Journal of Archaeological Science 34 (2007) 335e343 http://www.elsevier.

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The impact of manuring on nitrogen isotope ratios in cereals: archaeological implications for reconstruction of diet and crop management practices
A. Bogaard a,*, T.H.E. Heaton b, P. Poulton c, I. Merbach d
a

Department of Archaeology, University of Nottingham, University Park, Nottingham NG7 2RD, UK b NERC Isotope Geosciences Laboratory, British Geological Survey, UK c Rothamsted Research, UK d Bad Lauschstadt Experimental Station, Umweltforschungszentrum Leipzig-Halle, Germany Received 22 February 2006; accepted 21 April 2006

Abstract Recent archaeological studies of human diet have used stable nitrogen isotope ratios (d15N) from human bone collagen to infer the relative importance of terrestrial plant and animal foods. This approach is based on widely observed enrichment of d15N up the food chain, plants having distinctly lower values than the herbivores that consume them. Studies of early farming diets in Britain, Denmark and Germany have tended to detect relatively high d15N values (e.g. c. 9&), interpreted as evidence of a diet largely based on animal products, though archaeobotanical evidence for crop cultivation (e.g. carbonised cereal grain and chaff) is widespread. This paper investigates the impact of manuring on d15N values in modern cereals, and of charring on these cereal values. The results from two long-term experiments demonstrate that manuring signicantly raises d15N in cereal grain and chaff. Depending on manuring levels and frequency, it appears that human diets with a major component of such grain would conventionally be interpreted as indicating a largely animal-based diet or a mixed plant/animal diet. Moreover, preliminary analyses of experimentally charred grain and chaff from manured and unmanured conditions are promising for the extraction of reliable ancient d15N values from archaeobotanical cereal remains. The wider implications of these results, and the need for further work, are discussed. 2006 Elsevier Ltd. All rights reserved.
Keywords: Nitrogen; Stable isotopes; Manuring; Cereals; Neolithic; Crop husbandry

1. Introduction Stable carbon and nitrogen isotope ratios are now routinely used to infer aspects of past human diets (e.g. [40,42,54, 55,62]). Carbon isotope ratios (d13C values) can potentially distinguish between terrestrial and marine foods and/or C3 and C4 pathway plants [15,53,61]. Nitrogen isotope ratios (d15N values) are used to infer the trophic level of food based

* Corresponding author. Tel.: 44 115 951 4815; fax: 44 115 951 4812. E-mail address: amy.bogaard@nottingham.ac.uk (A. Bogaard). 0305-4403/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.jas.2006.04.009

on increases in d15N values up the food chain, herbivores having distinctly higher values than the plants that they eat (e.g. [17,43,60,66]). In combination, carbon and nitrogen isotope ratios have been used to reconstruct ancient human diets and have, for example, played a key role in debate over the nature of the MesolithiceNeolithic transition in north-west Europe (e.g. [53,54,62,64]). The isotopic technique of reconstructing ancient human diet is particularly attractive given the difculty of inferring the relative dietary contribution of animals and plants from their remains on archaeological sites (e.g. [14]). Recent applications of the isotopic method of dietary reconstruction in Britain [52,54,62], Denmark [55] and southern

