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The ongoing transition toward electric vehicles (EVs) is changing materials used for vehicle production, of which the consequences for the environmental performance of EVs are not well understood and managed. We demonstrate that electrification coupled with lightweighting of automobiles will lead to significant changes in the industry's demand not only for battery materials but also for other materials used throughout the entire vehicle. Given the automotive industry's substantial consumption of raw materials, changes in its material demands are expected to trigger volatilities in material prices, consequently impacting the material composition and attractiveness of EVs. In addition, the materials recovered during end-of-life recycling of EVs as the vehicle fleet turns over will impact recycled material supplies both positively and negatively, impacting material availabilities and the economic incentive to engage in recycling. These supply chain impacts will influence material usage and the associated environmental performance of not only the automotive sector but also other metal-heavy industries such as construction. In light of these challenges, we propose the need for new research to understand the dynamic materials impacts of the EV transition that encompasses its implications on EV adoption and fleet life cycle environmental performance. Effectively coordinating the coevolution of material supply chains is crucial for making the sustainable transition to EVs a reality.

The U.S. EPA MOVES3 model was used to assess the impact of the large-scale introduction of electric vehicles on emissions of criteria pollutants (CO, hydrocarbons [HC], NOx, and particulate matter [PM]) and CO 2 from the U.S. light-duty vehicle fleet. Large reductions in emissions of these criteria pollutants occurred in 2000-2020. These trends are expected to continue through 2040 driven by turnover of the conventional fleet with old vehicles being replaced by battery electric vehicles (BEVs) and by new internal combustion engine vehicles (ICEVs) with modern emission control systems. Without the introduction of BEVs, the absolute emissions of CO, NOx, HC, and PM2.5 from the U.S. light-duty vehicle fleet are expected to decrease by approximately 61, 88, 55, and 20% from 2020 to 2040. Introduction of BEVs with market share increasing linearly to 100% in 2040 provides additional benefits, which, combined with ICEV fleet turnover, would lead to decreases of absolute emissions of CO, NOx, HC, and PM2.5 of approximately 77, 94, 71, and 37% from 2020 to 2040. Reductions in CO 2 emissions follow a similar pattern. Large decreases in criteria pollutant and CO 2 emissions from light duty vehicles lie ahead.

Increased use of vehicle electrification to reduce greenhouse gas (GHG) emissions has led to the need for an accurate and comprehensive assessment of the carbon footprint of traction batteries. Unfortunately, there are few lifecycle assessments (LCAs) of commercial lithium-ion batteries available in the literature, and those that are available focus on the cradle-to-gate stage, often with little or no consideration of the use phase. To address this shortfall, we report both cradle-to-gate and use-phase GHG emissions for the 2020 Model Year Ford Explorer plug-in hybrid electric vehicle (PHEV) NMC622 battery. Using primary industry data for battery design and manufacturing, cradle-to-gate emissions are estimated to be 1.38 t CO 2 e (101 kg CO 2 e/kWh), with 78% from materials and parts production and 22% from cell, module, and pack manufacturing. Using mass-induced energy consumptions of 0.6 and 1.6 kWh/(100 km 100 kg) for charge-depleting and -sustaining modes, respectively, the mass-induced use-phase emission of the battery is estimated to be 1.04 t CO 2 e. We show that battery emissions during the cradle-to-gate and use phases are comparable and that both phases need to be considered. A holistic and harmonized LCA approach that includes battery use is required to reduce carbon footprint uncertainties and guide future battery designs.

Catalysts can undergo structural changes during the reaction, affecting the number and/or the shape of active sites. For example, Rh can undergo interconversion between nanoparticles and single atoms when CO is present in the reaction mixture. Therefore, calculating a turnover frequency in such cases can be challenging as the number of active sites can change depending on the reaction conditions. Here, we use CO oxidation kinetics to track Rh structural changes occurring during the reaction. The apparent activation energy, considering the nanoparticles as the active sites, was constant in different temperature regimes. However, in a stoichiometric excess of O 2 , there were observed changes in the pre-exponential factor, which we link to changes in the number of active Rh sites. An excess of O 2 enhanced CO-induced Rh nanoparticle disintegration into single atoms, affecting catalyst activity. The temperature at which these structural changes occur depend on Rh particle size, with small particle sizes disintegrating at higher temperature, relative to the temperature required to break apart bigger particles. Rh structural changes were also observed during in situ infrared spectroscopic studies. Combining CO oxidation kinetics and spectroscopic studies allowed us to calculate the turnover frequency before and after nanoparticle redispersion into single atoms., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Accurate, fast, and flexible approaches for contact angle estimation in molecular dynamics simulations are of great importance for characterization of surface wettability, especially for machine learning approaches which would usually require thousands of computational contact angle evaluations for training and prediction purposes. However, evaluation of the contact angle from molecular simulations is typically a human-intensive process, which hinders the required fast throughput. To address this challenge, here a flexible and automated contact angle estimation tool, ContactAngleCalculator, is developed to meet these new requirements. In contrast to the current widely used computational approaches that are laborious and human intensive, this code is based on the concepts of the coarse-graining technique and equivalent contact area and volume of the droplet. Once the parameters are determined for a target liquid, it can automatically estimate the contact angle of different time points of one case or multiple cases by only one click. This tool is targeted for integration with machine learning methods, in which it can substantially streamline and reduce human labor and time in a computational contact angle estimation.

The COVID-19 pandemic has accelerated the growth of e-commerce and automated warehouses, vehicles, and robots and has created new options for grocery supply chains. We report and compare the greenhouse gas (GHG) emissions for a 36-item grocery basket transported along 72 unique paths from a centralized warehouse to the customer, including impacts of micro-fulfillment centers, refrigeration, vehicle automation, and last-mile transportation. Our base case is in-store shopping with last-mile transportation using an internal combustion engine (ICE) SUV (6.0 kg CO 2 e). The results indicate that emissions reductions could be achieved by e-commerce with micro-fulfillment centers (16-54%), customer vehicle electrification (18-42%), or grocery delivery (22-65%) compared to the base case. In-store shopping with an ICE pick-up truck has the highest emissions of all paths investigated (6.9 kg CO 2 e) while delivery using a sidewalk automated robot has the least (1.0 kg CO 2 e). Shopping frequency is an important factor for households to consider, e.g. halving shopping frequency can reduce GHG emissions by 44%. Trip chaining also offers an opportunity to reduce emissions with approximately 50% savings compared to the base case. Opportunities for grocers and households to reduce grocery supply chain carbon footprints are identified and discussed.

