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The protection of Earth's stratospheric ozone (O 3 ) is an ongoing process under the auspices of the universally ratified Montreal Protocol and its Amendments and adjustments. A critical part of this process is the assessment of the environmental issues related to changes in O 3 . The United Nations Environment Programme's Environmental Effects Assessment Panel provides annual scientific evaluations of some of the key issues arising in the recent collective knowledge base. This current update includes a comprehensive assessment of the incidence rates of skin cancer, cataract and other skin and eye diseases observed worldwide; the effects of UV radiation on tropospheric oxidants, and air and water quality; trends in breakdown products of fluorinated chemicals and recent information of their toxicity; and recent technological innovations of building materials for greater resistance to UV radiation. These issues span a wide range of topics, including both harmful and beneficial effects of exposure to UV radiation, and complex interactions with climate change. While the Montreal Protocol has succeeded in preventing large reductions in stratospheric O 3 , future changes may occur due to a number of natural and anthropogenic factors. Thus, frequent assessments of potential environmental impacts are essential to ensure that policies remain based on the best available scientific knowledge., (© 2024. The Author(s).)

The Chinese central government has initiated pilot projects to promote the adoption of gasoline containing 10%v ethanol (E10). Vehicle emissions using ethanol blended fuels require investigation to estimate the environmental impacts of the initiative. Five fuel formulations were created using two blending methods (splash blending and match blending) to evaluate the impacts of formulations on speciated volatile organic compounds (VOCs) from exhaust emissions. Seven in-use vehicles covering China 4 to China 6 emission standards were recruited. Vehicle tests were conducted using the Worldwide Harmonized Test Cycle (WLTC) in a temperature-controlled chamber at 23 °C and -7 °C. Splash blended E10 fuels led to significant reductions in VOC emissions by 12%-75%. E10 fuels had a better performance of reducing VOC emissions in older model vehicles than in newer model vehicles. These results suggested that E10 fuel could be an option to mitigate the VOC emissions. Although replacing methyl tert-butyl ether (MTBE) with ethanol in regular gasoline had no significant effects on VOC emissions, the replacement led to lower aromatic emissions by 40%-60%. Alkanes and aromatics dominated approximately 90% of VOC emissions for all vehicle-fuel combinations. Cold temperature increased VOC emissions significantly, by 3-26 folds for all vehicle/fuel combinations at -7 °C. Aromatic emissions were increased by cold temperature, from 2 to 26 mg/km at 23 °C to 33-238 mg/km at -7 °C. OVOC emissions were not significantly affected by E10 fuel or cold temperature. The ozone formation potential (OFP) and secondary organic aerosol formation potential (SOAFP) of splash blended E10 fuels decreased by up to 76% and 81%, respectively, compared with those of E0 fuels. The results are useful to update VOC emission profiles of Chinese vehicles using ethanol blended gasoline and under low-temperature conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

This Assessment Update by the Environmental Effects Assessment Panel (EEAP) of the United Nations Environment Programme (UNEP) considers the interactive effects of solar UV radiation, global warming, and other weathering factors on plastics. The Assessment illustrates the significance of solar UV radiation in decreasing the durability of plastic materials, degradation of plastic debris, formation of micro- and nanoplastic particles and accompanying leaching of potential toxic compounds. Micro- and nanoplastics have been found in all ecosystems, the atmosphere, and in humans. While the potential biological risks are not yet well-established, the widespread and increasing occurrence of plastic pollution is reason for continuing research and monitoring. Plastic debris persists after its intended life in soils, water bodies and the atmosphere as well as in living organisms. To counteract accumulation of plastics in the environment, the lifetime of novel plastics or plastic alternatives should better match the functional life of products, with eventual breakdown releasing harmless substances to the environment., (© 2024. The Author(s).)

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.

