WO2021172738A1 - Procédé pour l'estimation de la concentration en hydrocarbures aromatiques polycycliques par l'utilisation d'une analyse à longueurs d'onde multiples - Google Patents

Procédé pour l'estimation de la concentration en hydrocarbures aromatiques polycycliques par l'utilisation d'une analyse à longueurs d'onde multiples Download PDF

Info

Publication number
WO2021172738A1
WO2021172738A1 PCT/KR2021/000265 KR2021000265W WO2021172738A1 WO 2021172738 A1 WO2021172738 A1 WO 2021172738A1 KR 2021000265 W KR2021000265 W KR 2021000265W WO 2021172738 A1 WO2021172738 A1 WO 2021172738A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
wavelength
benzo
concentration
pyrene
Prior art date
Application number
PCT/KR2021/000265
Other languages
English (en)
Korean (ko)
Inventor
이지현
김성훈
Original Assignee
재단법인 한국화학융합시험연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 재단법인 한국화학융합시험연구원 filed Critical 재단법인 한국화학융합시험연구원
Publication of WO2021172738A1 publication Critical patent/WO2021172738A1/fr

Links

Images

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
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • 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
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry

Definitions

  • the present invention relates to a method for estimating the concentration of polyaromatic hydrocarbons using multi-wavelength analysis, and more particularly, to output fluorescence wavelength values for a plurality of polyaromatic hydrocarbons (PAHs) in a 3D scan, and output fluorescence wavelength values It relates to a method for estimating the concentration for polyaromatic hydrocarbon substances using
  • PAHs polyaromatic hydrocarbons
  • CO2 carbon dioxide
  • NOx nitrogen oxides
  • PM particulate matter
  • the flag state approves those with equivalent performance or more, and the flag state refers to the guidelines set by the organization, and the environment and human beings should not be harmed. is specifying
  • EGCS consists of a variety of technologies and, depending on the design, a significant amount of washing water is discharged from the EGCS into the ocean. Since the effluent contains chemicals and residues, the IMO is providing guidelines for EGCS to prove that the washing water sprayed to wash the exhaust gas is not harmful to the marine environment. The guidelines state that flushing water must be continuously monitored and recorded when EGCS is operated in ports, harbors or estuaries to reduce ship emissions.
  • vessels equipped with EGCS require continuous monitoring of related items after treatment of washing water and before final discharge, and must be equipped with compulsory pH, polycyclic aromatic hydrocarbon (PAH), and turbidity sensors.
  • PAHs polyaromatic hydrocarbons
  • the maximum continuous polyaromatic hydrocarbons (PAHs) concentration contained in the washing water should be 50 ⁇ g/L PAHphe or more in terms of phenanthrene equivalent than the influent concentration, and the flow rate of the washing water passing through the EGCS is 45 t/MWh or fuel oil combustion. It is standardized for 80% of the rated power of the device.
  • the polyaromatic hydrocarbon (PAHs) concentration can be adjusted upward or downward according to the flow rate of the washing water, but when the flow rate exceeds 2.5 t/MWh, fluorescence analysis must be used.
  • the conventional fluorescence analysis method measures only a specific material and calculates the result value by applying a correction factor determined by the manufacturer to the measured material. In this case, the actual measured value and the result value are different, and when washing water is used as a medium, there is a problem that an accurate analysis cannot be derived because the interference wavelength and the main wavelength for matching cannot be considered.
  • the technical problem to be achieved by the present invention is to output fluorescence wavelength values for a plurality of polyaromatic hydrocarbons (PAHs) materials in a 3D scan, and use the output fluorescence wavelength values to concentration for a plurality of polycyclic aromatic hydrocarbons (PAHs) materials
  • PAHs polyaromatic hydrocarbons
  • a standard sample containing polyaromatic hydrocarbons is analyzed by fluorescence to excitation wavelengths. ), obtaining an emission wavelength and a sensitivity value, scanning the obtained excitation wavelength, emission wavelength and sensitivity value and outputting the obtained excitation wavelength, emission wavelength and sensitivity value as a 3D graph, using the output 3D graph, the sensitivity value having the maximum value extracting , obtaining a dominant wavelength range corresponding to the extracted sensitivity value, generating a calibration curve graph using the obtained sensitivity value, and polycyclic aromatic hydrocarbon (PAHs) material for which the concentration is to be measured. and measuring the concentration of the measurement target sample by fluorescence analysis of the measurement target sample in the dominant wavelength range, and applying the sensitivity value obtained by the fluorescence analysis to the calibration curve graph.
  • PAHs polycyclic aromatic hydrocarbon
  • the standard sample may be analyzed for fluorescence by irradiating a light source having a wavelength range of 200 nm to 700 nm.
  • the excitation wavelength, the emission wavelength and the sensitivity value are generated in the form of a contour plot, the excitation wavelength is represented by the X-axis, the emission wavelength is represented by the Y-axis, and the sensitivity value is Z can be expressed as an axis.
  • the generating of the calibration curve graph may include generating a first point using a concentration value and a sensitivity value obtained by fluorescence analysis of the standard sample; Obtaining respective sensitivity values by irradiating a light source having a range, generating a second point and a third point by using the obtained sensitivity value and concentration value, the first point, the second point, and the third point It may include generating a calibration curve using the calibration curve, and obtaining a linear equation from the calibration curve.
