CN101762558A - Matrix modifier for determining heavy metals absorbed by graphite furnace atoms and preparing method - Google Patents
Matrix modifier for determining heavy metals absorbed by graphite furnace atoms and preparing method Download PDFInfo
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- CN101762558A CN101762558A CN201010028121A CN201010028121A CN101762558A CN 101762558 A CN101762558 A CN 101762558A CN 201010028121 A CN201010028121 A CN 201010028121A CN 201010028121 A CN201010028121 A CN 201010028121A CN 101762558 A CN101762558 A CN 101762558A
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Abstract
The invention discloses a matrix modifier for determining heavy metals absorbed by graphite furnace atoms, and a preparing method. The matrix modifier is colloid palladium, and the preparing method of the matrix modifier comprises the following steps of: weighing 0.024g-0.036g of palladium chloride, and placing into a reacting container; converting into H2PdC14.nH2O by using concentrated hydrochloric acid; adding 0.030g of polyvinylpyrrolidone; then, slowly adding 60mL of mixing solution of methanol and water, continuously stirring and uniformly mixing in the adding process, placing the solution into a water bath tank for refluxing by heating for 90 minutes, and then taking out a brown colloid solution which is the target palladium. The novel matrix modifier can achieve high podzolizing temperature, the interference matrix can be effectively removed in the podzolizing stage, and the purpose for reducing or eliminating the interference is achieved. The colloid palladium prepared by the invention has uniform particle distribution, and no obvious aggregation phenomenon.
Description
Technical field
The present invention relates to a kind of matrix modifier and preparation method who is used for determining heavy metals absorbed by graphite furnace atoms.
Background technology
Heavy metal is meant that generally atomic weight greater than 55 metal, mostly is transitional element.As copper, lead, zinc, iron, cobalt, nickel, manganese, cadmium, mercury, tungsten, molybdenum, gold, silver etc.Although heavy metals such as manganese, copper, zinc are the needed trace elements of vital movement, it is necessary that most of heavy metal such as mercury, lead, cadmium etc. are not vital movement institute, and all heavy metals are all harmful above finite concentration.In addition, though arsenic does not belong to heavy metal, because of its source and harm all similar to heavy metal, study so list the heavy metal class usually in, the discussion.Along with toxicologic progress, the nerve and the chronic toxicity of heavy metals such as lead, mercury, thallium, arsenic are more and more clearly illustrated, and meanwhile, problems such as industrial expansion and environmental pollution also make heavy metal element more and more nearer from daily life.
Along with the spectrophotometric widespread use of present sampling Graphite Furnace Atomic Absorption with to the raising of the accuracy requirement of trace heavy metal ultimate analysis, how to reduce effectively even eliminate matrix in the determining heavy metals and disturb and become one of important topic.Constant temperature atomization, the graphite-pipe coating, Zeeman effect button background, technology such as pulse heating technique and matrix modifier have applied to the analysis of sampling Graphite Furnace Atomic Absorption at present, all can eliminate matrix within the specific limits to some extent and disturb, improve sensitivity and improve precision.Matrix improves technology, promptly refer in testing sample solution, add a certain chemical reagent, thereby the matrix composition is transformed into more volatile compound, or be more stable compound with element transformation to be measured, so that allow higher ashing temperature, can more effectively remove the interference matrix in the ashing stage, reach the purpose that reduces or eliminates interference.This technology since 1973 are proposed by Ediger, development rapidly, and towards efficiently, economy is easy to prepare with the novel matrix modifier direction of preserving constantly progressive.The palladium matrix modifier be exactly wherein study comparatively successful typical case.
The compound palladium matrix modifier that is suggested the earliest is a palladium bichloride, the oxide of Metal Palladium and palladium is considered to the activity form of palladium matrix modifier usually, one class matrix modifier is a palladium bichloride, the compound of palladiums such as palladium nitrate, this class improver substantially all needs logical hyperthermia to make it to be converted into the palladium of active character, such pre-treatment mode can make increases 30-40% analysis time, and can not stablize the volatility analyte; Another kind of then is the potpourri of palladium compound and reductive agent, and the major defect of this class improver may be that its reappearance is not good.
