CN108896670A - PPCPs pollutant rapid screening detection method in Drinking Water - Google Patents
PPCPs pollutant rapid screening detection method in Drinking Water Download PDFInfo
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Abstract
The present invention relates to analytical chemistry, field of food safety, the in particular to detection method of drinking water.PPCPs class dirt rapid detection method in a kind of Drinking Water, the database of 112 kinds of PPCPs is established based on retention time, parent ion and daughter ion accurate molecular weight, for the confirmation screening of target analytes, and peak area is extracted based on level-one parent ion and realizes accurate quantitative analysis.Method includes：It prepares 112 kinds of PPCPs compound standard liquid, sample extraction, sample purification, chromatography, mass spectral analysis, establish screening database, data processing.This method quickly, accurate, high sensitivity, screening range it is wide, carry out Risk Monitoring for water quality and provide the strong technological means of one kind, effective guarantee can be provided for food safety Regulation.
Description
Technical field
The present invention relates to analytical chemistry, field of food safety, the in particular to detection method of drinking water.
Background technique
Drug and personal-care supplies (Pharmaceutical and Personal Care Products, PPCPs) exist
The disease treatment of human and animal and the use of personal hygiene have had the history in many years, however as a kind of " emerging
Environmental contaminants ", increasingly cause the extensive concern of people.(the environmental science .2017.38 such as Zhang Panwei, Zhou Huaidong (5):
1852-1862), from a wealth of sources, including various prescription medicines, non-prescribed medicine, cosmetics and cleaning chemical products etc., commonly known as
" spurious persistence " pollutant, (Q Yan, X Gao, et al. Chemospere, 2014,99 (3):160-170) PPCPs is main
Entered in environment by works liquor, human body is generally entered by drinking water, it is most straight in PPCPs to become Human body package
One of main intake approach is connect, (energy research and information .2015.31 (3) such as Ji Guixia, Wang Xue company:142-147) and by
Proving may there are certain risks to ecological environment and human health.(Q Q Zhang,G G Ying, et al.Environ
Sci Technol,2015,49(11):6772-82)。
The PPCPs worldwide such as U.S., Britain, Spain, Japan, South Korea, Costa Rica and Thailand
It is detected in state's water environment, detection level is from ng/L~μ g/L, and its source in water environment and distribution are quite wide
It is general.(D Azanu,B Styrishave,et al.Sci Total Environ.2018.(622):293-305；W j Deng,
N Li,Ecotox Environ Safe.2016.(125):121-127) such as Mychelle A uses liquid chromatography-tandem matter
Spectrometry is to the earth's surface of Rio de Daneiro, BRA and drinks aquametry beta-lactam, macrolides, fluoroquinolones, sulfonamide
46 kinds of analyte antibiotic of class and pyran.The quantitative limit surface water of this method be 3~38ng/L, drinking water be 0.5 to
64ng/L.In the 25-1000ng/L range of linearity, R2 is greater than 0.94.Testing result shows Amoxicillin in surface water, head
Cefalexin and the content of sulfamethoxazole are up to 105ng/L, erythromycin, and the content of azithromycin and clarithromycin is up to 35ng/
L.Clarithromycin, Cefaclor, oxacillin, sulfamethoxazole and troleandomycin are also detected in drinking water, and concentration is big
In 10ng/L.(M A.Monteiro,B F.Spisso,et al.J.Braz.Chem.Soc.2018,29(4)： 801-813.)
In recent years, China also increasingly pays close attention to the PPCP pollutant in water environment.It waste water, natural water, soil,
In deposit even drinking water, also widely it detected.(H Chen,L Jing,et al.Sci Total
Environ.2018.(618)409–418；J Du, H X Zhao, S S Liu, et al.Sci Total
Environ.2017.(595):521–527；S N Zhao,X H Liu,et al.Sci Total Environ.2016.
(569):1350-1358.) such as .Hexing Wang passes through isotopic dilution-two dimension ultra performance liquid chromatography and high-resolution
Quadrupole rod flight time mass spectrum joint technology measures 21 kinds of common antibiotics (5 kinds of macrolides, 2 kinds of interior acyls of β-in water sample
Amine, 3 kinds of Tetracyclines, 4 kinds of fluoroquinolones, 4 kinds of sulfamidos and 3 kinds of phenols).Drinking water includes Municipal water distribution systems
The bucket of 46 terminals of different location originally 45 bottled water samples and 8 different brands of water sample and 14 generic brand
Fill water sample.In 21 kinds of antibiotic, Florfenicol and Thiamphenicol are only found in tap water, median concentration is respectively
6.4-8.9ng/L only has found Florfenicol, concentration range 1-6ng/L, barreled in three bottled water samples of same brand
Antibiotic is not found in water.(H X Wang,B Wang, et al.Environ Sci Tech Let,2016.50(5):
2692-2699.) of heap of stone wait of gold analyzes 13 kinds of sulfa antibiotics in East China using efficient liquid phase tandem mass spectrum method
Distribution characteristics in source water the result shows that, 13 kinds of sulfa antibiotics have different degrees of detection in source water, total dense
Degree is 10.5ng/L-238.5ng/L.(gold is of heap of stone, and Jiang Lei waits environmental science .2016.37 (7):2515-2510.)
