Journal of Archaeological Science (1999) 26, 1473–1482

Article No. jasc.1998.0434, available online at http://www.idealibrary.com on

Evidence for Varying Patterns of Exploitation of Animal

Products in Different Prehistoric Pottery Traditions Based on
Lipids Preserved in Surface and Absorbed Residues
Stephanie N. Dudd and Richard P. Evershed*
Organic Geochemistry Unit, School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, U.K.

Alex M. Gibson†
The Clwyd Powys Archaeological Trust, 20 High Street, Welshpool, Powys SY21 7JP, U.K.

(Received 18 August 1998, revised manuscript accepted 2 March 1999)

The excavation of a barrow at Upper Ninepence, Walton in the Welsh Borderlands, U.K., revealed two phases of
occupation associated with two different ceramic traditions, namely Grooved Ware (2500 ) and Peterborough Ware
(3000 ). The Grooved Ware and Peterborough Ware pits seem to have a mutually exclusive distribution on the site.
Screening of the sherds for lipid residues has revealed the presence of remnant fats in a remarkably well-preserved state
considering the age of the finds. Investigations of various chemical characteristics of the remnant fats from absorbed
and carbonized residues have enabled distinctions to be drawn between fats from non-ruminant (e.g. porcine) and
ruminant (e.g. ovine or bovine) origins. Significantly, both ruminant and non-ruminant fats are found associated with
the Grooved Ware whereas only ruminant fats are found associated with the Peterborough Ware. The assignments are
based upon the distributions of solvent-extractable lipid components and the compound-specific stable carbon isotope
values of the major n-alkanoic acids. The results reveal differences in vessel use and indicate possible changes in patterns
of animal exploitation or dietary preferences between the two phases of occupation. The results illustrate the
importance of residue analysis in archaeological investigations, particularly at prehistoric sites where evidence from
faunal remains is limited or absent.  1999 Academic Press

Keywords: GROOVED WARE, PETERBOROUGH WARE, POTSHERDS, NEOLITHIC, ORGANIC

RESIDUES, STABLE CARBON ISOTOPES, FATTY ACIDS, TRIACYLGLYCEROLS, GC-C-IRMS,
HTGC-MS.

Introduction extensive pit digging and structural activity. Locally

made Grooved ware, flint and carbonized debris were
Upper Ninepence recovered from pits and stake-holes (Gibson, 1999).

