Richards Et Al

8/12/2019 Richards Et Al

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International Journal of OsteoarchaeologyInt. J. Osteoarchaeol.13: 37 45 (2003)Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/oa.654

Sulphur Isotopes in PalaeodietaryStudies: a Review and Results from aControlled Feeding Experiment

M. P. RICHARDS,a* B. T. FULLER,b,c M. SPONHEIMER,d,e T. ROBINSONf

ANDL. AYLIFFEe

a Department of Archaeological Sciences, University of Bradford, Bradford, West

Yorkshire, UKb Research Laboratory for Archaeology and the History of Art, University of Oxford,

Oxford, UKc Department of Biochemistry, University of Oxford, Oxford, UKd Department of Biology, University of Utah, Salt Lake City, Utah, USAe Department of Geology & Geophysics, University of Utah, Salt Lake City, Utah, USAf Department of Animal and Veterinary Sciences, Brigham Young University, Provo,

Utah, USA

ABSTRACT Recent advances in mass spectrometry now allow relatively routine measurements of sulphurisotopes (34S) in small samples (>10 mg) of tissue from archaeological human, plant, and faunalsamples. 34S values of human and faunal bone collagen can indicate residence or migrationand can provide palaeodietary information. Here we present a review of applications of sulphurisotopes to archaeological materials, and we also present preliminary results from one of thefew controlled feeding experiments undertaken for sulphur isotopes. This study indicates thatthere is relatively little fractionation (1) between diet and body protein (keratin) 34S values

for modern horses on a protein adequate C3 plant diet. In contrast, horses fed a possible lowprotein C4 feed have a diet to hair fractionation of+4 that could be the result of the input ofendogenous sulphur from the recycling of body proteins. Copyright 2003 John Wiley & Sons,Ltd.

Key words:stable isotopes; sulphur; migration; palaeodiet; collagen; keratin

Introduction

There have been relatively few applications ofsulphur isotopes to archaeological organic mate-rial, such as bone collagen or hair keratin. Thisis due to the time-consuming laboratory prepara-tion and large sample sizes traditionally required.Recent advances in mass spectrometry now allowmeasurement of sulphur isotope values in rela-tively small organic samples with much simplersample preparation methods, permitting routine

* Correspondence to: Department of Archaeological Sciences,University of Bradford, Bradford, West Yorkshire BD7 1DP, UK.e-mail: [email protected]

sulphur isotope analysis in conjunction with anal-

ysis of carbon and nitrogen isotopes (Richards

et al., 2001).

The stable isotope composition of sulphur(34S) in human and faunal tissues reflects the34S

values of foods consumed. Local food web 34S

values are controlled by the34S values of under-

lying local bedrock, atmospheric deposition, and

microbial processes active in soils. Therefore, like

strontium and lead isotopes in bone mineral (Sealy

et al., 1995; Price et al., 2000), human and faunal

sulphur isotope values can be used to establish

the local food web sulphur isotope values. These

Copyright 2003 John Wiley & Sons, Ltd. Accepted 25 September 2002


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38 M. P. Richardset al.

values can then be used to identify local and extra-local (migrants) individuals in a region, providing

the extra-local individuals were from a localitywith sufficiently different environmental34S val-ues. Additionally, 34S values have the potential toprovide palaeodietary information supplementaryto 13C and 15N measurements perhaps indi-cating the consumption of freshwater resources.Below we review the environmental factors thatinfluence 34S values, as well as review the fewmeasurements of34S in human tissue.

There are few published controlled feedingexperiments that have measured 34S fraction-ation between diet and consumer tissue 34S

values for mammals. Clearly, this fractionationmust be established before 34S can be used totrack migration, residential mobility or diet. Wereport here preliminary results from a controlledfeeding experiment where 34S values of horsehair and diet were measured for two individualsthat were fed C3and C4 diets.

