CN106483185A - The method that HG ICP MS measures rare and scatter element germanium and tellurium in geology - Google Patents
The method that HG ICP MS measures rare and scatter element germanium and tellurium in geology Download PDFInfo
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Abstract
The invention discloses a kind of method that HG ICP MS measures rare and scatter element germanium and tellurium in geology, including：Weigh geological sample in the politef inner canister of Enclosed sample bullet, to geological sample pretreatment；Configuration hydride generation system, introduces sample, bronsted lowry acids and bases bronsted lowry solution respectively, and the hydride of generation is sent in plasma by carrier gas after gas-liquid separation and is measured；Calibration curve and method detection limit, with 3 times of standard deviation calculation, and consider that diluted sample multiple 1000 obtains the detection limit of Ge and Te.The sensitivity of present invention acquisition signal Analysis and stability are higher, and the relative standard deviation of 20 Ge and Te signal intensitys of METHOD FOR CONTINUOUS DETERMINATION is respectively 8.3% and 2.1%；Te detection limit is lower than the detection limit 0.1 μ g/g directly being measured using the molten sample ICP MS of uncovered tetracid, is applied to analyze actual sample and can provide accurate result.
Description
Technical field
The invention belongs to geology composition measurement technical field, dilute scattered unit in more particularly, to a kind of HG-ICP-MS mensure geology
Plain germanium and the method for tellurium.
Background technology
Germanium and tellurium all belong to rare and scatter element, and also known as dispersed elements, they do not form independent deposit in nature, and with miscellaneous
The dispersion of matter state is present in the mineral of other elements, also known as dispersed elements.Their contents in the earth's crust are very low, and distribution is again
Disperse very much, most associations are in non-ferrous metal, coal and iron mine etc..In recent years, with China to three dilute metal strategic resources
Investigation and the attention looking for miner to make, the analysis method research about germanium and tellurium gets more and more, and is concentrated mainly on its separation and concentration side
Face.There is scholar's research to add the organic reagent of a small amount of carbon containing in the solution, ICP-MS can be improved to a certain extent and measure difficult electricity
From the signal-to-background ratio of element, improve the detection limit of element, applied and measured in the application of rare and scatter element in ICP-MS.
In existing geology, to there is analysis result inaccurate for rare and scatter element germanium and tellurium assay method.
Content of the invention
It is an object of the invention to provide a kind of HG-ICP-MS measure rare and scatter element germanium and tellurium in geology method it is intended to
Solve rare and scatter element germanium and tellurium assay method in existing geology and there is the inaccurate problem of analysis result.1. it is existing geology sample
In product, rare and scatter element germanium and tellurium Accurate Determining provide probability.2., in the presence of also can be for explaining organic reagent, ICP-MS measures dilute
During scattered element, the mechanism of signal enhanced sensitivity phenomenon provides foundation.
The present invention is achieved in that a kind of method that HG-ICP-MS measures rare and scatter element germanium and tellurium in geology, described
The method that HG-ICP-MS measures rare and scatter element germanium and tellurium in geology includes：Weigh geological sample in the polytetrafluoro of Enclosed sample bullet
In ethylene inner canister, to geological sample pretreatment；Configuration hydride generation system, introduces sample, bronsted lowry acids and bases bronsted lowry solution respectively, produces
Raw hydride is sent in plasma by carrier gas after gas-liquid separation and is measured；Calibration curve and method detection limit, with 3 times
Standard deviation calculation, and consider that diluted sample multiple 1000 obtains the detection limit of Ge and Te.
Further, described geological sample pretreatment comprises the following steps：
Weigh geological sample 0.0500g in the politef inner canister of Enclosed sample bullet, add 0.5mL Fluohydric acid. and
0.5mL nitric acid, on electric hot plate, 130 DEG C of heating evaporations, to closely dry, are subsequently adding 1.0mL Fluohydric acid. and 0.5mL nitric acid, cover interior
Lid, loads in steel bushing, tightens steel bushing lid, molten sample bullet is put in baking oven, heats 24h in 185 ± 5 DEG C.Uncap after cooling, take
Go out politef inner canister, be placed in electric hot plate and steam to closely dry, add 0.5mL nitric acid to be evaporated to closely do, repeat this operation once；
Add the nitric acid of 1.5mL 50%, be again loaded into closing in steel bushing, be placed in 150 DEG C of heated at constant temperature 8h in baking oven.Cold
But take out afterwards, uncap, dilute with water is simultaneously weighed into 50mL, as analytical solution after shaking up.
Further, described hydride generation system is 0.1% hydrogen-oxygen being made up of 20% hydrochloric acid+2% potassium borohydride
Change potassium.
Further, described carrier gas flux is 0.95L/min.
Further, described calibration curve and method detection limit method are：Pipette appropriate Ge and Te mixed standard solution, use
2% nitric acid stepwise dilution becomes 0.0 μ g/L, 1.0 μ g/L, 5.0 μ g/L, 10.0 μ g/L, 50.0 μ g/L standard series, collection 74Ge and
The signal of 125Te, draws calibration curve, and its linearly dependent coefficient is 0.9999.
Further, the condition of described mensure is as follows：ICP-MS Instrument working parameter is：Radio-frequency power 1300W, atomization air flow
Measure as 0.95L/min, cooling gas flow 14L/min, secondary air amount 0.80L/min, sampling depth 80step, scan mode is
Jump peak, scanning times 50, resolution is 100；Germanium and tellurium select respectively74Ge and125Te is analysis isotope；
Described calibration curve and method detection limit specifically include：Pipette germanium, tellurium mixed standard solution in right amount, use 2% nitric acid
Stepwise dilution becomes 0.0,1.0,5.0,10.0,50.0 μ g/L standard series, gathers under optimal instrument condition according to experimental technique74Ge and125The signal intensity of Te, draws calibration curve；
Parallel assay is carried out to 11 parts of sample blank solution, with 3 times of standard deviation calculation, and considers diluted sample multiple
1000 calculating detection limit DL=3 σ * 1000.
Further, described politef inner canister is provided with phase calculation module, the phasometer of described phase calculation module
The method calculated includes：
Receipt signal y (t) is expressed as：
Y (t)=x (t)+n (t)；
Wherein, x (t) is digital modulation signals, and n (t) is the impulsive noise of standard S α S distribution；MASK and MPSK modulates, x
T the analytical form of () is expressed as：
Wherein, N is sampling number, anFor the information symbol sending, in MASK signal, an=0,1,2 ..., M-1, M are
Order of modulation, in mpsk signal, an=ej2πε/M, ε=0,1,2 ..., M-1, g (t) represent rectangle molding pulse, TbRepresent symbol
Number cycle, fcRepresent carrier frequency, carrier wave initial phaseIt is equally distributed random number in [0,2 π]；
The expression formula on kth passage n-th road signal x (t) is：
X (t)=expj { ω0(t+τk+nTs)+1/2μ(t+τk+nTs)2, k=0,1 ...；N=0,1,2 ...
