Effect of dispersion on adsorption of atrazine by aqueous suspensions of fullerenes

With the widespread application of fullerenes, it is critical to assess their environmental behaviors and their impacts on the transport and bioavailability of organic contaminants. The effects of fullerene particle size, chemistry of the solution, and natural organic matter on the adsorption of atrazine by aqueous dispersions of fullerenes (C(60)) were investigated in this work. The results showed that the Polanyi-Manes model could fit the adsorption isotherms well. Smaller sizes of fullerene particles led to increased available sites and, consequently, enhanced the adsorption of atrazine on C(60). However, intensely dispersed C(60) systems might not possess suitably high adsorptive capacities due to surface chemistry change. Adsorption of atrazine by aqueous dispersions of C(60) increased with a decrease in the pH of the solution. Introduction of humic acid significantly reduced the size of the C(60) particles, and resulted in the increase of the adsorption amount. Fullerene materials, once released into the aquatic environment, are inclined to form aqueous suspensions with different degrees of dispersion, which would greatly affect the transport and fate of organic contaminants.     

Bacteriophage inactivation by UV-A illuminated fullerenes: role of nanoparticle-virus association and biological targets

Inactivation rates of the MS2 bacteriophage and (1)O(2) generation rates by four different photosensitized aqueous fullerene suspensions were in the same order: aqu-nC(60) < C(60)(OH)(6) ≈ C(60)(OH)(24) < C(60)(NH(2))(6). Alterations to capsid protein secondary structures and protein oxidation were inferred by detecting changes in infrared vibrational frequencies and carbonyl groups respectively. MS2 inactivation appears to be the result of loss of capsid structural integrity (localized deformation) and the reduced ability to eject genomic RNA into its bacterial host. Evidence is also presented for possible capsid rupture in MS2 exposed to UV-A illuminated C(60)(NH(2))(6) through TEM imagery and detection of RNA infrared fingerprints in ATR-FTIR spectra. Fullerene-virus mixtures were also directly visualized in the aqueous phase using a novel enhanced darkfield transmission optical microscope fitted with a hyperspectral imaging (HSI) spectrometer. Perturbations in intermolecular extended chains, HSI, and electrostatic interactions suggest that inactivation is a function of the relative proximity between nanoparticles and viruses and (1)O(2) generation rate. MS2 log survival ratios were linearly related to CT (product of (1)O(2) concentration C and exposure time T) demonstrating the applicability of classical Chick-Watson kinetics for all fullerenes employed in this study. Results suggest that antiviral properties of fullerenes can be increased by adjusting the type of surface functionalization and extent of cage derivatization thereby increasing the (1)O(2) generation rate and facilitating closer association with biological targets.     

Estimates of embodied global energy and air-emission intensities of Japanese products for building a Japanese input-output life cycle assessment database with a global system boundary

To build a life cycle assessment (LCA) database of Japanese products embracing their global supply chains in a manner requiring lower time and labor burdens, this study estimates the intensity of embodied global environmental burden for commodities produced in Japan. The intensity of embodied global environmental burden is a measure of the environmental burden generated globally by unit production of the commodity and can be used as life cycle inventory data in LCA. The calculation employs an input-output LCA method with a global link input-output model that defines a global system boundary grounded in a simplified multiregional input-output framework. As results, the intensities of embodied global environmental burden for 406 Japanese commodities are determined in terms of energy consumption, greenhouse-gas emissions (carbon dioxide, methane, nitrous oxide, perfluorocarbons, hydrofluorocarbons, sulfur hexafluoride, and their summation), and air-pollutant emissions (nitrogen oxide and sulfur oxide). The uncertainties in the intensities of embodied global environmental burden attributable to the simplified structure of the global link input-output model are quantified using Monte Carlo simulation. In addition, by analyzing the structure of the embodied global greenhouse-gas intensities we characterize Japanese commodities in the context of LCA embracing global supply chains.     

Behavioral and physiological changes in Daphnia magna when exposed to nanoparticle suspensions (titanium dioxide, nano-C60, and C60HxC70Hx)

Little is known aboutthe impact manufactured nanoparticles will have on aquatic organisms. Previously, we demonstrated that toxicity differs with nanoparticle type and preparation and observed behavioral changes upon exposure to the more lethal nanoparticle suspensions. In this experiment, we quantified these behavioral and physiological responses of Daphnia magna at sublethal nanoparticle concentrations. Titanium dioxide (TiO2) and fullerenes (nano-C60) were chosen for their potential use in technology. Other studies suggest that addition of functional groups to particles can affect their toxicity to cell cultures, but it is unknown if the same is true at the whole organism level. Therefore, a fullerene derivative, C60HxC70Hx, was also used to examine how functional groups affect Daphnia response. Using a high-speed camera, we quantified several behavior and physiological parameters including hopping frequency, feeding appendage and postabdominal curling movement, and heart rate. Nano-C60 was the only suspension to cause a significant change in heart rate. Exposure to both nano-C60 and C60HxC70Hx suspensions caused hopping frequency and appendage movement to increase. These results are associated with increased risk of predation and reproductive decline. They indicate that certain nanoparticle types may have impacts on population and food web dynamics in aquatic systems.     

