APPLICATION OF NUCLEAR MAGNETIC RESONANCE

SPECTROSCOPY TO THE ANALYSIS OF ORGANIC

ARCHAEOLOGICAL MATERIALS

E.L. Ghisalberti and I.M. Godfrey

Summary-The application of nuclear magnetic resonance (NMR) spectroscopy to the analysis of organic
archaeological materials can provide valuable information to conservation scientists, conservators and archae-
ologists. In this review the usefulness of the NMR technique and the breadth of possible applications are illus-
trated. The technique and its scope are briefly described. Details of the use of NMR spectroscopy to identify
the nature and composition of organic residues, to aid in determining the provenance of such residues and its
application to the analysis and determination of the extent of degradation of archaeological materials are pre-
sented.

Introduction

Nuclear magnetic resonance (NMR) spectroscopy infancy, many of the applications described in this
has become an important addition to the collection review seem to have been tentative trials with a new
of techniques available to analytical chemists. When technique. Consequently the results obtained often
instruments became commercially available in the appear as isolated facts: individual pieces of a larger
1950s, NMR was rapidly enlisted by organic jigsaw puzzle. There is little doubt that as the tech-
chemists and employed in the task of determining nique gains wider acceptance and is more consis-
the structure of organic molecules. Initially, only tently applied, it will help to disclose more complete
proton NMR spectroscopy was available. This and satisfying answers. It is hoped that this review
allows detection and differentiation of hydrogens in will stimulate interest in this technique and encour-
a molecule according to their particular chemical age its application to answering some of the ques-
environments. However, with the development of tions faced in archaeological conservation and
more sophisticated instrumental techniques, in par- research.
ticular computer data acquisition, the detection of
numerous other nuclei became possible. Further-
more, whereas the technique was for some time limi- Nature of organic archaeological residues
ted to the analysis of liquid or solid samples
dissolved in a suitable solvent, the application of the In recent years there has been increasing interest by
cross polarization/magic angle spinning (CP/MAS) archaeological chemists in examining organic mate-
technique now allows the analysis of solid samples rials. This is perhaps due to the realization that
such as wood, coal, glasses and metal oxides. organic materials are often more preserved than
The theory underpinning the NMR technique is previously recognized [1, 2]. The identification of
derived from quantum mechanics and the instrumen- organic residues can provide direct evidence of
tation required is both sophisticated and expensive. ancient activities, as opposed to inferences from lit-
It is not our intention to cover the fundamentals of erary and iconographic records.
the technique in detail, nor to convey the impression In the past, the analysis of organic residues posed
that conservators, museum scientists and archaeolo- significant problems. Usually there was little mater-
gists need to familiarize themselves with the theoreti- ial available and the integrity of these fragile
cal background. The purpose of this review is to remains was often uncertain. Furthermore, in most
illustrate the usefulness of the technique and the cases analytical instrumentation was not sensitive
breadth of applications in the characterization of enough to provide detailed information on these
organic archaeological remains. It seems timely to samples. Modern developments in this field are now
review examples of its application, thus providing a providing spectroscopic and chromatographic tech-
starting point for some workers and an update for niques which are both sensitive and specific, yield-
others. As the use of NMR analytical techniques in ing information at the molecular and structural
conservation and archaeological studies is still in its levels.
Typical naturally occurring organic materials
Received November 1997 include oils, fats, waxes, resins, dyes, gums, carbo-

Studies in Conservation 43 (1998) 215-230 215


hydrates, proteins, bituminous materials and cellu-
losic materials. They embrace a great variety of
properties, ranging from tensile, pliant, tough mate-
rials such as skins and leather to plastic and mal-
leable adhesives [I). These compounds were and
still are of vital importance in everyday life and
when isolated from archaeological sites enable the
archaeologist and the archaeochemist to gain an
insight into the lives and practices, including trade,
diet, and food processing and storage, of past gen-
erations [2-{j).
From the time that these substances are produced
and used, they are subjected to environmental con-
ditions that are capable of altering the original
material. The deterioration of organic materials has
been considered elsewhere [7], but a few aspects are
pertinent to this discussion. The individual proper-
ties of organic materials determine the extent to
which these substances are able to resist leaching
and environmental degradation.
Some materials, such as fats and cellulosic mate-
rials, can undergo chemical or microbial changes
which modify the original components, while others
such as dammar, mastic and frankincense retain
their characteristic composition for thousands of
years [8, 9]. Even amber, which is many millions of
years old, does not appear to be a completely poly-
meric matrix, protection having been conferred on
the core by the weathered outer layer [7). Thus,
despite its tendency to decay, the integrity of some
of the residual organic archaeological material is
often maintained, thereby providing a source of
valuable archaeological information.
Analysis of organic archaeological materials
Elemental analysis, infrared (IR), ultraviolet (UV)
spectroscopy, gas chromatography (GC), gas chro-
matography-mass spectrometry (GC-MS), pyrolysis
GC, thin layer chromatography (TLC), high perfor-
mance liquid chromatography (HPLC) and amino
acid analysis are the more common techniques that
have been used, either singly or in combination, to
characterize organic archaeological materials [8,
10--15). NMR spectroscopy is complementary to
these.
The single factor which distinguishes NMR from
other techniques iSt,that it gives a fingerprint for
each particular type of nucleus examined. In com-
parison with other established methods, the main
advantages offered by this technique are the follow-
ing. In solution NMR spectroscopy all the compo-
nents comprising the organic residue can be
analyzed at the same time. Although this is true
also for IR and UV spectroscopy, the greater reso-
lution possible with NMR makes this a superior
216
--
E.L. Ghisalberti and I.M. Godfrey
technique. Once the NMR data have been obtained
and analyzed, an informed decision can be made on
the selection of other analytical techniques.
Furthermore, with I3C NMR additional informa-
tion can be deduced about the nature of the func-
tional groups present.
GC and GC-MS are powerful techniques for the
analysis of trace amounts of materials, a particular
advantage considering the very small amounts of
archaeological material that are usually made avail-
able for analysis. As both techniques discriminate
on the basis of volatility, however, it is not uncom-
mon to find that the major component (or compo-
nents) in a mixture is insufficiently volatile to
migrate through the column. Derivatization of the
sample may not fully overcome this problem and,
because it involves a chemical reaction, incomplete
reaction and the formation of by-products can
complicate matters. Despite the above-mentioned
disadvantages, GC and GC-MS are the techniques
usually employed when information is needed
regarding the composition of small amounts of
complex mixtures of organic archaeological
residues.
Solid-state NMR does not discriminate on the,
grounds of solubility, as is the case for UV and
solution IR spectroscopy. Indeed, it is considered
that CP/MAS NMR is the only analytical technique
that gives quantitative information about the rela-
tive amounts of extractable and non-extractable
compounds in residues [16]. From I3C and IH
NMR spectral data, the classes of compounds com-
prising the organic residue can often be deduced a
priori. This is not the case for any of the other
techniques. It has been stated that 'the profile of
types of carbon in the carbon-13 NMR spectrum
provides the same sort of information for organic
materials that the profile of elements does for inor-
ganic materials such as pottery, glass or metals'
[17).
As with any analytical technique, NMR spec-
troscopy has its disadvantages. Compared to GC-
MS it lacks sensitivity and resolving power when
dealing with complex mixtures. A further problem
often encountered is the very small amount of
archaeological material that is available for analy-
sis. Quantitation of individual components in a
mixture can also be difficult. Unlike MS, the only
indication of the molecular weight of the organic
substances under consideration comes from the
inference about the class of compounds involved.
Not least important are factors such as the fact that
instrumentation is less readily accessible and inter-
pretation of spectra requires considerable expertise.
It is not the aim of this publication to discuss in
detail the relative advantages and disadvantages of
the various analytical techniques. A discussion of
Studies in Conservation 43 (1998) 215-230
Application of NMR spectroscopy to the analysis of organic archaeological materials

