2-BUTANONE
Method no.: |
84 |
|
Matrix: |
Air |
|
Target concentration: |
200 ppm (590 mg/m3) |
|
Procedure: |
Samples are collected by drawing air through glass sampling
tubes containing Carbosieve S-III (carbon based
molecular sieve) adsorbent. Samples are desorbed with a mixture of
99/1 (v/v) carbon disulfide
(CS2)/dimethylformamide (DMF) in the
presence of anhydrous sodium sulfate and are analyzed by GC using a
flame ionization detector. |
|
Recommended air volume and sampling rate: |
3 L at 0.05 L/min |
|
Reliable quantitation limit: |
79.9 ppb (236 µg/m3) |
|
Standard error of estimate at the target
concentration: (Section 4.7.) |
8.4% |
|
Status of method: |
Evaluated method. This method has been subjected to the
established evaluation procedures of the Organic Methods Evaluation
Branch. |
|
Date: July 1990 |
Chemist: Donald
Burright |
Organic Methods Evaluation Branch OSHA Analytical
Laboratory Salt Lake City, Utah
1.General Discussion
1.1. Background
1.1.1. History
2-Butanone is one of the industrial solvents that exhibit storage
stability problems when collected with charcoal sampling tubes. This
problem was overcome in OSHA Method 16, where samples were collected
with silica gel sampling tubes and analyzed on a GC equipped with a
flame ionization detector (FID) after desorption with dimethyl
sulfoxide (DMSO). (Ref.5.1.) In order to attain adequate sampler
capacity, the sampling procedure of OSHA Method 16 requires two
standard size (6-mm o.d. × 4-mm i.d.× 7
cm) silica gel tubes connected in series.
The purpose of this evaluation was to develop a sampling and
analytical procedure for 2-butanone that would avoid
the inconvenience of using two sampling tubes in series, as
recommended in OSHA Method 16, and preserve the storage stability
not achievable with charcoal sampling tubes. These goals were
accomplished by using sampling tubes containing carbon molecular
sieve adsorbent, Carbosieve S-III. Carbosieve
S-III has been used earlier in OSHA Method 69 (Ref.
5.2.) to overcome a capacity problem with acetone, a ketone similar
to 2-butanone. The use of Carbosieve S-III
also permitted to use of a 99/1 (v/v) carbon
disulfide/dimethylformamide desorbing solution, which is less
detrimental to analytical GC columns than the dimethyl sulfoxide
required in OSHA Method 16.
This procedure does not invalidate OSHA Method 16, but provides
an alternative to the inconvenience of using sampling tubes
connected in series.
1.1.2. Toxic effects (This section is for information only and
should not be taken as the basis of OSHA policy.)
Inhalation of vapors may cause headache, nausea, vomiting,
dizziness, drowsiness, irritation of the respiratory tract, and loss
of consciousness. Contact with skin or eyes may cause irritation.
Prolonged exposure may cause dermatitis. Liquid may cause permanent
eye damage. Ingestion may cause nausea, vomiting, headaches,
dizziness, gastrointestinal irritation. (Ref. 5.3.) The TLV for
2-butanone (200 ppm) and the STEL (300 ppm) was
established to prevent any injurious effects and to minimize
complaints about odor and irritation. (Ref. 5.4.) The OSHA PEL has
been established equal to the TLV.
1.1.3. Workplace exposure
In 1985, 244 million kilograms were produced in the United
States. The major uses of 2-butanone in 1981 were as
follows: solvent for vinyl coatings, 30%; solvent for adhesives,
18%; solvent for acrylic coatings, 11%; solvent for other coatings,
7%; solvent for magnetic tapes, 7%; extraction solvent for lube oil
dewaxing, 5%; solvent for printing inks, 5%. (Ref. 5.5.) In 1978,
NIOSH estimated that over 3 million workers are potentially exposed
to 2-butanone in the United States (Ref.5.6.).
