CN102967574A - Method for fast enriching and detecting trace amount of As (V) and Cr (VI) contained in water by filling microcolumn by utilizing fiber - Google Patents
Method for fast enriching and detecting trace amount of As (V) and Cr (VI) contained in water by filling microcolumn by utilizing fiber Download PDFInfo
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- CN102967574A CN102967574A CN2012105331622A CN201210533162A CN102967574A CN 102967574 A CN102967574 A CN 102967574A CN 2012105331622 A CN2012105331622 A CN 2012105331622A CN 201210533162 A CN201210533162 A CN 201210533162A CN 102967574 A CN102967574 A CN 102967574A
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Abstract
The invention provides a method for detecting a trace amount of As (V) and Cr (VI) which are contained in a water sample, and particularly relates to a method for enriching As (V) and Cr (VI) by filling quaternary ammonium fibers into a microcolumn and utilizing a solid-phase extraction method and detecting As (V) and Cr (VI) by adopting an ultraviolet spectrophotometry, relating to the technical field of waste water detection. The method solves the technical problem that the analysis of a trace amount of metal ions contained in the water sample is limited on water treatment as the conventional detection method is insufficient in selectivity and detection limit due to matrix effect and other interference existing during the analysis of the trace amount of metal ions contained in the water sample. The method for enriching As (V) and Cr (VI) by filling the quaternary ammonium fibers into the microcolumn and utilizing the solid-phase extraction method and detecting As (V) and Cr (VI) by adopting the ultraviolet spectrophotometry comprises the following steps: filling self-made quaternary ammonium ion exchange fibers into the microcolumn; placing into a solid-phase adsorption separation device so that As (V) and Cr (VI) are adsorbed to the self-made quaternary ammonium ion exchange fibers; and detecting eluted analytes by adopting the ultraviolet spectrophotometry. The method disclosed by the invention has the characteristics of simple process, little time consumption and easiness and convenience for operation without special pretreatment of the water sample and can meet the requirements for trace amount analysis by respectively achieving the detection limits of As (V) and Cr (VI) at 0.2 ppb and 0.8 ppb.
Description
Technical field
The present invention relates to waste water detection technique field, specifically, relate to a kind of fiber microtrabeculae that utilizes, enrichment also detects underwater trace As (V) and the method for Cr (VI).
The invention still further relates to the using method of above-mentioned analytical equipment.
Background technology
Heavy metal arsenic and chromium are two kinds of elements that toxicity is very large, even low concentration still has very large harmfulness.They in water environment mainly with inorganic form (Cr (III)/Cr (VI), As (III)/As (V)) and organic form exist, these heavy metal ion are difficult to degrade in environment, can be concentrated by water environment enrichment in the aquatic organism object, enter human body (animal) through food chain, cause various diseases and disorder.Therefore currently detect in the urgent need to arsenic and chromium to trace, in order to understand its harmfulness.
Existing atomic absorption spectrography (AAS), ICP-MS, chemoluminescence method, ICP-OES, ultraviolet spectrophotometry has been widely used in the detection of trace element, and in these methods, atomic absorption spectrography (AAS) sensitivity is low, the multielement simultaneous determination difficulty; ICP-MS is expensive, vulnerable to pollution; The chemoluminescence method pre-service is complicated, poor selectivity.In addition, still there is the inferior position of detectability deficiency in these methods for trace or when disturbing serious water sample analysis, have restricted its practice.Measure after utilizing the SPE solid phase extraction techniques with tested element preenrichment, can greatly reduce detectability, traditional preenrichment such as liquid-liquid extraction method, ionic liquid preenrichment method, chemical precipitation method, ion exchange process, these methods exist uses toxic reagent, cost is high, poor stability, the defective of taking reagent, complex operation.It is large that ion-exchange fibre has contact area, and absorption and drip washing resolution speed are fast, and resistance to flow is little, large, the easy reusable advantage of adsorbance.At present with the existing many reports of its research as adsorbent.
