Designation: D 6414 – 01 (Reapproved 2006)

Standard Test Methods for

Total Mercury in Coal and Coal Combustion Residues by
Acid Extraction or Wet Oxidation/Cold Vapor Atomic
Absorption1
This standard is issued under the fixed designation D 6414; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope 3. Terminology
1.1 These test methods cover procedures to determine the 3.1 For definitions of terms used in this standard, refer to
total mercury content in a sample of coal or coal combustion Terminology D 121.
residue.
1.2 The values stated in SI units are regarded as the 4. Summary of Test Method
standard. 4.1 Test Method A—Mercury in the analysis sample is
1.3 This standard does not purport to address all of the solubilized by heating the test sample at a specified tempera-
safety concerns, if any, associated with its use. It is the ture in a mixture of nitric and hydrochloric acids. The acid
responsibility of the user of this standard to establish appro- solutions produced are transferred into a vessel in which the
priate safety and health practices and determine the applica- mercury is reduced to elemental mercury. The mercury vapor is
bility of regulatory limitations prior to use. determined by flameless cold-vapor atomic absorption spec-
troscopy.
2. Referenced Documents 4.2 Test Method B—Mercury in the analysis sample is
2.1 ASTM Standards: 2 solubilized by heating the test sample in a mixture of nitric and
D 121 Terminology of Coal and Coke sulfuric acids with vanadium pentoxide.4 The acid solutions
D 1193 Specification for Reagent Water produced are transferred into a vessel in which the mercury is
D 2013 Practice for Preparing Coal Samples for Analysis reduced to elemental mercury. The mercury vapor is deter-
D 3173 Test Method for Moisture in the Analysis Sample of mined by flameless cold-vapor atomic absorption spectros-
Coal and Coke copy.
D 3180 Practice for Calculating Coal and Coke Analyses NOTE 1—Mercury and mercury salts can be volatilized at low tempera-
from As-Determined to Different Bases tures. Precautions against inadvertent mercury loss should be taken when
D 5142 Test Methods for Proximate Analysis of the Analy- using this method.
sis Sample of Coal and Coke by Instrumental Procedures
IEEE/ASTM SI 10 Standard for Use of the International 5. Significance and Use
System of Units (SI): The Modern Metric System 5.1 The emission of mercury during coal combustion can be
E 691 Practice for Conducting an Interlaboratory Study to an environmental concern.
Determine the Precision of a Test Method 5.2 When representative test portions are analyzed accord-
2.2 ISO Standard3 ing to one of these procedures, the total mercury is represen-
ISO 5725-6:1994 Accuracy of measurement methods and tative of concentrations in the sample.
results-Part 6
6. Apparatus
1
6.1 Apparatus for Test Method A:
These test methods are under the jurisdiction of ASTM Committee D05 on Coal
and Coke and are the direct responsibility of Subcommittee D05.29 on Major
6.1.1 Analytical Balance, with a sensitivity of 0.1 mg.
Elements in Ash and Trace Elements of Coal. 6.1.2 Atomic Absorption Spectrophotometer, with a flame-
Current edition approved April 1, 2006. Published April 2006. Originally less cold-vapor mercury analysis system.
approved in 1999. Last previous edition approved in 2001 as D 6414 - 01. 6.1.3 Digestion Vessels, 100- to 250-mL bottles with an
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
O-ring seal and screw cap. Bottle must be compatible for use
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
3
Available from International Organization for Standardization (ISO), 1 rue de
4
Varembé, Case postale 56, CH-1211, Geneva 20, Switzerland. Crock, J. G., Open-File Report, U.S. Geological Survey, 87–84, p.19.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 D 6414 – 01 (2006)
with aqua regia. Polycarbonate and HDPE are acceptable. mercury standard stock solution to 500 mL with deionized
Bottles and cap assemblies shall be washed in 1-to-1 HCl then water. Further dilute 10 mL of this intermediate solution to 1 L
dried before each use. with deionized water.
8.6 Nitric Acid—Concentrated (HNO3, sp. gr. 1.42).
NOTE 2—Other bottle and cap assemblies may be used provided they
are compatible for use with aqua regia at a temperature of 80°C. 8.7 Hydrochloric Acid—Concentrated (HCl, sp. gr. 1.19).
8.8 Sodium Chloride/Hydroxylamine Sulfate Solution—
6.1.4 Heat Source, a water bath capable of maintaining a Dissolve 12 g 6 0.01 g of sodium chloride and 12 g 6 0.01 g
temperature of 80°C. of hydroxylamine sulfate in water and dilute to 100 mL.
