CN108254481B - Method for rapidly detecting multi-class medicines, personal care products and pesticides in water - Google Patents
Method for rapidly detecting multi-class medicines, personal care products and pesticides in water Download PDFInfo
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Abstract
The invention provides a method for rapidly detecting various medicines, personal care products and pesticides in water, which comprises the following steps: taking a water sample to be detected, and pretreating the water sample to be detected to obtain a sample to be detected; the method comprises the following steps of (1) carrying out liquid chromatography-tandem mass spectrometry detection on a sample to be detected by adopting one or more groups of the following five detection conditions respectively, and realizing qualitative analysis and quantitative detection on various drugs, personal care products and pesticides in the water sample to be detected: (a) the mobile phase is formic acid-ammonium formate aqueous solution and acetonitrile, and the ionization mode is electrospray ionization positive mode; (b) the mobile phase is formic acid aqueous solution and acetonitrile, and the ionization mode is electrospray ionization positive mode; (c) the mobile phase is acetic acid-ammonium acetate water solution and acetonitrile, and the ionization mode is an electrospray ionization negative mode; (d) the mobile phase is water and acetonitrile, and the ionization mode is an electrospray ionization negative mode; (e) the mobile phase is formic acid-ammonium formate aqueous solution and acetonitrile, and the ionization mode is electrospray ionization positive mode.
Description
Technical Field
The invention relates to the technical field of environmental monitoring, in particular to a method for rapidly detecting various medicines, personal care products and pesticides in water.
Background
Drugs and personal care products (PPCPs) include various prescription and over-the-counter drugs (e.g., antibiotics, anti-inflammatory drugs, sedatives, lipid-regulating drugs, antiepileptics, etc.) and personal care products (e.g., synthetic perfumes, developers, sunscreens, mosquito repellents, and sanitizers in cosmetics), which are classified into various classes by chemical class, including sulfonamides, quinolones, tetracyclines, macrolides, and hormones. As an emerging pollutant, PPCPs have proved to have potential harm to human health and ecological environment, and at present, PPCPs have become a research hotspot in the field of water environment.
Agricultural chemicals are used as one of important materials for agricultural production activities, and are mainly used for controlling plant diseases and insect pests to ensure grain yield, and they are classified into insecticides, fungicides, herbicides, and the like according to their uses, and into various categories such as organic phosphorus, organic chlorine, carbamates, triazines, azoles, and the like according to their chemical structures. With the continuous use of large quantities of pesticides and even abuse, the problem of pesticide contamination in water has become a global problem of contamination.
The PPCPs and pesticides in water generally cannot be directly analyzed by an analyzer due to limited minimum detection capability of the analyzer and impurity interference of a water environment sample, and are concentrated and extracted to a concentration level which can be measured by the analyzer after certain pretreatment.
In summary, the existing analysis methods for PPCPs and pesticides in water have the defects of single detection type, long analysis time consumption, high analysis cost and the like. In view of the reasons that PPCPs and pesticides in water are various and potential harm to ecological environment and human health is not negligible, the establishment of the method capable of rapidly detecting the PPCPs and the pesticide pollutants in the water has important practical significance.
Disclosure of Invention
In view of this, the present invention provides a method for rapidly detecting multiple classes of drugs, personal care products and pesticides in water. The method can realize the simultaneous detection of more than 100 PPCPs and pesticides, and has the advantages of high detection speed and accuracy.
The invention provides a method for rapidly detecting various medicines, personal care products and pesticides in water, which comprises the following steps:
(1) taking a water sample to be detected, and carrying out pretreatment on the water sample to be detected to obtain a sample to be detected;
(2) and performing liquid chromatography-tandem mass spectrometry detection on the sample to be detected by adopting one or more groups of the following five detection conditions respectively to realize qualitative analysis and quantitative detection on various drugs, personal care products and pesticides in the water sample to be detected:
(a) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: formic acid-ammonium formate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization positive mode;
(b) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: aqueous formic acid, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization positive mode;
(c) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: acetic acid-ammonium acetate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization negative mode;
(d) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: water, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization negative mode;
(e) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: formic acid-ammonium formate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is electrospray ionization positive mode.
Optionally, the mobile phase gradient elution procedure in the (a) detection condition is:
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；
the mobile phase gradient elution procedure in the detection condition (b) is as follows:
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；
the mobile phase gradient elution procedure in the detection condition (c) is as follows:
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；
the mobile phase gradient elution procedure in the detection condition (d) is as follows:
0min：60％A，40％B；4.0min：50％A，50％B；4.5min：0％A，100％B；4.6min-8min：60％A，40％B；
the mobile phase gradient elution procedure in the detection condition (e) is as follows:
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 the detecting conditions (a) - (e), the flow rate of the mobile phase is 0.2m L/min-0.25 m L/min.
Alternatively, in the (a) and the (e), the formic acid-ammonium formate aqueous solution is obtained by mixing formic acid and an ammonium formate aqueous solution, the concentration of the ammonium formate in the ammonium formate aqueous solution is 4 mmol/L-6 mmol/L, the volume fraction of the formic acid in the formic acid-ammonium formate aqueous solution is 0.04% -0.06%, in the (b), the volume fraction of the formic acid in the formic acid aqueous solution is 0.1% -0.2%, in the (c), the acetic acid-ammonium acetate aqueous solution is obtained by mixing acetic acid and an ammonium acetate aqueous solution, the concentration of the ammonium acetate in the ammonium acetate aqueous solution is 4-6 mmol/L, and the volume fraction of the acetic acid in the acetic acid-ammonium acetate aqueous solution is 0.04% -0.06%.
Optionally, the sample to be detected is loaded into the chromatographic column in an amount of 10. mu. L-15. mu. L.
Optionally, the scanning mode of the mass spectrum is a multi-reaction monitoring mode, the detector is a triple quadrupole rod, the mass spectrum conditions of the electrospray ionization positive mode are that the ion source temperature is 120-150 ℃, the taper hole voltage is 10V-60V, the capillary voltage is 3.5KV-4.0KV, the desolvation gas temperature is 380-400 ℃, the desolvation gas flow rate is 600L/h-700L/h, the taper hole gas flow rate is 50L/h-60L/h, and the collision energy is 5V-40V, the mass spectrum conditions of the electrospray ionization negative mode are that the ion source temperature is 120-150 ℃, the taper hole voltage is 10V-60V, the capillary voltage is 3.0KV-3.5KV, the desolvation gas temperature is 380-420 ℃, the desolvation gas flow rate is 600L/h-700L/h, the taper hole gas flow rate is 50L/h-60L/h, and the collision energy is 5V-40V.
