CN108426971B - Method for rapidly detecting microcystin in water - Google Patents
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Abstract
The invention discloses a method for rapidly detecting microcystin in water, which comprises the following steps of 1, filtering an obtained water sample, then enriching and purifying by using a transition metal sulfide nano material, then rapidly passing a water body through a filter, adjusting the pH value range of the water sample to be 1-5, and finally eluting by using pure water and methanol; and 2, analyzing and determining the treated water sample by using an ultra-high performance liquid chromatography-tandem mass spectrometry combined technology. After a water sample is enriched and purified by a transition metal sulfide nano material, the sensitivity of MC-LR and MC-RR can reach 20ng/L and 10ng/L respectively by matching with an ultra-high performance liquid chromatography-tandem mass spectrometry combined technology, and the whole process time is less than 20min, so that the dual requirements of an environmental monitoring department on the timeliness and the accuracy of microcystin detection can be completely met. The standard addition experiment proves that the recovery rate of the method for the drinking water sample reaches 97-105%, the recovery rate of the waste water sample reaches 83-99%, and the relative standard deviation is less than 5%. The method has the characteristics of high sensitivity, high analysis speed, strong method selectivity, simple operation and the like.
Description
Technical Field
The invention relates to a method for detecting microcystins in water, in particular to a method for rapidly detecting microcystins in water by copper sulfide nanomaterial enrichment-high performance liquid chromatography-electrospray tandem mass spectrometry.
Background
The phenomenon of water bloom caused by eutrophication of water bodies has caused a great deal of environmental problems in the past decades, and among them, water bloom events such as Taihu lake and Dian lake have been receiving wide attention all over the world. During the bloom process, a large amount of algae are gathered and toxic products, namely algal toxins, are discharged, and serious threats are caused to various organisms in the environmental water body. Microcystins (MCs) are one of the most common types of Microcystins, and many algae produce Microcystins, which are a group of monocyclic heptapeptide substances with two variable amino acids. To date, 80 different subtypes of microcystins have been discovered, depending on the degree of methylation, hydroxylation, epimerization and variable amino acids. The microcystins are most common and most toxic and widely studied by using MC-LR with variable amino acids of leucine (L) and arginine (R), and the two variable amino acids are the second toxic and most extensive MC-RR with arginine (R). Because of the existence of extremely strong organ toxicity such as liver, kidney and the like and strong carcinogenicity, the microcystins are considered as environmental pollutants seriously threatening the health of wild animals and plants and human beings and are widely concerned, and all countries in the world have limited requirements on the concentration of the microcystins in water bodies.
During the outbreak of the bloom, the environmental monitoring department has dual requirements of timeliness and accuracy for the detection of the microcystins. Generally, the sampling is continuously carried out within several hours during the outbreak period to monitor the continuous change of the content of the microcystins, so that the monitoring of the microcystins is preferably required to be completed within 1 hour. The 'surface water environmental quality standard' GB 3838-2002 has a standard limit requirement of 1.0 mu g/L for MC-LR, but the actual monitoring usually requires that the content of the microcystin in the water body is less than 0.1 mu g/L, so that the content change process of the microcystin in the water body is facilitated.
