X射线衍射技术在烧骨实验研究中的初步应用

doi:10.16359/j.1000-3193/AAS.2021.0042

人类学学报 ›› 2021, Vol. 40 ›› Issue (03): 513-525.doi: 10.16359/j.1000-3193/AAS.2021.0042cstr: 32091.14.j.1000-3193/AAS.2021.0042

X射线衍射技术在烧骨实验研究中的初步应用

黄超¹^,²^,³(), 张双权¹^,²^,³()

1.中国科学院脊椎动物演化与人类起源重点实验室,中国科学院古脊椎动物与古人类研究所,北京 100044
2.中国科学院生物演化与环境卓越创新中心,北京 100044
3.中国科学院大学,北京 100049

收稿日期:2020-12-18 修回日期:2021-02-18 出版日期:2021-06-15 发布日期:2021-06-24
通讯作者: 张双权
作者简介:黄超（1991-）,男, 中国科学院古脊椎动物与古人类研究所博士研究生,研究方向为旧石器时代动物考古学。E-mail: huangchao@ivpp.ac.cn
基金资助:
中国科学院战略性先导科技专项(XDB26030203);国家自然科学基金面上项目(41772025);国家自然科学基金面上项目(41672023)

Preliminary application of the X-rays diffraction technique in experimental study of burnt bones

HUANG Chao¹^,²^,³(), ZHANG Shuangquan¹^,²^,³()

1. Laboratory for Vertebrate Evolution and Human Origins of CAS at the Institute of Vertebrate Paleontology and Paleoanthropology, Chinese Academy of Sciences, Beijing 100044, China
2. CAS Center for Excellence in Life and Paleoenvironment, Beijing 100044
3. University of Chinese Academy of Sciences, Beijing 100049

Received:2020-12-18 Revised:2021-02-18 Online:2021-06-15 Published:2021-06-24
Contact: ZHANG Shuangquan

摘要/Abstract

摘要：

烧骨作为考古遗址中较为常见的一类特征遗物,对研究古人类用火行为有着重要的意义。过往研究表明,骨骼在加热过程中,其内部晶体会根据加热程度的不同产生不同的变化。骨骼在加热前的状态,能够在一定程度上反映古人类对骨骼进行热处理的动机与目的。为了了解骨骼在焚烧前的初始状态是否会对其内部晶体产生不同的影响,本研究利用56件现生羊骨进行了烧骨实验。实验设置了带肉骨、剔肉骨和干骨三种不同初始状态的骨骼,并在前人的研究基础上进一步细化了焚烧温度和时间参数。焚烧完成后,利用X射线衍射技术对所有样品进行了分析并观察其衍射图的差异。实验结果显示,骨骼有机质含量的多少,骨骼内部元素的不同,在一定的温度和时间条件下,会对骨骼内晶体的形成产生不同的影响。文章最后探讨了这种差异在考古研究中运用的可能性。

关键词: 烧骨, 实验考古学, 动物考古学, 生物考古学, XRD, 骨骼矿物

Abstract:

Burnt bones are commonly found in archaeological sites and they are significant to a due understanding of the uses of fire by prehistoric humans. Previous studies have shown that the crystalline state of burnt bones will change differently under varying heating intensities. In order to understand whether the initial states of bones will have some effects on their crystalline states after burning, 56 sheep bones were burned in this study. We prepared three different initial states of bones (fleshed, defleshed and dry), and we further refined the temperature and time parameters of incineration. All samples were analyzed by using XRD. We find that the different initial states did have an effect on the crystalline states of bones after their burning, under certain temperature and time conditions. We also discussed the possibility of the application of this discovery in archaeological research.

Key words: Burnt bone, Experimental archaeology, Zooarchaeology, Bioarchaeology, XRD, Bone mineral

中图分类号:

Q915.86

黄超, 张双权. X射线衍射技术在烧骨实验研究中的初步应用[J]. 人类学学报, 2021, 40(03): 513-525.

HUANG Chao, ZHANG Shuangquan. Preliminary application of the X-rays diffraction technique in experimental study of burnt bones[J]. Acta Anthropologica Sinica, 2021, 40(03): 513-525.

