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

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

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

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

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.     

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.     

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.     

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.     

Mobilization of aluminium and deposition on fish gills during sea salt episodes--catchment liming as countermeasure

Episodic events may be critical with respect to aluminium (Al) toxicity in moderately acidified salmon rivers. The present work demonstrates that sea salt episodes enhance the toxicity of Al in acidic rivers. The documented sea salt episode (300 [micro sign]M Cl) mobilized positively charged Al species (0.4 to 1.1 [micro sign]M Al(i)), enhanced the Al accumulation on fish gills (0.9 to 10 [micro sign]mol g(-1) dw) and caused increased stress responses (6 to15 mM blood glucose) in fish. Accumulated Al on gills remained high several days after the episode. The presented results are based on a six-week field study in two tributary rivers on the west coast of Norway. Changes in the river water qualities and Al speciation were followed using in situ fractionation techniques. Al accumulation on gills and stress responses were followed for Atlantic salmon (Salmo salar) kept in tanks continually exposed to the changing water quality. The potential mobilization of Al from the two catchments was studied by extracting soils with diluted seawater (salinity of 3). To counteract Al toxicity, one of the tributary catchments has been limed. The potential mobility of Al by sea salt was lower in limed soils compared to acid soils, and the Al deposition on fish gills (<3.5 [micro sign]mol g(-1) dw) and associated stress responses stayed low during the sea salt episode in the river draining the limed catchment. Thus, for acid river systems in coastal areas, catchment liming should be considered as a useful countermeasure for Al toxicity.     

Source characterisation of atmospheric platinum group element deposition into an ombrotrophic peat bog

Platinum, palladium, rhodium, iridium and osmium were found to be enriched relative to their expected natural concentrations in peat samples from Thoreau's Bog, an ombrotrophic peat bog in Concord, Massachusetts. The source of osmium into the bog was determined from its isotopic composition (187Os/188Os). Osmium is composed of 4% lithogenic osmium from atmospheric soil dust, 41% of anthropogenic osmium and 55% of osmium from a non-lithogenic, non anthropogenic source, with rain being a likely candidate for the latter. Significant anthropogenic and rain contributions are also expected for iridium. In contrast, platinum, palladium and rhodium are almost exclusively anthropogenic. The larger enrichments of platinum, palladium and rhodium indicate that automobile catalysts are the source of platinum group elements to Thoreau's bog. The bog is located approximately 300 m from a major road and, therefore, the occurrence of platinum elements is evidence for regional dispersion of these metals. The absence of a clear trend following the introduction of catalysts indicates that platinum group elements are not quantitatively conserved in peat with downward leaching and plants playing an important role in the accumulation of platinum group elements.     

Exploratory study of suspended sediment concentrations downstream of harvested peat bogs

Peat bog harvesting is an important industry in many countries, including Canada. To harvest peat, bogs are drained and drainage water is evacuated towards neighboring rivers, estuaries or coastal waters. High suspended sediment concentrations (SSC) were found in the drainage water at one particular site during the 2001–2002 spring seasons in New Brunswick (Canada). The main objective of this study was to verify this observation at other sites, compare SSC levels leaving harvested peat bogs with those leaving an unharvested bog, and to determine if high SSC events happen only in Spring or all year round. Suspended sediment concentrations were monitored downstream of three harvested peat bogs and an unharvested reference bog located in New Brunswick during the ice free seasons of 2003–2004. On average, SSC at the harvested sites exceeded 25 mg/l, which is the recommended daily maximum concentration, 72% of the time, while the same concentration was exceeded 30% of the time at the unharvested sites. SSC were found to be significantly higher at harvested sites than at the reference sites for all seasons. The highest SSC medians were recorded in the Fall but SSC was elevated in all seasons. High SSC levels in receiving waters may be caused by field ditching activities and insufficient sediment controls. Findings suggest the NB Peat Harvesting 25 mg/l SSC guideline should be reviewed.     

Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analyses

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.     

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.     