An effective method that can produce a large amount of Kraft lignin with improved homogeneity is strongly desired for Kraft lignin's high-value applications and scientific advancements. Herein, a one-pot acid-catalyzed liquefaction method was developed to recover Kraft lignin directly from black liquor. The recovery rate and properties of the recovered lignin were affected by the reaction time, reaction temperature, moisture content (MC), pH, and acid categories. The highest lignin recovery rate of 75% was achieved when the concentrated black liquor (MC = 25%) reacted with methanol at pH = 7 and 160 °C for 10 min using acetic acid as the catalyst. Most of the recovered lignin from this method showed an average molecular weight (Mw) value less than 2000 Da and a polydispersity (PDI) value less than 2.0. Such a PDI value was lower than that of current acid precipitated lignin (around 2.2-5.4). The recovered lignin was directly used to replace 20% of the petroleum-based polyol in the formula of a flexible polyurethane (PU) foam, and it was found that the molecular weight characteristics of the lignin affected the physical and mechanical properties of the flexible PU foams. The recovered lignin with the Mw value of 1600 Da and the PDI value of 1.8 was able to maintain the major physical and mechanical properties of the flexible PU foams. This study provided a promising way to recover lignin with improved homogeneity from black liquor with the potential to customize lignin properties to meet the requirements of downstream processes., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The use of cellulose has considerable promise in a wide range of industrial applications but is hampered by degradation in mechanical properties due to ambient moisture uptake. Existing models of equilibrium moisture content can predict the impact of these effects, but at present, the dynamical, atomic-scale picture of water ingress into cellulose is lacking. The present work reports nonequilibrium molecular simulations of the interface between cellulose and water aimed at capturing the initial stages of two simultaneous dynamical processes, water ingress into cellulose and cellulose dissolution into water. These simulations demonstrate that the process depends on the temperature and chain length in the amorphous region, where high temperatures can induce more mass exchange and short chains can easily detach from amorphous cellulose. A cooperative mechanism that involves both chemical and physical aspects, namely, hydrogen bonding and chain intertwining, respectively, is proposed to interpret the incipient dual ingress/dissolution process. Outcomes of this work will provide a foundation for cellulose functionalization strategies to impede moisture uptake and preserve the mechanical properties of nanocellulose in applications.

Increased E-commerce and demand for contactless delivery during the COVID-19 pandemic have fueled interest in robotic package delivery. We evaluate life cycle greenhouse gas (GHG) emissions for automated suburban ground delivery systems consisting of a vehicle (last-mile) and a robot (final-50-feet). Small and large cargo vans (125 and 350 cubic feet; V125 and V350) with an internal combustion engine (ICEV) and battery electric (BEV) powertrains were assessed for three delivery scenarios: (i) conventional , human-driven vehicle with human delivery; (ii) partially automated , human-driven vehicle with robot delivery; and (iii) fully automated , connected automated vehicle (CAV) with robot delivery. The robot's contribution to life cycle GHG emissions is small (2-6%). Compared to the conventional scenario, full automation results in similar GHG emissions for the V350-ICEV but 10% higher for the V125-BEV. Conventional delivery with a V125-BEV provides the lowest GHG emissions, 167 g CO 2 e/package, while partially automated delivery with a V350-ICEV generates the most at 486 g CO 2 e/package. Fuel economy and delivery density are key parameters, and electrification of the vehicle and carbon intensity of the electricity have a large impact. CAV power requirements and efficiency benefits largely offset each other, and automation has a moderate impact on life cycle GHG emissions.

Metal-organic frameworks (MOFs) are promising materials for hydrogen storage that fail to achieve expected theoretical values of volumetric storage density due to poor powder packing. A strategy that improves packing efficiency and volumetric hydrogen gas storage density dramatically through engineered morphologies and controlled-crystal size distributions is presented that holds promise for maximizing storage capacity for a given MOF. The packing density improvement, demonstrated for the benchmark sorbent MOF-5, leads to a significant enhancement of volumetric hydrogen storage performance relative to commercial MOF-5. System model projections demonstrate that engineering of crystal morphology/size or use of a bimodal distribution of cubic crystal sizes in tandem with system optimization can surpass the 25 g/L volumetric capacity of a typical 700 bar compressed storage system and exceed the DOE targets 2020 volumetric capacity (30 g/L). Finally, a critical link between improved powder packing density and reduced damage upon compaction is revealed leading to sorbents with both high surface area and high density.

Modern automobiles are composed of more than 2000 different compounds comprising 76 different elements. Identifying supply risks across this palette of materials is important to ensure a smooth transition to more sustainable transportation technologies. This paper provides insight into how electrification is changing vehicle composition and how that change drives supply risk vulnerability by providing the first comprehensive, high-resolution (elemental and compound level) snapshot of material use in both conventional and hybrid electric vehicles (HEVs) using a consistent methodology. To make these contributions, we analyze part-level data of material use for seven current year models, ranging from internal combustion engine vehicles (ICEV) to plug-in hybrid vehicles (PHEVs). With this data set, we apply a novel machine learning algorithm to estimate missing or unreported composition data. We propose and apply a metric of vulnerability, referred to as exposure, which captures economic importance and susceptibility to price changes. We find that exposure increases from $874 per vehicle for ICEV passenger vehicles to $2344 per vehicle for SUV PHEVs. The shift to a PHEV fleet would double automaker exposure adding approximately $1 billion per year of supply risk to a hypothetical fleet of a million vehicles. The increase in exposure is largely not only due to the increased use of battery elements like cobalt, graphite, and nickel but also some more commonly used materials, most notably copper.

This study examines the compatibility of multielectrolyte additives for NMC-silicon lithium-ion batteries. Research studies with Si-based anodes have shown stable reversible cycling using electrolytes containing fluoroethylene carbonate (FEC). At the same time, the electrolyte additive, tris(trimethylsilyl) phosphite (TTMSP), has shown to improve the electrochemical performance of nickel-rich layered cathodes, such as LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC). However, the combination of these electrolyte additives for the realization of a full-cell NMC-Si lithium-ion battery has not been previously explored. Changes in the electrochemical performance (capacity retention, internal cell resistance, and electrochemical impedance) in half-cells are studied as the ratio of TTMSP and FEC is tuned. At the optimal TTMSP/FEC ratio of 0.33 (T1F3), the NMC-Si full-cells achieve a 2× longer cycle life when compared to the FEC-rich (T0F4) electrolyte. Moreover, T1F3 full-cells demonstrate 1.5 mAh/cm 2 areal capacities and high-capacity retention (25% more than T0F4). A detailed investigation of the electrode-electrolyte interfaces is conducted by using time-of-flight secondary ion mass spectroscopy (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The chemical species depth profiles and elemental analysis illustrate adequate hydrogen fluoride (HF) scavenging. These results demonstrate the synergistic effects of electrolyte additives in minimizing the capacity degradation in NMC-Si full-cells by effectively stabilizing the electrode-electrolyte interfaces.

