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: E3294 − 23 An American National Standard

Standard Guide for

Forensic Analysis of Geological Materials by Powder X-Ray
Diffraction1
This standard is issued under the fixed designation E3294; 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 2. Referenced Documents

1.1 This guide covers techniques and procedures for the use 2.1 ASTM Standards:2
of powder X-ray diffraction (XRD) in the forensic analysis of C1365 Test Method for Determination of the Proportion of
geological materials (to include soils, rocks, sediments, and Phases in Portland Cement and Portland-Cement Clinker
materials derived from them such as concrete), to enable Using X-Ray Powder Diffraction Analysis
non-consumptive identification of solid crystalline materials D934 Practices for Identification of Crystalline Compounds
present as single components or multi-component mixtures. in Water-Formed Deposits By X-Ray Diffraction
1.2 This guide makes recommendations for the preparation E620 Practice for Reporting Opinions of Scientific or Tech-
of geological materials for powder XRD analysis with adapta- nical Experts
tions for samples of limited quantity, instrumental configura- E1492 Practice for Receiving, Documenting, Storing, and
tion to generate high-quality XRD data, identification of Retrieving Evidence in a Forensic Science Laboratory
crystalline materials by comparison to published diffraction E2917 Practice for Forensic Science Practitioner Training,
iTeh Standards
data, and forensic comparison of XRD patterns from two or
more samples of geological materials to support criminal
Continuing Education, and Professional Development
Programs

(https://standards.iteh.ai)
investigations. E3272 Guide for Collection of Soils and Other Geological
Evidence for Criminal Forensic Applications
1.3 Units—The values stated in SI units are to be regarded
2.2 ISO Standard:3
long-standing tradition of expressingDocument
X-ray wavelengths and Preview
as standard. Other units are avoided, in general, but there is a
ISO/IEC 17025:2017 General Requirements for the Compe-
tence of Testing and Calibration Laboratories
lattice spacing in units of Ångströms (Å). One Ångström =
10–10 meter (m) = 0.1 nanometer (nm). 3. Terminology
ASTM E3294-23
1.4 This standard is intended for use by competent forensic
https://standards.iteh.ai/catalog/standards/sist/d3888858-5b1b-4986-a11b-ddc41629ccc8/astm-e3294-23
science practitioners with the requisite formal education,
3.1 Definitions of Terms Specific to This Standard:
3.1.1 Bragg equation or Bragg’s law, n—describes the
discipline-specific training (see Practice E2917), and demon- physical phenomenon of X-ray scattering from a crystallo-
strated proficiency to perform forensic casework. graphic three-dimensional lattice plane as nλ=2dsinθ, in which
1.5 This standard does not purport to address all of the n is any integer, λ is the wavelength of the X-ray, d is the
safety concerns, if any, associated with its use. It is the crystal plane separation, also known as d-spacing, and θ is the
responsibility of the user of this standard to establish appro- angle between the crystal plane and the diffracted beam, also
priate safety, health, and environmental practices and deter- known as the Bragg Angle.
mine the applicability of regulatory limitations prior to use. 3.1.2 crystal, n—a homogeneous, solid body of a chemical
1.6 This international standard was developed in accor- element or compound, having a regularly repeating atomic
dance with internationally recognized principles on standard- arrangement that can be outwardly expressed by plane faces
ization established in the Decision on Principles for the (adapted from Ref (1)).4
