|
Method no.: |
PV2139 |
|
|
Control no.: |
T-PV2139-01-0408-CH |
|
|
Target Concentration: NIOSH
REL: ACGIH TLV: |
100 mg/m3 100
mg/m3 200 mg/m3 |
|
|
Procedure: |
Samples are collected by drawing a
known volume of air through glass sampling tubes containing coconut
shell charcoal. Samples are extracted with 99:1 carbon disulfide
(CS2):N,N-dimethylformamide (DMF) and analyzed by GC using a flame
ionization detector (GC/FID). |
|
|
Recommended sampling time and sampling
rate: |
200 min at 0.1 L/min (20 L) |
|
|
Reliable quantitation limit: |
4.79 mg/m3 |
|
|
Status of method: |
Partially validated method. This
method has been subjected to the established evaluation procedures
of the Method Development Team and is presented for information and
trial use. |
|
|
September 2004 |
Yogi C. Shah |
|
|
For problems with
accessibility in using figures and illustrations in this method,
please contact the author at (801) 233-4900. |
|
|
Chromatography Team Industrial Hygiene Chemistry
Division OSHA Salt Lake Technical Center Sandy UT 84070-6406
|
1.
General Discussion
1.1 Background
1.1.1 History
OSHA presently uses NIOSH
Method 15501
(Naphtha) for kerosene. That method requires sampling on
coconut-shell charcoal, sample extraction with carbon disulfide,
and analysis by GC-FID. Kerosene is defined as "A refined
petroleum solvent (predominantly C9-C16 hydrocarbon, which is
typically a mixture of 25% normal paraffins, 11% branched
paraffins, 30% monocycloparraffins,12% dicycloparaffins, 1%
tricycloparrafins, 16% mononuclear aromatics and 5% dinuclear
aromatics"2.
This partially-validated method work was performed to
document analytical practices detailed in OSHA Method 48
(Petroleum Distillate Fractions) for kerosene. An important
analytical practice discussed in Method 483
was the use of "non-source" petroleum distillate fractions (PDF)
as analytical standards. Source PDF was defined as the bulk
material actually in use at the workplace and that was presumed
to be the source of the workplace contamination. Non-source PDF
was defined as a substitute for the same generic PDF, but not
the actual material in use at the workplace. Method 48 showed
that non-source PDF can be used as analytical standards in place
of source PDF. This is permissible because similar FID responses
are observed for different hydrocarbons. Results presented in
Method 48 showed that no significant differences were obtained
in sample analysis when using either a source or non-source PDF
to calibrate the FID response.
A single number
representing FID response to kerosene is obtained by summing
detector response of GC peaks that elute in the "kerosene
envelope". The kerosene envelope is determined with the
professional judgment of the analyst by comparison of analytical
standard chromatograms to air sample chromatograms. Any major
component (or components) observed in air samples can be
identified by GC/MS and than quantitated separately from
kerosene. The FID response for this component(s) is then
subtracted from the summed response for the air sample. The FID
response of extraction solvent components is also subtracted
from the summed response for the air sample and also for the
analytical standards. An in-house computer program has been
developed at SLTC for this purpose.
The target level
selected for this evolution was 100 mg/m3 (the NIOSH REL)
because of kerosene’s designation by ACGIH as an A3 substance,
"Confirmed Animal Carcinogen with Unknown Relevance to
Humans"4.
The results of an extraction efficiency study for
kerosene extracted from charcoal tubes with 99:1(CS2:DMF) was
98.2%. Kerosene was found to be well retained on charcoal tubes,
with 98.6% retention efficiency after 20 L of air had been drawn
through the each tube, and the ambient storage stability
recovery was 98.6% on day 14.
1.1.2 Toxic effects (This
section is for information only and should not be taken as the
basis of OSHA policy.)5,6
ACGIH lists kerosene as an A3 substance, "Confirmed
Animal Carcinogen with Unknown Relevance to Humans". The major
effects of exposure to kerosene are headache, drowsiness, and
irritation of the eyes, nose and lungs. Contact dermatitis (skin
irritation) may occur with prolonged and repeated contact.
Target organs include the respiratory system, nervous system and
mucous membranes. The LD50 is 2835 mg/kg orally in rabbits.
