Historic Copper Research Articles

Effect of Composts, Lime and Diammonium Phosphate on the Phytoavailability of Heavy Metals in a Copper Mine Tailing Soil

Soil samples from a historic copper mine tailing site at the Parys Mountain, North Wales (UK) were amended with green waste compost (GC), GC+30% sewage sludge (GCS), lime and diammonium phosphate (DAP), to determine the effect of amendments on DTPA- and Ca(NO 3) 2-extractable metals in the mine tailing and on the phytoavailability of heavy metals by a lettuce ( Lactuca sativa L.). Both compost were added at the rate of 10% by weight, lime was added as calcium carbonate equivalent (pH = 7) and DAP at a 2 300 mg kg −1 soil level. The experiment was arranged in randomised complete design with three replicates in pots under control environment. Addition of lime resulted in the largest reduction in metal extractability with DTPA and Ca(NO 3) 2 and phytoavailability of Cu, Fe and Zn while DAP was effective in lowering Pb extractability and phytoavailability. With exception of Zn, all other metals extracted decreased with time after amendment applications. The distribution of heavy metals between and within the four procedures of potentially bioavailable sequential extraction (PBASE) varied significantly ( P < 0.001). Stronger relationships were noted between the metals extracted with PBASE SE1 and Cu, Pb ( P < 0.01) and Fe ( P < 0.001) in the lettuce. These results indicate that addition of lime is sufficient to restore the vegetative cover to a high metal mine waste while DAP is good for stabilizing Pb, but its detrimental role on plant growth and the risk associated with presence of N in DAP (through N leaching) may restrict its chances for remediation of contaminated sites.

Physiological Aspects of Cadmium and Nickel Toxicity in the Lichens Peltigera rufescens and Cladina arbuscula Subsp. mitis

This study was undertaken with the aim of investigating the effect of Cd2+ and Ni2+ containing solutions on selected physiological parameters (metal uptake, chlorophyll a fluorescence, assimilation pigment composition, thiobarbituric acid-reactive substance production, and ergosterol content) in the lichens Peltigera rufescens and Cladina arbuscula subsp. mitis growing on historic copper mine-spoil heaps at Ľubietova-Podlipa, Slovakia. Physiological measurements did not confirm significantly higher sensitivity to Cd and Ni of the cyanolichen P. rurescens compared to the green-algal lichen C. arbuscula subsp. mitis. Under natural conditions, C. arbuscula subsp. mitis is able to grow directly on copper mine heaps of Central Slovakia, while P. rufescens grows only on their margins. A crucial factor for this limited distribution of P. rufescens may be, at least in part, the higher intracellular accumulation of metals. Although lichen photobionts are generally regarded as key elements of lichen sensitivity, further research is necessary to elucidate this point since the higher levels of intracellular Cd and Ni do not allow to regard cyanobacterial photobionts of P. rufescens as more sensitive than the eukaryotic ones of C. arbuscula subsp. mitis.

Physiological comparison of copper toxicity in the lichens Peltigera rufescens (Weis) Humb. and Cladina arbuscula subsp. mitis (Sandst.) Ruoss

Peltigera rufescens (Weis) Humb. with a prokaryotic photobiont Nostoc sp. and Cladina arbuscula subsp. mitis (Sandst.) Ruoss with a eukaryotic photobiont Trebouxia sp. were studied to determine the copper sensitivity of lichens with different algal symbionts. Samples growing on historic copper mine-spoil heaps at Ľubietová–Podlipa, Slovakia were assessed for physiological parameters, including total and intracellular uptake of copper, assimilation pigmentation, activity of photosystem II, ergosterol levels, thiobarbituric acid reactive substances and water-soluble protein content. Our results indicate that P. rufescens was more sensitive to copper exposure than C. arbuscula subsp. mitis.

The effect of uric acid on outdoor copper and bronze

Bird droppings are often quoted as a decay agent for outdoor goods, in particular buildings and statues. Undoubtedly, they represent one of the major causes of aesthetic damage on outdoor materials, but the real chemical damage they are able to induce, in particular on metals, is not so well studied. This work focused on the short term role of uric acid, the main constituent of bird urine, with respect to copper, which make such an important contribution to architectural elements of buildings and outdoor sculpture. Preliminary results of laboratory tests and analyses on real exposed samples showed that uric acid chemically affects copper and bronzes: the surface of the metal is modified and copper urates formed. Also natural patina, formed on statues and roof, react with uric acid, even if it seems to afford some protection toward bird droppings. In general, experimental results confirm that the potential chemical damage by bird droppings is significant when considering external cultural heritage such as statues, metal monuments and buildings with historic copper roofs.

Historical copper and manganese levels in cattle feeds in Bavaria, Germany

Purpose. It has been repeatedly speculated that a deficiency in copper (Cu) or an excessive provision with dietary manganese (Mn) could play a role in spongiform encephalopathies [bovine (BSE) and others]. Therefore, commercial cattle feeds were screened for their content of these minerals.Design. The historical development of the levels of Cu and Mn in Bavarian cattle feeds was evaluated and the levels compared with feeding recommendations.Materials and methods. We report declared Cu and Mn contents from proprietary cattle feeds sold in Bavaria between 1978 and 1998.Results. Mn contents in ruminant feeds were generally high, and there was a trend of increasing Mn levels in ruminant feeds between 1980 and 1990, which was in synchrony with an increase in internationally recommended Mn levels for ruminants. Recently, the recommendations have been modified again to lower levels.Conclusion. Although no causative connection to the occurrence of BSE can be made, the practice of high Mn supplementation of propri...

English

To protect the Ocoee River in Tennessee (USA) from acidity and metals loadings from historical copper mining and processing activities, OXY USA is conducting removal actions to alleviate contaminant discharges from North Potato Creek (NPC). One such action is construction of an innovative in- pit lime treatment facility at the South Mine Pit designed to treat NPC flows up to a 10-yr, 24-hr storm of 1,649 m 3 /min (972 cfs) prior to discharge to the Ocoee River. OXY USA performed an Engineering Evaluation / Cost Analysis (EE/CA) to identify and evaluate alternatives to address contaminant discharges from North Potato Creek to the Ocoee River. The alternative that was determined to best meet the evaluation criteria was the in-pit treatment alternative. The in-pit treatment system treats the entire 10-yr, 24-hour storm flow of NPC by adding lime to raise the pH to the level required to precipitate dissolved metals and then settling the precipitated solids in an existing 8.1 hectare (20 acre) abandoned surface mine pit. The treatment system utilizes the existing surface mine pit as a settling pond. The in-pit treatment facility was constructed for 15% of the estimated cost of a conventional lime treatment facility capable of treating comparable NPC flows. The NPC Water Treatment Plant operations began in January 2005 and results show that reductions in aluminum, copper, iron, manganese, zinc, and other dissolved metals loading of over 360 kg (790 lbs.) per day to the Ocoee River are being achieved.

The Moonta-Wallaroo mining district, South Australia: A geophysical perspective

Located on the Yorke Peninsula in South Australia, the Moonta-Wallaroo area is an important area of historical copper mining. Hydrothermal copper-gold-silver sulphide mineralisation occurs in Palaeoproterozoic and Mesoproterozoic metamorphic and igneous rocks, but there is no outcrop of these basement rocks due to subdued relief and extensive sedimentary cover. The lack of outcrop, plus the complexity of the local geology, means that basement geological maps of the area are largely speculative. An interpretation of semi-regional aeromagnetic data from the area suggests the basement comprises meta-igneous rocks overlain to the east by an increasing thickness of sedimentary and/or meta-sedimentary cover. Anomalies interpreted to be of stratigraphic origin are quite well developed in areas of meta-sedimentary rocks, and regional strike is interpreted as trending northeast-southwest. Linear anomalies to the north and west of the Wallaroo Mines are interpreted as resulting from magnetite deposited in faults during a regional iron-rich metasomatic event. Based on this interpretation, a major east-west/northeast-southwest trending deformation zone is recognised, interpreted as a locus of reverse and dextral faulting. The entire study area is cross-cut by late brittle faults that trend mainly northwest-southeast. This interpretation/structural scenario is consistent with mine-scale structural studies in both the Moonta and Wallaroo Mines, although, the resolution of the aeromagnetic data is insufficient to map deposit-scale structures. Ground-based geophysical exploration in the Moonta-Wallaroo area is hindered by the generally electrically conductive environment and the presence of cultural features, such as wire fences. However, surface and downhole time-domain EM surveys have successfully located massive-sulphide mineralisation comprising the Poona and Wheal Hughes deposits. The Poona deposit has also been shown to give rise to an IP response, and there is evidence that the lodes elsewhere in the Moonta area are also associated with IP anomalies.

Western Tasmanian Regional Minerals Program (part 2): airborne electromagnetic data – quality control and interpretation

Recent regional scale helicopter electromagnetic (HEM) data acquired on the west and northwest coasts of Tasmania have demonstrated the powerful geological mapping capabilities of the HEM technique. Quality control for the survey was provided by analysis of repeat data from daily test lines, and comparison with surface geophysical data. Data have been interpreted by conductivity-depth imaging, complemented by layered-earth inversion of selected lines. The maximum depth of investigation for the HEM survey has been determined to be around 150 m, based on both theoretical calculations and the results of conductivity-depth imaging. A preliminary interpretation of the HEM data is presented for the Balfour region. The HEM survey has clearly differentiated previously unmapped units within the Proterozoic Rocky Cape Group, and has defined several major structural trends within the survey area. A large number of bedrock conductors have been identified in the HEM data, particularly close to the historic copper mining centre of Balfour.

Toxicity of copper to Quercus robur (English Oak) seedlings from a copper-rich soil

Wisniewski, L. and Dickinson, N.M. Toxicity of copper to Quercus robur (English Oak) seedlings. ––Acorns were germinated after collection from a mature Q. robur woodland at an historic copper mine site in Cheshire, England, and from an uncontaminated reference site. Hydroponic screening trials of seedlings using 0.5 mg Cu l −1 in 25% Hoagland's solution found no growth differences between sites of origin that indicated tolerance. Copper accumulated in the roots, with restricted transport to foliage. Prolonged exposure caused gross perturbations of root morphology, reduced root and shoot growth, and leaf chlorosis. Pre-exposure of seedlings to low levels of copper and repeated exposure provided little evidence for acclimation to the metal. Damage to photosynthetic systems was reflected in altered chlorophyll ratios and carotenoid pigments, including those related to the xanthophyll cycle. Zeaxanthin biosynthesis was not a particularly sensitive or reliable indicator of plant stress. It is concluded that survival of oak seedlings in the field is related to soil or rhizosphere processes mediating copper mobility, rather than to physiological tolerance or plant acclimation.

Metal levels in body tissues, forage and fecal pellets of elk ( Cervus elaphus) living near the ore smelters at Sudbury, Ontario

Ontario’s only free-ranging elk herd located at Burwash–French River has been subjected to the influence of historic copper–nickel–iron (Cu–Ni–Fe) ore smelting operations within the Sudbury area. Metal levels in selected body tissues, preferred forage items and fecal pellets were determined, and their potential effects on health and reproductive viability assessed. Significant age effects were apparent in 13 out of 31 tissue metal values obtained, with most age-related differences attributable to elevated concentrations in fetal tissues. Cu and zinc (Zn) levels were four to six times higher in livers and one and a half to two times higher in the bones of fetuses as compared to post-natal animals. Enhanced pre-natal tissue burdens were also noted for cobalt (Co), Ni and lead (Pb) in muscles. However, mean cadmium (Cd) levels in kidney, liver and muscle tissues, as well as hepatic Fe concentrations, showed significant increases with age. Although Cd levels in the kidneys of older elk were still well below the reported threshold for irreversible organ damage, and not considered to be health-threatening, detailed histological study of the cortical tissues for subtle pathotoxicological effects may be warranted. Unlike renal and hepatic tissues, Cd concentrations in skeletal muscle were minimal and within levels considered acceptable for human consumption. Forage species collected in the elk range generally showed higher (two to eight times) Ni and Fe levels than the corresponding plants from a non-contaminated reference site. The highest Ni and Fe burdens were carried by eastern white cedar, a preferred winter food item for elk. No consistent site-related trends were demonstrated by Cu, Zn, Co, Pb, chromium (Cr) and Cd forage levels. Mean metal concentrations in fecal pellets generally exceeded the mean composite forage levels by a factor of 3, except for Ni, which was five times more concentrated in feces. Significantly elevated Ni and Fe levels in preferred browse species and fecal pellets of the Sudbury-area elk could be of concern and warrant further investigation.

PIXE and RBS as a tool for the analysis of historic copper halfpennies

RBS and PIXE microbeam analysis is used to investigate the trace element concentrations as well as the surface corrosion of counterfeited copper halfpennies from the mid 18th century. PIXE elemental mapping was used to identify regions with a minimum of light element contamination which could be used for accurate trace element determinations. RBS analysis of selected points on the map could be used to confirm the absence of corrosion or contamination, and in addition yielded valuable information on the composition and structure of the corrosion layers.

Anthropogenic Copper Inventories and Mercury Profiles from Lake Superior: Evidence for Mining Impacts

During the past 150 years, the mining industry discharged more than a billion tons of tailings along Lake Superior shorelines and constructed numerous smelters in the watershed. Given the vast size of Lake Superior, were sediment profiles at locations far offshore impacted by nearshore activities? Did copper and associated precious metal mining modify regional fluxes for copper and mercury? Samples from thirty sediment cores document that background concentrations of copper are high (mean 60.9 ± 7.0 μg/g), due to the proximity of natural ore sources. Anthropogenic inventories uncorrected for focusing also are high, ranging from 20 to 780 μg/cm 2 (mean 187 ± 54 μg/cm 2). Focusing factor corrections decrease the mean estimate and reduce variance (144 ± 24 μg/cm 2). Several approaches to estimating inputs suggest that only 6 to 10% of historic copper deposition originated directly from atmospheric sources, emphasizing terrestrial sources. Moreover, coastal sediment cores often show synchronous early increases in copper and mercury with buried maxima. Around the Keweenaw Peninsula, twenty-two cores trace high copper and mercury inventories back to mill and smelting sources. Direct assays of ores from thirteen mine sites confirm a natural amalgam source of mercury in the stamp mill discharges. Core records from inland lakes (Michigamme Project) also reveal patterns of copper and mercury inputs from a variety of mining sources: historic tailing inputs, amalgam assay releases, and atmospheric smelter plumes.

In Situ Copper Toxicity Tests: Applying Likelihood Ratio Tests to Daphnia pulex Incubations in Keweenaw Peninsula Waters

Copper toxicity was examined in the Keweenaw Waterway and Gay region using in situ mortality tests. Daphnia pulex were placed in shell vials at thirteen field sites selected to encompass copper contamination from tailing piles to undisturbed shoreline environments. Likelihood Ratio Tests statistically compared mortality patterns between sites. In ponds on stamp sand piles, Daphnia survivorship was very low as dissolved copper concentrations greatly exceeded laboratory-derived LC 50 values. Survivorship at shoreline stamp sand sites in Torch Lake, the most disturbed region, was also low, demonstrating a “halo” effect around shoreline piles. Survivorship was much better in Portage Lake and in wetland sites, probably because of lower Cu concentrations and organic complexing. Daphnia's ability to tolerate dissolved copper concentrations above laboratory LC 50 values suggests that much of the dissolved copper in the Keweenaw Waterway is complexed and non-available. Non-bioavailable ratios (NRs) were determined by means of 96-hour EPA-protocol laboratory toxicity tests, and results were compared with laboratory copper ion tests. Although one site showed that seepage of humic-rich groundwater through stamp sands might enhance dissolved copper levels, in general the mean total copper levels found in the Keweenaw Waterway system were lower than reported 20 years ago, suggesting that the system is recovering from historic copper contamination.

Heavy metals in the Hamps and Manifold valleys, North Staffordshire, U.K.: Partitioning of metals in floodplain soils

The catchments of the rivers Hamps and Manifold in North Staffordshire are contaminated with base metals; soils and sediments have been sampled from the floodplains and analysed. Periods of historic copper mining in the Hamps valley and lead and copper mining in the Manifold released metalliferous sediments and these were transported and incorporated into floodplains downstream. Sequential chemical extractions on the samples showed much of the cadmium to be easily exchanged (up to 70%), and there was evidence for the translocation of cadmium down a soil profile over some 100 years. Only low concentrations of lead and copper were extracted easily, and for lead the Fe/Mn oxide and the organic fractions were the most important (up to 75% and up to 70% in different instances). For copper the organic fraction dominated.

Thule and Historic Copper Use in the Copper Inuit Area

The extensive use of native copper by historic Copper Inuit has been felt to be a fairly recent development, inspired in one way or another by indirect European contact. This conclusion seems to be based on the comparison of ethnographic historic collections and archaeological prehistoric ones. However, an examination of archaeological collections dating from the historic period suggests that copper and other metals are much less frequent in archaeological samples than in functioning, ethnographically-described assemblages. The difference appears to be due to curation, which in turn is a product of the high value and durability of metal. Archaeological collections from the prehistoric Thule culture in the area show a frequency of copper tools that is actually higher than the frequency of all metals at late nineteenth-century sites. This study illustrates some of the difficulties inherent in uncritical use of ethnographic data to solve archaeological problems.

Copper econometric models

There are three copper econometric models in the open literature: Arthur D. Little (ADL) model, Fisher et al. (FCB) model, and Charles River Associates (CRA) model. This paper explains these models, re-estimates their coefficients by using identical data (for the period from 1957–1973), synthesizes a copper econometric model by tailoring various elements of the models into a composite model, and compares several of the output of this composite model with actual past data. The three models vary in the extent of their coverage. In general, the ADL model concentrates on U.S. refined copper market, the FCB model covers the international copper primary market more thoroughly than the U.S. market, and the CRA model is evenly distributed between the international and U.S. primary markets. All three models use almost the same exogenous variables for the input information. The three models examined show almost identical strength and weaknes in simulating copper markets. Based on historical copper market relationships, the three models apparently are not able to predict future markets efficiently. For example, none of the three models could have predicted dramatical copper price creases in 1973. The Penn Composite Model, properly combined to contain only the strength of the ADL and FCB models, has improved model predictability, but it is still far from satisfactory. The model can be greatly polished if it takes into account copper companies' production schemes and government's intentions simultaneously.

Historic Church's Copper Roof Good After 213 Years

An examination of English-made copper sheets taken from the roof of Christ Church, Philadelphia, Pa. after 213 years' exposure shows a weathering loss of 0.007-inch at thinnest areas, equivalent to a corrosion rate of 0.000033-inch per year. It is believed the essentially rural character of the atmosphere during early exposure of these sheets has contributed to their life. Recent corrosion tests on copper sheets in an industrial atmosphere, show somewhat higher rates. Rockwell hardness of 15T 61 to 63 indicated the sheets on the church had been finished with a slight temper. Screws driven through the center of some sheets twenty years ago restricted expansion and contraction and caused fatigue cracks. Some of the 3-inch wrought iron nails originally used to fasten the copper pans to the roof boards had corroded through at the roof line, possibly as a result of condensation.