Supporting Information
Insights into tetracycline adsorption onto kaolinite and montmorillonite: Experiments and modeling
Yanping Zhao1, Xueyuan Gu2, Shiyin Li1, Ruiming Han1, Guoxiang Wang1*
Affiliations: 1 Jiangsu Key Laboratory of Environmental Change and Ecological Construction, Jiangsu Center for Collaborative Innovation in Geographical Information Resource Development and Application, School of Geographical Science, Nanjing Normal University, Nanjing 210023, China, 2 State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China
* Corresponding author ()
Number of pages: 12
Number of figures: 4
Number of tables: 5
Fig. S1–Structure of tetracycline (TC).The regions framed by dashed lines represent the structural moieties associated with the three acidic dissociation constants (pKa).
Fig. S2–Speciation of TC under different pHs.
Fig. S3 –ATR-FTIR difference spectra of TC on goethite surface at different pH values (indicated).
Fig. S4–Modeled surface speciation diagrams of TC, with different initial concentration, adsorption onto kaolinite (KT, 0.023, 0.045 and 0.11 mM) and montmorillonite (MT, 0.11 and 0.23 mM), in 0.01 M NaNO3 solution, 25 °C, at 1 g L-1 and 0.2 g L-1, respectively. Symbols are experimental data and lines are fitted using the parameters in Table 1.
Table. S1 -A summary of the FTIR vibration characteristics of the TC adsorbed onto soil minerals
Literature / Wavenumbers (cm-1)1668
(a) / 1608
(b) / 1579
(c) / 1505
(d) / 1448
(e) / 1400
(f) / 1267
(g) / 1229
(h) / 1186
(i)
[1] / C=O
(amide) / C=O
(ring A) / C=O
(ring C) / -NH / C-C / - / - / - / -
[2] / -NH2 / C=O
(ring A) / C=O
(ring C) / -NH / C-C / -CH3 / C-N / - / -
[3] / - / -NH / OH10,12 / -NH / - / -NH / - / - / -
[4] / C=O
(amide) / C=C / -NH / - / C-C / - / - / - / -
[5] / C=O
(amide) / C=O
(ring A) / C=O
(ring C) / -NH2 / - / - / - / - / -
[6] / TC vibrations were much weaker compared to those sorbed to montmorillonite
[7] / C=O
(amide) / C=C / -NH / - / -CH3 / - / C-N / - / -
[8] / C=O
(amide) / -NH2 / C=C / - / -CH3 / - / C-N / C-N / C-O
This study / amideC=O / C=O
(ring A) / C=O
(ring C) / C=C / -NH / -CH3 / C-N / C-N / C-O
Table. S2–A summary of previous studies on surface characteristics, surface protonation and electrolyte adsorption equilibrium constants, and capacitances for kaolinite
salt / ASm2 g-1 / logK0a1 / logK0a2 / logK
X-.H+ / logK0cation / logK0
anion / C1
F m-2 / C2
F m-2 / Adsorptiondata / Parameterestimation / SCM
NaNO3 / 13.6 / 2.1 / -8.1 / 2.1 / - / - / - / - / [9] / [10] / DLM
NaNO3 / 22.0 / 2.77 / -6.77 / 7.30 / -6.21 / -1.0 / 2.4 / 0.2 / [11] / [11] / TLM
CaCl2 / 23.6 / - / - / - / - / - / 1.5 / 5.0 / [12-14] / [13] / CD-M
NaCl / - / 5.0 / -11.2 / - / -8.6 / 7.5 / 1.2 / 0.2 / [15-18] / [17, 18] / TLM
NaNO3 / 12.3 / 2.77 / -6.77 / 6.21 / - / - / 2.4 / 0.2 / [19, 20] / [20] / TLM
NaNO3 / 12.0 / 6.52 / -11.1 / - / -9.06 / 8.52 / 2.0 / 0.2 / [21, 22] / [22] / TLM
NaCl / 8.58 / 4.23 / -6.86 / - / -2.35 / 5.50 / 3.8 / 0.2 / [23] / [23] / TLM
KCl / 23.6 / 7.89 / -9.05 / - / -9.20 / 7.90 / 1.0 / 0.2 / [24] / [25, 26] / TLM
KClO4 / 25.0 / 5.70 / -11.4 / - / -9.15 / -1.75 / 1.2-2.4 / 0.2 / [27] / [28, 29] / TLM
Table. S3– A summary of previous studies on surface characteristics, surface protonation and electrolyte adsorption equilibrium constants, and capacitances for montmorillonite
salt / ASm2 g-1 / logK0a1 / logK0a2 / logK
X-.H+ / logK0
cation / logK0
anion / C1
F m-2 / C2
F m-2 / Adsorptiondata / Parameterestimation / SCM
NaCl / - / 5.0 / -11.2 / - / -8.6 / 7.5 / 1.2 / 0.2 / [15-18] / [17, 18] / TLM
CaCl2 / 23.6 / - / - / - / - / - / 1.5 / 5.0 / [12-14] / [13] / CD-M
CaCl2, NaCl / 80 / 7.5 / -10.0 / - / - / - / 1.4 / 0.2 / [30] / [30] / TLM
NaCl / 760 / - / - / - / - / - / 1.27 / 0.94 / [31] / [31] / TLM
NaCl / - / - / - / - / - / - / 1-2 / 0.55 / [32] / [32] / TLM
1
Table. S4-Species/component matrix used in FITEQL for the batch adsorption data to calculate TC binding constants on kaolinite
Species / ComponentsPSI(0) / PSI(beta) / PSI(d) / H2TC0 / ≡SOH0 / ≡X-∙Na+ / Na+ / NO3- / H+
1 / H3TC+ / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0 / 1
2 / H2TC0 / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0 / 0
3 / HTC- / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0 / -1
4 / TC2- / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0 / -2
5 / ≡SOH2+ / 1 / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 1
6 / ≡SOH0 / 0 / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0
7 / ≡SO- / -1 / 0 / 0 / 0 / 1 / 0 / 0 / 0 / -1
8 / ≡SO-∙Na+ / -1 / 1 / 0 / 0 / 1 / 0 / 1 / 0 / -1
9 / ≡SOH2+∙NO3- / 1 / -1 / 0 / 0 / 1 / 0 / 0 / 1 / 1
10 / ≡X-∙Na+ / -1 / 1 / 0 / 0 / 0 / 1 / 0 / 0 / 0
11 / ≡X-∙H+ / -1 / 1 / 0 / 0 / 0 / 1 / -1 / 0 / 1
12 / ≡SOH0∙H2TC0 / 0 / 0 / 0 / 1 / 1 / 0 / 0 / 0 / 0
13 / ≡SOH0∙HTC- / 0 / -1 / 0 / 1 / 1 / 0 / 0 / 0 / -1
14 / ≡X-∙ H3TC+ / -1 / 1 / 0 / 1 / 0 / 1 / -1 / 0 / 1
15 / ≡X-∙ H2TC0 / -1 / 0 / 0 / 1 / 0 / 1 / -1 / 0 / 0
16 / OH- / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 0 / -1
17 / H+ / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 1
Table. S5-Species/component matrix used in FITEQL for the batch adsorption data to calculate TC binding constants on montmorillonite
Species / ComponentsPSI(0) / PSI(beta) / PSI(d) / H2TC0 / ≡SOH0 / ≡X-∙Na+ / Na+ / NO3- / H+
1 / H3TC+ / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0 / 1
2 / H2TC0 / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0 / 0
3 / HTC- / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0 / -1
4 / TC2- / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0 / -2
5 / ≡SOH2+ / 1 / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 1
6 / ≡SOH0 / 0 / 0 / 0 / 0 / 1 / 0 / 0 / 0 / 0
7 / ≡SO- / -1 / 0 / 0 / 0 / 1 / 0 / 0 / 0 / -1
8 / ≡SO-∙Na+ / -1 / 1 / 0 / 0 / 1 / 0 / 1 / 0 / -1
9 / ≡SOH2+∙NO3- / 1 / -1 / 0 / 0 / 1 / 0 / 0 / 1 / 1
10 / ≡X-∙Na+ / -1 / 1 / 0 / 0 / 0 / 1 / 0 / 0 / 0
11 / ≡X-∙H+ / -1 / 1 / 0 / 0 / 0 / 1 / -1 / 0 / 1
12 / ≡X-∙ H3TC+ / -1 / 1 / 0 / 1 / 0 / 1 / -1 / 0 / 1
13 / ≡X-∙ H2TC0 / -1 / 0 / 0 / 1 / 0 / 1 / -1 / 0 / 0
14 / ≡SOH0∙HTC- / 0 / -1 / 0 / 1 / 1 / 0 / 0 / 0 / -1
15 / OH- / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 0 / -1
16 / H+ / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 1
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