  • the first point, the second point, and the third point can be determined using the highest sensitivity value among the detected sensitivity values. have.
  • the first point, the second point, and the third point may be determined using an average value calculated from each of the detected sensitivity values. .
  • the polycyclic aromatic hydrocarbon (PAHs) material is naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene.
  • pyrene (Pyrene), benzo (a) anthracene (Benzo (a) anthracene), chrysene (Chrysene), benzo (k) fluoranthene (Benzo (k) fluoranthene), benzo (b) b) fluoranthene), benzo (a) pyrene (Benzo (a) pyrene), indeno (1,2,3-cd) pyrene (Indeno (1,2,3-cd) pyrene), dibenz (a, h ) may include at least one of anthracene (Dibenz(a,h)anthracene) and benzo(g,h,i)perylene.
  • the dominant wavelength range of naphthalene includes an excitation wavelength including a range of 250 nm to 300 nm and an emission wavelength including a range of 305 nm to 370 nm,
  • the dominant wavelength range of acenaphthylene may include an excitation wavelength including a range of 255 nm to 320 nm and an emission wavelength including a range of 310 nm to 380 nm.
  • the dominant wavelength range of Acenaphthene includes an excitation wavelength including a range of 260 nm to 320 nm and an emission wavelength including a range of 310 nm to 380 nm, and the dominant wavelength range of Fluorene is , an excitation wavelength comprising the range of 240 nm to 310 nm, and an emission wavelength comprising the range of 290 nm to 350 nm.
  • the dominant wavelength range of the phenanthrene includes an excitation wavelength including the range of 230 nm to 305 nm and an emission wavelength including the range of 335 nm to 420 nm, and the dominant wavelength range of the anthracene is , an excitation wavelength comprising the range of 230 nm to 270 nm and 305 nm to 390 nm, and an emission wavelength comprising the range of 370 nm to 440 nm.
  • the dominant wavelength range of the fluoranthene includes an excitation wavelength including the range of 250 nm to 295 nm and 310 nm to 375 nm, and an emission wavelength including the range of 400 nm to 540 nm, and the pyrene (Pyrene) ) may include an excitation wavelength comprising the range of 255 nm to 280 nm and 290 nm to 345 nm, and an emission wavelength comprising the range of 360 nm to 435 nm.
  • the dominant wavelength range of the benzo (a) anthracene includes an excitation wavelength including the range of 250 nm to 310 nm and 320 nm to 370 nm, and an emission wavelength including the range of 380 nm to 460 nm
  • the dominant wavelength range of Chrysene may include an excitation wavelength including a range of 240 nm to 330 nm and an emission wavelength including a range of 350 nm to 420 nm.
  • the dominant wavelength range of the benzo (k) fluoranthene is an excitation wavelength including the range of 250 nm to 330 nm and 355 nm to 415 nm, and an emission wavelength including the range of 390 nm to 485 nm Including, the dominant wavelength range of the benzo (b) fluoranthene (Benzo (b) fluoranthene), the excitation wavelength including the range of 250 nm to 310 nm and 320 nm to 380 nm, and the range of 385 nm to 530 nm It may include an emission wavelength that includes
  • the dominant wavelength range of the benzo (a) pyrene includes an excitation wavelength including the range of 250 nm to 310 nm and 330 nm to 400 nm, and an emission wavelength including the range of 390 nm to 450 nm
  • the main wavelength range of the indeno (1,2,3-cd) pyrene is an excitation wavelength including the range of 260 nm to 325 nm and 335 nm to 395 nm and an emission wavelength comprising the range of 450 nm to 580 nm.
  • the dominant wavelength range of the dibenz (a,h) anthracene includes an excitation wavelength including a range of 265 nm to 355 nm and an emission wavelength including a range of 380 nm to 440 nm And, the dominant wavelength range of the benzo (g, h, i) perylene (Benzo (g, h, i) perylene), the excitation wavelength including the range of 260 nm to 310 nm and 355 nm to 395 nm, and 390 nm to emission wavelengths including the range of 470 nm.
  • the concentration of each of a plurality of polyaromatic hydrocarbons (PAHs) can be estimated, and the respective sensitivity (Intensity) and dominant wavelength of each of the plurality of polyaromatic hydrocarbons (PAHs) can be 3D Because it is output as a scan, it is easy to identify, and the concentration can be estimated by the prepared calibration curve, so it has the effect of real-time measurement in the field.
  • FIG. 1 is a block diagram of a multi-wavelength analysis apparatus according to an embodiment of the present invention.
  • FIG. 2 is a flowchart illustrating a method for estimating the concentration of polyaromatic hydrocarbons according to an embodiment of the present invention.
  • 3A to 3P are diagrams showing the results of fluorescence analysis of standard samples containing 16 polycyclic aromatic hydrocarbons (PAHs), respectively, in 3D graphs.
  • PAHs polycyclic aromatic hydrocarbons
  • FIG. 4 is a flowchart for explaining step S240 shown in FIG. 2 .
  • FIG. 5 is a diagram for explaining a calibration curve graph generated in step S244 shown in FIG. 4 .
  • PAHs polycyclic aromatic hydrocarbons
  • FIG. 1 is a block diagram of a multi-wavelength analysis apparatus according to an embodiment of the present invention.
  • the multi-wavelength analysis apparatus 100 includes a fluorescence analysis unit 110 , a dominant wavelength extraction unit 120 , a calibration curve generation unit 130 , and a concentration estimation unit 140 . ) is included.
  • the fluorescence analysis unit 110 fluorescence analyzes polyaromatic hydrocarbons (PAHs) material, and scans the analysis result and outputs it as a 3D graph.
  • PAHs polyaromatic hydrocarbons
  • a standard sample formed by diluting a polycyclic aromatic hydrocarbon (PAHs) material with water is quantitatively analyzed by the fluorescence analysis unit 110 .
  • the fluorescence analyzer 110 obtains an excitation wavelength range, an emission wavelength range, and a sensitivity value by measuring fluorescence emitted by irradiating light to the input standard sample.
