Agricultural practices in a high-altitude valley of the Southern

Andes: new insights from organic residue analysis from La

Ciénega valley, Argentina (ca. 200 BCE-900 CE)
Agustina V. Fiorani 
(

mvazque3@nd.edu
)
University of Notre Dame
Ana Fundurulić 
Sapienza Università di Roma
Ana Manhita 
/ Laboratório HERCULES - Herança Cultural, Estudos e Salvaguarda Universidade de Évora
Valeria Franco Salvi 
National Scientific and Technical Research Council
Cristina Barrocas Dias 
Universidade de Évora

Research Article

Keywords: Organic residue, GC-MS, food production, villager societies, pottery

Posted Date: November 23rd, 2022

DOI: https://doi.org/10.21203/rs.3.rs-2278015/v1

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Abstract
The consolidation of villager life in the Southern Andes implied profound transformations in human lifeways and groups’
relations with the landscape with the adoption of settled life and food production economies. Contributions from archaeological
sciences can cast light into these research questions providing, for example, new information about patterns of susbsistence
strategies. In this paper, we present the first organic residue analysis on ceramic containers of early villager societies of
Northwestern Argentina (La Cienéga valley, ca. 200 BCE-900 CE) through two simultaneous lipid extraction methods
(H2SO4/MeOH and CHCl3/MeOH). We aimed to put to test the existent characterization of the study area as a peripheric herding
settlement evaluating the subsistence strategies and food economies of villager groups through the lens of absorbed organic
residues in pottery. Preliminary evidence obtained in this article indicated a predominance of biomarkers associable to vegetable
products in the vessels (i.e. maize) and a lower contribution of animal fats. Furthermore, a comparison and evaluation of the
performance of each extraction method for specific compounds is given.

1. Introduction
Around 200 BCE, human groups inhabiting the southern-east of Northwestern Argentina (NWA) went through a series of novel
transformations in their lifeways and in their relations with the world in what is known in Archaeology as the Formative Period
(Olivera 2001; Tarragó 1999; Núñez Regueiro 1974). People settled in the high altitude and mesothermic valleys and ravines,
developed different ways of building, making vessels, and carry out ritual practices generating a complex picture of ways of being
in the world anchored in the domestic realm (Salazar 2014; Scattolin et al. 2009). All these changes in inter relationality,
cosmologies, and material expressions succeeded behind, or in parallel with a more profound transformation of people's
interactions with their immediate landscapes and other nonhuman beings, resulting in the adoption of settled life and food
production economies.

Although domestication of plants (nor animals) was not local, the incorporation of domesticated species is probed in the region
around 1000 BCE (Oliszewski & Arrenguez 2015; Lema 2013) and was well consolidated by the first millennium CE in a fully
villager-like setting (Kornstanje et al. 2015; Franco Salvi et al. 2013). Broadly, local economies were oriented to the cultivation of
crops such as maize, quinoa, gourds, and beans in sophisticated agricultural settings, although without the abandonment of
gathering practices (Korstanje et al. 2015). Together with the evidence of plant management and exploitation, material remains
indicate also the herding of Andean camelids (i.e. Lama glama). This was interpreted as result of the existence of specialized
herding settlements or nodal points (Lazzari 1999), or of the early articulation of zonal complementarity relations between
different ecological niches (e.g. Murra’s [1975] archipelagos model) in which animal resources were barter for vegetable foods (or
other type of valuable foodstuffs such as salt) generally in arid or high altitude environments where agriculture seems, for the
modern eye, unlikely.

Yet, most of research about farming practices in the NWA has been restricted to traditional material indicators, such as botanic
and archaeozoological remains, specialized architecture (e.g. field systems), and ecological suitability (including soil analysis)
(Kornstanje et al. 2015). This has proven to be highly fruitful to the understanding of village lifeways, but it has also reproduced
biases regarding 1) the environmental and economic conditions and possibilities of each ecological niche (i.e. what kind of
activities can be developed), 2) the overall site formation process, and 3) the composition and interpretation of the archaeological
record (i.e. the need of agricultural infrastructure for farming). Recent archaeometric developments and the opening of new
research avenues supported by the application of archaeological science, have proved to be useful to improve and nuance
archaeological inferences, illuminate anthropological questions about the past, and overcome (or at least, recall) biases in
academic production. In consonance, organic residue analysis has proven to provide insights into past food production and local
economies reveling “hidden” aspects of materiality that have been not preserved otherwise (Roffet-Salque et al. 2017: 621).

For our purposes, the possibility to get direct chemical evidence of the presence of animal and plant foodstuffs in ceramic
containers (Dudd et al. 2019) can help us evaluate the subsistence strategies and farming practices put in place by Formative
Period villager groups in NWA overcoming the above described constrains of tradicional archaeological approaches. Specifically,
we aim to apply archaeological chemistry techniques to cast light into the local economy of La Ciénega (Tucumán, Argentina), a
small high altitude valley with intense prehispanic occupation. The area has been traditionally characterized as a specialized
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herding settlement subsidiary of other agricultural villages of NWA based on a combination of historical, ethnographic, and
environmental data that attempted to explain the lack of visible archaeological remains that could be associated with agricultural
production (Cremonte 2003). In this article, we argue that the absence until the moment of visible material indicators of
agriculture (mainly, terraces or other crop management architecture structures), is not enough to sustain a model of ecological
complementarity in which La Ciénega performed as a pastoral village. Additionally, we argue that biomolecular analysis can open
a new avenue to a better understanding of villager lifeways and food production in La Ciénega.

