Download - Physicochemical Controls On Transport of Veterinary Pharmaceuticals And Hormones To Surface Waters
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
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0 20 40 60 80 100 120 140 160 180 2000
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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
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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
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40
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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
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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
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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
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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
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1.0
0 1 2 3 4 5 6 70.0
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0 1 2 3 4 5 6 70.0
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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!