Enrichment Factors Of Pb Research Articles

Humic acids role in Br accumulation along two ombrotrophic peat bog profiles

Scientific results about the role of peatlands as sink or source of bromine are rather antithetic. Although several attempts have been performed to correlate Br content and peat decomposition/humification, the role of humic acids (HAs) as possible sink of this element has not been previously investigated. Two peat cores (2H and 2T), collected from the ombrotrophic bog Etang de la Gruère (Switzerland), were divided in several slices from which humic acids were successively extracted. Bromine content was determined in both peat and corresponding HAs samples using an Energy-dispersive miniprobe X-ray fluorescence multielement analysis (EMMA-XRF). Data show a greater “affinity” of Br for HAs rather than for corresponding bulk peat samples, especially in the first 24 cm of depth where Br concentration in HAs is 3.5 times higher than the one in peat; in particular, approximately 40% (average value) of the total Br in peat is stably incorporated into HAs molecules. Further, the observed correlation between the Br content in HAs and the Pb enrichment factor in peat, especially in the upper part of both profiles, suggests a possible role of HAs as geochemical sink of Br atmospheric deposition. Consequently, humification processes occurring in peat could promote Br accumulation in HAs, thus reflecting the deposition rate of this trace element.

Contamination assessment of copper, lead, zinc, manganese and nickel in street dust of Baoji, NW China

Street dusts collected from Baoji, NW China were analyzed for Cu, Pb, Zn, Mn and Ni by using PANalytical PW-2403 wavelength dispersive X-ray fluorescence spectrometry and assessed the contamination level of heavy metals on the basis of geoaccumulation index (I(geo)), enrichment factor (EF), pollution index (PI) and integrated pollution index (IPI). The results indicate that, in comparison with Chinese soil, street dusts in Baoji have elevated metal concentrations as a whole. The concentrations of heavy metals investigated in this paper are compared with the reported data of other cities. The calculated results of I(geo) and EF of heavy metals reveal the order of I(geo) and EF are Pb>Zn>Cu>Ni>Mn. The high I(geo) and EF for Pb, Zn and Cu in street dusts indicate that there is a considerable Pb, Zn and Cu pollution, which mainly originate from traffic and industry activities. The I(geo) and EF of Mn and Ni are low and the assessment results indicate an absence of distinct Mn and Ni pollution in street dusts. The assessment results of PI also support Pb, Zn and Cu in street dusts presented serious pollution, and IPI indicates heavy metals of street dust polluted seriously.

Major to ultra trace elements in rainfall collected in suburban Tokyo

Major to ultra trace elements such as rare earth elements (REEs), platinum group elements (PGEs) in 20 rainfall events from suburban Tokyo were determined by inductively coupled plasma mass spectrometry (ICP-MS). Anion species were also determined by an ion chromatography (IC). The concentrations of PGEs were so low that only Pt was detected in some rainfall events. Enrichment factors (EFs), refer to soil and sea salt components, were calculated for the measured elements (with Al and Na as references). Be, (Na), Mg, (Al), Si, Cl, K, Fe, Rb, Sr, REEs (except La, Gd), Ta, and U were mostly originated from natural materials (soil and sea salt). For Li, B, Ca, Mn, Sr, Ba, and Cs, the contribution of natural materials was significant. EFs for Cu, Zn, As, Se, Sb, Cd, Pb, Bi, Ag, Te, Au, Pt, SO 4-S and NO 3-N exceeded 100 indicating non-crustal, non-sea salt origin, presumably anthropogenic; however, contribution of volcanic gases could not be excluded for As, Se, Te and Bi. Pt seemed to be uniformly distributed worldwide and a catalyst for automobile emission control may be the main source. Au also showed uniform distribution. On the other hand, EFs for Zr, Nb, Hf and Th were less than unity. Probably these elements resided in acid resistant refractory fine minerals that did not decompose with acid treatment, and did not evaporate and ionize in the ICP. An alternative explanation is that the concentration of these elements was lower in the soil of the sampling area than the average crust. In the crust normalized REE pattern plot, La, Eu and Gd showed clear positive anomalies. La and Gd could have anthropogenic components. A possible source of La and Gd is cracking catalyst for petrol refining, but this source does not fully explain the anomaly. The source of Gd may also be Gd-DTPA (Gadolinium (III) diethyltriaminepentaacetic acid) used for Magnetic Resonance Imaging (MRI) contrast agents. The Eu origin may be soil with higher concentration than the crust average.

