CN108593756B - Quick detection device of trace steroid in water - Google Patents
Quick detection device of trace steroid in water Download PDFInfo
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- CN108593756B CN108593756B CN201810705360.XA CN201810705360A CN108593756B CN 108593756 B CN108593756 B CN 108593756B CN 201810705360 A CN201810705360 A CN 201810705360A CN 108593756 B CN108593756 B CN 108593756B
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- 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
Abstract
The invention relates to a rapid detection device for trace steroid in a water body. Comprises a mass spectrometer, an ionization mechanism and a sample processing mechanism; the sample processing mechanism comprises a volatile solvent introducing mechanism, a heating transmission mechanism and an evaporation enrichment spraying mechanism; the conical nozzle in the evaporation enrichment injection mechanism corresponds to a mass spectrum inlet of the mass spectrometer, and an ionization region is arranged above the conical nozzle and the mass spectrum inlet; when the device works, the first carrier gas and the volatile solvent are mixed to form a first mixed gas, and then the first mixed gas and the second carrier gas are combined to obtain a second mixed gas; when the temperature of the evaporating cavity reaches the Leidenford effect point of the sample to be detected, adding the solution to be detected into a sample tank of the evaporating cavity; the tested solution generates a Leidenford effect under the action of the second mixed gas and the third carrier gas, and is sprayed into an ionization region through a conical nozzle; the steroid molecules are ionized into steroid ions; and is sucked into a mass spectrometer, and mass spectrograms and selective ion flow diagrams of steroid detected objects are obtained through detection of the mass spectrometer.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to a rapid detection device for trace steroid in a water body.
Background
Steroid is also called steroid, is a kind of lipid, it has very strong endocrine disturbance and biological activity, and can cause human reproductive disorder, abnormal behavior, endocrine disturbance and even cancer, etc. at very low concentration. The steroid in the environment mainly comes from excretion of human beings and vertebrates, use of artificially synthesized steroid drugs and wastewater discharge of hospitals and pharmaceutical enterprises. Since the sewage treatment plant cannot completely remove the steroid substances, the residual steroid substances are discharged into the environmental water. The research shows that the ecological steroid environmental effect in the water body is most direct, and the steroid substances in the water body can cause sex interference to aquatic organisms at extremely low concentration, and various diseases can be caused by drinking the water body and eating organisms polluted by the water body by human beings. Therefore, the accurate determination of the residual steroid in the water body is an important means for risk assessment and pollution control, and is also a basis for ensuring environmental safety and food safety.
In recent years, research on steroid detection is receiving more and more attention, and along with development of technology and general concern of people on food and environmental safety, requirements on sensitivity of a detection method are also increasing. Typical analytical methods used for detecting steroids include high performance liquid chromatography (High performance liquid chromatography, HPLC), liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (Gas chromatography-mass spectrometry, GC-MS), but these methods have long analysis time and large reagent consumption, and cannot meet the requirements of modern detection methods for rapidness and accuracy. Therefore, some rapid mass spectrometry methods have been developed, and ionization methods that are often used include electrospray ionization (Electrospray ionization, ESI), atmospheric pressure chemical ionization (Atmospheric pressure chemical ionization, APCI), and matrix-assisted laser desorption ionization (Matrix assisted laser desorption ionization, MALDI), but these ionization sources require at least two steps of sample pretreatment of the sample to be measured, and the conversion of samples of different material forms into analysis samples is complicated. In the beginning of the twentieth century, desorption electrospray ionization (Desorption electrospray ionization, DESI) mass spectrometry methods have emerged for direct rapid analysis of complex samples, however, this method has a clear polarity discrimination for the substances tested, and some weakly polar and nonpolar substances have very low ionization efficiency, and since steroids are a class of tetracyclic aliphatic compounds, most of which are very weakly polar substances, it is difficult to detect using the above analysis methods. In addition, dielectric barrier discharge ionization (Dielectric barrier discharge ionization, DBDI) is suitable for non-thermal stability and ionization of weak polar and nonpolar substances as a soft ionization source due to its low temperature and mild ionization characteristics. In 2014 subhraker i Saha et al, the combination of the leidenfrost effect (Leidenfrost phenomenon) with DBDI detected steroid substances with high sensitivity. When a liquid drips onto an object whose boiling point is far above that of the liquid, a layer of vapor is formed between the liquid drips and the scalding surface, which acts as a heat insulator to a certain extent, since the heat transfer of the vapor is much slower than that of the liquid, and the liquid evaporates at a much slower rate, a phenomenon known as the leidenfrost effect. The subhrasanti Saha and the like utilize the phenomenon to slowly evaporate the sample solvent and then release the molecules of the to-be-detected object, and compared with a thermal analysis method at a lower temperature, the thermal analysis method has the advantage that the analysis sensitivity is improved. However, the ionization mode used in the method is dielectric barrier discharge ionization, fragment ions are generated in sample molecules in the ionization process, and when an environment water body substrate sample with complex components is tested, an inaccurate quantitative result is easily caused, and the repeatability and the sensitivity are reduced. In addition, the method needs to perform extraction and sample pretreatment before testing, and the sample to be tested can be enriched and purified to obtain lower detection limit and better recovery rate, so that the requirements of a modern analysis method on accurate, sensitive and high-flux detection of the trace sample to be tested can not be met. In addition, the dielectric barrier discharge ionization ion source needs to use high-voltage power to generate plasma, helium is needed as carrier gas, the power consumption of the device is high, the volume is large, and the consumable is expensive.
