CN108020628A - A kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry - Google Patents
A kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01N30/08—Preparation using an enricher
Abstract
The invention discloses a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry, belong to water environment protection detection technique field, mainly include the following steps that：(1) water sample pre-processes；(2) the enrichment purification of sample, rinse is carried out to solid phase microextraction column first with pressurized deionized water and improves adsorption area, recycle alive activated solution bis-activated to solid phase microextraction column progress top layer and depth, finally will carry out absorption, elution and the filtering of target analytes；3) detected using high pressure liquid chromatography tandem mass spectrum；4) interpretation of result：The content of sulfanilamide (SN) in water sample is calculated according to the concrete water quality weighed and the concentration detected：In short, detection method is easy, quick, analyze speed is fast, detection limit is low, and TIANZHU XINGNAO Capsul stabilization is 92% 100%, and relative standard deviation is small, greatly improves work efficiency.
Description
Technical field
The invention belongs to water environment protection detection technique field, and in particular to one kind utilizes high pressure liquid chromatography tandem mass spectrum
The method of sulfanilamide (SN) in method measure water.
Background technology
In recent years, antibiotic is largely used to human clinical and livestock-raising, these medicines can enter by all means
Into water body and soil, constitute a serious threat to ecological environment and health.Sulfa drugs is using earliest a kind of people
Work synthetic antibiotic medicine, its residual life in the environment, is longer, is a kind of emerging pollutant.The abuse of sulfa drugs can be led
Its accumulation and residual in animal body is caused, the allergic reaction and flora imbalance of people can be caused, while also result in human body
Pathogen antibody-resistant bacterium is on the increase.
Sulfanilamide (SN) is the important intermediate of sulfa drugs, synthesizes the primary raw material of sulfa drugs, except for produce crystallization
Sulfanilamide (SN) is for external application outside anti-inflammatory, can also synthesize other sulfa drugs such as sulphoamidine, kynix, sulfamethyldiazine etc..
Sulphadiazine is widely used in treating and preventing many animals disease always and promotes growth of animal, but sulfanilamide (SN)
The abuse of pyrimidine also results in its accumulation and residual in animal body, can cause the allergic reaction and flora imbalance of people, at the same time
The pathogen antibody-resistant bacterium also resulted in human body is on the increase.Country has formulated the number medicine big absolutely such as including sulphadiazine
The off-drug period of thing and monitoring means are remained accordingly, American-European Countries disable part sulfa drugs, but in reality
In the production of border, operator reduces the death rate, increases economic efficiency, still can abuse this medicine to accelerate growth of animal
Thing is so as to cause remaining generation.At present, accumulation, transfer, conversion of the China to antibiotic medicine in aquatic and terrestial enviornment
And to various biological influences, system research is also lacked, therefore, carries out the formulation of antibiotic environment and behavior study and counter-measure
Work extremely important.
Detection method currently used for disulfonamide mainly has a bioassay method, immunoassay, chromatography, and color/
Mass spectrometric hyphenated technique etc..Wherein microbiological method detection speed is fast, but sensitivity and accuracy be not high, and qualitative can only examine
Survey；Immuno analytical method is a kind of scalping choosing method, and the testing result of the big animal derived sample of impurity interference can be inaccurate, and
It is difficult to solve the problems, such as non-specific adsorption；Although good, the poor repeatability of thin-layered chromatography selectivity.
The content of the invention
For sulfanilamide (SN) in the prior art detection limit is higher, the rate of recovery is low, relative deviation is larger technical problem, the present invention
A kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry is provided.