6.1.5 Syringe and Filter, a 20-cm3 syringe and a 1-µm PTFE 8.9 Potassium Permanganate Solution (5 g/100 mL)—
filter to fit syringe. Dissolve 5 g of potassium permanganate (KMnO4) in water
6.2 Apparatus for Test Method B: and dilute to 100 mL.
6.2.1 Analytical Balance, with a sensitivity of 0.1 mg. 8.10 Stannous Chloride Solution (100 g/L)—Dissolve 100 g
6.2.2 Atomic Absorption Spectrophotometer, with a flame- of stannous chloride dihydrate (SnCl2·2 H2O) in 300 mL of
less cold-vapor mercury analysis system. concentrated hydrochloric acid (HCl, sp. gr. 1.19) and CAU-
6.2.3 Digestion Vessels, 16- by 150-mm disposable glass TIOUSLY dilute to 1 L with water. This solution is stable for
test tubes. approximately one week if refrigerated.
6.2.4 Heat Source, an aluminum block with 18-mm holes to 8.11 Certified Reference Material (CRM)—Use Certified
accommodate the disposable test tubes. The block shall be Reference Material (CRM) coals with dry-basis mercury val-
capable of slowly reaching and maintaining a final temperature ues for which confidence limits are issued by a recognized
of 150°C. The block can be heated by placing it on a hot plate certifying agency such as the National Institute of Standards
or it can contain its own internal heating elements. and Technology (NIST). It is recommended that the user verify
the value with the certifying agency before using the CRM coal
7. Sample for quality control purposes.
7.1 Prepare the analysis sample in accordance with Method
D 2013 by pulverizing the material to pass a 250-µm (No. 60) 9. Procedure
sieve. 9.1 Preparation of Test Solution A (Extraction Step):
7.2 Analyze separate test portions for moisture content in 9.1.1 Weigh a test portion of approximately 1 g of the
accordance with Test Method D 3173 or Test Methods D 5142. sample into a digestion bottle. Record the weight (Ws) to the
nearest 0.0001 g.
Test Method A for the Analysis of Mercury by Using Acid 9.1.2 Quantitatively add 2 mL of concentrated nitric acid
Extraction and 6 mL of concentrated hydrochloric acid to the digestion
bottle and secure the cap.
8. Reagents 9.1.3 Transfer the digestion bottle and contents to a water
8.1 Purity of Reagents—Reagent grade chemicals shall be bath that has been heated to 80°C and heat for 1 h. Secure the
used. Unless otherwise indicated, it is intended that all reagents digestion bottle in such a way as to keep the contents below the
shall conform to the specifications of the Committee on surface of the water.
Analytical Reagents of the American Chemical Society where 9.1.4 After 1 h, remove the digestion bottle and allow to
such specifications are available.5 Other grades can be used cool to room temperature.
provided it is first ascertained that the reagent is of sufficiently
NOTE 3—Caution: Carefully relieve the pressure by slowly removing
high purity to permit its use without lessening the accuracy of the cap.
the determination.
8.2 Purity of Acids—Use trace metal purity grade acids or 9.1.5 Add 36.5 mL of water and mix the contents.
equivalent. Redistilled acids are acceptable. 9.1.6 Add 5 mL of 5 % potassium permanganate solution.
8.3 Purity of Water—Use water equivalent to ASTM Type II Allow the mixture to stand for 10 min.
reagent water of Specification D 1193. 9.1.7 Add 0.5 mL of the hydroxylamine sodium chloride
8.4 Mercury Standard Stock Solution [1000 ppm (1000 solution and mix. If a pink color persists for more than 1 min,
µg/mL)]—Dissolve 1.0800 g of mercury (II) oxide (HgO) in a add an additional 0.5 mL of the hydroxylamine sodium
minimum volume of HCl (1+1) and dilute to 1 L with water. chloride solution and mix. Note the total volume and record
Alternatively, use a commercially available stock solution this volume (V) for use in the final calculations.
specifically prepared for atomic absorption spectrometry. 9.2 Preparation of Reagent Blank—Prepare a reagent blank
8.5 Mercury Standard Solution (100 ng/mL)—Prepare the by repeating the procedure in 9.1 but without the test portion of
mercury standard solution fresh daily. Dilute 5 mL of the the sample.
9.3 Preparation of Control Sample:
9.3.1 Prepare a test portion of a CRM coal for analysis using
the procedure described in 9.1. Record the expected value of
5
Reagent Chemicals, American Chemical Society Specifications, American mercury, the certified value in the coal, as CRME.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
9.3.2 Alternatively, weigh a test portion of 1 g of a CRM.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and After the addition of the nitric and hydrochloric acids to the
National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD. digestion bottle, add mercury standard solution (8.5). The