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Germany [20,21] have been interpreted to suggest the following:  Neolithic communities made little use of marine foods, obtaining most of their protein from a combination of terrestrial animals and C3 plants  d15N values are generally consistent with a largely animalbased diet, suggesting that C3 plants played a limited dietary role (despite widespread archaeobotanical evidence for cereal use) While there has been lively debate over the interpretation of these results as they relate to marine versus terrestrial resources (e.g. [29,39,44]), the issue of terrestrial animal- versus plant-based foods has received less attention. Durrwachter et al. [21] have recently summarised a number of issues surrounding the interpretation of d15N as a reection of the relative importance of plant- and animal-based foods. First, isotope analysis of archaeological remains of mammals is commonly undertaken on collagen separated from bone, and the 15N-enrichment in bone collagen relative to dietary protein values may be higher (e.g. up to 5&) than the commonly assumed c. 3& [5,19]. Second, there is a lack of information available on d15N in ancient plant remains, largely, according to Durrwachter et al. [21], because they are generally not ad equately preserved to permit analysis. As a result, assumptions have to be made using generalised plant values and archaeological herbivore bone collagen. Third, d15N may tend to reect the meat portion of the diet since animal foods are generally richer in protein than plant foods, with the result that d15N values are particularly insensitive to low or moderate consumption of plant foods [21]. Durrwachter et al. [21] conclude, however, that d15N values can be used to distinguish heavy plant consumers from heavy animal consumers. The aim of this paper is to begin exploring the potential range of variability in plant d15N values, specically those for cultivated cereals, in order to set archaeological reconstructions of human diet and crop husbandry practices on a rmer foundation. Cereal stable isotope values may be affected by alterations to the growing environment introduced by ancient farmers; variation in d13C in cereals, for example, has been related to water economy and irrigation in arid environments (e.g. [3,4,47]). A factor that could directly affect cereal d15N values is manuring e the application of animal dung to cultivation plots in order to restore nutrients and enhance crop yields. High d15N values in animal manure largely result from the preferential loss of 14N in volatile gaseous ammonia, leaving residual ammonium relatively enriched in 15N. This ammonium is subsequently converted to nitrate with high d15N values, which is taken up by plants [28,35,37]. Nitrates are the major source of nitrogen used for the biosynthesis of plant amino acids, which eventually end up in the bone collagen of consumers [58]. Previous studies suggest that the application of animal manure raises d15N values in soil and plants (e.g. [10,16,63,68,70,71]). Van Klinken et al. [67] note that a manuring effect on plant values would have a signicant impact on d15N in human consumers. These authors conclude,

Thus, there is a need to check for anthropogenic effects in the archaeological food chain, which can be done by measuring associated plant and animal remains [67, original italics]. In their study of Neolithic diet in central Europe, Durrwachter et al. [21] have also stressed that isotopic information from ancient plant remains, especially crops, would serve to greatly enhance the accuracy of human dietary reconstructions. Chemical and soil micromorphological studies of ancient soils (palaeosols) can provide direct evidence for manuring (e.g. [12,13,22,24,63]). In agricultural landscapes cultivated over many centuries, however, such evidence is rarely preserved and the practice can only be inferred indirectly, from spreads of sherds and other inorganic inclusions across the landscape (e.g. [1,68]), or from ecological characteristics of arable weeds associated with crop remains in archaeological deposits (e.g. [33,34]). An archaeobotanical study of weed assemblages and crop husbandry practices in Neolithic central Europe by Bogaard [6] concluded that manuring was a likely cause of frequent high fertility, and similar inferences have been made for south-east Europe [26]. Indeed, one reading of the Neolithic package of plant and animal domesticates is that it was precisely such integration of plant and animal (by-)products that enabled farming to successfully spread across a range of environments [6,7,8]. From this perspective, it is plausible that relatively high d15N values in Neolithic human remains from central Europe and elsewhere are due, at least in part, to a manuring effect. In order to assess the potential impact of manuring on the reconstruction of human diet, this paper considers new data on d15N in cereals grown under manured and unmanured conditions at two long-term experimental stations: Rothamsted, Hertfordshire, England [23,57] and Bad Lauchstadt, Leipzig Halle, Germany [36]. These data on cereals grown under known conditions can be used to assess how far the d15N values in cereal grain and chaff are affected by manuring, and hence the impact that manuring in the past would theoretically have on values in human bone collagen. This study is the rst of its kind to look at the effects of manuring on cereal d15N values through time using long-term experimental data. A second aim of this paper is to consider the impact of charring on d15N cereal values, since charred grains and chaff represent the most widespread form of archaeobotanical evidence for cultivation.

