Copper (Cu) containing fungicides have been used for more than one century in Europe on agricultural soils, such as vineyard soils. Total Cu concentrations in such soils can exceed toxicological limits that are commonly derived using artificially spiked soils. This study surveyed Cu toxicity in vineyard soils with reference to soils spiked with CuCl(2). Soil was collected in six established European vineyards. At each site, samples representing a Cu concentration gradient were collected. A control (uncontaminated) soil sampled nearby the vineyard was spiked with CuCl(2). Toxicity was tested using standard ecotoxicity tests: two plant assays (Lycopersicon esculentum Miller (tomato) and Hordeum vulgare L. (barley) growth), one microbial assay (nitrification) and one invertebrate assay (Enchytraeus albidus reproduction). Maximal total Cu concentrations in the vineyard sites ranged 435-690 mg Cu kg(-1), well above the local background (23-105 mg Cu kg(-1)). Toxicity in spiked soils (50% inhibition) was observed at added soil Cu concentrations from 190 to 1039 mg Cu kg(-1) (mean 540 mg Cu kg(-1)) depending on the assay and the site. In contrast, significant adverse effects were only found for three bioassays in vineyard samples of one site and for two bioassays in another site. Biological responses in these cases were more importantly explained by other soil properties than soil Cu. Overall, no Cu toxicity to plants, microbial processes and invertebrates was observed in vineyard soil samples at Cu concentrations well above European Union limits protecting the soil ecosystem.
The fate of iron (Fe) may affect that of phosphorus (P) and arsenic (As) in natural waters. This study addresses the removal of Fe, P, and As from streams in lowland catchments fed by reduced, Fe-rich groundwater (average: 20 mg Fe L(-1)). The concentrations of dissolved Fe (<0.45 μm) in streams gradually decrease with increasing hydraulic residence time (travel time) of the water in the catchment. The removal of Fe from streamwater is governed by chemical reactions and hydrological processes: the oxidation of ferrous iron (Fe(II)) and the subsequent formation of particulate Fe oxyhydroxides proceeds as the water flows through the catchment into increasingly larger streams. The Fe removal exhibits first-order kinetics with a mean half-life of 12 h, a value in line with predictions by a kinetic model for Fe(II) oxidation. The Fe concentrations in streams vary seasonally: they are higher in winter than in summer, due to shorter hydraulic residence time and lower temperature in winter. The removal of P and As is much faster than that of Fe. The average concentrations of P and As in streams (42 μg P L(-1) and 1.4 μg As L(-1)) are 1 order of magnitude below those in groundwater (393 μg P L(-1) and 17 μg As L(-1)). This removal is attributed to fast sequestration by oxidizing Fe when the water enters oxic environments, possibly by adsorption on Fe oxyhydroxides or by formation of ferric phosphates. The average P and As concentrations in groundwater largely exceed local environmental limits for freshwater (140 μg P L(-1) and 3 μg As L(-1)), but in streams, they are below these limits. Naturally occurring Fe in groundwater may alleviate the environmental risk associated with P and As in the receiving streams.
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Boron (B) affects plant growth in soil at B doses (mg added B kg -1 soil) that appear in the range of natural background B concentrations. A study was set up to determine B bioavailability by testing B toxicity to plant as affected by soil properties and ageing after soil dosing. Nineteen soils (pH 4.4-7.8) and 3 synthetic soils (sand-peat mixtures) were amended with 7 doses of H 3 BO 3 . Barley root elongation was determined immediately after B amendment and after 1 and 5 months ageing. Soil solution B concentrations increased linearly with added B concentrations with almost no detectable adsorption. In contrast, the ratio of aqua regia soluble B/soil solution B in unamended soils (no B added) was 10-25 times higher than in B amended soils at similar aqua regia soluble B concentrations illustrating a much lower B availability in unamended soils.Soil solution B concentrations did not decrease by ageing. The toxic B doses or soil B concentrations that decreased barley root growth by 10% (EC10 values) varied about tenfold (respectively 3-27 mg added B kg -1 and 5-52 mg B kg -1 ) among soils. Corresponding thresholds in soil solution varied less than fourfold (16-59 mg B l -1 ). Soil ageing for 5 months did not significantly change EC10 and EC50 values, expressed either as total soil B or as soil solution B, unless in 1 soil. Variability in EC10 and EC50 values was explained by various soil properties (soil moisture content, background B, %clay, cation exchange capacity), but covariance of these properties with the soil moisture content suggest that B dilution is the critical factor explaining B toxicity. It is concluded that effects of B amendments do not decrease by ageing and that soil solution B or B doses corrected for soil moisture content may be used as an index for B toxicity across different soils.
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