In this paper, we present the preliminary evidence of the biomolecular analysis of 13 potsherds analyzed by gas chromatography-
mass spectrometry (GC-MS). This is, until the date, the only application of organic residue analysis in specifically early villager
contexts of Northwestern Argentina. Additionally, because lipids were extracted by two different methodologies in the same
sample (H2SO4/MeOH and CHCl3/MeOH), our analysis sheds light on the strengths and limits of each methodology for
archaeological purposes. Our study is also the first until the date to apply lipid analysis to archaeological ceramics of villager
groups combining a double-methodology of extraction that allows the comparison of suitability and efficiency of each method.
We argue that biomolecular analysis is a valuable methodology to gain insight into discrete practices of daily life at the intrasite
and the domestic scale, and that it constitutes a line of research important to be explored systematically in the future for the
opportunities it yields to put to test archaeological models of food production and local economies.

2. Organic Residue Analysis As A Tool For The Study Of Local Economies

Information derived from organic residues in ceramic containers provides important information about past practices in
archaeological research. Chemical fingerprints of products known to have been exploited in the past (and their degradation
products) can be identified through high resolution techniques (e.g. GC-MS, GC-C-IRMS) to identify food prepared or stored within
a pot.

Certain classes of biomarkers allow chemical identification at the species level, since some of them are only synthesized by one
or a small group of plant and/or animal species (e.g., eurucic acid produced by Brassicaceae vegetables) (Evershed et al. 1991;
Colombini et al. 2005). Nevertheless, in some cases, metabolic pathways and biological processes are shared by related
organisms and, therefore, many compounds cannot be assigned to a particular product, especially in the case of biomolecules
such as lipids (Eerkens 2007: 90). Despite this lack of specificity at the species level, organic residue analysis can be highly
informative regarding the origin of the conserved residues distinguishing animal (carcass and dairy) from vegetable sources (oils,
waxes and resins) (Evershed 2008; Historic England 2017; Dunne et al. 2019).

Plant oils and animal fats can be distinguished in preserved archaeological residues, although not without careful consideration
(Whelton et al. 2021). Animal fats are characterized by high abundances of free fatty acids (saturated and monounsaturated),
triacylglycerols (usually degraded as di- and monoacylglycerols), and cholesterol (which can be found together with its
degradation products,7-keto-cholesterol, 5α-cholestanol, coprostanol, campestanol and cholesta-4-ene-3-6-diol) (Evershed 2008;
Šoberl et al. 2008; Historic England 2017). Plant materials produce large amounts of phytosterols, higher amounts of C16:0,
unsaturated fatty acids and their oxidation derivatives (i.e. hidroxy fatty acids and dicarboxylic acids) (Evershed 2008; Šoberl et
al. 2008), and especifically: 1) for oils, saturated fatty acids (C16:0 and C18:0), hydroxy fatty acids, dicarboxylic acids, 2) for
waxes, wax esters, long chain n-alkanols, and even numbered long chain fatty acids (Historic England 2017). A higher level of
resolution can be achieved through the use of compound-specific stable carbon analysis of fatty acids (Whelton et al. 2021).

When applied to specific archaeological problems, biomarkers can be useful to reconstruct ancient economic practices and
systems, complex foodways, and food habits (Dudd et al. 2019; Roffet-Salqué 2017). Lipid analysis provides direct chemical
evidence of food processing through the characterization of absorbed residues in pottery’ walls (Dudd et al. 2019), whereas other
(and complementary) lines of evidence indicate indirect or successive instances of the food webs (e.g., farming, grinding,
disposal). Despite their usefulness, absorbed residues do not represent single-use events, rather they are the result of the repetition
or accumulation of culinary practices over time, and therefore, individualized conclusions cannot be easily extrapolated from
them (Evershed 2008). But, because of the same accumulation of uses, organic residue analysis yields the possibility of
elucidating the contribution of certain types of commodities to the overall food system, which for example has proven a valuable

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proxy to cast light into the Mesolithic-Neolithic transition in the Old World (Copley et al. 2003; Evershed et al. 2008; Cramp &
Evershed 2015 Debono Spiteli et al. 2016; Dunne et al. 2016; Cramp et al. 2019, among others).

In Argentina, the application of organic residue analysis has contributed to the knowledge of the uses of specific pottery types,
ritual practices, and regional socio-political transformations (e.g., feasting during the Inca conquest). Foodways and subsistence
strategies have received less attention, generally focused on the study of hunter gatherer societies and the exploitation of marine
resources (Frère et al. 2010; Pérez et al. 2013; Otero et al. 2014; Stoessel et al. 2015; Chaile et al. 2018). To the date, no lipid
studies have been conducted to investigate early villager societies of NWA (a long-term study of maize consumption considered a
few samples taken from an early context, see Lantos et al. 2015).

This gap in the literature is striking, especially considering the historical tradition of archaeobotanical studies among early villager
societies in Argentina (Capparelli et al. 2007). This can be explained by the reproduction of a well extended assumption in NWA
archaeology that links indissociably ecological suitability with particular economies. In the mesothermic valleys, villagers groups
based their subsistence on agriculture with permanent settlements placed near water sources and appropriate lands for the crops
(Olivera 2001). Herding and gathering would have been complementary strategies in these economies without substantive weight
in the overall diet (Olivera 2001). Opposite to it, high-altitude groups concentrated their economy in camelid herding, with well-
established logistic networks to structure a complex system of nodal settlements. There, the adoption of agriculture may have
been an economic strategy that tended to reduce the risk in a highly unpredictable and harsh environment (Olivera 2001). Isotopic
data obtained in puna (high-altitute dry plateau) and intermontane valley sites may point toward that interpretation (Killián Galván
et. al 2021). Yet, sites emplaced in high altitude environments do count with complex agricultural systems and an extensive
amount of land under cultivation, combining both intensive and extensive cultivation (Quesada 2006; Delfino et al. 2015).
Furthermore, recent research on isotopic contributions to diet showed unexpected and counter-intuitive evidence of subsistence
strategies in villager economies (Killián Galván et al. 2021).

