Forensic Science International, 17 (1981) 253 - 263 253

0 Elsevier Sequoia S.A., Lausanne -Printed in The Netherlands

THE QUANTITATIVE ANALYSIS OF GLASS BY INDUCTIVELY

COUPLED PLASMA-ATOMIC-EMISSION SPECTROMETRY: A FIVE-
ELEMENT SURVEY

T. CATTERICK and D. A. HICKMAN

Metropolitan Police Forensic Science Laboratory, 109 Lambeth Road, London SE1 7LP
(Great Britain)
(Received August 5, 1980; in revised form October 6, 1980; accepted December 10,
1980)

Summary

Approximately 350 glass samples of known origin, encompassing most of the types
of glass likely to be encountered in forensic science casework, have been analysed by
inductively coupled plasma-atomic-emission spectrometry. The samples included 123
window glasses, 56 vehicle glasses, 91 container glasses and 58 tableware glasses. The
analytical procedure provided the quantitative levels of manganese, iron, magnesium,
aluminium and barium in the samples. The data for the elemental concentrations, together
with refractive index, are presented in histogram form.

Introduction

When examining glass as evidential material the forensic scientist may

be required to answer either or both of the following questions: (1) to what
type or class of glass does an unknown sample belong? (i.e. classification);
and (2) are suspect and control glass samples indistinguishable, possibly
indicating a common origin? (i.e. discrimination). In order to avoid confu-
sion over this terminology, we find that the term discrimination is most
usefully applied to the differentiation of samples of the same type of glass
(for example, window) having similar refractive indices (RIs); the differenti-
ation of samples having similar RIs but belonging to different classes is
essentially a problem of classification.
A partial answer to the above two questions is provided by the measure-
ment of physical properties such as density and RI. The determination of RI
has found considerable use as a discrimination test in forensic science, but it
is a poor test for classification due to the large degree of overlap between the
RI distributions of sheet and container glasses (Fig. 1) [ 11. It has been
known for some time that chemical analysis of glass samples will provide
additional information, and this approach has been investigated by a number
of workers using such techniques as neutron activation analysis [2, 31,
emission spectrography [4, 51, atomic-absorption spectrometry [6 - 81,
spark source mass spectrometry [ 9 - 131 and X-ray fluorescence spectrometry
[14 - 161.
254

Fig. 1. Refractive index (RI) distributions for sheet (A) and container (B) glasses.

It is our aim at the Metropolitan Police Forensic Science Laboratory to

employ, whenever possible, quantitative methods for glass analysis. Quantita-
tive results are appealing since, in addition to allowing comparisons of the
analyses performed for a given case, they enable the generation of reference
data which will be valid for direct comparisons with the results of other
workers using quantitative techniques, irrespective of any differences in the
techniques or instrumental conditions employed. Such analyses can also be
related to manufacturers’ formulae or to batch compositions. It is possible to
build up a data bank of quantitative glass analyses, possibly computer-based,
which can be used for searching purposes, or for numerical methods of
classification. The quantitative analyses in such a data bank will be time-
independent.
For the above reasons we favour quantitative methods based on atomic
spectrometry for glass analysis, rather than techniques such as spark source
mass spectrometry and X-ray fluorescence spectrometry where the results
are generally expressed as elemental ratios. We have in the past employed
both d.c. arc-atomic-emission spectrography [ 51 and atomic-absorption
spectrometry [6, 71. In order to overcome some of the drawbacks of these
methods an inductively coupled plasma-atomic-emission spectrometric
(ICP-AES) procedure has recently been introduced for the multi-element
analysis of small (200 - 500 pg) fragments of glass [ 171, though it is possible
to analyse as little as 70 pg by this method. Instrumentation developed in
this laboratory enables the sequential determination of five elements in a
dissolved glass sample to be accomplished in under five minutes.
The work reported in this communication was undertaken with the
purpose of building up a reference collection of quantitative analyses of glass
samples representative of the types of glass likely to occur in forensic science
casework. Such a collection of data is of obvious value to forensic scientists
in interpreting their analyses. The major survey of window glasses reported
by Goode et al. [2] has proved to be extremely valuable, but unfortunately
it is restricted to one type of glass. Approximately 540 samples taken from
scenes of fire (giving a distribution representative of the whole window
population of 1968 - 1969) were analysed for twenty elements by neutron
activation analysis, and the quantitative results reported as frequency distri-
butions.
 255