2. Materials and methods Two long-term experiments of over one hundred years duration, including one with archive cereal samples going back to the rst decade of the experiment, were selected in order to assess the long-term effects of farmyard manure application on d15N in cereals. Details of the two experiments are given in Table 1. The Broadbalk Wheat Experiment at Rothamsted, Hertfordshire studies winter wheat (Triticum aestivum L.) cultivation under various treatments. One plot (plot 22; previously plot 2 or 2B) is treated only with farmyard manure. This

A. Bogaard et al. / Journal of Archaeological Science 34 (2007) 335e343 Table 1 Details of the experimental plots samples for isotopic analysis Experiment Broadbalk, Rothamsted Static fertilization experiment, Bad Lauchstadt Location Hertfordshire, England Leipzig-Halle, Germany Period 1844present 1902present Cropping Winter wheat Manuring treatment(s) Cattle manure, 35 t/ha every year Cattle manure, 20 and 30 t/ha every second year Soil type Chromic luvisol; inty-silty clay loam over clay-with-ints Haplic chernozem; loess

337

References [23,57]

Sugar beet-spring barley-potatoeswinter wheat

[2,36]

plot receives annual dressings of cattle manure at the rate of 35 t (fresh weight) per hectare each year. Such a level of application is equivalent to the annual manure production of about three cattle over one hectare [56, cf. 41]. A control plot (plot 3) has received no farmyard manure or mineral fertilizers since 1844. The Bad Lauchstadt experiment consists of a four-course crop rotation (including winter wheat, T. aestivum L.) and two different manuring levels: 20 or 30 t of farmyard manure (Stalldung, fresh weight) per hectare every second year in plots 12 and 6, respectively. A control plot (plot 18) receives no inputs. Samples of at least 20 whole wheat plants were collected just before harvest time in 2004 from manured and control plots in both experiments. Grain and rachis (the stalk segments to which spikelets are attached in the cereal ear) harvested from 20 plants were randomly subsampled (using a rife box) to provide bulk samples for analysis. All bulk samples analysed consisted of c. 20e30 grains or rachis segments. The selection of rachis for measurement, in addition to grain, is due to the fact that it is identiable to species and is widely preserved archaeologically (e.g. in charred form). Archive samples of grain and rachis from Rothamsted for the years 1852, 1895, 1935 and 1965 were also subsampled to provide bulk samples for analysis. These years were chosen to provide spread across the period covered by the archive (1844e2005). Additionally, unpublished measurements of cereal grain from the manured and control plots in 1991 were included along with the new data (Smolinska, unpublished data 1991). The archives for Bad Lauchstadt consisted of grain from recent years only; archive samples of wheat grain from 2001 to 2002 were subsampled to provide bulk samples for analysis. While the aim of bulk sampling was to explore variation between treatments and variation through time, detailed sampling of individual plants was conducted to enable investigation of variation in d15N within a single cereal ear and between plants. Samples of grain and rachis from individual spikelets of four cereal plants e two ears from two different plants harvested in the 2004 control plot, and two ears from two different plants harvested in the 2004 manured plot at Rothamsted e were taken for analysis. Table 2 summarises the individual grain and rachis samples analysed. Random subsamples of material harvested from Rothamsted and Bad Lauchstadt in 2004 were also subjected to charring in order to ascertain the impact of this process on d15N values. Subsamples of wheat grain and rachis (c. 20e30 grains or

