8.

30

Mercury in Ambient Air

D. J. SIBBETT

(1974, 1982)

B. G. LIPTK

(1995)

R. S. SALTZMAN

(2003)

Methods of Detection:

A. Ultraviolet, flameless atomic absorption

B. Atomic absorption spectrophotometer
C. Gold-film sensor
D. Colorimetric titration
E. Gas chromatography
F. Atomic fluorescence
G. Neutron activation

Regulatory Levels
for Emissions:

100, 50, 10, and perhaps 5 g/m

Range, in Ambient Air:

1 to 200 ng/m

Ranges of Analyzers:

A. 0 to 400 volumetric ppb

3
B. 0 to 45 or 0 to 75 g/m
3
C. 0 to 2 mg/m

Sensitivity:

A. 1.0 ng/m is about the best attainable

3
B. 0.1 g/m
3
C. 0.003 mg/m
F. 0.1 ppm in liquid impinger sample

Inaccuracy:

A. 2% on direct measurement, 10% with concentrators

3
C. 5% at 0.1 mg/m

Costs:

A. Laboratory analyzer alone costs about $25,000; process analyzer alone costs about
$30,000; an integrated samplerdetector system costs about $45,000 or more
B. $100,000 and up
C. Battery-operated, portable gold-film sensor with small flow pump costs $5000

Partial List of Suppliers:

(For a more complete list of suppliers of gas chromatographs, see Section 8.12; for
atomic absorption analyzer suppliers, see Section 8.22; for ultraviolet analyzers, see
Section 8.61; and for autotitrators, see Section 8.66.)
ABB (A) (www.abb.com/analytical)
AMETEK, Process and Analytical Instruments Co. (A, C) (www.ametekpi.com)
Aurora Instruments (www.aurora-instr.com)
Bacharach Inc. (www.bacharach-inc.com)
Brucks Rand LLC (www.brooksrand.com)
Buck Scientific (www.bucksci.com)
Cetac (www.cetac.com)
Cole-Parmer (www.coleparmer.com)
Davis Inotek Instr. (www.inotek.com)
EcoChem Analytics (www.ecochem.biz)
Fisher Scientific (www.fishersci.com)
LECO Corp. (www.leco.com)
Leeman Labs Inc. (www.leemanlabs.com)
Mercury Instr. GmbH (www.mercury-instruments.de)
Milestone (www.milestonesc.com)

1407
2003 by Bla Liptk

1408

Analytical Instrumentation

Perkin-Elmer Corp. (A, B) (www.instruments.perkinelmer.com)

P.S. Analytical (www.psanalytical.com)
Rigaku MSC (www.rigakumsc.com)
Roentec GmbH (www.roentec.de)
Shimadza Scientific Instruments (A,B)
Sick (A) (www.sickmahaihak.com)
Tekran Inc. (www.tekran.com)
Thermo Automation Syst. (www.thermo.com)

INTRODUCTION
Because the mercury concentration of interest in ambient air
3
is in the range of nanograms per cubic meter (ng/m ), no
direct method of analysis exists and all measurements require
the use of concentrators in sampling systems. Therefore, this
section will start with descriptions of the various sampling
and concentrator designs.
Instruments used in the measurement of mercury in air
or gas samples are covered in other sections of this handbook:
chromatographs in Section 8.12, atomic absorption spectrophotometers in Section 8.22, ultraviolet analyzers in Section
8.61, and autotitrators in Section 8.66. Therefore, the treatment of these analyzers is not very detailed here.
Air saturated with mercury will contain between 4 and
3
100 mg/m of mercury in the temperature range between 45
and 110F (7 and 43C). Since saturation is not even
approached under normal circumstances when the air is moving, sensitive analytical and sampling methods are needed
when data are required on the actual ambient levels of mercury. For practical use, the methods employed must be relatively insensitive to interference and be otherwise appropriate
for the collection of data under a wide range of operating
conditions. For regulatory purposes, related to emissions,
three or four levels of sensitivity are of importance: 100, 50,
3
10, and perhaps 5 g/m of mercury in the air. Accuracy
within 10% at these levels is required. However, ambient
air monitoring requires the ability to determine levels in the
3
1 to 200 mg/m range.
Sample Collection and Concentration
Collection of mercury samples for accurate determination of
concentrations found at ambient conditions or in industrial
plants requires that:
1. The size of the sample taken must be adequate to
satisfy the sensitivity threshold requirements of the
analytical technique utilized.
2. The rate of sampling must be controlled so that efficient collection is achieved.
3. The sampling interval selected must be appropriate for
the required monitoring function.
4. The collection device or procedure must be compatible
in capacity and chemical reactivity of material components with the levels and properties of mercury and
mercury compounds to be sampled.

