富氯造岩矿物中溴的分子结构

doi:10.13745/j.esf.sf.2020.5.54

地学前缘 ›› 2020, Vol. 27 ›› Issue (5): 10-13.DOI: 10.13745/j.esf.sf.2020.5.54

所属专题： Research Articles (English)

• 成因矿物学研究基础:矿物识别及定量化表征 • 上一篇下一篇

富氯造岩矿物中溴的分子结构

Yuanming Pan¹(), Ning Chen¹^,², Jianfeng Zhu³, Neelege Hopps¹, Eli Wiens¹, Jinru Lin¹^,⁴

1.Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK S7N 5E2, Canada
2.Canadian Light Source, University of Saskatchewan, Saskatoon, SK S7N 0X4, Canada
3.Saskatchewan Structural Sciences Centre, University of Saskatchewan, SK S7N 5C9, Canada
4.Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang, Liaoning 110016, P. R. China

收稿日期:2020-03-21 修回日期:2020-05-19 出版日期:2020-09-25 发布日期:2020-09-25
作者简介:E-mail address: yuanming.pan@usask.ca
基金资助:
The Natural Science and Engineering Research Council (NSERC) of Canada Discovery Grants(169994-201);The Natural Science and Engineering Research Council (NSERC) of Canada Discovery Grants(2018-04106)

Local structural environments of bromine in chlorine-rich minerals: Insights from Br K-edge XAS and ⁸¹Br MAS NMR spectroscopy

Yuanming Pan¹(), Ning Chen¹^,², Jianfeng Zhu³, Neelege Hopps¹, Eli Wiens¹, Jinru Lin¹^,⁴

1. Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK S7N 5E2, Canada
2. Canadian Light Source, University of Saskatchewan, Saskatoon, SK S7N 0X4, Canada
3. Saskatchewan Structural Sciences Centre, University of Saskatchewan, SK S7N 5C9, Canada
4. Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang, Liaoning 110016, P. R. China

Received:2020-03-21 Revised:2020-05-19 Online:2020-09-25 Published:2020-09-25

摘要/Abstract

摘要：

卤族元素诸如氯和溴作为地球化学示踪剂,常用于指示岩浆、变质岩和热液的来源和演化过程。而认清溴在造岩矿物中的形态和结构有助于丰富和完善其在地质环境演变中的示踪作用。但是,溴在造岩矿物中的含量极低导致大多数结构分析方法都无法使用,因此造岩矿物中微量溴的结构研究极具挑战性。本文采用 ⁸¹Br魔角旋转核磁共振(MAS NMR)光谱和同步辐射吸收光谱(XAS)技术,首次对富氯造岩矿物中的微量溴进行了结构分析。结果表明溴离子在方硼石中的微区结构不同于该矿物中三配位Cl原子的结构环境,而与Mg₃B₇O₁₃Br中八面体配位的溴离子相似,表明即使在微量条件下也存在域偏析。而对其他富氯造岩矿物的Br K边X光吸收近边结构(XANES)光谱白线峰的位置和扩展X射线吸收精细结构(EXAFS)分析表明微量溴离子替代了这些矿物中氯的位置,导致局部结构扭曲膨胀。溴离子在造岩矿物中的这一微观结构研究结果可为探索氯和溴在地质演变过程的指示作用提供新的科学依据。

关键词: 卤族元素, 溴, 造岩矿物, 魔角旋转核磁共振, X光吸收光谱, 地球化学示踪

Abstract:

