Duration: 10/01/2010 to 09/30/2015

Administrative Advisor(s):

NIFA Reps:

Non-Technical Summary

Statement of Issues and Justification

A. The need as indicated by stakeholders.
Agricultural practices affect air, soil, and water quality for both rural and urban communities. The impacts flow both ways. Activities in urban settings affect soil and water quality for rural and agricultural use, while public concern and regulatory authority to protect the environment impel efforts to preserve and improve environmental quality. Efficient management and effective regulation will optimize environmental and health protection without crippling the economy, rural or urban.
The focus of Multistate Project NC-1022 is the behavior of particulate matter in size ranges capable of movement through air and water. Although this encompasses sizes from silt (2 - 50 µm) to the sub-micrometer range, never has the importance of assessing the impact of nanoparticles been so important. A 2003 report to CSREES from a National Planning Workshop outlines the potential benefits of nanotechnology to agriculture and food systems. Two of the concerns of the report, however, are (1) the potential for a backlash from the public similar to what has happened with genetic engineering and (2) a lack of knowledge of the environmental behavior of nanoparticles (Scott and Chen, 2003). The report states:
Novel materials developed through materials science and engineering are critical to the advancement of agriculture and food systems. Natural nanoparticles in soil, water, and air must be understood to the point that their characteristics and behavior can be controlled so that this natural resource may be more fully utilized. Agricultural practices also create and disperse nanoparticles. The environmental abundance of nanoparticles produced by agriculture must be understood and any negative effects mitigated.
Echoing this view is that of numerous government, industry, environmental and academic leaders from DuPont and Environmental Defense and committees of the Science Council of Japan and the British Royal Society. These and others have called for extensive research on identifying and assessing the potential risks of nanomaterials to human health and the environment. {Service, 2005}According to the National Science Foundation, nanotechnology will have a $1 trillion impact on the global economy while, at the time of the article, less than $46 million has gone to studies of nanomaterials impact on health and the environment from the largest funding sources--U.S. federal sources and the European Community.
The agricultural research community should take a lead role in such research. Not only are agricultural and food systems poised to benefit from nanotechnology, but have the research expertise and infrastructure in the land grant university system to determine the risks and benefits of nanoparticles. Project NC-1022 has been able to extend that expertise and infrastructure to national user facilities that make state of the art instrumentation and computer power available to our focus on particulate matter in air, soil, and water. Continuing this project will allow us to reap the benefits of the contacts we have established and expertise we have gained in the past.
B. The importance of the work and the consequences if not done.
The reactivity of soils with respect to plant nutrient elements and environmental toxins is to a very great extent dependent on reactions that involve particles with diameters of tens of micrometers or less (silt, clays, microbes, nanoparticles). Because these fine particles in soils are contained in a very complex mixture it is often impossible to gain a mechanistic understanding of processes governing the retention and mobility of many chemical species in soils by traditional techniques. For example, it is well known that the phosphorus is associated with fine particles (Hanley and Murphy, 1970), but the exact chemistry of these particles is not well understood. Recent work has demonstrated the utility of synchrotron x-ray microprobe spectroscopy for the study of the chemistry of P in the fine fraction of soils (Bloom, personal communications 2009). Copper, zinc and lead are enriched in the fine fraction of soil and the particle size is an important factor for the bioaccessibility of these elements (Madrid et al., 2008). A mechanistic understanding of the role of particle size in mobility and bioaccessibility will require a detailed understanding of the chemistry of soil particles at a scale that is only possible using advanced spectroscopic and microscopic instruments.
Recently questions concerning the environmental fate of nanoparticles arising from agricultural operations and from the manufacture, use or disposal of consumer products has arisen. Little is known about the toxicology and environmental behavior of these particles. These particles are very difficult to study because the particles are < 100 nm. The NC-1022 group is well poised to address the problems presented by the analytical difficulties that nanoparticles present. Our current access to synchrotron sources and the cooperation that has developed among members will serve to help solve the difficult problem of completely characterizing nanoparticles with a focus on their environmental and agricultural impact.
Without the combined efforts of the NC_1022 membership, agricultural research is at risk of falling behind in terms of using state-of-the-art instrumentation to solve problems related to particulate behavior in the environment. The availability of nutrients in sustainable systems depends on reactions at particulate surfaces that often must be observed at the microscopic scale. The transport of toxic contaminants is governed by the movement, dissolution, and nucleation of particulate matter. Microscopic and spectroscopic methods are needed to follow such particles, determine their static and dynamic composition, and to determine their availability to living organisms. The situation may be likened to the current ability to characterize microbial communities in natural systems by the analysis of genetic material. Without the application of molecular tools, we will not have the required knowledge to advance agricultural systems to minimize inputs and contamination while optimizing production and economy.
C. The technical feasibility of the research.
A common thread that runs through much environmental research is the importance of processes that operate simultaneously on different spatial and temporal scales. For instance, major questions surround particulate matter affecting rural air, soil, and water quality. The technical feasibility of applying synchrotron-based methods to a wide range of sample sizes and chemical compositions is amply supported by the current scientific literature. The utilization of a combination of techniques to accomplish full characterization of particles and to relate these properties to behavior in complex systems has become increasingly important and successful. We will extend these tested approaches to agricultural systems.
D. The advantages for doing the work as a multi-state effort.
There are several advantages in doing this project as a multi-state effort. First, particulate matter (PM) is transported across state and regional boundaries by both air and water making it a regional rather than local problem. Second, just as urban PM emissions vary considerably from one metropolitan area to another, we can expect rural PM emissions also vary because livestock industry, crops, farming practices, soils, and water chemistry vary regionally. Third, the central focus of this project (integrated modern instrumentation, including synchrotron microspectroscopy) demands extensive cooperation among members: sharing experience with specific facilities and analytical techniques and sharing disciplinary expertise (soil, water, and air chemistry, microbiology, etc.). Fourth, this project has two implicit strategies for reaching its objectives. It will continue to promote the use of synchrotron sources to push the envelope in terms of micro-spectroscopic characterization of particles and will integrate synchrotron techniques with other state-of-art-tools provided by national labs and universities. The latter logically begins with sharing samples and data for multiple analyses but would yield optimal progress if the collaborations went deeper. In the past, synchrotron research by soil scientists primarily focused on industrial contaminants, i.e., metals and metalloids. There are many opportunities now with micro-focused techniques to study agricultural contaminants such as metals, phosphate, etc. in biosolid amended soils and biosolid materials that will link more basic soil science with applied soil science, particularly in the area of nutrient management. Finally, the members have already established an excellent record of multi-state collaboration. There is no reason this will diminish.
E. What the likely impacts will be from successfully completing the work.
This project will enhance our ability to assess the impact of micro- and nano-sized particles on processes taking place in agricultural and natural ecosystems by elucidating links between particulate (physical, biological and chemical) properties and their role in the sustainability and productivity of those systems. Research activities coordinated under this project will result in a catalog of physical and chemical properties of particulates related to agriculture production and of evaluations of the rate and transfer mechanisms of particulates through the environment.
A greater number of scientists from state agricultural experiment stations will be utilizing the advanced analytical facilities funded by DOE and NSF to address important questions related to environmental protection and agricultural production. This will lead to the development a better understanding of the behavior of pollutant and nutrient elements and compounds associated with fine particles in soil, water and air.

