Effects of ozone on species composition in an upland grassland.

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

Hydrochloric acid: an overlooked driver of environmental change.

Research on the ecosystem impacts of acidifying pollutants, and measures to control them, has focused almost exclusively on sulfur (S) and nitrogen (N) compounds. Hydrochloric acid (HCl), although emitted by coal burning, has been overlooked as a driver of ecosystem change because most of it was considered to redeposit close to emission sources rather than in remote natural ecosystems. Despite receiving little regulatory attention, measures to reduce S emissions, and changes in energy supply, have led to a 95% reduction in United Kingdom HCl emissions within 20 years. Long-term precipitation, surface water, and soil solution data suggest that the near-disappearance of HCl from deposition could account for 30-40% of chemical recovery from acidification during this time, affecting both near-source and remote areas. Because HCl is highly mobile in reducing environments, it is a more potent acidifier of wetlands than S or N, and HCl may have been the major driver of past peatland acidification. Reduced HCl loadings could therefore have affected the peatland carbon cycle, contributing to increases in dissolved organic carbon leaching to surface waters. With many regions increasingly reliant on coal for power generation, HCl should be recognized as a potentially significant constituent of resulting emissions, with distinctive ecosystem impacts.

Harmful effects of atmospheric nitrous acid on the physiological status of Scots pine trees.

An open top chamber experiment was carried out in the summer of 2003 to examine the effect of nitrous acid (HONO) gas on the physiological status of Scots pine saplings (Pinus sylvestris). Four-year-old pine trees were exposed to two different levels of HONO gas (at ca. 2.5 ppb and 5.0 ppb) and a control (filtered air) from early evening to early morning (18:00-6:00), in duplicate open top chambers. Significant decreases in the ratios of chlorophylls a to b, an increase in the carbon to nitrogen (C/N) ratio, and a reduction of maximum yield of PS II (F(v)/F(m)) in pine needles were also observed after the 2 months' fumigation. Cation contents of pine needles were also decreased by the fumigation with HONO gas. The results could be explained by the harmful effects of OH radicals, generated from photolysis of HONO gas, and/or aqueous phase HONO (NO(2)(-)/HONO), on the photosynthetic capacity of pine needles.

Secondary air pollutants and forests--new perspectives.

Air pollution has been known to affect forests for over a century, and many of the mechanisms of pollutant deposition and effects have been established, at least for forest trees. Changes in air quality as a result of emission controls in Europe and North America, or as a result of rapid industrialisation in southern and eastern Asia, have highlighted new pollution problems. This paper, by reference to recent publications, highlights two areas where more research is required: the interactions of photochemical oxidants with biogenic emissions of volatile organic compounds, and their impact on ecological signalling; and the role of atmospheric particles in changing the leaf surface environments in forests.

Progress in understanding the sources, deposition and above-ground fate of trichloroacetic acid.

AIM AND SCOPE: This paper is a companion to the recent review paper by Laturnus et al. (2005) on TCA in soils, presenting a complementary review of knowledge gaps in the sources and fate of trichloroacetic acid (TCA) in plants. MAIN FEATURES: The review considers the various sources of TCA precursors, including the question of how much atmospheric TCA comes from naturally-produced precursors, and addresses the implications of climate change on atmospheric TCA formation. Models of the conversion of precursors to TCA in the atmosphere are critically compared with field measurements of concentrations, deposition and budgets; data on the quantitative relationships between gas-phase TCA, particulate TCA, and TCA dissolved in rain and clouds are reviewed. Methods for quantifying TCA are summarised, along with a description of what the different techniques measure, and how results can be compared. A distinction is made between 'extractable' TCA and 'total' TCA in vegetation. Evidence for the various pathways by which TCA enters plants is given, including the in situ production of TCA in leaves. This leads to a better understanding of how plant tissue concentrations depend on uptake, production and removal rates. Finally, knowledge of the toxic effects of TCA on plants and TCA metabolism in plant tissues is summarised. RESULTS AND DISCUSSION: The discussion highlights knowledge gaps, and is intended to aid the reader in interpreting previously published results through identifying where different ways of expressing data have been used, and the consequent conclusions that can be drawn. CONCLUSION AND FURTHER RESEARCH DIRECTIONS: Recommendations are given for future research directions--in identifying precursor sources, quantifying heterogeneous atmospheric processes, recognising and quantifying uptake pathways, and elucidating the biochemical mechanisms involved in sequestering and degrading TCA inside leaves.

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.

Practical considerations for addressing uncertainties in monitoring bulk deposition.

