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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.

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.

Peat cores from three bogs in southern Ontario provide a complete, quantitative record of net rates of atmospheric Hg accumulation since pre-industrial times. For comparison with modern values, a peat core extending back 8000 years was used to quantify the natural variations in Hg fluxes for this region, and their dependence on climatic change and land use history. The net mercury accumulation rates were separated into "natural" and "excess" components by comparing the Hg/Br ratios of modern samples with the long-term, pre-anthropogenic average Hg/Br. The average background mercury accumulation rate during the pre-anthropogenic period (from 5700 years BC to 1470 AD) was 1.4 +/- 1.0 microg m(-2) per year (n = 197). The beginning of Hg contamination from anthropogenic sources dates from AD 1475 at the Luther Bog, corresponding to biomass burning for agricultural activities by Native North Americans. During the late 17th and 18th centuries, deposition of anthropogenic Hg was at least equal to that of Hg from natural sources. Anthropogenic inputs of Hg to the bogs have dominated continuously since the beginning of the 19th century. The maximum Hg accumulation rates decrease in the order Sifton Bog, in the City of London, Ontario (141 microg Hg m(-2) per year), Luther Bog in an agricultural region (89 microg Hg m(-2) per year), and Spruce Bog which is in a comparatively remote, forested region (54 microg Hg m(-2) per year). Accurate age dating of recent peat samples using the bomb pulse curve of 14C shows that the maximum rate of atmospheric Hg accumulation occurred during AD 1956 and 1959 at all sites. In these (modern) samples, the Hg concentration profiles resemble those of Pb, an element which is known to be immobile in peat bogs. The correlation between these two metals, together with sulfur, suggests that the predominant anthropogenic source of Hg (and Pb) was coal burning. While Hg accumulation rates have gone into strong decline since the late 1950's, Hg deposition rates today still exceed the average natural background values by 7 to 13 times.

Vanadium, Cr, and Ni accumulating in a Swiss peat bog since 12 370 14C yr B.P. have been measured using inductively coupled plasma-mass spectrometry (ICP-MS) after acid dissolution in a microwave autoclave. Strict quality control schemes were applied to guarantee the accuracy of the applied analytical methodology. The concentration gradients in the peat column and comparison with Pb indicate that V, Cr, and Ni are effectively immobile in the ombrotrophic section of the peat profile but that Ni is added to the minerotrophic peat layers by chemical weathering of the underlying sediments. The lowest metal concentrations were found during the Holocene climate optimum (5320-8230 14C yr B.P.) when "natural background" values averaged 0.55 +/- 0.13 microg g(-1) V, 0.76 +/- 0.17 microg g(-1) Cr, and 0.46 +/- 0.09 microg g(-1) Ni (n = 18); given the average bulk density (0.05 g/cm3) and accumulation rate (0.05 cm/ yr) of peat in this zone, the corresponding atmospheric fluxes are approximately 14, 19, and 12 microg m(-2) yr(-1) for V, Cr, and Ni, respectively. The highest concentrations of V, Cr, and Ni were found during the Younger Dryas cold climate event (centered at 10 590 14C yr B.P.) when background values were exceeded by about 40 times. Elevated concentrations and accumulation rates were also found at 8230 and 5320 14C yr B.P., which are consistent with the elevated dust fluxes recorded by Greenland ice cores. By far the greatest contribution of the three elements to the peat inventory is atmospheric soil dust, and the metal fluxes vary not only with climate change but also land-use history (especially the beginning of forest clearing for agriculture ca. 6 millennia ago). The V/Sc, Cr/Sc, and Ni/ Sc ratios were remarkably similar to their corresponding ratios in the earth's crust until the onset of the Industrial Revolution (240 14C yr B.P.), which largely validates the use of crustal concentrations for calculating enrichment factors (EF) for these elements. In modern samples, the EFs of V, Cr, and Ni reach maximum values between 2.4 and 4.1, relative to background; anthropogenic emissions are a more likely explanation of the elevated EFs than either plant uptake or chemical diagenesis. This study demonstrates the usefulness of peat bogs as archives of atmospheric metal deposition and underpins the potential of peat cores to help distinguish between lithogenic and anthropogenic metal sources.

