0 évaluation0% ont trouvé ce document utile (0 vote)
35 vues26 pages
Semiquantitative spot tests, which are cheap, quick, and easy to apply, are employed as an initial phase of analysis. Spot Tests can be combined with gas chromatography-mass spectroscopy and inductively coupled plasma-optical emission spectrometry analysis. This approach can save both time and research funds.
Semiquantitative spot tests, which are cheap, quick, and easy to apply, are employed as an initial phase of analysis. Spot Tests can be combined with gas chromatography-mass spectroscopy and inductively coupled plasma-optical emission spectrometry analysis. This approach can save both time and research funds.
Semiquantitative spot tests, which are cheap, quick, and easy to apply, are employed as an initial phase of analysis. Spot Tests can be combined with gas chromatography-mass spectroscopy and inductively coupled plasma-optical emission spectrometry analysis. This approach can save both time and research funds.
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. References Arrhenius, O. (1929). Die phosphatfrge. Zeitschrift fr Pflanzenernhrung, Dungung, und Bodenkunde Teil B, 10, 185194. Barba, L. (1986). La Qumica en el Estudio de reas de Actividad. In L. Manzanilla (Ed.), Unidades Habitacionales Mesoamericanas y sus reas de Actividad (pp. 2139). Mxico: UNAM. Barba, L., & Bello, G. (1978). Anlisis de fosfato en el piso de una casa habitacin actual. Notas Antropolgicas, 24, 188193. Barba, L., & Denis, P. (1985). Actividades humanas y anlisis qumico de los suelos: El caso de Osumacinta Viejo, Chiapas. Memorias de la XVII Mesa Redonda de la Sociedad Mexicana de Antropologa, II, 263277. Barba, L., & Lazos, L. (2000). Chemical analysis of floors for the identification of activity areas: a review. Antropologa y Tcnica, 6, 5970. Barba, L., & Ortiz, A. (1992). Anlisis qumico de pisos de ocupacin: un caso etnogrfico en Tlaxcala, Mxico. Latin American Antiquity, 3(1), 6382. Barba, L., de Pierrebourg, F., Trejo, C., Ortiz, A., & Link, K. (1995). Activits humaines refletes dans les sols d'units d'habitation contemporaine et prehispanique du Yucatan (Mexique): tudes chimiques, ethnoarchologiques et archologiques. Revue d'Archomtrie, 19, 7995. Barba, L., Lazos, L., Link, K., Ortiz, A., & Lpez Lujn, L. (1998). La arqueometra en la Casa de la guilas. Arqueologa Mexicana, 6(31), 2027. Barba, L., Lazos, L., Ortiz, A., Link, K., & Lpez Lujn, L. (1997). La arquitectura sagrada y sus dioses. Estudio geofsico y qumico de la Casa de la Aguilas, Tenochtitlan, Mexico. Revista de Arqueologa Espaola Ao, XVIII, 4453. Barba, L. A., Ortiz, A., Link, K.F., Lpez Lujan, L. and Lazos, L. (1996). The Chemical Analysis of Residues in Floors and the Reconstruction of Ritual Activities at the Templo Mayor, Mexico. In Archaeological Chemistry: Organic, Inorganic and Biochemical Analysis. Chemical Society of America pp.139156 Barba, L., Rodrguez, R., & Crdoba, J. L. (1991). Manual de Tcnicas Microqumicas de Campo para la Arqueologa. Cuadernos de Investigacin, IIA. Mxico: UNAM. Bianchi, G. (2004). Castello di Donoratico. I risultati delle prime campagne di scavo (20002002). Firenze: Edizioni Insegna del Giglio. Bull, I. D., Elhmmali, M. M., Roberts, D. J., & Evershed, R. P. (2003). The application of steroid biomarkers to track the abandonment of a roman wastewater course at the Agora (Athens, Greece). Archaeometry, 45, 149161. Charters, S., & Evershed, R. P. (1995). Evidence for the mixing of fats and waxes in archaeological ceramics. Archaeometry, 37(1), 