CN103528980B - Utilize the flame atomic absorption spectrometry method of trace lead, cadmium in thiomalic acid modified silica-gel separation and concentration-mensuration water sample - Google Patents
Utilize the flame atomic absorption spectrometry method of trace lead, cadmium in thiomalic acid modified silica-gel separation and concentration-mensuration water sample Download PDFInfo
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Abstract
The invention discloses a kind of flame atomic absorption spectrometry method utilizing trace lead, cadmium in thiomalic acid modified silica-gel separation and concentration-mensuration water sample.Take macro porous silica gel as carrier, thiomalic acid is that functional molecular has prepared thiomalic acid modified silica-gel, with thiomalic acid modified silica-gel for adsorbent carries out dynamic separate and enrich to plumbous, cadmium and sets up flame atomic absorption spectrometry detection method.In 0.5-10.0 μ g/mL concentration range, in eluent, Pb (II) absorbance and its concentration are good linear relationship: A=0.0122*C-0.0011(C: μ g/mL); In 0.1-5.0 μ g/mL concentration range, in eluent, Cd (II) absorbance and its concentration are good linear relationship: A=0.1898*C+0.01(C: μ g/mL); The method measures Pb (II), the detection limit of Cd (II) is respectively 12.41,0.79ng/mL.Invention increases sensitivity and the selectivity of detection, the detection for low concentration Pb (II), Cd (II) is easy to robotization.
Description
Technical field
The present invention relates to a kind of method utilizing chemical modification to prepare adsorbent concentration and separation and atomic absorption spectrum coupling Rapid Determination of Trace Lead, cadmium.
Background technology
Along with the propelling of global industry process, heavy metal lead, cadmium pollution cause great threat to the mankind, therefore, in the urgent need to research and develop sensitive, fast, plumbous, cadmium separation and concentration technology easily, to meet the needs of the aspects such as environment measuring.
At present, method that is plumbous in separation and concentration water, cadmium has chemical precipitation method, chemical reduction method, ion exchange process, biological treatment and absorption method etc.Wherein, absorption method because it is easy, efficient and adsorbent is renewable is widely used with recycling.And in various solid adsorption material, silica gel adsorption performance is good, stable chemical nature.Direct use silica gel is as adsorbent for separating of enrichment, and its selectivity is not high, therefore, the silicone hydroxyl of Silica Surface must be utilized to carry out chemical modification and prepare selective absorbent, then detects after carrying out separation and concentration plumbous in sample solution, cadmium.
The flame atomic absorption spectrometry method of trace lead, cadmium in thiomalic acid modified silica-gel separation and concentration-mensuration water sample is utilized not have correlative study temporarily at present.
Summary of the invention
The invention reside in the flame atomic absorption spectrometry method that trace lead, cadmium in a kind of high selectivity separation and concentration-mensuration water sample are provided.
Conceive as follows: although silica gel adsorption performance is good, stable chemical nature, directly use silica gel as adsorbent for separating of enrichment, its selectivity is not high, therefore, usually utilizes the silicone hydroxyl of Silica Surface to carry out modification.By amidation process, thiomalic acid is modified ammonification Silica Surface, thus improve the selectivity of silica gel absorber enriched lead, cadmium, the sensitivity of raising Flame Atomic Absorption Spectrometry Determination trace lead, cadmium and antijamming capability.In this experiment, utilize thiomalic acid modified silica-gel as microtrabeculae adsorbent, plumbous in complicated substrate sample solution, cadmium can be carried out dynamic enrichment and be separated, reduce manual steps, improve the reappearance and precision that measure.
The present invention relates to dynamic microcolumn separation and enrichment and the coupling of atomic absorption light spectral method.When plumbous in testing sample solution, cadmium is by the microtrabeculae that is loaded with adsorbent, plumbous, cadmium and Silica Surface thiomalic acid generation Absorptive complex wave, then with eluent by lead, cadmium wash-out carry out Atomic Absorption Spectrometry.
