Designation: D3223 − 17

Standard Test Method for

Total Mercury in Water1
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
1.1 This test method covers the determination of total latory agencies as a hazardous material that can cause serious
mercury in water in the range from 0.5 to 10.0 µg Hg/L (1).3 medical issues. Mercury, or its vapor, has been demonstrated to
The test method is applicable to fresh waters, saline waters, and be hazardous to health and corrosive to materials. Caution
some industrial and sewage effluents. It is the user’s responsi- should be taken when handling mercury and mercury contain-
bility to ensure the validity of this test method for waters of ing products. See the applicable product Safety Data Sheet
untested matrices. (SDS) for additional information. Users should be aware that
1.1.1 The analyst should recognize that the precision and selling mercury and/or mercury containing products into your
bias of this standard may be affected by the other constituents state or country may be prohibited by law.
in all waters, as tap, industrial, river, and wastewaters. The cold 1.7 This standard does not purport to address all of the
vapor atomic absorption measurement portion of this method is safety concerns, if any, associated with its use. It is the
applicable to the analysis of materials other than water responsibility of the user of this standard to establish appro-
(sediments, biological materials, tissues, etc.) if, and only if, an priate safety and health practices and determine the applica-
initial procedure for digesting and oxidizing the sample is bility of regulatory limitations prior to use. For specific hazard
carried out, ensuring that the mercury in the sample is statements, see 1.6 and 7.8.
converted to the mercuric ion, and is dissolved in aqueous 1.8 This international standard was developed in accor-
media (2, 3). dance with internationally recognized principles on standard-
1.2 Both organic and inorganic mercury compounds may be ization established in the Decision on Principles for the
analyzed by this procedure if they are first converted to Development of International Standards, Guides and Recom-
mercuric ions. Using potassium persulfate and potassium mendations issued by the World Trade Organization Technical
permanganate as oxidants, and a digestion temperature of Barriers to Trade (TBT) Committee.
95°C, approximately 100 % recovery of organomercury com-
2. Referenced Documents
pounds can be obtained (2, 4).
2.1 ASTM Standards:4
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-
1.5 A method for the disposal of mercury-containing wastes chromate Oxygen Demand) of Water
is also presented (Appendix X1) (5). D1426 Test Methods for Ammonia Nitrogen In Water
D2777 Practice for Determination of Precision and Bias of
1
Applicable Test Methods of Committee D19 on 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
D3370 Practices for Sampling Water from Closed Conduits
in Water. D4691 Practice for Measuring Elements in Water by Flame
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.
2
Adapted from research investigations by the U. S. Environmental Protection
4
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 [email protected]. For Annual Book of ASTM
3
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.
 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
3.2.2 continuing calibration verification, n—a solution (or NOTE 1—Take care to avoid contamination of the apparatus with
mercury. An effective way to clean all glassware is to soak all glass
set of solutions) of known concentration used to verify freedom apparatus, pipets, beakers, aeration tubes, and reaction flasks in nitric acid
from excessive instrumental drift; the concentration is to cover (HNO3) (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 system is shown in Fig. 1 and the schematic arrangement of the
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
4. Summary of Test Method atomic absorption instrument is suitable if it has an open-
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
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 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
addition of potassium permanganate. Concentrations as high as B—60-W light bulb H—Atomic absorption detector
20 mg/L of sulfide as sodium sulfide do not interfere with the C—Rotameter, 1 L of air per minute J— Gas washing bottle containing
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/L have 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
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

