The many Wonders of Fe EDTA Room Temperature

"The many Wonders of Fe. EDTA: Room Temperature Incineration of Pollutants, and A Model for Biological Oxidations. " Frank Cheng Associate Professor of Chemistry University of Idaho Moscow, ID 83844 -2343 Email: ifcheng@uidaho. edu Tel. : 208 -885 -6387 Fax: 208 -885 -6173 Homepage: http: //www. chem. uidaho. edu/faculty/ifcheng/ 9/15/2020 University of Idaho - Boise State 1

EDTA – A brief history n Ethylenediaminetetraacetic acid n 1930’s Ferdinand Munz first synthesizes EDTA as a substitute for amino acids in textile processing. n Annual Production 100, 000 metric tons. http: //www. chm. bris. ac. uk/motm/edtah. ht m 9/15/2020 University of Idaho - Boise State 2

EDTA • Finds widespread use in food, cosmetic and pharmaceutical preparations • Newer uses – manufacture of textiles and in paper-pulp bleaching q. Swedish pulping industry where the use of EDTA has increased from 2, 000 metric tons to about 8, 000 metric tons per year from 1990 to 2000. Ekland, B; Bruno, E; Lithner, G. ; Hans, B. ; “Use of Etheylenediaminetetraacetic acid in Pulp Mills and Effects on Metal Mobility and Primary Products”; Environ. Toxicol. Chem. ; 2002; 21(5), 1040 -1051. 9/15/2020 University of Idaho - Boise State 3

EDTA – Modern Uses http: //en. wikipedia. org/wiki/EDTA n n n Industrial cleaning: complexation of Ca and Mg ions, binding of heavy metals. Detergents: complexation of Ca and Mg (reduction of water hardness). Pulp and paper industry: complexation of heavy metals during chlorine-free bleaching, stabilization of hydrogen peroxide. Textile industry: complexation of heavy metals, bleach stabilizer. Food: added as preservative to prevent catalytic oxidation by metal ions or stabilizer and for iron fortification. Personal care: added to cosmetics to work in synergy with preservatives and to improve product stability. 9/15/2020 University of Idaho - Boise State 4

EDTA – Modern Uses http: //en. wikipedia. org/wiki/EDTA n n n n Oil production: added into the borehole to inhibit mineral precipitation. Dairy and beverage industry: cleaning of bottles from milk stains. Flue gas cleaning: removal of NOx. Medicine: used in chelation therapy (brand name Endrate®, marketed by Hospira; generic product is also on the market) for acute hypercalcemia and mercury and has been used for lead poisoning. Used in dentistry as a root canal irrigant to remove compounds of organic and inorganic debris (smearlayer). Added to many soft drinks containing ascorbic acid and sodium benzoate, to reduce the formation of benzene (a carcinogen). Can be used in the recovery of used lead acid batteries. 9/15/2020 University of Idaho - Boise State 5

Metal Complexes http: //en. wikipedia. org/wiki/EDTA n n Agrochemicals: Fe, Zn and Cu fertilizer, especially in calcareous soils. Hydroponics: iron-EDTA is used to prevent the iron from precipitating out of nutrient solutions. Photography: use of Fe(III)EDTA as oxidizing agent. Scavenging metal ions: in biochemistry and molecular biology, ion depletion is commonly used to inactivate enzymes which could damage DNA or proteins 9/15/2020 University of Idaho - Boise State 6

Complexation of Fe(II/III) with EDTA n p. Ka 1 -6 = 0. 0, 1. 5, 2. 0, 2. 66, 6. 16, 10. 24 n Kf(Fe. II) = 1014. 32 n Kf(Fe. III) = 1025. 1 9/15/2020 University of Idaho - Boise State 7

Cyclic voltammetry http: //en. wikipedia. org/wiki/Cyclic_voltammetry red 0. 7 volts ox n Applied potential waveform to electrode n ox + e- = red 9/15/2020 E 0 = 0. 7 volts University of Idaho - Boise State 8

The Cyclic Voltammogram ox + e- red Start E End E ox + e- <-- red 9/15/2020 University of Idaho - Boise State 9

Cyclic Voltammetry of Fe(II/III)EDTA n 1. 0 m. M Fe. IIIEDTA n p. H 7. 40, 0. 1 M HEPES buffer n 10 m. V/sec n C disk electrode Fe. IIIEDTA + e- Fe. IIEDTA 9/15/2020 University of Idaho - Boise State 10

