KURZE
@J-J@FIIBMITTEILUNGEN
Naturwissenschaften 81, 546 (1994) © Springer-Verlag 1994
Introduction
In the area "New Technologies in the
Arts", the Federal Ministry of Research
and Technology (BMFT) sponsors pro-
jects in which questions, e.g., regarding
humanities, are to be investigated by
means of scientific methods and in-
struments involving a dialogue between
cultural scientists, applied scientists, and
engineers. In particular, the know-how of
research centers, universities, and in-
Naturwissenschaften 81, 546-548 (1994) © Springer-Verlag 1994
A Method for Classifying Multidimensional Data
with Respect to Uncertainties of Measurement
and Its Application to Archaeometry*
Th. Beier and H. M o m m s e n
Institut for Strahlen- u n d Kernphysik der Universit~tt, D-53115 Bonn
Classifying multidimensional data is an
indispensable task in many fields of re-
search [11. In geology, for example, rocks
are grouped with respect to their chemical
or mineralogical composition. The
elemental concentrations are determined
by techniques of modern multielemental
analysis [2]. In archaeometry, provenance
studies on ancient pottery are carried out
in the same way, assuming that potters at
different production sites exploited dif-
ferent clay beds. The trace-element pat-
tern of a clay bed is thought to be unique
in the world, thus reference material (e.g.,
misfired vessels) allows one to establish a
"chemical fingerprint" of a workshop [3].
A piece with questionable origin, but the
* This study was supported by the Bundes-
ministerium ft~r Forschung und Technologie
(BMFT), core program "Einsatz neuer Techno-
logien in den Geisteswissenschaften".
546
dustries, which has already resulted from
sponsoring by the BMFT, should be used.
The following articles should give a short
but representative survey of some results
recently gained by projects sponsored
under the aims of the above program.
The questions to be answered belong pri-
marily to the wide field of archaeology,
art history, and literature. The use of
scientific methods and technical ap-
same chemical composition as a group of
reference material, was most probably
made at the same place.
The first step in provenance studies of
pottery is the establishment of groups of
shards of the same provenance on the
basis of "similarity" between the concen-
tration patterns. In a second step, it is
tested by statistical methods whether a
sample of yet unknown origin can be
assumed to belong to one of the already
established groups and therefore is of the
same origin. The first step mainly requires
the calculation of a "dissimilarity coeffi-
cient" [11 between two data vectors )? and
37. Each of them represents a shard with its
chemical composition, and each entry in
these vectors is the concentration value of
one element. An example of a dissimilari-
ty coefficient is the Euclidean distance
lY-37 1. The smaller it is, the more similar
the data points are assumed to be. A more
Naturwissenschaften 81 (1994)
paratuses is mainly aimed at the deter-
mination of composition, age, shape, and
location of cultural objects, documents,
or historic sites.
Dr. H.-J. Krebs
Forschungszentrum Jiilich, Projekttrttger Er-
forschung kondensierter Materie und Neue
Technologienin den Geisteswissenschaftendes
Bundesministeriums fiir Forschung und Tech-
nologie
elaborated coefficient is the Mahalanobis
distance [1] (Eq. 1 below), which takes in-
to account relationships (correlations) be-
tween the variables, an essential feature
for a reliable classification [4]. Up to now
none of the existing coefficients was able
to take into account the imperfect nature
of the data, such as statistical errors of
measurement or even systematic distor-
tions in the measured concentration pat-
terns, for example, dilution effects due to
different amounts of temper [3]. In an in-
vestigation of valuable material, it is often
impossible to repeat a measurement, so a
consideration of all forms of "imperfect-
ness" is most desirable.
We will outline a dissimilarity coefficient,
which is not only able to handle all the
problems mentioned so far, but can also
be used in a new grouping and assigning
procedure based on a "filter" process. All
other existing coefficients require an
established classification algorithm, such
as Principal Component Analysis [5] or
Cluster Analysis [1], which are known to
be not completely satisfying for grouping
pottery according to their chemical com-
position [6].
To start with the Mahalanobis distance,
we emphasize that it can be used only
when groups of related data points and
© Springer-Verlag 1994
thus "chemical fingerprints" have already
been established. Their covariance matrix
C is used for assigning or rejecting further
data points E to a group with mean ~0 by
calculating the "reduced" squared
Mahalanobis distance
d2M,red(.~,&) = 2 t (.~- ~o) C-1(.~-.~o) . (1)
m the same effect.
t denotes the transpose of a vector, m is
the number of elements under considera-
tion. The factor l/m is introduced for
normalization in case of single missing
numbers. For group members, Eq. (1) is
distributed as z Z / m , if C is known exact-
ly. Thus, a membership test is equivalent
to the well-known )CZ-test in data analy-
sis, and Eq. (1) can serve as a "filter" to
sort out data points statistically similar to
a reference value.
Individual errors of measurement, how-
ever, are not considered in this "filter"
method either. Sometimes they are esti-
mated later from the grouping results. But
if they are known prior to any statistical
analysis for each value, and C is indepen-
not differ by their individual concentra-
tion values, but by a factor common to
most or all of the single numbers. This
can be explained by natural "dilution",
e.g., due to a different amount of temper
containing few or none of the trace ele-
ments measured. Technical irregularities
(for example, weighing errors) result in
By introducing a new degree of freedom,
however, it is possible to consider dilution
effects in Eq. (2) as well. If two data
points Y and fl and their error matrices are
given, the extended form of Eq. (2) can be
written as
2 ~
1
dm+v,,clit,~ed(X,y ) = t(fE- y)
rn-I
(3)
•(f2S~+S~)-~(fE-2).
~15
o
d
= 9
f is in the beginning an unknown "dilu-
tion factor", which has to be determined
by minimizing Eq. (3) with respect to f
(method of effective variance [8]). Using
this filter instead of Eq. (2) leads to a
much quicker formation of groups [7].
Here again it is possible to use a group
with mean Y0 and covariance matrix C in-
stead of the second data point )7.
The consideration of both dilution effects
and precision of measurement in Eq. (3)
also results in a better separation of dif-
ferent reference patterns, as shown in
Fig. 1. As an example, all Mycenaean
shards were chosen which belong either to
the Mycenae or the Tiryns group [9] of
our own data. The Tiryns pattern was
used as reference value £0. The results of
the filter process are shown for the "old"
Mahalanobis distance Eq. (1) and for the
new form Eq. (3), including both preci-