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.
A—Reaction flask G—Hollow cathode mercury lamp 7.6 Flowmeter, capable of measuring an air flow of 1 L/min.
B—60-W light bulb H—Atomic absorption detector
C—Rotameter, 1 L of air per minute J—Vent to hood
7.7 Aeration Tubing—A straight glass frit having a coarse
D— Absorption cell with quartz windows K— Recorder, any compatible model porosity is used in the reaction flask. Clear flexible vinyl plastic
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 %
potassium iodide solution
reaction flask to the absorption cell.
F—Glass tube with fritted end 7.8 Lamp—A small reading lamp containing a 60-W bulb is
FIG. 2 Schematic Arrangement of Equipment for Mercury Mea-
used to prevent condensation of moisture inside the cell. The
surement by Cold Vapor Atomic Absorption Technique Open lamp shall be positioned to shine on the absorption cell
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
mercury using the cold vapor technique in the working range placed in the line to prevent moisture in the absorption cell.
specified may be used. Direct reading instruments are also (Warning—If the presence of organic vapors is expected, the
acceptable. purity of the drying agent should be determined to establish the
7.2.1 Mercury Hollow Cathode Lamp. absence of traces of free perchloric acid in the salt. This is to
7.2.2 Simultaneous Background Correction—Background prevent the formation of perchloric esters, some of which are
correction may be necessary to compensate for molecular known to be violently explosive compounds.)
absorption that can occur at this mercury wavelength. It is the 7.9 Reaction Flask—A 250- to 300-mL glass container fitted
analyst’s responsibility to determine the applicable use. with a rubber stopper may be used.
7.3 Recorder—Any multirange variable speed recorder that
is compatible with the ultraviolet (UV) detection system is 8. Reagents
suitable. 8.1 Purity of Reagents—Reagent grade chemicals shall be
7.4 Absorption Cell—The cell (Fig. 3) is constructed from used in all tests. Unless otherwise indicated, it is intended that
glass 25.4-mm outside diameter by 114 mm (Note 2). The ends all reagents shall conform to the specifications of the Commit-
are ground perpendicular to the longitudinal axis and quartz tee on Analytical Reagents of the American Chemical Society.5
windows (25.4-mm diameter by 1.6 mm thickness) are ce- Other grades may be used, provided it is first ascertained that
mented in place. Gas inlet and outlet ports (6.4-mm diameter) the reagent is of sufficiently high purity to permit its use
are attached approximately 12 mm from each end. The cell is without lessening the accuracy of the determination.
strapped to a support and aligned in the light beam to give
maximum transmittance. 5
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
to water shall be understood to mean reagent water conforming collected in polyethylene bottles (6).
to Specification D1193, Type I. Other reagent water types may 9.3 Samples shall be preserved with HNO3 (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 HNO3. 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 (HgCl2) in a mixture of 75 mL 14 days of collection. However, acid must be added at least 24 hours
of water and 10 mL of HNO3 (sp gr 1.42) and dilute to 100 mL before analysis to dissolve any metals that adsorb to the container walls.
with water. A purchased mercury stock solution of appropriate This could reduce hazards of working with acids in the field when
known purity is also acceptable. appropriate.

