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.

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.

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.

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.

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.

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.

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.

Environmental influences on the development of spruce needle cuticles.

Seedlings of Norway [Picea abies (L.) Karst.], red (P. rubens Sarg.), black [P. mariana (Mill) B.S.P.] and white [P. glauca (Moench.) Voss] spruce were grown from bud break to bud set outdoors, in the greenhouse, and in controlled environment chambers. The outdoor and greenhouse treatments also included adjacent shaded (50%) seedlings. The effects of growth environment on needle epicuticular wax production and morphology, and on needle wettability were investigated. Red and black spruce exhibited free growth in addition to determinate growth, but only in the greenhouse. Although relative growth rate was significantly lower for seedlings grown outdoors, there were no differences in wax morphology between outdoor- and greenhouse-grown seedlings, Wax deposits on controlled environment seedlings were significantly more crystalline. Wax tubes were crystallized in 'tufts'. There were significant differences in wax amounts recovered between species and treatments. Wax amounts relative to needle dry weights decreased in the order greenhouse > outdoors > controlled environment. Shaded red and black spruce produced significantly more wax than unshaded. Needles from seedlings grown in controlled environment chambers had the largest needle/droplet contact angles. These data indicate that seedling growth environment affects needle epicuticular wax characteristics and wettability. Studies designed to investigate factors determined by needle surface phystcochemical characteristics should include a consideration of growth environment.

Quantification of frost damage in plant tissues by rates of electrolyte leakage.

A method for assessing frost hardiness of plant tissues [using shoots of Picea rubens Sarg. syn P. rubra (Du Roi) Link] has been developed based upon the rate of electrolyte leakage from shoots immersed in distilled water after exposure to a range of freezing treatments. The relationship between conductivity (the electrolyte concentration in solution) and time has been shown to follow an asymptotic curve, which may be represented by a first-order equation: Ct -Co = Cauto -Co - C-kt ) where C1 is the conductivity at time t, Co is the initial conductivity, Cauto is the conductivity after autoclaving and k is the first-order rate constant (units time-1 ). The rate of electrolyte leakage (k) varies directly with the extent of tissue damage. In P. rebens a rate of 0-4%, h-1 distinguished between shoots which eventually died, and shoots which remained alive. A minimum of 3 conductivity measurements (after 1 day, 5 days and after autoclaving) is required for a reliable estimate of k. This objective, quantitative method of assessing frost hardiness may therefore be used directly to estimate LT50 values within a population.

Influence of acidic mist on frost hardiness and nutrient concentrations in red spruce seedlings: 1. Exposure of the foliage and the rooting environment.

Two-year-old red spruce (Picea rubens Sarg.) was grown in replicated open-top chambers supplied with charcoal-filtered air near Edinburgh, Scotland. Between May and November 1989, plants were exposed to four mist treatments, three containing sulphuric acid and ammonium nitrate in equimolar concentrations at 0.005 mol m-3 (pH 5) or 1.0 mol m-3 (pH 27), and a fourth treatment with sulphuric acid alone at 1.0 mol m3 (equivalent to 2 mm precipitation). Two dose rates were used for the pH 2.7 treatment equivalent to 2 and 8 mm of rain per week. Three subtreatments (soil surface exposed to mist, addition of extra sulphuric acid to the soil surface, exclusion of mist from the soil) were included in each chamber. Frost hardiness was assessed by measuring rates of electrolyte leakage after controlled freezing of detached shoots. At the end of October, frost hardiness, expressed as the lethal temperature for 50% of shoots (LT50 ), was decreased by 8 °C in the 8 mm wk-1 treatment at pH 27, compared to pH 5. The 2 mm wk-1 treatment at pH 2.7 had no effect on frost hardiness either when ammonium nitrate was present or absent (i.e. sulphuric acid only). Excluding mist from the soil, and adding extra sulphuric acid, both increased frost hardiness by about 3 °C when compared with uncovered soil. Excluding mist from the soil increased the amount of foliage initiated and produced inside the chambers but neither subtreatment, excluding the mist nor providing additional sulphuric acid to the soil affected foliar nutrient concentrations. Mist of pH 27 as sulphuric acid alone and in combination with ammonium nitrate both enhanced N uptake. Several observations concerning the effect of acidic mist on frost hardiness were confirmed by this study: (i) preventing mist from reaching the soil/roots, improving conditions for root growth can ameliorate the effects of acidic mist on shoot growth and frost hardiness; (ii) the effect was determined by the ion dose but not by the ion concentration in the mist; (iii) the effect was primarily mediated through foliar absorption; (iv) the presence of high foliar nitrogen concentrations did not increase frost hardiness when foliar sulphur concentrations were also high; (v) low N concentrations were more important for frost hardiness than high foliar N concentrations.