We argue that biomolecular research and analysis is complementary to archaeobotanical research and an important proxy to cast
light into ancient subsistence strategies and quotidian practices of villager groups. Moreover, we hold that biomolecular research
provides nuanced models of adoption of food economies based on ecological suitability, especially in cases where other lines of
evidence (macro and micro botanic remains, farming agriculture, zooarchaeological remains) are absent or are inconclusive.

3. La Ciénega Valley: Ecological Possibilities And Archaeological Data

The southern Calchaquí valleys are a range of adjacent valleys and high-altitude ravines in the southern-east end of NWA with
agropastoral occupations encompassing a range from 200 BCE to the present day (Salazar & Kuijt 2016; Olisewski 2010;
Scattolin et al. 2009; Aschero & Ribotta 2007; Cremonte 2003; Berberián & Nielsen 1988; González & Núñez Regueiro 1960)
(Fig. 1). Located among the mid and high-altitude valleys, La Ciénega (Fig. 1) has an altitude that ranges between 2400 and 2800
m.a.s.l. with a semi-arid climate and it is part of the foggy glasslands, a transition area between the montane forest (higher step
of the Yungas) and the dry plateau (Puna) (Cabrera 1976).

Local vegetation in La Ciénega is well suited to the cold and wet weather, and it is resistant to the cloud covers, mists and rains
that affect the valley, especially during the winter (Cremonte 1996). The valley is covered by moorland vegetation, with grasslands,
shrublands and other low-growing plants that can prosper in acidic soils (Fig. 2). In the lower parts, there are small forests of
Alnus acuminata, whereas, in more elevated hills, populations of Polylepis australis bitter predominate (Cremonte 1996). In the
floodplains and on the margins of streams grow different types of tall grasses and rushes of families such as Juncaceae and
Cyperaceae, that may have been used for basketry (Cremonte 1996). Additionally, Cremonte (1996) mentions the use of several
medicinal herbs as Proustia cuneifolia, Satureja parvifolia, and Acantholippia hastulata, among others.

Although there are archaeological records of wild camelid species, domesticated Lama glama and cervids (e.g Mazama
americana), currently there are no camelid herds in the valley, and farming activities are limited to sheep herding (Franco Salvi
2020; Cremonte 1996). It is worthy to mention that the cold and wet climate in La Ciénega offers good opportunities for the
grazing of camelids, with several and dense grasses and marshes that could sustain enough fodder for big llama herds in the
past (Cremonte 1996). This setting allows a seasonal pastoralism circuit, moving to higher altitude lands during the winter and

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middle-altitude pasture lands during the warmer months, around the northern Tafí valley (Fig. 1) and the puna (Cremonte 1996).
This interpretation is based on ethnographic data recorded in other intermontane valleys (e.g., El Cajón, see Fig. 1) and slightly
inspired by modern sheep herding practices.

Today, people living in La Ciénega participate in small-scale sheep grazing and secondary products exploitation. Cremonte (1996)
mentions isolated cases of horticulture by some inhabitants, mainly vegetables and potatoes that are grown in stone enclosures
(‘corralitos de piedra’). As it was referred to by local commoners in the late eighties, they complemented their subsistence basis by
the exchange of meat for crops (mainly maize) and wood with other groups in the eastern montane forest, as the Anfama valley
(Fig. 1) (Cremonte 1996). Indeed, Anfama possesses highly fertile lands, where several crops (e.g., maize, squashes, beans) can
be easily farmed almost without any artificial watering, and excellent wood resources for fuel and construction are also available
(Salazar et al. 2021). Nevertheless, in La Ciénega, soil studies show that the conditions are optimal for agriculture and the climate
is not too harsh (Cremonte 1996), so it is possible to think of agriculture in the past that was very possibly interrupted during the
colony. It may be that a consequence of the Hispanic conquest in the area is the abandonment of the cultivation habit, as has
already been observed in other sectors of the Argentine Northwest (Lorandi 1988).

Although prehispanic occupations were recorded as early as the end of the 19th century (Quiroga 1899), systematic
archaeological research has been scarce (Cremonte 1996, 2003) until the date. Cremonte (2003) observed that La Ciénega was
associated with the nearby Tafí villages due to its similarities in settlement patterns, constructive techniques, architecture, and
material culture (mainly domestic wares). For her, “La Ciénega settlements seems to have had a peripheral and frontier nature
regarding the cultural center of Tafí, probably in a subsidiary ecological zone that allowed the configuration of a herding economy
[simultaneously connected] with broader trade networks, to plains and lowlands of the East and to the North” (Cremonte 2003: 58,
translated by the author).

This interpretation is inspired by a zonal complementarity model in which Andean societies share an ideal of self-sufficiency
anchored at the household and community level (Murra 1975; Aldenfer and Stanish 1993; Nielsen 2015). In summary, because
Andean geography imposes great ecological constraints to human economies and their subsistence in relatively short distances,
Andean groups seem to have developed a novel use of space, economic exploitation and social organization founded in a local
ideal of self-sufficiency. Through the effective colonization of different ecological niches by displaced households, an ethnic
group could secure communal access to complementary resources without the consolidation of specialized traders or proto-
market mechanisms (Murra 1975; Nielsen 2015). Therefore, the apparent cultural homogeneity observed in prehispanic
occupations placed in different ecological zones should be explained by this political-cultural-economic strategy. Although
alternative explanations have been proposed for the southern Andes (Nuñez & Dillehay 2011; Nielsen 2015), the zonal
complementary model remains highly influential in the archaeology of the region.

