CN108593756A - The device for fast detecting of trace steroids in a kind of water body - Google Patents
The device for fast detecting of trace steroids in a kind of water body Download PDFInfo
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- CN108593756A CN108593756A CN201810705360.XA CN201810705360A CN108593756A CN 108593756 A CN108593756 A CN 108593756A CN 201810705360 A CN201810705360 A CN 201810705360A CN 108593756 A CN108593756 A CN 108593756A
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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
Abstract
The present invention relates to a kind of device for fast detecting of trace steroids in water body.Including mass spectrograph, ionization mechanism and sample treatment mechanism；Sample treatment mechanism includes solvent flashing retraction mechanism, heat transfer mechanism and evaporation enrichment injection equipment；Conical nozzle in evaporation enrichment injection equipment corresponds to mass spectrometric mass spectrum entrance, and the top between conical nozzle and mass spectrum entrance is ionized space；When work, the first carrier gas for being passed through is mixed to form the first gaseous mixture with solvent flashing, then converges with the second carrier gas being passed through to obtain the second gaseous mixture；The temperature of chamber to be evaporated reach sample to be tested Leiden Fu Luosi special efficacys should point, will detected solution be added evaporation cavity sample cell in；Detected solution generates Leiden Fu Luosi special efficacys under the second gaseous mixture and third carrier gas effect and answers, and sprays into ionized space by conical nozzle；Steroid molecule is ionized to steroids ion；And it is inhaled into mass spectrograph, the mass spectrogram for obtaining steroids measured object and selection ion flow graph are detected through mass spectrograph.
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular to the quick detection dress of trace steroids in a kind of water body
It sets.
Background technology
Steroids is also known as steroidal, is one kind of lipid, it has extremely strong endocrine disrupting and bioactivity, extremely low
Just it can cause human body dysgenesia, abnormal behavior, endocrine disturbance even cancer etc. under concentration.Steroids in environment mainly comes
Derived from the discharge of wastewater of the draining of people and vertebrate, the use of artificial synthesized steroid medicine and hospital, pharmacy corporation.Due to
Sewage treatment plant cannot be fully erased to steroid substances, and remaining steroids will be discharged into environment water.The study found that
Steroids Impacts on ecology and environment in water body is the most direct, is present in steroid substances in water body not only at much lower concentrations
Sexual interference can be caused to aquatile, while the mankind drink these water bodys and the edible biology through water pollution and can also cause respectively
Kind disease.It is thus the important means for carrying out risk assessment and prevention and cure of pollution to the Accurate Determining of remaining steroids in water body,
It is also the basis for ensureing Environmental security and food security.
In recent years, the research of steroids context of detection receives more and more attention, with the development of science and technology and people
To the general concern of food and Environmental security, the requirement in terms of detection method sensitivity is also higher and higher.It is usual to detect steroids
The analysis method used has high performance liquid chromatography（High performance liquid chromatography, HPLC）、
Liquid Chromatography-Mass Spectrometry（Liquid chromatography-mass spectrum, LC-MS）With gas-chromatography-matter
Compose combination method（Gas chromatography-mass spectrum, GC-MS）, but these method analysis times it is longer and
It is big to consume amount of reagent, modern measure method cannot be met and fast and accurately required.Therefore some quick mass spectrometric analysis methods are met the tendency of
And give birth to, the ioning method being commonly used has electron spray ionisation（Electrospray ionization, ESI）, atmospheric pressure
Learn ionization（Atmospheric pressure chemical ionization, APCI）It is ionized with Matrix Assisted Laser Desorption
（Matrix assisted laser desorption ionization, MALDI）Deng, still, these ionization sources needs pair
Sample to be tested carries out the sample pretreatment of at least two steps, and the sample of different material form is transformed into analysis sample, operation compared with
It is complicated.In earlier 2000s, occur can be used for the desorption electrospray ionization that complex sample is directly quickly analyzed
（Desorption electrospray ionization, DESI）Mass spectrometric analysis method, however this method is for surveyed object
There are apparent polarity to discriminate against for matter, some low poles and nonpolar substance ionizing efficiency are very low, since steroids is one kind four
The very weak substance of cycloaliphatic hydrocarbon compound, mostly polarity uses the more difficult detection of above-mentioned analysis method.In addition to this, dielectric impedance
Electric discharge ionization（Dielectric barrier discharge ionization, DBDI）As a kind of soft ionization source Yin Qiwen
It spends low and ionizes mild feature, be suitble to the ionization of non-thermostable and low pole and apolar substance.2014
Subhrakanti Saha etc. answer Leiden Fu Luosi special efficacys（Leidenfrost phenomenon）Combine height with DBDI
Sensitivity it detected steroid substances.When liquid, which drops in one piece, far to be surpassed on the object of its boiling point, in drop and blanching table
One layer of steam can be formed between face, since the heat transfer ratio liquid of steam is more slowly, this layer of steam plays heat-insulated to a certain extent
Effect so that the speed of liquid evaporation is slowed down significantly, this phenomenon is referred to as Leiden Fu Luosi special efficacys and answers.Subhrakanti
Saha etc. releases determinand molecule again after making sample solvent slow evaporation using this phenomenon, with the Thermal desorption under lower temperature
Method compares the sensitivity for improving analysis.However the ionization mode that this method uses is dielectric barrier discharge ionization, sample
Molecule will produce fragment ion in ionization process, when test composition complex environment aqueous samples sample, easily cause quantitative
As a result inaccurate, while repeatability and sensitivity can also reduce.Moreover, this method is needed before test by extracting this
Sample pretreatment step will could obtain lower detection limit and the preferable rate of recovery, still not after sample to be tested enriching and purifying
The testing requirements that Modern Methods are accurate to trace sample to be tested, sensitive and high-throughput can be met.In addition to this, dielectric impedance
Electric discharge ionization ion source needs to generate plasma using high voltage power supply, and helium is needed to do carrier gas, and the power consumption of device is very high,
Volume is larger, and consumptive material is expensive.
