Comparative study of the temporal evolution of atmospheric lead deposition in Scotland and eastern Canada using blanket peat bogs.

The temporal evolution of atmospheric lead deposition and its possible sources were assessed in eastern Canada and in western Scotland, using blanket peat bogs as geochemical archives. Short cores were taken from two remote sites located close to the sea. Significant lead enrichments in the upper layers at both sites reflect the increasing emission of lead into the atmosphere due to anthropogenic activities during the last century. At the Scottish site, a region under aeolian influence from Europe, anthropogenic derived lead could be recognized by the distinctive unradiogenic composition (206Pb/207Pb ratios down to approximately 1.115), being clearly different from the pre-industrial values (206Pb/207Pb approximately 1.166). In contrast, the lead pollution in eastern Canada (influenced by North American sources) is identified by a more radiogenic lead isotope composition (206Pb/207Pb ratios up to approximately 1.199) compared to preindustrial values (206Pb/207Pb approximately 1.161). Emission inventories and isotope characteristics suggest that industrial (coal burning, mining) and traffic (leaded gasoline) outputs are the most likely sources during the first and the second half of the 20th century, respectively, in both, western Scotland and eastern Canada alike. The Scottish record is in line with previous studies of past atmospheric lead deposition. However, the Canadian deposit suggests that the wind derived, pre-industrial lead, is less radiogenic as previously implied using sediment archives. These results are thus the first to report pre-industrial lead isotope ratios and concentrations of atmospheric derived aerosols in North America.

Anthropogenic impacts in North Poland over the last 1300 years--a record of Pb, Zn, Cu, Ni and S in an ombrotrophic peat bog.

Lead pollution history over Northern Poland was reconstructed for the last ca. 1300 years using the elemental and Pb isotope geochemistry of a dated Polish peat bog. The data show that Polish Pb-Zn ores and coal were the main sources of Pb, other heavy metals and S over Northern Poland up until the industrial revolution. After review of the potential mobility of each element, most of the historical interpretation was based on Pb and Pb isotopes, the other chemical elements (Zn, Cu, Ni, S) being considered secondary indicators of pollution. During the last century, leaded gasoline also contributed to anthropogenic Pb pollution over Poland. Coal and Pb-Zn ores, however, remained important sources of pollution in Eastern European countries during the last 50 years, as demonstrated by a high (206)Pb/(207)Pb ratio (1.153) relative to that of Western Europe (ca. 1.10). The Pb data for the last century were also in good agreement with modelled Pb inventories over Poland and the Baltic region.

Spatial distribution of natural enrichments of arsenic, selenium, and uranium in a minerotrophic peatland, Gola di Lago, Canton Ticino, Switzerland.

Gola di Lago is a small (ca. 3 ha), minerotrophic peatland in Canton Ticino, southern Switzerland. Chemical analyses of peat show remarkable concentrations of As, Se, and U. Coring at regular intervals (19 sites) revealed several zones of pronounced accumulation, with As concentrations up to 350 mg kg(-1) (2000 mg kg(-1) on a mineral matter basis). Both Fe and S are also enriched at this depth, suggesting that redox-related transformations have affected all three elements. High concentrations of Se (up to 28 mg kg(-1)) and U (up to 470 mg kg(-1)) were also detected, representing on a mineral matter basis 350 and 2900 mg kg(-1), respectively. An intermittent stream entering the peatland contained up to 400 microg of As L(-1), but the permanent stream leaving the mire contains <2 microg L(-1). A three-dimensional map of the spatial distribution of As shows that the main source of As is the intermittent stream and not the basal, mineral sediment underlying the peatland. Arsenic is highly enriched not only in shallow peat layers at the interface between the stream and peatland today but also in deeper peat layers in the center of the mire, at what must have been the stream-peat interface in the past. By sequential extraction of fresh peat samples, 100% of the As could be extracted from a shallow sample but only 19% from a sample taken from the deeper layers. In both cases, most of the As was associated with the organic matter fraction (73% and 57% respectively). Although this peatland is an effective geochemical trap for As in the stream waters, the mechanisms of removal remain unclear.

Use of Br and Se in peat to reconstruct the natural and anthropogenic fluxes of atmospheric Hg: A 10000-year record from Caribou Bog, Maine.

