ASTM D6052-97(2003)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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 2003)
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 (e) 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
3.2 The K spectral emission lines are used for elements
majorelementconcentrationsbyenergy-dispersiveX-rayfluo-
Si-Ba.
rescence spectrometry (EDXRF) in liquid hazardous waste
3.3 The Lspectralemissionlinesareusedforelementswith
(LHW).
atomic numbers greater than Ba.
1.2 This test method has been used successfully on numer-
ous samples of aqueous and organic-based LHW for the
4. Significance and Use
determination of the following elements: Ag, As, Ba, Br, Cd,
4.1 The elemental analysis of liquid hazardous waste is
Cl,Cr,Cu,Fe,Hg,I,K,Ni,P,Pb,S,Sb,Se,Sn,Tl,V,andZn.
often important for regulatory and process specific require-
1.3 This test method is applicable for other elements (Si-U)
ments. This test method provides the user an accurate, rapid
not listed in 1.2.
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-
5.1 Spectral Overlaps (Deconvolution):
priate safety and health practices and determine the applica-
5.1.1 Samples containing a mixture of elements often ex-
bility of regulatory limitations prior to use.
hibit X-ray emission line overlap. Modern Si (Li) detectors
generally provide adequate resolution to minimize the effects
2. Referenced Documents
ofspectraloverlap.Incaseswhereemissionlineoverlapexists,
2.1 ASTM Standards:
techniques of peak fitting exist for extracting corrected analyte
C 982 Guide for Selecting Components for Energy-
emissionlineintensities.Forexample,thePbLa“lineoverlaps
Dispersive X-ray Fluorescence (XRF) Systems
with the AsKa.” The PbLb line can be used to avoid this
D1193 Specification for Reagent Water
overlap and theAsK lines can then be resolved from the PbLa
2.2 Other ASTM Documents:
overlap.Theactuallinesusedforanyparticularelementshould
ASTMDataSeriesDS46 X-rayEmissionWavelengthsand
3 be such that overlaps are minimized. Follow the EDXRF
KeV Tables for Nondiffractive Analysis
manufacturer’s recommendation concerning spectral deconvo-
3. Summary of Test Method lution. Reference should be made toASTM Data Series DS 46
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
limitation in the development and expanding use of this
This test method is under the jurisdiction ofASTM Committee D34 on Waste instrumental technique. Using well understood XRF principles
Management and is the direct responsibility of Subcommittee D34.01.06 on
for controlling matrix effects, for example, dilution and matrix
Analytical Methods.
modification using lithium borate fusion and addition of heavy
Current edition approved March 10, 2003. Published June 2003. Originally
absorbers, a matrix can be stabilized. Using calcined alumina
approved in 1997. Last previous edition approved in 1997 as D6052–97.
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
EDXRF analysis.
Standards volume information, refer to the standard’s Document Summary page on
5.2.2 The response range of this test method should be
the ASTM website.
linear with respect to the elements of interest and their
Available from ASTM Headquarters, Customer Service.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959, United States.
D6052–97 (2003)
TABLE 1 Recommended Standards Ranges
regulatory or process control, or both, action thresholds. Large
concentration variations of element or matrix, or both, compo- Low Con- High Con- High Con-
Low Con-
centration centration centration
nents in LHW samples can result in non-linear X-ray intensity
Analyte Analyte centration
Range, Range, Range,
Range, mg/kg
response at increasing element concentrations.