Invention content
Low in order to solve dosing accuracy, poor repeatability, sensitivity is inadequate, and detection limit is higher, and sample to be tested must be located in advance
The problems such as reason, sample consumption volume is big, and device consumptive material costliness power consumption is high, the present invention provides trace steroids in a kind of water body
Device for fast detecting.
The device for fast detecting of trace steroids includes mass spectrograph and ionization mechanism in a kind of water body, further includes sample treatment
Mechanism.
The sample treatment mechanism includes that solvent flashing retraction mechanism, heat transfer mechanism and evaporation are enriched with injection equipment,
The conical nozzle 15 of the evaporation enrichment injection equipment corresponds to the mass spectrometric mass spectrum entrance 21；15 He of the conical nozzle
Top between mass spectrum entrance 21 is ionized space, and the top of the mass spectrum entrance is equipped with ionization source；With going out for the ionization source
Unthreaded hole corresponding position is equipped with third carrier gas pipe 17, and third carrier gas pipe 17 is equipped with third flowmeter 18；
The solvent flashing retraction mechanism includes solvent flashing storage tank 5, and the side of solvent flashing storage tank 5 is equipped with the first carrier gas pipe 2,
Bottom in solvent flashing storage tank 5 is stretched into one end of first carrier gas pipe 2, and 2 other end of the first carrier gas pipe is located at solvent flashing storage tank 5
The overhanging end of outside, the first carrier gas pipe 2 is equipped with first flowmeter 3；
The heat transfer mechanism includes supervisor 10 and heating muff 12；One end of the supervisor 10 is L-shaped input end, supervisor
10 other end is outlet end, and 10 middle part sides of supervisor are connected to the second carrier gas pipe 8；The second carrier gas pipe 8 is equipped with second
Flowmeter 9；The input end of supervisor 10 is stretched by the top of solvent flashing storage tank 5 in solvent flashing storage tank 5, the heating muff 12
It is set on the supervisor 10 of outlet end side；
The evaporation enrichment injection equipment includes the ontology of tubulose, and one end of ontology is conduit 13, and the other end of ontology is taper
The middle part of nozzle 15, ontology is evaporation cavity 14；Side is radially provided with sample cell 141 in the evaporation cavity 14, same with sample cell 141
Corresponding 14 other side of evaporation cavity of axis offers sample holes 142, and lid 16 is set at sample holes 142；The evaporation is enriched with spraying machine
The conduit 13 of structure be connected to be responsible for 10 outlet end；
When work, the first carrier gas 1 and the solvent flashing 4 that are passed through are mixed to form the first gaseous mixture 6, then with the second carrier gas 7 for being passed through
Converge to form the second gaseous mixture 11；The temperature of chamber 14 to be evaporated reach detected solution Leiden Fu Luosi special efficacys should point, will be tested
The sample cell 141 of evaporation cavity 14 is added in solution, and detected solution generates Leiden in the case where the second gaseous mixture 11 and third carrier gas 19 act on
Not Loews special efficacy is answered, and enters ionized space by conical nozzle spray 15；Steroid molecule is ionized to steroids ion；And it is inhaled
Enter mass spectrograph, the mass spectrogram for obtaining steroids measured object and selection ion flow graph are detected through mass spectrograph；
It is in positive ion mode when work, applies the voltage of -0.5~-6 kV on mass spectrum entrance 21, flows through mass spectrograph sample feeding pipe 23
The flow velocity of external dry gas 22 is 1~10 L/min, and temperature is 100~400 DEG C；Volatilization in solvent flashing storage tank 5 is molten
Agent 4 is toluene；The first carrier gas 1 is passed through in first carrier gas pipe 2, the second carrier gas 7 being passed through in the second carrier gas pipe 8, third carrier gas pipe
17 are passed through third carrier gas 19, and first carrier gas 1, the second carrier gas 7 and third carrier gas 19 are nitrogen；Nitrogen in first carrier gas 1
Gas velocity is 20 ~ 100 ml/min, and the nitrogen flow rate in the second carrier gas 7 is 100 ~ 500 ml/min, the nitrogen in third carrier gas 19
Gas velocity is 50 ~ 400 ml/min.
