NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.

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Designation: D1976 − 18

Standard Test Method for

Elements in Water by Inductively-Coupled Plasma Atomic
Emission Spectroscopy1
This standard is issued under the fixed designation D1976; 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.

1. Scope* D1129 Terminology Relating to Water

1.1 This test method covers the determination of dissolved, D1193 Specification for Reagent Water
total-recoverable, or total elements in drinking water, ground D2777 Practice for Determination of Precision and Bias of
water, surface water, domestic, commercial or industrial Applicable Test Methods of Committee D19 on Water
2,3
wastewaters, within the following concentration ranges: D3370 Practices for Sampling Water from Closed Conduits
D4841 Practice for Estimation of Holding Time for Water
1.2 It is the user’s responsibility to ensure the validity of the
Samples Containing Organic and Inorganic Constituents
test method for waters of untested matrices.
D5673 Test Method for Elements in Water by Inductively
1.3 The values stated in SI units are to be regarded as Coupled Plasma—Mass Spectrometry
standard. No other units of measurement are included in this D5744 Test Method for Laboratory Weathering of Solid
standard. Materials Using a Humidity Cell
1.4 This standard does not purport to address all of the D5810 Guide for Spiking into Aqueous Samples

iTeh Standards
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
D5847 Practice for Writing Quality Control Specifications
for Standard Test Methods for Water Analysis
D6234 Test Method for Shake Extraction of Mining Waste
(https://standards.iteh.ai)
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use. by the Synthetic Precipitation Leaching Procedure
For specific hazard statements, see Note 2 and Section 9. D8006 Guide for Sampling and Analysis of Residential and
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1.5 This international standard was developed in accor-
dance with internationally recognized principles on standard-
Commercial Water Supply Wells in Areas of Exploration
and Production (E&P) Operations
ization established in the Decision on Principles for the E1915 Test Methods for Analysis of Metal Bearing Ores and
Development of International Standards, Guides and Recom- Related Materials for Carbon, Sulfur, and Acid-Base
ASTM D1976-18Characteristics
mendations issued by the World Trade Organization Technical
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Barriers to Trade (TBT) Committee. E2242 Test Method for Column Percolation Extraction of
Mine Rock by the Meteoric Water Mobility Procedure
2. Referenced Documents
2.2 USEPA Standards:2
2.1 ASTM Standards:4
Method 200.7 Determination of Metals and Trace Elements
D1066 Practice for Sampling Steam
in Water and Wastes by Inductively Coupled Plasma-
1
Atomic Emission Spectrometry
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. 3. Terminology
Current edition approved July 1, 2018. Published July 2018. Originally approved
in 1991. Last previous edition approved in 2012 as D1976 – 12. DOI: 10.1520/ 3.1 Definitions:
D1976-18. 3.1.1 For definitions of terms used in this standard, refer to
2
The detailed report of EPA Method Study 27, Method 200.7 is available from Terminology D1129.
the National Technical Information Service, 5285 Port Royal Road, Springfield, VA.
A summary of the project is available from the U.S. Environmental Protection 3.2 Definitions of Terms Specific to This Standard:
Agency, Environmental Monitoring and Support Laboratory, Cincinnati, OH,
http://www.epa.gov.
3.2.1 calibration blank, n—a volume of water containing
3
Fishman, M. J. and Friedman, L., “Methods for Determination of Inorganic the same acid matrix as the calibration standards (see 11.1).
Substances in Water and Fluvial Sediments,” U.S. Geological Survey Techniques of
Water-Resources Investigations, Book 5, Chapter D1066, Open File Report 85-495,
3.2.2 calibration standards, n—a series of known standard
1985, p. 659–671. solutions used by the analyst for calibration of the instrument
4
For referenced ASTM standards, visit the ASTM website, www.astm.org, or (preparation of the analytical curve) (see 8.9).
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on 3.2.3 instrumental detection limit, n—the concentration
the ASTM website. equivalent to a signal, due to the analyte, that is equal to three

