CN105203622B - It is a kind of to determine the isotopic ratio of lead and the method for identifying the red bayberry place of production in strawberry tree different parts sample - Google Patents

It is a kind of to determine the isotopic ratio of lead and the method for identifying the red bayberry place of production in strawberry tree different parts sample Download PDF

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CN105203622B
CN105203622B CN201510696404.3A CN201510696404A CN105203622B CN 105203622 B CN105203622 B CN 105203622B CN 201510696404 A CN201510696404 A CN 201510696404A CN 105203622 B CN105203622 B CN 105203622B
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nitric acid
lead
strawberry tree
acid
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CN105203622A (en
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钟莺莺
冯睿
俞雪钧
殷居易
樊苑牧
倪梅林
劳华均
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NINGBO ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU TECHNICAL CENTER OF PEOPLE'S REPUBLIC OF CHINA
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NINGBO ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU TECHNICAL CENTER OF PEOPLE'S REPUBLIC OF CHINA
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Abstract

The isotopic ratio of lead and the method for identifying the red bayberry place of production in strawberry tree different parts sample are determined the invention discloses a kind of：Weigh strawberry tree different parts sample and carry out pre-treatment, after micro-wave digestion, with SR Resin B-tree fat Shu Zhi Jing Huas, afford lead sample, then detect to obtain the isotopic ratio of lead in lead sample using hot surface ionization mass spectrometer.Correlation distribution map can be done according to the isotopic ratio of the lead of the sample of different sources same area, the place of production situation of the strawberry tree sample for identifying the unknown place of production.The present invention quickly determines the isotopic ratio of lead in strawberry tree different parts sample using hot surface ionization mass spectrometer first, can be traced to the source for red bayberry and provide a kind of science, independent, unmodifiable identity authentication information, and method is reliable and stable.Especially for the product between extensive area, its difference can be effectively distinguished.The inventive method detection efficiency is high；And testing result precision is high, effect is good.

Description

It is a kind of to determine the isotopic ratio of lead in strawberry tree different parts sample and identify red bayberry The method in the place of production
Technical field
The present invention relates to the technical field of analytical chemistry, and in particular to a kind of to determine lead in strawberry tree different parts sample Isotopic ratio and the method for identifying the red bayberry place of production.
Background technology
The globalization of food products market and food safety affair take place frequently, and increase the public attention degree of food place of production mark, Consumer is caused increasingly to pay close attention to food sources.The trackability of food is studied, corresponding food tracing system is established and is to ensure that One important means of food security.Place of production tracing technology is also widely used to move/derived food is planted, such as water fruits and vegetables, paddy Class, milk, meat etc..
The specificity that rapid test paper Source Tracing technology is mainly based upon in the agricultural product for screening different regions source refers to Mark, developing effectively accurate modernization detection technique turns into the emphasis of agricultural product tracing technology.Based on this, develop one in recent years The investigative technique that the relevant rapid test paper of series is traced to the source, covers gas-chromatography (GC), liquid chromatogram (HPLC), inductive etc. Gas ions mass spectrograph (ICP-MS), Capillary Electrophoresis (CE), near infrared spectrum (IR), uv-vis spectra (UV-Vis), core The methods of magnetic resonance (NMR), the region of product spy is identified by determining in separate sources agricultural product specific component difference Sign.But the in fact, shadow of the difference of each side such as plant agricultural products etc. are applied fertilizer, meteorological condition and agricultural land soil feature Ring, animal-derived food can also be influenceed by factors such as feed species, feeding patternses, and factors above causes rapid test paper to identify Uncertainty and complexity greatly increase, it is also to accurately identify the urgent of rapid test paper to be essential to develop more effective tracing technology Ask.
In nature, organism constantly experience carries out physics, chemistry, Biochemical processes with external environment, such as evaporates With condense, crystallize and dissolve, absorption and desorption, diffusion and thermal diffusion etc..These processes all can cause isotope to be fractionated (certain naturally The measurable change of " weight " isotope and " light " isotopic ratio of kind element).For example,13C/12C and the photosynthesis of plant way Footpath is relevant,15N/14N and soil environment and agricultural fertilizer are closely related,18O/16O and2H/1H and the close phase of environmental condition of region Close,87Sr/86Sr, Pb and geological conditions are closely related.Therefore, the measure of natural isotopic abundance can provide plant " class first Type " (C, N isotopic ratio) and region source (isotopic ratio such as H, O, Sr).The composition difference of isotope carry environment because The information of son, reflect the environmental condition residing for organism.And caused by this species diversity is exactly the natural fractionation effect of isotope, because This, isotope nature fractionation effect just can be as the general principle and foundation of tracing technology as it.Isotopics are biologies One kind " natural fingerprint " of body, and not changing with the change of chemical addition agent, can be provided for foodstuff traceability a kind of science, solely Identity authentication information that is vertical, unmodifiable and being flowed with whole food chain.