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee. 2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
1 3
This guide is under the jurisdiction of ASTM Committee E30 on Forensic Available from International Organization for Standardization (ISO), ISO
Sciences and is the direct responsibility of Subcommittee E30.01 on Criminalistics. Central Secretariat, Chemin de Blandonnet 8, CP 401, 1214 Vernier, Geneva,
Current edition approved Nov. 1, 2023. Published November 2023. Originally Switzerland, https://www.iso.org.
4
approved in 2022. Last previous edition approved in 2022 as E3294 – 22. DOI: The boldface numbers in parentheses refer to the list of references at the end of
10.1520/E3294-23. this standard.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 E3294 − 23
3.1.3 crystal lattice, n—the three-dimensional regularly re- 3.1.12 Rietveld refinement, n—a procedure for carrying out
peating set of points that represent the translational periodicity a crystal-structure refinement using X-ray or neutron powder
of a crystal structure. diffraction data, in which an entire powder pattern is simulated
3.1.3.1 Discussion—Each lattice point has identical sur- for a trial structure(s) and matched against the observed
roundings. Lattice is the abstract pattern used to describe the powder pattern; atomic parameters and other variables are
internal geometric structure of crystals. Lattice and structure modified to achieve an acceptable fit between the calculated
are not synonymous, as structure refers to the real mineral and observed powder patterns (adapted from Ref (1)).
material (adapted from Ref (1)). 3.1.13 unit cell, n—the smallest group of atoms of a crystal
3.1.4 crystalline, adj—having a crystal structure or a regular lattice that has the overall symmetry of a crystal of that
arrangement of atoms in a crystal lattice. substance, and from which the entire lattice can be built up by
3.1.5 d-spacing, n—in diffraction of X-rays by a crystal, the repetition in three dimensions.
distance or separation between successive and identical parallel 3.1.14 X-ray diffraction (XRD), n—the diffraction of a beam
planes in the crystal lattice; d-spacing is expressed as d in the of X-rays, usually by the three-dimensional periodic array of
Bragg equation (adapted from Ref (1)). atoms in a crystal that has periodic repeat distances (lattice
3.1.6 diffractometer, n—an instrument that records either dimensions) of the same order of magnitude as the wavelength
powder or single-crystal X-ray diffraction patterns. of the X-rays (1).
3.1.7 known sample, n—known samples of geological ma- 3.1.15 X-ray diffraction pattern or diffractogram, n—the
terial are intentionally collected, typically from crime scene or characteristic interference pattern obtained when X-rays are
alternate locations, for comparison to a questioned sample. diffracted by a crystalline substance; the geometry of the
pattern is a function of the repeat distances (lattice dimensions)
3.1.7.1 Discussion—Geological materials are typically more
of the periodic array of atoms in the crystals; the intensities of
heterogeneous than manufactured materials, so a greater num-
the diffracted beams give information about the atomic
ber of known samples of geological material are needed to
arrangement, and unit-cell dimensions (adapted from Ref (1)).
represent the range of variation (see Guide E3272). Reference
sample and control sample are synonyms of known sample. 3.1.16 X-ray powder diffraction, n—diffraction of a beam of
iTeh Standards
3.1.8 mineral, n—a naturally occurring inorganic element or
compound having an orderly internal structure and character-
X-rays by planes of atoms in a powdered crystalline sample;
the powders are prepared so they ideally represent all possible

