Historical perspective of heavy metals contamination (Cd, Cr, Cu, Hg, Pb, Zn) in the Seine River basin (France) following a DPSIR approach (1950-2005).

The Driver-Pressures-State-Impact-Response approach is applied to heavy metals in the Seine River catchment (65,000 km(2); 14 million people of which 10 million are aggregated within Paris megacity; 30% of French industrial and agricultural production). The contamination pattern at river mouth is established on the particulate material at different time scales: 1930-2000 for floodplain cores, 1980-2003 for suspended particulate matter (SPM) and bed-sediments, 1994-2003 for atmospheric fallout and annual flood deposits. The Seine has been among the most contaminated catchments with maximum contents recorded at 130 mg kg(-1) for Cd, 24 for Hg, 558 for Pb, 1620 for Zn, 347 for Cu, 275 for Cr and 150 for Ni. Today, the average levels for Cd (1.8 mg kg(-1)), Hg (1.08), Pb (108), Zn (370), Cu (99), Cr (123) and Ni (31) are much lower but still in the upper 90% of the global scale distribution (Cr and Ni excepted) and well above the natural background values determined on pre-historical deposits. All metal contents have decreased at least since 1955/65, well before metal emission regulations that started in the mid 1970's and the metal monitoring in the catchment that started in the early 1980's. In the last 20 y, major criteria changes for the management of contaminated particulates (treated urban sludge, agricultural soils, dredged sediments) have occurred. In the mid 1990's, there was a complete shift in the contamination assessment scales, from sediment management and water usage criteria to the good ecological state, now required by the 2000 European Directive. When comparing excess metal outputs, associated to river SPM, to the average metal demand within the catchment from 1950 to 2000, the leakage ratios decrease exponentially from 1950 to 2000 for Cd, Cr, Cu, Pb and Zn, meanwhile, a general increase of the demand is observed: the rate of recycling and/or treatment of metals within the anthroposphere has been improved ten-fold. Hg environmental trajectory is very specific: there is a marked decontamination from 1970 to 2000, but the leakage ratio remains very high (10 to 20%) during this period. Drivers and Pressures are poorly known prior to 1985; State evolution since 1935 has been reconstructed from flood plain cores analysis; Impacts were maximum between 1950 and 1970 but remained unknown due to analytical limitation and lack of awareness. Some Responses are lagging 10 y behind monitoring and have much evolved in the past 10 y.

Critical budget of metal sources and pathways in the Seine River basin (1994-2003) for Cd, Cr, Cu, Hg, Ni, Pb and Zn.

River basin metal pollution originates from heavy industries (plating, automobile) and from urban sources (Paris conurbation: 2740 km(2), 9.47 million inhabitants). The natural sources of metal have been found to be limited due to sedimentary nature of this catchment and to the very low river sediment transport (10 t km(-2) y(-1)). Several types of data have been collected to build the metal budget within the whole Seine River basin: field surveys, economical statistics and environmental models. Environmental contamination and related fluxes have been measured on atmospheric fallout, rural streams particles, and Seine River particles upstream and downstream of Paris and at river mouth. Metal pathways and budgets have been set up for (i) a typical cultivated area, (ii) a Paris combined sewer system, (iii) Paris conurbation and (iv) the whole catchment metal retention effect in floodplain and dredged material. Metal fluxes to the estuary have been decomposed into natural, urban domestic and other sources. The latter are within 1-2 orders of magnitude larger than waste water fluxes directly released into rivers according to an industrial census. These fluxes have been further compared to the annual use (1994-2003) of these metals. Metal excess fluxes exported by the river are now a marginal leak of metal inputs to the catchment (i.e. "raw" metals, metals in goods, atmospheric fallout), generally from 0.2 to 5 per thousand. However, due to the very limited dilution power in this basin, the contamination of particles is still relatively high. The Seine River basin is gradually storing metals, mostly in manufactured products used in construction, but also in various waste dumps, industrial soils, agricultural and flood plain soils.

Decrease of atmospheric deposition of heavy metals in an urban area from 1994 to 2002 (Paris, France).

Total atmospheric deposition, i.e. both wet and dry ones, was sampled during three different sampling periods between 1994 and 2002. The aim of this study is to determine the temporal variation of the atmospheric deposition fluxes of four heavy metals (Cd, Cu, Pb and Zn) in an urban area (Paris region, France). The global pattern shows a decrease of the fluxes for most of elements during this period. Indeed, the atmospheric deposition fluxes measured in 2001-2002 were lower than those measured during the 1994-1997 period by factors reaching 16, 2.5, 4 and 7.5 at Créteil and 7, 1, 6 and 4.5 at Chatou for Cd, Cu, Pb and Zn, respectively. At the Paris site, the decreasing factors were 2.5 and 3 for Cd and Pb, respectively while Cu and Zn fluxes were nearly similar during the whole studied period.

Sources, distribution and variability of hydrocarbons and metals in atmospheric deposition in an urban area (Paris, France).