Rb-Sr and Pb isotopic systems are classical Isotope Datings and indicators, be widely used in geoscience, Cosmochemistry and environmental science.For Rb-Sr and Pb isotope assays, thermal ionization mass spectrometer (TIMS) has less matter Fractionation, relatively low memory effect, higher sensitivity and measuring accuracy are measured, therefore TIMS is always treated as above-mentioned isotope assay Most accurate instrument.However, requirement of the TIMS analyses for sample is extremely harsh, must go to before test except a large amount of matrix elements and Isobary, high-purity component to be measured are the premises of high-precision TIMS analyses.Sample point is carried out using ion-exchange chromatography From and enrichment, have that background is low, many advantages such as simple to operation, be the main technology of preparing used at present.
Lead has 4 kinds of natural isotopes, i.e.,204Pb、206Pb、207Pb and208Pb.Wherein204Pb half-life period is 1.4 × 1017 Year, half-life period is very long, and typically all it is handled as stable reference isotope.And206Pb、207Pb and208Pb is then U and Th Decay production, its abundance are constantly changing.Due to the isotope ratio value changes of lead can be precisely measured out with mass spectrum come, therefore this Kind change is normally used for the marker of environmental pollution.Because each department are on geologic structure, geological age and content of mineral substances Have differences and the difference of each department rainfall distribution, the isotopics for causing different regions lead are different.Therefore, the same position of lead Element composition has regionalism.Metallic element in plant largely comes from soil and surface water, the same position of lead in plant Therefore element composition also has geographical indicator.Therefore, these ratio difference can be accurately determined using mass spectrum, judges the production of plant Ground.
The content of the invention
The present invention is aiming at the above-mentioned state of the art, there is provided a kind of isotope for determining lead in strawberry tree different parts sample Ratio and the method for identifying the red bayberry place of production.
The technical solution adopted by the present invention is：
It is a kind of to determine the isotopic ratio of lead and the method for identifying the red bayberry place of production, the side in strawberry tree different parts sample Method comprises the following steps：
(1) isotopic ratio of lead in strawberry tree different parts sample is determined：
(A) sample pre-treatments：Strawberry tree different parts sample is weighed, the strawberry tree different parts sample includes red bayberry sample Product, strawberry tree Leaf samples, strawberry tree branch samples, red bayberry tree root sample or strawberry tree root soil sample, then add respectively Enter digestive reagent, obtain biased sample a, b, c, d or e, be respectively placed in microwave dissolver and cleared up, microwave dissolver is set Heating schedule be：5min is raised to 400w, keeps 5min, then 5min to rise to 800w, keeps 5min, cooling down to room temperature, institute Obtain mixed liquor heating to be evaporated, centrifuged after being dissolved with 3mol/L nitric acid, it is standby to respectively obtain digestion solution a, b, c, d or e；
It is described to weigh strawberry tree different parts sample, digestive reagent is separately added into, obtains biased sample a, b, c, d or e, is had Body presses following operation：
(a) red bayberry sample is weighed, concentrated nitric acid is added, obtains biased sample a, the volumetric usage of the concentrated nitric acid is with red bayberry sample The quality of product is calculated as 10mL/g；
(b) weigh strawberry tree Leaf samples, add concentrated nitric acid, obtain biased sample b, the volumetric usage of the concentrated nitric acid with The quality of strawberry tree Leaf samples is calculated as 18mL/g；
(c) weigh strawberry tree branch samples, add concentrated nitric acid, obtain biased sample c, the volumetric usage of the concentrated nitric acid with The quality of strawberry tree branch samples is calculated as 20mL/g；
(d) weigh strawberry tree tree root sample, add concentrated nitric acid, obtain biased sample d, the volumetric usage of the concentrated nitric acid with The quality of strawberry tree tree root sample is calculated as 23~24mL/g；
(e) strawberry tree root soil sample is weighed, it is 5 to add volume ratio：1 chloroazotic acid and the mix acid liquor of hydrofluoric acid, are obtained To biased sample e, the volumetric usage of the mix acid liquor is calculated as 40mL/g with the quality of strawberry tree root soil sample；
(B) sample purification：By SR Resin-B resin wet method dress posts, pillar 2~3 is alternately cleaned with 1+1 nitric acid and water It is secondary, then successively with 1+1 nitric acid, 6mol/L hydrochloric acid and washing post, then the nitric acid balance pillar with 3mol/L, step is taken respectively (A) digestion solution a, b, c, d or e upper prop prepared, first eluted, then eluted with 0.03mol/L nitric acid, Ran Houyong with 3mol/L nitric acid 6mol/L hydrochloric acid elutes lead, collects lead eluent in polytetrafluoroethylene (PTFE) sample dissolving cup, is placed on electric hot plate and is evaporated, then add dense Nitric acid dissolves, and seals 150 DEG C of heating 1h, then uncaps, and is evaporated in 150 DEG C, respectively obtains lead sample a, b, c, d, e；
