Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄-K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l-¹), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l-¹ and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g-¹ of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g-¹.

In the study area physical and chemical factors control the composition of surface and groundwaters, which in turn determine the water quality of the “Biviere di Gela” lake. These factors combine to create diverse water types which change their compositional character spatially as rainfall infiltrates the soil zone, moves down a topographically defined flow path, and interacts with bedrock minerals. Low-salinity waters, which represent the initial stage of underground circulation, start dissolving calcium carbonate from the local rocks. The progressive increase in salinity, characterized by substantially higher Ca, SO₄, Na and Cl concentrations, suggests that dissolution of CaSO₄ and NaCl is an important process during water-rock interactions. The “Biviere di Gela” lake is often separated into two units (Lago Grande and Lago Piccolo). “Lago Grande” water is generally of Na-SO₄-Cl-type, whereas “Lago Piccolo” water is of Na-Cl-SO₄-type. Their total content of dissolved salts varies with season, the amount of rainfall, and inflow of ground and drainage water. Over time, an increasing trend towards greater salinity and also sudden changes in the relative abundances of Cl and SO₄ have been recorded for the “Lago Grande.” The isotope composition of the lake water appears to be affected by inflow of ground and surface waters and also by evaporative loss. The nitrate content of waters from the recharge basin is of particular concern because it contributes to lake eutrophication. The trace element contents do not evidence the presence of any significant metal contamination of lake waters, although a future potential hazard of metals bioaccumulation by the aquatic biota must be taken into consideration. Finally, a water balance for the basin shows that a drop in precipitation of about 20% might be critical for lake survival.

Aquatic macrophytes are well known accumulators for heavy metals, the reason why they are used as bioindicators for water quality and in phytoremediaton strategies. This study reports on the elemental concentrations in four free-floating aquatic macrophytes (S. auriculata; P. stratiotes; E. crassipes and E. azurea) growing in two water reservoirs (Santana e Vigário, Rio de Janeiro State, Brazil) of an electric power plant that receive input from the polluted Paraíba do Sul River. Filtered water samples and water suspended solids from these environments were also analysed. Inductively coupled plasma mass spectrometry was used as the principal method, allowing the determination of up to 41 elements, including the rare-earth elements (REEs) and other trace metals not assayed before in these macrophytes. The results show that all elements studied are accumulated by the macrophytes with concentration ratios (CR = [plant]: [water]) varying from about 1,000 to 200,000, based on the dry weight of the plant species. With a few exceptions, highest accumulations were observed in E. crassipes in which CRs increase in the sequence: Cu < Mo < Cr < Pb < Tl < Fe < La < Zn < Ce< Mn. Surprisingly high CRs (e.g. Ce: 74,000) and corresponding mass concentrations were observed for the rare-earth elements (e.g. [summation operator]REE: 112 mg kg-¹), also measured in the water suspended particle fraction. The results show that this fraction acts as an effective sink for trace metals in the aquatic system studied and seems to play also an important role in the transfer of metals from water to the plant species.

Vegetation both physically and biochemically influences denitrification in wetlands. Litter from various plant species supplies various amounts and qualities of organic carbon to denitrifying bacteria, and may thus affect denitrification capacity. We explore whether there is seasonal variation in the denitrification potential in stands of Glyceria maxima, Phragmites australis, Typha latifolia, and Potamogeton pectinatus (the stands differed in terms of which species was predominant). Experiments and measurements investigated whether denitrification potential was related to organic matter and its availability to denitrifying bacteria, suitability for bacterial growth, and amount in the wetland. Availability of organic material, as measured in the slurries, was highest in the G. maxima and P. pectinatus samples, with the highest availability in May and August. However, when the samples were closer to wetland conditions, i.e., intact sediment cores containing litter and organic sediment, the denitrifying capacity was highest in the cores from G. maxima stands, but lowest in P. pectinatus cores. In addition, the denitrification potential of the intact cores was highest in November. Differences in denitrification capacity between the slurries and intact sediment cores, considering the organic material of the plant species and the seasonal pattern, were attributed to differences in the amount of plant litter generated.

In freshwater environments direct biological effect of ultraviolet radiation (UVR) result from absorption of specific wavelengths by macromolecules and alteration of biochemical processes. Indirect effects are related to UVR interaction with water and dissolved organic carbon to form chemically reactive species (ROS: reactive oxygen species). Zooplankton photoprotection includes mycosporine-like amino acids, pigments, production of quenching agents and antioxidant enzymes. The relative importance of each mechanism would depend on the organisms. In this study, we determined the antioxidant enzyme activities Catalase (CAT) and Glutathione-S-transferase (GST) in the copepod Boeckella gracilipes and the cladoceran Ceriodaphnia dubia in three Andean lakes of the North-Patagonia region. There were differences in antioxidant enzymes expression between copepods and cladocerans. CAT was significantly higher in C. dubia than in B. gracilipes whereas GST was similar in both species. The comparison of B. gracilipes enzyme activity in the three lakes showed also differences in GST but not in CAT. DOC decreases the exposure by absorption of UVR but simultaneously acts as photosensitizer producing ROS and their successive toxic products in the surface waters. We discuss that comparisons among lakes of different DOC should be considered carefully because lake physico-chemicals parameters, as well as food web structure, will difficult any predictions on the net effect of DOC.

To evaluate the acid deposition reduction negotiated for 2010 within the UNECE LRTAP Gothenburg Protocol, sulphur and nitrogen deposition time-series (1880-2100) were compared to critical loads of acidity on five French ecosystems: Massif Central basalt (site 1) and granite (2); Paris Bassin tertiary sands (3); Vosges mountains sandstone (4) and Landes eolian sands (5). The SAFE model was used to estimate the response of soil solution pH and [graphic removed] ratio to the deposition scenario. Among the five sites, critical loads were exceeded in the past at sites 3, 4 and 5. Sites 3 and 4 were still expected to exceed in 2010, the Protocol year. Further reduction of atmospheric deposition, mainly nitrogen, would be needed to achieve recovery on these ecosystems. At sites 3, 4 and 5, the delay between the critical load exceedance and the violation of the critical chemical criterion was estimated to be 10 to 30 years in the top soil and 50 to 90 years in the deeper soil. At site 5, a recovery was expected in the top soil in 2010 with a time lag of 10 years. Unexpectedly, soil pH continued to decrease after 1980 in the deeper soil at sites 2 and 5. This time lag indicated that acidification moved down the soil profile as a consequence of slow base cation depletion by ion exchange. This delayed response of the soil solution was the result of the combination of weathering rates and vegetation uptake but also of the relative ratio between base cation deposition and acid compounds.

Many national exposure programmes have been performed in tropical and subtropical climates during the last 50 years. However, ambitious programmes involving more than a few countries are scarce. In this paper a recently formed network of test sites is described involving 12 test sites in Asia (India, Vietnam, Thailand, Malaysia and China including Hong Kong) and four test sites in Africa (South Africa, Zambia and Zimbabwe). This effort is part of the 2001-2004 Swedish International Development Agency (SIDA) funded Programme on Regional Air Pollution in Developing Countries (RAPIDC). Corrosion attack after one (2002-2003) year of exposure (carbon steel, zinc, copper, limestone and paint coated steel) are presented together with environmental data (SO₂, NO₂, HNO₃, O₃, particles, amount and pH of precipitation, temperature and relative humidity) for all the test sites. The obtained corrosion values are substantially higher than expected for limestone, higher than expected for carbon steel and lower than expected for zinc compared to values calculated using the best available dose-response functions.

Studies on N losses from ornamental plantings - other than turf - are scant despite the ubiquity of these landscaping elements. We compared pore water NO₃ and extractable soil NO₃ and NH₄ in areas with turf, areas with seven different types of ornamental landscape plantings, and a native woodland. Turf areas received annual N inputs of ~48 kg ha-¹ and annual flowers received ~24 kg N ha-¹ at the time of planting. None of the other areas were fertilized during the course of the study. Data were collected on 23 occasions between June 2002 and November 2003. Pore water NO₃ concentrations at a 60-cm depth - based on pooled data - were highest (1.4 to 7.8 mg NO₃-N l-¹) under ground covers, unplanted-mulched areas, turf, deciduous trees, and evergreen trees, with no differences among these vegetation types. Lower values were observed under woodlands, annual and perennial flowers, and evergreen and deciduous shrubs. Pore water NO₃ concentrations exceeded the drinking water regulatory limit of 10 mg NO₃-N l-¹ under ground covers, turf and unplanted-mulched areas in 39, 20 and 10% of samples, respectively. Leaching losses of NO₃-N over 18 months ranged from 0.17 kg N ha-¹ in the woodlands to 34.97 kg N ha-¹ under ground covers. Annual NO₃ losses under unplanted-mulched areas and ground covers were approximately twice the average N input (10 kg N ha-¹ year-¹) from atmospheric deposition. Extractable NO₃ in woodland soils (0.5 μg NO₃-N g-¹) was lower than for all other vegetation types (3.1-7.8 μg NO₃-N g-¹). Extractable NH₄ levels were highest in woodlands, deciduous trees, and annual flowers (6.7-10.1 μg NH₄-N g-¹). Most vegetation types appear to act as net N sinks relative to atmospheric inputs, whereas unplanted-mulched areas and areas planted with ground covers act as net sources of NO₃ to groundwater.

Ammonia fluxes from application of anaerobically-digested slurry (ADS) and chemical fertilizer (CF) to flooded forage rice (Oryza sativa L.) in Japan were measured using a dynamic flow-through chamber method in lysimeters. The CF was applied at a rate of 300 N ha-¹ (three times) as ammoniacal-N fertilizer, and the ADS was applied to the lysimeters at total rates equivalent to 75, 100 and 150 kg N ha-¹, by broadcasting uniformly into the floodwater at three or six times (equal splits) between 17th June and 17th November, 2005. The emission fluxes for the first 2 days after application were very high from ADS, the highest values being 679 compared with a maximum of 156 mg N m-² d-¹ from CF. Most (61-93%) of the ammonia loss occurred during the first 5 days after each application of fertilizer. The total N loss as ammonia from ADS (29.6-51.7%) was much higher than from CF (12.2%). The highest fluxes were observed in August (2005) when air temperature was highest. More ammonia was lost from the ADS applied at the early stages (i.e. root taking, tiller stages) than at later stages (i.e. elongation, fruiting stages) of rice growth.

The hydrolysis of 4-Nitrophenylphosphate (NPP) in the presence of Ferrous and Ferric ions in Oil in water microemulsion media was investigated. The reaction was monitored by measuring the absorbance of the nitrophenolate ion produced in the reaction aliquots with time. The order of effectiveness of the microemulsion system towards the hydrolysis of NPP was found to be cationic > anionic> aqueous in the presence of Ferrous, Ferric and Turnbull's blue at neutral pH. The result of the present investigation enriches our understanding of the possible roles polymetallic ions play in hydrolysis reactions. The reactions mimic the roles of purple acid phosphatases in the hydrolysis of phosphate esters. The application of the above systems for environmental decontamination of organophosphates is also envisoned.