CN102944551B - A kind of Cd 2+detection method - Google Patents
A kind of Cd 2+detection method Download PDFInfo
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Abstract
The invention provides a kind of Cd
2+detection method.The method adopts the water miscible and carbohydrate polymer aqueous solution with reductibility react with gold or silver salt solution, obtains having the gold of carbohydrate polymer modification or the aqueous solution of Nano silver grain, makes Cd by electrostatic adsorption
2+be adsorbed on the surface of this gold or Nano silver grain, then add sulfhydryl compound, make itself and Cd
2+interact, the compound of one deck cadmium is formed on surface that is golden or Nano silver grain, the surface plasmon absorption intensity of gold or Nano silver grain and peak position is caused to change, the color of gold or silver nano-particle solution, ultravioletvisible absorption intensity and peak value is caused to change, therefore directly utilize naked eyes or ultraviolet-visible pectrophotometer, whether just can detect fast in solution containing Cd
2+, realize Cd in solution
2+quick, easy colorimetric detection, be applicable to the water investigation in lake, river, sewage detection, and food, blood, Cd in urine
2+detection.
Description
Technical field
The present invention relates to Cd
2+detection method, particularly relate to a kind of simple based on on-the-spot nucleocapsid mode, fast, Sensitive Detection Cd
2+method.
Background technology
Along with the fast development of industry, Industrial " three Waste " (waste water,waste gas and industrial residue) harm to environment becomes increasingly conspicuous.A large amount of heavy metals flows into river, lake and ocean with waste water, causes polluting.Heavy metal pollution has become one of subject matter of China's environmental pollution.Along with the growing interest of people's environmental pollution, in environment, the detection of heavy metal ion seems and becomes more and more important.Particularly heavy metal cadmium (Cd), its primary pollution source is the waste water of the discharges such as plating, mining, smelting, dyestuff, battery and chemical industry.Cadmium can produce respiratory tract to stimulate, and long-term exposure can cause anosmia, gum macula lutea or gradually become yellow circle; Cadmium compound not easily by intestinal absorption, but through breathing by body absorption, can lodge in liver or kidney works the mischief, and especially with the most obvious to kidney damage, also can cause osteoporosis and the disease such as softening.Therefore, in order to prevent cadmium to the pollution of environment, must carry out environmental protection work, the environmental health standards of strict implement cadmium, realize field quick detection, give warning in advance.
At present, common detection heavy metal, comprises cadmium ion (Cd
2+) technical method have atomic absorption spectrography (AAS), inductively coupled plasma mass spectrometry method, inductively coupled plasma-emission spectrometry, electrochemical process and ultraviolet-visible spectrophotometry.Although the Application comparison of these methods is ripe, there is not high, the required instrument price costliness of sensitivity, carry the problem such as inconvenience, on-the-spot promptness difference.Such as, there is mensuration element spectral line and have the shortcomings such as interference, sensitivity are not high, analysis time is long, the range of linearity is little in atomic absorption spectrography (AAS); Although inductively coupled plasma mass spectrometry method detects, restriction is low, and it is expensive, and vulnerable to pollution; Compared with inductively coupled plasma mass spectrometry method, inductively coupled plasma-emission spectrometry sensitivity is lower slightly; The on-the-spot promptness of electrochemical process is poor and serious with ion interference.Comparatively speaking, ultraviolet-visible spectrophotometry has and analyzes fast and the simple feature of instrument.
In addition, have in document and utilize cadmium ion to cause golden nanometer particle gathering to detect method report (the Ying Xue of cadmium ion in aqueous solution, Hong Zhao, Analyst, 2011, DOI:10.1039/c1an15238f), but modify owing to using buffer solution and multi-step, make experimental procedure more numerous and diverse.
In sum, at present in the urgent need to fast, the technical method of Site Detection cadmium ion in time, but because all restrictions make more difficultly in water solution system to realize this technology, therefore, strong, the testing result favorable reproducibility of simplicity of design, portable, highly sensitive and stability, cadmium ion detection method that required cost is low are imperative.
Summary of the invention
Technical matters to be solved by this invention is for the above-mentioned state of the art, provides one simply, fast, delicately can detect Cd
2+method.