2
 D 6414 – 01 (2006)
volume of mercury standard solution to be added should yield 9.4.4 Analysis of the Reagent Blank—Determine the absor-
an amount of mercury approximately equivalent to that in the bance (Ab) of the reagent blank using the procedure described
CRM coal (Note 4). in 9.4.3.
9.3.3 Calculate the expected value of mercury CRME as 9.4.5 Analysis of the Quality Control Sample—Determine
follows the absorbance (Aqs) of the quality control sample using the
CRME 5 ~Wcrm*CRM 1 Vstandard*0.1!/Wcrm (1) procedure described in 9.4.3.

where: Test Method B for the Analysis of Mercury by Using Wet

Wcrm = dry weight of the CRM coal used for prepa- Oxidation Extraction
ration of the quality control sample, g;
CRM = certified value of mercury in the quality con- 10. Reagents
trol sample; 10.1 Purity of Reagents—Reagent grade chemicals shall be
Vstandard = volume of mercury standard solution added to
used. Unless otherwise indicated, it is intended that all reagents
the digestion bottle, mL; and
shall conform to the specifications of the Committee on
0.1 = the concentration of the mercury standard
Analytical Reagents of the American Chemical Society where
solution, µg/mL.
such specifications are available.5 Other grades can be used
NOTE 4—A test portion of 0.9-g dry weight of a CRM coal with 0.11 provided it is first ascertained that the reagent is of sufficiently
g/g (110 ng/g) of mercury is weighed out as a quality control sample. To high purity to permit its use without lessening the accuracy of
yield an amount approximately equivalent to that present in the CRM coal, the determination.
0.9 mL of the mercury standard solution is added to the digestion bottle
after the addition of the nitric and hydrochloric acids. CRME calculates to
10.2 Purity of Acids—Use trace metal purity grade acids or
0.21 µg/g. equivalent. Redistilled acids are acceptable.
10.3 Purity of Water—Use water equivalent to ASTM Type
9.4 Atomic Absorption Analyses:
II reagent water of Specification D 1193.
9.4.1 Instrument Conditions—Follow the instrument manu-
10.4 Mercury Standard Stock Solution [1000 ppm (1000
facturers recommended procedure to align the optical cell in
µg/mL)]—Dissolve 1.0800 g of mercury (II) oxide (HgO) in a
the beam path of the atomic absorption spectrophotometer and
minimum volume of HCl (1+1) and dilute to 1 L with water.
optimize the performance of the instrument and the flameless
Alternatively, use a commercially available stock solution
cold-vapor apparatus.
specifically prepared for atomic absorption spectrometry.
9.4.2 Instrument Calibration:
10.5 Mercury Standard Solution (100 ng/mL)—Prepare the
9.4.2.1 Prepare 50 mL of 0.5, 1, 3, 5, and 10 ng/mL (ppb) of
mercury standard solution fresh daily. Dilute 5 mL of the
mercury calibration standards in a solution of 10 % HCl by
