ASTM D3223-17

Standard Test Method for Total Mercury in Water

SIGNIFICANCE AND USE
5.1 The presence of mercury in industrial discharge, domestic 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.
SCOPE
1.1 This test method2 covers the determination of total mercury in water in the range from 0.5 to 10.0 μg Hg/L (1).3 The test method is applicable to fresh waters, saline waters, and some industrial and sewage effluents. It is the user's responsibility to ensure the validity of this test method for waters of untested matrices.  
1.1.1 The analyst should recognize that the precision and bias of this standard may be affected by the other constituents in all waters, as tap, industrial, river, and wastewaters. The cold vapor atomic absorption measurement portion of this method is applicable to the analysis of materials other than water (sediments, biological materials, tissues, etc.) if, and only if, an initial procedure for digesting and oxidizing the sample is carried out, ensuring that the mercury in the sample is converted to the mercuric ion, and is dissolved in aqueous media (2, 3).  
1.2 Both organic and inorganic mercury compounds may be analyzed by this procedure if they are first converted to mercuric ions. Using potassium persulfate and potassium permanganate as oxidants, and a digestion temperature of 95°C, approximately 100 % recovery of organomercury compounds can be obtained (2, 4).  
1.3 The range of the test method may be changed by instrument or recorder expansion or both, and by using a larger volume of sample.  
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.5 A method for the disposal of mercury-containing wastes is also presented (Appendix X1) (5).  
1.6 Warning—Mercury has been designated by many regulatory agencies as a hazardous material that can cause serious medical issues. Mercury, or its vapor, has been demonstrated to be hazardous to health and corrosive to materials. Caution should be taken when handling mercury and mercury containing products. See the applicable product Safety Data Sheet (SDS) for additional information. Users should be aware that selling mercury and/or mercury containing products into your state or country may be prohibited by law.  
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see 1.6 and 7.8.  
1.8 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 31-May-2017
• ICS: 13.060.50 - Examination of water for chemical substances
• Technical Committee: D19 - Water
• Drafting Committee: D19.05 - Inorganic Constituents in Water

Relations

• Replaces: ASTM D3223-12 - Standard Test Method for Total Mercury in Water
• Effective Date: 01-Jun-2017
• Refers: ASTM D1129-13(2020)e2 - Standard Terminology Relating to Water
• Effective Date: 01-May-2020
• Refers: ASTM D1245-17 - Standard Practice for Examination of Water-Formed Deposits by Chemical Microscopy
• Effective Date: 01-Jun-2017
• Refers: ASTM D4841-88(2013)e1 - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 01-Jan-2013
• Refers: ASTM D4841-88(2013) - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 01-Jan-2013
• Refers: ASTM D2777-12 - Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
• Effective Date: 15-Jun-2012
• Refers: ASTM D1252-06(2012) - Standard Test Methods for Chemical Oxygen Demand (Dichromate Oxygen Demand) of Water
• Effective Date: 15-Jun-2012
• Refers: ASTM D4691-11 - Standard Practice for Measuring Elements in Water by Flame Atomic Absorption Spectrophotometry
• Effective Date: 01-Sep-2011
• Refers: ASTM D5810-96(2011) - Standard Guide for Spiking into Aqueous Samples
• Effective Date: 01-May-2011
• Refers: ASTM D1245-11 - Standard Practice for Examination of Water-Formed Deposits by Chemical Microscopy
• Effective Date: 01-May-2011
• Refers: ASTM D3370-10 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 01-Dec-2010
• Refers: ASTM D512-10 - Standard Test Methods for Chloride Ion In Water
• Effective Date: 15-Sep-2010
• Refers: ASTM D1129-10 - Standard Terminology Relating to Water
• Effective Date: 01-Mar-2010
• Refers: ASTM D3370-08 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 01-Oct-2008
• Refers: ASTM D4841-88(2008) - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 15-Jul-2008

Overview

The ASTM D3223-17 “Standard Test Method for Total Mercury in Water” is a crucial analytical standard developed by ASTM International. This method specifies procedures for determining total mercury concentrations in water, including fresh water, saline water, and certain industrial and sewage effluents. The standard addresses a range from 0.5 to 10.0 μg Hg/L, helping industries and regulatory agencies accurately monitor mercury, a highly toxic contaminant. Given mercury’s impact on human health and the environment, robust and standardized monitoring, as provided by ASTM D3223-17, is essential for compliance with water quality regulations.

Key Topics

• Measurement Range and Applicability

  • Precisely measures total mercury in waters containing 0.5 to 10.0 μg Hg/L.
  • Applicable to diverse matrices: tap water, industrial discharge, river water, wastewater, and some saline waters.
  • Both organic and inorganic mercury compounds can be determined if properly converted to mercuric ions.

