Alkaline air: changing perspectives on nitrogen and air pollution in an ammonia-rich world.

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 (nushadir, 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 nushadir 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 SO2 and NOx emissions leaves atmospheric NH3 in excess in many areas, contributing to particulate matter (PM2.5) 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 NH3 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'.

Long-term interactive effects of N addition with P and K availability on N status of Sphagnum.

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 (NH4+, Nred) or nitrate (NO3-, Nox) 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 Nred 56 PK were comparable with those for Nred 56, although N concentrations in Sphagnum stems for Nred 56 PK were lower than those for Nred 56. While dissolved inorganic nitrogen (DIN) concentrations in pore water for Nred 56 PK were not different from Nred 56, they were lower for Nox 56 PK than for Nox 56 whose stage of N saturation had not advanced compared to Nred 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.

The cost of surviving nitrogen excess: energy and protein demand in the lichen Cladonia portentosa as revealed by proteomic analysis.

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 NO3- mainly affecting the energetic metabolism and NH4+ 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 NO3-, while a futile cycle of protein production can be hypothesized to be induced by NH4+ 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.

Sphagnum can 'filter' N deposition, but effects on the plant and pore water depend on the N form.

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.

Inertia in an ombrotrophic bog ecosystem in response to 9 years' realistic perturbation by wet deposition of nitrogen, separated by form.

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.

Direct and indirect effects of ammonia, ammonium and nitrate on phosphatase activity and carbon fluxes from decomposing litter in peatland.

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.

Stress responses of Calluna vulgaris to reduced and oxidised N applied under 'real world conditions'.

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.

Differential responses of UK upland plants to nitrogen deposition.

Native upland species, Nardus stricta, Eriophorum vaginatum, Erica cinerea and Vaccinium vitis-idaea were given 3 or 60 kg N ha-1 yr-1 , over 2 yr, applied as a mist (NH4 NO3 ). The high N treatment increased above-ground biomass in all four species, but only significantly in E. cinerea, E. vaginatum and N. stricta. Biomass increases in E. vaginatum and N. stricta resulted from enhanced tiller production rather than shoot elongation. Root growth increased in N. stricta, so that root∶shoot ratio in this species was unchanged by N. Root growth in E. vaginatum, E. cinerea and V. vitis-idaea did not respond to N and their root∶shoot ratios decreased. Tissue N concentrations increased in both shoots and roots of all species in response to N. The accumulated foliar N did not increase the proportion of N allocated to Rubisco and the photosynthetic capacities of N. stricta, E. vaginatum and V. vitis-idaea were unchanged. Thus growth responses to N were due to altered allocation rather than increased rate of photosynthesis per unit leaf area. The high N treatment increased flower production significantly in E. cinerea but not in the other species. Although in this experiment dwarf shrubs were more responsive than graminoids to N, in the field at current N inputs the enhanced tillering of the graminoids may be more competitively advantageous, especially where gaps develop in the canopy. Thus increasing N deposition may lead to increased grassiness of upland heath, and in particular, a spread of N. stricta.

Influence of episodes of summer O3 on δ5 and δ9 fatty acids in autumnal lipids of Norway spruce [Picea abies (L.) Karst].

Current year needles from 5 yr-old Norway spruce trees, which had been exposed to either episodes of atmospheric O3 , or periodic mistings with simulated acid rainwater throughout three summer periods, were-analyzed for changes in molar percentages and ratios of fatty acids isolated from different lipids at the time of maximum winter hardening. No significant changes due to acidic misting were detected but significant decreases in the degree of unsaturation off both C 16 and C18 , fatty acids, the molar percentage of δ5,9,12,15 , and the molar ratio δ5,9 18: 2 to δ9,12 18:2 in monogalactosyl diglyceride (MGDG) due to summer 03 exposures were found. Molar percentages and ratios of fatty acids did not change much in other lipids bur these changes in plastidie MGDG could be traced to a significant effect of summer O3 on the δ4 - and δ12 -desaturases acting upon phosphatidyl choline (PC) in the endoplasmic reticulum. The replacement of the δ6 -subset of C18 fatty acids by an equivalent δ5 -series throughout was confirmed by Gas chromatography and mass spectrometry Molecular modelling also showed that the δ5 forms, which resembled the δ5 -isomers, are very different in shape to the δ5 -series and this may account, in part, for the extremely low winter temperatures from which Norway spruce needles may recover.