1.1.4. Physical properties and other descriptive information
(Ref.5.7., unless otherwise stated)
CAS no.: |
78-93-3 |
molecular weight: |
72.11 |
chemical formula: |
CH3COCH2CH3 |
melting point: |
-86.4°C |
boiling point: |
79.6°C |
vapor pressure: |
10.33 kPa (77.5 mmHg) at 20°C |
vapor density: |
2.41 (air=1) |
specific gravity: |
0.805 (water=1) |
explosive limits: |
1.8% (lower) (Ref.5.8.) 11.5% (upper) (Ref.5.8.) |
self-ignition temperature: |
516°C (Ref.5.8.) |
flash point: |
-6°C (Ref.5.9.) |
odor: |
sharp, fragrant, acetone-like |
odor threshold: |
2 ppm |
appearance: |
colorless liquid |
solubility: |
27 g/100 mL of water; soluble in most common organic
liquids |
synonyms: |
MEK; methyl ethyl ketone; ethyl methyl ketone; methyl
acetone |
The analyte air concentrations throughout this method are
based on the recommended sampling and analytical parameters. Air
concentrations listed in ppm and ppb are referenced to 25°C and
101.3 kPa (760 mmHg). |
1.2. Limit defining parameters
1.2.1. Detection limit of the analytical procedure
The detection limit of the analytical procedure is 0.141 ng per
injection (1.0-µL injection with a 5:1 split). This is
the amount of analyte that will give a peak whose height is
approximately 5 times the height of the baseline noise. (Section
4.1.)
1.2.2. Detection limit of the overall procedure
The detection limit of the overall procedure is 0.707 µg per
sample (79.9 ppb or 236 µg/m3). This is
the amount of analyte spiked on the sampling device that allows
recovery of an amount of analyte equivalent to the detection limit
of the analytical procedure. (Section 4.2.)
1.2.3. Reliable quantitation limit
The reliable quantitation limit is 0.707 µg per sample (79.9 ppb
or 236 µg/m3). This is the smallest amount
of analyte spiked on the sampling device that can be quantitated
within the requirements of a recovery of at least 75% and a
precision (±1.96 SD) of ±25% or better. (Section 4.3.)
The reliable quantitation limit and detection limits
reported in the method are based upon optimization of the
instrument for the smallest possible amount of analyte. When
the target concentration of analyte is exceptionally higher
than these limits, they may not be attainable at the routine
operating parameters. |
1.2.4. Instrument response to the analyte
The instrument response over the concentration range of 0.5 to 2
times the target concentration is linear. (Section 4.4.)
1.2.5. Recovery
The recovery of 2-butanone from samples used in
17-day storage test remained above 80.1% when the
samples were stored at about 22°C. (Section 4.5., regression line of
Figure 4.5.1.)
1.2.6. Precision (analytical procedure only)
The pooled coefficient of variation obtained from replicate
determinations of analytical standards at 0.5, 1 and 2 times the
target concentration is 0.0172. (Section 4.6.)
1.2.7. Precision (overall procedure)
The precision at the 95% confidence level for the 17-day ambient
temperature storage test is ±16.4%. (Section 4.7.) This includes an
additional ±5% for pump error. The overall procedure must provide
results at the target concentration that are ±25% or better at the
95% confidence level.
1.2.8. Reproducibility
Six samples collected from a controlled test atmosphere and a
draft copy of this procedure were given to a chemist unassociated
with this evaluation. The samples were analyzed after 7 days of
refrigerated storage. No individual sample result deviated from its
theoretical value by more than the precision reported in Section
1.2.7. (Section 4.8.)
1.3. Advantages
1.3.1. This procedure allows the use of a single standard size
(6-mm o.d.× 4-mm i.d.× 7 cm) adsorbent
tube for the collection of 2-butanone.
1.3.2. The desorbing solvent is no longer DMSO, which has a
detrimental effect on GC columns.
1.4. Disadvantages
1.4.1. The fine mesh size of Carbosieve S-III
(60/80) results in a greater pressure drop across the sample tube
than occurs with the conventional silica gel sampling tube. This
results in the need for the 0.05 L/min sampling rate.
1.4.2. The recommended sample size is 3 L as opposed to the 10 L
sample size of previous methods.
2. Sampling Procedure
2.1. Apparatus
2.1.1. Samples are collected using a personal sampling pump
calibrated to within ±5% of the recommended flow rate with the
sampling device attached.
2.1.2. Samples are collected with 4-mm i.d. × 6-mm o.d.× 7.0 cm
glass sampling tubes packed with two sections of 60/80 mesh
Carbosieve S-III. The front section contains 130 mg and
the back section contains 65 mg of adsorbent. The sections are held
in place with glass wool plugs. For this evaluation, Supelco's
ORBO-91 Carbosieve S-III tubes (catalog
no.2-0360) were used.
2.2. Reagents
No sampling reagents are required.
2.3. Technique
2.3.1. Immediately before sampling, break off the ends of the
Carbosieve S-III tube. All tubes should be from the
same lot.
2.3.2. Attach the sampling tube to the sampling pump with
flexible tubing. It is desirable to utilize sampling tube holders
which have a protective cover that shield the employee from the
sharp, jagged end of the sampling tube. Position the tube so that
sampled air first passes through the 130-mg section.
2.3.3. Air being sampled should not pass through any hose or
tubing before entering the sampling tube.
2.3.4. Attach the sampler vertically in the worker's breathing
zone in such a manner that it does not impede work performance or
safety.
2.3.5. After sampling for the appropriate time, remove the
sampler and seal the tube with plastic end caps. Wrap each sample
end-to-end with a Form OSHA-21 seal.
2.3.6. Submit at least one blank sampler with each set of
samples. Handle the blank sampler in the same manner as the other
samples except draw no air through it.
2.3.7. Record sample volumes (in liters of air) for each sample,
along with any potential interferences.
2.3.8. Ship any bulk samples in a container separate from the air
samples.
2.4. Sampler capacity
The sampling capacity of the front section of a Carbosieve
S-III sampling tube was determined by sampling a
controlled test atmosphere containing 400 ppm (1080
mg/m3, 77% relative humidity) of
2-butanone at ambient temperature. The sampling rate was
0.0516 L/min. The 5% breakthrough air volume was 11.1 L.(Section 4.9.)
2.5. Desorption efficiency
2.5.1. The average desorption efficiency for
2-butanone from Carbosieve S-III adsorbent
was 98.6% over the range of 0.5 to 2 times the target
concentration.(Section 4.10.1.)
2.5.2. Desorbed samples remain relativity stable for at least 24
h.(Section 4.10.2.)
2.6. Recommended air volume and sampling rate
2.6.1. For time-weighted average samples, the recommended air
volume is 3 L collected at 0.05 L/min (1-h samples).
The 3-L air volume was selected so that the sampling
time would be consistent with other sampling procedures using
Carbosieve S-III.
2.6.2. For short-term exposure limit samples, the recommended air
volume is 0.75 L collected at 0.05 L/min (15-min
samples).
2.6.3. When short-term exposure limit samples are required, the
reliable quantitation limit becomes larger. For example, the
reliable quantitation limit is 0.320 ppm (0.943
mg/m3) for 2-butanone when
0.75 L is collected.
2.7. Interferences (sampling)
2.7.1. It is not known if any compounds will severely interfere
with the collection of 2-butanone on Carbosieve
S-III. In general, the presence of other contaminant
vapors in the air will reduce the capacity of Carbosieve
S-III to collect 2-butanone.
2.7.2. Suspected interferences should be reported to the
laboratory with submitted samples.
2.8. Safety precautions (sampling)
2.8.1. The sampling equipment should be attached to the worker
in such a manner that it will not interfere with work performance or
safety.
2.8.2. All safety practices that apply to the work area being
sampled should be followed.
2.8.3. Protective eyewear should be worn when breaking the ends
of the glass Carbosieve S-III tubes.
3. Analytical Procedure
3.1. Apparatus
3.1.1. A GC equipped with a flame ionization detector (FID). A
Hewlett-Packard 5890 Gas Chromatograph equipped with a
7673A Autosampler and an FID was used in this evaluation.
3.1.2. A GC column capable of separating 2-butanone
and the internal standard from the desorbing solvent and any
potential interferences. A 30-m × 0.32-mm
i.d. SUPELCOWAX 10 (0.25-µm film thickness) capillary
column (Supelco Inc.) was used in this evaluation.
3.1.3. An electronic integrator or some other suitable means of
measuring detector response. A Hewlett-Packard 5895A GC
ChemStation was used in this evaluation.
3.1.4. Two-milliliter vials with polytetrafluoroethylene-lined
caps.
3.1.5. A dispenser capable of delivering 1.0 mL of desorbing
solution is used to prepare standards and samples. If a dispenser is
not available, a 1.0-mL volumetric pipet may be used.
3.2. Reagents
3.2.1. 2-Butanone. Reagent grade or better should
be used. The 2-butanone (b&j brand HIGH PURITY
SOLVENT) used in this evaluation was purchased from American Burdick
& Jackson (Muskegon, MI).
3.2.2. Carbon disulfide, CS2. Reagent
grade or better CS2 should be used. The
CS2 (REAGENT ACS) was purchased from
Fisher Scientific (Fair Lawn, NJ). In this evaluation, benzenefree
CS2 was used. The
CS2 had been passed through Molecular
Sieve 13X (45/60 mesh) to remove the benzene contamination. Fifty
grams of molecular sieve should remove the benzene from 1 L of
carbon disulfide.
3.2.3. Dimethylformamide, DMF. Reagent grade or better should be
used. The DMF (b&j brand HIGH PURITY SOLVENT) used in this
evaluation was purchased from American Burdick & Jackson
(Muskegon, MI).
3.2.4. Sodium sulfate, anhydrous. Sodium sulfate is used as a
drying agent. The sodium sulfate (AR grade) used in this evaluation
was purchased from Mallinckrodt (Paris, KY).
3.2.5. Desorbing solution. This consists of a solution of 99:1
(v/v) benzene-free CS2/DMF.
An internal standard such as ethyl benzene can be used.
3.2.6. Ethyl benzene. This was used as the internal standard in
the desorbing solution. The solution is prepared by adding 250 µL of
ethyl benzene to 1 L of desorbing solution. The ethyl benzene
(reagent grade) used in this evaluation was purchased from Eastman
Kodak (Rochester, NY).
3.3. Standard preparation
3.3.1.Prepare concentrated stock standards by diluting the
2-butanone with DMF. Prepare working analytical
standards by injecting microliter amounts of concentrated stock
standards into 2-mL vials containing 1 mL of desorbing
solution delivered from the same dispenser used to desorb samples.
For example, to prepare a target level standard, inject 10 µL of a
stock solution containing 177 mg/mL 2-butanone in DMF
into 1 mL of desorbing solution.
3.3.2. Prepare a sufficient number of analytical standards to
generate a calibration curve. Ensure that the amount of
2-butanone found in the samples is bracketed by the
range of the standards. Prepare additional standards if necessary.
3.4. Sample preparation
3.4.1. Remove the plastic caps from the sample tube and
carefully transfer each section of the adsorbent to separate vials.
Discard the glass tube and glass wool plugs.
3.4.2. Add approximately 150 mg of anhydrous sodium sulfate to
each sample.
3.4.3. Add 1.0 mL of desorbing solution to each vial and
immediately seal the vials with
polytetrafluoroethylene-lined caps.
3.4.4. Shake the vials vigorously several times during the next
30 min.
3.5. Analysis
3.5.1. Analytical conditions
GC conditions |
|
|
temperatures: |
40°C (column) 200°C (injector) 220°C (detector) |
temp program: |
hold initial temp 1.0 min, increase temp at 5°C/min to
65°C, then increase temp at 25°C/min to 190°C. |
column gas flow: |
1.2 mL/min (hydrogen) |
septum purge: |
1.5 mL/min (hydrogen) |
injection size: |
1.0 µL (5:1 split) |
column: |
30 m × 0.32-mm i.d. capillary SUPELCOWAX 10 (0.25-µm
film thickness) |
retention times: |
2.75 min (2-butanone) 5.75 min (ethyl
benzene) |
|
FID conditions |
|
hydrogen flow: |
34 mL/min |
air flow: |
450 mL/min |
nitrogen makeup flow: |
33 mL/min |
chromatogram: |
Figure 3.5.1. |
3.5.2. Measure detector response using a suitable method such as
electronic integration.
3.5.3. An internal standard (ISTD) calibration method is used. A
calibration curve can be constructed by plotting micrograms of
2-butanone per sample versus
ISTD-corrected response of standard injections. Bracket
the samples with freshly prepared analytical standards over a range
of concentrations.
3.6. Interferences (analytical)
3.6.1. Any compound that produces an FID response and has a
similar retention time as the analyte or internal standard is a
potential interference. If any potential interferences were
reported, they should be considered before samples are desorbed.
Generally, chromatographic conditions can be altered to separate an
interference from the analyte.
3.6.2. Retention time on a single column is not considered proof
of chemical identity. Analysis by an alternate GC column or
confirmation by mass spectrometry are additional means of
identification.
3.7. Calculations
The analyte concentration for samples is obtained from the
appropriate calibration curve in terms of micrograms per sample,
uncorrected for desorption efficiency. The air concentration is
calculated using the following formulae. The back (65-mg)
section is analyzed primarily to determine if there was any
breakthrough from the front (130-mg) section during
sampling. If a significant amount of analyte is found on the back
section (e.g., greater than 25% of the amount found on the front
section), this should be reported with sample results. If any analyte
is found on the back section, it is added to the amount on the front
section. This total amount is then corrected by subtracting the total
amount (if any) found on the blank.
mg/m3 = |
(micrograms of analyte per sample, blank
corrected)
(liters of air sampled) (desorption
efficiency) |
ppm = |
(mg/m3)
(24.46)
(molecular weight of analyte) |
where 24.46 = molar volume (liters) at 101.3 kPa (760
mmHg) and 25°C
molecular weight = 72.11
3.8. Safety precautions (analytical)
3.8.1. Restrict the use of all chemicals to a fume hood.
3.8.2. Avoid skin contact and inhalation of all chemicals.
3.8.3. Wear safety glasses and a lab coat at all times while in
the laboratory areas.
4. Backup Data
4.1. Detection limit of the analytical procedure
The detection limit of the analytical procedure is 0. 141 ng per
injection, based on a 1.0-µL injection (with a 5:1 split)
of a 0.707 µg/mL standard. This amount produced a
2-butanone peak whose height is about 5 times the height
of the baseline noise. A chromatogram of the detection limit of the
analytical procedure is shown in Figure 4.1.
4.2. Detection limit of the overall procedure
The detection limit of the overall procedure is 0.707 µg per sample
(79.9 ppb or 236 µg/m3). The injection size
listed in the analytical procedure (1.0 µL, 5:1 split) was used in the
determination of the detection limit of the overall procedure. Eight
vials containing 130 mg of Carbosieve S-III resin were
spiked with 0.707 µg of 2-butanone. The samples were
desorbed about 24 h after being spiked.
Table 4.2. Detection Limit of the Overall Procedure
for 2-Butanone
|
sample no. |
µg spiked |
µg recovered |
|
1 |
0.707 |
0.677 |
2 |
0.707 |
0.689 |
3 |
0.707 |
0.743 |
4 |
0.707 |
0.756 |
5 |
0.707 |
0.747 |
6 |
0.707 |
0.720 |
7 |
0.707 |
0.722 |
8 |
0.707 |
0.739 |
|
4.3. Reliable quantitation limit data
The reliable quantitation limit is 0.707 µg per sample (79.9 ppb or
236 µg/m3). The injection size listed in the
analytical procedure (1.0 µL, 5:1 split) was used in the determination
of the reliable quantitation limit. Eight vials containing 130 mg of
Carbosieve S-III resin were liquid-spiked
with 0.707 µg of 2-butanone. Because the recovery of
2-butanone from the spiked samples was greater than 75%
and had a precision of ±25% or better, the detection limit of the
overall procedure and reliable quantitation limit are the same.
Table 4.3. Reliable Quantitation Limit (Based on
samples and data of Table 4.2.)
|
percent recovered |
statistics |
|
95.8 |
97.4 |
= |
102.4 |
105.1 |
SD = |
4.0 |
106.9 |
Precision = |
(1.96)(±4.0) |
105.6 |
= |
±7.8 |
101.8 |
102.1 |
104.5 |
|
4.4. Instrument response to 2-butanone
The instrument response to 2-butanone over the range
of 0.5 to 2 times the target concentration is linear with a slope of
14.47 (in ISTD-corrected area counts per
microgram/milliliter). The precision of the response to
2-butanone was determined by multiple injections of
2-butanone standards. The data below is presented
graphically in Figure 4.4.
Table 4.4. Instrument Response to
2-Butanone Injection Split =
5:1
|
× target concn µg/mL |
0.5× 885 |
1× 1770 |
2× 3540 |
|
area counts |
12714 |
25768 |
50082 |
|
13154 |
25721 |
51115 |
12992 |
26147 |
51561 |
13173 |
26068 |
50283 |
12749 |
25967 |
50497 |
12629 |
25817 |
52899 |
12676 |
25528 |
50759 |
13062 |
25527 |
53058 |
|
|
12894 |
25818 |
51282 |
|
4.5. Storage data
Storage samples are generated by sampling the recommended air
volume at the recommended sampling rate from a test atmosphere at 80%
relative humidity containing 2-butanone at the target
concentration. Samples were generated by sampling from an atmosphere
containing 2-butanone at 2 times the target
concentration. Thirty-six storage samples were collected
by sampling a dynamically generated atmosphere containing 1080
mg/m3 or 400 ppm of 2-butanone
and 77% relative humidity for 30 min at 0.05 L/min.
One-half of the tubes was stored in a freezer
(-20°C) and the other half was stored in a closed drawer
at ambient temperature (about 22°C). At 3-4 day
intervals, three samples were selected from each of the two storage
sets and analyzed. The results are listed below and shown graphically
in Figures 4.5.1.
and 4.5.2.
Table 4.5. Storage Test of
2-Butanone
|
storage time |
|
% recovery |
|
% recovery |
(days) |
|
(ambient) |
|
(refrigerated) |
|
0 |
|
116.2 |
103.1 |
98.0 |
|
116.2 |
103.1 |
98.0 |
|
97.0 |
87.9 |
97.7 |
97.0 |
87.9 |
97.7 |
4 |
96.8 |
94.1 |
99.9 |
99.9 |
93.9 |
89.0 |
7 |
84.1 |
87.2 |
88.6 |
96.6 |
86.3 |
87.7 |
11 |
83.0 |
87.9 |
80.1 |
91.7 |
89.0 |
89.3 |
14 |
77.8 |
77.0 |
81.9 |
91.1 |
89.3 |
93.6 |
17 |
87.9 |
82.4 |
90.5 |
82.3 |
92.7 |
91.2 |
|
4.6. Precision (analytical method)
The precision of the analytical procedure is defined as the pooled
coefficient of variation determined from replicate injections of
2-butanone standards at 0.5, 1 and 2 times the target
concentration. Based on the data of Table 4.4., the coefficients of
variation (CV) for the three levels and the pooled coefficient of
variation () were calculated and are listed
below.
Table 4.6. Precision of the Analytical Method
(Based on the Data of Table 4.4.)
|
× target concn µg/mL |
0.5× 885 |
1× 1770 |
2× 3540 |
|
SD1 |
225 |
231 |
1147 |
CV |
0.01746 |
0.00895 |
0.02236 |
|
= 0.0172 |
1 standard deviation is in
area counts |
4.7. Precision (overall procedure)
The precision of the overall procedure is determined from the
storage data. The determination of the standard error of estimate
(SEE) for a regression line plotted through the graphed storage data
allows the inclusion of storage time as one of the factors affecting
overall precision. The SEE is similar to the standard deviation,
except it is a measure of dispersion of data about a regression line
instead of about a mean. It is determined with the following equation:
where |
n = k
= k = |
total no. of data points 2 for linear
regression 3 for quadratic regression |
|
Yobs =
Yest =
|
observed % recovery at a given
time estimated % recovery from the regression line at the
same given time |
An additional 5% for pump error is added to the SEE by the addition
of variances. The precision at the 95% confidence level is obtained by
multiplying the SEE (with pump error included) by 1.96 (the
z-statistic from the standard normal distribution at the
95% confidence level). The 95% confidence intervals are drawn about
their respective regression line in the storage graph as shown in
Figure 4.5.1.
The data for Figure 4.5.1. was used to determine the SEE of ±8.4% and
the precision of the overall procedure of ±16.4%.
4.8. Reproducibility data
Six samples, collected from a dynamically generated atmosphere
containing 2-butanone, were given to a chemist
unassociated with this study. The samples were generated by drawing a
423-ppm test atmosphere through sampling tubes for
20-60 min at approximately 0.050 L/min. The samples were
analyzed after being stored for 7 days at 5°C. No sample result had a
deviation greater than the precision of the overall procedure, which
is ±16.4%.
Table 4.8. Reproducibility Data
|
µg spiked |
µg recovered |
% recovered |
% deviation |
|
3490 |
2978 |
85.3 |
-14.7 |
3680 |
3275 |
89.0 |
-11.0 |
1763 |
1608 |
91.2 |
-8.8 |
1774 |
1633 |
92.1 |
-7.9 |
1215 |
1082 |
89.1 |
-10.9 |
1173 |
1113 |
94.9 |
-5.1 |
|
4.9. Sampler capacity
Sampler capacity was determined by sampling from a dynamically
generated atmosphere of 400 ppm (1080 mg/m3)
2-butanone with a Carbosieve S-III sampling
tube that contained only the front section. The tube was followed by a
whole Carbosieve S-III sampling tube. The backup tube was
periodically changed over a 4 h time. The relative humidity of the
test atmosphere was 77%. The sampling rate was 0.0516 L/min. The air
volumes listed below are the midpoints of each sampling interval plus
the total of all preceding sampling intervals. The data is graphically
shown in Figure 4.9.
Table 4.9. Breakthrough on the Carbosieve
S-III Tube
|
air vol (L) |
sample time (min) |
downstream (mg/m3) |
breakthrough (%) |
|
2.322 |
45.0 |
0 |
0 |
5.031 |
97.5 |
0 |
0 |
5.805 |
112.5 |
0 |
0 |
6.631 |
128.5 |
0 |
0 |
7.405 |
143.5 |
0 |
0 |
8.179 |
158.5 |
0 |
0 |
8.953 |
173.5 |
0 |
0 |
9.727 |
188.5 |
0 |
0 |
10.50 |
203.5 |
18.5 |
1.71 |
11.27 |
218.5 |
75.4 |
6.99 |
12.05 |
233.5 |
206.6 |
19.1 |
|
4.10. Desorption efficiency and stability of desorbed samples
4.10.1. Desorption efficiency
The desorption efficiency (DE) of 2-butanone was
determined by liquid-spiking 130-mg
portions of Carbosieve S-III adsorbent with
2-butanone at 0.5 to 2 times the target concentrations.