Halogens such as Cl and Br as geochemical tracers for constraining the sources and evolution of magmatic, metamorphic and hydrothermal systems require knowledge about their structural environments in both rock-forming minerals and coexisting melts/fluids. However, structural studies of Br in rock-forming minerals are challenging due to its exceedingly low concentrations that are not amendable to most structural techniques. In this study, we have conducted the first structural investigation of Br as a trace constituent in selected Cl-rich rock-forming minerals by use of combined ⁸¹Br magic angle spin nuclear magnetic resonance (MAS NMR) spectroscopy and Br K-edge synchrotron X-ray absorption spectroscopy (XAS). The whiteline positions of the Br K-edge X-ray absorption near-edge structure (XANES) spectra vary systematically with the coordination numbers of the Cl atoms, except for that in boracite. Similarly, fittings of extended X-ray absorption fine structure (EXAFS) data support the substitution of Br^- for Cl^-, with significant local expansions. However, the local structural environment of Br in boracite from EXAFS fittings differs from this of the three-coordinated Cl atom in this mineral but is similar to that of the octahedrally coordinated Br in cubic Mg₃B₇O₁₃Br, suggesting a domain segregation even at the trace level. These local structural data provide new insights into the Br/Cl behavior in geological systems.

Key words: Halogens, Bromine, Rock-forming minerals, MAS NMR, XAS, Geochemical tracer

中图分类号:

Yuanming Pan, Ning Chen, Jianfeng Zhu, Neelege Hopps, Eli Wiens, Jinru Lin. 富氯造岩矿物中溴的分子结构[J]. 地学前缘, 2020, 27(5): 10-13.

Yuanming Pan, Ning Chen, Jianfeng Zhu, Neelege Hopps, Eli Wiens, Jinru Lin. Local structural environments of bromine in chlorine-rich minerals: Insights from Br K-edge XAS and ⁸¹Br MAS NMR spectroscopy[J]. Earth Science Frontiers, 2020, 27(5): 10-13.

图/表 14

Table 1 Summary of samples investigated in this study.

No	Name/Formula	Source	Br (ppm)	References
1	NaBr	chemical (Alfar Aesar)
2	Mg₃B₇O₁₃Br	synthetic		1
3	boracite	Boron, California, USA	NA	1
4	marialite	Mpwapwa, Tanzania	1877±12	2,3
5	sodalite	South Africa	234±3	2,3
6	chlorapatite	Bob’s Lake, Ontario, Canada	75	2
7	chlorapatite	Dashkesan deposit, Azerbaijan	<0.5	4
8	potassic-chloro-hastingsite	Dashkesan deposit, Azerbaijan	<0.5	4
9	Cl-rich hornblende	Lofoton, Nordland, Norway	NA	5

Fig.1 81Br MAS NMR spectrum of synthetic Mg3B7O13Br showing a single resonance signal with the central transition at approximately ~11.8 ppm and negligible nuclear quadrupolar contribution, and the spinning side bands as weak satellite peaks.

Fig.2 Br K-edge XANES spectra of chlorine-rich minerals in comparison with the model compound NaBr.

Fig.3 R space curve fittings of Br K-edge EXAFS data of the model compound NaBr.

Table 2 Fittings of Br K-edge EXAFS data of the model compound NaBr.

No	Model			Fitted Parameters
No	Path	CN	R (Å)	CN	R (Å)	DW
1	Br-Na	6	2.986	6.0±0.5	2.90±0.02	0.0012±0.0010
2	Br-Br	12	4.224	9.5±0.5	4.16±0.02	0.0100^*
3	Br-Na	8	5.174	8.0±0.5	5.09±0.02	0.0020±0.0010
				$S 02$ =0.9, E₀=-5.2 eV, χ²=51750, residual=20.2, F-Test: 0.99998; Exp.Error: 0.00023, χ² w/o err: 0.0566, reduced χ²: 1647, R range: 1.8-5.1 Å

Table 2 Fittings of Br K-edge EXAFS data of the model compound NaBr.

