CN108254481A - A kind of method of multi-class drug and personal care articles and pesticide in quick detection water - Google Patents

A kind of method of multi-class drug and personal care articles and pesticide in quick detection water Download PDF

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Publication number
CN108254481A
CN108254481A CN201611251506.5A CN201611251506A CN108254481A CN 108254481 A CN108254481 A CN 108254481A CN 201611251506 A CN201611251506 A CN 201611251506A CN 108254481 A CN108254481 A CN 108254481A
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formic acid
phase extraction
pesticide
solid
extraction column
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CN201611251506.5A
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CN108254481B (en
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罗茜
许美佳
杨致
杨致一
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation

Abstract

The present invention provides a kind of method of multi-class drug and personal care articles and pesticide in quick detection water, including：Water sample to be measured is taken, water sample to be measured progress pre-treatment is obtained into detected sample；Detected sample is respectively adopted to one or more groups of carry out Liquid Chromatography-Tandem Mass Spectrometry detections in following five groups of testing conditions, realizes the qualitative analysis to multi-class drug and personal care articles and pesticide in water sample to be measured and quantitative detection：(a) mobile phase is formic acid formic acid aqueous ammonium and acetonitrile, and ionization pattern is electro-spray ionization holotype；(b) mobile phase is aqueous formic acid and acetonitrile, and ionization pattern is electro-spray ionization holotype；(c) mobile phase is ethyl aqueous ammonium and acetonitrile, and ionization pattern is electro-spray ionization negative mode；(d) mobile phase is water and acetonitrile, and ionization pattern is electro-spray ionization negative mode；(e) mobile phase is formic acid formic acid aqueous ammonium and acetonitrile, and ionization pattern is electro-spray ionization holotype.

Description

A kind of method of multi-class drug and personal care articles and pesticide in quick detection water
Technical field
The present invention relates to environmental monitoring technology fields, and in particular to multi-class drug and individual protect in a kind of quick detection water The method of reason product and pesticide.
Background technology
Drug and personal care articles (PPCPs) include various prescriptions and non-prescription drugs (such as antibiotic, antiphlogistic, town Quiet dose, lipid regulating agent and antiepileptic etc.) and personal care articles (synthetic perfume, developer, opacifier in such as cosmetics, Culicifuge and disinfectant etc.), by chemical classes can be divided into sulfamido, quinolones, Tetracyclines, macrolides and Multiple classifications such as steroids.As a kind of emerging pollutant, PPCPs has been found to have human health and ecological environment latent It is endangering, at present, PPCPs has become a research hotspot in water environment field.
Pesticide is mainly used for disease and pest control to ensure grain as one of substance input important in Agricultural Activities Yield can be divided into insecticide, fungicide and herbicide etc. by purposes, can then be divided by its chemical constitution organophosphor, organochlorine, Multiple classifications such as carbamate, triazines and azole.It is even abused with a large amount of use that continue of pesticide, pesticide in water Pollution problem has become a global pollution problem.
Drug and personal care articles (PPCPs) and pesticide are as the organic pollution being concerned in water environment, in recent years, Countries in the world expand extensive research to the residual of PPCPs in water environment and pesticide, environmental behaviour and home to return to.It is reported that The PPCPs and pesticide concentration level detected in water body in g/L grades of ng/L- μ, belongs to organic micro-pollutant.Due to analyzer The impurity of the lowest detection ability finite sum environmental water sample of device interferes, and PPCPs and pesticide generally can not directly carry out instrument in water Device is analyzed, and need to pass through certain pre-treatment, by its concentration extraction to the measurable concentration level of instrument.At present, although have compared with More pre-treating methods and analytical technology are exploited for the pollution condition of PPCPs and pesticide in assessment water, but most of analysis side Method is only applicable to PPCPs or is only applicable to pesticide, and the scope of application is only limitted to certain one kind in PPCPs and pesticide.
In conclusion existing at present, for the analysis method of PPCPs and pesticide in water, in the presence of detecting, type is single, analyzes The shortcomings of time-consuming and analysis cost is high.In view of PPCPs and pesticide variety are various and its ecological environment and the mankind are good in water body The reasons such as health potential hazard is very important, establishing a kind of can quickly detect the side of multi-class PPCPs and insecticide pollution in water Method has important practical significance.
Invention content
In consideration of it, the present invention provides the sides of multi-class drug and personal care articles and pesticide in a kind of quick detection water Method.The method of the present invention can realize while detect more than 100 kinds of PPCPs and pesticide have detection fast and accurately advantage.
The present invention provides a kind of method of multi-class drug and personal care articles and pesticide in quick detection water, including：
(1) water sample to be measured is taken, the water sample to be measured is carried out pre-treatment obtains detected sample；
(2) detected sample is respectively adopted to one or more groups of carry out liquid phase colors in following five groups of testing conditions Spectrum-tandem mass spectrum detection, realizes the qualitative analysis to multi-class drug and personal care articles and pesticide in water sample to be measured and determines Amount detection：
(a) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Formic acid-formic acid aqueous ammonium, B phases：Acetonitrile is adopted With gradient elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype；
(b) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Aqueous formic acid, B phases：Acetonitrile is washed using gradient De-, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype；
(c) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Acetic acid-ammonium acetate solution, B phases：Acetonitrile is adopted With gradient elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization negative mode；
(d) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Water, B phases：Acetonitrile, using gradient elution, column temperature For room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization negative mode；
(e) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Formic acid-formic acid aqueous ammonium, B phases：Acetonitrile is adopted With gradient elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype.
Optionally, eluent gradient elution program is in (a) testing conditions：
0min-0.5min：95%A, 5%B；3.0min：75%A, 25%B；9.0min：65%A, 35%B；13.5min： 20%A, 80%B；14.0min：0%A, 100%B；14.1min-19.0min：95%A, 5%B；
Eluent gradient elution program is in (b) testing conditions：
0min-0.5min：90%A, 10%B；3.5min：70%A, 30%B；4.5min：60%A, 40%B；7.5min： 10%A, 90%B；8.5min：0%A, 100%B；8.6min-10.0min：90%A, 10%B；
Eluent gradient elution program is in (c) testing conditions：
0min-0.5min：70%A, 30%B；4.5min：20%A, 80%B；5.0min：0%A, 100%B；5.1min- 9.0min：70%A, 30%B；
Eluent gradient elution program is in (d) testing conditions：
0min：60%A, 40%B；4.0min：50%A, 50%B；4.5min：0%A, 100%B；4.6min-8min： 60%A, 40%B；
Eluent gradient elution program is in (e) testing conditions：
0min-0.5min：95%A, 5%B；8.0min：40%A, 60%B；11.0min：0%A, 100%B； 11.1min-16.0min：95%A, 5%B.
Optionally, in (a)-(e) testing conditions, the flow velocity of the mobile phase is 0.2mL/min-0.25mL/min.
Optionally, in (a) and (e), the formic acid-formic acid aqueous ammonium is mixed by formic acid and formic acid aqueous ammonium It arrives, a concentration of 4mmol/L-6mmol/L of ammonium formate in the formic acid aqueous ammonium, first in the formic acid-formic acid aqueous ammonium The volume fraction of acid is 0.04%-0.06%；In (b), the volume fraction of formic acid is 0.1%- in the aqueous formic acid 0.2%；In (c), the acetic acid-ammonium acetate solution is mixed to get by acetic acid and ammonium acetate solution, the ammonium acetate A concentration of 4-6mmol/L of ammonium acetate in aqueous solution, in the acetic acid-ammonium acetate solution, the volume fraction of the acetic acid is 0.04%-0.06%.
Optionally, the sample size of the detected sample in the chromatography column is 10 μ L-15 μ L.
