Anthropogenic gadolinium anomalies and rare earth elements in the water of Atibaia River and Anhumas Creek,Southeast Brazil

The concentrations of rare earth elements (REE), measured in water samples from Atibaia River and its tributary Anhumas Creek, Brazil, present excess of dissolved gadolinium. Such anthropogenic anomalies of Gd in water, already described in other parts of the world, result from the use of stable and soluble Gd chelates as contrast agents in magnetic resonance imaging. Atibaia River constitutes the main water supply of Campinas Metropolitan area, and its basin receives wastewater effluents. The REE concentrations in water samples were determined in 0.22-μm pore size filtered samples, without and after preconcentration by solid-phase extraction with bis-(2-ethyl-hexyl)-phosphate. This preconcentration method was unable to retain the anthropogenic Gd quantitatively. The probable reason is that the Gd chelates dissociate slowly in acidic media to produce the free ion that is retained by the phosphate ester. Strong correlations between Gd and constituents or parameters associated with effluents confirmed the source of most Gd in water samples as anthropogenic. The shale-normalized REE patterns of Atibaia River and Anhumas Creek water samples showed light and heavy REE enrichment trends, respectively. Also, positive Ce anomalies in many Atibaia River samples, as well as the strong correlations of the REE (except Gd) with terrigenous elements, imply that inorganic colloidal particles contributed to the REE measured values.     

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.     

Cycling of rare earth elements in the atmosphere in central Tokyo

Concentrations of 14 rare earth elements (REEs) in six size classes of airborne particulate matter (APM) (<0.43, 0.43-0.65, 0.65-1.1, 1.1-2.1, 2.1-11, and >11 μm) and in two different phases (suspended particulate and dissolved) in rainwater were determined by inductively coupled plasma mass spectrometry (ICP-MS). Positive Eu and Tb anomalies were observed in size-classified APM. These anomalies may be due to large emissions of Eu and Tb to the atmosphere resulting from the recent change in Japan from the use of cathode-ray tubes to plasma displays in television sets (Eu and Tb) and from the widespread use of magneto-optical disks (Tb). The light REEs were enriched in fine APM particles (diameter < 1.1 μm). Because compositions of La/Ce/Sm in fine APM (diameter < 1.1 μm) were similar to those in automobile catalyst, the light REE enrichment was attributed to automobile emissions. In contrast, the REE distribution pattern in the suspended particulate phase in rainwater was similar to that in coarse APM (diameter > 2.1 μm), and a positive Tb anomaly was observed, suggesting that coarse particles easily become trapped in rain droplets. A negative Eu anomaly was observed in the dissolved phase in rainwater, but not in APM or in the suspended particulate phase in rainwater. Unlike other REEs, Eu can exist as both bivalent and trivalent ions in nature, and Eu-selective dissolution from or adsorption onto the trapped particles of Eu might account for the negative anomaly. These results show that atmospheric REE cycling is affected by the physico-chemical properties of APM.     

Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.     

Fraction characteristics of rare earth elements in the surface sediment of Bohai Bay, North China

Surface sediment samples were collected at 27 stations of Bohai Bay, North China. Sequential extractions were carried out in this study. REE were leached out from four labile fractions: Exchangeable (L1), bound to carbonates (L2), bound to Fe–Mn oxides (L3), bound to organic matter (L4), and the remainder was residual (R5). The total contents of REE fluctuate slightly in Bohai Bay, and are mainly concentrated in the middle region, showing relatively higher levels in the north than that in the south of Bohai Bay. Percentages of L1, L2, L3, L4, and R5 for REE suggest that the residual fraction accounts for the major component of REE, whereas Fe–Mn oxides also play important roles in combining labile REE. As the REE complex is not stabilized, the competition of complex could induce dissociation of the complex and redistribution of the REE in various environments. According to REE patterns and Y/Ho ratios of samples, REE are not anthropogenic or oceanic sources but riverine input, whereas suitable environment varieties can slightly affect the patterns and fractionations of REE. As powerful tracers for the variable of environment, higher anomaly of Eu and Ce in southern regions indicates a greater reduction in the condition of surface sediment in the south than that in the north of Bohai Bay.     