A peat core from a Swiss bog represents 2110 14C years of peat accumulation and provides a continuous record of atmospheric rare earth element (REE) deposition. This is the first study providing a time-series of all REE originating from the atmosphere. Concentrations of the 14 REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) were determined using inductively coupled plasma-mass spectrometry (ICP-MS) after dissolution of 200 mg aliquots of age-dated peat samples with 3 ml HNO3 and 0.1 ml HBF4 at 240 degrees C in a microwave autoclave. Strict quality control schemes were applied to ensure the accuracy of the applied analytical methodology. Previous analyses of selected REE by instrumental neutron activation analysis (INAA) in the same set of peat samples revealed that INAA frequently under- or overestimated REE concentrations in a systematic manner. Concentration profiles obtained for all REE were almost identical, except for Ce and Eu. Calculation of enrichment factors (EF) revealed a distinct depletion of heavy REE relative to light REE in peat samples since the beginning of the 19th century which marks the onset of the Industrial Revolution in Europe, suggesting a pronounced influence by anthropogenic activities. Enrichments of REE calculated using Sc as a reference element exceeded unity, relative to the Upper Continental Crust. Overall, EF in all peat samples ranged from 1.96 for Sm to 2.34 for Gd, with considerably lower EF for Ce (1.82) and Eu (1.44), respectively. A significant enrichment of all REE which may have been caused by military activities, was observed in the peat sample dating from World War II (1944); this exceptional sample, however, is not enriched in Ce. The concentration profiles of REE were similar but not identical to those of other lithogenic, conservative reference elements such as Sc, Y, Al, Zr and Ti. While it has been suggested that individual REE concentrations or the sum of REE can be used as a reference parameter to calculate crustal EF in environmental samples the data presented here indicates that anthropogenic emissions of REE cannot simply be ignored.

Peat cores from two bogs were used to reconstruct changes in net atmospheric mercury deposition in Switzerland for the past 2-3 millennia. The two records were compared to assess the reliability of peat cores as archives of atmospheric mercury deposition. Net mercury accumulation rates and Hg(ex), an indicator of significant anthropogenic mercury contamination, were calculated for both cores. Both records showed stable background values (0.5-1.9 and 1.0-3.0 microg of Hg m(-2) yr(-1)). In both profiles, mercury accumulation rates began to increase during the 12th century, and Hg(ex) appeared during the 14th century. The late 19th and early 20th centuries have been studied in detail. The profiles match well with the history of local and global mercury emissions. The magnitude of increase from the pre-anthropogenic to anthropogenic period was also very similar in both records. Although the two sites are botanically very similar and lie only 3.5 km apart, accumulation rates at TGE were generally higher than those at EGR. This indicates that, although such records can be used to determine the chronologies of and relative changes in rates of atmospheric mercury deposition, differences in rates of mercury accumulation rates between sites do not necessarily indicate differences in deposition rates of mercury from the atmosphere.

Peat cores were collected from three minerogenic peatlands in Switzerland: La Tourbière des Genevez (TGE), in Canton Jura; Gola di Lago (GDL), in Canton Ticino; and Mauntschas (MAU), in Canton Grisons. Chemical analyses of the pore waters and the peats document the increasingly minerogenic character with depth. In particular, the Sr concentration profile in the peats reflects the growing importance of mineral sediment dissolution with increasing distance below the peat surface. Despite this circumstance, Pb concentrations are greatest in the surface layers, and decrease with depth. Thus, dissolution of the basal sediments at these sites appears to be an unimportant source of Pb, compared with atmospheric deposition. Twenty-one new radiocarbon age dates for the three cores provide a chronology of Pb enrichment, and these are consistent with the record of atmospheric Pb deposition recorded by the ombrotrophic peat bog 'Etang de la Gruère' (EGR). Sediment samples from TGE and EGR were reacted at pH 5 with ammonium acetate to dissolve the carbonate fraction, filtered, and the residues analyzed using XRF. These analyses show that much of the Ca, Mg, Sr and Mn is lost when the carbonate fraction is dissolved, but this process does not measurably affect Pb. This finding suggests that carbonate dissolution dominates the weathering of the sediments underlying these peat deposits, but this fraction does not contain significant concentrations of Pb. Minerogenic peat deposits such as those described here, therefore, can serve as reliable archives of atmospheric Pb deposition, provided that mineral dissolution in the underlying sediments does not contribute measurably to the Pb inventory of the peat profile.

The accumulation of selected trace elements (Cu, Ni, Zn, Pb, As) in the surface peat layer of an ombrotrophic bog 2.4 km from a Cu-Ni smelter at Harjavalta, Finland was studied using a peat core. A reference core was taken from an ombrotrophic bog at a background site, Hietajärvi, in eastern Finland. Element concentrations were analysed from 1-cm slices and enrichment factors (EF) were calculated. The enrichment factors of both Cu and Ni in the Harjavalta peat bog are extremely high compared to the Hietajärvi site. However, only the 6-cm surface peat Pb values are higher in Harjavalta compared to Hietajärvi. Precipitation was collected during 1992-1996, in the vicinity of the Harjavalta smelter, in order to estimate the current atmospheric deposition load. Comparison between the precipitation and peat data reveals that at Harjavalta the surface peat is relatively much more polluted than the current precipitation. The variation in EF of the Harjavalta peat core with respect to depth shows two patterns: Cu and Pb are similar, as are Ni, Zn and As. The vertical gradient in Harjavalta Cu EF suggests that Cu supplied to the peat by atmospheric deposition is very well preserved by the bog.