U
pper Ninepence was a major excavation
carried out by the Clwyd Powys Archaeo-
logical Trust (CPAT) as part of the Walton
Basin project, comprising a Bronze Age barrow which
covered a number of pits and postholes representing a
Neolithic settlement. The excavation of the Neolithic
pits revealed deposits of flint, ceramics and charred
plant material. These were thought to be derived from
a domestic context due to the presence of waste flint
debris and well-used scrapers as the predominant tool
type. Microwear analysis of the lithic artefacts suggests
that inter alia leather and bone working were carried
out at the settlement. In the Grooved Ware phase,
archaeological finds were more numerous, with more
*For correspondence.
†Present address: English Heritage, Fort Cumberland, Fort
Cumberland Road, Eastney, Portsmouth PO4 9LD, U.K.
1473
0305–4403/99/121473+10 $30.00/0
Due to the absence of faunal remains in any of the
features, there was no direct evidence at the site to
indicate animal husbandry, or indeed to enable the
identification of any animal exploitation at this site.
The fundamental difference between the Peterborough
and Grooved Ware is that the former was found
associated with the earlier period (c. 3000 ), while the
latter was exclusively found in the later Neolithic
contexts (c. 2500 ). Radiocarbon dates indicate
that the two periods are unlikely to have overlapped
(Gibson, 1999).
Identification of lipid residues
Fats and waxes entrapped as absorbed or carbonized
residues associated with ceramic vessels during the
processing of natural materials in antiquity are
 1999 Academic Press
1474 S. N. Dudd et al.
surprisingly well protected from chemical decay and
microbial attack (Heron & Evershed, 1993) and can be
retrieved and identified even after several thousands of
years of burial. The application of modern analytical
techniques enables even highly degraded remnants of
natural commodities to be characterized and identified
(Evershed, Heron & Goad, 1990; Evershed et al., 1994,
1997). Often, data obtained from organic residue
analysis provide the only evidence for the exploitation
and processing of animal commodities or leafy vege-
tables, particularly at sites exhibiting a paucity of
environmental evidence. To date the use of chemical
analyses in the reconstruction of vessel use at various
sites in the U.K. has enabled the identification of
animal fats (Needham & Evans, 1987; Evershed et al.,
1992), beeswax (Needham & Evans, 1987; Charters
et al., 1995), birch bark tar (Charters et al., 1993b) and
the epicuticular waxes of leafy vegetables (Evershed,
Heron & Goad, 1991; Evershed et al., 1992, 1994;
Charters et al., 1997).
The identification of ancient commodities based on
lipid residues in pottery is inevitably complicated by
the degradative processes occurring during vessel use
and burial. However, reliable identifications can be
made based on the structures of individual components
and comparison of lipid profiles with modern reference
samples and degraded materials produced in labora-
tory simulation experiments (Evershed, Charters
& Quye, 1995; Dudd, Regert & Evershed, 1998).
Degraded animal fats are by far the most commonly
identified residues found in association with pottery
vessels, and are characterized by a readily recognizable
distribution of free fatty acids, monoacylglycerols,
diacylglycerols and intact triacylglycerols. However,
identification of the particular type of animal from
which the fat is derived is much less straightforward
and complicated to some extent by chemical and
microbiological alteration (Evershed et al., 1992;
Dudd, Regert & Evershed, 1998). To date, distinctions
have been made based primarily upon the distributions
of free fatty acids present (Needham & Evans, 1987;
Rottländer, 1990); however, new approaches are
required in order to make unambiguous distinctions
between remnant fats derived from different animal
species.
For example, the use of stable isotopes in archaeol-
ogy was first explored by Morton & Schwarcz (1988)
who investigated the bulk
13C and
15N values of
organic residues thought to originate from the C4
cereal maize. Hastorf & DeNiro (1985) and Sherriff et
al. (1995) also used stable isotope measurements to
characterize prehistoric carbonized plant and animal
remains, respectively. However, the first application of
compound-specific stable carbon isotope measure-
ments to archaeological samples was reported by
Evershed et al. (1994). The
13C values obtained
for individual components in solvent extracts of
pottery vessels from the Raunds area project,
Northamptonshire, confirmed that the lipids being
investigated were from C3 plants. The distributions of
components were consistent with the lipids in the
potsherds having derived from Brassica species, such as
cabbage. We have recently developed this approach
further and, by utilizing fundamental differences in
the stable carbon isotope composition of the fatty
acid component of the adipose fat in the major
domesticates, have been able to make clear distinctions
between remnant fats of different origins in archaeo-
logical ceramics (Evershed et al., 1997; Dudd &
Evershed, 1998; Mottram et al., 1999). These differ-
ences in stable isotope values were paralleled by differ-
ences in fatty acid composition, although the former
were deemed to be diagenetically more robust.
In this paper we present the results of chemical
analyses of lipid extracts from both Early and Late
Neolithic vessels from the Upper Ninepence exca-
vation. A combination of criteria have been con-
sidered, including the characterization of solvent
extractable lipid components by high temperature gas
chromatography (HTGC) and GC-mass spectrometry
(GC-MS) and the application of compound-specific
stable carbon isotope analysis to measure
13C values
of the major n-alkanoic acids.
Materials and Methods
Samples
Full descriptions of the samples used in this study are
given in Table 1. Seventeen sherds from both the Early
and Late Neolithic phases were provided, six of which
were covered with thick (c. 1–2 mm), black carbonized
residues on one side. The sample set comprised sherds
from five Peterborough Ware and 12 Grooved Ware
vessels. Reference ruminant fats were supplied by
Manor Farm, Brockley where animals were raised on
unimproved C3 pasture. Reference C3 pig fat was
supplied by Baker’s Abattoir, Nailsea and the U.S.
Department of Agriculture in Beltsville, Maryland,
U.S.A. Reference horse fats were supplied by Potter’s
Abbatoir, Bishops Sutton. The diets of all reference
animals were known to be entirely C3 in composition.
Reference beech nuts and acorns were collected from
local woodland. Reference whey was prepared in the
laboratory by warming milk samples and allowing
them to stand overnight.
Solvent extraction of archaeological samples
Lipid analyses of potsherds have been performed using
our established protocol, (Evershed, Heron & Goad,
1990; Charters et al., 1993a) whereby approximately
2 g were taken and their surfaces cleaned using a
modelling drill to remove any exogenous lipids (e.g.
soil or finger lipids due to handling). The samples
were then ground to a fine powder, accurately weighed
and a known amount (20 g) of internal standard
(n-tetratriacontane) added. The lipids were extracted
 Prehistoric Patterns of Exploitation of Animal Products 1475

