New Tools in the Water Technology Toolbox Swellable Organosilica Materials forReversible Extractions of Dissolved Organics and Metals Paul L. Edmiston College of Wooster Contact Information: email@example.com ACS Fall Meeting 2012, Philadelphia, PA Ensuring the Sustainability of Critical Materials and Alternatives
High Volume Waste Streams, Very Little Attention “The solution to pollution is dilution.” When something outlasts a certain degree of usefulness, we wish it to disappear. Since matter cannot be destroyed, a convenient disposal method is dilution. Two high volume waste streams that are hard to dilute due to volume, but may hold great resource potential: 1. Produced Water 2. Stormwater Runoff
Produced Water: Energy-Water Nexus Produced water is the water from petroleum production. 800 billion gallons of produced water every year. Current practice onshore: Reinjection Current Practice off-shore: Overboard Average 10 water: 1 oil ratio Produced water contains: dissolved organics production chemicals NORMS organic acids metals ions salt
Oil Sand Production: Energy-Water Nexus Steam assisted gravity drain (SAGD) water 300 million gallons per day by 2030.
How much organic in produced water?Just considering dissolved hydrocarbon and BTEX ~ 250 ppm250 ppm x 800 billion gallons = 250 million gal of gasoline eq. Enough gasoline to supply U.S. needs for 1 day.**U.S. Energy Administration http://www.eia.gov/tools/faqs/faq.cfm?id=23&t=10
How much organic in produced water?Just considering dissolved hydrocarbon and BTEX ~ 250 ppm250 ppm x 800 billion gallons = 250 million gal of gasoline eq. Enough gasoline to supply U.S. needs for 1 day.* Extraction of dissolved components has a substantial thermodynamic barrier. Need to overcome entropy.*U.S. Energy Administration http://www.eia.gov/tools/faqs/faq.cfm?id=23&t=10
Aryl-Bridged Mesoporous Silica That Swells: Osorb® No solvent 150 µm 200 nm +Solvent OCH3 H3 CO Si CH2CH2 OCH3 OCH3 CH2 CH2 Si OCH3 OCH3Surface area: 400-600 m2/gPore volume: 0.6-1.5 mL/g
Force Generation Upon SwellingOrganic liquids Hydrocarbon vapors propane 600 liquid = acetone 500Force N/g 400 300 200 methane 100 0 0 1 2 3 4 Volume increase (v/v) Max force 600 N/g (61,000 w/w) Work = 0.8 ± 0.1 J/g ΔHswell = 5.2 ± 1.2 J/g Entropically driven process Max 1x w/w change for condensable 300% ΔV, 650% Δmass vapors when p=p0 13% volume,
P ro d u c e d Wa te r Tre a tm e n tOs o rb ® re m o ve s a wid e ra n g e o f o rg a n ic s fro m wa te r:
Absorption Model hydrophobic barrier1 Matrix tension 2 void volume new surface area Dissolved hydrocarbons3 4 Continued matrix expansion
Absorption Model: Solid Solvent Extra c tio n o f 30 Co m p o u n d sOs o rb ® a c ts a s a “s o lid s o lve n t” th a t u s e s b y Os o rb vs . lo g Ko wm e c h a n ic a l re la xa tio n a s a n a d d itio n a l d rivin gfo rc e fo r a b s o rp tio n o f o rg a n ic s fro m wa te r.Expansion is endothermic indicating a decrease inentropy (∆Smatrix) that is a significant energy termmanifested by fact that swelling can producemechanical forces that exceed 400N/g.In g e n e ra l, th e re is a o n e o rd e r o f m a g n itu d eg re a te r p a rtitio n c o e ffic ie n t fo r a b s o rp tio n b yOs o rb c o m p a re d to liq u id -liq uid e xtra c tio n d u e k = Osorb/water equilibrium partition coefficientto th e c o n trib u tio n fro m m a trix e xp a n s io n . Kow = octanol-water partition coefficient Conditions : contaminant concentration 100 ppm, 0.5% w/v Osorb per volume of solution, T=25°C.
