CN104614435A - Method for separating and measuring nano-silver and silver ions - Google Patents
Method for separating and measuring nano-silver and silver ions Download PDFInfo
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- CN104614435A CN104614435A CN201510063410.5A CN201510063410A CN104614435A CN 104614435 A CN104614435 A CN 104614435A CN 201510063410 A CN201510063410 A CN 201510063410A CN 104614435 A CN104614435 A CN 104614435A
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Abstract
The invention relates to a method for separating and measuring nano-silver and silver ions; the nano-silver and the silver ion are separated and measured online by adopting hollow fibre flow field flow fractionation and inductively coupled plasma massspectrometry; and separation and measurement of the nano-silver and the silver ions of various particle sizes are realized through a hollow fibre film separation channel by selecting different mobile phases, radial velocities, focusing times, elution flow rates, sampling amounts, cation exchange resins and eluent conditions. The method disclosed by the invention has the advantages of being high in separation efficiency, low in detection limit, simple to operate, good in reproducibility, high in anti-interference capability and the like; and the method is expected to further separate and measure the nano-silver and the silver ions in complex substrate water, such as exit and entrance water of a sewage treatment plant, and industrial wastewater.
Description
Technical field
The invention belongs to Environmental Analytical Chemistry field, relate to a kind of method of separation determination Nano Silver and silver ion, relate more specifically to a kind of method measuring Nano Silver and silver ion based on hollow fiber flow field-flow fractionation-inductivity coupled plasma mass spectrometry combined system ON-LINE SEPARATION.
Background technology
Nano Silver is most widely used at present, studies one of more nano material (S Wagner, AGondikas, E Neubauer, et al, Angew.Chem.Int.Ed.2014,53,12398 – 2419).Nano Silver is inevitably discharged in environment in production, processing, use, disposal process.Therefore, the environmental effect of Nano Silver and biosafety issues have caused extensive concern (L Geranio, MHeuberger, B Nowack, Environ.Sci.Technol.2009,43,8113-8118).Existing a large amount of report is pointed out, the environmentally safe and health of Nano Silver exists potential negative effect (XL Han, LLai, FF Tian, et al.Small 2012,8,2680-2689).Research shows, Nano Silver and silver ion have different environmental behaviours, and can mutually transform in actual environment.Such as, Nano Silver can discharge silver ion in wet environment or water body, and the Nano Silver therefore in actual environment can exist with variforms such as the silver ion of Nano Silver, Nano Silver aggregation, complex state and free state silver ions.Meanwhile, the silver ion in actual water body, under humic acid effect, can be reduced to Nano Silver (YG Yin, JF Liu, GBJiang, ACS Nano, 2012,6,7910-7919).In addition, toxicologic study shows, Nano Silver and silver ion have different poisonous effects (E Navarro, F Piccapietra, B Wagner, et al, Environ.Sci.Technol.2008,42,8959-8964).For environment and the health risk of scientific evaluation Nano Silver and silver ion, need the self-characteristic understanding Nano Silver and silver ion.Up to the present, Nano Silver and silver ion existence in the environment, migration, conversion and toxicity are known little about it, in part because of lack to Nano Silver and silver ion concentrated, be separated and quantitative method.Therefore, in the urgent need to set up Nano Silver and silver ion effectively be separated and detection method to guarantee its safety applications.
Flow field-flow fractionation technology is a kind of very effective nano material isolation technics, this technical know-how effectively can be separated the particle of 10nm-1000 μm, but to the particle of below 10nm, particularly more difficult (SKR Williams is measured for ion and separation of small molecuies, JR Runyon, AAAshames, Anal.Chem.2011,83,634-642).
Hollow fiber flow field-flow fractionation technology is called as third generation flow field-flow fractionation technology, and compared with traditional flow field-flow fractionation technology, its separation chamber has semipermeable hollow fiber film make by being embedded in open metal or glass tube.In detachment process, axia flow is ordered about particle and is moved to detecting device direction along the internal face of hollow fiber, and ion or Small molecular flow out (AZattoni, S Casolari by the aperture of chamber wall, DC Rambaldi, et al, Anal.Chem., 2007,3,310-323).Hollow fiber flow field-flow fractionation technology has that degree of separation is high, operating cost is low, simple to operate, easily and the feature such as the conventional detecting device coupling such as uv-vis spectra, dynamic light scattering, but the report had not yet to see about hollow fiber flow field-flow fractionation-inductivity coupled plasma mass spectrometry combined system, and there are no the report that pass hollow fiber flow field-flow fractionation systematic position system is applied in Nano Silver and silver ion separation determination.
