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. 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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.