Related, Current and Previous Work

A. Current Multi-State Projects Related to NC-1022:
The multi-state projects listed below are related to our proposed project in some manner. The potential for duplication arises either from the research focus of the project or its approach. Several projects address chemical aspects of soil and water quality but no other project integrates air, soil and water quality nor do any of these projects employ a integration of state-of-the-art instrumentation. This project would renew NC-1022, which promoted synchrotron methods in soil and water quality research. This project broadens the scope to include other modern spectroscopic, computer, and microscopic methods and sharpens the approach to emphasize biogeochemical interfaces and element cycling.
NRSP003: The National Atmospheric Deposition Program (NADP)
NC1031: Nanotechnology and Biosensors
NC1178: Impacts of Crop Residue Removal for Biofuel on Soils (formerly NC1017)
B. Summary of Previous Work from NC-1022:
Group meetings: A two-day meeting was held at Argonne National Laboratory June 20-21, 2005. Participants were: Beyrouty, Craig, Purdue Univ.; Bleam, William, Univ. Wisconsin; Bloom, Paul, Univ. Minnesota; Illman, Barbara, USDA-Forest Service, Madison, WI; Loeppert, Richard, Texas A&M Univ.; Schulze, Darrell, Purdue Univ.; Shea, Patrick, Univ. Nebraska; Sparks, Donald, Univ. Delaware; Steenhuis, Tammo, Cornell Univ.; Strawn, Daniel, Univ. Idaho; Taylor, Robert, Alabama A&M Univ.; and Teppen, Brian, Michigan State Univ. On June 20 research presentations were given to enable discussions of capabilities and methods of synchrotron work. A June 21 business meeting was held and a tour of the Advanced Photon Source followed.
The group met July 9, 2006 in Philadelphia in conjunction with the World Congress of Soil Science. Participants were: Bertsch, Paul, Univ. of Georgia; Cavallaro, Nancy, USDA Representive; Gimenez, Daniel, Rutgers Univ.; Harsh, James, Washington State Univ.; Hesterberg, Dean, NC State Univ.; Loeppert, Richard, Texas A&M Univ.; Mairelis, Gedi, Rutgers Univ.; Schlautmann, Mark, Clemson Univ.; Schulze, Darrell, Purdue Univ.; Smucker, Alvin, Michigan State Univ.; Strawn, Daniel, Univ. Idaho ; Teppen, Brian, Michigan State Univ.; and Turco, Ron, Purdue Univ. Presentations were made at the WCSS symposium Synchrotron Spectromicroscopy of Particulate Matter Affecting Air, Water and Soil organized by Will Bleam and Paul Bertsch. Fifteen papers were submitted. This symposium served as an outlet to a broader scientific audience for new research developments from members of NC-1022. The group decided to pursue funding to support a conference to explore a cross-disciplinary effort between atmospheric science and soil science and the potential to utilize synchrotron-based micro-spectroscopic techniques to better understand particle processes in agricultural systems. A conference grant was submitted to the NRI-USDA and funds were received. The group is discussing the thematic goals of the conference and planning for a conference in 2011 to avoid conflicts in 2010, especially with the WSSC and International Humic Substances Society Conference. Members interested in renewing the project with a new proposal met in Pittsburgh in November 2009 to refine the objectives of the proposal and assign tasks in proposal preparation. Attending were Dan Strawn, Jim Harsh, Dick Loeppert, Ron Turco, Nancy Cavallaro, Alvin Smucker, Daniel Gimenez, Kang Xia, Paul Bloom, Lyle Prunty, and Don Sparks. A timeline for preparation was developed and writing was assigned.
Group Accomplishments: Soil quality, health, and productivity are important components of agricultural productivity, natural resource protection and productivity, water quality, and environmental stewardship. Soil chemical processes are integral to all of these components. Members of the group used synchrotron spectroscopy and microscopy to better understand the biogeochemical reactions occurring in soils and air particulates. Results from the groups research are providing better remediation strategies, improved agricultural practices, and protection of soil resources. Beamtime at the synchrotron facilities is obtained by peer-review of proposals. Group members have applied for beamtime and been allocated time at all of the major facilities. Utilizing the beamlines provide impetus for beamline scientists and engineers to design the capabilities of the beamlines to accommodate environmentally relevant samples. Publishing in highly regarded journals helps raise the stature of group members, making our beamtime request proposals more likely to be appropriated beamtime.
Group members have published numerous papers in international research journals on molecular speciation and transformation of chemicals associated with environmental particles. This work includes, but is not limited to, studies of metal, metalloid, and xenobiotic availability to plants and microorganisms as affected by particle-element interactions (Howe, 2003; Khan, 2009; Masue, 2007; Hossain, 2008; Bloom, 2005; Khwaja, 2006; Qian, 2002; Skyllberg, 2006; Yoon, 2005; Jackson, 2005; Jackson, 2006; Punshon, 2005; Punshon, 2005; Sowder, 2003; Van Nostrand, 2007; Roberts, 2007; Roberts, 2007; Wendling, 2005; Wendling, 2005); toxicity and uptake of nanoparticles (Ma, 2009); bioavailability of plant nutrients (Hossain, 2009; Johnson, 2006); distribution and speciation of particle-associated elements in soil (Oram, 2008; Ryser, 2006; Strawn, 2008; Strawn, 2009; Livi, 2009; McNear, 2005; Paul, 2006; Scheidegger, 1996; Seiter, 2008; Toor, 2006; Chen, 2005; Mashal, 2005; Mon, 2005); transformations of metals and compounds on particle surfaces (Langell et al., 200x; Jackson, 2006; Powell, 2006; Punshon, 2003; Van Nostrand, 2007; Vacca, 2005; Ginder-Vogel, 2009; Hunger, 2008; Power, 2005; Usher, 2005; Zhu, 2009; Arroyo, 2005; Mashal, 2004; Mashal, 2005); adsorption of organics to soil minerals (Aggarwal, 2006; Aggarwal, 2006; Aggarwal, 2007; Charles, 2006; Charles, 2006; Charles, 2008; Li, 2006; Li, 2007; Liu, 2009; Pereira, 2007; Rana, 2009; Roberts, 2006; Wang, 2009) mobility of colloids and nanoparticles in soils (Chen, 2005; Mashal, 2005; Shang, 2008); and the role of soil particle surface on aggregation of soil particles and macro- and micro-porosity of soils (Kravchenko, 2009; Park, 2005; Peng, 2006; Peng, 2007; Peth, 2008; Pietola, 2006; Smucker, 2007).
C. Other related work:
Air Quality: Airborne emissions of particulates from confined animal feeding operations (CAFOs), such as poultry houses, are a major environmental issue facing the animal industry and regulatory agencies. In many areas of the USA, urbanization has resulted in increased population density in agricultural areas. Additionally, the movement toward larger, more concentrated animal production facilities has increased concerns over odor, particulate matter, and gaseous emissions (Marsh et al., 2003). Residents and environmental agencies have expressed increasing concern about the transport of particulates from the CAFOs and impacts on human health. It is not known if the particulates carry contaminants, such as toxic metals and metalloids, that could be harmful. The national ambient air quality standards (NAAQS) include two criteria pollutants directed toward particulates: particulate matter with an aerodynamic diameter less than 10 microns (PM10) and particulate matter with an aerodynamic diameter less than 2.5 microns(PM2.5). PM10 is scheduled to be replaced by PMcoarse, defined as particulate matter with an aerodynamic diameter between 10 and 2.5 microns. Livestock buildings, especially confined animal feeding operations (CAFOs), are a major source of gaseous and particulate matter emissions. The negative impact of these emissions on environmental and human health has raised concerns among federal and state regulatory agencies, including the Environmental Protection Agency (EPA) and state environmental agencies. As a result, air quality regulations, once limited to industry, are now being applied to agriculture.
Fate of Particulate-Associated Toxic Elements: Ammonia-related odor complaints are often the source of conflict among poultry growers, integrators, and residential neighbors; however, from a human and environmental health perspective, it is critical to understand the heavy metal concentration, distribution, and speciation in both PMcoarse and PM2.5. PMcoarse is inhalable; PM2.5 is both inhalable and respirable; and the health effects posed by each size range are likely to be different. Poultry house PM is generated by both the bird and bedding materials and contains pulverized fecal material, feed particles, feathers and epidermal fragments of skin. The dust particles may contain high levels of ash, nitrogen, calcium, iron, zinc, copper, arsenic, magnesium, and/or aluminum (Ellen, et al., 2000; Nakaue, et al., 1981). Wet and dry deposition of these particles may result in heavy metal contamination of the surrounding landscape. In addition to concentration, the environmental toxicity of heavy metals is determined in large part by their speciation (i.e., oxidation state, mineralogy), which determines a metals bioavailability and mobility. Arsenic, for example, generally exists in the environment as either As(III), which is highly mobile in the environment and toxic, or As(V), which is less toxic and mobile. Additionally, trace metals often serve as unique tracers of PM from specific point sources (Reinard et al., 2007). It is possible that the distribution of metals within poultry house PM will provide a means for tracking these emissions in the environment. In a similar vein, Bloom and Toner are using an x-ray microprobe at the Advanced Photon Source (APS) beamline 2-ID-B to study the chemistry P in soils heavily impacted with sewage sludge. In these soils most of the P is in the <5 micrometer size fraction. Toner is also using beam lines 20-BM-B and 13-BM-B at APS to study arsenic in aquifer materials where well waters exceed the USEPA maximum contaminant levels for drinking water (Bloom, pers. comm., Univ. Minnesota).
Environmental Impacts of Nanoparticles: Despite the realized and predicted benefits of nanotechnology, concerns surrounding potential negative impacts to the environment and human health cannot be dismissed (Colvin, 2003; Masciangioli and Zhang, 2003; Service, 2004; Wiesner et al., 2006; Warheit, 2004; Dagani and Washington, 2003; Kovochich et al., 2007; Meyer et al., 2009), as information on potential effects to human and ecological receptors accumulates (Nel et al., 2009; Klaine et al., 2008). Still, the field is in its infancy and unifying principles have yet to be identified. Moreover, despite early exposure assessments (Koelmans et al., 2008; Auffan et al., 2009) suggesting that manufactured nanomaterials (MNMs) currently being produced in high tonnage (i.e., Ag, TiO2, ZnO, CeO2) are most likely to accumulate in biosolids (BS) from wastewater treatment processes (WWTP) and ultimately in soil, most work has focused on aquatic systems leaving a critical gap in our knowledge of MNM behavior and effects in terrestrial ecosystems. The problem is complex, considering the vast diversity in chemical composition, size, shape, and surface chemical properties of MNMs, as well as the range of receptor species and cell lines investigated (Wiesner et al., 2006; Klaine et al., 2008; Auffan et al., 2009; Kovochich et al., 2007). As the utilization of MNMs is currently in an exponential growth phase (Meyer et al., 2009) there is great urgency to assess risks to humans and the environment and determine the necessity of mitigation actions.
There is a compelling need to examine the terrestrial transport, fate, bioavailability, and effects of MNMs under environmentally realistic scenarios. The soil resource forms the base of the ecosystem services pyramid, which ultimately controls the function of natural and managed ecosystems, delivering food, feed, fiber, and renewable fuels as well as sufficient high quality water. Thus, the potential impacts of MNMs released to soil on terrestrial ecosystem function as well as potential terrestrial-based pathways for human exposure must be understood to evaluate direct and indirect risks (Robichaud et al., 2009; Kiser et al., 2009). At the same time the ability to isolate and measure manufactured MNMs in soil and other environmental samples, including biota is extremely challenging and requires a suite of advanced analytical techniques. Among these are synchrotron based X-ray microanalysis along with HR-TEM and advanced separations/detection methods, such as asymmetric flow field flow fractionation coupled to dynamic laser light scattering, UV, Fluorescence, and ICP-MS detectors.