CV of Fe(II/III)EDTA in the presence of O 2 n Electrocatalytic (EC’) Voltammetry 2 Figure 1. Cyclic voltammetric curves on a p. H =3 sample A 1. 5 1 u. A A) 0. 1 m. M Fe. IIIEDTA and O 2 saturated, B) 0. 1 m. M Fe. IIIEDTA only, 0. 5 B B 0 -0. 5 0. 3 0. 2 0. 1 0 scan rate = 5 m. V/s. 9/15/2020 -0. 1 -0. 2 -0. 3 -0. 4 V University of Idaho - Boise State 11

n The reducing current is amplified and oxidizing current is absent in EC’ Electrochemical mechanism reduction coupled with a homogeneous reaction 9/15/2020 University of Idaho - Boise State 12

Kinetic Realities Fe. IIIEDTA efast Fe. IIEDTA Electrode O 2 eslow O 2. - 9/15/2020 University of Idaho - Boise State 13

Mediated Electron Transfer Catalytic Current Electrode e- Fe. IIIEDTA O 2 fast Fe. IIEDTA 9/15/2020 University of Idaho - Boise State fast O 2. - 14

The Fenton Reaction n Fe. IIIEDTA + e- = Fe. IIEDTA n Fe. IIEDTA + H 2 O 2 = Fe. IIIEDTA + HO- + HO∙ (fast) n H 2 O 2 + e- = HO- + HO∙ (slow) 9/15/2020 University of Idaho - Boise State 15

EC’ Voltammetry with the Fenton Reaction Mechanism 9/15/2020 University of Idaho - Boise State 16

Summary of Voltammetry n EC’ mechanisms of n Fenton Reaction q q n Fe. IIIEDTA + e- = Fe. IIEDTA + H 2 O 2 = Fe. IIIEDTA + HO- + HO∙ Oxygen Reduction q q 9/15/2020 Fe. IIIEDTA + e- = Fe. IIEDTA + O 2 = Fe. IIIEDTA + O 2. University of Idaho - Boise State 17

Outline of Investigation n I] Room Temperature and Pressure Combustion of Organic Pollutants and Nerve Agent Surrogates – The Search for a Green Oxidant n II] A Model for the Role of Calcium and Zinc in Biological Oxidations n III] A Detector for Peroxide-Based Explosives 9/15/2020 University of Idaho - Boise State 18

The search for a “green” oxidant n Problems with chlorine based bleaching methods. n Prefer low temperature and pressures, energy savings n Oxygen is the ultimate green oxidant. n Oxygen is kinetically stable 9/15/2020 University of Idaho - Boise State 19

Overall Goals of Our Green Oxidation Program § The destruction or neutralization of xenobiotics, including nerve agents and chlorinated pesticides using green oxidation chemistry. § Focus on non-biological oxygen activation to eliminate the need for tricky enzyme based systems 9/15/2020 University of Idaho - Boise State 20

Molecular Oxygen n O 2 is kinetically stable n Oxygen’s two unpaired electrons make it difficult to accept a bonding pair n Partially reduced oxygen 9/15/2020 University of Idaho - Boise State 21

Reactive Oxygen Forms • O=O • b. o. = 2 120 kcal/mol +e- • O-O • b. o. = 1. 5 80 kcal/mol G +4 e+4 H+ +2 e+2 H+ HO-OH b. o. = 1 50 kcal/mol 2 H 2 O 9/15/2020 University of Idaho - Boise State 22

Molecular Oxygen as a Facile Oxidant • Diagram showing reaction oxygen intermediates between O 2 and H 2 O. • H+ left out for simplicity. 9/15/2020 University of Idaho - Boise State 23

The Fenton Reaction H 2 O 2 + e- HO • + HOFe(II) Fe(III) + e. Fe(II) + H 2 O 2 Fe(III) + HO • + HO- H. J. H. Fenton. J. Chem. Soc. 1894, 65, 889. F. Haber and J. J. Weiss. Proc. Roy. Soc. London, Ser. A. 1934, 147, 332. 9/15/2020 University of Idaho - Boise State 24

Oxygen Activation n Biological q 9/15/2020 cytochrome P 450 enzymes, monooxygenase University of Idaho - Boise State 25

