Role of methanogenesis on the biotransformation of organic micropollutants during anaerobic digestion

SUPPLEMENTARY DATA Role of methanogenesis on the biotransformation of organic micropollutants during anaerobic digestion Lorena Gonzalez-Gil *, a, Miguel Mauricio-Iglesias a, Denisse Serrano a, b, Juan M. Lema a, Marta Carballa a a Department of Chemical Engineering, School of Engineering, Universidade de Santiago de Compostela, Rúa Lope Gómez de Marzoa, E-15782 Santiago de Compostela, Spain b Department of Water and Environmental Sciences, Instituto Tecnológico de Sonora, 5 de febrero 818 sur, Colonia Centro, 85000 Ciudad Obregón, México *Corresponding Author E-mail addresses: [email protected], [email protected], [email protected], [email protected], ma[email protected] 1 Contents S1. Physicochemical characteristics of selected OMPs ........................................... 2 S2. Parameter estimation .......................................................................................... 3 S3. Analysis of organic micropollutants .................................................................. 4 S4. Methanogenic reactors operation ....................................................................... 5 S5. Sorption of OMPs in digested sludge ................................................................ 7 S6. Biotransformation kinetics ................................................................................. 7 S7. Biotransformation rate constants in the methanogenic step ............................ 14 S8. Biotransformation phase .................................................................................. 15 S9. Removal of OMPs during sewage sludge AD ................................................. 16 References .................................................................................................................. 17 2 S1. Physicochemical characteristics of selected OMPs Table S1. Application and main physicochemical properties of the selected OMPs. OMP Application MW (g/mol) s (mg/L) H (atm m3/mol) pKa log Kow ERY Antibiotic 733.9 1.4 5.4·10-29 8.9 3.1 ROX Antibiotic 837.1 0.02 5.0·10-31 9.1 2.8 SMX Antibiotic 253.3 610 6.4·10-13 6.2 0.9 TMP Antibiotic 290.3 400 2.4·10-14 7.1 0.9 FLX Antidepressant 309.3 60 8.9·10-8 9.8 4.1 CBZ Anticonvulsant 236.3 112 1.1·10-10 15.9 2.5 DZP Anxiolytic 284.7 50 3.6·10-9 3.4 2.8 E1 Estrogen 270.4 30 3.8·10-10 10.3 3.1 E2 Estrogen 272.4 3.6 3.6·10-11 10.3 4.0 EE2 Contraceptive/ estrogen 296.4 11.3 7.9·10-12 10.3 3.7 ADBI Fragrance 244.4 0.22 2.1·10-4 ‒ 5.9 HHCB Fragrance 258.4 1.8 1.3·10-4 ‒ 5.9 AHTN Fragrance 258.4 0.21 2.6·10-4 ‒ 5.8 IBP Anti-inflammatory 206.3 21 1.5·10-6 4.9 4.0 NPX Anti-inflammatory 230.3 15.9 3.4·10-10 4.2 3.2 DCF Anti-inflammatory 296.2 2.4 4.7·10-12 4.2 4.2 OP Surfactant 206.3 3.1 8.5·10-6 ≈10 5.5 NP Surfactant 220.4 7.0 3.4·10-5 ≈10 5.8 TCS Antiseptic 289.5 10 5.0·10-9 7.7 4.7 BPA Fungicide/plasticizer 228.3 120 1.0·10-11 10.1 3.3 Molecular weight (MW), Henry’s law constant (H), solubility at 25 °C (s), acid dissociation constant (pKa), octanolwater coefficient (Kow). Data obtained from DrugBank and PhysProp databases and from Varhanickova et al. (1995). 3 S2. Parameter estimation The pseudo-first order kinetic constant was estimated by least-square fitting of the results of the kinetic experiments to equation S1. 