(https://standards.iteh.ai)
istic chemical composition, crystal form(s), and physical
properties, or an element or chemical compound that is
crystal orientations to the X-ray beam (adapted from Ref (1)).

4. Summary of Guide
Document Preview
crystalline and that has formed as a result of geological or
pedogenic (soil-formed) processes (adapted from Ref (1)). 4.1 Powder X-ray diffraction produces results related to the
3.1.8.1 Discussion—Artificial and biogenic crystalline ma- crystal structure(s) of one or more crystalline components of
terials are not minerals but can occur in geological materials the material being analyzed that can allow phase identification.
(for example, cement powder, lime, lye, biogenic ASTM E3294-23
calcite, 4.2 This guide recommends specific techniques and proce-
https://standards.iteh.ai/catalog/standards/sist/d3888858-5b1b-4986-a11b-ddc41629ccc8/astm-e3294-23
biogenic hydroxyapatite, bricks) and can be detected by XRD. dures for XRD analysis of geological materials in forensic
3.1.9 phase, n—a part of a chemical system that is casework, including XRD analysis of minimally modified
homogeneous, physically distinct and at least hypothetically materials, small quantities of material (a common limitation in
separable, and which has single or continuously variable forensic casework), and in situ XRD of material adhering to a
chemical and mechanical properties (adapted from Ref (1)). substrate.
3.1.10 provenance, n—a place of origin; specifically, the 4.3 XRD patterns are compared to reference databases as
area from which the constituent materials of a sedimentary means of identifying the crystalline constituents of a sample.
rock or facies are derived (adapted from Ref (1)).
4.4 XRD can be used to determine the crystal structure of a
3.1.10.1 Discussion—In the context of forensic provenance
material, but this is not described in this guide.
analysis, geological material is analyzed and interpreted to
estimate or limit the geographic or environmental conditions of 4.5 XRD patterns from various samples are compared to
the source of this material to provide an investigative lead. For each other for forensic comparison and provenance purposes.
example, soil on a shovel can be examined to aid in the search
for a clandestine grave, typically by comparison of observa- 5. Significance and Use
tions to reference data. Geographic attribution is an alternative 5.1 The overarching goals of the forensic analysis of geo-
term for provenance. logical materials include (A) identification of an unknown
3.1.11 questioned sample, n—geological evidence of un- material (see 11.3), (B) analysis of soils, sediments, or rocks to
known origin, or a questioned sample, typically consists of restrict their possible geographic origins as part of a prov-
debris adhering to an evidentiary object (for example, tire, enance analysis (see 11.4), and (C) comparison of two or more
wheel well, garment, shoe, digging tool); exogenous soil left at samples to assess if they could have originated from the same
a crime scene (transferred from a shoe/tire, or adhering to a source or to exclude a common source based on observation of
re-buried body/object); or debris recovered from within a body exclusionary differences (see 11.5). XRD is only one analytical
(nasal, stomach, or lung contents). method that can be applied to the evidentiary samples in

2
 E3294 − 23
service of these distinct goals. Guidance for the analysis of 6.2.2 A McCrone Micronizing Mill5 (9), or other mills;
forensic geological materials can be found in Refs (2-4). 6.2.3 Filtration apparatus (10).
5.2 Within the analytical scheme of geological materials, 6.3 Sample Holders:
XRD analysis is used to: identify the crystalline components 6.3.1 Bulk sample holders can be used when sample volume
within a sample; identify the crystalline components separated is sufficient to fill them.
from a mixture, typically clay-sized material (see 8.8), or a 6.3.2 Sample holders with minimal contribution to the
selected particle class for which additional analysis is needed diffraction pattern are recommended for many applications.
(see 8.11); or compare two or more samples based on the Two “zero background” sample holder substrates are:
identified crystalline phases or diffraction patterns (see 11.5). 6.3.2.1 A silicon crystal cut parallel to the 510 plane;
5.2.1 Non-destructive XRD analysis can be performed in 6.3.2.2 A quartz crystal cut 6° from the 0001 plane.
situ on geological material adhering to a substrate (see 8.12.3). 6.3.3 Filters or other substrates can be used, but they could
5.2.2 The most common forensic applications of XRD to contribute to the background signal. In interpretation of dif-
geological materials are (A) identification or confirmation of a fraction patterns, this background should be considered.
selected phase or fraction of a sample (see 8.12), (B) identifi- 6.4 Reference Materials:
cation of minerals in the clay-sized fractions of soils (see 8.8), 6.4.1 Standard Reference Materials—Standard reference
and (C) identification of the phases of the hydrated cement materials, commonly silicon, corundum, or microcrystalline
component of concrete or mortar. quartz, are available from NIST (National Institute of Stan-
5.3 This guide is intended to be used with other methods of dards and Technology) or some instrument manufacturers.
analysis (for example, polarized light microscopy, scanning Standard reference materials are used to document peak
electron microscopy, palynology) within a more comprehen- position, resolution/peak width, and intensity of the diffraction
sive analytical scheme for the forensic analysis or comparison peaks.
of geological materials. 6.4.2 Mineral reference materials.
5.3.1 Comprehensive criteria for forensic comparisons of 6.4.3 Crystalline materials for “internal calibration” or ref-
geological material integrating multiple analytical methods and erence material mixed into the analyte.