mg/kg mg/kg mg/kg
Ag 5 600 Zn 5 600
6. Apparatus
Ba 5 600 As 5 600
P 0.1% 5% Se 5 600
6.1 Energy-dispersive X-ray Fluorescence Spectrometer,
S 0.05% 5% Br 10 5000
capableofmeasuringthewavelengthsoftheelementslistedin
Cl 0.05% 5% Cd 5 600
1.2. Refer to Guide C982 for system specifications.
K 0.1% 5% Sb 5 600
V 5 600 Sn 5 600
6.2 Analytical Balance, capable of weighing to 0.001 g.
Cr 5 600 I 5 600
Fe 5 600 Hg 5 600
7. Reagents and Materials
Ni 5 600 Tl 5 600
Cu 5 600 Pb 5 600
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, where
7.10 Sample Cups, vented.
such specifications are available. Other grades may be used,
7.11 Helium, He—minimum 99.99 purity for use as a
provided it is first ascertained that the reagent is of sufficiently
chamber purge gas for the analysis of Cl, P and S. This
high purity to permit its use without lessening the accuracy of
numerical purity is intended to specify a general grade of
the determination.
helium. Ultra-high purity helium is not required for this test
7.2 Purity of Water—Unlessotherwiseindicated,references
method.
to water shall be understood to mean meeting the numerical
requirements of Type II water as defined by Specification 8. Sample
D1193.
8.1 Because of the potential heterogeneous nature of LHW,
7.3 Aluminum Oxide, Al O —pre-calcined at 1500°C, ap-
2 3
allpossibleeffortsshouldbemadetoensurethatrepresentative
proximately 100 to 125 mesh.
samples are taken.
7.4 Aqueous or organic-basedAtomicAbsorption 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, con-
elements not listed are also available.
ditioning, preparation and maintenance of the XRF spectrom-
eter.
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
9.2 When required, reference spectra should be obtained
can be considered as % mass/mass (m/m).
from pure element standards for all deconvoluted elements.
9.3 Spectral and matrix interferences as listed in the Inter-
7.5 1-bromonaphthalene, trichlorobenzene, iodobenzoic
ferences section must be addressed per the manufacturer’s
acid, triethyl phosphate and dithiodiglycol are the recom-
recommendations.
mended standards for the elements Br, Cl, I, P and S,
respectively.
10. Calibration and Standardization
7.6 Low Molecular Weight Polyethylene Glycol (PEG 400,
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
Al O tosuitablestandardconcentrationsasdeterminedbythe
2 3
NOTE 2—Potential low level Cr, Fe or Ni (<20 mg/kg ) contamination
user’s analytical requirements. Table 1 gives recommended
due to the use of stainless steel may exist. Other suitable materials would
concentration ranges for regression. Standards can be single or
be tungsten carbide, Zr or Ta.
multi-element mixtures. Standard solutions are generally
7.9 Thin-film Support.
mixed with Al O at a ratio of 3:1.
2 3
NOTE 3—The user should select a thin-film support that provides for
NOTE 4—Morethanonestandardelement(s)solutioncanbeaddedtoa
maximum transmittance and is resistant to typical components in LHW.
single15gAl O massprovidedthetotalmassofstandardis5g.Thiswill
2 3
The thin-film supports used in the development of this test method were
maintain the proper 3:1 ratio while allowing mixtures of potentially
a polypropylene base and a high-purity, 4 µm polyester film.
incompatible elements to be combined in a single standard.
10.2.1 The number of standards required to produce cali-
brations is dependent on the number of elements to be
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
determined. Generally, two calibrations are produced, the first
listed by the American Chemical Society, see Analar Standards for Laboratory
is to determine potentially major elements such as halogens, S
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
& P.The second is to determine trace elements, typically toxic
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. metalsandheavyelements.Theminimumnumberofstandards
D6052–97 (2003)
required can be determined from the following equation: standards. The setup of a particular manufacturer’s fundamen-
minimum standards required=number elements determined tal parameters method may require a high and low concentra-
plustwo.Bothoftheabovecalibrationsshoulduseaminimum tion or mid-range concentration for each element present to
oftenstandardseachtocovertheelementconcentrationranges determinetheinitialsensitivityfortheelementsinthealumina
shown in Table 1 and to ensure that adequate data is available matrix.Othermanufacturersprovidetheinitialsensitivitywith
to assess spectral overlaps as described in 5.1. the added option to align the sensitivity to a specific matrix
10.3 The Al O +element(s) specimen is placed into an type for more accurate determinations using a single similar
2 3
XRFsamplecupsupportedbyasuitablethin-film.Thesample standard containing the elements of interest. By measuring the
is gently tapped on a flat, hard surface to settle the powder X-ray intensity (cps) for each element and using the above
against the thin-film support and ensure there are no air gaps. determined sensitivity factor for each element plus various
10.3.1 The standard specimen in the sample cups is placed equations to account for X-ray absorption and enhancement
in the spectrometer’s sample holder avoiding any contact with effects, the concentration of all elements present can be
the film or rough handling that may disturb the standards. estimated. The exact equations used will differ for each
