Zimmerman Lab Group

Enabling the Integrated Biorefinery

ngelenge
There is an increasing demand to produce energy and materials from renewable resources.  Full utilization of biomass feedstocks, analogous to petroleum refining, is critical to reduce economic and environmental barriers to large-scale fuel production.  To advance this goal and the implementation of the integrated biorefinery, Zimmerman’s group has made novel and significant contributions to the fundamental chemistry and underlying process engineering to produce value-added chemicals from biomass [2] as well as assessment of environmental benefits and impacts.  We have focused on surfactants as a chemical class, assessing renewable feedstocks [3], developing the novel, patented class of c-glycosides, and established green transformations for their production [4]. 
 
Further, for the last several years, Zimmerman’s group has been developing new approaches for microalgal feedstocks for the production of fuels and chemicals.   Our group has uniquely combined empirical and life cycle data to suggest optimal applications of biobased feedstocks and process train selection considering resource and energy inputs as well as biomolecular composition [5, 6, 7, 8].  We have demonstrated the viability of supercritical carbon dioxide as an extraction solvent for wet biomass meeting or exceeding the performance of organic solvents while providing increased selectivity, decreased hazards, and minimized downstream processing [9].  Expanding on these findings, a selective, efficient, one-pot separation technology for the extraction and transesterification of lipids from crude biomass for fuel as well as higher value applications has been demonstrated [10].  This novel system relies on thermodynamically favorable phase behavior in a low temperature, moderate pressure carbon dioxide-expanded methanol system. 
 
Funding
Connecticut Innovations Challenge, Adding value to Biomass Pathways-Sustainable Energies: Innovative technologies involving biomass conversion processes and equipment to produce fuels, power or bio-based chemicals, co-PI @ 40% (with PI AgriFuels, LLC @ 60%) total budget $150,000, 2013-2014
 
Center for Business and the Environment at Yale:  Greening Supply Chains: Enabling Sustainability Beyond Firm Boundaries, PI, total budget $75,000, 2012-2014
 
National Science Foundation:  Exploring the Relationships between Gene Regulation and Microbial Ecology for the Sustainable Production of Microalgae-based Biofuels, co-PI, total budget $300,000, 2009-2013
 
United States Department of Agriculture: Transformation of lignin into building blocks for protective coatings, PI, total budget $500,000, 2009-2013
 
 
References
  
  1. Foley, P., E.S. Beach, and J.B. Zimmerman, Algae as a Source of Renewable Chemicals: Opportunities and Challenges. Green Chemistry, 2011. 13(6): p. 1399-1405.
  2. Foley, P., Phimphachanh, A., Beach, E., Zimmerman, J.B., Anastas, P.T., Linear and Cyclic C-Glycosides as Surfactants. Green Chemistry, 2011. 13(2): p. 321-325.

  3. Foley, P., Kermanshahi pour, A., Beach, E.S., Zimmerman, J.B., Derivation and Synthesis of Renewable Surfactants. Chemical Society Reviews, 2012. 14(4): p. 1499-1518.

  4.  Soh, L., Montazeri, M., Haznedaroglu, B.Z., Kelly, C., Peccia, J., Eckelman, M.J., Zimmerman, J.B., Evaluating Microalgal Integrated Biorefinery Schemes:  Empirical Controlled Growth Studies and LIfe Cycle Assessment. Bioresource Technology, 2013: p. in press.

  5. Brentner, L.B., M.J. Eckelman, and J.B. Zimmerman, Combinatorial life cycle assessment to inform process design of industrial production of algal biodiesel. Environmental Science & Technology, 2011. 45(16): p. 7060-7067.

  6. Peccia, J., Haznedaroglu, B., Gutierrez, J., Zimmerman, J.B., Nitrogen supply is an important driver of sustainable microalgae biofuel production. Trends in Biotechnology, 2013. 31(3): p. 134-138.

  7. Beach, E., Eckelman, M.J., Cui, Z., Brentner, L., Zimmerman, J.B., Preferential technological and life cycle environmental performance of chitosan flocculation for harvesting of the green algae Neochloris oleoabundans. Bioresource Technology, 2012, 121: p. 445-449.

  8. Soh, L. and J.B. Zimmerman, Biodiesel Production Potential of Algal Lipids Extracted with Supercritical Carbon Dioxide. Green Chemistry, 2011. 13(6): p. 1422-1429.

Novel, green sorbents to remove inorganic contaminants from aqueous systems

Arsenic Beads
Although significant advances have helped to address water-quality and water-quantity issues, many challenges still exist for technology research, development, and implementation, including understanding the water-energy nexus for infrastructure systems [1-4].  Zimmerman’s group has conducted groundbreaking research in evaluating and developing materials for use in water and wastewater treatment applications, including natural coagulants [5] and novel sorbents for arsenic and selenium, while understanding and quantifying possible implications [6-9].  Collectively, this work has discovered and demonstrated new material platforms for water treatment that meet or exceed current performance standards but also align with the principles of sustainability.  Specifically, this work has demonstrated (i) the synergistic benefits of abundant, non-toxic, and in some cases photoactive nano-metal oxides with a waste biopolymer to adsorb inorganic contaminants in multiple redox states, (ii) the benefits of the sorbents in terms of enhanced sorptive capacity, passive separation, regeneration/reuse, and ease of operation, and (iii) their appropriateness (i.e., robustness, ease of operation, use of natural sunlight) and potential implementation for small-scale drinking water systems in the United States as well as West Bengal, India and Bangladesh.
 
Funding
Environmental Protection Agency:  National Center for Reinventing Aging Infrastructure for Nutrient Management, co-PI, total budget $2,000,000, 2013-2017
 
National Science Foundation:  Targeted Design of Biomaterials for Water Treatment:  Arsenic Removal and Recovery, PI, total budget $325,000, 2009-2013
 
 
National Science Foundation: BE MUSES: Collaborative Research: Modeling and Analyzing the Use, Efficiency, Value and Governance of Water as a Material in the Great Lakes Region Through an Integrated Approach, PI, total budget $2,000,000, 2007-2014
 
National Science Foundation: Mechanistic Laboratory and Field Evaluation of Sustainable Point-of-Use Water Treatment Technologies to Remove Turbidity and Deactivate Coliform Bacteria, co-PI, total budget $400,000, 2006-2009
 
 
References
  1. Zimmerman, J.B., Mihelcic, J.R., Smith, J.A., Global stressors on water quality and quantity. Environmental Science & Technology, 2008. 42(12): p. 4247-4254.
  2. Boyle, C., Mudd, G., Mihelcic, J., Anastas, P., Collins, T., Culligan, P., Edwards, M., Gabe, J., Gallagher, P., Handy, S., Kao, J.J., Krumdieck, S., Lyles, L.D., Mason, I., McDowall, R., Pearce, A., Riedy, C., Russell, J., Schnoor, J.L., Trotz, M., Venables, R., Zimmerman, J.B., et al., Delivering Sustainable Infrastructure that Supports the Urban Built Environment. Environmental Science & Technology, 2010. 44(13): p. 4836-4840.

  3.  Mo, W., Nasiri, F., Eckelman, M.J., Zhang, Q., Zimmerman, J.B., Measuring the Embodied Energy in Drinking Water Supply Systems: A Case Study in The Great Lakes Region. Environmental Science & Technology, 2010. 44(24): p. 9516-9521.

  4. Wang, R., Eckelman, M.J., Zimmerman, J.B., Consequential Environmental and Economic Life Cycle Assessment of Green and Gray Stormwater Infrastructures for Combined Sewer Systems. Environmental Science & Technology, 2013.

  5. Miller, S.M., Fugate, E.J., Craver, V.O., Smith, J.A., Zimmerman, J.B., Toward understanding the efficacy and mechanism of Opuntia spp. as a natural coagulant for potential application in water treatment. Environmental Science & Technology, 2008. 42(12): p. 4274-4279.

  6. Miller, S.M., Zimmerman, J. B., Novel, Bio-Based, Photoactive Arsenic Sorbent: TiO2-1 Impregnated Chitosan Bead. Water Research, 2010. 44(19): p. 5722-5729.

  7. Miller, S.M., Spaulding, M., Zimmerman, J.B., Optimization of capacity and kinetics for a novel bio-based arsenic sorbent, TiO2-impregnated chitosan bead. Water Research, 2011. 45(17): p. 5745-5754.

  8. Yamani, J., Lounsbury, A.W., Zimmerman, J.B., Adsorption of Selenite and Selenate by Nanocrystalline Aluminum Oxide, Neat and Impregnated in Chitosan Beads. Water Research, 2013: p. in press.

  9. Yamani, J.S., Miller, S.M., Spaulding, M.L., Zimmerman, J.B., Enhanced arsenic removal using mixed metal oxide impregnated chitosan beads. Water Research, 2012. 46(14): p. 4427-4434.