Alternatively, the substance detectable by said detection condition (a) includes norfloxacin, enoxacin, ofloxacin, ciprofloxacin, pefloxacin, fleroxacin, lomefloxacin, danofloxacin, enrofloxacin, cinoxacin, sarafloxacin, sparfloxacin, difloxacin, moxifloxacin, oxolinic acid, sulfaquinoxaline, nalidixic acid, flumequine, sulfamethoxydiazine, sulfanilamide, sulfaguanidine, sulfacetamide, sulfamoisopyrimidine, sulfadiazine, cefradine, lincomycin, sulfapyridine, sulfathiazole, trimethoprim, sulfamethoxazole, olprine, sulfamethoxazole, sulfamethazine, sulfamonomethoxazole, sulfamethazine, sulfamonomethoxazole, sulfamethoxydiazine, sulfadimidine, sulfadimethoxine, sulfaphenacetin, clarithromycin, roxithromycin, trenbolone, noberone, 19-norgestrel, testosterone, 24-norgestrel, metoprolol, megestrol, norgestrel, megestrol, norgestrel, doxine, doxolol, meglumine, doxine, doxolol, meglumine, doxolol, doxolo;
substances detectable by the detection condition (b) include 4-anhydrotetracycline epimer, anhydrotetracycline epimer α -apolipoprotein-oxytetracycline, β -apolipoprotein-oxytetracycline, epimecycline, tetracycline, doxycycline, minocycline, epimeromycin, oxytetracycline, epimeanhydroaurycin, demeclocycline, epimeromycin, chlortetracycline, amoxicillin, metronidazole, and dimetridazole;
substances detectable by the detection condition (c) include benzenesulfonamide, chloramphenicol, prednisone, prednisolone, cortisone, hydrocortisone, naproxen, ketoprofen, 6 α -methylprednisolone, fluoromethalone, dexamethasone, beclomethasone, flumethasone, hydrocortisone acetate, budesonide, triamcinolone acetonide, fluocinolone acetonide, ibuprofen, gemfibrozil, triclosan, triclocarban, and clobetasol propionate;
substances detectable by the detecting condition (d) include triamcinolone, estriol, aldosterone, bisphenol a, 17 α -estradiol, 17 α -ethinylestradiol, estrone, diethylstilbestrol, estradiol and hexadienestrol;
substances detectable by the detection condition (e) include methamidophos, atrazine isopropyl, acephate, aldicarb sulfoxide, omethoate, pymetrozine, monocrotophos, asulam, oxydisup, acetamiprid, dimethoate, imidacloprid, trichlorfon, triazophos, fenamiphos, isoprocarb, terbuthylazine, dichlorvos, anilinophos, thiodicarb, dichlorvos, fenobucarb, prometryn, terbuthylazine, acetochlor, tebuconazole, terbufos sulfone, malathion, tebufenozide, terbufos, diazinon, butachlor, anilofos, profenofos and bentazon.
Optionally, the pretreatment operation of the water sample to be detected includes: taking a water sample to be detected, filtering, adding a complexing agent, uniformly mixing, adjusting the pH value of the water sample to be 6.0-7.0 to obtain a first sample to be detected, performing solid-phase extraction on the first sample to be detected, eluting after extraction, collecting eluent to obtain an extracting solution containing various types of medicines, personal care products and pesticides, and concentrating to obtain the sample to be detected.
Optionally, the extraction column used in the solid-phase extraction includes a weak anion exchange solid-phase extraction column, a hydrophilic lipophilic balance solid-phase extraction column and an activated carbon solid-phase extraction column which are sequentially connected in series in an upper-middle-lower order, and the first sample to be tested sequentially flows through the weak anion exchange solid-phase extraction column, the hydrophilic lipophilic balance solid-phase extraction column and the activated carbon solid-phase extraction column.
Optionally, the weak anion exchange solid phase extraction column comprises a WAX column, the hydrophilic lipophilic balance solid phase extraction column comprises a H L B column, and the activated carbon solid phase extraction column comprises an AC2 column.
Optionally, after extraction, splitting the weak anion exchange solid-phase extraction column, the hydrophilic lipophilic balance solid-phase extraction column and the activated carbon solid-phase extraction column which are connected in series, and eluting the weak anion exchange solid-phase extraction column, the hydrophilic lipophilic balance solid-phase extraction column and the activated carbon solid-phase extraction column respectively; the weak anion exchange solid-phase extraction column is eluted by formic acid-methanol solution and methyl tert-butyl ether-methanol solution in sequence, the hydrophilic and lipophilic balance solid-phase extraction column is eluted by formic acid-methanol solution, and the active carbon solid-phase extraction column is eluted by ammonium acetate-methanol solution.
Optionally, the volume percentage of formic acid in the formic acid-methanol solution is 2% to 5%, the volume ratio of methyl tert-butyl ether to methanol in the methyl tert-butyl ether-methanol solution is 9:1, and the concentration of ammonium acetate in the ammonium acetate-methanol solution is 20 mmol/L to 40 mmol/L.
Optionally, the flow rate of the first sample to be tested in the weak anion exchange solid phase extraction column, the hydrophilic lipophilic balance solid phase extraction column and the activated carbon solid phase extraction column is from 5m L/min to 10m L/min.
Optionally, the elution rate of each eluent in the weak anion exchange solid phase extraction column, the hydrophilic lipophilic balance solid phase extraction column and the activated carbon solid phase extraction column is 1m L/min-2 m L/min.
Optionally, the complexing agent includes ethylenediaminetetraacetic acid or disodium ethylenediaminetetraacetate, and the addition amount of the complexing agent is 0.2g to 0.5g of complexing agent added to each liter of the water sample to be detected.
The method adopts the liquid chromatography-tandem mass spectrometry to carry out qualitative and quantitative analysis on the multi-class medicines, personal care products and pesticides in the water sample, qualitatively screens the PPCPs and pesticide pollutants possibly existing in the sample by using a retention time locking and characteristic ion pair locking mode, effectively eliminates false positives, and has accurate detection result.
Drawings
FIG. 1 is a graph showing the results of normalized recovery of representative PPCPs and pesticide contaminants from various types of water (ultrapure water, tap water, and surface water) in example 1;
FIG. 2 is a total ion current chromatogram of 35 pesticides and their internal standards in the water sample to be tested in example 1;
FIG. 3 is a selective ion chromatogram of sulfadiazine of example 1;
FIG. 4 is a selective ion chromatogram of ciprofloxacin in example 1;
FIG. 5 is a selective ion chromatogram of testosterone in example 1;
FIG. 6 is a selective ion chromatogram of progesterone from example 1;
FIG. 7 is a selective ion chromatogram of atenolol in example 1;
FIG. 8 is a selective ion chromatogram of the tetracyclines (4-anhydro-4-differentially and anhydro-tetracycline) of example 1;
FIG. 9 is a selective ion chromatogram of metronidazole in example 1;
FIG. 10 is a selective ion chromatogram of prednisone in example 1;
FIG. 11 is a selective ion chromatogram of gemfibrozil in example 1;
FIG. 12 is a selective ion chromatogram of estriol in example 1;
FIG. 13 is a selective ion chromatogram of methamidophos in example 1.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
The embodiment of the invention provides a method for quickly extracting and detecting multi-class medicines, personal care products and pesticides in water, which comprises the following steps:
(1) taking a water sample to be detected, and carrying out pretreatment on the water sample to be detected to obtain a sample to be detected;
(2) and performing liquid chromatography-tandem mass spectrometry detection on the sample to be detected by adopting one or more groups of the following five detection conditions respectively to realize qualitative analysis and quantitative detection on various drugs, personal care products and pesticides in the water sample to be detected:
(a) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: formic acid-ammonium formate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization positive mode;
(b) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: aqueous formic acid, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: ionization mode is electrospray ionization positive mode (ESI +);
(c) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: acetic acid-ammonium acetate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization negative mode (ESI-);
(d) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: water, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization negative mode;
(e) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: formic acid-ammonium formate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is electrospray ionization positive mode.
