Throughfall and bulk deposition of dissolved organic nitrogen to holm oak forests in the Iberian Peninsula: Flux estimation and identification of potential sources.

Deposition of dissolved organic nitrogen (DON) in both bulk precipitation (BD) and canopy throughfall (TF) has been measured for the first time in the western Mediterranean. The study was carried out over a year from 2012 to 2013 at four evergreen holm oak forests located in the Iberian Peninsula: two sites in the Province of Barcelona (Northeastern Spain), one in the Province of Madrid (central Spain) and the fourth in the Province of Navarra (Northern Spain). In BD the annual volume weighted mean (VWM) concentration of DON ranged from 0.25 mg l(-1) in Madrid to 1.14 mg l(-1) in Navarra, whereas in TF it ranged from 0.93 mg l(-1) in Barcelona to 1.98 mg l(-1) in Madrid. The contribution of DON to total nitrogen deposition varied from 34% to 56% in BD in Barcelona and Navarra respectively, and from 38% in Barcelona to 72% in Madrid in TF. Agricultural activities and pollutants generated in metropolitan areas were identified as potential anthropogenic sources of DON at the study sites. Moreover, canopy uptake of DON in Navarra was found in spring and autumn, showing that organic nitrogen may be a supplementary nutrient for Mediterranean forests, assuming that a portion of the nitrogen taken up is assimilated during biologically active periods.

Influences on and patterns in total gaseous mercury (TGM) at Harwell, England.

Total gaseous mercury (TGM) was monitored during 2013 at the rural monitoring site, Harwell, England using the Tekran 2537A monitoring system. Average TGM for the year was 1.45 ± 0.24 ng m(-3). This is comparable to other northern hemisphere studies, but on average 0.5 ng m(-3) higher than at its sister monitoring station at Auchencorth Moss, Scotland, but 14% lower than that found in a similar study at the same location of 1.68 ng m(-3) in 1995/6. Using wind sector analysis we show the important influence of local emissions, with our data showing that the largest influence on TGM observed is that of the adjacent Science & Innovation campus, making the site more a 'suburban background'. By using co-located measurements of black carbon and sulphur dioxide as tracers, we present an initial investigation into the impact of the closure of Didcot A coal fired power station, which ceased operating in March 2013. Further analysis using air mass back trajectories shows the long-range contribution to TGM from continental Europe, and that the lowest levels are associated with marine air masses from the west.

Patterns and source analysis for atmospheric mercury at Auchencorth Moss, Scotland.

Gaseous elemental (GEM), particulate bound (PBM) and gaseous oxidised (GOM) mercury species were monitored between 2009 and 2011 at the rural monitoring site, Auchencorth Moss, Scotland using the Tekran speciation monitoring system. GEM average for the three year period was 1.40±0.19 ng m(-3) which is comparable with other northern hemisphere studies. PBM and GOM concentrations are very low in 2009 and 2010 with geometric mean (×/÷standard deviation) PBM values of 2.56 (×/÷3.44) and 0.03 (×/÷17.72) pg m(-3) and geometric mean (×/÷standard deviation) GOM values of 0.11 (×/÷4.94) and 0.09 (×/÷8.88) pg m(-3) respectively. Using wind sector analysis and air mass back trajectories, the importance of local and regional sources on speciated mercury are investigated and we show the long range contribution to GEM from continental Europe, and that the lowest levels are associated with polar and marine air masses from the north west sector.

The cycling of organic nitrogen through the atmosphere.

Atmospheric organic nitrogen (ON) appears to be a ubiquitous but poorly understood component of the atmospheric nitrogen deposition flux. Here, we focus on the ON components that dominate deposition and do not consider reactive atmospheric gases containing ON such as peroxyacyl nitrates that are important in atmospheric nitrogen transport, but are probably not particularly important in deposition. We first review the approaches to the analysis and characterization of atmospheric ON. We then briefly summarize the available data on the concentrations of ON in both aerosols and rainwater from around the world, and the limited information available on its chemical characterization. This evidence clearly shows that atmospheric aerosol and rainwater ON is a complex mixture of material from multiple sources. This synthesis of available information is then used to try and identify some of the important sources of this material, in particular, if it is of predominantly natural or anthropogenic origin. Finally, we suggest that the flux of ON is about 25 per cent of the total nitrogen deposition flux.

