D 5954 PDF
D 5954 PDF
D 5954 PDF
Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D5954 98 (2006)
NOTE 2All glass and plastic ware coming into contact with the sample where such specifications are available.6 Other grades may be
must be acid washed with 20 % nitric acid and thoroughly rinsed with used, provided it is first ascertained that the reagent is of
water.
sufficiently high purity to permit its use without lessening the
5.7 Quartz Tubing, approximately 24 in. long and 1-in. accuracy of the determination.
outside diameter, to be used for the preparation of the gold- 6.2 Reagent WaterReagent water, conforming to Type II
coated silica. of Specification D1193, shall be used for preparation of
5.8 Quartz Wool to be used for sorbent (gold-coated silica) reagents and washing of the quartz tubing.
packing. 6.3 Gold ChlorideDissolve 2 g of gold chloride
5.9 Fused Silica or Quartz Beads, 60/80 mesh, to be used (HAuCl43H2O) in approximately 10 mL of water (Warning
for the preparation of the gold-coated silica. Poison).
5.10 Tube Furnace, approximately 8 to 10 cm in length, to 6.4 Sulfuric Acid, (concentrated, H2SO4, relative density
be used for the preparation of the gold-coated silica and the 1.84) (WarningPoison).
mercury desorption. It must be capable of maintaining tem- 6.5 Nitric Acid, (concentrated, HNO3, relative density 1.42)
peratures up to 750 6 25C over a 4-cm length. A Variac or (WarningPoison).
other temperature control device may be required.
6.6 Nitric Acid, (20 %)Mix 1 volume of concentrated
NOTE 3A shorter sampling tube and a shorter tube furnace may be nitric acid with 4 volumes of water.
used as long as the specified temperature can be maintained.
6.7 Mercury, triple distilled (WarningPoison).
5.11 Silicone Tubing, 14-in. inside diameter for connections.
6.8 Mercury Standard Stock Solution, (1000 g/mL)
5.12 Stainless Steel Tubing, 14- and 18-in outside diameter, Dissolve 1.080 g of mercury (II) oxide (HgO) in a minimal
various lengths, for connections. amount of HCl (1 + 1). Dilute to 1 L with water.
5.13 Gastight Tube Fittings, 14-in. nylon or TFE- 6.9 Mercury Standard Intermediate Solution, (10 g/mL)
fluorocarbon construction, gastight end-cap type, plus one Add 10.00 mL of the mercury standard stock solution to
stainless steel T fitting. approximately 500 mL of water. Add 0.5 mL of concentrated
nitric acid and dilute to 1 L with water. Prepare this standard
5.14 Precision Gastight Syringe, 500 L, equipped with a
solution daily.
needle with a side port opening.
6.10 Mercury Standard Working Solution, (100 ng/mL)
NOTE 4A digital syringe is recommended for better accuracy and Add 1.00 mL of the mercury standard intermediate solution to
precision in calibration.
approximately 50 mL of water. Add 0.05 mL of concentrated
5.15 Septum Material, GC grade, low bleed type, made nitric acid and dilute to 100 mL with water. If micropipets are
from silicone. not available, this standard may be prepared by serial dilution
5.16 Water Bath or Constant Temperature Apparatus, ca- of the mercury standard intermediate solution. Prepare this
pable of regulating a sealed vial of mercury to 26 6 0.05C. standard solution daily.
6.11 Air, PP grade, or carbon filtered.
5.17 Sealed Vial of Mercury, prepared from a 250-mL glass
bottle with a TFE-fluorocarbon septum cap and triple distilled 6.12 Hydrogen, PP grade (WarningFlammable).
elemental mercury. 6.13 Nitrogen, PP grade.
5.18 Thermocouple, for monitoring tube furnace tempera- 6.14 Sulfur Impregnated Carbon, used to filter carrier gases.
tures.
7. Procedure for the Preparation of the Gold-Coated
5.19 Heating Tape, capable of maintaining a temperature of Beads
50 to 60C, to heat trace tubing from the outlet end of the
sampling tube to the inlet port of the AAS cell. A Variac or 7.1 Soak the silica beads in concentrated sulfuric acid
other temperature control device may be required. overnight to remove any coating or contamination. Silica beads
used for GC operations are often deactivated by silanization
5.20 Stainless Steel 6-Port Switching Valve, 18 in. for carrier and this coating must be removed. Wash thoroughly with
gas control (optional). reagent water and dry.