(C) using the isotopic ratio of hot surface ionization mass spectrometer measure lead：
(C-1) pretreatment of sample band
Rhenium band is first put into immersion 30min~60min in ethanol, after taking-up is dried, rhenium band is spoted weld on sample introduction support, Degassing in device of air is subsequently placed in, the rhenium band pre-processed；
(C-2) the painting sample of lead
The 20mmol/L phosphoric acid that 1 μ L are pipetted with micropipettor is added on the rhenium band center of pretreatment, and energization is evaporated, then adds 1 μ On L silica gel cast charge to phosphoric acid, energization is evaporated, and lead sample a, b, c, d, e prepared by step (B) are used into mass fraction 3% respectively Nitric acid dissolving, then put respectively at the silica gel of rhenium band, energization is evaporated, at sample be added dropwise 1 μ L silica gel cast charges, be powered Energization reddening sample band after being evaporated, then sample introduction support is loaded to the sample disc of hot surface ionization mass spectrometer；
(C-3) the mass spectrum isotopic ratio detection of lead
Hot surface ionization mass spectrometer vacuumizes, and vacuum reaches 3 × 10-7During Pa, rhenium band is heated, tested, by temperature At 1250 ± 50 DEG C, detection obtains the isotopic ratio of lead for degree control207Pb/206Pb and208Pb/206Pb；
(2) the isotopic ratio identification red bayberry place of production of lead is utilized
According to the method for step (1), the sample of the strawberry tree different parts of different sources is taken to determine the isotope of lead respectively Ratio, the isotopic ratio of the lead of the sample of different sources same area is taken to do correlation distribution map, available for identifying unknown production The place of production situation of the strawberry tree sample on ground.
In the step (A), red bayberry sample, strawberry tree Leaf samples, red bayberry branch samples, strawberry tree tree root sample or poplar Japanese apricot root soil sample is respectively by red bayberry, red bayberry leaf, strawberry tree branch, strawberry tree tree root or strawberry tree root soil After drying with ceramic scissors cut it is small after, then ground with mortar obtained.
The strawberry tree root soil typically takes the soil of root 5~20cm depths, preferably takes root 10cm depths Soil.
In the step (A), the microwave dissolver is preferably using the Multiwave3000 microwaves of Anton Paar company production Clear up instrument.
In the step (B), the nitric acid of the 1+1 is by concentrated nitric acid and water by volume 1：1 mixed preparing obtains.
In the step (B), the SR Resin-B resins are produced by Trskem companies.
In the step (B), after eluting lead with 6mol/L hydrochloric acid, generally require cleaning and live again pillar, the cleaning is lived again The step of pillar is：6mol/L hydrochloric acid, 1+1 nitric acid and washing post are used successively.
Further, preferably described step (B) operates by the following method：
By SR Resin-B resin wet method dress posts, pillar is alternately cleaned 2~3 times with 1+1 nitric acid and water, then successively with The 1+1 of 5 times of column volumes nitric acid, the 6mol/L hydrochloric acid of 10 times of column volumes and the washing post of 10 times of column volumes, then with 5 times of column volumes 3mol/L nitric acid balance pillar, take respectively step (A) prepare digestion solution a, b, c, d or e upper prop, first with 15 times of column volumes The elution of 3mol/L nitric acid, then eluted with the 0.03mol/L nitric acid of 12.5 times of column volumes, then with the 6mol/L of 15 times of column volumes Hydrochloric acid elutes lead, collects lead eluent in polytetrafluoroethylene (PTFE) sample dissolving cup, is placed on electric hot plate and is evaporated, and it is molten then to add concentrated nitric acid Solution, 150 DEG C of heating 1h are sealed, then uncapped, be evaporated in 150 DEG C, respectively obtain lead sample a, b, c, d, e；Again successively with 10 times of posts The water of the 6mol/L hydrochloric acid of volume, the 1+1 of 10 times of column volumes nitric acid and 10 times of column volumes cleans pillar of living again；
In the step (C-1), device of air is gone to remove device of air using mass spectrum filament, degassing can be used successively with 1A and 4A Each degassing 15min of electric current, that is, the rhenium band pre-processed.
In the step (C-2), the silica gel cast charge is prepared in the following proportions：Weigh 0.1g silicic acid and be fully ground, Successively with after the nitric acid of mass fraction 10% and water washing 3~5 times, centrifugation, abandoning supernatant, residue adds 10mL0.1mol/L Phosphoric acid simultaneously shakes up, and the silica gel cast charge is made.
