effective state cadmium in extracting solution is calculated.
5. according to the method described in claim 4, it is characterized by:
While step S120 prepares extracting solution, blank sample is prepared, prepares the method for blank sample the following steps are included: respectively
The ethanol solution 25mL of 1mol/L ammonium chloride solution 25mL and 80% is added in 250mL polytetrafluoroethylene (PTFE) Centrifuge Cup, using super
Sound washer is cleaned by ultrasonic 30min under 160W power, then is centrifuged 20min under the revolving speed of 4000rpm through centrifuge, takes supernatant
Liquid obtains extracting solution after crossing 0.45 μm of filter membrane, the HNO for being 1% with concentration3Solution is settled to 100mL, and blank sample is made；
Step S220 measures biologically effective state cadmium in extracting solution by standard curve using icp ms
The step of concentration are as follows:
S221), the HNO for being 1% by blank sample concentration3Solution injects inductively coupled plasma constitution after diluting 10-100 times
In spectrometer, the intensity of available Cd is measured with running parameter identical with icp ms in step S214
Value substitutes into regression equation, the concentration of biologically effective state cadmium in blank sample is calculated；
S222), by extracting solution inject icp ms in, with inductively coupled plasma body in step S214
The identical running parameter of mass spectrograph measures the intensity value of available Cd, substitutes into regression equation, biology in extracting solution, which is calculated, to be had
Imitate the concentration of state cadmium；
S223), pass through formula c=c1-c0Determine the concentration of biologically effective state cadmium in extracting solution, in formula, c0It is raw in blank sample
The concentration of object available Cd, unit ng/mL, similarly hereinafter；c1For biologically effective state cadmium in extracting solution is calculated in step S222
Concentration, unit ng/mL, similarly hereinafter.
6. according to the method described in claim 5, it is characterized by: in step S214, step S221 and step S222, inductance coupling
Close the running parameter of plasma mass spectrograph are as follows: wriggling pump speed: 48rpm, scanning times: 30 times, duplicate measurements number: 5 times, sample
Product promote the time: 40s, scavenging period: 45s, nebulizer flow: 0.87L/min, plasma torch power: 1000W.
7. according to the method described in claim 1, it is characterized by:
In step S321, the pedotheque identical in quality with the pedotheque measured in step 310 is weighed, using micro-wave digestion
Method extracts total cadmium in pedotheque, includes the following steps:
S3211), weigh and be placed in polytetrafluoroethylene (PTFE) with the pedotheque identical in quality of the pedotheque measured in step 310 and disappear
It solves in tank, chloroazotic acid 6mL is added, is put into microwave dissolver, is cleared up according to predetermined micro-wave digestion program, it is cold after resolution
But to room temperature, digestion solution is transferred in polytetrafluoroethylene (PTFE) crucible, after low temperature catches up with acid on electric hot plate, is transferred to volumetric flask, is used
The HNO that concentration is 1%3Solution is settled to 100mL and prepare liquid is made；
S3212), the HNO for being 1% with concentration3Solution injects inductivity coupled plasma mass spectrometry after prepare liquid is diluted 10-100 times
In instrument, the intensity value of total cadmium is measured with running parameter identical with icp ms in step S214, is substituted into
The concentration of total cadmium in prepare liquid is calculated in regression equation.
8. according to the method described in claim 7, it is characterized by: being carried out in step S3211 according to predetermined micro-wave digestion program
Resolution includes the following steps:
S3211a), 2 minutes are kept the temperature after microwave dissolver is warming up to 120 DEG C with the heating rate of 20 DEG C/min；
S3211b), 5 minutes are kept the temperature after microwave dissolver is warming up to 150 DEG C with the heating rate of 7.5 DEG C/min；
S3211c), wave resolution instrument keeps the temperature 40 minutes after being warming up to 185 DEG C with the heating rate of 7 DEG C/min.
