ASTM D4190-15(2023)
(Test Method)Standard Test Method for Elements in Water by Direct-Current Plasma Atomic Emission Spectroscopy
Standard Test Method for Elements in Water by Direct-Current Plasma Atomic Emission Spectroscopy
SIGNIFICANCE AND USE
5.1 This test method is useful for the determination of element concentrations in many natural waters. It has the capability for the simultaneous determination of up to 15 separate elements. High analysis sensitivity can be achieved for some elements, such as boron and vanadium.
SCOPE
1.1 This test method covers the determination of dissolved and total recoverable elements in water, which includes drinking water, lake water, river water, sea water, snow, and Type II reagent water by direct current plasma atomic emission spectroscopy (DCP).
1.2 The information on precision and bias may not apply to other waters.
1.3 This test method is applicable to the 15 elements listed in Annex A1 (Table A1.1) and covers the ranges in Table 1.
1.4 This test method is not applicable to brines unless the sample matrix can be matched or the sample can be diluted by a factor of 200 up to 500 and still maintain the analyte concentration above the detection limit.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.7 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D4190 − 15 (Reapproved 2023)
Standard Test Method for
Elements in Water by Direct-Current Plasma Atomic
Emission Spectroscopy
This standard is issued under the fixed designation D4190; 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
D1193 Specification for Reagent Water
1.1 This test method covers the determination of dissolved
D2777 Practice for Determination of Precision and Bias of
and total recoverable elements in water, which includes drink-
Applicable Test Methods of Committee D19 on Water
ing water, lake water, river water, sea water, snow, and Type II
D3370 Practices for Sampling Water from Flowing Process
reagent water by direct current plasma atomic emission spec-
Streams
troscopy (DCP).
D4841 Practice for Estimation of Holding Time for Water
1.2 The information on precision and bias may not apply to
Samples Containing Organic and Inorganic Constituents
other waters.
D5810 Guide for Spiking into Aqueous Samples
1.3 This test method is applicable to the 15 elements listed
D5847 Practice for Writing Quality Control Specifications
in Annex A1 (Table A1.1) and covers the ranges in Table 1.
for Standard Test Methods for Water Analysis
1.4 This test method is not applicable to brines unless the E1097 Guide for Determination of Various Elements by
sample matrix can be matched or the sample can be diluted by Direct Current Plasma Atomic Emission Spectrometry
a factor of 200 up to 500 and still maintain the analyte
concentration above the detection limit.
3. Terminology
1.5 The values stated in SI units are to be regarded as
3.1 Definitions—For definitions of terms used in this test
standard. No other units of measurement are included in this
method, refer to Terminology D1129.
standard.
3.2 Definitions of Terms Specific to This Standard:
1.6 This standard does not purport to address all of the
3.2.1 total recoverable element, n—a descriptive term relat-
safety concerns, if any, associated with its use. It is the
ing to the elemental forms recovered in the acid-digestion
responsibility of the user of this standard to establish appro-
procedure specified in this test method.
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
4. Summary of Test Method
1.7 This international standard was developed in accor-
dance with internationally recognized principles on standard-
4.1 Elements are determined, either sequentially or
ization established in the Decision on Principles for the
simultaneously, by DCP.
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical 4.2 Matrix enhancement or suppression of the emission
Barriers to Trade (TBT) Committee. signal can be minimized by the addition of 2000 mg/L of
lithium ion to all standards, samples, and blanks.
2. Referenced Documents
2 4.3 Dissolved elements are determined by atomizing a
2.1 ASTM Standards:
filtered and acidified sample directly with no pretreatment.
D1066 Practice for Sampling Steam
4.4 If the sample is clear, total recoverable elements are
This test method is under the jurisdiction of ASTM Committee D19 on Water
determined in the same manner as dissolved elements except
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents
that sample is unfiltered and acidified.
in Water.
Current edition approved Dec. 1, 2023. Published January 2024. Originally
4.5 If there are large particles (non-colloidal) the total
approved in 1982. Last previous edition approved in 2015 as D4190 – 15. DOI:
10.1520/D4190-15R23.
recoverable elements are determined on a portion of the sample
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
after a hydrochloric-nitric acid digestion (12.2 – 12.5). The
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
same digestion procedure is used to determine all total recov-
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. erable elements in this test method.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4190 − 15 (2023)
TABLE 1 Solutions for Analysis
on Analytical Reagents of the American Chemical Society
Element Concentration Range where such specifications are available. Other grades may be
Aluminum 50 to 200 μg/L used, provided it is first ascertained that the reagent is of
Beryllium 50 to 1000 μg/L
sufficient purity to permit its use without lessening the accu-
Boron 50 to 1000 μg/L
racy of the determination.
