Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1 + QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth. Kinetically defined metal fractions mimic mobility aspects of heavy metals.

The proper use of bioaccumulation in the assessment of environmental quality involves accounting for chemical fluxes in organisms. Cadmium (Cd) accumulation kinetics in a soil-plant-snail food chain were therefore investigated in the field under different soil contamination (from 0 to 40 mg kg-1), soil pH (6 and 7) and season. Allowing for an accurate and sensitive assessment of Cd transfer to snails, toxicokinetics appears an interesting tool in the improvement of risk assessment procedures and a way to quantify metal bioavailability for a defined target. On the basis of uptake fluxes, snails proved to be sensitive enough to distinguish moderate soil contaminations. The soil pH did not appear, in the range studied, as a modulating parameter of the Cd transfer from soil to snail whereas the season, by influencing the snail mass, may modify the internal concentrations. The present data specifying a time integrated assessment of environmental factors on metal bioavailability and transfer to terrestrial snails should ensure their rational use in environmental biomonitoring. Toxicokinetics and uptake fluxes can be used to describe the environment contamination by Cd, its bioavailability and transfer to Helix aspersa snails in the field.

Expansion of aquaculture has increased concern over its environmental impact. The composition of effluents from intensive aquaculture is well documented, but few data on extensive aquaculture are available. During 12 draining operations, 523 water samples were collected downstream from six extensively-managed fishponds in northeastern France. Study ponds had surface areas of 2-620 ha and were managed for production of Cyprinids and Percids. Concentrations of total suspended solids, total phosphorus, and Kjeldahl nitrogen in effluents from the ponds were greatest during the final stage of draining. Loads of phosphorus were higher than those reported for effluents of more intensive aquaculture ponds in the USA, but the source of the potential pollutants was catchments and sediment rather than feeds and fertilizer. It will be necessary to reduce the water drawdown rate during the fishing stage and possibly implement other best management practices to prevent the TSS concentration from exceeding 1 g/L. Effluent phosphorus loads were higher than those reported for more intensive aquaculture ponds, but the pollutant source was catchments rather than feeds and fertilizers.

To investigate the consequences of acidification and metal accumulation on the biology of aquatic bryophytes, the acid-tolerant liverwort Scapania undulata (L.) Dum. and the acid-sensitive moss Rhynchostegium riparioides (Hedw.) Cardot were transplanted from one stream to two other streams of differing acidity (pH 5.20 and 6.38). The bryophytes were collected in a circumneutral (pH 6.57) stream in the Vosges Mountains. Metal accumulation was semi-quantitatively measured in shoots by energy dispersive TEM X-ray spectroscopy (EDXS). After 1 month, the two species remained green without alteration signs. Although no marked ultrastructural damage was observed in either species, some cells seemed to be necrotic, with flattened chloroplasts, in R. riparioides. Lipid droplet accumulation was observed in some leaf cells of S.undulata when transplanted to the most acidic stream. Metal was mostly localised in the cell wall, and was only sometimes detected in small vacuoles. Under acidic conditions, R. riparioides showed the highest relative amount of Al and the lowest amount of Fe, whereas the acid-tolerant bryophyte species S. undulata contained more Fe and less Al. The capability to limit the uptake of metals into the cytoplasm varies according to the bryophyte species. This could be an explanation of the tolerance of S. undulata to acidification.

The contamination of 27 urban topsoils has been assessed around two lead and zinc smelters (Metaleurop Nord and Umicore) in the North of France. Eighteen trace elements have been analysed (Ag, As, Bi, Cd, Co, Cr, Cu, Hg, In, Ni, Pb, Sb, Se, Sn, Tl, Th, U and Zn). The investigation included the study of the vertical distribution of Cd, Pb and Zn as indicators of pollution. It was shown that Cd, In, Pb, Sb and Zn were major pollutants followed in lesser quantities by Ag, Bi, Cu and Hg. In addition, As, Ni, Se, Sn and Tl were present at levels slightly higher than regional agricultural values. The other elements (Co, Cr, Th and U) were at endogenous levels. The observations have highlighted the strong heterogeneity of the physico-chemical parameters of urban soils and the existence of heavy contamination of the under layers by Cd, Pb and Zn. A potential transfer of metals from the topsoil to the deeper layers and especially Cd and Zn, is not excluded. Indeed the soil rework is not the only factor explaining contamination level of the deeper layers of the studied soils. The comparison of the studied element concentrations in urban soils with nearby local agricultural values shows that the dust emission originating from the Metaleurop and Umicore smelters were not the only source of contamination. Thus a large contamination of the studied urban soils by Sb and In could be explained by domestic combustion of coal for heating.

PM₁₀ particles were collected over three sites in France. The first one, Montagney was a rural site that was considered as a reference site. The second site Saclay, close to a highway, was used to study the influence of the traffic. The third site was Dunkerque, one of the most industrial areas in France for the production of steel, aluminium and petroleum refinement. More than 50 element concentrations were determined by instrumental neutron activation analysis and inductively coupled plasma-mass spectrometry. Comparisons between Saclay and Montagney shown that some elements, considered as crustal elements had similar concentration variations and weak (close to 1) enrichment factors. Elements with enrichment factors higher than 10 shown in Montagney correlated variations, with a Winter maximum, that should be due to Winter heating sources. Over Saclay, most of elements with high enrichment factors were attributed to the dense traffic of the highway. This is particularly true for Mn, Fe, Zn, Ba, Sb, Cu. Some additional elements correlated also, without a particular origin that can be ascertained. In Dunkerque, the most important industry is steel production. Correlation studies shown that Tl, Cs, Ba, Ag, Cu, Rb, Se, Mn, Pb concentration variations were closely associated to the Fe concentration variations. The second polluting industry is aluminium production. Correlation studies allowed to associate Ni, Y, Co, V, rare earth elements, Ti, Sr, Th, U, Ca, Sc, concentration variations to the aluminium concentration variations. A third important industry is petroleum refinement. The only element observed here and that is suspected to be emitted more specifically is La, used in cracking processes. An important enrichment of La with respect to Ce is observed. A strong decrease of the ratio Cl/Na was observed over the three sites, between the beginning of the experiment in Autumn 2005, and its end in Spring 2006. This was attributed to a release of gaseous HCl, produced by acidification of aerosols by other pollutants like NO x and SO x , that should have been oxidized to NO₂ and SO₃, then dissolved in the aerosols. The effects responsible for the loss of Cl, represents a large surface and long-term pollution event over the North of France. This work allowed a characterization of the heavy metal concentrations of the aerosol that will sustain results published in a companion paper, and that concerned the bio-accumulation of metals by Scleropodium purum, simultaneously exposed in the same sites.

The Marais Vernier is the largest freshwater wetland in the Seine Estuary in northern France. It is in a heavily urbanized and industrialized region and could be affected by atmospheric deposition and by fluvial input of contaminants in water diverted from the Seine River. To evaluate contaminant histories in the wetland and the region, sediment cores were collected from two open-water ponds in the Marais Vernier: the Grand-Mare, which was connected to the Seine by a canal from 1950 to 1996, and the Petite Mare, which has a small rural watershed. Diversions from the Seine to the Grand-Mare increased sedimentation rates but mostly resulted in low contaminant concentrations and loading rates, indicating that the sediment from the Seine was predominantly brought upstream by tidal currents from the estuary and was not from the watershed. Atmospheric sources of metals dominate inputs to the Petite Mare; however, runoff of metals from vehicle-related sources in the watershed might contribute to the upward trends in concentrations of Cr, Cu, and Zn. Estimates of atmospheric deposition using the Petite Mare core are consistent with measured deposition in the region and are mixed (similar for Hg and Pb; larger for Cd, Cu, and Zn) compared with deposition estimated from sediment cores in the northeastern United States. A local source of PAHs in the watershed of the Petite Mare is indicated by higher concentrations, higher accumulation rates, and a different, more petrogenic, PAH assemblage than in the Grand-Mare. The study illustrates how diverse sources and transport pathways can affect wetlands in industrial regions and can be evaluated using sediment cores from the wetland ponds.

The aim of this in situ study was to investigate the fatty acid (FA) composition and content in roots and shoots of Lolium perenne and Trifolium repens, grown under heavy metal stress (Cd, Pb, Zn). The composition of FA was quite similar for the two plants and the two organs; main FA were palmitic acid (C16:0), oleic acid (C18:1), linoleic acid (C18:2) and linolenic acid (C18:3). For both plants, the major FA that characterized the roots was C18:2 whereas C18:3 was the prominent FA in shoots. For the first sampling (S1), in the roots of L. perenne and T. repens, polyunsaturated fatty acids (PUFA) were affected by metal contamination while, in the second sampling (S2), PUFA were affected in the shoots of the two plants. This alteration of PUFA was well correlated with the bioaccumulation factor of metals which decreased in roots and increased in shoots with the time. Moreover, a positive correlation was found between the PUFA decrease and the malondialdehyde (MDA) content, indicating the occurrence of a lipid peroxidation induced by the metal stress.