Concrete steps are as follows:
(1) thiomalic acid modified silica-gel absorbent preparation:
Take 30-70 order microsphere silica gel 30g, be placed in 250mL there-necked flask, install condenser pipe, add the hydrochloric acid that 150.0mL concentration is 6.0mol/L, heating makes solution return and mechanical raking 5-6 hour, cooled and filtered goes out silica gel, and washing to wash solution with distilled water by silica gel is neutral (whether having chlorion with the silver nitrate inspection wash solution that mass percent is 2%), and vacuum drying obtains activated silica gel.
Take the above-mentioned activated silica gel of 30.0g, be placed in 250ml there-necked flask, add the chemical pure gamma-aminopropyl-triethoxy-silane (KH550) after 100.0mL analysis pure toluene and 10.0-15.0mL distilation respectively, mechanical raking also adds hot reflux 6 hours, cooled and filtered solid product, respectively wash solid product 3 times with analysis pure toluene, absolute ethyl alcohol, after vacuum drying, obtain γ-Aminopropyl silica gel (APSG).
Take 4.5-6.0g thiomalic acid, be dissolved in 150ml and analyze pure N, in dinethylformamide (DMF), then add 1.0-1.5g successively and analyze pure N-hydroxy-succinamide (NHS), 8.5-9.0g analyzes pure 1-ethyl-(3-dimethylamino-propyl) carbodiimide hydrochloride (EDCHCl) and makes it to dissolve, finally add the above-mentioned γ-Aminopropyl silica gel of 30.0g, stirring at normal temperature filtered out solid product after 24 hours, respectively with analyzing pure N, dinethylformamide (DMF), each 5 times of absolute ethanol washing solid product, the drying of suction filtration final vacuum obtains thiomalic acid modified silica-gel (TMSG).
(2) thiomalic acid modified silica-gel separation and concentration lead, cadmium:
By peristaltic pump, self-made miniature post, ((7cm × 0.5mmi.d.), polyfluortetraethylene pipe (0.8mmi.d) and jointing are formed separation and concentration device.First a small amount of glass wool beyond the Great Wall in pillar one end before dress post, upper prop loads adsorbent thiomalic acid modified silica-gel prepared by step (1) in a wet process, then fills in a small amount of glass wool, and compacting also connects, utilize peristaltic pump that redistilled water is pumped into micro-column, for subsequent use after washing; The separation and concentration step of Pb (II) is as follows: Pb (II) solution of pH=6.0 is passed through micro-column with 1.8mL/min flow velocity, then wash away not by the ion adsorbed in micro-column with the blank solution of 5.0mLpH=6.0 with 1.8mL/min flow velocity, with 10.0mL1.0mol/LHCl with the reverse wash-out of 3.0mL/min flow velocity by the Pb (II) adsorbed; The separation and concentration step of Cd (II) is as follows: Cd (II) solution of pH=8.0 is passed through micro-column with 1.8mL/min flow velocity, then wash away not by the ion adsorbed in micro-column with the blank solution of 5.0mLpH=8.0 with 1.8mL/min flow velocity, with 10.0mL1.0mol/LHCl with the reverse wash-out of 3.6mL/min flow velocity by the Cd (II) adsorbed.Elute soln is used for follow-up Atomic Absorption Spectrometry.
(3) detection method:
Determining instrument: atomic absorption spectrophotometer (AAS) (Beijing Puxi General Instrument Co., Ltd); Measure the instrument condition of Pb element: wavelength 283.3nm, slit 0.5nm, lamp current 2.0mA, burner height 5.0mm, acetylene flow 1500mL/min, air mass flow 5000mL/min; Measure the instrument condition of Cd element: wavelength 228.8nm, slit 0.5nm, lamp current 2.0mA, burner height 5.0mm, acetylene flow 1500mL/min, air mass flow 5000mL/min; Utilize the Pb (II) in Flame Atomic Absorption Spectrometry Determination above-mentioned steps (2) gained eluent or Cd (II) concentration.
