ASTM D3223-02(2007)e1

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D3223 − 02(Reapproved 2007)
Standard Test Method for
Total Mercury in Water
This standard is issued under the fixed designation D3223; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.
´ NOTE—Reference to Practice D2777 – 77 was editorially updated to D2777 – 06 in August 2007.
1. Scope 1.5 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
1.1 This test method covers the determination of total
responsibility of the user of this standard to establish appro-
mercury in water in the range from 0.5 to 10.0 µg Hg/L (1).
priate safety and health practices and determine the applica-
Thetestmethodisapplicabletofreshwaters,salinewaters,and
bility of regulatory limitations prior to use. For specific hazard
some industrial and sewage effluents. It is the user’s responsi-
statements, see 7.8 and 10.8.2.
bility to ensure the validity of this test method for waters of
untested matrices.
2. Referenced Documents
1.1.1 The analyst should recognize that the precision and
2.1 ASTM Standards:
bias of this standard may be affected by the other constituents
D512 Test Methods for Chloride Ion In Water
inallwaters,astap,industrial,river,andwastewaters.Thecold
D1129 Terminology Relating to Water
vaporatomicabsorptionmeasurementportionofthismethodis
D1193 Specification for Reagent Water
applicable to the analysis of materials other than water
D1245 Practice for Examination of Water-Formed Deposits
(sediments,biologicalmaterials,tissues,etc.)if,andonlyif,an
by Chemical Microscopy
initial procedure for digesting and oxidizing the sample is
D1252 Test Methods for Chemical Oxygen Demand (Di-
carried out, ensuring that the mercury in the sample is
chromate Oxygen Demand) of Water
converted to the mercuric ion, and is dissolved in aqueous
D1426 Test Methods for Ammonia Nitrogen In Water
media (2,3).
D2777 Practice for Determination of Precision and Bias of
1.2 Both organic and inorganic mercury compounds may be Applicable Test Methods of Committee D19 on Water
analyzed by this procedure if they are first converted to D3370 Practices for Sampling Water from Closed Conduits
mercuric ions. Using potassium persulfate and potassium D4691 Practice for Measuring Elements in Water by Flame
permanganate as oxidants, and a digestion temperature of Atomic Absorption Spectrophotometry
95°C, approximately 100 % recovery of organomercury com-
D4841 Practice for Estimation of Holding Time for Water
pounds can be obtained (2,4). Samples Containing Organic and Inorganic Constituents
D5810 Guide for Spiking into Aqueous Samples
1.3 The range of the test method may be changed by
D5847 Practice for Writing Quality Control Specifications
instrument or recorder expansion or both, and by using a larger
for Standard Test Methods for Water Analysis
volume of sample.
3. Terminology
1.4 Amethod for the disposal of mercury-containing wastes
is also presented (Appendix X1) (5).
3.1 Definitions: For definitions of terms used in this test
method, refer to Terminology D1129.
4. Summary of Test Method
This test method is under the jurisdiction of ASTM Committee D19 on Water
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents
4.1 The test method consists of a wet chemical oxidation
in Water.
which converts all mercury to the mercuric ion; reduction of
Current edition approved Aug. 1, 2007. Published August 2007. Originally
mercuric ions to metallic mercury, followed by a cold vapor
approved in 1979. Last previous edition approved in 2002 as D3223 – 02. DOI:
10.1520/D3223-02R07E01.
Adapted from research investigations by the U. S. Environmental Protection
Agency’s Analytical Quality Control Laboratory, Cincinnati, OH, and Region IV For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Surveillance and Analysis Division, Chemical Services Branch, Athens, GA. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
The boldface numbers in parentheses refer to the references at the end of this Standards volume information, refer to the standard’s Document Summary page on
test method. the ASTM website.
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D3223 − 02 (2007)
atomic absorption analysis (1,2).Ageneral guide for flame and
vapor generation atomic absorption applications is given in
Practice D4691.
4.2 Cold vapor atomic absorption analysis is a physical
method based on the absorption of ultraviolet radiation at a
wavelength of 253.7 nm by mercury vapor. The mercury is
reduced to the elemental state and aerated from solution in
either a closed recirculating system or an open one-pass
system. The mercury vapor passes through a cell positioned in
the light path of an atomic absorption spectrophotometer.
Absorbance is measured as a function of mercury concentra-
tion.