rachis segments) were charred in a low-oxygen atmosphere (wrapped in aluminium foil) at 230  C for 2e24 h e conditions that have proved suitable to reproduce undistorted archaeological charred grain and rachis [M. Charles and G. Jones pers comm.; cf. 65]. Charring was carried out at the Department of Archaeology, University of Nottingham, in a digitally controlled chamber furnace. At the NERC Isotope Geosciences Laboratory, Keyworth, all samples were homogenised using a freezer mill, weighed into tin capsules, and combusted in an elemental analyser (Thermo Finnigan Flash EA) on-line to an isotope ratio mass spectrometer (Thermo Finnigan Delta XL). Sample 15 N/14N ratios were calculated as d15N values versus atmospheric N2, on the basis of comparison with samples of a laboratory plant standard whose d15N value was determined by comparison with IAEA-N-1 (assuming d15N of IAEA-N1 0.4& [31]). 3. Results 3.1. Within- and between-plant variations in grain and rachis d15N The results for grain and rachis internodes from the individual spikelets of four wheat ears harvested in 2004 at Rothamsteds Broadbalk experiment (two ears from two plants harvested in the control plot, and two ears from two plants harvested in the manured plot) are shown in Fig. 1. Values for grain were reasonably constant. The rachis displayed greater variation, typically showing a decline in d15N from the basal spikelet to the terminal spikelet. Variations between individual plants must also be expected. Thus, from the data in Fig. 1, average grain d15N values differed by only 0.1& between the two ears from the plants harvested in the control plot (Plants 1 and 2), but by 1.3& between the two plants harvested in the manured plot (Plants
Table 2 Summary of samples from individual plants harvested in 2004 at Rothamsted; NIL control plot; FYM farmyard manure Grain Plant Plant Plant Plant 1, 2, 3, 4, ear ear ear ear 1 2 3 4 (NIL) (NIL) (FYM) (FYM) 17 19 23 21 spikelets spikelets spikelets spikelets Rachis Not analysed 19 spikelets 23 spikelets 21 spikelets

Note: 1 grain and 1 rachis internode per spikelet were analyzed.

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A
+1.0 0.0

ROTHAMSTED within-ear variation. NIL, plant 1

B
+1.0 0.0

ROTHAMSTED within-ear variation. NIL, plant 2

d15N vs AIR

d15N vs AIR
0 2 4 6 8 10 12 14 16 18

-1.0 -2.0 -3.0 -4.0 -5.0

-1.0 -2.0 -3.0 -4.0 -5.0 0 2 4 6 8 10 12 14 16 18 20

Spikelet position
Grain

Spikelet position
Grain Rachis

C
+8.0 +7.0 +6.0

ROTHAMSTED within-ear variation. FYM, plant 3

D
+8.0 +7.0 +6.0

ROTHAMSTED within-ear variation. FYM, plant 4

d15N vs AIR

d15N vs AIR
0 5 10 15 20 25

+5.0 +4.0 +3.0 +2.0 +1.0 0.0 -1.0

+5.0 +4.0 +3.0 +2.0 +1.0 0.0 -1.0 0 5 10 15 20 25

Spikelet position
Grain Rachis

Spikelet position
Grain Rachis

Fig. 1. d15N values for grain and rachis internodes from the individual spikelets of four wheat ears: (a) plant 1, control plot at Rothamsted; (b) plant 2, control plot at Rothamsted; (c) plant 3, manured plot at Rothamsted; and (d) plant 4, manured plot at Rothamsted. Rachis from plant 1 was not measured.

3 and 4). In another study, d15N values for whole wheat plants (excluding roots) from plots treated with farmyard manure and inorganically-fertilized plots ranged over 2& (1 SD 0.8 and 1.0& for two groups of n 5; Poulton unpublished data 1991). 3.2. Differences in grain and rachis d15N between manured and control plots Tables 3a and b and Fig. 2 summarise the results for bulk samples per treatment and year. Elevated d15N values are associated with manured versus control treatments at Rothamsted and Bad Lauchstadt, and these differences are visible in both grain and rachis. Several points are worth noting from these results. First, a manuring effect is evident from the earliest archive samples available at Rothamsted (1852), less than 10 years after the experiment began (in 1844). Second, manured and control values in both experiments remain fairly constant through