Influence of acidic mist on frost hardiness and nutrient concentrations in red spruce seedlings: 2. Effects of misting frequency and rainfall exclusion.

Two-year-old red spruce (Picea rubens Sarg.) of Pittston provenance and 3-yr-old plants of Chatham provenance were exposed to acid mist in replicated open-top chambers supplied with charcoal-filtered air near Edinburgh, Scotland. Plants of Chatham provenance had already been exposed to acid mist throughout the previous growing season. The plants were exposed to mist, equivalent to 4 mm rainfall per week, containing an equimolar mixture of sulphuric acid and ammonium nitrate at pH 2.5 or pH 5.0 (1.6 or 0.01 mol m3 ) from May to November. This weekly dose was delivered at a low frequency (2 mm twice a week), or high frequency (1 mm on 4 consecutive days each week) to chambers fitted with ceilings to exclude rain. The low frequency dose was also applied to chambers without ceilings, to examine the effect of natural washing by rain. Frost hardiness, estimated by exposing detached shoots to controlled freezing and then measuring rates of electrolyte leakage, was determined during the misting period at the end of October and in December. Foliar nutrient concentrations were measured during the dormant period after treatment had ceased. At the end of October, plants which had received acid mist were less frost hardy than plants receiving mist at pH 5. The temperature causing 50% shoot death (LT50 ) increased by 6 °C for low frequency application, and by 10 °C at high frequency, relative to the plants receiving mist at pH 5. Exclusion of ambient rainfall had no detectable effect on the frost hardiness response to acid mist. In December, 3 wk after the cessation of misting, all plants were more frost hardy than in October. Significant effects of the acid mist treatment could no longer be detected. Differences in nutrient concentrations were small among treatments, although K+ concentrations in the low frequency treatment with acid mist with rain exclusion were 50 % below those in other treatments. Ca concentrations were 50% larger in the acid mist treatment with rain exclusion than without. The data suggested enhanced sulphate uptake resulting from increasing the frequency of exposure, but the increase was not significant. There was no clear relationship between the pattern of frost hardiness and nutrient concentrations except for S, which was 30% smaller in the control plants (pH 5) than in the high frequency pH 2.5 treatments. It is concluded that excluding rainfall, an experimental artifact introduced in evaluating effects of acid mist, does not influence the frost hardiness response of red spruce seedlings. The much greater effect of exposure to the same dose at double the frequency suggests that such experiments may underestimate effects in the field, if those trees are exposed to more frequent episodes of polluted cloud water than experimental plants.

The influence of acid mists on growth, dry matter partitioning, nutrient concentrations and mycorrhizal fruiting bodies in red spruce seedlings.