Wherein, ω0It is the initial angular velocity of output waveform, t is the time, and n represents the sequence number of way in every passage, and μ represents
Chirp rate, TsIt is the sampling period, τkRepresent the corresponding time difference of kth channel signal start-phase；
The phase place of kth passage the n-th road signalMake such as down conversion：
OrderPk.n=μ (τk+nTs)、Qk.n=ω0(τk+nTs)+1/2μ(τk+nTs)2, then above formula
Can turn to：
WhereinOn the basis of phase place, when signal attribute parameter is fixing, Pk.n、Qk.nAlso it is definite value, therefore also serve as joining
Number input；One offset phase of increase on the basis of master phase is all regarded in the waveform output on other roads asObtain；
Frequency domain data Y to each sampling instant p (p=0,1,2 ...)n(p, q), q=0,1,2 ..., Nfft- 1 is Nfft
The IFFT conversion of point, obtains p sampling instant corresponding time domain frequency hopping source signal, uses yn(p,qt)(qt=0,1,2 ..., Nfft-1)
Represent；
The time domain frequency hopping source signal y that all moment are obtainedn(p,qt) merge process, obtain final time domain frequency hopping
Source signal is estimated, concrete formula is as follows：
Here Kc=NfftThe sampling number that/C, C are spaced for Short Time Fourier Transform adding window, NfftLength for FFT.
Further, it is provided with synchronized orthogonal Frequency Hopping Signal blind source separating module, described synchronized orthogonal frequency hopping in described baking oven
The synchronized orthogonal Frequency Hopping Signal blind source separation method of signal blind source separating module includes：
Step one, is derived from the frequency hopping letter of multiple synchronized orthogonal frequency hopping radio sets using the array antenna received containing M array element
Number, each road receipt signal is sampled, the M road discrete time-domain mixed signal after being sampledm
=1,2 ..., M；
Step 2, carries out overlapping adding window Short Time Fourier Transform to M road discrete time-domain mixed signal, obtains M mixing letter
Number time-frequency domain matrixP=0,1 ..., P-1, q=0,1 ..., Nfft- 1, wherein P table
Show total window number, NfftRepresent FFT length；(p, q) represents time-frequency index, and specific time-frequency value is
Here NfftRepresent the length of FFT, p represents adding window number of times, TsRepresent sampling interval, fsRepresent sample frequency, C is integer,
Represent the sampling number at Short Time Fourier Transform adding window interval, C<Nfft, and Kc=Nfft/ C is integer that is to say, that using
The Short Time Fourier Transform of overlapping adding window；
Step 3, to the frequency-hopping mixing signal time-frequency domain matrix obtaining in step 2
Carry out pretreatment；RightCarry out low-yield pretreatment, that is, in each sampling instant p, willThe value that amplitude is less than thresholding ε sets to 0, and obtains
The setting of thresholding ε can determine according to the average energy of receipt signal；Find out p moment (p=0,1,2 ... P-1) non-zero
Time-frequency numeric field data, useRepresent, whereinRepresent the response of p moment time-frequencyCorresponding frequency indices when non-zero, to these non-zero normalization pretreatment, obtain
Pretreated vector b (p, q)=[b1(p,q),b2(p,q),…,bM(p,q)]T, wherein：
Step 4, estimates jumping moment and the corresponding normalized hybrid matrix of each jump of each jump using clustering algorithm
Column vector, Hopping frequencies；
According to step 4, step 5, estimates that the normalization hybrid matrix column vector obtaining estimates that time-frequency domain is jumped
Frequency source signal；Which this moment index belongs to and jump is judged to all sampling instants index p, concrete grammar is：IfThen represent that moment p belongs to l and jumps；IfThen represent that moment p belongs to the 1st
Jump；All moment p that l (l=1,2 ...) is jumpedl, estimate the time-frequency numeric field data of this jump each frequency hopping source signal, computing formula is such as
Under：
Step 6, splices to the time-frequency domain frequency hopping source signal between different frequency hopping points；Estimate that l jumps correspondingIndividual
Incident angle, usesRepresent the corresponding incident angle of l n-th source signal of jump,Computing formula as follows：
Represent that l jumps n-th hybrid matrix column vector estimating to obtainM-th element, c represents the light velocity,
I.e. vc=3 × 108Meter per second；Judge that l (l=2,3 ...) jumps right between the source signal that the source signal estimated and the first jump are estimated
Should be related to, judgment formula is as follows：
Wherein mn (l)Represent that l jumps the m estimatingn (l)Individual signal and first is jumped n-th signal estimated and is belonged to same source
Signal；By different frequency hopping point estimation to the signal belonging to same source signal be stitched together, as final time-frequency domain source
Signal estimation, uses YnTime-frequency domain estimated value in time frequency point (p, q) for n-th source signal of (p, q) expression, p=0,1,2 ....,
P, q=0,1,2 ..., Nfft- 1, that is,
Step 7, according to source signal time-frequency domain estimated value, recovers time domain frequency hopping source signal.
Further, it is provided with signal detection module, the signal detecting method bag of described signal detection module in described baking oven
Include：
Mid frequency for known radio frequency or modulated intermediate frequency signal and bandwidth B c of the signal being likely to be received；
The first step, the radio frequency in Reived_V1 or Reived_V2 or if sampling signal are believed for fo single-frequency with frequency
Number it is mixed, obtained signal x1；
Second step, removes the high fdrequency components of signal x1 using low pass filter A, and the three dB bandwidth of low pass filter A is more than divides
Analysis bandwidth B s, obtains signal x2, now x2 is the signal of zero intermediate frequency, and the signal with a width of Bs is affected by wave filter A
Very little, negligible；
3rd step, because x2 has been zero intermediate frequency signals, therefore Fo=0, N is carried out to signal x2FFTThe FFT computing of points,
Then modulus, and by front NFFT/ 2 points are stored in VectorF, save the amplitude spectrum of signal x2 in VectorF；
4th step, analysis bandwidth Bs is divided into the equal Block, N=3,4 of N block ... .., each Block will enter
The a width of Bs/N of band of row operation, if the low-limit frequency that will analyze bandwidth Bs is FL, FL=0, then nBlock block, n=1...N,
Corresponding frequency separation scope is [FL+ (n-1) Bs/N, FL+ (n) Bs/N] respectively, by frequency range corresponding in VectorF
Frequency point distributes to each block, and the VectorF point range that wherein nBlock divides is [Sn, Sn+kn], whereinRepresent the number of every section of Frequency point got, and
Represent is starting point, and fs is signal sampling frequencies, and round (*) represents the computing that rounds up；
5th step, seeks the energy ∑ of its frequency spectrum to each Block | |2, obtain E (n), n=1...N；
6th step, averages to vectorial E
7th step, try to achieve vectorial E variance and
8th step, update flag bit flag, flag=0, the front testing result of expressions be no signal, this kind of under the conditions of,
Only work as σsum>It is judged to currently detected signal, flag is changed into 1 during B2；Work as flag=1, represent that a front testing result is to have
Signal, this kind of under the conditions of, only work as σsum<It is judged to during B1 currently be not detected by signal, it is thresholding that flag is changed into 0, B1 and B2
Value, with theoretical simulation, empirical value is given, B2>B1；
According to flag bit, 9th step, controls whether subsequent demodulation thread etc. is opened：Flag=1, opens subsequent demodulation thread
Deng otherwise closing subsequent demodulation thread.
