HYDROCARBONS, BP 36°-216 °C 1500

FORMULA: Table 1 MW: Table 1 CAS: Table 1 RTECS: Table 1

METHOD: 1500, Issue 3 EVALUATION: PARTIAL Issue 1: 15 August 1990

Issue 3: 15 March 2003

OSHA : Table 2 PROPERTIES: Table 1

NIOSH: Table 2
ACGIH: Table 2

COMPOUNDS: cyclohexane n-heptane n-octane

(Synonyms in Table 1) cyclohexene n-hexane n-pentane
n-decane methylcyclohexane n-undecane
n-dodecane n-nonane

SAMPLING MEASUREMENT

SAMPLER: SOLID SORBENT TUBE [1] TECHNIQUE: GAS CHROMATOGRAPHY, FID [1]
(coconut shell charcoal, 100 mg/50 mg)
ANALYTE: Hydrocarbons listed above
FLOW RATE: Table 3
DESORPTION: 1 mL CS2 ; stand 30 min
VOL-MIN: Table 3
-MAX: Table 3 INJECTION
VOLUME: 1 µL
SHIPMENT: Routine
TEMPERATURES
SAMPLE -INJECTION: 250 °C
STABILITY: 30 days @ 5 °C -DETECTOR: 300 °C
-COLUMN: 35 °C (8 min) - 230 °C (1 min)
BLANKS: 10% of samples ramp (7.5 °C /min)

CARRIER GAS: Helium, 1 mL/min

ACCURACY
COLUMN: Capillary, fused silica, 30 m x 0.32-mm
RANGE STUDIED: Table 3 ID; 3.00-µm film 100% dimethyl
polysiloxane
BIAS: Table 3
CALIBRATION: Solutions of analytes in CS 2
OVERALL PRECISION (Ö r T ): Table 3
RANGE: Table 4
ACCURACY: Table 3
ESTIMATED LOD: Table 4

PRECISION ( þ r ): Table 4

APPLICABILITY: This method may be used for simultaneous measurements; however, interactions between analytes may
reduce breakthrough volumes and alter analyte recovery.

INTERFERENCES: At high humidity, the breakthrough volumes may be reduced. Other volatile organic solvents such as
alcohols, ketones, ethers, and halogenated hydrocarbons are potential interferences.

OTHER METHODS: This method is an update for NMAM 1500 issued on August 15, 1994 [2] which was based on methods
from the 2nd edition of the NIOSH Manual of Analytical Methods: S28, cyclohexane [3]; S82, cyclohexene [3]; S89, heptane [3];
S90, hexane [3]; S94, methylcyclohexane [3]; S378, octane [4]; and S379, pentane [4].

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

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REAGENTS: EQUIPMENT:

1. Eluent: Carbon disulfide *, low benzene, 1. Sampler: glass tube, 7 cm long, 6-mm OD,
chrom ato graphic quality. 4-mm ID, flame-sealed ends, containing two
2. Analytes, reage nt gra de.* sections of activated coconut shell charcoal
3. Helium, prepurified and filtered. (front = 100 mg, back = 50 mg) separated by
4. Hydrogen, prepurified and filtered. a 2-mm urethane foam plug. A silylated glass
5. Air, prepurified and filtered. wool plug precedes the front section, and a
3-mm urethane foam plug follows the back
section. Tubes are comm ercially available.
* See SPECIAL PRECAUTIONS 2. Personal sampling pumps (0.01 to 1.0 L/min,
Table 3) with flexible tubing.
3. Gas chromatograph, FID, integrator, and a
Rtx-1 or equivalent capillary column
(page 150 0-1).
4. Glass a utos am pler vials (2-m L) with
PTFE-lined caps.
5. Pipettes (1-mL) and pipette bulb.
6. Syringes (10, 25, 100, and 250 µL).
7. Volum etric flasks (10-m L).

SPECIAL PRECAUTIONS: Carbon disulfide is tox ic and extre m ely flam m able (flash point = -30°C ).
Prepare samples and standards in a well-ventilated hood.