• Test Method Outline

  • Utilizes wet chemical oxidation and reduction steps, converting all mercury to a measurable form.
  • Mercury is quantified via cold vapor atomic absorption spectrophotometry (CVAAS), a highly sensitive technique for low-level mercury detection.

• Sample Handling and Quality Control

  • Emphasizes careful sample preservation to ensure reliability.
  • Requires thorough quality control, including use of calibration standards, blanks, duplicates, spikes, and independent reference materials.
  • Recognizes potential matrix interferences and mandates user validation for new or untested waters.

• Safety and Environmental Considerations

  • Highlights the hazardous nature of mercury and provides guidelines for safe handling and proper waste disposal.
  • Offers specific instructions for neutralizing and disposing of mercury-containing wastes.

Applications

ASTM D3223-17 supports a wide range of applications in environmental monitoring and regulatory compliance:

• Water Quality Testing
  • Essential for regulatory bodies and laboratories monitoring mercury in drinking water, effluents, and natural water bodies.
• Industrial Compliance
  • Used by facilities to monitor discharges and ensure compliance with local, national, and international mercury limits.
• Environmental Remediation
  • Applied in assessing contaminated sites, supporting risk evaluations and remediation efforts.
• Public Health Protection
  • Guides utilities and agencies in minimizing mercury exposure from potable water supplies.

With its highly sensitive cold vapor atomic absorption approach, the standard is reliable for assessing trace levels of mercury in diverse environmental and industrial settings.

Related Standards

Several ASTM standards complement D3223-17, supporting comprehensive water analysis and effective laboratory practice:

• ASTM D512: Test Methods for Chloride Ion in Water
• ASTM D1129: Terminology Relating to Water
• ASTM D1193: Specification for Reagent Water
• ASTM D1252: Test Methods for Chemical Oxygen Demand of Water
• ASTM D1426: Test Methods for Ammonia Nitrogen in Water
• ASTM D2777: Practice for Determination of Precision and Bias of Test Methods for Water
• ASTM D4691: Practice for Measuring Elements in Water by Flame Atomic Absorption Spectrophotometry
• ASTM D5847: Practice for Writing Quality Control Specifications for Water Analysis Methods

These related water analysis standards help ensure consistent, reliable results and extend the analytical capabilities of laboratories and regulatory agencies.

