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

doi:10.13745/j.esf.sf.2020.5.54

Abstract

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

CLC Number:

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.

Figures/Tables 14

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

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

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

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

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

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

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

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

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

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

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

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