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Pilot Tests of Adsorptive Media Arsenic Pilot Tests of Adsorptive Media Arsenic Treatment Technologies in the Arsenic Water Treatment Technologies in the Arsenic Water

Technology PartnershipTechnology Partnership

Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company,for the United States Department of Energy’s National Nuclear Security Administration

under contract DE-AC04-94AL85000.

Malynda Aragon Malynda Aragon Malcolm SiegelMalcolm Siegel

Sandia National LaboratoriesSandia National LaboratoriesAlbuquerque, NMAlbuquerque, NM

February 7, 2006February 7, 2006

Sandia Team MembersSandia Team Members

Tom Hinkebein, Malcolm Siegel, Malynda Aragon, Alicia Aragon, Randy Everett, William Holub Jr., Jerome Wright, Justin Marbury, Emily Wright, Bryan Dwyer, Michelle Shedd, Carolyn Kirby, Paul McConnell, Hongting Zhao, Linnah Neidel, Nik Rael, Andres Sanchez, David Stromberg

Why Is Sandia Pilot Testing?Why Is Sandia Pilot Testing?Scatter plots of BV*As vs. pH and SiO

Note: these contain data from various sources, including pilot and RSSCT

studies

6.5 7.0 7.5 8.0 8.5 9.0

0

1000000

2000000

3000000

4000000

5000000

6000000

BV

*As

pH

Why Is Sandia Pilot Testing?Why Is Sandia Pilot Testing?

10 20 30 40 50 60 70

0

1000000

2000000

3000000

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6000000

BV

*As

SiO

Scatter plots of BV*As vs. pH and SiO

Note: these contain data from various sources, including pilot and RSSCT

studies

Outline

• The Arsenic Water Technology Partnership• Site selection • Concepts for Pilot Demonstration Tests• Initial Tests in New Mexico

– Socorro, Anthony, Rio Rancho• Future work

– Jemez Pueblo, Socorro (Phase 2), Oklahoma• Summary

Arsenic Water TechnologyArsenic Water TechnologyPartnership BackgroundPartnership Background

• Congressional Appropriation - $10M FY03 – FY05• DOE- funded peer-reviewed, cost-shared research program to develop and demonstrate innovative technologies for removal and disposal of arsenic from drinking water• Partner Roles

– Bench-Scale Studies (AwwaRF)– Demonstration Studies (Sandia)– Economic Analysis/Outreach (WERC)

• Focus on small systems – 40% of resources directed to rural and Native American utility needs– Minimize costs - capital, operating, maintenance– Minimize residual quantities & disposal costs

Sandia Pilot Test ConceptsSandia Pilot Test Concepts

• Side-by-side demonstrations of technologies tested by AwwaRF bench-scale program, WERC design contest, or commercial technologies vetted through Vendor Forums– Test duration: 3 – 9 months– Test size: 0.3 – 10 gpm – Different technology classes: adsorptive media,

Coagulation/Filtration, membranes, electrochemical• Cooperative effort between Sandia, Technology

Owner and Site Owner• Test Protocols developed with help from NSF

International, academia, industry during 2004-2005

Things we look for in a pilot siteThings we look for in a pilot site

• As concentration (>10 ppb)• Example ground water composition that will help other

communities– pH, TDS, foulants such as Fe, Mn, silica, and organics– As(III)/As(V)– Competing ions (V, SO4, etc. )– Other contaminants of concern/benefit (e.g, Ra, U, ClO4, F)

• Small size of system to be treated (< 10,000 users)• Community support facilitates rapid deployment

– Water utility– Municipal government

• Ability to deal with residuals/treated effluent• Rural and Native American communities that would benefit

from assistance

Sites in New MexicoSites in New Mexico

Anthony

Socorro

Jemez Pueblo

Rio Rancho

New Mexico Pilot Sites New Mexico Pilot Sites ––Water Quality Summary (Average Values)Water Quality Summary (Average Values)

1.000.900.500.50F (ppm)0.02.00.00.2NO3 (ppm N)2.00.50.80.5TOC (ppm)290160180130Alkalinity (ppm CaCO3)

7706201400340Conductivity (µS/cm)

7.57.67.78.0pH1.20.150.50.04Fe (ppm)155557044Ca (ppm CaCO3)2410018029SO4 (ppm)50273725SiO2 (ppm)<115211V (ppb)

20 / 1919 / < 120 / 1842 / <2Total As/As(III), ppb

Jemez PuebloRio RanchoAnthonySocorro

RED = above EPA Primary MCL; BLUE = above EPA secondary MCL

First Community Pilot: Socorro, NMFirst Community Pilot: Socorro, NM

• 100% groundwater source for drinking water

• 2 warm springs (90oF) provide 500 gpm, 35 – 55 ppb As(V) by gravity flow.

• Formerly site of tap for bottled water company;

• Optimal F for oral health• Phase 1: Feb-Oct 2005

– Tested• Fe oxides: AD33, ARM200• Resin - ArseneXnp

• Ti-oxide - Metsorb• Zr-oxide - Isolux

– EBCT study of AD33• 3,4,5 min

First Community Pilot: Socorro, NMFirst Community Pilot: Socorro, NM

0.20.3N/A0.30.3BW FR, gpm

0.40.30.50.30.30.30.4Water FR, gpm

4.74.50.395.64.52.23Media V, L39.238.51048.138.519.325.7Hmedia, inches60601060603939Hcol, inches

NoNoYes(0.5µm)

NoNoNoNoPre-filtration required?

340.205422EBCT, min.

8.162368HLR, gpm/ft2

ArsenXnp

(S5)ARM 200

(S4)Isolux 302M

(S7)AD-33(S8-10)

MetSorb(S6)

Vendor Media

Socorro Pilot Phase I and IIa EventsSocorro Pilot Phase I and IIa EventsSB, SC = Influent; S4 = ARM200 (FeOx); S5 = ArseneXnp (resin); S6 = Metsorb (TiOx); S7 = Isolux (ZrOx); S8-10 = AD33 (FeOx)

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10/4/

2005

As

(ppb

)

SB SC S4 S5 S6 S7 S8 S9 S10

pH adjusted to 6.8

Media Performance: Socorro, NMMedia Performance: Socorro, NMS4 = ARM200 (FeOx); S5 = ArseneXnp (resin); S6 = Metsorb (TiOx);S7 = Isolux (ZrOx); S8-10 = AD33 (FeOx)

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Bed Volumes

As

(ppb

)

S4 S5 S6 S7 S8 S9 S10

Incoming Arsenic: 40-50 ppb

Media Performance in Socorro, NMMedia Performance in Socorro, NM

• Arsenic Removal Capacity

> 4.622.232.102.261.15Capacity at C/Co = 0.8

>270,00063,00053,00087,00033,000BV at C/Co = 0.8

0.150.380.350.600.88Depletion - C/Co at 35K BV

3.011.671.751.391.17Capacity at 35K BV, mg/g

3.561.671.380.700.60Capacity at 10 ppb, mg/g

43,00032,00027,00013,0008,600BV to 10 ppb

AD33(FeOx)

Isolux (ZrOx)

*ArseneXnp

(Resin)Metsorb (TiOx)

ARM200(FeOx)

Parameter

*ArseneXnp batch was defective

Media Performance in Socorro, NMMedia Performance in Socorro, NM

• Effect of EBCT on Arsenic Removal Capacity

>3.47> 4.624.03Capacity at C/Co = 0.8

>235,000>270,00084,000BV at C/Co = 0.8

0.120.150.50Depletion - C/Co at 35K BV

2.923.012.59Capacity at 35K BV, mg/g

3.473.561.95Capacity at 10 ppb, mg/g

42,00043,00024,000BV to 10 ppb

5 min4 min2 minAD33Parameter

Hydraulic Test Results: Socorro, NMHydraulic Test Results: Socorro, NM

Results: Physical Observations• Sieve Analysis: 0.8-29% loss• Particle Size Uniformity: All media had Cu < 5, most <2.5

(fairly uniform)• Surface Area: Doesn’t seem to control As removal – the

media with the smallest surface area had the highest capacity

• Each column reacted differently to operating conditions– Media was lost due to backwashing– Media compacted throughout pilot experiment

RSSCT Results: Socorro, NMRSSCT Results: Socorro, NM

AD33 - 2 min EBCT

00.20.40.60.8

1

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Bed Volumes Treated

Nor

mal

ized

As

C/C

o

PD RSSCT

CD RSSCT

Pilot

AD33- 4 min EBCT

00.20.40.60.8

1

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Bed Volumes Treated

Nor

mal

ized

As

C/C

o

PD RSSCT

Pilot

CD RSSCT

AD33 - 5 min EBCT

00.20.40.60.8

1

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Bed Volumes Treated

Nor

mal

ized

As

C/C

o

PD RSSCT

CD RSSCT

Pilot

RSSCT Results: Socorro, NMRSSCT Results: Socorro, NM

ArseneXnp

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Bed Volumes Treated

Norm

aliz

ed A

s C/

Co PD RSSCT

Pilot

ARM 200

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0.6

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Bed Volumes Treated

Nor

mal

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As

C/C

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Metsorb

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Nor

mal

ized

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C/C

o PD RSSCT

Pilot

Objective of RSSCTsObjective of RSSCTs

• Apply RSSCTs to site specific waters to aid in the design of pilot studies and full-scale treatment systems