1.1.3 Workplace exposure7,8
Kerosene is used as a fuel in kerosene lamps, flares,
and stoves. It is also used as a degreaser. Kerosene is used as
a fuel in jet-propelled aircraft and also as a fuel in some
other engines.
1.1.4 Physical properties and other
descriptive information9,10
CAS number: |
8008-20-6 |
IMIS11: |
K107 |
RTECS number: |
OA5500000 |
molecular weight: |
170 (approximately,
C9 to C16 hydrocarbons) |
melting point: |
-51 °C |
boiling point: |
175-325 °C |
appearance: |
colorless to pale
straw |
density: |
0.8 - 0.81g/mL |
odor: |
odorless |
flash point: |
65-85 °C |
molecular formula: |
C9 to
C16 hydrocarbon |
synonyms: |
kerosine; coal oil; fuel oil
no.1; range oil |
solubility: |
Insoluble in water, miscible
in all petroleum solvents |
|
|
structural
composition: |
composition varies greatly
and includes C9 to C16 hydrocarbons
(aliphatic and aromatic) with a boiling range of about 175
to 325 °C |
This method was evaluated according to the OSHA
SLTC “Evaluation Guidelines for Air sampling Methods utilizing
Chromatographic analysis"12.
The Guidelines define analytical parameters, specify required
laboratory tests, statistical calculations and acceptance criteria.
The analyte air concentrations throughout this method are based on
the recommended sampling and analytical parameters.
1.2 Detection limit of the overall
procedure (DLOP) and reliable quantitation limit (RQL)
Different kerosenes may have similar constituents but not
have similar concentrations of these constituents, therefore, no
single representative component can be used to determine DLOP or
RQL. The DLOP is measured as mass per sample and expressed as
equivalent air concentrations, based on the recommended sampling
parameters. Ten samplers were spiked with equal descending
increments of analyte, such that the highest sampler loading was
200µg of kerosene. These spiked samplers were analyzed with the
recommended analytical parameters, and the data obtained used to
calculate the required parameters (standard error of estimate and
slope) for the calculation of the DLOP. The slope was 300 and the
SEE was 2875.4. The RQL is considered to be the lower limit for
precise quantitative measurements. It is determined from the
regression line parameters obtained for the calculation of the
DLOP, providing 75% to 125% of the analyte is recovered. The DLOP
and RQL were 28.8µg and 95.8µg, respectively. The recovery at the
RQL was 93.2%.
Table 1.2 DLOP and RQL for Kerosene
|
mass
per sample (Fg) |
area
counts (FVAS) |
|
0 |
0 |
40 |
6374 |
60 |
10949 |
80 |
15490 |
100 |
26314 |
120 |
30828 |
140 |
34276 |
160 |
42240 |
180 |
51870 |
200 |
57569 |
|
|
|
Figure 1.2.1 DLOP and RQL for
kerosene. |
|
Below
is a chromatogram of kerosene near the RQL concentration.
|
Figure 1.2.2
Chromatogram of kerosene near the RQL. (Key: (1) DMF, (2)
P-cymene. Kerosene is the series of unnumbered peaks eluting
between 7 and 25 min.) | 2. Sampling Procedure
All safety practices
that apply to the work area being sampled should be followed. The
sampling equipment should be attached to the worker in such a manner
that it will not interfere with work performance or safety.
2.1 Apparatus
2.1.1 Samples are collected using a personal
sampling pump calibrated, with the sampling device attached, to
within ±5% of the recommended flow rate.
2.1.2 Samples
are collected with 7-cm x 4-mm i.d. x 7-mm o.d. glass sampling
tubes packed with two sections (100/50 mg) of coconut shell
charcoal. The sections are held in place and separated with
glass wool plugs. For this evaluation, commercially prepared
sampling tubes were purchased from SKC, Inc. (catalog no.
226-01, lot 2000). 2.2 Reagents
None required
2.3 Technique
2.3.1 Immediately before sampling, break off the
ends of the flame-sealed tube to provide an opening
approximately half the internal diameter of the tube. Wear eye
protection when breaking tube ends. Use tube holders to minimize
the hazard of broken glass. All tubes should be from the same
lot.
2.3.2 The smaller section of the adsorbent tube is
used as a back-up and is positioned nearest the sampling pump.
Attach the tube holder to the sampling pump so that the
adsorbent tube is in an approximately vertical position with the
inlet facing down during sampling. Position the sampling pump,
tube holder and tubing so they do not impede work performance or
safety.
2.3.3 Draw air to be sampled directly into the
inlet of the tube holder. The air being sampled is not to be
passed through any hose or tubing before entering the sampling
tube.
2.3.4 After sampling for the appropriate time,
remove the adsorbent tube and seal it with plastic end caps.
Seal each sample end-to-end with an OSHA-21 form as soon as
possible.
2.3.5 Submit at least one blank sample with
each set of samples. Handle the blank sample in the same manner
as the other samples except draw no air through it.
2.3.6 Record sample air volumes (liters), sampling time
(minutes) and sampling rate (L/min) for each sample, along with
any potential interferences on the OSHA-91A form.
2.3.7
Submit the samples to the laboratory for analysis as soon as
possible after sampling. If delay is unavoidable, store the
samples at refrigerator temperature. Ship any bulk samples
separate from the air samples. 2.4 Extraction
efficiency
The extraction efficiency was determined by
liquid-spiking front sections of charcoal tubes with kerosene at
0.1 to 2 times the target concentration. These samples were stored
overnight at ambient temperature and then extracted for 30 minutes
with occasional shaking, and analyzed.
The mean extraction
efficiency over the studied range was 98.2 %. The wet extraction
efficiency was determined at 1 times the target concentration by
liquid spiking the analyte onto charcoal tubes which had 20 L
humid air (absolute humidity of 15.9 mg/L of water, about 80%
relative humidity at 22.2 °C) drawn through them. The mean
recovery for the wet samples was 100.5%.
Table 2.4 Extraction Efficiency (%) of Kerosene
|
level
|
sampler number
|
|
x
target concn |
mg
per sample |
1 |
2 |
3 |
4 |
5 |
mean |
|
0.1 |
0.2 |
96.0 |
98.0 |
93.0 |
95.0 |
95.0 |
95.4 |
0.2 |
0.4 |
97.3 |
99.0 |
98.8 |
100.0 |
97.3 |
98.5 |
0.5 |
1.0 |
100.0 |
100.7 |
99.6 |
100.5 |
99.6 |
100.1 |
1.0 |
2.0 |
99.5 |
99.2 |
99.3 |
99.2 |
95.1 |
98.5 |
2.0 |
4.0 |
101.3 |
95.2 |
100.2 |
100.4 |
95.4 |
98.5 |
|
|
|
|
|
|
|
|
1.0
(wet) |
2.0 |
99.4 |
100.6 |
100.6 |
102.4 |
99.4 |
100.5 |
| 2.5 Retention
efficiency
Six charcoal tubes were spiked with 4.0 mg of
kerosene in the front section of the tubes and allowed to
equilibrate for 6 h. The tubes had 20 L humid air (absolute
humidity of 15.9 mg/L of water, about 80% relative humidity at
22.2°C) pulled through them at 0.1 L/min. The samples were
extracted and analyzed. The mean retention recovery was 98.6%.
There was no analyte found on the backup section of any of the
tubes.
Table 2.5 Retention Efficiency (%) of
Kerosene |
|
|
sample number
|
section |
1 |
2 |
3 |
4 |
5 |
6 |
mean |
|
front
of spiked tube |
99.8 |
99.0 |
99.2 |
98.6 |
97.2 |
97.8 |
98.6 |
rear of
spiked tube |
0.0 |
00.0 |
00. |
00.0 |
00.0 |
00.0 |
00.0 |
total |
99.8 |
99.0 |
99.2 |
98.6 |
97.2 |
97.8 |
98.6 |
| 2.6 Sample
storage
Nine charcoal tubes were each spiked with 2.0 mg
of kerosene. They were allowed to equilibrate for 6 h, then 20 L
of air, with an absolute humidity of 15.7 milligrams of water per
liter of air (about 80% relative humidity at 22.2°C), was drawn
through them. Three samples were analyzed immediately, and the
rest were sealed and stored at room temperature. Three more were
analyzed after 7 days of storage and the remaining three after 14
days of storage.
Table 2.6 Storage Test for Kerosene (%
Recovery)
|
sample number |
time
(days) |
1 |
2 |
3 |
mean |
|
0 |
99.4 |
100.9 |
100.6 |
100.3 |
7 |
97.3 |
98.8 |
98.0 |
98.0 |
14 |
99.6 |
96.6 |
99.5 |
98.6 |
| 2.7 Recommended
air volume and sampling rate
Based on the data collected
in this evaluation, 20-L air samples should be collected at a
sampling rate of 0.1 L/min for 200 minutes.
2.8
Interferences (sampling)
2.8.1 There are no known compounds that will
severely interfere with the collection of kerosene.
2.8.2 Suspected interferences should be reported to the
laboratory with submitted samples.
3. Analytical
Procedure
Adhere to the rules set down in your Chemical
Hygiene Plan. Avoid skin contact and inhalation of all chemicals and
review all appropriate MSDSs.
3.1 Apparatus
3.1.1 A gas chromatograph equipped with an FID. An
Agilent 6890 plus Series Gas Chromatograph equipped with a 7683
Automatic Sampler was used in this evaluation.
3.1.2 A
GC column capable of separating kerosene from the extraction
solvent, internal standard and any potential interference. A
60-m x 0.32-mm i.d. capillary RTX Volatiles with a 0.5µm df
(Restek Corporation, Bellefonte PA) was used in the evaluation.
3.1.3 An electronic integrator or some other suitable
means of measuring peak areas. A Waters Millennium32 Data System
was used in this evaluation. An in-house computer program for
summing and subtracting selected solvent peaks was used to
calculate kerosene FID response.
3.1.4 Glass vials with
poly(tetrafluoroethylene)-lined caps. Two-mL vials were used in
this evaluation.
3.1.5 A dispenser capable of delivering
1.0 mL of extracting solvent to prepare standards and samples.
If a dispenser is not available, a 1.0-mL volumetric pipet may
be used.
3.1.6 Volumetric flasks. Ten-milliliter and
other convenient sizes for preparing standards.
3.1.7
Calibrated 10-µL syringe for preparing standards. 3.2
Reagents
3.2.1 Kerosene, reagent grade. Aldrich 99% (lot
06411KU ) was used in this evaluation.
3.2.2 Carbon
disulfide, reagent grade. Omni-Solv® 99.99% (lot CX0397-3) was
used in this evaluation.
3.2.3 N,N-Dimethylformamide (DMF), reagent grade.
Aldrich 99.9% (lot DU010523) was used in this evaluation.
3.2.4 p-Cymene, reagent grade.
Aldrich 99% (lot 11703TR) was used in this evaluation.
3.2.5 The extraction solvent was 0.25µL/mL p-cymene as internal standard in CS2/DMF
(99/1). p-Cymene was used as the
internal standard because it did not interfere with kerosene
peaks. n-Hexyl benzene was not used as the internal standard
because it eluted with kerosene peaks.
3.2.6 GC grade
nitrogen, air, and hydrogen. 3.3 Standard preparation
3.3.1 Prepare working analytical standards by
injecting microliter amounts of kerosene into volumetric flasks
containing the extraction solvent. An analytical standard at a
concentration of 2 mg/mL is equivalent to 100 mg/m3 based on a
20-L air volume.
3.3.2 Bracket sample results with
working standard concentrations. If sample concentrations are
higher than the concentration range of prepared standards,
prepare and analyze additional standards with at least as high a
concentration as the highest sample to confirm the linearity of
response. Otherwise, dilute the sample with extracting solvent
to obtain a concentration within the existing standard range.
The range of standards used in this study was from 0.2 to 4
mg/mL, which is equivalent to 0.1 to 2 times target
concentration based on a 20-L air sample. 3.4 Sample
preparation
3.4.1 Remove the plastic end caps from the sample
tubes and carefully transfer the adsorbent sections to separate
2-mL vials. Discard the glass tube, glass wool and foam plug.
3.4.2 Add 1.0 mL of extraction solvent to each vial
using the same dispenser as used for preparation of standards.
3.4.3 Immediately seal the vials with
poly(tetrafluoroethylene)-lined caps.