dent of 2, propagation of errors yields an more

samples
extended form of Eq. (1): >
X X
X X X 0 0 O0
2 + ~ J'g X X X XXX X X X 0 0 0 0 0 0 0 0 0 0 0 O0 0
d M + U, red( x, )CO) = - - (X-- Xo) (Sx -}- C ) - t X X !XXX XXX X X XXX X X X XO0 X 0 0 DO0 0 0 0 0 0 0 0 O0
m o , XXtXX.g.XX~X, XXX~(XX, XXXXX r XXX,XOX£)XO~ ~ , 13XOX.XX,Y.XI3XI)O~3,XO.XBOBXI), DX
1 2 3 4 5 6 7 8 9 10 11 12 13
a
• ( 2 - 2o) . (2) d2M, red
27

S~ is a diagonal matrix containing the X

X
24
squares of the uncertainties of the indi- X
X
vidual concentrations. Replacing C by the 21 XX
matrix of squared errors, Sp of another XX
XX
data point j and replacing 2 0 by 07 in the 18 XX
formula, Eq. (2) can also be used to deter- XX
XX
mine data points similar to each other. 15 ~(XX
-XXX
The limitation of applicability of the XXX
Mahalanobis distance to groups already 12 XXX
-XXX
established can therefore be dropped, XXX 0
when statistical errors of measurement 9 - XXX 0 0 0
-XXX 0 0 0 0
are known and considered. So it is possi- XXX 0 0 O0 O0

I
ble to form new groups of data points 6 XXX 0 0 0 000000 fewmore
XXXX 0 0 0 0 000000 samples
with respect to their statistical indistinct- XXXXX 0000 0 O0 0 0 0 0 0 0 0 0 - >
ness. Using these "core" groups and their 3 XXXXX 0000000 000000000 0 O0
XXXXX 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 000
covariances, more similar samples can be XXXXX 000000000000000000000000000 O0 0
X X . X X ~ X ~ , p DODDt D,ODDOD£)DDDD.ODDODDBDODDBBODDDDD, DD£)p 0~_,, i O , , £11,,~
found by applying the filter process again 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13
to the dataset [7]. Successively, the whole b
d2M+U,dil, red
grouping can be done, where establish-
ment of and assignment to groups are Fig. 1. Comparison of the existing Mahalanobis filter (a) and the new version (b). The values ob-
tained by using Eqs. (1) and (3), respectively, are displayed for each of the samples belonging to
performed by the same algorithm.
the Tiryns (X) and Mycenae (0) groups (77 and 164 shards, respectively).The Tiryns group values
In evaluating the trace element patterns of serve as reference pattern. 26 elements [9] were used for calculation. A suitable filter should yield
ancient ceramics, it appears that using both small d~ed values for all group members and a good separation from the rest of the dataset.
Eq. (2) or any established method is not The dashed line indicates the 95°70 confidence level of ZZed statistics, which may serve as a
sufficient. Closely related pieces often do "cutoff" value for group membership

