# Aliphatic Aldehydes (2018)

​ALIPHATIC ALDEHYDES FORMULA: Table 1
MW: Table 1
METHOD: 2018
2018
CAS: Table 1
EVALUATION: PARTIAL
OSHA : Table 2 NIOSH: Table 2 ACGIH: Table 2
RTECS: Table 1 Issue 1: 15 March 2003
PROPERTIES: Table 1
COMPOUNDS AND SYNONYMS: See Table 3
SAMPLING SAMPLER:
CARTRIDGE (containing silica gel coated with acidified 2,4dinitrophenylhydrazine)
FLOW RATE:
0.1 to 1.5 L/min
VOL-MIN: -MAX:
1 L @ 0.68 to 1.3 mg/m3 15 L @ 7.0 to 15 mg/m3
SHIPMENT:
Ship cold (0 to 5 o C).
SAMPLE STABILITY: BLANKS:
MEASUREMENT TECHNIQUE:
HPLC; UV DETECTION
ANALYTE:
2,4-dinitrophenylhydrazones of aldehydes (Table 1)
EXTRACTION:
Elution with 10 mL of carbonyl-free acetonitrile
INJECTION VOLUME:
20 µL
MOBILE PHASE:
Acetonitrile:water (see Table 1 for percentages); 1.3 mL/min
COLUMN:
Stainless steel, 3.9 x 150 mm, packed with 5-µm C-18, Symmetry™ or equivalent
DETECTOR:
UV @ 360 nm
CALIBRATION:
Standard solutions of aldehydeDNPH derivatives in acetonitrile
RANGE:
See Table 4 [1]
ESTIMATED LOD:
See Table 4
PRECISION ( þ r ):
See Table 5 [1]
>30 days @ 5 o C [1] 2 to 10 field blanks per set 6 to 10 media blanks per set
ACCURACY RANGE STUDIED:
Not studied
BIAS:
Not determined
OVERALL PRECISION ( Ö rT ):
Not determined
ACCURACY:
Not determined
APPLICABILITY: Working ranges are approximately 0.05 to 15 mg/m3 (approximately 0.02 to 4 ppm) for 15-L air samples for the four aldehydes. This method can be used for the determination of acetaldehyde and valeraldehyde for OSHA STEL and PEL exposures. Upper limits of the method for the Supelco sampler are 105, 183, 50, and 50 µg per sample for acetaldehyde, propionaldehyde, valeraldehyde, and isovaleraldehyde, respectively. INTERFERENCES: Ozone has been observed to consume the 2,4-dinitrophenylhydrazine (2,4-DNPH) reagent and to degrade the DNPH derivative of formaldehyde [2]. Thus, ozone may degrade other aldehyde-DNPH derivatives. An ozone scrubber may be attached to the inlet of the sampler to remove ozone from the air; this scrubber may contain granular potassium iodide to reduce ozone to oxygen. Ketones and other aldehydes can react with 2,4-DNPH; the derivatives produced, however, generally are separated chromatographically from the analyte of interest. OTHER METHODS: ASTM method D5197-97 and EPA compendium method TO-11A are applicable to the same four aldehydes and employ air samplers containing DNPH-coated silica gel [3,4]. NIOSH methods 2538 [5] and 3507 [6] and OSHA method 68 [7] are other methods for determination of acetaldehyde in air. OSHA method 85 is applicable to valeraldehyde and employs DNPH on glass fiber filters [8].
