CN113686986A - Method for simultaneously detecting 6 artificial sweeteners in municipal sludge by ultrasonic-solid phase extraction-liquid chromatography-mass spectrometry - Google Patents
Method for simultaneously detecting 6 artificial sweeteners in municipal sludge by ultrasonic-solid phase extraction-liquid chromatography-mass spectrometry Download PDFInfo
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/02—Column chromatography
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
A method for simultaneously detecting 6 artificial sweeteners in municipal sludge by ultrasonic-solid phase extraction-liquid chromatography-mass spectrometry belongs to the field of environmental analysis. 6 artificial sweetener standard substances of acesulfame potassium, sodium cyclamate, saccharin, sucralose, aspartame and neotame are respectively prepared into mother liquor, then, the mother liquor is diluted step by step to prepare a plurality of standard mixed solutions with concentration gradients, a standard curve is established, the artificial sweetener components are separated by an Aglient high performance liquid chromatography column, each artificial sweetener is qualitatively determined by retention time and mass-to-charge ratio in a gradient elution mode, and the 6 artificial sweeteners are quantitatively determined by eliminating instrument errors and matrix influences by an internal standard method. The municipal sludge sample is freeze-dried, ground and sieved, and the volume ratio of 0.1g of the sieved sample to 5mL is 1: 1, performing ultrasonic extraction centrifugation after mixing, adjusting the pH of supernatant to 3, performing purification and concentration by solid phase extraction, and finally performing detection and analysis by a high performance liquid chromatography tandem mass spectrometer. The method has the advantages of low detection limit, high sensitivity and strong reliability.
Description
Technical Field
The invention belongs to the field of environmental analysis, and particularly relates to a method for simultaneously detecting 6 artificial sweeteners in municipal sludge.
Background
The artificial sweetener is a sucrose substitute substance which is synthesized by artificial chemistry or is obtained by secondary processing of natural substance extracts, is widely added into food beverages, personal care products, medicaments and feeds due to high sweetness, low calorie, difficult metabolism by organisms and non-decayed tooth, and effectively meets the requirement of people and patients (diabetes, obese consumers and decayed tooth patients) who pursue healthy life style on sweetness.
As the amount of artificial sweeteners used increases, their detection rate and occurrence concentration in the environment are attracting much attention. The concentration of artificial sweeteners such as Saccharin (SAC), acesulfame potassium (ACE), Aspartame (ASP), cyclamate (CYC) and Sucralose (SUC) in various water bodies reaches the level of mu g/L-mg/L, and the ACE detected in some groundwater is as high as 4.71 mu g/L, which further proves the universality of environmental pollution of the artificial sweeteners. Although artificial sweeteners have proven to be non-toxic to humans at acceptable daily intake concentrations of 5-50 mg/kg body weight per day, their environmental impact is increasingly being determined, typical examples being the interference of SUC with photosynthesis processes and adverse effects on the physiological and motor behaviour of daphnia magna.
Sewage treatment plants are a major source of artificial sweeteners into the environment. Because the artificial sweetener has extremely strong polarity and is difficult to be metabolized by microorganisms, the artificial sweetener is difficult to be completely degraded by the treatment process of the conventional sewage treatment plant, and most of the artificial sweetener is discharged into the receiving water body along with the effluent of the sewage treatment plant. In addition, part of the artificial sweetener adsorbed on the sludge can enter the soil environment along with the agriculture of the municipal sludge. Because the artificial sweetener has high water solubility and is difficult to exist and stay in a solid phase, the artificial sweetener from sludge is often ignored, recent researches prove that the content of ACE, SAC, CYC, ASP and SUC in the dry weight of sludge in a secondary sedimentation tank of a sewage plant reaches 0.15-6.28 mug/g, and high residue and continuous exposure pose potential threats to soil environment and crops. Therefore, aiming at the problem of ecological safety of municipal sludge in agriculture, an analysis method with low detection limit, high sensitivity, good selectivity and strong reliability is needed to be established to accurately determine the content of the artificial sweetener in a complex solid matrix sample such as municipal sludge.