mercury standard stock solution to 500 mL with deionized
serial dilution of the mercury standard solution.
water. Further dilute 10 mL of this intermediate solution to 1 L
9.4.2.2 Add a specified volume (Vcal) of a calibration
with deionized water.
solution to the reduction flask or reduction system.
10.6 Nitric Acid—Concentrated (HNO3, sp. gr. 1.42).
NOTE 5—If an autosampler equipped with a peristaltic pump is used for 10.7 Hydrochloric Acid—Concentrated (HCl, sp. gr. 1.19).
delivery of both calibration and analyses sample solutions to the reduction 10.8 Sulfuric Acid—H2SO4, sp. gr. 1.83).
system, a specific volume is not required. 10.9 Vanadium Pentoxide, V2O5—Remove traces of mer-
9.4.2.3 Either manually or by means of an autosampling cury by roasting the V2O5 in a fume hood at a temperature
device begin the analyses of the calibration solution by adding below 690°C, the melting point of V2O5, in a porcelain dish
enough stannous chloride solution so as to ensure complete using a muffle furnace or a Fisher burner.
reduction of the mercury in the calibration solution. NOTE 7—Warning: V2O5 is highly toxic, an irritant, and a possible
9.4.2.4 Record the absorbance of the calibration standard. mutagen.
Repeat for each calibration standard.
9.4.3 Analysis of Test Solution A: 10.10 Stannous Chloride Solution (100 g/L)—Dissolve 100
9.4.3.1 Using the 20-cm3 syringe, draw Test Solution A into g of stannous chloride dihydrate (SnCl2·2H2O) in 300 mL of
the syringe. concentrated hydrochloric acid (HCl, sp. gr. 1.19) and CAU-
9.4.3.2 Fit the syringe with a 1-µm filter. TIOUSLY dilute to 1 L with water. This solution is stable for
9.4.3.3 Filter a volume equivalent to Vcal of Test Solution A approximately one week if refrigerated.
into the reduction flask or reduction system. 10.11 Sodium Dichromate, 25 % (w/v) Solution—Dissolve
25 g of Na2Cr2O7·2H2O in water and dilute to 100 mL.
NOTE 6—A laboratory centrifuge may also be used to separate the 10.12 Complex Reducing Solution—Dissolve 30 g of hy-
solids from the test solution. droxylamine hydrochloride and 30 g of sodium chloride (NaCl)
9.4.3.4 Determine the absorbance (As) of the Test Solution in approximately 500 mL of water. Slowly add 100 mL of
A using the procedure described in 9.4.2. concentrated sulfuric acid. Allow the solution to cool, then
9.4.3.5 Using 10 % HCl, dilute test solutions with mercury dilute to 1 L with water.
absorbances greater than the highest calibration standard to 10.13 Certified Reference Material (CRM)—Use Certified
give an estimated absorbance equivalent to the 3-ng/mL Reference Material (CRM) coals with dry-basis mercury val-
calibration standard and reanalyze. ues for which confidence limits issued by a recognized
9.4.3.6 Record the dilution factor as DF. certifying agency such as NIST. It is recommended that the