Evaluation of a fluorometric method for measuring low concentrations of ammonia in ambient air

A fluorometric method developed for measuring low concentrations of ammonium in marine and freshwater ecosystems was adapted for the analysis of ammonia in ambient air. The modified method entails collection of samples on an acid-treated solid adsorbent followed by analysis using a fluorometer. Optimal results were obtained using a commercially available sorbent tube containing 100 mg of acid-treated silica gel for sample collection, and an analytical protocol consisting of sample desorption in DI water, addition of orthopthaldialdehyde (OPA) working reagent, and room temperature incubation. Method accuracy and precision were evaluated by comparing experimentally determined quantities of ammonia to expected levels for sample loadings ranging from 0.16 [micro sign]g to 550 [micro sign]g-accuracy was generally within +/-20%. The estimated LOQ for the method is 0.08 [micro sign]g ammonia per sample which represents a 25-375-fold improvement in sensitivity compared to current NIOSH and OSHA methods for the measurement of ammonia in ambient air. The new method should be useful for applications requiring measurement of low concentrations of ammonia using personal sampling equipment or in the characterization of short-term fluctuations of ammonia concentrations in air.     

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.     

Mercury wet deposition in rural Korea: concentrations and fluxes

The characteristics of Hg wet deposition were investigated in a rural area of Korea from August 2006 to July 2008. The volume weighted mean (VWM) Hg(T) concentration and cumulative Hg(T) flux were 8.8 ng L(-1) and 9.4 μg m(-2) per year, respectively. The VWM Hg(T) concentration varied seasonally, similar to the seasonal pattern in atmospheric Hg(p) concentration. The enhancement of both VWM Hg(T) and atmospheric Hg(p) concentrations in spring and winter was likely caused by the long-range transport of Hg from China. Monthly VWM Hg(T) and atmospheric Hg(p) concentrations were well correlated (R(2) = 0.36); however, there was no correlation between VWM Hg(T) and RGM (reactive gaseous mercury) concentrations, suggesting that Hg(p) was responsible for the majority of the Hg in wet deposition at this site. The VWM Hg(T) concentration in snow was statistically higher than in rain. In addition, the atmospheric Hg(p) concentration appeared to be elevated for snow events as well. This suggests that both elevated Hg(p) concentrations and the enhanced scavenging efficiency of snow for Hg(p) were responsible for the elevated VWM Hg(T) concentrations measured during snow events.     

Mercury trends in fish from rivers and lakes in the United States, 1969�C2005

A national dataset on concentrations of mercury in fish, compiled mainly from state and federal monitoring programs, was used to evaluate trends in mercury (Hg) in fish from US rivers and lakes. Trends were analyzed on data aggregated by site and by state, using samples of the same fish species and tissue type, and using fish of similar lengths. Site-based trends were evaluated from 1969 to 2005, but focused on a subset of the data from 1969 to 1987. Data aggregated by state were used to evaluate trends in fish Hg concentrations from 1988 to 2005. In addition, the most recent Hg fish data (1996?C2005) were compared to wet Hg deposition data from the Mercury Deposition Network (MDN) over the same period. Downward trends in Hg concentrations in fish from data collected during 1969?C1987 exceeded upward trends by a ratio of 6 to 1. Declining Hg accumulation rates in sediment and peat cores reported by many studies during the 1970s and 1980s correspond with the period when the most downward trends in fish Hg concentrations occurred. Downward Hg trends in both sediment cores and fish were also consistent with the implementation of stricter regulatory controls of direct releases of Hg to the atmosphere and surface waters during the same period. The southeastern USA had more upward Hg trends in fish than other regions for both site and state aggregated data. Upward Hg trends in fish from the southeastern USA were associated with increases in wet deposition in the region and may be attributed to a greater influence of global atmospheric Hg emissions in the southeastern USA. No significant trends were found in 62% of the fish species from six states from 1996 to 2005. A lack of Hg trends in fish in the more recent data was consistent with the lack of trends in wet Hg deposition at MDN sites and with relatively constant global emissions during the same time period. Although few significant trends were observed in the more recent Hg concentrations in fish, it is anticipated that Hg concentrations in fish will respond to changes in atmospheric Hg deposition, however, the magnitude and timing of the response is uncertain.     

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.     

