timothy k. tsukamoto, ph.d

Overviews of Two Advanced AMDOverviews of Two Advanced AMDTreatment Technologies: Semi-Treatment Technologies: Semi-

passivepassiveSulfate Reducing Bioreactors andSulfate Reducing Bioreactors andthe Rotating Cylinder Treatment the Rotating Cylinder Treatment

System System July 2008July 2008

Timothy K. Tsukamoto, Ph.D.Timothy K. Tsukamoto, Ph.D.

RCTS™

Semi-passive BioreactorsSemi-passive Bioreactors Timothy K. Tsukamoto, Ph.D.Timothy K. Tsukamoto, Ph.D.

(775) 321-8100 (775) 321-8100www.iwtechnologies.com

http://www.iwtechnologies.com/

Options for Treatment

AdvantagesAdvantages DisadvantagesDisadvantagesBioreactor Bioreactor and other and other passive passive systemssystems

1.1. Mostly PassiveMostly Passive 1.1. Requires spaceRequires space2.2. Lifetime limitedLifetime limited3.3. Higher capital costHigher capital cost

Caustic Caustic additionaddition

1.1. Semi-passiveSemi-passive2.2. Easily implementedEasily implemented

1.1. Higher chemical Higher chemical costcost

2.2. Increased sludge Increased sludge volumevolume

3.3. Adds sodium to Adds sodium to waterwater

Lime Lime precipitationprecipitation

1.1. Removes sulfateRemoves sulfate2.2. Decreases TDSDecreases TDS

1.1. Higher capital costHigher capital cost2.2. Requires some O&MRequires some O&M

Types of Bioreactors Passive BioreactorsPassive Bioreactors

-The carbon or energy source is part of the substrate.-The carbon or energy source is part of the substrate.-Once the degradable carbon sources are depleted, -Once the degradable carbon sources are depleted, treatment efficiency falls off.treatment efficiency falls off.-Metals are precipitated within the matrix.-Metals are precipitated within the matrix.-Plugging and short circuiting leads to decreased -Plugging and short circuiting leads to decreased treatment efficiency.treatment efficiency.

Semi-Passive BioreactorsSemi-Passive Bioreactors-The carbon source is added to the influent water-The carbon source is added to the influent water-The majority of the metals are precipitated outside of -The majority of the metals are precipitated outside of the bioreactor.the bioreactor.-Flushing built into the matrix.-Flushing built into the matrix.-All three contribute to a longer lasting system-All three contribute to a longer lasting system

Passive BioreactorsPassive Bioreactors-The carbon or energy source is part of the -The carbon or energy source is part of the

substrate.substrate.-Once the degradable carbon sources are -Once the degradable carbon sources are

depleted, depleted, treatment efficiency falls off.treatment efficiency falls off.

-Metals are precipitated within the matrix.-Metals are precipitated within the matrix.-Plugging and short circuiting leads to -Plugging and short circuiting leads to

decreased decreased treatment efficiency.treatment efficiency. Semi-Passive BioreactorsSemi-Passive Bioreactors

-The carbon source is added to the influent -The carbon source is added to the influent waterwater

-The majority of the metals are precipitated -The majority of the metals are precipitated outside of outside of the bioreactor.the bioreactor.

-Flushing built into the matrix.-Flushing built into the matrix.-All three contribute to a longer lasting system-All three contribute to a longer lasting system

Sulfate-reducing Activity

Passive Bioreactors Passive Bioreactors 0.3 moles per cubic meter per day0.3 moles per cubic meter per day

limited to about 1 meter deeplimited to about 1 meter deepso 0.3 moles per square meter per dayso 0.3 moles per square meter per day

Semi-passive BioreactorSemi-passive Bioreactor0.56 moles per cubic meter per day0.56 moles per cubic meter per daycan go much deepercan go much deeperSo for Leviathan Bioreactor 3 meters deep So for Leviathan Bioreactor 3 meters deep 1.68 moles per square meter per day1.68 moles per square meter per day

Leviathan MineOriginal Manure Substrate at the Leviathan Mine.