iTeh Standards
provenance estimations (see 11.4) are not included and are 6.4.3.1 Common crystalline materials that can be used
beyond the scope of this guide. include zincite (zinc oxide), halite (sodium chloride), diamond,
silver, corundum, or another crystalline substance that is absent
6. Apparatus and Materials
(https://standards.iteh.ai)
6.1 Powder X-Ray Diffractometer:
from the sample and that does not, or minimally, interferes with
sample diffraction peaks, as demonstrated by prior sample

ured with a 2θ or θ - θ geometry. Document Preview

6.1.1 Powder X-ray diffractometers are commonly config- analysis or prior knowledge of the sample.
6.5 Powder XRD Reference Data—Reference diffraction
6.1.2 Alternative instrumentation configurations permit si- data for known materials are available as: powder XRD
multaneous collection of diffracted beams at multiple angles
ASTM E3294-23 patterns that are digital or graphical data representing the
(stationary position sensitive detectors), or transmission pow- intensity of the diffracted X-ray beam versus degrees 2θ (for a
https://standards.iteh.ai/catalog/standards/sist/d3888858-5b1b-4986-a11b-ddc41629ccc8/astm-e3294-23
der XRD. specified X-ray wavelength); tables of diffraction peaks listing
6.1.3 The X-ray tubes in XRD most commonly have copper the degrees 2θ or the d-spacing (Å), the relative intensity of
targets, generating a Kα1,2 wavelength (λ) of 0.15418 nm these peaks, and the crystallographic plane (defined by h, and
(1.5418 Å). k, and l) causing the diffraction; and modelled diffraction
6.1.3.1 X-ray tubes with cobalt targets (Co Kα1,2λ of patterns derived from crystal structure data. Several commer-
0.17902 nm or 1.7902 Å) reduce fluorescence in XRD of cial and freely available sources are listed below; however, this
iron-bearing materials (5). list is not inclusive. The source of reference data should be
6.1.4 Parallel Beam Optics, if available, could be beneficial considered when used to identify phases within the XRD
for: samples that are not flat (see 8.12.1); in situ analysis, pattern of an unknown sample.
(8.12.3), or micro-XRD (8.12.4), but can reduce the diffraction 6.5.1 Commercial Sources of Powder XRD Patterns and
signal (6). Adaptations to achieve parallel beam optics include: Structural Data:
6.1.4.1 Göbel mirrors, 6.5.1.1 International Centre for Diffraction Data (ICDD,
6.1.4.2 Polycapillary collimators (7), PDF or Powder Diffraction File) (11).
NOTE 1—The parallel beam adaptations need to be matched to the 6.5.1.2 NIST Inorganic Crystal Structure Database (ICSD)
specific applications. (12).
6.5.2 Free Sources of XRD Patterns and Structural Data of
6.1.5 Spinning Sample Stage, if available, could be benefi-
Geological Material:
cial for samples of limited quantity.
6.1.6 Adjustable XYZ Tri-axial Goniometer Head, if 5
The McCrone Micronizing Mill (McCrone Microscopes and Accessories, 850
available, could be beneficial for samples of limited quantity.
Pasquinelli Drive, Westmont, IL 60559) is the only suitable commercial product for
6.2 Sample Milling and Preparation Equipment—The fol- the optimal particle size reduction of geological materials for quantitative powder
XRD (8) known to the committee at this time. If you are aware of alternative
lowing materials can be helpful in sample preparation.
suppliers, please provide this information to ASTM International Headquarters.
6.2.1 Mortar and pestle composed of agate, alumina, or Your comments will receive careful consideration at a meeting of the responsible
ceramic; technical committee,1 which you may attend.