The technical solution of invention is：A kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry, it is main
Comprise the following steps：
(1) water sample pre-processes：200-300ml water samples are taken, PBS buffer is added and is diluted to 500-1000ml, in environment temperature
Spend at 10-20 DEG C, to centrifuge 10-15min with 3800-5000rpm rotating speeds, removing large granular impurity in water removal, supernatant is taken, in institute
State and HCl adjusting liquid is added in supernatant, adjusting PH is 2-3, sealing and standing 1-2min, is then 2.2-2.7 μm with equipped with aperture
The filter negative pressure leaching of filter membrane, carries out pre-filtering, obtains primary filtrate；
(2) the enrichment purification of sample：
S1：The column that pressurizeed is carried out to solid phase microextraction column with 150-160psi first with deionized water, to solid phase microextraction
After the current 20-30s of column end, then pressure is adjusted to 120-125psi and is intake, to outlet water at tail end 10-20s；First with deionization
Water carries out rinse to solid phase microextraction column, and higher pressure can also increase the adsorbable face of filler in solid phase microextraction column
Product；
S2：500-1200 μ A electric currents are passed through in activated solution, and solid phase microextraction column is carried out surely with 120-125psi
Activation process is determined, to outlet water at tail end 30-40s；Activated solution belt current flows through solid phase microextraction column, profound can activate filler,
Improve the absorption limit of filler；
S3：The filtered fluid is entered into solid phase microextraction column with 120-125psi, makes target analytes absorption micro- in solid phase
On adsorption stuffing in extraction column, the solution for flowing through solid phase microextraction column is collected in end；
S4：The methanol solution for taking 6-10ml concentration to be 70-80% enters solid phase microextraction column with 120-125psi, in S3
The solid phase microextraction column containing target analytes eluted, eluent is flowed into receiving flask from end；
S5：The eluent is blown using nitrogen and is settled to 1-3ml, recycles aperture to be carried out for 0.2-0.22um filter membranes
Filter, obtains refined filtration liquid；
(3) detection of sample：
A) the preparation of standard solution：Standard Stock solutions are taken, are diluted step by step with diluent solution, it is respectively 0 to obtain concentration,
10,20,50,80,100ppb standard working solution；
B the standard working solution and the refined filtration liquid) are detected using high pressure liquid chromatography tandem mass spectrum；
(4) interpretation of result：Containing for sulfanilamide (SN) in water outlet is calculated using formula according to the concrete water quality weighed and the concentration detected
Amount.
Further, the formula isWherein, W is water sample sulfanilamide (SN) content, unit ug/L；C is digestion solution
Middle sulfanilamide (SN) concentration, unit ug/L；V1 accumulates for volume, unit ml；V2 is sample volume, unit ml.
Further, the high pressure liquid chromatography tandem mass spectrometer main working parameters are：Quota ion pair 173/93,
ESI sources, positive ion mode, spray voltage 3.96KV, chromatographic column BEH-C18, column temperature are 35 DEG C, and mobile phase A is 0.1% formic acid,
Mobile phase B is methanol, and the volume ratio of the mobile phase A and Mobile phase B is 2:8, remove solvent gas flow velocity 600L/hr.
Further, the activated solution includes in percentage by weight：15.4-18.2% acetic acid, 12.1-14.3%
Sodium chloride, 7.5-8.0% amino acid ion liquids, 25.5-35.5% methanol, surplus are pure water, wherein, wherein, amino acid from
Sub- liquid can activate the surface of filler in solid phase microextraction column, improve its adsorption energy as surfactant
Power, acetic acid can adjust the pH value of activating solution, it is kept acid, in addition, acetic acid, sodium chloride are as electrolyte, additionally it is possible to draw
The direction of electrical conduction current, carries out deep activation to solid phase microextraction column, is greatly improved the adsorption rate of filler in solid phase microextraction column.
Further, in the S2 of step (2), neodymium is placed at the 5-10cm apart from the bottom of the solid phase microextraction column
Magnet, activated solution carry out linear advancement under the effect of the pressure, and the setting of neodium magnet can make the electric current for being passed through activated solution
Rotate, even if its spiral shape promotes, can helper activity solution filler in solid phase microextraction column is carried out comprehensive to swash
Living, neodium magnet was placed closely, then may make electric current eddy generation, easily cause electrolyte to be accumulated, be unfavorable for solid phase microextraction
The full activation of column, and place too far, then it is little on electric current influence, fall flat.
Further, the diluent solution is the methanol solution containing 0.1% formic acid, the volume of the formic acid and methanol
Than for 2:8.
Further, the filter membrane in the step (1) is glass fibre filter membrane, and the filter membrane in step (2) is polyamide
Composite membrane, wherein, glass fibre filter membrane intensity is good, can bear the big suction filtered, the pore size filter of polyamide composite film
Small, filter effect is higher than common filter membrane.
Further, the polyamide composite film before use, by polyamide composite film concentration for 70-80%, temperature
Spend in the methanol solution for 35-50 DEG C and soak 1-10min, make polyamide composite film complete swelling, remove the storage agent of film surface
And impurity.