Disclosure of Invention
The invention provides a rapid detection device for trace steroid in a water body, which aims to solve the problems of low quantitative accuracy, poor repeatability, insufficient sensitivity, high detection limit, necessary pretreatment of a sample to be detected, large sample consumption volume, high consumption of consumable materials of the device, high power consumption and the like.
The rapid detection device for trace steroid in water body comprises a mass spectrometer, an ionization mechanism and a sample processing mechanism.
The sample processing mechanism comprises a volatile solvent introducing mechanism, a heating transmission mechanism and an evaporation enrichment injection mechanism, wherein a conical nozzle 15 of the evaporation enrichment injection mechanism corresponds to a mass spectrum inlet 21 of the mass spectrometer; an ionization region is arranged above the space between the conical nozzle 15 and the mass spectrum inlet 21, and an ionization source is arranged above the mass spectrum inlet; a third carrier gas pipe 17 is arranged at the position corresponding to the light outlet hole of the ionization source, and a third flowmeter 18 is arranged on the third carrier gas pipe 17;
the volatile solvent introducing mechanism comprises a volatile solvent storage tank 5, a first air carrying pipe 2 is arranged on one side of the volatile solvent storage tank 5, one end of the first air carrying pipe 2 extends into the inner bottom of the volatile solvent storage tank 5, the other end of the first air carrying pipe 2 is positioned outside the volatile solvent storage tank 5, and a first flowmeter 3 is arranged at the extending end of the first air carrying pipe 2;
the heating transmission mechanism comprises a main pipe 10 and a heating sleeve 12; one end of the main pipe 10 is an L-shaped inlet end, the other end of the main pipe 10 is an outlet end, and one side of the middle part of the main pipe 10 is communicated with the second gas carrying pipe 8; a second flowmeter 9 is arranged on the second carrier gas pipe 8; the inlet end of the main pipe 10 extends into the volatile solvent storage tank 5 from the top of the volatile solvent storage tank 5, and the heating sleeve 12 is sleeved on the main pipe 10 at one side of the outlet end;
the evaporation enrichment injection mechanism comprises a tubular body, one end of the body is a guide pipe 13, the other end of the body is a conical nozzle 15, and the middle part of the body is an evaporation cavity 14; a sample groove 141 is radially arranged on one side in the evaporation cavity 14, a sample injection hole 142 is formed on the other side of the evaporation cavity 14 coaxially corresponding to the sample groove 141, and a cover 16 is arranged at the sample injection hole 142; the guide pipe 13 of the evaporation enrichment injection mechanism is communicated with the outlet end of the main pipe 10;
when the device works, the introduced first carrier gas 1 is mixed with the volatile solvent 4 to form a first mixed gas 6, and then is combined with the introduced second carrier gas 7 to form a second mixed gas 11; the temperature of the evaporating cavity 14 reaches the Leidenford effect point of the solution to be detected, the solution to be detected is added into the sample tank 141 of the evaporating cavity 14, the solution to be detected generates the Leidenford effect under the action of the second mixed gas 11 and the third carrier gas 19, and the solution to be detected is sprayed 15 into an ionization region through a conical nozzle; the steroid molecules are ionized into steroid ions; and is sucked into a mass spectrometer, and mass spectrograms and selective ion flow diagrams of steroid detected objects are obtained through detection of the mass spectrometer;
when the device works in a positive ion mode, a voltage of-0.5 to-6 kV is applied to a mass spectrum inlet 21, the flow rate of the dry gas 22 flowing through the outside of a mass spectrometer sample inlet tube 23 is 1-10L/min, and the temperature is 100-400 ℃; the volatile solvent 4 in the volatile solvent storage tank 5 is toluene; the first carrier gas 1 is introduced into the first carrier gas pipe 2, the second carrier gas 7 is introduced into the second carrier gas pipe 8, the third carrier gas 19 is introduced into the third carrier gas pipe 17, and the first carrier gas 1, the second carrier gas 7 and the third carrier gas 19 are all nitrogen; the flow rate of nitrogen in the first carrier gas 1 is 20-100 ml/min, the flow rate of nitrogen in the second carrier gas 7 is 100-500 ml/min, and the flow rate of nitrogen in the third carrier gas 19 is 50-400 ml/min.