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.     

Biodiesel production in a semiarid environment: a life cycle assessment approach

While the use of biodiesel appears to be a promising alternative to petroleum fuel, the replacement of fossil fuel by biofuel may not bring about the intended climate cooling because of the increased soil N2O emissions due to N-fertilizer applications. Using a life cycle assessment approach, we assessed the influence of soil nitrous oxide (N2O) emissions on the life cycle global warming potential of the production and combustion of biodiesel from canola oil produced in a semiarid climate. Utilizing locally measured soil N2O emissions, rather than the Intergovernmental Panel on Climate Change (IPCC) default values, decreased greenhouse gas (GHG) emissions from the production and combustion of 1 GJ biodiesel from 63 to 37 carbon dioxide equivalents (CO2-e)/GJ. GHG were 1.1 to 2.1 times lower than those from petroleum or petroleum-based diesel depending on which soil N2O emission factors were included in the analysis. The advantages of utilizing biodiesel rapidly declined when blended with petroleum diesel. Mitigation strategies that decrease emissions from the production and application of N fertilizers may further decrease the life cycle GHG emissions in the production and combustion of biodiesel.     

Full chain energy analysis of biodiesel from Jatropha curcas L. in Thailand

Biodiesel production from Jatropha curcas Linnaeus (JCL) has been considered for partial substitution of diesel fuel for transportation in Thailand. The aim of this study is to investigate the energy consumption for long-term investment (20 years) of Jatropha Methyl Ester (JME) production in Thailand using a life cycle approach. Apart from the average result, two scenarios--best and worst case--are set up to illustrate the range of results due to the variety of management practices. The main contributors to the energy use are JCL cultivation, transesterification, and transportation process. The net energy gain (NEG) and net energy ratio (NER) of biodiesel and coproducts from the life cycle of JCL are 4720 GJ/ha and 6.03, respectively. Even if only biodiesel is considered without coproducts, the NER is 1.42, still higher than 1. The study will support decision makers in the energy policy sector to make informed decisions vis-a-vis promotion of JCL plantations for biodiesel.     

Fullerene-Enhanced Accumulation of p,p'-DDE in Agricultural Crop Species

The effect of C(60) fullerene exposure on the accumulation of dichlorodiphenyldichloroethylene (p,p'-DDE; DDT metabolite) by Cucurbita pepo L. (zucchini), Glycine max L. (soybean), and Solanum lycopersicum L. (tomato) was determined. The plants were grown in 125 mL jars of vermiculite amended with 0 or 40 mg of C(60) fullerenes. Prior to planting, the jars were amended with 40 mL solution containing 100 ng/mL of p,p'-DDE with 0 or 100 mg/L humic acid. During three weeks of growth, plants were watered with the same p,p'-DDE containing solutions. Total shoot p,p'-DDE levels in nonfullerene exposed tomato, soybean, and zucchini were 26.9, 131, and 675 ng, respectively; total root DDE content for the three plants was 402, 5970, and 5830 ng, respectively. Fullerenes increased the shoot p,p'-DDE content of zucchini by 29%; contaminant levels in soybean shoots were decreased by 48% but tomato shoot content was unaffected. The root and total plant p,p'-DDE content of all three species was significantly increased by fullerene exposure; enhanced contaminant uptake ranged from 30 to 65%. Humic acid, regardless of fullerene presence or plant type, significantly decreased the p,p'-DDE uptake. Fullerenes were detected in the roots of all plants but were not detected in plant shoots in the initial study. In a follow up study with zucchini designed to maximize biomass for extraction, over half the analyzed stems contained fullerenes at 60.5 to 4490 ng/g. These findings show that the carbon-based nanomaterials may significantly alter the accumulation and potentially the toxicity of cocontaminants in agricultural systems.     