Currently, there are several methods for detecting artificial sweeteners such as: gas chromatography, spectrophotometry, capillary electrophoresis, ion chromatography, high performance liquid chromatography and the like, which have certain defects such as low sensitivity, few types of detected sweeteners, easy influence of impurities in samples and the like due to the obvious difference of physicochemical properties, electrochemical properties and spectral properties of different artificial sweeteners. The high performance liquid chromatography-tandem mass spectrometry detection method can be used for simultaneously detecting various artificial sweeteners, the result of qualitative and quantitative analysis is more reliable, the detection limit and the quantitative limit are lower, the analysis time is shorter, and the analysis and detection requirements on environmental samples are effectively met. However, the existing mature analysis and detection method is mainly used for monitoring the artificial sweetener in food, beverage and water, is not developed around the municipal sludge and other complex matrix solid samples, has the problems of complex pretreatment steps, long purification time consumption, incomplete purification and the like, and limits the development of rapid, sensitive and reliable detection of the artificial sweetener in the municipal sludge and other solid samples. Therefore, the method is considered from the physical property, the sludge combination characteristic and the detection efficiency of the artificial sweetener, and the method for simultaneously detecting 6 kinds of artificial sweeteners in municipal sludge is developed, so that the method is beneficial to mastering the trend characteristics of the municipal sludge and the artificial sweetener in the agricultural process, and the ecological safety of soil and crops is guaranteed.
The invention content is as follows:
the invention provides a method for simultaneously detecting 6 artificial sweeteners in municipal sludge by ultrasonic-solid phase extraction-liquid chromatography-mass spectrometry, which can solve the problem that the prior art is difficult to accurately, efficiently and stably detect various artificial sweeteners in a complex environment matrix, and has the advantages of small using amount of solvents and samples, and simple and effective extraction process.
The technical scheme adopted by the invention for solving the technical problems is that the method for simultaneously detecting 6 artificial sweeteners in municipal sludge by ultrasonic-solid phase extraction-liquid chromatography-mass spectrometry comprises the following steps:
A. dissolving 1mg of standard substances of acesulfame potassium, sodium cyclamate, saccharin, sucralose, aspartame and neotame in 10mL of a volume ratio of 1: 1 methanol/ultrapure water is used as mother liquor, the concentration of the mother liquor is 100mg/L, and then the mother liquor is diluted step by step to prepare seven standard mixed solutions, and the concentrations of the standard mixed solutions are 1 mug/L, 5 mug/L, 10 mug/L, 50 mug/L, 100 mug/L, 200 mug/L and 500 mug/L.
B. Taking an internal standard substance of sodium cyclamate-d40.1mg, dissolving in 100mL of a volume ratio of 1: 1 methanol/ultrapure water is used as a mother liquor of an internal standard substance, and the concentration of the mother liquor is 1 mg/L.
C. And adding the internal standard solution into the seven standard mixed solutions to ensure that the concentration of the internal standard substance in the seven standard mixed solutions is 20 mug/L for the detection and analysis of the liquid chromatography-mass spectrometry.
D. Separating the artificial sweetener by adopting an agent high performance liquid chromatography column (ZORBAX Eclipse Plus), taking ultrapure water and acetonitrile solution with the mass percent of 95% as mobile phases, adding ammonium formate and formic acid into the two mobile phases, wherein the concentration of the ammonium formate in each mobile phase is 0.32g/L, the mass percent of the formic acid is 0.1%, passing through corresponding 0.22 mu m filter membranes before the mobile phases are put on a machine, performing ultrasonic degassing, the flow rate of the mobile phases is 0.4mL/min, the sample feeding amount of a sample is 15 mu L, and performing gradient elution.