The manuscript reviews the research on economic and environmental benefits of second-life electric vehicle batteries (EVBs) use for energy storage in households, utilities, and EV charging stations. Economic benefits depend heavily on electricity costs, battery costs, and battery performance; carbon benefits depend largely on the electricity mix charging the batteries. Environmental performance is greatest when used to store renewable energy such as wind and solar power. Inconsistent system boundaries make it challenging to compare the life cycle carbon footprint across different studies. The future growth of second-life EVB utilization faces several challenges, including the chemical and electrical properties and states of health of retired EVBs, the rapidly decreasing costs of new batteries, and different operational requirements. Measures to mitigate these challenges include the development of efficient diagnostic technologies, comprehensive test standards, and battery designs suitable for remanufacturing. Further research is needed based on real-world operational data and harmonized approaches., Competing Interests: The authors declare that they have no competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

The International Union of Pure and Applied Chemistry (IUPAC) has a long tradition of supporting the compilation of chemical data and their evaluation through direct projects, nomenclature and terminology work, and partnerships with international scientific bodies, government agencies and other organizations. The IUPAC Interdivisional Subcommittee on Critical Evaluation of Data (ISCED) has been established to provide guidance on issues related to the evaluation of chemical data. In this first report we define the general principles of the evaluation of scientific data and describe best practices and approaches to data evaluation in chemistry.

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.

Smog chambers interfaced with in situ FT-IR detection were used to investigate the kinetics and mechanisms of the Cl atom, OH radical, and O 3 initiated oxidation of ( Z )- and ( E )-1,2-dichloroethene (CHClCHCl) under atmospheric conditions. Relative and absolute rate methods were used to measure k (Cl + ( Z )-CHClCHCl) = (8.80 ± 1.75) × 10 -11 , k (Cl + ( E )-CHClCHCl) = (8.51 ± 1.69) × 10 -11 , k (OH + ( Z )-CHClCHCl) = (2.02 ± 0.43) × 10 -12 , k (OH + ( E )-CHClCHCl) = (1.94 ± 0.43) × 10 -12 , k (O 3 + ( Z )-CHClCHCl) = (4.50 ± 0.45) × 10 -21 , and k (O 3 + ( E )-CHClCHCl) = (1.02 ± 0.10) × 10 -19 cm 3 molecule -1 s -1 in 700 Torr of N 2 /air diluent at 298 ± 2 K. Pressure dependencies for the Cl atom reaction kinetics were observed for both isomers, consistent with isomerization occurring via Cl atom elimination from the chemically activated CHCl-CHCl-Cl adduct. The observed products from Cl initiated oxidation were HC(O)Cl (117-133%), CHCl 2 CHO (29-30%), and the corresponding CHClCHCl isomer (11-20%). OH radical initiated oxidation gives HC(O)Cl as a major product. For reaction of OH with ( E )-CHClCHCl, ( Z )-CHClCHCl was also observed as a product. A significant chlorine atom elimination channel was observed experimentally (HCl yield) and supported by computational results. Photochemical ozone creation potentials of 12 and 11 were estimated for ( Z )- and ( E )-CHClCHCl, respectively. Finally, an empirical kinetic relationship is explored for the addition of OH radicals or Cl atoms to small alkenes. The results are discussed in the context of the atmospheric chemistry of ( Z )- and ( E )-CHClCHCl.

We argue that there is a need for a more precise of PFAS in a way that avoids including compounds with single CF 3 -, -CF 2 -, or CF- groups and excludes TFA and compounds that degrade to just give TFA. An example that meets this need is the definition by the U.S. Environmental Protection Agency of PFAS as "per- and polyfluorinated substances that structurally contain the unit R-(CF 2 )-C(F)(R 1 )R 2 . Both the CF 2 and CF moieties are saturated carbons and none of the R groups (R, R 1 , or R 2 ) can be hydrogen". Adoption of this definition, or one like it, would place future technical and regulatory discussions of the environmental impacts of organo-fluorine compounds on a sounder technical footing by focusing PFAS discussions and regulation on long-chain perfluoroalkyl sulfonic acids and perfluoroalkyl carboxylic acids.

Expanded use of novel oil extraction technologies has increased the variability of petroleum resources and diversified the carbon footprint of the global oil supply 1 . Past life-cycle assessment (LCA) studies overlooked upstream emission heterogeneity by assuming that a decline in oil demand will displace average crude oil 2 . We explore the life-cycle greenhouse gas emissions impacts of marginal crude sources, identifying the upstream carbon intensity (CI) of the producers most sensitive to an oil demand decline (for example, due to a shift to alternative vehicles). We link econometric models of production profitability of 1,933 oilfields (~90% of the 2015 world supply) with their production CI. Then, we examine their response to a decline in demand under three oil market structures. According to our estimates, small demand shocks have different upstream CI implications than large shocks. Irrespective of the market structure, small shocks (-2.5% demand) displace mostly heavy crudes with ~25-54% higher CI than that of the global average. However, this imbalance diminishes as the shocks become bigger and if producers with market power coordinate their response to a demand decline. The carbon emissions benefits of reduction in oil demand are systematically dependent on the magnitude of demand drop and the global oil market structure., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

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.

