ASTM C1234-11(2019)

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: C1234 − 11 (Reapproved 2019)
Standard Practice for
Preparation of Oils and Oily Waste Samples by High-
Pressure, High-Temperature Digestion for Trace Element
Determinations
This standard is issued under the fixed designation C1234; 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 other regulatory procedures or requirements, such as the U.S.
Environmental Protection Agency (EPA) SW-846 and EPA-
1.1 This practice covers a high-pressure, high-temperature
600/4-79-020documents.Thisdigestionpracticeisdesignedto
digestion technique using the high-pressure asher (HPA) for
provide a high level of accuracy and precision, but does not
preparation of oils and oily waste specimens for determination
replace or override any regulatory requirements for sample
of up to 28 different elements by inductively coupled plasma-
preparation.
atomic emission plasma spectroscopy (ICP-AES), cold-vapor
atomic absorption spectroscopy (CVAAS), and graphite fur-
1.6 This practice uses hazardous materials, operations, and
nace atomic absorption spectroscopy (GFAAS), inductively
equipment at high pressure (90 bars to 110 bars, 89 atm to
2 2
coupled plasma-mass spectrometry (ICPMS), and radiochemi-
108 atm, or 1305 lb⁄in. to 1595 lb⁄in. ) and high
cal methods. Oily and high-percentage organic waste streams
temperatures, up to 320 °C, and therefore poses significant
from nuclear and non-nuclear manufacturing processes can be
hazards if not operated properly.
successfully prepared for trace element determinations by
1.7 The values stated in SI units are to be regarded as
ICP-AES, CVAAS, and GFAAS. This practice is applicable to
standard. No other units of measurement are included in this
thedeterminationoftotaltraceelementsinthesemixedwastes.
standard.
Specimenspreparedbythispracticecanbeusedtocharacterize
1.7.1 Exception—Pressure measurements are given in lb/in.
organic mixed waste streams received by hazardous waste
units.
treatment incinerators and for total element characterization of
1.8 This standard does not purport to address all of the
the waste streams.
safety concerns, if any, associated with its use. It is the
1.2 This practice is applicable only to organic waste streams
responsibility of the user of this standard to establish appro-
that contain radioactivity levels that do not require special
priate safety, health, and environmental practices and deter-
personnel or environmental protection from radioactivity or
mine the applicability of regulatory limitations prior to use.
other acute hazards.
Specific warning statements are given in Section 10.
1.3 A list of elements determined in oily waste streams is
1.9 This international standard was developed in accor-
found in Table 1.
dance with internationally recognized principles on standard-
1.4 This practice has been used successfully to completely
ization established in the Decision on Principles for the
digestalargevarietyofoilsandoilymixedwastestreamsfrom Development of International Standards, Guides and Recom-
nuclear processing facilities. While the practice has been used
mendations issued by the World Trade Organization Technical
to report data on up to 28 trace elements, its success should not Barriers to Trade (TBT) Committee.
be expected for all analytes in every specimen. The overall
nature of these oily wastes tends to be heterogeneous that can
2. Referenced Documents
affect the results. Homogeneity of the prepared sample is
2.1 ASTM Standards:
critical to the precision and quality of the results.
D1193 Specification for Reagent Water
1.5 This practice is designed to be applicable to samples
E177 Practice for Use of the Terms Precision and Bias in
whose preparation practices are not defined, or not suitable, by
ASTM Test Methods
This practice is under the jurisdiction of ASTM Committee D02 on Petroleum
Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcom-
mittee D02.03 on Elemental Analysis. For referenced ASTM Standards, visit the ASTM website, www.astm.org, or
Current edition approved May 1, 2019. Published June 2019. Originally contact ASTM Customer Service at service@astm.org. ForAnnual Book of ASTM
approved in 1993. Last previous edition approved in 2016 as C1234 – 11 (2016). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/C1234-11R19. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
C1234 − 11 (2019)
TABLE 1 List of Elements and Applicable Lower Concentration TABLE 2 HPA Temperature Program for Oils and Oily Waste
Ranges Samples
Lower Reportable Starting Ending
Element Analysis Method Phase Time, min
A
Limit, µg/g Temperature, °C Temperature, °C
Aluminum 3.3 ICP-AES 1 100 30 125
Antimony 8.3 ICP-AES or GFAAS 2 125 60 300
Arsenic 8.3 ICP-AES or GFAAS 3 300 60 300
Barium 0.17 ICP-AES 425 30 25
Beryllium 0.05 ICP-AES 50 0 0
Boron 0.67 ICP-AES
Cadmium 0.50 ICP-AES or GFAAS
Calcium 0.67 ICP-AES
Chromium 1.7 ICP-AES
Cobalt 0.83 ICP-AES
4. Summary of the Practice
Copper 0.67 ICP-AES
Iron 0.67 ICP-AES
4.1 Oil or oily waste specimens are digested in nitric and
Lead 8.3 ICP-AES or GFAAS
hydrochloric acids using HPAhigh-pressure, high-temperature
Lithium 0.67 ICP-AES
Magnesium 0.08 ICP-AES equipment. Prepared specimens of 0.2 g to 0.7 g will provide
Manganese 0.17 ICP-AES
enough solution for analysis by CVAAS, ICP-AES, and
Mercury 0.03 CVAAS
GFAAS for up to 28 elements.
