CN112730574B - Method for rapidly and high-throughput detecting aldicarb, aldicarb sulfoxide and aldicarb sulfone in environmental water body - Google Patents
Method for rapidly and high-throughput detecting aldicarb, aldicarb sulfoxide and aldicarb sulfone in environmental water body Download PDFInfo
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- QGLZXHRNAYXIBU-WEVVVXLNSA-N aldicarb Chemical compound CNC(=O)O\N=C\C(C)(C)SC QGLZXHRNAYXIBU-WEVVVXLNSA-N 0.000 title claims abstract description 93
- YRRKLBAKDXSTNC-UHFFFAOYSA-N Aldicarb sulfonyl Natural products CNC(=O)ON=CC(C)(C)S(C)(=O)=O YRRKLBAKDXSTNC-UHFFFAOYSA-N 0.000 title claims abstract description 73
- YRRKLBAKDXSTNC-WEVVVXLNSA-N Aldoxycarb Chemical compound CNC(=O)O\N=C\C(C)(C)S(C)(=O)=O YRRKLBAKDXSTNC-WEVVVXLNSA-N 0.000 title claims abstract description 73
- BXPMAGSOWXBZHS-CYBMUJFWSA-N Aldicarb sulphoxide Natural products CNC(=O)ON=CC(C)(C)[S@@](C)=O BXPMAGSOWXBZHS-CYBMUJFWSA-N 0.000 title claims abstract description 71
- BXPMAGSOWXBZHS-UITAMQMPSA-N [(z)-(2-methyl-2-methylsulfinylpropylidene)amino] n-methylcarbamate Chemical compound CNC(=O)O\N=C/C(C)(C)S(C)=O BXPMAGSOWXBZHS-UITAMQMPSA-N 0.000 title claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
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- 238000004885 tandem mass spectrometry Methods 0.000 claims description 27
- 239000012224 working solution Substances 0.000 claims description 21
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- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000000861 blow drying Methods 0.000 claims description 4
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- 235000017060 Arachis glabrata Nutrition 0.000 description 1
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- 208000005623 Carcinogenesis Diseases 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
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Abstract
The invention provides a rapid and high-flux detection method for aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body, and belongs to the technical field of analysis and detection. The sample pretreatment method in the detection method provided by the invention is simple, does not consume organic solvents, is simple to operate and time-saving, and can realize high-throughput detection of aldicarb and metabolites thereof in environmental water; the invention overcomes the defects of uneven sampling and poor parallelism of DART ion sources by optimizing the sample application position, sample application method, ionization temperature and sample injection rate of the TIP head, and realizes the quantitative analysis of aldicarb and metabolites thereof in environmental water. The data of the examples show that the detection limits of the detection method provided by the invention on aldicarb, aldicarb sulfoxide and aldicarb sulfone are respectively 0.5 mug/L, 0.1 mug/L and 0.1 mug/L, the recovery rates are respectively 94-102%, 94-118% and 95-109%, and the precision is less than 10%.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a rapid and high-flux detection method for aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body.
Background
Aldicarb is a carbamate insecticide and acaricide, and is widely used for various crops such as cotton, peanut, corn and the like. Aldicarb will rapidly oxidize to the more stable aldicarb sulfoxide after spraying, and will oxidize to the more stable aldicarb sulfone. 40-60 wt% of aldicarb and its metabolite falls into soil in the spraying process, and finally enters into water body through the actions of leaching and the like of the soil, thereby causing human body exposure. Because aldicarb and its metabolites have potential toxicity of carcinogenesis, teratogenesis and mutagenesis, the existence of aldicarb and its metabolites in different water bodies can threaten the health of human bodies to different degrees. The World Health Organization (WHO) regulations on drinking water quality rules prescribe that the limit of aldicarb (including aldicarb sulfone and aldicarb sulfoxide) in drinking water be 10 mug/L; the limit standards of aldicarb, aldicarb sulfoxide and aldicarb sulfone in drinking water are respectively 3, 2 and 4 mug/L, and the sum of the three can not exceed 7 mug/L. The limit requirements for the content of aldicarb in groundwater of different grades are also carried out in GB/T14848-2017 groundwater quality standard in China.
