CN106706584A - Portable fluorescence detector applicable to analysis of trace ammonia and nitrogen in seawater - Google Patents
Portable fluorescence detector applicable to analysis of trace ammonia and nitrogen in seawater Download PDFInfo
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- CN106706584A CN106706584A CN201611251960.0A CN201611251960A CN106706584A CN 106706584 A CN106706584 A CN 106706584A CN 201611251960 A CN201611251960 A CN 201611251960A CN 106706584 A CN106706584 A CN 106706584A
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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Abstract
The invention provides a portable fluorescence detector applicable to analysis of trace ammonia and nitrogen in seawater. The detector comprises a power supply, a constant current circuit, a constant voltage circuit, a light source, a first monochromator, a second monochromator, a fluorescence flow cell, a photomultiplier and a detection mounting device, wherein the power supply is connected with the light source through the constant current circuit and connected with the photomultiplier through the constant voltage circuit; the detection mounting device comprises a mounting casing and a casing cover, and a channel I used for embedding the fluorescence flow cell, a notch I used for embedding the first monochromator and a notch II used for embedding the second monochromator are formed in one side surface of the mounting casing. Seawater samples are prevented from being polluted in the transportation and storage process, and the requirements for miniaturization and good stability due to the fact that ammonia and nitrogen usually need on-site or in-situ determination are met. The portable fluorescence detector which is applicable to analysis of trace ammonia and nitrogen is studied by use of the modular, miniaturized, specialized and intelligent design concept, and the performance of the detector is inspected.
Description
Technical field
Extra large underwater trace ammonium nitrogen is can be applied to the invention belongs to application oceanographic equipment Instrument technology field, more particularly to one kind
The Portable fluorescence detector of analysis.
Background technology
Fluorescence detector as fluorimetry hardcore, sensitivity and performance parameter directly affect assay method
Performance.At present, the ammonium nitrogen fluorescence detector that researcher the uses typically larger commercial apparatus of volume.Such as Amornthammarong
Deng[1,2]Use F1080 (Japanese Hitachi companies) and L-2485 fluorescence detectors (Japanese Hitachi companies)；Waich etc.[3]
Use LS-50B fluorescence detectors (PerkinElmer companies of the U.S.)；Huang etc.[4]Using L-7480, (Japanese Hitachi is public
Department) fluorescence detector；Frank etc.[5]Use F1000 (Japanese Hitachi companies) fluorescence detector.Most of detector is high
The fluorescence detector of adapted, body in effect liquid phase chromatogram (HPLC, High Performance Liquid Chromatography)
Product is larger, expensive, and because fluorescence flow cell is smaller, pond pressure is larger.
Present analysis instrument on the basis of classical optics, chemistry and electronics, by computer hardware and software, to
Intelligent direction develops.Modularization, miniaturization, customizations, are the main design thoughts of present analysis instrument[6].The module of instrument
Change is that the hardware cell of function phase in instrument is same or correlation is sorted out, and is designed to various modules[7].Miniaturization and lightweight are then
Occupancy of the instrument to lab space is reduced as far as possible, or it is more portable, beneficial to user's operation.It is general that customizations refer to removal
The other functions of logical instrument, multi-functional labyrinth is replaced using relatively simple part, is such as used in spectrophotometer
Optical filter replaces prism or grating.Modularization, miniaturization, customizations not only reduce equipment instrument, and enhancing shock resistance, more
Adaptation is used in ambient scene.
The content of the invention
In order to solve above-mentioned technical problem, it is an object of the invention to provide one kind can avoid seawater sample transport,
Pollution is introduced during preservation, ammonium nitrogen generally needs at the scene or in-site detecting, must using miniaturization, good stability it is portable
Fluorescence detector.Research application modularization of the present invention, miniaturization, customizations, intelligentized design concept, developing one kind can apply
In the Portable fluorescence detector of extra large underwater trace ammonium nitrogen analysis, and investigate the performance of detector.
