Physicochemical Controls On Transport of Veterinary Pharmaceuticals And Hormones To Surface Waters
•Download as PPTX, PDF•
1 like•1,052 views
This document summarizes research on the physicochemical controls of transport of veterinary pharmaceuticals and hormones to surface waters. The research examined how sorption to soil phases and facilitated transport by fine particles can influence the fate and transport of antibiotics in the environment. Completed and ongoing work is described that examines the long-term sorption kinetics of lincomycin to biochars under varying conditions, as well as the potential for biochar particles to facilitate the transport of antibiotics through saturated porous media. The research aims to better understand how biochar amendments may reduce the transport and bioavailability of antibiotics in soil.
Recommended
More Related Content
What's hot
What's hot (20)
Similar to Physicochemical Controls On Transport of Veterinary Pharmaceuticals And Hormones To Surface Waters
Similar to Physicochemical Controls On Transport of Veterinary Pharmaceuticals And Hormones To Surface Waters (20)
More from National Institute of Food and Agriculture
More from National Institute of Food and Agriculture (20)
Recently uploaded
Recently uploaded (20)
Physicochemical Controls On Transport of Veterinary Pharmaceuticals And Hormones To Surface Waters
- 1. Physicochemical Controls on Transport of Veterinary Pharmaceuticals and Hormones to Surface Waters Cheng-Hua Liu, Ya-Hui Chuang, Wei Zhang, Hui Li, Brian J. Teppen, Stephen A. Boyd Department of Plant, Soil and Microbial Sciences, Michigan State University, East Lansing, MI Javier M. Gonzalez, National Soil Erosion Research Lab, USDA-ARS, West Lafayette, IN Cliff T. Johnston, Dept. of Agronomy, Purdue University, West Lafayette, IN Washington, DC, October 12, 2016
- 2. 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?
- 3. Antibiotics in ecosystems exert selection pressure on bacteria for antibiotic resistance.
- 4. Futures Magazine, AgBioResearch, MSU Spring/Summer, 2015 Black carbon (BC) up to 45% of SOC Czimczik & Masiello, 2007 BC on average 13.7% of SOC Reisser et al., 2016 DBC about 11% of DOC in surface waters Jaffé 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
- 5. 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)
- 6. 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 14 0 20 40 60 80 100 Fraction(%) 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.
- 7. 0 20 40 60 80 100 120 140 160 180 200 0 200 400 600 800 1000 0 20 40 60 80 100 120 140 160 180 200 0 200 400 600 800 1000 0 20 40 60 80 100 120 140 160 180 200 0 200 400 600 800 1000 0 20 40 60 80 100 120 140 160 180 200 0 200 400 600 800 1000 BM300 BM400 BM500 BM600 DM300 DM400 DM600 PS300 PS400 PS500 PS600 qt (g/g) Time (day) RDW500 DDM500 DDM600 CDM500 CDMW500 WW500 𝒒 𝒕 = 𝑲𝒊𝒅 𝒕 𝟏/𝟐 + 𝑪 Long-termsorptionkinetics Intra-particlediffusionmodel Short-term fast surface reaction Long-term slow pore diffusion Biochar had long-term sequestration potential for antibiotics.
