CN108918720A - A kind of gas chromatographic detection device based on point discharge atom spectrum - Google Patents
A kind of gas chromatographic detection device based on point discharge atom spectrum Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 41
- 238000001228 spectrum Methods 0.000 title abstract description 13
- 238000004817 gas chromatography Methods 0.000 claims abstract description 28
- 239000013307 optical fiber Substances 0.000 claims abstract description 12
- 238000002470 solid-phase micro-extraction Methods 0.000 claims abstract description 10
- 238000001675 atomic spectrum Methods 0.000 claims abstract 7
- 239000007789 gas Substances 0.000 claims description 85
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000000559 atomic spectroscopy Methods 0.000 claims 3
- 230000003044 adaptive effect Effects 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 15
- 230000004888 barrier function Effects 0.000 abstract description 13
- 230000005284 excitation Effects 0.000 abstract description 9
- 239000012491 analyte Substances 0.000 abstract description 7
- 238000000295 emission spectrum Methods 0.000 abstract description 5
- 238000010183 spectrum analysis Methods 0.000 abstract description 2
- 238000002076 thermal analysis method Methods 0.000 abstract 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 48
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 41
- 229910052753 mercury Inorganic materials 0.000 description 41
- 238000004458 analytical method Methods 0.000 description 23
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 17
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- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
本发明公开一种基于尖端放电原子光谱的气相色谱检测装置，属于光谱分析技术领域，所述检测器包括：尖端放电装置，光谱检测器件。目标分析物通过固相微萃取富集后，在气相色谱仪的进样口中进行热解析，分析物经气相色谱分离后进入尖端放电微等离子体被原子化并激发，尖端放电装置的出口通过光纤连接所述光谱检测器件，所述检测器件通过检测元素特征发射波长从而对目标物进行分析。本发明提供的技术方案，利用尖端放电(PD)的微等离子体激发能力强和装置简单、紧凑、便携、微型化的特点,相较于现有的基于介质阻挡放电/微波等离子体原子发射光谱的气相色谱检测装置，其灵敏度更高，死体积更小，且能够长时间稳定工作。
The invention discloses a gas chromatography detection device based on a tip discharge atomic spectrum, which belongs to the technical field of spectrum analysis. The detector includes a tip discharge device and a spectrum detection device. After the target analyte is enriched by solid-phase microextraction, thermal analysis is carried out in the inlet of the gas chromatograph. After the analyte is separated by gas chromatography, it enters the tip discharge micro-plasma to be atomized and excited. The outlet of the tip discharge device passes through the optical fiber The spectrum detection device is connected, and the detection device analyzes the target object by detecting the characteristic emission wavelength of the element. The technical solution provided by the present invention utilizes the characteristics of strong micro-plasma excitation ability of tip discharge (PD) and simple, compact, portable and miniaturized devices, compared with the existing dielectric barrier discharge/microwave plasma atomic emission spectrum based The advanced gas chromatography detection device has higher sensitivity, smaller dead volume, and can work stably for a long time.
Description
Technical field
The present invention relates to field of spectral analysis technology more particularly to a kind of based on the highly sensitive of point discharge atom spectrum
And dead volume and dead time small gas chromatographic detection device.
Background technique
The method of Elemental Speciation Analysis mainly passes through combination instrument and realizes at present, these combination instruments generally include efficiently
The chromatographic isolations instruments such as liquid chromatogram (HPLC), gas-chromatography (GC) and Capillary Electrophoresis (CE) and Atomic absorption (AAS), original
The combination of the detecting instruments such as sub- fluorescence (AFS), inductively coupled plasma atomic emission spectrum and mass spectrum (ICP-OES/MS).?
