Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • 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
  • G01N21/64—Fluorescence; Phosphorescence
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • 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
  • G01N21/64—Fluorescence; Phosphorescence
  • G01N21/645—Specially adapted constructive features of fluorimeters
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • 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
  • G01N21/64—Fluorescence; Phosphorescence
  • G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/84—Systems specially adapted for particular applications
  • G01N21/85—Investigating moving fluids or granular solids
  • G01N21/8507—Probe photometers, i.e. with optical measuring part dipped into fluid sample
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
  • G01N33/18—Water
  • G01N33/182—Specific anions in water
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
  • G01N33/18—Water
  • G01N33/1886—Water using probes, e.g. submersible probes, buoys
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N2201/00—Features of devices classified in G01N21/00
  • G01N2201/02—Mechanical
  • G01N2201/021—Special mounting in general
  • G01N2201/0218—Submersible, submarine
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N2201/00—Features of devices classified in G01N21/00
  • G01N2201/06—Illumination; Optics
  • G01N2201/062—LED's
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N2201/00—Features of devices classified in G01N21/00
  • G01N2201/12—Circuits of general importance; Signal processing
  • G01N2201/127—Calibration; base line adjustment; drift compensation

Definitions

• the present invention relates to a submersible fluorimeter intended to be mounted on an underwater system for the study of fluorescent aromatic compounds in the aquatic environment, each aromatic compound having at least one fluorophore, of the type comprising:
• an excitation module adapted to excite the fluorophore
• a detection module adapted to detect light emitted by the excited fluorophore.
• Fluorescence is a spectroscopic method widely used for twenty years to study the distribution, composition and dynamics of dissolved organic matter (MOD) in the aquatic environment.
• MOD dissolved organic matter
• MOD-F fluorescent MOD composition
• Phe polycyclic aromatic hydrocarbons
• Try tryptophan
• PAHs polycyclic aromatic hydrocarbons
• humic substance such as terrestrial humic acids (AHT) and marine humic acids (AHM).
• the submersible optical sensors are essentially fluorometers, photometers or scatterometers which, via the fluorescence properties, absorbance or diffusion of the material, measure biogeochemical variables.
• Underwater or autonomous platforms or devices including gliders, floaters, fixed or drifting buoys, propeller vehicles (AUVs) and remote-controlled robots (ROVs), some of them between them can stay from a few weeks or months (“gliders") to a few years (float-profilers) at sea.
• gliders float-profilers
• ROVs remote-controlled robots
• the aim of the invention is to propose a submersible fluorimeter which makes it possible to study the main fluorescent aromatic compounds present in the aquatic environment and which can be mounted on all types of existing underwater devices.
• the subject of the invention is a fluorimeter of the aforementioned type, characterized in that the excitation module comprises a first light source having a first UV LED and having a first wavelength of less than 300 nm.
• the first wavelength may be substantially equal to 250 nm
• the detection module may comprise a first photodiode, a first collimation lens and a first interference optical filter,
• the first interference optical filter may be centered substantially on 360 nm or on 427 nm,
• the fluorimeter may comprise a fixing part adapted to be fixed on the underwater system and a measurement part adapted to be immersed,
• the measurement part may comprise a protective cover against ambient light
• the fluorimeter may have a substantially cylindrical shape
• the excitation module may comprise a second light source having a second UV LED and having a second wavelength of less than 300 nm, the first and second wavelengths being different from each other; the second wavelength may be substantially equal to 280 nm,
• the detection module may comprise a second photodiode, a second collimation lens and a second interference optical filter,
• the second interference optical filter may be centered substantially at 340 nm or at 405 nm,
• the fluorimeter may be suitable for studying polycyclic aromatic hydrocarbons such as phenanthrene, amino acids such as tryptophan, and tracers of sources of organic matter such as terrestrial humic acids and marine humic acids,
• the fluorimeter can be adapted to descend to depths of up to 1000 m, -
• the fluorimeter can be adapted to be mounted on any type of underwater system, autonomous or hard-wired, such as gliders, floats-profilers, fixed or drifting buoys, propeller vehicles and robots. remotely.