Traditional peat sample preparation methods such as drying at high temperatures and milling may be unsuitable for Hg concentration determination in peats due to the possible presence of volatile Hg species, which could be lost during drying. Here, the effects of sample preparation and natural variation on measured Hg concentrations are investigated. Slight increases in mercury concentrations were observed in samples dried at room temperature and at 30 degrees C (6.7 and 2.48 ng kg(-1) h(-1), respectively), and slight decreases were observed in samples dried at 60, 90 and 105 degrees C (2.36, 3.12 and 8.52 ng kg(-1) h(-1), respectively). Fertilising the peat slightly increased Hg loss (3.08 ng kg(-1) h(-1) in NPK-fertilised peat compared to 0.28 ng kg(-1) h(-1) in unfertilised peat, when averaged over all temperatures used). Homogenising samples by grinding in a machine also caused a loss of Hg. A comparison of two Hg profiles from an Arctic peat core, measured in frozen samples and in air-dried samples, revealed that no Hg losses occurred upon air-drying. A comparison of Hg concentrations in several plant species that make up peat, showed that some species (Pinus mugo, Sphagnum recurvum and Pseudevernia furfuracea) are particularly efficient Hg retainers. The disproportionally high Hg concentrations in these species can cause considerable variation in Hg concentrations within a peat slice. The variation of water content (1.6% throughout 17-cm core, 0.97% in a 10 x 10 cm slice), bulk density (40% throughout 17-cm core, 15.6% in a 10 x 10 cm slice) and Hg concentration (20% in a 10 x 10 cm slice) in ombrotrophic peat were quantified in order to determine their relative importance as sources of analytical error. Experiments were carried out to determine a suitable peat analysis program using the Leco AMA 254, capable of determining mercury concentrations in solid samples. Finally, an analytical protocol for the determination of Hg concentrations in solid peat samples is proposed. This method allows correction for variation in factors such as vegetation type, bulk density, water content and Hg concentration in individual peat slices. Several subsamples from each peat slice are air dried, combined and measured for Hg using the AMA254, using a program of 30 s (drying), 125 s (decomposition) and 45 s (waiting). Bulk density and water content measurements are performed on every slice using separate subsamples.

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.

An efficient method was developed for the analysis of selected PCBs and PAHs in dry peat samples. The method includes a shaking extraction using acetone and hexane followed by the purification of the crude extract by gel permeation chromatography (GPC) which turned out to be the key clean-up step. The method was used to determine seven indicator PCBs and 16 EPA-PAHs in individual sections of an ombrotrophic peat core in south-west Switzerland. The maximum concentrations of PCBs (19 microg sigma PCBs/kg dm) were found at a peat depth of 10-15 cm which is estimated to correspond to a time period of 1976-1960 whereas the PAH profile showed a maximum (2853 microg sigma PAHs/kg dm) at a depth of 20-25 cm which represents circa 1951-1930. Compared to these maxima, the concentrations of PAHs in the top layer (1990-1986) are six times lower, but the decline in PCBs is only 38%. The concentration profiles are generally consistent with known changes in contaminant emissions, and suggest that more detailed studies of ombrogenic peat bog profiles could be used for detailed reconstructions of the changing atmospheric fluxes of these and other organic contaminants.

The aim of this study was to obtain an overview of trace element concentrations in Swiss forest soils and to critically assess the measured values with respect to anthropogenic input vs. lithogenic background. Twenty-three sites were selected which represent a broad range of natural forest sites, bedrock material and soil types of Switzerland. At each site, samples were collected from all genetic soil horizons down to a C or B/C horizon. Total concentrations of As, Cr, Cu, Ni, Pb, and Zn in all samples were determined by X-ray fluorescence spectrometry. There were distinct differences in the geological background values estimated from the concentrations measured in the samples from the lowest soil horizon. Background concentrations for Cr and Ni were lowest in granite and gneiss, whereas Pb and Zn were highest in limestone and marl. Enrichment or depletion of the trace elements was assessed using Zr as reference element. Within the same profile, the six trace elements showed completely different enrichment/depletion patterns with depth. The various natural processes and anthropogenic inputs that can lead to these patterns are critically discussed. Based on this critical assessment, pollution of the investigated forest soils was found to be most severe for Pb and Zn and to a somewhat lesser extent for As and Cu, whereas anthropogenic input of Cr and Ni seems to be less important. The data suggest that a critical evaluation of enrichment factors is a better tool to assess soil pollution with trace elements than the use of maximum allowable concentrations (MAC) for topsoil samples. The enrichment factors calculated as described here consider the effects of geological variation on metal abundances whereas the MAC does not. In order to obtain an estimate of soil solution concentrations, water extracts of the samples collected from a subset of 10 soil profiles were analyzed for the same trace elements. Solubility of all elements generally decreased with soil depth. An exception was Cr, Cu, and Ni solubility in the humus layer, which was lower than in the underlying mineral horizon. For all elements, solubility was higher for the collective of soil samples depleted in this element when compared to the samples, in which the element was enriched.

