Photosynthetic stimulation and stomatal conductance (Gs) depression in Quercus ilex leaves at a CO2 spring suggested no down-regulation. The insensitivity of Gs to a CO2 increase (from ambient 1500 to 2000 μmol mol-1) suggested stomatal acclimation. Both responses are likely adaptations to the special environment of CO2 springs. At the CO2-enriched site, not at the control site, photosynthesis decreased 9% in leaves exposed to 2x ambient O3 concentrations in branch enclosures, compared to controls in charcoal-filtered air. The stomatal density reduction at high CO2 was one-third lower than the concomitant Gs reduction, so that the O3 uptake per single stoma was lower than at ambient CO2. No significant variation in monoterpene emission was measured. Higher trichome and mesophyll density were recorded at the CO2-enriched site, accounting for lower O3 sensitivity. A long-term exposure to H2S, reflected by higher foliar S-content, and CO2 might depress the antioxidant capacity of leaves close to the vent and increase their O3 sensitivity. Very high CO2 concentrations did not compensate for the effects of O3 on holm oak photosynthesis.

Human activity is changing air quality and climate in the US Pacific Northwest. In a first application of non-metric multidimensional scaling to a large-scale, framework dataset, we modeled lichen community response to air quality and climate gradients at 1416 forested 0.4 ha plots. Model development balanced polluted plots across elevation, forest type and precipitation ranges to isolate pollution response. Air and climate scores were fitted for remaining plots, classed by lichen bioeffects, and mapped. Projected 2040 temperatures would create climate zones with no current analogue. Worst air scores occurred in urban-industrial and agricultural valleys and represented 24% of the landscape. They were correlated with: absence of sensitive lichens, enhancement of nitrophilous lichens, mean wet deposition of ammonium >0.06 mg l-1, lichen nitrogen and sulfur concentrations >0.6% and 0.07%, and SO2 levels harmful to sensitive lichens. The model can detect changes in air quality and climate by scoring re-measurements. Lichen-based air quality and climate gradients in western Oregon and Washington are responsive to regionally increasing nitrogen availability and to temperature changes predicted by climate models.

The study uses measured and calculated data on airborne pollutants, particularly nitrogen (ranges between 28 to 43 kg N*ha-1*yr-1) and sulphur (10 to 18 kg SO4-S*ha-1*yr-1), in order to assess their long-term (1992 to 2005) effects on bryophytes at the UN-ECE Integrated Monitoring site 'Zöbelboden' in Austria. Bryophytes were used as reaction indicators on 20 epiphytic plots using the IM monitoring method and on 14 terrestrial plots using standardised photography. The plots were recorded in the years 1992, 1993, 1998, and 2004/2005. Most species remained stable in terms of their overall population size during the observed period, even though there were rapid turnover rates of a large percentage of species on all investigated plots. Only a few bryophytes (Hypnum cupressiforme, Leucodon sciuroides) responded unambiguously to N and S deposition. Nitrogen deposition had a weak but significant effect on the distribution of bryophyte communities. However, the time shifts in bryophyte communities did not depend on total deposition of N and S. Bryophytes show ambiguous response to airborne pollutants during 14 years of monitoring in a forest ecosystem.

Concern regarding the impacts of continued nitrogen and sulfur deposition on ecosystem health has prompted the development of critical acid load assessments for forest soils. A critical acid load is a quantitative estimate of exposure to one or more pollutants at or above which harmful acidification-related effects on sensitive elements of the environment occur. A pollutant load in excess of a critical acid load is termed exceedance. This study combined a simple mass balance equation with national-scale databases to estimate critical acid load and exceedance for forest soils at a 1-km2 spatial resolution across the conterminous US. This study estimated that about 15% of US forest soils are in exceedance of their critical acid load by more than 250 eq ha-1 yr-1, including much of New England and West Virginia. Very few areas of exceedance were predicted in the western US. This simple mass balance equation estimated that 17% of US forest soils exceed their critical acid load by more than 250 eq ha-1 yr-1, and these areas are predominantly located in the northeastern US.

Industrial soils near Zn-Pb mines and metallurgical plants in the vicinity of Olkusz (southern Poland) are exposed to high environmental stress related to heavy metal pollution (Zn, Pb, Cd, Mn, Fe, Tl and As) from waste disposal sites and primary ores. X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectrometry analyses (EDS) and Atomic Absorption Spectroscopy (AAS) were used to analyse rhizosphere soil samples from the area. The mineral composition of the rhizosphere soils was determined. Carbonates of lead, cadmium and zinc, arsenic-lead sulphosalts and other minerals occurring on the root epiderm are described. Mineral aggregates of secondary origin include polymineralic spherules containing high concentrations of Zn (up to 2.3%), Pb (up to 0.7%), Fe (up to 23%), Cd (up to 427 mg kg-¹) and Tl (up to 139 mg kg-¹). Processes on the rhizoplane, and in the zone where plant-root exudation solutions are active, promote the crystallization of metalliferous minerals. ESEM is recommended as an efficient method for examining alteration occurring in the rhizosphere environment.

Lowland heath is an internationally important habitat type that has greatly declined in abundance throughout Western Europe. In recent years this has led to a growing interest in the restoration of heathland on agricultural land. This generally requires the use of chemical treatments to return soil chemical conditions to those appropriate for the support of heathland ecosystems. However, the potential for negative impacts on the environment due to the potential of these treatments to increase the availability of trace metals via raised soil acidity requires investigation. A large-scale field study investigated the effect of two chemical treatments used in heathland restoration, elemental sulphur and ferrous sulphate, on soil acidity and whether it is possible to predict the effect of the treatments on availability of two potentially toxic cations (Al and Cd) in the soil along with their subsequent accumulation in the shoots of the grass Agrostis capillaris. Results showed that both treatments decreased soil pH, but that only elemental sulphur produced a pH similar to heathland soil. The availability of Al, measured by extraction with 1 M ammonium nitrate, could not be predicted by soil pH, depth in the soil and total Al concentration in the soil. By contrast, availability of Cd could be predicted from these three variables. Concentrations of both Al and Cd in the shoots of A. capillaris showed no significant relationship with the extractable concentration in the soil. Results are discussed in light of the possible environmental impacts of the chemical restoration techniques.

Emissions of sulphur and oxidized nitrogen compounds in Europe have been reduced following a series of control measures during the last two decades. These changes have taken place during a period in which the primary gases and the wet deposition throughout Europe were extensively monitored. Since the end of the 1970s, for example land based sulphur emissions declined by between 90 and 70% depending on the region. Over the same period the total deposition of sulphur and its partitioning into wet and dry deposition have declined, but the spatial pattern in the reduction in deposition differs from that of emission and has changed with time. Such non-linearities in the emission-deposition relationship are important to understand as they complicate the process of assessing the effects of emission reduction strategies. Observed non-linearities in terrestrial sulphur emission-deposition patterns have been identified in north west Europe due to increases in marine emissions, and are currently slowing the recovery of freshwater ecosystems. Changes in the relative amounts of SO₂ and NH₃ in air over the last two decades have also changed the affinity of terrestrial surfaces for SO₂ and have therefore changed the deposition velocity of SO₂ over substantial areas. The consequence of this effect has been the very rapid reduction in ambient SO₂ concentration in some of the major source areas of Europe, where NH₃ did not change much. Interactions between the different pollutants, generating non-linearities are now being incorporated in long-range transport models to simulate the effects of historical emission trends and to provide projections into the future. This paper identifies non-linearities in emission deposition relationships for sulphur and nitrogen compounds in Europe using data from the EMEP long-rang transport model and measured concentration fields of the major ions in precipitation and of SO₂ and NO₂ in surface air.

Many lakes in the Adirondack Mountains, New York, have acidified over the past century due to acidic atmospheric deposition. More recently, most monitored lakes have shown signs of chemical recovery (increase in acid neutralizing capacity) as sulfur deposition levels have declined in response to the Clean Air Act and other emissions control legislation. We used measured and modeled trends in past lakewater acidification and projections of future recovery from acidification to extrapolate results from judgment samples of intensively studied lakes to the population of acid-sensitive Adirondack lakes. Simulations were developed for 70 watersheds using the Model of Acidification of Groundwater in Catchments (MAGIC) to classify lakes according to their sensitivity to change in atmospheric S and N deposition. MAGIC simulations suggested that the modeled Adirondack Long-Term Monitoring Project (ALTM) and Adirondack Effects Assessment Project (AEAP) lakes were largely among the lakes in the population that had acidified most between 1850 and 1990. Most of the modeled ALTM/AEAP lakes were within the top 36% of acid sensitivity, based on model projections of past acidification and future chemical recovery, compared with the 1,829 Adirondack lakes in EPA's Environmental Monitoring and Assessment Program (EMAP) statistical frame. Results of this research will allow fuller utilization of data from on-going chemical and biological monitoring and process-level studies by providing a basis for regionalization of findings and developing/refining relationships among watershed characteristics, chemical change, and biological responses to changing levels of acidic deposition.

The sampling and analysis properties of 1-stage and 2-stage filter-pack methods were studied in detail in monitoring of sulphur and nitrogen containing inorganic gases and particles (sulphur dioxide, sulphate, sum of nitric acid and nitrate and total ammonium). The limit of detection and the limit of quantitation for 24-h samples were estimated using the results of a short-term field experiment completed with available data from long-term monitoring and internal quality assurance. Furthermore, the combined expanded measurement uncertainty including sampling and analysis (Uₜₒₜ) was estimated for filter-pack methods in order to give a tool for distinguishing long-term trends in air quality from the measurement variability. Uₜₒₜ was found to be very near the analytical uncertainty when measuring higher air concentration levels, being ± 4.0% for sulphur concentrations > 1.0 μg m⁻³, ± 3.0% for sulphate concentrations > 0.5 μg m⁻³, ± 3.5% for the sum of nitrate and nitric acid concentrations > 0.3 μg m⁻³ and ± 4.5% for total ammonium concentrations > 0.8 μg m⁻³. At the lower air concentration range Uₜₒₜ increases significantly due to the field blank values. The precision of the 24-h filter-pack sample results expressed by means of modified median absolute difference (M.MAD) and coefficient of variance (CoV) gave 8.3% for sulphur dioxide and 5.4% for particulate sulphate. For the sum of gaseous nitric acid and particulate nitrate the CoV was 5.5% and for total ammonium 4.3%. In addition the suitability of the 24-h filter-pack methods in weekly sampling was proved.

BACKGROUND, AIMS AND SCOPE: Sediments of the Spittelwasser creek are highly polluted with organic compounds and heavy metals due to the discharge of untreated waste waters from the industrial region of Bitterfeld-Wolfen, Germany over the course of more than one century. However, relatively few data have been published about the chloroorganic contamination of the sediment. This paper reports on the content of different (chloro)organic compounds with special emphasis on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and chlorobenzenes. Existing concepts for the remediation of Spittelwasser sediment include the investigation of natural attenuation processes, which largely depend on the presence of an intact microbial food web. In order to gain more insight in terms of biological activity, we analyzed the capacity of sediment microflora to degrade organic matter by measuring the activities of extracellular hydrolytic enzymes involved in the biogeochemical cycling of carbon, nitrogen, phosphorus and sulfur. Furthermore, the detection of physiologically active bacteria in the sediment, particularly of those known for their capability to reductively dehalogenate organochlorine compounds, illustrates the potential for intrinsic bioremediation processes. METHODS: PCDD/F and chlorobenzenes were analyzed by gas chromatography(GC)/mass spectrometry and GC/flame ionization detection, respectively. The activities of hydrolytic enzymes were determined from freshly sampled sediment layers using 4-methylumbelliferyl (MUF) or 7-amino-4-methylcoumarin-conjugated model compounds and kinetic fluorescence measurements. Physiologically active bacteria from different sediment layers were microscopically visualized by fluorescence in situ hybridization (FISH). Specific bacteria were identified by 16S rRNA gene amplification and sequencing. RESULTS AND DISCUSSION: The PCDD/F congener profile was dominated by dibenzofurans. In addition, the presence of specific tetra and pentachlorinated dibenzofurans supported the assumption that extensive magnesium production was one possible source for the high contamination. A range of other chloroorganic compounds, including several isomers of chlorobenzenes, hexachlorocyclohexane and 1,1,1-trichloro-2,2-bis (p-chlorophenyl)ethane (DDT), was present in the sediment. Activities of extracellular hydrolytic enzymes showed a strong decrease in those sediment layers that were characterized by high contents of absorbable organic halogen (AOX), indicating disturbed organic matter decay. Interestingly, an abnormal increase of cellulolytic enzyme activities below the organochlorine-rich layers was observed, possibly caused by residual cellulose from discharges of sulfite pulping wastes. FISH revealed physiologically active bacteria in most sediment layers from the surface down to the depth of about 60 cm, including members of Desulfitobacterium (D.) and Sulfurospirillum. The presence of D. dehalogenans was confirmed by its partial 16S rRNA gene sequence. CONCLUSION: Results of chemical sediment analyses demonstrated high loads of organochlorine compounds, particularly of PCDD/F. Several years after stopping the waste water discharge to Spittelwasser creek, this sediment remains a main source for pollution of the downstream river system by way of the ongoing mobilization of sediment during high floods. As indicated by our enzyme activity measurements, the decomposition potential for organic matter is low in organochlorine-rich sediment layers. In contrast, the comparably higher enzyme activities in less organochlorine-polluted sediment layers as well as the presence of physiologically active bacteria suggest a considerable potential for natural attenuation. RECOMMENDATIONS AND PERSPECTIVE: From our data we strongly recommend to explore the degradative capacity of sediment microorganisms and the limits for in situ activity towards specific sediment pollutants in more detail. This will give a sound basis for the integration of bioremediation approaches into general concepts to reduce the risk that permanently radiates from this highly contaminated sediment.