Korean Journal of Mineralogy and Petrology (광물과 암석)

The Petrological Society of Korea & The Mineralogical Society of Korea (한국암석학회 & 한국광물학회)
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Effect of Lead Content on Atomic Structures of Pb-bearing Sodium Silicate Glasses: A View from 29Si NMR Spectroscopy

납 함량에 따른 비정질 Pb-Na 규산염의 원자 구조에 대한 고상 핵자기 공명 분광분석 연구

  • Lee, Seoyoung (School of Earth and Environmental Sciences, Seoul National University) ;
  • Lee, Sung Keun (School of Earth and Environmental Sciences, Seoul National University)
  • 이서영 (서울대학교 지구환경과학부) ;
  • 이성근 (서울대학교 지구환경과학부)
  • Received : 2021.08.04
  • Accepted : 2021.09.16
  • Published : 2021.09.30
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Abstract

Lead (Pb) is one of the key trace elements, exhibiting a peculiar partitioning behavior into silicate melts in contact with minerals. Partitioning behaviors of Pb between silicate mineral and melt have been known to depend on melt composition and thus, the atomic structures of corresponding silicate liquids. Despite the importance, detailed structural studies of Pb-bearing silicate melts are still lacking due to experimental difficulties. Here, we explored the effect of lead content on the atomic structures, particularly the evolution of silicate networks in Pb-bearing sodium metasilicate ([(PbO)x(Na2O)1-x]·SiO2) glasses as a model system for trace metal bearing natural silicate melts, using 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy. As the PbO content increases, the 29Si peak widths increase, and the maximum peak positions shift from -76.2, -77.8, -80.3, -81.5, -84.6, to -87.7 ppm with increasing PbO contents of 0, 0.25, 0.5, 0.67, 0.86, and 1, respectively. The 29Si MAS NMR spectra for the glasses were simulated with Gaussian functions for Qn species (SiO4 tetrahedra with n BOs) for providing quantitative resolution. The simulation results reveal the evolution of each Qn species with varying PbO content. Na-endmember Na2SiO3 glass consists of predominant Q2 species together with equal proportions of Q1 and Q3. As Pb replaces Na, the fraction of Q2 species tends to decrease, while those for Q1 and Q3 species increase indicating an increase in disproportionation among Qn species. Simulation results on the 29Si NMR spectrum showed increases in structural disorder and chemical disorder as evidenced by an increase in disproportionation factor with an increase in average cation field strengths of the network modifying cations. Changes in the topological and configurational disorder of the model silicate melt by Pb imply an intrinsic origin of macroscopic properties such as element partitioning behavior.

납(lead; Pb)은 지구 형성 초기의 원시 맨틀(primitive mantle)에서부터 현재 지구로의 진화 과정 이해에 중요한 정보를 제공하는 미량 원소 중 하나이다. 납은 지구 내부 및 지각에서 다양한 화성 과정에 수반하는 규산염 광물과 용융체 내에 차별적으로 분배된다. 원소 분배 계수 변화는 규산염 용융체 구조와 밀접한 관련이 있을 것으로 알려져 있다. 따라서 본 연구의 목적은 납이 포함된 규산염 용융체의 자세한 구조를 밝히고, 조성에 따라 변화하는 구조와 특성, 특히 규산염 광물과 용융체 간의 원소 분배 계수와의 관계를 제시하는 것이다. 본 연구에서는 고상 NMR 분광분석을 수행하여 비정질 Pb-Na 규산염의 자세한 원자 구조를 확인하였다. 자연계 마그마 용융체의 모델 시스템으로 납이 포함된 비정질 유리 시료[(PbO)x(Na2O)1-x]·SiO2를 소듐과 납의 단종 Na2SiO3에서 PbSiO3까지 다양한 조성의 비정질을 합성하였으며(x=0, 0.25, 0.33, 0.50, 0.67, 0.86, 1) 납의 함량에 따른 규소 주변 원자 환경의 변화를 확인할 수 있는 29Si MAS NMR 분광분석을 수행하였다. 29Si MAS NMR 결과 납 함량에 따라 피크의 폭이 넓어지고 피크 최대값의 위치는 -76.2, -77.8, -80.3, -81.5, -84.6, -87.7 ppm으로 이동하였다. 규소와 결합된 연결 산소의 양인 Qn 환경 변화를 정량적으로 분리하기 위하여 29Si NMR 스펙트럼에 대한 시뮬레이션을 수행하였다. 시뮬레이션은 조성에 따라 NBO/T로 나타낸 중합도가 일정하면서 Qn 환경의 화학적 차폐 이동을 가정한 경우 가우시안 함수의 조합으로 진행하였다. 그 결과 규소 주변 원자 환경 변화에 기인한 화학적 차폐의 이동이 시사된다. Na2SiO3의 경우 Q2가 지배적으로 존재하며 Q1 및 Q3가 비슷한 비율로 존재하였으나 소듐 대신 납이 포함되면서 Q2가 감소하고 Q1 및 Q3가 증가하면서 Qn 환경의 불균화가 증가하였다. 29Si NMR 스펙트럼에 대한 시뮬레이션 결과는 납을 포함한 비정질 규산염에서 조성에 따른 배열 무질서도 및 위상 무질서도 증가를 지시한다. 본 결과로부터 평균 양이온 세기(average cation field strengths)에 따른 불균화 상수(disproportionation factor)의 변화를 정량화하였다. 무질서도의 증가와 비정질의 구조 변화가 납을 포함한 미량 원소의 분배 계수를 감소시킬 것으로 예상된다.

Keywords

Acknowledgement

본 연구는 이성근 교수에게 지원된 한국연구재단과제(NRF-2020R1A3B2079815)로 수행되었습니다. 사독해주신 익명의 심사위원 두 분과 유봉철 편집장님께 깊은 감사를 드립니다.

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