At present, detection methods of aldicarb and metabolites thereof at home and abroad mainly comprise gas chromatography, high performance liquid chromatography and high performance liquid chromatography tandem mass spectrometry, and the methods all require a lengthy separation process in the detection process, and consume too much time and energy. In addition, when the detection method is used for detecting the aldicarb and the metabolites thereof in the water body environment, the pretreatment process of the sample is needed, the common pretreatment process of the aldicarb in the water body is complicated in steps, long in time consumption and high in cost, and the mass detection of the sample is difficult to realize.
The real-time direct analysis ion source is widely applied to the fields of drug discovery and development, food and drug safety control and detection, judicial identification, clinical examination, material analysis, natural product quality identification and the like. There are few reports on the detection of pesticide residues in environmental water bodies.
Due to the principle of directly analyzing an ion source in real time, the pure water solvent needs to consume excessive energy to gasify water molecules when detecting, so that the energy for a target compound in unit time is reduced, the detection sensitivity is reduced, and the actual detection requirement cannot be met.
Disclosure of Invention
In view of the above, the invention aims to provide a rapid and high-throughput detection method for aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body. The detection method provided by the invention has the advantages of simple pretreatment method, environmental protection and high detection sensitivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a rapid and high-flux detection method of aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body, which comprises the following steps:
centrifuging the environmental water body to be detected, and filtering the obtained supernatant with a 0.22 mu m filter membrane to obtain a sample to be detected;
detecting the sample to be detected by using a real-time direct analysis tandem mass spectrometry method to obtain the total ion flow peak intensity of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the sample to be detected;
based on the total ion flow peak intensity-concentration standard curve corresponding to aldicarb, aldicarb sulfoxide and aldicarb sulfone, the detection of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the environmental water body is realized;
the parameters of the real-time direct analysis tandem mass spectrometry comprise real-time direct analysis ion source parameters and MS/MS parameters;
the real-time direct analysis of ion source parameters includes:
ionized gas: helium gas;
ion gas flow rate: 2mL/min;
ion source: a positive ion mode;
sample injection mode: 12Dip-itSamplers mode;
sample application amount: 10-20 mu L;
sample injection rate: 0.6-0.7 mm/s;
ionization temperature: 300 ℃;
gate voltage: 150-200V;
distance of ion source outlet from mass spectrometry sample inlet: 2-4 cm;
vacuum degree of external pump: -70 to-90 kPa;
TIP head spotting position: the lower end of the TIP head is 1-5 mm;
TIP head spotting mode: after the TIP head is spotted, the TIP head is placed on a heating plate in parallel for drying, and the drying time is less than or equal to 10min.
Preferably, the temperature of the heating plate is 30-50 ℃; the blow-drying is carried out at a gas flow rate of 0.05 MPa.
Preferably, the MS/MS parameters include:
capillary voltage: 2.8-3.4 kV;
ion source temperature: 100-120 ℃;
desolventizing gas flow: 0L/h;
taper hole air flow: 0L/h;
acquisition mode: multiple reaction monitoring.
Preferably, the rotational speed of the centrifugation is 8000-15000 r/min and the time is 3-10 min.
Preferably, the method for establishing the standard curve of total ion flow peak intensity-concentration corresponding to aldicarb, aldicarb sulfoxide and aldicarb sulfone comprises the following steps:
preparing a series of mixed standard working solutions; the series of mixed standard working fluids comprise a first mixed standard working fluid, a second mixed standard working fluid, a third mixed standard working fluid and a fourth mixed standard working fluid; the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the first mixed standard working solution are 50ng/mL, 10ng/mL and 10ng/mL respectively; the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the second mixed standard working solution are respectively 10ng/mL, 2ng/mL and 2ng/mL, the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the third mixed standard working solution are respectively 5ng/mL, 1ng/mL and 1ng/mL, and the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the fourth mixed standard working solution are respectively 0.5ng/mL, 0.1ng/mL and 0.1ng/mL;
detecting the series of mixed standard working solutions by using a real-time direct analysis tandem mass spectrometry method to obtain the total ion flow peak intensities of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the series of mixed standard working solutions;
linearly fitting the total ion peak intensities and concentrations of the aldicarb, the aldicarb sulfoxide and the aldicarb sulfone to obtain a aldicarb total ion peak intensity-concentration standard curve, a aldicarb sulfoxide total ion peak intensity-concentration standard curve and an aldicarb sulfone total ion peak intensity-concentration standard curve;
the parameters of the real-time direct analysis tandem mass spectrometry are consistent with the technical scheme.