• the fluorimeter comprises an electrical circuit comprising a plurality of printed circuits positioned one below the other.
• the electronic circuit comprises three four-layer printed circuits, an excitation circuit controlling the excitation module, a detection circuit controlling the detection module and a control circuit.
• the detection circuit is provided with an analog-digital converter.
• the control circuit uses the digital data from the analog-digital converter to synchronize the excitation module and the detection module.
• the fluorimeter has a substantially cylindrical shape around an axis of revolution, the three circuits being positioned one below the other so as to be substantially parallel to each other and concentric about the axis of revolution.
• FIG. 1 is a side view of a fluorometer according to the invention.
• FIG. 2 is an exploded perspective view from above of the fluorometer of Figure 1;
• Figure 3 is an exploded perspective view from below of the fluorometer of Figure 1;
• FIG. 4 is a sectional view of a portion of the fluorometer of Figure 1;
• Figure 5 is a perspective view of a portion of the fluorometer of Figure 1; - Figure 6 is a top view of a portion of the fluorometer of Figure 1; and
• FIG. 7 is a diagram illustrating the principle of operation of the fluorometer of Figure 1.
• Figure 1 illustrates a fluorimeter 10 adapted to be mounted on an underwater system (not shown) for the simultaneous study of two fluorescent aromatic compounds in the aquatic environment.
• the fluorimeter 10 comprises a fixing part 12 adapted to be fixed on the underwater system and a measuring part 14 adapted to be immersed in the water so as to be in contact with the measuring medium, such as the fresh or marine water.
• the fixing portion 12 comprises a housing 16 comprising a substantially cylindrical body 18 of axis AA extended at one end by a substantially annular collar 20.
• the flange 20 has an outer diameter greater than that of the body 18.
• the body 18 and the collar 20 delimit respective inner chambers separated from one another by a partition wall 21.
• the partition wall 21 has four through openings 21A, 21B, 21C and 21D for the passage of light between the inside and the outside of the fluorimeter 10 as will be explained in more detail later.
• the housing 16 is made from aluminum, the flange 20 being integral with the body 18.
• the partition wall 21 consists of an insert, fixed, for example by gluing, to the flange 20.
• the fixing portion 12 comprises a plate 22 for sealing the end of the body 18 opposite the flange 20.
• the shutter plate 22 has a disc shape of diameter substantially equal to the diameter of the body 18.
• the closure plate 22 is made of aluminum and attached to the body 18, for example by gluing.
• the measuring portion 14 includes a substantially domed cap 24.
• the cover 24 has a central portion for receiving optical components and delimits two optical measuring channels V1 and V2 in each of which water can flow as will be seen later.
• the cover 24 is made from polyurethane resin so as to protect the measuring portion 14 from the ambient natural light.
• the cover 24 is fixed to the casing 16 by two assembly screws 26 passing through two diametrically opposed connecting holes 28A, formed on the circumference of the cap 24 and two diametrically opposite connecting orifices 28B formed on the circumference of the collar 20, the connecting holes 28A, 28B being arranged in pairs.
• the fluorimeter 10 is fixed in the dry compartment of the underwater system by two fixing screws 30 passing through two diametrically opposite fixing holes 32A formed on the circumference of the cover 24 and two diametrically opposite fixing holes 32B arranged on the circumference of the collar. 20, the fixing holes 32A, 32B being arranged in correspondence two by two.
• the fixing orifices 32A, 32B are angularly offset relative to the respective connecting orifices 28A, 28B by an angle substantially equal to 90 °.
• O-rings 34 for example two in number, are provided on the body
• the fluorimeter 10 is adapted to simultaneously detect / quantify two fluorescent aromatic compounds of interest, an aromatic compound being associated with an optical measurement channel and each aromatic compound having its own fluorophore.
