Physicochemical Controls on Transport of Veterinary Pharmaceuticals and Hormones

to Surface WatersCheng-Hua Liu, Ya-Hui Chuang, Wei Zhang, Hui Li,

Brian J. Teppen, Stephen A. BoydDepartment of Plant, Soil and Microbial Sciences, Michigan

State University, East Lansing, MIJavier M. Gonzalez, National Soil Erosion Research Lab,

USDA-ARS, West Lafayette, INCliff T. Johnston, Dept. of Agronomy, Purdue University, West

Lafayette, INWashington, DC, October 12, 2016

U.S.: about 14,600 tons of antibiotics in livestock production

China: about 84,240 tons of antibiotics in livestock production

Antibiotics have been widely detected in soils, sediments, and waters.

Why Antibiotics?

Antibiotics in ecosystems exert selection pressure on bacteria for antibiotic resistance.

Futures Magazine, AgBioResearch, MSUSpring/Summer, 2015

Black carbon (BC) up to 45% of SOCCzimczik & Masiello, 2007

BC on average 13.7% of SOCReisser et al., 2016

DBC about 11% of DOC in surface watersJaffé et al., 2013

Physicochemical control on fate and transport of antibiotics Sorption to soil phases Facilitated transport of

antibiotics by fine particles

Lehmann, 2007. Nature

Biochar soil amendment to reduce the transport & bioavailability of antibiotics

Biochar amended Soil

leaching selective pressure

Plant uptake

Sorption

Primary soil geosorbents: amorphous organic matter (AOM), black carbon (BC) & clay (CL)

Sequestration of lincomycin Lincomycin, one of lincosamides, is persistent and

frequently detected in the environment.

MW: 406.54 g/mol logKow: 0.2

Sw: 927 mg L-1

pKa: 7.6 0 2 4 6 8 10 12 140

20

40

60

80

100

Frac

tion

(%)

pH

pKa = 7.6

LMC+ LMC0

Cheng-Hua Liu

Liu, C.-H.; Chuang, Y.-H.; Li, H.; Teppen, B. J.; Boyd, S. A.; Gonzalez, J. M.; Johnston, C. T.; Lehmann, J.; Zhang, W., Sorption of Lincomycin by Manure-Derived Biochars from Water. J. Environ. Qual. 2016, 45, (2), 519-527.

0 20 40 60 80 100 120 140 160 180 2000

200

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800

1000

0 20 40 60 80 100 120 140 160 180 2000

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1000

0 20 40 60 80 100 120 140 160 180 2000

200

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800

1000

0 20 40 60 80 100 120 140 160 180 2000

200

400

600

800

1000

BM300 BM400 BM500 BM600

DM300 DM400 DM600

PS300 PS400 PS500 PS600

q t (g

/g)

Time (day)

RDW500 DDM500 DDM600 CDM500 CDMW500 WW500

𝒒𝒕=𝑲 𝒊𝒅 𝒕𝟏 /𝟐+𝑪

Long-term sorption

kinetics

Intra-particle diffusion model

Short-term fast surfacereaction

Long-term slow pore diffusion

Biochar had long-term sequestration potential for antibiotics.

0 100 200 300 400 500 600 700 8000

100

200

300

400

500

600

700 BM600 pH = 6.0 BM600 pH = 9.8 Langmuir

q t (g

/g)

Ct (g/L)

LMC

LMC

LMC

Electrostatic interactions

LMC

Non-electrostatic interactions

LMC

LMC

0 2 4 6 8 10 12 140

20

40

60

80

100

Frac

tion

(%)

pH

pKa = 7.6

LMC

Non-electrostatic interactions

2-day quasi-sorption isotherm

Biochar surface

pH << pkapH =6

Biochar surface

pH >> pkapH =10

0 0.01 0.05 0.1200

300

400

500

600 BM600 pH = 6.0 BM600 pH = 9.8

Am

ount

linc

omyc

in s

orbe

d (

g/g)

NaCl Concentration (M)

pH and ionic strength effects

LMC

LMC

0 2 4 6 8 10 12 140

20

40

60

80

100

Frac

tion

(%)

pH

pKa = 7.6

Na

Na

Na

pH << pKa

LMC

LMC

LMC

Biochar surface

Na

Na

Na

Na

Na

LMC

Na

Na

Biochar surface

pH >> pKa

antibiotics

OC release

Extractable OC released from bull manure biochar (produced by 300oC) in DI water

Dissolved BC = 11% of DOC in surface water

BM

300

BM

400

BM

500

BM

600

DM

300

DM

400

DM

600

PS30

0PS

400

PS50

0PS

600

CD

M50

0C

DM

W50

0D

DM

500

DD

M60

0FW

500

FW60

0R

DM

500

PW50

0PW

600

WW

500

YL50

0B

S500

TS50

0TW

500

AR

S450

CS3

00C

S400

CS6

00O

K30

0O

K40

0O

K60

0Pi

300

Pi40

0Pi

600

MC

600

KW

450

DSW

_C

B50

0B

SG50

0B

P300

BP4

50B

P600

BG

300

BG

450

BG

600

0

4

8

12

16

20

24

28

Extr

acta

ble

orga

nic

carb

on (%

)

ADOC WDOC BDOC

Base-extractable OC could be up to 24% of total carbon in biochars

Facilitated antibiotics transport by fine biochar particles

inlet

outletAB

A: Background SolutionB: Antibiotics/BC Suspension

Peristaltic Pump

Fraction Collector

Column

UV-Vis

LC/MSMS

Solution pH 7Lincomycin (LCM)pKa 7.6, 80% cationsOxytetracycline (OTC)pKa 3.2, 7.5, 8.9; 74% zwitterionsSulfamethoxazole (SMX)pKa 1.6, 5.7; 95% anions

0 1 2 3 4 5 6 70.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 1 2 3 4 5 6 70.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 1 2 3 4 5 6 70.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

C/C 0

LCM only BC/LCM_Free LCM BC/LCM_BC-co-transported LCM

Pore volume

0.1 mM 1 mM 10 mM

IS(mM) MR(%)Free-LCM BC-sorbed LCM Total

LCM 0.1 49.4 - 49.41 86.6 - 86.6

10 96.5 - 96.5LCM-BC 0.1 3.3 75.4 78.7

1 7.6 16.9 24.410 15.8 2.0 17.8

Colloid-facilitated transport has higher environmental risk

Solute transport has higher environmental risk

Desorption from immobile BC should also be concerned

Completed and ongoing work Sorption screening test of 35 biochar samples under pH 6

and pH 9 for 2 and 30 days, respectively (completed) 180-day sorption kinetics and two-day quasi-equilibrium

sorption studies for 4 biochar samples (completed) 360-day long-term sorption kinetics for 17 biochars

(completed) Attenuation effect of sorption by organic acids

(completed) Quantification and characterization of extractable organic

carbon from biochar (completed) Facilitated transport of antibiotics by fine biochar

particles: ionic strength (completed), and pH effect (ongoing)

Rainfall simulation study with soil box (ongoing)

Peer-Reviewed Journal PublicationsLiu, C.-H., Y.-H. Chuang, H. Li, B.J. Teppen, S.A. Boyd, J.M. Gonzalez, C.T. Johnston, J. Lehmann, and W. Zhang. 2016. Sorption of lincomycin by manure-derived biochars from water. Journal of Environmental Quality, 45(2), 519-527.Stoof, C.R., A.I. Gevaert, C. Baver, B. Hassanpour, V.L. Morales, W. Zhang, D. Martin, S.K. Giri, and T.S. Steenhuis. 2016. Can pore-clogging by ash explain post-fire runoff? International Journal of Wildland Fire, 25(3), 294-305.Wang, B., W. Zhang, H. Li, H. Fu, X. Qu, and D. Zhu. 201_. Micropore clogging by dissolved black carbon: A new perspective on sorption irreversibility and kinetics of hydrophobic organic contaminants to black carbon. Environmental Pollution (in revision).Liu, C.-H., Y.-H. Chuang, H. Li, B.J. Teppen, S.A. Boyd, and W. Zhang. 201_. Dependence of lincomycin sorption on biochar physicochemical properties (in preparation).Liu, C.-H., Y.-H. Chuang, H. Li, B.J. Teppen, S.A. Boyd, and W. Zhang. 201_. Long-term sorption kinetics of lincomycin to manure-derived biochars (in preparation).Liu, C.-H., Y.-H. Chuang, H. Li, S.A. Boyd, J. Lehmann, B.J. Teppen, J.D. Mao, and W. Zhang. 201_. Quantification and characteristics of dissolved organic matter released from biochars (in preparation).Liu, C.-H., Y.-H. Chuang, H. Li, J.P. Zarnetske, S.A. Boyd, B.J. Teppen, and W. Zhang. 201_. Black carbon nanoparticles facilitated transport of antibiotics in saturated porous media (in preparation).

12 conference presentations & 16 invited presentations.3 graduate students, 1 postdoc, 1 visiting student, & 1 high school student.

Acknowledgment

• Collaborators: Drs. Yingjie Zhang (MSU), Bin Gao (UF), Johannes Lehmann (Cornell), Jingdong Mao (Old Dominion Univ.), Verónica L. Morales (ETH Zurich), Dongqiang Zhu (Peking University).

The research was supported by Agriculture and Food Research Initiative Competitive Grant No. 2013-67019-21377 from the USDA National Institute of Food and Agriculture.

Thank you!