CN103505907B - A kind of online solid phase micro-extraction method of flow injection and device thereof - Google Patents
A kind of online solid phase micro-extraction method of flow injection and device thereof Download PDFInfo
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Abstract
The invention discloses sample-pretreating method and the special purpose device thereof of the online SPME of a kind of flow injection, this device mainly comprises the SPME post of being filled by integral post in an arm, a six-way valve, two peristaltic pumps, sampling valves.Before sample analysis, six-way valve is placed in extraction position, SPME post inside the Pass sample is entered by six-way valve under the effect of sampling valve and peristaltic pump, complete and after collecting waste liquid bottle until sample stream, switch six-way valve and start elution action at once, the target components be enriched on extraction column is transported in detecting instrument the analysis carrying out next step by eluent.The present invention is applicable to extracting and enriching drinking water, surface water and low-viscosity (mobile) liquid Gold Samples being belonged to element, and simple to operation, sample requirement is little, can analyze continuously and on-line preconcentration by batch.
Description
Technical field
The invention belongs to environmental analysis and analytical chemistry field, relate to sample-pretreating method and the related device thereof of the online SPME of a kind of flow injection, utilize the method can realize the on-line preconcentration of SPME.
Background technology
Along with the quickening of process of industrialization and scale, the heavy metal element in entered environment gets more and more, and enters human body further by drinking water or food chain, finally has influence on the health of the mankind.Therefore, the metal element analyse in food security, environmental monitoring and living things system just becomes one of important research contents.For metal element analyse, the key step of sample pretreatment process has: dissolve, filter, clear up, extraction etc., and wherein, extraction is most important step.Roughly, extraction can be divided into liquid-liquid extraction and liquid-solid extraction according to form, can be divided into ion-exchange, absorption, chelating three kinds of modes of action according to principle.Complete because SPE (SPE) has concentration and separation one step, easy and simple to handle, regenerating easily, easily be automated, the feature such as environmental protection more favored, SPE becomes current topmost sample pretreatment mode.But, commercialization solid-phase extraction device, as extraction cylinder and extracting disk complex operation, expensive.Meanwhile, SPE still needs the sample pre-treatments of relative complex, the dissatisfactory situation of the rate of recovery.
Solid phase micro-extraction technique is a kind of new extraction and separation technology grown up on SPE basis, owing to avoiding using solvent or use a small amount of solvent, becomes latest generation sample treatment technology, and is expected to finally replace SPE.Since 1975 Flow Injection Analysis (FIA) concept proposed first after, because it can carry out under nonequilibrium dynamic condition, and adaptability is extensive, analysis efficiency is high, sample and reagent consumption few, accuracy of detection is high, the advantages such as equipment is simple, obtain over more than 20 year and develop rapidly, be widely used in a lot of field, particularly with the Instrument crosslinking such as FT-IR, AAS, ICP-AES, ICP-MS, UV-VIS, CE, for realization in real time, online, in-situ study detects and provides effective means.This project is devoted to, by SPME technology and flow injection (FI) and inductively coupled plasma atomic emission spectrometer (ICP-AES) coupling, to set up the analytical method of heavy metal ion in series of samples.
Summary of the invention
First technical problem to be solved by this invention provides a kind of flow injection online solid phase micro-extraction method for the above-mentioned state of the art, on the reservation former advantageous basis of SPME sample-pretreating method, realize the on-line preconcentration of metal ion in water sample.
Second technical problem to be solved by this invention is the online solid-phase micro-extracting device of a kind of flow injection, can be realized the on-line preconcentration of metal ion in water sample by this device.
The present invention solves the technical scheme that above-mentioned first technical problem adopt: the online solid phase micro-extraction method of a kind of flow injection, it is characterized in that adopting the online solid-phase micro-extracting device of following flow injection to carry out, concrete steps are: before sample analysis, six-way valve is placed in extraction position, sample liquid enters in-tube solid-phase micro-extraction column by six-way valve under the effect of sampling valve and peristaltic pump, flows in waste liquid bottle again through stripped sample liquid from sample pipeline; After having extracted, switch six-way valve and start wash-out position, the target components eluted, with certain flow velocity drip washing in-tube solid-phase micro-extraction column, is then conveyed into the detection analysis that Atomic Emission Spectrometer AES carries out next step by eluent.
