, 13, 528 540 Supplementary material Long-term responses in soil solution and stream-water chemistry at Hubbard Brook after experimental addition of wollastonite Shuai Shao, A Charles T. Driscoll, A,E Chris E. Johnson, A Timothy J. Fahey, B John J. Battles C and Joel D. Blum D A Department of Civil and Environmental Engineering, 151 Link Hall, Syracuse University, Syracuse, NY 13244, USA. B Department of Natural Resources, G16 Fernow Hall, Cornell University, Ithaca, NY 14853, USA. C Department of Environmental Science, Policy and Management, 137 Mulford Hall #3114, University of California, Berkeley, CA 94720, USA. D Department of Earth and Environmental Sciences, 1100 North University Avenue, University of Michigan, Ann Arbor, MI 48109, USA. E Corresponding author. Email: ctdrisco@syr.edu Page 1 of 8
Table S1. Ca, Si, Ca : Si, Al i and Ca : Al i in Oa, Bh and Bs horizons soil solutions, before (1999) and after (2000 and 2011) wollastonite application to watershed 1 (W1) at the Hubbard Brook Experimental Forest (HBEF) X = arithmetic mean, s.d. = standard deviation. Both alternative hypotheses (year > or < year) and null hypotheses (year year) were tested by two sample t-test based on P value, using the significance level of 0.01 for all tests Parameter Horizons X ± s.d. Significant differences Ca (μmol L 1 ) Oa 19.6 ± 14.8 38.9 ± 32.6 39.8 ± 29.2 1999 < 2000, P < 0.0001 1999 < 2011, P < 0.0001 Bh 17.3 ± 7.7 28.6 ± 20.4 23.3 ± 16.7 1999 < 2000, P = 0.0001 1999 < 2011, P = 0.0046 Bs Si (μmol L 1 ) Oa 14.1 ± 7.2 73.2 ± 38.8 20.8 ± 11.8 207.4 ± 131.5 22.9 ± 19.1 1999 < 2000, P < 0.0001 1999 < 2011, P = 0.0002 97.9 ± 44.2 1999 < 2000, P < 0.0001 1999 < 2011, P < 0.0001 Bh 82.6 ± 37.2 121.8 107.7 ± 43.6 1999 < 2000, P < 0.0001 1999 < 2011, P < 0.0001 Ca : Si Bs 62.3 ± 28.9 135.9 ± 98.4 83.4 ± 20.2 1999 < 2000, P < 0.0001 1999 < 2011, P < 0.0001 Oa 0.32 ± 0.31 0.18 ± 0.12 0.41 ± 0.27 1999 > 2000, P < 0.0001 1999 2011, P = 0.0164 Bh 0.24 ± 0.18 0.18 ± 0.18 0.21 ± 0.10 1999 > 2000, P = 0.0094 1999 2011, P = 0.8721 Bs 0.27 ± 0.24 0.14 ± 0.09 0.29 ± 0.26 1999 > 2000, P < 0.0001 1999 2011, P = 0.3324 Al i (μmol L 1 ) Oa 10.2 ± 8.3 6.5 ± 7.0 3.2 ± 2.7 1999 > 2000, P = 0.001 1999 > 2011, P < 0.0001 Bh 10.6 ± 11.5 7.0 ± 6.0 5.2 ± 3.3 1999 2000, P = 0.057 1999 > 2011, P < 0.0001 Bs 10.2 ± 8.3 9.0 ± 6.9 5.5 ± 3.7 1999 2000, P = 0.1916 1999 > 2011, P < 0.0001 Ca : Al i Oa 3.9 ± 9.7 9.5 ± 13.8 24.5 ± 49.8 1999 < 2000, P = 0.0046 1999 < 2011, P = 0.0011 Bh 3.2 ± 3.2 7.7 ± 9.4 5.1 ± 4.4 1999 < 2000, P < 0.0001 1999 < 2011, P = 0.0018 Bs 3.0 ± 3.5 3.7 ± 5.3 25.9 ± 90.2 1999 2000, P = 0.1948 1999 2011, P = 0.0217 Page 2 of 8
