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.
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.
Sphagnum moss was collected from 21 ombrotrophic (rain-fed) peat bogs surrounding open pit mines and upgrading facilities of Athabasca bituminous sands in Alberta (AB). In comparison to contemporary Sphagnum moss from four bogs in rural locations of southern Germany (DE), the AB mosses yielded lower concentrations of Ag, Cd, Ni, Pb, Sb, and Tl, similar concentrations of Mo, but greater concentrations of Ba, Th, and V. Except for V, in comparison to the "cleanest", ancient peat samples ever tested from the northern hemisphere (ca. 6000-9000 years old), the concentrations of each of these metals in the AB mosses are within a factor of 3 of "natural, background" values. The concentrations of "heavy metals" in the mosses, however, are proportional to the concentration of Th (a conservative, lithophile element) and, therefore, contributed to the plants primarily in the form of mineral dust particles. Vanadium, the single most abundant trace metal in bitumen, is the only anomaly: in the AB mosses, V exceeds that of ancient peat by a factor of 6; it is therefore enriched in the mosses, relative to Th, by a factor of 2. In comparison to the surface layer of peat cores collected in recent years from across Canada, from British Columbia to New Brunswick, the Pb concentrations in the mosses from AB are far lower.
Adopting recently developed clean laboratory techniques, antimony (Sb) and scandium (Sc) deposition were measured in a 63.72 m-long ice core (1842-1996) and a 5 m deep snow pit (1994-2004) collected on Devon Island, Canadian High Arctic. Antimony concentrations ranged from 0.07 to 108 pg g(-1) with a median of 0.98 pg g(-1)(N= 510). Scandium, used as a conservative reference element, revealed that dust inputs were effectively constant during the last 160 years. The atmospheric Sb signal preserved in the ice core reflects contamination from industrialisation, the economic boom which followed WWII, as well as the comparatively recent introduction of flue gas filter technologies and emission reduction efforts. Natural contributions to the total Sb inventory are negligible, meaning that anthropogenic emissions have dominated atmospheric Sb deposition throughout the entire period. The seasonal resolution of the snow pit showed that aerosols deposited during the Arctic winter, when air masses are derived mainly from Eurasia, show the greatest Sb concentrations. Deposition during summer, when air masses come mainly from North America, is still enriched in Sb, but less so. Snow and ice provide unambiguous evidence that enrichments of Sb in Arctic air have increased 50% during the past three decades, with two-thirds being deposited during winter. Most Sb is produced in Asia, primarily from Sb sulfides such as stibnite (Sb2S3), but also as a by-product of lead and copper smelting. In addition there is a growing worldwide use of Sb in automobile brake pads, plastics and flame retardants. In contrast to Pb which has gone into decline during the same interval because of the gradual elimination of gasoline lead additives, the enrichments of Sb have been increasing and today clearly exceed those of Pb. Given that the toxicity of Sb is comparable to that of Pb, Sb has now replaced Pb in the rank of potentially toxic trace metals in the Arctic atmosphere.
This is the ®rst study to report on the determination of Sb species in urine. To this end, HPLC was coupled online to an ICP-MS instrument using ultrasonic nebulization (USN) or hydride generation (HG) for sample introduction into the ICP-MS. The high chloride concentration in urine seriously hampered the chromatographic separation of Sb(V) and Sb(III) on the Dionex AS14 anion exchange column. Distinct signal suppression, shifting of retention times and severe peak broadening did not allow the application to urine samples. Progress to avoid these problems in HPLC-USN-ICP-MS could be made by employing a Hamilton PRP-X100 anion-exchange column. However, Na eluting in the void volume of the column gave rise to a Na-induced peak overlapping with the Sb(V) signal when USN was used to aspirate the HPLC eluents into the plasma. Therefore, a HG system was placed between the HPLC and ICP-MS instrumentation to overcome this dilemma. Thus, Sb(V) and Sb(III) were separated in urine with the PRP-X100 column using 20 mM EDTA at pH 4.7 as the mobile phase. Similarly, an ION-120 anion-exchange column was employed to separate trimethylantimony dichloride (TMSbCl 2) and Sb(V) with a mobile phase containing 2 mM NH 4 HCO 3 and 1 mM tartaric acid at pH 8.5. Detection limits of 20 ng l 21 , 12 ng l 21 and 8 ng l 21 for Sb(V), TMSbCl 2 and Sb(III), respectively, could be established in a 1z2 diluted urine matrix. The developed HPLC-HG-ICP-MS method was applied to the speciation of Sb in the urine of occupationally exposed and non-exposed subjects. Additionally, two lyophilised urine reference materials were investigated. Sb(V) was by far the predominant Sb species, followed by TMSbCl 2. Only ultratraces of Sb(III), if any detectable, could be found. The sum of the concentrations of Sb(V), Sb(III) and TMSbCl 2 in urine samples ranged between 51 and 78% of their total Sb concentrations.
Antimony concentrations were determined in 132 brands of bottled water from 28 countries. Two of the brands were at or above the maximum allowable Sb concentration for drinking water in Japan (2 µg/L). Elevated concentrations of Sb in bottled waters are due mainly to the Sb 2 O 3 used as the catalyst in the manufacture of polyethylene terephthalate (PET(E)). The leaching of Sb from PET(E) bottles shows variable reactivity. In 14 brands of bottled water from Canada, Sb concentrations increased on average 19% during 6 months storage at room temperature, but 48 brands of water from 11 European countries increased on average 90% under identical conditions. A mineral water from France in PET(E), purchased in Germany, yielded 725 ng/L when first tested, but 1510 ng/L when it was stored for 6 months at room temperature; the same brand of water, purchased in Hong Kong, yielded 1990 ng/L Sb. Pristine groundwater containing 1.7 ( 0.4 ng/L Sb (n ) 6) yielded 26.6 ( 2.3 ng/L Sb (n ) 3) after storage in PET-(E) bottles from Canada for 6 months versus 281 ( 38 ng/L Sb (n ) 3) in PET(E) bottles from Germany. Tap water bottled commercially in PET(E) in December 2005 contained 450 ( 56 ng/L Sb (n ) 3) versus 70.3 ( 0.3 ng/L Sb (n ) 3) when sampled from a household faucet in the same village (Bammental, Germany), and 25.7 ( 1.5 ng/L Sb (n ) 3) from a local artesian flow.
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.
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