To achieve the above object, present invention employs following technical scheme：
The present invention provides a kind of Portable fluorescence detector that can be applied to trace ammonium nitrogen analysis, including power supply, Constant Electric Current
Road, constant voltage circuit, light source, the first monochromator, the second monochromator, fluorescence flow cell (2), photomultiplier (PMT) (3) and detection
Erecting device (1)；
Power supply is connected by constant-current circuit with light source, and power supply is connected by constant voltage circuit with photomultiplier (PMT) (2),
Detection erecting device (1) is provided with use including installing housing (11) and cap (12) on the one side for installing housing (11)
In the groove I for setting fluorescence flow cell (2) and for setting the notch I of the first monochromator (141), for setting the second monochrome
The notch II of device (142)；
The groove II (15) for setting fluorescence flow cell (2) is provided with cap (12) one side and for setting
The slotted eye I (171) of one monochromator (141), the slotted eye II (172) for setting the second monochromator (142)；
Housing (11) and cap (12) clamping will be installed so that fluorescence flow cell (2) is closely embedded in groove I and groove
In ditch II (15), the first monochromator (141) is embedded in notch I and slotted eye I (171), the second monochromator (142) is embedded in notch
II and slotted eye II (172)；
Fluorescence flow cell (2) excites light window including inlet pipeline (21), outlet pipeline (22), flow cell cavity, two
With a transmitting light window, inlet pipeline (21) and outlet pipeline (22) be by fluorescence flow cell (2) top entrance and with stream
Logical cell cavity body phase connection, wherein：Flow cell cavity is in black powder, and two excite light window and a transmitting light window white
Transparence；
Being provided with two in installation housing (11) excites optical channel and a transmitting optical channel, notch I and notch II to distinguish
Optical channel is excited to be interconnected with corresponding, the light for exciting the light source (131) of optical channel outer end to send installed in two is passed through respectively
Cross the first monochromator (141), the second monochromator (142) and along each exciting optical channel, excite light window to be irradiated into fluorescence
In the flow cell cavity of flow cell (2), and it is set to produce fluorescence signal；
Photomultiplier (PMT) can receive flow cell by the second monochromator along transmitting optical channel, transmitting light window
Fluorescence signal in cavity.
As preferred：Two excite light window and a transmitting light window to be opened in the difference of fluorescence flow cell (2) respectively
On side, in four prisms cylinder shape, two excite window to be located at (2) two phases of fluorescence flow cell respectively to the fluorescence flow cell (2)
To on side, the light that light source sends is by the first monochromator and along exciting exciting on optical channel, alignment fluorescence flow cell (2)
Light window circulates in cell cavity body；Photomultiplier (PMT) is by the second monochromator along transmitting optical channel, alignment launching light
Fluorescence signal in window reception flow cell cavity.
As preferred：The profile size of fluorescence flow cell (2)：Length × width × height is 12.5mm × 12.5mm × 45mm, stream
Logical pond cavity size：Length × width × height is 5mm × 5mm × 5mm, two exciting light window sizes：Length × height is 5mm × 3mm,
Launching light window size：Length × height is 5mm × 5mm.
As preferred：Light source is 365nm UV-LED, and fluorescence flow cell (2) is to use quartz material.
As preferred：First monochromator includes the exciting light optical filtering that centre wavelength is 365nm, a width of 15 ± 2nm of half-wave zone
Piece, the second monochromator includes that centre wavelength is 425nm, the launching light optical filter of a width of 15 ± 2nm of half-wave zone.
Compared with prior art, present invention has the advantages that：
The invention provides a kind of Portable fluorescence detector for being exclusively used in trace ammonium nitrogen analysis.It includes UV-LED light
The stuck-module of source, optical filter, modularization PMT detecting elements, the fluorescence flow cell of customized processing and designed, designed processing.This hair
Bright fluorescence detector, for PMT powers, using constant-current circuit for UV-LED powers, reduces the fluctuation of signal using constant voltage circuit.