In an embodiment of the present invention, the pretreatment operation of the water sample to be tested includes: taking a water sample to be detected, filtering, adding a complexing agent, uniformly mixing, adjusting the pH value of the water sample to be 6.0-7.0 to obtain a first sample to be detected, performing solid-phase extraction on the first sample to be detected, eluting after extraction, collecting eluent to obtain an extracting solution containing various types of medicines, personal care products and pesticides, and concentrating to obtain the sample to be detected. Wherein, the filtration operation can adopt a glass fiber filter membrane for filtration. Specifically, the pore size of the glass fiber filter membrane can be 0.2 μm to 0.7. mu.m. Optionally, the glass fiber filter membrane is dried at 450 ℃ for 6 hours before filtration.
In an embodiment of the invention, the complexing agent optionally comprises ethylenediaminetetraacetic acid or disodium ethylenediaminetetraacetate (Na)2EDTA), the addition amount of the complexing agent is 0.2g-0.5g of the complexing agent added into each liter of water sample to be detected. The invention utilizes the complexing agent to complex Ca in water2+And Mg2+And the metal ions and the trace heavy metal ions are contained, so that the complexation of macrolide antibiotics and tetracycline antibiotics with the metal ions is inhibited, and PPCPs pollutants are not interfered during the subsequent water sample enrichment.
In the embodiment of the invention, ammonia water or formic acid can be used for adjusting the pH value of the water sample, and the pH value of the water sample can be specifically adjusted to 6.0-6.2.
In an embodiment of the invention, an extraction column adopted by solid-phase extraction comprises a weak anion exchange solid-phase extraction column, a hydrophilic lipophilic balance solid-phase extraction column and an activated carbon solid-phase extraction column which are sequentially connected in series according to an upper order, a middle order and a lower order, and a first sample to be detected sequentially flows through the weak anion exchange solid-phase extraction column, the hydrophilic lipophilic balance solid-phase extraction column and the activated carbon solid-phase extraction column.
The weak anion exchange solid-phase extraction column has strong adsorption capacity on strong-acid compounds, the hydrophilic and lipophilic balance solid-phase extraction column has hydrophilic and lipophilic properties, and has good adsorption capacity on polar, medium-polar and hydrophobic compounds; the active carbon solid phase extraction column has strong adsorption capacity on strong polar organic matters (such as methamidophos and acephate) in water. The method is a high-flux extraction method, and water sample enrichment is performed by adopting a mode of connecting a weak anion exchange solid-phase extraction column, a hydrophilic lipophilic balance solid-phase extraction column and an activated carbon solid-phase extraction column in series, so that the PPCPs and pesticide pollutants with different physicochemical properties can be extracted from a water sample at the same time to the greatest extent.
The method comprises the following steps of activating an extraction column used for solid phase extraction by sequentially using methanol and ultrapure water before extraction, specifically, activating the extraction column used for solid phase extraction by sequentially using 6-10m L methanol and 6-10m L ultrapure water, and keeping the extraction column wet in the activation process.
In an embodiment of the invention, optionally, the flow rate of the first sample to be tested in the weak anion exchange solid phase extraction column, the hydrophilic lipophilic balance solid phase extraction column and the activated carbon solid phase extraction column is from 5m L/min to 10m L/min.
In the embodiment of the invention, after extraction, the sample bottle and the extraction column adopted by solid phase extraction are washed by a small amount of ultrapure water, residual water in the extraction column is pumped as much as possible, and then elution is carried out.
In the embodiment of the invention, after extraction, a weak anion exchange solid-phase extraction column, a hydrophilic lipophilic balance solid-phase extraction column and an activated carbon solid-phase extraction column which are connected in series are split, and the weak anion exchange solid-phase extraction column, the hydrophilic lipophilic balance solid-phase extraction column and the activated carbon solid-phase extraction column are respectively eluted, wherein the weak anion exchange solid-phase extraction column is sequentially eluted by a formic acid-methanol solution and a methyl tert-butyl ether-methanol solution, the hydrophilic lipophilic balance solid-phase extraction column is eluted by a formic acid-methanol solution, and the activated carbon solid-phase extraction column is eluted by an ammonium acetate-methanol solution.
The invention ensures that the pollutants are completely eluted and the impurities are kept on the extraction column as much as possible by optimizing the combination conditions of the elution solvent, thereby achieving the effect of further purifying the sample.
In the embodiment of the invention, the extracting solution is concentrated, when the volume of the extracting solution is concentrated to about 0.15m L, the volume of the extracting solution is determined to 1m L by using a volume determining solvent, the extracting solution is uniformly mixed and passes through a membrane, and the membrane can be directly measured or diluted to be measured.
In the embodiment of the invention, the constant volume solvent is formic acid-acetonitrile aqueous solution, wherein the formic acid-acetonitrile aqueous solution is obtained by mixing formic acid and acetonitrile aqueous solution, the volume ratio of acetonitrile to water in the acetonitrile aqueous solution is 5:95, and the volume percentage of formic acid in the formic acid-acetonitrile aqueous solution is 1%. Optionally, the membrane of the sample after the volume fixing is GHP Syring Filter (0.2 μm,13 mm); the sample after being filtered can be selectively diluted by 10 to 100 times according to the type of the water sample.
The invention can realize the simultaneous extraction of various medicines, personal care products and pesticides in water through the pretreatment operation, and can avoid the subsequent influence of metal ions on enrichment and detection through the complexing of the complexing agent; the method can maximally enrich the multi-class medicines, personal care products and pesticides in water by connecting the three extraction columns in series, and is favorable for subsequent detection.
In an embodiment of the present invention, the mobile phase gradient elution procedure in the detection condition (a) is as follows:
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；
the mobile phase gradient elution procedure in the detection condition (b) is as follows:
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；
the mobile phase gradient elution procedure in the detection condition (c) is as follows:
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；
the mobile phase gradient elution procedure in the detection condition (d) is as follows:
0min：60％A，40％B；4.0min：50％A，50％B；4.5min：0％A，100％B；4.6min-8min：60％A，40％B；
the mobile phase gradient elution procedure in the detection condition (e) is as follows:
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 the embodiment of the present invention, one or more groups of five groups of detection conditions may be respectively adopted to perform liquid chromatography-tandem mass spectrometry detection according to the condition of the sample to be detected and the condition of the substance to be detected, for example, five groups of detection conditions may be adopted to perform detection or only one group of detection conditions may be adopted to perform detection. Alternatively, after each set of measurements is completed, the column is rinsed with acetonitrile and ultrapure water in a volume ratio of 50:50 for at least 10 minutes, then with acetonitrile for at least 10 minutes, and then subjected to the next set of measurements.