Objectives

1. 1. Determine the physical, chemical, and biological nature of particulate matter, including nanoparticles, derived from agricultural practices, processes, and operations and from the production, use, and disposal of consumer products, as they impact air, water, and soil quality and associated health, economic, and environmental impacts, including ecological sustainability and agricultural production.
   
2. 2. Determine those particulate matter properties that control the cycling, biological availability, and uptake (by microorganisms, plants, animals) of nanoparticles, nutrients, carbon, and toxic substances in air, water, and soil systems. This will include characterization and modeling of chemical behavior at interfaces in air, water, and soil systems that govern the transfer of particulate matter and dissolved components among environmental phases.
   
3. 3. Upgrade the skills of project participants to do research in heterogeneous environmental systems at the micro- and nano-meter scale. This will include: (a) integration of modern analytical instruments and techniques that can provide data to answer the complex questions raised in the first two objectives; (b) to educate participants and the wider the community of agricultural researchers in the use and availability of these techniques and instruments; and (c) to interact with national laboratory facilities at Argonne, Brookhaven, and Hanford to promote their use in the agricultural sciences and assist in the development and acquisition of equipment and expertise relevant to the agricultural science community.
   

Methods

Objectives 1 and 2. In order to understand the complex interactions that govern the weathering, transport, toxicity, mobility, and availability of particulates in complex agricultural systems, an integrated approach is required. Synchrotron-based techniques have emerged as powerful tools for determining the chemical speciation of a wide variety of toxic elements in moist soil samples, waste-forms, and biological specimens with little or no chemical pretreatment at detection limits and spatial resolutions that, on the average, exceed those of conventional methods by several orders-of-magnitude. At the same time, more conventional techniques have continued to improve in terms of resolution, sensitivity, and ability to perform under realistic conditions, such as those found in the vicinity of a plant root. By integrating a range of analytical methods, we can study both the nature of particulate matter and its behavior under a variety of environmental conditions. Environmental particles are characterized by physical heterogeneity and chemical complexity. High spatial resolution and chemical specificity is critical for understanding the biogeochemistry of key elements such as iron. Tools that allow one to access the nm-µm spatial scales of heterogeneity and complexity in samples are essential for obtaining interpretable results. For example, the reactivity and bioavailability of iron is dictated by speciation. Direct measurement of speciation in bulk materials generally produces an average signal that is not decipherable. The large suite of nano-particulate mineral phases, complexes with natural organic matter, and associations with microbial biofilms are best assessed directly and individually through X-ray nano-probe or micro-probe measurements. An additional advantage of many modern instruments (e.g., synchrotron-based x-ray absorption instruments, electron microscopes, scanning force microscopes) is compatibility with samples in ambient conditions--liquid water and ambient or relevant pressure. The past decade has witnessed significant advances in technologies related to spatially resolved X-ray spectroscopic techniques, both as a result of advances in X-ray optics, focusing devices, and detectors and because of greater availability of high brilliance synchrotron facilities world-wide. This includes the Advanced Photon Source (APS) at the Argonne National Laboratory, the Advanced Light Source (ALS) in Berkeley CA, the updated Stanford Synchrotron Radiation Lightsource (SSRL), and the National Synchrotron Light Source II (NSLS-II) that is under construction at the Brookhaven National Laboratory. The result is that spatially resolved synchrotron-based X-ray fluorescence (XRF), X-ray absorption near edge structure spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have become mainstream techniques in a number of scientific disciplines and are providing molecular- level information not previously available using other techniques. While there exists a variety of micro-analytical techniques that have long been used in these disciplines, synchrotron-based spatially resolved X-ray fluorescence spectroscopy (XRF), XANES, EXAFS spectroscopy, and X-ray diffraction (XRD) are emerging as important methods that complement characterization by traditional techniques, as well as by other emerging methods, such as spatially resolved luminescence, FTIR, and Raman spectroscopy. The reasons for this are the elemental specificity, low detection limits, non-destructive nature of the measurement, the ability, in many instances, to examine samples in situ, and the ability to extract information on valence states and on specific bonding environments or molecular forms of target elements in complex matrices. X-ray fluorescence has been long used as a technique for determining elemental concentrations in a variety of matrices (Bertsch and Hunter 2001). Synchrotron-based XRF techniques have decreased the detection limits by several orders-of-magnitude over conventional XRF techniques, being in the 50-100 ng g-1 range for many elements at third generation synchrotron facilities. Additionally, the enhanced brilliance of modern synchrotron facilities and advances in focusing optics, allow for spatial resolution down to approximately 1 µm for hard X-rays (>3 keV). In the soft X-ray energy range (<1keV), new tools such as scanning transmission X-ray microscopy (STXM) at the ALS provide ~20 nm spatial resolution for imaging, elemental/chemical mapping, and spectroscopy. The ability to access both hard and soft X-rays allows the investigation of most important nutrient elements (P, S, B, N and C), as well as transition and heavier elements. Spatially resolved XRF imaging has become a critical complementary technique that is a prerequisite for conducting spatially resolved X-ray absorption spectroscopy (XAS) and XRD for samples with heterogeneous distributions of target elements. Because spatially resolved XRF is a relatively rapid method, it can be used to efficiently examine complex samples to determine if there is heterogeneous elemental distributions on a spatial scale that is resolvable by the technique. It is now widely accepted that specific information on the composition, surface characteristics, and morphology of particulate matter is prerequisite to the development of a comprehensive understanding of toxic element and nutrient behavior in soils and sediments. For example, phosphorous interacts with oxide surfaces to form strong chemical complexes that may reduce its availability to plants or transport to ground and surface waters. On the other hand, colloidal transport by wind or water may hasten the mobility of phosphorous while removing it from a cropping system. The nature of not only the P-soil interaction, but the nature of the particle itself and its susceptibility to movement must be determined. This cannot be done by any one instrument or investigator. We will apply a mixture of spectroscopic, computational, and analytical methods to particles in complex systems such as soils and sediments under environmentally relevant conditions, for example on moist samples using minimal or no chemical pretreatment. Our members are directly involved in the application of these methods to environmental particles. James Harsh will use cryo-electron microscopy to characterized biofilm-mineral-root interactions in a microcosm environment. Dan Strawn is conducting research on Fe speciation in poorly crystalline nanoparticles that occur in nature using XAFS, Mossbauer, and infrared spectroscopy. This project is using facilities at SSRL, and NASA research centers. He will use NMR, infrared, and electron spectroscopy to characterize mineral and C speciation in biochar. The project has microbial and plant growth components. Steven Andersons efforts and expertise are in the area of physical characterization using computed microtomography of soil materials using both the NSLS and APS facilities. He and his collaborators are working to characterize wind transported materials as affected by agroforestry buffers. Paul Bertsch is one of the pioneers in the application of x-ray absorption spectroscopy and fluorescence to the the