METHOD #: 245.

5 (Issued 1974)

TITLE: Mercury In Sediment (Manual Cold Vapor

Technique)

ANALYTE: CAS # Hg Mercury 7439-97-6

INSTRUMENTATION: AA

1.0 Scope and Application

1.1 This procedure(1) measures total mercury (organic ✣ inorganic) in soils,

sediments, bottom deposits and sludge type materials.
1.2 The range of the method is 0.2 to 5 Fg/g. The range may be extended above or
below the normal range by increasing or decreasing sample size or through
instrument and recorder control.

2.0 Summary of Method

2.1 A weighed portion of the sample is digested in aqua regia for 2 minutes at
95°C, followed by oxidation with potassium permanganate. Mercury in the
digested sample is then measured by the conventional cold vapor technique.
2.2 An alternate digestion(2) involving the use of an autoclave is described in (8.2).

3.0 Sample Handling and Preservation

3.1 Because of the extreme sensitivity of the analytical procedure and the
omnipresence of mercury, care must be taken to avoid extraneous
contamination. Sampling devices and sample containers should be ascertained
to be free of mercury; the sample should not be exposed to any condition in
the laboratory that may result in contact or air-borne mercury contamination.
3.2 While the sample may be analyzed without drying, it has been found to be
more convenient to analyze a dry sample. Moisture may be driven off in a
drying oven at a temperature of 60°C. No mercury losses have been observed
by using this drying step. The dry sample should be pulverized and
thoroughly mixed before the aliquot is weighed.

4.0 Interferences

4.1 The same types of interferences that may occur in water samples are also
possible with sediments, i.e., sulfides, high copper, high chlorides, etc.
4.2 Volatile materials which absorb at 253.7 nm will cause a positive interference.
In order to remove any interfering volatile materials, the dead air space in the
BOD bottle should be purged before the addition of stannous sulfate.

5.0 Apparatus
5.1 Atomic Absorption Spectrophotometer (See Note 1): Any atomic absorption
unit having an open sample presentation area in which to mount the
 absorption cell is suitable. Instrument settings recommended by the particular
manufacturer should be followed.
NOTE 1: Instruments designed specifically for the measurement of mercury
using the cold vapor technique are commercially available and may be
substituted for the atomic absorption spectrophotometer.
5.2 Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or
equivalent.
5.3 Recorder: Any multi-range variable speed recorder that is compatible with the
UV detection system is suitable.
5.4 Absorption Cell: Standard spectrophotometer cells 10 cm long, having quartz
end windows may be used. Suitable cells may be constructed from plexiglass
tubing, 1 " O.D. X 4-1/2". The ends are ground perpendicular to the
longitudinal axis and quartz windows (1" diameter X 1/16" thickness) are
cemented in place. Gas inlet and outlet ports (also of plexiglass but 1/4" O.D.)
are attached approximately 1/2" from each end. The cell is strapped to a
burner for support and aligned in the light beam to give the maximum
transmittance.
NOTE 2: Two 2" X 2" cards with one inch diameter holes may be placed over
each end of the cell to assist in positioning the cell for maximum transmittance.
5.5 Air Pump: Any peristaltic pump capable of delivering 1 liter of air per minute
may be used. A Masterflex pump with electronic speed control has been found
to be satisfactory. (Regulated compressed air can be used in an open one-pass
system.)
5.6 Flowmeter: Capable of measuring an air flow of 1 liter per minute.
5.7 Aeration Tubing: Tygon tubing is used for passage of the mercury vapor from
the sample bottle to the absorption cell and return. Straight glass tubing
terminating in a coarse porous frit is used for sparging air into the sample.
5.8 Drying Tube: 6" X 3/4" diameter tube containing 20 g of magnesium
perchlorate (See Note 3). The apparatus is assembled as shown in the
accompanying diagram.
NOTE 3: In place of the magnesium perchlorate drying tube, a small reading
lamp with 60W bulb may be used to prevent condensation of moisture inside
the cell. The lamp is positioned to shine on the absorption cell maintaining the
air temperature in the cell about 10°C above ambient.

6.0 Reagents

6.1 Aqua Regia: Prepare immediately before use by carefully adding three
volumes of conc. HCl to one volume of conc. HNO3.
6.2 Sulfuric Acid, 0.5 N: Dilute 14.0 mL of conc. sulfuric acid to 1 liter.
6.3 Stannous Sulfate: Add 25 g stannous sulfate to 250 mL of 0.5 N sulfuric acid
(6.2). This mixture is a suspension and should be stirred continuously during
use.
6.4 Sodium Chloride-Hydroxylamine Sulfate Solution: Dissolve 12 g of sodium
chloride and 12 g of hydroxylamine sulfate in distilled water and dilute to 100
mL.
NOTE 4: A 10% solution of stannous chloride may be substituted for (6.3) and
hydroxylamine hydrochloride may be used in place of hydroxylamine sulfate
in (6.4).
 6.5 Potassium Permanganate: 5% solution, w/v. Dissolve 5 g of potassium
permanganate in 100 mL of distilled water.
6.6 Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 mL of
distilled water. Add 10 mL of conc. nitric acid and adjust the volume to 100.0
mL. 1.0 mL = 1.0 mg Hg.
6.7 Working Mercury Solution: Make successive dilutions of the stock mercury
solution (6.6) to obtain a working standard containing 0.1 Fg/mL. This
working standard and the dilution of the stock mercury solutions should be
prepared fresh daily. Acidity of the working standard should be maintained at
0.15% nitric acid. This acid should be added to the flask as needed before the
addition of the aliquot.