The present invention solves the problems of the technologies described above taked technical scheme: a kind of Cd
2+detection method, the method, in conjunction with noble metal nano particles technology and spectral analysis technique, based on noble metal nano particles and the thiol compound system of finishing, utilizes noble metal nano particles and thiol compound and Cd
2+between interaction, the resonance absorption of noble metal nano particles surface plasma is caused to change, thus cause noble metal nano particles color and ultravioletvisible absorption intensity or peak position to change, directly differentiated the change of solution colour by naked eyes or simple instrument and equipment, realize the Cd detected fast in solution system
2+, specifically comprise the steps:
Step 1, stir condition under, by a certain amount of golden salt or silver salt solution and water miscible in right amount and there is the carbohydrate polymer aqueous solution of reductibility, and add appropriate strong basic reagent, obtained after reaction certain hour have the golden nanometer particle of carbohydrate polymer modification or the aqueous solution of Nano silver grain;
The aqueous solution of step 2, having of getting that the above-mentioned steps 1 of certain volume the obtains golden nanometer particle that carbohydrate polymer modifies or Nano silver grain, regulates this solution ph to 9 ~ 11 with alkaline solution, obtains detecting liquid;
Step 3, in the detection liquid that step 2 is obtained, measure out the identical detection liquid sample product of two parts of volumes; Preparation is not containing Cd
2+solution solution as a comparison, add respectively in two parts of described detection liquid sample product by comparative solution and with the isopyknic solution to be detected of comparative solution, form the first mixed liquor and the second mixed liquor;
Step 4, equal-volume, isocyatic thiol compound aqueous solution added respectively the first mixed liquor with and the second mixed liquor in, after hybrid reaction is stable, the first mixed liquor after observing response and the color of the second mixed liquor change, if there is color change, then there is Cd in solution to be detected
2+, and Cd
2+concentration is higher than 10
-7mol/L; If there is not color change, then Cd in solution to be detected
2+concentration is lower than 10
-7mol/L;
Or, equal-volume, isocyatic thiol compound aqueous solution are added respectively the first mixed liquor with and the second mixed liquor in, after hybrid reaction is stable, contrast ultravioletvisible absorption intensity, the peak value of reacted second mixed liquor and the first mixed liquor, if its ultravioletvisible absorption intensity, peak value change, then there is Cd in solution to be detected
2+if, unchanged, then there is not Cd in solution to be detected
2+.
In technique scheme:
In described step 1, silver salt includes but not limited to as one or more in silver nitrate, silver acetate, trifluoroacetic acid silver, trifluoro-methane sulfonic acid silver, silver hexafluoroantimonate and silver tetrafluoroborate; Gold salt include but not limited in chlorauride, aurous chloride, gold chloride, potassium chloroaurate and sodium chloraurate one or more.
In described step 1, water miscible and the carbohydrate polymer with reductibility includes but not limited to maltose, lactose, galactose, fructose, glucosan; Be preferably water-soluble polyhydroxyl carbohydrate polymer, water-soluble polyhydroxyl carbohydrate polymer includes but not limited to one or both the mixing in fructose, glucosan, soluble starch; Wherein, glucosan includes but not limited to glucosan 100,000 (namely molecular weight is the glucosan of 100,000), glucosan 140,000, glucosan 200,000, macrodex ten thousand etc.
In described step 1, strong basic reagent include but not limited in NaOH, potassium hydroxide, baryta hydrate one or more mixing.
In described step 2, alkaline solution includes but not limited to one or more the mixing in sodium hydroxide solution, potassium hydroxide, baryta hydrate.
In described step 2, after regulating, solution ph is preferably 9.1 ~ 10.1.
In described step 4, thiol compound includes but not limited to ATS (Ammonium thiosulphate), thiosalicylic acid, thioacetic acid, thiomicoler's ketone, thiosemicarbazide, thioglycolic acid, thioacetamide, is preferably thioacetamide.
Further discovery, in the hybrid reaction process in above-mentioned steps 4, if Cd in described solution to be detected
2+concentration higher, then the reaction time is shorter, and namely the color change required time of reaction solution is shorter, and the reaction time of general color change is 5 ~ 120 minutes.This hybrid reaction process also can be monitored the ultravioletvisible absorption intensity of reaction solution or the change of peak position by ultraviolet-visual spectrometer and observe, therefore can monitor preferably by ultraviolet-visual spectrometer the course of reaction obtained and determine the required reaction monitoring time, to guarantee that this hybrid reaction occurs completely, such as, Cd
2+concentration is 10
-7the detection time of mol/L is for being more than or equal to 30 minutes.