E. Each artificial sweetener is characterized by retention time and mass-to-charge ratio, and 6 artificial sweeteners are quantified by eliminating the influence of instrument errors and matrixes by an internal standard method to obtain a regression equation and a correlation coefficient of the concentration and the response value of each artificial sweetener.
F. The municipal sludge sample is frozen and dried, ground and sieved by a sieve with the aperture of 100 meshes (0.15mm), 0.1g of the sieved sample is weighed, and 500ng of each of 6 artificial sweetener standards is added into the sample, and then vortex oscillation is carried out for 5min to balance for 30 min.
G. Adding a standard-balanced municipal sludge sample into a 5mL municipal sludge sample with a volume ratio of 1: 1, performing ultrasonic extraction reaction in an ultrasonic generator for 30min, then centrifuging for 5min at 10000rpm, collecting supernatant into a polypropylene tube, and performing ultrasonic extraction reaction on the mixture by using a volume ratio of 1: 1 methanol/ultrapure water was diluted to 10mL (adjusted to pH-3).
H. Further purifying and concentrating the supernatant through solid phase extraction, adding 6mL of methanol to balance an Oasis HLB solid phase extraction column for 3min, adding 6mL of ultrapure water with pH 2 to wash the solid phase extraction column, adding 10mL of labeled supernatant to pass through the column, wherein the flow rate of the passing through the column is 1mL/min, adding 10mL of ultrapure water with pH 2 to wash impurities, draining for 30min after passing through the column, and adding 6mL of the mixture with the volume ratio of 1: eluting with 1 methanol/ethyl acetate at flow rate of 1mL/min for 5min, and blow-drying the eluate with nitrogen blowing instrument under water bath heating at 40 deg.C to constant volume of 1 mL.
I. Before carrying out liquid quality analysis, a 0.22 mu m PVDF needle type filter membrane is used for filtering a constant volume sample, and an internal standard substance is added, wherein the concentration of the internal standard substance is 20 mu g/L.
J. Taking a sample to be analyzed and detected in the step I, taking the sample volume of 15 mu L, separating by adopting an active high performance liquid chromatography column, taking ultrapure water and acetonitrile solution with the mass percentage of 95% as mobile phases, adding ammonium formate and formic acid into the two mobile phases, wherein the concentration of the ammonium formate in each mobile phase is 0.32g/L, the mass percentage of the formic acid is 0.1%, carrying out gradient elution, determining the quality of each artificial sweetener through the retention time and the mass-to-charge ratio, and obtaining the concentrations of 6 artificial sweeteners including acesulfame potassium, sodium cyclamate, saccharin, sucralose, aspartame and neotame by using an internal standard method.
The method has the advantages that the content of 6 artificial sweeteners in complex solid samples such as municipal sludge can be quickly, accurately and reliably obtained, and a powerful monitoring means is provided for the safety of the municipal sludge agricultural process.
Compared with the prior art, the invention establishes the ultrasonic-solid phase extraction-liquid chromatography-mass spectrometry combined simultaneous detection method of 6 artificial sweeteners including acesulfame, sodium cyclamate, saccharin, sucralose, aspartame and neotame in municipal sludge. The method is rapid, accurate and stable, extraction elution solvents with different solvent ratios and different pH values are optimally compared, the used solvents and samples are small in quantity, the content of 6 artificial sweeteners can be simultaneously measured, the detection limit is 0.8-43.2 ng/g, the recovery rate can reach 75-94%, and the pretreatment and the on-machine analysis of the samples can be completed within 2 hours. The sludge sample and the solvent are less in dosage, the pretreatment method is rapid and easy to operate, the detection limit of the sample is low, the recovery rate is high, and the accuracy and the sensitivity meet the requirements. The method can meet the requirement of detecting the trace artificial sweetener in the solid samples of complex matrixes such as sludge and the like.
