Polycyclic Aromatic Hydrocarbons (PAHs) molecular diagnostic ratios (MDRs) are unitless concentration ratios of pair-PAHs with the same molecular weight (MW); MDRs have long been used as a tool for PAHs source identification purposes. In the present paper, the efficiency of the MDR methodology is evaluated through the use of a multimedia fate model, the calculation of characteristic travel distances (CTD) and the estimation of air concentrations for individual PAHs as a function of distance from an initial point source. The results show that PAHs with the same MW are sometimes characterized by substantially different CTDs and therefore their air concentrations and hence MDRs are predicted to change as the distance from the original source increases. From the assessed pair-PAHs, the biggest CTD difference is seen for Fluoranthene (107 km) vs. Pyrene (26 km). This study provides a strong indication that MDRs are of limited use as a source identification tool.

Polycyclic Aromatic Hydrocarbons (PAHs) molecular diagnostic ratios (MDRs) are unitless concentration ratios of pair-PAHs with the same molecular weight (MW); MDRs have long been used as a tool for PAHs source identification purposes. In the present paper, the efficiency of the MDR methodology is evaluated through the use of a multimedia fate model, the calculation of characteristic travel distances (CTD) and the estimation of air concentrations for individual PAHs as a function of distance from an initial point source. The results show that PAHs with the same MW are sometimes characterized by substantially different CTDs and therefore their air concentrations and hence MDRs are predicted to change as the distance from the original source increases. From the assessed pair-PAHs, the biggest CTD difference is seen for Fluoranthene (107 km) vs. Pyrene (26 km). This study provides a strong indication that MDRs are of limited use as a source identification tool. | acceptedVersion

We examined copper (Cu) absorption, distribution and toxicity and the role of a silicon (Si) supplementation in the bamboo Phyllostachys fastuosa. Bamboos were maintained in hydroponics for 4 months and submitted to two different Cu (1.5 and 100 μm Cu2+) and Si (0 and 1.1 mM) concentrations. Cu and Si partitioning and Cu speciation were investigated by chemical analysis, microscopic and spectroscopic techniques. Copper was present as Cu(I) and Cu(II) depending on plant parts. Bamboo mainly coped with high Cu exposure by: (i) high Cu sequestration in the root (ii) Cu(II) binding to amino and carboxyl ligands in roots, and (iii) Cu(I) complexation with both organic and inorganic sulfur ligands in stems and leaves. Silicon supplementation decreased the visible damage induced by high Cu exposure and modified Cu speciation in the leaves where a higher proportion of Cu was present as inorganic Cu(I)S compounds, which may be less toxic.

We examined copper (Cu) absorption, distribution and toxicity and the role of a silicon (Si) supplementation in the bamboo Phyllostachys fastuosa. Bamboos were maintained in hydroponics for 4 months and submitted to two different Cu (1.5 and 100 mm Cu2þ) and Si (0 and 1.1 mM) concentrations. Cu and Si partitioning and Cu speciation were investigated by chemical analysis, microscopic and spectroscopic techniques. Copper was present as Cu(I) and Cu(II) depending on plant parts. Bamboo mainly coped with high Cu exposure by: (i) high Cu sequestration in the root (ii) Cu(II) binding to amino and carboxyl ligands in roots, and (iii) Cu(I) complexation with both organic and inorganic sulfur ligands in stems and leaves. Silicon supplementation decreased the visible damage induced by high Cu exposure and modified Cu speciation in the leaves where a higher proportion of Cu was present as inorganic Cu(I)S compounds, which may be less toxic. (Résumé d'auteur)

Intra-specific variability of root biomass production (RP) of six rooted macrophytes, i.e. Juncus effusus, Phragmites australis, Schoenoplectus lacustris, Typha latifolia, Phalaris arundinacea, and Iris pseudacorus grown from clones, in response to Cu exposure was investigated. Root biomass production varied widely for all these macrophytes in control conditions (0.08 μM) according to the sampling site. Root biomass production of T. latifolia and I. pseudacorus in the 2.5–25 μM Cu range depended on the sampling location but not on the Cu dose in the growth medium. For P. australis, J. effusus, S. lacustris, and P. arundinacea, an intra-specific variability of RP depending on both the sampling location and the Cu-dose was evidenced. This intra-specific variability of RP depending on the sampling location and of Cu-tolerance for these last four species suggests that Cu constitutive tolerance for all rooted macrophytes is not a species-wide trait but it exhibits variability for some species.