Summary of the invention
Technical matters to be solved by this invention provides a kind of matrix modifier and preparation method who is used for determining heavy metals absorbed by graphite furnace atoms, the invention provides new matrix modifier and can reach higher ashing temperature, can more effectively remove the interference matrix in the ashing stage, reach the purpose that reduces or eliminates interference.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: be used for the matrix modifier of determining heavy metals absorbed by graphite furnace atoms, described matrix modifier is a colloid palladium.
Described colloid palladium is applied to the sampling Graphite Furnace Atomic Absorption of lead, arsenic, mercury, cadmium, thallium, selenium, tin, germanium and measures.
A kind of preparation method of the above-mentioned matrix modifier that is used for determining heavy metals absorbed by graphite furnace atoms comprises the steps: to take by weighing the 0.024g-0.036g palladium bichloride and places reaction vessel, is converted into H with concentrated hydrochloric acid
2PdCl
4NH
2O adds the 0.030g polyvinylpyrrolidone again, slowly add then the first alcohol and water mixed solution 60mL, continuous stirring and evenly mixing in the adition process places the water bath reflux to take out after 90 minutes solution, the brown colloidal solution that obtains is colloid palladium.
Particularly, the concentration of described palladium bichloride is 0.4mg/mL-0.6mg/mL.
The concentration of described polyvinylpyrrolidone is 0.5mg/mL.
The concentration of above-mentioned palladium bichloride, the concentration of polyvinylpyrrolidone are and add its concentration in solution behind solid palladium chloride, the solid polyethylene pyrrolidone.
The volume ratio of described first alcohol and water is 1: 1.
Because the palladium of metallic state has shown very high effectiveness stablizing on the volatile analyte, so the colloid palladium matrix modifier is very potent in reaction.It can either drying stage promptly with element interaction to be measured, not reacting with the overwhelming majority's matrix under the temperature of appropriateness again changes, and can preserve for a long time and do not lose efficacy.After deliberation, the result confirms with colloid palladium to eliminate sodion as matrix modifier, and chlorion has an effect preferably during sulfate ion and glucose disturb, and compares with other matrix modifier, has verified the superiority of part.Colloid palladium is a kind of matrix modifier that is rich in prospect at present.
To sum up, the invention has the beneficial effects as follows:
1, the invention provides new matrix modifier and can reach higher ashing temperature, can more effectively remove the interference matrix, reach the purpose that reduces or eliminates interference in the ashing stage.
2, the preparation method of matrix modifier provided by the invention, the colloid palladium even particle distribution of preparation does not have obvious agglomeration.
Description of drawings
Fig. 1 is a colloid palladium transmission electron microscope phenogram;
Fig. 2 is that ethanol, water volume ratio are the transmission electron microscope picture of the colloid palladium of preparation in 1: 1;
Fig. 3 is that methyl alcohol, water volume ratio are the Electronic Speculum phenogram of the colloid palladium of preparation in 7: 3 o'clock;
Fig. 4 is that methyl alcohol, water volume ratio are the Electronic Speculum phenogram of the colloid palladium of preparation in 3: 7 o'clock;
Fig. 5 is 1200 ℃ of colloid palladium improvers of ashing temperature sample signal;
Fig. 6 is 1200 ℃ of no improver standard signals of ashing temperature;
Fig. 7 is the arsenic sample mark-on signal graph that adopts sampling Graphite Furnace Atomic Absorption to measure;
Fig. 8 is the arsenic sample signal figure that adopts sampling Graphite Furnace Atomic Absorption to measure;
Fig. 9 is the thallium standard signal figure that adopts sampling Graphite Furnace Atomic Absorption to measure;
The thallium sample signal figure that Figure 10 adopts sampling Graphite Furnace Atomic Absorption to measure;
Figure 11 is the cadmium standard signal figure that adopts sampling Graphite Furnace Atomic Absorption to measure;
Figure 12 is the cadmium sample signal figure that adopts sampling Graphite Furnace Atomic Absorption to measure.
Embodiment
Embodiment 1:
1, the preparation of colloid palladium
In round-bottomed flask, take by weighing 0.024g-0.036g (0.4mg/mL-0.6mg/mL) palladium bichloride, be converted into H with concentrated hydrochloric acid
2PdCl
4NH
2O, add 0.030g (0.5mg/mL) polyvinylpyrrolidone (PVP) again, slowly add then 1: 1 first alcohol and water mixed solution 60mL, continuous stirring and evenly mixing in the adition process, place the water bath reflux to take out after 90 minutes solution, the brown colloidal solution that obtains is colloid palladium.
