The Study of Archaeological Floors: Methodological

Proposal for the Analysis of Anthropogenic Residues

by Spot Tests, ICP-OES, and GC-MS
William D. Middleton & Luis Barba & Alessandra Pecci & James H. Burton &
Agustin Ortiz & Laura Salvini & Roberto Rodriguez Surez
Published online: 19 June 2010
#
Springer Science+Business Media, LLC 2010
Abstract The identification of chemical activity residues on archaeological surfaces
requires the analysis of large numbers of samples, which can be costly and time
consuming. Researchers wishing to apply sediment chemistry often are confronted with
a dilemma of which technique to use and how to accommodate sediment chemistry into
their budget. We propose an approach to the identification of chemical activity residues
in which semiquantitative spot tests, which are cheap, quick, and easy to apply, are
employed as an initial phase of analysis in order to leverage the results of more time-
consuming and costly instrumental techniques. Three examples that pair spot tests with
gas chromatography-mass spectroscopy and inductively coupled plasma-optical
emission spectrometry analysis show that spot tests successfully identify areas of
interest. This approach can save both time and research funds.
Keywords Activity area analysis
.
Phosphorus
.
Chemical activity residues
.
Spot tests
.
GC-MS
.
ICP-OES
J Archaeol Method Theory (2010) 17:183208
DOI 10.1007/s10816-010-9088-6
W. D. Middleton (*)
Department of Material Culture Sciences, Rochester Institute of Technology, Rochester,
NY 14623-5604, USA
e-mail: wdmgss@rit.edu
L. Barba
:
A. Ortiz
Instituto de Investigaciones Antropolgicas, UNAM, Mexico, Mexico
A. Pecci
Archaeometric Laboratory, Department of Archaeology, University of Siena, Siena, Italy
J. H. Burton
Laboratory for Archaeological Chemistry, University of WisconsinMadison, Madison, WI, USA
L. Salvini
Centro di Analisi e Determinazioni Strutturali, University of Siena, Siena, Italy
R. R. Surez
Universidad de la Habana, La Habana, Cuba
Introduction
The archaeological analysis and interpretation of architectural space (the interpre-
tation of the function and the patterning of activities within and around buildings and
structures) has traditionally relied on formal architectural analysis, spatial analysis,
artifact distribution, paleobotanical and faunal remains, the byproducts of production
activities, and other physical residues of past human behavior. As early as the 1920s,
the potential of chemical activity residues on occupied surfaces was recognized
(Arrhenius 1929), but chemical analysis was neither widely nor intensively applied
until the 1970s, when the analysis of chemical residues in floors was introduced to
Mesoamerican archaeology (Barba and Bello 1978). Since its renaissance in
Mesoamerica, the analysis of chemical residues in occupied surfaces has become a
powerful technique to define the functionality of architectural spaces and has been
applied extensively and increasingly throughout Mesoamerica and other parts of the
world (Barba and Bello 1978; Barba and Denis 1985; Barba and Ortiz 1992;
Manzanilla 1993; Middleton and Price 1996; Middleton et al. 2005; Snchez and
Caabate, 1998; Terry et al. 2000; Wells et al. 2000).
One result of this renaissance of chemical residue studies is a proliferation of
methodologies for their detection and interpretation. We see variation in the class of
residues identified, in the techniques for their extraction and quantification, and in
sampling strategy. Different techniques entail radically different cost and time
requirements, as well as providing different types and quantities of data. In the face
of such methodological heterogeneity, one might be tempted to ask what is the
right technique?, but this would miss the point: each of the many techniques offers
a trade-off between three principal variables: time, cost, and data, so the right
technique, in fact, often depends on the research question, its data requirements,
and the funding available for chemical studies. We think that the question that we
should be asking and the question that we concern ourselves with here, is how can
the multiplicity of techniques for the analysis of chemical residues on occupied
surfaces be employed to most expediently and economically provide the data
necessary to address the research question at hand.
During the first half-century, in which archaeologists were using chemical activity
residues on floors and other occupied or utilized surfaces (roughly the 1920s to the
1970s), the techniques used were largely drawn from soil science (e.g., Arrhenius 1929;
Cook and Heizer 1962, 1965; Heidenreich et al. 1971). These techniques produced
accurate, precise, and reproducible quantitative results, but determinations had to be
made for single elements, compounds, or other properties, one at a time. As a result,
the analysis of large numbers of samples for multiple properties was prohibitively time-
consuming and costly. This fact, more than anything else, can account for recognized
potential of chemical activity residues being so sparsely utilized prior to the 1970s.
In the late 1970s, Barba and Bello (1978) introduced the use of chemical spot
tests to the study of archaeological house floors in Mesoamerica. While these spot
tests provide only qualitative or semiquantitative results, they can be used to
elucidate multiple properties rapidly and inexpensively. As a result, the use of
chemical activity residues saw increasingly widespread use in archaeology.
By the end of the 20th century, advances in instrumentation had made fine-
grained, quantitative analysis increasingly feasible. In organic chemistry, advances
184 Middleton et al.
such as gas chromatography-mass spectroscopy (GC-MS) greatly facilitated the
precise identification of organic molecules. In inorganic chemistry, advances such as
inductively coupled plasma-optical emission spectroscopy (ICP-OES) made it
possible to make rapid determinations of multiple elements for large numbers of
samples. These advances in instrumentation have opened the field of chemical
activity residues to scholars from such diverse disciplines as archaeology, chemistry,
and soil science. Not surprisingly, they bring with them a range of different
techniques for the identification and analysis of these residues.