The current common analysis methods for microcystins mainly comprise two major types, namely biochemical methods and instrument analysis methods. The biochemical method mainly adopts an enzyme-linked analysis method, is simple, efficient and rapid, has the detection limit of 0.05-1.0 mu g/L, and has the sensitivity improved by 1000 times than that of a high performance liquid chromatography instrument. On one hand, the method needs to use a microcystin monoclonal antibody, and the preparation of the monoclonal antibody is difficult, so that the monoclonal antibody needs to be imported and is expensive; on the other hand, the method has poor selectivity and is easy to generate false positive phenomenon. The instrumental analysis method mainly adopts high performance liquid chromatography or high performance liquid chromatography-tandem mass spectrometry. The high performance liquid chromatography has low sensitivity, needs high-power enrichment so as to detect a batch of samples within 4-6 hours, and cannot meet the requirement of rapid and timely analysis of water bloom monitoring; and the adopted ultraviolet detector has poor selectivity and is easy to have false positive phenomenon. The high performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) is an analysis method developed in recent years for detecting algal toxins, and has good specificity and high sensitivity. However, the detection limit of the general LC-MS for the microcystins MC-LR and MC-RR is about 1.0 mug/L, and the detection limit for most of the instruments requiring 0.1 mug/L has a certain difference. If the sample is enriched, solid phase extraction or solid phase microextraction is usually adopted. Solid phase extraction needs to consume a large amount of solvent and a large amount of time, the concentration of microcystin in water changes rapidly, reporting within 1 hour is usually required, and the solid phase extraction cannot meet the requirement of rapid monitoring; the solid phase micro-extraction is more suitable for a thermal desorption method, is suitable for substances with stronger volatility, and is not very suitable for the microcystins with the molecular weight of about 1000. Therefore, a rapid, simple, sensitive and efficient enrichment method for enriching microcystins in water and detecting microcystins by combining high performance liquid chromatography-tandem mass spectrometry is urgently needed.
The transition metal sulfide has special physical and chemical properties such as electricity, optics, magnetism, catalysis and lubrication due to the unique internal structure and organization, and is widely applied to the fields of solar cells, pigments, lubricants, catalysts, gas sensors, infrared detectors and the like. In recent years, the research of nanomaterials and nanotechnology has received high attention, and as the particle size decreases, the number of surface atoms, the surface area, the surface energy, and the surface binding energy of nanomaterials have all increased greatly. Because the surface atoms lack adjacent atoms, have unsaturation and are easy to combine with other atoms to be stabilized, the nano material has strong adsorption capacity and can reach adsorption balance in a short time, so the application of the nano material in the adsorption field is also concerned and favored by people. Therefore, the transition metal sulfide nanometer material has various effects of the nanometer particles besides the unique internal organization and structure of the transition metal sulfide nanometer material, and the application of the transition metal sulfide nanometer material in the adsorption field provides a new idea for the related research of sample pretreatment. However, no report of the application of transition metal sulfide in the detection of algal toxin exists at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for rapidly detecting microcystins in water by copper sulfide nano material enrichment-high performance liquid chromatography-electrospray tandem mass spectrometry, which is used for enriching and purifying the microcystins and analyzing MC-LR and MC-RR by the high performance liquid chromatography-tandem mass spectrometry, solves the problem of insufficient sensitivity when the microcystins are directly detected by the high performance liquid chromatography-tandem mass spectrometry, can realize the detection of the microcystins within 20 minutes, and has the characteristics of high sensitivity, high analysis speed, strong method selectivity, simple operation and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for rapidly detecting microcystins in water by copper sulfide nanomaterial enrichment-high performance liquid chromatography-electrospray tandem mass spectrometry comprises the following steps:
step 1, filtering the obtained water sample, adding a transition metal sulfide nano material for enrichment and purification, quickly passing the water body through a filter, adjusting the pH value range of the water sample to be 1-5, and finally eluting with pure water and methanol.
And 2, analyzing and determining the processed sample by using an ultra-high performance liquid chromatography-tandem mass spectrometry combined technology.
In order to optimize the technical scheme, the adopted measures further comprise:
and (3) filtering the water sample obtained in the step (1) by using a 0.2-micrometer polypropylene filter membrane, adding 2-10 mg of copper sulfide nano material cleaned by methanol and pure water, carrying out vortex mixing, and carrying out ultrasonic treatment for 2min for enrichment and purification.
The transition metal sulfide nano material is preferably a copper sulfide nano material.
The preparation method of the copper sulfide nano material comprises the following specific steps: adding 0.2-1.0 g of CuSO4·5H2Dissolving O and 0.2-1.0 g of Polyvinylpyrrolidone (PVC) in deionized water, and dropwise adding 0.1-1.0 mol/L of NaOH and 1-2 ml of CS under stirring2And transferring the mixture to a hydrothermal reaction kettle after 10 minutes, keeping the mixture at 140 ℃ for 18 hours, cooling the mixture to room temperature after the hydrothermal reaction, washing the mixture by using deionized water and ethanol, and drying the mixture at 60 ℃ for 6 hours in vacuum.