Atmospheric wet deposition of soluble macro-nutrients in the Cilician Basin, north-eastern Mediterranean sea

In order to estimate wet deposition atmospheric fluxes of macro-nutrients into the eastern Mediterranean coastal waters, soluble inorganic phosphate (PO4(3-)), nitrate (NO3-) and nitrite (NO2-) concentrations in precipitation (from February 1996 to June 1997) have been measured at a coastal sampling site, Erdemli, Turkey. Water-soluble inorganic PO4(3)-P, a reactive, bioavailable, limiting macro-nutrient in the oligotrophic waters of the eastern Mediterranean was studied with respect to its contribution to biological productivity. Reactive PO4(3-)-P and NO2(-) + NO3(-)-N concentrations were found to be highly variable in rainwater samples. One of the aims of the study was to determine the contribution of dust transport to the soluble macro-nutrient budget of the eastern Mediterranean. No differences were found between the mean reactive P and NO(2-) + NO3(-)-N concentrations of "red rain" and normal rain events. Most likely as a result of low solubility of crustal phosphorus, dust episodes were not found to be important sources of reactive P, in terms of wet deposition. The annual wet deposition fluxes of reactive PO4(3-)-P and NO2(-) + NO3(-)-N into the Cilician Basin were respectively estimated to be 0.010 g P m(-2) per year and 0.23 g N m(-2) per year, which are comparable to the fluxes from land-based sources in the north-eastern Mediterranean. The incorporation of water soluble bioavailable PO4(3-)-P and NO2(-) + NO3(-)-N delivered via atmospheric wet deposition could be responsible for approximately 3.3% (0.40 g C m(-2) per year) and 11.0% (1.31 g C m(-2) per year) respectively, of the mean annual new production in the north-eastern Mediterranean.     

The success of elutriate tests in extended prediction of water quality after a dredging operation under freshwater and saline conditions

Dredging simulation by elutriate tests accurately predicted concentrations of Hg, Cu, Mn and Fe released to the water column from contaminated sediment to within 1 order of magnitude. Hg and Cu concentrations increased by up to 7-fold after dredging, but declined to background concentrations within 48 h. Maximum loadings of Hg and Cu coincided with Fe and total organic carbon (TOC) water column concentrations, suggesting Hg and Cu are adsorbed onto particulates of Fe oxides and organic material. Seasonal changes in redox potential and temperature did not significantly affect metal release from sediments. Saline water did not cause significant increases in contaminant release from sediments to the water column over that observed for freshwater. Water quality standards of 1 µg l^–1 Hg and 28 µg l^–1 Cu as annual averages were not breached by dredging operations. Long-term effects of dredging on Hg and Cu availability, due to deposition of contaminated material as surficial sediments, is, however, of concern.     

Mass loading of nickel and uranium on plant surfaces: application of laser ablation-ICP-MS

Transport of contaminated sediments from a former radiological settling pond results in the deposition of U and Ni in the Lower Tims Branch (LTB)(Aiken, SC, USA). Uranium is unavailable for plant uptake, but elevated U and Ni concentrations associated with foliage of understory plants suggested mass loading. Mass loading of contaminated soil on Andropogon elliottii Chapman (Poaceae) was investigated using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The technique allows for rapid quantitative elemental depth profiling. Fresh washed and unwashed leaves (n= 5) from the contaminated area were compared with those from an uncontaminated area, analysing Ni and U at ten randomly chosen points on each leaf. Nickel and U concentrations differed significantly between washed and unwashed leaves from LTB. Particles on unwashed leaves measured up to 300 [micro sign]m in diameter, and were enriched with U. Uranium was detected on the surface of the leaf, whereas Ni was detected within leaf tissues. In unwashed LTB leaves, Ni and U concentrations did not significantly differ in areas with and without visible particles, suggesting that there were much smaller particles, indistinguishable at [times]100 magnification, which contributed to the overall metal burden. Washing removed the majority of the Ni and U on the surface, but residual U and Ni was detected. Irregularities in the leaf surface, such as scars from herbivory contained elevated U concentrations despite a washing step, presumably from trapping soil particles. Laser ablation ICP-MS revealed that mass loading makes a significant contribution to the contaminant burden of understory plants at LTB.