Late glacial (17,060-13,400 cal yr BP) sedimentary and paleoenvironmental evolution of the Sekhokong Range (Drakensberg), southern Africa.

Southern Africa sits at the junction of tropical and temperate systems, leading to the formation of seasonal precipitation zones. Understanding late Quaternary paleoclimatic change in this vulnerable region is hampered by a lack of available, reliably-dated records. Here we present a sequence from a well-stratified sedimentary infill occupying a lower slope basin which covers 17,060 to 13,400 cal yr BP with the aim to reconstruct paleoclimatic variability in the high Drakensberg during the Late Glacial. We use a combination of pollen, total organic carbon and nitrogen, δ13C, Fourier transform infrared spectroscopy attenuated total reflectance (FTIR-ATR) spectral and elemental data on contiguous samples with high temporal resolution (10 to 80 years per sample). Our data support a relatively humid environment with considerable cold season precipitation during what might have been the final stage of niche-glaciation on the adjoining southern aspects around 17,000 cal yr BP. Then, after an initial warmer and drier period starting ~15,600 cal yr BP, we identify a return to colder and drier conditions with more winter precipitation starting ~14,380 cal yr BP, which represents the first local evidence for the Antarctic Cold Reversal (ACR) in this region. On decadal to centennial timescales, the Late Glacial period was one marked by considerable climatic fluctuation and bi-directional environmental change, which has not been identified in previous studies for this region. Our study shows complex changes in both moisture and thermal conditions providing a more nuanced picture of the Late Glacial for the high Drakensburg.

Testing the applicability of dendrochemistry using X-ray fluorescence to trace environmental contamination at a glassworks site.

The potential of dendrochemistry as a tool for tracing anthropogenic contamination at a glassworks site in southeastern Sweden was investigated through a multidisciplinary approach combining continuous high-resolution time series of tree rings and sediment profiles. Tree cores from Scots pine (Pinus sylvestris), Norway spruce (Picea abies) and European aspen (Populus tremula) were analysed for their elemental composition using an energy dispersive X-ray fluorescence (ED-XRF) technique. Sediment cores were sampled along a transect extending from the pollution point source to unpolluted areas and analysed using core-scanning-XRF (CS-XRF). High contaminant concentrations in the soil were found for As (≈2000 ppm), Pb (>5000 ppm), Ba (≈1000 ppm) and Cd (≈150 ppm). The concentrations decreased with depth and distance from the pollution source. The dendrochemical analyses revealed alterations in the Barium, Chlorine and Manganese profiles, allowing the identification of seven potential asynchronous releases from the glassworks. Our results suggest that differences in the response of tree species to elemental uptake together with soil chemical properties dictate the success of dendrochemistry as an environmental monitoring tool.

Mineral dust as a driver of carbon accumulation in northern latitudes.

Peatlands in northern latitudes sequester one third of the world's soil organic carbon. Mineral dusts can affect the primary productivity of terrestrial systems through nutrient transport but this process has not yet been documented in these peat-rich regions. Here we analysed organic and inorganic fractions of an 8900-year-old sequence from Store Mosse (the "Great Bog") in southern Sweden. Between 5420 and 4550 cal yr BP, we observe a seven-fold increase in net peat-accumulation rates corresponding to a maximum carbon-burial rate of 150 g C m-2 yr-1 - more than six times the global average. This high peat accumulation event occurs in parallel with a distinct change in the character of the dust deposited on the bog, which moves from being dominated by clay minerals to less weathered, phosphate and feldspar minerals. We hypothesize that this shift boosted nutrient input to the bog and stimulated ecosystem productivity. This study shows that diffuse sources and dust dynamics in northern temperate latitudes, often overlooked by the dust community in favour of arid and semi-arid regions, can be important drivers of peatland carbon accumulation and by extension, global climate, warranting further consideration in predictions of future climate variability.

Industrial-era lead and mercury contamination in southern Greenland implicates North American sources.