Table 1. Details of Grooved Ware and Peterborough Ware from the Upper Ninepence excavation (Walton U9D 94) and descriptions of absorbed
(AR) and carbonized (CR) residues analysed

Feature Lipid content Vessel

Sherd no. (context no.) Decoration (g/g) contents**

Peterborough Ware (c. 3000 )

P1a AR Pit 13 (3) Twisted cord impressions as multiple horizontal lines. Incised 120* FFA, MCK
P1b AR Pit 13 (3) decoration in diagonal lines on inside of vessel 104* DAF, MCK
P1 CR Pit 13 (3) Trace –
P3 AR Mound (2) Incised internal crosshatching. 338* DAF
Birdbone impressions on top of rim
P5 AR Pit 16 (17) Oblique fingernail impressions 210* FFA, MCK
P10 AR Pit 6 (7) Random fingernail impressions 13 –
Grooved Ware (c. 2500 )
P21 AR Pit 198 (289) Trace –
P21 CR Pit 198 (289) Trace –
P28 AR Pit 198 (289) Double cordon with fingernail impressions 0 –
P28 CR Pit 198 (289) 0 –
P33 AR Pit 154 (155) Large barrel-shaped vessel. Well-defined horizontal and vertical 13 –
cordons. Largely undecorated
P33 CR Pit 154 (155) 434* DAF
P34 AR Pit 154 (155) Internal and upper part of outer surface decorated with incised 0 –
triangular motifs
P37 AR Pit 198
(199/289) Pit
198 (191)
P38 AR Pit 154 (155) 12 DAF
P38 CR Pit 154 (155) 314* DAF
P39 AR Pit 154 (155) Similar to P33 7 DAF
P39 CR Pit 154 (155) 669* DAF
P48 AR Pit 198 Trace –
(199/289)
P62 AR (87) Trace –
P65 AR (294) Trace –
P66 AR (133) 118* DAF
P68 AR (133) Internally decorated vessel. Interior has incised 247* DAF
motifs—triangular with herringbone or oblique infill
P68 CR (133) 279 DAF

*Selected samples analysed by GC-C-IRMS.

