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Ammonia and ammonium have received less attention than other forms of air pollution, with limited progress in controlling emissions at UK, European and global scales. By contrast, these compounds have been of significant past interest to science and society, the recollection of which can inform future strategies. Sal ammoniac ( nūshādir , nao sha ) is found to have been extremely valuable in long-distance trade ( ca AD 600-1150) from Egypt and China, where 6-8 kg N could purchase a human life, while air pollution associated with nūshādir collection was attributed to this nitrogen form. Ammonia was one of the keys to alchemy-seen as an early experimental mesocosm to understand the world-and later became of interest as 'alkaline air' within the eighteenth century development of pneumatic chemistry. The same economic, chemical and environmental properties are found to make ammonia and ammonium of huge relevance today. Successful control of acidifying SO 2 and NO x emissions leaves atmospheric NH 3 in excess in many areas, contributing to particulate matter (PM 2.5 ) formation, while leading to a new significance of alkaline air, with adverse impacts on natural ecosystems. Investigations of epiphytic lichens and bog ecosystems show how the alkalinity effect of NH 3 may explain its having three to five times the adverse effect of ammonium and nitrate, respectively. It is concluded that future air pollution policy should no longer neglect ammonia. Progress is likely to be mobilized by emphasizing the lost economic value of global N emissions ($200 billion yr -1 ), as part of developing the circular economy for sustainable nitrogen management. This article is part of a discussion meeting issue 'Air quality, past present and future'.

Although it is generally accepted that δ 15 N in lichen reflects predominating N isotope sources in the environment, confirmation of the direct correlation between lichen δ 15 N and atmospheric δ 15 N is still missing, especially under field conditions with most confounding factors controlled. To fill this gap and investigate the response of lichens with different tolerance to atmospheric N deposition, thalli of the sensitive Evernia prunastri and the tolerant Xanthoria parietina were exposed for ten weeks to different forms and doses of N in a field manipulation experiment where confounding factors were minimized. During this period, several parameters, namely total N, δ 15 N and chlorophyll a fluorescence, were measured. Under the experimental conditions, δ 15 N in lichens quantitatively responded to the δ 15 N of released gaseous ammonia (NH 3 ). Although a high correlation between the isotopic signatures in lichen tissue and supplied N was found both in tolerant and sensitive species, chlorophyll a fluorescence indicated that the sensitive species very soon lost its photosynthetic functionality with increasing N availability. The most damaging response to the different N chemical forms was observed with dry deposition of NH 3 , although wet deposition of ammonium ions had a significant observable physiological impact. Conversely, there was no significant effect of nitrate ions on chlorophyll a fluorescence, implying differential sensitivity to dry deposition versus wet deposition and to ammonium versus nitrate in wet deposition. Evernia prunastri was most sensitive to NH 3 , then NH 4 + , with lowest sensitivity to NO 3 - . Moreover, these results confirm that lichen δ 15 N can be used to indicate the δ 15 N of atmospheric ammonia, providing a suitable tool for the interpretation of the spatial distribution of NH 3 sources in relation to their δ 15 N signal., (Copyright © 2018. Published by Elsevier B.V.)

