Soil contamination may contribute to forest decline, by altering nutrient cycling and acquisition by plants. This may hamper the establishment of a woody plant cover in contaminated areas, thus limiting the success of a restoration program. We studied the nutritional status of planted saplings of Holm oak (Quercus ilex subsp. ballota (Desf.) Samp.), white poplar (Populus alba L.), and wild olive tree (Olea europaea var. sylvestris Brot.) in the Guadiamar Green Corridor (SW Spain) and compared it with established adult trees. Soils in this area were affected by a mine-spill in 1998 and a subsequent restoration program. The spill resulted in soil acidification, due to pyrite oxidation, and deposited high concentrations of some trace elements. In some sites, we detected a phosphorus deficiency in the leaves of Q. ilex and O. europaea saplings, as indicated by a high N:P ratio (>16). For O. europaea, soil contamination explained 40% of the variability in leaf P and was negatively related to chlorophyll content. Soil pH was a significant factor predicting the variability of several nutrients, including Mg, P, and S. The uptake of Mg and S by P. alba was greater in acidic soils. The monitoring of soil pH is recommended since long-term effects of soil acidification may negatively affect the nutritional status of the trees.

17 pages, 7 figures, 7 tables, 62 references. We thank Dr. Luis V. García for his statistical advice and Olga Cazalla (Centre for Scientific Instrumentation, University of Granada) for the ICP-MS measurements. We are grateful to José María Alegre and Isabel Ibáñez for their help in different stages of the study and to an anonymous reviewer for the comments on a previous version of the manuscript. | Soil contamination may contribute to forest decline, by altering nutrient cycling and acquisition by plants. This may hamper the establishment of a woody plant cover in contaminated areas, thus limiting the success of a restoration program. We studied the nutritional status of planted saplings of Holm oak (Quercus ilex subsp. ballota (Desf.) Samp.), white poplar (Populus alba L.), and wild olive tree (Olea europaea var. sylvestris Brot.) in the Guadiamar Green Corridor (SW Spain) and compared it with established adult trees. Soils in this area were affected by a mine-spill in 1998 and a subsequent restoration program. The spill resulted in soil acidification, due to pyrite oxidation, and deposited high concentrations of some trace elements. In some sites, we detected a phosphorus deficiency in the leaves of Q. ilex and O. europaea saplings, as indicated by a high N:P ratio (>16). For O. europaea, soil contamination explained 40% of the variability in leaf P and was negatively related to chlorophyll content. Soil pH was a significant factor predicting the variability of several nutrients, including Mg, P, and S. The uptake of Mg and S by P. alba was greater in acidic soils. The monitoring of soil pH is recommended since long-term effects of soil acidification may negatively affect the nutritional status of the trees. | We acknowledge the Regional Ministry of Environment (Junta de Andalucía) for supporting this study within the SECOVER research program and the Spanish Ministry of Education for a PFU grant awarded to M.T. Domínguez. | Peer reviewed

To evaluate adverse impacts of metal pollution originating from smelting activities on the aquatic ecosystem of Deûle river in northern France, water samples were collected from five selected stations along a contaminated region of this river (during two surveys: April-June 2005 and April-May 2007). All samples were analysed using inductively coupled plasma (ICP) atomic emission spectroscopy and/or ICP-mass spectrometry. Both the concentrations of dissolved and particulate elements were determined, and analytical data were compared with national and international water/particle quality guidelines as well as with some values reported in the literature for polluted rivers. For all the metals studied (i.e. Cd, Cr, Cu, Mn, Ni, Pb and Zn), our investigations showed that the effects of the dissolved phase on this aquatic medium were weak, according to water quality status established by US Environmental Protection Agency, USEPA (1994, 1999). Conversely, the levels of metals in suspended particulate matter were found to be much higher than local background contents and natural reference levels in French catchments. These levels were further quantified as “serious” contamination, i.e. above the “red” range that was previously elaborated by most existing metal-contamination scales in French basins of similar geology. The affinity of these metals for the particulate phase in Deûle waters follows the order: Cd >Cr > Pb > Zn = Mn > Cu > Ni. The trace metals released from anthropogenic activities were found to be partly bound to the reactive particulate phase, calcite, which is sensitive to physico-chemical variations occurring in the river ecosystem. To appraise the risk of ecotoxicity by metals, predictions on the ability to release metallic pollutants from calcite into waters were made successfully by testing three equilibrium geochemical speciation models (JCHESS, VISUAL MINTEQ and WINHUMIC) in which soluble organic matter was taken into account. Calculations showed that metal-water-calcite systems in Deûle River are close to thermodynamic equilibrium with generation of solid solutions, MeαCa₁₋αCO₃, by (co)precipitation and/or adsorption reactions. On the basis of results mentioned here, more measurements of river chemistry and assessments of predictive capabilities of chosen water-quality guidelines with time would be developed in aquatic and calcareous areas for controlled dredging operations or other treatment engineering works.

To evaluate adverse impacts of metal pollution originating from smelting activities on the aquatic ecosystem of DeA >> le river in northern France, water samples were collected from five selected stations along a contaminated region of this river (during two surveys: April-June 2005 and April-May 2007). All samples were analysed using inductively coupled plasma (ICP) atomic emission spectroscopy and/or ICP-mass spectrometry. Both the concentrations of dissolved and particulate elements were determined, and analytical data were compared with national and international water/particle quality guidelines as well as with some values reported in the literature for polluted rivers. For all the metals studied (i.e. Cd, Cr, Cu, Mn, Ni, Pb and Zn), our investigations showed that the effects of the dissolved phase on this aquatic medium were weak, according to water quality status established by US Environmental Protection Agency, USEPA (1994, 1999). Conversely, the levels of metals in suspended particulate matter were found to be much higher than local background contents and natural reference levels in French catchments. These levels were further quantified as "serious" contamination, i.e. above the "red" range that was previously elaborated by most existing metal-contamination scales in French basins of similar geology. The affinity of these metals for the particulate phase in DeA >> le waters follows the order: Cd > Cr > Pb > Zn = Mn > Cu > Ni. The trace metals released from anthropogenic activities were found to be partly bound to the reactive particulate phase, calcite, which is sensitive to physico-chemical variations occurring in the river ecosystem. To appraise the risk of ecotoxicity by metals, predictions on the ability to release metallic pollutants from calcite into waters were made successfully by testing three equilibrium geochemical speciation models (JCHESS, VISUAL MINTEQ and WINHUMIC) in which soluble organic matter was taken into account. Calculations showed that metal-water-calcite systems in DeA >> le River are close to thermodynamic equilibrium with generation of solid solutions, Me alpha Ca(1-)alpha CO(3), by (co)precipitation and/or adsorption reactions. On the basis of results mentioned here, more measurements of river chemistry and assessments of predictive capabilities of chosen water-quality guidelines with time would be developed in aquatic and calcareous areas for controlled dredging operations or other treatment engineering works.

Sulfonamide antibiotics can enter agricultural soils by fertilisation with contaminated manure. While only rough estimations on the extent of such applications exist, this pathway results in trace level contamination of groundwater. Therefore, we studied the transport of three sulfonamides in leachates from field lysimeters after application of a sulfonamide-contaminated liquid manure. In a 3-year period, the sulfonamides were determined in 64% to 70% of all leachate samples at concentrations between 0.08 to 56.7 µg L⁻¹. Furthermore, sulfonamides were determined in leachates up to 23 months after application, which indicated a medium- to long-term leaching risk. Extreme dry weather conditions resulted in highest dislocated amounts of sulfonamides in two of the three treatments. Furthermore, soil management such as tillage and cropping affected the time between application and breakthrough of sulfonamides and the intra-annual distribution of sulfonamide loads in leachates. Although the total sulfonamide leaching loads were low, the concentrations exceeded the limit value of the European Commission of 0.1 µg biocide L⁻¹ in drinking water in more than 50% of all samples. Furthermore, the medium-term mean concentration of the sulfonamides ranged from 0.08 and 4.00 µg L⁻¹, which was above the limit value of the European Commission in 91 out of 158 samples. Therefore, sulfonamides applied to soils in liquid manure under common agricultural practice may cause environmental and health risks which call for a setting up of more long-term studies on the fate of antibiotics.

Sulfonamide antibiotics can enter agricultural soils by fertilisation with contaminated manure. While only rough estimations on the extent of such applications exist, this pathway results in trace level contamination of groundwater. Therefore, we studied the transport of three sulfonamides in leachates from field lysimeters after application of a sulfonamide-contaminated liquid manure. In a 3-year period, the sulfonamides were determined in 64% to 70% of all leachate samples at concentrations between 0.08 to 56.7 µg L−1. Furthermore, sulfonamides were determined in leachates up to 23 months after application, which indicated a medium- to long-term leaching risk. Extreme dry weather conditions resulted in highest dislocated amounts of sulfonamides in two of the three treatments. Furthermore, soil management such as tillage and cropping affected the time between application and breakthrough of sulfonamides and the intra-annual distribution of sulfonamide loads in leachates. Although the total sulfonamide leaching loads were low, the concentrations exceeded the limit value of the European Commission of 0.1 µg biocide L−1 in drinking water in more than 50% of all samples. Furthermore, the medium-term mean concentration of the sulfonamides ranged from 0.08 and 4.00 µg L−1, which was above the limit value of the European Commission in 91 out of 158 samples. Therefore, sulfonamides applied to soils in liquid manure under common agricultural practice may cause environmental and health risks which call for a setting up of more long-term studies on the fate of antibiotics.

Background, aim and scope Pulp and paper mills generate a plethora of pollutants depending upon the type of pulping process. Efforts to mitigate the environmental impact of such effluents have been made by developing more effective biological treatment systems in terms of biochemical oxygen demand, chemical oxygen demand, colour and lignin content. This study is the first that reports an evaluation of the effects of a tertiary treatment by fungi (Pleurotus sajor caju, Trametes versicolor and Phanerochaete chrysosporium and Rhizopus oryzae) on individual organic compounds of a Eucalyptus globulus bleached kraft pulp and paper mill final effluent after secondary treatment (final effluent). Material and methods The tertiary treatment with P. sajor caju, T. versicolor and P. chrysosporium and R. oryzae was performed in batch reactors, which were inoculated with separate fungi species and monitored throughout the incubation period. Samples from effluent after secondary and after tertiary treatment with fungi were analysed for both absorbance and organic compounds. The samples were extracted for organic compounds using solid-phase extraction (SPE) and analysed by gas chromatography-mass spectrometry (GC/MS). The efficiencies of the SPE procedure was evaluated by recovery tests. Results A total of 38 compounds (carboxylic acids, fatty alcohols, phenolic compounds and sterols) were identified and quantified in the E. globulus bleached kraft pulp mill final effluent after secondary treatment. Recoveries from the extraction procedure were between 98.2% and 99.9%. The four fungi species showed an adequate capacity to remove organic compounds and colour. Tertiary treatment with R. oryzae was able to remove 99% of organic compounds and to reduce absorbance on 47% (270 nm) and 74% (465 nm). P. sajor caju, T. versicolor and P. chrysosporium were able to remove 97%, 92% and 99% of organic compounds, respectively, and reduce 18% (270 nm) to 77% (465 nm), 39% (270 nm) to 58% (465 nm) and 31% (270 nm) to 10% (465 nm) of absorbance, respectively. Discussion The wide variety of organic compounds found in the final effluent must be due to the degradation of E. globulus wood in pulp and paper mill. The concentrations of organic compounds in the final effluent of E. globulus bleached kraft pulp mill were in residual levels maybe due to the secondary treatment. The recovery tests showed the effectiveness of the extraction procedure, and no losses of analyte were suspected in the analytical determinations. Lignin derivatives such as vanilic acid, syringic acid, guaiacol, syringol and phloroglucinol were totally removed by R. oryzae, but the 47% absorbance reduction obtained at 270 nm suggests that these species were not able to complete degradation of lignin macromolecular compounds. Conclusions The organic compounds (carboxylic acids, fatty alcohols, phenolic compounds and sterols) were removed more efficiently by tertiary treatment with R. oryzae or P. chrysosporium, followed by P. sajor caju and T. versicolor. Regarding the removal of both colour and organic compounds, the tertiary treatment with R. oryzae was the most efficient. Recommendations and perspectives In order to reduce the deleterious impacts of paper mill effluents, efforts have been made to develop more effective advanced tertiary treatments. This study may serve as a basis of characterisation, in terms of organic compounds of E. globulus bleached kraft pulp mill final effluent after secondary treatment and as an effort to understand the effects of tertiary treatments with fungi on low concentrations of organic compounds from biological secondary treatment.

Pulp and paper mills generate a plethora of pollutants depending upon the type of pulping process. Efforts to mitigate the environmental impact of such effluents have been made by developing more effective biological treatment systems in terms of biochemical oxygen demand, chemical oxygen demand, colour and lignin content. This study is the first that reports an evaluation of the effects of a tertiary treatment by fungi (Pleurotus sajor caju, Trametes versicolor and Phanerochaete chrysosporium and Rhizopus oryzae) on individual organic compounds of a Eucalyptus globulus bleached kraft pulp and paper mill final effluent after secondary treatment (final effluent). The tertiary treatment with P. sajor caju, T. versicolor and P. chrysosporium and R. oryzae was performed in batch reactors, which were inoculated with separate fungi species and monitored throughout the incubation period. Samples from effluent after secondary and after tertiary treatment with fungi were analysed for both absorbance and organic compounds. The samples were extracted for organic compounds using solid-phase extraction (SPE) and analysed by gas chromatography-mass spectrometry (GC/MS). The efficiencies of the SPE procedure was evaluated by recovery tests. A total of 38 compounds (carboxylic acids, fatty alcohols, phenolic compounds and sterols) were identified and quantified in the E. globulus bleached kraft pulp mill final effluent after secondary treatment. Recoveries from the extraction procedure were between 98.2% and 99.9%. The four fungi species showed an adequate capacity to remove organic compounds and colour. Tertiary treatment with R. oryzae was able to remove 99% of organic compounds and to reduce absorbance on 47% (270 nm) and 74% (465 nm). P. sajor caju, T. versicolor and P. chrysosporium were able to remove 97%, 92% and 99% of organic compounds, respectively, and reduce 18% (270 nm) to 77% (465 nm), 39% (270 nm) to 58% (465 nm) and 31% (270 nm) to 10% (465 nm) of absorbance, respectively. The wide variety of organic compounds found in the final effluent must be due to the degradation of E. globulus wood in pulp and paper mill. The concentrations of organic compounds in the final effluent of E. globulus bleached kraft pulp mill were in residual levels maybe due to the secondary treatment. The recovery tests showed the effectiveness of the extraction procedure, and no losses of analyte were suspected in the analytical determinations. Lignin derivatives such as vanilic acid, syringic acid, guaiacol, syringol and phloroglucinol were totally removed by R. oryzae, but the 47% absorbance reduction obtained at 270 nm suggests that these species were not able to complete degradation of lignin macromolecular compounds. The organic compounds (carboxylic acids, fatty alcohols, phenolic compounds and sterols) were removed more efficiently by tertiary treatment with R. oryzae or P. chrysosporium, followed by P. sajor caju and T. versicolor. Regarding the removal of both colour and organic compounds, the tertiary treatment with R. oryzae was the most efficient. In order to reduce the deleterious impacts of paper mill effluents, efforts have been made to develop more effective advanced tertiary treatments. This study may serve as a basis of characterisation, in terms of organic compounds of E. globulus bleached kraft pulp mill final effluent after secondary treatment and as an effort to understand the effects of tertiary treatments with fungi on low concentrations of organic compounds from biological secondary treatment. | published