Potential release pathways, environmental fate, and ecological risks of carbon nanotubes

Carbon nanotubes (CNTs) are currently incorporated into various consumer products, and numerous new applications and products containing CNTs are expected in the future. The potential for negative effects caused by CNT release into the environment is a prominent concern and numerous research projects have investigated possible environmental release pathways, fate, and toxicity. However, this expanding body of literature has not yet been systematically reviewed. Our objective is to critically review this literature to identify emerging trends as well as persistent knowledge gaps on these topics. Specifically, we examine the release of CNTs from polymeric products, removal in wastewater treatment systems, transport through surface and subsurface media, aggregation behaviors, interactions with soil and sediment particles, potential transformations and degradation, and their potential ecotoxicity in soil, sediment, and aquatic ecosystems. One major limitation in the current literature is quantifying CNT masses in relevant media (polymers, tissues, soils, and sediments). Important new directions include developing mechanistic models for CNT release from composites and understanding CNT transport in more complex and environmentally realistic systems such as heteroaggregation with natural colloids and transport of nanoparticles in a range of soils.     

Environmental impacts of remediation of a trichloroethene-contaminated site: life cycle assessment of remediation alternatives

The environmental impacts of remediation of a chloroethene-contaminated site were evaluated using life cycle assessment (LCA). The compared remediation options are (i) in situ bioremediation by enhanced reductive dechlorination (ERD), (ii) in situ thermal desorption (ISTD), and (iii) excavation of the contaminated soil followed by off-site treatment and disposal. The results showed that choosing the ERD option will reduce the life-cycle impacts of remediation remarkably compared to choosing either ISTD or excavation, which are more energy-demanding. In addition to the secondary impacts of remediation, this study includes assessment of local toxic impacts (the primary impact) related to the on-site contaminant leaching to groundwater and subsequent human exposure via drinking water. The primary human toxic impacts were high for ERD due to the formation and leaching of chlorinated degradation products, especially vinyl chloride during remediation. However, the secondary human toxic impacts of ISTD and excavation are likely to be even higher, particularly due to upstream impacts from steel production. The newly launched model, USEtox, was applied for characterization of primary and secondary toxic impacts and combined with a site-dependent fate model of the leaching of chlorinated ethenes from the fractured clay till site.     

Natural and anthropogenic ethanol sources in north america and potential atmospheric impacts of ethanol fuel use

We used an ensemble of aircraft measurements with the GEOS-Chem chemical transport model to constrain present-day North American ethanol sources, and gauge potential long-range impacts of increased ethanol fuel use. We find that current ethanol emissions are underestimated by 50% in Western North America, and overestimated by a factor of 2 in the east. Our best estimate for year-2005 North American ethanol emissions is 670 GgC/y, with 440 GgC/y from the continental U.S. We apply these optimized source estimates to investigate two scenarios for increased ethanol fuel use in the U.S.: one that assumes a complete transition from gasoline to E85 fuel, and one tied to the biofuel requirements of the U.S. Energy Indepence and Security Act (EISA). For both scenarios, increased ethanol emissions lead to higher atmospheric acetaldehyde concentrations (by up to 14% during winter for the All-E85 scenario and 2% for the EISA scenario) and an associated shift in reactive nitrogen partitioning reflected by an increase in the peroxyacetyl nitrate (PAN) to NO(y) ratio. The largest relative impacts occur during fall, winter, and spring because of large natural emissions of ethanol and other organic compounds during summer. Projected changes in atmospheric PAN reflect a balance between an increased supply of peroxyacetyl radicals from acetaldehyde oxidation, and the lower NO(x) emissions for E85 relative to gasoline vehicles. The net effect is a general PAN increase in fall through spring, and a weak decrease over the U.S. Southeast and the Atlantic Ocean during summer. Predicted NO(x) concentrations decrease in surface air over North America (by as much 5% in the All-E85 scenario). Downwind of North America this effect is counteracted by higher NO(x) export efficiency driven by increased PAN production and transport. From the point of view of NO(x) export from North America, the increased PAN formation associated with E85 fuel use thus acts to offset the associated lower NO(x) emissions.     

