CN102854238A - Method for determination analysis of multiple heavy metals in environmental medium or biological sample - Google Patents
Method for determination analysis of multiple heavy metals in environmental medium or biological sample Download PDFInfo
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Abstract
The invention relates to a method for determination analysis of multiple heavy metals in an environmental medium or a biological sample. The method realizes determination of heavy metals such as Cd, Pb, As, Sb, Cu, Zn, Ni and Cr in an environmental medium and a biological sample by a microwave digestion-inductively coupled plasma mass spectrometry method, and belongs to a heavy metal element quantitative analysis method in the field of analytical chemistry. The method comprises the following steps of carrying out freeze drying of a sample, crushing, sieving, preserving the sieved sample in a drier, in determination analysis, weighing 0.1 to 1.0g of the sample, putting the sample into a Teflon digestion tank, adding 10 to 20ml of a mixed acid into the sample, carrying out pre-digestion of the sample for 20 to 40min, adding 0.5 to 2.0ml of hydrogen peroxide into the digested sample, putting the digested sample with hydrogen peroxide into a microwave digestion instrument, carrying out digestion by a programmed temperature method, then removing the acid in the digested sample, adding 2ml of hydrogen peroxide into the digested sample, putting the digested sample with hydrogen peroxide on a heating plate, carrying out digestion at a temperature of 110 DEG C for 5min, cooling to a room temperature, carrying out volume metering, and filtering for next determination. The method is suitable for different environmental mediums and biological samples and has high sensitivity, a low detection limit, a wide application range and a wide application prospect.
Description
Technical field
The present invention relates to chemical analysis field, it is the determination and analysis method of various heavy in a kind of surrounding medium or the biological sample, specifically, be the method that a kind of micro-wave digestion-inductively coupled plasma mass spectrometry is measured various heavy in surrounding medium and the biological sample.
Background technology
Micro-wave digestion is present the most frequently used Specimen eliminating method, its utilize in the microwave heating closed container digestion solution (various acid, part alkali lye and salt) thereby and sample various samples are dissolved fast.Because during ICP-MS working sample content of beary metal, its salinity to sample has high requirement, therefore, generally selects various acid as digestion solution.For environmental sample, surrounding medium sample such as soil, sediment etc. are cleared up because containing more and complicated being difficult to of matrix of indissoluble mineral matter, and the problems such as the sample content of organic matter is too high, fat emulsification then easily appear in biological sample because of the existence that contains protein, carbohydrate, phenols, oil substances.Therefore, commonly use the acid of the single uses such as the selected nitric acid of digestion solution, hydrochloric acid and can't satisfy clearing up of above-mentioned sample, need employing acid mixture such as chloroazotic acid, contrary chloroazotic acid etc. as the digestion solution of sample.
Chloroazotic acid is the most frequently used acid mixture, and being nitric acid and hydrochloric acid is configured with the volume ratio of 1:3.It can be used for dissolving and comprise many metals and the alloys such as steel, high-temperature alloy steel, aluminium alloy, antimony, chromium and platinum group metal, and iron ore, phosphate rock, slag and not diffluent mercury, arsenic, cobalt and plumbous sulfide.Contain a series of strong oxidizers such as nitric acid, chlorine and nitrosyl chloride in the chloroazotic acid, the chlorion that also has simultaneously high concentration, the oxidability of chloroazotic acid is stronger than nitric acid, and some are insoluble to the metals like gold, platinum etc. of nitric acid can be by aqua regia dissolution, and therefore chloroazotic acid is called as the king in " water ".The reaction equation of aqua regia dissolution gold and platinum is as follows:
Au+HNO
3+4HCl====H[AuCl
4]+NO+2H
2O
3Pt+4HNO
3+18HCl====3H
2[PtCl
6]+4NO+8H
2O
Although chloroazotic acid has the strong oxidability of the inert metals such as dissolving gold, platinum.But for the surrounding medium sample, although chloroazotic acid can pickling go out part metals from soil or sedimental silicate substrate, can't effectively dissolve fully.Use aqua regia dissolution element to be measured to be used for measuring mud such as the method for EPA3050B, soil, plumbous in the sediment, the contents of heavy metal elements such as cadmium, it is a non-method of clearing up fully, constituent content in the silicate sturcture can not dissolved out (http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/3050b.pdf), the analysis result of sample also is lower than EPA3052(and dissolves matrix with nitric acid-HF system, a method of clearing up fully, http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/3052.pdf).In addition, for biological sample, a high proportion of hydrochloric acid use amount also can cause the emulsification of oil substances.Therefore, chloroazotic acid can't be as the optimal digestion solution of environmental sample.
