Supplementary Material s87

Supplementary Material

Table S1. Extractability of contaminants and Fe in 0.2 M NH4-oxalate in the dark after 2 hours, and Fe/As molar ratio in the oxalate fraction.

Sample/ Fe As Cu Pb Zn Fe/As Fe As Cu Pb Zn Fe/As type <250 m fraction <11 m fraction wt% mg/kg mg/kg mg/kg mg/kg mol/ wt% mg/kg mg/kg mg/kg mg/kg mol/

(%) (%) (%) (%) (%) mol (%) (%) (%) (%) (%) mol Mine 2.458 6277 624 16.8 4304 4.553 11560 1052 31.0 6857 1 12 waste (33) (68) (71) (16) (61) 5 (42) (99) (82) (14) (62) 2 Mine 2.575 11620 68 7.6 43 3.950 17320 114 15.1 66 10 waste (28) (75) (24) (4) (15) 3 (29) (98) (29) (3) (19) 3 Mine 1.742 5421 226 13.9 540 3.654 9905 389 33.0 809 11 waste (26) (56) (54) (6) (67) 4 (34) (73) (57) (6) (68) 4 Mine 1.695 6049 264 2.3 59 3.275 11000 490 5.1 119 13 waste (22) (51) (53) (3) (30) 4 (24) (79) (59) (3) (36) 5 Mine 1.652 6511 99 7.7 198 2.956 11880 149 14.8 319 10 waste (26) (59) (52) (6) (55) 3 (29) (86) (56) (5) (61)

Urban 0.412 227 47 9.1 347 0.733 421 67 19.6 581 61 6 24 soil (19) (68) (59) (10) (76) (34) (89) (68) (11) (80) Urban 0.535 1020 77 13.3 1190 0.862 1940 86 19.8 1377 27 7 7 soil (19) (77) (42) (12) (57) (22) (99) (71) (10) (98) Urban 2.031 5805 892 37.5 2010 3.012 7778 1011 65.8 2464 12 8 5 soil (31) (56) (64) (22) (54) (42) (87) (76) (26) (59) Urban 0.860 2434 107 13.0 366 1.509 4101 184 18.1 658 17 9 5 soil (21) (57) (57) (9) (59) (27) (93) (73) (7) (78) Urban 0.308 94 33 5.1 138 0.581 329 84 6.0 355 83 10 44 soil (15) (57) (49) (14) (63) (24) (82) (71) (7) (83) Urban 0.575 713 84 14.8 168 0.984 1220 137 19.4 261 32 11 11 soil (21) (72) (60) (24) (64) (28) (81) (69) (16) (68)

Road 0.554 48 37 6.3 174 1.165 143 150 11.8 549 329 12 155 dust (20) (38) (32) (11) (65) (29) (88) (71) (11) (97) Road 0.403 177 54 6.5 79 0.956 632 274 17.1 298 76 13 31 dust (14) (45) (49) (11) (57) (23) (88) (85) (18) (86) Road 0.540 111 28 7.0 145 1.276 324 133 10.8 506 138 14 65 dust (21) (64) (29) (21) (68) (35) (92) (73) (12) (97) Road 0.375 37 40 6.1 162 0.998 137 125 11.4 460 353 15 136 dust (13) (43) (45) (22) (79) (24) (87) (71) (16) (97) Road 0.333 776 40 8.9 48 1.240 2890 164 12.5 214 22 16 6 dust (11) (55) (35) (19) (50) (25) (93) (65) (12) (71)

Extractability values in parentheses calculated as a percentage of the total concentration in the respective <250 m or <11 m fractions. Table S2. Bioaccessible contaminants in mine waste, urban soil and road dust samples extracted with SBRC-G (<250 m fraction) and Gamble’s solutions (<11 m fraction).

Sample/type As Cu Pb Zn As Cu Pb Zn <250 m fraction <11 m fraction mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg (%) (%) (%) (%) (%) (%) (%) (%) 1 Mine waste 556 (6) 332 (38) 6 (6) 3260 (46) 674 (6) 10 (0.7) <0.1 (0.0) 4 (0.0) 2 Mine waste 552 (4) 21 (7) <0.5 (<0.2) 6 (2) 1072 (6) 6 (1) <0.1 (0.0) <1 (<0.3) 3 Mine waste 399 (4) 123 (30) 1 (0.5) 337 (42) 476 (4) 23 (3) <0.1 (0.0) <1 (<0.1) 4 Mine waste 520 (4) 161 (32) <0.5 (<0.6) 23 (12) 503 (4) 10 (1) <0.1 (0.0) <1 (<0.3) 5 Mine waste 795 (7) 61 (32) 5 (4) 136 (38) 1008 (7) 3 (1) <0.1 (0.0) <1 (<0.2)

6 Urban soil 29 (9) 7 (9) 23 (26) 205 (45) 19 (4) 2 (2) 0.5 (0.3) 2 (0.3) 7 Urban soil 170 (13) 34 (19) 19 (17) 931 (45) 253 (13) 5 (4) <0.1 (<0.1) 2 (0.1) 8 Urban soil 435 (4) 615 (44) 15 (9) 1925 (51) 400 (5) 51 (4) 0.2 (0.1) 8 (0.2) 9 Urban soil 399 (9) 34 (18) 12 (8) 269 (43) 246 (6) 6 (2) <0.1 (0.0) <1 (<0.1) 1 Urban soil 12 (7) 6 (9) 8 (22) 94 (43) 19 (5) 3 (2) 0.4 (0.5) <1 (<0.2) 0 1 Urban soil 66 (7) 21 (15) 11 (18) 140 (53) 52 (4) 5 (3) <0.1 (<0.1) <1 (<0.3) 1

1 Road dust 6 (5) 23 (20) 18 (33) 106 (40) 9 (6) 7 (3) 0.2 (0.2) <1 (<0.2) 2 1 Road dust 17 (4) 48 (43) 8 (14) 42 (30) 29 (4) 17 (5) <0.1 (<0.1) <1 (<0.3) 3 1 Road dust 13 (7) 18 (19) 11 (32) 107 (50) 21 (6) 8 (5) <0.1 (<0.1) <1 (<0.2) 4 1 Road dust 9 (10) 27 (30) 12 (43) 119 (68) 10 6) 7 (4) 0.2 (0.3) <1 (<0.2) 5 1 Road dust 147 (10) 24 (21) 7 (15) 32 (33) 168 (5) 5 (2) <0.1 (<0.1) <1 (<0.3) 6

Bioaccessibility values in parentheses calculated as a percentage of the total concentration in the respective <250 m or <11 m fractions.