The invention provides a rapid and high-flux detection method of aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body, which comprises the following steps: centrifuging the environmental water body to be detected, and filtering the obtained supernatant with a 0.22 mu m filter membrane to obtain a sample to be detected; detecting the sample to be detected by using a real-time direct analysis tandem mass spectrometry method to obtain the total ion flow peak intensity of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the sample to be detected; detection of aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body is realized based on a total ion flow peak intensity-concentration standard curve corresponding to aldicarb, aldicarb sulfoxide and aldicarb sulfone. The detection method has the advantages of simple sample pretreatment method, no consumption of organic solvents, simple operation and time saving, and can realize the high-flux detection of aldicarb and metabolites thereof in environmental water; the invention overcomes the defects of uneven sampling and poor parallelism of DART ion sources by optimizing the sample application position of the TIP head, the sample application method of the TIP head, the ionization temperature and the sample injection rate, and realizes accurate and high-sensitivity quantitative analysis of aldicarb and metabolites thereof in environmental water. The data of the examples show that the detection limits of the detection method provided by the invention on aldicarb, aldicarb sulfoxide and aldicarb sulfone are respectively 0.5 mug/L, 0.1 mug/L and 0.1 mug/L, the recovery rates are respectively 94-102%, 94-118% and 95-109%, and the precision is less than 10%.
Drawings
FIG. 1 is a graph comparing the response of the total ion peak intensities of aldicarb, aldicarb sulfoxide and aldicarb sulfone at different ionization temperatures;
FIG. 2 is a graph comparing responses of peak intensities of total ion flows of aldicarb, aldicarb sulfoxide and aldicarb sulfone at different sample injection rates;
FIG. 3 is a graph comparing the response of the peak intensities of the total ion flows of aldicarb, aldicarb sulfoxide and aldicarb sulfone at different external pump vacuum levels;
FIG. 4 is a graph comparing the response of peak intensities of the total ion flux of various spotting amounts of aldicarb, aldicarb sulfoxide and aldicarb sulfone;
FIG. 5 is a graph comparing the response of the total ion peak intensities of aldicarb, aldicarb sulfoxide and aldicarb sulfone at different spot locations.
Detailed Description
The invention provides a rapid and high-flux detection method of aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body, which comprises the following steps:
centrifuging the environmental water body to be detected, and filtering the obtained supernatant with a 0.22 mu m filter membrane to obtain a sample to be detected;
detecting the sample to be detected by using a real-time direct analysis tandem mass spectrometry method to obtain the total ion flow peak intensity of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the sample to be detected;
detection of aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body is realized based on a total ion flow peak intensity-concentration standard curve corresponding to aldicarb, aldicarb sulfoxide and aldicarb sulfone.
The invention centrifugates the water body of the environment to be detected, and the obtained supernatant passes through a 0.22 mu m filter membrane to obtain the sample to be detected. In the invention, the rotation speed of the centrifugation is preferably 8000-15000 r/min, preferably 13000r/min; the time is preferably 3 to 10 minutes, more preferably 5 minutes.
After the liquid to be detected is obtained, the invention utilizes a real-time direct analysis tandem mass spectrometry (DART-MS/MS) to detect the sample to be detected, and the total ion flow peak intensity of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the sample to be detected is obtained.
In the present invention, the parameters of the real-time direct analysis tandem mass spectrometry include real-time direct analysis ion source (DART) parameters and MS/MS parameters; the real-time direct analysis of ion source parameters includes:
ionized gas: helium gas;
ion gas flow rate: 2mL/min;
ion source: a positive ion mode;
sample injection mode: 12Dip-itSamplers mode;
sample application amount: 10 to 20. Mu.L, preferably 10. Mu.L;
sample injection rate: 0.6 to 0.7mm/s, particularly preferably 0.6mm/s;
ionization temperature: 300 ℃;
gate voltage: 150 to 200V, preferably 200V;
distance of ion source outlet from mass spectrometry sample inlet: 2-4 cm, preferably 3cm;
vacuum degree of external pump: -70 to-90 kPa, particularly preferably-70 kPa;
TIP head spotting position: the lower end of the TIP head is 1-5 mm, preferably 2-4 mm, and particularly preferably 2mm;
TIP head spotting mode: after the TIP head is spotted, the TIP head is placed on a heating plate in parallel for drying, wherein the drying time is less than or equal to 10min; the temperature of the heating plate is preferably 30-50 ℃, and particularly preferably 45 ℃; the blow-drying is preferably carried out at a gas flow rate of 0.05 MPa.