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 2 of 10 REAGENTS: 1. Aldehyde-DN PH deriva tives, >99% pure (available from Supelco, Inc., or Aldrich Chem ical Co.). 2. Acetonitrile, high purity solvent for HPLC and pes ticide analysis, low ca rbon yl content.* 3. Calibration stock solutions. Accurately weigh 10 mg of DNPH derivatives in separate 10mL volumetric flasks. Add acetonitrile to the 10-mL m ark of each flask. Store at 5 oC in airtight containers 30 days or less. 4. Acetalde hyde, 99% pure .* 5. Propionaldehyde, 97% pure .* 6. Valeralde hyde, 97% pure .* 7. Isovaleraldehyde, 97 % pure .* 8. W ater, deionized (DI water). 9. Acetaldehyde fortification stock solution, 2.40 mg/m L. Measure 155 µL of cold (0 oC) acetaldehyde with a cold (0 oC) 500-µL syringe. D issolve in 35 m L of cold DI water in a 50-mL volumetric flask. Add DI water (-20 oC) to the 50-mL m ark. Use within 15 m in of preparation.** 10. Propionaldehyde fortification stock solution, 2.40 mg/mL. Dissolve 154 µL of 97% propionaldehyde in 35 mL of acetonitrile in a 50-m L flask. Add ac etonitrile to the 50-mL m ark.*** 11. Valeraldehyde fortification stock solution, 2.40 mg/mL. Dissolve 154 µL of 97% valeraldehyde in acetonitrile in a 50-mL volumetric flask. Add acetonitrile to the 50m L m ark.*** 12. Isovaleraldehyde fortification stock solution, 2.40 mg/mL. Dissolve 152 µL of 97% isovaleraldehyde in acetonitrile in a 50-mL volumetric flask. Add acetonitrile to the 50m L m ark.***
EQUIPMENT: 1. Sam pler: Plastic holder containing 0.35 g of 150 to 250-µm (60-100 mesh) silica gel coate d with 1.0 m g of 2,4-dinitrophenylhydrazine which has been acidified. Pressure drop across sampler should be less than 28 inches o f water (7 k Pa) at 1.5 L/m in. Sam plers are comm ercially available [Supelco S10 Lp DN PH cartridge, cat. No . 2-10 14; a similar type of sampler is manufactured by W aters Corp. (Sep-Pak XPoSure Aldehyde Sam pler, pa rt No. W AT 047 205 )]. 2. Personal sampling pump, 0.1 to 1.5 L/min, with flexible connecting tubing. 3. Vials, 20-mL, 4-mL, glass, PFTE-lined rubber septa in caps for airtight seals. 4. Liquid chrom atograph with UV detector, recorder, integrator, and column. (See page 201 8-1.) 5. Syringes, 100-µL, 500-µL, and 10-mL. 6. Volumetric flasks, 5-mL, 10-mL, and 50-mL. 7. Ozone scrubber (optional), available from W aters Corp., Milford, MA. 8. Aluminum foil, or black electrical tape (optional).
See SPECIAL PRECAUTIONS
freezer compartment of a refrigerator for at least 45 m inutes . Mak e sure there is no w ater in th e ne edle which wo uld fre eze and clog the needle.
within 30 minutes of preparation or kept chilled in an ice bath.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 3 of 10
SPECIAL PRECAUTIONS: Acetaldehyde is a severe eye irritant, lachrymator, mutagen, confirmed animal carcinogen, human cancer suspect agent and possible sensitizer [9]. Contact of acetaldehyde with air may cause the formation of explosive peroxides, and contact of the peroxides with heat or flam e m ay cause fires or exp losion s. Fire and exp losion m ay result from con tact of ace taldeh yde with strong oxidizers. Acetaldehyde is an extreme fire hazard; flash point = -37.8 oC (closed cup). Allow excess acetaldehyde in the glass ampule to evaporate in a fume hood. Propionaldehyde, valeraldehyde, and isovaleraldehyde are eye and skin irritants. Evidence for the potential carcinogenicity of propionaldehyde and valeraldehyde is inconclusive [9]. These three aldehydes are incompatible with strong oxidizers and are dangerous fire hazards (flash points = 17.8 oC, 12.2 oC and -1 oC, respectively). Bottles of these aldehydes should be flushed with nitrogen after use. Work with all aldehydes in a fume hood. The DNPH reagent [11] and aliphatic aldehydes are light sensitive [10]. Also, DNPH is a suspect carcinogen. Acetonitrile is toxic and is a fire hazard (flash point = 12.8 oC). SAMPLING: 1. Calibrate each pe rsona l sam pling pum p with a represe ntative sam pler in line. If desirable, attach a representative ozone scrubber to the inlet of the sam pler. How ever this method has not been evaluated with an ozone scrubber in line. 2. Open sam pler packet and remove end caps. 3. Attach sampler to the sampling pump with flexible tubing. Th e W ate rs sam pler is bi-directional and can be c onn ecte d at either en d. NOTE: If sampling is to be performed in intense sunlight, protection of the DNPH -coated silica gel bed in the sampler from intense light would be suggeste d in ord er to prevent possible photodecomposition of the DNPH reagent [11] and the aldehyde derivatives. If desirable, wrap a portion of the sampler with aluminum foil or black electrical tape. 4. Sam ple 1 to 15 L of air at 0.1 to 1.5 L/min. 5. Plac e en d ca ps o nto the sa m pler and s eal sa m pler in an en velop e. Pro tect sam ples from hea t. 6. Ship samples cold (0 to 5 oC). Ship blanks in a sep arate container.
