ASTM D6052-97(2016)
(Test Method)Standard Test Method for Preparation and Elemental Analysis of Liquid Hazardous Waste by Energy-Dispersive X-Ray Fluorescence
Standard Test Method for Preparation and Elemental Analysis of Liquid Hazardous Waste by Energy-Dispersive X-Ray Fluorescence
SIGNIFICANCE AND USE
4.1 The elemental analysis of liquid hazardous waste is often important for regulatory and process specific requirements. This test method provides the user an accurate, rapid method for trace and major element determinations.
SCOPE
1.1 This test method covers the determination of trace and major element concentrations by energy-dispersive X-ray fluorescence spectrometry (EDXRF) in liquid hazardous waste (LHW).
1.2 This test method has been used successfully on numerous samples of aqueous and organic-based LHW for the determination of the following elements: Ag, As, Ba, Br, Cd, Cl, Cr, Cu, Fe, Hg, I, K, Ni, P, Pb, S, Sb, Se, Sn, Tl, V, and Zn.
1.3 This test method is applicable for other elements (Si-U) not listed in 1.2.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
General Information
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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: D6052 − 97 (Reapproved 2016)
Standard Test Method for
Preparation and Elemental Analysis of Liquid Hazardous
Waste by Energy-Dispersive X-Ray Fluorescence
This standard is issued under the fixed designation D6052; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope samplemixtureistransferredintoadisposablesamplecupand
placed in the spectrometer for analysis.
1.1 This test method covers the determination of trace and
majorelementconcentrationsbyenergy-dispersiveX-rayfluo- 3.2 The K spectral emission lines are used for elements
rescence spectrometry (EDXRF) in liquid hazardous waste
Si-Ba.
(LHW).
3.3 The Lspectralemissionlinesareusedforelementswith
1.2 This test method has been used successfully on numer-
atomic numbers greater than Ba.
ous samples of aqueous and organic-based LHW for the
determination of the following elements: Ag, As, Ba, Br, Cd,
4. Significance and Use
Cl,Cr,Cu,Fe,Hg,I,K,Ni,P,Pb,S,Sb,Se,Sn,Tl,V,andZn.
4.1 The elemental analysis of liquid hazardous waste is
1.3 This test method is applicable for other elements (Si-U)
often important for regulatory and process specific require-
not listed in 1.2.
ments. This test method provides the user an accurate, rapid
method for trace and major element determinations.
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
5. Interferences
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
5.1 Spectral Overlaps (Deconvolution):
bility of regulatory limitations prior to use.
5.1.1 Samples containing a mixture of elements often ex-
hibit X-ray emission line overlap. Modern Si (Li) detectors
2. Referenced Documents
generally provide adequate resolution to minimize the effects
2.1 ASTM Standards:
ofspectraloverlap.Incaseswhereemissionlineoverlapexists,
C982 Guide for Selecting Components for Energy-
techniques of peak fitting exist for extracting corrected analyte
Dispersive X-Ray Fluorescence (XRF) Systems (With-
emissionlineintensities.Forexample,thePbLα“lineoverlaps
drawn 2008)
with the AsKα.” The PbLβ line can be used to avoid this
D1193Specification for Reagent Water
overlap and theAsK lines can then be resolved from the PbLα
2.2 Other ASTM Documents:
overlap.Theactuallinesusedforanyparticularelementshould
ASTM Data Series DS 46X-ray Emission Wavelengths and
be such that overlaps are minimized. Follow the EDXRF
KeV Tables for Nondiffractive Analysis
manufacturer’s recommendation concerning spectral deconvo-
lution. Reference should be made toASTM Data Series DS 46
3. Summary of Test Method
for detailed information on potential line overlaps.
3.1 Aweighed portion of activated alumina and sample are
5.2 Matrix Interferences (Regression):
combined in a mixing vessel and shaken until well mixed.The
5.2.1 Matrix interference in the measurement of “as re-
ceived” LHW samples using EDXRF has been the principle
This test method is under the jurisdiction ofASTM Committee D34 on Waste
limitation in the development and expanding use of this
Management and is the direct responsibility of Subcommittee D34.01.06 on
instrumental technique. Using well understood XRF principles
Analytical Methods.
Current edition approved Sept. 1, 2016. Published September 2016. Originally
for controlling matrix effects, for example, dilution and matrix
approved in 1997. Last previous edition approved in 2008 as D6052–97 (2008).
modification using lithium borate fusion and addition of heavy
DOI: 10.1520/D6052-97R16.
absorbers, a matrix can be stabilized. Using calcined alumina
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
andtheaboveprinciplesmatricesarestabilizedforquantitative
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
EDXRF analysis.
the ASTM website.
5.2.2 The response range of this test method should be
The last approved version of this historical standard is referenced on
linear with respect to the elements of interest and their
www.astm.org.