To study the long-range transport of atmospheric pollutants from lower latitude industrial areas to the Arctic, we analysed a peat core spanning the last ~700cal.yr (~1300-2000CE) from southern Greenland, an area sensitive to atmospheric pollution from North American and Eurasian sources. A previous investigation conducted in the same location recorded atmospheric lead (Pb) pollution after ~1845, with peak values recorded in the 1970s, and concluded that a North American source was most likely. To confirm the origin of the lead, we present new Pb isotope data from Sandhavn, together with a high-resolution record for mercury (Hg) deposition. Results demonstrate that the mercury accumulation rate has steadily increased since the beginning of the 19th century, with maximum values of 9.3µgm-2yr-1 recorded ~1940. Lead isotopic ratios show two mixing lines: one which represents inputs from local and regional geogenic sources, and another that comprises regional geogenic and pollution sources. Detrending the Pb isotopic ratio record (thereby extracting the effect of the geogenic mixing) has enabled us to reconstruct a detailed chronology of metal pollution. The first sustained decrease in Pb isotope signals is recorded as beginning ~1740-1780 with the lowest values (indicating the highest pollution signature) dated to ~1960-1970. The 206Pb/207Pb ratio of excess Pb (measuring 1.222, and reflecting pollution-generated Pb), when compared with the Pb isotopic composition of the Sandhavn peat record since the 19th century and the timing of Pb enrichments, clearly points to the dominance of pollution sources from North America, although it did not prove possible to further differentiate the emissions sources geographically.

Early atmospheric metal pollution provides evidence for Chalcolithic/Bronze Age mining and metallurgy in Southwestern Europe.

Although archaeological research suggests that mining/metallurgy already started in the Chalcolithic (3rd millennium BC), the earliest atmospheric metal pollution in SW Europe has thus far been dated to ~3500-3200 cal.yr. BP in paleo-environmental archives. A low intensity, non-extensive mining/metallurgy and the lack of appropriately located archives may be responsible for this mismatch. We have analysed the older section (>2100 cal.yr. BP) of a peat record from La Molina (Asturias, Spain), a mire located in the proximity (35-100 km) of mines which were exploited in the Chalcolithic/Bronze Age, with the aim of assessing evidence of this early mining/metallurgy. Analyses included the determination of C as a proxy for organic matter content, lithogenic elements (Si, Al, Ti) as markers of mineral matter, and trace metals (Cr, Cu, Zn, Pb) and stable Pb isotopes as tracers of atmospheric metal pollution. From ~8000 to ~4980 cal.yr. BP the Pb composition is similar to that of the underlying sediments (Pb 15 ± 4 µg g(-1); (206)Pb/(207)Pb 1.204 ± 0.002). A sustained period of low (206)Pb/(207)Pb ratios occurred from ~4980 to ~2470 cal.yr. BP, which can be divided into four phases: Chalcolithic (~4980-3700 cal.yr. BP), (206)Pb/(207)Pb ratios decline to 1.175 and Pb/Al ratios increase; Early Bronze Age (~3700-3500 cal.yr. BP), (206)Pb/(207)Pb increase to 1.192 and metal/Al ratios remain stable; Late Bronze Age (~3500-2800 cal.yr. BP), (206)Pb/(207)Pb decline to their lowest values (1.167) while Pb/Al and Zn/Al increase; and Early Iron Age (~2800-2470 cal.yr. BP), (206)Pb/(207)Pb increase to 1.186, most metal/Al ratios decrease but Zn/Al shows a peak. At the beginning of the Late Iron Age, (206)Pb/(207)Pb ratios and metal enrichments show a rapid return to pre-anthropogenic values. These results provide evidence of regional/local atmospheric metal pollution triggered by the earliest phases of mining/metallurgy in the area, and reconcile paleo-environmental and archaeological records.

Anthropogenic forcings on the surficial osmium cycle.

Osmium is among the least abundant elements in the Earth's continental crust. Recent anthropogenic Os contamination of the environment from mining and smelting activities, automotive catalytic converter use, and hospital discharges has been documented. Here we present evidence for anthropogenic overprinting of the natural Os cycle using a ca. 7000-year record of atmospheric Os deposition and isotopic composition from an ombrotrophic peat bog in NW Spain. Preanthropogenic Os accumulation in this area is 0.10 +/- 0.04 ng m(-2) y(-1). The oldest strata showing human influence correspond to early metal mining and processing on the Iberian Peninsula (ca. 4700-2500 cal. BP). Elevated Os accumulation rates are found thereafter with a local maximum of 1.1 ng m(-2) y(-1) during the Roman occupation of the Iberian Peninsula (ca. 1930 cal. BP) and a further increase starting in 1750 AD with Os accumulation reaching 30 ng m(-2) y(-1) in the most recent samples. Osmium isotopic composition ((187)Os/(188)Os) indicates that recent elevated Os accumulation results from increased input of unradiogenic Os from industrial and automotive sources as well as from enhanced deposition of radiogenic Os through increased fossil fuel combustion and soil erosion. We posit that the rapid increase in catalyst-equipped vehicles, increased fossil fuel combustion, and changes in land-use make the changes observed in NW Spain globally relevant.