Fe°, EDTA, Air (ZEA) system n. Fe(0), EDTA, & air n. The only nonbiological system known to date that can activate O 2 under RTP and produce a facile oxidizing species capable of extensively degrading xenobiotics n. Organophosphorous agents n. Halocarbons n. Organics IF Cheng, et al, Ind. & Eng. Chem. Res. 2003, 42(21), 5024 -5030. 9/15/2020 University of Idaho - Boise State 26

Zero-Valent Iron Remediation of Halocarbons n Iron as a reducing agent for halogenated organics n Fe(0) + R-X + H 2 O Fe 2+ + R-H + OH- + X- 9/15/2020 University of Idaho - Boise State 27

Appearance of oxidation products n Fe(0) + R-X + H 2 O Fe 2+ + R-H + OH- + X- n Oxidized Hydrocarbons/LMW carboxylates 9/15/2020 University of Idaho - Boise State 28

Fe°, EDTA, Air (ZEA) system III Fe EDTA Fe 0 O 2 - e . - O 2 + 2 H+ II Fe EDTA 2+ Fe + EDTA II Fe EDTA 9/15/2020 + H 2 O 2 III - Fe EDTA + HO University of Idaho - Boise State + HO· 29

Outline of ZEA Research n Introduction q q n General Reaction Scheme q n 9/15/2020 EDTA q Chlorinated phenols q Organophosphorus and UXO compounds Mechanisms q n Zero-valent iron/EDTA/air (ZEA) system Degradation Kinetics and Reaction Products q n Environmental Impact of EDTA The RTP Dioxygen Activation Rate-limiting Step Conclusions University of Idaho - Boise State 30

Concerns about EDTA q q q Many industrial chelating agents are not degradable by methods currently found in wastewater treatment facilities Not readily biodegradable Considerable quantities of EDTA pass through wastewater treatment facilities in the form of Fe. IIIEDTA, as high as 18µM. Sillanpaa, Mika; Orma, Marjatt; Ramo, Jaakko; Oikair; “The importance of ligand speciation in environmental research: a case study”; The Science of the Total Environment; 2001; 267, 2331. Sillanpaa, M; Pirkanniemi, K. ; “Recent Developments in Chelate Degradation”; Environmental Technology, 2001, 22, 791. Kari, F. G. ; Giger W; Modeling the Photochemical Degradation of Ethylenediaminetetraacetate in the River Glatt; Environmental Science and Technology; 1995, 29, 2814. Nirel, P. et. al. ; Method for EDTA Speciation Deteremination: Application to Sewage Treatment Plant Effluents; Wat. Res; 1998; 32, 3615. Kari, F. G. and Giger W. ; Speciation and fate of EDTA in municipal wasterwater treatment. Wat. Res. , 1996, 30, 122 -134. 9/15/2020 University of Idaho - Boise State 31

Concerns about EDTA n Questions regarding the ability to mobilize metals in the environment. q q q n Currently not being monitored or treated at waste water treatment facilities Concern for heavy metal mobility and longer bioavailability of metals to aquatic plants and animals Stable in aquatic environment EDTA is anthropogenic and long-lived. 9/15/2020 University of Idaho - Boise State 32

Goals • The destruction or neutralization of EDTA (xenobiotics) • Search for in situ conditions that will aid in the reduction in the release of EDTA in emerging green chemistries. Inexpensive & Safe Processes. • Room Temperature and Pressure Conditions (RTP) • Common Reagents – Long Term Storage • No Specialized Catalysts • System that may be incorporated into existing water treatment systems 9/15/2020 University of Idaho - Boise State 33

Experimental Setup 1 m. M EDTA (Total Vol. 50 m. L) 2. 5 g Fe° 30 -40 mesh Aldrich Open to the Atmosphere 125 ml round bottom flask Aliquots were taken directly from reaction vessel, diluted, filtered and injected into HPLC stir bar 2. 5 g Fe° 9/15/2020 Bioanalytical Systems – RPM controlled stir plate University of Idaho - Boise State 34

Evidence for Production of Reactive Oxygen Species n ROS q n O 2 - • , H 2 O 2, HO. , Fe. IV=O, etc. Two Analyses were performed q q Thiobarbituric acid-reactive substances (TBARS) assay Addition of known radical scavenger, 1 -butanol 9/15/2020 University of Idaho - Boise State 35

Suppression of EDTA degradation with the addition of Radical Scavenger 1 -butanol is a • OH radical scavenger (■) kobs = -1. 11 M-1 hr-1 (▲)kobs = -0. 08 M-1 hr-1 with 5 m. M 1 -butanol (2. 5 g ZVI g, 1. 00 m. M EDTA, open to air) Mantzavinos D; Water Res. 2004 Jul; 38(13): 3110 -8. J Hazard Mater. 2004 Apr 30; 108(1 -2): 95 -102. 9/15/2020 University of Idaho - Boise State 36

