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.

The experiment was carried out on a short rotation coppice culture of poplars (POP-EUROFACE, Central Italy), growing in a free air carbon dioxide enriched atmosphere (FACE). The specific objective of this work was to study whether elevated CO2 and fertilization (two CO2 treatments, elevated CO2 and control, two N fertilization treatments, fertilized and unfertilized), as well as the interaction between treatments caused an unbalanced nutritional status of leaves in three poplar species (P. x euramericana, P. nigra and P. alba). Finally, we discuss the ecological implications of a possible change in foliar nutrients concentration. CO2 enrichment reduced foliar nitrogen and increased the concentration of magnesium; whereas nitrogen fertilization had opposite effects on leaf nitrogen and magnesium concentrations. Moreover, the interaction between elevated CO2 and N fertilization amplified some element unbalances such as the K/N-ratio. CO2 enrichment reduced foliar nitrogen and increased the magnesium concentration in poplar.

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.

The effects of harvesting on the long-term mass balances of calcium (Ca), magnesium (Mg) and potassium (K) were evaluated on a regional level in Sweden. A new high-resolution weathering database was used together with estimates of total deposition, losses through harvest and leaching. Estimates were made for pine and spruce separately and for two harvesting intensity scenarios: stem harvesting and whole-tree harvesting. The mass balance calculations showed net losses of Ca and Mg in almost the whole country for both scenarios. The losses were smaller for pine than for spruce. The K balances were mainly positive for pine but negative for spruce. Leaching was a main factor in the mass balances, especially for Ca and Mg. Whole-tree harvesting in spruce forests led to substantially higher net losses of K and Ca than stem harvesting, according to the calculations. In the whole-tree harvesting scenario in spruce forests the estimated yearly net losses of Ca, Mg and K corresponded to at least 5%, 8% and 3% of the pools of exchangeable base cations, respectively, at 25% of the analysed sites. If losses of this magnitude continue the depletion of the pools of Ca, Mg and K may lead to very low base saturation of the soils, possibly accompanied by negative effects on soil fertility, runoff water quality, tree vitality and tree growth within a forest rotation in parts of Sweden. Avoiding whole-tree harvesting can improve the situation substantially for K, but the losses of Ca and Mg will still be significant.

Extraction of natural gas from a confined coal aquifer requires the pumping of large amounts of groundwater, commonly referred to as produced water. Produced water from the extraction of coalbed natural gas is typically disposed into nearby constructed discharge ponds. The objective of this study was to collect produced water samples at outfalls and corresponding discharge ponds and monitor pH, electrical conductivity (EC), calcium (Ca), magnesium (Mg), sodium (Na), and alkalinity. Outfalls and corresponding discharge ponds were sampled from five different watersheds including Cheyenne River (CHR), Belle Fourche River (BFR), Little Powder River (LPR), Powder River (PR), and Tongue River (TR) within the Powder River Basin (PRB), Wyoming from 2003 to 2005. From Na, Ca, and Mg measurements, sodium adsorption ratios (SAR) were calculated, and used in a regression model. Results suggest that outfalls are chemically different from corresponding discharge ponds. Sodium, alkalinity, and pH all tend to increase, possibly due to environmental factors such as evaporation, while Ca decreased from outfalls to associated discharge ponds due to calcite precipitation. Watersheds examined in this study were chemically different form each other and most discharge ponds with in individual watersheds tended to increase in Na and SAR from 2003 to 2005. Since discharge pond water was chemically changing as a function of watershed chemistry, we predicted SAR of discharge pond water using a regression model. The predicted discharge pond water results suggested a high correlation (R ² = 0.83) to discharge well SAR. Overall, results of this study will be useful for landowners, water quality managers, and industry in properly managing produced water from the natural gas extraction.

Aluminum in acidic conditions is toxic to plants. Aluminum tolerance in some plant species has been ascribed to arbuscular mycorrhizal fungal symbiosis. In this study, the application of aluminum was found to inhibit mycelia development of saprobe fungi Fusarium concolor and Trichoderma koningii and the hyphal length of the arbuscular mycorrhizal fungi Glomus mosseae and Glomus deserticola in vitro. Several levels of aluminum were applied to Eucalyptus globulus plants and inoculated with arbuscular mycorrhizal fungi alone or together with both saprobe fungi. The application of 1,500 mg kg⁻¹ decreased the shoot and root dry weight, chlorophyll content and total P, Mg, and Ca concentrations in the shoot of E. globulus. However, both mycorrhizal fungi G. mosseae and G. deserticola inoculated alone increased the shoot dry weight of Eucalyptus, compared with a non- arbuscular mycorrhizal inoculated control treated with 1,500 mg kg⁻¹ of aluminum. When 1,500 mg kg⁻¹ of aluminum was applied, T. koningii increased the effect of G. deserticola on the shoot weight of eucalyptus, whereas with 3,000 mg kg⁻¹, shoot weight and arbuscular mycorrhizal colonization decreased in all treatments. With 1,500 mg kg⁻¹, the highest accumulation of aluminum in the shoot was obtained when G. deserticola was inoculated together with T. koningii. The possibility of manipulating an arbuscular mycorrhizal inoculation together with a saprobe fungus confers a high aluminum resistance in E. globulus. The effect of such combined inoculation is particularly important in some Chilean volcanic acid soils, mainly those which have been intensively cropped and are without lime addition, which facilitates the increase of phytotoxic aluminum species and limits their agricultural use. Therefore, such dual inoculation in field conditions deserves further investigation. Overall, the arbuscular mycorrhizal and saprobe fungi contribute to the increase in resistance of E. globulus to aluminium.

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.

Background, Aim and Scope Acid deposition has become a concern in south China in recent years. This phenomenon has increased to a dramatic extent with the large use of cars and coal- fueled power plants. As a consequence, soils are becoming acidified and their element dynamics will change. A decrease in the nutrient availability will lead to slower plant growth and maybe to a change in the forest type with current species being replaced by new ones with less nutrient requirements. Because of these reasons, it is important to understand how the dynamics of elements will change and what mechanism is part of the process. This knowledge is important for modeling the acidification process and either finding ways to counter it or to predict its consequences. The primary purpose of this study was to provide information about how the dynamics of K, Na, Ca, Mg and P are affected by acid deposition in a typical forest in southern China. Materials and Methods: Experimental soils and saplings were collected directly from the monsoon evergreen broad-leaved forest in Dinghushan. All saplings were transplanted individually into ceramic pots in August 2000 and placed in an open area near their origin site. Pot soils were treated weekly from October, 2000 to July, 2002 with an acidic solution at pH 3.05, pH 3.52, pH 4.00 or pH 4.40, or with tap water as a control. The concentrations of SO42-, NO3-, K+, Na+, Ca2+, Mg2+ and available P and the pH were measured in soil and leachate samples taken at different times. The sapling leaves were collected and their element concentrations were measured at the end of the experiment. Results: Concentrations of soil exchangeable Ca and Mg decreased quickly over time, although only Ca showed changes with the acidic solution treatment and soil exchangeable K was stable because of soil weathering. Leaching of K, Mg and Ca was dependent upon the treatment acidity. Soil available P decreased slowly without any correlation with the acidity of the treatment. All the NO3- added by the treatment was taken up by the plants, but the SO42- added accumulated in the soil. Discussion: Amongst the plant species, Schima superba was little affected by the treatment, the leaf P content was affected in Acmena acuminatissima plants and Cryptocarya concinna was the most susceptible species to soil acidification, with a marked decrease of the leaf K, Ca and Mg concentrations when the treatment acidity increased. Conclusions: Simulated acid deposition affected the dynamics of K, Ca and Mg in the monsoon evergreen broad-leaved forest. The dynamics of Ca in the soil and of K, Mg and Ca in the soil leachates were affected by the acidic solution treatment. If such a soil acidification occurs, Cryptocarya concinna will be amongst the first affected species, but Schima superba will be able to sustain a good growth and mineral nutrition. Recommendations and Perspectives: Acid deposition will lead to imbalance the nutrient elements in the evergreen broad-leaved forest because of accelerated leaching losses of soil exchangeable Ca and Mg. Measures should be developed to slow down soil acidification or nutrient decrease.