图/表 15

图 1 羟基磷灰石标准样品粉末衍射图及其主要衍射峰括号内的数字为衍射峰指数,是XRD中表征物相衍射峰的一种方式/The number in brackets is the diffraction peak index, which is a way to characterize the phase diffraction peaks in XRD

Fig.1 The powder diffraction pattern of hydroxyapatite standard sample and its main peaks

图2 三种初始状态的实验骨骼示例图 (a)加热前（unheated bones）;(b)加热后（heat-treated bones）

Fig.2 Three initial states of experimental bones

图3 参考Person等人利用衍射图计算羟基磷灰石结晶度方法

Fig.3 The Definition of the crystallinity index on the diffractogram of hydroxyapatite, according to Person, et al

图4 未经马弗炉加热的骨骼样品粉末衍射图 (a)新鲜骨骼（Flresh bone）;(b)干骨（Dry bone）。可以看到未经马弗炉加热的干骨已经能初步识别衍射峰300和202

Fig.4 Powder diffraction pattern of bone samples before heating in a muffle furnace

图5 带肉骨骼在不同加热温度下的粉末衍射图,加热时间为120 min

Fig.5 Powder diffraction patterns of fleshed bones heat-treated from 300°C to 800°C for 120 min

图6 剔肉骨骼在不同加热温度下的粉末衍射图,加热时间为120 min

Fig.6 Powder diffraction patterns of defleshed bones heat-treted from 300°C to 800°C for 120 min

图7 干骨在不同加热温度下的粉末衍射图,加热时间为120 min

Fig.7 Powder diffraction patterns of dry bones heat-treated from 300°C to 800°C for 120 min

图8 带肉骨在不同加热时间下的粉末衍射图,加热温度为300°C

Fig.8 Powder diffraction patterns of fleshed bones heat-treated at 300°C from 30 min to 240 min

图9 剔肉骨在不同加热时间下的粉末衍射图,加热温度为300°C

Fig.9 Powder diffraction patterns of defleshed bones heat-treated at 300°C from 30 min to 240 min

图10 干骨在不同加热时间下的粉末衍射图,加热温度为300°C

Fig.10 Powder diffraction patterns of dry bones heat-treated at 300°C from 30 min to 240 min

表 1 加热时间120 min的样品结晶度

Tab.1 The crystallinity index of the samples heated for 120 min

骨骼状态 Sample status 加热温度 Temperature	带肉骨 Fleshed bone	剔肉骨 Defleshed bone	干骨 Dry bone
300 °C	0.13	0.14	0.25
350 °C	0.13	0.15	0.19
400 °C	0.21	0.11	0.17
450 °C	0.14	0.1	0.21
500 °C	0.23	0.17	0.14
550 °C	0.22	0.18	0.31
600 °C	0.45	0.38	0.41
650 °C	1.19	0.76	0.52
700 °C	1.27	1.2	0.96
750 °C	1.26	1.21	0.87
800 °C	1.47	1.33	1.2

表 2 加热温度为300 °C 的样品结晶度

Tab.2 The crystallinity index of the samples heated at 300°C

骨骼状态 Sample Status 加热时间 Time	带肉骨 Fleshed bone	剔肉骨 Defleshed bone	干骨 Dry bone
30 min	0.12	0.13	0.31
60 min	0.14	0.14	0.21
90 min	0.11	0.13	0.36
120 min	0.13	0.14	0.25
150 min	0.14	0.14	0.19
180 min	0.19	0.13	0.28
210 min	0.22	0.13	0.31
240 min	0.15	0.13	0.24

图11 三种初始状态的骨骼在600 °C -800 °C 的衍射图峰型对比 (a) 600°C -750°C的带肉骨（Fleshed bones）;(b) 600°C -750°C的剔肉骨（Defleshed bones）;(c) 600°C -750°C的干骨（Dry bones）;(d) 800°C三种初始状态的骨骼（three initial states of bones: blue line-dry bone; red line-defleshed bone; black line-fleshed bone）。加热时间均为120 min,X轴为衍射角2θ（X axis represents 2θ）。

Fig.11 Powder diffraction patterns of three initial states of bones heat-treated from 600 °C to 800 °C for 120min

图12 不同加热时间的三种初始状态骨骼的衍射图细节对比左: 带肉骨（Fleshed bones）; 中: 剔肉骨（Defleshed bones）; 右:干骨（Dry bones）。加热温度300 °C。2θ范围为25°-35°

Fig.12 A detailed comparison of the diffraction patterns of three initial state of bones heat-treated at 300°C from 30 min to 240min

图13 实验中观察到的在三种初始状态骨骼中生成的附加相左:带肉骨/Fleshed bones）; 中: 剔肉骨（Defleshed bones）; 右:干骨（Dry bones)。加热时间为120 min（heat-treated from 650°C to 800°C for 120 min)。黑色箭头所指为附加相的衍射峰所在位置,该附加相极有可能为Ca3(PO4)2 /The peaks positions are pointed out with black arrows (2θ: 30°-40°)

Fig.13 The peaks of tricalcium phosphate Ca3(PO4)2 are found in three initial states of bones

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X射线衍射技术在烧骨实验研究中的初步应用

Preliminary application of the X-rays diffraction technique in experimental study of burnt bones

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