• the fluorimeter 10 comprises an excitation module 40 adapted to excite the fluorophores and a detection module 42 adapted to detect the light emitted by the excited fluorophores.
• a fluorophore that is to say a fluorescent compound
• it goes from its fundamental electronic state to an excited electronic state.
• the return to the ground state is done by very fast emission of a lower energy photon, and thus a longer wavelength, than that of the excitation photon because there is a loss of energy by relaxation.
• the light emitted by the fluorophore is the fluorescence light (or emission light). Therefore, a fluorophore is characterized by a specific pair of wavelengths: an excitation wavelength ⁇ and a transmission wavelength ⁇ m, AEm always being greater than AEx.
• the intensity of the fluorescence light of the fluorophore is proportional to its concentration in the medium under consideration.
• Most fluorophores are aromatic compounds that exhibit a cyclic molecular structure.
• the excitation module 40 comprises a first light source 44 for the optical measuring channel V1 and a second light source 46 for the optical measuring channel V2.
• the first and second light sources 44, 46 are selective light sources of the UV LED type, which make it possible to excite at a specific wavelength the fluorophores of interest present in the medium under study.
• the detection module 42 comprises, for each measuring channel V1 and V2, a photon detector 48, 50, an interference optical filter, only the filter 54 of the measurement channel V2 is visible in FIG. 7, and an optical system 56, 58.
• the photon detectors 48, 50 are non-wavelength photon detectors that measure the fluorescence light intensity of the fluorophores.
• the photon detectors 48, 50 are silicon photodiodes.
• the optical filters 54 make it possible to select the emission wavelengths AEm which are detected by the photodiodes 48, 50.
• the optical systems 56, 58 make it possible to redirect the flows of excitation and fluorescence light in the desired directions.
• each optical system 56, 58 comprises a biconvex lens quartz, only the lens 62 of the measuring path V2 is visible in Figure 7, and a prism 64, 66 quartz inclined at 45 °.
• the optical systems 56, 58 comprise a common quartz port 68.
• the optical components that are specific to the targeted fluorophore are the LED and the interference filter.
• the optical measuring channel V1 of the fluorimeter 10 is dedicated to the detection / quantification of phenanthrene (Phe), which is a polyaromatic hydrocarbon (PAH) with three fused rings of benzene (C 14 H 10 ).
• Phe is one of the most abundant PAHs in the aquatic environment and is one of the most fluorescent PAHs with a maximum of AEX / AEm fluorescence: 235-255 / 345-370 nm.
• Phe is a good indicator of oil contaminations in the aquatic environment.
• UV LED 44 emitting at 250 nm and an interference filter centered at 360 nm (AEx1 / AEm1: 250/360 nm).
• the bandwidths (FWHM for Full Width Half Maximum) of the LED 44 and the filter are 12 nm.
• the measurement channel V1 (AEx1 / AEm3: 250/427 nm) becomes operative for the detection / quantification of terrestrial humic acids (AHT) .
• AHTs which have a maximum fluorescence at AEx / AEm: 230-260 / 400-440 nm, are good tracers of source of organic matter.
• the optical measuring channel V2 of the fluorimeter 10 is dedicated to the detection / quantification of tryptophan (Try), which is an aromatic amino acid ( ⁇ ⁇ 12 ⁇ 2 0 2 ). Try, which has one of these Aex / AEm fluorescence maxima: 265-285 / 335-360 nm, is a good indicator of the presence of fecal bacteria and contamination by wastewater.
• UV LED 46 emitting at 280 nm and an interference filter 54 centered at 340 nm (AEx2 / AEm2: 280/340 nm).
• the FWHMs of the LED 46 and the filter 54 are 12 nm.
• the measurement channel V2 (AEx2 / AEm4: 280/405 nm) becomes operative for the detection / quantification of marine humic acids (AHM ).
• AHMs which have a maximum fluorescence at AEx / AEm: 280-310 / 380-420 nm, are good tracers of organic matter source.