Optionally, the mass spectrographic scan mode be multiple-reaction monitoring pattern, detector be triple quadrupole bar, the EFI Mist ionization holotype Mass Spectrometry Conditions be：Ion source temperature is 120 DEG C -150 DEG C, orifice potential 10V-60V, capillary electricity It presses as 3.5KV-4.0KV, desolvation temperature is 380 DEG C -400 DEG C, Desolvention gas velocity 600L/h-700L/h, taper hole gas Flow velocity is 50L/h-60L/h, collision energy 5V-40V；The Mass Spectrometry Conditions of the electro-spray ionization negative mode are：Ion source Temperature is 120 DEG C -150 DEG C, orifice potential 10V-60V, capillary voltage 3.0KV-3.5KV, desolvation temperature 380 DEG C -420 DEG C, Desolvention gas velocity 600L/h-700L/h, taper hole gas velocity 50L/h-60L/h, collision energy 5V- 40V。
Optionally, Norfloxacin, Enoxacin, oxygen fluorine sand are included by the detectable substance of the testing conditions (a) Star, Ciprofloxacin, Pefloxacin, fleraxacin, Lomefloxacin, Danofloxacin, Enrofloxacin, cinoxacin, Sarafloxacin, department Pa sand star, Difloxacin, Moxifloxacin, oxolinic acid, sulfaquinoxaline, acidum nalidixicum, flumequine, 5-methoxysulfadiazine, sulfanilamide (SN), Sulphaguanidine, sulfacetamide, sulfaisodimidine, sulphadiazine, Cefradine, lincomycin, sulfapryidine, sulfanilamide (SN) thiophene Azoles, methoxybenzyl aminopyrimidine, sulfamethyldiazine, sulfamethazole, Ormetoprim, sulfamethizole, sulfamerazine, sulfanilamide (SN) Methoxy pyrazine, daimeton, cistosulfa, fanasil, azithromycin, sulfamethoxazole, sulfanilamide (SN) Sulfafurazole, sulfadimethoxine, sulfaphenazolum, anhydroerythromycin, clarithromycin, roxithromycin, Trenbolone, promise Dragon, boldenone, 19-norandrosterone, testosterone, norethindrone, 17 α-methyltestosterone, 21 α-hydroxyprogesterone, stanozolol, androstenedione, table testis Ketone, D- dl-Norgestrels, 17 α-hydroxyprogesterone, Medroxyprogesterone, progesterone, danazol, megestrol acetate, Medroxyprogesterone Acetate, acetic acid Chlormadinone, paracetamol, can iron be peaceful, salbutamol, Cimetidine, atenolol, Majorem, Lamotrigine, Mei Tuo Luo Er, digoxin, Venlafaxine, Metadelphene, carbamazepine, benzene draw hamming, Prozac, Citalopram and diltiazem；
4- epianhydrotetracyclines, dehydration tetracycline, α-load are included by the detectable substance of the testing conditions (b) Lipoprotein-terramycin, β-apolipoprotein-terramycin, epitetracyclin, tetracycline, fortimicin, minocycline, difference to Terramycin, terramycin, difference are to dehydration aureomycin, demeclocycline, chlorquatrimycin, aureomycin, Amoxicillin, metronidazole and diformazan Nitre azoles；
By the detectable substance of the testing conditions (c) include benzsulfamide, chloramphenicol, prednisone, prednisolone, Cortisone, hydrocortisone, naproxen, Ketoprofen, 6 alpha-methylprednisolones, fluorometholone, dexamethasone, beclomethasone, Flumethasone, cellulose acetate hydrogen fluorine cortisone, budesonide, Triamcinolone acetonide, fluocinolone acetonide, brufen, Gemfibrozil Capsules, triclosan, trichlorine card Class and clobetasol propionate；
By the detectable substance of the testing conditions (d) include triamcinolone, estriol, aldosterone, bisphenol-A, 17 α- Estradiol, the female alcohol of 17 alpha-acetylenes, oestrone, diethylstilbestrol, hexestrol and dienestrol；
Acephatemet is included by the detectable substance of the testing conditions (e), removes deisopropyl-atrazine, acetyl methylamine The careless spirit of phosphorus, Tinidazole glucose injection, omethoate, pymetrozine, Azodrin, sulphur, metilomerkaptofosoksid, Acetamiprid, Rogor, imidacloprid, metrifonate, aphid Go out phosphorus, fenamiphos sulfoxide, Mobucin, remove ethyl Garagard, DDVP, aniline phosphorus sulfone, thiodicarb, molinate, Bassa, put out Tianjin, Garagard, Acetochlor, Tebuconazole, Terbufos sulfone, malathion, tebufenozide, terbucarb, diazinon, butachlor, anilofos, Profenofos and bentazone.
Optionally, the pre-treatment operation of the water sample to be measured includes：Water sample to be measured is taken, after filtering, adds in complexing agent, mixing Afterwards, it is 6.0-7.0 to adjust water sample pH value, obtains first and treats test sample, treats that test sample carries out Solid Phase Extraction by described first, is washed after extraction It is de-, eluent is collected, obtains the extracting solution containing multi-class drug and personal care articles and pesticide, after concentration, obtains described treat Detect sample.
Optionally, the extraction column that the Solid Phase Extraction uses includes the weak anionic being sequentially connected in series according to the sequence of upper, middle and lower Solid-phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid-phase extraction column are exchanged, described first treats that test sample flows successively Solid-phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid-phase extraction column are exchanged through the weak anionic.
Optionally, the weak anionic exchange solid-phase extraction column includes WAX columns, the hydrophilic-lipophilic balance solid-phase extraction column Including HLB columns, the activated carbon solid-phase extraction column includes AC2 columns.
Optionally, after extraction, by the weak anionic of series connection exchange solid-phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and Activated carbon solid-phase extraction column is split, and exchanges solid-phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and work to weak anionic respectively Property charcoal solid-phase extraction column is eluted；The weak anionic exchanges solid-phase extraction column and uses formic acid-methanol solution and methyl successively Tertbutyl ether-methanol solution elution, the hydrophilic-lipophilic balance solid-phase extraction column is using formic acid-methanol solution elution, the work Property charcoal solid-phase extraction column using ammonium acetate-methanol solution elution.
Optionally, in the formic acid-methanol solution percentage by volume of formic acid for 2%-5%, the methyl tertiary butyl ether(MTBE)- The volume ratio of methyl tertiary butyl ether(MTBE) and methanol is 9 in methanol solution:1, ammonium acetate is a concentration of in the ammonium acetate-methanol solution 20mmol/L-40mmol/L。
Optionally, described first treat that test sample is consolidated in weak anionic exchange solid-phase extraction column, the hydrophilic-lipophilic balance Flow velocity in phase extraction column and the activated carbon solid-phase extraction column is 5mL/min-10mL/min.
Optionally, each eluent exchanges solid-phase extraction column, the hydrophilic-lipophilic balance Solid Phase Extraction in the weak anionic Elution speed in column and the activated carbon solid-phase extraction column is 1mL/min-2mL/min.
Optionally, the complexing agent includes ethylenediamine tetra-acetic acid or disodium ethylene diamine tetraacetate, the addition of the complexing agent Measure the complexing agent to add in 0.2g-0.5g in water sample to be measured every liter described.
The present invention carries out the multi-class drug in water sample and personal care articles and pesticide using liquid chromatography-tandem mass spectrometry Qualitative and quantitative analysis is locked with characteristic ion using retention time to that may be present in the mode qualitatively screening sample of locking PPCPs and pesticide pollutant, effectively eliminate false positive, and testing result is accurate.
Description of the drawings
Fig. 1 is representativeness PPCPs and pesticide in different type water body (ultra-pure water, tap water and surface water) in embodiment 1 The recovery of standard addition result of pollutant；
Fig. 2 is 35 kinds of pesticides and its interior target total ion chromatogram in water sample to be measured in embodiment 1；
Fig. 3 is the selection chromatography of ions figure of sulphadiazine in embodiment 1；
Fig. 4 is the selection chromatography of ions figure of Ciprofloxacin in embodiment 1；
Fig. 5 is the selection chromatography of ions figure of testosterone in embodiment 1；
Fig. 6 is the selection chromatography of ions figure of progesterone in embodiment 1；
Fig. 7 is the selection chromatography of ions figure of atenolol in embodiment 1；
Fig. 8 is the selection chromatography of ions figure of Tetracyclines (4- epianhydrotetracyclines and dehydration tetracycline) in embodiment 1；
Fig. 9 is the selection chromatography of ions figure of metronidazole in embodiment 1；
Figure 10 is the selection chromatography of ions figure of prednisone in embodiment 1；
Figure 11 is the selection chromatography of ions figure of Gemfibrozil Capsules in embodiment 1；
Figure 12 is the selection chromatography of ions figure of estriol in embodiment 1；
Figure 13 is the selection chromatography of ions figure of acephatemet in embodiment 1.
Specific embodiment
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as Protection scope of the present invention.
