An Ecological and Chemical Assessment of Copper Contaminated Streams in the Keweenaw Peninsula

The copper mining boom in Michigan's Upper Peninsula ended in the mid-1960s, but the historical mining still affects the region to this day. Earlier studies conducted in the Keweenaw have shown that trace metals in the sediments negatively affect benthic macroinvertebrate populations. However, because the concentrations of trace metals that are observed to be toxic often differ significantly between the laboratory and the environment, a better method for determining toxic levels of trace metals in the natural environment is desirable in order to establish surface water quality guidelines that effectively protect aquatic life. There were four research objectives for this research project. First, to determine if trace-level concentrations of copper can result in detectable ecological impacts even in the presence of high dissolved organic carbon (DOC). Second, to determine if there is a "safe" concentration of total dissolved copper below which there is little to no ecological impairment. Third, to establish which streams in the Keweenaw Peninsula have been most impacted by elevated levels of total dissolved copper. Fourth, to use this information to evaluate revisions to the water quality criterion for copper that were recently proposed by the Michigan Department of Environmental Quality (MDEQ). In order to collect water quality and macroinvertebrate data, two sampling surveys of approximately 50 streams were completed in the spring and summer of 2012. Our findings demonstrate that negative ecological impacts can be detected even in the presence of high concentrations of DOC. The majority of surveyed streams showed evidence of total dissolved copper concentrations that were elevated above background levels. Our findings suggest that there are detectable negative impacts below the current water quality standard for copper in many Keweenaw streams. The diversity of benthic macroinvertebrates and the number of species present has been reduced as a result of exposure to copper. Additionally, the multimetric approach used by MDEQ is unable to detect copper impairment in local streams due to the use of several insensitive metrics. The proposed changes to the copper criterion would increase the amount of total dissolved copper allowable despite the fact that approximately 25% of streams sampled have aquatic chemistries that would leave them vulnerable to high levels of copper ions.

Cut slope design for the access to an underground copper mine

Slope stability analysis is a major area of research in geotechnical engineering. That being said, very little is written in the geotechnical engineering literature on the design of box-cuts. The goal of this thesis will be to investigate the proper design of a boxcuts, and to design a box-cut for access to an underground copper mine. Issues that need to be considered in the box-cut design include, long term dewatering design, slope stability analysis, and erosion control. The soils at the project site were extremely low permeability, as a result a system of ejectors was designed both to improve the stability of the slopes and prevent flooding. Based on the results of limit equilibrium analysis and finite element analysis, a slope design of two horizontal on one vertical was selection, with a rock fill buttress providing reinforcement. Finally, Michigan DOT standards for seeding were used to provide erosion control

Syntheses and structures of molybdenum and tungsten complexes capable of epoxidaton and copper coordination polymers and dendrimers