Peat cores taken from eight Swiss peatlands were used to calculate inventories of anthropogenic Pb using either Sc or Zr to quantify Pb derived from rock weathering. The shapes of the Pb/Sc and Pb/Zr profiles suggest that Pb was supplied exclusively by atmospheric deposition at all sites. At one of the sites (Etang de la Gruère), anthropogenic Pb was calculated using both Sc and Zr as the conservative reference element. Lithogenic Pb determined using Sc was twice that obtained using Zr, possibly because Zr resides only in zircons which are dense compared to pyroxene and amphibole which are the main Sc-bearing phases in the earth's crust. However, the inventory of 'natural' Pb (supplied almost entirely by soil dust) is dwarfed by the anthropogenic inventory such that anthropogenic Pb calculated using Sc and Zr agree to within 5%. The total amount of anthropogenic Pb accumulated in the bogs was calculated by simply adding the mass of anthropogenic Pb for each peat slice over the length of each core. Cumulative, anthropogenic Pb calculated in this way ranged from 1.0 to 9.7 g/m2 and showed pronounced regional differences: the site south of the Alps (Gola di Lago in Canton Ticino) with direct exposure to the heavily industrialized region of northern Italy received nearly 10 times more anthropogenic Pb as the sites in more remote alpine regions (Schöpfenwaldmoor in Canton Berne, and Mauntschas in Canton Grisons). The approach used here to calculate cumulative, anthropogenic, atmospheric Pb (CAAPb) is simple and robust, independent of the chronology of Pb deposition, and makes no assumptions about the immobility of Pb within the peat profile. Given the worldwide distribution of peat bogs, it should be possible to undertake continental and global inventories of atmospheric metal deposition, for both the natural and anthropogenic components of most trace metals of environmental interest.

The visual uniformity of tropical peat swamp forest masks the considerable variation in forest structure that has evolved in response to differences and changes in peat characteristics over many millennia. Details are presented of forest structure and tree composition of the principal peat swamp forest types in the upper catchment of Sungai Sebangau, Central Kalimantan, Indonesia, in relation to thickness and hydrology of the peat. Consideration is given to data on peat geochemistry and age of peat that provide evidence of the ombrotrophic nature of this vast peatland and its mode of formation. The future sustainability of this ecosystem is predicted from information available on climate change and human impact in this region.

A peat core from a bog in northwest Spain provides a record of the net accumulation of atmospheric mercury since 4000 radiocarbon years before the present. It was found that cold climates promoted an enhanced accumulation and the preservation of mercury with low thermal stability, and warm climates were characterized by a lower accumulation and the predominance of mercury with moderate to high thermal stability. This record can be separated into natural and anthropogenic components. The substantial anthropogenic mercury component began approximately 2500 radiocarbon years before the present, which is near the time of the onset of mercury mining in Spain. Anthropogenic mercury has dominated the deposition record since the Islamic period (8th to 11th centuries A.D.). The results shown here have implications for the global mercury cycle and also imply that the thermal lability of the accumulated mercury can be used not only to quantify the effects of human activity, but also as a new tool for quantitative paleotemperature reconstruction.

An Energy-dispersive Miniprobe Multielement Analyzer (EMMA) was designed and constructed for sensitive, rapid, and non-destructive analysis of trace elements (As, Cr, Cu, Fe, Ga, Ge, Hf, Mn, Ni, Pb, Rb, Se, Sr, Th, Y, U, Zn) in small (e.g. 50 microm) samples such as individual mineral grains from rocks. An alternative configuration of the EMMA instrument is described here for use with larger samples such as powders of coal, soil, sediments, and plant materials. To minimize heterogeneity problems, a larger X-ray beam size (0.1 x 6 mm) was used by installing a different collimator, and the sample holder rotated 25 times per minute. Using this approach, Rb, Sr, Cu, Zn and Pb were measured in peat samples collected from bogs in Switzerland and northern Scotland. The detection limit for Pb, for example, is approximately 0.3 microg/g which is one order of magnitude better than conventional XRF analyzers. For comparison, Pb was also measured in acid digests of the same samples using GFAAS. The Pb results obtained using EMMA are comparable to the GFAAS data for the continental peat samples. However, in the Cl-rich samples from the maritime bogs, the GFAAS signal was strongly suppressed, and an accurate comparison of the two methods was not possible. The EMMA technique, therefore, has three advantages over conventional GFAAS: first, no sample dissolution is required; second, several elements of interest are determined simultaneously; and third, the EMMA technique is not subject to matrix interferences.