time. Third, rachis d15N values are consistently lower than those in grain. It can also be noted here that d15N values in cereal straw and leaves are also lower than those in grain (Smolinska, unpublished data 1991). Fourth, grain and rachis from the lower level of manure application at Bad Lauchstadt
Table 3a Results for the analysis of bulk samples from Rothamsted (na material not available for analysis; nd not determined; NIL control plot; Fym farmyard manure) Year d15N Grain Nil 1852 1895 1935 1965 1991 2004 2.7 2.9 4.0 0.7 0.6 0.8 FYM 5.8 7.8 8.3 7.4 8.6 6.6 Rachis Nil na 0.6 0.4 2.5 na 2.6 FYM na 5.0 7.1 5.3 na 3.4 %N Grain Nil 1.8 1.9 1.8 2.0 1.5 1.5 FYM 2.0 1.8 nd 2.3 2.0 1.9 Rachis Nil na nd 0.6 0.3 na nd FYM na nd 0.6 0.8 na nd

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Table 3b Results for the analysis of bulk samples from Bad Lauchstadt (na material not available for analysis; NIL control plot; FYM1 biennial 20 t/ha, FYM2 biennial 30 t/ha) Year d15N Grain Nil 2001 2002 2004 1.0 0.1 0.8 FYM1 4.1 2.7 3.2 FYM2 5.7 4.1 3.4 Rachis Nil na na -1.3 FYM1 na na 0.9 FYM2 na na 2.2 %N Grain Nil 1.2 1.4 1.1 FYM1 1.1 1.4 1.3 FYM2 1.3 1.5 1.3 Rachis Nil na na 0.2 FYM1 na na 0.3 FYM2 na na 0.3

(FYM1) is associated with lower d15N values than the higher level (FYM2). The even higher rate of yearly manure application at Rothamsted is associated with the highest d15N values, though it should be noted that the control plot values at Rothamsted also tend to be higher than those at Bad Lauchstadt. Overall, it is clear that manuring has a distinct impact on d15N values in both cereal grain and rachis. Moreover, the low levels of natural variation within and between plants reviewed above would not obscure the manuring effect on d15N values. 3.3. The impact of charring on d15N values in wheat grain and rachis Work by DeNiro and Hastorf [18] on charred plant remains (seeds and tubers) from Peruvian archaeological sites showed that d15N in charred plant material was similar to that in modern counterparts, suggesting that charring did not bias the signature. Fig. 3 shows the results of preliminary analyses on the impact of charring, with d15N values in wheat grain (Fig. 3a) and rachis (Fig. 3b) harvested in 2004 from the manured and control plots at Rothamsted and Bad Lauchstadt, and charred at 230  C under low-oxygen conditions for up to 24 h. Fig. 3a indicates that charring causes only minor distortion of d15N values in grain and that the manuring effect is not

obscured. The distortion of d15N values in rachis is more marked (Fig. 3b), and the relative position of the control plots at the two experiments is reversed after 2 h charring, but the contrast between manured and control plots remains intact. 4. Discussion With enrichment of c. 3& from one trophic level to the next, the conventional wisdom is that bone collagen from humans having a largely plant-based diet would have d15N values of c. 6& (assuming plant values of c. 3&), while a diet based on herbivores should result in values of c. 9& (assuming herbivore values of c. 6&). A mixed diet in which both plants and animals played a major role would lie between 6 and 9& (e.g. [52]). Neolithic values for human bone collagen recently reported from southern Germany, Denmark, the west coast of Scotland and southern Britain (Table 4) have been interpreted as evidence that diets were largely animalbased (southern German sites, Danish sites, western Scottish sites, some Hambledon Hill samples, Parc le Breos) or, in some cases in southern Britain (Hazleton, West Kennet, some Hambledon Hill samples), a mixed diet of plant- and animal-based foods. The d15N values of Neolithic crops, however, could have a major impact on the interpretation of such results. The