The further defined technical scheme is as follows:
the mass spectrometer is a mass spectrometer such as a time-of-flight mass spectrometer or a quadrupole mass spectrometer.
The ionization source is a vacuum ultraviolet discharge lamp 20.
The inner diameter of the main pipe 10 is 10-15 mm; the conical nozzle 15 is coaxial with the mass spectrum inlet 21, and the distance between the conical nozzle 15 and the mass spectrum inlet 21 in the horizontal direction is 15-20 mm.
The light outlet of the vacuum ultraviolet discharge lamp 20 is perpendicular to the mass spectrum inlet 21, the distance between the light outlet and the mass spectrum inlet 21 in the horizontal direction is 5-10 mm, and the distance in the vertical direction is 2-8 mm.
The inner diameter of the conduit 13 is 6 to 8 mm, and the outer diameter is the same as the inner diameter of the main pipe 10.
The sample groove 141 in the evaporation cavity 14 is a hemispherical groove with a depth of 4 mm, and the diameter of the sample inlet 142 is 4-7 mm.
The nozzle of the conical nozzle 15 is provided with an overhanging tubular nozzle, the inner diameter of the tubular nozzle is 2 mm, and the length of the tubular nozzle is 3-8 mm.
The first, second and third flowmeters 3, 9 and 18 are all float flowmeters.
The beneficial technical effects of the invention are as follows:
1. the adopted atmospheric pressure photoionization ion source has higher ionization efficiency on steroid substances, does not need sample pretreatment operation, and is suitable for detecting the steroid substances in various natural water bodies. Atmospheric pressure mass spectrometry methods commonly used for analysis of steroid substances are as follows: electrospray ionization (Electro spray ionization, ESI) and desorption electrospray ionization (Desorption electrospray ionization, DESI) present a significant polarity discrimination for the species being tested, and are very inefficient for some weakly polar and non-polar species; the steroid molecules contain hydroxyl or carbonyl, have weak polarity, and have poor ionization effect by using the method; atmospheric pressure photo-ionization source is a soft ionization source, is nonpolar and is relatively easier to detect and analyze for steroid substances. Atmospheric photoionization is used as an open type ion source, has higher tolerance to sample matrixes, is less interfered by salts in matrixes and can obtain better test results without pretreatment operation for the water matrixes compared with electrospray ionization (Electrospray ionization, ESI) and atmospheric chemical ionization (Atmospheric pressure chemical ionization, APCI), so that the device is more suitable for various natural water matrixes, such as river water, surface water, domestic water, industrial wastewater and the like.
2. The device has accurate qualitative and quantitative properties and good stability. The atmospheric pressure photoionization source adopted by the device has low ionization energy, is a mild ionization source, ionizes the molecules of the object to be detected into molecular ions by emitting photons of 10.6 and eV, almost does not generate fragment ions, and improves the accuracy and stability of mass spectrometry qualitative and quantitative properties; the relative standard deviation calculated when the device continuously tests methyltestosterone with the concentration of 100 pg/ml for five times is only 8.14%, and the relative standard deviation obtained when methyltestosterone with the concentration of 50ng/ml is tested within three days is only 3.98%, which indicates that the device has good stability and repeatability; the quantitative range can reach 3 orders of magnitude when the methyltestosterone is tested by the device, and the methyltestosterone can be accurately quantified in the concentration range from 100 pg/ml to 250 ng/ml, so that the quantitative requirement of the conventional test of the environmental water body is met.
3. The device has high sensitivity, low detection limit and small sample consumption. The device utilizes the Leidenfrost effect in the test, when a liquid drop is dropped on a metal surface with the temperature far exceeding the boiling point of the liquid drop, a layer of steam is formed between the liquid drop and the scalding surface, the steam plays a role in heat insulation to a certain extent because the heat transfer of the steam is much slower than that of the liquid, the liquid drop is not boiled rapidly but evaporates slowly, the phenomenon is called the Leidenfrost effect, and the temperature of the metal surface where the physical phenomenon occurs is called the Leidenfrost effect point (Leidenfrost temperature); the whole sample evaporation enrichment mechanism in the device is made of stainless steel metal materials, the temperature is kept at the Leidenfrost effect point of the test solution, liquid drops are dripped on a sample groove 141 of the sample evaporation enrichment mechanism during the test, the liquid drops slowly evaporate on the sample groove 141, steroid molecules are immediately released at the moment of complete evaporation of the liquid drop solvent, and the steroid molecules are effectively enriched and concentrated in the process; the conical nozzle 15 in the sample evaporation enrichment mechanism is designed to be funnel-shaped, so that the molecular distribution is more concentrated when steroid molecules are sprayed to an ionization region by the sample evaporation enrichment mechanism; the sample tank 141 and the cover 16 of the evaporating cavity 14 can effectively avoid the escape of steroid molecules in the test process, the design of the structure of the sample evaporating and enriching mechanism improves the sensitivity of the device test, the detection limit of the device for progesterone molecules is only 10 pg/mL, and the sensitivity is improved by 3 orders of magnitude compared with the LC-APCI-MS/MS method (the detection limit of progesterone molecules is 6 ng/mL); the improvement of sensitivity can meet the analysis and detection of trace samples, breaks the limit of the test volume of the samples, and can complete the test by only one drop of solution in the experiment because of the special structure of the sample evaporation and enrichment mechanism of the device, the test volume is only 2-10 mu L, and the sample consumption is smaller compared with the test volume of 50 mu L in the DBDI-MS/MS method.