Further, described wave filter is provided with state observation module, the signal processing method bag of described state observation module
Include：
Dq axle capacitance voltage uCdWith uCq, dq axle grid side electric current i1dWith i1qAnd dq axle current transformer side electric current i2dWith i2qFor
System state variables, and wherein current transformer side electric current i2dWith i2qCan be directly obtained by current transformer side current sensor；
For realizing the state observation on dq axle, analyze the situation of monophase system, the monophase system differential of wave filter first
Equation arranges and is：
The output equation formula of LCL filter arranges and is：
i2=[1 0 0] [i2i1uC]T(2)
Due to rank { [1 0 0] }=1, therefore the state variable of reconstruct is needed to be [i1uC]T, two will be decomposed into by original system
Individual subsystem, does not respectively need the subsystem reconstructing and the subsystem needing reconstruct, does not wherein need the subsystem reconstructing to be referred to as
For non-reconstruction subsystem, it is formula (1) the first row；The subsystem needing reconstruct is referred to as reconstruction subsystem, the table of non-reconstruction subsystem
Reaching formula is：
Wherein, after equal sign, Section 2 is the coupling matrix of reconstruction subsystem to non-reconstruction subsystem, defines this matrix and attaches most importance to
The output of structure subsystem, and because it is 1 rank, therefore it is as follows to be expressed as η：
Then the expression formula of reconstruction subsystem is：
The proper polynomial of reconstruction subsystem：
Its limit real part in the imaginary axis, the expectation limit of observation is designed in Left half-plane, that is, has negative real part for 0, sees
The limit surveyed is p1=-pr+pi·j、p2=-pr-piJ, observation error feedback matrix isIt is expressed as：
Estimate [i1uC]T, reconstruction subsystem is designed as follows：
By itsItem moves on the left of equal sign, and formula (8) is made with conversion writing：
Define dimensionality reduction observation state be：
According to dimensionality reduction Observation Theory, the state space equation of this observation：
The state variable expression formula of so observation is：
Thus obtain the characteristic equation of dimensionality reduction observation：
Then configuration observation error feedback matrix and dimensionality reduction observation limit real part are had with the relation of imaginary part：
The method that the HG-ICP-MS that the present invention provides measures rare and scatter element germanium and tellurium in geology, establishes HG-ICP-MS and surveys
Determine the analysis method of rare and scatter element germanium and tellurium in geological sample.With 20% hydrochloric acid+2% potassium borohydride (0.1% hydroxide in experiment
Potassium medium) as optimal hydride generation system, 0.95L/min is optimal carrier gas flux, obtains the sensitive of signal Analysis
Degree and stability are higher, the relative standard deviation respectively 8.3% and 2.1% of 20 Ge and Te signal intensitys of METHOD FOR CONTINUOUS DETERMINATION, residual
The basic cleaning in 200s of remaining Ge and Te signal intensity in ICP-MS finishes.Ge and Te detection limit is respectively 0.007 μ g/g
With 0.006 μ g/g, wherein Te detection limit than the detection limit (0.1 μ g/g) directly being measured using the molten sample ICP-MS of uncovered tetracid more
Low, it is applied to analysis actual sample and can provide accurate result.Voluntarily set capable hydride generation system, simple, practical, dismounting side
Just, by optimizing hydride reaction condition come control stability, good separating effect, good stability.Through national standard reference material
Rock Series sample is verified, the method is reliable, accurately, and has certain practicality, can be used in conventional geological sample Ge and
The analysis of Te.The present invention is mainly based upon hydride and occurs to play separation and concentration to microscratch amount target analytes, and ICP-
The highly sensitive advantage of MS and the research that launches, have been effectively combined both advantages, thus improve the accuracy of analysis, fall
The low detection limit of method, the Accurate Determining that other can be produced with the micro-trace elements of hydride provides certain method reference.This
The synchronized orthogonal Frequency Hopping Signal blind source separation method that invention provides, under conditions of not knowing any channel information, according only to connecing
The mixed signal of the multiple Frequency Hopping Signals receiving, estimates frequency hopping source signal, can be less than source signal number in reception antenna number
Under conditions of, blind estimate is carried out to multiple Frequency Hopping Signals, with only Short Time Fourier Transform, amount of calculation is little, easily realize,
Moreover it is possible to estimate to partial parameters while blind separation is carried out to Frequency Hopping Signal, practical, have stronger popularization with
Using value.
Brief description
Fig. 1 is the method flow diagram that HG-ICP-MS provided in an embodiment of the present invention measures rare and scatter element germanium and tellurium in geology.
Fig. 2 is the relation schematic diagram of flow rate of carrier gas provided in an embodiment of the present invention and signal intensity.
Fig. 3 is the relation schematic diagram of scavenging period provided in an embodiment of the present invention and signal intensity.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
Below in conjunction with the accompanying drawings the application principle of the present invention is explained in detail.
As shown in figure 1, the embodiment of the present invention HG-ICP-MS measure geology in rare and scatter element germanium and tellurium method include with
Lower step：
S101：Accurately weigh geological sample (rock) 0.0500g in the politef inner canister of Enclosed sample bullet, add
0.5mL Fluohydric acid. and 0.5mL nitric acid, on electric hot plate, low temperature (130 DEG C about) heating evaporation, to closely dry, is subsequently adding 1.0mL
Fluohydric acid. and 0.5mL nitric acid, cover inner cap, load in steel bushing, tighten steel bushing lid, molten sample bullet is put in baking oven, in 185 ± 5
DEG C heating 24h.Uncap after cooling, take out politef inner canister, be placed in electric hot plate and steam to closely dry, add 0.5mL nitric acid to steam
It is sent to closely dry, repeat this operation once；
S102：Add the nitric acid of 1.5mL 50%, be again loaded into closing in steel bushing, be placed in 150 DEG C of heated at constant temperature in baking oven
8h.Take out after cooling, uncap, dilute with water is simultaneously weighed into 50mL, as analytical solution after shaking up；
S103：Prepare 20% hydrochloric acid+2% potassium borohydride (0.1% potassium hydroxide medium) as hydride generation body
System, introduces sample, bronsted lowry acids and bases bronsted lowry solution respectively, and the hydride of generation is sent by carrier gas (flow is 0.95L/min) after gas-liquid separation
Enter in plasma and be measured；
S104：Calibration curve and method detection limit, pipette appropriate Ge and Te mixed standard solution, dilute step by step with 2% nitric acid
It is interpreted into 0.0 μ g/L, 1.0 μ g/L, 5.0 μ g/L, 10.0 μ g/L, 50.0 μ g/L standard series, according to experimental technique in optimal instrument
Under the conditions of gather the signal of 74Ge and 125Te, draw calibration curve, its linearly dependent coefficient is 0.9999；
S105：With 3 times of standard deviation calculation, and consider that diluted sample multiple 1000 obtains the detection limit of Ge and Te.
Condition determination is as follows：ICP-MS (Thermo company of the U.S., model X SeriesII) Instrument working parameter is：Radio frequency
Power 1300W, atomization gas (Ar) flow is 0.95L/min, cooling gas flow 14L/min, and secondary air amount 0.80L/min is adopted
Sample depth 80step, scan mode is to jump peak, scanning times 50, and resolution is 100；
Germanium and tellurium select respectively74Ge and125Te is analysis isotope.
