Verification of a National Emission Inventory and Influence of On-road Vehicle Manufacturer-Level Emissions.

Road vehicles make important contributions to a wide range of pollutant emissions from the street level to global scales. The quantification of emissions from road vehicles is, however, highly challenging given the number of individual sources involved and the myriad factors that influence emissions such as fuel type, emission standard, and driving behavior. In this work, we use highly detailed and comprehensive vehicle emission remote sensing measurements made under real driving conditions to develop new bottom-up inventories that can be compared to official national inventory totals. We find that the total UK passenger car and light-duty van emissions of nitrogen oxides (NOx) are underestimated by 24-32%, and up to 47% in urban areas, compared with the UK national inventory, despite agreement within 1.5% for total fuel used. Emissions of NOx at a country level are also shown to vary considerably depending on the mix of vehicle manufacturers in the fleet. Adopting the on-road mix of vehicle manufacturers for six European countries results in up to a 13.4% range in total emissions of NOx. Accounting for the manufacturer-specific fleets at a country level could have a significant impact on emission estimates of NOx and other pollutants across the European countries, which are not currently reflected in emission inventories.

An increasing role for solvent emissions and implications for future measurements of volatile organic compounds.

Volatile organic compounds (VOCs) are a broad class of air pollutants which act as precursors to tropospheric ozone and secondary organic aerosols. Total UK emissions of anthropogenic VOCs peaked in 1990 at 2,840 kt yr-1 and then declined to approximately 810 kt yr-1 in 2017 with large reductions in road transport and fugitive fuel emissions. The atmospheric concentrations of many non-methane hydrocarbons (NMHC) in the UK have been observed to fall over this period in broadly similar proportions. The relative contribution to emissions from solvents and industrial processes is estimated to have increased from approximately 35% in 1990 to approximately 63% in 2017. In 1992, UK national monitoring quantified 19 of the 20 most abundant individual anthropogenic VOCs emitted (all were NMHCs), but by 2017 monitoring captured only 13 of the top 20 emitted VOCs. Ethanol is now estimated to be the most important VOC emitted by mass (in 2017 approx. 136 kt yr-1 and approx. 16.8% of total emissions) followed by n-butane (52.4 kt yr-1) and methanol (33.2 kt yr-1). Alcohols have grown in significance representing approximately 10% of emissions in 1990 rising to approximately 30% in 2017. The increased role of solvent emissions should now be reflected in European monitoring strategies to verify total VOC emission reduction obligations in the National Emissions Ceiling Directive. Adding ethanol, methanol, formaldehyde, acetone, 2-butanone and 2-propanol to the existing NMHC measurements would provide full coverage of the 20 most significant VOCs emitted on an annual mass basis. This article is part of a discussion meeting issue 'Air quality, past present and future'.

Simplified speciation and atmospheric volatile organic compound emission rates from non-aerosol personal care products.

Volatile organic compounds (VOCs) emitted from personal care products (PCPs) can affect indoor air quality and outdoor air quality when ventilated. In this paper, we determine a set of simplified VOC species profiles and emission rates for a range of non-aerosol PCPs. These have been constructed from individual vapor analysis from 36 products available in the UK, using equilibrium headspace analysis with selected-ion flow-tube mass spectrometry (SIFT-MS). A simplified speciation profile is created based on the observations, comprising four alcohols, two cyclic volatile siloxanes, and monoterpenes (grouped as limonene). Estimates are made for individual unit-of-activity VOC emissions for dose-usage of shampoos, shower gel, conditioner, liquid foundation, and moisturizer. We use these values as inputs to the INdoor air Detailed Chemical Model (INDCM) and compare results against real-world case-study experimental data. Activity-based emissions are then scaled based on plausible usage patterns to estimate the potential scale of annual per-person emissions for each product type (eg, 2 g limonene person-1  yr-1 from shower gels). Annual emissions from non-aerosol PCPs for the UK are then calculated (decamethylcyclopentasiloxane 0.25 ktonne yr-1 and limonene 0.15 ktonne yr-1 ) and these compared with the UK National Atmospheric Emissions Inventory estimates for non-aerosol cosmetics and toiletries.

Have vehicle emissions of primary NO2 peaked?

Reducing ambient concentrations of nitrogen dioxide (NO2) remains a key challenge across many European urban areas, particularly close to roads. This challenge mostly relates to the lack of reduction in emissions of oxides of nitrogen (NOx) from diesel road vehicles relative to the reductions expected through increasingly stringent vehicle emissions legislation. However, a key component of near-road concentrations of NO2 derives from directly emitted (primary) NO2 from diesel vehicles. It is well-established that the proportion of NO2 (i.e. the NO2/NOx ratio) in vehicle exhaust has increased over the past decade as a result of vehicle after-treatment technologies that oxidise carbon monoxide and hydrocarbons and generate NO2 to aid the emissions control of diesel particulate. In this work we bring together an analysis of ambient NOx and NO2 measurements with comprehensive vehicle emission remote sensing data obtained in London to better understand recent trends in the NO2/NOx ratio from road vehicles. We show that there is evidence that NO2 concentrations have decreased since around 2010 despite less evidence of a reduction in total NOx. The decrease is shown to be driven by relatively large reductions in the amount of NO2 directly emitted by vehicles; from around 25 vol% in 2010 to 15 vol% in 2014 in inner London, for example. The analysis of NOx and NO2 vehicle emission remote sensing data shows that these reductions have been mostly driven by reduced NO2/NOx emission ratios from heavy duty vehicles and buses rather than light duty vehicles. However, there is also evidence from the analysis of Euro 4 and 5 diesel passenger cars that as vehicles age the NO2/NOx ratio decreases. For example the NO2/NOx ratio decreased from 29.5 ± 2.0% in Euro 5 diesel cars up to one year old to 22.7 ± 2.5% for four-year old vehicles. At some roadside locations the reductions in primary NO2 have had a large effect on reducing both the annual mean and number of hourly exceedances of the European Limit Values of NO2.

Secondary organic aerosol formation from a large number of reactive man-made organic compounds.

A photochemical trajectory model has been used to examine the relative propensities of a wide variety of volatile organic compounds (VOCs) emitted by human activities to form secondary organic aerosol (SOA) under one set of highly idealised conditions representing northwest Europe. This study applied a detailed speciated VOC emission inventory and the Master Chemical Mechanism version 3.1 (MCM v3.1) gas phase chemistry, coupled with an optimised representation of gas-aerosol absorptive partitioning of 365 oxygenated chemical reaction product species. In all, SOA formation was estimated from the atmospheric oxidation of 113 emitted VOCs. A number of aromatic compounds, together with some alkanes and terpenes, showed significant propensities to form SOA. When these propensities were folded into a detailed speciated emission inventory, 15 organic compounds together accounted for 97% of the SOA formation potential of UK man made VOC emissions and 30 emission source categories accounted for 87% of this potential. After road transport and the chemical industry, SOA formation was dominated by the solvents sector which accounted for 28% of the SOA formation potential.