Environmental impact of pyrolysis of mixed WEEE plastics part 1: Experimental pyrolysis data

Growth in waste electrical and electronic equipment (WEEE) is posing increasing problems of waste management, partly resulting from its plastic content. WEEE plastics include a range of polymers, some of which can be sorted and extracted for recycling. However a nonrecyclable fraction remains containing a mixture of polymers contaminated with other materials, and pyrolysis is a potential means of recovering the energy content of this. In preparation for a life cycle assessment of this option, described in part 2 of this paper set, data were collected from trials using experimental pyrolysis equipment representative of a continuous commercial process operated at 800 °C. The feedstock contained acrylonitrile-butadiene-styrene and high impact polystyrene with high levels of additives, and dense polymers including polyvinylchloride, polycarbonate, polyphenylene oxide, and polymethyl methacrylate. On average 39% was converted to gases, 36% to oils, and 25% remained as residue. About 35% of the gas was methane and 42% carbon monoxide, plus other hydrocarbons, oxygen and carbon dioxide. The oils were almost all aromatic, forming a similar mixture to fuel oil. The residue was mainly carbon with inorganic compounds from the plastic additives and most of the chlorine from the feedstock. The results showed that the process produced around 70% of the original plastic weight as potential fuel.     

Assessing the impact of nanomaterials on anaerobic microbial communities

As the technological benefits of nanotechnology begin to rapidly move from laboratory to large-scale industrial application, release of nanomaterials to the environment is inevitable. Little is known about the fate and effects of nanomaterials in nature. Major environmental receptors of nanomaterials will be soil, sediment, and biosolids from wastewater treatment. Analysis of anaerobic microbial activity and communities provides needed information about the effects of nanoparticles in certain environments. In this study, biosolids from anaerobic wastewater treatment sludge were exposed to fullerene (C60) in order to model an environmentally relevant discharge scenario. Activity was assessed by monitoring production of CO2 and CH4. Changes in community structure were monitored by denaturing gradient gel electrophoresis (DGGE), using primer sets targeting the small subunit rRNA genes of Bacteria, Archaea, and Eukarya. Findings suggest that C60 fullerenes have no significant effect on the anaerobic community over an exposure period of a few months. This conclusion is based on the absence of toxicity indicated by no change in methanogenesis relative to untreated reference samples. DGGE results show no evidence of substantial community shifts due to treatment with C60, in any subset of the microbial community.     

Environmental impact of pyrolysis of mixed WEEE plastics part 2: Life cycle assessment

Waste electrical and electronic equipment (WEEE) contains up to 25% plastics. Extraction of higher quality fractions for recycling leaves a mix of plastic types contaminated with other materials, requiring the least environmentally harmful disposal route. Data from trials of pyrolysis, described in part 1 of this paper set, were used in a life cycle assessment of the treatment of WEEE plastics. Various levels of recycling of the sorted fraction were considered, and pyrolysis was compared with incineration (with energy recovery) and landfill for disposal of the remainder. Increased recycling gave reduced environmental impact in almost all categories considered, although inefficient recycling decreased that benefit. Significant differences between pyrolysis, incineration and landfill were seen in climate change impacts, carbon sent to landfill, resources saved, and radiation. There was no overall "best" option. Landfill had the least short-term impact on climate change so could be a temporary means of sequestering carbon. Incineration left almost no carbon to landfill, but produced the most greenhouse gases. Pyrolysis or incineration saved most resources, with the balance depending on the source of electricity replaced by incineration. Pyrolysis emerged as a strong compromise candidate since the gases and oils produced could be used as fuels and so provided significant resource saving without high impact on climate change or landfill space.     

Uraninite and fullerene in atmospheric particulates

Particulates emitted from coal-burning power plants typically contain very small amounts of uranium (<10 ppm). Because of the extremely low concentrations, the form of the uranium has been unknown. Using a variety of advanced electron microscopy techniques, we have identified for the first time nanocrystals of uraninite, UO2+x, encapsulated in carbonaceous matter (< or = 50 nm) similar to fullerene. We have also identified, for the first time, closely associated fullerenes, C60. The "carbon-caged" nanocrystals of uraninite are protected from the immediate oxidation that would lead to increased mobility of uranium in the environment. Still, the presence of uranium in the very fine fraction of atmospheric particulates provides another pathway for radiation exposure.     