9. according to the method described in claim 2, it is characterized by:
Step S410 weighs 1-5g pedotheque, extracts seven phase cadmiums using modified seven footwork of Tessier, determines seven
The content of phase cadmium, includes the following steps:
S411), the extracting solution of seven phase cadmiums is prepared
S4111), water-soluble state cadmium extracting solution is prepared
1-5g pedotheque is weighed in 250mL polytetrafluoroethylene (PTFE) Centrifuge Cup, 25mL ultrapure water is added, in 20-30 DEG C of temperature
Lower oscillation 2h is centrifuged 20min under the revolving speed of 3000rpm through centrifuge, and after taking supernatant to cross 0.45 μm of filter membrane, water-soluble state is made
Cadmium extracting solution；
S4112), ion-exchange state cadmium extracting solution is prepared
The magnesium chloride solution 25mL that concentration is 1mol/L is added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup, in 20-30 DEG C of temperature
Degree is lower to vibrate 2h, is centrifuged 20min under the revolving speed of 4000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, ion is made
Exchange state cadmium extracting solution；
S4113), carbonate combine state cadmium extracting solution is prepared
The sodium acetate solution 25mL that concentration is 1mol/L is added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup, in 20-30 DEG C of temperature
Degree is lower to vibrate 5h, is centrifuged 20min under the revolving speed of 4000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, carbonic acid is made
Salt reference state cadmium extracting solution；
S4114), Fe-Mn oxide cadmium extracting solution is prepared
In the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup be added concentration be 0.25mol/L hydroxylamine hydrochloride 50mL and concentration be
The hydrochloric acid solution 50mL of 0.25mol/L, 20-30 DEG C at a temperature of vibrate 6h, be centrifuged under the revolving speed of 4000rpm through centrifuge
20min after taking supernatant to cross 0.45 μm of filter membrane, obtains Fe-Mn oxide cadmium extracting solution；
S4115), weak Organic Cadmium extracting solution is prepared
The sodium pyrophosphate 50mL that concentration is 0.1mol/L is added in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup, controls pH value in 9-11
In range, 20-30 DEG C at a temperature of vibrate 3h, be centrifuged 20min under the revolving speed of 4000rpm through centrifuge, take supernatant mistake
After 0.45 μm of filter membrane, weak Organic Cadmium extracting solution is made；
S4116), strong Organic Cadmium extracting solution is prepared
S4116a), the hydrogen peroxide 5mL and concentration that addition concentration is 30% in the residue of polytetrafluoroethylene (PTFE) Centrifuge Cup are 70%
Nitric acid 3mL, 80-86 DEG C at a temperature of keep 1.5h；
S4116b), the hydrogen peroxide 3mL that concentration is 30% is added, keeps 70min；
S4116c), the ammonium acetate 2.5mL that concentration is 3.2mol/L is added and is diluted to 25mL with ultrapure water, stands at room temperature
10h is centrifuged 20min under the revolving speed of 4000rpm through centrifuge, after taking supernatant to cross 0.45 μm of filter membrane, strong Organic Cadmium is made
Extracting solution；
S4117), residual form cadmium extracting solution is prepared
Residual form cadmium extracting solution is prepared using the method for step S4116；
S412), the content of seven phase cadmiums is determined
Water-soluble state cadmium, ion-exchange state cadmium, carbonate combine state cadmium, Fe-Mn oxide are determined using step S200-S310 respectively
The content of cadmium, weak Organic Cadmium, strong Organic Cadmium and residual form cadmium.
10. according to the method described in claim 2, it is characterized by:
In the verifying of step S400, including measure and calculation recovery of standard addition, the measure and calculation recovery of standard addition include following step
It is rapid:
The extracting solution with the extracting solution same volume measured in step S220 is measured, it is raw in the pedotheque determined according to step S310
The content of object available Cd is added cadmium standard solution 0.5-10mL and mixed solution is made, and is determined using step S200-S310 mixed
The content for closing cadmium in solution, passes through formula
Calculate the recovery of standard addition of cadmium；In formula:
P is recovery of standard addition, similarly hereinafter；
CMark-onFor the concentration of cadmium in mixed solution, unit ng/mL, similarly hereinafter；
VStandardFor the volume of the cadmium standard solution of addition, unit mL, similarly hereinafter.
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