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.

This study examined the effects of heavy metals and plant arsenic uptake on soil arsenic distribution. Chemical fractionation of an arsenic-contaminated soil spiked with 50 or 200 mg kg-1 Ni, Zn, Cd or Pb was performed before and after growing the arsenic hyperaccumulator Pteris vittata L for 8 weeks using NH4Cl (water-soluble plus exchangeable, WE-As), NH4F (Al-As), NaOH (Fe-As), and H2SO4 (Ca-As). Arsenic in the soil was present primarily as the recalcitrant forms with Ca-As being the dominant fraction (45%). Arsenic taken up by P. vittata was from all fractions though Ca-As contributed the most (51-71% reduction). After 8 weeks of plant growth, the Al-As and Fe-As fractions were significantly (p < 0.01) greater in the metal-spiked soils than the control, with changes in the WE-As fraction being significantly (p = 0.007) correlated with plant arsenic removal. The plant's ability to solubilize soil arsenic from recalcitrant fractions may have enhanced its ability to hyperaccumulate arsenic. Arsenic taken up by P. vittata was from all fractions with most from the Ca-fraction.

Tobacco plants transformed with TaLCT1 were cultured on Knop's medium with modified calcium concentrations (0.01-3 mM) in the presence of Pb2+, and in soil contaminated by lead. A 4-5 μM Pb2+ administered in the presence of 1 mM Ca2+ inhibited the root growth of transgenic plants to much lesser degree than of control plants, whereas in the presence of 3 mM Ca2+ no differences were found between the studied lines. The reduction of Pb2+ toxicity in the presence of 1 mM Ca2+ was not accompanied by a change in the lead tissue concentration. However, when Ca2+ level in the medium was lowered to 0.01 mM, several fold higher root/shoot Pb ratio in transgenic plants was observed, twofold increase in the total amount of metal accumulated, and lower concentration of Pb in the xylem sap. Results suggest the involvement of TaLCT1 in the regulation of Ca-dependent Pb-detoxification, and under conditions of low calcium in lead uptake and distribution. Ca2+-dependent Pb2+ detoxification and uptake was regulated by TaLCT1.

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.

Increasing environmental concentrations of platinum group metals (PGMs), in particular platinum (Pt), rhodium (Rh) and palladium (Pd), from catalytic converters has been reported worldwide. The impact of these three metals on the uptake and use of essential mineral nutrients was examined using two plant models: the submerged aquatic plant, Elodea canadensis, and the terrestrial emergent plant, Peltandra virginica. Plants were grown for 2 weeks in nutrient solutions with either Pt⁴⁺ at concentrations between 0.05 and 5 mg/L, or a 0.1 mg/L Pt⁴⁺, Rh³⁺, Pd²⁺ mixture. Some treatments received additional Ca²⁺, Zn²⁺, or humic acid (with varying pH) to study how these conditions affected PGM uptake. Metal concentration analyses were conducted using a graphite furnace atomic absorption spectrometer (GFAAS) or an inductively coupled plasma emission spectrometer (ICP). Growth response was assessed through total chlorophyll content. There was significant Pt accumulation in plant tissues, from 55 to 326 times the concentration in nutrient solution. At pH 8, the addition of humic acid doubled Pt accumulation in comparison to the control. Additional exogenous minerals did not significantly affect PGM uptake, nor did the uptake of PGMs interfere with the uptake of Ca, Fe or Cu. Synthesis of chlorophyll in new shoots was not affected by Pt accumulation; however, visible chlorosis was observed in older shoots at 5 ppm Pt. Roadside Daucus carota samples from four heavy traffic locations in Dutchess County (New York) were also assessed for PGM content. Pt, Pd and Rh concentrations averaged 14.6, 10.2, and 0.7 μg/g, respectively.

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.

Buffer capacity analysis of open atmospheric gas-liquid systems containing main acidic and basic atmospheric pollutants was carried out. Usually the buffer capacity is considered as a function of pH as an independent variable. In this work the buffer capacity is analysed including the dependence of pH on the composition of a system. Such an approach allows finding an important, from the viewpoint of atmospheric water acidification, relationship between the gas phase composition and the buffer capacity. It was found that buffer capacity of the open gas-liquid systems may be very high and it may cause the liquid phase pH to remain at low levels. The buffer capacity of the analysed systems is most strongly affected by the simultaneous presence of ammonia and strong acids in the gas phase. The higher concentrations of strong acid gases the lower NH₃ concentration is sufficient to achieve high buffer capacity. In the presence of strong acid gases, calcium ions affect both the buffer capacity and the liquid phase pH only at low NH₃ concentrations. High buffer capacity of open gas-liquid systems may be one of the reasons why the reduction in emissions of acidic gas pollutants has little effect on decrease in atmospheric water acidity.

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.

In response to reduced sulphur emissions, there has been a large decrease in sulphate ( [graphic removed] ; -0.97 μeq l-¹ year-¹) and hydrogen (-1.18 μeq l-¹ year-¹) ion concentration in bulk precipitation between 1980 and 2000 at Plastic Lake in central Ontario. The benefit of this large reduction in [graphic removed] deposition on stream water chemistry was assessed using the gauged outflow from a conifer-forested catchment (PC1; 23.3 ha), which is influenced by a small wetland located immediately upstream of the outflow. Sulphate concentrations declined, but not significantly due to large inter-annual variation in [graphic removed] concentration. Between 1980 and 2000, there were significant increases in dissolved organic carbon, ammonium and potassium concentration likely reflecting increased mineralisation in the wetland. Calcium concentrations in PC1 decreased during the two decade period (-2.24 μeq l-¹ year-¹), as a consequence there was no improvement in stream pH and the Ca:Al ratio in PC1 continued to decline. A similar response was noted in an upland-draining sub-catchment of PC1-08 that has been monitored since 1987. Despite large reductions in [graphic removed] deposition and almost complete retention of nitrogen in soil, there has been no improvement (in terms of pH) in stream water at PC1 due to a combination of soil acidification and climatic (droughts, increased mineralisation) perturbations.

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.