Energy storage can reduce peak power consumption from the electricity grid and therefore the cost for fast-charging electric vehicles (EVs). It can also enable EV charging in areas where grid limitations would otherwise preclude it. To address both the need for a fast-charging infrastructure as well as management of end-of-life EV batteries, second-life battery (SLB)-based energy storage is proposed for EV fast-charging systems. The electricity grid-based fast-charging configuration was compared to lithium-ion SLB-based configurations in terms of economic cost and life cycle environmental impact in five U.S. cities. Compared to using new batteries, SLB reduced the levelized cost of electricity (LCOE) by 12-41% and the global warming potential (GWP) by 7-77%. Photovoltaics along with SLB reduced the use of grid electricity and provided higher GWP and cumulative energy demand (CED) reduction compared to only using SLB. The LCOE of the SLB-based configurations was sensitive to SLB cost, lifetime, efficiency, and discount rate, whereas the GWP and CED were affected by SLB lifetime, efficiency, and the required enclosure materials. Solar insolation and electricity pricing structures were key in determining the configuration, which was economically and environmentally suitable for a location.

This work features the first-time use of poly(trimethylene terephthalate) (PTT), a biobased engineering thermoplastic, for fused deposition modeling (FDM) applications. Additives such as chain extenders (CEs) and impact modifiers are traditionally used to improve the processability of polymers for injection molding; as a proof of concept for their use in FDM, the same strategies were applied to PTT to improve its printability. The filament processing conditions and printing parameters were optimized to generate complete, warpage-free samples. The blends were characterized through physical, thermal, viscoelastic, and morphological analyses. In the optimal blend (90 wt % PTT, 10 wt % impact modifier, and 0.5 phr CE), the filament diameter was improved by ∼150%, the size of the spherulites significantly decreased to 5% of the ∼26 μm spherulite size found in neat PTT, and the melt flow index decreased to ∼4.7 g/10 min. From this blend, FDM samples with a high impact performance of ∼61 J/m were obtained, which are comparable to other conventional FDM thermoplastics. The ability to print complete and warpage-free samples from this blend suggests a new filament feedstock material for industrial and home-use FDM applications. This paper discusses methods to improve hard-to-print polymers and presents the improved printability of PTT as proof of these methods' effectiveness., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Electrification and lightweighting technologies are important components of greenhouse gas (GHG) emission reduction strategies for light-duty vehicles. Assessments of GHG emissions from light-duty vehicles should take a cradle-to-grave life cycle perspective and capture important regional effects. We report the first regionally explicit (county-level) life cycle assessment of the use of lightweighting and electrification for light-duty vehicles in the U.S. Regional differences in climate, electric grid burdens, and driving patterns compound to produce significant regional heterogeneity in the GHG benefits of electrification. We show that lightweighting further accentuates these regional differences. In fact, for the midsized cars considered in our analysis, model results suggest that aluminum lightweight vehicles with a combustion engine would have similar emissions to hybrid electric vehicles (HEVs) in about 25% of the counties in the US and lower than battery electric vehicles (BEVs) in 20% of counties. The results highlight the need for a portfolio of fuel efficient offerings to recognize the heterogeneity of regional climate, electric grid burdens, and driving patterns.

Mass adoption of electric vehicles (EVs) is widely viewed as essential to address climate change and requires a compelling case for ownership worldwide. While the manufacturing costs and technical capabilities of EVs are similar across regions, customer needs and economic contexts vary widely. Assessments of the all-electric-range required to cover day-to-day driving demand, and the climate and economic benefits of EVs, need to account for differences in regional characteristics and individual travel patterns. To meet this need travel profiles for 1681 light-duty passenger vehicles in China, the U.S., and Germany were used to make the first consistent multiregional comparison of customer and greenhouse gas (GHG) emission benefits of EVs. We show that despite differences in fuel prices, driving patterns, and subsidies, the economic benefits/challenges of EVs are generally similar across regions. Individuals who are economically most likely to adopt EVs have GHG benefits that are substantially greater than for average drivers. Such "priority" EV customers have large (32%-63%) reductions in cradle-to-grave GHG emissions. It is shown that low battery costs (below approximately $100/kWh) and a portfolio of EV offerings are required for mass adoption of electric vehicles.

Electrification of transportation offers clear national energy security benefits but unclear climate benefits. With the current heterogeneity of grid electricity mix in China, greenhouse gas (GHG) benefits of battery electric vehicles (BEVs) vary dramatically with location. Currently, compared to baseline conventional gasoline vehicles, BEVs in north and northeastern Chinese provinces have very modest (∼10-20%) well-to-wheel (WTW) GHG benefits, whereas BEVs in southern provinces have substantial benefits (∼50%). With the expected transition to a more renewable electricity mix documented here, regional effects will largely disappear and the benefits of BEVs will be substantial (∼60-70% lower than current internal combustion engine vehicles (ICEVs) and ∼10-40% lower than 2030 advanced hybrid electric vehicles (HEVs)) across the whole of China by 2030. GHG emissions from BEVs in Chinese cities (Beijing, Shanghai, Chongqing, and Pearl River Delta) and United States cities and regions (New York; Washington, DC; Chicago; New England; Texas; and California) in 2015 and 2030 are evaluated and compared. BEVs in Chinese cities will still have substantially higher WTW GHG emissions than those in New York, New England, and California in 2030.

A two-dimensional heterogeneous mathematical model was developed and validated to study the effect of relative humidity on volatile organic compound (VOC) adsorption onto activated carbon. The dynamic adsorption model consists of the macroscopic mass, momentum, and energy conservation equations and includes a multicomponent adsorption isotherm to predict the competitive adsorption equilibria between VOC and water vapor, which is described by an extended Manes method. Experimental verifications show that the model predicted the breakthrough profiles during competitive adsorption of the studied VOCs (2-propanol, acetone, n-butanol, toluene, 1,2,4-trimethylbenzene) at relative humidity range 0-95% with an overall mean relative absolute error (MRAE) of 11.8% for dry (0% RH) conditions and 17.2% for humid (55 and 95% RH) conditions, and normalized root-mean-square error (NRMSE) of 5.5 and 8.4% for dry and humid conditions, respectively. Sensitivity analysis was also conducted to test the robustness of the model in accounting for the impact of relative humidity on VOC adsorption by varying the adsorption temperature. Good agreement was observed between the experimental and simulated results with an overall MRAE of 12.4 and 7.1% for the breakthrough profiles and adsorption capacity, respectively. The model can be used to quantify the impact of carrier gas relative humidity during adsorption of contaminants from gas streams, which is useful when optimizing adsorber design and operating conditions.