6. Reagents 6
Reagent Chemicals, American Chemical Society Specifications , American
6.1 Purity of ReagentsReagent grade chemicals shall be Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
used in all tests. Unless otherwise indicated, it is intended that
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
all reagents shall conform to the specifications of the Commit- and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
tee on Analytical Reagents of the American Chemical Society, MD.
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D5954 98 (2006)
7.2 Add 50 g of acid washed silica beads to 10 mL of gold natural gas sample should flow from the sampling point (with
chloride solution. This will result in a 2 % loading of gold on a pressure regulator) into the first sampling tube (Tube 1),
the silica substrate. Add a minimal amount of water, if followed by the second tube (Tube 2), and finally the rotameter
necessary, to form a slurry. Heat on a hot plate with stirring flow control device.
until most of the water evaporates. Let the beads air-dry until
9.2 The distance from the sampling point to the sampler
the apparent moisture is evaporated. The color may change
should be minimized because mercury is easily absorbed on
from yellow to a yellowish orange.
tubing lines and sampling equipment. The entire sampling
7.3 Pack the coated beads into the 1-in. outside diameter system must be passivated with the sample gas before any
quartz tube with quartz wool plugs at either end and begin sampling, especially if low levels of mercury are expected.
heating using a tube furnace with a nitrogen purge. Slowly Stainless steel tubing must be used for connections upstream of
raise the temperature from ambient to 170C to dry thoroughly. the pressure regulator. High density TFE-fluorocarbon or
A heat gun may be used to remove condensed moisture stainless steel tubing is preferred for connections downstream
downstream of the furnace. The color of the beads will begin of the regulator. Flexible silicone tubing may be used to make
to turn orange and then purplish. This may take 1 to 2 h to short connections to sampling tubes. Any pumps, metering
complete depending on how much moisture is present. valves, and so forth or other flow- and pressure-controlling
NOTE 5Caution: Moisture and oxygen must be removed and the devices should be located downstream of the sampler if
beads completely dry before hydrogen gas is introduced. possible. The entire sampling line should be heated to prevent
7.4 Switch the gas to hydrogen and slowly raise the tem- condensation, especially when a pressure reduction device is
perature to 250C to reduce the gold ion to metallic gold. As used to step down the pressure for sampling.
the temperature rises, HCl vapors are generated from the tube 9.3 Ascertain that the sample can be obtained at a pressure
and may appear as a smoky haze. A yellowish haze may be not exceeding 15 psig (10 psig is preferable) and a flow of 1 to
seen on the inside walls of the quartz tube. The reaction is 2.5 L/min (2 L/min is preferable). Pressure- and flow-control
complete when this haze either disappears or does not change devices may be required. A total flow volume measurement
over a 15- to 20-min period. Do not allow the temperature of device, such as a dry test meter, can be used to record the exact
the furnace to rise above 250C since gold chloride will amounts of gas sampled for more accurate sampling.
sublimate at 265C. This procedure may take 2 to 3 h to
complete. 9.4 Using a calibrated rotameter, installed upstream of the
total flow measurement device, determine an approximate flow
NOTE 6Caution: The gas stream exiting from the tube furnace should
be directed into a flask containing water to absorb the HCl gas generated control setting for the selected flow at the applied pressure.
as the gold ion is reduced. This will save time when setting up the sampling tubes and will
condition the sampling system.
7.5 Raise the furnace temperature to approximately 400C
over a 10-min period. Switch the gas to nitrogen and continue 9.5 Remove the fitting on one end of each tube and join the
heating up to 500 to 550C for an additional 10 min. Remove two tubes end-to-end with a short piece of silicone tubing.
the quartz tube from the furnace and allow to cool under the
nitrogen purge. 9.6 Connect the back end of the sampling tube assembly
(Tube 2) to the rotameter and connect the front end of the
8. Procedure for the Preparation of the Sampling Tubes sampling tube assembly (Tube 1) to the sampling point.
8.1 Wash each 14-in. outside diameter quartz tube with 20 % Carefully open the sampling valve and quickly adjust the flow
HNO3, rinse with water, and dry in an oven at 105C. control (and pressure if necessary) to obtain the required
flowrate. Record the time and flow data at the start of sampling.