4. The device has simple structure, low material consumption and low power consumption. The carrier gas used by the device is nitrogen, and is relatively low in cost and easy to obtain compared with helium, argon and the like used by the DBDI-MS/MS method; the heating mantle 12 and the vacuum ultraviolet discharge lamp 20 used in the present method have very little power consumption, except for the mass spectrometer.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention.
Fig. 2 (a) is a schematic structural diagram of a sample evaporation enrichment injection mechanism.
FIG. 2 (b) is a cross-sectional view of the sample evaporative enrichment injection mechanism.
FIG. 3 is a mass spectrum obtained by testing a river water sample in the positive ion mode of a mass spectrometer according to the present invention.
Figure 4 is a flow chart of selected ions obtained in the present invention when methyltestosterone in river water is tested in the positive ion mode of the mass spectrometer.
Figure 5 is a standard graph obtained by testing methyltestosterone standard solutions in the positive ion mode of a mass spectrometer according to the present invention.
Fig. 6 is a mass spectrum obtained by testing a surface water sample in a positive ion mode of a mass spectrometer according to the present invention.
Fig. 7 is a selective ion flow diagram obtained in the present invention when testing progesterone in surface water in mass spectrometer positive ion mode.
Fig. 8 is a standard graph obtained by testing a progesterone standard solution in the positive ion mode of a mass spectrometer according to the present invention.
Number in the upper diagram: the device comprises a first carrier gas 1, a first carrier gas pipe 2, a first flowmeter 3, a volatile solvent 4, a volatile solvent storage tank 5, a first mixed gas 6, a second carrier gas 7, a second carrier gas pipe 8, a second flowmeter 9, a main pipe 10, a second mixed gas 11, a heating jacket 12, a conduit 13, an evaporation cavity 14, a conical nozzle 15, a cover 16, a third carrier gas pipe 17, a third flowmeter 18, a third carrier gas 19, a vacuum ultraviolet discharge lamp 20, a mass spectrum inlet 21, a drying gas 22 and a mass spectrometer sample injection pipe 23.
Detailed Description
The invention is further described by way of examples with reference to the accompanying drawings.
Example 1
Referring to fig. 1, a rapid detection device for trace steroid in a water body comprises a mass spectrometer, an ionization mechanism and a sample processing mechanism, wherein the mass spectrometer is a time-of-flight mass spectrum.
The sample processing mechanism comprises a volatile solvent introducing mechanism, a heating transmission mechanism and an evaporation enrichment spraying mechanism, wherein an overhanging tubular nozzle is arranged at the nozzle of the conical nozzle 15 of the evaporation enrichment spraying mechanism, the inner diameter of the tubular nozzle is 2 mm, and the length of the tubular nozzle is 6 mm. The conical nozzle 15 of the evaporative enrichment injection mechanism is coaxial with the mass spectrometry inlet 21 of the mass spectrometer, and the distance between the conical nozzle 15 and the mass spectrometry inlet 21 in the horizontal direction is 18 mm. An ionization region is arranged above the evaporation enrichment injection mechanism between the conical nozzle 15 and the mass spectrum inlet 21 of the mass spectrometer, and an ionization source is arranged above the mass spectrum inlet 21 and is a vacuum ultraviolet discharge lamp 20. A third carrier tube 17 is installed at a position corresponding to the light outlet hole of the vacuum ultraviolet discharge lamp 20, and a third flowmeter 18 is installed on the third carrier tube 17. The exit aperture of the vacuum uv discharge lamp 20 was perpendicular to the mass spectrometry entrance 21, the distance between the exit aperture and the mass spectrometry entrance 21 in the horizontal direction was 7 mm, and the distance in the vertical direction was 5 mm.
The volatile solvent introducing mechanism comprises a volatile solvent storage tank 5, a first air carrying pipe 2 is arranged on one side of the volatile solvent storage tank 5, one end of the first air carrying pipe 2 extends into the inner bottom of the volatile solvent storage tank 5, the other end of the first air carrying pipe 2 is positioned outside the volatile solvent storage tank 5, and a first flowmeter 3 is arranged on the extending end of the first air carrying pipe 2.