*A Summary of Changes section appears at the end of this standard

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1
 D1976 − 18
TABLE 1 Summary of Tested Concentration Ranges toring during exploration, hydraulic fracturing, production,
Element From To Unit closure and reclamation activities related to oil and gas
Aluminum 0.083 1.43 µg/mL operations (see Guide D8006).
Antimony 0.411 1.41 µg/mL 5.2.1 Minimum analyses include arsenic, barium, iron,
Arsenic 0.083 0.943 µg/mL
Barium 0.030 250 µg/mL magnesium, sodium, calcium, manganese, and lead.
Beryllium 0.017 0.076 µg/mL 5.2.2 Boron, potassium, chromium, selenium, cadmium,
Boron 0.330 1.18 µg/mL
Cadmium 0.018 0.776 µg/mL
and strontium may be required on a site specific basis.
Calcium 0.400 1100 µg/mL 5.2.3 The most abundant elements in oil and gas produced
Chromium 0.025 0.47 µg/mL water are sodium, potassium, lithium, magnesium, calcium,
Cobalt 0.058 0.843 µg/mL
Copper 0.017 0.189 µg/mL
strontium, iron, silica, phosphorus, and sulfur.
Iron 0.074 2.34 µg/mL 5.3 The test method is useful for multi-element analysis of
Lead 0.085 0.943 µg/mL
Lithium 0.800 450 µg/mL acid rock drainage and other major and some trace elements in
Magnesium 0.073 4.62 µg/mL mining influenced water.
Manganese 0.017 0.94 µg/mL
Molybdenum 0.073 1.09 µg/mL 5.4 Where low quantitation limits are required, Test Method
Nickel 0.043 0.943 µg/mL D5673 may be applicable.
Phosphorus 10.0 310 µg/mL
Potassium 8.00 5200 µg/mL 5.5 The test method is also useful for testing leachates and
Selenium 0.083 0.755 µg/mL
Silica 1.00 3000 µg/mL
effluents for ore and mining and metallurgical waste charac-
Silver 0.017 0.189 µg/mL terization tests including Test Methods D6234, E2242, D5744,
Sodium 5.00 3500 µg/mL and solutions from the Biological Acid Production Potential
Strontium 0.500 500 µg/mL
Sulfur 2.00 600 µg/mL
and Peroxide Acid Generation Methods in the Appendix of Test
Thallium 0.126 0.953 µg/mL Methods E1915.
Vanadium 0.041 1.877 µg/mL
Zinc 0.068 0.759 µg/mL
6. Interferences

iTeh Standards
times the standard deviation of a series of ten replicate
6.1 Several types of interference effects may contribute to
inaccuracies in the determination of trace elements. These
interferences can be summarized as follows:
3.2.4 laboratory control (https://standards.iteh.ai)
measures of a reagent-blank signal at the same wavelength.
6.1.1 Spectral interferences can be categorized as (1) over-
sample, n—a solution with the
lap of a spectral line from another element; (2) unresolved