Summary of ZEA system and O 2 n n n Both TBARS and butanol tests indicate that ZEA system is able to produce facile oxidant from air at RTP Rare form of abiotic O 2 activation at RTP Identity of oxidant isn’t clear q q 9/15/2020 HO· Fe. IV=O University of Idaho - Boise State 37

Degradation of EDTA by ZEA reaction 1 m. M EDTA (50 m. L, aqueous) 2. 5 g Fe° + air 9/15/2020 University of Idaho - Boise State 38

Carbon Balance - Total Organic Carbon*, ESI-MS**, HPLC# Trapping of the volatile gases using Tenax® showed no volatile organic carbon of molecular weight C 4 and above released from the system during the course of the reaction 9/15/2020 University of Idaho - Boise State 39

Products of ZEA System n None of the products of EDTA are significant metal chelation agents. n All are more easily biodegraded. n The ZEA system has proven successful at the degradation of other organic xenobiotics. n n n 9/15/2020 Halocarbons Organophosphorus Organics University of Idaho - Boise State 40

Organophosphorous Nerve Agents and Nitrated Explosive Surrogates TNT surrogate, nitrobenzene (985 ppm) was decomposed in 24 hours. VX surrogate, malathion (49 ppm) was consumed in 4 hours, to give diethyl succinate. Malathion was the only pollutant to give a byproduct detectable by GC-FID. 9/15/2020 University of Idaho - Boise State 41

Malathion Degradation DES malathion max: 4 -6 hrs PO 43 - + SO 42 - : 0. 0593 m. M (14% yield) (24 hrs) PO 42 - 9/15/2020 : 0. 0825 m. M (19 % yield) (24 hrs) University of Idaho - Boise State malaoxon Max: 7 hrs 42

Kinetics of Malathion Degradation Malathion Diethyl Succinate (DES) GC/FID chromatograph: each data point indicates an individual reaction vial extracted using 50/50 hexane/ethyl acetate, error bars indicate the standard deviation between three measurements of each sample vial. 9/15/2020 University of Idaho - Boise State 43

Kinetically stable organic products from ZEA degradation. iminodiacetic acid (degrades after 12 hrs) propionic acid Degradation products for 9/15/2020 bicarbonate succinic acid Oxalic acid -EDTA -Malathion -4 -chlorophenol -pentachlorophenol -phenol University of Idaho - Boise State 44

Overall Scheme (simplified) This study Beenackers Ing. Eng. Chem. Res. 1992, 32, 2580 Van Eldik Inorg. Chem, 1997, 36, 4115 -4120 25. 5 k. J/mol 27. 2 k. J/mol 33. 9 k. J/mol Metal dissolution: n Fe(0) Fe 2+ + 2 e- (1) Complex formation n Fe 2+ + EDTA Fe. IIEDTA (2) Homogeneous O 2 activation: n 2 Fe. IIEDTA + O 2 + 2 H+ 2 Fe. IIIEDTA + H 2 O 2 (3) Fenton Reaction n Fe. IIEDTA + H 2 O 2 Fe. IIIEDTA + OH • + OH- (4) EDTA degradation: n OH • + Fe. EDTA Fe 2+/3+ + EDTA* (5) § EDTA* = damaged EDTA Redox Cycling: n Fe. IIIEDTA + e- Fe. IIEDTA (6) • Step 3 is Rate-Limiting 9/15/2020 University of Idaho - Boise State 45

Voltammetric Studies n n ZEA reaction rate is dependent on p. H 2. 5 < p. H < 4. 5 LMW Acids Self Buffers the ZEA reaction at 3. 5 Oxygen Activation Rates Measured By Cyclic Voltammetry 9/15/2020 University of Idaho - Boise State 46

CV of Fe(II/III)EDTA in the presence of O 2 n Electrocatalytic (EC’) Voltammetry 2 Figure 1. Cyclic voltammetric curves on a p. H =3 sample A 1. 5 1 u. A A) 0. 1 m. M Fe. IIIEDTA and O 2 saturated, B) 0. 1 m. M Fe. IIIEDTA only, 0. 5 B B 0 -0. 5 0. 3 0. 2 0. 1 0 scan rate = 5 m. V/s. 9/15/2020 -0. 1 -0. 2 -0. 3 -0. 4 V University of Idaho - Boise State 47