The heat transfer mechanism includes a main tube 10 and a heating sleeve 12. The inner diameter of the main pipe 10 is 12 mm, one end of the main pipe 10 is an L-shaped inlet end, the other end of the main pipe 10 is an outlet end, and one side of the middle part of the main pipe 10 is communicated with the second gas carrying pipe 8; a second flowmeter 9 is arranged on the second carrier gas pipe 8; the inlet end of the main pipe 10 extends into the volatile solvent storage tank 5 from the top of the volatile solvent storage tank 5, and the heating sleeve 12 is sleeved on the main pipe 10 at one side of the outlet end.
The first, second and third flowmeters 3, 9 and 18 are all float flowmeters.
Referring to fig. 2 (a) and 2 (b), the evaporation enrichment injection mechanism comprises a tubular body, one end of the body is a conduit 13, the inner diameter of the conduit 13 is 7 mm, and the outer diameter is the same as the inner diameter of the main pipe 10; the other end of the body is a conical nozzle 15, and the middle part of the body is an evaporation cavity 14. A sample groove 141 is radially arranged on one side in the evaporation cavity 14, a sample injection hole 142 is formed on the other side of the evaporation cavity 14 coaxially corresponding to the sample groove 141, and a cover 16 is arranged at the sample injection hole 142. The sample groove 141 in the evaporation cavity 14 is a hemispherical groove with the depth of 4 mm, and the diameter of the sample inlet 142 is 6 mm; the conduit 13 of the evaporative enrichment injection mechanism communicates with the outlet end of the main pipe 10.
The working principle of the invention is described as follows:
a first carrier gas 1 is introduced from a first carrier gas pipe 2, a volatile solvent 4 is converted from a liquid state into a gaseous state through a bubbling method, and the gaseous state is mixed in a volatile solvent storage tank 5 to obtain a first mixed gas 6; then merging the mixed gas with a second carrier gas 7 which is introduced by a second carrier gas pipe 8 to obtain a second mixed gas 11; a third carrier gas 19 is introduced through a third carrier gas pipe 17; after the temperature of the evaporating cavity 14 reaches the leidenfrost effect point of the test solution, placing the test solution containing steroid molecules into the sample groove 141 of the evaporating cavity 14 through the sample inlet 142, and covering the sample inlet 142 with the cover 16; under the purge of the mixed gas 11, the test solution generates a leidenfrost effect in the sample tank 141, the solvent evaporates slowly, steroid molecules are released immediately at the moment of complete evaporation of the solvent, and the steroid molecules are sprayed out to reach an ionization region through the conical nozzle 15 of the evaporation enrichment spraying mechanism; the energy of photons emitted by the vacuum ultraviolet discharge lamp 20 in the ionization region that are absorbed by the steroid molecules are ionized into steroid ions; the steroid ions are immediately absorbed into the mass spectrometer by the mass spectrometer sampling tube 23 after being scattered into the mass spectrometry area, and the mass spectrogram and the selective ion flow chart of the steroid molecules are obtained after the detection of the mass spectrometer.
When the device works in a positive ion mode, a voltage of-3.5 kV is applied to the mass spectrum inlet 21, the flow rate of the dry gas 22 flowing through the outside of the mass spectrum sample inlet tube 23 is 5L/min, and the temperature is 325 ℃; the volatile solvent 4 in the volatile solvent storage tank 5 is toluene; the first carrier gas 1 is introduced into the first carrier gas pipe 2, the second carrier gas 7 is introduced into the second carrier gas pipe 8, the third carrier gas 19 is introduced into the third carrier gas pipe 17, and the first carrier gas 1, the second carrier gas 7 and the third carrier gas 19 are all nitrogen; the nitrogen flow rate in the first carrier gas 1 was 40 ml/min, the nitrogen flow rate in the second carrier gas 7 was 350 ml/min, and the nitrogen flow rate in the third carrier gas 19 was 100 ml/min.
The device is applied to the detection of methyltestosterone in river water.
A series of standard solutions were first prepared. Accurately weighing methyltestosterone 100 mg, placing into a 10 ml volumetric flask, dissolving with methanol, and fixing volume to obtain mother liquor 1 with methyltestosterone concentration of 10 mg/ml; using methanol to carry out gradient dilution on the mother liquor 1 to obtain mother liquor 2 with methyltestosterone concentration of 2.5 mg/ml, 1 mg/ml, 500 ng/ml, 100 ng/ml, 50ng/ml, 10 ng/ml and 1 ng/ml in sequence; accurately weighing medroxyprogesterone acetate 5 mg, putting into a 10 ml volumetric flask, dissolving with methanol, and fixing the volume to obtain an internal standard 1 with the medroxyprogesterone acetate concentration of 500 ng/ml; diluting the internal standard 1 by 10 times by using methanol to obtain an internal standard 2 with the concentration of medroxyprogesterone acetate of 50 ng/ml; according to mother liquor 2: internal standard 2: deionized water: the methyltestosterone concentration was formulated as a series of standard solutions of 250 ng/ml, 100 ng/ml, 50ng/ml, 10 ng/ml, 5 ng/ml, 1 ng/ml and 100 pg/ml in the order of volume ratio of methanol=1:1:1:7.