In these combination instrumental methods, gas-chromatography-atom spectrum is because of simple, portable, quick analysis, low cost and offer member
Plain characteristic information becomes one of Elemental Speciation Analysis method the most widely studied and used at present.Meanwhile purging supplementary set and solid phase
The sample treatments technologies such as micro-extraction (SPME) are easy in conjunction with gas-chromatography, are significantly improved detection sensitivity, are reduced detection
Limit eliminates matrix interference and spectra1 interfer-.Although GC-AAS AFS ICP-OES ICP-MS be successfully used for each element form
Analysis, but their instruments and operating cost are higher, are difficult to bear in some developing countries and regions.Further, since GC and original
Sub-light spectrum combination needs long transmission line and complicated heating and temperature controlling device, and analyte condensation is adhered to tube wall and causes serious note
Recall effect, background with higher.Although these disadvantages can partially be overcome by shortening transmission line, commercial atomic spectrograph
Big size is still the unlimited obstacle for shortening delivery tube.Therefore, exploitation miniaturization, inexpensively, low energy consumption and low gas consumption
The atomic spectrograph of expense and to be used as GC detector further to overcome disadvantages mentioned above be attractive.
In the past few decades, various minisize plasma bodies have been used as reliable and effective atomic emission spectrum
(OES) excitaton source, including dielectric barrier discharge (DBD), capacitance coupling plasma (CCP) minimize MIP, low-power consumption ICP,
Point discharge (PD), solution cathode glow discharging (SCGD), liquid electrode plasma (LEP) etc..With usual plasma
If ICP is compared with MIP, microplasma has more compact and simpler appliance arrangement, lower gas and energy consumption,
It is convenient to operate, and can be used for constructing field analysis portable instrument.Therefore, microplasma OES can be used as AAS/AFS/ICP-OES/
ICP-MS, which is potentially substituted, is used as GC detector, it can as close possible to GC chromatographic column outlet, to improve sensitivity,
Analyte is reduced to the maximum extent to lose and reduce power consumption.Recently, DBD-OES is used successfully as multichannel and element is special
Property GC detector, determines halogenated hydrocarbons, volatility carbon compound and mercury shape.DBD-OES system is significant reduce instrument and
Analysis cost, the shortcomings that alleviating traditional GC detector based on atomic spectrograph.
Point discharge is another nonequilibrium state microplasma, it can also be generated under room temperature and atmospheric pressure
And it maintains.Compared with DBD, PD has higher excitation energy, can be significantly expanded and directly survey suitable for microplasma OES
Fixed element species range.In addition, being mentioned when PD is used as the substitute of DBD by the sensitivity that micro- plasma OES measures carbon
It is at least 10 times high.Sensitivity can be improved as GC detector in PD, because its volume is much smaller than DBD, PD being capable of maximum limit
Reduce dead volume and dead time in degree ground.Therefore, the present invention is used using PD-OES as a kind of powerful and compact GC detector
In the morphological analysis of highly sensitive mercury.In order to further increase sensitivity, simplifying sample pre-treatments and reduce matrix interference, adopt
Use headspace solid-phase microextraction (HS-SPME) as the sampling technique of GC-PD-OES.
Summary of the invention
The present invention is intended to provide a kind of gas chromatographic detection device based on point discharge atom spectrum, compared to existing
The gas chromatographic detection device based on dielectric barrier discharge, sensitivity is higher, and dead volume and dead time are shorter, and can
Long-term stable work.
In order to achieve the above objectives, the technical solution adopted by the present invention is as follows：
A kind of gas chromatographic detection device based on point discharge atom spectrum, including：Solid-phase micro-extracting device, gas phase
Chromatograph, detector；The solid-phase micro-extracting device includes fibre abstraction head；The detector includes：Point discharge device,
CCD detector part；On the fibre abstraction head enrichment detection object, fibre abstraction head be inserted into the gas chromatograph into
In sample mouth；The outlet of the gas chromatograph connects the import of the point discharge device, the outlet of point discharge device
The CCD detector part is connected by optical fiber.