• the fluorimeter 10 thus allows the simultaneous detection / quantification of two aromatic compounds of interest in the aquatic environment, a single compound being detected optically, and for each channel, the choice can be made between two compounds depending on the interference filter used. .
• the optical channel V1 (LED 250 nm, filter 360 or 427 nm) is dedicated to the measurement of
• the optical path V2 (LED 280 nm, 340 or 405 nm filter) is dedicated to the measurement of the Try or the AHM.
• V1 / V2 There are four possible combinations in V1 / V2: Phe / Try, AHT / Try, Phe / AHM and AHT / AHM.
• the choice of a configuration is made by the user when ordering the fluorometer.
• the configuration can be changed at any time by the manufacturer at the request of the user, for example depending on the type of oceanographic mission to be performed.
• the UV LEDs 44, 46 are each disposed in an excitation sleeve 70, 72 and associated with a biconvex quartz lens, only the lens 76 of the measurement path V2 is visible in FIG. 7.
• the excitation bushings 70, 72 are positioned vertically upwards, diametrically opposite, adjacent the axis A-A and facing the through openings 21 A, 21 B of the partition wall 21.
• the photodiodes 48, 50 are each arranged in a detection socket 78,
• the detection bushes 78, 80 are positioned vertically upwards, diametrically opposed, adjacent to the corresponding excitation bushings 70, 72 and facing the through openings 21 C, 21 D of the partition wall 21.
• the prisms 64, 66 are embedded in the central portion of the cover 24 so as to be symmetrical with respect to the axis A-A.
• the quartz window 68 is received in the inner chamber formed by the flange 20 of the housing 16 and fixed for example by gluing.
• the fluorimeter 10 further comprises a control module 82 comprising, for each measuring channel V1, V2, a reference detector 84, 86 which measures the intensity of the radiation emitted by the respective LED 44, 46 so as to correct the signal of fluorescence of possible fluctuations of the LED 44, 46.
• the reference detectors 84, 86 are silicon photodiodes which are each arranged in a control socket 88, 90.
• the control bushes 88, 90 are positioned vertically upwards, diametrically opposite and adjacent the corresponding excitation bushings 70, 72 and the corresponding detection bushes 78, 80.
• the fluorimeter 10 comprises an electronic system 92 supplying the two measurement channels V1 and V2.
• the electronic system 92 is thus common with the two optical paths.
• the electronic system 92 comprises three four-layer printed circuits: an excitation circuit 94 dedicated to controlling the LEDs 44, 46, a detection circuit 96 used for driving the silicon photodiodes 48, 50, 84, 86 and a circuit control 98.
• the detection circuit 96 is also used to convert the signals recorded by the silicon photodiodes 48, 50, 84 and 86. This conversion is an analog-to-digital conversion.
• the detection circuit 96 comprises an analog-to-digital converter able to perform analog-to-digital conversions.
• the control circuit 98 is, according to the example of FIGS. 4 and 5, able to receive the digital data coming from the detection circuit 96.
• control circuit 98 makes it possible to control the synchronization of the LEDs 44 and 46 and the photodiodes 48, 50, 84, 86.
• control circuit 98 serves as the I2C interface between the fluorimeter 10 and the underwater vehicle that receives it.
• An I2C interface is an easy interface to implement.
• the electronic system 92 provides many advantages. It makes it possible to obtain a large dynamic measurement that can be adjusted.
• the integration time of the measurement can thus be highly varied by the user.
• the integration time of the measurement corresponds to the time interval during which an LED 44, 46 is lit and during which the fluorescence light signal is measured by the associated photodiode 48, 50, 84, 86.
• the integration time varies from 2 ms (milliseconds) to 2000 ms.
• the capacitance of the capacitor of the analog-to-digital converter of the detection circuit 96 can also vary greatly, especially at the request of the user.
• this electrical capacitance can be worth a plurality of values.
• the capacity is equal to 3 pF (picofarads), 12 pF, 25 pF, 36 pF, 50 pF, 60 pF, 73 pF or 87.5 pF.