3.2.5 reagent blank, n—a volume Document

of water containing the Preview
certified concentration(s) of the analytes.
overlap of molecular band spectra; (3) background contribution
from continuous or recombination phenomena; and (4) back-
same matrix as the calibration standards, carried through the ground contribution from stray light from line emission of high
entire analytical procedure. concentration elements.
3.2.6 total, n—the concentration determined on an ASTM D1976-18
unfiltered 6.1.1.1 The effects described in 6.1.1 can be compensated
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sample following vigorous digestion (see 12.3). for by utilizing a computer correction of the raw data, requiring
3.2.7 total-recoverable, adj—determinable by the digestion the monitoring and measurement of the interfering element.
method that is included in this procedure (see 12.2). The second effect may require selection of an alternate wave-
length. The third and fourth effects can usually be compensated
4. Summary of Test Method for by a background correction adjacent to the analyte line.
4.1 Elements are determined, either sequentially or 6.1.1.2 Table 2 lists some interference effects for the rec-
simultaneously, by inductively-coupled argon plasma optical ommended wavelengths given in Table 2. The data in Table 2
emission spectroscopy. are intended for use only as a rudimentary guide for the
indication of potential spectral interferences. For this purpose,
4.2 A background correction technique may be used to linear relations between concentration and intensity for the
compensate for variable background contribution from high analytes and the interferents can be assumed.
concentrations of major and trace elements. 6.1.1.3 Only those interferents listed in Table 2 were inves-
5. Significance and Use tigated for the analytes in Table 3. The blank spaces in Table 2
indicate that measurable interferences were not observed for
5.1 This test method is useful for the determination of the interferent concentrations listed in Table 4. Generally,
element concentrations in many natural waters and wastewa- interferences were considered as discernible if the interferent
ters. It has the capability for the simultaneous determination of produced interference peaks or background shifts that corre-
up to 29 elements. High sensitivity analysis and larger dynamic sponded to 2 to 5 % of the peaks generated by the analyte
range can be achieved for some elements that are difficult to concentrations listed in Table 3.
determine by other techniques such as Flame Atomic Absorp- 6.1.2 Physical interferences are generally considered to be
tion. effects associated with the sample nebulization and transport
5.2 The test method is useful for multi-element analysis of processes. Such properties as change in viscosity and surface
domestic and commercial well produced drinking water for tension can cause significant inaccuracies, especially in
metals and nonmetals for use in baseline analysis and moni- samples that may contain high dissolved solids or acid

2
 D1976 − 18
TABLE 2 Analyte Concentration Equivalents, mg/L, Arising from Interferents at the 100 mg/L LevelA
Wavelength, Interferent
Analyte
nm Al Ca Cr Cu Fe Mg Mn Ni Ti V
Aluminum 308.215 ... ... ... ... ... ... 0.21 ... ... 1.4
Antimony 206.833 0.47 ... 2.9 ... 0.08 ... ... ... 0.25 0.45
Arsenic 193.696 1.3 ... 0.44 ... ... ... ... ... ... 1.1
Barium 455.403 ... ... ... ... ... ... ... ... ... ...
Beryllium 313.042 ... ... ... ... ... ... ... ... 0.04 0.05
Boron 249.773 0.04 ... ... ... 0.32 ... ... ... ... ...
Cadmium 226.502 ... ... ... ... 0.03 ... ... 0.02 ... ...
Calcium 317.933 ... ... 0.08 ... 0.01 0.01 0.04 ... 0.03 0.03
Chromium 267.716 ... ... ... ... 0.003 ... 0.04 ... ... 0.04
Cobalt 228.616 ... ... 0.03 ... 0.005 ... ... 0.03 0.15 ...
Copper 324.754 ... ... ... ... 0.003 ... ... ... 0.05 0.02
Iron 259.940 ... ... ... ... ... 0.12 0.12 ... ... ...
Lead 220.353 0.17 ... ... ... ... ... ... ... ... ...
Magnesium 279.079 ... 0.02 0.11 ... 0.13 0.002 0.25 ... 0.07 0.12
Manganese 257.610 0.005 ... 0.01 ... 0.002 ... ... ... ... ...
Molybdenum 202.030 0.05 ... ... ... 0.03 ... ... ... ... ...
Nickel 231.604 ... ... ... ... ... ... ... ... ... ...
Selenium 196.026 0.23 ... ... ... 0.09 ... ... ... ... ...
Silicon 288.158 ... ... 0.07 ... ... ... ... ... ... 0.01
Sodium 588.995 ... ... ... ... ... ... ... ... 0.08 ...
Thallium 190.864 0.30 ... ... ... ... ... ... ... ... ...
Vanadium 292.402 ... ... 0.05 ... 0.005 ... ... ... 0.02 ...
Zinc 213.856 ... ... ... 0.14 ... ... ... 0.29 ... ...
A
See Table 4 for concentrations used.