The technical solution further limited is as follows：
The mass spectrograph is the mass spectrographs such as flight time mass spectrum or level four bars mass spectrum.
The ionization source is vacuum ultraviolet discharge lamp 20.
The internal diameter of the supervisor 10 is 10~15 mm；The conical nozzle 15 and mass spectrum entrance 21 are coaxial, conical nozzle 15
It is 15~20 mm the distance between in the horizontal direction with mass spectrum entrance 21.
The light hole of the vacuum ultraviolet discharge lamp 20 exists perpendicular to mass spectrum entrance 21, the light hole and mass spectrum entrance 21
The distance between horizontal direction is 5~10 mm, distance in vertical direction is 2~8 mm.
The internal diameter of the conduit 13 is 6~8 mm, and outer diameter is identical as the internal diameter of supervisor 10.
The hemispherical groove that sample cell 141 in the evaporation cavity 14 is 4 mm deeply, a diameter of the 4~7 of sample holes 142
mm。
The nozzle of the conical nozzle 15 is equipped with overhanging tubulose spout, and the internal diameter of tubulose spout is 2 mm, length 3
~8 mm.
The first flowmeter 3, second flowmeter 9 and third flowmeter 18 are suspended body flowmeter.
The advantageous effects of the present invention embody in the following areas：
1. the atmospheric pressure photoionization ion source used is higher for steroid substances ionizing efficiency, is not necessarily to sample pretreatment operates,
It is suitble to the detection of steroid substances in various natural waters.It is usually used in analyzing the atmospheric pressure mass spectrometric analysis method of steroid substances
Such as：Electron spray ionisation（Electro spray ionization, ESI）With desorption electron spray ionisation（Desorption
electrospray ionization, DESI）Deng discriminating against there are apparent polarity for surveyed substance, to some low poles and
Nonpolar substance ionizing efficiency is very low；Contain hydroxyl or carbonyl in steroid molecule, polarity is weaker, uses above method electricity
It is poor from effect；Atmospheric pressure photoionization source is a kind of soft ionization source, in contrast it is solid that analysis classes are more readily detected in nonpolarity discrimination
Alcohols material.Atmospheric pressure photoionization is as a kind of open type ion source relative to electron spray ionisation（Electrospray
ionization, ESI）And atmospheric pressure chemical ionization（Atmospheric pressure chemical ionization,
APCI）For the tolerance higher of sample substrate is not necessarily to by the interference smaller of salt in matrix for aqueous samples
Pretreatment operation can be obtained preferable test result, thus the present apparatus is more suitable for various natural water matrix, such as river water,
Surface water, domestic water, industrial wastewater etc..
2. the present apparatus is qualitative and quantitative accurate, stability is good.The present apparatus use atmospheric pressure photoionization source ionizing energy compared with
It is low, be a kind of mild ionization source, this ionization source by emit the photon of 10.6 eV by determinand molecular ionization be molecule from
Son is nearly free from fragment ion, improves mass spectrometry and quantitative Stability and veracity；Present apparatus follow-on test five times
The relative standard deviation being calculated when the methyltestosterone of a concentration of 100 pg/ml is only 8.14 %, and test concentrations are within three days
The relative standard deviation that the methyltestosterone of 50ng/ml obtains is only 3.98 %, illustrates that the stability of the present apparatus and repeatability are fine；
Quantification range can reach 3 magnitudes when the present apparatus tests methyltestosterone, from 100 pg/ml to the concentration range of 250 ng/ml
It is interior it is equal can to methyltestosterone carry out accurate quantitative analysis, meet the quantitative requirement of environment water routine test.