Intra-specific variability of root biomass production (RP) of six rooted macrophytes, i.e. Juncus effusus, Phragmites australis, Schoenoplectus lacustris, Typha latifolia, Phalaris arundinacea, and Iris pseudacorus grown from clones, in response to Cu exposure was investigated. Root biomass production varied widely for all these macrophytes in control conditions (0.08 μM) according to the sampling site. Root biomass production of T. latifolia and I. pseudacorus in the 2.5–25 μM Cu range depended on the sampling location but not on the Cu dose in the growth medium. For P. australis, J. effusus, S. lacustris, and P. arundinacea, an intra-specific variability of RP depending on both the sampling location and the Cu-dose was evidenced. This intra-specific variability of RP depending on the sampling location and of Cu-tolerance for these last four species suggests that Cu constitutive tolerance for all rooted macrophytes is not a species-wide trait but it exhibits variability for some species.

International audience | Intra-specific variability of root biomass production (RP) of six rooted macrophytes, i.e. Juncus effusus, Phragmites australis, Schoenoplectus lacustris, Typha latifolia, Phalaris arundinacea, and Iris pseudacorus grown from clones, in response to Cu exposure was investigated. Root biomass production varied widely for all these macrophytes in control conditions (0.08 μM) according to the sampling site. Root biomass production of T. latifolia and I. pseudacorus in the 2.5–25 μM Cu range depended on the sampling location but not on the Cu dose in the growth medium. For P. australis, J. effusus, S. lacustris, and P. arundinacea, an intra-specific variability of RP depending on both the sampling location and the Cu-dose was evidenced. This intra-specific variability of RP depending on the sampling location and of Cu-tolerance for these last four species suggests that Cu constitutive tolerance for all rooted macrophytes is not a species-wide trait but it exhibits variability for some species.

The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the 110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectroscopy. After two weeks of ageing the E-values for Ag decreased by 20–90% with a further decrease of 10–40% after six months. The overall decrease in labile Ag for all soils after the 6 month ageing period was 50–100%. The ageing was more rapid and pronounced in the alkaline soils. XANES results for Ag in soils indicated that for the majority of soils the added Ag+ was reduced to metallic Ag over time, and associations with Fe-oxohydroxides and reduced S groups in organic matter also decreased Ag lability. Strong positive correlations were found between metallic Ag and non-labile Ag and between organic carbon and Ag bonded with S species.

Abstract not available | Lara Settimio, Mike J. McLaughlin, Jason K. Kirby, Kate A. Langdon, Enzo Lombi, Erica Donner, Kirk G. Scheckel

The influence of earthworm activity on soil-to-plant metal transfer was studied by carrying out six weeks mesocosms experiments with or without lettuce and/or earthworms in soil with a gradient of metal concentrations due to particles fallouts. Soil characteristics, metal concentrations in lettuce and earthworms were measured and soil porosity in the mesocosms was determined. Earthworms increased the soil pH, macroporosity and soil organic matter content due to the burying of wheat straw provided as food. Earthworm activities increased the metals concentrations in lettuce leaves. Pb and Cd concentrations in lettuce leaves can increase up to 46% with earthworm activities … These results and the low correlation between estimated by CaCl2 and EDTA and measured pollutant phytoavailability suggest that earthworm bioturbation was the main cause of the increase. Bioturbation could affect the proximity of pollutants to the roots and soil organic matter.

International audience | The influence of earthworm activity on soil-to-plant metal transfer was studied by carrying out six weeks mesocosms experiments with or without lettuce and/or earthworms in soil with a gradient of metal concentrations due to particles fallouts. Soil characteristics, metal concentrations in lettuce and earthworms were measured and soil porosity in the mesocosms was determined. Earthworms increased the soil pH, macroporosity and soil organic matter content due to the burying of wheat straw provided as food. Earthworm activities increased the metals concentrations in lettuce leaves. Pb and Cd concentrations in lettuce leaves can increase up to 46% with earthworm activities ... These results and the low correlation between estimated by CaCl2 and EDTA and measured pollutant phytoavailability suggest that earthworm bioturbation was the main cause of the increase. Bioturbation could affect the proximity of pollutants to the roots and soil organic matter.

In the Mezquital valley, untreated wastewater (45 m(3) s(-1)) from Mexico City is used for the irrigation of around 900 km(2) of agricultural soil. High concentrations of metals including methylmercury (3.8+/-2.5 ng l(-1)) and lead (0.16+/-0.05 mg l(-1)) were measured in anoxic wastewater canals. Downstream, dissolved, and particulate polymetallic (Hg, Pb, Cr.) concentrations decreased by factors 10 to 1,000 in the Tula River (which received a mix of fresh and wastewater) due to the dilution and oxidation of surface water, and to the decrease of contaminants concentration in wastewater downstream irrigated soils. However, dissolved and particulate methylmercury concentrations (0.06 to 0.33 ng l(-1) and 1.6 to 4.5 g kg(-1), respectively) remained elevated in comparison to other natural hydrosystems. The monitoring of an irrigation event and the distribution of metals in a soil profile irrigated for more than 80 years showed that metals were retained in the draining tilled layer. The oxic conditions and slightly acidic pH (similar to 6.5) in this layer were found favorable for metal adsorption and co-precipitation with redox-sensitive elements (Fe, Mn) and suggestively for mercury demethylation. In the downstream Tula River and groundwater, almost all metallic concentrations remained below guideline thresholds. Only, dissolved As and Pb concentrations remained two to five times above thresholds for drinking water, highlighting a potential health risk for approximately 500,000 people who use groundwater as water supply.

In the Mezquital valley, untreated wastewater (45 m³ s⁻¹) from Mexico City is used for the irrigation of around 900 km²of agricultural soil. High concentrations of metals including methylmercury (3.8 ± 2.5 ng l⁻¹) and lead (0.16 ± 0.05 mg l⁻¹) were measured in anoxic wastewater canals. Downstream, dissolved, and particulate polymetallic (Hg, Pb, Cr…) concentrations decreased by factors 10 to 1,000 in the Tula River (which received a mix of fresh and wastewater) due to the dilution and oxidation of surface water, and to the decrease of contaminants concentration in wastewater downstream irrigated soils. However, dissolved and particulate methylmercury concentrations (0.06 to 0.33 ng l⁻¹and 1.6 to 4.5 μg kg⁻¹, respectively) remained elevated in comparison to other natural hydrosystems. The monitoring of an irrigation event and the distribution of metals in a soil profile irrigated for more than 80 years showed that metals were retained in the draining tilled layer. The oxic conditions and slightly acidic pH (~6.5) in this layer were found favorable for metal adsorption and co-precipitation with redox-sensitive elements (Fe, Mn) and suggestively for mercury demethylation. In the downstream Tula River and groundwater, almost all metallic concentrations remained below guideline thresholds. Only, dissolved As and Pb concentrations remained two to five times above thresholds for drinking water, highlighting a potential health risk for approximately 500,000 people who use groundwater as water supply.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA [TR2_IRSTEA]TED | Five estrogenic hormones (unconjugated+conjugated fractions) and 10 beta blockers were analyzed in three wastewater treatment plant (WWTP) effluents and receiving river waters in the area of Lyon, France. In the different samples, only two estrogens were quantified: estrone and estriol. Some beta blockers, such as atenolol, acebutolol, and sotalol, were almost always quantified, but others, e.g., betaxolol, nadolol, and oxprenolol were rarely quantified. Concentrations measured in river waters were in the nanogram per liter range for estrogens and between 0.3 and 210 ng/L for beta blockers depending on the substance and the distance from theWWTP outfall. The impact of the WWTP on the receiving rivers was studied and showed a clear increase in concentrations near the WWTP outfall. For estrogens, the persistence in surface waters was not evaluated given the low concentrations levels (around 1 ng/L). For beta blockers, concentrations measured downstream of the WWTP outfall were up to 16 times higher than those measured upstream. Also, the persistence of metoprolol, nadolol, and propranolol was noted even 2 km downstream of the WWTP outfall. The comparison of beta blocker fingerprints in the samples collected in effluent and in the river also showed the impact of WWTP outfall on surface waters. Finally, a tentative environmental risk evaluation was performed on 15 sites by calculating the ratio of receiving water concentrations to predicted non-effect concentrations (PNEC). For estrogens, a total PNEC of 5 ng/L was considered and these substances were not linked to any potential environmental risk (only one site showed an environmental risk ratio above 1). Unfortunately, few PNECs are available and risk evaluation was only possible for 4 of the 10 beta blockers studied: acebutolol, atenolol, metoprolol, and propranolol. Only propranolol presented a ratio near or above 1, showing a possible environmental risk for 4 receiving waters out of 15.

Five estrogenic hormones (unconjugated + conjugated fractions) and 10 beta blockers were analyzed in three wastewater treatment plant (WWTP) effluents and receiving river waters in the area of Lyon, France. In the different samples, only two estrogens were quantified: estrone and estriol. Some beta blockers, such as atenolol, acebutolol, and sotalol, were almost always quantified, but others, e.g., betaxolol, nadolol, and oxprenolol were rarely quantified. Concentrations measured in river waters were in the nanogram per liter range for estrogens and between 0.3 and 210 ng/L for beta blockers depending on the substance and the distance from the WWTP outfall. The impact of the WWTP on the receiving rivers was studied and showed a clear increase in concentrations near the WWTP outfall. For estrogens, the persistence in surface waters was not evaluated given the low concentrations levels (around 1 ng/L). For beta blockers, concentrations measured downstream of the WWTP outfall were up to 16 times higher than those measured upstream. Also, the persistence of metoprolol, nadolol, and propranolol was noted even 2 km downstream of the WWTP outfall. The comparison of beta blocker fingerprints in the samples collected in effluent and in the river also showed the impact of WWTP outfall on surface waters. Finally, a tentative environmental risk evaluation was performed on 15 sites by calculating the ratio of receiving water concentrations to predicted non-effect concentrations (PNEC). For estrogens, a total PNEC of 5 ng/L was considered and these substances were not linked to any potential environmental risk (only one site showed an environmental risk ratio above 1). Unfortunately, few PNECs are available and risk evaluation was only possible for 4 of the 10 beta blockers studied: acebutolol, atenolol, metoprolol, and propranolol. Only propranolol presented a ratio near or above 1, showing a possible environmental risk for 4 receiving waters out of 15.

7th International PCB Workshop - Chemical mixtures in a complex world, Arcachon, FRANCE, MAY 27-31, 2012 | International audience | Human activities are emitting persistent organic pollutants (POPs) to the environment. These compounds have raised concerns about the risk of transfer through the food chain via animal products. They are characterized by a strong persistence in environmental matrices and a lipophilicity which may lead to their accumulation in fat tissues. In EU Regulations (no. 1881/2006, 1259/2011), maximum acceptable levels for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs), and dioxin-like or nondioxin-like polychlorinated biphenyls (PCBs) in food of animal origin have been set. Transfer rates from contaminated fodder to milk have been established: for PCBs, the rate of transfer varies from 5 to 90 % and for PCDD/Fs from 1 to 40 %. The differential transfer of the compounds towards milk is related to the hydrophobicity of the pollutants and to their metabolic susceptibility. According to numerous authors, soil is the major reservoir for POPs, and its involuntary ingestion by farm animals reared outdoors may be the main cause of animal product contamination (meat, milk, or eggs). Recent studies seem to indicate that soil is a real risk matrix in terms of transfer of pollutants to the food chain. A POP crisis management is extremely difficult, since it impacts many farmers located in the contaminated area. The question arising is to know if livestock contaminated by POPs may be decontaminated and further used for their initial purpose. Recent data demonstrate that the decontamination process appear feasible and depends on initial level of contamination or the physiological status of the animals.

Human activities are emitting persistent organic pollutants (POPs) to the environment. These compounds have raised concerns about the risk of transfer through the food chain via animal products. They are characterized by a strong persistence in environmental matrices and a lipophilicity which may lead to their accumulation in fat tissues. In EU Regulations (no. 1881/2006, 1259/2011), maximum acceptable levels for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs), and dioxin-like or nondioxin-like polychlorinated biphenyls (PCBs) in food of animal origin have been set. Transfer rates from contaminated fodder to milk have been established: for PCBs, the rate of transfer varies from 5 to 90 % and for PCDD/Fs from 1 to 40 %. The differential transfer of the compounds towards milk is related to the hydrophobicity of the pollutants and to their metabolic susceptibility. According to numerous authors, soil is the major reservoir for POPs, and its involuntary ingestion by farm animals reared outdoors may be the main cause of animal product contamination (meat, milk, or eggs). Recent studies seem to indicate that soil is a real risk matrix in terms of transfer of pollutants to the food chain. A POP crisis management is extremely difficult, since it impacts many farmers located in the contaminated area. The question arising is to know if livestock contaminated by POPs may be decontaminated and further used for their initial purpose. Recent data demonstrate that the decontamination process appear feasible and depends on initial level of contamination or the physiological status of the animals.