-down-flow reactor approximately 3ft deep. -ineffective at treating AMD after 1 year. -the source of manure substrate for the column experiments that

follow.

Leviathan Mine

Six Weeks of Treatment

One Year of Treatment

7-27-93 7-1-94

Influent Effluent Influent Effluent

pH 4.78 6.97 4.7 6.45

Temperature C 9.9 15.6 8.4 13.1

alkalinity - 1458.00 - 269

Al 41.0 <0.02 48 0.24

As 0.41 0.023 0.28 0.015

Fe 310 2.8 380 260

Ni 1.8 0.01 2.1 0.01

Sulfate 1690 1190 2070 1910

Leviathan MineSulfate concentrations vstime for Leviathan underdrain site4-3-97 to 7-10-98.

Time (Days)

0 100 200 300 400 500

Sul

fate

con

c. (m

g/L)

0

500

1000

1500

2000

2500

3000

influenteffluent

Iron concentrations vstime for Leviathan underdrain site4-3-97 to 7-10-98.

Time (days)

0 100 200 300 400 500

Iron

conc

(mg/

L)

0

100

200

300

400

500

600

influent effluent

Leviathan Mine

Improved flow distributionImproved flow distribution Improved matrixImproved matrix Improved sludge captureImproved sludge capture

Leviathan Mine

Leviathan Mine

Pretreatment Pond Bioreactor 1 Bioreactor 2 Settling Pond 1 Settling Pond 2

Oxidizing AerationTrench

Sodium HydroxideAnd Ethanol Delivery

Sodium HydroxideDelivery

Infiltration Pond

Leviathan Mine

Aspen seep

Pretreatment Pond

Bioreactor 1 Bioreactor 2 Settling Pond 1 Settling Pond 2

Oxidizing AerationTrench

Ethanol DeliverySodium Hydroxide

Delivery

Infiltration Pond

Recycle Line

Bypass Line

Leviathan Mine

Leviathan Mine

ConstitueConstituentnt

Aspen Aspen SeepSeep

Bioreactor Bioreactor 1 effluent1 effluent

Bioreactor Bioreactor 2 effluent2 effluent

DischargeDischarge Discharge Discharge objectivesobjectives

pHpH 2.932.93 6.796.79 6.866.86 7.667.66 6-96-9SOSO44 15301530 10901090 10801080 11701170 NANAAlAl 2828 <0.5<0.5 <0.5<0.5 <0.5<0.5 4.04.0FeFe 9999 0.160.16 0.130.13 0.040.04 2.02.0NiNi 0.500.50 0.150.15 0.050.05 0.10.1 0.840.84CuCu 0.620.62 0.020.02 0.010.01 0.010.01 0.0260.026ZnZn 0.730.73 0.020.02 0.020.02 0.060.06 0.210.21

Leviathan MinepH

Time (days)

0 100 200 300 400 500 6002

3

4

5

6

7

8

9

10

Influent pH Effluent pretreatment pond Effluent pond 1 pH Effluent pond 2 pH Pond3 Pond4 Discharge

2004

no base studyrecirculation

Sulfate

Time (days)

0 100 200 300 400 500 600

Sul

fate

Con

cent

ratio

ns (m

g/L)

600

800

1000

1200

1400

1600

1800

0

10

20

30

40

50

60

Influent Effluent pretreatment pond Effluent pond 1 Effluent pond 2 Pond 3 Pond 4 Discharge Flow

2004


Leviathan MineIron

Time (days)

0 100 200 300 400 500 600

Iron

Con

cent

ratio

n (m

g/L)

0

20

40

60

80

100

120

140

0

10

20

30

40

50

60

Influent Effluent pretreatment pond Effluent pond 1 Effluent pond 2 Pond3 Pond4 Discharge Flow

2004


Aluminum

Time (days)

0 100 200 300 400 500 600

Al C

once

ntra

tion

(mg/

L)

0

10

20

30

40

Influent Effluent pretreatment pond Effluent pond 1 Effluent pond 2 Pond3 Pond4 Discharge

2004


Leviathan MineNickel

Time (days)

0 100 200 300 400 500 600

Nic

kel C

once

ntra

tion

(mg/

L)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0

10

20

30

40

50

60


2004


Copper

Time (days)

0 100 200 300 400 500 600

Cu

Con

cent

ratio

ns (m

g/L)

0.0

0.2

0.4

0.6

0.8

Flow

(L/m

in)

0

10

20

30

40

50

60


2004


Leviathan MineZinc

Time (days)

0 100 200 300 400 500 600

Zinc

Con

cent

ratio

n (m

g/L)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

0

10

20

30

40

50

60


2004


Leviathan Mine

Nacimiento Mine

Nacimiento MineConstituents of Concern for Nacimiento well field.