As improvement, described sample liquid and eluent are in the state of continuous-flow in whole extraction elution process, the volume of described sample liquid and eluent is 8 ~ 12mL, flow velocity is 0.1 ~ 0.5mL/min, in sample liquid, metal ion (as cobalt ions) concentration is 0.1 ~ 3.0 μ g/mL, extraction time is 20 ~ 40min, elution time 15 ~ 30min.
Preferably, described volume is 10mL, and flow velocity is 0.3mL/min, and concentration of metal ions is 1.0 μ g/mL, and extraction time is 30min, elution time 20min.
Finally, described in-tube solid-phase micro-extraction column is made up of disposable syringe plastic tube, adopts in-situ polymerization technology synthesis monoblock type epoxy resin-matrix porous polymer as extraction phase in pipe.
The present invention solves the technical scheme that above-mentioned second technical problem adopt: the online solid-phase micro-extracting device of a kind of flow injection, it is characterized in that the online solid-phase micro-extracting device of described flow injection comprises in-tube solid-phase micro-extraction column, six-way valve, peristaltic pump and sampling valve, wherein six-way valve is connected with sample liquid, eluent, in-tube solid-phase micro-extraction column, Atomic Emission Spectrometer AES injection port respectively; Peristaltic pump is two, and be located between sampling valve and six-way valve for one, another is located between in-tube solid-phase micro-extraction column and waste liquid bottle; By six-way valve, realize the sample introduction extraction of in-tube solid-phase micro-extraction column and the switching of elution process.
As improvement, described in-tube solid-phase micro-extraction column is made up of disposable syringe plastic tube, and internal diameter is not more than 0.5mm, and length is not more than 8cm, is filled with Monolithic Columns as extraction phase in column jecket.
As preferably, described extraction phase is porous epoxy resin base polyalcohol, is to adopt situ aggregation method to synthesize in pipe.
Improve, described waste liquid bottle is two again, one for collecting sample introduction extraction time more than liquid, liquid more than when another is for collecting wash-out.
Finally, described six-way valve is provided with extraction position and wash-out position, and when being placed in extraction position, sample liquid communicates with the pipeline of in-tube solid-phase micro-extraction column, and remaining liquid is collected by a waste liquid bottle; When being placed in wash-out position, eluent communicates with in-tube solid-phase micro-extraction column, and target components is transported to Atomic Emission Spectrometer AES detects, and remaining liquid is collected by another waste liquid bottle.
Compared with prior art, the invention has the advantages that: the in-tube solid-phase micro-extraction column material in apparatus of the present invention is hollow disposable syringe needle tubing, adopt in-situ polymerization technology in column jecket, synthesize monoblock type epoxy resin-matrix porous polymer extraction phase, target components is in extraction column after adsorption equilibrium, wash-out, enter in the injector of Atomic Emission Spectrometer AES through transfer tube, simple and practical.Extract utilizing target components in the complete paired samples of this device and in elution process, only need a switching action of six-way valve, therefore operate very easy.Sample requirement of the present invention is little, favorable reproducibility, can analyze continuously and on-line preconcentration by batch, can be used for the detection of the field metallic elements such as ambient water quality, food, biochemistry.