Naturwissenschaften 81 (t994) © Springer-Verlag 1994 547

sion of measurement and dilution. The
"old" filter rejects most of the Tiryns
samples as group members, mainly due to
dilution effects. Also, there is no clear
separation between both groups, whereas
the extended form is not only able to find
all the group members, but also separates
them well from the other samples. This
feature can be observed in all our prove-
nance studies. So the consideration of
both errors of measurement and dilution
effects by using a filter Eq. (3) results in
a much higher certainty in forming of
groups and assigning questionable shards
to reference patterns already established.
Naturwissenschaften 81, 548-550 (1994)
Environmental Scanning Electron Microscopy and
Its Application to Archaeological Studies*
M. Ft~ting and H. Schnarr
Fraunhofer-Institut far Werkstoffmechanik, D-06120 Halle
M. Becker
Landesamt ft~r archfiologische Denkmalpflege Sachsen-Anhalt, D-06114 Halle
Since 1988 environmental scanning elec-
tron microscopes have been commercially
available. However, the idea of compen-
sating the negative charging of noncon-
ductive specimens in the scanning elec-
tron microscope by a small amount of
positive gas ions is more than 20 years
older [1]. The ultimate design of the envi-
ronmental scanning electron microscope
(ESEM)E3 is based on two pressure-limit-
ing apertures which separate the specimen
chamber containing gases having a pres-
sure of at least 50 Tort from the high-vac-
uum column, including the ultra-high-
vacuum LaB6 electron gun. The gas ful-
fills three functions. It discharges non-
* This study was supported by the Bundes-
ministerium ft~r Forschung und Technologie
(BMFT), core program "Einsatz neuer Teehno-
logien in den Geisteswissenschaften".
The authors would like to dedicate this article
to the memory o f their colleague and friend
Jiirgen Hopfe, who recently passed away, in
grateful acknowledgement of the constant en-
couragement and help he provided through his
constructive criticism and ideas.
548
One of us (Th. B.) is indebted to the "Stu-
dienstiftung des deutschen ¥olkes" for
the support by a Ph.D. fellowship.
Received June 14, 1994
1. Sneath, P.H., Sokal, R.R.: Numerical Tax-
onomy. San Francisco: Freeman 1973
2. Skoog, D.A., Leary, J.J.: Principles of In-
strumental Analysis. Orlando: Saunders
1992
@ Springer-Verlag 1994
conductive specimens, it facilitates the de-
tection of electrons as an amplifying me-
dium, and near-equilibrium vapor pres-
sures may prevent or retard specimens
from drying.
Because of the easy imaging of noncon-
ductive, moist or wet specimens, ESEM
enables the routine use of scanning elec-
tron microscopy for archaeological re-
search. To gain first-hand experience in
1991, the Bundesministerium ft~r For-
schung und Technologie offered a grant
for a project to advance the application of
environmental scanning electron micros-
copy to the field of archaeometric re-
search. The Germanic grave of a "prince"
found in Gommern near Magdeburg in
1990 was investigated. The valuable evi-
dence found in the grave enabled the ex-
amination of the abundant collection of
different materials in various states.
The preferred methods of investigation
used for archaeometric research are non-
destructive or nearly nondestructive, since
only small quantities of material are nec-
essary. This condition can be fulfilled by
environmental scanning electron micros-
copy in a narrower sense, if the samples
Naturwissenschaften 81 (1994) © Springer-Verlag 1994
3. Perlman, I., Asaro, E, in: Science and Ar-
chaeology, p. 182 (R. H. Brill, ed.). London:
MIT Press 1971
4. Harbottle, G.: Radiochemistry 3, 33 (1976)
5. Murtagh, E, Heck, A.: Multivariate Data
Analysis. Dordrecht: Reidel i987
6. Pollard, A.M., in: Proc. 22nd Syrup. on Ar-
chaeometry, p. 56 (A. Aspinall, S.E. War-
ren, eds.). University of Bradford 1983
7. Beier, Th., Mommsen, H.: Archaeometry
36, 287 (1994)
8. Barker, D.R., Diana, L.M.: Am. J. Phys.
42, 224 (1974)
9. Mommsen, H., Beier, T., Diehl, U., Podzu-
welt, Ch.: J. Archaeol. Sci. 19, 295 (1992)
are small enough to fit in the specimen
chamber. Otherwise, small fractions or
microscopically small particles of the
sample can be investigated as representa-
tive materials, if all the features of interest
can be assumed to occur in this sample.
Conventional scanning electron microsco-
py routinely enables the imaging of solely
conductive or conductively coated speci-
mens. However, nearly all the objects in
which the archaeologists are interested
have a nonconductive surface: with the
exception of metals, all specimens consist
of nonconductive materials. In addition,
organic or strongly corroded materials
may be hydrated, thus becoming most un-
stable in the vacuum of the microscope.
However, metals are usually coated with
thick, nonconducting oxide layers or with
a nonconducting protective layer of wax
or lacquer, which demands extensive
preparations if conventional scanning
electron microscopy is to be applied. In
archaeological research, conventional
SEM has not been established to the same
extent as in materials research. On the
other hand, all these difficulties of imag-
ing archaeological specimens are avoided
by applying environmental scanning elec-
tron microscopy [2].
However, this is only the least advantage
the ESEM offers. Identifying materials
solely by imaging requires experience in
interpreting the morphology at this mi-
croscopic level. Experience can only be
gained by applying conventional or envi-
ronmental scanning electron microscopy
due to the inherent typical contrast mech-