The pH value of the water sample is preferably adjusted by using ammonia water and formic acid in the step 1.
The conditions of the liquid chromatography apparatus in the step 2 are as follows: the liquid chromatography apparatus used was an AcquityUPLC system, which separated microcystins in the sample by an Acquity UPLC BEH C18 chromatography column: acquity UPLC BEH C18, 1.7 μm, 2.1 × 100 mm; column temperature: 40 ℃; mobile phase: the phase A is acetonitrile, the phase B is 0.1% formic acid water, the initial proportion is 5% phase A, after 0.5min, the linear increase is carried out to 60% phase A, after 1.5min, the linear increase is carried out to 100% phase A, the linear increase is carried out to 2.5min, and after 2.6min, the phase A starts to be balanced by 5% phase A to 3 min. Flow rate: 0.3 mL/min; sample introduction amount: 10 mu L of the solution; .
The tandem mass spectrometry conditions in the step 2 are as follows: the tandem mass spectrometer used was a Quattro Premier XE triple quadrupole mass spectrometer, electrospray ionization ESI; the scanning mode is as follows: scanning positive ions; the detection mode is as follows: detecting multiple reactions; capillary voltage: 3.0 Kv; source temperature: 110 ℃; the temperature of the desolvation: 380 ℃; desolventizing flow rate: 600L/hr; taper hole air flow rate: 50L/hr; the mass analysis parameters for two common microcystins were: the cone hole voltage of MC-LR is 80V, the collision energy is 50eV, the parent ion/daughter ion reaction channel is 995.5>134.9, the cone hole voltage of MC-RR is 50V, the collision energy is 30eV, and the parent ion/daughter ion reaction channel is 520.0> 134.9.
Compared with the prior art, the method for rapidly detecting microcystins in water by copper sulfide nanomaterial enrichment-high performance liquid chromatography-electrospray tandem mass spectrometry has the following advantages:
1. compared with the current common detection method after direct filtration, the method purifies and concentrates the water sample by filling the copper sulfide nano material, reduces the interference of other impurities in the water, improves the detection sensitivity, and can better meet the requirements of analysis and monitoring;
2. compared with the existing sample pretreatment means, the method can complete analysis within 20 minutes by enriching the copper sulfide nano material, and better meets the requirement of rapid analysis;
3. the method has high recovery rate and good repeatability, and even if a mass spectrometer with lower sensitivity is adopted, the sensitivity of MC-LR and MC-RR in water can respectively reach 20ng/L and 10ng/L, which are far lower than the limit value standard of microcystins in water in China.
Drawings
FIG. 1 is a chromatogram for detecting two kinds of microcystins by the method.
FIG. 2 is a standard curve of two microcystin standard substances at 5 concentration standards analyzed by an instrument.
Detailed Description
Embodiments of the present invention are described in further detail below with reference to the accompanying drawings.
Fig. 1 to 1 are schematic diagrams of detection according to the present invention.
FIG. 1 is a chromatogram for detecting two kinds of microcystins by the method, and the separation effect of the two kinds of microcystins is good.
Fig. 2 is a standard curve of two microcystin standard substances with 5 concentration standards, which is analyzed by an instrument and meets the quality control requirement of actual monitoring.
A detection instrument: the ultra-high performance liquid chromatography instrument used in the experiment is an Acquity UPLC system, and the tandem mass spectrometer used in the experiment is a Quattro Premier XE triple quadrupole mass spectrometer.
The invention relates to a method for rapidly detecting microcystin in water by copper sulfide nanomaterial enrichment-high performance liquid chromatography-electrospray tandem mass spectrometry, which comprises the following steps:
step 1, filtering the obtained water sample, adding a transition metal sulfide nano material for enrichment and purification, quickly passing the water body through a filter, adjusting the pH value range of the water sample to be 1-5, and finally eluting with pure water and methanol.