To sum up the study found that presence of the PPCPs in Drinking Water has been undisputable fact, however its broad categories,
Including antibiotic, anodyne, anti-inflammatory drug, depressor, contraceptive, fungicide etc., and content is very low, however before existing sample
Reason technology for various PPCPs detergent power it is limited, cause PPCPs in water sample screening range and dosing accuracy by
Limitation.Therefore, need to develop effective Sample Pretreatment Technique Used and high accuracy detection means to the trace PPCPs in water sample
Pollutant carries out high flux examination and quantitative analysis.
Summary of the invention
The purpose of the present invention is logical for analysis existing for PPCPs pollutant detection technique in Drinking Water and method
Measure low, detection not exclusively, the low problem of low efficiency, poor accuracy, sensitivity, it is dirty to provide PPCPs class in a kind of Drinking Water
Object rapid detection method is related to 14 classes, covers 112 kinds of PPCPs pollutants.And based on retention time, parent ion and daughter ion essence
True molecular weight establishes the database of 112 kinds of PPCPs, which can be water head site water quality
Safety detection screening provides new method, new technology, provides the necessary technical supports, solves for water quality safety monitoring, early warning and law enforcement
Without PPCPs pollutant rapid screening detection method in Drinking Water national standard of having determined, detection efficiency is improved, shortens detection week
Phase reduces testing cost, ensures the food safety of domestic and international consumer.
The present invention is that technical solution used by solving above-mentioned purpose is：PPCPs class dirt is fast in a kind of Drinking Water
Fast detection method.
(1) 112 kinds of PPCPs compound standard liquid are prepared
Establish the Test database of 112 kinds of PPCPs compounds：Wherein 112 kinds of PPCPs pollutants include sulfamido antibacterial
Medicine, beta-lactam antibiotic, Comprecin, hormone anti-inflammatory drugs, macrolides, nitro glyoxaline, amino first
Esters of gallic acid, Tetracyclines, beta blocker class, diabetes class, asthma antibechic class, antipyretic-antalgic class, anti-inflammatory class, killing insect, mite
Mushroom, the purity of 112 kinds of PPCPs organic pollutants is all larger than 98.3%, and configures concentration with methanol for following standard sample
The mother liquor of 100 μ g/mL, hybrid standard working solution dilution in acetonitrile are placed in -18 DEG C of refrigerator and save to 1 μ g/mL；
Standard working curve working solution：Take hybrid standard working solution 0.5mL with 5% methanol constant volume into 5mL volumetric flask, i.e.,
Obtain the solution of 100 ng/mL.Further according to needing to be diluted working solution step by step with 5% methanol solution.Since 112 kinds of PPCPs have
The response of machine pollutant is different, so diluted concentration is step by step by working solution：0.1ng/mL, 1ng/mL, 2ng/mL, 5ng/
ML, 10ng/mL, 20ng/mL, 25ng/mL, 40ng/mL, 50ng/mL, 80ng/mL, 100ng/mL；
(2) sample extraction
50mL Drinking Water sample is respectively taken, acid or basic treatment is carried out to sample respectively, adds concentrated hydrochloric acid and ammonium hydroxide,
So that its pH value is adjusted to 3 and 7, is then respectively adding 25mg EDTA, oscillation dissolution.
(3) sample purification
Prepared sample is purified using SPE column (Cleanert PEP-2), activates SPE with 3mL methanol in advance
Column.Balance：SPE column used in sample is extracted for acid condition, the ultrapure water of 3mL (pH=3), nature under gravity is added
It drips, retains the water of about 1 mL in SPE column；SPE column used in sample is extracted for alkaline condition, 3mL (pH=10) is added
Ultra-pure water solution is dripped naturally under gravity, retains the water of about 1mL in SPE column.Loading：25mL large volume column tube is passed through
Adapter is connected to above SPE column, the 50mL water sample of preparation is transferred in pipe, under the action of vacuum pump, with 8mL/min
To the speed loading of 10mL/min, the liquid in SPE column is drained after end of the sample；Then under the action of vacuum pump, 3mL
Ultrapure water (pH=7) elutes twice, finally drains the liquid in SPE column.Elution：Under the effect of gravity, with 1mL methanol/second
Nitrile (v/v=1:1) it elutes 3 times, merges eluent, be dried with nitrogen at 40 DEG C, redissolved with the methanol aqueous solution of 1mL 20%,
Upper machine measurement.