The ammonium nitrogen standard specimen of METHOD FOR CONTINUOUS DETERMINATION 100nmol/L in 90min, RSD is 0.8% (n=38), illustrates fluorescence detector stabilization of the present invention
Property is preferable.Compare fluorescence detector of the present invention and commodity PMT-FL fluorescence detectors, fluorescence detector small volume of the present invention, weight
Gently, cheap, stability is slightly better than commercial detector.If it is sensitivity to define working curve slope, fluorescence inspection of the present invention
The remolding sensitivity PMT-FL fluorescence detectors for surveying device are high by about 11.4%.And, fluorescence detector of the present invention can be prevented effectively from bubble
Interference to signal.
Brief description of the drawings
Fig. 1 is the principle schematic of Portable fluorescence detector in the present invention.
Fig. 2 is the schematic diagram of the fluorescence flow cell that final choice is used in the present invention.
Fig. 3 is, as detector, to scan UV-LED with USB2000+ fiber spectrometers (Ocean Optics companies of the U.S.)
Emission spectrum schematic diagram.
The schematic diagram of the emission spectrum of Fig. 4 halogen tungsten lamps+exciting light optical filter.
The schematic diagram of the emission spectrum of Fig. 5 halogen tungsten lamps+launching light optical filter.
Fig. 6 power supply circuit design drawings of the invention.
Schematic diagram when PMT, LED, optical filter and unassembled fluorescence flow cell in Fig. 7 present invention.
Schematic diagram after PMT, LED, optical filter and fluorescence flow cell are assembled into one in Fig. 8 present invention.
The stability test of Fig. 9 fluorescence detectors of the present invention
Figure 10 fluorescence detectors of the present invention determine working curve (A, fluoroscopic examination of the present invention of ammonium nitrogen with PMT-FL detectors
Device；B, PMT-FL detector)
Figure 11 is that front and rear fluorescence flow cell schematic diagram is transformed in the present invention.
Figure 12 is detection signal (A, fluorescence detector of the present invention of fluorescence detector of the present invention and PMT-FL；B, PMT-FL
Detector).
Reference：Detection erecting device (1), fluorescence flow cell (2), photomultiplier (3),
Housing (11), cap (12), the first monochromator (141), the second monochromator (142), slotted eye I (171), slotted eye are installed
II (172), inlet pipeline (21), outlet pipeline (22), light source (131).
Specific embodiment
Specific embodiment of the invention is made a detailed explanation below in conjunction with the accompanying drawings.
1.2 mentalities of designing
As shown in Fig. 1~12, the present invention provides a kind of Portable fluorescence inspection that can be applied to extra large underwater trace ammonium nitrogen analysis
Device is surveyed, mainly including light source, monochromator (the first monochromator and the second monochromator), 4 portions of fluorescence flow cell and photomultiplier
Point, Fig. 1 is the schematic diagram of Portable fluorescence detector.The light sent by light source, it is (monochromatic also known as exciting light through the first monochromator
Device) after, required excitation wavelength is isolated, it is used to excite tested molecule, when the molecular transition that is excited returns ground state, to four sides
Launch fluorescence from all directions.To eliminate the influence of incident light and scattering light to fluoroscopic examination, selection is examined in the direction vertical with exciting light
Fluorescence is surveyed, and adds the second monochromator.Light intensity signal is received by photomultiplier (PMT), then by a series of analog-to-digital conversions and
Signal amplifies, and obtains digitized fluorescence signal[8]。
The special Portable fluorescence detector of this chapter research trace ammonium nitrogen analysis.Using small volume, good stability it is ultraviolet
Light emitting diode (UV-LED, Ultraviolet-Light Emitting Diode) as light source, optical filter as monochromator,
Designed, designed fluorescence flow cell, makes it possess function not by aeration.With high sensitivity, modular photomultiplier
(PMT, Photomultiplier Tube) detects fluorescence.In power supply circuit, using constant-current circuit for UV-LED powers, constant pressure electricity
Road powers for photomultiplier (PMT), to ensure that output signal has signal to noise ratio higher.