Preferably, the point discharge device includes：Closed discharging chamber, two metal electrodes, exhaust emission tube
Road, high voltage power supply device；The tip of described two metal electrodes is each passed through two opposite side walls of the discharging chamber, and two
The tail end of a metal electrode is respectively positioned on outside the discharging chamber；Have between making a reservation between the tip of described two metal electrodes
Away from the tail end of two metal electrodes connects the output end of the high voltage power supply device；It is put with described in the exhaust emission tube road
Electric cavity connection.
Preferably, the discharging chamber is cylinder；Described two metal electrodes are located on same horizontal line；It is described
The lower end surface of discharging chamber is equipped with the first opening, and first opening is connected through a screw thread T-type pipe, the gas chromatograph
The outlet of capillary column is inserted into T-type pipe, and the outlet is made to enter discharging chamber and in two metal electrode lines
The interface of point, capillary column and T-type pipe passes through silica gel sealing；The side wall on the discharging chamber top is equipped with the second opening,
One end of the optical fiber passes through discharging chamber connection second opening, and the other end of optical fiber connects the CCD detector
Part.
Preferably, the material of described two metal electrodes is tungsten.
Preferably, the high voltage power supply device includes：Contact voltage regulator and transformer；The output of the contact voltage regulator
The input terminal of end connection transformer, the output end of transformer are separately connected the tail end of two metal electrodes.
Preferably, the T-type pipe includes upper interface, lower interface and side interface；The upper interface and lower interface are located at same
On axis, the side interface is set between the upper interface and lower interface；The upper interface and first opening pass through screw thread
Adaptation connection, the lower interface are adapted to connection with the outlet of the gas chromatograph；The side interface inputs discharge gas,
The discharge gas is identical as the carrier gas in the gas chromatograph；The T-type tubing matter is quartz；The T type pipe range
10mm, internal diameter 2.0mm, outer diameter 2.5mm.
Preferably, the discharge gas and the carrier gas are argon gas.
Preferably, in the gas chromatograph argon gas flow velocity be 60 milliliters/per minute；The high voltage power supply device
Output voltage is 2.9kV；Preset space length between the tip of described two metal electrodes is 3mm.
Preferably, a height of 10 ± 0.5mm of the discharging chamber, basal diameter are 22 ± 0.5 mm；The discharging chamber
Internal diameter be 8 ± 0.5mm.
Gas chromatographic detection device provided in an embodiment of the present invention based on point discharge atomic emission spectrum for the first time will
Gas chromatograph and point discharge device and CCD detecting element are combined, since point discharge is by the tip of two needlepoint electrodes
Between a kind of nonequilibrium state atmosphere gas electric discharge for generating, compared to dielectric barrier discharge, have stronger excitation ability and
The longer service life.Also, point discharge device is smaller than dielectric barrier discharge device volume, so that entire structure of the detecting device
It is simpler, compact, while capillary column outlet is closer from plasma, dead volume and dead time are smaller, and experiment shows this
The gas chromatographic detection device based on point discharge atom spectrum that inventive embodiments provide is based on medium compared to existing
The gas chromatographic detection device of barrier discharge, sensitivity is higher, and detection time is shorter, and being capable of long-term stable work.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the embodiment of the present invention；
Fig. 2 is the sectional view of point discharge device and interface T-type pipe in the embodiment of the present invention；
Fig. 3 is the top view of point discharge device in the embodiment of the present invention；
Connection schematic diagram of the Fig. 4 between mesohigh of embodiment of the present invention power supply unit and two metal electrodes；
Fig. 5 a is the spectrogram that argon gas makees DBD-OES generation under conditions of carrier gas；Fig. 5 b argon gas is made under conditions of carrier gas
The spectrogram that PD-OES is generated；Fig. 5 c is 30 μ g L under HS-SPME-GC-PD-OES and HS-SPME-GC-DBD-OES system-1