Although there is considerable variation in the techniques used by various
scholars to extract and identify various chemical activity residues, we do not see this
as a major concern. Empirically, many, if not most techniques yield useful,
comprehensible results. For the most part, scholars are working with the resources
they have at their disposal and addressing specific research questions of interest to
them. We do not see this as an issue of any particular technique being intrinsically
better than any other. Instead, we are interested in exploring how different
techniques can be employed in tandem to maximize data recovery and minimize cost
and time requirements.
We present three examples in which spot tests are paired (rather than compared)
with instrumental analyses. The spot tests, which are quick, cheap, and easy but
semiquantitative, provide a preliminary assay of the sampled area. These results can
then be used to select sub-areas or sub-sets of samples that are likely to provide
useful results with more precise, quantitative instrumental analyses (GC-MS and
ICP-OES). With this staged sampling and analysis strategy, it is possible to sample
the largest possible area with spot tests and to focus the more costly and time-
consuming instrumental analyses on the areas where they are most likely to provide
useful data.
Chemical Activity Residues
The utility of chemical activity residues stems from the fact that many human
activities generate residues that are deposited on the surface upon which the activity
took place. These residues can vary in size from the macro-scale, such as lithic
flakes, bone fragments, pieces of plant or animal tissue, wood chips, etc., to the
micro-scale, such as ions and molecules in solution and fine particulates produced by
sawing, grinding, abrasion, crushing, mechanical dissolution, and so on. Unlike the
macro-scale residues which can be physically picked or swept up and discarded,
micro-scale residues can be absorbed by and incorporated into the surface on which
they are deposited (Barba 1986; Barba and Ortiz 1992; Middleton 1998; Middleton
and Price 1996).
Both organic and inorganic residues gradually accumulate in the pores of the
material and/or become chemically bound to or complexed with various constituents
of the material (for example, organic colloids adsorbed by clay particles), while areas
that were not in contact with the activity residues remain chemically clean.
Although some residues are more labile than others, once the residues have been
absorbed by the surface, there tends to be relatively little movement outside of the
physical disturbance of the surface itself (Middleton 1998). Because surfaces such as
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 185
plastered or beaten earth floors tend to be fairly homogenous in nature, the residues
have the effect of altering the chemical composition of the surface. This is the same
principle employed in the analysis of organic residues in ceramics to reconstruct
patterns of ceramic use. Pottery vessels are, as plastered floors, originally clean
when they are manufactured. During their use, they absorb the substances that come
in contact with them. The chemical analysis of residues in pottery allows the
identification of the substances stored or cooked in the vessels (Condamin et al.
1976; Evershed 1993; Evershed et al. 2002; Evershed et al. 2001).
While the detection of chemical activity areas is fairly straightforward, the
identification of the behaviors that generated the residues is not, particularly in the
case of inorganic chemistry. Equifinality, the existence of multiple pathways to the state
result, say a high concentration of phosphorus, is a problem. Phosphorus, for example, is
an extremely good indicator of human activity because it is ubiquitous in the organic
materials that humans use: plant and animal tissue, bone, wood ash, etc. all contribute
high levels of phosphorus to a floor surface. Therefore, multiple properties must be
assessed to differentiate between different residue sources (see Middleton 2004). In
order to make these distinctions, ethnoarchaeological studies are an absolute necessity
(Barba and Ortiz 1992; Middleton 1998, 2004; Middleton and Price 1996).
Ethnoarchaeological studies in present-day beaten earth and plaster-floored
houses allow us to match chemical activity residues to the behaviors that generate
them. Food preparation and consumption, for instance, are characterized by the use
of substances containing organic compounds such as proteins, fats, oils, and resins,
as well as inorganic compounds such as phosphates, that are absorbed by the
surfaces on which they are deposited. Wood ash tends to elevate concentrations of
potassium, manganese, sodium, and phosphorus, whereas in situ burning can be
identified through the thermal alteration of clays which enhances the extractability of
iron and aluminum. Ethnoarchaeological studies also provide a caveat to the overly
simplistic interpretation of chemical activity residues. A single space often is used
for more than one single activityit may be used simultaneously, sequentially, or
cyclically for a series of different activities. Therefore, it is a mistake to assume that
there is always a one-to-one correspondence between a single chemical activity
residue and a single activity (see Dore and Lpez Varela, this volume).
Thus, anthropogenic chemical activity residues can be a powerful tool for the
interpretation of architectural space and the identification of patterns of activity.
Numerous studies over the past three decades have validated the approach and have
demonstrated that a variety of analytical techniques can be applied to different types
of samples from interior and exterior surfaces with a variety of treatments, such as
stuccoed, plastered, or earthen floors, as well as exterior spaces (Barba 1986; Barba
and Denis 1985; Barba and Lazos 2000; Barba and Ortiz 1992; Linderholm and
Lundberg 1994; Lpez Varela et al. 2005; Middleton 1998, 2004; Middleton and
Price 1996; Middleton et al. 2005; Ortiz and Barba 1993; Terry et al. 2000; Wells et
al. 2000). Nevertheless, chemical activity residues constitute only one set of data,
and the interpretation of archaeological spaces must also be based on the
interpretation of other traditional archaeological indicators such as the distribution
of ceramics, lithics, animal bones, and botanic remains, the presence of features such
as fireplaces, altars, storage bins, or other structures, and to architectonic character-
istics such as rooms size, the presence/absence of windows, doors, and other spaces.
186 Middleton et al.
Sampling and Analysis Problems
The study of anthropogenic chemical activity residues on archaeological surfaces
requires the analysis of a large number of samples. In order to capture the footprint
of all activities, extensive surfaces must be intensively sampled: complete rooms, the
whole archaeological structures, and even whole sectors of a site should be sampled.
Depending on the scale of the landscapes, sites, and/or intra-site structures that have
to be studied, as well as the goals of the study, different sampling strategies may be
called for (see Wells, this volume).