3
 E3294 − 23
6.5.2.1 The RRUFF Project (13) integrating the American fractionation, the XRD patterns for comparison should be
Mineralogist Crystal Structure Database. derived from the same particle size fraction.
6.5.2.2 The Crystallography Open Database or COD (14) 8.3.2 Other physical or chemical treatments should be
integrating the American Mineralogist Crystal Structure Data- similar for direct comparison of XRD patterns (for example,
base. drying, crystallite orientation, glycolation, selective dissolution
6.5.3 Sources of Powder XRD Tables of Geological and (28), grinding, type of sample holder).
Related Materials: 8.4 Sample Quantity—Diffraction data suitable for phase
6.5.3.1 Table 5.18 of Brown and Brindley (15). identification can be acquired from very thin samples (see
6.5.3.2 Common soil minerals in Table 4-1 of Ref (16). 8.12.2), but a powder thickness of at least ~100 µm is optimal
6.5.3.3 Common minerals in clay-sized material (17). (16, 29).
6.5.3.4 Clay mineral-specific diffraction data (16, 18-21). 8.4.1 If samples are thinner than ~100 µm and if the sample
6.5.3.5 Cement- and concrete-specific data (Ref (22), see holder is not a low background material (see 6.3.2), contribu-
Test Method C1365). tion from the sample holder should be considered in the
6.6 Powder XRD Analysis Software for Phase Identifica- interpretation of the diffraction pattern.
tion: 8.4.2 The minimum sample required for acquisition of XRD
6.6.1 Diffractometer manufacturers typically provide data suitable for phase identification will vary by sample
instrument-specific, high-quality peak detection and phase composition, but several milligrams on a zero background
identification software. sample holder can be sufficient (2).
6.6.2 Alternatively, there are additional commercial (for 8.5 Sample Particle Size—An optimal sample for powder
example, Jade (23)) and no cost software packages (for XRD data acquisition consists of fine particles, typically less
example, CrystalSleuth (13), ReX (24), or GSAS II (25); see than 10-20 µm diameter (8, 16, 29).
review in Ref (26)). 8.5.1 Reduction of Particle Size—Samples of limited quan-
tity are often ground using a mortar and pestle (16, 29).
7. Hazards 8.5.1.1 Grinding in a liquid medium such as acetone or an

iTeh Standards
7.1 X-rays are a hazardous source of ionizing radiation and
should be contained within the safety shielding of a commer-
alcohol is recommended. Grinding in water, while possible,
will destroy potentially soluble minerals (for example, salts

(https://standards.iteh.ai)
cial diffractometer whenever the X-ray tube is energized. The such as halite or gypsum). Certain minerals can be altered by
X-ray source should be registered with the appropriate juris- aggressive grinding (29, 10).
dictions. 8.5.1.2 Particle reduction mills (such as a McCrone Micron-
Document
7.2 The X-ray tube requires high voltages that present a risk Preview
of electrocution if instrument safety mechanisms are over-
izing Mill) produce an ideal narrow particle range of the right
size for powder XRD (8) but are not recommended for samples
ridden. of limited quantity.
ASTM E3294-23 NOTE 3—To preserve the grain morphology and to permit subsequent
https://standards.iteh.ai/catalog/standards/sist/d3888858-5b1b-4986-a11b-ddc41629ccc8/astm-e3294-23
8. Sample Preparation grain selection, it can be prudent NOT to grind samples of very limited
quantity. See 8.12.1.
8.1 Recommend sample preparation methods are described NOTE 4—Contributions from the micronizing media should be consid-
below for acquisition of high-quality XRD data, but useful ered when interpreting powder diffraction profiles.
XRD data can be produced with minimal sample modification 8.6 Sample Placement on Sample Holder—Powders should
(for example, in situ analysis (8.12.3), or from samples of be placed into a clean sample holder, with the powder surface
limited quantity (8.12.1, 8.12.2, 8.12.4). flush with the top of the sample holder to align with the
8.2 Sub-sampling of Particle Assemblages—Representative focusing circle of the diffractometer.
sub-sampling of particulates can be achieved with a sample 8.6.1 Samples too small to fill a sample holder can be placed
splitter, or cone and quartering, both of which can be imprac- directly on a low background substrate.
tical for samples of limited quantity (27). 8.6.2 The powder should ideally cover the entire area
8.2.1 An alternative method of representative sub-sampling irradiated by the X-ray beam, which will depend on the
that is appropriate for small quantities of powder, is first instrument configuration and the 2θ scan range, but is not
mixing the particles, moistening to cause particle adhesion, required with a zero-background sample holder.
then scooping of one or more sub-samples. 8.7 Random Particle Orientation—With the exception of
NOTE 2—Systematic sub-sampling of particulates is crucial for quan- samples intentionally prepared with a preferred orientation (see
titative XRD methods (see 10.6) to minimize bias in both particle size and 8.8.3), powders should be prepared to confer random orienta-
modal abundance of particle type. tion of crystals.
8.3 Sample Treatments for Comparisons—Sample treat- 8.7.1 Avoid pressing too hard on the powder surface to
ments should be similar when comparing diffraction patterns of maintain random orientation of the crystals.
geological materials (questioned-to-known, questioned-to- 8.7.2 Clay minerals, common in soils, are particularly
questioned, or known-to-known) (see 11.5). susceptible to preferred orientation (9, 10, 16, 21).
8.3.1 If there is a distinct particle size difference between 8.7.3 Use of a side-loading sample holder can minimize
samples, and if there is sufficient material to conduct size these effects (9, 10).

