Feasibility of Water Treatment Technologies for Arsenic and Fluoride Removal

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Feasibility of Water Treatment Technologies for Arsenic and Fluoride Removal AWWA Water Quality Technology Conference 17 November 2004; Arsenic I Brian C. Pickard, P.E., R.S. U.S. Army Center for Health Promotion and Preventive Medicine Aberdeen Proving Ground, MD Muhammad Bari, P.E. Chief, Environmental Division, Fort Irwin, CA 1

Report Documentation Page Form Approved OMB No. 0704-0188 Public reporting burden for the collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden, to Washington Headquarters Services, Directorate for Information Operations and Reports, 1215 Jefferson Davis Highway, Suite 1204, Arlington VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to a penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. 1. REPORT DATE NOV 2004 2. REPORT TYPE N/A 3. DATES COVERED - 4. TITLE AND SUBTITLE Feasibility of Water Treatment Technologies for Arsenic and Fluoride Removal 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) U.S. Army Center for Health Promotion and Preventive Medicine Aberdeen Proving Ground, MD 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR S ACRONYM(S) 12. DISTRIBUTION/AVAILABILITY STATEMENT Approved for public release, distribution unlimited 11. SPONSOR/MONITOR S REPORT NUMBER(S) 13. SUPPLEMENTARY NOTES Presented at the AWWA Water Quality Technology Conference November 2004, The original document contains color images. 14. ABSTRACT 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT UU a. REPORT unclassified b. ABSTRACT unclassified c. THIS PAGE unclassified 18. NUMBER OF PAGES 35 19a. NAME OF RESPONSIBLE PERSON Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18

Project Background Current Operations and Consumptive Use Contaminant Overviews Data Collection Treatment Alternative Analysis & Considerations Treatment Alternatives Screening Conclusions Overview 2

Project Background Location: : Fort Irwin, CA, approximately 35 miles northeast of Barstow, California, in the north-central part of the Mojave Desert Source Water: : 11 groundwater wells from three distinct geologic basins (Irwin, Bicycle, and Langford) Water ater Demand: : Fort Irwin houses the Army s s National Training Center, so water demand fluctuates due to troop rotations and seasonal irrigation Source Water Contaminants of Concern Arsenic (As) > future MCL of 0.010 mg/l (January 2006) Fluoride (F) > State MCL of 2 mg/l 3

Relative Basin Contributions to Total Monthly Water Production 160 140 120 Bicycle Langford Irwin Total 100 Million Gallons 80 60 40 20 0 Jan-03 Feb-03 Mar-03 Apr-03 May-03 Jun-03 Jul-03 Aug-03 Sep-03 Date 4

Existing Operations - Two Systems? Dual-line line (domestic and potable) water distribution system Domestic Water: chlorinated groundwater at the wellhead (bathing, irrigation, toilet flushing, etc); Potable Water: 0.15 MGD Reverse Osmosis (RO) plant for potable water 5

Consumptive Use Conundrum In defining a Public Water System in 1996 SDWA Amendments, EPA broadened the definition of consumptive use to more than just drinking, stating human consumption includes drinking, bathing, showering, cooking, dishwashing, and maintaining oral hygiene All consumptive use water, not just the RO-treated potable portion, would need to meet SDWA requirements, including compliance with arsenic and fluoride MCLs 6

Treatment Requirements Co-removal treatment technology for As and F Arsenic Rule, January 2001, revised arsenic MCL from 50 µg/l to 10 µg/l, enforceable mid-january 2006 Fluoride MCL is 2 mg/l (CDHS; SDWA is 4 mg/l) WTP design flow will increase from 0.15 to 5.0 MGD and employ 1-line 1 distribution system Design/construction of a new, full-scale WTP First priority: water conservation Consider waste flows 7

Contaminant Overviews 8

Contaminant Overview: Arsenic Occurrence Common, naturally-occurring drinking water contaminant originating from arsenic-containing containing rocks and soil, transported to natural waters via erosion, dissolution and air emission Man-made sources: mining and smelting operations; agricultural applications; and the use/disposal of industrial products Arsenite, As(III); neutral surface charge vs. Arsenate, As(V), negative surface charge Health Effects - Both cancerous and non-cancerous effects Class A human carcinogen, with low arsenic exposure (< 0.05 mg/l) linked to cancer of the skin, liver, lung and bladder Large arsenic doses (above 60 mg/l) can cause death; lower doses (0.30-30 mg/l) may cause stomach and intestinal irritation and nervous system disorders 9

Contaminant Overview: Fluoride Occurrence contained in minerals, fluorspar (fluorite) and apatite (calcium fluorides) and released as fluoride ions when contacted with GW, thus fluoride is found naturally in all waters Typical GW concentrations range from trace to greater than 5 mg/l, with deeper GW generally having higher fluoride concentrations Health Effects Drinking water fluoride concentrations greater than 4 mg/l can cause bone disease in adults and tooth mottling (discoloring) in children Moderate fluoride levels (0.7 to 1.2 mg/l, temperature-dependent) in drinking water are beneficial to children during the time they y are developing permanent teeth 10

Data Collection 11

Onsite Data Collection Supplement existing source water data Source water characteristics significantly affect treatment alternative selection (ph, TDS, sulfate, silica) Field Arsenic Speciation Kits- only reliable way to determine source water arsenic forms Particulate versus dissolved (soluble) Reduced [As(III)] versus oxidized [As(V)] 12

13

Total As Dissolved As Speciated As (III) 14

Source Water Characterization Results Fluoride (mg/l) Parameter Arsenic (µg/l) Total As(III) As(V) Source Water Aquifer Range Range Bicycle Lake 1.1 to 4.5 < 2.0 to 30.3 <10% 90% Langford Lake 4.4 to 9.9 7.9 to 15.8 < 1% 99% Irwin 8.0 to 10.6 32.2 to 40.1 < 5% 95% California State MCL 2.0 Current: 50 µg/l; Future: 10 µg/l Source Water Aquifer Parameter (mg/l) ph Sulfate TDS Silica Bicycle Lake 7.6 to 7.9 110 to 130 590 to 650 60 to 125 Langford Lake 8.2 to 8.5 105 to 150 480 to 560 25 to 35 Irwin 8.1 132 130 85 15

Treatment Alternative Analysis & Considerations 16

Water Quality Treatment Goals Water Quality Goal Constituent (mg/l, unless noted) Primary MCL Arsenic 1 0.0080 -- -- Fluoride 1 1.6 -- -- Nitrate 1 8.0 (as N) Secondary MCL ph 6.5-8.5 -- -- Color 15 units -- -- Turbidity 5 units -- -- Odor - Threshold 3 units -- -- Iron 0.3 -- -- Manganese 0.05 -- -- Alkalinity > 30 mg/l CaCO 3 -- -- Corrosivity 0 to 0.05 LSI -- -- Recommended Upper 2 Short Term 2 TDS 500 1,000 1,500 Sulfate 250 500 600 Chloride 250 500 600 1 - design for 80% of the MCL; 2 - Per California regulations. 17

Treatment Avoidance & Blending Non-treatment treatment: contributions of targeted source water wells are either eliminated or combined such that the product water entering the distribution system meets the arsenic and fluoride MCLs Sidestream Treatment: treating only a portion of the source water, so that subsequent blending with the untreated portion produces finished water that meets arsenic and fluoride MCLs 18

Q Mass Balance Equation SS = Q 1 C As / F,1 ε C Blending Strategies ( 1 σ ) As / F,1 C MCL 19

Treatment Options Best Available Technologies (BATs) Arsenic Activated Alumina (AA) Ion Exchange (IX) Fluoride AA RO Reverse Osmosis (RO) Electrodialysis Reversal (EDR) Oxidation/Filtration Enhanced Coagulation/Filtration Enhanced Lime Softening 20

Co-removal BATs Removal Efficiency As F Water Loss Optimal Conditions Operator Skill Activated Alumina (AA) 95% 85-95% 1-2% ph 5.5-8.3 (decreased efficiency at high ph); < 360 mg/l SO 4 ; < 1,000 mg/l TDS; < 250 mg/l Cl, < 0.5 mg/l Fe; < 0.05 mg/l Mn; < 4 mg/l TOC; < 30 mg/l Silica; < 0.3 NTU Turbidity; Low Reverse Osmosis (RO) > 95% 85-95% 40-60% < 30 mg/l silica for <15% water loss; (per RO manufacturers) No particulates. Medium Other Treatment Technologies Removal Efficiency As F Water Loss Optimal Conditions Operator Skill Electrodialysis Reversal (EDR) > 95% 85-95% 3 20-30% Treats most waters without preference; Process efficiency not affected by silica; Most economical for TDS of 3,000-5,000 mg/l; Medium Coagulation/ Micro-Filtration (C/MF) 90% NS 5% ph 5.5-8.5 High Iron Based Sorbents up to 98% No 1-2% ph 6-8.5 (decreased efficiency at high ph); < 1 mg/l PO 4 ; < 0.3 NTU Turbidity; Low Ion Exchange (IX) 95% No 1-2% ph 6.5-9 (decreased efficiency at high ph); < 50 mg/l SO 4 ; < 500 mg/l TDS; < 5 mg/l NO 3, < 0.3 NTU Turbidity; High Point of use/point of entry Devices 95% Vary Vary Scaled down versions of IX, AA, RO processes. Low 21

