Journal of Archaeological Science 34 (2007) 1379e1390

http://www.elsevier.com/locate/jas

Investigating the presence of ancient absorbed organic residues in

groundstone using GCeMS and other analytical techniques: a residue
study of several prehistoric milling tools from central California
Tammy Buonasera*
Department of Anthropology, University of Arizona, 1009E South Campus Drive, Tucson, AZ 85721-0030, USA
Received 10 August 2006; received in revised form 27 October 2006; accepted 28 October 2006

Abstract

Analysis of absorbed organic molecules in groundstone could provide a valuable means to study resource use and processing in antiquity. The
following study analyzed extracts from the surfaces of several central California milling tools to assess whether organic residues remained from
prehistoric resource processing. It also sought to determine which source identification methods are likely to be successful at providing infor-
mation about the type, or even the specific identify, of resources that were processed. Lipids (primarily fatty acids) were analyzed using GCeMS
and the presence of phenolic compounds was assessed with UV-Vis spectroscopy. Milling surfaces were compared to previously broken surfaces
from the same tool with the assumption that both surfaces had been exposed to similar post-depositional conditions. Results supported the pres-
ence of ancient residues in milling tools. A higher concentration of fatty acids was recovered from milling surfaces than paired broken surfaces.
Furthermore, measurable amounts of azelaic acid (an oxidation product of some unsaturated fatty acids) were present in most milling surfaces,
but not in broken surfaces. However, results also indicated that environmentally absorbed lipids formed a significant portion of the total lipid
content. Thus, it is suggested that future analyses employ a biomarker approach, rather than criteria based on ratios of common fatty acids, to
identify sources of organic residues in prehistoric milling tools.
2006 Elsevier Ltd. All rights reserved.

Keywords: Gas chromatographyemass spectrometry; Lipids; Fatty acids; Phenolic compounds; Groundstone; Milling tools

1. Introduction et al., 2001; Eerkens, 2002; Evershed et al., 1991; Rafferty,

Gas chromatography (GC) and gas chromatographyemass
spectrometry (GCeMS) have been used to analyze absorbed
organic residues in archaeological materials for three decades
(Condamin et al., 1976; Evershed, 1993; Evershed et al., 1999;
Marchbanks, 1989; Patrick et al., 1985; Skibo, 1992). Most ap-
plications have targeted lipid residues in ceramics and many
have provided direct evidence for the use of various foods
and other natural resources in antiquity (Copley, 2003; Copley
* Tel.: 1 520 327 1646.
E-mail address: tyb@email.arizona.edu
2002, 2006; Reber et al., 2004; Spangenberg et al., 2006).
As with archaeological ceramics, ancient lipids and other or-
ganic residues might remain within the porous matrix of
groundstone materials. If present, such residues could provide
data to better characterize relationships between milling tool
forms and resource processing in prehistory. Analysis of ab-
sorbed residues in groundstone could be used to detect early
processing of resources, such as acorn or maize, that later be-
came important dietary staples. It could help evaluate whether
changes in tool form correspond more closely to changes in
the overall strategy of resource processing (with the same suite
of resources), or to the incorporation of new items in the diet
(Adams, 1999; Wright, 1994). Analysis of absorbed organic

0305-4403/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jas.2006.10.028
1380 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390
molecules might also inform us about the preparation and use
of pharmacologically active substances in antiquity (Edwards
et al., 2004; Hall et al., 1990; Rafferty, 2002, 2006).
Despite this potential, very few studies have investigated
the presence of lipid residues (or other organic compounds)
in groundstone tools (Burton, 2003; Quigg et al., 2001). Of
those that have been undertaken, most assume that essentially
all lipids recovered from milling tools were introduced during
prehistoric use, and at least one (Quigg et al., 2001) has inter-
preted lipids using identification criteria (fatty acid ratios) de-
veloped for residues from ancient ceramics. This approach
may be problematic for many reasons. First, it has been dem-
onstrated that measurable amounts of fatty acids are present
within the first few millimeters of unmodified/unused rocks
(T. Buonasera, 2005)dthe same range from which samples
of groundstone are collected (Burton, 2003; Quigg et al.,
2001). Because fatty acids (and other lipids) are ubiquitous en-
vironmental components, it is possible that lipids absorbed
from the soil could mistakenly be interpreted as the remains
of prehistoric foods. Second, residues present in groundstone
could differ in important ways from those encountered in ce-
ramics. Most studies of absorbed residues in ceramics have
targeted sherds from cooking vessels (Eerkens, 2005;
Evershed, 1993; Evershed et al., 1991, 1992, 1997, 1999;
Heron et al., 1991; Malainey et al., 1999; Marchbanks,
1989). This is an important consideration because exposure
to high temperatures not only alters the lipid profile of foods
(Evershed, 1993; Evershed et al., 1992), butdbecause heat in-
creases the fluidity of lipidsdshould also increase the amount
of lipids absorbed. Lipids from milling tools (that have not
been re-used as cooking stones or other heat reservoirs) are un-
likely to have been altered in this manner. Finally, the compo-
sition and porosity of rock and ceramic matrices might differ
in ways that affect the absorption and protection of residues.
The following study tested whether residues from ancient
milling activities might remain in groundstone tools. It also
assessed which methods are likely to provide reliable informa-
tion about the type, or even the specific identify, of resources
that may have been processed.
Organic residues were extracted from surfaces of five cen-
tral California milling tools and analyzed. A paired sample
design was employed that compared milling surfaces with
broken unused surfaces from the same tools. All broken sur-
faces that were sampled had a patina and were broken either
during use, or some time after deposition (but well before
excavation). They served as controls for post-depositional
absorption and were assumed to contain (predominantly)
lipids absorbed from the soil. Thus, if any residues from pre-
historic milling activities were present, milling surfaces were
expected to have a greater concentration of lipids than broken
unused surfaces. It was also expected that types and propor-
tions of fatty acids in milling surfaces should differ from
those in broken unused surfaces. GC/MS was used to analyze
lipids (primarily fatty acids) and UV-Vis spectroscopy was
used to test whether phenolic compounds (potential molecular
markers of acorn processing) might be present in some mill-
ing tools.
1.1. GCeMS and lipid analysis in archaeology
GCeMS is a powerful analytical tool that allows for the
separation, identification and quantification of extremely
small (109 g) amounts of analytes. Lipids are a broad class
of biomolecules that are relatively insoluble in water; they
include fats, oils, waxes, terpenes and sterols (Christie,
2003; Gunstone, 1999; Harwood and Russell, 1984). They
are good target molecules for archaeology because their in-
herent hydrophobicity limits loss through groundwater
leaching. And, although lipids have less taxonomic specific-
ity, they are present in greater quantities and less susceptible
to degradation than either nucleic acids or proteins
(Evershed, 1993; Evershed et al., 1992).
Fatty acids are the most abundant and commonly occurring
type of lipid; they are long chain carboxylic acids and often
form part of more complex lipids (Christie, 2003; Gunstone,
1999; Kates, 1986). The carbon chains of saturated fatty acids
are fully substituted with hydrogen, while unsaturated fatty
acids contain one or more CeC double bond. Fatty acids are
abbreviated with the notation Cx:y, where x is the number of
carbon atoms and y designates the number of CeC double
bonds. In general, plant oils contain a greater proportion of un-
saturated fatty acids and animal fats have a more saturated
profile (Christie, 2003; Gunstone, 1999; Harwood and Russell,
1984; Kates, 1986).
Some analyses have used experimentally determined ra-
tios of common fatty acids to identify whether certain types
of vessels, or ceramics from a given region, were associated
with a broad resource category such as meat, fish, roots,
greens, or seeds (Eerkens, 2005; Malainey et al., 1999;
Marchbanks, 1989). Difficulties interpreting these ratios
are created by the ubiquity of most fatty acids, potential
mixtures from multiple sources, and differing rates of deg-
radation among fatty acids (e.g. unsaturated fatty acids,
like C18:1, degrade much more rapidly than saturated
ones, like C16:0).
Other studies have focused on the presence of more
unique compounds, or biomarkers, as a means to identify
the use of specific resources or substances (such as pine
resin, cabbage, and tobacco) in antiquity (Eerkens, 2002;
Evershed et al., 1991; Garnier et al., 2003; Hall et al.,
1990; Rafferty, 2002, 2006). More recently, many studies
have employed compound specific stable isotope analysis
(CSIA) to provide identifications (Berstan et al., 2004;
Copley, 2003; Copley et al., 2001; Evershed et al., 1997,
1999; Reber et al., 2004; Spangenberg et al., 2006). While
these methods may help circumvent problems such as
mixing and degradative changes associated with ratios of
common fatty acids, they are limited by the infrequent
occurrence of known biomarkers and a lack of detailed
chemical knowledge about many native plants and
animals. Often, this necessitates a significant amount of
work be done beforehand to identify markers that are spe-
cific to particular resources, resistant to degradation, and
present in high enough quantities to be suitable for
detection.
 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390 1381