characterization and impacts of nanoparticles in the environment. Objective 3. While there is growth in the number of micro- and nano-probe instruments at synchrotron facilities worldwide, the scientific user base for these tools in earth and environmental science is under developed. Specifically, these types of instrument lines are frequently over subscribed and it can be difficult to gain access. Due to the scarcity of instrument time, fully developed research programs where statistically responsible sampling can be employed are limited. An additional, and more problematic issue for new synchrotron users is gaining the knowledge required to conduct high-quality measurements and analyze, interpret, and publish meaningful data. We will facilitate the transfer of synchrotron-radiation expertise to new instrument users, and play a key role in helping these tools fulfill their promise for high-quality, high-impact environmental research over the next decade. Currently, NC_1022 has two representatives on the Board of Governors of the Consortium of Advance Radiation Sources at the Advanced Photon Source (APS) of Argonne National LaboratoryWill Bleam, who will continue, and Darrell Schulze, who will not be a member of the new project. Kang Xia will be our new second representative and we will appoint an alternative representative to fill in when one member is unable to attend. These representatives voice our scientific concerns to CARS and help implement upgrades relevant to agricultural/environmental issues. For example, current upgrades to Sector 13 will extend the range of elements that can be characterized by the microprobe to below sulfur, opening an avenue to examine particles and elements critical to agricultural concerns such as Ca, Al, Si, K, and Cl. The upgrade will also reduce the focused spot size to as small as 250 nm, bringing microprobe techology to the nanoparticle realm. Our group is the only participant of the CARS groups (EnviroCARS) that is addressing environmental and agricultural concerns. Other advanced analytical techniques are also at available at national advanced analytical centers. The Environmental Molecular Science laboratory (EMSL) is a national scientific user facility at the Pacific Northwest National Laboratory that has a number of instruments that could be of use for the study of soils and sediments. This includes spatially resolved luminescence (FTIR, and Raman spectroscopy) and various electron spectroscopy techniques including HREELS and UHV surface chemistry. An NMR facility is available, which includes eleven NMR spectrometers, ranging from 300 MHz to 900 MHz with capabilities for high-field liquid-state, solid-state, and micro-imaging techniques. Washington State University has a faculty memberProf. Kerry Hipps--on the EMSL user committee and Harsh, who has served on this committee in the past, communicates regularly with him on needs for environmental research. The Molecular Science Computing Facility at EMSL is a unique facility equipped with a high-performance supercomputer, computational resources, and expert staff tailored to address computational challenges at multiscale in the environmental sciences. Computational approaches in combination with experimental investigations make it possible to couple phenomena across scales (from molecular to ecosystem levels) to generate mechanistic understanding of complex interactions in the environment. For example, at the EMSL environmental computational modeling has been used to address complex environmental cleanup problems, to advance the understanding of aerosol chemistry, and to explore the environmental behavior and toxicity of nano particles (Bose et al, 2009; Wan et al., 2008, 2009; Zhang et al., 2009; Hess et al., 2009). Specialized instrument facilities, funded by the National Science Foundation and located at universities around the country, also have instruments that can assist in meeting the objectives of NC-1022. Our members can help educate new usersgraduate students, scientists, and educatorsin the application of modern instrumentation to characterization of particulate matter. This can be accomplished through seminars, symposia, books, cooperative proposals, and organized tours at national facilities. As discussed above, we will continue to interact with users groups and administration of synchrotron and other major instrument facitilities, such the EMSL to open them to our members and other researchers in the agricultural community. We have been successful in this in the past and will expand to facilities beyond the synchrotron sources. Management Plan: The members of this project will seek funding from the USDA Agriculture and Food Research Initiative Competitive Grants Program, National Science Foundation Geobiology, Hydrology, and Ecology Programs, the Department of Energys Environmental Remediation Sciences Program, and other funding sources for projects that will use national and university user facilities to accomplish tasks that require integration of multiple instrumentation. This is the essence of Objectives 1 and 2. To facilitate cooperation among project participants we will organize annual meetings for sharing of ideas and research results. When possible, these meetings will be held on sites of advanced analytic facilities. Discussions with facility scientists and facility tours will be part of the meetings. In addition we will host a Bouyoucos symposium on uses of synchrotron x-ray techniques in soil science in 2011. The project leaders will edit a synthesis document describing the accomplishments of this project in terms of scientific and social advances. All members are responsible for creating links to user facilities and conveying information on availability and capabilities to the membership. Will Bleam and Kang Xia, as representatives on the current CARS Board of Governors for the APS, will communicate upgrades, proposal deadlines, and new capabilities of the facility.

Measurement of Progress and Results

Outputs

• Publications in peer-reviewed journals: The journals will include high-impact journals in the field of particulate science, including Environmental Science and Technology, Langmuir, SSSAJ, and Geochimica Cosmochimica Acta.
• Presentations at national/international meetings: These include those of the American Chemical Society, American Geophysical Union, American Society of Agronomy, and Clay Minerals Society.
• Proposals submitted to private, federal, and multinational funding sources: NSF, DOE, AFRI.
• Annual meetings of NC-1022 group that coordinate with tours of national user facilities, symposia at national society meetings, and conferences organized by NC-1022 participants.
• Bouyoucos Conference to be organized and held summer, 2011. Organizers are Alvin Smucker, Paul Bloom, Brandy Toner, and Steven Anderson.
• Output 6 A synthesis documente.g., a monograph on advanced instrumentation applied to particulate matterwill be published by the end of the project.

Outcomes or Projected Impacts

• Generate new fundamental knowledge of the properties of micro-and nano-meter scale particles in air, soil, and water. We will examine particles in agricultural systems that directly impact the availability of nutrients and to water and living organisms. Microscopic and spectroscopic methods will be used to characterize the locations, bonding mechanisms, and concentrations of P, K, Fe, micronutrients, and contaminant species associated with organic and inorganic particles.
• Characterization of particles will be combined with macroscopic studies to link the thermodynamics and kinetics of dissolution and transport to the microscopic and molecular characterization in order to link particle properties with environmental behavior. We will develop mechanistic models for the partitioning of material at interfaces to link micro- and nano-meter scale processes to mass transfer at larger scales. These models will be applied to environmental and agricultural systems, including interactions between minerals and plant roots, atmosphere and air-borne particles, sediment and water, and nanoparticles and microbial cells.
• Increase the utilization of national laboratory supported advanced analytical techniques by agricultural scientists. Members will use their contacts and influence on user committees of national laboratories and other service centers to gain access to state-of-the-art instrumentation. In addition, they will inform other members of the availability and capabilities of instrumentation through seminars, email, and posts to the project homepage. Each member will work to educate and encourage colleagues and collaborators at their institutions in the use and means of accessing modern instrumentation, including synchrotron sources and national user facilities.