Adsorption Considerations Competing Ions Activated Alumina 2 ( OH ) O > F > HSeO3 > TOC > SO4 H 3 3 2 AsO4 > Si 3 AsO OH > H > Ion Exchange (IX) SO 2 3 2 2 4 > HAsO4 > NO, CO3 > NO > Cl IX is not a BAT for F removal; and SO 4- over 50 mg/l precludes IX as an economically viable technology (all source water > 100 mg/l sulfate) 22

Membrane Considerations Silica concentrations of 75 mg/l will limit RO water recovery to about 60%, per manufacturer experience. Source water varies from 25-125 mg/l silica Pretreatment for silica removal may be needed prior to RO (dependent on pilot-scale testing results). EDR, which uses electrical current, instead of pressure, to remove ionic contaminants is not affected by silica concentrations 23

Waste Stream Considerations AA - acid (ph adjustment) and caustic (media regeneration) RO/EDR - Concentrated brine discharge Disposal Options Direct discharge to evaporation ponds (100% water loss) Indirect discharge to WWTP (partial GW recharge) Vapor compression unit near zero discharge, but $$$ Sludge Criteria for Landfill Disposal Sludge must have no free liquids - Paint Filter Test Final sludge/spent media must be non-hazardous for landfill EPA has TCLP; CA has WET (F salts) 24

AA Treatment Train 25

RO/EDR Treatment Train 26

Cost COST ($) TREATMENT ALTERNATIVE Capital O&M/yr ALTERNATIVE #1: STATUS QUO - Maintain current operations, including separate 0 155,000 domestic and potable water systems. ALTERNATIVE #2: ACTIVATED ALUMINA - Construct AA columns at central location; - Pre and post treatment (ph/filtration) likely needed; - Blending used to decrease hydraulic loading; - Periodic regeneration/disposal of spent media. 4.3M 455,000 ALTERNATIVE #3: REVERSE OSMOSIS/ELECTRODIALYSIS - Construct membrane units at central location; - Pre and post treatment (filtration, conditioning chemicals, ph/alkalinity adjustment), as needed; - Blending used to decrease hydraulic loading; - Multiple pass design may minimize water loss. RO 15.0M EDR 13.0M RO 1.35M EDR 950,000 *Note: Site-specific cost factors may increase the AA capital cost to approximately $7.6M, per Fort Irwin Facilities Personnel 27

Treatment Alternatives Screening 28

Screening Criteria Each treatment alternative was screened against seven relevant criteria Except for cost, all criteria were qualitative, and rated on a scale of 1 to 7 (7 being best, and 1 being worst) Criteria scores were then summed to derive an overall alternatives ranking, with the highest scoring alternative being the preferred choice Criteria were weighted (2:1) toward regulatory compliance, water conservation and cost 29

Treatment Alternatives Criteria Wght #1 STATUS QUO #2 AA ADSORPTION #3 RO/ EDR Regulatory Compliance.2 1 (0.2) 6 (1.2) 7 (1.4) Water Conservation.2 6 (1.2) 6 (1.2) 2 (0.4) Cost.2 1* (0.2) 6 (1.2) 3 (0.6) Implementation.1 1 (0.1) 5 (0.5) 4 (0.4) Production Capacity.1 1 (0.1) 5 (0.5) 4 (0.4) Public Perception and Acceptance.1 1 (0.1) 5 (0.5) 5 (0.5) Occupational & Environmental.1 4 (0.4) 3 (0.3) 3 (0.3) Raw Score 49 15 36 28 Weighted Score (7) (2.3) (5.4) (4.0) * - based on potential non-compliance penalties 30

Search for Comparable Facility 29 Palms AA WTP - 3 MGD Design flow Located in the Hi-Desert Water District in Yucca Valley, California GW source concentrations: As: < 5 µg/l; F: 5-75 7 mg/l; 250 mg/l of TDS Blending: bypass 25% of the raw water Provides excellent treatment, endorsed by operators Novel precipitation/spray irrigation system (salt brush) Pilot-plant studies favored AA over RO/EDR 31

Conclusions 32

Treatment Technology Considerations Consider: Source water characteristics: As forms, ph, competing ions, silica, etc. Non-treatment options BATs; also look for comparable facilities Waste flows and sludge disposal For Fort Irwin: AA was the recommended treatment technology Conduct pilot-plant plant studies to verify effectiveness 33

Acknowledgements The presenter would like to thank the following people for their support of and input into this project: Mr. Mike Wright, Lead Operator, 29 Palms Water Treatment Plant Mr. Fred Rubel, P.E., Rubel Engineering Mr. Art Lundquist, USACHPPM 34

Questions? Contact Information Brian Pickard, P.E., R.S. USACHPPM, Water Supply Management Program Phone: (410) 436-8226 Email: brian.pickard@apg.amedd.army.mil 35