1.2. Regional context
For the following study, milling tools were selected from
curated assemblages of several central northern California
sites (COL 158, COL 247, and COL 267, and BUT 294)
(White, 2002, 2003). Together, these sites span a time frame
from roughly 4500 BP to 300 BP and encompass a shift in
milling technology from millingslabs and handstones to mor-
tars and pestles (Basgall, 1987; White, 2002, 2003; Wohlge-
muth, 1996). The ability to identify residues on milling tools
could be important for evaluating relationships between tech-
nology and subsistence change in this region. The shift to mor-
tar and pestle technology, visible after about 2500 BP in
central northern California, has long been associated with in-
tensive acorn processing and a more sedentary lifestyle, while
earlier concentrations of millingstones are assumed to repre-
sent the processing of small hard seeds (Basgall, 1987;
Baumhoff, 1963; Driver and Massey, 1957; Gifford, 1971;
Heizer, 1958; Johnson, 1984; Kroeber, 1925; Mikkelsen,
1985; Wohlgemuth, 1996).
However, recent archaeobotanical studies in this region
have revealed that acorns may have played an important, but
perhaps different, role in earlier subsistence patterns (White,
2002, 2003). Acorns were the dominant large seed recovered
from all levels at COL 247, and the earliest levels of this
site predate the regional shift in milling technology by almost
2000 years (White, 2003). This raises several questions. How
were acorns processed in earlier contexts? And, how much
was this shift related to changes in the types of resources ex-
ploited vs. changes in the way they were processeddperhaps
related to changes in desired end-products, and/or to changes
in resource characteristics created by long-term storage (T.Y.
Buonasera, 2005; White, 2002, 2003).
2. Materials and methods
The millingslab and handstones all postdate, and the mortar
and pestles all predate, 2500 BP (cal.).
All artifacts sampled came from curated assemblages that
had previously been cleaned with water. Samples (ap-
prox.0.5e2.0 g) were removed from the first 2 mm of rock sur-
faces using a drill fitted with a carbide steel bit. (For one pair of
very hard surfaces, it was necessary to use a diamond encrusted
bit.) Samples from the same tool were differentiated by labeling
A for the milling surface, and B for the broken unused (control)
surface. Only broken surfaces with a patina and without signs of
either fresh breaks or re-use were included in testing.
Of the eight milling tools, two pestles lacked broken, unused
surfaces and are not considered further here (but see T.Y. Buo-
nasera, 2005). In addition, one of the handstones was very no-
ticeably burned. Because heating between 200e400 C has
been shown to destroy all oxygenated organic compounds in
clay (Johnson et al., 1988), the burned handstone was not in-
cluded in paired testing. Thus, only five surface pairs were
used to determine whether fatty acid concentration was greater
in milling surfaces than in the corresponding broken surfaces.
Two soil samples were also analyzed for comparison to mill-
ing tool residues. Unfortunately neither sample was truly ideal.
One was freshly obtained from COL 267, and thus not subjected
to the same length of curation as milling tools from this site.
The other was (out of necessity) retrieved from a few grams
of soil found remaining in the heavy fraction of a previously
processed, but unanalyzed, flotation sample from COL 247.
In order to test lipid absorption and preservation, Blue Oak
(Quercus douglassi) acorns that had been dried and stored for
about eight months were pounded for one hour with an andes-
itic cobble. This experimental pestle was then stored outside
for an additional month prior to extraction. The milling surface
was sampled at two depths, 0e1 mm (positive control 1) and
1e2 mm (positive control 2). In addition, several fresh acorns
and an old acorn from a Late Prehistoric cache (dated
300 years BP) (White, 1988) were also analyzed.

2.1. Sample 2.2. Extraction

Eight milling tools were selected for analysis: four pestles, A modified Bligh and Dyer method was used to extract all
one mortar, two handstones, and one millingslab (Table 1). samples, as well as two sample blanks (T.Y. Buonasera, 2005;