**DAF, degraded animal fats; FFA, free fatty acids; MCK, mid-chain ketones.

with a mixture of chloroform and methanol (2:1 v/v).
Following separation from the ground potsherd the
solvent was evaporated under N2 to obtain the total
lipid extract (TLE).
Carbonized residues were scraped from the surfaces
of the sherds using a scalpel and powdered using a
pestle and mortar. Extractions then proceeded as for
the powdered sherd.
Preparation of trimethylsilyl derivatives
Portions of the total lipid extracts were derivatized
using N,O-bis(trimethylsilyl)trifluoroacetamide (20 l;
70C; 20 min) and analysed by HTGC and GC-MS.
Preparation of fatty acid methyl esters (FAMEs)
Methanolic sodium hydroxide (5% v/v) was added to
the TLE and heated (70C; 1 h). Following neutraliz-
ation, lipids were extracted into hexane and the solvent
reduced by rotary evaporation. FAMEs were prepared
by reaction with BF3-methanol (14% w/v; 2 ml; 70C;
1 h). The methyl ester derivatives were extracted with
diethyl ether and the solvent removed under nitrogen.
FAMEs were redissolved in hexane for analysis by GC
and gas chromatography-combustion-isotope ratio
mass spectrometry (GC-C-IRMS).
High temperature gas chromatography (HTGC)
The GC analyses were performed on a Hewlett
Packard 5890 gas chromatograph (Palo Alto, CA,
U.S.A.), coupled to an Opus V PC using HP Chem-
station software, which provided instrument control,
data acquisition and post-run data processing facilities.
Samples were introduced by on-column injection into a
15 m0·32 mm i.d. fused silica capillary, coated with
DB1 stationary phase (immobilized dimethyl poly-
siloxane, 0·1 m film thickness; J & W Scientific,
Folsom, CA, U.S.A.). The temperature programme
consisted of a 2 min isothermal hold at 50C followed
by a ramp from 50 to 350C at 10C/min. The
1476 S. N. Dudd et al.
temperature was then held at 350C for 10 min; hydro-
gen was used as carrier gas. Flame ionization detection
was used to monitor the column effluent.
Gas chromatography-mass spectrometry (GC-MS)
GC-MS analyses were performed using a Finnigan
4500 quadrupole mass spectrometer directly coupled to
a Carlo Erba 5160 Mega series gas chromatograph
with on-column injection. Operating conditions were
as follows: ion source, 170C; emission current, 400 A
and electron energy, 70 eV. The GC-MS interface was
maintained at a temperature of 350C. Spectra were
recorded over the range m/z 50–850 every 1·5 s. Data
were acquired and processed using a Finnigan INCOS
data system. The GC operating conditions were the
same as those described above except that helium was
used as carrier gas.
Gas chromatography-combustion-isotope ratio mass
spectrometry (GC-C-IRMS)
Analyses were carried out using a Varian 3400 gas
chromatograph (Walnut Creek, CA, U.S.A.) attached
to a Finnigan MAT Delta-S isotope ratio monitoring
mass spectrometer (Bremen, Germany) via a modified
Finnigan MAT combustion interface. The GC column
used was a 25 m0·32 mm i.d. WCOT fused silica
capillary, coated with CP-Wax-52 CB stationary phase
(polyethylene glycol, 0·2 m film thickness). The tem-
perature programme consisted of three ramps from 40
to 150C at 15C/min, from 150 to 220C at 4C/min
and from 220 to 240C at 15C/min remaining at 240C
for 15 min and helium was used as carrier gas. The
Cu/Ni/Pt reactor was maintained at a temperature of
860C. The mass spectrometer source pressure was
610
6 mbar. Samples were injected via a septum
equipped temperature programmable injector (SPI).
Carbon isotope ratios are expressed relative to VPDB,

13C (‰)=1000 [(Rsample
Rstandard)/Rstandard], where
R is 13C/12C. Analytical error expected is0·3‰.
Bulk isotope values were measured on homogenized
plant materials and whey using an NC 2500 elemental
analyser coupled with the Finnigan MAT Delta-S
isotope ratio monitoring mass spectrometer via an
open split interface.
Results
Trimethylsilyl derivatives of solvent extracts of 17
absorbed residues and six carbonized residues were
screened by HTGC in order to establish the presence or
absence of lipid residues. The lipid content of each
sample, expressed in g/g of powdered sherd, is given
in Table 1. Ten out of the 17 sherds analysed contained
amounts of lipid residues considered to be signifi-
cant (< 5 g/g). Notably, the mean lipid content in
absorbed residues from the Peterborough Ware was
50% higher (mean=157 g/g) than in the Grooved
16:0 18:0
100
IS
Relative intensity (%)
50T
52T
54T
17:0 18:1 48T
17:0 br 20:0 46T
15:0
14:0 34D
44T
32D
16M
18M 36D
0
10 20 30
Retention time (min)
Figure 1. HTGC profile of the trimethylsilylated total lipid extract
from P68, an absorbed residue from an internally decorated vessel
from the Grooved Ware assemblage. Note that the major peaks in
the chromatogram have been expanded off scale to reveal detail of
the minor constituents. Peak identities are: 14:0, 15:0, 16:0, etc.
correspond to n-alkanoic acids with 14, 15 and 16 carbon atoms,
respectively; 17:0 br refers to a branched-chain alkanoic acid with 17
carbon atoms; 18:1 refers to a monounsaturated n-alkanoic acid
containing 18 carbon atoms; 16M and 18M refer to mono-
acylglycerols containing 16 and 18 acyl carbon atoms, respectively
(the 1-isomer elutes before the 2-isomer); 32D, 34D, etc. are di-
acylglycerols containing 32, 34, etc. acyl carbon atoms respectively
(the 1,2-isomer elutes before the 1,3-isomer); 44T, 46T, etc. corre-
spond to triacylglycerols bearing 44, 46 etc. acyl carbon atoms,
respectively; IS=internal standard (n-tetratriacontane) added at the
extraction stage to enable quantification of lipid.
Ware (mean=79 g/g). In all cases the lipid residues
were identified as degraded animal fats and, remark-
ably, even after 4500 years of burial, intact triacyl-
glycerols were still detectable. A typical degraded
animal fat profile obtained by gas chromatographic
(GC) analysis of Grooved Ware vessel P68 is shown in
Figure 1. Degraded animal fats are characterized by
this distribution of free fatty acids, mono- and diacyl-
glycerols, resulting from hydrolysis of intact triacyl-
glycerols, the latter being the major constituents of
fresh animal fats.
Mid-chain ketones (C31, C33 and C35), formed
during heating of vessel and their contents to tempera-
tures in excess of 300C (Evershed et al., 1995; Raven
et al., 1997) were identified in the three Peterborough
Ware sherds containing greater than 100 g/g of lipid.
These components are present in sherds P1a and b and
P5 (Table 1) and are shown in the GC profile in Figure
2. The presence of these components in the lipid
residues indicates that the vessels were held in direct
contact with hot embers during use or failure. How-
ever, significantly, none of these diagnostic mid-chain
ketones have been found in the residues associated
with the Grooved Ware. Mid-chain ketones occur
widely in higher plants and bacteria (Kolattukudy,
1976) and nonacosanone (C29 mid-chain ketone),
shown to derive from the leaf waxes of Brassica sp.,
and hentriacontanone (C31 mid-chain ketone), possibly
from Allium porrum (leek) have been found preserved
in archaeological potsherds (Evershed et al., 1992,
1994, 1995). However, the components found in the

