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MBASTER
FORENSIC APPLICATIONS OF TRACE ELEMENTS IN HAIR*
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L. C. Bate and F. F. Dyer
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NOV 2 9 1968
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Analytical Chemistry Division
Oak Ridge National Laboratory
2.0 $ 1.08; 58
Oak Ridge, Tennessee
Conf.660937_1
I. Introduction
The individualization of people by the trace elements in their hair
appears to be probable on a laboratory scale when multiple hair strands
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are analyzed. The reasons for this technique showing promise are due to
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the following conditions: (1) a relatively large number of trace elements
can be precisely measured, (2) all the hairs can be ascribed to their respec-
tive donors and therefore the hair-to-hair variability is made small, and
(3) the conditions of the samples can be closely controlled to prevent con-
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tamination.
In most criminal cases, however, these conditions are not met and the
practical application of the method continues to be seriously in doubt.
To date, at least four criminal cases in which trace element comparisons
were a part of the evidence have gone before United States courts. The
evidence was accepted by the court in only one case. It remains to be
seen if the three failures of this type of evidence to be legally acceptable
will affect future cases.
II. Factors Affecting Identification
Barring the influence of contamination and changes with time after
a sample of hair is removed from a person, the problem of matching a
SURAT
.
*Research sponsored by the U. S. Atomic Energy Commission under contract
with the Union Carbide Corporation.
LEGAL NOTICE
This report was prepared as an account of Government sponsored work. Neither the United
States, nor the Commission, nor any person acting on behalf of the Commission:
A. Makes any warranty or representation, expressed or implied, with respect to the accu-
racy, completeness, or usefulness of the information contained in this roport, or that the use
of any information, apparatus, method, or process disclosed in this report may not Infringe
privately owned rights; or
B. Assumes any liabilities with respect to the use of, or for damages resulting from the
use of any information, apparatus, method, or process disclosed in this report.
As used in the above, "person actag on behalf of the Commission" includes any em-
ployee or contractor of the Commission, or employee of such contractor, to the extent that
such employee or contractor of the Commission, or employee of such contrio or prepares,
disseminates, or provides access to, any Information pursuant to his employment or contract
with the Commission, or his employment with such contractor,

RELEASED FOR ANNOUNCEMENT
IN NUCLEAR SCIENCE ABSTRACTS
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sample of hair to its donor is probabilistic in nature. The chance of
making a correct match depends on (1) differences in trace element con-
tents between persons, the between-persons variability and (2) the com-
bined effects of variations in hairs from the same heads, the within-
limit
person variability, and experimental errors.
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It is becoming increasingly clear that variations among hairs from
the same heads are significant and may prohibit comparisons when only
a few hairs are available. We have been asked to attempt comparisons
in several criminal cases in which only one hair was found at the crime
site. Our experience with single hairs indicate that the within-person
variability is too large to permit one hair to be matched to a donor.
.
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The reasons for hairs from the same head having different trace
elemert concentrations have not been fully explained. The evidence ob- ..
tained thus far indicates that adsorption of trace elements from environ-
mental sources, e.g., water, perspiration, cosmetic agents, etc., is
responsible for most of the trace elements in hair. It is known that
hairs of widely different ages occur on a person's headl) because some
are grrwing and some are not. One would expect, therefore, that if
environment adsorption is the primary source of trace elements, those of
different ages and lengths as well as those in different positions would
exhibit differences in concentrations.
Residues from dust, perspiration, cosmetics, and other material that
are on the surface of the hair must be removed before the trace elements
in the hair are measured. After a thorough study of cleaning hair by
various methods 12,5), it was concluded that the most desirable method to
clean hair is with a non-ionic detergent--Kyro EO. This method compares
.:
favorably with normal "in situ" washing of hair to remove surface con-
tamination from the hair. The washing procedure consists of adding three
drops Kyro EO to 20 mi redistilled water containing the hairs in a pre-
cleaned plastic vial. The hairs are washed by shaking the vial for five
minutes. The hairs are rinsed in redistilled water. This procedure is
repeated two times with
the weshing time increased to 20 minutes instead
of five minutes.
Table I illustrates the amounts of the trace elements
removed in each wash.
III. Adsorption of Trace Elements in Hair
The belief that environmental adsorption alters the trace element
composition of hair is based on the following observations.
certain dyes and medicinal agents.
(2) The concentration of most trace elements increases with distance
from the scalp toward the outer ends.
(3) Radioiodine given to thyroid patients is soon found strongly
adsorbed in the outer parts of the patients' hair.
(4) When hair samples are placed in aqueous solutions, almost all
elements present will adsorb to an extent much greater than
1.
44
their respective concentrations found in untreated hair.
Results are shown in Figure I for trace elements measured in the hair
.
of a small boy with a scalp disease. The abnormally high concentrations
iu.
4
5
of several elements were undoubtedly caused by a salve used to treat the
1.
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boy's head.
Analytical results are shown in Table II for sectioned portions of
long strands of hair. The significant increase shown for trace element
.