Contrary chloroazotic acid also is Le Fute (Lefort) chloroazotic acid, is the potpourri of three parts of nitric acid and a hydrochloric acid, and its oxidisability is stronger than chloroazotic acid, can dissolve the sulfide of the metal such as Ag, Hg, Mo and Fe, Mn, Ge.The reaction of contrary chloroazotic acid is different with chloroazotic acid, and its reactional equation is:
3HNO
3+HCl?====?H
2[(N
3O
8)Cl]+2H
2O
H
2[(N
3O
8)Cl]====?[(N
3O
8)Cl]
2-?+?2H
+
This complex of most of formation in the contrary chloroazotic acid also can obtain with fuming nitric aicd (two contractings, three nitric acid) dissolving hydrogen chloride.This cooperation still easily is decomposed into Cl without being colourless under normal conditions
2, NO
2, N
2O
4Therefore be salmon pink, also be referred to as traditionally red acid, in fact so-called " red acid " is complex H
2[(N
3O
8) Cl].H
2[(N
3O
8) Cl] ionization becomes ion fully in aqueous solution.Being the strong acid with strong oxidizing property, is pure substance under the 700KPa pressure, is the transparency liquid of colorless oil, decomposes under the normal temperature to produce nitrogen oxides and aobvious Chinese red, and strongly is fuming.This complex acid oxidisability is very strong, and its negative ion has good coordination.Therefore, be more suitable in the clearing up of the higher environmental and biological materials of organic matter, and it cooperates hydrofluorite to use the problem of clearing up that also can solve the surrounding medium samples such as soil, sediment.Simultaneously, nitric acid, hydrochloric acid and hydrofluorite are compared sulfuric acid, perchloric acid etc. and are all easily eliminated under lower temperature, can effectively avoid high temperature to catch up with the loss of the element to be measured that acid causes.
Atomic absorption spectrum (AAS), inductively coupled plasma emission/spectrum (ICP-AES) and inductively coupled plasma/mass spectrum (ICP-MS) are the Main Analysis instruments of content of beary metal in the working sample.Wherein, ICP-MS because of it has that detection limits is low, the range of linearity is wide, can detect simultaneously multiple element and efficiently, a plurality of advantages such as sample analysis ability fast, be widely used in this field at present.For environmental sample, because the matrix of sample is comparatively complicated, need that the heavy metal element kind that detects is more, the concentration difference between each element is larger, so how can be by rationally, effectively technical method reduces that ICP-MS analyzes that mass spectrum when measuring disturbs, matrix acid is disturbed, double-charge ion disturbs, matrix disturbs, ionization is disturbed and the influence factors such as space charge effect are the key points of problem.At present, can eliminate the interfering ion that hydrochloric acid, hydrofluorite etc. form in the digestion solution by catching up with sour mode, and control the acid concentration of element to be measured, thereby the matrix that reduces in the ICP-MS analytic process disturbs.But that usually selects catches up with sour temperature substantially more than 140 ℃, can cause the loss of the multiple volatile heavy metals such as As, Sb.Such as AsCl
3And SbCl
3Boiling point be respectively 130 ℃ and 220 ℃, the existence of hydrochloric acid in the sample solution can cause both boiling points further to reduce, thus the As in the sample solution and Sb also can form AsCl with chlorion
3And SbCl
3And a large amount of volatilizations.
Obviously, existing method can not satisfy the analysis of the more and environmental sample that concentration difference is larger of more complicated, the to be measured element of matrix.Therefore, this method forms a kind of determination and analysis method that is applicable to various heavy in the environmental sample by the change to prior art.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, form that a kind of sample applicability is wide, simple to operate, the determination and analysis method of various heavy in the surrounding medium that can clear up simultaneously and the biological sample.
The determination and analysis method of various heavy in the surrounding medium that the present invention proposes and the biological sample, concrete steps are as follows:
(1). the micro-wave digestion of surrounding medium or biological sample
Surrounding medium sample or biological sample are crossed 80-100 mesh sieve (the time spent is not put in the exsiccator and preserves) after freeze drying, pulverizing, take by weighing sample 0.1-1.0 g(and be accurate to 0.0001 g) in the teflon counteracting tank, add 10-20 ml Mixed Acids Digestion liquid surrounding medium sample or biological sample are cleared up 20-40 min in advance, add afterwards 0-2.0 ml hydrogen peroxide, put it in the microwave dissolver, adopt the method for temperature programme that it is cleared up; After clearing up, the sample after clearing up is caught up with acid operation, add afterwards 2 ml hydrogen peroxide, continue on the heating plate 110 ℃ and disappear and boil 5 min.After being cooled to room temperature, be settled to 10 ml or 25 ml with the salpeter solution of 2-5%, filter, obtain the constant volume testing sample.