- 8. 0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 BM600 pH = 6.0 BM600 pH = 9.8 Langmuir qt (g/g) Ct (g/L) LMC LMC LMC Electrostatic interactions LMC Non-electrostatic interactions LMC LMC 0 2 4 6 8 10 12 14 0 20 40 60 80 100 Fraction(%) pH pKa = 7.6 LMC Non-electrostatic interactions 2-day quasi-sorption isotherm Biochar surface pH << pkapH =6 Biochar surface pH >> pkapH =10
- 9. 0 0.01 0.05 0.1 200 300 400 500 600 BM600 pH = 6.0 BM600 pH = 9.8 Amountlincomycinsorbed(g/g) NaCl Concentration (M) pH and ionic strength effects LMC LMC 0 2 4 6 8 10 12 14 0 20 40 60 80 100 Fraction(%) 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
- 10. antibiotics OC release Extractable OC released from bull manure biochar (produced by 300oC) in DI water Dissolved BC = 11% of DOC in surface water BM300 BM400 BM500 BM600 DM300 DM400 DM600 PS300 PS400 PS500 PS600 CDM500 CDMW500 DDM500 DDM600 FW500 FW600 RDM500 PW500 PW600 WW500 YL500 BS500 TS500 TW500 ARS450 CS300 CS400 CS600 OK300 OK400 OK600 Pi300 Pi400 Pi600 MC600 KW450 DSW_ CB500 BSG500 BP300 BP450 BP600 BG300 BG450 BG600 0 4 8 12 16 20 24 28 Extractableorganiccarbon(%) ADOC WDOC BDOC Base-extractable OC could be up to 24% of total carbon in biochars
- 11. Facilitated antibiotics transport by fine biochar particles inlet outlet A B A: Background Solution B: Antibiotics/BC Suspension Peristaltic Pump Fraction Collector Column UV-Vis LC/MSMS Solution pH 7 Lincomycin (LCM) pKa 7.6, 80% cations Oxytetracycline (OTC) pKa 3.2, 7.5, 8.9; 74% zwitterions Sulfamethoxazole (SMX) pKa 1.6, 5.7; 95% anions
- 12. 0 1 2 3 4 5 6 7 0.0 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 7 0.0 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 7 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 C/C0 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 - 49.4 1 86.6 - 86.6 10 96.5 - 96.5 LCM-BC 0.1 3.3 75.4 78.7 1 7.6 16.9 24.4 10 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
- 13. 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)
- 14. Peer-Reviewed Journal Publications Liu, 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.
- 15. 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!
Editor's Notes
- Good morning, I am Wei Zhang, and the PD for this project. The other co-PDs are Hui Li, Brian Teppen, and Stephen Boyd at MSU, Javier Gonzalez at National Soil Erosion Research Lab of ARS, and Cliff Johnston at Purdue University. I would like to thank NIFA for this opportunity to share some of our results. In this project, we are studying physicochemical factors that influence the transport of pharmaceuticals and hormones to surface waters.
- So in this project, we focused on an important group of pharmaceuticals, i.e., antibiotics. Antibiotics are emerging contaminants that have been widely detected in our soils, sediments, and waters. The driver for this proliferation is the overuse by humans and animal agriculture. For instance, the US and China are two largest users of antibiotics, the majority of which are used in livestock production and then released into our environment.
- Once in the environment, antibiotics can exert selection pressure on bacteria to develop and maintain antibiotic resistance. If antibiotic resistance proliferation continues at current rate, by 2050, it will cause up to 10 million deaths every year, the majority of which will happen in Asia, Africa, and Latin America. But North America and Europe will also have significant numbers.
- To tackle antibiotic resistance problem, we believe that soil and environmental science community can play important roles. Therefore, this project is aimed to study what factors control the transport of antibiotics in soil and water environment, and how we could manage the transport risks. The project mainly focuses on sorption of antibiotics by soil components, and facilitated transport of antibiotics by fine particles. In particular, this project investigates black carbon interaction with antibiotics. Black carbon is produced by thermal decomposition of organic materials under oxygen-limited conditions (i.e., pyrolysis). It can be produced from wildfire, fuel combustion, or pyrolysis bioenergy production. Black carbon from engineered pyrolysis reactors is also called biochar.
- Therefore, this project particularly investigated biochar soil amendment as a mitigation strategy for reducing the transport of antibiotics. There are three primary soil geosorbents: amorphous organic matter, black carbon, and clay. If we look at the diagram on the upper right corner, the fraction of sorbed tetracycline in black carbon at lower aqueous-phase tetracycline concentration was much greater than clay and AOM. Therefore, black carbon or biochar may be used to sequester antibiotics. If we add biochar to soils, due to sorption of antibiotics to biochar, their transport to shallow groundwater that eventually flows into surface water by tile drainage or lateral flow can be reduced. Antibiotics uptake by crops and bacteria can also be decreased, which is being looked at in other projects.