1.3 instrumentations
The main design from fluorescence flow cell of making of Portable fluorescence detector in the present invention, light source, monochromator and
The selection of detecting element, power supply circuit is designed and produced, and detector housing is made etc., and several aspects are started with.
1.3.1 the design of fluorescence flow cell
Fluorescence flow cell is one of core component of Portable fluorescence detector in the present invention, should meet following bar
Part：(1) the pond body product of fluorescence flow cell is small, prevents measured object and current-carrying over-mixed and influences the peak height and peak shape of signal；
(2) light path design of incident light and launching light is reasonable, to avoid exciting light and launching light from excessively being lost in light path；(3) enter
Penetrate light window and detection window is sufficiently large, to ensure sensitivity；(4) fluorescence flow cell will be beneficial to the discharge of bubble.Due to ammonium
The excitation wavelength of azepine derivatives preferably selects quartz in ultraviolet region (365nm), fluorescence flow cell material.In recent years, researcher
Attempt developing new fluorescence flow cell[9].Such as Horstkotte[10]In 2011, make a kind of new using lucite
Fluorescence flow cell, determines seawater trace ammonium nitrogen, and method detection is limited to 13nmol/L.The fluorescence flow cell is economical and practical, but, one
Part fluorescence can be absorbed by PMMA；And PMMA not acid and alkali-resistances, it is soluble in organic solvent., Amornthammarong in 2013
Deng[11]The structure of fluorescence flow cell is simplified, fluorescence flow cell is made with the preferable fluorinated ethylene propylene (FEP) pipe of light transmission.It is this to set
Meter reduces the pond body product of fluorescence flow cell.Its interference for having the disadvantage the easy stimulated luminescence of launching light and veiling glare, background fluorescence compared with
By force, corresponding detector sensitivity is relatively low.
Various trials have been done in present invention research in the design of fluorescence flow cell, and Fig. 2 show this research final choice to be made
Fluorescence flow cell (customized, city of Jiangsu Pu Xi optical elements factory).Fluorescence flow cell appearance and size (length × width × height)
It is 12.5mm × 12.5mm × 45mm, pond inside dimension (length × width × height) is 5mm × 5mm × 5mm, and pond body product is about 125 μ L, swashs
The luminous window size with launching light is 5mm × 5mm.
1.3.2 the selection of light source, monochromator and detecting element
1.3.2.1 the selection of light source
The light source of Portable fluorescence detector of the present invention has high-pressure sodium lamp, xenon lamp, xenon-mercury-arc lamp, flash lamp, LED, solid
Laser, tunable dye laser etc..Because fluorescence intensity is directly proportional to excitating light strength[12], light intensity is stronger, stability compared with
Good light source is the first-selection of Portable fluorescence detector of the present invention.Xenon lamp is current commodity Portable fluorescence detector of the invention
Most common light source.Xenon lamp spectrum covers ultra-violet (UV) band and visible region (250-800nm), and good stability, light intensity is stronger；But,
Xenon lamp volume is larger, and high pressure conditions are in during work, and the stability requirement to the output voltage, electric current of power supply circuit is higher.Gu
Body laser monochromaticjty is good, and launching light light intensity is stronger, and the angle of divergence is small.Use the laser-Induced Fluorescence Detection skill of solid state laser
Art, is widely used in the analysis of biological and environment organic matter[13,14].But, solid state laser volume is larger, expensive.
Using the LED of semiconductor light emitting technology because luminous efficiency is high, energy consumption is low, monochromaticjty is good, long service life, compact and price just
Preferably, as the first-selection of various portable and field assay instrument.