Accompanying drawing explanation
Fig. 1 is the connection diagram of apparatus of the present invention: wherein Fig. 1 a is sample extraction position, and sample liquid flow carries out dynamic extraction absorption schematic diagram through extraction column; Fig. 1 b is sample elution position, and eluent stream carries out dynamic desorption target components through extraction column, and target components enters the schematic diagram of Atomic Emission Spectrometer AES through transfer tube;
Fig. 2 is the curve map that extraction time affects adsorbance;
Fig. 3 is the curve map that sample substrate pH value affects adsorbance.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
As shown in Figure 1, the online solid-phase micro-extracting device of a kind of flow injection, this device comprises in-tube solid-phase micro-extraction column 1, six-way valve 3, two peristaltic pumps 2 and 4, sampling valve 5 and waste liquid bottle W1 and W2; Described in-tube solid-phase micro-extraction column 1 makes in disposable injection of plastic pipe by being synthesized by epoxy resin-matrix porous polymer, and internal diameter is not more than 0.5mm, and length is not more than 8cm; Six-way valve 3 is connected with sample liquid A, eluent B, in-tube solid-phase micro-extraction column 1, Atomic Emission Spectrometer AES injection port respectively; Wherein peristaltic pump 2 is between in-tube solid-phase micro-extraction column 1 and waste liquid bottle W1, for controlling the flow velocity of solution through in-tube solid-phase micro-extraction column 1, peristaltic pump 4 between six-way valve 3 and sampling valve 5, for completing the importing of experiment reagent;
In described device, six-way valve 3 position be in Fig. 1 a is sample dynamic extraction position in in-tube solid-phase micro-extraction column 1, sample liquid A passes through sampling valve 5 with certain flow velocity under the effect of peristaltic pump 4, extraction passage is entered by six-way valve 3, flowing through in-tube solid-phase micro-extraction column 1 and complete dynamic extraction, is finally to waste liquid bottle W1; Six-way valve 3 position be in Fig. 1 b is sample from in-tube solid-phase micro-extraction column 1 by wash-out and the wash-out position transferred to inductively coupled plasma atomic emission spectrometer (ICP-AES) or other analytical instrument, eluent B passes through sampling valve 5 with certain flow velocity under the effect of peristaltic pump 4, wash-out passage is entered by six-way valve 3, flow through in-tube solid-phase micro-extraction column 1 and complete wash-out, sample is transferred to inductively coupled plasma atomic emission spectrometer (ICP-AES) or other analytical instrument from in-tube solid-phase micro-extraction column 1 by wash-out, is finally to waste liquid bottle W2.
Before sample extraction is analyzed, first six-way valve 3 is placed in extraction position.During extractive analysis, sample liquid A communicates with the pipeline of in-tube solid-phase micro-extraction column 1, regulate the pressure of peristaltic pump 4 by sample liquid by sampling valve 5 import pipe, regulate the flow velocity of Stress control sample liquid A through in-tube solid-phase micro-extraction column 1 of peristaltic pump 2, remaining liquid is collected by waste liquid bottle W1; After having extracted, six-way valve 3 is switched to wash-out position, with the every adjustment operation of above-mentioned extractive analysis, eluent B drip washing in-tube solid-phase micro-extraction column 1, and target components is transported to Atomic Emission Spectrometer AES detects, remaining liquid is collected by waste liquid bottle W2.In sample pretreatment process, described water sample is in the state of continuous-flow; The volume of described water sample is 10mL, and flow velocity is 0.3mL/min, and in water sample, the concentration of cobalt ions is 10 μ g/mL; Described in-tube solid-phase micro-extraction column adopts epoxy resin-matrix porous polymer material to make.
Optimum choice below with regard to extraction conditions carries out description of test:
I. experimental section:
1.1. instrument and reagent
FIA-3110 flow injection analyzer (Beijing Jitian Instrument Co., Ltd.).2100DV inductively coupled plasma atomic emission spectrometer (Perkin-Elmer Instrument Ltd.).All experiments water is Milli-Q (Millipore, USA).Monoblock type epoxy resin-matrix SPME post in homemade pipe.
1.0mg/mLCo
3+storing solution is by analyzing pure CoCl
36H
2o deionized water is prepared.Co
3+standard working solution is diluted to desired concn by storing solution deionized water.Dust technology and ammoniacal liquor is adopted to regulate the pH value of working solution.