Total atmospheric deposition, i.e., both wet and dry deposition, was sampled during 11 months in the "Ile-de-France" region, France. Monthly fluxes of aliphatic hydrocarbons (AHs), polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs) were studied at three representative sites (two urbanised and one semiurban). A combination of spatial and temporal variability of total fluxes and pollutant fingerprints allows a better understanding of atmospheric pollutant dynamics over this region. In the whole studied area, aggregated total atmospheric fluxes of AHs, PAHs and HMs range from 19 to 33 mg m(-2) y(-1), 99 to 161 mug m(-2) y(-1) and 48 to 103 mg m(-2) y(-1), respectively. The highest values are observed in Paris centre, reflecting the importance of the urban centre as a source of pollutants, with a decline in many atmospheric deposits when moving away from urban areas. The seasonal distribution of these pollutants suggests the impact of residential heating on urban atmospheric deposition of hydrocarbons and the increase of dust loads containing HMs during summer. The qualitative study performed on atmospheric deposition data highlights the main sources of pollutants. Aliphatic fingerprints suggest a marked contribution of biogenic inputs to aliphatic contamination in the whole Ile-de-France region and slight petroleum inputs in urban areas. Aromatic fingerprints, characterised by the great predominance of phenanthrene, fluoranthene and pyrene, associated with some specific ratio values, suggest the mixture of petrogenic and pyrolytic contaminations of atmospheric deposition in the whole "Ile-de-France" region. HM distribution shows the presence of anthropogenic sources of Al and Fe in this area and the stationary sources (incinerators and plants) as a significant source of Si, S and Sb in the urban atmosphere. Moreover, a pollutant mix phenomenon, occurring in such an urban atmosphere, shows a significant influence on atmospheric deposition at the semiurban site.

Trace metal determination in total atmospheric deposition in rural and urban areas.

The wet, dry and total atmospheric depositions of some metals (Al, Cd, Cr, Cu, Fe, Na, Pb and Zn) were sampled at two sites and atmospheric fallout fluxes were determined for these locations. This work, led by two different research groups, allowed to reach two main goals: to define a simple analytical procedure to secure accurate shipboard sampling and analysis of atmospheric deposition, and to assess anthropogenic impacts of heavy metals to the environment. The first step about the validation step showed that the prevalent deposition type was dry deposition which represents 40, 60 and 80% for Cd, Cu and Pb, respectively. This prevalence of dry deposition in total atmospheric fallout supported the necessity of funnel wall rinsing which contains 30, 50 and 40% of collected Cd, Cu and Pb, respectively. Moreover, the reproducibility of atmospheric deposition collection was determined. The second step was performed by comparing two sampling sites. A rural sampling site, situated in Morvan's regional park (250 km south-east of Paris), was chosen for its isolation from any local and regional contamination sources. Fluxes obtained in this area were compared with those obtained at an urban site (Créteil, suburb of Paris) allowing comparison between urban and rural areas and demonstrating the impact of anthropogenic activities on atmospheric deposition of Cr, Cu and Pb.

Sensitive detection of organophosphorus pesticides using a needle type amperometric acetylcholinesterase-based bioelectrode. Thiocholine electrochemistry and immobilised enzyme inhibition.

An acetylcholinesterase (AChE) based amperometric bioelectrode for a selective detection of low concentrations of organophosphorus pesticides has been developed. The amperometric needle type bioelectrode consists of a bare cavity in a PTFE isolated Pt-Ir wire, where the AChE was entrapped into a photopolymerised polymer of polyvinyl alcohol bearing styrylpyridinium groups (PVA-SbQ). Cyclic voltammetry, performed at Pt and AChE/Pt disk electrodes, confirmed the irreversible, monoelectronic thiocholine oxidation process and showed that a working potential of +0.410 V vs. Ag/AgCl, KCl(sat) was suitable for a selective and sensitive amperometric detection of thiocholine. The acetylthiocholine detection under enzyme kinetic control was found in the range of 0.01-0.3 U cm(-2) of immobilised AChE. The detection limit, calculated for an inhibition ratio of 10%, was found to reach 5 microM for dipterex and 0.4 microM for paraoxon. A kinetic analysis of the AChE-pesticide interaction process using Hanes-Woolf or Lineweaver-Burk linearisations and secondary plots allowed identification of the immobilised enzyme inhibition process as a mixed one (non/uncompetitive) for both dipterex and paraoxon. The deviation from classical Michaelis Menten kinetics induced from the studied pesticides was evaluated using Hill plots.

Determination of aliphatic hydrocarbons in urban runoff samples from the "Le Marais" experimental catchment in Paris centre.

Aliphatic hydrocarbons were assessed in runoff and waste waters from an urban catchment located in Paris. Runoff were sampled from different types of urban surfaces (11 roofs representing four different covering materials, two courtyards and six streets). Waste water samples were collected at the catchment outlet during dry and wet weather periods as well. This paper gives an overview of the results on the concentration and distribution points of view for both the particulate and the dissolved phases. Results were discussed on the basis of the median. Accordingly, the temporal variability was taken into account. Thus, the concentration medians ranged from 345 to 827, from 297 to 790, and from 393 to 1,359 microg L(-1) in the roof, courtyard and street samples, respectively. The levels found at the catchment outlet during dry and wet weather periods were of the same order of magnitude, i.e. 700 microgL(-1). The particulate phase represented 85% of the total aliphatic hydrocarbon content whatever the sample.