Available from ASTM Headquarters, Customer Service. regulatory or process control, or both, action thresholds. Large
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959. United States
D6052 − 97 (2016)
TABLE 1 Recommended Standards Ranges
concentration variations of element or matrix, or both, compo-
nents in LHW samples can result in non-linear X-ray intensity Low Con- High Con- High Con-
Low Con-
centration centration centration
response at increasing element concentrations.
Analyte Analyte centration
Range, Range, Range,
Range, mg/kg
mg/kg mg/kg mg/kg
6. Apparatus
Ag 5 600 Zn 5 600
Ba 5 600 As 5 600
6.1 Energy-dispersive X-ray Fluorescence Spectrometer,ca-
P 0.1% 5% Se 5 600
pable of measuring the wavelengths of the elements listed in
S 0.05% 5% Br 10 5000
1.2. Refer to Guide C982 for system specifications.
Cl 0.05% 5% Cd 5 600
K 0.1% 5% Sb 5 600
6.2 Analytical Balance, capable of weighing to 0.001 g.
V 5 600 Sn 5 600
Cr 5 600 I 5 600
7. Reagents and Materials Fe 5 600 Hg 5 600
Ni 5 600 Tl 5 600
7.1 Purity of Reagents—Reagent grade chemicals shall be
Cu 5 600 Pb 5 600
used in all tests. Unless otherwise indicated, it is intended that
all reagents conform to the specifications of the Committee on
Analytical Reagents of theAmerican Chemical Society, where
a polypropylene base and a high-purity, 4 µm polyester film.
such specifications are available. Other grades may be used,
7.10 Sample Cups, vented.
provided it is first ascertained that the reagent is of sufficiently
7.11 Helium, He—minimum 99.99 purity for use as a
high purity to permit its use without lessening the accuracy of
chamber purge gas for the analysis of Cl, P and S. This
the determination.
numerical purity is intended to specify a general grade of
7.2 Purity of Water—Unless otherwise indicated, references
helium. Ultra-high purity helium is not required for this test
to water shall be understood to mean meeting the numerical
method.
requirements of Type II water as defined by Specification
D1193.
8. Sample
7.3 Aluminum Oxide, Al O —pre-calcined at 1500°C, ap-
2 3 8.1 Because of the potential heterogeneous nature of LHW,
proximately 100 to 125 mesh.
allpossibleeffortsshouldbemadetoensurethatrepresentative
samples are taken.
7.4 Aqueous or organic-based Atomic Absorption Standards
(AAS),1000mg/LfortheelementsAg,As,Ba,Cd,Cr,Cu,Fe,
9. Preparation of Apparatus
Hg,K,Ni,Pb,Sb,Se,Sn,Tl,V,andZn.Standardsolutionsfor
9.1 Follow the manufacturer’s instructions for set-up,
elements not listed are also available.
conditioning, preparation and maintenance of the XRF spec-
NOTE 1—AAS standards are typically presented in mass/vol units. The
trometer.
density of these solutions can be considered as unity (that is, 1) thus they
can be considered as % mass/mass (m/m).
9.2 When required, reference spectra should be obtained
from pure element standards for all deconvoluted elements.
7.5 1-bromonaphthalene, trichlorobenzene, iodobenzoic
acid, triethyl phosphate and dithiodiglycol are the recom-
9.3 Spectral and matrix interferences as listed in the Inter-
mended standards for the elements Br, Cl, I, P and S,
ferences section must be addressed per the manufacturer’s
respectively.
recommendations.
7.6 Low Molecular Weight Polyethylene Glycol (PEG 400,
10. Calibration and Standardization
or equivalent) or Water is used for producing method blank.
10.1 The spectrometer must be calibrated using an appro-
7.7 High-Density Polyethylene (HDPE) Wide-mouth,
priate reference element(s) at a minimum frequency as recom-
Round, Screw-Cap Bottles, 50 to 60 mL capacity.
mended by the manufacturer.
7.8 Mixing Balls, approximately 1 cm diameter, stainless
10.2 Analytical standards should be prepared gravimetri-
steel or equivalent.
cally by blending the solution or pure element standards with
NOTE 2—Potential low level Cr, Fe or Ni (<20 mg/kg ) contamination
Al O tosuitablestandardconcentrationsasdeterminedbythe
2 3
due to the use of stainless steel may exist. Other suitable materials would
user’s analytical requirements. Table 1 gives recommended
be tungsten carbide, Zr or Ta.
concentration ranges for regression. Standards can be single or
7.9 Thin-film Support.
multi-element mixtures. Standard solutions are generally
mixed with Al O at a ratio of 3:1.
NOTE 3—The user should select a thin-film support that provides for
2 3
maximum transmittance and is resistant to typical components in LHW.
