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We analyzed sediment cores collected from three equatorial zone lakes in the Rwenzori Mountains of Uganda for Hg and dated them using 210Pb. The results show that the lakes have been contaminated by anthropogenic Hg from atmospheric deposition and that the onset of Hg pollution in the region began at least by the late 19th century. Mercury accumulation in all sediment cores increased by about 3-fold since the mid-19th century, a similar increase to that shown in other remote regions worldwide. These results from tropical high-elevation sites are the first for this region and contribute to our understanding of global Hg pollution trends. The atmospheric boundary layer is at a higher altitude in equatorial areas than at midlatitudes, and therefore, Hg deposition in these regions may not be enhanced by diurnal penetration of tropospheric air and associated reactive gaseous mercury as has been reported for mountain lakes at higher latitudes. Furthermore, the relatively low abundance of atmospheric oxidants may limit the amount of gaseous elemental mercury oxidized to the reactive gaseous form in equatorial Africa. These Rwenzori Hg records therefore have important implications for the understanding of Hg dynamics at high elevations in equatorial regions.

The Tibetan Plateau is described as the "Roof of the World" averaging over 4000 m above sea level; it is remote, isolated, and presumed to be a pristine region. In order to study the history of atmospheric mercury (Hg) pollution and its spatial variation across the Plateau, lakes were chosen from three areas forming a north to south transect. Sediment cores were taken from three sites in each area and dated using the radionuclides 210Pb and 137Cs. Analysis of the cores yielded the first comprehensive Hg reconstructions for the Plateau, showing clear Hg pollution at all sites. The first indication of Hg pollution is much earlier than the onset of the industrial revolution in Europe, but the most significant pollution increase is from the 1970s, followed by a further marked increase from the 1990s. The mean post-2000 atmospheric pollution Hg accumulation rates for the sampling sites were estimated at between 5.1 and 7.9 microg m(-2) yr(-1). The increase in Hg pollution over the last few decades is synchronous with the recent economic development in Asia (especially China and India), and pollution Hg levels continue to increase. Furthermore, contemporary sediment Hg accumulation rate data are in broad agreement with Hg deposition values derived from global models that attribute pollution to sources mainly within southeast Asia. As most of the sites are exceptionally remote and situated above the atmospheric boundary layer, these results underline the need to understand the local Hg cycle in both regional and global context.

This paper describes the first results of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in sediment cores of Admiralty Bay, Antarctica. These markers were used to assess the local input of anthropogenic materials (particulate and organic compounds) as a result of the influence of human occupation in a sub-Antarctic region and a possible long-range atmospheric transport of combustion products from sources in South America. The highest SCPs and PAHs concentrations were observed during the last 30 years, when three research stations were built in the area and industrial activities in South America increased. The concentrations of SCPs and PAHs were much lower than those of other regions in the northern hemisphere and other reported data for the southern hemisphere. The PAH isomer ratios showed that the major sources of PAHs are fossil fuels/petroleum, biomass combustion and sewage contribution generally close to the Brazilian scientific station.

Concentrations are reported of hexabromocyclododecanes (HBCDs) and tetrabromobisphenol-A (TBBP-A) in water (n = 27), sediment (n = 9), and fish samples (n = 30) from nine English lakes. Seasonal variation in concentrations in water is minimal. Concentrations of TBBP-A range from 140 to 3200 pg L(-1) (water), 330 to 3800 pg g(-1) dry weight (sediment), and <0.29 to 1.7 ng g(-1) lipid weight (fish). Those of SigmaHBCDs range between 80 and 270 pg L(-1) (water), 880 and 4800 pg g(-1) dry weight (sediment), and 14 and 290 ng g(-1) lipid weight (fish). Aqueous concentrations of SigmaHBCDs and TBBP-A are significantly positively correlated, indicating a common source. Average +/-sigma(n) "freely-dissolved" phase proportions are 47 +/- 4.7% (SigmaHBCDs) and 61 +/- 2.9% (TBBP-A). Average field-derived bioaccumulation factors are 5900, 1300, 810, and 2100 for alpha-, beta-, gamma-, and SigmaHBCDs, respectively. Tetrabromocyclododecadienes are detected in all sediments, with pentabromocyclododecenes present in some. This suggests HBCD degrades via sequential loss of HBr. The delta-HBCD meso form was quantified in 43% of fish samples (1.0-11% SigmaHBCDs). Its absence from temporally and spatially consistent water and sediment samples suggests it is formed via bioisomerization. While HBCD chiral signatures are racemic in water and sediment, our data reveal enantiomeric enrichment of (-)alpha-HBCD and (+)gamma-HBCD in fish.