SAMPLE PREPARATION: 7. a. Elute the aldehyde derivatives from the cartridge samplers with 10-m L qu an tities of a ce ton itrile. Collect effluent (ca. 9.5 mL) from each sampler in a separate 10-mL volumetric flask. b. Add acetonitrile to the 10-mL m ark of the volumetric flask for each sample. NOTE: Carbonyl content of acetonitrile can be determined by passing 10 mL of the solvent through a cartridge of DNPH-coated silica gel and analyzing by HPLC. Contents of aldehydes of interest should be below the respective LODs.
CALIBRATION AND QUALITY CONTRO L: 8. Ca librate daily with at leas t six wo rking standa rds over the ra nge of interest. a. Calculate the concentrations of the aldehyde-DNPH derivatives in the calibration stock solutions (about 1000 µg/mL). Calculate the equivalent concentrations of the free aldehydes in solution by multiplying the derivative concentrations by 0.197, 0.244, 0.324, and 0.324 (molecular weights of acetaldehyde, propionaldehyde, valeraldehyde and isovaleraldehyde divided by the molecular weights of the correspo nding aldehyde-DN PH d erivatives, respectively). b. Prepare a series of dilutions (working standards) from 0.01 to 10 or 20 µg/mL (ranges of equivalent concentrations of free aldehydes from values be low the detection lim its to values c orrespo nding to upper lim its of the analytical range). The working stand ards (standard solutions) are stable for more than a month when stored at 5 oC in the dark in airtight containers; however, it is suggested that fresh wo rking sta ndards be pre pared weekly. c. Trans fer 3-m L aliquots of working standa rds to 4-m L vials and analyze (steps 11, 13 and 14). d. Prepare calibration graphs, peak areas or heights vs. µg free aldehydes per sample.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 4 of 10 9. Determine recoveries (R) of aldehydes from samplers in the calibration range (step 8). Prepare three sorbent beds at each of five concen tration levels for each aldehyde plus three m edia blanks. Re covery is exp ecte d to be near 100% for acetaldehyde, propionaldehyde, and valeraldehyde and about 86% for isovaleraldehyde. a. Prepare series of dilutions of fresh fortification stock solutions in the range of 50 to 300 µg/mL in 20m L vials (one dilution fo r eac h fortification level for eac h alde hyde). Cap vials tigh tly. Use acetaldehyde fortification solutions within 15 minutes of preparation or significant losses of acetaldehyde may occur. Use propionaldehyde, valeraldehyde and isovaleraldehyde fortification solutions within 30 m inutes of preparation (a limit of 30 minutes is preca utionary). b. Fortify beds of sorben t. Usin g a 100-µL syringe, measure 20 to 90 µL of the particular aldehyde solution. Penetrate the center of the frit at the inlet of the sampler with the needle of the syringe. Inject the solution into the cente r of the sorb ent bed. It is recom m end ed that each s am pler be fortified with only one injection of 90 µL of less. Injection of an exces sive volume of solution may lead to incom plete reaction of aldehyde with DNPH. c. Prepare the fortified sam ples (steps 7a an d 7b). d. Transfer 3-m L aliquots of sam ples to 4-m L vials a nd a nalyze togeth er with working standards (steps 11, 13 and 14 ). e. Prepare graph of peak height vs. concentration of aldehyde in µg/sample for each of the aldehydes. f. Ca lculate recovery (R) for each sample by dividing the quantity of aldehyde found in the sample by the quantity of aldehyde applied. g. Prepare g raphs of R vs. µg of aldehyde found (rec overed). 10. Fortify three quality control samples and three analyst samples with known quantities of free aldehyde and aldehyde-DNPH in separate experiments. Analyze these samples to ensure that the calibration and recovery graphs are in control.