3. present apparatus high sensitivity, detection limit is low, and sample consumption is small.Leiden Fu Luosi is utilized in test in the present apparatus
Special efficacy is answered, and when drop, which drops in a deblocking temperature, far surpasses the metal surface of its boiling point, one can be formed between drop and blanching surface
Layer steam, since the heat transfer ratio liquid of steam is more slowly, this layer of steam plays heat-insulated effect to a certain extent, and drop is no longer
Rapid boiling but slow evaporation, this phenomenon are called Leiden Fu Luosi special efficacys and answer, the gold that this physical phenomenon can be made to occur
Metal surface temperature is called Leiden Fu Luosi special efficacys should point（Leidenfrost temperature ）；Sample evaporation in the present apparatus
Enrichment mechanism is integrally stainless steel metal material, and temperature be maintained at test solution Leiden Fu Luosi special efficacys should point, test
When drop dropped on the sample cell 141 of sample evaporation enrichment mechanism, drop slow evaporation on sample cell 141, steroids point
Son is deflected and released suddenly in the moment of drop solvent evaporating completely, and steroid molecule is concentrated by effective enrichment in this process；
Conical nozzle 15 in sample evaporation enrichment mechanism is designed to funnel-form, when steroid molecule evaporates the spray of enrichment mechanism by sample
Molecular distribution is more concentrated when directive ionized space；The sample cell 141 and lid 16 of evaporation cavity 14 during the test may be used
Effectively to avoid escaping for steroid molecule, the design of the above sample evaporation enrichment mechanism structure from improving the spirit of device to test
Sensitivity, the present apparatus only has 10 pg/mL for the detection limit of progesterone molecule, relative to LC-APCI-MS/MS methods（Progesterone
The detection of molecule limits 6 ng/mL）For sensitivity improve 3 magnitudes；The raising of sensitivity can meet point of trace samplings
Analysis detection, has broken the limitation to sample test volume, due to the special sample evaporation enrichment mechanism structure of the present apparatus, when experiment
Only need a drop solution that test can be completed, test volume only has 10 μ L of 2-, relative to test volume in DBDI-MS/MS methods
Sample consumption smaller for 50 μ L.
4. the present apparatus is simple in structure, consumptive material is cheap, small power consumption.The carrier gas that the present apparatus uses is nitrogen, compared to DBDI-
Relative moderate is easy to get for helium and argon gas that MS/MS methods use etc.；In addition to mass spectrograph, 12 He of heating mantle that this method uses
Power consumption all very littles of 20 the two parts of vacuum ultraviolet discharge lamp.
Description of the drawings
Fig. 1 is schematic structural view of the invention.
Fig. 2（a）The structural schematic diagram of enrichment injection equipment is evaporated for sample.
Fig. 2（b）The sectional view of enrichment injection equipment is evaporated for sample.
Fig. 3 is the mass spectrogram that the present invention tests that river water sample obtains under mass spectrograph positive ion mode.
The selection ion stream that Fig. 4 is obtained when being the methyltestosterone of the invention tested in river water under mass spectrograph positive ion mode
Figure.
Fig. 5 is the canonical plotting that the present invention tests that methyltestosterone standard solution obtains under mass spectrograph positive ion mode.
Fig. 6 is the mass spectrogram that the present invention tests that surface water obtains under mass spectrograph positive ion mode.
The selection ion stream that Fig. 7 is obtained when being the progesterone of the invention tested in surface water under mass spectrograph positive ion mode
Figure.
Fig. 8 is the canonical plotting that the present invention tests that progesterone standard solution obtains under mass spectrograph positive ion mode.
Serial number in upper figure：First carrier gas 1, the first carrier gas pipe 2, first flowmeter 3, solvent flashing 4, solvent flashing storage tank 5,
First gaseous mixture 6, the second carrier gas pipe 8, second flowmeter 9, the 10, second gaseous mixture 11 of supervisor, heating mantle 12, is led second carrier gas 7
Pipe 13, evaporation cavity 14, conical nozzle 15, lid 16, third carrier gas pipe 17, third flowmeter 18, third carrier gas 19, vacuum ultraviolet
Discharge lamp 20, mass spectrum entrance 21, dry gas 22, mass spectrograph sample feeding pipe 23.
Specific implementation mode
Below in conjunction with the accompanying drawings, the present invention is further described by embodiment.
Embodiment 1
Referring to Fig. 1, the device for fast detecting of trace steroids includes mass spectrograph, ionization mechanism and sample treatment machine in a kind of water body
Structure, mass spectrograph are flight time mass spectrum.
Sample treatment mechanism includes that solvent flashing retraction mechanism, heat transfer mechanism and evaporation are enriched with injection equipment, described
The nozzle of the conical nozzle 15 of evaporation enrichment injection equipment is equipped with overhanging tubulose spout, and the internal diameter of tubulose spout is 2 mm,
Length is 6 mm.The conical nozzle 15 and mass spectrometric mass spectrum entrance 21 of the evaporation enrichment injection equipment are coaxial, conical nozzle
15 and mass spectrum entrance 21 be 18 mm the distance between in the horizontal direction.15 He of conical nozzle of the evaporation enrichment injection equipment
Top between mass spectrometric mass spectrum entrance 21 is ionized space, and the top of the mass spectrum entrance 21 is equipped with ionization source, is ionized
Source is vacuum ultraviolet discharge lamp 20.Third carrier gas pipe 17, third are installed with the light hole corresponding position of vacuum ultraviolet discharge lamp 20
Third flowmeter 18 is installed on carrier gas pipe 17.The light hole of vacuum ultraviolet discharge lamp 20 is perpendicular to mass spectrum entrance 21, light hole
It is the distance between in the horizontal direction 7 mm with mass spectrum entrance 21, distance in vertical direction is 5 mm.
