Determining the geochemical fingerprint of the lead fallout from the Notre-Dame de Paris fire: Lessons for a better discrimination of chemical signatures.

On 2019, the fire of Notre-Dame de Paris cathedral ("NDdP") spread an unknown amount of lead (Pb) dust from the roof of the cathedral over Paris. No data describing the geochemical fingerprint of the roof lead, as well as no particle collected during the fire, were available: a post-hoc sampling was performed. To discriminate the potential environmental impact of the fire from multiple Pb sources in Paris, it was mandatory to define unequivocally the fire dust geochemical signature. A dedicated and in hindsight geochemistry-based strategy was developed to eliminate any source of potential contamination due to sampling substrates or previously deposited dust. Radiogenic Pb isotopic signatures (206Pb/207Pb and 208Pb/206Pb ratios) and elemental ratios were determined in 23 Pb-rich samples collected inside NDdP. We determined that the dust collected on wood substrates on the first floor was most representative of fire emissions. These samples were the analyzed for the 4 Pb isotopes (204, 206, 207, 208) and the fire dust signature is characterized by ratio values of 206Pb/207Pb: 1.1669-1.1685, 208Pb/206Pb: 2.0981-2.1095, 208Pb/204Pb: 38.307-38.342, 207Pb/204Pb: 15.633-15.639 and 206Pb/204Pb: 18.242-18.275. In addition, the fire dust presents typical element-to-Pb ratio. This fingerprint was compared to the signatures of the known local Pb sources. The geochemical fingerprint of the fire is significantly different from that of the dominant urban Pb source. This will allow future evaluation of the contribution of the fire to Paris Pb pollution and of the real extent of the area affected by the Pb-containing dust plume. Moreover, the geographical origin of Pb used for the roof restauration and the spire building was identified. These findings open new ways to study the Pb sources in historical monuments for environmental impacts evaluation, as well as for historical perspectives.

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).

Lead contamination of the Seine River, France: geochemical implications of a historical perspective.

Four sediment cores collected in the Seine River basin and dated between 1916 and 2003 were analyzed for lead concentrations and isotopic composition. In all four cores, the measured Pb concentration (up to 460 mg kg(-1)) lies significantly above the natural background (27-40 mg kg(-1)), although a significant decrease (down to 75 mg kg(-1)) was observed during the second half of the 20th century which can be explained by the reduction of lead emissions. The (206)Pb/(207)Pb ratio measured in these samples indicates that the main source of Pb used in the Paris conurbation is characterized by a "Rio Tinto" signature (defined as (206)Pb/(207)Pb=1.1634 ± 0.0001). A high contribution, up to 25%, from the leaded gasoline (characterized by (206)Pb/(207)Pb=1.08 ± 0.02) is revealed in the Seine River downstream Paris, indicating that lead from the leaded gasoline is preferentially released to the river. The dominating Pb signature in the Paris conurbation that is currently sampled through incinerators fumes ((206)Pb/(207)Pb=1.1550 ± 0.0005) and waste water treatment plant ((206)Pb/(207)Pb=1.154 ± 0.002), represents a mixture of highly recycled lead from the Rio Tinto mine and lead from leaded gasoline (imprinted by the low (206)Pb/(207)Pb of the Broken Hill mine). This signature is called "urban" rather than "industrial", because it is clearly distinct from the Pb that is found in areas contaminated by heavy industry, i.e. the heavy industries located on the Oise River which used lead from European ores characterized by high (206)Pb/(207)Pb ratios (~1.18-1.19) and possibly a minor amount of North American lead ((206)Pb/(207)Pb ratios>1.20). The "urban" signature is also found in a rural area upstream of Paris in the 1970's. At the Seine River mouth in 2003, Pb with an urban signature represents 70% of the total Pb sediment content, with the 30% remaining corresponding to natural Pb.