Molecular mechanisms of organic contaminant interactions in soils.

MOLECULAR MECHANISMS OF ORGANIC CONTAMINANT INTERACTIONS IN SOILS.

Sponsoring Institution

National Institute of Food and Agriculture

Project Status

COMPLETE

Funding Source

HATCH

Reporting Frequency

Annual

Accession No.

0176496

Grant No.

(N/A)

Cumulative Award Amt.

(N/A)

Proposal No.

(N/A)

Multistate No.

(N/A)

Project Start Date

Oct 1, 2012

Project End Date

Sep 30, 2017

Grant Year

(N/A)

Program Code

[(N/A)]- (N/A)

Recipient Organization
PURDUE UNIVERSITY
(N/A)
WEST LAFAYETTE,IN 47907

Performing Department
Agronomy

Non Technical Summary
Our overall program is centered on understanding the environmental fate, exposure, and toxicology of organic contaminants in soils. These compounds include pesticides, pharmaceuticals, mycotoxins, dioxins, dibenzofurans, polyaromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs). In this project, we propose to characterize poorly understood mechanistic processes that control sorption and transformation of these compounds to whole soils and soil constituents.

Animal Health Component

(N/A)

Research Effort Categories

Basic

(N/A)

Applied

(N/A)

Developmental

(N/A)

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
104	0110	2000	100%

Knowledge Area
104 - Protect Soil from Harmful Effects of Natural Elements;

Subject Of Investigation
0110 - Soil;

Field Of Science
2000 - Chemistry;

Keywords

sorption

hydrophobic organic contaminants

Goals / Objectives
Due to their exceptionally low water solubilities, many hydrophobic organic contaminants (HOCs) such as polychlorinated dioxins and furans (PCDD/Fs) are strongly and extensively bound to soil and sediment particles. Because many HOCs are highly resistant to natural chemical or biological decomposition, sorption is a primary determinant of their environmental fates and impacts. Importantly, adsorption to soil/sediment particles may modify the bioavailabilities and toxicities of HOCs in unknown ways. The major goals of this project are: (1) to advance fundamental understanding of HOC sorption by the dominant geosorbents comprising soils/sediments, viz. clays, amorphous organic matter and carbonaceous materials, especially at very low environmentally relevant (ppt-ppb) concentrations where carbonaceous geosorbents are hypothesized to control soil-water distribution, (2) determine the differential bioaccessibilities/bioavailabilities of HOCs sorbed to each key geosorbent type using physiologically based extraction fluid, and mammalian models, and (3) test the hypothesis that relationships between HOC sorption by individual geosorbents and subsequent bioaccessibility/bioavailability of these bound HOCs can be extended to predict site-specific toxicity responses to PDD/Fs present in whole soils/sediments.

Project Methods
The geosorbents selected include clay minerals, soil amorphous organic matter and carbonaceous geosorbents. The clay minerals to be examined for HOC sorption will focus on smectites and kaolinite. The smectites will be studied because their large surface areas (~800 m2/g) can be relatively nonpolar , which accounts for the large adsorption capacity of many smectites for NOCs (Boyd et al., 2011) . Adsorption of dibenzo-p-dioxin, a model HOC, by smectites can greatly exceed that by soil organic matter (Liu et al., 2009; Rana et al., 2009), so we will characterize PCDD sorption to a range of smectites for which we already have data using DD (Liu et al., 2009). We include kaolinite because it is very common in soils and a dominant mineral in the ball clays that exhibit dioxin accumulation in the environment (Ferrario and Byrne, 2000; Ferrario et al., 2000). The amorphous organic matter samples will be represented by Pahokee peat soil and Elliott soil humic acid standards obtained from the International Humic Substances Society. A series of CGs will be prepared by pyrolyzing plant materials to biochars, and these CGs will be the primary focus of our work on sorption and bioavailability. To prepare biochars, substrate samples will be rinsed with water, oven dried, then fed into a stainless cylinder reactor that fits inside the furnace of a bench-scale pyrolyzer. The cylinder reactor will be purged with N2 gas to achieve the proper O2 content (< 0.5%), then the reactor and furnace will be purged again with N2 and sealed for pyrolysis under computer control. The resultant biochars will be sieved to obtain the < 0.5 mm fraction. The biochars prepared using this approach will be characterized for elemental (C, O, N) analysis, 13C NMR spectroscopy (Fuertes et al., 2010; Knicker et al., 2008) and Raman (Sadezky et al., 2005) spectroscopy, SEM and TEM analysis, CEC, AEC, zeta potential, and particle-size distribution. To accomplish these objectives, experiments will combine traditional sorption measurements with spectroscopic and theoretical models. Batch equilibrium sorption measurements will be obtained on whole soils and soil constituents using chromatographic and related methods. In addition, in situ spectroscopic techniques will be used to study these sorption processes that include FTIR, ATR-FTIR, diffuse reflectance FTIR, Raman, Raman, surface enhanced Raman, and NMR methods. In addition, some measurements may synchrotron-based light sources, such as the Advanced Photon Source. Other characterization methods that will be used include powder X-ray diffraction (powder XRD), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), controlled humidity gravimetric FTIR analysis, and UV-visible-near infrared spectroscopy.

Progress 10/01/12 to 09/30/17

Outputs
Target Audience:Soil scientists, clay mineralogists and toxicologist. Also chemical industry related to energy sector. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?During this project a number of graduate students and postdocs were trained. We have a close working relationship with Michigan State University and we exchanged students and postdocs for additional training. How have the results been disseminated to communities of interest?We have published a significant number of papers during this project period and have presented these papers and scientific meetings including the American Chemical Society, The Clay Minerals Society, and Soil Science Society of America. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? During this project we have focused on the bioavailability of sorbed contaminants to black carbon. Working with the Center for Integrative Toxicology at Michigan State University, we have carefully prepared black carbon samples containing known amounts of 2,3,7,8 tetrachlorodibenzo-dioxin (TCDD) and used these in mouse exposure study. Unlike our earlier work on clay minerals, TCDD sorbed to black carbon showed little bioavailability. For the first time we have demonstrated reduced bioavailability of dioxins using a geosorbent. This opens the door for using activated carbon to remediate contaminated soils.

Publications

Type: Journal Articles Status: Published Year Published: 2013 Citation: Y. N. Ma, T. R. Filley, C. T. Johnston, S. E. Crow, K. Szlavecz, and M. K. McCormick. The combined controls of land use legacy and earthworm activity on soil organic matter chemistry and particle association during afforestation. Org.Geochem. 58:56-68, 2013.
Type: Journal Articles Status: Published Year Published: 2013 Citation: Reynolds, J. G., Johnston, C. T., and Agnew, S. F. A Molality-Based BET Equation for Modeling the Activity of Water Sorbed on Clay Minerals. Clays and Clay Minerals . 2012 60 (6) 599-609.
Type: Journal Articles Status: Published Year Published: 2013 Citation: C. S. El Mohtar, A. Bobet, M. C. Santagata, V. P. Drnevich, and C. T. Johnston. Liquefaction Mitigation Using Bentonite Suspensions. Journal of Geotechnical and Geoenvironmental Engineering 139 (8):1369-1380, 2013.
Type: Book Chapters Status: Published Year Published: 2013 Citation: Schoonheydt, R. A. and Johnston, C. T. Surface and interface chemistry of clay minerals. In Handbook of Clay Science, 2nd, ed.; Bergaya, F.; Theng, B. K. G.; Lagaly, G. Eds.; Elsevier: Amsterdam, 2013;Chapter 3.1-39
Type: Journal Articles Status: Published Year Published: 2013 Citation: Schoonheydt, R.A. and Johnston, C.T. 2013. Surface and interface chemistry of clay minerals. Chap 5 In Handbook of Clay Science. 2nd Edition, Part A. Fundamentals. Ed. Bergaya, F., Theng, B. K. G., and Lagaly, G. Elsevier, Amsterdam. Pages 139-172
Type: Journal Articles Status: Published Year Published: 2014 Citation: Yeasmin, S., Singh, B., Kookana, R.S., Farrell, M., Sparks, D.L., and Johnston, C.T. 2014. Influence of mineral characteristics on the retention of low molecular weight organic compounds: A batch sorption-desorption and ATR-FTIR study. Journal of Colloid and Interface Science 432, 246-257.
Type: Journal Articles Status: Published Year Published: 2014 Citation: Best, N.B., Hartwig, T., Budka, J.S., Bishop, T.J., Brown, E., Potluri, D.P.V., Cooper, B.R., Premachandra, G.S., Johnston, C.T., and Shulz, B. 2014. Soilless plant growth media influence the efficacy of phytohormones and phytohormone inhibitors. PLOS ONE -accepted June 2014.
Type: Journal Articles Status: Published Year Published: 2014 Citation: Blasioli, S., Martucci, A., Paul, G., Gigli, L., Cossi, M., Johnston, C.T., Marchese, L., and Braschi, I. 2014. Removal of sulfamethoxazole sulfonamide antibiotic from water by high silica zeolites: A study of the involved host-guest interactions by a combined structural, spectroscopic, and computational approach. Journal of Colloid and Interface Science 419, 148-159
Type: Journal Articles Status: Published Year Published: 2014 Citation: Ramos, M.E., Garcia-Palma, S., Rozalen, M., Johnston, C.T., and Huertas, F.J. 2014. Kinetics of montmorillonite dissolution: An experimental study of the effect of oxalate. Chemical Geology 363, 283-292
Type: Journal Articles Status: Published Year Published: 2014 Citation: El Mohtar, C.S., Bobet, A., Drnevich, V.P., Johnston, C.T., and Santagata, M.C. 2014. Pore pressure generation in sand with bentonite: from small strains to liquefaction. Geotechnique 64, 108-117.
Type: Journal Articles Status: Published Year Published: 2015 Citation: Liu, C.; Gu, C.; Yu, K.; Li, H.; Teppen, B. J.; Johnston, C. T.; Boyd, S. A.; Zhou, D. M., Integrating Structural and Thermodynamic Mechanisms for Sorption of PCBs by Montmorillonite. Environmental Science & Technology 2015, 49 (5), 2796-2805.
Type: Journal Articles Status: Accepted Year Published: 2015 Citation: J.A. Greathouse, D.L. Geatches, D.Q. Pike, H.C. Greenwell, C.T. Johnston, J. Wilcox, R T. Cygan. Methylene Blue Adsorption on the Basal Surfaces of Kaolinite: Structure and Thermodynamics from Quantum and Classical Molecular Simulation. Clays and Clay Minerals. (Accepted 13 May 2015)
Type: Journal Articles Status: Published Year Published: 2014 Citation: Santagata, M., Clarke J.P., Bobet, A. Drnevich, V.P., El Mohtar, C.S., Huang, P.T., Johnston, C.T. (2014) Rheology of concentrated bentonite dispersions treated with sodium pyrophosphate for application in mitigating earthquake-induced liquefaction. Applied Clay Science 99, 24-34.
Type: Journal Articles Status: Published Year Published: 2015 Citation: C. Gibsona, T.D. Berry, R. Wang, C.T. Johnston, Y. Jiang, J.A. Bird, T.R. Filley. Weathering of pyrogenic organic matter induces fungal oxidative enzyme response in single culture inoculation experiments. Organic Geochemistry
Type: Journal Articles Status: Published Year Published: 2015 Citation: S. Yeasmin, B. Singh, C.T. Johnston, D.L. Sparks. An evaluation of pre-treatment procedures used for mid infrared spectroscopic study of soil organic matter. Geoderma
Type: Book Chapters Status: Published Year Published: 2016 Citation: Johnston,C.T. Surface chemistry of oil sands clay minerals. Book chapter in "Clay Minerals and Geotechnical Engineering of Tailings" Eds. O. Omotoso and H. Kaminsky.
Type: Book Chapters Status: Published Year Published: 2014 Citation: Hem,S.L. and Johnston,C.T. (2014) Production And Characterization Of Aluminum-Containing Adjuvants, in Vaccine Development and Manufacturing, Eds. P. Wen, E., Ellis, R. and S. Pujar, N.John Wiley & Sons, Inc., Hoboken, NJ, USA. doi: 10.1002/9781118870914.ch11
Type: Journal Articles Status: Published Year Published: 2016 Citation: Ochoa-Cornejo, F., Bobet, A., Johnston, C.T., Santagata, M. and Sinfield, J.V. (2016) Cyclic behavior and pore pressure generation in sands with laponite, a super-plastic nanoparticle. Soil Dynamics and Earthquake Engineering, 88, 265-279.
Type: Journal Articles Status: Published Year Published: 2016 Citation: Singh, B., Fang, Y. and Johnston, C.T. (2016) A fourier-transform infrared study of biochar aging in soils. SOIL SCIENCE SOCIETY OF AMERICA JOURNAL, 80, 613-622.
Type: Journal Articles Status: Published Year Published: 2015 Citation: Greathouse, J.A., Geatches, D.L., Pike, D.Q., Greenwell, H.C., Johnston, C.T., Wilcox, J. and Cygan, R.T. (2015) Methylene blue adsorption on the basal surface of kaolinite: Structure and thermodynamics from quantum and classical molecular simulation. Clays and Clay Minerals, 63, 185-198
Type: Journal Articles Status: Published Year Published: 2016 Citation: Liu, C.H., Chuang, Y.H., Li, H., Teppen, B.J., Boyd, S.A., Gonzalez, J.M., Johnston, C.T., Lehmann, J. and Zhang, W. (2016) Sorption of lincomycin by manure-derived biochars from water. JOURNAL OF ENVIRONMENTAL QUALITY, 45, 519-527.
Type: Journal Articles Status: Published Year Published: 2016 Citation: Gibson, C., Berry, T.D., Wang, R.Z., Spencer, J.A., Johnston, C.T., Jiang, Y., Bird, J.A. and Filley, T.R. (2016) Weathering of pyrogenic organic matter induces fungal oxidative enzyme response in single culture inoculation experiments. Organic Geochemistry, 92, 32-41.
Type: Journal Articles Status: Published Year Published: 2015 Citation: Liu, C., Gu, C., Yu, K., Li, H., Teppen, B.J., Johnston, C.T., Boyd, S.A. and Zhou, D.M. (2015) Integrating structural and thermodynamic mechanisms for sorption of pcbs by montmorillonite. ENVIRONMENTAL SCIENCE & TECHNOLOGY, 49, 2796-2805
Type: Book Chapters Status: Published Year Published: 2015 Citation: Hem, S.L. and Johnston, C.T. (2015) Production and characterization of aluminum containing adjuvants. Pp. 319-346. In E.P. Wen, R. Ellis, and N.S. Pujar, Eds. Vaccine development and manufacturing,John Wiley & Sons Inc, Hoboken.
Type: Journal Articles Status: Published Year Published: 2017 Citation: Ochoa-Cornejo, F., A. Bobet, A. El Howayek, C.T. Johnston, M. Santagata and J.V. Sinfield. 2017. Discussion on: "Laboratory investigation of liquefaction mitigation in silty sand using nanoparticles" Eng.Geol.204:23-32. Engineering Geology 216: 161-164. doi:10.1016/j.enggeo.2016.11.015.
Type: Journal Articles Status: Published Year Published: 2017 Citation: Stedtfeld, R.D., J.B. Sallach, R.B. Crawford, T.M. Stedtfeld, M.R. Williams, H. Waseem, C.T. Johnston, H. Li, B.J. Teppen, N.E. Kaminski, S.A. Boyd, J.M. Tiedje and S.A. Hashsham. 2017. TCDD administered on activated carbon eliminates bioavailability and subsequent shifts to a key murine gut commensal. Appl. Microbiol. Biotechnol. 101: 7409-7415. doi:10.1007/s00253-017-8460-9.
Type: Journal Articles Status: Published Year Published: 2017 Citation: Yeasmin, S., B. Singh, C.T. Johnston and D.L. Sparks. 2017. Evaluation of pre-treatment procedures for improved interpretation of mid infrared spectra of soil organic matter. Geoderma 304: 83-92. doi:10.1016/j.geoderma.2016.04.008.
Type: Journal Articles Status: Published Year Published: 2017 Citation: Boyd, S.A., J.B. Sallach, Y. Zhang, R. Crawford, H. Li, C.T. Johnston, B.J. Teppen and N.E. Kaminski. 2017. Sequestration of TCDD by activated carbon eliminates bioavailability and the suppression of immune function in mice. Environmental Toxicology and Chemistry. doi:10.1002/etc.3815.
Type: Journal Articles Status: Published Year Published: 2017 Citation: J,S. Clemente, Beauchemin, S., MacKinnon, T., Martin, J., Johnston,C.T., Joern, B. (2017) Initial biochar properties related to the removal of As, Se, Pb, Cd, Cu, Ni, and Zn from an acidic suspension. Chemosphere 170, 216-224.
Type: Book Chapters Status: Published Year Published: 2017 Citation: Johnston, C.T. 2017. Infrared Studies of Clay Mineral-Water Interactions. In: W. P. Gates, J. T. Kloprogge, J. Madejova and F. Bergaya, editors, Infrared and Raman Spectroscopies of Clay Minerals. Elsevier Ltd., Amsterdam, Netherlands. p. 288-309.
Type: Journal Articles Status: Published Year Published: 2017 Citation: Yeasmin, S., B. Singh, C.T. Johnston and D.L. Sparks. 2017. Organic carbon characteristics in density fractions of soils with contrasting mineralogies. Geochimica Et Cosmochimica Acta 218: 215-236. doi:10.1016/j.gca.2017.09.007.
Type: Journal Articles Status: Published Year Published: 2017 Citation: Zhang, S., Q.F. Liu, F. Gao, X.G. Li, C. Liu, H. Li, et al. 2017. Mechanism Associated with Kaolinite Intercalation with Urea: Combination of Infrared Spectroscopy and Molecular Dynamics Simulation Studies. Journal of Physical Chemistry C 121: 402-409. doi:10.1021/acs.jpcc.6b10533.
Type: Book Chapters Status: Published Year Published: 2017 Citation: Masek, O. and C.T. Johnston. 2017. Thermal analysis for biochar characterization. In: B. Singh, M. Camps-Arbestain and J. Lehmann, editors, Biochar - A guide to analytical methods. CSIRO Publishing, Clayton South VIC, Australia. p. 283-294.
Type: Book Chapters Status: Published Year Published: 2017 Citation: Johnston, C.T. 2017. Biochar analysis by Fourier transform infrared spectroscopy. In: B. Singh, M. Camps and J. Lehmann, editors, Biochar - A guide to analytical methods. CSIRO Publishing, Clayton South, VIC, Australia. p. 199-213.

