|
Method no.: |
ID-140 |
|
|
Matrix: |
Air |
|
|
OSHA Permissible Exposure
Limits Mercury Vapor (Final Rule
Limit): Mercury (Transitional Limit): |
0.05 mg/m3 (TWA) 0.1
mg/m3 as total mercury (TWA) |
|
|
Collection Device: |
A passive or an active sampling device
are available. Both devices use HydrarR or hopcalite as
the solid sorbent. |
|
|
Recommended Sampling Rate
Passive Dosimeter:
Active Sampler: |
0.020 L/min (@ 20 °C and 101
kPa) 0.20 L/min |
|
|
Recommended Air Volume Range
Passive Dosimeter: Active
Sampler: |
9.6 L 3 to 100 L |
|
|
Analytical Procedure: |
The sorbent is digested using nitric
acid and hydrocloric acid. The mercury in the sample is reduced to
elemental mercury using stannous chloride and analyzed using a cold
vapor-atomic absorption spectrophotometer. |
|
|
Detection Limit
Qualitative Passive Dosimeter: Active
Sampler: |
0.002 mg/m3 for a
240-min (4.8 L)sample 0.00067 mg/m3 for
a 75-min (15 L) sample |
|
|
Quantitative
Passive Dosimeter: Active Sampler: |
0.004 mg/m3 for a
240-min (4.8 L) sample 0.0013 mg/m3 for a
75-min (15 L) sample |
|
|
Precision and Accuracy
Passive Dosimeter Validation Range:
CVT(pooled) |
0.061 to 0.20
mg/m3 0.039 |
|
|
Bias |
+0.008 |
|
|
Overall Error |
±8.6% |
|
|
Method Classification: |
Validated Method |
|
|
Date (Date Revised): |
1987 (June, 1991) |
|
|
Please note: For problems
with accessibility in using figures and illustrations in this
method, please contact the author at (801) 233-4900. |
Commercial manufacturers and products mentioned in this method are
for descriptive use only and do not constitute endorsements by
USDOL-OSHA. Similar products from other sources can
be substituted.
|
Division of Physical Measurements and Inorganic
Analyses OSHA Technical Center Sandy, Utah
|
1.
Introduction
This method
describes the collection of airborne elemental mercury in a passive
dosimeter or active sampling device and subsequent analysis using a
cold vapor-atomic absorption spectrophotometer
(CV-AAS).
1.1. Principle
The mercury
dosimeter samples the workplace atmosphere by controlled diffusion
into the badge while the active sampler uses a calibrated sampling
pump. The mercury vapor entering either passive or active device
is collected on a solid sorbent (HydrarR or hopcalite)
which has an irreversible affinity for mercury (8.1., 8.2.). After
sample collection the sorbent is initially dissolved with
concentrated nitric acid and then hydrochloric acid. Stannous
chloride is added to an aliquot of the sample to generate mercury
vapor. This vapor is then driven into an absorption cell of a
flameless atomic absorption spectrophotometer for analysis.
1.2. History
Previously,
mercury samples were collected on iodine-impregnated
charcoal contained in glass tubes. The treated charcoal was
analyzed for mercury by placing it in a tantalum sampling boat and
then heating to drive the mercury vapor into the beam of an atomic
absorption spectrophotometer (8.3.). The amount of mercury was
determined by absorbance at253.7 nm. The detection limit was
approximately 0.1 µg. Drawbacks with this method were:
- The mercury vapor and hence the entire sample was
immediately lost into the surrounding atmosphere
- The method was imprecise at lower sample loadings
(8.4.)
- The analytical technique was somewhat
tedious
Hopcalite solid
sorbent (8.5.) was substituted in place of the iodine-impregnated
charcoal for mercury vapor sampling. Previously, hopcalite had
been used in respirator cartridges for carbon monoxide and
consisted of oxides of copper, manganese, cobalt, and silver
(8.6.). Analysis of recent batches of hopcalite used for mercury
collection indicate the composition was mainly oxides of manganese
and copper.
HydrarR has been used as a
substitute for collecting mercury vapor and is very similar in
composition to hopcalite. A ceramic material, insoluble in nitric
and hydrochloric acid, is present in the HydrarR but
not in the hopcalite.
1.3. Advantages and Disadvantages
1.3.1. These sampling and analytical techniques have
adequate sensitivity for measuring workplace atmospheric
concentrations of elemental mercury.