Table S2. Ca and Si concentrations in Oa, Bh and Bs horizon soil solutions, before (1999) and after (2000 and 2011) wollastonite application to three sub-watersheds of watershed 1 (W1) at the Hubbard Brook Experimental Forest (HBEF) hardwood zone (LH). X = arithmetic mean, s.d. = standard deviation. Both alternative hypotheses (year > or < year) and null hypotheses (year year) were tested by two sample t-test based on P value, using the significance level of 0.001 for all tests Parameter Sub-watershed Horizon X ± s.d. Significant differences Ca (μmol L 1 ) SFB Oa 14.8 ± 12.5 44.7 ± 27.4 46.1 ± 26.4 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bh 9.5 ± 5.6 25.7 ± 20.1 25.3 ± 15.8 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bs 10.1 ± 6.2 13.9 ± 11.4 29.3 ± 20.2 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 HH Oa 36.1 ± 25.2 45.7 ± 21.7 57.8 ± 26.7 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bh 22.9 ± 9.1 37.7 ± 6.7 28.2 ± 17.2 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bs 18.2 ± 2.7 22.1 ± 7.8 16.9 ± 7.1 1999 < 2000 P < 0.0001 1999 2011 P = 0.4646 LH Oa 34.3 ± 15.6 63.5 ± 48.5 28.1 ± 10.1 1999 < 2000 P < 0.0001 1999 2011 P = 0.7751 Bh 21.9 ± 7.2 26.8 ± 8.6 19.1 ± 1.5 1999 < 2000 P < 0.0001 1999 2011 P = 0.5938 Bs 19.8 ± 3.5 27.8 ± 11.1 11.2 ± 3.6 1999 < 2000 P < 0.0001 1999 2011 P = 0.9332 Si (μmol L 1 ) SFB Oa 65.4 ± 22.3 227.6 ± 55.8 84.4 ± 16.1 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bh 74.7 ± 30.4 190.9 ± 60.9 84.6 ± 21.1 1999 < 2000 P < 0.0001 1999 2011 P = 0.0261 Bs 55.4 ± 22.6 141.5 ± 99.8 67.8 ± 23.4 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 HH Oa 87.8 ± 19.2 233.4 ± 101.6 103.8 ± 32.6 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bh 76.4 ± 28.3 195.5 ± 88.3 97.5 ± 37.1 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bs 59.2 ± 17.1 123.5 ± 42.4 81.7 ± 13.5 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 LH Oa 72.6 ± 11.5 299.2 ± 132.4 93.2 ± 23.8 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bh 79.5 ± 11.2 114.4 ± 20.9 105.5 ± 33.2 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bs 73.5 ± 25.4 99.2 ± 23.7 88.1 ± 8.4 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Page 3 of 8
Table S3. Ca : Si and Al i concentrations in Oa, Bh and Bs horizon soil solutions, before (1999) and after (2000 and 2011) wollastonite application to three sub-watersheds of watershed 1 (W1) at the Hubbard Brook Experimental Forest (HBEF) hardwood zone (LH). X = arithmetic mean, s.d. = standard deviation. Both alternative hypotheses (year > or < year) and null hypotheses (year year) were tested by two sample t-test based on P value, using the significance level of 0.001 for all tests Parameter Sub-watershed Horizon X ± s.d. Significant differences Ca : Si SFB Oa 0.18 ± 0.12 0.20 ± 0.12 0.59 ± 0.27 1999 2000 P = 0.0823 1999 < 2011 P < 0.0001 Bh 0.14 ± 0.18 0.13 ± 0.11 0.30 ± 0.10 1999 2000 P = 0.6187 1999 < 2011 P < 0.0001 Bs 0.21 ± 0.24 0.10 ± 0.09 0.43 ± 0.26 1999 2000 P = 0.3658 1999 < 2011 P < 0.0001 HH Oa 0.45 ± 0.21 0.20 ± 0.12 0.56 ± 0.27 1999 > 2000 P < 0.0001 1999 2011 P = 0.4859 Bh 0.31 ± 0.11 0.19 ± 0.08 0.29 ± 0.17 1999 > 2000 P < 0.0001 1999 2011 P = 0.8381 Bs 0.31 ± 0.17 0.16 ± 0.07 0.21 ± 0.21 1999 > 2000 P < 0.0001 1999 > 2011 P < 0.0001 LH Oa 0.46 ± 0.32 0.21 ± 0.15 0.35 ± 0.22 1999 > 2000 P < 0.0001 1999 > 2011 P < 0.0001 Bh 0.28 ± 0.17 0.23 ± 0.14 0.11 ± 0.05 1999 2000 P = 0.0213 1999 > 2011 P < 0.0001 Bs 0.27 ± 0.09 0.28 ± 0.15 0.13 ± 0.05 1999 2000 P = 0.9215 1999 > 2011 P < 0.0001 Al i (μmol L 1 ) SFB Oa 11.8 ± 8.2 7.8 ± 5.4 2.2 ± 1.8 1999 > 2000 P < 0.0001 1999 > 2011 P < 0.0001 Bh 17.2 ± 11.9 11.1 ± 5.8 4.8 ± 1.4 1999 > 2000 P < 0.0001 1999 > 2011 P < 0.0001 Bs 15.4 ± 9.8 14.2 ± 3.7 7.5 ± 4.7 1999 2000 P = 0.1056 1999 > 2011 P < 0.0001 HH Oa 9.5 ± 0.9 5.1 ± 1.3 0.5 ± 0.3 1999 > 2000 P < 0.0001 1999 > 2011 P < 0.0001 Bh 12.1 ± 5.8 6.4 ± 0.4 7.8 ± 3.3 1999 > 2000 P < 0.0001 1999 > 2011 P < 0.0001 Bs 14.7 ± 8.9 12.9 ± 3.2 9.5 ± 3.7 1999 2000 P = 0.0618 1999 > 2011 P < 0.0001 LH Oa 6.3 ± 3.2 3.3 ± 2.2 2.0 ± 1.8 1999 > 2000 P = 0.0019 1999 > 2011 P < 0.0001 Bh 6.1 ± 3.2 4.6 ± 1.8 5.8 ± 2.4 1999 2000 P = 0.0858 1999 2011 P = 0.9721 Bs 7.5 ± 2.9 5.7 ± 2.8 5.8 ± 0.7 1999 > 2000 P < 0.0001 1999 2011 P = 0.0161 Page 4 of 8
Table S4. Ca : Al i in Oa, Bh and Bs soil solutions, before (1999) and after (2000 and 2011) wollastonite application to three subwatersheds of watershed 1 (W1) at the Hubbard Brook Experimental Forest (HBEF) hardwood zone (LH). X = arithmetic mean, s.d. = standard deviation. Both alternative hypotheses (year > or < year) and null hypotheses (year year) were tested by two sample t-test based on P value, using the significance level of 0.001 for all tests Parameter Sub-watershed Horizon X ± s.d. Significant differences Ca : Al i SFB Oa 1.2 ± 2.3 5.7 ± 8.2 20.6 ± 24.8 1999 < 2000 P = 0.0003 1999 < 2011 P = 0.0001 Bh 0.7 ± 2.7 2.3 ± 2.5 5.3 ± 4.1 1999 < 2000 P < 0.0001 1999 < 2011 P < 0.0001 Bs 0.6 ± 1.3 1.1 ± 0.8 3.9 ± 1.5 1999 2000 P = 0.0012 1999 2011 P = 0.0186 HH Oa 4.2 ± 2.9 9.2 ± 7.8 108.4 ± 130.8 1999 2000 P = 0.0058 1999 2011 P = 0.0018 Bh 1.9 ± 2.6 5.9 ± 4.9 3.6 ± 2.7 1999 < 2000 P = 0.0001 1999 2011 P = 0.0215 Bs 2.1 ± 3.8 1.7 ± 4.4 1.8 ± 0.7 1999 2000 P = 0.1515 1999 2000 P = 0.2759 LH Oa 5.5 ± 2.9 19.5 ± 12.2 16.7 ± 7.3 1999 < 2000 P = 0.0001 1999 < 2011 P < 0.0001 Bh 3.8 ± 3.1 6.5 ± 9.6 2.1 ± 0.9 1999 2000 P = 0.0412 1999 2011 P = 0.3318 Bs 3.4 ± 2.7 4.8 ± 3.9 1.9 ± 1.2 1999 2000 P = 0.0918 1999 2011 P = 0.2376 Page 5 of 8
Table S5. Ca, Si, Ca : Si, ANC, and Al i concentrations in stream water before (1999) and after (2000 and 2011) wollastonite application to watershed 1 (W1) at the Hubbard Brook Experimental Forest (HBEF) X = arithmetic mean, s.d. = standard deviation. Both alternative hypotheses (year > or < year) and null hypotheses (year year) were tested by two sample t-test based on P value, using the significance level of 0.05 for all tests Parameter X ± s.d. Significant differences Ca (μmol L 1 ) 18.4 ± 5.1 48.1 ± 13.9 22.1 ± 7.2 1999 < 2000, P < 0.0001 1999 < 2011, P = 0.0035 Si (μmol L 1 ) 65.1+ ± 9.2 125.8 ± 38.7 76.6 ± 12.2 1999 < 2000, P < 0.0001 1999 < 2011, P < 0.0001 Ca : Si 0.27 ± 0.06 0.39 ± 0.13 0.26 ± 0.06 1999 < 2000, P < 0.0001 1999 2011, P = 0.6892 ANC (μeq L 1 ) 6.2 ± 18.1 3.0 ± 11.5 4.14 ± 23.4 1999 < 2000, P = 0.0005 1999 2011, P = 0.3161 Al i (μmol L 1 ) 10.3 ± 3.9 4.4 ± 3.1 3.02 ± 1.9 1999 > 2000, P < 0.0001 1999 > 2011, P < 0.0001 Page 6 of 8
Table S6. Ca, Si, Ca : Si, ANC, and Al i concentrations in stream water before (1999) and after (2000 and 2011) wollastonite application to three sub-watersheds of watershed 1 (W1) at the Hubbard Brook Experimental Forest (HBEF) hardwood zone (LH). X = arithmetic mean, s.d. = standard deviation. Both alternative hypotheses (year > or < year) and null hypotheses (year year) were tested by two sample t-test based on P value, using the significance level of 0.01 for all tests Parameter Subwatershed X ± s.d. Significant differences Ca (μmol L 1 ) SFB 10.7 ± 1.4 40.6 ± 8.1 21.7 ± 2.8 1999 < 2000, P < 0.0001 1999 < 2011, P < 0.0001 HH 20.3 ± 3.4 43.9 ± 11.2 18.9 ± 2.3 1999 < 2000, P < 0.0001 1999 2011, P = 0.7894 LH 20.9 ± 3.7 53.9 ± 2.1 19.1 ± 2.1 1999 < 2000, P < 0.0001 1999 2011, P = 0.9541 Si (μmol L 1 ) SFB 54.7 ± 11.3 188.0 ± 66.0 65.7 ± 11.6 1999 < 2000, P = 0.0026 1999 < 2011, P = 0.0184 HH 58.5 ± 5.2 109.7 ± 21.9 73.6 ± 7.0 1999 < 2000, P < 0.0001 1999 < 2011, P < 0.0001 Ca : Si LH 68.5 ± 4.7 122.6 ± 20.7 82.7 ± 9.7 1999 < 2000, P < 0.0001 1999 < 2011, P < 0.0001 SFB 0.17 ± 0.04 0.23 ± 0.05 0.34 ± 0.07 1999 2000, P = 0.023 1999 < 2011, P < 0.0001 HH 0.29 ± 0.06 0.41 ± 0.12 0.26 ± 0.05 1999 < 2000,P = 0.0006 1999 2011, P = 0.9397 LH 0.29 ± 0.06 0.44 ± 0.11 0.23 ± 0.05 1999 < 2000, P < 0.0001 1999 2011, P = 0.9997 ANC (μeq L 1 ) SFB 34.0 ± 23.1 12.38 ± 2.6 10.9 ± 43.3 1999 < 2000, P = 0.0085 1999 2011, P = 0.0084 HH 11.1 ± 9.4 1.6 ± 5.8 11.9 ± 13.3 1999 < 2000, P = 0.0007 1999 2011, P = 0.5826 LH 6.3 ± 9.4 10.9 ± 10.8 5.1 ± 16.4 1999 < 2000, P < 0.0001 1999 2011, P = 0.3859 Al i (μmol L 1 ) SFB 13.1 ± 2.3 5.9 ± 2.2 3.2 ± 0.7 1999 > 2000, P = 0.0037 1999 > 2011, P = 0.0002 HH 13.9 ± 2.9 5.9 ± 3.1 4.3 ± 2.2 1999 > 2000, P = 0.0005 1999 > 2011, P < 0.0001 LH 8.7 ± 1.8 1.0 ± 1.3 1.9 ± 1.0 1999 > 2000, P < 0.0001 1999 > 2011, P < 0.0001 Page 7 of 8
Table S7. The responses of Ca, Si and Ali concentrations in Oa, Bh and Bs horizons soil solutions, and stream water among three subwatersheds to the wollastonite addition to watershed 1 of the Hubbard Brook Experimental Forest (HBEF) hardwood zone (LH). We define the treatment effect as = 2011 1999. The null hypotheses (SFB HH LH) and alternative hypotheses (at least two are different) were tested using one-way ANOVA. If we rejected the null hypotheses for one-way ANOVA, then we performed a pairwise mean comparison to identify which response differs from which response. The significance level of 0.05 was used for all tests Parameter Horizon = 2011 1999 Sub-watersheds SFB HH LH differences Ca (μmol L 1 ) Oa 25.2 21.8 6.6 SFB HH > LH Bh 10.3 8.9 11.7 SFB HH LH Bs 16.1 0.5 7.5 SFB > LH > HH Stream 11.3 1.7 2.3 SFB > HH LH Si (μmol L 1 ) Oa 18.6 16.7 20.6 SFB HH LH Bh 17.9 20.6 25.5 SFB HH LH Bs 16.4 20.1 16.6 SFB HH LH Stream 4.5 6.3 7.4 SFB HH LH Ali (μmol L 1 ) Oa 9.6 9.0 4.8 SFB HH > LH Bh 7.7 4.9 0.3 SFB HH > LH Bs 7.5 4.8 1.5 SFB HH > LH Stream 6.4 6.8 4.3 SFB HH LH Page 8 of 8