The hot surface ionization mass spectrometer that the step (C) uses is preferably Thermo Triton Plus mass spectrographs.
Further, the step (C-2) preferably presses following operation：
The 20mmol/L phosphoric acid that 1 μ L are pipetted with micropipettor is added on the rhenium band center of pretreatment, and energization 0.8A is evaporated, then Add on 1 μ L silica gel cast charges to phosphoric acid, energization is evaporated, and lead sample a, b, c, d, e prepared by step (B) are used into mass fraction respectively 3% nitric acid dissolving, is then put at the silica gel of rhenium band respectively, and energization is evaporated, and 1 μ L silica gel cast charges are added dropwise at sample, Energization 2.2A reddening sample band after energization is evaporated, then sample introduction support is loaded to the sample disc of hot surface ionization mass spectrometer.
When the step (C) determines the isotopic ratio of lead using hot surface ionization mass spectrometer, typically marked using SRM981 Sample as Quality Control sample come judge detection reliability and method reliability, this be well known to a person skilled in the art.
The present invention also provides a kind of method for determining the isotopic ratio of lead in strawberry tree different parts sample, methods described Comprise the following steps：
(A) sample pre-treatments：Strawberry tree different parts sample is weighed, the strawberry tree different parts sample includes red bayberry sample Product, strawberry tree Leaf samples, strawberry tree branch samples, red bayberry tree root sample or strawberry tree root soil sample, then add respectively Enter digestive reagent, obtain biased sample a, b, c, d or e, be respectively placed in microwave dissolver and cleared up, microwave dissolver is set Heating schedule be：5min is raised to 400w, keeps 5min, then 5min to rise to 800w, keeps 5min, cooling down to room temperature, institute Obtain mixed liquor heating to be evaporated, centrifuged after being dissolved with 3mol/L nitric acid, it is standby to respectively obtain digestion solution a, b, c, d or e；
It is described to weigh strawberry tree different parts sample, digestive reagent is separately added into, obtains biased sample a, b, c, d or e, is had Body presses following operation：
(a) red bayberry sample is weighed, concentrated nitric acid is added, obtains biased sample a, the volumetric usage of the concentrated nitric acid is with red bayberry sample The quality of product is calculated as 10mL/g；
(b) weigh strawberry tree Leaf samples, add concentrated nitric acid, obtain biased sample b, the volumetric usage of the concentrated nitric acid with The quality of strawberry tree Leaf samples is calculated as 18mL/g；
(c) weigh strawberry tree branch samples, add concentrated nitric acid, obtain biased sample c, the volumetric usage of the concentrated nitric acid with The quality of strawberry tree branch samples is calculated as 20mL/g；
(d) weigh strawberry tree tree root sample, add concentrated nitric acid, obtain biased sample d, the volumetric usage of the concentrated nitric acid with The quality of strawberry tree tree root sample is calculated as 23~24mL/g；
(e) strawberry tree root soil sample is weighed, it is 5 to add volume ratio：1 chloroazotic acid and the mix acid liquor of hydrofluoric acid, are obtained To biased sample e, the volumetric usage of the mix acid liquor is calculated as 40mL/g with the quality of strawberry tree root soil sample；
(B) sample purification：By SR Resin-B resin wet method dress posts, pillar 2~3 is alternately cleaned with 1+1 nitric acid and water It is secondary, then successively with 1+1 nitric acid, 6mol/L hydrochloric acid and washing post, then the nitric acid balance pillar with 3mol/L, step is taken respectively (A) digestion solution a, b, c, d or e upper prop prepared, first eluted, then eluted with 0.03mol/L nitric acid, Ran Houyong with 3mol/L nitric acid 6mol/L hydrochloric acid elutes lead, collects lead eluent in polytetrafluoroethylene (PTFE) sample dissolving cup, is placed on electric hot plate and is evaporated, then add dense Nitric acid dissolves, and seals 150 DEG C of heating 1h, then uncaps, and is evaporated in 150 DEG C, respectively obtains lead sample a, b, c, d, e；
(C) using the isotopic ratio of hot surface ionization mass spectrometer measure lead：
(C-1) pretreatment of sample band
Rhenium band is first put into immersion 30min~60min in ethanol, after taking-up is dried, rhenium band is spoted weld on sample introduction support, Degassing in device of air is subsequently placed in, the rhenium band pre-processed；
(C-2) the painting sample of lead
The 20mmol/L phosphoric acid that 1 μ L are pipetted with micropipettor is added on the rhenium band center of pretreatment, and energization is evaporated, then adds 1 μ On L silica gel cast charge to phosphoric acid, energization is evaporated, and lead sample a, b, c, d, e prepared by step (B) are used into mass fraction 3% respectively Nitric acid dissolving, then put respectively at the silica gel of rhenium band, energization is evaporated, at sample be added dropwise 1 μ L silica gel cast charges, be powered Energization reddening sample band after being evaporated, then sample introduction support is loaded to the sample disc of hot surface ionization mass spectrometer；
(C-3) the mass spectrum isotopic ratio detection of lead
Hot surface ionization mass spectrometer vacuumizes, and vacuum reaches 3 × 10-7During Pa, rhenium band is heated, tested, by temperature At 1250 ± 50 DEG C, detection obtains the isotopic ratio of lead for degree control207Pb/206Pb and208Pb/206Pb。
Compared with prior art, it is as follows the advantages of this method：
The present invention quickly determines the isotope of lead in strawberry tree different parts sample using hot surface ionization mass spectrometer first Ratio, the ratio be strawberry tree one kind " natural fingerprint ", and do not change with the change of chemical addition agent, can be traced to the source for red bayberry A kind of science is provided, independent, the unmodifiable and identity authentication information that is flowed with whole food chain, method is reliably steady It is fixed.Especially for the product between extensive area, its difference can be effectively distinguished.This method is in pretreatment process with acid It is few, environmental protection；Cross that the post time is short, can realize the quick separating of lead element, detection efficiency is high；This method passes through sample pre-treatments, Matrix influence is small, and interference is few, and testing result precision is high, and effect is good.