(4) chromatography
Chromatographic column:Accucore RP-MS(Thermo Scientific,100×2.1mm,2.6μm)；Column temperature：40℃；
Mobile phase A：0.1% formic acid-aqueous solution；Mobile phase B：0.1% formic acid-methanol solution；Flow velocity:0.3mL/min；Sample volume:
10μL；Separate gradient：5%B (0min) -5%B (2min) -30%B (7min) -90%B (11min) -90%B (13min) -
5%B (16min).
(5) mass spectral analysis
Scan pattern：Positive ion mode；Capillary temperature：320℃；Heating temperature：320℃；Sheath gas：N2Flow velocity 40arb；
Assist gas：N2Flow velocity 10arb；Spray voltage is (Spray Voltage)：3200V；Lens voltage：50V；Scan pattern is
Full MS/dd-MS2, first mass spectrometric (MS) parameter setting：The resolution ratio R=70,000, AGC target of full scan:1×
106, maximum residence time (Maximum IT)：100ms, scanning range m/z 100~1000；Second order ms (MS/MS) parameter
Setting：Resolution ratio R=17,500, AGC target： 2×105, maximum residence time (Maximum IT)：50ms.
(6) screening database is established
The database of 112 kinds of PPCPs is established based on retention time, parent ion and daughter ion accurate molecular weight.To 112 kinds
PPCPs compound uses Full MS/dd-MS2Mode is analyzed, obtain the retention time of object, parent ion, fragment from
The information such as sub- accurate mass number and ionized form.Then 112 kinds of compounds simulate using Xcalibur software broken
It splits, fragment ion masses number practical in each compound second order ms figure and theoretical accurate mass number deviation is less than 5ppm, and rich
Degree is in first five strong ion as fragments characteristic ion.Finally by 112 kinds of PPCPs Compound Retention times, the theoretical essence of parent ion
The theoretical accurate mass number of true mass number and feature secondary fragment ions, establishes screening database.
(7) data processing
Only do qualitatively screening analysis：Redissolution sample after acidic extraction and alkalinity are extracted respectively takes 0.4mL, upper machine after mixing
Detection and analysis, if desired do quantitative analysis, and the chemical characteristic of reference compound carries out corresponding acid or alkalinity and extracts sample
Processing, then individually sample introduction is analyzed.
In described (1) step, the Test database of 112 kinds of PPCPs compounds is established, wherein 112 kinds of PPCPs pollutant tools
Body is：
In described (2) step：If desired it does qualitative and does quantitative analysis simultaneously：Be referred to the chemical characteristic of compound into
Row is corresponding acid or alkalinity extracts sample treatment, and then individually sample introduction is analyzed.Water sample pre-treatment is divided into 2 groups, and one group is acid
Property under the conditions of extract, another group to extract under alkaline condition, final upper machine testing respectively.If only doing qualitatively screening analysis：It will be sour
Property extract and alkalinity extract after redissolution sample with respectively taking 0.4mL, machine testing is gone up after mixing.
In described (2) step, sample extraction, the PPCPs compound that according to the form below acidic extraction or alkalinity are extracted respectively：
In described (3) step, if experiment purpose is screening pollutant, soda acid is extracted and redissolves liquid etc. than mixing LC-MS/
MS analysis；If experiment purpose is certain quantitative pollutant, soda acid is extracted redissolve liquid progress respectively.
The information of 112 kinds of PPCPs analytes in described (6) step：
The application has significant innovation compared with similar technique：1. establishing 112 kinds of PPCPs in water (is related to 14 class packets
Include disulfonamide, beta-lactam antibiotic, Comprecin, hormone anti-inflammatory drugs, macrolides, nitro
It is imidazoles, carbamates, Tetracyclines, beta blocker class, diabetes class, asthma antibechic class, antipyretic-antalgic class, anti-inflammatory
Class, killing insect, mite mushroom) screening database.2. having developed efficient Sample Pretreatment Technique, Drinking Water is realized
In 112 kinds of PPCPs pollutants the processing of quick and high-recovery；Type is comprehensive, at present without this detection in water quality detection
Mesh.3. being based on level four bars-electrostatic orbit ion trap high-resolution mass spectrometer, the fast of PPCPs compound in Drinking Water is realized
Fast screening and high sensitivity quantitation analysis.
(1) Test database of 112 kinds of PPCPs compounds is established, and based on retention time, parent ion and daughter ion essence
True molecular weight realizes the qualitatively screening analysis of hundreds of PPCPs class compound in water.
(2) research establish in water quality 112 kinds of PPCPs compounds sample purification and ultra performance liquid chromatography-level four bars/
The qualitatively screening and Simultaneous Quantitative Analysis method of electrostatic field orbit trap high resolution mass spectrum；This method quickly, accurate, high sensitivity, sieve
It looks into that range is wide, carries out Risk Monitoring for water quality and provide a kind of strong technological means, can be provided for food safety Regulation effectively
It ensures.