No	Model			Fitted Parameters
No	Path	CN	R (Å)	CN	R (Å)	DW
1	Br-Na	6	2.986	6.0±0.5	2.90±0.02	0.0012±0.0010
2	Br-Br	12	4.224	9.5±0.5	4.16±0.02	0.0100^*
3	Br-Na	8	5.174	8.0±0.5	5.09±0.02	0.0020±0.0010
				$S 02$ =0.9, E₀=-5.2 eV, χ²=51750, residual=20.2, F-Test: 0.99998; Exp.Error: 0.00023, χ² w/o err: 0.0566, reduced χ²: 1647, R range: 1.8-5.1 Å

Fig.4 R space curve fittings of Br K-edge EXAFS data of sodalite from South Africa.

Table 3 Fittings of Br K-edge EXAFS data of sodalite.

No	Model			Fitted Parameters
No	Path	CN	R (Å)	Path	CN	R (Å)	DW
1	Cl-Na	4	2.738	Br-Na	4.0±0.5	2.84±0.02	0.0100^*
2	Cl-O	12	4.306	Br-O	12.0±0.5	4.26±0.02	0.0100^*
3	Cl-O	12	4.496	Br-O	12.0±0.5	4.45±0.02	0.0077±0.0010
4	Cl-Na	4	4.958	Br-Na	4.0±0.5	4.89±0.02	0.0050±0.0010
5	Cl-Al	12	4.968	Br-Al	12.0±0.5	4.90±0.02	0.0060±0.0010
6	Cl-Si	12	4.968	Br-Si	12.0±0.5	5.02±0.02	0.0062±0.0010
				$S 02$ =0.7, E₀=6.0 eV, χ²=11379, residual=27.6, F-Test: 0.99827; Exp.Error: 0.00051, reduced χ²: 36, χ² w/o err: 0.0022, R range: 1.9-5.1 Å

Table 3 Fittings of Br K-edge EXAFS data of sodalite.

No	Model			Fitted Parameters
No	Path	CN	R (Å)	Path	CN	R (Å)	DW
1	Cl-Na	4	2.738	Br-Na	4.0±0.5	2.84±0.02	0.0100^*
2	Cl-O	12	4.306	Br-O	12.0±0.5	4.26±0.02	0.0100^*
3	Cl-O	12	4.496	Br-O	12.0±0.5	4.45±0.02	0.0077±0.0010
4	Cl-Na	4	4.958	Br-Na	4.0±0.5	4.89±0.02	0.0050±0.0010
5	Cl-Al	12	4.968	Br-Al	12.0±0.5	4.90±0.02	0.0060±0.0010
6	Cl-Si	12	4.968	Br-Si	12.0±0.5	5.02±0.02	0.0062±0.0010
				$S 02$ =0.7, E₀=6.0 eV, χ²=11379, residual=27.6, F-Test: 0.99827; Exp.Error: 0.00051, reduced χ²: 36, χ² w/o err: 0.0022, R range: 1.9-5.1 Å

Fig.5 R space curve fittings of Br K-edge EXAFS data of marialite (ON70 from Mpwapwa, Tanzania).

Table 4 Fittings of Br K-edge EXAFS data of marialite.

No	Model			Fitted Parameters
No	Path	CN	R (Å)	Path	CN	R (Å)	DW
1	Cl-Na	4	2.848	Br-Na	1.8±0.5	2.98±0.02	0.0100^*
2	Cl-O	4	3.982	Br-O	4.0±0.5	3.65±0.02	0.0050±0.0010
3	Cl-O	8	4.010	Br-O	8.0±0.5	3.85±0.02	0.0066±0.0010
4	Cl-O	8	4.203	Br-O	8.0±0.5	4.43±0.02	0.0095±0.0010
5	Cl-Si	8	4.377	Br-Si	8.0±0.5	4.32±0.02	0.0100^*
6	Cl-Al	8	4.484	Br-Al	8.0±0.5	4.54±0.02	0.0050±0.0010
7	Cl-O	8	4.601	Br-O	8.0±0.5	4.56±0.02	0.0050±0.0010
				$S 02$ =0.5, E₀=4.7 eV, χ²=10358, residual=29.7, F-Test: 0.38535; Exp.Error: 0.00017, reduced χ²: 33.1, χ² w/o err: 0.00026, R range: 1.7-5.6 Å

Table 4 Fittings of Br K-edge EXAFS data of marialite.