3
 D 6414 – 01 (2006)
user verify the value with the certifying agency before using 11.4.2.4 Either manually or by means of an autosampling
the CRM coal for quality control purposes device begin the analyses of the calibration solution by adding
enough complex reducing solution and stannous chloride
11. Procedure solution to ensure complete reduction of the mercury in the
11.1 Preparation of Test Solution B: calibration solution.
11.1.1 Weigh a test portion of 0.15 g of the test sample into 11.4.2.5 Record the absorbance of the calibration standard
a 16- by 150-mm disposable test tube. Record the weight (Ws) (Note 9). Repeat for each calibration standard.
to the nearest 0.0001 g. NOTE 9—Automated flow injection systems may have to be modified to
11.1.2 Add approximately 0.1 g of V2O5, 3.5 mL of con- include mixing loops when analyzing samples digested by Method B.
centrated HNO3, and 1.5 mL of concentrated H2SO4. Swirl to Typical over-the-counter mixing loops are made using 4-mm outer
mix the contents. Place the test tube in the aluminum heating diameter glass tubing wrapped around a 14-mm-diameter mandrel. With-
out the mixing loops, foaming in the gas-phase separator may occur. The
block and cover with a watch glass.
foaming interferes with the transfer of mercury vapor from the gas-phase
11.1.3 Adjust the temperature of the heating block so that it separator to the absorption cell of the cold-vapor atomic absorption
gradually reaches a temperature of 150°C in 4 h. Maintain spectrophotometer. Descriptions and diagrams of a manifold used for the
heating at this temperature for 16 h. automated generation of mercury vapor from samples digested according
11.1.4 After heating, carefully remove the test tube from the to Method B are given by J. G. Crock and others.4 Automated flow
aluminum heating block, allow to cool, and dilute the solution injection systems that have been modified to include mixing loops can also
to a final volume of 15 mL (V) with water. Securely cap the test be used to analyze samples digested by Test Method A.
tube and mix the contents. Centrifuge the test tube and its 11.4.3 Analysis of Test Solution B:
contents for 5 min at 1000 rpm. 11.4.3.1 Add a volume equivalent to Vcal of Test Solution B
11.2 Reagent Blank—Prepare a reagent blank by repeating into the reduction flask or reduction system.
the procedure in 11.1 but without the test portion of the sample. 11.4.3.2 Determine the absorbance (As) of the Test Solution
11.3 Quality Control Sample: B using the procedure described in 11.4.2.
11.3.1 Prepare a CRM coal for analysis using the procedure 11.4.3.3 Using 3N H2SO4, dilute test solutions with mercury
described in 11.1. Record the certified value as CRM. absorbances greater than the highest calibration standard to
11.3.2 Alternatively, weigh a test portion of 0.15 g of a give an estimated absorbance equivalent to the 3-ng/mL
CRM. After the addition of the nitric acid, add mercury calibration standard and reanalyze. Record the dilution factor
standard solution (10.5) to the test tube. The volume of the as DF.
mercury standard solution to be added should yield an amount 11.4.3.4 Analysis of the reagent blank—Determine the ab-
of mercury approximately equivalent to that in the CRM coal sorbance (Ab) of the reagent blank using the procedure
(Note 8). Calculate the expected value CRME of mercury described in 11.4.2.
using Eq 1. 11.4.3.5 Analysis of the quality control sample—Determine
NOTE 8—A test portion of 0.15 g of a CRM coal with 0.11 µg/g (110 the absorbance (Aqs) of the quality control sample using the
ng/g) of mercury is weighed out as a quality control sample. To yield an procedure described in 11.4.2.
amount approximately equivalent to that present in the CRM coal, 0.15
mL of the mercury standard solution is added to the test tube after the 12. Calculation
addition of the nitric acid. CRME calculates to 0.21 µg/g.
12.1 These calculations apply to both Test Method A and
11.4 Atomic Absorption Analyses: Test Method B.
11.4.1 Instrument Conditions—Follow the instrument 12.1.1 Calculate the dry weight of each test portion of
manufacturers’ recommended procedure to align the optical sample prepared for analysis as follows
cell in the beam path of the atomic absorption spectrophotom- Wds 5 ~~100 – Ma! * Ws!/100 (2)
eter and optimize the performance of the instrument and the
flameless cold vapor apparatus. where:
11.4.2 Instrument Calibration: Wds = dry sample weight, g;
11.4.2.1 Prepare 500-mL calibration standards of 0.5, 1, 3, Ws = weight of test portion of sample; and
5, and 10 ng/mL (ppb) of mercury by diluting in water aliquots Ma = moisture in the analysis sample calculated according
of the mercury standard solution (10.4) in 115 mL of concen- to Test Method D 3173 or Test Methods D 5142.
trated HNO3, 50 mL of concentrated H2SO4, and 10 mL of the 12.2 Quality Control:
25 % (w/v) sodium dichromate solution. Prepare fresh calibra- 12.2.1 Calculation of Mercury Concentration of the Quality
tion standards every three months. Control Sample:
11.4.2.2 Prepare a 500-mL dilution solution by mixing 115 12.2.1.1 Absorbance matching—Calculate the concentra-
mL of concentrated HNO3, 50 mL of concentrated H2SO4, and tion of mercury in ppm (µg/g) in the quality control sample as
10 mL of the 25 % (w/v) sodium dichromate solution and Mercury ppm ~µg/g! dry basis 5 DF 3 ~V/Vds! 3 C
diluting to the mark with water. Prepare dilution solution every 3 [~A – Ab!/~Ac – Ab!# (3)
three months.
11.4.2.3 Add a specified volume, Vcal, not to exceed 15 mL where:
of a calibration solution to the reduction flask or reduction A = absorbance of the quality control (Aqs) or analysis
system. sample (A);