Using Br and Se as reference elements, the natural and anthropogenic fluxes of atmospheric Hg were reconstructed for the past 10,000 years using peat cores from Caribou Bog, ME. In the ombrotrophic peat layers, the average background Hg accumulation rate (AR) was 1.7 +/- 1.3 microg m(-2) year(-1) which is comparable with the natural rate of atmospheric Hg accumulation reported in other retrospective studies. The average Hg AR determined using all peat samples dating from preindustrial times, including minerotrophic peat, was slightly greater (3.1 +/- 2.3 microg m(-2) year(-1)) which may reflect differences in canopy interception due to the changes in plant communities, aquatic inputs, or possibly climatic factors. The maximum Hg AR (32 microg m(-2) year(-1)) occurred ca. 1961 A.D. In samples predating the settlement by Europeans, there is a linear correlation between the AR of Hg and those of Br and Se; this relationship allows both Br and Se to be used to calculate the natural AR of Hg (Hgnat). The difference between Hg AR and Hg(nat) is the Hg AR in excess of background (Hg(ex)). Because Hg(ex) was positive only after ca. 1840 A.D., it is assumed to represent the anthropogenic Hg component. By the late 19th century, Hg(ex) deposition was equal to the natural flux. At the peak in Hg deposition in 1961 A.D., Hgex made up >90% of total atmospheric Hg deposition. The AR in the uppermost peat decreased to 25% of peak values by 2000 A.D.

Comparison of atmospheric deposition of copper, nickel, cobalt, zinc, and cadmium recorded by Finnish peat cores with monitoring data and emission records.

This study aims to determine the extent to which the accumulation rates of Cu, Ni, Co, Zn, and Cd in peat cores agree with established histories of atmospheric emission from local pointsources. Metals accumulating in three Finnish peat cores with known metal deposition histories have been measured using inductively coupled plasma-sector field mass spectrometry. Samples were age-dated using both 210Pb and 14C (bomb pulse curve). At the Outokumpu (OUT) site as well as the low-background site Hietajärvi (HIJ), 210Pb age dates are in excellent agreement with the 14C bomb pulse curve method results, and the precision is between 1 and 10 years for most of the samples; at the Harjavalta (HAR) site, precision is > 6 years. Mean regional "background" concentrations have been calculated from deeper peat layers of the HIJ site (microg g(-1)): Cu, 1.3 +/- 0.2 (n = 62); Co, 0.25 +/- 0.04 (n = 71); Cd, 0.08 +/- 0.01 (n = 23); and Zn, 4 +/- 2 (n = 40). For layers accumulated within the past 100 years, accumulation rates (ARs) have been calculated. At sites with < 0.06 g m(-2) cumulative Ni inventory (HIJ and OUT), ARs of Cu and Co trace the known metal deposition histories very well. At HAR, where metal inventories are much greater, Cu and Co are mobile. ARs of Zn were between 3 and 30 mg m(-2) year(-1) and those of Cd between 24 and 140 microg m(-2) year(-1) at all sites and are independent of the chronology of their inputs from the atmosphere.

Atmospheric mercury accumulation rates between 5900 and 800 calibrated years BP in the High Arctic of Canada recorded by peat hummocks.

In this paper, we present the first comprehensive long-term record of preanthropogenic rates of atmospheric mercury accumulation in dated peat deposits for the High Arctic of Canada. Geochemical studies of two peat hummocks from Bathurst Island, Nunavut reveal substantial inputs from soil dust (titanium), marine aerosols (bromine), and mineral-water interactions (uranium). Mercury, however, was supplied to these peat mounds exclusively by atmospheric deposition. Mercury concentration measurements and age dating of the peat profiles indicate rather constant natural "background" mercury flux of ca. 1 microgram per square meter per year from 5900 to 800 calibrated years BP. These values are well within the range of the mercury fluxes reported from other Arctic locations, but also by peat cores from southern Canada that provide a record of atmospheric Hg accumulation extending back 8000 years. Thus, preanthropogenic Hg fluxes in the Arctic were not significantly different from atmospheric Hg fluxes in the temperate zone. In preindustrial times, therefore, the High Arctic was no more important as a sink for global atmospheric mercury than was the temperate zone.

Identifying the sources and timing of ancient and medieval atmospheric lead pollution in England using a peat profile from Lindow bog, Manchester.

A peat core from Lindow bog near Manchester, England, was precisely cut into 2 cm slices to provide a high-resolution reconstruction of atmospheric Pb deposition. Radiocarbon and (210)Pb age dates show that the peat core represents the period ca. 2000 BC to AD 1800. Eleven radiocarbon age dates of bulk peat samples reveal a linear age-depth relationship with an average temporal resolution of 18.5 years per cm, or 37 years per sample. Using the Pb/Ti ratio to calculate the rates of anthropogenic, atmospheric Pb deposition, the profile reveals Pb contamination first appearing in peat samples dating from ca. 900 BC which clearly pre-date Roman mining activities. Using TIMS, MC-ICP-MS, and SF-ICP-MS to measure the isotopic composition of Pb, the (208)Pb/(206)Pb and (206)Pb/(207)Pb data indicate that English ores were the predominant sources during the pre-Roman, Roman, and Medieval Periods. The study shows that detailed studies of peat profiles from ombrotrophic bogs, using appropriate preparatory and analytical methods, can provide new insight into the timing, intensity, and predominant sources of atmospheric Pb contamination, even in samples dating from ancient times.

Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analyses.

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.