(3) fill up the detectability of PPCPs compound in China's Drinking Water, can in drinking water antibiotic,
The traces such as hormone, anti-inflammatory drug (ng/L~μ g/L order of magnitude) substance is detected.
Detailed description of the invention
Fig. 1 is the extraction chromatography of ions figure of 112 kinds of PPCPs compounds, and wherein concentration is 20ng/mL.
Fig. 2 is the extraction chromatography figure of 112 kinds of PPCPs.
Specific embodiment
Invention is further described in detail combined with specific embodiments below, but the invention is not limited to specific implementations
Example.
PPCPs pollutant rapid screening detection method in Drinking Water,
1.1 key instrument equipment
Ultra performance liquid chromatography-level four bars/electrostatic field orbit trap high resolution mass spectrum (Q-Exactive plus, Thermo
Scientific, USA), match heatable electric spray ion source (HESI)；High pressure liquid chromatography (DionexUltiMate
3000, USA)；Solid-phase extraction device (Supelco-24, USA)；Nitrogen evaporator (Organomation N-EVAP 112, USA)；
1.2 main agents and consumptive material
Methanol (HPLC grades, German Merk company)；Formic acid (HPLC grades, Shanghai ANPEL Scientific Instrument Co., Ltd.)；Second two
Amine tetraacethyl dihydrate (EDTA disodium salt dehydrate C10H14N2Na2O82H2O) (purity
99.999%, Macklin)；Concentrated hydrochloric acid (excellent pure grade, 36~38%, three factory of Tianjin chemical reagent)；Ammonium hydroxide (analyzes pure, state
Chemical reagent Co., Ltd of medicine group)；Filter membrane (0.45 μm, Agilent company of the U.S.)；Large volume column tube and connection conversion head
(25mL, Tianjin Ai Jieer Science and Technology Ltd.)；Cleanert PEP-2 (60mg/3mL, Ai Jieer)；High purity water is through Milli-Q
Superpure water machine purifies to obtain；The purity of 112 kinds of PPCPs pollutants is all larger than 98.3%, is purchased from Sigma respectively,
Dr.EhrenstorferGmbh, First standard and TRC company.
Specific detecting step is as follows：
1. preparing 112 kinds of PPCPs compound standard liquid
1.1 establish the Test database of 112 kinds of PPCPs compounds：100 μ g/ of concentration is configured with methanol by following standard specimen
The mother liquor of mL is placed in -18 DEG C of refrigerator and saves.Specific 112 kinds of PPCPs organic pollutants are shown in Table 1.
1.2 hybrid standard working solutions：10 μ L are respectively taken from single mark methanol solution of 100 μ g/mL, with 900 μ L dilution in acetonitrile,
And be stored in Brown Glass Brown glass bottles and jars only, it is placed in -18 DEG C of refrigerators and saves.The concentration of PPCPs organic contamination is equivalent to 1 μ g/mL
(1000ng/mL)。
1.3 standard working curve working solutions：Take hybrid standard working solution 0.5mL 5% methanol constant volume to 5mL volumetric flask
In to get arrive 100ng/mL solution.Further according to needing to be diluted working solution step by step with 5% methanol solution.Due to 112 kinds
The response of PPCPs organic pollutant is different, so diluted concentration is step by step by working solution：0.1ng/mL, 1ng/mL, 2ng/
ML, 5ng/mL, 10ng/mL, 20 ng/mL, 25ng/mL, 40ng/mL, 50ng/mL, 80ng/mL, 100ng/mL.
2. sample extraction
2.1 sample pretreatment
By water sample 10000rpm centrifuge, it is centrifuged 5min, 0.45 μm of film filtering is crossed, removes particulate material, take 50mL
Filtered water sample is into 50mL centrifuge tube.(in general Drinking Water is very clean, does not have to this step, if other earth's surfaces
Water seems that the muddy water quality of comparison can take the pre-treatment step.)
2.2 addition recovery experiments
1 μ g/mL (2.2.12) is mixed into 112 kinds of PPCPs standard liquids and adds 10 μ L, 20 μ L, 40 μ L respectively into 50mL water sample,
Corresponding pitch-based sphere is：0.2 μ g/L, 0.4 μ g/L, 0.8 μ g/L.
2.3 sample preparation
(a) acidic extraction：15 μ L concentrated hydrochloric acids are added into 50mL water sample, so that its pH value is adjusted to 3,25mg is then added
EDTA, oscillation dissolution.
(b) alkalinity is extracted：150 μ L ammonium hydroxide are added into 50mL water sample, so that its pH value is adjusted to 10,25mg is then added
EDTA, oscillation dissolution.