And 2, analyzing and determining the processed sample by using an ultra-high performance liquid chromatography-tandem mass spectrometry combined technology.
In order to optimize the technical scheme, the adopted measures further comprise:
and (3) filtering the water sample obtained in the step (1) by using a 0.2-micrometer polypropylene filter membrane, adding 2-10 mg of copper sulfide nano material cleaned by methanol and pure water, carrying out vortex mixing, and carrying out ultrasonic treatment for 2min for enrichment and purification.
The transition metal sulfide nano material is preferably a copper sulfide nano material.
The preparation method of the copper sulfide nano material comprises the following specific steps: adding 0.2-1.0 g of CuSO4·5H2Dissolving O and 0.2-1.0 g of Polyvinylpyrrolidone (PVC) in deionized water, and dropwise adding 0.1-1.0 mol/L of NaOH and 1-2 ml of CS under stirring2And transferring the mixture to a hydrothermal reaction kettle after 10 minutes, keeping the mixture at 140 ℃ for 18 hours, cooling the mixture to room temperature after the hydrothermal reaction, washing the mixture by using deionized water and ethanol, and drying the mixture at 60 ℃ for 6 hours in vacuum.
The pH value of the water sample is preferably adjusted by using ammonia water and formic acid in the step 1.
The conditions of the liquid chromatography apparatus in the step 2 are as follows: the liquid chromatography apparatus used was an AcquityUPLC system, which separated microcystins in the sample by an Acquity UPLC BEH C18 chromatography column: acquity UPLC BEH C18, 1.7 μm, 2.1 × 100 mm; column temperature: 40 ℃; mobile phase: the phase A is acetonitrile, the phase B is 0.1% formic acid water, the initial proportion is 5% phase A, after 0.5min, the linear increase is carried out to 60% phase A, after 1.5min, the linear increase is carried out to 100% phase A, the linear increase is carried out to 2.5min, and after 2.6min, the phase A starts to be balanced by 5% phase A to 3 min. Flow rate: 0.3 mL/min; sample introduction amount: 10 mu L of the solution; .
The tandem mass spectrometry conditions in the step 2 are as follows: the tandem mass spectrometer used was a Quattro Premier XE triple quadrupole mass spectrometer, electrospray ionization ESI; the scanning mode is as follows: scanning positive ions; the detection mode is as follows: detecting multiple reactions; capillary voltage: 3.0 Kv; source temperature: 110 ℃; the temperature of the desolvation: 380 ℃; desolventizing flow rate: 600L/hr; taper hole air flow rate: 50L/hr; the mass analysis parameters for two common microcystins were: the cone hole voltage of MC-LR is 80V, the collision energy is 50eV, the parent ion/daughter ion reaction channel is 995.5>134.9, the cone hole voltage of MC-RR is 50V, the collision energy is 30eV, and the parent ion/daughter ion reaction channel is 520.0> 134.9.
And (3) calculating the result by using an external standard curve method, and calculating the concentration of the algal toxin in the water sample on a standard curve according to the peak area response of the quantitative ions, wherein the calculation formula is as follows:
C=( A—b) / ab
wherein: c-concentration of algal toxin, μ g/L;
a-the peak area of the quantitative ion;
b-intercept of the standard curve;
a is the slope of the standard curve;
b-concentration factor.
Example 1:
preparing a copper sulfide nano material:
0.2g of CuSO4·5H2O and 0.2g Polyvinylpyrrolidone (PVC) were dissolved in deionized water, and 0.5mol/L NaOH and 2ml CS were added dropwise with stirring2And transferring the mixture to a hydrothermal reaction kettle after 10 minutes, keeping the mixture at 140 ℃ for 18 hours, cooling the mixture to room temperature after the hydrothermal reaction, washing the mixture by using deionized water and ethanol, and drying the mixture at 60 ℃ for 6 hours in vacuum.
