Geogenic Pb Research Articles

Lead in sediments and suspended particulate matter of the German Bight: natural versus anthropogenic origin

Sediments (568) and suspended particulate matter (SPM, 302 samples) of the southern German Bight and the adjacent tidal flat areas were analysed for selected major elements (Al, Fe, K), trace metals (Mn, Pb), and 206Pb/ 207Pb ratios using XRF, ICP–OES, ICP–MS. For selected samples a leaching procedure with 1 M HCl was used to estimate the Pb fraction associated with labile phases (e.g. Mn/Fe-oxihydroxide coatings) in contrast to the resistant mineral matrix. Enrichment factors versus average shale (EFS) reveal elevated Pb contents for all investigated sediments and SPM in the following order: Holocene tidal flat sediments (HTF, human-unaffected) <recent tidal flat sediments (RTF) <Helgoland Island mud hole sediments (MH) <nearshore SPM (SPM concentration>5 mg l −1) < offhore SPM (<5 mg l −1). Besides pollution, RTF contain elevated amounts of natural Pb-rich materials (K-feldspars and heavy minerals) due to a man-made high-energy environment (dike building) in comparison to HTF. 206Pb/ 207Pb ratios of RTF (1.192±0.019) are similar to the local geogenic background, determined from HTF (1.207±0.008). In contrast, Pb isotope ratios of nearshore SPM (1.172±0.007) and offshore SPM (1.166±0.012) show a distinct shift towards the anthropogenic/atmospheric signal of 1.11–1.14. This difference between RTF and SPM supports the assumption of low deposition rates of fine material in the intertidal systems. As the 206Pb/ 207Pb ratios of SPM do not reach the pure anthropogenic signal, the adsorbed Pb fraction was examined (leaching). However, the leachates also contained large amounts of geogenic Pb (SPM ≈40%, recent sediments ≈60%). The authors assume that the uptake of natural Pb occurs in nearshore waters, presumably in the turbid intertidal systems. Possible sources for dissolved Pb are mobilisation during weathering (geogenic signal) and dissolution of oxihydroxide coatings with subsequent release from porewaters, and unspecific riverine input. Comparatively small parts of SPM leave the coastal water mass and reach the open North Sea. This process therefore leads to a decontamination of the tidal flat sediments. Due to more pronounced atmospheric input, the offshore SPM becomes enriched in anthropogenic Pb as indicated by decreasing 206Pb/ 207Pb ratios with increasing distance from the coast.

ISOTOPIC EVALUATION OF Pb OCCURRENCES IN THE RIVERINE ECOSYSTEMS OF THE KANKAKEE WATERSHED, ILLINOIS‐INDIANA1

ABSTRACT: Environmental background levels of Pb were measured in ponds, river waters, sediments, suspended sediments, rocks, and air particulates within the Kankakee watershed during the period of 1995 to 1999. Stable isotopic Pb distinguished airborne Pb and its incorporation into riverine wetland sediments from geogenic Pb measured in river sediments. The provenance of the naturally‐occurring Pb is from carbonate bedrock and contributes comparable concentrations in riverbank sediments (25.9–30.4 mg kg−1) as Pb found in wetland sediments (18.6–24.8 mg kg−1). Estimates of anthropogenic Pb contributions from airfall into the Kankakee wetlands were found to be near 0.43–0.71 Bq cm−2 yr−1 during 1995 to 1999. While leachable Pb data suggests the uppermost layers of pond sediments were disturbed, 210Pb analyses from undisturbed sedimentation suggests Pb‐bearing sediments accumulate approximately 0.46–0.51 cm yr−1 in the ponds within the riparian zones. Transboundary Pb pollution from aerosols of industrial Pb across the Great Lakes occurs, but Pb isotopy indicates that the Pb concentrations are comparable to natural concentrations of Pb in both waters and sediments within the Kankakee watershed.

Pb isotopes in sediments of Lake Constance, Central Europe constrain the heavy metal pathways and the pollution history of the catchment, the lake and the regional atmosphere

Pb isotope ratios and Pb concentrations of well-dated sediments of Lake Constance, Central Europe have been analyzed using thermal ion mass spectrometry. Sequential extraction studies indicated isotope homogeneity of the leachable Pb components within the investigated layers. Since the middle of the 19th century a significant anthropogenic Pb component appeared in the lake sediments, and rapidly approached concentration levels similar to that of the geogenic Pb background (20 ppm) at the beginning of the 20th century. Anthropogenic Pb was predominantly transferred to the lake sediments via the atmosphere. Pb sources were coal combustion, industrial ore processing and leaded gasoline. The flux of a fluvial Pb component to the lake sediments, additive to atmospheric Pb deposition, peaked in about 1960. This flux is attributed to (re)mobilization of Pb from polluted parts of the lake catchment, and indicates the change of catchment soils from a pollution sink to a heavy metal source. The strong reduction of anthropogenic Pb in the uppermost lake sediments since the 1960’s has been caused by advances of environmental protection. The lake sediments record the changing fluxes and the isotope composition of the deposited aeolian Pb pollution. During the 20th century aeolian Pb fluxes to the lake sediments were in the range of 1–4 μg/cm 2/a. During peak emission periods of gasoline Pb to the atmosphere (1960–1990) the aerosol Pb isotope composition was rather constant ( 206Pb/ 207Pb: 1.12–1.13) and probably a mixture of Canadian and Australian with Russian and Central European Pb types. Aeolian Pb isotope and Pb flux trends in the lake sediments as a whole agree well with the trends found in Alpine glaciers (Döring et al., 1997a,b) and in ombrotrophic peat bogs of Switzerland (Shotyk et al., 1996). However, different industrial Pb components were deposited in the archives of aeolian pollution during the early 20th century.