As a key constituent of their protective cell wall all mycobacteria produce a large structural component, the mycolyl-arabinogalactan (mAG) complex, which has at its core a galactan moiety of alternating beta-(1-->5) and beta-(1-->6) galactofuranosyl residues. Galactan biosynthesis is essential for mycobacterial viability and thus inhibitors of the enzymes involved in its assembly are potential drugs for the treatment of mycobacterial diseases, including tuberculosis. Only two galactofuranosyltransferases, GlfT1 and GlfT2, are responsible for the biosynthesis of the entire galactan domain of the mAG and we report here the first high-throughput assay for GlfT2. Successful implementation of the assay required the synthesis of multi-milligram amounts of the donor for the enzyme, UDP-Galf, 1, which was achieved using a chemoenzymatic approach. We also describe an improved expression system for GlfT2, which provides a larger amount of active protein for the assay. Kinetic analysis of 1 and a known trisaccharide acceptor for the enzyme, 2, have been carried out and the apparent K(m) and k(cat) values obtained for the latter are in agreement with those obtained using a previously reported radiochemical assay. The assay has been implemented in 384-well microtiter plates, which will facilitate the screening of large numbers of potential GlfT2 inhibitors, with possible utility as novel anti-TB drugs.

Two galactosyl transferases can apparently account for the full biosynthesis of the cell wall galactan of mycobacteria. Evidence is presented based on enzymatic incubations with purified natural and synthetic galactofuranose (Galf) acceptors that the recombinant galactofuranosyl transferase, GlfT1, from Mycobacterium smegmatis, the Mycobacterium tuberculosis Rv3782 ortholog known to be involved in the initial steps of galactan formation, harbors dual beta-(1-->4) and beta-(1-->5) Galf transferase activities and that the product of the enzyme, decaprenyl-P-P-GlcNAc-Rha-Galf-Galf, serves as a direct substrate for full polymerization catalyzed by another bifunctional Galf transferase, GlfT2, the Rv3808c enzyme.

The major structural component of the cell wall of Mycobacterium tuberculosis is a lipidated polysaccharide, the mycoyl-arabinogalactan-peptidoglycan (mAGP) complex. This glycoconjugate plays a key role in the survival of the organism, and thus, enzymes involved in its biosynthesis have attracted attention as sites for drug action. At the core of the mAGP is a galactan composed of D-galactofuranose residues attached via alternating beta-(1-->5) and beta-(1-->6) linkages. A single enzyme, glfT, has been shown to synthesize both glycosidic linkages. We report here the first high-level expression and purification of glfT by expression of the Rv3808c gene in Escherichia coli C41(DE3). Following a three-step purification procedure, 3-7 mg of protein of >95% purity was isolated from each liter of culture. We subsequently probed the substrate specificity of glfT by evaluating a panel of potential mono- and oligosaccharide substrates and demonstrated, for the first time, that trisaccharides are better substrates than disaccharides and that one disaccharide, in which the terminal D-galactofuranose residue is replaced with an L-arabinofuranose moiety, is a weak substrate. Kinetic characterization of the enzyme using four of the oligosaccharide acceptors gave K(m) values ranging from 204 microM to 1.7 mM. Through the use of NMR spectroscopy and mass spectrometry, we demonstrated that this recombinant enzyme, like the wild-type protein, is bifunctional and can synthesize both beta-(1-->6) and beta-(1-->5)-linkages in an alternating fashion. Access to purified glfT is expected to facilitate the development of high-throughput assays for the identification of inhibitors of the enzyme, which are potential antituberculosis agents.