(4) drafting of standard working curve:
Pb (II) standard solution of 10.0mLpH=6.0 or Cd (II) standard solution of pH=8.0 are carried out separation and concentration and Atomic Absorption Spectrometry according to step (2) and step (3); In 0.5-10.0 μ g/mL concentration range, in eluent, Pb (II) absorbance and its concentration are good linear relationship: A=0.0122*C-0.0011, C are concentration, and its unit is μ g/mL, linearly dependent coefficient r=0.9993; In 0.1-5.0 μ g/mL concentration range, in eluent, Cd (II) absorbance and its concentration are good linear relationship: A=0.1898*C+0.01, C are concentration, and its unit is μ g/mL, linearly dependent coefficient r=0.9994.
(5) mensuration that is plumbous in test sample, cadmium content is treated:
Pb (II) sample solution of pH=6.0 or Cd (II) sample solution of pH=8.0 are carried out separation and concentration and Atomic Absorption Spectrometry according to step (2) and step (3), obtains absorbance A; Finally calculate Pb in sample solution (II) or Cd (II) concentration C according to calibration curve.
Instant invention overcomes the complex operation that existing static separation technology exists, the shortcomings such as step is complicated, reappearance is bad, improve sensitivity and the selectivity of detection better, and detection that is plumbous for super low concentration, cadmium is easy to robotization.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of thiomalic acid modified silica-gel in the present invention.
Embodiment
Embodiment:
(1) thiomalic acid modified silica-gel absorbent preparation:
Take 30-70 order microsphere silica gel 30g, be placed in 250mL there-necked flask, install condenser pipe, add the hydrochloric acid that 150.0mL concentration is 6.0mol/L, heating makes solution return and mechanical raking 5 hours, cooled and filtered goes out silica gel, and washing to wash solution with distilled water by silica gel is neutral (whether having chlorion with the silver nitrate inspection wash solution that mass percent is 2%), and vacuum drying obtains activated silica gel.
Take the above-mentioned activated silica gel of 30.0g, be placed in 250ml there-necked flask, add the chemical pure gamma-aminopropyl-triethoxy-silane (KH550) after 100.0mL analysis pure toluene and 13.0mL distilation respectively, mechanical raking also adds hot reflux 6 hours, cooled and filtered solid product, with analyzing each 3 times of pure toluene, absolute ethanol washing solid product, after vacuum drying, obtain γ-Aminopropyl silica gel (APSG).
Take 5.0g thiomalic acid, be dissolved in 150ml and analyze pure N, in dinethylformamide (DMF), then add that 1.2g analyzes pure N-hydroxy-succinamide (NHS), 9g analyzes pure 1-ethyl successively-(3-dimethylamino-propyl) carbodiimide hydrochloride (EDCHCl) make it to dissolve, finally add the above-mentioned γ-Aminopropyl silica gel of 30.0g, stirring at normal temperature filtered out solid product after 24 hours, respectively with analyzing each 5 times of pure DMF, absolute ethanol washing solid product, the drying of suction filtration final vacuum obtains thiomalic acid modified silica-gel (TMSG).Absorbent preparation flow process is as Fig. 1.
(2) thiomalic acid modified silica-gel separation and concentration lead, cadmium:
By peristaltic pump, self-made miniature post, ((7cm × 0.5mmi.d.), polyfluortetraethylene pipe (0.8mmi.d) and jointing are formed separation and concentration device.First a small amount of glass wool beyond the Great Wall in pillar one end before dress post, upper prop loads adsorbent thiomalic acid modified silica-gel prepared by step (1) in a wet process, then fills in a small amount of glass wool, and compacting also connects, utilize peristaltic pump that redistilled water is pumped into micro-column, for subsequent use after washing; The separation and concentration step of Pb (II) is as follows: Pb (II) solution of pH=6.0 is passed through micro-column with 1.8mL/min flow velocity, then wash away not by the ion adsorbed in micro-column with the blank solution of 5.0mLpH=6.0 with 1.8mL/min flow velocity, with 10.0mL1.0mol/LHCl with the reverse wash-out of 3.0mL/min flow velocity by the Pb (II) adsorbed; The separation and concentration step of Cd (II) is as follows: Cd (II) solution of pH=8.0 is passed through micro-column with 1.8mL/min flow velocity, then wash away not by the ion adsorbed in micro-column with the blank solution of 5.0mLpH=8.0 with 1.8mL/min flow velocity, with 10.0mL1.0mol/LHCl with the reverse wash-out of 3.6mL/min flow velocity by the Cd (II) adsorbed.Elute soln is used for follow-up Atomic Absorption Spectrometry.