Milestones

(2010): 1. Final Report Working Group formed to prepare report for previous project; 2. User Facility Group Formation. This group will determine the availability and composition of modern user facilities and report the protocol for submitting proposals and collaborating with facility scientists; 3. Organizing committee formed for planning of Bouyoucos Conference--plan developed.

(2011): 1. Hold Bouyoucos Conference; 2. A Proposal Working Group formed to gather information on funding sources for particulate research that updates the membership and looks for opportunities for multi-investigator proposals using NC-1022 membership.

(2012): 1.Publication of the Results of the Bouyoucos Conference in a special issue of a high impact soil science journal; 2. Develop New and Evaluate Existing Relations with User Facilities. Using the special relationship between NC1022 and national synchrotron facilities such as APS as a model, form similar bonds with national labs, including EMSL, the Advanced Light Source (Berkeley), and user facilities at universities.

(2013): Submission of Multi-Investigator Proposals to appropriate federal agencies (2012-2015). The proposal preparation will be coordinated by the Proposal Working Group.

(2014): 1. Plan for symposia at international meetings that showcase NC-1022 accomplishments; 2. Evaluate success of multi-investigator proposal submissions.

(2015): 1. Prepare synthesis document of project accomplishments and future research needs; 2. Discuss potential for future Multistate project.

Projected Participation

View Appendix E: Participation

Outreach Plan

1. Continuation and expansion of relations with national user facilities including membership on user committees, submission of white papers on user facility needs for agriculture, and interaction with specific facility scientists to develop instruments and methods germane to agricultural research2. Develop complementary research methods to solve difficult problems in particulate matter characterization an behavior requiring multi-instrumental expertise and availability. . To stimulate this outreach objective we will first develop the white paper on user facility needs and capabilities for agriculture. This will serve to focus member skills, interests, and needs. Step one of white paper planning will be to organize a sub-committee to lead white paper development. The subcommittee will survey Group members on their advanced analytical needs for agriculture research. The white paper will be used as a directive when communicating Group activities and interests to funding agencies and synchrotron development groups. It will serve as an advocacy document that members can use when interacting with facility governing boards. This document will be posted on the Project Homepage.

3. Hold workshops, conferences, and short courses that educate agricultural scientists as to the availability, application, and use of modern instruments for particulate matter research. Members will present their research at professional society meetings to educate other scientists of the value and capabilities of advanced molecular scale facilities. The group is also organizing a Bouyoucos conference on advanced molecular methods for studying soil processes that will have both specialists and non-specialists, including students, in attendance. Because most Group members are have State Agriculture Experiment Station (AES) appointments, research that utilizes advanced analytical facilities will be reported to constituents (e.g., Ag-day), and AES members and administrators.

Organization/Governance

Governance of the multi-state project will lie with three elected positions: chair, vice-chair and secretary. Each position is assigned specific tasks and is held for two years with officers rotating through the positions as follows: the chair steps down, the vice-chair becomes chair, the secretary becomes vice-chair and a newly elected individual becomes secretary. Appointed last meeting: Harsh (chair), Daniel Gimenez (vice-chair), and Daniel Strawn (secretary).
The chair is responsible for organizing the technical program for the upcoming "all hands" meeting. Each official group on the multi-state project is required to present a research report at each "all hands" meeting. If synchrotron funding is secured, each group allocated synchrotron time (Objective 3) during a given year is required to attend the "all hands" meeting and present a research report. The research report will consist of an abstract and either an oral presentation or a poster presentation. If synchrotron funding is secured, the chair will be the official liaison with funding source(s) and synchrotron facilities consistent with Objective 3. The vice-chair is responsible for organizing the logistics for the "all hands" meeting: selecting a venue, reserving rooms suitable for research presentations and the business meeting, arranging housing, etc. The secretary is responsible for all communication with official members of the multi-state project and, if synchrotron funding is secured, individuals allocated synchrotron time through Objective 3. The secretary is also responsible for preparing the annual report for the multi-state project, which will include the proceedings of the "all hands" meeting: minutes of the business meeting, the technical program, and the abstracts of all research reports.

All members are responsible for creating links to user facilities and conveying information on availability and capabilities to the membership. For example, William Bleam and Kang Xia, as representatives on the current CARS Board of Governors for the APS, will communicate upgrades, proposal deadlines, and new capabilities of the facility. James Harsh will keep members apprised of developments and RFPs from the EMSL at Pacific Northwest Laboratory. He also has access to the Geoanalytical Services Laboratory at Washington State University, which runs a high level radioisotope lab. Daniel Strawn will inform members of the capabilities and access to the Stanford Synchrotron Radiation Light Source and NASA research centers. Other members have experience with many facilities across the country and can expand their role to bring this knowledge to the membership. Steven Anderson uses synchrotron facilities at Brookhaven National Synchrotron Light Source (NSLS) and is using a FEI Quanta 600 FEG Extended Vacuum Scanning Electron Microscope (ESEM) at the University of Missouris Electron Microscopy Core Facility. This instrument can allow evaluation of specimens to a nm-scale without the need for particle coating. Paul Bloom uses the APS and the Canadian Light Source and is on the board of directors of the International Humic Substances Society, an organization that is interested in the micro and nano scale behavior of natural organic matter and its interactions with inorganic components in soil. These linkages and more will serve to expand the groups ability to access instrumentation and collaborate with colleagues on research at the cutting edge of particle characterization and behavior and to bring this knowledge to the agricultural community.

Literature Cited

Aggarwal, V., H. Li, and B.J. Teppen. 2006a. Triazine adsorption by saponite and beidellite clay minerals. Environmental Toxicology and Chemistry 25:392-399.

Aggarwal, V., H. Li, S.A. Boyd, and B.J. Teppen. 2006b. Enhanced sorption of trichloroethene by smectite clay exchanged with Cs+. Environmental Science & Technology 40:894-899.

Aggarwal, V., Y.Y. Chien, and B.J. Teppen. 2007. Molecular simulations to estimate thermodynamics for adsorption of polar organic solutes to montmorillonite. European Journal of Soil Science 58:945-957.
Arroyo, L.J., F. Li, B.J. Teppen, C.T. Johnston, and S.A. Boyd. 2005. Oxidation of 1-naphtmol coupled to reduction of structural Fe3+ in smectite. Clays and Clay Minerals 53:587-596.

Auffan, M., J. Rose, M.R. Wiesner, and J.-Y. Bottero, 2009. Chemical stability of metallic nanoparticles: A parameter controlling their potential cellular toxicity in vitro. Environ. Pollut., 157(4):1127-1133.

Beauchemin, S., D. Hesterberg, and M. Beauchemin. 2002. Principal component analysis approach for modeling sulfur K-XANES spectra of humic acids. Soil Science Society of America Journal 66:83-91.

Bloom, P.R., A.R. Khwaja, and P.L. Brezonik. 2005. Hg2+ bonding in soil humic acid and equilibrium partitioning in suspension. Geochimica Et Cosmochimica Acta 69:A542-A542.

Bose, S., M.F. Hochella, Y.A. Gorby, D.W. Kennedy, D.E. McCready, A.S. Madden, and B.H. Lower. 2009. Bioreduction of hematite(nanoparticles by the dissimilatory iron reducing bacterium Shewanella(oneidensis MR-1. Geochimica et Cosmochimica Acta 73:14.


Brown, T.T., R.T. Koenig, D.R. Huggins, J.B. Harsh, and R.E. Rossi. 2008. Lime effects on soil acidity, crop yield, and aluminum chemistry in direct-seeded cropping systems. Soil Science Society of America Journal 72:634-640.

Butler, D.M., D.H. Franklin, M.L. Cabrera, A.S. Tasistro, K. Xia, and L.T. West. 2008. Evaluating aeration techniques for decreasing phosphorus export from grasslands receiving manure. Journal of Environmental Quality 37:1279-1287.

Charles, S., B.J. Teppen, H. Li, D.A. Laird, and S.A. Boyd. 2006a. Exchangeable cation hydration properties strongly influence soil sorption of nitroaromatic compounds. Soil Science Society of America Journal 70:1470-1479.