Further, the PBS buffer is included by percent by volume：15-26%NaCl, 12-14%KCl, 7-9%
Na2HPO4, 6-8%KH2PO4, surplus ddH2O。
Compared with prior art, beneficial effects of the present invention are：
(1) present invention is in the enrichment purification of sample, first with the deionized water of 150-160psi to solid phase microextraction column
Rinse is carried out, higher pressure can also increase the adsorbable area of filler in solid phase microextraction column.
(2) for the present invention after rinse is carried out to solid phase microextraction column using pressurized deionized water, recycling is passed through electric current
Activated solution activates solid phase microextraction column, wherein, amino acid ion liquid in activated solution as surfactant,
The surface of filler in solid phase microextraction column can be activated, improve its adsorption ability, acetic acid can adjust activating solution
PH value, its is kept acid, in addition, acetic acid, sodium chloride are as electrolyte, additionally it is possible to guide sense of current, it is micro- to solid phase
Extraction column carries out deep activation, is greatly improved the adsorption rate of filler in solid phase microextraction column.
(3) present invention places neodium magnet, work of the activated solution in pressure also at the bottom 5-10cm of solid phase microextraction column
Linear advancement is carried out under, the electric current that the setting of neodium magnet can make to be passed through activated solution rotates, even if its spiral shape pushes away
Into, can helper activity solution comprehensive activation is carried out to filler in solid phase microextraction column, neodium magnet was placed closely, then possibility
It can make electric current eddy generation, easily cause electrolyte to be accumulated, be unfavorable for the full activation of solid phase microextraction column, and place too far,
It is then little on electric current influence, fall flat.
In short, detection method is easy, quick, analyze speed is fast, detection limit is low, and TIANZHU XINGNAO Capsul stabilization exists
80%-100%, and relative standard deviation is small, greatly improves work efficiency.
Brief description of the drawings
Fig. 1 is the testing result figure that the embodiment of the present invention 1-3 carries out sulfanilamide (SN) mark-on reclaims in water；
Fig. 2 is the result point to carrying out measuring by method processing of the invention after the mark-on (100ng/ml) of sulfanilamide (SN) in water
Butut.
Embodiment
Embodiment 1
A kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry, is mainly included the following steps that：
(1) water sample pre-processes：200ml water samples are taken, PBS buffer is added and is diluted to 500ml, are 10 DEG C in environment temperature
Under, 10min is centrifuged with 3800rpm rotating speeds, large granular impurity in water removal is removed, takes supernatant, HCl tune is added in the supernatant
Liquid is saved, it is 2, sealing and standing 1min to adjust PH, is then taken out with equipped with aperture for the filter negative pressure of 2.7 μm of glass fibre filter membranes
Filter, carries out pre-filtering, obtains primary filtrate；Wherein, the PBS buffer is included by percent by volume：15%NaCl, 12%KCl,
7%Na2HPO4, 6%KH2PO4, surplus ddH2O。
(2) the enrichment purification of sample：
S1：The column that pressurizeed is carried out to solid phase microextraction column with 150psi first with deionized water, to solid phase microextraction column end
After holding current 20s, then pressure is adjusted to 120psi and is intake, to outlet water at tail end 10s；First with deionized water to solid phase microextraction
Column carries out rinse, and higher pressure can also increase the adsorbable area of filler in solid phase microextraction column；
S2：500 μ A electric currents are passed through in activated solution, and solid phase microextraction column stablize at activation with 120psi
Reason, to outlet water at tail end 30s；Activated solution belt current flows through solid phase microextraction column, can the profound suction for activating filler, improving filler
Attached limit；The activated solution includes in percentage by weight：15.4% acetic acid, 12.1% sodium chloride, 7.5% amino acid from
Sub- liquid, 25.5-% methanol, surplus are pure water, wherein, wherein, amino acid ion liquid, can be to solid as surfactant
The surface of filler is activated in phase extraction column, improves its adsorption ability, and acetic acid can adjust the pH value of activating solution, make
It keeps acid, in addition, acetic acid, sodium chloride are as electrolyte, additionally it is possible to guides sense of current, solid phase microextraction column is carried out
Deep activation, is greatly improved the adsorption rate of filler in solid phase microextraction column.In addition, apart from the bottom of the solid phase microextraction column
Neodium magnet is placed at portion 5cm, activated solution carries out linear advancement under the effect of the pressure, and the setting of neodium magnet can make to be passed through work
Change solution electric current rotate, even if its spiral shape promote, can helper activity solution to filler in solid phase microextraction column into
The comprehensive activation of row, neodium magnet was placed closely, then may make electric current eddy generation, easily cause electrolyte to be accumulated, unfavorable
In the full activation of solid phase microextraction column, and place too far, then it is little on electric current influence, fall flat.