This paper describes lake sediment spheroidal carbonaceous particle (SCP) profiles from Laguna Chica San Pedro, located in the Biobío Region, Chile (36 degrees 51' S, 73 degrees 05' W). The earliest presence of SCPs was found at 16 cm depth, corresponding to the 1915-1937 period, at the very onset of industrial activities in the study area. No SCPs were found at lower depths. SCP concentrations in Laguna Chica San Pedro lake sediments were directly related to local industrial activities. Moreover, no SCPs were found in Galletué lake (38 degrees 41' S, 71 degrees 17.5' W), a pristine high mountain water body used here as a reference site, suggesting that contribution from long distance atmospheric transport could be neglected, unlike published data from remote Northern Hemisphere lakes. These results are the first SCP sediment profiles from Chile, showing a direct relationship with fossil fuel consumption in the region. Cores were dated using the 210Pb technique.

The human ABO(H) blood group A and B antigens are generated by the homologous glycosyltransferases A (GTA) and B (GTB), which add the monosaccharides GalNAc and Gal, respectively, to the cell-surface H antigens. In the first comprehensive structural study of the recognition by a glycosyltransferase of a panel of substrates corresponding to acceptor fragments, 14 high resolution crystal structures of GTA and GTB have been determined in the presence of oligosaccharides corresponding to different segments of the type I (alpha-l-Fucp-(1-->2)-beta-D-Galp-(1-->3)-beta-D-GlcNAcp-OR, where R is a glycoprotein or glycolipid in natural acceptors) and type II (alpha-l-Fucp-(1-->2)-beta-D-Galp-(1-->4)-beta-d-GlcNAcp-OR) H antigen trisaccharides. GTA and GTB differ in only four "critical" amino acid residues (Arg/Gly-176, Gly/Ser-235, Leu/Met-266, and Gly/Ala-268). As these enzymes both utilize the H antigen acceptors, the four critical residues had been thought to be involved strictly in donor recognition; however, we now report that acceptor binding and subsequent transfer are significantly influenced by two of these residues: Gly/Ser-235 and Leu/Met-266. Furthermore, these structures show that acceptor recognition is dominated by the central Gal residue despite the fact that the L-Fuc residue is required for efficient catalysis and give direct insight into the design of model inhibitors for GTA and GTB.

The historical record of the input of pyrolysis-derived pollutants via the atmosphere, i.e. black carbon (BC), polycyclic aromatic hydrocarbons (PAH) and spheroidal carbonaceous particles (SCP) was measured in the sediments of three remote alpine lakes situated in the Julian Alps, northwest Slovenia. Parallel sedimentary trends for BC, PAH and SCP were observed across the Julian Alps and relationships among these contaminants are discussed. Inputs of these pyrolytic-contaminants to sediments of remote lakes started to rise at the end of the 19th century, while their peak inputs were observed in the mid-20th century, amounting up to 6.0 gm(-2) yr(-1) for BC, 5200 x 10(4) m(-2) yr(-1) for SCP and 2900 microg m(-2) yr(-1) for PAH. In the last two to three decades, inputs decreased substantially, by a factor of up to 3 for BC, 7 for SCP and at least 3 for PAH.

Background: cis-AB enzymes are rare glycosyltransferases that synthesize both blood group A and B antigens. We have identified a large cohort of Korean cis-AB blood donors and studied the N-acetylgalactosaminyltransferase (glycosyltransferase A, GTA) and galactosyltransferase (glycosyltransferase B, GTB) activity of their cis-AB serum enzymes., Materials and Methods: The cis-AB01 allele was identified by PCR-RFLP (polymerase chain reaction-restriction fragment length polymorphism) in 60 donors collected at the Gwangju-Chonnam Red Cross Blood Center. Enzyme assays of this cis-AB enzyme were performed on available serum samples from 16 donors with the cis-AB01/O genotype and three with the cis-AB01/A genotype., Results: In cis-AB donors with an O allele, both the GTA and GTB activity of the cis-AB enzyme were markedly reduced compared to normal A and B controls (29% and 27%, respectively). This is consistent with the behaviour predicted from kinetic studies of a recombinant model of the corresponding AAAB enzyme., Conclusion: Although variable, cis-AB enzymes feature reduced GTA and GTB activities., Summary: Cis-AB enzymes feature variable but reduced GTA and GTB activities with relatively weaker GTB activity, consistent with the weak agglutination present on forward typing with anti-B.