When investigating the pattering of activities at a domestic scale, a fairly small-
sample interval is called for; studies typically use between 50 cm and 1 m (Barba
and Lazos 2000); however, the number of samples collected for any given space
increases exponentially as the sampling interval decreases in size. As a consequence,
with a sample area of any size, it is necessary to analyze hundreds or even thousands
of samples. For instance, in the study of the Oztoyahualco apartment compound in
Teotihuacan (Ortiz and Barba 1993), close to 500 samples were analyzed. For the
Teopancazco compound, in the same archaeological site, more than 800 samples
have already been analyzed, and the project is not finished yet (Pecci 2000; Pecci et
al. 2010). At atahyk, Turkey, over 650 samples were analyzed (Middleton et al.
2005).
Whatever the sample interval is, the number of samples to be analyzed increases
with the sample density and dimensions of the area to be covered. This also
increases both the money and the time spent in collecting and processing the samples
as well as shipping them if they are not to be analyzed in the field. These economic
and logistic factors become important considerations in planning and executing a
study.
A second and even more important issue in the use of anthropogenic chemical
activity residues for the functional analysis of archaeological structures is the
selection of which technique or techniques will be used in the study. Such questions
as: What kind of analysis is the right one? or Are some techniques more useful to
detect specific compounds than others?, and Which technique will tell me what I
most need to know? are all extremely relevant, but so too is What do I have the
time and funding to do?.
As mentioned above, different research groups have developed different techniques
in the last decades. Since the late 1970s, the Archaeometric Laboratory of the Instituto
de Investigaciones Antropologicas at the UNAM, Mexico has focused on the use of
spot test analyses for a variety of sediment attributes that allow the rapid processing
of large numbers of samples, in the field if necessary, to study the distribution of
chemical compounds in order to elucidate the different uses archaeological spaces.
These spot tests can detect the presence of phosphates, carbonates, fatty acids, protein
residues, carbohydrates and to measure the pH level (Barba et al. 1991). These studies
have been supplemented, both in Mexico and in Italy, with GC-MS analysis of organic
residues to better understand the origin of the organic acids found with the spot tests
(Barba et al. 1998; Pecci 2004; Pecci et al. 2010).
On the other side, Middleton, Burton, Wells, Terry, Parnell (Middleton and Price
1996; Parnell et al. 2002; Middleton 2004; Wells et al. 2000; Wells 2004), and
others have applied ICP-OES focused to the analyses of approximately a dozen
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 187
major elements, some of which are particularly useful in the archaeological
interpretation. It is a very precise quantitative analytical technique that provides
copious data that are amenable to powerful inferential statistical analysis. Richard
Terry and his group, in the Brigham Young University have concentrated their
attention on the development of quantitative analysis for phosphates in soil samples,
focusing upon the study of large open areas such as plazas (Terry et al. 2000).
A Comparison of Techniques
Archaeologists have therefore to make some choices on the number of samples to be
analyzed and on the analytical techniques to be used depending on time, resources,
and goals of the project. Below, we compare the various capabilities, requirements,
and drawbacks to three major techniques for the detection of chemical activity
residues. We reiterate, however, that this is decidedly not from the point of view of
any of the techniques being superior to any of the others. Furthermore, this is not
intended to be to be a comprehensive comparison of techniques, but rather a
comparison of the techniques that we have employed in our research.
Spot Tests
As stated above, spot tests established in Mexico are aimed at detecting the presence
of phosphates, carbonates, fatty acids, protein residues, and carbohydrates at a
semiquantitative level, and measuring the pH value (Barba et al. 1991). They are
simple techniques of analysis that can be performed by trained archaeologists and
students in the field if necessary (in a laboratory exercise, one of the authors has a
class of 20 students that analyze 100 sediment samples and plot their data in a single
class period using the Eidt Ring Test (Eidt 1973)). Spot tests are quick and cheap
compared to other techniques. As a consequence of using spot tests, it is possible to
analyze a large number of samples quickly at a very low cost.
Once the results of each spot test are obtained, they are plotted on the archaeological
map of the site or on the architectonic plan of the structure in order to obtain distribution
maps for each compound. These maps show the concentrations or absence of the
compounds. Comparing the distribution maps of all the chemical indicators to the
presence of archaeological materials and the architectural characteristics of the space, it
is possible to identify activity areas. Both the presence and absence of specific
compounds can provide useful information on the utilization of space.
The advantages of spot test analysis are evident. On the other hand, they also have
disadvantages such as providing only a relative idea of the abundance of the chemical
residues. Furthermore, with spot tests, it is feasible to detect organic acids' presence, but
it is not possible to identify their origin, and therefore know if they are related to resins,
waxes, fats, or oils. Protein residues likewise cannot be related to a particular origin.
In the interpretation of the activities performed in specific spaces, it is important
to correlate the results of all the chemical compounds analyzed. For instance, food
preparation activity areas are usually characterized by concentrations of fatty acids,
protein residues, phosphates, and carbohydrates present in the food that will be
associated with high values of pH due to the presence of ash as a combustion
188 Middleton et al.
byproduct. The animal stables are mainly characterized by the homogenous high
values of phosphates but low levels of other chemical indicators.
Gas Chromatography-Mass Spectrometry
As discussed above, spot tests cannot give information on the origin of the organic
residues often constituted by complex mixtures. Frequently, it is necessary to identify
each component of these mixtures, and for this purpose, gas chromatography coupled
with mass spectrometry (GC-MS) is one of the most suitable techniques. This kind of
analysis allows the separation and identification of many substances, lipids in particular.