Calibration curve and method detection limit specifically include：Pipette germanium, tellurium mixed standard solution in right amount, with 2% nitric acid step by step
It is diluted to 0.0,1.0,5.0,10.0,50.0 μ g/L standard series, gather under optimal instrument condition according to experimental technique74Ge
With125The signal intensity of Te, draws calibration curve.
Parallel assay is carried out to 11 parts of sample blank solution, with 3 times of standard deviation calculation, and considers diluted sample multiple
1000 calculating detection limit DL=3 σ * 1000.
Further, described politef inner canister is provided with phase calculation module, the phasometer of described phase calculation module
The method calculated includes：
Receipt signal y (t) is expressed as：
Y (t)=x (t)+n (t)；
Wherein, x (t) is digital modulation signals, and n (t) is the impulsive noise of standard S α S distribution；MASK and MPSK modulates, x
T the analytical form of () is expressed as：
Wherein, N is sampling number, anFor the information symbol sending, in MASK signal, an=0,1,2 ..., M-1, M are
Order of modulation, in mpsk signal, an=ej2πε/M, ε=0,1,2 ..., M-1, g (t) represent rectangle molding pulse, TbRepresent symbol
Number cycle, fcRepresent carrier frequency, carrier wave initial phaseIt is equally distributed random number in [0,2 π]；
The expression formula on kth passage n-th road signal x (t) is：
X (t)=expj { ω0(t+τk+nTs)+1/2μ(t+τk+nTs)2, k=0,1 ...；N=0,1,2 ...
Wherein, ω0It is the initial angular velocity of output waveform, t is the time, and n represents the sequence number of way in every passage, and μ represents
Chirp rate, TsIt is the sampling period, τkRepresent the corresponding time difference of kth channel signal start-phase；
The phase place of kth passage the n-th road signalMake such as down conversion：
OrderPk.n=μ (τk+nTs)、Qk.n=ω0(τk+nTs)+1/2μ(τk+nTs)2, then above formula
Can turn to：
WhereinOn the basis of phase place, when signal attribute parameter is fixing, Pk.n、Qk.nAlso it is definite value, therefore also serve as joining
Number input；One offset phase of increase on the basis of master phase is all regarded in the waveform output on other roads asObtain；
Frequency domain data Y to each sampling instant p (p=0,1,2 ...)n(p, q), q=0,1,2 ..., Nfft- 1 is Nfft
The IFFT conversion of point, obtains p sampling instant corresponding time domain frequency hopping source signal, uses yn(p,qt)(qt=0,1,2 ..., Nfft-1)
Represent；
The time domain frequency hopping source signal y that all moment are obtainedn(p,qt) merge process, obtain final time domain frequency hopping
Source signal is estimated, concrete formula is as follows：
Here Kc=NfftThe sampling number that/C, C are spaced for Short Time Fourier Transform adding window, NfftLength for FFT.
Further, it is provided with synchronized orthogonal Frequency Hopping Signal blind source separating module, described synchronized orthogonal frequency hopping in described baking oven
The synchronized orthogonal Frequency Hopping Signal blind source separation method of signal blind source separating module includes：
Step one, is derived from the frequency hopping letter of multiple synchronized orthogonal frequency hopping radio sets using the array antenna received containing M array element
Number, each road receipt signal is sampled, the M road discrete time-domain mixed signal after being sampledm
=1,2 ..., M；
Step 2, carries out overlapping adding window Short Time Fourier Transform to M road discrete time-domain mixed signal, obtains M mixing letter
Number time-frequency domain matrixP=0,1 ..., P-1, q=0,1 ..., Nfft- 1, wherein P table
Show total window number, NfftRepresent FFT length；(p, q) represents time-frequency index, and specific time-frequency value is
Here NfftRepresent the length of FFT, p represents adding window number of times, TsRepresent sampling interval, fsRepresent sample frequency, C is integer,
Represent the sampling number at Short Time Fourier Transform adding window interval, C<Nfft, and Kc=Nfft/ C is integer that is to say, that using
The Short Time Fourier Transform of overlapping adding window；
Step 3, to the frequency-hopping mixing signal time-frequency domain matrix obtaining in step 2
Carry out pretreatment；RightCarry out low-yield pretreatment, that is, in each sampling instant p, willThe value that amplitude is less than thresholding ε sets to 0, and obtains
The setting of thresholding ε can determine according to the average energy of receipt signal；Find out p moment (p=0,1,2 ... P-1) non-zero
Time-frequency numeric field data, usesRepresent, whereinRepresent the response of p moment time-frequencyCorresponding frequency indices when non-zero, to these non-zero normalization pretreatment, obtain
Pretreated vector b (p, q)=[b1(p,q),b2(p,q),…,bM(p,q)]T, wherein：
Step 4, estimates jumping moment and the corresponding normalized hybrid matrix of each jump of each jump using clustering algorithm
Column vector, Hopping frequencies；
According to step 4, step 5, estimates that the normalization hybrid matrix column vector obtaining estimates time-frequency domain frequency hopping
Source signal；Which this moment index belongs to and jump is judged to all sampling instants index p, concrete grammar is：IfThen represent that moment p belongs to l and jumps；IfThen represent that moment p belongs to the 1st
Jump；All moment p that l (l=1,2 ...) is jumpedl, estimate the time-frequency numeric field data of this jump each frequency hopping source signal, computing formula is such as
Under：
Step 6, splices to the time-frequency domain frequency hopping source signal between different frequency hopping points；Estimate that l jumps correspondingIndividual
Incident angle, usesRepresent the corresponding incident angle of l n-th source signal of jump,Computing formula as follows：
Represent that l jumps n-th hybrid matrix column vector estimating to obtainM-th element, c represents the light velocity,
I.e. vc=3 × 108Meter per second；Judge that l (l=2,3 ...) jumps right between the source signal that the source signal estimated and the first jump are estimated
Should be related to, judgment formula is as follows：
Wherein mn (l)Represent that l jumps the m estimatingn (l)Individual signal and first is jumped n-th signal estimated and is belonged to same source
Signal；By different frequency hopping point estimation to the signal belonging to same source signal be stitched together, as final time-frequency domain source
Signal estimation, uses YnTime-frequency domain estimated value in time frequency point (p, q) for n-th source signal of (p, q) expression, p=0,1,2 ....,
P, q=0,1,2 ..., Nfft- 1, that is,
Step 7, according to source signal time-frequency domain estimated value, recovers time domain frequency hopping source signal.
