Philippe Branchu

Three centuries of heavy metal pollution in Paris (France) recorded by urban speleothems

The first record of urban speleothems used to reconstruct the history of heavy metal pollution of shallow groundwaters is presented. Two speleothems grew during the last 300 years in an underground aqueduct in the north-eastern part of Paris. They display high Pb, Mn V, Cu, Cd and Al concentrations since 1900 due to the urbanization of the site which triggered anthropogenic contamination of the water feeding the speleothems. Surprisingly, these heavy metal concentrations are also high in the oldest part. This early pollution could come from the use of Parisian waste as fertilizers in the orchards and vineyards cultivated above the aqueduct before urbanization. Lead isotopes were measured in these carbonates as well as in lead artifacts from the 17th-18th centuries ((206)Pb/(207)Pb=1.180+/-0.003). The mean (206)Pb/(207)Pb ratio, for one of the speleothems is 1.181+/-0.003 unvarying with time. These lead signatures are close to those of coal and old lead from northern European mines, lower than the natural background signature. It confirms that the high metal concentrations found come from anthropogenic pollution. Conversely, the lead isotopic composition of the second speleothem presents two temporal trends: for the oldest levels, the mean value (1.183+/-0.003) is similar to the first speleothem. For the youngest part, a lower value (1.172+/-0.005) is recorded, evidencing the contribution of a new lead source at the beginning of the industrial revolution. Pb isotopes were also measured in recent samples from a nearby superficial site. The first sample is a recent (AD 1975+/-15 years) deposit ((206)Pb/(207)Pb=1.148+/-0.003), and the second, a thin subactual layer ((206)Pb/(207)Pb=1.181+/-0.002). These data are compatible with the adding of anthropogenic sources (leaded gasoline and industrial lead from Rio Tinto ore).

Spatial distribution of heavy metals in the surface soil of source-control stormwater infiltration devices - Inter-site comparison.

Stormwater runoff infiltration brings about some concerns regarding its potential impact on both soil and groundwater quality; besides, the fate of contaminants in source-control devices somewhat suffers from a lack of documentation. The present study was dedicated to assessing the spatial distribution of three heavy metals (copper, lead, zinc) in the surface soil of ten small-scale infiltration facilities, along with several physical parameters (soil moisture, volatile matter, variable thickness of the upper horizon). High-resolution samplings and in-situ measurements were undertaken, followed by X-ray fluorescence analyses and spatial interpolation. Highest metal accumulation was found in a relatively narrow area near the water inflow zone, from which concentrations markedly decreased with increasing distance. Maximum enrichment ratios amounted to >20 in the most contaminated sites. Heavy metal patterns give a time-integrated vision of the non-uniform infiltration fluxes, sedimentation processes and surface flow pathways within the devices. This element indicates that the lateral extent of contamination is mainly controlled by hydraulics. The evidenced spatial structure of soil concentrations restricts the area where remediation measures would be necessary in these systems, and suggests possible optimization of their hydraulic functioning towards an easier maintenance. Heterogeneous upper boundary conditions should be taken into account when studying the fate of micropollutants in infiltration facilities with either mathematical modeling or soil coring field surveys.

Urbanization impact on sulfur content of groundwater revealed by the study of urban speleothem-like deposits: Case study in Paris, France

Speleothem-like deposits that develop underground in urban areas are an archive of the environmental impact of anthropic activities that has been little studied so far. In this paper, the sulfate content in shallow groundwater from northern Paris (France) is compared with the sulfur content in two 300-year-old urban carbonate deposits that grew in a historical underground aqueduct. The present-day waters of the aqueduct have very high sulfur and calcium contents, suggesting pollution from gypsum dissolution. However, geological gypsum levels are located below the water table. Sulfur content was measured by micro-X-ray fluorescence in these very S-rich carbonate deposits (0.5 to 1% of S). A twofold S increase during the second half of the 1800s was found in both samples. These dates correspond to two major periods of urbanization above the site. We discus three possible S sources: anthropic sources (industries, fertilizers…), volcanic eruptions and input within the water through gypsum brought for urbanization above the studied site (backfill with quarry waste) since the middle of the 19th century. For the younger second half of the studied section, S input from gypsum brought during urbanization was confirmed by the study of isotopic sulfur composition (δ34S=+15.2‰ at the top). For the oldest part, several sulfur peaks could be related to early industrial activity in Paris, that caused high local air pollution, as reported in historical archives but also to historical gypsum extraction. This study provides information on the origin and timing of the very high SO42- levels measured nowadays within the shallow groundwater, thus demonstrating the interest in using carbonate deposits in urban areas as a proxy for the history of urbanization or human activities and their impact on water bodies.

Field performance of two biofiltration systems treating micropollutants from road runoff

The treatment efficiency of a vegetative filter strip and a biofiltration swale treating heavily loaded road runoff are evaluated. Concentrations measured in water drained from the two systems are compared to those in untreated road runoff collected from a reference catchment for a wide range of contaminants including organic carbon, nutrients (N and P), trace metals, and organic micropollutants (polycyclic aromatic hydrocarbons (PAH), total petroleum hydrocarbons (TPH), alkylphenols, bisphenol-A, phthalates), in both total and dissolved phases. Predominantly particulate pollutants, including Pb, Zn and PAH, were very efficiently removed (around 90%) for most events. However, poor particulate removal was observed during a winter period. Relatively few pollutants were significantly removed in the dissolved phase and observed concentration reductions tended to be lower than those of suspended solids and associated pollutants; as such, lower removals were observed for total concentrations of moderately particulate micropollutants, including bisphenol-A, alkylphenols and phthalates. In addition, some pollutants appear to be emitted from various biofilter components (filter media, drainage and lining materials), as low or negative concentration removals were observed during the first months of operation of the biofiltration swale.