Environmental life cycle assessment of Italian mozzarella cheese: Hotspots and improvement opportunities

The present study investigated a cradle-to-grave life cycle assessment to estimate the environmental impacts associated with Italian mozzarella cheese consumption. The differences between mozzarella produced from raw milk and mozzarella produced from curd were studied, and differences in manufacturing processes have been emphasized in order to provide guidance for targeted improvements at this phase. Specifically, the third-largest Italian mozzarella producer was surveyed to collect site-specific manufacturing data. The Ecoinvent v3.2 database was used for secondary data, whereas SimaPro 8.1 was the modeling software. The inventory included inputs from farm activities to end of life disposal of wasted mozzarella and packaging. Additionally, plant-specific information was used to assign major inputs, such as electricity, natural gas, packaging, and chemicals to specific products; however, where disaggregated information was not provided, milk solids allocation was applied. Notably, loss of milk solids was accounted during the manufacture, moreover mozzarella waste and transport were considered during distribution, retail, and consumption phases. Feed production and animal emissions were the main drivers of raw milk production. Electricity and natural gas usage, packaging (cardboard and plastic), transport, wastewater treatment, and refrigerant loss affected the emissions from a farm gate-to-dairy plant gate perspective. Post-dairy plant gate effects were mainly determined by electricity usage for storage of mozzarella, transport of mozzarella, and waste treatment. The average emissions were 6.66 kg of CO₂ equivalents and 45.1 MJ of cumulative energy demand/kg of consumed mozzarella produced directly from raw milk, whereas mozzarella from purchased curd had larger emissions than mozzarella from raw milk due to added transport of curd from specialty manufacturing plants, as well as electricity usage from additional processes at the mozzarella plant that are required to process the curd into mozzarella. Normalization points to ecotoxicity as the impact category most significantly influenced by mozzarella consumption. From a farm gate-to-grave perspective, ecotoxicity and freshwater and marine eutrophication are the first and second largest contributors of mozzarella consumption to average European effects, respectively. To increase environmental sustainability, an improvement of efficiency for energy and packaging usage and transport activities is recommended in the post-farm gate mozzarella supply chain.     

Prospective environmental life cycle assessment of nanosilver T-shirts

A cradle-to-grave life cycle assessment (LCA) is performed to compare nanosilver T-shirts with conventional T-shirts with and without biocidal treatment. For nanosilver production and textile incorporation, we investigate two processes: flame spray pyrolysis (FSP) and plasma polymerization with silver co-sputtering (PlaSpu). Prospective environmental impacts due to increased nanosilver T-shirt commercialization are estimated with six scenarios. Results show significant differences in environmental burdens between nanoparticle production technologies: The "cradle-to-gate" climate footprint of the production of a nanosilver T-shirt is 2.70 kg of CO(2)-equiv (FSP) and 7.67-166 kg of CO(2)-equiv (PlaSpu, varying maturity stages). Production of conventional T-shirts with and without the biocide triclosan has emissions of 2.55 kg of CO(2)-equiv (contribution from triclosan insignificant). Consumer behavior considerably affects the environmental impacts during the use phase. Lower washing frequencies can compensate for the increased climate footprint of FSP nanosilver T-shirt production. The toxic releases from washing and disposal in the life cycle of T-shirts appear to be of minor relevance. By contrast, the production phase may be rather significant due to toxic silver emissions at the mining site if high silver quantities are required.     