113127. Charters, S., Evershed, R. P., Quye, A., Blinkhorn, P. W., & Reeves, V. (1997). Simulation experiments for determining the use of ancient pottery vessels: the behaviour of epicuticular leaf wax during boiling of a leafy vegetable. Journal of Archaeological Science, 27, 127. Condamin, J., Formenti, F., Metais, M. O., Michel, M., & Bond, P. (1976). The application of gas chromatography to the tracing of oil in ancient anphorae. Archaeometry, 18(2), 195201. Cook, S. F. and Heizer, R.F. (1962) Chemical Analysis of the Hotchkiss Site. Reports of the University of California Archaeological Survey No. 57, Part 1 Berkeley, University of California Cook, S. F. and Heizer, R.F. (1965) Studies on the Chemical Analysis of Archaeological Sites. University of California Publications in Anthropology No. 2 Berkeley: University of California Di Pasquale, G., Pecci, A., Corbino, C. A., Buonincontri, M. P., Donnini, D., Mori Secci, M., Pignattelli, S., Salvini, L., and Terzani, M (2010). Approccio integrato allo studio dellalimentazione e dellambiente a Firenze nel XIII secolo: risultati preliminari. In Cantini, F., Cianferoni, C., Francovich R. and Scampoli, E. (eds.), Firenze prima degli Uffizi. Lo scavo di via de Castellani. Contributi per unarcheologia urbana fra tardo antico ed et moderna, Edizioni Insegna del Giglio, Firenze (in press). 206 Middleton et al. Dudd, S., Regert, M., & Evershed, R. (1998). Assessing microbial lipid contributions during laboratory degradations of fats and oils pure triacylglycerols absorbed in ceramic potsherds. Organical Geochemistry, 29(57), 13451354. Eidt, R. (1973). A rapid chemical field test for archaeological site surveying. American Antiquity, 38, 206 210. Evershed, R. (1993). Biomolecular archaeology and lipids. World Archaeology, 25(1), 7493. Evershed, R., Dudd, S., Copely, M., Berstan, R., Scott, A., Mottram, H., et al. (2002). Chemistry of archaeological animal fats. Accounts of Chemical Research, 35(8), 660668. Evershed, R., Dudd, S. N., & Lockehart, M. J. (2001). Lipids in Archaeology. In D. R. Brothwell & A. M. Pollard (Eds.), Handbook of Archaeological Science (pp. 331349). Chichister: John Wiley and Son Ltd. Guash-Jan, M. R., Iberno Gmez, M., Andrs-Lacueva, C., Juregui, O., & Lamuela-Ravents, R. M. (2004). Liquid chromatography with mass spectrometry in Tandem mode applied for the identification of wine markers in residues from ancient Egyptian vessels. Analytical Chemistry, 76(6), 16721677. Heidenreich, C.E., Hill, A.R., Lapp, D.M., and Navratil, S. (1971) Soil and environmental analysis at the Robitaille site. In Hurley, W. M. and Heidenreich, C. E. (eds). Palaeoecology and Ontario Prehistory, Research Report 2, Department of Anthropology, University of Toronto, pp. 179237 Lazos, L. (1997). Propuesta para el Anlisis Qumico Sistemtico de Pisos Arqueolgicos en el Estudio de reas de Actividad, Masters thesis. Mexico: UNAM. Linderholm, J., & Lundberg, E. (1994). Chemical characterization of various archaeological soil samples using main and trace elements determined by inductively coupled plasma atomic emission spectrometry. Journal of Archaeological Science, 21, 303314. Lpez Varela, S., Ortiz, A., & Pecci, A. (2005). Ethnoarchaeological study of chemical residues in a "living" household in Mexico (pp. 1922). Amsterdam: Geoarchaeological and Bioarchaeological Studies. Vrije Universiteit. Manzanilla, L. (1993). Anatoma de un Conjunto Residencial Teotihuacano en Oztoyahualco, 2 vols IIA. Mxico: UNAM. Middleton, W.D. (1998). Craft specialization at Ejutla, Oaxaca, Mexico: An archaeometric study of the