Little information exists concerning the long-term interactive effect of nitrogen (N) addition with phosphorus (P) and potassium (K) on Sphagnum N status. This study was conducted as part of a long-term N manipulation on Whim bog in south Scotland to evaluate the long-term alleviation effects of phosphorus (P) and potassium (K) on N saturation of Sphagnum (S. capillifolium). On this ombrotrophic peatland, where ambient deposition was 8 kg N ha -1 yr -1 , 56 kg N ha -1 yr -1 of either ammonium (NH 4 + , N red ) or nitrate (NO 3 - , N ox ) with and without P and K, were added over 11 years. Nutrient concentrations of Sphagnum stem and capitulum, and pore water quality of the Sphagnum layer were assessed. The N-saturated Sphagnum caused by long-term (11 years) and high doses (56 kg N ha -1 yr -1 ) of reduced N was not completely ameliorated by P and K addition; N concentrations in Sphagnum capitula for N red 56 PK were comparable with those for N red 56, although N concentrations in Sphagnum stems for N red 56 PK were lower than those for N red 56. While dissolved inorganic nitrogen (DIN) concentrations in pore water for N red 56 PK were not different from N red 56, they were lower for N ox 56 PK than for N ox 56 whose stage of N saturation had not advanced compared to N red 56. These results indicate that increasing P and K availability has only a limited amelioration effect on the N assimilation of Sphagnum at an advanced stage of N saturation. This study concluded that over the long-term P and K additions will not offset the N saturation of Sphagnum., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Pristine bogs, peatlands in which vegetation is exclusively fed by rainwater (ombrotrophic), typically have a low atmospheric deposition of reactive nitrogen (N) (<0.5kgha -1 y -1 ). An important additional N source is N 2 fixation by symbiotic microorganisms (diazotrophs) in peat and mosses. Although the effects of increased total airborne N by anthropogenic emissions on bog vegetation are well documented, the important question remains how different N forms (ammonium, NH 4 + , versus nitrate, NO 3 - ) affect N cycling, as their relative contribution to the total load strongly varies among regions globally. Here, we studied the effects of 11years of experimentally increased deposition (32 versus 8kgNha -1 y -1 ) of either NH 4 + or NO 3 - on N accumulation in three moss and one lichen species (Sphagnum capillifolium, S. papillosum, Pleurozium schreberi and Cladonia portentosa), N 2 fixation rates of their symbionts, and potential N losses to peat soil and atmosphere, in a bog in Scotland. Increased input of both N forms led to 15-90% increase in N content for all moss species, without affecting their cover. The keystone species S. capillifolium showed 4 times higher N allocation into free amino acids, indicating N stress, but only in response to increased NH 4 + . In contrast, NO 3 - addition resulted in enhanced peat N mineralization linked to microbial NO 3 - reduction, increasing soil pH, N concentrations and N losses via denitrification. Unexpectedly, increased deposition from 8 to 32kgha -1 y -1 in both N forms did not affect N 2 fixation rates for any of the moss species and corresponded to an additional input of 5kgNha -1 y -1 with a 100% S. capillifolium cover. Since both N forms clearly show differential effects on living Sphagnum and biogeochemical processes in the underlying peat, N form should be included in the assessment of the effects of N pollution on peatlands., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Main Conclusion: Different nitrogen forms affect different metabolic pathways in lichens. In particular, the most relevant changes in protein expression were observed in the fungal partner, with NO 3 - mostly affecting the energetic metabolism and NH 4 + affecting transport and regulation of proteins and the energetic metabolism much more than NO 3 - did. Excess deposition of reactive nitrogen is a well-known agent of stress for lichens, but which symbiont is most affected and how, remains a mystery. Using proteomics can expand our understanding of stress effects on lichens. We investigated the effects of different doses and forms of reactive nitrogen, with and without supplementary phosphorus and potassium, on the proteome of the lichen Cladonia portentosa growing in a 'real-world' simulation of nitrogen deposition. Protein expression changed with the nitrogen treatments but mostly in the fungal partner, with NO 3 - mainly affecting the energetic metabolism and NH 4 + also affecting the protein synthesis machinery. The photobiont mainly responded overexpressing proteins involved in energy production. This suggests that in response to nitrogen stress, the photobiont mainly supports the defensive mechanisms initiated by the mycobiont with an increased energy production. Such surplus energy is then used by the cell to maintain functionality in the presence of NO 3 - , while a futile cycle of protein production can be hypothesized to be induced by NH 4 + excess. External supply of potassium and phosphorus influenced differently the responses of particular enzymes, likely reflecting the many processes in which potassium exerts a regulatory function.