The a length of 365nm of optimum excitation wave of ammonium nitrogen fluorescent derivative, optimal launch wavelength is 425nm.Present invention research makes
With 365nm UV-LED (packed by metal casing, purchased from Yuan Chuan Electronics Co., Ltd.s of Shenzhen) as light source.What the said firm provided
UV-LED optical parametrics are listed in table 1.1.With USB2000+ fiber spectrometers (Ocean Optics companies of the U.S.) as detector,
The emission spectrum of UV-LED is scanned, as shown in Figure 3.
The optical parametric of the UV-LED of table 1.1
1.3.2.2 the selection of monochromator
Monochromator mainly has grating and optical filter etc..The monochromator of common Portable fluorescence detector of the invention generally by
Grating, slit, prism, stepper motor and machine driven system composition, it is complex, be not suitable for Portable fluorescence of the present invention
Detector.Optical filter has the advantages that simple, cheap, and its manufacturing technology has reached level higher, and monochromaticjty is preferable；It is suitable
Share in portable, customizations fluorescence detectors.
The exciting light and launching light optical filter of this research institute are customized from Beijing Jinji Aomeng Technology Co., Ltd..The public affairs
The centre wavelength for taking charge of the exciting light optical filter for providing is 365nm, and the centre wavelength of launching light optical filter is 425nm, half-wave bandwidth
It is 15 ± 2nm.Using LS-1-LL halogen tungsten lamps (Ocean Optics companies of the U.S.) as light source, USB2000+ fiber spectrums
Instrument (Ocean Optics companies of the U.S.) scans halogen tungsten lamp and is filtered by exciting light optical filter and launching light respectively as detector
Emission spectrum after piece, is shown in Fig. 4 and Fig. 5.The practical center wavelength of exciting light optical filter is obtained for 371.7nm, launching light filter
The practical center wavelength of mating plate is 429.0nm, substantially meets the measure demand of ammonium azepine derivatives.
1.3.2.3 the selection of detecting element
Faint optical signal is converted into electric signal by detecting element, after the amplified circuit of signal amplifies, by analog-to-digital conversion electricity
Road is converted to the receivable data signal of host computer.Conventional detecting element include charge coupled array, photovoltaic cell,
Vacuum photo tube, silicon photoelectric diode, PMT etc..The sensitivity of PMT is high, the response time is short, can detect faint optical signal, is
The optimum detection element of high sensitivity fluorescence detector.By modularized design, photo-signal amplifies electricity to current commodity PMT
Road and analog to digital conversion circuit are integrated in inside PMT, and user need to only provide the supply voltage of stabilization for PMT.
The PMT of this research institute is bought from Sens-Tech companies of Britain.PMT requirement supply voltages are 5 ± 0.25V.Originally grind
Study carefully PMT is directly connected with computer by RS232 ports, (National Instruments are public in the U.S. using Labview 8.2
Department) write PC control software record output signal.
1.3.3 circuit design and circuit board making
Power supply circuit is mainly UV-LED and provides the operating voltage of 3.6V and the operating current of 20mA, in addition, PMT need to be supplied
The stable power-supplying voltage of 5 ± 0.25V.Therefore, constant voltage circuit constitutes driving voltage and drives using switch-type stabilized chip LM2575,
The burning voltage of 5 ± 0.25V is provided；Power supply module caloric value can be reduced simultaneously.Constant-current circuit is using OP07 amplifiers and precisely
Reference voltage chip TL430 is constituted and is compared chopping wave constant current circuit, is increased using transistor 8050 and driven, precisely electric to provide 20mA
Stream drives UV-LED.The circuit of design is as shown in Figure 6.
1.3.4 detector assembling
When designing and producing the stuck-module of fluorescence flow cell and optical filter, from black material polyformaldehyde (POM,
Polyformaldehyde).POM intensity is high, wearability is good, organic solvent-resistant and weak acid, easy to process.PMT, LED, optical filter
And fluorescence flow cell assembling after detector it is as shown in Figure 7.The fixed of optical filter uses embedded design, if changing optical filter,
Can be realized by dismantling the POM modules.