Further, it is provided with signal detection module, the signal detecting method bag of described signal detection module in described baking oven
Include：
Mid frequency for known radio frequency or modulated intermediate frequency signal and bandwidth B c of the signal being likely to be received；
The first step, the radio frequency in Reived_V1 or Reived_V2 or if sampling signal are believed for fo single-frequency with frequency
Number it is mixed, obtained signal x1；
Second step, removes the high fdrequency components of signal x1 using low pass filter A, and the three dB bandwidth of low pass filter A is more than divides
Analysis bandwidth B s, obtains signal x2, now x2 is the signal of zero intermediate frequency, and the signal with a width of Bs is affected by wave filter A
Very little, negligible；
3rd step, because x2 has been zero intermediate frequency signals, therefore Fo=0, N is carried out to signal x2FFTThe FFT computing of points,
Then modulus, and by front NFFT/ 2 points are stored in VectorF, save the amplitude spectrum of signal x2 in VectorF；
4th step, analysis bandwidth Bs is divided into the equal Block, N=3,4 of N block ... .., each Block will be carried out
The a width of Bs/N of band of computing, if the low-limit frequency that will analyze bandwidth Bs is FL, FL=0, then nBlock block, n=1...N, institute is right
The frequency separation scope answered is [FL+ (n-1) Bs/N, FL+ (n) Bs/N] respectively, by the Frequency point of frequency range corresponding in VectorF
Distribute to each block, the VectorF point range that wherein nBlock divides is [Sn, Sn+kn], whereinRepresent the number of every section of Frequency point got, and
Represent is starting point, and fs is signal sampling frequencies, and round (*) represents the computing that rounds up；
5th step, seeks the energy ∑ of its frequency spectrum to each Block | |2, obtain E (n), n=1...N；
6th step, averages to vectorial E
7th step, try to achieve vectorial E variance and
8th step, update flag bit flag, flag=0, the front testing result of expressions be no signal, this kind of under the conditions of,
Only work as σsum>It is judged to currently detected signal, flag is changed into 1 during B2；Work as flag=1, represent that a front testing result is to have
Signal, this kind of under the conditions of, only work as σsum<It is judged to during B1 currently be not detected by signal, it is thresholding that flag is changed into 0, B1 and B2
Value, with theoretical simulation, empirical value is given, B2>B1；
According to flag bit, 9th step, controls whether subsequent demodulation thread etc. is opened：Flag=1, opens subsequent demodulation thread
Deng otherwise closing subsequent demodulation thread.
Further, described wave filter is provided with state observation module, the signal processing method bag of described state observation module
Include：
Dq axle capacitance voltage uCdWith uCq, dq axle grid side electric current i1dWith i1qAnd dq axle current transformer side electric current i2dWith i2qFor
System state variables, and wherein current transformer side electric current i2dWith i2qCan be directly obtained by current transformer side current sensor；
For realizing the state observation on dq axle, analyze the situation of monophase system, the monophase system differential of wave filter first
Equation arranges and is：
The output equation formula of LCL filter arranges and is：
i2=[1 0 0] [i2i1uC]T(2)
Due to rank { [1 0 0] }=1, therefore the state variable of reconstruct is needed to be [i1uC]T, two will be decomposed into by original system
Individual subsystem, does not respectively need the subsystem reconstructing and the subsystem needing reconstruct, does not wherein need the subsystem reconstructing to be referred to as
For non-reconstruction subsystem, it is formula (1) the first row；The subsystem needing reconstruct is referred to as reconstruction subsystem, the table of non-reconstruction subsystem
Reaching formula is：
Wherein, after equal sign, Section 2 is the coupling matrix of reconstruction subsystem to non-reconstruction subsystem, defines this matrix and attaches most importance to
The output of structure subsystem, and because it is 1 rank, therefore it is as follows to be expressed as η：
Then the expression formula of reconstruction subsystem is：
The proper polynomial of reconstruction subsystem：
Its limit real part in the imaginary axis, the expectation limit of observation is designed in Left half-plane, that is, has negative real part for 0, sees
The limit surveyed is p1=-pr+pi·j、p2=-pr-piJ, observation error feedback matrix isIt is expressed as：
Estimate [i1uC]T, reconstruction subsystem is designed as follows：
By itsItem moves on the left of equal sign, and formula (8) is made with conversion writing：
Define dimensionality reduction observation state be：
According to dimensionality reduction Observation Theory, the state space equation of this observation：
The state variable expression formula of so observation is：
Thus obtain the characteristic equation of dimensionality reduction observation：
Then configuration observation error feedback matrix and dimensionality reduction observation limit real part are had with the relation of imaginary part：
With reference to experiment, the application principle of the present invention is further described.
1 experimental section
1.1 instruments and working condition
Icp mses (model Xseries II, company of Thermo company of the U.S.), Instrument working parameter
For：Radio-frequency power 1300W, atomization gas (Ar) flow is 0.95L/min, cools down gas (Ar) flow 14.0L/min, auxiliary gas (Ar)
Flow 0.80L/min, sampling depth 80step, scan mode is to jump peak mode, scanning times 50 times, and resolution is 100.High-purity
Argon (＞ 99.99%).Germanium and tellurium select 74Ge and 125Te respectively as analysis isotope.
1.2 standard solution and main agents
Germanium, tellurium mixed standard solution：Concentration is 10mg/L, is provided by China National Measuring Science Research Inst..
It is pure that Fluohydric acid., nitric acid, hydrochloric acid, potassium borohydride, potassium hydroxide are analysis.Water is deionized water (>=18M Ω
cm).
1.3 samples decompose and HG-ICP-MS test
Accurately weigh geological sample (rock) 0.0500g in the politef inner canister of Enclosed sample bullet, add 0.5mL
Fluohydric acid. and 0.5mL nitric acid, on electric hot plate, low temperature (130 DEG C about) heating evaporation is to closely dry.It is subsequently adding 1.0mL hydrogen fluorine
Acid and 0.5mL nitric acid, cover inner cap, load in steel bushing, tighten steel bushing lid, molten sample bullet is put in baking oven, add in 185 ± 5 DEG C
Hot 24h.Uncap after cooling, take out politef inner canister, be placed in electric hot plate and steam to closely dry, add 0.5mL nitric acid to be evaporated to
Closely dry, repeat this operation once.Add the nitric acid of 1.5mL 50%, be again loaded into closing in steel bushing, be placed in 150 DEG C of perseverances in baking oven
Temperature heating 8h.Take out after cooling, uncap, dilute with water is simultaneously weighed into 50mL, as analytical solution after shaking up, do flow process empty simultaneously
In vain.
Prepare 20% hydrochloric acid+2% potassium borohydride (0.1% potassium hydroxide medium) as hydride generation system, on
When machine measures, introduce sample, bronsted lowry acids and bases bronsted lowry solution in the form of threeway respectively, the hydride of generation is after gas-liquid separation by carrier gas
(flow is 0.95L/min) is sent in plasma and is measured.
2 results and discussion
There is the determination of system in 2.1 hydrides
Hydride is produced by liquid phase reactor, and the reaction condition of different Element generation hydrides has very big difference, examines
Examine the result of the test that each element in differential responses system produces hydride.Often use in general hydride generation system hydrochloric acid+
Potassium borohydride reaction system, wherein acid base concentration have considerable influence for the generation of hydride, and the present invention is in Ge, Te content
In the mixed standard solution of 10 μ g/L, investigate and in hydrochloric acid+potassium borohydride reaction system, be best suitable for Ge and Te generation hydride
Acid base concentration.
