1、Designation: D5197 091D5197 16Standard Test Method forDetermination of Formaldehyde and Other CarbonylCompounds in Air (Active Sampler Methodology)1This standard is issued under the fixed designation D5197; the number immediately following the designation indicates the year oforiginal adoption or, i
2、n the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1 NOTEAdded research report information to Section 13 editorially in September 2010.1. Scope1.
3、1 This test method coverspresents a procedure for the determination of formaldehyde (HCHO) and other carbonyl compounds(aldehydes and ketones) in air. Other carbonyl compounds that have been validated for determination successfully quantified bythis method include acetaldehyde, acetone, propanal (pr
4、opionaldehyde), methacrolein, 2-butanone (methyl ethyl ketone),butyraldehyde, benzaldehyde, isovaleraldehyde, valeraldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, hexanal, and2,5-dimethylbenzaldehyde. Acrolein and crotonaldehyde can not be determined quantitatively using the analytical pro
5、ceduredescribed in 10.2 due to the formation of multiple derivative peaks and the instability of the peak ratios2,3. However, the proceduredescribed in the Annex A has been used by the U.S. Environmental Protection Agency to estimate acrolein and crotonaldehydeconcentrations in standard atmospheres
6、following special precautions.1.2 This test method involves drawing air through a cartridge containing silica gel coated with 2,4-dinitrophenylhydrazine(DNPH) reagent. Carbonyl compounds readily form stable derivatives with the DNPH reagent. The DNPH derivatives areanalyzed for parent aldehydes and
7、ketones utilizing high performance liquid chromatography (HPLC). The sampling procedure isa modification of U.S. EPA Method TO-11A (see 2.2).1.3 This test method is based on the specific reaction of carbonyl compounds with DNPH in the presence of an acid to formstable derivatives according to the re
8、action shown in Fig. 1, (where: both R and R1 are alkyl or aromatic groups (ketones), orboth,either, or eitherboth R or R1 is a hydrogen atom (aldehydes). The determination of formaldehyde and other carbonylcompounds, as DNPH derivatives, is similar to that of U.S. EPA Method TO-11A in that it utili
9、zes HPLC with UV detection asthe analytical finish. The detection limits have been extended to applicability of this test method is extended beyond the statedapplicability of TO-11Ato include other carbonyl compounds that can be determined as outlinedstated in Section 10.2.4. This testmethod is suit
10、able for determination of formaldehyde and other carbonyl compounds in the concentration range fromapproximately 10 ppb to 1 ppm (v/v). Lower concentrations may be determined with careful control of contamination, appropriateselection of flow rate and sampling duration.1.4 The sampling method gives
11、a time-weighted average (TWA) sample. It can be used for long-term (1 to 24 h) or short-term(5 to 60 min) sampling of air for formaldehyde. Shorter sampling times or low flow rates will result in higher detection limits andmay result in greater variation in co-located sampler results. Tests should b
12、e performed over a duration and a flow rate that allowsthe data quality objective of the project to be achieved. Sample times for other carbonyls, such as acetaldehyde, may be limitedto short term (1).2 The data provides total concentrations of carbonyl compounds from which time weighted average con
13、centrationscan be calculated.1.5 This test method instructs the user on how to prepare sampling cartridges from commercially available chromatographicgrade silica gel cartridges3 by the application of acidified DNPH to each cartridge.1 This test method is under the jurisdiction of ASTM Committee D22
14、 on Air Quality and is the direct responsibility of Subcommittee D22.05 on Indoor Air.Current edition approved Nov. 1, 2009Oct. 1, 2016. Published December 2009November 2016. Originally approved in 1991. Last previous edition approved in 20032009as D5197 03.D5197 091. DOI: 10.1520/D5197-09E01.10.152
15、0/D5197-16.2 Levin, J. O., and Lindahl, R., “Aldehyde Measuring Methods Using DNPH-coated FiltersSummary and Conclusions,” Proceedings of the Workshop “SamplingProject”, Mol, Belgium, June 2728, 1986.The boldface numbers in parentheses refer to a list of references at the end of this standard.3 Clar
16、k, W. L., Biller, W. F., Tejada, S. B., Siegl, W. O., Rosenhamer, D., Newkirk, M. S., and Crowley, R. J., “Round Robin Analysis of Alcohol and Carbonyl SyntheticExhaust Samples,” SAE Technical Paper Series, Paper 941944, 1994, pp. 7187.3 The cartridge used in the development and performance evaluati
17、on of this test method was the Sep-Pak Plus Silica cartridge. The sole source of supply of the cartridgeknown to the committee at this time is Waters Associates, 34 Maple Street, Milford, MA 01757. If you are aware of alternative suppliers, please provide this informationto ASTM Headquarters. Your c
18、omments will receive careful consideration at a meeting of the responsible technical committee,Other manufactures make similar products.1which you may attend.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been mad
19、e to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.Copy