The typical chromatogram of methyl mercury and inorganic mercury standard solution and blank solution；
Fig. 6 a be various concentration methyl mercury and inorganic mercury HS-SPME-GC-PD-OES and HS-SPME-GC-PD-OES not
With the chromatogram signal strength comparison under system；Fig. 6 b is that methyl mercury graticule compares under different systems；Fig. 6 c is under different systems
The comparison of inorganic mercury graticule；
Fig. 7 a is influence diagram of the argon gas flow velocity to present apparatus sensitivity；Fig. 7 b is discharge voltage to present apparatus sensitivity
Influence diagram；Fig. 7 c is influence diagram of the electrode distance to present apparatus sensitivity；
Fig. 8 a is chromatogram of the various concentration mercury standard liquid by HS-SPME-GC-PD-OES；Fig. 8 b is 0.05ugL-1It arrives
1ugL-1The enlarged drawing of standard liquid chromatogram；Fig. 8 c is methyl mercury concentration (0.2ugL-1~50ugL-1) and its HS-SPME-GC-PD-
OES mercury emission peak peak area relational graph；Fig. 8 d is inorganic mercury concentration (0.05ugL-1~50ugL-1) and its HS-SPME-GC-
PD-OES mercury emission peak peak area relational graph；
Fig. 9 a is the precision of HS-SPME-GC-DBD-OES system；Fig. 9 b is the essence of HS-SPME-GC-PD-OES system
Density；
In Fig. 1 to Fig. 4,1 is solid-phase micro-extracting device, and 2 be gas chromatograph, and 31 be point discharge device, and 32 be CCD
Device is detected, 33 be optical fiber, and 301 be metal electrode, and 311 be exhaust emission tube road, and 341 be contact voltage regulator, and 351 be rainbow
Lamp transformer, 11 be fibre abstraction head, and 4 be cavity, and 5 be T-type pipe end suitable for reading, and 6 be T-type pipe side port end, and 7 be mouth under T type pipe
End, 8 be capillary outlet end, and 9 be O-ring seal.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing, to the present invention
It is further elaborated.
Fig. 1 is the structural schematic diagram of the embodiment of the present invention, including：Solid-phase micro-extracting device 1, gas chromatograph 2, detection
Device；The solid-phase micro-extracting device 1 includes fibre abstraction head 11；The detector includes：Point discharge device 31, CCD detection
Device 32；On the fibre abstraction head 11 enrichment detection object, fibre abstraction head 11 be inserted into the gas chromatograph 2 into
In sample mouth；The outlet of the gas chromatograph 2 connects the import of the point discharge device 31, and analyte is from capillary column
It by atomization and is excited under the action of point discharge microplasma after outflow, the outlet of point discharge device 31 passes through light
The 33 connection CCD detector part 32 of fibre, the point discharge microplasma and CCD detector part form it is novel based on
The gas chromatography detector of atom spectrum selects mercury characteristic emission wavelength 253.65nm as Detection wavelength, for the first time for mercury
Elemental Speciation Analysis.
Specifically, the point discharge device 31 includes：Closed discharging chamber, two metal electrodes 301, exhaust gas row
Pipeline 311 out, high voltage power supply device；The tip of described two metal electrodes 301 is each passed through the discharging chamber two relatively
Side wall, the tail end of two metal electrodes 301 is respectively positioned on outside the discharging chamber；The tip of described two metal electrodes 301
Between there is preset space length, the tail end of two metal electrodes 301 connects the output end of the high voltage power supply device；The exhaust gas
Discharge line 311 is connected to the discharging chamber；The import of the point discharge device 31 and the outlet of point discharge device 31
It is set on the discharging chamber.
In the present embodiment, by the outer chamber 331 be designed as it is cylindrical be equipped with window, window material be glass or
The thermostable transparents material such as quartz, to facilitate through the discharge scenario inside the observation of inner chamber body upper surface；Two metal electrodes
301 are located on same horizontal line；The lower end surface of cavity is equipped with the first opening, and first opening connects the gas-chromatography
The outlet of instrument；The side wall on cavity top is equipped with the second opening, and one end of the optical fiber 33 passes through cavity connection second and opens
Mouthful, the other end of optical fiber 33 connects the CCD detector part 32；The optical fiber 33 is horizontally disposed.Preferably, described two gold
The material for belonging to electrode 301 is tungsten.