Cadmium 50 to 1000 μg/L
Chromium 50 to 1000 μg/L
8.2 Purity of Water—Unless otherwise indicated, reference
Cobalt 50 to 1000 μg/L
to water shall be understood to mean reagent water conforming
Copper 50 to 1000 μg/L
Iron 50 to 1000 μg/L
to Type I of Specification D1193. Other reagent water types
Lead 200 to 1000 μg/L
may be used, provided it is first ascertained that the water is of
Manganese 50 to 1000 μg/L
sufficiently high purity to permit its use without lessening the
Mercury 50 to 1000 μg/L
Nickel 50 to 1000 μg/L
bias and precision of the determination. Type II water was
Strontium 50 to 1000 μg/L
specified at the time of round robin testing of this test method.
Vanadium 50 to 1000 μg/L
Zinc 50 to 1000 μg/L
8.3 Stock Solutions—Preparation of stock solutions for each
element is listed in Annex A3 (Table A3.1) or use commer-
cially available, ICP Grade, stock standards.
3, 4
NOTE 1—The volatility of mercury compounds, especially the
8.4 Filter Paper—Purchase suitable filter paper. Typically
chlorides, makes it necessary to use considerable care in digesting samples
the filter papers have a pore size of 0.45 μm membrane.
containing these elements. The samples must not be boiled unless
Material such as fine-textured, acid-washed, ashless paper, or
provision is made to prevent loss by volatilization.
glass fiber paper are acceptable. The user must first ascertain
5. Significance and Use
that the filter paper is of sufficient purity to use without
adversely affecting the bias and precision of the test method.8.4
5.1 This test method is useful for the determination of
element concentrations in many natural waters. It has the
NOTE 3—Depending on the manufacturer, these filters have been found
capability for the simultaneous determination of up to 15
to be contaminated to various degrees with heavy metals. Care should be
exercised in selecting a source of these filters. A good practice is to wash
separate elements. High analysis sensitivity can be achieved
the filters with nitric acid and reagent water before filtering a sample.
for some elements, such as boron and vanadium.
8.5 High Purity Hydrochloric Acid, (HCl), (sp gr 1.19),
6. Interferences
concentrated hydrochloric acid.
6.1 For commonly occurring matrix elements the following
8.6 Hydrochloric Acid, (1 + 1)—Add one volume of HCl
spectral interferences have been observed:
(sp gr 1.19) to one volume of water.
6.1.1 Calcium, magnesium, and boron interfere with lead at
8.7 Lithium Carbonate, ultrapure.
405.78 nm.
6.1.2 Calcium interferes with chromium at 425.43 nm. 8.8 Lithium Solution (40 000 mg ⁄L)—Dissolve 213 g of
ultrapure lithium carbonate in a minimum amount of HCl (sp
6.1.3 Magnesium interferes with cadmium at 214.44 nm.
gr 1.19) and dilute to 1 L with water.
6.1.4 Iron interferes with cobalt at 345.35 nm and
240.73 nm.
8.9 Concentrated Nitric Acid, (HNO ), (sp gr 1.42)—High-
6.1.5 Cobalt interferes with nickel at 341.48 nm.
purity acid can be prepared by distillation of concentrated nitric
acid from a sub-boiling quartz still or it can be commercially
NOTE 2—The exact magnitude of these interferences has not been
determined since it depends on the concentration of the calibration purchased.
standards used and the sample matrix.
8.10 Dilute Nitric Acid, (1+1)—Add one volume of HNO
6.2 Some additional possible interferences are listed in
(sp. gr. 1.42) to one volume of water.
Annex A2 (Table A2.1) so that the analyst may be aware of and
8.11 Dilute Nitric Acid, (1 + 499)—Add one volume of
test for them.
HNO (sp gr 1.42) to 499 volumes of water.
7. Apparatus
NOTE 4—If a high reagent blank is obtained on either HNO or HCl,
distill the acid or use high purity acid. When HCl is distilled, an azeotropic
7.1 See the manufacturer’s instruction manual for installa-
mixture is obtained (approximately 6 N HCl); therefore, whenever
tion and operation of DCP spectrometers, refer to Guide E1097
concentrated HCl is specified in the preparation of a reagent or in the
for information on DCP spectrometers.
procedure, use double the amount if distilled acid is used.