5. Significance and Use
5.1 The presence of mercury in industrial discharge, domes-
tic discharge, and potable water is of concern to the public
because of its toxicity. Regulations and standards have been
established that require the monitoring of mercury in water.
This test method provides an analytical procedure to measure
total mercury in water.
A—Reaction flask G—Hollow cathode mercury lamp
B—60-W light bulb H—Atomic absorption detector
C—Rotameter, 1 L of air per minute J— Gas washing bottle containing
6. Interference
0.25 % iodine in a 3 % potassium io-
dide solution
6.1 Possible interference from sulfide is eliminated by the
D— Absorption cell with quartz windows K—Recorder, any compatible model
additionofpotassiumpermanganate.Concentrationsashighas
E— Air pump, 1 L of air per minute
20 mg/L of sulfide as sodium sulfide do not interfere with the
F—Glass tube with fritted end
recovery of added inorganic mercury from distilled water (2).
FIG. 1 Schematic Arrangement of Equipment for Mercury Mea-
6.2 Copper has also been reported to interfere; however,
surement by Cold Vapor Atomic Absorption Technique Closed
copper concentrations as high as 10 mg/Lhave no effect on the
Recirculating System
recovery of mercury from spiked samples (2).
6.3 Seawaters, brines, and industrial effluents high in chlo-
mercury using the cold vapor technique in the working range
rides require additional permanganate (as much as 25 mL). specified may be used.
During the oxidation step chlorides are converted to free
7.2.1 Mercury Hollow Cathode Lamp.
chlorine which will also absorb radiation at 253.7 nm. Care 7.2.2 Simultaneous Background Correction—Background
must be taken to assure that free chlorine is absent before
correction may be necessary to compensate for molecular
mercury is reduced and swept into the cell. This may be absorption that can occur at this mercury wavelength. It is the
accomplished by using an excess of hydroxylamine sulfate
analyst’s responsibility to determine the applicable use.
reagent (25 mL). The dead air space in the reaction flask must
7.3 Recorder—Any multirange variable speed recorder that
also be purged before the addition of stannous sulfate. Both
is compatible with the ultraviolet (UV) detection system is
inorganic and organic mercury spikes have been quantitatively
suitable.
recovered from sea water using this technique (2).
7.4 Absorption Cell—The cell (Fig. 3) is constructed from
6.4 Volatile organic materials that could interfere will be
glass 25.4-mm outside diameter by 114 mm (Note 2).The ends
removed with sample digestion as described in 11.2 through
are ground perpendicular to the longitudinal axis and quartz
11.4.
windows (25.4-mm diameter by 1.6 mm thickness) are ce-
mented in place. Gas inlet and outlet ports (6.4-mm diameter)
7. Apparatus
are attached approximately 12 mm from each end. The cell is
NOTE 1—Take care to avoid contamination of the apparatus with
strapped to a support and aligned in the light beam to give
mercury. Soak all glass apparatus, pipets, beakers, aeration tubes, and
maximum transmittance.
reaction flasks in nitric acid (HNO ) (1 + 1), and rinse with mercury-free
water before use.
NOTE 2—An all-glass absorption cell, 18 mm in outside diameter by
7.1 The schematic arrangement of the closed recirculating
200 mm, with inlet 12 mm from the end, 18-mm outside diameter outlet
in the center, and with quartz windows has been found suitable. Methyl
systemisshowninFig.1andtheschematicarrangementofthe
methacrylate tubing may also be used.
open one-pass system is shown in Fig. 2.
7.5 Air Pump—A peristaltic pump, with electronic speed
7.2 Atomic Absorption Spectrophotometer—A commercial
control, capable of delivering 1 L of air per minute may be
atomic absorption instrument is suitable if it has an open-
used. Regulated compressed air can be used in the open
burner head area in which to mount an absorption cell, and if
one-pass system.
it provides the sensitivity and stability for the analyses. Also
instruments designed specifically for the measurement of 7.6 Flowmeter, capable of measuring an air flow of 1 L/min.
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D3223 − 02 (2007)
lamp shall be positioned to shine on the absorption cell
maintaining the air temperature in the cell about 10°C above
ambient. Alternatively, a drying tube, 150 by 18 mm in
diameter, containing 20 g of magnesium perchlorate, may be
placed in the line to prevent moisture in the absorption cell.
(Warning—If the presence of organic vapors is expected, the
purityofthedryingagentshouldbedeterminedtoestablishthe
absence of traces of free perchloric acid in the salt. This is to
prevent the formation of perchloric esters, some of which are
known to be violently explosive compounds.)