In the present embodiment, the high voltage power supply device includes：Contact voltage regulator 341 and gas tube sign transformer 351；It is described
The input terminal of the output end connection gas tube sign transformer 351 of contact voltage regulator 341, the output end difference of gas tube sign transformer 351
Connect the tail end of two metal electrodes 301.Contact voltage regulator 341 belongs to adjustable auto-transformer configuration, for adjusting voltage,
Its principle is：The equably coiling on annular core, facet of the brush under spring pressure effect with winding wire
Tight connecting contact, rotation axis drive brush, slide brush along coil surface, change brush contact position, i.e. change transformation
The primary and secondary turn ratio of device, so as to make output voltage obtain smooth electrodeless adjusting, input electricity in range of regulation
Pressure is 220V.Gas tube sign transformer 351 is for obtaining high pressure.Fig. 4 is contact voltage regulator 341 and transformer 351 and two gold
Belong to the connection schematic diagram between electrode.
Further, T-type pipe, the T-type are additionally provided between first opening and the outlet of the gas chromatograph
Pipe includes upper interface, lower interface and side interface；The upper interface and lower interface are located on same axis, and the side interface is set to
Between the upper interface and lower interface；The upper interface is adapted to connection with first opening, and carries out gas by "O"-ring
Close property protection, the lower interface are adapted to connection with the outlet of the gas chromatograph；The side interface inputs discharge gas,
The discharge gas is identical as the carrier gas in the gas chromatograph.In the present embodiment, the discharge gas and the carrier gas are equal
For argon gas.Increase T-type pipe purpose be：The analyte that gas chromatograph outlet comes out is blown by increased discharge gas
Into point discharge device (i.e. in inner chamber body), so that analyte faster, is more easily entered atomization excitation apparatus, (i.e. tip is put
In the cavity of electric installation).Argon gas employed in the present embodiment is high-purity argon gas.
In the present embodiment, in the gas chromatograph flow velocity of argon gas be 60 milliliters/per minute；The high voltage supply dress
The output voltage set is 2.9kV；Preset space length between the tip of described two metal electrodes is 3mm.
Below by taking specific experiment as an example, further illustrate the working principle of the present apparatus, and to the beneficial effect of the present apparatus into
Row verifying：
We realize the morphological analysis of mercury using the present apparatus by taking mercury as an example.Before sample introduction, we are by mercury shape object
They are derivatized to volatile compound by matter derivatization (tetraethyl boron sodium), are then carried out using the method for solid phase microextraction
The injection port of the fibre abstraction head insertion gas chromatograph of solid phase microextraction is finally carried out Thermal desorption, through gas-chromatography by extraction
It after instrument separation, into point discharge device atomization and excites, data acquisition is carried out using CCD, realizes mercury and methyl mercury
Analysis.
By a hand sampling handle and a fibre abstraction head, (coating supporting core is Fused to solid phase microextraction
Silica/SS, fiber coat are 65 μm of PDMS/DVB) composition.Gas-chromatography (GC7820A) is equipped with HP-5 capillary chromatographic column
(30m×0.32mm i.d.×0.25 μm).Point discharge (point discharge, PD) device includes a polytetrafluoroethyl-ne
The tungsten bar of alkene cavity, the window of glass material and two sharpenings.Detector further includes that (wavelength acquisition range is CCD
200-400nm) and optical fiber.High voltage power supply device is made of a contact voltage regulator and a gas tube sign transformer.Using above-mentioned
The purpose of device is that common alternating current is converted to specific voltage first with contact voltage regulator then to supply gas tube sign transformer generation
High-frequency high-voltage.Point discharge device is attached with gas chromatograph by T-type pipe.Carrier gas and discharge gas are high-purity
Argon gas.Mercury object is excited in PD microplasma, selects the mercury characteristic emission spectral line of 253.65nm as detection wave
It is long.