8. Reagents 9. Precautions
9.1 Emission intensities are affected by changing viscosity
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that so it is important to control the viscosity of blanks, standards,
reagents shall conform to the specifications of the Committee
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington,
Standard Methods of Chemical Analysis, Editor, N. H. Furman, Vol 1, Sixth DC. For suggestions on the testing of reagents not listed by the American Chemical
Edition, pp. 107 and 657. Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
Smith, G. F., The Wet Chemical Oxidation of Organic Compositions, The G. U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
Frederick Smith Chemical Co., 1965. copeial Convention, Inc. (USPC), Rockville, MD.
D4190 − 15 (2023)
and samples within reasonable limits. Reagent water standards 20 mL. Take care to see that the samples do not boil. Loss of
should not be used to analyze oil field brines. Alternatively, sample could result from bumping or spattering.
matrix matching or the method of additions can be used.
NOTE 7—For samples with high levels of dissolved solids, the amount
of reduction in volume is left to the discretion of the analyst.
9.2 Organic solvents, such as alcohol, acetone, and methyl
NOTE 8—Many laboratories have found block digestion systems a
ethyl ketone have been observed to enhance emission intensity.
useful way to digest samples for trace metals analysis. Systems typically
This enhancement effect must be compensated for when
consist of either a metal or graphite block with wells to hold digestion
organic solvents are known to be present. Alternatively, matrix
tubes. The block temperature controller must be able to maintain unifor-
matching or the method of additions can be used. mity of temperature across all positions of the block. 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 tubes should come
10. Sampling
with a certificate of analysis to demonstrate suitability for their intended
purpose.
10.1 Collect the samples in accordance with the applicable
standards, Practice D1066 or Practices D3370.
12.5 Cool and filter (8.4) the samples, if necessary, through
a fine ashless filter paper into 100.0 mL volumetric flasks.
10.2 Preserve the samples by immediately adding high
Wash the filter paper three times with water and adjust to
purity nitric acid to adjust the pH to two at the time of
volume.
collection. Normally 2 mL of HNO is required per liter of
sample. If only dissolved elements are to be determined, (Note
12.6 Atomize each solution and record its emission intensity
5) filter the sample through a 0.45 μm membrane filter before
or concentration. Atomize HNO (1 + 499) (8.11) between
acidification. The holding time for the sample may be calcu-
samples.
lated in accordance with Practice D4841.
13. Calculation
NOTE 5—Alternatively, the pH may be adjusted in the laboratory if the
13.1 Calculate the concentration of elements in each
sample is returned within 14 days. However, acid must be added at least
24 h before analysis to dissolve any metals that adsorb to the container
sample, in μg/L, using the calibrations established in 11.3.
walls. This could reduce hazards of working with acids in the field when
Modern DCP instruments will provide the results in the
appropriate.
calibrated concentration units.
13.2 Multiply the results for dissolved elements by the
11. Calibration and Standardization
dilution factor of 1.05 to correct for the required addition of
11.1 Prepare 100 mL of a blank and at least four standard
lithium solution (12.1).
solutions to bracket the expected concentration range of the
NOTE 9—The correction does not need to be applied to samples
samples to be analyzed by diluting 5.0 mL of lithium solution
analyzed using the total recoverable process because those samples are
(see 8.8) and an appropriate volume of stock solution with
adjusted to volume. If the block digestion systems reflux the samples
HNO (1 + 499). Prepare the blank and standards each time the
without any loss of volume the dilution factor will need to be applied.
test is to be run or as determined by Practice D4841.
14. Precision and Bias
11.2 Analyze at least four working standards containing
14.1 To facilitate handling and distribution for round robin
concentrations of each element that bracket the expected
testing, three concentrated solutions were prepared. These were
sample concentration, prior to analysis of samples, to calibrate
acidified solutions of 15 elements.
the instrument. Atomize the blank and standards and record the
emission intensity or concentration. Atomize HNO (1 + 499)
3 14.2 The concentrated solutions, when diluted according to
between each standard.
directions, yielded solutions for analysis with the composition
as shown in Table 2. A total of eight laboratories and thirteen
11.3 Using the instrument software verify that the instru-
operators participated in this study.
ment calibration is within user acceptable QC limits.
14.2.1 Type II water was specified at the time of round robin
testing of this test method.
12. Procedure
14.3 Precision—The precision of this test method for the
12.1 To determine dissolved elements, add 5.0 mL of
elements tested within their respective ranges of concentration
lithium solution (see
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