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(12) United States Patent (10) Patent No.: US 7,892,436 B2 Gadgil (45) Date of Patent: Feb

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(12) United States Patent (10) Patent No.: US 7,892,436 B2 Gadgil (45) Date of Patent: Feb USOO7892436B2 (12) United States Patent (10) Patent No.: US 7,892,436 B2 Gadgil (45) Date of Patent: Feb. 22, 2011 (54) COMPOSITIONS AND METHODS FOR (58) Field of Classification Search ................. 210/679, REMOVING ARSENIC IN WATER 210/682, 683, 684, 688, 748.1, 748.15, 748.13, 210/749, 756, 758, 198.1, 200, 201, 202, (75) I tor: Ashok J th. Gadgil, El Cerrito, CA 210/205, 206, 209,502.1, 506, 911, 912, VO te aganntn Uradgil, El Uerrillo, 210/913, 668, 669; 428/406; 502/.406, 407; 106/DIG. 1 (73) Assignee: The Regents of the University of See application file for complete search history. California, Oakland, CA (US) (56) References Cited (*) Notice: Subject to any disclaimer, the term of this U.S. PATENT DOCUMENTS patent is extended or adjusted under 35 3,926,659 A * 12/1975 Bernhard et al. ............ 106,418 U.S.C. 154(b) by 449 days. (Continued) (21) Appl. No.: 11A912.104 FOREIGN PATENT DOCUMENTS y x- - - 9 CA 1067 627 A1 12, 1979 (Continued) (22) PCT Filed: Apr. 25, 2006 OTHER PUBLICATIONS Schweitzer, P., "Corrosion-Resistant Linings and Coatings' 2001, (86). PCT No.: PCT/US2OO6/O15664 Marcel Dekker, Inc. p. 266.* (Continued) S371 (c)(1), Primary Examiner Matthew O Savage (2), (4) Date: Oct. 19, 2007 Assistant Examiner—Lucas Stelling (87) PCT Pub. No.: WO2006/116421 (74) Attorney, Agent, or Firm Kilpatrick Townsend & y x- - - Stockton LLP PCT Pub. Date: Nov. 2, 2006 (57) ABSTRACT (65) Prior Publication Data Compositions and methods and for contaminants from water US 2008/O197081 A1 Aug. 21, 2008 are provided. The compositions comprise ferric hydroxide • 1- us and ferric oxyhydride coated Substrates for use in removing Related U.S. Application Data the contaminant from the water. Contacting water bearing the (60) Provisional application No. 60/674,835, filed on Apr. contaminanttami twith win the substratsubstrates can substanuallybstantially reaucered con 25, 2005, provisional application No. 60/679,393, taminant levels therein.- Methods of oxidizing the contami filed on Mav 9, 2005 nants in water to facilitate their removal by the ferric hydrox y 9, ide and ferric oxyhydride coated substrates are also provided. (51) Int. Cl. The contaminants include, but are not limited to, arsenic, CO2F I/42 (2006.01) Selenium, uranium, lead, cadmium, nickel, copper, Zinc, CO2F I/32 (2006.01) chromium and Vanadium, their oxides and soluble salts thereof. (52) U.S. Cl. ....................... 210/668; 210/669; 210/682: 210/688; 210/748.13: 210/913 9 Claims, 6 Drawing Sheets Aqueous R8cy Feso, 7 Ho (G)coalashcal as pH-6.3-iwi, addition Mix Product step it fertis oxide complex on H coalash Excess NaO Arsenic laced wate Reactic Pure was Productstep 4 A. Rinse with Ferrous salt solution (e.g., ferrous sulfate) B. Rinse with water US 7,892.436 B2 Page 2 U.S. PATENT DOCUMENTS Clayton, Mark, "A race to fix a 30-year-old 'solution” Water Con serve, dated Feb. 17, 2005., url: http://www.waterconserve.info/ar 4,046,687 A 9, 1977 Schulze ticles/reader.asp?linkid=39318, pp. 1-4. 4,112,063 A 9, 1978 Buxbaum et al. Cliford, Dennis, “Anion Exchange with Choloride-form Strong-Base 4,366,128 A 12/1982 Weir et al. Resins.” http://web.mit.edu/murcott/www.arsenic/templates/ 5,043,080 A * 8, 1991 Cater et al. ............ 210,748.15 14UHouston.htm. Univ of Houston (US), p. 1-2, (Feb. 14, 2005). 5,075,010 A * 12/1991 Zhang ........ ... 210,643 Das, Dipankar, et al. "A Simple Household Device to Remove 5,369,072 A * 1 1/1994 Benjamin et al. ............. 502/84 Arsenic from Groundwater and Two Years Performance Report of 5,556,545 A 9, 1996 Volcher et al. Arsenic Removal Plant for Treating Ground water with Community 5,603,838 A 2f1997 Misra et al. Participation.” School of Environment Studies, Jadavpur University, 5,635,073. A 6, 1997 Aktor et al. Calcutta-700 032, India pp. 231-250. 5,858,249 A 1/1999 Higby Database Biosis 'Online Biosciences Information Service, Philadel 6,042,731 A 3, 2000 Bonnin phia, PA, US; Sep. 2002, Lin Chiu-Yue et al. “Removal of pollutants 6, 197,201 B1 3, 2001 Misra et al. from wastewater by coalbottomash” XP002331129 Database acces 6,200,482 B1 3, 2001 Winchester et al. Sion No. PREV200300040842 abstract and Journal of Environment 6,248,241 B1* 6/2001 Christensen et al. ........ 21Of715 Science and Health Parta Toxic-Hazardous Substances and Environ 6,613,230 B2 9, 2003 Krulik et al. mental Engineering, vol. A37, No. 8, Sep. 2002, pp. 1509-1522, 6,824,690 B1 1 1/2004 Zhao et al. ISSN: 1093-4529. 6,914,034 B2 T/2005 Vo Edwards, Marc, et al. Adsorptive filtration using coated Sand: a new 2002.000311.6 A1 1/2002 Golden approach for treatment of metal-bearing wastes.” 1989, pp. 1523 2002fOO36172 A1 3/2002 Del Signore 1533. 2002fO113023 A1 8, 2002 Krulik et al. Gadgil, Ashok, et al. "Arsenic Removal from Drinking Water.” 2003/0116504 A1 6/2003 Vempati Lawrence Berkeley National Lab (US), p. 1-11, (Feb. 1, 2004). 2003/O183579 A1 10/2003 Bandyopadhya et al. Gilles, Greg, et al., “Arsenic Reduction Challenges in India and 2004.0089608 A1 5, 2004 Vo Bangladesh.” Water Conditioning and Purification, 2000, 3 pp. 2004/0101971 A1 5, 2004 Voice et al. Joshi, Arun, et al. “Removal of Arsenic from Ground Water by Iron 2004/O108275 A1 6, 2004 Shaniuk Oxide-Coated Sand.” Journal of Environmental Engineering, 1996, 2005/0059549 A1* 3/2005 Vo ............................. 5O2/406 pp. 769-771. 2005, O250644 A1 1 1/2005 Gadgil Krotz, Dan “Water Filter Could Help Millions of Bangladeshis.” Research News, url: http://www.lbl.gov/Science-Articles/Archive? FOREIGN PATENT DOCUMENTS EETD-Gadgil-water-filter.html, dated Jan. 21, 2005, retrieved on Apr. 22, 2005, pp. 1-3. JP 56-046240 * 4f1981 Lawrence Berkeley National Laboratory, “Environmental Energy WO WO 2004/064078 A2 T 2004 Technologies Division; News.” 2005, vol. 6, No. 1, pp. 1-12. McMullin, Michael, “High Efficienciency Low-Cost Arsenic Adsor OTHER PUBLICATIONS bent for Drinking Water.” ADI International, Inc. (Canada), p. 1-9, Report on Ernest Orlando Lawrence Laboratory: Laboratory (Mar. 1, 2004). Directed Research and Development Program, FY 2006, p. (v) and Patoczka HMM. Jurek, et al. “Trace Heavy Metals Removal with 42.