A
+10.0 +8.0 +6.0

+10.0 +8.0 +6.0

d15N vs AIR

d15N vs AIR

+4.0 +2.0 0.0 -2.0 -4.0 1852

+4.0 +2.0 0.0 -2.0 -4.0 2001

1895

1935

1965 1991 2004

2002

2003

2004

years sampled
FYM gr NIL gr FYM ra NIL ra

years sampled
FYM2 gr FYM1 gr NIL gr FYM2 ra FYM1 ra NIL ra

Fig. 2. d15N values for bulk samples of grain and rachis from (a) Rothamsted and (b) Bad Lauchstadt. NIL control plot; FYM farmyard manure (annual 35t/ha); FYM1 biennial 20t/ha, FYM2 biennial 30t/ha.

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A
+8.0 +7.0 +6.0

+6.0 +5.0 +4.0

d15N vs AIR

d15N vs AIR
0 5 10 15 20 25 30

+5.0 +4.0 +3.0 +2.0 +1.0 0.0

+3.0 +2.0 +1.0 0.0 -1.0 -2.0 -3.0 0 5 10 15 20 25 30

Time (hours)
Roth Nil Roth FYM BadL NIL BadL FYM1 BadL FYM2

Time (hours)
Roth Nil Roth FYM BadL NIL BadL FYM1 BadL FYM2

Fig. 3. The effect of charring at 230  C and its duration on d15N in grain and rachis (0 h uncharred): (a) grain; (b) rachis. Roth Rothamsted; BadL Bad Lauchstadt.

data from modern experiments reported here suggest that a diet largely based on manured cereals could result in Neolithic humans having fairly high d15N values e i.e. resembling those resulting from a largely animal-based diet, or a mixed plant- and animal-based diet. Thus, with trophic enrichment of c. 3&, the bulk samples of manured cereal grain from Rothamsted (c. 6 to 8&) would be expected to yield values of c. 9 to 11& in consumers (resembling a largely animalbased diet), with the lower levels of biennial manuring at Bad Lauchstadt (grain values of c. 3 to 6&) yielding values of c. 6 to 9& in consumers (resembling a mixed plant- and animal-based diet). If Neolithic farming in southern Germany, Denmark and Britain was of the permanent, small-scale and intensive type resembling gardening [6,7,8,26; cf. 9], long-term manuring

comparable to the applications at Rothamsted (equivalent to the manure of c. 3 cattle per hectare each year) is not implausible. It is likely that manure inputs, along with other labourintensive measures, varied somewhat from year to year depending on a range of factors (labour, livestock, weather, etc.) [26,27; cf. 59]. Thus, variation among human d15N values at well-sampled sites such as Hambledon Hill could reect variability in crop growing conditions through time or among households, rather than diets ranging from mixed plant/animal to largely animal-based [52]. The measurement of d15N in associated faunal remains is widely accepted as a critical factor in the interpretation of human d15N values. Values for domestic cattle and sheep from the Neolithic sites in Germany and Britain are shown in Table 4. Interpretation of some human d15N values as indicative of

Table 4 Summary of Neolithic d15N values from bone collagen of humans (adults), domestic cattle and sheep (excluding juvenile animals) in southern Germany, Denmark and Britain; n number of samples Site Herxheim, Germany Trebur, Germany Ostrup, Store Amose, Denmark Undlose, Store Amose, Denmark Bodal, Store Amose, Denmark Aldersro, Denmark Carding Mill Bay Crarae Hambledon Hilla Parc le Breos Hazletonb West Kennetb
a b

Period LBK HinkelsteinGrossgartach TRB TRB TRB TRB Earlier Neolithic Earlier Neolithic Earlier Neolithic Earlier Neolithic Earlier Neolithic Earlier Neolithic

Human d15N min 7.8 8.5 9.9

Human d15N max 12.1 10.5 10.0

Human d15N average 9.9 9.7 10.0 8.2 8.0

n 21 40 2 1 1 6 9 3 56 8 5 3

Cattle d15N 7.0 5.7 (ave)

n 1 5

Sheep d15N 6.2 (ave)

