Acidification and recovery of aquatic ecosystems in south central Ontario, Canada: regional application of the MAGIC model

International audienceThe dynamic model MAGIC was applied to 25 lakes in south-central Ontario, Canada using a regional modelling methodology. Soil and lake water chemistry for each lake catchment was simulated for the period 1850?2050. Sulphate (SO42?) deposition forecasts were derived from recently proposed emission reductions, which correspond roughly to a 50% reduction in SO42? deposition by 2010 from the 2000 baseline. Changes in SO42? deposition had a significant impact on lake chemistry. Simulated lake water chemistry showed a recovery potential under the current deposition scenario; by 2050 concentration levels recovered to values predicted for the early 1900s. Moreover, simulated future lake water chemistry showed significant recovery compared to 1975 levels. However, although regional simulations predict that base cation losses have decreased in recent years, soils in the region will continue to acidify with Ca2+ losses dominating depletion of the exchangeable pool. Base cation losses from the exchangeable pool are currently buffering lakes against the impacts of acid deposition; ultimately base cation inputs into the lakes will decrease as exchangeable base cation pools become depleted. Further emission reductions are necessary to ensure continued recovery from acidification. Keywords: regional dynamic model, sulphate, acid neutralising capacity, critical loads, lake chemistry, soil base saturatio

Modelling reversibility of Central European mountain lakes from acidification: Part I - the Bohemian forest

International audienceA dynamic, process-based acidification model, MAGIC7, has been applied to three small, strongly acidified lakes in the Bohemian Forest, the Czech Republic. The model was calibrated for a set of experimental records on lake water composition over the 1984?2000 period, and produced hindcast concentrations that compared well, even with older (40-year) irregular determinations of nitrate, chloride and pH. Water and soil chemistry forecasts up to 2050 were based on reductions in S and N emissions presupposed by the Gothenburg Protocol. Modelled sulphate and chloride concentrations were predicted to decrease to the levels at the beginning of the 20th century by 2050. The lake water carbonate buffering system is predicted to be re-established in only two lakes (Cerné and Ple?né), with current soil base saturations of 12-15%. Concentrations of ionic aluminium species decreased sharply, from 110 ?eq l-1 in the mid-1980s to the current ~40 ?eq l-1, and were predicted to decrease below 10 ?eq l-1 in the 2020s. Diatom-inferred pH in pre-industrial times was substantially lower than modelled pH. It is suggested that the diatom pH, based almost entirely on non-planktonic species, is biased by inwash of diatoms from more acidic tributaries into the sediment of these small lakes. Generally significant results can be summarised as follows: (1) Simulated sulphate levels agree well with observations during acidification progress and retreat only for values of soil SO42- adsorption capacity three to six times (20 to 40 ?eq kg-1) higher than those found experimentally. This implies a further mechanism of S retention and release in addition to physical sulphate adsorption to Fe and Al oxides of soils. (2) The catchments' ability to retain deposited N appeared to decline after ~1950 but this was not connected with a sufficient change in the C:N ratio of the soils. Agreement between modelled and observed concentrations of nitrate was therefore achieved by empirical restriction of N retention in the soils. Based on their current ability to retain N, the catchments will remain N-saturated and could, temporarily, produce more inorganic N than they receive due to additional nitrate production from soil N-organic pools. This situation has occurred already in the Cerné Lake catchment. (3) Differences in responses of individual lakes can be attributed to different land usages over the past several centuries as well as to differences in geology and primary production. Keywords: MAGIC, atmospheric deposition, N retention, diatom-inferred pH, sulphate, nitrate, base cations, aluminium, Czech Republi

Probable changes in lake chemistry in Canada's Atlantic Provinces under proposed North American emission reductions

International audienceAtlantic Canada, located in the extreme north-eastern portion of North America, receives acid precipitation from all major acid emission sources on the eastern part of the continent. The region was glaciated and has thin soils over a generally poorly acid buffering bedrock. Because of regional topography, large groupings of lakes occur in a number of regions. Environment Canada and the Government of New Brunswick have operated lake sampling networks in trend detection studies and have concentrated their work on these lake groupings. The MAGIC model has been applied to these lakes and their catchments to see: a) what initial water chemistry conditions existed before acidification began, b) what the chemistry was like during the worst of regional acid deposition, and c) what it would be like under deposition conditions predicted for new Canadian and US emission reduction proposals. While pH, sulphate, acid neutralisation capacity (ANC) and the sum of the base cations (SBC) of all lakes have been significantly affected by acid deposition, water chemistry conditions are now considerably better than they were in 1975, at the worst of the deposition. However, a 50% reduction in acid deposition from Year 2000 deposition amounts will not return water chemistry to original conditions in most of the region. Keywords: Atlantic Canada, monitoring networks, acidification, predictions, MAGI

