Hydroperoxymethyl thioformate (HPMTF) is a newly identified major oxidation product of dimethyl sulfide (DMS). It is speculated that it could act as a major reservoir of marine sulfur, but its fate in the atmosphere is currently unknown. In this study, we have investigated the formation of HPMTF through the oxidation of DMS by OH, NO3 and Cl radicals and its losses through photolysis, OH oxidation, dry deposition, and wet deposition using the global 3-dimensional chemical transport model, STOCHEM-CRI. The model results suggest that the distribution of loss processes for HPMTF are photolysis (46%) and wet deposition (31%) with additional contributions from dry deposition (13%) and OH oxidation (10%). The global burden and the tropospheric lifetime of HPMTF are found to be 0.052 Tg and 0.5 days, respectively. The model integrations agree well with both aircraft derived measurements of HPMTF over the ocean surface between 80 °N and 85 °S latitudes and ground-based measurements made in the central Amazon. These ground-based data reveal a clear diurnal cycle with a maximum during midday, consistent with other recently reported data and possibly due to the dominance of the photochemical production rather than the photolytic loss. Accounting for HPMTF chemistry results in a significant decrease in boundary layer levels of SO2 and H2SO4 but increases in sulfate aerosol in the upper troposphere. We suggest that these changes could have important consequences on preindustrial to present-day radiative forcing from sulfate aerosol.

Perfluorooctanoic acid, PFOA, is one of the many concerning pollutants in our atmosphere; it is highly resistant to environmental degradation processes, which enables it to accumulate biologically. With direct routes of this chemical to the environment decreasing, as a consequence of the industrial phase out of PFOA, it has become more important to accurately model the effects of indirect production routes, such as environmental degradation of precursors; e.g., fluorotelomer alcohols (FTOHs). The study reported here investigates the chemistry, physical loss and transport of PFOA and its precursors, FTOHs, throughout the troposphere using a 3D global chemical transport model, STOCHEM-CRI. Moreover, this investigation includes an important loss process of PFOA in the atmosphere via the addition of the stabilised Criegee intermediates, hereby referred to as the “Criegee Field.” Whilst reaction with Criegee intermediates is a significant atmospheric loss process of PFOA, it does not result in its permanent removal from the atmosphere. The atmospheric fate of the resultant hydroperoxide product from the reaction of PFOA and Criegee intermediates resulted in a ≈0.04 Gg year−1 increase in the production flux of PFOA. Furthermore, the physical loss of the hydroperoxide product from the atmosphere (i.e., deposition), whilst decreasing the atmospheric concentration, is also likely to result in the reformation of PFOA in environmental aqueous phases, such as clouds, precipitation, oceans and lakes. As such, removal facilitated by the “Criegee Field” is likely to simply result in the acceleration of PFOA transfer to the surface (with an expected decrease in PFOA atmospheric lifetime of ≈10 h, on average from ca. 80 h without Criegee loss to 70 h with Criegee loss).

Trifluoroacetic acid (TFA), a highly soluble and stable organic acid, is photochemically produced by certain anthropogenically emitted halocarbons such as HFC-134a and HFO-1234yf.Both these halocarbons are used as refrigerants in the automobile industry and the high global warming potential of HFC-134a has promoted regulation of its use. Industries are transitioning to the use of HFO-1234yf as a more environmentally friendly alternative. We investigated the environmental effects of this change and found a thirty-three-fold increase in the global burden of TFA from an annual value of 65 tonnes formed from the 2015 emissions of HFC-134a, to a value of 2200 tonnes formed from an equivalent emission of HFO-1234yf. The percentage increase in surface TFA concentrations resulting from the switch from HFC-134a to HFO-1234yf remains substantial with an increase of up to 250-fold across Europe. The increase in emissions greater than the current emission scenario of HFO-1234yf is likely to result in significant TFA burden as the atmosphere is not able to disperse and deposit relevant oxidation products. The 2 Criegee intermediate initiated loss process of TFA reduces the surface level atmospheric lifetime of TFA by up to 5 days (from 8 days to 3 days) in tropical forested regions.