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
500 mL of water and 2 mL of HNO3 (sp gr 1.42) and dilute to 10.1 Transfer 0, 1.0, 2.0, 5.0, and 10.0 mL-aliquots of the
1 L with water. Prepare fresh daily. standard mercury solution containing 0 to 1.0 µg of mercury to
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.
10.0 mL of the intermediate mercury standard into a mixture of
500 mL of water and 2 mL of HNO3 (sp gr 1.42) and dilute to 10.2 Mix thoroughly and add cautiously 5 mL of H2SO4 (sp
1 L with water. Prepare fresh daily. gr 1.84) and 2.5 mL of HNO3 (sp gr 1.42) to each flask.
8.6 Nitric Acid (sp gr 1.42)—Concentrated nitric acid NOTE 7—Loss of mercury may occur at elevated temperatures.
However, with the stated amounts of acid the temperature rise is only
(HNO3). 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 mL of KMnO4 solution (8.7) to each bottle and
detection limit, distill the HNO3 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 K2S2O8 solution (8.8) to each flask, heat
50 g of potassium permanganate (KMnO4) in water and dilute
for 2 h in a water bath at 95°C, and cool to room temperature.
to 1 L.
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. The pump may be allowed to run continuously through-
of potassium persulfate (K2S2O8) in water and dilute to 1 L.
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) to reduce the excess permanganate, as evident by
hydroxylamine sulfate [(NH2OH)2H2SO4] in water and dilute
loss of solution color. Refer to Note 4.
to 1 L.
10.7 After waiting 30 s treat each flask individually by
NOTE 4—The analyst may wish to use hydroxylamine hydrochloride
instead of hydroxylamine sulfate. The analyst should dissolve 12 g of
adding 5 mL of the SnSO4 solution (8.10) and immediately
hydroxylamine hydrochloride in 100 mL of Type I water. attach the bottle to the aeration apparatus forming a closed
system. Refer to Note 5.
8.10 Stannous Sulfate Solution (100 g/L)—Dissolve 100 g
of stannous sulfate (SnSO4) in water containing 14 mL of 10.8 After the absorbance has reached a maximum and the
H2SO4 (sp gr 1.84) and dilute to 1 L. This mixture is a recorder pen has leveled off, prepare the system for the next
suspension and should be mixed continuously when being standard by one of the following procedures:
applied as a reagent. 10.8.1 Closed Recirculating System—Open the bypass valve
and continue aeration until the absorbance returns to its
NOTE 5—The analyst may wish to use stannous chloride instead of
stannous sulfate. Stannous chloride crystal (100 g in 50 mL) should be
minimum value. Close the bypass valve, remove the stopper
dissolved in concentrated HCl. The solution is heated and cooled until and frit from the reaction flask, and continue the aeration.
dissolved and diluted to 1 L. 10.8.2 Open One-Pass System—Remove the stopper and frit
8.11 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid from the reaction flask, open the valve, and evacuate the
(H2SO4). system with vacuum until the absorbance returns to its mini-
mum value. Close the valve and continue aeration.
9. Sampling (Warning—Because of the toxic nature of mercury vapor,
precaution must be taken to avoid its inhalation. Therefore, a
9.1 Collect the samples in accordance with Practices bypass has been included in the system to either vent the
D3370. The holding time for the samples can be calculated in mercury vapor into an exhaust hood or pass the vapor through
accordance with Practice D4841. some absorbing media such as: (a) equal volumes of 0.1 N
9.2 Collect samples in acid-washed glass or high density- KMnO4 solution and 10 % H2SO4, or (b) 0.25 % iodine in 3 %
hard polyethylene bottles. Samples shall be analyzed within 38 KI solution.)
 D3223 − 17
10.9 Proceed with the standards and directly read the One hundred and one laboratories from the United States and
concentration of the standard or construct a standard curve by Canada, including federal, state and local agencies, universities
plotting peak height versus micrograms of mercury. and private and industrial groups, participated in the interlabo-
ratory study.
11. Procedure
NOTE 9—If the analyst uses hydroxylamine hydrochloride instead of
11.1 Transfer 100 mL or an aliquot diluted to 100 mL
hydroxylamine sulfate and stannous chloride instead of stannous sulfate,
containing not more than 1.0 µg of mercury to a reaction flask. then it is the analyst’s responsibility to determine the precision and bias of
11.2 Add cautiously 5 mL of H2SO4 (sp gr 1.84) and 2.5 mL this test method.
of HNO3 (sp sr 1.42) mixing after each addition (10.8.2). 13.2 Eight water sample concentrates were prepared in
11.3 Add 15 mL of KMnO4 solution (8.7) to each sample sealed glass ampules by dissolving weighed amounts of
bottle. Shake and add additional portions of KMnO4 solution reagent grade chemicals in reagent water, Type II, to produce
until the purple color persists for at least 15 min. accurately known concentrations of inorganic and organic
mercury. All eight samples contained the same ratio of inor-
11.4 Add 8 mL of K2S2O8 solution (8.8) to each flask and
ganic to organic mercury, 40 to 60, as mercuric chloride and
heat for 2 h in a water bath (between 65°C and 95°C) making
methyl mercury chloride, respectively.
certain that the samples do not boil and cool to room
temperature. 13.3 Each laboratory was instructed to dilute a separate