Modelling the effects of acid deposition: refinements, adjustments and inclusion of nitrogen dynamics in the MAGIC model

International audienceThe MAGIC model of the responses of catchments to acidic deposition has been applied and tested extensively over a 15 year period at many sites and in many regions around the world. Overall, the model has proven to be robust, reliable and useful in a variety of scientific and managerial activities. Over the years, several refinements and additions to MAGIC have been proposed and/or implemented for particular applications. These adjustments to the model structure have all been included in a new version of the model (MAGIC7). The log aluminium ? pH relationship now does not have to be fixed to aluminium trihydroxide solubility. Buffering by organic acids using a triprotic analog is now included. Dynamics of nitrogen retention and loss in catchments can now be linked to soil nitrogen and carbon pools. Simulation of short-term episodic response by mixing fractions of different water types is also possible. This paper presents a review of the conceptual structure of MAGIC7 relating to long-term simulation of acidification and recovery, describes the conceptual basis of the new nitrogen dynamics and provides a comprehensive update of the equations, variables, parameters and inputs for the model. Keywords: process-based model, acid deposition, recover

Assessing emission reduction targets with dynamic models: deriving target load functions for use in integrated assessment

International audienceInternational agreements to reduce the emission of acidifying sulphur (S) and nitrogen (N) compounds have been negotiated on the basis of an understanding of the link between acidification related changes in soil and surface water chemistry and terrestrial and aquatic biota. The quantification of this link is incorporated within the concept of critical loads. Critical loads are calculated using steady state models and give no indication of the time within which acidified ecosystems might be expected to recover. Dynamic models provide an opportunity to assess the timescale of recovery and can go further to provide outputs which can be used in future emission reduction strategies. In this respect, the Target Load Function (TLF) is proposed as a means of assessing the deposition load necessary to restore a damaged ecosystem to some pre-defined acceptable state by a certain time in the future. A target load represents the deposition of S and N in a defined year (implementation year) for which the critical limit is achieved in a defined time (target year). A TLF is constructed using an appropriate dynamic model to determine the value of a chemical criterion at a given point in time given a temporal pattern of S and N deposition loads. A TLF requires information regarding: (i) the chemical criterion required to protect the chosen biological receptor (i.e. the critical limit); (ii) the year in which the critical limit is required to be achieved; and (iii) time pattern of future emission reductions. In addition, the TLF can be assessed for whole regions to incorporate the effect of these three essentially ecosystem management decisions. Keywords: emission reduction, critical load, target load, dynamic model, recovery tim

Modelling the ecosystem effects of nitrogen deposition: Model of ecosystem retention and loss of inorganic nitrogen (MERLIN)

A catchment-scale mass-balance model of linked carbon and nitrogen cycling in ecosystems has been developed for simulating leaching losses of inorganic nitrogen. The model (MERLIN) considers linked biotic and abiotic processes affecting the cycling and storage of nitrogen. The model is aggregated in space and time and contains compartments intended to be observable and/or interpretable at the plot or catchment scale. The structure of the model includes the inorganic soil, a plant compartment and two soil organic compartments. Fluxes in and out of the ecosystem and between compartments are regulated by atmospheric deposition, hydrological discharge, plant uptake, litter production, wood production, microbial immobilization, mineralization, nitrification, and denitrification. Nitrogen fluxes are controlled by carbon productivity, the C:N ratios of organic compartments and inorganic nitrogen in soil solution. Inputs required are: 1) temporal sequences of carbon fluxes and pools- 2) time series of hydrological discharge through the soils, 3) historical and current external sources of inorganic nitrogen; 4) current amounts of nitrogen in the plant and soil organic compartments; 5) constants specifying the nitrogen uptake and immobilization characteristics of the plant and soil organic compartments; and 6) soil characteristics such as depth, porosity, bulk density, and anion/cation exchange constants. Outputs include: 1) concentrations and fluxes of NO3 and NH4 in soil solution and runoff; 2) total nitrogen contents of the organic and inorganic compartments; 3) C:N ratios of the aggregated plant and soil organic compartments; and 4) rates of nitrogen uptake and immobilization and nitrogen mineralization. The behaviour of the model is assessed for a combination of land-use change and nitrogen deposition scenarios in a series of speculative simulations. The results of the simulations are in broad agreement with observed and hypothesized behaviour of nitrogen dynamics in growing forests receiving nitrogen deposition

Recovery from acidification of lochs in Galloway, south-west Scotland, UK: 1979-1998

International audienceThe Galloway region of south-west Scotland has historically been subject to long-term deposition of acidic precipitation which has resulted in acidification of soils and surface waters and subsequent damage to aquatic ecology. Since the end of the 1970s, however, acidic deposition has decreased substantially. The general pattern is for a rapid decline in non-marine sulphate in rainwater over the period 1978-1988 followed by stable concentrations to the mid-1990s. Concentrations of nitrate and ammonium in deposition have remained constant between 1980 and 1998. Seven water quality surveys of 48 lochs in the Galloway region have been conducted between 1979 and 1998. During the first 10 years, from 1979, there was a major decline in regional sulphate concentrations in the lochs, which was expected to have produced a decline in base cations and an increase in the acid neutralising capacity. But sea-salt levels (as indicated by chloride concentrations) were approximately 25% higher in 1988 than in 1979 and thus short-term acidification due to sea-salts offset much of the long-term recovery trend expected in the lochs. During the next 10 years, however, the chloride concentrations returned to 1979 levels and the lochs showed large increases in acid neutralising capacity despite little change in sulphate concentrations. From the observed decline in sulphate deposition and concentrations of sulphate in the lochs, it appears that approximately 75% of the possible improvement in acid neutralising capacity has already occurred over the 20-year period (1979-1998). The role of acid deposition as a driving factor for change in water chemistry in the Galloway lochs is confounded by concurrent changes in other driving variables, most notably, factors related to episodic and year-to-year variations in climate. In addition to inputs of sea-salts, climate probably also influences other chemical signals such as peaks in regional nitrate concentrations and the sharp increase in dissolved organic carbon during the 1990s. Keywords: acidification, recovery, Galloway, sulphur, nitroge

Abstract This study applied the Model of Acidification

of Groundwater in Catchments (MAGIC) to estimate the sensitivity of 66 watersheds in the Southern Blue Ridge Province of the Southern Appalachian Mountains, United States, to changes in atmospheric sulfur (S) deposition. MAGIC predicted that stream acid neutralizing capacity (ANC) values were above 20 μeq/L in all modeled watersheds in 1860. Hindcast simulations suggested that the media

A Bayesian palaeoenvironmental transfer function model for acidified lakes

A Bayesian approach to palaeoecological environmental reconstruction deriving from the unimodal responses generally exhibited by organisms to an environmental gradient is described. The approach uses Bayesian model selection to calculate a collection of probability-weighted, species-specific response curves (SRCs) for each taxon within a training set, with an explicit treatment for zero abundances. These SRCs are used to reconstruct the environmental variable from sub-fossilised assemblages. The approach enables a substantial increase in computational efficiency (several orders of magnitude) over existing Bayesian methodologies. The model is developed from the Surface Water Acidification Programme (SWAP) training set and is demonstrated to exhibit comparable predictive power to existing Weighted Averaging and Maximum Likelihood methodologies, though with improvements in bias; the additional explanatory power of the Bayesian approach lies in an explicit calculation of uncertainty for each individual reconstruction. The model is applied to reconstruct the Holocene acidification history of the Round Loch of Glenhead, including a reconstruction of recent recovery derived from sediment trap data.The Bayesian reconstructions display similar trends to conventional (Weighted Averaging Partial Least Squares) reconstructions but provide a better reconstruction of extreme pH and are more sensitive to small changes in diatom assemblages. The validity of the posteriors as an apparently meaningful representation of assemblage-specific uncertainty and the high computational efficiency of the approach open up the possibility of highly constrained multiproxy reconstructions

Radiative association and inverse predissociation of oxygen atoms

The formation of \mbox{O}_2 by radiative association and by inverse predissociation of ground state oxygen atoms is studied using quantum-mechanical methods. Cross sections, emission spectra, and rate coefficients are presented and compared with prior experimental and theoretical results. At temperatures below 1000~K radiative association occurs by approach along the $1\,{}^3\Pi_u$ state of \mbox{O}_2 and above 1000~K inverse predissociation through the \mbox{B}\,{}^3\Sigma_u^- state is the dominant mechanism. This conclusion is supported by a quantitative comparison between the calculations and data obtained from hot oxygen plasma spectroscopy.Comment: submitted to Phys. Rev. A (Sept. 7., 1994), 19 pages, 4 figures, latex (revtex3.0 and epsf.sty