Arsenic incorporation in synthetic struvite (NH4MgPO4·6H2O): A ...
Arsenic incorporation in synthetic struvite (NH4MgPO4·6H2O): A synchrotron XAS and single-crystal EPR study Jinru Lin1, Ning Chen1,2, Yuanming Pan1,* 1
Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK S7N 5E2, Canada, Tel: 306-966-5699, Fax: 306-966-8593; Email: [email protected]
2
Canadian Light Source, University of Saskatchewan, Canada
Supplementary Information
Figure S1. Representative powder X-ray diffraction patterns of synthetic struvite and boussingaultite. Also shown for comparison are their respective reference patterns from the Inorganic Crystal Structure Database (ICSD).
Figure S2. SEM image showing a doubly-terminated, prismatic crystal of synthetic struvite (I-8)
Figure S3. Arsenic contents in synthetic struvite as a function of pH. Squares and circles denote data from Series I and II experiments. Uncertainties are shown or smaller than the symbols.
Figure S4. Line-position data (road maps) of Center II in struvite: a) and b) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, c) approximately parallel to the (001) face at ν = ~9.386 GHz, and d) approximately parallel to the (100) face at ν = ~9.386 GHz.
Figure S5. Line-position data (road maps) of Center I in struvite: a) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, b) approximately parallel to the (001) face at ν = ~9.386 GHz, c) approximately parallel to the (100) face at ν = ~9.386 GHz, and d) approximately parallel to the (010) face at ν = ~9.360 GHz.
Figure S6. Line-position data (road maps) of Center III in struvite: a) and b) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, c) approximately parallel to the (001) face at ν = ~9.386 GHz, and d) approximately parallel to the (100) face at ν = ~9.386 GHz.
Figure S7. Line-position data (road maps) of Center IV in struvite: a) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, b) approximately parallel to the (001) face at ν = ~9.386 GHz, c) approximately parallel to the (100) face at ν = ~9.386 GHz, and d) approximately parallel to the (010) face at ν = ~9.360 GHz.
Figure S8. Line-position data (road maps) of Center V in struvite: a) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, b) approximately parallel to the (001) face at ν = ~9.386 GHz, c) approximately parallel to the (100) face at ν = ~9.386 GHz, and d) approximately parallel to the (010) face at ν = ~9.360 GHz.
Table S1. Spin Hamiltonian parameters of five [AsO3]2− radicals in struvite at 295 K Matrix (Y)
k
Principal value/direction Yk θk(°) φk(°)
RMSD (mT)
Center I 0 1 2.00431(4) 1.6(9) 270 g 0 −0.00008(4) 2 2.00399(4) 90 2.00431(4) 3 2.00154(4) 88.3(9) 90 75 0.132 A( As) 56.576(6) 0 0 1 72.950(6) 93.8(2) 90 (mT) 72.910(5) 2 56.581(5) 2.8(2) 90 −0.817(5) 56.622(5) 3 56.576(5) 90 180 A(1H)† 0.271 0 0 1 0.688 30 270 (mT) 0.375 2 0.271 90 0 −0.180 0.584 3 0.271 60 90 Center II 2.00254(7) 0.00020(9) 0.00162(9) 1 2.00467(6) 37.1(9) 353(4) g 2.00291(7) -0.00030(7) 2 2.00298(7) 85(3) 258(2) 2.00343(6) 3 2.00122(6) 53(1) 165(3) 75 0.167 A( As) 69.038(9) -3.61(1) -7.27(1) 1 76.457(9) 52.7(2) 158.1(2) (mT) 61.523(9) 2.898(8) 2 60.210(9) 38.4(8) 321(5) 66.165(8) 3 60.059(9) 81(2) 61(2) Center III 2.0034(1) 0 0 1 2.00419(7) 71(1) 90 g 2.00392(7) 0.00079(5) 2 2.0034(1) 90 0 2.00188(5) 3 2.00161(5) 19(1) 270 0.158 A(75As) 58.27(1) 0 0 1 74.620(6) 19.4(2) 270 (mT) 59.989(9) -5.155(7) 2 58.271(9) 90 0 72.803(6) 3 58.172(9) 70.6(2) 90 Center IV 2.00322(6) 0 0 1 2.00349(6) 7(1) 90 g 2.00114(6) 0.00031(7) 2 2.00322(6) 90 0 0.134 2.00345(6) 3 2.00110(6) 97(1) 90 75 A( As) 62.975(6) 0 0 1 79.976(9) 92.1(2) 90 (mT) 79.951(9) -0.652(8) 2 62.975(6) 90 0 62.962(7) 3 62.937(7) 2.1(2) 90 Center V 2.00287(9) 0 0 1 2.00330(8) 7(2) 90 g 2.00108(8) 0.00030(9) 2 2.00287(9) 90 0 2.00326(8) 3 2.00104(8) 97(2) 90 75 0.193 A( As) 67.62(1) 0 0 1 84.771(9) 93.8(2) 90 (MHz) 84.694(8) -1.14(1) 2 67.64(1) 3.8(2) 90 67.71(1) 3 67.62(1) 90 0 Polar angle (θ) and azimuthal angle (φ) are relative to the crystallographic axes b and a, respectively. †, two equivalent matrices A(1H) are obtained from spectral simulations. 2.00399(4)
0 2.00154(4)
Table S2. Selected bond distances and directions in struvite (Pmn21: a = 6.955 (1), b = 6.142 (1), c = 11.218 (2) Å)
Bond
Distance (Å)
P-O3 P-O3 P-O2 P-O1 P-H4 P-H4 Mg-OW1 Mg-OW2 Mg-OW31 Mg-OW32 Mg-OW41 Mg-OW42
1.5417 1.5417 1.5440 1.5402 2.6699 2.6699 2.1158 2.1125 2.0763 2.0763 2.0553 2.0553
θ (°) 61.2 61.2 23.1 86.2 28.1 28.1 27.2 29.3 70.1 70.1 71.1 71.1
φ (°) 20.3 159.7 270 90 5.1 264.9 270 270 39.1 140.9 139.2 40.8
Polar angle (θ) and azimuthal angle (φ) are relative to the crystallographic axes b and a, respectively.
Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK S7N 5E2, Canada, Tel: 306-966-5699, Fax: 306-966-8593; Email: [email protected]
2
Canadian Light Source, University of Saskatchewan, Canada
Supplementary Information
Figure S1. Representative powder X-ray diffraction patterns of synthetic struvite and boussingaultite. Also shown for comparison are their respective reference patterns from the Inorganic Crystal Structure Database (ICSD).
Figure S2. SEM image showing a doubly-terminated, prismatic crystal of synthetic struvite (I-8)
Figure S3. Arsenic contents in synthetic struvite as a function of pH. Squares and circles denote data from Series I and II experiments. Uncertainties are shown or smaller than the symbols.
Figure S4. Line-position data (road maps) of Center II in struvite: a) and b) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, c) approximately parallel to the (001) face at ν = ~9.386 GHz, and d) approximately parallel to the (100) face at ν = ~9.386 GHz.
Figure S5. Line-position data (road maps) of Center I in struvite: a) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, b) approximately parallel to the (001) face at ν = ~9.386 GHz, c) approximately parallel to the (100) face at ν = ~9.386 GHz, and d) approximately parallel to the (010) face at ν = ~9.360 GHz.
Figure S6. Line-position data (road maps) of Center III in struvite: a) and b) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, c) approximately parallel to the (001) face at ν = ~9.386 GHz, and d) approximately parallel to the (100) face at ν = ~9.386 GHz.
Figure S7. Line-position data (road maps) of Center IV in struvite: a) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, b) approximately parallel to the (001) face at ν = ~9.386 GHz, c) approximately parallel to the (100) face at ν = ~9.386 GHz, and d) approximately parallel to the (010) face at ν = ~9.360 GHz.
Figure S8. Line-position data (road maps) of Center V in struvite: a) approximately parallel to the (101) crystal face at ν = ~9.386 GHz, b) approximately parallel to the (001) face at ν = ~9.386 GHz, c) approximately parallel to the (100) face at ν = ~9.386 GHz, and d) approximately parallel to the (010) face at ν = ~9.360 GHz.
Table S1. Spin Hamiltonian parameters of five [AsO3]2− radicals in struvite at 295 K Matrix (Y)
k
Principal value/direction Yk θk(°) φk(°)
RMSD (mT)
Center I 0 1 2.00431(4) 1.6(9) 270 g 0 −0.00008(4) 2 2.00399(4) 90 2.00431(4) 3 2.00154(4) 88.3(9) 90 75 0.132 A( As) 56.576(6) 0 0 1 72.950(6) 93.8(2) 90 (mT) 72.910(5) 2 56.581(5) 2.8(2) 90 −0.817(5) 56.622(5) 3 56.576(5) 90 180 A(1H)† 0.271 0 0 1 0.688 30 270 (mT) 0.375 2 0.271 90 0 −0.180 0.584 3 0.271 60 90 Center II 2.00254(7) 0.00020(9) 0.00162(9) 1 2.00467(6) 37.1(9) 353(4) g 2.00291(7) -0.00030(7) 2 2.00298(7) 85(3) 258(2) 2.00343(6) 3 2.00122(6) 53(1) 165(3) 75 0.167 A( As) 69.038(9) -3.61(1) -7.27(1) 1 76.457(9) 52.7(2) 158.1(2) (mT) 61.523(9) 2.898(8) 2 60.210(9) 38.4(8) 321(5) 66.165(8) 3 60.059(9) 81(2) 61(2) Center III 2.0034(1) 0 0 1 2.00419(7) 71(1) 90 g 2.00392(7) 0.00079(5) 2 2.0034(1) 90 0 2.00188(5) 3 2.00161(5) 19(1) 270 0.158 A(75As) 58.27(1) 0 0 1 74.620(6) 19.4(2) 270 (mT) 59.989(9) -5.155(7) 2 58.271(9) 90 0 72.803(6) 3 58.172(9) 70.6(2) 90 Center IV 2.00322(6) 0 0 1 2.00349(6) 7(1) 90 g 2.00114(6) 0.00031(7) 2 2.00322(6) 90 0 0.134 2.00345(6) 3 2.00110(6) 97(1) 90 75 A( As) 62.975(6) 0 0 1 79.976(9) 92.1(2) 90 (mT) 79.951(9) -0.652(8) 2 62.975(6) 90 0 62.962(7) 3 62.937(7) 2.1(2) 90 Center V 2.00287(9) 0 0 1 2.00330(8) 7(2) 90 g 2.00108(8) 0.00030(9) 2 2.00287(9) 90 0 2.00326(8) 3 2.00104(8) 97(2) 90 75 0.193 A( As) 67.62(1) 0 0 1 84.771(9) 93.8(2) 90 (MHz) 84.694(8) -1.14(1) 2 67.64(1) 3.8(2) 90 67.71(1) 3 67.62(1) 90 0 Polar angle (θ) and azimuthal angle (φ) are relative to the crystallographic axes b and a, respectively. †, two equivalent matrices A(1H) are obtained from spectral simulations. 2.00399(4)
0 2.00154(4)
Table S2. Selected bond distances and directions in struvite (Pmn21: a = 6.955 (1), b = 6.142 (1), c = 11.218 (2) Å)
Bond
Distance (Å)
P-O3 P-O3 P-O2 P-O1 P-H4 P-H4 Mg-OW1 Mg-OW2 Mg-OW31 Mg-OW32 Mg-OW41 Mg-OW42
1.5417 1.5417 1.5440 1.5402 2.6699 2.6699 2.1158 2.1125 2.0763 2.0763 2.0553 2.0553
θ (°) 61.2 61.2 23.1 86.2 28.1 28.1 27.2 29.3 70.1 70.1 71.1 71.1
φ (°) 20.3 159.7 270 90 5.1 264.9 270 270 39.1 140.9 139.2 40.8
Polar angle (θ) and azimuthal angle (φ) are relative to the crystallographic axes b and a, respectively.