Archaeological investigations have resumed in recent years by the Equipo de Arqueología del Sur de las Cumbres Calchaquíes in
collaboration with the local indigenous community of the Tafí valley, as part of a wider research project focused on the long-term
historical trajectories and everyday practices of villager communities settled in the Calchaquíes valleys (Salazar et al. 2021;
Franco Salvi 2020). Although Cremonte’s previous work in the region remains as a groundbreaking contribution, the consideration
of new architectural and contextual evidence (e.g. in-situ grinding stones, botanic macro- and micro- remains) is casting doubt
into the marginal exploitation of vegetable resources in La Ciénega and its traditional characterization of the valley as a herding
spot.

4. Materials And Methods

Archaeological background

Fieldwork at site Lomita del Medio, located in the middle section of La Ciénega valley provided the opportunity to cast light into
material practices and daily life within early villagers in the south Calchaquí valleys. The site is a household complex formed by a
series of circular enclosures (n = 18) with three patios placed in N-S way All rooms are connected through one of these courtyards
that yields the only exit. It is possible that the house unit was created by joining two separate clusters attaching a new patio
between. At the moment, there were fully excavated structure R90, R91, R93 and R94 (Fig. 3a) from where a large material

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assemblage was recovered and several archaeological features were identified, allowing to propose an intensive use of the
domestic cluster during the first millennium CE (Franco Salvi 2020).

Radiocarbon samples of charred wood recovered from the central hearth of R94 (Fig. 3b,c,d) have been dated to 1543 ± 23 466 cal
CE (95, 4% probability) (charred wood) 1486 ± 23, 640 cal CE (95,4% probability) (charred wood). The R94 enclosure particularly is
associated with a kitchen space dedicated to the processing and cooking of foodstuffs. The presence of material indicators
typical of food preparation and cooking setting, including the presence of a formal hearth, several broken vessels, lithic artifacts
(knifes, hammers) and knapped flakes, grinding stones (manos and metates), and botanic macro and micro remains (e.g.,
Geoffroea decorticans, Zea mays) (Franco Salvi 2020).

To better understand local economy and daily food production, 13 sherd samples from the site were analyzed by GC-MS for lipid
analysis (Table 1). The selection was made considering size, morphology and type-petrographic group of the ceramic sherd but
also its storage conditions for organic residue analysis. Due to the preferential conservation of absorbed lipid in vessels, rims
were preferred in the case of cooking and service vessels, and bases were considered in the case of dry storage vessels (Evershed
2008). For analysis all samples were unwashed, did not exhibit evidence of handling or contamination agents, and were stored in
aluminum foil without contact with plastics (Evershed 2008; Historic England 2017; Whelton et al. 2021).

The ceramic samples analyzed, were classified into three petrographic groups (coarse granitic, fine granitic, and metamorphic).
Granitic groups are interpreted as being produced locally, whereas metamorphic groups are associated with the Candelaria style
(Srur 2001) and were considered non-local for the La Ciénega valley (Cremonte 2003; Vazquez Fiorani 2021). Due to the
technological and morphological suitability of ceramic pastes for specific activities (temper, porosity, wall thickness, vessel shape,
and surface treatments) we were able to determine functional differences within the groups.

Coarse granitic samples are characterized by porous and thick brownish pastes without surface treatments. Technological
choices related to raw material selection and paste recipes suggest that they were manufactured so as to consider thermal shock
resistance (e.g high amounts of quartz as temper) and friability during handling in mind. The vessels are associated with shapes
such as simple contour pots and open bowls with mouths bigger than 20 cm in diameter. Although fine granitic samples do not
exhibit compositional differences compared with coarse granitic ones, they are composed by dense and thinner brownish to
grayish pastes that are easily distinguishable by naked eye and optical petrography. Morphological reconstruction of fine granitic
samples, allows the identification of service ware, such as small open bowls (< 20 cm) and constricted neck jars. Metamorphic
samples are vessels with coarse pastes and decorated with incised dots made in rolling pits of clay. Nevertheless, it is hard to
ascribe them to cooking activities rather they could have been used as containers for already prepared foods on special
occasions, although use as non-utilitarian vessels cannot be excluded.

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 Table 1
List of samples selected for organic residue analysis by GC-MS.
SAMPLE ID Type Morphology Inferred function Vessel part

LDM_R94_m7 Coarse granitic Bowl Service Rim

LDM_R94_m8 Fine granitic Bowl Service Rim

LDM_R94_m10 Coarse granitic Vessel Storage Base

LDM_R94_m13 Metamorphic Unkown Service Rim

LDM_R94_m14 Coarse granitic Pot Cooking Rim

LDM_R94_m15 Coarse granitic Pot Storage Base

LDM_R94_m16 Coarse granitic Pot Cooking Rim

LDM_R94_m17 Coarse granitic Bowl Service Rim

LDM_R94_m19 Coarse granitic Pot Cooking Rim

LDM_R94_m21 Metamorphic Jar Service Rim

LDM_R94_m27 Fine granitic Pot Cooking Rim

LDM_R94_m33 Fine granitic Bowl Service Rim

LDM_R94_m40 Coarse granitic Flat bowl Bowl Rim

Sample preparation and lipid extraction

Initial ceramic sampling employed a chasing tool and a hammer in order to separate a small fragment for thin-sectioning without
contaminating the entire sample. Afterwards, ceramics were cleaned mechanically using a Dremel 3000 multi-tool with a diamond
wheel point of 4.4 mm to remove soil residues and to remove any possible contamination due to handling and/or storage that
might influence the chemical analyses. After cleaning, ceramics were ground with a mortar and pestle made of agate, which was
cleaned with CHCl3/MeOH (2:1) solution and milli-Q water between samples. The samples were ground until obtaining a fine
powder of approximately less than 10 µm. Then, they were sub-sampled from approximately 4 g of powder for lipid extraction and
2 g for chemical-mineralogical characterization.

