1、Designation: D 6348 03Standard Test Method forDetermination of Gaseous Compounds by Extractive DirectInterface Fourier Transform Infrared (FTIR) Spectroscopy1This standard is issued under the fixed designation D 6348; the number immediately following the designation indicates the year oforiginal ado
2、ption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.INTRODUCTIONThis extractive FTIR based field test method is used to quantify gas p
3、hase concentrations of multipletarget analytes from stationary source effluent. Because an FTIR analyzer is potentially capable ofanalyzing hundreds of compounds, this test method is not analyte or source specific. The analytes,detection levels, and data quality objectives are expected to change for
4、 any particular testing situation.It is the responsibility of the tester to define the target analytes, the associated detection limits for thoseanalytes in the particular source effluent, and the required data quality objectives for each specific testprogram. Provisions are included in this test me
5、thod that require the tester to determine criticalsampling system and instrument operational parameters, and for the conduct of QA/QC procedures.Testers following this test method will generate data that will allow an independent observer to verifythe valid collection, identification, and quantifica
6、tion of the subject target analytes.1. Scope1.1 This field test method employs an extractive samplingsystem to direct stationary source effluent to an FTIR spec-trometer for the identification and quantification of gaseouscompounds. This test method is potentially applicable for thedetermination of
7、compounds that (1) have sufficient vaporpressure to be transported to the FTIR spectrometer and (2)absorb a sufficient amount of infrared radiation to be detected.1.2 This field test method provides near real time analysis ofextracted gas samples from stationary sources. Gas streamswith high moistur
8、e content may require conditioning to mini-mize the excessive spectral absorption features imposed bywater vapor.1.3 This field test method requires the preparation of asource specific field test plan. The test plan must include thefollowing: (1) the identification of the specific target analytes(2)
9、 the known analytical interferents specific to the test facilitysource effluent (3) the test data quality necessary to meet thespecific test requirements and (4) the results obtained from thelaboratory testing (see Annex A1 for test plan requirements).1.4 The FTIR instrument range should be sufficie
10、nt tomeasure from high ppm(v) to ppb(v) and may be extended tohigher or lower concentrations using any or all of the followingprocedures:1.4.1 The gas absorption cell path length may be eitherincreased or decreased,1.4.2 The sample conditioning system may be modified toreduce the water vapor, CO2, a
11、nd other interfering compoundsto levels that allow for quantification of the target com-pound(s), and1.4.3 The analytical algorithm may be modified such thatinterfering absorbance bands are minimized or stronger/weakerabsorbance bands are employed for the target analytes.1.5 The practical minimum de
12、tectable concentration is in-strument, compound, and interference specific (see Annex A2for procedures to estimate the achievable minimum detectableconcentrations (MDCs). The actual sensitivity of the FTIRmeasurement system for the individual target analytes dependsupon the following:1.5.1 The speci
13、fic infrared absorptivity (signal) and wave-length analysis region for each target analyte,1.5.2 The amount of instrument noise (see Annex A6), and1.5.3 The concentration of interfering compounds in thesample gas (in particular, percent moisture and CO2), and theamount of spectral overlap imparted b
14、y these compounds in thewavelength region(s) used for the quantification of the targetanalytes.1.5.4 Any sampling system interferences such as adsorptionor outgassing.1.6 Practices E 168 and E 1252 are suggested for additionalreading.1.7 This standard does not purport to address all of thesafety con
15、cerns associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and1This test method is under the jurisdiction of Committee D22 on Sampling andAnalysis of Atmospheres and is the direct responsibility of Subcommittee D22.03on Ambient Atmospheres and
16、 Source Emissions.Current edition approved October 1, 2003. Published December 2003. Originallyapproved in 1998. Last previous edition approved in 1998 as D 6348 - 98.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.health practices a
17、nd to determine the applicability of regula-tory limitations prior to use. Additional safety precautions aredescribed in Section 9.2. Referenced Documents2.1 ASTM Standards:2D 1356 Terminology Relating to Sampling and Analysis ofAtmospheresD 3195 Practice for Rotameter CalibrationE 168 Practice for
18、General Techniques of Infrared Quanti-tative AnalysisE 1252 Practice for General Techniques for Obtaining In-frared Spectra for Qualitative Analysis2.2 EPA Methods (40 CFR Part 60 Appendix A)3Method 1 - Sample and Velocity Traverses for StationarySourcesMethod 2 Series - Determination of Stack Gas V
19、elocity andVolumetric Flow Rate (Type S Pitot Tube)Method 3 Series - Gas Analysis for Carbon Dioxide, Oxy-gen, Excess Air, and Dry Molecular WeightMethod 4 Series - Determination of Moisture Content inStack Gases3. Terminology3.1 See Terminology D 1356 for definition of terms relatedto sampling and
20、analysis of atmospheres.3.2 Definitions of Terms Specific to This StandardThissection contains the terms and definitions used in this testmethod and those that are relevant to extractive FTIR basedsampling and analysis of stationary source effluent. Whenpossible, definitions of terms have been drawn
21、 from authori-tative texts or manuscripts in the fields of air pollutionmonitoring, spectroscopy, optics, and analytical chemistry.3.2.1 absorbance, nthe negative logarithm of the trans-mission, A = -log (I/I0), where I is the transmitted intensity ofthe light and I0is the incident intensity.3.2.2 a
22、bsorptivity, adjthe amount of infrared radiationthat is absorbed by each molecule.3.2.3 analyte spiking, nthe process of quantitatively co-adding calibration standards with source effluent to determinethe effectiveness of the FTIR measurement system to quantifythe target analytes.3.2.4 analytical al
23、gorithm, nthe method used to quantifythe concentration of the target analytes and interferences ineach FTIR Spectrum. The analytical algorithm should accountfor the analytical interferences by conducting the analysis in aportion of the infrared spectrum that is the most unique for thatparticular com
24、pound.3.2.5 analytical interference, nthe physical effects ofsuperimposing two or more light waves. Analytical interfer-ences occur when two or more compounds have overlappingabsorbance bands in their infrared spectra.3.2.6 apodization, va mathematical transformation car-ried out on data received fr
25、om an interferometer to reduce theside lobes of the measured peaks. This procedure alters theinstruments response function. There are various types oftransformation; the most common forms are boxcar, triangular,Happ-Genzel, and Beer-Norton functions.3.2.7 background spectrum, nthe spectrum taken in
26、theabsence of absorbing species or sample gas, typically con-ducted using dry nitrogen or zero air in the gas cell.3.2.8 bandwidth, adjthe width of a spectral feature asrecorded by a spectroscopic instrument. This width is listed asthe full width at the half maximum of the feature or as the halfwidt
27、h at the half maximum of the spectral feature. This is alsoreferred to as the line width (1).43.2.9 beam splitter, na device located in the interferom-eter that splits the incoming infrared radiation into two separatebeams that travel two separate paths before recombination.3.2.10 Beers law, nthe pr
28、incipal by which FTIR spectraare quantified. Beers law states that the intensity of a mono-chromatic plane wave incident on an absorbing medium ofconstant thickness diminishes exponentially with the numberof absorbers in the beam. Strictly speaking, Beers law holdsonly if the following conditions ar
29、e met: (1) perfectly mono-chromatic radiation (2) no scattering (3) a beam that is strictlycollimated (4) negligible pressure-broadening effects (2, 3).For an excellent discussion of the derivation of Beers law, see(4).3.2.11 calibration transfer standard, na certified calibra-tion standard that is
30、used to verify the instrument stability on adaily basis when conducting sampling.3.2.12 classical least squares, na common method ofanalyzing multicomponent infrared spectra by scaled absor-bance subtraction.3.2.13 condenser system,(dryer), na moisture removalsystem that condenses water vapor from t
31、he source effluent toprovide a dry sample to the FTIR gas cell. Part of the sampleconditioning system.3.2.14 cooler, na device into which a quantum detector isplaced for maintaining it at a low temperature in an IR system.At a low temperature, the detector provides the high sensitivitythat is requir
32、ed for the IR system. The two primary types ofcoolers are a liquid nitrogen Dewar and a closed-cycle Stirlingcycle refrigerator.3.2.15 electromagnetic spectrum, nthe total set of allpossible frequencies of electromagnetic radiation. Differentsources may emit over different frequency regions. All ele
33、c-tromagnetic waves travel at the same speed in free space (5).3.2.16 extractive FTIR, na means of employing FTIR toquantify concentrations of gaseous components in stationarysource effluent. It consists of directing gas samples to the FTIRcell without collection on sample media.3.2.17 fingerprint r
34、egion, nthe region of the absorptionspectrum of a molecule that essentially allows its unequivocalidentification. For example, the organic fingerprint regioncovers the wave number range from 650 to 1300 cm1(6).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Custo
35、mer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Available from Superintendent of Documents, U. G. Government PrintingOffice, Washington, DC 20402.4The boldface numbers in parentheses refer to the li
36、st of references at the end ofthe standard.D63480323.2.18 Fourier transform, va mathematical transform thatallows an aperiodic function to be expressed as an integral sumover a continuous range of frequencies (7). The interferogramrepresents the detector response (intensity) versus time, theFourier
37、transform function produces intensity as a function offrequency.3.2.19 frequency position, nthe accepted exact spectralline position for a specific analyte.Awave number or fractionalwavenumber is used to determine whether spectral shifts haveoccurred with time.3.2.20 FTIR, nan abbreviation for Fouri
38、er transforminfrared. A spectroscopic instrument using the infrared portionof the electromagnetic spectrum. The working component ofthis system is an interferometer. To obtain the absorptionspectrum as a function of frequency, a Fourier transform of theoutput of the interferometer must be performed.
39、 For anin-depth description of the FTIR, see (8).3.2.21 fundamental CTS, na NIST traceable referencespectrum with known temperature and pressure, that has beenrecorded with an absorption cell that has been measured usingeither a laser or other suitably accurate physical measurementdevice.3.2.22 infr
40、ared spectrum, nthat portion of the electromag-netic spectrum that spans the region from about 10 cm1toabout 12 500 cm1. It is divided (6) into (1) the near-infraredregion (from 12 500 to 4000 cm1), (2) the mid-infrared region(from 4000 to 650 cm1), and (3) the far-infrared region (from650 to 10 cm1
41、).3.2.23 instrument function, nthe function superimposedon the actual absorption line shape by the instrument. This issometimes referred to as the slit function; a term taken frominstruments that use slits to obtain resolution.3.2.24 instrument specific reference spectra, nreferencespectra collected
42、 on the instrument that collects the actualsample spectra. The instrument specific reference spectra areused in the analytical algorithm.3.2.25 intensity, nthe radiant power per unit solid angle.When the term spectral intensity is used, the units are watts persteradian per nanometre. In most spectro
43、scopic literature, theterm intensity is used to describe the power in a collimatedbeam of light in terms of power per unit area per unitwavelength. However, in the general literature, this definitionis more often used for the term irradiance,ornormal irradi-ance (9, 10).3.2.26 interferogram, nthe ef
44、fects of interference that aredetected and recorded by an interferometer, the output of theFTIR and the primary data are collected and stored (8, 10).3.2.27 interferometer, nany of several kinds of instru-ments used to produce interference effects. The Michelsoninterferometer used in FTIR instrument
45、s is the most famous ofa class of interferometers that produce interference by thedivision of amplitude (11).3.2.28 irradiance, nradiant power per unit projected areaof a specified surface. This has units of watts per squarecentimetre. The term spectral irradiance is used to describe theirradiance a
46、s a function of wavelength. It has units of watts persquare centimetre per nanometre (9).3.2.29 laser, nan acronym for the term light amplificationby stimulated emission of radiation. A source of light that ishighly coherent, both spatially and temporally (1).3.2.30 light, nstrictly, light is define
47、d as that portion of theelectromagnetic spectrum that causes the sensation of vision. Itextends from about 25 000 cm1to about 14 300 cm1(5).3.2.31 system mechanical response time, nthe amount oftime that is required to obtain a stable instrument responsewhen directing a non-retained calibration stan
48、dard through theentire sampling system3.2.32 minimum detectable concentration, nthe minimumconcentration of a compound that can be detected by aninstrument with a given statistical probability. Usually thedetection limit is given as three times the standard deviation ofthe noise in the system. In th
49、is case, the minimum concentra-tion can be detected with a probability of 99.7 % (9, 12). SeeAnnexA2 of this standard for a series of procedures to measureMDC.3.2.33 native effluent concentration, nthe underlying ef-fluent concentration of the target analytes.3.2.34 noise equivalent absorbance (NEA), nthe peak-to-peak noise in the spectrum resulting from the acquisition oftwo successive background spectra.3.2.35 path length, nthe distance that the sample gasinteracts with the infrared radiation.3.2.36 peak-to-peak noise, nthe absolute d