Blacklock et al. [ 51 measured the concentrations of aluminium, barium,

calcium, iron, magnesium and manganese in approximately 100 sheet, 48
container and 40 tableware glasses. These quantitative results were obtained
by emission spectrography and were reported as histograms. Hughes et al.
[6], using atomic-absorption spectrometry, measured the concentrations of
magnesium and manganese in 58 sheet, 42 container and 38 tableware glasses
and presented the data as histograms. Since some suppression of magnesium
was observed, the reported values for this element are lower than the true
values. This suppression was found to be due to the digestion procedure
employed, and was eliminated by use of an HF-HCl acid (1: 2) mixture [ 71.
Winstanley [ 181, using a modification of the atomic-absorption method
proposed by Howden et al. [ 81, analysed 84 glasses (43 flat glasses together
with a mixture of 41 containers, drinking glasses and bulbs) for magnesium
and iron content, and presented the results as a plot of FesOs us. MgO con-
centrations.
The various workers using X-ray fluorescence spectrometry [14 - 161
have not, in general, reported any results from specific surveys of glass,
although Dudley et al. [19] tabulated the peak area ratios to calcium of
eleven elements for 100 glass samples, being 50 pairs of one window and one
non-window glass, matched for RI. The RIs were evenly distributed over the
range 1.5151 - 1.5234; i.e. the glasses did not reflect the distributions found
in practice (Fig. 1). The actual types of the “non-window” glasses were not
specified.
German and Scaplehorn [9], using spark source mass spectrometry,
reported the relative levels of up to fifteen elements in eight samples of
window glass. No refractive index values were given, and magnesium was not
determined. In a subsequent paper [lo] twenty window glasses of RI
1.5157 - 1.5159 were analysed, and the results for twelve elements were
reported as ratios to the total ion beam. Magnesium was again not reported.
In the report of a survey of headlamp glasses by the same group of workers
[ll] , the elemental concentrations of fifteen elements were tabulated for
fifteen headlamps, eight sealed-beam headlamps and six auxiliary lamps,
being the products of at least fourteen different British, Continental,
American and Canadian manufacturers. A later paper by the same workers
[12] reported the results of a survey of British container glass. They listed
thirteen elemental concentrations for seventeen colourless containers from
two major manufacturers, nine colourless containers from seven smaller
firms, and twenty coloured containers from a number of manufacturers.
The elements determined for the survey reported in this paper were
selected with the primary purpose of classifying glass samples. Although
the determination of a large number of parameters such as elemental concen-
trations should provide the best chance of achieving satisfactory classifica-
tion (and discrimination) [ 201, if a small number of elements can be selected
that achieves effectively the same classification as a larger number, then
savings in instrument and operator time will result. Obviously, any such
selection of elements must also be related to the elemental sensitivities and
256

detection limits of the analytical technique to be employed. Various workers

in the field of elemental analysis of glass for forensic purposes have made
recommendations as to the best classifying and discriminating elements. The
relevant literature will be reviewed in our study of the selection of the best
elements for classification and discrimination [ 31 . With the primary concern
of classification, we have selected the five elements manganese, iron, magne-
sium, aluminium and barium for the routine analysis of glass samples by
ICP-AES. Lithium, cobalt, arsenic, rubidium and antimony may also be
useful classifying variables, but the concentrations of some of these elements
in glass samples are below the analytical ranges of ICP-AES [ 21, 221.
Approximately 350 glasses of various types and of known origin have
been analysed by the ICP-AES procedure, and the results are presented here
as a collection of reference data. The data have also been examined by a
number of pattern recognition techniques in order to assess the five-element
analysis as an aid to classifying unknown glass samples; this work, together
with a discussion of the discrimination attainable within the sheet glass group
by the use of the same five elements, is reported separately [ 231.