5.0-mL aliquot of each concentrate to 1 L with reagent water
NOTE 8—Many laboratories have found block digestion systems a
useful way to digest samples for trace metals analysis. Systems typically and to 1L with a natural water or wastewater of their choice.
consist of either a metal or graphite block with wells to hold digestion Then, the laboratory was instructed to perform a single analysis
tubes. The block temperature controller must be able to maintain unifor- on each of the resulting sixteen samples. The natural water was
mity of temperature across all positions of the block. The digestion block also analyzed without a spike to determine the background
must be capable of maintaining a temperature between 65°C and 95°C. level of mercury.
For trace metals analysis, the digestion tubes should be constructed of
polypropylene and have a volume accuracy of at least 0.5 %. All lots of 13.4 The precision of this test method within the range from
tubes should come with a certificate of analysis to demonstrate suitability 0.2 to 10 µg/L mercury may be expressed as follows:
for their intended purpose. If a block digestion system is used, reduced
In reagent water, Type II:
volumes of samples and reagents will be required. Make sure that the
reagent volumes maintain the same proportions as in the macro method. S t 5 0.307X10.183
11.5 Turn on the circulating system and adjust its rate to 1 S 0 5 0.076X10.293
L/min. The pump may be allowed to run continuously through-
out the entire series of samples. In natural waters:
11.6 Add 6 mL of sodium chloride-hydroxylamine sulfate S t 5 0.386X10.107
solution (8.9) to reduce the excess permanganate as evident by S 0 5 0.145X10.023
loss of solution color. Refer to Note 4. where:
11.7 Wait 30 s and add 5 mL of SnSO4 solution (8.10) to St = overall precision,
each flask individually and immediately attach it to the aeration S0 = single-operator precision, and
apparatus. Refer to Note 5. X = determined concentration of mercury, µg/L.
11.8 Continue as described in 10.8. 13.5 Bias—Recoveries of known amounts of mercury are
12. Calculation shown in Table 1.
12.1 Read directly from the instrument or determine the 13.6 These data apply to fresh water, saline waters, and
peak height of the unknown from the recorder chart and read some industrial and sewage effluents. It is the analyst’s
the micrograms of mercury from the standard curve. responsibility to ensure the validity of the test method to waters
of other matrices or to a particular matrix.
12.2 Calculate the mercury concentration in the sample as
follows: 13.7 Precision and bias for this test method conform to
Practice D2777 – 77, which was in place at the time of
Mercury ~ total! , µg/L 5 ~ W 3 1000! /S (1)
collaborative testing. Under the allowances made in 1.4 of
where: Practice D2777 – 13, these precision and bias data do meet
W = mercury in aliquot determined from calibration curve, existing requirements for interlaboratory studies of Committee
µg, and D19 test methods.
S = aliquot used for analysis, mL.
14. Quality Control (QC)
13. Precision and Bias (7, 8)6 14.1 In order to be certain that analytical values obtained
13.1 ASTM and the U.S. Environmental Protection Agency using these test methods are valid and accurate within the
conducted a joint study of this test method in October 1972. confidence limits of the test, the following QC procedures must
be followed when analyzing mercury.
6
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D19-1019. Contact ASTM Customer
Service at [email protected].
 D3223 − 17
TABLE 1 Determination of Precision and Bias within the limits given in Table 1. If a concentration other than
Statistically the recommended concentration is used, refer to Practice
Amount Amount Significant, Overall D5847 for information on applying the F test and t test in
Degrees of
Added, Found, % Bias 95 % Precision,
µg/L Hg µg/L Hg Confidence St
Freedom evaluating the acceptability of the mean and standard devia-
Level tion.
Reagent water, Type II
0.21 0.418 +99.0 yes 0.226 71
14.4 Laboratory Control Sample (LCS):
0.27 0.450 +66.7 yes 0.213 70 14.4.1 To ensure that the test method is in control, prepare
0.51 0.653 +28.0 yes 0.377 75 and analyze a LCS containing a mid-range concentration of
0.60 0.744 +24.0 yes 0.344 71
3.4 3.49 +0.03 no 0.71 74
mercury with each batch (laboratory-defined or 20 samples).
4.1 4.28 +3.9 no 0.80 73 The laboratory control samples for a large batch should cover
8.8 8.48 −3.6 no 1.56 72 the analytical range when possible. It is recommended, but not
9.6 9.38 −2.3 no 1.67 72
Natural water of choice
required to use a second source, if possible and practical for the
0.21 0.349 +66.2 yes 0.174 56 LCS. The LCS must be taken through all of the steps of the
0.27 0.414 +53.3 yes 0.262 59 analytical method including sample preservation and pretreat-
0.51 0.674 +32.2 yes 0.381 64
0.60 0.709 +18.2 yes 0.359 61
ment. The result obtained for the LCS shall fall within 615 %
3.4 3.41 +0.3 no 0.71 66 of the known concentration.
4.1 3.81 −7.1 yes 0.72 62 14.4.2 If the result is not within these limits, analysis of
8.8 8.77 −0.34 no 1.68 63
9.6 9.10 −5.2 no 1.98 60
samples is halted until the problem is corrected, and either all
the samples in the batch must be reanalyzed, or the results must
be qualified with an indication that they do not fall within the
performance criteria of the test method.