Solvent flashing retraction mechanism includes solvent flashing storage tank 5, and the side of solvent flashing storage tank 5 is equipped with the first carrier gas pipe
2, bottom in solvent flashing storage tank 5 is stretched into one end of the first carrier gas pipe 2, and 2 other end of the first carrier gas pipe is located at solvent flashing storage tank 5
Outside, first flowmeter 3 is installed on the overhanging end of the first carrier gas pipe 2.
Heat transfer mechanism includes supervisor 10 and heating muff 12.The internal diameter of supervisor 10 is 12 mm, and the one end for being responsible for 10 is
L-shaped input end, the other end for being responsible for 10 are outlet end, and 10 middle part sides of supervisor are connected to the second carrier gas pipe 8；Second carrier gas pipe
Second flowmeter 9 is installed on 8；The input end of supervisor 10 is stretched by the top of solvent flashing storage tank 5 in solvent flashing storage tank 5,
Heating muff 12 is sleeved on the supervisor 10 of outlet end side.
First flowmeter 3, second flowmeter 9 and third flowmeter 18 are suspended body flowmeter.
Referring to Fig. 2（a）And Fig. 2（b）, evaporation enrichment injection equipment includes the ontology of tubulose, and one end of ontology is conduit 13,
The internal diameter of conduit 13 is 7 mm, and outer diameter is identical as the internal diameter of supervisor 10；The other end of ontology is conical nozzle 15, the middle part of ontology
For evaporation cavity 14.Side is radially provided with sample cell 141 in evaporation cavity 14, another with the coaxial corresponding evaporation cavity 14 of sample cell 141
Side offers sample holes 142, and lid 16 is equipped at sample holes 142.Sample cell 141 in evaporation cavity 14 is the hemisphere of deep 4 mm
Connected in star, a diameter of 6 mm of sample holes 142；Evaporation enrichment injection equipment conduit 13 be connected to be responsible for 10 outlet end.
The operation principle of the present invention is described as follows：
First carrier gas 1 is passed through by the first carrier gas pipe 2, solvent flashing 4 is converted to gaseous state by Bubbling method by liquid, and molten volatilizing
Mixing, obtains the first gaseous mixture 6 in agent storage tank 5；Converge to obtain second with the second carrier gas 7 that the second carrier gas pipe 8 is passed through again and mix
Gas 11；Third carrier gas 19 is passed through by third carrier gas pipe 17；The temperature of chamber 14 to be evaporated reaches the Leiden Fu Luosite of test solution
After effect point, the test solution containing steroid molecule is put by sample holes 142 in the sample cell 141 of evaporation cavity 14, and
Close the lid 16 at sample holes 142；Solution is tested under the purging of gaseous mixture 11, Leiden not Lip river is generated in sample cell 141
This special efficacy is answered, solvent slow evaporation, and in the moment of solvent evaporating completely, steroid molecule is deflected and released suddenly, and is enriched with by evaporating
The conical nozzle 15 of injection equipment, which sprays, reaches ionized space；Steroid molecule absorbs the vacuum ultraviolet discharge lamp 20 of ionized space
The energy for the photon launched is ionized to steroids ion；Steroids ion drifts after mass analysis region immediately by mass spectrum
Instrument sample feeding pipe 23 sucks in mass spectrograph, and the mass spectrogram and selection ion flow graph of steroid molecule are obtained after mass spectrograph detects.
It is in positive ion mode when work, applies the voltage of -3.5 kV on mass spectrum entrance 21, flows through mass spectrograph sample feeding pipe 23
The flow velocity of external dry gas 22 is 5 L/min, and temperature is 325 DEG C；Solvent flashing 4 in solvent flashing storage tank 5 is first
Benzene；The first carrier gas 1 is passed through in first carrier gas pipe 2, the second carrier gas 7 being passed through in the second carrier gas pipe 8, third carrier gas pipe 17 is passed through
Three carrier gas 19, first carrier gas 1, the second carrier gas 7 and third carrier gas 19 are nitrogen；Nitrogen flow rate in first carrier gas 1 is
40 ml/min, the nitrogen flow rate in the second carrier gas 7 are 350 ml/min, and the nitrogen flow rate in third carrier gas 19 is 100 ml/
min。
The present apparatus is applied to the detection of methyltestosterone in river water below.
Series standard solution is prepared first.100 mg of methyltestosterone accurately is weighed, is put into 10 ml volumetric flasks, uses methanol
Simultaneously constant volume is dissolved, the mother liquor 1 of a concentration of 10 mg/ml of methyltestosterone is obtained；Using methanol to 1 gradient dilution of mother liquor, methyltestosterone is obtained
Concentration is followed successively by 2.5 mg/ml, 1 mg/ml, 500 ng/ml, 100 ng/ml, 50 ng/ml, 10 ng/ml and 1 ng/ml's
Mother liquor 2；5 mg of medroxyprogesterone acetate accurately is weighed, is put into 10 ml volumetric flasks, using methanol dissolving and constant volume, obtains acetic acid
The internal standard 1 of a concentration of 500 ng/ml of Medroxyprogesterone；10 times are diluted to internal standard 1 using methanol, it is a concentration of to obtain medroxyprogesterone acetate
The internal standard 2 of 50 ng/ml；According to mother liquor 2：Internal standard 2：Deionized water：Methanol=1:1:1:7 volume ratio prepare methyltestosterone concentration according to
Secondary is 250 ng/ml, 100 ng/ml, 50 ng/ml, 10 ng/ml, 5 ng/ml, 1 ng/ml and the serial of 100 pg/ml are marked
Quasi- solution.