Well ID Al Cd Cu Fe Pb Mn Ni Zn Sulfate pHMW-2 0.94 ND 2.54 63.3 0.0039 0.777 0.1 8.58 980 5.6

MW-5 0.41 ND 0.065 1.63 0.0057 0.065 0.02 1.76 190 6.5MW-6 1.38 ND 0.79 13.8 0.0119 0.088 ND 0.09 260 5.2MW-9 3.73 ND 0.74 10.4 0.005 0.304 0.06 3.02 450 3.6MW-10 28.6 0.01 20.8 124 0.0267 1.53 0.18 13.1 1,960 3.2MW-11 43.3 0.012 57.6 261 0.0913 2.73 0.25 20.5 1,760 2.7MW-12 0.36 ND 0.21 9.92 0.0019 11.3 0.06 0.17 1,730 6.9MW-14 0.36 ND 0.51 7.62 0.0085 3.27 0.02 0.12 860 7.5MW-21 70.5 0.018 116 324 0.111 16.2 0.36 28.2 2,930 2.9MW-32 0.17 ND 0.08 1.61 0.0095 0.084 ND 0.21 250 6.9MW-33 9.03 0.01 157 159 0.0024 2.71 0.37 25.4 1,630 4.0MW-35 0.65 0.028 O.41 1.36 3.77 0.146 0.03 2.57 30 6.2MW-36 0.21 ND 0.02 3.59 0.0017 0.343 ND 0.06 750 7.2

Nacimiento Mine

The Rotating Cylinder Treatment The Rotating Cylinder Treatment System™System™

Timothy K. Tsukamoto, Ph.D.Timothy K. Tsukamoto, Ph.D. (775) 321-8100 (775) 321-8100

www.iwtechnologies.com

http://www.iwtechnologies.com/

CONFIDENTIALITY PROPRIETARY INFORMATION NOTICE

All information delivered in this presentation relating to the Rotating Cylinder Treatment System (“RCTS”), US Patent No. 7,011,745 is patented technology proprietary to Ionic Water Technologies, Inc. The presentation’s content related to IWT’s technologies shall not be used for any purpose by any recipient or viewer hereof without the express written consent of Ionic Water Technologies, Inc.

RCTS CONCEPTRotating perforated cylinders add oxygen from the atmosphere to the water

Energy efficient 10 hp system treats up to 500 gpm

Aggressive agitation optimal reagent efficiencyReduced lime costs

Low maintenance rotor maintenance on most sites2 to 3 times per year (takes 3 to 4 hours)

Small footprint most units are mobile

Effective Aeration and Oxidation

Less Sludge produced

Faster sludge settling

Chemistry and Chemistry and StoicheometryStoicheometry

For Hydrated Lime

Ca(OH)2 + M 2+ M(OH)2 (s) + Ca 2+ Ca 2+ + SO4 2- CaSO4

Gypsum generally precipitates to ~ 2,000 mg/L

For Sodium Hydroxide

2 NaOH + M 2+ M(OH)2 (s) + Na + Sodium remains soluble

Chemistry and Chemistry and StoicheometryStoicheometry

CaO=1 Na(OH)=1.43Ca(CO)3=1.78

If 2000 mg/L acidity then need= 1120

mg/L of CaO and 1600 mg/L of NaOH and 920 mg/L will be Na

Lime Precipitation

Add lime (CaO) or Ca(OH)2 to raise the pHPrecipitate metals as hydroxidesPrecipitate sulfate as gypsumRequires oxygen addition if there is significant dissolved iron, manganeseOxygen addition is typically accomplished with large compressors

and air diffusers and tanks Lime addition requires thorough mixing due to it’s low solubility and slow dissolution rate.Mixing is typically accomplished with large mixers inside reaction tanksLabor and energy demanding

Iron Hydroxide Solubility with Respect to pHpH vs Total Iron Solubility Diagram for Ferrous and Ferric Hydroxide Precipitation.