Long-term additions of nitrogen (N) to peatlands have altered bryophyte growth, species dominance, N content in peat and peat water, and often resulted in enhanced Sphagnum decomposition rate. However, these results have mainly been derived from experiments in which N was applied as ammonium nitrate (NH4NO3), neglecting the fact that in polluted areas, wet deposition may be dominated either by NO3(-) or NH4(+). We studied effects of elevated wet deposition of NO3(-) vs. NH4(+) alone (8 or 56kgNha(-1)yr(-1) over and above the background of 8kgNha(-1)yr(-1) for 5 to 11years) or combined with phosphorus (P) and potassium (K) on Sphagnum quality for decomposers, mass loss, and associated changes in hummock pore water in an ombrotrophic bog (Whim). Adding N, especially as NH4(+), increased N concentration in Sphagnum, but did not enhance mass loss from Sphagnum. Mass loss seemed to depend mainly on moss species and climatic factors. Only high applications of N affected hummock pore water chemistry, which varied considerably over time. Overall, C and N cycling in this N treated bog appeared to be decoupled. We conclude that moss species, seasonal and annual variation in climatic factors, direct negative effects of N (NH4(+) toxicity) on Sphagnum production, and indirect effects (increase in pH and changes in plant species dominance under elevated NO3(-) alone and with PK) drive Sphagnum decomposition and hummock C and N dynamics at Whim., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The ability of Sphagnum moss to efficiently intercept atmospheric nitrogen (N) has been assumed to be vulnerable to increased N deposition. However, the proposed critical load (20kgNha(-1)yr(-1)) to exceed the capacity of the Sphagnum N filter has not been confirmed. A long-term (11years) and realistic N manipulation on Whim bog was used to study the N filter function of Sphagnum (Sphagnum capillifolium) in response to increased wet N deposition. On this ombrotrophic peatland where ambient deposition was 8kgNha(-1)yr(-1), an additional 8, 24, and 56kgNha(-1)yr(-1) of either ammonium (NH4(+)) or nitrate (NO3(-)) has been applied for 11years. Nutrient status of Sphagnum and pore water quality from the Sphagnum layer were assessed. The N filter function of Sphagnum was still active up to 32kgNha(-1)yr(-1) even after 11years. N saturation of Sphagnum and subsequent increases in dissolved inorganic N (DIN) concentration in pore water occurred only for 56kgNha(-1)yr(-1) of NH4(+) addition. These results indicate that the Sphagnum N filter is more resilient to wet N deposition than previously inferred. However, functionality will be more compromised when NH4(+) dominates wet deposition for high inputs (56kgNha(-1)yr(-1)). The N filter function in response to NO3(-) uptake increased the concentration of dissolved organic N (DON) and associated organic anions in pore water. NH4(+) uptake increased the concentration of base cations and hydrogen ions in pore water though ion exchange. The resilience of the Sphagnum N filter can explain the reported small magnitude of species change in the Whim bog ecosystem exposed to wet N deposition. However, changes in the leaching substances, arising from the assimilation of NO3(-) and NH4(+), may lead to species change., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Nitrogen (N) deposition impacts natural and semi-natural ecosystems globally. The responses of vegetation to N deposition may, however, differ strongly between habitats and may be mediated by the form of N. Although much attention has been focused on the impact of total N deposition, the effects of reduced and oxidised N, independent of the total N deposition, have received less attention. In this paper, we present new analyses of national monitoring data in the UK to provide an extensive evaluation of whether there are differences in the effects of reduced and oxidised N deposition across eight habitat types (acid, calcareous and mesotrophic grasslands, upland and lowland heaths, bogs and mires, base-rich mires, woodlands). We analysed data from 6860 plots in the British Countryside Survey 2007 for effects of total N deposition and N form on species richness, Ellenberg N values and grass:forb ratio. Our results provide clear evidence that N deposition affects species richness in all habitats except base-rich mires, after factoring out correlated explanatory variables (climate and sulphur deposition). In addition, the form of N in deposition appears important for the biodiversity of grasslands and woodlands but not mires and heaths. Ellenberg N increased more in relation to NHx deposition than NOy deposition in all but one habitat type. Relationships between species richness and N form were habitat-specific: acid and mesotrophic grasslands appear more sensitive to NHx deposition while calcareous grasslands and woodlands appeared more responsive to NOy deposition. These relationships are likely driven by the preferences of the component plant species for oxidised or reduced forms of N, rather than by soil acidification., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Ammonia (NH3) empirical critical levels for Europe were re-evaluated in 2009, based mainly on the ecological responses of lichen communities without acknowledging the physiological differences between oligotrophic and nitrophytic species. Here, we compare a nitrogen sensitive lichen (Evernia prunastri) with a nitrogen tolerant one (Xanthoria parietina), focussing on their physiological response (Fv/Fm) to short-term NH3 exposure and their frequency of occurrence along an NH3 field gradient. Both frequency and Fv/Fm of E. prunastri decreased abruptly above 3 μg m(-3) NH3 suggesting direct adverse effects of NH3 on its photosynthetic performance. By contrast, X. parietina increased its frequency with NH3, despite showing decreased capacity of photosystem II above 50 μg m(-3) NH3, suggesting that the ecological success of X. parietina at ammonia-rich sites might be related to indirect effects of increased nitrogen (NH3) availability. These results highlight the need to establish NH3 critical levels based on oligotrophic lichen species., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Wet deposition of nitrogen (N) occurs in oxidized (nitrate) and reduced (ammonium) forms. Whether one form drives vegetation change more than the other is widely debated, as field evidence has been lacking. We are manipulating N form in wet deposition to an ombrotrophic bog, Whim (Scottish Borders), and here report nine years of results. Ammonium and nitrate were provided in rainwater spray as NH4 Cl or NaNO3 at 8, 24 or 56 kg N ha(-1)  yr(-1) , plus a rainwater only control, via an automated system coupled to site meteorology. Detrimental N effects were observed in sensitive nonvascular plant species, with higher cumulative N loads leading to more damage at lower annual doses. Cover responses to N addition, both in relation to form and dose, were species specific and mostly dependent on N dose. Some species were generally indifferent to N form and dose, while others were dose sensitive. Calluna vulgaris showed a preference for higher N doses as ammonium N and Hypnum jutlandicum for nitrate N. However, after 9 years, the magnitude of change from wet deposited N on overall species cover is small, indicating only a slow decline in key species. Nitrogen treatment effects on soil N availability were likewise small and rarely correlated with species cover. Ammonium caused most N accumulation and damage to sensitive species at lower N loads, but toxic effects also occurred with nitrate. However, because different species respond differently to N form, setting of ecosystem level critical loads by N form is challenging. We recommend implementing the lowest value of the critical load range where communities include sensitive nonvascular plants and where ammonium dominates wet deposition chemistry. In the context of parallel assessment at the same site, N treatments for wet deposition showed overall much smaller effects than corresponding inputs of dry deposition as ammonia., (© 2013 John Wiley & Sons Ltd.)