S3：The filtered fluid is entered into solid phase microextraction column with 120psi, makes target analytes absorption in solid phase microextraction
On adsorption stuffing in column, the solution for flowing through solid phase microextraction column is collected in end；
S4：The methanol solution for taking 6ml concentration to be 70% enters solid phase microextraction column with 120psi, to containing target in S3
The solid phase microextraction column of analyte is eluted, and eluent is flowed into receiving flask from end；
S5：The eluent is blown using nitrogen and is settled to 1ml, is that 0.2um polyamide composite films are in concentration by aperture
70%th, temperature is to soak 1min in 50 DEG C of methanol solution, makes polyamide composite film complete swelling, removes the storage agent of film surface
And impurity.Recycle 0.22um polyamide composite films filtered to eluent, obtain refined filtration liquid；
(3) detection of sample：
A) the preparation of standard solution：Standard Stock solutions are taken, are diluted step by step with diluent solution, it is respectively 0 to obtain concentration,
10,20,50,80,100ppb standard working solution；The diluent solution is the methanol solution containing 0.1% formic acid, the first
The volume ratio of acid and methanol is 2:8.
B the standard working solution and the refined filtration liquid) are detected using high pressure liquid chromatography tandem mass spectrum；
The high pressure liquid chromatography tandem mass spectrometer main working parameters are：Quota ion pair 173/93, ESI sources, just from
Subpattern, spray voltage 3.96KV, chromatographic column BEH-C18, column temperature are 35 DEG C, and mobile phase A is 0.1% formic acid, and Mobile phase B is first
Alcohol, the volume ratio of the mobile phase A and Mobile phase B is 2:8, remove solvent gas flow velocity 600L/hr.
(4) interpretation of result：Containing for sulfanilamide (SN) in water outlet is calculated using formula according to the concrete water quality weighed and the concentration detected
Amount.
The formula is
Wherein, W is water sample sulfanilamide (SN) content, unit ug/L；C be digestion solution in sulfanilamide (SN) concentration, unit ug/L；V1 is appearance
Volume, unit ml；V2 is sample volume, unit ml.
Embodiment 2
A kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry, is mainly included the following steps that：
(1) water sample pre-processes：250ml water samples are taken, PBS buffer is added and is diluted to 750ml, are 15 DEG C in environment temperature
Under, 13min is centrifuged with 4400rpm rotating speeds, large granular impurity in water removal is removed, takes supernatant, HCl tune is added in the supernatant
Liquid is saved, it is 2.5, sealing and standing 1.5min to adjust PH, is then born with equipped with aperture for the filter of 2.5 μm of glass fibre filter membranes
Pressure filters, and carries out pre-filtering, obtains primary filtrate；Wherein, the PBS buffer is included by percent by volume：20.5%NaCl,
13%KCl, 8%Na2HPO4, 7%KH2PO4, surplus ddH2O。
(2) the enrichment purification of sample：
S1：The column that pressurizeed is carried out to solid phase microextraction column with 155psi first with deionized water, to solid phase microextraction column end
After holding current 25s, then pressure is adjusted to 123psi and is intake, to outlet water at tail end 15s；First with deionized water to solid phase microextraction
Column carries out rinse, and higher pressure can also increase the adsorbable area of filler in solid phase microextraction column；
S2：850 μ A electric currents are passed through in activated solution, and solid phase microextraction column stablize at activation with 123psi
Reason, to outlet water at tail end 35s；Activated solution belt current flows through solid phase microextraction column, can the profound suction for activating filler, improving filler
Attached limit；The activated solution includes in percentage by weight：16.8% acetic acid, 13.2% sodium chloride, 7.75% amino acid
Ionic liquid, 30.5% methanol, surplus are pure water, wherein, wherein, amino acid ion liquid, can be right as surfactant
The surface of filler is activated in solid phase microextraction column, improves its adsorption ability, and acetic acid can adjust the pH value of activating solution,
Its is kept acid, in addition, acetic acid, sodium chloride are as electrolyte, additionally it is possible to guide sense of current, to solid phase microextraction column into
Row deep activation, is greatly improved the adsorption rate of filler in solid phase microextraction column.In addition, apart from the solid phase microextraction column
Neodium magnet is placed at the 7.5cm of bottom, activated solution carries out linear advancement under the effect of the pressure, and the setting of neodium magnet can make to lead to
The electric current for entering activated solution rotates, though its spiral shape promote, can helper activity solution to being filled out in solid phase microextraction column
Material carries out comprehensive activation, and neodium magnet was placed closely, then may make electric current eddy generation, easily cause electrolyte to be accumulated,
Be unfavorable for the full activation of solid phase microextraction column, and place too far, then it is little on electric current influence, fall flat.
