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ES 120 TOXICS IN THE ENVIRONMENT LECTURE 3: ELEMENTS SCOPE OF LECTURE • Important elements in ecotoxicology KEEP IN MIND THAT: • Elements are neither created nor destroyed • Elements are non-degradable • Human activity increases bioavailability of elements by: – Release from lithosphere into biosphere – Redistribution in biosphere – Changing the form of elements (e.g. from Cr(III) to Cr(VI) or N2 into NOx) – Changing environmental conditions (e.g. a decreased pH caused by acid rain facilitates assimilation of aluminum) MERCURY • AKA quick silver • Neurotoxin, especially organomercury compounds (methylmercury) • Most applications are obsolete (pigments, fungicides, thermometers, dental amalgams, batteries) • Still used in gold mining and released at coal burning • Complex environmental cycling Cinnabar CADMIUM • Rare element, most common in zinc ores • Resembles zinc, which in part explains its toxicity • Binds strongly to ligands, especially S containing • Applications: Ni-Cad batteries, plastics stabilizer, rubber vulcanization, pigments Greenockite LEAD Galena • Abundant in earth crust and widely distributed because of past uses • Very malleable, heavy, low melting point. • Common past applications: plumbing, pigment, insecticide (lead arsenate) anti-knock additive (tetra-ethyl lead) • Present applications include crystal, ceramics, weights, car batteries. COPPER • Important since antiquity • Alloys: bronze, brass, gold (<24K) • Good conductor: high end cooking pots, electronics • Used as pesticide (antifouling, bactericide) and wood preservative Chalcopyrite, CuFeS2 Navajo jewelry with turquoise Copper and gold plated roofs, Alexander Nevski cathedral, Sofia NICKEL • Common element in earth crust • Used in alloys to prevent corrosion, such as in coins and in stainless steel (with iron, chromium, molybdenum and/or vanadium) • Some nickel compounds are carcinogenic; may cause dermatitis in sensitive individuals Limonite, (Fe,Ni)O(OH) Pentlandite, (Fe,Ni)9S8 CHROMIUM Crocoite, PbCrO4 Chromite, FeCr2O4 • Occurs predominantly as Cr(III) and Cr(VI) • Cr(III) is essential micronutrient • Cr(VI) is especially toxic • Toxicant in Erin Brokovitz movie • Used in alloys (stainless steel), chrome plating, paints, tanning and wood preservation TIN • Very malleable, low melting point, metal pulverizes below 13oC • Used since antiquity as metal (utensils, toys, foil – now mostly replaced by aluminum) and in bronze (weaponry, statues) • Used as anticorrosive (tin plating) • Of most environmental concern are the organo-tin compounds, such as tri-butyltin (TBT, antifouling agent) Casserite, SnO2 Medieval tin plate Arsenic • High levels in some ores and water sources (Bangladesh) • King of poisons and poison of kings since antiquity • Used as wood preservative and in metal alloys • Past uses: pesticide (lead arsenate), rat poison, pigment. Arsenopyrite, FeAsS Victim of arsenic? HALOGENS • Reactive elements: F2, Cl2, Br2, I2 • When covalently bound to organic compounds, they increase the persistence and toxicity of those compounds – see next lecture • Cl2 is a major industrial base chemical • House hold uses: disinfectant (bleach, betadine) and discoloring agent (bleach), carbonate remover (hydrochloric acid in bath tub & tile cleaners) PHOSPHORUS Dead zone in the Gulf of Mexico Red tide, massive growth of toxic dinoflagellates • Major nutrient • Fertilizer (phosphate), causes algal blooms and anoxia in aquatic and marine environments NITROGEN • Major nutrient • Fertilizer (nitrate, ammonium), causes algal blooms and anoxia in aquatic and marine environments • As NOx major airpollutant causing smog and contributing to the weathering of alkaline stone Smog in Los Angeles SULFUR • Ancient pesticide (SO2) • Preservative (sulfite) • Major air pollutant (SO2), released with the burning of sulfur rich fuel (coal) • Causes acid rain (SO2 turns into sulfuric acid) RADIOACTIVE POLLUTANTS • Radioactive isotopes disintegrate to form eventually stable elements while emitting - a radiation (helium ions), - b radiation (high energy electrons) - g radiation (photons with extremely small wave lengths) and/or - neutrons DAMAGE POTENTIAL Damage due to radioactivity depends on: • • • • Type of emission Energy content of emission Rate of disintegration Potential of an isotope to accumulate in the body PLEASE NOTE THAT • Radiation does not lead to contamination • A short half-life implies a lot of radiation and potential damage in a short time; waste management is easy • A long half-life implies relatively little radiation over an extended period; waste management is problematic EXAMPLES • • • • • • • 14C, naturally formed in the atmosphere, long half life, used in dating 3H (tritium), low energy, medium half life, used in tracer studies 131I, short half life, used to assess the functioning of the thyroid gland Radioactive isotopes of essential elements, used in biochemical studies 60C, used in radiotherapy Cs, Sr and I isotopes of major concern in nuclear fall out U and Pu isotopes, nuclear fuel, extremely toxic as chemicals LATEST CONCERN: NANOPARTICLES • Size is in the nanometer range • Size and shape are determinants for toxicity • Metal oxides and fullerenes (“bucky balls”) • Explosive increase in production, applications EXAMPLES OF NANOPARTICLES • ZnO – antibacterial, antifungal, anti-corrosion, catalytic, and UV filtering properties: In paint, plastic, textiles; catalyst for methanol synthesis, personal care products, sunscreen • TiO2 - high UV absorption, photocatalytic activity germicidal, and thermal stability: In pigments, cosmetics cosmetics, hard coatings, plastics, toners Next Lecture • Organic Toxicants • Homework: – PE: 1.2, 1.3 – Assignment: Table on Metals, Metalloids and Non-Metals due next week but start now: it is a long assignment you don’t want to complete in one session