CN102435703A - Method for simultaneously detecting multiple microcystins in water - Google Patents
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- CN102435703A CN102435703A CN2011103806374A CN201110380637A CN102435703A CN 102435703 A CN102435703 A CN 102435703A CN 2011103806374 A CN2011103806374 A CN 2011103806374A CN 201110380637 A CN201110380637 A CN 201110380637A CN 102435703 A CN102435703 A CN 102435703A
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Abstract
A method for simultaneously detecting multiple microcystins in a water sample measures the multiple microcystins in the water by adopting solid phase extraction-liquid chromatography, and comprises the following steps: 1) preparing standard solutions of various microcystins, and preparing a standard curve by adopting a liquid chromatography reversed-phase extraction column; 2) performing solid phase extraction enrichment on a pretreated water sample to be detected by adopting an HLB solid phase extraction column, eluting by using methanol containing trifluoroacetic acid with the volume concentration of 0.1-0.15%, drying eluent under nitrogen flow, and adding methanol for dissolving to prepare a solution to be detected; 3) and (3) determining the solution to be determined in the step (2) by adopting a liquid chromatography reversed-phase extraction column, and comparing the determination result with a standard curve to obtain the content of various microcystins in the water to be determined. The method has the advantages of environment-friendly water sample pretreatment, easy operation, high enrichment multiple, good reproducibility and capability of quickly and accurately analyzing the content of 5 trace microcystins in the water environment.
Description
Technical field
The invention belongs to the detection technique field of water environment pollution thing.Be particularly related to the detection method of multiple trace Microcystin in a kind of water body, specifically be directed against the detection method of multiple trace Microcystin in the surface water.
Background technology
(microcystin is that the toxin that the blue-green algae apoptosis is produced was detrimental to health through food chain, causes hepatic injury after body eutrophication took place MC) to Microcystin.Result of study shows that the content of MCs is very little in the eutrophication water, is merely ng/L or μ g/L level, therefore, detects trace MCs and requires analytical approach to have higher sensitivity, accuracy and repeatability.80~nineties of 20th century; China mainly uses enzyme linked immunological absorption (ELISA) method to detect the MCs in the eutrophication water; The ELISA method has efficiently, fast, characteristics such as sensitivity height; But its antibody is to set up to a certain MC usually, and is not high to the cross reactivity of other types MCs, can not detect some isomeride of MCs.Along with the development of chromatographic technique, can carry out detection by quantitative to the MCs of different isomerization body,
Usually adopt high performance liquid chromatography (HPLC) method to detect trace MCs in the eutrophication water at present.Characteristics such as HPLC has accurately, sensitivity, favorable reproducibility are the MCs detection methods that developed country such as WHO, Great Britain and America and China authoritative institution are recommended.Research in the past utilizes HPLC mainly to analyze MC-LR, and analysis time is generally greater than 10min.Yet according to methylate, the difference of hydroxylation, isomerisation degree and variable amino acid, had been found that and therefore, only detected the hypotype of 80 kinds of Microcystins MC-LR and can not satisfy the requirement of people far away drinking water safety.Given this, need set up a kind of economy, fast, sensitive, accurately and can analyze the analytical approach of multiple MCs (MC-RR, YR, LR, LA and LY) simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of method that detects multiple Microcystin in the water simultaneously, with economical, fast, sensitive, analyze multiple Microcystin simultaneously accurately.
For realizing above-mentioned purpose; The method that detects multiple Microcystin in the water sample simultaneously provided by the invention; Be to adopt SPE-liquid chromatography that multiple Microcystin in the water (MC-RR, MC-YR, MC-LR, MC-LA and MC-LY) is measured, its key step comprises:
1) standard solution of the multiple Microcystin of preparation adopts liquid chromatography reversed phase extraction post preparation standard curve;
2) adopt the HLB solid-phase extraction column to carry out solid phase extraction concentration pretreated water sample to be measured, with the methanol-eluted fractions that contains volumetric concentration 0.1-0.15% trifluoroacetic acid, eluent flows down at nitrogen and dries up, and adds dissolve with methanol and processes solution to be measured;
3) solution to be measured with step 2 adopts liquid chromatography reversed phase extraction post to measure, and measures result and typical curve relatively, obtains the content of various Microcystins in the water to be measured.
Described method, wherein, the reversed phase extraction post is C18 post, C8 post or C2 post.
Described method, wherein, the pre-service of water sample to be measured is the water wettability nylon miillpore filter negative pressure leaching through 0.45 μ m.
