Journal of Archaeological Science 35 (2008) 2171e2178 http://www.elsevier.

com/locate/jas

A new calibration of the XRD technique for the study of archaeological burned human remains
` Malgosa a, T.J.U. Thompson b, Stefano Enzo c Giampaolo Piga a,*, Assumpcio
a

Unitat dAntropologia, Department de Biologia Animal, Biologia Vegetal i Ecologia, Universitat Autonoma de Barcelona, 08193 Bellaterra, Spain b School of Science & Technology, University of Teesside, TS1 3BA Middlesbrough, UK c Department of Chemistry, University of Sassari, Via Vienna 2, 07100 Sassari, Italy Received 14 June 2007; received in revised form 6 September 2007; accepted 1 February 2008

Abstract A new calibration of human bones as a function of programmed temperature (200e1000  C) and time (0, 18 and 60 min) is presented and discussed in order to investigate the issues related to the study of cremated bone remains by using the powder X-ray diffraction approach. The experimental results conrm the growth of hydroxylapatite crystallites as a function of the applied temperature, with a sigmoid behaviour that has been parameterized to the experimental data points. Particularly, it was observed that the thermal treatments for 60 min anticipate of about 100  C the effects that are otherwise observed after the treatments for 0 min. The developed procedure was subsequently applied to cremated remains of various archaeological sites of Spain and supplied precise information not only about the temperature reached during the funerary rites, but also on the presumed duration for the cremation. 2008 Elsevier Ltd. All rights reserved.
Keywords: Cremated bones; Hydroxylapatite; Powder X-ray diffraction

1. Introduction The study of cremated human remains is of considerable importance in anthropology and frequently coincides with issues common to archaeology and forensics. For example it appears particularly interesting to be able to assess the temperature reached by civilizations using cremations within their funerary practices and to estimate a possible time scale for the re treatment of bodies. This also represents useful information concerning the re and materials technology of the time. In addition to this, an investigation of re temperatures seems advisable in order to conrm or reject the possibility of occasional non-ritualistic res in civilizations where the use of funerary rites has never been veried in depth (Piga et al., in press).

* Corresponding author. Tel.: 34 07840935. E-mail address: kemiomara@yahoo.it (G. Piga). 0305-4403/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.jas.2008.02.003

In a rst instance, a visual investigation of the remains is able to suggest whether the bones have been subjected to re. However, these problems can be suitably and objectively addressed with a powder X-ray diffraction approach for the hydroxylapatite (HA) mineral phase, which is the main inorganic phase in bones. Since 1975 (Bonucci and Graziani, 1975) it has been demonstrated that high temperatures of re treatments induce a growth of the average crystallite size of HA, which can be appreciated relatively well from the line broadening/sharpening analysis of diffraction peaks. In the rst critical study of its kind, Shipman et al. (1984) investigated the microscopic morphology of various osteological materials and used X-ray diffraction in order to assess whether specimens of unknown taphonomic history were burnt and the maximum temperature reached by those specimens. These investigations are based on the fact that heating the bones causes a sharpening of diffraction patterns, attributed to increased crystallite size and decreased lattice strain of osteological phases.