4
 E3294 − 23
8.8 Clay Mineral Analysis Methods—XRD analysis is one treatments can irreversibly alter the evidence, but solvation is
of the principal means of differentiating minerals in the reversible and can be informative.
clay-sized fraction (<2 µm diameter) of soils and sedimentary
8.9 Standard Addition for Internal Calibration—Due to the
rocks as these particles are too small to be analyzed by optical
limitations often encountered with evidentiary samples, it is
microscopy. Clay minerals are phyllosilicates commonly found
not always possible to achieve the ideal sample height,
in the clay-sized particle range. Because clay minerals have
particularly for in situ XRD. Because sample height is critical
significant effects on soil chemical and physical properties,
for both phase identification and comparison (see 10.7.3), the
specific sample preparation protocols have been developed to
use of an internal standard represents one way to ensure
functionally differentiate among these minerals by XRD analy-
accurate knowledge of peak position (° 2θ). Alternatively, the
sis.
presence of another independently established phase (such as
8.8.1 Dispersion of Samples—Dispersion of minerals in an quartz) can also be used to serve as an internal peak position
aqueous solution is useful both for separation of size fractions calibrant.
to segregate clay sized material for XRD (see 8.8.2), and for
removal of fine materials coating sand and silt grains prior to 8.10 Standard Addition for Quantification—For quantitative
grain mount preparation for analysis by light microscopy. XRD analysis (see 10.6), a common approach is to add a
8.8.1.1 Commonly a dispersant/surfactant is added in trace specified weight percent (~10 to 20 weight %) of an internal
amounts to aid dispersion. Sonication in an ultrasonic bath or standard (see 6.4.3) to the sample, usually corundum, or zincite
with an ultrasonic probe aids in dispersion. (31).
8.8.1.2 The presence of carbonates or gypsum can interfere 8.10.1 Standards should be absent from the sample and
with dispersion but standard methods to remove these minerals should lack preferred orientation.
are not recommended for samples of limited quantity. 8.10.2 This approach is not recommended for samples of
NOTE 5—Dispersion in water will destroy potentially soluble minerals
limited quantity.
(for example, salts such as halite). 8.11 Segregation and Concentration of a Sample Compo-
8.8.2 Separation of Clay-sized Fraction—To separate the nent:

iTeh Standards
clay-sized fraction (<2 µm), the sample is typically dispersed in 8.11.1 The segregation and concentration of a component
water (see 8.8.1) and allowed to settle a known distance for a can be done using a range of methods including hand picking
known length of time (either under gravity or in a centrifuge) particles, density separation, magnetic separation, or selective
(https://standards.iteh.ai)
in accordance with Stokes’ Settling Law (19, 21).
8.8.3 Oriented Samples—To analyze clay minerals by XRD,
dissolution (29, 28, 32).
8.11.2 Physical concentration of a component of a mixture