The present apparatus is used for the feasibility of mercury morphological analysis：
Because this be established for the first time using point discharge low temperature microplasma as excitaton source it is a kind of simple, compact, sensitive
Degree height and the small novel gas chromatographic detector of dead volume have been preliminary experiment verifying GC-PD-OES for mercury morphological analysis first
Feasibility, wherein GC is gas chromatograph, and PD is point discharge device, and OES is atomic emission spectrum.In order to assess its
Performance compares it with GC-DBD-OES, and wherein DBD is dielectric barrier discharge.Two kinds of systems determine 10 milliliters respectively
30ugL-1Inorganic mercury standard solution, as a result as shown in Fig. 5 a and 5b.In addition to strong OH (283,309, and 319nm), N2(316,
358 and 380nm) and NH (337nm) molecular emission peak, standard solution signal subtracted the net signal that argon gas background signal obtains
Show that the characteristic emission line 253.65nm of mercury under two kinds of systems can be distinguished obviously.Unlike, GC-PD-OES is also
It can significantly observe another emission lines of the mercury at 365.01nm.These results not only prove that GC-PD-OES measures mercury
The feasibility of element, while proving that PD has excitation ability more stronger than DBD, the potentiality with highly sensitive mercury morphological analysis.
In order to verify feasibility of the GC-PD-OES for mercury morphological analysis, analyzed respectively with constructed device and GC-DBD-OES
30ugL-1The mixed standard solution and blank solution of inorganic mercury and methyl mercury.Compare blank and standard solution in mercury emission line
GC signal peak at 253.65nm, and the result of it and GC-DBD-OES are compared, as a result as shown in Figure 5 c, wherein DBD
For dielectric barrier discharge device.Illustrate that GC-PD-OES and GC-DBD-OES can separate well inorganic mercury and methyl mercury,
And peak type is good, can be used for mercury morphological analysis.Pass through comparison simultaneously, it has been found that GC-PD-OES has compared to GC-DBD-OES
There is shorter analysis time, which imply that GC-PD-OES has smaller dead volume.This may be due to point discharge chamber
Caused by body is more much smaller than dielectric barrier discharge cavity.Dielectric barrier discharge is replaced with point discharge, in addition to being obviously shortened analysis
Time and dead volume, we can also be observed that the signal strength at mercury emission line 253.65nm is 5 times of GC-DBD-OES
Left and right.This not only has benefited from the strong excitation ability of point discharge, also leans on capillary outlet end and microplasma enough
It is close related.These behavioral illustrations microplasmas excitation ability and structure are for establishing a kind of quick, high-sensitivity analysis method
Importance.It joined 1 milliliter of NaAc_HAc buffer solution (pH=5,0.2M) in the above blank and standard solution
With 1 milliliter of 1% tetraethyl boron sodium derivating agent, 10 milliliters of total volume.Substance after derivative passes through solid phase microextraction (SPME)
Mode extracted, then gas chromatograph injection port carry out analytical analysis.Two systems sample derivatization and solid phase
Micro-extraction (HS-SPME) condition and GC condition are consistent, while PD-OES and DBD-OES is in respective optimal conditions.
In order to further verify PD with high sensitivity and smaller dead volume, We conducted following experiments.