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However, subsequently Bartsiokas and Middleton (1992), with the aim of characterizing and dating recent and fossil animal and human bones, suggested measuring a so-called crystallization index from their diffraction patterns, which can be mainly ascribed to the presence of natural apatite phase. The crystallization index, which is strictly related to the peak sharpening effects, was actually dened as the intensity ratio of (300)/(202) line proles of hexagonal apatite, which normally occur as shoulder of the most intense (211) line in the 2q angular range from 31 to 35 when using Cu Ka radiation. A linear correlation between crystallinity index and bone age was reported over a period length of more than 106 years. It should also be noted that another crystallinity index was almost concomitantly dened by Person et al. (1995) using more peaks belonging to the same angular range. It is clear that the two above mentioned lines of work may be conicting especially if the bones were subjected simultaneously to both physical effects of burning and annealing across very long periods of time. This is further complicated but the fact that there have been very few studies exploiting this technique in 20 years since its rst serious adoption. Studies by Newesely (1988), Holden et al. (1995), Stiner et al. (1995) and Rogers and Daniels (2002) have supercially investigated this source of information, but lack the cohesive nature necessary to allow one to overcome these sort of conicts. However, in a sufciently short period of time it seems that the two effects can be assumed well distinct. As a matter of fact, the time period investigated by Bartsiokas and Middleton requires some millions of years to observe signicant changes in the crystallization index, which is a quantity determined with an error bar of few percent. This means that the crystallinity index may be regarded virtually unchanged in a period in the order of 10,000 years, that is, in a period of archaeological and forensic relevance. In order to further extend the validities of methodologies which appeared in the literature we present here a calibration protocol of a sample of bone as a function of selected temperatures of treatment in a range (200e1000  C), keeping also into account the duration of burning (0, 18 and 60 min) thus enabling a better simulation of a real ring process. In particular, we analysed the behaviour of the bone sample for some intermediate temperatures (650, 750, 775, 825 and 850  C) to closely investigate and describe the two-stage growth regime of HA previously observed around 700  C (Enzo et al., 2007). Holden et al. (1995), Rogers and Daniels (2002) and recently Kalsbeek and Richter (2006) have also recorded key crystalline changes within this temperature range. Within anthropology, this temperature range is signicant because it is during this transition that the size of the bone alters to a statistically signicant degree (Shipman et al., 1984; Thompson, 2005). This in turn will not only impact on microstructural studies of bone, but also on macroscopic analysis with a view to determining a biological prole (sex determination, age-at-death estimation, etc.) of the burned individual. The accuracy of such biological or osteological proles is dependent on the use of unmodied bone. This is true for both metric and

morphological anthropological techniques. Therefore it is essential that we understand the osseous changes during this temperature range so that it is possible to create either new techniques devised specically for burned bone or new methods of statistically correcting the output of current anthropological techniques when used on burned bone (Thompson, 2005). Furthermore, a more solid appreciation of these changes will allow archaeologists to differentiate burned bone from non-burned bone using XRD as has been attempted so infrequently (Stiner et al., 1995). The kinetics of crystallite growth is followed in relation to the temperature and time duration in order to quickly and reliably evaluate the various aspects involved in the cremation process. In fact, with this approach it will be possible to make an accurate estimation of both temperature and likely time duration of the cremation rite. We have started our analysis from a dry ancient bone. Bohnert et al. (1998) observed that for total incineration of a body via cremation about 2 h is necessary at a constant temperature of 800  C, while for destruction of the eshy parts about 50 min is believed to be needed. Thus, in view of a selected temperature ramp with scanning rate of 20  C/min, our selected times appear to be coherent with a real cremation process. In spite of this we have directly checked our results by treating fresh pig bones at some selected temperatures and times of annealing. Of course it is not guaranteed absolutely that the ramp heating process applied in the furnace laboratory is accurately reproducing a real re even when the effects brought about the specimens are perfectly compatible and identied. We also acknowledge that, in real-world circumstances, the consumption and destruction of organic material may inuence the top temperature of the heating process of bone inorganic phase but not the consequent growth mechanism of crystallites. Subsequently our calibration is applied to some cremated human bones coming from various archaeological Spanish sites belonging to different historical ages, where we have investigated the powder patterns and, from the measured average crystallite size, temperature and time of treatment are estimated. 2. Materials For the kinetics study of the bone subjected to selected temperatures and times we have used 34 human femoral fragments collected in the Giant Tomb La Testa (Santa Teresa di Gallura, Sassari), belonging to the Nuragic era (Tedde et al., 1994). In order to verify the occurrence of a different behaviour with respect to ancient dry human bones some pieces of eshy pig bones were also treated according to the present protocol. The calibration was applied to cremated remains from Spain, details of which are given in Table 1. 3. Methods The samples used for calibration were heat-treated with a heating rate of 20  C/min at selected temperatures (200e 1000  C for 0, 18 and 60 min) in air using a NEY mufe

