Lisa M. Colosi

Environmental Life Cycle Comparison of Algae to Other Bioenergy Feedstocks

Algae are an attractive source of biomass energy since they do not compete with food crops and have higher energy yields per area than terrestrial crops. In spite of these advantages, algae cultivation has not yet been compared with conventional crops from a life cycle perspective. In this work, the impacts associated with algae production were determined using a stochastic life cycle model and compared with switchgrass, canola, and corn farming. The results indicate that these conventional crops have lower environmental impacts than algae in energy use, greenhouse gas emissions, and water regardless of cultivation location. Only in total land use and eutrophication potential do algae perform favorably. The large environmental footprint of algae cultivation is driven predominantly by upstream impacts, such as the demand for CO(2) and fertilizer. To reduce these impacts, flue gas and, to a greater extent, wastewater could be used to offset most of the environmental burdens associated with algae. To demonstrate the benefits of algae production coupled with wastewater treatment, the model was expanded to include three different municipal wastewater effluents as sources of nitrogen and phosphorus. Each provided a significant reduction in the burdens of algae cultivation, and the use of source-separated urine was found to make algae more environmentally beneficial than the terrestrial crops.

Pilot-scale data provide enhanced estimates of the life cycle energy and emissions profile of algae biofuels produced via hydrothermal liquefaction.

Life cycle assessment (LCA) has been used widely to estimate the environmental implications of deploying algae-to-energy systems even though no full-scale facilities have yet to be built. Here, data from a pilot-scale facility using hydrothermal liquefaction (HTL) is used to estimate the life cycle profiles at full scale. Three scenarios (lab-, pilot-, and full-scale) were defined to understand how development in the industry could impact its life cycle burdens. HTL-derived algae fuels were found to have lower greenhouse gas (GHG) emissions than petroleum fuels. Algae-derived gasoline had significantly lower GHG emissions than corn ethanol. Most algae-based fuels have an energy return on investment between 1 and 3, which is lower than petroleum biofuels. Sensitivity analyses reveal several areas in which improvements by algae bioenergy companies (e.g., biocrude yields, nutrient recycle) and by supporting industries (e.g., CO2 supply chains) could reduce the burdens of the industry.

Algae biodiesel has potential despite inconclusive results to date.

A meta-analysis of several published life cycle assessments of algae-to-energy systems was developed to better understand the environmental implications of deploying this technology at large scales. Taken together, results from these six studies seemed largely inconclusive because of differences in modeling assumptions and system boundaries. To overcome this, the models were normalized using a generic pathway for cultivating algae in open ponds, converting it into biodiesel, and processing the nonlipid fraction using anaerobic digestion. Meta-analysis results suggest that algae-based biodiesel would result in energy consumption and greenhouse gas emissions on par with terrestrial alternatives such as corn ethanol and soy biodiesel. Net energy ratio and normalized greenhouse gas emissions were 1.4 MJ produced/MJ consumed and 0.19 kg CO(2)-equivalent/km traveled, respectively. A scenario analysis underscores the extent to which breakthroughs in key technologies are needed before algae-derived fuels become an attractive alternative to conventional biofuels.

Comparison of algae cultivation methods for bioenergy production using a combined life cycle assessment and life cycle costing approach.

Algae are an attractive energy source, but important questions still exist about the sustainability of this technology on a large scale. Two particularly important questions concern the method of cultivation and the type of algae to be used. This present study combines elements of life cycle analysis (LCA) and life cycle costing (LCC) to evaluate open pond (OP) systems and horizontal tubular photobioreactors (PBRs) for the cultivation of freshwater (FW) or brackish-to-saline water (BSW) algae. Based on the LCA, OPs have lower energy consumption and greenhouse gas emissions than PBRs; e.g., 32% less energy use for construction and operation. According to the LCC, all four systems are currently financially unattractive investments, though OPs are less so than PBRs. BSW species deliver better energy and GHG performance and higher profitability than FW species in both OPs and PBRs. Sensitivity analyses suggest that improvements in critical cultivation parameters (e.g., CO(2) utilization efficiency or algae lipid content), conversion parameters (e.g., anaerobic digestion efficiency), and market factors (e.g., costs of CO(2) and electricity, or sale prices for algae biodiesel) could alter these results.