In order to determine Cd in solution to be detected further
2+concentration range, can use Cd in colorimetric determination solution to be detected
2+concentration range, specific as follows: first to formulate color standards, color and this color standards of the second mixed solution then step 4 obtained carry out colorimetric control, determine Cd in solution to be detected
2+concentration range.Wherein, color standards is formulated as follows:
Many parts of volumes identical detection liquid sample product A, B, C, D is measured out in the detection liquid that step 2 is obtained The Cd of preparation variable concentrations
2+solution is solution a, b, c, d as a comparison ... each comparative solution is added respectively in each detection liquid sample product, then add the isocyatic thiol compound aqueous solution with the equal-volume described in step 4 wherein to mix, wait for quietly after solution colour vary stable as color standards.
Further discovery, in above-mentioned steps 4, according to the second mixed solution relative to the first mixed solution ultravioletvisible absorption intensity or peak position change, can calculate Cd in solution to be detected
2+content.
In order to accurately determine the Cd in solution to be detected further
2+concentration, as preferably, can reflect Cd in mixed solution if provided
2+the canonical plotting of concentration and ultravioletvisible absorption strength relationship, the ultraviolet-visible spectral absorbance values of such as mixed solution and Cd
2+the curve map of concentration, or relatively ultraviolet-visible absorption value (the ultraviolet-visible spectral absorbance values ÷ of relative ultraviolet-visible absorption value=blank detects mixed liquor ultraviolet-visible spectral absorbance values) and Cd
2+the curve map of concentration, the ultravioletvisible absorption intensity of the second mixed liquor obtained by the present invention or peak position and this canonical plotting contrast, thus obtain Cd in the second mixed liquor
2+concentration.The concrete method for drafting of this canonical plotting is as follows:
First, according to a series of different Cd of compound method preparation of second mixed liquor reacted in described step 4
2+the aqueous solution of concentration, detects its ultravioletvisible absorption intensity respectively when wavelength is 200nm ~ 1000nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, and the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting;
Found through experiments, when canonical plotting is drawn, described Cd
2+the determined wavelength of ultravioletvisible absorption intensity be preferably 650nm.
In addition, Cd of the present invention
2+detection method also has Cd
2+selectivity, has anti-interference to other anions and canons.That is, whether can accurately be judged in system containing Cd by detection method of the present invention
2+even if this system also comprises interfering ion, as Ba
2+, Ca
2+, Pb
2+, Mn
2+, Cr
3+, Hg
2+, Ni
2+, Cl
-, CO
3 2-, SO
4 2-, L-His, L-Lys, L-Thr etc.
In the present invention, detected solution can be water sample in environment, also can be the solution that the water-soluble or organic solvent of other samples is formed, as the solution formed after the environmental sample process in solid-state environmental sample, air, and food samples, urine, blood etc. in biomedicine are dissolved in the solution formed in water or alcoholic environment.
The inventive method is not only applicable to Cd in water solution system
2+detection, and can be used for detecting the cadmium ion in aqueous solution that the blood of solid-state environment sample, people and animals etc. or body fluid goods or floating dust in an atmosphere or food samples obtain after treatment.Because the amount of cadmium metal ion contained detected in sample is different, to such an extent as to the time speed of the color of noble metal nano particles solution change and being of different shades, the detection detected cadmium metal ion being carried out to quantitative and qualitative analysis can be realized.
In sum, the invention provides a kind of novel method for detecting cadmium ion in solution, the method adopts water miscible and the carbohydrate polymer aqueous solution with reductibility prepares golden nanometer particle or Nano silver grain as reductive agent, stabilizing agent and surfactant, obtained have the golden nanometer particle of carbohydrate polymer modification or the aqueous solution of Nano silver grain, makes Cd by electrostatic adsorption
2+be adsorbed on the surface of this golden nanometer particle or Nano silver grain, then add sulfhydryl compound, make itself and Cd
2+interact, the compound of one deck Cd is formed on the surface of golden nanometer particle or Nano silver grain, thus cause the surface plasmon absorption intensity of golden nanometer particle or Nano silver grain and peak position to change, the color of golden nanometer particle or silver nano-particle solution, ultravioletvisible absorption intensity and peak value is caused to change, therefore directly utilize naked eyes or ultraviolet-visible pectrophotometer to judge, whether just can detect fast in solution containing Cd
2+, realize Cd in solution
2+quick, easy colorimetric detection.Preferably, in conjunction with color standards, Cd in solution to be detected can be determined further
2+concentration range.More preferably, in conjunction with Cd
2+the canonical plotting of concentration and ultravioletvisible absorption strength relationship, can accurately detect Cd in detected aqueous solution further
2+levels.