And (3) according to the parameter setting device, after the device reaches experimental conditions, preparing a standard curve by using the series of standard solutions, wherein the series of standard solutions at the moment are the test solutions. Respectively testing serial standard solutions in sequence from low concentration to high concentration, sucking 10 μl of the test solution by using a pipetting gun with a measuring range of 20 μl, dripping into the evaporation cavity 14, timely closing the cover 16, immediately collecting spectrum, and ending collecting spectrum after 1 min; the method comprises the steps of taking the peak integral area in a selected ion flow diagram of methyltestosterone in figure 4 collected by a mass spectrometer as a quantitative basis, taking the concentration of a test solution as an X axis, taking the ratio of the peak area of the selected ion flow diagram of methyltestosterone to the peak area of medroxyprogesterone acetate as a Y axis, establishing a standard curve shown in figure 5, fitting the standard curve to obtain a linear regression equation of y=0.066x+0.104, and obtaining a correlation coefficient R 2 0.99784, the dynamic range is 0.1-250 ng/ml.
River water samples were treated as follows, and a test solution was prepared using a mother liquor 2 having methyltestosterone concentration of 100 ng/ml, according to mother liquor 2: internal standard 2: river water: the mother solution 2 is diluted according to the volume ratio of methanol=1:1:1:7, and a river water solution with the methyltestosterone theoretical concentration of 10 ng/ml is obtained, and the river water solution at the moment is the test solution for the next step of test.
After the device has reached experimental conditions, a pipette with a measuring range of 20 μl is used to suck 10 μl of the test solution, the test solution is directly dripped into the evaporation cavity 14, the cover 16 is timely closed, the spectrum is immediately collected, the spectrum collection is finished after 1 min, the mass spectrum of the river water sample of FIG. 3 is obtained, and methyltestosterone (m/z 303.2319) is accurately tested. And the peak area of the selected ion flow diagram of methyltestosterone and medroxyprogesterone acetate is obtained, the ratio of the peak area of the selected ion flow diagram of methyltestosterone and medroxyprogesterone acetate obtained by the test is substituted into the linear regression equation of the standard curve, and the methyltestosterone concentration obtained by the test is 10.577 ng/ml and the recovery rate is 105.77 percent.
Example 2
The device construction and operation principle are the same as in example 1.
The different structural and process data in the device are described as follows:
the main pipe 10 has an inner diameter of 10 mm; the conical nozzle 15 is coaxial with the mass spectrometry inlet 21, and the distance between the conical nozzle 15 and the mass spectrometry inlet 21 in the horizontal direction is 15 mm.
The exit aperture of the vacuum ultraviolet discharge lamp 20 is perpendicular to the mass spectrum entrance 21, the distance between the exit aperture and the mass spectrum entrance 21 in the horizontal direction is 8, and the distance in the vertical direction is 6.
The inner diameter of the conduit 13 is 6 mm and the outer diameter is the same as the inner diameter of the main pipe 10.
The sample groove 141 in the evaporation chamber 14 is a hemispherical groove with a depth of 4 mm, and the diameter of the sample inlet 142 is 4 mm.
The nozzle of the conical nozzle 15 is provided with an overhanging tubular nozzle, the inner diameter of which is 2 mm and the length of which is 3 mm.
When the device works in the positive ion mode, a voltage of-3 kV is applied to the mass spectrum inlet 21, the flow rate of the dry gas 22 flowing through the outside of the mass spectrum sample inlet tube 23 is 3L/min, and the temperature is 350 ℃; the volatile solvent 4 in the volatile solvent storage tank 5 is toluene; the first carrier gas 1 is introduced into the first carrier gas pipe 2, the second carrier gas 7 is introduced into the second carrier gas pipe 8, the third carrier gas 19 is introduced into the third carrier gas pipe 17, and the first carrier gas 1, the second carrier gas 7 and the third carrier gas 19 are all nitrogen; the nitrogen flow rate in the first carrier gas 1 was 60 mL/min, the nitrogen flow rate in the second carrier gas 7 was 330 mL/min, and the nitrogen flow rate in the third carrier gas 19 was 200 mL/min.
The device of this example was applied to the detection of progesterone in surface water as follows.