An analysis of total gaseous mercury (TGM) concentrations across the UK from a rural sampling network.

Total gaseous mercury was collected at ten sites, which comprise part of the UK rural heavy metals monitoring network, between 2005 and 2008. Using the gold amalgam technique to capture total gaseous mercury, samples were analysed using a Tekran 2537A mercury vapour analyser. The data showed no upward or downward trend in atmospheric mercury concentrations over the period, with 4 year average concentrations between 1.3 and 1.9 ng m(-3), which are in line with other studies' observed northern hemispheric background concentrations of between 1.5 and 1.7 ng m(-3). Using data from nine of the sites, we were able to show seasonality within the data and through kriging we were able to interpolate the TGM concentrations over the UK, revealing a south-east to north-west declining concentration gradient. Using continuous speciated mercury measurements from one of the network sites, we show through wind sector analysis and air-mass back trajectories that this spatial trend is likely to be due to air masses moving over the UK from continental Europe on easterly winds. The levels of TGM recorded in the south-east of the UK also more closely match observed background TGM levels on the continent, which could indicate that the TGM concentrations from the north of the UK are a better reflection of the true North Atlantic atmospheric mercury background level.

Experimental field estimation of organic nitrogen formation in tree canopies.

The content of organic N has been shown in many studies to increase during the passage of rain water through forest canopies. The source of this organic N is unknown, but generally assumed to come from canopy processing of wet or dry-deposited inorganic N. There have been very few experimental studies in the field to address the canopy formation or loss of organic N. We report two studies: a Scots pine canopy exposed to ammonia gas, and a Sitka spruce canopy exposed to ammonium and nitrate as wet deposition. In both cases, organic N deposition in throughfall was increased, but only represented a small fraction (<10%) of the additional inorganic N supplied, suggesting a limited capacity for net organic N production, similar in both conifer canopies under Scottish summertime conditions, of less than 1.6 mmol N m(-2) mth(-1) (equivalent to 3 kg N ha(-1) y(-1)).

The production and degradation of trichloroacetic acid in soil: results from in situ soil column experiments.

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.

Agricultural ammonia emissions inventory and spatial distribution in the North China Plain.

An agricultural ammonia (NH(3)) emission inventory in the North China Plain (NCP) on a prefecture level for the year 2004, and a 5 x 5 km(2) resolution spatial distribution map, has been calculated for the first time. The census database from China's statistics datasets, and emission factors re-calculated by the RAINS model supported total emissions of 3071 kt NH(3)-N yr(-1) for the NCP, accounting for 27% of the total emissions in China. NH(3) emission from mineral fertilizer application contributed 1620 kt NH(3)-N yr(-1), 54% of the total emission, while livestock emissions accounted for the remaining 46% of the total emissions, including 7%, 27%, 7% and 5% from cattle, pigs, sheep and goats, and poultry, respectively. A high-resolution spatial NH(3) emissions map was developed based on 1 x 1 km land use database and aggregated to a 5 x 5 km grid resolution. The highest emission density value was 198 kg N ha(-1) yr(-1).

Evidence for changing the critical level for ammonia.

The current critical level for ammonia (CLE(NH3)) in Europe is set at 8mug NH(3) m(-3) as an annual average concentration. Recent evidence has shown specific effects of ammonia (NH(3)) on plant community composition (a true ecological effect) at much smaller concentrations. The methods used in setting a CLE(NH3) are reviewed, and the available evidence collated, in proposing a new CLE(NH3) for different types of vegetation. For lichens and bryophytes, we propose a new CLE(NH3) of 1 microg NH(3) m(-3) as a long-term (several year) average concentration; for higher plants, there is less evidence, but we propose a CLE(NH3) of 3+/-1 microg NH(3) m(-3) for herbaceous species. There is insufficient evidence to provide a separate CLE(NH3) for forest trees, but the value of 3+/-1 microg NH(3) m(-3) is likely to exceed the empirical critical load for N deposition for most forest ecosystems.