Two-year-old spruce (Picea rubens Sarg.) seedlings were exposed to acid mists containing equimolar ammonium sulphate and nitric acid giving treatments of pH 2.5, 3.0 and 5.0. Acid mist treatments were applied twice weekly from late July until early October, 1987, when the plants were harvested. There were no significant differences in biomass accumulation or in height growth between treatments, but marked differences in root morphology were found. Significantly larger amounts of coarse roots were produced in the pH 5.0 acid mist treatment and plants in the pH 3.0 treatment produced significantly greater amounts of fine roots. Plants receiving acid mists of pH 3.0 or less had a greater frequency of fine root branches along their coarse roots. Production of mycorrhizal fruiting bodies of Thelephora terrestris Ehrenb.: Fr. was significantly greater (P < 0.001) at pH 5.0 than in the other treatments. Plants in the pH 2.5 and 3.0 treatments contained larger concentrations of N, 1.54 and 1.12% and S, 0.52 and 0.28% respectively, than those receiving acid mist at pH 5.0, i.e. 1.00 and 0.21% respectively. However, the between treatment differences of tissue nutrient concentrations were small relative to the differences in inputs between treatments. Foliar S exceeded concentrations recommended for nursery stock by 50 and 150% at pH 3.0 and 2.5 respectively.

Visible foliar injury of red spruce seedlings subjected to simulated acid mist.

Two-year-old red spruce seedlings [Picea rubens Sarg. syn. P. rubra (Du Roi) Link] were subjected to 6 simulated acid mist treatments (pH 2.5, 2.7, 3.0, 3.5, 4.0, 5.0) in a replicated experiment using open-top chambers. Acid mist solutions containing equimolar (NH4 )2 SO4 , and HNO3 were applied twice weekly for 22 weeks, each application being equivalent to 2 mm of precipitation. Visible symptoms of foliar damage were observed on the 3 most acidic mist treatments (pH 2.5, 2.7, 3.0). The inputs of nitrogen, sulphur and acidity in the most acidic treatment were 55, 42, 1,3 kg ha-1 , respectively, over a 10 week period. The plants subjected to the pH 2.5 treatment were found to be most severely damaged with approximately 40% foliar necrosis after 10 weeks of treatment. On approximately 80% of seedlings, necrosis was confined to current year needles only. These damaged needles were initially light brown or light orange in colour turning a deeper red 3 to 5 weeks after initial necrosis. Percentage foliar damage was linearly related to concentration (of NH4 + , NO3 - , SO4 2- and H+ ) with 62% foliar damage in the pH 2.5 treatment after a 22-week period. Spray application stopped in December 1987. Observations during the following spring showed that the pH 2.5 and pH 3 treatments induced earlier Hushing, requiring 60 day °C less thermal time than the pH 5-0 treatment. In 1988, this decrease in thermal requirement was equivalent to flushing 11 days earlier. There was no evidence of acid mist treatments inducing bud mortality.

Effects of acid mist on the frost hardiness of red spruce seedlings.

Seedlings of red spruce [Picea rubens Sarg. syn. P. rubra (Du Roi) Link] were exposed to mists containing equimolar (NH4 , SO4 and HNO3 at pHs of 2.5, 2.7, 3.0, 35, 4.0 or 5.0. The mists were applied twice each week, amounting to 2 mm precipitation equivalent on each occasion, between July and December, to open-top chambers supplied with charcoal-filtered air. Frost hardiness of shoots excised from seedlings was determined on 6 occasions starting on 21 September, and was found to be strongly influenced by acid mist treatments, seedlings subject to the most acidic mists being the least frost hardy. On 21 September when the first sample was taken the lethal temperature for killing 50% of shoots (LT50 ) was - 11 °C for the least acidic (pH 5.0) mist and - 7 °C for the most acidic (pH 2.5). By 19 October, the LT50 s of pH 5.0 and pH 2.5 mists were -27 and -15 °C respectively. All intermediate treatments ranked according to treatment concentration, with the smaller concentrations causing lower LT.50 values. The treatment at pH 30 provided S and N inputs to the seedlings similar to those experienced by red spruce at elevations of about 1000 m in the southern Appalachians. At pH 3.0, the frost hardiness LT10 during October was typically 8 °C higher than the pH 5.0 treatment, leading to a significant increase in the probability of frost damage at the LT10 level in an average October. The proximity of minimum night temperatures during September to December to the LT10 temperatures of red spruce shoots receiving large inputs of SO4 2- , NO3 - , NH4 + and H+ suggests that decreases in frost hardiness caused by intercepted cloud water containing large concentrations of these ions may play a significant part in the observed decline at mountain-top locations.