Substituting conventional materials with lightweight materials is an effective way to reduce the life cycle greenhouse gas (GHG) emissions from light-duty vehicles. However, estimated GHG emission reductions of lightweighting depend on multiple factors including the vehicle powertrain technology and efficiency, lightweight material employed, and end-of-life material recovery. We developed a fleet-based life cycle model to estimate the GHG emission changes due to lightweighting the U.S. light-duty fleet from 2016 to 2050, using either high strength steel or aluminum as the lightweight material. Our model estimates that implementation of an aggressive lightweighting scenario using aluminum reduces 2016 through 2050 cumulative life cycle GHG emissions from the fleet by 2.9 Gt CO 2 eq (5.6%), and annual emissions in 2050 by 11%. Lightweighting has the greatest GHG emission reduction potential when implemented in the near-term, with two times more reduction per kilometer traveled if implemented in 2016 rather than in 2030. Delaying implementation by 15 years sacrifices 72% (2.1 Gt CO 2 eq) of the cumulative GHG emission mitigation potential through 2050. Lightweighting is an effective solution that could provide important near-term GHG emission reductions especially during the next 10-20 years when the fleet is dominated by conventional powertrain vehicles.

The reaction of perfluorooctanoic acid with the smallest carbonyl oxide Criegee intermediate, CH 2 OO, has been measured and is very rapid, with a rate coefficient of (4.9 ± 0.8) × 10 -10 cm 3 s -1 , similar to that for reactions of Criegee intermediates with other organic acids. Evidence is shown for the formation of hydroperoxymethyl perfluorooctanoate as a product. With such a large rate coefficient, reaction with Criegee intermediates can be a substantial contributor to atmospheric removal of perfluorocarboxylic acids. However, the atmospheric fates of the ester product largely regenerate the initial acid reactant. Wet deposition regenerates the perfluorocarboxylic acid via condensed-phase hydrolysis. Gas-phase reaction with OH is expected principally to result in formation of the acid anhydride, which also hydrolyzes to regenerate the acid, although a minor channel could lead to destruction of the perfluorinated backbone.

Although recent studies of connected and automated vehicles (CAVs) have begun to explore the potential energy and greenhouse gas (GHG) emission impacts from an operational perspective, little is known about how the full life cycle of the vehicle will be impacted. We report the results of a life cycle assessment (LCA) of Level 4 CAV sensing and computing subsystems integrated into internal combustion engine vehicle (ICEV) and battery electric vehicle (BEV) platforms. The results indicate that CAV subsystems could increase vehicle primary energy use and GHG emissions by 3-20% due to increases in power consumption, weight, drag, and data transmission. However, when potential operational effects of CAVs are included (e.g., eco-driving, platooning, and intersection connectivity), the net result is up to a 9% reduction in energy and GHG emissions in the base case. Overall, this study highlights opportunities where CAVs can improve net energy and environmental performance.

This article presents a cradle-to-grave (C2G) assessment of greenhouse gas (GHG) emissions and costs for current (2015) and future (2025-2030) light-duty vehicles. The analysis addressed both fuel cycle and vehicle manufacturing cycle for the following vehicle types: gasoline and diesel internal combustion engine vehicles (ICEVs), flex fuel vehicles, compressed natural gas (CNG) vehicles, hybrid electric vehicles (HEVs), hydrogen fuel cell electric vehicles (FCEVs), battery electric vehicles (BEVs), and plug-in hybrid electric vehicles (PHEVs). Gasoline ICEVs using current technology have C2G emissions of ∼450 gCO 2 e/mi (grams of carbon dioxide equivalents per mile), while C2G emissions from HEVs, PHEVs, H 2 FCEVs, and BEVs range from 300-350 gCO 2 e/mi. Future vehicle efficiency gains are expected to reduce emissions to ∼350 gCO 2 /mi for ICEVs and ∼250 gCO 2e /mi for HEVs, PHEVs, FCEVs, and BEVs. Utilizing low-carbon fuel pathways yields GHG reductions more than double those achieved by vehicle efficiency gains alone. Levelized costs of driving (LCDs) are in the range $0.25-$1.00/mi depending on time frame and vehicle-fuel technology. In all cases, vehicle cost represents the major (60-90%) contribution to LCDs. Currently, HEV and PHEV petroleum-fueled vehicles provide the most attractive cost in terms of avoided carbon emissions, although they offer lower potential GHG reductions. The ranges of LCD and cost of avoided carbon are narrower for the future technology pathways, reflecting the expected economic competitiveness of these alternative vehicles and fuels.

A comprehensive component-level assessment of several strategic and minor metals (SaMMs), including copper, manganese, magnesium, nickel, tin, niobium, light rare earth elements (LREEs; lanthanum, cerium, praseodymium, neodymium, promethium, and samarium), cobalt, silver, tungsten, heavy rare earth elements (yttrium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium), and gold, use in the 2013 model year Ford Fiesta, Focus, Fusion, and F-150 is presented. Representative material contents in cars and light-duty trucks are estimated using comprehensive, component-level data reported by suppliers. Statistical methods are used to accommodate possible errors within the database and provide estimate bounds. Results indicate that there is a high degree of variability in SaMM use and that SaMMs are concentrated in electrical, drivetrain, and suspension subsystems. Results suggest that trucks contain greater amounts of aluminum, nickel, niobium, and silver and significantly greater amounts of magnesium, manganese, gold, and LREEs. We find tin and tungsten use in automobiles to be 3-5 times higher than reported by previous studies which have focused on automotive electronics. Automotive use of strategic and minor metals is substantial, with 2013 vehicle production in the United States, Canada, EU15, and Japan alone accounting for approximately 20% of global production of Mg and Ta and approximately 5% of Al, Cu, and Sn. The data and analysis provide researchers, recyclers, and decision-makers additional insight into the vehicle content of strategic and minor metals of current interest.