In test, concentration of hydrochloric acid increases to 30%, potassium borohydride concentration from 1% and increases to 4% from 0.5%.Result shows,
When concentration of hydrochloric acid constantly increases, Ge and Te sensitivity first significantly increases and then tends towards stability；With potassium borohydride concentration not
Disconnected increase, Ge and Te sensitivity all constantly increases, but bad stability (RSD becomes big), when potassium borohydride concentration is 4%, acid
Alkali reaction is too violent, a large amount of gas consumptions of generation energy of plasma, leads to plasma to stop working.In addition, hydroboration
Potassium can decompose in acid medium quickly, but quite stable in alkaline medium.Experiment finds to add appropriate potassium hydroxide can have
Effect improves the stability of solution of potassium borohydride, and that is, when concentration of potassium hydroxide is too big, alkalescence is too strong, it will consume substantial amounts of hydrochloric acid
And lead to analytical element signal intensity to reduce；When concentration of potassium hydroxide is too little, potassium borohydride is unstable, and constantly has minute bubbles
Produce the stability of impact peristaltic pump.
Final choice 20% hydrochloric acid+2% potassium borohydride (0.1% potassium hydroxide medium) of the present invention is Ge and Te hydride
React system.
The impact of 2.2 flow rate of carrier gass
In HG-ICP-MS, the effect of carrier gas is extremely important, for bringing the hydride of generation after gas-liquid separation into
In gas ions, the impact to signal intensity for its uninterrupted is very big.The different flow rate of carrier gass of the effects to the Ge of 10 μ g/L and
The impact of Te signal intensity.
Figure it is seen that when carrier gas flux is too little, signal intensity is especially little, mainly due to produced hydrogenation
Thing is not brought in plasma effectively, and with the slowly increase of carrier gas flux, intensity is gradually increased, fast to after peaking
Speed reduces；When carrier gas flux is too big, gas-liquid separation is not complete, and a small amount of liquid can enter in plasma with carrier gas, causes
Plasma extinguishment.In general, the carrier gas flux of HG-ICP-MS is higher than the carrier gas flux under general mode, finally this reality
Testing establishment 0.95L/min is optimal carrier gas flux.
2.3 stability tests and the research of hydride reaction residual effect
The hydride generator of present invention design belongs to continuous flow- type hydride generator, continuous sample introduction during work, hydrogen
Compound reacts and is in a kind of dynamic equilibrium, and the stability of signal depends on the stability of reaction itself.The present invention is to containing Ge
It is the mixed standard solution parallel assay 20 times of 10 μ g/L with Te, the relative standard deviation (RSD) of its signal intensity is respectively
8.3% and 2.1%, show that the stability of this hydride generator is preferable.
On the other hand, the hydride reaction system of this dynamic equilibrium, signal response value remains a successive value, can facilitate
Integration and measurement；But because solution all of in generator will pass through gas-liquid separation, there may be some theoretically not anti-
Completely sample solution should remain on gas-liquid separation wall, cause certain memory effect, cleaning is relatively difficult.From
The residual effect in ICP-MS for the hydride generation system that Fig. 3 can be seen that present invention development lasts about 200s greatly, relatively holds
Easy cleaning.
2.4 coexisting ion interference tests
Using hydride generator as the sample introduction system of ICP-MS, tested element can be made to separate with matrix in itself,
In addition tested element enters in plasma with carrier gas in gaseous form, and in plasma, anhydrous solution introduces, thus can reduce
The formation of multi-atomic ion.This is a cancellation potential mass spectrum interference, also there is certain doing in hydride reaction part
Disturb, this interference mostlys come from the coexistence elements that can affect or disturb Element generation hydride to be measured.
The effects may produce the disturbed condition of several elements of interference to Ge and Te.By DZ/T0130-2006
《Geological and mineral laboratory test quality management regulation》, in geological sample the measurement result allowable error of Ge and Te should 20%～
Between 30%, the present invention to be calculated with relative error≤20%, and result shows：10000 times of Cu, 800 times of Se, 600 times
Bi, 200 times of As and Sb have no significant effect to the mensure of Ge；8000 times of Cu, 500 times of As, 200 times of Se, 150 times of Bi
With Sb, Te is measured and have no significant effect.
2.5 method and technology indexs
2.5.1 calibration curve and method detection limit pipette appropriate Ge and Te mixed standard solution, dilute step by step with 2% nitric acid
It is interpreted into 0.0 μ g/L, 1.0 μ g/L, 5.0 μ g/L, 10.0 μ g/L, 50.0 μ g/L standard series, according to experimental technique in optimal instrument
Under the conditions of gather the signal of 74Ge and 125Te, draw calibration curve, its linearly dependent coefficient is 0.9999.
Under experiment condition of the present invention, parallel assay is carried out to 11 parts of sample blank solution, with 3 times of standard deviation calculation,
And consider that diluted sample multiple 1000 obtains the detection limit respectively 0.007 μ g/g and 0.006 μ g/g of Ge and Te.
2.5.2 method accuracy
Under the experiment condition of the present invention, choose national standard material Rock Series sample parallel assay 5 times come the side of measurement
The precision of method and accuracy, simultaneously for the practicality of verification method, adopt the actual rock of industry standard test before choosing
Sample carries out check analysiss, and result is listed in table 1.As it can be seen from table 1 the measured value of Ge and Te and its recommendation in standard substance
Substantially identical, precision all within 8%, tie by the measured value of Ge and the analysis of emission spectrometry (DZG20-05) in actual sample
Really consistent.
The Te content of actual sample is relatively low, adopts uncovered tetracid molten with reference to ICP-MS analysis general rule (DZ, T0223-2001)
Sample ICP-MS directly measures, and because the detection limit (0.1 μ g/g) that the method measures Te is higher than its content value, therefore cannot provide mensure
Value, and method of the present invention detection limit is lower, can provide accurate measurement result.
The measurement result of table 1 rock standard substance and method compare
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of HG-ICP-MS measures the method for rare and scatter element germanium and tellurium in geology it is characterised in that described HG-ICP-MS surveys
The method determining rare and scatter element germanium and tellurium in geology includes：Weigh geological sample in the politef inner canister of Enclosed sample bullet,
To geological sample pretreatment；Configuration hydride generation system, introduces sample, bronsted lowry acids and bases bronsted lowry solution, the hydride of generation respectively
Sent in plasma by carrier gas after gas-liquid separation and be measured；Calibration curve and method detection limit, in terms of 3 times of standard deviations
Calculate, and consider that diluted sample multiple 1000 obtains the detection limit of Ge and Te.
2. HG-ICP-MS as claimed in claim 1 measures the method for rare and scatter element germanium and tellurium in geology it is characterised in that institute
State geological sample pretreatment to comprise the following steps：
Weigh geological sample 0.0500g in the politef inner canister of Enclosed sample bullet, add 0.5mL Fluohydric acid. and 0.5mL
Nitric acid, on electric hot plate, 130 DEG C of heating evaporations, to closely dry, be subsequently adding 1.0mL Fluohydric acid. and 0.5mL nitric acid, cover inner cap, dress
Enter in steel bushing, tighten steel bushing lid, molten sample bullet is put in baking oven, heat 24h in 185 ± 5 DEG C, uncap after cooling, take out poly-
Tetrafluoroethene inner canister, is placed in electric hot plate and steams to closely dry, add 0.5mL nitric acid to be evaporated to closely do, repeat this operation once；
Add the nitric acid of 1.5mL 50%, be again loaded into closing in steel bushing, be placed in 150 DEG C of heated at constant temperature 8h in baking oven, after cooling
Take out, uncap, dilute with water is simultaneously weighed into 50mL, as analytical solution after shaking up.