Direct damage to vegetation caused by acid rain and polluted cloud: definition of critical levels for forest trees.

The concept of critical levels was developed in order to define short-term and long-term average concentrations of gaseous pollutants above which plants may be damaged. Although the usual way in which pollutants in precipitation (wet deposition) influence vegetation is by affecting soil processes, plant foliage exposed to fog and cloud, which often contain much greater concentrations of pollutant ions than rain, may be damaged directly. The idea of a critical level has been extended to define concentrations of pollutants in wet deposition above which direct damage to plants is likely. Concentrations of acidity and sulphate measured in mountain and coastal cloud are summarised. Vegetation at risk of injury is identified as montane forest growing close to the cloud base, where ion concentrations are highest. The direct effects of acidic precipitation on trees are reviewed, based on experimental exposure of plants to simulated acidic rain, fog or mist. Although most experiments have reported results in terms of pH (H(+) concentration), the accompanying anion is important, with sulphate being more damaging than nitrate. Both conifers and broadleaved tree seedlings showing subtle changes in the structural characteristics of leaf surfaces after exposure to mist or rain at or about pH 3.5, or sulphate concentration of 150 micromol litre(-1). Visible lesions on leaf surfaces occur at around pH 3 (500 micromol litre(-1) sulphate), broadleaved species tending to be more sensitive than conifers. Effects on photosynthesis and water relations, and interactions with other stresses (e.g. frost), have usually been observed only for treatments which have also caused visible injury to the leaf surface. Few experiments on the direct effects of polluted cloud have been conducted under field conditions with mature trees, which unlike seedlings in controlled conditions, may suffer a growth reduction in the absence of visible injury. Although leaching of cations (Ca(2+), Mg(2+), K(+)) is stimulated by acidic precipitation, amounts leached are small compared with root uptake, unless soils have been impoverished. This aspect of the potential effects of acidic precipitation is best considered in terms of the long-term critical-load of pollutants to the soil. Given the practical difficulties in monitoring cloud water composition, a method for defining critical levels is proposed, which uses climatological average data to identify the duration and frequency of hill cloud, and combines this information with measured or modelled concentrations of particulate sulphate in the atmosphere, to derive cloud water concentrations as a function of cloud liquid water content. For forests within 100 m of the cloud base the critical levels of particulate sulphate, corresponding to solution concentrations in the range 150-500 micromol litre(-1), are in the range 1-3.3 microg S m(-3). These concentrations are observed over much of central Europe, suggesting that many montane forests are at risk of direct effects of fossil-fuel-derived pollutants in cloud.

Effects of airborne volatile organic compounds on plants.