---

Keywords: ASTM D3223-17, mercury in water, total mercury analysis, cold vapor atomic absorption, water quality standards, environmental compliance, mercury monitoring, toxic metals in water, trace analysis, laboratory quality control.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D3223 − 17
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 U.S. Department of Defense.
1. Scope* 1.6 Warning—Mercury has been designated by many regu-
2 latory agencies as a hazardous material that can cause serious
1.1 This test method covers the determination of total
3 medicalissues.Mercury,oritsvapor,hasbeendemonstratedto
mercury in water in the range from 0.5 to 10.0 µg Hg/L (1).
be hazardous to health and corrosive to materials. Caution
Thetestmethodisapplicabletofreshwaters,salinewaters,and
should be taken when handling mercury and mercury contain-
some industrial and sewage effluents. It is the user’s responsi-
ing products. See the applicable product Safety Data Sheet
bility to ensure the validity of this test method for waters of
(SDS) for additional information. Users should be aware that
untested matrices.
selling mercury and/or mercury containing products into your
1.1.1 The analyst should recognize that the precision and
state or country may be prohibited by law.
bias of this standard may be affected by the other constituents
1.7 This standard does not purport to address all of the
inallwaters,astap,industrial,river,andwastewaters.Thecold
safety concerns, if any, associated with its use. It is the
vaporatomicabsorptionmeasurementportionofthismethodis
responsibility of the user of this standard to establish appro-
applicable to the analysis of materials other than water
priate safety and health practices and determine the applica-
(sediments,biologicalmaterials,tissues,etc.)if,andonlyif,an
bility of regulatory limitations prior to use. For specific hazard
initial procedure for digesting and oxidizing the sample is
statements, see 1.6 and 7.8.
carried out, ensuring that the mercury in the sample is
1.8 This international standard was developed in accor-
converted to the mercuric ion, and is dissolved in aqueous
dance with internationally recognized principles on standard-
media (2, 3).
ization established in the Decision on Principles for the
1.2 Both organic and inorganic mercury compounds may be
Development of International Standards, Guides and Recom-
analyzed by this procedure if they are first converted to
mendations issued by the World Trade Organization Technical
mercuric ions. Using potassium persulfate and potassium
Barriers to Trade (TBT) Committee.
permanganate as oxidants, and a digestion temperature of
95°C, approximately 100 % recovery of organomercury com-
2. Referenced Documents
pounds can be obtained (2, 4).
2.1 ASTM Standards:
1.3 The range of the test method may be changed by
D512 Test Methods for Chloride Ion In Water
instrument or recorder expansion or both, and by using a larger
D1129 Terminology Relating to Water
volume of sample.
D1193 Specification for Reagent Water
1.4 The values stated in SI units are to be regarded as
D1245 Practice for Examination of Water-Formed Deposits
standard. No other units of measurement are included in this
by Chemical Microscopy
standard.
D1252 Test Methods for Chemical Oxygen Demand (Di-
chromate Oxygen Demand) of Water
1.5 Amethod for the disposal of mercury-containing wastes
D1426 Test Methods for Ammonia Nitrogen In Water
is also presented (Appendix X1) (5).
D2777 Practice for Determination of Precision and Bias of
Applicable Test Methods of Committee D19 on Water
This test method is under the jurisdiction of ASTM Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents
D4691 Practice for Measuring Elements in Water by Flame
in Water.
Current edition approved June 1, 2017. Published June 2017. Originally Atomic Absorption Spectrophotometry
approved in 1979. Last previous edition approved in 2002 as D3223 – 12. DOI:
10.1520/D3223-17.
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 [e-mail]. 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.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3223 − 17
D4841 Practice for Estimation of Holding Time for Water During the oxidation step chlorides are converted to free
Samples Containing Organic and Inorganic Constituents chlorine which will also absorb radiation at 253.7 nm. Care
D5810 Guide for Spiking into Aqueous Samples must be taken to assure that free chlorine is absent before
D5847 Practice for Writing Quality Control Specifications mercury is reduced and swept into the cell. This may be
for Standard Test Methods for Water Analysis accomplished by using an excess of hydroxylamine sulfate
reagent (25 mL). The dead air space in the reaction flask must
3. Terminology
also be purged before the addition of stannous sulfate. Both
3.1 Definitions: inorganic and organic mercury spikes have been quantitatively
3.1.1 For definitions of terms used in this standard, refer to recovered from sea water using this technique (2).
Terminology D1129.
6.4 Volatile organic materials that could interfere will be
3.2 Definitions of Terms Specific to This Standard: removed with sample digestion as described in 11.2 through
3.2.1 continuing calibration blank, n— a solution contain-
11.4.
ing no analytes (of interest) which is used to verify blank
response and freedom from carryover. 7. Apparatus