TABLE 3 Analyte Elemental Concentrations Tested for TABLE 4 Interferent Elemental Concentrations for Analytes
InterferentsA TestedA
Analytes
Al
iTeh Standards mg/L
10
Interferents
Al
mg/L
1000

(https://standards.iteh.ai)
As 10 Ca 1000
B 10 Cr 200
Ba 1 Cu 200
Be 1 Fe 1000
Ca
Cd
Co
Document Preview 1
10
1
Mg
Mn
Ni
1000
200
200
Cr 1 Ti 200
Cu 1 V 200
Fe ASTM D1976-18
1 A
This table indicates concentrations used for interference measurements in Table
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Mg
Mn
1
1
2.
Na 10
Ni 10
Pb 10 6.1.2.2 Reports indicate that better control of the argon flow
Sb 10
Se 10 rate improves instrument performance. This control of the
Si 1 argon flow rate can be accomplished with the use of mass flow
Tl 10 controllers.
V 1
Zn 10 6.1.3 Chemical interferences are characterized by molecular
A
This table indicates concentrations used for interference measurements in Table
compound formation, ionization effects, and solute vaporiza-
2. tion effects. Normally these effects are not pronounced with the
inductively coupled plasma (ICP) technique; however, if
observed, they can be minimized by careful selection of
operating conditions (incident power, plasma observation
concentrations, or both. The use of a peristaltic pump may position, and so forth), by buffering the sample, by matrix
lessen these interferences. If these types of interferences are matching, and by standard addition procedures. These types of
operative, they must be reduced by dilution of these samples or interferences can be highly dependent on matrix type and the
utilization of standard addition techniques, or both. specific analyte.
6.1.2.1 Salt buildup at the tip of the nebulizer is another 6.2 Analysis for silica precludes the use of borosilicate
problem that can occur from high dissolved solids. This salt glassware due to potential contamination.
buildup affects aerosol flow rate that can cause instrumental
drift. To control this problem, wet the argon prior to 7. Apparatus
nebulization, use a tip washer, or dilute the sample. 7.1 See the manufacturer’s instruction manual for installa-
NOTE 1—Periodic inspection and cleaning of the nebulizer and torch tion and operation of inductively-coupled argon plasma spec-
components are highly recommended. trometers. Table 5 lists elements for which this test method

