# Alcohols Combined (1405)

​ALCOHOLS COMBINED Formulas: Table 1
MW: Table 1
METHOD: 1405, Issue 1
CAS: Table 2
RTECS: Table 2
EVALUATION: PARTIAL
PROPERTIES:
OSHA : Table 2 NIOSH: Table 2 ACGIH: Table 2
COMPOUNDS:
1405
(1) n-butyl alcohol (2) sec-butyl alcohol (3) isobutyl alcohol
(4) n-propyl alcohol (5) allyl alcohol (6) diacetone alcohol
Issue 1: 15 March 2003
Table 1
(7) cyclohexanol (8) isoamyl alcohol (9) methyl isobutyl carbinol
SYNONYMS: See Table 3.
SAMPLING SAMPLER:
MEASUREMENT
SOLID SORBENT TUBE (Coconut shell charcoal, 100 mg/50 mg)
TECHNIQUE:
GAS CHROMATOGRAPHY, FID
ANALYTE:
Compounds above
DESORPTION:
1 mL 5% 2-propanol in CS2
INJECTION VOLUME:
1 µL
FLOW RATE: 0.01 to 0.2 L/min
VOL-MIN: -MAX:
Compounds: (1-3 ) 2L 10 L
(4-9) 1L 10 L
SHIPMENT:
Routine
SAMPLE STABILITY:
See Evaluation of Method.
BLANKS:
2 to 10 field blanks per set
TEMPERATURE -INJECTION: 220 °C -DETECTOR: 250 - 300 °C -COLUMN: 35 °C (7 minutes), to 60 °C at 5 °C/minute, hold 5 minutes, up to 120 °C at 10 °C /minute, hold 3 minutes. CARRIER GAS:
He, 4 mL/min
COLUMN:
Capillary, fused silica, 30 m x 0.32-mm ID; 0.5 µm film polyethylene glycol, DBwax or equivalent
CALIBRATION:
Solutions of analyte in eluent (internal standard optional)
RANGE:
See EVALUATION OF METHOD.
ACCURACY RANGE STUDIED: Not studied [1, 2]. BIAS:
Not determined
OVERALL PRECISION ( Ö r T ):
Not determined
ACCURACY:
Not determined
ESTIMATED LOD: 1 µg each analyte per sample PRECISION:
See EVALUATION OF METHOD.
APPLICABILITY: This method may be used to determine two or more of the specified analytes simultaneously.
INTERFERENCES: High humidity reduces sampling capacity. Less volatile compounds may displace more volatile compounds on the charcoal.
OTHER METHODS: This method combines and updates Methods 1401 and 1402, NMAM, Fourth Edition, Issue 2. Estimated LOD for each analyte is approximately ten times lower than that of the old methods.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALC OH OLS CO MB INED : MET HO D 140 5, Issue 1, dated 15 M arch 200 3 - Page 2 o f 6 EQUIPMENT:
REAGENTS: 1. 2. 3. 4. 5.
6. 7. 8. 9. 10.
Ca rbon disulfide, chrom atog raph ic grade.* 2-Propa nol, ch rom atog raph ic grade.* He xan e, chrom atog raph ic grade.* He ptan e, chrom atog raph ic grade.* Desorbing solution: Carbon disulfide with 5% (v/v) 2-propanol and 0.05% (v/v) hexane as an internal standard. NOT E: n-Undecane, 0.1 (v/v) or other suitable standard can be used. Analyte(s). Stock solution, 100 mg/mL. Prepare solutions of each analyte in heptane. Nitrogen, purified. Hydrogen, prepurified. Air, compressed, filtered.
1. Sam pler: Glass tube, 7-cm long, 6-mm OD, 4mm ID, flame-sealed ends, containing two sectio ns of a ctivate d (6 00 °C) coconut s hell charcoal (front - 100 mg; back - 50 mg) separated by a 2-mm urethane foam plug follows the back section. Pressure drop across the tube at 1 L/min airflow must be less tha n 3.4 k Pa . Tubes are com m ercially available. 2. Personal sampling pump, 0.01 to 0.2 L/min, with flexible connecting tubing. 3. Gas chromatograph, FID, integrator and colum n (page 14 05-1). 4. Vials, glass, 2-mL, PTFE -lined crimp caps. 5. Syringe, 10-µL, readable to 0.1 µL. 6. Volumetric flasks, 2 mL.