• Having a large dynamic range of adjustable measurement has the advantage of allowing a good tunability of the sensitivity of the fluorometer 10.
• the measurement strategy employed can also take into account the underwater vehicle on which the fluorimeter 10 is integrated.
• the three circuits 94, 96, 98 are positioned one below the other so as to be substantially parallel to each other and concentric with axis A-A.
• the three circuits 94, 96, 98 are oriented upwards, ie towards the measurement channels V1 and V2.
• the electronic system 92 thus makes it possible to considerably reduce the bulk of the fluorimeter 10. In particular, it is avoided that wires or connectors are scattered inside the fluorimeter 10.
• all the optical components of fluorimeter 10 are of UV grade quality to be completely transparent to UV radiation of short wavelengths emitted by the LEDs.
• the fluorimeter 10 is an autonomous sensor behaving electrically as a module I2C "slave” compared to a controller I2C "master”, in this case the central computer of the underwater system.
• the fluorimeter 10 comprises four measuring channels which operate simultaneously: a pathway for the determination of Phe, a way for the dosage of the Try, a channel for the control of the LED 44 (associated with the Phe) and a channel for the control of the LED 46 (associated with the Try).
• the fluorimeter 10 has reduced dimensions, of the order of 75.6 mm in diameter and 75 mm in length.
• the weight of the fluorimeter 10 is also reduced, of the order of 300 g.
• the materials (aluminum, polyurethane) and the mechanical architecture used ensure that the fluorometer 10 has a pressure resistance of up to 100 bar, ie 1000 m of depth.
• the fluorimeter 10 is supplied with 10-12 V by the batteries or the batteries of the underwater system and consumes about 50 mA at 12 V, or about 0.6 W.
• the operation of the fluorometer 10 is explained below with reference to FIG. 7 and for the measurement channel V2 of the Try.
• the photon flux emitted by the UV LED 46 is collimated / focused by the lens 76, passes through the quartz window 68 and finally arrives at the quartz prism 66 which is positioned in the extension of the excitation sleeve 72.
• the prism 66 directs the flow of photons towards the outside of the fluorimeter 10, that is to say in the surrounding medium (freshwater or marine), to excite the target molecules present.
• the two prisms 64, 66 are arranged symmetrically with respect to the axis A-A, the radiations coming from the two LEDs 44, 46 are returned in opposite directions and there is therefore no risk of disturbance of a optical path by the other.
• the excited molecules emit a fluorescent light in return, a fraction of which passes through the porthole 68 and enters the detection socket 80.
• the interference filter 54 passes the wavelength AEm of interest by absorbing all the other wavelengths.
• the flow of photons of interest which passes through the filter 54 is then collimated / focused by the lens 62 to be optimally collected by the photodiode 50 which converts the received light signal into an electrical signal.
• the control socket 90 is used to control the flow of photons emitted by the LED 46.
• a piece of optical fiber 100 makes it possible to transfer a certain quantity of photons emitted by the LED 46 to the reference photodiode 86. As photons emitted by the LED 46 change over time, the fluorescence measurement can be corrected by the control measurement, the fluorescence intensity being directly proportional to the intensity of the excitation light.
• the invention thus proposes a submersible two-channel fluorometer for UV light sources of short wavelengths (less than 300 nm) for the detection / quantification of targeted aromatic compounds in the aquatic environment.
• the fluorimeter according to the invention is designed, from the mechanical point of view (very small size and weight) and electrical (very low consumption), to be easily integrated on any type of platform / underwater autonomous or wired: gliders or " gliders >>, float-profilers, propeller vehicles (AUVs), buoys, remote-controlled robots (ROVs), etc.
• the fluorimeter according to the invention can be adapted for the analysis of a single aromatic compound or of several aromatic compounds, depending on the space available to accommodate the fluorometer on the underwater system.

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• 2011
  • 2011-03-04 FR FR1151780A patent/FR2972260B1/fr active Active
• 2012
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