  • the fluorescence analyzer 110 scans the obtained excitation wavelength range, emission wavelength range, and sensitivity value and outputs it as a 3D graph.
  • the fluorescence analysis unit 110 is included in the multi-wavelength analysis apparatus 100, but it is provided as a separate fluorescence analysis apparatus and the analyzed fluorescence analysis result is transferred to the multi-wavelength analysis apparatus 100. It can also be passed to
  • the dominant wavelength extraction unit 120 extracts a wavelength range corresponding to the point at which the sensitivity value is the highest using the output 3D graph.
  • polyaromatic hydrocarbons PAHs
  • PAHs polyaromatic hydrocarbons
  • the dominant wavelength extraction unit 120 extracts the dominant wavelength corresponding to the highest sensitivity value of each of the 16 polycyclic aromatic hydrocarbons (PAHs).
  • the dominant wavelength includes an excitation wavelength range and an emission wavelength range.
  • the calibration curve generating unit 130 generates a calibration curve indicating the concentration corresponding to the extracted sensitivity value.
  • the calibration curve generator 130 generates a graph composed of an x-axis indicating a concentration value of a polyaromatic hydrocarbon (PAHs) material and a y-axis indicating a sensitivity value.
  • the calibration curve generating unit 130 generates a point using the concentration value and the sensitivity value obtained from the sample including the polycyclic aromatic hydrocarbon (PAHs) material.
  • the calibration curve generating unit 130 generates a first point in order to calculate an accurate concentration. That is, the calibration curve generator 130 generates a first point by using the sensitivity value extracted when a standard sample for a polycyclic aromatic hydrocarbon (PAHs) substance of known concentration is analyzed.
  • PAHs polycyclic aromatic hydrocarbon
  • the calibration curve generating unit 130 generates additional second and third points by using the concentration values and sensitivity values obtained from a plurality of samples for analysis having different concentrations from the standard sample, and the generated first to third points are generated. Connect the points to create a calibration curve.
  • the concentration estimator 140 detects a sensitivity value by fluorescence analysis of a measurement target sample belonging to 16 polycyclic aromatic hydrocarbons (PAHs) substances of unknown concentration in the dominant wavelength range, and uses the detected sensitivity value as a pre-generated calibration curve By substituting into , the concentration of the sample to be measured is estimated.
  • PAHs polycyclic aromatic hydrocarbons
  • PAHs polyaromatic hydrocarbon
  • the fluorescence analyzer 110 fluorescence analyzes a standard sample including a polyaromatic hydrocarbon (PAHs) material (S210).
  • PAHs polyaromatic hydrocarbon
  • PAHs polyaromatic hydrocarbons
  • the standard sample includes 16 polycyclic aromatic hydrocarbons (PAHs), and the fluorescence analysis unit 110 performs fluorescence analysis while knowing the type and concentration of the standard sample.
  • PAHs polycyclic aromatic hydrocarbons
  • the polyaromatic hydrocarbon (PAHs) material is naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, Fluoranthene, Pyrene, Benzo(a)Anthracene, Chrysene, Benzo(k) Fluoranthene, Benzo(b) fluoranthene (Benzo (b) fluoranthene), benzo (a) pyrene (Benzo (a) pyrene), indeno (1,2,3-cd) pyrene (Indeno (1,2,3-cd) pyrene), and at least one of dibenz(a,h)anthracene and benzo(g,h,i)perylene.
  • PAHs polyaromatic hydrocarbon
  • the fluorescence analyzer 110 has setting values shown in Table 1 below.
  • the values set in Table 1 are set in consideration of the maximum sensitivity of the fluorescence analyzer 110 , and the set values may be adjusted according to the fluorescence analyzer 110 .
  • the fluorescence analyzer 110 exposes a light source to the input standard sample for 20 ms to perform fluorescence analysis of the polycyclic aromatic hydrocarbon (PAHs) material contained in the standard sample.
  • the irradiated light source has a wavelength range of 200 nm to 700 nm to be applicable to all 16 polycyclic aromatic hydrocarbons (PAHs) materials.
  • the fluorescence analyzer 110 performs fluorescence analysis on a standard sample to obtain an excitation wavelength, an emission wavelength, and a sensitivity value, and scans the obtained excitation wavelength, emission wavelength, and sensitivity value and outputs it as a 3D graph (S220).
  • the fluorescence analyzer 110 outputs a 3D graph in which the excitation wavelength is represented by the x-axis, the emission wavelength is represented by the y-axis, and the sensitivity value is represented by the z-axis.
  • the ranges of the x-axis and the y-axis are set from 200 nm to 700 nm, respectively.
  • the dominant wavelength extraction unit 120 extracts a sensitivity value having the highest sensitivity peak for each of the 16 polyaromatic hydrocarbons (PAHs) using the output 3D graph, and extracts the main wavelength corresponding to the extracted sensitivity value.
  • the wavelength is detected (S230).
  • 3A to 3P are diagrams showing the results of fluorescence analysis of standard samples containing 16 polycyclic aromatic hydrocarbons (PAHs), respectively, in 3D graphs.
  • PAHs polycyclic aromatic hydrocarbons
  • FIG. 3A is a diagram illustrating a result of fluorescence analysis of a standard sample containing naphthalene in a 3D graph.
  • the dominant wavelength extraction unit 130 fluorescence analyzes a standard sample containing naphthalene, and looking at the wavelength range corresponding to the obtained sensitivity value, the excitation wavelength is 250 nm to 300 nm. and the emission wavelength corresponds to 305 nm to 370 nm.
  • the excitation wavelength range and emission wavelength range extracted as described above are selected as the dominant wavelength for naphthalene.
  • FIG. 3B is a diagram illustrating a result of fluorescence analysis of a standard sample containing acenaphthylene in a 3D graph.
  • the dominant wavelength extraction unit 130 fluorescence analyzes a standard sample containing acenaphthylene, and looking at the wavelength range corresponding to the obtained sensitivity value, the excitation wavelength is 255 nm to It corresponds to 320 nm, and the emission wavelength corresponds to 310 nm to 380 nm.
  • the extracted excitation wavelength range and emission wavelength range are selected as the dominant wavelength for Acenaphthylene.
  • FIG. 3c is a graph showing the results of fluorescence analysis of a standard sample containing acenaphthene in 3D form.
  • the dominant wavelength extraction unit 130 fluoresces a standard sample containing acenaphthene, and looking at the wavelength range corresponding to the obtained sensitivity value, the excitation wavelength is 260 nm to 320 nm. and the emission wavelength corresponds to 310 nm to 380 nm.
  • the extracted excitation wavelength range and emission wavelength range are selected as the dominant wavelength for Acenaphthene.
  • FIG. 3D is a diagram illustrating a result of fluorescence analysis of a standard sample containing fluorene in a 3D graph.
  • the dominant wavelength extractor 130 fluoresces a standard sample containing fluorene, and looking at the wavelength range corresponding to the obtained sensitivity value, the excitation wavelength is 240 nm to 310 nm and the emission wavelength corresponds to 290 nm to 350 nm.
  • the extracted excitation wavelength range and emission wavelength range are selected as the dominant wavelength for fluorene.
  • FIG. 3E is a graph showing the results of fluorescence analysis of a standard sample containing phenanthrene in 3D form.
  • the dominant wavelength extractor 130 fluorescence analyzes a standard sample containing phenanthrene, and looking at the wavelength range corresponding to the obtained sensitivity value, the excitation wavelength is 230 nm to 305 nm and the emission wavelength corresponds to 335 nm to 420 nm.
  • the extracted excitation wavelength range and emission wavelength range are selected as the dominant wavelength for phenanthrene.
  • FIG. 3f is a graph showing the results of fluorescence analysis of a standard sample containing anthracene in 3D form.
  • the dominant wavelength extractor 130 acquires a sensitivity value using a 3D graph representing a result of fluorescence analysis of a standard sample containing anthracene.
  • the dominant wavelength extractor 130 may select a dominant wavelength band for each of the corresponding two groups.
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 230 nm to 270 nm
  • the emission wavelength corresponds to 370 nm to 440 nm.
  • the excitation wavelength corresponding to the sensitivity value having the peak value corresponds to 305 nm to 390 nm
  • the emission wavelength corresponds to 370 nm to 440 nm.
  • Each extracted excitation wavelength range and emission wavelength range is selected as a dominant wavelength for anthracene.
  • FIG. 3G is a graph showing the results of fluorescence analysis of a standard sample containing fluoranthene in 3D form.
  • the dominant wavelength extractor 130 obtains a sensitivity value using a 3D graph according to a result of fluorescence analysis of a standard sample containing fluoranthene.
  • the dominant wavelength extractor 130 may select the dominant wavelength band for each of the corresponding two groups. have.
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 250 nm to 295 nm
  • the emission wavelength corresponds to 400 nm to 540 nm.
  • an excitation wavelength corresponding to a sensitivity value having a peak value corresponds to 310 nm to 375 nm
  • an emission wavelength corresponds to 400 nm to 540 nm.
  • Each extracted excitation wavelength range and emission wavelength range is selected as the dominant wavelength for fluoranthene.
  • Figure 3h is a diagram showing a 3D graph showing the result of fluorescence analysis of a standard sample containing pyrene (Pyrene).
  • the dominant wavelength extractor 130 acquires a sensitivity value using a 3D graph representing a result of fluorescence analysis of a standard sample containing pyrene.
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 255 nm to 280 nm
  • the emission wavelength corresponds to 360 nm to 435 nm.
  • the excitation wavelength corresponding to the sensitivity value having the peak value corresponds to 290 nm to 345 nm
  • the emission wavelength corresponds to 360 nm to 435 nm.
  • Each extracted excitation wavelength range and emission wavelength range is selected as the dominant wavelength for Pyrene.
  • Figure 3i is a diagram showing a 3D graph showing the result of fluorescence analysis of a standard sample containing benzo (a) anthracene (Benzo (a) anthracene).
  • the dominant wavelength extraction unit 130 obtains a sensitivity value using a 3D graph according to the result of fluorescence analysis of a standard sample containing benzo (a) anthracene. .
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 250 nm to 310 nm
  • the emission wavelength corresponds to 380 nm to 460 nm.
  • the excitation wavelength corresponding to the sensitivity value having the peak value corresponds to 320 nm to 370 nm
  • the emission wavelength corresponds to 380 nm to 460 nm.
  • Each extracted excitation wavelength range and emission wavelength range is selected as a dominant wavelength for benzo(a)anthracene.
  • 3J is a diagram illustrating a 3D graph showing the result of fluorescence analysis of a standard sample containing Chrysene.
  • the dominant wavelength extraction unit 130 fluorescence analyzes a standard sample containing Chrysene, and looking at the wavelength range corresponding to the obtained sensitivity value, the excitation wavelength is 240 nm to 330 nm and the emission wavelength corresponds to 350 nm to 420 nm.
  • the extracted excitation wavelength range and emission wavelength range are selected as the dominant wavelength for Chrysene.
  • FIG. 3K is a graph showing the results of fluorescence analysis of a standard sample containing benzo(k)fluoranthene in 3D form.
  • the dominant wavelength extraction unit 130 obtains a sensitivity value using a 3D graph according to the result of fluorescence analysis of a standard sample containing benzo (k) fluoranthene. acquire
  • the dominant wavelength extractor 130 extracts the dominant wavelength for each of the corresponding two groups. You can select a band.
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 250 nm to 330 nm
  • the emission wavelength corresponds to 390 nm to 485 nm.
  • the excitation wavelength corresponding to the sensitivity value having the peak value corresponds to 355 nm to 415 nm
  • the emission wavelength corresponds to 390 nm to 485 nm.
  • Each extracted excitation wavelength range and emission wavelength range is selected as the dominant wavelength for benzo(k)fluoranthene.
  • FIG. 3L is a graph showing the results of fluorescence analysis of a standard sample containing benzo(b) fluoranthene in 3D form
  • the dominant wavelength extraction unit 130 calculates the sensitivity value using a 3D graph according to the result of fluorescence analysis of a standard sample containing benzo(b) fluoranthene. acquire
  • the dominant wavelength band can be selected for each of the two groups. have.
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 250 nm to 310 nm
  • the emission wavelength corresponds to 385 nm to 530 nm.
  • an excitation wavelength corresponding to a sensitivity value having a peak value corresponds to 320 nm to 380 nm
  • an emission wavelength corresponds to 385 nm to 530 nm.
  • Each extracted excitation wavelength range and emission wavelength range is selected as the dominant wavelength for benzo(b) fluoranthene.
  • 3m is a diagram illustrating a 3D graph showing the result of fluorescence analysis of a standard sample containing benzo (a) pyrene.
  • the dominant wavelength extraction unit 130 obtains a sensitivity value using a 3D graph according to the result of fluorescence analysis of a standard sample containing benzo (a) pyrene. .
  • the dominant wavelength extractor 130 for each of the corresponding two groups.
  • the dominant wavelength band can be selected.
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 250 nm to 310 nm
  • the emission wavelength corresponds to 390 nm to 450 nm.
  • the excitation wavelength corresponding to the sensitivity value having the peak value corresponds to 330 nm to 400 nm
  • the emission wavelength corresponds to 390 nm to 450 nm.
  • Each of the extracted excitation wavelength range and emission wavelength range is selected as the dominant wavelength for benzo(a)pyrene.
  • 3n is a diagram illustrating a 3D graph showing the result of fluorescence analysis of a standard sample containing indeno (1,2,3-cd) pyrene.
  • the dominant wavelength extraction unit 130 fluorescence analysis of a standard sample containing indeno (1,2,3-cd) pyrene (Indeno (1,2,3-cd) pyrene)
  • a sensitivity value is obtained using a 3D graph representing the result.
  • indeno (1,2,3-cd) pyrene (Indeno (1,2,3-cd) pyrene) was detected in the peak form of sensitivity values in each of the two groups, so the dominant wavelength extraction
  • the unit 130 may select a dominant wavelength band for each of the two corresponding groups.
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 260 nm to 325 nm
  • the emission wavelength corresponds to 450 nm to 580 nm.
  • the excitation wavelength corresponding to the sensitivity value having a peak value corresponds to 335 nm to 395 nm
  • the emission wavelength corresponds to 450 nm to 580 nm.
  • Each extracted excitation wavelength range and emission wavelength range is selected as the dominant wavelength for indeno(1,2,3-cd)pyrene.
  • Figure 3o is a diagram showing a 3D graph showing the result of fluorescence analysis of a standard sample containing dibenz (a,h) anthracene (Dibenz (a,h) anthracene).
  • the dominant wavelength extraction unit 130 fluorescence analysis of the standard sample containing dibenz (a,h) anthracene (Dibenz (a,h) anthracene), corresponding to the obtained sensitivity value at this time
  • the excitation wavelength corresponds to 265 nm to 355 nm
  • the emission wavelength corresponds to 380 nm to 440 nm.
  • the extracted excitation wavelength range and emission wavelength range are selected as dominant wavelengths for Dibenz(a,h)anthracene.
  • FIG. 3p is a graph showing the result of fluorescence analysis of a standard sample containing benzo(g,h,i)perylene in 3D form;
  • the dominant wavelength extraction unit 130 3D showing the result of fluorescence analysis of a standard sample containing benzo(g,h,i)perylene Acquire the sensitivity value using the graph.
  • the dominant wavelength extractor 130 can select the dominant wavelength band for each of the two corresponding groups.
  • the excitation wavelength corresponding to the sensitivity value having the peak value in the first group corresponds to 260 nm to 310 nm
  • the emission wavelength corresponds to 390 nm to 470 nm.
  • the excitation wavelength corresponding to the sensitivity value having the peak value corresponds to 355 nm to 395 nm
  • the emission wavelength corresponds to 390 nm to 470 nm.
  • Each extracted excitation wavelength range and emission wavelength range is selected as a dominant wavelength for benzo(g,h,i)perylene.
  • the dominant wavelength including all 16 polycyclic aromatic hydrocarbons (PAHs) materials has an excitation wavelength in the range of 230 nm or more and 415 nm or less, and an emission wavelength in the range of 290 nm or more and 580 nm or less. (emission).
  • PAHs polycyclic aromatic hydrocarbons
  • the calibration curve generator 130 obtains a calibration curve graph using the extracted sensitivity value and concentration value (S240).
  • FIG. 4 is a flowchart for explaining step S240 shown in FIG. 2
  • FIG. 5 is a view for explaining a calibration curve graph generated in step S244 shown in FIG. 4 .
  • the calibration curve generator 130 generates a first point for each standard sample by using the concentration and sensitivity values obtained through 16 standard samples ( S241 ).
  • the calibration curve generator 130 displays the first point on the calibration curve graph by using the concentration value and the sensitivity value of the standard sample obtained in step S230.
  • the concentration value and the sensitivity value of the standard sample obtained through FIGS. 3A to 3P are designated as the first point as the x-coordinate value and the y-coordinate value, respectively.
  • -cd)pyrene (Indeno(1,2,3-cd)pyrene) and benzo(g,h,i)perylene two sensitivity values were detected, A sensitivity value having a higher value among the two detected sensitivity values may be applied as the y-coordinate value of the first point, or an average value of the two sensitivity values may be applied as the y-coordinate value of the first point.
  • the fluorescence analyzer 110 additionally fluoresces two samples for analysis having different concentrations for each polyaromatic hydrocarbon (PAHs) material to determine the respective sensitivity values. Acquire (S242).
  • two samples for analysis are set to have a lower concentration than the reference sample, but may be set to have a higher concentration than the reference sample.
  • the prepared sample for analysis is analyzed for fluorescence by the fluorescence analyzer 110 .
  • the fluorescence analyzer 110 irradiates the light source having the dominant wavelength range extracted in step S230 to the sample for fluorescence analysis.
  • the excitation wavelength range of 250 nm to 300 nm and the emission wavelength range of 305 nm to 370 nm are the dominant wavelength ranges. Fluorescence analysis is performed by irradiation.
  • the calibration curve generator 130 when the fluorescence analysis of the two samples for analysis is completed, the calibration curve generator 130 generates a second point and a third point by using the concentration and sensitivity values obtained from the two samples for analysis (S243). ).
  • a sensitivity value obtained from a standard sample having a concentration of 0.5% is 280 cnt
  • a sensitivity value obtained from a sample for analysis having a concentration of 0.2% is 100 cnt
  • a sample for analysis having a concentration of 0.1% It is assumed that the sensitivity value obtained from is 40 cnt.
  • the calibration curve generation unit 130 has a first point having a coordinate value of (0.5, 280), a second point having a coordinate value of (0.2, 100), and a third point having a coordinate value of (0.1, 40). are input into the graph.
  • the sensitivity value having the higher value among the two detected sensitivity values may be applied as the y-coordinate value of the second and third points.
  • the average value of the two sensitivity values may be applied as the y-coordinate values of the second and third points.
  • the calibration curve generation unit 130 generates a calibration curve using the generated first point, second point, and third point (S244).
  • the calibration curve generating unit 130 generates a straight line passing through the input first point, the second point, and the third point closest to each other.
  • the x-axis of the calibration curve graph shown in FIG. 5 represents the concentration value
  • the y-axis represents the sensitivity value
  • a calibration curve is generated using three points using one standard sample and two samples for analysis.
  • points may be obtained using more samples.
  • the calibration curve generation unit 130 obtains a straight line equation using the generated three points (S245).
  • the calibration curve generating unit 130 derives a linear equation using the first to third points, and the derived linear equation is expressed by Equation 1 below.
  • the calibration curve generating unit 130 evaluates the linearity of the generated calibration curve, and the evaluation of the linearity of the calibration curve is use value.
  • coefficient of determination is a coefficient indicating how much the generated straight line is correlated with the first to third points, and is used as an indicator to check whether the data obtained by the actual analysis is well located on the straight line. in other words, A value of 1 indicates that the analysis data and the calibration curve are in agreement, which corresponds to an ideal value.
  • the concentration estimator 140 fluoresces the measurement target sample for which the concentration is to be measured, and estimates the concentration by substituting the obtained sensitivity value into the previously generated calibration curve (S250).
  • the sample to be measured is one of 16 polycyclic aromatic hydrocarbons (PAHs) materials, and since the main wavelengths for the excitation wavelength and emission wavelength of the light source are already determined for each material type in step S230, the fluorescence analysis unit 110 ) is the determined dominant wavelength band, and fluorescence analysis is performed on the sample to be measured.
  • PAHs polycyclic aromatic hydrocarbons
  • the fluorescence pumice unit 110 acquires a sensitivity value in a corresponding dominant wavelength band with respect to the sample to be measured.
  • the concentration estimator 140 estimates the corresponding concentration value by substituting the sensitivity value received from the fluorescence analyzer 110 into the previously generated calibration curve.
  • PAHs polycyclic aromatic hydrocarbons
  • the concentration estimator 140 substitutes the sensitivity value having a higher value among the two detected sensitivity values into the linear equation to determine the concentration. It may be estimated or the concentration may be estimated by substituting the average value of the two sensitivity values into the linear equation.
  • PAHs polycyclic aromatic hydrocarbon
  • a calibration curve is obtained using the dominant wavelength range and sensitivity value respectively obtained from 16 polycyclic aromatic hydrocarbons (PAHs) materials, and the measurement target sample is measured using the linearity of the obtained calibration curve. concentration can be estimated.
  • PAHs polycyclic aromatic hydrocarbons
  • PAHs polyaromatic hydrocarbon
  • the multi-wavelength analysis method can estimate the concentration of each of the 16 polyaromatic hydrocarbons (PAHs), and each sensitivity to the 16 polyaromatic hydrocarbons (PAHs) substances (Intensity) ) and the dominant wavelength are output as 3D scan, so it is easy to identify, and the concentration can be estimated by the prepared calibration curve, so it has the effect of real-time measurement in the field.
  • PAHs 16 polyaromatic hydrocarbons
  • Intensity Intensity