MEASUREMENT: 11. Set the liquid chromatograph according to manufacturer’s recomm endations and to conditions given on page 2018-1 and in Table 1. 12. Transfer an aliquot of the sam ple solution from ste p 7.b. to a 4-m L vial. C ap the vial. 13. Injec t a 20-µL sam ple aliqu ot. 14. Mea sure peak height or peak area. If a sample peak is larger than the largest standard peak, dilute an aliquot of the rem aining sam ple so lution, reanalyze, and apply appropriate dilution factor in the calculations. 15. To ensure validity of the samples, identify those samples which contain more than 105, 183, 50 or 50 µg of acetaldehyde, propionaldehyde, valeraldehyde or isovaleraldehyde per sample, respectively. The cap acity of the samplers may have been exceeded for these samples, and collection of smaller samples would be warranted.
CALCULATIONS: 16. Determine m ass , µg, of aldehyde, W , foun d in the sam ple an d the average m edia blank , B, from the appropriate calibration graph. 17. Calculate conce ntration, C, of the aldehyde in the air volume sa m pled, V (L).
NO TE : :g/L = m g/m 3
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 5 of 10 EVALUATION OF METHOD: The backup data report for this method development contains the data on recovery and breakthrough stud ies for eac h of th e alde hydes.[1] This method was evaluated with Supelco S10 LpDNPH sam plers and free (underivatized) acetaldehyde, propionaldehyde, valera ldehyde, an d isov aleraldehyde. Recoveries were determined after fortification of six sam plers in each set with known quantities of free aldehyde (see Table 5). W hile acetaldehyde, propionaldehyde and valeraldehyde showed average recoveries greater than 90%, average recoveries of isovaleraldehyde in Table 5 were in the 80% range; the reason for these relatively low recoveries is unclear. For sto rage stu dies, s ix sam plers in each set were fortified with 3.00-µg of free aldehyde and stored at 5 oC in the dark (see Table 6). Also, liquid standards (standard solutions of aldehyde-DNPH de rivatives in acetonitrile) were stored at 5 °C in the dark in vials with airtight caps (see Table 6). Limits of detection and quantitation were determined by least squares calculations with series of s ix standard solutions of aldehydeDN PH d erivatives in acetonitrile (see T able 4). This method also was evaluated for butyraldehyde-DNPH and free butryaldehyde on Supelco S10 LpDNPH samplers. Recoveries decreased from 98% to 79% when quantities applied increased from 1.5 :g to 20 :g. The negative slope caus ed difficulty or amb iguity in applying recove ry factors to quantities found. This method is not re com m end ed fo r butyraldehyde. Crotonaldehyde and acrolein were also studied. The recoveries of crotonaldehyde (crotonaldehyde-DNPH) and acrolein (acrolein-DNPH ) were found to be very low (less than 30%). This method is not recomm ended for either of these co m pou nds [12]. In each bre ak through stu dy, a pair of sam plers in series was connecte d to an air pump. A glass U-tube (a Schwa rtz drying tube) preceded the front sampler. For dry air, an impinger of dried, indicating silica gel preceded the U-tube. For