2003 by Bla Liptk

5. Effects of potential interference must be avoided.

6. Elapsed time between collection and analysis must be
minimized in order to avoid losses.
7. It must be possible to evaluate all unknown factors in
collection and analysis by using the appropriate calibration procedures.
In the sampling of mercury and its compounds from the
air, two basic procedures are available. These procedures utilize either the chemical reactivity of the sampled components
in various aqueous media or the extraordinarily efficient extraction (amalgamation) of mercury from air by the noble metals.
In the latter case, reduction of mercury compounds to
elemental mercury is required before the sampling process
is carried out. Currently, a wet chemical procedure for sampling is recommended by the Environmental Protection
Agency. This procedure requires considerable labor and
upkeep to perform effectively.

Impinger Collection Methods

In conjunction with the publication of the National Emission
1
Standards for Hazardous Air Pollutants, the Environmental
Protection Agency has published two methods for sampling
and analyzing mercury in gaseous and particulate emissions.
The methods are similar with the exception that particulates
must be sampled isokinetically, whereas gaseous samples are
passed through filters to remove particles. This latter procedure requires equilibration of the filter prior to generation of
accurate data at low mercury levels.
In principle, samples are drawn through acidic aqueous
iodine monochloride solutions utilizing stringent controls over
flow rates, acidity, and other process variables. This procedure
gives excellent recovery of organic mercury compounds and
of mercury vapor. Samples obtained with this procedure may
be stored.
Particulate Sampling Figure 8.30a shows the sampling
train utilized for particulate and vapor samples. It consists of
a Pyrex-lined, heated probe section containing a thermocouple for temperature measurement and a pair of pitot tubes
and a manometer for gas flow measurement. This section is
followed by five impingers of the SmithGreenburg type
placed in an ice bath and a filter for particle removal prior to
passage of the gases through the two final absorber stations.

8.30 Mercury in Ambient Air

STACK
WALL

FILTER
HOLDER

HEATED
AREA

THERMOMETER
CHECK
VALVE

IMPINGERS

PROBE

1409

FIG. 8.30c
Absorption tube mercury collection device.
ICE
BATH

REVERSE-TYPE
PITOT-TUBE

BY-PASS MAIN VACUUM

VALVE VALVE GAUGE

PITOT MANOMETER

VACUUM
LINE

AIR INLET

OUTLET

ORIFICE

AIR-TIGHT
PUMP
DRY TEST METER

FIG. 8.30a
Particulate-sampling train.
PROBE

FIG. 8.30d
Mercury gas-sampling tube.

MIDGET IMPINGERS

ACID ABSORBING TUBE

ICE BATH

ROTAMETER
DRY GAS
METER

VALVE
PUMP

FIG. 8.30b
Vapor-sampling train.

These components are followed by miscellaneous components for control and calibration of the sample airflow.
For sampling particulates, the initial rate of gas flow is
2 scfh (57 slph). Flow should be maintained at a rate proportional to the flow through the stack sampled.
Vapor Sampling Figure 8.30b shows a simpler technique
used for sampling of vapors without particulates. In this
method, particulates are removed by a filter, at the inlet into
the absorption train. Samples obtained by this procedure may
be analyzed by a procedure utilizing a flameless atomic
absorption spectrophotometer, which has been accepted by
the Environmental Protection Agency for investigations.
A number of other collection procedures employing
impingers have been examined. These utilize water, ethyl alcohol, isopropyl alcohol, potassium permanganatesulfuric acid,
potassium permanganatenitric acid, or iodinepotassium
iodine. However, for effective collection of alkyl mercury compounds, acidic iodine monochloride solutions are preferable.
Amalgamation on Wettable Metals
A number of less laborious methods of sampling mercury
vapor, compounds, and particulates have been developed that
utilize absorption (amalgamation) of vapor on silver, gold,
and alloys of these materials. In order to sample particulates