the possibilities and limitations of the various ana-

lytical techniques and the implications for conserva-
tion treatment, particularly in studies of organic
residues found in association with ceramics, has
been published recently [16].

Scope of the NMR technique

NMR can be defined as the absorption and emis-
sion of electromagnetic radiation by nuclei of cer-
tain atoms when they are placed in a magnetic field.
The majority of elements in the Periodic Table have
at least one isotope capable of NMR but a number
of common nuclei, including 12C, 160 and J2S, do !
not possess this magnetic property. Nuclei
detectable by NMR include IH, DC, 19F,23Na, 27Al, Figure 1 Proton N M R spectrum of the acidic frac-
29Siand 31p (Table I). The NMR spectrum is pre- tion obtained from modern Stockholm tar (spectrum
sented as a graph of intensity of absorption of obtained for a solution of the sample in deuterochlo-
radio frequency (proportional to the number of roform using a Braker AM-300 spectrometer operat-
nuclei involved) against the frequency of the radia- ing at 300MHz).
tion absorbed (which depends on the chemical envi-
ronment of the nuclei). This gives rise to two
parameters: the area (integral) of an absorption sig- deuterated solvents are used so as to avoid interfer-
nal and the frequency of absorption, commonly ence by solvent protons. Deuterated water is suit-
called the chemical shift and designated as B in able for water-soluble samples.
parts per million (ppm) (see Figures 1-6). By using As little as 0.5mg of a compound (molecular
empirical correlations between chemical shift and weight -400) is sufficient to obtain a IH NMR
chemical environment, detailed structural informa- spectrum in 10 minutes, the minimum amount
tion about a compound can be obtained. For the required being dependent on the molecular weight
analysis of mixtures, the area of the absorption of the compound and the operating field of the
peaks attributable to different components allows instrument. For DC NMR the same solvents are
the relative proportion of each to be determined. used, although interference signals from the carbon
Spectra are most commonly obtained using solu-
tions of the sample in common organic solvents.
For IH NMR spectra, carbon tetrachloride or

Table 1 Common nuclei amenable to NMR analysis

Isotope Natural Sensitivity *

abundance (%) (%)

IH 99.98 100
7Li 92.58 27
liB 80-42 13
DC 1.108 0.018
5N 0.37 0.0003
170 0.04 0.001
19F 100 83
23Na 100 9.25
27Al 100 21
.10 - ...
29Si 4.7 0.03 Figure 2 Carbon-13 NMR spectrum of the acidic
31p 100 6.6 fraction obtained from modern Stockholm tar (spec-
59CO 100 28 trum obtained for a solution of the sample in deute-
rochloroform using a Braker AM-300 spectrometer
*Product of relative sensitivity and natural abundance. operating at 75MHz).

Studies in Conservation 43 (1998) 215-230 217


. tive measurements [18, 19].
~;.r1,
Figure 3 Proton NMR spectrum of the acidic frac-
tion from pitch from the wreck of the 'Mary Rose'
( J545) (conditions:asfor FigureJ).
atoms of the solvent need to be recognized. With
modern instruments, as little as Img of a com-
pound (molecular weight -400) is sufficient, but
about 24 hours would be required to accumulate a
reasonable spectrum. In general the amounts
required for specific nuclei are directly related to
their sensitivity (Table I) and are inversely related
to the molecular weight of the compound. For solid
samples, approximately 50-250mg of material are
required. When relatively abundant nuclei such as
sodium (Na), phosphorus (P) or aluminium (AI) are
studied, smaller amounts of materials will produce
satisfactory spectra.
Figure4 Carbon-J3 NMR spectrum of the acidic
fraction from pitch from the wreck of the 'Mary
Rose' (J545) (conditions: as for Figure 2).
218
E.L. Ghisalberti and I.M. Godfrey
Although there is no loss of sample in NMR
spectroscopy, the requirements for obtaining spec-
tra are such that the material form of the sample is
destroyed, with solids being either dissolved in a
liquid or powdered. One of its advantages, how-
ever, is that, because no material is consumed dur-
ing the analysis, it can be employed at the outset of
an investigation, providing information that can
guide the selection of complementary analytical
methods. In many cases, NMR can be a stand-
alone technique. Given the ready availability of I3C
NMR spectroscopy, it is important to correct the
mistaken belief that it cannot be used for quantita-
Applications
NMR spectroscopy has been used as a means of
identifying organic archaeological remains, provid-
ing information about their provenance and deter-
mining both the nature and the extent of
degradation. In addition, although the NMR tech-
nique has not yet been specifically applied to the
examination of past technological practices, inci-
dental information gleaned from comparative stud-
ies allows limited conclusions to be drawn in this
area (see below). Information of the type mentioned
above is of obvious interest and use to both conser-
vators and archaeologists.
Identification and characterization of organic
residues
With the advent of NMR spectroscopy, the charac-
terization of organic materials at the molecular
level has been simplified. A knowledge of the
cIass(es) of compound(s) contained in a sample is of
primary importance in resolving questions about its
conservation treatment, provenance and likely uses.
Since NMR spectra provide signals characteristic of
particular types of compounds, a single measure-
ment can provide data which often allow unam-
biguous identification of residues to be made. In
addition, the presence of signals characteristic of a
class of compounds often allows components of
mixtures to be identified. Integration of the charac-
teristic signals provides an estimate of the relative
proportions of these components.
Although a full description of signals which char-
acterize particular chemical groups and classes of
compounds is beyond the scope of this review,
some illustrative NMR spectra are shown. These
spectra show signals typically associated with ter-
penoid-based pine resins (Figures 1-4) and of a
complex mixture which contains a wax ester as the
Studies in Conservation 43 (1998) 215-230
Application of NMR spectroscopy to the analysis of organic archaeological materials