An embodiment of the present invention provides multi-class drug and personal care articles and pesticide in a kind of rapid extraction and detection water Method, including：
(1) water sample to be measured is taken, the water sample to be measured is carried out pre-treatment obtains detected sample；
(2) detected sample is respectively adopted to one or more groups of carry out liquid phase colors in following five groups of testing conditions Spectrum-tandem mass spectrum detection, realizes the qualitative analysis to multi-class drug and personal care articles and pesticide in water sample to be measured and determines Amount detection：
(a) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Formic acid-formic acid aqueous ammonium, B phases：Acetonitrile is adopted With gradient elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype；
(b) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Aqueous formic acid, B phases：Acetonitrile is washed using gradient De-, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype (ESI+)；
(c) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Acetic acid-ammonium acetate solution, B phases：Acetonitrile is adopted With gradient elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization negative mode (ESI-)；
(d) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Water, B phases：Acetonitrile, using gradient elution, column temperature For room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization negative mode；
(e) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Formic acid-formic acid aqueous ammonium, B phases：Acetonitrile is adopted With gradient elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype.
In embodiment of the present invention, the pre-treatment operation of the water sample to be measured includes：Water sample to be measured is taken, after filtering, is added in Complexing agent, after mixing, it is 6.0-7.0 to adjust water sample pH value, obtains first and treats test sample, treats that test sample carries out solid phase extraction by described first It takes, is eluted after extraction, collect eluent, obtain the extracting solution containing multi-class drug and personal care articles and pesticide, after concentration, Obtain the detected sample.Wherein, glass fiber filter filtering can be used in the filter operation.Specifically optionally, glass fibers The aperture for tieing up filter membrane can be 0.2 μm -0.7 μm.Optionally, before filtering, it is small that glass fiber filter need to dry 6 under the conditions of 450 DEG C When.
In embodiment of the present invention, optionally, complexing agent includes ethylenediamine tetra-acetic acid or disodium ethylene diamine tetraacetate (Na2EDTA), complexing agent of the addition of complexing agent to add in 0.2g-0.5g in every liter of water sample to be measured.The present invention utilizes complexing Ca in agent complexing water2+And Mg2+Metal ions and micro heavy ion are waited, so as to inhibit macrolide antibiotics and Fourth Ring The complexing of plain class antibiotic and metal ion, PPCPs pollutants are interference-free during ensuring that follow-up water sample is enriched with.
In embodiment of the present invention, ammonium hydroxide can be used or formic acid adjusts the pH value of water sample, it specifically can be by the pH value tune of water sample For 6.0-6.2.
In embodiment of the present invention, the extraction column that Solid Phase Extraction uses is weak including being sequentially connected in series according to the sequence of upper, middle and lower Anion-exchange solid phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid-phase extraction column, first treats test sample successively It flows through weak anionic and exchanges solid-phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid-phase extraction column.The present invention one In specific embodiment, the weak anionic exchanges solid-phase extraction column and includes WAX columns, the hydrophilic-lipophilic balance solid-phase extraction column Including HLB columns, the activated carbon solid-phase extraction column includes AC2 columns.
Wherein, weak anionic exchanges solid-phase extraction column has stronger adsorption capacity to highly acid compound, and hydrophilelipophile is put down The solid-phase extraction column that weighs has hydrophilic and lipophilic attribute, has preferable adsorption energy to polarity, middle polarity and hydrophobic compound Power；Activated carbon solid-phase extraction column has stronger adsorption capacity to organic matter highly polar in water (such as acephatemet and orthene).It adopts The side of solid-phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid-phase extraction column three columns in series is exchanged with weak anionic Formula carries out water sample enrichment, utmostly ensures that multi-class PPCPs and insecticide pollution with different physicochemical properties can be simultaneously It is extracted from water sample, is a kind of extracting method of high throughput.
Optionally, before extraction, the extraction column that Solid Phase Extraction uses is activated successively using methanol and ultra-pure water. Specifically, the extraction column that Solid Phase Extraction uses using 6-10mL methanol and 6-10mL ultra-pure waters is activated successively, activated Extraction column moistening is kept in journey.In the embodiment of the invention, successively using 6mL methanol and 6mL ultra-pure waters to WAX columns into Row activation, successively activates HLB columns and AC2 columns using 10mL methanol and 10mL ultra-pure waters.Optionally, in activation process, The flow velocity of methanol or ultra-pure water is 1mL/min-2mL/min.
In embodiment of the present invention, optionally, first treats that test sample is put down in weak anionic exchange solid-phase extraction column, hydrophilelipophile Flow velocity in weighing apparatus solid-phase extraction column and activated carbon solid-phase extraction column is 5mL/min-10mL/min.
In embodiment of the present invention, after extraction, the extraction column that is used with a small amount of ultrapure water sample bottle and Solid Phase Extraction, And the residual moisture in extraction column is drained as possible, then eluted.
In embodiment of the present invention, after extraction, it is solid that the weak anionic of series connection is exchanged into solid-phase extraction column, hydrophilic-lipophilic balance Phase extraction column and activated carbon solid-phase extraction column are split, and exchange solid-phase extraction column, hydrophilic-lipophilic balance solid phase to weak anionic respectively Extraction column and activated carbon solid-phase extraction column are eluted；The weak anionic exchanges solid-phase extraction column and uses formic acid-methanol successively Solution and methyl tertiary butyl ether(MTBE)-methanol solution elution, the hydrophilic-lipophilic balance solid-phase extraction column are washed using formic acid-methanol solution De-, the activated carbon solid-phase extraction column is using ammonium acetate-methanol solution elution.Optionally, formic acid in the formic acid-methanol solution Percentage by volume for 2%-5%, the volume ratio of methyl tertiary butyl ether(MTBE) and methanol is in the methyl tertiary butyl ether(MTBE)-methanol solution 9:1, a concentration of 20-40mmol/L of ammonium acetate in the ammonium acetate-methanol solution.Still optionally further, formic acid-methanol solution The percentage by volume of middle formic acid is 2%, a concentration of 20mmol/L of ammonium acetate in the ammonium acetate-methanol solution.The present invention one In specific embodiment, the weak anionic exchanges solid-phase extraction column and uses 8mL formic acid-methanol solution and 8mL methyl- terts successively Butyl ether-methanol solution is eluted, and the hydrophilic-lipophilic balance solid-phase extraction column is washed using 8mL formic acid-methanol solution De-, the activated carbon solid-phase extraction column is eluted using 10mL ammonium acetates-methanol solution.Optionally, each eluent is described Weak anionic exchanges washing in solid-phase extraction column, the hydrophilic-lipophilic balance solid-phase extraction column and the activated carbon solid-phase extraction column De- speed is 1mL/min-2mL/min.
Wherein, the present invention is by optimizing eluting solvent combination condition, so as to get pollutant is all eluted and as far as possible will Impurity is retained on extraction column, so as to achieve the effect that further to purify sample.
In embodiment of the present invention, extracting solution is concentrated, when liquid product to be extracted is concentrated into about 0.15mL, uses constant volume Solvent is settled to 1mL, and film is crossed after mixing, can it is directly to be measured or after diluting it is to be measured.Optionally, in a manner that water-bath nitrogen is blown Extracting solution is concentrated；Still optionally further, bath temperature is 40 DEG C, and nitrogen flow rate is so that extracting solution liquid level is slightly recessed Preferably.
In embodiment of the present invention, the constant volume solvent be formic acid-acetonitrile solution, wherein, formic acid-acetonitrile solution by Formic acid and acetonitrile solution are mixed to get, and the volume ratio of acetonitrile and water is 5 in acetonitrile solution:95, formic acid is in formic acid-acetonitrile water The percentage by volume of solution is 1%.Optionally, the film that sample is crossed after constant volume for GHP Syringe Filter (0.2 μm, 13mm)；Sample can be 10-100 times according to water sample type selective dilution after crossing film.
The present invention is operated by pre-treatment, it can be achieved that extract multi-class drug and personal care articles and pesticide in water simultaneously, It, can be to avoid the metal ion subsequently influence to being enriched with and detecting by the complexation of metal ions of complexing agent；Pass through three kinds of extractions Drug multi-class in water and personal care articles and pesticide can be farthest enriched with by the mode of column series connection, be contributed to subsequent Detection.