Table 1
Sample information
Site Accession Provenience BP (cal.) Form Material Condition
COL 267 370-7-16 Locus A, S3, 0-60 350e1100 Pestle (functional end flat) Sandstone Fragment, caliche
on broken end
COL 267 N/A Locus A, S3, 30-60 350e1100 N/A Soil Fresh
BUT 294 32-1102 Surface 520 Mortar (hopper) Andesite Fragment, plow scars
COL 158 328-83-01 Surface 740 Pestle (functional end tapered) Sandstone Fragment, caliche
on broken end
COL 247 327-170-02 Burial 9, matrix 3205 Handstone (wedge shape) Metased Fragment, very hard
COL 247 327-07 A2, 40-60 2755e3295 Milling slab (flat, thin) Sandstone Fragment
COL 247 327-162-04 Burial 5, matrix 3205 Handstone (disc shape) Dacite Fragment, burned
COL 247 N/A A1, 50-60 275 5e3295 N/A Soil Curated
Pos./Neg. ctrl.a N/A Surface Andesite Positive control
used to pound acorns
a
Cobble from dry shore of the West Branch of the Feather River, Butte County, CA.
1382 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390
Kates, 1986). Although most archaeological lipid analyses
have used a Folch extraction (but see Patrick et al., 1985),
two factors made the Bligh and Dyer procedure preferable.
First, the author had prior success using this method to extract
lipids from purported cooking rocks (T. Buonasera, 2005).
Second, because the Bligh and Dyer method employs water,
methanol and chloroform (1:2:0.8 v/v) (CMW) which then
separates into a non-polar (chloroform) and a polar (metha-
nol/water) phase during extraction, it was believed that it
would allow for the concurrent extraction and separation of
more polar compounds like phenols. (The Folch method
uses a single chloroform and methanol (2:1 v/v) phase;
Christie, 2003; Kates, 1986).
2.3. Derivatization of lipid fraction
Lipid extracts (in chloroform) were dried under a gentle
stream of nitrogen and then transesterified into fatty acid
methyl esters (FAMES) by adding 3 ml of 4% sulfuric acid
in methanol to each tube and heating (85e90  C, 60 min.).
The mixture was neutralized and FAMES were recovered
with hexane. The hexane was removed under nitrogen and
50 ml of chloroform was added to the dry FAMES. Samples
were stored at 20  C until analyzed.
2.4. Polar fraction
In order to concentrate compounds in the polar fraction,
and because it could influence the absorption spectra, metha-
nol was removed from the combined water and methanol
phase by rotary evaporation. Samples were stored at 20  C
until analyzed.
2.5. Instrumentation and compound identification
Lipid extracts (FAMES) were analyzed on a HP 6890 GC
coupled to a HP 5976 MS. An HP 5 MS fused silica capillary
column was used. Helium was the carrier gas. Samples (1 ml)
were auto injected and the injection temperature was main-
tained at 275  C. Column temperature was ramped from 40
to 140  C at 20  C per minute, then from 140 to 280  C at
4  C per minute and held at 280  C for 3 min.
Peak areas were integrated using HP Chemstation software.
Peaks were identified by comparison to ion fragmentation pat-
terns from the NIST mass spectral database (NIST98) and also
by comparison to retention times for external standards (Su-
pelco 37).
One sample containing camphor (370-7-9) was analyzed
further with the help of Dr. Chris Nichols (CSU, Chico) who
ran an aliquot of this sample on a different HP 6890 GC fitted
with a chiral column (Rt-b DexSE from Restek). A d,l-cam-
phor standard (Sigma) was analyzed first to determine the
best parameters for separation of the two chiral molecules.
The sample was then injected under the same parameters
and resultant peaks were identified by comparing retention
times.
The polar fractions of several samples were analyzed on
a HP 8453 UV-Vis spectrophotometer. Absorption was
scanned between 250 to 600 nm. Gallic acid, the primary phe-
nolic component of tannins in acorns, has a UV spectrum with
a single maximum absorbance at 275e277 nm, while ellagic
acid, the second most abundant phenolic component, has
a more complex spectrum (Cantos et al., 2003).
2.6. Analysis
Total amounts of fatty acids were calculated by summing
the areas of each fatty acid peak and comparing this to the
peak area for a known amount of external standard (C16:0).
The Wilcoxon signed rank test was used to determine whether
milling surfaces contained greater amounts of lipids than bro-
ken surfaces.
In an attempt to simplify and standardize qualitative compar-
isons, fatty acids were divided into four general categoriesd
each having some interpretive value: % Saturated, % Short
chain, % Odd chain, and % Long, saturated. In addition, the
presence of several less ubiquitous lipids (d,l-camphor, erucic
acid, and azelaic acid) added substantially to the comparison
and interpretation of residues.
% Saturated is the relative percentage of saturated fatty
acids. In modern samples, this value can generally be used
to separate animal fat from plant oil. This value tends to in-
crease significantly in ancient contexts because unsaturated
fatty acids are much more susceptible to degradation than sat-
urated fatty acids (Evershed, 1992, 1993).
% Short chain was defined here as the percentage of
fatty acids 6, 8, 9, and 10 carbons in length. Short chain
fatty acids are present only in low/trace quantities in
many plant and animal fats and oils (milk fat being an ex-
ception) (Christie, 2003; Copley, 2003; Gunstone, 1999;
Harwood and Russell, 1984). Short chain fatty acids can re-
sult from the degradation of medium and long chain acids
(Burton, 2003; Cantos et al., 2003; Evershed et al., 1992);
however, short chain acids are much more water soluble
and volatile than medium and longer chain fatty acids
(Christie, 2003; Evershed et al., 1992; Gunstone, 1999)
and were not expected to accumulate beyond low/trace
quantities. In the present study, greater quantities of these
fatty acids were assumed to derive from contamination
with modern lipids.
% Odd chain was used as a proxy for bacterial lipids/activ-
ity. These fatty acids are typically found in only trace quanti-
ties in plant and animal fats, but often comprise a significant
proportion of bacterial fatty acids (Christie, 2003; Evershed
et al., 1992; Gunstone, 1999).
% Long, saturated was defined as saturated fatty acids 20,
22, 23, and 24 carbons in lengthdlonger chain fatty acids may
have been present, but were beyond the identification capabil-
ities of this study. Although plant oils and animal fats usually
contain only small quantities of saturated fatty acids 20 or
more carbons in length, plant waxes, naturally abundant in
the surface of leaves and the skin of berries and fruit, typically
contain high amounts of saturated fatty acids from 20 to 30
 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390 1383