Optionally, the total run time of the chromatography column in the (a) - (e) detection conditions is 19min, 10min, 9min, 8min and 16min in sequence.
Optionally, the flow rate of the mobile phase in the (a) - (e) assay conditions is from 0.20m L/min to 0.25m L/min, further optionally, the flow rate of the mobile phase in the (a) - (e) assay conditions is, in order, 0.20m L/min, 0.25m L/min, 0.25m L/min, 0.25m L/min, and 0.20m L/min.
Optionally, in (a) and (e), the formic acid-ammonium formate aqueous solution is obtained by mixing formic acid and ammonium formate aqueous solution, the concentration of ammonium formate in the ammonium formate aqueous solution is 4-6 mmol/L, the volume fraction of formic acid in the formic acid-ammonium formate aqueous solution is 0.04% -0.06%, in (b), the volume fraction of formic acid in the formic acid aqueous solution is 0.1% -0.2%, in (c), the acetic acid-ammonium acetate aqueous solution is obtained by mixing acetic acid and ammonium acetate aqueous solution, the concentration of ammonium acetate in the ammonium acetate aqueous solution is 4-6 mmol/L, the volume fraction of acetic acid in the acetic acid-ammonium acetate aqueous solution is 0.04% -0.06%, further preferably, the concentration of ammonium formate in the ammonium formate aqueous solution is 4 mmol/L, the volume fraction of formic acid in the formic acid-ammonium formate aqueous solution is 0.04%, the volume fraction of formic acid in the formic acid aqueous solution is 0.1%, the concentration of ammonium acetate-ammonium acetate aqueous solution is 4 mmol/L, the concentration of ammonium acetate in the ammonium acetate aqueous solution is L%, and the volume fraction of ammonium acetate in the aqueous solution is 0.04% -L%.
In the embodiment of the invention, the sample to be detected is fed into the chromatographic column in an amount of 10-15 mu L. in the specific embodiment, the sample to be detected is fed into the chromatographic column in an amount consistent with that of the standard solution. further preferably, the sample to be detected is fed into the chromatographic column in an amount of 10 mu L.
In the embodiment of the invention, the scanning mode of the mass spectrum is a multi-reaction monitoring mode, the detector is a triple quadrupole rod, the mass spectrum conditions of the electrospray ionization positive mode are that the ion source temperature is 120-150 ℃, the taper hole voltage is 10V-60V, the capillary voltage is 3.5KV-4.0KV, the desolvation gas temperature is 380-400 ℃, the desolvation gas flow rate is 600L/h-700L/h, the taper hole gas flow rate is 50L/h-60L/h, the collision energy is 5V-40V, the mass spectrum conditions of the electrospray ionization negative mode are that the ion source temperature is 120-150 ℃, the taper hole voltage is 10V-60V, the capillary voltage is 3.0KV-3.5KV, the desolvation gas temperature is 380-420 ℃, the desolvation gas flow rate is 600L/h-700/h, the taper hole flow rate is 50L/h-60/h, the collision energy is 5V-40V, the ion desorption gas flow rate is 600V-L/h, the taper hole energy is 50V-60V, the electrospray ionization temperature is 10V-60 h, the capillary collision energy is 10V, the electrospray ionization voltage is 10V-3.5 h, the capillary collision energy is 10V-10V, the electrospray ionization collision energy is 10V-60V, the ion source temperature is 10-10V, the capillary tube collision energy is 10V, the electrospray ionization temperature is 10V-60V-10V, the capillary tube collision energy is 10V-10V, the capillary tube collision energy is preferably, the electrospray ionization temperature is 10V collision energy.
In the embodiment of the invention, the quantification is carried out by an internal standard method. Further optionally, quantitative internal standards of the multi-class medicines, the personal care products and the pesticides are added into the sample to be detected, so that the relative quantification of the multi-class medicines, the personal care products and the pesticides detected in the water sample to be detected is carried out; specifically, optionally, the quantitative internal standards comprise 5 PPCPs quantitative internal standards and 1 pesticide quantitative internal standard, and the 5 PPCPs quantitative internal standards are sulfamethoxazole respectively13C6, medroxyprogesterone d3, salbutamol d9, gemfibrozil d6 and diethylstilbestrol d4, the 5 PPCPs internal standards are prepared into a mixed standard, sulfamethoxazole13The concentrations of C6, medroxyprogesterone d3, salbutamol d9, gemfibrozil d6 and diethylstilbestrol d4 are 1ppm, 1ppm, 1ppm, 10ppm and 10ppm in sequence, the mixed standard addition amount is 10 mu L, and the 1 pesticide quantitative internal standard is thiabendazole d6, the concentration is 1ppm, and the addition amount is 10 mu L.
The invention relatively quantifies the multi-class drugs, personal care products and pesticides detected in a water sample to be detected, and each class of compounds is relatively quantified corresponding to the internal standard thereof by adopting a peak area ratio method. The method uses an internal standard method for quantification, and can accurately obtain the contents of the PPCPs and the pesticides in the water sample to be detected.
Examples of the present invention substances detectable by the detection conditions (a) to (e) include the compounds shown in table 1 below.
The method provided by the invention can detect at least 130 PPCPs and 35 pesticides in water.
In the embodiment of the invention, an electrospray ionization source and a multi-reaction monitoring (MRM) mode are adopted to detect a target object in a sample, the target object is introduced into a collision chamber to collide with inert gas molecules to crack the inert gas molecules by setting different taper hole voltages and collision energy, and then the generated fragment ions, namely the daughter ions, are scanned and detected to obtain related structural information. And performing qualitative analysis by using all the acquired characteristic ions and the abundance ratio among the ions, and performing quantitative analysis by using the relation between the response and the concentration of the characteristic ions with the highest abundance. The multiple reaction monitoring ion pairs and mass spectrum related parameters for each compound are shown in table 1.
TABLE 1 Multi-reaction monitoring ion-pair and mass spectrum related parameter table for each compound
Remarking: the daughter ion 1 is a quantitative ion, and the daughter ion 2 is a qualitative ion; -indicating not detected;
when the pesticide is detected under the detection condition (e), the set mass spectrum condition is that the ionization mode is an electrospray ionization positive mode, but when a subsequent instrument actually detects the pesticide, according to the property of the bentazone, the ionization mode is converted into an electrospray ionization negative mode for ionization when the retention time of the bentazone is close to the retention time of the bentazone, so that the mass spectrum information of the bentazone is obtained, and when other pesticide compounds are detected subsequently, the ionization positive mode is converted into the electrospray ionization mode. Namely, under the detection condition (e), except for bentazone, the electrospray ionization negative mode is adopted, and the other pesticide compounds are in the electrospray ionization positive mode.
The invention can carry out qualitative and quantitative analysis on various types of medicines, personal care products and pesticides in a water sample by adopting the detection condition of liquid chromatography-tandem mass spectrometry, qualitatively screens PPCPs and pesticide pollutants possibly existing in the sample by using a retention time locking and characteristic ion pair locking mode, effectively eliminates false positives, and has accurate detection result.