3
 D1976 − 18
TABLE 5 Suggested Wavelengths and Estimated Detection on Analytical Reagents of the American Chemical Society.5
LimitsA The high sensitivity of inductively-coupled argon plasma
Wavelength, Estimated detection limit, atomic emission spectrometry may require reagents of higher
Element
nmB µg/LC
purity. Stock standard solutions are prepared from high purity
Aluminum 308.215 45
Arsenic 193.696 53 metals, oxides, or nonhydroscopic reagent grade salts using
Antimony 206.833 32 Types I, II, and III reagent water, and ultrapure acids. Other
Barium 455.403 2
Beryllium 313.042 0.3
grades may be used, provided it is first ascertained that the
Boron 249.773 5 reagent is of sufficient purity to permit its use without lessening
Cadmium 226.502 4 the accuracy of the determination.
Calcium 317.933 10
Chromium 267.716 7 8.2 Purity of Water—Unless otherwise indicated, reference
Cobalt 228.616 7 to water shall be understood to mean reagent water conforming
Copper 324.754 6
Iron 259.940 7 to Type I, II, or III of Specification D1193. It is the analyst’s
Lead 220.353 42 responsibility to assure that water is free of interferences. Other
Lithium 670.784 4 reagent water types may be used provided it is first ascertained
Magnesium 279.079 30
Manganese 257.610 2 that the water is of sufficiently high purity to permit its use
Molybdenum 202.030 8 without adversely affecting the precision and bias of the test
Nickel 231.604 15 method. Type II water was specified at the time of round robin
Phosphorous 214.914 76
Potassium 766.491 700 testing of this test method.
Selenium 196.026 75
Silica 288.158 27
8.3 Aqua Regia—Mix three parts hydrochloric acid (sp gr
Silver 328.068 7 1.19) and one part concentrated nitric acid (sp gr 1.42) just
Sodium 588.995 29 before use.
Strontium 421.552 0.77
Sulfur 182.037 3 NOTE 2—Exercise caution when mixing this reagent, use of a fume
Thallium 190.864 40 hood is recommended.
Vanadium 292.402 8
8.4 Argon—Welding grade equivalent or better.
iTeh Standards
Zinc 213.856 2
A
8.5 Hydrochloric Acid (1 + 1)—Add 1 volume of hydro-
Winge, R. K., Fassel, V. A., Peterson, V. J., and Floyd, M. A., “Inductively
Coupled Plasma-Atomic Emission Spectroscopy,” An Atlas of Spectral Information,
chloric acid (sp gr 1.19) ultrapure or equivalent to 1 volume of
(https://standards.iteh.ai)
Elsevier Science Publishing Co., Inc., New York, NY, 1985.
B water.
The wavelengths listed are recommended because of their sensitivity and overall
acceptance. Other wavelengths may be substituted if they can provide the needed
8.6 Nitric Acid (1 + 1)—Add 1 volume of nitric acid (sp gr
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sensitivity and are treated with the same corrective techniques for spectral
interference (see 6.1.1). 1.42) ultrapure or equivalent to 1 volume of water.
C
The estimated detection limits as shown are taken from Winge et al.,A USEPA
8.7 Nitric Acid (1 + 499)—Add 1 volume of nitric acid (sp
Method 200.7, or task group data. They are given as a guide for approximate
detection limits for the listed wavelengths. The actual test method instrumental
detection limits are sample-dependent and may vary as the sample matrix varies gr 1.42) ultrapure or equivalent to 499 volumes of water.
(see 3.2.3). ASTM D1976-18 8.8 Stock Solutions—Preparation of example stock solutions
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for each element is listed in Table 6. Use of commercially
prepared certified stock solutions is recommended.
applies, with recommended wavelengths and typical estimated 8.9 Mixed Calibration Standard Solutions—Prepare mixed
instrumental detection limits using conventional pneumatic calibration standard solutions by combining appropriate vol-
nebulization. Actual working detection limits are sample de- umes of the stock solutions in volumetric flasks (see Note 3).
pendent and as the sample matrix varies, these detection limits Prior to preparing mixed standards, each stock solution should
may also vary. In time, other elements may be added as more be analyzed separately to determine possible spectral interfer-
information becomes available and as required. ence or the presence of impurities. Care should be taken when
7.1.1 Use of a vacuum or purged path is necessary for preparing the mixed standards to ensure the elements are
determination of sulfur. compatible and stable. It is common practice to have all or
7.1.2 Use of glass in the sample path may not be acceptable nearly all elements in one mixed calibration standard.
for silica, use of an inert material is recommended to avoid NOTE 3—Mixed calibration standards will vary depending on the
silica contamination.
5
Reagent Chemicals, American Chemical Society Specifications, American
8. Reagents and Materials Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
listed by the American Chemical Society, see Annual Standards for Laboratory
8.1 Purity of Reagents—Reagent grade chemicals shall be
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
used in all tests. Unless otherwise indicated, it is intended that and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
reagents shall conform to the specifications of the Committee MD.