carbons long (Christie, 2003; Gunstone, 1999; Harwood and Table 2

Russell, 1984). Amounts of fatty acids in samples
Erucic acid (C22:1) is a relatively uncommon fatty acid Sample Form Material Weight Fatty acid
that is rarely found in more than trace amounts in most fats (g) (mg/g)a
and oils. It is present in high quantities in the seed oil of 370-7-16A Pestle Sandstone 2.05 4.02
members of the mustard family (Cruciferae) (Christie, 2003; 370-7-16B Sandstone 1.97 0.07
COL 267 soil Soil 3.00 2.49
Gunstone, 1999; Harwood and Russell, 1984). 32-1102A Mortar Andesite 1.66 6.34
Azelaic acid (nonanedioic acid, C9), is a dicarboxylic acid 9 32-1102B Andesite 1.18 3.84
carbons in length. It is formed by oxidation of D9 fatty acids 328-83-01A Pestle Sandstone 1.67 12.22
C18:1, C18:2 and C18:3 (Christie, 2003; Passi et al., 1993; 328-83-01B Sandstone 1.71 3.88
Regert et al., 1998; Tumosa and Mecklenburg, 2003). Seed 327-170-2A Mano Metased 1.09 60.28
327-170-2B Metased 0.43 19.57
oils typically contain high amounts of these fatty acids and, 327-07-09A Milling slab Sandstone 4.93 6.26
consequently, azelaic acid is a well known component of ran- 327-07-09B Sandstone 1.99 1.73
cid seed oils and ancient seed oil residues (Banks and Hilditch, 327-162-04A Mano Dacite 0.43 10.56
1933; Passi et al., 1993; Regert et al., 1998; Tumosa and 327-162-04B Dacite 0.33 18.00
Mecklenburg, 2003). COL 247 soil Soil 3.05 5.08
Neg. ctrl Andesite 0.68 1.83
Camphor is a bicyclic terpene with a restricted natural distri- Pos. ctrl 1 (0-1 mm) Andesite 1.25 178.01
bution. It is known to occur in several plants (as d-camphor) but Pos. ctrl 2 (1-2 mm) Andesite 0.99 77.27
its largest natural source is the bark of the Asian camphor laurel a
Calculated by reference to external standard.
(Cinnamomum camphora) (Duke, 1992). As natural sources are
inadequate to supply commercial demand, it is commonly syn- For the five unburned milling tools, this difference was signif-
thesized (as d,l-camphor) from a-pinene obtained from turpen- icant at P 0.05. On average, broken surfaces contained
tine (Duke, 1992; Sybilska and Asztemboiska, 2002). about one-third the amount of fatty acids as functional surfaces
(Table 2, Fig. 1).
2.7. Phenolic compounds Table 2 contains information on sample size (g), fatty acid
concentration (mg/g), and material and tool type. Although
In some cases, phenolic compounds or their degradation most samples were in the range of 1e2 g, difficulty sampling
products, phenolic acids, have been used as specific bio- some rocks (because they were very hard) resulted in several
markers for the source of ancient residues (Arpino and samples being less than a gram. Thus, there was some concern
Moreau, 1977; Garnier et al., 2003; McGovern et al., 1996; that lipid content might be linked with sample size.
Michel and McGovern, 1993). Because acorns contain high Fatty acid concentration was not correlated with sample
levels of hydrolyzable tannins (Cantos et al., 2003; Johns size (R2 0.07) (Fig. 2); however, concentration was probably
and Duquette, 1991; Merriam, 1918), phenolic acids (stable affected by particle size. The milling tool (327-170-2) with the
compounds derived from the breakdown of these tannins) highest fatty acid content (60 mg/g for surface A, and 20 mg/g
might remain as indicators of acorn processing. However, phe- for surface B) was the only tool sampled with a diamond en-
nolic compounds are much more water soluble than lipids, and crusted bit, which produced a finer rock dust than the carbide
it is unknown whether they might be present in measurable steel bits.
amounts in groundstone materials. As might be expected, lipid concentration decreased with
Most archaeological studies of phenolic compounds have depth for the milling surface of the andesitic cobble used to
focused on wine or grape products and have used FTIR and
liquid chromatography (McGovern et al., 1996; Michel and 70
McGovern, 1993). Others have created volatile derivatives of surface A
phenolic compounds and analyzed them via GCeMS (Arpino surface B
60
and Moreau, 1977;Garnier et al., 2003). This study used UV-
Vis spectroscopy simply to indicate whether or not measurable 50
amounts of phenolic compounds are present in groundstone.
The primary phenolics in acorns have previously been shown 40
ug/g

to be either gallic acid derivatives, with a maximum absor-

30
bance at 275e277 nm, or ellagic acid derivatives, with
a more complex spectrum (Cantos et al., 2003). 20

3. Results 10

3.1. Comparison of fatty acid quantities 0

370-7-16 32-1102 328-83-01 327-170-2 327-07-09
milling tool
Except for the burned handstone, all milling surfaces had
higher concentrations of lipids than paired control surfaces. Fig. 1. Fatty acid concentrations in paired milling tool surfaces.
1384 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390
70
60
50
Total fatty Acid (ug g-1)
40 R2 = 0.069
30
20
10
0
0 1 2 3 4 5
Sample weight (g)
Fig. 2. Fatty acid concentration by weight for all milling tool samples (n16)
(T. Y. Buonasera, 2005).
experimentally process acorns. The outer 0e1 mm had a fatty
acid concentration of 178 mg/g, while the 1e2 mm sample had
a fatty acid concentration of 77 mg/g (Table 2). The negative
control from the same rock had a low concentration of fatty
acids (1.8 mg/g), lower than all milling surfaces and most bro-
ken surfaces (Table 3).
The fresh soil from COL 267 (S8, 30e60 mm) had
a fatty acid concentration of about 2.5 mg/g, lower than all
functional surfaces and most broken surfaces (Table 2). The
curated soil from COL 247 had a higher concentration of
fatty acids (5.1 mg/g) but was still lower than most milling
surfaces.
3.2. Qualitative comparisons
Typical TICs (total ion chromatograms) are shown in
Fig. 3. Table 3 lists the area and relative percentage of mea-
sured fatty acids for all samples. Table 4 breaks the informa-
tion from Table 3 into four percentages: % Saturated, %
Short, % Long saturated, and % Odd. Table 4 also lists the per-
centage of azelaic acid (C9) relative to the total amount of
fatty acid.
No large, or patterned, differences in % saturated or % odd
chain fatty acids were noted between paired surfaces (except
the functional surface of the milling slab, which had a high rel-
ative amount of 18:1). However, both soil samples were more
unsaturated, and had lower proportions of odd chain fatty
acids, than any milling tool surface (milling surface, or broken
surface).
Other qualitative differences in fatty acid distributions did
exist between most surface pairs (Tables 3 and 4). In particu-
lar, azelaic acid (C9) was present in measurable quantities in
the milling surface of several tools, but not in any broken, un-
used surfaces (Table 4). Similarly, erucic acid (22:1) was de-
tected in the milling surfaces of two tools, but was not
detected in any broken surfaces (Table 3). It was found in a rel-
atively high proportion (11%) in one pestle (328-83-1A), and
also in the millingslab (327-7-9A). It was also present in the
COL 247 soil sample.
It was not possible to compare the distribution of lipids
between the paired surfaces of 370-7-16 because the broken
surface of this tool had lipid quantities too low to measure
(Table 3). The milling surface contained d,l-camphor. Analysis
on the chiral column revealed two equivalent peaks (indicating
a racemic mixture) corresponding to peaks for the d,l-camphor
standard (Figs. 4 and 5). This surface also had one of the high-
est relative amounts of short chain fatty acids (7.5%) (Table 4).
Sample blanks contained very few substances. In fact, other
than some decanedioic acid detected in sample blank 1, nei-
ther sample blank contained any measurable amounts of fatty
6
acids, alkanes, sterols or dicarboxylic acids (Table 3).
The UV-Vis spectrum of the polar fraction from the hopper
mortar revealed a pattern of absorbance similar to the polar
fraction of acorns (Fig. 6). Similar spectra were not observed
for the sample blank, negative control for acorn milling, or
COL 267 soil sample.
4. Discussion
Quantitative and qualitative differences existed between
most surface pairs, supporting the possibility that ancient or-
ganic residues remain within the functional surface of some
milling tools. With the exception of the one burned specimen,
all milling surfaces had higher total fatty acid concentrations
than broken, unused surfaces from the same tool. While this
could simply be the result of longer soil exposure, differences
in lipid distribution provided further support that residues in
milling surfaces were derived, at least in part, from different
sources than those in broken, unused surfaces.
Of all the evidence gleaned from GCeMS of the lipid frac-
tion, perhaps most suggestive was the pattern observed for the
presence of azelaic acid. Measurable amounts of this com-
pound were detected in most milling surfaces, but not in any
broken, unused surfaces. Furthermore, the amount of azelaic
acid was not correlated simply with overall quantities of fatty
acids (R2 0.10).
Measurable amounts of azelaic acid were also recovered
from the old acorn, and in the aged positive controls for
acorn processingdbut were not present in the negative control
rock or fresh acorn samples (Table 4). Azelaic acid is pro-
duced in small quantities from the oxidation of D9 fatty acids
such as oleic (18:1), linoleic (18:2), and linolenic acids (18:3)
(Passi et al., 1993), typically found in high proportions in seed
oils (Christie, 2003; Gunstone, 1999; Harwood and Russell,
Table 3
Relative percentages of fatty acids in samples
Samples Fatty acids Total