Note the Minimum Solubility for Manganese Precipitation is Between pH 9 and 10.

(Taken from USEPA 1983).

Improved Oxygen Addition

O2 = Qw x Fe x 7.14 x 10 -5O2 = Theoretical O2 demand (lb O2/hr)Qw = Acid mine drainage flow rate (gal/min)Fe = Fe 2+ initial concentration (mg/L)

U.S. Environmental Protection Agency (USEPA). 1983. Design Manual: Neutralization of Acid Mine Drainage. EPA-600/2-83-001.

Type of Aeration Pounds of O2 delivered per horsepower-hour

Mechanical surface aeration 3.0-3.5

Submerged turbine aerators utilizing dual impeller turbines

2.5-3.0

RCTS 600 gallon four rotor 9.0

Elizabeth Mine

Results from StartupResults from StartupTable 1. Results for samples taken at various pH with and without settling. All samples were taken at an influent flow rate of

approximately 32 gpm.

Sample ID Initial pH FeT Fe2+ Mn Al Cu Zn 24 hour pH

Influent 6.13 710 715

A (24 hours settling) 11.35 0.46 0.24 0.50 0.03 0.00 0.35 10.56

B (24 hours settling) 10.29 0.05 0.00 0.02 9.12

C (24 hours settling) 9.64 0.38 0.14 0.40 0.01 0.00 0.00 9.23

D (24 hours settling) 9.45 0.28 0.03 0.00 8.90

E (24 hours settling) 9.08 0.40 0.06 0.40 8.42

F (24 hours settling) 8.06 1.18 0.07 3.00 7.85

G (24 hours settling) 7.52 1.44 0.02 2.30 7.34

H (24 hours settling) 6.83 3.22 0.08 7.80 6.66

I (24 hours settling) 6.08 84.50 10.65 8.00 5.42

J (24 hours settling) 5.60 54.00 4.42

K (sampled from unit and filtered immediately no settling ) 9.80 0.20 0.00 0.20

Pond 7-26 (not filtered) 7.51 0.36 0.26 1.80

Pond 7-27 (filtered) 0.05 0.04 0.70

Pond 7-28-08 (not filtered) 7.54 0.10 0.03

Iron and Manganese Iron and Manganese OxidationOxidation

The Effect of pH on Oxidation Rates for Iron and Manganese. All experiments were conducted at dissolvediron and manganese concentrations of less than 5 x 10-4 M. (a) oxygenation of Fe 2+ in bicarbonate solutions(b) oxygenation of Mn 2+ in bicarbonate solutions (c) oxidation of Mn 2+ in bicarbonate solutions (autocatalytic plot)(d) Effect of pH on oxidation rates (taken from Faust and Aly 1981)

Sunshine Mine

Residence time in RCTS 1 to 2 minutes

Mn ppm after treatment

0

2

4

6

8

10

12

14

16

18

8 8.5 9 9.5 10 10.5 11

operating pH

Mn

ppm

1 hr settle

3 hr settle

1 hr filter

1 day

2 day

Figure 1

LEVIATHAN MINE, NORTHERN CALIFORNIALEVIATHAN MINE, NORTHERN CALIFORNIAATLANTIC RICHFIELD SITE 2007ATLANTIC RICHFIELD SITE 2007

HydraulicCapacity(gallons)

AverageFlowRate(gpm)

SystemResidence

Time(minutes)

