CN108760799A - A kind of Stable isotope ratio assay method carrying out sample dynamic dilution based on Thermal Conductivity signal - Google Patents
A kind of Stable isotope ratio assay method carrying out sample dynamic dilution based on Thermal Conductivity signal Download PDFInfo
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Abstract
The present invention relates to a kind of Stable isotope ratio assay methods carrying out sample dynamic dilution based on Thermal Conductivity signal, including：Standard items are converted to multigroup reference gas, then each group reference gas is diluted, record dilution ratio；The TCD values and IRMS values for detecting each group reference gas, establish the linear calibration curve of TCD values and IRMS values；And establish the dilution ratio relation table of dilution ratio and the IRMS signal values；Sample to be tested is converted under test gas；The TCD values for detecting the under test gas, substitute into the linear calibration curve, find out the IRMS calculated values of the under test gas, then are substituted into dilution ratio relation table, obtain corresponding dilution ratio；The under test gas is diluted accordingly, the IRMS detected values of the under test gas after detection is diluted, you can.Method provided by the invention is measured based on thermal conductivity detector (TCD) signal, realizes the automatic dilution of sample concentration signal, easy to operate without accurately controlling sample quality, has practicability.
Description
Technical field
The present invention relates to a kind of Stable isotope ratio assay methods, belong to stable isotope detection technique research field.
Background technology
In recent years, stable isotope mass spectrometer technology (IRMS) have been widely used environment, ocean, agricultural, the administration of justice and
Food inspection etc..One is installed simultaneously the elemental analyser and a Tai Gaoling of conflagration and pyrolytic conversion double-reactor
Sensitivity stable isotope is combined (EA-IRMS) than mass spectrograph, can carry out the more members of totality N, C, S, O and H in different type sample
The detection of plain isotope ratio.In previous work, technical staff strictly controls sample and claims usually using the balance of superelevation accuracy
Weight keeps sample ions stream signal and reference signal consistent as possible, can guarantee high-precision and the accuracy of isotope analysis in this way,
But unusual time and effort consuming, even the concentration of element of ex ante analysis unknown sample is needed to be precisely weighed again sometimes.Therefore, it develops
A kind of sample signal automatic dilution method of simplicity simplifies time-consuming accurate weighing step, for stable isotope detection technique
Promotion and widely application be of great significance.
Invention content
The purpose of the present invention is overcome the deficiencies in the prior art, establish a kind of based on the progress of thermal conductivity detector (TCD) (TCD) signal
Stable isotope ratio (IRMS) assay method of sample dynamic dilution.
Specifically, method provided by the invention includes the following steps：
(1) the more parts of standard items that object element content is different are taken, are converted to respectively containing target element in elemental analyser
Multigroup reference gas of element；Each group reference gas is diluted with inert gas again, records dilution ratio；
(2) the TCD signal values of each group reference gas after being diluted with thermal conductivity detector (TCD) detection, with Stable isotope ratio matter
Spectrometer measures the IRMS signal values of each group reference gas after dilution, establishes the TCD signal values and the IRMS signal values
Linear calibration curve；
(3) the dilution ratio relation table of the dilution ratio and the IRMS signal values of each group reference gas is established；
(4) sample to be tested is taken, under test gas identical with the reference gas is converted in elemental analyser；
(5) the TCD signal values of the under test gas are detected with thermal conductivity detector (TCD), and it is bent to substitute into linear gauging obtained by step (2)
In line, the IRMS signal calculated values of the under test gas are found out, then will be dilute obtained by IRMS signals calculated value substitution step (3)
It releases in proportionate relationship table, obtains corresponding dilution ratio；
(6) under test gas is diluted with inert gas according to step (5) dilution ratio for obtaining, then with stabilization
The IRMS value detection signals of under test gas after the dilution of isotopic ratio Mass Spectrometer Method, you can.
The targeted sample to be tested of method provided by the invention is mainly food；Preferably meat (such as pork), fruit
(such as apple), vegetables or grain.Processing should be dried in sample to be tested before being detected.To ensure that testing result is accurate, institute
The sampling amount for stating sample to be tested is preferably 0.1~10mg.