In embodiment of the present invention, eluent gradient elution program is in (a) testing conditions：
0min-0.5min：95%A, 5%B；3.0min：75%A, 25%B；9.0min：65%A, 35%B；13.5min： 20%A, 80%B；14.0min：0%A, 100%B；14.1min-19.0min：95%A, 5%B；
Eluent gradient elution program is in (b) testing conditions：
0min-0.5min：90%A, 10%B；3.5min：70%A, 30%B；4.5min：60%A, 40%B；7.5min： 10%A, 90%B；8.5min：0%A, 100%B；8.6min-10.0min：90%A, 10%B；
Eluent gradient elution program is in (c) testing conditions：
0min-0.5min：70%A, 30%B；4.5min：20%A, 80%B；5.0min：0%A, 100%B；5.1min- 9.0min：70%A, 30%B；
Eluent gradient elution program is in (d) testing conditions：
0min：60%A, 40%B；4.0min：50%A, 50%B；4.5min：0%A, 100%B；4.6min-8min： 60%A, 40%B；
Eluent gradient elution program is in (e) testing conditions：
0min-0.5min：95%A, 5%B；8.0min：40%A, 60%B；11.0min：0%A, 100%B； 11.1min-16.0min：95%A, 5%B.
Optionally, the substance situation that the embodiment of the present invention can be detected according to detected sample situation and needs, respectively Using one or more groups of carry out liquid chromatography-tandem mass spectrometry detections in five groups of testing conditions, five groups of detector bars such as may be used Part is detected or is detected only with one group of testing conditions.Optionally, it needs with acetonitrile and surpasses after every group of measure Pure water by volume 50:50 ratio rinses chromatographic column at least 10 minutes, is then rinsed at least 10 minutes with acetonitrile, subsequently into Next group of detection.
Optionally, the total run time of the chromatographic column in (a)-(e) testing conditions be followed successively by 19min, 10min, 9min, 8min and 16min.
Optionally, in (a)-(e) testing conditions, the flow velocity of mobile phase is 0.20mL/min-0.25mL/min.Into one Optionally, the flow velocity of the mobile phase in (a)-(e) testing conditions is followed successively by 0.20mL/min, 0.25mL/min, 0.25mL/ to step Min, 0.25mL/min and 0.20mL/min.
Optionally, in (a) and (e), the formic acid-formic acid aqueous ammonium is mixed to get by formic acid and formic acid aqueous ammonium, A concentration of 4-6mmol/L of ammonium formate in the formic acid aqueous ammonium, the volume point of formic acid in the formic acid-formic acid aqueous ammonium Number is 0.04%-0.06%；(b) in, the volume fraction of formic acid is 0.1%-0.2% in the aqueous formic acid；(c) in, institute It states acetic acid-ammonium acetate solution to be mixed to get by acetic acid and ammonium acetate solution, ammonium acetate is dense in the ammonium acetate solution It spends for 4-6mmol/L, in the acetic acid-ammonium acetate solution, the volume fraction of the acetic acid is 0.04%-0.06%.Into one It walks preferably, a concentration of 4mmol/L of ammonium formate in the formic acid aqueous ammonium, formic acid in the formic acid-formic acid aqueous ammonium Volume fraction be 0.04%%；The volume fraction of the middle formic acid of the aqueous formic acid is 0.1%；Acetic acid-the ammonium acetate Aqueous solution is mixed to get for acetic acid and ammonium acetate solution, a concentration of 4mmol/L of ammonium acetate, institute in the ammonium acetate solution It states in acetic acid-ammonium acetate solution, the volume fraction of the acetic acid is 0.04%.
In embodiment of the present invention, the sample size of the detected sample in the chromatography column is 10-15 μ L.Specific embodiment party In formula, the sample size of detected sample in the chromatography column should be consistent with the sample size of standard solution.It is further preferred that it treats The sample size for detecting sample is 10 μ L.
In embodiment of the present invention, the mass spectrographic scan mode is multiple-reaction monitoring pattern, and detector is triple quadrupole Bar, the Mass Spectrometry Conditions of the electro-spray ionization holotype are：Ion source temperature is 120 DEG C -150 DEG C, orifice potential 10V- 60V, capillary voltage 3.5KV-4.0KV, desolvation temperature are 380 DEG C -400 DEG C, Desolvention gas velocity 600L/h- 700L/h, taper hole gas velocity 50L/h-60L/h, collision energy 5V-40V；The mass spectrum of the electro-spray ionization negative mode Condition is：Ion source temperature is 120 DEG C -150 DEG C, orifice potential 10V-60V, capillary voltage 3.0KV-3.5KV, precipitation Agent temperature degree is touched for 380 DEG C -420 DEG C, Desolvention gas velocity 600L/h-700L/h, taper hole gas velocity 50L/h-60L/h Energy is hit as 5V-40V.It is further preferred that the Mass Spectrometry Conditions of the electro-spray ionization holotype are：Ion source temperature is 120 DEG C, orifice potential 10V-60V, capillary voltage 3.5KV, desolvation temperature is 380 DEG C, and Desolvention gas velocity is 600L/h, taper hole gas velocity 50L/h, collision energy 5V-40V；The Mass Spectrometry Conditions of the electro-spray ionization negative mode are： Ion source temperature is 120 DEG C, orifice potential 10V-60V, capillary voltage 3.0KV, and desolvation temperature is 380 DEG C, is taken off Solvent stream speed is 600L/h, taper hole gas velocity 50L/h, collision energy 5V-40V.
In embodiment of the present invention, using inner mark method ration.Still optionally further, it is added in detected sample multi-class The quantitative internal standard of drug and personal care articles and pesticide, so as to the multi-class drug detected in water sample to be measured and personal nursing Product and pesticide carry out relative quantification；Specifically optionally, the quantitative internal standard quantifies internal standard including 5 kinds of PPCPs and a kind of pesticide quantifies Internal standard, it is respectively sulfamethoxazole that 5 kinds of PPCPs, which quantify internal standard,13C6, Medroxyprogesterone d3, salbutamol d9, Gemfibrozil Capsules d6 and oneself This 5 kinds of PPCPs internal standards are made into mixed mark, sulfamethoxazole by the female phenol d4 of alkene13C6, Medroxyprogesterone d3, salbutamol d9, Ji Feiluo The concentration of neat d6 and diethylstilbestrol d4 is followed successively by 1ppm, 1ppm, 1ppm, 10ppm and 10ppm, and it is 10 μ L to mix mark addition；1 kind Benzene Anthelvet d6 is designated as in pesticide is quantitative, a concentration of 1ppm, addition is 10 μ L.
The present invention carries out relative quantification to the multi-class drug and personal care articles and pesticide that are detected in water sample to be measured, adopts With peak area ratio method, correspond to its internal standard per a kind of compound and carry out relative quantification.The present invention, can using inner mark method ration Accurately obtain the content of the PPCPs and pesticide in water sample to be measured.
The embodiment of the present invention includes the change shown in following table 1 by substance detectable testing conditions (a)-(e) Close object.
Method provided by the invention can at least detect 130 kinds of PPCPs and 35 kinds of pesticides in water.
In embodiment of the present invention, the present invention is using in electron spray ionisation source, multiple-reaction monitoring (MRM) mode detection sample Object, by setting different orifice potentials and collision energy, by object importing collision cell touched with Inert gas molecule It hits and is allowed to crack, detection then is scanned to fragment ion, that is, daughter ion of generation, to obtain relevant structural information.It utilizes Whole characteristic ions of acquisition and interionic abundance than carrying out qualitative analysis, with the highest characteristic ion response of abundance with it is dense The relationship of degree carries out quantitative analysis.The multiple-reaction monitoring ion pair and mass spectrum relevant parameter table of each compound are listed in table 1.
The multiple-reaction monitoring ion pair of 1 each compound of table and mass spectrum relevant parameter table
Remarks：Daughter ion 1 is quota ion, and daughter ion 2 is qualitative ion；- represent not detect；
Wherein, when pesticide is detected using testing conditions (e), the Mass Spectrometry Conditions that set as ionization pattern be electron spray Holotype is ionized, but subsequent instrumentation is when actually detected, according to the property of bentazone, close to bentazone retention time When be converted into electro-spray ionization negative mode and ionized, so as to obtain the Information in Mass Spectra of bentazone, subsequently detect again Electro-spray ionization holotype can be converted into during other agricultural chemical compounds.I.e. in testing conditions (e), except bentazone for electron spray from Sonization negative mode, remaining agricultural chemical compound are electro-spray ionization holotype.
The present invention can be to the multi-class drug in water sample and personal nursing using liquid chromatography-tandem mass spectrometry testing conditions Product and pesticide carry out qualitative and quantitative analysis, using retention time locking with characteristic ion to the mode qualitatively screening sample of locking In PPCPs and pesticide pollutant that may be present, effectively eliminate false positive, and testing result is accurate.