(2). the mensuration of surrounding medium or Heavy Metal Contents in Biological Samples
With 10 times of above-mentioned constant volume testing sample dilutions, adopt icp ms (ICP-MS) that the content of beary metal of deciding in the testing sample after diluting is measured.When content of beary metal is lower than 20 ppb in the testing sample after the dilution, the constant volume testing sample is analyzed mensuration with ICP-MS again; When content of beary metal is higher than 200ppb in the testing sample after the dilution, by the minimizing sample weighting amount, or increase constant volume testing sample volume method, repeating step (1) re-starts micro-wave digestion to sample.
(3) the sample content of beary metal is quantitative
When carrying out surrounding medium sample or biological sample analysis, also need simultaneously bioassay standard blank, typical curve, method blank and standard specimen, be used for the quantitative of surrounding medium sample or biological sample content of beary metal and quality error control;
Standard is blank: do not take by weighing any sample of constant volume testing sample, standard model and standard solution, carry out its content of beary metal of time-and-motion study of step (2), 10 standard blank of METHOD FOR CONTINUOUS DETERMINATION are calculated 3 times of standard errors of these 10 standard blank, obtain the sample detection lower limit;
Typical curve: take by weighing in the world or standard solution that the chemical standard material research centre of authorized by state is bought according to the concentration stepwise dilution of typical curve to 0-200ppb, carry out the operation of step (2), and measure its content of beary metal, form the quantitative typical curve of sample content of beary metal;
Method is blank: do not add surrounding medium sample or biological sample in the teflon counteracting tank, micro-wave digestion is carried out in operation according to step (1), and according to its content of beary metal of time-and-motion study of step (2), carry out quantitatively according to typical curve, as the blank value of assay method;
Standard model: take by weighing in the world or standard substance that the chemical standard material research centre of authorized by state is bought carries out the operation of step (1) and step (2), carry out quantitatively according to typical curve, the subtraction method blank is calculated the measured value of standard model afterwards, measured value and standard value are compared, guarantee that measured value in standard value error allowed band, analyzes quality control;
Testing sample: content of beary metal and sample detection lower limit that constant volume testing sample ICP-MS measures are compared, be lower than and detect lower limit and think and do not detect, be higher than the detection lower limit and then according to typical curve it carried out quantitatively, the subtraction method blank is calculated the content of beary metal that obtains testing sample afterwards.
Among the present invention, described heavy metal comprises cadmium (Cadmium, Cd), plumbous (Lead, Pb), arsenic (Arsenic, As), antimony (Antimony, Sb), copper (Copper, Cu), zinc (Zinc, Zn), in nickel (Nickel, Ni) or the chromium (Chromium, Cr) more than one.
Among the present invention, described surrounding medium sample comprises: in the solid samples such as particle in soil, sediment, dust, Atmospheric particulates or the water any.
Among the present invention, described biological sample comprises: plant roots, stem, leaf or the Different Organs tissues such as flower and fruit, the Different Organs tissues such as the muscle of the multiple biologies such as fish, shell-fish, amphibian animal, reptiles, birds or beasts, liver, kidney, brain or ovum, or in people's the hair etc. any.
Among the present invention, described Mixed Acids Digestion liquid is selected from: nitric acid: the volume ratio of hydrochloric acid be in contrary chloroazotic acid, nitric acid, hydrochloric acid or the hydrofluorite of 3:1 more than one.For the surrounding medium sample, preferred Mixed Acids Digestion liquid is contrary chloroazotic acid and hydrofluorite; For biological sample, preferred Mixed Acids Digestion liquid is contrary chloroazotic acid.
Among the present invention, the method for described microwave dissolver temperature programme be with sample temperature step by step, minute time be warming up to 220 ℃ from 50 ℃.Clear up biological sample (such as root of plant etc.) for surrounding medium sample and difficulty, preferred heating schedule is as shown in table 1, namely being warming up to 100 ℃ of heating-up times from 50 ℃ is 3 minutes, being warming up to 150 ℃ of heating-up times from 100 ℃ is 2 minutes, being warming up to 180 ℃ of heating-up times from 150 ℃ is 2 minutes, being warming up to 200 ℃ of heating-up times from 180 ℃ is 2 minutes, and being warming up to 220 ℃ of heating-up times from 200 ℃ is 2 minutes, and the complexity of clearing up per sample at last kept 15-40 minute at 220 ℃; The sample (such as people's hair, biological muscles and viscera tissue, fruit and blade etc.) of preferred heating schedule easily clear up to(for) biological sample etc. is as shown in table 2, namely being warming up to 100 ℃ of heating-up times from 50 ℃ is 3 minutes, being warming up to 150 ℃ of heating-up times from 100 ℃ is 2 minutes, being warming up to 180 ℃ of heating-up times from 150 ℃ is 2 minutes, being warming up to 200 ℃ of heating-up times from 180 ℃ is 2 minutes, and the complexity of clearing up per sample at last kept 8-20 minute at 200 ℃.