The method for rapidly detecting the multi-class medicines, the personal care products and the pesticides in the water is accurate and rapid, can simultaneously detect various pollutants, and provides a method for rapidly screening and quantitatively evaluating the pollution conditions and risks of the PPCPs and the pesticides in various water bodies; the method provided by the invention has potential application value in the aspects of screening and preliminary investigation of a large amount of water samples.
Example 1:
a method for rapidly detecting multiple classes of drugs, personal care products and pesticides in water, comprising:
(1) sample pretreatment:
this example selects different classes of representative PPCPs and pesticide-based contaminants and performs a spiking recovery experiment using ultrapure water from Millipore ultrapure water machine, usa to determine the choice of elution solvent.
Adding standard water sample, weighing 500m L ultrapure water, adding 5m L20 g/L of Na into the water sample2EDTA aqueous solution, after mixing evenly, using a proper amount of ammonia water to adjust the pH value of the water sample to 6.00-6.20, then adding 100 mu L PPCPs mixed standard (1 mu g/m L) and 50 mu L pesticide mixed standard (2 mu g/m L), wherein the concentration level of each monomer pollutant (PPCPs or pesticide) in the ultrapure water sample after adding the standard is 0.2 mu g/L, and after fully mixing evenly, using the ultrapure water for standby without adding the mixed standard;
and (3) activating the solid phase extraction column, namely activating the solid phase extraction column by using Oasis WAX Cartridge (150mg,6m L), Oasis H L BCartridge (500mg,6m L) and Sep-Pak AC2Plus Short Cartridge (400mg,85 mu m) in sequence and 6-10m L methanol and 6-10m L ultrapure water, wherein the extraction column needs to be kept wet in the activation process, closing the solid phase extraction device when the surface of the ultrapure water in the extraction column is about 1mm away from the upper-layer sieve plate, and filling the solid phase extraction column with the ultrapure water for later use.
And (3) adding a standard water sample for extraction and enrichment, namely connecting the activated solid phase extraction column in series according to the sequence of WAX column (upper), H L B column (middle) and AC2 (lower), then connecting the standard water sample with the WAX column through a large-volume sampling tube, opening a solid phase extraction device for enriching the standard water sample, wherein the enrichment speed is 5-10m L/min, flushing a sample bottle and the solid phase extraction small column by using a small amount of ultrapure water (about 6-10m L) after the enrichment is finished, and draining residual water in the small column as much as possible.
Elution solvent is one of the important reasons for affecting the recovery of compounds in water, and in the case of fixed other extraction conditions, the solid phase extraction column was eluted with different combinations of organic solvents, in this example the organic solvents used for the experiments included formic acid-methanol solution with a formic acid volume fraction of 2%, methyl tert-butyl ether-methanol solution (methyl tert-butyl ether and methanol in a volume ratio of 9:1), dichloromethane-methanol solution (dichloromethane and methanol in a volume ratio of 8:2), aqueous ammonia-methanol solution with an aqueous ammonia volume fraction of 5%, and ammonium acetate-methanol solution with a concentration of 20 mmol/L ammonium acetate. WAX column and H L B column were successively used formic acid-methanol solution with a formic acid volume fraction of 2% (WAX 1 and H L B1 in Table 2), methyl tert-butyl ether-methanol solution (volume ratio of 9:1) (WAX 2 and H L B2 in Table 2), dichloromethane-methanol solution (volume ratio of 8:2) (WAX 3 and H L B3 in Table 2) and aqueous ammonia water solution of 5965) (WAX 368 and ammonium acetate-methanol-2 (WAX 3 and ammonium acetate-3 in a concentration of 20 and ammonium acetate-methanol-ethanol-methanol-3 in a concentration (WAX 2 in a volume fraction of 2 and a concentration of L in each of 2 and a concentration of a single elution in a single elution of a single elution solvent (WAX-butanol-.
Concentrating the collected eluates with soft nitrogen gas in 40 deg.C water bath, stopping nitrogen blowing when the volume of the eluate is concentrated to about 0.15m L, adding 1% formic acid-acetonitrile water (acetonitrile/water volume ratio of 5:95) solution to 1m L, transferring the solution to 2m L brown sample bottle, adding PPCPs and agricultural chemicalsThe quantitative internal standard of the pesticide comprises 5 PPCPs quantitative internal standards and 1 pesticide quantitative internal standard, and the 5 PPCPs quantitative internal standards are sulfamethoxazole respectively13C6, medroxyprogesterone d3, salbutamol d9, gemfibrozil d6 and diethylstilbestrol d4, the 5 PPCPs internal standards are prepared into a mixed standard, sulfamethoxazole13The concentrations of C6, medroxyprogesterone d3, salbutamol d9, gemfibrozil d6 and diethylstilbestrol d4 are 1ppm, 1ppm, 1ppm, 10ppm and 10ppm in sequence, the mixed standard addition amount is 10 mu L, the 1 pesticide quantitative internal standard is thiabendazole d6, the concentration is 1ppm, the addition amount is 10 mu L, and the determination is carried out by a Waters ultra performance liquid chromatography-tandem mass spectrometer (UP L C-MS/MS).
(2) The chromatographic and mass spectrometric conditions were:
the detection is carried out by a Waters ultra-performance liquid chromatography-tandem mass spectrometer (UP L C-MS/MS), the used analytical column is ACQUITY UP L C BEH C18cartridge (2.1 × 100mm,1.7 mu m), the column temperature is room temperature (20 ℃), the sample injection amount is 10 mu L, the ionization mode is ESI + and ESI according to different detection compounds, the detector is a Triple Quadrupole (TQD), PPCPs and pesticide pollutants are respectively detected by liquid chromatography-tandem mass spectrometry according to the types and the ionization modes by adopting the following five groups of detection conditions, and the detection is specifically:
(a) the ionization mode is ESI +, the mobile phase is formic acid-ammonium formate aqueous solution (formic acid volume fraction is 0.04%, ammonium formate concentration in ammonium formate aqueous solution is 4mM) (A) and acetonitrile (B), the mobile phase gradient elution program is 0min-0.5 min: 95% A, 5% B, 3.0 min: 75% A, 25% B, 9.0 min: 65% A, 35% B, 13.5 min: 20% A, 80% B, 14.0 min: 0% A, 100% B, 14.1min-19.0 min: 95% A, 5% B, the flow rate is 0.2m L/min;
(b) the ionization mode is ESI +, the mobile phase is formic acid water solution (A) with 0.1% formic acid volume fraction and acetonitrile (B), the mobile phase 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, the flow rate is 0.25m L/min;
(c) the ionization mode is ESI-, the mobile phase is acetic acid-ammonium acetate aqueous solution (acetic acid volume fraction is 0.04%, concentration of ammonium acetate in ammonium acetate aqueous solution is 4mM) (A) and acetonitrile (B), the mobile phase gradient elution program is 0min-0.5 min: 70% A, 30% B, 4.5 min: 20% A, 80% B, 5.0 min: 0% A, 100% B, 5.1min-9.0 min: 70% A, 30% B, the flow rate is 0.25m L/min;
(d) the ionization mode is ESI-, the mobile phase is water (A) and acetonitrile (B), and the mobile phase gradient elution program is 0 min: 60% A, 40% B, 4.0 min: 50% A, 50% B, 4.5 min: 0% A, 100% B, 4.6min-8 min: 60% A, 40% B, the flow rate is 0.25m L/min;
(e) the ionization mode is ESI +, the mobile phase is formic acid-ammonium formate aqueous solution (formic acid volume fraction is 0.04%, ammonium formate concentration in ammonium formate aqueous solution is 4mM) (A) and acetonitrile (B), and the mobile phase gradient elution program is 0min-0.5 min: 95% A, 5% B, 8.0 min: 40% A, 60% B, 11.0 min: 0% A, 100% B, 11.1min-16.0 min: 95% A, 5% B, and the flow rate is 0.2m L/min.