humid air, an impinger of water preceded the U-tube. Known quantities of free aldehyde in solution were placed into the U-tube, and the pump drew air through the system at 1 L/min. Upper limits of the method for acetaldehyde and propionaldehyde were calculated as two-thirds of the smallest quantities of aldehyde placed into the U-tube which gave rise to 5% breakthrough. For these two aldehydes, breakthrough took p lace earlier in hum id air than in dry air or laboratory air; this humidity effect was reversed in the c ase of form aldehyde [13]. How ever, quantities of valeraldehyde and isovaleraldehyde generally did not break through the front samplers, and excessive quantities of valeraldehyde and isovaleraldehyde remained on the front samplers without reaction with D NP H. T hus , upper lim its of the method for valeraldehyde and isovaleraldehyde could not be determined from quantities of aldehyde which ga ve rise to 5% breakthrough. Upper limits of valeraldehyde and isovaleraldehyde were calculated as two-thirds of the largest quantities of aldehydes place d into the Utube which gave rise to a mas s balance or a n ear m ass balanc e (see Ba ckup Data R eport [1]). Since the sampler does not have a backup section for determination of breakthrough, the worker conducting sampling in the field may connect two samplers in series in the cases of acetaldehyde and propionaldehyde. The back pressure of the sampling train will be higher and a lower flow rate may be required. Use of backup sam plers in the field for valeraldehyde and isovaleraldehyde wou ld be m eaningless bec ause ex cessive quantities of these aldehydes are tra ppe d on the fro nt sam pler without re action with DNPH and breakthrough to backup samplers may never occur. Alternatively, sampling without a backup sampler may be conducted even whe n high con cen trations of aldehydes and ketones are anticipated if the sampling period is minimal and the flow rate of the pump is low. Although this method m ay be useful for determ ining aroma tic aldehydes in the air, it would be very difficult or im possible to evaluate th is m eth od with free (u nderivatized) aro m atic aldehydes. A rom atic aldehydes, such as benzaldehyde, undergo rap id oxidation in air to form the corresponding carboxylic acids, su ch as benzo ic acid. The capability to separate valeraldehyde-DNPH from isovaleraldehyde-DNPH by HPLC was investigated. Twenty microliters of a single acetonitrile solution containing valeraldehyde-DNPH at 2 µg/mL and isovaleraldehyde-DNPH at 1 µg/mL (equivalent concentrations of und erivatized alde hydes) was inje cted into NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 6 of 10 the HPLC when the mobile phase consisted of 66:34 acetonitrile:water at 1.3 mL/m in. Retention times of valeraldehyde-DNPH and isovaleraldehyde-DNPH were 7.82 and 7.32 m in, respectively. Although two sharp peak s were observed, th e separatio n was only partial. This method can be used with SKC aldehyde samplers (DNPH-coated silica gel tubes, catalogue No. 226119) for aceta ldehyde, propionaldehyde, valeraldehyde, and isovaleraldehyde with modifications (see APP EN DIX ).
