Environmental Chemistry at the University of Minnesota
Department of Soil, Water & Climate
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Surface Chemistry & Environmental Quality
Platinum Nanoparticulates in Diesel Fuel Emissions

The platinum (Pt) nanoparticle project is a new collaboration between the University of Minnesota - Twin Cities (Brandy Toner) and the University of Wisconsin - Madison (Martin Shafer and James Schauer) to examine Pt speciation in aerosols emitted from diesel burning engines. Platinum is added to diesel fuel as a soluble organic compound along with another organo-metallic, such as Ce, to improve combustion. In the engine, the Pt compounds are reduced and form nano- to micrometer scale, Pt-coated, Ce-carrier particles that exit the vehicle through the tailpipe.  Platinum-amended fuels (Pt-FBC) are currently approved in Europe for broad use, and in the US for many specialty diesel vehicles.  Martin Schafer and co-workers recently completed a study of Pt and Ce emissions from diesel engines burning a Pt-FBC (Shafer et al., 2006). Schafer et al. determined that in the "engine-out" emissions of water-soluble Pt represented nearly 3 % of total emissions and a large fraction of the water soluble Pt (44 ± 8%) was present as nanometer-sized particles.  The current toxicology paradigm is that for environmental Pt to exhibit significant human toxicity it must be in specific water soluble forms.  In occupational exposure settings Pt-compounds can be powerful allergens and several studies suggest that the increase in the incidence of asthma may, in part, be related to environmental Pt exposure.  Although chemical speciation dictates the toxicity and reactivity of these Pt-coated nano-particulate materials, to date, there is little definitive information on Pt speciation in environmental particles since operational definitions and measurements for Pt toxicity have been the standard. Through our collaboration, we will be conducting spatially-resolved Pt X-ray absorption spectroscopic (micro-XAS) measurements on Pt-FBC emissions to:  (1) determine Pt speciation within particulate Pt-FBC emissions, (2) track speciation changes due to reactions occurring in the environment, and (3) assess the toxicity of Pt-FBC particulate emissions. 

Shafer, M.M., J.J. Schauer, W. Copan, J. Peter-Hoblyn, B. Sprague, and J. Valentine (2006).  Investigation of platinum and cerium from use of a fuel-based catalyst.  SAE Journal – 2006-01-1517.  

Arsenic Sequestration by Industrial By-Products

The arsenic sequestration project is a new collaboration between the University of Minnesota - Twin Cities (Brandy Toner) and University of Wisconsin - Madison (Craig Benson, Seung-Hak Lee, and Stacy Metz) to examine the mechanism(s) of arsenic (As) removal from water by an industrial by-product, iron foundry slag.  Arsenic contamination of drinking water, from natural and anthropogenic sources, is a common environmental phenomenon that raises great concerns about human health.  The U.S. Environmental Protection Agency has assigned a 10 microgram per liter Maximum Contaminant Level for arsenic in drinking water.  Therefore, development of cost-effective technologies to achieve this low concentration of As in water are in great demand (for a review, see Choong et al., 2007).  Stacy Metz and co-workers have examined the removal of arsenate and arsenite from water by iron foundry slag materials produced in Wisconsin.  Iron foundary slags contain oxides of Si, Al, Ca, Mg, and Fe, as well as pure Fe (Metz, 2007), and represent an opportunity to use an industrial waste product for water remediation.  Through our collaboration, we have begun conducting synchrotron-radiation X-ray absorption spectroscopic studies of the Fe and As speciation within reacted iron foundry slag materials to determine the mechanism(s) of As sequestration by these materials.

Choong, T.S.Y, Chuah, T.G., Robiah, Y., Koay, G.F.L, and Azni, I. (2007) Arsenic toxicity, health hazards and removal techniques from water: an overview. Desalination 217:139-166.

Metz, S.E. (2007) Iron foundry slags as reactive materials for arsenic removal from groundwater.  M.S.Thesis in Geological Engineering. University of Wisconsin - Madison.            
Atrazine Degradation by Manganese Oxide Minerals
*Under Construction*



Treated Wastewater & Biosolids in Soils: Phosphorus Speciation, Transport, and Accumulation

The phosphorus (P) speciation project is a new collaboration in the Department of Soil, Water, and Climate between Paul Bloom and Brandy Toner.  Paul Bloom has secured funding through an international collaboratory program, BARD - Binational Agricultural Research and Development Fund, to examine P speciation in wastewater (TWW) and biosolid (BS) treated soil.

*There is currently funding for a postdoctoral researcher on this project.*  

It is well-documented that P accumulates in soils after prolonged irrigation with TWW or application of biosolids, however, there is limited knowledge of P chemical forms in TWW and BS treated soils. The different P forms can have a wide range of availability to plants and mobility in surface runoff and down a soil profile, into shallow groundwater and drainage. In the proposed research, we shall study the fate of sewage-originated P (sewage-P, including TWW-P and BS-P) in soils of Israel and Minnesota in micro (particle surface), meso (microcosms, lysimeters), and whole field and profile depth scales, focusing of the processes of retention, transformations, transport, accumulation, and leaching. The study will make use of existing fields in both countries with long known history of TWW or BS application. We shall combine common methods of P extractions and fractionation with advanced tools of SEM-EDXS, synchrotron X-ray micro X-ray fluorescence (XRF) and micro X-ray absorption near edge structure (XANES) 
spectroscopy to identify modes and processes of P retention and accumulation. The knowledge gained in this study will lead to maximizing the beneficial use of TWW and BS and minimize adverse effects on the environment through P loss to surface and ground waters. It is also believed that the procedures developed in this project will have the potential to be used for other important P systems (e.g., application of manures or various effluents) after proper modification.

References:
Hettiarachchi, G.M., K.G. Scheckel, J.A. Ryan, S.R. Sutton, and M. Newville. 2006. µ-XANES and µ-XRF investigations of metal binding mechanisms in biosolids. J. Environ. Qual. 35: 342-35.

Pierzynski, G. M. Logan, T. J. Traina, S. J. Bigham, J. M. Phosphorus chemistry and mineralogy in excessively fertilized soils: quantitative analysis of phosphorus-rich particles. Soil Science Society of America Journal. 1990. 54: 6, 1576-1583.

Sato, S., D. Solomon, C. Hyland, Q. Ketterings, and J. Lehmann. 2005. Phosphorus speciation in manure and manure-amended soils using XANES spectroscopy. Environ. Sci. Technol. 39:7485-749


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