Therefore, detection method of the present invention is simple, flexible design, do not need large-scale instrument and equipment, there is high sensitivity and selectivity, and sampling amount is few, be applicable to the detection of the various solution such as lake, water quality of river investigation, sewage effluent water quality detection, the urgent water safety detection of outdoor activities and domestic water, and may be used for the detection of food, blood, urine, range of application is wider.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Embodiment 1: Cd in water sample
2+detection
(1) Cd of variable concentrations is configured
2+aqueous solution: by the Cd of difference amount
2+join in ultrapure water and prepare various known Cd
2+the aqueous solution of concentration, as 0M, 5 × 10
-3m, 1 × 10
-3m, 5 × 10
-4m, 1 × 10
-4m, 5 × 10
-5m, 1 × 10
-5m, 5 × 10
-6m, 1 × 10
-6m, 5 × 10
-7m, 1 × 10
-7m, 5 × 10
-8m, 1 × 10
-8m etc.
(2) preparation detects liquid: by 0.2g macrodex heating for dissolving in 100mL ultrapure water, room temperature is cooled to after dissolving, under the condition stirred, add the chlorauric acid solution of 5mL 0.5mM, continue the sodium hydroxide solution dripping 2mL 0.1M, after reaction 2h, obtained golden nanometer particle aqueous solution of modifying containing macrodex; Measure this golden nanometer particle aqueous solution appropriate as detection liquid sample product, regulate its pH to 9.20 ~ 10.20 with the sodium hydrate aqueous solution of 0.1mol/L, for subsequent use as detection liquid;
(3) bore hole color standards series: test tube A, B, C, D, E, F, G, H of preparing same size ... respectively to the detection liquid added in each test tube in 9.0mL above-mentioned (2), continue the Cd respectively to adding each concentration obtained in above-mentioned (1) in each test tube
2+solution 0.5mL, shakes up; Continue respectively to adding equal-volume isoconcentration (0.5mL 10 in each test tube
-4m) thioacetyl amine aqueous solution mixing, wait for the change of aqueous solution color quietly, this series is as color standards; Find to work as Cd
2+concentration is lower than 1 × 10
-7during M, solution colour does not change or does not substantially change;
(4) Cd in water sample to be detected
2+detection: prepare and the test tube of (3) same size, get in (2) and detect liquid 9.0mL, add water sample 0.5mL to be detected, shake up, continue to add 0.5mL 10
-4m thioacetyl amine aqueous solution, obtains the mixed solution containing water sample to be measured after 10min, this is contained 0M concentration C d in the mixed solution color of water sample to be measured and color standards series
2+the color of aqueous solution compares, if color changes, then shows in water sample to be checked containing Cd
2+if without color change, then show Cd in water sample to be measured
2+concentration is lower than 1 × 10
-7m.
(5) if obtained in this water sample to be measured containing Cd by above-mentioned (4)
2+, in order to determine Cd in this water sample to be detected further
2+concentration range, adopt colourimetry to carry out, contain the mixed solution color of water sample to be measured by this and color standards series carries out colorimetric control, observe its color and be in concentration ranges position, thus determine Cd in water sample to be measured
2+concentration range.
(6) color standards series concentration Cd in measurement of ultraviolet-visible spectrophotometer above-mentioned (3) is used
2+the absorbance of aqueous solution, wavelength coverage is 200nm ~ 800nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting; Mixed solution containing water sample to be measured in (4) is also carried out the measurement of ultraviolet-visible pectrophotometer, and the result of gained is compared with canonical plotting, Cd in this water sample to be measured can be obtained
2+concentration.
Embodiment 2: Cd in industrial and mineral company water sample
2+detection
(1) water sampling to be detected: at the sample location of industrial and mineral company discharge of wastewater mouth at set intervals (as 1h, 2h ...) gather water sample, then mixed in equal amounts becomes biased sample, regulates its pH to make it be alkalescence afterwards with NaOH, in order to avoid affect Detection results, obtain water sample to be detected;
(2) preparation detects liquid: as described in the step (2) in embodiment 1;
(3) bore hole color standards series: as described in the step (3) in embodiment 1;
(4) Cd in water sample to be measured
2+detection: basic as described in the step (4) in embodiment 1, about 15min obtains the mixed solution containing water sample to be measured, this is contained 0M concentration C d in the mixed solution color of water sample to be measured and color standards series
2+the color of aqueous solution compares, and color changes, and the mixed solution containing water sample to be measured darkens, and is aubergine, then show in water sample to be checked containing Cd
2+, and its concentration is higher than 10
-7m.In order to determine Cd in this water sample to be detected further
2+concentration range, adopt colourimetry to carry out, contain the mixed solution color of water sample to be measured by this and color standards series carries out colorimetric control, observe its color and be in concentration ranges position, thus determine Cd in water sample to be measured
2+concentration range, thus determine whether to reach the condition that sewage can discharge.