S3：The filtered fluid is entered into solid phase microextraction column with 123psi, makes target analytes absorption in solid phase microextraction
On adsorption stuffing in column, the solution for flowing through solid phase microextraction column is collected in end；
S4：The methanol solution for taking 8ml concentration to be 75% enters solid phase microextraction column with 123psi, to containing target in S3
The solid phase microextraction column of analyte is eluted, and eluent is flowed into receiving flask from end；
S5：The eluent is blown using nitrogen and is settled to 2ml, is that 0.21um polyamide composite films are in concentration by aperture
75%th, temperature is to soak 5.5min in 42.5 DEG C of methanol solution, makes polyamide composite film complete swelling, removes the storage of film surface
Deposit agent and impurity.Recycle 0.21um polyamide composite films filtered to eluent, obtain refined filtration liquid；
(3) detection of sample：
A) the preparation of standard solution：Standard Stock solutions are taken, are diluted step by step with diluent solution, it is respectively 0 to obtain concentration,
10,20,50,80,100ppb standard working solution；The diluent solution is the methanol solution containing 0.1% formic acid, the first
The volume ratio of acid and methanol is 2:8.
B the standard working solution and the refined filtration liquid) are detected using high pressure liquid chromatography tandem mass spectrum；
The high pressure liquid chromatography tandem mass spectrometer main working parameters are：Quota ion pair 173/93, ESI sources, just from
Subpattern, spray voltage 3.96KV, chromatographic column BEH-C18, column temperature are 35 DEG C, and mobile phase A is 0.1% formic acid, and Mobile phase B is first
Alcohol, the volume ratio of the mobile phase A and Mobile phase B is 2:8, remove solvent gas flow velocity 600L/hr.
(4) interpretation of result：Containing for sulfanilamide (SN) in water outlet is calculated using formula according to the concrete water quality weighed and the concentration detected
Amount.
The formula is
Wherein, W is water sample sulfanilamide (SN) content, unit ug/L；C be digestion solution in sulfanilamide (SN) concentration, unit ug/L；V1 is appearance
Volume, unit ml；V2 is sample volume, unit ml.
Embodiment 3
A kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry, is mainly included the following steps that：
(1) water sample pre-processes：300ml water samples are taken, PBS buffer is added and is diluted to 1000ml, are 20 DEG C in environment temperature
Under, 15min is centrifuged with 5000rpm rotating speeds, large granular impurity in water removal is removed, takes supernatant, HCl tune is added in the supernatant
Liquid is saved, it is 3, sealing and standing 2min to adjust PH, is then taken out with equipped with aperture for the filter negative pressure of 2.2 μm of glass fibre filter membranes
Filter, carries out pre-filtering, obtains primary filtrate；Wherein, the PBS buffer is included by percent by volume：15%NaCl, 12%KCl,
9%Na2HPO4, 6%KH2PO4, surplus ddH2O。
(2) the enrichment purification of sample：
S1：The column that pressurizeed is carried out to solid phase microextraction column with 160psi first with deionized water, to solid phase microextraction column end
After holding current 30s, then pressure is adjusted to 125psi and is intake, to outlet water at tail end 20s；First with deionized water to solid phase microextraction
Column carries out rinse, and higher pressure can also increase the adsorbable area of filler in solid phase microextraction column；
S2：1200 μ A electric currents are passed through in activated solution, and solid phase microextraction column stablize at activation with 125psi
Reason, to outlet water at tail end 40s；Activated solution belt current flows through solid phase microextraction column, can the profound suction for activating filler, improving filler
Attached limit；The activated solution includes in percentage by weight：18.2% acetic acid, 14.3% sodium chloride, 8.0% amino acid from
Sub- liquid, 35.5% methanol, surplus are pure water, wherein, wherein, amino acid ion liquid, can be to solid as surfactant
The surface of filler is activated in phase extraction column, improves its adsorption ability, and acetic acid can adjust the pH value of activating solution, make
It keeps acid, in addition, acetic acid, sodium chloride are as electrolyte, additionally it is possible to guides sense of current, solid phase microextraction column is carried out
Deep activation, is greatly improved the adsorption rate of filler in solid phase microextraction column.In addition, apart from the bottom of the solid phase microextraction column
Neodium magnet is placed at portion 10cm, activated solution carries out linear advancement under the effect of the pressure, and the setting of neodium magnet can make to be passed through
The electric current of activated solution rotates, though its spiral shape promote, can helper activity solution to filler in solid phase microextraction column
Comprehensive activation is carried out, neodium magnet was placed closely, then may make electric current eddy generation, easily cause electrolyte to be accumulated, no
Beneficial to the full activation of solid phase microextraction column, and place too far, then it is little on electric current influence, fall flat.