Interference is produced to signal to avoid natural light from leaking into detector, shell need to be added for detector, strengthen lucifuge.Using
Polyvinyl chloride (PVC, Polyvinyl Chloride) plate of thickness about 2mm, by design size dicing, uses between each
Aluminum corner brace is connected.Solution import and export, relay indicating light etc. are fixed on front panel, power switch, RS232 signal output ports
Etc. being fixed on rear board.The fluorescence detector being made is as shown in Figure 8.
The performance of 1.4 detectors
Wasted Water by FIA-Fluorimetry (FI-FL) analysis system is built, using fluorescence detector of the present invention.With ultra-pure water
Used as current-carrying, ammonium nitrogen mark-on sample investigates the performance of fluorescence detector of the present invention, and most receive choosing in the market as sample
(commodity PMT-FL flow analysis fluorescence detectors, FIA-Lab Instruments are public in the U.S. for the Portable fluorescence detector of welcome
Department) it is compared with fluorescence detector of the present invention.
1.4.1 stability
Detector light source and detecting element are investigated in the case where working long hours, the stability of output signal.Take
The ammonium nitrogen mark-on sample of 100nmol/L, with FI-FL method METHOD FOR CONTINUOUS DETERMINATION 90min, is as a result shown in Fig. 9 as sample.Sample fluorescence signal
Relative standard deviation be 0.8% (n=38), it is seen that the stability of fluorescence detector of the present invention is preferable.
1.4.2 the comparing of fluorescence detector of the present invention and commercial detector
1.4.2.1 control experiment
Homemade detector is connected with commodity PMT-FL, collectively as the detector of FI-FL analysis systems, while determining
The fluorescence signal of sample.The standard working curve solution in 0-300nmol/L concentration ranges is determined, is determined 4 times per sample, obtain work
Make curve as shown in Figure 10.If it is detection sensitivity, as shown in Figure 10, fluorescence detector of the present invention to define working curve slope
Remolding sensitivity commodity PMT-FL fluorescence detectors are high by about 11.4%.
7.4.2.2 influence of the bubble to detection signal
The interference of bubble is most common problem in spectral method of detection.To reduce influence of the bubble to signal, generally need
At detector taphole back-pressure is produced plus the polyether-ether-ketone pipe of small-bore.The fluorescence of this research designed, designed is circulated
Pond is slightly transformed, and it is 5mm × 3mm (long × high) that order excites light window, and it is 5mm × 5mm (long × high) to keep transmitting light window, is changed
Fluorescence flow cell schematic diagram before and after making is as shown in figure 11.In the FI-FL analysis systems built, by fluorescence detector of the present invention
Connected with commodity PMT-FL detectors, while determining the fluorescence signal of sample.The flow velocity of reagent R1 and R2 is 0.20mL/min, sample
Product are 1.34mL/min with rate of Carrier Stream, remove the internal diameter 0.25mm being placed at detector taphole to produce back-pressure
PEEK is managed.Using ultra-pure water as current-carrying, the mark-on sample in the range of ammonium nitrogen concentration 0-300nmol/L is determined, is determined 4 times per sample,
The sample signal that two kinds of detectors of record are obtained, is shown in Figure 12.
Excite light window smaller due to improved self-control fluorescence flow cell, and minute bubbles are gathered in fluorescence flow cell
Top is excluded with solution, and exciting light will not be radiated on bubble, therefore bubble will not produce fluorescence signal or interfering noise.By Figure 12
Understand, fluorescence detector of the present invention can be prevented effectively from interference of the bubble to signal, better than commodity PMT-FL detectors.
1.4.2.3 performance parameter is compared
Fluorescence detector of the present invention is listed in table 1.2 with the parameter of commodity PMT-FL detectors.Fluoroscopic examination body of the present invention
Product is smaller, and weight is lighter, cheap, and sensitivity and stability are slightly better than commercial detector.But, fluorescence detector of the present invention
Background fluorescence be significantly higher than PMT-FL detectors, can be by the setting of upper computer software, by background fluorescence in practical application
Zero, does not interfere with the measure of sample.
The fluorescence detector of the present invention of table 1.2 compares with the parameter of PMT-FL detectors
1.5 brief summaries of the present invention
(1) have developed a kind of Portable fluorescence detector for being exclusively used in trace ammonium nitrogen analysis.It includes UV-LED light sources, filter
The stuck-module of mating plate, modularization PMT detecting elements, the fluorescence flow cell of customized processing and designed, designed processing.
(2) fluorescence detector of the present invention, using constant-current circuit for UV-LED powers, is subtracted using constant voltage circuit for PMT powers
The small fluctuation of signal.The ammonium nitrogen standard specimen of METHOD FOR CONTINUOUS DETERMINATION 100nmol/L in 90min, RSD is 0.8% (n=38), illustrates this hair
Bright fluorescence detector stability is preferable.
(3) fluorescence detector relatively more of the present invention and commodity PMT-FL fluorescence detectors, fluorescence detector small volume of the present invention,
Lightweight, cheap, stability is slightly better than commercial detector.If it is sensitivity to define working curve slope, of the invention glimmering
The remolding sensitivity PMT-FL fluorescence detectors of photodetector are high by about 11.4%.And, fluorescence detector of the present invention can be prevented effectively from
Interference of the bubble to signal.
Document is as follows referenced by present invention：
[1]Amornthammarong N.,Zhang J.Z.Shipboard fluorometric flow analyzer
for high-resolution underway measurement of ammonium in seawater[J]
.Analytical Chemistry,2008,80(4):1019-1026.
[2]Amornthammarong N.,Zhang J.Z.,Ortner P.B.An autonomous batch
analyzer for the determination of trace ammonium in natural waters using
fluorometric detection[J].Analytical Methods,2011,3(7):1501-1506.
[3]Waich K.,Borisov S.,Mayr T.,Klimant I.Dual lifetime referenced
trace ammonia sensors[J].Sensors and Actuators B:Chemical,2009,139(1):132-
138.
[4]Huang G.,Hou J.,Zhou X.L.A measurement method for atmospheric
ammonia and primary amines based on aqueous sampling,OPA derivatization and
HPLC analysis[J].Environmental Science&Technology,2009,43(15):5851-5856.
[8]Frank C.,Schroeder F.Using sequential injection analysis to
improve system and data reliability of online methods:determination of
ammonium and phosphate in coastal waters[J].Journal of Analytical Methods in
Chemistry,2007.
[6] development [D] the Xiamen University of Wen Yuyun multichannels nutritive salt automatic analysis system, 2004.
[7] cutting edge technology of model generation good fortune development of analytical instrumentation and new thought [J] Modern Scientific Instruments, 2000,3:
10-13.
[8] department of chemistry of Wuhan University Instrumental Analysis [M] Beijing:Higher Education Publishing House, 2001.
[9]Bey S.K.A.K.,Connelly D.P.,Legiret F.E.,Harris A.J.K.,Mowlem M.C.A
high-resolution analyser for the measurement of ammonium in oligotrophic
seawater[J].Ocean Dynamics,2011,61(10):1555-1565.
[10]Horstkotte B.,Duarte C.M.,Cerdà V.A miniature and field-
applicable multipumping flow analyzer for ammonium monitoring in seawater
with fluorescence detection[J].Talanta,2011,85(1):380-385.
[11]Amornthammarong N.,Zhang J.Z.,Ortner P.B.,Stamates J.,Shoemaker
M.,Kindel M.W.A portable analyser for the measurement of ammonium in marine
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[12] golden hook, king this of honor XRF [M] Beijing are permitted:Science Press, 2006.