Spatial distribution and transport of heavy metals in soil, ponded-surface water and grass in a pb-contaminated watershed as related to land-use practices

The aim of this study was to investigate the spatial distribution of heavy metal in soil and evaluate the dissolution of metal from soil to ponded-surface water, leaching through soil profiles and metal uptake in grass as related to different land-use practices. The data provided a scientific basis for best-management practices for land use in Khli Ti watershed. The watershed has a Pb-contamination problem from the previous operation of a Pb-ore concentrator and abandoned Zn-Pb mine. Sampling sites were selected from a land-use map, with land-use types falling into the following four categories: forest, agricultural land, residential area and road. Soil, ponded-surface water, grass samples and soil profiles were collected. The study related soil characteristics from different land-use practices and locations with observed metal concentrations in ponded-surface water and soil. High enrichment factors of Pb and As in soil were found. Partitioning coefficient, K(d) values were in the order: Cr > Pb > Ni > Cu > Cd > Zn. Soil disturbance from land-use activities including tillage and traffic increased leaching of trace metal from soils. Pb in soil was significantly taken up by grass even though the Transfer Factor, TF values were rather low. Agricultural activities in the watershed must be limited. Moreover, land encroachments in the upper and middle part of the watershed which have high potential of Pb must be strictly controlled in order to reduce the Pb contamination from non-point sources.

Sources and Evolution of Anthropogenic Lead in Dated Sediments from Lake Clair, Québec, Canada

Two sediments cores were collected from the deepest part of Lake Clair (Québec, Canada) to assess the historical sources of Pb additions to the lake. The cores were collected by divers by carefully inserting a Plexiglas tube into the sediments. To determine the stratigraphic ages of the sediments, (210)Pb and (137)Cs activities were counted by gamma-ray spectroscopy. Lead concentrations and isotopic ratios were performed by inductively coupled plasma-mass spectrometry (ICP-MS), following digestion of the samples with a mixture of HF, HNO(3), and HClO(4) acids and Pb separation by anion-exchange chromatography. Starting at the middle of the 19th century, Pb content of the sediments increased until 1975. The maximum Pb enrichment factor of 35 times (relative to the natural background) was found in sediments deposited in 1975. At this time, excess Pb flux was estimated to be about 0.03 g m(-2) yr(-1). Before 1872, the Pb isotopic ratios were relatively stable (mean (206)Pb/(207)Pb = 1.20 +/- 0.01), reflecting the natural Pb background. Between 1872 and 1894, the source of anthropogenic Pb was highly radiogenic as shown by the Pb isotopic signatures of the sediments (mean (206)Pb/(207)Pb = 1.22 +/- 0.01), possibly reflecting deforestation and agricultural developments in the St.-Lawrence Valley. Between 1894 and 1937, widespread use of industrial and domestic charcoals may explain the isotopic composition of Pb accumulated in the sediments (mean (206)Pb/(207)Pb = 1.19 +/- 0.01). From 1937 to 1975, Pb isotopic compositions became less radiogenic ((206)Pb/(207)Pb from 1.18 to 1.17) even though elemental Pb abundance reached extremely high values (623 mg kg(-1)). This isotopic shift reflects increased use of alkyl-lead in gasoline. For sediments accumulated between 1967 and 1996, the U.S. contribution to anthropogenic Pb accumulated in Lake Clair sediments amounted to between 30 and 63%.