7.9 ReactionFlask—A250-to300-mLglasscontainerfitted
with a rubber stopper may be used.
8. Reagents
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society.
Other grades may be used, provided it is first ascertained that
the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
8.2 Purity of Water—Unless otherwise indicated, references
towatershallbeunderstoodtomeanreagentwaterconforming
A—Reaction flask G—Hollow cathode mercury lamp
to Specification D1193 Type I. Other reagent water types may
B—60-W light bulb H—Atomic absorption detector
be used, provided it is first ascertained that the water is of
C—Rotameter, 1 L of air per minute J—Vent to hood
sufficiently high purity to permit its use without adversely
D— Absorption cell with quartz windows K— Recorder, any compatible model
E— Compressed air, 1 L of air per min- L— To vacuum through gas washing
affecting the bias and precision of the test method. Type II
ute bottle containing 0.25 % iodine in a 3 %
water was specified at the time of round-robin testing of this
potassium iodide solution
F—Glass tube with fritted end test method.
8.3 Mercury Solution, Stock (1 mL = 1 mg Hg)—Dissolve
FIG. 2 Schematic Arrangement of Equipment for Mercury Mea-
surement by Cold Vapor Atomic Absorption Technique Open 0.1354 g of mercuric chloride (HgCl ) in a mixture of 75 mL
One-Pass System
of water and 10 mLof HNO (sp gr 1.42) and dilute to 100 mL
with water.
8.4 Mercury Solution, Intermediate (1 mL = 10 µg Hg)—
Pipet 10.0 mL of the stock mercury solution into a mixture of
500 mL of water and 2 mL of HNO (sp gr 1.42) and dilute to
1 L with water. Prepare fresh daily.
8.5 Mercury Solution, Standard (1 mL = 0.1 µg Hg)—Pipet
10.0mLoftheintermediatemercurystandardintoamixtureof
500 mL of water and 2 mL of HNO (sp gr 1.42) and dilute to
1 L with water. Prepare fresh daily.
NOTE 1—The length and outside diameter of the cell are not critical. 8.6 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
The body of the cell may be of any tubular material but the end windows
(HNO ).
mustbeofquartzbecauseoftheneedforUVtransparency.Thelengthand
diameter of the inlet and outlet tubes are not important, but their position NOTE 3—If the reagent blank concentration is greater than the method
detection limit, distill the HNO or use a spectrograde acid.
may be a factor in eliminating recorder noise.There is some evidence that
displacement of the air inlet tube away from the end of the cell results in
8.7 Potassium Permanganate Solution (50 g/L)—Dissolve
smoother readings. A mild pressure in the cell can be tolerated, but too
50 g of potassium permanganate (KMnO ) in water and dilute
much pressure may cause the glued-on end windows to pop off. Cells of
to1L.
this type may be purchased from various supply houses.
FIG. 3 Cell for Mercury Measurement by Cold-Vapor Technique
8.8 Potassium Persulfate Solution (50 g/L)—Dissolve 50 g
of potassium persulfate (K S O ) in water and dilute to 1 L.
2 2 8
7.7 Aeration Tubing—A straight glass frit having a coarse
porosityisusedinthereactionflask.Clearflexiblevinylplastic
Reagent Chemicals, American Chemical Society Specifications, American
tubing is used for passage of the mercury vapor from the
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
reaction flask to the absorption cell. listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
7.8 Lamp—Asmall reading lamp containing a 60-W bulb is
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
used to prevent condensation of moisture inside the cell. The MD.
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D3223 − 02 (2007)
8.9 Sodium Chloride-Hydroxylamine Sulfate Solution (120 10.7 After waiting 30 s treat each flask individually by
g/L)—Dissolve 120 g of sodium chloride (NaCl) and 120 g of adding 5 mLof the SnSO solution and immediately attach the
hydroxylamine sulfate [(NH OH) H SO ] in water and dilute bottle to the aeration apparatus forming a closed system. Refer
2 2 2 4
to1L. to Note 5.
10.8 After the absorbance has reached a maximum and the
NOTE 4—The analyst may wish to use hydroxylamine hydrochloride
instead of hydroxylamine sulfate. The analyst should dissolve 12 g of recorder pen has leveled off, prepare the system for the next
hydroxylamine hydrochloride in 100 mL of Type I water.
standard by one of the following procedures:
10.8.1 Close
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