Embodiment 3: Cd in soil
2+detection
(1) water sampling to be detected: do multi-point sampling in same soil sampling place, then mix, join in ultrapure water by mixed pedotheque, quiescent setting is until upper liquid presents transparent, then get its upper liquid and the upper liquid alkalization that will obtain, obtain water sample to be detected;
(2) preparation of liquid is detected: as described in the step (2) in embodiment 1;
(3) bore hole color standards series: as described in the step (3) in embodiment 1;
(4) Cd in soil water sample
2+detection: basic as described in the step (4) in embodiment 1, about 20min obtains the mixed solution containing water sample to be measured, this is contained 0M concentration C d in the mixed solution color of water sample to be measured and color standards series
2+the color of aqueous solution compares, and color does not change, then show Cd in water sample to be measured
2+concentration is lower than 1 × 10
-7m.
(5) in order to whether accurately confirm further in this water sample to be detected containing Cd
2+and this Cd
2+concentration has much, uses color standards series concentration Cd in measurement of ultraviolet-visible spectrophotometer above-mentioned (3)
2+the absorbance of aqueous solution, wavelength coverage is 200nm ~ 800nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting; Mixed solution containing water sample to be measured in (4) is also carried out the measurement of ultraviolet-visible pectrophotometer, and the result of gained is compared with canonical plotting, Cd in this water sample to be measured can be obtained
2+concentration.
Embodiment 4: pellet Cd in air
2+in detection
(1) water sampling to be detected: by having the sampling thief of certain cutting characteristic, the air of certain volume is extracted with constant speed, the suspended particulate substance that then in air, particle diameter is less than 100 μm is trapped within the filter membrane of constant weight, the suspended particle NaOH collected is alkalized, it is made to dissolve, obtained water sample to be detected;
(2) preparation of liquid is detected: as described in the step (2) in embodiment 1;
(3) bore hole color standards series: as described in the step (3) in embodiment 1;
(4) Cd in water sample to be detected
2+detection: basic as described in the step (4) in embodiment 1, about 15min obtains the mixed solution containing water sample to be measured, this is contained 0M concentration C d in the mixed solution color of water sample to be measured and color standards series
2+the color of aqueous solution compares, and color does not change, then show Cd in water sample to be measured
2+concentration is lower than 1 × 10
-7m, is namely considered as in this water sample to be detected not containing Cd
2+.
(5) in order to whether accurately confirm further in this water sample to be detected containing Cd
2+and this Cd
2+concentration, uses color standards series concentration Cd in measurement of ultraviolet-visible spectrophotometer above-mentioned (3)
2+the absorbance of aqueous solution, wavelength coverage is 200nm ~ 800nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting; Mixed solution containing water sample to be measured in (4) is also carried out the measurement of ultraviolet-visible pectrophotometer, and the result of gained is compared with canonical plotting, Cd in this water sample to be measured can be obtained
2+concentration.
Embodiment 5: Cd in lake water water sample
2+detection:
(1) water sampling to be detected: with water sampling bottle in river, certain depth (20 ~ 50cm) place of three different locations, lake gathers water sample, then regulate its pH in alkalescence with NaOH, in order to avoid affect Detection results, obtain water sample S5.1 ~ S5.3 to be detected;
(2) preparation of liquid is detected: as described in the step (2) in embodiment 1;
(3) bore hole color standards series: as described in the step (3) in embodiment 1;
(4) Cd in water sample to be detected
2+detection: basic as described in the step (4) in embodiment 1, prepare three with test tube first, the second, third of (3) middle same size; Respectively to adding the above-mentioned detection liquid of 9.0mL in test tube; Then in test tube, add 0.5mL water sample S5.1 ~ S5.3 to be detected, shake up; Continue respectively to adding the isocyatic thioacetyl amine aqueous solution (0.5mL 10 of equal-volume in test tube first, second, third
-4m) mix, observe 0M concentration C d in the color of aqueous solution in test tube first, second, third and color standards series
2+the color of aqueous solution; In 5min, if the color of solution deepens relative to standard colorimetric solution colour in test tube first and second, then judge in water sample containing Cd
2+; And by finding after contrast that in first, concentration of cadmium ions is 10
-5m is to 10
-6between M; In 20min, if the color of solution deepens relative to standard colorimetric solution colour in test tube second, then judge Cd in water sample
2+concentration is 10
-6m is to 10
-7between M; And the solution colour in test tube third does not change after 30min, ultraviolet-visible pectrophotometer is needed to determine Cd further
2+content;
(5) in order to accurately confirm Cd in this water sample to be detected further
2+concentration, uses color standards series concentration Cd in measurement of ultraviolet-visible spectrophotometer above-mentioned (3)
2+the absorbance of aqueous solution, wavelength coverage is 650nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting; Mixed solution containing water sample S5.1 ~ S5.3 to be measured in (4) is also carried out the measurement of ultraviolet-visible pectrophotometer, and the result of gained is compared with canonical plotting, obtain Cd in this water sample to be measured
2+concentration; The concentration results of last average S5.1, S5.2, S5.3 is determined in water sample containing Cd
2+concentration.