• Significantly reduce time and costs associated with pilot studies

• Two RSSCT designs:• Proportional Diffusivity: duration 2-5 weeks• Constant Diffusivity: duration 2-10 days

• Breakthrough curves from PD and CD RSSCTs should bracket breakthrough curves from pilot columns but so far results are not consistent.

Phase II Studies in SocorroPhase IIa:• Capacity extension tests of spent media

– pH adjustment by CO2 gas– Interrupted flow

Phase IIb:• Side-by side comparisons of 5 media at 2 pH levels

pH = (8: ambient and 6.8:CO2 gas)– ArseneXnp – QC’d batches– Isolux – larger cartridge for more ‘reliable’ BV– Kemiron – FeOx media– SANS – Sandia proprietary media– Metsorb – TiOx media

• Evaluate inadvertent effects of treatment– Loss of pH control and arsenic spike

Second Community Pilot: Anthony, NM Second Community Pilot: Anthony, NM (Desert Sands MDWCA)(Desert Sands MDWCA)

• 100% groundwater source for drinking water

• Warm springs (~85oF) provide 240-270 gpm, 20 ppb As - mainly As(III).

• High sulfates, TDS• Intermittent Flow Operation• Media Tested

– FeOx: AD33, ARM200, CFH12– ZrOx: Isolux– TiOx: Metsorb, Adsorbsia GTO– Resins: ASM-10HP, ArseneXnp

• Phase 2: Coated media December 2005

– La, Fe, Mg-coated diatomaceous earth

– FeOx-Coated GAC– Fe-coated silicate– Also: re-loaded ArseneXnp

column

0.30.12295063

0.9810 x 18

Kemiron CFH 12

0.30.30.30.3Water Flowrate (gpm)0.120.120.120.12Media Volume (ft3)29292929Media Depth (in)50505050Column Height (in)6666Loading Rate (gpm/ft2)3333EBCT (min)

0.80.720.760.48Bulk Density (g/ml)10 x 6016 x 6012 x 4010 x 35Mesh Size

DowAdsorbsia

GTO

HydroglobeMetsorb

EngelhardARM 200

AdedgeAD33

Pilot ScaleDesign Parameters

0.30.30.3Water Flowrate (gpm)0.120.12Media Volume (ft3)2929Media Depth (in)33Column Diameter (in)66Patent pending

radial flowcartridge system

42”cartridge height

Loading Rate (gpm/ft2)330.5EBCT (min)

0.740.810.86Bulk Density (g/ml)20 x 4016 x 50< 400Mesh Size

ResinTechASM10 HP

PuroliteArseneXnp

MEIIsolux

Pilot ScaleDesign Parameters

DES

ERT

SAN

DS

DES

IGN

INFO

Media Performance: Anthony, NMMedia Performance: Anthony, NMS1=Isolux (ZrOx); S4 = CFH12 (FeOx); S5 =AD33 (FeOx); S6 = ARM200 (FeOx);S7=Adsorbsia GTO (TiOx); S8=Metsorb (TiOx); S9=ArseneXnp; S11=NXT-2

0

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25

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Bed Volumes

Ars

enic

(As)

- pp

b

S1 S4 S5 S6 S7 S8 S9 S10 S11

Incoming Arsenic: 20-22

Speciation of Arsenic: Anthony, NMSpeciation of Arsenic: Anthony, NM

0

5

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25

8/16/2

005

8/23/2

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9/6/20

059/1

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59/2

0/200

59/2

7/200

510

/4/20

0510

/11/20

0510

/18/20

0510

/25/20

0511

/1/20

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/8/20

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/15/20

0511

/22/20

0511

/29/20

0512

/6/20

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/13/20

0512

/20/20

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/27/20

051/3

/2006

As

(ppb

)

12/3/05:Added extra retention time for HOCL

10/21/05:Speciating correctly in the field now

Many of the samples maybe bad, due to incorrect

speciation technique

Media Performance: Anthony, NMMedia Performance: Anthony, NM

• Backwashing:– Some media have required

monthly backwashing (~2,000 bed volumes)

– Others have required bi-monthly backwashing (~4,000 bed volumes)

– A few have required little or no backwashing

• Most media haven’t compressed much (compressed<10% of original height)

• Can see iron oxide forming at top of ZrOx media and pre-filter

Third Community Pilot: Rio Rancho, NMThird Community Pilot: Rio Rancho, NM• 100% groundwater source for

drinking water• Deep well (800 ft) provides

2000 gpm, 20 ppb As (mainly As V).

