A Biotic Ligand Model was developed predicting the effect of cobalt on root growth of barley (Hordeum vulgare) in nutrient solutions. The extent to which Ca2+, Mg2+, Na+, K+ ions and pH independently affect cobalt toxicity to barley was studied. With increasing activities of Mg2+, and to a lesser extent also K+, the 4-d EC50Co2+ increased linearly, while Ca2+, Na+ and H+ activities did not affect Co2+ toxicity. Stability constants for the binding of Co2+, Mg2+ and K+ to the biotic ligand were obtained: log KCoBL = 5.14, log KMgBL = 3.86 and log KKBL = 2.50. Limited validation of the model with one standard artificial soil and one standard field soil showed that the 4-d EC50Co2+ could only be predicted within a factor of four from the observed values, indicating further refinement of the BLM is needed. Biotic Ligand Models are not only a useful tool to assess metal toxicity in aquatic systems but can also be used for terrestrial plants.

Simple mass balance equations (SMBE) of critical acid loads (CAL) in forest soil were developed to assess potential risks of air pollutants to ecosystems. However, to apply SMBE reliably at large scales, SMBE must be tested for adequacy and uncertainty. Our goal was to provide a detailed analysis of uncertainty in SMBE so that sound strategies for scaling up CAL estimates to the national scale could be developed. Specifically, we wanted to quantify CAL uncertainty under natural variability in 17 model parameters, and determine their relative contributions in predicting CAL. Results indicated that uncertainty in CAL came primarily from components of base cation weathering (BCw; 49%) and acid neutralizing capacity (46%), whereas the most critical parameters were BCw base rate (62%), soil depth (20%), and soil temperature (11%). Thus, improvements in estimates of these factors are crucial to reducing uncertainty and successfully scaling up SMBE for national assessments of CAL.

The aim of this study was to evaluate the suitability of the (Ca + Mg + K)/Al and the Ca/Al ratios in soil solution as chemical criteria for forest condition in critical load calculations for forest ecosystems. The tree species Norway spruce, Sitka spruce and beech were studied in an area with high deposition of sea salt and nitrogen in the south-western part of Jutland, Denmark. Throughfall and soil water were collected monthly and analysed for pH, NO₃-N, NH₄-N, K, Ca, Mg, DOC and Altot. Organic Al was estimated using DOC concentrations. Increment and defoliation were determined annually, and foliar element concentrations were determined every other year. The throughfall deposition was highest in the Sitka spruce stand (maximum of 40 kg N ha-¹yr-¹) and lowest in the beech stand (maximum of 11 kg N ha-¹yr-¹). The Sitka spruce stand leached on average 12 kg N ha-¹yr-¹ during the period 1988-1997 and leaching increased throughout the period. Only small amounts of N were leached from the Norway spruce stand whereas almost no N was leached from the beech stand. For all tree species, both (Ca + Mg + K)/Al and Ca/Al ratios decreased in soil solution at 90 cm depth between 1989 and 1999, which was mainly caused by a decrease in concentrations of base cations. The toxic inorganic Al species were by far the most abundant Al species at 90 cm depth. At the end of the measurement period, the (Ca + Mg + K)/Al ratio was approximately 1 for all species while the Ca/Al ratio was approximately 0.2. The lack of a trend in the increment rates, a decrease in defoliation as well as sufficient levels of Mg and Ca in foliage suggested an unchanged or even slightly improved health condition, despite the decreasing and very low (Ca + Mg + K)/Al and Ca/Al ratios. The suitability of these soil solution element ratios is questioned as the chemical criteria for soil acidification under field conditions in areas with elevated deposition rates of sea salts, in particular Mg.

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.

Fluxes of principal anions and cations with bulk and throughfall deposition during the growing period (April-September) were investigated for three years (2001-2003) at three sites differently exposed to the second biggest Lithuanian city - Kaunas. Fluxes of all investigated anions (SO₄ ²-, NO₃ - and Cl-) and most cations were found to be the highest in suburban area to compare with both - Rural and urban sites. The highest seasonal variability of monthly ion fluxes and the highest differences between throughfall and bulk fluxes (net throughfall) were recorded in suburban area. The highest throughfall enrichment by sulphur was detected in spring and the beginning of summer (April, May) in urban and especially in suburban sites. For nitrogen compounds (NO₃ -, NH₄ ⁺) positive net throughfall values were characteristic for urban and suburban sites and negative for rural site almost during the entire growing period. Uptake of NH₄ ⁺ ions was detected to be much higher of that for nitrates in rural area (46% vs. 22%). The most intensive enrichment of throughfall fluxes by K⁺ ions took place during the summer time (May, June, July), however, intensity of potassium leaching at the same amount of precipitation was the highest in suburban area.