Evaluation of yeast strains as possible agents for trace enrichment of metal ions in aquatic environments

Sorption properties of six yeast strains were evaluated for trace enrichment of metal ions; Cd 2+, Cr 3+, Cr 6+, Cu 2+, Pb 2+, and Zn 2+ from aqueous environments. Metal concentration was determined by flame atomic absorption spectrometry (FAAS). The results showed that trace enrichment of the metals under study with yeast, was dependent on the pH and available metal ions. Enrichment time of 30 min gave an optimum metal uptake. The presence of Na +, K +, and Ca 2+ suppressed the uptake of Pb by less than 5%, but suppressed the uptake of Zn by between 15 and 25%. Mg 2+, Cu +, Cu 2+, Cr 3+ Cr 6+, Cd 2+, and Zn 2+ suppressed the uptake of Pb by between 25 and 35%, and that of Zn by between 15 and 25%. For both Pb and Zn, Cd had the highest suppression of 35 and 30%, respectively for baker's yeast ( Saccharomyces cerevisiae). Baker's yeast achieved enrichment factors (EF) of 23, 4, 100, and 1 for dam water, stream water, treated wastewater, and industrial effluent samples for Cu, Pb, Zn, and Cr, respectively. The recoveries of optimised Cd and Cr samples spiked with 2 μg ml −1 of the metal could reach up to 90%, but never exceeded 66% for 10 μg ml −1 samples. For Cu and Pb, the recoveries generally increased independent of concentration, however they were not as high as those for Zn, which exceeded 90% for all the samples spiked with 10 μg ml −1 of the metal. S. cerevisiae PR 61/3 had the highest EF for Cr as compared to the other yeast strains. S. cerevisiae PRI 60/78 was the only yeast strain which was able to enrich Cd in all the samples. Baker's yeast had the highest EFs for Cu and Zn as compared to the other yeast strains without pH adjustment of the water samples. Candida tropicalis attained the highest EFs for Pb as compared to the other yeast strains. The results indicate that all the yeast strains used had a high affinity for Zn based on the EF values achieved. The results from these studies demonstrate that yeast is a viable trace metal enrichment agent that can be used freely suspended in solution to enrich metal ions at relatively low concentrations. This has ramifications on the traditional methods of sampling, sample collection, and transportation from remote sampling sites.

Determination of Trace Amounts of Lead and Copper in Water Samples by Flame Atomic Absorption Spectrometry after Cloud Point Extraction

The need for highly reliable methods for the determination of trace metals is recognized in analytical chemistry and environmental science. A method based on the cloud-point extraction (CPE) technique for the trace analysis of Pb and Cu in water samples is described in this study. The analytes in the initial aqueous solution are complexed with pyrogallol, and 0.1%(w/v) Triton X-114 is added as surfactant. Following phase separation at <TEX>$50^{\circ}C$</TEX>, based on the cloud point of the mixture and dilution of the surfactant-rich phase with acidified methanolic solution, the enriched analytes are determined by flame atomic absorption spectrometry. After optimization of the complexation and extraction conditions, the enrichment factors of Pb and Cu were found to be 72 and 85, respectively. Under optimum conditions, the preconcentration of 60 mL of samples in the presence of 0.1%(w/v) Triton X-114 permitted the detection of 0.4 <TEX>${\mu}gL^{?1}$</TEX> of Pb and 0.05 <TEX>${\mu}gL^{?1}$</TEX> of Cu. The proposed method was applied successfully to the determination of Pb and Cu in water samples.