Spheroidal carbonaceous particles (SCPs) provide an unambiguous indication of atmospherically deposited contamination from industrial sources. SCP data from a 12 year annual sediment trapping and coring programme at 14 lakes based on the UK Acid Waters Monitoring Network, were used to consider temporal trends in deposition and to compare these with measured non-marine sulphate fluxes. Results show good temporal coherence across a broad area of northern UK and that SCP deposition levels and are now at their lowest since the 1940s, in agreement with modelled sulphate data. SCP fluxes show reasonable linearity with measured non-marine sulphate depositional fluxes from the nearest UK Acid Deposition Monitoring Network sites, especially over the post-flue-gas desulphurisation period, but comparisons prior to 1972 are not possible due to lack of data. We speculate on whether palaeolimnological SCP data might be used to reconstruct the history of non-marine sulphate fluxes from industrial sources.

Background: Few studies have investigated the reaction kinetics and interactions with nucleotide donor and acceptor substrates of mutant human ABO glycosyltransferases. Previous work identified a B(w) allele featuring a 556G>A polymorphism giving rise to a weak B phenotype. This polymorphism is predicted to cause a M186V amino-acid mutation within a highly conserved series of 16 amino acids present both in both blood group A- and blood group B-synthesizing enzymes. These residues are known as the disordered loop because their location cannot be determined in the crystal structure of the enzyme. Another patient has been identified with a 556G>A B(w) allele and the kinetics of the resulting mutant glycosyltransferase were studied., Study Design and Methods: Serologic testing with murine and human reagents, amplification of the coding regions of exons 6 and 7, and DNA sequencing were performed with standard protocols. Enzyme kinetic studies utilized a model of human GTB M186V expressed in Escherichia coli with radiolabeled UDP-galactose and UDP-N-acetylgalactosamine as donor substrates and synthetic H-disaccharide as acceptor following standard protocols., Results: The patient's red blood cells demonstrated a weak, but not mixed-field, B phenotype. Kinetic studies on the mutant enzyme revealed diminished activity (k(cat) = 0.15 per sec with UDP-galactose compared to 5.1 per sec for wild-type GTB) and elevated K(m) values for all substrates., Conclusion: This enzyme with a mutation in the disordered loop produces weak B antigen expression because of greatly decreased enzyme activity and reduced affinity for B-donor and acceptor substances.

Despite advances in human islet isolation, islet yield remains inconsistent and unreliable. In recent studies, it has been suggested that serine proteases, in particular trypsin, have been shown to have a damaging effect on islet yield. This study evaluated enzyme activity levels throughout 42 human islet isolation procedures. Trypsin, chymotrypsin, and elastase activity was determined spectrophotometrically using suitable chromophoric substrates. The results of the islet isolations were rated as successful (n = 19) or unsuccessful (n = 23) based on the islet yield and functionality. The enzyme activity profiles of the isolations were compared. No significant differences in donor-related variables were found in this study. However, in the successful isolations, a significantly greater amount (85.6 ± 1.9%; p = 0.0017) of the pancreas was digested in a significantly shorter digestion time (19.7 ± 0.6 min; p = 0.0054) compared with 74.8 ± 2.5% of digested tissue in 22.6 ± 0.7 min in the poor isolations. This study showed no significant effect of serine protease levels on the outcome of islet isolations, regardless of enzyme inhibitor supplementation. These data suggest that serine protease activity does not sufficiently affect islet yield. However, the data show that the most successful human islet isolations are achieved when the maximum amount of tissue is digested in the shortest amount of time. This suggests that further understanding of the isolation process should focus on the role of the collagenase digestion solution in the dissociation of the endocrine-exocrine tissue connection.