The present invention is by the extraction of solid phase microtrabeculae and ultraviolet spectrophotometry coupling, use it for enrichment and the detection of underwater trace As (V) and Cr (VI), that the method has is easy and simple to handle, sample need not special pre-treatment, highly sensitive, adsorption capacity and enrichment factor are large, the advantage of renewable recycling.
Summary of the invention
The technical matters that is difficult for detection in order to solve the underwater trace heavy metal ion; Given this, the invention provides a kind of fiber-filled microtrabeculae device enrichment As (V) and Cr (VI) of utilizing, can realize detection to trace As (V) and Cr (VI) with the ultraviolet spectrophotometry coupling, it is fast that the method has not only kept solid phase microtrabeculae sample introduction speed, the advantage that enrichment times is high, and this fibrous material elution speed is fast, reuses respond well.
For achieving the above object, the Solid-Phase Extraction method is as follows:
The first step with the homemade quaternary ammonium type ion-exchange fibre length 25mm that packs into, in the tygon microtrabeculae of diameter 0.5mm, is made solid-phase extraction column;
Second step, with the fiber microtrabeculae, flow circuit control valve, little threeway and pick-up unit connect, and concrete method of attachment is:
The washing device that will hold the sampling device of sample and hold eluent is connected to the two ends of little threeway 1, is being provided with flowrate control valve between sampling device and the little threeway 1 and between washing device and the little threeway 1,
Waste liquid cylinder and eluent container are connected to the two ends of little threeway 2,
By the 3rd port of little threeway 1 and the 3rd port of little threeway 2, quaternary ammonium type fiber solid phase microtrabeculae is connected between little threeway 1 and the little threeway 2,
Be assembled into thus the separation and concentration device;
The 3rd step, with the flow velocity washing stream 1～2min of rare nitric acid with 0.5～1.5mL/min, then neutral to the pH value with the flow velocity washing stream of 8～12mL/min with pure water successively;
The 4th step, sample to be transferred in certain pH 3.5～5.0 scopes, the flow velocity of control 1～3mL/min is by the separation and concentration device, and analyte is retained on the fiber, and the waste liquid that is not adsorbed will flow in the end liquid;
In the 5th step, will be enriched in metallic element wash-out on the microtrabeculae with the eluant, eluent of minute quantity with the flow velocity of 0.5～1.5mL/min;
In the 6th step, the metallic element on the analyte microtrabeculae of enrichment is detected with the ultraviolet spectrometry photometry.Rare nitric acid of above-mentioned using method, except special instruction is arranged, its concentration is 0.5～1.5mol/L.
Above-mentioned eluant, eluent is ammoniacal liquor, rare NaOH, the mixed solution of ammoniacal liquor-ammonium chloride.
Above-mentioned detection method, detecting wavelength for As (V) is 880nm, detecting wavelength for Cr (VI) is 540nm.
The present invention is take the quaternary ammonium salt ion-exchange fibre as the Solid-Phase Extraction sorbing material, it is used for heavy metal ion enrichment, it is low to have cost, the advantage that adsorption capacity is large, the exchange capacity of fiber is 3.2mmol/g, and 95～100 times of enrichment times can be used for the analysis of trace heavy metal, compare with standard reference material, measurement result conforms to standard value.
Ultimate principle of the present invention is: homemade quaternary ammonium type ion-exchange fibre is filled microtrabeculae inside, place the solid phase adsorption tripping device, in the scope with sample pH value modulation 3.5～5.0, As (V) and Cr (VI) are adsorbed on the fiber, then use the eluent of few volume with the analyte wash-out, after adding chromogenic reagent, detect its concentration with ultraviolet spectrophotometry.This detection method is simple, and bioaccumulation efficiency is high, and easily operation is reusable with the fiber after the absorption of particular elutriated liquid wash-out.
Advantage and the effect of this method are as follows:
1. employing differential of the present invention has greatly reduced the consumption of filler from enriching column; And long pillar can be realized As (V) and Cr (VI) adsorption and enrichment so that sample solution and filler have sufficient duration of contact.
