CN105548125A - Determination of trace arsenic in high-copper-content sample with atomic fluorescence spectrometry - Google Patents
Determination of trace arsenic in high-copper-content sample with atomic fluorescence spectrometry Download PDFInfo
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Abstract
The invention discloses a determination method of trace arsenic in a high-copper-content sample with an atomic fluorescence spectrometry and belongs to the field of analysis detection. The determination method is characterized by comprising the following steps: reducing copper in a digested sample solution into cuprous iodide by potassium iodide and precipitating copper in a form of cuprous iodide; adding thiocyanate and precipitating free cuprous ions in the solution in a form of cuprous thiocyanate with relatively high stability and relatively low solubility; after filtering and making the volume constant, determining the arsenic content in the sample solution; and calculating the content of the arsenic in the sample. With the adoption of the method, copper in the sample solution and thiourea and potassium borohydride, which are needed by an experiment, are effectively prevented from reacting to generate sediment. The method is simple and reliable and has high accuracy and good repeatability.
Description
Technical field
The invention belongs to analysis detection field, relate to the method using atomic fluorescence spectrometry to survey trace arsenic, and get rid of the method for copper interference in sample.
Background technology
Arsenic is a kind of nonmetalloid, has bio-toxicity and accumulative, and human body takes in the food polluted by arsenic for a long time can be very unfavorable to health, and therefore arsenic is listed in the harmful element of emphasis monitoring in food hygiene detection.
At present, in GB29210-2012 " national food safety standard food additives copper sulphate ", the limitation of arsenic is required be≤0.0003%, in HG2932-1999 " feed-grade bluestone ", the limitation of arsenic is required be≤0.0004%, GB13078-2001 " forage health standard " limitation of arsenic in copper sulphate is required be≤0.0005%.In standard, the assay method of regulation arsenic content has arsenic spot method, silver salt method, hydride generation atomic fluorescence photometry, and above method of analyzing and researching respectively has relative merits, and detection method is very important accurately to set up a simple and fast.
Arsenic spot method utilizes metallic zinc to act on acid the hydrogen producing gaseous state, the hydrogen of nascent state reacts generation with the micro-arsenite in sample again and has volatile arsenic hydride, produce yellow to brown arsenic spot when arsenic hydride runs into mercuric bromide test paper, by this arsenic spot again with under same condition, the arsenic spot that produces of the standard arsenic solution of same operation carries out color and compares, and judges the content of arsenic in sample.The method judges that the content of arsenic in sample compares by carrying out range estimation with the arsenic spot that standard arsenic solution produces, containing certain subjectivity, data objectively can not show the real content of surveyed arsenic in sample, and error is comparatively large, does not reach accuracy requirement to the mensuration of trace arsenic; And the method running program too very complicated, be unfavorable for the content of express-analysis arsenic in sample; Extremely toxic substance arsenic trioxide must be used when the more important thing is and make arsenic spot, great injury be caused to experimenter's health, great pollution is caused to environment.
Silver salt method is that after first the high price arsenic cleared up in sample being completely reduced to As (III) with potassium iodide, stannous chloride, As (III) is produced hydrogen in statu nascendi by zinc granule and acid and is reduced to arsenic hydride.The chloroform soln of diethylin dithiocarbonic acid silver absorbs arsenic hydride and forms yellow or brown silver sol, and its shade is directly proportional to arsenic content, measures with spectrophotometric colo.The method workload is large, operating difficulties, and sense cycle is long; Moreover the organic reagents such as the methenyl choloride that the method will be used affect by solvent volatilization, analyze less stable; And reagent toxicity used by the method is comparatively large, causes certain injury, also cause certain pollution to environment to experimenter's health.
Atomic fluorescence spectrometry first under thiourea and ascorbic acid-hydrochloric acid medium, As (V) prereduction is become As (III), and then the potassium hydroxide solution of solution and potassium borohydride reacts and generates AsH
3, AsH in Ar-H flame
3decompose and excited by as hollow cathode lamp, discharging fluorescence.By atomic fluorescence spectrophotometer, measure its fluorescence intensity, and calculate its massfraction.When the method surveys Copper mass fraction very high sample, following problem will be run into:
1. find in experiment, in the solution copper ion massfraction when being greater than 0.03%, add thiourea and ascorbic acid-hydrochloric acid when carrying out prereduction, white precipitate will be generated and suspend in the solution, after 5 minutes concuss, white precipitate does not dissolve.