Relevance of emissions timing in biofuel greenhouse gases and climate impacts

Employing life cycle greenhouse gas (GHG) emissions as a key performance metric in energy and environmental policy may underestimate actual climate change impacts. Emissions released early in the life cycle cause greater cumulative radiative forcing (CRF) over the next decades than later emissions. Some indicate that ignoring emissions timing in traditional biofuel GHG accounting overestimates the effectiveness of policies supporting corn ethanol by 10-90% due to early land use change (LUC) induced GHGs. We use an IPCC climate model to (1) estimate absolute CRF from U.S. corn ethanol and (2) quantify an emissions timing factor (ETF), which is masked in the traditional GHG accounting. In contrast to earlier analyses, ETF is only 2% (5%) over 100 (50) years of impacts. Emissions uncertainty itself (LUC, fuel production period) is 1-2 orders of magnitude higher, which dwarfs the timing effect. From a GHG accounting perspective, emissions timing adds little to our understanding of the climate impacts of biofuels. However, policy makers should recognize that ETF could significantly decrease corn ethanol's probability of meeting the 20% GHG reduction target in the 2007 Energy Independence and Security Act. The added uncertainty of potentially employing more complex emissions metrics is yet to be quantified.     

Environmental impacts of algae-derived biodiesel and bioelectricity for transportation

Algae are a widely touted source of bioenergy with high yields, appreciable lipid contents, and an ability to be cultivated on marginal land without directly competing with food crops. Nevertheless, recent work has suggested that large-scale deployment of algae bioenergy systems could have unexpectedly high environmental burdens. In this study, a "well-to-wheel" life cycle assessment was undertaken to evaluate algae's potential use as a transportation energy source for passenger vehicles. Four algae conversion pathways resulting in combinations of bioelectricity and biodiesel were assessed for several relevant nutrient procurement scenarios. Results suggest that algae-to-energy systems can be either net energy positive or negative depending on the specific combination of cultivation and conversion processes used. Conversion pathways involving direct combustion for bioelectricity production generally outperformed systems involving anaerobic digestion and biodiesel production, and they were found to generate four and fifteen times as many vehicle kilometers traveled (VKT) per hectare as switchgrass or canola, respectively. Despite this, algae systems exhibited mixed performance for environmental impacts (energy use, water use, and greenhouse gas emissions) on a "per km" basis relative to the benchmark crops. This suggests that both cultivation and conversion processes must be carefully considered to ensure the environmental viability of algae-to-energy processes.     

Tannic acid adsorption and its role for stabilizing carbon nanotube suspensions

Dissolved organic matter (DOM) has been reported to stabilize carbon nanotube (CNT) suspensions, which increases concern over the subsequent transport and behavior of CNTs. However, it is unknown exactly which compounds or functional groups cause the stabilization of CNTs in natural environments. Naturally occurring tannic acid (TA), which has a large number of aromatic functional groups, was used as a surrogate of DOM to investigate its interaction with CNTs. CNT suspendability in TA solution increased with increasing CNT diameter without the aid of sonication. Sorption affinity of CNTs for TA increased with decreasing CNT diameter, positively related to their surface area. A two-stage sorption model was proposed to illustrate the interaction between CNTs and TA. TA molecules may be adsorbed first onto CNTs with aromatic rings binding to the surface carbon rings via pi-pi interactions, until forming a monolayer; the TA monolayer then further sorbed the dissolved TA by hydrogen bonds and other polar interactions. The sorbed TA increased the steric repulsion between individual CNTs, which might disperse the relatively loose CNT aggregates and result in the stabilization of large-diameter CNTs in TA solution. The sorption and suspending processwere also examined bytransmission electron microscopy, providing further evidence for the above proposed CNT-TA interactions. This study implies that widely distributed TA may promote the mobility and transport of CNTs in natural aqueous environments.     

Environmental impacts of cultured meat production

Cultured meat (i.e., meat produced in vitro using tissue engineering techniques) is being developed as a potentially healthier and more efficient alternative to conventional meat. Life cycle assessment (LCA) research method was used for assessing environmental impacts of large-scale cultured meat production. Cyanobacteria hydrolysate was assumed to be used as the nutrient and energy source for muscle cell growth. The results showed that production of 1000 kg cultured meat requires 26-33 GJ energy, 367-521 m(3) water, 190-230 m(2) land, and emits 1900-2240 kg CO(2)-eq GHG emissions. In comparison to conventionally produced European meat, cultured meat involves approximately 7-45% lower energy use (only poultry has lower energy use), 78-96% lower GHG emissions, 99% lower land use, and 82-96% lower water use depending on the product compared. Despite high uncertainty, it is concluded that the overall environmental impacts of cultured meat production are substantially lower than those of conventionally produced meat.     