Despite advances in human islet isolations, there remain inconsistencies in human islet yield and viability after collagenase digestion. It has been suggested that trypsin may contribute to the proteolysis of collagenase and the destruction of islet cells, or possibly exert indirect effects on the pancreas by activating other endogenous serine proenzymes. This study evaluated the effects of serine proteases on collagenase activity and profiled the kinetics of serine protease activity throughout human islet isolations with and without addition of Pefabloc, a serine protease inhibitor. Cadaveric pancreases were perfused in the presence (n = 12) and absence of Pefabloc (0.4 mmole; n = 8). Samples were collected before and throughout the digestion process and were assayed for trypsin, chymotrypsin, and elastase activity. A study of the enzyme kinetics of serine proteases throughout human islet isolations showed an increase in activity levels throughout the digestion period. There was a significant difference in the chymotrypsin (1342 +/- 503 and 384 +/- 71 units) and elastase (7.94 +/- 1.1 and 2.761 +/- 0.69 units) levels between the control and Pefabloc-supplemented isolations, respectively. There was no significance difference noted among the trypsin (88 +/- 27 and 54 +/- 18 units) levels between the control and Pefabloc-supplemented isolations, respectively. This demonstrates that serine proteases are effectively inhibited by Pefabloc during the islet isolation process. These data show that the presence of serine proteases may likely damage the islets upon prolonged digestion of the pancreatic tissue.

Human islet isolation consists of a digestion phase, dilution phase, and purification phase. Recent evidence suggests that inconsistencies in islet yields are attributed to the activation of endogenous enzymes of the donor pancreas during the digestion phase. Therefore, following the digestion phase, it is important to inhibit these enzymes by the addition of an inhibitor to the dilution phase. In this study, we report the endogenous pancreatic enzyme levels after the purification phase and the effects of potential inhibitors on the proteases of interest. Results at the end of the purification phase indicated that chymotrypsin retained approximately 20% of the activity observed after the digestion phase, whereas trypsin, elastase, and collagenase retained approximately 2.5%, 2%, and 3.5% of the activity, respectively, demonstrating that added inhibitors are not fully effective. Potential enzyme inhibitors, human albumin, fetal calf serum, and aprotinin, were incubated with trypsin, chymotrypsin, elastase, and collagenase and assayed for activity. Fetal calf serum and aprotinin showed strong inhibitory actions toward trypsin and chymotrypsin. Aprotinin completely inhibited the tryptic activity; however, it did not inhibit human chymotrypsin or elastase activity. Human albumin showed minimal inhibition and was shown to act as a competitive inhibitor. This study clearly demonstrates that low amounts of endogenous pancreatic enzymes remain active at the end of the human islet isolation procedure and that the added inhibitors at the dilution are not fully effective at inhibiting the enzymes.

Introduction: Recent evidence has suggested that inconsistencies in human islet yield and viability after collagenase digestion is attributed to the activation of endogenous enzymes of the cadaveric donor pancreas. A study of the enzyme kinetics of serine proteases throughout human islet isolations showed a significant increase in activity levels throughout the digestion period. Following the digestion, it is important to further inhibit these enzymes by the addition of an inhibitor to the dilution media., Aim: To report the levels of endogenous pancreatic enzymes remaining after human islet isolation and the effects of three potential enzyme inhibitors on the proteases., Methodology: Human albumin, fetal calf serum, and the protease inhibitor aprotinin were incubated with the trypsin, chymotrypsin, elastase, and collagenase and were assayed for activity., Results: Results at the final stage indicated that chymotrypsin retained 21.0 +/- 7.5% (mean +/- SE; n = 20) of the activity observed at the conclusion of the enzymatic digestion phase of the isolation process, whereas trypsin, elastase, and collagenase retained 3.0 +/- 1.5%, 2.1 +/- 0.6%, and 3.9 +/- 0.9%, respectively. Fetal calf serum and aprotinin showed strong inhibitory effects against bovine pancreatic trypsin; however, they showed a weak inhibitory effect against elastase. Supplementation with aprotinin failed to inhibit human chymotrypsin and elastase. Human albumin showed minimal inhibition and was shown to serve only as a competitive inhibitor. No inhibition to collagenase was observed with human albumin, fetal calf serum, or aprotinin., Conclusions: This study clearly demonstrates that low amounts of endogenous pancreatic enzymes remain active throughout the human islet isolation process and that the added inhibitors at the end of the isolation process are not fully effective at inhibiting the enzymes.