Embodiment 6: Cd in electrical equipment, Electroplate Factory's water sample
2+detection:
(1) water sampling to be detected: at the sample location of discharge of wastewater mouth at set intervals (as 1h, 2h ...) gather water sample, then mixed in equal amounts becomes biased sample, mix four points of sample S6.1 ~ S6.4 respectively, its pH is regulated to make it be alkalescence with NaOH afterwards, in order to avoid affect Detection results, obtain water sample to be detected;
(2) preparation of liquid is detected: as described in the step (2) in embodiment 1;
(3) bore hole color standards series: as described in the step (3) in embodiment 1;
(4) Cd in water sample to be detected
2+detection: basic as described in the step (4) in embodiment 1, prepare four with test tube first, the second of (3) middle same size, third, fourth; Respectively to adding the above-mentioned detection liquid of 9.0mL in test tube; Then in test tube, add 0.5mL water sample S6.1 ~ S6.4 to be detected, shake up; Continue respectively to test tube first, second, third, add the isocyatic thioacetyl amine aqueous solution (0.5mL 10 of equal-volume in fourth
-4m) mix, observe 0M concentration C d in the color of aqueous solution in test tube first and test tube second and color standards series
2+the color of aqueous solution; In 10min, if the color of solution deepens relative to standard colorimetric solution colour in test tube first and second, then judge in water sample containing Cd
2+; And pass through than finding after colour contrast that in first, concentration of cadmium ions is 10
-5m is to 10
-6between M; In 20min, if the color of solution deepens relative to standard colorimetric solution colour in test tube second, and pass through than finding after colour contrast that second intermediate ion concentration is 10
-6m is to 10
-7between M; And the solution colour of test tube third, fourth does not change after 30min, ultraviolet is needed to determine ion concentration further;
(5) color standards series concentration Cd in measurement of ultraviolet-visible spectrophotometer above-mentioned (3) is used
2+the absorbance of aqueous solution, wavelength coverage is 650nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting; Mixed solution containing water sample S6.1 ~ S6.4 to be measured in (4) is also carried out the measurement of ultraviolet-visible pectrophotometer, and the result of gained is compared with canonical plotting, Cd in this water sample to be measured can be obtained
2+concentration.The concentration results of last average S6.1, S6.2, S6.3, S6.4 is determined in water sample containing Cd
2+concentration, learn whether electrical equipment, waste water from plating plant can discharge according to national standard.
Embodiment 7: Cd in human urine
2+detection
(1) liquid sample to be detected gathers: from infection from hospital urine sample three parts of S7.1 ~ S7.3, regulates its pH to make it be alkalescence, in order to avoid affect Detection results, obtain water sample to be detected with NaOH;
(2) preparation of liquid is detected: as in embodiment 1 as described in step (2);
(3) bore hole color standards series: as described in the step (3) in embodiment 1;
(4) Cd in urine
2+detection: basic as described in the step (4) in embodiment 1, prepare three with test tube first, the second of (3) middle same size, third, fourth; Respectively to adding the above-mentioned detection liquid of 9.0mL in test tube; Then in test tube, add 0.5mL blood sample S7.1 ~ S7.3 to be detected, shake up; Continue respectively to test tube first, second, third, add the isocyatic thioacetyl amine aqueous solution (0.5mL 10 of equal-volume in fourth
-4m) mix, observe 0M concentration C d in the color of aqueous solution in test tube first and test tube second and color standards series
2+the color of aqueous solution; In 5min, if the color of solution does not change in test tube first, second, third, then judge Cd in sample
2+concentration is lower than 10
-5in M, 30min, if the color of solution does not change in test tube test tube first, second, third, then judge Cd in water sample
2+concentration is lower than 10
-7m; Ultraviolet is needed to determine ion concentration further.