Drawings
FIG. 1 is a chromatogram of an artificial sweetener according to an embodiment of the invention
Detailed Description
Specifically, the method for simultaneously detecting 6 artificial sweeteners in municipal sludge by ultrasonic-solid phase extraction-liquid chromatography-mass spectrometry comprises the following steps:
A. dissolving 1mg of standard substances of acesulfame potassium, sodium cyclamate, saccharin, sucralose, aspartame and neotame in 10mL of a volume ratio of 1: 1 methanol/ultrapure water is used as mother liquor, the concentration of the mother liquor is 100mg/L, and then seven standard mixed solutions are prepared by stepwise dilution, wherein the concentrations of the standard mixed solutions are 1 mug/L, 5 mug/L, 10 mug/L, 50 mug/L, 100 mug/L, 200 mug/L and 500 mug/L.
B. Taking an internal standard substance of sodium cyclamate-d40.1mg, dissolving in 100mL of a volume ratio of 1: 1 methanol/ultrapure water is used as a mother liquor of an internal standard substance, and the concentration of the mother liquor is 1 mg/L.
C. And adding the internal standard solution into the seven standard mixed solutions to ensure that the concentration of the internal standard substance in the seven standard mixed solutions is 20 mug/L for the detection and analysis of the liquid chromatography-mass spectrometry.
D. Separating the artificial sweetener by adopting an agent high performance liquid chromatography column (ZORBAX Eclipse Plus), taking ultrapure water and acetonitrile solution with the mass percent of 95% as mobile phases, adding ammonium formate and formic acid into the two mobile phases, wherein the concentration of the ammonium formate in each mobile phase is 0.32g/L, the mass percent of the formic acid is 0.1%, passing through corresponding 0.22 mu m filter membranes before the mobile phases are put on a machine, performing ultrasonic degassing, the flow rate of the mobile phases is 0.4mL/min, the sample feeding amount of a sample is 15 mu L, and performing gradient elution.
E. Each artificial sweetener is characterized by retention time and mass-to-charge ratio, and 6 artificial sweeteners are quantified by eliminating the influence of instrument errors and matrixes by an internal standard method to obtain a regression equation and a correlation coefficient of the concentration and the response value of each artificial sweetener.
F. The municipal sludge sample is frozen and dried, ground and sieved by a sieve with the aperture of 100 meshes (0.15mm), 0.1g of the sieved sample is weighed, and 500ng of each of 6 artificial sweetener standards is added into the sample, and then vortex oscillation is carried out for 5min to balance for 30 min.
G. Adding the municipal sludge sample with the added standard balance into 5mL of a mixture with the volume ratio of 1: 1 and 5: 3, extracting and reacting in an ultrasonic generator for 30min, comparing the effects of extracting agents with different proportions, optimizing the method of ultrasonic extraction liquid, then centrifuging for 10min at 10000rpm, collecting supernatant liquid to a polypropylene tube, and mixing the supernatant liquid with the mixture of the extracting agents in a volume ratio of 1: 1 methanol/ultrapure water was diluted to 10mL and the pH was adjusted according to the solid phase extraction protocol.
H. And further purifying and concentrating the supernatant through solid-phase extraction, constructing 3 solid-phase extraction schemes using different activated equilibrium solutions, impurity washing solutions and eluents by considering the chemical properties of the artificial sweetener and the characteristics of a solid-phase extraction column, and optimizing the solid-phase extraction schemes according to the recovery rate. Adding 6mL of methanol activating solution to balance the Oasis HLB solid phase extraction column for 3min, adding 6mL of impurity washing solution to wash impurities of the solid phase extraction column, adding 10mL of labeled supernatant to pass through the column at the column flow rate of 1mL/min, adding 10mL of impurity washing solution to wash impurities, draining for 30min after passing through the column, adding 6mL of eluent to elute and drain for 5min, and drying the eluent by using a nitrogen blowing instrument under the water bath heating condition at 40 ℃ to achieve the constant volume of 1 mL.
