Long Term Trends in Sulphur and Nitrogen Deposition in Europe and the Cause of Non-linearities

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.     

Deposition Loads of Sulphur and Nitrogen in Germany

High spatial resolution maps of deposition loads in Germanyare produced as an input for abatement strategy research andfor critical loads exceedance calculations on a nationalscale. In this paper methods ofmapping total deposition loads in Germany and preliminarymaps of nitrogen and sulphur deposition loads for the year1993 are presented. A comparison of these mapping resultswith EMEP deposition mapping results has been carried out.The differences in the results of the German national and theEuropean EMEP mapping, due to different databases anddifferent methods, are quantified and discussed. Highresolution maps of deposition loads are compared to Europeanlow resolution maps on the same temporal and spatial scale,assuming that on average both should lead to similar results.However, the average differencescalculated for 23 EMEP 150 × 150 km² grid cells over Germanywere found to be 33% higher for sulphur (S) total depositionby the German method 65% higher for S dry deposition and1% lower for S wet deposition. The German results fornitrogen (N) total deposition are 2% higher than the EMEPresult 22% higher for N dry deposition and 10% lower for Nwet deposition.     

Neutralisation of Sulphur Dioxide Deposition in a Coniferous Canopy

Previously, it has been observed that the internal circulation (ion leakage) of calcium from a coniferous forest is caused by uptake of sulphur dioxide (SO₂). Here we show that this correlation was not changed when the forest floor is covered with a roof. The reaction takes place in the canopy and is not influenced by deposition and root uptake of calcium and sulphate. The ion leakage of calcium is linked to the loss of acidity in throughfall. The process can, for one of the catchments, schematically be written: SO₂ + H₂O + 0.5 O₂ + 0.58 CaA₂→ SO₄ ^2- + 0.94 H⁺ + 0.58 Ca²⁺ + 1.16 HA, in which A denotes the anion to a weak acid. This reaction also takes place today when the SO₂ concentration is very low, but when the precipitation is still acidic. The ion leakage of manganese also is caused by the uptake of SO₂, but only 0.12 manganese ions are released per SO₂ molecule.     

Critical Loads of Acidity for Surface Waters in South-Central Ontario, Canada: Regional Application of the First-Order Acidity Balance (FAB) Model

Major sulphur emission control programs have been implemented in North America, resulting in current emissions being ～30% less than those in 1980. However, the level of acidic deposition remaining is still unlikely to promote widespread recovery of aquatic ecosystems. The First-order Acidity Balance (FAB) model has been applied to south-central Ontario (285 lakes in the Muskoka River Catchment) to evaluate the need for further reductions in emissions. As a result of the past decline in deposition, the proportion of lakes with critical loads exceedance has dropped substantially; however, further reductions in sulphur and nitrogen emissions are required to eliminate critical loads exceedance. Based on bulk deposition of sulphate and nitrogen (41.1 mmol_c m^-2 yr^-1 and 62.5 mmol_c m^-2 yr^-1, respectively) for the period 1995–1999, 166 lakes (58.3%) exceedcritical loads. Even with full implementation of SO₂ abatementprograms in Canada (achieved in 1994) and the United States (legislated for 2010), critical loads will be exceeded in a large proportion (46.6%) of the study lakes.     

Emission Models and Inventories for Local Greenhouse Gas Emissions Assessment: Experience in the East Midlands Region of the Uk

This paper considers how regional greenhouse gas emissioninventories can be determined. It presents a greenhousegas emissions inventory, by source, for the East Midlandsthat has been compiled as part of a regional study intoclimate change impacts in the United Kingdom. This hasused available local data, and national emissions datawith appropriate scaling factors. Total greenhouse gasemissions for the region are estimated to be 59 milliontonnes of carbon dioxide equivalent (CO₂ equivalent)for 1997. Of these emissions, approximately 86% werecarbon dioxide emissions, 7% methane emissions, and 5%were nitrous oxide, with emissions of hydrofluorocarbons(HFCs), perfluorocarbons (PFCs) and sulphur hexafluoride(SF₆) contributing less than 2% of total emissions.     

Effects of Climate Events on Elemental Fluxes from Forested Catchments in Ontario, Canada: Modelling Drought-Induced Redox Processes

One of the principal influences on elemental fluxes from forestedcatchments in south-central Ontario is the atmospheric deposition rate of strong acids. While sulphate deposition has decreased by ～40% in the past two decades, nitrate deposition has remained unchanged and is now equivalent to sulphate deposition. Sulphate concentrations in headwater lakes and their inflows have decreased, but much less than expected based on the anticipated direct response of the catchments. Reduction-oxidation (redox) processes occurring in wetlands have been identified as the reasonfor delayed recovery, and climate events as controlling these redoxprocesses. A new version of the biogeochemical model MAGIC (modelof acidification of groundwater in catchments) with a wetland compartment that incorporates redox processes driven by climate events has been generated. The application of MAGIC to a subcatchmentof Plastic Lake in south-central Ontario indicates that the basic structure of the model appears to be consistent with the observeddata. Moreover, the wetland component was essential in reproducingthe observed trends, which include sulphate retention in non-droughtyears and re-oxidation of previously stored (reduced) sulphur in drought years.     

Natural and Anthropogenic Changes in The Chemistry of Six UK Mountain Lakes, 1988 to 2000

Trends have been analysed for 12 years ofchemical data from six mountain lakes in the UK AcidWaters Monitoring Network (AWMN). With minimal localanthropogenic impacts, these sites offer the bestavailable opportunity for clear identification of surfacewater chemical response to external factors, whethernatural or anthropogenic. Results indicate that naturalclimatic variations have had a major impact on lakechemistry, through fluctuations in (i) intensity ofstorms, which cause dilution of weathering-derived basecations, and/or displacement of hydrogen and aluminiumions on soil exchange sites by deposited marine basecations; and (ii) winter temperature, which is thought tobe inversely related to spring nitrate (NO₃) maxima.Both climatic factors can be linked to the North AtlanticOscillation. For the first decade of AWMN monitoringthese natural `confounding factors' to a significantextent obscured any recovery from acidification due todeclining anthropogenic sulphur deposition. However, theadditional data presented here provide strengtheningevidence for chemical recovery at a number of sites, atwhich decreases in sulphate (SO₄), acidity andlabile aluminium can now be identified. It is believedthat changes at these sensitive mountain lake sites mayherald more widespread recovery in UK surface waters aspollutant emissions decline further. However, largeincreases in dissolved organic carbon, and hence inorganic acidity, may have partially offset reductions inmineral acidity. The cause of these increases remainsuncertain, but may be linked to climatic change.     

Use of the Dynamic Model `MAGIC' to Predict Recovery Following Implementation of the Gothenburg Protocol

Reduction of sulphur deposition causesrecovery of acidified surface waters. Processes in thecatchment delay recovery. The acidification model MAGICwas applied to the Vikedal and Tovdal rivers in southernNorway. Response in water chemsitry is delayed by 10–20 yr. The delay is due to release of old sulphate atVikedal and cation exchange at Tovdal. Assuming that theGothenburg protocol is fully implemented by the year2010, much of the predicted increase of ANC will occur inthe next 10 yr with a levelling off by about 2040. Ifnitrogen leaching increases in the future, however,recovery of ANC will not be as rapid, nor as complete.Critical load for acidity calculated by steady-statemodels is confirmed by the MAGIC predictions. Futurerequirement for mitigation measures such as liming willdecrease in the future as acid deposition decreases. Bythe year 2046 the liming requirement will be reduced byabout 45% at Vikedal and 65% at Tovdal. One of the mainpurposes of the Norwegian national monitoring programmeis to provide documentation of changes in environmentalquality due to long-range transported air pollutants.Modelling applications such as this clearly show that thedata fill this purpose.     

Dry Deposition Monitoring in Europe

Between 1993 and 1999 two EU funded projects wereexecuted aimed at (i) the development of drydeposition monitoring methods for core sites andlarge scale application, (ii) the installation andrunning of three core sites in Europe and (iii) the improvement and validation of models used forregional application. This article provides anoverview of the development of depositionmonitoring stations and the main results of thethree core sites, which were operated between1995 and 1998. Furthermore, the results of thedevelopment of a low cost monitoring system arepresented. Continuous measurements were made ofboth wet and dry deposition of sulphur andnitrogen components and base cations. The 4 yearsof data show a decrease in sulphur loads and notrend for the other components. It is shown thatthe surface affinities for sulphur depositionalso changed during the years, underpinning theneed for dry deposition monitoring. A conditionaltime average gradient system was successfullydeveloped and tested and provides a good meansfor low cost monitoring of dry deposition fluxes.The costs can be reduced by a factor of 3–4 without losing the accuracy of the annual average gas fluxes.     

Control of GHG emission at the microbial community level

All organic material eventually is decomposed by microorganisms, and considerable amounts of C and N end up as gaseous metabolites. The emissions of greenhouse relevant gases like carbon dioxide, methane and nitrous oxides largely depend on physico-chemical conditions like substrate quality or the redox potential of the habitat. Manipulating these conditions has a great potential for reducing greenhouse gas emissions. Such options are known from farm and waste management, as well as from wastewater treatment. In this paper examples are given how greenhouse gas production might be reduced by regulating microbial processes. Biogas production from manure, organic wastes, and landfills are given as examples how methanisation may be used to save fossil fuel. Methane oxidation, on the other hand, might alleviate the problem of methane already produced, or the conversion of aerobic wastewater treatment to anaerobic nitrogen elimination through the anaerobic ammonium oxidation process might reduce N2O release to the atmosphere. Changing the diet of ruminants, altering soil water potentials or a change of waste collection systems are other measures that affect microbial activities and that might contribute to a reduction of carbon dioxide equivalents being emitted to the atmosphere.     

Uncertainty in Estimation of Wet Deposition of Sulphur

A model is described for predicting wet deposition ofsulphur in Britain from rainfall and site measurementsof ion concentration in precipitation. This modelincludes orographic enhancement of both rainfall andion concentration. The model output is comparedagainst available measurement data. Sensitivity anduncertainty analyses are used to predict the outputuncertainty. If the stated assumptions can be shown tobe correct, the wet deposition for Britain at the 5 kmscale is accurate to ±35% across the country. Theanalyses show a larger uncertainty in central Englandand a possible bias towards underestimation of wetdeposition, the latter being of importance incalculating critical load exceedances in remote areas.     

Novel Mercury Oxidant and Sorbent for Mercury Emissions Control from Coal-fired Power Plants

The authors have successfully developed novel efficient and cost-effective sorbent and oxidant for removing mercury from power plant flue gases. These sorbent and oxidant offer great promise for controlling mercury emissions from coal-fired power plants burning a wide range of coals including bituminous, sub-bituminous, and lignite coals. A preliminary analysis from the bench-scale test results shows that this new sorbent will be thermally more stable and cost-effective in comparison with any promoted mercury sorbents currently available in the marketplace. In addition to the sorbent, an excellent elemental mercury (Hg(0)) oxidant has also been developed, and will enable coal-fired power plants equipped with wet scrubbers to simultaneously control their mercury emissions as well as their sulfur oxides emissions. This will work by converting all elemental mercury to an oxidized form which will be removed by the wet scrubber. This will result in significant cost savings for mercury emissions control to the atmosphere, and will help in keeping electric costs low. The sorbent and oxidant will benefit from the utilization of a waste stream from the printed circuit board (PCB) industry, and would thus be environmentally beneficial to both of the utility and electronics industries. The sorbent also demonstrated thermal stability up to 350°C, suggesting a possibility of an application in pulverized coal-fired power plants equipped with hot-side electrostatic precipitators and coal gasification plants.     

The GANE Roof Project: The impact of reduced N & S deposition and experimental warming in an acid grassland

A field-based system used to quantify the response of acid grassland to reduced atmospheric nitrogen and sulphur deposition, and to investigate the effects of elevated soil temperature on acid grassland development is described. The system is based on 12 retractable roofs, covering undisturbed experimental plots of acid grassland and three controls. Nine roofs are used to exclude natural precipitation and three roofs used to retain emitted IR radiation at night. An irrigation system has been developed to simulate natural precipitation, allowing for the application of specific treatment regimes of ambient, reduced nitrogen and reduced nitrogen/sulphur deposition beneath the nine rain exclusion plots. Plant, soil parameters, leachate chemistry and gaseous fluxes are being monitored and initial results on soil water chemistry are described. Warming appeared to enhance nitrate concentrations in soil water but this was not sustained beyond the first year of treatment. In contrast, the deposition reduction treatments decreased soil water nitrate concentrations within a few weeks of reducing deposition. This was not observed for other solutes such as sulphate or ammonium suggesting a more direct link between deposition of nitrate and leaching losses.     

The GANE Roof Project: The impact of reduced N & S deposition and experimental warming in an acid grassland

A field-based system used to quantify the response of acid grassland to reduced atmospheric nitrogen and sulphur deposition, and to investigate the effects of elevated soil temperature on acid grassland development is described. The system is based on 12 retractable roofs, covering undisturbed experimental plots of acid grassland and three controls. Nine roofs are used to exclude natural precipitation and three roofs used to retain emitted IR radiation at night. An irrigation system has been developed to simulate natural precipitation, allowing for the application of specific treatment regimes of ambient, reduced nitrogen and reduced nitrogen/sulphur deposition beneath the nine rain exclusion plots. Plant, soil parameters, leachate chemistry and gaseous fluxes are being monitored and initial results on soil water chemistry are described. Warming appeared to enhance nitrate concentrations in soil water but this was not sustained beyond the first year of treatment. In contrast, the deposition reduction treatments decreased soil water nitrate concentrations within a few weeks of reducing deposition. This was not observed for other solutes such as sulphate or ammonium suggesting a more direct link between deposition of nitrate and leaching losses.     

Modelling Seasonal Dynamics from Temporal Variation in Agricultural Practices in the UK Ammonia Emission Inventory

Most ammonia (NH₃) emission inventories have been calculated on an annual basis and do not take into account the seasonal variability of emissions that occur as a consequence of climate and agricultural practices that change throughout the year. When used as input to atmospheric transport models to simulate concentration fields, these models therefore fail to capture seasonal variations in ammonia concentration and dry and wet deposition. In this study, seasonal NH₃ emissions from agriculture were modelled on a monthly basis for the year 2000, by incorporating temporal aspects of farming practice. These monthly emissions were then spatially distributed using the AENEID model (Atmospheric Emissions for National Environmental Impacts Determination). The monthly model took the temporal variation in the magnitude of the ammonia emissions, as well as the fine scale (1-km) spatial variation of those temporal changes into account to provide improved outputs at 5-km resolution. The resulting NH₃ emission maps showed a strong seasonal emission pattern, with the highest emissions during springtime (March and April) and the lowest emissions during summer (May to July). This emission pattern was mainly influenced by whether cattle were outside grazing or housed and by the application of manures and fertilizers to the land. When the modelled emissions were compared with measured NH₃ concentrations, the comparison suggested that the modelled emission trend corresponds fairly well with the seasonal trend in the measurements. The remaining discrepancies point to the need to develop functional parametrisations of the interactions with climatic seasonal variation.     

Cost-effectiveness Analysis of Reducing the Emission of Nitrogen Oxides in Asia

The purpose of this study is to evaluate cost-effective reduction strategies for nitrogen oxides (NO _x ) in the Asian region. The source-receptor relationships of the Lagrangian “puff” model of long-range transportation, ATMOS-N, were used to calculate the wet/dry deposition of the nitrogen (N) in Asia. Critical loads of N deposition in Asia were calculated from the relationships between the critical load of sulfur (S) and balance of N in and out using the data of S critical load of RAINS-ASIA. The cost functions of N reduction of Asian countries were derived by the regression analysis with the data of cost functions of European countries used in RAINS. In order to assess the environmental impact, the gaps between N deposition and critical load of N were calculated. The emission of NO _x was reduced in some cases of this model, and the changes of gaps between N deposition and critical load were observed as well as the changes of the reduction cost. It is shown that a uniform reduction of NO _x emissions by countries in Asia is not cost-effective strategy.     

Direct and Indirect Effects of Soil Pollution by Lignite Mining

Lignite mining and processing has caused a pronounced impact both directly and indirectly on soils and ecosystems across large areas of the former GDR. We studied soils of pine forest ecosystems at sites affected by severe alkaline dust and sulphur deposition, stemming from lignite fired power plant emission, and at dumped sites from lignite mining. In this paper we summarize our main results and evaluate the long-term impact of lignite mining and combustion on the environment. The pine ecosystems on naturally developed soils show a clear effect of deposition history along a former deposition gradient with distinct changes in chemical properties of organic surface layers and mineral soil as well as in element turnover and cycling rates. Afforested sites on mining dumps are directly affected by the composition of the dumped substrates. Over a large area (800 km²) these substrates are dominated by Tertiary sediments with varying amounts of lignitic particles and pyrite that result in phytotoxic site conditions (pH < 3, high salt and metal contents). High amelioration doses of liming material (up to 200 t ha⁻¹) were applied for restoration purposes. We studied the development of these sites over a period of 60 years using a false-time series approach. Beside the extreme soil conditions, element budgets of these sites are characterized by very high element release rates over decades caused by pyrite oxidation and primary mineral weathering.     

Emissions from mesoscale in situ oil fires: the mobile 1991 experiments

A series of 14 mesoscale burns were conducted in 1991 to study various aspects of oil burning in situ. Extensive sampling and monitoring of these burns were conducted to determine the emissions. This was done at two downwind ground stations, one upwind ground station and in the smoke plume using a blimp and a remote-controlled helicopter. Particulate samples in air were taken and analyzed for polycyclic aromatic hydrocarbons (PAHs). PAHs were found to be lower in the soot than in the starting oil. Metals in the oil were found concentrated in the residue and could not be measured in soot samples using conventional industrial hygiene sampling techniques. Particulates in the air were measured by several means and found to be greater than recommended exposure levels only up to 150 m downwind at ground level. Combustion gases including carbon dioxide, sulphur dioxide and carbon monoxide did not reach exposure level maximums. These gases were emitted over a broad area around the fire and are not directly associated with the plume trajectory. Volatile organic compound (VOCs) emissions are extensive from fires, but the levels are less than those emitted from a non-burning test spill. Over 50 compounds were identified and quantified, several at possible levels of concern up to 200 m downwind. Water under the burns was analyzed; no analytes of concern could be found at the detection levels of the methods. The burn residue was analyzed for the same compounds as the air particulate samples. The residue contained elevated amounts of metals. PAHs were at a lower concentration in the residue than in the starting oil, however there is a slight differential concentration increase in some higher molecular weight species. Overall, indications from these mesoscale trials are that emissions from in situ burning are low in comparison to other sources of emissions and result in concentrations of air contaminants that are below exposure limits beyond 500 m downwind.     

Ls－811－2硫磺回收催化剂的开发及应用

介绍了Ｌｓ－８１１－２催化剂的研制及在克劳斯硫磺回收装置上的工业应用，实践证明，此催化剂的活性已达到国内外同类催化剂的水平，并具有生产工艺流程简单、无三废污染、原料易得及成本较低等特点。此催化剂的开发，为生产硫磺回收催化剂开辟了新的原料路线及制备方法。     

Recycling of high purity selenium from CIGS solar cell waste materials

Copper indium gallium diselenide (CIGS) is a promising material in thin film solar cell production. To make CIGS solar cells more competitive, both economically and environmentally, in comparison to other energy sources, methods for recycling are needed. In addition to the generally high price of the material, significant amounts of the metals are lost in the manufacturing process. The feasibility of recycling selenium from CIGS through oxidation at elevated temperatures was therefore examined. During oxidation gaseous selenium dioxide was formed and could be separated from the other elements, which remained in solid state. Upon cooling, the selenium dioxide sublimes and can be collected as crystals. After oxidation for 1 h at 800 °C all of the selenium was separated from the CIGS material. Two different reduction methods for reduction of the selenium dioxide to selenium were tested. In the first reduction method an organic molecule was used as the reducing agent in a Riley reaction. In the second reduction method sulphur dioxide gas was used. Both methods resulted in high purity selenium. This proves that the studied selenium separation method could be the first step in a recycling process aimed at the complete separation and recovery of high purity elements from CIGS.