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

SUPPLEMENTARY DATA Role o me hanogenesis on he bio ans o ma ion o o ganic mic opollu an s du ing anae obic diges ion Lo ena Gonzalez-Gil *, a, Miguel Mau icio-Iglesias a, Denisse Se ano a, b, Juan M. Lema a, Ma a Ca balla a a Depa men o Chemical Enginee ing, School o Enginee ing, Uni e sidade de San iago de Compos ela, Rúa Lope Gómez de Ma zoa, E-15782 San iago de Compos ela, Spain b Depa men o Wa e and En i onmen al Sciences, Ins i u o Tecnológico de Sono a, 5 de eb e o 818 su , Colonia Cen o, 85000 Ciudad Ob egón, México *Co esponding Au ho E-mail add esses: [email p o ec ed], [email p o ec ed], [email p o ec ed], [email p o ec ed], ma[email p o ec ed] 1 Con en s S1. Physicochemical cha ac e is ics o selec ed OMPs ........................................... 2 S2. Pa ame e es ima ion .......................................................................................... 3 S3. Analysis o o ganic mic opollu an s .................................................................. 4 S4. Me hanogenic eac o s ope a ion ....................................................................... 5 S5. So p ion o OMPs in diges ed sludge ................................................................ 7 S6. Bio ans o ma ion kine ics ................................................................................. 7 S7. Bio ans o ma ion a e cons an s in he me hanogenic s ep ............................ 14 S8. Bio ans o ma ion phase .................................................................................. 15 S9. Remo al o OMPs du ing sewage sludge AD ................................................. 16 Re e ences .................................................................................................................. 17 2 S1. Physicochemical cha ac e is ics o selec ed OMPs Table S1. Applica ion and main physicochemical p ope ies o he selec ed OMPs. OMP Applica ion MW (g/mol) s (mg/L) H (a m m3/mol) pKa log Kow ERY An ibio ic 733.9 1.4 5.4·10-29 8.9 3.1 ROX An ibio ic 837.1 0.02 5.0·10-31 9.1 2.8 SMX An ibio ic 253.3 610 6.4·10-13 6.2 0.9 TMP An ibio ic 290.3 400 2.4·10-14 7.1 0.9 FLX An idep essan 309.3 60 8.9·10-8 9.8 4.1 CBZ An icon ulsan 236.3 112 1.1·10-10 15.9 2.5 DZP Anxioly ic 284.7 50 3.6·10-9 3.4 2.8 E1 Es ogen 270.4 30 3.8·10-10 10.3 3.1 E2 Es ogen 272.4 3.6 3.6·10-11 10.3 4.0 EE2 Con acep i e/ es ogen 296.4 11.3 7.9·10-12 10.3 3.7 ADBI F ag ance 244.4 0.22 2.1·10-4 ‒ 5.9 HHCB F ag ance 258.4 1.8 1.3·10-4 ‒ 5.9 AHTN F ag ance 258.4 0.21 2.6·10-4 ‒ 5.8 IBP An i-in lamma o y 206.3 21 1.5·10-6 4.9 4.0 NPX An i-in lamma o y 230.3 15.9 3.4·10-10 4.2 3.2 DCF An i-in lamma o y 296.2 2.4 4.7·10-12 4.2 4.2 OP Su ac an 206.3 3.1 8.5·10-6 ≈10 5.5 NP Su ac an 220.4 7.0 3.4·10-5 ≈10 5.8 TCS An isep ic 289.5 10 5.0·10-9 7.7 4.7 BPA Fungicide/plas icize 228.3 120 1.0·10-11 10.1 3.3 Molecula weigh (MW), Hen y’s law cons an (H), solubili y a 25 °C (s), acid dissocia ion cons an (pKa), oc anol- wa e coe icien (Kow). Da a ob ained om D ugBank and PhysP op da abases and om Va hanicko a e al. (1995). 3 S2. Pa ame e es ima ion The pseudo- i s o de kine ic cons an was es ima ed by leas -squa e i ing o he esul s o he kine ic expe imen s o equa ion S1. 𝑘𝑏𝑖𝑜𝑙 =a gmin ∑(𝐶𝑇(𝑡)−𝐶𝑇,𝑒𝑥𝑝)2 Equa ion S1 whe e CT was ob ained acco ding o equa ion 2 o he manusc ip : 𝐶𝑇= 𝐶0·𝑒(− 1 𝐻𝑅𝑇−𝑘𝑏𝑖𝑜𝑙·𝑋𝑉𝑆𝑆)·𝑡 To ob ain a obus es ima ion o kbiol a boo s ap p ocedu e was ollowed o de e mine he expec ed alue and he con idence in e al o he pa ame e . The p ocedu e was done as ollows: i) Es ima e he esiduals (e) o equa ion S1 by equa ion S2, which a e used o simula e he expe imen al e o in he measu emen s; 𝑒 =𝐶𝑇(𝑡)−𝐶𝑇,𝑒𝑥𝑝 Equa ion S2 ii) Simula e new expe imen al esul s (C*T,exp) by andomly adding some o he esiduals o he expe imen al da a; 𝐶∗𝑇,𝑒𝑥𝑝 =𝐶𝑇,𝑒𝑥𝑝 +𝑒𝑗 whe e ej is a andom a iable ej ∈ e Equa ion S3 iii) Ca y ou he leas squa e es ima ion o k*biol o he new simula ed da a by using equa ion S1. i ) I e a e h ough s eps ii) and iii) un il con e gence (numbe o i e a ions = 1000) on a dis ibu ion o kbiol and use his dis ibu ion o ind he expec ed alue and i s con idence in e al. 4 S3. Analysis o o ganic mic opollu an s Table S2. Limi s o quan i ica ion (LOQ) and eco e y anges (n=3) o OMPs in he liquid and solid phase o he me hanogenic sludge. LOQ Reco e y ange (%) 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. Me hanogenic eac o s ope a ion Figu e S1. Pe o mance o he me hanogenic eac o s (MR1 le side and MR2 igh side) du ing he whole ope a ion. O ganic loading a e (OLR) and me hane p oduc ion (CH4) a e ep esen ed in he uppe g aphs, while pH, ola ile suspended solids (VSS) and in e media e/ o al alkalini y a io (IA/TA) a e depic ed in he bo om g aphs. G ey a eas highligh he pe iods when he kine ic expe imen s wi h OMPs we e conduc ed. 6 Table S3. A e age eeding cha ac e is ics o me hanogenic eac o s du ing bo h s eady- s a e ope a ional s ages (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 Ace ic acid (HAc, g/L) 4.7 ± 0.3 9.5 ± 0.4 P opionic acid (g/L) 1.7 ± 0.1 3.3 ± 0.1 Bu y ic acid (g/L) 1.4 ± 0.1 2.7 ± 0.1 To al 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 T ace concen a ions o mic o-nu ien s (Fe, Ca, Mg, C , Co, Cu, Mn, Mo, Ni, Se, Zn, B) we e added acco ding o Angelidaki and Sande s (2004). 7 S5. So p ion o OMPs in diges ed sludge Table S4. Pa i ioning coe icien s (log Kd) epo ed o anae obically diges ed sludge. The a e age ange ep esen s he minimum and he maximum alues om li e a u e. log Kd OMP Gonzalez-Gil e al. (2016) Ca balla e al. (2007) Na umiya e al. (2013) Cla a e al. (2011) I ashechkin e al. (2004) A e age ange 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. Bio ans o ma ion kine ics The concen a ions measu ed in he liquid and solid phase o he me hanogenic e luen du ing he h ee kine ic expe imen s a e displayed in Figu es S2. An a e age me hanogenic kine ics ob ained om he h ee expe imen s is shown as well. Excep o NP, EE2, SMX, TMP, and NPX, he esul ing a e age alues p esen ed a low de ia ion, meaning ha he concen a ions o OMPs measu ed in h ee kine ic expe imen s we e qui e simila . Mo eo e , con inuous lines depic he concen a ion pa e ns o OMPs in bo h phases i solely washou was he esponsible o he emo al. The e o e, he di e ence be ween he washou line and he expe imen al poin co esponds o bio ans o ma ion. 8 Fig. S2a. Measu ed concen a ions in he liquid (blue diamonds) and solid (o ange squa es) phases o hyd ophobic compounds (G oup 3). Con inuous lines show he emo al o he OMP by washou in he liquid (blue) and solid phase (o ange). OLR=1 (Kine ic I) OLR=1 (Kine ic II) OLR=2 (Kine ic III) AVERAGE 15 S8. Bio ans o ma ion phase Fig. S3. Con ibu ion o each phase o he o al me hanogenic bio ans o ma ion o OMPs. The appa en bio ans o ma ions measu ed in he solid (BS) and liquid phases (BL) a e ep esen ed by he o ange, lowe ba s and by he blue, uppe ba s, espec i ely. 16 S9. Remo al o OMPs du ing sewage sludge AD Table S6. Summa y o epo ed OMPs emo al du ing AD o sewage sludge unde simila ope a ional condi ions. The a e age emo al was calcula ed wi h he mean alue o each e e ence and o hose cases whe e wo comple ely di e en alues we e epo ed bo h we e conside ed. OMP AD emo al (%) Gonzalez-Gil e al. (2016) Ca balla e al. (2007) Na umiya e al. (2013) Sama as e al. (2014) Malmbo g & Magné (2015) Cla a e al. (2011) Pa e akis e al. (2012) Be ge sen e al. (2012) Yang e al. (2016) A e age 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 ‒ ‒ ‒ ‒ ‒ ‒ ‒ ‒ ‒ ‒ Ope a ional condi ions Con inuous diges e 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 Subs a e* MixS MixS MixS MixS MixS SS MixS & PS SS PS Tempe a u e (°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 p ima y and seconda y sewage sludge; PS: p ima y sludge; SS: sewage sludge ( ype no speci ied). 17 Re e ences Be ge sen, O., Øs nes, K., Vasskog, T., 2012. 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