NOTE 1—Take care to avoid contamination of the apparatus with
3.2.2 continuing calibration verification, n—a solution (or
mercury. An effective way to clean all glassware is to soak all glass
setofsolutions)ofknownconcentrationusedtoverifyfreedom
apparatus, pipets, beakers, aeration tubes, and reaction flasks in nitric acid
from excessive instrumental drift; the concentration is to cover
(HNO ) (1 + 1), and rinse with mercury-free water or reagent before use.
the range of calibration curve.
7.1 The schematic arrangement of the closed recirculating
3.2.3 total recoverable mercury, n—a descriptive term
systemisshowninFig.1andtheschematicarrangementofthe
relating to the metal forms of mercury recovered in the acid
open one-pass system is shown in Fig. 2.
digestion procedure specified in this test standard.
7.2 Atomic Absorption Spectrophotometer—A commercial
atomic absorption instrument is suitable if it has an open-
4. Summary of Test Method
burner head area in which to mount an absorption cell, and if
4.1 The test method consists of a wet chemical oxidation
it provides the sensitivity and stability for the analyses. Also
which converts all mercury to the mercuric ion; reduction of
instruments designed specifically for the measurement of
mercuric ions to metallic mercury, followed by a cold vapor
atomicabsorptionanalysis (1, 2).Ageneralguideforflameand
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.
6. Interference
6.1 Possible interference from sulfide is eliminated by the
A—Reaction flask G—Hollow cathode mercury lamp
additionofpotassiumpermanganate.Concentrationsashighas B—60-W light bulb H—Atomic absorption detector
C—Rotameter, 1 L of air per minute J— Gas washing bottle containing
20 mg/L of sulfide as sodium sulfide do not interfere with the
0.25 % iodine in a 3 % potassium io-
recovery of added inorganic mercury from distilled water (2).
dide solution
D— Absorption cell with quartz windows K—Recorder, any compatible model
6.2 Copper has also been reported to interfere; however,
E— Air pump, 1 L of air per minute
copper concentrations as high as 10 mg/Lhave no effect on the
F—Glass tube with fritted end
recovery of mercury from spiked samples (2).
FIG. 1 Schematic Arrangement of Equipment for Mercury Mea-
6.3 Seawaters, brines, and industrial effluents high in chlo-
surement by Cold Vapor Atomic Absorption Technique Closed
rides require additional permanganate (as much as 25 mL). Recirculating System
D3223 − 17
NOTE 1—The length and outside diameter of the cell are not critical.
The body of the cell may be of any tubular material but the end windows
mustbeofquartzbecauseoftheneedforUVtransparency.Thelengthand
diameter of the inlet and outlet tubes are not important, but their position
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
smoother readings. A mild pressure in the cell can be tolerated, but too
much pressure may cause the glued-on end windows to pop off. Cells of
this type may be purchased from various supply houses.
FIG. 3 Cell for Mercury Measurement by Cold-Vapor Technique
7.5 Air Pump—A peristaltic pump, with electronic speed
control, capable of delivering 1 L of air per minute may be
used. Regulated compressed air can be used in the open
one-pass system.
7.6 Flowmeter, capable of measuring an air flow of 1 L/min.
A—Reaction flask G—Hollow cathode mercury lamp
B—60-W light bulb H—Atomic absorption detector
7.7 Aeration Tubing—A straight glass frit having a coarse
C—Rotameter, 1 L of air per minute J—Vent to hood
porosityisusedinthereactionflask.Clearflexiblevinylplastic
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
tubing is used for passage of the mercury vapor from the
ute bottle containing 0.25 % iodine in a 3 %
reaction flask to the absorption cell.
potassium iodide solution
F—Glass tube with fritted end
7.8 Lamp—Asmall reading lamp containing a 60-W bulb is
used to prevent condensation of moisture inside the cell. The
FIG. 2 Schematic Arrangement of Equipment for Mercury Mea-
lamp shall be positioned to shine on the absorption cell
surement by Cold Vapor Atomic Absorption Technique Open
One-Pass System 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.
mercury using the cold vapor technique in the working range
(Warning—If the presence of organic vapors is expected, the
specified may be used. Direct reading instruments are also
purityofthedryingagentshouldbedeterminedtoestablishthe
acceptable.
absence of traces of free perchloric acid in the salt. This is to
7.2.1 Mercury Hollow Cathode Lamp.
prevent the formation of perchloric esters, some of which are
7.2.2 Simultaneous Background Correction—Background
known to be violently explosive compounds.)
correction may be necessary to compensate for molecular
absorption that can occur at this mercury wavelength. It is the
7.9 ReactionFlask—A250-to300-mLglasscontainerfitted
analyst’s responsibility to determine the applicable use.
with a rubber stopper may be used.
7.3 Recorder—Any multirange variable speed recorder that
8. Reagents
is compatible with the ultraviolet (UV) detection system is
suitable. 8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
7.4 Absorption Cell—The cell (Fig. 3) is constructed from
all reagents shall conform to the specifications of the Commit-
glass 25.4-mm outside diameter by 114 mm (Note 2).The ends
tee onAnalytical Reagents of theAmerican Chemical Society.
are ground perpendicular to the longitudinal axis and quartz