If desired it does qualitative and does quantitative analysis simultaneously：The chemical characteristic for being referred to compound carries out corresponding acid or alkali
Property extract sample treatment, then individually sample introduction is analyzed.Water sample pre-treatment is divided into 2 groups, and one group is to extract under acid condition,
Another group, to extract under alkaline condition, is finally gone up machine testing respectively.It is particularly adapted to the compound that acidic extraction or alkalinity are extracted
It is shown in Table 1.If only doing qualitatively screening analysis：Redissolution sample after acidic extraction and alkalinity are extracted is mixed with 0.4mL is respectively taken
Upper machine testing after conjunction.
1 112 kinds of PPCPs organic pollutants of table and extracting mode
3. sample purification
Prepared sample is purified using SPE column (Cleanert PEP-2), activates SPE with 3mL methanol in advance
Column.Balance：SPE column used in sample is extracted for acid condition, the ultrapure water of 3mL (pH=3), nature under gravity is added
It drips, retains the water of about 1 mL in SPE column；SPE column used in sample is extracted for alkaline condition, 3mL (pH=10) is added
Ultra-pure water solution is dripped naturally under gravity, retains the water of about 1mL in SPE column.Loading：25mL large volume column tube is passed through
Adapter is connected to above SPE column, the 50mL water sample of preparation is transferred in pipe, under the action of vacuum pump, with 8mL/min
To the speed loading of 10mL/min, the liquid in SPE column is drained after end of the sample；Then under the action of vacuum pump, 3mL
Ultrapure water (pH=7) elutes twice, finally drains the liquid in SPE column.Elution：Under the effect of gravity, with 1mL methanol/second
Nitrile (v/v=1:1) it elutes 3 times, merges eluent, be dried with nitrogen at 40 DEG C, redissolved with the methanol aqueous solution of 1mL 20%,
Upper machine measurement.
4. chromatography
Chromatographic column:Accucore RP-MS(Thermo Scientific,100×2.1mm,2.6μm)；Column temperature：40℃；
Mobile phase A：0.1% formic acid-aqueous solution；Mobile phase B：0.1% formic acid-methanol solution；Flow velocity:0.3mL/min；Sample volume:
10μL；Separate gradient：5%B (0min) -5%B (2min) -30%B (7min) -90%B (11min) -90%B (13min) -
5%B (16min).
5. mass spectral analysis
Scan pattern：Positive ion mode；Capillary temperature：320℃；Heating temperature：320℃；Sheath gas：N2Flow velocity 40arb；
Assist gas：N2Flow velocity 10arb；Spray voltage is (Spray Voltage)：3200V；Lens voltage：50V；Scan pattern is
Full MS/dd-MS2, first mass spectrometric (MS) parameter setting：The resolution ratio R=70,000, AGC target of full scan:1×
106, maximum residence time (Maximum IT)：100ms, scanning range m/z 100~1000；Second order ms (MS/MS) parameter
Setting：Resolution ratio R=17,500, AGC target： 2×105, maximum residence time (Maximum IT)：50ms.
6. establishing screening database
The database of 112 kinds of PPCPs is established based on retention time, parent ion and daughter ion accurate molecular weight.To 112 kinds
PPCPs compound uses Full MS/dd-MS2Mode is analyzed, obtain the retention time of object, parent ion, fragment from
The information such as sub- accurate mass number and ionized form.Then 112 kinds of compounds simulate using Xcalibur software broken
It splits, fragment ion masses number practical in each compound second order ms figure and theoretical accurate mass number deviation is less than 5ppm, and rich
Degree is in first five strong ion as fragments characteristic ion.Finally by 112 kinds of PPCPs Compound Retention times, the theoretical essence of parent ion
The theoretical accurate mass number of true mass number and feature secondary fragment ions, establishes screening database.
Information such as 2 institutes of table such as theoretical molecular weight, fragment ion, retention time, the clastotype of specific PPCPs compound matter
Show.Fig. 1 is the extraction chromatography of ions figure (concentration 20ng/mL) of 112 kinds of PPCPs compounds.Result of study shows 112 kinds
The available good separation of PPCPs class compound, and there is lower detection lower bound, it can satisfy water quality trace analysis
Demand.According to the accurate mass number of retention time and parent ion, daughter ion, detected PPCPs class can be qualitatively and quantitatively determined
Compound, can for Dalian water head site water quality safety detect screening new method, new technology are provided, for water quality safety monitoring, early warning and
Law enforcement provides the necessary technical support.