The study of rare earth elements in farmer's well waters of the Podwiśniówka acid mine drainage area (south-central Poland)

The principal objective of the current study was to elucidate the potential influence of acid mine drainage (AMD) pond on neighboring farmer's wells in the Podwi?niówka area (south-central Poland), using North American Shale Composite (NASC)-normalized rare earth element (REE) concentration profiles. The well waters generally displayed a distinctly positive Eu anomaly similar to that of parent rocks and AMD sediment. In contrast, the AMD pit pond water exhibited the typical roof-shaped NASC-normalized REE concentration pattern with a strong positive Gd anomaly. The low pH (mean of 2.9) of this pond water is induced by oxidation of pyrite that occurs in quartz veins and rocks exposed in the abandoned Podwi?niówka quarry. The principal source of REEs in turn is a crandallite series of aluminum–phosphate–sulfate (APS) minerals (gorceixite with florencite and Ce-bearing goyazite) that prevail in most clayey shales. These data indicate that the REE contents of the AMD pit pond and well waters are linked to bedrock mineralogy and lithology, but not to pyrite mineralization. The diverse REE patterns of NASC-normalized REE concentrations of the AMD and well waters may suggest complex sorption and desorption processes that occur at the rock–water interface influenced by different pH, Eh, temperature, and other factors. This is evidenced by a presence of strong positive Ce anomaly in the rocks, a lack of Ce anomaly in the AMD water and sediment, and the dominant negative anomaly of this element in the well waters. Variations in correlation coefficients (r ²) of REE concentrations between the rocks and the well waters may also result from a different contribution of quartzites, clayey shales, or tuffites to the REE signal of well waters as well as from mixing of shallow groundwater with infiltrating rainwater or meltwater with different REE profiles.     

Heavy Metal Pollution of Surface Soil in the Thrace Region, Turkey

Abstact Samples of surface soil were collected at 73 sites in the Thrace region, northwest part of Turkey. Two complementary analytical techniques, epithermal neutron activation analysis (ENAA) and atomic absorption spectrometry (AAS) with flame and graphite furnace atomization were used to determine 35 elements in the soil samples. Concentrations of As, Cd, Co, Cu, Mn, Ni, Pb and Zn were determined using AAS and GF AAS, and ENAA was used for the remaining 27 elements. Results for As, Ba, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu Eu, Fe, Hf, I, In, K, La, Mn, Mo, Na, Nd, Ni, Pb, Rb, Sb, Sc, Sm, Sr, Ta, Tb, Th, Ti, U, V and Zn are reported for the first time for soils from this region. The results show that concentrations of most elements were little affected by the industrial and other anthropogenic activities performed in region. Except for distinctly higher levels of Pb, Cu, Cd and Zn in Istanbul district than the median values for the Thrace region, the observed distributions seem to be mainly associated with lithogenic variations. Spatial distributions of As, Cd, Cr, Cu, Ni, Pb and Zn were plotted in relation to the concentration values in soil using Geographic Information System (GIS) technology     

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.     

Fractionation of elements by particle size of ashes ejected from Copahue Volcano,Argentina

The volcano Copahue, Neuquén province, Argentina has shown infrequent explosive eruptions since the 18th century. Recently, eruptive activity and seismicity were registered in the period July-October, 2000. As a consequence, ash clouds were dispersed by winds and affected Caviahue village located at about 9 km east of the volcano. Samples of deposited particles from this area were collected during this episode for their chemical analysis to determine elements of concern with respect to the health of the local population and its environment. Different techniques were used to evaluate the distribution of elements in four particle size ranges from 36 to 300 microm. X-ray powder diffraction (XRD) was selected to detect major components namely, minerals, silicate glass, fragments of rocks and sulfurs. Major and minor elements (Al, Ca, Cl, Fe, K, Mg, Mn, Na, S, Si and Ti), were detected by energy dispersive X ray analysis (EDAX). Trace element (As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, U, V and Zn) content was quantified by inductively coupled plasma-mass spectrometry (ICP-MS). Nuclear activation analysis (NAA) was employed for the determination of Ce, Co, Cs, Eu, Hf, La, Lu, Rb, Sc, Sm, Ta and Yb. An enrichment was observed in the smallest size fraction of volcanic ashes for four elements (As, Cd, Cu and Sb) of particular interest from the environmental and human health point of view.     

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.     