major component with a pine resin as a minor com-

ponent (Figures 5 and 6). These spectra were cho-
sen to demonstrate how comparison with authentic
materials can be used to identify organic materials
and also how characteristic signals can be used to
identify classes of compounds that make up a com-
plex mixture.
In this section, examples of the identification of
organic archaeological materials using primarily
proton and carbon-13 NMR are presented, together
with relevant information about the preparation of
samples for analysis and the rationale for any
deductions.
! ., ,:.
Oils, fats and waxes
One of the first published applications of IH NMR Figure 5 Proton NMR spectrum of the contents of
analysis to archaeological samples was described in a majolica jar from the wreck of the 'Batavia'
1974 [20]. A dark brown liquid contained in a glass ( 1629) (conditions: as for Figure 1). Spectrum
flask, dated sixth-fourth century BC (Syria), was reproduced with permission from AlMA Bulletin
analyzed by IH NMR to determine its nature and 14(1) (1990) 5.
composition. The sample, dissolved in deutero-
chloroform, gave a spectrum which clearly indicated
the substance to be predominantly oleic acid (or a materials resolved the question of the composition
soluble oleate salt) together with some saturated of four non-metallic document seals [21]. The aim
analogue(s). The presence of this saturated analogue was to characterize the chemicals present in these
was deduced from the characteristic signal for the seals, which have been stored in collections in
double bond protons (85) which had an area (inte- Britain since the mediaeval period, with a view to
gral) corresponding to 1.3 protons per molecule using materials of similar composition in restora-
instead of 2, expected for pure oleate. The NMR tion work. Three royal seals were selected for
spectrum closely matched that of oleic acid and analysis, those of the British sovereigns Stephen
those of calcium and potassium oleate, but lacked (1135-54 AD), John (1199-1216 AD) and William IV
signals for the glyceryl unit present in olive oil (83% (1830-37 AD), as well as one mediaeval seal of
oleic, 6% palmitic, 4% stearic and 7% linoleic acid). unknown provenance. The spectra of the chloro-
If the original sample was olive oil, it must have form-soluble material from the first two seals and
undergone hydrolysis on storage. Nevertheless, it is from the last were comparable to those obtained
significant that, despite the age of the sample, com- from both modern and ancient beeswax (c. four-
plete oxidation or polymerization of the unsaturated teenth century). This is striking confirmation that
fatty acid had not occurred. This identification of waxes possess long-term chemical and microbial
the oil sample was confirmed by subsequent
infrared and gas chromatographic analyses.
A similar analysis of a solid residue from a pil-
grim flask of the third century AD from the
Rhineland showed that 70% of the sample consisted
of a mixture of saturated fatty acids (and/or their
soluble salts) with an average chain length of 14 to
16 carbon atoms (myristic and palmitic acids) [20].
This case provides a good example of the comple-
mentarity of analytical techniques. NMR spec-
troscopy provided an indication of the class of
compound involved. This information allowed the ... .~
analyst to select GC as the next technique, and the
appropriate conditions, to determine the number Figure6 Carbon-I3 NMR spectrum of the contents
and quantitate the amounts of the individual com- of a majolica jar from the wreck of the 'Batavia'
ponents in the mixture. (1629) (conditions: as for Figure 2). Spectrum
One of the first applications of 13CNMR spec- reproduced with permission from 'AlMA Bulletin'
troscopy to the analysis of organic archaeological 14(1) (1990) 5.