Nisin variants and fragments were reacted with glutathione, and the products of the reactions were analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and liquid chromatography/mass spectrometry (LC-MS). Reactions between glutathione and either [Ala5]nisin or [Ala33]nisin resulted in products with two glutathione molecules conjugated to one nisin variant molecule. Only one glutathione molecule was added to [Ala5,Ala33]nisin. Fragmentation of the nisin molecule resulted in nisin 1-12, nisin 1-20, and nisin 1-32 fragments. Each fragment retained two dehydro residues, which subsequently underwent reaction with glutathione. The data indicated that the dehydroalanine residues of nisin are sites of addition for glutathione. Such addition renders the nisin molecule inactive.

Six sediment cores, from Lochnagar, Loch Chon and Loch Grannoch in Scotland, Burnmoor Tarn in the English Lake District, Llyn Llagi in the Snowdonia region of Wales and Banbury Reservoir in London, were taken in order to study the distribution of Hg temporally and historically in lake sediments across the UK. These cores were dated using the spheroidal carbonaceous particle technique. The cores show that all sites across the UK have been contaminated by Hg. There is a rapid increase in Hg concentration during the last approximately 200 years at all rural sites. In the 95 year record from Banbury Reservoir in London the sediments show high Hg concentrations (380-840 ngg(-1)) throughout. Inter-site differences in Hg concentrations and profiles may be explained by impacts of afforestation, composition of the sediments and the provenance of the Hg including catchment in-wash influences. For example, catchment contributions result in a sharp peak (1606 ngg(-1)) in the Hg concentration profile in the core taken from Loch Chon in the Trossachs region of Scotland. Mercury fluxes were calculated for the sediment cores and show that over the last few decades these UK sites, except Lochnagar, would fall into the upper range for European rural areas.

Background: Recent evidence has suggested that inconsistencies in human-islet yields after collagenase digestion are attributed to the activation of endogenous enzymes of the cadaveric donor pancreas. Inhibition of protease activity by Pefabloc (0.4 mM; Roche Biochemicals Inc., Indianapolis, IN) has recently been shown to improve human-islet isolation after prolonged cold storage of the pancreas. In this study, we have hypothesized that this improvement was because of the inhibition of three key serine proteases., Methods: Twenty cadaveric pancreases were perfused in the presence (n=12) and absence (n=8) of Pefabloc added at the time of distention using a customized perfusion device. Samples were collected throughout the digestion process and were assayed for trypsin, chymotrypsin, elastase, and total protease activity., Results: In all cases, the enzyme activity levels remained lower in the presence of Pefabloc as compared with the control samples. There was significantly higher chymotrypsin and elastase activity in the control group, but not trypsin or total protease activity, from the time following loading of the enzyme onto the pancreas until the stopping of the enzymatic digestion phase (dilution)., Conclusions: Pefabloc was shown to be an effective protease inhibitor throughout the entire digestion process. Pefabloc supplementation did not significantly effect the dilution time or the islet yield in this study; however, these data show that serine proteases are effectively inhibited by Pefabloc during the clinical islet process.

Inconsistencies in human islet yields after collagenase digestion have been attributed to the activation of endogenous enzymes of the donor pancreas. It has been suggested that pancreatic serine proteases contribute to the proteolysis of collagenase. This study defined the effects of endogenous enzymes within the pancreas on pancreas dissociation during collagenase digestion. Levels of collagenase activity from samples taken throughout several steps in islet isolation procedures, both with and without the addition of the serine protease inhibitor Pefabloc, were determined by a spectrophotometric assay using N-[3-(2-furyl)acryloyl]-Leu-Gly-Pro-Ala as the substrate. Results clearly demonstrated that the level of collagenase activity remains stable throughout the isolation procedure despite differences in the donor factors from several cadaveric donor pancreases. This was further demonstrated by observing no difference in activity levels after incubating commercial collagenase preparations with serine proteases and analyzing by means of collagenase activity and SDS-PAGE. These data show that the presence of serine proteases does not affect the level of collagenase activity; however, they likely damage the islet cells upon prolonged digestion of the pancreatic tissue. Further efforts at examining exogenous and endogenous enzyme levels may result in the development of an enzyme cocktail that is both stable and effective for digesting the human pancreas while preserving islet function and viability.