Experimental

Sample preparation
The glass samples were placed in polythene bags and crushed. This was
followed by cleaning the crushed samples with concentrated nitric acid for
30 minutes, washing three times with double-distilled water and once with
ethanol, and drying in an oven at 60 “C.

RI determination
The RIs of the glass samples had been measured previously by observa-
tion of the BeckC line in sodium light using a microscope fitted with a
Mettler hot stage and controller. A calibrated silicone oil was used as the
immersion medium.

ICP-AES instrumentation
The instrumental system is essentially the same as that described pre-
visouly [ 171, with the exception that the signal processing has been auto-
mated by the addition of a Commodore PET microcomputer. The computer
is used to examine each spectral scan to find the peak maximum, to average
the peak values for the duplicate scans over a particular wavelength region,
and to store these data in the computer memory.

ICP-AES procedure
The principal steps are as follows. Fragments of suitable size (usually
200 - 500 Mug)of the washed glass samples are weighed on a microbalance,
placed in polystyrene tubes and digested with 0.5 ml of an HF-HCl acid
(1:2) mixture. Then 0.5 ml of a 1 pg ml - ’ chromium solution is added as an
 257

internal standard and the mixture is diluted to 3.5 ml with double-distilled

water. Using ultrasonic nebulisation each solution is aspirated into an induc-
tively coupled plasma, and the wavelength regions of interest are scanned
sequentially by means of a control unit coupled to a monochromator and
photomultiplier tube detector. The ultrasonic nebuliser is designed to
accommodate the polystyrene tubes which are used for sample digestion and
dilution, and thus the risks of contamination and sample loss are kept to a
minimum.
Multi-element standard solutions, the acid content of which is matched
to that of the sample solutions, are placed at the beginning and end of each
analytical run. A program has been written for the PET microcomputer
which will ratio all peaks in a single run to the chromium peak in that run,
construct lines of best fit to the calibration data, and which will, given the
sample weights, use the stored peak height to chromium peak height ratios
to calculate the absolute levels of manganese, iron, magnesium, aluminium
and barium in the samples.
The use of chromium as an internal standard is satisfactory for the vast
majority of glass samples since the level of chromium in these glasses (less
than approximately 20 pg g-‘) does not alter significantly the peak size of
the chromium added as internal standard. Some coloured glasses, especially
green glasses, do contain high concentrations of chromium, and for the
analysis of these glasses cobalt was employed as the internal standard since
d.c. arc-atomic-emission spectrography of the coloured glasses showed that
only one (blue) glass contained a high concentration of this element.

Results and discussion

Precision and accuracy

A sample of commercially produced sheet glass (refractive index,
1.5171) is employed as an “in-house” standard, and duplicate or triplicate
analyses of this sample are carried out in each analytical run. The results for
this “standard” glass (assessed in terms of both precision and accuracy) will
indicate any malfunction in a given run. The glass has now been analysed
many times by the ICP-AES procedure; some pertinent analytical results are
given in Table 1. Over an l&month period the coefficients of variation for
the short-term precision remained fairly constant. These figures refer of
course to an optimum situation but such precision values can be applied
when suspect and control samples are analysed in the same run (i.e. in a
discrimination test). For classification purposes a glass analysis must be
compared with a collection of analyses carried out months, or possibly years,
previously. The long-term precision values are used in such comparisons; the
values in Table 1 refer to determinations made during an 18-month period
by different operators using different standard solutions.
The variation in magnitude of the coefficients of variation reflects the
demands of the analysis; for example, magnesium occurs in glass at the per-
258

TABLE 1
Analysis of “standard” sheet glass by ICP-AES

Mn (pm) Fe (%) Mg (%) Al (%) Ba (ppm)

