Atmospheric deposition of silver and thallium since 12 370 14C years BP recorded by a Swiss peat bog profile, and comparison with lead and cadmium

A peat core from an ombrotrophic bog in Switzerland provides the first complete, long-term record (14 500 years) of atmospheric Ag and Tl deposition. The lack of enrichment of Ag and Tl in the basal peat layer shows that mineral dissolution in the underlying sediments has not contributed measurably to the Ag and Tl inventories in the peat column, and that Ag and Tl were supplied exclusively by atmospheric deposition. The temporal and spatial distribution of modern peaks in Ag and Tl concentrations are similar to those of Pb which is known to be immobile in peat profiles. Silver and Tl, therefore, are effectively immobile in the peat bog also, allowing an atmospheric deposition chronology to be reconstructed. Silver concentrations vary by up to 114x and Tl up to 241x. While Holocene climate change and land use history can explain the variation in metal concentrations and enrichment factors (EF) in ancient peats (i.e. pre-dating the Roman Period), anthropogenic sources have to be invoked to explain the very high EF values (up to 123 in the case of Ag and 12 in the case of Tl) in peat samples since the middle of the 19th Century. The "natural background" EF of Tl in ancient peats is remarkably close to unity, indicating a lack of significant enrichment of this element in atmospheric aerosols due to chemical weathering of crustal rocks. Silver, on the other hand, shows a pronounced enrichment from 8030 to 5230 (14)C years BP (12x compared to crustal rocks); this may be due to weathering phenomena or biological processes, both of which are driven by climate. Even compared to the natural enrichment of Ag during the mid-Holocene, however, the enrichments of Ag and Tl in modern peats from the Industrial Period are at least an order of magnitude greater. The Pb/Ag and Tl/Ag ratios show that Pb and Tl are preferentially released, compared to Ag, during smelting of argentiferous Pb ores mined during the Roman and Medieval Periods.     

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.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Contamination of Canadian and European bottled waters with antimony from PET containers

Using clean lab methods and protocols developed for measuring Sb in polar snow and ice, we report the abundance of Sb in fifteen brands of bottled water from Canada and forty-eight from Europe. Comparison with the natural abundance of Sb in pristine groundwaters, water bottled commercially in polypropylene, analyses of source waters prior to bottling, and addition of uncontaminated groundwater to PET bottles, provides unambiguous evidence of Sb leaching from the containers. In contrast to the pristine groundwater in Ontario, Canada containing 2.2 +/- 1.2 ng l(-1) Sb, 12 brands of bottled natural waters from Canada contained 156 +/- 86 ng l(-1) and 3 brands of deionized water contained 162 +/- 30 ng l(-1); all of these were bottled in PET containers. Natural water from Ontario bottled in polypropylene contained only 8.2 +/- 0.9 ng l(-1). Comparison of three German brands of water available in both glass bottles and PET containers showed that waters bottled in PET contained up to 30 times more Sb. To confirm that the elevated Sb concentrations are due to leaching from the PET containers, water was collected in acid-cleaned LDPE bottles from a commercial source in Germany, prior to bottling; this water was found to contain 3.8 +/- 0.9 ng l(-1) Sb (n = 5), compared with the same brand of water purchased locally in PET bottles containing 359 +/- 54 ng l(-1) (n = 6). This same brand of water in PET bottles, after an additional three months of storage at room temperature, yielded 626 +/- 15 ng l(-1) Sb (n = 3). Other German brands of water in PET bottles contained 253-546 ng l(-1) Sb (n = 5). The median concentration of Sb in thirty-five brands of water bottled in PET from eleven other European countries was 343 ng l(-1) (n = 35). As an independent check of the hypothesis that Sb is leaching from PET, the pristine groundwater from Canada (containing 2.2 +/- 1.2 ng l(-1) Sb) was collected from the source using PET bottles from Germany: this water contained 50 +/- 17 ng l(-1) Sb (n = 2) after only 37 days, even though it was stored in the refrigerator, and 566 ng l(-1) after six months storage at room temperature.     