Other grades may be used, provided it is first ascertained that
windows (25.4-mm diameter by 1.6 mm thickness) are ce-
the reagent is of sufficiently high purity to permit its use
mented in place. Gas inlet and outlet ports (6.4-mm diameter)
without lessening the accuracy of the determination.
are attached approximately 12 mm from each end. The cell is
strapped to a support and aligned in the light beam to give
maximum transmittance. Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
NOTE 2—An all-glass absorption cell, 18 mm in outside diameter by
listed by the American Chemical Society, see Annual Standards for Laboratory
200 mm, with inlet 12 mm from the end, 18-mm outside diameter outlet
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
in the center, and with quartz windows has been found suitable. Methyl and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
methacrylate tubing may also be used. MD.
D3223 − 17
8.2 Purity of Water—Unless otherwise indicated, references days if collected in glass bottles, and within 13 days if
towatershallbeunderstoodtomeanreagentwaterconforming collected in polyethylene bottles (6).
to Specification D1193, Type I. Other reagent water types may
9.3 Samples shall be preserved with HNO (sp gr 1.42) to a
be used, provided it is first ascertained that the water is of
pH of 2 or less immediately at the time of collection, normally
sufficiently high purity to permit its use without adversely
about 2 mL/L of HNO . If only dissolved mercury is to be
affecting the bias and precision of the test method. Type II
determined, the sample, before acidification shall be filtered
water was specified at the time of round-robin testing of this
through a 0.45-µm membrane filter using an all-glass filtering
test method.
apparatus.
8.3 Mercury Solution, Stock (1 mL = 1 mg Hg)—Dissolve
NOTE 6—Alternatively, the pH may be adjusted in the laboratory within
0.1354 g of mercuric chloride (HgCl ) in a mixture of 75 mL
14 days of collection. However, acid must be added at least 24 hours
of water and 10 mLof HNO (sp gr 1.42) and dilute to 100 mL
before analysis to dissolve any metals that adsorb to the container walls.
This could reduce hazards of working with acids in the field when
with water.Apurchased mercury stock solution of appropriate
appropriate.
known purity is also acceptable.
8.4 Mercury Solution, Intermediate (1 mL = 10 µg Hg)—
10. Calibration
Pipet 10.0 mL of the stock mercury solution into a mixture of
10.1 Transfer 0, 1.0, 2.0, 5.0, and 10.0 mL-aliquots of the
500 mL of water and 2 mL of HNO (sp gr 1.42) and dilute to
standard mercury solution containing 0 to 1.0 µg of mercury to
1 L with water. Prepare fresh daily.
a series of reaction flasks. Add enough water to each flask to
8.5 Mercury Solution, Standard (1 mL = 0.1 µg Hg)—Pipet
make a total volume of 100 mL.
10.0mLoftheintermediatemercurystandardintoamixtureof
10.2 Mix thoroughly and add cautiously 5 mLof H SO (sp
2 4
500 mL of water and 2 mL of HNO (sp gr 1.42) and dilute to
gr 1.84) and 2.5 mL of HNO (sp gr 1.42) to each flask.
1 L with water. Prepare fresh daily.
NOTE 7—Loss of mercury may occur at elevated temperatures.
8.6 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
However, with the stated amounts of acid the temperature rise is only
(HNO ).
about 13°C (25–38°C) and no losses of mercury will occur (2).
NOTE 3—If the reagent blank concentration is greater than the method
10.3 Add 15 mLof KMnO solution (8.7) to each bottle and
detection limit, distill the HNO or use a spectrograde acid.
allow to stand at least 15 min.
8.7 Potassium Permanganate Solution (50 g/L)—Dissolve
10.4 Add 8 mL of K S O solution (8.8) to each flask, heat
2 2 8
50 g of potassium permanganate (KMnO ) in water and dilute
for2hina water bath at 95°C, and cool to room temperature.
to1L.
10.5 Turn on the circulating pump and adjust its rate to 1
8.8 Potassium Persulfate Solution (50 g/L)—Dissolve 50 g
L/min.Thepumpmaybeallowedtoruncontinuouslythrough-
of potassium persulfate (K S O ) in water and dilute to 1 L.
2 2 8
out the entire series of samples.
8.9 Sodium Chloride-Hydroxylamine Sulfate Solution (120
10.6 Add 6 mL of sodium chloride-hydroxylamine sulfate
g/L)—Dissolve 120 g of sodium chloride (NaCl) and 120 g of
solution(8.9)toreducetheexcesspermanganate,asevidentby
hydroxylamine sulfate [(NH OH) H SO ] in water and dilute
2 2 2 4
loss of solution color. Refer to Note 4.
to1L.
10.7 After waiting 30 s treat each flask individually by
NOTE 4—The analyst may wish to use hydroxylamine hydrochloride
adding 5 mL of the SnSO solution (8.10) and immediately
instead of hydroxylamine sulfate. The analyst should dissolve 12 g of
attach the bottle to the aeration apparatus forming a closed
hydroxylamine hydrochloride in 100 mL of Type I water.
system. Refer to Note 5.
8.10 Stannous Sulfate Solution (100 g/L)—Dissolve 100 g
10.8 After the absorbance has reached a maximum and the
of stannous sulfate (SnSO ) in water containing 14 mL of
recorder pen has leveled off, prepare the system for the next
H SO (sp gr 1.84) and dilute to 1 L. This mixture is a
2 4
standard by one of the following procedures:
suspension and should be mixed continuously when being
10.8.1 ClosedRecirculatingSystem—Openthebypassvalve
applied as a reagent.
and continue aeration until the absorbance returns to its
NOTE 5—The analyst may wish to use stannous chloride instead of