Parametric assessment of climate change impacts of automotive material substitution

Quantifying the net climate change impact of automotive material substitution is not a trivial task. It requires the assessment of the mass reduction potential of automotive materials, the greenhouse gas (GHG) emissions from their production and recycling, and their impact on GHG emissions from vehicle use. The model presented in this paper is based on life cycle assessment (LCA) and completely parameterized, i.e., its computational structure is separated from the required input data, which is not traditionally done in LCAs. The parameterization increases scientific rigor and transparency of the assessment methodology, facilitates sensitivity and uncertainty analysis of the results, and also makes it possible to compare different studies and explain their disparities. The state of the art of the modeling methodology is reviewed and advanced. Assessment of the GHG emission impacts of material recycling through consequential system expansion shows that our understanding of this issue is still incomplete. This is a critical knowledge gap since a case study shows thatfor materials such as aluminum, the GHG emission impacts of material production and recycling are both of the same size as the use phase savings from vehicle mass reduction.     

Uncertainty analysis of life cycle greenhouse gas emissions from petroleum-based fuels and impacts on low carbon fuel policies

The climate change impacts of U.S. petroleum-based fuels consumption have contributed to the development of legislation supporting the introduction of low carbon alternatives, such as biofuels. However, the potential greenhouse gas (GHG) emissions reductions estimated for these policies using life cycle assessment methods are predominantly based on deterministic approaches that do not account for any uncertainty in outcomes. This may lead to unreliable and expensive decision making. In this study, the uncertainty in life cycle GHG emissions associated with petroleum-based fuels consumed in the U.S. is determined using a process-based framework and statistical modeling methods. Probability distributions fitted to available data were used to represent uncertain parameters in the life cycle model. Where data were not readily available, a partial least-squares (PLS) regression model based on existing data was developed. This was used in conjunction with probability mixture models to select appropriate distributions for specific life cycle stages. Finally, a Monte Carlo simulation was performed to generate sample output distributions. As an example of results from using these methods, the uncertainty range in life cycle GHG emissions from gasoline was shown to be 13%-higher than the typical 10% minimum emissions reductions targets specified by low carbon fuel policies.     

Ozone impacts of natural gas development in the Haynesville Shale

The Haynesville Shale is a subsurface rock formation located beneath the Northeast Texas/Northwest Louisiana border near Shreveport. This formation is estimated to contain very large recoverable reserves of natural gas, and during the two years since the drilling of the first highly productive wells in 2008, has been the focus of intensive leasing and exploration activity. The development of natural gas resources within the Haynesville Shale is likely to be economically important but may also generate significant emissions of ozone precursors. Using well production data from state regulatory agencies and a review of the available literature, projections of future year Haynesville Shale natural gas production were derived for 2009-2020 for three scenarios corresponding to limited, moderate, and aggressive development. These production estimates were then used to develop an emission inventory for each of the three scenarios. Photochemical modeling of the year 2012 showed increases in 2012 8-h ozone design values of up to 5 ppb within Northeast Texas and Northwest Louisiana resulting from development in the Haynesville Shale. Ozone increases due to Haynesville Shale emissions can affect regions outside Northeast Texas and Northwest Louisiana due to ozone transport. This study evaluates only near-term ozone impacts, but the emission inventory projections indicate that Haynesville emissions may be expected to increase through 2020.     