The mass spectrum conditions of the electrospray ionization positive mode are that the ion source temperature is 120 ℃, the taper hole voltage is 10V-60V, the capillary voltage is 3.5KV, the desolvation gas temperature is 380 ℃, the desolvation gas flow rate is 600L/h, the taper hole gas flow rate is 50L/h, and the collision energy is 5V-40V, the mass spectrum conditions of the electrospray ionization negative mode are that the ion source temperature is 120 ℃, the taper hole voltage is 10V-60V, the capillary voltage is 3.0KV, the desolvation gas temperature is 380 ℃, the desolvation gas flow rate is 600L/h, the taper hole gas flow rate is 50L/h, and the collision energy is 5V-40V, and monitoring ion pairs with each PPCPs and pesticide compounds and related parameters of the mass spectrum are shown in Table 1.
(3) Method verification
1. Linear range and detection limit
The method comprises the steps of preparing PPCPs and pesticide standard products with different concentrations, preparing each concentration of standard product into 1m L, adding the same amount of PPCPs and pesticide quantitative internal standard as the step (1) respectively, mixing uniformly, and then carrying out on-machine detection, processing data measured on the on-machine by using Target L ynx to obtain a corresponding standard curve, wherein a linear regression equation corresponding to the standard curve is Y-aX + b, Y-peak area × (concentration of the quantitative internal standard/peak area of the quantitative internal standard) of an object to be detected, and X-concentration of a compound to be detected, the linear range of each PPCPs and pesticide and subsequent quantification can be judged by the standard curve, and the results show that the method has good linearity, the linear correlation coefficient of most compounds (more than 96 percent) is more than 0.99 in the concentration range of 0.001-200 mu g/L.
2. Recovery test
And (3) quantifying by adopting an internal standard method, simultaneously analyzing a standard sample and a non-standard sample, and comparing the difference value of the concentration measured by the two samples with a known standard adding amount to obtain the standard adding recovery rate of the representative PPCPs and the pesticide in different water bodies. The results are shown in Table 2.
TABLE 2 recovery of representative PPCPs and pesticides in% -under different elution solvent conditions
Note that WAX1 and H L B1 indicate that the elution solvents used were 2% formic acid-methanol solutions, WAX2 and H L B2 indicate that the elution solvents used were methyl tert-butyl ether-methanol solutions, WAX3 and H L B3 indicate that the elution solvents used were dichloromethane-methanol solutions, WAX4 and H L B4 indicate that the elution solvents used were 5% ammonia-methanol solutions, and AC21 and AC22 indicate that the elution solvents used were 20 mmol/L ammonium acetate-methanol solutions and dichloromethane-methanol solutions, respectively, R1 indicates that the WAX column was eluted with the first two elution solvents (2% formic acid-methanol solution and methyl tert-butyl ether-methanol solution), while H L B and AC2 columns were eluted with the first elution solvent only (H L B was 2% formic acid-methanol solution, AC2 column was ammonium acetate-methanol solution), R2 indicates that the WAX column was eluted with four elution solvents, and AC L was eluted with four elution solvents.
The results show that when the WAX column adopts the first 2 elution solvents (formic acid-methanol solution and methyl tert-butyl ether-methanol solution) and the H L B column and the AC2 column only adopt the 1 st elution solvent (formic acid-methanol solution and ammonium acetate-methanol solution respectively) for elution, satisfactory recovery rates (except that the recovery rate of sulfamethazine is 45.6 percent and the recovery rate of diethyltoluamide is 145.8 percent, the recovery rates of the rest compounds are in the range of 60 to 140 percent) can be obtained, and the screening requirement of high-flux pollutants in the invention can be met.
(4) Determination of actual samples
1. The elution conditions are that WAX column is eluted by formic acid-methanol solution with 2% formic acid volume fraction of 8m L, 8m L methyl tert-butyl ether-methanol solution (volume ratio of methyl tert-butyl ether to methanol is 9:1) and ammonia-methanol solution with 5% ammonia volume fraction of 8m L, H L B column is eluted by formic acid-methanol solution with 2% formic acid volume fraction of 8m L and ammonia-methanol solution with 8m L methyl tert-butyl ether-methanol solution (volume ratio of methyl tert-butyl ether to methanol is 9:1) and ammonia-methanol solution with 5% ammonia volume fraction of 8m 3525, elution is carried out by a mixed elution method of formic acid-methanol solution with 2% formic acid volume fraction and 8m L methyl tert-butyl ether-methanol solution (volume ratio of methyl tert-butyl ether to methanol is 9:1) and elution method of elution by using L m and 358 m L methyl tert-butyl ether-methanol solution with 2% formic acid volume fraction, and elution concentration of two kinds of elution solutions with different concentrations of PPCPCPCPCPS and pesticides are measured by a combined method of adding PPC and concentrating the same volume ratio of PPC 2-20, and concentrating the elution method of PPC, and concentrating the elution method of samples without adding standard water samples to obtain the difference of elution method of elution and concentrating the difference of PPC 2 and the elution method of elution.
In FIG. 1, R1 represents WAX column sequentially eluting with formic acid-methanol solution with a formic acid volume fraction of 2% and 8m L methyl tert-butyl ether-methanol solution (the volume ratio of methyl tert-butyl ether to methanol is 9:1) while H L B column and AC2 column respectively elute PPCPs and a pesticide contaminant recovery rate only with 8m L1 formic acid-methanol solution with a formic acid volume fraction of 2% and 10m L ammonium acetate-methanol solution with a concentration of 20 mmol/L ammonium acetate-methanol solution, R2 represents WAX column sequentially eluting with formic acid-methanol solution with a formic acid volume fraction of 8m L4, 8m L methyl tert-butyl ether-methanol solution (the volume ratio of methyl tert-butyl ether to methanol is 9:1) and 8m L aqueous ammonia-methanol solution with a volume fraction of 5% and H L B column sequentially eluting with formic acid-methanol solution with a formic acid volume fraction of 2% and 8m L methyl tert-methanol solution (the volume ratio of 9:1) and 8m L ammonia-methanol, and a concentration of 5% to 5% aqueous ammonia-methanol, and a concentration of 5% to a concentration of cefaclonidine, a compound represents MCT, a to a compound, a compound represents MCT, a compound represents a compound, a compound represents a compound, a compound represented by 8m 3617, a compound represented by a compound, a compound represented by 8m 3617, a compound by a compound, a compound represented by a compound, a compound represented by a compound, a compound represented by a compound.
