Hyperfine Interactions 150: 73–89, 2003.

73
© 2003 Kluwer Academic Publishers. Printed in the Netherlands.

Early Pottery Making in Northern Coastal Peru.

Part I: Mössbauer Study of Clays

I. SHIMADA1, W. HÄUSLER2, T. HUTZELMANN2 and U. WAGNER2

1 Southern Illinois University, Carbondale 62901, USA
2 Physik-Department E15, Technische Universität München, 85747 Garching, Germany

Abstract. We report on an investigation of several ancient clays which were used for pottery making
in northern coastal Peru at a kiln site from the Formative period (ca. 2000–800 BC) in the Poma Canal
and at a Middle Sicán pottery workshop in use between ca. AD 950 and 1050 at Huaca Sialupe in
the lower La Leche valley. Neutron activation analysis, 57 Fe Mössbauer spectroscopy and X-ray
diffraction were used for the characterisation of the clays. The changes that occur in iron-bearing
compounds in the clays depending on the kiln atmosphere and on the maximum firing temperature
were studied by Mössbauer spectroscopy and X-ray diffraction. Laboratory firing series under vary-
ing controlled conditions were performed to obtain a basic understanding of the different reactions
taking place in the clays during firing. The results can be used as models in the interpretation of the
Mössbauer spectra observed in ancient ceramics from the same context.

Key words: Mössbauer spectroscopy, X-ray diffraction, pottery clays, firing of clay.

1. Introduction
Clay was an important raw material for prehistoric man [1, 2]. The understanding
of its behaviour during firing under various conditions is essential in the recon-
struction of early pottery production. What is needed for assessing the possible or
probable firing conditions of ancient ceramics is a large set of reference data for
samples fired under various conditions. To find the appropriate clay deposits for
comparative laboratory studies is often difficult, but unfired pottery or bricks, un-
fired clay stoppers [3] or mudplaster from wattle and daub houses [4] may be used
instead. In the course of our investigations of ceramics from northern coastal Peru a
systematic laboratory study of the firing behaviour of local clays from two pottery
workshops was performed as a precondition for assessing pottery production in this
region. The results of this study will be reported in some detail in this paper.

2. Description of the material

Between 1985 and 1990 many well-preserved pottery kilns from the Formative
period (ca. 2000–800 BC) were excavated along the modern Poma Canal in the
Poma National Historical Sanctuary in the middle La Leche valley [5]. The kilns
were built [6] into a local clay-rich stratum. Clay from this stratum was used for
74 I. SHIMADA ET AL.

laboratory model experiments and for making replica vessels and test specimens
for field firing experiments. It will be called clay Batán Grande and is listed as
24/34 in our Munich database.
In 1999 and 2001 a Middle Sicán pottery workshop in use between about AD
950 and 1050 was excavated at Huaca Sialupe in the lower La Leche valley, about
25 km southwest of the Poma Canal site [7]. Several unfired clays found at the
workshop were investigated in detail. Firing studies were performed on clay from
an unfired clay brick (39/80) from a kiln structure and on a clay (39/312) from a
modern adobe brick-making pit at the south end of the site. During the excavation
in 2001, lumps of clay and unfired sherds were found at the Huaca Sialupe work-
shop. These finds proved to be perfect model materials and were also investigated.

3. Methods

In a first step all clays were characterised by neutron activation analysis [8] together
with sherds from the different sites to verify that they have the same element com-
position as local ceramics and hence can justifiably be used as model materials
[9, 10]. X-ray diffraction (XRD) [11] was applied for the identification of the clay
and associated minerals present in the chosen model materials. The main method
used to study the firing behaviour is 57 Fe Mössbauer spectroscopy [12, 13] because
of its unique potential to record changes of the iron-bearing compounds during
the firing of clay. Especially the sensitivity to changes caused by different kiln
atmospheres provides valuable information.