The information table of 2 112 kinds of PPCPs analytes of table
。
1. the selection of water sample extraction conditions
In order to guarantee that analysans is effectively extracted from sample, carried out respectively using acidic extraction and alkalinity extraction
Sample pre-treatments, Screening analysis.This experiment is by investigating the water sample point that 112 kinds of PPCPs compound pitch-based spheres are 0.2 μ g/L
Not Cai Yong acidic extraction method and alkali extraction method, analyzed through the concentration of SPE column purification, LC-MS/MS, calculate the gained rate of recovery and determine
Best sample pre-treating method.The results show that the method that wherein 33 kinds of PPCPs class compounds are applicable in acidic extraction, 41 kinds
The method that PPCPs class compound is suitble to alkalinity to extract, other 38 kinds of compound alkali carries acid mention, as cephalo-type is suitable for acid
It extracts, xacin-series, sulfamido, nitro glyoxaline are suitable for alkaline extraction mostly.Therefore, for variety classes PPCPs in water sample
Analysis, the chemical characteristic that should refer to compound select extracting method appropriate.
2. the selection of Mass Spectrometry Conditions
This research adds the second order ms scanning mode (Full of data dependence using the first mass spectrometric full scan of high resolution mass spectrum
MS/ dd-MS2), the highest instrumental response value of analyte, has carried out the optimization of all mass spectrometry parameters in order to obtain.In full scan
In mode, mass resolution is most important to the selectivity of target substance and sensitivity.When resolution ratio increases, mass spectrum can
The accurate molecular mass of accurate extraction of analytes, causes sensitivity to improve, otherwise, when resolution ratio reduces, it may extract and target
The chaff interferent that substance has identical fragment is marked, leads to false positive results occur.But when resolution ratio increases, under scanning of the mass spectrum rate
Drop, causes chromatographic peak profile to be deteriorated, influences quantitative result accuracy.Therefore the chromatographic peak profile based on analyzed substance, selection are needed
Optimum resolution.Many experiments the result shows that, first mass spectrometric (MS) scanning resolution R is set as 70,000 second order ms by us
(MS/MS) resolution ratio R is set as 17, and the extraction chromatography figure of 500,112 kinds of PPCPs is shown in Fig. 2, the resolution ratio of 112 kinds of PPCPs of gained
It is preferable with separating degree.
3. the foundation and verifying of screening database
This research makes full use of the advantage of Q-Orbitrap high resolution mass spectrum, uses Full to 112 kinds of PPCPs compounds
MS/dd-MS2Mode is analyzed, and retention time, parent ion, fragment ion accurate mass number and the ionization of object are obtained
The information such as form.Then simulation fragmentation is carried out to 112 kinds of compounds using Xcalibur software, by each compound second order ms
Practical fragment ion masses number and theoretical accurate mass number deviation are less than 5ppm in figure, and abundance is in first five strong ion conduct
Fragments characteristic ion.It is finally that 112 kinds of PPCPs Compound Retention times, parent ion theory accurate mass number and feature second level is broken
The theoretical accurate mass number of piece ion is established screening database (as shown in table 2), the screening for PPCPs in water.
In order to verify the reliability of this screening method, when sample addition concentration level is 0.2 μ g/L, 107 kinds of PPCPs chemical combination
Object is identified that a kind of PPCPs compound is shown " NotFound " by " Confirmed ", and 4 kinds of PPCPs compounds are shown
" Identified " is suspicious, and confirmation rate reaches 95.5%；When sample addition concentration level is 0.4 μ g/L, 109 kinds of PPCPsization
It closes object and is identified that 3 kinds of PPCPs compounds show that " Identified " is suspicious, and confirmation rate reaches by " Confirmed "
97.3%；When sample addition concentration level is 0.8 μ g/L, 111 kinds of PPCPs compounds are identified by " Confirmed ", a kind
PPCPs compound shows that " Identified " is suspicious, and confirmation rate reaches 99.1%.
4. methodology validation
4.1 linear ranges and detection limit
Using the extraction chromatography peak area of object parent ion as ordinate y, using the concentration of object as abscissa x, draw
Standard curve.All PPCPs compounds linear relationship in suitable range is good, related coefficient (R2) it is all larger than 0.99,
The target compound of low concentration is added in blank distilled water, the corresponding concentration of signal-to-noise ratio S/N=10 is the quantitative limit of method, is seen
Table 3.
3 112 kinds of PPCPs linear equations of table and detection limit
4.2 rate of recovery and precision
Using Watson distilled water as blank sample, the method for adding 112 kinds of PPCPs standard solution thereto is added
Assay recovery is added to measure.It has been substantially carried out 3 horizontal addition experiments (0.2 μ g/L, 0.4 μ g/L, 0.8 μ g/L), Mei Geshui
It is flat to be repeated 6 times.Average recovery rate range when pitch-based sphere is 0.2 μ g/L is 60.7%~129.5%, coefficient of variation model
Enclose is 1.4%~17.8%；Average recovery rate range when pitch-based sphere is 0.4 μ g/L is 60.1%~122.6%, is become
Different coefficient range is 1.3%~15.8%；Average recovery rate range when pitch-based sphere is 0.8 μ g/L is 63.1%~
120.1%, coefficient of variation range is 1.1%~10.7%.Specific data are shown in Table 4.The result shows that the high throughput rapid screening
Detection technique can be used for the detection of routine analysis, can detect screening for water head site water quality safety and provide new method, new technology,
It provides the necessary technical support for water quality safety monitoring, early warning and law enforcement.