3. HG-ICP-MS as claimed in claim 1 measures the method for rare and scatter element germanium and tellurium in geology it is characterised in that institute
Stating hydride generation system is 0.1% potassium hydroxide being made up of 20% hydrochloric acid+2% potassium borohydride；
Described carrier gas flux is 0.95L/min；
Described calibration curve and method detection limit method are：Pipette Ge and Te mixed standard solution, become with 2% nitric acid stepwise dilution
0.0 μ g/L, 1.0 μ g/L, 5.0 μ g/L, 10.0 μ g/L, 50.0 μ g/L standard series, the signal of collection 74Ge and 125Te, draw
Calibration curve, its linearly dependent coefficient is 0.9999.
4. HG-ICP-MS as claimed in claim 1 measures the method for rare and scatter element germanium and tellurium in geology it is characterised in that institute
The condition stating mensure is as follows：ICP-MS Instrument working parameter is：Radio-frequency power 1300W, atomization gas flow is 0.95L/min, cold
But throughput 14L/min, secondary air amount 0.80L/min, sampling depth 80step, scan mode is to jump peak, scanning times 50,
Resolution is 100；Germanium and tellurium select respectively74Ge and125Te is analysis isotope；
Described calibration curve and method detection limit specifically include：Pipette germanium, tellurium mixed standard solution in right amount, with 2% nitric acid step by step
It is diluted to 0.0,1.0,5.0,10.0,50.0 μ g/L standard series, gather under optimal instrument condition according to experimental technique74Ge
With125The signal intensity of Te, draws calibration curve；
Parallel assay is carried out to 11 parts of sample blank solution, with 3 times of standard deviation calculation, and considers that diluted sample multiple 1000 is counted
Calculate detection limit DL=3 σ * 1000.
5. HG-ICP-MS as claimed in claim 1 measures the method for rare and scatter element germanium and tellurium in geology it is characterised in that institute
State politef inner canister and be provided with phase calculation module, the method for the phase calculation of described phase calculation module includes：
Receipt signal y (t) is expressed as：
Y (t)=x (t)+n (t)；
Wherein, x (t) is digital modulation signals, and n (t) is the impulsive noise of standard S α S distribution；MASK and MPSK modulates, x's (t)
Analytical form is expressed as：
Wherein, N is sampling number, anFor the information symbol sending, in MASK signal, an=0,1,2 ..., M-1, M are modulation
Exponent number, in mpsk signal, an=ej2πε/M, ε=0,1,2 ..., M-1, g (t) represent rectangle molding pulse, TbRepresent symbol week
Phase, fcRepresent carrier frequency, carrier wave initial phaseIt is equally distributed random number in [0,2 π]；
The expression formula on kth passage n-th road signal x (t) is：
X (t)=expj { ω0(t+τk+nTs)+1/2μ(t+τk+nTs)2, k=0,1 ...；N=0,1,2 ...
Wherein, ω0It is the initial angular velocity of output waveform, t is the time, and n represents the sequence number of way in every passage, and μ represents that frequency modulation is oblique
Rate, TsIt is the sampling period, τkRepresent the corresponding time difference of kth channel signal start-phase；
The phase place of kth passage the n-th road signalMake such as down conversion：
OrderPk.n=μ (τk+nTs)、Qk.n=ω0(τk+nTs)+1/2μ(τk+nTs)2, then above formula can change
For：
WhereinOn the basis of phase place, when signal attribute parameter is fixing, Pk.n、Qk.nAlso it is definite value, therefore also serve as parameter defeated
Enter；One offset phase of increase on the basis of master phase is all regarded in the waveform output on other roads asObtain；
Frequency domain data Y to each sampling instant p (p=0,1,2 ...)n(p, q), q=0,1,2 ..., Nfft- 1 is NfftPoint
IFFT converts, and obtains p sampling instant corresponding time domain frequency hopping source signal, uses yn(p,qt)(qt=0,1,2 ..., Nfft- 1) represent；
The time domain frequency hopping source signal y that all moment are obtainedn(p,qt) merge process, obtain final time domain frequency hopping synthesizer letter
Number estimate, concrete formula is as follows：
Here Kc=NfftThe sampling number that/C, C are spaced for Short Time Fourier Transform adding window, NfftLength for FFT.
6. HG-ICP-MS as claimed in claim 1 measures the method for rare and scatter element germanium and tellurium in geology it is characterised in that institute
State and in baking oven, be provided with synchronized orthogonal Frequency Hopping Signal blind source separating module, described synchronized orthogonal Frequency Hopping Signal blind source separating module
Synchronized orthogonal Frequency Hopping Signal blind source separation method includes：
Step one, is derived from the Frequency Hopping Signal of multiple synchronized orthogonal frequency hopping radio sets, to each using the array antenna received containing M array element
Road receipt signal is sampled, the M road discrete time-domain mixed signal after being sampled
Step 2, carries out overlapping adding window Short Time Fourier Transform to M road discrete time-domain mixed signal, obtains M mixed signal
Time-frequency domain matrix
P=0,1 ..., P-1, q=0,1 ..., Nfft- 1, wherein P represent total window number, NfftRepresent FFT length；(p, q)
Represent time-frequency index, specific time-frequency value isHere NfftRepresent the length of FFT, p represents adding window
Number of times, TsRepresent sampling interval, fsRepresent sample frequency, C is integer, represents the sampled point at Short Time Fourier Transform adding window interval
Number, C<Nfft, and Kc=Nfft/ C is integer that is to say, that using the Short Time Fourier Transform of overlapping adding window；
Step 3, to the frequency-hopping mixing signal time-frequency domain matrix obtaining in step 2Enter
Row pretreatment；RightCarry out low-yield pretreatment, that is, in each sampling instant p, willThe value that amplitude is less than thresholding ε sets to 0, and obtains
The setting of thresholding ε can determine according to the average energy of receipt signal；Find out p moment (p=0,1,2 ... P-1) non-zero
Time-frequency numeric field data, useRepresent, whereinRepresent the response of p moment time-frequencyCorresponding frequency indices when non-zero, to these non-zero normalization pretreatment, obtain
Pretreated vector b (p, q)=[b1(p,q),b2(p,q),…,bM(p,q)]T, wherein：
Step 4, using clustering algorithm estimate the jumping moment of each jump and each jump corresponding normalized mixed moment array to
Amount, Hopping frequencies；
According to step 4, step 5, estimates that the normalization hybrid matrix column vector obtaining estimates time-frequency domain frequency hopping source signal；To institute
Sampling instant index p is had to judge which this moment index belongs to and jump, concrete grammar is：If
Then represent that moment p belongs to l and jumps；IfThen represent that moment p belongs to the 1st jump；L (l=1,2 ...) is jumped
All moment pl, estimate the time-frequency numeric field data of this jump each frequency hopping source signal, computing formula is as follows：
Step 6, splices to the time-frequency domain frequency hopping source signal between different frequency hopping points；Estimate that l jumps correspondingIndividual incidence
Angle, usesRepresent the corresponding incident angle of l n-th source signal of jump,Computing formula as follows：
Represent that l jumps n-th hybrid matrix column vector estimating to obtainM-th element, c represents the light velocity, i.e. vc
=3 × 108Meter per second；Judge that l (l=2,3 ...) jumps corresponding between the source signal estimated and the source signal that first jumps estimation
Relation, judgment formula is as follows：
Wherein mn (l)Represent that l jumps the m estimatingn (l)Individual signal and first is jumped n-th signal estimated and is belonged to same source letter
Number；By different frequency hopping point estimation to the signal belonging to same source signal be stitched together, as final time-frequency domain source letter
Number estimate, use YnTime-frequency domain estimated value in time frequency point (p, q) for n-th source signal of (p, q) expression, p=0,1,2 ...., P,
Q=0,1,2 ..., Nfft- 1, that is,
Step 7, according to source signal time-frequency domain estimated value, recovers time domain frequency hopping source signal.