T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390

c6:0 c8:0 C9:0 c10:0 c11:0 c12:0 c13:0 c14:1 c14:0 c15:0 c16:1 c16:0 c17:0 c18:2 c18:1 c18:0 c20:1 c20:0 c21:0 c22:1 c22:0 c23:0 c24:0
370-7-16A 0.6 0 5.3 1.7 0 10.8 0 1.8 11.0 3.1 8.5 25.3 0 0 11.8 10.2 0 1.5 0 0 2.8 1.4 4.2 100
370-7-16B 0 0 0 0 0 0 0 0 0 0 0 100 0 0 0 0 0 0 0 0 0 0 0 100
COL 267 soil 0 0 0 0 0 0 0 0 20.4 0 31.3 20.1 0 2.0 11.6 3.1 0 1.4 0 0 3.7 1.5 5.0 100
32-1102A 0 0 0 0 0 5.9 0.7 0 15.9 3.4 4.4 35.0 2.3 0.9 8.6 14.3 0 1.4 0 0 0 0 7.1 100
32-1102B 0 0 0 0 0 2.5 0 0 18.1 3.8 9.6 36.4 2.6 0 10.0 12.2 0 0.0 0 0 0 0 4.8 100
328-83-1A 0.5 2.1 6.3 1.6 0.6 7.3 0.4 0 9.1 1.7 1.9 28.5 0.8 0 6.4 14.0 0 3.5 0 11.2 2.6 0 1.5 100
328-83-1B 0 0 4.0 0 0 0 0 0 8.5 1.5 1.6 38.7 0 0 14.7 21.3 0 4.5 0 0 2.9 0 2.4 100
327-170-2A 0 0 0 0.2 0 3.8 0.3 1.1 6.8 4.2 7.5 27.9 1.4 2.0 13.3 12.6 0 3.1 0 0 6.6 0 9.4 100
327-170-2B 0 0 0 0 0 2.0 0 1.6 9.6 4.7 10.5 34.1 2.0 1.8 16.8 12.3 0 1.1 0 0 0 0 3.6 100
327-7-9A 0 0 0 0 0 2.4 0.3 0.5 5.5 1.7 3.0 22.5 0.9 1.7 42.0 11.8 0 0.7 0 5.0 0.8 0.3 1.0 100
327-7-9B 0 0 0 0 0 25.6 0 0 8.2 3.3 2.3 28.2 0 0 10.5 11.3 0 0.0 0 0 4.0 0 6.5 100
327-162-4A 0 0 0 0 0 2.9 0 0 10.4 2.1 6.1 37.8 1.8 1.8 18.7 18.3 0 0.0 0 0 0 0 0 100
327-162-4B 0 0 0 0 0 1.6 0 0 6.6 3.9 11.3 37.7 1.9 2.0 17.9 14.8 0 0 0 0 0 0 2.4 100
COL 247 soil 0 0 0.5 0 0.4 0 0.3 0 16.3 0 2.1 15.8 0 0 51.8 6.0 0 0.2 0 5.2 0.8 0 0.7 100
Neg. ctrl. 0 0 0 0 0 13.6 0 0 12.4 0 0 45.8 0 0 11.8 16.4 0 0 0 0 0 0 0 100
Pos.ctrl. 1 0 0 0 0 0 0 0 0 0.1 0 0.2 18.1 0.1 1.1 75.5 3.6 0.4 0.5 0 0 0.2 0 0.1 100
Pos.ctrl. 2 0 0 0 0 0 0 0 0 0.3 0 0.5 17.2 0.1 4.2 73.4 3.5 0.4 0.4 0 0.1 0 0 0 100
Sample blank 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Sample blank 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Blue oak 0 0 0 0 0 0 0 0 0 0 0.1 18.6 0.1 19.1 58.8 2.7 0.1 0.2 0 0 0.2 0 0.1 100
Black oak 0 0 0 0 0 0 0 0 0 0 0.1 15.6 0 28.1 51.7 1.8 0 2.8 0 0 0 0 0 100
Tan oak 0 0 0 0 0 0.3 0 0 0.2 0 0.2 19.0 0 35.9 40.9 2.8 0 0.2 0 0 0.2 0 0.3 100
Old acorna 0 0 0 0 0 0.1 0 0 0.4 0.2 0.4 20.3 0.3 19.8 41.8 9.4 0.2 0.9 0.2 0.2 0.2 0.5 5.0 100
a
From cache dated to approximately 300 BP (White, 1988).

1385
1386 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390

Table 4 linolenic acids were once present in several milling surfaces,

Percentages of fatty acid types and additional lipid components detected in but not in unused surfaces (even those with high fatty acid
samples
concentrations) and may indicate the presence of degraded
Sample % Sat.a % Shortb % Longc % Odd Azelaic seed oil from prehistoric milling activities.
acidd
Erucic acid (C22:1) was detected in the milling surfaces of
370-7-16A 77.8 7.5 10.0 9.8 0 two tools, but not in any broken surfaces. It was found in a rel-
370-7-16B 100.0 0 0 0 0
COL 267 soil 55.2 0 11.6 1.5 0
atively high proportion (11%) in one pestle (328-83-1A), and
32-1102A 86.0 0 8.5 6.3 4.0 also in the millingslab (327-7-9A). This fatty acid is not pres-
32-1102B 80.4 0 4.8 6.5 0 ent in many species (although it is typically found in seed oils
328-83-1A 80.5 10.6 7.6 9.8 1.8 of Cruciferae) (Christie, 2003; Gunstone, 1999; Harwood and
328-83-1B 83.8 4.0 9.7 5.5 0 Russell, 1984) so it might be used to indicate the processing of
327-170-2A 76.1 0.2 19.0 5.9 1.6
327-170-2B 69.4 0 4.7 6.7 0
more specific resources. A search of several phytochemical da-
327-7-9A 47.9 0 2.8 3.2 1.2 tabases revealed that it is also present in some chenopodium
327-7-9B 87.2 0 10.5 3.3 0 species (Duke, 1992; Wood et al., 1993) and in lupine (seeds)
327-162-4A 73.4 0 0 3.9 0 and some beans (Duke, 1992). Charred seeds belonging to
327-162-4B 68.9 0 2.4 5.8 0 Chenopodium sp. and to unidentified members of Fabaceae
COL 247 soil 40.9 0.5 1.7 1.2 2.5
Neg. ctrl. 88.2 0 0 0 0
(the family to which both lupine and beans belong) were
Pos.ctrl. 1 23.2 0 0.8 0.1 1.7 well represented at COL 247 (White, 2003).
Pos.ctrl. 2 21.9 0 0.4 0.1 1.9 The milling surface of a wedge shaped handstone from COL
Sample blank 1 0 0 0 0 0 247, with an associated date of about 3200 BP, had the highest
Sample blank 2 0 0 0 0 0 proportion of saturated long chain fatty acids of all tools (19%).
Blue oak 22.0 0 0.6 0.1 0
Black oak 20.1 0 2.8 0 0
It also contained azelaic acid. While azelaic acid might be from
Tan oak 23.0 0 0.7 0 0 degraded seed oils, the high percentage of saturated long chain
Old acorna 37.7 0 6.8 1.3 0.2 fatty acids could indicate the presence of plant waxes from pro-
a
% sat percentage of all saturated fatty acids. cessing leafy plants and/or berries. Future characterization of
b
% short percentage of c6:0 c8:0 c9:0 c10:0. waxes in native plants may lead to more specific identifications
c
% long percentage of c20:0 c21:0 c22:0 c23:0 c24:0. for the source of some residues in milling tools.
d
% azelaic acid is relative to total fatty acids.

1984). Azelaic acid has been detected in ancient residues and 4.1. Soil samples
rancid seed oils (Banks and Hilditch, 1933; Regert et al., 1998;
Tumosa and Mecklenburg, 2003). The presence of this com- Soil samples had less saturated profiles and lower propor-
pound implies that greater amounts of oleic, linoleic, and/or tions of odd chain fatty acids than milling surfaces or broken

Fig. 3. Total ion chromatograms of the broken surface (top) and the milling surface (bottom) of a handstone (327-170-2).
 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390
Fig. 4. Chromatogram of d,l-camphor standard.
surfaces, which may indicate that lipids in rock surfaces are
more degraded than those in the soil samples. Because resi-
dues in the broken unused surfaces also appeared more de-
graded than those in the soil samples, it seems that soil
lipids may be absorbed and retained in rocks in a manner
that does not directly reflect the soil lipid content. Perhaps (al-
though lipids in the soil are being continually replaced) fatty
acids from the surrounding soil find their way into rock matri-
ces very slowly, so that the overall profile is significantly al-
tered by degradative processes before appreciable amounts
can accumulate. Because these materials differ, soil samples
alone should not be considered an adequate control for post-
depositional absorption in rock surfaces.
These soil results are somewhat at odds with conclusions
from a well known study comparing lipids from pottery sherds
to soil adhering to their surface (Heron et al., 1991), and it
must be noted that the two soil samples used in this study
were less than ideal. The COL 267 soil was freshly acquired
and, so, not exposed to the same conditions as the curated
milling tools. In addition, the soil sample from COL 247
may have absorbed lipids from materials with which it was
stored. Because the soil samples for this site could not be lo-
cated, a sample was collected from a small amount of soil
found remaining in the heavy fraction of a previously pro-
cessed, but unanalyzed, flotation sample that contained many
bits of shell, bone, fire cracked rock and other debris. The
COL 247 sample contained twice the amount of fatty acids
Fig. 5. Portion of chromatogram from 370-07-16A corresponding to d,l-
camphor.
1387
as the fresh soil sample, and also had a profile that included
azelaic acid, erucic acid, and a high relative percentage of
C18:1. A future study using more appropriate soil samples
for comparison to both artifact surfaces and controls is neces-
sary to better gauge the degree and manner in which rocks ab-
sorb lipids from the soil.
4.2. Negative and positive controls for acorn milling
The acorn milling experiment showed that the absorbed
fatty acid concentration decreased by more than half between
the first and second millimeter of the milling surface (Table 2).
However, the distribution of fatty acids was very similar for
both depths (Table 3). In addition, both positive controls con-
tained azelaic acid, while the negative control (taken from the
same rock prior to pounding acorns) contained none (Table 4).
It would be interesting to determine through future experimen-
tation how lipids are deposited with increased processing time
and what the upward capacity of absorption might be.
4.3. The burned handstone
The milling surface of the burned handstone from COL 247
did not have a higher amount of fatty acids than the broken
surface from the same tool; indeed, surface B had a greater
concentration of fatty acids than surface A. In addition, the
profiles of both surfaces appeared very similar and neither sur-
face contained azelaic acid (Tables 3 and 4).
These results might be explained by a past heating event.
Prior research (Johnson et al., 1988) has shown that firing
clay at temperatures between 200e400  C results in the de-
struction of all oxygenated organic molecules, in effect, re-
moving all traces of fatty acids from freshly fired ceramics.
If the use-life of this artifact ended as a heat reservoir, then
any fatty acids absorbed from its previous use as a milling
tool might have been destroyed. Yet, new lipids could have
been absorbed from sources it was in contact with after it
cooled.
4.4. Contamination
Evidence for contamination from modern lipids, probably
due to handling in the field or lab, was detected in at least
one milling toolda pestle (370-7-16) from COL 267. This
was based on the presence of a relatively large amount of short
chain acids (especially in the absence of azelaic acid, another
likely degradative by-product) as well as the presence of syn-
thetic camphor. The camphor was determined to be of syn-
thetic origin because it was present as a racemic mixture
(Figs. 4 and 5). Due to mechanisms involved in biosynthesis,
natural systems produce camphor predominantly in the d-
form, while synthetically produced camphor is most easily
and commonly prepared as an equal mixture of d- and l-forms
(Sybilska and Asztemboiska, 2002). Synthetic camphor is
found in many topical products including some cosmetics
and lip balms (Sybilska and Asztemboiska, 2002). It is also
a component of some sunscreens (Schakel et al., 2004).
1388 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390
Fig. 6. UV spectra of blue oak acorn. Spectra for hopper mortar (32-1102) surfaces are inset.
4.5. Phenolics
The pattern of UV absorption observed in the hopper mortar
fragment is suggestive, but by no means conclusive, for the
presence of acorn phenolics. This is because the absorbance
of different molecular species in a solution is additive, and
the polar fraction was not purified but contained mixtures of
unknown compounds. However, the results do indicate that
some compounds which together absorb similarly over the
same UV range as acorn phenolics are present. In light of
this, a future study aimed at detecting specific phenolics in
acorns and milling tools from this region may be worthwhile.
Future research identifying phenolics in milling tools and in
native species of acorns could lead to a biomarker for acorn
processing.
4.6. Applications
The goals of this study were to test whether ancient ab-
sorbed organic residues could be detected in groundstone ma-
terials, and to begin defining areas for future methodological
investigation and improvement. Yet, some statements should
be made regarding future applications for central California
and broader contexts. In California, additional work character-
izing specific phenolic compounds in acorns might lead to
a biomarker for acorn residue. If acorn residue was detected
on numerous milling slabs and/or handstones prior to the ma-
jor technological shift in milling equipment, it would provide
evidence that acorns found in cultural deposits predating this
shift were processed (at least sometimes) by the same grinding
and manual leaching method associated with mortars and
pestles. This would have bearing on the timing and process
of resource intensification proposed for this region. In addi-
tion, the detection of erucic acid and other less ubiquitous
lipids suggests the worth of future studies aimed at character-
izing the chemical composition of certain weedy plants like
chenopodium. Finding biomarkers for this and other potential
proto-domesticates could lead to new information about their
use and processing in many contexts.
5. Conclusions
Overall, results supported the presence of ancient residues
in the milling surface of groundstone tools. This presence
was supported by a significantly higher total fatty acid concen-
tration in milling surfaces than in broken unused surfaces from
the same tools, and by qualitative differences in lipid profiles
between most surface pairs. Perhaps most significantly, the oc-
currence of azelaic acid was consistent with residues high in
oleic acid (C18:1), linoleic acid (C18:2) and/or linolenic
acid (C18:3) having once been present in most milling sur-
faces, but not in any broken surfaces.
Total fatty acid concentrations in broken (control) surfaces
of the milling tools averaged about 30% of those encountered
on the milling surfaces, suggesting that there may have been
a significant contribution from environmentally absorbed
lipids. A contribution of this magnitude would influence iden-
tifications based on ratios of common fatty acids.
Thus, potential identifications must rely on lipids with
greater taxonomic specificity, such as waxes, terpenes, less
common fatty acids, and/or other compounds (e.g. phenolics)
that are be restricted to particular resources. In some regions
(e.g., where maize, a C4 plant, was introduced to a predomi-
nately C3 environment; Reber et al., 2004) compound-specific
stable isotope analysis could be quite successful. Development
of a more comprehensive database on the chemical composi-
tion of native plant and animal resources is essential to these
approaches; armed with greater information, target molecules
and analytical techniques can then be tailored to particular
questions at hand.
More research on the presence and identification of ancient
residues in stone materials should be conducted. Especially
 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390
critical, is a better understanding of the nature and extent of
lipid absorption from the post-depositional environment. Fur-
ther research investigating absorbed organic residues in
groundstone milling tools could lead to a valuable new source
of data about resources use and processing in prehistory.
Acknowledgments
Materials for this project were provided through the Ar-
chaeological Research Program at California State University,
Chico. I am indebted to the Chemistry Department at CSU,
Chico for the use of their GCeMS and their technical assis-
tance. Thanks to Dr. Jelmer Eerkens, Dr. Suzanne Fish, and
to two anonymous reviewers for reading and commenting on
this manuscript. Any errors of fact or omission are my own.
References
Adams, J.L., 1999. Refocusing the role of food-grinding tools as correlates for
subsistence strategies in the U.S. Southwest. American Antiquity 64, 475e
498.
Arpino, P., Moreau, J.P., 1977. Gas chromatographic-mass spectrometric anal-
ysis of tannin hydrolysates from the ink of ancient manuscripts (XIth to
XVIth Century). Journal of Chromatography 134, 433e439.
Banks, A., Hilditch, T.P., 1933. A note on the composition of some fatty
materials found in ancient Egyptian tombs. Analyst 58, 265e269.
Basgall, M.E., 1987. Resource intensification among hunter-gatherers: acorn
economies in prehis-toric California. Research in Economic Anthropology
9, 21e52.
Baumhoff, M.A., 1963. Ecological determinants of aboriginal California pop-
ulations. California University Publications in American Archaeology and
Ethnology 49, 155e236.
Berstan, R., Dudd, S.N., Copley, M.S., Morgan, E.D., Quye, A.,
Evershed, R.P., 2004. characterization of bog butter using a combination
of molecular and isotopic techniques. Analyst 129, 270e275.
Buonasera, T., 2005. Fatty acid analysis of prehistoric burned rocks: a case
study from central California. Journal of Archaeological Science 36,
957e965.
Buonasera, T.Y., 2005. Analysis of Fatty Acids and Other Organic Compounds
in Prehistoric Milling Tools From Central California Using GCeMS and
UV-Vis Spectroscopy, MA Thesis, California State University, Chico.
Burton, M., 2003. Gas chromatography/mass spectrometry analysis of organic
residues in ceramic and ground stone artifacts from INY-1317 and INY-
1991. In: Byrd, B.F., . Hale, M. (Eds.), Lacustrian Lifestyles Along Owens
Lake: NRHP Evaluation of 15 Prehistoric Sites for the Olancha/Cartago
Four-Lane Project, U.S. Route 395. Department of Transportation, Central
California Cultural Resources Branch, Inyo County, California, pp. 515e535.
Cantos, E., Espin, J.C., Lopez-Bote, C., De La Hoz, L., Ordonez, J.A.,
Thomas- Barberan, F.A., 2003. Phenolic compounds and fatty acids
from acorns (Quercus spp.), the main dietary constituent of free-ranged
Iberian pigs. Journal of Agricultural and Food Chemistry 51, 6248e6255.
Christie, W.W., 2003. Lipid Analysis, 3rd edition. The Oily Press, Bridge-
water, UK.
Condamin, J.F., Formenti, M.O., Metais, M.M., Blond, P., 1976. The
application of gas chromatography to the tracing of oil in ancient
amphorae. Archaeometry 18, 195e201.
Copley, M.S., 2003. Direct chemical evidence for widespread dairying in
prehistoric Britain. Proceedings of the National Academy of Sciences
100, 1524e1529.
Copley, M.S., Rose, P.J., Clapham, A., Edwards, D.N., Horton, M.C.,
Evershed, R.P., 2001. Detection of palm fruit lipids in archaeological pot-
tery from Qasr Ibrim, Egyptian Nubia. Proceedings of the Royal Society,
London B 268, 593e597.
1389
Driver, H., Massey, W., 1957. Comparative Studies of North American In-
dians. American Philosophical Society, Philadelphia, p. 235.
Duke, J.A., 1992. Handbook of Phytochemical Constituents of GRAS Herbs
and Other Economic Plants. CRC Press, Boca Raton.
Edwards, H.G.M., Sibley, M.G., Derham, B., Heron, C.P., 2004. Raman
spectroscopy of archaeological samples from the barber-surgeons me-
dicine chest on the Mary Rose. Journal of Raman Spectroscopy 35,
746e753.
Eerkens, J.W., 2002. The Preservation and Identification of Pinon Resins by
GCeMS in Pottery from the Western Great Basin. Archaeometry 44,
95e105.
Eerkens, J.W., 2005. GCeMS Analysis of Fatty Acid Ratios of Archaeological
Potsherds from the Western Great Basin of North America. Archaeometry
47, 83e102.
Evershed, R.P., 1992. Chemical composition of a bog body adipocere. Ar-
chaeometry 34, 253e265.
Evershed, R.P., 1993. Biomolecular archaeology and lipids. World Archaeol-
ogy 25, 74e93.
Evershed, R.P., Heron, C., Goad, L.J., 1991. Epicuticular wax components pre-
served in ancient potsherds as chemical indicators of soft tissue vegetables
in ancient diets. Antiquity 65, 540e544.
Evershed, R.P., Heron, C., Charters, S., Goad, L.J., 1992. The survival of food