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.

Asia Pacific (AP) is the largest regional vehicle market and accounted for 48% of global sales in 2019. Air quality is a pressing issue in many AP countries and together with increased vehicle sales has led to intense scrutiny of vehicle emissions. The heterogeneity of socio-economic features and transportation patterns in AP countries has resulted in different emission levels and control policies. We present an assessment of the historical and future emissions of on-road transportation and strategies to tackle emission challenges. First, we collected historical country-level population, economic development, vehicle ownership, and transportation policy data from 1900 to 2020, and forecast future development of on-road transportation activity (both passenger and freight) based on its historical relationship with socio-economic development through 2050. We considered major countries (China, India, Japan, South Korea, Australia) individually and other AP countries as a group. Second, we generated a series of emission control scenarios with various stringency levels after a comprehensive review of vehicle control measures implemented in AP countries. The control packages included transportation mode shifts, pollutant emission standards, fuel consumption standards, fuel and powertrain diversification, improvement in fuel quality, and economic and transportation policies. Localized emission factors for greenhouse gases (GHGs) and criteria air pollutants (carbon monoxide (CO), nitrogen oxides (NO x ), and particulate matter (PM)) were collected and estimated in line with the emission control measures. Third, we estimated historical and future emissions of AP on-road transportation from 1900 to 2050. The results showed that major air pollutants (NO x , CO, and PM 2.5 ) from on-road vehicles peaked in 2000-2010 and are now declining despite increasing vehicle population. Control of GHGs is more challenging than for criteria air pollutants. In our reference scenario where existing policies and emission standards are implemented and new technologies are adopted according to national plans, road transportation GHG emissions in AP peak in approximately 2040.

Human activity has led to increased atmospheric concentrations of many gases, including halocarbons, and may lead to emissions of many more gases. Many of these gases are, on a per molecule basis, powerful greenhouse gases, although at present-day concentrations their climate effect is in the so-called weak limit (i.e., their effect scales linearly with concentration). We published a comprehensive review of the radiative efficiencies (RE) and global warming potentials (GWP) for around 200 such compounds in 2013 (Hodnebrog et al., 2013, https://doi.org/10.1002/rog.20013). Here we present updated RE and GWP values for compounds where experimental infrared absorption spectra are available. Updated numbers are based on a revised "Pinnock curve", which gives RE as a function of wave number, and now also accounts for stratospheric temperature adjustment (Shine & Myhre, 2020, https://doi.org/10.1029/2019MS001951). Further updates include the implementation of around 500 absorption spectra additional to those in the 2013 review and new atmospheric lifetimes from the literature (mainly from WMO (2019)). In total, values for 60 of the compounds previously assessed are based on additional absorption spectra, and 42 compounds have REs which differ by >10% from our previous assessment. New RE calculations are presented for more than 400 compounds in addition to the previously assessed compounds, and GWP calculations are presented for a total of around 250 compounds. Present-day radiative forcing due to halocarbons and other weak absorbers is 0.38 [0.33-0.43] W m -2 , compared to 0.36 [0.32-0.40] W m -2 in IPCC AR5 (Myhre et al., 2013, https://doi.org/10.1017/CBO9781107415324.018), which is about 18% of the current CO 2 forcing., (©2020. The Authors.)

Smog chamber/FTIR techniques were used to investigate the kinetics and mechanism of the Cl atom and OH radical initiated oxidation of 2,2-dichloroethanol at (296 ± 1) K. Relative rate methods were used to measure k(Cl + CHCl 2 CH 2 OH) = (5.87 ± 0.96) × 10 -12 and k(OH + CHCl 2 CH 2 OH) = (5.54 ± 1.94) × 10 -13 cm 3 molecule -1 s -1 . Chlorine atom initiated oxidation of CHCl 2 CH 2 OH in one atmosphere of air gives HCOCl, CHCl 2 CHO, and COCl 2 in yields of (62 ± 5)%, (39 ± 10)%, and (8 ± 2)%, respectively. The rate constant k(Cl + CHCl 2 CHO) = (8.3 ± 16) × 10 -12 cm 3 molecule -1 s -1 was determined and the IR spectra of CHCl 2 CHO is reported for the first time. The atmospheric lifetime for CHCl 2 CH 2 OH is estimated as 21 days. The experimental results are discussed in the context of the atmospheric chemistry of chlorinated alcohols.

