Interactions of Emerging Contaminants- with Functionalized Biochar

Prof John L Zhou, Md. B. Ahmed School of Civil and Environmental Engineering UTS 21 August 2018 Graphics created by by created Graphics volupta re conecum Ullupta doluptuam. et pe evelignis BIOCHAR 2018 2 Outline of the Talk

1. residues in the environment

2. Preparation and characterization of functionalized biochar

3. Application of functionalized biochar in antibiotic removal from

water and wastewater

4. Conclusions BIOCHAR 2018 3 Emerging Contaminants in the Environment

• Pharmaceuticals and personal care products (PPCPs) • Nano-materials • Disinfection by-products • New pesticides • Degradation products

Halpern et al. (2008) Science 319, 948 BIOCHAR 2018 4 Pharmaceutical Residues in the Environment • Of the greatest concern worldwide are pharmaceuticals, in particular antibiotic residues: ü Produced in large quantity, e.g. > 25000 tons per annum produced in China alone. ü Between 80-90% are excreted unmetabolized once consumed in human and animals. ü Poorly removed in sewage treatment plants. ü Potential to cause antibiotic resistance, leading to the so-called “superbugs” with antibiotic resistance genes. BIOCHAR 2018 5 Comparative Removal Efficiency of Emerging Contaminants

Ahmed et al. (2017) JHM 323, 274-298 BIOCHAR 2018 6 Antibiotic Resistance Germs Take a Bite Out of Antibiotics

D-CYCLOSERINE KANAMYCIN SISOMICIN CARBENICILLIN DICLOXACILLIN PENICILLIN G VANC OM YC IN Taste test. Harvard University researchers Morten SULFAMETHIZOLE SULFISOXAZOLE Sommer and Gautam Dantas and colleagues used soil samples from a Massachusetts forest and a cornfield (inset) to screen for antibiotic-eating Growth No Growth microbes.

Science (2008) 320, 33 BIOCHAR 2018 7 Antibiotics in Water and Sediments from Mariculture Sites in China

Chen et al. (2017) STOTEN 580, 1175 BIOCHAR 2018 8 Outline of the Talk

1. Antibiotic residues in the environment

2. Preparation and characterization of functionalized biochar

3. Application of functionalized biochar in antibiotic removal from

water and wastewater

4. Conclusions BIOCHAR 2018 9 Why Biochar and Functionalized Biochar?

1000000 • Biochar is a C-rich product obtained Lower price Higher price 100000 when biomass is heated at elevated temperature in a closed reactor with little 10000 or no available air. 1000 • Functionalized biochar (fBC) is obtained

100 when biochar is further treated either

10 chemically or physically in order to

Price of adsorbent ($/kg) improve its functional groups and 1 sorption performance.

0.1 BCs ACs Resins MWCNTs SWCNTs Adsorbent Ahmed et al. (2015) STOTEN 532, 112-126 BIOCHAR 2018 10 Preparation of Biochar and Functionalized Biochar

Wash & Pyrolysis at Increased N Crushed into Cut into 2 Cooling at Biomass drying at 380 °C for 2 h pressure 10 psi at desired size, Biochar small sizes room 105 °C at 2 psi 380 °C for 15 min temp. wash with DI (BBC380) & drying

Gasses Outlet N2 Inlet Vent

Pyrolyser Head Soaking in Wash 50% Leave at Heated at Cooling with DI & Biochar phosphoric 50 °C for 600 °C for 2 adjust Screws in room fBC acid 3 h h at 2.0 psi temp. pH to solution 7.0 and Valve dry Pyrolysis Chamber Pyrolysis

Furnace

N2 Cylinder BIOCHAR 2018 11 Physicochemical Properties of Biochar & fBC

Sample Composition data

Yielddry basis (%) Moisture content (%) Ash (%) Volatile mater (%) Fixed carbon (%)