Brief description of the drawings
The correlation distribution map of the isotopic ratio of the lead of Fig. 1 different sources red bayberry samples.
Embodiment
Technical scheme is described in further detail with reference to embodiments, but protection scope of the present invention is not It is limited to this.
The measure of the isotopic ratio of the lead of the Cixi place of production strawberry tree different parts sample of embodiment 1
Red bayberry sample, strawberry tree Leaf samples, red bayberry branch samples, strawberry tree tree root sample or strawberry tree root soil sample Product are to be cut after respectively drying red bayberry, red bayberry leaf, strawberry tree branch, strawberry tree tree root or strawberry tree root soil with ceramics Knife cut it is small after, then ground with mortar obtained.
(1) 1g red bayberry samples are weighed respectively, add 10mL concentrated nitric acids；0.5g Leaf samples, add 9mL concentrated nitric acids；0.3g The pedotheque of red bayberry usage tree root 10cm depths, add 10mL chloroazotic acid and 2mL hydrofluoric acid；0.5g strawberry tree branch samples, add 10mL concentrated nitric acids；0.3g strawberry tree tree root samples, add 7mL concentrated nitric acids；
It is respectively put into microwave dissolver (Multiwave3000 of Anton Paar company production) and is cleared up, heating schedule 400w is raised to for 5min, keeps 5min, then 5min to rise to 800w, keeps 5min, cooling down to room temperature., will after the completion of resolution Mixing liquid is transferred to 15mL polytetrafluoroethylene (PTFE) sample dissolving cups, is positioned over 150 DEG C of heating on electric hot plate and is evaporated, with 1mL3mol/L nitric acid Centrifuged after dissolving, it is standby to obtain digestion solution.
(2) by SR Resin-B resins (Trskem companies produce, 100-150 μm of particle diameter) wet method dress post, each pillar dress The SR Resin-B resins of 200 μ l volumes.Pillar is alternately cleaned with 1+1 nitric acid and water 3 times, then successively with 1mL1+1 nitre Acid, 2mL6mol/L hydrochloric acid and 2mL washing posts, 1mL3mol/L nitric acid balance pillar, the digestion solution sample for taking step (1) to prepare The upper pillars of 0.5mL, eluted with 3mL3mol/L nitric acid, the elution of 2.5mL0.03mol/L nitric acid, 3mL6mol/L hydrochloric acid elution lead, then 2mL6mol/L hydrochloric acid is used successively, and post is washed in 2mL1+1 nitric acid and 2mL water reuse (treatments.The lead eluted with 3mL6mol/L hydrochloric acid is collected to elute Liquid is placed on electric hot plate 150 DEG C and is evaporated in 5mL polytetrafluoroethylene (PTFE) sample dissolving cups, adds 1mL concentrated nitric acids, seals 150 DEG C of heating 1h, lid is opened, 150 DEG C are evaporated, and it is standby to obtain lead sample.
(3) isotopic ratio of hot surface ionization mass spectrometer (Thermo Triton Plus mass spectrographs) measure lead
The pretreatment of sample band
First rhenium band is put into ethanol and soaks 40min, after taking-up is dried, rhenium band is spoted weld on plug-in unit, is subsequently placed in matter Spectrum filament is gone in device of air (Beijing Yi Guanjing instrument Science and Technology Ltd.), successively with each degassing 15min of 1A and 4A electric current, is obtained The rhenium band of pretreatment.