Because of the existence of anisotropic surface energy with respect to the hexagonal close-packed (hcp) lattice structure, magnesium alloy dendrite prefers to grow along certain crystallographic directions and exhibits a complex growth pattern. To disclose the underlying mechanism behind the three-dimensional (3-D) growth pattern of magnesium alloy dendrite, an anisotropy function was developed in light of the spherical harmonics and experimental findings. Relevant atomistic simulations based on density functional theory were then performed to determine the anisotropic surface energy along different crystallographic directions, and the corresponding anisotropic strength was quantified via the least-square regression. Results of phase field simulations showed that the proposed anisotropy function could satisfactorily describe the 3-D growth pattern of the α-Mg dendrite observed in the experiments. Our investigations shed great insight into understanding the pattern formation of the hcp magnesium alloy dendrite at an atomic level., Competing Interests: The authors declare no competing financial interest.

The oxidation of 2-butyl radicals (and to a lesser extent 1-butyl radicals) has been studied over the temperature range of 298-735 K. The reaction of Cl atoms (formed by 360 nm irradiation of Cl 2 ) with n-butane generated the 2-butyl radicals in mixtures of n-C 4 H 10 , O 2 , and Cl 2 at temperatures below 600 K. Above 600 K, 2-butyl radicals were produced by thermal combustion reactions in the absence of chlorine. The yields of the products were measured by gas chromatography using a flame ionization detector. Major products quantified include acetone, acetic acid, acetaldehyde, butanone, 2-butanol, butanal, 1- and 2- chlorobutane, 1-butene, trans-2-butene, and cis-2-butene. At 298 K, the major oxygenated products are those expected from bimolecular reactions of 2-butylperoxy radicals (butanone, 2-butanol, and acetaldehyde). As the temperature rises to 390 K, the butanone decreases while acetaldehyde increases because of the increased rate of 2-butoxy radical decomposition. Acetone and acetic acid first appear in significant yield near 400 K, and these species rise slowly at first and then sharply, peaking near 525 K at yields of ∼25 and ∼20 mol %, respectively. In the same temperature range (400-525 K), butanone, acetaldehyde, and 2-butanol decrease rapidly. This suggests that acetone and acetic acid may be formed by previously unknown reaction channels of the 2-butylperoxy radical, which are in competition with those that lead to butanone, acetaldehyde, and 2-butanol. Above 570 K, the yields of acetone and acetic acid fall rapidly as the yields of the butenes rise. Experiments varying the Cl atom density, which in turn controls the entire radical pool density, were performed in the temperature range of 410-440 K. Decreasing the Cl atom density increased the yields of acetone and acetic acid while the yields of butanone, acetaldehyde, and 2-butanol decreased. This is consistent with the formation of acetone and acetic acid by unimolecular decomposition channels of the 2-butylperoxy radical, which are in competition with the bimolecular channels that form butanone, acetaldehyde, and 2-butanol. Such unimolecular decomposition channels would be unlikely to proceed through conventional transition states because those states would be very constrained. Therefore, the possibility that these decomposition channels proceed via roaming should be considered. In addition, we investigated and were unable to fit our data trends by a simplified ketohydroperoxide mechanism.

The literature analyzing the fuel saving, life cycle greenhouse gas (GHG) emission, and ownership cost impacts of lightweighting vehicles with different powertrains is reviewed. Vehicles with lower powertrain efficiencies have higher fuel consumption. Thus, fuel savings from lightweighting internal combustion engine vehicles can be higher than those of hybrid electric and battery electric vehicles. However, the impact of fuel savings on life cycle costs and GHG emissions depends on fuel prices, fuel carbon intensities and fuel storage requirements. Battery electric vehicle fuel savings enable reduction of battery size without sacrificing driving range. This reduces the battery production cost and mass, the latter results in further fuel savings. The carbon intensity of electricity varies widely and is a major source of uncertainty when evaluating the benefits of fuel savings. Hybrid electric vehicles use gasoline more efficiently than internal combustion engine vehicles and do not require large plug-in batteries. Therefore, the benefits of lightweighting depend on the vehicle powertrain. We discuss the value proposition of the use of lightweight materials and alternative powertrains. Future assessments of the benefits of vehicle lightweighting should capture the unique characteristics of emerging vehicle powertrains.

Direct tracking of lithium ions with time and spatial resolution can provide an important diagnostic tool for understanding mechanisms in lithium ion batteries. A fluorescent indicator of lithium ions, 2-(2-hydroxyphenyl)naphthoxazole, was synthesized and used for real-time tracking of lithium ions via widefield fluorescence microscopy. The fluorophore can be excited with visible light and was shown to enable quantitative determination of the lithium ion diffusion constant in a microfluidic model system for a plasticized polymer electrolyte lithium battery. The use of widefield fluorescence microscopy for in situ tracking of lithium ions in batteries is discussed.

Assessing the life-cycle benefits of vehicle lightweighting requires a quantitative description of mass-induced fuel consumption (MIF) and fuel reduction values (FRVs). We have extended our physics-based model of MIF and FRVs for internal combustion engine vehicles (ICEVs) to electrified vehicles (EVs) including hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and battery electric vehicles (BEVs). We illustrate the utility of the model by calculating MIFs and FRVs for 37 EVs and 13 ICEVs. BEVs have much smaller MIF and FRVs, both in the range 0.04-0.07 L e /(100 km 100 kg), than those for ICEVs which are in the ranges 0.19-0.32 and 0.16-0.22 L/(100 km 100 kg), respectively. The MIF and FRVs for HEVs and PHEVs mostly lie between those for ICEVs and BEVs. Powertrain resizing increases the FRVs for ICEVs, HEVs and PHEVs. Lightweighting EVs is less effective in reducing greenhouse gas emissions than lightweighting ICEVs, however the benefits differ substantially for different vehicle models. The physics-based approach outlined here enables model specific assessments for ICEVs, HEVs, PHEVs, and BEVs required to determine the optimal strategy for maximizing the life-cycle benefits of lightweighting the light-duty vehicle fleet.

We report the first cradle-to-gate emissions assessment for a mass-produced battery in a commercial battery electric vehicle (BEV); the lithium-ion battery pack used in the Ford Focus BEV. The assessment was based on the bill of materials and primary data from the battery industry, that is, energy and materials input data from the battery cell and pack supplier. Cradle-to-gate greenhouse gas (GHG) emissions for the 24 kWh Ford Focus lithium-ion battery are 3.4 metric tonnes of CO2-eq (140 kg CO2-eq per kWh or 11 kg CO2-eq per kg of battery). Cell manufacturing is the key contributor accounting for 45% of the GHG emissions. We review published studies of GHG emissions associated with battery production to compare and contrast with our results. Extending the system boundary to include the entire vehicle we estimate a 39% increase in the cradle-to-gate GHG emissions of the Focus BEV compared to the Focus internal combustion engine vehicle (ICEV), which falls within the range of literature estimates of 27-63% increases for hypothetical nonproduction BEVs. Our results reduce the uncertainties associated with assessment of BEV battery production, serve to identify opportunities to reduce emissions, and confirm previous assessments that BEVs have great potential to reduce GHG emissions over the full life cycle and provide local emission free mobility.