The rate of recovery and relative standard deviation (RSD) under the different addition concentration of table 4
。
A kind of quick, simple sample-pretreating method of this research and development, and it is based on ultra performance liquid chromatography-level Four
Bar/electrostatic field orbit trap high resolution mass spectrum realizes in water quality rapid screening and the quantitative analysis of 112 kinds of PPCPs.This method
In we the database of 112 kinds of PPCPs is established based on retention time, parent ion and daughter ion accurate molecular weight, be used for target
The confirmation screening of analyte, and peak area can be extracted based on level-one parent ion and realize accurate quantitative analysis.For Screening analysis, work as sample
When product concentration level is greater than 0.2 μ g/L, the confirmation rate of PPCPs can reach 95.5% or more；For quantitative analysis, linear model
When being trapped among 0.1-100ng/mL, the quantitative limit range of 112 kinds of PPCPs is 0.002-0.8 μ g/L, and 3 horizontal additions are tested flat
Equal rate of recovery range is 60.1%~129.5%, and coefficient of variation range is 1.1%~17.8%.This method is quick, accurate, clever
Sensitivity is high, screening range is wide, carries out Risk Monitoring for water quality and provides a kind of strong technological means, can supervise for food safety
Pipe provides effective guarantee.
Claims (6)
1. PPCPs class dirt rapid detection method in a kind of Drinking Water, which is characterized in that
(1) 112 kinds of PPCPs compound standard liquid are prepared
Establish the Test database of 112 kinds of PPCPs compounds：Wherein 112 kinds of PPCPs pollutants include 14 classes：Sulfamido is anti-
Bacterium medicine, beta-lactam antibiotic, Comprecin, hormone anti-inflammatory drugs, macrolides, nitro glyoxaline, amino
Formate ester, Tetracyclines, beta blocker class, diabetes class, asthma antibechic class, antipyretic-antalgic class, anti-inflammatory class, killing insect, mite
Mushroom；The purity of 112 kinds of PPCPs organic pollutants is all larger than 98.3%, and configures 100 μ of concentration with methanol for standard sample
The mother liquor of g/mL, hybrid standard working solution dilution in acetonitrile are placed in -18 DEG C of refrigerator and save to 1 μ g/mL；
Standard working curve working solution：Take hybrid standard working solution 0.5mL with 5% methanol constant volume into 5mL volumetric flask to get arriving
The solution of 100ng/mL, further according to needing to be diluted working solution step by step with 5% methanol solution, due to 112 kinds of PPCPs organic contaminations
Object response is different, so diluted concentration is step by step by working solution：0.1ng/mL, 1ng/mL, 2ng/mL, 5ng/mL, 10ng/
ML, 20ng/mL, 25ng/mL, 40ng/mL, 50ng/mL, 80ng/mL, 100ng/mL；
(2) sample extraction
50mL Drinking Water sample is respectively taken, acid or basic treatment is carried out to sample respectively, concentrated hydrochloric acid and ammonium hydroxide is added, makes it
PH value is adjusted to 3 and 7, is then respectively adding 25mg EDTA, oscillation dissolution；
(3) sample purification
Prepared sample is purified using SPE column (Cleanert PEP-2), activates SPE column with 3mL methanol in advance；
Balance：SPE column used in sample is extracted for acid condition, the ultrapure water of 3mLpH=3 is added, is dripped naturally under gravity
Under, retain the water of about 1mL in SPE column；SPE column used in sample is extracted for alkaline condition, the ultrapure of 3mL (pH=10) is added
Aqueous solution is dripped naturally under gravity, retains the water of about 1mL in SPE column；
Loading：25mL large volume column tube is connected to above SPE column through adapter, the 50mL water sample of preparation is transferred in pipe,
Under the action of vacuum pump, with the speed loading of 8mL/min to 10mL/min, the liquid in SPE column is drained after end of the sample；
Then under the action of vacuum pump, 3mL ultrapure water (pH=7) is eluted twice, finally drains the liquid in SPE column；
Elution：Under the effect of gravity, with 1mL methanol/acetonitrile (v/v=1:1) it elutes 3 times, merges eluent, the nitrogen at 40 DEG C
Drying is redissolved with the methanol aqueous solution of 1mL 20%, upper machine measurement；
(4) chromatography
Chromatographic column:Accucore RP-MS(Thermo Scientific,100×2.1mm,2.6μm)；Column temperature：40℃；Flowing
Phase A：0.1% formic acid-aqueous solution；Mobile phase B：0.1% formic acid-methanol solution；Flow velocity:0.3mL/min；Sample volume:10μL；
Separate gradient：5%B (0min) -5%B (2min) -30%B (7min) -90%B (11min) -90%B (13min) -5%B
(16min)；
(5) mass spectral analysis
Scan pattern：Positive ion mode；Capillary temperature：320℃；Heating temperature：320℃；Sheath gas：N2Flow velocity 40arb；Auxiliary