Surface ozone concentrations and ecosystem health: past trends and a guide to future projections.

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.

Interactions of forests with secondary air pollutants: some challenges for future research.

The effects of ozone and other photochemical oxidants on individual trees have been studied for several decades, but there has been much less research on the potential effects on entire forest ecosystems. Given that ozone and other oxidants affect the production and subsequent fate of biogenic volatile organic compounds that act as signalling molecules, there is a need for more detailed study of the role of oxidants in modifying trophic interactions in forests. Deposition of fine particulates to forests may act as a source of nutrients, but also changes leaf surface properties, increasing the duration of surface wetness and modifying the habitat for epiphytic organisms, leading to increased risks from pathogens. Even where this pathway contributes a relatively small input of nutrients to forests, the indirect effects on canopy processes and subsequent deposition to the forest floor in throughfall and litter may play a more important role that has yet to be fully investigated.

The influence of nitrogen in stemflow and precipitation on epiphytic bryophytes, Isothecium myosuroides Brid., Dicranum scoparium Hewd. and Thuidium tamariscinum (Hewd.) Schimp of Atlantic oakwoods.

The spatial relationship between the concentration and deposition of the major ions in precipitation and stemflow and their influence on the tissue nitrogen concentration of three epiphytic bryophytes on Quercus petraea (Matt) Liebl. and Q. robur L. was investigated at seven UK Atlantic oak woodland sites with a range of total N deposition of 55-250 mmol m(-2). The main driver of change in tissue N concentrations of three epiphytic bryophytes (Isothecium myosuroides Brid. (Eurhynchium myosuroides (Brid.) Schp.), Dicranum scoparium Hewd. and Thuidium tamariscinum (Hewd.) Schimp.) was total N deposition in stemflow, dominated by ammonium deposition. The three epiphytic species also showed strong relationships between tissue N concentration and total N deposition in rainfall but a poor correlation with total N ion concentration in rainfall. This study shows that epiphytic bryophytes utilise stemflow N and thus increase their risk from inputs of total N deposition compared to terricolous species at the same site.

Impacts of climate change on the fate and behaviour of pesticides in surface and groundwater--A UK perspective.

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.

Vegetation composition of roadside verges in Scotland: the effects of nitrogen deposition, disturbance and management.

Vehicular emissions of NO(x) and NH(3) result in elevated concentrations of nitrogen at roadside verges. To determine the extent that vehicular nitrogen emissions, disturbance and management affect the vegetation composition of road verges, a survey of 92 verges in Scotland was carried out with sites stratified by background nitrogen deposition and road type. NO(x) and NH(3) concentrations were monitored at 15 key sites for a year, and showed a decreasing gradient with increasing distance from the road. Ellenberg fertility indices of the vegetation communities also showed a general decrease with increasing distance from the road, but there was no straightforward correlation with NO(x) and NH(3) air concentrations between sites. Cover of bare ground, ruderal species and salt-tolerant species were highest at the verge edge. The proximity of the verge to traffic is important both in terms of NO(x) and NH(3) gradients, but also for deposited salt, grit and physical disturbance.

Peroxyacetyl nitrate in eastern Scotland.

Peroxyacetyl nitrate (PAN) concentrations in air were sampled hourly from 1994 to 1998 at a rural site 15 km south-west of Edinburgh, in eastern Scotland. Annual average concentrations were between 0.1 and 0.15 nl l(-1), with episodes up to 3 nl l(-1) in long-range transported polluted air. PAN concentrations were approximately log-normally distributed. The concentrations measured are the result of a balance between photochemical production rates and removal by thermal decomposition and dry deposition. In general, there was a poor correlation between PAN and ozone concentrations at this rural site except during episodes of photochemical pollution, when the PAN/O(3) volume ratio exceeded 0.01. The PAN/NO(x) volume ratio had a median value of 0.015 but ranged up to 0.25. There was a pronounced seasonal maximum in PAN concentrations in late spring, and a strong diurnal cycle only in April-June, with a maximum at 1700 h. Individual episodes, with concentrations up to 3 nl l(-1), could be traced over distances of ca. 1000 km, with rapid changes in concentration as the prevailing winds advected polluted air masses across the site.