No	Model			Fitted Parameters
No	Path	CN	R (Å)	Path	CN	R (Å)	DW
1	Cl-Na	4	2.848	Br-Na	1.8±0.5	2.98±0.02	0.0100^*
2	Cl-O	4	3.982	Br-O	4.0±0.5	3.65±0.02	0.0050±0.0010
3	Cl-O	8	4.010	Br-O	8.0±0.5	3.85±0.02	0.0066±0.0010
4	Cl-O	8	4.203	Br-O	8.0±0.5	4.43±0.02	0.0095±0.0010
5	Cl-Si	8	4.377	Br-Si	8.0±0.5	4.32±0.02	0.0100^*
6	Cl-Al	8	4.484	Br-Al	8.0±0.5	4.54±0.02	0.0050±0.0010
7	Cl-O	8	4.601	Br-O	8.0±0.5	4.56±0.02	0.0050±0.0010
				$S 02$ =0.5, E₀=4.7 eV, χ²=10358, residual=29.7, F-Test: 0.38535; Exp.Error: 0.00017, reduced χ²: 33.1, χ² w/o err: 0.00026, R range: 1.7-5.6 Å

Fig.6 R space curve fittings of Br K-edge EXAFS data of Cl-rich hornblende (potassic-ferro-chloro-sadanagaite) from Lofoton, Nordland, Norway.

Table 5 Fittings of Br K-edge EXAFS data of Cl-rich hornblende.

No	Model			Fitted Parameters
No	Path	CN	R (Å)	Path	CN	R (Å)	DW
1	Cl-Fe	1	2.42	Br-Fe	0.9±0.5	2.56±0.02	0.0065^*
2	Cl-Fe	2	2.49	Br-Fe	1.8±0.5	2.74±0.02	0.0100^*
3	Cl-K	1	3.28	Br-K	1.2±0.5	3.07±0.02	0.0038±0.0010
4	Cl-O	10	3.15	Br-O	9.8±0.5	3.29±0.02	0.0050±0.0010
5	Cl-Al	4	3.30	Br-Al	4.2±0.5	3.35±0.02	0.0068±0.0010
6	Cl-Si	2	3.40	Br-Si	2.2±0.5	3.36±0.02	0.0059±0.0010
				$S 02$ =0.9, E₀=-1.4 eV, χ²=22235, residual=19.3, F-Test: 0.9923; Exp.Error: 0.00026, reduced χ²: 70, χ² w/o err: 0.0014, R range: 1.6-4.2 Å

Table 5 Fittings of Br K-edge EXAFS data of Cl-rich hornblende.

No	Model			Fitted Parameters
No	Path	CN	R (Å)	Path	CN	R (Å)	DW
1	Cl-Fe	1	2.42	Br-Fe	0.9±0.5	2.56±0.02	0.0065^*
2	Cl-Fe	2	2.49	Br-Fe	1.8±0.5	2.74±0.02	0.0100^*
3	Cl-K	1	3.28	Br-K	1.2±0.5	3.07±0.02	0.0038±0.0010
4	Cl-O	10	3.15	Br-O	9.8±0.5	3.29±0.02	0.0050±0.0010
5	Cl-Al	4	3.30	Br-Al	4.2±0.5	3.35±0.02	0.0068±0.0010
6	Cl-Si	2	3.40	Br-Si	2.2±0.5	3.36±0.02	0.0059±0.0010
				$S 02$ =0.9, E₀=-1.4 eV, χ²=22235, residual=19.3, F-Test: 0.9923; Exp.Error: 0.00026, reduced χ²: 70, χ² w/o err: 0.0014, R range: 1.6-4.2 Å

Fig.7 R space curve fittings of Br K-edge EXAFS data of synthetic Mg3B7O13Br.