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 Nr are on land (240 Tg N yr(-1)) within soils and vegetation where reduced Nr contributes most of the input through the use of fertilizer nitrogen in agriculture. Leakages from the use of fertilizer Nr contribute to nitrate (NO3(-)) in drainage waters from agricultural land and emissions of trace Nr compounds to the atmosphere. Emissions, mainly of ammonia (NH3) from land together with combustion related emissions of nitrogen oxides (NOx), contribute 100 Tg N yr(-1) to 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 NO3 contribute 40-70 Tg N yr(-1) to 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 Nr is buried in sediments, the remainder being denitrified back to the atmosphere as N2 or 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 Nr in 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 10(2)-10(3) years), the lifetime is a few decades. In the ocean, the lifetime of Nr is 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 Nr from which it is produced.

Previous studies have shown a correspondence between the abundance of particular plant species and methane flux. Here, we apply multivariate analyses, and weighted averaging, to assess the suitability of vegetation composition as a predictor of methane flux. We developed a functional classification of the vegetation, in terms of a number of plant traits expected to influence methane production and transport, and compared this with a purely taxonomic classification at species level and higher. We applied weighted averaging and indirect and direct ordination approaches to six sites in the United Kingdom, and found good relationships between methane flux and vegetation composition (classified both taxonomically and functionally). Plant species and functional groups also showed meaningful responses to management and experimental treatments. In addition to the United Kingdom, we applied the functional group classification across different geographical regions (Canada and the Netherlands) to assess the generality of the method. Again, the relationship appeared good at the site level, suggesting some general applicability of the functional classification. The method seems to have the potential for incorporation into large-scale (national) greenhouse gas accounting programmes (in relation to peatland condition/management) using vegetation mapping schemes. The results presented here strongly suggest that robust predictive models can be derived using plant species data (for use in national-scale studies). For trans-national-scale studies, where the taxonomic assemblage of vegetation differs widely between study sites, a functional classification of plant species data provides an appropriate basis for predictive models of methane flux., (© 2012 Blackwell Publishing Ltd.)

• Peat bogs have accumulated more atmospheric carbon (C) than any other terrestrial ecosystem today. Most of this C is associated with peat moss (Sphagnum) litter. Atmospheric nitrogen (N) deposition can decrease Sphagnum production, compromising the C sequestration capacity of peat bogs. The mechanisms underlying the reduced production are uncertain, necessitating multifactorial experiments. • We investigated whether glasshouse experiments are reliable proxies for field experiments for assessing interactions between N deposition and environment as controls on Sphagnum N concentration and production. We performed a meta-analysis over 115 glasshouse experiments and 107 field experiments. • We found that glasshouse and field experiments gave similar qualitative and quantitative estimates of changes in Sphagnum N concentration in response to N application. However, glasshouse-based estimates of changes in production--even qualitative assessments-- diverged from field experiments owing to a stronger N effect on production response in absence of vascular plants in the glasshouse, and a weaker N effect on production response in presence of vascular plants compared to field experiments. • Thus, although we need glasshouse experiments to study how interacting environmental factors affect the response of Sphagnum to increased N deposition, we need field experiments to properly quantify these effects., (© 2012 The Authors. New Phytologist © 2012 New Phytologist Trust.)

