Copper (Cu)

1. Copper (Cu) -Latin origin -(cuprum) Roman town of Cyprus -Similar to Ag, Au -Pure copper is pink/ copper exposed to air (oxidized) is reddish orange -Ductile/ high Thermal and Electrical conductivity

2. Chemical properties • Cu+1 (cuprous), Cu+2 (cupric), Cu+3, Cu+4 Water-Soluble Reacts w/ atmospheric Oxygen Copper Corrosion

3. Chemical Properties • Oxygen-containing ammonia solutions give water-soluble complexes with copper • Hydrochloric acid/hydrogen peroxide also react with copper chlorides to form copper(II) salts • Copper(II) chloride and copper (+0) comproportionate to form copper(I) chloride

4. Production History • Most copper (Copper Sulfide) is extracted from large open pit mines • Crushed ores are subjected to froth flotation or bioleaching • Heating the material with silica removes the iron slag and drops the copper matte to the bottom • The copper matte is roasted to oxidize the sulfides • The resulting blister copper is heated and blown with natural gas to remove oxygen • Electro-refining (electro-platting) the im-pure copper produces pure copper

5. Production History Copper sulfides Copper carbonates Copper Oxides

6. Uses and Applications • Bronze Age- (Alloying of copper with zinc or tin to make brass and bronze) right after the Chalcolithic age • Currency Weapons/Tools • Construction Art Sculptures • Electrical Wires Roofing/Plumbing • Machinery Wood Preservative • Fungicide Biostatic Property Antimicrobial Antibiofouling

7. Mode of Entry into Aquatic environment • Copper Water Pipes • Contaminated Drinking water (excess CuS) • Runoff ladened w/excess CuS sprayed on fruits and vegetables

8. Reactivity w/ Water and other prop. • Dissolved in Water • In form of salts • Cu+3 and +4 form fluoride complexes • 29 Isotopes of copper • 63Cu,65Cu are stable (63Cu 69% of naturally occurring) • 67Cu and above,64Cu and below are very unstable • 68mCu (3.8 min half-life) • 62Cu and 64Cu have significant applications. 64Cu used in X-ray imaging and treating cancer

9. Toxicity to aquatic life • Copper strongly adsorbs into organic matter making it an effective algaecide • At acute toxic levels, copper effects fish, invertebrates, and amphibians equally • The deleterious effects of copper are seen more commonly in the organs of aquatic organisms than terrestrial organisms • mollusks have a higher potential to bioconcentrate copper than do fish • effects on bird growth rates and egg production • Requires high concentrations to effect mammals • liver cirrhosis, kidney necrosis, brain necrosis, and even fetal mortality can occur

10. Modes of toxicity • Essential in hemocyanin and cytochrome c oxidase in aerobic respiration • Acute toxic levels enter the organism through ingestion from food or water • Free copper causes toxicity as it generates reactive oxygen species; superoxide, hydrogen peroxide, the hydroxyl radical • These damage proteins, lipids and DNA

11. Modes of Toxicity • Redox Cycling of Cu(II) in the body • Cu(II) strongly catalyzes the oxidation of TBHQ to TBQ • TBQH comes from BHA; a food preservative and possible antioxidant • However, oxidation of TBQH produces reactive oxidative species H(2)O(2) • Leads to extensive DNA strand breaks butylatedhydroxyanisole (BHA) 2-tert-butyl(1,4)hydroquinone (TBHQ) 2-tert-butyl(1,4)paraquinone (TBQ)

12. Biochemical metabolism • Alterations in the levels of glycerol, phospholipids, glycerides, sterols, sterol esters and free fatty acids due to copper sulphate treatment in mantle and digestive gland of mollusc • Possible mechanism of detoxification, prevalent in this fresh water mollusc • Mammals have efficient mechanisms to regulate copper such that they are generally protected from excess dietary copper levels

13. Modes of detoxification • Metallothionein • Localized in the Golgi apparatus and a cysteine-rich protein • Capacity to bind heavy metals through the thiol group of its cysteine residues • Provides regulation of physiological heavy metals (Cu, Zn) • Therefore, may protect against oxidative stress

14. Copper as a possible detoxifier of halogenated compounds • Fenton's reaction for degradation of perchloroethene (volatile organic compound) • Copper accelerates the reaction of iron (III)with hydrogen peroxide to generate increased amounts of hydroxyl and superoxide radicals • These radicals can react with a variety of VOCs and mineralize them • Enabling targeted VOC extraction from effected areas

15. Bibliography Slide 1: Inorganic Chemistry. San Diego: Academic Press; 2001 S2: Inorganic Chemistry. San Diego: Academic Press; 2001 S3: Nature's building blocks: an A-Z guide to the elements., Oxford University Press. pp. 121–125; 2011 S4: Chemistry of the Elements., 2nd ed. Oxford; 1997 S5: The Elements, in Handbook of Chemistry and Physics 81st edition. S6: Encyclopedia of the History of Technology. London ; New York: Routledge. pp. 13;48–66 S7: Copper Toxicity., The Eck Institute of Applied Nutrition and Bioenergetics; 1999 S8: Evaluation of Nuclear and Decay Properties., Nuclear Physics A., Atomic Mass Data Center; 729 S9: Principles of bioinorganic chemistry., University Science Books:1994 S10: DNA damage caused by reactive oxygen species originating from a copper-dependent oxidation of the 2-hydroxy catechol of estradiol. Carcinogenesis 15 (7): 1421–142 S11: Copper redox-dependent activation of 2-tert-butyl(1,4)hydroquinone: formation of reactive oxygen species and induction of oxidative DNA damage in isolated DNA and cultured rat hepatocytes. Mutat Res. 2002 Jul 25;518(2):123-33 S12: SUS Environmental Protection Agency., http://www.epa.gov/pesticides/factsheets/copper-alloy-products.htm S13: Metallothioneins and Related Chelators. Metal Ions in Life Sciences. 5. Cambridge: RSC Publishing., Sigel, A.; Sigel, H.; Sigel, R.K.O., ed (2009) S14: A possible mechanism of detoxification of copper, in the fresh water mollusc, LymnaealuteolaPhysiolPharmacol. 1993 Oct-Dec