A comparison of antimony and lead profiles over the past 2500 years in Flanders Moss ombrotrophic peat bog, Scotland

Two cores collected in 2001 and 2004 from Flanders Moss ombrotrophic peat bog in central Scotland were dated (14C, 210Pb) and analysed (ICP-OES, ICP-MS) to derive and compare the historical atmospheric deposition records of Sb and Pb over the past 2500 years. After correction, via Sc, for contributions from soil dust, depositional fluxes of Sb and Pb peaked from ca. 1920-1960 A.D., with >95% of the anthropogenic inventories deposited post-1800 A.D. Over the past two centuries, trends in Sb and Pb deposition have been broadly similar, with fluctuations in the anthropogenic Sb/Pb ratio reflecting temporal variations in the relative input from emission sources such as the mining and smelting of Pb ores (in which Sb is commonly present, as at Leadhills/Wanlockhead in southern Scotland), combustion of coal (for which the Sb/Pb ratio is approximately an order of magnitude greater than in Pb ores) and exhaust emissions (Pb from leaded petrol) and abrasion products from the brake linings (Sb from heat-resistant Sb compounds) of automobiles. The influence of leaded petrol has been most noticeable in recent decades, firstly through the resultant minima in Sb/Pb and 206Pb/207Pb ratios (the latter arising from the use of less radiogenic Australian Pb in alkylPb additives) and then, during its phasing out and the adoption of unleaded petrol, complete by 2000 A.D., the subsequent increase in both Sb/Pb and 206Pb/207Pb ratios. The extent of the 20th century maximum anthropogenic enrichment of Sb and Pb, relative to the natural Sc-normalised levels of the Upper Continental Crust, was similar at approximately 50- to 100-fold. Prior to 1800 A.D., the influence of metallurgical activities on Sb and Pb concentrations in the peat cores during both the Mediaeval and Roman/pre-Roman periods was discernible, small Sb and Pb peaks during the latter appearing attributable, on the basis of Pb isotopic composition, to the mining/smelting of Pb ores indigenous to Britain.     

Two thousand years of atmospheric rare earth element (REE) deposition as revealed by an ombrotrophic peat bog profile,Jura Mountains,Switzerland

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.     

Scottish peat bog records of atmospheric vanadium deposition over the past 150 years: comparison with other records and emission trends

Cores from four Scottish ombrotrophic peat bogs were used to reconstruct the historical record of atmospheric vanadium (V) deposition in Scotland over the last 150 years. The general similarity of V and Pb concentration profile trends in (210)Pb-dated cores from each of the sites strongly suggested that V, like Pb, is essentially immobile in ombrotrophic peat. After allowance via use of the conservative element Ti for the contribution of soil dust V, the deposition of anthropogenic V was found to be greatest (～ 1.3 to 2.0 mg m(-2) y(-1)) in the mid-20(th) century before decreasing to 0.1-0.3 mg m(-2) y(-1) in the early years of the 21(st) century. The latter values were in good agreement with directly measured atmospheric V fluxes at nearby sites, a finding also observed in the case of Pb. The decline in peat-core-derived fluxes for both V and Pb from 1970 to 2004, however, was not as large as the decline in official UK emission estimates for the two metals during this period. This, along with an order of magnitude discrepancy between the anthropogenic V/Pb ratios at the peat core surface and the higher values of the ratio for UK emissions in the early 2000s, suggests that the recently revised UK emissions data for V may perhaps still be overestimated and/or that some previously deposited Pb is being resuspended in the atmosphere.     

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.     

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.     

Predominant anthropogenic sources and rates of atmospheric mercury accumulation in southern Ontario recorded by peat cores from three bogs: comparison with natural "background" values (past 8000 years)

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.     

Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

强酸型离子交换纤维富集-火焰原子吸收测定水中痕量铜、铅、镉、镍

通过强酸型离子交换纤维柱,在同一水样中同时富集和洗脱了铜、铅、镉、镍,采用火焰原子吸收光谱法测定,并对富集条件及洗脱条件、干扰因素进行了探讨。该方法简便易行,回收率在96.1%~105.5%之间,测定的相对标准偏差小于5.0%。     

Daily dietary intakes of zinc,copper, lead,and cadmium as determined by duplicate portion sampling combined with either instrumental analysis or the use of food composition tables,Shiraz, Iran

Estimation of essential and toxic element intakes is crucial to evaluate the risks of deficiency or toxicity. The purpose of this study was to investigate and also to compare the dietary intakes of zinc (Zn) and copper (Cu) by adults living in Shiraz, Iran, determined by two procedures: duplicate portion sampling of 21 hospital meals combined with either instrumental analysis (voltammetric measurement) or the use of food composition tables (FCTs). The level of exposure to lead (Pb) and cadmium (Cd) was evaluated as well. The daily Zn intakes of both methods were not significantly different and were higher than the RDA values except the value measured by the instrumental analysis which was lower than the RDA established for a male adult. Daily intake of Cu determined by instrumental analysis was significantly lower and closer to RDA for adults compared with the value estimated by FCTs. The dietary intakes of Pb and Cd were 313 and 61 % of the respective provisional tolerable weekly intakes (PTWIs), respectively. The accuracy of two methods used for estimation of Zn intake was similar. In the case of Cu, the use of FCTs, in which the influence of environmental conditions and dietary habits of meal preparation is not taken into account, overestimated dietary intake. The risk of zinc deficiency was found in adult males. Moreover, the estimated intake of Pb, but not Cd, could be a cause of concern for Shiraz population. Thus, conducting regular periodic studies to assess the dietary intake of mentioned elements are recommended.     

Comparison of arsenic, cadmium, chromium, lead, manganese, mercury and selenium in feathers in bald eagle (Haliaeetus leucocephalus), and comparison with common eider (Somateria mollissima), glaucous-winged gull (Larus glaucescens), pigeon guillemot (Cepphus columba), and tufted puffin (Fratercula cirrhata) from the Aleutian Chain of Alaska

There is an abundance of field data for levels of metals from a range of places, but relatively few from the North Pacific Ocean and Bering Sea. In this paper we examine the levels of arsenic, cadmium, chromium, lead, manganese, mercury and selenium in feathers from common eiders (Somateria mollissima), glaucous-winged gulls (Larus glaucescens), pigeon guillemots (Cepphus columba), tufted puffins (Fratercula cirrhata) and bald eagles (Haliaeetus leucocephalus) from the Aleutian Chain of Alaska. Our primary objective was to test the hypothesis that there are no trophic levels relationships for arsenic, cadmium, chromium, lead, manganese, mercury and selenium among these five species of birds breeding in the marine environment of the Aleutians. There were significant interspecific differences in all metal levels. As predicted bald eagles had the highest levels of arsenic, chromium, lead, and manganese, but puffins had the highest levels of selenium, and pigeon guillemot had higher levels of mercury than eagles (although the differences were not significant). Common eiders, at the lowest trophic level had the lowest levels of some metals (chromium, mercury and selenium). However, eiders had higher levels than all other species (except eagles) for arsenic, cadmium, lead, and manganese. Levels of lead were higher in breast than in wing feathers of bald eagles. Except for lead, there were no significant differences in metal levels in feathers of bald eagles nesting on Adak and Amchitka Island; lead was higher on Adak than Amchitka. Eagle chicks tended to have lower levels of manganese than older eagles.