The assessment of the deposition of both wet (rain and cloud) and dry sedimenting particles is a prerequisite for estimating element fluxes in ecosystem research. Many nations and institutions operate deposition networks using different types of sampler. However, these samplers have rarely been characterized with respect to their sink properties. Major errors in assessing bulk deposition can result from poor sampling properties and defective sampling strategies. Relevant properties are: sampler geometry and material, in particular the shape of the rim; sink properties for gases and aerosols; and microbial transformations of the collected samples. An adequate number of replicates allows the identification of samples which are contaminated, in particular by bird droppings. The paper discusses physical and chemical properties of the samplers themselves. The dependence of measurement accuracy on the number of replicates and the sampling area exposed is discussed. Recommendations are given for sampling strategies, and for making corrections and substitution of missing data.

Atmospheric nitrogen compounds-issues related to agricultural systems.

Workable pollution abatement policies and effective legislation must be based on sound science. However, despite many years of research, there are still uncertainties about the effects of atmospheric nitrogen compounds on crops and other vegetation. This paper reviews the current state of knowledge of the main compounds, focussing on the concentrations and combinations of pollutants that occur in rural areas. The sources, concentrations and effects of oxidised, reduced and organic nitrogen compounds are considered in turn, then the effects of deposited nitrogen on ecosystems are discussed. Research priorities on the effects of deposited nitrogen in Europe and the USA are compared. Finally, the review leads to a list of issues for discussion and recommendations for research.

Ecological effects of sulfur dioxide, fluorides, and minor air pollutants: recent trends and research needs.

The regulation of the emissions of 'traditional' primary air pollutants (fluorides, sulfur dioxide) has changed the pattern of exposure of ecological systems, with greatly reduced exposure close to sources, but with a smaller effect in some remote areas. Measurements show that recovery is occurring at some sites, in fresh water chemistry (reduced acidity) and in sensitive biota (sustainable fish populations). However, the pattern of change in exposure has not always been simply related to emission reductions. An understanding of responses to recent changes will improve our predictions of the response to future emission changes, both locally and globally. As exposure to 'traditional' pollutants is reduced, the potential for other pollutants to have effects becomes more evident. In the aqueous phase, we need to understand the role of soluble and suspended organics, but this also means explicit recognition of the possibility of phase exchange, and the role of photolytic reactions on plant, soil, and water surfaces. Do highly reactive free radicals in the atmosphere, formed by the action of sunlight on volatile organic compounds, have direct effects on plants? Organic compounds and heavy metals may be bioactive as gases and particles, but for many potentially toxic compounds, the experimental evidence for biotic response is very limited. To evaluate the potential effects of pollutants, we need to understand the pathways by which airborne pollutants enter and react within ecosystems. For vegetation, we have to consider bidirectional fluxes, and distinguish among uptake through stomata, through leaf surfaces, or through roots. There are several challenges for the future. (1) Can we devise experiments that permit exposure of vegetation to gases, particles, and/or aqueous pollutants at 'realistic' concentrations? (2) Can we include the potential interactions with photolytically derived free radicals, and the dynamics of exchange? (3) How do we allow for responses to pollutant mixtures, or the simultaneous exposure to pollutants in gas, particle, and aqueous phases? The recognition of the importance of the dynamic exchange of pollutants between phases will be the key to the development of effective experimental approaches to evaluating cause-effect relationships between pollutant mixtures and ecosystem responses.

The global nitrogen cycle in the twenty-first century.

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.

Effects of land use on surface-atmosphere exchanges of trace gases and energy in Borneo: comparing fluxes over oil palm plantations and a rainforest.

This paper reports measurements of land-atmosphere fluxes of sensible and latent heat, momentum, CO(2), volatile organic compounds (VOCs), NO, NO(2), N(2)O and O(3) over a 30 m high rainforest canopy and a 12 m high oil palm plantation in the same region of Sabah in Borneo between April and July 2008. The daytime maximum CO(2) flux to the two canopies differs by approximately a factor of 2, 1200 mg C m(-2) h(-1) for the oil palm and 700 mg C m(-2) h(-1) for the rainforest, with the oil palm plantation showing a substantially greater quantum efficiency. Total VOC emissions are also larger over the oil palm than over the rainforest by a factor of 3. Emissions of isoprene from the oil palm canopy represented 80 per cent of the VOC emissions and exceeded those over the rainforest in similar light and temperature conditions by on average a factor of 5. Substantial emissions of estragole (1-allyl-4-methoxybenzene) from the oil palm plantation were detected and no trace of this VOC was detected in or above the rainforest. Deposition velocities for O(3) to the rainforest were a factor of 2 larger than over oil palm. Emissions of nitrous oxide were larger from the soils of the oil palm plantation than from the soils of the rainforest by approximately 25 per cent. It is clear from the measurements that the large change in the species composition generated by replacing rainforest with oil palm leads to profound changes in the net exchange of most of the trace gases measured, and thus on the chemical composition of the boundary layer over these surfaces.

Responses of herbaceous plants to urban air pollution: effects on growth, phenology and leaf surface characteristics.

Vehicle exhaust emissions are a dominant feature of urban environments and are widely believed to have detrimental effects on plants. The effects of diesel exhaust emissions on 12 herbaceous species were studied with respect to growth, flower development, leaf senescence and leaf surface wax characteristics. A diesel generator was used to produce concentrations of nitrogen oxides (NO(x)) representative of urban conditions, in solardome chambers. Annual mean NO(x) concentrations ranged from 77 nl l(-l) to 98 nl l(-1), with NO:NO(2) ratios of 1.4-2.2, providing a good experimental simulation of polluted roadside environments. Pollutant exposure resulted in species-specific changes in growth and phenology, with a consistent trend for accelerated senescence and delayed flowering. Leaf surface characteristics were also affected; contact angle measurements indicated changes in surface wax structure following pollutant exposure. The study demonstrated clearly the potential for realistic levels of vehicle exhaust pollution to have direct adverse effects on urban vegetation.

Addressing analytical uncertainties in the determination of trichloroacetic acid in soil.

Soil is an important compartment in the environmental cycling of trichloroacetic acid (TCA), but soil TCA concentration is a methodologically defined quantity; analytical methods either quantify TCA in an aqueous extract of the soil, or thermally decarboxylate TCA to chloroform in the whole soil sample. The former may underestimate the total soil TCA, whereas the latter may overestimate TCA if other soil components (e.g. humic material) liberate chloroform under the decarboxylation conditions. The aim of this work was to show that extraction and decarboxylation methods yield different TCA concentrations because the decarboxylation method can also determine "bound" TCA. Experiments with commercial humic acid solutions showed there was no additional chloroform formation under decarboxylation conditions, and that all TCA in a TCA-humic acid mixture could be quantitatively determined (108 +/- 13%). Anion exchange resin was used as a provider of solid-phase TCA binding; only 5 +/- 1% of a TCA solution mixed with the resin was present in the aqueous extract subsequently separated from the resin, yet the decarboxylation method yielded mass balance (123 +/- 22%) with TCA remaining in the resin. In aqueous extraction of a range of soil samples (with or without added TCA spike), the decarboxylation method was able to satisfactorily account for TCA in the extractant + residue post-extraction, compared with whole-soil TCA (+ spike) pre-extraction: e.g. mass balances for unspiked soil from Sikta spruce and larch forest were 99 +/- 8% and 93 +/- 6%, respectively, and for TCA-spiked forest and agricultural soils were 114 +/- 13% and 102 +/- 2%. In each case recovery of TCA in the extractant was substantially less than 100%(<20% for unspiked soils, <55% for spiked soils). Extraction efficiencies were generally lower in more organic soils. The results suggest that analytical methods which utilise aqueous extraction may underestimate whole-soil TCA concentrations. Application of both methodologies together may enhance insight into TCA behaviour in soil.

Long-term exposure of Sitka spruce seedlings to trichloroacetic acid.

Trichloroacetic acid (TCA) has been implicated as an airborne pollutant responsible for adverse effects on forest health. There is considerable debate as to whether TCA observed in trees and forest soils is derived from atmospheric deposition or from in situ production. This experiment reports the results from treating 4-year-old Sitka spruce (Picea sitchensis (Bong.) Carr) plants in a greenhouse over a growing season with TCA supplied either to the soil or to the foliage at concentrations of 10 and 100 ng mL(-1). Similar uptake of TCA by needles was observed for both modes of treatment, with significant accumulation of TCA (300 ng g(-1) dry wt) at the higher concentration. Larger concentrations in stem tissue were seen for the foliar-applied TCA (280 ng g(-1)) than for the soil-applied TCA (70 ng g(-1)), suggesting that direct stem uptake may be important. Six months after treatments stopped, TCA concentrations in the needles of plants exposed to 100 ng mL(-1) TCA were still enhanced, showing that biological degradation of TCA in needles was slow over the winter. By contrast, no significant enhancement of TCA in soil could be detected in the directly treated soils even during the experiment. The protein content of needles treated with the higher concentration of TCA by either route was significantly smaller than for the controls, but there was no effect of TCA on the conjugation of 1-chloro-2,4-dinitrobenzene in roots nor on the conjugation of 1,2-dichloro-4-nitrobenzene in needles.