Characteristics and sources of 2002 super dust storm in Beijing

On 20 March, 2002, a super dust storm attacked Beijing, which was stronger than any dust storm ever recorded. The concentration of total suspended particulates (TSP) reached 10.9 mg · m−3, 54 times as high as the national air quality standard. The concentrations of major crustal elements, such as Ca, Al, Fe, Na, Mg and Ti, were 30–58 times higher than those in non-dust storm days. The concentrations of pollution elements, such as Zn, Cu, Pb, As, Cd and S, were also about several or even nearly ten times higher than those in normal days. The enrichment factors of Pb, As, Cd and S in PM2.5 were as high as 12.7, 29.6, 43.5, 28.4, indicating that these pollutants came from the mixing of mineral aerosol with pollution aerosol emitted by pollution sources on the way of dust storm’s long-range transport. The overlap of invaded air mass from dust with pollution air mass from Beijing local area was another reason for the enhancement of pollutants. During dust storm, fine particles (PM2.5) accounted for 30% of TSP and pollutants in PM2.5 accounted for even as high as 45%–69% of TSP. The increase of pollutants after dust storm proved further that mineral aerosol, especially the fine particles from dust storm favored the transformation and accumulation of pollutants. It must be noted that Fe (II) was detected again in this dust storm, which provided new evidence for the mechanism of coupling and feedback between iron and sulfur in the atmosphere and the ocean. The increase of both pollutants and nutrient, Fe(II), during dust storm illuminated that dust storm is an important factor affecting the global environment change.

Evaluation of metal contamination in coastal sediments of the Bay of Bengal, India: geochemical and statistical approaches

Surface sediment samples collected from the inner shelf region of the Bay of Bengal, were analysed for the major elements and total and acetic acid available trace elements (Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Si, Zn) to evaluate geochemical processes influencing their distribution. Major elemental analysis showed that the sediments had high concentrations of Si and relatively low concentrations of Al and Fe. Both major elemental and trace metal concentrations indicated that the sediments represent weathered products of granite and charnockite. Normalization of metals to Al indicated relatively high enrichment factors for Pb, Cd, Zn and Cr. The higher proportions of nondetrital Pb (66%), Cd (41%) and Co (28%) reveal metal contamination due to anthropogenic inputs. Factor analysis (FA) identified six possible types of sedimentological and geochemical associations. The dominant factor accounting for 26.9% of the total variance identifies an anthropogenic input and accumulation of nondetrital Cd, Co, Cr, Ni and Pb. Association of these metals with CaCO 3 reveals that shell fragments in the surface sediments are likely act as a carrier phase for nondetrital metals. The results are discussed in the context of the sources and pathways of elements in the Bay of Bengal.

Biodiversity and trace element content of epiphytic bryophytes in urban and extraurban sites of southern Italy

In the present study epiphytic bryophytes were employed as a model system in an integrated way both as bioindicators at species, population and community levels and as bioaccumulators of airborne trace elements. Twenty sites with Quercus ilex trees were chosen in a Mediterranean area both in urban and natural locations, with an altitude ranging from 0 to about 500 m a.s.l., in coastal and inland areas (Campania, Italy). Data on the presence of species, cover values and phenology were recorded for each site and the Index of Atmospheric Purity (IAP) was calculated. The data matrix of frequency/cover × species was analysed by multivariate methods. Data obtained clearly show that in urban sites the number of species and IAP values are lower, and that acrocarpous mosses and vegetative reproduction occur more frequently. Contents of trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, Zn) were measured in four species and concentrations were normalised to the soil pattern by calculating the Enrichment Factor (EF). The results show the large contribution of resuspended soil particles to the chemical composition of the analysed bryophytes. All the examined species were enriched in Cd, Cu and Zn, and in some cases showed high EF for Pb. The differences among epiphytic bryophyte vegetation are discussed in order to evaluate suspected alterations due to human impact and/or environmental change.

China’ s first exploration of Chukchi Sea and its adjacent waters in the arctic — A study on lead geochemistry of atmospheric aerosol

The Pb concentrations of atmospheric aerosol in the Chukchi Sea of the Arctic vary within the range of 0.167–0.962 ng/m3, with an average of 0.532 ng/m3. These concentration values are 200 times higher than the natural background values of snow samples there. Calculation of the Pb enrichment factor of aerosol indicates that the ocean- and continent-source lead account for 9.23% and 0.01%, respectively, but industrially released Pb accounts for more than 90% of the atmospheric Pb. The Pb isotopic composition of aerosol has revealed that the sources of lead from industrial lead that causes pollution include mainly the western part of North America, East Europe and the former Soviet Union. The calculation of the total fallout flux of Pb indicates that the mean value of input flux into the Chukchi Sea is 0.02 mgm-2 a-1, equivalent to that of southern Pacific but slightly lower than that of northern Indian Sea and southern Atlantic. It is evidenced that the Pb input flux into the Chukchi Sea is far lower than that off the Baltic Sea, the North Sea and the Mediterranean Sea.