Summary of the invention
The object of this method is to provide a kind of method measuring Nano Silver and silver ion based on hollow fiber flow field-flow fractionation-inductivity coupled plasma mass spectrometry combined system ON-LINE SEPARATION, to overcome the shortcoming in prior art.
For achieving the above object, the method of separation determination Nano Silver provided by the invention and silver ion, hollow fiber flow field-flow fractionation-inductivity coupled plasma mass spectrometry coupling ON-LINE SEPARATION is adopted to measure Nano Silver and silver ion, with Middle hollow fiber membrane passage, select different mobile phases, radial flow velocity, focal time, elution flow rate, sample size, Zeo-karb and eluant, eluent condition, realize the separation determination of various grain diameter nano silver and silver ion.
Wherein, hollow-fibre membrane is regenerated cellulose, polysulfones, polyethersulfone or polyacrylonitrile.
Wherein, mobile phase is lauryl sodium sulfate, Triton X-114 or FL-70 aqueous solution, and concentration is 0.05-0.2% (v/v).
Wherein, radial flow velocity selects 0.5-0.7mL/min.
Wherein, focal time is 2.5-4min.
Wherein, axial flow velocity selects 0.7-1.2mL/min.
Wherein, sample feeding amount is 35-60 μ L.
Wherein, Zeo-karb is hydrogen type cation exchange resin, sodium form Zeo-karb or chlorine-based strong alkali anion exchange resins.
Wherein, eluant, eluent is hypo solution, and concentration is 3-5mM.
Compare with the method for silver ion with existing separation determination Nano Silver, this method has the following advantages:
1) highly sensitive, the detection limit of Nano Silver and silver ion is respectively 1.2 μ g/L and 1.6 μ g/L.
2) Nano Silver separation efficiency is high, and degree of separation is greater than 1.5 [R=2 (t
r2-t
r1)/(W
1+ W
2), t
rretention time and the peak width at adjacent two peaks is respectively] with W.
3) reproducible, the relative standard deviation (RSD) repeating sample introduction for three times is all less than 5%.
4) easy and simple to handle.
Accompanying drawing explanation
Fig. 1 is hollow fiber flow field-flow fractionation-inductivity coupled plasma mass spectrometry combined system structural drawing.
Fig. 2 is radial flow velocity on the impact of two kinds of grain diameter nano silver (10nm and 20nm) degree of separation and peak area.
Fig. 3 is focal time on the impact of two kinds of grain diameter nano silver (10nm and 20nm) degree of separation and peak area.
Fig. 4 is the impact of axial flow velocity on two kinds of grain diameter nano silver (10nm and 20nm) degree of separation.
Fig. 5 is the impact of eluant strength on the silver ion recovery.
Embodiment
Technical scheme of the present invention is: in mobile phase, add surfactant, select hollow-fibre membrane as split tunnel, through optimizing the experiment conditions such as radial flow velocity, focal time, elution speed, sample size, Zeo-karb, eluant, eluent, different-grain diameter Nano Silver can be realized be separated with the effective of silver ion, therefore, method of the present invention will be with a wide range of applications in environment measuring field.
Below in conjunction with accompanying drawing, the present invention is described in detail.
Referring to Fig. 1, is hollow fiber flow field-flow fractionation-inductivity coupled plasma mass spectrometry combined system structural drawing that the present invention adopts.The material of split tunnel wherein can select regenerated cellulose, polysulfones, polyethersulfone, polyacrylonitrile etc.; The material of split tunnel is adopted to be polyethersulfone in an embodiment of the present invention.
The dispersiveness that surfactant can improve nano-Ag particles is added in mobile phase, the present invention is by investigating the aqueous solution of the conventional surfactant such as lauryl sodium sulfate, Triton X-114, FL-70 respectively, and the surfactant agent of selecting in an embodiment of the present invention is FL-70 aqueous solution.The present invention examines FL-70 concentration of aqueous solution further in 0.05-0.2% (v/v) scope, to the separating property of Nano Silver and silver ion, FL-70 concentration is selected to be that 0.1% (v/v) is as optimum surfactant concentration in an embodiment of the present invention.