3.4.4 Shake the
vials vigorously by hand several times during the next 30
minutes. 3.5 Analysis
3.5.1 Analytical conditions.
GC conditions
|
|
column: |
100 °C for 5 min,
5 °C /min to 220 °C, final time 2 min |
zone
temperatures: |
220 °C
(injector) 250 °C (detector) |
run time: |
31 min |
column gas
flow: |
3.0 mL/min
(hydrogen) |
injection size: |
1.0µL (10:1
split) |
column: |
60-m x 0.32-mm
i.d. capillary RTX Volatiles (0.5-µm df) |
retention times: |
3.2 min (carbon
disulfide); 4.4 min (benzene contaminate in the carbon
disulfide); 7.1 min (DMF); 13.3 min (p-cymene); (kerosene
is the series of unnumbered peaks eluting between 7 and 30
min) |
|
|
FID conditions
|
|
hydrogen flow: |
30 mL/min |
air flow: |
400 mL/min |
makeup flow: |
25 mL/min
(nitrogen) |
|
Figure 3.5.1
Chromatogram of 2.0 mg/mL kerosene in the extraction
solvent. (key: (1) CS2, (2) benzene, (3) DMF, (4)
p-cymene) |
3.5.2 Peak areas are measured by an integrator or
other suitable means.
3.5.3 An internal standard (ISTD)
calibration method is used. A calibration curve can be
constructed by plotting ISTD-corrected response of standard
injections versus micrograms of analyte per sample. An in-house
computer program for summing of peaks and subtracting solvent
peaks was used to calculate kerosene values. Bracket the samples
with freshly prepared analytical standards over a range of
concentrations. 3.6
Interferences (analytical)
3.6.1 Any compound that produces a GC response and
has a elution time in the kerosene peak envelope is a potential
interference. If any potential interferences were reported, they
should be considered before samples are extracted. If any large
unknown peak is observed and is identified, or if a chemical was
identified as an interference by the IH, its GC response can be
subtracted from the summed kerosene value and then quantitated
as an individual analyte.
3.6.2 When necessary, the
identity or purity of an analyte peak may be confirmed by mass
spectrometry or by another analytical procedure.
4. Calculations
The amount of analyte per sampler is obtained from the
appropriate calibration curve in terms of micrograms per sample,
uncorrected for extraction efficiency. This total amount is then
corrected by subtracting the total amount (if any) found on the
blank. The air concentration is calculated using the following
formula.
|
where: |
CM is concentration by
weight (mg/m3) |
M is micrograms per sample |
V is liters of air sampled |
EE is extraction
efficiency, in decimal
form | |
5. Recommendations for Further Study
Collection, reproducibility, and other detection limit
studies need to be performed to make this a fully validated method.
References
1. NIOSH Manual of
Analytical Methods, 4th ed; U.S. Department of Health and Human
Services, Center for Disease Control and Prevention, National
Institute for Occupational Safety and Health : Cincinnati, OH,
Method 1550.
2. NIOSH Pocket Guide, www.cdc.gov (accessed
08/15/04).
3. OSHA Method 48, Petroleum Distillate
Fractions, www.osha.gov (accessed 05/15/20023)
4. 2004 TLV
and BEIs, Threshold Limit values for Chemical Substances and
Physical Agents, American Conference of Governmental Industrial
Hygienists, (ACGIH): Cincinnati, OH, 2004.
5. Budavari,S.
Ed, The Merck Index, 12th edition, Merck & Co. Inc., Rawhay,
N.J., 1997, p 903.
6. MSDS: Brown oil,
www.brownoil.com/msdskerosene.htm (accessed 06/08/2003).
7.
Budavari,S. The Merck Index , 12th edition Merck & Co. Inc.,
Rawhay, N.J., 1997, p 903.
8. MSDS: Brown oil,
www.brownoil.com/msdskerosene.htm (accessed 06/02/2004).
9.
MSDS: Brown oil, www.brownoil.com/msdskerosene.htm (accessed
06/02/2004).
10. Budavari,S. Ed, The Merck Index , 12th
edition Merck & Co. Inc., Rawhay, N.J., 1997, p 903.
11.
OSHA Chemical Sampling Information, http://www:osha.gov (accessed
06/02/2004).
12. Burright, D.; Chan, Y.; Eide, M.; Elskamp,
C.; Hendricks, W.; Rose, M. C. Evaluation Guidelines For Air
Sampling Methods Utilizing Chromatographic Analysis; OSHA Salt Lake
Technical Center, U.S. Department of Labor: Salt Lake City, UT,
1999. |
|
| |