Platinum-group metals (PGMs) are technological and economic enablers of many industrial processes. This important role, coupled with their limited geographic availability, has led to PGMs being labeled as "critical materials". Studies of future PGM flows have focused on trends within material flows or macroeconomic indicators. We complement the previous work by introducing a novel technoeconomic model of substitution among PGMs within the automotive sector (the largest user of PGMs) reflecting the rational response of firms to changing prices. The results from the model support previous conclusions that PGM use is likely to grow, in some cases strongly, by 2030 (approximately 45% for Pd and 5% for Pt), driven by the increasing sales of automobiles. The model also indicates that PGM-demand growth will be significantly influenced by the future Pt-to-Pd price ratio, with swings of Pt and Pd demand of as much as 25% if the future price ratio shifts higher or lower even if it stays within the historic range. Fortunately, automotive catalysts are one of the more effectively recycled metals. As such, with proper policy support, recycling can serve to meet some of this growing demand.

Smog chambers with in situ FTIR detection were used to measure rate coefficients in 700 Torr of air and 296 ± 2 K of: k(Cl+(CF3)2CHOCH3) = (5.41 ± 1.63) × 10(-12), k(Cl+(CF3)2CHOCHO) = (9.44 ± 1.81) × 10(-15), k(Cl+CF3C(O)OCH3) = (6.28 ± 0.98) × 10(-14), k(OH+(CF3)2CHOCH3) = (1.86 ± 0.41) × 10(-13), and k(OH+(CF3)2CHOCHO) = (2.08 ± 0.63) × 10(-14) cm(3) molecule(-1) s(-1). The Cl atom initiated oxidation of (CF3)2CHOCH3 gives (CF3)2CHOCHO in a yield indistinguishable from 100%. The OH radical initiated oxidation of (CF3)2CHOCH3 gives the following products (molar yields): (CF3)2CHOCHO (76 ± 8)%, CF3C(O)OCH3 (16 ± 2)%, CF3C(O)CF3 (4 ± 1)%, and C(O)F2 (45 ± 5)%. The primary oxidation product (CF3)2CHOCHO reacts with Cl atoms to give secondary products (molar yields): CF3C(O)CF3 (67 ± 7)%, CF3C(O)OCHO (28 ± 3)%, and C(O)F2 (118 ± 12)%. CF3C(O)OCH3 reacts with Cl atoms to give: CF3C(O)OCHO (80 ± 8)% and C(O)F2 (6 ± 1)%. Atmospheric lifetimes of (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3 were estimated to be 62 days, 1.5 years, and 220 days, respectively. The 100-year global warming potentials (GWPs) for (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3 are estimated to be 6, 121, and 46, respectively. A comprehensive description of the atmospheric fate of (CF3)2CHOCH3 is presented.

Light-duty vehicles (LDVs) in the United States and elsewhere are required to meet increasingly challenging regulations on fuel economy and greenhouse gas (GHG) emissions as well as criteria pollutant emissions. New vehicle trends to improve efficiency include higher compression ratio, downsizing, turbocharging, downspeeding, and hybridization, each involving greater operation of spark-ignited (SI) engines under higher-load, knock-limited conditions. Higher octane ratings for regular-grade gasoline (with greater knock resistance) are an enabler for these technologies. This literature review discusses both fuel and engine factors affecting knock resistance and their contribution to higher engine efficiency and lower tailpipe CO2 emissions. Increasing compression ratios for future SI engines would be the primary response to a significant increase in fuel octane ratings. Existing LDVs would see more advanced spark timing and more efficient combustion phasing. Higher ethanol content is one available option for increasing the octane ratings of gasoline and would provide additional engine efficiency benefits for part and full load operation. An empirical calculation method is provided that allows estimation of expected vehicle efficiency, volumetric fuel economy, and CO2 emission benefits for future LDVs through higher compression ratios for different assumptions on fuel properties and engine types. Accurate "tank-to-wheel" estimates of this type are necessary for "well-to-wheel" analyses of increased gasoline octane ratings in the context of light duty vehicle transportation.

Lightweighting is a key strategy to improve vehicle fuel economy. Assessing the life-cycle benefits of lightweighting requires a quantitative description of the use-phase fuel consumption reduction associated with mass reduction. We present novel methods of estimating mass-induced fuel consumption (MIF) and fuel reduction values (FRVs) from fuel economy and dynamometer test data in the U.S. Environmental Protection Agency (EPA) database. In the past, FRVs have been measured using experimental testing. We demonstrate that FRVs can be mathematically derived from coast down coefficients in the EPA vehicle test database avoiding additional testing. MIF and FRVs calculated for 83 different 2013 MY vehicles are in the ranges 0.22-0.43 and 0.15-0.26 L/(100 km 100 kg), respectively, and increase to 0.27-0.53 L/(100 km 100 kg) with powertrain resizing to retain equivalent vehicle performance. We show how use-phase fuel consumption can be estimated using MIF and FRVs in life cycle assessments (LCAs) of vehicle lightweighting from total vehicle and vehicle component perspectives with, and without, powertrain resizing. The mass-induced fuel consumption model is illustrated by estimating lifecycle greenhouse gas (GHG) emission benefits from lightweighting a grille opening reinforcement component using magnesium or carbon fiber composite for 83 different vehicle models.

Metal-organic frameworks (MOFs) are an emerging class of microporous, crystalline materials with potential applications in the capture, storage, and separation of gases. Of the many known MOFs, MOF-5 has attracted considerable attention because of its ability to store gaseous fuels at low pressure with high densities. Nevertheless, MOF-5 and several other MOFs exhibit limited stability upon exposure to reactive species such as water. The present study quantifies the impact of humid air exposure on the properties of MOF-5 as a function of exposure time, humidity level, and morphology (i.e., powders vs pellets). Properties examined include hydrogen storage capacity, surface area, and crystallinity. Water adsorption/desorption isotherms are measured using a gravimetric technique; the first uptake exhibits a type V isotherm with a sudden increase in uptake at ∼50% relative humidity. For humidity levels below this threshold only minor degradation is observed for exposure times up to several hours, suggesting that MOF-5 is more stable than generally assumed under moderately humid conditions. In contrast, irreversible degradation occurs in a matter of minutes for exposures above the 50% threshold. Fourier transform infrared spectroscopy indicates that molecular and/or dissociated water is inserted into the skeletal framework after long exposure times. Densification into pellets can slow the degradation of MOF-5 significantly, and may present a pathway to enhance the stability of some MOFs.