NOTE4—Morethanonestandardelement(s)solutioncanbeaddedtoa
The thin-film supports used in the development of this test method were
single15gAl O massprovidedthetotalmassofstandardis5g.Thiswill
2 3
maintain the proper 3:1 ratio while allowing mixtures of potentially
incompatible elements to be combined in a single standard.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
10.2.1 The number of standards required to produce cali-
listed by the American Chemical Society, see Analar Standards for Laboratory
brations is dependent on the number of elements to be
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
determined. Generally, two calibrations are produced, the first
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. is to determine potentially major elements such as halogens, S
D6052 − 97 (2016)
& P.The second is to determine trace elements, typically toxic the composition of materials without the use of a suite of
metalsandheavyelements.Theminimumnumberofstandards standards. The setup of a particular manufacturer’s fundamen-
required can be determined from the following equation: tal parameters method may require a high and low concentra-
minimum standards required=number elements determined tion or mid-range concentration for each element present to
plustwo.Bothoftheabovecalibrationsshoulduseaminimum determinetheinitialsensitivityfortheelementsinthealumina
oftenstandardseachtocovertheelementconcentrationranges matrix.Othermanufacturersprovidetheinitialsensitivitywith
shown in Table 1 and to ensure that adequate data is available the added option to align the sensitivity to a specific matrix
to assess spectral overlaps as described in 5.1. type for more accurate determinations using a single similar
standard containing the elements of interest. By measuring the
10.3 The Al O +element(s) specimen is placed into an
2 3
X-ray intensity (cps) for each element and using the above
XRFsamplecupsupportedbyasuitablethin-film.Thesample
determined sensitivity factor for each element plus various
is gently tapped on a flat, hard surface to settle the powder
equations to account for X-ray absorption and enhancement
against the thin-film support and ensure there are no air gaps.
effects, the concentration of all elements present can be
10.3.1 The standard specimen in the sample cups is placed
estimated. The exact equations used will differ for each
in the spectrometer’s sample holder avoiding any contact with
manufacturer.
the film or rough handling that may disturb the standards.
10.4.2.1 Followthemanufacturer’sfundamentalparameters
10.4 Two methods of calibration are available.
set-up recommendations. The stoichiometric set-up of the
10.4.1 Method A—Empiricalcalibrationmethodusingasuit
fundamental parameters method for the analysis of the LHW
ofstandardconcentrations.Standardconcentrationsarelimited
mixed with alumina should allow for the manual input of a
to 600 mg/kg forAg,As, Ba, Br, Cd, Cr, Cu, Fe, Hg, I, K, Ni,
fixed 75% Al O concentration and the use of carbon as a
2 3
Pb, Sb, Se, Sn, Tl, V, and Zn. Standard concentrations are
balance estimate of the solvent/aqueous phase with the ele-
limited to 5% for Cl, P, S, and other light elements (that is,
ments of interest determined directly according to the prin-
=22 and <0.5% for Br). The limits ensure staying within the
ciples of 10.4.2.
linear range and due to the limited concentration range of
10.4.3 Two control samples are needed for monitoring
available traceable standards. The standards should provide a
instrument stability. One control sample is a blank preparation
linear response of element intensity to concentration. Serial
using PEG or the low concentration drift correction monitor
dilutions of analyte standards can be used to set up the
used in 10.4.1.1. The other sample is a stable mixture contain-
calibration for each element. Multi-element standards can then
ing a suitable range and number of elements (for example, S,
be used to assess the deconvolution requirements of the
V, Zn, Pb, and Ba) at concentrations near the middle of the
spectrometer and check for calibration linearity.
calibration ranges. A mixture of leftover samples/standards,
NOTE 5—Standards may be diluted into the linear range using low
spiked with element concentrations as needed and carefully
molecular weight polyethylene glycol (PEG) or water. The choice of
mixed may be used.
diluent is dependent upon whether the original standard solution is
10.4.4 Restandardization should be carried out whenever
aqueous- or organic-based. For example, a 5000 mg/kg organic-based Pb
quality control results defined in Section 14 are outside data
standardsolutioncanbedilutedintothe0–600mg/kgrangebycombining
and mixing 15 g of Al O +0.5 g of 5000 mg/kg Pb standard solu-
2 5 quality objectives as determined by the user. Method A: The
tion+4.5 g PEG. This yields a ten-fold dilution yielding a prepared
initiallinearregressionsareperformedonlyonceasper10.4.1.
standard concentration of 500 mg/kg.
A day zero measurement of the drift correction monitors,
10.4.1.1 Drift Correction Monitors—To correct for instru-
10.4.1.1 during the set-up of the initial regression allows for
mentaldrift,usephysicallystable,soliddisksorpressedpellets
subsequent re-calibration to be performed using the two
containing at least one element measured under each instru-
standardsdefinedin10.4.1.1,viaarestandardizationprocedure
mental condition used. At least two disks are necessary to
in order to check the values of the slope and intercept for each
correct both sensitivity and base-line drifts.
...