2. the sample solution of large volume flows through microtrabeculae, and with the eluent wash-out of small size, so that trace heavy metal ion has obtained the enrichment of more efficient, enrichment times can reach 100 times.
3. device of the present invention is fairly simple, and instrument equipment is common common, such as operation valve, and iron stand, shelf bottle, simple to operate, velocity of separation is fast, has greatly shortened the time of separation and concentration.
4. employing the method, under optimal condition, adsorption column can reach more than 95% at the sample recovery rate of 0.2～50.0ppb As (V) and Cr (VI) content, can carry out fast enrichment and detect.
Description of drawings:
Fig. 1 relates to the device process flow diagram of separation and concentration of the present invention
P1, P2: flow control valve
W1, W2: little threeway
C: pre-separation enrichment microtrabeculae
Embodiment
According to Fig. 1 coupling arrangement, test the performance of above-mentioned method for separating and concentrating
The enrichment of the present invention's design detects concrete technology:
Further narrate the present invention below in conjunction with embodiment:
Specific embodiment 1
The separating column of preparation fiber-filled amount 25mg, be that the solution of 0.8ppb transfers to about pH5.0 with 100mLAs (V) concentration, coutroi velocity 3mL/min flows through enriching apparatus, then the fiber after adsorbing take flow velocity as the 0.5mL/min wash-out with the 1mL eluent, add developer, use UV spectrophotometer measuring, the detection wavelength is 880nm, and As (V) recovery is reached 95.2%.
Specific embodiment 2
The separating column of preparation fiber-filled amount 25mg, be that the solution of 4ppb transfers to about pH5.0 with 100mLAs (V) concentration, coutroi velocity 3mL/min flows through enriching apparatus, then the fiber after adsorbing take flow velocity as the 0.5mL/min wash-out with the 1mL eluent, add developer, use UV spectrophotometer measuring, the detection wavelength is 880nm, and As (V) recovery is reached 95.8%.
Specific embodiment 3
The separating column of preparation fiber-filled amount 25mg, be that the solution of 10ppb transfers to about pH5.0 with 100mLAs (V) concentration, coutroi velocity 1mL/min flows through enriching apparatus, then the fiber after adsorbing take flow velocity as the 0.5mL/min wash-out with the 1mL eluent, add developer, use UV spectrophotometer measuring, the detection wavelength is 880nm, and As (V) recovery is reached 96.3%.
Specific embodiment 4
The separating column of preparation fiber-filled amount 25mg, be that the solution of 0.2ppb transfers to about pH4.0 with 100mLCr (VI) concentration, coutroi velocity 3mL/min flows through enriching apparatus, then the fiber after adsorbing take flow velocity as the 0.5mL/min wash-out with the 1mL eluent, add developer, use UV spectrophotometer measuring, the detection wavelength is 540nm, and Cr (VI) recovery is reached 95.9%.
Specific embodiment 5
The separating column of preparation fiber-filled amount 40mg, be that the solution of 4ppb transfers to about pH4.0 with 100mL Cr (VI) concentration, coutroi velocity 3mL/min flows through enriching apparatus, then the fiber after adsorbing take flow velocity as the 0.5mLl/min wash-out with the 1mL eluent, add developer, use UV spectrophotometer measuring, the detection wavelength is 540nm, and Cr (VI) recovery is reached 96.3%.
Specific embodiment 6
The separating column of preparation fiber-filled amount 25mg, be about the solution modulation pH4.0 of 10ppb with 100mL Cr (VI) concentration, coutroi velocity 1mL/min flows through enriching apparatus, then the fiber after adsorbing take flow velocity as the 0.5mL/min wash-out with the 1mL eluent, add developer, detect with the uv-spectrophotometric agent, the detection wavelength is 540nm, and Cr (VI) recovery is reached 96.4%.