Natural heavy metal and metalloid concentrations in sediments of the Minho River estuary (Portugal): baseline values for environmental studies

Forty-nine surface sediment samples from the Minho estuary sector between Tui and Caminha were analyzed for grain-size contents, Al, As, Cr, Cu, Hg, Li, Pb, Sn, and Zn concentrations. Selected heavy metal (Cu, Cr, Hg, and Zn) and metalloid (As and Sn) distributions were normalized against Al and Li with the main goal of compensating for natural grain-size variability and to separate natural from anthropogenic contributions, by using a combination of normalization techniques (definition of regional geochemical baselines (RGB) and determination of enrichment factors (EF)). Lead did not reveal a significant relationship with Al and Li. Aluminum explained more variance than Li for As, Cu, Hg, and Zn. Assuming the general non-impacted metal character of the Minho River estuary sediments, RGBs are defined for differentiating between natural and anthropogenic contributions. Based on RGB defined for each heavy metal/metalloid, the degree of enrichment is estimated through the determination of EF. Despite the relatively low total heavy metal and metalloid concentrations, the defined RGB identifies a set of samples characterized by presenting As, Cu, Cr, Hg, and Zn enrichments relatively to expected natural levels. Mercury is the element showing the highest level of enrichment relative to the baseline values being spread through all the study area. Tin present enrichments relatively to Al and or Li always lower than 1.5 suggesting natural contributions.     

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.     

The impact of an industrial complex on freshly deposited sediments, Chener Rahdar river case study, Shiraz, Iran

Concentrations of elements (As, Co, Cu, Ni, Mo, Pb, V, and Zn) are studied in the sediments of two adjacent stretches of Chenar Rahdar river. The first stretch (S1) is influenced by urban and arable land wastewater, and the second (S2) is mainly loaded with industrial effluents. The average abundance order of heavy metals content in S1 sediments is Ni > V > Zn > Cu > Co > As > Pb > Mo and in S2 sediments is Ni > Zn > V > Cu > Mo > Pb > Co > As. The maximum average concentration for these heavy metals (except for As) occurs in the S2 sediments. The contamination factor (CF) base of background in S1 for eight analyzed elements is moderate. The CF for Cu, Zn, and Pb in S2 sediments is considerable. The highest CF in S1 and S2 sediments is observed for Mo (CF = 10.95 and 12.41) and indicates very high contamination. The application of modified degree of contamination values (mC_d) indicates low and high degree of contamination (1.89–4.15) in S1 and S2, respectively. Calculated enrichment factors (EF) reveal enrichment of Mo and As in S1 and Zn, Cu, Mo, and Pb in S2 compared to the average abundances of background level. The maximum EF for Mo is 7.61 (significant enrichment), while Pb, Zn, and Cu with maximum EF between 2 and 5 indicate moderate contamination. Principal component analysis (PCA) shows distinctly different elemental associations in S1 and S2 sediments. The strong association of Zn, Co, Ni, Sc, Cu, Al and Fe in S1 suggests a similar source. The results of PCA for Zn, Pb, Mo and Cu in S2 (componente2) indicate that these metals are influenced by anthropogenic activity. Also, high loading heavy metals with OC (0.97) indicate that organic carbon plays a significant role in the distribution and sorption of these heavy metals in the sediments. Factor analysis indicates that As and Mo behave differently in sediment samples.     

Relations between sulphate,ammonia, nitrate,acidity and trace element concentrations in tree bark in The Netherlands

Bark flakes were sampled in a biomonitoring survey throughout The Netherlands. Tree species used were oak (65 samples) and non-oak (58 samples) (poplar, elm, willow). Bark elemental analysis was carried out for As, Br, Ca, Cd, Ce, Co, Cr, Cs, Fe, Hg, K, La, Na, Ni, Pb, Rb, Sb, Sc, Se, Sm, Th, and Zn. Furthermore, bark acidity, SO₄, NH₄ and NO₃ were determined. Further variables introduced into the data-set were DIST (closest distance to sea water) and the dummy variably OAK (tree species).Straightforward multivariate correlation analysis was performed to check the effects on bark metal retention of the non-metal pollutants SO₄, NH₄ and NO₃, and of bark acidity. The OAK variable served to identify species-specific metal and non-metal pollutant behaviour. The DIST variable was used to visualize geography(source)-related variations in bark metal and non-metal pollutant concentrations, and to account for the non-random distribution of OAK and non-OAK tree species.The results indicate that the non-oak and oak bark samples may be combined to form 123 samples containing data-set for As, Br, Cd, Ce, Co, Fe, La, Na, Sc, Sm, Th, Zn, NH₄, NO₄, SO₄ and acidity, but not for Rb, Cs, Se, K, Ni, Pb and Sb (species-specific) and for Ca and Hg (H⁺-dependent). In the presented data-set, bark sulphate, ammonia and nitrate could not be shown to significantly affect bark metal retention.     