16:0 18:0
IS
100
Relative intensity (%)
17:0
18:1
20:0
17:0 br
33K
16M
14:0 18M 31K
15:0
0 Peterborough Ware and the Grooved Ware and
10 20
Retention time (min)
Figure 2. HTGC profile of the trimethylsilylated total lipid extract
from P1b. Peak identities are as for Figure 1. The mid-chain ketones,
indicated as 31K, 33K and 35K, comprise 31, 33 and 35 carbon
atoms, respectively. N.B. The chromatograms in Figures 1 & 2 were
run on different days and on different columns, thus the retention
times are slightly different. All peak assignments were confirmed by
GC-MS.
Peterborough Ware are clearly identifiable as conden-
sation products of acyl lipids formed during the vessel
use. There was no evidence for the processing of leafy
vegetables in any of the samples analysed, although
abundant carbonized plant material (cereal grains) has
been found in the same archaeological features as the
potsherds (Gibson, 1995). Cereal processing would not
result in deposits in the vessels of long-chain alkyl
components of the class described above.
No correlation has been found between the type of
decoration on the surface of the vessels (Table 1) and
the presence or absence of absorbed residues. Three
sherds from the Grooved Ware assemblage, namely
P33, P38 and P39, exhibited low abundances of lipid
absorbed in the porous microstructure of the ceramic,
but very significant quantities of lipid preserved in the
carbonized residues adhering to the inner walls of the
pot. All three vessels were recovered from the same
archaeological feature (pit 154) and preservation may
have been influenced by the burial environment. The
trace amounts of lipid extracted from the carbonized
residues adhering to P1, P21 and P28 may be a
function of the degree of carbonization or the nature of
the original deposit, or a combination of the two.
Furthermore, none of the sherds from pit 198, includ-
ing P21 P28, P37 and P48, contained significant lipid
residues and both sherds from context 133 contained
more than 100 g/g of lipid. Interestingly, the occur-
rence of residues appears to correlate with the context
from which they were deposited/recovered. Whether
this relates to the original mode of use of vessels or the
nature of the burial environment is not clear at this
stage.
The
13C values obtained by compound-specific
stable carbon isotope analysis of the FAMEs in three
absorbed residues from the Peterborough Ware (P1, P3
and P5), two absorbed residues from the Grooved
Ware (P66 and P68) and three carbonized residues
Prehistoric Patterns of Exploitation of Animal Products 1477
from the Grooved Ware (P33, P38 and P39) are plotted
in Figure 3. The
13C values of the archaeological
samples are compared with values for fresh reference
50T
52T
fat obtained from animals reared on diets which are, as
far as possible, isotopically representative of the
48T
archaeological period. These include cattle, sheep and
30D
35K
34D pig adipose fats and cattle and sheep milk fats since
32D
these animals are believed to have been the major
46T 54T
36D domesticates in Neolithic Britain. Clearly, there is a
44T distinction between the absorbed residues from the
30 between the absorbed and carbonized residues from
the Grooved Ware, based on differences in the
13C
values of the C16:0 and C18:0 fatty acids. The two
absorbed archaeological fats from the Grooved Ware
cluster near to the non-ruminant (e.g. porcine) refer-
ence fats while the three from the Peterborough Ware
plot with the ruminant (e.g. ovine and bovine) refer-
ence fats. The carbonized residues adhering to three
Grooved Ware vessels plotted with the ruminant fats.
Indeed, the majority of the remnant fats exhibiting
more depleted values appear to cluster with the refer-
ence ruminant milk fats rather than the ruminant
adipose fats. An analogous distinction between rumi-
nant and non-ruminant origin based on the stable
carbon isotopic composition of fatty acid methyl esters
has also been made between remnant fats in sherds
from an assemblage of lamps and ‘‘dripping’’ dishes
from a later (Mediaeval) site at Causeway Lane,
Leicestershire (Evershed et al., 1997; Mottram et al.,
1999).
Differences in the isotopic compositions of remnant
fats are supported by differences in the intact triacyl-
glycerol distributions in the extracts (Figure 4). The
remnant fats from Peterborough Ware vessels P1, P3
and P5 and Grooved Ware vessels P33, P38 and P39
contained a broad distribution of triacylglycerols rang-
ing between C40 or C42 and C54 (number of acyl
carbons) while the Grooved Ware extracts from P66
and P68 showed, in contrast, a relatively narrow
distribution ranging from C44 to C54 with a much lower
abundance of the C44 and C46 triaclyglycerols. These
distributions are comparable with those seen in
modern ruminant and non-ruminant fats, respectively,
and have been widely reported previously (Christie,
1978, 1981; Enser, 1991 and references therein). A
further subtle distinction can be seen between the
triacylglycerol distributions in the ruminant fats from
the two vessel types, with the Peterborough Ware
consisting of relatively low abundances of the C42, C44
and C46 triacylglycerols. This distribution is more
characteristic of ruminant adipose fats while the
greater abundance of the lower carbon number tri-
acylglycerols is characteristic of degraded dairy fats
(Dudd & Evershed, 1998).
Consideration was also given to the distributions of
major n-alkanoic (fatty) acids in the extracts prepared
as fatty acid methyl esters. In the knowledge that
non-ruminant fats contain either greatly reduced or
1478 S. N. Dudd et al.

