Occurrence of Native Copper Near Jefferson City, Montana

Sometime prior to 1870, a group of prospectors made what was believed to be a "rich strike' on one of the tributaries of Prickly Pear Creek in Jefferson County, Montana. Instead of striking it rich, they had uncovered a native copper deposit, worthless to them because of its limited extent and remote location, but now of much interest to the geologist, and to the mining engineer because of its possible commercial value.

First-principle study of native defects in CuScO2 and CuYO2

This paper studies the electronic structure and native defects intransparent conducting oxides CuScO2 and CuYO2 using the first-principle calculations. Some typical native copper-related and oxygen-related defects, such as vacancy, interstitials, and antisites in their relevant charge state are considered. The results of calculation show that, CuMO2 (M = Sc, Y) is impossible to shown-type conductivity ability. It finds that copper vacancy and oxygen interstitial have relatively low formation energy and they are the relevant defects in CuScO2 and CuYO2. Copper vacancy is the most efficient acceptor, and under O-rich condition oxygen antisite also becomes important acceptor and plays an important role in p-type conductivity.

Mineralogical composition, copper and d18O at DSDP Site 59-448

Alteration in a submarine remnant volcanic arc should leave an important record of (1) the mineralogy of sea water-volcanic arc rock interaction; (2) the chemistry of solid reaction products; (3) the isotopic characteristics of such reactions (Muehlenbachs and Clayton, 1972; Spooner, Beckinsale, et al , 1977; Spooner, Chapman, et al., 1977); (4) the metallogenesis within such a sequence (Mitchell and Bell, 1973); and (5) the geothermal gradient during the alteration. The volcaniclastic breccias, tuffs, and igneous units of Sites 448 (993 m) and 451 (930.5 m) on the Palau-Kyushu and West Mariana ridges, respectively, are particularly suited for such studies because the thick sequences have remained submarine throughout their history, seemingly unaffected by magmatic or hydrothermal events after cessation of volcanic activity. Also, shipboard observations indicated a change in alteration products with depth. At both sites the igneous units and volcaniclastic rocks were altered to brownish clays and zeolites near the top of the volcanic sequence; to bright blue green clays and zeolites at moderate depths; and to very dark, nearly opaque, forest green clays and zeolites at still greater depths. Native copper occurs both as disseminated pockets in the volcaniclastic breccias and vesicular basalts and as veins in the breccias; native copper is restricted to stratigraphic levels characterized by the absence of sulfides or oxides of copper and iron. Although some native copper is found in vesicles of basalts and may be orthomagmatic, most of it is clearly secondary. Near dikes and sills, higher sulfur fugacity conditions caused the precipitation of iron and copper sulfides with an absence of native copper (Garrels and Christ, 1965). The occurrence of native copper may be an initial stage of Cu metallogenesis that forms porphyry coppers in island arcs (Mitchell and Bell, 1973). This study will address primarily the possibility that hydrothermal sea water interaction with volcanic arc rocks has created the mineralogical and isotopic zonation in Leg 59 cores. Hydrothermal activity can be expected in a rapidly growing island arc and is probably the result of a high geothermal gradient prevalent during arc magmatic activity. The chemical character of the alteration is further discussed by Hajash (1981).

Identification, functional expression and kinetic analysis of two primary amine oxidases from Rhodococcus opacus

Two native copper-containing amine oxidases (EC 1.4.3.21) have been isolated from Rhodococcus opacus and reveal phenotypic plasticity and catalytic activity with respect to structurally diverse natural and synthetic amines. Altering the amine growth substrate has enabled tailored and targeted oxidase upreg-ulation, which with subsequent treatment by precipitation, ion exchange and gel filtration, achieved a 90–150 fold purification. MALDI-TOF mass spectrometric and genomic analysis has indicated multiple gene activation with complex biodegradation pathways and regulatory mechanisms. Additional post-purification characterisation has drawn on the use of carbonyl reagent and chelating agent inhibitors. Michaelis–Menten kinetics for common aliphatic and aromatic amine substrates and several structural analogues demonstrated a broad specificity and high affinity with Michaelis constants (K M) ranging from 0.1 to 0.9 mM for C 1 –C 5 aliphatic mono-amines and <0.2 mM for a range of aromatic amines. Potential exploitation of the enzymatic versatility of the two isolated oxidases in biosensing and bioprocessing is discussed.

湖南麻阳砂岩型自然铜矿床地质及地球化学研究

麻阳铜矿有着悠久的开采历史，被誉为“江南第一古矿”，该矿不仅为古人提供了大量的铜资源，也是现今湖南省最大的铜矿。麻阳铜矿床位于麻阳县与辰溪县交界处，地处沅麻盆地中段，南部接近雪峰山，矿体赋存于白垩系红层砂岩中，严格受地层控制。 长期以来，雪峰山地区一直是地学界研究华南构造格局的重点地区，但沅麻盆地作为雪峰山构造带的次级构造单元受关注程度相对较低。20世纪60年代，多家单位在沅麻盆地开展铜、石油、煤、石膏普查和区域地质测量工作，先后在发现了麻阳(九曲湾)、黄双、杉木溪等12处自然铜/辉铜矿矿床(矿化点)。麻阳铜矿正式投产后，对铜矿床乃至沅麻盆地地质研究工作几乎处于停滞状态。20世纪90年代，开展的区域基础地质填图和麻阳铜矿床储量扩大的相关研究，对矿床地质描述、沉积相分析等做了进一步的工作，但对矿床地球化学所做工作甚少，对麻阳铜矿中自然铜矿化形成机理的认识还存在较大的分歧。本文在深入的野外地质工作基础上，对矿区及雪峰山地区岩石、矿石进行了细致的显微鉴定，并对矿石中各类矿物进行了详细的电子探针分析；系统分析了矿区及雪峰山地区各地质单元(地质体)的主量元素、微量元素、稀土元素、同位素等地球化学特征，结合前人研究主要取得如下结论性成果： (1) 通过主、微量元素地球化学分析，确定区域上沅麻盆地及其源区沉积岩、岩浆岩都具有壳源特征，碎屑物源为活动大陆边缘及岛弧区；矿区碎屑物源区主要经历基性斜长石风化阶段，风化程度不高。 (2) 麻阳铜矿床以及盆地内其他自然铜/辉铜矿矿化点大体都产在盆地靠近雪峰山一侧，赋矿地层为晚白垩系红层，矿体具有多层性的，但严格受透水性较好的灰白色-灰绿色砂岩控制，产状与砂岩乃至红色围岩产状完全一致，无穿插现象。横向上变化沿走向发育短，倾向长且可呈树枝(鸟足)状，但矿体消失部位多为河道相砂岩相变带。矿区发育褶皱构造和同沉积以及后期与褶皱有关的多组断裂，对矿体有破坏和再富集双重作用，但地层对矿化制约更明显。 (3) 麻阳铜矿床矿区碎屑物质来源于雪峰山地区，在矿石中发现的大量原生含自然铜矿化硅质碎屑是铜的最终来源。从碎屑结构上看，这种含铜碎屑与沉积硅质岩相似，但自然铜的铅同位素组成暗示铜的来源与白马山岩体印支期花岗岩、花岗闪长岩关系密切，而明显不同于雪峰山地区出露的前寒武系变质岩以及寒武系黑色页岩(二者都含有硅质岩夹层)，因此推断，含铜碎屑可能是与白马山岩体印支期花岗岩、花岗闪长岩活动有关的热水或热液产物。盆地成矿的铜，少部分由机械搬运以碎屑形式搬运至沉积区，并受原地淋滤；绝大部分可能是在风化区溶解由流水(地表水或地下水)带入沉积盆地。 (4) 外来的铜在生物硫富集的层位，与硫结合形成辉铜矿矿化。绝大部分铜在缺硫环境下，因成矿流体物化条件的变化快速沉积形成自然铜矿化。主矿化期发生在沉积期，成矿环境为低温、弱还原条件，流体为含硫酸根、氯离子的高盐度流体，有机质在成矿过程中可能起到一定的作用。 (5) 麻阳铜矿床主成矿期矿化形成后，矿体受同沉积及后期断裂的改造，在断裂附近形成矿化再富集，同沉积及后期断裂中都发现热液特征的石膏、自然铜脉，说明断裂活动时的热液作用对矿床有改造作用。 (6) 虽然麻阳铜矿床具有矿物组合、矿物产出的特殊性，但其成矿过程可能是特定的物化条件下的简单模式：风化-搬运-沉淀-改造。

Flows with 'Cu-type' characteristics at ODP Hole 104-642E (Table 1)

Native Cu occurs in amygdules, fractures and groundmass of tholeiites from Ocean Drilling Program Site 642 on the Vøring Plateau. Similar occurrences have been reported in other tholeiites of the early Tertiary North Atlantic Volcanic Province drilled at Deep Sea Drilling Project Sites 342 on the Vøring Plateau and 553 on the Rockall Plateau. The flows containing the native Cu have distinctive alteration patterns characterized by the combination of reddened flow tops, distinctive pastel coloration of the upper parts of the flows, relative abundance of celadonite, and the presence of native Cu. These associations suggest that subaerial weathering and subsequent seawater-basalt interaction are related to the occurrence of native Cu. An additional factor may be the increase in compatibility of Cu in silicates and Fe- Ti oxides that may accompany sub-solidus oxidation of basaltic flows. Native Cu occurrences in Site 642 tholeiites have some striking similarities to the large native Cu deposits in the Precambrian basalts of the Keweenaw Peninsula, Michigan, that are suggestive of similar mineralization processes.

Minerals, geochemistry and x-ray power characteristics at DSDP Sites 54-424, 60-458 and 60-459

Secondary minerals filling veins and vesicles in volcanic basement at Deep Sea Drilling Project Sites 458 and 459 indicate that there were two stages of alteration at each site: an early oxidative, probably hydrothermal, stage and a later, low-temperature, less oxidative stage, probably contemporaneous with faulting in the tectonically active Mariana forearc region. The initial stage is most evident in Hole 459B, where low-Al, high Fe smectites and iron hydroxides formed in vesicles in pillow basalts and low-Al palygorskite formed in fractures. Iron hydroxides and celadonite formed in massive basalts next to quartz-oligoclase micrographic intergrowths. Palygorskite was found in only one sample near the top of basement in Hole 458, but it too is associated with iron hydroxides. Palygorskite has previously been reported only in marine sediments in DSDP and other occurrences. It evidently formed here as a precipitate from fluids in which Si, Mg, Fe, and even some Al were concentrated. Experimental data suggest that the solutions probably had high pH and somewhat elevated temperatures. The compositions of associated smectites resemble those in hydrothermal sediments and in basalts at the Galapagos mounds geothermal field. The second stage of alteration was large-scale replacement of basalt by dioctahedral, trioctahedral, or mixed-layer clays and phillipsite along zones of intense fracturing, especially near the bottom of Holes 458 and 459B. The basalts are commonly slickensided, and there are recemented microfault offsets in overlying sediments. Native copper occurs in one core of Hole 458, but associated smectites are dominantly dioctahedral, unlike Hole 459B, where they are mainly trioctahedral, indicating nonoxidative alteration. The alteration in both holes is more intense than at most DSDP ocean crust sites and may have been augmented by water derived from subducting ocean crust beneath the fore-arc region.

More favorable combination of circumstances could hardly have been desired : a bottom to top examination of the Pittsburgh and Boston Mining Company's Cliff Mine

The Cliff Mine, an archaeological site situated on the Keweenaw Peninsula of Michigan, is the location of the first successful attempt to mine native copper in North America. Under the management of the Pittsburgh & Boston Mining Company from 1845-1879, two-third of the Cliff’s mineral output was in the form of mass copper, some pieces of which weighed over 5 tons when removed from the ground. The unique nature of mass copper and the Cliff Mine’s handling of it make it one of the best examples of early mining processes in the Keweenaw District. Mass copper only constituted 2% of the entire product of the Lake Superior copper districts, and the story of early mining on the Peninsula is generally overshadowed by later, longer running mines such as the Calumet & Helca and Quincy Mining Companies. Operating into the mid-twentieth century, the size and duration of these later mines would come to define the region, though they would not have been possible without the Cliff’s early success. Research on the Cliff Mine has previously focused on social and popular history, neglecting the structural remains. However, these remains are physical clues to the technical processes that defined early mining on the Keweenaw. Through archaeological investigations, these processes and their associated networks were documented as part of the 2010 Michigan Technological Archaeology Field School’s curriculum. The project will create a visual representation of these processes utilizing Geographic Information Systems software. This map will be a useful aid in future research, community engagement and possible future interpretive planning.

Copper, Zinc-Superoxide Dismutase from Clinically Isolated Escherichia coli: Cloning, Analysis of sodC and Its Possible Role in Pathogenicity

Superoxide dismutase has been discovered within the periplasm of several Gram-negative pathogens. We studied the Cu,Zn-SOD enzyme in Escherichia coli isolated from clinical samples (stool samples) collected from patients suffering from diarrhea. Antibiogram studies of the isolates were carried out to determine the sensitive and resistant strains. The metal co-factor present in the enzyme was confirmed by running samples in native gels and inhibiting with 2 mM potassium cyanide. A 519 bp sodC gene was amplified from resistant and sensitive strains of Escherichia coli. Cloning and sequencing of the sodC gene indicated variation in the protein and amino acid sequences of sensitive and resistant isolates. The presence of sodC in highly resistant Escherichia coli isolates from diarrheal patients indicates that sodC may play role in enhancing the pathogenicity by protecting cells from exogenous sources of superoxide, such as the oxidative burst of phagocytes. The presence of SodC could be one of the factors for bacterial virulence.

Native and modified LDL activate extracellular signal-regulated kinases in mesangial cells

Glycation and/or oxidation of LDL may promote diabetic nephropathy. The mitogen-activated protein kinase (MAPK) cascade, which includes extracellular signal-regulated protein kinases (ERKs), modulates cell function. Therefore, we examined the effects of LDL on ERK phosphorylation in cultured rat mesangial cells. In cells exposed to 100 microg/ml native LDL or LDL modified by glycation, and/or mild or marked (copper-mediated) oxidation, ERK activation peaked at 5 min. Five minutes of exposure to 10-100 microg/ml native or modified LDL produced a concentration-dependent (up to sevenfold) increase in ERK activity. Also, 10 microg/ml native LDL and mildly modified LDL (glycated and/or mildly oxidized) produced significantly greater ERK activation than that induced by copper-oxidized LDL +/- glycation (P <0.05). Pretreatment of cells with Src kinase and MAPK kinase inhibitors blocked ERK activation by 50-80% (P <0.05). Native and mildly modified LDL, which are recognized by the native LDL receptor, induced a transient spike of intracellular calcium. Copper-oxidized (+/- glycation) LDL, recognized by the scavenger receptor, induced a sustained rise in intracellular calcium. The intracellular calcium chelator (EGTA/AM) further increased ERK activation by native and mildly modified LDL (P <0.05). These findings demonstrate that native and modified LDL activate ERKs 1 and 2, an early mitogenic signal, in mesangial cells and provide evidence for a potential link between modified LDL and the development of glomerular injury in diabetes.

Quantification of malondialdehyde and 4-hydroxynonenal adducts to lysine residues in native and oxidized human low-density lipoprotein

Malondialdehyde (MDA) and 4-hydroxynonenal (HNE) are major end-products of oxidation of polyunsaturated fatty acids, and are frequently measured as indicators of lipid peroxidation and oxidative stress in vivo. MDA forms Schiff-base adducts with lysine residues and cross-links proteins in vitro; HNE also reacts with lysines, primarily via a Michael addition reaction. We have developed methods using NaBH4 reduction to stabilize these adducts to conditions used for acid hydrolysis of protein, and have prepared reduced forms of lysine-MDA [3-(N epsilon-lysino)propan-1-ol (LM)], the lysine-MDA-lysine iminopropene cross-link [1,3-di(N epsilon-lysino)propane (LML)] and lysine-HNE [3-(N epsilon-lysino)-4-hydroxynonan-l-ol (LHNE)]. Gas chromatography/MS assays have been developed for quantification of the reduced compounds in protein. RNase incubated with MDA or HNE was used as a model for quantification of the adducts by gas chromatography/MS. There was excellent agreement between measurement of MDA bound to RNase as LM and LML, and as thiobarbituric acid-MDA adducts measured by HPLC; these adducts accounted for 70-80% of total lysine loss during the reaction with MDA. LM and LML (0.002-0.12 mmol/ mol of lysine) were also found in freshly isolated low-density lipoprotein (LDL) from healthy subjects. LHNE was measured in RNase treated with HNE, but was not detectable in native LDL. LM, LML and LHNE increased in concert with the formation of conjugated dienes during the copper-catalysed oxidation of LDL, but accounted for modification of <1% of lysine residues in oxidized LDL. These results are the first report of direct chemical measurement of MDA and HNE adducts to lysine residues in LDL. LM, LML and LHNE should be useful as biomarkers of lipid peroxidative modification of protein and of oxidative stress in vitro and in vivo.

DRIFT and DRUV spectroscopy methods for studying the interaction of metal compounds with native cellulose

Dissertação de mestrado, Qualidade em Análises, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2015

A Cu tolerant population of the earthworm Dendrodrilus rubidus (Savigny, 1862) at Coniston Copper Mines, Cumbria, UK

Dendrodrilus rubidus were sampled from a mine spoil soil at Coniston Copper Mine, an abandoned Cu mine in Cumbria, UK and a Cu-free control site. Earthworms were maintained for 14 d in both Kettering loam and a Moorland soil amended with Cu nitrate. Mortality, condition index, weight change and tissue concentration were determined. In both soils D. rubidus native to the mine site were able to tolerate significantly higher soil Cu concentrations (MWRT, p <= 0.001), and exhibited significantly less change in weight (t-test, p <= 0.001) and a lower loss in condition (t-test, p <= 0.001) than control earthworms. For a given soil Cu concentration tissue Cu concentrations were greater in the mine site earthworms. Low cocoon production and viability from the mine site population prevented the determination of toxicity parameters on the F1 generation and may be an indicator of the cost of tolerance to the population. (c) 2007 Elsevier Ltd. All rights reserved.

Mechanisms by which cysteine can inhibit or promote the oxidation of low density lipoprotein by copper

Oxidised low density lipoprotein (LDL) may play a role in atherogenesis. We have investigated some of the mechanisms by which the thiol cysteine and the disulphide cystine can influence the oxidation of LDL by copper ions. Cysteine or cystine (100 PM) inhibited the oxidation of native LDL by copper in a simple phosphate buffer. One of the mechanisms by which cysteine (or more likely its oxidation products in the presence of copper) and cystine inhibited LDL oxidation was by decreasing the binding of copper to LDL (97% inhibition). Cysteine, but not cystine, rapidly reduced Cu2+ to Cu+. This may help to explain the antioxidant effect of cysteine as it may limit the amount of Cu2+ that is available to convert alpha-tocopherol in LDL into the prooxidant alpha-tocopherol radical. Cysteine (but not cystine) had a prooxidant effect, however, toward partially oxidised LDL in the presence of a low copper concentration, which may have been due to the rapid breakdown of lipid hydroperoxides in partially oxidised LDL by Cu+ generated by cysteine. To prove that cysteine can cause the rapid breakdown of lipid hydroperoxides in LDL, we enriched LDL with lipid hydroperoxides using an azo initiator in the absence of copper. Cysteine, but not cystine, increased the rate of lipid hydroperoxide decomposition to thiobarbituric acid-reactive substances (TBARS) in the presence of copper. (C) 2003 Elsevier Ireland Ltd. All rights reserved.

Kinetic role of a histidine residue in the T1 copper site of the laccase from Rigidoporus lignosus

Laccases (benzendiol:oxygen oxidoreductases; EC 1.10.3.2) catalyze the oxidation of a broad range of substrates, such as polyphenols, dyes and pollutants, and thus these enzymes are widely applied in industrial, biotechnological and environmental fields. In order to improve their biotechnological applications, a deep knowledge of structural factors involved in controlling their activity, in various experimental conditions and on different substrates, is required. In the present study, a laccase from the mushroom Rigidoporus lignosus was kinetically characterized. In particular, the stability, the effects of pH, ionic strength and fluoride ion concentration on the kinetic parameters were investigated, using three di-hydroxy-benzene isomers (1,2-dihydroxy-benzene, 1,3-dihydroxy-benzene and 1,4-dihydroxy-benzene) as substrates. The catalytic constant values of the laccase showed a bell-shaped pH profile, with the same optimum pH and pK(a) values for all tested substrates. This behavior appears to be due to the presence of an ionizable residue in the enzyme active site. To identify this residue, the enzyme was derivatized with diethylpyrocarbonate to modify accessible histidine residues, which, according to structural data, are present in the active site of this enzyme. The kinetic behavior of the derivatized laccase was compared with that of the native enzyme and the derivatized residues were identified by mass spectrometry. Mass spectrometry and kinetic results suggest the main role of His-457 in the control of the catalytic activity of laccase from R. lignosus. (C) 2013 Elsevier B.V. All rights reserved.