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K.,Kita K.,Tonokura K.Comparison of laser-induced fluorescence and
chemiluminescence measurements of NO2at an urban site[J].Atmospheric
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2001,20(6):96-99。
Claims (5)
1. a kind of Portable fluorescence detector that can be applied to extra large underwater trace ammonium nitrogen analysis, it is characterised in that including power supply, perseverance
Current circuit, constant voltage circuit, light source, the first monochromator, the second monochromator, fluorescence flow cell (2), photomultiplier (3) and detection
Erecting device (1)；
Power supply is connected by constant-current circuit with light source, and power supply is connected by constant voltage circuit with photomultiplier (2), the detection peace
Assembling device (1) is provided with for setting fluorescence including installing housing (11) and cap (12) on the one side for installing housing (11)
The groove I of flow cell (2) and for setting the notch I of the first monochromator (141), for setting the second monochromator (142)
Notch II；
The groove II (15) for setting fluorescence flow cell (2) is provided with cap (12) one side and for setting the first list
The slotted eye I (171) of color device (141), the slotted eye II (172) for setting the second monochromator (142)；
Housing (11) and cap (12) clamping will be installed so that fluorescence flow cell (2) is closely embedded in groove I and groove II
(15) in, the first monochromator (141) is embedded in notch I and slotted eye I (171), the second monochromator (142) is embedded in the He of notch II
Slotted eye II (172)；
Fluorescence flow cell (2) excites light window and one including inlet pipeline (21), outlet pipeline (22), flow cell cavity, two
Individual transmitting light window, inlet pipeline (21) and outlet pipeline (22) are to be entered by the top of fluorescence flow cell (2) and and flow cell
Cavity is connected, wherein：Flow cell cavity is in black powder, and two excite light window and a transmitting light window white transparent
Shape；
Two be provided with housing (11) excite optical channel and a transmitting optical channel installing, notch I and notch II respectively with it is right
The optical channel that excites answered is interconnected, and the light that the light source (131) of optical channel outer end sends is excited installed in two respectively through the
One monochromator (141), the second monochromator (142) simultaneously circulate along each exciting optical channel, exciting light window to be irradiated into fluorescence
In the flow cell cavity in pond (2), and it is set to produce fluorescence signal；Photomultiplier is logical along launching light by the second monochromator
Road, transmitting light window can receive the fluorescence signal in circulation cell cavity body.
2. a kind of Portable fluorescence detector that can be applied to extra large underwater trace ammonium nitrogen analysis according to claim 1,
Characterized in that, two excite light window and a transmitting light window to be opened in respectively on the not ipsilateral of fluorescence flow cell (2),
In four prisms cylinder shape, two excite window to be located at (2) two opposite flanks of fluorescence flow cell respectively to the fluorescence flow cell (2)
On, the light that light source sends excite light window on optical channel, alignment fluorescence flow cell (2) by the first monochromator and along exciting
Circulate in cell cavity body；Photomultiplier is by the second monochromator along transmitting optical channel, alignment launching light window reception stream
Fluorescence signal in logical cell cavity body.
3. a kind of Portable fluorescence detector that can be applied to extra large underwater trace ammonium nitrogen analysis according to claim 1,
Characterized in that, the profile size of fluorescence flow cell (2)：Length × width × height is 12.5mm × 12.5mm × 45mm, and circulate cell cavity
Body size：Length × width × height is 5mm × 5mm × 5mm, two exciting light window sizes：Length × height is 5mm × 3mm, launching light
Window size：Length × height is 5mm × 5mm.
4. a kind of Portable fluorescence detector that can be applied to extra large underwater trace ammonium nitrogen analysis according to claim 1,
Characterized in that, light source (131) is 365nm UV-LED, fluorescence flow cell (2) is to use quartz material.
5. a kind of Portable fluorescence detector that can be applied to extra large underwater trace ammonium nitrogen analysis according to claim 1,
Characterized in that, the first monochromator includes that centre wavelength is 365nm, the exciting light optical filter of a width of 15 ± 2nm of half-wave zone, second
Monochromator includes that centre wavelength is 425nm, the launching light optical filter of a width of 15 ± 2nm of half-wave zone.
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