Claims (8)
1. method of utilizing fiber-filled microtrabeculae fast enriching to detect the underwater trace heavy metal said method comprising the steps of: the microtrabeculae preparation, and the device assembling, example enrichment, the analyte wash-out, analyte determination, device cleans:
A. microtrabeculae preparation
The first step: preparation quaternary ammonium type ion-exchange fibre, place baking oven in 60 ° of lower oven dry, preserve under the low temperature;
Second step: described quaternary ammonium type ion-exchange fibre is filled in the tygon microtrabeculae, makes pre-separation enrichment microtrabeculae;
B. device assembling
The washing device that will hold the sampling device of sample and hold eluent is connected to the two ends of little threeway (1), is being provided with flowrate control valve between sampling device and the little threeway (1) and between washing device and the little threeway (1),
Waste liquid cylinder and eluent container are connected to the two ends of little threeway (2),
By the 3rd port of little threeway (1) and the 3rd port of little threeway (2), pre-separation enrichment microtrabeculae is connected between little threeway (1) and the little threeway (2),
Be assembled into thus the separation and concentration device;
C. example enrichment
Sample is adjusted between pH3.5～5.0,, contact with adsorbing medium successively by described separation and concentration device with the flow velocity of 1～3mL/min, then the metallic element of pre-separation is adsorbed on the fiber, and other interference matrixes flow out with waste liquid;
D. analyte wash-out
Elute with the metallic element that the flow velocity of 0.5～1.5mL/min will be enriched on the pre-separation enrichment microtrabeculae with the eluant, eluent of few volume;
E. analyte determination
With the eluent that obtains instrument determination and analysis;
F. device cleans
The first step is with the flow velocity washing stream 1～2min of rare nitric acid with 1～5mL/min;
Second step, with pure water with the flow velocity of 8～12mL/min washing stream to remove residual ion, so that regeneration.
2. the method for claim 1 is characterized in that, the described quaternary ammonium type ion-exchange fibre among the step a has many N (CH
3)
3Positively charged adsorption site.
3. the method for claim 1 is characterized in that, the loading of the described quaternary ammonium type ion-exchange fibre among the step a is 20～30mg.
4. the method for claim 1 is characterized in that, the described microtrabeculae specification among the step a is long 15～25mm, diameter 0.4～0.6mm.
5. the method for claim 1 is characterized in that, the metallic element concentration of the described pre-separation among the step c namely is between 0.2～50ppb in the ppb level.
6. the method for claim 1 is characterized in that, the described eluent in the steps d is one or more in NaOH aqueous solution, ammoniacal liquor, the ammoniacal liquor-ammonium chloride mixed solution.
7. the method for claim 1 is characterized in that, the described pick-up unit among the step e is the ultraviolet spectrometry photometry.
8. the method for claim 1 is characterized in that, the concentration of the described rare nitric acid among the step f is 0.5～2mol/L.
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| CN103837525A (en) * | 2014-03-07 | 2014-06-04 | 山东省科学院海洋仪器仪表研究所 | Device and method for measuring total chromium of water body by flow-injection chemiluminiscence method by enriching and eluting |
| CN111330311A (en) * | 2020-02-13 | 2020-06-26 | 浙江大学 | Phase-change induced target enrichment method |
| CN115343370A (en) * | 2021-05-13 | 2022-11-15 | 中国石油天然气股份有限公司 | System and method for quickly separating lithium element driven by micro-pressure of infusion bottle |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103837525A (en) * | 2014-03-07 | 2014-06-04 | 山东省科学院海洋仪器仪表研究所 | Device and method for measuring total chromium of water body by flow-injection chemiluminiscence method by enriching and eluting |
| CN103837525B (en) * | 2014-03-07 | 2016-01-20 | 山东省科学院海洋仪器仪表研究所 | Enrichment elution flow injected chemical luminescence method measures the device and method of the total chromium of water body |
| CN111330311A (en) * | 2020-02-13 | 2020-06-26 | 浙江大学 | Phase-change induced target enrichment method |
| CN111330311B (en) * | 2020-02-13 | 2021-02-23 | 浙江大学 | Phase-change induced target enrichment method |
| CN115343370A (en) * | 2021-05-13 | 2022-11-15 | 中国石油天然气股份有限公司 | System and method for quickly separating lithium element driven by micro-pressure of infusion bottle |
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Application publication date: 20130313 |