On powdered samples a H2SO4/MeOH (acidic extraction, Method 1) and CHCl3/MeOH (2:1, v/v) (chloroform-methanol extraction,
Method 2) lipid extraction was conducted (Reber 2021).

Method 1: First, 2 g of powdered ceramic were mixed with 20 µL of n-tetratriacontane (1mg/mL) (standard) and put in a tube.
Next, 5 ml of H2SO4/MeOH (2% v/v) were added and heated up at 70ºC for 2 h with a magnetic spin. pH < 3 was checked with a
pH paper. Afterwards, samples were centrifuged for 10 minutes at 2500 rpm. Clear supernatant was decanted in a second tube per
sample, and then, added 2mL of ultrapure H20. Next, 3 mL of hexane was added to the potsherd residue and vortexed for two
minutes at 2500 rpm. The hexene supernatants from tube 1 were added to tube 2 and then, vortexed again. The operation was
repeated three times and then, hexane fractions from tube 2 were removed to a clean vial 3 with a pipette. Hexane was added to
the remaining H2SO4/MeOH/H20 solution in tube 2 and vortexed. Again, hexane fractions were added to the clean vial 3. Last
steps were repeated twice. Then, the extract in vial 3 was evaporated under N2 until dry.

Finally, for the total lipid extraction samples in both extractions, TLE, were redissolved in a vial with 250 µL of hexane and
transferred to the small GC vials. Then, the extract was evaporated under N2 until dryness. For derivatization, 50 µL of hexane and
50µL of BSFTA/TMCS were added. Next, the vial was closed tightly and placed in the microwave for 30 seconds at 700W, after
which it was dried again under N2.. For the GC-MS analysis the extracts were dissolved in 100µL of hexane and transferred into
small tubes for the GC autosampler.

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Method 2: 2g of ground sherds samples was transferred in a centrifuge tube and mixed with 20 µL of n-tetratriacontane
(1mg/mL) (standard) and 2mL of CHCl3/MeOH (2:1,v/v) solution. The tubes with the internal standard were ultrasonicated for 15
minutes and then centrifuged for 15 minutes at 2500 rpm. The solvent was removed by decanting to a vial. Ultrasonication and
centrifugation were repeated again with the remaining solid in the tube after adding the solvent again. Afterwards, the extract was
dried using a water bath at 40º C, under a stream of nitrogen.

Finally, for the total lipid extraction samples in both extractions, TLE, were redissolved in a vial with 250 µL of hexane and
transferred to the small GC vials. Then, the extract was evaporated under N2 until dryness. For derivatization, 50 µL of hexane and
50µL of BSFTA/TMCS were added. Next, the vial was closed tightly and placed in the microwave for 30 seconds at 700W, after
which it was dried again under N2.. For the GC-MS analysis the extracts were dissolved in 100µL of hexane and transferred into
small tubes for the GC autosampler.

GC-MS conditions and organic compound identification

The organic extracts were analyzed by Shimadzu GC2010 gas chromatographer coupled to a Shimadzu GCMS-QP2010 ultra
mass spectrometry. The capillary column used for separation was a Phenomenex Zebron-ZB-5HT (15 m length, 0,25 mm internal
diameter, 0,10µm film thickness). The conditions of method utilization for GC were column oven temperature (50ºC), injection
volume of 1 µL and temperature 250ºC in spitless injection mode, and a sampling time of 1 minute. The carrier gas was He (prim.
Press. 300–500) with linear velocity of 62.4 (cm/sec). Pressure was set at 31.5 kPa with a total flow of 152.5 mL/min and the
column flow 1.48 mL/min. Purge flow was 3 mL/min in spitless mode.

Gas chromatography temperature program started at 50°C for 2 min, ramped up to 150°C, then to 250°C, and finally increased to
350°C, at which point it was held for 2 min. Total program time: 67.33 min. MS Ion source temperature was placed at 240°C, and
the interface temperature was maintained at 280°C. The mass spectrometer was programmed to acquire data between 40 and
850 m/z. After running by GC-MS, Peak assignment was done using the National Institute of Standards and Technology (NIST)
and Wiley mass spectra libraries, through AMDIS software.

5. Results And Interpretation Of Results

The samples analyzed by GC-MS provide insights into what foods people processed and / or stored in ceramic containers.
Internal standard and derivatization products were identified in all samples, indicating an effective extraction and derivatization
procedure in both extractions (for an example of the obtained chromatograms, please see Fig. 4). All samples exhibited preserved
organic compounds associated with archaeological biomarkers (see supplementary information for a list of compounds identified
with the two extraction methodologies used in the different samples). The presence of unsaturated and polyunsaturated fatty
acids (e.g. C18:1, C18:2) in some samples suggests a good rate of preservation. Despite the careful handling of the samples,
some compounds associated with post-depositional contamination due to handling or storage (e.g., phthalates) were also
identified.

The acidified methanol method achieves a higher recovery of absorbed lipids, especially in shards with low concentrations (Correa
Ascencio & Evershed 2014; Reber 2021), as the ones analyzed here. A recent study conducted by Reber (2021) comparing
chloroform/methanol and acidic methanol extraction methods pointed to the improved specificity and confidence of results in the
latter case, with higher yields of neutral compounds and fatty acids (e.g. isoprenoid fatty acids, ketones, plant sterols, terpenoids,
and long-chain alkanols like C32:OH AL and C34:OH AL. Indeed, acidic extractions are optimal as a screening and interpretative
step in a project focusing on plant processing, followed if required by a chloroform/methanol extraction to evaluate acyl lipids or
alkanol content (Reber 2021: 15). Nevertheless, the use of a stronger extractant could generate a compositional information loss
due to the mentioned hydrolysis of acylglycerols and wax esters (Correa Ascencio & Evershed 2014). In this case, there was a
recovery of wax esters with the acidic methanol from some sherds, indicating that the recovery power of this solvent mixture
might overcome its hydrolysis potential in some situations.