2003 by Bla Liptk

and compounds of mercury, the trapping procedure must be

preceded by a decomposition step. A catalytic process that
achieves this objective is described later.
Examples of procedures for collecting elemental mercury
vapor include the method shown in Figure 8.30c, which
shows a simple absorption tube filled with gold or silver wool.
The tube may be sized to satisfy any specific parameters of
the sampled gas stream. Fine wire may also be used as packing for flow rates under 50 l/min, and mercury vapor removal
can be made quantitative. Gold materials are required for
gases containing hydrogen sulfide or sulfur dioxide.
When a simple absorption tube of this type is employed,
the mercury vapor collected may be released for analysis in
a flameless atomic absorption spectrometer (AAS) by utilizing an induction furnace (Section 8.22). In this procedure,
extensively used by the U.S. Geological Survey, a continuously flowing airstream is used to pass the pulse of the
mercury vapor into the AAS cell. This pulse is generated
during the heating in the furnace.
Sampling Tubes The Canadian Department of the Environment employs a versatile method of sampling of gas streams.
It uses a packing, which consists of finely woven silver mesh
(Figure 8.30d). One version of the sampling tube is 5 in. (125
mm) high and utilizes a 1 in. (6-mm)-inner-diameter Pyrex
4
tubing. Separation between the inner and outer tube is 3 in.
64
(0.1 mm). In order for this collection procedure to function
effectively, relatively low airflow rates through the wire mesh
must be used. Sampling rates of 1 to 5 l/min have been
employed, but long sampling periods are required to make
measurements at low air concentrations.
Figure 8.30e shows the schematics of a collection device,
which is contained in an integrated mercury analyzer. In the
collection section of this device, air at rates from 0.03 to 7
scfm (1 to 200 l/min) is passed through a grid containing 160
ft (48 m) of 22-gauge wire arranged in a carefully spaced
annulus. Mercury vapor is desorbed by direct passage of

1410

Analytical Instrumentation

INSTRUMENT WALL

WIRE WINDINGS

SYNCRONIZED

ROTARY
CHOPPER

PHOTOMETER
FLAME
AC
AMPLIFIER

AIR INLET

FIG. 8.30e
Mercury collection device.

HOLLOWCATHODE
LAMP

RECORDER

FUEL
OXIDANT
MONOCHROMATOR
SAMPLE

electrical current through the wire. Analysis is achieved by

the flameless atomic absorption method in a photometer.

FIG. 8.30f
Atomic absorption spectrophotometer.

Activated Absorption
Use of a silver on a charcoal absorbent is highly efficient and
may be used to remove mercury vapor from many gas
streams. Extraction of the mercury vapor as a concentrated
pulse for analysis, however, is relatively difficult. Induction
heating is required to maximize the vapor concentration.
Trapping is also possible with iodine-activated charcoal and
mineral wool. Regeneration of these materials for repeated
use presents difficulties not yet resolved.
Conversion of Mercury Vapors
In order to analyze for total mercury including particulates
and vapor, reduction of compounds such as mercuric chloride, mercuric sulfide, dimethyl and diethyl mercury, pesticides, and fungicides to the elemental form must be achieved.
Three techniques are in use: 1) thermal decomposition at
1500 to 2000F (816 to 1093C); 2) catalytic reduction or
disproportionation, usually at 1200 to 1300F (648 to 704C)
over materials such as cupric oxides; and 3) chemical conversion in solutions such as acidic iodine monochloride.
Commercial equipment is available, which may be used in
conjunction with sampling and analysis instrumentation.
Methods of Detection
No direct analytical method is capable of attaining accurate
measurements in the range required for ambient air without
the use of a concentrator, discussed earlier.
Ultraviolet Light Absorption
A wide variety of methods have been developed to measure
airborne mercury-containing materials in the atmosphere
based on the strong absorption of ultraviolet light at 253.7
nm by an elemental mercury vapor. Since many other compounds absorb light in this range, although they do that at a
much higher concentration than does mercury, some method
of separating out these interferences is needed when low
levels of mercury are to be measured.
Atomic Absorption Spectrophotometry Mercury is conveniently analyzed by atomic absorption techniques because
the elemental vapor exists in atomic form under normal ambient conditions. Thus, when a cloud of mercury vapor is