minimum value. Close the bypass valve, remove the stopper
stannous sulfate. Stannous chloride crystal (100 g in 50 mL) should be
and frit from the reaction flask, and continue the aeration.
dissolved in concentrated HCl. The solution is heated and cooled until
10.8.2 OpenOne-PassSystem—Removethestopperandfrit
dissolved and diluted to 1 L.
from the reaction flask, open the valve, and evacuate the
8.11 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
system with vacuum until the absorbance returns to its mini-
(H SO ).
2 4
mum value. Close the valve and continue aeratio
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D3223 − 12 D3223 − 17
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 U.S. Department of Defense.
1. Scope*
2 3
1.1 This test method covers the determination of total mercury in water in the range from 0.5 to 10.0 μg Hg/L (1). The test
method is applicable to fresh waters, saline waters, and some industrial and sewage effluents. It is the user’s responsibility to ensure
the validity of this test method for waters of untested matrices.
1.1.1 The analyst should recognize that the precision and bias of this standard may be affected by the other constituents in all
waters, as tap, industrial, river, and wastewaters. The cold vapor atomic absorption measurement portion of this method is
applicable to the analysis of materials other than water (sediments, biological materials, tissues, etc.) if, and only if, an initial
procedure for digesting and oxidizing the sample is carried out, ensuring that the mercury in the sample is converted to the mercuric
ion, and is dissolved in aqueous media (2, 3).
1.2 Both organic and inorganic mercury compounds may be analyzed by this procedure if they are first converted to mercuric
ions. Using potassium persulfate and potassium permanganate as oxidants, and a digestion temperature of 95°C, approximately
100 % recovery of organomercury compounds can be obtained (2, 4).
1.3 The range of the test method may be changed by instrument or recorder expansion or both, and by using a larger volume
of sample.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 A method for the disposal of mercury-containing wastes is also presented (Appendix X1) (5).
1.6 Warning—Mercury has been designated by many regulatory agencies as a hazardous material that can cause serious
medical issues. Mercury, or its vapor, has been demonstrated to be hazardous to health and corrosive to materials. Caution should
be taken when handling mercury and mercury containing products. See the applicable product Safety Data Sheet (SDS) for
additional information. Users should be aware that selling mercury and/or mercury containing products into your state or country
may be prohibited by law.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use. For specific hazard statements, see 7.81.6 and 10.8.27.8.
1.8 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D512 Test Methods for Chloride Ion In Water
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
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 in Water.
Current edition approved Sept. 1, 2012June 1, 2017. Published September 2012June 2017. Originally approved in 1979. Last previous edition approved in 2002 as
ε1
D3223 – 02 (2007)D3223 . – 12. DOI: 10.1520/D3223-12. 10.1520/D3223-17.
Adapted from research investigations by the U. S. Environmental Protection Agency’s Analytical Quality Control Laboratory, Cincinnati, OH, and Region IV Surveillance
and Analysis Division, Chemical Services Branch, Athens, GA.
The boldface numbers in parentheses refer to the references at the end of this test method.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3223 − 17
D1245 Practice for Examination of Water-Formed Deposits by Chemical Microscopy
D1252 Test Methods for Chemical Oxygen Demand (Dichromate Oxygen Demand) of Water
D1426 Test Methods for Ammonia Nitrogen In Water
D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits
D4691 Practice for Measuring Elements in Water by Flame Atomic Absorption Spectrophotometry
D4841 Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
D5810 Guide for Spiking into Aqueous Samples
D5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis
3. Terminology
3.1 Definitions:
3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.
3.2 Definitions—Definitions of Terms Specific to This Standard:For
3.2.1 continuing calibration blank, n— a solution containing no analytes (of interest) which is used to verify blank response and
freedom from carryover.
3.2.2 continuing calibration verification, n—a solution (or set of solutions) of known concentration used to verify freedom from
excessive instrumental drift; the concentration is to cover the range of calibration curve.definitions
3.2.3 total recoverable mercury, n—a descriptive term relating to the metal forms of mercury recovered in the acid digestion
procedure specified in this test standard. of terms used in this test method, refer to Terminology D1129.
4. Summary of Test Method
4.1 The test method consists of a wet chemical oxidation which converts all mercury to the mercuric ion; reduction of mercuric
ions to metallic mercury, followed by a cold vapor atomic absorption analysis (1, 2). A general 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 concentration.
5. Significance and Use
5.1 The presence of mercury in industrial discharge, domestic 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.