Atmospheric Pb deposition in Spain during the last 4600 years recorded by two ombrotrophic peat bogs and implications for the use of peat as archive

Two ombrotrophic peat bogs in Northwestern Spain provided a history of 4600 years of Pb accumulation. Highest Pb concentrations (84–87 μg g −1) were found near the bogs’ surface, but there were also other significant peaks (6–14 μg g −1), indicating pre-industrial atmospheric pollution. The enrichment factors (EFs) in both cores show a remarkably similar record. Atmospheric Pb pollution dates back to at least approximately 2500 years ago, reaching a first maximum during the Roman period. For the last 300 years, Pb EFs significantly increased due to industrial development, but the uppermost samples of the bogs show decreasing Pb EFs, probably due to the phasing out of leaded gasoline. These results are also supported by 206Pb/ 207Pb isotope ratios, as they continuously decrease from ca. 3000 BP until 2000 BP (from 1.275 at 4070 14C years BP to 1.182), indicating the growing importance of non-radiogenic Pb released from Iberian ores by ancient mining. Peat samples at a 3–5-cm depth are even less radiogenic ( 206Pb/ 107Pb=1.157), indicating the strong influence of leaded gasoline. Despite the common history shared by the two bogs, striking differences were found for Pb enrichment, whether this was calculated by normalising to the Pb/Ti ratio of the upper continental crust or to the Pb/Ti ratios of peats from pre-anthropogenic times. This effect seems to be related to differences in Ti accumulation in both bogs, possibly due to physical fractionation of the airborne dust during wind transport. Enrichment has to be carefully considered when comparing the results obtained for different bogs, since our results suggest that normalising to crustal proportions is meaningless when the bulk of the deposition in an area is strongly influenced by short- and medium-range dust transport.

Geochemistry of the peat bog at Etang de la Gruère, Jura Mountains, Switzerland, and its record of atmospheric Pb and lithogenic trace metals (Sc, Ti, Y, Zr, and REE) since 12,370 14C yr BP

A 650 cm core from a Swiss bog represents 12,370 14C years of peat accumulation and provides the first complete record of atmospheric Pb deposition for the entire Holocene. Excess, non-atmospheric Sr in the peat was calculated by normalizing Sr/Sc to crustal abundance; this was used to differentiate between the ombrogenic section of the bog in which inorganic solids are supplied exclusively by atmospheric deposition and the minerogenic zone where mineral-water interactions contribute metals to the peat. While sediment dissolution contributes significantly to the Sr inventory of the minerogenic section of the peat profile, there is no measurable effect of this process on the Pb burden. Isotopic analyses (204Pb, 206Pb, 207Pb, 208Pb) show that effectively all of the Pb in the peat profile was supplied exclusively from the atmosphere.To separate natural and anthropogenic Pb, Sc was selected over Ti, Y, Zr, Hf and REE as a conservative, reference element which is supplied by soil dust aerosols derived from rock weathering. Enrichment factors (EF) were calculated using the Pb/Sc ratio in the peat samples, normalized to the “natural, background” Pb/Sc which is found in peats dating from 8030 to 5320 14C yr BP. The results show that anthropogenic source have dominated the supply of atmospheric Pb to the peat core continuously since 3000 14C yr BP. The aerosols supplied to the bog can be divided into 3 classes: a) Pre-Anthropogenic (older than 3000 14C yr BP with Pb EF < 2 and 206Pb/207Pb > 1.194); b) Pre-Industrial (dating from 3000–240 14C yr BP, with Pb EF ≥ 2 but <20 and 206Pb/207Pb 1.193–1.179); c) Industrial (more recent than 240 14C yr BP, with Pb EF > 20 and 206Pb/207Pb < 1.179).Elevated soil dust fluxes are observed at 5320, 8230 and 10,590 14C yr BP; the latter corresponds to the Younger Dryas. Aluminum, Zr, Hf, and REE/Sc ratios also are elevated at the same depths, suggesting differences in particle size, wind strength, or source regions. Pre-Anthropogenic aerosols deposited since 8230 14C yr BP reveal Pb/Sc which is significantly higher, and 206Pb/207Pb which is less radiogenic, than during the early Holocene. While the trend toward increasing Pb/Sc could be due to chemical weathering and soil development, this could not explain the shift in Pb isotopic composition. The changes which took place at 8230 14C BP, therefore, may be related to a large scale climatic reorganization which, at present, is poorly understood.