2, the quality control of colloid palladium
A colloid palladium solution example is dropped on the copper mesh that is coated with carbon film, dry naturally.On transmission electron microscope, observe.The size of metallic particles and size distribution thereof are by carrying out obtaining behind the statistical measurement to being not less than 200 particles on the electromicroscopic photograph after amplifying.
Measure the content of beary metal of the colloid palladium matrix modifier of preparation with graphite furnace atomic absorption photometer, monitor its background content.
3, the application of colloid palladium
The colloid palladium that this method prepares can be applicable to lead, arsenic, and mercury, cadmium, thallium, selenium, the sampling Graphite Furnace Atomic Absorption of tin and germanium is measured.The ashing temperature after it improves and the ashing temperature of common matrix modifier see Table 1.
Table 1 colloid palladium and common matrix modifier ashing temperature are relatively
Annotate: * is the ashing temperature of no matrix modifier
Referring to Fig. 5, shown in Figure 6, be respectively 1200 ℃ of colloid palladium improvers of ashing temperature sample signal, 1200 ℃ of no improver standard signals of ashing temperature, by diagram as can be known, after adding matrix modifier of the present invention in the testing sample solution, can allow higher ashing temperature, can more effectively remove the interference matrix in the ashing stage, reach the purpose that reduces or eliminates interference.
In the preparation method of colloid palladium, to the selection of alcohol
Attempted methyl alcohol and ethanol respectively with the combination of water.As seen from Figure 2, the colloid palladium agglomeration of second alcohol and water preparation is obvious, and the colloidal particle size size distribution is inhomogeneous, and particle diameter is all less.The colloid palladium Electronic Speculum phenogram of methanol-water preparation is seen Fig. 1, and the volume ratio of first alcohol and water is 1: 1 among Fig. 1, and the colloid palladium even particle distribution of preparation does not have obvious agglomeration, and particle shape is rule.So select the first alcohol and water as solvent.
The methyl alcohol ratio
Examined or check the influence that different methyl alcohol and water volume ratio form colloid palladium.The methanol-water gained colloid palladium Electronic Speculum figure of 1: 1 volume ratio sees Fig. 1, even particle distribution, and size is consistent.The colloid palladium Electronic Speculum phenogram of the methanol-water preparation of 7: 3 volume ratios is seen Fig. 3, the obvious agglomeration of colloid palladium particle, and dispersion degree is relatively poor, and adhesion is arranged between the particle.The colloid palladium of the methanol-water of 3: 7 volume ratios is seen Fig. 4 through the transmission electron microscope phenogram, finds from figure, and small size particle is more, and certain gathering is arranged.Therefore take all factors into consideration and select the methanol aqueous solution of 1: 1 volume ratio preferable.
The palladium bichloride consumption
Determine colloid palladium particle diameter and the distribution no significant difference that the palladium bichloride of 0.4mg/mL-0.6mg/mL (with respect to methanol aqueous solution) prepares by condition experiment.
The quality control of colloid palladium
A colloid palladium solution example is dropped on the copper mesh that is coated with carbon film, dry naturally.On transmission electron microscope, observe.The size of metallic particles and size distribution thereof are by carrying out obtaining behind the statistical measurement to being not less than 200 particles on the electromicroscopic photograph after amplifying.
Measure the content of beary metal of the colloid palladium matrix modifier of preparation with graphite furnace atomic absorption photometer, monitor its background content.
Embodiment 2:
Food arsenic is measured
Arsenic easily combines with sulfydryl, thereby causes that enzyme, coenzyme and the protein biologically active and the function that contain sulfydryl change.Arsenic is determined as conventional project in the food.Food samples is constant volume after acid digestion, the sampling Graphite Furnace Atomic Absorption spectrophotometric determination.Sample introduction 20 μ L, colloid palladium matrix modifier volume 5 μ L.Program sees Table 2.Signal is seen Fig. 7, Fig. 8.
The colloid palladium matrix modifier of table 2 arsenic-sampling Graphite Furnace Atomic Absorption is measured program
Referring to Fig. 7, shown in Figure 8, be respectively food samples mark-on and food samples background signal under 1200 ℃ of colloid palladium improvers of ashing temperature, as seen from the figure, after adding matrix modifier of the present invention in the testing sample solution, the peak shape symmetry is sharp-pointed, and interference can effectively be deducted, and sample is quantitatively accurate.
Embodiment 3:
The urine thallium is measured
Thallium and compound thereof belong to the hypertoxic type material, the tool property accumulated.Main infringement central nervous system, peripheral nerve and liver kidney also can cause trichomadesis.The urine thallium is an index of biological monitoring preferably.Graphite furnace atomic absorption photometer is measured, but the urine sample direct injection analysis.Sample introduction 15 μ L, colloid palladium matrix modifier 5 μ L.Program sees Table 3.Signal is seen Fig. 9, Figure 10.
The colloid palladium matrix modifier of table 3 thallium-sampling Graphite Furnace Atomic Absorption is measured program
Fig. 9,10 is respectively 1100 ℃ of colloid palladium improvers of ashing temperature and participates in thallium standard and poisoning urine sample signal down, as seen from the figure, after adding matrix modifier of the present invention in the biological material specimens solution, ashing temperature increase space is obviously strengthened, and matrix interference can effectively be reduced and deduct.
Embodiment 4:
The food cadmium is measured
Cadmium is in cell and contain carboxyl, amino, and the protein molecular combination of sulfydryl forms insoluble cadmium protein salt, causes the enzyme system inactivation.Disturb the metabolism of indispensable elements such as copper, cobalt, zinc, influence kidney merit liver function.Bring out prostate cancer and respiratory cancer, can teratogenesis.It also is one of heavy metal of routine monitoring in the food.Food behind acid digestion constant volume, the sampling Graphite Furnace Atomic Absorption spectrophotometric determination.Sample introduction 15 μ L, colloid palladium matrix modifier volume 5 μ L.Program sees Table 4.Signal is seen Figure 11, Figure 12.
The colloid palladium matrix modifier of table 4 cadmium-sampling Graphite Furnace Atomic Absorption is measured program
Figure 11,12 represents to add 1200 ℃ of following cadmium standards of ashing temperature and food samples measured signal behind the colloid palladium improver respectively, as seen from the figure, add matrix modifier of the present invention, can realize significantly improving of ashing temperature, stablize composition to be measured, and then reduce and disturb, finish the cadmium content of foodstuff matrix complex sample is measured.
Embodiment 5:
Food is plumbous to be measured
Plumbous toxicity is bigger, and the saturnism meeting causes the porphyrin metabolism disorder, causes the protoheme dyssynthesis; It can also combine with protein sulfhydryl, suppresses the cellular respiration pigment and generates.The food sample behind acid digestion constant volume, sampling Graphite Furnace Atomic Absorption spectrophotometric determination lead.Sample introduction 15 μ L, colloid palladium matrix modifier volume 5 μ L.Program sees Table 5.Signal is seen Fig. 5.
The colloid palladium matrix modifier of table 5 lead-sampling Graphite Furnace Atomic Absorption is measured program
Fig. 5 has shown and has added behind the colloid palladium improver plumbous measured signal in ashing temperature 1200 ℃ of following food samples, can find out, adds matrix modifier of the present invention, interference in the matrix reduces because of the raising of ashing temperature, remainingly can be taken as background deduction, the peak shape symmetry does not have obvious broadening yet.
Claims (7)
1. be used for the matrix modifier of determining heavy metals absorbed by graphite furnace atoms, it is characterized in that, described matrix modifier is a colloid palladium.
2. the matrix modifier that is used for determining heavy metals absorbed by graphite furnace atoms according to claim 1 is characterized in that, described colloid palladium is applied to the sampling Graphite Furnace Atomic Absorption of lead, arsenic, mercury, cadmium, thallium, selenium, tin, germanium and measures.