20、right ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States11.6 The sampling flow rate, as described in this test method, has been validated for sampling rates up to 1.5 L/min. L/min forformaldehyde. This flow rate limitation is principally due to th
21、e high pressure drop (8 kPa at 1.0 L/min) across the user preparedsilica gel cartridges which have a particle size of 55 to 105 m. These cartridges are not generally compatible with battery-poweredpumps used in personal sampling equipment (for example, those used by industrial hygienists.hygienists)
22、.1.7 Alternatively, pre-coated DNPH silica gel cartridges are also commercially available and may be substituted provided theycan be demonstrated to perform equivalently.equivalently (2). Some of these use silica gel of a larger particle size that results ina lower pressure drop across the cartridge
23、. These low pressure drop cartridges may be more suitable for sampling air usingbattery-powered personal sampling pumps.1.8 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.9 This standard does not purport to address all of t
24、he safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:4D1193 Specification for Reag
25、ent WaterD1356 Terminology Relating to Sampling and Analysis of AtmospheresD3195 Practice for Rotameter CalibrationD3631 Test Methods for Measuring Surface Atmospheric PressureD3686 Practice for SamplingAtmospheres to Collect Organic Compound Vapors (Activated Charcoal TubeAdsorption Method)E177 Pra
26、ctice for Use of the Terms Precision and Bias in ASTM Test MethodsE682 Practice for Liquid Chromatography Terms and Relationships2.2 EPA Methods:5MethodTO-11A EPA-625/R-96/010b, Compendium of Methods for the Determination ofToxic Organic Compounds inAmbientAir, U.S. Environmental Protection Agency,
27、Research Triangle Park, NC, January 1999EPA-600/R-98/004 Quality Assurance Handbook for Air Pollution Measurement Systems, Volume 2, Part 1Ambient AirQuality Monitoring Program Quality System Development, U.S. Environmental Protection Agency, Research Triangle Park,NC, August 19987EPA-600/4-83-027 T
28、echnical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air,U.S. Environmental Protection Agency, Research Triangle Park, NC, June 1983 (PB90-187 014/AS)73. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this test method, refer to Terminology D
29、1356 and Practice E682.3.2 Definitions of Terms Specific to This Standard:4 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the
30、ASTM website.5 Available from the U.S. Environmental Protection Agency, http:/www.epa.gov/ttn/amtic/airtox.html, or the U.S. Department of Commerce, National TechnicalInformation Service, 5285 Port Royal Rd., Springfield, VA22161.United States Environmental ProtectionAgency (EPA), William Jefferson
31、Clinton Bldg., 1200 PennsylvaniaAve., NW, Washington, DC 20460, http:/www.epa.gov.FIG. 1 Reaction of Carbonyl CompoundsD5197 1623.2.1 All other pertinent abbreviations and symbols are defined when first cited in this test method.4. Summary of Test Method4.1 Aknown volume of indoor air is drawn throu
32、gh a prepacked silica gel cartridge coated with acidified DNPH, at a samplingrate of 0.5 to 1.21.5 L/min for an appropriate period of time. Both sampling rate and time are dependent upon carbonylconcentrations in the test atmosphere.4.2 After sampling, the sample cartridges are individually capped a
33、nd placed in individual bottles or other sealable containers.Sample identifying tags or labels are attached and the individual sample containers are then placed in a friction-top can or othersuitable sealable secondary container with a pouch of charcoal for transport to the laboratory for analysis.
34、Charcoal may only beuseful if sampling chemicals other than formaldehyde and acetaldehyde. The cartridges are placed in cold storage stored at 10 % at 25C) is required for effective ozone removal when using KI (9). A denuder is constructed of 1 m of may beconstructed by filling a 1-m section of 0.64
35、-cm outside diameter by 0.46-cm inside diameter copper tubing, that is filled tubingwith a saturated solution of KI in water, allowed allowing the solution to stand for a few minutes (;5), drained and dried (5),draining the solution and drying the tubing with a stream of clean air or nitrogen for ab
36、out 1 h. The capacity of the ozone denuderas described is about 100 ppm(v)-hour of ozone.ppmv-hour of ozone. Test aldehydes (formaldehyde, acetaldehyde,propionaldehyde, benzaldehyde, and p-tolualdehyde) that were dynamically spiked into an ambient sample air stream passedthrough the denuder. Scrubbe
37、rs may be constructed by impregnating 37-mm cellulose fiber filters with 0.6M KI solution.D5197 1636.4.3 Test aldehydes (formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and p-tolualdehyde) that were dynamicallyspiked into an ambient sample air stream passed through the denuder with practi
38、cally no losses.TABLE A1.1 Stability of Extracted Components on Storage of Spiked CartridgesAElapseddaysaftercartridgeextractionAcrolein x-Acrolein Unknown Crotonx-Croton Acrolein+x-Acrolein1 442.4 685.4 53.5 768.8 343.6 1127.81 446.3 697.7 51.0 752.5 375.8 1144.11 420.6 637.2 52.3 735.9 352.3 1057.