4
 D1976 − 18
TABLE 6 Preparation of Example Element Stock SolutionsA,B 10.1.1 Analysis for silica precludes the use of borosilicate
Element (Compound) Weight, g Solvent glassware due to potential contamination.
Al 0.1000 HCl (1 + 1)
Sb 0.1000 Aqua regia 10.2 Preserve the samples by immediately adding nitric acid
As2O3 C 0.1320 Water + 0.4 g NaOH to adjust the pH to 2 at the time of collection. Normally, 2 mL
BaCl2E 0.1516 HCl (1 + 1) of HNO3 is required per L of sample. If only dissolved
Be 0.1000 Aqua regia
H3BO3 0.5716 Water elements are to be determined, filter the sample through a
Cd 0.1000 HNO3 (sp gr 1.42) 0.45-µm membrane filter before acidification (see Note 4). The
CaCO3F 0.2498 Water + HCl (1 + 1) holding time for the sample may be calculated in accordance
Cr 0.1000 HCl (1 + 1)
Co 0.1000 HNO3 (1 + 1) with Practice D4841.
Cu 0.1000 HNO3 (1 + 1)
Fe 0.1000 HNO3 (sp gr 1.42) NOTE 4—Depending on the manufacturer, some filters have been found
Pb 0.1000 HNO3 (sp gr 1.42) to be contaminated to various degrees with heavy metals. Care should be
Li2CO3 0.5323 HNO3 (1 + 1) exercised in selecting a source for these filters. It is good practice to wash
Mg 0.1000 HNO3 (1 + 1) the filters with dilute nitric acid and a small portion of the sample before
Mn 0.1000 HNO3 (1 + 1) filtering.
Ni 0.1000 HNO3 (sp gr 1.42)
NH4H2PO4 0.3745 HCl (1 + 9) 11. Calibration and Standardization
KCl 0.1907 Water
(NH4)2MoO4 0.2043 Water 11.1 Calibrate the instrument over a suitable concentration
Na2SeO4 D 0.2393 Water range for the elements chosen by atomizing the calibration
Na2SiO3·5H2O 0.3531 Water
Ag 0.1000 HNO3 (sp gr 1.42)
blank and mixed standard solutions and recording their con-
NaCl 0.2542 Water centrations and signal intensities.
SrCO3 0.1685 HCl (1 + 9)
Na2SO4 0.4431 Water NOTE 5—Because the precision and bias for the original test method
TlNO3 0.1303 Water was obtained using a two-point calibration, it was recommended that the
NH4VO3 0.2297 HNO3 (1 + 1) instrument be calibrated using that procedure as outlined in the test
Zn 0.1000 HNO3 (1 + 1) method for those elements. Use of a blank and four point calibration is
A
Example element stock solutions, 1.00 mL = 100 µg of metal. Dissolve the listed preferred (15.2).

iTeh Standards
weights of each compound or metal in 20 mL of specified solvent and dilute to 1
11.1.1 Multiple-point calibration standards may be used,
L. The metals may require heat to increase rate of dissolution.
B and it is the user’s responsibility to ensure the validity of the
Where water is used as the solvent, acidify with 10 mL of HNO3 (sp gr 1.42) and