Transformation and Removal of Tetrabromobisphenol A from Water in the Presence of Natural Organic Matter via Laccase-Catalyzed Reactions: Reaction Rates, Products, and Pathways

The widespread occurrence of the brominated flame retardant tetrabromobisphenol A (TBBPA) makes it a possible source of concern. Our experiments suggest that TBBPA can be effectively transformed by the naturally occurring laccase enzyme from Trametes versicolor. These reactions follow second-order kinetics, whereby apparent removal rate is a function of both substrate and enzyme concentrations. For reactions at different initial concentrations and with or without natural organic matter (NOM), reaction products are identified using liquid or gas chromatography with mass spectrometry. Detailed reaction pathways are proposed. It is postulated that two TBBPA radicals resulting from a laccase-mediated reaction are coupled together via interaction of an oxygen atom on one radical and a propyl-substituted aromatic carbon atom on the other. A 2,6-dibromo-4-isopropylphenol carbocation is then eliminated from the radical dimer. All but one of the detected products arise from either substitution or proton elimination of the 2,6-dibromo-4-isopropylphenol carbocation. Three additional products are identified for reactions in the presence of NOM, which suggests that reaction occurs between NOM and TBBPA radical. Data from acute immobilization tests with Daphnia confirm that TBBPA toxicity is effectively eliminated by laccase-catalyzed TBBPA removal. These findings are useful for understanding laccase-mediated TBBPA reactions and could eventually lead to development of novel methods to control TBBPA contamination.

Evaluating the Sustainability of Ceramic Filters for Point-of-Use Drinking Water Treatment

This study evaluates the social, economic, and environmental sustainability of ceramic filters impregnated with silver nanoparticles for point-of-use (POU) drinking water treatment in developing countries. The functional unit for this analysis was the amount of water consumed by a typical household over ten years (37,960 L), as delivered by either the POU technology or a centralized water treatment and distribution system. Results indicate that the ceramic filters are 3-6 times more cost-effective than the centralized water system for reduction of waterborne diarrheal illness among the general population and children under five. The ceramic filters also exhibit better environmental performance for four of five evaluated life cycle impacts: energy use, water use, global warming potential, and particulate matter emissions (PM10). For smog formation potential, the centralized system is preferable to the ceramic filter POU technology. This convergence of social, economic, and environmental criteria offers clear indication that the ceramic filter POU technology is a more sustainable choice for drinking water treatment in developing countries than the centralized treatment systems that have been widely adopted in industrialized countries.

Peroxidase‐mediated degradation of perfluorooctanoic acid

Concentrations of aqueous-phase perfluorooctanoic acid (PFOA), a representative perfluorinated aliphatic (PFA) compound, are shown to be reduced effectively via reaction with horseradish peroxidase (HRP), hydrogen peroxide, and a phenolic cosubstrate (4-methoxyphenol). Reaction rate profiles are pseudo-first order, yielding an apparent best-fit removal rate constant of k1 = 0.003/min (r2 = 0.96, n = 14). Approximately 68% depletion of the parent compound and 98% depletion of its related acute aquatic toxicity are achieved in 6 h. Because no PFOA removal is observed in the absence of cosubstrate and/or following consumption thereof, we conclude that radical intermediate species generated during reaction between HRP and 4-methoxyphenol mediate nonspecific depletion of PFOA and that these intermediates may be sufficiently reactive to sever the extremely stable C-F bonds of PFOA. These results are consistent with measurements of reaction by-products, including fluoride ion and various aliphatic species of shortened chain length. Based on these findings, we conclude that PFA degradation may occur via one of two mechanisms: Kolbe decarboxylation followed by stepwise conversion of -CF2 units to CO2 and fluoride ion, or radical abstraction from a double bond with subsequent fragmentation. Our results indicate that under appropriate conditions, enzymatic degradation may comprise a natural transformation pathway for PFAs. Moreover, we anticipate that appropriately engineered enzymatic processes may hold promise for treatment of PFOA-contaminated waters. This, to the best of our knowledge, is the first report to substantiate the efficacy of HRP-catalyzed reactions for contaminant removal via degradative reactions versus polymerization reactions.

Fate and transport of atorvastatin and simvastatin drugs during conventional wastewater treatment

This research investigates the environmental behavior of two widely prescribed cholesterol-lowering statin drugs that are expected to be present at significant concentrations in wastewater influents, namely: atorvastatin and simvastatin. Batch biodegradation experiments suggest that both statins are well degraded during secondary treatment, and removal rates exhibit a substrate-enhancement model reflecting elements of both first-order behavior and cometabolism. Resulting biodegradation parameters are used in conjunction with literature sorption parameters to construct a mass-balance model of statin concentrations during conventional treatment. Model results exhibit excellent accuracy compared to measurements from a medium-sized WWTP in the Southeastern USA. Influent concentrations of 1.56 μg L(-1) and 1.23 μg L(-1) were measured for atorvastatin and simvastatin. Results also suggest that 85-90% of each drug is removed during conventional treatment, with sorption accounting for less than 10% of overall removal. Expected effluent concentrations are orders of magnitude less than previously reported ecotoxicity thresholds for both drugs. Overall, results suggest statin active ingredients do not pose a significant environmental threat. It is recommended that future work characterize the fate of statin metabolites and that the same mass-balance modeling approach be used to assess other highly-prescribed pharmaceutical drugs.

Generation of Branched-Chain Fatty Acids through Lipoate-Dependent Metabolism Facilitates Intracellular Growth of Listeria monocytogenes

The gram-positive bacterial pathogen Listeria monocytogenes has evolved mechanisms to rapidly replicate in the host cytosol, implying efficient utilization of host-derived nutrients. However, the contribution of host nutrient scavenging versus that of bacterial biosynthesis toward rapid intracellular growth remains unclear. Nutrients that contribute to growth of L. monocytogenes include branched-chain fatty acids (BCFAs), amino acids, and other metabolic intermediates generated from acyl-coenzyme A, which is synthesized using lipoylated metabolic enzyme complexes. To characterize which biosynthetic pathways support replication of L. monocytogenes inside the host cytosol, we impaired lipoate-dependent metabolism by disrupting two lipoate ligase genes that are responsible for bacterial protein lipoylation. Interrupting lipoate-dependent metabolism modestly impaired replication in rich broth medium but strongly inhibited growth in defined medium and host cells and impaired the generation of BCFAs. Addition of short BCFAs and amino acids restored growth of the A1A2-deficient (A1A2-) mutant in minimal medium, implying that lipoate-dependent metabolism generates amino acids and BCFAs. BCFAs alone rescued intracellular growth and spread in L2 fibroblasts of the A1A2- mutant. Lipoate-dependent metabolism was also required in vivo, as a wild-type strain robustly outcompeted the lipoylation-deficient mutant in a murine model of listeriosis. The results of this study suggest that lipoate-dependent metabolism contributes to both amino acid and BCFA biosynthesis and that BCFA biosynthesis is preferentially required for intracellular growth of L. monocytogenes.

Peroxidase-mediated removal of endocrine disrupting compound mixtures from water

Several classes of oxidative enzymes have shown promise for efficient removal of endocrine disrupting compounds (EDCs) that are resistant to conventional wastewater treatments. Although the kinetics of reactions between individual EDCs and selected oxidative enzymes are well documented in the literature, there has been little investigation of reactions with EDC mixtures. This makes it impossible to predict how enzyme-mediated treatment systems will perform since wastewater effluents generally contain multiple EDCs. This paper reports pseudo-first order rate constants for a model oxidative enzyme, horseradish peroxidase (HRP), during single-substrate (k1) and mixed-substrate (k1-MIX) reactions. Measured values are compared with literature values of three Michaelis-Menten parameters: half-saturation constant (KM), enzyme turnover number (kCAT), and the ratio kCAT/KM. Published reports had suggested that each of these could be correlated with HRP reactivity towards EDCs in mixtures, and empirical results from this study show that KM can be used to predict the sequence of EDC removal reactions within a particular mixture. We also observed that k1-MIX values were generally greater than k1 values and that compounds exhibiting greatest estrogenic toxicities reacted most rapidly in a given mixture. Finally, because KM may be tedious to measure for every EDC of interest, we have constructed a quantitative structure-activity relationship (QSAR) model to predict these values. This model predicts KM quite accurately (R2=89%) based on two molecular characteristics: molecular volume and hydration energy. Its accuracy makes this QSAR a useful tool for predicting which EDCs will be removed most efficiently during enzyme treatment of EDC mixtures.