(3) detection method:
Determining instrument: atomic absorption spectrophotometer (AAS) (Beijing Puxi General Instrument Co., Ltd); Measure the instrument condition of Pb element: wavelength 283.3nm, slit 0.5nm, lamp current 2.0mA, burner height 5.0mm, acetylene flow 1500mL/min, air mass flow 5000mL/min; Measure the instrument condition of Cd element: wavelength 228.8nm, slit 0.5nm, lamp current 2.0mA, burner height 5.0mm, acetylene flow 1500mL/min, air mass flow 5000mL/min; Utilize the Pb (II) in Flame Atomic Absorption Spectrometry Determination above-mentioned steps (2) gained eluent or Cd (II) concentration.
(4) drafting of standard working curve:
Pb (II) standard solution of 10.0mLpH=6.0 or Cd (II) standard solution of pH=8.0 are carried out separation and concentration and Atomic Absorption Spectrometry according to step (2) and step (3); In 0.5-10.0 μ g/mL concentration range, in eluent, Pb (II) absorbance and its concentration are good linear relationship: A=0.0122*C-0.0011, C are concentration, and its unit is μ g/mL, linearly dependent coefficient r=0.9993; In 0.1-5.0 μ g/mL concentration range, in eluent, Cd (II) absorbance and its concentration are good linear relationship: A=0.1898*C+0.01, C are concentration, and its unit is μ g/mL, linearly dependent coefficient r=0.9994.
(5) mensuration that is plumbous in test sample, cadmium content is treated:
Pb (II) sample solution of 100mlpH=6.0 or Cd (II) sample solution of pH=8.0 are carried out separation and concentration and Atomic Absorption Spectrometry according to step (2) and step (3), obtains absorbance A; Finally calculate Pb in sample solution (II) or Cd (II) concentration C according to calibration curve, calculate the recovery, result is as shown in table 1.
Table 1: sample determination and mark-on recovery test data
Claims (1)
1. the flame atomic absorption spectrometry method of trace lead, cadmium in thiomalic acid modified silica-gel separation and concentration-mensuration water sample, is characterized in that concrete steps are as follows:
(1) thiomalic acid modified silica-gel absorbent preparation:
Take 30-70 order microsphere silica gel 30g, be placed in 250mL there-necked flask, install condenser pipe, adding 150.0mL concentration is 6.0mol
/the hydrochloric acid of L, heating makes solution return and mechanical raking 5-6 hour, and cooled and filtered goes out silica gel, and it is neutral for washing silica gel to wash solution with distilled water, whether have chlorion with the silver nitrate inspection wash solution that mass percent is 2%, vacuum drying obtains activated silica gel;
Take the above-mentioned activated silica gel of 30.0g, be placed in 250ml there-necked flask, add the chemical pure gamma-aminopropyl-triethoxy-silane after 100.0mL analysis pure toluene and 10.0-15.0mL distilation and KH550 respectively, mechanical raking also adds hot reflux 6 hours, cooled and filtered solid product, wash solid product successively 3 times with analysis pure toluene, absolute ethyl alcohol, after vacuum drying, obtain γ-Aminopropyl silica gel and APSG;
Take 4.5-6.0g thiomalic acid, be dissolved in 150ml and analyze pure N, in dinethylformamide and DMF, then add 1.0-1.5g successively and analyze pure N-hydroxy-succinamide and NHS, 8.5-9.0g analyzes pure 1-ethyl-(3-dimethylamino-propyl) carbodiimide hydrochloride and EDCHCl and makes it to dissolve, finally add the above-mentioned γ-Aminopropyl silica gel of 30.0g, stirring at normal temperature filtered out solid product after 24 hours, respectively with analyzing pure N, dinethylformamide, each 5 times of absolute ethanol washing solid product, the drying of suction filtration final vacuum obtains thiomalic acid modified silica-gel and TMSG,
(2) thiomalic acid modified silica-gel separation and concentration lead, cadmium:
