Julie B. Zimmerman

Combinatorial Life Cycle Assessment to Inform Process Design of Industrial Production of Algal Biodiesel

The use of algae as a feedstock for biodiesel production is a rapidly growing industry, in the United States and globally. A life cycle assessment (LCA) is presented that compares various methods, either proposed or under development, for algal biodiesel to inform the most promising pathways for sustainable full-scale production. For this analysis, the system is divided into five distinct process steps: (1) microalgae cultivation, (2) harvesting and/or dewatering, (3) lipid extraction, (4) conversion (transesterification) into biodiesel, and (5) byproduct management. A number of technology options are considered for each process step and various technology combinations are assessed for their life cycle environmental impacts. The optimal option for each process step is selected yielding a best case scenario, comprised of a flat panel enclosed photobioreactor and direct transesterification of algal cells with supercritical methanol. For a functional unit of 10 GJ biodiesel, the best case production system yields a cumulative energy demand savings of more than 65 GJ, reduces water consumption by 585 m(3) and decreases greenhouse gas emissions by 86% compared to a base case scenario typical of early industrial practices, highlighting the importance of technological innovation in algae processing and providing guidance on promising production pathways.

Algae as a source of renewable chemicals: opportunities and challenges

Algae are being explored as a sustainable energy feedstock, having potential to reduce dependence on petrofuels and offset greenhouse gas emissions. Economic considerations and principles of green design suggest that if algae-to-fuel technology is to be successful, biofuels must be produced simultaneously with value-added co-products. At present, the algae industry is centered around a limited number of products, such as low-volume/high-value speciality nutrients. New products for medium- and high-volume markets will be needed as biomass production increases in scale. This Perspective highlights non-fuel applications of algal biomass that have received relatively little attention to date but are promising for future development. It is our goal to draw attention to some of the unique opportunities that algae present with respect to biochemical composition as compared to lignocellulosic energy crops.

Fate of sucralose through environmental and water treatment processes and impact on plant indicator species.

The degradation and partitioning of sucralose during exposure to a variety of environmental and advanced treatment processes (ATP) and the effect of sucralose on indicator plant species were systematically assessed. Bench scale experiments were used to reproduce conditions from environmental processes (microbial degradation, hydrolysis, soil sorption) and ATPs (chlorination, ozonation, sorption to activated carbon, and UV radiation). Degradation only occurred to a limited extent during hydrolysis, ozonation, and microbial processes indicating that breakdown of sucralose will likely be slow and incomplete leading to accumulation in surface waters. Further, the persistence of sucralose was compared to suggested human tracer compounds, caffeine and acesulfame-K. In comparison sucralose exhibits similar or enhanced characteristics pertaining to persistence, prevalence, and facile detection and can therefore be considered an ideal tracer for anthropogenic activity. Ecological effects of sucralose were assessed by measuring sucrose uptake inhibition in plant cotelydons and aquatic plant growth impairment. Sucralose did not inhibit plant cotelydon sucrose uptake, nor did it effect frond number, wet weight, or growth rate in aquatic plant, Lemna gibba. Though sucralose does not appear toxic to plant growth, the peristent qualities of sucralose may lead to chronic low-dose exposure with largely unknown consequences for human and environmental health.

Challenges in Developing Biohydrogen as a Sustainable Energy Source: Implications for a Research Agenda

The U.S. Department of Energys Hydrogen Program aims to develop hydrogen as an energy carrier to decrease emissions of greenhouse gases and other air pollutants and reduce the use of fossil fuels. However, current hydrogen production technologies are not sustainable as they rely heavily on fossil fuels, either directly or indirectly through electricity generation. Production of hydrogen by microorganisms, biohydrogen, has potential as a renewable alternative to current technologies. The state-of-the-art for four different biohydrogen production mechanisms is reviewed, including biophotolysis, indirect biophotolysis, photofermentation, and dark fermentation. Future research challenges are outlined for bioreactor design, optimization of bioreactor conditions, and metabolic engineering. Development of biohydrogen technologies is still in the early stages, although some fermentation systems have demonstrated efficiencies reasonable for implementation. To enhance the likelihood of biohydrogen as a feasible system to meet future hydrogen demands sustainably, directed investment in a strategic research agenda will be necessary.

Nitrogen supply is an important driver of sustainable microalgae biofuel production

Favorable growth characteristics continue to generate interest in using triacylglycerides (TAGs) produced from microalgae for biodiesel feedstocks. In this opinion article, we suggest that due to the energy consumption associated with the production of external nitrogen fertilizers, the manner in which nitrogen is supplied to microalgae biorefineries will be an important driver of energy yields, sustainability, and commercial success. Schemes including the reuse of urban wastewater represent improvements on the overall energy balance, but will not allow for significant production of biofuels unless the nitrogen from the non-TAG portions of microalgae is recycled. Approaches to recycling nitrogen require an improved understanding of the tradeoffs between the different potential uses of the non-TAG microalgal portion (i.e., energy production via anaerobic digestion or thermal catalytic processes), and the development of nitrogen separation technologies.

Biodiesel production: the potential of algal lipids extracted with supercritical carbon dioxide

Supercritical carbon dioxide (scCO2) was used to extract components of interest from Scenedesmus dimorphus, a microalgae species, under varied algal harvesting and extraction conditions. Liquid chromatography-mass spectrometry (LC-MS) was used to quantify the concentration of fatty acid methyl esters (FAME) and the FAME profile of transesterified lipids, phospholipids and pigments extracted under varied supercritical temperatures and pressures. The scCO2 extraction results are compared with conventional solvent extraction to evaluate differences in the efficiency and nature of the extracted materials. Algae harvested by centrifugation (vs.lyophilization) demonstrated a similar extraction efficiency in scCO2, indicating potential energy benefits by avoiding conventional algal mass dehydration prior to extraction. Centrifuged algae and optimized extraction conditions (6000 psi; 100 °C) resulted in comparable FAME yields to conventional processes, as well as increased selectivity, reflected in the decreased pigment, nitrogen and phospholipid contamination of the FAME. Cell pre-treatments—sonication, microwave, bead beating and lyophilization—showed an enhancement in extraction yield in both conventional solvent and scCO2 extraction, allowing for improved extraction efficiencies. This study suggests that scCO2, a green solvent, shows great potential for algal lipid extraction for the sustainable production of biodiesel.

Impact of Surface Functionalization on Bacterial Cytotoxicity of Single-Walled Carbon Nanotubes

The addition of surface functional groups to single-walled carbon nanotubes (SWNTs) is realized as an opportunity to achieve enhanced functionality in the intended application. At the same time, several functionalized SWNTs (fSWNTs), compared to SWNTs, have been shown to exhibit decreased cytotoxicity. Therefore, this unique class of emerging nanomaterials offers the potential enhancement of SWNT applications and potentially simultaneous reduction of their negative human health and environmental impacts depending on the specific functionalization. Here, the percent cell viability loss of Escherichia coli K12 resulting from the interaction with nine fSWNTs, n-propylamine, phenylhydrazine, hydroxyl, phenydicarboxy, phenyl, sulfonic acid, n-butyl, diphenylcyclopropyl, and hydrazine SWNT, is presented. The functional groups range in molecular size, chemical composition, and physicochemical properties. While physiochemical characteristics of the fSWNTs did not correlate, either singularly or in combination, with the observed trend in cell viability, results from combined light scattering techniques (both dynamic and static) elucidate that the percent loss of cell viability can be correlated to fSWNT aggregate size distribution, or dispersity, as well as morphology. Specifically, when the aggregate size polydispersity, quantified as the width of the distribution curve, and the aggregate compactness, quantified by the fractal dimension, are taken together, we find that highly compact and narrowly distributed aggregate size are characteristics of fSWNTs that result in reduced cytotoxicity. The results presented here suggest that surface functionalization has an indirect effect on the bacterial cytotoxicity of SWNTs through the impact on aggregation state, both dispersity and morphology.

Novel, bio-based, photoactive arsenic sorbent: TiO2-impregnated chitosan bead.

A novel sorbent for arsenic, TiO(2)-impregnated chitosan bead (TICB), has been synthesized and successfully tested. Kinetic plots, pH dependence, isotherm data, and bead morphology are reported. Equilibrium is achieved after 185 h in batch experiments with exposure to UV light. The TICB system performs similarly to the mass equivalent of neat TiO(2) nanopowder. The point of zero charge (pzc) for TICB was determined to be 7.25, and as with other TiO(2)-based arsenic removal technologies, the optimal pH range for sorption is below this pH(pzc). Without exposure to UV light, TICB removes 2198 μg As(III)/g TICB and 2050 μg As(V)/g TICB. With exposure to UV light, TICB achieves photo-oxidation of As(III) to As(V), the less toxic and more easily sequestered arsenic form. UV irradiation also results in enhanced arsenic removal, reaching sorption capacities of 6400 μg As/g TICB and 4925 μg As/g TICB, where arsenic is initially added as As(III) and As(V), respectively. Because the TICB system obviates filtration post-treatment, TICB is superior to TiO(2) nanopowder from the perspective of implementation for decentralized water treatment.

Enhanced arsenic removal using mixed metal oxide impregnated chitosan beads

Mixed metal oxide impregnated chitosan beads (MICB) containing nanocrystalline Al₂O₃ and nanocrystalline TiO₂ were successfully developed. This adsorbent exploits the high capacity of Al₂O₃ for arsenate and the photocatalytic activity of TiO₂ to oxidize arsenite to arsenate, resulting in a removal capacity higher than that of either metal oxide alone. The composition of the beads was optimized for maximum arsenite removal in the presence of UV light. The mechanism of removal was investigated and a mode of action was proposed wherein TiO₂ oxidizes arsenite to arsenate which is then removed from solution by Al₂O₃. Pseudo-second order kinetics were used to validate the proposed mechanism. MICB is a more efficient and effective adsorbent for arsenic than TiO₂-impregnated chitosan beads (TICB), previously reported on, yet maintains a desirable life cycle, free of complex synthesis processes, toxic materials, and energy inputs.

Preferential technological and life cycle environmental performance of chitosan flocculation for harvesting of the green algae Neochloris oleoabundans

Dewatering of the green algae Neochloris oleoabundans by flocculation was investigated for chitosan biopolymer, ferric sulfate, and alum. Chitosan was found to be most effective flocculant, with an optimum dose of 100mg/L algae broth. Zeta potential measurements suggest the mechanism involves both adsorption and charge neutralization processes. Life cycle assessment (LCA) was used to compare the chitosan method to other flocculation methods as well as centrifugation and filtration/chamber press processes. LCA showed that among these techniques, flocculation by chitosan is the least energy intensive and had the lowest impacts across all other categories of environmental impacts. The results are discussed in the overall context of biofuel production from algal biomass.