4. Firing procedures

The studied firing procedures are listed in Table I. Isochronal firing (IC) is the most
frequently used model procedure. Firing temperatures were increased in steps of
50◦ C from 50◦ C to 1000◦ C or above. Oxidizing firing (O) took place in air in a
laboratory furnace. For firing under reducing conditions (R) the samples were kept
in closed quartz vessels filled with charcoal. A new sample was used for each firing.
Routinely a duration of 48 h was chosen for firing in air to ensure that all reactions
taking place at a given temperature reach their equilibrium. Firing in a reducing
environment generally lasted for 3 h. For both oxidising and reducing firing the
samples were put into the cold kiln and heated to the maximum temperature within
2 h. At the end of the firing period the power was switched off and the samples
were allowed to cool together with the furnace, which took about 1 h.
Isothermal firing (IT) studies were performed to obtain information on the speed
of reactions at certain temperatures. For short heating times the samples were
inserted into and taken out of the hot furnace.
MÖSSBAUER STUDY OF CLAYS 75
Table I. Laboratory firing cycles used in this work. T is the firing tem-
perature, t the waiting time at the individual temperatures. (O) stands for
oxidising firing in air and (R) for firing in a reducing environment. If a
range of temperatures is given, the samples are heated to all temperatures
within this range, in steps of 50◦ C and with a new sample for each step.
Temperatures for O and R processes are separated by semicolons. IC means
isochronal and IT isothermal annealing

Procedure T (◦ C) t (h) Representative for:

O IC 50–1200 48 Kiln with sufficient draft

R–O IC 800; 50–1200 3; 48 Closed kiln; oxidation at the
end of the firing
R IC 50–1000 3 Closed kiln with excess fuel
O–R IC 700–800; 800 48; 3 Kiln with sufficient draft;
closed at the end of firing
O IT 400, 500, 700, 0.17–48 Influence of the duration of
850 firing in air
R–O IT 800; 3; Influence of duration of
700, 800, 900 0.17–48 firing in air after reduction

5. Mössbauer spectroscopy

5.1. ROOM - TEMPERATURE STUDY OF CLAYS FROM BATÁN GRANDE AND

HUACA SIALUPE

Mössbauer studies of clay Batán Grande have already been published [1, 14, 15].
Systematic investigations of unfired material from Huaca Sialupe are described
here. A comparison of room-temperature (RT) Mössbauer spectra of the clays
from Batán Grande (24/34) and from the unfired brick from Sialupe (39/80) is
shown in Figure 1 together with the respective X-ray diffractograms. The (RT)
Mössbauer spectra of the clays exhibit the small Fe3+ quadrupole splitting of 0.5–
0.7 mm/s common in unfired clays and characteristic for structural iron and for
accessory superparamagnetic iron oxides in the clay. XRD scans show that all
clays contain a similar mix of clay minerals, whereas the contents of quartz and
feldspars differ. Clay Batán Grande contains more 14 Å minerals (mainly chlorite)
than clay Sialupe. This accounts for its excellent handling properties, for which this
clay was chosen as the raw material for making the replica vessels for field firing
experiments [16]. Clay Sialupe contains up to 10% of the iron as epidote [17],
which is easily recognised in the Mössbauer spectra by its large Fe3+ quadrupole
splitting of 2.0 mm/s.
76 I. SHIMADA ET AL.

Figure 1. RT Mössbauer spectra (left) and the respective XRD-scans (right) of two clays from
Sialupe (39/80 and 39/354) and one from Batán Grande (24/34). The 14 Å peak is much stronger in
the clay from Batán Grande than in the clay from Huaca Sialupe.

In clay Batán Grande about 20% of the iron is present as goethite and, to a minor
extent, as hematite. The goethite and some of the hematite are superparamagnetic at
RT. Thus in the RT Mössbauer spectra the quadrupole doublet of the superparamag-
netic oxides is superimposed on the Fe3+ doublet of the clays (Figure 2). At 4.2 K
the goethite exhibits the typical six line Mössbauer pattern with a hyperfine field
of 50 T, which can easily be distinguished from the pattern of hematite with a field
of 53 T. The oxide phases can be extracted by treatment with bicarbonate buffered
dithionite (DCB) [18]. This is a simple method to determine the amount of oxidic
phases in the clays. A broad background due to slow paramagnetic relaxation [19]
of structural Fe3+ appears at 4.2 K in the DCB extracted sample.