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D6052 − 97 (Reapproved 2016)
Standard Test Method for
Preparation and Elemental Analysis of Liquid Hazardous
Waste by Energy-Dispersive X-Ray Fluorescence
This standard is issued under the fixed designation D6052; 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 sample mixture is transferred into a disposable sample cup and
placed in the spectrometer for analysis.
1.1 This test method covers the determination of trace and
major element concentrations by energy-dispersive X-ray fluo-
3.2 The K spectral emission lines are used for elements
rescence spectrometry (EDXRF) in liquid hazardous waste Si-Ba.
(LHW).
3.3 The L spectral emission lines are used for elements with
1.2 This test method has been used successfully on numer- atomic numbers greater than Ba.
ous samples of aqueous and organic-based LHW for the
determination of the following elements: Ag, As, Ba, Br, Cd, 4. Significance and Use
Cl, Cr, Cu, Fe, Hg, I, K, Ni, P, Pb, S, Sb, Se, Sn, Tl, V, and Zn.
4.1 The elemental analysis of liquid hazardous waste is
1.3 This test method is applicable for other elements (Si-U)
often important for regulatory and process specific require-
not listed in 1.2.
ments. This test method provides the user an accurate, rapid
method for trace and major element determinations.
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
5. Interferences
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
5.1 Spectral Overlaps (Deconvolution):
bility of regulatory limitations prior to use.
5.1.1 Samples containing a mixture of elements often ex-
hibit X-ray emission line overlap. Modern Si (Li) detectors
2. Referenced Documents
generally provide adequate resolution to minimize the effects
2.1 ASTM Standards:
of spectral overlap. In cases where emission line overlap exists,
C982 Guide for Selecting Components for Energy-
techniques of peak fitting exist for extracting corrected analyte
Dispersive X-Ray Fluorescence (XRF) Systems (With-
emission line intensities. For example, the PbLα “line overlaps
drawn 2008)
with the AsKα.” The PbLβ line can be used to avoid this
D1193 Specification for Reagent Water
overlap and the AsK lines can then be resolved from the PbLα
2.2 Other ASTM Documents:
overlap. The actual lines used for any particular element should
ASTM Data Series DS 46 X-ray Emission Wavelengths and
be such that overlaps are minimized. Follow the EDXRF
KeV Tables for Nondiffractive Analysis
manufacturer’s recommendation concerning spectral deconvo-
lution. Reference should be made to ASTM Data Series DS 46
3. Summary of Test Method
for detailed information on potential line overlaps.
3.1 A weighed portion of activated alumina and sample are
5.2 Matrix Interferences (Regression):
combined in a mixing vessel and shaken until well mixed. The
5.2.1 Matrix interference in the measurement of “as re-
ceived” LHW samples using EDXRF has been the principle
This test method is under the jurisdiction of ASTM Committee D34 on Waste
limitation in the development and expanding use of this
Management and is the direct responsibility of Subcommittee D34.01.06 on
instrumental technique. Using well understood XRF principles
Analytical Methods.
Current edition approved Sept. 1, 2016. Published September 2016. Originally for controlling matrix effects, for example, dilution and matrix
approved in 1997. Last previous edition approved in 2008 as D6052 – 97 (2008).
modification using lithium borate fusion and addition of heavy
DOI: 10.1520/D6052-97R16.
absorbers, a matrix can be stabilized. Using calcined alumina
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
and the above principles matrices are stabilized for quantitative
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
EDXRF analysis.
the ASTM website.
5.2.2 The response range of this test method should be
The last approved version of this historical standard is referenced on
linear with respect to the elements of interest and their
www.astm.org.
Available from ASTM Headquarters, Customer Service. regulatory or process control, or both, action thresholds. Large
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6052 − 97 (2016)
TABLE 1 Recommended Standards Ranges
concentration variations of element or matrix, or both, compo-
nents in LHW samples can result in non-linear X-ray intensity Low Con- High Con- High Con-
Low Con-
centration centration centration
response at increasing element concentrations.
Analyte Analyte centration
Range, Range, Range,
Range, mg/kg
mg/kg mg/kg mg/kg
6. Apparatus
Ag 5 600 Zn 5 600
Ba 5 600 As 5 600
6.1 Energy-dispersive X-ray Fluorescence Spectrometer, ca-
P 0.1 % 5 % Se 5 600
pable of measuring the wavelengths of the elements listed in
S 0.05 % 5 % Br 10 5000
1.2. Refer to Guide C982 for system specifications.
Cl 0.05 % 5 % Cd 5 600
K 0.1 % 5 % Sb 5 600
6.2 Analytical Balance, capable of weighing to 0.001 g.
V 5 600 Sn 5 600
Cr 5 600 I 5 600
7. Reagents and Materials Fe 5 600 Hg 5 600
Ni 5 600 Tl 5 600
7.1 Purity of Reagents—Reagent grade chemicals shall be
Cu 5 600 Pb 5 600
used in all tests. Unless otherwise indicated, it is intended that
all reagents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society, where
a polypropylene base and a high-purity, 4 µm polyester film.
such specifications are available. Other grades may be used,
7.10 Sample Cups, vented.
provided it is first ascertained that the reagent is of sufficiently
7.11 Helium, He—minimum 99.99 purity for use as a
high purity to permit its use without lessening the accuracy of
chamber purge gas for the analysis of Cl, P and S. This
the determination.
numerical purity is intended to specify a general grade of
7.2 Purity of Water—Unless otherwise indicated, references
helium. Ultra-high purity helium is not required for this test
to water shall be understood to mean meeting the numerical
method.
requirements of Type II water as defined by Specification
D1193.