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.

Interest and investment in electric vertical takeoff and landing aircraft (VTOLs), commonly known as flying cars, have grown significantly. However, their sustainability implications are unclear. We report a physics-based analysis of primary energy and greenhouse gas (GHG) emissions of VTOLs vs. ground-based cars. Tilt-rotor/duct/wing VTOLs are efficient when cruising but consume substantial energy for takeoff and climb; hence, their burdens depend critically on trip distance. For our base case, traveling 100 km (point-to-point) with one pilot in a VTOL results in well-to-wing/wheel GHG emissions that are 35% lower but 28% higher than a one-occupant internal combustion engine vehicle (ICEV) and battery electric vehicle (BEV), respectively. Comparing fully loaded VTOLs (three passengers) with ground-based cars with an average occupancy of 1.54, VTOL GHG emissions per passenger-kilometer are 52% lower than ICEVs and 6% lower than BEVs. VTOLs offer fast, predictable transportation and could have a niche role in sustainable mobility.

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.

Photochemical reactors were used to study the kinetics and mechanisms of reactions of Cl atoms and OH radicals with hexa- and penta-fluorobenzene (C6F6, C6F5H) in 700 Torr total pressure of N2, air, or O2 diluent at 296 ± 2 K. C6F6 and C6F5H undergo ring-opening following 254 nm UV irradiation, but with small quantum yields (φ < 0.03). Reaction of Cl atoms with C6F6 proceeds via adduct formation, while the reaction of Cl atoms with C6F5H proceeds via hydrogen abstraction and adduct formation. C6F6-Cl and C6F5H-Cl adducts decompose rapidly (k ∼ 105-106 s-1) reforming the reactants, and react with Cl atoms to form products. The fraction of adduct reacting with Cl atoms increases with steady state Cl atom concentration, resulting in an increasing apparent effective Cl atom rate constant. The rate constant for the H-abstraction channel for Cl + C6F5H is estimated at (7.3 ± 5.7) × 10-16 cm3 molecule-1 s-1. Establishment of the equilibrium between the adducts and the aromatic reactant + Cl occurs rapidly with equilibrium constants of K([adduct]/[aromatic][Cl]) = (1.96 ± 0.11) × 10-16 and (9.28 ± 0.11) × 10-17 cm3 molecule-1 for C6F6 and C6F5H, respectively. Reaction of the adducts with O2 occurs slowly with estimated rate constants of <7 and <4 × 10-18 cm3 molecule-1 s-1 for C6F6-Cl and C6F5H-Cl, respectively. The rate constants for reaction of OH radicals with C6F6 and C6F5H were determined to be (2.27 ± 0.49) × 10-13 and (2.56 ± 0.62) × 10-13 cm3 molecule-1 s-1, respectively. UV and IR spectra of C6F6 and C6F5H at 296 ± 1 K were collected and calibrated. Results are discussed in the context of available literature data for reactions of Cl atoms and OH radicals with halogenated aromatic compounds.

The chemical mechanisms of the OH radical, Cl-atom and O3 initiated oxidation of (Z)-CF3CH[double bond, length as m-dash]CHCl were studied at 296 ± 1 K in 10-700 Torr air of N2/O2 diluent. Cl atoms add to the [double bond splayed left]C[double bond, length as m-dash]C[double bond splayed right] double bond: 12 ± 5% to the terminal carbon and 85 ± 5% to the central carbon. In 700 Torr of air the products are CF3CHClCHO, HCOCl, CF3COCl, CF3CHO, (E)-CF3CH[double bond, length as m-dash]CHCl, CF3C(O)CHCl2, and CF3CHClCOCl. The yield of (E) isomer was dependent on total pressure, but independent of O2 partial pressure; consistent with isomerization occurring via Cl atom elimination from the chemically activated rather than the thermalized CF3CHCHCl-Cl adduct. The rate constant for (Z)-CF3CH[double bond, length as m-dash]CHCl + Cl was measured at low pressure (10-15 Torr) and found to be indistinguishable from that determined at 700 Torr total pressure, whereas the low pressure rate constant for (E)-CF3CH[double bond, length as m-dash]CHCl was 36% smaller. G4MP2 ab initio calculations showed that the (E) isomer is 1.2 kcal mol-1 more stable than the (Z) isomer. Cl atom elimination from the adduct will preferentially form the (E) isomer and hence the rate of CF3CH[double bond, length as m-dash]CHCl loss will be more sensitive to pressure for the (Z) than the (E) isomer. Reaction of (Z)-CF3CH[double bond, length as m-dash]CHCl with OH radicals gives CF3CHO, HCOCl, (E)-CF3CH[double bond, length as m-dash]CHCl, and HCl. A significant chlorine atom elimination channel was observed experimentally, and supported by computational results. The oxidation products of the reaction of O3 with (Z)- and (E)-CF3CH[double bond, length as m-dash]CHCl were determined with no evidence of isomerization. The results are discussed with respect to the atmospheric chemistry and environmental impact of (Z)- and (E)-CF3CH[double bond, length as m-dash]CHCl.