SAMPLING:

1. Calibrate each personal sampling pump with a representative sampler in line.

2. Break the ends of the sam pler im m ediately before sa m pling. Attach the sampler to a personal sampling
pump with flexible tubing.
3. Sa m ple at an accurately known flow rate between 0.01 and 0.2 L/min (0.01 to 0.05 L/m in for n-pentane)
for a total sample size as shown in Table 3.
4. Ca p the sam plers with plastic (not rub ber) cap s an d pa ck sec urely for shipm ent.

SAMPLE PREPARATION:

5. Place the front and back sorbent sections of the sampler tube in separate vials. Include the glass wool
plug in the vial with the front sorbent section. Discard the foam plugs.
6. Ad d 1.0 m L carbon disulfide to each vial. Attac h crim p cap to each vial im m ediate ly.
7. Allow to stand at least 30 min with occasional agitation.

CALIBRATION AND QUALITY CONTRO L:

8. Ca librate daily with at leas t six wo rking standa rds from below the LOD to 10 times the LO Q. Additional
sta ndards m ay be added to exte nd the calibra tion curve if ne cessary.
a. Add known amounts of analytes to carbon disulfide in 10-mL volumetric flasks and dilute to the mark.
Prepare additional standards by serial dilution in 10-mL volumetric flasks.
b. Analyze with samp les and blanks (steps 11 and 12).
c. Prepare a calibration graph (pe ak area of analyte vs. µg of analyte per sam ple).
9. Determine the desorption efficiency (DE) at least once for each batch of charcoal used for sampling in the
calibra tion ran ge (s tep 8).
a. Prepare three tubes at each of five levels plus three media blanks.
b. Rem ove and disca rd the back sorbent sec tion of a med ia blank sam pler.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 HYD RO CAR BO NS, BP 36-216 °C : MET HO D 150 0, Issue 3, dated 15 M arch 200 3 -Page 3 of 8

c. Inject a know n am ount of stock solution (5 to 25 µL) directly onto the front sorbent section with a
microliter syringe.
d. Allow the tubes to air equilibrate for several m inutes , then cap the tub es a nd a llow to stand overnight.
e. Deso rb (steps 5 through 7 ) and analyze with standards and blank s (steps 11a nd 12).
f. Prepare a graph of DE vs. µg analyte recovered.
10. Analyze at leas t three qua lity control blind spik es a nd three a nalyst spike s to ins ure th at the calibration
grap h an d DE graph are in c ontro l.

MEASUREMENT:

11. Set the gas chromatograph according to the manufacturer's recomm endations and to the conditions given
on pag e 15 00-1 . Inject a 1-µL aliquot manually using a solvent flushing technique or with an autosam pler.
NOTE: If the pea k area is abo ve the linear ra nge of the working standard s, dilute w ith solve nt, reanalyze
and apply the appropriate dilution factor in the calculations.

Analyte Approximate Retention Time (min)

n-pentane 7.5
solvent (CS2) 9.6
n-hexane 13.0
cyclohexane 16.1
cyclohexene 16.8
n-heptane 17.7
methylcyclohexane 18.9
n-octane 21.6
n-nonane 24.9
n-decane 27.8
n-undecane 30.5
n-dodecane 32.9
NOTE: Retention tim es m ay vary slightly due to column manufacturer and age of column, and be
influen ced by other GC ins trum enta l param eters .
12. Measure the peak area.

CALCULATIONS:

13. Determine the mass, µg (corrected for DE), of analyte 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 back (B b) sorbent sections.
NO TE: If W b > W f / 10, report breakthrough and possible sample loss.
14. Calculate the concentration, C, of analyte in the air volume, V(L), sampled:

NO TE : :g/L = m g/m 3

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 HYD RO CAR BO NS, BP 36-216 °C : MET HO D 150 0, Issue 3, dated 15 M arch 200 3 -Page 4 of 8

EVALUATION OF METHOD:

Issues 1 and 2:

Precisions and biases (Table 3) were determ ined by analyzing generated atm osphe res containing one-ha lf,
one, and two times the OSHA standard. Table 3 does not contain data for n-decane, n-dodecane and n-
heptane since they were not evaluated previously. Generated concentrations were independently verified.
Breakthrough cap acities were de term ined in dry air. Storage stability was assessed at 7, 14, and 30 days.
Measurement precisions (Table 4) were determined by spiking sampling media with amounts corresponding
to one-half, one, and two times the OSH A standard for nominal air volumes. Desorption efficiencies for spiked
sam plers con taining only one co m pou nd e xce ede d 75 % [2,3,4,8 ].