𝑘𝑏𝑖𝑜𝑙 =argmin ∑(𝐶𝑇(𝑡)−𝐶𝑇,𝑒𝑥𝑝)2 Equation S1 where CT was obtained according to equation 2 of the manuscript: 𝐶𝑇= 𝐶0·𝑒(− 1 𝐻𝑅𝑇−𝑘𝑏𝑖𝑜𝑙·𝑋𝑉𝑆𝑆)·𝑡 To obtain a robust estimation of kbiol a bootstrap procedure was followed to determine the expected value and the confidence interval of the parameter. The procedure was done as follows: i) Estimate the residuals (e) of equation S1 by equation S2, which are used to simulate the experimental error in the measurements; 𝑒 =𝐶𝑇(𝑡)−𝐶𝑇,𝑒𝑥𝑝 Equation S2 ii) Simulate new experimental results (C*T,exp) by randomly adding some of the residuals to the experimental data; 𝐶∗𝑇,𝑒𝑥𝑝 =𝐶𝑇,𝑒𝑥𝑝 +𝑒𝑗 where ej is a random variable ej ∈ e Equation S3 iii) Carry out the least square estimation of k*biol for the new simulated data by using equation S1. iv) Iterate through steps ii) and iii) until convergence (number of iterations = 1000) on a distribution of kbiol and use this distribution to find the expected value and its confidence interval. 4 S3. Analysis of organic micropollutants Table S2. Limits of quantification (LOQ) and recovery ranges (n=3) of OMPs in the liquid and solid phase of the methanogenic sludge. LOQ Recovery range (%) OMP Liquid (ng/L) Solid (ng/g) Liquid Solid ERY 3 0.6 90-110 65-80 ROX 3 0.6 80-90 55-65 SMX 15 3 85-90 55-60 TMP 15 3 70-75 55-60 FLX 3 0.6 30-35 45-50 CBZ 15 3 65-75 70-80 DZP 15 3 50-60 60-70 E1 30 6 40-50 60-70 E2 30 6 60-70 60-70 EE2 30 6 60-80 60-75 ADBI 150 30 45-55 120-150 HHCB 150 30 40-60 120-150 AHTN 150 30 35-50 130-160 IBP 60 12 130-150 120-140 NPX 75 15 110-120 100-120 DCF 300 60 120-140 130-140 OP 60 12 60-70 120-140 NP 60 12 60-70 120-140 TCS 150 30 55-65 110-130 BPA 75 15 110-120 70-80 5 S4. Methanogenic reactors operation Figure S1. Performance of the methanogenic reactors (MR1 left side and MR2 right side) during the whole operation. Organic loading rate (OLR) and methane production (CH4) are represented in the upper graphs, while pH, volatile suspended solids (VSS) and intermediate/total alkalinity ratio (IA/TA) are depicted in the bottom graphs. Grey areas highlight the periods when the kinetic experiments with OMPs were conducted. 6 Table S3. Average feeding characteristics of methanogenic reactors during both steadystate operational stages (OLR=1 and 2 g COD/L d). OLR=1 g COD/L d OLR=2 g COD/L d pH 6.3 ± 0.7 6.4 ± 0.6 Acetic acid (HAc, g/L) 4.7 ± 0.3 9.5 ± 0.4 Propionic acid (g/L) 1.7 ± 0.1 3.3 ± 0.1 Butyric acid (g/L) 1.4 ± 0.1 2.7 ± 0.1 Total VFA (g HAceq/L) 7.9 ± 0.7 15.9 ± 0.5 COD (g/L) 9.5 ± 1.0 18.8 ± 1.0 NH4Cl (g/L) 0.6 0.6 KH2PO4 (g/L) 0.4 0.4 Trace concentrations of micro-nutrients (Fe, Ca, Mg, Cr, Co, Cu, Mn, Mo, Ni, Se, Zn, B) were added according to Angelidaki and Sanders (2004). 7 S5. Sorption of OMPs in digested sludge Table S4. Partitioning coefficients (log Kd) reported for anaerobically digested sludge. The average range represents the minimum and the maximum values from literature. log Kd OMP Gonzalez-Gil et al. (2016) Carballa et al. (2007) Narumiya et al. (2013) Clara et al. (2011) Ivashechkin et al. (2004) Average range TCS 3.56-4.35 3.56-4.35 AHTN 4.22-4.86 3.7-4.43 2.60-2.90 2.60-4.86 HHCB 2.58-5.14 3.45-4.3 2.58-5.14 FLX 2.44-3.44 2.44-3.44 E2 2.22-3.34 2.30-2.83 2.22-3.34 E1 1.76-2.91 2.18-2.77 1.76-2.91 BPA 2.09-2.30 2.09-2.30 TMP 1.92-2.86 1.92-2.86 ERY 1.60-3.10 1.60-3.10 ROX 2.52-3.97 1.14-1.92 1.90-3.30 1.14-3.97 EE2 1.21-1.40 2.08-2.85 1.21-2.85 DZP 1.85-1.88 1.85-1.88 DCF 1.26-2.18 1.90-2.20 1.26-2.20 CBZ 1.60-2.27 1.31-1.83 1.60-2.00 1.31-2.27 SMX 0.77-1.79 0.77-1.79 IBP 1.03-1.76 1.00-1.78 1.00-1.78 NPX 1.03-1.71 1.03-1.71 S6. Biotransformation kinetics The concentrations measured in the liquid and solid phase of the methanogenic effluent during the three kinetic experiments are displayed in Figures S2. An average methanogenic kinetics obtained from the three experiments is shown as well. Except for NP, EE2, SMX, TMP, and NPX, the resulting average values presented a low deviation, meaning that the concentrations of OMPs measured in three kinetic experiments were quite similar. Moreover, continuous lines depict the concentration patterns of OMPs in both phases if solely washout was the responsible for the removal. Therefore, the difference between the washout line and the experimental point corresponds to biotransformation. 8 Fig. S2a. Measured concentrations in the liquid (blue diamonds) and solid (orange squares) phases of hydrophobic compounds (Group 3). Continuous lines show the removal of the OMP by washout in the liquid (blue) and solid phase (orange). OLR=1 (Kinetic I) OLR=1 (Kinetic II) OLR=2 (Kinetic III) AVERAGE 15 S8. Biotransformation phase Fig. S3. Contribution of each phase to the total methanogenic biotransformation of OMPs. The apparent biotransformations measured in the solid (BS) and liquid phases (BL) are represented by the orange, lower bars and by the blue, upper bars, respectively. 16 S9. Removal of OMPs during sewage sludge AD Table S6. Summary of reported OMPs removal during AD of sewage sludge under similar operational conditions. The average removal was calculated with the mean value of each reference and for those cases where two completely different values were reported both were considered. OMP AD removal (%) Gonzalez-Gil et al. (2016) Carballa et al. (2007) Narumiya et al. (2013) Samaras et al. (2014) Malmborg & Magnér (2015) Clara et al. (2011) Paterakis et al. (2012) Bergersen et al. (2012) Yang et al. (2016) Average SMX 80 100 100 ‒ ‒ ‒ ‒ ‒ ‒ 93 ± 12 NPX 100 85 ‒ 85 85 ‒ ‒ ‒ 90 89 ± 7 TMP 75 ‒ 100 ‒ 100 ‒ ‒ ‒ 90 91 ± 12 NP ‒ ‒ ‒ 35 ‒ ‒ 0/100 ‒ ‒ 45 ± 51 FLX 70 ‒ ‒ ‒ 0 ‒ ‒ 30 30 33 ± 29 EE2 65 40/95 ‒ ‒ 0 ‒ 20 ‒ ‒ 44 ± 37 TCS 15 ‒ 30 65 ‒ ‒ ‒ ‒ 50 40 ± 22 Musks 10 60 ‒ ‒ ‒ 0/45 ‒ ‒ ‒ 29 ± 28 BPA ‒ ‒ ‒ 80 ‒ ‒ ‒ ‒ 0 40 ± 40 E1+E2 0 80 ‒ ‒ 0 ‒ 50 ‒ ‒ 33 ± 39 CBZ 40 5 0 ‒ 15 ‒ ‒ ‒ 0 11 ± 15 DZP 50 30 ‒ ‒ ‒ ‒ ‒ ‒ ‒ 40 ± 10 ERY ‒ ‒ 45 ‒ ‒ ‒ ‒ ‒ ‒ 45 ROX 85 95 65 ‒ ‒ ‒ ‒ ‒ ‒ 82 ± 15 DCF ‒ 0/80 25 95 25 ‒ ‒ ‒ 0 38 ± 41 IBP 30 45 ‒ 95 30 ‒ ‒ ‒ 10 42 ± 32 OP ‒ ‒ ‒ ‒ ‒ ‒ ‒ ‒ ‒ ‒ Operational conditions Continuous digester Lab-scale Lab-scale Full-scale Lab-scale Lab-scale Full-scale Lab-scale Lab-scale Full-scale OMPs spike No Yes No Yes Yes No No Yes No Substrate* MixS MixS MixS MixS MixS SS MixS & PS SS PS Temperature (°C) 37 37 30-55 37 37 37 35 37 35 HRT (d) 20-30 10-30 20-30 20 20 15-20 30 20 15-30 *MixS: mixed primary and secondary sewage sludge; PS: primary sludge; SS: sewage sludge (type not specified). 17 References Bergersen, O., Østnes, K., Vasskog, T., 2012. 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