14.2 Calibration and Calibration Verification: 14.5 Method Blank:
14.2.1 Analyze at least three working standards containing 14.5.1 Analyze a reagent water test blank with each
concentrations of mercury that bracket the expected sample laboratory-defined batch. The concentration of mercury found
concentration prior to analysis of samples to calibrate the in the blank should be less than 0.5 times the lowest calibration
instrument. standard. If the concentration of mercury is found above this
14.2.2 Verify instrument calibration after standardization by level, analysis of samples is halted until the contamination is
analyzing a standard at the concentration of one of the eliminated, and a blank shows no contamination at or above
calibration standards. The absorbance shall fall within 4 % of this level, or the results must be qualified with an indication
the absorbance from the calibration. Alternately, the concen- that they do not fall within the performance criteria of the test
tration of a mid-range standard should fall within 615 % of the method.
known concentration. Analyze a calibration blank to verify 14.6 Matrix Spike (MS):
system cleanliness. The blank result should be less than the 14.6.1 To check for interferences in the specific matrix
method reporting limit. being tested, perform a MS on at least one sample from each
14.2.3 If calibration cannot be verified, recalibrate the laboratory-defined batch by spiking an aliquot of the sample
instrument. with a known concentration of mercury and taking it through
14.2.4 It is recommended to analyze a continuing calibra- the analytical method.
tion blank (CCB) and continuing calibration verification 14.6.2 The spike concentration plus the background concen-
(CCV) at a 10 % frequency. The CCB result should be less than tration of mercury must not exceed the high calibration
the method reporting limit. The CCV results should fall within standard. The spike must produce a concentration in the spiked
the expected precision of the method or 615 % of the known sample that is 2 to 5 times the analyte concentration in the
concentration. unspiked sample, or 10 to 50 times the detection limit of the
14.3 Initial Demonstration of Laboratory Capability: test method, whichever is greater.
14.3.1 If a laboratory has not performed the test before, or if 14.6.3 Calculate the percent recovery of the spike (P) using
there has been a major change in the measurement system, for the following formula:
example, new analyst, new instrument, etc., a precision and P 5 100 @ A ~ V s 1V ! 2 B V s #
bias study must be performed to demonstrate laboratory (2)
CV
capability.
14.3.2 Analyze seven replicates of a standard solution where:
prepared from an Independent Reference Material containing a A = analyte known concentration (µg/L) in spiked sample,
mid-range concentration of mercury. The matrix and chemistry B = analyte known concentration (µg/L) in unspiked
of the solution should be equivalent to the solution used in the sample,
collaborative study. Each replicate must be taken through the C = known concentration (µg/L) of analyte in spiking
complete analytical test method including any sample preser- solution,
vation and pretreatment steps. Vs = volume (mL) of sample used, and
14.3.3 Calculate the mean and standard deviation of the V = volume (mL) of spiking solution added.
seven values and compare to the acceptable ranges of bias in 14.6.4 The percent recovery of the spike shall fall within the
Table 1. This study should be repeated until the recoveries are limits based on the analyte concentration, listed in Guide
 D3223 − 17
D5810, Table 1. If the percent recovery is not within these using an F test. Refer to 6.4.4 of Practice D5847 for informa-
limits, a matrix interference may be present in the sample tion on applying the F test.
selected for spiking. Under these circumstances, one of the 14.7.3 If the result exceeds the precision limit, the batch
following remedies must be employed: the matrix interference must be reanalyzed or the results must be qualified with an
must be removed, all samples in the batch must be analyzed by indication that they do not fall within the performance criteria
a test method not affected by the matrix interference, or the of the test method.
results must be qualified with an indication that they do not fall 14.8 Independent Reference Material (IRM):
within the performance criteria of the test method. Note: 14.8.1 In order to verify the quantitative value produced by
acceptable spike recoveries are dependent on the concentration the test method, analyze an IRM submitted as a regular sample
of the component of interest. See Guide D5810 for additional (if practical) to the laboratory at least once per quarter. The
information. concentration of the reference material should be in the
14.7 Duplicate: concentration mid-range for the method chosen. The value
14.7.1 To check the precision of sample analyses, analyze a obtained must fall within the control limits established by the
sample in duplicate with each batch. If the concentration of the laboratory.
analyte is less than five times the detection matrix spike
duplicate (MSD) should be used. 15. Keywords
14.7.2 Calculate the standard deviation of the duplicate 15.1 atomic absorption; cold vapor technique; mercury;
values and compare to the precision in the collaborative study total mercury