Issue 3:

The desorption efficiency, at levels ranging from 10 times the LOQ to 0.1 times the REL, was determined by
spiking known am oun ts of analytes (in CS 2) on coconut shell charcoal tubes. All analytes exhibited accepta ble
desorption efficiency recovery results at six levels evaluated.

Each analyte was evaluated for its storage stability. Sorbent tubes were spiked at approximately 100 µg and
stored in a drawer for 7 days, then transferred to a refrigerator at 5° C. Samples were analyzed after 7, 14,
and 30 days. A ll analyte s had accepta ble rec overies (>9 0% ), except cyc lohexene, which had a 30 day
recovery of 85% [1].

REFERENCES:

[1] Pende rgrass SM and M ay L, Backup Data R eport, ACS /CEM B/DAR T/NIO SH (19 99).
[2] NIOSH[1994]. Hydrocarbons, BP 36-136°C. In: Eller PM, ed. NIOSH M anual of Analytical Methods,
4th rev. ed. Cincinnati, OH: U.S. Department of Health and Human Services, Public Health Service,
Centers for Disease Control, National Institute for Occupational Safety and Health, DHHS (NIOSH)
Publication No. 94-113.
[3] NIOSH M anual of Analytical Methods, 2nd. ed., V. 2, S28, S82, S89, S90, S94, U.S. Department of
Health, Educa tion, and W elfare, Publ. (NIOSH ) 77-157-B (19 77).
[4] NIOSH M anual of Analytical Methods, 2nd. ed., V. 3., S378, S379, U.S. Department of Health,
Educa tion, and W elfare, Publ. (NIOSH ) 77-157-C (1977).
[5] Code of Federal Regulations; Title 29 (Labor), Parts 1900 to 1910; U.S. Government Printing Office,
W ashington, (1989); 29 CFR 1910.1000.
[6] NIOSH Recom mendations for Occupational Safety and Health. U.S. Department of Health and
Hum an Services, D HH S (NIO SH) P ublication No . 92-100 (1992 ).
[7] 1993 T hreshold Lim it Values for Chem ical Substances and Physical Agents an d Biological Exposure
Indices. ACG IH, Cincinnati, OH (1993).
[8] Documentation of the NIOSH Validation Tests, S28, S82, S89, S90, S94, S378, S379, U.S.
Depa rtmen t of Health, Education, and W elfare, Publ. (NIOSH ) 77-185 (197 7).

AUTHORS:

Issues 1 and 2:

R. Alan Lunsford, Ph.D., NIOSH/DPSE

Issue 3:

Stephanie M. Pendergrass, NIOSH/DART and Leroy R. May, NIOSH/PRL

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

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TABLE 1. SYNONY MS, FORM ULA, MO LECULAR WEIGHT , PROPERTIES

Boiling Vapor P ressure De nsity

Nam e/ Em pirical Molecular Point @ 25°C @ 25°C
Syn onym s Fo rm ula W eight (°C) (m m Hg) (kPa ) (g/mL)