1.3.2. The passive
dosimeter used for collection of mercury vapor is small,
lightweight, and requires no sampling pumps. Also, the dosimeter
housing is reusable; therefore, cost per measurement is kept to
a minimum.
1.3.3. The collected mercury sample is stable
for at least 30 days.
1.3.4. Sample preparation for
analysis involves simple procedures.
1.3.5. Either
sampling device can be analyzed in any laboratory equipped with
a CV-AAS.
1.3.6. A disadvantage with the
passive dosimeter is particulate compounds cannot be collected
with the device. A separate sampling pump and collection media
should be used for particulate collection.
1.3.7.
Another disadvantage with the dosimeter is sample rate
dependence on face velocity. The dosimeter should not be used in
areas where the air velocity is greater than 229 m/min (750
ft/min) since erratic increases in sampling rate may occur.
1.3.8. A disadvantage with the active device is the
dependence on a calibrated pump to take the sample.
1.4. Toxic Effects (This section
is for information only and should not be taken as a basis for
OSHA policy.)
Exposure to elemental mercury vapor can
occur via the respiratory tract and skin. Possible symptoms from
an acute exposure include severe nausea, vomiting, abdominal pain,
bloody diarrhea, kidney damage, and death. These symptoms usually
present themselves within 10 days of exposure. Potential symptoms
from a chronic exposure include inflammation of the mouth and
gums, excessive salivation, loosening of the teeth, kidney damage,
muscle tremors, jerky gait, spasms of the extremities, personality
changes, depression, irritability, and nervousness (8.7., 8.8.).
1.5. Workplace Exposure
Occupations with potential exposure to mercury and its
compounds are listed (8.8.):
amalgam makers |
fur
processors |
bactericide makers |
gold extractors |
barometer makers |
histology technicians |
battery makers, mercury |
ink makers |
boiler makers |
insecticide makers |
bronzers |
investment casting
workers |
calibration instrument
makers |
jewelers |
cap loaders, percussion |
laboratory workers,
chemical |
carbon brush makers |
lampmakers, fluorescent |
caustic soda makers |
manometer makers |
ceramic workers |
mercury workers |
chlorine makers |
miners, mercury |
dental amalgam makers |
neon light makers |
dentists |
paint makers |
direct current meter workers |
paper makers |
disinfectant makers |
percussion cap makers |
disinfectors |
pesticide workers |
drug makers |
photographers |
dye makers |
pressure gage makers |
electric apparatus makers |
refiners, mercury |
electroplaters |
seed handlers |
embalmers |
silver extractors |
explosive makers |
switch makers, mercury |
farmers |
tannery workers |
fingerprint detectors |
taxidermists |
fireworks makers |
textile printers |
fungicide makers |
thermometer makers |
fur preservers |
wood preservative
workers |
1.6. Properties (8.7., 8.8.)
Elemental mercury (CAS No. 7439-97-6) is a
silver-white, heavy, mobile, liquid metal at room
temperature. Some physical properties and data for mercury
are:
Atomic Number |
80 |
Atomic Symbol |
Hg |
Atomic Weight |
200.61 |
Freezing Point |
-38.87 °C |
Boiling Point |
356.90 °C |
Density |
13.546 g/mL (20 °C) |
Synonyms |
Quicksilver,
Hydrargyrum |
The high vapor pressure of mercury at normal
temperatures combined with the potential toxicity makes good
control measures necessary to avoid exposure. Also, the
concentration of mercury vapor in the air rapidly increases as the
temperature increases. To illustrate, listed below are vapor
pressures of mercury, and mercury concentrations of air after
saturation with mercury vapor at different temperatures:
Vapor Pressure-Saturation Concentration of
Mercury at Various Temperatures
|
|
Temperature |
Vapor Pressure |
Mercury
Concentration |
|
°C |
°F |
(torr) |
(µg/m3) |
|
|
0 |
32.0 |
0.000185 |
2,180 |
|
10 |
50.0 |
0.000490 |
5,880 |
|
20 |
68.0 |
0.001201 |
13,200 |
|
24 |
75.2 |
0.001691 |
18,300 |
|
28 |
82.4 |
0.002359 |
25,200 |
|
30 |
86.0 |
0.002777 |
29,500 |
|
32 |
89.6 |
0.003261 |
34,400 |
|
36 |
96.8 |
0.004471 |
46,600 |
|
40 |
104.0 |
0.006079 |
62,600 |
| 2.
Range
2.1. The qualitative and
quantitative detection limits for the analytical procedure are
0.01 µg and 0.02 µg mercury, respectively (8.9.).
2.2. Working Range
The
range of the analytical procedure has been determined to be 0.1 to
2 µg mercury. Using the analytical conditions specified, a
nonlinear response was noted above 2 µg. 3. Method Performance
3.1. The SKC HydrarR
gas monitoring dosimeter badge for mercury (SKC Inc., Eighty Four,
PA) was evaluated at 80% RH and 25 °C over the range of 0.061 to
0.203 mg/m3 using a dynamic generation system (8.2.).
The pooled coefficient of variation (CVT) for badge
samples taken in this concentration range was 0.039. The average
recovery was 100.8% and the overall error was ±8.6%.
In a
separate study, active samplers were spiked with mercury in the
range of 1 to 2.5 µg. The mean recovery of these 125 quality
control samples was 96.9% with a CV1 of 0.106 (8.10.).
3.2. In storage stability studies,
the mean recoveries of HydrarR samples analyzed 5, 14,
and 30 days after collection were within ±10% of the known
generated concentration (8.2.).
3.3. The HydrarR active
sampling device was compared using linear regression statistics to
the dosimeter in a field study (8.11.). The dosimeter results
agreed well with the active sampler and are summarized below
(Note: A correlation coefficient and slope = 1 would indicate
ideal agreement):
Number of paired samples |
(N) |
= |
26 |
Concentration Range |
|
= |
0.01 to 0.7
mg/m3 |
Correlation coefficient |
(r) |
= |
0.985 |
Intercept |
(a) |
= |
0.017 |
Slope |
(b) |
= |
0.960 |
Standard deviation of the
slope |
(Sb) |
= |
0.038 | 4. Interferences
4.1. Sampling:
Particulate
mercury compounds are a positive interference; however, the badge
does not sample particulates and the glass wool of the active
sampler prevents particulate from entering the sorbent. Chlorine
in the sampled air does not interfere when using
HydrarR or hopcalite sorbent. The chlorine does react
with available mercury vapor in the air to presumably form
mercuric chloride (8.12.). Workplaces containing both chlorine and
mercury should be sampled for both mercury vapor and particulate.
4.2. Analysis:
Organic-free deionized water should be used during sample
and standard preparation. Any compound with the same absorbance
wavelength as mercury (253.7 nm) can be a positive interference.
Some volatile organic compounds (i.e. benzene, toluene, acetone,
carbon tetrachloride) absorb at this wavelength and are considered
analytical interferences. They occur as contaminants in the
reagents used during sample preparation. These compounds are not
expected to be retained on HydrarR or hopcalite during
sample collection. Analytical interferences are rendered
insignificant by using organic-free deionized water
and at least reagent grade chemicals or by blank subtraction.
Increasing the concentration of nitric acid in the samples
or standards appears to produce an elevated background signal. The
nitric acid concentration in the samples and standards should not
be greater than 10%. 5.
Sampling
[Note: A prefilter
assembly, consisting of a mixed-cellulose ester filter
in a polystyrene cassette, can be used with the active samplers.
Although a significant loss of mercury vapor, presumably due to the
prefilter assembly, has been noted when using this type of sampling
train (8.12.), these results were not duplicated in a series of
recent experiments(8.13.).]
5.1. Equipment
Either
tubes or dosimeters can be used to collect mercury vapor. The
dosimeter should not be used when:
- The air velocity of the sampling site is greater than 229
m/min (750 ft/min)
- The operation being sampled is characterized by extremely
poor hygienic practices and splashing of mercury on the badge
may occur
- Determination of compliance to the Transitional Permissible
Exposure Limit (PEL) to total mercury is necessary and mercury
particulate appears to be present in the workplace atmosphere
The tube can be used to determine
compliance with the Transitional PEL of 0.1 mg/m3
(TWA) as total mercury
(vapor + particulate). The badge can only collect mercury
vapor. For Ceiling exposures to particulate mercury, or for wipe
and bulk sampling and analysis consult reference 8.14. for further
information.
5.1.1. PASSIVE DOSIMETER:
Gas monitoring
dosimeter badge and pouch containing a HydrarR
capsule [badge - cat. no. 520-03, pouch - cat. no.
520-02 (SKC Inc., Eighty Four, PA)]. The capsule
contains 800 mg of sorbent.
5.1.2. ACTIVE
SAMPLER:
HydrarR or hopcalite sampling
tubes (cat. no. 226-17-1 or 226-17-lA,
SKC, Inc., Eighty Four, PA). These are 6-mm o.d. ×
70-mm long glass tubes which contain 200 mg of
sorbent.
Note: Before use, the active sampling tubes must be examined for
movement of the the solid sorbent into the glass wool. See
Section 5.3.1. for further details.
5.1.3. Sampling pumps capable of
sampling at 0.2 liters per minute (L/min).
5.1.4. Assorted flexible tubing.
5.1.5. Stopwatch and bubble tube
or meter for pump calibration.
5.2. Sampling Procedure - PASSIVE DOSIMETER
5.2.1. Assemble the components
of the mercury monitoring badge according to manufacturer
instructions (8.1.).
Note: A foam insert must be placed
in the Model 520-03 dosimeter to hold the capsule
in place (8.13.).
5.2.2. Record the sampling start
time, sampling site temperature, and atmospheric pressure.
Remove the protective cap and then place the dosimeter in the
breathing zone of the employee. The suggested sampling time for
the dosimeter is 8 h.
5.2.3. Immediately after
sampling, carefully remove the sorbent capsule from the
dosimeter and place it in the sorbent pouch. Fold the pouch top
twice and press it flat to seal the capsule inside the pouch.
Record the sampling stop time, final temperature, and
atmospheric pressure. Calculate and record the total sampling
time, average temperature, and pressure.
5.3. Sampling Procedure - ACTIVE SAMPLER
5.3.1. Calibrate each personal
sampling pump with an active sampler in-line using
a flow rate of about 0.2 L/min.
Note: A prefilter assembly consisting of a
mixed-cellulose ester filter, polystyrene cassette,
and a minimum
amount of Tygon tubing can be used if:
- particulate mercury compounds may present a problem during
sampling or
- the hopcalite or HydrarR contained in the
active sampling tube has migrated to the glass wool plug.
Before use, the active sampling
tubes must be examined for movement of the solid sorbent into
the glass wool. Certain lots of HydrarR or hopcalite
have been noted as being very friable or having a sorbent
particle-size range small enough as to allow
migration. This movement can easily be noted - the glass wool in
the sampling tube appears somewhat discolored (darkened) from
the small sorbent particles. If sorbent migration has occurred,
a prefilter assembly is recommended. The recommended sampling
flow rate is also 0.2 L/min with the
prefilter-sampling tube-pump assembly.
5.3.2. Connect a sampling tube
(or sampling assembly) to a calibrated pump using flexible
tubing. If a prefilter is used, connect it to the sampling tube
with a minimum amount of Tygon tubing. Connect the other end of
the sampling tube to the pump. Place the sampling tube (or
assembly) in the breathing zone and the pump in an appropriate
position on the employee.
5.3.3. Use an air volume in the
range of 3 to 100 L to collect the mercury in the workplace air.
Record the total volume.
5.3.4. Replace the plastic end
caps on the active sampler after sampling is completed.
5.4. Sample Shipment
5.4.1. Securely wrap each
sorbent pouch or active sampling tube end-to-end
with an OSHA Form 21 sample seal. Also seal and prepare
cassettes if a prefilter assembly was used.
5.4.2. Submit at least one blank
sample with each set of samples. The blank sample should be
handled in the same manner as the other samples except that an
air sample is not taken.
5.4.3. Request the laboratory to
analyze the samples for mercury. Submit any pertinent sampling
information to the lab. Record if a prefilter
assembly was used.
5.4.4. Ship the sealed pouches
and used dosimeter housings, or active sampling tubes to the
laboratory in appropriate containers as soon as possible. The
filter/cassette assembly can also be submitted for mercury
particulate analysis; however, sampling periods may be longer
than reflected in exposure regulations. The PEL for mercury
particulate is a Ceiling(8.14.) and the vapor is a TWA PEL.
6.
Analysis
6.1. Safety Precautions
6.1.1. Wear safety glasses, lab
coat, and gloves at all times.
6.1.2. Handle acid solutions
with care. Avoid direct contact of acids with work area
surfaces, eyes, skin, and clothes. Flush acid solutions which
contact the skin or eyes with copious amounts of cold water.
6.1.3. Prepare solutions
containing hydrochloric acid in an exhaust hood and store in
narrow-mouthed bottles.
6.1.4. Keep B.O.D. bottles
containing stannous chloride/hydrochloric acid solutions capped
when not in use to prevent inhalation of noxious vapors.
6.1.5. Exercise care when using
laboratory glassware. Do not use chipped pipets, volumetric
flasks, beakers or any glassware with sharp edges exposed.
6.1.6. Never pipet by mouth.
6.1.7. When scoring the glass of
active samplers to remove the sorbent before analysis, score
with care. Apply only enough pressure to scratch a clean mark on
the glass. Use a paper towel or cloth to support the opposite
side while scoring. Moisten the mark with DI H2O and
wrap the tube in cloth before breaking. If the tube does not
break easily, re-score. Dispose of glass in a waste
receptacle specifically designed and designated for
broken-glass.
6.1.8. Always purge the mercury
from the CV-AAS into an exhaust vent.
6.1.9. Occasionally monitor the
CV-AAS for mercury vapor leaks using an appropriate
direct reading instrument.
6.2. Equipment - Cold Vapor
Analysis
(Note: Specific equipment is listed for
illustration only)
6.2.1. Atomic absorption
spectrophotometer (model 503, Perkin-Elmer,
Norwalk, CT).
6.2.2. Mercury hollow cathode
lamp or electrodeless discharge lamp and power supply.
6.2.3. Biological Oxygen Demand
(B.O.D.) bottles, borosilicate glass, 300 mL.
6.2.4. Peristaltic pump, 1.6 to
200 mL range, and controller, 1-100 rpm range
(Masterflex model 7553-30 with model 7015 head,
Cole-Parmer, Chicago, IL).
6.2.5. Quartz absorption cell,
22-mm (7/8 in) o.d. × 152-mm (6 in)
long (part no. 303-3101,
Perkin-Elmer).
6.2.6. Heating tape.
6.2.7. Variable transformer
50-60 Hz, 10 A, 120 V input, 0-140 V
output, 1.4 kW (Superior Electric, Bristol, CT).
6.2.8. Tygon peristaltic pump
tubing (part no. N06409-15, Cole-Parmer) and glass
tubing.
6.2.9. Aerator (part no.
0303-3102, Perkin-Elmer).
6.2.10. Chart recorder.
6.2.11. Desiccant (Drierite,
W.A. Hammond Drierite Co., Xenia, OH).
6.2.12. Volumetric flasks,
volumetric pipets, beakers, and other laboratory glassware.
6.2.13. Automatic pipets,
adjustable, 0.1 to 5.0 mL range (models P-1000 and
P-5000, Rainin Instruments Co., Woburn, MA).
6.2.14. Glass tube scorer, or
needle, 21 to 25 gauge - for removing metal screens in
dosimeters or glass wool from tubes. A piece of bent wire can
also be used.
6.2.15. Exhaust vent.
6.3. Reagents - All reagents
should be at least reagent grade.
Stannous chloride,
(SnCl2)
6.3.1. Deionized water (DI
H2O), organic-free.
6.3.2. Hydrochloric acid (HCl),
concentrated (36.5 to 38%), with a mercury concentration less
than 0.005 ppm.
6.3.3. Mercury standard stock
solution, 1,000 µg/mL: Use a commercially available certified
standard or, alternatively, dissolve 1.0798 g of dry mercuric
oxide (HgO) in 50 mL of 1:1 hydrochloric acid and then dilute to
1 L with DI H2O. Store this reagent in a dark
environment, preferably in an amber colored container.
6.3.4. Nitric acid
(HNO3), concentrated (69 to 71%), with a mercury
concentration less than 0.005 ppm.
6.3.5. Nitric acid, 1:1:
Carefully add equal portions of concentrated HNO3 and
DI H2O.
6.3.6. Nitric acid, 10%:
Carefully add 100 mL concentrated HNO3 to 900 mL DI
H2O.
6.3.7. Stannous chloride
(SnCl2) solution, 10%: Dissolve 20 g SnCl2
in 100 mL concentrated HCl. Slowly and carefully pour this
solution into 100 mL DI H2O and then mix well.
Transfer and store the final solution in a capped B.O.D. bottle
to prevent oxidation. Prepare this solution before each new
analysis.
6.4. Glassware Preparation
6.4.1. Clean the B.O.D. bottles
and stoppers with 1:1 HNO3 and thoroughly rinse with
DI H2O prior to use.
6.4.2. Rinse all other glassware
with 10% nitric acid and then with DI H2O prior to
use. Air dry all 50-mL volumetric flasks to be used
in sample preparation.
6.5. Standard Preparation
6.5.1. Prepare a 1 µg/mL mercury
standard by making appropriate ten-fold serial
dilutions of the 1,000 µg/mL mercury standard stock solution
with 10% HNO3.
6.5.2. Prepare working mercury
standards (ranging from 0.1 to 2.0 µg) and reagent blanks immediately prior to use. A few standards at
each concentration should be made. Add an appropriate aliquot of
the 1 µg/mL standard to a clean B.O.D. bottle containing enough
10% HNO3 to bring the total volume to 100 mL. A
suggested dilution scheme is given:
|
Mercury Standard (µg) |
Aliquot (mL)* |
Final Volume (mL) |
|
Reagent Blank |
0 |
100 |
0.1 |
0.1 |
100 |
0.2 |
0.2 |
100 |
0.5 |
0.5 |
100 |
1.0 |
1.0 |
100 |
1.5 |
1.5 |
100 |
2.0 |
2.0 |
100 |
* Aliquot taken
from 1 µg/mL standard prepared in Section 6.5.1. |
|
6.6. Sample Preparation [Note: A
hooked needle or piece of fine wire is useful to remove the
dosimeter screen or glass wool (active sampler) and the sorbent
particles.]
6.6.1. DOSIMETER
Open each sample pouch and
remove the sorbent capsule. Carefully remove the screen from the
top of the capsule without losing any sorbent. Carefully pour
the sorbent into a clean, dry 50-mL flask without
spilling any. Discard the screen and empty capsule.
6.6.2. ACTIVE
SAMPLER
Score the tube with a glass tube cutter
(also see Section 6.1.7.) and then break open the front section
of the tube above the glass wool. An alternative approach to
scoring and breaking is to carefully remove the glass wool with
a bent wire or needle.
- If a prefilter was not used
during sampling, place the glass wool and sorbent into
separate 50-mL volumetric flasks.
- If a prefilter was used and the
glass wool appears to contain hopcalite or Hydrar, the glass
wool can be analyzed along with the sorbent. Carefully
transfer the glass wool and sorbent to a 50-mL
volumetric flask without losing any of the particles.
6.6.3. Prefilter
Prepare and analyze any
prefilters according to reference 8.14.
6.6.4. Add 2.5 mL of
concentrated HNO3 followed by 2.5 mL concentrated HCl
to each volumetric flask [Note: To minimize any loss of mercury
through a change in oxidation state, the HNO3 is
added before the HCl (8.5.)].
6.6.5. Gently swirl the sample
occasionally for approximately 1 h. If HydrarR was
used to collect the sample, the dark brown solution will also
contain some undissolved clear to white-tan colored
ceramic material.
6.6.6. Carefully dilute to a
50-mL total volume with DI H2O. The
final sorbent sample solution will be
light blue or blue-green. This is a good place to
stop if the analysis cannot be completed the same day.
6.7. Analysis - Instrument
Parameters
6.7.1. Set up the
CV-AAS as illustrated in Figure 1.
6.7.2. Wrap the heating tape
around the quartz cell and then turn on the variable
transformer. The heat setting on the tape should be sufficient
to prevent water vapor condensation in the absorption cell.
6.7.3. Place the aerator in a
B.O.D. bottle which contains approximately ½ to 1 inch of
desiccant. Operate the peristaltic pump for approximately 30 min
at full speed to remove any water vapor from the system.
6.7.4. Operate the hollow
cathode or electrodeless discharge mercury lamp at the
manufacturer's recommended current or power rating.
6.7.5. Use the following
settings (Note: The mentioned instrument settings are for
specific models used at the OSHA-SLCAL. If
instrumentation other than what is specified in Section 6.2. is
used, please consult the instrument manufacturer's
recommendations.):
Atomic Absorption
Spectrophotoineter:
Slit |
0.7 nm |
Signal |
Repeat Mode |
Function |
ABS |
Mode |
ABS |
Range |
UV |
Wavelength |
253.7 nm |
Filter |
Out |
EM Chopper |
Off |
Phase |
Normal | Strip Chart
Recorder:
Chart Speed |
5 mm/min |
Chart Range |
10
mV |
6.7.6. Optimize the ENERGY meter
reading at 253.7 nm.
6.7.7. Align the beam of the
mercury lamp so it passes directly through the center of the
quartz cell windows. This can be accomplished by adjusting the
burner height, depth, and angle knobs to give a minimum
ABSORBANCE reading.
6.7.8. Operate the peristaltic
pump at full speed. Rinse the aerator with DI H2O and
insert it into a holder in the exhaust vent.
6.7.9. Perform the following
steps to obtain a baseline signal near an absorbance of
zero:
- start the chart recorder,
- set the spectrophotometer absorbance reading to zero,
- wait until the baseline stops drifting,
- set the reading to zero again.
6.8. Analysis
6.8.1. Samples: Immediately before analyzing, transfer an
appropriate aliquot of the sample solution to a clean B.O.D.
bottle containing enough 10% HNO3 solution to bring
the total volume to 100 mL. The transfer must be done with a
volumetric pipet.
6.8.2. Standards: Immediately before analyzing, prepare
standards according to instructions listed in Section 6.5.2.
6.8.3. Deliver 5 mL of the 10%
SnCl2 solution with an automatic pipet to a B.O.D.
bottle containing a standard, reagent blank, or sample to be
analyzed. Immediately place the aerator into the solution with
the peristaltic pump operating at full speed.
6.3.4. Record the maximum
absorbance reading and label the signal produced on the strip
chart.
6.8.5. Stop the pump, remove the
B.O.D. bottle from the CV-AAS and stopper it. Rinse
the aerator with DI H2O and insert it into a holder
in the exhaust vent. Turn the pump on at full speed until the
CV-AAS system is purged of mercury and the baseline
returns to zero.
6.8.6. If the absorbance reading
of a sample is greater than the highest standard at any time during analysis, immediately remove the B.O.D. bottle from
the CV-AAS. Purge the system following the
procedure listed in Section 6.8.5. Take a smaller aliquot or
dilute the high concentration sample and
re-analyze. Make any necessary sample dilutions
with 10% HNO3 and use the appropriate dilution factor
when calculating results.
6.8.7. Repeat Sections 6.8.3.
through 6.8.5. for each prepared standard, reagent blank, or
sample.
6.9. Analytical Recommendations
6.9.1. It is recommended to
analyze the reagent blank, lowest, and highest standard two or
three times each to check for contamination, reproducibility,
and sensitivity before starting the sample analysis. A 2.0-µg
mercury standard should give a three-quarter to
full-scale deflection on the chart recorder and an
absorbance unitreading of about 0.850 when using the equipment
and conditions specified. The lowest and highest standard should
provide a linear response and the lowest standard should be at
least two to three times the blank signal.
6.9.2. It is also recommended to
analyze an entire series of standards (including the reagent
blank) at the beginning and end of the sample analysis to ensure
standard readings are reproducible. As a general guideline,
standard readings should be within ±10% throughout the analysis.
6.9.3. A standard near the
concentration range of the samples should be analyzed after
every four to five samples.
6.9.4. Quality control (QC)
samples should be prepared and analyzed using the same matrix
and analytical conditions as the samples. If possible, the QC
samples should be generated from an independent source.
6.9.5. Approximately 10% of the
samples should be reanalyzed. 7. Calculations
7.1. Use a least squares
regression program to plot a concentration-response
curve of peak absorbance versus the amount (µg) of mercury in each
standard.
7.2. Determine the amount (µg) of
mercury, A, corresponding to the peak absorbance in each analyzed
sample aliquot from this curve.
7.3. Calculate the total amount
(µg) of mercury, W, in each sorbent or glass wool sample:
W = |
(A) (sample
volume, mL) (DF)
(aliquot, mL) | Where:
DF = Dilution Factor (if none, DF = 1)
7.4. A blank correction is made
for each sample (Note: When using the reagents and conditions
specified, previous blank results have been less than 1 µg).
Calculate the concentration of mercury in each sorbent or glass
wool sample:
mercury mg/m =
|
W - Wb
air volume, L |
Where:
Wb |
= |
Total µg of mercury in the
blank sample. |
Air vol |
= |
Sampling time × flow rate (for
ACTIVE SAMPLERS) |
(Note: |
For PASSIVE DOSIMETERS, the
sampling rate is affected by temperature and pressure. To
correct for this, use: |
Air vol = ST × 0.020 × (T1/T2)
1.5 ×
(P2/P1)
Where:
ST |
= |
Sampling time (min) |
0.020 |
= |
Sampling rate (L/min) at 20 °C
and 760 torr |
T1 |
= |
Sampling site temperature
(K) |
T2 |
= |
293 K |
P1 |
= |
Sampling site pressure
(torr) |
P2 |
= |
760
torr |
7.5. Reporting Results to the
Industrial Hygienist
For PASSIVE DOSIMETER samples, report
results to the industrial hygienist as mg/m3 mercury
vapor.
For ACTIVE SAMPLERS, report results as:
- mg/m3 mercury vapor
- mg/m3 total mercury
For mercury vapor result a): If a
prefilter was used and the glass wool and sorbent were
combined:
mercury vapor =
glass wool + sorbent | The prefilter (if used) was present during sampling
to assure that mercury particulate was not trapped in the glass
wool.
For total mercury result (b): The sum of the mercury
found in the sorbent (vapor), glass wool, and prefilter (if used)
for each active sampler is considered. This result is used to
determine compliance to the Transitional PEL for total mercury.
The Transitional PEL considers both the vapor and particulate
fractions of mercury.
Any mercury particulate found on the
prefilter can be assessed for compliance with the Ceiling PEL for
mercury. See reference 8.14. for further details.
If
sampling information has not been provided by field personnel,
results are reported in total micrograms. 8. References
8.1. SKC
Inc.: Gas Monitoring Dosimeter Badge for
Mercury (Operating Instructions). Eighty Four, PA: SKC
Inc., no publication date given.
8.2. Occupational Safety and Health Administration Technical
Center: Evaluation of Mercury Solid
Sorbent Passive Dosimeter by J. Ku (OSHA-SLTC Backup Report
for Method No. ID-140). Salt Lake City, UT, Revised
1989.
8.3. Moffitt, A.E., Jr. and R.E.
Kupel: A Rapid Method Employing Impregnated Charcoal and
Atomic Absorption Spectroscopy for the Determination of Mercury.
Am. Ind. Hyg. Assoc. J. 32: 614 (1971).
8.4. McCammon, C.S., Jr., S.L. Edwards,
R.D. Hull, and W.J. Woodfin: A Comparison of Four Personal
Sampling Methods for the Determination of Mercury Vapor. Am. Ind. Hyg. Assoc. J. 41:
528-531 (1980).
8.5. Rathje,
A.O. and D.H. Marcero: Improved Hopcalite Procedure for the
Determination of Mercury Vapor in Air by Flameless Atomic
Absorption. Am. Ind. Hyg. Assoc. J. 37:
331 (1976).
8.6. Sax, N.I. and R.J. Lewis
Sr., ed.: Hawley's Condensed Chemical
Dictionary. 11th ed. New York: Van Nostrand Reirihold Co.,
1987.
8.7. Windholz, M., ed.:
The Merck Index. 10th ed. Rahway, NJ:
Merck & Co. Inc., 1983.
8.8. National
Institute for Occupational Safety and Health: Criteria for a Recommended Standard -- Occupational
Exposure to Inorganic Mercury (DHEW/NIOSH Pub. No.
HSM-73-11024). Cincinnati, OH: National Institute for
Occupational Safety and Health, 1973.
8.9. Occupational Safety and Health Administration
Analytical Laboratory: Detection Limit
Study for Mercury Cold Vapor Analysis by C. Merrell. Salt
Lake City, UT. 1987 (unpublished).
8.10. Occupational Safety and Health Administration
Analytical Laboratory: Quality Control
Data - Mercury Cold Vapor Analysis by B. Babcock. Salt Lake
City, UT. 1987 (unpublished).
8.11. Occupational Safety and Health Administration
Analytical Laboratory: An Evaluation of
Mercury Vapor Sampling Devices by R. Cee, J. Ku, E.
Zimowski, S. Edwards, and J. Septon (OSHA-SLCAL Product Evaluation
No. PE-6). Salt Lake City, UT. 1987
8.12.
Menke, R. and G. Wallis: Detection of
Mercury in Air in the Presence of Chlorine and Water Vapor. Am. Ind. Hyg. Assoc. J. 41:
120-124 (1980).
8.13. Occupational Safety and Health Administration Technical
Center: An Evaluation of Hopcalite
Sampling Methods for Mercury by J. Septon. Salt Lake City,
UT. In progress (unpublished).
8.14. Occupational Safety and Health Administrations
Technical Center: Mercury Particualte in
Workplace Atmospheres (OSHA-SLTC Method No.
ID-145). Salt Lake City, UT. 1989
Cold
Vapor-Atomic Absorption Spectrophotometer for
Mercury Analysis
Figure
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