* Ferric Chloride.” Presented at Water Environment Federation Indus trial Wastes Technical Conference, Nashville, TN, 1998, 14 pp. “Berkeley Lab Currents' url: http://www.lbl.gov/Publications/Cur Pescovitz, David. “Community Water Works.” Lab Notes, url: http:// rents/Archive/Dec-03-2004.html retrieved on Jun. 12, 2005, 18 pp. www.coe.berkeley.edu/labnotes/0405/gadgil.html, dated Apr. 2005, “The Arsenic Removal Project; the arsenic crisis.” Blue Planet Run, retrieved on Apr. 22, 2005, pp. 1-3. 2004, pp. 1-6. Tang-Quan, "Sci-Tech Clean Water for Bangladesh.” The Daily Cali Ali, Ashraf M., et al., “Development of Low-cost Technologies for fornian, url: http://www.dailycal.org/particle.php?id=17465, Removal of Arsenic from Groundwater.” Technologies for Arsenic retrieved on: Feb. 7, 2005, pp. 1-2. Removal from Drinking Water, pp. 99-120. Thirunavukkarasu, O.S., et al. “Removal of Arsenic in Drinking Apyron Technologies, "Apyron Technologies and the University of Water by Iron Oxide-Coated Sand and Ferrihydrite-Batch Studies.” Houston Awarded Grant for Arsenic Removal Program.” Air and Water Qual. Res J. Canada, vol. 36 (No. 1), p. 55-70. (Apr. 11, 2001). Water Treatment Solutions, www.apyron.com/news al.html (US), p. 1, (Jun. 28, 1999). * cited by examiner U.S. Patent Feb. 22, 2011 Sheet 1 of 6 US 7,892,436 B2 FIG. 1 Aqueous Recycle Recycle FeSO, 7 HO ...wa. Arm&mdaswww.wt RaW Coalash Hydrated ferous oxide complex on Coal ash surface ...rsssrss&srow.8xrurviewisrev-assassissarwaxes Assemble Arsenic reactor laced Wate Disposal FeO+ 5HO + 2As > 2FeAsO+ 1 OH" -- Complexed Reaction Product step i3 Product step #4 Analyze CMS A. Rinse with Ferrous salt solution (e.g., ferrous sulfate) B. Rinse with Water U.S. Patent Feb. 22, 2011 Sheet 2 of 6 US 7,892,436 B2 FG, 2. OO Bangladesh Arsenic Stc. ... s. s Initial Arsenic concentration a 2400 ppb St 5 3, i O s 8e p 2. s s i. 3. O 500 1OOO 1500 2000 2500 Cumulative Treated Volume (ml) (With 5 gram LBNL media) U.S. Patent Feb. 22, 2011 Sheet 3 of 6 US 7,892,436 B2 FIG 3 U.S. Patent Feb. 22, 2011 Sheet 4 of 6 US 7,892.436 B2 FIG. 4 U.S. Patent Feb. 22, 2011 Sheet 5 of 6 US 7,892,436 B2 FIGS LBNL Media Removal Kinetics on Lab-spiked Water ar d 's r 50 ppb. (Bangladesh littit; s current US limit) CD g 2O 30 Time (minutes) U.S. Patent Feb. 22, 2011 Sheet 6 of 6 US 7,892,436 B2 F.G. 6 US 7,892,436 B2 1. 2 COMPOSITIONS AND METHODS FOR arsenic through drinking water is associated with cancer of REMOVING ARSENIC IN WATER the lungs, bladder, skin, liver, and kidneys. Other health stud ies have indicated that consumption of drinking water con RELATED APPLICATIONS taminated with arsenic can cause other kinds of serious harm, including developmental defects, still birth, and spontaneous This application claims priority benefit of U.S. Provisional abortions as well as heart attacks, strokes, diabetes mellitus, Patent Application Ser. No. 60/674,835, filed Apr. 25, 2005 and high blood pressure. Arsenic ingestion can also injure the and of U.S.
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