Charles, S.M., H. Li, B.J. Teppen, and S.A. Boyd. 2006b. Quantifying the availability of clay surfaces in soils for adsorption of nitrocyanobenzene and diuron. Environmental Science & Technology 40:7751-7756.

Charles, S.M., B.J. Teppen, H. Li, and S.A. Boyd. 2008. Fractional availability of smectite surfaces in soils for adsorption of nitroaromatic compounds in relation to soil and solute properties. Soil Science Society of America Journal 72:586-594.

Chen, G., M. Flury, J.B. Harsh, and P.C. Lichtner. 2005. Colloid-facilitated transport of cesium in variably saturated Hanford sediments. Environmental Science & Technology 39:3435-3442.

Colvin, V. L. 2003. The potential environmental impact of engineered nanomaterials. Nat. Biotechnol., 21(10):1166-1170.

Dagani, R., and C.E. Washington. 2003. Nanomaterials: safe or unsafe? Chem. Engineer. News, April 28, 2003:30-33.

Deng, Y.J., J.B. Dixon, G.N. White, R.H. Loeppert, and A.S.R. Juo. 2006. Bonding between polyacrylamide and smectite. Colloids and Surfaces a-Physicochemical and Engineering Aspects 281:82-91.

Ellen, H.H., R.W. Bottcher, E. von Wachenfelt, and H. Takai. 2000. Dust levels and control methods in poultry houses. Journal of Agricultural Safety and Health 6(4): 275-282.

Everhart, J.L., D. McNear, E. Peltier, D. van der Lelie, R.L. Chaney, and D.L. Sparks. 2006. Assessing nickel bioavailability in smelter-contaminated soils. Science of the Total Environment 367:732-744.

Fernando, W., K. Xia, and C.W. Rice. 2005. Sorption and desorption of ammonium from liquid swine waste in soils. Soil Science Society of America Journal 69:1057-1065.

Ferrell, J.A., W.K. Vencill, K. Xia, and T.L. Grey. 2005. Sorption and desorption of flumioxazin to soil, clay minerals and ion-exchange resin. Pest Management Science 61:40-46.

Ginder-Vogel, M., G. Landrot, J.S. Fischel, and D.L. Sparks. 2009. Quantification of rapid environmental redox processes with quick-scanning x-ray absorption spectroscopy (Q-XAS). Proceedings of the National Academy of Sciences of the United States of America 106:16124-16128.

Hanley , P.K. and M.D. Murphy. 1970. Phosphate forms in particle size separates of Irish soils in relation to drainage and parent materials. Soil Sci. Soc. Am Proc . 34:587-590.

Hess, N.J., G.K. Schenter, M.R. Hartman, L.L. Daemen, T.E. Proffen, S.M. Kathmann, C.J. Mundy, M.A. Hartl, D.J. Heldebrant, A.C. Stowe, and T. Autrey. 2009. Neutron Powder Diffraction(and Molecular Simulation Study of the Structural Evolution of Ammonia Borane(from 15 to 340 K. Journal of Physical(Chemistry A 113:12.

Hossain, M.B., M. Jahiruddin, G.M. Panaullah, R.H. Loeppert, M.R. Islam, and J.M. Duxbury. 2008. Spatial variability of arsenic concentration in soils and plants, and its relationship with iron, manganese and phosphorus. Environmental Pollution 156:739-744.

Hossain, M.B., M. Jahiruddin, R.H. Loeppert, G.M. Panaullah, M.R. Islam, and J.M. Duxbury. 2009. The effects of iron plaque and phosphorus on yield and arsenic accumulation in rice. Plant and Soil 317:167-176.

Howe, J.A., R.H. Loeppert, V.J. Derose, D.B. Hunter, and P.M. Bertsch. 2003. Localization and speciation of chromium in subterranean clover using XRF, XANES, and EPR spectroscopy. Environmental Science & Technology 37:4091-4097.

Hunger, S., J.T. Sims, and D.L. Sparks. 2008. Evidence for struvite in poultry litter: Effect of storage and drying. Journal of Environmental Quality 37:1617-1625.

Jackson, B.P., J.C. Seaman, and P.M. Bertsch. 2006. Fate of arsenic compounds in poultry litter upon land application. Chemosphere 65:2028-2034.

Jackson, B.P., J.F. Ranville, P.M. Bertsch, and A.G. Sowder. 2005. Characterization of colloidal and humic-bound Ni and U in the "dissolved" fraction of contaminated sediment extracts. Environmental Science & Technology 39:2478-2485.

Johnson, S.E., and R.H. Loeppert. 2006. Role of organic acids in phosphate mobilization from iron oxide. Soil Science Society of America Journal 70:222-234.

Khan, M.A., M.R. Islam, G.M. Panaullah, J.M. Duxbury, M. Jahiruddin, and R.H. Loeppert. 2009. Fate of irrigation-water arsenic in rice soils of Bangladesh. Plant and Soil 322:263-277.

Khwaja, A.R., P.R. Bloom, and P.L. Brezonik. 2006. Binding constants of divalent mercury (Hg2+) in soil humic acids and soil organic matter. Environmental Science & Technology 40:844-849.

Kiser, M.A., P. Westerhoff, T. Benn, Y. Wang, J. Perez-Rivera, and K. Hristovski. 2009. Titanium Nanomaterial Removal and Release from Wastewater Treatment Plants. Environ. Sci. Technol. 43:6757-6763.

Klaine, S. J., P.J.J. Alvarez, G.E. Batley, T.F. Fernandes, R.D. Handy, D.Y. Lyon, S. Mahendra, M.J. McLaughlin, and J.R. Lead. 2008. Nanomaterials in the environment: Behavior, fate, bioavailability, and effects. Environ. Toxicol. Chem. 27(9):1825-1851.

Koelmans, A. A., B. Nowack, and M.R. Wiesner. 2009. Comparison of manufactured and black carbon nanoparticle concentrations in aquatic sediments. Environ. Pollut., 157(4):1110-1116.

Kovochich, M., T.Xia, J. Xu, J. Yeh, A. and Nel, A. 2007. Principles and Procedures to Assess Nanomaterial Toxicity. pp. 205-230. In: M. Wiesner and J-Y. Bottero (eds.) Environmental Nanotechnology - Applications and Impacts of Nano-materials. McGraw Hill: New York. 540 pp.

Kravchenko, A.N., M.A. Martin, A.J.M. Smucker, and M.L. Rivers. 2009. Limitations in Determining Multifractal Spectra from Pore-Solid Soil Aggregate Images. Vadose Zone Journal 8:220-226.

Lafferty, B.J., and R.H. Loeppert. 2005. Methyl arsenic adsorption and desorption behavior on iron oxides. Environmental Science & Technology 39:2120-2127.

Langell, M.A., E. Kadossov, H. Boparai, and P. Shea. 2009. Effect of sodium dithionite on the surface composition of iron-containing aquifer sediment. Surf. Interface Anal. 41:941-950.

Li, H., B.J. Teppen, D.A. Laird, C.T. Johnston, and S.A. Boyd. 2006. Effects of increasing potassium chloride and calcium chloride ionic strength on pesticide sorption by potassium- and calcium-smectite. Soil Science Society of America Journal 70:1889-1895.

Li, H., T.R. Pereira, B.J. Teppen, D.A. Laird, C.T. Johnston, and S.A. Boyd. 2007. Ionic strength-induced formation of smectite quasicrystals enhances nitroaromatic compound sorption. Environmental Science & Technology 41:1251-1256.

Liu, C., H. Li, B.J. Teppen, C.T. Johnston, and S.A. Boyd. 2009. Mechanisms Associated with the High Adsorption of Dibenzo-p-dioxin from Water by Smectite Clays. Environmental Science & Technology 43:2777-2783.

Livi, K.J.T., G.S. Senesi, A.C. Scheinost, and D.L. Sparks. 2009. Microscopic Examination of Nanosized Mixed Ni-Al Hydroxide Surface Precipitates on Pyrophyllite. Environmental Science & Technology 43:1299-1304.
Ma, H.B., P.M. Bertsch, T.C. Glenn, N.J. Kabengi, and P.L. Williams. 2009. Toxicity of manufactured zinc oxide nanoparticles in the nematode Caenorhabditis elegans. Environmental Toxicology and Chemistry 28:1324-1330.