Document Preview
many methods are designed to intentionally create samples in
which the platy clay minerals are oriented parallel to the
diffraction focal plane, selecting for the 00l lattice spacing.
will aid in its identification when it is otherwise present below
the XRD detection limit (see 10.7.4) in a bulk sample.
8.11.3 Segregation of the hydrated cement component of
This can be achieved by: concrete prior to XRD enhances the signal of the cement
ASTMout
8.8.3.1 Allowing a clay mineral suspension to sediment E3294-23
phases that are useful in cement comparisons
https://standards.iteh.ai/catalog/standards/sist/d3888858-5b1b-4986-a11b-ddc41629ccc8/astm-e3294-23
and dry on the sample holder, 8.11.4 Hydrated cement can show zoning around aggregate
8.8.3.2 Filtering it through a membrane filter and transfer- grains and near the concrete surface; thus, sampling and
ring the sediment film on the filter to the sample holder, analysis from representative zones of the evidentiary samples
8.8.3.3 Generating an XRD pattern of the material in situ on is recommended.
the filter, or
8.8.3.4 Smearing a dense clay paste across the sample 8.12 Adaptations of XRD Methods to Evidentiary Samples
holder. of Limited Quantity—Evidentiary geological materials are
8.8.3.5 Diffraction patterns derived from oriented samples commonly limited in quantity or may be adhered to other items
should not be compared to standard powder XRD reference in which removal could lead to loss of evidence. Several
data by search-match methods due to the suppression of all optional adaptations of sample preparation and XRD methods
peaks except 00l. can be applied based on the sample characteristics, and
8.8.4 Clay Treatments—The clay-sized fraction (<2 µm availability of equipment (8.12.1 – 8.12.4).
diameter) of soils or other geological material can be subjected 8.12.1 Unground Scant Sample—To preserve grain mor-
to treatments prior to sequential XRD analysis aiding differ- phology and to permit subsequent grain selection, XRD pat-
entiation among clay mineral varieties (10, 18, 19, 21, 30; terns can be acquired from unground particles of geological
section 7A1 in Ref (20); Table 4.2 in Ref (16)). Common material.
treatments include: 8.12.1.1 A collection of “large” unground grains (fine sand
8.8.4.1 Saturation with Mg2+, K+, or Li+; to coarse silt sized) can be placed directly on a sample holder.
8.8.4.2 Solvation with glycerin, ethylene glycol, or forma- 8.12.1.2 A preparation of scant material consisting of large
lin; or (over 25 µm), or uneven-sized particles will have an uneven
8.8.4.3 Heating to specific temperatures, typically 300 °C, surface and will likely have few diffracting crystals (29).
400 °C, 500 °C, or 550 °C. 8.12.1.3 Longer data acquisition times and a rotating sample
8.8.4.4 For samples of limited quantity, application of cation stage are recommended for scant samples to acquire sufficient
saturation or heat treatment is not recommended because these signal for peak detection and phase identification.

5
 E3294 − 23
8.12.1.4 The resulting diffraction peaks from unground 8.12.4.1 Better results for µXRD require a focused, colli-
samples could be displaced (see 10.7.3) and peaks could mated X-ray beam (see 6.1.4).
broaden due to the uneven sample height (9). 8.12.4.2 Use of an adjustable XYZ tri-axial goniometer
8.12.1.5 Use of parallel beam optics can mitigate the arti- head (6.1.6) can assist mitigating focal plane offset, and the
facts of an uneven sample surface (6). presence of fewer diffraction domains in samples of limited
8.12.2 Ground Scant Sample—A small subsample can be quantity.
ground in a mortar in a solvent and pipetted onto the center of 8.12.4.3 Sample preparations for µXRD include: miniatur-
a zero background sample holder, minimizing the amount of ized sample holders, enclosure within a glass capillary, or
morphologically modified material. attachment to a filament extended to the focal plane.
8.12.2.1 Scant samples often require increased data collec- 8.12.4.4 Use of a sample rotational mechanism, either a
tion time to acquire sufficient signal for peak detection and rotational stage or a spinning needle, will improve detection of
phase identification. diffraction peaks (36).
8.12.2.2 The minimum sample quantity required for XRD 8.12.4.5 µXRD methods can be applied to individual par-
will vary between geological materials. ticles or to powders.
8.12.3 In Situ XRD Pattern Collection—In certain types of
9. XRD Data Acquisition
evidence, geological materials are present in trace amounts,
either as intact fragments or as a collection of particles, on an 9.1 Range of 2θ Angles or d-Spacing:
object such as a bullet, fabric, or shoe outsole. When removal 9.1.1 Soils, Sediments, and Rocks—The important diffrac-
of the geological material from its substrate could lead to loss tion peaks for soil, sediment and rocks typically occur for a
or modification of evidence, it is beneficial to create an in situ d-spacing range of 2.9 nm to 0.13 nm; 3° to 70° 2θ for Cu-Kα
XRD pattern by mounting the object in or near to the focal X-rays, 29 Å to 1.3 Å (31).
surface of the X-ray diffractometer (examples are described in
NOTE 7—The lowest angles of 2θ (largest d-spacings) in this range are
6, 32-34). useful for the analysis of clay minerals, particularly mixed-layer clay
8.12.3.1 Acquiring in situ XRD patterns is non- minerals. Some diffractometers will not permit scanning below 5° 2θ.