- Because of the time limit, we cannot show everything we have accomplished in this project. We will highlight some of most interesting results. Here we used lincomycin as example because it is persistent and frequently detected in the environment. Lincomycin is hydrophilic and very soluble in water. Its pKa is 7.6. Therefore, at pH much lower than 7.6, it is cation, and at pH much higher than 7.6, it is a neutral molecule.
- First, we will look at some long-term kinetics data. Most of biochar had continued sorption of lincoymcin over 6 months. This long-term sorption was due to slow diffusion of lincomycin molecules into the interior of biochar pore space. This was supported by the good fitting of kinetic data with intra-particle diffusion model. Therefore, biochar could have long-term sequestration potential for antibiotics.
- Then, we investigated short-term sorption isotherms. Taking one biochar as example, lincomycin sorption was much higher at lower pH of 6 than at higher pH of 10. Now I would like remind everyone about the pH-dependent speciation of lincomycin on the right. Biochar surface is negatively charged. Therefore, at higher pH, lincomycin sorption was controlled by non-electrostatic interactions, and at lower pH, lincomycin sorption was controlled by both non-electrostatic and electrostatic interactions.
- We also found that lincomycin sorption decreased with increasing solution ionic strength at lower pH and remained constant at higher pH. This was because at higher pH non-electrostatic interaction was not influenced by ionic strength, but at lower pH there was competition between Na+ and lincomycin. This is important finding, and we will come back to this when discussing the transport results.
- Now let’s shift to a slightly different but relevant topic. It has been known for some time now that biochar can release a substantial amount of organic matter to water. This 2013 science paper argues that charcoal could release dissolved black carbon which eventually flows from soil to surface water. I would also like to highlight a 2014 paper by Spokas et al., reporting that biochar could be physically disintegrated to release biochar colloids and nanoparticles. In a recent 2016 paper, Qu et al. characterized chemical and structural properties of dissolved black carbon. In our own work we also found that up to 24% of total carbon in biochar could be extracted by a dilute base solution. So our question is how the release of organic carbon will influence the sorption and transport of antibiotics. In this presentation, we will mainly focus on the facilitated transport of antibiotics by biochar nanoparticles.
- Here we show you the experimental design. The transport experiments were conducted at solution pH 7 for three antibiotics, lincomycin, oxytetracycline, and sulfamethoxazole. But we will only have time to discuss the results of lincomycin. We have two treatments: in the first one, we injected antibiotics-only solution into saturated sand column and then flushed it out with antibiotics-free background solution; in the second one, we injected the mixture of antibiotics and biochar nanoparticles, and then flushed the column with the background solution. We measured antibiotics concentration and biochar nanoparticle concentrations in the effluent to establish the breakthrough curves (BTCs) as shown in the next slide.
- The experiments were performed in 0.1 mM, 1 mM, and 10 mM KCl background solutions. Black squares are the BTCs of lincomycin-only treatment. With increasing ionic strength, the transport of lincomycin through saturated sand column increased. Now you probably remember that this could be due to the competition from other cations. Red circles are the BTCs of free lincomycin in water in the antibiotics/biochar mixture treatment, and blue triangels are the BTCs of biochar-associated lincoymcin. Clearly, some of BC-associated lincomycin was transported out of the column. In particular, at 0.1 mM, the total lincomcyin transported was even increased to 79% of injected lincomycin from 49% without BC. Therefore, BC could facilitate the transport of lincomycin at lower ionic strength, but could promote lincomycin retention at higher ionic strength.
- Here we listed other work in this project that we didn’t have time to go over today. The pH effect on facilitated antibiotics transport and rainfall simulation study with soil box are still ongoing.
- Now we would like to briefly mention some outcome of this project. Two papers were published, one paper currently under revision, and four more manuscripts under preparation. We have also given 12 conference presentations, and 16 invited talks. The project supported 3 graduate students, 1 postdoc, 1 visiting student, and 1 high school student.
- With that, I would like to acknowledge the funding support from NIFA and thank our collaborators. Thank you!