5.2. FIRING OF CLAY BATÁN GRANDE AND CLAY SIALUPE

An overview of the firing behaviour of clay Batán Grande (sample 24/34) and of
clay Sialupe (39/80) is given in Figures 3 and 4, where the RT Mössbauer spectra
MÖSSBAUER STUDY OF CLAYS 77

Figure 2. RT and 4.2 K Mössbauer spectra of untreated clay Batán Grande (left) and the respective
spectra after DCB extraction (right). Note the different velocity scales for the RT and 4.2 K spectra.
Note the different velocity scales.

taken after oxidising firing in air (O), after firing in air preceded by a reduction at
800◦ C (RO) and after firing in a reducing atmosphere (R) are plotted against the
firing temperatures. Of all samples Mössbauer spectra were also measured at 4.2 K.
In this manner the transformations taking place in different clays on firing under
varying conditions can be followed in detail.
During firing in air (O) Fe2+ oxidises below 500◦ C. A second Fe3+ quadrupole
doublet with a large splitting of around 2 mm/s, characteristic for the mineral
epidote, is clearly visible in the spectra of clay Sialupe (Figures 1 and 4, top).
Formation of hematite is dominant in the high-temperature region above 800◦ C.
The Fe2+ species formed during the 3 h reduction at 800◦ C are rather stable
during the subsequent firing in air. Their oxidation to Fe3+ begins at about 400◦ C
and is complete only after firing at 700◦ C.
During the reducing firing (R), reaction begins only at 400◦ C, probably be-
cause at lower temperatures oxygen does not react with the carbon to form carbon
monoxide, which then reacts with the iron in the clay. At higher temperatures
more and more Fe2+ species form. Finally iron metal, easily recognisable by its
small magnetic field of 30.5 T, forms at 900◦ C in clay Sialupe and at 1000◦ C in
clay Batán Grande. In clay Sialupe a small amount of magnetite forms during the
reducing firing at and above 900◦ C.
Some of the Mössbauer parameters obtained from the spectra of Figure 4 are
shown in Figure 5. For oxidising treatment the temperature dependence of the
quadrupole splitting of the Fe3+ doublet, Q-Fe3+ , exhibits the typical increase
on firing between 350◦ C and about 650◦ C attributable to the dehydroxylation of
78 I. SHIMADA ET AL.

Figure 3. Three-dimensional plots of the RT Mössbauer spectra of clay Batán Grande (24/34) fired
in air for 48 h (O, top), fired in air for 48 h after a preceding reduction at 800◦ C for 3 h (RO, middle),
and fired in a reducing environment for 3 h (R, bottom).

the clay minerals. The kink at 600◦ C arises from the decomposition of chlorite
[20]. During reoxidation after a 3 h reduction at 800◦ C (RO) Q-Fe3+ never reaches
values above 1.2 mm/s and begins to decrease again around 600◦ C up to firing
temperatures of 850◦ C. It remains well below the Q-Fe3+ values obtained during
firing in air without a preceding reduction. This difference (cf. Figure 5, middle)
allows one to decide whether otherwise undistinguishable samples have been fired
in air only or have experienced a reduction before being oxidised at the end of the
firing cycle.
Fe2+ species formed during reduction of clay minerals at 800◦ C are definitely
more stable than Fe2+ compounds originally present in the clays. The most prob-
able compound to form during reduction of clays at high temperatures is her-
cynite [21]. However, we could not identify hercenite by XRD, possibly because
of its bad crystallinity. Reduction at high temperatures leads to a component with a
MÖSSBAUER STUDY OF CLAYS 79

Figure 4. Three-dimensional plots of the RT Mössbauer spectra of clay Sialupe (39/80) fired in air
for 48 h (O, top), fired in air for 48 h after a preceding reduction at 800◦ C for 3 h (RO, middle), and
fired in a reducing environment for 3 h (R, bottom).

broad single line, presumably wüstite. It is difficult to separate from the other Fe2+
components and also could not be identified by XRD, probably again due to poor
crystallinity. Iron metal forming around 900◦ C and above is easily identified by its
small hyperfine field but is of little interest in archaeological ceramics because of
its instability during burial.
The firing behaviour of clay Sialupe is very similar to that of clay Batán Grande,
as is illustrated by Figure 6. This similarity gives us some confidence that these
clays can serve as reference materials for the finds of archaeological ceramics of
the larger area of the Poma National Historical Sanctuary. There is, however, one
80 I. SHIMADA ET AL.