We are interested in the syntheses of new complexes and in their characterization by single crystal X-ray diffraction techniques. Once we understand the structures, studies aimed at understanding uses of these complexes in the field of catalytic epoxidation using complexes soluble in water and syntheses of thin films (not assessed) were conducted. The syntheses, characterization and catalytic properties of a series of mononuclear, dinuclear and tetranuclear molybdenum and tungsten oxo complexes are described. The syntheses and structural characterization of two copper coordination polymers with 3,5-dihydroxylbenzoate ligand, and five paddlewheel shaped copper dendrimers coordinated with Fréchet-type dendrons are also detailed. The background of this dissertation is outlined in Chapter 1. Chapter 2 describes the syntheses, and characterization of two new mononuclear molybdenum(VI) and tungsten(VI) oxo complexes, MoO2Cl2(OPPh2CH2OH)2, and WO2Cl2(OPPh2CH2OH)2, bearing hydrophilic phosphine oxide ligand. The catalytic properties of these complexes for the epoxidation of cis-cyclooctene were also studied. Two new dinuclear molybdenum(VI) and tungsten(VI) oxo complexes Mo2O4Cl2[(HOCH2)PhPOO]2, and (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, bearing organophosphinate ligand are described in Chapter 3 and 4. Chapter 4 and 5 describes the syntheses and characterization of tetranuclear molybdenum(V) oxo complexes bearing various organophosphinate ligands. The catalytic abilities of these complexes for the epoxidation of cis-cyclooctene in the presence of hydrogen peroxide as oxidant were explored as well. Various spectroscopic methods, such as IR, UV-vis, and NMR are used to characterize the nature of these complexes. Crystal structures of compounds MoO2Cl2(OPPh2CH2OH)2, WO2Cl2(OPPh2CH2OH)2, Mo2O4Cl2[(HOCH2)PhPOO]2, (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, and Mo4(µ3-O)4(µ-O2PR2)4O4 (R=Ph, Me, ClCH2, o-C6H4(CH2)2) are also presented. The syntheses, and structural characterization of three copper(II) coordination polymers bearing 3,5-dihydroxybenzoate ligand are described in Chapter 6. Two copper(II) coordination polymers, [Cu2(3,5-dhb)2(pyridine)4]n, and [Cu2(3,5-dhb)4]n were afforded based on different amount of pyridine used in the reaction. The structures of these complexes are further built into 2D or 3D networks via inter or intra hydrogen bonds. The syntheses and structural characterization of the zinc(II) monomer, Zn(3,5-dhb)2(pyridine)2 is also described in this Chapter. Chapter 7 describes the syntheses, and characterization of five dendronized dicopper complexes bearing different generations of Fréchet-type dendrons. The structures of 3,5- bis(benzoyloxl)benzoic acid, 3,5-(PhCOO)2PhCOOH (G1), Cu2(3,5-dhb)4(THF)2, Cu2(G1)4(pyridine)2, and Cu2(G1)4(CH3OH)2 were characterized unambiguously by single X-ray diffraction. In addition, all compounds were characterized by FT-IR, UV-vis spectroscopy and elemental analyses.

Parameter identification of a copper-zeolite SCR catalyst model using reactor data

The selective catalytic reduction system is a well established technology for NOx emissions control in diesel engines. A one dimensional, single channel selective catalytic reduction (SCR) model was previously developed using Oak Ridge National Laboratory (ORNL) generated reactor data for an iron-zeolite catalyst system. Calibration of this model to fit the experimental reactor data collected at ORNL for a copper-zeolite SCR catalyst is presented. Initially a test protocol was developed in order to investigate the different phenomena responsible for the SCR system response. A SCR model with two distinct types of storage sites was used. The calibration process was started with storage capacity calculations for the catalyst sample. Then the chemical kinetics occurring at each segment of the protocol was investigated. The reactions included in this model were adsorption, desorption, standard SCR, fast SCR, slow SCR, NH3 Oxidation, NO oxidation and N2O formation. The reaction rates were identified for each temperature using a time domain optimization approach. Assuming an Arrhenius form of the reaction rates, activation energies and pre-exponential parameters were fit to the reaction rates. The results indicate that the Arrhenius form is appropriate and the reaction scheme used allows the model to fit to the experimental data and also for use in real world engine studies.

Gender on the Range: Feminine Strategies in the 1913 Michigan Copper Strike

In the autumn of 1913, a small, remote Michigan mining community attracted national attention as miners and management found themselves embroiled in a conflict that would prove no easy victory for either side. The strike came as a shock to management, who, with the help of a nearly perfected paternal system, had come to expect a generally docile and compliant workforce. But what was even more shocking was the involvement of the miners’ wives in the strike effort, and the lengths they went to in order to keep men from crossing the picket line. This paper focuses on that effort, arguing that the women of the Michigan copper country developed strike strategies that were derived from their domestic experience, and justified their involvement through maternal arguments. However, these public actions allowed the management to disregard the respect and courtesy generally given to the domestic sphere as police and private agents perpetrated a number of home invasions in an attempt to break the strike. The involvement of women in male dominated labor disputes (mining, steel productions) has been largely ignored in the literature due to their indirect connection to the company as wives and not workers. This paper seeks to remedy this gap, and gain a better understanding of that indirect relationship. Sources include newspaper articles, private correspondence, public investigation records, and oral histories, found largely in the Michigan Tech Archives and Copper Country Historical Collections, Michigan Technological University, Michigan.