Sulphur isotopes in plants and animals

There are four stable isotopes of sulphur:32S(95.02%), 33S(0.75%), 34S(4.21%), and36S(0.02%) (Trust & Fry, 1992). The ratio betweenthe two most abundant isotopes, 32S and 34Sis defined as the 34S value which is measuredrelative to the meteorite standard Canyon DiabloTroilite (now the Vienna CDT) (Coplen &Krouse, 1998). Sulphur is an abundant element.There are two significant isotopically uniform Sreservoirs: the earths metallic core, with a 34S

value near 0, and oceanic sulphate (SO4),

with a34S value near +20. Sedimentary rocksare the largest reservoir of sulphur near theearths surface, but isotopic values for sedimentary

sulphur are highly variable depending on rocktype and age (Faure, 1977). Plants receive themajority of their sulphur through their roots assulphate, which is derived from the weatheringof local geological formations. Plants can alsoobtain sulphur from the atmosphere by wet or drydeposition. Wet deposition is the incorporationof sulphur falling to earth in water droplets fromsea spray or acid rain (H2SO4), whereas drydeposition results from the uptake of SO2 gas.The amount of atmospheric sulphur absorbed

varies depending upon location and plant species,but in some cases 25 to 35% of the plants sulphur

can be obtained in this way even if there areadequate amounts of soil sulphate (Brady & Weil,1999). Once obtained by the plant, most sulphuris stored in organic molecules such as amino acidsand sulphate esters. The 34S value of plants is

variable depending upon location and geology,with values falling between the extremes of 22to +22 (Peterson & Fry, 1987).

In animals, sulphur is an essential element forgrowth and survival that must be obtained fromthe diet. It is predominantly found in the aminoacids of cysteine, methionine, and taurine as

well as in various vitamins and cofactors suchas thiamine, vitamin B, biotin, and coenzyme A.In modern and archaeological bone, sulphur isdistributed throughout the inorganic matrix ascalcium sulphate(CaSO4)and within the proteincollagen as methionine with a frequency of fiveresidues per 1000 (Eastoe, 1955). The sulphurin hair is primarily derived from the amino acidcysteine (112 residues per 1000) although thereis a small contribution from methionine (fiveresidues per 1000) (Valkovic, 1977).

There are significant differences among the34S values of plant and animal specimens

from freshwater and marine ecosystems. Modernmarine organisms have34S values close to+20whereas freshwater organisms can have a widerange of 34S values, between 22 to +22(Peterson & Fry, 1987; Mekhtiyeva et al., 1976).The wide range of freshwater 34S values is largelydue to the reduction of sulphate ions (SO4

) tohydrogen sulphide (H2S) by anaerobic bacteriathat dwell in the sediments of rivers and lakes(Faure, 1977). These anaerobic bacteria generateenergy for survival by using sulphate in placeof molecular oxygen as an electron acceptor

during the oxidation of organic matter. Sinceit is thermodynamically easier to break a 32SObond versus a 34SO bond, the final H2S that isexcreted is significantly depleted in 34S. In somecases this 34S depletion can reach 50 dependingupon season and environmental conditions suchas moisture, aeration, temperature, and pH(Faure, 1977).

This difference between freshwater and marine34S values has been used in a number of modernecological studies, for example to discriminate

Copyright 2003 John Wiley & Sons, Ltd. Int. J. Osteoarchaeol.13: 37 45 (2003)


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Sulphur Isotopes in Palaeodietary Studies 39

between lake dwelling and migratory ocean fishthat co-existed in freshwater lakes in northern

Canada (Hesslein et al., 1991). A food webanalysis of modern fauna from the CanadianArctic was able to distinguish between continental(terrestrial) and coastal (marine) based diets usingsolely 34S values (Krouse & Herbert, 1988).Terrestrial animals and birds had values lessthan +10 whereas mammals from more marineenvironments, such as polar bears, had valuesranging between +16 and +18 reflecting theirconsumption of seals.

While these studies show the potential ofusing sulphur isotopic analysis in (palaeo)dietary

research, it should be noted that 34

S valuesdo not necessarily reflect consumption of marineprotein, as they can also register the proximityof the dietary protein source to the sea. This isa result of the so-called sea spray effect, whichcan carry sulphur particles inland and cause thecoastal soil 34S values to be similar to those of theocean (Wadleigh et al., 1994). In some cases thissea spray effect may only extend a few kilometersinland from the ocean (Robinson, 1987). In othercases, entire islands (e.g., New Zealand) can havesoil 34S values related to those of marine water(Kusakabe et al., 1976). In order to help distinguishbetween the consumption of marine resourcesand proximity to the ocean in an archaeologicalpopulation, 13C and 15N measurements mustbe made in conjunction with34S values.