Example 2:
enriching a water sample:
after a water sample is filtered by a 0.2-micron polypropylene filter membrane, 8mg of copper sulfide nano material cleaned by methanol and pure water is added, and after vortex mixing, enrichment and purification are carried out by ultrasonic for 2 min. Then the water body quickly passes through a filter, and finally, pure water and methanol are used for elution.
Example 3:
effect of elution solvent and elution volume on the experiment:
as the detection is carried out by liquid chromatography, the solvent is only selected from methanol (MeOH) and Acetonitrile (ACN), and under the condition that the addition amount is 2.0 mu g/L, the recovery rate experiment is carried out on the solvent and the elution volume, and the results are shown in Table 1, the elution effect of the methanol and the acetonitrile is similar, and the elution volume is optimal to 200 mu L.
TABLE 1 Effect of elution solvent and elution volume on recovery
Example 4:
drawing a standard curve:
standard curves were prepared using a 5:95 acetonitrile/water solvent standard to formulate 5 standard solutions of phycotoxin at concentrations of 1. mu.g/L, 5. mu.g/L, 10. mu.g/L, 20. mu.g/L, and 50. mu.g/L, and the results were as follows:
TABLE 2 measurement of standard curves
| # | 1 | 5 | 10 | 20 | 50 | a | b | R2 |
| MC-LR | 142 | 426 | 730 | 1436 | 3492 | 68.8 | 68.4 | 0.9998 |
| MC-RR | 267 | 794 | 1495 | 2955 | 7176 | 103.4 | 141.5 | 0.9999 |
Example 5:
the pH of the water sample was adjusted to 1.5-9 with ammonia and formic acid, as shown in Table 3, the recovery of both algal toxins was best at pH 2.
TABLE 3 influence of pH of water sample on recovery
Example 6:
influence of extraction material properties on recovery:
purification and extraction efficiencies depend on the choice of extraction material, C2, C8, C18, silica gel, SCX (cation exchanger) were selected for comparison. When different extraction materials were used, the recovery rate was the best when C18 was used as the extraction material, as shown in Table 4, when the addition amount was 2.0 and 10.0. mu.g/L.
TABLE 4 Effect of extraction materials on recovery
Example 7:
detection of algal toxins in drinking water:
and (3) taking 10mL of filtered drinking water into a sample bottle, adding 6mg of copper sulfide nano material cleaned by methanol and pure water, carrying out vortex mixing, and carrying out ultrasonic enrichment and purification for 2 min. The pH was adjusted to 2 with formic acid and then eluted with pure water and methanol. Repeating the labeling for 7 times to obtain 7 parts of labeled liquid to be detected.
And (3) analyzing the liquid to be detected by ultra-high performance liquid chromatography-tandem mass spectrometry under the analysis conditions as above. No algal toxins were detected in the drinking water samples, and the precision and recovery of the spiked samples are shown in the table below.
TABLE 5 determination of the precision and recovery of drinking water samples
As can be seen from the table, the normalized recovery of both algal toxins ranged from 97-105%, with relative standard deviations of 3.15% and 2.67%, respectively.
Example 8:
detection of algal toxins in industrial wastewater:
and (3) taking 10mL of filtered industrial wastewater into a sample bottle, adding 10mg of copper sulfide nano material cleaned by methanol and pure water, carrying out vortex mixing, and carrying out ultrasonic treatment for 2min for enrichment and purification. The pH was adjusted to 2 with formic acid and then eluted with pure water and methanol. Repeating the labeling for 7 times to obtain 7 parts of labeled liquid to be detected.
And (3) analyzing the liquid to be detected by ultra-high performance liquid chromatography-tandem mass spectrometry under the analysis conditions as above. No algal toxins were detected in the wastewater samples, and the precision and recovery of the spiked samples are shown in the table below.
TABLE 6 wastewater sample precision and recovery determination
As can be seen from the table, the normalized recovery of both algal toxins ranged from 83-99% with relative standard deviations of 3.62% and 5.58%, respectively.
