CN105203622A - Method for determining ratio of lead isotopes in sample of different parts of waxberry tree and identifying origin of waxberry - Google Patents
Method for determining ratio of lead isotopes in sample of different parts of waxberry tree and identifying origin of waxberry Download PDFInfo
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Abstract
The invention discloses a method for determining a ratio of lead isotopes in a sample of different parts of a waxberry tree and identifying an origin of waxberry. The method comprises the following steps: measuring a sample of different parts of the waxberry tree, preprocessing the sample, digesting the sample by virtue of microwave, purifying the sample by utilizing SR resin-B resin, eluting to obtain a lead sample, and then detecting the lead sample by adopting a thermal surface ionization mass spectrometry to obtain a ratio of lead isotopes in the lead sample. A correlation distribution map can be drawn according to the ratio of the lead isotopes of the sample of the same part in different origins and can be used for identifying the origin situation of the waxberry tree sample of an unknown origin. The thermal surface ionization mass spectrometry is first used for rapidly determining the ratio of lead isotopes in the sample of different parts of the waxberry, a scientific, independent and invariable identify identification information can be provided for tracking the waxberry source, and the method is reliable and stable. Particularly for the products of a large-sized area, the difference can be effectively distinguished. The method is high in detection efficiency; moreover, the detection result is high in precision and good in effect.
Description
Technical field
The present invention relates to the technical field of analytical chemistry, be specifically related to a kind ofly to measure in strawberry tree different parts sample plumbous isotopic ratio and identify the method in the red bayberry place of production.
Background technology
Globalization and the food safety affair of food products market take place frequently, and increase the public attention degree of food place of production mark, cause consumer more and more to pay close attention to food sources.The trackability of research food, setting up corresponding food tracing system is guarantee an important means of food security.Place of production tracing technology has also been widely used in moving/plant derived food, as fruit, vegetables, cereal, milk, meat etc.
Rapid test paper Source Tracing technology is mainly based on the specific index screened in the agricultural product in source, different regions, and exploitation effectively modernization detection technique accurately becomes the emphasis of agricultural product tracing technology.Based on this, the investigative technique that a series of relevant rapid test paper of development in recent years is traced to the source, cover gas chromatography (GC), liquid chromatography (HPLC), icp ms (ICP-MS), Capillary Electrophoresis (CE), near infrared spectrum (IR), the methods such as uv-vis spectra (UV-Vis), nuclear magnetic resonance (NMR), identify the regional feature of this product by measuring specific component difference in separate sources agricultural product.But in fact, plant agricultural product etc. are subject to the impact of the difference of each side such as fertilising, meteorological condition and agricultural land soil feature, animal-derived food also can be subject to the impact of the factors such as feed kind, feeding patterns, above factor makes the uncertainty of rapid test paper identification and complicacy greatly increase, and developing more effective tracing technology is also the active demand accurately identifying rapid test paper.
Occurring in nature, biosome constantly experiences and carries out physics, chemistry, Biochemical processes with external environment, such as evaporation and condensation, crystallization and dissolve, absorption and desorption, diffusion and thermal diffusion etc.These processes all can cause isotope nature fractionation (the measured change of certain element " weight " isotope and " gently " isotopic ratio).Such as,
13c/
12c is relevant with the photosynthesis approach of plant,
15n/
14n and soil environment and agricultural fertilizer closely related,
18o/
16o and
2h/
1the environmental baseline of H and region is closely related,
87sr/
86sr, Pb and geologic condition closely related.Therefore, first the mensuration of natural isotopic abundance can provide plant " type " (C, N isotopic ratio) and source, region isotopic ratios such as () H, O, Sr.Isotopic composition difference carries the information of envirment factor, the environmental baseline of reflection residing for biosome.And this species diversity just isotopic natural fractionation effect cause, therefore, isotope nature fractionation effect just becomes its ultimate principle that can be used as tracing technology and foundation.Isotopics are one " natural fingerprint " of biosome, and do not change with the change of chemical addition agent, can for foodstuff traceability provide a kind of science, independently, identity authentication information that is unmodifiable and that flow with whole food chain.
Rb-Sr and Pb isotopic system is classical Isotope Dating and indicators, is widely used in geoscience, cosmochemistry and environmental science.For Rb-Sr and Pb isotope assay, thermal ionization mass spectrometer (TIMS) has less mass fractionation, lower memory effect, higher sensitivity and measuring accuracy, and therefore TIMS is regarded as above-mentioned isotope assay instrument the most accurately always.But TIMS analyzes very harsh for the requirement of sample, must remove a large amount of matrix element and isobary before test, high-purity component to be measured is the prerequisite that high precision TIMS analyzes.Adopting ion-exchange chromatography to carry out sample separation and enrichment, have the many advantages such as background is low, simple to operation, is the main technology of preparing adopted at present.
Lead has 4 kinds of natural isotopes, namely
204pb,
206pb,
207pb and
208pb.Wherein
204the half life period of Pb is 1.4 × 10
17year, the half life period is very long, generally all it is treated as stable reference isotope process.And
206pb,
207pb and
208pb is then that the decay of U and Th is produced, and its abundance is in continuous change.Because the isotopic ratio change of lead accurately can be measured with mass spectrum, therefore this change is normally used for the marker of environmental pollution.Because each department there are differences and the difference of each department rainfall distribution on geologic structure, geological age and content of mineral substances, the isotopics causing different regions lead are different.Therefore, lead isotope composition has regionalism.Metallic element major part in plant comes from soil and surface water, and therefore the lead isotope composition in plant also has geographical indicator.Therefore, these ratio difference of mass spectrum Accurate Measurement can be utilized, judge the place of production of plant.
Summary of the invention
The present invention is exactly for the above-mentioned state of the art, provides a kind of and to measure in strawberry tree different parts sample plumbous isotopic ratio and identify the method in the red bayberry place of production.
The technical solution used in the present invention is:
To measure in strawberry tree different parts sample plumbous isotopic ratio and identify the method in the red bayberry place of production, said method comprising the steps of:
(1) isotopic ratio plumbous in strawberry tree different parts sample is measured:
(A) sample pre-treatments: take strawberry tree different parts sample, described strawberry tree different parts sample comprises red bayberry sample, strawberry tree Leaf samples, strawberry tree branch samples, red bayberry tree root sample or strawberry tree root soil sample, then add respectively and clear up reagent, obtain biased sample a, b, c, d or e, be placed in microwave dissolver respectively to clear up, the heating schedule arranging microwave dissolver is: 5min is raised to 400w, keep 5min, 5min rises to 800w again, keep 5min, cooling down is to room temperature, gained mixed liquor heating evaporate to dryness, with centrifugal after 3mol/L nitric acid dissolve, obtain digestion solution a respectively, b, c, d or e is for subsequent use,
Describedly take strawberry tree different parts sample, add respectively and clear up reagent, obtain biased sample a, b, c, d or e, concrete by following operation:
A () takes red bayberry sample, add red fuming nitric acid (RFNA), obtains biased sample a, and the volumetric usage of described red fuming nitric acid (RFNA) counts 10mL/g with the quality of red bayberry sample;
B () takes strawberry tree Leaf samples, add red fuming nitric acid (RFNA), obtains biased sample b, and the volumetric usage of described red fuming nitric acid (RFNA) counts 18mL/g with the quality of strawberry tree Leaf samples;
C () takes strawberry tree branch samples, add red fuming nitric acid (RFNA), obtains biased sample c, and the volumetric usage of described red fuming nitric acid (RFNA) counts 20mL/g with the quality of strawberry tree branch samples;
D () takes strawberry tree tree root sample, add red fuming nitric acid (RFNA), obtains biased sample d, and the volumetric usage of described red fuming nitric acid (RFNA) counts 23 ~ 24mL/g with the quality of strawberry tree tree root sample;
E () takes strawberry tree root soil sample, adding volume ratio is the chloroazotic acid of 5:1 and the mix acid liquor of hydrofluorite, obtains biased sample e, and the volumetric usage of described mix acid liquor counts 40mL/g with the quality of strawberry tree root soil sample;
(B) sample purification: by SRResin-B resin wet method dress post, with the nitric acid of 1+1 and water alternately cleaning pillar 2 ~ 3 times, then successively with the nitric acid of 1+1, 6mol/L hydrochloric acid and washing post, again with the nitric acid balance pillar of 3mol/L, get digestion solution a prepared by step (A) respectively, b, c, d or e upper prop, first use the drip washing of 3mol/L nitric acid, use the drip washing of 0.03mol/L nitric acid again, then use 6mol/L hydrochloric acid wash-out plumbous, collect plumbous eluent in the molten sample cup of teflon, be placed in evaporate to dryness on electric hot plate, then add red fuming nitric acid (RFNA) to dissolve, seal 150 DEG C of heating 1h, uncap again, in 150 DEG C of evaporates to dryness, obtain plumbous sample a respectively, b, c, d, e,
(C) hot surface ionization mass spectrometer is adopted to measure plumbous isotopic ratio:
(C-1) pre-service of sample belt
First rhenium band is put into ethanol and soak 30min ~ 60min, take out after drying, rhenium band is spoted weld on sample introduction support, be then placed in the device that degass and degas, obtain pretreated rhenium band;
(C-2) plumbous painting sample
The 20mmol/L phosphoric acid pipetting 1 μ L with micropipettor is added on pretreated rhenium band central authorities, energising evaporate to dryness, add 1 μ L silica gel cast charge again on phosphoric acid, energising evaporate to dryness, plumbous sample a, b, c, d, e of step (B) being prepared use the nitric acid dissolve of massfraction 3% respectively, then the silica gel place in rhenium band is put respectively, energising evaporate to dryness, 1 μ L silica gel cast charge is dripped again in sample place, be energized after energising evaporate to dryness reddening sample belt, then sample introduction support loaded the sample disc of hot surface ionization mass spectrometer;
(C-3) plumbous mass spectrum isotopic ratio detects
Hot surface ionization mass spectrometer vacuumizes, and vacuum tightness reaches 3 × 10
-7during Pa, rhenium band is heated, tests, temperature is controlled at 1250 ± 50 DEG C, detect and obtain plumbous isotopic ratio
207pb/
206pb and
208pb/
206pb;
(2) the plumbous isotopic ratio qualification red bayberry place of production is utilized
According to the method for step (1), get the isotopic ratio of the sample determination lead of the strawberry tree different parts of Different sources respectively, the isotopic ratio getting the lead of the sample of Different sources same area does correlativity distribution plan, can be used for the place of production situation of the strawberry tree sample identifying the unknown place of production.
In described step (A), red bayberry sample, strawberry tree Leaf samples, red bayberry branch samples, strawberry tree tree root sample or strawberry tree root soil sample be respectively by after red bayberry, strawberry tree leaf, strawberry tree branch, strawberry tree tree root or the drying of strawberry tree root soil with ceramic scissors cut little after, then grind obtained with mortar.
Described strawberry tree root soil generally takes the soil of root 5 ~ 20cm depths, preferably takes the soil of root 10cm depths.
In described step (A), the Multiwave3000 microwave dissolver that described microwave dissolver preferably adopts Anton Paar company to produce.
In described step (B), the nitric acid of described 1+1 be by red fuming nitric acid (RFNA) and water by volume 1:1 mixed preparing obtain.
In described step (B), described SRResin-B resin is produced by Trskem company.
In described step (B), after 6mol/L hydrochloric acid wash-out lead, generally need cleaning to live again pillar, the live again step of pillar of described cleaning is: use 6mol/L hydrochloric acid successively, the nitric acid of 1+1 and washing post.
Further, preferred described step (B) operates by the following method:
By SRResin-B resin wet method dress post, with the nitric acid of 1+1 and water alternately cleaning pillar 2 ~ 3 times, then successively with the nitric acid of the 1+1 of 5 times of column volumes, the washing post of the 6mol/L hydrochloric acid of 10 times of column volumes and 10 times of column volumes, again with the nitric acid balance pillar of the 3mol/L of 5 times of column volumes, get digestion solution a prepared by step (A) respectively, b, c, d or e upper prop, first use the 3mol/L nitric acid drip washing of 15 times of column volumes, use the 0.03mol/L nitric acid drip washing of 12.5 times of column volumes again, then use the 6mol/L hydrochloric acid wash-out of 15 times of column volumes plumbous, collect plumbous eluent in the molten sample cup of teflon, be placed in evaporate to dryness on electric hot plate, then add red fuming nitric acid (RFNA) to dissolve, seal 150 DEG C of heating 1h, uncap again, in 150 DEG C of evaporates to dryness, obtain plumbous sample a respectively, b, c, d, e, use the 6mol/L hydrochloric acid of 10 times of column volumes more successively, the water of the nitric acid of the 1+1 of 10 times of column volumes and 10 times of column volumes cleans pillar of living again,
In described step (C-1), the device that degass can adopt mass spectrum filament to degas device, degass to adopt and successively respectively to degas 15min with the electric current of 1A and 4A, namely obtain pretreated rhenium band.
In described step (C-2), described silica gel cast charge is by following proportions: take 0.1g silicic acid and fully grinding, after using massfraction 10% nitric acid and water washing 3 ~ 5 times successively, centrifugal, abandoning supernatant, residue adds 10mL0.1mol/L phosphoric acid and shakes up, obtained described silica gel cast charge.
The hot surface ionization mass spectrometer that described step (C) adopts is preferably ThermoTritonPlus mass spectrometer.
Further, described step (C-2) is preferably by following operation:
The 20mmol/L phosphoric acid pipetting 1 μ L with micropipettor is added on pretreated rhenium band central authorities, energising 0.8A evaporate to dryness, add 1 μ L silica gel cast charge again on phosphoric acid, energising evaporate to dryness, plumbous sample a, b, c, d, e of step (B) being prepared use the nitric acid dissolve of massfraction 3% respectively, then the silica gel place in rhenium band is put respectively, energising evaporate to dryness, 1 μ L silica gel cast charge is dripped again in sample place, be energized after energising evaporate to dryness 2.2A reddening sample belt, then sample introduction support loaded the sample disc of hot surface ionization mass spectrometer.
When described step (C) adopts hot surface ionization mass spectrometer to measure plumbous isotopic ratio, the general SRM981 of employing standard specimen judges the reliability of reliability and the method detected as Quality Control sample, this well known to a person skilled in the art.
The present invention also provides a kind of method measuring isotopic ratio plumbous in strawberry tree different parts sample, said method comprising the steps of:
(A) sample pre-treatments: take strawberry tree different parts sample, described strawberry tree different parts sample comprises red bayberry sample, strawberry tree Leaf samples, strawberry tree branch samples, red bayberry tree root sample or strawberry tree root soil sample, then add respectively and clear up reagent, obtain biased sample a, b, c, d or e, be placed in microwave dissolver respectively to clear up, the heating schedule arranging microwave dissolver is: 5min is raised to 400w, keep 5min, 5min rises to 800w again, keep 5min, cooling down is to room temperature, gained mixed liquor heating evaporate to dryness, with centrifugal after 3mol/L nitric acid dissolve, obtain digestion solution a respectively, b, c, d or e is for subsequent use,
Describedly take strawberry tree different parts sample, add respectively and clear up reagent, obtain biased sample a, b, c, d or e, concrete by following operation:
A () takes red bayberry sample, add red fuming nitric acid (RFNA), obtains biased sample a, and the volumetric usage of described red fuming nitric acid (RFNA) counts 10mL/g with the quality of red bayberry sample;
B () takes strawberry tree Leaf samples, add red fuming nitric acid (RFNA), obtains biased sample b, and the volumetric usage of described red fuming nitric acid (RFNA) counts 18mL/g with the quality of strawberry tree Leaf samples;
C () takes strawberry tree branch samples, add red fuming nitric acid (RFNA), obtains biased sample c, and the volumetric usage of described red fuming nitric acid (RFNA) counts 20mL/g with the quality of strawberry tree branch samples;
D () takes strawberry tree tree root sample, add red fuming nitric acid (RFNA), obtains biased sample d, and the volumetric usage of described red fuming nitric acid (RFNA) counts 23 ~ 24mL/g with the quality of strawberry tree tree root sample;
E () takes strawberry tree root soil sample, adding volume ratio is the chloroazotic acid of 5:1 and the mix acid liquor of hydrofluorite, obtains biased sample e, and the volumetric usage of described mix acid liquor counts 40mL/g with the quality of strawberry tree root soil sample;
(B) sample purification: by SRResin-B resin wet method dress post, with the nitric acid of 1+1 and water alternately cleaning pillar 2 ~ 3 times, then successively with the nitric acid of 1+1, 6mol/L hydrochloric acid and washing post, again with the nitric acid balance pillar of 3mol/L, get digestion solution a prepared by step (A) respectively, b, c, d or e upper prop, first use the drip washing of 3mol/L nitric acid, use the drip washing of 0.03mol/L nitric acid again, then use 6mol/L hydrochloric acid wash-out plumbous, collect plumbous eluent in the molten sample cup of teflon, be placed in evaporate to dryness on electric hot plate, then add red fuming nitric acid (RFNA) to dissolve, seal 150 DEG C of heating 1h, uncap again, in 150 DEG C of evaporates to dryness, obtain plumbous sample a respectively, b, c, d, e,
(C) hot surface ionization mass spectrometer is adopted to measure plumbous isotopic ratio:
(C-1) pre-service of sample belt
First rhenium band is put into ethanol and soak 30min ~ 60min, take out after drying, rhenium band is spoted weld on sample introduction support, be then placed in the device that degass and degas, obtain pretreated rhenium band;
(C-2) plumbous painting sample
The 20mmol/L phosphoric acid pipetting 1 μ L with micropipettor is added on pretreated rhenium band central authorities, energising evaporate to dryness, add 1 μ L silica gel cast charge again on phosphoric acid, energising evaporate to dryness, plumbous sample a, b, c, d, e of step (B) being prepared use the nitric acid dissolve of massfraction 3% respectively, then the silica gel place in rhenium band is put respectively, energising evaporate to dryness, 1 μ L silica gel cast charge is dripped again in sample place, be energized after energising evaporate to dryness reddening sample belt, then sample introduction support loaded the sample disc of hot surface ionization mass spectrometer;
(C-3) plumbous mass spectrum isotopic ratio detects
Hot surface ionization mass spectrometer vacuumizes, and vacuum tightness reaches 3 × 10
-7during Pa, rhenium band is heated, tests, temperature is controlled at 1250 ± 50 DEG C, detect and obtain plumbous isotopic ratio
207pb/
206pb and
208pb/
206pb.
Compared with prior art, the advantage of the method is as follows:
The present invention utilizes isotopic ratio plumbous in hot surface ionization mass spectrometer Fast Measurement strawberry tree different parts sample first, this ratio be strawberry tree one " natural fingerprint ", and do not change with the change of chemical addition agent, can trace to the source for red bayberry and a kind of science is provided, independently, identity authentication information that is unmodifiable and that flow with whole food chain, method is reliable and stable.Special in the product between extensive area, can effectively distinguish its difference.The method is few with acid in pretreatment process, environmental protection; Spend the post time short, can realize the quick separating of lead element, detection efficiency is high; The method is through sample pre-treatments, and matrix impact is little, and interference is few, and testing result precision is high, effective.
Accompanying drawing explanation
The correlativity distribution plan of the isotopic ratio of the lead of Fig. 1 Different sources red bayberry sample.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail, but protection scope of the present invention is not limited thereto.
The mensuration of the isotopic ratio of the lead of embodiment 1 Cixi place of production strawberry tree different parts sample
Red bayberry sample, strawberry tree Leaf samples, red bayberry branch samples, strawberry tree tree root sample or strawberry tree root soil sample be respectively by after red bayberry, strawberry tree leaf, strawberry tree branch, strawberry tree tree root or the drying of strawberry tree root soil with ceramic scissors cut little after, then grind obtained with mortar.
(1) take 1g red bayberry sample respectively, add 10mL red fuming nitric acid (RFNA); 0.5g Leaf samples, adds 9mL red fuming nitric acid (RFNA); The pedotheque of 0.3g strawberry tree root 10cm depths, adds 10mL chloroazotic acid and 2mL hydrofluorite; 0.5g strawberry tree branch samples, adds 10mL red fuming nitric acid (RFNA); 0.3g strawberry tree tree root sample, adds 7mL red fuming nitric acid (RFNA);
Put into microwave dissolver (Multiwave3000 that Anton Paar company produces) respectively to clear up, heating schedule is that 5min is raised to 400w, keep 5min, then 5min rises to 800w, and keep 5min, cooling down is to room temperature.After having cleared up, mixing material is proceeded to the molten sample cup of 15mL teflon, be positioned over 150 DEG C of heating evaporates to dryness on electric hot plate, with centrifugal after 1mL3mol/L nitric acid dissolve, obtain digestion solution for subsequent use.
(2) by SRResin-B resin (Trskem company produces, 100-150 μm of particle diameter) wet method dress post, each pillar fills the SRResin-B resin of 200 μ l volumes.With the nitric acid of 1+1 and water alternately cleaning pillar 3 times, then post is washed with 1mL1+1 nitric acid, 2mL6mol/L hydrochloric acid and 2mL successively, 1mL3mol/L nitric acid balance pillar, get pillar on digestion solution sample 0.5mL prepared by step (1), with the drip washing of 3mL3mol/L nitric acid, the drip washing of 2.5mL0.03mol/L nitric acid, 3mL6mol/L hydrochloric acid wash-out is plumbous, use 2mL6mol/L hydrochloric acid successively again, post is washed in 2mL1+1 nitric acid and 2mL water reuse (treatment.The plumbous eluent of collection 3mL6mol/L hydrochloric acid wash-out, in the molten sample cup of 5mL teflon, is placed in 150 DEG C of evaporates to dryness on electric hot plate, then adds 1mL red fuming nitric acid (RFNA), and seal 150 DEG C of heating 1h, uncap, 150 DEG C of evaporates to dryness, obtain plumbous sample for subsequent use.
(3) hot surface ionization mass spectrometer (ThermoTritonPlus mass spectrometer) measures plumbous isotopic ratio
The pre-service of sample belt
First rhenium band is put into ethanol and soak 40min, after taking-up is dried, rhenium band is spoted weld on plug-in unit, be then placed in mass spectrum filament and degas device (Beijing Yi Guanjing instrument Science and Technology Ltd.), successively respectively to degas 15min with the electric current of 1A and 4A, obtain pretreated rhenium band.
Plumbous painting sample
With plumbous sample prepared by the nitric acid dissolve step (2) of massfraction 3%, the 20mmol/L phosphoric acid of 1uL is pipetted in pretreated rhenium band central authorities with micropipettor, energising 0.8A evaporate to dryness, add 1 μ L silica gel cast charge again on phosphoric acid, energising evaporate to dryness, and then by the plumbous sampling point after dissolving in the silica gel place of rhenium band, energising evaporate to dryness, 1 μ L silica gel cast charge is dripped again in sample place, be energized after energising evaporate to dryness 2.2A reddening sample belt, then sample introduction support loaded the sample disc of hot surface ionization mass spectrometer.
Described silica gel cast charge is prepared by the following method: take 0.1g silicic acid and fully grinding, and after using massfraction 10% nitric acid and water washing 3 times successively, centrifugal, abandoning supernatant, residue adds 10mL0.1mol/L phosphoric acid and shakes up, obtained described silica gel cast charge.
Plumbous mass spectrum isotopic ratio detects
Hot surface ionization mass spectrometer vacuumizes, and treat mass spectrometer normal operation, vacuum tightness reaches 3 × 10
-7during Pa, rhenium band is heated, temperature is controlled at 1250 ± 50 DEG C, measure plumbous isotopic ratio
207pb/
206pb and
208pb/
206pb.
Acquired results sees the following form 1
Table 1:
Embodiment 2
Get the red bayberry sample in Cixi, Yuyao, three places of production, Wenzhou, measure plumbous isotopic ratio according to the method step of embodiment 1
207pb/
206pb and
206pb/
208pb, does correlativity distribution plan, and as shown in Figure 1, Fig. 1 can find out, there is significant difference between the isotope ratio Distribution value of the lead in three places of production, each own different distributed area.Therefore Fig. 1 may be used for the red bayberry differentiating Different sources.To the red bayberry sample in the unknown place of production, measure plumbous isotopic ratio
207pb/
206pb and
206pb/
208which distributed area Pb, observe its numeric distribution near, then can be accredited as the place of production of this distributed area.
Claims (8)
1. to measure in strawberry tree different parts sample plumbous isotopic ratio and identify the method in the red bayberry place of production, it is characterized in that said method comprising the steps of:
(1) isotopic ratio plumbous in strawberry tree different parts sample is measured:
(A) sample pre-treatments: take strawberry tree different parts sample, described strawberry tree different parts sample comprises red bayberry sample, strawberry tree Leaf samples, strawberry tree branch samples, red bayberry tree root sample or strawberry tree root soil sample, then add respectively and clear up reagent, obtain biased sample a, b, c, d or e, be placed in microwave dissolver respectively to clear up, the heating schedule arranging microwave dissolver is: 5min is raised to 400w, keep 5min, 5min rises to 800w again, keep 5min, cooling down is to room temperature, gained mixed liquor heating evaporate to dryness, with centrifugal after 3mol/L nitric acid dissolve, obtain digestion solution a respectively, b, c, d or e is for subsequent use,
Describedly take strawberry tree different parts sample, add respectively and clear up reagent, obtain biased sample a, b, c, d or e, concrete by following operation:
A () takes red bayberry sample, add red fuming nitric acid (RFNA), obtains biased sample a, and the volumetric usage of described red fuming nitric acid (RFNA) counts 10mL/g with the quality of red bayberry sample;
B () takes strawberry tree Leaf samples, add red fuming nitric acid (RFNA), obtains biased sample b, and the volumetric usage of described red fuming nitric acid (RFNA) counts 18mL/g with the quality of strawberry tree Leaf samples;
C () takes strawberry tree branch samples, add red fuming nitric acid (RFNA), obtains biased sample c, and the volumetric usage of described red fuming nitric acid (RFNA) counts 20mL/g with the quality of strawberry tree branch samples;
D () takes strawberry tree tree root sample, add red fuming nitric acid (RFNA), obtains biased sample d, and the volumetric usage of described red fuming nitric acid (RFNA) counts 23 ~ 24mL/g with the quality of strawberry tree tree root sample;
E () takes strawberry tree root soil sample, adding volume ratio is the chloroazotic acid of 5:1 and the mix acid liquor of hydrofluorite, obtains biased sample e, and the volumetric usage of described mix acid liquor counts 40mL/g with the quality of strawberry tree root soil sample;
(B) sample purification: by SRResin-B resin wet method dress post, with the nitric acid of 1+1 and water alternately cleaning pillar 2 ~ 3 times, then successively with the nitric acid of 1+1, 6mol/L hydrochloric acid and washing post, again with the nitric acid balance pillar of 3mol/L, get digestion solution a prepared by step (A) respectively, b, c, d or e upper prop, first use the drip washing of 3mol/L nitric acid, use the drip washing of 0.03mol/L nitric acid again, then use 6mol/L hydrochloric acid wash-out plumbous, collect plumbous eluent in the molten sample cup of teflon, be placed in evaporate to dryness on electric hot plate, then add red fuming nitric acid (RFNA) to dissolve, seal 150 DEG C of heating 1h, uncap again, in 150 DEG C of evaporates to dryness, obtain plumbous sample a respectively, b, c, d, e,
(C) hot surface ionization mass spectrometer is adopted to measure plumbous isotopic ratio:
(C-1) pre-service of sample belt
First rhenium band is put into ethanol and soak 30min ~ 60min, take out after drying, rhenium band is spoted weld on sample introduction support, be then placed in the device that degass and degas, obtain pretreated rhenium band;
(C-2) plumbous painting sample
The 20mmol/L phosphoric acid pipetting 1 μ L with micropipettor is added on pretreated rhenium band central authorities, energising evaporate to dryness, add 1 μ L silica gel cast charge again on phosphoric acid, energising evaporate to dryness, plumbous sample a, b, c, d, e of step (B) being prepared use the nitric acid dissolve of massfraction 3% respectively, then the silica gel place in rhenium band is put respectively, energising evaporate to dryness, 1 μ L silica gel cast charge is dripped again in sample place, be energized after energising evaporate to dryness reddening sample belt, then sample introduction support loaded the sample disc of hot surface ionization mass spectrometer;
(C-3) plumbous mass spectrum isotopic ratio detects
Hot surface ionization mass spectrometer vacuumizes, and vacuum tightness reaches 3 × 10
-7during Pa, rhenium band is heated, tests, temperature is controlled at 1250 ± 50 DEG C, detect and obtain plumbous isotopic ratio
207pb/
206pb and
208pb/
206pb;
(2) the plumbous isotopic ratio qualification red bayberry place of production is utilized
According to the method for step (1), get the isotopic ratio of the sample determination lead of the strawberry tree different parts of Different sources respectively, the isotopic ratio getting the lead of the sample of Different sources same area does correlativity distribution plan, can be used for the place of production situation of the strawberry tree sample identifying the unknown place of production.
2. the method for claim 1, it is characterized in that in described step (A), red bayberry sample, strawberry tree Leaf samples, red bayberry branch samples, strawberry tree tree root sample or strawberry tree root soil sample be respectively by after red bayberry, strawberry tree leaf, strawberry tree branch, strawberry tree tree root or the drying of strawberry tree root soil with ceramic scissors cut little after, then grind obtained with mortar.
3. the method for claim 1, is characterized in that in described step (A), the Multiwave3000 microwave dissolver that described microwave dissolver adopts Anton Paar company to produce.
4. the method for claim 1, is characterized in that in described step (B), the nitric acid of described 1+1 be by red fuming nitric acid (RFNA) and water by volume 1:1 mixed preparing obtain.
5. the method for claim 1, is characterized in that in described step (B), after 6mol/L hydrochloric acid wash-out lead, cleans pillar of living again according to the following steps: successively with nitric acid and the washing post of 6mol/L hydrochloric acid, 1+1.
6. the method for claim 1, is characterized in that described step (B) operates by the following method:
By SRResin-B resin wet method dress post, with the nitric acid of 1+1 and water alternately cleaning pillar 2 ~ 3 times, then successively with the nitric acid of the 1+1 of 5 times of column volumes, the washing post of the 6mol/L hydrochloric acid of 10 times of column volumes and 10 times of column volumes, again with the nitric acid balance pillar of the 3mol/L of 5 times of column volumes, get digestion solution a prepared by step (A) respectively, b, c, d or e upper prop, first use the 3mol/L nitric acid drip washing of 15 times of column volumes, use the 0.03mol/L nitric acid drip washing of 12.5 times of column volumes again, then use the 6mol/L hydrochloric acid wash-out of 15 times of column volumes plumbous, collect plumbous eluent in the molten sample cup of teflon, be placed in evaporate to dryness on electric hot plate, then add red fuming nitric acid (RFNA) to dissolve, seal 150 DEG C of heating 1h, uncap again, in 150 DEG C of evaporates to dryness, obtain plumbous sample a respectively, b, c, d, e, use the 6mol/L hydrochloric acid of 10 times of column volumes more successively, the water of the nitric acid of the 1+1 of 10 times of column volumes and 10 times of column volumes cleans pillar of living again.