Two high resolution terrestrial records of atmospheric Pb deposition from New Brunswick, Canada, and Loch Laxford, Scotland.

Environmental archives like peat deposits allow for the reconstruction of both naturally and anthropogenically forced changes in the biogeochemical cycle of Pb as well as the quantification of past and present atmospheric Pb pollution. However, records of atmospheric Pb deposition from pre-industrial times are lacking. In a publication by Weiss et al. [Weiss, D., Shotyk, W., Boyle, E.A., Kramers, J.D., Appleby, P.G., Cheburkin, A.K., Comparative study of the temporal evolution of atmospheric lead deposition in Scotland and eastern Canada using blanket peat bogs. Sci Total Environ 2002;292:7-18]. Pb isotopes data measured by Q-ICP-MS and TIMS, concentration and enrichment data was presented for sites in eastern Canada (PeW1) and northwestern Scotland (LL7c), dating to 1586 A.D and 715 A.D., respectively. Here these same cores are re-analysed for Pb isotopes by MC-ICP-MS thereby acquiring 204Pb data and improving on the original data in terms of resolution and temporal coverage. Significant differences were found between the Q-ICP-MS/TIMS and MC-ICP-MS measurements, particularly at PeW1. These discrepancies are attributed to the problematic presence of organic matter during sample preparation and analysis complicated by the heterogeneity of the organic compounds that survived sample preparation steps. The precision and accuracy of Pb isotopes in complex matrices like peat is not always well estimated by industrial standards like NIST-SRM 981 Pb. Lead pollution histories at each site were constructed using the MC-ICP-MS data. The entire LL7c record is likely subject to anthropogenic additions. Contributions from local mining were detected in Medieval times. Later, coal use and mining in Scotland, Wales and England became important. After industrialization (ca. 1885 A.D.) contributions from Broken Hill type ores and hence, leaded petrol, dominate atmospheric Pb signatures right up to modern times. At PeW1 anthropogenic impacts are first distinguishable in the late 17th century with the mining and use of local coal. After industrialization (ca. 1810 A.D.), coal and petrol are the main Pb sources. A comprehensive estimate of the natural atmospheric background 206Pb/207Pb signature in eastern Canadian aerosols is made with a value of approximately 1.19.

Lead penetration and leaching in a complex temperate soil profile.

The documented loss of anthropogenic Pb from soil organic horizons and its migration into the mineral soil below has raised several environmental concerns, especially over the leaching of Pb into groundwater aquifers and subsequently into other environmental compartments of the ecosystem. Here, a complex colluvial soil formed over the last 10,000 years in NW Spain is studied. The objective is to evaluate the behavior of Pb in soils, including its migration rates and the potential use of complex soils as archives of atmospheric Pb pollution. To this end, Pb concentrations and Pb isotope ratios for total soil, and for acid-extractable (0.5 M HNO3) and residual fractions were determined. We show that the acid-extractable fraction is more radiogenic than the residual one in most of the soil profile and that this relationship is reversed in the surface layers (< 15 cm) where pollution is greatest. Radiogenic Pb seems to have been leached out during rock weathering and pedogenesis of the soil. Comparison with a nearby peat record of atmospheric Pb deposition over the last 8 kyears demonstrates that though signals from pollution are detected in the soil record, the soil itself does not provide an accurate reconstruction of Pb deposition. On the basis of the history of soil formation the most likely Pb migration rate is estimated at approximately 0.01 cm year(-1). At this migration rate Pb would be retained in the soil column for approximately 20 kyear. In other words, there is no evidence for the relatively rapid movement of Pb into the soil.

Impact of automobile emissions on the levels of platinum and lead in Accra, Ghana.

Examination of car fleet records in Accra demonstrates an increasing proportion of catalytic converter-equipped cars in the relatively old car fleet (average age 13 years) due to their import from developed countries. However, only leaded petrol is sold in Ghana. Lead anti-knocking additives, which are known to affect catalyst activity and promote thermal sintering and mechanical abrasion, may increase Pt emissions. This possible synergism prompted the concomitant determination of Pb and Pt levels in road dust and roadside soils in Ghana. Both metals followed traffic density with higher concentrations in urban areas compared to remote sites. In urban areas, the range for Pb (365 +/- 93 microg g(-1) for dust and 291 +/- 76 microg g(-1) for soil) reflects precatalyst levels in Europe and the US, while the range for Pt (39 +/- 24 ng g(-1) for dust and 15 +/- 5.3 ng g(-1) for soil) is typical for the same countries. The elevated Pt concentrations were unexpected due to recent introduction of catalysts to Ghana compared to the prolonged use of catalysts in Europe and the US.