I. Before carrying out liquid quality analysis, a 0.22 mu m PVDF needle type filter membrane is used for filtering a constant volume sample, and an internal standard substance is added, wherein the concentration of the internal standard substance is 20 mu g/L.
J. Taking a sample to be analyzed and detected in the step I, taking the sample volume of 15 mu L, separating by adopting an active high performance liquid chromatography column, taking ultrapure water and acetonitrile solution with the mass percentage of 95% as mobile phases, adding ammonium formate and formic acid into the two mobile phases, carrying out gradient elution with the mass percentage of the formic acid of 0.32g/L and the mass percentage of the ammonium formate of 0.1%, determining the quality of each artificial sweetener by using the retention time and the mass-to-charge ratio, and obtaining the concentrations of 6 artificial sweeteners including acesulfame, sodium cyclamate, saccharin, sucralose, aspartame and neotame by using an internal standard method.
The present invention is further illustrated by the following test examples and examples, but the scope of the present invention is not limited to the embodiments described.
1. Experimental part
1.1 reagents and instruments
High performance liquid chromatography tandem mass spectrometer (Agilent 1290-; a solid phase extraction device (Supelco-547044); a freeze-drying device (FT 1D-50); a nitrogen blower (LDLX-MTN-2800D); ultrasonic cleaning machines (KQ-500 DE); a high-speed centrifuge (H1850); a water purifier (Milli Q Direct 8); vortex oscillator (Kylin-Bell).
The organic solvent comprises methanol, acetonitrile and ethyl acetate which are all chromatographically pure, ammonium formate is chromatographically pure, formic acid is analytically pure, hydrochloric acid is analytically pure and ultrapure water;
artificial sweetener standard: the acesulfame potassium, sodium cyclamate, saccharin, sucralose, aspartame, neotame) standard products are all high-purity (> 97.7%);
internal standard substance: cyclamate-d 4;
and (3) mixing the standard substance in a volume ratio of 1: 1, preparing 100mg/L of methanol/ultrapure water into a standard mixed solution containing 6 artificial sweeteners, and storing the mixed solution in a shade at the temperature of minus 20 ℃;
and (3) mixing the internal standard substance by using a volume ratio of 1: 1, preparing 1mg/L internal standard substance stock solution by using methanol/ultrapure water, and storing in a shading mode at the temperature of minus 20 ℃;
standard curve: and (3) preparing standard mixed solution by stepwise dilution, wherein 7 standard mixed solutions with concentration gradients of 1 mu g/L, 5 mu g/L, 10 mu g/L, 50 mu g/L, 100 mu g/L, 200 mu g/L and 500 mu g/L are prepared, an internal standard substance is added to ensure that the concentration of the internal standard substance is 20 mu g/L, and the standard curve is established by performing liquid chromatography-mass spectrometry analysis.
1.2 Instrument detection Condition and evaluation
Instrument chromatographic conditions: an active high performance liquid chromatography column (ZORBAX Eclipse Plus, 4.5X 150mm, 3.5 μm) was used; the mobile phase adopts water (mobile phase A) and acetonitrile with the mass percent of 95% (mobile phase B), ammonium formate and formic acid are added into the mobile phase, the concentration of the ammonium formate in each mobile phase is 0.32g/L, the mass percent of the formic acid is 0.1%, and the flow rate of the mobile phase is 0.4 mL/min; the sample amount of the sample is 15 mu L; the elution mode was a gradient elution, as shown in Table 1.
TABLE 1 gradient elution procedure
| Time (min) | Mobile phase A (%) | Mobile phase B (%) | Flow rate (mL/min) |
| 0 | 95 | 5 | 0.4 |
| 10 | 50 | 50 | 0.4 |
| 12 | 50 | 50 | 0.4 |
| 12.06 | 95 | 5 | 0.4 |
| 15 | 95 | 5 | 0.4 |
Mass spectrum conditions of the instrument: an electrospray ionization source (ESI) is adopted, and the mode is set to be a negative ionization multi-reaction monitoring mode. Nitrogen (99.99%) was used as the spray drying gas and argon (99.99%) was used as the collision gas. Each target compound optimizes one daughter ion with a high response value as a quantitative ion, and the other daughter ion with a relatively low response value as a qualitative ion, and the multiple reaction monitoring parameters are shown in table 2.