4
 D 6414 – 01 (2006)

Ac = absorbance of the calibration standard nearest A; where:

Ab = absorbance of the blank; mercury ppm (µg/g) = the mercury value of sample calcu-
C = concentration of the calibration standard, ng/mL; lated according to Eq 3 or Eq 5 in
DF = dilution factor, if any; µg/g and
V = volume of the analysis solution; and CRME = the expected value of mercury in the
Wds = dry sample weight, g. quality control sample in µg/g.
12.2.1.2 Calibration curve: 12.2.2.3 If the mercury recovery is between MLR– and
12.2.1.2.1 Prepare a calibration curve by plotting absor- MLR+, then proceed with calculation of the concentration of
bance of calibration standard minus blank response versus the mercury in the analysis samples.
concentration of the calibration solution in ng/mL. For the 12.2.2.4 If the mercury recovery is not between MLR– and
number of standards specified in this test method, it is MLR+, then check one or all of the following:
recommended that a linear fit of the form y = mx + b be used. 12.2.2.4.1 If absorbance matching was used to calculate the
Other fits can be used but can require the preparation of concentration of the quality control sample, recalculate the
additional standards to ensure adequate degrees of freedom are mercury recovery using two other calibration standards. If the
maintained (Note 10). mercury recovery calculated using both standards falls within
NOTE 10—It is recommended that a minimum five calibration standards the limits of MLR– and MLR+, prepare another portion of the
be used for a linear fit, six for a quadratic, seven for a cubic, and so forth. standard upon which the original mercury recovery was based.
This approach allows for the rejection of a particular calibration standard Determine the absorbance of the new calibration standard.
for a curve while maintaining adequate degrees of freedom. If the mercury recovery calculated from the absorbance of
12.2.1.2.2 Calculate the net absorbance for the quality the new standard is within the MLR– and MLR+ limits, then
control sample as follows proceed with calculation of the concentration of mercury in the
analysis samples.
Anet 5 A – Ab (4)
12.2.2.4.2 If a calibration curve was used to calculate the
where: concentration of the quality control sample, examine the curve
A = absorbance of the quality control (Aqs) or analysis for points that deviate significantly from the curve. Recalculate
sample (A) and the regression eliminating the suspect point(s) (Note 10). If the
Ab = absorbance of the blank. value for the CRM falls within the MLR– and MLR+ limits
12.2.1.2.3 Read the concentration of the quality control based on the recalculated regression, then prepare another
sample from the calibration curve as Cs. portion of the standard(s) eliminated from the regression.
12.2.1.2.4 Calculate the concentration of mercury in ppm Determine the absorbance of the new standard(s). Recalculate
(µg/g) in the quality control sample as follows the regression incorporating the new standards. If the calcu-
Mercury ppm ~µg/g! dry basis 5 DF 3 ~V/Wds! 3 Cs (5) lated mercury recovery of for CRME is within the MLR– and
MLR+ limits, then proceed with calculation of the concentra-
where: tion of mercury in the analysis samples.
Cs = concentration of the quality control sample read 12.2.2.4.3 Verify the concentration of the mercury standard
from the calibration curve, ng/mL; solution from which the calibration standards have been
DF = is the dilution factor, if any; prepared. Prepare a new mercury standard solution from the
V = volume of the analysis solution; and mercury standard stock solution. From the new mercury
Wds = dry sample weight, g. standard solution, prepare a 2-ng/mL mercury solution and a
12.2.2 Calculation of Mercury Recovery in the Quality 4-ng/mL mercury solution. Determine the absorbance of the
Control Sample: two solutions and of the quality control sample. Recalculate the
12.2.2.1 Calculate the CRM confidence factor as follows mercury recovery. If the recalculated values both fall within the
CRMF 5 100 * ~mercury limits/mercury value! (6) MLR– and MLR+ limits, then the original mercury standard
solution is suspect. Prepare fresh calibration solutions from the
where: new mercury standard solution and reanalyze a separate aliquot
mercury limits = the confidence limits from the certificate of the test solutions.
issued by the certifying agency and 12.2.2.5 If it is not possible to reconcile the mercury
mercury value = the mercury value issued by the certifying
recovery within the limits of MLR– and MLR+, then discard all
agency.
solutions and repeat the analysis of all samples.
If CRMF is greater than 30 %, then the mercury recovery
12.3 Calculations for Test Samples—Provided the condi-
limits (MLR) are:
tions in 12.2 are satisfied, calculate the mercury content of the
MLR+ = 100 + CRMF
test samples using the same equation (Eq 3, or Eq 4, Eq 5) as
MLR– = 100 – CRMF.
for the quality control sample.
If CRMF is less than or equal to 30 %, then the MLR are:
MLR+ = 130 13. Report
MLR– = 70. 13.1 Report the results of the mercury analysis on a dry
12.2.2.2 Calculate the mercury recovery from the quality sample basis.
control sample as follows 13.2 Procedures for converting the value obtained on the
Mercury recovery 5 ~mercury ppm ~µg/g!/CRME! 3 100 (7) analysis sample to other basis are described in Practice D 3180.