(https://standards.iteh.ai)
test method. Regardless of the calibration procedure used,
dilute to 1 L. See Section 8 for concentration of acids. Commercially available
standards may be used. Alternative salts or oxides may also be used.
C
Add 2 mL of HNO3 (sp gr 1.42) and dilute to 1 L.
appropriate quality control (QC) is required to verify the
D calibration curve at the anticipated concentration range(s)
Document Preview
Add 1 mL of HNO3 (sp gr 1.42) and dilute to 1 L.
E
F
Dry for 1 h at 180°C. before proceeding to the sample analysis. It is recommended
Dry for 1 h at 180°C. Add to approximately 600 mL of water and dissolve
that the calibration blank and standard(s) be matrix matched
cautiously with a minimum of dilute HCl. Dilute to 1 L with water.
with the same acid concentration contained in the samples.
ASTM D1976-1812. Procedure
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12.1 To determine dissolved elements, proceed with 12.4.
number of elements being determined. An example of mixed calibration
standards for the simultaneous determination of 20 elements is as follows: 12.2 When determining total-recoverable elements, choose
Mixed Standard Solution I—manganese, beryllium, cadmium, lead, and zinc a volume of a well mixed, acid-preserved sample appropriate
Mixed Standard Solution II—copper, vanadium, iron, and cobalt for the expected level of elements.
Mixed Standard Solution III—molybdenum, arsenic, and selenium 12.2.1 Transfer the sample to a beaker (use tetrafluoroeth-
Mixed Standard Solution IV—aluminum, chromium, and nickel
Mixed Standard Solution V—antimony, boron, magnesium, silver, and ylene or equivalent for silica analysis) and add 2 mL of HNO3
thallium (1 + 1) and 10 mL of HCl (1 + 1) and heat on a steam bath or
8.10 Reagent Blank—This must contain all the reagents and hot plate until the volume has been reduced to near 25 mL,
be the same volume as used in the processing of the samples. making certain the sample does not boil. Cool the sample, and
The reagent blank must be carried through the complete if necessary filter or let insoluble material settle to avoid
procedure and contain the same acid concentration in the final clogging of the nebulizer. Adjust to the original sample
solution as the sample solution used for analysis. volume. To determine total-recoverable elements, proceed with
12.4.
9. Hazards 12.3 When determining total elements, choose a volume of
9.1 The toxicity or carcinogenicity of each reagent used in well mixed, acid-preserved sample appropriate for the ex-
this test method has not been precisely defined; however, each pected level of elements.
chemical should be treated as a potential health hazard. NOTE 6—Addition of HF acid may be required in order to effect
Adequate precautions should be taken to minimize personnel complete dissolution of all siliceous material, so this digestion method
exposure to chemicals used in this procedure. will result in low results for samples containing insoluble silica.
12.3.1 Transfer the sample to a beaker (use tetrafluoroeth-
10. Sampling ylene or equivalent for silica analysis). Add 3 mL of HNO3 (sp
10.1 Collect the samples in accordance with Practices gr 1.42). Place the beaker on a hot plate and cautiously
D1066 or Practices D3370 as applicable. evaporate to near dryness, making certain that the sample does

5
 D1976 − 18
not boil and that no area of the bottom of the beaker is allowed 13.2 If dilutions are required, apply the appropriate dilution
to go dry. Cool the beaker and add 5 mL of HNO3 (sp gr 1.42). factor to sample values.
Cover the beaker with a watch glass (use tetrafluoroethylene or 13.3 Report results in the calibration concentration units.
equivalent for silica analysis) and return it to the hot plate.
Increase the temperature of the hot plate so a gentle reflux 14. Precision and Bias6
action occurs. Continue heating, adding additional acid as
necessary, until the digestion is complete (generally indicated 14.1 The original precision and bias data for this test
when the digestate is light in color or does not change in method are based on an interlaboratory study conducted by the
appearance with continued refluxing). Again, evaporate to near U.S. Environmental Protection Agency.2
dryness and cool the beaker. Add 10 mL of HCl (1 + 1) and 15 14.2 The test design of the study meets the requirements of
mL of water per 100 mL of final solution and warm the beaker Practice D2777 – 86 for elements listed in this test method
gently for 15 min to dissolve any precipitate or residue during the original testing.
resulting from evaporation. Allow the sample to cool, wash the 14.2.1 The test design was based on a form of the analysis
beaker walls and watch glass with water, and if necessary, filter of variance applying the approach and methods of the Youden
or let insoluble material settle to avoid clogging the nebulizer. Unit block design. In the Youden nonreplicate approach to
Adjust to the original sample volume. To determine total determining the precision and bias of the analytical method,
elements, proceed with 12.4. pairs of samples of similar but different concentrations are
analyzed. The key in the Youden approach is to estimate
NOTE 7—Many laboratories have found block digestion systems a
useful way to digest samples for trace metals analysis. Systems typically precision from analyses of Youden pairs rather than through
consist of either a metal or graphite block with wells to hold digestion replicate analyses. In the referenced study, five Youden pairs of
tubes. The block temperature controller must be able to maintain unifor- spike materials were prepared (Guide D5810). Six water types
mity of temperature across all positions of the block. For trace metals were included. Only the data from reagent water and surface
analysis, the digestion tubes should be constructed of polypropylene and
water are presented here. Each water type was spiked with
have a volume accuracy of at least 0.5 %. All lots of tubes should come
with a certificate of analysis to demonstrate suitability for their intended three of the five Youden pairs with the exception of reagent
purpose. water, which was spiked with all five Youden pairs. Each water
iTeh Standards
12.4 Atomize each solution to record its emission intensity
or concentration. A sample rinse of HNO3 (1 + 499) is recom-
sample was prepared for analysis by both a total and a
total-recoverable digestion procedure. A total of twelve labo-