Concentrations of ammonia and nitrogen dioxide at roadside verges, and their contribution to nitrogen deposition.

Bimonthly integrated measurements of NO2 and NH3 have been made over one year at distances up to 10 m away from the edges of roads across Scotland, using a stratified sampling scheme in terms of road traffic density and background N deposition. The rate of decrease in gas concentrations away from the edge of the roads was rapid, with concentrations falling by 90% within the first 10 m for NH3 and the first 15 m for NO2. The longer transport distance for NO2 reflects the production of secondary NO2 from reaction of emitted NO and O3. Concentrations above the background, estimated at the edge of the traffic lane, were linearly proportional to traffic density for NH3 (microg NH3 m(-3) = 1 x 10(-4) x numbers of cars per day), reflecting emissions from three-way catalysts. For NO2, where emissions depend strongly on vehicle type and fuel, traffic density was calculated in terms of 'car equivalents'; NO2 concentrations at the edge of the traffic lane were proportional to the number of car equivalents (microg NO2 m(-3) = 1 x 10(-4) x numbers of car equivalents per day). Although absolute concentrations (microg m(-3)) of NH3 were five times smaller than for NO2, the greater deposition velocity for NH3 to vegetation means that approximately equivalent amounts of dry N deposition to road side vegetation from vehicle emissions comes from NH3 and NO2. Depending on traffic density, the additional N deposition attributable to vehicle exhaust gases is between 1 and 15 kg N ha(-1) y(-1) at the edge of the vehicle lane, falling to 0.2-10 kg N ha(-1) y(-1) at 10 m from the edge of the road.

Fluxes of trichloroacetic acid through a conifer forest canopy.

Controlled-dosing experiments with conifer seedlings have demonstrated an above-ground route of uptake for trichloroacetic acid (TCA) from aqueous solution into the canopy, in addition to uptake from the soil. The aim of this work was to investigate the loss of TCA to the canopy in a mature conifer forest exposed only to environmental concentrations of TCA by analysing above- and below-canopy fluxes of TCA and within-canopy instantaneous reservoir of TCA. Concentrations and fluxes of TCA were quantified for one year in dry deposition, rainwater, cloudwater, throughfall, stemflow and litterfall in a 37-year-old Sitka spruce and larch plantation in SW Scotland. Above-canopy TCA deposition was dominated by rainfall (86%), compared with cloudwater (13%) and dry deposition (1%). On average only 66% of the TCA deposition passed through the canopy in throughfall and stemflow (95% and 5%, respectively), compared with 47% of the wet precipitation depth. Consequently, throughfall concentration of TCA was, on average, approximately 1.4 x rainwater concentration. There was no significant difference in below-canopy fluxes between Sitka spruce and larch, or at a forest-edge site. Annual TCA deposited from the canopy in litterfall was only approximately 1-2% of above-canopy deposition. On average, approximately 800 microg m(-2) of deposited TCA was lost to the canopy per year, compared with estimates of above-ground TCA storage of approximately 400 and approximately 300 microg m(-2) for Sitka spruce and larch, respectively. Taking into account likely uncertainties in these values ( approximately +/- 50%), these data yield an estimate for the half-life of within-canopy elimination of TCA in the range 50-200 days, assuming steady-state conditions and that all TCA lost to the canopy is transferred into the canopy material, rather than degraded externally. The observations provide strong indication that an above-ground route is important for uptake of TCA specifically of atmospheric origin into mature forest canopies, as has been shown for seedlings (in addition to uptake from soil via transpiration), and that annualized within-canopy elimination is similar to that in controlled-dosing experiments.