8.2 Place a 1-cm length of quartz wool at one end of a tube. Mark the direction the sample gas flowed through the tube.
8.3 Add 0.5 g of the gold-coated beads to a quartz tube
9.7 Flow the sample through the sampling tube for the
(oriented vertically) and gently tap the contents to eliminate air
desired amount of time, periodically checking that the flow is
spaces. The final length of gold-coated beads should be
staying close to what it originally was and adjusting it if
approximately 2.5 cm and centered within the tube.
necessary. Typical volumes of gas range from 50 to 100 L. A
8.4 Add a final 1-cm length of quartz wool to the opposite smaller volume of gas should be used for a sample containing
end of the tube. a high concentration of mercury. The optimal range that should
8.5 Bake out each tube using an air purge at 800C at be collected is between 2 and 300 ng of mercury. The capacity
approximately 500 mL/min for at least 15 min. The air should of the sorbent is much higher, approximately 7 g, but a
be filtered through HGR carbon and a clean tube packed with loading at this level should be avoided as the collection
gold-coated beads to remove any traces of mercury that may be efficiency is lessened and the linearity of the atomic absorption
present. spectrophotometer exceeded.
8.6 Seal the end of each tube with a gastight fitting. 9.8 At the end of the sampling period, record the final time
and flow data, disconnect both tubes, and replace all of the
9. Sampling Procedure endcaps tightly on the tubes. Securely attach a label to each of
9.1 Two sampling tubes will be used, with the second tube the tubes, labeling the front tube as Tube 1 and the back tube
providing a check for breakthrough from the first tube. The (connected to the rotameter) as Tube 2.
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D5954 98 (2006)
10. Calibration Procedure recorded and monitored. A 100-L aliquot of the headspace
10.1 Test Method ACalibration Using an Aqueous Stan- over mercury in a sealed vial is equivalent to 2.15-ng mercury
dard: at 26C. The temperature must be closely regulated because the
vapor pressure of mercury is very dependent on temperature. A
10.1.1 Standards are prepared using concentrations appro-
change of 2C results in a 15 % difference in the amount of
priate to the level of mercury collected on the sampling tube.
mercury in the vapor sampled. Sufficient time must be allowed
Different mercury loading will require different volumes or
between headspace withdrawals to allow the mercury vapor
different concentrations, or both, of the mercury working
phase to equilibrate.
standard. To prepare a 20-ng standard, slowly add a 200-L
10.2.7 The following table gives the amount of mercury in
aliquot of the aqueous working mercury standard to a gold-
100-L aliquots of the headspace over mercury in a sealed vial
coated silica tube. After 15 min, or a contact time long enough
at different temperatures.
to ensure adsorption of the mercury onto the gold, wash the
tube interior with four 0.5-mL aliquots of water. Temperature, C Nanogram Mercury in 100 L
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D5954 98 (2006)
full integration. A spare standard tube should be used for this breakthrough occurred. The final concentration is determined
purpose. A typical peak will span 30 s. by addition of the two results.
NOTE 9Optional: A 6-port switching valve can be used to preheat the A1B
tube with no flow for approximately 15 s. Preheating with a stopped flow Mercury, mg/m 3 5 (1)
C
will allow mercury detection with sharper and earlier peaks. Integration
timing will need to be adjusted. A spare standard tube can be used to check where:
peak timing. An ideal run time is 60 s with a typical peak width of 20 to A = ng mercury present in Tube 1,
30 s. B = ng mercury present in Tube 2, and
11.7 Remove the tube from the furnace after the mercury C = volume of sample gas, L (at STP).
peak has evolved (if any) and allow the furnace temperature to
reequilibrate. Remove the used tube from the air line and 13. Precision and Bias
repeat 11.4 on subsequent tubes containing standards and 13.1 The precision of this test method is not known to have
samples. been obtained in accordance with currently accepted guide-
12. Calculation lines. Data are still being collected to obtain reliable repeat-
ability and reproducibility information. The relative percent
12.1 Construct a calibration curve for the range of mercury standard deviation of the standard should not exceed 5 %.
selected by plotting peak areas in absorbance-seconds against
ng mercury. The calibration curve should be prepared with 13.2 Since no suitable certified reference material for mer-
standards spanning the range of expected mercury concentra- cury in natural gas is currently available, no statement on
tion in the gas samples. Depending on the path length of the absolute bias can be made for this test method.
atomic absorption spectrometer quartz analysis cell, and the 13.3 Multiple standards should always be prepared to im-
parameters of the specific instrument used, linearity up to prove the repeatability, and the peak areas compared to
300-ng mercury may be achieved. previous analyses.
12.2 Determine the ng of mercury present in the sample
tubes by reference to the calibration curve. The results from 14. Keywords
Tube 1 and Tube 2 are calculated separately to determine if 14.1 gaseous fuels; mercury sampling; natural gas
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