Electrocatalytic currents at -200 m. V at 5 m. V/s. 9/15/2020 University of Idaho - Boise State 48

2. 5 < p. H < 4. 5 Free Fe 2+ Fe. IIEDTA Fe. II(OH)2 EDTA Fe. II(OH)EDTA Fe. IIH 9/15/2020 2 EDTA Fe. IIHEDTA (MLH) University of Idaho - Boise State 49

Fe(II)HEDTA or MLH is responsible for oxygen activation N N N Fe I 9/15/2020 II COOH N N Fe COOH HOOC O 2 COOH N HOOC N COOH III University of Idaho - Boise State 50

Conclusions n This system is a viable option for the destruction of a variety of pollutants and has a strong possibility for scale up. n The only system known to date that can obtain non-biological Oxygen Activation at room temperature and pressure to produce reactive oxygen species that are capable of fully degrading pollutants to LMW carboxylates and inorganic forms n Due to the duality of EDTA acting as both a pro-oxidant and antioxidant, controlling the [EDTA] is imperative to the success of the process. n Rate-limiting steps is (are) oxygen activation n Fe. IIEDTA may provide insights into biological oxygen activation 9/15/2020 University of Idaho - Boise State 51

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Reactive Oxygen Species (ROS) in Biology 9/15/2020 University of Idaho - Boise State 53

ROS and Inflammation Phagocytes Infections -viruses -bacteria -parasites Foreign Substances -smoke -asbestos Damaged Tissue -heat -mechanical -UV 9/15/2020 Activation of Inflammatory Cells University of Idaho - Boise State ROS RNS 54

ROS and Inflammation Cl. O 2. H 2 O 2 NO. 9/15/2020 University of Idaho - Boise State HOCl + Ca 2+ ONOO. - 55

Iron Enzymes and the Fenton Reaction Hemes/Cytochromes Oxygenases Oxidases H 2 O 2 + reducing agent HO. • All Fe-containing enzymes are quite good Fenton Reaction agents. • Oxidative Stress 9/15/2020 University of Idaho - Boise State 56

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Inflammation The Good Inflammation protects the body • Destroys invading pathogens • Dissolves damaged tissue The Bad Chronic or prolong inflammation Allergies and Autoimmune Diseases • All the many types of allergies • Many of the autoimmune diseases 9/15/2020 University of Idaho - Boise State 58

Role of Calcium in Inflammation 9/15/2020 University of Idaho - Boise State 59

Role of Calcium in Inflammation n Enhances Oxidative Processes in Inflammation ROS n n Paradoxically Redox Inactive, i. e. always Ca 2+ Inflammation { H 2 O 2. - Ca 2+ Role in Biological Oxidations Not Well Understood 9/15/2020 University of Idaho - Boise State 60

Inflammation Sequence Fe. II apoenzyme HO· ROS Inflammation { H 2 O 2 Cl- HOCl Fe. IIenzyme O 2. NO ONOO- Ca 2+ ? 9/15/2020 University of Idaho - Boise State 61

The Low MW Iron Pool Fe. II apoenzyme HO· ROS Inflammation { H 2 O 2 Cl- HOCl Fe. IIenzyme O 2. NO ONOO- Ca 2+ ? Fe Fe released into LMW pool ROS 9/15/2020 University of Idaho - Boise State 62

Ligands for the LMW Fe pool n n n Glutamate Citrate Phosphates, e. g. ATP, ADP, GTP, etc. Amino Acids Peptides Proteins (HMW) 9/15/2020 University of Idaho - Boise State 63

Fe(II/III)EDTA as a model for physiological LMW Fe 9/15/2020 University of Idaho - Boise State 64

The concentration ratio of [Chelate/Ligand]: [Fe] is very high n Physiological Concentration Mobile (Free) Iron ≈ 10 -9 M n [Chelates/Ligand] ≈ 10 -3 M n Does this have any effect of the reactivity of LMW-Fe in the Fenton Rxn? 9/15/2020 University of Idaho - Boise State 65

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Fe. II/IIIEDTA CV in [Fe]: [EDTA] at 1: 10 and 1: 1 9/15/2020 University of Idaho - Boise State 67