According to the invention, through optimizing the point application position of the TIP head, the point application mode of the TIP head, the point application quantity, the sample application rate and the ionization temperature, the defects of uneven sampling and poor parallelism of the DART ion source are overcome, and the sensitivity of the detection method is improved.
In the present invention, the MS/MS parameters include:
capillary voltage: 2.8-3.4 kV, preferably 3.2kV;
ion source temperature: 100-120 ℃, preferably 120 ℃;
desolventizing gas flow: 0L/h;
taper hole gas: 0L/h;
acquisition mode: multiple reaction monitoring.
In the present invention, the mass spectrum parameters of aldicarb, aldicarb sulfoxide and aldicarb sulfone are shown in table 1 under the detection of the above-described real-time direct analysis of ion source parameters and MS/MS parameters.
Table 1 mass spectral parameters of aldicarb, aldicarb sulfoxide and aldicarb sulfone
After the total ion peak intensities of the aldicarb, the aldicarb sulfoxide and the aldicarb sulfone in the sample to be detected are obtained, the invention realizes detection of the aldicarb, the aldicarb sulfoxide and the aldicarb sulfone in the environmental water body based on the total ion peak intensity-concentration standard curve corresponding to the aldicarb, the aldicarb sulfoxide and the aldicarb sulfone.
In the present invention, the method for establishing the standard curve of the total ion flow peak intensity-concentration of the aldicarb, the aldicarb sulfoxide and the aldicarb sulfone preferably comprises the following steps:
preparing a series of mixed standard working solutions; the series of mixed standard working fluids comprise a first mixed standard working fluid, a second mixed standard working fluid, a third mixed standard working fluid and a fourth mixed standard working fluid; the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the first mixed standard working solution are 50ng/mL, 10ng/mL and 10ng/mL respectively; the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the second mixed standard working solution are respectively 10ng/mL, 2ng/mL and 2ng/mL, the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the third mixed standard working solution are respectively 5ng/mL, 1ng/mL and 1ng/mL, and the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the fourth mixed standard working solution are respectively 0.5ng/mL, 0.1ng/mL and 0.1ng/mL;
detecting the series of mixed standard working solutions by using a real-time direct analysis tandem mass spectrometry method to obtain the total ion flow peak intensities of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the series of mixed standard working solutions;
and linearly fitting the total ion peak intensities and concentrations of the aldicarb, the aldicarb sulfoxide and the aldicarb sulfone to obtain a aldicarb total ion peak intensity-concentration standard curve, a aldicarb sulfoxide total ion peak intensity-concentration standard curve and an aldicarb sulfone total ion peak intensity-concentration standard curve.
The method for preparing the series of mixed standard working fluids is not particularly limited, and the mixed standard working fluids can be prepared by a preparation method of the mixed standard working fluids which is well known to a person skilled in the art.
In the present invention, the parameters of the real-time direct analysis tandem mass spectrometry are preferably consistent with the above technical solutions, and will not be described herein.
The method of the linear fitting is not particularly limited, and a linear fitting method well known to those skilled in the art may be adopted.
The following is a detailed description of the rapid, high throughput detection methods of aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental body of water provided by the present invention, but they should not be construed as limiting the scope of the invention.
The parameters of the real-time direct analytical tandem mass spectrometry used in the examples below include
The real-time direct analysis of ion source parameters:
ionized gas: helium gas;
ion gas flow rate: 2mL/min;
ion source: a positive ion mode;
sample injection mode: 12Dip-itSamplers mode;
sample application amount: 10. Mu.L;
sample injection rate: 0.6mm/s;
ionization temperature: 300 ℃;
gate voltage: 200V;
distance of ion source outlet from mass spectrometry sample inlet: 3cm;
vacuum degree of external pump: -70kPa;
TIP head spotting position: the lower end of the TIP head is 2mm;
TIP head spotting mode: after the TIP head is spotted, the TIP head is placed on a heating plate at 45 ℃ in parallel, and blow-drying is carried out by using the gas flow rate of 0.05 MPa;
the MS/MS parameters include:
capillary voltage: 3.2kV;
ion source temperature: 120 ℃;
desolventizing gas flow: 0L/h;
taper hole gas: 0L/h;
acquisition mode: multiple reaction monitoring.
The test solutions used in examples 1 to 6 were standard mixtures of aldicarb, aldicarb sulfoxide and aldicarb sulfone each having a concentration of 100 ppd.