This permits the interpretations of the residues absorbed in the archaeological floors and
ceramics, through the identification of specific markers that are characteristics of the
different substances (Evershed et al. 2001).
For example, it is possible to distinguish between animal and vegetal fats. In
particular, it allows identifying vegetable oils. Furthermore, GC-MS permits the
identification of markers characteristic of other vegetal substances common in
ancient European diet such as wine (Guash-Jan et al. 2004) and Brassicaceae
(Charters and Evershed 1995; Charters et al. 1997). The presence of animal stables
can also be detected monitoring the presence of coprostanol (Bull et al. 2003;
Evershed et al. 2001). On the other hand, Mesoamerican ritual areas were enriched
with blood and copal. Resins burnt during ceremonies were detected by GC-MS
analysis (Barba et al. 1996). The advantages of GC-MS are therefore evident, and
they are particularly related to the possibilities of knowing the specific substances
involved in ancient activities. On the other hand, the main disadvantage of this kind
of chemical analysis consists mainly in the complex and expensive instrumentation
required. Furthermore, the sample preparation is time consuming, as preparing a
group of 10 samples can take 1 day for each extraction, and the analysis of each
prepared sample lasts more or less 1 h (not taking into account the time needed for
the interpretation). Considering that different procedures are often carried out to
extract different compounds (Mottram et al. 1999; Guash-Jan et al. 2004), it can be
an extremely time-consuming technique. The study of the distribution of organic
residues on archaeological floors requires the analyses of many samples, and
probably for these reasons, no case studies exist as far as we know of this kind of
study performed only by GC-MS analysis.
Inductively Coupled Plasma-Optical Emission Spectrometry Analysis
Another approach to studying archaeological floors and the function of archaeolog-
ical structures is the use of ICP-OES analysis of an acid extract of floor sediment
samples. This technique is particularly useful in the identification of anthropogenic
chemical residues present in archaeological surfaces (Middleton 1998, 2004;
Middleton and Price 1996; Middleton et al. 2005). It entails the characterization of
a suite of elements that includes both anthropogenic and geochemical indicators,
thus making it possible to distinguish between anthropogenic and natural processes
in the composition of the archaeological surfaces. A variety of extraction techniques
can be used, ranging from a buffered neutral extraction to a total digestion (Middleton
2004), the particular technique employed in a given case depends upon the purpose
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 189
and goals of the study. In the present study, samples were extracted at room
temperature in a weak acid for the period of 2 weeks (see Middleton and Price 1996).
The advantages of this technique is that it is highly sensitive to subtle differences
in the chemical composition of floor sediments, making it possible to distinguish
between a wide range of human activities and to distinguish between human
activities and geochemical processes. The copious quantitative data produced by this
technique readily lend themselves to powerful inferential statistical analysis. Factor
Analysis of Principal Components and Numerical Classification recognize patterns
of covariance in the enrichment and depletion of elemental concentrations in the data
that help to identify the patterns of activity that took place upon the surface. Both the
raw data and derivative statistics, such as factor scores, can be surface plotted to
provide a visual aid to the interpretation of patterns of activity. Both the distribution
of the factor scores and raw elemental data often mirror the areas of most intense
activities and reflect activities such as food preparation and washing or the
contribution of human metabolic byproducts in the soil. Because data can range
over several orders of magnitude, data are usually converted to a logarithmic scale
for analysis and surface plotting (Middleton 2004; Middleton and Price 1996).
Although a powerful technique, there are limitations to this approach, particularly
in comparison to spot tests in the field. Foremost, the length of time involved in
sample preparation and extraction would bar this approach for use in the field in
most cases, whereas spot tests can provide immediate results in the field, which can
be used to guide excavation and interpretation. A second and significant drawback is
the cost of the instrument. Beyond instrument cost, however, ICP-OES analysis is
fairly economical. Finally, although sensitive to some constituents of organic matter
such as phosphorus, ICP-OES analysis cannot identify organic compounds. See
Table 1 for a schematic comparison of the various techniques.
A Step Further: Integrated Approaches, Examples
Above, we have outlined some of the issues in the identification of chemical activity
residues and their analysis. With these points in mind, we show some examples in
the following paragraphs of how different techniques can be integrated in such a way
that the strengths of one technique (spot tests) can be used to leverage the strengths
of another (GC-MS and ICP-OES) to maximize the data obtained while keeping the
time and expense of analysis to a minimum. These examples also show that while
spot tests are less precise and only semiquantitative, they successfully identify the
same areas of interest that the instrumental techniques do, even if they cannot as
effectively elucidate the activities that created them. The first two examples
presented are related to the integration of spot tests and GC-MS, while the last
one is concerned with the spot tests, ICP-OES integration, and comparison.
Example 1Ritual Activities in Templo Mayor (Mexico)
Among the most impressive discoveries made in Templo Mayor (Mexico City)
during the fieldwork in 1978, was the House of the Eagles structure that
corresponds to Phase VI of the Templo Mayor (ca. 14861502 A.D.) (Barba et al.
190 Middleton et al.
1997; Barba et al. 1998). The House of the Eagle Warriors comprises five main areas
(rooms 14, and the patio; Fig. 1). The floors of the entire house are made of lime
plaster, a mixture of hydrated lime and ground tezontle (fragments of volcanic
scoriaceous rock).