TABLE 2 multiple reaction monitoring parameters for targets
Instrumental analysis method evaluation: the mother solution of the standard solution is diluted step by step to prepare the standard solutions with various concentration gradients, the concentration range is 1 ng/L-1 mg/L, and the lowest concentration of each target compound which can be detected by an instrument is determined through computer detection. Thereafter, constant concentration experiments were performed based on the lowest concentration that can be detected for each target, 6 replicates were set for each group, and method precision was expressed as the standard deviation of the replicates. Wherein, the detection limit of the instrument is 3 times of the signal-to-noise ratio, and the quantification limit is 10 times of the signal-to-noise ratio. The evaluation results of the instrumental analysis method are shown in table 3.
TABLE 3 instrumental analysis method evaluation
| Target object | Standard curve R2 | Detection Limit (ng/L)/RSD (%) | Quantitative limit (ng/L)/RSD (%) |
| Acesulfame potassium | 0.998 | 2.1/1 | 5.0/4 |
| Sodium cyclamate | 0.999 | 6.2/2 | 30.2/5 |
| Saccharin | 0.996 | 22.1/3 | 72.7//9 |
| Aspartame | 0.994 | 6.5/4 | 19.7/12 |
| Neotame | 0.999 | 8.2/5 | 26.3/18 |
| Sucralose | 0.999 | 345.1/7 | 1150.3/22 |
1.3 ultrasonic extraction of municipal sludge
The municipal sludge sample is frozen and dried, ground and sieved by a sieve with the aperture of 100 meshes (0.15mm), 0.1g of the sieved sample is weighed, and 500ng of each of 6 artificial sweetener standards is added into the sample, and then vortex oscillation is carried out for 5min to balance for 30 min. Adding a standard-balanced municipal sludge sample into a 5mL municipal sludge sample with a volume ratio of 1: 1 and volume ratio 5: extracting and reacting in an ultrasonic generator for 30min after 3 methanol/ultrapure water, comparing extraction effects, then centrifuging for 10min at 10000rpm, collecting supernatant to a polypropylene tube, and mixing the supernatant with a solvent with a volume ratio of 1: 1 to 10mL of methanol/ultrapure water, and the pH was adjusted according to the solid phase extraction protocol.
1.4 purification and concentration by solid phase extraction
The supernatant was further purified and concentrated by solid phase extraction. Considering the chemical properties of the artificial sweetener and the characteristics of the solid phase extraction column, 3 solid phase extraction schemes using different activating solutions, impurity washing solutions and eluents are constructed, specifically, see table 4, 6mL of methanol is added to activate and balance the Oasis HLB solid phase extraction column for 3min, 6mL of the impurity washing solution is added to wash impurities of the solid phase extraction column, 10mL of the labeled supernatant is added to pass through the column, the flow rate of the passing through the column is 1mL/min, 10mL of the impurity washing solution is added to wash impurities, the column is drained for 30min after passing through the column, 6mL of the eluent is added to elute and drain for 5min, a nitrogen blowing instrument is used for blowing the eluent under the water bath heating condition at 40 ℃ to fix the volume of 1mL, and the internal standard substance is added to perform liquid-mass spectrometry analysis.
TABLE 4 solid phase extraction protocol
TABLE 5 recovery of solid phase extraction
TABLE 6 recovery rate of ultrasonic-solid phase extraction of municipal sludge sample
1.5 ultrasonic-solid phase extraction-liquid chromatography-Mass Spectrometry method evaluation
A0.1 g sample of the tagged sludge was extracted using established procedures and the artificial sweetener itself contained in the sample was obtained by testing the same batch of untagged sample and subtracted as background value. The detection limit of the method is 3 times the signal-to-noise ratio, the quantification limit is 10 times the signal-to-noise ratio, and the precision of the method is obtained by setting parallel samples (n is 3) and calculating the standard deviation between the parallel samples. The evaluation results are shown in Table 7.