–23

Porcine
–25 adipose

P66

P68
–27

Equine
adipose
–29
δ C18:0 (‰)
13

–31 Ruminant
adipose

P1
P5
–33
P33cr
P3

P38cr
Milk

–35

P39cr

–37
–32 –30 –28 –26 –24
δ13C16:0 (‰)

Figure 3. Plot of the
13C values for the major n-alkanoic acid (C16:0 and C18:0) components of the lipid extracts of potsherds from the Walton
assemblage. Remnant fats from the Grooved Ware are represented by filled circles ( ) and the Peterborough Ware by open circles ( ). The

13C values obtained for the fats of modern reference animals, including bovine and caprine (ruminant), porcine (non-ruminant) adipose fat,
ruminant milk fat and horse fat are shown for comparison. The
13C values of the individual fatty acids were determined exactly according to
the conditions given in Woodbury et al. (1995) with corrections for the addition of the derivatizing methyl carbon. The stable carbon isotope
values of the modern reference fats are also corrected for the post-Industrial Revolution effects of fossil fuel burning (Friedli et al., 1986). The
ringed fields encompass the ranges for reference animal fats with the ranges crossing at the arithmetic mean. The numbers of different reference
fats analysed were: pig adipose fat, N=4; ruminant adipose fat, N=9; equine adipose fat, N=10; milk fat, N=7. P1 is a mean of the values
obtained from two different sherds from the same vessel.

none of the branched-chain components which are the ratio of C17:0 (branched-chain) and C18:0 fatty acids
present in reasonably high abundance in ruminant fats, in the archaeological extracts was investigated (Figure
due to bacterial synthesis in the gut (Christie, 1981), 5). C17:0 and C18:0 were also chosen on account of their
 Prehistoric Patterns of Exploitation of Animal Products 1479

Peterborough Ware
100 100
P3 P1

0 0
40 42 44 46 48 50 52 54 40 42 44 46 48 50 52 54

Grooved Ware
Relative abundance

100 100 100 100

P33cr P38 P38cr P39cr

0 0 0 0
40 42 44 46 48 50 52 54 40 42 44 46 48 50 52 54 40 42 44 46 48 50 52 54 40 42 44 46 48 50 52 54

100 100 100

P66 P68 P68cr

0 0 0
40 42 44 46 48 50 52 54 40 42 44 46 48 50 52 54 40 42 44 46 48 50 52 54
Acyl carbon number
Figure 4. Distributions of intact triacylglycerols in total lipid extracts from absorbed and carbonized residues from Walton sherds. The relative
abundance of each component was calculated by measuring the peak area in the HTGC profile.

0.03
similar molecular weights and structures, reasoning
they will be open to similar diagenetic influences,
particularly dissolution in ground waters. There is 0.025
excellent correlation between the ratios of these com-
Ratio C17:0 (branched):C18:0

ponents and the origins assigned to the fats by the

isotopic analyses and triacylglycerol distributions. The 0.02
archaeological ‘‘dairy’’ fats comprised a significantly
higher ratio of C17:0 (branched-chain):C18:0 fatty acids 0.015
than the extracts believed to be of non-ruminant
origin. However, the greatest distinction seen was that
between the ‘‘dairy’’ fats and the ruminant ‘‘adipose’’ 0.01
fats from the Grooved Ware and Peterborough Ware,
respectively, supporting different sources for these two
0.005
groups of fats.

0
Discussion P3 P1 P1 P5 P39 P33 P38
Peterborough Ware Grooved Ware
One of the most unexpected findings from these
Archaeological extracts
analyses is the remarkable preservation which has been
afforded (over several thousands of years) to the lipid Figure 5. Histograms illustrating differences in the ratios of
abundance of C17:0 branched-chain and C18:0 alkanoic acids in
moieties absorbed within the matrix of the ceramic Peterborough and Grooved Ware extracts. The relative abundance
vessels or encapsulated within the carbonized, visible of each component was calculated by measuring the peak area in the
residues. The relatively high quantities of absorbed fats HTGC profile.
1480 S. N. Dudd et al.

Sample
–20 pi nce
t

g e

tP n
66

tP n
68

rn

)
et

s' ey
ilk
fa

nu
pi enc

ac to

ac o
di

co

ow h
tr alt
tr al
e
g

m
(c W
ch
A
er

er

ex W

ex W

ee
ef

ef
–22
R

B
–24
δ13C (‰)

–26

–28

–30
Figure 6.
13C values for C16:0 and C18:0 fatty acids in reference pig fat and archaeological non-ruminant fat from Walton compared with bulk
values ( ) for diets. The
13C values for C16:0 ( ) and C18:0 ( ) fatty acids in the reference fats reflect the bulk values obtained for the diet.
The values for the fatty acids in the archaeological fats may have been influenced by the contribution of relatively depleted 13C components,
e.g. nuts and whey, in the diet. Error bars indicate the instrumental error ( 0·3‰). All values are a mean of triplicate determinations.

and evidence that the vessel contents were strongly
heated is consistent with the use of the Early Neolithic
Peterborough Ware vessels as ‘‘cooking’’ pots. The
Later Neolithic Grooved Ware contained a lower
concentration of absorbed lipid with the absence of
mid-chain ketones, suggesting that vessels had not been
heated to such high temperatures (possibly not heated
directly over a flame).
Although the number of vessels studied is rather
small, it appears from the results obtained that non-
ruminant animals were not being exploited (or were
less important) for their meat at Walton in the
Peterborough phase. It should be stressed though that
it is not possible to determine with certainty the relative
importance of the different domesticates. The analyses
have provided evidence to indicate that meat was being
processed in ceramic vessels; however, other methods
of preparation such as cooking on a spit may have been
important in cooking some meats. There is no chemical
evidence to show that leafy vegetables were prepared in
the same vessels as the meat and therefore they may
have been eaten raw or processed separately. This
observation is consistent with the results of analyses of
many other prehistoric vessels we have studied from
U.K. sites (Dudd, Evershed & Berstan, unpublished
data).
Recent microwear analysis of flint supports differ-
ences between the Peterborough and Grooved Ware
phases, with the flints from the former exhibiting a
complete range of agricultural uses whilst the Grooved
Ware assemblage seems to show wear predominantly
from hide preparation and bone working (R. Donahue,
pers. comm.). The apparent increase in the occurrence
of pigs in the Grooved Ware phase is in keeping with
Grooved Ware faunal assemblages elsewhere; for
example, at Durrington Walls where the preponder-
ance of young pig has been regarded as evidence for
feasting (Wainwright & Longworth, 1971). It is inter-
esting that the three vessels associated with remnant
fats identified as ‘‘dairy’’ residues all have carbonized
residues adhering to them which also contain high
abundances of lipid. This is quite consistent with the
use of these vessels for the heat treatment of dairy
products at reasonably high temperatures since they
are very susceptible to burning, producing thick
charred deposits.
The chemical data have provided us with the
first evidence for the use of secondary products from
ruminant livestock at Walton and also the use of
ceramic vessels for processing of dairy and meat
products. The heating of dairy products suggests either
that they were being pasteurized or that they were
being processed, e.g. to produce cheese or yogurt.
Interestingly, the remnant non-ruminant fats from
Walton are more depleted by approximately 2‰ com-
pared to the reference C3-fed pig fats. Figure 6 shows
the
13C values for fatty acids in the reference pig and
the archaeological fats from P66 and P68 compared
with the bulk values for the diet of the reference
animals. Also shown are bulk values obtained for
examples of foodstuffs which may have contributed to
the diet of pigs in antiquity, including acorns, beech
nuts and whey (Grigson, 1982; Ryder, 1983a). The

13C values of the fatty acids in the reference pig fat
reflect the bulk value obtained for the diet. These
values correlate very well with those reported in Stott

et al. (1997) in studies of lipid extracts of bone from
C3-fed pigs. It is possible that the more depleted values
seen for the archaeological porcine fats (compared with
the reference fats) reflect a contribution in the diet
from isotopically depleted foodstuffs, such as beech nut
kernels or whey which are relatively less depleted in 13C
than the C3 diet of the reference pig. It is well known
that cheese-makers traditionally kept pigs to consume
whey, the by-product of cheese production, and this is
still the case in Romania, southern Russia and south-
ern Poland today (Ryder, 1983a, b). Additionally, pigs
are thought to have been allowed to root in woodland
for nuts and where housed over winter they may have
been fed collected nuts as an additional source of
protein and carbohydrate (Grigson, 1982). Whey in the
diet may also account for the fact that we have detected
low abundances of branched-chain fatty acid compo-
nents in the archaeological non-ruminant fats (St. John
et al., 1987; Busboom et al., 1991) which we would not
normally expect to see in porcine fats, although a
possible exogenous bacterial source for these compo-
nents cannot be completely ruled out (Dudd, Regert &
Evershed, 1998).
Conclusions
The Walton sherds are some examples of the earliest
vessels from which the origins of the absorbed residues
have been classified and the remarkable preservation
of residues is comparable to those from vessels
from much later periods. Although caution must be
observed in determining the origins of fats based
purely on the free fatty acid abundances, the use of a
combination of distributional data obtained by HTGC
and compound-specific stable carbon isotope measure-
ments is certainly a very promising new development in
the analysis of organic residues in prehistoric pottery.
The use of stable carbon isotope ratios in species
classification is very much still in the development
stage and should not yet be considered a routine
technique, although through this work we have begun
to demonstrate the potential which exists for using
this technique to extend archaeological interpretations.
The chemical analysis of prehistoric food residues has
allowed an insight into the trends in food procurement
of Neolithic populations before the development of
culinary skills and dietary preferences which occurred
alongside advances in animal husbandry and crop
farming. This information could not have been
obtained in any other way than through organic
residue analyses due to the lack of faunal evidence at
the site. It is anticipated that this new approach will be
of significant use in interpretations of lipid residues
from other, larger prehistoric sites where pottery
vessels have survived in greater numbers. This study
confirms that the feasibility of this approach is not
constrained by the age of the samples since stable
isotope ratios appear to provide a robust chemical
signal even after 5000 years of burial.
Prehistoric Patterns of Exploitation of Animal Products 1481
Acknowledgements
We would like to gratefully acknowledge Julian and
Eliza Ridge for their help in providing reference fats
and CPAT for archaeological samples and funding.
NERC are thanked for a research grant (GR3/10153)
and for support of mass spectrometry facilities (F14/6/
13).
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