S3：The filtered fluid is entered into solid phase microextraction column with 125psi, makes target analytes absorption in solid phase microextraction
On adsorption stuffing in column, the solution for flowing through solid phase microextraction column is collected in end；
S4：The methanol solution for taking 10ml concentration to be 80% enters solid phase microextraction column with 125psi, to containing mesh in S3
The solid phase microextraction column of mark analyte is eluted, and eluent is flowed into receiving flask from end；
S5：The eluent is blown using nitrogen and is settled to 3ml, is that 0.22um polyamide composite films are in concentration by aperture
80%th, temperature is to soak 1min in 50 DEG C of methanol solution, makes polyamide composite film complete swelling, removes the storage agent of film surface
And impurity.Recycle 0.2um polyamide composite films filtered to eluent, obtain refined filtration liquid；
(3) detection of sample：
A) the preparation of standard solution：Standard Stock solutions are taken, are diluted step by step with diluent solution, it is respectively 0 to obtain concentration,
10,20,50,80,100ppb standard working solution；The diluent solution is the methanol solution containing 0.1% formic acid, the first
The volume ratio of acid and methanol is 2:8.
B the standard working solution and the refined filtration liquid) are detected using high pressure liquid chromatography tandem mass spectrum；
The high pressure liquid chromatography tandem mass spectrometer main working parameters are：Quota ion pair 173/93, ESI sources, just from
Subpattern, spray voltage 3.96KV, chromatographic column BEH-C18, column temperature are 35 DEG C, and mobile phase A is 0.1% formic acid, and Mobile phase B is first
Alcohol, the volume ratio of the mobile phase A and Mobile phase B is 2:8, remove solvent gas flow velocity 600L/hr.
(4) interpretation of result：Containing for sulfanilamide (SN) in water outlet is calculated using formula according to the concrete water quality weighed and the concentration detected
Amount.
The formula is
Wherein, W is water sample sulfanilamide (SN) content, unit ug/L；C be digestion solution in sulfanilamide (SN) concentration, unit ug/L；V1 is appearance
Volume, unit ml；V2 is sample volume, unit ml.
Interpretation of result
The testing result that sulfanilamide (SN) mark-on reclaims in water are carried out to the embodiment of the present invention 1-3 is as shown in table 1：
Method processing after mark-on (100ng/ml) to carrying out sulfanilamide (SN) in water by the present invention measures distribution of results figure such as
Shown in Fig. 2：
1 the embodiment of the present invention 1-3 of table carries out the testing result of sulfanilamide (SN) mark-on reclaims in water
Canonical plotting is obtained according to table 1 and drafting relevant parameter, as shown in Figure 1.
Wherein, relevant parameter is：
Correlation coefficent:R=0.999669, r^2=0.999338
Calibration curve:873.038*X+722.573
Response type:External Std,Area
Curve type:Linear,Origin:Exclude,Weighting:1/X,Axis trans:None
Method processing after mark-on (100ng/ml) to carrying out sulfanilamide (SN) in water by the present invention measures distribution of results figure such as
Shown in Fig. 2.
From table 1 and Fig. 2, by the processing measured value of this programme after the mark-on (100ng/ml) to carrying out sulfanilamide (SN) in water
Respectively 92.9,94.9,93.7ng/ml, rate of recovery stabilization is in 92-100%.