Table 1 Schematic Comparison of Spot Tests and Instrumental Analytical Techniques
Spot tests Instrumental analysis
Organic Fatty acids, proteins, carbohydrates GC-MS
Advantages: rapid, inexpensive,
high volume, can be done on-site
Advantages: high precision, quantitative,
detection of multiple compounds
Disadvantages: single tests,
semiquantitative
Disadvantages: low volume, high sample
preparation time, moderate analytical time,
moderately expensive, requires laboratory
Inorganic Phosphates, carbonates, pH ICP-OES
Advantages: rapid, inexpensive,
high volume, can be done on-site
Advantages: high precision, rapid, detection
of multiple elements, high volume
Disadvantages: single tests,
semiquantitative (except pH)
Disadvantages: moderate sample preparation
time, moderately expensive, requires laboratory
Fig. 1 Schematic diagram of the Templo Mayor
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 191
A large number of ancient documents testify the kind of activities and the
materials that might be involved in the activities carried out in this area. For instance,
in the Tudela Codex (1980), several individuals are practicing self-mortification in
front of a deity, inserting the blooded spines in a zacatapayolli and burning copal
(Bursera jorullensis) in the braziers (Figs. 2 and 3). This historical information in
conjunction with an accurately documented excavation and well-preserved floors,
provided a unique opportunity to test the hypotheses on the rituals carried out in the
area, to identify the precise areas where they took place and to identify the
substances used by the priests.
Samples were collected from the plastered floors of each of the four rooms. All
the samples were analyzed with spot tests carried out in the Archaeometry
Laboratories of IIA-UNAM following the procedures established by Barba et al.
(1991). The results of the spot tests (Fig. 4) show that one of the intensively used
areas was located in front of the main altar in room 2. Here, high contents of lipids
were probably related with the burning of resins in front of the main altar and in the
braziers. Other areas in which spot tests have high values are the entrances. In rooms
3 and 4 and in the patio, the highest values are directly associated with the location
of the braziers and altars. In some of these areas, the presence of fatty acids is
strongly related with the distribution of other organic residues, such as carbohydrates
and proteins. This is probably due to the blood offerings. In general, the highest
levels of fatty acids and other chemical indicators were found in the areas around the
braziers and in front of the ceramic sculptures and the zacatapayolli representations,
where rituals should be carried out.
Fig. 2 Aztec ritual, Tudela Codex
192 Middleton et al.
Based on the results of the spot tests and the distribution maps, 20 samples were
analyzed with GC-MS at the Laboratorio de Cromatografa de Gases of the
Department of Analytical Chemistry of the UNAM following the methodology
developed in Evershed's laboratory in Bristol (Evershed 1993). The GC-MS analysis
permitted the identification of differences between the organic acids found in the
main altar and those found at secondary altars, suggesting that different materials
were involved in specific rituals. The residues present in the samples taken from the
close to the main altar were characterized by high molecular weight and were
identified as copal residues (Barba et al. 1996). The samples recovered from
secondary altars showed, in general, fatty acids with lower molecular weight.
The chemical analysis of the floors of the House of the Eagles showed the
presence of three main areas for ritual. They were located in front of the altars,
around the braziers, and in the entryways, where clay figures representing Eagle
Warriors and Mictlantecuhtli were found. In those places, ritual activities involved
the spilling of fluids on the floor, whose chemical compounds were absorbed and
fixed and whose analysis permitted the reconstruction of past human activities.
Furthermore, the analyses carried out at the Templo Mayor of Tenochtitlan
showed that where spot tests indicated the presence of high concentration of lipids in
front of the main altar, GC-MS analyses confirmed the data and showed that the fats
were mainly due to the burning of copal and other resins, confirming the ritual
function of the area investigated. Due to the order used for applying combined spot
test and GC-MS, it was possible to determine the relative content of organic acids in
the 500 samples, to represent their distribution, to select eight of the samples for
Fig. 3 Self mortification, Codex Maglabechiano
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 193
further analysis depending on the chemical results, and to conduct a very specific
study to verify the presence of copal.
This is an example of the use of spot tests for the study of many samples, which is
necessary for the study of activity areas, but also for the screening based on chemical
data of samples that need more specific analyses.
Example 2Food Production Activities in Donoratico (Italy)
In Italy, an integrated approach that used spot tests and GC-MS analyses has been
applied in the study of several sites, in order to understand the function of different
areas. At first, ethnoarchaeological cases were studied (Pecci 20032004), in order
to understand how different activities could be related to chemical traces, following
Fig. 4 a Distribution of fatty acids. b Distribution of phosphorus
194 Middleton et al.
the methodology established in Mexico at the end of the seventies (Barba and Bello
1978; Barba and Denis 1985).
There was a need to go back to this kind of studies because the majority of the
substances used and consumed in Precolumbian Mesoamerica were quite different
from the European ones, so that some of the enrichment patterns established for
Mexico might have different interpretations in Italy. For example, wine and olive oil
that did not exist in Mesoamerica were widely produced, consumed, and stored in
Europe. For this reason, modern production areas of these products were sampled.
Stables were also sampled, as animal breeding was an important activity in Europe.
Furthermore, some experiments were carried out cooking different meat broths and
vegetable soups (traditionally Italian) in unglazed coarse ware ceramics (Pecci 2003
2004). All the samples were analyzed with spot tests at the Archaeometry
Laboratory of the Department of Archaeology of the University of Siena. Some of
the samples were recovered from the wine and olive oil production areas, and all the
experimental samples were analyzed also with GC-MS at the Centro di Analisi e
Determinazioni Strutturali (CIADS) of the University of Siena. Comparing the
results of the two approaches, it is interesting to note that when the presence of
organic acids was detected with spot tests, the analyses performed with GC-MS
confirmed it; and when no fatty materials were detected with spot tests, the analyses
with GC-MS again confirmed their absence.
One of the projects in which the systematic combination of the two approaches
was applied was the study of some structures of a Medieval Castle in Central
Tuscany, Donoratico (Bianchi 2004). The site was excavated under the scientific
direction of Prof. R. Francovich and the field direction of Prof. G. Bianchi of the
Department of Archaeology of the University of Siena, as part of the Medieval
Landscape Project.