REFERENCES: [1]
[2]
[3]
[4]
[5]
[6]
[7] [8] [9]
[10] [11] [12] [13]
[14]
Tucker SP [2002]. Aliphatic Aldehydes Backup Data Report for method 2018 for acetaldehyde, propionaldehyde, valeraldehyde, and isovaleraldehyde (butyraldehyde and crotonaldehyde), C incinnati, OH: unpublished report. National Institute for Occupational Safety and Health, DART. Kleindienst TE, Corse EW , and Blanchard FT [1998]. Evaluation of the Performance of DNPH-Coated Silica Gel and C 18 Cartridges in the Measurement of Formaldehyde in the Presence and Absence of Ozo ne. E nviron m enta l Scien ce & Te chn ology, 32(1), 124-130. ASTM [2001]. Method D5197-97, Standard Test Method for Determination of Formaldehyde and Other Carbonyl Com pounds in Air (Active Sampler Methodology). Atmospheric Analysis, Occupational Health and Safety, Protective Clothing, 1103, W est Conshohocken, PA: American Society for Testing and Mate rials, A ST M Inte rnatio nal. U.S. EPA [1999]. Compendium Method TO-11A: Determination of Formaldehyde in Ambient Air Using Adsorbent Cartridge Followed by High Performance Liquid Chromatography (HPLC), Compendium of Methods for the De term ination of T oxic O rganic C om pounds in Am bient Air, Second Edition, U.S. Environmental Protection Agency, Center for Environmental Research Information, Office of Research and Development, W ashington, DC. EPA/625/R-96/010b. NIOSH [1994]. Acetaldehyde by GC , m etho d 2538. In: E ller PM , Cassinelli ME, eds. NIOSH M anual of Ana lytical Method s, 4 th ed., U.S. De partm ent of He alth and H um an Servic es, Pu blic Health Service, Centers for Disease Control and Prevention, National Institute for Occupational Safety and Health, Cincinnati, OH. DHHS (NIOSH) Publication No. 94-113. NIOSH [1994]. Acetaldehyde by Bubbler and HPLC, method 3507. NIOSH Manual of Analytical Methods, 4 th ed., Eller PM, Cassinelli ME, eds., U.S. Department of Health and Hu m an Servic es, Pu blic He alth Service, Centers for D isease C ontro l and P reve ntion, N ationa l Institute for Occu pation al Safety and Health, Cincinnati, OH. DHHS (NIOSH) Publication No. 94-113. OSHA [1990]. Acetaldehyde, method 68, OSHA A nalytical Methods Ma nua l, 2 nd ed., U.S. Department of Labor, Occupational Safety and Health Administration, Salt Lake City, UT. OSHA [1990]. Valeraldehyde, method 85, OSHA Analytical Me thod s M anu al, 2 nd ed., U.S. Department of Labor, Occupational Safety and Health Administration, Salt Lake City, UT. NIOSH [1991]. Current Intelligence B ulletin 55, Carciongen icity of Acetaldehyde and Malonaldehyde, and Mutagenicity of Related Low-Molecular-W eight Aldehydes. U.S. Department of Health and Human Services, Pub lic Health Service, Centers for Disease Control, N ationa l Institute fo r Occu pation al Safety and Health, Cincinnati, OH. DHHS (NIOSH) Publication No. 91-112. Pacak ova V, Ko nas M, and K otvalova V [1985]. Reaction Gas Chrom atography: Study of the Photodecomposition of Selected Substances, Chromatographia 20 (3), 164-172. Otson R and Fellin P [1998]. A Review of Techniques for Measurement of Airborne Aldehydes. Science of th e T otal Environ m ent, 77 (2/3), 95-131. Risner CH [1995]. High Perform ance Liquid Ch rom ato graphic De term ination of M ajo r Carbonyl Co m pou nds from Various Sou rces in Am bient Air, J. C hrom atog r. Sci., 33 (4), 168-176. NIOSH [1994]. Formaldehyde by HPLC, m ethod 2016, issue 2, NIOSH Manual of Analytical Methods, 4 th ed., Eller PM, Cassinelli ME, eds., U.S. Department of Health and Human Services , Pub lic Health Service, Centers for Disease Control and Prevention, National Institute for Occupational Safety and Health, Cincinnati, OH. DHHS (NIOSH) Publication No. 94-113. NIOSH [1998]. NIO SH /OS HA Oc cup ationa l Hea lth Guidelines for Chem ical Hazards, U.S. Department of Health and Human Services, Public Health Service, Centers for D isease C ontro l, Nation al Institute for Oc cup ationa l Safe ty and H ealth, C incinn ati, OH . DHHS (NIOSH) Publication No. 88-118, Supplement 1-OHG. For sale by the Superintendent of Docum ents, U.S. Government Printing Office, W ashington, DC 20402.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 7 of 10 [15] [16]
Sa x’s Dange rous Properties of In dus trial Ma terials [2000 ]. Vol. 3, 10th ed., Lewis RJ sr, ed., John W iley & Sons, Inc., New York. Handbook of T oxic and Hazardo us C hem icals and C arcinogens [1991]. Vol. 2, S ittig M, ed., GZ Noyes Publications, Park Ridge, NJ, p. 1633.