Studies in Conservation 43 (1998) 215-230 219


stability. The spectrum of the later seal of William
IV, on the other hand, showed only traces of
beeswax (&60-75 for the -CH2-O-C0- group
and 0175 ppm for the -COO- group) and greater
amounts of compounds bearing a spectral resem-
blance to those known to be present in colophony
(rosin). The tell-tale resonances between 0110-150
ppm indicated the presence in this later seal of aro-
matic compounds, possibly diterpenoid, and miti-
gated against the presence of shellac (composed of
tricyclic sesquiterpenes with no aromatic groups).
The Dutch East Indiaman, the Batavia, was
wrecked in 1629 AD at the Abrolhos Islands, off the
coast of Western Australia. During excavations, a
majolica jar (broken on the wreck site) was found
to contain a solid lump of resin whose shape mir-
rored that of the original container. This material,
after air-drying, has a soft, brown and powdery
outer layer, with the inner core consisting of a dark
brown sticky substance. The NMR spectra (Figures
5 and 6) of this inner material [22] indicated the
presence of wax esters, unsaturated fatty esters and
small amounts of a pine resin which showed a num-
ber of signals corresponding to those present in the
spectra of modern pine rosins [23]. The contents of
the majolica jar appear to be similar in composition
to that found for an ointment recovered from the
wreck site of the Amsterdam (Dutch East Indiaman
beached at Hastings, UK, in AD 1748) and identi-
fied as Unguentum basi/icum by gas, liquid and thin
layer chromatography, UV and IR spectroscopy.
This ointment was 'capable of purifying and heal-
ing ulcers and which removes all splinters and also
draws out tumours' [24].
A stone axe-head, found amongst a collection of
flint pebble ballast and heavily concreted iron shot,
was raised from the HMS Sirius (AD 1790) wreck
site, Norfolk Island, and has been identified as
being of Australian Aboriginal origin. A coating on
the surface of the artifact was found to be soluble
in dichloromethane. Removal of the solvent left
IOmg of a waxy solid. Analysis by IH and I3C
NMR revealed the presence of di- and triglycerides
[22]. Clearly the axe-head residue is composed of a
mixture of fatty materials, the high degree of un sat-
uration (one for every ester group) favouring a veg-
etable or microbiological origin. Confirmation of
the origin of this residue would be best achieved by
an analysis of the sterols using GC and GC-MS.
Wood tars, pitches and bituminous materials
In a major study of tars and pitches of Tudor and
Etruscan origin, a number of analytical techniques
were used to identify the components in the archae-
ological samples [25]. Six samples of tar and pitch
from the wreck of the Mary Rose (Tudor, AD
220
E.L. Ghisalberti and I.M. Godfrey
1509-1545), a sample of pitch from an Etruscan
shipwreck (c. 600 BC)and samples of contemporary
tars were compared using GC, GC-MS, IR and IH
NMR (60MHz) spectroscopy. The results of these
analyses led to the conclusion that the Etruscan
sample and the Mary Rose tars and pitches were
similar to each other and to modern 'Stockholm
tar' (a good quality wood tar obtained by destruc-
tive distillation of Pinus sylvestris) produced in
Scandinavia or Russia. As it is known that pitch
was imported from Russia during the Tudor period,
it is probable that the Mary Rose samples came
from this source [26]. These samples were different
to other tarry materials derived from natural
sources: coal tar, peat tar, North Sea crude oil and
a tar derived from Norway spruce (Picea abies).
The remarkable preservation of the organic mater-
ial, in the case of the Etruscan sample a period of
2500 years, supports the optimistic view that ancient
organic materials are amenable to analysis and that
environmental influences do not necessarily alter the
nature of the sample in a significant way.
We also had the opportunity of examining a
sample of the Mary Rose tar (82 S1296/7: tar recov-
ered from a barrel in hold). Proton NMR
(300M Hz) and I3C NMR (75MHz) spectroscopy
were used in the analysis [22]. The predominance of
retene was inferred from signals at 0H8.5 (due to
polycyclic aromatic protons) and the cluster of sig-
nals at 0eI20-l30 (polycyclic aromatic carbons).
The other major component, dehydroabietic acid
(2), could also be distinguished. In the original
paper, the presence of these compounds was deter-
mined by the application of GC-MS. This example
shows the amount of information that can be
obtained using NMR spectroscopy, particularly in
identifying the class of compounds involved.
Nevertheless, the importance of GC-MS in the
detection of minor components and quantitation
should not be underestimated.
In addition to analyzing tar from the Mary Rose,
NMR techniques have been used in the analysis of
pitch samples from five Western Australian ship-
wreck sites: those of the Vergulde Draeck (AD
1656), Rapid (AD 1811), Belinda (AD 1824), Eglinton
(AD 1852) and Fanny Nicholson (AD 1872) [22]. All
samples, with the exception of that from the Fanny
Nicholson, have at least a pine tar component. Pitch
from the Fanny Nicholson has spectral features simi-
lar to those expected for coal tar (OH6.5-9.O,
0ell6--132). Pitch from the Belinda contains both
pine resin and components typical of those expected
for coal tar. The reason for the presence of such a
mixture is a matter for conjecture. It may have
been used to enhance the working properties of the
tar (ease of application, permeability), to alter the
preservative properties of the brew, or even to
Studies in Conservation 43 (1998) 215-230
Application of NMR spectroscopy to the analysis of organic archaeological materials

stretch the use of a dwindling resource (pine tar). It ivory, onyx, vulcanite, bakelite and epoxy resins.
may also be speculated that the combined effect of From these preliminary studies, it appears that jet
developing industrialization and declining European can be placed within the general ranks of lignite
forests are reflected in the origins of the tars and and sub-bituminous coal and that its structure con-
pitches examined. tains a large proportion of polynuclear aromatic
The similarity of the spectra obtained from sam- hydrocarbons with significant levels of quaternary
ples from the Mary Rose, the Vergulde Draeck and carbons, some of which carry an oxygen sub-
the Eglinton indicates not only a common source stituent.
for these samples (retorted pine resin from Pinus
sylvestris) but also that pitch production practices Resins
were similar over many centuries.
Two pitch samples recovered from the Rapid The importance and use of resins in ancient times
were also analyzed. One sample, used as caulking have been summarized [7, 9]. A determination of
(RP 5575/3), was scraped from planking, while the the structure and composition of resin often allows
other (RP 4287) was isolated from a stoneware jar. its origin to be deduced, thereby providing valuable
The spectra of these two samples, while clearly indi- information to archaeologists. Modern methods of
cating a pinewood origin, were sufficiently different analysis are being applied increasingly in attempts
from those of the vessels mentioned above to sug- to characterize and identify the sources of resins.
gest that they originated from a different source, NMR has not been widely used in the analysis of
possibly a pine species other than Pinus sylvestris. archaeological resins but, given the activity in
This is consistent with the origin of these vessels, aspects of resin characterization with this technique,
the Mary Rose, Vergulde Draeck and the Eglinton this is likely to change. The following example illus-
being European built and the Rapid, American trates the information which can be gained from
built. Of additional interest was the use of the the application of NMR.
NMR spectra to prove that some caulking pitch A resin was found amongst a variety of ship's
had not dripped fortuitously into the stoneware jar stores (spare clench rings, bolts, musket parts) at
when the vessel was burnt to the waterline. Intimate the Sirius wreck site. The sample was a small irreg-
contact between the acidic oak timbers and the ular lump of material (SI 436; 15mm length). A
caulking pitch induced chemical changes in the portion of this sample was readily soluble in polar
pitch (such as hydrolysis of methyl esters) which organic solvents such as acetone (propanone) and
were reflected in its NMR spectra. These changes methanol. The absence of signals between 80.5-3.0
were not evident in the spectra of the pitch from in the IH NMR spectrum, and between &0-55 in
the stoneware jar. the 13C-NMR spectrum, clearly argues for the
A combination of thin layer chromatography, IH absence of terpenoid components [22]. On the other
and 13CNMR and mass spectrometry was used to hand, both spectra contained signals attributable to
identify the presence of betulin in an early Iron Age cinnamoyl esters (3 in Figure 7), chalcone (4), fla-
wood tar excavated in Lower Austria [27]. vanone aglycones and glycosides (5). This mixture
Identification of betulin in this sample confirmed of aromatic compounds is clearly of plant origin,
the assumption that birch had been used in the but does not arise from a terpenoid-based resin
preparation of the archaeological wood tar. (dammar, copal, pine resin). Of the more common
Solid state 13CNMR spectroscopy has been used resins, this mixture more closely resembles that
to characterize samples of jet from England and found in Xanthorrhoea resin. This genus is charac-
Spain [28]. Jet, the second most important gem- teristic of the drier Australian regions. All species
stone after amber, is derived from wood and, from of this genus exude resins which are known to have
its appearance and physical properties, ranks been used as adhesives by Aboriginals for fixing
between peat and bituminous material. The NMR spear or axe heads to wooden shafts.
spectra clearly showed the presence of phenolic A new method, utilizing adsorption chromatogra-
-
functionalities (& 150) and quaternary aromatic phy followed by IH and 13CFT-NMR, was used to
carbons (& - 130).Associatedwiththeseresonances isolate and characterize ambrein from ambergris
were signals between &10-50 arising from saturated [29]. Application of this technique to an approxi-
aliphatic carbons lacking strongly electronegative mately 85-year-old sample of suspected ambergris
groups (for example oxygen and nitrogen). from the New Bedford Whaling Museum (Mas-
Importantly, the spectra of these samples bore no sachusetts, USA) demonstrated that ambrein was
resemblance to those of anthracite or bituminous still retained as a major constituent after prolonged
coal (higher coal rank) or peat (lower coal rank). storage under ambient conditions.
Furthermore, the spectra were clearly different to NMR spectroscopy has the potential to become a
those from materials derived from horn, glass, very powerful technique for the analysis of archaeo-