Madrid, F., M. Biasioli, and F. Ajmone-Marsan. 2008. Availability and bioaccessibility of metals in fine particles of some urban soils. Archives of Environmental Contamination and Toxicology 55:21-32.

Marsh, L.S., S.W. Gray, G.L. Van Wicklen and T. Crouse. 2003. Performance evaluation of the SanScent air scrubber for removal of dust, ammonia and hydrogen sulfide from the exhaust air of a swine nursery. ASAE Paper No. 034052. St. Joseph, Mich.: ASAE.

Mashal, K., J.B. Harsh, and M. Flury. 2005. Clay mineralogical transformations over time in hanford sediments reacted with simulated tank waste. Soil Science Society of America Journal 69:531-538.

Mashal, K., J.B. Harsh, M. Flury, A.R. Felmy, and H.T. Zhao. 2004. Colloid formation in Hanford sediments reacted with simulated tank \waste. Environmental Science & Technology 38:5750-5756.

Masciangioli, T. and W. Zhang. 2003. Environmental technologies at the nanoscale. Environ. Sci. Technol. 37(5):102A-108A.

Masue, Y., R.H. Loeppert, and T.A. Kramer. 2007. Arsenate and arsenite adsorption and desorption behavior on coprecipitated aluminum : iron hydroxides. Environmental Science & Technology 41:837-842.

McNear, D.H., E. Peltier, J. Everhart, R.L. Chaney, S. Sutton, M. Newville, M. Rivers, and D.L. Sparks. 2005. Application of quantitative fluorescence and absorption-edge computed microtomography to image metal compartmentalization in Alyssum murale. Environmental Science & Technology 39:2210-2218.

Meyer, D., M. Curran, and M. Gonzalez. 2009. An examination of existing data for the industrial manufacture and use of nanocomponents and their role in the life cycle impact of nanoproducts. Environ. Sci. Technol. 43(5):1256-1263.

Mon, J., Y.J. Deng, M. Flury, and J.B. Harsh. 2005. Cesium incorporation and diffusion in cancrinite, sodalite, zeolite, and allophane. Microporous and Mesoporous Materials 86:277-286.

Nakaue, H.S., J.K. Kolliker, D.R. Buhler, and G.H. Arscott. 1981. Distribution of inorganic elements in poultry house dust. Poultry Science 60:1386-1391.

Nel, A. E., L. Mädler, L., D. Velegol, T. Xia, E. Hoek, P. Somarsundaran, F. Klaessig, V. Castranova, and M. Thompson. 2009. Understanding biophysicochemical interactions at the nano-bio interface. Nat. Mat., 8:543-557.

Oram, L.L., D.G. Strawn, M.A. Marcus, S.C. Fakra, and G. Moller. 2008. Macro- and microscale investigation of selenium speciation in blackfoot river, Idaho sediments. Environmental Science & Technology 42:6830-6836.

Park, E.J., and A.J.M. Smucker. 2005. Erosive strengths of concentric regions within soil macroaggregates. Soil Science Society of America Journal 69:1912-1921.

Paul, K.W., J.D. Kubicki, and D.L. Sparks. 2006. Quantum chemical calculations of sulfate adsorption at the Al- and Fe-(Hydr)oxide-H2O interface-estimation of Gibbs free energies. Environmental Science & Technology 40:7717-7724.

Peng, X., R. Horn, and A. Smucker. 2007. Pore shrinkage dependency of inorganic and organic soils on wetting and drying cycles. Soil Science Society of America Journal 71:1095-1104.

Peng, X., R. Horn, S. Peth, and A. Smucker. 2006. Quantification of soil shrinkage in 2D by digital image processing of soil surface. Soil & Tillage Research 91:173-180.

Pereira, T.R., D.A. Laird, C.T. Johnston, B.J. Teppen, H. Li, and S.A. Boyd. 2007. Mechanism of dinitrophend herbicide sorption by smectites in aqueous suspensions at varying pH. Soil Science Society of America Journal 71:1476-1481.

Peth, S., R. Horn, F. Beckmann, T. Donath, J. Fischer, and A.J.M. Smucker. 2008. Three-dimensional quantification of intra-aggregate pore-space features using synchrotron-radiation-based microtomography. Soil Science Society of America Journal 72:897-907.

Pietola, L., and A.J.M. Smucker. 2006. Elimination of non-root residue by computer image analysis of very fine roots. Computers and Electronics in Agriculture 53:92-97.

Powell, B.A., M.C. Duff, D.I. Kaplan, R.A. Fjeld, M. Newville, D.B. Hunter, P.M. Bertsch, J.T. Coates, P. Eng, M.L. Rivers, S.R. Sutton, I.R. Triay, and D.T. Vaniman. 2006. Plutonium oxidation and subsequent reduction by Mn(IV) minerals in Yucca Mountain tuff. Environmental Science & Technology 40:3508-3514.

Power, L.E., Y. Arai, and D.L. Sparks. 2005. Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface. Environmental Science & Technology 39:181-187.

Punshon, T., P.M. Bertsch, A. Lanzirotti, K. McLeod, and J. Burger. 2003. Geochemical signature of contaminated sediment remohilization revealed by spatially resolved X-ray microanalysis of annual rings of Salix nigra. Environmental Science & Technology 37:1766-1774.

Punshon, T., A. Lanzirotti, S. Harper, P.M. Bertsch, and J. Burger. 2005a. Distribution and speciation of metals in annual rings of black willow. Journal of Environmental Quality 34:1165-1173.

Punshon, T., B.P. Jackson, A. Lanzirotti, W.A. Hopkins, P.M. Bertsch, and J. Burger. 2005b. Application of synchrotron x-ray microbeam spectroscopy to the determination of metal distribution and speciation in biological tissues. Spectroscopy Letters 38:343-363.

Qian, J., U. Skyllberg, W. Frech, W.F. Bleam, P.R. Bloom, and P.E. Petit. 2002. Bonding of methyl mercury to reduced sulfur groups in soil and stream organic matter as determined by X-ray absorption spectroscopy and binding affinity studies. Geochimica Et Cosmochimica Acta 66:3873-3885.

Rana, K., S.A. Boyd, B.J. Teppen, H. Li, C. Liu, and C.T. Johnston. 2009. Probing the microscopic hydrophobicity of smectite surfaces. A vibrational spectroscopic study of dibenzo-p-dioxin sorption to smectite. Physical Chemistry Chemical Physics 11:2976-2985.

Reinard, M.S., K. Adou, J.M. Martini, M.V. Johnston. 2007. Source characterization and identification by real-time single particle mass spectrometry. Atmospheric Environment 41:9397-9409.

Roberts, M.G., H. Li, B.J. Teppen, and S.A. Boyd. 2006. Sorption of nitroaromatics by ammonium- and organic ammonium-exchanged smectite: Shifts from adsorption/complexation to a partition-dominated process. Clays and Clay Minerals 54:426-434.

Roberts, M.G., C.L. Rugh, H. Li, B.J. Teppen, and S.A. Boyd. 2007a. Geochemical modulation of bioavailability and toxicity of nitroaromatic compounds to aquatic plants. Environmental Science & Technology 41:1641-1645.

Roberts, M.G., C.L. Rugh, H. Li, B.J. Teppen, and S.A. Boyd. 2007b. Reducing bioavailability and phytotoxicity of 2,4-dinitrotoluene by sorption on K-smectite clay. Environmental Toxicology and Chemistry 26:358-360.

Robichaud, C.O., A.E. Uyar, M.R. Darby, L.G. Zucker, and M.R. Wiesner. 2009. Estimates of Upper Bounds and Trends in Nano-TiO2 Production As a Basis for Exposure Assessment. Environ. Sci. Technol. 43:4227-4233.

Ryser, A.L., D.G. Strawn, M.A. Marcus, S. Fakra, J.L. Johnson-Maynard, and G. Moller. 2006. Microscopically focused synchrotron X-ray investigation of selenium speciation in soils developing on reclaimed mine lands. Environmental Science & Technology 40:462-467.