8. Sample
7.3 Aluminum Oxide, Al O —pre-calcined at 1500°C, ap-
2 3 8.1 Because of the potential heterogeneous nature of LHW,
proximately 100 to 125 mesh.
all possible efforts should be made to ensure that representative
samples are taken.
7.4 Aqueous or organic-based Atomic Absorption Standards
(AAS), 1000 mg/L for the elements Ag, As, Ba, Cd, Cr, Cu, Fe,
9. Preparation of Apparatus
Hg, K, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn. Standard solutions for
elements not listed are also available. 9.1 Follow the manufacturer’s instructions for set-up,
conditioning, preparation and maintenance of the XRF spec-
NOTE 1—AAS standards are typically presented in mass/vol units. The
trometer.
density of these solutions can be considered as unity (that is, 1) thus they
can be considered as % mass/mass (m/m).
9.2 When required, reference spectra should be obtained
7.5 1-bromonaphthalene, trichlorobenzene, iodobenzoic from pure element standards for all deconvoluted elements.
acid, triethyl phosphate and dithiodiglycol are the recom-
9.3 Spectral and matrix interferences as listed in the Inter-
mended standards for the elements Br, Cl, I, P and S,
ferences section must be addressed per the manufacturer’s
respectively.
recommendations.
7.6 Low Molecular Weight Polyethylene Glycol (PEG 400,
10. Calibration and Standardization
or equivalent) or Water is used for producing method blank.
10.1 The spectrometer must be calibrated using an appro-
7.7 High-Density Polyethylene (HDPE) Wide-mouth,
priate reference element(s) at a minimum frequency as recom-
Round, Screw-Cap Bottles, 50 to 60 mL capacity.
mended by the manufacturer.
7.8 Mixing Balls, approximately 1 cm diameter, stainless
10.2 Analytical standards should be prepared gravimetri-
steel or equivalent.
cally by blending the solution or pure element standards with
NOTE 2—Potential low level Cr, Fe or Ni (<20 mg/kg ) contamination
Al O to suitable standard concentrations as determined by the
2 3
due to the use of stainless steel may exist. Other suitable materials would
user’s analytical requirements. Table 1 gives recommended
be tungsten carbide, Zr or Ta.
concentration ranges for regression. Standards can be single or
7.9 Thin-film Support.
multi-element mixtures. Standard solutions are generally
mixed with Al O at a ratio of 3:1.
NOTE 3—The user should select a thin-film support that provides for
2 3
maximum transmittance and is resistant to typical components in LHW.
NOTE 4—More than one standard element(s) solution can be added to a
The thin-film supports used in the development of this test method were
single 15 g Al O mass provided the total mass of standard is 5 g. This will
2 3
maintain the proper 3:1 ratio while allowing mixtures of potentially
incompatible elements to be combined in a single standard.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
10.2.1 The number of standards required to produce cali-
listed by the American Chemical Society, see Analar Standards for Laboratory
brations is dependent on the number of elements to be
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
determined. Generally, two calibrations are produced, the first
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. is to determine potentially major elements such as halogens, S
D6052 − 97 (2016)
& P. The second is to determine trace elements, typically toxic the composition of materials without the use of a suite of
metals and heavy elements. The minimum number of standards standards. The setup of a particular manufacturer’s fundamen-
required can be determined from the following equation: tal parameters method may require a high and low concentra-
minimum standards required = number elements determined tion or mid-range concentration for each element present to
plus two. Both of the above calibrations should use a minimum determine the initial sensitivity for the elements in the alumina
of ten standards each to cover the element concentration ranges matrix. Other manufacturers provide the initial sensitivity with
shown in Table 1 and to ensure that adequate data is available the added option to align the sensitivity to a specific matrix
to assess spectral overlaps as described in 5.1. type for more accurate determinations using a single similar
standard containing the elements of interest. By measuring the
10.3 The Al O + element(s) specimen is placed into an
2 3
X-ray intensity (cps) for each element and using the above
XRF sample cup supported by a suitable thin-film. The sample
determined sensitivity factor for each element plus various
is gently tapped on a flat, hard surface to settle the powder
equations to account for X-ray absorption and enhancement
against the thin-film support and ensure there are no air gaps.
effects, the concentration of all elements present can be
10.3.1 The standard specimen in the sample cups is placed
estimated. The exact equations used will differ for each
in the spectrometer’s sample holder avoiding any contact with
manufacturer.
the film or rough handling that may disturb the standards.