The field of study where sulphur isotopicanalysis may have its greatest impact is in thedetection of residence and migration within apopulation. Geochemical research indicates that34S values are heavily dependent on geographicallocation, which is a reflection of the localgeology and atmospheric sulphur compositionof the area (Faure, 1977; Krouse & Herbert 1988;

Brownlow, 1996). This geographically distinct34S isotopic signature was used in conjunctionwith 15N measurements to assign the originof milk samples from alpine regions in Europe(Rossmann et al., 1998). The study found thatthe 34S values obtained from the milk proteincasein were similar to the 34S values of soilsfrom the area in which the cattle were grazed. Inaddition, cattle that had grazed on soils that weresimilar in geological age had similar milk 34S

values. Krouse & Herbert (1988) also observed

a large variation in 34S from migratory moosein the Canadian Arctic, which they attributed to

variations in the local geology along the migrationroutes. Katzenberg & Krouse (1989) conducted astudy of the potential of 34S and 13C isotopesto discriminate between modern humans from

various geographical locations. They obtainedhuman hair samples from five different countries(Brazil, India, Japan, Canada, and Australia) andplotted the 34S values versus the 13C values.While there was some overlap in the values, it waspossible to distinguish among the individuals fromdifferent geographic regions, and they arguedthat this type of analysis held promise as a

tool for identifying geographic origin in humanforensic studies.

Applications of sulphur isotopes toarchaeological material

There have only been a handful of applicationsof sulphur isotope analysis in archaeology ascompared to the large body of data fromcarbon and nitrogen isotope analysis. Whilethe importance of the information obtained(or obtainable) from 34S measurements was

realized by H.R. Krouse and others 15 yearsago (Krouse et al., 1987), the large sample sizeneeded and laborious methods employed fororganic samples limited the use of sulphur inarchaeological studies. In the past few years,many of these problems have been solved andit is now possible to conduct isotopic sulphuranalysis by continuous flow isotope ratio massspectrometry (CF-IRMS) (Giesemannet al., 1994;Morrison et al., 2000). Themethod entails minimalpreparation (samples are placed in tin boats andcombusted) and the procedure is automated so

that many measurements can be made in a singlerun. In addition, due to the decrease in thenumber of extraction procedures, there is lesschance for fractionation during pretreatment. Thegreatest advantage for archaeological research isthe reduction in sample size to ca. 10 mg ofpurified bone collagen for a single measurement.

Using traditional methods of sulphur isotopeanalysis, Mackoet al. (1999) measured34S valuesof hair (which has a much higher S contentthan bone) from Egyptian and South American



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mummies. They found significant differences in34S values from inland Egyptian and coastal

South American mummies. The majority of thecoastal South American mummy samples had high34S values (ca. 15), which could reflect both amarine diet, as well as a coastal location (due tothe sea spray effect). Analysis of 13C and 15N

values confirmed that high 34S values were due atleast in part to consumption of marine food. Theinland Egyptian samples had34S values less than10, which they argue is indicative of their moreinland location. A similar pattern of inland/coastaldifferences in South American mummy sampleswas found by Iversonet al. (1992).

For archaeological bone collagen (rather thanhair), the first34S values were reported by Leachet al. (1996) on a collection of human and animalremains from several South Pacific archaeologicalsites spanning the last 1000 years in age. Thispioneering study found a definite marine 34Ssignal in humans and fauna that subsisted onmarine protein and resided at coastal locations.They also used34S values to distinguish betweena European who lived and died on the South Islandin the 19th century (+2), and a local Mororiwho lived and died on the Chatham Islands (+14to +17), thereby confirming the possibility

of detecting immigrants. In addition, this studydemonstrated that there is sufficient sulphur inarchaeological bone collagen for isotopic analysis,and that the loss and degradation of methioninehad not compromised the integrity of the sulphurisotopic composition.

The first measurements conducted on smallsamples of ancient bone collagen from Europeanarchaeological sites were by Richardset al. (2001).Using a Europa continuous flow isotope ratio massspectrometer, 27 collagen samples ranging in agefrom ca. 6500 BC to 1300 AD were analysed

from nine archaeological sites. The samples wereselected to determine how bone34S values wererelated to archaeological and isotopic indicationsof marine food consumption. The results showedthat all of the collagen samples obtained fromcoastal regions had a clear 34S marine signaturealthough only some of these had a marine 13Csignal (indicating marine food diets). These datafurther support the notion that for individualsliving close to the ocean, 34S values alone are notreliable indicators of marine protein consumption

(unless coupled with 13C or 15N measurements)as a result of the sea spray effect. Measurements of

human bone collagen samples from inland regionsof England and the Ukraine did not have 34Smarine signals but were consistent with predictedlocal sedimentary sulphate values.