A series of standard solutions were first prepared. Accurately weighing progesterone 100 mg, placing into a 10 ml volumetric flask, dissolving with methanol, and fixing volume to obtain mother liquor 1 with progesterone concentration of 10 mg/ml; gradient dilution of mother liquor 1 with methanol gave mother liquor 2 with a concentration of progesterone of 5 mg/ml, 2.5 mg/ml, 1 mg/ml, 500 ng/ml, 100 ng/ml, 50ng/ml, 10 ng/ml and 1 ng/ml in this order; accurately weighing medroxyprogesterone acetate 5 mg, putting into a 10 ml volumetric flask, dissolving with methanol, and fixing the volume to obtain an internal standard 1 with the medroxyprogesterone acetate concentration of 500 ng/ml; diluting the internal standard 1 by 10 times by using methanol to obtain an internal standard 2 with the concentration of medroxyprogesterone acetate of 50 ng/ml; according to mother liquor 2: internal standard 2: deionized water: the resulting mother liquor 2 was treated with methanol=1:1:1:7 in volume ratio, respectively, to obtain a series of standard solutions with progesterone concentrations of 500 ng/ml, 250 ng/ml, 100 ng/ml, 50ng/ml, 10 ng/ml, 5 ng/ml, 1 ng/ml and 100 pg/ml, in that order.
And (3) according to the parameter setting device, after the device reaches experimental conditions, preparing a standard curve by using the series of standard solutions, wherein the series of standard solutions at the moment are the test solutions. Respectively testing serial standard solutions in sequence from low concentration to high concentration, sucking 10 μl of the test solution by using a pipetting gun with a measuring range of 20 μl, directly dripping into the evaporation cavity 14, timely closing the cover 16, immediately collecting spectrum, and ending collecting spectrum after 1 min; taking the peak integral area in figure 7 collected by a mass spectrometer as a quantitative basis, taking the concentration of a test solution as an X axis, taking the ratio of the peak area of a selected ion flow graph of progesterone and medroxyprogesterone acetate as a Y axis, establishing a standard curve as shown in figure 8, fitting the standard curve to obtain a linear regression equation of y=0.074x+0.034, and obtaining a correlation coefficient R 2 0.99890, the dynamic range is 0.1-500 ng/ml.
Surface water samples were treated as follows, using a mother liquor 2 with a progesterone concentration of 100 ng/ml to prepare a test solution according to mother liquor 2: internal standard 2: surface water: the mother solution 2 is diluted according to the volume ratio of methanol=1:1:1:7, so that a surface water solution with the theoretical concentration of progesterone of 10 ng/ml is obtained, and the surface water solution at this time is the test solution for the next step of test.
After the device has reached experimental conditions, a pipette with a measuring range of 20 μl is used to suck 10 μl of the test solution, the test solution is directly dripped into the evaporation cavity 14, the cover 16 is timely closed, the spectrum is immediately collected, the spectrum collection is finished after 1 min, the quality spectrum of the surface water sample of FIG. 6 is obtained, and the progesterone (m/z 315.2319) is accurately tested. And the peak area of the selected ion flow diagram of the progesterone and the medroxyprogesterone acetate is obtained, the ratio of the peak area of the selected ion flow diagram of the progesterone and the medroxyprogesterone acetate obtained by the test is substituted into the linear regression equation of the standard curve, and the concentration of the progesterone obtained by the test is 10.661 ng/ml and the recovery rate is 106.61 percent.
Claims (9)
1. A rapid detection device for trace steroid in water body comprises a mass spectrometer and an ionization mechanism; the method is characterized in that: the device also comprises a sample processing mechanism;
the sample processing mechanism comprises a volatile solvent introducing mechanism, a heating transmission mechanism and an evaporation enrichment injection mechanism, wherein a conical nozzle (15) of the evaporation enrichment injection mechanism corresponds to a mass spectrum inlet (21) of the mass spectrometer; an ionization region is arranged above the space between the conical nozzle (15) and the mass spectrum inlet (21), and an ionization source is arranged above the mass spectrum inlet; a third carrier gas pipe (17) is arranged at the position corresponding to the light outlet hole of the ionization source, and a third flowmeter (18) is arranged on the third carrier gas pipe (17);
the volatile solvent introducing mechanism comprises a volatile solvent storage tank (5), a first carrier gas pipe (2) is arranged on one side of the volatile solvent storage tank (5), one end of the first carrier gas pipe (2) stretches into the inner bottom of the volatile solvent storage tank (5), the other end of the first carrier gas pipe (2) is positioned outside the volatile solvent storage tank (5), and a first flowmeter (3) is arranged at the extending end of the first carrier gas pipe (2);
the heating transmission mechanism comprises a main pipe (10) and a heating sleeve (12); one end of the main pipe (10) is an L-shaped inlet end, the other end of the main pipe (10) is an outlet end, and one side of the middle part of the main pipe (10) is communicated with the second gas carrying pipe (8); a second flowmeter (9) is arranged on the second carrier gas pipe (8); the inlet end of the main pipe (10) extends into the volatile solvent storage tank (5) from the top of the volatile solvent storage tank (5), and the heating sleeve (12) is sleeved on the main pipe (10) at one side of the outlet end;