The present invention examines the performance of radial flow velocity separation determination Nano Silver (10nm and 20nm) and silver ion within the scope of 0.2-1.0mL/min, as seen from Figure 2, when radial flow velocity increases progressively gradually, the degree of separation of two kinds of grain diameter nano silver increases gradually, the peak area of small particle diameter Nano Silver reduces simultaneously, may lose due to part small particle diameter Nano Silver in focusing.Consider, the present invention recommends radial flow velocity to be 0.5-0.7mL/min, selects 0.7mL/min as the radial flow velocity of the best in an embodiment of the present invention.
The present invention examines the separating property to Nano Silver (10nm and 20nm) within the scope of focal time 1-6min, as seen from Figure 3, along with focal time increases, the degree of separation of two kinds of grain diameter nano silver increases gradually, the peak area of Nano Silver increases simultaneously, but retention time is also along with increase.Consider, the present invention recommends focal time to be 2.5-4min, selects 4min as the optimum focusing time in an embodiment of the present invention.
The present invention examines axial flow velocity separating property to Nano Silver (10nm and 20nm) within the scope of 0.3-2.3mL/min, as seen from Figure 4, the degree of separation impact of axial flow velocity on two kinds of grain diameter nano silver is little, but affects the appearance time of Nano Silver.Consider, the axial flow velocity that the present invention recommends is 0.7-1.2mL/min, selects 0.8mL/min as best axial flow velocity in an embodiment of the present invention.
The present invention examines hydrogen type cation exchange resin, sodium form Zeo-karb, chlorine-based strong alkali anion exchange resins to the separation and concentration performance of silver ion, consider, select sodium form Zeo-karb as optimum absorbent separation and concentration silver ion in an embodiment of the present invention.
Refer to Fig. 5, the present invention examines eluent concentration of sodium thiosulfate when changing within the scope of 0-50mM, the recovery of silver ion takes the lead in increasing, having the trend reduced gradually after reaching maximal value, may be because excessive sodium thiosulfate disturbs the mensuration of inductivity coupled plasma mass spectrometry to silver ion.Consider, the eluate concentration that the present invention recommends is 3-5mM, selects 5mM sodium thiosulfate as silver ion eluant, eluent in an embodiment of the present invention.
The present invention examines the separating property of sample size to Nano Silver (10nm and 20nm) within the scope of 2.5-100 μ L, consider, the sample feeding amount that the present invention recommends is 35-60 μ L, selects 50 μ L samples as best sample size in an embodiment of the present invention.
Concrete scheme of the present invention is:
Selection material is hollow-fibre membrane (the internal diameter 0.90mm of polyethersulfone; External diameter 1.50mm; Length 200mm, molecular cut off 10kDa), ram pump (LC-10AT VP, Shimadzu) in being separated for field flow, the high precision of mobile phase solution transports, metering valve is for controlling the flow rate of hollow-fibre membrane entrance and exit in focusing, and T-valve and four-way valve are for controlling to focus on, being separated and the switching of elution process.Sample is by the manual microsyringe (7752i of high speed liquid chromatography HPLC being furnished with quantitative loop (50 μ L), Hamilton) stream is entered, sodium form Zeo-karb is used for on-line preconcentration silver ion, Inductively coupled plasma mass spectrometry (ICP) is for the on-line checkingi of Nano Silver and silver ion, mobile phase is the aqueous solution (0.1%, v/v) of FL-70.In focusing, switch respectively four-way valve to metering valve direction, T-valve (A) to detecting device direction, T-valve (B) to middle sampling valve direction, radial flow velocity selects 0.7mL/min, and focal time is 4min.In detachment process, switch respectively four-way valve to sampling valve direction, T-valve (A) to waste liquid direction, T-valve (B) to detecting device direction, radial flow velocity selects 0.7mL/min, and axial flow velocity is 0.8mL/min.In elution process, switch respectively four-way valve to metering valve direction, T-valve (A) to detecting device direction, T-valve (B) is to middle sampling valve direction, select 5mM sodium thiosulfate as silver ion eluant, eluent, elution flow rate is 1.0mL/min.
The present invention is further illustrated by the following examples.
Embodiment 1: the separation determination of Nano Silver and silver ion in lake water and river
(1) selection of separation condition:
Selection material is hollow-fibre membrane (the internal diameter 0.90mm of polyethersulfone; External diameter 1.50mm; Molecular cut off 10kDa), during ram pump (LC-10AT VP, Shimadzu) is separated for field flow, the high precision of mobile phase solution transports; Sample is by the manual microsyringe (7752i of high speed liquid chromatography HPLC being furnished with quantitative loop (10 μ L), Hamilton) stream is entered, sodium form Zeo-karb (Amberlite IR120) is for on-line preconcentration silver ion, inductivity coupled plasma mass spectrometry and workstation (7700, Agilent) (λ=420nm) is for the on-line checkingi of Nano Silver and silver ion, mobile phase is the aqueous solution (0.1%, v/v) of FL-70.Silver ion eluant, eluent is 5mM sodium thiosulfate solution.