iTeh Standards
consumptive, leaving the sample available for other analytical
methods (for example, chemical analysis, DNA extractions; or
9.1.2 Cement—The important diffraction peaks of cement
typically occur between 0.763 nm to 0.175 nm; 11.5° to 52.2°
minimally manipulated bullet for toolmark examination).
(https://standards.iteh.ai)
2θ for Cu-Kα X-rays, 7.63 Å to 1.75 Å (see Test Method
8.12.3.2 When a clean area of the substrate is present and C1365).
compatible with the instrument geometry, collection of a
Document Preview
9.2 Factors Affecting Diffraction Intensity—Several factors
background diffraction pattern from an area of the substrate
affect the intensity of resultant diffraction peaks, including:
without the geological material can enable identification of
possible diffraction peaks originating from the interaction of 9.2.1 Intensity of incident X-rays on the sample is affected
the substrate with the X-ray beam. For example, kaolinite is by the X-ray tube’s age and tuning, the type of the X-ray tube,
ASTM E3294-23and the focusing slits used.
added in the production of many rubber materials (tires,
https://standards.iteh.ai/catalog/standards/sist/d3888858-5b1b-4986-a11b-ddc41629ccc8/astm-e3294-23
footwear), and when identified in the substrate should be NOTE 8—Use of high energy X-ray sources at synchrotron facilities
considered in the in situ XRD analysis of geological material allows the XRD-based detection of low abundance and poorly crystalline
adhering to such items. materials in forensic geological materials (37), but these facilities are not
easily accessible to most forensic examiners.
8.12.3.3 If heterogeneous sample deposition is suspected,
collection of multiple diffraction patterns from the in situ 9.2.2 Scan rate of the diffractometer (typically expressed in
sample can capture the intra-sample variability. ° 2θ per second, or count time per step increment).
8.12.3.4 Diffraction peak position shifts due to the irregular 9.2.3 Sensitivity of the X-ray detector.
height of the in situ sample should be taken into consideration 9.2.4 Quantity and crystallinity of the sample.
(Sample displacement, see 10.7.3). NOTE 9—Certain minerals inherently produce strong diffraction peaks
8.12.3.5 Displacement artifacts of in situ samples can be (for example, quartz). For samples with very little material, poor
mitigated with the use of parallel beam optics (see 6.1.4). crystallinity, or with very small crystal sizes, use of slower scan rates
could enable detection of pertinent XRD peaks.
8.12.3.6 To account for possible peak displacement with in
situ XRD analyses, samples can be reanalyzed after the 9.3 XRD Data Quality Assurance Practices:
addition of a crystalline standard, known to be absent from the 9.3.1 XRD methods should be validated prior to use in
samples, to allow for a displacement correction. casework.
NOTE 10—ISO/IEC 17025-2017 provides guidance on criteria to be
NOTE 6—These standards should amount to less than ~10 weight %
evaluated during method validation.
applied by uniformly sprinkling over the sample(s). Example standards
include zincite (zinc oxide), halite (sodium chloride), diamond, corundum, 9.3.2 Periodically, an XRD pattern should be collected from
or another crystalline substance that is clearly absent in the XRD scan a standard reference material (for example, silicon, corundum,
made prior to its addition.
or microcrystalline quartz; see 6.4.1), under specified condi-
8.12.4 µXRD—Standard powder XRD methods can be tions; a reasonable frequency for this check is every month of
adapted for the analysis of small samples (micro-XRD) (see 6, use, when an instrument is serviced, and when the instrument
32-35) performance is suspect.