6. Interference
6.1 Possible interference from sulfide is eliminated by the addition of potassium permanganate. Concentrations as high as 20
mg/L of sulfide as sodium sulfide do not interfere with the recovery of added inorganic mercury from distilled water (2).
6.2 Copper has also been reported to interfere; however, copper concentrations as high as 10 mg/L have no effect on the
recovery of mercury from spiked samples (2).
6.3 Seawaters, brines, and industrial effluents high in chlorides require additional permanganate (as much as 25 mL). During
the oxidation step chlorides are converted to free chlorine which will also absorb radiation at 253.7 nm. Care must be taken to
assure that free chlorine is absent before mercury is reduced and swept into the cell. This may be accomplished by using an excess
of hydroxylamine sulfate reagent (25 mL). The dead air space in the reaction flask must also be purged before the addition of
stannous sulfate. Both inorganic and organic mercury spikes have been quantitatively recovered from sea water using this
technique (2).
6.4 Volatile organic materials that could interfere will be removed with sample digestion as described in 11.2 through 11.4.
7. Apparatus
NOTE 1—Take care to avoid contamination of the apparatus with mercury. Soak all An effective way to clean all glassware is to soak all glass apparatus,
pipets, beakers, aeration tubes, and reaction flasks in nitric acid (HNO ) (1 + 1), and rinse with mercury-free water or reagent before use.
7.1 The schematic arrangement of the closed recirculating system is shown in Fig. 1 and the schematic arrangement of the open
one-pass system is shown in Fig. 2.
7.2 Atomic Absorption Spectrophotometer—A commercial atomic absorption instrument is suitable if it has an open-burner head
area in which to mount an absorption cell, and if it provides the sensitivity and stability for the analyses. Also instruments designed
specifically for the measurement of mercury using the cold vapor technique in the working range specified may be used. Direct
reading instruments are also acceptable.
D3223 − 17
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
0.25 % iodine in a 3 % potassium io-
dide solution
D— Absorption cell with quartz windows K—Recorder, any compatible model
E— Air pump, 1 L of air per minute
F—Glass tube with fritted end
FIG. 1 Schematic Arrangement of Equipment for Mercury Measurement by Cold Vapor Atomic Absorption Technique Closed Recircu-
lating System
7.2.1 Mercury Hollow Cathode Lamp.
7.2.2 Simultaneous Background Correction—Background correction may be necessary to compensate for molecular absorption
that can occur at this mercury wavelength. It is the analyst’s responsibility to determine the applicable use.
7.3 Recorder—Any multirange variable speed recorder that is compatible with the ultraviolet (UV) detection system is suitable.
7.4 Absorption Cell—The cell (Fig. 3) is constructed from glass 25.4-mm outside diameter by 114 mm (Note 2). The ends are
ground perpendicular to the longitudinal axis and quartz windows (25.4-mm diameter by 1.6 mm thickness) are cemented in place.
Gas inlet and outlet ports (6.4-mm diameter) are attached approximately 12 mm from each end. The cell is strapped to a support
and aligned in the light beam to give maximum transmittance.
NOTE 2—An all-glass absorption cell, 18 mm in outside diameter by 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 methacrylate tubing may also be used.
7.5 Air Pump—A peristaltic pump, with electronic speed control, capable of delivering 1 L of air per minute may be used.
Regulated compressed air can be used in the open one-pass system.
7.6 Flowmeter, capable of measuring an air flow of 1 L/min.
7.7 Aeration Tubing—A straight glass frit having a coarse porosity is used in the reaction flask. Clear flexible vinyl plastic tubing
is used for passage of the mercury vapor from the reaction flask to the absorption cell.
7.8 Lamp—A small reading lamp containing a 60-W bulb is used to prevent condensation of moisture inside the cell. The 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 purity of the drying agent
should be determined to establish the 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 Reaction Flask—A 250- to 300-mL glass container fitted with a rubber stopper may be used.
D3223 − 17
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—Vent to hood
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
ute bottle containing 0.25 % iodine in a 3 %
potassium iodide solution
F—Glass tube with fritted end
FIG. 2 Schematic Arrangement of Equipment for Mercury Measurement by Cold Vapor Atomic Absorption Technique Open One-Pass
System
NOTE 1—The length and outside diameter of the cell are not critical. The body of the cell may be of any tubular material but the end windows must
be of quartz because of the need for UV transparency. The length and diameter of the inlet and outlet tubes are not important, but their position 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 smoother
readings. A mild pressure in the cell can be tolerated, but too much pressure may cause the glued-on end windows to pop off. Cells of this type may be
purchased from various supply houses.
FIG. 3 Cell for Mercury Measurement by Cold-Vapor Technique
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 Committee on Analytical Reagents of the American 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.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed by