The results in fig. 1 show that the elution solvent and the elution mode selected in the embodiment of the invention can achieve better recovery rate for different types of water bodies. Therefore, the method can be suitable for simultaneously detecting multiple classes of PPCPs and pesticide pollutants in different types of water bodies. Therefore, the detection method provided by the embodiment of the invention is proved to be feasible through experimental simulation and actual water sample screening. In the simulation of the standard recovery experiment, the recovery rate of most compounds is in the range of 60-140%, and the result is satisfactory.
2. Detecting PPCPs and pesticide pollutants in an actual surface water sample;
to further verify the feasibility of the method for rapidly detecting multiple classes of drugs, personal care products and pesticides in water provided by the embodiment of the invention, 10 actual surface water samples were collected in the embodiment, each surface water sample was filtered by a 0.7 μm glass fiber filter membrane and then 2L was measured, and 20m L20 g/L of Na was added to the water samples2And (3) uniformly mixing the EDTA aqueous solution, adjusting the pH value of the water sample to 6.00-6.20 by using a proper amount of ammonia water, and fully and uniformly mixing for later use. The steps of enriching, concentrating, detecting on the machine and the like of the water sample are all as described in the above, and all the eluents of 3 solid phase extraction columns of each water sample need to be collected in the same K-D concentrator when the solid phase extraction columns are eluted. The experimental methods used in the above examples are all conventional methods unless otherwise specified. Materials, reagents and the like used in the above examples are commercially available unless otherwise specified.
The results of screening representative PPCPs and pesticide contaminants in actual surface water samples are shown in table 3. Wherein, the total ion flow chromatogram of the 35 pesticide compounds detected under the detection condition (e) is shown in fig. 2.
TABLE 3 screening results for representative PPCPs and pesticide contaminants in actual surface Water samples
Note that the concentration of each compound in the table is ng/L, and nd indicates no detection.
The results in table 3 show that the method provided by the embodiment of the invention can screen and quantitatively analyze PPCPs and pesticide pollutants possibly existing in the surface water sample. Therefore, the method can be used for fast, accurate and high-flux screening and analysis of the multiple classes of PPCPs and pesticide pollutants in the water.
As shown in FIG. 2, the abscissa in FIG. 2 is retention time (min), the ordinate is intensity (%), the numerals in FIG. 2 are 1-methamidophos, 2-deisopropylatrazine, 3-acephate, 4-aldicarb sulfoxide, 5-omethoate, 6-pymetrozine, 7-monocrotophos, 8-asulam, 9-sulforaphane, 10-acetamiprid, 11-dimethoate, 12-imidacloprid I, 13-trichlorfon, 14-aphifos, 15-fenamiphos sulfoxide, 16-isoprocarb, 17-deethylterbuthylazine, 18-dichlorvos, 19-anilinophosulfone, 20-thiodicarb, 21-grass, 22-buticarb, 23-promethazine, 24-terbuthylazine, 25-acetochlor, 26-tebuconazole, 27-terbufos sulfone, 28-malathion, 29-tebufenozide, 30-terbufos, 31-diazinon, 32-butachlor, 33-anilofos, 34-profenofos, 35-bentazone, IS-thiabendazole-d 6; as can be seen from fig. 2, the pesticidal compound was able to be detected well under this condition.
The embodiment of the invention also provides a selective ion chromatogram of a part of compounds, as shown in figures 3-13. Figures 3-13 sequentially represent selective ion chromatograms for sulfadiazine, ciprofloxacin, testosterone, progesterone, atenolol, tetracyclines (retention time RT ═ 6.30 for 4-epimeric anhydrotetracycline, RT ═ 6.67 for anhydrotetracycline), metronidazole, prednisone, gemfibrozil, estriol, and methamidophos; the upper graph in each graph corresponds to the quantitative ions and the lower graph corresponds to the qualitative ions. In FIGS. 3 to 13, the abscissa represents retention time (min) and the ordinate represents intensity (%).
In conclusion, the embodiment of the invention establishes the method for rapidly and effectively analyzing and detecting the multi-class medicines, personal care products and pesticides in water with strong qualitative capability and high sensitivity by optimizing the enrichment and separation conditions of the target substances, the chromatographic conditions and the mass spectrum conditions. The detection sensitivity, the separation degree and the reproducibility of each compound are good, and a method is provided for rapidly screening and quantitatively evaluating the pollution conditions and risks of PPCPs and pesticides in various water bodies.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A method for rapidly detecting multi-class medicines, personal care products and pesticides in water is characterized by comprising the following steps:
taking a water sample to be detected, and carrying out pretreatment on the water sample to be detected to obtain a sample to be detected, wherein the pretreatment operation of the water sample to be detected comprises the following steps: taking a water sample to be detected, filtering, adding a complexing agent, uniformly mixing, adjusting the pH value of the water sample to be 6.0-7.0 to obtain a first sample to be detected, carrying out solid-phase extraction on the first sample to be detected, eluting after extraction, collecting eluent to obtain an extracting solution containing various drugs, personal care products and pesticides, concentrating to obtain the sample to be detected, wherein an extraction column adopted by the solid-phase extraction comprises a weak anion exchange solid-phase extraction column, a hydrophilic lipophilic balance solid-phase extraction column and an active carbon solid-phase extraction column which are sequentially connected in series according to the upper-middle-lower order, and the first sample to be detected sequentially flows through the weak anion exchange solid-phase extraction column, the hydrophilic lipophilic balance solid-phase extraction column and the active carbon solid-phase extraction column; after extraction, splitting a weak anion exchange solid-phase extraction column, a hydrophilic lipophilic balance solid-phase extraction column and an active carbon solid-phase extraction column which are connected in series, and respectively eluting the weak anion exchange solid-phase extraction column, the hydrophilic lipophilic balance solid-phase extraction column and the active carbon solid-phase extraction column; the weak anion exchange solid-phase extraction column is eluted by formic acid-methanol solution and methyl tert-butyl ether-methanol solution in sequence, the hydrophilic and lipophilic balance solid-phase extraction column is eluted by formic acid-methanol solution, and the active carbon solid-phase extraction column is eluted by ammonium acetate-methanol solution;
and performing liquid chromatography-tandem mass spectrometry detection on the sample to be detected by adopting one or more groups of the following five detection conditions respectively to realize qualitative analysis and quantitative detection on various drugs, personal care products and pesticides in the water sample to be detected:
(a) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: formic acid-ammonium formate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization positive mode;
(b) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: aqueous formic acid, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization positive mode;