(5) color standards series concentration Cd in measurement of ultraviolet-visible spectrophotometer above-mentioned (3) is used
2+the absorbance of aqueous solution, wavelength coverage is 650nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting; Mixed solution containing S7.1 ~ S7.3 in (4) is also carried out the measurement of ultraviolet-visible pectrophotometer, and the result of gained is compared with canonical plotting, Cd in this water sample to be measured can be obtained
2+concentration.The concentration results of last average S7.1 ~ S7.3 is determined in water sample containing Cd
2+concentration.
Embodiment 8: Cd in blood of human body goods
2+detection
(1) liquid sample to be detected gathers: from infection from hospital patient blood goods, utilize strong acid dissolution, process, strong acid amount used and blood sample ratio 4:1, filtration obtains clear liquid, its pH is regulated to make it be alkalescence with NaOH afterwards, in order to avoid affect Detection results, obtain water sample to be detected three parts of S8.1 ~ S8.3;
(2) preparation of liquid is detected: as embodiment 1(1) as described in (2);
(3) bore hole color standards series: as described in the step (3) in embodiment 1;
(4) Cd in blood sample
2+detection: basic as described in the step (4) in embodiment 1, prepare three with test tube first, the second, third of (3) middle same size; Respectively to adding the above-mentioned detection liquid of 9.0mL in test tube; Then in test tube, add 0.5mL blood sample S8.1 ~ S8.3 to be detected, shake up; Continue respectively to adding the isocyatic thioacetyl amine aqueous solution (0.5mL 10 of equal-volume in test tube first, second, third
-4m) mix, observe 0M concentration C d in the color of aqueous solution in test tube first and test tube second and color standards series
2+the color of aqueous solution; In 5min, if the color of test tube test tube first, second, the third solution does not change, then judge Cd in water sample
2+concentration is lower than 10
-5m; In 15min, if the color of solution does not change in test tube test tube first, second, third, then judge Cd in water sample
2+concentration is lower than 10
-6m; In 30min, if the color of solution does not change in test tube test tube first, second, third, then judge Cd in water sample
2+concentration is lower than 10
-7m; Ultraviolet is needed to determine ion concentration further;
(5) color standards series concentration Cd in measurement of ultraviolet-visible spectrophotometer above-mentioned (3) is used
2+the absorbance of aqueous solution, wavelength coverage is 650nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting; Mixed solution containing S8.1 ~ S8.3 in (4) is also carried out the measurement of ultraviolet-visible pectrophotometer, and the result of gained is compared with canonical plotting, Cd in this water sample to be measured can be obtained
2+concentration.The concentration results of last average S8.1 ~ S8.3 is determined in water sample containing Cd
2+concentration;
By calculating Cd in three experiments
2+concentration is respectively 6 × 10
-9m, 10
-9m, 2 × 10
-9m, all lower than 2.5 × 10
-7the upper limit of concentration of cadmium ions in M(normal human blood sample).
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any amendments and improvement etc. made in spirit of the present invention, all should be included within protection scope of the present invention.
Claims (9)
1. a Cd
2+detection method, it is characterized in that: specifically comprise the steps:
Step 1, stir condition under, by a certain amount of golden salt or silver salt solution and water miscible in right amount and there is the carbohydrate polymer aqueous solution of reductibility, and add appropriate strong basic reagent, obtained after reaction certain hour have the golden nanometer particle of carbohydrate polymer modification or the aqueous solution of Nano silver grain;
The described water miscible and carbohydrate polymer with reductibility comprise in maltose, lactose, glucosan one or more;
The aqueous solution of step 2, having of getting that the above-mentioned steps 1 of certain volume the obtains golden nanometer particle that carbohydrate polymer modifies or Nano silver grain, regulates this solution ph to 9 ~ 11 with alkaline solution, obtains detecting liquid;
Step 3, in the detection liquid that step 2 is obtained, measure out the identical detection liquid sample product of two parts of volumes; Preparation is not containing Cd
2+solution solution as a comparison, add respectively in two parts of described detection liquid sample product by comparative solution and with the isopyknic solution to be detected of comparative solution, form the first mixed liquor and the second mixed liquor;
Step 4, equal-volume, isocyatic thiol compound aqueous solution, thiomicoler's ketone aqueous solution, thiosemicarbazide aqueous solution or thioacetyl amine aqueous solution are added in the first mixed liquor and the second mixed liquor respectively, after stable reaction to be mixed, the color of the first mixed liquor after observing response and reacted second mixed liquor, there is color change if the color of reacted first mixed liquor and reacted second mixed liquor is different, then there is Cd in solution to be detected
2+, and Cd
2+concentration is higher than 10
-7mol/L; If there is not color change, then Cd in solution to be detected
2+concentration is lower than 10
-7mol/L;
Or, equal-volume, isocyatic thiol compound aqueous solution, thiomicoler's ketone aqueous solution, thiosemicarbazide aqueous solution or thioacetyl amine aqueous solution are added in the first mixed liquor and the second mixed liquor respectively, after stable reaction to be mixed, contrast ultravioletvisible absorption intensity, the peak value of reacted second mixed liquor and reacted first mixed liquor, if the ultravioletvisible absorption intensity of reacted second mixed liquor and reacted first mixed liquor, peak value is different changes, then there is Cd in solution to be detected
2+; If unchanged, then there is not Cd in solution to be detected
2+.