An accelerating global energy demand, paired with the harmful environmental effects of fossil fuels, has triggered the search for alternative, renewable energy sources. Biofuels are arguably a potential renewable energy source in the transportation industry as they can be used within current infrastructures and require less technological advances than other renewable alternatives, such as electric vehicles and nuclear power. The literature suggests biofuels can negatively impact food security and production; however, this is dependent on the type of feedstock used in biofuel production. Advanced biofuels, derived from inedible biomass, are heavily favoured but require further research and development to reach their full commercial potential. Replacing fossil fuels by biofuels can substantially reduce particulate matter (PM), carbon monoxide (CO) emissions, but simultaneously increase emissions of nitrogen oxides (NOx), acetaldehyde (CH3CHO) and peroxyacetyl nitrate (PAN), resulting in debates concerning the way biofuels should be implemented. The potential biofuel blends (FT-SPK, HEFA-SPK, ATJ-SPK and HFS-SIP) and their use as an alternative to kerosene-type fuels in the aviation industry have also been assessed. Although these fuels are currently more costly than conventional aviation fuels, possible reduction in production costs has been reported as a potential solution. A preliminary study shows that i-butanol emissions (1.8 Tg/year) as a biofuel can increase ozone levels by up to 6% in the upper troposphere, highlighting a potential climate impact. However, a larger number of studies will be needed to assess the practicalities and associated cost of using the biofuel in existing vehicles, particularly in terms of identifying any modifications to existing engine infrastructure, the impact of biofuel emissions, and their chemistry on the climate and human health, to fully determine their suitability as a potential renewable energy source.

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The contribution of NOx emissions and background O3 to the sources and partitioning of the oxidants [OX(=O3+NO2)] at the Marylebone Road site in London during the 2000s and 2010s has...

Ambient concentrations of 22 volatile organic compounds (VOCs) measured at London Marylebone Road (LMR), an urban traffic site, and London Eltham (LE), an urban background site, were analyzed over a period of 23 years to assess the impact of pollution control strategies. A significant decrease in ambient concentration is seen for the majority of VOCs analyzed with total VOC burden decreasing by 76% and 59% for LMR and LE, respectively, across the period studied. This is likely as a result of legislative controls. This analysis was extended to consider the dominant contribution of VOCs to ozone formation at the sites utilizing photochemical ozone creation potential (POCP) values.Similarly, the overall reactivity of the VOC burden at the sites has resulted in a significant decrease of 11% and 7% per year in ozone formation potential (OFP) for LMR and LE, respectively. At LMR, the declines in OFP for VOCs associated with road traffic emissions are all in good agreement at 11%-13% decrease per year. Reasonable agreement is also seen at LE with a decrease of 6%-11% per year in OFP of the VOCs related to traffic sources. VOCs related to non-traffic sources, namely ethane and propane from natural gas leakage, did not see a significant decline over the study period at either site. The variation and composition of the overall VOC burden was compared across three decadal time periods (1997-2000, 2001-2010, 2011-2019) and saw an increase in significance of these pollutants at both sites. At LMR, ethane and propane moved from the fifth and eleventh largest contributors to total VOC burden in 1997-2000 to the first and second largest contributors in 2011-2019. At LE, a similar trend is seen with ethane and propane becoming the first and second largest contributors in the most recent time period, up from second and eighth at the beginning of the dataset. The similarity between these sites suggests such pollutants are not sufficiently controlled under current legislation. The increase in significance of ethane and propane was mirrored in their contribution to ozone generation potential at both sites but ethene continues to dominate in contribution to OFP. At LMR, etheneThis is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

The concentrations of benzene and 1,3-butadiene in urban, suburban, and rural sites of the U.K. were investigated across 20 years (2000–2020) to assess the impacts of pollution control strategies. Given the known toxicity of these pollutants, it is necessary to investigate national long-term trends across a range of site types. We conclude that whilst legislative intervention has been successful in reducing benzene and 1,3-butadiene pollution from vehicular sources, previously overlooked sources must now be considered as they begin to dominate in contribution to ambient pollution. Benzene concentrations in urban areas were found to be ~5-fold greater than those in rural areas, whilst 1,3-butadiene concentrations were up to ~10-fold greater. The seasonal variation of pollutant concentration exhibited a maximum in the winter and a minimum in the summer with summer: winter ratios of 1:2.5 and 1:1.6 for benzene and 1,3-butadiene, respectively. Across the period investigated (2000–2020), the concentrations of benzene decreased by 85% and 1,3-butadiene concentrations by 91%. A notable difference could be seen between the two decades studied (2000–2010, 2010–2020) with a significantly greater drop evident in the first decade than in the second, proving, whilst previously successful, legislative interventions are no longer sufficiently limiting ambient concentrations of these pollutants. The health impacts of these pollutants are discussed, and cancer impact indices were utilized allowing estimation of cancer impacts across the past 20 years for different site types. Those particularly vulnerable to the adverse health effects of benzene and 1,3-butadiene pollution are discussed.