Incomplete regeneration of activated carbon loaded with organic compounds results in heel build-up that reduces the useful life of the adsorbent. In this study, microwave heating was tested as a regeneration method for beaded activated carbon (BAC) loaded with n-dodecane, a high molecular weight volatile organic compound. Energy consumption and desorption efficiency for microwave-heating regeneration were compared with conductive-heating regeneration. The minimum energy needed to completely regenerate the adsorbent (100% desorption efficiency) using microwave regeneration was 6% of that needed with conductive heating regeneration, owing to more rapid heating rates and lower heat loss. Analyses of adsorbent pore size distribution and surface chemistry confirmed that neither heating method altered the physical/chemical properties of the BAC. Additionally, gas chromatography (with flame ionization detector) confirmed that neither regeneration method detectably altered the adsorbate composition during desorption. By demonstrating improvements in energy consumption and desorption efficiency and showing stable adsorbate and adsorbent properties, this paper suggests that microwave heating is an attractive method for activated carbon regeneration particularly when high-affinity VOC adsorbates are present.

China's oil imports and greenhouse gas (GHG) emissions have grown rapidly over the past decade. Addressing energy security and GHG emissions is a national priority. Replacing conventional vehicles with electric vehicles (EVs) offers a potential solution to both issues. While the reduction in petroleum use and hence the energy security benefits of switching to EVs are obvious, the GHG benefits are less obvious. We examine the current Chinese electric grid and its evolution and discuss the implications for EVs. China's electric grid will be dominated by coal for the next few decades. In 2015 in Beijing, Shanghai, and Guangzhou, EVs will need to use less than 14, 19, and 23 kWh/100 km, respectively, to match the 183 gCO2/km WTW emissions for energy saving vehicles. In 2020, in Beijing, Shanghai, and Guangzhou EVs will need to use less than 13, 18, and 20 kWh/100 km, respectively, to match the 137 gCO2/km WTW emissions for energy saving vehicles. EVs currently demonstrated in China use 24-32 kWh/100 km. Electrification will reduce petroleum imports; however, it will be very challenging for EVs to contribute to government targets for GHGs emissions reduction.

We present a global analysis of CO2 emission reductions from the light-duty vehicle (LDV) fleet consistent with stabilization of atmospheric CO2 concentration at 450 ppm. The CO2 emission reductions are described by g CO2/km emission targets for average new light-duty vehicles on a tank-to-wheel basis between 2010 and 2050 that we call CO2 glide paths. The analysis accounts for growth of the vehicle fleet, changing patterns in driving distance, regional availability of biofuels, and the changing composition of fossil fuels. New light-duty vehicle fuel economy and CO2 regulations in the U.S. through 2025 and in the EU through 2020 are broadly consistent with the CO2 glide paths. The glide path is at the upper end of the discussed 2025 EU range of 68-78 g CO2/km. The proposed China regulation for 2020 is more stringent than the glide path, while the 2017 Brazil regulation is less stringent. Existing regulations through 2025 are broadly consistent with the light-duty vehicle sector contributing to stabilizing CO2 at approximately 450 ppm. The glide paths provide long-term guidance for LDV powertrain/fuel development.

Engine-out and tailpipe emissions of NOx, CO, nonmethane hydrocarbons (NMHC), nonmethane organic gases (NMOG), total hydrocarbons (THC), methane, ethene, acetaldehyde, formaldehyde, ethanol, N2O, and NH3 from a 2006 model year Mercury Grand Marquis flexible fuel vehicle (FFV) operating on E0, E10, E20, E30, E40, E55, and E80 on a chassis dynamometer are reported. With increasing ethanol content in the fuel, the tailpipe emissions of ethanol, acetaldehyde, formaldehyde, methane, and ammonia increased; NOx and NMHC decreased; while CO, ethene, and N2O emissions were not discernibly affected. NMOG and THC emissions displayed a pronounced minimum with midlevel (E20-E40) ethanol blends; 25-35% lower than for E0 or E80. Emissions of NOx decreased by approximately 50% as the ethanol content increased from E0 to E30-E40, with no further decrease seen with E55 or E80. We demonstrate that emission trends from FFVs are explained by fuel chemistry and engine calibration effects. Fuel chemistry effects are fundamental in nature; the same trend of increased ethanol, acetaldehyde, formaldehyde, and CH4 emissions and decreased NMHC and benzene emissions are expected for all FFVs. Engine calibration effects are manufacturer and model specific; emission trends for NOx, THC, and NMOG will not be the same for all FFVs. Implications for air quality are discussed.

Lightweighting is a key strategy used to improve vehicle fuel economy. Replacing conventional materials (e.g., steel) with lighter alternatives (e.g., aluminum, magnesium, and composites) decreases energy consumption and greenhouse gas (GHG) emissions during vehicle use, but often increases energy consumption and GHG emissions during materials and vehicle production. Assessing the life-cycle benefits of mass reduction requires a quantitative description of the mass-induced fuel consumption during vehicle use. A new physics-based method for estimating mass-induced fuel consumption (MIF) is proposed. We illustrate the utility of this method by using publicly available data to calculate MIF values in the range of 0.2-0.5 L/(100 km 100 kg) based on 106 records of fuel economy tests by the U.S. Environmental Protection Agency for 2013 model year vehicles. Lightweighting is shown to have the most benefit when applied to vehicles with high fuel consumption and high power. Use of the physics-based model presented here would place future life cycle assessment studies of vehicle lightweighting on a firmer scientific foundation.

Gasoline direct injection (GDI) is a new engine technology intended to improve fuel economy and greenhouse gas emissions as required by recently enacted legislative and environmental regulations. The development of this technology must also ensure that these vehicles meet new LEV III and Tier 3 emissions standards as they phase in between 2017 and 2021. The aim of the present paper is to examine, at least for a small set, how the PM emissions from GDI vehicles change over their lifetime. The paper reports particle mass and number emissions of two GDI vehicles as a function of mileage up to 150K miles. These vehicles exhibit PM emissions that are near or below the upcoming 3 mg/mi FTP and 10 mg/mi US06 mass standards with little, if any, deterioration over 150K miles. Particle number emissions roughly follow the previously observed 2 × 10(12) particles/mg correlation between solid particle number and PM mass. They remained between the interim and final EU stage 6 solid particle count standard for gasoline vehicles throughout the mileage accumulation study. These examples demonstrate feasibility to meet near-term 3 mg/mi and interim EU solid particle number standards, but continued development is needed to ensure that this continues as further fuel economy improvements are made.