Nickel 1.7 ICP-AES
Potassium 100 ICP-AES
Selenium 8.3 ICP-AES or GFAAS
5. Significance and Use
Silver 1.0 ICP-AES
Sodium 3.3 ICP-AES 5.1 This practice is useful for preparation of difficult-to-
Strontium 0.07 ICP-AES
digest, primarily oils and oily wastes, specimens for trace
Thallium 1.7 GFAAS
element determinations of up to 28 elements by atomic
Titanium 0.50 ICP-AES
Vanadium 0.83 ICP-AES
absorption or plasma emission techniques. Specimen prepara-
Zinc 0.17 ICP-AES
tion by high-pressure ashing is primarily applicable to speci-
Zirconium 0.83 ICP-AES
menswhosepreparationbyEPASW-846protocolsiseithernot
A
Lower reportable limits are based on a 0.3 g sample diluted to a final volume of
applicable or not defined. This sample preparation practice is
50 mL. These limits should only be used as a guide.Actual values are instrument
and sample dependent. applicable for the trace element characterization of mixed oily
wastes for use by waste treatment facilities such as incinerators
or waste stabilization facilities.
2.2 US EPA Standards:
6. Interferences
EPA-600/4-79-020 Methods for ChemicalAnalysis of Water
and Wastes
6.1 Preparation of samples for trace element determinations
SW-846 Test Methods for Evaluating Solid Waste, Physical/
is subject to matrix and chemical interferences. Although the
Chemical Methods
HPA practice is designed to totally digest most matrices, there
are some matrix types that are not applicable to this practice,
3. Terminology
for example, highly reactive substances (explosives), ex-
3.1 Definitions: tremely flammable materials, and some silicone-based lubri-
3.1.1 heating block, n—aluminum block used to hold cants.
samples inside the HPA autoclave/pressure chamber.
7. Apparatus
3.1.2 HPA-TC controller, n—computer interface between
HPA autoclave and an IBM-compatible computer. 7.1 HPA High-Pressure Asher —High-pressure, high-
temperature autoclave under computer control allowing com-
3.1.3 pressure chamber, n—chamber within the HPA auto-
plete digestion of difficult specimens using mineral acids. The
clave where heating block filled with samples is placed. The
system includes:
chamber is designed to hold pressures up to 200 bar (197 atm
7.1.1 Compatible computer with hard drive and with one
or 2900 lb⁄in. ) and temperatures up to 320 °C.
open RS-232C serial interface.
3.1.4 safety lid vent stack, n—top plate and cylinder that
7.1.2 HPA-TC temperature controller—this device provides
covers the autoclave pressure chamber.
the interface between the HPA autoclave and the computer by
3.1.5 sample vessel, n—sample container, constructed of
means of RS-232C serial interface.
quartz or glassy carbon, designed for use in the HPA.
7.1.3 HPA autoclave unit.
3.1.6 temperature program, n—software program which 7.1.4 HPAsample vessels, appropriate size and construction
for specimen type and mineral acid used.
controls the temperature ramping of the HPA during the run.
The program used for preparation of oil samples is shown in
Table 2.
The sole source of supply of the apparatus known to the committee at this time
isAnton Paar K. G., Graz,Austria. If you are aware of alternative suppliers, please
AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments, provide this information toASTM International Headquarters. Your comments will
732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http:// receive careful consideration at a meeting of the responsible technical committee,
www.access.gpo.gov. which you may attend.