Here, several rooms couldn't be interpreted solely on the basis of the excavation
data and the study of recovered materials such as ceramics, metals, and botanic and
animal remains. Chemical analyses of floors were therefore carried out (Pecci 2004).
As in the Templo Mayor case study, spot tests were carried out on all the samples
recovered from the floors of the rooms. Some of the samples that were analyzed with
the spot tests, which showed to be enriched in lipids, were selected and subjected to
GC-MS analyses.
The results obtained for the study of a cellar room of the twelfth century,
characterized by a small channel that lead directly outside the site defensive wall,
were particularly interesting (Fig. 5). The room was at first interpreted, based on the
architectural characteristics, as a possible stable or a cellar to store food, in particular
olive oil. The presence of the channel suggested that it was used to get rid of the
waste and that the activity carried out in the room was probably a dirty one. The
results of the spot tests were consistent with the hypothesis of a stable, because high
values of phosphates were present (Fig. 6). However, organic acids and protein
residues were present as well, which is not typical of this kind of space (Fig. 7).
Five samples were therefore selected for the GC-MS analysis in order to identify
excrement markers, such as coprostanol (Bull et al. 2003; Di Pasquale et al. 2010)
or/and olive oil markers, such as oleic, azelaic, and 9,10-dihydroxyoctadecanoic
acids (Condamin, et al. 1976; Dudd, et al. 1998). The analysis with GC-MS on the
samples didn't show the typical compounds that are usually found in stables (such as
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 195
Fig. 5 The so-called cellar. On the top, it is possible to see the channel
Fig. 6 Distribution map of the results obtained with spot test for the determination of phosphates in the
samples of the cellar
196 Middleton et al.
coprostanol), nor olive oil traces, as C18:1 was very small, C16:0 and C18:0 were
the main components of the chromatograms and no azelaic nor 9,10-dihyroxyocta-
decanoic acids, usually considered the markers of olive oil, were identified (Fig. 8).
These results, together with the presence of cholesterol, indicated on the contrary
that the fatty acids had an animal origin and suggested that the room was a food
preparation or production area. Here, animals were probably killed and/or some
animal products, such as meet or cheese, could have been prepared and the waste
thrown out of the room through the channel.
In the same site of Donoratico, a Late Medieval round structure was sampled and
analyzed to support the archaeological hypothesis that it was a device for oil
production (Fig. 9). In order to test this hypothesis, not only the structure, but also
the floor around it was sampled, as the sampling of modern oil mills showed that oil
production also leaves traces on the floors (Pecci 20032004). The spot tests didn't
show any presence of fatty acid in the plaster of the structure and of the floor around
it (Fig. 9). The GC-MS analysis of four samples confirmed the absence of fatty
acids, and in particular, of olive oil (no relatively high values of C18:1, no azelaic,
nor 9,10-dihydroxyoctadecanoic acids were identified). Therefore, the structure
probably was not used to produce olive oil (as originally thought) but for something
else. The absence of lipids in the samples shown by the spot tests and the GC-MS
analysis suggests the grinding of some substances that didn't leave fatty residues.
Fig. 7 Distribution map of the results obtained with spot test for the determination of organic acids in the
samples of the cellar
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 197
Fig. 9 Possible mill and distribution map of the results obtained with spot test for the determination of
organic acids in the samples of the mill and the floor around it
Fig. 8 Chromatogram obtained with the GC-MS analysis of one sample of the channel of the cellar
198 Middleton et al.
These data, together with the form of the structure, suggest that it might be a mill for
flour production.
The entire site of Donoratico is under investigation, but these examples already
show how the information coming from different approaches can help in
understanding the use of some rooms, and more in general, some aspects of the
life of the ancient inhabitants of Donoratico and their economy. The results obtained
suggest that the two different approaches to the study of the organic acids present in
archaeological materials (spot tests and GC-MS analyses) are complementary and
can be successfully combined in archaeological research for the study of both floors
and ceramics. Again, as in the Templo Mayor case study, the fact that there was an
order in the application of the techniques (at first, all samples were analyzed with
spot tests, and afterwards, only some of them were tested with GC-MS) gave good
results. Additionally, it is important to stress that the results show that absence of
residues is an important archaeological indicator, as is their presence.
Example 3Muxucuxcab (Yucatan, Mexico)
The third case study that we present concerns the comparison of the data obtained
with the analysis of samples carried out with spot tests and ICP-OES. In this case, all
the samples were analyzed with both techniques. As stated above, in order to verify
the reliability of spot tests for the identification of phosphate and carbonate analysis
and to eventually establish the relationship between the two techniques, the same
samples were analyzed with semiquantitative techniques (spot tests) to determine
pH, carbonate, and phosphate content at the UNAM and with ICP-OES at the
Laboratory for Archaeological Chemistry at the University of WisconsinMadison.
Here, the samples were analyzed following the multi-elemental protocol established
there: room-temperature, weak acid extraction process followed by determination of
the elemental concentrations using ICP-OES. Elemental concentrations for elements
that have proven to be strong anthropogenic indicators (e.g., Na, Mg, Ca, P) as well
as elements that are more reflective of geochemical processes (e.g., Al, Fe, Mn) were
determined.
The Archaeological Prospection Laboratory of the UNAM in the Nineties
undertook an ethnoarchaeological study of a recently abandoned household in
Muxucuxcab, Yucatn, Mexico (Barba et al. 1995). The study site is a large
domestic compound. It has been occupied on-and-off since the colonial period and
was finally abandoned about 30 years ago. During its occupation, a number of
structures were constructed, none of which were simultaneously occupied (Fig. 10).