The painting sample of lead
The lead sample prepared with the nitric acid dissolving step (2) of mass fraction 3%, pipettes 1uL's with micropipettor In the rhenium band center of pretreatment, energization 0.8A is evaporated 20mmol/L phosphoric acid, then is added on 1 μ L silica gel cast charges to phosphoric acid, is powered and is steamed Dry, then again by the lead sampling point after dissolving at the silica gel of rhenium band, energization is evaporated, and 1 μ L silica gel cast charges are added dropwise at sample, Energization 2.2A reddening sample band after energization is evaporated, then sample introduction support is loaded to the sample disc of hot surface ionization mass spectrometer.
The silica gel cast charge is prepared by the following method：Weigh 0.1g silicic acid and be fully ground, use mass fraction successively After 10% nitric acid and water washing 3 times, centrifugation, abandoning supernatant, residue adds 10mL0.1mol/L phosphoric acid and simultaneously shakes up, and institute is made State silica gel cast charge.
The mass spectrum isotopic ratio detection of lead
Hot surface ionization mass spectrometer vacuumizes, and treats mass spectrograph normal operation, and vacuum reaches 3 × 10-7During Pa, rhenium band is added Temperature, by temperature control at 1250 ± 50 DEG C, determine the isotopic ratio of lead207Pb/206Pb and208Pb/206Pb。
Acquired results see the table below 1
Table 1：
Embodiment 2
Cixi, Yuyao, the red bayberry sample in three, Wenzhou place of production are taken, the same position of lead is determined according to the method and step of embodiment 1 Plain ratio207Pb/206Pb and206Pb/208Pb, correlation distribution map is done, as shown in figure 1, Fig. 1 can be seen that the lead in three places of production Isotope ratio Distribution value between significant difference be present, each own different distributed area.Therefore Fig. 1 can be used for differentiating not With the red bayberry in the place of production.To the red bayberry sample in the unknown place of production, the isotopic ratio of lead is determined207Pb/206Pb and206Pb/208Pb, observation Its numeric distribution can then be accredited as the place of production of the distributed area close to which distributed area.

Claims (8)

  1. Determine the isotopic ratio of lead and the method for identifying the red bayberry place of production, its feature in strawberry tree different parts sample 1. a kind of and exist In the described method comprises the following steps：
    (1) isotopic ratio of lead in strawberry tree different parts sample is determined：
    (A) sample pre-treatments：Weigh strawberry tree different parts sample, the strawberry tree different parts sample include red bayberry sample, Strawberry tree Leaf samples, strawberry tree branch samples, red bayberry tree root sample or strawberry tree root soil sample, are then respectively adding and disappear Reagent is solved, biased sample a, b, c, d or e is obtained, is respectively placed in microwave dissolver and is cleared up, the liter of microwave dissolver is set Warm program is：5min is raised to 400w, keeps 5min, then 5min to rise to 800w, keeps 5min, cooling down to room temperature, and gained mixes Close liquid heating to be evaporated, centrifuged after being dissolved with 3mol/L nitric acid, it is standby to respectively obtain digestion solution a, b, c, d or e；
    It is described to weigh strawberry tree different parts sample, digestive reagent is separately added into, biased sample a, b, c, d or e is obtained, specifically presses Operate below：
    (a) red bayberry sample is weighed, concentrated nitric acid is added, obtains biased sample a, the volumetric usage of the concentrated nitric acid is with red bayberry sample Quality is calculated as 10mL/g；
    (b) strawberry tree Leaf samples are weighed, concentrated nitric acid is added, obtains biased sample b, the volumetric usage of the concentrated nitric acid is with red bayberry The quality of leaf subsample is calculated as 18mL/g；
    (c) strawberry tree branch samples are weighed, concentrated nitric acid is added, obtains biased sample c, the volumetric usage of the concentrated nitric acid is with red bayberry The quality of tree branch samples is calculated as 20mL/g；
    (d) strawberry tree tree root sample is weighed, concentrated nitric acid is added, obtains biased sample d, the volumetric usage of the concentrated nitric acid is with red bayberry The quality of tree tree root sample is calculated as 23~24mL/g；
    (e) strawberry tree root soil sample is weighed, it is 5 to add volume ratio：1 chloroazotic acid and the mix acid liquor of hydrofluoric acid, are mixed Sample e is closed, the volumetric usage of the mix acid liquor is calculated as 40mL/g with the quality of strawberry tree root soil sample；