Described method, wherein, the HLB solid-phase extraction column carries out activation in advance, and the order of activation is: 10mL chromatographically pure methyl alcohol, 15-20mL ultrapure water, flow velocity is<1mL/min.
Described method, wherein, the condition of solid phase extraction concentration is: flow velocity 2-5mL/min, enrichment finishes final vacuum and drains 1min, and eluent flow rate is less than 1mL/min.
Described method, wherein, the liquid chromatogram measuring condition is: adopting methyl alcohol and volume ratio 0.01-0.03% trifluoroacetic acid ultrapure water is moving phase, flow velocity 1mL/min, 30 ℃ of column ovens; The volume ratio of methyl alcohol: 0-5min is 55%, and 6-10min is 65%, and 10.0min is 55% and is maintained until 12min.
The present invention adopts SPE-high performance liquid chromatography to realize enrichment and quantitative measurement to trace Microcystin in the water environment sample, and operation is simple, analyzes quick and precisely.At present, Shang Weijian has and detection method of the present invention and the similar relevant report of effect thereof.
Description of drawings
Fig. 1 is the chromatogram of 5 kinds of MCs hybrid standard article solution of 1 μ g/mL, and peak sequence is MC-RR:3.916min; MC-YR:5.344min; MC-LR:6.917min; MC-LA:9.733min; MC-LY:10.316min.
Embodiment
The detection method of 5 kinds of trace Microcystins (MC-RR, MC-YR, MC-LR, MC-LA and MC-LY) is following in the water body provided by the invention:
1) water sample pre-service
Utilize successively 10mL chromatographically pure methyl alcohol, 15-20mL ultrapure water activation Waters company HLB (500mg, 6cc) solid-phase extraction column, control flow velocity less than 1mL/min;
2) enrichment method
Utilize 10mL to contain the pure methanol-eluted fractions HLB post of 0.1% trifluoroacetic acid (volume fraction), the control flow velocity is less than 1mL/min, and eluent is collected in the 10mL point end glass centrifuge tube; Eluent flows down slowly to blow until near at nitrogen and does; Add 1mL dissolve with methanol residue, whirlpool mixes, and is to be measured;
3) utilize 5 kinds of MCs of high performance liquid chromatography (HPLC) detection by quantitative
Chromatographic column: ZORBAX 300SB C18,4.6mm * 150mm * 5 μ m;
Gradient elution: adopting methyl alcohol and the ultrapure water that contains 0.02% trifluoroacetic acid is moving phase; The ratio of methyl alcohol: 0-5min maintains 55%, and 6min rises to 65%, and 6-10min maintains 65%; Be maintained until 12min 10.0min roll back 55%, above number percent is percent by volume;
4) drawing standard curve carries out quantitative measurement with external standard method
5) mensuration of sample
Gather water sample to be measured, 1 and 2 pair of water sample carries out pre-service and enrichment method set by step, 3 carries out liquid chromatographic detection set by step again, and the typical curve that obtains with step 4 relatively, finally obtains the content of 5 kinds of MCs in the water sample to be measured through converting.
The invention has the beneficial effects as follows and adopt high performance liquid chromatography that 5 kinds of different Microcystins are carried out quantitative measurement respectively, operation is simple, analyzes quick and precisely.The detection means of 5 kinds of trace Microcystins in the water body of environmental friendliness, easy operating, especially provide a kind of environmental friendliness, easy operating, enrichment multiple height, favorable reproducibility, can be fast the method for multiple Microcystin in the analyzing water body simultaneously.
Below in conjunction with most preferred embodiment the detection method of 5 kinds of trace Microcystin concentration in the water environment of the present invention is explained.
1) pre-service of water sample
Get the 2000ml water sample; Through water wettability nylon miillpore filter (Whatman; 0.45 μ m) carry out negative pressure leaching, filtrating is collected in the Brown Glass Brown glass bottles and jars only, utilizes the HLB solid-phase extraction column of solid-phase extraction device activation Waters company; The order of activation is: 10mL chromatographically pure methyl alcohol, 15-20mL ultrapure water, flow velocity is<1mL/min.
2) enrichment method
Adopt big volume sampling thief that water sample is connected with solid-phase extraction device, start vacuum pump, filtrating is carried out solid phase extraction concentration, the control flow velocity is at 2-5mL/min; Enrichment finishes final vacuum and drains 1min, to remove moisture, utilizes 10ml to contain the pure methanol-eluted fractions HLB post of 0.1% trifluoroacetic acid (volume fraction); The control flow velocity is less than 1mL/min; Eluent is collected in the 10mL point end glass color comparison tube, and eluent flows down slowly to blow until near at nitrogen and does, and adds 1ml dissolve with methanol residue; Whirlpool mixes, and is to be measured.
3) concentration of 5 kinds of MCs of efficient liquid phase chromatographic analysis
The condition that high performance liquid chromatography is selected: high performance liquid chromatograph: comprise the quaternary infusion pump; Automatic sampler, U.S. Agilent company, 1260 types; Agilent chromatogram management software (B.04.02 version) carries out instrument control, data processing and quantitative Analysis, U.S. Agilent company.
Chromatographic column: ZORBAX 300SB C18 (4.6mm * 150mm * 5 μ m), Agilent company.Adopting methyl alcohol and 0.02% trifluoroacetic acid ultrapure water is moving phase, and flow velocity is 1mL/min, and the eluent gradient condition sees table 1 for details, and the column oven condition is 30 ℃.The eluent gradient condition is as shown in table 1.
4) drafting of typical curve is carried out quantitative measurement with external standard method
The drafting of described external standard method typical curve: the MC-RR, YR, LR, LA, the LY that use the pure dissolve with methanol 100 μ g of 1mL respectively; Be mixed with the single mark of the 5 kinds of MC stostes of 100 μ g/mL, get MC-RR, YR, LR, LA, the single mark of the LY stoste of 100 μ L more respectively, using pure methyl alcohol to be mixed with concentration is that the mixed standard solution of 10 μ g/mL is as storing solution; The hybrid standard storing solution is diluted to the standard solution of series concentration with chromatographically pure methyl alcohol; Adopting liquid chromatography to analyze, is respectively horizontal ordinate with concentration, and peak area is that ordinate returns; Obtain 5 typical curves, be used for the amount of working sample analyte.
5) mensuration of the sample and the recovery
Gather water sample to be measured, 1 pair of water sample carries out pre-service set by step, 2 carries out liquid chromatographic detection set by step again, and with the above-mentioned typical curve that obtains relatively, finally obtain the content of 5 kinds of MCs in the mud sample to be measured through converting.
Adopt same water sample, to its mixed standard solution that adds 5 kinds of MCs, 1 pair of water sample carries out pre-service set by step by the amount of 0.5 μ g/L, 2 carries out the content of 5 kinds of MCs of liquid chromatographic detection set by step again, and carries out the recovery according to following formula and calculate:
In the formula:
The R-recovery, %;
C-adds the content of 5 kinds of MCs of standard solution water sample, μ g/mL;
C
0-do not add the content of 5 kinds of MCs of standard solution water sample, μ g/mL.
Below enumerate three instances detection method of the present invention is further specified, but do not limit the present invention.
The water sample in body difficult to understand park, 2000mL Beijing; Add the mixed standard solution of 5 kinds of MCs of the 1 μ g/L of 100 μ L to it; Fully shake up, (Whatman, 0.45 μ m) carries out negative pressure leaching through water wettability nylon miillpore filter; With the HLB solid-phase extraction column enrichment method of 10mL chromatographically pure methyl alcohol, the activation of 15-20mL ultrapure water, the control flow velocity is at 2~5mL/min through in advance for filtrating.Enrichment finishes final vacuum and drains 1min, and 10mL contains the pure methanol-eluted fractions HLB post of 0.1% trifluoroacetic acid, and eluent is collected in the 10mL point end glass color comparison tube; Eluent flows down slowly to blow until near at nitrogen and does; Add 1ml dissolve with methanol residue, whirlpool mixes, and is to be measured.
Utilize the above-mentioned testing sample of liquid chromatogram measuring, the result sees table 2.
The water sample in 2000mL Taihu Lake (31 ° of 21 ' 24.22 " N; 120 ° 1 ' 25.80 " E); Through water wettability nylon miillpore filter (Whatman; 0.45 μ m) carry out negative pressure leaching, with the HLB solid-phase extraction column enrichment method of 10mL chromatographically pure methyl alcohol, the activation of 15-20mL ultrapure water, the control flow velocity is at 2~5mL/min through in advance for filtrating.Enrichment finishes final vacuum and drains 1min, and 10mL contains the pure methanol-eluted fractions HLB post of 0.1% trifluoroacetic acid, and eluent is collected in the 10mL point end glass color comparison tube; Eluent flows down slowly to blow until near at nitrogen and does; Add 1ml dissolve with methanol residue, whirlpool mixes, and is to be measured.
Utilize the concentration of 5 kinds of MCs in the above-mentioned testing sample of liquid chromatogram measuring.Result of calculation obtains, and it is that RR, YR, LR, LY, LA situation are: 0.1645,0.0497,0.8027,0.1435,0.2163 μ g/L that Taihu Lake (31 ° of 21 ' 24.22 " N, 120 ° 1 ' 25.80 " E) water body detects 5 kinds of MCs.
The water sample in 2000mL Chaohu (31 ° of 35 ' 23.53 " N; 117 ° 47 ' 57.05 " E); Through water wettability nylon miillpore filter (Whatman; 0.45 μ m) carry out negative pressure leaching, with the HLB solid-phase extraction column enrichment method of 10mL chromatographically pure methyl alcohol, the activation of 15-20mL ultrapure water, the control flow velocity is at 2~5mL/min through in advance for filtrating.Enrichment finishes final vacuum and drains 1min, and 10mL contains the pure methanol-eluted fractions HLB post of 0.1% trifluoroacetic acid, and eluent is collected in the 10mL point end glass color comparison tube; Eluent flows down slowly to blow until near at nitrogen and does; Add 1ml dissolve with methanol residue, whirlpool mixes, and is to be measured.
Utilize the concentration of 5 kinds of MCs in the above-mentioned testing sample of liquid chromatogram measuring.0.3407,0.1655, ND (not detecting), 0.1364,0.0688 μ g/L result of calculation obtains, and it is that RR, YR, LR, LY, LA situation are that Chaohu water sample (31 ° of 35 ' 23.53 " N, 117 ° 47 ' 57.05 " E) detects 5 kinds of MCs:.
Table 1
Table 2: the water sample recovery of standard addition situation in body difficult to understand park, Beijing
Claims (7)
1. a method that detects multiple Microcystin in the water sample simultaneously adopts SPE-liquid chromatography that multiple Microcystin in the water is measured, and its key step comprises:
1) standard solution of the multiple Microcystin of preparation adopts liquid chromatography reversed phase extraction post preparation standard curve;
2) adopt the HLB solid-phase extraction column to carry out solid phase extraction concentration pretreated water sample to be measured, with the methanol-eluted fractions that contains volumetric concentration 0.1-0.15% trifluoroacetic acid, eluent flows down at nitrogen and dries up, and adds dissolve with methanol and processes solution to be measured;
3) solution to be measured with step 2 adopts liquid chromatography reversed phase extraction post to measure, and measures result and typical curve relatively, obtains the content of various Microcystins in the water to be measured.
2. method according to claim 1, wherein, multiple Microcystin is MC-RR, MC-YR, MC-LR, MC-LA and MC-LY.
3. method according to claim 1, wherein, the reversed phase extraction post is C18 post, C8 post or C2 post.
4. method according to claim 1, wherein, the pre-service of water sample to be measured is the water wettability nylon miillpore filter negative pressure leaching through 0.45 μ m.
5. method according to claim 1, wherein, the HLB solid-phase extraction column carries out activation in advance, and the order of activation is: 10mL chromatographically pure methyl alcohol, 15-20mL ultrapure water, flow velocity is<1mL/min.
6. method according to claim 1, wherein, the condition of solid phase extraction concentration is: flow velocity 2-5mL/min, enrichment finishes final vacuum and drains 1min, and eluent flow rate is less than 1mL/min.
7. method according to claim 1, wherein, the liquid chromatogram measuring condition is: adopting methyl alcohol and volume ratio 0.01-0.03% trifluoroacetic acid ultrapure water is moving phase, flow velocity 1mL/min, 30 ℃ of column ovens; The volume ratio of methyl alcohol: 0-5min is 55%, and 6-10min is 65%, and 10.0min is 55% and is maintained until 12min.
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Cited By (8)
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CN103048398A (en) * | 2012-12-05 | 2013-04-17 | 上海应用技术学院 | Method for determining microcystin MC-LR in water body |
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CN111912986A (en) * | 2020-08-17 | 2020-11-10 | 清华大学 | Broad-spectrum type microcystin enzyme-linked immunoassay kit |
CN113655147A (en) * | 2021-08-17 | 2021-11-16 | 中国环境科学研究院 | Method for detecting microcystin in water |
CN115200968A (en) * | 2022-09-19 | 2022-10-18 | 深圳市环境科学研究院 | Method for purifying various cyanobacteria toxins from algal bloom water body |
CN116642980A (en) * | 2023-05-10 | 2023-08-25 | 临沂大学 | Method for preparing microcystin imprinting material by plasma polymerization and application |
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