2. find in experiment, in the solution copper ion massfraction when being greater than 0.005%, when measuring arsenic content in solution by atomic fluorescence spectrophotometer, solution and potassium borohydride react and generate black particle and be adsorbed on tube wall, are difficult to clean.This measurement result is seriously on the low side simultaneously, and data reliability is not high.
Summary of the invention
The object of the invention is to improve atomic fluorescence method measure containing the trace arsenic in copper sample height.Major embodiment be following some:
1. quick.Simplify experiment, control testing cost;
2. environmental protection.Avoid using the poisonous reagent such as arsenic trioxide, methenyl choloride to damage experimenter's health;
3. anti-interference.Utilize the features such as atomic fluorescence spectrophotometer spectral line is simple, co-existing element interference is little, can micro amount of arsenic be detected fast and accurately;
4. first with potassium iodide, copper reduction in sample solution is become Cu (I), and precipitate with cuprous iodide form, then with thiocyanate, the free Cu (I) in solution is precipitated with the cuprous rhodanide form that solubleness is less;
Sedimentation equilibrium COEFFICIENT K
sp (CuSCN)=2.0 × 10
-13, K
sp (CuI)=2.0 × 10
-12.
K
sp (CuSCN)k
sp (CuI)1/10th.
5. after the precipitate reduction of potassium iodide and thiocyanate, guarantee that solution does not generate white precipitate and suspends in the solution when following thiourea and ascorbic acid-hydrochloric acid to carry out prereduction, and solution and potassium borohydride react and do not generate black particle.
Note: sedimentation equilibrium coefficient derives from " analytical chemistry study course ", Li Kean edits. BJ University Press, 2005,748 pages.
Technical scheme of the present invention is: first use potassium iodide that the Cu (II) in sample solution is reduced into Cu (I), and precipitate with cuprous iodide form, again with thiocyanate by the free Cu (I) in solution, precipitate with the cuprous rhodanide form that solubleness is less.In pre-treatment, control initial copper ion in solution, and the mass ratio of the iodide ion added and thiocyanate ion is in 0 ~ 1: 4: 2 scopes.When reaction gained sample solution carries out prereduction with thiourea and ascorbic acid-hydrochloric acid, white precipitate can not be generated and suspend in the solution, and solution and potassium borohydride react and also can not generate black particle.
Its step is as follows:
1. reagent configuration
1.1 liquor kalii iodides: accurately take potassium iodide 100.0 grams, stand-by in constant volume to 100mL volumetric flask after being dissolved in water;
1.2 thiocyanate salt solutions (this method select thiocyanate be potassium rhodanate): accurately take potassium rhodanide 100.0 grams, stand-by in constant volume to 100mL volumetric flask after being dissolved in water;
1.3 thiourea and ascorbic acid solution: accurately take thiocarbamide 10.0 grams and 10.0 grams, ascorbic acid, stand-by in constant volume to 100mL volumetric flask after being dissolved in water;
2. sample pretreatment
Type per sample, selects one to carry out pre-service to sample from following two kinds of disposal routes.
2.1 food additives copper sulphate and the sample pretreatment of feed addictive copper sulphate
Take 5.0g sample, be accurate to 0.0001g, be placed in 100mL beaker, for subsequent use after adding the water-soluble solution of about 10mL.
2.2 mineral element Feed Sample pre-service
Take 0.5 ~ 2.0g sample, be accurate to 0.0001g, be placed in 100mL beaker, add suitable quantity of water wetting after, slowly add 10 ~ 15mL hydrochloric acid, be diluted with water to about 30mL, boil, until cool for subsequent use after remaining about 10mL.
3. in sample, eliminate the process of copper interference
Get above-mentioned (2) and prepare sample solution, react than in 0 ~ 1: 4: 2 scopes with initial copper ion and the iodide ion added and thiocyanate ion reaction mass, that is: 20mL liquor kalii iodide (1.1) is added, stir fully with glass bar, now sample solution is bronzing, and is attended by the generation of brown color precipitation.In sample solution, add 10mL potassium rhodanate solution (1.2) again, stir with glass bar.Stir after 5 minutes, solution is bronzing, and brown color precipitation becomes canescence, continue to stir until brown color is converted into canescence completely, filter, washing filter residue 3 times, merging filtrate, transfer in 100mL volumetric flask, add 5mL hydrochloric acid, 5mL thiourea and ascorbic acid solution (1.3), constant volume is to scale, shake up, leave standstill 30min, to be measured.