Studies in Conservation 43 (1998) 215-230 221

 EL Ghisalberti and I.M. Godfrey

logical resins, since it can be used to distinguish Table 2 Types of resins and classes of compounds
between resins of different botanical origin. For contributing to their composition
example, the aromatic resins originating from
Xanthorrhoea or Liquidambar species can be differ- Origin of resin Principal components
entiated from the diterpene-containing resins from
the families Coniferae and Leguminosae, from the Pinaceae
triterpene resins of the dammar and mastic type, Pinus (rosin), Abies (balsam), bicyclic and tricyclic
from shellac and from Japanese lacquer. We have Larix (Venice turpentine) diterpenes
compiled a list of resins which are of interest in
Cupressaceae
archaeology (Table 2). These have been grouped
Tetraclinis (sandarac), bicyclic and tricyclic
under the class(es) of compound(s) that dominates
Juniperus. Cupressus diterpenes
their composition. NMR spectroscopy can be used
to distinguish between groups and it may be possi- Araucariaceae
ble, by comparison with spectra of standard sam- Agathis (kauri, manila), bicyclic and tricyclic
ples, to distinguish resins from within a group. Araucaria diterpenes
With the advent of solid-state NMR techniques,
Leguminosae
resins that are insoluble in organic solvents can also Hymenaea, (Zanzibar, bicyclic diterpenes
be studied. This is illustrated by a recent study [17]
Brazil copal)
in which the structure of oriental lacquer was
Copaifera (copaibas) sesquiterpenes and
probed using solid-state NMR techniques. This lac-
quer was in use in China more than 3700 years ago bicyclic diterpenes
as a protective and decorative coating. The I3C Dipterocarpaceae
NMR spectrum of lacquer obtained from nine- Balanocarpus, Shorea, tetracyclic and
teenth- and twentieth-century artifacts supported an Hopea (dammar), pentacyclic
oligomeric structure for the cured lacquer, informa- Pistacia (mastic) triterpenes
tion not previously available by other techniques. Burseraceae
Amyris, Bursera, Canarium sesquiterpenes and
Protein-containing material
pentacyclic
Solid-state I3C high resolution NMR spectroscopy triterpenes
was applied to archaeological silk recovered from Commiphora (myrrh) pentacyclic
the coffins of three lords of the Fujiwara clans triterpenes
(twelfth century in north-eastern Japan) to deter- Boswellia (frankincense) pentacyclic
mine the mole fractions of glycine residues present triterpenes
[30]. A comparison of the fractions of glycine
Styracaceae
residues and indices adopted in the study of archae-
Styrax (benzoin) coniferyl benzoate
ological silk (cross-section of the filament and circu-
larity coefficient) with estimated temperatures of the and triterpenes
twelfth century revealed a negative correlation Hamamelidaceae
between the fractions and the temperatures and Liquidambar triterpenes and
positive correlations between the other two indices aromatic compounds
and the temperatures. From this study the authors Anacardiaceae
were able to conclude that warmer temperatures
Rhus (Japanese lacquer), urushiol (phenolics)
produce silk with a lower fraction of glycine Anacardium
residues, a higher cross-section of filament and a
higher circularity coefficient. Liliaceae
Xanthorrhoea (accroides) aromatic pigments
Provenance studies Leguminosae
Myroxylon benzyl benzoate and
Fossil resins coniferyl benzoate
Insect resin
The chemical composition of amber was first ana-
Laccifer (shellac) fatty esters and
lyzed over 100 years ago. Modern analysis has
sesquiterpenes
relied on IR spectroscopy, GC-MS and more
recently I3CNMR (CP-MAS) spectroscopy.
Fossil resins are largely insoluble in common Early NMR studies were therefore restricted to the
organic solvents because of their polymeric nature. analysis of pyrolysates of amber and, for compari-

222 Studies in Conservation 43 (1998) 215-230

---
Application of NMR spectroscopy to the analysis of organic archaeological materials