The targeted object element of method provided by the invention can be N, C, S, O, H etc..Specifically, the target element
Element can be nitrogen, and the reference gas that standard items convert at this time is N2.The object element may be carbon, this
When the reference gas that converts of standard items be CO2。
Standard items of the present invention are preferably urea.In actually detected, step (1) preferably takes the quality to be respectively
The more parts of urea standard items of 0.129mg, 0.188mg, 0.262mg, 0.344mg, 0.460mg, 0.540 mg.
The conversion process of standard items or sample to be tested passes through conflagration or high anneal crack in the reaction tube of elemental analyser
Solution carries out.Specifically, the standard items are converted in the reaction tube of elemental analyser by conflagration or Pintsch process
Reference gas；The sample to be tested is converted to gas to be measured in the reaction tube of elemental analyser by conflagration or Pintsch process
Body.
As a preferred embodiment of the present invention, during the conversion, elemental analyser includes following parameter：Reaction
Furnace temperature is 970~990 DEG C；Molecular sieve chromatography column temperature is 45~65 DEG C；Flow rate of carrier gas is 80~120mL/min；It is purged into
Sample mouth flow velocity is 180~220 mL/min；Pure O2Injection flow velocity is 160~190mL/min；The note oxygen time is 1~5s.
In order to improve the accuracy of detection, the reference gas and under test gas being converted in elemental analyser need to be passed through first
Over-molecular sieve chromatographic column is isolated and purified, then carries out subsequent step.
The present invention is diluted purpose to reference gas and essentially consists in, and each group reference gas is diluted to make it
IRMS signal values are in the range of 5000mv~7000mv.The present invention is controlled signal value in the model by largely putting into practice discovery
The interior accuracy that can greatly improve final sample to be tested testing result is enclosed, deviation is reduced.Wherein, when object element is nitrogen,
The IRMS signal values are m/z 28N2 +The signal value of ion stream.When object element is carbon, the IRMS signal values are m/z
44CO2 +The signal value of ion stream.
The present invention is all made of conventional method known in the art to the dilution of gas.Such as：It can to the dilution of reference gas
It is carried out using the device with gas dilution function being connected to after elemental analyser.Again for example：Dilution under test gas
It is carried out using the dynamic dilution function module of elemental analyser.
In step (2) of the present invention, the minimum of TCD signal values and IRMS signal values can be automatically obtained by instrument software
Two multiply linear equation, to establish linear calibration curve.In the step (3), established automatically using instrument work package each
The dilution ratio relation table of the dilution ratio and the IRMS signal values of group reference gas.When object element is nitrogen, IRMS is used
M/z 28N2 +Current ion signal value establishes linear calibration curve and establish dilution ratio with dilution ratio with TCD signal values closes
It is table.When object element is carbon, with the m/z 44CO of IRMS2 +Current ion signal value establishes linear gauging song with TCD signal values
Line and establish dilution ratio relation table with dilution ratio.
The method that Stable isotope ratio mass spectrograph of the present invention measures IRMS signals is specially：With stable isotope ratio
Ion source in value mass spectrograph under test gas is ionized into the isotopic molecules of multiple and different mass-to-charge ratioes containing object element from
The molecular ion of son, the difference mass-to-charge ratio is detached under magnetic fields and is received by multiple general Faraday cups, by putting
The above process is converted to voltage signal by big device, and the Stable isotope ratio of object element is finally gone out by system-computed.When described
Under test gas is N2When, the isotopic molecule ion of corresponding multiple and different mass-to-charge ratioes containing object element is respectively m/z
28N2 +、m/z 29N2 +With m/z 30N2 +.When the under test gas is CO2When, corresponding multiple and different matter containing object element
Lotus than isotopic molecule ion be respectively m/z 44CO2 +、m/z 45CO2 +With m/z 46CO2 +。
Method provided by the invention realizes the automatic dilution of sample concentration signal, without accurately controlling sample quality, grasps
Make simplicity, there is practicability.
Description of the drawings
Fig. 1 is the m/z 28N of TCD signal values and IRMS that the embodiment of the present invention 1 provides2 +Current ion signal value calibration curve
Figure.