Progress 10/01/15 to 09/30/16

Outputs
Target Audience:Our target audience is mainly the scientific community that we reach through our journal publications and presentations at scientific meetings. During this reporting period our research group made presentations at The Clay Minerals Society Annual Meetings and the Soil Science Society of American Annual Meetings Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?All of the research projects require dedicated graduate students to perform the work. Students are learning new research methods and learning how to communicate these results to different audiences and through journal publications. For this project period, we had a Ph.D. level scientist (Dr. Premachandra who manages the laboratory), 3 Ph.D. students and 1 M.Sc. student, and two undergraduates working in the lab. How have the results been disseminated to communities of interest?The results were presented at the Annual Meetings of The Clay Minerals Society in Atlanta in the summer of 2016. What do you plan to do during the next reporting period to accomplish the goals?We are continuing to make progress in this area and will continue our efforts into the coming reporting period.

Impacts
What was accomplished under these goals? This past year we have focused on the bioavailability of sorbed contaminants to black carbon. Working with the Center for Integrative Toxicology at Michigan State University, we have carefully prepared black carbon samples containing known amounts of 2,3,7,8 tetrachlorodibenzo-dioxin (TCDD) and used these in mouse exposure study. Unlike our earlier work on clay minerals, TCDD sorbed to black carbon showed little bioavailability. We are currently studying the sorption mechanisms of TCDD and related contaminants to black carbon.

Publications

Type: Journal Articles Status: Published Year Published: 2016 Citation: Ochoa-Cornejo, F., Bobet, A., Johnston, C.T., Santagata, M. and Sinfield, J.V. (2016) Cyclic behavior and pore pressure generation in sands with laponite, a super-plastic nanoparticle. Soil Dynamics and Earthquake Engineering, 88, 265-279.
Type: Journal Articles Status: Published Year Published: 2016 Citation: Singh, B., Fang, Y. and Johnston, C.T. (2016) A fourier-transform infrared study of biochar aging in soils. SOIL SCIENCE SOCIETY OF AMERICA JOURNAL, 80, 613-622.
Type: Journal Articles Status: Published Year Published: 2015 Citation: Greathouse, J.A., Geatches, D.L., Pike, D.Q., Greenwell, H.C., Johnston, C.T., Wilcox, J. and Cygan, R.T. (2015) Methylene blue adsorption on the basal surface of kaolinite: Structure and thermodynamics from quantum and classical molecular simulation. Clays and Clay Minerals, 63, 185-198.
Type: Journal Articles Status: Published Year Published: 2016 Citation: Liu, C.H., Chuang, Y.H., Li, H., Teppen, B.J., Boyd, S.A., Gonzalez, J.M., Johnston, C.T., Lehmann, J. and Zhang, W. (2016) Sorption of lincomycin by manure-derived biochars from water. JOURNAL OF ENVIRONMENTAL QUALITY, 45, 519-527.
Type: Journal Articles Status: Published Year Published: 2016 Citation: Gibson, C., Berry, T.D., Wang, R.Z., Spencer, J.A., Johnston, C.T., Jiang, Y., Bird, J.A. and Filley, T.R. (2016) Weathering of pyrogenic organic matter induces fungal oxidative enzyme response in single culture inoculation experiments. Organic Geochemistry, 92, 32-41.
Type: Journal Articles Status: Published Year Published: 2015 Citation: Liu, C., Gu, C., Yu, K., Li, H., Teppen, B.J., Johnston, C.T., Boyd, S.A. and Zhou, D.M. (2015) Integrating structural and thermodynamic mechanisms for sorption of pcbs by montmorillonite. ENVIRONMENTAL SCIENCE & TECHNOLOGY, 49, 2796-2805.
Type: Book Chapters Status: Published Year Published: 2015 Citation: Hem, S.L. and Johnston, C.T. (2015) Production and characterization of aluminum containing adjuvants. Pp. 319-346. In E.P. Wen, R. Ellis, and N.S. Pujar, Eds. Vaccine development and manufacturing,John Wiley & Sons Inc, Hoboken.

Progress 10/01/14 to 09/30/15

Outputs
Target Audience:Our target audience is mainly the scientific community that we reach through our journal publications and presentations at scientific meetings. During this reporting period our research group made presentations at The Clay Minerals Society Annual meetings Changes/Problems:No major changes. What opportunities for training and professional development has the project provided?All of the research projects require dedicated graduate students to perform the work. Students are learning new research methods and learning how to communicate these results to different audiences and through journal publications. We currently have a Ph.D. level scientist (Dr. Premachandra who manages the laboratory), 3 Ph.D. students and 1 M.Sc. student, and two undergraduates working in the lab. How have the results been disseminated to communities of interest?Yes, results were presented at a International Biochar conference held in Sydney, Australia in Dec of 2014, a Oilsands Clay Conference held in Calgary in April of 2015, as a Distinguished Lecture given to the University of Albera in May of 2015, and to joint meetings of The Clay Minerals Societry and Euroclay in Edinborough, Scotland in July of 2015. What do you plan to do during the next reporting period to accomplish the goals?We are continuing to make progress in this area and will continue our efforts into the coming reporting period.