Routine measurements of volatile organic compounds (VOCs) in air have shown that average concentrations are very much smaller than those used in laboratory experiments designed to study the effects of VOCs on plants. However, maximum hourly concentrations of some VOCs can be 100 times larger than the average, even in rural air. Experimental studies have rarely extended for longer than a few days, so there is little information on potential long-term effects of exposure to small concentrations. This review considers the available evidence for long-term effects, based on laboratory and field data. Previous reviews of the literature from Germany and the USA are cited, prior to an assessment of the effects of individual VOCs. Although hydrocarbons from vehicle exhausts have been implicated in the observed effects on roadside vegetation, the evidence suggests that it is the nitrogen oxides in the exhaust gases that are mostly responsible. There is evidence that aromatic hydrocarbons can be metabolised in plants, although the fate of the metabolites is not known. There is a large literature on the effects of ethylene, because of its role as a plant hormone. Effects have been reported in the field, in response to industrial emissions, and dose-response experiments over several weeks in laboratory studies have clearly identified the potential for effects at ambient concentrations. The main responses are morphological (e.g. epinasty), which may be reversible, and on the development of flowers and fruit. Effects on seed production may be positive or negative, depending on the exposure concentration. Chlorinated hydrocarbons have been identified as potentially harmful to vegetation, but only one long-term experiment has studied dose-response relationships. As for ethylene, the most sensitive indication of effect was on seed production, although long-term accumulation of trichloroacetic acid in tissue may also be a problem. There is little evidence of the direct effects of oxygenated hydrocarbons on plants. Plants are a significant emission source of short-chain alcohols, aldehydes and ketones. Peroxyacetyl nitrate (PAN) has a well-documented history as damaging to vegetation. There have been few long-term experimental studies despite the field evidence for damaging effects. Early studies in California have been followed by more recent data from east Asia, but there is still a dearth of information on the potential for effects of PAN and related peroxyacyl nitrates on vegetation typical of regions around tropical and sub-tropical cities where PAN pollution is increasingly important. The lack of long-term measurements, coupled with the available evidence that effects are not linearly related to 'dose' measured as the product of exposure concentration and time, means that the possibility of adverse effects of VOCs on vegetation cannot be safely rejected, particularly in urban and industrial areas. Although reproductive processes (flowering, seed production) appear to be most sensitive, there have been no experimental studies on subsequent seed viability and the consequences at the ecosystem level of changes to plant phenology. The potential for VOC metabolites to accumulate in plant tissue has been demonstrated, but any subsequent effects on herbivores and phytophagous insects have yet to be investigated.

Regional variation in surface properties of Norway spruce and scots pine needles in relation to forest decline.

Measurements of leaf wettability (contact angle), amounts of epicuticular wax and of surface dust are reported for Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L) Karst) trees growing at 12 sites in Europe from SW Germany to NE Scotland. At each site, three year classes (current year, 1 and 2-year-old) of needles were sampled from the mid-crown of up to 12 trees. Trees were selected at random from two strata, those showing visible decline symptoms (i.e. loss of needles or discoloration) and those apparently healthy. Needles for analysis were taken from apparently healthy (green) shoots in both cases. There were no significant differences between 'declining' and 'healthy' trees within sites, suggesting that leaf surface properties reflect environmental exposure rather than plant response. There were significant differences between sites, particularly for Norway spruce, which may be related to environmental factors including air pollution. Contact angles were consistently smaller at low-altitude sites in Britain and The Netherlands than at high-altitude sites in Germany where forests show decline symptoms. Leaf wettability decreased (contact angles increased) with wax amount and increased with dust amount. Leaf surface properties integrate environmental influences over long periods, and may be useful in identifying sites 'at risk' of developing decline symptoms, but causal relationships cannot be deduced without further direct experimentation.

Particulate and dissolved organic carbon in cloud water in southern Scotland.