3. the described preparation method who is used for the matrix modifier of determining heavy metals absorbed by graphite furnace atoms of claim 1 is characterized in that, comprises the steps: to take by weighing the 0.024g-0.036g palladium bichloride and places reaction vessel, is converted into H with concentrated hydrochloric acid
2PdCl
4NH
2O adds the 0.030g polyvinylpyrrolidone again, slowly add then the first alcohol and water mixed solution 60mL, continuous stirring and evenly mixing in the adition process places the water bath reflux to take out after 90 minutes solution, the brown colloidal solution that obtains is colloid palladium.
4. the preparation method who is used for the matrix modifier of determining heavy metals absorbed by graphite furnace atoms according to claim 3 is characterized in that, the concentration of described palladium bichloride is 0.4mg/mL-0.6mg/mL.
5. the preparation method who is used for the matrix modifier of determining heavy metals absorbed by graphite furnace atoms according to claim 3 is characterized in that, the concentration of described polyvinylpyrrolidone is 0.5mg/mL.
6. the preparation method who is used for the matrix modifier of determining heavy metals absorbed by graphite furnace atoms according to claim 3 is characterized in that, the volume ratio of described first alcohol and water is 1: 1.
7. the method for quality control of the prepared colloid palladium of a claim 3 is characterized in that, comprises the steps: a colloid palladium solution example is dropped on the copper mesh that is coated with carbon film, dries naturally; Observe on transmission electron microscope, the size of metallic particles and size distribution thereof are by to carrying out being not less than 200 particles behind the statistical measurement on the electromicroscopic photograph after amplifying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102706817A (en) * | 2012-06-04 | 2012-10-03 | 广西中烟工业有限责任公司 | Method for determining content of lead in hot melt adhesive |
| CN103265581A (en) * | 2013-06-08 | 2013-08-28 | 西安凯立化工有限公司 | Method for preparing bis(diphenylphosphino)alkane palladium dichloride complex |
| CN103698293A (en) * | 2013-12-30 | 2014-04-02 | 武汉新华扬生物股份有限公司 | Method for detecting cadmium of enzyme preparation |
| CN104458613A (en) * | 2014-12-02 | 2015-03-25 | 安徽皖仪科技股份有限公司 | Method for detecting trace metal elements in benzene |
| CN107367473A (en) * | 2017-07-07 | 2017-11-21 | 上海烟草集团有限责任公司 | A kind of method of chromium content in measure papermaking-method reconstituted tobaccos |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806489A (en) * | 1987-03-06 | 1989-02-21 | Varian Associates | Matrix modifier and method for modifying a matrix to improve analysis of metal constituents during graphite furnace atomic absorption spectroscopy |
| US5102626A (en) * | 1987-03-06 | 1992-04-07 | Varian Associates, Inc. | Matrix modifier for modifying a matrix to improve analysis of metal constituents during graphite furnace atomic absorption spectroscopy |
| CN1165199A (en) * | 1996-05-09 | 1997-11-19 | 厦门大学 | Solid matrix improver for graphate furnace atomic absorption and its manufacturing method |
| CN101294896B (en) * | 2008-06-23 | 2010-12-01 | 中国烟草总公司郑州烟草研究院 | Method for measuring cadmium content in smoke tipping paper |
-
2010
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102706817A (en) * | 2012-06-04 | 2012-10-03 | 广西中烟工业有限责任公司 | Method for determining content of lead in hot melt adhesive |
| CN102706817B (en) * | 2012-06-04 | 2014-12-03 | 广西中烟工业有限责任公司 | Method for determining content of lead in hot melt adhesive |
| CN103265581A (en) * | 2013-06-08 | 2013-08-28 | 西安凯立化工有限公司 | Method for preparing bis(diphenylphosphino)alkane palladium dichloride complex |
| CN103265581B (en) * | 2013-06-08 | 2016-03-30 | 西安凯立新材料股份有限公司 | A kind of preparation method of two (diphenylphosphine) alkane palladium chloride title complex |
| CN103698293A (en) * | 2013-12-30 | 2014-04-02 | 武汉新华扬生物股份有限公司 | Method for detecting cadmium of enzyme preparation |
| CN104458613A (en) * | 2014-12-02 | 2015-03-25 | 安徽皖仪科技股份有限公司 | Method for detecting trace metal elements in benzene |
| CN107367473A (en) * | 2017-07-07 | 2017-11-21 | 上海烟草集团有限责任公司 | A kind of method of chromium content in measure papermaking-method reconstituted tobaccos |
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