A critical load data base was developed for Europe and Northern Asia using the latest data bases on soils, vegetation, climate and forest growth. Critical loads for acidity and nutrient nitrogen for terrestrial ecosystems were computed with the Simple Mass Balance model. The resulting critical loads are in accordance with critical loads from previous global empirical studies, but have a much higher spatial resolution. Critical loads of acidity are sensitive to both the chemical criterion and the critical limit chosen. Therefore a sensitivity analysis of critical loads was performed by employing different chemical criteria. A critical limit based on an acid neutralizing capacity (ANC) of zero resulted in critical loads that protect ecosystems against toxic concentrations of aluminium and unfavourable Al/Bc ratios, suggesting that ANC could be an alternative to the commonly used Al/Bc ratio. Critical loads of nutrient nitrogen are sensitive to the specified critical nitrate concentration, especially in areas with a high precipitation surplus. If limits of 3¿6 mg N l¿1 are used for Western Europe instead of the widely used 0.2 mg N l¿1, critical loads double on average. In low precipitation areas, the increase is less than 50%. The strong dependence on precipitation surplus is a consequence of the simple modelling approach. Future models should explore other nitrogen parameters (such as nitrogen availability) instead of leaching as the factor influencing vegetation changes in terrestrial ecosystems.

This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration as Pb(II). However, Cd(II) and Zn(II) did not seem to compete with Pb(II) for strong binding sites of SRFA. These two metals did compete with Pb(II) for the weaker binding sites of SRFA. Heterogeneity of SRFA was found to play a crucial role in metal-SRFA interactions. The environmental significance of this research for freshwater is that even at relatively low Pb(II) loadings, the metals associated with lead in minerals, e.g. Cu(II), may successfully compete with Pb(II) for the same binding sites of the naturally occurring organic complexants, with the result that some of the Pb(II) may exist as free Pb²⁺ ions, which has been reported to be one of the toxic forms of Pb in aquatic environment.

The immobilization of lead by the reaction with phosphate bearing materials is a promising remediation method for contaminated soils. Low soluble neo-formed lead-phosphate phases similar to chloropyromorphite [Pb₅(PO₄)₃Cl], can control availability and mobility of lead in the environment, and consequently reduce human exposure, if soils are the main contamination pathway. We used three phosphate source materials [NaH₂(PO₄)₃, commercial superphosphate and phosphate rock] to study lead immobilization in soil and mining waste samples. Products were examined after 1, 3 and 6 months of contact. The samples are from a contaminated area by former Pb mining and smelting activities, in southeastern Brazil, where epidemiological studies showed high lead blood levels in local population. The PBET (physiological based extraction test) bioaccessibility test was used to measure changes in the amount of soluble lead after sample treatment. Results show that the most efficient phosphate source was NaH₂(PO₄)₃, which reduced lead solubility to 92% in acidic gastric conditions after the first month of contact. Superphosphate and phosphate rock also diminished Pb solubility, but the effect was more time dependent. None specific Pb-phosphate phases could be identified by XRD in whole treated samples, but the Pb-Ca-P elemental associations, observed on SEM images and EDS spectra of portions of the samples, combined with the reduced solubility, indicate that more insoluble lead phases were formed after the treatment. Based in these results, the in site phosphate application on soils to induce lead immobilization should be considered as a possible alternative to reduce human exposure at the area.

The distribution of nonylphenol ethoxylates (NPEOn) and their derivatives of nonylphenol (NP) and nonylphenoxy ethoxy acetic acids (NPEnC) in the sediments of a relatively closed freshwater reservoir was investigated using sediment layers sliced from undisturbed sediment cores collected with a gravity core sampler at three sampling sites (St. 1, St. 2 and St. 3) along the water flow direction. The relationships between the bound content of these compounds and the sediment organic matter as well as the likely transformation pathways were evaluated. The total content of NPEOn (n = 1-15) fell in 84.6-336.5, 59.9-135.5 and 77.0-623.4 μg/kg-dry for all sliced layers at St.1, St.2 and St.3, respectively, with the content of individual NPEOn species showing a general decreasing trend with the attached molar number of the ethoxy (EO) chain. Compared to each detected NPEOn species, the bound content of NP was much higher, falling in 73.2-248.4, 79.9-358.2 and 25.5-1,988.4 μg/kg-dry at St. 1, St. 2 and St. 3, respectively. A general increasing trend of the NP content along the water flow direction of the reservoir was revealed. NPEnC (n = 1-10) varied in 1.93-4.12, 2.85-9.84 and 1.05-19.1 μg/kg-dry for sediment at the respective site of St. 1, St. 2 and St. 3, with the averaged values at these sites (2.91, 4.71 and 6.72 μg/kg-dry) showing an increasing trend from the upstream to the downstream. For NPEnC, a parametric trend of increases in the content of NPE₁C, NPE₂C and NPE₃C with the bound sediment organic matter (9.06-11.8%) seemed to be existent. Furthermore, the computed magnitudes of NPEO₁-₂/NPEO₁-₁₅, NP/NPEO₁-₁₅ and NPEC₁-₁₀/NPEO₁-₁₅ suggested that non-oxidative hydrolytic transformation was probably prevailing within the sedimented mud phase of the reservoir, with the oxidative hydrolytic transformation pathway being less involved.

The content of Pb, Cd, Mn, K, Ca, Mg and ²⁰⁶Pb/²⁰⁷Pb isotope ratios in spruce tree rings (Picea abies) and peat cores from the Brdy Hills area (10 km W of the Pb smelter) were compared with those in spruce tree rings in the vicinity of the Pb smelter. Maximum Pb content in tree rings (up to 60 mg kg-¹ Pb) corresponds to a peak of metallurgical production in the mid 1970s and highest smelter emissions in the early 1970s. The Pb concentration curves obtained from peat deposit profiles closely correlate with the Pb concentrations in tree rings at both sampling sites. The small differences between the individual tree cores, with the identical general trend, may be attributed to the difference in distance from the smelter and the altitude of each sampling site. Similar behaviour to Pb can be observed for Cd and Ca. Lead isotope composition in tree rings (²⁰⁶Pb/²⁰⁷Pb ~1.143-1.174) is controlled mainly by the smelter emissions (²⁰⁶Pb/²⁰⁷Pb ~1.16-1.17), with the exception of the youngest segments from the more distant locality from the smelter, which yield isotopic signatures corresponding to car-emission Pb (²⁰⁶Pb/²⁰⁷Pb ~1.143-1.150). Higher content of Mn, Mg and Ca in tree rings corresponding to the 1970s and 1980s may be related to soil chemistry changes caused by acid deposition. In addition, an increase in K, Mg (and in some cases also Mn) in the youngest part of wood cores corresponds to the physiological processes in sapwood, and may be influenced by a decrease in Pb in organic soil horizons, which limited the cycling of basic inorganic nutrients.

In order to estimate acute-to-chronic toxicity ratios (ACRs) relevant to a coldwater stream community, we exposed rainbow trout (Oncorhynchus mykiss) to cadmium (Cd), lead (Pb), and zinc (Zn) in 96-h acute and 60+ day early-life stage (ELS) exposures. We also tested the acute and sublethal responses of a mayfly (Baetis tricaudatus) and a midge (Chironomus dilutus, formerly C. tentans) with Pb. We examine the statistical interpretation of test endpoints and the acute-to-chronic ratio concept. Increasing the number of control replicates by 2 to 3x decreased the minimum detectable differences by almost half. Pb ACR estimates mostly increased with increasing acute resistance of the organisms (rainbow trout ACRs <[almost equal to] mayfly < Chironomus). The choice of test endpoint and statistical analysis influenced ACR estimates by up to a factor of four. When calculated using the geometric means of the no- and lowest-observed effect concentrations, ACRs with rainbow trout and Cd were 0.6 and 0.95; Zn about 1.0; and for Pb 3.3 and 11. The comparable Pb ACRs for the mayfly and Chironomus were 5.2 and 51 respectively. Our rainbow trout ACRs with Pb were about 5-20x lower than earlier reports with salmonids. We suggest discounting previous ACR results that used larger and older fish in their acute tests.

A novel silicate mesoporous material, SBA-15 supported Fe₂O₃, was synthesized by post-synthesis method via ultrasonic-assisted route. The desulfurization test from a gas mixture containing 0.1 vol% H₂S was carried out over SBA-15 supported Fe₂O₃ in a fixed-bed system at atmospheric pressure and room temperature. The effects of the chemical nature of Fe₂O₃ and the textural properties of the material on desulfurization capacity were studied. Materials before and after the desulfurization test were characterized using nitrogen adsorption, XRD, TEM, FTIR, XPS, ICP and other standard methods. The characterization results suggest that modification process does not change the two-dimensional hexagonal mesostructure of SBA-15. Iron species disperses inside channels and the outside surface in the crystalline phase of iron oxide. The material with iron content of 31.3 wt% presented highest H₂S uptake capacity. Structural properties of the material also play important roles in desulfurization performance besides the catalytic effects of iron oxide. The basic feature of material and enough oxygen supply are benefit for the reaction. SBA-15 supported Fe₂O₃ can be an effective alternative to capture H₂S from gas streams.

Historic and current agricultural and industrial activities have resulted in accumulation of Cd, Cu, Pb and Zn in soil. To estimate potential risks for ecosystems, agriculture and water quality, an integrated risk assessment was performed for The Netherlands. Risks of metal contamination were assessed on a national scale by comparing present soil concentrations of Cd, Pb, Cu and Zn with critical concentrations of those metals in view of agricultural impacts, ecological impacts and impacts on the quality of groundwater and surface waters. Results show that present soil metal concentrations cause few risks for agriculture or ecosystems; for less than 2% of the surface area present metal levels exceed critical limits. Critical limits for groundwater are only significantly exceeded for Pb (17% of the area), but critical limits for surface water are exceeded throughout the country for Cu and Zn. Taking critical limits used in The Netherlands, the area where exceedances take place is nearly negligible for Cd and low for Pb (less than 3%), but much larger (between 40% and 50%) for both Cu and Zn. Results from this study suggest that accumulation of heavy metals in Dutch soils at present primarily affects the quality of surface waters. This stresses the need for harmonization of soil and water policy. Measures to reduce the load in surface waters to meet target levels, under conditions like those prevailing in The Netherlands, are bound to have an impact on land management.

The arsenic bioavailability in the bed sediments from the Anllóns River (NW Spain) has been assessed by using several analytical approaches. A six-step sequential fractionation was compared to three general availability tests: the Toxicity Characteristic Leaching Procedure (TCLP) extraction, which estimates the leaching potential of As and its effect on the survival of microorganisms (Vibrio fischeri), an extraction with 1 M HCl extraction, which estimates the bioavailability to higher plants, and a physiologically based extraction test (PBET), which estimates the bioavailability to superior animals. Arsenic was found to be mainly associated to the least mobile fractions: bound to Fe-Al oxides and in the residual phase. Among the three single extractants considered, the PBET extracted the highest As concentrations (1-11% of the total As). The TCLP extracts showed toxicity to Vibrio fischeri whereas for the plants evaluated, aqueous extracts did not show adverse effects.