7.0 Calibration

7.1 Transfer 0, 0..5, 1.0, 2.0, 5.0 and 10 mL aliquots of the working mercury
solution (6.7) containing 0 to 1.0 ug of mercury to a series of 300 mL BOD
bottles. Add enough distilled water to each bottle to make a total volume of 10
mL. Add 5 mL of aqua regia (6.1) and heat 2 minutes in a water bath at 95°C.
Allow the sample to cool and add 50 mL distilled water and 15 mL of KMnO4
solution (6.5) to each bottle and return to the water bath for 30 minutes. Cool
and add 6 mL of sodium chloride-hydroxylamine sulfate solution (6.4) to
reduce the excess permanganate. Add 50 mL of distilled water. Treating each
bottle individually, add 5 mL of stannous sulfate solution (6.3) and
immediately attach the bottle to the aeration apparatus. At this point, the
sample is allowed to stand quietly without manual agitation. The circulating
pump, which has previously been adjusted to rate of 1 liter per minute, is
allowed to run continuously. The absorbance, as exhibited either on the
spectrophotometer or the recorder, will increase and reach maximum within 30
seconds. As soon as the recorder pen levels off, approximately 1 minute, open
the bypass value and continue the aeration until the absorbance returns to its
minimum value (See Note 5). Close the bypass value, remove the fritted tubing
from the BOD bottle and continue the aeration. Proceed with the standards
and construct a standard curve by plotting peak height versus micrograms of
mercury.
NOTE 5: Because of the toxic nature of mercury vapor precaution must be
taken to avoid its inhalation. Therefore, a bypass has been included in the
system to either vent the mercury vapor into an exhaust hood or pass the
vapor through some absorbing media, such as:
a) equal volumes of 0.1 N KmnO4 and 10% H2 SO4
b) 0.25% iodine in a 3% KI solution.
A specially treated charcoal that will absorb mercury vapor is also available
from Barnebey and Cheney, E. 8th Ave., and North Cassidy St., Columbus,
Ohio 43219, Cat. #580-13 or #580-22.

8.0 Procedure

8.1 Weigh triplicate 0.2 g portions of dry sample and place in bottom of a BOD
bottle. Add 5 mL of distilled water and 5 mL of aqua regia (6.1). Heat 2
minutes in a water bath at 95°C. Cool, add 50 mL distilled water and 15 mL
potassium permanganate solution (6. 5) to each sample bottle. Mix thoroughly
 and place in the water bath for 30 minutes at 95°C. Cool and add 6 mL of
sodium chloride-hydroxylamine sulfate (6.4) to reduce the excess
permanganate. Add 55 mL of distilled water. Treating each bottle individually,
add 5 mL of stannous sulfate (6.3) and immediately attach the bottle to the
aeration apparatus. Continue as described under (7.1).
8.2 An alternate digestion procedure employing an autoclave may also be used. In
this method S mL of conc. H2SO4 and 2 mL of conc. HNO3 are added to the 0.2
g of sample. 5 mL of saturated KMnO4 solution is added and the bottle
covered with a piece of aluminum foil. The samples are autoclaved at 121°C
and 15 lbs. for 15 minutes. Cool, make up to a volume of 100 mL with distilled
water and add 6 mL of sodium chloride hydroxylamine sulfate solution (6.4) to
reduce the excess permanganate. Purge the dead air space and continue as
described under (7.1).

9.0 Calculation

9.1 Measure the peak height of the unknown from the chart and read the mercury
value from the standard curve.
9.2 Calculate the mercury concentration in the sample by the formula:

9.3 Report mercury concentrations as follows: Below 0.1 Fg/gm, <0.1; between 0.1
and 1 Fg/gm, to the nearest 0.01 Fg; between 1 and 10 Fg/gm, to nearest 0.1
Fg; above 10 Fg/gm, to nearest Fg.
10.0 Precision and Accuracy

10.1 The following standard deviations on replicate sediment samples were

recorded at the indicated levels; 0.29 Fg/g ± 0.02 and 0.82 ug/g ±0.03.
Recovery of mercury at these levels, added as methyl mercuric chloride, was
97% and 94%, respectively.

Bibliography

1. Bishop, J. N., "Mercury in Sediments", Ontario Water Resources Comm., Toronto,

Ontario, Canada, 1971.
2. Salma, M., private communication, EPA Cal/Nev Basin Office, Almeda, California.