METHOD DEVELOPED BY: Samuel P. Tucker, Ph.D., NIOSH/DART
TABLE 1. PROPERTIES AND OTHER INFORMATION Compound
Formula
CAS
RTECS
MW
Density @ 20 o C (g/mL) a
CH3 -CHO
75-07-0
AB1925000
44.05
0.788
20.8
51:49
propionaldehyde
CH3 -CH2 -CHO
123-38-6
UE0350000
58.09
0.807
49
54:46
valeraldehyde
CH3 -(CH2 )3 -CHO
110-62-3
YV3600000
86.13
0.8095
102
66:34
590-86-3
ES3450000
86.13
0.803
90
66:34
CH3
b
Mobile Phase Percentages of Acetonitrile and Water (v/v)
acetaldehyde
isovaleraldehyde a
BP (o C)
l
CH3 -CH-CH2 -CHO
b
Density of acetaldehyde at 16 oC The temp erature for this density of isovaleraldehyde was not spe cified but is assumed to be room temperature.
TABLE 2. EXPOSURE LIMITS AND CONVER SION FACTORS. Expo sure Lim its Compound
acetaldehyde propionaldehyde valeraldehyde isovaleraldehyde
Conversion Factor ppm to m g/m 3 @ NTP
OSHA REL
NIOSH PEL
ACG IH TLV
(ppm)
(ppm)
(ppm)
200
lowest feasible level
25 ppm (ceiling)
1 pp m = 1.80 m g/m 3
none
none
none
1 pp m = 2.38 m g/m 3
50
50
50
1 pp m = 3.52 m g/m 3
none
none
none
1 pp m = 3.52 m g/m 3
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 8 of 10
TABLE 3. ALIPHATIC ALDEHYDES AND SYNONYMS Aldehyde
S ynonym s
acetaldehyde
ethanal, acetic aldehyde, ethylaldehyde, acetylaldehyde
propionaldehyde
propanal, propylaldehyde, methylacetaldehyde, propaldehyde, propylic aldehyde
valeraldehyde
n-valeraldehyde, penta nal, valeral, valeric aldehyde, am yl aldehyde, valeric acid aldehyde, butyl formal
isovaleraldehyde
isovaleral, isopentald ehyde, isovaleric aldehyde, 3-m eth ylbutan al, 3-methylbutyraldehyde, isoamyl aldehyde
TABLE 4. ANALYTICAL LIMITS OF THE METHOD LOD (µg/sample)
LOQ (µg/sample)
Calibration Range (µg/sample)
Maximu m Sam pler Cap acity a (µg/sample)
acetaldehyde
0.2
0.68
0.68 to >150
105
propionaldehyde
0.3
0.89
0.89 to >150
183
valeraldehyde
0.4
1.30
1.30 to >150
50
isovaleraldehyde
0.2
0.79
0.79 to >150
50
Compound
a
The maxim um sam pler capacity is the upper limit of the method (explained in text). The numbers shown apply to the Supelco sampler, which contains 1 mg of DNPH. Predicted capacities of the W aters sampler are 90% of these values.