SPE CIAL PR ECAU TIO NS: Carbon disulfide is toxic and an acute fire and explosion hazard (flash point = -30 °C); all work with it must be done in a hood. Propanol, hexane, and heptane are flamm able. Analytes should be han dled in a fume hood. W ear gloves, safety glasses, and app ropriate protective clothing.
SAMPLING: 1. Calibrate each personal sampling pump with a representative sampler in line. 2. Break the ends of the sampler imm ediately before sampling. Attach sampler to personal sampling pump with flexible tubing. 3. Sam ple at a n ac curately kn own flow ra te betwee n 0.01 an d 0.2 L/m in for a total sam ple size of 1 to 10 L (2 to 10 L for n-butan ol, sec-butanol, and isobutyl alcohol). 4. Ca p the sam plers with plastic (not rub ber) cap s and pa ck sec urely for shipm ent.
SAMPLE PREPARATION: 5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard the glass wool and foam plugs. 6. Ad d 1.0 m L desorbing solution (DS) to each vial. Attac h crim p cap to each vial. 7. Allow to stand 30 min with occasional agitation.
CALIBRATION AND QUALITY CONTRO L: 8. Calibrate daily with at least six working standards covering the range of samples. a. Add know n am oun ts of a nalyte to D S in 2-m L volum etric flas ks and dilute to the m ark . b. Analyze together with samp les and blanks (steps 11 and 12). c. Prepare calibration graph (ratio of peak area of analyte to peak area of internal standard vs. µg analyte. 9. Dete rm ine desorption efficiency (DE) at least once for each batch of c harcoal used for sam pling in the calibration range (step 8). Prepare three tubes at each of five levels plus tree media blanks. a. Rem ove and disca rd back sorbent sec tion of a med ia blank sam pler. b. Inject a known amount of stock solution directly onto front sorbent section with a microliter syringe. NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALC OH OLS CO MB INED : MET HO D 140 5, Issue 1, dated 15 M arch 200 3 - Page 3 o f 6 c. Ca p the tube. Allow to stand overnight. d. Deso rb (steps 5 through 7 ) and analyze together with working standards (steps 11 and 12). e. Prepare a graph of DE vs. µg analyte recovered. 10. Analyze three quality control bind spikes and three analyst spikes to insure that the calibration graph and D E graph are in control.
MEASUREMENT: 11. Set gas chromatograph according to manufacturer’s recomm endations and to conditions given on pag e 14 05-1 . Inject s am ple aliqu ot m anu ally using solve nt flush technique o r with autos am pler. NOTE: If pea k area is abo ve the linear ra nge of the working standard s, dilute w ith eluent, reanalyze, and apply the appropriate dilution factor in calculations. 12. Measure peak area. Divide the peak area of analyte by the peak area of internal standard on the same chrom atogram.
CALCULATIONS: 13. Determ ine the ma ss, µg (correc ted for DE) of an alyte found in the sam ple front (W f) and back (W b) sorbent sec tions and in the average m edia blank front (B f) and (B b) sorben t sec tions. NO TE: If W b > W f/10, report breakthrough and possible sample loss. 14. Calculate conce ntration, C, of analyte in the air volume sam pled, V (L):
NO TE : :g/L = m g/m 3
EVALUATION OF METHOD: Previous Evaluations [2] This method, NIOSH 1405, combines and updates NIOSH Methods 1401 and 1402. Methods 1401 an 1402 were based on the 2nd edition NMAM Methods S66 (n-butyl alcohol), S53 (sec-butyl alcohol), S64 (isobutyl alcohol), S62 (n-propyl alcohol), S52 (allyl alcohol), S55 (diacetone alcohol), S54 (cyclohexan ol), S58 (isoamyl aocohol), and S60 (methyl isobutyl carbinol) which were issued on January 17, 1975 [3] and validated using 10-L air s am ples of atm ospheres generated by injec tion of the pure alcohol into dry air using a calibrated syringe drive [1]. No