Informing the Design of Safer Chemicals and Nanomaterials

ChemicalAssays[1]
Chemists have developed considerable expertise in designing chemicals for specific industrial or pharmaceutical functions, but to date little progress has been made in minimizing undesired biological and environmental behavior.   Zimmerman’s work has made significant contributions to advance rational design of safer chemcials as demonstrated by the first set of property-based guidelines for a diverse group of chemicals with reduced acute [2] and chronic aquatic toxicity [3] resulting in a two- to five-fold increase in the likelihood of designing a chemical with little to no aquatic toxicity concern [4].  This approach has also been demonstrated for epoxides as a chemical class and mutagenicity as the toxicological endpoint of concern [5].
 
Beyond molecular design, similar approaches are needed for nanomaterials, an emerging class of substances with novel and desirable properties but uncertain implications for human and ecosystem health, particularly given the amount of waste generated during synthesis [6].  To further characterize the toxicity potential of carbon nanotubes and to inform the design of safer nanomaterials, Zimmerman’s group established relationships between physiochemical characteristics and cytotoxic potential for both single-walled (SWNTs) [7] and multi-walled carbon nanotubes (MWNTs) [8].   We have shown for the first time that aggregation state, not surface functionalization characteristics, correlate to loss in cell viability for SWNTs.  While there was precedent literature suggesting that MWNTs were of significantly lower concern for cyctotoxicity than SWNT, we have uniquely established that MWNT antimicrobial activity can be controlled and manipulated through oxidation and selective reduction realizing the same antimicrobial activity as SWNTs.   This allows for an enhanced understanding of the causal relationship between fundamental physiochemical properties and cytotoxic mechanism in order to both advance functional design and to minimize unintended consequences of CNTs.  This work also reinforces the hypothesis that molecules and materials can be rationally designed by understanding and manipulating key physical chemical properties to minimize or eliminate hazardous impacts on human health and the environment.
 
Funding
National Science Foundation/Environmental Protection Agency:  Networks for Sustainable Molecular Design and Synthesis, co-PI, total budget $4,400,00, 2013-2017
 
Environmental Protection Agency:  Networks for Characterizing Chemical Life Cycle: Life Cycle of Nanomaterials, Senior Personnel, total budget $4,400,000, 2013-2017
 
National Science Foundation:  A Workshop on the Molecular Design of Commercial Chemicals for Minimal Unintended Biological Activity, co-PI, total budget $90,500, 2012-2014
 
National Science Foundation:  Designing and Integrating Life Cycle Assessment Methods for Nanomanufacturing Scale-up, co-PI, total budget $1,670,000, 2012-2016
 
National Science Foundation:  Design of Safer Carbon-Based Nanomaterials:  The Impact of Surface Modifications on Toxicity and Environmental Fate and Transport, PI, total budget $360,000, 2009-2013
 
References
  1. Voutchkova, A.M., Kostal, J., Steinfeld, J.B., Emerson, J.W., Brooks, B.W., Anastas, P.T., Zimmerman, J.B., Towards rational molecular design: derivation of property guidelines for reduced acute aquatic toxicity. Green Chemistry, 2011. 13(9): p. 2373 - 2379.
  2. Voutchkova-Kostal, A.M., Kostal, J., Connors, K.A., Brooks, B.W., Anastas, P.T., Zimmerman, J.B., Towards rational molecular design for reduced chronic aquatic toxicity. Green Chemistry, 2012. 14(4): p. 1001-1008.

  3. Voutchkova-Kostal, A.; Kostal, J.; Anastas, P. T.; Zimmerman, J. B. “Computational Approaches for Molecular Design for Reduced Toxicity - A Case Study: Acute Toxicity to the Pimephales Promelas”, Proceedings of the National Academies, in revision.

  4. Kostal, J., Voutchkova,-Kostal, A., Weeks, B., Zimmerman, J.B., Anastas, P.T., A Free Energy Approach to the Prediction of Olefin and Epoxide Mutagenicity and Carcinogenicity. Chemical Research in Toxicology, 2012. 25(12): p. 2780-2787.

  5. Eckelman, M.J., Zimmerman, J.B., Anastas, P.T., Toward green nano. E-factor analysis of several nanomaterial syntheses. Journal of Industrial Ecology, 2008. 12(3): p. 316-328.

  6. Pasquini, L.M., Hashmi, S.M., Sommer, T.J., Elimelech, M., Zimmerman, J.B., Impact of Surface Functionalization on Bacterial Cytotoxicity of Single-Walled Carbon Nanotubes. Environmental Science & Technology, 2012. 46(11): p. 6297-6305.

  7. Pasquini, L.M., Sekol, R.C., Taylor, A.D., Pfefferle, L.D., Zimmerman, J.B., Realizing Comparable Oxidative and Cytotoxic Potential of Single- and Multiwalled Carbon Nanotubes through Annealing. Environmental Science & Technology, 2013. 47(15): p. 8775-8783.

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