The method of multi-class drug and personal care articles and pesticide in quick detection water provided by the invention, method is accurate, Quickly, multiple pollutant can be detected simultaneously, be the pollution condition of PPCPs and pesticide in rapid screening and quantitative assessment various water bodies Method is provided with risk；Method provided by the invention has potential application in terms of a large amount of water sample screenings are carried out with preliminary investigation Value.
Embodiment 1：
A kind of method of multi-class drug and personal care articles and pesticide in quick detection water, including：
(1) sample pre-treatments：
The present embodiment chooses different classes of representational PPCPs and pesticide pollutant, using being derived from the U.S. The ultra-pure water of Millipore ultrapure water machines carries out recovery testu, to determine the selection of eluting solvent.
It is prepared by mark-on water sample：500mL ultra-pure waters are measured, the Na of 5mL 20g/L is added in into water sample2EDTA aqueous solutions mix Close uniformly after, with appropriate ammonium hydroxide adjust water sample pH value be 6.00-6.20, then add in 100 μ L PPCPs mix mark (1 μ g/mL) and 50 μ L pesticides mix mark (2 μ g/mL), and the concentration level of each monomer contamination object (PPCPs or pesticide) is in ultrapure water sample after mark-on 0.2μg/L.After abundant mixing, for use.Ultra-pure water is taken, is not added with mixed mark, for use；
Solid-phase extraction column activates：Solid-phase extraction column is Oasis WAX Cartridge (150mg, 6mL), Oasis HLB Cartridge (500mg, 6mL) and Sep-Pak AC2Plus Short Cartridge (400mg, 85 μm), uses 6- successively 10mL methanol, 6-10mL ultra-pure waters activate solid-phase extraction column, notice that extraction column will keep moistening in activation process.Work as extraction When taking that ultrapure water level is away from upper sieve plate 1mm or so in column, solid-phase extraction device is closed, and solid-phase extraction column is filled ultrapure Water, for use.
Mark-on water sample extracting and enriching：By the solid-phase extraction column activated by WAX columns (on)+HLB columns (in)+AC2 (under) it is suitable Sequence is connected, and then mark-on water sample is connected with WAX columns by large volume sampling pipe, is opened solid-phase extraction device and is carried out mark-on water sample Enrichment, enrichment rate 5-10mL/min.After enrichment, rinse sample bottle with a small amount of ultra-pure water (about 6-10mL) and solid phase extracts Pillar is taken, and drains residual moisture in pillar as possible.
Eluting solvent is the one of the major reasons for influencing the compound rate of recovery in water, in the situation for fixing other extraction conditions Under, solid-phase extraction column is eluted using different organic solvents combination, organic solvent includes first used in experiment in the present embodiment Formic acid-methanol solution, the methyl tertiary butyl ether(MTBE)-methanol solution (volume of methyl tertiary butyl ether(MTBE) and methanol that sour volume fraction is 2% Than being 9:1), (volume ratio of dichloromethane and methanol is 8 to dichloro methane-methanol:2), ammonium hydroxide volume fraction is 5% ammonia Water-methanol solution and a concentration of 20mmol/L ammonium acetates-methanol solution of ammonium acetate.WAX columns and HLB columns use formic acid volume successively Formic acid-methanol solution (being represented in table 2 with WAX1 and HLB1), the methyl tertiary butyl ether(MTBE)-methanol solution (volume ratio that score is 2% It is 9:1) (volume ratio is 8 for (being represented in table 2 using WAX2 and HLB2), dichloro methane-methanol:2) (in table 2 with WAX3 and HLB3 is represented) and ammonium hydroxide volume fraction eluted for 5% ammonia water-methanol solution (being represented in table 2 with WAX4 and HLB4), often The elution volume of kind eluting solvent is 8mL and each eluent is individually undertaken in K-D inspissators；AC2 columns use second successively Sour ammonium concentration is ammonium acetate-methanol solution (being represented in table 2 with AC21) of 20mmol/L and dichloro methane-methanol (dichloro The volume ratio of methane and methanol is 8:2) it (represents) to be eluted with AC22 in table 2, the elution volume of each eluting solvent is 10mL and each eluent is individually undertaken in K-D inspissators.
Collected each eluent is concentrated under 40 DEG C of water bath conditions with soft nitrogen, when effluent volume concentrates It is blown to nitrogen is stopped during about 0.15mL, is that (acetonitrile and water volume ratio are 5 to 1% formic acid-acetonitrile water with formic acid volume fraction:95) solution It is settled to 1mL.Solution after constant volume is transferred in 2mL brown sample bottles, adds in PPCPs and pesticide quantifies internal standard, quantitative internal standard Internal standard is quantified including 5 kinds of PPCPs and a kind of pesticide quantifies internal standard, and it is respectively sulfamethoxazole that 5 kinds of PPCPs, which quantify internal standard,13C6, first This 5 kinds of PPCPs internal standards are made into mixed mark by hydroxyprogesterone d3, salbutamol d9, Gemfibrozil Capsules d6 and diethylstilbestrol d4, and sulfalene is disliked Azoles13C6, Medroxyprogesterone d3, salbutamol d9, Gemfibrozil Capsules d6 and diethylstilbestrol d4 concentration be followed successively by 1ppm, 1ppm, 1ppm, 10ppm and 10ppm, it is 10 μ L to mix mark addition；Benzene Anthelvet d6, a concentration of 1ppm are designated as in a kind of pesticide is quantitative, addition is 10μL.It is measured with Waters ultra performance liquid chromatographies-tandem mass spectrum combined instrument (UPLC-MS/MS).
(2) chromatography and Mass Spectrometry Conditions are：
It is measured with Waters ultra performance liquid chromatographies-tandem mass spectrum combined instrument (UPLC-MS/MS).Analytical column used For ACQUITY UPLC BEH C18cartridge (2.1 × 100mm, 1.7 μm), column temperature is room temperature (~20 DEG C), and sample size is 10 μ L, ionization pattern are divided into ESI+ and ESI- according to detection compound difference, and detector is triple quadrupole bar (TQD).PPCPs and Pesticide pollutant is respectively adopted following five groups of testing conditions by its classification and ionization mode and carries out liquid chromatography-tandem mass spectrometry inspection It surveys, specially：
(a) ionization pattern is ESI+, and mobile phase is that (formic acid volume fraction is 0.04% to formic acid-formic acid aqueous ammonium, formic acid A concentration of 4mM of ammonium formate in aqueous ammonium) (A) and acetonitrile (B), eluent gradient elution program be：0min-0.5min： 95%A, 5%B；3.0min：75%A, 25%B；9.0min：65%A, 35%B；13.5min：20%A, 80%B；14.0min： 0%A, 100%B；14.1min-19.0min：95%A, 5%B；Flow velocity is 0.2mL/min；
(b) ionization pattern is ESI+, and mobile phase is the aqueous formic acid (A) and acetonitrile that formic acid volume fraction is 0.1% (B), eluent gradient elution program is：0min-0.5min：90%A, 10%B；3.5min：70%A, 30%B；4.5min： 60%A, 40%B；7.5min：10%A, 90%B；8.5min：0%A, 100%B；8.6min-10.0min：90%A, 10%B； Flow velocity is 0.25mL/min；
(c) ionization pattern is ESI-, and mobile phase is acetic acid-ammonium acetate solution (acetic acid volume fraction 0.04%, acetic acid A concentration of 4mM of ammonium acetate in aqueous ammonium) (A) and acetonitrile (B), eluent gradient elution program be：0min-0.5min： 70%A, 30%B；4.5min：20%A, 80%B；5.0min：0%A, 100%B；5.1min-9.0min：70%A, 30%B； Flow velocity is 0.25mL/min；
(d) ionization pattern is ESI-, and mobile phase is for water (A) and acetonitrile (B), eluent gradient elution program：0min： 60%A, 40%B；4.0min：50%A, 50%B；4.5min：0%A, 100%B；4.6min-8min：60%A, 40%B；Stream Speed is 0.25mL/min；
(e) ionization pattern is ESI+, and mobile phase is that (formic acid volume fraction is 0.04% to formic acid-formic acid aqueous ammonium, formic acid A concentration of 4mM of ammonium formate in aqueous ammonium) (A) and acetonitrile (B), eluent gradient elution program be：0min-0.5min： 95%A, 5%B；8.0min：40%A, 60%B；11.0min：0%A, 100%B；11.1min-16.0min：95%A, 5%B, Flow velocity is 0.2mL/min.