In addition to archaeological human collagenmeasurements, 34S values were obtained frommodern faunal collagen collected from aroundthe UK. The modern samples from England hadlow 34S values that were attributed to anthro-pogenic sulphur pollution. The only modern34Smeasurements that resembled those from archae-ological materials were from less polluted areas of

coastal North Wales and the interior of northernScotland. Thus, it seems that archaeological mate-rial could provide an effective source from whichto obtain baseline 34S measurements for thedetermination of the amount of sulphur pollutionwithin a region.

Sulphur isotope fractionation inmammals

It is necessary to establish the degree, if any,of fractionation between dietary and body tissue34S values, as well as an understanding of thefractionation when geological sulphur enters thebiosphere. In marine, freshwater, and terrestrialplants, there is only a slight isotopic fractionationduring sulphate incorporation and reduction.Plants are typically depleted in 34S by ca.1.5 relative to their sulphate sources (Trust& Fry, 1992). Like plants, there seems to belittle isotopic fractionation of sulphur in animals,although there are few published studies onthis topic. Feeding experiments conducted ongypsy moth caterpillars found a trophic level

shift in 34

S of +1.3, and brook trout hada similar 34S enrichment of +1.2 to +1.4(Petersonet al., 1985). In a study of muscle tissueand hair from bears and other animals fromYellowstone National Park and British Columbia,Kesteret al. (2001) observed a slight depletion in34S between consumer and food source. To datethere has only been one controlled feeding studythat has measured the 34S isotopic fractionationbetween the diet and tissues of mammals. Thisstudy used pigs fed isotopically known diets



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(acorns or feed), and measured the liver 34Svalues from these animals (Gonz alez-Martinet al.,

2001). The results indicated that there was littledifference between dietary and liver34S values.

Katzenberg & Krouse (1989) have published theonly studythat attempts to examine the amount offractionation between diet and tissue in humans.They measured animal feed, meat, milk, eggsand human hair from a Hutterite community inCalgary, Canada. Since Hutterites tend to maketheir own food rather than consume processedfood, they were viewed as an approximate closedsystem. The 34S values from animal feed andhuman food items ranged from 0 to+5, whereas

the human hair samples had values near +3.While the exact magnitude of the fractionationwas not obtained, this study demonstrated that itwas small in comparison to the34S values of thediet. In addition, analysis of kidney stones andother tissue samples from humans such as hair,nails, blood and urine found that there was little34S variation (1 to 2) among tissues of thesame individual (Krouseet al., 1987).

Sulphur isotope fractionation inmodern horses on a controlled diet

Here, we present the first results from our on-going study to measure the degree of diet-tissue34S fractionation in mammals in a controlledfeeding experiment, undertaken as part of thelarger Stable Isotope Biology (SIB) project, whichis a joint venture of Brigham Young Universityand the University of Utah. For this study wefed two adult horses (the male Dandy and thefemale Sassy) three different controlled hay dietsover a period of nine months. The horses werehoused in a covered enclosure and had no access

to other food sources during the period of theexperiment. Temperature changed dramaticallyduring the experiment, but was not correlatedwith stable carbon, nitrogen, or sulphur isotope

values (Sponheimer, unpublished data). Neitherhorse was reproductively active during the courseof the experiment. Hay and water were providedad libitum. The study began with both horses on alocal Utah grass hay diet (Bromus inermis) , a C3plant(34S 10.8) with 9% crude protein. Theyonly stayed on these initial diets for seven weeks,

however, as they had been consuming a similarlocal hay for the previous several years, so they

were largely equilibrated with the diet before theadvent of the study. After this acclimation period,the horses were switched to an isonitrogenousgrass hay from near the California/Mexico border(Cynodon dactylon), a C4plant, that had a different34S value (34S 1.9). They remained onthis diet for a period of 21 weeks, which was morethan ample time for diet-hair isotope equilibrationin nitrogen (Sponheimeret al., 2002). Both horseswere then switched to a high-protein (19% crudeprotein) local Utah alfalfa hay (Medicago sativa),a C3 plant, with a sulphur isotope composition

that was nearly identical to that of the initial localhay(34S 10.5). They remained on this dietfor another 19 weeks until the completion of theexperiment, at which point tail hair was obtainedfrom each individual.

While many strands of tail hair were obtainedfrom each individual, we only present data fromone strand for each individual in this paper. Thetail hairs of Dandy and Sassy were pre-treatedwith a 2 : 1 chloroform:methanol soak for 6 hat room temperature, after which the sampleswere rinsed in deionized water and then dried atapproximately 40 C overnight. Individual hairs

were cut into 1.5 cm sections starting at the skinend (sample number 1) for 34S measurement(Table 1). Sample pretreatment was undertakenat the stable isotope laboratory at the Departmentof Archaeological Sciences, University of Brad-ford, UK, and isotope measurements were madeat Iso-Analytical, Cheshire, UK. Each hair strandhad approximately 4 5% sulphur, and the repro-ducibility on seven measurements of the standardIAEA-S and seven measurements of the standardNBS 1577A were between 0.20.3(1).

As can been seen in Figure 1, there are clear

trends in both horses. The data from Dandy areclearer, because Dandys hair grew more slowlyand all three diets are in evidence. In contrast,the 18 cm analysed for Sassy were not sufficientto capture the initial experimental diet, thus onlythe final two diets are in evidence. For Dandy, forhair sections older than section nine (section tenand greater), when the experiment began, we cansee a clear equilibration with local hay34S. Afterthis section there is a sharp decrease in 34S,indicative of the change from the localBromushay



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Table 1. 34S and %S values for tail hair segments of two horses, Dandy and Sassy as well as three types of feed.Errors on the 34S measurements are 0.3(1)

Sample number Sulphur content(%)

34S()

Sample number Sulphur content(%)

34S()

MSS Dandy 1 4.74 6.00 MSS Dandy 30 4.26 8.45MSS Dandy 2 4.78 9.15 MSS Dandy 31 4.31 8.62MSS Dandy 3 4.45 8.97 MSS Dandy 32 4.29 8.72MSS Dandy 4 4.20 8.50 MSS Dandy 33 4.37 9.18MSS Dandy 5 4.40 7.37 MSS Dandy 34 4.52 9.04MSS Dandy 6 4.68 3.05 MSS Sassy 1 4.34 6.29MSS Dandy 7 4.88 1.90 MSS Sassy 2 4.60 5.19MSS Dandy 8 4.65 2.34 MSS Sassy 3 4.54 8.69MSS Dandy 9 4.69 3.60 MSS Sassy 4 3.98 9.47MSS Dandy 10 4.89 3.46 MSS Sassy 5 4.46 8.68MSS Dandy 11 4.64 10.31 MSS Sassy 6 4.23 8.25MSS Dandy 12 3.73 11.02 MSS Sassy 7 4.06 7.93MSS Dandy 13 4.50 10.33 MSS Sassy 8 4.74 9.28MSS Dandy 14 4.34 9.95 MSS Sassy 9 4.29 5.45MSS Dandy 15 4.06 10.07 MSS Sassy 10 4.38 1.96MSS Dandy 16 4.12 10.06 MSS Sassy 11 4.39 1.28MSS Dandy 17 4.10 10.41 MSS Sassy 12 4.39 1.52MSS Dandy 18 4.34 9.85 MSS Sassy 13 4.46 1.56MSS Dandy 19 4.27 9.56 MSS Sassy 14 4.71 2.34MSS Dandy 20 4.42 9.18 Medicago sativa(C3) 0.15 10.71MSS Dandy 21 4.56 8.72 Medicago sativa(C3) 0.15 10.76MSS Dandy 22 4.45 8.62 Medicago sativa(C3) 0.15 10.02MSS Dandy 23 4.22 9.03 Cynodon dactylon(C4) 0.58 2.00MSS Dandy 24 4.50 11.36 Cynodon dactylon(C4) 0.91 1.82MSS Dandy 25 4.49 10.89 Cynodon dactylon(C4) 0.70 1.79MSS Dandy 26 4.29 10.52 Bromus inermis(C3) 0.28 10.58MSS Dandy 27 4.47 9.39 Bromus inermis(C3) 0.28 11.18MSS Dandy 28 4.44 8.97 Bromus inermis(C3) 0.26 10.51MSS Dandy 29 4.28 8.62

-5

-4

-3

-2

-1

01

2

3

4

5

6

7

8

9

10

11

12

13

1415

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36

Hair section (1.5 cm each)

34S

Dandy

Sassy

Scalp

Bromus inermis C3

Medicago sativaC3

Cynodon dactylonC4

Most recent hair

Dietary change reflected in hair

Older hair

Time

Figure 1. 34S values of tail hair segments from the horses Dandy and Sassy. 34S values of diets are indicated on the graph.Errors on the 34S measurements are 0.3 (1).