Biomass 5.61 12.93 63.83 26.67

BBC380 43.50

1MbBBC600

Initial pH 1.62 3.00 4.35 6.13 10.00

Final pH 1.15 2.74 3.39 4.09 8.28

Zeta potential (mV) 5.34±0.32 -3.25±0.24 -12.76±1.23 -19.6±1.15 -45.9±4.67

Sample EDS analysis BET surface area BJH Adsorption pore diameter

C % O% P% Molar O/C BBC380 81.18 18.83 - 0.232 0.50 m2 g-1 113.5 Å 1MbBBC600 51.96 39.52 8.16 0.761 1.12 m2 g-1 83.8 Å 1 BIOCHAR 2018 12 SEM of BBC380 and 1MbBBC600 BIOCHAR 2018 13 Raman Spectra of fBC FTIR Spectra of fBC

Zeta Potential Value of fBC is 2.20 BIOCHAR 2018 14 XPS Spectra of fBC Name Peak BE Atomic % Surface group Assignment C (1s) A 284.8 56.98 C=C Graphitic carbon C (1s) B 286.27 13.6 C-O- Phenolic, alcoholic, etheric C (1s) C 287.8 4.15 C=O Carbonyl or quinone C (1s) D 289 3.13 COO- Carboxyl or ester C (1s) E 290.54 2.77 C=O/ C=C Carbonate, ocluded CO, p-electrons in aromatic ring C (1s) F 292.35 1.13 π-π* transition The transition due to conjugation N (1s) 401.47 0.8 C–N+H-C Forms of quaternary nitrogen, protonated pyridinic ammonium ions, nitrogen atoms replacing carbon in graphene, O (1s) B 533.3 8.52 C-O- Oxygen singly bonded to carbon in aromatic rings, in phenols and ethers O (1s) A 531.62 4.8 C=O Oxygen doubly bonded to carbon

P (2p) 133.79 2.3 C-O-PO3 Polyphosphates and/or phosphates BIOCHAR 2018 15 Outline of the Talk

1. Antibiotic residues in the environment

2. Preparation and characterization of functionalized biochar

3. Application of functionalized biochar in antibiotic removal from

water and wastewater

4. Conclusions BIOCHAR 2018 16 Single and Competitive Sorption of Sulfonamides by fBC

H2N CH3 pK a1 O SMT N R S 1 NH O H N pK N CH STZ 2 a2 3 pK SMT a1 O N SMX S R NH 2 O pK S 3D structures H2N a2 STZ pK a1 O + + + SMT / SMX /STZ - - - N O SMT / SMX /STZ S R NH 3 O pK CH3 a2 0 0 0 SMX SMT / SMX /STZ

Sulfonamide structures

H2N

O +/- +/- +/- SMT / SMX /STZ S NH R 1/R2/R3 Sulfonamide species O General formula of sulfonamides BIOCHAR 2018 17 pH Effect on Sorption

• Functionalized biochar can sorb antibiotics in both single and competitive mode • Sorption capacity for antibiotics was three times higher in single mode than in competitive mode • Sorption capacity decreases as > > sulfamethazine • Solution pH is a significant parameter for removing ionisable sulfonamides • Sorption is mostly governed by the H-bond formation

and π-π interactions Ahmed et al. (2017) CEJ 311, 348-358 BIOCHAR 2018 18 Proposed Sorption Mechanism

- H δ + SMX O δ .. π O R N S NH2 SMT - .. π δ - δ H N S NH R O + 2 δ STZ at low pH + + Hδ O For neutral molecules π - π EDA - Lewis acid base interaction δ Diffusion .. O O H O: OH OH ligend exchange with -OH - δ P O group but not favorable O H π π H π OH R

O π O Higher electron density π NH - δ O H O S O - CAHB + δ + δ δ H O at high pH O + π δ .. - - π EAA δ - π H N π π π - + 2 π S N R δ δ O H O O at higher pH where H H N O 2.. negative species O O exist (less favorable) H O CAHB - - δ- .. Oδ R N S π NH2 .. + - δ δ H N S N 2 π R O - at higher pH where negative species + δ O δ + Where, exist(mostly favored) Hδ R=R /R /R 1 2 3