Impacts
What was accomplished under these goals? This past year we have continued to develop a better understanding of sorption processes for black carbon, amorphous soil organic matter, and clay minerals. I have particiapted in a 'ring-trial' experiment on biochar characterization with approximately 20 research scientists around the world. At Purdue, we have developed novel methods using thermal and spectroscopic analysis to characterize biochars. We have continued to improve our understanding of the bioavailability of sorbed toxic molecules using a mouse model. These results were presented at the Clay Minerals Society meettings in Edinborough, Scotland. We are working in collaboration with researchers at Michigan State University to investigate how contaminants bind into black carbon

Publications

Type: Journal Articles Status: Published Year Published: 2015 Citation: Liu, C.; Gu, C.; Yu, K.; Li, H.; Teppen, B. J.; Johnston, C. T.; Boyd, S. A.; Zhou, D. M., Integrating Structural and Thermodynamic Mechanisms for Sorption of PCBs by Montmorillonite. Environmental Science & Technology 2015, 49 (5), 2796-2805.
Type: Journal Articles Status: Accepted Year Published: 2015 Citation: J.A. Greathouse, D.L. Geatches, D.Q. Pike, H.C. Greenwell, C.T. Johnston, J. Wilcox, R T. Cygan. Methylene Blue Adsorption on the Basal Surfaces of Kaolinite: Structure and Thermodynamics from Quantum and Classical Molecular Simulation. Clays and Clay Minerals. (Accepted 13 May 2015)
Type: Journal Articles Status: Published Year Published: 2014 Citation: Santagata, M., Clarke J.P., Bobet, A. Drnevich, V.P., El Mohtar, C.S., Huang, P.T., Johnston, C.T. (2014) Rheology of concentrated bentonite dispersions treated with sodium pyrophosphate for application in mitigating earthquake-induced liquefaction. Applied Clay Science 99, 24-34.
Type: Journal Articles Status: Submitted Year Published: 2015 Citation: C. Gibsona, T.D. Berry, R. Wang, C.T. Johnston, Y. Jiang, J.A. Bird, T.R. Filley. Weathering of pyrogenic organic matter induces fungal oxidative enzyme response in single culture inoculation experiments. Organic Geochemistry
Type: Journal Articles Status: Submitted Year Published: 2015 Citation: S. Yeasmin, B. Singh, C.T. Johnston, D.L. Sparks. An evaluation of pre-treatment procedures used for mid infrared spectroscopic study of soil organic matter. Geoderma
Type: Book Chapters Status: Submitted Year Published: 2016 Citation: Johnston,C.T. Surface chemistry of oil sands clay minerals. Book chapter in "Clay Minerals and Geotechnical Engineering of Tailings" Eds. O. Omotoso and H. Kaminsky.
Type: Book Chapters Status: Published Year Published: 2014 Citation: Hem,S.L. and Johnston,C.T. (2014) Production And Characterization Of Aluminum-Containing Adjuvants, in Vaccine Development and Manufacturing, Eds. P. Wen, E., Ellis, R. and S. Pujar, N.John Wiley & Sons, Inc., Hoboken, NJ, USA. doi: 10.1002/9781118870914.ch11

Progress 10/01/13 to 09/30/14

Outputs
Target Audience: Our target audience is mainly the scientific community that we reach through our journal publications and presentations at scientific meetings. During this reporting period our research group made presenations that annual Soil Science Society of America Meetings and The Clay Minerals Society Annual meetings. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? We have a Ph.D. level scientist, three Ph.D. students and two undergraduate students working in this area. How have the results been disseminated to communities of interest? Yes, results were presented at the Soil Science Society Meetings in Tampa, Fl (December of 2013) and The Clay Minerals Society Annual Meetings at Texax A&M in May of 2014. What do you plan to do during the next reporting period to accomplish the goals? We are continuing to make progress in this area and will continue our efforts into the coming reporting period.

Impacts
What was accomplished under these goals? This past year we have continued to develop a better understanding of sorption processes for black carbon, amorphous organic matter, clay minerals and organoclays. These results were presented at two national conferences (Soil Science Society of America, and the Clay Minerals Society). We are working in collaboration with researchers at Michigan State University to investigate how contaminants bind into black carbon.

Publications

Type: Journal Articles Status: Published Year Published: 2013 Citation: Schoonheydt, R.A. and Johnston, C.T. 2013. Surface and interface chemistry of clay minerals. Chap 5 In Handbook of Clay Science. 2nd Edition, Part A. Fundamentals. Ed. Bergaya, F., Theng, B. K. G., and Lagaly, G. Elsevier, Amsterdam. Pages 139-172.
Type: Journal Articles Status: Published Year Published: 2014 Citation: Yeasmin, S., Singh, B., Kookana, R.S., Farrell, M., Sparks, D.L., and Johnston, C.T. 2014. Influence of mineral characteristics on the retention of low molecular weight organic compounds: A batch sorption-desorption and ATR-FTIR study. Journal of Colloid and Interface Science 432, 246-257.
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Best, N.B., Hartwig, T., Budka, J.S., Bishop, T.J., Brown, E., Potluri, D.P.V., Cooper, B.R., Premachandra, G.S., Johnston, C.T., and Shulz, B. 2014. Soilless plant growth media influence the efficacy of phytohormones and phytohormone inhibitors. PLOS ONE -accepted June 2014.
Type: Journal Articles Status: Published Year Published: 2014 Citation: Blasioli, S., Martucci, A., Paul, G., Gigli, L., Cossi, M., Johnston, C.T., Marchese, L., and Braschi, I. 2014. Removal of sulfamethoxazole sulfonamide antibiotic from water by high silica zeolites: A study of the involved host-guest interactions by a combined structural, spectroscopic, and computational approach. Journal of Colloid and Interface Science 419, 148-159.
Type: Journal Articles Status: Published Year Published: 2014 Citation: Ramos, M.E., Garcia-Palma, S., Rozalen, M., Johnston, C.T., and Huertas, F.J. 2014. Kinetics of montmorillonite dissolution: An experimental study of the effect of oxalate. Chemical Geology 363, 283-292.
Type: Journal Articles Status: Published Year Published: 2014 Citation: El Mohtar, C.S., Bobet, A., Drnevich, V.P., Johnston, C.T., and Santagata, M.C. 2014. Pore pressure generation in sand with bentonite: from small strains to liquefaction. Geotechnique 64, 108-117.

Progress 10/01/12 to 09/30/13

Outputs
Target Audience: Our primary target audience is the scientific community where research is disseminated through publications in peer review journal articles and scientific meetings. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? We have three Ph.D. students working on different aspects of organic solute / black carbon interactions. How have the results been disseminated to communities of interest? Yes, These results were presented at three national conferences (American Chemical Society, Soil Science Society of America, and the Clay Minerals Society). What do you plan to do during the next reporting period to accomplish the goals? We are continuing to study these interactions. At present, we are very interested in biochar and its physiochemical properties.

Impacts
What was accomplished under these goals? This past year we have made progress in our understanding of sorption processes on contrasting geosorbents. These results were presented at threenational conferences (American Chemical Society, Soil Science Society of America, and the Clay Minerals Society). We been studying sorption of nonpolar solutes on clay minerals, modified clay minerals (organoclays), amorphous organic matter and black carbon. Sorption processes on black carbon, in particular, are complex related to the aqueous solubility of the solute.We are also finding that naturally occurring black carbon in soils may be both a sink and a source of highly toxic organic solutes, including PCDDs and PCDFs.

Publications

Type: Journal Articles Status: Published Year Published: 2013 Citation: Y. N. Ma, T. R. Filley, C. T. Johnston, S. E. Crow, K. Szlavecz, and M. K. McCormick. The combined controls of land use legacy and earthworm activity on soil organic matter chemistry and particle association during afforestation. Org.Geochem. 58:56-68, 2013.
Type: Journal Articles Status: Published Year Published: 2013 Citation: Reynolds, J. G., Johnston, C. T., and Agnew, S. F. A Molality-Based BET Equation for Modeling the Activity of Water Sorbed on Clay Minerals. Clays and Clay Minerals . 2012 60 (6) 599-609.
Type: Journal Articles Status: Published Year Published: 2013 Citation: C. S. El Mohtar, A. Bobet, M. C. Santagata, V. P. Drnevich, and C. T. Johnston. Liquefaction Mitigation Using Bentonite Suspensions. Journal of Geotechnical and Geoenvironmental Engineering 139 (8):1369-1380, 2013.
Type: Book Chapters Status: Published Year Published: 2013 Citation: Schoonheydt, R. A. and Johnston, C. T. Surface and interface chemistry of clay minerals. In Handbook of Clay Science, 2nd, ed.; Bergaya, F.; Theng, B. K. G.; Lagaly, G. Eds.; Elsevier: Amsterdam, 2013;Chapter 3.1-39

Progress 10/01/11 to 09/30/12

Outputs
OUTPUTS: An invited paper was presented at the 49th annual meetings of The Clay Minerals Society Meetings held in Golden, CO in July 7-11, 2012 entitled "Spectroscopic, molecular dynamics and sorption studies of PCDDs and PAHs interactions with four contrasting geosorbents" coauthored by colleagues at Michigan State University (Boyd, Teppen, Li, Liu), EPA (Barth), and Tetra Tech Inc. (Chattopadhyay). In addition, I was invited to present a summary of my final project "Baseline characterization of oil sands clay minerals" to the Bitumen Production Fundamental Research Group (BPFRG) of the Canadian Oil Sands Network for Research and Development (CONRAD) in 16 Sept 2012 in Edmonton, Alberta. During this trip to Canada, I also visited and presented my research to Shell and Total in Calgary, Alberta. I was an invited keynote speaker at a student-led First Annual Ecological Sciences and Engineering (ESE) Keystone Series held on January 25th 2012 where I presented an overview of the issues in the Athabasca Oil Sands. I was also an invited speaker to the Purdue Geotechnical Society Workshop held on April 13, 2012 where I presented a talk titled "Understanding clays in oil sands processes. How the clay particle beat the 100,000 ton per hour process". PARTICIPANTS: Kiran Rana, Ph.D. Student, working on dioxins (funded by NIEHS and USDA). Bushra Khan, Postdoctoral Research Associate, working on dioxins (NIEHS and USDA). Kamol Das, Ph.D. Student, working on dioxin (NIEHS and USDA). Dr. G. Premachandra, assists with all laboratory work. Visiting Scholar. Beatriz Gamiz, Ph.D. Student, working on the interaction of herbicides with naturally occurring organoclays. (University of Sevilla, Spain). Continue to collaborate with Profs. Brian Teppen, Hui Li, Stephen A. Boyd, and Tom Pinnavaia at Mich. State University. Collaborate with Prof. Tim Filley in Earth and Atmospheric Sciences at Purdue on a NSF Funded project on earthworms / carbon stability. Collaborate with Antonia Bobet, Marika Santagata and Joe Sinfield on a NSF funded project looking at clay minerals and soil liquefaction. Collaborate with Patricia Maurice at the Univ. of Notre Dame on siderophores. Collaborate with David Bish at Indiana Unviversity on the surface chemistry of clay minerals. TARGET AUDIENCES: Soil scientists, clay mineralogists and toxicologist. Also chemical industry related to the Athabasca Oil Sands and the Department on Energy on storage of nuclear waste. PROJECT MODIFICATIONS: No major changes to report

Impacts
Our collective research is providing new insight about how organic pollutants are attenuated by different soil constituents. In particular, we have shown that clay minerals exchanged with weakly hydrated cations have a higher-than-expected affinity for planar hydrophobic contaminants such as dioxins. Although bound to the clay surface, related research in our group has shown that these toxic chemicals still have high bioavailability.

Publications

Johnston, C.T., Premachandra, G.S., Szabo, T., Lok, J., and Schoonheydt, R.A. (2012) Interaction of Biological Molecules with Clay Minerals: A Combined Spectroscopic and Sorption Study of Lysozyme on Saponite. Langmuir 28, 611-619.
Liu, C., Li, H., Johnston, C.T., Boyd, S.A., and Teppen, B.J. (2012) Relating Clay Structural Factors to Dioxin Adsorption by Smectites: Molecular Dynamics Simulations. Soil Science Society of America Journal 76, 110-120.
Johnston, C.T., Khan, B., Barth, E.F., Chattopadhyay, S., and Boyd, S.A. (2012) Nature of the Interlayer Environment in an Organoclay Optimized for the Sequestration of Dibenzo-p-dioxin. Environmental Science & Technology 46, 9584-9591.
Gamiz, B., Celis, R., Hermosin, M.C., Cornejo, J., and Johnston, C.T. (2012) Preparation and characterization of spermine-exchanged montmorillonite and interaction with the herbicide fluometuron. Applied Clay Science 58, 8-15.
Favaretto, N., Norton, L.D., Johnston, C.T., Bigham, J., and Sperrin, M. (2012) Nitrogen and Phosphorus Leaching as Affected by Gypsum Amendment and Exchangeable Calcium and Magnesium. Soil Science Society of America Journal 76, 575-585.

Progress 10/01/10 to 09/30/11

Outputs
OUTPUTS: An invited keynote paper was given at for the annual meeting of The Mineralogical Society of Korea on 26 May 2011 entitled "Probing the nanoscale architecture of clay mineralRole of Clay Minerals" in Jinju, Korea. I also presented a Departmental Seminar to the Division of Environmental and Ecological Engineering at Korea University (Seoul, Korea)entitled "Controlling the Fate of Exceptionally Toxic Organic Contaminants in the Environment" on 24 May 2011. On this trip I also visited Japan and gave two invited seminars. The first was given at the University of Tokyo on 30 May 2011 entitled "Role of clay minerals in controlling the fate of radioactive 134,137Cs in soils". Several news agencies were present and I was interviewed by Tokyo Broadcasting Corporation after this seminar. The second talk was given at the National Institute of Materials Science in Tskuba, Japan on 31 May 2011. In August 2011, I was invited to give an invited talk at the Bouyoucus Confernece held in Estes Park, CO entitled "Surface chemistry and biophysics of microbial attachment and protection mechanisms during airborne transport of microbes". This talk was co-authored by Prof. James Tiedje at Michigan State University. In September 24-29 of 2011, I presented two oral presentations and one poster presentation at the Annual Meetings of The Clay Minerals Society held in Lake Tahoe, NV. The first talk was titled "Suppresion of humoral immune responses by 2,3,7,8-tetrachlorodibenzo-p-dioxin intercalated in smectite clay". The second oral presentation was titled "Synthesis and characterization of an organoclay geosorbent for the removal of hydrophobic organic contaminants". PARTICIPANTS: Kiran Rana, Ph.D. Student, working on dioxins (funded by NIEHS and USDA). Bushra Khan, Postdoctoral Research Associate, working on dioxins (NIEHS and USDA). Kamol Das, Ph.D. Student, working on dioxin (NIEHS and USDA). Dr. G. Premachandra, assists with all laboratory work. Elaine Mihelc, postbaccalaureate, working the chemistry of aluminum (DOE). Visiting Scholar. Beatriz Gamiz, Ph.D. Student, working on the interaction of herbicides with naturally occurring organoclays. (University of Sevilla, Spain) Sept-Nov, 2011, Visiting Scholar Carlo Fellet from the University of Bologna, Italy (Feb-April of 2011) looking at pesticide interactions with clay minerals. Continue to collaborate with Profs. Brian Teppen, Hui Li, Stephen A. Boyd, and Tom Pinnavaia at Mich. State University. Collaborate with Prof. Tim Filley in Earth and Atmospheric Sciences at Purdue on a NSF Funded project on earthworms / carbon stability. Collaborate with Antonia Bobet, Marika Santagata and Joe Sinfield on a NSF funded project looking at clay minerals and soil liquefaction. Collaborate with Patricia Maurice at the Univ. of Notre Dame on siderophores. Collaborate with David Bish at Indiana Unviversity on the surface chemistry of clay minerals. TARGET AUDIENCES: Soil scientists, clay mineralogists and toxicologits. Also chemical industry related to the Athabasca Oilsands and the Deparment on Energy on storage of nuclear waste. PROJECT MODIFICATIONS: No major changes to report

Impacts
We recently reported on the bioavailability of dioxins bound to clay minerals:Boyd, S.A., Johnston, C.T., Pinnavaia, T.J., Kaminski, N.E., Teppen, B.J., Li, H., Khan, B., Crawford, R.B., Kovalova, N., Kim, S-S., Shao, H., Gu, C., and Kaplan, B. L.F. Suppression of Humoral Immune Responses by 2,3,7,8-Tetrachlorodibenzo-p-Dioxin Intercalated in Smectite Clay. Environmental Toxicology and Chemistry 30(12), 2748-2755 (2011). Chlorinated dioxins are among the most toxic chemicals known to man. It has been assumed that when these types of compounds are bound to soil particles, their bioavailability is reduced. We observed that this is not the case for the geosorbents we tested. The most toxic dioxin congener is 2,3,7,8-TCDD. When bound to clay particles, it had the same bioavailability as when delivered to mice in corn oil. This result has potentially important implications in establishing 'safe' concentrations in soils.

Publications

Schoonheydt, R.A. and Johnston, C.T. 2011. The Surface Properties of Clay Minerals. Chapter 10 in Layered Mineral Structures and their Application in Advanced Technologies. M.F. Brigatti and A. Mottana (eds.) European Mineralogical Union and the Mineralogical Society of Great Britain & Ireland. p. 335-370.
Bobet, A., Hwang, J., Johnston, C.T., et al. One-dimensional consolidation behavior of cement-treated organic soil. Canadian Geotechnical Journal, 48(7), 1100-1115 (2011).
Gu, C., Liu, C., Ding, Y.J., Li, H., Teppen, B.J., Johnston, C.T., and Boyd, S.A. Clay Mediated Route to Natural Formation of Polychlorodibenzo-p-dioxins. Environmental Science & Technology 45, 3445-3451 (2011).
C. Liu, H. Li, C.T. Johnston, S.A. Boyd, B.J. Teppen. Relation of Clay Structural Factors to Dioxin Adsorption by Smectites: Empirical Evidence and Molecular Dynamics Simulations. Soil Science Society of America Journal 76, (In press, posted online)(2011).
Gu, C., Liu, C., Johnston, C.T., Teppen, B.J., Li, H., and Boyd, S.A. Pentachlorophenol Radical Cations Generated on Fe(III)-Montmorillonite Initiate Octachlorodibenzo-p-dioxin Formation in Clays: Density Functional Theory and Fourier Transform Infrared Studies. Environmental Science & Technology 45, 1399-1406 (2011).
Jia, H.Z., Gu, C., Boyd, S.A., Teppen, B.J., Johnston, C.T., Song, C.Y., and Li, H. Comparison of Reactivity of Nanoscaled Zero-Valent Iron Formed on Clay Surfaces. Soil Science Society of America Journal 75, 357-364 (2011).
Boyd, S.A., Johnston, C.T., Pinnavaia, T.J., Kaminski, N.E., Teppen, B.J., Li, H., Khan, B., Crawford, R.B., Kovalova, N., Kim, S-S., Shao, H., Gu, C., and Kaplan, B. L.F. Suppression of Humoral Immune Responses by 2,3,7,8-Tetrachlorodibenzo-p-Dioxin Intercalated in Smectite Clay. Environmental Toxicology and Chemistry 30(12), 2748-2755 (2011).
Jia, H.Z., Gu, C., Boyd, S.A., Teppen, B.J., Johnston, C.T., Song, C.Y., and Li, H. Comparison of Reactivity of Nanoscaled Zero-Valent Iron Formed on Clay Surfaces. Soil Science Society of America Journal 75, 357-364 (2011).
Boyd, S., Johnston, C.T., Laird, D.A., Teppen, B.J., Li, H. 2011. Comprehensive Study of Organic Contaminant Adsorption by Clays: Methodologies, Mechanisms, and Environmental Implications. Chapter 2 in Biophysico-Chemical Processes of Anthropogenic Organic Compounds in Environmental Systems. B. Xing, N. Senesi and P.M. Huang (eds.) John Wiley & Sons, Inc. p.51-71.

Progress 10/01/09 to 09/30/10

Outputs
OUTPUTS: An invited keynote paper was given at the 19th World Congress of Soil Science in Brisbane, Australia (August 2010) entitled "Role of Clay Minerals in Controlling the Fate of Exceptionally Toxic Organic Contaminants in the Environment". Also presented an invited paper at the Australia Clay Minerals Society Meeting entitled "Interaction of proteins on clay surfaces" (Brisbane, Australia, August, 2010). I was invited to Michican State Univeristy to present a departmental seminar (Crop and Soil Science) entitled "Probing the nanoscale architecture of clay minerals". I presented a poster at the Department of Energy Waste Managmenet Technical Exchange Conference in Atlanta, GA (Nov 2010) entitled "Role of Aluminum Dimer in the Aluminum Solubility for Hanford Wastes". A posted was presented at the 89th Congress of the Societa Italiana di Mineralogia e Petrologia entitled "Introductive study on the interactions of hydrohcloride tetracycline with expandable clay minerals" by L. Gigli, G. Premachandra and C.T. Johnston. We will present next month at the American Geophysical Union Conference in San Fransisco a paper entitled "Teasing Apart the Influence of Past Land Use and Current Invertebrate Processes on the Controls of Soil Organic Matter Stabilization in Eastern Deciduous Forests, USA" by Y. Ma, T.R. Filley, C.T. Johnston, K. Szlavecz, M. McMcormick, C. Thayer and J. Jourdain. PARTICIPANTS: Kiran Rana, Ph.D. Student, working on dioxins (funded by NIEHS and USDA). Bushra Khan, Postdoctoral Research Associate, working on dioxins (NIEHS and USDA). Kamol Das, Ph.D. Student, working on dioxin (NIEHS and USDA). Dr. G. Premachandra, assists with all laboratory work. Elaine Mihelc, postbaccalaureate, working the chemistry of aluminum (DOE). Sonia Blasioli,Postdoctoral Research Associate,working on the interaction of antibiotics with clay minerals.(University of Bologna, Italy) Visiting Scholar. Beatriz Gamiz, Ph.D. Student, working on the interaction of herbicides with naturally occurring organoclays. (University of Sevilla, Spain) Visiting Scholar. Elena Ramos, Ph.D. Student, working on the solubility of ingested clay minerals (University of Granda, Spain) Visiting Scholar. Lara Gigli, Ph.D. Student, working on the interaction of antibiotics with clay minerals (University of Bologna, Italy) Visiting Scholar. Continue to collaborate with Profs. Brian Teppen, Hui Li, Stephen A. Boyd, and Tom Pinnavaia at Mich. State University. Collaborate with Prof. Tim Filley in Earth and Atmospheric Sciences at Purdue on a NSF Funded project on earthworms / carbon stability. Collaborate with Antonia Bobet, Marika Santagata and Joe Sinfield on a NSF funded project looking at clay minerals and soil liquefaction. Collaborate with Patricia Maurice at the Univ. of Notre Dame on siderophores. Collaborate with David Bish at Indiana Unviversity on the surface chemistry of clay minerals. TARGET AUDIENCES: Soil scientists, clay mineralogists and toxicologits. Also chemical industry related to the Athabasca Oilsands and the Deparment on Energy on storage of nuclear waste. PROJECT MODIFICATIONS: No major changes to report.

Impacts
Our work on the environmental fate of dioxins and their interaction with environmental particles has taken several new turns. The first is focused on the bioavailability of sorbed dioxins to animals. We are working with the Center of Integrative Toxicology at Michigan State University and have found that sorbed dioxins appear to be highly available to mice through orgal gevage. In addition, we have found that dioxins can form on clay minerals in the presence of iron and this may have implications for the dioxin budget in soils. We are now working with the leading laboratory on dioxins in the EPA to assess dioxin availability in a broad range of geosorbents. We have gained new insight into the chemistry of aluminum that may impact how high level nuclear waste is processed in a project funded by the Department of Energy.

Publications

Jia, H., Gu, C., Boyd, S.A., Teppen, B.J., Johnston, C.T., Song, C., Li, H. Comparison of Reactivity of Nanoscaled Zero-Valent Iron Formed on Clay Surfaces. Soil Science Society of America Journal, 75, (In press, posted online)(2011).
Kang, D.H., Schwab, A.P., Johnston, C.T., and Banks, M.K. Adsorption of iron cyanide complexes onto clay minerals, manganese oxide, and soil. Journal of Environmental Science and Health Part A-Toxic/Hazardous Substances & Environmental Engineering 45, 1391-1396 (2010).
Chen, W.R., Ding, Y.J., Johnston, C.T., Teppen, B.J., Boyd, S.A., and Li, H. Reaction of Lincosamide Antibiotics with Manganese Oxide in Aqueous Solution. Environmental Science & Technology 44, 4486-4492 (2010).
Johnston, C.T. Probing the nanoscale architecture of clay minerals. Clay Minerals 45, 245-279 (2010).
Kogure, T., Elzea-Kogel, J., Johnston, C.T., and Bish, D.L. Stacking Disorder in A Sedimentary Kaolinite. Clays and Clay Minerals 58, 62-71. (2010)

Progress 10/01/08 to 09/30/09

Outputs
OUTPUTS: A series of talks were given at the 46th Annual Meetings of the Clay Minerals Society, June 5-11, 2009, in Billings Montana. These talks included the following (titles of the papers in CAPS): NANO CONFINED WATER IN CLAY MINERALS Marika Santagata, Gnasiri Premachandra and Cliff T. Johnston SODIUM PYROPHOSPHATE - BENTONITE SUSPENSIONS FOR USE IN LIQUEFACTION MITIGATION Julia P. Clarke, A. Bobet, V.P. Drnevich, Chadi El Mohtar, Cliff T. Johnston and Marika Santagata A COMPREHENSIVE ANALYSIS OF ORGANIC CONTAMINANT ADSORPTION BY CLAYS Stephen A. Boyd, Cliff T. Johnston, David A. Laird, Brian J. Teppen and Hui Li PROBING THE MICROSCOPIC HYDROPHOBICITY OF SMECTITE SURFACES Cliff. T. Johnston, Kiran Rana, Stephen A. Boyd, Brian J. Teppen and Thomas J. Pinnavaia. In addition, the following talks were given at the XIV International Clay Conference in Castellaneta Marina (TA) Italy in June 14-20, 2009. Cliff t. Johnston*, Robert A. Schoonheydt, Gnanasiri S. Premachandra, Tamas Szabo LYSOZYME SORPTION ON SMECTITE Julia P. Clarke, Antonio Bobet, Vincent P. Drnevich, Chadi El Mohtar, Cliff T. Johnston, Marika Santagata* SODIUM PYROPHOSPHATE - BENTONITE SUSPENSIONS FOR USE IN LIQUEFACTION MITIGATION M. Elena Ramos*, Cliff T. Johnston, F. Javier Huertas SPECTROSCOPIC STUDY OF ORGANIC LIGANDS ADSORPTION ON MONTMORILLONITE. The following presentation was one of five plenary session talks given to an international conference of approximately 1000 people. Cliff T. Johnston Purdue University - USA Role of Clay Minerals in Controlling the Fate of Dioxins in the Environment Marika Santagata*, Gnasiri Premachnadra, Cliff T. Johnston NANO CONFINED WATER IN CLAY MINERALS In addition, the following invited talk was given at the 19th Annual Goldschmidt Conference in Davos, Switzerland on June 21, 2009 Maurice, P.A., Haack, E.A., Quicksall, A.N., Hunter, E., and Johnston, C.T. (2009) Sorption of Pb and desferrioxamine to montmorillonite. Geochimica et Cosmochimica Acta 73, A851-A851. PARTICIPANTS: We continue to work closely with Stephen A. Boyd, Brian J. Teppen, Hui Li, and Thomas Pinnavaia at Michigan State University. Boyd, Teppen, Li are in the Crop and Soil Science Departemnt; Pinnavaia is in Chemistry. We also collaborate with David Laird at National Soil Tilth Laboratory in Iowa. On siderophores, we are working with Patricia Maurice at the University of Notre Dame. On structural disorder in clay minerals, we are working David L. Bish and Haydn Murray in the Department of Geological Sciences at Indiana University, Bloomington, IN and with Prof. Toshiro Kogure at the Univeristy of Tokyo, Japan. We have an active collaboration with the Department of Civil Engineering at Purdue University with Prof. Marika Santagata, Antonio Bobet, Joe Sinfield and Vince Drenivich. Partner organizations include Michigan State University Departments of Soil and Crop Science and Chemistry, the University of Notre Dame Department of Geoscience and Civil Engineering, the National Soil Tilth Lab, Indiana University Department of Geology, Purdue University Department of Civil Engineering, University of Tokyo Department of Geoscience, Katholieke University in Leuven, Belgium, TARGET AUDIENCES: Soil scientist and toxicologists PROJECT MODIFICATIONS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Our main target audience continues to be getting quality publications out into the relevant scientific literature. I note that we have 21 jointly co-authored publications with Michigan State University and these are highly cited papers. We have strong records of publication with the Katholieke University of Leuven, Belgim and with Indiana University in Bloomington, IN. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Working with my colleagues at Michigan State University (Boyd, Teppen, Li) we have made progress in developing our understanding about how pesticides and pollutants bind to soil constituents. We have shown that clay minerals play a more significant role in regulating the fate and transport of a diverse group of chemicals than previously thought. Much of our work in the past focused on more polar organics. In collaboration with researchers at Michigan State University, we are applying these concepts to the study of nonpolar organic solutes that include dioxins, polychlorinated biphenyls, and polyaromatic hydrocarbons. To test these ideas further we are now investigating the bioavailability of sorbed toxic compounds in animal studies working the Center of Integrative Toxicology at MSU. We are continuing to work with researchers at the University of Notre Dame looking at how microbially produced siderophores interact with mineral surfaces in soils. These naturally produced compounds have very high affinities for clay surfaces and enhance their dissolution. We are also investigating how natural soil organic matter binds to mineral surfaces. Working in collaboration with Prof. Tim Filley in the Earth and Atmospheric Sciences Department at Purdue we are studing the chemical alteration trajector of forest litter as impacted by invasive earthworms. In addition, we have have developed a spectroscopic method to study structural disorder in clay minerals.

Publications

Liu, C.; H. Li, B.J. Teppen, C. T. Johnston, and S. A. Boyd. Mechanisms Associated with the High Adsorption of Dibenzo-p-dioxin from Water by Smectite Clays. Environ. Sci.& Technol. 43 (8): 2777- 2783 (2009)
K. Rana, S. A. Boyd, B. J. Teppen, H. Li, C. Liu, and C. T. Johnston. Probing the microscopic hydrophobicity of smectite surfaces. A vibrational spectroscopic study of dibenzo-p-dioxin sorption to smectite. Physical Chemistry Chemical Physics, 11 (15): 2976-2985 (2009).
Boyd, S. A.; Johnston, C. T.; Laird, D. A.; Teppen, B. J., Li, H., Comprehensive study of organic contaminant adsorption by clays: methodologies, mechanisms and environmental implications. IUPAC Series In Press 2010
Szabo,T.; R. Mitea, H. Leeman, G.S. Premachandra, C.T. Johnston, M. Szekeres; I. Dekany, R.A. Schoonheydt. Adsorption of protoamine and papain proteins on saponite. Clays and Clay Minerals 56(5): 494-504 (2008)

Progress 10/01/07 to 09/30/08

Outputs
OUTPUTS: Identify the chemical mechanisms that govern the sorption, biotic- and abiotic degradation transformation of organic contaminants in soils. Compounds of interest are pesticides, mycotoxins, pharmaceuticals, polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and dioxins and include water, nutrients, metals, and oxyanions. Our goal is to determine how these types of compounds will interact with soils and soil constituents and to help develop predictive transport models. We are developing new experimental approaches to study the chemistry and reactivity of the soil-water interface. Also we are studying chemical and biological processes occurring in the rhizosphere. For example, we are interested in the biogeochemical changes induced by seasonal flooding. In addition, we are interested in studying how organic acids and siderophores impact soil chemistry and such processes as Fe- and Al-availability/toxicity in plants. Coupled biological and chemical measurements will be conducted using a recently constructed soil biogeochemical reactor. PARTICIPANTS: We continue to work closely with Stephen A. Boyd, Brian J. Teppen, Hui Li, and Thomas Pinnavaia at Michigan State University. Boyd, Teppen, Li are in the Crop and Soil Science Departemnt; Pinnavaia is in Chemistry. We also collaborate with David Laird at National Soil Tilth Laboratory in Iowa. On siderophores, we are working with Patricia Maurice at the University of Notre Dame. On structural disorder in clay minerals, we are working David L. Bish and Haydn Murray in the Department of Geological Sciences at Indiana University, Bloomington, IN and with Prof. Toshiro Kogure at the Univeristy of Tokyo, Japan. TARGET AUDIENCES: Soil scientist and toxicologists PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
During the past year we have continued to make progress in our understanding about how pesticides and related chemicals bind to soil constituents. We are developing a solid molecular understanding about the structure and reactivity of clay minerals and their role in regulating the fate and transport of a diverse group of chemicals. Much of our work in the past focused on more polar organics. In collaboration with researchers at Michigan State University, we are applying these concepts to the study of nonpolar organic solutes that include dioxins, polychlorinated biphenyls, and polyaromatic hydrocarbons. In addition, we are now working with researchers at the University of Notre Dame looking at how microbially produced siderophores interact with mineral surfaces in soils. These naturally produced compounds have very high affinities for clay surfaces and enhance their dissolution. We are also investigating how natural soil organic matter binds to mineral surfaces. Working in collaboration with Prof. Tim Filley in the Earth and Atmospheric Sciences Department at Purdue we are studing the chemical alteration trajector of forest litter as impacted by invasive earthworms. In addition, we have have developed a spectroscopic method to study structural disorder in clay minerals.

Publications

C.T. Johnston, J. Elzea-Kogel, D.L. Bish and H.H. Murray. 2008. Low temperature FTIR study of structural disorder in kaolin group minerals. Clays and Clay Minerals. 56 (4): 470-485.
E.A. Haack, C.T. Johnston, and P.A. Maurice. 2008. Mechanisms of hydroxamic acid siderophore sorption to homoionic smectite and siderophore-enhanced release of structural Fe3+. Geochimica et Cosmochimica Acta. 72 (14): 3381-3397
T. R. Pereira, D.A. Laird, M. L. Thompson, C. T. Johnston, B. J. Teppen, H. Li, and S.A. 2008. Boyd. Role of smectite quasicrystal dynamics in adsorption of dinitrophenol. Soil Sci.Soc.Am.J. 72 (2):347-354
T.R. Filley, McCormick, M.K., Crow, S.E.; Szlavecz, K.; Whigham, D.F.; Johnston, C.T.; van den Heuvel, R.N. 2008. Comparison of the chemical alteration trajectory of liriodendron tulipifera litter among forests with different invasive earthworm activity. J. Geophysical Research Biogeosciences. 113, G01027
S. A. Goldberg, C.T. Johnston, D.L. Suarez, S.M. Lesch. 2008. Mechanisms of molybdenum adsorption on soil minerals evaluated using vibrational spectroscopy and surface complexation modeling. Chapter 9 in Adsorption of Metals by Geomedia II. M.O. Barnett and D.B. Kent (eds.) Elsevier book series "Developments in Earth and Environmental Sciences 7". p. 235-266 2008.
T. R. Pereira, D.A. Laird, C. T. Johnston, B. J. Teppen, H. Li, and S.A. Boyd. 2007. Mechanism of dinitrophenol Herbicide Sorption on Smectites in Aqueous Suspensions at varying pH. Soil Science Society of America Journal. 71(5): 1476-1481
J. R. Schoonover, W. P. Steckle, Jr., C. T. Johnston, Y. Wang, A. M. Gillikin, and R.A. Palmer. 2007. Humidity-Dependent Dynamic Infrared Linear Dichroism Study of a Poly(Ester Urethane) Spectrochimica Acta Part A. Vol 67 (1) 208-213.
S.L. Hem, C.T. Johnston, H. Hogenesch. 2007. Imject Alum is not an alternative to aluminum hydroxide adjuvant or aluminum phosphate adjuvant. 25 (27): 4985-4986.
I.W. Wait, C.T. Johnston, E.R. Blatchley. 2007. The influence of oxidation reduction potential and water treatment processes on quartz lamp sleeve fouling in ultraviolet disinfection reactors. Water Research 2007 41(11):2427-2436.

Progress 10/01/06 to 09/30/07

Outputs
OUTPUTS: During the past year we have continued to develop a successful collaboration with researchers at Michigan State University (B.Teppen, S.A. Boyd, H. Li), the National Soil Tilth Lab (David Laird, USDA-ARS Ames, Iowa), the National Soil Erosion Lab (Darrell Norton, USDA-ARS in West Lafayette, IN), the National Soil Salinity Laboratory (Sabine Goldberg, USDA-ARS Riverside, CA) in studying how pesticides and related contaminants interact with soil constituents. Our overall goal is to develop an improved understanding about the molecular level processes that govern how anthropogenic compounds interact in soils with an emphasis on the role of soil minerals. In the last year, we have examined the binding mechanisms for the following compounds with soil minerals: dibenzo-p-dioxin, polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), glyphosate, nitroaromatic compounds, phosphate and molybdate. TARGET AUDIENCES: Soil scientists and regulatory officials.

Impacts
Our collaborative research is providing new information about the role of soil minerals in binding semi-polar and non-polar organic compounds in soil. Originally, the role of soil minerals was presumed to play a negligible role in binding these types of compounds because mineral surfaces were known to be hydrophilic. However, our research has proven that a growing list of compounds, even very non-polar compounds such as dibenzo-p-dioxin, can bind significantly to soil minerals. This research will help to develop predictive models for the fate and transport of non-polar and semi-polar compounds in soils.

Publications

H. Li, T.R. Pereira, B. J. Teppen, D.A. Laird, C.T. Johnston, and S.A. Boyd. 2007. Ionic strength-induced formation of Smectite Quasicrystals Change Upon Sorption of Nitroaromatic Compounds. Environmental Science and Technology 41(4): 1251-1256.
R.H.A. Ras, C.T. Johnston, R.A. Schoonheydt. 2007. Relation between s-polarized and p-polarized internal reflection spectra: Application for the spectral resolution of perpendicular vibrational modes. J. Phys. Chem. A, 111 (36) 8787-8791.
T. Szabo, M. Szekeres, I. Dekany, C. Jackers, S. De Feyter, C.T. Johnston, and R.A. Schoonheydt. 2007. Layer-by-layer construction of ultrathin hybrid films with proteins and clay minerals. J. Phys. Chem. C 111, 12730-12740.
R.H.A. Ras, Y. Umemura, C.T. Johnston, A. Yamagishi and R.A. Schoonheydt. Ultrathin Hybrid Films of Clay Minerals. 2007. Invited Review. Physical Chemistry Chemical Physics 9(8): 918-932.

Progress 10/01/05 to 09/30/06

Outputs
For the past seven years we have developed a successful collaboration with researchers at Michigan State University (B.Teppen, S.A. Boyd, H. Li) and the National Soil Tilth Lab (David Laird, USDA-ARS Ames, Iowa) in studying how pesticides and related chemicals interact with soil constituents. Our overall goal is to develop an improved understanding about the molecular level processes that govern how anthropogenic organic compounds interact in soils with an emphasis on the role of soil minerals. We have developed a coupled experimental-theoretical approach that combines modern spectroscopic methods with computational quantum chemical methods and traditional sorption methods. Initially, our work focused on nitroaromatic pesticides (e.g., DNOC, DINSOSEB and related nitroaromatics). This has recently been expanded to include triazines and carbamatate pesticides. In a closely related effort we have been funded as part of the NIEHS superfund project to look at these types of interactions for polychrorinated biphenyls, polyaromatic hydrocarbons, and dioxins. This effort is being coordinated by researchers at Michigan State University. Here at Purdue, we have a funded specific cooperative agreement between Purdue and the USDA-ARS National Soil Erosion Lab with Darrell Norton to look at these types of interactions for glyphosate in soils. Results have been presented at a number of different meetings including invited presentations at the International Clay Minerals - Groupe France Argille (held in France, June, 2006) and at the American Chemical Society Meetings (San Francisco, CA, September 2006). We have also been active extending these concepts to developing an improved fundamental understanding of clay particles. An exciting collaboration has developed with the Katholieke University in Leuven, Belgium, University of Szeged, Hungary and the University of Tokyo, Japan looking at developing sophisticated methods to functionalize and characterize ultra thin films of clay particles that are only 1 nanometer thick. An invited review to the prestigious journal Chemical Physics Physical Chemistry has just been accepted.

Impacts
Our research is providing new insight about the way that agricultural chemicals move, are retained and transformed in soil. This research is being extended to new classes of chemicals including carbamate and triazine pesticides, glyphosate, PCBs, PAHs, and dioxins.. In addition, we are developing a broader understanding about the fundamental properties of soil constituents and their reactivity at the nanoscale.

Publications

Ras, R.H.A., Johnston, C.T., Schoonheydt, R.A. Chemical instability of octadecylammonium monolayers. Chemical Communications (32): 4095-4097 (2005)
Arroyo,, L.J., Li, H., Teppen, B.J., Johnston, C.T. Boyd, S.A. Oxidation of 1-naphthol coupled to reduction of structural Fe3+ in smectite. Clays and Clay Minerals 53(6): 587-596 (2005).
Sato, H., Ono, K., Johnston, C.T., Yamagishi, A. First-Principles Studies on the Elastic Constants of a 1: 1 Layered Kaolinite Mineral. American Mineralogist 90(11-12): 8124-8126 (2005).
Fernandes de Oliveira, M.F., Johnston, C.T., Premachandra, G.S., Teppen, B.J., Li, H., Laird, D.A., Zhu, D., Boyd, S.A. Spectroscopic Study of Carbaryl Sorption on Smectite from Aqueous Suspension. Environmental Science & Technology 39: 9123-9129 (2005).
J. R. Schoonover, W. P. Steckle, Jr., C. T. Johnston, Y. Wang, A. M. Gillikin, and R.A. Palmer. Humidity-Dependent Dynamic Infrared Linear Dichroism Study of a Poly(Ester Urethane) Spectrochimica Acta Part A. (http://dx.doi.org/10.1016/j.saa.2006.07.015)(2006).
Schoonheydt, R.A. and Johnston, C.T. Surface and interface chemistry of clay minerals. Chapter 3 in Handbook of Clay Science I in Series Developments in Clay Science. Eds. F. Bergaya, B.K.G. Theng & G. Lagaly, Elsevier Science LTD. Pages 87-112, ISBN-13 978-0-08-044183-2 (2006)
H Li, B.J. Teppen, D.A. Laird, C.T. Johnston, S.A. Boyd. Effects of increasing potassium chloride and calcium chloride ionic strength on pesticide sorption by potassium- and calcium smectite. Soil Science Society of America Journal 2006 70: 1889-1895 (2006).

Progress 10/01/04 to 09/30/05

Outputs
For the past six years we have had a successful collaboration with researchers at Michigan State University (B.Teppen, S.A. Boyd, H. Li) and the National Soil Tilth Lab (David Laird, USDA-ARS Ames, Iowa) in studying how pesticides and related chemicals interact with soil constituents. Our overall goal is to develop an improved understanding about the molecular level processes that govern pesticide interactions in soils. We have developed a coupled experimental-theoretical approach that combines modern spectroscopic methods with computational quantum chemical methods and traditional sorption methods. In the last year we have started to look at a broader range of chemicals. Much of our prior work was focused on nitroaromatics (e.g., DNOC, DINSOSEB and related nitroaromatics). This past year we have studied the interaction of an important class of pesticides, the carbamates, with soil minerals. These compounds have a very different modality of surface interaction where the interaction of the compound with the soil surface is influenced by the nature of the exchangeable cation in a very different mechanism from that of the nitroaromatics. The concepts that are coming out of this collective work are starting to be tested at the field scale. In addition, working with L.D. Norton at the National Soil Erosion Laboratory, we have continued to study the molecular mechanisms of anhydrous ammonia with Midwestern soils. We have found that the nature of the exchangeable cation (i.e., Ca2+ versus Mg2+) plays an important role governing the retention of anhydrous ammonia in agricultural soils. Results have been presented at a number of different meetings including invited presentations at the International Clay Conference held in Tokyo (August, 2005) and at the American Chemical Society Meetings (San Diego, CA, March 2005), and at the annual meetings of The Clay Minerals Society (Burlington, Vermont, June, 2005). We have also been active extending these concepts to developing an improved fundamental understanding of clay particles. An exciting collaboration has developed with the Katholieke University in Leuven, Belgium looking at developing sophisticated methods to functionalize and characterize ultra thin films of clay particles that are only 1 nanometer thick. On the theoretical side, we are collaborating with a group of computational chemists at the University of Tokyo modeling from first principles the fundamental properties of clay particles.

Impacts
Our research is providing new insight about the way that agricultural chemicals move, are retained and transformed in soil. This research is being extended to new classes of chemicals including carbamate and triazine pesticides. In addition, we are developing a broader understanding about how water and plant nutrients (e.g., anhydrous ammonia) interact with soils. Concepts are being integrated into our teaching program and undergraduate and graduate students are developing new skills in agriculurally-related concepts in nanoscience.

Publications

Johnston, C.T., Boyd, S.A., Teppen, B.J., Sheng G., 2004. Sorption of Nitroaromatic Compounds on Clay Surfaces. in Handbook of Layered Materials for Catalytic Applications, S. M. Auerbach, K. A. Carrado, P. K. Dutta, Eds., Marcel-Dekker: NY, pp. 155-189
Arroyo LJ, Li H, Teppen BJ, Johnston, C.T., Boyd, S.A. 2004. Hydrolysis of carbaryl by carbonate impurities in reference clay SWy-2 J. Agric. Food Chem. 52:8066-8073.
Schoonheydt, R.A. and Johnston, C.T. 2005. Surface and interface Chemistry of clay minerals. Chapter 2 in Handbook of Clay Science Eds. F. Bergaya, B.K.G. Theng & G. Lagaly, Elsevier Science LTD. In press
Dontsova, K.M., Norton, L.D., Johnston, C.T. 2005. Calcium and magnesium effects on ammonia adsorption by soil clays. Soil Science Society of America Journal 69:1225-1232.
Chappell, M.A., Laird D.A., Thompson M.L., Li H., Teppen B.J., Aggarwal V., Johnston C.T., Boyd S.A. 2004. Influence of smectite hydration and swelling on atrazine sorption behavior. Environmental Science & Technology 39:3150-3156.
Ras, R.H.A., Nemeth, J., Johnston, C.T., Dekany, I., Schoonheydt, R.A. 2004. Orientation and conformation of octadecyl rhodamine B in hybrid Langmuir-Blodgett monolayers containing clay minerals. Physical Chemistry Chemical Physics 6:5347-5352
Ras, R.H.A., Johnston, C.T., Schoonheydt, R.A. 2005. Chemical instability of octadecylammonium monolayers Chemical Communications (Advanced Article first published 7/13/2005, DOI: 10.1039/b504483a).
Arroyo,, L.J., Li, H., Teppen, B.J., Johnston, C.T. Boyd, S.A. 2005. Reduction of structural Fe3+ in smectite coupled to oxidation of 1-naphthol. In Press. Clays and Clay Minerals.
Sato, H., Ono, K., Johnston, C.T., Yamagishi, A. 2005. First-Principles Studies on the Elastic Constants of a 1: 1 Layered Kaolinite Mineral. In Press. American Mineralogist.
Fernandes de Oliveira, M.F., Johnston, C.T., Premachandra, G.S., Teppen, B.J., Li, H., Laird, D.A., Zhu, D., Boyd, S.A. 2005. Spectroscopic Study of Carbaryl Sorption on Smectite from Aqueous Suspension. In Press Environmental Science & Technology

Progress 10/01/03 to 09/29/04

Outputs
We have continued to make significant progress in our understanding of pesticide interactions with soil constituents. Working in collaboration with researchers at Michigan State University (B.Teppen, S.A. Boyd, Hui Li) and the National Soil Tilth Lab (David Laird, USDA-ARS Ames, Iowa) we have made progress in understanding how nitroaromatic compounds, triazines, and carbamates interact with soil minerals. We have studied how different exchangeable cations (e.g., Ca2+, Mg2+, and K+) significantly influence how these compounds interact with clay surfaces. This has been applied by some very basic but ground-breaking technology related to how clay minerals function at the molecular level. For the first time, working in collaboration with a research group in Belgium and the Katholieke University in Leuven, we have isolated and studied a layer containing only one-layer of 1 nm thick clay particles. This has far reaching implications to study how clay minerals influence water, nutrient, and pesticide interactions in soil.

Impacts
For the first time, we have been able to isolate and study a single layer of clay particles. This is an important result that will allow us to develop an improved understanding about how pesticides and related chemicals move through soils and interact with soil constituents. In addition, this may help in the design of improved ways of making new materials that will attenuate pesticides and reduce their mobility in natural systems.

Publications

Li, H.; Teppen, B.J; Johnston, C.T.; Boyd, S.A., Thermodynamics of Nitroaromatic Compound Adsorption from Water by Smectite Clay. Web release date of 18 Sept. 2004 Environmental Science and Technology (2004)
Dontsova, K.M.; Norton, L.D.; Johnston, C.T.; Bigham, J.M., Influence of exchangeable cations on water adsorption by soil clays. Soil Science Society of America, 68 (4):1218-1227 (2004).
Sato, H.; Ono, K.; Johnston, C.T.; Yamagishi, A. First-Principle Study on Polytype Structures of 1:1 Dioctahedral Phyllosilicates. In Press American Mineralogist (200X).
Jiang, D; Premachandra, G.S.; Johnston, C.T.; Hem, S.L. Structure and antigen adsorption properties of calcium phosphate adjuvant. Available on line 23 July 2004. Vaccine (2004).
Johnston, C.T.; Hem, S.L.; Guenin, E.; Mattai, J. Afflito. Potentiometric/turbidometric titration of aluminum compounds. J. Cos. Sci, 54, 113-118 (2003).
Ras, R.H.A.; Nemeth, J.; Johnston, C.T.; Dekany, I.; Schoonheydt, R.A. Infrared reflection absorption spectroscopy study of smectite clay monolayers Thin Solid Films 466 (1-2) 291-294 (2004)
Ras, R.H.A.; Nemeth, J.; Johnston, C.T.; DiMasi, E.; Dekany, I.; Schoonheydt, R.A.. Hybrid Langmuir Blodgett Monolayers containing Clay Minerals: Effect of Clay Concentration and Layer Charge Density on the Film Formation. Phys. Chem. Chem. Phys. (PCCP). 6 (16): 4174-4184 2004
Li, H.; Teppen, B.J.; Laird, D.A.; Johnston, C.T.; Boyd, S.A. Geochemical modulation of pesticide sorption on smectite clays. Web release date of 16 Sep 2004. Environmental Science and Technology (2004)

Progress 10/01/02 to 09/30/03

Outputs
Working in collaboration with researchers at the National Soil Tilth Lab (David Laird, USDA-ARS Ames, Iowa) and Michigan State University (B.Teppen, S.A. Boyd), we have continued to make progress in understanding the molecular level processes that govern pesticide interaction in soils. Using spectroscopic methods, combined with modern computational quantum chemical methods and traditional sorption methods, we have gained new insight about how pesticides interact with soil surfaces. We have found that clay minerals play a more important role than previously thought. Compounds studied include atrazine, DNOC, DINSOSEB and carbaryl. In soils, organic matter and minerals are often associated such that it is unclear how the presence of the former component influences the sorptive properties of the latter one. We have studied the sorption and desorption of the herbicides 4,6-dinitro-o-cresol, and dichlobenil by Ca2+-, K+-smectites, and humic acid-smectite complexes, using batch-equilibrations and x-ray diffraction (XRD). Greater sorption of 4,6-dinitro-o-cresol compared with dichlobenil was observed for both smectites and humic acid-smectite complexes. For both pesticides, K+ smectites were more effective sorbents than Ca2+ smectites, with the lower,charge-density Clay (SWy-2) displaying a greater sorption capacity than the higher charge-density clay (SAz-1). In addition, we have studied the sorption of selected pesticides from aqueous solution using sorption and spectroscopic methods.

Impacts
For the first time, we have been able to isolate and study a single layer of clay particles. This is an important result that will allow us to develop an improved understanding about how pesticides and related chemicals move through soils and interact with soil constituents. In addition, this may help in the design of improved ways of making new materials that will attenuate pesticides and reduce their mobility in natural systems.

Publications

Hou, X. , D. L. Bish, S. L. Wang, C. T. Johnston and R.J. Kirkpatrick . 2003. Hydration, Expansion, Structure, and Dynamics of Layered Double Hydroxides. American Mineralogist. 88:167-179
Johnston, C. T. , S. A. Boyd, B. J. Teppen and G. Sheng. 2003. Sorption of Nitroaromatic Compounds on Clay Surfaces. Handbook of Layered Materials for Catalytic Applications. Marcel-Dekker, NY. New York, New York. S.M. Auerbach, K.A. Carrado, P.K. Dutta. 1:155-190; Chap 4.
Li, H. , G. Sheng, B. J. Teppen, C. T. Johnston and S.A. Boyd. 2003. Sorption and Desorption of Pesticides by Clay Minerals and Humic Acid-Clay Complexes. Soil Science Society of America Journal. 67:122-131.
Schoonover, J. R. , S. L. Zhang and C. T. Johnston. 2003. Raman Spectroscopy and Principal Factor Analysis of Concentrated A1203-Na20-H20 Solutions. Journal of Raman Spectroscopy. 34:404-412.
Wang, S. L. , C. T. . Johnston, D. L. Bish, J. L. White and S.L. Hem. 2003. Water-Vapor Adsorption and Surface Area Measurement of Poorly Crystalline Boehmite.. Journal of Colloid and Interface Science. 260:26-35
Jiang, D. , C. T. Johnston and S. L. Hem. 2003. Using Rate of Acid Neutralization of Characterize Aluminum Phosphate Adjuvant.. Pharmaceutical Development and Technology. 8:349-356.
Ras, R. H. A. , C. T. Johnston, E. A. Franses, R. Ramaekers and G. Maes P. Foubert F.C. DeSchryver R.A. Schoonheydt . 2003. Polarized infrared study of hybrid Langmuir-Blodgett monolayers containing clay mineral nanoparticles. Langmuir. 19:4295-3902.
Dera, P. , C. Prewitt, D. L. Bish, S. Japel and C.T. Johnston. 2003. Pressure-Controlled Polytypism in Hydrous Layered Materials.. American Mineralogist. 88:1428-1435.

Progress 10/01/01 to 09/30/02

Outputs
Working with researchers at Michigan State University (B.Teppen, S.A. Boyd), we have made progress in developing a better understanding of the molecular level processes that govern pesticide retention in soils. Using spectroscopic methods combined with modern computational quantum chemical methods and traditional sorption methods we have gained new insight about how pesticides interact with soil surfaces. We have found that clay minerals play a more important role than previously thought. Compounds studied include atrazine, DNOC, DINSOSEB and carbaryl. Using Raman spectroscopy, we have obtained new information about the chemistry of waste formed by aluminum and alkaline, or caustic sodium compounds, mixing with high level radioactive material. This knowledge will be applied to the permanent disposal of the 53 million gallons of radioactive material held in 177 giant underground tanks at the Hanford site. Most of the storage tanks are at least 50 years old, 30 years older than the original intended usage, according to the Tri-Party Agreement, a consortium of the DOE, the U.S. Environmental Protection Agency and the Washington State Department of Ecology. Of the 177 tanks, 149 of them are have only one outer wall, and 67 of these single shelled tanks are suspected to have leaked an estimated one million gallons of high level waste. We have gained new information about the chemistry of aluminum in these very concentrated waste solutions. The significance of that is related to two different areas: minimizing high level nuclear waste volume for permanent storage, and eventually determining what happens to the material when it leaks out of the tank. At the bulk scale, clays are inert and not particularly useful. But, like other materials, clays at the nanoscale don't behave in the linear, simple fashion that they do on a larger scale. And that variable behavior makes them very useful in a variety of applications. But it also means that how we think about clays in the environment may be wrong. Inert at the bulk scale, individual clay particles have an electrical charge that varies along the surface of the particle. The distance between charge sites can vary between one and three nanometers, and that is important because organic molecules, such as pesticides, have similar dimensions. Now we can develop a molecular picture of what's happening in these types of structures. This finding means that chemicals that were thought to rush by clay as they passed through the soil may in fact be held up for a time. Or, the chemicals may even be chemically degraded by the surface of the clay. The manipulation and understanding of clays at the nanoscale is important for many areas. Many new plastics contain clays, as do vaccines used to protect human and animal health. These vaccines are made up of two parts, a biological protein attached to an inorganic particle, similar to a clay particle, which delivers the vaccine within the body. Along with Stanley Hem, Purdue professor of physical pharmacy, we are working to better understand the structure of these particles in vaccines so that the next generation of vaccines will be more effective.

Impacts
Researchers armed with a laser are closer to knowing how to prepare millions of gallons of highly radioactive nuclear waste for permanent storage. Using Raman spectroscopy we have been the first to describe the chemistry of waste formed by aluminum and alkaline, or caustic sodium compounds, mixing with high-level radioactive material. This knowledge will be applied to the permanent disposal of the 53 million gallons of radioactive material held in 177 giant underground tanks at the Department of Energy's Hanford Nuclear Reservation in Richland, Wash. For a large group of pesticides, the conventional wisdom was that they had little to do with clay surfaces. For the most part, these would interact with organic material in the soil. But, now that we're developing more sophisticated ways to look at these systems, we're finding that some pesticides have greater affinity for clay surfaces than for organic materials in the soil. This allows us to develop better models of how these compounds are going to behave in the environment.

Publications

Johnston, C.T., and Tombacz, E. Surface Chemistry of Soil Minerals. 2002. Chapter 2 in "Soil Mineralogy with Environmental Applications" J. Dixon and D. Schulze (eds.) SSSA Book Series: 7 pages 37-68.
Micheli, E., Madari, B., Tombacz E. Johnston C.T., 2002. Tillage - soil organic matter relationships in long-term experiments in Hungary and Indiana. Chapter 4. p. 565-581. Agricultural Practices and Polices for Carbon Sequestration in Soil. Adv. Soil Sci. CRC Press, Boca Raton, FL.
Johnston, C.T. and S.L. Wang. 2002. Applications of vibrational spectroscopy in soil and environmental sciences. In "Handbook of Vibrational Spectroscopy" Eds. P.R. Griffiths and J.C. Chalmers. John Wiley, New York, New York. Volume 4. Applications in Industry Materials and the Physical Sciences, pp. 3192-3206.
Sheng, G., Johnston, C.T., Teppen, B.J., Boyd, S.A. 2002. Dinitrophenol herbicide sorption from water by montmorillonites. Clays Clay Minerals. 50: 25-34.
Johnston, C.T., Wang, S.L., Hem, S.L. 2002. Measuring the surface area of aluminum hydroxide adjuvant. J. Pharmaceutical Sciences. 91:1702-1706.
Johnston, C.T., Agnew, S.F., Schoonover, J.R., Kenney, J.W., Page, B., Osborn, J. and Corbin, R. 2002. Raman study of aluminum speciation in simulated alkaline nuclear waste. Environmental Science and Technology. 36:2451-2458.
Johnston, C.T., Bish, D.L., Dera, P., Wang, S.L., Agnew, S.F., and Kenney, J.W. 2002. Novel pressure-induced phase transformations in hydrous layered materials. Geophysical Research Letters. 10:1029-1033.

Progress 10/01/00 to 09/30/01

Outputs
During the past year we have made significant progress in the area developing a better understanding of processes occurring in soils related to the fate and transport of pesticides, nutrients, and other compounds in soils. We use molecular level tools (spectroscopic methods) combined with macroscopic measurements (sorption) to work on applied problems in soils. We have been working closely with researchers at Michigan State University (S. Boyd, B. Teppen) to study pesticide interactions in soils. We have found that for a surprisingly wide range of compounds, soil minerals play a dominant role in the retention of pesticides. Using a combined strategy of spectroscopic, sorption, structural, and theoretical modeling methods we have shown how pesticides like DNOC, Carbaryl, TNT, and atrazine interact with soil minerals. Working with S. Goldberg at U.S. Salinity Laboratory, we have used a similar approach to study how As(III) and As(V) interact with soil components. Related to these studies, we are developing new methods to study soil particles in aqueous suspension. Other research projects have focused on making and characterizing a synthetic soil like material from coal ash and pharmaceutical byproducts.

Impacts
We have determined how certain types of pesticides are bound to soil minerals. This is important because soil minerals have been neglected in pesticide transport and retention models where the role of soil organic matter has been emphasized. Depending on the type of compound, we have shown that soil minerals can be the dominant sorptive phase.

Publications

Guest, C.; Johnston, C.T.; King, J.; Tishmack, J.K.; and Norton, L.D. 2001. Synthetic soil from composting coal combustion byproducts and an industrial biosolid. Journal of Environmental Quality. 30:246-253.
Goldberg, S., Johnston, C.T. 2001. Mechanisms of arsenic adsorption on amorphous oxides evaluated using macroscopic measurements, vibrational spectroscopy, and surface complexation modeling. Journal of Colloid and Interface Science 234:204-216.
Johnston, C.T., and Premachandra, G.S. 2001. Polarized ATR-FTIR study of smectite in aqueous suspension. Langmuir 17: 3712-3718.
Boyd, S.A., Sheng, G.; Teppen, B.J.; Johnston, C.T. 2001. Mechanisms for the adsorption of substituted nitrobenzenes by smectite clays. Environ. Sci. Technol., 35 (21), 4227 -4234.
Sheng, G.Y., Johnston, C.T., Teppen B.J., Boyd, S.A. 2001. Potential contributions of smectite clays and organic matter to pesticide retention in soils J Agr. Food Chem 49: 2899-2907.
Johnston, C.T.; Olivera, M.F., Teppen, B.J.; Sheng, G.; Boyd, S.A. 2001. Spectroscopic study of nitroaromatic-smectite sorption mechanisms. Enviorn. Sci. Technol., In press.
Sheng, G.; Johnston, C.T.; Teppen, B.J.; Boyd, S.A. 2001. Adsorption of dinitrophenol herbicides from water by montmorillonites. Clays and Clay Minerals In press.
Johnston, C.T.; and Tombacz, E. 2001. Surface Chemistry of Soil Minerals. Chapter 2 in "Environmental Soil Mineralogy" J. Dixon and D. Schulze (eds.) In press.
Johnston, C.T. and S.L. Wang. 2001. Applications of vibrational spectroscopy in soil and environmental sciences. In "Handbook of Vibrational Spectroscopy" Eds. P.R. Griffiths and J.C. Chalmers. John Wiley, New York, New York. In press.

Progress 10/01/99 to 09/30/00

Outputs
We have made progress during the past year to develop an improved understanding of the structure and reactivity of soil particles. We have reported that the structure and property of water sorbed to soil minerals is very different from that of "bulk" water. The nature of these polarized water molecules at the soil-water interface dictate and regulate many of the important surface processes that occur in soils, such as cation exchange and sorption. We have used advanced molecular-based methods to gain new information about how pesticides interact with soil minerals. In particular, we have used in situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and Raman methods to study pesticide sorption on soil particles. We have found that certain types of pesticides (e.g., nitroaromatic containing compounds such as dinoseb and DNOC), have a very high affinity for soil minerals. We have studied how these compounds interact with soil minerals have determined that electrostatic and hydrophobic surface forces contribute to stabilize the pesticide. In addition to pesticides, we have also examined the interaction of water, several amines (ammonia, ammonium, and hydrazine), and several oxyanions (phosphate and arsenic compounds) with soil minerals. In general, our research program is focused on the interface between water and the solid mineral and organic phases in soils. This interface is important because it controls the retention, transformation, and transport of nutrients and pollutants, provides physical support for plants and microorganisms, influences water quality, and controls the rheological properties of soils. Although much is known about the general behavior of pollutants and nutrients in soil and subsurface environments, relatively little is known about the chemical mechanisms underlying this behavior. To this end, we are studying how pollutants (e.g., pesticides) and nutrients (e.g, phosphate) interact with soil particles at the molecular level using a combined approach of spectroscopic and macroscopic methods. We have used a new method, micro-Raman spectroscopy, to study the structure of gibbsite, one of the most common forms of aluminum oxide found in soils and subsurface environments. Although gibbsite has been studied extensively over the past 40 years, a detailed understanding about its reactive features was lacking.

Impacts
We have shown that certain types of pesticides are strongly bound to soil minerals. For certain pesticides (e.g., dinitro-o-cresol, dinoseb, carbaryl, atrazine), sorption on soil clays can exceed that of soil organic matter. This information will contribute to the development of improved models to predict pesticide fate and transport in soils

Publications

Xu, W., Johnston, C.T., Parker, P. and Agnew, S.F. 2000. Infrared study of water sorption on SWy-1 and SAz-1 montmorillonite. Clays and Clay Minerals, 48:120-131, 2000.
Wang, S.L., Johnston, C.T. 2000. Assignment of the structural OH stretching bands of gibbsite. American Mineralogist, 85:739-744, 2000.
Burrell, L.S.; Johnston, C.T., Schulze, D., Klein, J., White, J.L., Hem, S.L. 2000. Aluminum phosphate adjuvants prepared by precipitation at constant pH. Part I: Composition and structure. Vaccine. 19:275-281, 2000.
Burrell, L.S.; Johnston, C.T., Schulze, D., Klein, J., White, J.L., Hem, S.L. 2000. Aluminum phosphate adjuvants prepared by precipitation at constant pH. Part II: Physiochemical properties. Vaccine, 19:282-287, 2000.
Johnston, C.T.; Eckert, J., Dotson, L., Bish, D.L. 2000. Vibrational spectroscopic study of the 1.035 and 0.95 nm kaolinite-hydrazine intercalation complexes. Journal of Physical Chemistry. 104: (33) 8080-8088, 2000.
Guest, C.; Johnston, C.T.; King, J.; Tishmack, J.K.; and Norton, L.D.2000. Synthetic soil from composting coal combustion byproducts and an industrial biosolid. In Press. Journal of Environmental Quality.
Johnston, C.T.; and Tombacz, E. 2000. Surface Chemistry of Soil Minerals. Chapter 2 in "Environmental Soil Mineralogy" J. Dixon and D. Schulze (eds.) In press.
Goldberg, S., Johnston, C.T. 2000. Mechanisms of arsenic adsorption on amorphous oxides evaluated using macroscopic measurements, vibrational spectroscopy, and surface complexation modeling. In press. Journal of Colloid and Interface Science.
Johnston, C.T. 2000. Application of IR and Raman spectroscopy in Soil and Environmental Science. Handbook of Vibrational Spectroscopy. P.R. Griffiths and J. Chalmers ed. In press.

Progress 10/01/98 to 09/30/99

Outputs
Our research program is focussed on the interface between water and the solid mineral and organic phases in soils. This interface is important because it controls the retention, transformation, and transport of nutrients and pollutants, provides physical support for plants and microorganisms, influences water quality, and controls the rheological properties of soils. Although much is known about the general behavior of pollutants and nutrients in soil and subsurface environments, relatively little is known about the chemical mechanisms underlying this behavior. To this end, we are studying how pollutants (e.g., pesticides) and nutrients (e.g, phosphate) interact with soil particles at the molecular level. Contributions during the past year include work in three areas. First, we have contributed to the understanding of what the reactive soil mineral features look like on a molecular scale using micro-Raman spectroscopy. Working in collaboration with researchers at Los Alamos National Laboratory (Dr. Bish) on kaolin group minerals, we have provided the definitive experimental data about the locations of the hydrogen atoms. There are very few mineral systems where this type of detailed information has been obtained. This type of experimental data represents an important step in being able to model reactions occurring on soil surfaces. Secondly, we have continued to study how soil particles react with water itself. The importance of water and its controlling influence on the Earth's crust is a useful starting point for understanding the surface reactivity of soils. Water is the only naturally occurring inorganic liquid on Earth and is directly responsible for shaping and transforming the surfaces of soil minerals. On a molecular scale, we have examined in detail how water molecules interact with clay surfaces and how the presence of water regulates processes including cation exchange, soil erosion, retention of nutrients, and the degradation of pollutants. Working in collaboration with Prof. Stephen Boyd at Michigan State University, we are studying pesticide sorption on expandable clay minerals, such as smectites. We are finding that the amount of pesticide sorption occurring on these clays can be considerably higher than from soil organic matter. Soil organic matter has been traditionally viewed as the dominant sorptive phase for most pesticides in soil environments. We are studying the mechanisms of how pesticide sorption occurs using a combined approach of sorption (HPLC) and spectroscopic methods.

Impacts
New information has been obtained about how pesticides are retained in soils. For certain pesticides (e.g., dinitro-o-cresol, dinoseb), sorption on soil clays greatly exceeds that of soil organic matter. This information will contribute to the development of improved models to predict pesticide fate and transport in soils.

Publications

Johnston, C.T., Helsen, J., Schoonheydt, R. and Bish, D.L. Single-crystal Raman spectroscopic study of dickite. 1998. American Mineralogist, 83: 75-84. Bhatti, J.S., Comerford, N.B. and Johnston C.T. 1998. Influence of soil organic matter removal and pH on oxalate sorption onto a spodic horizon. Soil Sci. Soc. Am. J. 62:152-158.
Bhatti, J.S., Johnston, C.T. and Comerford, N.B. 1998. Influence of oxalate and soil organic matter on sorption and desorption of phosphate onto a Spodic horizon. Soil Sci. Soc. Am. J. 62:1089-1095.
Robinson, S., Johnston, C.T. and Reddy, K.R. 1998. Combined chemical and 31P NMR spectroscopic analysis of phosphorus in wetland organic soils. Soil Science, 163: 705-713.
Madari, B., Micheli, E., Czinkota, I., Johnston, C.T. and Graveel, J.G. 1998. Soil organic matter as indicator of changes in the environment. Anthropogenic influences: Tillage Agrokem Es Talajtan 47, 121-132.
Norton, L.D.; Altieri, R.; Johnston, C.T. 1998. Co-utilization of by-products for soil improvement and erosion control. Beneficial Co-utilization of Agricultural-Municipal and Industrial Byproducts. S. Brown (ed.) Klure Publ, Dordrecht, Netherlands, pp. 163-174.
Davis, W.M., Erickson, C.L., Johnston, C.T, Delfino, J.J. and Porter, J.E. 1999. Quantitative Fourier Transform Infrared spectroscopic investigation of humic substance functional group composition. Chemosphere 38: 2913-2928.
Lin, L., Johnston, C.T., Blatchley E.R. 1999. Inorganic Fouling at Quartz: Water Interfaces in Ultraviolet Photoreactors I: Chemical Characterization, Water Research 33: 3321-3329.
Lin, L., Johnston, C.T., Blatchley. E.R. 1999. Inorganic Fouling at Quartz: Water Interfaces in Ultraviolet Photoreactors II: Temporal and Spatial Distributions, Water Research 33: 3330-3338.
Lin, L., Johnston, C.T., Blatchley E.R., 1999. Inorganic Fouling at Quartz: Water Interfaces in Ultraviolet Photoreactors III: Numerical Modeling, Water Research 33: 3339-3347

Progress 10/01/97 to 09/30/98

Outputs
During the past year we developed a new spectroscopic method to study constituents using laser Raman spectroscopy. In Ref. (1) we have published the first-reported single-crystal Raman study of a clay mineral. This method provides information about what the structure and reactive surfaces of micro-crystalline soil constituents "look" like on a molecular scale. At the present time, we are extending this method to study other commonly occurring minerals in soil environments, which include gibbsite and brucite. Working in collaboration with Nick Comerford at the University of Florida, we examined the interaction of organic acids with Spodosols of the southeastern USA. Using a combined approach of wet chemical and spectroscopic methods, oxalate was been shown to strongly influence the availability of PO4 and the stability of soil organic matter (Refs. 2-3) in these soils. Oxalate is a naturally occurring organic acid that is produced by plant roots. There is interest at the present time to extend these studies on Spodosols to examine the interaction of organic acids with Ultisols and Oxisols. A detailed understanding about the chemical forms of phosphorus (P) in soils and sediments is lacking. This is due, in part, to the limited experimental methods that are available that can distinguish between inorganic and organic forms of P in soils. Working together with Steve Robinson (Univ. of Reading, UK) and Ramesh Reddy (Univ. of Florida) we successfully used a new method, P31 NMR spectroscopy, to study the chemical forms of P in selected wetland soils (Ref. 4). Land application of coal combustion byproducts (CCBs) mixed with solid organic wastes, such as municipal sewage sludge, has become increasingly popular as a means of productively using what were once considered waste products. However, little is known about the long-term consequences of land application of CCB-solid organic waste mixes. In Ref. 5 we have reported on the chemical and mineralogical properties of a soil-like material obtained from a mixture of coal combustion byproducts (CCBs from the Purdue Power Plant Po) with a solid organic waste (fermentation byproduct from Eli Lilly). This study represented the preliminary basis for a large-scale, ongoing composting project at Purdue University to make synthetic soil. To date 5000 metric tons of synthetic soil have been produced.

Impacts
(N/A)

Publications

1. Johnston, C.T.; Helsen, J.; Schoonheydt, R.; and Bish, D.L. 1998. Single crystal Raman Spectroscopic study of Dickite. American Mineralogist, 83: 75-84
2. Bhatti, J.S.; Comerford, N.B.; Johnston C.T. 1998. Influence of soil organic matter removal and pH on oxalate sorption onto a spodic horizon. Soil Sci. Soc. Am. J. 62:152-158.
3. Bhatti, J.S.; Johnston, C.T.; and Comerford, N.B. 1998. Influence of oxalate and soil organic matter on sorption and desorption of phosphate onto a Spodic horizon. Soil Sci. Soc. Am. J. 62:1089-1095.
4. Robinson, J.S., Johnston C.T., Reddy K.R. 1998, Combined chemical and P-31-NMR spectroscopic analysis of phosphorus in wetland organic soils Soil Science 163, 705-713.
5. Norton, L.D.; Altieri, R.; Johnston, C.T. 1998, Co-utilization of by-products for soil improvement and erosion control. Beneficial Co-utilization of Agricultural-Municipal and Industrial Byproducts. Ed. S. Brown. Klure Publ, Dordrecht, Netherlands. In Press