The increasing adoption of intelligent transportation system (ITS) data in smart-city initiatives worldwide has offered unprecedented opportunities for improving transportation air quality management. In this paper, we demonstrate the effective use of ITS and other traffic data to develop a link-level and hourly-based dynamic vehicle emission inventory. Our work takes advantage of the extensive ITS infrastructure deployed in Nanjing, China (6600 km 2 ) that offers high-resolution, multi-source traffic data of the road network. Improved than conventional emission inventories, the ITS data empower the strength of revealing significantly temporal and spatial heterogeneity of traffic dynamics that pronouncedly impacts traffic emission patterns. Four urban districts account for only 4% of the area but approximately 30%-40% of vehicular emissions (e.g., CO 2 and air pollutants). Owing to the detailed resolution of road network traffic, two types of emission hotspots are captured by the dynamic emission inventory: those in the urban area dominated by urban passenger traffic, and those along outlying highway corridors reflecting inter-city freight transportation (especially in terms of NO X ). Fine-grained quantification of emissions reductions from traffic restriction scenarios is explored. ITS data-driven emission management systems coupled with atmospheric models offer the potential for dynamic air quality management in the future., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The OH-initiated photo-oxidation of perfluoro ethyl vinyl ether (C2F5OCF[double bond, length as m-dash]CF2, PEVE) in air (298 K, 50 and 750 Torr total pressure) was studied in a photochemical reactor using in situ detection of PEVE and its products by Fourier transform IR absorption spectroscopy. The relative rate technique was used to derive the rate coefficient, k1, for the reaction of PEVE with OH as k1 = (2.8 ± 0.3) × 10-12 cm3 molecule-1 s-1. The photo-oxidation of PEVE in the presence of NOx at 1 bar results in formation of C2F5OCFO, FC(O)C(O)F and CF2O in molar yields of 0.50 ± 0.07, 0.46 ± 0.07 and 1.50 ± 0.22, respectively. FC(O)C(O)F and CF2O are formed partially in secondary, most likely heterogeneous processes. At a reduced pressure of 50 Torr, the product distribution is shifted towards formation of FC(O)C(O)F, indicating the important role of collisional quenching of initially formed association complexes, and enabling details of the reaction mechanism to be elucidated. An atmospheric photo-oxidation mechanism for PEVE is presented and the environmental implications of PEVE release and degradation are discussed.

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.

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.

Evaluating technology options to mitigate the climate impacts of road transportation can be challenging, particularly when they involve a tradeoff between long-lived emissions (e.g., carbon dioxide) and short-lived emissions (e.g., methane or black carbon). Here we present trends in short- and long-lived emissions for light- and heavy-duty transport globally and in the U.S., EU, and China over the period 2000-2030, and we discuss past and future changes to vehicle technologies to reduce these emissions. We model the tradeoffs between short- and long-lived emission reductions across a range of technology options, life cycle emission intensities, and equivalency metrics. While short-lived vehicle emissions have decreased globally over the past two decades, significant reductions in CO 2 will be required by mid-century to meet climate change mitigation targets. This is true regardless of the time horizon used to compare long- and short-lived emissions. The short-lived emission intensities of some low-CO 2 technologies are higher than others, and thus their suitability for meeting climate targets depends sensitively on the evaluation time horizon. Other technologies offer low intensities of both short-lived emissions and CO 2 .