Figure 5. RT Mössbauer parameters obtained for clay Sialupe (39/80) subjected to the three firing
cycles, O, RO, and R. Q-Fe3+ is the quadrupole splitting of the main Fe3+ doublet, A-Fe3+ and
A-Fe2+ are the fractional areas of the Fe3+ and Fe2+ doublets and Anm is the cumulated fractional
area of all species that show no magnetic splitting.
MÖSSBAUER STUDY OF CLAYS 81

Figure 6. Comparison of the firing curves of clay Batán Grande (BTG, open symbols) with those of
clay Huaca Sialupe (Sia, full symbols) after firing in air for 48 h.

interesting difference between the Q-Fe3+ curves for the two materials. The kink
near 600◦ C attributed to the dehydroxylation of chlorite is more pronounced for
clay Batán Grande than for clay Sialupe. This tallies well with the XRD observation
of more chlorite in Clay Batán Grande than in clay Sialupe (Figure 1).

6. X-ray diffraction

To supplement the Mössbauer data, the transformations taking place during firing
of the clays Batán Grande and Sialupe were also studied by X-ray diffraction
(Figure 7). The layer silicates observed in the untreated clay Sialupe (39/80) are
mica, kaolinite and 14 Å layer silicates, mainly chlorite. Amphiboles and feldspars
are also present. Already after heating to 300◦ C, the typical kaolinite peak is di-
minished in intensity, after heating to 400◦ C only traces of it are left. Kaolinite
is supposed to transform to metakaolinite shortly below 450◦ C [22], but in the
present case may do so at lower temperatures due to the long duration of the
heating.
Chlorite decomposes near 650◦ C [20], mica is still seen in the X-ray diffrac-
tograms after firing at 900◦ C but decomposes during firing at 950◦ C. Only the
XRD peaks of feldspars and quartz persist on firing at 1000◦ C. XRD data can
thus be helpful in setting upper limits for the firing temperatures of archaeological
ceramics according to which minerals are still present. On the other hand, when a
mineral is no longer present in the ceramics but is known to have been present in
the raw clay, the decomposition temperature of this mineral sets a lower limit to
the firing temperature.
82 I. SHIMADA ET AL.

Figure 7. Selected X-ray diffractograms of clay Sialupe (39/80) heated in air to different tempera-
tures for 48 h.

7. Firing under varying conditions

Mössbauer spectra observed in Formative pottery from Chólope in the Poma Re-
serve could be reproduced by firing clay Batán Grande under reducing conditions
with an oxidizing step at the end of the firing cycle [15]. This firing procedure was
frequently used in early pottery production. To reproduce the Mössbauer patterns
of Sicán blackware, a type of ceramics typical for the Middle Sicán period [7],
varying firing cycles had to be applied [10]. A wide range of data for varying firing
conditions is therefore needed.
Firing first under oxidising and then under reducing conditions is of essence in
this context. In Figures 8 and 9 we present spectra for clay Batán Grande first fired
in air for 48 h at 700◦ C and 900◦ C and then reduced with charcoal at temperatures
between 500◦ C and 900◦ C. This sequence of firing steps would be representative
for first firing with ample admission of air into the kiln, which is closed at the end of
the firing in order to obtain black pottery. The oxidizing firing at 700◦ C turns out to
have but little influence on the result of the subsequent reduction, since at 700◦ C the
clays lose the hydroxyl groups but still retain their layer structure. The Fe2+ formed
during the reduction step will therefore still be part of this layer structure. Oxida-
tion at 900◦ C, however, causes a complete breakdown of the layer structure and
induces different reactions during the subsequent reduction. On reduction between
MÖSSBAUER STUDY OF CLAYS 83

Figure 8. RT and 4.2 K Mössbauer spectra of clay Batán Grande first oxidised for 48 h at 700◦ C and
then reduced for 3 h at temperatures between 500 and 800◦ C. The spectra were taken with the source
of 57 Co in Rh having the same temperature as the absorber. Note the different velocity scales.
84 I. SHIMADA ET AL.

Figure 9. RT and 4.2 K Mössbauer spectra of clay Batán Grande first oxidised for 48 h at 900◦ C and
then reduced for 3 h at temperatures between 500 and 800◦ C. The spectra were taken with the source
of 57 Co in Rh having the same temperature as the absorber. Note the different velocity scales.
MÖSSBAUER STUDY OF CLAYS 85

700◦ C and 900◦ C the Fe2+ quadrupole doublets at RT have a rather wide range of
splittings while the amount of magnetically ordered Fe2+ species observed at 4.2 K
increases. This is most probably due to the formation of spinels like hercynite,
which order magnetically at low temperatures if they contain enough iron [19].
A difference in the duration of the reduction is of little influence.