5
 D 6414 – 01 (2006)
13.3 Report the recovery of mercury in the quality control the NIST and SARM values and those obtained in the
sample. interlaboratory study are given in Table 2.
13.4 Report the digestion method used.
TABLE 2 Comparison of Certified Values for NIST 1630a, NIST
14. Precision and Bias 2692b, and SARM 20 with Interlaboratory Study Values for Total
Mercury in Coal
14.1 Precision—The precision data of this test method for
Reference RR Value, CRM Value, Bias, Significant
the determination of mercury in coal are shown in Table 1. The CRM ppm ppm ppm (95 % Confidence Level)
precision characterized by the repeatability (Sr, r) and repro- NIST 1630a 0.0947 0.0938 0.0009 no
ducibility (SR, R) is described in Table A1.1 in Annex A1. NIST 2692b 0.1187 0.1333 –0.0146 yes
14.1.1 Repeatability Limit (r)—The value below which the SARM 20 0.22 0.25 –0.03 yes
absolute difference between two test results of separate and
consecutive test determinations, carried out on the same
NOTE 11—Whenever possible, the analysis of several reference mate-
sample in the same laboratory by the same operator using the rials, spanning the concentration range of interest, is the most meaningful
same apparatus on samples taken at random from a single way to investigate measurement bias. When a matrix match is possible the
quantity of homogeneous material, may be expected to occur uncertainty in sample measurements can be equated to that observed in
with a probability of approximately 95 %. measurement of the Certified Reference Material (CRM). When such a
14.1.2 Reproducibility Limit (R)—The value below which match is not possible, but a CRM with a related matrix is available, the test
the absolute difference between two test results, carried out in sample uncertainty may be related to those observed when measuring the
different laboratories using samples taken at random from a CRM. Different methods of measurement of a property may not be
capable of equal repeatability. Accordingly, instances could arise where
single quantity of material that is as homogeneous as possible, the method of measurement has greater variability than that or those used
may be expected to occur with a probability of approximately in certification of the CRM.6
95 %.
14.3 An interlaboratory study, designed consistent with
14.2 Bias—Certified Reference Materials NIST 1630a,
Practice E 691, was conducted in 1999. Eleven labs partici-
NIST 2692b, and SARM 20 were included in the interlabora-
pated. The details of the study and supporting data are given in
tory study to ascertain possible bias between reference material
Research Report RR: D-5 1026 filed at ASTM headquarters.
values and those determined by this method. A comparison of
15. Keywords
TABLE 1 Concentration Range and Limits for Repeatability and 15.1 coal; coal combustion residues; cold-vapor atomic
Reproducibility for Mercury in Coal absorption; mercury
Concentration Repeatability Limit Reproducibility Limit
Range, ppm r R 6
ISO 5725-6:1994 Accuracy of measurement methods and results-Part 6: Use in
Hg 0.032–0.585 0.012 + 0.11 –
x 0.003 + 0.25 –
x practice of accuracy values, Section 4.2.3 Comparison with a reference value for one
laboratory.

ANNEX

(Mandatory Information)

A1. PRECISION STATISTICS

A1.1 The precision of this test method, characterized by TABLE A1.1 Repeatability (Sr, r) and Reproducibility (SR, R)
repeatability (Sr, r) and reproducibility (SR, R) has been Parameters Used for Calculation of Precision Statement
determined for the following materials as listed in Table A1.1. Material Average Sr SR r R
hvAb NIST 2692b 0.118667 0.011488 0.014959 0.032166 0.041885
hvCb SARM 20 0.222542 0.015326 0.016086 0.042912 0.045041
A1.2 Repeatability Standard Deviation (Sr)—The standard FGD A-1 0.585 0.026418 0.057547 0.073971 0.161133
deviation of test results obtained under repeatability condi- FGD A-2 0.321167 0.018197 0.023715 0.050952 0.066402
hvAb Pennsylvania 0.114292 0.007706 0.010234 0.021575 0.028656
tions.
hvBb Ohio 0.116708 0.00599 0.009411 0.016771 0.026351
hvBb Colorado 0.032 0.001772 0.003732 0.004961 0.01045
A1.3 Reproducibility Standard Deviation (SR)—The stan- sub A Wyoming 0.087458 0.009753 0.012924 0.027309 0.036187
lig A Texas 0.111083 0.0125 0.016317 0.035 0.045688
dard deviation of test results obtained under reproducibility hvAb NIST 1630a 0.09475 0.00634 0.007655 0.017752 0.021433
conditions.

6
 D 6414 – 01 (2006)

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