This study focuses on the southwest quadrant of the compound, which had been
most recently occupied (Fig. 11).
Pierrebourg excavated the site and collected sediment samples for chemical
analysis. Samples were collected at a 2-m interval for exterior spaces and a 1-m
interval for interior spaces. In addition, the former residents of the household were
able to provide a descriptive narrative of life and activities in the household. With
these data in hand, it was possible to assess the impact of formation processes on
both the material and chemical archaeological records and the fidelity with which
these records could be interpreted. Years later, the same samples were sent to the
Laboratory for Archaeological Chemistry at the University of WisconsinMadison,
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 199
where James Burton analyzed the samples following the multi-elemental protocol.
Together, the results provide us with a good example of how specific activities
generate identifiable residues.
Fig. 10 The Muxucuxcab study site
Fig. 11 The sampled area at Muxucuxcab
200 Middleton et al.
The distribution of artifacts recovered generally follows the pattern of chemical
enrichment of pH, carbonates, and phosphates. pH values are elevated, that is, more
alkaline, around the structures, particularly the kitchen area, and in the washing area
(Fig. 12). Sources for pH enrichment include wood ash, lime, or calcium hydroxide
used in processing maize (nixtamalization). The pattern for phosphates' enrichment
shows that the space around the structures, the washing areas, and the latrine have
relatively high levels, as does a peripheral area at the eastern edge of the sampled
area. Sources for phosphate enrichment include organic matter and human metabolic
byproducts. Organic matter often accumulates in peripheral areas, and this area also
is adjacent to the latrine, so the distribution isn't surprising. Carbonates are enriched
in the areas around the structure, the washing area, and the latrine. Much of the
carbonate enrichment is probably due to nixtamalization and residue from washing.
In general, patterns of chemical enrichment are clearer in the areas of more
intense human activity. The patterns of chemical enrichment also show that exterior
spaces around the structures are more intensively enriched than the interior spaces.
This pattern, although it might be surprising, is quite typical of many of the
ethnoarchaeological study sites that have been investigated by the UNAM
Prospection Laboratory (Barba and Ortiz 1992), particularly when house size is
relatively small. Also in Neolithic China, the same pattern can be observed
(Middleton et al. 2010). This is a clear indication that exterior spaces must be as
intensively investigated as interior spaces in domestic archaeology.
While not identical, UW results fairly closely follow those patterns found in the
UNAM study. Typically, an ICP-OES analysis is carried out for concentrations of 12
elements, but problems with the instrument forced to use only nine at that time:
aluminum, barium, calcium, iron, magnesium, manganese, phosphorus, strontium,
and zinc. This is unfortunate because several of the excluded elements are
particularly useful anthropogenic or geochemical indicators. The pattern of calcium
enrichment (Fig. 13) rather closely mirrors that of carbonates and is reflecting
essentially the same factors. It shows that the main residue is calcium carbonate as a
byproduct of the use of calcium hydroxide as lime during the use of this space. Lime
was used to soften the corn kernels, and the calcium hydroxide solution was spilled
over the floor. Lime was also used as a powder over the fecal materials in the latrine,
and finally, lime was a byproduct of the clothes washing process.
Fig. 12 Spot test results, pH, phosphate, and carbonate
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 201
Phosphorus enrichment does not follow that of spot test phosphate that well
(Fig. 13): phosphorus enrichment is more tightly restricted to the kitchen, washing
areas, and the latrine. Sources for phosphorus enrichment are the same as for
phosphate enrichment, but a difference in the extraction process is likely selecting
phosphorous that is bound differently in the soil matrix.
A detailed examination of each element and its patterns of enrichment would be
too long, but when we look at their distributions, we can see some interesting
patterns. Some elements, such as strontium and magnesium, have a fairly strong
pattern of covariation with calcium (Fig. 14). They are also related with the chemical
similarities of these elements that reflect the intense levels of activity in the areas
around the kitchen, washing area, and latrine: in this case, most likely associated
with food residues. Other elements, such as iron and zinc have entirely independent
patterns of enrichment (Fig. 15). Iron is relatively depleted in and around the
structures and washing area, probably reflecting sediment deflation due to heavy
traffic, while zinc is clearly reflecting activities in the latrine. Finally, aluminum and
barium appear to reflect primarily geochemical processes. Their patterns of
enrichment appear to be following sediment characteristics rather than any human
activity. These patterns can help us to understand natural variation in the sediment
that might have an influence on the anthropogenic residues that we detect.
As stated above, although multi-elemental characterization is more expensive and
time-consuming than semiquantitative techniques, one important asset is that it
Fig. 13 ICP-OES results, calcium, and phosphorus
Fig. 14 ICP-OES results, strontium, and magnesium
202 Middleton et al.
provides copious data that are amenable to powerful inferential statistical analysis,
such as cluster analysis and principal component analysis, which explore relation-
ships between multiple variables that are difficult or impossible to identify through
descriptive statistics alone. In this case, Principal Components Analysis allows us to
identify three principal components that account cumulatively for over 90% of the
observed variation. Principal component one is determined by the covariance of
calcium, magnesium, phosphorus, and strontium (Fig. 16). The distribution of the
factor scores, clearly mirrors the areas of most intense domestic activity and reflect
such activities as food preparation, cooking, and washing. Principal component two
is determined by the covariance of aluminum and barium (Fig. 16). The distribution
of factor scores here is most likely reflecting the composition of the parent sediment.
Principal component three is determined by zinc alone, and the distribution of factor
scores appears to reflect the contribution of human metabolic byproducts to the
sediment (Fig. 16).