    (B) sample purification：By SR Resin-B resin wet method dress posts, pillar is alternately cleaned 2~3 times with 1+1 nitric acid and water, so Afterwards successively with 1+1 nitric acid, 6mol/L hydrochloric acid and washing post, then the nitric acid balance pillar with 3mol/L, take step (A) to make respectively Standby digestion solution a, b, c, d or e upper prop, first eluted with 3mol/L nitric acid, then eluted with 0.03mol/L nitric acid, then use 6mol/ L hydrochloric acid elutes lead, collects lead eluent in polytetrafluoroethylene (PTFE) sample dissolving cup, is placed on electric hot plate and is evaporated, then add concentrated nitric acid Dissolving, 150 DEG C of heating 1h are sealed, then uncapped, be evaporated in 150 DEG C, respectively obtain lead sample a, b, c, d, e；
    (C) using the isotopic ratio of hot surface ionization mass spectrometer measure lead：
    (C-1) pretreatment of sample band
    Rhenium band is first put into immersion 30min~60min in ethanol, after taking-up is dried, rhenium band is spoted weld on sample introduction support, then Degassing in device of air is placed in, the rhenium band pre-processed；
    (C-2) the painting sample of lead
    The 20mmol/L phosphoric acid that 1 μ L are pipetted with micropipettor is added on the rhenium band center of pretreatment, and energization is evaporated, then adds 1 μ L silicon On glue cast charge to phosphoric acid, energization is evaporated, and lead sample a, b, c, d, e prepared by step (B) uses the nitre of mass fraction 3% respectively Acid dissolving, is then put at the silica gel of rhenium band respectively, and energization is evaporated, and 1 μ L silica gel cast charges are added dropwise at sample, and energization is evaporated Energization reddening sample band afterwards, then sample introduction support is loaded to the sample disc of hot surface ionization mass spectrometer；
    (C-3) the mass spectrum isotopic ratio detection of lead
    Hot surface ionization mass spectrometer vacuumizes, and vacuum reaches 3 × 10-7During Pa, rhenium band is heated, tested, by temperature control For system at 1250 ± 50 DEG C, detection obtains the isotopic ratio of lead207Pb/206Pb and208Pb/206Pb；
    (2) the isotopic ratio identification red bayberry place of production of lead is utilized
    According to the method for step (1), the sample of the strawberry tree different parts of different sources is taken to determine the isotopic ratio of lead respectively, The isotopic ratio of the lead of the sample of different sources same area is taken to do correlation distribution map, available for the poplar for identifying the unknown place of production The place of production situation of Japanese apricot sample.
  2. 2. the method as described in claim 1, it is characterised in that in the step (A), red bayberry sample, strawberry tree Leaf samples, Red bayberry branch samples, strawberry tree tree root sample or strawberry tree root soil sample are respectively by red bayberry, red bayberry leaf, strawberry tree Branch, strawberry tree tree root or strawberry tree root soil dry after with ceramic scissors cut it is small after, then ground with mortar obtained.
  3. 3. the method as described in claim 1, it is characterised in that in the step (A), the microwave dissolver uses Anton Paar The Multiwave3000 microwave dissolvers of company's production.
  4. 4. the method as described in claim 1, it is characterised in that in the step (B), the nitric acid of the 1+1 be by concentrated nitric acid and Water by volume 1：1 mixed preparing obtains.
  5. 5. the method as described in claim 1, it is characterised in that in the step (B), with 6mol/L hydrochloric acid elute lead after, by with Lower step cleans pillar of living again：Successively with 6mol/L hydrochloric acid, 1+1 nitric acid and washing post.
  6. 6. the method as described in claim 1, it is characterised in that the step (B) operates by the following method：
    By SR Resin-B resin wet method dress posts, pillar is alternately cleaned 2~3 times with 1+1 nitric acid and water, then successively with 5 times The 1+1 of column volume nitric acid, the 6mol/L hydrochloric acid of 10 times of column volumes and the washing post of 10 times of column volumes, then with 5 times of column volumes 3mol/L nitric acid balance pillar, digestion solution a, b, c, d or e upper prop for taking step (A) to prepare respectively, first with 15 times of column volumes 3mol/L nitric acid elutes, then is eluted with the 0.03mol/L nitric acid of 12.5 times of column volumes, then with the 6mol/L salt of 15 times of column volumes Pickling takes off lead, collects lead eluent in polytetrafluoroethylene (PTFE) sample dissolving cup, is placed on electric hot plate and is evaporated, and it is molten then to add concentrated nitric acid Solution, 150 DEG C of heating 1h are sealed, then uncapped, be evaporated in 150 DEG C, respectively obtain lead sample a, b, c, d, e；Again successively with 10 times of posts The water of the 6mol/L hydrochloric acid of volume, the 1+1 of 10 times of column volumes nitric acid and 10 times of column volumes cleans pillar of living again.
  7. 7. the method as described in claim 1, it is characterised in that in the step (C-2), the silica gel cast charge by comparing below Example is prepared：Weigh 0.1g silicic acid and be fully ground, successively with after the nitric acid of mass fraction 10% and water washing 3~5 times, centrifugation, abandon Supernatant is removed, residue adds 10mL0.1mol/L phosphoric acid and shaken up, and the silica gel cast charge is made.
  8. A kind of 8. method for determining the isotopic ratio of lead in strawberry tree different parts sample, it is characterised in that methods described includes Following steps：
    (A) sample pre-treatments：Weigh strawberry tree different parts sample, the strawberry tree different parts sample include red bayberry sample, Strawberry tree Leaf samples, strawberry tree branch samples, red bayberry tree root sample or strawberry tree root soil sample, are then respectively adding and disappear Reagent is solved, biased sample a, b, c, d or e is obtained, is respectively placed in microwave dissolver and is cleared up, the liter of microwave dissolver is set Warm program is：5min is raised to 400w, keeps 5min, then 5min to rise to 800w, keeps 5min, cooling down to room temperature, and gained mixes Close liquid heating to be evaporated, centrifuged after being dissolved with 3mol/L nitric acid, it is standby to respectively obtain digestion solution a, b, c, d or e；
    It is described to weigh strawberry tree different parts sample, digestive reagent is separately added into, biased sample a, b, c, d or e is obtained, specifically presses Operate below：
    (a) red bayberry sample is weighed, concentrated nitric acid is added, obtains biased sample a, the volumetric usage of the concentrated nitric acid is with red bayberry sample Quality is calculated as 10mL/g；
    (b) strawberry tree Leaf samples are weighed, concentrated nitric acid is added, obtains biased sample b, the volumetric usage of the concentrated nitric acid is with red bayberry The quality of leaf subsample is calculated as 18mL/g；
    (c) strawberry tree branch samples are weighed, concentrated nitric acid is added, obtains biased sample c, the volumetric usage of the concentrated nitric acid is with red bayberry The quality of tree branch samples is calculated as 20mL/g；
    (d) strawberry tree tree root sample is weighed, concentrated nitric acid is added, obtains biased sample d, the volumetric usage of the concentrated nitric acid is with red bayberry The quality of tree tree root sample is calculated as 23~24mL/g；
    (e) strawberry tree root soil sample is weighed, it is 5 to add volume ratio：1 chloroazotic acid and the mix acid liquor of hydrofluoric acid, are mixed Sample e is closed, the volumetric usage of the mix acid liquor is calculated as 40mL/g with the quality of strawberry tree root soil sample；
    (B) sample purification：By SR Resin-B resin wet method dress posts, pillar is alternately cleaned 2~3 times with 1+1 nitric acid and water, so Afterwards successively with 1+1 nitric acid, 6mol/L hydrochloric acid and washing post, then the nitric acid balance pillar with 3mol/L, take step (A) to make respectively Standby digestion solution a, b, c, d or e upper prop, first eluted with 3mol/L nitric acid, then eluted with 0.03mol/L nitric acid, then use 6mol/ L hydrochloric acid elutes lead, collects lead eluent in polytetrafluoroethylene (PTFE) sample dissolving cup, is placed on electric hot plate and is evaporated, then add concentrated nitric acid Dissolving, 150 DEG C of heating 1h are sealed, then uncapped, be evaporated in 150 DEG C, respectively obtain lead sample a, b, c, d, e；
    (C) using the isotopic ratio of hot surface ionization mass spectrometer measure lead：
    (C-1) pretreatment of sample band
    Rhenium band is first put into immersion 30min~60min in ethanol, after taking-up is dried, rhenium band is spoted weld on sample introduction support, then Degassing in device of air is placed in, the rhenium band pre-processed；
    (C-2) the painting sample of lead
    The 20mmol/L phosphoric acid that 1 μ L are pipetted with micropipettor is added on the rhenium band center of pretreatment, and energization is evaporated, then adds 1 μ L silicon On glue cast charge to phosphoric acid, energization is evaporated, and lead sample a, b, c, d, e prepared by step (B) uses the nitre of mass fraction 3% respectively Acid dissolving, is then put at the silica gel of rhenium band respectively, and energization is evaporated, and 1 μ L silica gel cast charges are added dropwise at sample, and energization is evaporated Energization reddening sample band afterwards, then sample introduction support is loaded to the sample disc of hot surface ionization mass spectrometer；
    (C-3) the mass spectrum isotopic ratio detection of lead
    Hot surface ionization mass spectrometer vacuumizes, and vacuum reaches 3 × 10-7During Pa, rhenium band is heated, tested, by temperature control For system at 1250 ± 50 DEG C, detection obtains the isotopic ratio of lead207Pb/206Pb and208Pb/206Pb。
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CN107424003A (en) * 2017-05-05 2017-12-01 浙江省农业科学院 A kind of red bayberry place of production source tracing method based on isotope ratio rate and multielement
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