son, with samples obtained in a similar way from common palaeobotanical source, or family of
pine resin [9]. The fraction boiling at 170-180°C sources, related to Agathis (Araucariaceae) that had
from pine resin shows the presence of p-cymene (6) a broad geographical distribution during Triassic,
and possibly m-cymene (7). Oil of amber, obtained Cretaceous and Early Triassic times [39]. Slight
by destructive distillation of amber, yielded only a spectral variations, primarily in line width, were
small amount of a fraction at 160-180°C. The IH attributed to differences in age and maturity of the
NMR spectrum of this fraction lacks the prominent samples. The results of these studies provide some
signals characteristic of the isopropyl group of p- insight into the provenance, the botanical origin
and m-cymene. Although these were preliminary and the chemical structure of the samples, and the
results, they provided early evidence of the non-cor- structural changes that have occurred during aging.
respondence between the constituents of Baltic There is some debate, however, as to whether
amber and those of pine resin. changes in the intensity of the exocyclic methylene
Infrared analyses show that Baltic amber (succi- resonances can be used as a measure of fossilization
nite) can be distinguished, but this technique cannot and diagenesis and hence as a relative dating mech-
differentiate the non-Baltic fossil resins of Europe anism for amber [40].
[31]. GC-MS is suitable for determining the In this context, an issue that begs a solution is
amounts and types of compounds which are soluble the question of whether the small amounts of solu-
in organic solvents and are volatile, or can be made ble (largely unpolymerized) components reflect the
so by derivatization. Solid-state CP/MAS l3C NMR chemical nature of the original resin or whether, as
is particularly useful in providing information suggested [31], the soluble fraction represents those
about the carbon skeleton of the bulk (polymeric) constituents which cannot take part in polymeriza-
material and has been adapted to the study of solid tion processes. The observation that exposure of a
samples from European, American, Australian and freshly cut surface of amber leads to noticeable
New Zealand sites [31-39]. changes is pertinent [7]. Also interesting are the
Studies using this technique have revealed that 12 findings obtained by application of GC-MS and l3C
samples of Mexican ambers collected from two NMR (CP/MAS) on a fossil resin associated with
sites, although having different colours, gave essen-
tially the same spectra [36]. These, in turn, showed
small differences when compared to Dominican
ambers, themselves quite variable, and distinct dif-
ferences to Baltic ambers. A wide range of Baltic
ambers produce reliably constant NMR spectra
showing absorption resonances at 8170-190 (attrib-
utable to -COO- groups), at 8110 and 150 2. Dchydroabictic acid
1.Rctenc
(C=CH2), 8128 and 140 (di- and trisubstituted
double bonds), 860-70 (oxygen substituted carbons) R,O
and 810-40 (three main peaks due to saturated car-
bons). Differences between these and more AIO 0
southerly ambers could be detected and rational- 4. Chalcone ~Iructure
ized. group
(R =OH. OOly or OCH))
(R. =H, ooly or OCH)
3. Cinnamoyl
(R=OH or OCH,J
Apart from this fingerprinting, more important
facets of the structure can be deduced [31, 33]. For

W
instance, the spectra obtained from the succinite 1R
R'O
type appear to be consistent with the presence of a I'"h 0 ~
labdane diterpene (bicyclic) precursor (8), whereas
rumanite and similar types appear to be derived RIO 0

from a tricyclic abietane diterpene (9). Differences 5. F!avmwnc structure 6. [J-Cymenc 7. ",>Cymenc
between these ambers and those of New World (R = 011. OGly or OCH)

amber have also been noted by NMR spectroscopy

[37]. l3C NMR was used to show that Dominican
amber (20-35 million years old) was produced by a
species very closely related to the African plant
species Hymenaea verrucosa. In contrast, Mexican
amber (20-24 million years old) is different to both 8. A labdane dilcrpcnc 9. An abiclanc dilcrpc:nc 10. A guaiacyl unh
(R=.IIk.yl or H)
[33]. A recent l3C NMR study of older fossil resins (communic <1cid) (abiclicilcid)

from Alaska, Canada, the United States, Green-

land, Europe and south-western Asia suggested a Figure 7 Structural formulae.