EC’ CV of Fe. II/IIIEDTA (1: 1) with H 2 O 2 n n n Fe. IIIEDTA + e- = Fe. IIEDTA + H 2 O 2 = Fe. IIIEDTA + HO- + HO∙ (fast) H 2 O 2 + e- = HO- + HO∙ (slow) 9/15/2020 University of Idaho - Boise State 68

EC’ current measured at -700 m. V various ratios of [Fe]: [Ligand] 9/15/2020 University of Idaho - Boise State 69

Excess molar EDTA and other Chelates suppress Fenton Rxn kinetics = 102 -104 n Fe. II-OOH(EDTA) + Excess EDTA Fe. II(EDTA) + HOOH (see references below) n V. Zang, R. van Eldik “Kinetics and Mechanism of the Autoxidation of Iron(II) Induced through Chelation by Ethylenediaminetetracetate and Related Ligands” Inorganic Chemistry 1990, 29, 1705 -1711. n Ariane Brausam, Rudi van Eldik “Further Mechanistic Information on the Reaction Bewteen Fe. IIIEDTA and Hydrogen Peroxide: Observations of a Second Reaction Step and Importance of p. H” Inorganic Chemistry, 2004, 43, 5351 -5359. n [1] Walling, C. , Kurz, M. , Schugar, H. J. 1970 “The Iron(III)-Ethylenediaminetetraacetic Acid-Peroxide System” Inorganic Chemistry, 9(4), 931 -937 9/15/2020 University of Idaho - Boise State 70

Hypothesized Role of Calcium in Inflammation 9/15/2020 University of Idaho - Boise State 71

Ca 2+ increases Fenton Rxn Kinetics in high [EDTA]: [Fe] ratios n Recovery of Fenton reactivity of Fe complexes by addition of Ca 2+. n 1: 50 [Fe. III]: [citrate] n 1: 20 [Fe. III]: [NTA] 1: 10 [Fe. III]: [EDTA] n n Other common conditions: 0. 1 m. M Fe 3+, 22. 8 m. M H 2 O 2, and p. H 7. 4 HEPES, carbon disk electrode, 10 m. V/s sweep rate 9/15/2020 University of Idaho - Boise State 72

Table 1: Stability Constants for M: L complexes Log β 1 Ca+2 Fe+3 Ethylenediaminetetraacetic Acid (EDTA) (HOOCCH 2)2 NCH 2 N(CH 2 COOH)2 10. 65 14. 32 25. 1 Nitrilotriacetic Acid (NTA) (HOOCCH 2)3 N 6. 3 8. 9 15. 9 Citric Acid HOOCCH 2 CH(OH)(COOH)-CH 2 COOH 3. 45 4. 4 11. 5 • Ca 2+ uptakes excess metal binding capacity without displacing Fe. II or Fe. III • Optimizes Fe. IIEDTA to the 1: 1 molar ratio form 9/15/2020 University of Idaho - Boise State 73

Fe. II apoenzyme HO· ROS Inflammation { H 2 O 2 Cl- HOCl Fe. IIenzyme O 2. NO ONOO- Ca 2+ High [L]: [Fe. II] Oxidatively inactive Fe released into LMW pool Ca 2+ optimized [L]: [Fe. II] Oxidatively active 9/15/2020 University of Idaho - Boise State 74

Fe. II apoenzyme HO· ROS { Inflammation H 2 O 2 Cl- HOCl Fe. IIenzyme O 2. - Fe released into LMW pool NO ONOOHigh [L]: [Fe. II] inactive Ca 2+ redox cycling H 2 O 2 HO· Damage to DNA Lipids Proteins optimized [L]: [Fe. II] active 9/15/2020 University of Idaho - Boise State 75

Conclusions II n Fe. II/IIIEDTA is a good model for LMW physiological iron n Ca 2+ part of the inflammation cascade to optimize Fe chelation sphere for the Fenton Rxn. 9/15/2020 University of Idaho - Boise State 76

Other studies using Fe. EDTA n Sensor for Peroxide Based Explosives n O 2 reduction catalysts for fuel cells 9/15/2020 University of Idaho - Boise State 77

Acknowledgements Derek Laine Funding NIH Kenichi Shimizu NSF Simon Mc. Allister NASA Ruhba Ponraj Mark D. Engelmann, Ph. D. 2003 Tina Noradoun, Ph. D. 2005 Ryan Hutcheson, B. S. 2004 EPRI BLM UI Rob Bobier, B. S. 2002 Terry Hiatt, B. S. 2000 9/15/2020 University of Idaho - Boise State 78

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