We review the ecological consequences of N deposition on the five Mediterranean regions of the world. Seasonality of precipitation and fires regulate the N cycle in these water-limited ecosystems, where dry N deposition dominates. Nitrogen accumulation in soils and on plant surfaces results in peaks of availability with the first winter rains. Decoupling between N flushes and plant demand promotes losses via leaching and gas emissions. Differences in P availability may control the response to N inputs and susceptibility to exotic plant invasion. Invasive grasses accumulate as fuel during the dry season, altering fire regimes. California and the Mediterranean Basin are the most threatened by N deposition; however, there is limited evidence for N deposition impacts outside of California. Consequently, more research is needed to determine critical loads for each region and vegetation type based on the most sensitive elements, such as changes in lichen species composition and N cycling., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Peatlands in the northern hemisphere have accumulated more atmospheric carbon (C) during the Holocene than any other terrestrial ecosystem, making peatlands long-term C sinks of global importance. Projected increases in nitrogen (N) deposition and temperature make future accumulation rates uncertain. Here, we assessed the impact of N deposition on peatland C sequestration potential by investigating the effects of experimental N addition on Sphagnum moss. We employed meta-regressions to the results of 107 field experiments, accounting for sampling dependence in the data. We found that high N loading (comprising N application rate, experiment duration, background N deposition) depressed Sphagnum production relative to untreated controls. The interactive effects of presence of competitive vascular plants and high tissue N concentrations indicated intensified biotic interactions and altered nutrient stochiometry as mechanisms underlying the detrimental N effects. Importantly, a higher summer temperature (mean for July) and increased annual precipitation intensified the negative effects of N. The temperature effect was comparable to an experimental application of almost 4 g N m(-2)  yr(-1) for each 1°C increase. Our results indicate that current rates of N deposition in a warmer environment will strongly inhibit C sequestration by Sphagnum-dominated vegetation., (© 2011 The Authors. New Phytologist © 2011 New Phytologist Trust.)

Here we investigate the response of soils and litter to 5 years of experimental additions of ammonium (NH4), nitrate (NO3), and ammonia (NH3) to an ombrotrophic peatland. We test the importance of direct (via soil) and indirect (via litter) effects on phosphatase activity and efflux of CO2. We also determined how species representing different functional types responded to the nitrogen treatments. Our results demonstrate that additions of NO3, NH4 and NH3 all stimulated phosphatase activity but the effects were dependent on species of litter and mechanism (direct or indirect). Deposition of NH3 had no effect on efflux of CO2 from Calluna vulgaris litter, despite it showing signs of stress in the field, whereas both NO3 and NH4 reduced CO2 fluxes. Our results show that the collective impacts on peatlands of the three principal forms of nitrogen in atmospheric deposition are a result of differential effects and mechanisms on individual components., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

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))., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

*Effects of nitrogen (N) enrichment on the heathland lichen Cladonia portentosa were quantified to test the hypothesis that modified N : phosphorus (P) relationships observed in this species in N-polluted natural environments are a direct effect of increased N deposition, and to evaluate potential confounding effects of N form and P availability. *Cladonia portentosa was harvested from experimental plots in lichen-rich peatland vegetation (background total N deposition of 8 kg N ha(-1) yr(-1)) treated for 4 yr with additional wet N deposition at 0, 8, 24 and 56 kg N ha(-1) yr(-1) as either NH(4)(+) or NO(3)(-), and with or without P added at either 0.6 or 4 kg P ha(-1) yr(-1). *Nitrogen enrichment increased thallus N concentration, N : P mass ratio and phosphomonoesterase (PME) activity by factors of up to 1.3, 1.4 and 1.7, respectively, effects being independent of N form. Phosphomonoesterase activity was tightly related to thallus N : P ratio with additions of P at 4 kg ha(-1) yr(-1) depressing PME activity by a factor of 0.4. *Nitrogen enrichment induces P-limitation in C. portentosa with attendant changes in chemical and physiological characteristics that could be used as sensitive biomarkers with which to detect low levels of N pollution.

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.

Effects and implications of reduced and oxidised N, applied under 'real world' conditions, since May 2002, are reported for Calluna growing on an ombrotrophic bog. Ammonia has been released from a 10 m line source generating monthly concentrations of 180-6 microg m(-3), while ammonium chloride and sodium nitrate are applied in rainwater at nitrate and ammonium concentrations below 4mM and providing up to 56 kg N ha(-1) year(-1) above a background deposition of 10 kg N ha(-1) year(-1). Ammonia concentrations, >8 microg m(-3) have significantly enhanced foliar N concentrations, increased sensitivity to drought, frost and winter desiccation, spring frost damage and increased the incidence of pathogen outbreaks. The mature Calluna bushes nearest the NH3 source have turned bleached and moribund. By comparison the Calluna receiving reduced and oxidised N in rain has shown no significant visible or stress related effects with no significant increase in N status.

This preliminary study investigated the effects of enhanced nitrogen (NH4NO3 at 48 kg ha(-1) y(-1)), sulphur (Na2SO4 at 50 kg ha(-1) y(-1)), acidified nitrogen and sulphur (H2SO4 + NH4NO3) at pre-stated doses (pH 2.5), and acidified nitrogen and sulphur deposition at double these doses on the ectomycorrhizal community associated with a 13-year-old Sitka spruce (Picea sitchensis) forest. Sulphur deposition had little impact on below ground ectomycorrhizal diversity, but stimulated sporocarp production. Nitrogen inputs increased below ground colonisation compared to acidified nitrogen and sulphur, largely due to an increase in Tylospora fibrillosa colonisation. Sporocarp production and ectomycorrhizal root colonisation by Lactarius rufus were reduced in the nitrogen treated plots. These observations suggest that nitrogen deposition to a young plantation may suppress ectomycorrhizal fungi producing large sporocarps. It is proposed that enhanced nitrogen deposition increases ectomycorrhizal nitrogen assimilation, consuming more carbon and leaving less for extrametrical mycelium and sporocarp development.

Throughfall chemistry was studied in a mature Sitka spruce plantation in order to investigate canopy interactions, such as nitrogen absorption, cation leaching, and neutralization of rainfall passing through the canopy. The plantation had been exposed to six different simulated mist treatments including N (NH(4)NO(3)) and S (H(2)SO(4) at pH 2.5) in four replicated blocks since 1996. Throughfall and rainfall were collected from May to September 2000. The results showed that 30-35% of the applied N was retained by the canopy. There were linear relationships between the loss of H(+) and increased K(+), Mg(2+) and Ca(2+) deposition through the canopy. However these increases in K(+), Mg(2+) and Ca(2+) deposition accounted for only about 50% of total neutralization of the acidity. The relationship between the anion deficits in throughfall and the loss of H(+) implied that weak organic acid anions were involved in the neutralization of the acidity in throughfall.

Increased deposition of atmospheric N largely from intensive agriculture is affecting biodiversity and the composition of natural and semi-natural vegetation in Europe. The value of species based bioindicators such as the Ellenberg N index and measurements of total tissue N and free amino acids in key plant species, is described with reference to a mixed woodland downwind of a livestock farm in the Scottish Borders, operated for over 20 years with a measured spatial gradient of ammonia concentration (29-1.5 microg m(-3)). All the indicators examined showed a relationship with N deposition and provided some indication of vegetation change. Total tissue N and arginine concentrations were most closely linked with ammonia concentrations and N deposition, with r(2) values of >0.97 and >0.78 respectively.

Beech (Fagus sylvatica L.) seedlings were grown in an ambient or elevated CO2 concentration ([CO2]) either in small stands in microcosms for three to four seasons or individually in pots fertilized at different nutrient supply rates. Leaves at different stages of development, as well as stems and roots at the end of the growing season, were used for analysis of structural biomass and lignin. In elevated [CO2], lignification of leaves was slightly retarded compared with structural biomass production and showed a strong correlation with the activities of ionically, cell-wall-bound peroxidases but not with total soluble peroxidases or covalently wall-bound peroxidases. The effect of elevated [CO2] on lignin concentration of mature tissues was dependent on nutrient supply rate. In leaves and roots, elevated [CO2] increased the lignin concentration in dry mass in N-limited plants. In seedlings grown with high nutrient supply, the lignin concentration in dry mass was unaffected or diminished by elevated [CO2]. Because elevated [CO2] enhanced seedling growth in the high nutrient supply treatments, the total amount of lignin produced per seedling was higher in these treatments. We predict that long-term sequestration of carbon will increase as long as biomass production is stimulated by elevated [CO2] and that tissue quality will change depending on developmental stage and nutrient availability.

There has been increasing pressure on farmers in Europe to reduce the emissions of ammonia from their land. Due to the current financial climate in which farmers have to operate, it is important to identify ammonia control measures that can be adopted with minimum cost. The planting of trees around farmland and buildings has been identified as a potentially effective and low-cost measure to enhance ammonia recapture at a farm level and reduce long-range atmospheric transport. This work assesses experimentally what fraction of ammonia farm woodlands could potentially remove from the atmosphere. We constructed an experimental facility in southern Scotland to simulate a woodland shelterbelt planted in proximity to a small poultry unit. By measuring horizontal and vertical ammonia concentration profiles within the woodland, and comparing this to the concentration of an inert tracer (SF6) we estimate the depletion of ammonia due to dry deposition to the woodland canopy. Together with measurements of mean ammonia concentrations and throughfall fluxes of nitrogen, this information is used to provide a first estimate of the fraction of emitted ammonia that is recaptured by the woodland canopy. Analysis of these data give a lower limit of recapture of emitted ammonia, at the experimental facility, of 3%. By careful design of shelterbelt woodlands this figure could be significantly higher.

An eighteen-year-old clone of Sitka spruce (Picea sitchensis (Bong.) Carr) growing in the field was used to evaluate the whole tree response of 'mature' Sitka spruce to acid mist treatment. The mist, an equimolar mixture of H(2)SO(4) and NH(4)NO(3) at pH 2.5 with or without particles (soda glass ballotini < 20 microm diameter), was applied twice weekly (equivalent to 4 mm precipitation week(-1)) throughout the growing season, May-November 1990-1992. The annual dose of S, N, H applied as mist (at 51, 48 and 3.3 kg ha(-1), respectively) was 2.5 times that measured in the Scottish uplands. Throughout the experiment there was no evidence of visible injury symptoms, yet there was a highly significant reduction (p < 0.02) in the stem-area increment relative to the stem area at the start, measured using vernier dendrometer bands. There was no significant difference between the (acid mist + particle) and the acid mist only treatments. The mean relative stem-area increment over two complete growing seasons (1991-1992) was 65% for control trees, but only 53% for acid-misted trees.

Mature grafts of five Sitka spruce (Picea sitchensis (Bong.) Carr.) clones were exposed to simulated acid mist comprising an equimolar mixture of H(2)SO(4) and NH(4)NO(3) (1.6 and 0.01 mol m(-3)) at pH 2.5 and 5.0. Mist was applied to potted plants growing in open-top chambers on consecutive days, four times a week, at a precipitation equivalent of 1 mm per day. The total exposure to polluted mist was equivalent to three times that measured at an upland forest in SE Scotland. The aim of the experiment was to characterize the response of juvenile foliage produced by physiologically mature grafts (on seedling root stock) and compare it with the behaviour of juvenile foliage on seedlings. Development of visible foliar damage was followed through the growing season. Measurements of needle length, diameter, weight, surface area, surface was weight and wettability were made on current year needles to determine whether particular foliar characteristics increased susceptibility to injury. Significant amounts (> 10%) of visible needle damage was observed on only one of the five clones. Damage was most severe on the clone with the most horizontal branch and needle habit, but over the five clones there was no relationship between angle of branch display and damage. Likewise no combination of needle characteristics (length, width, area, amount of wax) was indicative of potential susceptibility. A comparison with previous acid misting experiments using seedlings suggests that juvenile foliage on physiologically mature trees is equally susceptible to visible injury as juvenile seedling foliage. Data of budburst differed among clones, and in this experiment exerted the over-riding influence on development of injury symptoms. Foliage exposed to a combination of strong acidity and high sulphate concentrations over the few weeks immediately following budburst suffered most visible injury. The absence of significant amounts of visible damage in UK forests probably reflects the general low susceptibility to visible injury of Sitka spruce exposed to acid mist.

This paper summarizes results from four experiments in which red spruce seedlings (Picea rubens Sarg.) were exposed to simulated acid mist containing SO 4 2- , NH 4- , NO 3 - and H + ions. Seedlings were grown in compost, with or without fertilizer, in charcoal filtered air in open-top chambers near Edinburgh, Scotland. Plants were sprayed from bud burst between May and November with mist containing different concentrations and combinations of the four major ions to provide a range of doses, which were applied at different frequencies. Reductions in frost hardiness expressed in terms of the temperature which killed 50% of shoots (LT 50 ) were significantly correlated with the dose of S received by the seedlings. Differences in foliar S concentrations between the controls and treated plants were correlated with S dose. Absolute S concentrations were, however, of limited use for predictive purposes. Seedlings appear to be more sensitive than older trees to S toxicity because the former have the greatest proportion of newly expanding needles which optimize conditions for foliar uptake. Seedlings are also least well equipped to export SO 4 2- ions since they have a smaller resource of older foliage to supplement their assimilate pool. In conditions which promote uncontrolled SO 4 2- ion uptake by foliage, i.e. high external SO 4 2- concentrations and incompletely formed cuticles, the potential exists for the internal build up of SO 4 2- ions. It is proposed that in the absence of sufficient assimilate and K the presence of these high concentrations of SO 4 2- ions in the apoplast or cytosol can lead to protein denaturation and loss of membrane integrity. Reductions in frost hardiness appear to result through direct attack by SO 4 2 ions on membrane proteins which impairs their function. Indirect effects on hardiness occur through both an increased consumption of sugars reducing the'pool'available for cryoprotection and a reduction in photosynthetic function, the ability to produce sugars. The presence of NO 3- N mitigates the toxic effects of SO 4 2 because SO 4 2 ions are consumed in assimilation processes which both utilize and are facilitated by the presence of large amounts of fertilizer N. High concentrations of SO 4 2 and H+ are found to be particularly toxic because of the synergistic effects these ions exert on their mutual uptake with devastating consequences for the control of cellular pH. Trees growing at high altitude sites are likely to be particularly sensitive to SO 4 2- toxicity because (1) their carbon balance is low, (2) cuticle development is poor and (3) levels of soil available Ca 2 tend to be low relative to Al 3+ so that membranes may already be weakened as a result of insufficient Ca 2+ ions for protein bridging.

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.

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 m 3 (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 (LT 50 ), 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.

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 m 3 ) 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 (LT 50 ) 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.

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.

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.

Differences in stem wood production were found among four clones of Picea sitchensis (Bong.) Carr. at both an agricultural and a forest site. Clonal rankings were not consistent between the sites. Four variables were identified that may influence stem wood production, foliage amount, total aboveground production per unit foliage, proportional allocation of production to new foliage and to branch wood thickening. Comparison of clonal performance between sites showed that stem wood production could be influenced by differences in each of these variables. The four variables were themselves determined by components of crown structure, these were (i) production of new branches from the main stem, (ii) the numbers and lengths of branchlets supported on branches from the main stem, (iii) foliage production per unit branchlet length and foliage longevity, and (iv) branch wood thickening per unit branch length. These components varied both among clones and between sites. Branch production from the mainstem varied among clones, and for some clones it varied substantially between sites. In some clones branch production was positively correlated with mainstem height increment. There were differences among clones in the way that branchlet production varied between the agricultural and forest sites. In the absence of needle fall, foliage weight/branch length varied threefold among clones, but for each clone, varied little between sites. Branch wood weight/branch length was generally greater when foliage weight/branch length was large, but total branch wood increment/tree was strongly influenced by total branch length. The dynamics of crown development and its relation to stem wood production are discussed with reference to (i) the importance of needle longevity, (ii) the importance of tallness and narrowness of crowns and (iii) the importance of branch thickening, a process that competes with stem growth in the utilization of photosynthate. It is concluded that although each of these factors may be important, none singly accounts for the observed differences in stem wood production among genotypes and the way these change in response to the environment.

It has been proposed that pollutants predispose Picea rubens Sarg. growing in the high Appalachians to frost damage. The pattern of autumn hardening of P. rubens growing at Whiteface Mountain, NY, and Newfound Gap, NC, was monitored by detaching shoots at 1-3 weekly intervals, air freighting them to Scotland, and freeze-testing them. The temperatures that produced freezing injury from August 1986 to January 1987 were compared with minimum air temperatures recorded in those months at nearby meteorological stations over 22 previous years. There was only weak evidence that the onset or degree of frost hardening was inadequate to protect the trees from direct freezing injury (as opposed to winter desiccation). Historically, minimum air temperatures occasionally fell below the lethal temperature for a 10% kill (LT(10)), but they rarely fell below the LT(50). The trees hardened rapidly in the autumn (max. 2.2 degrees C day(-1)) to between -30 degrees C and -40 degrees C by January (LT(50)), including trees showing visible decline on Clingman's Dome, TN. Individual trees differed in hardiness by up to 10 degrees C. It is concluded that any pollutant-induced susceptibility to freezing injury is insufficient, on its own, to account for forest decline in the Appalachians.

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 (NH 4 ) 2 SO 4 , and HNO 3 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 NH 4 + , NO 3 - , SO 4 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.

Seedlings of red spruce [Picea rubens Sarg. syn. P. rubra (Du Roi) Link] were exposed to mists containing equimolar (NH 4 , SO 4 and HNO 3 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 (LT 50 ) 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 LT 50 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 LT 10 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 LT 10 level in an average October. The proximity of minimum night temperatures during September to December to the LT 10 temperatures of red spruce shoots receiving large inputs of SO 4 2- , NO 3 - , NH 4 + 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.