The Thermodynamic Characteristics of Quartz E' Center and Their Significance
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摘要: 石英EPR是一种利用矿物吸收的累积辐射能进行测年的技术方法，尽管多用于第四纪，但石英E'心在热活化后极大增强的EPR信号为拓展EPR的测年范围提供了契机.然而石英E'心的热活化条件及形成转化机理存在诸多争议.通过对花岗岩和断层带样品施加人工γ辐照，并通过步进式的阶梯退火实验，运用电子顺磁共振技术测定了不同辐射条件及温度条件下的石英E'心信号强度，探讨了石英E'心的增长和成因机理.结果表明，石英E'心可在常温常规γ辐照和高温加热2种条件下增长，并分别探讨了常温和高温E'心的测年方法及其地质意义.常温E'心的信号强度在150℃以下相对稳定，可用常规附加剂量法标定EPR信号强度以求取累积辐射能，常用于测定第四纪范围内断层的形成年龄；石英E'心在热活化后信号得到极大增强，可测定第四纪前的地质年龄，但需采用已知年龄的石英E'心热力学峰值强度作标杆或通过高剂量的γ辐照或中子辐照使氧空位再生，建立石英氧空位的剂量响应曲线以标定高温E'心代表的累积辐射能.E'心的热力学峰值通过步进式的阶梯退火实验确定，其在高温和常温时的信号强度比(I2/I1)具有记录辐射能和地质计时的意义.Abstract: The electron paramagnetic resonance of quartz is a dating technique through accumulated irradiation energy absorbed by minerals. Although it is commonly used in Quaternary period,the greatly enhanced EPR signals of quartz E' center after thermal activation provide opportunity for extending the dating range of EPR,while there are many different opinions on the thermal activation physical conditions and the formation and transformation mechanism of quartz E' center. In this paper,through the artificial γ ray radiation and stepwise annealing experiments to the granite and fault zone samples,the quartz E' center signal intensities under different irradiation conditions and different temperatures are measured by EPR technique,and the growth and formation mechanisms of quartz E' center are studied. The results indicate that the signal intensity of quartz E' center can be enhanced by normal artificial γ ray radiation under room temperature and by high temperature heating. The dating method and geological significance of E' center at normal and high temperature is discussed separately. The signal intensity of normal E' center is relatively constant below 150℃,and can be calibrated to calculate the accumulated dose and date fault forming age within Quaternary by normal additive dose method. The signal intensity of quartz E' center can be greatly enhanced by thermal activation and can be used to date geological age before Quaternary,but the activated peak signal intensity of known age quartz E' center should be used as a benchmark or the oxygen vacancy should be regenerated by high-dose γ ray irradiation or neutron irradiation. Then,the dose response curve of oxygen vacancy in quartz can be fitted to calculate the accumulated irradiation energy represented by the high temperature E' center. The thermodynamic peak of E' center should be determined by stepped annealing experiment and its signal intensity ratio (I2/I1) at high temperature and room temperature has the geological significance of recording irradiation energy and geological age.
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图 1 不同样品E′心信号强度随温度变化
Fig. 1. The signal intensity of quartz E′ center in both samples at several temperature points
图 2 不同人工辐照剂量样品达到E′心峰值时的温度点
Fig. 2. The temperature points at which the peak signal intensities of E′ center are reached in samples with different artificial γ ray irradiation dose
图 3 不同辐照剂量样品在热力学试验后获取的E′心最大值
Fig. 3. The peak signal intensity of E′ center after thermodynamic experiments in samples with different artificial γ ray irradiation dose
图 4 样品1的自然样品不同方位下多次测量EPR信号强度的离散性
以样品1的自然样品为例，在完全相同的参数条件下，在0°、120°、240°三个方位下固定样品管位置重复测试6次，共测量18次，它们的标准偏差和相对标准偏差分别为1 759和7.2%
Fig. 4. The multiple measurement discrepancy of EPR signal intensity under different directions of natural sample of number 1
图 5 不同温度点下样品E′心信号强度的剂量响应关系
Fig. 5. The dose response relationship of E′ center signal intensity under several temperature points in both samples
图 6 样品I2/I1值与辐照剂量的关系
Fig. 6. The relationship between I2/I1 ratio of samples and artificial γ ray irradiation dose
图 7 氧空位、E′心、Al心的结构模型
据Rink and Odom(1991)改编. a.石英正常的晶格位置；b.连接硅原子的桥接氧移位，形成氧空位；c.氧空位处捕获一个自由电子，形成E′心；d. Al心
Fig. 7. Structure model of oxygen vacancy, E′ center and Al center
图 8 石英中E′心、Al心和Ti心在加热后EPR信号强度的变化
据Toyoda(2005).石英中Al心和Ti心的信号强度随温度升高而下降，而E′心在300 ℃左右信号强度达到最强后才开始下降
Fig. 8. Change of intensity of the EPR signals of the E′, Al and Ti centers in quartz
图 9 Al心和热处理E′心的剂量响应
据Toyoda and Hattori(2000)；Toyoda(2005)；Toyoda et al.(2016). Al心的强度增加而E′心在200 Gy以上饱和，表明饱和是由于氧空位的数量有限
Fig. 9. The dose response relationship of Al center and thermal activated E′ center
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