The methyl mercury and inorganic mercury standard liquid of a series of various concentrations are analyzed using GC-PD-OES and GC-DBD-OES, are tied
Fruit is as shown in Figure 6.From Fig. 6 a as can be seen that when the concentration of methyl mercury and inorganic mercury is lower than 5ugL-1When, under the same terms,
Under GC-DBD-OES system, methyl mercury and inorganic mercury all can't see apparent signal peak, and even if methyl mercury and inorganic mercury concentration
As low as 2ugL-1GC-PD-OES has apparent peak.The signal peak peak area and concentration that mercury compound generates under different systems
Canonical plotting such as Fig. 6 b, shown in 6c, the linearly dependent coefficient of all graticules is all larger than 0.97 as the result is shown.Meanwhile with GC-
DBD-OES is compared, and methyl mercury and inorganic mercury sensitivity enhance 17 and 6 times respectively under GC-PD-OES system.It is worth mentioning
It is that since tungsten bar electrode hardness is high, fusing point is high, is not lost in whole experiment process, and the service life is long, it can long-time stable use.
Above-mentioned analysis the result shows that, PD-OES is a kind of stronger gas chromatography detector, have be able to carry out mercury shape in complicated substrate
The feasibility and practicability of state analysis.
Influence of the point discharge condition to mercury morphological analysis sensitivity is investigated in this experiment.Including discharge gas argon gas flow velocity,
Discharge voltage and electrode distance.Select argon gas flow velocity per minute for 60 milliliters respectively, discharge voltage 2.9kV, electrode spacing
From experiment after being carried out for 3mm as optimum condition.As shown in Figure 7.We test GC-PD-OES's at optimum conditions
Analyze performance.The typical chromatogram and graticule figure of various concentration standard solution are as shown in Figure 8.The range of linearity of methyl mercury is
0.2~40ugL-1, the range of linearity of inorganic mercury is 0.05~40 ugL-1.The graticule linearly dependent coefficient of methyl mercury and inorganic mercury
It is all larger than 0.99.The detection of methyl mercury and inorganic mercury is limited to 0.010ugL-1And 0.0035ugL-1.Meanwhile we investigate
The precision of GC-PD-OES with GC-DBD-OES difference system determines 5 10 ugL respectively-1The standard solution of concentration calculates
Their relative standard deviation.As a result as shown in figure 9, wherein the relative standard of GC-PD-OES system methyl mercury and inorganic mercury is inclined
Poor RSD is respectively 3.5% and 1.7%, and the relative standard deviation RSD of GC-PD-OES system methyl mercury and inorganic mercury distinguishes
For 4.0% and 16.5%.
By being compared apparatus of the present invention with the performance of other similar systems, our system is with it as the result is shown
His system performance is suitable or is better than other systems.GC-DBD-OES, which is easy breakdown, to be used for a long time.Our system is more
Add compact portable, while device is simple, low energy consumption, electrode is not easy to be lost, low temperature plasma does not need additional cooling dress
It sets, stablize and can use for a long time, there is very big potential in terms of instrument miniaturization.
Gas chromatographic detection device provided in an embodiment of the present invention based on point discharge atom spectrum, for the first time by gas phase
Chromatograph and point discharge device and CCD detector part are combined, and are between the tip by two needlepoint electrodes due to point discharge
A kind of nonequilibrium state atmosphere gas electric discharge generated has stronger excitation ability and longer compared to dielectric barrier discharge
Service life.Also, point discharge device is smaller than dielectric barrier discharge device volume, so that entire structure of the detecting device is simpler
It is single, compact.Experiment shows the gas chromatographic detection device provided in an embodiment of the present invention based on point discharge atom spectrum, phase
Compared with the existing gas chromatographic detection device based on dielectric barrier discharge, sensitivity is higher, and detection time is shorter, and energy
Enough long-term stable works.
The present invention using the point discharge microplasma for having strong excitation ability, space small as excitaton source, uses for the first time
CCD detector part establishes a kind of high sensitivity, the miniaturization gas that dead volume is small, simple, compact, portable as detecting element
Phase chromatographic detector.With miniaturization gas chromatograph combination, the Elemental Speciation Analysis instrument of a miniaturization is constituted, is expected to
For field analysis.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, appoints
What those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, answer
It is included within the scope of the present invention.
Claims (9)
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