The Mass Spectrometry Conditions of electro-spray ionization holotype are：Ion source temperature is 120 DEG C, orifice potential 10V-60V, hair Tubule voltage is 3.5KV, and desolvation temperature is touched for 380 DEG C, Desolvention gas velocity 600L/h, taper hole gas velocity 50L/h Energy is hit as 5V-40V；The Mass Spectrometry Conditions of the electro-spray ionization negative mode are：Ion source temperature is 120 DEG C, orifice potential For 10V-60V, capillary voltage 3.0KV, desolvation temperature is 380 DEG C, Desolvention gas velocity 600L/h, taper hole air-flow Speed is 50L/h, collision energy 5V-40V.It is related to the monitoring ion pair and mass spectrum of pesticide compound with each PPCPs Parameter refers to table 1.
(3) method validation
1st, the range of linearity and detection limit
PPCPs and standard sample of pesticide containing various concentration are prepared, the standard items of each concentration are formulated as 1mL, Ran Houfen Not Jia Ru PPCPs same amount of with above-mentioned steps (1) and pesticide quantify internal standard, upper machine testing after mixing.Then it uses The data that TargetLynx surveys upper machine are handled, and obtain corresponding standard curve.The corresponding linear regression of standard curve Equation is Y=aX+b, the peak area of Y=determinands × (target concentration in quantitative/target peak area in quantitative), X=to be measuredization Close object concentration；Thus it can judge the range of linearity of each PPCPs and pesticide and subsequent quantitative by standard curve, the results showed that, this Method is linearly good, in the concentration range of 0.001-200 μ g/L, the linearly related system of most compounds (more than 96%) Number is all higher than 0.99.The method detection limit and method quantitative limit range of method provided in an embodiment of the present invention ng/L grades low, Available for analysis underwater trace PPCPs and pesticide.Illustrate in quick detection water provided in an embodiment of the present invention multi-class drug and The method of personal care articles and pesticide meets the requirement of analysis method.
2nd, recovery test
Using inner mark method ration, mark-on and not two kinds of sample analysis of mark-on need to be carried out at the same time, two kinds of samples of comparison measure dense The difference of degree and known mark-on amount, obtain the recovery of standard addition of representativeness PPCPs and pesticide in different water bodys.As a result such as 2 institute of table Show.
The rate of recovery situation (unit %) of representativeness PPCPs and pesticide under the conditions of the different eluting solvents of table 2
Remarks：WAX1 and HLB1 represent used in eluting solvent be 2% formic acid-methanol solution, used in WAX2 and HLB2 are represented Eluting solvent is methyl tertiary butyl ether(MTBE)-methanol solution, WAX3 and HLB3 represent used in eluting solvent it is molten for methylene chloride-methanol Eluting solvent used in liquid, WAX4 and HLB4 expressions is 5% ammonia water-methanol solution, and AC21 and AC22 then represent eluting solvent point It Wei not 20mmol/L ammonium acetates-methanol solution and dichloro methane-methanol.What R1 was represented is that the elution of WAX columns first two is molten Agent (2% formic acid-methanol solution and methyl tertiary butyl ether(MTBE)-methanol solution) elutes, and HLB columns and 2 columns of AC are only washed with the first The rate of recovery of desolventizing elution (HLB columns are 2% formic acid-methanol solution, and 2 columns of AC are ammonium acetate-methanol solution)；What R2 was represented It is that WAX columns are eluted with four kinds of eluting solvents, HLB columns are eluted with four kinds of eluting solvents, and 2 columns of AC are eluted with two kinds of eluting solvents The rate of recovery.
The result shows that when WAX columns, using preceding 2 kinds of eluting solvents, (formic acid-methanol solution and methyl tertiary butyl ether(MTBE)-methanol are molten Liquid) and HLB columns and AC2 columns only with the 1st kind of eluting solvent (being respectively formic acid-methanol solution and ammonium acetate-methanol solution) into The more satisfied rate of recovery can be obtained during row elution (except the rate of recovery of sulfamerazine is 45.6% and the rate of recovery of Metadelphene Other than 145.8%, the rate of recovery of remaining compound is in the range of 60%-140%), it can meet high-throughput in the present invention The screening demand of pollutant.
(4) measure of actual sample
1st, the feasibility for further eluting solvent selected by verification demonstrates all candidate eluting solvents and extracts different water bodys The recovery of standard addition of middle representativeness PPCPs and pesticide.Concrete operation step is as follows：Prepare different types of water sample --- it is ultrapure Water, tap water and surface water, wherein tap water and surface water are filtered through 0.7 μm of glass fiber filter.By above-mentioned experimental method Mark-on water sample preparation is carried out, the conditions such as the activation of solid-phase extraction column and the enrichment of water sample are same as described above.Elution requirement is WAX Column formic acid-methanol solution of the 8mL formic acid volume fraction for 2%, 8mL methyl tertiary butyl ether(MTBE)s-methanol solution (methyl tertiary butyl ether(MTBE) Volume ratio with methanol is 9:1) it is eluted with 8mL ammonium hydroxide volume fraction for 5% ammonia water-methanol solution, HLB columns 8mL formic acid Formic acid-methanol solution and the 8mL methyl tertiary butyl ether(MTBE)s-methanol solution (body of methyl tertiary butyl ether(MTBE) and methanol that volume fraction is 2% Product is than being 9:1) elution and AC2 columns a concentration of 20mmol/L ammonium acetates-methanol solution of 10mL ammonium acetates and 10mL dichloromethane- (volume ratio of dichloromethane and methanol is 8 to methanol solution:2) it elutes, each eluent is collected separately in K-D inspissators. Then the eluent mixed is concentrated as stated above, constant volume and upper machine testing.Using inner mark method ration, it need to be carried out at the same time and add Mark and not two kinds of sample analysis of mark-on, two kinds of samples of comparison measure the difference of concentration and known spiked levels, obtain different water bodys The recovery of standard addition of middle representativeness PPCPs and pesticide.Difference elution solution combination is to representativeness PPCPs and pesticide in different water bodys Recovery of standard addition the results are shown in Figure 1.
In Fig. 1, R1 represents WAX columns successively with the formic acid-methanol solution and 8mL methyl- terts that 8mL formic acid volume fraction is 2% (volume ratio of methyl tertiary butyl ether(MTBE) and methanol is 9 to butyl ether-methanol solution:1) elution and HLB columns and AC2 columns only use 8mL respectively When formic acid volume fraction is 2% formic acid-methanol solution and a concentration of 20mmol/L ammonium acetates of 10mL ammonium acetates-methanol solution elution The PPCPs of acquisition and the insecticide pollution rate of recovery.R2 represents WAX columns successively with formic acid-first that 8mL formic acid volume fraction is 2% (volume ratio of methyl tertiary butyl ether(MTBE) and methanol is 9 for alcoholic solution, 8mL methyl tertiary butyl ether(MTBE)s-methanol solution:And 8mL ammonium hydroxide volumes 1) Score is eluted for 5% ammonia water-methanol solution, the HLB columns formic acid-methanol solution and 8mL first that 8mL formic acid volume fraction is 2% (volume ratio of methyl tertiary butyl ether(MTBE) and methanol is 9 to base tertbutyl ether-methanol solution:1) elution and AC2 columns are dense with 10mL ammonium acetates (volume ratio of dichloromethane and methanol is the ammonium acetate-methanol solution and 10mL dichloro methane-methanols for spending for 20mmol/L 8:2) PPCPs and the insecticide pollution rate of recovery obtained when eluting.Compound in Fig. 1 (A) is respectively：1 represent sulphadiazine, 2 represent sulfamethoxazole, 3 represent benzsulfamide, 4 represent Norfloxacin, 5 represent Ofloxacin, 6 represent Ciprofloxacin, 7 represent Cortisone, 8 represent Triamcinolone acetonide, 9 represent epitetracyclin, 10 represent difference and represent boldenone to terramycin, 11,12 represent first hydroxyl Progesterone, 13 represent estriol, 14 represent 17 alpha-estradiols, 15 represent azithromycin.Compound in Fig. 1 (B) is respectively：16 generations Table brufen, 17 represent carbamazepine, 18 represent Citalopram, 19 represent Metadelphene, 20 represent chloramphenicol, 21 represent Ah Ti Lip river You, 22 represent salbutamol, 23 represent benzene draw hamming, 24 represent orthene, 25 represent Azodrin, 26 represent Aldicarb Asia Sulfone, 27 represent Bassa, 28 represent Garagard, 29 represent Acetamiprid, 30 represent Tebuconazole.