Claims (9)
- A kind of 1. method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry, it is characterised in that it is main include with Lower step：(1) water sample pre-processes：200-300ml water samples are taken, PBS buffer is added and is diluted to 500-1000ml, be in environment temperature At 10-20 DEG C, 10-15min is centrifuged with 3800-5000rpm rotating speeds, large granular impurity in water removal is removed, supernatant is taken, on described HCl is added in clear liquid and adjusts liquid, adjusting PH is 2-3, sealing and standing 1-2min, is then used equipped with 2.2-2.7 μm of aperture filter membrane Filter negative pressure leaching, carries out pre-filtering, obtains primary filtrate；(2) the enrichment purification of sample：S1：The column that pressurizeed is carried out to solid phase microextraction column with 150-160psi first with deionized water, to solid phase microextraction column end After holding current 20-30s, then pressure is adjusted to 120-125psi and is intake, to outlet water at tail end 10-20s；S2：500-1200 μ A electric currents are passed through in activated solution, and with 120-125psi solid phase microextraction column are carried out stablizing work Change is handled, to outlet water at tail end 30-40s；S3：The filtered fluid is entered into solid phase microextraction column with 120-125psi, makes target analytes absorption in solid phase microextraction On adsorption stuffing in column, the solution for flowing through solid phase microextraction column is collected in end；S4：The methanol solution for taking 6-10ml concentration to be 70-80% enters solid phase microextraction column with 120-125psi, to containing in S3 The solid phase microextraction column for having target analytes is eluted, and eluent is flowed into receiving flask from end；S5：The eluent is blown using nitrogen and is settled to 1-3ml, recycles 0.2-0.22um filter membranes to be filtered, obtains refined filtration Liquid；(3) detection of sample：A) the preparation of standard solution：Standard Stock solutions are taken, are diluted step by step with diluent solution, it is respectively 0,10 to obtain concentration, 20,50,80,100ppb standard working solution；B the standard working solution and the refined filtration liquid) are detected using high pressure liquid chromatography tandem mass spectrum；(4) interpretation of result：The content of sulfanilamide (SN) in water outlet is calculated using formula according to the concrete water quality weighed and the concentration detected.
- 2. a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry as claimed in claim 1, it is special Sign is that the formula isWherein, W is water sample sulfanilamide (SN) content, unit ug/L；C is sulfanilamide (SN) concentration in digestion solution, Unit is ug/L；V1 accumulates for volume, unit ml；V2 is sample volume, unit ml.
- 3. a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry as claimed in claim 1, it is special Sign is that the high pressure liquid chromatography tandem mass spectrometer main working parameters are：Quota ion pair 173/93, ESI sources, cation Pattern, spray voltage 3.96KV, chromatographic column BEH-C18, column temperature are 35 DEG C, and mobile phase A is 0.1% formic acid, and Mobile phase B is first Alcohol, the volume ratio of the mobile phase A and Mobile phase B is 2:8, remove solvent gas flow velocity 600L/hr.
- 4. a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry as claimed in claim 1, it is special Sign is that the activated solution includes in percentage by weight：15.4-18.2% acetic acid, 12.1-14.3% sodium chloride, 7.5-8.0% amino acid ion liquids, 25.5-35.5% methanol, surplus are pure water.
- 5. a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry as claimed in claim 1, it is special Sign is that the diluent solution is the methanol solution containing 0.1% formic acid, and the volume ratio of the formic acid and methanol is 2:8.
- 6. a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry as claimed in claim 1, it is special Sign is, the filter membrane in the step (1) is glass fibre filter membrane, and the filter membrane in step (2) is polyamide composite film.
- 7. a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry as claimed in claim 6, it is special Sign is, the polyamide composite film before use, by polyamide composite film concentration be 70-80%, temperature be 35-50 DEG C 1-10min is soaked in methanol solution, makes polyamide composite film complete swelling.
- 8. a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry as claimed in claim 1, it is special Sign is that the PBS buffer is included by percent by volume：15-26%NaCl, 12-14%KCl, 7-9%Na2HPO4, 6-8% KH2PO4, surplus ddH2O。
- 9. a kind of method that sulfanilamide (SN) in water is measured using high pressure liquid chromatography tandem mass spectrometry as claimed in claim 1, it is special Sign is that the filter membrane in the step (1) is glass fibre filter membrane.
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