• High sulfates, Vanadium, TDS• Phase 1: September 2005

Start– FeOx: AD33, CFH10– ZrOx: Isolux– TiOx: Adsorbsia GTO– Resins: ASM-10HP,

ARseneXnp

• Continuous Flow Operation• Pre-sieved media prior to

loading & initial backwash (> 60 mesh)

Third Community Pilot: Rio Rancho, NMThird Community Pilot: Rio Rancho, NM

0.40.40.40.40.40.4Backwash FR (gpm)

0.30.30.30.30.30.3Water FR (gpm)

0.120.120.120.120.12Media V (ft3)

2929292929Media Depth (in)

66Patent pendingradial flowcartridge system

42”cartridge

height

666HLR (gpm/ft2)330.5333EBCT (min)

0.740.810.860.980.80.48Bulk Density (g/ml)

20 x 4016 x 50< 40010 x 1810 x 6010 x 35Mesh Size

ResinTechASM10 HP

PuroliteArseneXnp

MEIIsolux

Kemiron CFH 10

DowAdsorbsia

AdedgeAD33

Pilot ScaleDesign Parameters

Media Performance: Rio Rancho, NMMedia Performance: Rio Rancho, NM

0

5

10

15

20

25

0 5000 10000 15000 20000 25000 30000 35000

Bed Volumes

As

(ppb

)

S1 S2 S3 S4 S5 S6

Incoming As between 20-25 ppb

S1=AD33 (FeOx); S2 = CFH10 (FeOx); S3 =ArseneXnp; S4 = ASM-10HP; S5=Adsorbsia GTO (TiOx); S6=Isolux (ZrOx)

Summary: Bed Volume ResultsSummary: Bed Volume Results

N/AMedia broke down at 2,400

N/ANXT-2

17,0008,000N/AASM-10HP

>20,000>10,00027,000ArseneXnp

>20,000>10,000N/AAdsorbsia GTO

N/A>10,00013,000Metsorb

>20,000>10,00032,000Isolux

>20,000>10,000N/ACFH12, CFH10

>20,000>10,00026,000/43,000/42,000 (2/4/5 min EBCT)

AD33

N/A>10,0009,000ARM200

Rio Rancho BV to 10 ppb breakthroughb

Desert Sands BV to 10 ppb breakthrougha

Socorro BV to 10 ppb breakthrough

Media

aPhase 1 not yet completebPhase 1completion data

Summary: ResultsSummary: Results

• Pilot studies have been completed or are in progress at three sites in New Mexico: Socorro, Anthony, and Rio Rancho.

• In general, the smaller the particle size of the media, the more susceptible the media is to incoming iron and/or particulate matter.

• These media require more backwashing than others. • Empty bed contact time (EBCT) does have an

affect on the relative performance of the media. • Most media vendors recommend 3-5 minutes EBCT• 3 minute EBCT is generally sufficient, in that higher

bed volumes to 10 ppb breakthrough are demonstrated regularly.

Summary: Future PlansSummary: Future Plans

• In 2006, the Arsenic Water Technology Partnership will undertakeseveral activities:– Rio Rancho will be restarted by early spring 2006; a new pilot

will also occur at this site– Phase 2 operations will begin at the Socorro site– A new pilot will start in Oklahoma – A new pilot will start at the Jemez Pueblo

• The Jemez Pueblo pilot demonstration site will :– Test Coagulation-filtration technologies– Test the effectiveness of various oxidizers for Arsenic (III)– Compare pilot scale data to full scale iron and manganese

removal plant.• Pilot-specific economic analyses will be performed at each site to

gain further insight to the relative performance of each of the media. These results will be used to supplement our partner, WERC, in their efforts to build the Comprehensive Arsenic Tool (CoAsT).

For More Information:For More Information:

Arsenic Partnership Websitehttp://www.arsenicpartners.org/

Sandia Websitehttp://www.sandia.gov/water/arsenic

WERC CoAsT Websitehttp://wercstation.nmsu.edu:8080/arsenic/AsTree.dsb