Device is set according to above-mentioned parameter, after device has reached experiment condition, is made using above-mentioned series standard solution
Standard curve, series standard solution at this time is to test solution.According to the sequence of concentration from low to high, test is respectively successively
Row standard solution is drawn test 10 μ l of solution using the liquid-transfering gun that range is 20 μ l, is instilled in evaporation cavity 14, and close in time
Lid 16 adopts spectrum immediately, terminates to adopt spectrum after 1 min；With in the selection ion flow graph of the collected Fig. 4 methyltestosterone of mass spectrograph
Peak integral area is quantitative basis, to test a concentration of X-axis of solution, with the selection ion stream of methyltestosterone and medroxyprogesterone acetate
The ratio between figure peak area be Y-axis, establish the standard curve such as Fig. 5 shown in, fit standard curve obtain equation of linear regression for y=
0.066x+0.104, relative coefficient R2It is 0.99784, dynamic range is 0.1 ~ 250 ng/ml.
Lower surface treatment river water sample prepares test solution, according to mother using the mother liquor 2 of a concentration of 100 ng/ml of methyltestosterone
Liquid 2：Internal standard 2：River water：Methanol=1:1:1:7 volume ratio dilutes mother liquor 2, obtains the river that methyltestosterone theoretical concentration is 10 ng/ml
Aqueous solution, river water solution at this time is the test solution tested in next step.
After device has reached experiment condition, test 10 μ l of solution are drawn using the liquid-transfering gun that range is 20 μ l, directly
It instills in evaporation cavity 14, and close the cover 16 in time, adopts spectrum immediately, terminate to adopt spectrum after 1 min, obtain Fig. 3 river water sample matter
Spectrogram has accurately tested out methyltestosterone（m/z 303.2319）.And obtain the selection of methyltestosterone and medroxyprogesterone acetate from
Subflow figure peak area, the ratio between selection ion flow graph peak area of methyltestosterone and medroxyprogesterone acetate that test is obtained substitute into above-mentioned
In the equation of linear regression of standard curve, a concentration of 10.577 ng/ml of methyltestosterone that test obtains is calculated, the rate of recovery is
105.77 %。
Embodiment 2
Device is built with operation principle with embodiment 1.
Different structured datas and process data are described as follows in device：
The internal diameter of supervisor 10 is 10 mm；The conical nozzle 15 and mass spectrum entrance 21 are coaxial, conical nozzle 15 and mass spectrum entrance 21
It is 15 mm the distance between in the horizontal direction.
The light hole of vacuum ultraviolet discharge lamp 20 is perpendicular to mass spectrum entrance 21, and the light hole and mass spectrum entrance 21 are in level
The distance between direction is that 8, distance in vertical direction is 6.
The internal diameter of conduit 13 is 6 mm, and outer diameter is identical as the internal diameter of supervisor 10.
Sample cell 141 in evaporation cavity 14 is the hemispherical groove of deep 4 mm, a diameter of 4 mm of sample holes 142.
The nozzle of conical nozzle 15 is equipped with overhanging tubulose spout, and the internal diameter of tubulose spout is 2 mm, and length is 3 mm.
When working in positive ion mode, applies the voltage of -3 kV on mass spectrum entrance 21, flow through outside mass spectrograph sample feeding pipe 23
Dry gas 22 flow velocity be 3 L/min, temperature be 350 DEG C；Solvent flashing 4 in solvent flashing storage tank 5 is toluene；The
The first carrier gas 1 is passed through in one carrier gas pipe 2, the second carrier gas 7 being passed through in the second carrier gas pipe 8, third carrier gas pipe 17 is passed through third load
Gas 19, first carrier gas 1, the second carrier gas 7 and third carrier gas 19 are nitrogen；Nitrogen flow rate in first carrier gas 1 is 60
ML/min, the nitrogen flow rate in the second carrier gas 7 are 330 mL/min, and the nitrogen flow rate in third carrier gas 19 is 200 mL/min.
The present embodiment device is applied to the detection of progesterone in surface water below.