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Rs.
concentrations with distance from the scalp has also been observed
by others. (4,5)
Several hair samples were obtained from the nape of the necks of
thyroid patients given 1311 at the Oak Ridge Institute of Nuclear Studies,
Soon after it was given, there was no evidence of 1911 in the hair. Samples
that were taken during the following four days contained an easily measur.
able and increasing amount of 1911. Duplicate samples taken from the
patients contained significantly different amounts of 1311. These re-
sults indicate clearly that a trace element can be rapidly eliminated
from the body in perspiration and adsorbed in hair. Differences between
duplicates also indicate a source of hair-to-hair variation of trace
elements. It was also shown that a part of the 2311 was strongly attached
to the hair by washing the samples with an aqueous solution of Kyro EO
(a non-ionic detergent). The fractions remaining after washing are shown
in Table III.
A simlated perspiration solution () was made and a radiotracer was
added with a known amount of stable ion. The pH of the solution was
controlled to be between 3 and 6 and the actual pH was recorded. A
100-mg hair sample was added, then shaken to ensure contact and allowed
to remain in the solution overnight. Sixteen hours later the solution
was removed and the hair rinsed with water. Radioactivity measurements
were made after this water rinse and again after a Kyro E0-washing.)
The results of these experiments measuring the amount of each element
adsorbed* on the hair is reported in Table Iv.)
* The term adsorption has been used to represent the attachment to hair
of elements in environmental media. It is not known whether this process
is one of adsorption or absorption (or both) according to the conventional
definitions of these terms.
.
The data show (Fig. 3) that cation adsorption for an element increases
as pH 7 is approached, while the amount of anion adsorption for an ement
decreases (Fig. 4).
The amounts of the element adsorbed by the hair depend on both the
.
pH of the solution in contact with the hair and the particular element
used.
IV. Methods of Comparing Analytical Results
.
The method used to compare the results of trace element measurements
of hair is pertinent both to laboratory study and criminal cases includ-
ing presentation in court. There has not been general agreement about
this aspect of the problem.
Comparison of data in graphical form as gamma-ray spectra should
be rejected because of its subjective nature. We believe that, for this
method of hair comparison to be placed on an objective basis, the trace
elements must be identified and measured quantitatively and these results
compared.
1.
Comparisons have been made of concentratior. or photopeak ratios. (5)
If this procedure is used, one of the elements in the sample can serve
as an internal standard. The small differences in exposure to neutron
Istusi
reasonable care is taken, experimental errors can be reduced nearly to
the limit set by counting statistics. It has been observed with samples
criar
16
of only a few hairs that the largest source of error is not experimental
error but the within person variability. For such samples comparisons
of ratios appears more to confuse than aid in matching hair samples. A
further argument against the use of ratios is that they are not unique
quantities as witnessed by the fact that 200: 3.00 equals 2:1. On the
-6-
baqis of ratios, therefore, two samp.les differing markedly in absolute
concentrations might appear similar. It should also be recognized that if
N elements are measured, only N-1 ratios are independent and can be com-
pared. Additional ratios are redundant.
The statistical method developed by J. B. Parker'°) for evaluating
the probabilities of mistakes in hair comparisons seems to be the most
useful one at present. The method takes into account between-person and
within-person variances but not possible correlations among the elements.
Results for all the elements measured are combined into a single criterion
for evaluating the probability that two samples come from the same person
and the fraction of the population that might show indistinguishable con-
centrations. With the exception of Coleman's study'°) in England and Wales,
no representative sampling has been made to permit application of a statis-
tical treatment. There is some doubt that the variations found by Coleme.no
can be extrapolated to another geographical location. There is doubt also
that a statistical statement can be made for a crime sample consisting on
only one hair.
V. Recommendations concerning Further Study of Hair Comparisons
Because the hairs found at a crime site cannot be a priori ascribed
to the same person, it will be necessary in most instances to consider each
one separately. Unless single hairs can be readily matched, there is little
need for extensive sampling of the population to determine the number of
people having similar trace element concentrations. We believe that a study
of single hairs should be made by simulating criminal cases. This procedure
would consist of the selection of 1 to 7 hairs per person from perhaps 10
persons. Duplicates would be taken in some of the cases from up
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to three individuals. The person collecting the sampjes would give them
to an activation analyst for analysis and matching. The analyst would
analyze each hair singly and would not know which samples, if any, were
duplicates. The analyst could make comparisons by the method of his
choice (graphical, quantitative measurements including statistical analysis),
but would report his findings only in terms of which samples match and which
do not match. The frequency of successes and failures in comparing samples
in a number of these cases would easily convince anyone of the value of
trace element comparisons. Such experiments in which only one or two hairs
were taken would be particularly instructive because they would correspond
closely to real criminal cases. Experiments of this type would yield data
amenable to statistical treatment (if the samples are representative of
the population) and they heighten the interest of the investigator.