Although the correspondence between spot test and ICP-OES analysis isn't
perfect, both techniques are sensitive to the same chemical residues and provide
essentially similar results. The lack of perfect correspondence between the
semiquantitative and quantitative results deserves a more thorough study, particu-
larly looking at mechanisms of extraction and how these might be influencing the
results. This study also demonstrates the importance of both ethnoarchaeological
Fig. 15 ICP-OES results, iron, and zinc
Fig. 16 ICP-OES results, principal components factors 1, 2, and 3
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 203
studies in sediment chemistry and the utility of making determinations of multiple
sediment properties.
Discussion
Experimental, ethnoarchaeological, and archaeological studies have shown that the
results obtained with the organic acid spot tests and results of the GC-MS analyses
are consistent with one another (Barba et al. 1996; Lazos 1997; Pecci 20032004).
In particular, the analyses carried out at the Templo Mayor of Tenochtitlan, in the
House of the Eagles showed that where spot tests indicated the presence of
concentration of organic acids in front of the main altar, GC-MS analyses confirmed
the data and showed that these concentrations were mainly due to the burning of
copal and other resins. This confirmed the ritual function of the area investigated.
In Italy, ethnoarchaeological studies of olive oil production areas, experiments in
the cooking of various meat broths and vegetables, the analysis of archaeological
samples taken from archaeological floors and ceramics, in particular at Donoratico,
gave similar results. Here as well, GC-MS analyses confirmed the presence of fatty
acids, as indicated by the spot tests and specified their origin. Furthermore, areas in
which had been provisionally identified as having been used for olive oil production
could be eliminated through their lack of organic residues. The comparison between
spot tests and ICP-OES showed that a good correspondence exists between
carbonates and calcium concentrations. Furthermore, the same disposal areas were
identified by both techniques using different markers: phosphates for the spot tests
and zinc and phosphorous for the ICP-OES. In all cases, the identification of the
analysis of residues was useful in the interpretation of the function of the
archaeological sites.
The stepwise application of spot test and more intensive instrumental analysis
appears to work well. In both cases, the results of spot tests were confirmed and
further elucidated through both GC-MS and ICP-OES analysis. The use of spot tests
provides useful data that can be obtained, if necessary, during field operations;
instrumental analysis can provide further insights into the sources of the residues
identified through spot tests. The lack of perfect correspondence between
semiquantitative phosphate analysis and quantitative phosphorous results deserves
a further study.
In general, these examples show that human activities leave detectable and
identifiable residues in the material upon which they take place and that their
chemical analysis can therefore be an extremely powerful tool in the interpretation of
the archaeological record, particularly if no other artifactual remains are available. A
second point is that both semiquantitative spot tests and GC-MS and quantitative
ICP-OES provide powerful insights into the nature of anthropogenic chemical
residues. While the precision of quantitative techniques is extremely useful, these
techniques are more expensive, time-consuming, and often impossible to apply in
the field.
The ICP-OES analyses are very efficient to determine the chemical enrichment
with inorganic residues and are especially good to determine metallic particles
produced by pre-industrial production activities. In addition, it provides reliable data
204 Middleton et al.
for statistical analysis for more specific information. GC-MS is very important for
identifying the specific origin of organic residues, particularly of food residues.
Spot tests are inexpensive, rapid, and can be easily performed in the lab or the
field. A number of scholars have published important results obtained through field
analysis (e.g., Terry et al. 2000). The results of pH, phosphate, and carbonate
determinations together with organic residues tests actually support essentially the
same inferences as those obtained through multi-elemental characterization. In some
other cases, spot tests (especially those that detect organic compounds) could give
information that is complementary to the ICP-OES data.
Conclusions
As a conclusion, we can suggest that the ideal investigation requires the
integration of different techniques for the chemical analysis of archaeological floors
that will allow us to achieve as much information as possible, with the optimum
costs and time. This is related to the financial resources of the projects, to the
available analytical instruments, the qualified personnel, the time allowed, and, of
course, the specific archaeological question.
Our proposal suggests an order with which the different techniques should be
applied. Simple techniques that allow the analysis of many samples with low costs
and short time should be applied first and, if possible, in the field. All the samples
from the entire investigated area should be analyzed with these techniques. Once
patterns have been recognized and hypotheses have been established, they can be
tested applying more sophisticated instrumental analyses.
ICP-OES analysis should be applied in order to obtain information about the
inorganic elements and their distributions. If possible, all the samples should also be
analyzed with this technique. If this is not possible, it would be particularly useful to
focus on specific areas that have been identified through spot tests as having a high
potential for yielding useful results, for example, areas in which metallic ions could
be present, such as in production areas or in ritual areas (cinnabar has been found in
ritual Mayan areas) and in the study of refuse patterns (as shown above, zinc is
related to latrines, refuse areas are rich in phosphorous). Terry et al. (2000)
suggested that market residues could be identified, providing information concerning
the use of these large open areas.
When archaeological problems deal with organic materials, GC-MS should be
carried out on specific samples in order to answer questions arising from spot test
analyses. As stated above, this analysis is particularly useful in identifying the
presence or absence of specific organic substances such as resins, food residues,
fecal material, etc. Although spot tests give reliable information on the function of
the structures and on the spatial distribution of activities, the interpretation is more
precise when the analysis is combined with the GC-MS data.
To conclude, another important point that must be stressed is that the
interpretation of anthropogenic sediments must be empirically based on ethno-
archaeological and experimental studies in which the patterns of residue formation
can be documented. Initially, sediment residue studies featured post hoc interpre-
tations of observed patterns of variation without empirical verification, what we
Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 205
might describe as a sort of laboratory-based armchair archaeology. You can't reliably
identify an activity if you don't know how the activity generates residues and how
those residues are incorporated into the porous materials. This is why ethno-
archaeological studies should have important part in archaeological investigation.
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