Fig. 2 is 44 CO of m/z of TCD signal values and IRMS that the embodiment of the present invention 2 provides2 +Current ion signal value calibration is bent
Line chart.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
Present embodiments provide a kind of nitrogen Stable isotope ratio carrying out sample dynamic dilution based on Thermal Conductivity signal
Assay method, the main agents and material being related to have：Urea sterling, dry pork (nitrogen content 7.17%).
The specific method is：Weigh 0.129 respectively, 0.188,0.262,0.344,0.460, the urea of 0.540mg in
In tin can, after the tin can consolidation equipped with urea is wrapped, EA-TCD-IRMS analyses are carried out, urea sample is in elemental analyser
N is converted in reaction tube2After (parameter setting of elemental analyser is as shown in table 1), TCD signals have been measured by TCD detectors
Value, and corresponding IRMS signal values are measured by isotope-ratio mass spectrometer, instrument software is established TCD signal values and is believed with IRMS automatically
Number value linear calibration curve, as shown in Figure 1.The dilution ratio and IRMS ion streams of nitrogen are established using instrument work package
The dilution ratio table of signal value correlations.
Appropriate pork sample (0.499mg, 0.22mg, 1.82mg) is weighed in tin can, and wraps up consolidation, then in element
Conflagration or Pintsch process are converted to corresponding under test gas in the reaction tube of analyzer.N2Through molecular sieve chromatography post separation
Afterwards, corresponding signal value is measured through TCD, corresponding IRMS signal values is calculated according to calibration curve, in conjunction with dilution ratio table
Under test gas is diluted to the signal strength consistent with reference gas.N after dilution2Stable isotope ratio measurement is carried out, is obtained
The nitrogen Stable isotope ratio of pork sample, and obtain the same pork sample δ of 3 different qualities15The standard deviation of N values is
0.15 ‰, meet the required precision of nitrogen isotope ratio measurement.
It is as shown in table 2 to analyze test result.
Table 1：The parameter setting of elemental analyser
| Parameter | Setting value |
| Reacting furnace temperature | 980℃ |
| Molecular sieve chromatography column temperature | 50℃ |
| Flow rate of carrier gas | 100mL/min |
| Purge injection port flow velocity | 200mL/min |
| Pure O2Injection | 175mL/min |
| Note the oxygen time | 3s |
Table 2：Pork sample analysis test result
Embodiment 2
Present embodiments provide a kind of carbon stable isotope ratio carrying out sample dynamic dilution based on Thermal Conductivity signal
Assay method, the main agents and material being related to have：Urea sterling, apple (freeze-dried powder, carbon content 39.24%).
The specific method is：Weigh 0.129 respectively, 0.188,0.262,0.344,0.460, the urea of 0.540mg in
In tin can, after the tin can consolidation equipped with urea is wrapped, EA-TCD-IRMS analyses are carried out, urea sample is in elemental analyser
CO is converted in reaction tube2After (parameter setting of elemental analyser is with table 1), TCD signal values have been measured by TCD detectors,
And corresponding IRMS signal values are measured by isotope-ratio mass spectrometer, instrument software establishes TCD signal values and IRMS signals automatically
The linear calibration curve of value, as shown in Figure 2.CO is established using instrument work package2Dilution ratio and IRMS current ion signals
It is worth the dilution ratio table of correlation.
Appropriate apple sample (1.739mg, 3.498mg, 6.249mg) is weighed in tin can, and wraps up consolidation, then in member
Conflagration or Pintsch process are converted to corresponding under test gas in the reaction tube of plain analyzer.CO2Through molecular sieve chromatography column point
From rear, corresponding signal value is measured through TCD, corresponding IRMS signal values are calculated according to calibration curve, in conjunction with dilution ratio
Under test gas is diluted to the signal strength consistent with reference gas by table.CO after dilution2Stable isotope ratio measurement is carried out,
The carbon stable isotope ratio of apple sample is obtained, and obtains the same apple sample δ of 3 different qualities13The standard deviation of C values
It is 0.15 ‰, meets the required precision of carbon isotope ratio measurement.
It is as shown in table 3 to analyze test result.