Duplicates in a simulated case made at ORNL could not be identified
by means of the number of trace elements that metched. In fact, there
were a number of erroneous selections. As a result of this study, we
believe it is not advisable at the present time for ciminal investi-
gators to attempt comparisons or single hairs found at a crime site. If
bundles of hair are found that can be a priori ascribed to one person,
comparisons might be feasible. Care must be taken to avoid comparisons
of hairs that may have been contaminated and to prevent the contamination
of samples after they are collected Solutions used to wasii hairs before
irradiation or mount hairs for other examinations must be shown to be
free of elements that will absorb. The fact that hair absorbs elements
from its environment will always make caution necessary in the criminal
Ali
.-B-
case. If controlled laboratory study shows that single hairs can be matched,
it would then be desirable to carefully study environmental effects in
simulated criminal cases. Such a study might delineate the environmental
conditions from which criminal investigators could safely take hairs for
trace-element comparison.
ACKNOWLEDGEMENT
We wish to acknowledge the assistance given by Roger Clautier of ORINS
in obtaining the hair samples after 13-I administration.
.
Literature Cited
1. F. M. Kerr, "The Detection and Measurement of Trace Elements in Human
Hair using Neutron Activation," Master's Thesis, University of Ottawa,
Canada, April 1964.
2. L. C. Bate, "The Use of Activation Analysis in Procedures for the
Removal and Characterization of the Surface Contaminants of Hair,"
J. of Forensic Sci. 10(1), 60 (Jan. 1965).
3. L. C. Bate and F. F. Dyer, "Trace Elements in Human Hair," Nucleonics
23(10), 74 (Oct. 1965).
4. F. W. Lima, H. Shibata, and I. T. Attalla, "Activation Analysis Applied
to Forensic Investigation. Some Observations on the Problem of Indi-
vidualization of Human Hair," presented at Symposium on Radiochemical
Methods of Analysis, paper SM-55/114. (IAEA, Salzburg, Austria, Oct.
1964.)
5. A. K. Perkons and R. E. Jervis, "Application of Radio-Activation
Analysis in Forensic Investigations," J. of Forensic Sci. I(4),
449 (1962).
6. W. S. Spector, Editor, "Handbook of Biological Data," WADC-TR 56-373,
p. 56 (1956).
7. L. C. Bate, "Adsorption and Elution of Trace Elements on Human Hair,"
Intern. I Appl. Radiation Isotopes 17 417 (1966).
8. R. F. Coleman, F. H. Cripps, 'and A. Stimson, "Interim Report on the
Determination of Trace Elements in Simple Hair by Neutron Activation
and the Application to Forensic Science, " AWRE 0-78/65, Aldermaston,
Berks, England, Aug. 1965.
US
11
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List of Figures
Fig. 1
Long Lived Radionuclides in Hair and Wash Solution of Individual
Wao Had a Scalp Condition (ORNL-Dws. 63-5184)
Fig. 2
Adsorption by Hair of Mn, Cu, and Zn from Simlated Perspiration
and Effects of Kyro EO Washing after Adsorption (ORNL-Dwg. 65-2262A)
Fig. 3
Adscrption of Cations – Fe, Co, Cu, Zn and Hg -- on Hair
(ORNL-Dwg. 65-7696)
Fig. 4
Adsorption of Anions -- I, Br, ci and Se – on Hair (ORNL-Dwg. 65-2263A)
.
.
Table I. Trace Elements Removed by Kyro EO
Sample
Wash
Wash
Br
Irace Element Concentrations. Mg/gm
Mo Na Br
0.35 259
3.6
0.08
D
0.04
NO
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2.5
0.83
0.01
1.4
ND
ND
NO
ND
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29.5
0.81
0.08
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560 11.3
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0.9
NDND
ND
ND
ND = not detected
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Table II. Trace Element concentration Measured as a function
of Distance from Scalp in Female Hair
Segment, cm
0-2
cu
14.8
2.4
Trace Elements, ug/gm
Hg
Au
0.85 10.7 x 102
1.08 3.4 x 10-2
6.4 x 10-2
7.4 x 10^2
2.00
15 x 102
16.2
0.76
6-8
Dinby
20.5
24.7
36.4
8-11
Table III. 1311 Remaining on Hair after Kyro Eo Washing
Person
1st Sample
Time Sample Taken
2nd sample
Time Sample Taken
hrs
hrs
A
33.0
72
120
55.9
45.1
120
35.1
120
B 44.5
C 24.6
D 22.5
38.1
F 42.0
34.0 = 11.5
* No sample taken
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Table IV. Concentration of Element Adsorbed on Hair
Element
Auts
Element Concentration, mg/& Hair
pH 3.5 pf 4.5 E 5.5
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LONG LIVED RADIONUCLIDES IN HAIR AND WASH SOLUTION
H920575
SAMPLE ZH-4
Irradiation time, 160 hr
Flux, 8 x 10"' n/cm2/sec
Decay time, to +60d
Geometry, 5 cm
Gain, 10 Kev/channel
COUNT RATE
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END

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12/ 23 / 66




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