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Effect of ferroferric oxide on batch anaerobic treatment of high strengthen synthetic wastewater Qidong Yin Graduate School at Shenzhen Tsinghua University Sep 16, 2016 Contents Background Materials and Methods Results and


  1. Effect of ferroferric oxide on batch anaerobic treatment of high strengthen synthetic wastewater Qidong Yin Graduate School at Shenzhen Tsinghua University Sep 16, 2016

  2. Contents • Background • Materials and Methods • Results and Discussions • Conclusions

  3. 1 Background

  4. 1.1 Anaerobic treatment • Anaerobic treatment is a sustainable technology • A severe environmental issue Water Pollution • Wastewater Resources Water Reuse • Energy Recovery Treatments Recycling • Methane Production Anaerobic Treatment • Sustainable Technology

  5. 1.1 Anaerobic treatment • Three-step mechanisms Hydrolysis/ Methanogenesis 1 3 Acidification Complex organic Small organic Acetate/ CH 4 , matters matters Formate/ H 2 CO 2 Hydrogenesis 2 /Acetogenesis • Syntrophic Communities: The complete conversion from organic matters to methane requires a microbial consortium composed of various types of species.

  6. 1.2 Interspecies electron transfer , IET • Interspecies electron transfer (IET) Interspecies H 2 transfer ( Methanothermus, Methanocaldococcus ) Interspecies formate transfer (Methanobacterium,Methanothermococcus) Direct interspecies electron transfer (Methanosaeta, Methanothermobacte, Methanosarcina) CH 4 , CO 2 Electron Transfer Production (H 2 /Formate) Acidogenic Methanogens bacteria Syntroph

  7. 1.3 Direct interspecies electron transfer, DIET • DIET is a new mechanism  DIET means acidogenic bacteria ( Geobacter ) can transfer electron to methanogens directly using its conductive pili or outer membrane cytochromes, rather than H 2 /Formate. acidogenic bacteria methanogen (Rotaru et al. 2013. A new model for electron flow during anaerobic digestion: direct interspecies electron transfer to Methanosaeta for the reduction of carbon dioxide to methane.)

  8. 1.3 Direct interspecies electron transfer, DIET • Conductive materials  Dosing conductive materials could accelerate the electron transfer among syntrophic communities. CH 4 , CO 2 Pili/Cytochromes Acidogenic Methanogens Conductive bacteria materials

  9. 1.3 Direct interspecies electron transfer, DIET • Conductive materials  Conductive materials can facilitate the methanogenesis. Conductive Carbon source Effect Reference materials Carbon Glucose/ Rotaru et al.,2014; materials Ethanol Liu et al.,2012; ( GAC/ carbon Facilitate CH 4 Chen et a.,2014; cloth/ biochar ) production Luo et al.,2015 rate/Shorten lag Magnetite Acetic acid/ phase /Facilitate the Kato et al.,2012; (Fe 3 O 4 )/ Propionic consumption of Carolina et al.,2014; Hematite acid/Butyric VFA Yamada et al.,2015; (Fe 2 O 3 ) acid/ Li et al.,2015; Beef extract Zhu et al.,2015

  10. 1.3 Direct interspecies electron transfer, DIET • Conductive materials  Conductive materials facilitated the production rate and shortened the lag phase during CH 4 production. (Luo et al. 2015) (Li et al. 2015)

  11. 1.4 Research Purposes The aims of this study were to – Examine the effect of conductive material Fe 3 O 4 on the performance of anaerobic treatment of high strengthen synthetic wastewater. – Compare the effect of Fe 3 O 4 on anaerobic sludge acclimated with different carbon substrates.

  12. 2 Materials and Methods

  13. 2 Materials and Methods • System operation  2 ASBR: Starch based reactor/ Tryptone based reactor  COD concentration: 3 g COD/L (starch or tryptone)  Starch and tryptone were used to represent carbohydrate and protein substrate, respectively. Operating conditions heater CH 4 、 CO 2 Parameter ASBR Volume 2 L synthetic effluent wastewater HRT 48 h SRT 33 d 35 ℃ Temperature sludge 23 h anaerobic ( 5min filling ) +1 h settling Operation mode gas flow meter ( 5min decanting ) mixer

  14. 2 Materials and Methods • Batch effect by the dosage of Fe 3 O 4 Hydrolysis/ Methanogenesis Acidification Complex organic Small organic Acetate, CH 4 , materials matters H 2 CO 2 Hydrogenesis /Acetogenesis • Operating condition Experimental conditions Parameter Value Effect of carbon by Fe 3 O 4 dosage : 10 g/L Fe 3 O 4  Conductive material Volume 500 mL Effect of Fe 3 O 4 dosage concentrations: 2.5 g/L, 5 g/L, 10 g/L, 15 g/L, 20 g/L. Mixer speed 170 rpm  Groups: Control group/ Fe 3 O 4 group 35 ℃ Temperature  Inoculated Sludge: taken from ASBRs

  15. 3 Results and Discussions

  16. 3.1 Batch experiments • Short term effect by the dosage of Fe 3 O 4 120 210 (b) (a) Tryptone- Tryptone- 100 180 Acetic acid CH 4 150 80 Acetic acid (mg/L) CH 4 (mL) 120 60 90 40 Control Control Fe 3 O 4 Fe 3 O 4 60 20 30 0 0 10 20 30 40 50 0 0 10 20 30 40 50 Time (h) Time (h)  The R max was increased by Ultimate Lag Maximum Correlation 35.3% and the lag time was Reactor CH 4 yield phase production coefficient λ (h) R 2 shortened by 48% after (mL) rate (mL/h) dosing Fe 3 O 4 . Control 117.3 5.0 5.1 0.999  Acetic acid consumption rate 112.5 2.6 6.9 0.995 Fe 3 O 4 was also improved.

  17. 3.1 Batch experiments • Short term effect by the dosage of Fe 3 O 4 80 250 (c) (d) Starch- Starch- 70 200 CH 4 60 Acetic acid Acetic acid (mg/L) 50 150 CH 4 (mL) 40 100 30 Control Control Fe 3 O 4 20 Fe 3 O 4 50 10 0 0 0 10 20 30 40 50 60 0 10 20 30 40 50 60 Time (h) Time (h)  The addition of Fe 3 O 4 had Ultimate Lag Maximum Correlation little effect on the CH 4 Reactor CH 4 yield phase production coefficient λ (h) (mL) rate (mL/h) R 2 production rate or the lag phase. Control 73.5 5.4 2.8 0.999  The produced acetic acid Fe 3 O 4 80 6.4 3.3 0.999 concentration was increased.

  18. 3.1 Batch experiments • Short term effect by the dosage of different Fe 3 O 4 concentrations 75 180 Tryptone- Tryptone- (b) (a) 160 60 CH 4 140 Acetic acid 120 Acetic acid (mg/L) Control 45 F2.5 100 CH 4 (mL) F5 80 F10 Control 30 F15 F2.5 60 F20 F5.0 F10 40 15 F15 F20 20 0 0 0 4 8 12 16 20 24 28 32 0 4 8 12 16 20 24 28 32 Time (h) Time (h) Ultimate Maximum Correlation  Generally, the R max was Lag phase Reactor CH 4 yield production coefficient λ (h) R 2 (mL) rate (mL/h) increased and the lag phase Control 77.35 9.19 4.31 0.9931 became shorter with the F2.5 72.67 7.51 4.98 0.9931 Fe 3 O 4 concentration. F5 66.56 6.96 5.19 0.9967  Acetic acid consumption rate F10 68/96 6.56 5.51 0.9981 was faster. F15 65.38 5.51 5.54 0.9980 F20 58.06 4.31 4.85 0.9963

  19. 3.1 Batch experiments • Short term effect by the dosage of different Fe 3 O 4 concentrations 55 160 Starch- (d) Starch- 50 (c) 140 45 Control CH 4 Acetic acid 120 F2.5 40 F5 Acetic acid (mg/L) 35 100 F10 CH 4 (mL) 30 F15 80 F20 25 Control F2.5 60 20 F5 15 F10 40 F15 10 F20 20 5 0 0 0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35 Time (h) Time (h) Ultimate Lag Maximum Correlation  Different Fe 3 O 4 concentrations Reactor CH 4 yield phase production coefficient λ (h) R 2 (mL) rate (mL/h) all led to longer lag phase. Control 45.37 4.28 3.04 0.9931  Only the R max of F2.5 and F5 F2.5 47.82 4.93 3.40 0.9931 increased. F5 52.57 4.92 3.48 0.9967  No significant improvement F10 44.71 6.37 2.98 0.9981 was found. F15 56.71 4.8 2.46 0.9980 F20 54.39 5.0 1.79 0.9963

  20. 3.1 Batch experiments • Short term effect of Fe 3 O 4 (10g/L) on hydrolysis and acidification phase of tryptone 700 600 500 VFAs (mg/L) 400 BES was added to inhibit the 300 activity of methanogens Control 200 Fe 3 O 4 (BES: 2-bromoethanesulfonic acid sodium 100 salt) 0 0 5 10 15 20 25 Time (h)  The control group and the Fe 3 O 4 group had similar trend of VFAs production, indicating that short term dosage of Fe 3 O 4 might not facilitate the hydrolysis and acidification of tryptone.  Similar results were obtained by the metabolic end product of hydrolysis and acidification, acetic acid.

  21. 3.1 Batch experiments • Short term effect of Fe 3 O 4 on methanation 80 Ultimate Lag Maximum Correlation 70 Reactor CH 4 yield phase production coefficient 60 Control λ (h) (mL) rate (mL/h) R 2 50 Fe 3 O 4 CH 4 (mL) 40 30 72.6 17.91 6.42 0.9915 Control 20 10 Fe 3 O 4 67.87 19.64 1.72 0.9828 0 0 10 20 30 40 50 60 Time (h)  Only acetate was added as carbon substrate, instead of tryptone.  Without hydrolysis and acidification, adding Fe 3 O 4 seemed to hinder the activities of methanogen.  The R max was decreased by 73.1% and the lag time was delayed by 9.7%.

  22. 3.2 Microbial community  Short-term effect – Microbial community 100 100 (a) (b) 80 80 Other Acidobacteria Methanosarcina Relative abundance (%) Raltive abundance (%) Synergistetes Methanosaeta Spirochaetes 60 60 Methanospirillum Chloroflexi Methanolinea Euryarchaeota Methanoculleus Proteobacteria 40 Methanothermobacter 40 Firmicutes Methanosphaera Bacteroidetes Methanobrevibacter Methanobacterium 20 20 0 0 Tryptone Starch Tryptone Starch  Methanosarcina (66.28%) was the dominant methanogen in the sludge acclimated with tryptone and Methanosarcina was proved to accept electrons via DIET.  Methanobacterium (92.80%) was predominant in the sludge acclimated with starch. And its ability of DIET is still controversial.

  23. 4 Conclusions

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