π electron acceptor BIOCHAR 2018 19 Sorption of Chloramphenicol

2.4x105 (a) STZ (b) 5 10 2.1x10 SMX 10 SMT 10 5 1.8x10 CP (c) 0 8 8 1.5x105 ) -1 ) -10 -1 5 6 1.2x10 SMZ 6

(L kg (L SMT

(mg g d

s -20 SMX q K 4 9.0x10 4 CP PSO kinetic model fit for STZ 4 PSO kinetic model fit for SMT 4 (mV) potential Zeta -30 6.0x10 PSO kinetic model fit for SMX 2 PSO kinetic model fit for CP PFO kinetic model fit for STZ 4 2 3.0x10 PFO kinetic model fit for SMT -40 Zeta potential of fBC PFO kinetic model fit for SMX Initial sorption solution pH 0 PSO kinetic model fit for CP pH = 2.2 0.0 pzc Equlibrium sorption solution pH 1 2 3 4 5 6 7 8 9 10 11 0 200 400 600 800 1000 1200 1400 1600 1800 2000 -50 0 0 1 2 3 4 5 6 7 8 9 10 11 pH Time (min) pH

(a) Effect of pH on Kd, (b) Sorption kinetics, (c) zeta potential of functionalized biochar Ahmed et al. (2017) BT 238, 306-3112 BIOCHAR 2018 20 Sorption of Chloramphenicol: Mechanism

Resonance Structures Sorption Affinity M echanisms Competitive Sorption Affinity: STZ> SMX> CP >SMT - p-electron acceptor sites OHO Cl d + At very low pH: O d - d + (i). Repulsion interactions + .. d R NH dS NH O NH Cl (ii). BC-OH + sulfonamides/CP = EDA interactions d- 2 + d N - d-O d At pH 4.0-4.25: - + - Sulfonamides, R= Hetrocyclic -O OH d (i). BC-COO .....H .... O2N-chloramphenicol = CAHB formations with EDA interactions rings for SM T, STZ & SM X Chloramphenicol (ii). BC-COO..H + sulfonamides (NHSO 2-/NH/ -NH 2/CH3) = H-bond formations

p-electron donor site At pH above 7.0: - + d - - d + d - (i). Repulsion interactions O d d ..+ .. (ii). Sulfonamides-N-+ H O = sulfonamides-NH + -OH+ O 2 O..H + + - - + - d d .. (iii). BC-O....H + N....sulfonamides =BC-O .....H .... N..sulfonamides = CAHB OH BC-C=O + BC-OH BC-COOH (iv). BC-OH + chloramphenicol (H /-OH/NO2/-NH-/-Cl) = H-bond formations

Comparative Treatment Trend: Deionized water> Lake water > Synthetic wastewater BIOCHAR 2018 21 Sorption of Antibiotics in Mixture Mode

Lake water Synthetic wastewater

STZ SMX STZ SMX SMT CP SMT CP 100 100 (a) (b)

80 80

60 60 Percentage Percentage

40 40

20 20 200 300 400 500 600 700 200 300 400 500 600 700 fBC dosage (mg L-1) fBC dosage (mg L-1) BIOCHAR 2018 22 (a) Effects of Sample Composition on Chloramphenicol Sorption (b) Regeneration of Functionalized Biochar at 300 oC

rd th fBC-2 (1st cycle) fBC-2 (3 cycle) fBC-2 (5 cycle) th th fBC-2 (2nd cycle) fBC-2 (4 cycle) fBC-2 (6 cycle) 100 3.0 Synthetic wastewater (a) (b) Lake water Deionized water 2.5 80 ) -1 2.0

M L M 60 μ 1.5 40 1.0 Residual conc. ( Percentage of removal of Percentage 20 0.5

0.0 0 Deionized water Synthetic water Lake water 0 10 20 30 40 50 60 Water type Dose (mg) Ahmed et al. (2017) STOTEN 609, 885-895 BIOCHAR 2018 23 SEM of fBC, nZVI-fBC and nFe3O4-fBC Composite (a-c) using SEM with energy dispersive spectrometer (EDS) and XRD pattern of nZVI (d).

(d) 1000 Fe

800 Fe

600 Fe2.66O4

Counts 400

Fe O 200 2.66 4 Ahmed et al. (2017) CEJ 322, 571-581 0

20 25 30 35 40 45 50 55 60 2? / degress BIOCHAR 2018 24 XPS of nZVI-fBC Composite before Sorption Experiments

45000 22500 (532.12, O= , Organic C-O) - 2 (533.45, O , Organic oxygen C=O) 40000 (284.8, C=C/ C-C, SP ) (a) (b) 20000

35000 (530.7, Metal oxide ) 17500 30000

25000 (289, -O-C=O/-COOH/-COOFe-) 15000

20000 12500 Counts/s (286.4, C-O)

15000 (287.6, C=O) 10000 * 10000 P-P

7500 5000

5000 292 291 290 289 288 287 286 285 284 283 282 539 538 537 536 535 534 533 532 531 530 529 528 527 526

12000 (725) (711.4) (c) 300000 (d) O1s C1s 11000

(720.3) (716.6) 250000

10000 Fe2P 200000 Fe2p 9000 150000 Counts/s

8000 100000 N1s

7000 50000 P2p

6000 729 726 723 720 717 714 711 708 705 700 600 500 400 300 200 100 Binding energy (eV) BIOCHAR 2018 25 Chloramphenicol Transformation By-products Identified by Their Retention Times (2.1 min, 2.7 min) by LC-MS/QTOF from Deionized Water (a) and Lake Water (b).

(a) ZVI (deionized water) before experiment 1.0x106 ZVI (deionized water) after experiment

8.0x105 Chloramphenicol (m/z, 323.0)

N-[1,3-dihydroxy-1-(4-aminophenyl)propan-2-yl]acetamide 6.0x105 (m/z, 223.1)

2-chloro-N-[1,3-dihydroxy-1-(4-aminophenyl)propan-2-yl]acetamide

(m/z, 257.0) 4.0x105

2.0x105 Counts (b) 2.0 2.5 3.0 3.5 4.0 4.5 5.0

(m/z 323.0) ZVI (lake surface water) before experiment 100 1.4x106 ZVI (lake surface water) after experiment 80

100 1.2x106 60 100 80 40

80 Abundancy (%) 1.0x106 60 20 60 0 5 40 300 310 320 330 340 350 8.0x10 Abundancy (%) 40 m/ z Abundancy (%)

20 20 6.0x105 0 0 210 220 230 240 250 240 250 260 270 280 m/ z m/ z 4.0x105 (m/z 223.1) (m/z 257.0)

2.0x105

2.0 2.5 3.0 3.5 4.0 4.5 5.0 Acquisition time (min) BIOCHAR 2018 26 Proposed Reduction and Dechlorination Mechanism for Chloramphenicol from Water and Wastewater

Fe0 (nZVI)+2H O-2e- 2+ - & nZVI-fBC composite nFe O -fBC composite 2 Fe + 2OH + H2 Transformation 3 4 (unstable) Reduction of nitro group: (Stable) Cl Cl Cl Cl Cl Cl Cl Cl HN O HO HN O 2e- HN O OH - HN O 2e- 2e HO HO HO OH OH OH H O N H H H (m/z, 323) O H H O N N N OH H Chloramphenicol NO HOAM AM Cl2

Cl De-chlorination: Cl Cl HN O HN O HO HO HN O 2e- OH OH HO OH H H -HCl H H H N N H N H 1 st P rodu ct (m /z, 257) H 2 nd P rodu ct (m /z, 223) H AM Cl2 4e- -2HCl BIOCHAR 2018 27 Chloramphenicol Transformation Products Highlighted by Their Retention Times after 10 min (a), 30 min (b), 150 min (c), and 12 h (d) Treatment using nZVI-fBC in synthetic wastewater

6 (a) 6 (b) 1.4x10 (m/z, 323.1) 1.4x10

(m/z, 323.1) 6 1.2x106 1.2x10

6 1.0x106 1.0x10

5 5 8.0x10 8.0x10

6.0x105 6.0x105

(m/z, 257) 5 (m/z, 257) 5 (m/z, 223) 4.0x10 (m/z, 223) 4.0x10

2.0x105 2.0x105

2.0 2.5 3.0 3.5 4.0 4.5 5.0 2.0 2.5 3.0 3.5 4.0 4.5 5.0 Counts

2.1x106 1.4x106 (c) (d)

1.8x106 1.2x106 (m/z, 323.1)

1.5x106 1.0x106 (m/z, 323.1) 1.2x106 8.0x105

9.0x105 6.0x105

5 6.0x10 (m/z, 223) 4.0x105 (m/z, 223) (m/z, 257) (m/z, 257) 3.0x105 2.0x105

2.0 2.5 3.0 3.5 4.0 4.5 5.0 2.0 2.5 3.0 3.5 4.0 4.5 5.0

Acquisition time (min) BIOCHAR 2018 28 Sorption and Reduction of Chloramphenicol using nZVI-fBC Composite (in the 1st cycle) followed by Sorption onto nFe3O4- fBC Composite

nZVI-fBC composite (reduction, 1st cycle) nFe O -fBC composite (sorption, 2nd cycle) nZVI-fBC composite (sorption, 1st cycle) 3 4 100 (a)

80

60

40 Removal (%) Removal

20

0 Deionized water Synthetic water Lake water Water type BIOCHAR 2018 29

Regeneration of nFe3O4-fBC Composite by Methanol for Repetitive Applications (up to 7 cycles) for Chloramphenicol

nd th nFe O -fBC 6th cycle nFe3O4-fBC 2 cycle nFe3O4-fBC 4 cycle 3 4 rd th th nFe O -fBC 3 cycle nFe O -fBC 5 cycle nFe3O4-fBC 7 cycle 100 3 4 3 4

80

60

40 Removal (%) Removal

20

0 Deionized water Synthetic water Lake water Water type BIOCHAR 2018 30

fBC-nZVI Composite

F e 3 O 4 , F e 2 O 3 , F eO O H and iron hydroxides in solu tion

100% Reduction of chloram phenicol -fBC )

Oxidation of nZVI 4

nZVI O 3 ( 70% sorption & Methylene Scrap iron 30% reduction of Chloramphenicol blue sorption chloramphenicol) sorption (100% ) (100% ) Transformation Regeneration & Application Eucalyptus fB C st wood to biochar in 1 cycle repetitions 2 to 7 after cycles -fBCcom posite 4 7 cycles O 3 nZVI-fBC Composite nZVI-fBC nFe High sorption performance sorption High Magnetic-fBC (i.e. nFe (i.e. Magnetic-fBC BIOCHAR 2018 31 TEM Images of (a) Unmodified nZVI and (b) S-nZVI; and (c) XRD Spectra of Unmodified nZVI and S-nZVI (1.0 g/L nZVI with 0.14 molar ratio of S/Fe)

Cao et al. (2017) EST 51, 11269-11277 RESEARCH TALK 32 Schematic Mechanism of Enhanced (FF) Removal by S-nZVI, (b) Mass Balance of FF and Dechlorinated FF during reaction, and (c) Pathway of FF Removal RESEARCH TALK 33 Conclusions 1. Antibiotic residues in the environment are of global concern due to potential adverse effects e.g. inducing antibiotic resistance genes. 2. Functionalized biochar has been prepared with significant capacity for the removal of antibiotic residues from water and wastewater. 3. H-bond formation, π-π electron donor acceptor and electrostatic interactions were the main sorption mechanisms at different pH. 4. Functionalized biochar is effective in immobilizing nZVI to form composite which can sorb and reduce antibiotic compounds. 5. Future research is needed to develop novel biochar-based composite materials for enhanced sorption and reduction capabilities, and with regeneration potential. Thank you for listening !

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