Assessment of Atmospheric Deposition of Heavy Metals and Other Elements in Belgrade Using the Moss Biomonitoring Technique and Neutron Activation Analysis

This study aimed at assessing atmospheric deposition of heavy metals and other elements using the moss genera Brachythecium sp. (B. rutabulum and B. salebrosum) and Eurhynchium sp. (E. hians and E. striatum) collected in autumn 2004 in the urban area of Belgrade. The concentrations of 36 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Mo, Sb, I, Cs, Ba, La, Ce, Sm, Tb, Dy, Hf, Ta, W, Hg, Th, U) were determined in moss and local topsoil samples by instrumental neutron activation analysis. The concentration of elements in moss positively correlated to those obtained for topsoil. High enrichment factors for As, Zn, Mo, Br, Sb, Se, Hg and Cl, calculated to continental crust composition, gave an evidence for anthropogenic impact on urban area, mainly due to intensive vehicular traffic and fossil fuel combustion. The concentration of elements in moss, characteristic for fossil fuel combustion, obtained in this study were substantially lower than in the previous investigation (2000) conducted in the area of Belgrade. The level of concentrations for V, Cr, Ni, and As in moss from this study correlated to those measured for neighboring countries, and were several times higher than the base-level data from low polluted areas. The level of accumulated elements in both investigated moss genera were similar and all studied species could be combined for biomonitoring purposes in urban areas.     

Platinum concentrations in Danish air samples determined by instrumental neutron activation analysis

Platinum, gold and calcium concentrations of 20 samples of airborne dust collected at two sampling sites between 1995 and 1997 in the city of Copenhagen, which suffers from heavy traffic, were determined by instrumental neutron activation analysis (INAA). INAA of platinum using the 199Au daughter of 199Pt was performed. Two interferences on the INAA of platinum were removed by calculations. The spectral interference on 199Au from the 47Sc daughter of 47Ca was removed by separating the 157-161 keV doublet peak into its components by calculating the counts due to 47Sc from the counts of the parent 47Ca. The contribution of 197Au to 199Au by two neutron absorption was corrected for using the ratio 198Au/199Au in a pure Au standard. From the INAA results, high platinum concentrations are present in air in the range 0.25-2.74 ng m-3 and gold concentrations in the range 0.10-1.96 ng m-3.     

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.     

A 100 year sedimentary record of heavy metal pollution in a shallow eutrophic lake, Lake Chaohu, China

This study has worked on the evaluation of the temporal and spatial evolution of heavy metal contamination in sediment taken from a shallow eutrophic lake, Lake Chaohu, China, over the last 100 years, and thereby used (137)Cs and (210)Pb dating, a PIRLA procedure, statistical analysis, geochemical normalization and a enrichment factor calculation (EF). Concentrations of 5174, 29?325, 10.7, 36.4, 20.4, 386.0, 21.1 and 38.4 mg kg(-1) for Ti, Fe, Co, Cr, Cu, Mn, Pb and Zn, respectively, are proposed as natural background values for the Lake Chaohu based on a PIRLA procedure. The contamination history from the last 100 years can be divided into two periods. Before the 1960s, heavy metal contamination did not occur and there was no spatial difference for heavy metal distribution. Since the 1960s, heavy metal enrichment and contamination has occurred, and the west half of the lake region showed a higher degree of contamination than the east half to various intensified anthropogenic activities. In the east half of the lake region, the anthropogenic source of heavy metals mainly originated from agricultural intensification, whereas in the west half of the lake it originated from city runoff and industry as well as agriculture. In all anthropogenic heavy metals, Co is only from industry.     

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.     

Geochemical assessment of metal concentrations in sediment core of Korangi Creek along Karachi Coast, Pakistan

Sediment core from Korangi Creek, one of the polluted coastal locations along the Karachi Coast Pakistan, was collected to trace the history of marine pollution and to determine the impact of industrial activity in the area. Down core variation of metals such as Ca, K, Mg, Al, S, Ti, V, Cr, Mn, Fe, Ni, Cu and Zn was studied in the 72.0 cm core. Nuclear analytical techniques, proton induced X-rays emission (PIXE), was employed to ascertain the chemical composition in sediment core. Grain size analysis and sediment composition of cored samples indicated that Korangi creek sediments are clayey in nature. Correlation matrix revealed a strong association of Ni, Cu, Cr and Zn with Fe and Mn. To infer anthropogenic input, enrichment factor (EF), degree of contamination and pollution load index were calculated. EF showed severe enrichment in surface sediment for Ni, Cu, Cr and Zn, indicating increased industrial effluents discharge in recent years. The study suggests that heavy metal discharge in the area should be regulated. If the present trend of enrichment is allowed to continue unabated, it is most likely that the local food web complexes in the creek might be at highest risk.