TABLE 5. AVERAGE RECOVERIES AND POOLED PRECISION OF MEASUREMENT Compound
b
Pooled RSD b
1.50 µg
3.00 µg
6.00 µg
12.0 µg
20.0 µg
106%
99%
108%
106%
100%
0.031
propionaldehyde
84%
94%
91%
92%
95%
0.028
valeraldehyde
91%
97%
94%
94%
98%
0.021
isovaleraldehyde
83%
84%
85%
88%
85%
0.030
acetaldehyde
a
Average Recovery at the Level Shown (n = 6)
a
Average recoveries were determined after fortification of Supelco samplers with free aldehydes in solution with a syringe. RSDs at all five levels for acetaldehyde and isovaleraldehyde were homogeneous by Bartlett’s test; thus, all five RS Ds for aceta ldehyde and isovaleraldehyde were poolable. Other pooled RSDs were based on three or four individual RSDs.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 9 of 10
TABLE 6. STABILITIES OF DNPH DERIVATIVES ON SAMPLER AND IN SOLUTION Concentration of Liquid Std.
(days)
Average Rec overy from Sampler (n = 6)
(µg/m L b)
Stability Period for Liquid Std. (days) d
acetaldehyde
30
102%
1.25
>36
propionaldehyde
32
104%
2.20
>35
valeraldehyde
30
105%
2.20
>35
3
90% c
2.20
>35
Compound
isovaleraldehyde
a b
c
d
Storage Perioda
Samplers were stored at 5 °C in the dark. Each liquid standard consisted of aldehyde-DNPH derivative in acetonitrile solution, and each concentration presented is the equivalent concentration of underivatized aldehyde. The average reco very of 90% is not an indication of deterioration of isovaleraldehyde-DNPH; compare the recovery of 90% with recoveries for isovaleraldehyde in Table 5. Liquid standards were stored at 5 °C in the dark in airtight containers.
TABLE 7. 5% BREAKTHRO UGH DATA AND STOICHIOMET RIC QUANTITIES. Compound
Amount of aldehyde found to show 5% breakth rou gh at a flo w rate of 1L/m in (µg/sample) (in Dry Air a)
(in Lab Air b)
Sto ichio metric Quantity ofAldehyded (µg/sample)
(in Hu m id Air c)
acetaldehyde
178
173
158
222 µg
propionaldehyde
322
290
274
293 µg
valeraldehyde
>>500
>>507
>>473
435 µg
isovaleraldehyde
>>400
>>498
>400
435 µg
a b c d
Estimated relative humidity of dry air was 10% at room temperature. The relative humidity of the laboratory air was not measured. Estimated relative humidity of humid air was 85% at room tem perature. The sto ichiom etric quantities shown are the theoretical maximum quantities of aldehydes which can react with 1 mg of DN PH o n the silica gel bed in the Supe lco sam pler.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALIPHATIC ALDEHYD ES: METHO D 2018, Issue 1, dated 15 March 2003 - page 10 of 10 APP EN DIX The SKC sam pler for aldehydes (DNPH-coated silica gel tube, catalogue No. 226-119) may be used for acetaldehyde, propionaldehyde, valeraldehyde and isovaleraldehyde with mo difications of this method. These modifications include the following. (a) The m aximum recomm ended air volum e sam pled probably should be less than 15 L for an air concen tration n ear 1 0 m g/m 3 (indicated on page 2018-1) because of the upper limits of the method for the SK C, Inc . sa m pler are probably sm aller than the upper lim its in this method (105, 183, 50 and 5 0 µg per s am ple for ace taldeh yde, propio naldehyde, valeraldehyde, and isovaleraldehyde, respectively). However, the maximum recomm ended air volumes for the SKC sam pler are unknown. (b) The procedu re for recovery of analyte from the sorbent wo uld be m odified ; i.e., placem ent of sorben t sec tions into vials and addition of solvent and possible use of ultrasonic bath. (c) A volume of solvent much sm aller than 10 m L ca n be use d for reco very. Howe ver, the m inim um volum e us ed s hou ld be te sted for ad equ ate recoveries. (d) Consequences of using a much sm aller volume of solvent for recovery include a lower LOD, a lower LOQ, the need for a different range of calibration standards, and the need for a different range of levels of fortification (section 8). (e) The maxim um volume of solution for fortification of the front sorbent bed m ust be sm aller than 90 µ L and sh ould be determ ined (section 8).
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition