Brief Summary of Minutes of Annual Meeting

1. Review and Members of Project Goal for Newly Accepted Proposal
   1. Provided status of renewed project.
   2. Discussed project goals.
   3. Discussed individual project interests that overlap goals.
2. Reports on activities for development and use of advanced microscopic molecular analysis in soils
   1. Each attendee related their research activity in terms of using advanced analytical tools in soil science.
   2. Discussion of needs to continue knowledge building to integrate new cutting edge tools in soil science.
3. Development of Dear colleague letter for INFEWS
   1. Discussed plans to submit white paper to ASA on Food Energy Water to tell NSF the research funding needs as assessed by agricultural researchers.
   2. Developed central theme of paper.
   3. Assigned writing jobs.
   4. Set timeline and action items.
4. Committee leadership
   1. Dan Strawn is the committee chair.
   2. Ganga Hettiarachchi is the vice chair and secretary.
5. Committee Reports
   1. Nancy Cavallero discussed USDA NIFA program emphasis areas and provided suggestions for developing projects that are responsive to calls.

Members of this project are applying a wide range of analytical tools to elucidate mechanisms of physical and chemical protection of carbon in soils, colloid transport through soil, removal of soil contaminants, effect of climate change on soil structure, storage and transport of soil water, and deposition of synthetic nanoparticles on the human respiratory system. More detailed description of research outcomes by the different groups is presented below.

Dr. Donald Sparks and Ph.D. candidate Audrey Gamble at the University of Delaware have collaborated with scientists at Brookhaven National Laboratory to test novel techniques for determining phosphorous (P) speciation in soils. Phosphorous is an environmentally-relevant element as both a nutrient required for crop growth and as a pollutant in eutrophic water supplies. The retention and mobilization of soil P is largely governed by the chemical form of P. Traditional methods to identify soil P forms often rely on chemical extractions which can introduce artifacts during analysis. To increase the fundamental understanding of soil P chemistry, a combination of X-ray fluorescence and X-ray absorption techniques were used to identify P forms without chemical alteration of soil samples. Data indicate the ability of X-ray fluorescence to correlate the presence of P with Ca, Fe, and Al in soils. Combined analysis with X-ray fluorescence and X-ray absorption spectroscopy can be used to identify mineral and sorbed forms of soil P; however, these techniques are limited in their ability to determine organic P forms. Upcoming technological advancements at Brookhaven National Laboratory will increase the capabilities of these techniques to evaluate P speciation in environmental samples.  These studies will enable scientists to recommend robust strategies for more efficient use of phosphorus on crops such that yields can be maximized, but at the same time, minimize phosphorus enrichment of waterways. This will help sustain both agriculture and the environment.

At Michigan State University Dr. Wei Zhang has been studying the fate and transport of fine particulate matter (i.e., colloids and engineered nanoparticles), and particulate sorbents for contaminant immobilization in soil and water. An article on arsenic sorption by magnetite nanoparticles was published, which elucidated the fundamental binding mechanisms of arsenate and arsenite on magnetite surface and novel redox transformation of sorbed arsenic upon exposure to oxygen during drying. This research has implications in using magnetite nanoparticles for in-situ groundwater remediation or for drinking water treatment of arsenic contamination. We also published an article on the effect of plant root exudates on the downward transport of smectite clay particles in sand, in comparison with humic acid. We reported that plant root exudates inhibited the transport of smectite clays, which was attributed to amino acid fraction of root exudates. This finding suggest that soil rhizosphere could slow the downward transport of clay and clay-associated contaminants. We have statistically evaluated the relationships between biochar properties and production parameter and feedstock type. The statistical tools reported in this study could be used to produce biochars with desirable properties, therefore facilitating development and adaptation of biochar technology.

At Michigan State University Dr. Alexandra Kravchenko continued assessment of micro-scale processes governing soil’s contribution to global cycling of carbon and nitrogen. Specifically, this year her group has conducted a review of the current state of knowledge of the role of pores as the major physical drivers behind processes of soil C sequestration and greenhouse-gas emissions. An in-depth assessment of a variety of mechanisms by which soil pores contribute to these processes and of a range of laboratory techniques that are used will lay the basis for further developments in micro-scale soil research.

Dr. Harsh at Washington State University is working on projects to understand the fate of technetium in the subsurface, as well as understanding how biuchar reacts in the environment. In order to understand the fate of Tc-99 as pertechnetate under the Hanford Site, perrhenate was used as an analog and reacted with solutions that simulated leaking radioactive tank wastes. Small amounts of nearly nonexchangeable perrhenate were incorporated into feldspathoid phases sodalite and cancrinite. Further studies showed that incorporation into sodalite is a function of anion size and other ions present in waste tanks, namely nitrate, nitrite, chloride, sulfate, and carbonate, outcompete perrhenate for sodalite sites. Perrhenate is likely to be a good analog for pertechnetate under the conditions studied. At WSU, biochar samples were produced from pyrolysis of pine wood, pine bark, and hybrid poplar at six temperatures to determine resulting changes in physical and chemical properties. Product mass decreased with increasing temperature while O/C and H/C ratios decreased. The changes were related to a loss of oxygenated volatiles with phenolic and carboxyl functional groups, which also exposed cavities less than one nm in diameter and increased specific surface area. Increasing temperature thus reduced negative surface charge density and increased hydrophobicity. Absolute values of properties varied with biochar source but relative changes with temperature were similar. Biochars formed at higher temperatures also formed less oxygenated functional groups when oxidized in air at 250C and showed less loss of microporosity.

At Virginia Tech, Dr. Kang is conducting research on peptides that specifically bind to montmorillonite (2:1 layersilicate) and kaolinite (1:1 layersilicate), hematite (Fe2O3), alumina (Al2O3), and silica (SiO2). They identified the peptides using the phage display technique. It was demonstrated, using synchrotron-based spectroscopy, that small peptides adsorbed at a titled angle relative to surface of montmorillonite, however, the binding motif of a peptide significantly affects the degree of molecular orientation angle. We found strong evidence of preferential accrual of peptides/proteins over other organic nitrogen compounds associate with soil minerals in three independent undisturbed ecosystems developed across 4000, 20,000, and 60,000-year chronosequences, respectively. The result from this investigation strongly support that peptide/protein-mineral interaction plays an important role in affecting terrestrial N cycle. We have found that the mineral-associated organic C consists of four major species: aromatic-C, phenolic-C, aliphatic-C, carboxylic-C, and O/N-alkyl-C. The mineral-associated organic C speciation composition varied significantly during the soil development for all 3 independent soil chronosequences. The results from this investigation suggest continuous mineral sequestration and stabilization of aliphatic-C and O/N-alkyl-C compounds during soil development, while the aromatic-C compounds associated with soil minerals were continuously transformed into other C species. Bioavailable amino acids and organic C speciation in soils of north-south and west-east transects of continental United States were assessed. This study suggested that precipitation has more impact on modifying amino acid composition and soil organic C speciation than temperature.

1. Mainelis’s laboratory at Rutgers University continued investigation of risks associated with nanotechnology-enabled consumer products. As part of this investigation, we analyzed potential release of particles from nanotechnology-enabled clothing, with particular focus on clothing with silver nanoparticles. The TEM as well as various other analytical methods were used to determine the presence and quantity of silver in acquired clothing items. The potential release of particles into the air when clothing is worn was simulated by using a rotary abraser (Taber Industries Inc.) with felt abrading wheels. The experiments were performed in a specially-designed glove-box and the released particles were measured using a Scanning Mobility Particle Sizer (TSI Inc.) and an Aerodynamic Particle Sizer (TSI Inc.). These measurements were performed with brand new items as well as items that have been washed multiple times to simulate their natural wear and tear. TEM analysis showed the presence of nanoparticles in most items labeled as having silver nanoparticles, but their size and abundance depended on a particular product. The data obtained so far show showed that simulated wear of the items resulted in the release of nano-sized particles as well as submicron and super-micron agglomerates. The mode of the released particles by number was in the 1-2 micron range. This ongoing study is showing that the use of investigated nanotechnology-enabled clothing could result in the release of nanoparticles into the air, potentially leading to particle inhalation exposure. 

At the University of Illinois, Dr. Stucki is conducting research on the the effects of redox reactions of iron (Fe) on the physical, chemical, and colloidal properties of soils and constituent clay minerals. Methods being used include Mössbauer spectroscopy, X-ray powder diffraction, infrared spectroscopy, UV-Vis-NIR spectroscopy, GC-MS, and chemical analyses for the oxidation states of Fe, N, and other redox-sensitive elements. During this year we have focused on three specific objectives. (1) Determine the amount of tetrahedral Fe(III) in dioctahedral smectite clay minerals; (2) Measure the Mossbauer recoil-free fraction for structural Fe(II) and Fe(III) in dioctahedral smectites, including its temperature dependence; and (3) Quantify the reduction of nitrate by redox-modified, reversed-charge smectites. The amount of tetrahedral Fe(III) in clay minerals historically has been very difficult to quantify. In collaboration with French colleagues, we have identified specific features in the mid-infrared spectrum and in the Mossbauer spectra that are attributable to tetrahedral Fe(III). These results complement one another and represent the most important advancement made in recent years in providing a reliable strategy for making this determination. Promising UV-Visible features were also identified that seem to be attributable to tetrahedral Fe(III), but these have yet to be fully evaluated. Research into these features is ongoing. The recoil-free fraction in Mossbauer spectroscopy is analogous to the absorption coefficient in the Beer-Lambert Law for UV-Visible spectroscopy, and, if known, makes possible the calculation of the amount of Fe(III) or Fe(II) species in the clay mineral structure from the relative peak areas obtained by curve deconvolution of the Mossbauer spectrum. Until now, the recoil-free fraction has never been measured for smectites, so Mossbauer spectra could only be used for semi-quantitative work. Our work toward this objective is not quite finished, but most of the data has been collected and will be analyzed during this academic year. We hope to have a finished result by this time next year. Our studies have clearly shown that structural Fe(II) in smectites is a powerful reductant for nitrate in the surrounding water, but natural coulombic repulsion between the nitrate and the negatively charged smectite surfaces must first be overcome. We demonstrated that this charge reversal can be achieved by the adsorption of natural polymeric organic cations, after which the nitrate can be completely removed from solution. Reduction products include nitrite and ammonium. Results from tests for gaseous reactions products are not yet available, but are in progress. The distribution of N reactants and products have also been measured in both the solution and solid phases. In summary, the use of advanced chemical and spectroscopic methods, such as Mossbauer and infrared spectroscopy, has made significant progress possible toward the achievement of the stated objectives for this project. 

Dr. Strawn at the University of Idaho conducts research on several projects that effect production of food, environmental quality, and water quality. Phosphorus loading to surface waters is one of the greatest water impairment issues in the United States, and as a result, confined animal feeding operations (CAFO) are facing increased pressure to accurately manage manure and liquid waste to prevent nutrient transport. In Idaho, many dairies are only a few decades old, and long-term effects of waste management practices on nutrient availability are unknown. Long-term effects such as reaching an ecological phosphorus threshold could occur that will threaten environmental sustainability and the dairy industry. We are researching phosphorus chemistry and reaction processes to anticipate long-term effects so that defensible nutrient-management plans can be developed and implemented. To do this we are using advanced synchrotron spectroscopy, including both K-edge and L-edge X-ray absorption spectroscopy. Results provide direct speciation information about P in the manure-amended soils.

1. Abdala, D.B., , P.A. Northrup, F.C. Vicentin, and D.L. Sparks. 2015. Residence time and pH effects on the bonding configuration of orthophosphate surface complexes at the goethite/water interface as examined by Extended X-Ray Absorption Fine Structure (EXAFS) spectroscopy. J. Colloid Inter. Sci. 442: 15–2.
2. Abdala, D.B., P. A. Northrup, Y. Arai and D. L. Sparks. 2015. Surface loading effects on orthophosphate surface complexation at the goethite/water interface as examined by extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. . Colloid Interface. 437: 297–303.
3. Abdala, D.B.,I.R. da Silva, L. Vergutz and D.L. Sparks. 2015. Long-term manure application effects on phosphorus speciation, kinetics and distribution in highly weathered agricultural soils. Chemosphere 119: 504-514.
4. Anderson, S.H. 2015.       Shrinkage crack polygon. pp. 1940-1944. In H. Hargitai and A. Kereszturi (eds.) Encyclopedia of Planetary Landforms. Springer, New York, New York.
5. Anderson, S.H., D.J. Heinze, and R.L. Peyton. 2015. Assessment of selected methods for estimating chemical transport parameters from computed tomographic imaging. Procedia Computer Science 61:460-465.
6. Anderson, S.H., J.L. Holmes, and R.L. Peyton. 2015. Tomography-measured spatial distributions of non-aqueous phase liquids in porous media. Procedia Computer Science 61:466-471.
7. Aramrak, S., M. Flury, J.B. Harsh and R.L. Zollars. 2014. Colloid Mobilization and Transport during Capillary Fringe Fluctuations. Environmental Science & Technology 48: 7272-7279.
8. Baffaut, C., F. Ghidey, E.J. Sadler, and S.H. Anderson. 2015. Long-term agro-ecosystem research in the central Mississippi River Basin: SWAT simulation of flow and water quality in the Goodwater Creek Experimental Watershed. J. Environ. Qual. 44:84-96.
9. Baker L.L., D.G. Strawn 2014. Temperature effects on synthetic nontronite crystallinity and implications for nontronite formation in Columbia River Basalts. Clays and Clay Minerals, 62:2, 89-101.
10. Baker L.L., R.D. Nickerson, D.G. Strawn 2014. XAFS study of iron-substituted allophane and imogolite. Clays and Clay Minerals, 62: 1, 20-34.
11. Chen, C, R. Kukkadapu and D.L. Sparks. 2015. Influence of coprecipitated organic matter on Fe2+(aq) -catalyzed transformation of ferrihydrite: Implications for carbon dynamics. Environ. Sci. Technol. 49 (18): 10927–10936.
12. Chen, C. and D.L. Sparks. 2015. Multi-elemental scanning transmission X-ray microscopy–near edge X-ray absorption fine structure spectroscopy assessment of organo–mineral associations in soils from reduced environments. Environmental Chemistry 12(1):64-73.
13. Fischel, M.H.H., J.S. Fischel, B.J. Lafferty and D.L. Sparks. 2015. The influence of environmental conditions on kinetics of arsenite oxidation by manganese-oxides. Geochem Trans16:15.
14. Han, T., Wren, M., DuBois, K., Therkorn, J., and Mainelis, G. (2015). Development of ATP Bioluminescence Method for Rapid Bioaerosol Quantification. Journal of Aerosol Science, 90: 114-123[1].
15. Isaacman, G., N.M. Kreisberg, L.D. Yee, D.R. Worton, A.W.H. Chan, J.A. Moss, S.V. Hering, and A.H. Goldstein, Online derivatization for hourly measurements of gas- and particle-phase semi-volatile oxygenated organic compounds by thermal desorption aerosol gas chromatography (SV-TAG), Atmos. Meas. Tech., 7, 4417-4429, doi:10.5194/amt-7-4417-2014, 2014.
16. Jaisi. 2015. Characterizing phosphorus speciation of Chesapeake Bay sediments using chemical extraction, 31P NMR, and X-ray absorption fine structure spectroscopy. Environ. Sci. Technol. 49 (1): 203–211.
17. Knappenberger, T., M. Flury, E.D. Mattson and J.B. Harsh. 2014. Does Water Content or Flow Rate Control Colloid Transport in Unsaturated Porous Media? Environmental Science & Technology 48: 3791-3799.
18. Kravchenko, A.N., W. C. Negassa, A. K. Guber, and M.L. Rivers. 2015. Protection of soil carbon within macro-aggregates depends on intra-aggregate pore characteristics. Scientific Reports 5.
19. Li, T.Q., Q. Tao, M.J.I. Shohag, MJI, X.E. Yang, D.L. Sparks and Y.C. Liang. 2015. Root cell wall polysaccharides are involved in cadmium hyperaccumulation in Sedum alfredii. Plant Soil 389:387-399.
20. Li, W., S. R. Joshi, G. Hou, D. J. Burdige , D. L. Sparks, and D. P.
21. Milani, N., G.M. Hettiarachchi, D.G. Beak, M. J. McLaughlin, J. K. Kirby, and S. P. Stacey. 2015. Fate of zinc oxide nanoparticles coated onto macronutrient fertilizers in an alkaline calcareous soil. PLoS ONE 10(5): e0126275.
22. Nash, P.R., K.A. Nelson, P.P. Motavalli, and S.H. Anderson. 2015. Corn yield response to managed drainage and polymer-coated urea. Agron. J. 107:435-441.
23. Negassa, W., A. K. Guber, A. N. Kravchenko, T.L. Marsh, B. Hildebrandt, and M. L. Rivers. 2015. Properties of soil pore space regulate pathways of plant residue decomposition and community structure of associated bacteria. PLoS One.
24. O’Brien, R. E., A. Laskin, J. Laskin, C. L. Rubitschun, J. D. Surratt, and A. H. Goldstein, Molecular characterization of Sand N-containing organic constituents in ambient aerosols by negative ion mode high resolution Nanospray Desorption Electrospray Ionization Mass Spectrometry: CalNex 2010 field study, J. Geophys. Res. Atmos., 119, 12,706–12,720,
25. Olsen, T. A., Huang, T. H., Kanissery, R., & Hudson, R. J. (2015). Mercury-Thiourea Complex Ion Chromatography: Advances in System Chemistry and Applications to Environmental Mercury Speciation Analysis. In ACS Symposium Series (Vol. 1210, pp. 101-114).
26. Osborne, L.R., L.L. Baker, D.G. Strawn. 2015. Lead Immobilization and Phosphorus Availability in Phosphate-Amended, Mine-Contaminated Soils. Journal of Environmental Quality 44:183-190.
27. Sadler, E.J., R.N. Lerch, N.R. Kitchen, S.H. Anderson, C. Baffaut, K.A. Sudduth, A.A. Prato, R.J. Kremer, E.D. Vories, D.B. Myers, R. Broz, R.J. Miles, and F.J. Young. 2015. Long-term agro-ecosystem research in the Central Mississippi River Basin: Introduction, establishment, and overview. J. Environ. Qual. 44:3-12.
28. Suliman, W., J.B. Harsh, N.I. Abu-Lail, A.-M. Fortuna, I. Dallmeyer and M. Garcia-Perez. 2016. Influence of feedstock source and pyrolysis temperature on biochar bulk and surface properties. Biomass & Bioenergy 84: 37-48.
29. Todd A. Olsen, Tina H. Huang, Ramdas Kanissery, Robert J. M. Hudson. Chapter 6, pp 115-151. Trace Materials in Air, Soil, and Water. Editor(s): Kendra R. Evans et al. Volume 1210 December 1, 2015. American Chemical Society
30. Wu, Y., W. Li, and D. L. Sparks. 2015. Effect of iron(II) on arsenic sequestration by δ-MnO2: Desorption studies using stirred-flow experiments and x-ray absorption fine-structure spectroscopy. Environ. Sci. Technol. 49 (22): 13360–13368.
31. Wu, Y., W. Li, and D. L. Sparks. 2015. The effects of iron(II) on the kinetics of arsenic oxidation and sorption on manganese oxides. JCIS 457: 319–328.
32. Zeiger, S.J., J.A. Hubbart, S.H. Anderson, and M.C. Stambaugh. 2015. Quantifying and modeling urban stream temperature: A central US watershed study.       Hydrological Processes. 29:.
33. Zhang, Y., B.J. Williams, A.H. Goldstein, K. Docherty, I.M. Ulbrich & J.L. Jimenez, A Technique for Rapid Gas Chromatography Analysis Applied to Ambient Organic Aerosol Measurements from the Thermal Desorption Aerosol Gas Chromatograph (TAG), Aerosol Science and Technology, 48:11, 1166-1182, 2014.