Lochnagar is a mountain lake located to the southeast of the Cairngorm Mountains in Scotland. The inputs and outputs of Hg and Pb and their distribution within the various ecosystem compartments were measured. Further, 17 sediment cores and 10 catchment peat cores were taken and dated using spheroidal carbonaceous particle (SCP) and 210Pb techniques. Total and anthropogenic Hg and Pb inventories since the 1860s for the lake basin and the catchment peats were calculated using this multiple core strategy. Hg sediment flux profiles based on the whole lake basin show that the flux to the sediments increased from the 1880s until the 1970s. This was followed by a relatively stable period (1970s to the present), during which the flux was approximately twice that of the 1880s. Similarly, the Pb flux increased from the 1860s until the 1940s and was also followed by a relatively stable period through to the present. Hg and Pb budgets for the whole catchment for 1998 indicated that 78% of the Hg and 91% of the Pb input to the lake were transported from the catchment. Hence, the expected decline resulting from the decrease in the atmospheric deposition of Pb was obscured in the sediment record. It is estimated that 77% of the total Hg and 90% of the total Pb deposited since the 1860s, and stored in the upper layers of the catchment peat soils, are from anthropogenic sources. The increased storage of Hg and Pb in the catchment implies that this will be a major source of these metals for the lake for many years. This will delay the restoration of the lake system, despite reductions in emissions to the atmosphere and subsequent deposition.

Anthropogenic trace metals enter the entire ecosystem of Lochnagar solely through atmospheric deposition. Trace metals, including Hg, have been monitored in atmospheric deposition and lake water, and measured in catchment vegetation, aquatic plants and zooplankton, revealing contamination levels in the ecosystem. Furthermore, 17 sediment cores were taken from different areas of the lake. Hg, Pb, Cd, Zn and Cu were analysed in all the cores, which show that the sediments have been heavily contaminated by these trace metals since the 1860s. The distribution of trace metals in the lake sediments was found to be heterogeneous, with concentrations in the surface sediments varying significantly: 110-250 ng/g, 100-360 microg/g, 39-180 microg/g, 0.3-1.9 microg/g and 8-25 microg/g for Hg, Pb, Zn, Cd and Cu, respectively. Trends in the concentration profiles for different trace metals in the same core are different, as are the trends of the profiles for the same metal in different cores. Hence, a single sediment core cannot represent the pollution history of the whole lake. As the soils and sediments contain a high proportion of plant debris and the debris has a high affinity for Hg, resulting in Hg enrichment. Hg was measured in plant debris (> 63 microm) separated from catchment soils and lake sediments. Plant debris may play an important role in storing and transferring Hg in this ecosystem.

Sediment cores taken from the deep basin of Loch Coire nan Arr in north-west Scotland were dated using 210Pb calibrated spheroidal carbonaceous particle (SCP) profiles and analysed for trace metals, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). These data show that the site is one of the least contaminated by atmospheric pollution in the UK. Peak concentrations of PAHs were found to be equivalent to background values at sites in the English Lake District. The date of concentration maxima for SCP, PCB and some metals were in agreement with previously published polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran (PCDD/F) data suggesting long-range industrial sources. The date of individual PAH concentration maxima were earlier, but concomitant with each other, possibly suggesting the influence of a local source. Comparison with remote European mountain lakes shows Loch Coire nan Arr to be one of the least contaminated sites in Europe with respect to PCBs, but more contaminated with respect to PAHs.