Pb and Sr isotopic evidence for sources of atmospheric heavy metals and their deposition budgets in northeastern North America

Concentrations of Al, Ba, Cd, Cu, Mg, Mn, Pb, Rb, Sr, and Zn, as well as Pb and Sr isotopic compositions were determined in samples of snowpack obtained during the 1998 winter season from northeastern North America. Median enrichment factors, relative to upper crustal abundances, for Cd, Cu, Mn, Pb, and Zn for all samples range from ca. 50 to 36,000 and are indicative of an anthropogenic origin. The Pb isotope ratios correlate with geographic location because snowpack from eastern Ontario and the northeastern USA are characterized by the most radiogenic 206Pb/ 207Pb ratios (ca. 1.18–1.19), and these decrease systematically in an easterly direction towards the Atlantic coast (ca. 1.16). The Pb isotope data for the 1998 samples of snowpack indicate that atmospheric pollution in this region of North America is dominated solely by a mixture of anthropogenic emissions from US ( 206Pb/ 207Pb ca. 1.20) and Canadian ( 206Pb/ 207Pb ca. 1.15) sources. This result contrasts with that obtained for 1997 snowpack from similar geographic regions, because the Pb isotope data for the latter suggest the involvement of an additional anthropogenic component, possibly that of Eurasian pollution transported over the high Arctic. This difference in the distribution pattern of atmospheric pollution over northeastern North America between the 1997 and 1998 winter seasons may be related to the El Niño phenomenon. Sr isotope data for all the 1998 snowpack samples define a large range in 87Sr/ 86Sr values but most are between 0.709 to 0.710, similar to the value of present-day seawater (ca. 0.7092). However, the majority of snowpack samples from eastern Ontario are characterized by lower 87Sr/ 86Sr ratios (<0.709), and these correlate negatively with their enrichment factors of Pb. Such trends suggest the presence of a relatively ‘unradiogenic’ source of anthropogenic Sr, possibly related to emissions from coal-fired power plants located in the western and midwestern regions of the USA. Annual depositional budgets estimated from 1998 snowpack indicate that those for Pb, Cd, and Cu are highest in eastern Ontario, and significantly lower in the remaining regions. The former reflect a “meteorological corridor” in northeastern North America, which coincides with heavily industrialized and densely populated areas. Depositional budgets of Zn are extremely high in all areas investigated and their exact source(s) remains enigmatic. These may reflect either an increase in atmospheric industrial emissions (since the 1980s), a lower residence time in the atmosphere, or particular chemical speciation that affects the deposition of Zn from the lower troposphere. Depositional budgets for Mn are also high and may be related to the combustion of Mn-bearing fossil fuels by automotive vehicles.

Volcanic and anthropogenic contribution to heavy metal content in lichens from Mt. Etna and Vulcano island (Sicily)

Major and trace element concentrations were determined in two lichen species ( Parmelia conspersa and Xanthoria calcicola) from the island of Vulcano and all around Mt. Etna. In both areas, the average concentrations of Al, Ca, Mg, Fe, Na, K, P and Ti are substantially greater than those of other elements. Several elements (Br, Pb, Sb, Au, Zn, Cu) resulted enriched with respect to the local substrates. The Br and Pb enrichment factors turned out to be the highest among those calculated in both areas. Data indicate that mixing between volcanic and automotive-produced particles clearly explains the range of Pb/Br shown by lichen samples. Sb is also enriched, revealing a geogenic origin at Vulcano and a prevailing anthropic origin at Mt. Etna. Distribution maps of the enrichment factors show a generalized enrichment of Au and Zn near Mt. Etna, whereas Cu appears to be enriched prevalently in the NE–SE area. The highest levels of Au and Cu at Vulcano occur E–SE from the craters, following the prevailing wind direction.