(c) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: acetic acid-ammonium acetate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization negative mode;
(d) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: water, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization negative mode;
(e) chromatographic conditions are as follows: the chromatographic column is a C18 column, and the mobile phase is: phase A: formic acid-ammonium formate aqueous solution, phase B: acetonitrile, gradient elution is adopted, and the column temperature is room temperature; mass spectrum conditions: the ionization mode is an electrospray ionization positive mode;
substances detectable by the detection condition (a) include norfloxacin, enoxacin, ofloxacin, ciprofloxacin, pefloxacin, fleroxacin, lomefloxacin, danofloxacin, enrofloxacin, cinoxacin, sarafloxacin, sparfloxacin, difloxacin, moxifloxacin, oxolinic acid, sulfaquinoxaline, nalidixic acid, flumequine, sulfamethoxydiazine, sulfaguanidine, sulfacetamide, sulfamethazine, cefradine, lincomycin, sulfapyridine, sulfathiazole, trimethoprim, sulfamethoxazole, olmeproline, sulfamethizole, sulfamethazine, methoxypyrazine, sulfamonomethoxazole, sulfamethazine, sulfamonomethoxazole, sulfamethoxazole, sulfadoxine, sulfamethoxydiazine, sulfamethoxazole, doxine, 19-norgestrel, testosterone, 24-metoprolol, metoclopramide, norgestrel, megestrol, meglumine, doxolol, meglumine, doxine, meglumine, doxolol, meglumine, doxolol α, doxolol, meglumine, doxolol;
substances detectable by the detection condition (b) include 4-anhydrotetracycline epimer, anhydrotetracycline epimer α -apolipoprotein-oxytetracycline, β -apolipoprotein-oxytetracycline, epimecycline, tetracycline, doxycycline, minocycline, epimeromycin, oxytetracycline, epimeanhydroaurycin, demeclocycline, epimeromycin, chlortetracycline, amoxicillin, metronidazole, and dimetridazole;
substances detectable by the detection condition (c) include benzenesulfonamide, chloramphenicol, prednisone, prednisolone, cortisone, hydrocortisone, naproxen, ketoprofen, 6 α -methylprednisolone, fluoromethalone, dexamethasone, beclomethasone, flumethasone, hydrocortisone acetate, budesonide, triamcinolone acetonide, fluocinolone acetonide, ibuprofen, gemfibrozil, triclosan, triclocarban, and clobetasol propionate;
substances detectable by the detecting condition (d) include triamcinolone, estriol, aldosterone, bisphenol a, 17 α -estradiol, 17 α -ethinylestradiol, estrone, diethylstilbestrol, estradiol and hexadienestrol;
substances detectable by the detection condition (e) include methamidophos, atrazine isopropyl, acephate, aldicarb sulfoxide, omethoate, pymetrozine, monocrotophos, asulam, oxydisup, acetamiprid, dimethoate, imidacloprid, trichlorfon, triazophos, fenamiphos, isoprocarb, terbuthylazine, dichlorvos, anilinophos, thiodicarb, dichlorvos, fenobucarb, prometryn, terbuthylazine, acetochlor, tebuconazole, terbufos sulfone, malathion, tebufenozide, terbufos, diazinon, butachlor, anilofos, profenofos and bentazon.
2. The method for rapid detection of multiple classes of drugs and personal care and pesticides in water according to claim 1, wherein the mobile phase gradient elution procedure in the (a) detection conditions is as follows:
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；
the mobile phase gradient elution procedure in the detection condition (b) is as follows:
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；
the mobile phase gradient elution procedure in the detection condition (c) is as follows:
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；
the mobile phase gradient elution procedure in the detection condition (d) is as follows:
0min：60％A，40％B；4.0min：50％A，50％B；4.5min：0％A，100％B；
4.6min-8min：60％A，40％B；
the mobile phase gradient elution procedure in the detection condition (e) is as follows:
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 rapid detection of multiple classes of drugs and personal care and pesticides in water according to claim 1, wherein the flow rate of said mobile phase in said (a) - (e) detection conditions is from 0.2m L/min to 0.25m L/min.
4. The method of claim 1, wherein the aqueous formic acid-ammonium formate solution of (a) and (e) is obtained by mixing formic acid with an aqueous ammonium formate solution, the concentration of ammonium formate in the aqueous ammonium formate solution is 4 mmol/L-6 mmol/L, the volume fraction of formic acid in the aqueous formic acid-ammonium formate solution is 0.04% -0.06%, the volume fraction of formic acid in the aqueous formic acid solution in (b) is 0.1% -0.2%, and the volume fraction of acetic acid-ammonium acetate in (c) is obtained by mixing acetic acid with an aqueous ammonium acetate solution, the concentration of ammonium acetate in the aqueous ammonium acetate solution is 4-6 mmol/L, and the volume fraction of acetic acid in the aqueous ammonium acetate-ammonium acetate solution is 0.04% -0.06%.
5. The method for rapid detection of multiple classes of drugs and personal care and pesticides in water according to claim 1, wherein the sample to be tested is applied to the chromatographic column in an amount of 10 μ L-15 μ L.
6. The method for rapidly detecting the multi-class drugs, personal care products and pesticides in water according to any one of claims 1 to 5, wherein the scanning mode of the mass spectrum is a multi-reaction monitoring mode, the detector is a triple quadrupole rod, the mass spectrum conditions of the electrospray ionization positive mode are that the ion source temperature is 120 ℃ to 150 ℃, the taper hole voltage is 10V to 60V, the capillary voltage is 3.5KV to 4.0KV, the desolvation gas temperature is 380 ℃ to 400 ℃, the desolvation gas flow rate is 600L/h to 700L/h, the taper hole gas flow rate is 50L/h to 60L/h, and the collision energy is 5V to 40V, and the mass spectrum conditions of the electrospray ionization negative mode are that the ion source temperature is 120 ℃ to 150 ℃, the taper hole voltage is 10V to 60V, the capillary voltage is 3.0KV to 3.5KV, the desolvation gas temperature is 380 ℃ to 420 ℃, the desolvation gas flow rate is 600L/h to 700/h, the taper hole voltage is 50V to 387, and the collision energy is 3.5 to L V to 40 h.
7. The method of claim 1, wherein the weak anion exchange solid phase extraction column comprises a WAX column, the hydrophilic lipophilic balance solid phase extraction column comprises a H L B column, and the activated carbon solid phase extraction column comprises an AC2 column.
8. The method of claim 1, wherein the formic acid-methanol solution contains 2% to 5% formic acid by volume, the methyl tert-butyl ether-methanol solution contains 9:1 methyl tert-butyl ether and methanol, and the ammonium acetate-methanol solution contains 20 mmol/L to 40 mmol/L ammonium acetate.
9. The method of claim 1, wherein the flow rate of the first sample to be tested in the weak anion exchange solid phase extraction column, the hydrophilic lipophilic balance solid phase extraction column, and the activated carbon solid phase extraction column is from 5m L/min to 10m L/min.
10. The method of claim 1, wherein the elution rate of each eluent in the weak anion exchange solid phase extraction column, the hydrophilic lipophilic balance solid phase extraction column, and the activated carbon solid phase extraction column is from 1m L/min to 2m L/min.
11. The method of claim 1, wherein the complexing agent comprises ethylenediaminetetraacetic acid or disodium ethylenediaminetetraacetate, and the amount of the complexing agent is 0.2g to 0.5g per liter of the water sample to be tested.
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