Regional characterization of freshwater Use in LCA: modeling direct impacts on human health

Life cycle assessment (LCA) is a methodology that quantifies potential environmental impacts for comparative purposes in a decision-making context. While potential environmental impacts from pollutant emissions into water are characterized in LCA, impacts from water unavailability are not yet fully quantified. Water use can make the resource unavailable to other users by displacement or quality degradation. A reduction in water availability to human users can potentially affect human health. If financial resources are available, there can be adaptations that may, in turn, shift the environmental burdens to other life cycle stages and impact categories. This paper proposes a model to evaluate these potential impacts in an LCA context. It considers the water that is withdrawn and released, its quality and scarcity in order to evaluate the loss of functionality associated with water uses. Regionalized results are presented for impacts on human health for two modeling approaches regarding affected users, including or not domestic uses, and expressed in disability-adjusted life years (DALY). A consumption and quality based scarcity indicator is also proposed as a midpoint. An illustrative example is presented for the production of corrugated board with different effluents, demonstrating the importance of considering quality, process effluents and the difference between the modeling approaches.     

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.     

Public health, climate, and economic impacts of desulfurizing jet fuel

In jurisdictions including the US and the EU ground transportation and marine fuels have recently been required to contain lower concentrations of sulfur, which has resulted in reduced atmospheric SO(x) emissions. In contrast, the maximum sulfur content of aviation fuel has remained unchanged at 3000 ppm (although sulfur levels average 600 ppm in practice). We assess the costs and benefits of a potential ultra-low sulfur (15 ppm) jet fuel standard ("ULSJ"). We estimate that global implementation of ULSJ will cost US$1-4bn per year and prevent 900-4000 air quality-related premature mortalities per year. Radiative forcing associated with reduction in atmospheric sulfate, nitrate, and ammonium loading is estimated at +3.4 mW/m(2) (equivalent to about 1/10th of the warming due to CO(2) emissions from aviation) and ULSJ increases life cycle CO(2) emissions by approximately 2%. The public health benefits are dominated by the reduction in cruise SO(x) emissions, so a key uncertainty is the atmospheric modeling of vertical transport of pollution from cruise altitudes to the ground. Comparisons of modeled and measured vertical profiles of CO, PAN, O(3), and (7)Be indicate that this uncertainty is low relative to uncertainties regarding the value of statistical life and the toxicity of fine particulate matter.     

Clay minerals affect the stability of surfactant-facilitated carbon nanotube suspensions

Carbon nanotubes (CNTs), because of their wide application, will inevitably enter aquatic systems, but the fate and transport of their suspensions in the environment are largely unknown. Clay minerals are expected to interact with CNT suspensions, affecting their fate and bioavailability. This study investigated the influence of clay minerals (kaolinite and montmorillonite) on the stability of surfactant (SDBS, CTAB, and TX100) facilitated multiwalled CNT (MWCNT) suspensions. Adsorption of the surfactants by MWCNTs and clay minerals was also examined. This is a first study on the interaction between clay minerals and surfactant-CNT suspensions. Sorption of SDBS by clay minerals and MWCNTs followed the order MWCNTs > montmorillonite approximately kaolinite; but sorption of CTAB and TX100 followed the order montmorillonite > MWCNTs > kaolinite. For SDBS suspended MWCNTs, introduction of montmorillonite and kaolinite could not change their stability; for CTAB suspended MWCNTs, both montmorillonite and kaolinite greatly deposited the suspended MWCNTs; for TX100 suspended MWCNTs, montmorillonite could partially deposit the suspended MWCNTs, whereas kaolinite showed minimal effect. Two mechanisms of clay minerals affecting MWCNT suspensions are (1) removal of surfactants by clay minerals from solution and MWCNT surface and (2) bridging between clay mineral and MWCNTs by surfactant.     