Atmospheric Pb Deposition since the Industrial Revolution Recorded by Five Swiss Peat Profiles: Enrichment Factors, Fluxes, Isotopic Composition, and Sources

Atmospheric Pb deposition since the Industrial Revolution was studied in western, central, and southern Switzerland using five rural peat bogs. Similar temporal patterns were found in western and central Switzerland, with two distinct periods of Pb enrichment relative to the natural background: between 1880 and 1920 with enrichments ranging from 40 to 80 times, and between 1960 and 1980 with enrichments ranging from 80 to 100 times. The fluxes also were generally elevated in those time periods: in western Switzerland between 1.16 and 1.55 μg cm-2 y-1 during the first period, and in western and central Switzerland between 0.85 and 1.55 μg cm-2 y-1 during the second period. Between the Industrial Revolution and 1985, nonradiogenic Pb became increasingly important in all five cores because of the replacement of coal by oil after ca. 1920, the use of Australian Pb in industry, and the extensive combustion of leaded gasoline after 1950. The introduction of unleaded gasoline in 1985 had a pronounced effect on the Pb deposition in all five cores. Enrichments dropped sharply (between 2 and 4 times), and the isotopic ratios reverted back toward (but not achieving) natural values. The cores from western and central Switzerland showed very similar isotopic trends throughout the time period studied, implying that these sites were influenced contemporaneously by similar pollution sources and atmospheric pathways. Southern Switzerland revealed a different record with respect to the Pb pollution: it was dominated by a single massive Pb enrichment dated between 1930 and 1950. During this period the Pb enrichment factor reached ∼200 times background and the Pb flux was ∼27 μg cm-2 y-1, more than an order of magnitude higher that at the western and central sites. This core also had significantly different post-1950 changes in the Pb isotope ratios.

Solvent impregnated hollow fibre for a selective preconcentration of Pb(II) in an on-line determination by flame atomic absorption spectrometry

A solvent impregnated hollow fibre (SIHF) module has been developed for the preconcentration of lead by using bis(2-ethylhexyl) phosphoric acid (DEHPA) dissolved in kerosene as extractant. The module has been designed for an on-line determination of trace amounts of lead(II) at mg l −1 (ppm) level by flame atomic absorption spectrometry (FAAS). The SIHF system is based on the metal liquid–liquid distribution between aqueous solutions of different acidity and the mentioned organic solution. The highest enrichment factor of Pb(II) was determined at pH=4.0 using a formic acid/formiate buffer solution. Preconcentration experiments were carried out at low lead(II) concentration (mg l −1 level) by using the SIHF module. This study includes the influence of hydrodynamic and chemical conditions on the loading and elution of Pb(II) on the SIHF, i.e., flow rate through the fibres, acidity of the eluent (as nitric acid concentration) and the chemical nature of the acid used in the elution. Breakthrough curves were determined for different sampling flow rates, 0.54 ml min −1 was selected to minimise the loading volume of Pb(II) sample. 0.1 M nitric acid was chosen as eluent solution, and perchloric acid also shows appropriate elution characteristics. The degree of concentration obtained for Pb(II) are of 10 fold the original concentration. The quantification limit for Pb(II) achieved with this preconcentration system is 0.17 mg l −1. The results obtained indicate that the SIHF system can be applied for on-line determination of trace amounts of lead(II) by FAAS.