Replacing conventional materials (steel and iron) with lighter alternatives (e.g., aluminum, magnesium, and composites) decreases energy consumption and greenhouse gas (GHG) emissions during vehicle use but may increase energy consumption and GHG emissions during vehicle production. There have been many life cycle assessment (LCA) studies on the benefits of vehicle lightweighting, but the wide variety of assumptions used makes it difficult to compare results from the studies. To clarify the benefits of vehicle lightweighting we have reviewed the available literature (43 studies). The GHG emissions and primary energy results from 33 studies that passed a screening process were harmonized using a common set of assumptions (lifetime distance traveled, fuel-mass coefficient, secondary weight reduction factor, fuel consumption allocation, recycling rate, and energy intensity of materials). After harmonization, all studies indicate that using aluminum, glass-fiber reinforced plastic, and high strength steel to replace conventional steel decreases the vehicle life cycle energy use and GHG emissions. Given the flexibility in options implied by the variety of materials available and consensus that these materials have substantial energy and emissions benefits, it seems likely that lightweighting will be used increasingly to improve fuel economy and reduce life cycle GHG emissions from vehicles.

The approximately 100 million tonne per year increase in the use of corn to produce ethanol in the U.S. over the past 10 years, and projections of greater future use, have raised concerns that reduced exports of corn (and other agricultural products) and higher commodity prices would lead to land-use changes and, consequently, negative environmental impacts in other countries. The concerns have been driven by agricultural and trade models, which project that large-scale corn ethanol production leads to substantial decreases in food exports, increases in food prices, and greater deforestation globally. Over the past decade, the increased use of corn for ethanol has been largely matched by the increased corn harvest attributable mainly to increased yields. U.S. exports of corn, wheat, soybeans, pork, chicken, and beef either increased or remained unchanged. Exports of distillers' dry grains (DDG, a coproduct of ethanol production and a valuable animal feed) increased by more than an order of magnitude to 9 million tonnes in 2010. Increased biofuel production may lead to intensification (higher yields) and extensification (more land) of agricultural activities. Intensification and extensification have opposite impacts on land use change. We highlight the lack of information concerning the magnitude of intensification effects and the associated large uncertainties in assessments of the indirect land use change associated with corn ethanol.

The title question was addressed using an energy model that accounts for projected global energy use in all sectors (transportation, heat, and power) of the global economy. Global CO(2) emissions were constrained to achieve stabilization at 400-550 ppm by 2100 at the lowest total system cost (equivalent to perfect CO(2) cap-and-trade regime). For future scenarios where vehicle technology costs were sufficiently competitive to advantage either hydrogen or electric vehicles, increased availability of low-cost, low-CO(2) electricity/hydrogen delayed (but did not prevent) the use of electric/hydrogen-powered vehicles in the model. This occurs when low-CO(2) electricity/hydrogen provides more cost-effective CO(2) mitigation opportunities in the heat and power energy sectors than in transportation. Connections between the sectors leading to this counterintuitive result need consideration in policy and technology planning.

Smog chamber/FTIR techniques were used to determine rate constants of k(Cl+n-butanol) = (2.21 +/- 0.38) x 10(-10) and k(OH+n-butanol) = (8.86 +/- 0.85) x 10(-12) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296 +/- 2K. The sole primary product identified from the Cl atom initiated oxidation of n-butanol in the absence of NO was butyraldehyde (38 +/- 2%, molar yield). The primary products of the Cl atom initiated oxidation of n-butanol in the presence of NO were (molar yield) butyraldehyde (38 +/- 2%), propionaldehyde (23 +/- 3%), acetaldehyde (12 +/- 4%), and formaldehyde (33 +/- 3%). The substantially lower yields of propionaldehyde, acetaldehyde, and formaldehyde as primary products in experiments conducted in the absence of NO suggests that chemical activation is important in the atmospheric chemistry of CH(3)CH(2)CH(O)CH(2)OH and CH(3)CH(O)CH(2)CH(2)OH alkoxy radicals. The primary products of the OH radical initiated oxidation of n-butanol in the presence of NO were (molar yields) butyraldehyde (44 +/- 4%), propionaldehyde (19 +/- 2%), and acetaldehyde (12 +/- 3%). In all cases, the product yields were independent of oxygen concentration over the partial pressure range of 10-600 Torr. The yields of propionaldehyde, acetaldehyde, and formaldehyde quoted above were not corrected for secondary formation via oxidation of higher aldehydes and should be treated as upper limits. The reactions of Cl atoms and OH radicals with n-butanol proceed 38 +/- 2 and 44 +/- 4%, respectively, via attack on the alpha-position to give an alpha-hydroxy alkyl radical which reacts with O(2) to give butyraldehyde. The results are discussed with respect to the atmospheric chemistry of n-butanol.

Smog chamber/FTIR techniques were used to study the atmospheric chemistry of 3-pentanol and determine rate constants of k(Cl+3-pentanol) = (2.03 +/- 0.23) x 10 (-10) and k(OH+3-pentanol) = (1.32 +/- 0.15) x 10 (-11) cm (3) molecule (-1) s (-1) in 700 Torr of N 2/O 2 diluent at 296 +/- 2 K. The primary products of the Cl atom initiated oxidation of 3-pentanol in the absence of NO were (with molar yields) 3-pentanone (26 +/- 2%), propionaldehyde (12 +/- 2%), acetaldehyde (13 +/- 2%) and formaldehyde (2 +/- 1%). The primary products of the Cl atom initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (51 +/- 4%), propionaldehyde (39 +/- 2%), acetaldehyde (44 +/- 4%) and formaldehyde (4 +/- 1%). The primary products of the OH radical initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (58 +/- 3%), propionaldehyde (28 +/- 2%), and acetaldehyde (37 +/- 2%). In all cases the product yields were independent of oxygen concentration over the partial pressure range 10-700 Torr. The reactions of Cl atoms and OH radicals with 3-pentanol proceed 26 +/- 2 and 58 +/- 3%, respectively, via attack on the 3-position to give an alpha-hydroxyalkyl radical, which reacts with O 2 to give 3-pentanone. The results are discussed with respect to the literature data and atmospheric chemistry of 3-pentanol.