InfluentpH

EffluentpH

FilterBagpH

EffluentDO mg/l

AverageLime

per Day

Conventional Tank Reactor

System 4000 30.38 131.67 4.73 7.88 8.12 4.22 398

Rotating Cylinder Treatment

System

1600 *includes

dosing tank 27.33 58.54 4.86 8.12 8.11 7.86 233

Comparison of RCTS with Conventional SystemLeviathan Mine

EMERGENCY TREATMENT AT THE LEVIATHAN MINE

2006Plowed the road April 9 and let the road dry.Mobilized the lime on April 12 and 13 via 4 wheel drive equipment.Mobilized the entire treatment system on April 13Started treating on April 14 and by 10 a.m April 15 the average pH of the pond was 8.4.Treated 24 hours/day with 2 man crew onsite an average of 4.6 hours/dayMet USEPA directivesTreated and actively discharged ~7.5 million gallons of water containing iron as high as 610 mg/L and aluminum as high as 490 mg/L.Removed ~ 180 m3 of sludge from the lined pond in 2 days

Comparison of RCTS with Conventional SystemLeviathan Mine

RCTS vs Conventional RCTS vs Conventional System Leviathan MineSystem Leviathan Mine

Water Treated per ton of lime

RCTS 150,000 gallonsConventional System 73,000 gallons

Empire Mine

Goals: To oxidize and precipitate the iron and co precipitate arsenic from solution. It was initially proposed that sodium hydroxide would be added to raise the pH from 6.6 approximately 8.0. The addition of base was not necessary (Degassing of carbon dioxide from the water)

HCO3- + H+ H2O + CO2

Nevada Pit Lake

Nevada Pit Lake•6 Billion gallon pit lake pH~2.9

•Utilize CaO fed through a silo

Utilize the RCTS and IWT lime grinder to slake the lime and dissolve it

•Add CaO at ~ 2.8 lbs/ min and slake with ~ 2 to 10 gpm to obtain a slurry of 3.5% to 17.5%

•Mix with between 50 and 300 gpm of water in the RCTS unit (lime dissolvesCompletely)

•Reintroduce with the ~6,000 gpm of water feeding the pit lake

•It will take ~ 1,000,000 lbs of CaO to neutralize 1 B gallons

•2.8 lbs/min ~ 120,000 lbs per month so we would neutralize ~ 1.5 B gallons per year

Cost ComparisonCost ComparisonCost to treat 1Bg of water

$ units Gallons tons Material Delivery Total Caustic $0.13 poundCaustic $1.66 gal 263,158 1,679 $436,842 $31,413 $468,255 12.76 #/galQuickLime $76.00 ton 2,000,000 533 $40,508 $15,015 $55,523 1.66 gallonKiln Dust* $8.00 ton 2213 $17,704 $63,535 $81,239 Delivery $ 18.71 tonNote* Kiln dust usage is ~4x Quicklime usage for equivilant CaOH

Cost to treat current lake volume of 5.6 Bg 3990 elev. Quick lime 76.00 tonMaterial Infrastructure Labor* Total Delivery $ 28.17 ton

Caustic $2,622,230 $10,000 $0 $2,632,230 QuickLime $310,927 $201,800 $135,000 $647,727Kiln Dust* $454,940 $201,800 $135,000 $791,740 Kiln Dust 8.00 ton

28.71 tonNote*IWT labor rate at $5,200/wk for 6 months Infrastructure for caustic is containment and piping

# of loads assuming 70,000#/truckCaustic 269QuickLime 85Kiln Dust 354

= $0.11/1000 gallons neutralized

Sludge Settling Sludge Settling Elizabeth MineElizabeth Mine

5 minutes 10 minutes 15 minutes

Sludge Sludge SettlingSettling

1hour 2 hour 4 hours

Sludge SettlingSludge Settling

7 hour 24 hour

Sludge SettlingSludge SettlingGrouse Creek Mine RCTS Settling vs Conventional System

A B C D A B C D 1 Minute Settling 2 Minute Settling

A= Conventional System with polymer and sulfideB= RCTS no polymer no sulfideC= RCTS with polymer no sulfideD= RCTS with polymer and sulfide

Sludge SettlingSludge Settling

A B C D A B C D 5 Minute Settling 20 Minute Settling

A= Conventional System with polymer and sulfideB= RCTS no polymer no sulfideC= RCTS with polymer no sulfideD= RCTS with polymer and sulfide

timothy k. tsukamoto, ph.d

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