10.4.2.1 Follow the manufacturer’s fundamental parameters
10.4 Two methods of calibration are available.
set-up recommendations. The stoichiometric set-up of the
10.4.1 Method A—Empirical calibration method using a suit
fundamental parameters method for the analysis of the LHW
of standard concentrations. Standard concentrations are limited
mixed with alumina should allow for the manual input of a
to 600 mg/kg for Ag, As, Ba, Br, Cd, Cr, Cu, Fe, Hg, I, K, Ni,
fixed 75 % Al O concentration and the use of carbon as a
2 3
Pb, Sb, Se, Sn, Tl, V, and Zn. Standard concentrations are
balance estimate of the solvent/aqueous phase with the ele-
limited to 5 % for Cl, P, S, and other light elements (that is,
ments of interest determined directly according to the prin-
= 22 and <0.5 % for Br). The limits ensure staying within the
ciples of 10.4.2.
linear range and due to the limited concentration range of
10.4.3 Two control samples are needed for monitoring
available traceable standards. The standards should provide a
instrument stability. One control sample is a blank preparation
linear response of element intensity to concentration. Serial
using PEG or the low concentration drift correction monitor
dilutions of analyte standards can be used to set up the
used in 10.4.1.1. The other sample is a stable mixture contain-
calibration for each element. Multi-element standards can then
ing a suitable range and number of elements (for example, S,
be used to assess the deconvolution requirements of the
V, Zn, Pb, and Ba) at concentrations near the middle of the
spectrometer and check for calibration linearity.
calibration ranges. A mixture of leftover samples/standards,
NOTE 5—Standards may be diluted into the linear range using low
spiked with element concentrations as needed and carefully
molecular weight polyethylene glycol (PEG) or water. The choice of
mixed may be used.
diluent is dependent upon whether the original standard solution is
10.4.4 Restandardization should be carried out whenever
aqueous- or organic-based. For example, a 5000 mg/kg organic-based Pb
standard solution can be diluted into the 0–600 mg/kg range by combining quality control results defined in Section 14 are outside data
and mixing 15 g of Al O + 0.5 g of 5000 mg/kg Pb standard solu-
quality objectives as determined by the user. Method A: The
2 5
tion + 4.5 g PEG. This yields a ten-fold dilution yielding a prepared
initial linear regressions are performed only once as per 10.4.1.
standard concentration of 500 mg/kg.
A day zero measurement of the drift correction monitors,
10.4.1.1 Drift Correction Monitors—To correct for instru-
10.4.1.1 during the set-up of the initial regression allows for
mental drift, use physically stable, solid disks or pressed pellets
subsequent re-calibration to be performed using the two
containing at least one element measured under each instru-
standards defined in 10.4.1.1, via a restandardization procedure
mental condition use
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D6052 − 97 (Reapproved 2008) D6052 − 97 (Reapproved 2016)
Standard Test Method for
Preparation and Elemental Analysis of Liquid Hazardous
Waste by Energy-Dispersive X-Ray Fluorescence
This standard is issued under the fixed designation D6052; 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
1.1 This test method covers the determination of trace and major element concentrations by energy-dispersive X-ray
fluorescence spectrometry (EDXRF) in liquid hazardous waste (LHW).
1.2 This test method has been used successfully on numerous samples of aqueous and organic-based LHW for the determination
of the following elements: Ag, As, Ba, Br, Cd, Cl, Cr, Cu, Fe, Hg, I, K, Ni, P, Pb, S, Sb, Se, Sn, Tl, V, and Zn.
1.3 This test method is applicable for other elements (Si-U) not listed in 1.2.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
C982 Guide for Selecting Components for Energy-Dispersive X-Ray Fluorescence (XRF) Systems (Withdrawn 2008)
D1193 Specification for Reagent Water
2.2 Other ASTM Documents:
ASTM Data Series DS 46 X-ray Emission Wavelengths and KeV Tables for Nondiffractive Analysis
3. Summary of Test Method
3.1 A weighed portion of activated alumina and sample are combined in a mixing vessel and shaken until well mixed. The
sample mixture is transferred into a disposable sample cup and placed in the spectrometer for analysis.
3.2 The K spectral emission lines are used for elements Si-Ba.
3.3 The L spectral emission lines are used for elements with atomic numbers greater than Ba.
4. Significance and Use
4.1 The elemental analysis of liquid hazardous waste is often important for regulatory and process specific requirements. This
test method provides the user an accurate, rapid method for trace and major element determinations.