Table 1 surrounding medium sample and the difficult preferred heating schedule of clearing up biological sample
| Step | Heating mode | Temperature (℃) | Time (minute) |
| 1 | The Gradient(gradient) | 100 | 3 |
| 2 | Gradient | 150 | 2 |
| 3 | Gradient | 180 | 2 |
| 4 | Gradient | 200 | 2 |
| 5 | Gradient | 220 | 2 |
| 6 | Step(constant temperature) | 220 | 15-40 |
Table 2 is easily cleared up the preferred heating schedule of biological sample
| Step | Heating mode | Temperature (℃) | Time (minute) |
| 1 | The Gradient(gradient) | 100 | 3 |
| 2 | Gradient | 150 | 2 |
| 3 | Gradient | 180 | 2 |
| 4 | Gradient | 200 | 2 |
| 5 | Step(constant temperature) | 200 | 8-20 |
Among the present invention, describedly catch up with acid operation, refer to catch up with acid under 110 ℃ of constant temperature, it is 0.4-0.6 ml that the acid in the counteracting tank is rushed to volume.
Among the present invention, when using hydrofluorite in the digestion process, it catches up with sour mode to be: under 110 ℃ of constant temperature, it is 0.5-1 ml that the acid in the counteracting tank is rushed to volume, adding the 3ml chloroazotic acid, to rush to volume be 0.5-1 ml again, and adding 3ml nitric acid, to rush to volume be 0.4-0.6 ml again.
Among the present invention, when using hydrochloric acid in the digestion process but not using hydrofluorite, it catches up with sour mode to be: under 110 ℃ of constant temperature, it is 0.5-1 ml that the acid in the counteracting tank is rushed to volume, and adding 3ml nitric acid, to rush to volume be 0.4-0.6 ml again.
Among the present invention, do not use hydrochloric acid and hydrofluorite in digestion process, it catches up with sour mode to be: under 110 ℃ of constant temperature, it is 0.4-0.6 ml that the acid in the counteracting tank is rushed to volume.
Among the present invention, the heavy metal concentration scope of described typical curve is at 0-200 ppb, and concentration gradient is got 4-6 point.
Among the present invention, described employing inductively coupled plasma emission mass spectrometer is blank to method, standard specimen, standard is blank, the condition that heavy metal in typical curve and the testing sample is tested is: plasma power 1500 w, carrier gas flux (high-purity argon) 0.7-0.75 L/min, compensator flow (high-purity argon) 0.2-0.3 L/min, reaction gas flow speed (high-pure helium) 0.08 L/min, the sample introduction degree of depth 8 mm, wriggling pump speed 0.1 rps, 2 ℃ of premixer's temperature, adopt Full Quant (3) analytical model, cadmium (Cd), arsenic (As), be 3 seconds the integral time of antimony (Sb), plumbous (Pb), copper (Cu), zinc (Zn), be 1 second the integral time of nickel (Ni) and chromium (Cr).
Among the present invention, described microwave dissolver is the middle high-pressure hermetic types such as Mile Stone ETHOS 1 or XT-9916.
The present invention compared with prior art has following advantage and beneficial effect:
(1) digestion procedure of the present invention have the sample applicability wide, simple to operate, can clear up simultaneously the advantages such as various heavy, compare other digestion procedure, for volatile heavy metals such as As, Sb, the loss amount in the digestion process is also minimum.
(2) method of testing of the present invention has highly sensitive, the advantages such as detectability is low, analysis speed is fast, dynamic linear wide ranges, compares other method of testing, and its mass spectrum disturbs can be ignored substantially.
Embodiment
The invention will be further elaborated below in conjunction with specific embodiment, and these embodiment only are not used in for explanation the present invention and limit the scope of the invention.
Embodiment 1
Soil constituent analytical standard material---middle and lower reach of Yangtze River soil (GBW07429) is purchased from the Geochemical Certified Reference Materials research centre.
Take by weighing respectively Soil standard sample 1.00082,0.99992 and 0.99952 g in the teflon counteracting tank, the counteracting tank of preparing simultaneously 1 sky is blank as method, (nitric acid: hydrochloric acid is 3:1 to add respectively the contrary chloroazotic acid of 10 ml, be domestic top grade pure) and 3ml hydrofluorite (the import top grade is pure) and sample slight mix concussion, putting into microwave dissolver behind the placement 20min clears up, clear up program as shown in table 1, wherein the digestion time of step 6 is made as 15 min.Clear up program operation complete after, treat that solution temperature is down to below 100 ℃ in the counteracting tank, open counteracting tank and be placed on and catch up with acid on the heating plate, the control temperature is 110 ℃.Steam to small size (approximately 0.5-1 ml) until digestion solution, add the 3ml chloroazotic acid and steam to small size (approximately 0.5-1 ml), add again 3ml nitric acid and steam to small size (approximately 0.5 ml).Add 2 ml hydrogen peroxide, continue on the heating plate 110 ℃ and disappear and boil 5 min.After the cooling, the salpeter solution with 4% with the sample constant volume, filters rear to be measured in 25 ml volumetric flasks.
The typical curve of the hybrid standard sample composition of preparation standard blank and 5 concentration gradients, the concentration gradient of 8 kinds of heavy metals to be measured is 0.5 ppb, 2 ppb, 10 ppb, 50 ppb and 200 ppb respectively.10 times of Sample Dilutions after will clearing up are measured heavy metal Cr, Ni, Cu, Zn, As and Pb content with standard model at inductively coupled plasma emission mass spectrometer, and sample stoste is measured heavy metal Cd and Sb content.Test condition is: 2 ℃ of plasma power 1500 w, carrier gas flux (high-purity argon) 0.75 L/min, compensator flow (high-purity argon) 0.25 L/min, reaction gas flow speed (high-pure helium) 0.08 L/min, the sample introduction degree of depth 8 mm, wriggling pump speed 0.1 rps, premixer's temperature, adopt Full Quant (3) analytical model, be 3 seconds the integral time of cadmium (Cd), arsenic (As), antimony (Sb), and be 1 second the integral time of plumbous (Pb), copper (Cu), zinc (Zn), nickel (Ni) and chromium (Cr).
Embodiment 2
Biochemical component standard substance---chicken (GBW10018) is purchased from the Geochemical Certified Reference Materials research centre.
Take by weighing respectively chicken standard model 0.29979,0.29952 and 0.30014 g in the teflon counteracting tank, the counteracting tank of preparing simultaneously 1 sky is blank as method, add respectively 10 ml nitric acid (domestic top grade is pure) and 1 ml hydroperoxy acid (domestic top grade is pure) and sample slight mix concussion, putting into microwave dissolver behind the placement 30min clears up, clear up program as shown in table 2, wherein the digestion time of step 4 is made as 20 min.Clear up program operation complete after, treat that solution temperature is down to below 100 ℃ in the counteracting tank, open counteracting tank and be placed on and catch up with acid on the heating plate, the control temperature is 110 ℃.Treat that digestion solution steams to small size (approximately 0.5 ml).Add 2 ml hydrogen peroxide, continue on the heating plate 110 ℃ and disappear and boil 5 min.After the cooling, the salpeter solution with 4% with the sample constant volume, filters rear to be measured in 10 ml volumetric flasks.
The typical curve of the hybrid standard sample composition of preparation standard blank and 5 concentration gradients, the concentration gradient of 8 kinds of heavy metals to be measured is 0.5 ppb, 2 ppb, 10 ppb, 50 ppb and 200 ppb respectively.10 times of Sample Dilutions after will clearing up are measured heavy metal Cu and Zn content with standard model at inductively coupled plasma emission mass spectrometer, and sample stoste is measured heavy metal Cr, Ni, As, Cd, Sb and Pb content.Test condition is: 2 ℃ of plasma power 1500 w, carrier gas flux (high-purity argon) 0.73 L/min, compensator flow (high-purity argon) 0.25 L/min, reaction gas flow speed (high-pure helium) 0.08 L/min, the sample introduction degree of depth 8 mm, wriggling pump speed 0.1 rps, premixer's temperature, adopt Full Quant (3) analytical model, be 3 seconds the integral time of cadmium (Cd), arsenic (As), antimony (Sb), and be 1 second the integral time of plumbous (Pb), copper (Cu), zinc (Zn), nickel (Ni) and chromium (Cr).
Embodiment 3
Biochemical component standard substance---spinach (GBW10015) is purchased from the Geochemical Certified Reference Materials research centre.
Take by weighing respectively spinach standard model 0.49854,0.50246 and 0.50345 g in the teflon counteracting tank, the counteracting tank of preparing simultaneously 1 sky is blank as method, (nitric acid: hydrochloric acid is 3:1 to add respectively the contrary chloroazotic acid of 10 ml, be domestic top grade pure) and 1 ml hydroperoxy acid (domestic top grade is pure) and sample slight mix concussion, putting into microwave dissolver behind the placement 30min clears up, clear up program as shown in table 2, wherein the digestion time of step 4 is made as 10 min.Clear up program operation complete after, treat that solution temperature is down to below 100 ℃ in the counteracting tank, open counteracting tank and be placed on and catch up with acid on the heating plate, the control temperature is 110 ℃.Steam to small size (approximately 0.5 ml) until digestion solution, add 3ml nitric acid and steam to small size (approximately 0.5 ml).Add 2 ml hydrogen peroxide, continue on the heating plate 110 ℃ and disappear and boil 5 min.After the cooling, the salpeter solution with 4% with the sample constant volume, filters rear to be measured in 10 ml volumetric flasks.
The typical curve of the hybrid standard sample composition of preparation standard blank and 5 concentration gradients, the concentration gradient of 8 kinds of heavy metals to be measured is 0.5 ppb, 2 ppb, 10 ppb, 50 ppb and 200 ppb respectively.10 times of Sample Dilutions after will clearing up are measured heavy metal Cu, Zn and Pb content with standard model at inductively coupled plasma emission mass spectrometer, and sample stoste is measured heavy metal Cr, Ni, As, Cd and Sb content.Test condition is: 2 ℃ of plasma power 1500 w, carrier gas flux (high-purity argon) 0.70 L/min, compensator flow (high-purity argon) 0.25 L/min, reaction gas flow speed (high-pure helium) 0.08 L/min, the sample introduction degree of depth 8 mm, wriggling pump speed 0.1 rps, premixer's temperature, adopt Full Quant (3) analytical model, be 3 seconds the integral time of cadmium (Cd), arsenic (As), antimony (Sb), and be 1 second the integral time of plumbous (Pb), copper (Cu), zinc (Zn), nickel (Ni) and chromium (Cr).
Embodiment 4
Biochemical component---bush branch and leaf Standard Reference Materials for Determination (GBW07602) is purchased from the Geochemical Certified Reference Materials research centre.
Take by weighing respectively bush branch and leaf standard model 0.49617,0.49635 and 0.49952 g in the teflon counteracting tank, the counteracting tank of preparing simultaneously 1 sky is blank as method, (nitric acid: hydrochloric acid is 3:1 to add respectively the contrary chloroazotic acid of 10 ml, be domestic top grade pure) and 1 ml hydroperoxy acid (domestic top grade is pure) and sample slight mix concussion, putting into microwave dissolver behind the placement 30min clears up, clear up program as shown in table 1, wherein the digestion time of step 5 is made as 20 min.Clear up program operation complete after, treat that solution temperature is down to below 100 ℃ in the counteracting tank, open counteracting tank and be placed on and catch up with acid on the heating plate, the control temperature is 110 ℃.Steam to small size (approximately 0.5 ml) until digestion solution, add 3ml nitric acid and steam to small size (approximately 0.5 ml).Add 2 ml hydrogen peroxide, continue on the heating plate 110 ℃ and disappear and boil 5 min.After the cooling, the salpeter solution with 4% with the sample constant volume, filters rear to be measured in 10 ml volumetric flasks.
The typical curve of the hybrid standard sample composition of preparation standard blank and 5 concentration gradients, the concentration gradient of 8 kinds of heavy metals to be measured is 0.5 ppb, 2 ppb, 10 ppb, 50 ppb and 200 ppb respectively.10 times of Sample Dilutions after will clearing up are measured heavy metal Cu, Zn and Pb content with standard model at inductively coupled plasma emission mass spectrometer, and sample stoste is measured heavy metal Cr, Ni, As, Cd and Sb content.Test condition is: 2 ℃ of plasma power 1500 w, carrier gas flux (high-purity argon) 0.70 L/min, compensator flow (high-purity argon) 0.25 L/min, reaction gas flow speed (high-pure helium) 0.08 L/min, the sample introduction degree of depth 8 mm, wriggling pump speed 0.1 rps, premixer's temperature, adopt Full Quant (3) analytical model, be 3 seconds the integral time of cadmium (Cd), arsenic (As), antimony (Sb), and be 1 second the integral time of plumbous (Pb), copper (Cu), zinc (Zn), nickel (Ni) and chromium (Cr).
Embodiment 5
Biochemical component standard substance---rice (GBW10010) is purchased from the Geochemical Certified Reference Materials research centre.
Take by weighing respectively Standard for Rice sample 0.50090,0.49863 and 0.49783 g in the teflon counteracting tank, the counteracting tank of preparing simultaneously 1 sky is blank as method, (nitric acid: hydrochloric acid is 3:1 to add respectively the contrary chloroazotic acid of 10 ml, be domestic top grade pure) and 1 ml hydroperoxy acid (domestic top grade is pure) and sample slight mix concussion, putting into microwave dissolver behind the placement 30min clears up, clear up program as shown in table 2, wherein the digestion time of step 4 is made as 8 min.Clear up program operation complete after, treat that solution temperature is down to below 100 ℃ in the counteracting tank, open counteracting tank and be placed on and catch up with acid on the heating plate, the control temperature is 110 ℃.Steam to small size (approximately 0.5 ml) until digestion solution, add 3ml nitric acid and steam to small size (approximately 0.5 ml).Add 2 ml hydrogen peroxide, continue on the heating plate 110 ℃ and disappear and boil 5 min.After the cooling, the salpeter solution with 4% with the sample constant volume, filters rear to be measured in 10 ml volumetric flasks.