C1234 − 11 (2019)
7.2 Ultrasonic Homogenizer—Specimen homogenizer us- types, an ultrasonic sonifier is very useful in providing a
ing ultrasonic disruption tip to homogenize specimens that homogeneous specimen. The sonifier uses high-frequency
cannot be mixed by hand. electrical energy transmitted through a converter to vibrate a
metal horn tip that is immersed in the sample. The vibration of
8. Reagents and Materials
thehorntipcausescavitationofmediumthatcausestheintense
8.1 Purity of Reagents—Chemicals used in the preparation agitation of the medium leading to very stable emulsions to be
formed, even between polar and non-polar liquids.
of spiking standards must be of ultra purity grade. Chemicals
and reagents used in the preparation practice must conform to 9.3.1 The sonification process will generate heat, and the
the specifications of the Committee on Analytical Reagents of specimen should be checked during the process. Specimen
the American Chemical Society, where such specifications are homogenization is determined by visual observation and is
available. Other grades may be used, provided it is first normally complete within 10 s to 60 s. If heat generation in the
ascertained that the reagent is of sufficient purity to permit its sample becomes a problem, determined by the temperature rise
use without lessening the accuracy of the determination. in the specimen, then the homogenization should be judged
complete when the sample temperature rises to this level, as
8.2 Reagent Water—References to water shall be under-
determined on a specimen-by-specimen basis. Process and
stood to mean reagent water as defined by Type 1 of Specifi-
observe each sample individually to obtain the best, most
cation D1193.
representative results. Specimens with low flash points are not
8.3 Nitric Acid (sp gr 1.42)—Ultra pure concentrated nitric
recommended for homogenization by this method.
acid (HNO ).
9.3.2 Process the specimen immediately to maintain its
8.4 Hydrochloric Acid (sp gr 1.19)—Ultra pure concen-
homogeneity.
trated hydrochloric acid (HCl).
10. Procedure
8.5 Hydrofluoric Acid (sp gr 0.988)—Ultra pure concen-
trated hydrofluoric acid (HF).
10.1 Weigh 0.2 g to 0.7 g of homogeneous sample into a
clean HPA vessel. The sample mass necessary for the HPA is
8.6 Matrix Spiking Standards—Multielement standards
matrix dependent, that is, organic or inorganic content, and
used for matrix spiking shall be of sufficient purity and
samples up to 2 g can be prepared. Sample sizes of 0.2 g to
accuracy and, where possible, traceable to accepted nationally
0.7 g are successful for highly organic specimens. The organic
known standards (that is, National Institute of Standards and
component of the specimen will have a direct effect on the
Technology (NIST) or EPA). Spiking standards used should
digestion in the HPA; the more organic a specimen, the more
yield spiked specimens with concentrations between 0.5 mg⁄L
internal pressure may be generated. Due to the closed-vessel
to 2 mg⁄L for most elements.
HPA technique, the possibility of a specimen venting during
9. Sample Preparation
the HPA digestion is proportional to its mass.
9.1 Homogeneous specimens are a requirement if suitable
10.2 Within a preparation batch, with the number of speci-
analytical precision is expected. Most oils and oily wastes
mens defined by the laboratory, the following quality control
requireadditionalstepstoprovidehomogeneousspecimensfor
samples should be included: a reagent blank containing all
preparation. If the sample is visibly clear or can be shaken to
reagentsusedintheprocedure,amatrixduplicatespecimenfor
provide a homogeneous specimen, no further pretreatment is
assessing precision, and a matrix-spiked specimen for assess-
necessary.
ing method accuracy. A batch size of ten specimens has been
successful for HPAdigestion performed on oily waste samples.
9.2 Liquid or aqueous specimens that are cloudy or contain
visible sediment or precipitates may require an ultrasonic bath
10.3 Exercise extreme caution when handling specimens
to resuspend settled material or maintain a homogeneous
during the pressure decomposition process, as spontaneous
specimen for preparation. The process of ultrasonic mixing
violent reactions may occur under adverse conditions. The
will generate heat, and warm the sample above ambient
safety design features of the HPA equipment allow for sample
temperature. A consideration of the original sample must be
explosive reactions to occur inside the pressure chamber
made as to the effect of ultrasonification on the sample. A
without adverse effects on the equipment or its operators. A
sample with a low boiling point, such as freon, may not be
tantalumrupturediskwillblowouttorelievethepressureifthe
applicable to ultrasonic mixing. Ultrasonification between
internal pressure of the sealed chamber should rise above
1 min to 5 min is effective for liquid or aqueous samples.
200 bars (197 atm or 2900 lb⁄in. ). (Warning—Adequate
laboratory facilities, such as fume hoods and controlled
9.3 It is difficult to obtain homogeneous specimens for
ventilation,alongwithnormalsafelaboratorytechniques,must
preparation from multi-phase liquids, oils, oily wastes, or
be used in this procedure. Due to the rupture disk feature, the
samples with large amounts of solid mat
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