Natural and anthropogenic enrichments of molybdenum, thorium, and uranium in a complete peat bog profile, Jura Mountains, Switzerland

A core from an ombrotrophic Swiss bog representing 12 370 (14)C years of peat accumulation was evaluated as a possible archive of atmospheric deposition of Mo, Th and U. Calcium, Sr, and Ba were also determined to quantify weathering inputs, Mn to follow possible redox transformations, and Rb to identify plant uptake. Each of these elements was determined using ICP-MS, following digestion in a microwave heated autoclave using 3 ml HNO(3) and 0.1 ml HBF(4). Calcium and Sr clearly identify the thickness of the ombrotrophic zone because they are enriched in the minerogenic zone relative to the concentration of mineral matter. The concentration of Ba, however, is proportional to the concentration of mineral matter in all samples, and is not added to peat column by weathering reactions at the peat-sediment interface. The lowest element concentrations are found during the Holocene climate optimum (5320 to 8030 (14)C year BP) with the following natural background values (n= 18): Mo 0.08 +/- 0.02 microg g(-1), U 0.029 +/- 0.008 microg g(-1), Ba 5.2 +/- 2.6 microg g(-1), Th 0.070 +/- 0.022 microg g(-1) and Rb 0.63 +/- 0.09 microg g(-1). By far the highest concentrations of Ba, Mn, Rb and Th were found during the Younger Dryas cold climate event (10 590 (14)C year BP) when the flux of atmospheric soil dust was at its post-glacial maximum. Molybdenum and U are elevated in concentration throughout the minerogenic zone because of sediment weathering and this masks the atmospheric signal in samples older than ca. 8000 (14)C year BP (ca. 9000 calendar years). Enrichment factors (EF) calculated using Sc as a conservative, lithogenic element shows that minerogenic peats are enriched in Mo up to 18x and U 26x, relative to the natural "background" values. During the two millennia prior to industrialisation, the accumulation rate of atmospheric Mo averaged 0.23 +/- 0.13 microg m(-2) year(-1). With the onset of the Industrial Revolution, Mo accumulation rates rapidly and continuously increased to approximately 10 microg m(-2) year(-1) in the late 1980s. These data suggest that Mo in atmospheric aerosols today is derived predominately from anthropogenic emissions. Uranium does not show the same enrichment pattern which suggests that steel-making rather than coal combustion is the primary source of atmospheric Mo contamination at this site.     

Winter arsenic pollution in 10 forest ecosystems in the mountainous border regions of the Czech Republic

Environmental Science and Pollution Research - Arsenic (As) concentrations and deposition fluxes were measured in snow and rime at 10 mountain-top sites near the borders between the Czech Republic...     

Natural abundance of Sb and Sc in pristine groundwaters, Springwater Township, Ontario, Canada, and implications for tracing contamination from landfill leachates

Using ICP-SMS and the clean lab methods and procedures developed for determining trace element concentrations in polar snow and ice, a lower limit of detection (LOD) of 30 pg l(-1) for Sb and 5 pg l(-1) for Sc was achieved, allowing the natural abundances of Sb and Sc to be measured in pristine groundwaters. Water samples were collected from natural flows and wells between Elmvale and Wyevale in Springwater Township, Ontario, Canada. The water in this region is derived from chemical reactions between meteoric fluids and the Quaternary sediments which cover the bedrock (dolomitic limestone) to depths of more than 100 m. The chemical composition of these waters (pH 8) is primarily a reflection of reactions between the percolating fluids with calcite and dolomite. The maximum concentration of Sb was 5.0 ng l(-1), and the average of all samples collected was 2.2 +/- 1.2 ng l(-1) (n = 34). The average concentration of Sc was 8.6 +/- 4.7 ng l(-1) (n = 28). The paucity of published Sb concentration data available for comparison is probably because most of the analytical methods commonly used to date, including GFAAS, HG-AAS, HG-AFS, INAA, and ICP-QMS, have lower limits of detection which are inadequate for reliably determining the natural abundance of Sb in many uncontaminated groundwaters. Also, the measurement of extremely low concentrations of Sb requires extra care to avoid possible contamination. Given the extensive use of Sb in plastics, we show that some of the containers used to collect and store samples, and for handling and preparing samples for chemical analyses, may be important sources of contamination in the laboratory. The Sb and Sc concentrations reported here should serve as reference values for this region, against which contamination by various human impacts in future could be compared.     