While the preferred embodiments of the present invention have been illustrated, various changes and modifications may be made by one skilled in the art without departing from the scope of the invention.
Claims (6)
1. A method for rapidly detecting microcystin in water is characterized by comprising the following steps: the method comprises the following steps:
step 1, filtering an obtained water sample through a 0.2-micrometer polypropylene filter membrane, adding 2-10 mg of a transition metal sulfide nano material cleaned by methanol and pure water, carrying out vortex mixing, carrying out ultrasonic treatment for 2min for enrichment and purification, quickly passing a water body through a filter, adjusting the pH value range of the water sample to be 1-5, and finally eluting with pure water and methanol;
step 2, analyzing and determining the processed sample by using an ultra-high performance liquid chromatography-tandem mass spectrometry (ULLC-MS/MS) technology;
the transition metal sulfide nano material is a copper sulfide nano material, and the preparation method comprises the following specific steps: adding 0.2-1.0 g of CuSO4·H2Dissolving O and 0.2-1.0 g of polyvinylpyrrolidone (PVP) in deionized water, and dropwise adding 0.1-1.0 mol/L NaOH and 1-2 ml of CS under stirring2And transferring the mixture to a hydrothermal reaction kettle after 10 minutes, keeping the mixture at 140 ℃ for 18 hours, cooling the mixture to room temperature after the hydrothermal reaction, washing the mixture by using deionized water and ethanol, and drying the mixture at 60 ℃ for 6 hours in vacuum.
2. The method for rapidly detecting microcystins in water as claimed in claim 1, wherein: the water samples include drinking water, surface water, ground water and industrial wastewater.
3. The method for rapidly detecting microcystins in water as claimed in claim 1, wherein: and in the step 1, ammonia water and formic acid are used for adjusting the pH value of the water sample.
4. The method for rapidly detecting microcystins in water as claimed in claim 1, wherein: the liquid chromatography instrument was used under the following conditions: the phase chromatography apparatus is an Acquity UPLC system, and microcystins in the sample are separated by an Acquity UPLC BEH C18 chromatography column: acquity UPLC BEH C18, 1.7um, 2.1 × 100 mm; column temperature: 40 ℃; mobile phase: the phase A is acetonitrile, the phase B is 0.1% formic acid water, the initial proportion is 5% of the phase A, the linear increment is carried out to 60% of phase A after 0.5min, the linear increment is carried out to 100% of phase A after 1.5min, the linear increment is maintained to 2.5min, and the phase A is balanced to 3min by 5% of phase A after 2.6 min; flow rate: 0.3 mL/min; sample introduction amount: 10 uL.
5. The method for rapidly detecting microcystins in water as claimed in claim 1, wherein: the tandem mass spectrometer used was a Quattro Premier XE triple quadrupole mass spectrometer.
6. The method for rapidly detecting microcystins in water as claimed in claim 1, wherein: the using conditions of the tandem mass spectrometer are as follows: the tandem mass spectrometer used was a Quattro Premier XE triple quadrupole mass spectrometer, electrospray ionization ESI; the scanning mode is as follows: scanning positive ions; the detection mode is as follows: detecting multiple reactions; capillary voltage: 3.0 Kv; source temperature: 110 ℃; the temperature of the desolvation: 380 ℃; desolventizing flow rate: 600L/hr; taper hole air flow rate: 50L/hr; the mass analysis parameters for two common microcystins were: the cone hole voltage of MC-LR is 80V, the collision energy is 50eV, the parent ion/daughter ion reaction channel is 995.5>134.9, the cone hole voltage of MC-RR is 50V, the collision energy is 30eV, and the parent ion/daughter ion reaction channel is 520.0> 134.9.
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Denomination of invention: A rapid method for detecting microcystins in water Effective date of registration: 20221027 Granted publication date: 20200320 Pledgee: China Construction Bank Co.,Ltd. Ningbo housing and urban construction sub branch Pledgor: ZHEJIANG ZHONGYI TESTING INSTITUTE CO.,LTD. Registration number: Y2022980019870 |