Gas：N2Flow velocity 10arb；Spray voltage is (Spray Voltage)：3200V；Lens voltage：50V；Scan pattern is Full
MS/dd-MS2, first mass spectrometric (MS) parameter setting：The resolution ratio R=70,000, AGC target of full scan:1×106, maximum
Residence time (Maximum IT)：100ms, scanning range m/z 100~1000；Second order ms (MS/MS) parameter setting：It differentiates
Rate R=17,500, AGC target：2×105, maximum residence time (Maximum IT)：50ms；
(6) screening database is established
The database of 112 kinds of PPCPs is established based on retention time, parent ion and daughter ion accurate molecular weight；To 112 kinds of PPCPs
Compound uses Full MS/dd-MS2Mode is analyzed, and it is accurate to obtain the retention time of object, parent ion, fragment ion
Then the information such as mass number and ionized form carry out simulation fragmentation, Jiang Gehua to 112 kinds of compounds using Xcalibur software
It closes practical fragment ion masses number and theoretical accurate mass number deviation in object second order ms figure and is less than 5ppm, and abundance is strong at first five
Ion as fragments characteristic ion, finally by 112 kinds of PPCPs Compound Retention times, parent ion theory accurate mass number and
The theoretical accurate mass number of feature secondary fragment ions, establishes screening database；
(7) data processing
Qualitatively screening analysis for PPCPs in water sample, the redissolution sample after acidic extraction and alkalinity are extracted respectively take 0.4mL,
Upper machine testing analysis after mixing, if desired does quantitative analysis, and the chemical characteristic of reference compound carries out corresponding acid or alkali
Property extract sample treatment, then individually sample introduction is analyzed.Quantitative analysis for PPCPs in water sample, is based primarily upon target analytes
Level-one parent ion peak area, quantified using external standard method, and analyzed using 3.3 software of Trace Finder.
2. PPCPs class dirt rapid detection method in a kind of Drinking Water according to claim 1, which is characterized in that
In described (1) step, the Test database of 112 kinds of PPCPs compounds is established, wherein 112 kinds of PPCPs pollutants are specifically shown in Table 1：
1 112 kinds of PPCPs organic pollutants of table and extracting mode
。
3. PPCPs class dirt rapid detection method in a kind of Drinking Water according to claim 1, which is characterized in that
In described (2) step：If desired do qualitative and do quantitative analysis simultaneously, the chemical characteristic of reference compound carry out it is corresponding acid or
Alkalinity extracts sample treatment, and then individually sample introduction is analyzed；Water sample pre-treatment is divided into 2 groups, and one group is to extract under acid condition,
Another group, to extract under alkaline condition, is finally gone up machine testing respectively；If only doing qualitatively screening analysis：Acidic extraction and alkalinity are mentioned
Upper machine testing after redissolution sample mixing after taking.
4. PPCPs class dirt rapid detection method in a kind of Drinking Water according to claim 2, which is characterized in that
In described (2) step, sample extraction, the PPCPs compound extracted respectively by 1 acidic extraction of table or alkalinity.
5. PPCPs class dirt rapid detection method in a kind of Drinking Water according to claim 1, which is characterized in that
In described (3) step, if experiment purpose is screening pollutant, soda acid is extracted and redissolves liquid etc. than mixing LC-MS/MS analysis；
If experiment purpose is certain quantitative pollutant, soda acid is extracted redissolve liquid progress respectively.
6. PPCPs class dirt rapid detection method in a kind of Drinking Water according to claim 1, which is characterized in that institute
The database for establishing 112 kinds of PPCPs in (6) step based on retention time, parent ion and daughter ion accurate molecular weight is stated, is shown in Table 2：
2 112 kinds of PPCPs screening databases of table
。
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| CN115128180A (en) * | 2022-05-31 | 2022-09-30 | 江苏康达检测技术股份有限公司 | Unified detection method for determining multiple PPCPs in water sample |
| CN115166101A (en) * | 2022-08-04 | 2022-10-11 | 南京理工大学 | Comprehensive screening method for comprehensively identifying new pollutants in water sample |
| CN116026958A (en) * | 2023-01-16 | 2023-04-28 | 南京大学 | High-throughput identification method for medicines and personal care products in blood |
| CN116026958B (en) * | 2023-01-16 | 2023-10-03 | 南京大学 | High-throughput identification method for medicines and personal care products in blood |
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