Fig. 1's the result shows that, eluting solvent and type of elution selected by the embodiment of the present invention are directed to different types of water Body can obtain the preferable rate of recovery.Therefore, it is multi-class in different type water body present invention may apply to detect simultaneously PPCPs and insecticide pollution.Therefore, detection method provided in an embodiment of the present invention by experimental simulation and actual water sample screening and It is proved to be feasible.In recovery testu simulation, the rate of recovery of most compounds is in the range of 60%-140% It is interior, it is as a result satisfactory.
2nd, the PPCPs and pesticide pollutant in practical surface water water sample are detected；
Further to verify multi-class drug and personal care articles and agriculture in quick detection water provided in an embodiment of the present invention The feasibility of the method for medicine, the present embodiment acquire 10 practical surface water water samples.Each surface water water sample is through 0.7 μm of glass fibers 2L is measured after dimension membrane filtration, the Na of 20mL 20g/L is added in into water sample2EDTA aqueous solutions after mixing, use appropriate amounts of ammonia Water adjusts water sample pH value as 6.00-6.20, after abundant mixing, for use.Enrichment, concentration and the upper machine testing of water sample and etc. such as Described in above-mentioned, and while eluting solid phase extraction column, need to collect all eluents of 3 solid phase extraction columns of each water sample In same K-D inspissators.Experimental method used in above-described embodiment is conventional method unless otherwise specified.On Material and reagent used in embodiment etc. is stated, unless otherwise specified, is commercially obtained.
The screening results of representativeness PPCPs and insecticide pollution are as shown in table 3 in practical earth's surface water sample.Wherein, detector bar The total ion chromatogram of 35 kinds of agricultural chemical compounds that part (e) detects is as shown in Figure 2.
The screening results of representativeness PPCPs and insecticide pollution in 3 practical surface water water sample of table
Remarks：The concentration unit of each compound is ng/L in table, and nd expressions do not detect.
Table 3 the result shows that, method provided in an embodiment of the present invention can be gone out that may be present in surface water water sample with screening PPCPs and insecticide pollution simultaneously can carry out quantitative analysis to it.Therefore, method of the invention can be used for multi-class in water Quick, the accurate and high-throughput Screening analysis of PPCPs and insecticide pollution.
As shown in Fig. 2, abscissa is retention time (min) in Fig. 2, ordinate is intensity (%), number 1- methylamines in Fig. 2 Phosphorus, 2- remove deisopropyl-atrazine, 3- orthenes, 4- Tinidazole glucose injections, 5- omethoates, 6- pymetrozines, 7- Azodrin, 8- Sulphur grass spirit, 9- metilomerkaptofosoksids, 10- Acetamiprids, 11- Rogor, 12- imidacloprids I, 13- metrifonate, 14- vamidothions, 15- fenamiphos are sub- Sulfone, 16- Mobucins, 17- remove ethyl Garagard, 18- DDVP, 19- aniline phosphorus sulfones, 20- thiodicarbs, 21- molinates, and 22- is secondary Ding Wei, 23- propazine, 24- Garagards, 25- Acetochlors, 26- Tebuconazoles, 27- Terbufos sulfones, 28- malathions, 29- worm acyls Hydrazine, 30- terbucarbs, 31- diazinons, 32- butachlors, 33- anilofos, 34- Profenofos, 35- bentazones, IS- benzene Anthelvet- d6；From figure 2 it can be seen that agricultural chemical compound can obtain good detection on this condition.
The embodiment of the present invention also provides the selection chromatography of ions figure of part of compounds, as shown in Fig. 3-13.Fig. 3-13 is successively Being represented as sulphadiazine, Ciprofloxacin, testosterone, progesterone, atenolol, Tetracyclines, (it is poor that retention time RT=6.30 corresponds to 4- To dehydration tetracycline, RT=6.67 corresponds to dehydration tetracycline), metronidazole, prednisone, Gemfibrozil Capsules, estriol and acephatemet Select chromatography of ions figure；Upper figure in every figure corresponds to quota ion, and figure below corresponds to qualitative ion.Abscissa is protects in Fig. 3-13 The time (min) is stayed, ordinate is intensity (%).
To sum up, the embodiment of the present invention is established qualitative by optimization aim object concentration and separation condition, chromatography and Mass Spectrometry Conditions Ability is strong, high sensitivity and fast and effeciently analysis detect the method for multi-class drug and personal care articles and pesticide in water. The detection sensitivity of each compound, separating degree and reproducibility are preferable, are PPCPs in rapid screening and quantitative assessment various water bodies With the pollution condition of pesticide method is provided with risk.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (15)

1. a kind of method of multi-class drug and personal care articles and pesticide in quick detection water, which is characterized in that including：
Water sample to be measured is taken, the water sample to be measured is carried out pre-treatment obtains detected sample；
The detected sample is respectively adopted to one or more groups of carry out liquid chromatography-tandem matter in following five groups of testing conditions Spectrum detection, realizes the qualitative analysis to multi-class drug and personal care articles and pesticide in water sample to be measured and quantitative detection：
(a) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Formic acid-formic acid aqueous ammonium, B phases：Acetonitrile, using ladder Degree elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype；
(b) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Aqueous formic acid, B phases：Acetonitrile, using gradient elution, Column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype；
(c) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Acetic acid-ammonium acetate solution, B phases：Acetonitrile, using ladder Degree elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization negative mode；
(d) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Water, B phases：Acetonitrile, using gradient elution, column temperature is room Temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization negative mode；
(e) chromatographic condition：Chromatographic column is C18 columns, and mobile phase is：A phases：Formic acid-formic acid aqueous ammonium, B phases：Acetonitrile, using ladder Degree elution, column temperature is room temperature；Mass Spectrometry Conditions：Ionization pattern is electro-spray ionization holotype.
2. the method for multi-class drug and personal care articles and pesticide in quick detection water as described in claim 1, feature It is, eluent gradient elution program is in (a) testing conditions：
0min-0.5min：95%A, 5%B；3.0min：75%A, 25%B；9.0min：65%A, 35%B；13.5min：20% A, 80%B；14.0min：0%A, 100%B；14.1min-19.0min：95%A, 5%B；
Eluent gradient elution program is in (b) testing conditions：
0min-0.5min：90%A, 10%B；3.5min：70%A, 30%B；4.5min：60%A, 40%B；7.5min：10% A, 90%B；8.5min：0%A, 100%B；8.6min-10.0min：90%A, 10%B；
Eluent gradient elution program is in (c) testing conditions：
0min-0.5min：70%A, 30%B；4.5min：20%A, 80%B；5.0min：0%A, 100%B；5.1min- 9.0min：70%A, 30%B；
Eluent gradient elution program is in (d) testing conditions：
0min：60%A, 40%B；4.0min：50%A, 50%B；4.5min：0%A, 100%B；4.6min-8min：60%A, 40%B；
Eluent gradient elution program is in (e) testing conditions：
0min-0.5min：95%A, 5%B；8.0min：40%A, 60%B；11.0min：0%A, 100%B；11.1min- 16.0min：95%A, 5%B.
3. the method for multi-class drug and personal care articles and pesticide in quick detection water as described in claim 1, feature It is, in (a)-(e) testing conditions, the flow velocity of the mobile phase is 0.2mL/min-0.25mL/min.
4. the method for multi-class drug and personal care articles and pesticide in quick detection water as described in claim 1, feature It is, in (a) and (e), the formic acid-formic acid aqueous ammonium is mixed to get by formic acid and formic acid aqueous ammonium, the first A concentration of 4mmol/L-6mmol/L of ammonium formate in sour aqueous ammonium, the volume point of formic acid in the formic acid-formic acid aqueous ammonium Number is 0.04%-0.06%；In (b), the volume fraction of formic acid is 0.1%-0.2% in the aqueous formic acid；It is described (c) in, the acetic acid-ammonium acetate solution is mixed to get by acetic acid and ammonium acetate solution, second in the ammonium acetate solution A concentration of 4-6mmol/L of sour ammonium, in the acetic acid-ammonium acetate solution, the volume fraction of the acetic acid is 0.04%- 0.06%.
5. the method for multi-class drug and personal care articles and pesticide in quick detection water as described in claim 1, feature It is, the sample size of the detected sample in the chromatography column is 10 μ L-15 μ L.