storage stability studies were performed. Overall precision and recoveries are shown Table 4, representing non-significant bias in each method. Current Evaluation [4] Meth ods for alcohols (n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, n-propyl alcohol, allyl alcohol, diacetone alcohol, cyclohexanol, isoamyl alcohol) were evaluated using analytes fortified on Anasorb CSC sorbent tubes (Lot #2000). Table 5 lists the desorption efficiency (DE) and precision for the compounds tested in the evaluation. Storage stability studies were performed at two different concentration levels: one at approximately 10 µg each analyte/sample for the low level, and the other at approximately 150 µg each analyte/sample for the high level. The sam ples w ere stored for 7, 14, 21, and 30 days at 5 °C. The res ults are sum m arized in Table 5.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALC OH OLS CO MB INED : MET HO D 140 5, Issue 1, dated 15 M arch 200 3 - Page 4 o f 6 REFERENCES: [1] [2]
[3] [4]
NIOSH [1977]. Docum entation of the NIOSH Validation Tests. Cincinnati, OH: U.S. Department of Health, Education, and W elfare, Publ. (NIOSH) 77-185. NIOSH [1994]. Methods 1401 and 1402. In: Eller PM, Cassinelli ME, eds. NIOSH M anual of Analytical Metho ds, 4 th ed. Cincinnati, OH: National Institute for Occupational Safety and Health, DHHS (NIOSH) Publication No. 94-113. Ta ylor DG , eds [1977]. NIO SH Ma nua l of Analytical Metho ds, 2 nd ed., V.2., Cincinnati, OH: U.S. Department of Health, Education, and W elfare. DHHS (NIOSH) Publication No. 77-157-B. Yoon YH, Perkins JB, Reynolds JM [2002]. Back-up Data Report for Alcohols Combined. DataChem Laboratories, Inc. under NIO SH c ontracts CD C-200 -95-2955 a nd CD C 200 -2001-080 00 (Augu st).
METHOD WRITTEN BY: Yound Hee Yoon, Ph.D. and James B. Perkins, DataChem Laboratories, Inc., Salt Lake City, Utah.
TABLE 1. PROPERTIES
Compound
Formula
mg/m3 = 1 ppm @ NTP
M.W.
Density (g/mL)
BP (°C)
VP @ 20°C, kPa (mm Hg)
n-Butyl alcohol
CH3 CH2 CH2 CH2 OH; C4 H1 0 O
3.03
74.12
0.810 @ 20 °C
117
0.56 (4.2)
sec-Butyl alcohol
CH3 CH(OH)CH2 CH3 ; C4 H1 0 O
3.03
74.12
0.808 @ 20 °C
99.5
1.7 (13)
Isobutyl alcohol
(CH3 )2 CHCH2 OH; C4 H1 0 O
3.03
74.12
0.806 @ 15 °C
108
1.2 (9)
n-Propyl alcohol
CH3 CH2 CH2 OH; C3 H8 O
2.46
60.09
0.805 @ 20 °C
97
2.0 (15)
Allyl alcohol
CH2 =CHCH2 OH; C3 H6 O2
2.37
58.08
0.854
96-97
2.3 (17)
Diacetone alcohol
(CH3 )2 C(OH)CH2 COCH3 ; C6 H1 2 O2
4.75
116.16
0.931 @ 25 °C
167.9
0.1 (0.8)
Cyclohexanol
C6 H1 2 O
4.09
100.16
0.962
161: MP=24
0.13 (1.0)
Isoamyl alcohol
(CH3 )2 CHCH2 CH2 OH; C5 H1 2 O
3.60
88.15
0.813 @ 15 °C
132
3.7 (28)
Methyl isobutyl carbinol
(CH3 )2 CHCH2 CH(OH)CH3 ; C6 H1 4 O
4.18
102.18
0.802
132
0.4 (3)
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALC OH OLS CO MB INED : MET HO D 140 5, Issue 1, dated 15 M arch 200 3 - Page 5 o f 6 TABLE 2. GENERAL INFORMATION Expo sure Lim its Compound
CAS #
RETECS #
OSHA (ppm)
NIOSH (ppm)
ACGIH (ppm)
n-Butyl alcohol
71-36-3
EO1400000
100 TWA
C 50 (skin)
C 50 (skin)
sec-Butyl alcohol
78-92-2
EO1750000
150 TWA
100 TWA; 150 STEL
100 TWA
Isobutyl alcohol
78-83-1
NP9625000
100 TWA
50 TWA
50 TWA
n-Propyl alcohol
71-23-8
UH8225000
200 TWA
200 TWA; 250 STEL(skin)
200 TWA; 250 STEL (skin)
Allyl alcohol
107-18-6
BA5075000
2 TWA; (skin)
2 TWA; 4 STEL (skin) (Group 1 Pesticide)
2 TWA; 4 STEL (skin)
Diacetone alcohol
123-42-2
SA9100000
50 TWA
50 TWA
50 TWA
Cyclohexanol
108-93-0
GV7875000
50 TWA
50 TWA (skin)
50 TWA (skin)
Isoamyl alcohol
123-51-3
EL5425000
100 TWA
100 TWA; 125 STEL(skin)
100 TWA; 125 STEL
Methyl isobutyl carbinol
108-11-2
SA7350000
25 TWA; (skin)
25 TWA; 40 STEL (skin)
25 TWA; 40 STEL (skin)
T AB LE 3. SY NO NY M S Compound
S ynonym s
(1) n-butyl alcohol
1-butan ol; n-buta nol; propyl carbinol.