4. typical curve
Accurately pipette 100.0 μ g/L arsenic standard solution 1mL, 2mL, 5mL, 8mL and 10mL respectively in 100mL volumetric flask, respectively add 5mL thiourea and ascorbic acid solution (1.3) and 5mL hydrochloric acid, the constant volume that adds water is to scale.This standard solution working curve concentration is 1 μ g/L, 2 μ g/L, 5 μ g/L, 8 μ g/L and 10 μ g/L.
5. instrument condition
6. examination with computer
With atomic fluorescence spectrophotometer, be that 5% hydrochloric acid is as current-carrying using volume fraction, with massfraction be 0.5% potassium hydroxide solution and massfraction be that the potassium borohydride mixed solution of 2.0% is for reductive agent, measure the fluorescent value of arsenic standard solution working curve and sample solution, drawing standard curve the content of arsenic in calculation sample.
Beneficial effect: beneficial effect of the present invention be following some:
1., with atomic fluorescence spectrometry, method simple and fast, avoids using the poisonous reagent such as arsenic trioxide, methenyl choloride to damage experimenter's health simultaneously;
2. survey arsenic by atomic fluorescence spectrophotometer, the features such as atomic fluorescence spectrophotometer spectral line is simple, co-existing element interference is little, can detect fast and accurately to micro amount of arsenic;
3. first with potassium iodide, copper reduction in sample solution is become Cu (I), and with cuprous iodide (K
sp (CnI)=1.1 × 10
-12) form precipitates, then add thiocyanate Cu (I) a small amount of in solution is precipitated with cuprous rhodanide form, guarantee that sample solution and thiocarbamide react and react with potassium borohydride and do not generate precipitation, thus guarantee that sample result is with a high credibility;
Embodiment
The present invention will be further described in conjunction with the embodiments, but limited the present invention never in any form, and any change made based on training centre of the present invention or improvement, all belong to protection scope of the present invention.
Embodiment 1
For food additives copper sulphate, with reference to " national food safety standard food additives copper sulphate ", sample is processed, be labeled as T1 and T2; And according to this programme potassium iodide-potassium rhodanate precipitate reduction copper ion processing sample, be labeled as T7 and T8; Contrast simultaneously only uses potassium iodide processing sample, is labeled as T3 and T4, only uses potassium rhodanate processing sample, be labeled as T5 and T6.After process, sample solution reacts with thiourea and ascorbic acid mixed solution respectively, and reacts with potassium hydroxide-solution of potassium borohydride, observing response phenomenon, and specific experiment process is as follows:
Take Salzburg vitriol 5.0g totally 8 parts respectively, be labeled as T-1, T-2, T-3, T-4, T-5, T-6, T-7 and T-8 respectively.
After T-1 and T-2 respectively adds the water-soluble solution of about 20mL, transfer in 100mL volumetric flask, with water constant volume to scale, shake up for subsequent use.
After T-3 and T-4 respectively adds the water-soluble solution of about 10mL, add the liquor kalii iodide 20mL that massfraction is 100% respectively, stir fully with glass bar and be filled in 100mL volumetric flask, with water constant volume to scale, shake up for subsequent use.
After T-5 and T-6 respectively adds the water-soluble solution of about 10mL, add the potassium rhodanate solution 10mL that massfraction is 100% respectively, stir fully with glass bar and be filled in 100mL volumetric flask, with water constant volume to scale, shake up for subsequent use.
After T-7 and T-8 respectively adds the water-soluble solution of about 10mL, add the liquor kalii iodide 20mL that massfraction is 100% respectively, stir fully with glass bar, adding massfraction is again that after the potassium rhodanate solution 10mL of 100%, continuation glass bar is filled in 100mL volumetric flask after stirring, with water constant volume to scale, shake up for subsequent use.
Get T-1, T-2, T-3, T-4, T-5, T-6, T-7 and T-8 solution 5mL respectively, (thiocarbamide massfraction is 10% with 0.5mL thiourea and ascorbic acid mixed solution, ascorbic acid massfraction is 10%) reaction, observe phenomena, reacting phenomenon is as described in table one.
Separately get T-1, T-2, T-3, T-4, T-5, T-6, T-7 and T-8 solution 5mL respectively in 10mL color comparison tube, (thiocarbamide massfraction is 10% to 0.5mL thiourea and ascorbic acid mixed solution respectively, ascorbic acid massfraction is 10%) and 0.5mL hydrochloric acid, shake up with after water constant volume, (potassium hydroxide massfraction is 0.5% with potassium hydroxide-potassium borohydride mixed solution, solution of potassium borohydride massfraction is 2.0%) reaction, observe phenomena, reacting phenomenon is as described in table one.
Table one sample reacting phenomenon
Embodiment 2
Trace arsenic in the Salzburg vitriol provide certain chemical reagent work is tested, and does recovery testu and Precision Experiment etc. simultaneously.
Take this sample 5.0g totally 20 parts respectively, be labeled as S-1, S-2, A-1, A-2, A-3, A-4, A-5, A-6, B-1, B-2, B-3, B-4, B-5, B-6, C-1, C-2, C-3, C-4, C-5 and C-6 respectively.After being dissolved in water respectively, add the liquor kalii iodide 20mL that massfraction is 100%, stir fully with glass bar, adding massfraction is that after the potassium rhodanate solution 10mL of 100%, continuation glass bar stirs, then be filled into respectively in 100mL volumetric flask, with water constant volume to scale, shake up (note: initial copper ion is 1: 4: 2 with the iodide ion added and thiocyanate ion reaction mass ratio herein).
Divide and get in above-mentioned solution 10mL to 50mL volumetric flask, add 2.5mL hydrochloric acid, (thiocarbamide massfraction is 10% to 2.5mL thiourea and ascorbic acid mixed solution, ascorbic acid massfraction is 10%), with water constant volume to scale, shake up rear standing 30min, to be measured.With doing blank test.
Accurately pipette 100.0 μ g/L arsenic standard solution 1mL, 2mL, 5mL, 8mL and 10mL respectively in 100mL volumetric flask, (thiocarbamide massfraction is 10% respectively to add 5mL thiourea and ascorbic acid solution, ascorbic acid massfraction is 10%) and 5mL hydrochloric acid, the constant volume that adds water is to scale.This standard solution working curve concentration is 1 μ g/L, 2 μ g/L, 5 μ g/L, 8 μ g/L and 10 μ g/L.
By atomic fluorescence spectrophotometer, be that 5% hydrochloric acid is as current-carrying using volume fraction, with massfraction be 0.5% potassium hydroxide solution and massfraction be that the potassium borohydride mixed solution of 2.0% is for reductive agent, measure arsenic standard solution working curve, with the fluorescent value of sample solution for Y, with the concentration of sample solution for X, experimental result is as follows: arsenic standard solution working curve regression equation is Y=117.3682 × X-0.9286, R2 is 0.9998.Surveying 12 blank, to obtain instrument detection limit be 0.0273 μ g/L.Experimental result shows, under repeated condition, RSD% is less than 5%.Mark-on level 0.2 μ g, 0.5 μ g, 1.0 μ g, the recovery is between 90% to 110%.
Table two sample determination result
Embodiment 3
Trace arsenic in food additives copper sulphate is measured.Take 5.0g food additives copper sulphate in 150mL beaker, after adding suitable quantity of water dissolving, add the liquor kalii iodide 20mL that massfraction is 100%, stir fully with glass bar, adding massfraction is that after the potassium rhodanate solution 10mL of 100%, continuation glass bar stirs, then be filled into (note: initial copper ion is 1: 4: 2 with the iodide ion added and thiocyanate ion reaction mass ratio herein) in 100mL volumetric flask, add 5mL hydrochloric acid, (thiocarbamide massfraction is 10% to 5mL thiourea and ascorbic acid mixed solution, ascorbic acid massfraction is 10%), with water constant volume to scale, shake up rear standing 30min, to be measured.With doing blank test and recovery testu.Compound concentration is respectively the arsenic standard solution working curve of 1 μ g/L, 2 μ g/L, 5 μ g/L, 8 μ g/L and 10 μ g/L.The fluorescence intensity of measurement standard solution working curve and sample solution is distinguished by atomic fluorescence spectrophotometer.Through calculating, in food additives copper sulphate, arsenic content is 0.028mg/kg.Mark-on level 0.2 μ g, the recovery is 96.4%.
Embodiment 4
Trace arsenic in feed-grade bluestone is measured.Take 5.0g feed-grade bluestone in 150mL beaker, after adding suitable quantity of water dissolving, add the liquor kalii iodide 20mL that massfraction is 100%, stir fully with glass bar, adding massfraction is that after the potassium rhodanate solution 10mL of 100%, continuation glass bar stirs, then be filled into (note: initial copper ion is 1: 4: 2 with the iodide ion added and thiocyanate ion reaction mass ratio herein) in 100mL volumetric flask, add 5mL hydrochloric acid, (thiocarbamide massfraction is 10% to 5mL thiourea and ascorbic acid mixed solution, ascorbic acid massfraction is 10%), with water constant volume to scale, shake up rear standing 30min, to be measured.With doing blank test and recovery testu.Compound concentration is respectively the arsenic standard solution working curve of 1 μ g/L, 2 μ g/L, 5 μ g/L, 8 μ g/L and 10 μ g/L.The fluorescence intensity of measurement standard solution working curve and sample solution is distinguished by atomic fluorescence spectrophotometer.Through calculating, in feed-grade bluestone, arsenic content is 0.13mg/kg.Mark-on level 1.0 μ g, the recovery is 105%.
Embodiment 5
Trace arsenic in mineral element feed is measured.Take 1.0g mineral element feed in 100mL beaker in tall form, add suitable quantity of water wetting after, after slow dropping 10 ~ 15mL hydrochloric acid, add water to about 30mL, boil and cool after solution remains about 10mL, add the liquor kalii iodide 20mL that massfraction is 100%, stir fully with glass bar, adding massfraction is that after the potassium rhodanate solution 10mL of 100%, continuation glass bar stirs, then be filled into (note: initial copper ion is 0.2: 4: 2 with the iodide ion added and thiocyanate ion reaction mass ratio herein) in 100mL volumetric flask, add 5mL hydrochloric acid, (thiocarbamide massfraction is 10% to 5mL thiourea and ascorbic acid mixed solution, ascorbic acid massfraction is 10%), with water constant volume to scale, shake up rear standing 30min, to be measured.With doing blank test and recovery testu.Compound concentration is respectively the arsenic standard solution working curve of 1 μ g/L, 2 μ g/L, 5 μ g/L, 8 μ g/L and 10 μ g/L.The fluorescence intensity of measurement standard solution working curve and sample solution is distinguished by atomic fluorescence spectrophotometer.Through calculating, mineral element Arsenic content is 0.69mg/kg.Mark-on level 0.5 μ g, the recovery is 94.7%.
Claims (2)
1. atomic fluorescence method height is containing the mensuration of trace arsenic in copper sample, it is characterized in that the interference getting rid of copper in sample with the following methods:
(1) first use potassium iodide that the Cu (II) in sample solution is reduced to Cu (I), and precipitate with cuprous iodide form;
(2) add thiocyanate again cuprous ion free in sample solution, precipitate with the form of cuprous rhodanide;
。
2. according to claim 1, it is characterized in that the mass ratio of initial copper ion and the iodide ion added and thiocyanate ion in control solution is in 0 ~ 1: 4: 2 scopes.
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| CN113495024A (en) * | 2021-07-02 | 2021-10-12 | 金川集团股份有限公司 | Sample pretreatment method for measuring arsenic in sodium sulfide solution by atomic fluorescence spectrometry |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108609644A (en) * | 2018-03-21 | 2018-10-02 | 陈亚 | A kind of recovery method of copper ion |
| CN108675484A (en) * | 2018-03-21 | 2018-10-19 | 陈亚 | A kind of recovery method of copper ion |
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| CN113495024A (en) * | 2021-07-02 | 2021-10-12 | 金川集团股份有限公司 | Sample pretreatment method for measuring arsenic in sodium sulfide solution by atomic fluorescence spectrometry |
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