10.4 Two methods of calibration are available. manufacturer.
10.4.1 MethodA—Empiricalcalibrationmethodusingasuit
10.4.2.1 Followthemanufacturer’sfundamentalparameters
ofstandardconcentrations.Standardconcentrationsarelimited
set-up recommendations. The stoichiometric set-up of the
to 600 mg/kg forAg,As, Ba, Br, Cd, Cr, Cu, Fe, Hg, I, K, Ni,
fundamental parameters method for the analysis of the LHW
Pb, Sb, Se, Sn, Tl, V, and Zn. Standard concentrations are
mixed with alumina should allow for the manual input of a
limited to 5% for Cl, P, S, and other light elements (that is, fixed 75% Al O concentration and the use of carbon as a
2 3
=22 and <0.5% for Br). The limits ensure staying within the
balance estimate of the solvent/aqueous phase with the ele-
linear range and due to the limited concentration range of
ments of interest determined directly according to the prin-
available traceable standards. The standards should provide a
ciples of 10.4.2.
linear response of element intensity to concentration. Serial
10.4.3 Two control samples are needed for monitoring
dilutions of analyte standards can be used to set up the
instrument stability. One control sample is a blank preparation
calibration for each element. Multi-element standards can then
using PEG or the low concentration drift correction monitor
be used to assess the deconvolution requirements of the
used in 10.4.1.1. The other sample is a stable mixture contain-
spectrometer and check for calibration linearity.
ing a suitable range and number of elements (for example, S,
V, Zn, Pb, and Ba) at concentrations near the middle of the
NOTE 5—Standards may be diluted into the linear range using low
calibration ranges. A mixture of leftover samples/standards,
molecular weight polyethylene glycol (PEG) or water. The choice of
diluent is dependent upon whether the original standard solution is spiked with element concentrations as needed and carefully
aqueous- or organic-based. For example, a 5000 mg/kg organic-based Pb
mixed may be used.
standardsolutioncanbedilutedintothe0–600mg/kgrangebycombining
10.4.4 Restandardization should be carried out whenever
and mixing 15 g of Al O +0.5 g of 5000 mg/kg Pb standard solu-
2 5
quality control results defined in Section 14 are outside data
tion+4.5 g PEG. This yields a ten-fold dilution yielding a prepared
quality objectives as determined by the user. Method A: The
standard concentration of 500 mg/kg.
initiallinearregressionsareperformedonlyonceasper10.4.1.
10.4.1.1 Drift Correction Monitors—To correct for instru-
A day zero measurement of the drift correction monitors,
mentaldrift,usephysicallystable,soliddisksorpressedpellets
10.4.1.1 during the set-up of the initial regression allows for
containing at least one element measured under each instru-
subsequent re-calibration to be performed using the two
mental condition used. At least two disks are necessary to
standardsdefinedin10.4.1.1,viaarestandardizationprocedure
correct both sensitivity and base-line drifts. One should pro-
in order to check the values of the slope and intercept for each
vide a high net count-rate similar to standards from the upper
regressed element. NOTE: Restandardization using drift cor-
endofthecalibrationrangeandtheothershouldprovidealow
rection monitors is often part of instrumental software. Follow
net count-rate similar to the blank. Measure the net count-rate
the manufacturer’s recommendations for the set-up of restan-
fo
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