The Arctic is recognized as an important focus for long-range transport of contaminants, such as mercury (Hg), from industrial regions at lower latitudes. In addition to large geographic gaps, there are few long-term retrospective time trends in arctic research, besides the Greenland ice record, to assess the onset of atmospheric pollution as well as to establish the rates of change in the terrestrial environment. In a study of sediments from 21 lakes along a 150 km transect from the coast to the ice sheet margin in the Søndre Strømfjord (Kangerlussuaq) region, we present stratigraphic evidence for elevated Hg inputs to this ice-free region on Greenland's west coast. Nineteen study lakes showed Hg concentration enrichments (HgEFconc) in surface compared to deeper sediments, with a mean HgEFconc of 3. Higher HgEFconc are found in lakes closest to the ice margin. The existence of this Hg gradient is supported by pollution Hg inventories in three 210Pb-dated cores. While 210Pb inventories and Pb pollution are higher at the coast, pollution Hg inventories are nearly 3-fold higher at the ice margin (570 micrograms m-2) than at the coast (210 micrograms m-2). These dated cores also indicate an onset of Hg pollution in the region beginning at least by the late 19th century but possibly as early as the 17th century.

Historical trends in the concentrations of toxaphene, its component homologue groups, and individual chlorobornane congeners were determined in a dated sediment core from a mountain lake, Lochnagar, in Scotland, U.K., representing the first such profiles outside of North America. The profile of total toxaphene showed a bimodal distribution with maxima in the mid-1970s and early 1990s unlike the unimodal PCB profile (maximum 1973) in the same core. The earlier toxaphene peak shows agreement with the U.S. source curve and therefore may correspond to modeled global patterns while the later peak may be dueto long-rangetransportfrom eastern and southern Europe or from still lower latitudes. Sediment toxaphene concentrations (14 ng/g dry wt (dw) at surface; 40 ng/g dw at maximum) and accumulation rates (surface 0.42 ng cm(-2) yr(-1); maximum 1.6 ng cm(-2) yr(-1)) were considerably higher than levels in untreated sites in the Great Lakes region and the Canadian Arctic and are equivalent to those reported for the Great Lakes themselves where there have been additional riverine inputs. Two toxaphene congeners, B6-923 and B7-1001, accounted for most of the hexa- and heptachlorobornanes, respectively. B6-923 and B7-1001 abundance ratios (relative to the sum of 12 chlorobornane congeners) had doubling times of 17 +/- 3 and 12 +/- 3 yr, respectively. Given the remoteness of the site from areas of toxaphene production and usage, the high sediment levels raise concerns over toxaphene levels in areas of Europe closer to sources, especially where sites are fished for human consumption. Further European data are needed for comparison.

Lochnagar is a remote mountain lake to the south-east of the Cairngorm region in Scotland. Its catchment receives anthropogenic trace metals solely from atmospheric deposition. Ten peat cores were taken from the catchment and analysis confirmed that they have been contaminated by trace metals. The peats have an high affinity for trace metals and this results in metal accumulation in the surface peat layers. The formation of trace metal sulphides may also reduce remobilisation. In this way, trace metals derived from atmospheric deposition have been scavenged and accumulated. In contaminated peat layers, 77.4% Hg, 89.6% Pb, 93.4% Cu, 72.4% Zn and 86.5% Cd of the total stored are from anthropogenic sources. The accumulated trace metals in the peats can potentially influence the lake system through erosion. Spheroidal carbonaceous particle (SCP) profiles were used to date the peat cores. By referring to the SCP profiles in the peats and comparing these with the trace metal profiles in the lake sediments, the mobility of trace metals in the catchment peats is confirmed.

The use of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for the detection of bacteriocins was investigated. A 30-s water wash of the sample on the MALDI-TOF MS probe was effective in removing contaminants of the analyte. This method was used for rapid detection of nisin, pediocin, brochocin A and B, and enterocin A and B from culture supernatants and for detection of enterocin B throughout its purification.

Although fly-ash particles are found in high concentrations in areas of high acid deposition little environmental work has been done on the inorganic ash sphere (IAS) component. Spatial and temporal trends of IAS in the UK show similar patterns to those of spheroidal carbonaceous particles (SCP), except that there appears to be a continuous background of IAS in the sediment record. The ratio IAS:SCP shows similar trends to both fuel-type changes as identified by SCP characterisation and historical fuel consumption records. Spatial comparisons between IAS:SCP in lake surface sediments, SCP characterisation results and known particle sources are also good. IAS concentrations in lake surface sediments and measured and modelled total, wet and dry sulphur are significantly correlated and show similar results to those of SCP studies.