the American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D3223 − 17
8.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to
Specification D1193, Type I. Other reagent water types may be used, provided it is first ascertained that the water is of sufficiently
high purity to permit its use without adversely affecting the bias and precision of the test method. Type II water was specified at
the time of round-robin testing of this test method.
8.3 Mercury Solution, Stock (1 mL = 1 mg Hg)—Dissolve 0.1354 g of mercuric chloride (HgCl ) in a mixture of 75 mL of water
and 10 mL of HNO (sp gr 1.42) and dilute to 100 mL with water. A purchased mercury stock solution of appropriate known purity
is also acceptable.
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 10.0 mL of the intermediate mercury standard 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.
8.6 Nitric Acid (sp gr 1.42)—Concentrated nitric acid (HNO ).
NOTE 3—If the reagent blank concentration is greater than the method detection limit, distill the HNO or use a spectrograde acid.
8.7 Potassium Permanganate Solution (50 g/L)—Dissolve 50 g of potassium permanganate (KMnO ) in water and dilute to 1
L.
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
8.9 Sodium Chloride-Hydroxylamine Sulfate Solution (120 g/L)—Dissolve 120 g of sodium chloride (NaCl) and 120 g of
hydroxylamine sulfate [(NH OH) H SO ] in water and dilute to 1 L.
2 2 2 4
NOTE 4—The analyst may wish to use hydroxylamine hydrochloride instead of hydroxylamine sulfate. The analyst should dissolve 12 g of
hydroxylamine hydrochloride in 100 mL of Type I water.
8.10 Stannous Sulfate Solution (100 g/L)—Dissolve 100 g of stannous sulfate (SnSO ) in water containing 14 mL of H SO (sp
4 2 4
gr 1.84) and dilute to 1 L. This mixture is a suspension and should be mixed continuously when being applied as a reagent.
NOTE 5—The analyst may wish to use stannous chloride instead of stannous sulfate. Stannous chloride crystal (100 g in 50 mL) should be dissolved
in concentrated HCl. The solution is heated and cooled until dissolved and diluted to 1 L.
8.11 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid (H SO ).
2 4
9. Sampling
9.1 Collect the samples in accordance with Practices D3370. The holding time for the samples can be calculated in accordance
with Practice D4841.
9.2 Collect samples in acid-washed glass or high density-hard polyethylene bottles. Samples shall be analyzed within 38 days
if collected in glass bottles, and within 13 days if collected in polyethylene bottles (6).
9.3 Samples shall be preserved with HNO (sp gr 1.42) to a pH of 2 or less immediately at the time of collection, normally about
2 mL/L of HNO . If only dissolved mercury is to be determined, the sample, before acidification shall be filtered through a 0.45-μm
membrane filter using an all-glass filtering apparatus.
NOTE 6—Alternatively, the pH may be adjusted in the laboratory if the sample is returned within 14 days. within 14 days of collection. However, acid
must be added at least 24 hours before analysis to dissolve any metals that adsorb to the container walls. This could reduce hazards of working with acids
in the field when appropriate.
10. Calibration
10.1 Transfer 0, 1.0, 2.0, 5.0, and 10.0 mL-aliquots of the standard mercury solution containing 0 to 1.0 μg of mercury to a series
of reaction flasks. Add enough water to each flask to make a total volume of 100 mL.
10.2 Mix thoroughly and add cautiously 5 mL of H SO (sp gr 1.84) and 2.5 mL of HNO (sp gr 1.42) to each flask.
2 4 3
NOTE 7—Loss of mercury may occur at elevated temperatures. However, with the stated amounts of acid the temperature rise is only about 13°C
(25–38°C) and no losses of mercury will occur (2).
10.3 Add 15 mL of KMnO solution (8.7) to each bottle and allow to stand at least 15 min.
10.4 Add 8 mL of K S O solution (8.8) to each flask, heat for 2 h in a water bath at 95°C, and cool to room temperature.
2 2 8
10.5 Turn on the circulating pump and adjust its rate to 1 L/min. The pump may be allowed to run continuously throughout the
entire series of samples.
10.6 Add 6 mL of sodium chloride-hydroxylamine sulfate solution (8.9) to reduce the excess permanganate, as evident by loss
of solution color. Refer to Note 4.
10.7 After waiting 30 s treat each flask individually by adding 5 mL of the SnSO solution (8.10) and immediately attach the
bottle to the aeration apparatus forming a closed system. Refer to Note 5.
D3223 − 17
10.8 After the absorbance has reached a maximum and the recorder pen has leveled off, prepare the system for the next standard
by one of the following procedures:
10.8.1 Closed Recirculating System—Open the bypass valve and continue aeration until the absorbance returns to its minimum
value. Close the bypass valve, remove the stopper and frit from the reaction flask, and continue the aeration.
10.8.2 Open One-Pass System—Remove the stopper and frit from the reaction flask, open the valve, and evacuate the system
with vacuum until the absorbance returns to its minimum value. Close the valve and continue aeration. (Warning—Because of
the toxic nature of mercury vapor, precaution must be taken to avoid its inhalation. Therefore, a bypass has been included in the
syste
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