2. Cd according to claim 1
2+detection method, it is characterized in that: in described step 1, silver salt comprise in silver nitrate, silver acetate, trifluoroacetic acid silver, trifluoro-methane sulfonic acid silver, silver hexafluoroantimonate and silver tetrafluoroborate one or more; Gold salt comprise in chlorauride, aurous chloride, gold chloride, potassium chloroaurate and sodium chloraurate one or more.
3. Cd according to claim 1
2+detection method, it is characterized in that: described strong basic reagent comprises one or more the mixing in NaOH, potassium hydroxide, baryta hydrate.
4. Cd according to claim 1
2+detection method, it is characterized in that: described water miscible and the carbohydrate polymer with reductibility is water-soluble polyhydroxyl carbohydrate polymer, comprise one or both the mixing in glucosan 100,000, glucosan 140,000, glucosan 200,000, macrodex ten thousand, soluble starch.
5. Cd according to claim 1
2+detection method, it is characterized in that: in described step 2, regulate after solution ph be 9.1 ~ 10.1.
6. Cd according to claim 1
2+detection method, it is characterized in that: in described step 4, thiol compound comprises at least one in thiosalicylic acid, thioacetic acid, thioglycolic acid.
7. Cd according to claim 1
2+detection method, it is characterized in that: formulate color standards, the color of second mixed solution reacted in step 4 and this color standards are carried out colorimetric control, determine Cd in solution to be detected
2+concentration range; Wherein, color standards is formulated as follows:
The identical detection liquid sample product of many parts of volumes are measured out in the detection liquid that step 2 is obtained; The Cd of preparation variable concentrations
2+solution is solution as a comparison, each comparative solution is added respectively in each detection liquid sample product, then add the aqueous solution identical with the equal-volume described in step 4, isocyatic thiol compound aqueous solution, thiomicoler's ketone aqueous solution, thiosemicarbazide aqueous solution or thioacetyl amine aqueous solution wherein and mix, waiting for quietly after solution colour vary stable as color standards.
8. Cd according to claim 1
2+detection method, it is characterized in that: drawing standard curve map, the ultravioletvisible absorption intensity of second mixed liquor reacted in step 4 and canonical plotting contrasted, obtains Cd in solution to be detected
2+concentration;
The method for drafting of described canonical plotting is: first, according to a series of different Cd of compound method preparation of first mixed liquor reacted in described step 4
2+the aqueous solution of concentration, detects its ultravioletvisible absorption intensity respectively when wavelength is 200nm ~ 1000nm, with the ultravioletvisible absorption intensity of each aqueous solution for ordinate, and the Cd in each aqueous solution
2+concentration is horizontal ordinate curve plotting, namely obtains canonical plotting.
9. the Cd according to claim arbitrary in claim 1 to 8
2+detection method, it is characterized in that: described solution to be detected is the solution formed after the water sample in environment, solid-state environmental sample process, the solution formed after environmental sample process in air, food samples are dissolved in the solution, the urine in biomedicine that are formed in water or alcoholic environment and are dissolved in the solution formed in water or alcoholic environment, or the solution that blood dissolves is formed in water or alcoholic environment.
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| 吕晓丽 等.一种简单合成氨基葡聚糖保护的金颗粒的方法.《吉林师范大学学报(自然科学版)》.2006,(第1期),第68-69页. * |
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