organization of household craft production. Ph.D. dissertation. Madison: University of Wisconsin Middleton, W. D. (2004). Identifying chemical activity residues in prehistoric house floors: a methodology and rationale for multi-elemental characterization of a mild acid extract of anthropogenic sediments. Archaeometry, 46(1), 4765. Middleton, W. D., & Price, T. D. (1996). Chemical analysis of modern and archaeological house floors by means of inductively coupled plasma-atomic emission spectroscopy. Journal of Archaeological Science, 23(5), 673687. Middleton, W. D., Price, T. D., & Mieggs, D. C. (2005). Chemical analysis of floor sediments for the identification of anthropogenic activity residues. In I. Hodder (Ed.), Inhabiting atalhyk: reports from the 199599 seasons (pp. 399412). Cambridge: McDonald Institute Monographs/British Institute of Archaeology at Ankara. Middleton, W.D., Underhill, A., Luan, F., Fang H., Yu H., and Cai F. (2010) Identification of Anthropogenic Chemical Activity Residues at Liangchengzhen, Shandong, China (in press) Mottram, H. R., Dudd, S. N., Lawrence, G. J., Stott, A. W., & Evershed, R. P. (1999). New chromatographic, mass spectrometric and stable isotope approaches to the classification of degraded animal fats preserved in archaeological pottery. Journal of Chromatography, 833(2), 209221. A. Ortiz, A., &Barba, L. (1993). La Qumica en el Estudio de reas de Actividad. In L. Manzanilla (Ed.), Anatoma de un Conjunto Residencial Teotihuacano en Oztoyahualco IIA, (pp. 617660). Mxico: UNAM. Parnell, J. J., Terry, R., & Nelson, Z. (2002). Soil chemical analysis applied as an interpretive tool for ancient human activities in Piedras Negras, Guatemala. Journal of Archaeological Science, 29, 379404. Pecci, A. (2000). Anlisis qumico y reas de actividad: estudio de caso en Teopancazco, Teotihuacan, Master Thesis in Anthropology (specialization in Archaeology). Mexico: UNAM. Pecci, A. (20032004). Per una definizione funzionale degli spazi e delle ceramiche all'interno degli insediamenti in corso di scavo: un progetto archeometrico, PhD thesis in Archaeology, University of Siena, Italy Pecci, A. (2004). Le analisi funzionali di alcuni livelli di vita bassomedievali. In G. Bianchi (Ed.), Castello di Donoratico. I risultati delle prime campagne di scavo (20002002 (pp. 9397). Florence: Edizioni Insegna del Giglio. Pecci, A., Ortiz, A., Barba, L. and Manzanilla, L. (2010). Interpretacin de actividades humanas con base en el anlisis qumico de los pisos del conjunto de Teopancazco, Teotihuacan. In Ortiz E., Liendo R. (eds.), VI Coloquio Bosh Gimpera, UNAM, Mexico (in press) Anthropogenic Residue Analysis by Instrumental/Qualitative Techniques 207 Snchez, A., & Caabate, M. (1998). Indicadores Qumicos para la Arqueologa. Jan: Universidad de Jan. Terry, R. E., Hardin, P. J., Houston, S. D., Nelson, S. D., Jackson, M. W., Carr, J., et al. (2000). Quantitative phosphorus measurement: a field test procedure for archaeological site analysis at Piedras Negras, Guatemala. Geoarchaeology, 15, 151166. Tudela, J. (1980). Cdice Tudela. Madrid: Ediciones Cultura Hispnica. Wells, E. C. (2004). Investigating activity patterns in prehispanic plazas: weak acid-extraction ICP-AES analysis of anthrosoles at classic period El Coyote, Northwestern Honduras. Archaeometry, 46(1), 67 84. Wells, E. C., Terry, R. E., Parnell, J. J., Hardin, P. J., Jackson, M. W., & Houston, S. D. (2000). Chemical analyses of ancient anthrosols in residential areas at Piedras Negras, Guatemala. Journal of Archaeological Science, 27, 449462. 208 Middleton et al.