Schafer, T., G. Buckau, R. Artinger, J.I. Kim, S. Geyer, M. Wolf, W.F. Bleam, S. Wirick, and C. Jacobsen. 2005. Origin and mobility of fulvic acids in the Gorleben aquifer system: implications from isotopic data and carbon/sulfur XANES. Organic Geochemistry 36:567-582.

Scheidegger, A.M., and D.L. Sparks. 1996. A critical assessment of sorption-desorption mechanisms at the soil mineral/water interface. Soil Science 161:813-831.

Scott, N., and H. Chen. 2003. Nanoscale science and engineering for agriculture and food systems. Cornell University, Washington, D.C.

Seaman, J.C., P.M. Bertsch, and D.I. Kaplan. 2007. Spatial and temporal variability in colloid dispersion as a function of groundwater injection rate within Atlantic coastal plain sediments. Vadose Zone Journal 6:363-372.

Seiter, J.M., K.E. Staats-Borda, M. Ginder-Vogel, and D.L. Sparks. 2008. XANES spectroscopic analysis of phosphorus speciation in alum-amended poultry litter. Journal of Environmental Quality 37:477-485.

Service, R. F. 2004. Key to cheaper, better nanotubes comes out in the wash. Science 306:1275-1277.
Service, R.F. 2005. Calls Rise for More Research on Toxicology of Nanomaterials, pp. 1609, Vol. 310. AAAS, Science.

Shang, J., M. Flury, J.B. Harsh, and R.L. Zollars. 2008. Comparison of different methods to measure contact angles of soil colloids. Journal of Colloid and Interface Science 328:299-307.

Skyllberg, U., P.R. Bloom, J. Qian, C.M. Lin, and W.F. Bleam. 2006. Complexation of mercury(II) in soil organic matter: EXAFS evidence for linear two-coordination with reduced sulfur groups. Environmental Science & Technology 40:4174-4180.

Smucker, A.J.M., E.J. Park, J. Dorner, and R. Horn. 2007. Soil micropore development and contributions to soluble carbon transport within macroaggregates. Vadose Zone Journal 6:282-290.

Sowder, A.G., P.M. Bertsch, and P.J. Morris. 2003a. Partitioning and availability of uranium and nickel in contaminated riparian sediments. Journal of Environmental Quality 32:885-898.

Strawn, D.G., and L.L. Baker. 2008. Speciation of cu in a contaminated agricultural soil measured by XAFS, mu-XAFS, and mu-XRF. Environmental Science & Technology 42:37-42.

Strawn, D.G., and L.L. Baker. 2009. Molecular characterization of copper in soils using X-ray absorption spectroscopy. Environmental Pollution 157:2813-2821.

Sutton, S.R., P.M. Bertsch, M. Newville, M. Rivers, A. Lanzirotti, and P. Eng. 2002. Microfluorescence and microtomography analyses of heterogeneous earth and environmental materials. Applications of Synchrotron Radiation in Low-Temperature Geochemistry and Environmental Sciences 49:429-483.

Tasistro, A.S., M.L. Cabrera, Y.B. Zhao, D.E. Kissel, K. Xia, and D.H. Franklin. 2007. Soluble phosphorus released by poultry wastes in acidified aqueous extracts. Communications in Soil Science and Plant Analysis 38:1395-1410.

Taylor, R.W., W.F. Bleam, T.D. Ranatunga, C.P. Schulthess, Z.N. Senwo, and D.R.A. Ranatunga. 2009. X-ray Absorption Near Edge Structure Study of Lead Sorption on Phosphate-Treated Kaolinite. Environmental Science & Technology 43:711-717.

Toor, G.S., S. Hunger, J.D. Peak, J.T. Sims, and D.L. Sparks. 2006. Advances in the characterization of phosphorus in organic wastes: Environmental andagronomic applications. Advances in Agronomy, Vol 89 89:1-72.

Usher, C.R., K.W. Paul, J. Narayansamy, J.D. Kubicki, D.L. Sparks, M.A.A. Schoonen, and D.R. Strongin. 2005. Mechanistic aspects of pyrite oxidation in an oxidizing gaseous environment: An in situ HATR-IR isotope study. Environmental Science & Technology 39:7576-7584.

Vacca, D.J., W.F. Bleam, and W.J. Hickey. 2005. Isolation of soil bacteria adapted to degrade humic acid-sorbed phenanthrene. Applied and Environmental Microbiology 71:3797-3805.

Van Nostrand, J.D., T.J. Khijniak, B. Neely, M.A. Sattar, A.G. Sowder, G. Mills, P.M. Bertsch, and P.J. Morris. 2007a. Reduction of nickel and uranium toxicity and enhanced trichloroethylene degradation to Burkholderia vietnamiensis PR1(301) with hydroxyapatite amendment. Environmental Science & Technology 41:1877-1882.

Van Nostrand, J.D., T.V. Khijniak, T.J. Gentry, M.T. Novak, A.G. Sowder, J.Z. Zhou, P.M. Bertsch, and P.J. Morris. 2007b. Isolation and characterization of four gram-positive nickel-tolerant microorganisms from contaminated sediments. Microbial Ecology 53:670-682.

Wan, J., T.K. Tokunaga, Y. Kim, Z. Wang, A. Lanzirotti, E. Saiz, and R.J. Serne. 2008. Effect of Saline Waste(Solution Infiltration Rates on Uranium Retention and Spatial Distribution in(Hanford Sediments. Environmental Science &(Technology 42:5.

Wan, J., Y. Kim, T.K. Tokunaga, Z. Wang, S. Dixit, C.I. Steefel, E. Saiz, M. Kunz, and N. Tamura. 2009. Spatially Resolved U(VI)(Partitioning and Speciation: Implications for Plume Scale Behavior of(Contaminant U in the Hanford Vadose Zone. Environmental Science &(Technology 43:6.

Wang, C.P., Y.J. Ding, B.J. Teppen, S.A. Boyd, C.Y. Song, and H. Li. 2009. Role of Interlayer Hydration in Lincomycin Sorption by Smectite Clays. Environmental Science & Technology 43:6171-6176.
Wendling, L.A., J.B. Harsh, C.D. Palmer, M.A. Hamilton, H.M. Dion, J.S. Boyle, and M. Flury. 2005a. Rhizosphere effects on cesium fixation sites of soil containing micaceous clays. Soil Science Society of America Journal 69:1652-1657.

Wendling, L.A., J.B. Harsh, T.E. Ward, C.D. Palmer, M.A. Hamilton, J.S. Boyle, and M. Flury. 2005b. Cesium desorption from lllite as affected by exudates from rhizosphere bacteria. Environmental Science & Technology 39:4505-4512.

Warheit, D. B., B.R. Laurence, K. L. Reed, D.H. Roach, G.A.M. Reynolds, and T.R. Webb. 2004. Comparative pulmonary toxicity assessment of single-wall carbon nanotubes in rats. Toxicol. Sci. 77(1):117-125.

Wiesner, M. R., G. V. Lowry, P. Alvarez, D. Dionysiou, and P. Biswas. 2006. Assessing the risks of manufactured nanomaterials. Environ. Sci. Technol. 40(14):4336-4345.

Xia, K., W. Bleam, and P.A. Helmke. 1997. Studies of the nature of binding sites of first row transition elements bound to aquatic and soil humic substances using X-ray absorption spectroscopy. Geochimica Et Cosmochimica Acta 61:2223-2235.

Yoon, S.J., L.M. Diener, P.R. Bloom, E.A. Nater, and W.F. Bleam. 2005. X-ray absorption studies of CH3Hg+-binding sites in humic substances. Geochimica et Cosmochimica Acta 69:1111-1121.

Zhang, G., J.M. Senko, S.D. Kelly, H. Tan, K.M. Kemner, and W.D. Burgos. 2009. Microbial reduction of(iron(III)-rich nontronite and uranium(VI). Geochimica et Cosmochimica Acta 73:15.

Zhu, M.Q., K.W. Paul, J.D. Kubicki, and D.L. Sparks. 2009. Quantum Chemical Study of Arsenic (III, V) Adsorption on Mn-Oxides: Implications for Arsenic(III) Oxidation. Environmental Science & Technology 43:6655-6661.

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