Series standard solution is prepared first.100 mg of progesterone accurately is weighed, is put into 10 ml volumetric flasks, uses methanol
Simultaneously constant volume is dissolved, the mother liquor 1 that progesterone concentrations are 10 mg/ml is obtained；Using methanol to 1 gradient dilution of mother liquor, progesterone is obtained
Concentration is followed successively by 5 mg/ml, 2.5 mg/ml, 1 mg/ml, 500 ng/ml, 100 ng/ml, 50 ng/ml, 10 ng/ml and 1
The mother liquor 2 of ng/ml；5 mg of medroxyprogesterone acetate accurately is weighed, is put into 10 ml volumetric flasks, using methanol dissolving and constant volume, is obtained
Obtain the internal standard 1 of a concentration of 500 ng/ml of medroxyprogesterone acetate；10 times are diluted to internal standard 1 using methanol, obtains medroxyprogesterone acetate
The internal standard 2 of a concentration of 50 ng/ml；According to mother liquor 2：Internal standard 2：Deionized water：Methanol=1:1:1:7 volume ratio is handled respectively
Obtained mother liquor 2 obtains progesterone concentrations and is followed successively by 500 ng/ml, 250 ng/ml, 100 ng/ml, 50 ng/ml, 10 ng/
The series standard solution of ml, 5 ng/ml, 1 ng/ml and 100 pg/ml.
Device is set according to above-mentioned parameter, after device has reached experiment condition, is made using above-mentioned series standard solution
Standard curve, series standard solution at this time is to test solution.According to the sequence of concentration from low to high, test is respectively successively
Row standard solution is drawn test 10 μ l of solution using the liquid-transfering gun that range is 20 μ l, is directly instilled in evaporation cavity 14, and in time
Close the cover 16 adopts spectrum immediately, terminates to adopt spectrum after 1 min；It is quantitative with the peak integral area in the collected Fig. 7 of mass spectrograph
Foundation selects the ratio between ion flow graph peak area for Y to test a concentration of X-axis of solution with progesterone and medroxyprogesterone acetate
Axis establishes the standard curve as shown in Fig. 8, and it is y=0.074x+0.034, phase that fit standard curve, which obtains equation of linear regression,
Close property coefficient R2It is 0.99890, dynamic range is 0.1 ~ 500 ng/ml.
Lower surface treatment surface water prepares test solution using the mother liquor 2 that progesterone concentrations are 100 ng/ml, according to
Mother liquor 2：Internal standard 2：Surface water：Methanol=1:1:1:7 volume ratio dilutes mother liquor 2, and acquisition progesterone theoretical concentration is 10 ng/ml
Earth's surface aqueous solution, earth's surface aqueous solution at this time is the test solution of test in next step.
After device has reached experiment condition, test 10 μ l of solution are drawn using the liquid-transfering gun that range is 20 μ l, directly
It instills in evaporation cavity 14, and close the cover 16 in time, adopts spectrum immediately, terminate to adopt spectrum after 1 min, obtain Fig. 6 surface waters
Mass spectrogram has accurately tested out progesterone（m/z 315.2319）.And obtain the selection of progesterone and medroxyprogesterone acetate
Ion flow graph peak area will be tested the ratio between obtained selection ion flow graph peak area of progesterone and medroxyprogesterone acetate and be substituted into
In the equation of linear regression for stating standard curve, it is 10.661 ng/ml, the rate of recovery that the progesterone concentrations that test obtains, which are calculated,
For 106.61 %.
Claims (9)
1. the device for fast detecting of trace steroids in a kind of water body, including mass spectrograph and ionization mechanism；It is characterized in that：Also wrap
Include sample treatment mechanism；
The sample treatment mechanism includes that solvent flashing retraction mechanism, heat transfer mechanism and evaporation are enriched with injection equipment, described
The conical nozzle of evaporation enrichment injection equipment（15）Correspond to the mass spectrometric mass spectrum entrance（21）；The conical nozzle（15）
With mass spectrum entrance（21）Between top be ionized space, the top of the mass spectrum entrance is equipped with ionization source；With the ionization source
Light hole corresponding position be equipped with third carrier gas pipe（17）, third carrier gas pipe（17）It is equipped with third flowmeter（18）；
The solvent flashing retraction mechanism includes solvent flashing storage tank（5）, solvent flashing storage tank（5）Side be equipped with the first carrier gas
Pipe（2）, the first carrier gas pipe（2）One end stretch into solvent flashing storage tank（5）Interior bottom, the first carrier gas pipe（2）The other end is waved
Send out solvent tank（5）Outside, the first carrier gas pipe（2）Overhanging end be equipped with first flowmeter（3）；
The heat transfer mechanism includes supervisor（10）And heating muff（12）；The supervisor（10）One end be L-shaped import
End, supervisor（10）The other end be outlet end, supervisor（10）Middle part side is connected to the second carrier gas pipe（8）；Second carrier gas
Pipe（8）It is equipped with second flowmeter（9）；Supervisor（10）Input end by solvent flashing storage tank（5）Top stretch into solvent flashing
Storage tank（5）It is interior, the heating muff（12）It is set in the supervisor of outlet end side（10）On；
The evaporation enrichment injection equipment includes the ontology of tubulose, and one end of ontology is conduit（13）, the other end of ontology is cone