8. Isothermal firing
8.1. FIRING IN AIR
Isothermal annealing experiments were performed at 400◦ C, 500◦ C, 700◦ C, and
850◦ C to establish how long it takes at different temperatures to obtain an equi-
librium state [1]. Experiments were performed on clay Batán Grande (24/34) for
firing times between 3 min and 48 h. Figure 10 shows the essential Mössbauer
parameters, i.e., the quadrupole splitting of the Fe3+ components, Q-Fe3+ , and
the fractional area of all nonmagnetic iron compounds, Anm , obtained from RT
Mössbauer spectra. The dehydroxylation leading to the increase of Q-Fe3+ from
about 0.7 mm/s to nearly 1.4 mm/s is virtually complete after a few minutes at
700◦ C. At 500◦ C the dehydroxylation reaction is more sluggish, but equilibrium
appears to have been reached after several hours. At 400◦ C the increase of Q-Fe3+
is still small and seems to have reached an equilibrium value of about 1 mm/s after
about 10 h.

Figure 10. Dependence of Q-Fe3+ (full symbols) and Anm (empty symbols) on the duration of
firing clay Batán Grande (39/80) for temperatures of 400, 500, 700, and 50◦ C, from [1].
86 I. SHIMADA ET AL.

At 850◦ C Q-Fe3+ increases steeply during the first 10 minutes. The heating-up
period of the samples must be of the order of a minute or less when the sample is
inserted into the hot furnace. Thus dehydroxylation at 850◦ C seems to take about
10 minutes and only then the decay of the dehydroxylated layer structure sets in,
which is why Q-Fe3+ reaches the high value of about 1.30 mm/s before decreasing
again. The decrease of Q-Fe3+ , which is due to the breakdown of the layer structure
of the clay minerals, is a much slower process that seems to be still incomplete after
48 h. These results show that kiln temperatures above 800◦ C reached only briefly
during the firing of ceramics may not be fully represented in the Mössbauer spectra
by a low Q-Fe3+ value. In such cases, the firing temperature as determined from
Mössbauer data may be lower than the true maximum temperature.

8.2. FIRING IN AIR AFTER A PRECEDING REDUCTION

Reducing firing at temperatures above about 700◦ C leaves the iron in ceramics
largely in divalent form. When specimens are then exposed to an oxidising at-
mosphere, the Fe2+ is reoxidised to Fe3+ . This has often happened with archae-
ological ceramics when the kiln was opened, either accidentally or on purpose,
towards the end of the firing cycle. It is therefore of importance in the interpretation
of Mössbauer data on such pottery to know how rapidly this reoxidation proceeds
at different temperatures.
Such a study was therefore performed on previously reduced samples of clay
Batán Grande (24/34). Treatment with charcoal in a closed vessel for 3 h at 800◦ C
leads to a nearly complete reduction of the iron in the clay to Fe2+ . This Fe2+
may still be incorporated in the dehydroxylated clay, or crystalline Fe2+ -bearing
spinels or other phases which may already have formed. The exact nature of these
phases has, however, not yet been determined. The presence of hercynite, FeAl2 O4 ,
which might form during heating in reducing conditions, could not be detected
by X-ray diffractometry. The Mössbauer spectra of the reduced clay also do not
unambiguously show the presence of hercynite, particularly since the actual spinel
phases may have more complicated Mössbauer patterns than pure FeAl2 O4 [21].
In Figure 11 the time dependence of reoxidation is shown for three different
temperatures. Structural Fe2+ in fresh clays is usually completely oxidised on firing
in air for 48 h at 500◦ C (Figures 3, 4 and 5). For clay that was previously reduced at
800◦ C the reoxidation is far from being complete after 48 h at 500◦ C (Figure 11).
Even at 600◦ C about 8% of the Fe2+ still survive 48 h annealing in air. Reoxidation
of Fe2+ at 700◦ C takes about 2 h to be nearly complete. After 1 h about 10% of
Fe2+ are still left.
These results show that reoxidation of reduced ceramics is quite sluggish even at
700◦ C. This fact needs to be taken into account when one interprets the Mössbauer
spectra of reoxidised ceramics, particularly those with surface layers of reoxidised
material and a gray, still largely reduced core, which is frequently encountered in
prehistoric pottery.
MÖSSBAUER STUDY OF CLAYS 87

Figure 11. Reoxidation of reduced samples of clay Batán Grande after a 3 h reduction with charcoal
at 800◦ C. The fractional area of Fe2+ remaining after different times of heating in air are shown for
reoxidation temperatures of 500, 600 and 700◦ C, from [1].