the evaporation enrichment injection mechanism comprises a tubular body, one end of the body is a guide pipe (13), the other end of the body is a conical nozzle (15), and the middle part of the body is an evaporation cavity (14); a sample groove (141) is radially formed in one side of the evaporation cavity (14), a sample injection hole (142) is formed in the other side of the evaporation cavity (14) coaxially corresponding to the sample groove (141), and a cover (16) is arranged at the sample injection hole (142); the guide pipe (13) of the evaporation enrichment injection mechanism is communicated with the outlet end of the main pipe (10);
when the device works, the first carrier gas (1) is introduced to be mixed with the volatile solvent (4) to form a first mixed gas (6), and then the first mixed gas is combined with the second carrier gas (7) to form a second mixed gas (11); the temperature of the evaporation cavity (14) reaches the Leidenford effect point of the solution to be detected, the solution to be detected is added into a sample tank (141) of the evaporation cavity (14), the solution to be detected generates the Leidenford effect under the action of a second mixed gas (11) and a third carrier gas (19), and is sprayed (15) into an ionization region through a conical nozzle; the steroid molecules are ionized into steroid ions; and is sucked into a mass spectrometer, and mass spectrograms and selective ion flow diagrams of steroid detected objects are obtained through detection of the mass spectrometer;
when the device works in a positive ion mode, a voltage of-0.5 to-6 kV is applied to a mass spectrum inlet (21), the flow rate of dry gas (22) flowing through the outside of a mass spectrometer sample injection pipe (23) is 1-10L/min, and the temperature is 100-400 ℃; the volatile solvent (4) in the volatile solvent storage tank (5) is toluene; a first carrier gas (1) is introduced into the first carrier gas pipe (2), a second carrier gas (7) is introduced into the second carrier gas pipe (8), a third carrier gas (19) is introduced into the third carrier gas pipe (17), and the first carrier gas (1), the second carrier gas (7) and the third carrier gas (19) are all nitrogen; the flow rate of nitrogen in the first carrier gas (1) is 20-100 mL/min, the flow rate of nitrogen in the second carrier gas (7) is 100-500 mL/min, and the flow rate of nitrogen in the third carrier gas (19) is 50-400 mL/min.
2. The rapid detection device for trace steroid in a body of water according to claim 1, wherein: the mass spectrometer is a mass spectrometer such as a time-of-flight mass spectrometer or a quadrupole mass spectrometer.
3. The rapid detection device for trace steroid in a body of water according to claim 1, wherein: the ionization source is a vacuum ultraviolet discharge lamp (20).
4. A rapid detection device for trace steroids in a body of water according to claim 3, characterized in that: the light outlet hole of the vacuum ultraviolet discharge lamp (20) is perpendicular to the mass spectrum inlet (21), the distance between the light outlet hole and the mass spectrum inlet (21) in the horizontal direction is 5-10 mm, and the distance between the light outlet hole and the mass spectrum inlet in the vertical direction is 2-8 mm.
5. The rapid detection device for trace steroid in a body of water according to claim 1, wherein: the inner diameter of the main pipe (10) is 10-15 mm; the conical nozzle (15) is coaxial with the mass spectrum inlet (21), and the distance between the conical nozzle (15) and the mass spectrum inlet (21) in the horizontal direction is 15-20 mm.
6. The rapid detection device for trace steroid in a body of water according to claim 1, wherein: the inner diameter of the conduit (13) is 6-8 mm, and the outer diameter is the same as the inner diameter of the main pipe (10).
7. The rapid detection device for trace steroid in a body of water according to claim 1, wherein: the sample groove (141) in the evaporation cavity (14) is a hemispherical groove with the depth of 4-mm, and the diameter of the sample inlet hole (142) is 4-7 mm.
8. The rapid detection device for trace steroid in a body of water according to claim 1, wherein: the nozzle of the conical nozzle (15) is provided with an overhanging tubular nozzle, the inner diameter of the tubular nozzle is 2 mm, and the length of the tubular nozzle is 3-8 mm.
9. The rapid detection device for trace steroid in a body of water according to claim 1, wherein: the first flowmeter (3), the second flowmeter (9) and the third flowmeter (18) are all float flowmeters.
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| CN112908830B (en) * | 2019-12-04 | 2022-05-06 | 中国科学院大连化学物理研究所 | Atmospheric pressure photoionization source device for detecting volatile organic compounds in water |
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| CN105588872A (en) * | 2016-03-02 | 2016-05-18 | 中国科学技术大学 | Quick on-line atmospheric photo ionization mass spectrum device for effective constituent in complex substrate |
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| CN105588872A (en) * | 2016-03-02 | 2016-05-18 | 中国科学技术大学 | Quick on-line atmospheric photo ionization mass spectrum device for effective constituent in complex substrate |
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