Organic compounds such as fatty acids, alcohols, alkanes monoacylglycerols (MAG’s), diacylglycerols (DAG’s), and sterols were
identified across samples, allowing to generate hypotheses about the possible foodstuffs processed in the vessels. To render

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organic residues information relevant for archaeological purposes, the structures and distributions of these molecules have to be
matched to the compounds and mixtures known to exist in organisms exploited in the past, although the analytical interpretation
is not always straightforward (Evershed 2008a: 898).

Alkanes are widely distributed within the samples, with the number of carbons going up to 36. They were identified in both
extraction procedures. Long chained alkanes such as n-hexadecane (C16), n-heptadecane (C17), n-octadecane (C18), n-
nonadecane (C19), n-eicosane (C20), n-docosane (C22), n-tetracosane (C24), n-hexacosane (C26), n-heptacosane (C27), n-
nonacosane (C29), n-triacontane (C30), and n-hentriacontane (C31) are found in all samples. Odd-chain n-alkanes are more
abundant in the analyzed samples when compared with even-numbered carbon n-alkanes. Although it is not conclusive, n-alkane
series ranging from C23 to C33 chain length are usually associated with the degradation of plant waxes (Šoberl et al. 2014).

Fatty alcohols were detected as free alcohols and as trimethylsilyl ether derivatives, including the following compounds: 1-
dodecanol (C12:OH AL), 1-tridecanol (C13:OH AL), 1-tetradecanol (C14:OH AL), 1-pentadecanol (C15:OH AL), 1-hexadecanol
(C16:OH AL), 1-heptadecanol (C17:OH AL), 1-octadecanol (C18:OH AL), 1-nonadecanol (C19:OH AL), 1-eicosanol (C20:OH AL), 1-
heneicosanol (C21:OH AL), 1-docosanol (C22:OH AL), 1-tetracosanol (C24:OH AL), 1-pentacosanol (C25:OH AL), 1-hexacosanol
(C26:OH AL), 1-heptacosanol (C27:OH AL), 1-octacosanol (C28:OH AL), 1-triacontanol (C30:OH AL) and 1-dotriacontanol (C32:OH
AL). It is likely that these alcohols are the result of the hydrolysis of epicuticular waxes’ esters, as they are found along with
straight-chain fatty acids (Beeston et al. 2006; Miller et al. 2020). The presence of n-dotriacontanol, (C32:OH AL), is especially
useful, as it is an unusual compound and has been used as a biomarker for the presence of maize in organic residues (Reber
2021:12).

Some samples also exhibited the presence of wax esters associated with palmitic and stearic acids, although they were only
identified in the stronger acidic methanol extraction. Esters ranging in chain length up to C64 (when found together with long-
chain alcohols and odd-carbon number n-alkanes) are usually related to plant resources (Šoberl et al. 2014). The absence of wax
esters in the chloroform methanol extraction (method 1) when compared to the acidic methanol method (method 2) may be
explained by the difference of polarity and pH of the solvents used and the interaction of the solvents with the bound insoluble
portion of residues.

Fatty acids were also more effectively recovered in the stronger acidic extraction. All samples yielded fatty acids, both as free fatty
acids and trimethylsilyl ester derivatives (the presence of free fatty acids indicate that the derivatization process prior to the GC
analysis was not complete). Palmitic (C16:0) and stearic acid (C18:0) are the most commonly identified compounds in organic
residues analysis, therefore they have little diagnostic value as biomarkers (Evershed 2008b). In the presence of plant products,
C16:0 chromatographic peak areas should be higher than C18:0 (Evershed 2008). Nevertheless, C16:0 is more water soluble, and
it might be erroneous to be making assumptions based solely on their ratio (Evershed 2008; Miller et al. 2020). Samples with an
almost sure plant origin can exhibit higher C18:0 peak areas due to the overrepresentation of this fatty acid when compared with
the more soluble palmitic acid. Results from samples presented in this thesis were not conclusive based on the C16:0/C18:0, with
data pointing to both plant and animal origin.

Apart from C16:0 and C18:0 fatty acids, saturated long-chain fatty acids with a carbon number range between C20 and C30 have
been identified in all samples in the acidic extraction, and in samples LDM_R94_m7, LDM_R94_m8, LDM_R94_m10,
LDM_R94_m14, LDM_R94_m15, LDM_R94_m19, LDM_R94_m21, LDM_R94_m33, and LDM_R94_m40, when extracted with the
chloroform/methanol method. Long-chain fatty acids might be related to degraded plant waxes (Buonasera 2007; Šoberl et al.
2014; Miller et al. 2020). Together with the presence of odd numbered carbon n-alkanes and even number chain fatty acid
alcohols, long-chain fatty acids may suggest a plant origin of absorbed residues (Evershed 2008b; Miller et al. 2020). Indeed,
eicosanoic (C20), docosanoic (C22), tetracosanoic (C24), and hexacosanoic (C26) acids (compounds present in our samples)
may suggest the presence of plant lipids as observed for a similar regional study by Lantos and collaborators (Lantos et al. 2018:
663). Furthermore, a combination of C19:0, C20:0, C21:0, C22:0 and C24:0 fatty acids similar to the one of this study was pointed
as evidence of plant waxes in ground stones of Northwestern Argentina (Babot 2004; Bonomo et al. 2012).