(2) sec-Butyl alcohol
2-butanol; methyl ethyl carbinol; 2-hydroxybutane.
(3) isobutyl alcohol
2-methyl-1-propanol; isopropyl carbinol; IBA.
(4) n-propyl alcohol
1-propanol; ethyl carbinol.
(5) allyl alcohol
2-propen-1-ol; 2-propenol; vinyl carbinol.
(6) diacetone alcohol
4-hydroxy-4-methyl-2-pentanone; 2-methyl-2-pentanol-4-one.
(7) cyclohexanol
hexalin; hydralin; hydroxycyclohenane; anol.
(8) isoamyl alcohol
3-m eth yl-1-buta nol; isobutylca rbinol; isopentyl alcohol.
(9) methyl isobutyl carbinol
MIBC ; 4-m eth yl-2-pentan ol; m eth yl am yl alcohol.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALC OH OLS CO MB INED : MET HO D 140 5, Issue 1, dated 15 M arch 200 3 - Page 6 o f 6 TABLE 4. PREVIOUS METHOD EVALUATION Range Studied [1] Breakthrougha
Overall Precision (ÖrT)
Recovery (%)
(mg/m3)
(µg / sample)
@ 2 X O S H A P EL
Avg. DE
Measurement Precision (Ör)
S66
0.065
100 .0
170 to 610
1,500 to 6,000
35 L
0.89
0.021
S53
0.066
107 .2
270 to 850
2,200 to 9,000
15 L
0.92
0.028
S64
0.073
100 .0
180 to 620
1,500 to 6,000
31 L
0.85
0.023
S62
0.075
103 .5
225 to 835
2,500 to 10,000
19 L
0.89
0.016
S52
0.111
98.8
1.8 to 8.4
20 to 100
>48 L
0.90
0.023
S55
0.104
91.8
140 to 510
1,100 to 4,700
>48 L
0.78
0.054
S54
0.080
98.9
95 to 380
1,000 to 4,000
>48 L
0.99
0.015
S58
0.077
107 .6
195 to 680
1,800 to 7,000
34 L
0.99
0.020
S60
0.080
101 .8
45 to 175
500 to 2,000
>48 L
0.99
0.035
Method
a) sampling done in dry air
TABLE 5. CURRENT METHOD EVALUATION
Compound
Range Studied (µg / sample)
Average DE
Measurement Precision ( Ö r)
Storag e Stability Levels Low (day)
High (day)
n-Butyl Alcohol
8 to 3,040
0.91
0.025
<7
30
sec-Butyl alcohol
8 to 3,030
0.96
0.016
30
30
Isobutyl alcohol
8 to 3,020
0.94
0.015
30
30
n-Propyl alcohol
8 to 3,020
0.92
0.015
14
30
9 to 152
0.80
0.026
<7
14
Diacetone alcohol
9 to 3,260
0.88
0.013
<7
7
Cyclohexanol
10 to 1,710
0.95
0.017
30
30
Isoamyl alcohol
8 to 1,450
0.92
0.017
14
30
Meth yl isobutyl carbinol
8 to 1,430
0.96
0.018
30
30
Allyl alcohol
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition