Alain Veron

Tracing the transport of anthropogenic lead in the atmosphere and in soils using isotopic ratios

The isotopic composition of lead in aerosols and soils in Israel is used to characterize the sources of anthropogenic lead in the region, to ascertain the isotopic composition of natural, rock-derived lead in specific areas, and to determine rates of anthropogenic lead migration in soils. The isotopic composition of lead currently emitted from cars in Israel (206Pb207Pb = 1.115 ± 2) is controlled by alkyl-lead produced in France and Germany. In addition to petrol-lead, two more sources of anthropogenic lead can be detected in sampled aerosols: the first one has low concentrations of lead (∼4 ng/m3) and 206Pb207Pb ∼ 1.157, and is most likely lead, emitted in Turkey, that traveled across the eastern Mediterranean basin; the second type of aerosols contains a mixture of lead emitted in several countries including Turkey, Greece, and Ukraine (206Pb207Pb value of 1.155–1.160; [Pb] ∼ 20–30 ng/m3). Anthropogenic lead is more accessible for acid leaching than natural lead, therefore, it is more labile in the soil. The isotopic composition of lead in the acid-leached fraction of near-road soil profiles record the histor of alkyl-lead emission in the country. Based on changes in the isotopic composition of lead with soil depth, it is estimated that anthropogenic lead migrates into the soil at approximately 0.5 cm/y. A soil profile from a relatively remote area is less contaminated by anthropogenic lead and displays a different distribution of lead isotopic values with depth. The isotopic composition of lead suggests that natural lead in soils developed on carbonate bedrock is derived from clays, either from the rock-esidue (the clay fraction in the carbonate bedrock), or from airborne clay, but not from lead released from the carbonate fraction in the rock.

Isotopic evidence of pollutant lead sources in Northwestern France

Abstract Ratios of stable lead isotopes (204Pb, 206Pb, 207Pb, 208Pb) are used to characterize both spatial and temporal variations in anthropogenic emissions of industrial lead aerosols to the atmosphere of northwestern France. Differences in isotopic compositions of aerosols collected from a rural area (Wimereux) in the Nord-Pas de Calais region along the English Channel in 1982–1983 (206Pb/207Pb=1.108±0.005) and 1994 (206Pb/207Pb=1.148±0.003) are paralleled by similar variations in urban aerosols within France during the same period (e.g., 206Pb/207Pb=1.115±0.008 from 1981–1989 and 1.143±0.006 from 1992–1995). These results correlate well with recent findings in the Mediterranean basin (Alleman, 1997) where this radiogenicity increase is clearly associated with industrial sources other than leaded gasoline that has remained relatively constant during its phasing out (206Pb/207Pb=1.08–1.11). Here we used archived data, air mass trajectories and aerosol diameters combined with isotopic signatures to confirm this trend at a regional scale. Indeed, the main industrial signatures from lead smelting (206Pb/207Pb=1.133±0.001) and steel metallurgy (206Pb/207Pb=1.196±0.015) in northwestern France appear more radiogenic than that of leaded gasoline. The shift in isotopic compositions also conform with the systematic change in the mean size (diameter) of aerosols at Wimereux, which ranged from 0.30 to 0.61 μm in 1982–1984 and from 0.70 to 0.89 μm in 1994.

European isotopic signatures for lead in atmospheric aerosols: a source apportionment based upon 206Pb/207Pb ratios

To investigate the capability of the lead isotope signature technique to support a source apportionment study at a Continental scale, atmospheric particulate matter was collected at Cap Gris-Nez (Eastern Channel, northern France), over one year (1995-1996). Four days retrospective trajectories of air masses were available during each sampling experiment. Twenty-eight samples, for which the origin of aerosols was unambiguously determined, were selected for isotopic measurements. Considering the Enrichment Factors, EF(Crust) of lead and its size distribution, we show that lead is mostly from anthropogenic origin and mainly associated with [0.4 < diameter < 0.9 microm] particles. The extent to which various Continental sources influence the lead abundance in aerosols is exhibited by considering both the lead concentration and the origin of air masses. Lead concentration is higher by a factor of approximately seven, when air masses are derived from Continental Europe, by comparison with marine air masses. Taking into account these concentrations and the vertical movements of air masses, we compare the different isotopic compositions using a statistical non-parametric test (Kolmogorov-Smirnov). We produce evidence that, for most of the cases, air masses originating from Continental Europe exhibit a more radiogenic composition (1.134 < 206Pb/207Pb < 1.172) than air masses coming from the United Kingdom (1.106 < 206Pb/207Pb < 1.124). Generally, lead isotopic compositions in aerosols are clearly distinct from the gasoline signatures in European countries, strongly suggesting that automotive lead is no longer the major component of this metal in the air. Gasoline and industrial isotopic signatures could explain the origin of lead in our aerosol samples. A source apportionment based upon 206Pb/207Pb ratios, suggests that the difference between British (206Pb/207Pb = 1.122 +/- 0.038) and Continental (206Pb/207Pb = 1.155 +/- 0.022) signatures may be largely explained by differences in the petrol lead content of aerosols (23-62% in Great Britain vs. 10-36% in Continental Europe).

