New Materials for Removal of Trace Impurities from Environmental Waters

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1 New Materials for Removal of Trace Impurities from Environmental Waters July, 2010 John Sawyer Life-Changing Research and Development Chemical and Environmental Technologies Health and Life Sciences Advanced Engineering Systems x847

2 Removing Pollutants from Water Various industries need to remove trace pollutants from aqueous sources in an economical manner Element Aqueous Limit (ppb) Typical Industry Selenium 4.7 Coal and phosphate mining Arsenic 10 Salt mining Mercury 2 (EPA); 0.02 (Ohio) Coal mining and combustion Aluminum 750 (acute);87 (chronic) Surface mining Iron 500 Deep mining Total Dissolved Solids 100,000 Natural gas 2

3 Selenium Environmental Effects Selenium is a necessary micronutrient Selenium compounds are necessary for survival of many species Excess selenium is harmful An excess of selenium replaces sulfur in proteins, resulting in inactivity Excessive selenium levels result in deformities or death. Birds, horses, cattle, fish have all been killed by excessively high levels of selenium Some micro-organisms take up dissolved selenium Elemental selenium is deposited in sediments Organo selenium is released into the biosphere Dissolved selenium is also taken up directly by other aquatic species Bioaccumulation of selenium may lead to excessive and toxic levels

4 Selenium Elemental selenium or naturally occurring selenides are insoluble. In the presence of water and oxygen the selenides oxidize to soluble selenates and selenites Selenium in rock naturally oxidizes and leaches at a slow rate In disturbed soils, the rate is increased due to increased exposure The selenium level in the groundwater increases above normal levels

5 Selenium Sources In most rocks and soils in the USA at the ppm level Distribution in US soils (USGS)

6 Liberty ZVI Technology Application of sound chemical engineering principles to enhance reactivity and mass transport of ZVI redox reactions. Chemistry: Step 1 : oxidation of solid ZVI iron which releases soluble iron (Fe II+ ) Step 2 : reduction of selenate (Se VI+ ) and selenite (Se IV+ ) to selenide (Se 2- ) Step 3 : oxidation of ferrous ions to ferric ions Step 4 : formation of ferric hydroxides with free hydroxyl ions (OH - ) Step 5 : formation of ferric hydroxide precipitate Step 6 : Selenite adsorbs onto the ferric/ferrous hydroxide 2 Fe 0 (s) + O H 2 O 2 Fe OH - SeO Fe 0 (s) + 4 H 2 O Se Fe + 8 OH - SeO Fe 0 (s) + H 2 O SeO Fe(OH) 2 4 Fe 2+ + O H 2 O 4 Fe OH - Fe OH - Fe(OH) 3

7 Liberty ZVI Technology Advantages Simple chemical reaction Relative ease in the removal of selenium concentrate for disposal Short retention time Construction and O&M costs significantly lower than other technologies Disadvantages May require filtration to remove TSS Sulfates are detrimental Does require post treatment for iron

8 Reactive Filtration Laboratory Development of variety of media that chemically remove pollutants from water sources Catalytic reactions Non-catalytic reactions Reactive filtration for nonhydrocarbon pollutants Selenium Arsenic Iron Aluminum Mercury 8

9 Proven Results 25 Lab Results: Se Removal Over Time 20 Se (ppb) Residence Time, Minutes

10 Residual Se after one hour Sulfate Effect on Selenium Removal Efficiency ppm Sulfate

11 Impact of Organic Acids on % Selenium Removal Activity by ZVI Per Cent Removal Residence time, minutes Acetic Citric Succinic Lactic Malic Adipic Oxalic

12 Selenium Remediation All Solutions require: Pretreatment to remove suspended solids to adjust ph Treatment to remove Selenium Post treatment to remove soluble iron Disposal of concentrated selenium material

13 Selenium Solution IP protected zero-valent iron technology meets EPA requirements. Successfully sold, installed, tested, and operational in WV and Idaho. Portable, passive, treats multiple contaminants, small footprint. Modular design for easy installation and expansion. Industry lowest cost solution.

14 Selenium Removal Pilot Plant in Idaho Performance under adverse conditions

15 Selenium Field Pilot Plant Selenium concentration - ppb Inlet Outlet

16 Mercury Sites Taken from:

17 Mercury Remediation Technologies Taken from:

18 Mercury Remediation Technologies Long term stabilization is still a concern New concepts are needed Mercury sulfide (cinnabar) is the ore from which mercury is refined Mercury selenide is a more stable and easily formed compound MATRIC has developed a process to take advantage of this

19 U S Patent 4,780,214 A blacklisted lake in Sweden was treated with soluble selenium to remove the mercury. Fig 3 is the mercury content in fish before and after treating the lake with soluble selenium.

20 U S Patent 4,780,214 Fig 2 is the mercury content in fish by year before and after treating the lake with soluble selenium. Larger (older) fish had higher levels, but greatly reduced levels of mercury in all sizes.

21 Mercury Removal Test Results (Preliminary) Hg Removal vs Residence Time Hg, ppb Residence Time in Minutes

22 Mercury Hg, Removal, % 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Mercury Removal vs Residence Time Selenium Formulation 1 Selenium Formulation 2 Selenium Formulation Residence Time in Minutes

23 Additional contaminants Aluminum Cr VI+ As Tc Cu Pb TCE/PCE

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