ASTM D6052-97

Standard Test Method for Preparation and Elemental Analysis of Liquid Hazardous Waste by Energy-Dispersive X-Ray Fluorescence

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, T1, 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

• Status: Historical
• Publication Date: 31-Dec-1996
• Technical Committee: D34 - Waste Management
• Drafting Committee: D34.01.06 - Analytical Methods

Relations

• Replaced By: ASTM D6052-97(2003) - Standard Test Method for Preparation and Elemental Analysis of Liquid Hazardous Waste by Energy-Dispersive X-Ray Fluorescence
• Effective Date: 10-Mar-2003

Standards Content (Sample)

NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
Designation: D 6052 – 97
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 D 6052; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope 4. Significance and Use
1.1 This test method covers the determination of trace and 4.1 The elemental analysis of liquid hazardous waste is
major element concentrations by energy-dispersive X-ray fluo- often important for regulatory and process specific require-
rescence spectrometry (EDXRF) in liquid hazardous waste ments. This test method provides the user an accurate, rapid
(LHW). method for trace and major element determinations.
1.2 This test method has been used successfully on numer-
5. Interferences
ous samples of aqueous and organic-based LHW for the
5.1 Spectral Overlaps (Deconvolution):
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. 5.1.1 Samples containing a mixture of elements often ex-
hibit X-ray emission line overlap. Modern Si (Li) detectors
1.3 This test method is applicable for other elements (Si-U)
not listed in 1.2. generally provide adequate resolution to minimize the effects
of spectral overlap. In cases where emission line overlap exists,
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the techniques of peak fitting exist for extracting corrected analyte
emission line intensities. For example, the PbLa “line overlaps
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- with the AsKa.” The PbLb line can be used to avoid this
overlap and the AsK lines can then be resolved from the PbLa
bility of regulatory limitations prior to use.
overlap. The actual lines used for any particular element should
2. Referenced Documents
be such that overlaps are minimized. Follow the EDXRF
2.1 ASTM Standards: manufacturer’s recommendation concerning spectral deconvo-
C 982 Guide for Selecting Components for Energy- lution. Reference should be made to ASTM Data Series DS 46
Dispersive X-ray Fluorescence (XRF) Systems for detailed information on potential line overlaps.
D 1193 Specification for Reagent Water 5.2 Matrix Interferences (Regression):
2.2 Other ASTM Documents: 5.2.1 Matrix interference in the measurement of “as re-
ASTM Data Series DS 46 X-Ray Emission Wavelengths ceived” LHW samples using EDXRF has been the principle
and KeV Tables for Nondiffractive Analysis limitation in the development and expanding use of this
instrumental technique. Using well understood XRF principles
3. Summary of Test Method
for controlling matrix effects, for example, dilution and matrix
3.1 A weighed portion of activated alumina and sample are
modification using lithium borate fusion and addition of heavy
combined in a mixing vessel and shaken until well mixed. The absorbers, a matrix can be stabilized. Using calcined alumina
sample mixture is transferred into a disposable sample cup and
and the above principles matrices are stabilized for quantitative
placed in the spectrometer for analysis. EDXRF analysis.
3.2 The K spectral emission lines are used for elements
5.2.2 The response range of this test method should be
Si-Ba. linear with respect to the elements of interest and their
3.3 The L spectral emission lines are used for elements with
regulatory or process control, or both, action thresholds. Large
atomic numbers greater than Ba. concentration variations of element or matrix, or both, compo-
nents in LHW samples can result in non-linear X-ray intensity
response at increasing element concentrations.
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
6. Apparatus
Analytical Methods.
6.1 Energy-dispersive X-ray Fluorescence Spectrometer,
Current edition approved Jan. 10, 1997. Published March 1997.
Annual Book of ASTM Standards, Vol 12.01.
capable of measuring the wavelengths of the elements listed in
Annual Book of ASTM Standards, Vol 11.01.
1.2. Refer to Guide C 982 for system specifications.
Available from ASTM Headquarters, Customer Service.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 6052
6.2 Analytical Balance, capable of weighing to 0.001 g. all possible efforts should be made to ensure that representative
samples are taken.
7. Reagents and Materials
9. Preparation of Apparatus
7.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that 9.1 Follow the manufacturer’s instructions for set-up, con-
all reagents conform to the specifications of the Committee on ditioning, preparation and maintenance of the XRF spectrom-
Analytical Reagents of the American ChemicalSociety, where eter.
9.2 When required, reference spectra should be obtained
such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently from pure element standards for all deconvoluted elements.
9.3 Spectral and matrix interferences as listed in the Inter-
high purity to permit its use without lessening the accuracy of
the determination. ferences section must be addressed per the manufacturer’s
recommendations.
7.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean meeting the numerical
10. Calibration and Standardization
requirements of Type II water as defined by Specification
10.1 The spectrometer must be calibrated using an appro-
D 1193.
priate reference element(s) at a minimum frequency as recom-
7.3 Aluminum Oxide, Al O —pre-calcined at 1500°C, ap-
2 3
mended by the manufacturer.
proximately 100 to 125 mesh.
10.2 Analytical standards should be prepared gravimetri-
7.4 Aqueous or organic-based Atomic Absorption Standards
cally by blending the solution or pure element standards with
(AAS), 1000 mg/L for the elements Ag, As, Ba, Cd, Cr, Cu, Fe,
Al O to suitable standard concentrations as determined by the
Hg, K, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn. Standard solutions for
2 3
user’s analytical requirements. Table 1 gives recommended
elements not listed are also available.
concentration ranges for regression. Standards can be single or
NOTE 1—AAS standards are typically presented in mass/vol units. The
multi-element mixtures. Standard solutions are generally
density of these solutions can be considered as unity (that is, 1) thus they
mixed with Al O at a ratio of 3:1.
2 3
can be considered as % mass/mass (m/m).
NOTE 4—More than one standard element(s) solution can be added to a
7.5 1-bromonaphthalene, trichlorobenzene, iodobenzoic
single 15 g Al O mass provided the total mass of standard is 5 g. This will
2 3
acid, triethyl phosphate and dithiodiglycol are the recom-
maintain the proper 3:1 ratio while allowing mixtures of potentially
mended standards for the elements Br, Cl, I, P and S,
incompatible elements to be combined in a single standard.
respectively.
10.2.1 The number of standards required to produce cali-
7.6 Low Molecular Weight Polyethylene Glycol (PEG 400,
brations is dependent on the number of elements to be
or equivalent) or Water is used for producing method blank.
determined. Generally, two calibrations are produced, the first
7.7 High-Density Polyethylene (HDPE) Wide-mouth,
is to determine potentially major elements such as halogens, S
Round, Screw-Cap Bottles, 50 to 60 mL capacity.
& P. The second is to determine trace elements, typically toxic
7.8 Mixing Balls, approximately 1 cm diameter, stainless
metals and heavy elements. The minimum number of standards
steel or equivalent.
required can be determined from the following equation:
NOTE 2—Potential low level Cr, Fe or Ni (<20 mg/kg ) contamination
minimum standards required = number elements determined
due to the use of stainless steel may exist. Other suitable materials would
plus two. Both of the above calibrations should use a minimum
be tungsten carbide, Zr or Ta.
of ten standards each to cover the element concentration ranges
7.9 Thin-film Support.
shown in Table 1 and to ensure that adequate data is available
to assess spectral overlaps as described in 5.1.
NOTE 3—The user should select a thin-film support that provides for
maximum transmittance and is resistant to typical components in LHW. 10.3 The Al O + element(s) specimen is placed into an
2 3
The thin-film supports used in the development of this test method were
XRF sample cup supported by a suitable thin-film. The sample
a polypropylene base and a high-purity, 4 μm polyester film.
is gently tapped on a flat, hard surface to settle the powder
7.10 Sample Cups, vented. against the thin-film support and ensure there are no air gaps.
7.11 Helium, He—minimum 99.99 purity for use as a
TABLE 1 Recommended Standards Ranges
chamber purge gas for the analysis of Cl, P and S. This
numerical purity is intended to specify a general grade of Low Con- High Con- High Con-
Low Con-
centration centration centration
helium. Ultra-high purity helium is not required for this test
Analyte Analyte centration
Range, Range, Range,
Range, mg/kg
method.
mg/kg mg/kg mg/kg
Ag 5 600 Zn 5 600
8. Sample
Ba 5 600 As 5 600
P 0.1 % 5 % Se 5 600
8.1 Because of the potential heterogeneous nature of LHW,
S 0.05 % 5 % Br 10 5000
Cl 0.05 % 5 % Cd 5 600
K 0.1 % 5 % Sb 5 600
Reagent Chemicals, American Chemical Society Specifications, American
V 5 600 Sn 5 600
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Cr 5 600 I 5 600
listed by the American Chemical Society, see Analar Standards for Laboratory
Fe 5 600 Hg 5 600
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia Ni 5 600 Tl 5 600
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, Cu 5 600 Pb 5 600
MD.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 6052
10.3.1 The standard specimen in the sample cups is placed effects, the concentration of all elements present can be
in the spectrometer’s sample holder avoiding any contact with estimated. The exact equations used will differ for each
the film or rough handling that may disturb the standards. manufacturer.
10.4 Two methods of calibration are available.
10.4.2.1 Follow the manufacturer’s fundamental parameters
10.4.1 Method A—Empirical calibration method using a suit set-up recommendations. The stoichiometric set-up of the
of standard concentrations. Standard concentrations are limited
fundamental parameters method for the analysis of the LHW
to 600 mg/kg for Ag, As, Ba, Br, Cd, Cr, Cu, Fe, Hg, I, K, Ni, mixed with alumina should allow for the manual input of a
Pb, Sb, Se, Sn, Tl, V, and Zn. Standard concentrations are
fixed 75 % Al O concentration and the use of carbon as a
2 3
limited to 5 % for Cl, P, S, and other light elements (that is, = 22 and <0.5 % for Br). The limits ensure staying within the
ments of interest determined directly according to the prin-
linear range and due to the limited concentration range of ciples of 10.4.2.
available traceable standards. The standards should provide a
10.4.3 Two control samples are needed for monitoring
linear response of element intensity to concentration. Serial
instrument stability. One control sample is a blank preparation
dilutions of analyte standards can be used to set up the
using PEG or the low concentration drift correction monitor
calibration for each element. Multi-element standards can then
used in 10.4.1.1. The other sample is a stable mixture contain-
be used to assess the deconvolution requirements of the
ing a suitable range and number of elements (for example, S,
spectrometer and check for calibration linearity.
V, Zn, Pb, and Ba) at concentrations near the middle of the
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
aqueous- or organic-based. For example, a 5000 mg/kg organic-based Pb
10.4.4 Restandardization should be carried out whenever
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-
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
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 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. One should pro-
regressed element. NOTE: Restandardization using drift cor-
vide a high net count-rate similar to standards from the upper
rection monitors is often part of instrumental software. Follow
end of the calibration range and the other should provide a low
the manufacturer’s recommendations for the set-up of restan-
net count-rate similar to the blank. Measure the net count-rate
dardization using two standards. Method B: Follow the manu-
for each element in the high concentration disk in such a way
facturer’s recommendations for the set-up of initial element
that the counting statistical error due to random fluctuation of
sensitivities and the appropriate fundamental parameters meth-
the X-ray flu
...