Unearthing potentials for decarbonizing the U.S. aluminum cycle

Global aluminum demand is anticipated to triple by 2050, by which time global greenhouse gas (GHG) emissions are advised to be cut 50-85% to avoid catastrophic climate impacts. To explore mitigation strategies systematically, a dynamic material flow model was developed to simulate the stocks and flows of the U.S. aluminum cycle and analyze the corresponding GHG emissions. Theoretical and realistic reduction potentials were identified and quantified. The total GHG emissions for the U.S. aluminum cycle in 2006 amount to 38 Mt CO(2)-equivalence. However, the U.S. has increasingly relied on imports of aluminum embodied in various products. The in-use stock is still growing fast in most product categories, which limits current scrap availability for recycling and emissions saving. Nevertheless, there is still large emission mitigation potential through recycling. The potentials from "100% old scrap collection" and "low emission energy" were each calculated to be higher than all process technology potential. Total emissions will decrease dramatically and mitigation priorities will change significantly under a stock saturation situation as much more old scrap becomes available for recycling. The nature of in-use stock development over the coming decades will be decisive for the aluminum industry to reach deeper emission cuts.     

Transformations of nanomaterials in the environment

Increasing use of engineered nanomaterials with novel properties relative to their bulk counterparts has generated a need to define their behaviors and impacts in the environment. The high surface area to volume ratio of nanoparticles results in highly reactive and physiochemically dynamic materials in environmental media. Many transformations, e.g. reactions with biomacromolecules, redox reactions, aggregation, and dissolution, may occur in both environmental and biological systems. These transformations and others will alter the fate, transport, and toxicity of nanomaterials. The nature and extent of these transformations must be understood before significant progress can be made toward understanding the environmental risks posed by these materials.     

The influence of vertical sorbed phase transport on the fate of organic chemicals in surface soils

Gaseous exchange between surface soil and the atmosphere is an important process in the environmental fate of many chemicals. It was hypothesized that this process is influenced by vertical transport of chemicals sorbed to soil particles. Vertical sorbed phase transport in surface soils occurs by many processes such as bioturbation, cryoturbation, and erosion into cracks formed by soil drying. The solution of the advection/diffusion equation proposed by Jury et al. to describe organic chemical fate in a uniformly contaminated surface soil was modified to include vertical sorbed phase transport This process was modeled using a sorbed phase diffusion coefficient, the value of which was derived from soil carbon mass balances in the literature. The effective diffusivity of the chemical in a typical soil was greater in the modified model than in the model without sorbed phase transport for compounds with log K(OW) > 2 and log K(OA) > 6. Within this chemical partitioning space, the rate of volatilization from the surface soil was larger in the modified model than in the original model by up to a factor of 65. The volatilization rate was insensitive to the value of the sorbed phase diffusion coefficient throughout much of this chemical partitioning space, indicating that the surface soil layer was essentially well-mixed and that the mass transfer coefficient was determined by diffusion through the atmospheric boundary layer only. When this process was included in a non-steady-state regional multimedia chemical fate model running with a generic emissions scenario to air, the predicted soil concentrations increased by upto a factor of 25,whilethe air concentrations decreased by as much as a factor of approximately 3. Vertical sorbed phase transport in the soil thus has a major impact on predicted air and soil concentrations, the state of equilibrium, and the direction and magnitude of the chemical flux between air and soil. It is a key process influencing the environmental fate of persistent organic pollutants (POPs).     

Food-miles and the relative climate impacts of food choices in the United States

Despite significant recent public concern and media attention to the environmental impacts of food, few studies in the United States have systematically compared the life-cycle greenhouse gas (GHG) emissions associated with food production against long-distance distribution, aka "food-miles." We find that although food is transported long distances in general (1640 km delivery and 6760 km life-cycle supply chain on average) the GHG emissions associated with food are dominated by the production phase, contributing 83% of the average U.S. household's 8.1 t CO2e/yr footprint for food consumption. Transportation as a whole represents only 11% of life-cycle GHG emissions, and final delivery from producer to retail contributes only 4%. Different food groups exhibit a large range in GHG-intensity; on average, red meat is around 150% more GHG-intensive than chicken or fish. Thus, we suggest that dietary shift can be a more effective means of lowering an average household's food-related climate footprint than "buying local." Shifting less than one day per week's worth of calories from red meat and dairy products to chicken, fish, eggs, or a vegetable-based diet achieves more GHG reduction than buying all locally sourced food.