Separation and concentration device is made up of peristaltic pump, self-made miniature post, polyfluortetraethylene pipe and jointing; First a small amount of glass wool beyond the Great Wall in pillar one end before dress post, upper prop loads adsorbent thiomalic acid modified silica-gel prepared by step (1) in a wet process, then fills in a small amount of glass wool, and compacting also connects, utilize peristaltic pump that redistilled water is pumped into micro-column, for subsequent use after washing; The separation and concentration step of Pb (II) is as follows: Pb (II) solution of pH=6.0 is passed through micro-column with 1.8mL/min flow velocity, then wash away not by the ion adsorbed in micro-column with the blank solution of 5.0mLpH=6.0 with 1.8mL/min flow velocity, with 10.0mL1.0mol/LHCl with the reverse wash-out of 3.0mL/min flow velocity by the Pb (II) adsorbed; The separation and concentration step of Cd (II) is as follows: Cd (II) solution of pH=8.0 is passed through micro-column with 1.8mL/min flow velocity, then wash away not by the ion adsorbed in micro-column with the blank solution of 5.0mLpH=8.0 with 1.8mL/min flow velocity, with 10.0mL1.0mol/LHCl with the reverse wash-out of 3.6mL/min flow velocity by the Cd (II) adsorbed; Elute soln is used for follow-up Atomic Absorption Spectrometry;
(3) detection method:
Determining instrument: atomic absorption spectrophotometer (AAS); Measure the instrument condition of Pb element: wavelength 283.3nm, slit 0.5nm, lamp current 2.0mA, burner height 5.0mm, acetylene flow 1500mL/min, air mass flow 5000mL/min; Measure the instrument condition of Cd element: wavelength 228.8nm, slit 0.5nm, lamp current 2.0mA, burner height 5.0mm, acetylene flow 1500mL/min, air mass flow 5000mL/min; Utilize the Pb (II) in Flame Atomic Absorption Spectrometry Determination above-mentioned steps (2) gained eluent or Cd (II) concentration;
(4) drafting of standard working curve:
Pb (II) standard solution of 10.0mLpH=6.0 or Cd (II) standard solution of pH=8.0 are carried out separation and concentration and Atomic Absorption Spectrometry according to step (2) and step (3); In 0.5-10.0 μ g/mL concentration range, in eluent, Pb (II) absorbance and its concentration are good linear relationship: A=0.0122*C-0.0011, C are concentration, and its unit is μ g/mL, linearly dependent coefficient
r=0.9993; In 0.1-5.0 μ g/mL concentration range, in eluent, Cd (II) absorbance and its concentration are good linear relationship: A=0.1898*C+0.01, C are concentration, and its unit is μ g/mL, linearly dependent coefficient
r=0.9994;
(5) mensuration that is plumbous in test sample, cadmium content is treated:
Pb (II) sample solution of pH=6.0 or Cd (II) sample solution of pH=8.0 are carried out separation and concentration and Atomic Absorption Spectrometry according to step (2) and step (3), obtains absorbance A; Finally calculate Pb in sample solution (II) or Cd (II) concentration according to calibration curve.
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| CN105688827B (en) * | 2016-01-31 | 2017-11-10 | 常州大学 | Porous-starch/thiomalic acid composite xerogel is applied to the Gardenia Yellow molecule in absorption water |
| CN107376872B (en) * | 2017-08-06 | 2020-01-21 | 桂林理工大学 | Preparation method of chitosan-soybean protein composite porous microspheres for lead adsorption |
| CN107442073A (en) * | 2017-08-06 | 2017-12-08 | 桂林理工大学 | For the preparation method for the crosslinking soybean protein microballoon for adsorbing cadmium |
| CN108088804B (en) * | 2017-12-04 | 2019-08-02 | 武汉大学 | A kind of measuring method of trace cadmium in water samples |
| CN115382900A (en) * | 2022-10-12 | 2022-11-25 | 成都理工大学 | Method for leaching and repairing heavy metal contaminated soil by using thiomalic acid |
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