Trichloroacetic acid cycling in Sitka spruce saplings and effects on sapling health following long term exposure.

Trichloroacetic acid (TCA, CCl(3)COOH) has been associated with forest damage but the source of TCA to trees is poorly characterised. To investigate the routes and effects of TCA uptake in conifers, 120 Sitka spruce (Picea sitchensis (Bong.) Carr) saplings were exposed to control, 10 or 100 microg l(-1) solutions of TCA applied twice weekly to foliage only or soil only over two consecutive 5-month growing seasons. At the end of each growing season similar elevated TCA concentrations (approximate range 200-300 ng g(-1) dwt) were detected in both foliage and soil-dosed saplings exposed to 100 microg l(-1) TCA solutions showing that TCA uptake can occur from both exposure routes. Higher TCA concentrations in branchwood of foliage-dosed saplings suggest that atmospheric TCA in solution is taken up indirectly into conifer needles via branch and stemwood. TCA concentrations in needles declined slowly by only 25-30% over 6 months of winter without dosing. No effect of TCA exposure on sapling growth was measured during the experiment. However at the end of the first growing season needles of saplings exposed to 10 or 100 microg l(-1) foliage-applied TCA showed significantly more visible damage, higher activities of some detoxifying enzymes, lower protein contents and poorer water control than needles of saplings dosed with the same TCA concentrations to the soil. At the end of each growing season the combined TCA storage in needles, stemwood, branchwood and soil of each sapling was <6% of TCA applied. Even with an estimated half-life of tens of days for within-sapling elimination of TCA during the growing season, this indicates that TCA is eliminated rapidly before uptake or accumulates in another compartment. Although TCA stored in sapling needles accounted for only a small proportion of TCA stored in the sapling/soil system it appears to significantly affect some measures of sapling health.

Fluxes and reservoirs of trichloroacetic acid at a forest and moorland catchment.

The concentrations and input/output fluxes of trichloroacetic acid (TCA) were measured in all relevant media for one year at a 0.86 km2 upland conifer plantation and moorland catchment in SW Scotland (n > 380 separate samples analyzed). Annual wet precipitation to the catchment was 2.5 and 0.4 m for rain and cloud, respectively. TCA input to the catchment for the year was 2100 g, predominantly in rainwater (86%), with additional input via cloudwater (13%) and gas plus particle dry deposition (1%). There were no seasonal trends in TCA deposition, and cloudwater concentration was not enhanced over rainwater. TCA in precipitation exceeded concentrations estimated using currently accepted routes of gas-phase oxidation from anthropogenic chlorinated hydrocarbon precursors, in agreement with previous studies. Export of TCA from the catchment in streamwater totalled 1970 g for the year of study. The TCA concentration in streamwater at outflow (median 1.2 microg L(-1)) was significantly greater than that before the stream had passed through the conifer plantation. To well-within measurement uncertainties, the catchment is currently at steady-state with respect to TCA input/output. The catchment reservoir of TCA was dominated by soils (approximately 90%), with the remainder distributed in forest litter (approximately 9%), forest branchwood and stemwood (approximately 0.7%), forest foliage (approximately 0.5%), and moorland foliage (approximately 0.1%). Although TCA is clearly taken up into foliage, which consequently may be important for the vegetation, this was a relatively minor process for TCA at the catchment scale. If it is assumed, on the basis of laboratory extraction experiments, that only approximately 20% of "whole soil" TCA measured in this work was water extractable, then total mass of TCA in the catchment is reduced from approximately 13 to approximately 3.5 kg. Comparing the latter value with the annual flux yields an average steady-state residence time for TCA in the catchment of approximately 1-2 y, if all TCA is involved in catchment turnover. Considering that other evidence indicates the lifetime of TCA in soil and biota is considerably shorter than this (weeks rather than years), the magnitude of the TCA reservoir is suggested to be strong evidence for net natural TCA production in soils and/or that the majority of TCA in the reservoir is not involved with external fluxes.