9. Conclusions

The firing behaviour of the clays from Batán Grande and Huaca Sialupe has been
studied extensively, in a wide temperature range and under a variety of chang-
ing firing conditions. With the results of these studies, an unsurpassed body of
reference data for the interpretation of Mössbauer and X-ray diffraction data on
archaeological ceramics from the Poma National Historical Sanctuary is avail-
able.
In fact the available reference data allow suggestions to be made for the firing
processes of all archaeological ceramics from the Poma region. But one should
always keep in mind that, for a given clay, a particular firing cycle, i.e., a partic-
ular succession in time of different kiln atmospheres and firing temperatures, will
lead to a well defined Mössbauer and XRD pattern. The inverse is not necessar-
ily true: identical or very similar Mössbauer and XRD patterns may result from
substantially different firing cycles. Consequently the reconstruction of ancient
firing conditions on the basis of Mössbauer and XRD data is not necessarily unam-
biguous. Therefore other methods, like optical and scanning electron microscopy
should be included in the assessment.
Isothermal annealing series have revealed that the time spent at certain tem-
peratures and a certain kiln atmosphere is of essence and the interplay of time
and temperature may be an important point in the reconstruction of ancient firing
conditions. This is especially true for the formation of the layer structure with a
black core and a brick coloured surface, which is frequently observed in prehistoric
pottery.
88 I. SHIMADA ET AL.

Acknowledgements
We should like to thank the German Research Council for its support of the ar-
chaeometric work. One of us (I.S.) is grateful to the National Geographic Society
for research grants in support of the 1989 excavations at Poma Canal and the 1999
and 2001 excavations at Huaca Sialupe. The Wenner-Gren Foundation and John
Heinz III Funds also provided generous support of the 1999 and 2001 field work,
respectively. Support for the 2000 laboratory work in Peru was provided by the
Southern Illinois University faculty research grant.

References
1. Wagner, U., Gebhard, R., Grosse, G., Hutzelmann, T., Murad, E., Riederer, J., Shimada, I. and
Wagner, F. E., Clay: An Important Raw Material for Prehistoric Man, Hyp. Interact. 117 (1998),
323–335.
2. Wagner, U., Gebhard, R., Murad, E., Shimada, I. and Wagner, F. E., The Role of Small Particles
in the Study of Archaeological Ceramics, In: J. L. Dormann and D. Fiorani (eds.), Magnetic
Properties of Fine Particles, North-Holland, 1992, pp. 381–392.
3. Riederer, J., Wagner, U. and Wagner, F. E., Mössbauer Study and Firing Conditions of Ancient
Egyptian Ceramics with Multicoloured Layers, Radiochem. Radioanal. Lett. 40 (1979), 319–
328.
4. Wagner, U., Wagner, F. E., Riederer, J., Ulbert, C., Tellenbach, M. and Müller-Karpe, H.,
Recent Ceramic Finds from Montegrande, Peru, Studied by Physical Methods, Proceedings
of the British Academy 5 (1988/89), 1–15.
5. Shimada, I., Chang, V., Wagner, U., Gebhard, R., Neff, H., Glascock, M. D. and Killick, D.,
Formative Ceramic Kilns and Production in Batán Grande, North Coast of Peru, In: I. Shimada
(ed.), Andean Ceramics: Technology, Organization and Approaches. MASCA Research Papers
in Science and Archaeology, Supplement to Vol. 15, University of Pennsylvania Museum of
Archaeology and Anthropology, Philadelphia, 1998, pp. 23–61.
6. Shimada, I., Elera, G. and Chang, V., Ecavaciones de Hornos de Cerámica de Época Formativa
en Batán Grande, Costa Norte del Perú, Gaceta Arqueológia Andina 5(20) (1990), 19–43.
7. Shimada, I. and Wagner, U., Peruvian Black Pottery Production and Metalworking: A Middle
Sicán Craft Workshop at Huaca Sialupe, MRS Bulletin 26(1) (2001), 25–30.
8. Glascock, M. D., Neff, H. and Vaughn, K. J., Instrumental Neutron Activation Analysis and
Multivariate Statistics for Pottery Provenance, In: U. Wagner (ed.), Mössbauer Spectroscopy in
Archaeology, Hyp. Interact., topical issue, Vol. I, to be published.
9. Wagner, U., Gebhard, R., Murad, E., Riederer, J., Shimada, I. and Wagner, F. E., Kiln Firing at
Batán Grande: Today and in Formative Times, In: D. A. Scott and P. Meyers (eds.), Archaeo-
metry of Pre-Columbian Sites and Artefacts, Proc. of a Symposium Organized by the UCLA
Institute of Archaeology and the Getty Conservation Institute Los Angeles, California, March
23–27, 1992, Getty Institution Press, 1994, pp. 67–84.
10. Shimada, I., Häusler, W., Jakob, M., Montenegro, J., Riederer, J. and Wagner, U., Early Pottery
Making in Northern Coastal Peru. Part IV: Mössbauer Study of Ceramics from Huaca Sialupe,
In: U. Wagner (ed.), Mössbauer Spectroscopy in Archaeology, Hyp. Interact. 150, topical issue,
Vol. II, 2003.
11. Stanjek, H. and Häusler, W., Basics of X-ray Diffraction, In: U. Wagner (ed.), Mössbauer
Spectroscopy in Archaeology, Hyp. Interact., topical issue, Vol. I, to be published.
12. Wagner, F. E. and Kyek, A., Mössbauer Spectroscopy in Archaeology: Introduction and Ex-
perimental Considerations, In: U. Wagner (ed.), Mössbauer Spectroscopy in Archaeology, Hyp.
Interact., topical issue, Vol. I, to be published.
MÖSSBAUER STUDY OF CLAYS 89