Interpretation Animal-based diet Animal-based diet Animal-based diet Animal-based diet Animal-based diet Animal-based diet Animal-based diet Animal-based diet Animal-based (10) or mixed (7 to 9) Animal-based diet Mixed diet Mixed diet

Reference [20,21] [20,21] [55] [55] [55] [55] [62] [62] [52] [52] [52] [52]

7.5 8.8 9.1 7.0 8.9 7.3 8.1

9.3 10.0 9.5 10.5 10.4 8.4 8.5

8.4 9.3 9.2 9.5 9.7 7.9 8.3

5.5 (ave)

5.0 (ave)

4.6 (ave)

Mostly adults according to Richards [52]; approximate values derived from scatter plot [52, Fig. 12.2]. Adult status of human remains uncertain [52].

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a largely animal-based diet rests on the fact the human samples tend to appear one trophic level higher (c. 3& higher) than associated herbivores (Table 4). The manuring of cereals in an intensive cultivation regime, however, provides an alternative explanation for this discrepancy, assuming that humans were the primary consumers of grain. Moreover, if arboreal vegetation (leafy or branch hay) provided an important source of fodder as has often been suggested for Neolithic central and western Europe (e.g. [25,38,49,50,51]), the low d15N associated with forest ecosystems (e.g. [30,46,69]) would tend to distinguish plant consumption between livestock and humans in terms of their d15N values. Furthermore, the results for rachis values from Rothamsted and Bad Lauchstadt suggest that d15N values in chaff tend to be lower and more variable than in grain, as is the %N content of chaff. Measurements of d15N in cereal straw and leaves likewise suggest that these are low relative to grain (Smolinska, unpublished data 1991). Even if livestock diets were supplemented with fodder consisting of the chaff by-products of manured cereals, therefore, the impact on their d15N would be reduced in comparison with human consumers of manured grain. One methodological issue to be addressed concerns the measurement of whole grain versus protein d15N values in manured and unmanured cereals. It has been assumed thus far that changes in d15N values caused by manuring largely reect changes in protein N isotope ratios. While this assumption appears justied from previous work on d15N values in proteins [11], further work is needed to conrm that whole grain and protein compound-specic d15N values show a similar manuring effect. A related methodological point, raised by Durrwachter et al. [21], is the need to characterise nitrogen stable isotope values for individual amino acids from bone collagen, in order to narrow down their potential dietary sources. Finally, the preliminary charring results are promising for the reliable measurement of d15N values in charred archaeobotanical material, but further work is needed to explore the full range of relevant crops and charring conditions, as well as to address issues of diagenesis and contamination in archaeological burial environments.

Acknowledgements This research was made possible by a grant-in-kind from the NERC Isotope Geosciences Facilities Steering Committee. We thank the Lawes Trust for access to the archived Rothamsted samples and Ursula Smolinska for the 1991 Broadbalk data. Rothamsted Research receives grant-aided support from the Biotechnology and Biological Sciences Research Council of the UK. We thank the UFZ Centre for Environmental Research Leipzig-Halle for providing the plant samples of the Static Fertilization Experiment Bad Lauchstadt and for alloca tion of archived grain samples. Finally, the authors are grateful to Oliver Craig, Glynis Jones, Rick Schulting and two anonymous reviewers for insightful comments on the paper.

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5. Conclusions The results of the analyses presented here support previous suggestions (e.g. [21,67]) that information on plant d15N values e and in particular those of potential staples e is critical for accurate assessment of animal- and plant-based foods in the human diet. The suggestions made here regarding alternative interpretations of Neolithic d15N values, however, must remain speculative until reliable measurements of archaeological plant d15N values are available. Archaeological plant values from Neolithic sites in north-west Europe would help to resolve the problem of equinality between a diet based largely on animal products and one based on manured cereals. Plant values may also be useful for the interpretation of similar d15N values from human samples in later periods (e.g. [32,45,48]).

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