APPENDIX

(Nonmandatory Information)

X1. DISPOSAL OF MERCURY-CONTAINING WASTES (5)

X1.1 Introduction X1.2.3 Stir in small portions of sodium thiosulfate solution

X1.1.1 The practices described in this Appendix may not be (40 to 50 %, w/v) while the combined alkaline wastes are still
legal in some jurisdictions. warm and until no further precipitation seems to occur.
X1.1.2 Mercury salts are components of the wastes from the X1.2.4 Allow the precipitate to settle and draw off a few
following ASTM determinations: Test Methods D1252, millilitres of the clear supernatant liquid making sure the pH is
D1426, and D512 and Practice D1245. Also, mercuric chloride still above 10, and then add an equal volume of sodium
is often used to preserve water samples for nitrogen and thiosulfate solution. If the supernatant still contains dissolved
phosphorus analysis. mercury, a precipitate will rapidly form, indicating that addi-
X1.1.3 Mercury salts may be retained most safely in the tional sodium thiosulfate shall be added to the waste slurry.
sulfide form at high pH. Acidic solutions should be neutralized
and combined with alkaline wastes and water samples contain- X1.2.5 Decant or siphon off the clear tested supernatant and
ing mercury preservatives. To precipitate mercury, a conve- discard it after the precipitate has settled.
nient source of the sulfide ion is sodium thiosulfate. However, X1.2.6 Wash the precipitate twice with water containing a
it should not be added to acidified wastes because of its rapid trace of NaOH, allow to settle, and discard both of the clear
decomposition to elemental sulfur. The sulfur which precipi- washings.
tates increases the volume of sludge which must be processed
and stored. X1.2.7 Dry the washed precipitate first in air, then in an
X1.1.4 Mercury sulfide is insoluble and is stable to most oven at a temperature no higher than 110°C.
reagents except aqua regia and bromine. Bacterial conversions X1.2.8 Store the dry solids until a sufficient quantity has
to methyl mercury is prevented by maintaining the pH above accumulated to justify shipment to a commercial reprocessor
10. (5).7 Metallic mercury and waste organomercurials should be
X1.2 Procedure stored in suitable airtight containers until a commercial repro-
X1.2.1 Dilute all combined acidic wastes to about twice cessor can be contacted for specific shipping instructions.7
their original volume. NOTE X1.1—It is the responsibility of the analyst to ensure that the
X1.2.2 Adjust the pH to greater than 7 by slowly adding supernatant and the precipitate are disposed of properly, meeting disposal
sodium hydroxide solution (40 to 50 %, w/v) with stirring and regulations.
combine this neutralized waste and any pooled alkaline wastes
with stirring. At this point the combined wastes should have a
pH of 10 or higher; if not, add sodium hydroxide until a pH of 7
Names of suitable reprocessors of mercury are available from ASTM Interna-
10 to 11 is attained. tional Headquarters.
 D3223 − 17

REFERENCES

(1) Hatch, W. R. and Ott, W. L., “Determination of Sub-Microgram (5) Dean, R. B., Williams, R. T., and Wise, R. H.,“ Disposal of Mercury
Quantities of Mercury by Atomic Absorption Spectrophotometry,” Wastes From Water Laboratories,” Environmental Science and
Analytical Chemistry, Vol 40, 1968, p. 2085. Technology, Vol 5, 1971, p. 1044.
(2) Kopp, J. F., Longbottom, M. C., and Lobring, L. B.,“ Cold Vapor (6) “Mercury Preservation Study,” Environmental Protection Agency,
Method for Determining Mercury,” Vol 64, 1972, p. 20. Region IV, Surveillance and Analysis Division, Athens, GA (not
(3) Uthe, J. F., Armstrong, F. A. J., and Stainton, M. P., “Mercury published).
Determination in Fish Samples by Wet Digestion and Flameless (7) “ASTM-EPA Method Study of Total Mercury in Water,” Environmen-
Atomic Absorption Spectrophotometry,” Journal of Fisheries Re- tal Protection Agency, Analytical Quality Control Laboratory,
search Board of Canada, Vol 27, 1970, p. 805. Cincinnati, OH, December 1972.
(4) “Mercury Recovery Study,” Environmental Protection Agency, Re-
(8) Water Quality Parameters, ASTM STP 573, 1975, pp. 566–580.
gion IV Surveillance and Analysis Division, Athens, GA (not pub-
lished).

SUMMARY OF CHANGES

Committee D19 has identified the location of selected changes to this standard since the last issue (D3223 –
12) that may impact the use of this standard. (Approved June 1, 2017.)

(1) Revised Section 1 to include warning information mercury. (5) Revised Note 8 to include information about the use of
(2) Revised Section 3 to updated and add terms. block digestion systems.
(3) Revised Note 6 to allow for pH of the samples in the (6) Revised Section 14.
laboratory.
(4) Revised 10.9 and 12.1 to allow for direct reading instru-
ments.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or [email protected] (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222
Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/