Example 1 selection of ionization temperature
The ionization temperature is a critical parameter affecting DART-MS/MS analysis results, and is optimized from the range of 250-400 ℃ in this example to obtain the optimal thermal analysis conditions. FIG. 1 is a graph comparing the response of the total ion peak intensities of aldicarb, aldicarb sulfoxide and aldicarb sulfone at different ionization temperatures. As can be seen from fig. 1: the response values of aldicarb, aldicarb sulfoxide and aldicarb sulfone were significantly higher at 300 ℃ than at other temperatures. The ionization temperature affects the response of the analyte by affecting the thermal analysis rate of the sample, which in turn affects the amount of compound entering the mass spectrometer per unit time.
Example 2 selection of sample Rate of auto sampler
The automatic sampler is characterized in that a TIP head with a sample is placed on a sampling frame of the automatic sampler, when the automatic sampler passes through an interface area of a DART ion source and a triple quadrupole mass spectrometer at a constant speed, the sample can be transferred to an ionization area of the ion source at the constant speed, and fig. 2 is a response comparison graph of the total ion flow peak intensities of aldicarb, aldicarb and aldicarb sulfone at different sample injection rates. As can be seen from fig. 2: when the sample injection rate is 0.6-0.7 mm/s, the best response value is obtained by the total ion flow spectrum diagram of aldicarb, aldicarb sulfoxide and aldicarb sulfone. The sample rate can be measured by affecting the sample's active time at the edge of the ionization region: when the sample injection speed is low, the moving time of the sample at the edge of the ionization region is increased, so that partial ionization is started when the sample does not reach the ionization region yet, and when the sample does not completely leave the ionization region, the next sample is partially started to be ionized, so that the problems of peak broadening of the sample and peak crossing of parallel samples are caused; when the sample injection rate is high, the passing time of the sample in the ionization center area is reduced, and the incomplete analysis of the sample is caused by the too short passing time, so that the sensitivity is reduced.
Example 3 selection of vacuum degree of external vacuum Pump
The external vacuum pump configured by the DART ion source has the function of stabilizing the vacuum degree of the triple quadrupole mass spectrometer and assisting in sampling. FIG. 3 is a graph comparing the response of the total ion peak intensities of aldicarb, aldicarb sulfoxide, and aldicarb sulfone at different external pump vacuum levels. As can be seen from fig. 3: when the vacuum degree of the external pump is-70 kPa, the response values of aldicarb, aldicarb sulfoxide and aldicarb sulfone are highest. Because of the ionization characteristic of the DART ion source, helium is blown into the mass spectrometer at the speed of 3L/min, and the instability of the vacuum degree of the mass spectrometer caused by the influence of the helium can be caused by the low vacuum degree of an external vacuum pump arranged on the DART ion source. Too high a vacuum can cause the sample to be drawn off the mass spectrum during entry into the mass spectrometer, reducing detection sensitivity.
Example 4 selection of Gate Voltage
In the embodiment, mixed standard substances with the same concentration are respectively adopted, and the grid voltage is optimized under the condition that the other parameters are unchanged, so that the result shows that when the grid voltage is 150V, the peak area of the mixed standard substances of aldicarb and the metabolites thereof is 26635; at a gate voltage of 200V, the peak area of the mixed standard substance of aldicarb and its metabolite was 26700. From the peak area it can be seen that: when the aldicarb and the metabolites thereof are analyzed, the corresponding influence on the aldicarb is small when the grid voltage fluctuates between 150 and 200V, and the detection requirement can be met.
Example 5 selection of spotting quantity
In the embodiment, mixed standard substances with the same concentration are respectively adopted, under the condition that the rest parameters are unchanged, the sample application amount is optimized, as shown in fig. 4, the comparison tests are respectively carried out on 5 mu L, 10 mu L, 15 mu L and 20 mu L in the range of 5 mu L to 20 mu L of sample application amount, and as can be seen from fig. 4, the peak response is obviously increased when the sample application amount is 10 mu L compared with the sample application amount of 5 mu L; when the spotting amount is 15 muL and 20 muL, the result is not much different from the spotting amount of 10 muL, because when the spotting amount is more than 10 muL, the spotting amount exceeds the carrying capacity of the front surface of the TIP head, and the solvent after spotting can diffuse to the back surface of the TIP head along with the TIP head, so that the ionization efficiency is affected. The results show that: the detection requirements can be met in the range of 10 to 20. Mu.L of spotting amount, but the response is optimal when the spotting amount is 10. Mu.L.