Studies in Conservation 43 (1998) 215-230 223


Dacridiumites mawsonii, an extinct species of
Podocarpaceae occurring on the South Island of
New Zealand during the Bortonian Age (Middle
Eocene) [41]. Whereas dehydroabietic acid (2) was
the main constituent in the solvent extractable por-
tion of the fossil resin, it did not appear to con-
tribute to the structure of the bulk polymer matrix.
The evidence for this conclusion relies largely on
the absence of a signal at M8, in the spectrum of
the latter, which was evident in the spectrum of (2)
and was assigned to the quaternary carbon at C4.
The absence of this in the spectrum of the polymer
is not surprising since the carboxylic acid group
involved in polymerization is attached to this car-
bon. In other words, the chemical environment
around C4 would be expected to be greatly differ-
ent in the polymerized species and in the unpoly-
merized material. It seems probable that fossilizing
resins are not subjected to the breakdown that
occurs in the early stages of coalification and there-
fore retain the composition of the original resin
[42].
Bituminous materials
In an investigation of the source of Babylonian
building asphalt, NMR spectroscopy and thermo-
gravimetry were used as the main analytical tools
[43]. Asphalt samples from three locations,
Babylon, Heet and Qayarah, were dissolved in
deuterochloroform and analyzed by IH and JJC
NMR spectroscopy. From the spectra obtained,
average structural parameters were calculated and
compared. The results indicated that the most prob-
able source of Babylonian building asphalt was the
Heet location, 200km north-east of Baghdad.
Determination of extent of deterioration
Wood
Since antiquity, wood has been the material of
choice for the fabrication of shelters, tools and
objects of art. Since wooden artifacts provide a
record of human activity and technology through
the ages, the characterization and preservation of
archaeological wood have attracted wide interest
[44].
Until recently, methods of wood analysis relied
on extractive techniques in which lignin, cellulose
and resin fractions were extracted with aqueous and
organic solvents [45]. This is regarded as unsatisfac-
tory because the composition of any fraction is
method dependent. High resolution solid state JJC
NMR is a particularly useful method for the com-
prehensive analysis of whole wood without recourse
to extraction or degradation. It can also be applied
224
E.L. Ghisalberti and I.M. Godfrey
to the study of wood processing and for distin-
guishing woods of different species [46]. The follow-
ing is a summary of recent applications of the
technique to archaeological and non-archaeological
samples.
Samples of a tree of the fossil gymnosperm
Phyllocladus trichomanoides, buried by a volcanic
eruption at Taupo, New Zealand, 2000 years ago,
were analyzed to determine whether micro-ecologi-
cal transformations had occurred and to determine
if physiological differences were apparent between
heartwood and sapwood [46]. The results obtained
showed that resonances due to lignin are present in
greater abundance in the heartwood, whereas the
carbohydrate (&105, 75, 66) content is greater in the
sapwood. Furthermore the lignin in both woods
appeared to be mainly based on guaiacyl units (10)
(&149, 134, assigned to non-protonated carbons by
dipolar dephasing), parts of which were crosslinked.
Similar examination of the inner and outer sections
of 450-year-old wood from a pylon under the old
city of Rotterdam disclosed significant differences
in carbohydrate content [47]. In contrast, inner and
outer sections from 10,000-year-old spruce wood
(Michigan, USA) had similar carbohydrate content.
JJC NMR spectroscopy has been applied to the
study of the steps that lead to coalification [48, 49].
Analysis of a series of decomposed and coalified
woods that increase in degree of coalification from
peat to lignite and higher ranks revealed chemical
structural trends that allow hypotheses to be made
about the sequence of events leading to the defunc-
tionalization of lignin [48].
Further studies, on non-archaeological samples,
have utilized JJC NMR spectroscopy to determine
the extent and nature of degradation of spruce and
birch by brown and white rot fungi [50, 51]. The
brown rot fungus was shown to preferentially
attack the carbohydrate components, removing
hemicelluloses at a faster rate than cellulose and
altering the lignin by a loss of methoxy groups.
Differences were noted between the effect of brown
rot fungi on spruce and birch, with decayed spruce
showing an increase in vanillic acid structures and
a-carbonyl moieties and birch suffering cleavage of
lignin [3-0-4 linkages rather than demethylation
[51]. White rot fungi were able to degrade exten-
sively both the carbohydrate components and the
lignin. A quantitative analysis revealed that spruce
lignin was degraded to 77% of its weight by brown
rot, and to 39% by white rot fungi [50].
Solid-state JJC NMR, Fourier transform infrared
(FTIR) spectroscopy and pyrolysis GC-MS tech-
niques have been used to analyze wood samples
from five historic Indian Ocean shipwrecks, includ-
ing the Dutch East Indiamen Batavia (1629) and
Vergulde Draeck (1656) and the more recent colo-
Studies in Conservation 43 (1998) 215-230
Application of NMR spectroscopy to the analysis of organic archaeological materials
nial wreck, the Day Dawn (1886) [52]. The results
from all three techniques strongly support each
other. Not surprisingly, the outermost parts of the
wood, those in more intimate contact with the
marine environment, were more severely degraded.
Varying degrees of carbohydrate loss occurred, with
the inner regions of the samples relatively un-
affected. Samples from one wreck, the James
Matthews (1841) which is located at an anaerobic
site, appeared to have undergone little or no degra-
dation, unlike the samples obtained from aerobic
sites. There appeared to be no correlation between
the age of the ships and degradation of the recov-
ered wood.
Analysis of the carbohydrate content of these
samples (the % carbon assigned as O-alkyl in the
NMR spectra) demonstrated that an inverse rela-
tionship exists between these measures and their
respective maximum water contents. As the latter
measure is commonly used to guide the choice of
conservation treatment, NMR analysis of wood has
the potential not only to provide detailed informa-
tion regarding the chemical processes that have
taken place upon prolonged immersion, but also to
~uide the actions of conservators.
The application of I3C solid-state NMR to the
analysis of two recently excavated samples of wood
indicated that the samples had been subjected to
quite different modes of degradation [53]. NMR
analysis of a sample of Eucalyptus tereticomis,
recovered from 17 metres below the seabed in
Botany Bay, New South Wales (radiocarbon date
of 8800 BP), demonstrated significant depletion of
lignin from the outer layers, indicating that the
sample had been subjected to extensive weathering
prior to burial. This conclusion was confirmed
when examination of a transverse surface revealed
the presence of internal checks caused when the
sample was naturally seasoned.
On the other hand, an as yet unidentified wood
sample recovered from a mineral sands deposit at
Beenup in the south-west of Western Australia
(estimated age of 10-30 million years) was found to
contain only lignin, all of the carbohydrate material
having been lost from the sample. As the most
commonly used conservation treatment for water-
logged wood uses polyethylene glycol (PEG), and
'elies on the formation of hydrogen bonds between
PEG and the substrate, the lack of hydrophilic car-
bohydrate in the Beenup samples may impact on
the success of any PEG treatment of this material.
Proton NMR imaging of three-dimensional
objects is an application of considerable promise. In
this technique, images are obtained of very thin
'slices' of relevant sections of an object without
actually cutting the sample. This image, which
maps the distribution of proton-containing species,
Studies in Conservation 43 (1998) 215-230
allows the distribution of water to be determined,
providing information regarding the internal struc-
ture and level of deterioration of a sample. Initially
this non-invasive technique was applied to the study
of human remains, with very brief reports outlining
approaches to the analysis of an Egyptian mummy
[54] and an Iron Age body recovered from a peat
moss bed in Cheshire [55]. In the latter case NMR
imaging revealed that although most of the internal
organs had disappeared, the stomach and last meal
were retained.
Investigations of the all-proton NMR imaging of
waterlogged wood demonstrated that this non-
destructive technique has promise both in assessing
wet archaeological wood and in monitoring the
ingress of consolidants into the wood structure [56,
57]. Unfortunately, degradation of the NMR image
occurs in the presence of paramagnetic materials
such as iron(II) and iron(III) salts, materials that
are often incorporated in wood recovered from
shipwreck sites. Although causing problems with
imaging, the effect of iron salts on the image can be
used diagnostically to demonstrate their presence
and also to monitor the effectiveness of iron
removal methods.
In order adequately to investigate the penetration
of consolidants into the wood structure it was nec-
essary to mask the protons present in water by iso-
topic substitution. When the proton contribution
from water was masked, good polymer selective
images were obtained, allowing the ingress of con-
solidants to be monitored in modern balsawood
model systems. It was demonstrated that conductive
vessels were the preferred access route for poly-
ethylene glycols with molecular weights up to 1500
and that polymer penetration was not uniform,
with high concentration patches occurring around
the most accessible routes. At this stage the process
cannot be applied to wet archaeological samples.
The replacement of water by deuterium oxide is
very expensive and removal of water by drying
prior to impregnation would be damaging.
Bone and ivory
Numerous studies have been directed towards the
analysis and characterization of fossil and archaeo-
logical bone, the majority focused on answering
questions regarding bone diagenesis, and suitability
for use in dating, genetic or dietary/habitat studies.
Although NMR techniques have been applied to
modern bone and its organic and inorganic compo-
nents [58-61], until recently these techniques had
not been applied to archaeological bone. A recent
study of fossil bone, however, utilized both X-ray
diffraction and NMR spectroscopy to identify the
carbonate environments associated with two of the
225