7. HG-ICP-MS as claimed in claim 1 measures the method for rare and scatter element germanium and tellurium in geology it is characterised in that institute
State and in baking oven, be provided with signal detection module, the signal detecting method of described signal detection module includes：
Mid frequency for known radio frequency or modulated intermediate frequency signal and bandwidth B c of the signal being likely to be received；
The first step, the radio frequency in Reived_V1 or Reived_V2 or if sampling signal are entered for fo simple signal with frequency
Row mixing, obtains signal x1；
Second step, removes the high fdrequency components of signal x1 using low pass filter A, and the three dB bandwidth of low pass filter A is more than analytic band
Wide Bs, obtains signal x2, now x2 is the signal of zero intermediate frequency, and the signal with a width of Bs is affected very little by wave filter A,
Negligible；
3rd step, because x2 has been zero intermediate frequency signals, therefore Fo=0, N is carried out to signal x2FFTThe FFT computing of points, then
Modulus, and by front NFFT/ 2 points are stored in VectorF, save the amplitude spectrum of signal x2 in VectorF；
4th step, analysis bandwidth Bs is divided into the equal Block, N=3,4 of N block ... .., each Block will enter row operation
The a width of Bs/N of band, if to analyze bandwidth Bs low-limit frequency be FL, FL=0, then nBlock block, n=1...N, corresponding
Frequency separation scope is [FL+ (n-1) Bs/N, FL+ (n) Bs/N] respectively, by the Frequency point distribution of frequency range corresponding in VectorF
To each block, the VectorF point range that wherein nBlock divides is [Sn, Sn+kn], wherein
Represent the number of every section of Frequency point got, andRepresent is starting point,
Fs is signal sampling frequencies, and round (*) represents the computing that rounds up；
5th step, seeks the energy ∑ of its frequency spectrum to each Block | |2, obtain E (n), n=1...N；
6th step, averages to vectorial E
7th step, try to achieve vectorial E variance and
8th step, update flag bit flag, flag=0, the front testing result of expressions be no signal, this kind of under the conditions of, only
Work as σsum>It is judged to currently detected signal, flag is changed into 1 during B2；Work as flag=1, represent that a front testing result is to have letter
Number, this kind of under the conditions of, only work as σsum<It is judged to during B1 currently be not detected by signal, it is threshold value that flag is changed into 0, B1 and B2,
With theoretical simulation, empirical value is given, B2>B1；
According to flag bit, 9th step, controls whether subsequent demodulation thread etc. is opened：Flag=1, opens subsequent demodulation thread etc., no
Then close subsequent demodulation thread.
8. HG-ICP-MS as claimed in claim 7 measures the method for rare and scatter element germanium and tellurium in geology it is characterised in that institute
State wave filter and be provided with state observation module, the signal processing method of described state observation module includes：
Dq axle capacitance voltage uCdWithDq axle grid side electric current i1dWith i1qAnd dq axle current transformer side electric current i2dWith i2qFor system
State variable, and wherein current transformer side electric current i2dWith i2qCan be directly obtained by current transformer side current sensor；
For realizing the state observation on dq axle, analyze the situation of monophase system, the monophase system differential equation of wave filter first
Formula arranges and is：
The output equation formula of LCL filter arranges and is：
i2=[1 0 0] [i2i1uC]T(2)
Due to rank { [1 0 0] }=1, therefore the state variable of reconstruct is needed to be [i1uC]T, two sons will be decomposed into by original system
System, does not respectively need the subsystem reconstructing and the subsystem needing reconstruct, does not wherein need the subsystem reconstructing to be referred to as non-
Reconstruction subsystem, is formula (1) the first row；The subsystem needing reconstruct is referred to as reconstruction subsystem, the expression formula of non-reconstruction subsystem
For：
Wherein, after equal sign, Section 2 is the coupling matrix of reconstruction subsystem to non-reconstruction subsystem, and defining this matrix is reconstruct
The output of system, and because it is 1 rank, therefore it is as follows to be expressed as η：
Then the expression formula of reconstruction subsystem is：
The proper polynomial of reconstruction subsystem：
Its limit real part in the imaginary axis, the expectation limit of observation is designed in Left half-plane, that is, has negative real part for 0, observation
Limit is p1=-pr+pi·j、p2=-pr-piJ, observation error feedback matrix isIt is expressed as：
Estimate [i1uC]T, reconstruction subsystem is designed as follows：
By itsItem moves on the left of equal sign, and formula (8) is made with conversion writing：
Define dimensionality reduction observation state be：
According to dimensionality reduction Observation Theory, the state space equation of this observation：
The state variable expression formula of so observation is：
Thus obtain the characteristic equation of dimensionality reduction observation：
Then configuration observation error feedback matrix and dimensionality reduction observation limit real part are had with the relation of imaginary part：
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| CN107037115A (en) * | 2017-04-17 | 2017-08-11 | 中国科学院海洋研究所 | A kind of ICP MS hydride sampling system and its method for detecting hydride |
| CN112288243A (en) * | 2020-10-19 | 2021-01-29 | 中国煤炭地质总局勘查研究总院 | Method and device for evaluating associated metal resources in coal |
| CN114577884A (en) * | 2022-05-06 | 2022-06-03 | 四川富临新能源科技有限公司 | PH value detection equipment for removing impurities in lithium iron phosphate and detection method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107037115A (en) * | 2017-04-17 | 2017-08-11 | 中国科学院海洋研究所 | A kind of ICP MS hydride sampling system and its method for detecting hydride |
| CN107037115B (en) * | 2017-04-17 | 2023-11-07 | 中国科学院海洋研究所 | ICP-MS hydride sampling system and hydride detection method thereof |
| CN112288243A (en) * | 2020-10-19 | 2021-01-29 | 中国煤炭地质总局勘查研究总院 | Method and device for evaluating associated metal resources in coal |
| CN112288243B (en) * | 2020-10-19 | 2021-07-23 | 中国煤炭地质总局勘查研究总院 | Method and device for evaluating associated metal resources in coal |
| CN114577884A (en) * | 2022-05-06 | 2022-06-03 | 四川富临新能源科技有限公司 | PH value detection equipment for removing impurities in lithium iron phosphate and detection method thereof |
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