An ultra-clean firn core from the Devon Island Ice Cap, Nunavut, Canada, retrieved using a titanium drill specially designed for trace element studies

An electromechanical drill with titanium barrels was used to recover a 63.7 m long firn core from Devon Island Ice Cap, Nunavut, Canada, representing 155 years of precipitation. The core was processed and analysed at the Geological Survey of Canada by following strict clean procedures for measurements of Pb and Cd at concentrations at or below the pg g(-1) level. This paper describes the effectiveness of the titanium drill with respect to contamination during ice core retrieval and evaluates sample-processing procedures in laboratories. The results demonstrate that: (1) ice cores retrieved with this titanium drill are of excellent quality with metal contamination one to four orders of magnitude less than those retrieved with conventional drills; (2) the core cleaning and sampling protocols used were effective, contamination-free, and adequate for analysis of the metals (Pb and Cd) at low pg g(-1) levels; and (3) results from 489 firn core samples analysed in this study are comparable with published data from other sites in the Arctic, Greenland and the Antarctic.     

Lithogenic, oceanic and anthropogenic sources of atmospheric Sb to a maritime blanket bog, Myrarnar, Faroe Islands

Antimony concentrations were measured in a core collected from Myrarnar, a blanket bog on the Faroe Islands which has been accumulating peat for more than six thousand years. The vertical distribution of Sb indicates that it has been supplied to the peat exclusively from the atmosphere. Despite the proximity to the ocean, the contribution of Sb to the peat from marine aerosols amounts to less than ca. 10% of the natural inputs. Although the peat core contains four notable layers of volcanic ash originating from Iceland, these have not contributed significantly to the Sb inventory. However, the distribution of Sb closely resembles that of Pb, with most of the Sb found in peats dating from the industrial period. Peat samples dating from the Roman Period are not only contaminated with Pb, but also with Sb. Lead is known to be immobile in peat bogs, and in Europe has been derived predominantly from industrial sources for thousands of years. The correlation between Sb and Pb in the peat core from the Faroe Islands supports the hypothesis that Sb is also effectively immobile in peat, and that ombrotrophic bogs are faithful archives of atmospheric Sb deposition. The data presented here also reinforces the view that natural Sb inputs during the past two centuries are dwarfed by industrial inputs, and that human activities have affected the atmospheric Sb cycle to a comparable extent to that of Pb. The natural rate of atmospheric Sb deposition recorded by the peat core (0.33 microg m(-2) year(-1)) is remarkably similar to the value obtained from a Swiss peat bog (Etang de la Gruère) in the samples dating from ca. 6000 to 9000 years ago (0.35 microg m(-2) year(-1)) which suggests that the background rates obtained from the peat cores have broader validity. Consistent with previous work, the data from the Faroe Islands suggests that the natural flux of Sb to the global atmosphere may have been overestimated by a factor of ten, and that the influence of human activities has been underestimated to the same extent.     

The desorption of antimony(V) from sediments, hydrous oxides, and clay minerals by carbonate, phosphate, sulfate, nitrate, and chloride

The desorption of antimony, Sb(V), from two sediment samples by phosphate, carbonate, sulfate, chloride, and nitrate at pH 8 was examined. One highly contaminated sediment sample was taken from an Sb mine (Goesdorf, Luxembourg); the other sample was the certified reference material PACS-2 (marine sediment). Phosphate was found to have a strong mobilizing ability, whereas that of carbonate was in general weaker. For comparison, and to understand better the possible importance of individual components of the sediments, desorption experiments were performed on pure phases (i.e., hydrous oxides of Fe, Mn, and Al) and the clay minerals kaolinite and montmorillonite. In the cases of hydrous metal oxides, Sb(V) was most effectively desorbed by phosphate, followed by carbonate. Phosphate also desorbed Sb(V) from the clay minerals, whereas carbonate had no effect. The pH dependence of adsorption of Sb(V) in the absence and presence of carbonate revealed that adsorption densities were higher (except in the case of montmorillonite) in the absence of carbonate, suggesting a competition between carbonate and [Sb(OH)] for surface sites generally and a lowering of surface charge in the case of hydrous aluminum oxide. The observations are unlikely to be due to ionic strength effects because activity coefficients in the blank and spiked solutions differ by <4%. Desorption experiments on sediments with varying concentrations of phosphate and carbonate demonstrated that at environmentally relevant concentrations, desorption by phosphate is negligible, whereas the effect of carbonate is not. Sulfate, chloride, and nitrate generally had little effect. The proportion of Sb desorbed in blank experiments coincides with that mobilized in the first fraction of the Bureau Communautaire de Référence (BCR) sequential extraction (easily exchangeable and carbonate-bound fraction).