Transport and retention of colloidal aggregates of C60 in porous media: effects of organic macromolecules, ionic composition, and preparation method

The physical-chemical behavior of the fullerene C60 in environmental and physiological media is of interest for understanding the potential transport, exposure, and impacts of these materials on organisms and ecosystems. We considerthe role of electrolyte composition and concentration, the effect of organic macromolecules, and the mode of preparation of colloidal aggregates of C60 (nC60) on the deposition of these colloids in a porous medium such as a groundwater aquifer or a water treatment filter. Results for nC60 deposition are qualitatively consistent with trends anticipated by theory. Deposition was found to increase with increasing ionic strength, the presence of polysaccharide-type organic matter, and lower Darcy velocities. Factors that will tend to decrease the retention of these materials in porous media include a low ionic strength and the presence of humic-like substances, while the ionic strengths typical of many natural waters and the presence polysaccharide-based natural organic matter, as may be produced by algae or bacteria, will tend to favor deposition and reduced potential for exposure. Variability in the method of preparing colloidal aggregates of fullerenes was observed to yield significant differences in nC60 properties and transport behavior.     

Size-exclusive nanosensor for quantitative analysis of fullerene C60

This paper presents the first development of a mass-sensitive nanosensor for the isolation and quantitative analyses of engineered fullerene (C??) nanoparticles, while excluding mixtures of structurally similar fullerenes. Amino-modified beta-cyclodextrin (β-CD-NH?) was synthesized and confirmed by 1HNMR as the host molecule to isolate the desired fullerene C??. This was subsequently assembled onto the surfaces of gold-coated quartz crystal microbalance (QCM) electrodes using N-dicyclohexylcarbodiimide/N-hydroxysuccinimide (DCC/NHS) surface immobilization chemistry to create a selective molecular configuration described as (Au)-S-(CH?)2-CONH-beta-CD sensor. The mass change on the sensor configuration on the QCM was monitored for selective quantitative analysis of fullerene C?? from a C??/C?? mixture and soil samples. About ~101?-101? C?? particles/cm2 were successfully quantified by QCM measurements. Continuous spike of 200 μL of 0.14 mg C?? /mL produced changes in frequency (-Δf) that varied exponentially with concentration. FESEM and time-of-flight secondary-ion mass spectrometry confirmed the validity of sensor surface chemistry before and after exposure to fullerene C??. The utility of this sensor for spiked real-world soil samples has been demonstrated. Comparable sensitivity was obtained using both the soil and purified toluene samples. This work demonstrates that the sensor has potential application in complex environmental matrices.     

Efficiency of Recrystallization Methods for the Purification of β-Cyclodextrin

Cyclodextrins are an important class of products made from starch, and have many applications in the food and other industries. Among the cyclodextrins, β-cyclodextrin (β-CD) is the most important and is produced in the largest amount. Some commercial preparations of β-CD contain contaminants which must be eliminated to enhance the purity of the product. The purity of β-CD was increased by four different methods, i.e. recrystallization in water, and purification with isopropanol, cyclohexane, or isopropanol and cyclohexane. Purity of β-CD following the isopropanol method was over 99%, but the yield was only 40%. After cyclohexane treatment or the combined treatment with isopropanol and cyclohexane, purity was also over 99%, but yield was over 60%. Contaminants in commercial β-CD may be soluble or insoluble. Some contaminants would be bound in the inclusion cavity, and elimination of such contaminants by recrystallization in water was not successful. The purity and endothermic energy changes of β-CD were also determined by differential scanning calorimetry.     

Life cycle assessment of switchgrass- and corn stover-derived ethanol-fueled automobiles

Utilizing domestically produced cellulose-derived ethanol for the light-duty vehicle fleet can potentially improve the environmental performance and sustainability of the transport and energy sectors of the economy. A life cycle assessment model was developed to examine environmental implications of the production and use of ethanol in automobiles in Ontario, Canada. The results were compared to those of low-sulfur reformulated gasoline (RFG) in a functionally equivalent automobile. Two time frames were evaluated, one near-term (2010), which examines converting a dedicated energy crop (switchgrass) and an agricultural residue (corn stover) to ethanol; and one midterm (2020), which assumes technological improvements in the switchgrass-derived ethanol life cycle. Near-term results show that, compared to a RFG automobile, life cycle greenhouse gas (GHG) emissions are 57% lower for an E85-fueled automobile derived from switchgrass and 65% lower for ethanol from corn stover, on a grams of CO2 equivalent per kilometer basis. Corn stover ethanol exhibits slightly lower life cycle GHG emissions, primarily due to sharing emissions with grain production. Through projected improvements in crop and ethanol yields, results for the mid-term scenario show that GHG emissions could be 25-35% lower than those in 2010 and that, even with anticipated improvements in RFG automobiles, E85 automobiles could still achieve up to 70% lower GHG emissions across the life cycle.     