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mended between samples. ratories participated in the study.
14.2.2 Type II water was specified for this round robin.
14.2.3 Twenty-seven different elements were included in the
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13. Calculation
study and individual measurements of precision and bias were
13.1 Include the blank in the calibration
NOTE 8—The original interlaboratory study subtracted reagent blanks
(see 8.10) from all samples. This subtraction was particularly important 6

for digested samples requiring large quantities of acids to ASTM

complete D1976-18
Supporting data have been filed at ASTM International Headquarters and may
the be obtained by requesting Research Report RR:D19-1144 and RR:D19-1198.
https://standards.iteh.ai/catalog/standards/sist/10f0d8ae-c136-4158-86a5-dd45b7a8e5ce/astm-d1976-18
digestion. Contact ASTM Customer Service at service@astm.org.

TABLE 7 Regression Equations for Bias and Precision, µg/L, Reagent Water versus Surface Water
(Aluminum, Antimony, Arsenic, Beryllium)
NOTE 1—X = mean recovery; C = true value for the concentration.
Water Type Aluminum Antimony Arsenic Beryllium
Total Digestion
Applicable concentration range (83 to 1434) (411 to 1406) (83 to 943) (17 to 76)
Reagent water, hard
Single-analyst precision So = 0.05X + 3.72 So = 0.23X − 50.17 So = 0.07X + 8.28 So = 0.02X + 0.18
Overall precision St = 0.07X + 9.34 St = 0.21X − 24.02 St = 0.11X + 2.96 St = 0.02X + 0.91
Bias X = 0.91C + 6.62 X = 0.74C + 2.27 X = 1.03C − 12.03 X = 1.02C − 1.92
Surface water, hard
Single-analyst precision So = 0.00X + 40.75 So = 0.11X − 0.14 So = 0.05X + 7.79 So = 0.00X + 0.85
Overall precision St = 0.10X + 67.23 St = 0.07X + 35.71 St = 0.10X + 10.55 St = 0.09X − 0.47
Bias X = 0.98C + 90.54 X = 0.88C − 55.19 X = 1.00C − 16.02 X = 1.00C − 0.89

Total-Recoverable Digestion
Applicable concentration range (83 to 1434) (411 to 1406) (83 to 943) (17 to 76)
Reagent water, soft
Single-analyst precision So = 0.05X + 25.05 So = 0.06X + 7.85 So = 0.07X + 6.12 So = 0.04X + 0.14
Overall precision St = 0.10X + 28.72 St = 0.05X + 20.10 St = 0.12X + 2.99 St = 0.07X − 0.47
Bias X = 0.93C + 28.40 X = 0.92C − 22.46 X = 1.01C − 2.08 X = 1.03C − 0.73
Reagent water, soft
Single-analyst precision So = 0.01X + 34.72 So = 0.06X + 0.97 So = 0.05X + 9.29 So = 0.02X + 0.43
Overall precision St = 0.10X + 74.75 St = 0.07X + 14.28 St = 0.11X + 1.82 St = 0.01X + 15.4
Bias X = 1.02C + 40.42 X = 0.95C − 34.50 X = 1.06C − 7.00 X = 1.04C − 2.08