Total particulate carbon (TPC), which includes both elemental carbon and particulate organic carbon, total suspended particulate matter (TSP) and dissolved organic carbon (DOC) were measured in 53 cloud water samples collected using a passive 'Harp-wire' cloud collector at weekly intervals at a hill-top site in southern Scotland (Dunslair Heights, 602 m above sea level) between December 1990 and April 1992. The concentrations of TPC, TSP and DOC were in the range 0.03-6.9 mg 1(-1) (median 1.05 mg l(-1)), 2.6-51.6 mg l(-1) (median 13.6 mg l(-1)) and 0.-14 mg l(-1) (median 3.6 mg l(-1)), respectively. The concentrations of TPC, TSP and DOC were greatest in winter (December-February), up to 6.9, 42 and 4.6 mg l(-1) respectively in 1990-1991 and up to 6.0, 51 and 14 mg l(-1), respectively, in 1991-1992. Particulate carbon in cloud water samples comprised 1-47% of the TSP. Concentrations of major anions (Cl(-), NO(-)(3), SO(2-)(4)) and pH were measured on the same water samples. Estimates of cloud liquid water content from January to April 1992 were derived from measured wind speeds and volumes of water collected. These estimates suggested that the air contained up to 1.2 microg TPC m(-3), 16 microg TSP m(-3) and 2.3 microg DOC m(-3), which are typical of concentrations to be expected in rural air. There was no correlation between concentrations of DOC in cloud water and either TPC or TSP, indicating that the sources and partitioning of DOC and TPC in the atmosphere are different. The largest concentrations of TPC coincided with the largest concentrations of non-marine sulphate, and although there was a significant linear correlation between the two sets of data, the log-transformed data were not correlated. Concentrations of TPC were significantly correlated with concentrations of other particulate matter (TSP-TPC), suggesting that similar sources and/or partitioning processes were involved in determining concentrations in cloud. Concentrations of DOC in cloud were significantly correlated (p < 0.02) with concentrations of nitrate, suggesting that sources of DOC were related to the emission and chemistry of nitrogen oxides. The very large concentrations of particulate carbon, especially in winter, indicate that carbon-catalysed oxidation of sulphur dioxide by molecular oxygen in cloud water may be a significant pathway when concentrations of hydrogen peroxide are small.

Exchange of organic solvents between the atmosphere and grass--the use of open top chambers.

Volatile organic compounds (VOC) are of increasing environmental significance as a result of continually increasing volumes of traffic on European roads. An open-top chamber fumigation system has been devised to investigate how these contaminants transfer between the atmosphere and the ground, and how they partition between and within air-plant-soil systems. Variation in chamber temperature, solar radiation in the chamber and chamber flow rate were identified as factors that affected final air concentrations. These were assessed and quantified for all individual chambers used--effectively characterising each chamber. The real-life VOC concentrations generated were stable and readily reproducible. Grass exposed to benzene, toluene, 1,1,1-trichloroethane and tetrachloroethene, respectively, equilibrated in response to a change in air concentration within hours. The rate of equilibration in exposed grass in all cases was independent of air temperature. 1,1,1-Trichloroethane and tetrachloroethene appear to be biologically inert demonstrating a simple physico-chemical approach to equilibrium, however, benzene and toluene do not appear independent of plant metabolic activity. Aqueous solubility can account for all of the toluene and benzene in the fumigated plant material.

Effects of acid mist on mature grafts of Sitka spruce. Part I. Frost hardiness and foliar nutrient concentrations.

Mature grafts of five clones of Sitka spruce (Picea sitchensis Bong. Sarg.) were exposed to simulated acid mist composed of an equimolar mixture of sulphuric acid and ammonium nitrate at pH 2.5 and pH 5.0 in open-top chambers from May to November 1991. Treatments were applied on consecutive days, four times a week. The pH 2.5 treatment provided an overall dose three times higher than that received by forests in upland areas of Britain. Frost hardiness was assessed in November by freezing detached current year shoots at a range of temperatures and assessing the rate of electrolyte leakage Foliar nutrient concentrations were determined on the same shoots. Acid mist at pH 2.5 significantly reduced frost hardiness in four of the five clones; the temperature causing 50% shoot death (LT50) was increased by 0 to 7 degrees C. The clones varied in their level of hardiness, one clone being exceptionally frost sensitive. The frost hardiness of the frost sensitive clone was found to be less perturbed by acid mist than the hardiness of the more frost resistant clones. Mature grafts showed a smaller reduction in hardiness at an equivalent dose than that found previously with Sitka spruce seedlings. Compared with seedlings, grafts had lower absolute concentrations of foliar sulphur. Exposure to acid mist at pH 2.5 increased %S in current year foliage by <0.05% compared with absolute increases of more than 0.10% in current year foliage of seedlings. We conclude that the effect of acid mist on frost hardiness is likely to be less on mature trees than on seedlings and that the increased frost risk to mature trees of Sitka spruce from occult deposition alone is small.