Example 6 selection of spotting locations
The difference in the spot location affects not only the parallelism between samples, but also the degree of ionization. This example shows that the ionization effect is optimal when the sample application position is between 1mm and 5mm from the lower end of the TIP head. When the spot is at the lowest end of the TIP as shown in fig. 5, the sample solution is easily diffused to the bottom of the TIP and the back of the TIP, so that the target substance cannot be ionized effectively. When the spot position is at a position of 5mm or more, the height of the ionization region is exceeded, so that the target substance cannot be effectively ionized. Thus, the optimal spot location selected in this application is between 1mm and 5mm below the TIP head.
Example 7
Comparison of the detection of aldicarb and aldicarb sulfoxide and aldicarb sulfone in the Water Environment with DART-MS/MS detection and LC-MS/MS detection
The LC-MS/MS technology adopted in the embodiment is used for detecting aldicarb and metabolites thereof according to the method of the national standard 'liquid chromatography-tandem mass spectrometry for measuring residual amounts of 450 pesticides and related chemicals in GB/T23214-2008 drinking water'. The DART-MS/MS and LC-MS/MS technologies are compared and analyzed from the aspects of sample pretreatment process, method detection limit and instrument detection time of 3.
4.1 pretreatment comparison of samples
In national standard GB/T23214-2008, the pretreatment method of the water body sample comprises 6 steps of sample weighing, liquid-liquid extraction, solid phase extraction, concentration, constant volume, detection and the like, the required reagent types are 6, and the total consumption of the reagent of a single sample is 71mL. When the DART-MS/MS technology established by the invention is used for detecting aldicarb and metabolites thereof in a water body environment, the sewage is required to be centrifuged, and other water body samples are only required to be detected after being subjected to membrane filtration, so that an organic solvent is not required, the detection flow is simplified, the detection time is shortened, the high-flux detection of the samples is realized, the reagent is saved, the cost is reduced, and the secondary pollution to the environment is reduced.
4.2 method detection Limit contrast
In national standard GB/T23214-2008, the detection limit of aldicarb sulfone is 2.14 mug/L, and the detection limit of aldicarb is 26.1 mug/L. When the DART-MS/MS technology is adopted to detect aldicarb and metabolites thereof in a water body environment, the detection limit of aldicarb sulfone is 0.1 mug/L, the detection limit of aldicarb is 0.5 mug/L, and the detection limit of aldicarb sulfoxide is 0.1 mug/L, which is far lower than the detection limit requirement specified in national standards.
4.3 detection time contrast
When three compounds in a water body are detected by an HPLC-MS/MS technology, the three compounds are separated by an HPLC system, and the processes of chromatographic column balancing, sample separation and chromatographic column flushing are needed, so that the time consumption is long; and when the environmental water is dirty, the purification means for sample pretreatment has higher requirements, otherwise, the blockage of a chromatographic column and the matrix effect of mass spectrum are easy to cause, so that the detection is influenced. Because of the in-situ ionization characteristic, the DART-MS/MS method rarely generates additive ions and rarely forms out-of-source ionization, so that different compounds in a mixed standard sample can be qualitatively determined according to molecular weight without chromatographic separation. After the DART ion source is connected with the MS/MS in series, a multi-reaction monitoring mode can be developed, the secondary separation and accuracy and qualitative advantages of the compound are realized through different fragment ions, the qualitative accuracy is improved, and meanwhile, the detection sensitivity of the technology is also greatly improved. The instrument analysis time of a single sample is only a few seconds, so that the in-situ high-flux detection of the water body sample is realized.
Example 8
Method detection limit, linear range and precision
The invention prepares the mixed standard solution of the target substances with different concentrations to be added into the measured sample, the same sample is collected for three times in parallel, the average value of the three times of parallel samples is used as the data of the final participation calculation, the signal to noise ratio is calculated by three times of signals, the result shows that the minimum detection limit of the detection method can reach the requirements of national standards, and the result is shown in Table 2.
The prepared standard series solution is measured according to the parameters of the real-time direct analysis tandem mass spectrometry, and the mass concentration (x, mug/L) of the target compound is used for carrying out linear regression analysis on the peak area (y), and the linear range, the correlation coefficient and the linear regression equation of each compound are shown in table 2.