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to the California/Mexico Cynodon hay. The hair34S reaches its lowest point at segment 6, after

which it dramatically increases when the diet waschanged to local Utah Medicago hay. Eventually,the hair34S values became close to those of the

Medicago hay, but were still depleted by about1. An almost identical pattern is observedfor Sassy, although the hair records only theCynodonhay diet and the subsequent switch to the

Medicagohay.Bothdata sets clearly demonstrate large changes

in hair 34S values as the horses feeds wereswitched through time. Interestingly, however,these data seem to indicate that diet-hair frac-

tionation is not constant on all diets. Mostconspicuously, it appears that when the dietswere switched to the Cynodonhay, their hair wasenriched in 34S by nearly 4 (but see discus-sion below). When switched to the localMedicagohay, however, hair values approached, but neverreached dietary34S values, suggesting a diet hairfractionation of about 1 for these horses. Weonly have data from Dandy on the local Bro-mus hay, and hair values and dietary 34S valuesappear nearly identical when on this hay. Thus,there appears to be a large diet-hair fractionationwhen horses are consumingCynodonhay, but rel-

atively little fractionation when they are on eitherof the local hays. This change in fractionationis not associated with temperature changes dur-ing the course of the experiment (Sponheimer,unpublished data). One possible explanation forthis patterning is that, even though the Cynodonand Bromus hays were isonitrogenous, digestibleprotein was lower for theCynodonhay than eitherof the local hays. There is some support for thisas both horses lost body mass when on this diet.This might have led to increased recycling of theirbody proteins, which had been formed while on

a local diet.The sulphur in hair is primarily derived from

cysteine and methionine. As cysteine is a non-essential amino acid, it can be synthesized fromother amino acids, serine and methionine. Theunusually high diet-hair fractionation seen duringthe consumption ofCynodonhay could have beenthe result of contributions from endogenous 34S-enriched sulphur atoms from methionine to formcysteine. If this explanation is correct, it meansthat the true diet-hair equilibrium would have only

been obtained once all of the horses metabolicallyactive tissues had turned over. In contrast, when

on nutritionally adequate diets there appears tobe a direct routing of the sulphur in cysteine andmethionine from the diet to hair protein.

While this study provides new experimentaldata for the magnitude of diet-hair fractionation ofsulphur isotopes in large mammalian herbivores,it is apparent that it only begins to address thisquestion for mammalian herbivores in general,much less for omnivorous or carnivorous species.Future studies are needed in which multipletaxa are raised on isotopically homogenousdiets from birth, which would eliminate the

protein recycling that has proven problematichere. Ideally, such studies would also test thepotential impact of feeding animals diets withdiffering amounts of protein, or more specifically,different amounts of sulphur-containing aminoacids such as cysteine and methionine. It islikely that diets that are deficient in sulphurcontaining amino acids will have very differentfractionation patterns (endogenous synthesis)compared to diets that have adequate levels ofcysteine and methionine (direct routing from dietto tissue).

Discussion and conclusions

We have presented a review of sulphur isotopesin the environment and their application toarchaeological studies. In addition, we haveargued that 34S measurements can providesupplementary palaeodietary evidence to 13Cand 15N measurements, and have the potentialto identify migration and residence locality in thearchaeological record. Finally, we have presentedthe results of one of the few controlled mammal

feeding experiments and observed that there isminimal (1) 34S fractionation between dietand consumer hair on a nutritionally adequateC3 diet. On a C4 diet that is likely to below in digestible protein we observed a 34Sfractionation of+4, which could be the result ofsulphur recycling from body proteins in additionto dietary sulphur intake. Future studies on animalsthat are raised on known34S diets from birth areneeded to support or challenge the fractionationpatterns seen in this study.



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Acknowledgements

We would like to thank Gundula Muldner forhelp with sample preparation. We are indebtedto Steve Brookes and Ian Begley at Isoanalyticalfor measuring the 34S values and to Paul Kochfor helpful suggestions and editing. We also wantto thank Thure Cerling, Denise Dearing, JimEhleringer, Jordan Hammer, Yasmin Rahman, andBev Roeder.

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