The Copper Strike of 1968-1969

In May of 1968, workers at the Kingston mine, a branch of the Calumet Division of Universal Oil Products walked off the site in protest of a safety issue involving a man-car. Knowing their contracts were due for negotiation in just a few months, the workers quickly returned, only to find themselves striking yet again just three months later, when negotiations failed. Requesting pay equal to that of the workers at the nearby White Pine mine was unacceptable to the heads of Universal Oil, the corporation which bought the long running Calumet & Hecla just a year earlier in 1968. The strike would last for nine months, ending in a total shutdown of all mining operations on the Keweenaw Peninsula, and bring an economic hardship to the area that would take decades to recover from. The Copper Strike of 1968-1969 is often forgotten, though extremely important to the story of the copper industry in Michigan, as well as to the United States. This paper has not yet been submitted.

“Beneath the Starry Flag”: the Flags and Songs of the 1913-14 Michigan Copper Strike as Image-making in the American Labor Movement

The 1913-14 Michigan copper strike is unlike many American labor actions of the period in that it did not include red flags or socialist anthems. Many of the most familiar photographs of the strike involve American flags, not red ones. Similarly, the songs mentioned in journalistic accounts of the strikers are American Civil War songs, not popular labor songs of the period. The few newly-written songs about the strike, published in the local newspapers, seem cautiously polite and espouse values such as patriotism, liberty and human rights. During a time when sections of the "friendly" press were concerned with labor presenting the correct image and avoiding unfavorable associations, the Copper Country strikers, and the W.F.M., seem to have been attempting to create a fresh narrative regarding what this strike was (and what it was not). This paper will consider elements of the Copper Country strike in the light of media coverage, prior to July 1913, of several American labor topics that might have influenced the way the strike was presented. Particular attention will be given to photographs, songs, and accounts from the 1912 Lawrence textile strike, as well as contemporaneous critiques of labor song lyrics. Most of this commentary will be drawn from the labor and socialist press, demonstrating that the 1913-14 Michigan copper strike occurred during a period in which the labor movement was struggling to craft and image that would display it as it wished to be seen. This paper has not yet been submitted.

A Balance Shifted: The Unionization of Michigan’s Lake Copper District, 1935-1955

Three decades after the unsuccessful 1913-1914 strike at the Lake District copper mines of Michigan, workers organized as Local 584 of the International Union of Mine, Mill, and Smelter Workers (Mine Mill) signed a union contract with Calumet & Hecla Consolidated Copper Company. C & H was the last and most significant of the region’s three major copper mining companies to unionize during the three-year period from 1939 to 1942. This paper tells the untold history of the successful union drives in the Lake District’s copper mines, starting with Copper Range Company in 1939 and encompassing the subsequent unionizations of Quincy Mining Company and finally C & H. The paper develops thematic connections between the 1913-1914, including Mine Mill’s lineage to the Western Federation of Miners, parallel ethnic dimensions, and, most significantly, the contrasting role of state authority between the two time periods. The paper carries the Lake District’s labor history forward to 1955 to include United Steelworkers’ successful challenge to Mine Mill in 1950 and the strike of 1955. This history also incorporates source material from the papers of highly influential union organizer and representative Eugene Saari, material which to date has not been integrated into the labor history of the region. This paper has not yet been submitted.

