ASTM D6052-97(2008)

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

SIGNIFICANCE AND USE
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

• Status: Historical
• Publication Date: 31-Jan-2008
• Technical Committee: D34 - Waste Management
• Drafting Committee: D34.01.06 - Analytical Methods

Relations

• Replaces: ASTM D6052-97(2003) - Standard Test Method for Preparation and Elemental Analysis of Liquid Hazardous Waste by Energy-Dispersive X-Ray Fluorescence
• Effective Date: 01-Feb-2008
• Replaced By: ASTM D6052-97(2016) - Standard Test Method for Preparation and Elemental Analysis of Liquid Hazardous Waste by Energy-Dispersive X-Ray Fluorescence
• Effective Date: 01-Sep-2016

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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 2008)
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 Feb. 1, 2008. Published March 2008. Originally
for controlling matrix effects, for example, dilution and matrix
approved in 1997. Last previous edition approved in 2003 as D6052–97(2003).
modification using lithium borate fusion and addition of heavy
DOI: 10.1520/D6052-97R08.
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 [e-mail]. 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 (2008)
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 ChemicalSociety, 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 (2008)
& 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. 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 oft
...