1.2. operating procedure
Six-way valve, see Fig. 1, before sample analysis, is first placed in extraction position (Fig. 1 a), by the pipeline communication of sample cell and extraction column by extraction equipment.During extraction, regulate the pressure of peristaltic pump 4, sample liquid A to be circulated pipeline by sampling valve, and regulate the Stress control sample liquid A of peristaltic pump 2 to flow out from extraction column in pipe with fixing flow velocity, the water sample through extraction flows into waste liquid bottle W1; After having extracted, six-way valve is placed in wash-out position (Fig. 1 b), regulates peristaltic pump 2 to control the flow velocity of eluent, with fixing flow velocity drip washing extraction column, then the target components eluted is conveyed into the detection analysis that Atomic Emission Spectrometer AES carries out next step.
When not illustrating in addition, all experiments are carried out all under the following conditions: volume of water sample is 10mL, and flow velocity is 0.3mL/min, and concentration of cobalt ions is 1.0 μ g/mL, monoblock type epoxy resin-matrix porous polymer extraction column in pipe.
II. result and discussion:
The optimization of 2.1 extraction conditions:
2.1.1 extraction flowing rate:
For investigating extraction flow velocity to the impact of adsorbance, adopt 0.1 respectively, 0.2, the extraction flow velocity of 0.3mL/min extracts cobalt ions solution.Result shows, extraction flow velocity is not on adsorbance impact significantly (adsorbance is respectively 0.0598,0.0668,0.0620mg/g).0.3mL/min is selected to extract, to ensure to obtain higher extraction efficiency in shorter extraction time.
2.1.2 extraction time optimization:
Investigate extraction time to the impact of adsorbance.As seen from Figure 2, adsorbance constantly increases along with the increase of time, when extraction time reaches 90min, occurs extraction equilibrium not yet.According to the non-equilibrium theory of SPME, under certain condition, extraction quantity and concentration linear.Take into account sensitivity and extraction efficiency, select the shorter analysis time that can meet actual needs, therefore select 30min as optimum extraction time.
2.1.3 sample substrate pH value is optimized:
In order to obtain the best extraction efficiency of cobalt ions, being become by cobalt ions solution preparation pH value to be 2 ~ 9, under fixing condition, investigating sample substrate pH value to the impact of adsorbance.As can be seen from Figure 3, when substrate pH is less than 3, the adsorbance of cobalt ions sharply declines; When pH value raises, when being between 3 ~ 7, adsorbance is without significant change; When pH value is greater than 7, adsorbance starts more slowly to decline.Based on the result that above pH optimizes, the pH value of subsequent experimental Quality control solution is 7.
2.2 elution requirement optimizations:
Adopt orthogonal arrage L
9(3
3) orthogonal test, eluting solvent composition, elution time and elution flow rate are analyzed.
Carry out range analysis (table 1) to experimental result, optimum washing engaging condition is elution time is 20min, is 5%HNO with mass fraction
3solution is with the elution flow rate of 0.3mL/min.
Table 1
2.3 methods existing is divided into, precision, detection limit:
The linear research of cobalt ions standard aqueous solution is found, within the scope of 0.1 ~ 3.0 μ g/mL, there is good linear relationship, equation of linear regression is y=95460.9x-5562.2, coefficient correlation is 0.9993, detection limit (S/N=3) is 0.03 μ g/mL, and the coefficient of variation (n=5) is less than 5%.
2.4 water determinations:
With optimal conditions, carry out recovery test by standard addition method to certain school's periphery field irrigation water sample, the rate of recovery is between 86.5% ~ 94.2%.
III. conclusion:
The present invention establishes the online Solid-phase Microextraction of flow injection in the application measuring cobalt ions content in water, cobalt ions in water sample from design on-line preconcentration system in pipe in the effect of epoxy resin-matrix SPME pillar, reach the object of on-line preconcentration, then adopt Inductively coupled plasma atomic emission spectrometry.Measure actual water sample, result is satisfactory.This system is expected to be applied to the on-line preconcentration of metal ion in waste water.
Claims (6)
1. the online solid phase micro-extraction method of flow injection, it is characterized in that adopting the online solid-phase micro-extracting device of following flow injection to carry out, concrete steps are: before sample analysis, six-way valve is placed in extraction position, sample liquid enters in-tube solid-phase micro-extraction column by six-way valve under the effect of sampling valve and peristaltic pump, flows in waste liquid bottle again through stripped sample liquid from sample pipeline; After having extracted, switch six-way valve and start wash-out position, the target components eluted, with certain flow velocity drip washing in-tube solid-phase micro-extraction column, is then conveyed into the detection analysis that Atomic Emission Spectrometer AES carries out next step by eluent;
The online solid-phase micro-extracting device of described flow injection comprises in-tube solid-phase micro-extraction column, six-way valve, peristaltic pump and sampling valve, and wherein six-way valve is connected with sample liquid, eluent, in-tube solid-phase micro-extraction column, Atomic Emission Spectrometer AES injection port respectively; Peristaltic pump is two, and be located between sampling valve and six-way valve for one, another is located between in-tube solid-phase micro-extraction column and waste liquid bottle; By six-way valve, realize the sample introduction extraction of in-tube solid-phase micro-extraction column and the switching of elution process;
Described sample liquid and eluent are in the state of continuous-flow in whole extraction elution process, the volume of described sample liquid and eluent is 8 ~ 12mL, flow velocity is 0.1 ~ 0.5mL/min, in sample liquid, concentration of metal ions is 0.1 ~ 3.0 μ g/mL, extraction time is 20 ~ 40min, elution time 15 ~ 30min;
Described in-tube solid-phase micro-extraction column is made up of disposable syringe plastic tube, adopts situ aggregation method synthesis, be filled with propane type epoxy resin of di phenolic group-diethylenetriamine porous polymer as extraction phase in pipe.
2. require the method described in 1 according to claims, it is characterized in that described volume is 10mL, flow velocity is 0.3mL/min, and concentration of metal ions is 1.0 μ g/mL, and extraction time is 30min, elution time 20min.
3. the online solid-phase micro-extracting device of flow injection in right 1 or 2 method, it is characterized in that the online solid-phase micro-extracting device of described flow injection comprises in-tube solid-phase micro-extraction column, six-way valve, peristaltic pump and sampling valve, wherein six-way valve is connected with sample liquid, eluent, in-tube solid-phase micro-extraction column, Atomic Emission Spectrometer AES injection port respectively; Peristaltic pump is two, and be located between sampling valve and six-way valve for one, another is located between in-tube solid-phase micro-extraction column and waste liquid bottle; By six-way valve, realize the sample introduction extraction of in-tube solid-phase micro-extraction column and the switching of elution process;
Described extraction phase is propane type epoxy resin of di phenolic group-diethylenetriamine porous polymer, is to adopt situ aggregation method to synthesize in pipe.
4. the online solid-phase micro-extracting device of flow injection according to claim 3, it is characterized in that described in-tube solid-phase micro-extraction column is made up of disposable syringe plastic tube, internal diameter is not more than 0.5mm, and length is not more than 8cm, is filled with Monolithic Columns as extraction phase in column jecket.
5. the online solid-phase micro-extracting device of flow injection according to claim 3, is characterized in that described waste liquid bottle is two, one for collecting sample introduction extraction time more than liquid, liquid more than when another is for collecting wash-out.
6. the online solid-phase micro-extracting device of flow injection according to claim 3, is characterized in that described six-way valve is provided with extraction position and wash-out position, and when being placed in extraction position, sample liquid communicates with the pipeline of in-tube solid-phase micro-extraction column, and remaining liquid is collected by a waste liquid bottle; When being placed in wash-out position, eluent communicates with in-tube solid-phase micro-extraction column, and target components is transported to Atomic Emission Spectrometer AES detects, and remaining liquid is collected by another waste liquid bottle.
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