residues: new methods of analysis, interpretation and application. Proceed-
ings of the British Academy 77, 187e208.
Evershed, R.P., Mottram, H.R., Dudd, S.N., Charters, S., Stott, A.W.,
Lawrence, G.J., 1997. New criteria for the identification of animal
fats preserved in archaeological pottery. Naturwissenschaften 84,
402e406.
Evershed, R.P., Dudd, S.N., Charters, S., Mottram, H., Stott, A.W., Raven, A.,
van Bergan, P.F., Bland, H.A., 1999. Lipids as carriers of anthropogenic
signals from prehistory. Philosophical Transactions of the Royal Society
of London B 354, 19e31.
Garnier, N., Richardin, P., Cheynier, V., Regert, M., 2003. Characterization of
thermally assisted hydrolysis and methylation products of polyphenols
from modern and archaeological vine derivatives using gas chromatogra-
phy-mass spectrometry. Analytica Chimica Acta 493, 137e157.
Gifford, E.W., 1971[1936]. Californian balanophagy. In: Heizer, R.F.,
Whipple, M.A. (Eds.), The California Indians: A Source Book, 2nd Edi-
tion. University of California Press, Berkeley, pp. 301e305.
Gunstone, F., 1999. Fatty Acid and Lipid Chemistry. Aspen Publishers,
Maryland.
Hall, G.D., Tarka Jr., S.M., Hurst, W.J., Stuart, D., Adams, R.E.W., 1990. Ca-
cao residues in ancient Maya vessels from Rio Azul, Guatamala. American
Antiquity 55, 138e143.
Harwood, J.L., Russell, N.J., 1984. Lipids in Plants and Microbes. George
Allen & Unwin, London.
Heizer, R.F., 1958. Prehistoric Central California: a problem in historical
developmental classification, University of California Archaeological
Survey Reports 41, 19e26.
Heron, C., Evershed, R.P., Goad, L.J., 1991. Effects of migration of soil lipids
on organic residues associated with buried potsherds. Journal of Archaeo-
logical Science 18, 641e659.
Johns, T., Duquette, M., 1991. Traditional detoxification of acorn bread with
clay. Biology of Food and Nutrition 25, 221e228.
Johnson, J.J., 1984. Groundstone Assemblages in Northeastern California,
Ph.D. Dissertation, University of California, Davis.
Johnson, J.S., Clark, J., Miller-Antonio, S., Robins, D., Schiffer, M.B.,
Skibo, J.M., 1988. Effects of firing temperature on the fate of naturally
occurring organic matter in clays. Journal of Archaeological Science 15,
403e414.
Kates, M., 1986. Techniques of Lipidology: Isolation, Analysis and Identifica-
tion of Lipids, 2nd edition. Elsevier Publishing, New York.
Kroeber, A.L., 1925. Handbook of the Indians of North America, Bulletin 78.
Bureau of American Ethnology of the Smithsonian Institution, Washington
DC, pp. 411e414.
Malainey, M.E., Przybylski, R., Sherriff, B.L., 1999. Identifying the former con-
tents of Late Precontact Period pottery vessels from Western Canada using
gas chromatography. Journal of Archaeological Science 26, 425e438.
1390 T. Buonasera / Journal of Archaeological Science 34 (2007) 1379e1390
Marchbanks, M.L., 1989. Lipid Analysis in Archaeology: An Initial Study of
Ceramics and Subsistence at the George C. Davis Site, M.A. Thesis, An-
thropology Department, University of Texas, Austin.
McGovern, P.E., Glusker, D.L., Exner, L.J., 1996. Neolithic Resinated Wine.
Nature 381, 480e481.
Merriam, C.H., 1918. The Acorn, a Possibly Neglected Source of Food. The
National Geographic Magazine 34, 129e137.
Michel, R.H., McGovern, P.E., 1993. The first wine and beer: chemical detec-
tion of ancient fermented beverages. Analytical Chemistry 65, 408e413.
Mikkelsen, P., 1985. A Study of Millingtool Form and Function Applied to the
North Coast Ranges, California. M.A. Thesis, California State University,
Sonoma.
Passi, S., Picardo, M., De Luca, C., Nazzaro-Porro, M., Rossi, L., Rotilio, G.,
1993. Saturated dicarboxylic acids as products of unsaturated fatty acid
oxidation. Biochimica et Biophysica Acta 1168, 190e198.
Patrick, M., de Koning, A.J., Smith, A.B., 1985. Gas liquid chromatographic
analysis of fatty acids in food residues from ceramics found in the South-
western Cape, South Africa. Archaeometry 27, 231e236.
Quigg, J.M., Malainey, M.E., Przybylski, R., Monks, G., 2001. No bones about
it: using lipid analysis of burned rock and groundstone residues to examine
Late Archaic subsistence practices in south Texas. Plains Anthropologist
46, 283e303.
Rafferty, S.M., 2002. Identification of nicotine by gas chromatography/mass
spectroscopy analysis of smoking pipe residue. Journal of Archaeological
Science 29, 897e907.
Rafferty, S.M., 2006. Evidence of early tobacco in Northeastern North
America? Journal of Archaeological Science 33, 453e458.
Reber, E.A., Dudd, S.N., van der Merwe, N.J., Evershed, R.P., 2004. Direct
detection of maize in pottery residues via compound specific stable carbon
isotope analysis. Antiquity 78, 682e691.
Regert, M., Bland, H.A., Dudd, S.N., van Bergen, P.F., Evershed, R.P., 1998.
Free and bound fatty acid oxidation products in archaeological ceramic
vessels. Proceedings of the Royal Society of London B 265, 2027e2032.
Schakel, D.J., Kalsbeek, D., Boer, K., 2004. Determination of sixteen UV fil-
ters in skincare formulations by high-performance liquid chromatography.
Journal of Chromatography A 1049, 127e130.
Skibo, J.M., 1992. Pottery Function: A Use Alteration Perspective. Plenum
Press, New York.
Spangenberg, J.E., Jacomet, S., Schibler, J., 2006. Chemical analysis of or-
ganic residues in archaeological pottery from Arbon Bleiche 3, Switzer-
landdevidence for dairying in the late Neolithic. Journal of
Archaeological Science 33, 1e13.
Sybilska, D., Asztemboiska, M., 2002. Chiral recognition of terpenoids in
some pharmaceuticals derived from natural sources. Journal of Biochemi-
cal and Biophysical Methods 54, 187e195.
Tumosa, C.S., Mecklenburg, M.F., 2003. Weight changes on oxidation of
drying and semi-drying oils. Collection Forum 18, 116e123.
White, G.G., 1988. Archaeological Investigations at Fort Mountain Rockshel-
ter (CA-CAL- 991), a Late Prehistoric Habitation Site in Central Calaveras
County, California. Northcentral Information Center of the California
Archaeological Inventory, California State University, Sacramento.
White, G.G., 2002. Cultural Diversity and Culture Change in Prehistoric Clear
Lake Basin: Final Report of the Anderson Flat Project No.13. Davis, CA:
Center for Archaeological Research at Davis.
White, G.G., 2003. Testing and Mitigation at Four Sites on the Level (3) Long
Haul Fiber Optic Alignment, Colusa County, California, Archaeological
Research Program Reports No. 42, California State University, Chico.
Wohlgemuth, E., 1996. Resource intensification in prehistoric Central Califor-
nia: evidence from the archaeobotanical data. Journal of California and
Great Basin Anthropology 18, 81e103.
Wood, S.G., Lawson, L.D., Fairbanks, D.J., Robinson, L.R., Andersen, W.R.,
1993. Seed lipid content and fatty acid composition of three Quinoa culti-
vars. Journal of Food Composition and Analysis 6, 41e44.
Wright, K., 1994. Ground-stone tools and hunter-gatherer subsistence in south-
west Asia: implications for the transition to farming. American Antiquity
52, 238e262.