First comprehensive peat depositional records for tin, lead and copper associated with the antiquity of Europe's largest cassiterite deposits

Tin, as a constituent of bronze, was central to the technological development of early societies, but cassiterite (SnO2) deposits were scarce and located distantly from the centres of Mediterranean civilizations. As Britain had the largest workable ore deposits in the ancient Western world, this has led to much historical speculation and myth regarding the long-distance trading of tin from the Bronze Age onwards. Here we establish the first detailed chronology for tin, along with lead and copper deposition, into undisturbed ombrotrophic (rain-fed) peat bogs located at Bodmin Moor and Dartmoor in the centre of the British tin ore fields. Sustained elevated tin deposition is demonstrated clearly, with peaks occurring at 100-400 and 700-1000 calendar years AD - contemporaneous with the Roman and Anglo-Saxon periods respectively. While pre-Roman Iron Age tin exploitation undoubtedly took place, it was on a scale that did not result in convincingly enhanced deposition of the metal. The deposition of lead in the peat record provides evidence of a pre-Roman metal-based economy in southwest Britain. Emerging in the 4th century BC, this was centred on copper and lead ore processing that expanded exponentially and then collapsed upon Roman colonization during the 1st century AD. (C) 2011 Elsevier Ltd. All rights reserved.

Nucleoside Azide-Alkyne Cycloaddition Reactions Under Solvothermal Conditions or Using Copper Vials in a Ball Mill

Novel nucleoside analogues containing photoswitchable moieties were prepared using 'click' cycloaddition reactions between 5 '-azido-5 '-deoxythymidine and mono- or bis-N-propargylamide-substituted azobenzenes. In solution, high to quantitative yields were achieved using 5mol% Cu(I) in the presence of a stabilizing ligand. 'Click' reactions using the monopropargylamides were also effected in the absence of added cuprous salts by the application of liquid assisted grinding (LAG) in metallic copper reaction vials. Specifically, high speed vibration ball milling (HSVBM) using a 3/32('') (2.38mm) diameter copper ball (62mg) at 60Hz overnight in the presence of ethyl acetate lead to complete consumption of the 5 '-azido nucleoside with clean conversion to the corresponding 1,3-triazole.

Yellow earthworms:Distinctive pigmentation associated with arsenic- and copper-tolerance in Lumbricus rubellus

Lumbricus rubellus Hoffmeister, inhabiting soil at the 19th century Devon Great Consols mine at Tavistock, Devon, UK, show high tolerance to Cu- and As-toxicity and frequently have a striking yellow coloration. Specimens from this site (mature and immature) and from an uncontaminated site on Lancaster University campus (mature) were photographed, and the slide images digitized and analyzed. All L. rubellus showed reddish-purple pigmentation of the body wall that declined in intensity posteriorly. The metal- and metalloid-resistant earthworms, whether mature or immature, showed yellowing in the posterior half of the body. The source of the coloration was intense yellow pigmentation of the chloragogenous tissue surrounding the alimentary canal. The yellow pigmentation is masked by reddish-purple body wall pigmentation anteriorly. Total As concentrations in tissues were determined for the anterior, middle and posterior sections of resistant and non-resistant L. rubellus. Highest concentrations were in the middle sections of the mature and immature resistant L. rubellus (36.17 ± 19.77 and 27.77 ± 9.02 mg As kg^-1, respectively). Resistant immature L. rubellus lost condition over 28 d in soil treated with 750 mg As kg^-1, possibly due to a higher metabolism, whilst there was no loss in condition for resistant mature L. rubellus in the treated soil. As far as the authors are aware, this is the first report of yellow pigmentation of this kind in earthworms. The pigmentation may provide a useful indicator of exposure/resistance to soil contamination. © 2002 Elsevier Science Ltd. All rights reserved.

Copper- and arsenate-induced oxidative stress in Holcus lanatus L. clones with differential sensitivity

The biochemical responses of Holcus lanatus L. to copper and arsenate exposure were investigated in arsenate-tolerant and -non-tolerant plants from uncontaminated and arsenic/copper-contaminated sites. Increases in lipid peroxidation, superoxide dismutase (SOD) activity and phytochelatin (PC) production were correlated with increasing copper and arsenate exposure. In addition, significant differences in biochemical responses were observed between arsenate-tolerant and -non-tolerant plants. Copper and arsenate exposure led to the production of reactive oxygen species, resulting in significant lipid peroxidation in non-tolerant plants. However, SOD activity was suppressed upon metal exposure, possibly due to interference with metallo-enzymes. It was concluded that in non-tolerant plants, rapid arsenate influx resulted in PC production, glutathione depletion and lipid peroxidation. This process would also occur in tolerant plants, but by decreasing the rate of influx, they were able to maintain their constitutive functions, detoxify the metals though PC production and quench reactive oxygen species by SOD activity.

Changes in epilithic biomasses and invertebrate community structure over a deposit metal concentration gradient in upland headwater streams

Stream bed metal deposits affect the taxon richness, density and taxonomic diversity of primary and secondary producers by a variety of direct or indirect abiotic and biotic processes but little is known about the relative importance of these processes over a deposit metal concentration gradient. Inorganic matter (IM), algal and non-photosynthetic detrital (NPD) dry biomasses were estimated for 10 monthly samples, between 2007 and 2008, from eight sites differing in deposit density. Invertebrate abundance, taxon richness and composition were also determined. Relations between these variables were investigated by canonical correspondence analysis (CCA), generalized estimating equation models and path analysis. The first CCA axis correlates with deposit density and invertebrate abundance, with lumbriculids and chironomids increasing in abundance with deposit density and all other taxa declining. Community structure changes significantly above a deposit density of approximately 8 mg cm, when algal biomass, invertebrate richness and diversity decline. Invertebrate richness and diversity were determined by direct effects of NPD biomass and indirect effects of IM. Algal biomass only had an effect on invertebrate abundance. Possible pH, oxygen, food and ecotoxicological effects of NPD biomass on the biota are discussed.