Short-term
(within-day)
November 1978
Mean 71 0.056 1.79 0.51 116
S.D. 5.9 0.0038 0.069 0.049 5.1
C.V. (%) 8.3 6.7 3.9 9.6 4.4
n 9 9 9 9 9

May 1980
Mean 82 0.061 1.83 0.50 108
S.D. 4.9 0.0046 0.085 0.030 10.2
C.V. (a) 5.9 7.5 4.6 6.0 9.4
n 10 10 10 10 10

Long-term
2-months
Mean 88 0.064 1.87 0.53 107
S.D. 9.3 0.009 0.13 3.060 13.7
C.V. (%) 10.6 14.0 7.0 11.3 12.8
n 21 21 21 21 21

18-months
Mean 86 0.064 1.88 0.52 110
S.D. 9.1 0.0082 0.14 0.058 15.6
C.V. (%) 10.6 12.7 7.4 11.2 14.2
n 87 87 87 87 87

centage level and is thus easier to determine than manganese which is present
at the 20 - 200 parts-per-million level. Iron determinations will lie some-
where between these two extremes, but may be subject to contamination.

Five-element survey
A total of 349 glass samples was analysed using the ICP-AES method.
The samples were selected from the glass collection at the Metropolitan
Police Forensic Science Laboratory on the basis of RI, using the criteria that
the distributions of the glasses should reflect the known RI distributions for
both sheet and non-sheet glasses, and that the area of overlap between sheet
and container glasses (Fig. 1) should be particularly well represented.
The samples comprised: 123 window glasses, all colourless except one
(green) sample; 91 container glasses, including 9 green, 1 blue-green and 10
brown or amber samples; 58 tableware glasses; 56 vehicle (windscreen and
other window) glasses, 4 of which were tinted; 6 headlamp glasses; 4 bulb
glasses, 1 spectacle lens and 10 miscellaneous samples (including mirrors, a
goldfish bowl and a television tube).
Fig. 2. Histograms of manganese concentrations for: (A) 349 glasses of various types; (B)
123 window glasses; (C) 56 vehicle glasses; (D) 91 container glasses; and (E) 58 tableware
glasses.

Fig. 3. Histograms of iron concentrations for: (A) 349 glasses of various types; (B) 123
window glasses; (C) 56 vehicle glasses; (D) 91 container glasses; and (E) 58 tableware
glasses.

The distribution for the six variables of manganese, iron, magnesium,

aluminium and barium concentrations and refractive index are presented as
histograms in Figs. 2 - 7. For each variable five histograms are given, being
the total 349 glasses, the 123 window glasses, the 56 vehicle glasses, the 91
container glasses and the 58 tableware glasses. The actual analytical results
for the remaining headlamp, bulb and miscellaneous samples are given in
Table 2. The large number of samples examined precludes a listing of all 349
analyses. Listings of the analytical results, however, may be obtained from
the authors.

Discussion
The presentation of multivariate data in histogram form is somewhat
unsatisfactory since no indication can be given of the relationships existing
between the measured variables in a given sample. By using the histograms,
however, a forensic scientist can interpret a glass analysis in terms of its
probability of occurrence within a given class, in a similar manner to the use
of published histograms of physical properties [ 241 for RI interpretations.
Examination of the histograms shows that, ‘in general, the distributions
of the elements do not follow any of the well-known distributions such as
260

30 A

20

10 II

Fig. 4. Histograms of magnesium concentrations for: (A) 349 glasses of various types; (B)
123 window glasses; (C) 56 vehicle glasses; (D) 91 container glasses; and (E) 58 tableware
glasses.