6. as claim 1-5 any one of them quickly detects the side of multi-class drug and personal care articles and pesticide in water Method, which is characterized in that the mass spectrographic scan mode be multiple-reaction monitoring pattern, detector be triple quadrupole bar, the EFI Mist ionization holotype Mass Spectrometry Conditions be：Ion source temperature is 120 DEG C -150 DEG C, orifice potential 10V-60V, capillary electricity It presses as 3.5KV-4.0KV, desolvation temperature is 380 DEG C -400 DEG C, Desolvention gas velocity 600L/h-700L/h, taper hole gas Flow velocity is 50L/h-60L/h, collision energy 5V-40V；The Mass Spectrometry Conditions of the electro-spray ionization negative mode are：Ion source Temperature is 120 DEG C -150 DEG C, orifice potential 10V-60V, capillary voltage 3.0KV-3.5KV, desolvation temperature 380 DEG C -420 DEG C, Desolvention gas velocity 600L/h-700L/h, taper hole gas velocity 50L/h-60L/h, collision energy 5V- 40V。
7. the method for multi-class drug and personal care articles and pesticide in quick detection water as described in claim 1, feature It is, it is husky to include Norfloxacin, Enoxacin, Ofloxacin, ring third by the detectable substance of the testing conditions (a) Star, Pefloxacin, fleraxacin, Lomefloxacin, Danofloxacin, Enrofloxacin, cinoxacin, Sarafloxacin, Sparfloxacin, two Flucloxacillin, Moxifloxacin, oxolinic acid, sulfaquinoxaline, acidum nalidixicum, flumequine, 5-methoxysulfadiazine, sulfanilamide (SN), sulphaguanidine, sulphur Amine vinegar acyl, sulfaisodimidine, sulphadiazine, Cefradine, lincomycin, sulfapryidine, sulphathiazole, methoxy benzyl ammonia Pyrimidine, sulfamethyldiazine, sulfamethazole, Ormetoprim, sulfamethizole, sulfamerazine, sulfamethoxazole, sulphur Sulfamonomethoxine between amine, cistosulfa, fanasil, azithromycin, sulfamethoxazole, sulfanilamide (SN) Sulfafurazole, Sulfadimethoxine, sulfaphenazolum, anhydroerythromycin, clarithromycin, roxithromycin, Trenbolone, nandrolone, boldenone, 19- Go first androsterone, testosterone, norethindrone, 17 α-methyltestosterone, 21 α-hydroxyprogesterone, stanozolol, androstenedione, epitestosterone, D- dl-Norgestrels, 17 α-hydroxyprogesterone, Medroxyprogesterone, progesterone, danazol, megestrol acetate, Medroxyprogesterone Acetate, chlormadinone acetate, hot breath is flutterred It bitterly, can iron be peaceful, salbutamol, Cimetidine, atenolol, Majorem, Lamotrigine, metoprolol, digoxin, Wen La Method is pungent, Metadelphene, carbamazepine, benzene draw hamming, Prozac, Citalopram and diltiazem；
4- epianhydrotetracyclines, dehydration tetracycline, α-load fat egg are included by the detectable substance of the testing conditions (b) In vain-terramycin, β-apolipoprotein-terramycin, epitetracyclin, tetracycline, fortimicin, minocycline, difference are mould to soil Element, terramycin, difference are to dehydration aureomycin, demeclocycline, chlorquatrimycin, aureomycin, Amoxicillin, metronidazole and diformazan nitre Azoles；
By the detectable substance of the testing conditions (c) include benzsulfamide, chloramphenicol, prednisone, prednisolone, can Pine, hydrocortisone, naproxen, Ketoprofen, 6 alpha-methylprednisolones, fluorometholone, dexamethasone, beclomethasone, fluorine rice Pine, cellulose acetate hydrogen fluorine cortisone, budesonide, Triamcinolone acetonide, fluocinolone acetonide, brufen, Gemfibrozil Capsules, triclosan, triclocarban and Clobetasol propionate；
Triamcinolone, estriol, aldosterone, bisphenol-A, 17 α-female two are included by the detectable substance of the testing conditions (d) Alcohol, the female alcohol of 17 alpha-acetylenes, oestrone, diethylstilbestrol, hexestrol and dienestrol；
By the detectable substance of the testing conditions (e) include acephatemet, go deisopropyl-atrazine, orthene, The careless spirit of Tinidazole glucose injection, omethoate, pymetrozine, Azodrin, sulphur, metilomerkaptofosoksid, Acetamiprid, Rogor, imidacloprid, metrifonate, aphid are gone out Phosphorus, Mobucin, removes ethyl Garagard, DDVP, aniline phosphorus sulfone, thiodicarb, molinate, Bassa, puts out fenamiphos sulfoxide Tianjin, Garagard, Acetochlor, Tebuconazole, Terbufos sulfone, malathion, tebufenozide, terbucarb, diazinon, butachlor, anilofos, Profenofos and bentazone.
8. as described in claim 1 detect the method for multi-class drug and personal care articles and pesticide in water, feature simultaneously It is, the pre-treatment operation of the water sample to be measured includes：Water sample to be measured is taken, after filtering, adds in complexing agent, after mixing, adjusts water Sample pH value is 6.0-7.0, obtains first and treats test sample, treats that test sample carries out Solid Phase Extraction by described first, is eluted after extraction, collection is washed De- liquid, obtains the extracting solution containing multi-class drug and personal care articles and pesticide, after concentration, obtains the detected sample.
9. as claimed in claim 8 detect the method for multi-class drug and personal care articles and pesticide in water, feature simultaneously It is, the extraction column that the Solid Phase Extraction uses includes exchanging solid phase extraction according to the weak anionic that the sequence of upper, middle and lower is sequentially connected in series Column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid-phase extraction column are taken, described first treats test sample followed by described weak the moon Ion Exchange Solid Phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid-phase extraction column.
10. the method for multi-class drug and personal care articles and pesticide in quick detection water as claimed in claim 9, feature It is, the weak anionic exchanges solid-phase extraction column and includes HLB columns including WAX columns, the hydrophilic-lipophilic balance solid-phase extraction column, The activated carbon solid-phase extraction column includes AC2 columns.
11. the method for multi-class drug and personal care articles and pesticide in quick detection water as claimed in claim 9, feature It is, after extraction, the weak anionic of series connection is exchanged into solid-phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid phase Extraction column is split, and exchanging solid-phase extraction column, hydrophilic-lipophilic balance solid-phase extraction column and activated carbon solid phase to weak anionic respectively extracts Column is taken to be eluted；The weak anionic exchanges solid-phase extraction column and uses formic acid-methanol solution and methyl tertiary butyl ether(MTBE)-first successively Alcoholic solution elutes, and the hydrophilic-lipophilic balance solid-phase extraction column is using formic acid-methanol solution elution, the activated carbon Solid Phase Extraction Column is using ammonium acetate-methanol solution elution.
12. the method for multi-class drug and personal care articles and pesticide in quick detection water as claimed in claim 11, special Sign is, the percentage by volume of formic acid is 2%-5% in the formic acid-methanol solution, the methyl tertiary butyl ether(MTBE)-methanol solution The volume ratio of middle methyl tertiary butyl ether(MTBE) and methanol is 9:1, a concentration of 20mmol/ of ammonium acetate in the ammonium acetate-methanol solution L-40mmol/L。
13. the method for multi-class drug and personal care articles and pesticide in quick detection water as claimed in claim 9, feature Be, described first treat test sample the weak anionic exchange solid-phase extraction column, the hydrophilic-lipophilic balance solid-phase extraction column and Flow velocity in the activated carbon solid-phase extraction column is 5mL/min-10mL/min.
14. the method for multi-class drug and personal care articles and pesticide in quick detection water as claimed in claim 11, special Sign is, each eluent exchanges solid-phase extraction column, the hydrophilic-lipophilic balance solid-phase extraction column and described in the weak anionic Elution speed in activated carbon solid-phase extraction column is 1mL/min-2mL/min.
15. the method for multi-class drug and personal care articles and pesticide in quick detection water as claimed in claim 8, feature It is, the complexing agent includes ethylenediamine tetra-acetic acid or disodium ethylene diamine tetraacetate, and the addition of the complexing agent is every liter of institute State the complexing agent that 0.2g-0.5g is added in water sample to be measured.
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CN109813823A (en) * 2019-04-04 2019-05-28 江苏省产品质量监督检验研究院 The HPLC analytical method of metronidazole and Norfloxacin in a kind of toothpaste
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CN115097024A (en) * 2022-05-31 2022-09-23 重庆市疾病预防控制中心(重庆市救灾防病应急处理中心) PPCPS detection method based on UPLC-MS/MS method
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