Treatment of Highly Impacted WaterPesticide waste Flow back waterComplex mixture of pesticides, dyes, TOC before = 265 ppmBTEX, surfactants TOC after = no detect(5% organics by weight) 0.4%w/v Osorb
Rare Earth Extraction from Shale Gas Water Rare earths elements are not rare, but formations of high concentration are hard to find. Found in alluvial deposits where freshwater meets salt water. Ideal location would be in ancient estuary environments. Many are buried in shale deposits. Hydraulic fracking is exploring deep shale deposits. Utica shale shows regions where rare earth element concentrations are in excess of 4,000 ppm. Exploring synergistic extraction of REEs and hydrocarbons in PW
Rare Earth Extraction from Shale Gas WaterChallenge is extracting REEfrom Group II cations.Creating a type of Osorb thatduplicates the multistageliquid-liquid extraction processuse in conventionalhydrometallurgical processesin a single core-shell particleGoals:1) Rapid sampling system using hand-held XRF2) Larger scale extraction system for PW.
Ex situ remediation: Produced water and flow back Funding from National Science Foundation and U.S. Department of Energy for pilot scale testing in the field, produced water and flow backTrailer and Skid-Mounted Systems Available (4-60 gal/min)Skid system tested by Texas A&M University
What critical materials are being lost? Nitrate and Phosphate55% of the energy input in domesticwheat production is nitrate fertilizer Economical supplies of phosphate areWoods J et al. Phil. Trans. R. Soc. B 2010;365:2991-3006 limited and can be depleted.
Rain Garden/Bioswale/BioretentionDesigned to slow the flow of stormwater and filter pollutants fromthe water before it eventually recharges ground water, seeps intothe municipal storm sewer system, or discharge into waterways Rain Garden, Bioswale, Bioretention System, Bioinfiltration System, Biofilter, Stormwater Wetland, Vegetated Buffer System
Rain Garden/Bioswale/Bioretention Multiple physical, chemical, and biological functions Limited adsorption capacity: - Short retention time - Poor removal of soluble pollutants - Not recommended at “hot spots”
Project Goals Title: Development of Physico-Chemically and Biologically Activated Swelling Organosilica-Metal Composites Filter Media in Bioretention Systems for Enhanced Remediation of Urban and Agricultural Stormwater Runoff Hypothesis: Properly amended Osorb-metal composites filter media in bioretention systems can remove a wide variety of stormwater runoff pollutants and significantly enhance overall treatment capacity of the systems Work Plan: Develop Osorb-based materials with embedded reactive metal particles including aluminum (Al0), iron (Fe0), magnesium (Mg0), zinc (Zn0), and nickel (Ni0) to capture organic pollutants and chemically degrade pollutants from runoff water
Osorb®-Metal Composites Al-Osorb Fe-Osorb Mg-Osorb Ni-Osorb Zn-Osorb - Researched new metal-Osorb composites - Examined reduction of motor oil, nitrate, phosphate, atrazine, estradiol, triclosan, and ethylene glycol - Continue research to determine reduction mechanism and longevity in Phase II funding
Column Tests:Osorb®-Metal Composites Fill Media Simulated Runoff PollutantsParameter Pollutants Concentration (mg/LPetrolum hydrocarbons Motor oil 1000 1000Nutrients Nitrate (NO3-N) 20 10 Phosphate (PO4-P) 10 10Herbicide Atrazine (C8H14ClN5) 1 0.5Pharmaceuticals 17α-Ethinylestradiol (C20H24O2) 1 0.5 Triclosan (C12H7Cl3O2) 0.5 1Antifreeze/deicer Ethylene glycol (C2H6O2) 1000 1000 Experimental Set-Up A total of seven simulated runoff event once a week Different contents (0%, 1%, 2%) of three Osorb-metals (Fe, Mg, and Zn) in soil base media: sand or soil mix
Iron-Osorb® Bioretention Systems OMR001&2 – Iron-Osorb Enviro-Swales (July 2012) Before After Before After
Field Tests:Iron-Osorb Enhanced Bioretention SystemSite views of field-scale experimental bioretention systems (rain gardens) installed at the campus of theCollege of Wooster, OH. One is a standard model, and one version is enhanced with Iron-Osorb.
Column Tests:Motor Oil Removal 1000 mg/L of motor oil loading Improved removal efficiency of motor oil with Osorb-Metals
Column Tests:Nitrate Removal 10 mg/L of NO3-N loading Up to 50% improved removal efficiency of NO3 with Osorb-Metals
Column Tests:Phosphate Removal 10 mg/L of PO4-P loading66 Up to 40% improved removal efficiency of PO4 with Osorb-Metals
Column Tests:Atrazine Removal 500 µg/L of atrazine loading Up to 60% improved removal efficiency of atrazine with Osorb-Metals
Field Tests:Nutrient Removal Lower effluent concentration of nutrients from iron-Osorb enhanced rain garden compared to standard rain garden
Column Tests:Soil Microbial Community Scanning electron microscope (SEM) images of soil mix control (a) and Fe-Osorb amended soil mix (b) in the saturated bioretention design after the completion of 3-month column experiments. Blue arrows indicate bacteria or other microorganisms.
What is Next? Currently developing a magnetically retrievable phosphate selective binding Osorb to amend agricultural bioswales for phosphate recovery and watershed protection.
Philadelphia is taking the lead!Green City, Clean Waters PlanAdministrator Lisa Jackson and Mayor Michael Nutter announced April 10, 2012 that the EPAand Philadelphia will join in advancing the use of cutting-edge green infrastructure technologiesto solve the city’s sewage overflows and create healthier neighborhoods for the city’s residents.The agreement specifically highlights Philadelphia’s capacity to serve as a model for citiesnationwide to embrace green infrastructure to manage stormwater runoff.
Acknowledgements and References Support: National Science Foundation U.S. Department of Energy Ohio EPA Collaborators: Dr. Hanbae Yang Edmiston, P. L.; Underwood, L. A. Absorption of Dissolved Organic Dr. Tatiana Eliseeva Speciestion a nd P urifica tionOrganically Modified Silica(2009). S e pa ra from Water Using Te chnology 66, 532-540 that Swells. Dr. Stephen Jolly Burkett, C. M.*; Underwood, L. A.*, Volzer, R. S.*; Baughman, J. A.*; Justin Keener Edmiston, P. L. Organic-Inorganic Hybrid Materials that Rapidly Swell in Non-Polar Liquids: Nanoscale Morphology and Swelling Mechanism. Che mis try of Ma te ria ls 20, 1312-1321 (2008). Students: Burkett, C. M.; Edmiston P. L.; Highly Swellable Sol-Gels Prepared by Zachary Harvey Chemical Modification of Silanol Groups Prior to Drying. J Non-Crys ta lline S olids ,351 , 3174-3178 (2005). Alison Chin Edmiston, P.L.; Campbell, D.P.; Gottfried, D.S.; Baughman, J.*; Timmers, Noel Mellor M.M.* Detection of Trinitrotoluene in the Parts-per-Trillion Range Using Waveguide Interferometry, S e ns or & Actua tors B. 143, 574-582 (2010). Christine Kasprisin Melissa Morgan www.absmaterials.com Paige Piper firstname.lastname@example.org 330-234-7999
Permeability to Organics vs. Water Vapor 7 Infrared Absorbance in Collection 6 propane 5 Chamber 4 3 2 1 H 2O 8 mm 1 mm 0 0 10 20 30 40 50 60 Time (min) IR spectrometer Osorb disk Gas cell Vent (100 mL) Propane + H2O(g)sat N2, 1 mL/minDiffusion cell – Osorb separated flow cells