Reaction of water-stable C60 aggregates with ozone

While the reactivity of C60 has been described in a variety of organic solvents, little information is available regarding aqueous-based reactions due to solubility limitations. In this study, a reaction between C60, as a nanoscale suspension, and dissolved ozone in the aqueous phase was investigated. Findings indicate a facile reaction occurs, resulting in aggregate dissolution concurrent with formation of water-soluble fullerene oxide species. Product analyses, including 13C NMR, MS (LDI), FTIR, UV-Vis, and XPS, indicate highly oxidized fullerene with an average of approximately 29 oxygen additions per molecule, arranged in repeating hydroxyl and hemiketal functionalities. These findings are significant in that they (1) demonstrate the feasibility of other aqueous-based fullerene chemistries, including those for alternative synthesis routes, which might otherwise be considered prohibitive on the basis of solubility limitations, and (2) imply that the aqueous reactivity of fullerene-based materials must be considered appropriately for accurate assessment of their transport, fate, and potential risk(s) in environmental systems.     

Life cycle assessment of Chinese shrimp farming systems targeted for export and domestic sales

We conducted surveys of six hatcheries and 18 farms for data inputs to complete a cradle-to-farm-gate life cycle assessment (LCA) to evaluate the environmental performance for intensive (for export markets in Chicago) and semi-intensive (for domestic markets in Shanghai) shrimp farming systems in Hainan Province, China. The relative contribution to overall environmental performance of processing and distribution to final markets were also evaluated from a cradle-to-destination-port perspective. Environmental impact categories included global warming, acidification, eutrophication, cumulative energy use, and biotic resource use. Our results indicated that intensive farming had significantly higher environmental impacts per unit production than semi-intensive farming in all impact categories. The grow-out stage contributed between 96.4% and 99.6% of the cradle-to-farm-gate impacts. These impacts were mainly caused by feed production, electricity use, and farm-level effluents. By averaging over intensive (15%) and semi-intensive (85%) farming systems, 1 metric ton (t) live-weight of shrimp production in China required 38.3 ± 4.3 GJ of energy, as well as 40.4 ± 1.7 t of net primary productivity, and generated 23.1 ± 2.6 kg of SO(2) equiv, 36.9 ± 4.3 kg of PO(4) equiv, and 3.1 ± 0.4 t of CO(2) equiv. Processing made a higher contribution to cradle-to-destination-port impacts than distribution of processed shrimp from farm gate to final markets in both supply chains. In 2008, the estimated total electricity consumption, energy consumption, and greenhouse gas emissions from Chinese white-leg shrimp production would be 1.1 billion kW·h, 49 million GJ, and 4 million metric tons, respectively. Improvements suggested for Chinese shrimp aquaculture include changes in feed composition, farm management, electricity-generating sources, and effluent treatment before discharge. Our results can be used to optimize market-oriented shrimp supply chains and promote more sustainable shrimp production and consumption.     

Velocity effects on fullerene and oxide nanoparticle deposition in porous media

Products of nanochemistry have been proposed in a number of applications ranging from soil stabilization and cosmetics to groundwater remediation. A fundamental understanding of the transport properties of these materials is essential to assess their efficacy and environmental impact in such applications. In this work, we consider the effect of flow on nanoparticle transport and deposition in porous media. The transport of three aqueous suspensions of fullerenes in a well-characterized porous medium is compared with that of two oxide nanomaterials at two flow rates. Despite significant differences in surface chemistry and size, the fullerenes exhibited an unexpected and similar breakthrough behavior at the higher flow rate. A striking characteristic of the fullerene breakthrough curves obtained at the higher Darcy velocity was an initial enhancement in nanoparticle deposition shortly after the passage of the first pore volume of suspension, followed by an increase in passage. This velocity-sensitive "affinity transition" in the initial deposition of nanoparticles in the porous medium was observed for fullerene-based materials only at the higher velocity and was in no case observed for silica or titania nanoparticles. The removal of fullerene-based nanoparticles was observed to converge to a level that was independent of flow velocity, suggesting that under these conditions time scales for attachment or reorganization on the surface are greater than the time scale for transport to collector surfaces.     

Formation of Pyrazines by Chitin Pyrolysis

Chitin, poly-β-(1–4)-N-acetyl-D-glucosamine, was heated at 300-500°C for 5-60 min to examine the potential of pyrazine formation from chitin pyrolysis. 2-Methyl-, 2,3-dimethyl- and 2,3,5-trimethyl-pyrazine were formed at 300°C and additionally, 2,5-dimethylpyrazine was found with increasing pyrolysis temperature up to 500°C. During 60 min of pyrolysis more than twice as much 2,3,5-trimethylpyrazine as 2,5-dimethylpyrazine was developed. Thus, altering time and temperature of chitin pyrolysis could be useful for the development of certain pyrazines that have food flavor applications.