13. Wagner, U., Wagner, F. E., Häusler, W. and Shimada, I., The Use of Mössbauer Spectroscopy
in Studies of Archaeological Ceramics, In: D. E. Creagh and D. A. Bradley (eds.), Radiation in
Art and Archaeometry, Elsevier, Amsterdam, 2000, pp. 417–443.
14. Wagner, U., Gebhard, R., Häusler, W., Hutzelmann, T., Riederer, J., Shimada, I., Sosa, J.
and Wagner, F. E., Reducing Firing of an Early Pottery Making Kiln at Batán Grande, Peru:
A Mössbauer Study, Hyp. Interact. 122 (1999), 163–170.
15. Wagner, U., Gebhard, R., Murad, E., Grosse, G., Riederer, J., Shimada, I. and Wagner, F. E.,
Formative Ceramics from the Andes and their Production: A Mössbauer Study, Hyp. Interact.
110 (1997), 165–176.
16. Shimada, I., Goldstein, D., Häusler, W., Sosa, J., Riederer, J. and Wagner, U., Early Pottery
Making in Northern Coastal Peru. Part II: Field Firing Experiments, In: U. Wagner (ed.),
Mössbauer Spectroscopy in Archaeology, Hyp. Interact. 150, topical issue, Vol. II, 2003.
17. Fehr, K. T. and Heuss-Assbichler, S., Intracrystalline Equilibria and Immiscibility along the
Join Clinozoisite-Epidote: an Experimental and 57 Fe Mössbauer Study, Neues Jahrb. Miner.
Abh. 172 (1997), 43–63.
18. Mehra, O. P. and Jackson, M. L., Iron Oxide Removal from Soils and Clays by a Dithionite-
Citrate System Buffered with Sodium Bicarbonate, Clays Clay Miner. 7 (1960), 317–327.
19. Wagner, F. E. and Wagner, U., Mössbauer Spectra of Clays and Ceramics, In: U. Wagner (ed.),
Mössbauer Spectroscopy in Archaeology, Hyp. Interact., topical issue, Vol. I, to be published.
20. Barnhisel, R. I. and Bertsch, P. M., Chlorites and Hydroxy-Interlayered Vermiculite and Smec-
tite, In: J. B. Dixon and S. B. Weed (eds.), Minerals in Soil Environments, 2nd edn, Soil Science
of America Book Series, Soil Science Society of America, Madison, Wisconsin, USA, 1989,
pp. 729–788.
21. Larsson, L., Neill, H. S. C. O. and Annersten, H., Crystal Chemistry of Synthetic Hercynite
(FeAl2 O4 ) from XRS Structural Refinements and Mössbauer Spectroscopy, Eur. J. Mineral. 4
(1994), 39–51.
22. Murad, E. and Wagner, U., Mössbauer Spectra of Kaolinite, Halloysite and the Firing Products
of Kalonite: New Results and a Reappraisal of Published Work, Neues Jahrb. Miner. 162(3)
(1991), 281–309.