• Energy Research

Previous work has indicated that the soil is important to understanding biogeochemical fluxes of trichloroacetic acid (TCA) in the rural environment, in forests in particular. Here, the hydrological and TCA fluxes through 22 in situ soil columns in a forest and moorland-covered catchment and an agricultural grassland field in Scotland were monitored every 2 weeks for several months either as controls or in TCA manipulation (artificial dosing) experiments. This was supplemented by laboratory experiments with radioactively-labelled TCA and with irradiated (sterilised) soil columns. Control in situ forest soil columns showed evidence of net export (i.e. in situ production) of TCA, consistent with a net soil TCA production inferred from forest-scale mass balance estimations. At the same time, there was also clear evidence of substantial in situ degradation within the soil ( approximately 70% on average) of applied TCA. The laboratory experiments showed that both the formation and degradation processes operate on time scales of up to a few days and appeared related more with biological rather than abiotic processes. Soil TCA activity was greater in more organic-rich soils, particularly within forests, and there was strong correlation between TCA and soil biomass carbon content. Overall it appears that TCA soil processes exemplify the substantial natural biogeochemical cycling of chlorine within soils, independent of any anthropogenic chlorine flux.

This paper reviews current understanding of the sources and sinks of ozone in the troposphere, recent studies of long-term trends, and the factors which have to be taken into consideration when constructing and interpreting future models of ozone concentration. The factors controlling surface O(3) concentrations are discussed initially to provide a basis for the ensuing discussion, followed by a summary of the evidence for recent trends in ground-level ozone concentrations, i.e. over the past 3 decades, which have shown a significant increase in the annual average in 'background' air typical of the unpolluted northern hemisphere. Closer to precursor sources, although urban winter concentrations have increased, rural peak spring and summer concentrations during ozone 'episodes' have decreased markedly in response to emissions reductions. In order to determine whether such trends are meaningful, the statistical techniques for determining temporal trends are reviewed. The possible causes of long-term trends in ozone are then discussed, with particular reference to the use of chemistry-transport models to interpret past trends. Such models are also used to make predictions of future trends in surface ozone concentrations, but few are comprehensive in integrating future climate changes with changes in land use and in emissions of ozone precursors. Guidance is given on the likely effects of climate/precursor/chemistry interactions so that model predictions can be judged.

Over the last two decades significant effort has been dedicated to understanding the fate and transport of pesticides in surface water and groundwater and to use this understanding in the development of environmental policy and regulation. However, there have been few studies that have investigated the relationships between pesticides and climate change, and where this work has been undertaken it has principally been in relation to the impacts of climate change on agricultural production rather than in the context of environmental protection. This study addresses that gap by reviewing how climate change may impact the fate and transport of pesticides in surface and groundwaters as a pre-cursor to quantitative studies. In order to structure the review, we have adopted a source-pathway-receptor approach where climate sensitivities of pesticide source terms, environmental pathways and receptors are reviewed. The main climate drivers for changing pesticide fate and behaviour are thought to be changes in rainfall seasonality and intensity and increased temperatures, but the effect of climate change on pesticide fate and transport is likely to be very variable and difficult to predict. In the long-term, indirect impacts, such as land-use change driven by changes in climate, may have a more significant effect on pesticides in surface and groundwaters than the direct impacts of climate change on pesticide fate and transport. The review focuses on climate change scenarios and case studies from the UK; however, the general conclusions can be applied more widely.

Global nitrogen fixation contributes 413 Tg of reactive nitrogen (Nr) to terrestrial and marine ecosystems annually of which anthropogenic activities are responsible for half, 210 Tg N. The majority of the transformations of anthropogenic Nrare on land (240 Tg N yr−1) within soils and vegetation where reduced Nrcontributes most of the input through the use of fertilizer nitrogen in agriculture. Leakages from the use of fertilizer Nrcontribute to nitrate (NO3−) in drainage waters from agricultural land and emissions of trace Nrcompounds to the atmosphere. Emissions, mainly of ammonia (NH3) from land together with combustion related emissions of nitrogen oxides (NOx), contribute 100 Tg N yr−1to the atmosphere, which are transported between countries and processed within the atmosphere, generating secondary pollutants, including ozone and other photochemical oxidants and aerosols, especially ammonium nitrate (NH4NO3) and ammonium sulfate (NH4)2SO4. Leaching and riverine transport of NO3contribute 40–70 Tg N yr−1to coastal waters and the open ocean, which together with the 30 Tg input to oceans from atmospheric deposition combine with marine biological nitrogen fixation (140 Tg N yr−1) to double the ocean processing of Nr. Some of the marine Nris buried in sediments, the remainder being denitrified back to the atmosphere as N2or N2O. The marine processing is of a similar magnitude to that in terrestrial soils and vegetation, but has a larger fraction of natural origin. The lifetime of Nrin the atmosphere, with the exception of N2O, is only a few weeks, while in terrestrial ecosystems, with the exception of peatlands (where it can be 102–103years), the lifetime is a few decades. In the ocean, the lifetime of Nris less well known but seems to be longer than in terrestrial ecosystems and may represent an important long-term source of N2O that will respond very slowly to control measures on the sources of Nrfrom which it is produced.

Northern hemispheric background concentrations of ozone are increasing, but few studies have assessed the ecological significance of these changes for grasslands of high conservation value under field conditions. We carried out a 3-year field experiment in which ozone was released at a controlled rate over three experimental transects to produce concentration gradients over the field site, an upland mesotrophic grassland located in the UK. We measured individual species biomass in an annual hay cut in plots receiving ambient ozone, and ambient ozone elevated by mean concentrations of approximately 4 ppb and 10 ppb in the growing seasons of 2008 and 2009. There was a significant negative effect of ozone exposure on herb biomass, but not total grass or legume biomass, in 2008 and 2009. Within the herb fraction, ozone exposure significantly decreased the biomass of Ranunculus species and that of the hemi-parasitic species Rhinanthus minor. Multivariate analysis of species composition, taking into account spatial variation in soil conditions and ozone exposure, showed no significant ozone effect on the grass component. In contrast, by 2009, ozone had become the dominant factor influencing species composition within the combined herb and legume component. Our results suggest that elevated ozone concentrations may be a significant barrier to achieving increased species diversity in managed grasslands.

Miscanthus × giganteus and short rotation coppice (SRC) willow (Salix spp.) are increasingly important bioenergy crops. Above-canopy fluxes and mixing ratios of volatile organic compounds (VOCs) were measured in summer for the two crops at a site near Lincoln, UK, by proton transfer reaction mass spectrometry (PTR-MS) and virtual disjunct eddy covariance. The isoprene emission rate above willow peaked around midday at ∼1 mg m−2 h−1, equivalent to 20 μg gdw−1 h−1 normalised to 30 °C and 1000 μmol m−2 s−1 PAR, much greater than for conventional arable crops. Average midday peak isoprene mixing ratio was ∼1.4 ppbv. Acetone and acetic acid also showed small positive daytime fluxes. No measurable fluxes of VOCs were detected above the Miscanthus canopy. Differing isoprene emission rates between different bioenergy crops, and the crops or vegetation cover they may replace, means the impact on regional air quality should be taken into consideration in bioenergy crop selection.