The typical curve of the hybrid standard sample composition of preparation standard blank and 5 concentration gradients, the concentration gradient of 8 kinds of heavy metals to be measured is 0.5 ppb, 2 ppb, 10 ppb, 50 ppb and 200 ppb respectively.10 times of Sample Dilutions after will clearing up are measured heavy metal Zn content with standard model at inductively coupled plasma emission mass spectrometer, and sample stoste is measured heavy metal Cr, Ni, Cu, As, Cd, Sb and Pb content.Test condition is: 2 ℃ of plasma power 1500 w, carrier gas flux (high-purity argon) 0.75 L/min, compensator flow (high-purity argon) 0.25 L/min, reaction gas flow speed (high-pure helium) 0.08 L/min, the sample introduction degree of depth 8 mm, wriggling pump speed 0.1 rps, premixer's temperature, adopt Full Quant (3) analytical model, be 3 seconds the integral time of cadmium (Cd), arsenic (As), antimony (Sb), and be 1 second the integral time of plumbous (Pb), copper (Cu), zinc (Zn), nickel (Ni) and chromium (Cr).
The invention belongs to the developing invention, for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Claims (12)
1. the determination and analysis method of various heavy in a surrounding medium and the biological sample is characterized in that concrete steps are as follows:
The micro-wave digestion of surrounding medium or biological sample
Surrounding medium sample or biological sample are crossed the 80-100 mesh sieve after freeze drying, pulverizing, take by weighing sample 0.1-1.0 g in the teflon counteracting tank, take by weighing 0.0001 g that is accurate to of sample, add 10-20 ml Mixed Acids Digestion liquid surrounding medium sample or biological sample are cleared up 20-40 min in advance, add afterwards 0.5-2.0 ml hydrogen peroxide, put it in the microwave dissolver, adopt the method for temperature programme that it is cleared up; After clearing up, the sample after clearing up is caught up with acid operation, add afterwards 2 ml hydrogen peroxide, continue on the heating plate 110 ℃ and disappear and boil 5 min; After being cooled to room temperature, be settled to 10 ml or 25 ml with the salpeter solution of 2-5%, filter, obtain the constant volume testing sample;
The mensuration of surrounding medium or Heavy Metal Contents in Biological Samples
With 10 times of above-mentioned constant volume testing sample dilutions, adopt icp ms that the content of beary metal in the testing sample after diluting is measured; When content of beary metal is lower than 20 ppb in the testing sample after the dilution, the constant volume testing sample is analyzed mensuration with icp ms again; When content of beary metal is higher than 200 ppb in the testing sample after the dilution, by the minimizing sample weighting amount, or increase constant volume testing sample volume method, repeating step (1) re-starts micro-wave digestion to sample;
(3) the sample content of beary metal is quantitative
When carrying out surrounding medium sample or biological sample analysis, also need simultaneously bioassay standard blank, typical curve, method blank and standard specimen, be used for the quantitative of surrounding medium sample or biological sample content of beary metal and quality error control;
Standard is blank: do not take by weighing any sample of constant volume testing sample, standard model and standard solution, carry out its content of beary metal of time-and-motion study of step (2), 10 standard blank of METHOD FOR CONTINUOUS DETERMINATION are calculated 3 times of standard errors of these 10 standard blank, obtain the sample detection lower limit;
Typical curve: take by weighing in the world or standard solution that the chemical standard material research centre of authorized by state is bought according to the concentration stepwise dilution of typical curve to 0-200ppb, carry out the operation of step (2), and measure its content of beary metal, form the quantitative typical curve of sample content of beary metal;
Method is blank: do not add surrounding medium sample or biological sample in the teflon counteracting tank, micro-wave digestion is carried out in operation according to step (1), and according to its content of beary metal of time-and-motion study of step (2), carry out quantitatively according to typical curve, as the blank value of assay method;
Standard model: take by weighing in the world or standard substance that the chemical standard material research centre of authorized by state is bought carries out the operation of step (1) and step (2), carry out quantitatively according to typical curve, the subtraction method blank is calculated the measured value of standard model afterwards, measured value and standard value are compared, guarantee that measured value in standard value error allowed band, analyzes quality control;
Testing sample: content of beary metal and sample detection lower limit that constant volume testing sample ICP-MS measures are compared, be lower than and detect lower limit and think and do not detect, be higher than the detection lower limit and then according to typical curve it carried out quantitatively, the subtraction method blank is calculated the content of beary metal that obtains testing sample afterwards.
2. method according to claim 1 is characterized in that described heavy metal comprises in cadmium, lead, arsenic, antimony, copper, zinc, nickel or the chromium more than one.
3. method according to claim 1 is characterized in that described surrounding medium sample comprises: in the particle solid sample in soil, sediment, dust, Atmospheric particulates or the water any.
4. method according to claim 1, it is characterized in that described biological sample comprises: plant roots, stem, leaf or the Different Organs tissues such as flower and fruit, the muscle of fish, shell-fish, amphibian animal, reptiles, birds or beasts, liver, kidney, brain or ovum, or in people's the hair any.
5. method according to claim 1 is characterized in that described Mixed Acids Digestion liquid is selected from: nitric acid: the volume ratio of hydrochloric acid be in contrary chloroazotic acid, nitric acid, hydrochloric acid or the hydrofluorite of 3:1 more than one.
6. method according to claim 1, the method that it is characterized in that described microwave dissolver temperature programme be with sample temperature step by step, minute time be warming up to 220 ℃ from 50 ℃; Clear up biological sample for surrounding medium sample and difficulty, heating schedule is: being warming up to 100 ℃ of heating-up times from 50 ℃ is 3 minutes, being warming up to 150 ℃ of heating-up times from 100 ℃ is 2 minutes, being warming up to 180 ℃ of heating-up times from 150 ℃ is 2 minutes, being warming up to 200 ℃ of heating-up times from 180 ℃ is 2 minutes, being warming up to 220 ℃ of heating-up times from 200 ℃ is 2 minutes, and the complexity of clearing up per sample kept 15-40 minute at 220 ℃; Easily clear up sample for biological sample etc., heating schedule is: being warming up to 100 ℃ of heating-up times from 50 ℃ is 3 minutes, being warming up to 150 ℃ of heating-up times from 100 ℃ is 2 minutes, being warming up to 180 ℃ of heating-up times from 150 ℃ is 2 minutes, being warming up to 200 ℃ of heating-up times from 180 ℃ is 2 minutes, and the complexity of clearing up per sample at last kept 8-20 minute at 200 ℃.
7. method according to claim 1 is characterized in that the described acid operation of catching up with, and refers to catch up with acid under 110 ℃ of constant temperature, and it is 0.4-0.6 ml that the acid in the counteracting tank is rushed to volume.
8. method according to claim 5, it is characterized in that when using hydrofluorite in the digestion process, it catches up with sour mode to be: under 110 ℃ of constant temperature, it is 0.5-1 ml that acid in the counteracting tank is rushed to volume, adding the 3ml chloroazotic acid, to rush to volume be 0.5-1 ml again, and adding 3ml nitric acid, to rush to volume be 0.4-0.6 ml again.
9. method according to claim 5, it is characterized in that when using hydrochloric acid in the digestion process but not using hydrofluorite, it catches up with sour mode to be: under 110 ℃ of constant temperature, it is 0.5-1 ml that the acid in the counteracting tank is rushed to volume, and adding 3ml nitric acid, to rush to volume be 0.4-0.6 ml again.
10. method according to claim 5 is characterized in that not using hydrochloric acid and hydrofluorite in digestion process, and it catches up with sour mode to be: under 110 ℃ of constant temperature, it is 0.4-0.6 ml that the acid in the counteracting tank is rushed to volume.
11. method according to claim 1 is characterized in that the heavy metal concentration scope of described typical curve at 0-200 ppb, concentration gradient is got 4-6 point.
12. method according to claim 1, it is characterized in that described employing inductively coupled plasma emission mass spectrometer is blank to method, standard model, standard is blank, the condition that heavy metal in typical curve and the testing sample is tested is: plasma power is 1500 w, under the high-purity argon condition, carrier gas flux is 0.7-0.75 L/min, the compensator flow is 0.2-0.3 L/min, reaction gas flow speed is 0.08 L/min, the sample introduction degree of depth 8 mm, wriggling pump speed 0.1 rps, 2 ℃ of premixer's temperature, adopt Full Quant (3) analytical model, cadmium, arsenic, be 3 seconds the integral time of antimony, lead, copper, zinc, be 1 second the integral time of nickel and chromium.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101963594A (en) * | 2010-08-13 | 2011-02-02 | 同济大学 | Method for analyzing trace antimony in solid environmental sample |
-
2012
- 2012-08-10 CN CN201210282564XA patent/CN102854238A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101963594A (en) * | 2010-08-13 | 2011-02-02 | 同济大学 | Method for analyzing trace antimony in solid environmental sample |
Non-Patent Citations (2)
| Title |
|---|
| 刘亚轩: "电感耦合等离子体质谱法在勘查地球化学样品分析中的应用研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 * |
| 梁淑轩等: "微波消解/ICP-MS测定水系沉积物中的9种重金属元素", 《光谱学与光谱分析》 * |
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Application publication date: 20130102 |