Ti and Pb Concentrations in Rainwater-Fed Bogs in Europe as Indicators of Past Anthropogenic Activities

Chemical and physical analyses of dated ombrotrophic peat cores from 8 European regions were undertaken to determine the effect of forest clearances, farming, mining and smelting on the composition of atmospheric aerosols. Elemental concentrations in peat were determined using XRF and the mean concentrations of Ti and Pb in peat as well as Pb enrichment factors (Pb EFs) were calculated for each region and for different time periods (Roman Times, Dark Ages, Middle Ages, modern times). The results show that the concentration of Ti, Pb and the calculated Pb EFs closely follow changes in land use history extending back thousands of years. Concentrations of Ti, for example, reflect changing soil dust inputs in response to forest clearing and agriculture. Lead emissions are characterized by considerable continental-scale variations: elevated concentrations and EFs during the Roman Period at most sites, very high concentrations and EFs in the Harz Mountains during the Medieval period, and elevated to high concentrations and EFs during modern times at all sites. The findings indicate that peat cores from ombrotrophic bogs are useful not only for quantifying temporal changes in metal emissions, but also for identifying spatial variations on scales ranging from regional to global.

Lead in Three Peat Bog Profiles, Jura Mountains, Switzerland: Enrichment Factors, Isotopic Composition, and Chronology of Atmospheric Deposition

One metre cores were taken from three peat bogs in the Jura Mountains of Switzerland: Etang de la Gruere (EGr), La Tourbiere des Genevez (TGe), and Praz Rodet (PRd). Dried peat samples were analyzed for lead (Pb) using the EMMA XRF and scandium (Sc) using INAA. Enrichment factors (EF) were calculated by normalizing to the background Pb/Sc ratio at EGr. Age dates were obtained using 210Pb (CRS Model) and confirmed using pollen chronostratigraphic markers in replicate cores. The isotopic composition of Pb in selected peat samples from EGr and TGe was determined using TIMS. Two pronounced peaks in Pb EF occur in the uppermost sections of all three bogs: the upper one corresponds to the late 1960's to late 1970's and the lower one to approximately 1900 to 1920. At EGr, sample 2f5 (11 cm, 86 µg/g Pb, EF = 91, and dated at A.D. 1967 ± 2) has an isotopic composition similar to that of leaded gasoline used in Berne in the 1970's. For comparison, the older peak at EGr (sample 2fl 1 at 29 cm, 84 µg/g Pb, EF = 79 and dated at A.D. 1905 ± 6) is significantly different. In contrast to these two samples, the isotopic composition of sample 2fl 5 (41 cm, 30 µg/g Pb, EF = 13 and pre-dating ca. A.D. 1800) approaches the present day "average terrestrial lead" and is likely to be predominately lithogenic. Therefore, the isotopic data show that the Pb introduced to the bog from leaded gasoline has not penetrated to this depth in the profile. A simple mass balance using the measured Pb concentrations and the isotopic compositions shows that vertical migration of gasoline Pb cannot explain the deeper, older peak in Pb EF. A more likely explanation is that the older peak reflects the rates of atmospheric Pb deposition during the first two decades of the 20th century. Taken together, the Pb concentrations, age dates, and isotopic data suggest that these peat profiles have preserved the record of changing rates of atmospheric Pb deposition. In addition, the results indicate that the isotopic composition of Pb deposited on the surface of the bogs gradually shifted away from lithogenic ratios as long ago as the middle of the 19th century, a change which clearly pre-dates the introduction of leaded gasoline.

Major Ionic and Trace Metal Constituents in Snow at Ester Dome, Fairbanks, Alaska.

Depth profiles of major anions, cations and trace metal concentration levels were measured on snow samples collected at Ester Dome, Fairbanks, Alaska, in March 1994. Both Ca2+ and Na+ occupies most of cations and significant amount of non-sea-salt Ca2+ exists, especially in late winter snow. Correlation between non-sea-salt SO42- and non-sea-salt Ca2+ plus non-sea-salt Mg2+ suggests that non-sea-salt SO42- in snow layer deposited in early winter was associated mostly with Ca and a little fraction with Mg. Depth profiles of enrichment factor based on Al for Mn and Ca show a similar variation with depth. Concentration levels and enrichment factors for Pb and V show an increasing trend near the surface, indicating increased input of industrial pollutants to Arctic atmosphere in late winter to spring.