39、72 436.3 697.6 57.9 804.8 381.0 1133.97 434.8 664.0 73.4 776.6 332.9 1098.78 405.5 575.1 76.4 719.2 323.6 980.68 432.0 638.2 78.2 767.4 320.6 1070.223 434.5 558.0 112.1 715.6 329.1 992.541 454.3 582.4 115.2 771.0 321.3 1036.841 452.9 518.1 23.0 774.9 314.3 971.041 427.0 562.5 109.6 731.4 322.7 989.5
40、64 464.4 642.0 85.6 778.9 328.5 1106.464 471.6 651.7 93.3 794.7 344.0 1123.364 433.7 585.1 77.4 727.3 307.6 1018.870 455.4 478.0 201.9 793.4 318.0 933.470 443.0 484.6 180.2 774.2 304.0 927.6Average 440.92 603.60 90.05 761.65 332.46 1044.52Std. dev. 16.65 71.54 46.72 27.99 22.08 73.30% rsd 3.78 11.85
41、 51.88 3.67 6.64 7.02TABLE 1 Interferences and Other Factors Impacting Sampling and Analysis of Carbonyls Using DNPH Impregnated Cartridges(Adapted From et al. (3)Section Agent or Parameter Influenced Species Interferences Remedy6.2 Ozone All Carbonyls Positive and negative artifactson carbonyl deri
42、vatives;baseline and retention timeshiftsSample with upstream ozonescrubber6.3 Nitrogen Dioxide and NitricOxideFormaldehyde andAcetaldehydeNitrogen dioxide and nitricoxide react with DNPH formingside products which may co-elute with formaldehyde andacetaldehyde derivative peaksBetter chromatographic
43、separation6.4 Relative Humidity (RH) Ketones, Carbonyls atextremesPoor ketone collectionefficiencies at nominalsampling flow rates, leading tolarge underestimation of ketoneconcentrations; relativehumidity below 10 % andabove 75 % can result in lowcarbonyl collection efficienciesUse alternative deri
44、vation agentfor ketones6.5 Polymerization Unsaturated Carbonyls Derivatives undergopolymerizationUse alternate quantificationmethod for acrolein,methacrolein, andcrotonaldehyde6.6 DNPH Reagent Contamination Formaldehyde and OtherCarbonylsFormaldehyde and othercarbonyls present in DNPHreagentPurify D
45、NPH byrecrystallization6.7 Co-elution All Carbonyls Isomeric aldehydes or ketonesmay co-elute with DNPHderivatives of carbonyls insampleBetter chromatographicseparation6.8 Sunlight All Carbonyls Artifacts may be created Store cartridges in opaquecontainers. Shield outdoorsamples6.9 Temperature All C
46、arbonyls High temperatures can causedisassociation of carbonyl-DNPH derivatives with loss ofthe carbonylStore cartridges at 75% RH) (10). Ketones are less reactive than aldehydes and are more readily impacted by the sampling conditions.Collection efficiencies of acetone and 2-butanone in atmospheres
47、 with relative humidity above 50 % can be as low as 20 % (3).Air temperature also may impact collection efficiency. If the ambient air temperature during sampling is below 15C, a heated inletprobe is recommended.6.5 Acrolein, methacrolein and crotonaldehyde should not be quantified using the analyti
48、cal procedure described in 10.2 dueto the formation of multiple derivative peaks (14-16). In an acidic environment in the presence of excess DNPH, the DNPHderivatives of acrolein, methacrolein and crotonaldehyde have been shown to partially transform into several compounds that haveUV spectra sugges
49、ting the presence of the DNPH chromophore. The sequential conversion of the carbonyl-DNP-hydrazone(monomer) to carbonyl-DNP-hydrazone-DNPH (dimer), and finally 2(carbonyl-DNP-hydrazone)-DNPH (trimer) has beendemonstrated (14). The chromatic response areas of the dimers and trimers have been summed in the past to estimate the6.10 Particles All Carbonyls Particulates collected on thesurface of the cartridge packingmay cause cartridge cloggingand baseline disturbanceFilter any acetonitrile extractwith visible particles prior toanalysis to prevent clogging ofHPLC6.