Fig. 5. Histograms of aluminium concentrations for: (A) 349 glasses of various types; (B)
123 window glasses; (C) 56 vehicle glasses; (D) 91 container glasses; and (E) 58 tableware
glasses.

normal or log normal A comparison of Fig. 7 with Fig. 1 shows that the
window and container glasses selected for analysis do reflect the RI distribu-
tions of these types of glass [ 11.
The elemental distributions of Figs. 2 - 6 are in fair agreement with the
distributions given in three other published surveys [ 2, 5, 61.
The vehicle histograms are similar in shape to the window ones for each
variable except magnesium. The magnesium distribution for window glasses
contains a number of glasses with low concentrations of magnesium, whereas
the vehicle distribution does not: the low magnesium samples represent flat
glass of old manufacture.
Relating the histograms to the problem of glass classification, the
manganese distributions show that this element separates sheet from table-
ware glasses to some extent, while the levels in container glass encompass
the ranges of both sheet and tableware glasses. Iron separates sheet from
 261

A
-60
1

I }20 E

I((nn
30 300 3oGuuqg-q
I 15050 15150 15250 RI

Fig. 6. Histograms of barium concentrations for: (A) 349 glasses of various types; (B)
123 window glasses; (C) 56 vehicle glasses; (D) 91 container glasses; and (E) 58 tableware
glasses.
Fig. 7. Histograms of refractive indices (RI) for: (A) 349 glasses of various types; (B) 123
window glasses; (C) 56 vehicle glasses; (D) 91 container glasses; and (E) 58 tableware
glasses.

tableware glasses, but the range for container glass covers both the sheet and
tableware groups, although the container glasses do show a greater overlap
with tableware and some separation from sheet. The variation in magnesium
levels in the glasses gives rise to excellent separation of the majority of sheet
glasses (i.e. modern sheet glass with high levels of magnesium) from the
majority of container glasses. The range for tableware overlaps both the con-
tainer and the sheet distributions. All the aluminium distributions overlap
and are similar in shape to each other. Aluminium is thus the worst elemental
variable, of the five studied here, for classifying glass samples. Barium
exhibits a good deal of overlap between the glass groups, but it does give
some separation between sheet and container glasses.

Conclusions

The glass survey reported in this paper comprises five-element analyses

on representative samples of the main types of glass likely to occur in foren-
sic science casework. These reference data are of potential use to forensic
262

TABLE 2
Analytical data for headlamp, bulb and miscellaneous glass samples

Sample Mn (ppm) Fe (%) Mg (%) Al (%) Ba (ppm) RI

Headlamp 23 0.017 0.087 0.38 11000 1.5172

Headlamp 6 0.013 1.37 0.42 10400 1.5174
Headlamp 15 0.016 0.072 0.43 13100 1.5178
Headlamp 17 0.029 1.18 0.47 9500 1.5232
Headlamp 9 0.018 0.67 0.53 4100 1.5172
Headlamp 18 0.022 0.064 1.58 16400 1.5214
Bulb 69 0.056 1.82 1.29 8150 1.5134
Bulb 85 0.083 1.73 0.73 120 1.5138
Bulb 14 0.046 2.18 1.12 5600 1.5108
Bulb 69 0.079 1.53 1.10 118 1.5128
Spectacle lens 5 0.005 0.42 0.52 16600 1.5231
Mirror 82 0.064 1.60 0.52 91 1.5180
TV Tube 85 0.030 0.015 2.40 59000 1.5172
Table top 90 0.081 2.34 0.57 122 1.5151
TV tube 52 0.023 0.012 1.93 57300 1.5159
Goldfish bowl 16 0.029 0.023 0.66 42 1.5192
Mirror 94 0.072 1.60 0.47 110 1.5179
Glass tray 170 0.017 0.010 0.10 14 1.5546
Mirror 98 0.060 2.00 0.50 79 1.5180
Green ornament 5020 0.232 0.045 0.068 172 1.5113
Black window glass 7000 0.088 2.75 0.33 86 1.5177

scientists for interpreting glass analyses, and may assist other workers who
undertake glass surveys using different analytical techniques.
The reference data presented here have been utilised in formulating a
method for classifying glass samples in forensic science; the details of this
classification scheme are given in a paper by Hickman [ 231.

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