TABLE 7 sludge sample analysis method detection limit and quantitation limit
2. Analysis of actual samples
The sample was taken from 4 sewage plants for analysis. Freeze-drying the sludge sample, grinding and sieving, weighing 0.1g, adding 5mL of the mixture with the volume ratio of 1: 1 of methanol/ultrapure water, performing extraction reaction in an ultrasonic generator for 30min, then centrifuging at 10000rpm for 10min, collecting supernatant into a polypropylene tube, and mixing the supernatant with a solvent in a volume ratio of 1: methanol/ultrapure water of 1 was diluted to 10mL, and the pH was adjusted to 3.
Further purifying and concentrating the supernatant through solid-phase extraction, adding 6mL of methanol to balance an Oasis HLB solid-phase extraction column for 3min, adding 6mL of methanol to wash impurities of the solid-phase extraction column, passing 50mL of the supernatant through the column at a flow rate of 1mL/min, adding 10mL of ultrapure water with pH of 2 to wash impurities, draining for 30min after passing through the column, and adding 6mL of the mixture in a volume ratio of 1: eluting with methanol/ethyl acetate of 1, draining for 5min, blow-drying the eluate with a nitrogen blowing instrument under the water bath heating condition of 40 deg.C to a constant volume of 1mL, adding an internal standard substance, and performing LC-MS analysis.
Taking a sample to be analyzed and detected, wherein the sample introduction amount is 15 mu L, separating by adopting an Aglient high performance liquid chromatography column, taking ultrapure water and acetonitrile with the mass percentage of 95% as mobile phases, adding ammonium formate and formic acid into the two mobile phases, wherein the concentration of the ammonium formate in each mobile phase is 0.32g/L, the mass percentage of the formic acid is 0.1%, performing gradient elution, determining the quality of each artificial sweetener by the retention time and the mass-to-charge ratio, and obtaining the concentrations of 6 artificial sweeteners of acesulfame, sodium cyclamate, saccharin, sucralose, aspartame and neotame by an internal standard method.
In 4 dewatered sludge samples of sewage treatment plants, 3 artificial sweeteners of sodium cyclamate, aspartame and neotame are detected together, and the concentration ranges are respectively 0.08-0.10 mug/g, nd-0.20 mug/g and nd-0.04 mug/g.
Claims (2)
1. A method for simultaneously detecting 6 artificial sweeteners in municipal sludge by ultrasonic-solid phase extraction-liquid chromatography-mass spectrometry is characterized by comprising the following steps:
taking 1mg of each of standard substances of acesulfame potassium, sodium cyclamate, saccharin, sucralose, aspartame and neotame, dissolving in 10mL of methanol/ultrapure water as mother liquor, wherein the volume ratio of the methanol to the ultrapure water is 1: 1, diluting the mother liquor by stages to prepare seven standard mixed solutions with the concentration of 1 mug/L, 5 mug/L, 10 mug/L, 50 mug/L, 100 mug/L, 200 mug/L and 500 mug/L respectively, wherein the concentration of the mother liquor is 100 mg/L;
taking an internal standard substance of sodium cyclamate-d40.1mg, dissolving in 100mL of a volume ratio of 1: 1, taking methanol/ultrapure water as mother liquor of an internal standard substance, wherein the concentration of the mother liquor of the internal standard substance is 1 mg/L;
adding an internal standard solution into the seven standard mixed solutions to enable the concentration of the internal standard substance in the seven standard mixed solutions to be 20 mug/L, and using the seven standard mixed solutions for LC-MS detection and analysis;