5. Interferences
5.1 Spectral Overlaps (Deconvolution):
5.1.1 Samples containing a mixture of elements often exhibit X-ray emission line overlap. Modern Si (Li) detectors generally
provide adequate resolution to minimize the effects of spectral overlap. In cases where emission line overlap exists, techniques of
peak fitting exist for extracting corrected analyte emission line intensities. For example, the PbLα “line overlaps with the AsKα.”
The PbLβ line can be used to avoid this overlap and the AsK lines can then be resolved from the PbLα overlap. The actual lines
This test method is under the jurisdiction of ASTM Committee D34 on Waste Management and is the direct responsibility of Subcommittee D34.01.06 on Analytical
Methods.
Current edition approved Feb. 1, 2008Sept. 1, 2016. Published March 2008September 2016. Originally approved in 1997. Last previous edition approved in 20032008
as D6052 – 97 (2008).(2003). DOI: 10.1520/D6052-97R08.10.1520/D6052-97R16.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 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 the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
Available from ASTM Headquarters, Customer Service.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6052 − 97 (2016)
used for any particular element should be such that overlaps are minimized. Follow the EDXRF manufacturer’s recommendation
concerning spectral deconvolution. Reference should be made to ASTM Data Series DS 46 for detailed information on potential
line overlaps.
5.2 Matrix Interferences (Regression):
5.2.1 Matrix interference in the measurement of “as received” LHW samples using EDXRF has been the principle limitation
in the development and expanding use of this instrumental technique. Using well understood XRF principles for controlling matrix
effects, for example, dilution and matrix modification using lithium borate fusion and addition of heavy absorbers, a matrix can
be stabilized. Using calcined alumina and the above principles matrices are stabilized for quantitative EDXRF analysis.
5.2.2 The response range of this test method should be linear with respect to the elements of interest and their regulatory or
process control, or both, action thresholds. Large concentration variations of element or matrix, or both, components in LHW
samples can result in non-linear X-ray intensity response at increasing element concentrations.
6. Apparatus
6.1 Energy-dispersive X-ray Fluorescence Spectrometer, capable of measuring the wavelengths of the elements listed in 1.2.
Refer to Guide C982 for system specifications.
6.2 Analytical Balance, capable of weighing to 0.001 g.
7. Reagents and Materials
7.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American ChemicalSociety, Chemical
Society, where such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the accuracy of the determination.
7.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean meeting the numerical
requirements of Type II water as defined by Specification D1193.
7.3 Aluminum Oxide, Al O —pre-calcined at 1500°C, approximately 100 to 125 mesh.
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7.4 Aqueous or organic-based Atomic Absorption Standards (AAS), 1000 mg/L for the elements Ag, As, Ba, Cd, Cr, Cu, Fe, Hg,
K, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn. Standard solutions for elements not listed are also available.
NOTE 1—AAS standards are typically presented in mass/vol units. The density of these solutions can be considered as unity (that is, 1) thus they can
be considered as % mass/mass (m/m).
7.5 1-bromonaphthalene, trichlorobenzene, iodobenzoic acid, triethyl phosphate and dithiodiglycol are the recommended
standards for the elements Br, Cl, I, P and S, respectively.
7.6 Low Molecular Weight Polyethylene Glycol (PEG 400, or equivalent) or Water is used for producing method blank.
7.7 High-Density Polyethylene (HDPE) Wide-mouth, Round, Screw-Cap Bottles, 50 to 60 mL capacity.
7.8 Mixing Balls, approximately 1 cm diameter, stainless steel or equivalent.
NOTE 2—Potential low level Cr, Fe or Ni (<20 mg/kg ) contamination due to the use of stainless steel may exist. Other suitable materials would be
tungsten carbide, Zr or Ta.
7.9 Thin-film Support.
NOTE 3—The user should select a thin-film support that provides for maximum transmittance and is resistant to typical components in LHW. The
thin-film supports used in the development of this test method were a polypropylene base and a high-purity, 4 μm polyester film.
7.10 Sample Cups, vented.
7.11 Helium, He—minimum 99.99 purity for use as a chamber purge gas for the analysis of Cl, P and S. This numerical purity
is intended to specify a general grade of helium. Ultra-high purity helium is not required for this test method.
8. Sample
8.1 Because of the potential heterogeneous nature of LHW, all possible efforts should be made to ensure that representative
samples are taken.
9. Preparation of Apparatus
9.1 Follow the manufacturer’s instructions for set-up, conditioning, preparation and maintenance of the XRF spectrometer.
9.2 When required, reference spectra should be obtained from pure element standards for all deconvoluted elements.
Reagent Chemicals, American Chemical Society Specifications, , American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D6052 − 97 (2016)
TABLE 1 Recommended Standards Ranges
Low Con- High Con- High Con-
Low Con-
centration centration centration
Analyte Analyte centration
Range, Range, Range,
Range, mg/kg
mg/kg mg/kg mg/kg
Ag 5 600 Zn 5 600
Ba 5 600 As 5 600
P 0.1 % 5 % Se 5 600
S 0.05 % 5 % Br 10 5000
Cl 0.05 % 5 % Cd 5 600
K 0.1 % 5 % Sb 5 600
V 5 600 Sn 5 600
Cr 5 600 I 5 600
Fe 5 600 Hg 5 600
Ni 5 600 Tl 5 600
Cu 5 600 Pb 5 600
9.3 Spectral and matrix interferences as listed in the Interferences section must be addressed per the manufacturer’s
recommendations.