Copper Range Railroad General Freight Department Rules and Regulations

http://digitalcommons.mtu.edu/copper_range/1000/thumbnail.jpg

Copper availability contributes to iron perturbations in human nonalcoholic fatty liver disease

BACKGROUND ; AIMS: Iron perturbations are frequently observed in nonalcoholic fatty liver disease (NAFLD). We aimed to investigate a potential association of copper status with disturbances of iron homeostasis in NAFLD. METHODS: We retrospectively studied 140 NAFLD patients and 25 control subjects. Biochemical and hepatic iron and copper parameters were analyzed. Hepatic expression of iron regulatory molecules was investigated in liver biopsy specimens by reverse-transcription polymerase chain reaction and Western blot analysis. RESULTS: NAFLD patients had lower hepatic copper concentrations than control subjects (21.9 +/- 9.8 vs 29.6 +/- 5.1 microg/g; P = .002). NAFLD patients with low serum and liver copper concentrations presented with higher serum ferritin levels (606.7 +/- 265.8 vs 224.2 +/- 176.0 mg/L; P < .001), increased prevalence of siderosis in liver biopsy specimens (36/46 vs 10/47 patients; P < .001), and with elevated hepatic iron concentrations (1184.4 +/- 842.7 vs 319.9 +/- 451.3 microg/g; P = .020). Lower serum concentrations of the copper-dependent ferroxidase ceruloplasmin (21.7 +/- 4.1 vs 30.4 +/- 6.4 mg/dL; P < .001) and decreased liver ferroportin (FP-1; P = .009) messenger RNA expression were found in these patients compared with NAFLD patients with high liver or serum copper concentrations. Accordingly, in rats, a reduced dietary copper intake was paralleled by a decreased hepatic FP-1 protein expression. CONCLUSIONS: A significant proportion of NAFLD patients should be considered copper deficient. Our results indicate that copper status is linked to iron homeostasis in NAFLD, suggesting that low copper bioavailability causes increased hepatic iron stores via decreased FP-1 expression and ceruloplasmin ferroxidase activity thus blocking liver iron export in copper-deficient subjects.

Copper Commando Index – vol. 1

Index for volume 1 (Aug. 1942-Aug. 1945) lists personal names, places, subjects; page and issue numbers.

Copper Commando Index – vol. 2

Index for volume 2 (Aug. 1942-Aug. 1945) lists personal names, places, subjects; page and issue numbers.

The Effect of the Cu:Fe''' Ratio Upon the Current Efficiency in the Electrolysis of a Copper Sulfate Solution Containing Iron Sulfate

It is a well-known fact that, in the electrolysis of a CuSO4 solution containing iron sulfate, using insoluble anodes, with the depletion of copper, the point is finally reached where the current efficiency becomes zero. This decrease in current efficiency is due to the oxidation of the ferrous sulfate to the ferric condition at the anode, by the oxygen liberated. The resulting ferric sulfate diffuses over to the cathode and there dissolves copper from the cathode according to the chemical equation Cu + Fe2 (SO4)3 = CuSO4 + 2FeSO4. This copper, which has been deposited at the cathode by the electric current, is thus redissolved by the Fe2(SO4)3. The solution of the copper causes at the same time a formation of FeSO4 which in turn diffuses over to the anode and is there oxidized to Fe2(SO4)3; and so the cycle continues, using electric current without rendering useful work. E. H. Larison has noted that a definite amount of ferric salts must be reduced to the ferrous condition before all the copper will remain on the cathode; he does not state, however, just what this point is. L. Addicks has plotted the relation between current efficiency and ferric sulphate content. The existence of the results scattered the points more or less, although the decrease in current efficiency with increased ferric sulphate content is clearly indicated. E. T.Kern has likewise noted that the smaller the amount of copper in the solution, the greater is the reduction of current efficiency. In this work, therefore, it was desired to determine what amount of ferric iron was permissible in a copper sulfate solution of definite concentration before the current efficiency would drop to zero, and what, if any, was the effect of definite Cu:Fe’’’ratio upon the current efficiency of the electrolysis.

Copper Commando Index - volumes 1, 2, and 3

Index for volumes 1, 2, and 3 (Aug. 1942 - Aug. 1945) lists personal names, places, subjects; page and issue numbers.