separating the artificial sweetener by adopting an agent high performance liquid chromatography column, taking ultrapure water and acetonitrile solution with the mass percent of 95% as mobile phases, adding ammonium formate and formic acid into the two mobile phases, wherein the concentration of the ammonium formate in each mobile phase is 0.32g/L, the mass percent of the formic acid is 0.1%, filtering the mobile phases with a 0.22 mu m filter membrane before being installed on a machine, performing ultrasonic degassing, and performing gradient elution, wherein the flow rate of the mobile phases is 0.4mL/min, and the sample introduction amount of a sample is 15 mu L;
each artificial sweetener is characterized by retention time and mass-to-charge ratio, 6 artificial sweeteners are quantified by an internal standard method, and a regression equation and a correlation coefficient of the concentration and the response value of each artificial sweetener are obtained;
freeze-drying a municipal sludge sample, grinding, sieving with a sieve with a pore size of 100 meshes, weighing 0.1g of the sieved sample, adding 500ng of each of 6 artificial sweetener standards into the sample, and then carrying out vortex oscillation for 5min to balance for 30 min;
adding a standard-balanced municipal sludge sample into a 5mL municipal sludge sample with a volume ratio of 1: 1, performing ultrasonic extraction reaction in an ultrasonic generator for 30min, then centrifuging for 5min at 10000rpm, collecting supernatant into a polypropylene tube, and performing ultrasonic extraction reaction on the mixture by using a volume ratio of 1: diluting the 1 methanol/ultrapure water to 10mL, and adjusting the pH of the supernatant to 3 by hydrochloric acid;
purifying and concentrating the supernatant through solid phase extraction, adding 6mL of methanol to balance and activate an Oasis HLB solid phase extraction column for 3min, adding 6mL of ultrapure water with the pH value of 2 to wash impurities in the solid phase extraction column, adding 10mL of labeled supernatant to pass through the column, wherein the flow rate of the passing through the column is 1mL/min, adding 10mL of ultrapure water with the pH value of 2 to wash impurities, draining for 30min after passing through the column, and adding 6mL of a volume ratio of 1: eluting with 1 methanol/ethyl acetate at flow rate of 1mL/min for 5min, blow-drying the eluate with a nitrogen blowing instrument under water bath heating at 40 deg.C to constant volume of 1 mL;
filtering the constant volume sample by using a PVDF needle type filter membrane with the thickness of 0.22 mu m before liquid quality analysis, and adding an internal standard substance, wherein the concentration of the internal standard substance is 20 mu g/L;
taking a sample to be analyzed and detected, wherein the sample introduction amount is 15 mu L, separating by adopting an active high performance liquid chromatography column, taking ultrapure water and acetonitrile solution with the mass percentage of 95% as mobile phases, adding ammonium formate and formic acid into the two mobile phases, wherein the concentration of the ammonium formate in each mobile phase is 0.32g/L, the mass percentage of the formic acid is 0.1%, performing gradient elution, determining the quality of each artificial sweetener by the retention time and the mass-to-charge ratio, and obtaining the concentrations of 6 artificial sweeteners of acesulfame, sodium cyclamate, saccharin, sucralose, aspartame and neotame by an internal standard method.
2. The method for simultaneously detecting 6 artificial sweeteners in a municipal sludge sample according to claim 1, wherein: eliminating the influence of instrument, artificial and matrix errors by adopting an internal standard method, wherein the volume ratio of 0.1g of sample to 5mL is 1: 1 for 30min, regulating the pH of a supernatant to 3, and performing solid phase extraction by using a methanol/ultrapure water mixed ultrasonic reaction, wherein the volume ratio of 6mL in the solid phase extraction is 1: 1, eluting with 1mL/min of methanol/ethyl acetate, and simultaneously analyzing 6 artificial sweeteners including acesulfame potassium, sodium cyclamate, saccharin, sucralose, aspartame and neotame in the municipal sludge sample.
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