cyclohexane C 6H 12 84.16 80.7 97.6 13.0 0.779

hexahydrobenzene
CAS # 110-82-7
RTECS GU6300000

cyclohexene C 6H 10 82.15 83.0 88.8 11.8 0.811

tetrahydrobenzene
CAS # 110-83-8
RTECS GW 2500000

n-decane C 10H 22 142.28 174 NA NA 0.730

CAS # 124-18-5
RTECS HD6550000

n-dodecane C 12H 26 170.34 216 .2 NA NA 0.750

CAS # 112-40-3
RTECS JR2125000

n-heptane C 7H 16 100.21 98.4 45.8 6.1 0.684

CAS # 142-82-5
RTECS MI7700000

n-hexane C 6H 14 86.18 68.7 151 .3 20.2 0.659

CAS # 110-54-3
RTECS MN9275000

methylcyclohexane C 7H 14 98.19 100 .9 46.3 6.2 0.769

CAS # 108-87-2
RTECS GV6125000

n-nonane C 9H 20 128.26 151 NA NA 0.718

CAS # 111-84-2
RTECS RA6115000

n-octane C 8H 18 114.23 125 .7 14.0 1.9 0.703

CAS # 111-65-9
RTECS RG8400000

n-pentane C 5H 12 72.15 36.1 512 .5 68.3 0.626

CAS # 109-66-0
RTECS RZ9450000

n-undecane C 11H 24 156.31 196 NA NA 0.740

hendecane
CAS # 1120-21 -4
RTECS YQ1525000

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

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TABLE 2. EXPOSU RE LIMITS, PPM [5-7]

OSHA NIOSH AC GIH m g/m 3

Substance TW A PEAK TW A C TLV STEL per ppm
cyclohexane 300 300 300 3.44
cyclohexene 300 300 300 3.36
n-decane none none none 5.82
n-dodecane none none none 6.97
n-heptane 500 85 440 400 500 4.10
a
n-hexane 500 50 50 3.52
methylcyclohexane 500 400 400 4.01
n-nonane none 200 200 5.25
n-octane 500 75 385 300 375 4.67
n-pentane 1000 120 610 600 750 2.95
n-undecane none none none 6.39

a
The ACG IH recomm endation for other hexane isomers is: TLV 500, STEL 1000.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

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TABLE 3. SAMPLING FLOWRATE a, VOLUM E, CAPACITY, RANGE, OVE RALL BIAS AND PRECISION [3, 4, 8]

Sam pling Rang e of Overall

Flow rate Volume (L) Breakthrough Volume Generated Samples Bias Precision Accuracy
Vol Concentration
b
Substance (L/min) MIN MAX (L) (m g/m 3) (m g/m 3) (%) (ÖrT) (%)

cyclohexane 0.01 - 0.2 2.5 5 7.6 1650 510-2010 1.1 0.060c ±11 .5
cyclohexene 0.01 - 0.2 5 7 10.4 2002 510-2030 10.6 0.073 ±20 .7
n-hexane 0.01 - 0.2 not studied - - - - - -
methylcyclohexane 0.01 - 0.2 4 4 6.1 4060 968-4060 -6.5 0.056 ±15 .0
n-nonane 0.01 - 0.2 4 4 5.9 3679 877-3679 -1.8 0.062 ±12 .5
n-octane 0.01 - 0.2 4 4 6.1 3941 940-3941 6.1 0.052 ±15 .2
n-pentane 0.01 -0.2 4 4 6.5 4612 1050-4403 -2.0 0.060 ±12 .1
n-undecane 0.01-0.05 2 2 3.1 5640 1476-6190 -8.4 0.055 ±16 .6

a
Minimum recomm ended flow is 0.01 L/min.
b
Approximately two-thirds the breakthrough volume.
c
Co rrected va lue ca lculated from data in Re f. 3

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

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TABLE 4. MEASUR EM ENT R ANGE AND PR ECISION [1, 3, 4, 8]

Measurement
LOD Range Precision
Substance (µg/sample) (µg) ( þ r)
a
cyclohexane 0.1 4 - 5300 0.012
a
cyclohexene 0.08 3 - 9700 0.014
n-decane 0.06 2 - 584 0.020
n-dodecane 0.05 2 - 600 0.027
n-heptane 0.06 2 - 16300 0.014
n-hexane 0.4 10 - 14500 0.011
methylcyclohexane 0.1 4 - 16100 0.013
n-nonane 0.04 1 - 574 0.018
n-octane 0.3 11 - 18900 0.022
n-pentane 0.6 19 - 11800 0.012
n-undecane 0.05 2 - 592 0.024

a
Corrected va lue, ca lculated from the data in [1,8].

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition