ASTM D5839-96

NOTICE: This standard has either been superseded and replaced by a new version or discontinued.
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Designation: D 5839 – 96
Standard Test Method for
Trace Element Analysis of Hazardous Waste Fuel by
Energy-Dispersive X-Ray Fluorescence Spectrometry
This standard is issued under the fixed designation D 5839; 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 applies to the determination of trace 4.1 The analysis of trace elements is often a regulatory and
element concentrations by energy-dispersive X-ray fluores- process specific requirement for facilities utilizing LHWF.
cence (EDXRF) spectrometry in typical liquid hazardous waste With proper instrument standardization, set-up, and quality
fuels (LHWF) used by industrial furnaces. control, this test method provides the user an accurate, rapid,
1.2 This test method has been used successfully on numer- nondestructive method for trace element determinations.
ous samples of LHWF that are mixtures of solvents, oils,
5. Interferences
paints, and pigments for the determination of the following
5.1 Spectral Overlaps:
elements: Ag, As, Ba, Cd, Cr, Hg, Ni, Pb, Sb, Se, and Tl.
1.3 This test method also may be applicable to elements not 5.1.1 Samples containing a mixture of elements often ex-
hibit X-ray emission line overlap. Modern Si (Li) detectors
listed above and to the analysis of trace metals in organic
liquids other than those used as LHWF. generally provide adequate resolution to minimize the effects
of spectrum overlaps on the analytical results of the LHWF. In
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the those cases where direct emission line overlap exists, spectral
deconvolution methods extract corrected analyte emission line
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- intensities. Table 1 lists the significant line overlaps observed
for the elements analyzed in LHWF. Follow the EDXRF
bility of regulatory limitations prior to use.
manufacturer’s recommendations concerning spectral decon-
2. Referenced Documents
volution of the emission lines.
2.1 ASTM Standards:
NOTE 1—Not all possible interferences are listed in Table 1. The LHWF
C 982 Guide for Selecting Components for Energy-
samples to be analyzed may have other emission line interferences not
Dispersive X-Ray Fluorescence (XRF) Systems
mentioned. Consult the manufacturer’s recommendations for optimum
deconvolution methods.
3. Summary of Test Method
5.2 Matrix Interferences:
3.1 A weighed portion of the sample is transferred to a
5.2.1 Large concentration variations of metal or matrix
porcelain evaporating dish and placed on a hot plate. The
components, or both, in LHWF samples can result in non-
sample is heated for 15 to 30 min at a temperature not
linear metal X-ray intensity response at increasing metal
exceeding 105°C to evaporate highly volatile components. The
concentrations. Untreated matrix interactions may have a
dish is removed from the hot plate and allowed to cool.
deleterious effect on metal determination accuracy. Matrix
Graphite powder is blended with the evaporated sample until a
interactions, if exhibited by the LHWF samples, must be
homogeneous paste is produced and the sample weight is
accounted for by method calibration.
recorded. The blended sample is inserted in a disposable
sample cup and placed in the X-ray spectrometer for analysis.
6. Apparatus
3.2 The K Spectral X-ray emission lines are used for Ag, As,
6.1 Energy Dispersive X-Ray Spectrometer, capable of mea-
Ba, Cd, Cr, Ni, Sb, and Se.
suring the wavelengths listed in Table 1. Refer to C 982 for
3.3 The L spectral X-ray emission lines are used for Hg, Pb,
system specifications.
and Tl.
6.2 Hot Plate, with temperature control to 105°C.
6.3 Analytical Balance, capable of weighing to 0.001 g.
6.4 Porcelain Evaporating Dishes, 70 to 150 mL capacity.
This guide is under the jurisdiction of ASTM Committee D-34 on Waste
Management and is the direct responsibility of Subcommittee D34.02 on Physical
7. Reagents and Materials
and Chemical Characterization.
7.1 Purity of Reagents—Use reagent grade chemicals in all
Current edition approved Jan. 10, 1996. Published March 1996.