Odd chain fatty acids (C15:0, C17:0, and C19:0) were identified in several samples, but only in specific cases do they appear
together (samples LDM_R94_m7, LDM_R94_m10, LDM_R94_m13, LDM_R94_m19, LDM_R94_m21, and LDM_R94_m27) (Table 3).

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The presence of odd numbered chain fatty acids is, nevertheless, usually associated with the presence of animal ruminant fats
(Eerkens 2005; Malainey 2013). Fatty acids such as C15:0, C17:0 and C19:0, as well as C18:1 and their isomers are associated
with the bacterial action of rumen during the digestion process (Evershed 2008; Lantos et al. 2020; Fernández Sancha et al. 2021).
These acids are generally used to propose the processing of andean camelid meat (Maier et al. 2007; Lantos et al. 2018; Chaile et
al. 2018; Lantos et al. 2020; Fernández Sancha et al. 2021, among others). In some cases, these biomarkers can also be the result
of bacterial contamination, but there are no further indicators of that (ergosterol is absent in all samples and only specific ones
exhibited this distribution of odd-chain fatty acids) (Lantos et al. 2017).

Additionally, it was possible to identify the presence of unsaturated fatty acids. Several samples yielded C16:1 (palmitoleic acid),
C17:1 (margaric acid), and C18:1 (oleic acid) (Fig. 4). Palmitoleic acid and oleic acid are widely distributed among the samples,
especially in the chloroform/methanol solvent extraction and their presence may be indicative of certain plant oils (Evershed
2008a).

Linoleic acid (C18:2) is the main constituent of maize and Prosopis, and their presence may suggest the processing or storage of
these plant resources (Naranjo et al. 2010; Perez et al. 2015; Lantos et al. 2015). The presence of linoleic acid in only one sample
can be explained by the high susceptibility to degradation of polyunsaturated fatty acids through prolonged cooking events and
burial environments (Evershed 2008a; Lundy et al. 2021; Whelton et al. 2021). Additionally, vessel re-use or mixture with animal
products usually tends to mask the presence of C18:2 (Lundy et al. 2021).

Triacylglycerols (TAGs) make up 95% of the lipids of the human diet, and they are found in fish, meat, seeds, nuts, and plants
(Historic England 2017). When present, they can cast light into fat sources, as well-preserved animal and plant fats have different
TAGs, but they are also subject to preferential degradation (Whelton et al. 2021). During burial, the ester bonds in the triglycerides
become hydrolyzed and a subsequent leaching of the fatty acids occurs, limiting the analytical scope of these biomarkers
(Whelton et al. 2021; Evershed 2008a). Therefore, only the best-preserved archaeological fats will contain TAGs (Manhita et al.
2015). Indeed, TAGs were not observed in the study, but some samples yielded their degradation products, di- and
monoacylglycerols (DAGs and MAGs) (Fig. 4).

Sterols are a very important source of information when evaluating organic residue origins, as they can be easily related to
specific sources (Evershed 2008a; Reber 2021). Animal products contain high amounts of cholesterol, while plant materials
produce large amounts of phytosterols and only very minor amounts of cholesterol (Evershed 2008a). Recently, it was proposed
on an experimental basis that free sitosterol is the most abundant sterol in maize, and that C18:1 fatty acid sterol esters should
dominate the sterol ester pattern when looking for this American crop (Miller et al. 2020). Similarly, Lantos and collaborators
suggest that stigmasterol and sitosterol are sterols present in species such as Prosopis, Phaseolus vulgaris and Chenopodium
quinoa in addition to Zea mays (Lantos et al. 2020). Unfortunately, only the samples LDM_R94_m10 and LDM_m13 exhibited a
degraded plant sterol compound, and also yields sterols like cholesterol (Fig. 4). Cholesterol was also found as traces in samples
LDM_R94_m40 and LDM_R94_m13 (Fig. 4). This might be explained by reiterated uses of the pots to prepare different recipes or
for the combination of different food products in the same vessel (Wheelton et al. 2021).

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 Table 3
Comparison of extracted odd-chain fatty acids and sterols with method 1 and method 2.
Sample ID C15 C17 C19 C18:1 Cholesterol

Method Method Method Method Method Method Method Method Method Method
1 2 1 2 1 2 1 2 1 2

LDM_R94_m7   x   x   x x      

LDM_R94_m8                    

LDM_R94_m10 x x x x x x x x x x

LDM_R94_m13 x x x x x x x x x  

LDM_R94_m14   x   x     x      

LDM_R94_m15             x x    

LDM_R94_m16             x      

LDM_R94_m17             x      

LDM_R94_m19 x   x   x   x x    

LDM_R94_m21 x x x x   x x x    

LDM_R94_m27   x   x   x x      

LDM_R94_m33 x x   x x x x      

LDM_R94_m40 x x x x     x x    

6. Conclusions
The study presented here revealed the processing of plant-based resources in the analyzed vessels, although with a possible (yet
limited) presence of animal foodstuffs. It is important overstate that plant origin products tend to be understated in organic
residue analysis due to the amount of fat in animal products versus in plant products (Whelton et al. 2021; Evershed 2008a),
therefore it could be possible to infer even a higher presence of vegetable-related lipids in our samples than detected here. A
pattern like this, with a predominance of vegetable oils and waxes has not been observed in similar archaeological sites in the
region, where camelid exploitation was recorded (Fernández Sancha et al. 2021; Lantos et al. 2020; Lantos et al. 2017).