2003 by Bla Liptk

ANHYDRONE
FILLED
DRYING
TUBE

FROM
FLOWMETER
AND AIR OR
NITROGEN
SUPPLY
GAS
WASHING
BOTTLE
SAMPLE

WATER
VAPOR
TRAP

VENT

10 CM
ABSORPTION
CELL

FIG. 8.30g
Apparatus for flameless atomic absorption.

irradiated at an appropriate wavelength, mercury atoms

absorb a portion of the energy of the beam.
In the standard atomic absorption technique, liquid samples are aspirated into an acetylene air flame where the atomic
mercury is released and the absorption of light at 253.7 nm
is measured by a spectrophotomultiplier (Figure 8.30f). The
sensitivity of 0.01 g of mercury per milliliter of sample is
readily attained by this procedure. A continuous series of
calibration checks are required for maximal precision and
accuracy.
Flameless Atomic Absorption Spectroscopy The burner
aspirator and flame indicated in the schematic of the conventional AAS (Figure 8.30f) may be replaced by a quartzwindowed glass cell, and the sample may be generated by
reducing an aqueous sample of mercury compounds to elemental mercury.
Figure 8.30g shows the apparatus that may be used in
conjunction with an AAS. In this procedure, a sample collected by utilizing a separate collection train is pipetted into
the gas washing bottle. To this is added a solution of a
reducing agent such as hydroxylamine sulfate or stannous
chloride, and the bottle is closed.
With clean air supplied at a rate of 1.3 l/min, aeration is
commenced and continued until a maximum peak height
readout is obtained on the recorder. By calibration against
acidic mercuric chloride standard solutions, the peak heights
obtained with unknown samples can be compared with the
calibration curve for direct determination of the mercuric ion
concentration. This value may be converted to the gas phase
concentration of mercury.

8.30 Mercury in Ambient Air

A number of commercial units are available that use the

principle of flameless atomic absorption spectroscopy for
determination of mercury. Some designs require that samples
be taken by use of a liquid-sampling train and transported to
the instrument, while others accept gas samples.
Other devices based on the use of absorption of radiation
at 253.7 nm have been developed by Barringer Research and
2
by Williston and Morris (Cordero Mining Company). The
Barringer method takes advantage of the pressure broadening
of the mercury emission lines to minimize interference
caused by other compounds.

1411

Gas Chromatography for Mercury Organics

Organic mercurials can be determined at levels of approximately 1 ppb by gas chromatographic methods. Samples must
be extracted into benzene and injected into a gas chromatographic column (Carbowax 20M on Chromasorb W) operating at 356F (180C), which separates methyl mercury, ethyl
mercury, methozyethyl mercury, phenyl mercury, and dimethyl mercury. Quantitation is obtained with an electron capture detector. Dimethyl mercury requires conversion into
methyl mercury halide for analysis, however. Precision is
reported to be about 12%, with 30% reliability.

Colorimetric Methods

Selenium Sulfide and Others Active selenium sulfide applied

to paper as a coating may be used to detect the presence of
elemental mercury vapor. The paper develops a black color
on exposure to air containing mercury. The degree of blackening is a function of the concentration of mercury and the
times of exposure. Quantitation may be made with a simple
densitometer.
Mercury can also be detected with copper, iodine paper,
selenium paper, and gold chloride on silica gel. These methods appear to have a limiting sensitivity in the 500 to
3
1000 g/m range and a measurement error of 5%.

2003 by Bla Liptk

Atomic Fluorescence Spectroscopy

Samples collected by any of the liquid impinger techniques
(Figures 8.30a and 8.30b) may be analyzed by use of atomic
fluorescence flame spectrophotometric methods. Figure 8.30h
provides a schematic diagram of a typical fluorescence spectrophotometer and of some typical calibration data. Figure
8.30i shows an actual x-ray fluorescence spectrometer. A
mercury concentration of 0.1 ppm in a collection fluid is the
detection limit of this method.