10. Calibration and Standardization
10.1 The spectrometer must be calibrated using an appropriate reference element(s) at a minimum frequency as recommended
by the manufacturer.
10.2 Analytical standards should be prepared gravimetrically by blending the solution or pure element standards with Al O to
2 3
suitable standard concentrations as determined by the user’s analytical requirements. Table 1 gives recommended concentration
ranges for regression. Standards can be single or multi-element mixtures. Standard solutions are generally mixed with Al O at a
2 3
ratio of 3:1.
NOTE 4—More than one standard element(s) solution can be added to a single 15 g Al O mass provided the total mass of standard is 5 g. This will
2 3
maintain the proper 3:1 ratio while allowing mixtures of potentially incompatible elements to be combined in a single standard.
10.2.1 The number of standards required to produce calibrations is dependent on the number of elements to be determined.
Generally, two calibrations are produced, the first is to determine potentially major elements such as halogens, S & P. The second
is to determine trace elements, typically toxic metals and heavy elements. The minimum number of standards required can be
determined from the following equation: minimum standards required = number elements determined plus two. Both of the above
calibrations should use a minimum of ten standards each to cover the element concentration ranges shown in Table 1 and to ensure
that adequate data is available to assess spectral overlaps as described in 5.1.
10.3 The Al O + element(s) specimen is placed into an XRF sample cup supported by a suitable thin-film. The sample is gently
2 3
tapped on a flat, hard surface to settle the powder against the thin-film support and ensure there are no air gaps.
10.3.1 The standard specimen in the sample cups is placed in the spectrometer’s sample holder avoiding any contact with the
film or rough handling that may disturb the standards.
10.4 Two methods of calibration are available.
10.4.1 Method A—Empirical calibration method using a suit of standard concentrations. Standard concentrations are limited to
600 mg/kg for Ag, As, Ba, Br, Cd, Cr, Cu, Fe, Hg, I, K, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn. Standard concentrations are limited to
5 % for Cl, P, S, and other light elements (that is,
and due to the limited concentration range of available traceable standards. The standards should provide a linear response of
element intensity to concentration. Serial dilutions of analyte standards can be used to set up the calibration for each element.
Multi-element standards can then be used to assess the deconvolution requirements of the spectrometer and check for calibration
linearity.
NOTE 5—Standards may be diluted into the linear range using low molecular weight polyethylene glycol (PEG) or water. The choice of diluent is
dependent upon whether the original standard solution is aqueous- or organic-based. For example, a 5000 mg/kg organic-based Pb standard solution can
be diluted into the 0–600 mg/kg range by combining and mixing 15 g of Al O + 0.5 g of 5000 mg/kg Pb standard solution + 4.5 g PEG. This yields a
2 5
ten-fold dilution yielding a prepared standard concentration of 500 mg/kg.
10.4.1.1 Drift Correction Monitors—To correct for instrumental drift, use physically stable, solid disks or pressed pellets
containing at least one element measured under each instrumental condition used. At least two disks are necessary to correct both
sensitivity and base-line drifts. One should provide a high net count-rate similar to standards from the upper end of the calibration
range and the other should provide a low net count-rate similar to the blank. Measure the net count-rate for each element in the
high concentration disk in such a way that the counting statistical error due to random fluctuation of the X-ray flux is less than
Pressed aluminum powder doped with the elements of interest has been found to be satisfactory. Preparation guidelines can be found in: Forte, M., “Fabrication and Use
of Permanent Monitors and Standards,” X-ray Spectrometry, 1983, Vol 3, pp. 115.
D6052 − 97 (2016)
0.5 % relative to the net count-rate. Counting times must be long enough to collect 40 000 net counts for each element in the
high-concentration disk. Use the same counting times when measuring the low concentration or blank disk.
10.4.2 Method B—Fundamental Parameters method. Most EDXRF manufacturers provide software capable of estimating the
composition of materials without the use of a suite of standards. The setup of a particular manufacturer’s fundamental parameters
method may require a high and low concentration or mid-range concentration for each element present to determine the initial
sensitivity for the elements in the alumina matrix. Other manufacturers provide the initial sensitivity with the added option to align
the sensitivity to a specific matrix type for more accurate determinations using a single similar standard containing the elements
of interest. By measuring the X-ray intensity (cps) for each element and using the above determined sensitivity factor for each
element plus various equations to account for X-ray absorption and enhancement effects, the concentration of all elements present
can be estimated. The exact equations used will differ for each manufacturer.
...
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