Shape nozzle（15）, the middle part of ontology is evaporation cavity（14）；The evaporation cavity（14）Interior side is radially provided with sample cell（141）, with
Sample cell（141）Coaxial corresponding evaporation cavity（14）The other side offers sample holes（142）, sample holes（142）Place sets lid
（16）；The conduit of the evaporation enrichment injection equipment（13）It is connected to supervisor（10）Outlet end；
When work, the first carrier gas for being passed through（1）With solvent flashing（4）It is mixed to form the first gaseous mixture（6）, then be passed through second
Carrier gas（7）Converge to form the second gaseous mixture（11）；Chamber to be evaporated（14）Temperature reach the Leiden Fu Luosi special efficacys of detected solution
Evaporation cavity is added in detected solution by Ying Dian（14）Sample cell（141）, detected solution is in the second gaseous mixture（11）With third carrier gas
（19）The lower generation Leiden Fu Luosi special efficacys of effect are answered, and are sprayed by conical nozzle（15）Enter ionized space；Steroid molecule is electric
From at steroids ion；And it is inhaled into mass spectrograph, the mass spectrogram for obtaining steroids measured object and selection ion are detected through mass spectrograph
Flow graph；
Positive ion mode, mass spectrum entrance are in when work（21）The upper voltage for applying -0.5~-6 kV, flows through mass spectrograph sample feeding pipe
（23）External dry gas（22）Flow velocity be 1~10 L/min, temperature be 100~400 DEG C；Solvent flashing storage tank（5）It is interior
Solvent flashing（4）For toluene；First carrier gas pipe（2）Inside it is passed through the first carrier gas（1）, the second carrier gas pipe（8）Second be inside passed through
Carrier gas（7）, third carrier gas pipe（17）It is passed through third carrier gas（19）, first carrier gas（1）, the second carrier gas（7）With third carrier gas
（19）It is nitrogen；First carrier gas（1）Interior nitrogen flow rate is 20~100 mL/min, the second carrier gas（7）Interior nitrogen flow rate
For 100~500 mL/min, third carrier gas（19）Interior nitrogen flow rate is 50~400 mL/min.
2. the device for fast detecting of trace steroids in a kind of water body according to claim 1, it is characterised in that：The matter
Spectrometer is the mass spectrographs such as flight time mass spectrum or level four bars mass spectrum.
3. the device for fast detecting of trace steroids in a kind of water body according to claim 1, it is characterised in that：The electricity
It is vacuum ultraviolet discharge lamp from source（20）.
4. the device for fast detecting of trace steroids in a kind of water body according to claim 2, it is characterised in that：It is described true
Empty EUV discharge lamp（20）Light hole perpendicular to mass spectrum entrance（21）, the light hole and mass spectrum entrance（21）In the horizontal direction
The distance between for 5~10 mm, distance be in vertical direction 2~8 mm.
5. the device for fast detecting of trace steroids in a kind of water body according to claim 1, it is characterised in that：The master
Pipe（10）Internal diameter be 10~15 mm；The conical nozzle（15）With mass spectrum entrance（21）Coaxially, conical nozzle（15）And mass spectrum
Entrance（21）It is 15~20 mm the distance between in the horizontal direction.
6. the device for fast detecting of trace steroids in a kind of water body according to claim 1, it is characterised in that：It is described to lead
Pipe（13）Internal diameter be 6~8 mm, outer diameter with supervisor（10）Internal diameter it is identical.
7. the device for fast detecting of trace steroids in a kind of water body according to claim 1, it is characterised in that：The steaming
Send out chamber（14）Interior sample cell（141）For the hemispherical groove of deep 4 mm, sample holes（142）A diameter of 4~7 mm.
8. the device for fast detecting of trace steroids in a kind of water body according to claim 1, it is characterised in that：The cone
Shape nozzle（15）Nozzle be equipped with overhanging tubulose spout, the internal diameter of tubulose spout is 2 mm, and length is 3~8 mm.
9. the device for fast detecting of trace steroids in a kind of water body according to claim 1, it is characterised in that：Described
Flow meters（3）, second flowmeter（9）With third flowmeter（18）It is suspended body flowmeter.
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| CN201810705360.XA CN108593756B (en) | 2018-07-02 | 2018-07-02 | Quick detection device of trace steroid in water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109030615A (en) * | 2018-11-03 | 2018-12-18 | 宁波华仪宁创智能科技有限公司 | Thermal desorption device and mass spectrometric analysis method |
| CN112908830A (en) * | 2019-12-04 | 2021-06-04 | 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 |
| CN112951701A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | In-situ thermal desorption ionization source for mass spectrometry |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109030615A (en) * | 2018-11-03 | 2018-12-18 | 宁波华仪宁创智能科技有限公司 | Thermal desorption device and mass spectrometric analysis method |
| CN112908830A (en) * | 2019-12-04 | 2021-06-04 | 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 |
| 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 |
| CN112951701A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | In-situ thermal desorption ionization source for mass spectrometry |
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| CN108593756B (en) | 2023-10-20 |
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