SOLID ANGLE VIEWED BY MONOCHROMATOR

FLAME
CELL

PHOTODETECTOR

MONOCHROMATOR

SOLID
ANGLE OF
EXCITATION

ELECTROMETERREADOUT

EXCITATION
SOURCE

FLUORESCENCE SIGNAL

Dithizone In this method, air is drawn through an acidic

solution (10% H2SO4) of potassium permanganate (4 g/100 ml),
where the elemental mercury, inorganic mercury compounds,
and the readily decomposable mercuryorganic compounds
are converted to mercuric ions.
Methyl mercury compounds require the use of permanganate at 212F (100C ). The determination of mercury may
be concluded colorimetrically whence the sample is titrated
with dithizone and compared with the colors developed by
standards. A spectrophotometer may also be used for quantitative comparison between the color developed by test samples and those of controlled standard quantities of mercury.
In the method developed by the American Conference of
Government Industrial Hygienists, the sample is collected
from the air by passing it through an aqueous solution of
iodine (0.25%) and potassium iodine (3%). Mercury is
extracted from a buffered solution (ammonium citrate,
hydroxylamine hydrochloride, and phenol red at pH 8.5) with
dithizone in chloroform (20 mg of dithizone/5 ml) until all
color is removed. After washing the chloroform phase, the
mercury is extracted into acidic (0.1 N HCL) potassium bromide (8%), shaken with a chloroform solution of 10 mg/l of
dithizone, and filtered through cotton into a colorimeter cell.
The optical density at 485 mm is used to determine the
mercury. Calibration is carried out with mercuric chloride.
The dithizone method is relatively insensitive, requiring
the use of large samples (about 10 g are required) when the
levels of mercury are low. It also requires considerable care
on the part of the chemist to avoid the loss of organic mercury
compounds.

Cd
TI
Hg

103

102
101
100
101
CONCENTRATION OF METAL, PPM

FIG. 8.30h
Atomic fluorescence spectrophotometer.

102

1412

Analytical Instrumentation

FIG. 8.30i
X-ray fluorescence spectrometer. (Courtesy of Roentec GmbH, Berlin, Germany.)

Other Analytical Procedures

A radiochemical procedure for the determination of mercury
vapor has been developed based on the isotopic exchange
that takes place when air samples containing mercury are
203
passed through a solution of Hg mercuric acetate. The
method potentially has good sensitivity but requires precautions, which are normal in handling radioisotopes.
Mercury that has been extracted from the air may be determined utilizing a neutron activation procedure. The measurement error and precision of this method is in the range of 2%.
References
1.
2.

Federal Register, Vol. 36, No. 234, December 7, 1971, pp. 23, 250.
Williston, S. H. and Morris, M. H., U.S. Patent 3,173,016, March 9,
1965; Williston, S. H., U.S. Patent 3,178,572, April 13, 1965.

Bibliography
Control Staff, Mysteries of Gold Film Sensors to be Studied, Control,
January 1989.

2003 by Bla Liptk

Denny, R. and Sinclair, R., Visible and Ultraviolet Spectroscopy, New York:
John Wiley & Sons, 1987.
Ewing, G. W., Ed., Instrumental Methods of Chemical Analysis, New York:
McGraw-Hill, 1981.
Guilbault, G. G., Ed., Fluorescence, New York: Marcel Dekker, 1967.
Hughes, T. J., The Finite Element Method, Dover Publishers, 2000.
Kwon, Y. W., The Finite Element Method Using MATLAB, Boca Raton, FL:
CRC Press, 2000.
Leithe, W., The Analysis of Air Pollutants, Ann Arbor, MI: Ann Arbor
Science Publishers, latest edition.
Mercury in Your Environment, www.rigakumsn.com/Hg/Hg-articles.shtml.
Meyers, R. A., Ed., Encyclopedia of Analytical Chemistry Instrumentation
and Applications, U.K.: John Wiley & Sons, 1999
Portable High-Performance Mercury Analyzer for Field Use Mercury
Sniffer, The Rigaku Journal, Vol. 15, 1998.
Seiler, H. and Sigel, H., Handbook on Toxicity of Inorganic Compounds,
New York: Marcel Dekker, 1988.
Smith, D. et al., EPAs Sampling and Analysis Methods Database, Chelsea,
MI: Lewis Publishers, 1990.
Vaughn, W. W., A Simple Mercury Vapor Detection for Geochemical Prospecting, Geological Survey Circular 540, U.S. Department of the
Interior, 1967.