7. the method for claim 1, it is characterized in that in described step (C-2), described silica gel cast charge is by following proportions: take 0.1g silicic acid and fully grinding, after using massfraction 10% nitric acid and water washing 3 ~ 5 times successively, centrifugal, abandoning supernatant, residue adds 10mL0.1mol/L phosphoric acid and shakes up, obtained described silica gel cast charge.
8. measure a method for isotopic ratio plumbous in strawberry tree different parts sample, it is characterized in that said method comprising the steps of:
(A) sample pre-treatments: take strawberry tree different parts sample, described strawberry tree different parts sample comprises red bayberry sample, strawberry tree Leaf samples, strawberry tree branch samples, red bayberry tree root sample or strawberry tree root soil sample, then add respectively and clear up reagent, obtain biased sample a, b, c, d or e, be placed in microwave dissolver respectively to clear up, the heating schedule arranging microwave dissolver is: 5min is raised to 400w, keep 5min, 5min rises to 800w again, keep 5min, cooling down is to room temperature, gained mixed liquor heating evaporate to dryness, with centrifugal after 3mol/L nitric acid dissolve, obtain digestion solution a respectively, b, c, d or e is for subsequent use,
Describedly take strawberry tree different parts sample, add respectively and clear up reagent, obtain biased sample a, b, c, d or e, concrete by following operation:
A () takes red bayberry sample, add red fuming nitric acid (RFNA), obtains biased sample a, and the volumetric usage of described red fuming nitric acid (RFNA) counts 10mL/g with the quality of red bayberry sample;
B () takes strawberry tree Leaf samples, add red fuming nitric acid (RFNA), obtains biased sample b, and the volumetric usage of described red fuming nitric acid (RFNA) counts 18mL/g with the quality of strawberry tree Leaf samples;
C () takes strawberry tree branch samples, add red fuming nitric acid (RFNA), obtains biased sample c, and the volumetric usage of described red fuming nitric acid (RFNA) counts 20mL/g with the quality of strawberry tree branch samples;
D () takes strawberry tree tree root sample, add red fuming nitric acid (RFNA), obtains biased sample d, and the volumetric usage of described red fuming nitric acid (RFNA) counts 23 ~ 24mL/g with the quality of strawberry tree tree root sample;
E () takes strawberry tree root soil sample, adding volume ratio is the chloroazotic acid of 5:1 and the mix acid liquor of hydrofluorite, obtains biased sample e, and the volumetric usage of described mix acid liquor counts 40mL/g with the quality of strawberry tree root soil sample;
(B) sample purification: by SRResin-B resin wet method dress post, with the nitric acid of 1+1 and water alternately cleaning pillar 2 ~ 3 times, then successively with the nitric acid of 1+1, 6mol/L hydrochloric acid and washing post, again with the nitric acid balance pillar of 3mol/L, get digestion solution a prepared by step (A) respectively, b, c, d or e upper prop, first use the drip washing of 3mol/L nitric acid, use the drip washing of 0.03mol/L nitric acid again, then use 6mol/L hydrochloric acid wash-out plumbous, collect plumbous eluent in the molten sample cup of teflon, be placed in evaporate to dryness on electric hot plate, then add red fuming nitric acid (RFNA) to dissolve, seal 150 DEG C of heating 1h, uncap again, in 150 DEG C of evaporates to dryness, obtain plumbous sample a respectively, b, c, d, e,
(C) hot surface ionization mass spectrometer is adopted to measure plumbous isotopic ratio:
(C-1) pre-service of sample belt
First rhenium band is put into ethanol and soak 30min ~ 60min, take out after drying, rhenium band is spoted weld on sample introduction support, be then placed in the device that degass and degas, obtain pretreated rhenium band;
(C-2) plumbous painting sample
The 20mmol/L phosphoric acid pipetting 1 μ L with micropipettor is added on pretreated rhenium band central authorities, energising evaporate to dryness, add 1 μ L silica gel cast charge again on phosphoric acid, energising evaporate to dryness, plumbous sample a, b, c, d, e of step (B) being prepared use the nitric acid dissolve of massfraction 3% respectively, then the silica gel place in rhenium band is put respectively, energising evaporate to dryness, 1 μ L silica gel cast charge is dripped again in sample place, be energized after energising evaporate to dryness reddening sample belt, then sample introduction support loaded the sample disc of hot surface ionization mass spectrometer;
(C-3) plumbous mass spectrum isotopic ratio detects
Hot surface ionization mass spectrometer vacuumizes, and vacuum tightness reaches 3 × 10
-7during Pa, rhenium band is heated, tests, temperature is controlled at 1250 ± 50 DEG C, detect and obtain plumbous isotopic ratio
207pb/
206pb and
208pb/
206pb.
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