mineral components of the sample, calcite and a
component containing carbonate in an apatitic
environment [62]. NMR spectroscopy was also able
to detect the small quantities of organic material
which remained in the original bone matrix.
Despite the occurrence of ivory in a variety of
archaeological contexts and its importance as a
material widely used both in the fabrication of
tools, ornaments and art objects and for trade,
there have been few investigations into the nature
and extent of the degradation of this material
[63-65]. No NMR studies have been reported
regarding the analysis of archaeological or historic
ivory.
Studies involving NMR, FTIR, X-ray diffraction
and elemental analyses of ivory recovered from the
wreck of the Dutch East Indiaman, the Vergulde
Draeck (1656), revealed interesting patterns of degra-
dation [66]. 31p solid-state NMR studies demon-
strated, as expected, that the inner regions of the
inorganic matrix were less degraded than the outer
regions. Interestingly, the application of J3C solid-
state NMR techniques to the same samples revealed
that the organic component of the ivory (collagen)
had been partially retained in the outermost layer
but completely lost from the core. As collagen pro-
vides the fibrous network which permeates the struc-
ture, its loss from regions within the ivory matrix
has obvious conservation implications.
NMR analyses of the type presented in this sec-
tion add to our knowledge of the degradation of
wood, bone and ivory under different environ-
ments. This knowledge is important if proper con-
servation of these materials is to be achieved. In
turn, this should ensure that the maximum amount
of archaeological information is retained during
treatment.
Concluding remarks
From the applications given above it is clear that
NMR spectroscopy is a powerful addition to the
range of techniques available for the analysis of
organic materials of archaeological interest.
The capability for examining samples in the solid
state should lead to more applications in those
cases where sufficient material is available. This
technique is particularly valuable for the study of
archaeological wood, bone, ivory, leather, and
materials containing extractable and non-
extractable residues [5].
The amount of information which can be
obtained from an NMR spectrum will be greatly
increased when databases of standard spectra are
assembled and become available. These would be
particularly useful in the analysis of archaeological
226
E.L. Ghisalberti and I.M. Godfrey
resins. The study of aging processes, particularly
those involving resins and varnishes [67], is another
area to which NMR spectroscopy could be applied.
In the last few years, NMR spectroscopy has
been applied to the analysis of geological minerals,
clays, ceramics and glasses, and even soil, plant and
microbial remains [68], all materials of some rele-
vance in archaeological studies. A recent study used
proton NMR spectroscopy to determine the degree
of hydration associated with a crystalline efflores-
cence which had been found on an Egyptian lime-
stone relief [69]. This efflorescence was identified as
a new crystalline salt that had not been previously
characterized.
NMR microscopy (high resolution imaging) is a
technique in which high quality two-dimensional
images of a solid object can be produced, the image
obtained being essentially a map of the distribution
of a particular nucleus in a solid object. This
emerging technique is finding numerous applica-
tions in materials science [70, 71] and can logically
be expected to extend to areas of interest to conser-
vators, conservation scientists and archaeologists.
Acknowledgements
The authors wish to thank the staff of the
Department of Maritime Archaeology, Western
Australian Museum, the Australian Bicentennial
Authority and the Norfolk Island Government for
providing pitch and resin samples (Batavia,
Vergulde Draeck, Eglinton, Rapid, Fanny Nicholson
and Sirius samples) and Professor Eglinton and Dr
Robinson (University of Bristol, UK) for supplying
a tar sample from the Mary Rose. The cooperation
of Dr Byrne (University of Western Australia) in
running the NMR spectra is gratefully acknowl-
edged.
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Authors
EMILIO GHISALBERTIobtained a PhD (1967) in
chemistry from the University of Western Australia.
After a period of post-doctoral work in Italy and
England he returned to the University of Western
Australia (1970) where he is currently an associate
professor in chemistry. His research interests have
focused on the chemistry and biosynthesis of nat-
ural products. More recently he has undertaken
research topics involving microbial interactions,
plant/pest interactions, natural pesticides and
ethnopharmacology. The potential of nuclear mag-
netic resonance techniques has sparked his interest
in archaeological and conservations topics. Address:
Department of Chemistry, University of Western
Australia, Nedlands. WA 6009, Australia.
IAN GODFREYobtained a BSc (1974) and PhD
(1981) in organic chemistry from the University of
Western Australia and a Diploma of Education
(1978) from the then Secondary Teachers College of
Western Australia. After teaching and lecturing for
eight years he was appointed curator of organic
materials in the Department of Materials Conser-
229
 EL Ghisalberti and I.M. Godfrey

vation of the Western Australian Museum (1987). toric Antarctic buildings. Address: Western
His research interests are the analysis and treatment Australian Museum, Department of Materials
of waterlogged organic materials and the develop- Conservation, WA Maritime Museum Building, Cliff
ment of methods for the in situ conservation of his- Street, Fremantle, WA 6160, Australia.

Resume-L'utilisation de la spectroscopie de resonance magnetique nucleaire (RMN) est susceptible de

fournir aux scientifiques, restaurateurs et archeologues, des resultats interessants en ce qui concerne ['analyse
d'objets archeologiques organiques. Cet article met en evidence ['utilite de la technique de RMN et l'elargisse-
ment possible de son champ d'application. On decrit bril?vement la technique et sa portee. Sont presentes
egalement des derails relatifs a son utilisation pour identifier la nature et la composition de residus organiques,
afin d'aider a determiner leur provenance, ainsi que son application pour ['analyse et la caracterisation des
degradations des materiaux archeologiques.

Zusammenfassung-Der vorliegende Bericht beschreibt die magnetische Kernresonanzspektroskopie, die als

Verfahren bei der Untersuchung organischer archiiologischer Materialien Restauratoren, Konser-
vierungswissenschaftlern und Archiiologen wertvolle lnformationen liefern kann. Die Autoren stellen die
Technik und die Vielzahl der Anwendungsmoglichkeiten vor. Der Nutzen liegt in der Moglichkeit der
ldentifikation organischer Bestandteile, der Hilfe bei der Bestimmung der Herkunft solcher Proben sowie der
Beurteilung des Grades der Zerstorung archiiologischer Materialien.

ResumeJ}-La aplicacion de espectrometria de resonancia nuclear magnerica (NMR) al anrilisis de materiales

arqueologicos organicos puede aportar valiosa informacion a los cientificos de la conservacion, conservadores y
arqueologos. En este articulo la utilidad de la tecnica NMR y la amplitud de sus aplicaciones son estudiadas.
Se describen brevemente la tecnica y su aplicacion. Se presentan, asi mismo, detalles del uso de la espec-
trometria NMR con el fin de determinar la naturaleza y composicion de residuos organicos, con la intencion
de conocer la procedencia de tales residuos y su aplicacion al analisis y determinacion del grado de deterioro
de [os materiales arqueologicos.

230 Studies in Conservation 43 (1998) 215-230