Annual Book of ASTM Standards, Vol 12.01. tests. Unless otherwise indicated, all reagents will conform to
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
D 5839
TABLE 1 Common Emission Line Spectral Interferences for
9.2 Obtain reference spectra from pure element standards
LHWF Analysis
for all analytes and interelement correction metals.
Lines
9.3 Address spectral interferences, as listed in 5.1.1, in
Element Spectral Interferences
Determined
accordance with manufacturer’s recommendations.
As Ka,Kb Pb La,HgLb,Tl La Lb
Cr Ka,Kb VKb,MnKa
10. Calibration and Standardization
Hg La,Lb As Kb,SeKa,PbLb,Tl La,BrKa
Ni Ka,Kb Cu Kb,CuKa
10.1 Calibrate the spectrometer to an appropriate reference
Pb La,Lb As Ka,SeKb Hg Lb Tl La,Tl Lb,BrKa,BrKb
element at the minimum frequency specified by the manufac-
Se Ka,Kb Pb Lb,HgLb,Tl Lb
Tl La,Lb As Ka,As Kb,SeKb,PbLa,BrKa,HgLa,HgLb
turer.
10.2 Analytical standards should be gravimetrically pre-
pared by blending the elemental standards and graphite listed
the specifications of the Committee on Analytical Reagents of
in Section 7. These preparations can contain single or multiple
the American Chemical Society where such specifications are
elements and should be prepared at combinations and ratios to
available. Other grades may be used, provided it is first
meet the user’s individual needs. For example, a Pb and Cd
ascertained that the reagent is of sufficient high purity to permit
standard at 125 ppm each could be prepared by gravimetrically
its use without lessening the accuracy of the determination.
combining 2 g oil-based Pb standard (500 ppm), 2 g oil-based
7.2 Use graphite powder, mixing grade, 44 μm, 325 mesh.
Cd standard (500 ppm) and 4 g graphite and blending to a
7.3 Use oil-based Ag, As, Ba, Cd, Cr, Hg, Ni, Pb, Sb and Se
homogeneous mixture. For this example, the Pb concentration
standards, 10 to 10 000 mg/kg depending on the user’s
is calculated as follows:
analytical requirements. If the results of this test method are to
Pb Standard Concentration 5 500 ppm
be used for compliance purposes, standards or a commercial
Pb Std. ~g!
source must be traceable to NIST or other certifying body. 3
graphite ~g!1 Cd Std. ~g!1 Pb Std. ~g!
Quality control samples for analyses done for compliance
(1)
purposes may need to be prepared with standards from a
10.3 The metals standard/graphite paste is placed in an XRF
different vendor or lot number.
sample cup and affixed with a thin-film support. The sample
7.4 Use oil or solvent-based Tl standard, 10 to 1000 mg/kg
cup is inverted and lightly tapped on a level surface until the
depending on the user’s analytical requirements. If the results
blended paste makes full contact (no air spaces) with the
of this test method are to be used for compliance purposes,
thin-film support.
standards or a commercial source must be traceable to NIST or
10.3.1 The standard blends in the sample cups are placed
other certifying body.
into the spectrometer’s designated sample holder. Avoid touch-
7.5 Use paraffinic base oil.
ing the thin-film, as this can further reduce transmittance.
7.6 Use sample cups, vented or unvented.
Initiate data acquisition for the desired elements according to
7.7 Use thin-film sample support.
the manufacturer’s instructions.
NOTE 2—The user should select a thin-film support that provides for
10.4 Two alternative standards calibration methods may be
maximum transmittance and is resistant to typical components in LHWF.
used:
The thin-film supports used in the development of this test method were
10.4.1 Test Method A (Empirical Calibration Method)—
4 μm Prolene.
Organic-based metals standards containing the metals of inter-
8. Sampling
est are prepared as described in 10.2. The standard metal
8.1 Because stratification or layering of liquid samples is concentrations must bracket the unknown LHWF concentra-
tion levels. If the standard concentrations are less than 0.1 %
possible, the laboratory sample should be thoroughly mixed by
shaking prior to withdrawing a portion for testing,
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