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Immunology (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Pathology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Optics & Photonics (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

La présente invention concerne un procédé pour l'estimation de la concentration en hydrocarbures aromatiques polycycliques par l'utilisation d'une analyse à longueurs d'onde multiples. Selon la présente invention, le procédé pour l'estimation de la concentration en hydrocarbures aromatiques polycycliques par l'utilisation d'un appareil d'analyse à longueurs d'onde multiples comprend les étapes consistant à : acquérir des longueurs d'onde d'excitation, des longueurs d'onde d'émission et des valeurs de sensibilité qui sont mesurées par analyse de fluorescence d'un échantillon étalon comprenant des hydrocarbures aromatiques polycycliques (HAP) ; balayer les longueurs d'onde d'excitation, les longueurs d'onde d'émission et les valeurs de sensibilité acquises devant être délivrées en sortie sous la forme d'un graphique en 3D ; extraire la valeur de sensibilité maximale par l'utilisation du graphique en 3D délivré en sortie et acquérir une plage de longueur d'onde dominante correspondant à la valeur de sensibilité extraite ; créer un graphique de courbe d'étalonnage à l'aide des valeurs de sensibilité acquises ; et réaliser une analyse de fluorescence, dans la plage de longueur d'onde dominante, sur un échantillon à mesurer comprenant des HAP dont la concentration doit être mesurée, et substituer les valeurs de sensibilité acquises par l'analyse de fluorescence dans le graphique de courbe d'étalonnage pour mesurer la concentration des HAP. Ainsi, selon la présente invention, la concentration de chacun des HAP peut être estimée, il est aisé d'identifier les HAP puisque la sensibilité et la longueur d'onde dominante de chacun des HAP sont délivrées en sortie par balayage en 3D, et il existe l'effet consistant à permettre une estimation de concentration par la courbe d'étalonnage créée, ce qui permet une mesure en temps réel sur un site.
PCT/KR2021/000265 2020-02-27 2021-01-08 Procédé pour l'estimation de la concentration en hydrocarbures aromatiques polycycliques par l'utilisation d'une analyse à longueurs d'onde multiples WO2021172738A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2020-0024430 2020-02-27
KR20200024430 2020-02-27
KR10-2020-0061466 2020-05-22
KR1020200061466A KR102184180B1 (ko) 2020-02-27 2020-05-22 다파장 분석을 이용한 다환방향족 탄화수소의 농도 추정 방법

Publications (1)

Publication Number Publication Date
WO2021172738A1 true WO2021172738A1 (fr) 2021-09-02

Family

ID=73641589

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2021/000265 WO2021172738A1 (fr) 2020-02-27 2021-01-08 Procédé pour l'estimation de la concentration en hydrocarbures aromatiques polycycliques par l'utilisation d'une analyse à longueurs d'onde multiples

Country Status (2)

Country Link
KR (1) KR102184180B1 (fr)
WO (1) WO2021172738A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102184180B1 (ko) * 2020-02-27 2020-11-27 재단법인 한국화학융합시험연구원 다파장 분석을 이용한 다환방향족 탄화수소의 농도 추정 방법
KR102374932B1 (ko) 2021-02-09 2022-03-16 대윤계기산업 주식회사 다환방향족 탄화수소 농도 측정 시스템
CN114813680B (zh) * 2022-04-22 2024-05-07 天津农学院 一种基于二维荧光相关谱分离测定水中腐殖酸的方法
CN114720446B (zh) * 2022-04-22 2024-06-18 天津农学院 基于荧光相关切谱分离腐殖酸定量分析多环芳烃的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002168789A (ja) * 2000-11-29 2002-06-14 Takashi Inaga 多環芳香族炭化水素類の検出法および装置
JP2003065956A (ja) * 2001-08-23 2003-03-05 Hitachi Ltd 蛍光ピーク検出方法及び分光蛍光光度計
KR20100074600A (ko) * 2008-12-24 2010-07-02 주식회사 포스코 혼합용액의 각 성분별 농도 측정방법
JP2016107235A (ja) * 2014-12-10 2016-06-20 水ｉｎｇ株式会社 分離膜の汚染状態分析方法、その方法を用いるろ過対象水の水質評価方法、及び分離膜の汚染状態分析方法を行うためのろ過システム
JP2017227577A (ja) * 2016-06-24 2017-12-28 オルガノ株式会社 水処理システムにおける水中の有機物評価方法及び水処理システム
KR102184180B1 (ko) * 2020-02-27 2020-11-27 재단법인 한국화학융합시험연구원 다파장 분석을 이용한 다환방향족 탄화수소의 농도 추정 방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030080533A (ko) * 2002-04-09 2003-10-17 자인테크놀로지(주) 자외선을 이용한 토양 유류 오염 실시간 측정 시스템 및측정 방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002168789A (ja) * 2000-11-29 2002-06-14 Takashi Inaga 多環芳香族炭化水素類の検出法および装置
JP2003065956A (ja) * 2001-08-23 2003-03-05 Hitachi Ltd 蛍光ピーク検出方法及び分光蛍光光度計
KR20100074600A (ko) * 2008-12-24 2010-07-02 주식회사 포스코 혼합용액의 각 성분별 농도 측정방법
JP2016107235A (ja) * 2014-12-10 2016-06-20 水ｉｎｇ株式会社 分離膜の汚染状態分析方法、その方法を用いるろ過対象水の水質評価方法、及び分離膜の汚染状態分析方法を行うためのろ過システム
JP2017227577A (ja) * 2016-06-24 2017-12-28 オルガノ株式会社 水処理システムにおける水中の有機物評価方法及び水処理システム
KR102184180B1 (ko) * 2020-02-27 2020-11-27 재단법인 한국화학융합시험연구원 다파장 분석을 이용한 다환방향족 탄화수소의 농도 추정 방법

Also Published As

Publication number Publication date
KR102184180B1 (ko) 2020-11-27

Similar Documents

Publication Publication Date Title
WO2021172738A1 (fr) Procédé pour l'estimation de la concentration en hydrocarbures aromatiques polycycliques par l'utilisation d'une analyse à longueurs d'onde multiples
JPS6471122A (en) Method of inspecting quality of reticle mask pattern and the like, its object for monitor and method of inspecting object
TW200604517A (en) Method and system for the inspection of a wafer
ATE500531T1 (de) Verfahren und anordnung zur bestimmung der fokusposition bei der abbildung einer probe
DE602004029378D1 (de) Vorrichtung und verfahren zur automatischen inspektion von materialbahnen
WO1999014706A3 (fr) Systeme d'inspection optique et de verification
JP5497988B2 (ja) インキスプリット修正方法
WO2002029886A3 (fr) Procede et appareil permettant d'inspecter la surface d'un substrat au moyen de techniques de profilage spectral
KR960032624A (ko) 포토마스크 패턴결함을 검사하는 장치 및 방법
WO2021066291A1 (fr) Scanner à ultrasons de type portatif et dispositif de balayage à ultrasons mobile pour la détection de défauts dans les zones soudées
WO2016039564A1 (fr) Appareil et procédé de détection de défauts de collage triple couche dans un transporteur de gnl
WO2009119983A2 (fr) Système de vérification d'un substrat fpd et de tranches à semi-conducteurs utilisant des images dupliquées
WO2022065595A1 (fr) Procédé et dispositif de mesure de signal de résistance permettant de surveiller la résistance d'une structure de matériau de réaction d'hydratation
DE69840684D1 (de) Vorrichtung und verfahren zur messung der zusammensetzung eines gases unter verwendung eines ionenleitenden elektrolyten
US8165384B1 (en) Defect classification
WO2022139013A1 (fr) Appareil de test de bruit de moteur et procédé de test utilisant un capteur ae
WO2009093840A2 (fr) Procédé et appareil destinés à estimer les caractéristiques de matériaux cibles au moyen d'informations de changement cinétique
KR100274594B1 (ko) 반도체 웨이퍼의 검사장치 및 검사방법.
WO2021020604A1 (fr) Appareil de mesure et procédé de mesure pour l'épaisseur et l'indice de réfraction d'un film mince multicouche, à l'aide d'une image d'interférence spectrale à résolution angulaire selon la polarisation
JP2005172649A (ja) 欠陥検査装置
WO2018097543A1 (fr) Appareil de détection de flammes et procédé de commande de flammes associé
JP2000258352A (ja) フォトマスク外観検査装置
WO2024071617A1 (fr) Système d'analyse d'état d'application et procédé associé
WO2021085864A2 (fr) Procédé et dispositif de classification d'objet basés sur un capteur d'image
WO2024101857A1 (fr) Dispositif de test de concentration d'application utilisant un éclairage couleur et une caméra, et procédé associé

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21760903

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21760903

Country of ref document: EP

Kind code of ref document: A1