Catchment and in-stream influences on metal concentration and ochre deposit density in upland streams, Northern Ireland

Metal concentrations from stream waters in two geological blocks in Northern Ireland were compared to determine the contributions of catchment characteristics and in-stream conditions. One block is composed of metamorphosed schist and unconsolidated glacial drift with peat or peaty podzol (mainly humic) soils, while the other block consists of tertiary basalt with brown earth and gley soils. Water samples were collected from 52 stream sites and analysed for Fe, Mn and Al as well as a range of other chemical determinands known to affect metal solubility. Densities of metal-rich ochre deposit were determined for stream bed stone samples. Higher conductivities and concentrations of bicarbonate, alkalinity, Ca and Mg occurred on basalt than on schist. Despite higher Fe and Mn oxide concentrations in basalt-derived non-humic soils, stream water concentrations were much lower and ochre deposit densities only one third of those on schist overlain by humic soils. Neither rock nor soil type predicted Al concentrations, but pH and dissolved oxygen did. Peat-generated acidity and the limited acid neutralising capacity of base-poor metamorphosed schist have resulted in elevated concentrations of metals and ochre deposit in surface waters.

Improved Efficiency for Partial Oxidation of Methane by Controlled Copper Deposition on Surface-Modified ZSM-5

The mono(μ-oxo) dicopper cores present in the pores of Cu-ZSM-5 are active for the partial oxidation of methane to methanol. However, copper on the external surface reduces the ratio of active, selective sites to unselective sites. More efficient catalysts are obtained by controlling the copper deposition during synthesis. Herein, the external exchange sites of ZSM-5 samples were passivated by bis(trimethylsilyl) trifluoroacetamide (BSTFA) followed by calcination, promoting selective deposition of intraporous copper during aqueous copper ion exchange. At an optimum level of 1–2 wt % SiO2, IR studies showed a 64 % relative reduction in external copper species and temperature-programmed oxidation analysis showed an associated increase in the formation of methanol compared with unmodified Cu-ZSM-5 samples. It is, therefore, reported that the modified zeolites contained a significantly higher proportion of active, selective copper species than their unmodified counterparts with activity for partial methane oxidation to methanol.

Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

Abstract The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

Effects of copper in plasma, gills, liver and muscle of seabream (Sparus aurata, Linnaeus 1758) juveniles

Dissertação de Mestrado, Aquacultura e Pescas, Faculdade de Ciências do Mar e do Ambiente, Universidade do Algarve, 2006

Unusual framework stabilization of Cu(II) and Cu(I) ions in a novel copper-substituted aluminophosphate with AEN topology prepared by one pot synthesis

A novel copper-substituted aluminophosphate (CuIST-2) has been synthesized using methylamine as a templating agent. X-Ray diffraction studies provide evidence for an AEN topology similar to the parent Cu-free IST-2.

Root ferric chelate reductase is regulated by iron and copper in straberry plants

In the present experiment, we studied the interaction between copper (Cu) and iron (Fe) in strawberry plants grown in nutrient solutions containing different concentrations of Fe. Plants grown in the absence of iron (Fe0) had the characteristic symptoms of Fe deficiency, with smaller chlorotic leaves, less biomass, acidification of the nutrient solution, and roots that were smaller and less ramified, while no symptoms of Fe deficiency were observed in plants grown with Fe. A greater amount of Cu was found in roots of chlorotic plants than in those grown with Fe, while plants grown with 20M of Fe (Fe20) in the nutrient solution had a greater amount of Fe compared with plants from the other treatments. Chlorotic plants (Fe0) and plants grown with the greatest level of Fe (Fe20) had a greater root ferric chelate reductase (FC-R; EC 1.16.1.17) activity compared with the other treatments with 5 or 10M Fe in the nutrient solution. The same pattern was obtained for relative FC-R mRNA concentration and for the sum of Fe and Cu contents in shoots (leaves plus crowns). The DNA obtained from amplification of the FC-R mRNA was cloned and several of the inserts analysed by single strand confirmation polymorphism (SSCP). Although there were different SSCP patterns in the Fe20 treatment, all the inserts that were sequenced were very similar, excluding the hypothesis of more than one FC-R mRNA species being present. The results suggest that Cu as well as Fe is involved in FC-R expression and activity, although the mechanism involved in this regulation is unknown so far. Both small contents of Fe and Cu in plants led to an over-expression of the FC-R gene and enhanced FC-R activity in strawberry roots.

Copper and lead removal by peanut hulls: equilibrium and kinetic studies

This research work aims to study the use of peanut hulls, an agricultural and food industry waste, for copper and lead removal through equilibrium and kinetic parameters evaluation. Equilibrium batch studies were performed in a batch adsorber. The influence of initial pH was evaluated (3–5) and it was selected between 4.0 and 4.5. The maximum sorption capacities obtained for the Langmuir model were 0.21 ± 0.03 and 0.18 ± 0.02 mmol/g, respectively for copper and lead. In bi-component systems, competitive sorption of copper and lead was verified, the total amount adsorbed being around 0.21 mmol of metal per gram of material in both mono and bi-component systems. In the kinetic studies equilibrium was reached after 200 min contact time using a 400 rpm stirring rate, achieving 78% and 58% removal, in mono-component system, for copper and lead respectively. Their removal follows a pseudo-second-order kinetics. These studies show that most of the metals removal occurred in the first 20 min of contact, which shows a good uptake rate in all systems.