These samples were stored overnight and then desorbed with desorbing
solution and analyzed. The average desorption efficiency over the
studied range was 98.6%.
Table 4.10.1. Desorption Efficiency of
2-Butanone
|
× target concn µg/mL |
0.5× 885 |
1× 1770 |
2× 3540 |
|
DE, % |
100.7 |
101.1 |
95.9 |
|
96.9 |
100.0 |
96.9 |
96.4 |
101.6 |
96.9 |
99.6 |
99.3 |
98.7 |
99.7 |
95.9 |
98.7 |
96.1 |
102.7 |
98.4 |
|
|
98.2 |
100.1 |
97.6 |
|
4.10.2. Stability of desorbed samples
The stability of desorbed samples was investigated by reanalyzing
the target concentration samples 24 h after initial analysis. The
original analysis was performed and the vials were not recapped
after injection. The samples were reanalyzed with fresh standards.
The average recovery, compared to the average recovery of the
original analysis, was 95.8 or a -4.3% change.
Table 4.10.2. Stability of Desorbed Samples
|
initial recovery (percent) |
recovery after 24 h (percent) |
percent change |
|
101.1 |
97.5 |
-3.6 |
100.0 |
95.9 |
-4.1 |
101.6 |
88.8 |
-12.8 |
99.3 |
97.7 |
-1.6 |
95.9 |
94.3 |
-1.6 |
102.7 |
100.3 |
-2.4 |
|
Figure 3.5.1. Chromatogram
of 2-butanone at 0.2 times the target concentration.
Figure 4.1. Chromatogram of
2-butanone at the detection limit, 0.141 ng per injection, injection split
= 5:1.
Figure 4.4. Instrument
response curve for 2-butanone, slope = 14.47 area counts per mirograms per
milliliter, injection split = 5:1.
Figure 4.5.1. Ambient
storage test for 2-butanone.
Figure 4.5.2. Refrigerated
storage test for 2-butanone.
Figure 4.9. Determination
of 5% breakthrought air volume.
5. References
5.1. "OSHA Analytical Methods Manual"; U.S. Department of Labor,
Occupational Safety and Health Administration; OSHA Analytical
Laboratory; Salt Lake City, UT, 1985; Method 16; American Conference
of Government Industrial Hygienists (ACGIH); Cincinnati, ISBN
0-936712-66-X.
5.2. Cummins, K.J. "OSHA Method No. 69; Acetone", OSHA Analytical
Laboratory, unpublished, Salt Lake City, UT 84165, March, 1988.
5.3. "Industrial Exposure and Control Technologies for OSHA
Regulated Hazardous Substances", U.S. Department of Labor,
Occupational Safety and Health Administration, Washington, D.C.
5.4. "Documentation of Threshold Limit Values and Biological
Indices" 5th ed.; American Conference of Government Industrial
Hygienists (ACGIH); Cincinnati, ISBN 0-036712-68-6, 1986;
p 395.
5.5. "Hazardous Substances Database", on-line database from U.S.
Department of Health and Human Services, National Library of Medicine,
Bethesda, MD.
5.6. "NIOSH Criteria for a Recommended Standard: Occupational
Exposure to Ketones", U.S. Department of Health, Education, and
Welfare, PHS/CDC/NIOSH, pp 23-24, June, 1978.
5.7. ChemInfo Database on CCINFO CD-R0M disc 89-2, Canadian Centre
for Occupational Health and Safety, Hamilton, Ontario.
5.8. CAMEO Database, National Oceanic and Atmospheric
Administration, Hazardous Materials Response Branch, Seattle, WA.
5.9. Papa, Anthony J., Sherman, Paul D. in "Kirk-Othmer
Encyclopedia of Chemical Technology"; 3rd ed. ; Grayson, M., Ed.; John
Wiley & Sons, New York, 1983, Vol. 13, p 899.
|