Fig.8 R space curve fittings of Br K-edge EXAFS data of boracite from Boron, California, USA.

Table 6 Fittings of Br K-edge EXAFS data of Mg3B7O13Br and boracite.

No.	Model			Mg₃B₇O₁₃Br			Boracite
No.	Path	CN	R(Å)	CN	R(Å)	DW	CN	R(Å)	DW
1	Br-Mg	6	3.01	5.6±0.5	3.03±0.02	0.0100^*	5.5±0.5	3.06±0.02	0.0100^*
2	Br-O	12	3.44	11.6±0.5	3.32±0.02	0.0030±0.0010	11.5±0.5	3.35±0.02	0.0052±0.0010
3	Br-B	4	3.50	4.4±0.5	3.63±0.02	0.0024±0.0010	4.4±0.5	3.58±0.02	0.0024±0.0010
4	Br-O	12	3.80	11.5±0.5	3.82±0.02	0.0019±0.0010	12.4±0.5	3.82±0.02	0.0096±0.0010
5	Br-B	12	4.26	11.5±0.5	4.22±0.02	0.0100^*	11.5±0.5	4.25±0.02	0.0100^*
				$S 02$ =0.6, E₀=-0.7 eV χ²: 150558.95 Residual: 10.1 F-Test: 0.00 Exp.Error: 0.000096 χ² w/o err: 0.0042 reduced χ²: 479 R range: 2.1-4.2 Å			$S 02$ =0.6, E₀=-6.0 eV χ²: 640440.89 Residual: 15.2 F-Test: 0.84 Exp.Error: 0.0000599 χ² w/o err: 0.0043 reduced χ²: 2059 R range: 2.2-4.3 Å

Table 6 Fittings of Br K-edge EXAFS data of Mg3B7O13Br and boracite.

No.	Model			Mg₃B₇O₁₃Br			Boracite
No.	Path	CN	R(Å)	CN	R(Å)	DW	CN	R(Å)	DW
1	Br-Mg	6	3.01	5.6±0.5	3.03±0.02	0.0100^*	5.5±0.5	3.06±0.02	0.0100^*
2	Br-O	12	3.44	11.6±0.5	3.32±0.02	0.0030±0.0010	11.5±0.5	3.35±0.02	0.0052±0.0010
3	Br-B	4	3.50	4.4±0.5	3.63±0.02	0.0024±0.0010	4.4±0.5	3.58±0.02	0.0024±0.0010
4	Br-O	12	3.80	11.5±0.5	3.82±0.02	0.0019±0.0010	12.4±0.5	3.82±0.02	0.0096±0.0010
5	Br-B	12	4.26	11.5±0.5	4.22±0.02	0.0100^*	11.5±0.5	4.25±0.02	0.0100^*
				$S 02$ =0.6, E₀=-0.7 eV χ²: 150558.95 Residual: 10.1 F-Test: 0.00 Exp.Error: 0.000096 χ² w/o err: 0.0042 reduced χ²: 479 R range: 2.1-4.2 Å			$S 02$ =0.6, E₀=-6.0 eV χ²: 640440.89 Residual: 15.2 F-Test: 0.84 Exp.Error: 0.0000599 χ² w/o err: 0.0043 reduced χ²: 2059 R range: 2.2-4.3 Å

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富氯造岩矿物中溴的分子结构

Local structural environments of bromine in chlorine-rich minerals: Insights from Br K-edge XAS and ⁸¹Br MAS NMR spectroscopy

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富氯造岩矿物中溴的分子结构

Local structural environments of bromine in chlorine-rich minerals: Insights from Br K-edge XAS and 81Br MAS NMR spectroscopy

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Local structural environments of bromine in chlorine-rich minerals: Insights from Br K-edge XAS and ⁸¹Br MAS NMR spectroscopy