Table 3：Apple sample analysis test result
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of Stable isotope ratio assay method being carried out sample dynamic dilution based on Thermal Conductivity signal, feature are existed
In including the following steps：
(1) the more parts of standard items that object element content is different are taken, are converted to respectively containing object element in elemental analyser
Multigroup reference gas；Each group reference gas is diluted with inert gas again, records dilution ratio；
(2) the TCD signal values of each group reference gas after being diluted with thermal conductivity detector (TCD) detection, with Stable isotope ratio mass spectrograph
The IRMS signal values for measuring each group reference gas after dilution establish the linear of the TCD signal values and the IRMS signal values
Calibration curve；
(3) the dilution ratio relation table of the dilution ratio and the IRMS signal values of each group reference gas is established；
(4) sample to be tested is taken, under test gas identical with the reference gas is converted in elemental analyser；
(5) the TCD signal values of the under test gas are detected with thermal conductivity detector (TCD), are substituted into linear calibration curve obtained by step (2),
The IRMS signal calculated values of the under test gas are found out, then the IRMS signals calculated value is substituted into thinner ratio obtained by step (3)
In example relation table, corresponding dilution ratio is obtained；
(6) under test gas is diluted with inert gas according to step (5) dilution ratio for obtaining, then with stablizing same position
The IRMS value detection signals of under test gas after plain ratio Mass Spectrometer Method dilution, you can.
2. according to the method described in claim 1, it is characterized in that, the sample to be tested is food；Preferably meat, fruit,
Vegetables or grain.
3. method according to claim 1 or 2, which is characterized in that the object element is nitrogen, reference gas N2；
Or, the object element is carbon, reference gas CO2。
4. according to the method described in claim 3, it is characterized in that, the standard items are urea；Preferably, it in step (1), takes
Quality is respectively the more parts of urea standard items of 0.129mg, 0.188mg, 0.262mg, 0.344mg, 0.460mg, 0.540mg.
5. according to the method described in claim 1, it is characterized in that, the standard items pass through in the reaction tube of elemental analyser
Conflagration or Pintsch process are converted to reference gas；
The sample to be tested is converted under test gas in the reaction tube of elemental analyser by conflagration or Pintsch process.
6. according to the method described in claim 5, it is characterized in that, during the conversion, elemental analyser includes as follows
Parameter：Reacting furnace temperature is 970~990 DEG C；
And/or molecular sieve chromatography column temperature is 45~65 DEG C；
And/or flow rate of carrier gas is 80~120mL/min；
And/or purging injection port flow velocity is 180~220mL/min；
And/or pure O2Injection flow velocity is 160~190mL/min；
And/or the note oxygen time is 1~5s.
7. according to the method described in claim 1,5 or 6, which is characterized in that the reference gas being converted in elemental analyser
And/or under test gas first passes through molecular sieve chromatography column and is isolated and purified, then carry out subsequent step.
8. according to the method described in claim 1, it is characterized in that, each group reference gas is diluted to ensure by step (1)
Its IRMS signal value is in the range of 5000mv~7000mv；
Preferably, when object element is nitrogen, the IRMS signal values are m/z 28N2 +The signal value of ion stream；Work as object element
For carbon when, the IRMS signal values be m/z 44CO2 +The signal value of ion stream.
9. according to the method described in claim 1, it is characterized in that, the Stable isotope ratio mass spectrograph measures IRMS signals
Method be specially：
Under test gas is ionized into multiple and different matter containing object element with the ion source in Stable isotope ratio mass spectrograph
Lotus than isotopic molecule ion, it is described difference mass-to-charge ratioes molecular ion detached under magnetic fields and by multiple general methods
The reception is drawn, the above process is converted to by voltage signal by amplifier, the stabilization of object element is finally gone out by system-computed
Isotopic ratio.
10. according to the method described in claim 9, it is characterized in that, when the under test gas is N2When, it is corresponding to contain target
The isotopic molecule ion of multiple and different mass-to-charge ratioes of element is respectively m/z 28N2 +、m/z 29N2 +With m/z 30N2 +；
When the under test gas is CO2When, the isotopic molecule ion point of corresponding multiple and different mass-to-charge ratioes containing object element
It Wei not m/z 44CO2 +、m/z 45CO2 +With m/z 46CO2 +。
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