G. Piga et al. / Journal of Archaeological Science 35 (2008) 2171e2178 Table 1 The most relevant information of the Spanish bones here examined Specimen VMS C-13 IP-A 1962-2 IP-A 10 IP-A 11 IP-B 13 SM03 urna iberica 1 SM03 urna iberica 2 MB1-E378-9 MB1-E378-96 MB1-E378-76 SP01 UE 1020 Provenance Necropolis Plac a de la Vila de Madrid (Barcelona) Necropolis of Sillot des Porros (S. Margalida, Mallorca) Necropolis of Sillot des Porros (S. Margalida, Mallorca) Necropolis of Sillot des Porros (S. Margalida, Mallorca) Necropolis of Sillot des Porros (S. Margalida, Mallorca) Necropolis of Santa Madrona (Riba-roja, Ribera dEbre) Necropolis of Santa Madrona (Riba-roja, Ribera dEbre) ` s, Alt. Penede ` s) Mas den Boixos (Pacs del Penede ` s, Alt. Penede ` s) Mas den Boixos (Pacs del Penede ` s, Alt. Penede ` s) Mas den Boixos (Pacs del Penede Necropolis de Sebes (Flix, Ribera dEbre) Type of burial Interred in tomb Interred in tomb Interred in tomb Interred in tomb Interred in tomb Funerary urn Funerary urn Interred in tomb Interred in tomb Interred in tomb Funerary urn Chronology

2173

IeIV century A.D. roman VIeII century B.C talayotic culture VIeII century B.C talayotic culture VIeII century B.C talayotic culture VIeII century B.C talayotic culture III century B.C. Iberic culture III century B.C. Iberic culture VIIeVI century B.C. Iberic culture VIIeVI century B.C. Iberic culture VIIeVI century B.C. Iberic culture VIIeVI century B.C. Iberic culture

X-ray Intensity / arb. un.

furnace. The specimens for X-ray investigations were powdered by manual grinding in an agate mortar. The X-ray diffraction (XRD) patterns were recorded overnight using Bruker D8, Philips PW-1050, Siemens D500, Rigaku D/MAX diffractometers in the BraggeBrentano ). The goniomgeometry with Cu Ka radiation (l 1.54178 A eter was equipped with a graphite monochromator in the diffracted beam and the patterns were collected with 0.05 of step size. The X-ray generator worked at a power of 40 kV and 30 mA and the resolution of the instruments (divergent and antiscatter slits of 0.5 ) was determined using a-SiO2 and a-Al2O3 standards free from the effect of reduced crystallite size and lattice defects. The powder patterns were collected in the angular range 15e120 in 2q and were analyzed according to the Rietveld (1967) method, using the programme MAUD (Lutterotti et al., 1998). This is an efcient approach that evaluates quantitatively the amount, structure and microstructural parameters of mineralogical phases keeping into account also the instrumental parameters. This is a necessary pre-requisite in order to correctly distinguish from the peak broadening the average crystallite size from the lattice disorder. The method may replace previous approaches that were adopted to study the bones based on an arbitrarily dened index of crystallinity. Thermo-gravimetry and differential thermal analyses (TGe DTA) were conducted using a Setaram instrument from room temperature up to 1500  C at a heating rate of 20  C/min in air. After reaching the nal temperature, the specimens were immediately allowed to cool down. 4. Results and discussion In Fig. 1 we report a comparison of the X-ray diffraction intensity of untreated ancient human bone, untreated recent human bone recovered from the grave yard ossuary of Sassari which is not more than 50 years old, and untreated pig bone here studied as a function of the scattering angle 2q in the range 15e120 . Experiments are data points, full curve is the Rietveld t calculated according to the contribution of the structure factors of hydroxylapatite (monoclinic, space group P21/c, rened lattice parameters a 9.440, and b 120.67 ) and calcite b 18.898, c 6.896 A

). As is usual in the (trigonal, R-3c, a 4.988, c 17.070 A present Rietveld approach, the curve difference between calculated and experimental data points is shown at the bottom, while the sequence of bars indicates the expected peak positions for each phase. From the proposed comparison it emerges that there is no sensible difference in the structure factors of human and animal bones here examined, whether they are fresh or dry and ancient. This may represent a strong point in order to use XRD as a probe for the possible burning of bones, whatever the animal or human origin. The quantitative Rietveld analysis points to the fact that hydroxylapatite is the main phase for bones. The structure of hydroxylapatite is also reported hexagonal, space group P63/ mmc but the monoclinic structure factor was preferred since it gave systematically better agreement factors dealing with our pattern collection. The peak proles of hydroxylapatite are very broad on account of the nanocrystalline condition of materials with very small average crystallite size and/or large lattice disorder. The average coherent diffraction domain calculated after separating strain from size effects according to

Untreated pig bone

Untreated ancient human bone

Untreated recent human bone

CaCO3 HA

40

80

120

Scattering Angle 2
Fig. 1. The XRD powder pattern of untreated ancient bone used as sample reference coming from the Giant Tomb of La Testa (Sassari). Experiments are data points, full line is the Rietveld renement on the basis of hydroxylapatite and calcite structure factors. The line at the bottom refers to the residuals, i.e., the difference between calculated and experimental square root intensities, which is indicative of the agreement obtained.

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. the Rietveld approach is in the range between 168 and 177 A Note that, apart from root mean square deviation problems, this result may be different from the gure normally obtained applying the Scherrer (1918) equation on the most intense peak. The value may also be distinct from the average particle size that can be evaluated using SAXS data, since the latter may refer to a collection of agglomerated crystallites (Guinier, 1963; Hiller et al., 2003; Thompson, 2005). Further, it should be kept in mind that average values from transmission electron microscopy observations refer to a surface weighted mean (Matyi et al., 1987). A weak component of calcite (ca. 3.0 wt%) was also identied in the pattern. The presence of calcite is to be expected in bones but this is not a rule. According to Wopenka and Pasteris (2005), the maximum amount of endogenous calcite in human bones may not exceed 7e8 wt%, as estimated from 3 CO2 3 groups that can substitute for PO4 in the hydroxylapatite structure. Fig. 2A shows the thermogravimetric (TG) and differential thermal analysis (DTA) curves of the ancient sample bone here studied as a function of the temperature. The TG curve shows a moderate weight loss of about 5% before 400  C with a broad exothermic peak which can be due to dehydroxylation. This observation is in qualitative fair agreement with recent `nez-Blanes TGeDTA curves reported by Odriozola and Mart (2007), where a larger weight loss of an apatite bone was reported. Also, in our curve a sharp weight loss occurs above the temperature of 800  C, which can be assigned to the loss of carbon dioxide from calcite according to the chemical reaction: CaCO3 2 CaO CO2 : The endothermic peak at the correspondent temperature is a further conrmation for this reaction (see also the XRD pattern analysis reported later). Further heating to 1500  C does not affect substantially the state of the bone in terms of transformation phenomena and/or weight loss. This interpretation may be in contrast with the work by Wang et al. (2004) and `nez-Blanes (2007), but is supported by Odriozola and Mart Kalsbeek and Richter (2006). Note that, the trace of another ancient bone recently published by us (Enzo et al., 2007)

did not show any sharp weight loss around 800  C. On the other hand, the bone here studied may be regarded unconventional because ancient. In fact in Fig. 2B we report the TGe DTA curves of a recent human bone. It can be seen that in this case there is not signicant evidence of CO2 evolution around 800  C. Also, the weight loss is higher in percentage probably due to the larger fraction of collagen in the recent bone. This is also conrmed by the exothermal wide peak located around 350  C. We report in Fig. 3 a selected portion of patterns from 30 to 39 in 2q referred to the specimens heated up to the temperatures of 700, 775, 800, 825, 850, 900 and 1000  C, respectively, which show the disappearance of calcite and the simultaneous appearance of calcium oxide as argued from the thermogram previously reported in Fig. 2. As it can be seen, the peak of calcium oxide occurring at 2q 37.5 starts to appear at 775  C, becomes evident at 800  C and increases with the temperature until 1000  C, this phase reaching its maximum amount. Line broadening analysis as a function of temperature and residence time for the hydroxylapatite phase allows to observe a clear evolution due to an average crystallite size increase which has been separated from the lattice strain. As it concerns the values for the lattice strain, these are better determined from the peak broadening at high angles (>80 in 2q) where unfortunately the intensity is very weak. This fact required a suitably long data collection strategy. It should be clear that these problems all together represent a further limitation for precise determination of the heat-treatment in unknown bones using comparative analyses. This so determined average crystallite sizes of the HA min units. eral phase are collected in Table 2 and given in A For temperatures from 200  C to around 650  C no significant growth appears to be induced. Also, the residence time of 18 and 60 min at these temperatures is not changing dramatically the microstructure, with only slight effects of grain growth, on account of a relative stability of the system. It is not so from 700  C (60 min) and higher temperatures, where an effect of sudden growth appears evident and further distinguishable in the temperature range 750e850  C, where three different growth processes can be evaluated.

A
Relative Weight fraction
1.00 0.95 0.90 0.85 0.80 200 TG

Ancient Sample bone

B
16 14 12 10 8 6 4 2 0 -2 -4 1.05

Recent bone
1.00 0.95 0.90 0.85 0.80 0.75 0.70 0 200 400 600 800 1000 1200 1400 TG Heat-flow

Heat flow

400

600

800 1000 1200 1400

Relative Weight fraction

heat flux/arb. un.

Temperature

Temperature

Fig. 2. (A, B): A comparison of TGeDTA curves for the ancient (left-side) and recent (right-side) bones, respectively. In the rst case the bone contains calcite which eventually evolves CO2 at high temperatures. This is not so for the recent bone, where a larger fraction of collagen seems to be present as it appears from the weight loss curves.

G. Piga et al. / Journal of Archaeological Science 35 (2008) 2171e2178

2175

CaO

1000

900

850

825

800 775

750

700

for the size determination In fact an upper limit of 1500 A is generally associated to this technique, depending from the collimation arrangement adopted. We may also note that the residence time of 60 min evidences an effect of crystallite growth that would be obtained at temperatures 100  C higher without any residence time. This allows to establish a condence degree for the applicability of the present experimental approach. Objections may be raised about the use of archaeological remains for this calibration, since the real re was conducted on bodies. For this reason we have performed a partial comparative test by using eshy pig bones. In Fig. 4 we present the XRD patterns of fresh pig bones as a function of some selected temperatures and residence times. Table 3 reports the average crystallite size deduced according to our Rietveld approach, which demonstrates a behaviour of the crystallite growth as a function of temperature very close to that observed for ancient dry bones. It may be concluded that the destruction by re of organic parts affects only slightly the heating process but does change signicantly the growth process of HA crystallites as a function of the temperature.
CaO HA

X-ray Intensity / arb. un.

30

32

34

36

38

Scattering Angle 2
Fig. 3. A selected range of the XRD patterns of sample bone treated at the indicated temperatures. It is evident that the progressive peak sharpening of hydroxylapatite as a function of the indicated temperatures, simultaneous to the appearance of CaO phase following the decarbonatation reaction which starts at 775  C.

1000-0min

900-18min

For specimens treated at temperatures higher than 850  C and for long residence times the determination of the average crystallite size may be of difcult reproducibility because of the instrument contribution. This problem was similarly experienced by Hiller et al. (2003).
Table 2 1010 m) Average crystallite size of the hydroxylapatite mineral phase (1 A Temperature ( C) Not burned 200 300 400 500 600 650 700 750 775 800 825 850 900 1000 0 min 170 175 180 195 202 204 213 229 268 350 432 732 923 1351 >1500 (1569) 18 min 175 184 203 202 240 226 294 611 836 1030 1120 1380 >1500 (1616) >1500 (2195) 60 min 175 188 205 210 256 258 486 800 920 1200 1254 1500 >1500 (2621) >1500 (2950)

X-ray Intesnity /arb. un.

800-18min

750-0min

700-60min

600-18min

500-0 min

20

40

60

80

100

120

Scattering Angle 2
Fig. 4. The XRD patterns (data points) and the Rietveld t (full lines) of ashy pig bone pieces subjected to selected temperature treatments and holding times indicated.

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G. Piga et al. / Journal of Archaeological Science 35 (2008) 2171e2178 Table 4 The best-t parameters of the three logistic curves represented in Fig. 3 Parameters A1 (xed) A2 x0 p 0 min 180 1597 845 24 18 min 180 2420 844 12 60 min 180 3528 860 12.46

Table 3 Average crystallite size of hydroxylapatite mineral phase obtained after the Rietveld investigation of pig bones heated at selected temperatures and holding times Temperature ( C) 500 600 700 750 800 900 1000 Residence (min) 0 18 60 0 18 18 0 Average crystallite ) size (20 A 203 243 482 269 1029 >1500 (1611) >1500 (1577)

At variance with the residence time the three sigmoidal curves are all located around 850  C. The p parameter is related to the sharp behaviour of the function.

The data compare very closely with analogue treatments carried out on human ancient bones.

The markedly different behaviour for the specimens treated above 650  C is clearly seen also in Fig. 5, where symbols refer to the measured crystallite size values as a function of temperature treatment. Restricting our attention to the specimens heated without any residence time, we can appreciate even with the logarithmic scale the rather sudden increase of the average crystallite size for temperatures around 750  C, in agreement with previous XRD observations. The growth process seems to proceed up to 1000  C in keeping with a sigmoidal growth-type law typical of most of the reactions in the solid state. The following equation (full lines) was t to the experimental data: y A2 A1 A2 =1 x=x0 p The optimized parameters that are presented in Table 4 have a precise physical meaning: A1 value was actually xed to the size dimension of HA for samples before any sensible growth; A2 is the size limit reached at the end of the growth

process; x0 is the temperature relevant to the ex point of the logistic curves and p is a parameter for the rate growth, likely dependent from scanning rate, temperature and residence time. Note that for the series at time residence of 0 min the growth phenomenon is particularly sharp in the range 750e 900  C, while for the other two curves the growth kinetics appears to occur in a more extended range from 600 to 1000  C where the relevant p values are quite close. 5. Study of Spanish burnt bones collection The patterns of 11 Spanish burned bones here presented are reported in Fig. 6. All specimens except for MB1-E378-96 show the dominant presence of HA with traces of calcite. Conversely, sample MB1-E378-96 is made up by phases typical of ash that is calcite, quartz and muscovite with only a fraction 30.0 wt% of HA. For some specimens the calcite amounts to ca. 19.0 wt%, suggesting a likely exogenous origin for this mineral (for example from the contact with ground of limestone). For all samples except for IP-B13 we may notice in the patterns a considerable peak sharpening, due to marked crystallite growth and lattice strain reduction which is induced by the occurred thermal treatment. These features can be appreciated in Fig. 7 where the patterns are reported in the conventional angular range 30e39 in 2q. Concerning the average crystallite size values and lattice strain, the 11 investigated specimens have supplied the results collected in Table 5. As it is surmised all the remains were subjected to re treatment at very high temperature (750e1000  C) except for specimens IP-B13 which turns out to be burned at lower temperatures (<500  C). The calculated high temperature values clearly show as in early ages the re technology in Spain was considerably effective and developed for crematory practices. 6. Conclusions A new and detailed protocol to estimate the temperature and possible duration of a funerary cremation rite was developed in the temperature range 200e1000  C for various residence times (0, 18 and 60 min) using the X-ray powder diffraction technique.

Average crystallyte size/

0 min 18 min 60 min

1000

100 100

200

300

400

500

600

700

800

900 1000 1100

Temperature / C
Fig. 5. The average crystallite size evolution for hydroxylapatite as a function of temperature treatment and residence times indicated. The experimental data from the Rietveld analysis have been tted with sigmoid curves of logistic type which are typical of physico-chemical growth processes. The scatter of data and curves gives an idea of the uncertainty related to the determination of the temperature treatment for a bone of unknown provenance.

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2177

MB1-E378-96

IP-A1962-2

IP-A11 VMS-C13

X-ray Intensity/arb. un.

X-ray Intensity

IP-A10

MB1-E378-76

SM-1

MB1-E378-9

SM-2 SP-01UE1020 IP-B13

20

40

60

80

100

120

20

30

40

50

60

70

80

90 100

Scattering Angle 2

Scattering Angle 2

Fig. 6. The experimental patterns (data points) and Rietveld t (full lines) of bones from Spanish sites here investigated. Note the signicant peak sharpening in all samples except for IPB-13, which testify for the re technology in use in Spain in ancient times.

The growth process undergone by the crystallites of the mineralogical phase hydroxylapatite follows a sigmoid trend of logistic type with a characteristic temperature around 850  C, as it was determined for the three times investigated. In the thermal treatment for 0 min the growth rate seems to be higher than for curves at subsequent times.

Thermal treatments for 60 min anticipate of about 100  C the effects that are otherwise observed after the treatments for 0 min. Based on these calibration curves, 11 cremated Spanish bones were investigated. It was established that they were subjected to re treatment at high temperatures in the range

MB1-E378-96 IP-A1962-2

X-ray Intensity/arb. un.

VMS-C13

IP-A11

X-ray Intensity

IP-A10

MB1-E378-76

SM-1

MB1-E378-9

SM-2 SP-01UE1020 IP-B13

33

36

30

33

36

Scattering Angle 2

Scattering Angle 2

Fig. 7. The patterns of Fig. 5 reported for comparative purposes in the angular range where originally a crystallinity index was dened. The t with full lines to experimental data points gives a condence test for the hydroxylapatite structure factor and model crystallite size parameters.

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Table 5 Possible evaluation of the temperature treatment to which the Spanish bones were likely subjected determined on the basis of the calibration procedure here conducted Sample code IP-A 1962-2 IP-A 10 IP-A 11 IP-B 13 SM03 urna iberica 1 SM03 urna iberica 2 SP01 UE 1020 MB1-76 MB1-E378-96 MB1-E379-9 VMS-C13 ) Average crystallite size (20 A >1500 (1829) >1500 (2784) >1500 (1850) 195 >1500 (2812) >1500 (2590) >1500 (2296) >1500 (2244) 1502 1202 581 Lattice disorder (103) 1 10 2 104 1 105 1 103 1.4 104 3.5 104 5 105 1 104 2.4 104 6 106 1.7 104
5

Temperature (30  C) 900 for longer than 18 min 1000 for <60 min or 900 for longer than 1 h 900 for longer than 18 min <500 1000 for <60 min or 900 for longer than 1 h 900 for shorter than 1 h 1000 for shorter than 18 min 1000 for longer than 18 min 850 for about 60 min 800 for about 60 min 750 for shorter than 18 min

750e1000  C, except for sample IP-B13 that turned out to be burned at lower temperatures (<500  C). For nine samples the cremation times were evaluated shorter than 1 h but for two of them the duration was longer. The high temperatures determined in the examined specimens clearly demonstrate that in various ancient ages of Spain to which samples are referring, the re technology was well developed and quite efcient even in funerary cremation rites. Acknowledgements G. Piga is particularly grateful to Prof. Vittorio Mazzarello, Prof. Andrea Montella and the Regione Autonoma della Sardegna for supporting his Master and back project. The authors expressly thank Vittorio Mazzarello, Xavier Exteve, Ethel , Jaume Noguera and Julia Beltran for supplying the Allue specimens collection here studied. References
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