As we mentioned before, lipid analysis does not allow for species level identification. Nonetheless, is it possible to tentatively
propose what were the possible vegetable species processed in these containers based on archaeological information. Vegetable
species known for having been exploited in La Ciénega are Andean crops such as: maize, potatoes, beans, and squash and
especially it was possible to recognize biomarkers usually associated with maize (Reber 2021). At the “Lomita del Medio” site, the
analyses revealed that maize, squash, and quinoa are present on the edges of lithic knives, but also meat fibers. Moreover, a large
number of diatoms were found. Archaeobotanical studies of the stone knifes allow us to argue that plant resources could be
processed in a humid environment due to the presence of diatoms. The biomolecular information adds up to the evidence of large
grinding stones exposed on the surface of several household complexes across the valley that show traces of use for grain
grinding, macro remains (i.e. maize and beans) (Cremonte 1996), and phytoliths and starches of squash and maize identified in
stone knifes (Franco Salvi personal communication). Further characterization of lipids’ isotopic ratio (GC-C-IRMS) could greatly
improve the resolution level and precision of this analysis.

Only three samples (LDM_R94_m10, LDM_R94_m13, LDM_R94_m21) fulfilled all the requirements (combination of odd-chain
fatty acids and C18:1 isomers) to allow us to infer the presence of ruminants fats, being two of these corresponding to service
wares, decorated nonlocal vessels (group C). The third sample with evidence of animal fats correspond to a plain cooking pot
(LDM_R94_m10, group A). The combination of FA and cholesterol make highly probable that this cooking pot may have been
used to process a combination of plant and animal resources, but we do not find evidence of ruminant fats in the rest of cooking

Page 11/21
pots (group A) or fine service vessels (group B). This fact raises the question of whether decorated vessels could have been used
for special occasions or events where non quotidian non staple foods were prepared and consumed. This could explain why we
do not found conclusive evidence of ruminant fats in any of the utilitarian wares intended for daily use (bowls, pots, and jars),
rather than in only in one cooking pot (that could have been used to prepare these “special” foods). Because the limited sample
analyzed here, we are not able to reach a more definitive point on this, although it does seem like a suggestive element to take into
account in future research and sampling targeting.

Although the data analyzed in this article is limited and the interpretations are tentative, it seems unlikely to support a model of
ecological zonal complementarity based on the exchange of animal products for crops in this stage of investigation. We consider,
nevertheless, that the results obtained here, contribute to underscore the previous characterization of La Ciénega as a herding-
based community, with marginal agricultural exploitation (Cremonte 2003). Previous research in the area suggested the
configuration of a herding economy in La Ciénega, suited to its arid and cold conditions instead of a fully developed agricultural
exploitation (Cremonte 2003). Ethnographic observations and oral histories recorded by the researcher contributed to the idea of
La Ciénega has a peripheral settlement mainly focused on pastoralist activities obtaining vegetable resources through exchange
or complementarity bonds with other groups. These interpretations, although possible, prevent us to fully giving account of the
archaeological record with plenty of evidence of vegetable processing and also it presupposes the unchanged continuity of
economic practices from prehispanic to modern times.

Furthermore, we suggest that it is not possible to fully understand past lifeways as closed systems that contain themselves and
remain unchanged across time. In that sense, local economies in the south Calchaquí valleys during prehispanic times seems to
subvert archaeological inferences with the incorporation of archaeometric techniques (for example with the application of stable
isotopes for diet, see Killián Galván et al. 2021) showing how daily life and quotidian practices were flexible instances in which
different elements were combined creatively and reflexively but without unique or fixed structures. Methodologies that can cast
light into discrete spheres of daily life and reconstruct activities at the microscale are particularly well suited to fulfill this aim.

Declarations
Statements and declarations

Ethical approval

Not applicable. 

Competing interests 

I declare that the authors have no competing interests as defined by Springer, or other interests that might be perceived to
influence the results and/or discussion reported in this paper.

Authors’ contributions

A. Wrote the main manuscript text, conducted the experiments, did the data acquisition/interpretation, prepared figures and tables
(including chromatograms)

B. Collaborated in the sample preparation of experiments and chromatogram preparation.

C. Oversaw the experiments and collaborate

D. Conducted archaeological fieldwork and collaborated in sample selection 

E. Reviewed data acquisition and interpretation

All authors reviewed the manuscript.

Funding

Page 12/21
This research was conducted and funded thanks to an Erasmus Mundus + joint master scholarship for the program
ARChaeological MATerials science (ARCHMAT) that the main author hold for the term 2019-2021. Several grants supported the
surveys and excavations conducted in La Ciénega valley, such as the internal grant SECyT-UNC (Consolidar Res SECyT 411/18)
(University of Cordoba) and FONCyT (Argentinian National Council of Science). The authors have no non-financial interests to
disclose.

Availability of data and materials 

Not applicable

Acknowledgments 

Several people collaborated with the fieldwork and lab work, especially J. Salazar, J. Montegú, R. Molar, L. Justiniano, J. Lopez
Lillo, and G. Moyano. The main author would like to thank for all the suggestions and contributions in proof reading to this
manuscript to J. Salazar, I. Kuijt and M. Chesson. The indigenous community of Tafí del Valle, the ones who own the land
ancestrally allowed us to work in the valley. Especially to the family of Hilda Santo Mamani and her partner, Rogelio Armando
Ayala. 

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Figures

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Figure 1

Northwestern Argentina map. The black circle demarks the area comprised by the southern Calchaquí valleys (and the localization
of La Ciénega valley), the more inclusive grey one, the intermontane valleys (Valles y quebradas) archaeological region

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Figure 2

La Ciénega valley landscape

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Figure 3

Lomita del Medio household complex a) R94 enclosure (kitchen) floor plant with principal features b) pits c) heart and grinding
stone d) secondary heart

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Figure 4

Chromatograms of a) LDM_R94_m10, b) LDM_R94_m33 c) LDM_R94_m13 from each type of vessel analyzed in this article

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