Isotopic evidence of pollutant lead transport from North America to the subtropical North Atlantic gyre

Abstract Lead isotope ratios have been measured in aerosols, seawater, and marine particles collected in 1990–1992 in the subtropical northeastern Atlantic Ocean as part of the JGOFS-EUMELI program. While the atmospheric input has unradiogenic 206 Pb 207 Pb ratios (1.158 ± 0.006), typical of the tradewinds bringing lead from European countries, all the samples collected in the water column have more radiogenic 206 Pb 207 Pb (from 1.170 to 1.196). This demonstrates that lead at the Eumeli sites contains a dominant input from American emissions, that has been circulated across the North Atlantic by the subtropical North Atlantic gyre. Using measurements in Sargasso Sea surface waters as an estimate of the isotopic composition of this input ( 206 Pb 207 Pb = 1.195 ± 0.004 ), we calculate a contribution of 42–57% from America in these waters. This demonstrates that American emissions still dominated lead contamination over the North Atlantic in the early 1990s, in spite of the early reduction of leaded gasoline in the USA. These results also give new evidence of the equilibrium between dissolved and particulate phases during scavenging processes.

Invasion of the abyssal North Atlantic by modern anthropogenic lead

While anthropogenic emissions have dramatically elevated lead concentrations in the North Atlantic troposphere and surface waters by orders of magnitude above natural levels [Murozumi et al., 1969; Schaule and Patterson, 1983; Boyle et al., 1986], it has been assumed that the relatively low lead levels in North Atlantic abyssal waters are not yet contaminated [Schaule and Patterson, 1981; Flegal and Patterson, 1983]. That misperception is redressed by the following stable lead isotopic composition data which reveal the advective transport of industrial lead into those deep basin waters through the formation of North Atlantic Deep Water (NADW). Additionally, spatial gradients in the isotopic signatures of anthropogenic lead within the North Atlantic abyss appear to serve as transient tracers of contaminant penetration rates.

Isotopic evidence of contaminant lead in the South Atlantic troposphere and surface waters

Abstract The third Intergovernmental Oceanographic Commission (IOC) Baseline Contaminant cruise (May–June 1996) has established the first lead isotopic compositions in the surface water and the atmosphere of the Equatorial and South Atlantic Ocean. These ratios have evidenced both anthropogenic and natural origins of lead along the cruise transect (from 33°S to 10°N). The isotopic gradients tentatively have been, attributed to aeolian as well as surface-water advective inputs from a suite of rather local and remote sources to the Southern Hemisphere. Relatively low 206Pb/207Pb ratios (x±sd) were encountered within the South Equatorial Current between 17°S and 5°S (1.156±0.003). Those were bracketed by more radiogenic ratios at higher latitudes in the Southern Hemisphere (33°S to 23°S), within the Brazil Current and the Subtropical Gyre (1.163±0.003), and in the Northern Hemisphere (0° to 10°N) (1.165±0.005). The latter were comparable to ratios of surface water in the North Atlantic Equatorial Ocean (1.169±0.006), under a combined contaminant influence of both North American westerlies (1.19–1.20) and European easterlies (1.155–1.165). That predominance of contaminant lead contrasts with the measurable presence of natural lead in surface waters of the Equatorial Ocean, which are attributed to aeolian inputs of Saharan dust. The ratios of lead in surface waters at higher latitudes in the South Atlantic are characteristic of anthropogenic lead aerosols also detected in Antarctic ice, and could substantiate as well the hypothesized aerosol recycling of lead by sea-spray emission in the far Southern Hemisphere. The atmospheric lead isotopic compositions (206Pb/207Pb) in bulk depositions (1.171±0.006), precipitation (1.171±0.006) and aerosols (1.168±0.011) were, generally, more radiogenic than the surface waters (1.162±0.005). Beside a poor representation of a short term atmospheric sampling, this difference could reflect a recent evolution in atmospheric lead emissions, which have not yet been reflected in oceanic surface waters. It may also be due, in part, to advective lead inputs from surface oceanic circulation of the South Equatorial Current.

Multitracer study of anthropogenic contamination records in the Camargue, Southern France

Contaminants are supplied to the coastal zone by the atmosphere, rivers and point sources like wastewaters or industrial area. Wetlands retain many of these contaminants and can be used to reconstruct sources and magnitudes of contaminant inputs. Radionuclides ((137)Cs, (210)Pb, (239)Pu and (240)Pu) and stable lead isotope ((206)Pb, (207)Pb) profiles were investigated in two cores collected in wetlands of the Rhône River delta, south of France (Camargue), to estimate the recent sediment accumulation rates and reconstruct the deposition of pollutants during the last century. One site was affected by storm or flood deposition from the Rhône river and showed the influence of Marcoule reprocessing plant releases on the plutonium isotopic ratios. The other site appears suitable for the reconstruction, even if mixing is evidenced at the surface by the radionuclides profiles. Plutonium isotopic ratios are characteristic of global fallout and the (210)Pb inventory of 4240 Bq m(-2) is approximately 30% higher than atmospheric deposit estimation. The pollutant lead inventory is 139 microg cm(-2), slightly higher than previous estimation from direct fallout. This difference can be partly due to an over-collection at this site (due to canopy cover) but also to variations with time in the deposition.

Anthropogenic metal contamination and sapropel imprints in deep Mediterranean sediments.

Sediment cores from the deep Balearic basin and the Cretan Sea provide evidence for the accumulation of Cd, Pd and Zn in the top few centimeters of the abyssal Mediterranean sea-bottom. In both cores, 206Pb/207Pb profiles confirm this anthropogenic impact with less radiogenic imprints toward surface sediments. The similarity between excess 210Pb accumulated in the top core and the 210Pb flux suggests that top core metal inventories reasonably reflect long-term atmospheric deposition to the open Mediterranean. Pb inventory in the western core for the past 100 years represents 20-30% of sediment coastal inventories, suggesting that long-term atmospheric deposition determined from coastal areas has to be used cautiously for mass balance calculations in the open Mediterranean. In the deeper section of both cores, Al normalized trace metal profiles suggest diagenetic remobilization of Fe, Mn, Cu and, to a lesser extent, Pb that likely corresponds to sapropel event S1.

Environmental imprints of climate changes and anthropogenic activities in the Ore Mountains of Bohemia (Central Europe) since 13 cal. kyr BP

We have measured pollen, aluminum, and lead abundances in a Czech peat bog at Bozi Dar in order to investigate the environmental impact of Holocene climate changes and mining activities in Central Europe. The pollen record shows a continuous vegetal cover since 13 kyr BP. Aluminum and pollen deposition characterize the Younger Dryas (YD) cold event at 12.3–11.0 kyr BP, within its expected time frame in Northern Europe. Aluminum fluxes reveal four other significant dust events with significant Asian and Saharan sources, as shown with variations in stable 204Pb, 206Pb, and 207Pb isotopes. Recurrent Asian incursions are seen at Bozi Dar during the YD and Mid-Holocene dust events (at 7.1, 6.5, and 5.9 kyr BP). These Asian imprints are also observed by Le Roux and colleagues during the YD in the nearest Holocene-long geochemical peat record from Switzerland (Etang de la Gruère). We do not see at Bozi Dar the distinct western European volcanic inputs identified in the Swiss peat by Shotyk and colleagues. However, isotopic ratios characteristics of Mediterranean airflows are evident at both locations during the Mid- and Late Holocene. The occurrence of these various air mass sources in Switzerland and the Czech Republic substantiates Holocene atmospheric circulation models in Central Europe with dominating zonal airflows during the Early Holocene, followed by a governing meridian dispersion during the Mid- and Late Holocene. Lead inputs at 5.1–4.3 and 1.9 kyr BP cannot be explained by increased dust deposition only. The 1.9 kyr event fits local Bohemian ore isotopic imprints of which isotopic signatures are seen as early as 2.2 kyr BP in our core, hence revealing the oldest ever environmental record of mining-related activities in the Czech Republic. Relatively elevated Pb deposition at 5.1 and 4.3 kyr BP are tentatively attributed to contamination that may be from local sources and/or long-range transport.

Lead isotopes reveal different sources of lead in balsamic and other vinegars

Fifty-eight brands of balsamic vinegars were analyzed for lead concentrations and isotopic compositions ((204)Pb, (206)Pb, (207)Pb, and (208)Pb) to test the findings of a previous study indicating relatively high levels of lead contamination in some of those vinegars--more than two thirds (70%) of them exceeded Californias State Maximum Level (34 μg/L) based on consumption rates ≥0.5 μg Pb per day. The lead isotopic fingerprints of all those vinegars with high lead concentrations were then found to be primarily anthropogenic. This isotopic analysis unquestionably reveals multiple contamination sources including atmospheric pollutant Pb and an unidentified contamination source, likely occurring after grape harvest. Organically grown grape vinegars display the same Pb content and isotopic signatures as other vinegars. This implies that pesticides might not be a significant source of pollutant Pb in vinegars. A significant post-harvest contamination would be inherited from chemicals added during production and/or material used during transport, processing or storage of these vinegars. This is consistent with the highest Pb levels being found in aged vinegars (112±112 μg/L) in contrast to other vinegars (41.6±28.9 μg/L) suggesting contamination during storage. It is, therefore, projected that lead levels in most vinegars, especially aged balsamic and wine vinegars, will decrease with improvements in their manufacture and storage processes consequential to recent concerns of elevated levels of lead in some vinegars.