In focusing, switch respectively four-way valve to metering valve direction, T-valve (A) to detecting device direction, T-valve (B) to middle sampling valve direction, radial flow velocity selects 0.7mL/min, and focal time is 4min.In detachment process, switch respectively four-way valve to sampling valve direction, T-valve (A) to waste liquid direction, T-valve (B) to detecting device direction, radial flow velocity selects 0.7mL/min, and axial flow velocity is 0.8mL/min.In elution process, switch respectively four-way valve to metering valve direction, T-valve (A) to detecting device direction, T-valve (B) is to middle sampling valve direction, select 5mM sodium thiosulfate as silver ion eluant, eluent, elution flow rate is 1.0mL/min.
(2) mensuration of Nano Silver and silver ion in reality
Adopt this hollow fiber flow field-flow fractionation-inductivity coupled plasma mass spectrometry combined system to adding target Nano Silver in Peking University's Wei Ming Lake lake water sample and Caobai River river sample and silver ion has carried out separation determination.The method is 80.2 ~ 95.0% (20 μ g/L, 10nm-AgNP) and 83.2 ~ 84.1% (20 μ g/L, Ag to the recovery adding Nano Silver and silver ion in standard specimen
+).
Claims (9)
1. the method for a separation determination Nano Silver and silver ion, hollow fiber flow field-flow fractionation-inductivity coupled plasma mass spectrometry coupling ON-LINE SEPARATION is adopted to measure Nano Silver and silver ion, with Middle hollow fiber membrane passage, select different mobile phases, radial flow velocity, focal time, elution flow rate, sample size, Zeo-karb and eluant, eluent condition, realize the separation determination of various grain diameter nano silver and silver ion.
2. method according to claim 1, wherein, hollow-fibre membrane is regenerated cellulose, polysulfones, polyethersulfone or polyacrylonitrile.
3. method according to claim 1, wherein, mobile phase is lauryl sodium sulfate, Triton X-114 or FL-70 aqueous solution.
4. method according to claim 1, wherein, radial flow velocity selects 0.5-0.7mL/min.
5. method according to claim 1, wherein, focal time is 2.5-4min.
6. method according to claim 1, wherein, axial flow velocity selects 0.7-1.2mL/min.
7. method according to claim 1, wherein, sample feeding amount is 35-60 μ L.
8. method according to claim 1, wherein, Zeo-karb is hydrogen type cation exchange resin, sodium form Zeo-karb or chlorine-based strong alkali anion exchange resins.
9. method according to claim 1, wherein, eluant, eluent is hypo solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107081271A (en) * | 2017-06-07 | 2017-08-22 | 中国科学院生态环境研究中心 | Nano material multidimensional isolates and purifies system |
| CN113125365A (en) * | 2021-04-16 | 2021-07-16 | 中国科学院生态环境研究中心 | Device and method for quantitatively identifying nano zinc oxide and zinc ions in solution |
| CN113933375A (en) * | 2021-10-19 | 2022-01-14 | 中国科学院生态环境研究中心 | Method and device for removing metal ions and retaining metal nanoparticles |
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| CN104297369A (en) * | 2014-09-28 | 2015-01-21 | 中国科学院生态环境研究中心 | Device and method for determining nanometer material through hollow fiber field-flow fractionation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107081271A (en) * | 2017-06-07 | 2017-08-22 | 中国科学院生态环境研究中心 | Nano material multidimensional isolates and purifies system |
| CN107081271B (en) * | 2017-06-07 | 2019-06-18 | 中国科学院生态环境研究中心 | Nano material multidimensional isolates and purifies system |
| CN113125365A (en) * | 2021-04-16 | 2021-07-16 | 中国科学院生态环境研究中心 | Device and method for quantitatively identifying nano zinc oxide and zinc ions in solution |
| CN113933375A (en) * | 2021-10-19 | 2022-01-14 | 中国科学院生态环境研究中心 | Method and device for removing metal ions and retaining metal nanoparticles |
| CN113933375B (en) * | 2021-10-19 | 2024-03-01 | 中国科学院生态环境研究中心 | Method and device for removing metal ions and retaining metal nano particles |
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