Recovery rate of adding mark
In view of the characteristics of DART-MS/MS in-situ ionization, the influence factors on the recovery rate in the embodiment are only reflected in the influence of the filter membrane and the ionization efficiency parameter. In order to verify the accuracy of the detection method provided by the invention, the detection limit, the 3-time detection limit and the 5-time detection limit concentration values are respectively selected and added into a sample, and the detection is carried out according to the real-time direct analysis tandem mass spectrometry, and the results are shown in Table 2.
Table 2 aldicarb, aldicarb sulfoxide and aldicarb sulfone linearity, limit of detection, precision table
As can be seen from table 2: the correlation coefficients of the 3 target substances are all larger than 0.98; carrying out 6 times of parallel experiments at the standard adding level of 10ng/mL, wherein the relative standard deviation is less than 10 percent, and the detection requirement is met; the recovery rate of the three target substances also meets the detection requirement.
Example 9 actual sample measurement
In order to more accurately verify the accuracy of the real-time direct analysis tandem mass spectrometry provided by the invention, the invention randomly extracts part of groundwater samples in Lanzhou market, and adopts a national standard method and a DART-MS/MS method to detect, so that the results are consistent, and 3 target substances are not detected.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. A rapid and high-throughput detection method for aldicarb, aldicarb sulfoxide and aldicarb sulfone in an environmental water body is characterized by comprising the following steps of:
centrifuging the environmental water body to be detected, and filtering the obtained supernatant with a 0.22 mu m filter membrane to obtain a sample to be detected; the rotational speed of the centrifugation is 13000r/min, and the time is 5min;
detecting the sample to be detected by using a real-time direct analysis tandem mass spectrometry method to obtain the total ion flow peak intensity of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the sample to be detected;
based on the total ion flow peak intensity-concentration standard curve corresponding to aldicarb, aldicarb sulfoxide and aldicarb sulfone, the detection of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the environmental water body is realized;
the parameters of the real-time direct analysis tandem mass spectrometry comprise real-time direct analysis ion source parameters and MS/MS parameters;
the real-time direct analysis of ion source parameters includes:
ionized gas: helium gas;
ion gas flow rate: 2mL/min;
ion source: a positive ion mode;
sample injection mode: 12Dip-it Samplers mode;
sample application amount: 10. Mu.L;
sample injection rate: 0.6mm/s;
ionization temperature: 300 ℃;
gate voltage: 200V;
distance of ion source outlet from mass spectrometry sample inlet: 3cm;
vacuum degree of external pump: -70kPa;
TIP head spotting position: the lower end of the TIP head is 2mm;
TIP head spotting mode: after the TIP head is spotted, the TIP head is placed on a heating plate in parallel for drying, and the drying time is less than or equal to 10min; the temperature of the heating plate is 45 ℃; the blow-drying is carried out at a gas flow rate of 0.05 MPa;
the MS/MS parameters include:
capillary voltage: 3.2kV;
ion source temperature: 120 ℃;
desolventizing gas flow: 0L/h;
taper hole gas: 0L/h;
acquisition mode: monitoring multiple reactions;
the method for establishing the standard curve of the total ion flow peak intensity-concentration of the aldicarb, the aldicarb sulfoxide and the aldicarb sulfone comprises the following steps:
preparing a series of mixed standard working solutions; the series of mixed standard working fluids comprise a first mixed standard working fluid, a second mixed standard working fluid, a third mixed standard working fluid and a fourth mixed standard working fluid; the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the first mixed standard working solution are 50ng/mL, 10ng/mL and 10ng/mL respectively; the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the second mixed standard working solution are respectively 10ng/mL, 2ng/mL and 2ng/mL, the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the third mixed standard working solution are respectively 5ng/mL, 1ng/mL and 1ng/mL, and the concentrations of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the fourth mixed standard working solution are respectively 0.5ng/mL, 0.1ng/mL and 0.1ng/mL;
detecting the series of mixed standard working solutions by using a real-time direct analysis tandem mass spectrometry method to obtain the total ion flow peak intensities of aldicarb, aldicarb sulfoxide and aldicarb sulfone in the series of mixed standard working solutions;
and linearly fitting the total ion peak intensities and concentrations of the aldicarb, the aldicarb sulfoxide and the aldicarb sulfone to obtain a aldicarb total ion peak intensity-concentration standard curve, a aldicarb sulfoxide total ion peak intensity-concentration standard curve and an aldicarb sulfone total ion peak intensity-concentration standard curve.
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