How could the Gold King Mine be treated with passive treatment

How could the Gold King Mine water be treated with passive treatment techniques?

Jim Gusek, PE 1

4/14/2016

How could the Gold King Mine water be treated with passive

treatment techniques?

Jim Gusek, P.E.Sovereign Consulting Inc.

Lakewood, Colorado

ROCKY MOUNTAIN WATER ENVIRONMENT ASSOCIATION SEMINAR APRIL 14, 2016 - GOLDEN, COLORADO

Outline

• Gold King Site• Passive Treatment Biogeochemistry• Conceptual Gold King Passive

Treatment Design(s)• Source Control Concepts


Jim Gusek, PE 2

4/14/2016

The Gold King Site (1/3)

2 miles

US Bureau of Reclamation, 2015




Jim Gusek, PE 3

4/14/2016



Mine Water Treatment Options

• Active (Treatment by “Brute Force” using chemicals, energy, labor, & infrastructure to produce clean water in the shortest time & smallest possible footprint)

• Passive (Treatment capitalizes on the low-energy

dynamics that Mother Nature employs at ambient temperatures)

• Combination active/passive (hybrids)


Jim Gusek, PE 4

4/14/2016

“Natural” Attenuation

Mother Nature is pretty talented; to remediate heavy metals situations, She uses:

Sequential

Ecological

eXtraction

processes that have evolved over millennia (Thanks, C. Darwin)

What Is the Passive Treatment Process?

Passive Treatment of MIW involves the:

Sequential

Ecological

eXtraction

Of metals in a man-made but naturalistic bio-system


Jim Gusek, PE 5

4/14/2016

Iron Stromatolites & Fe/Mn Nodules

Shark Bay, Australia

Fe/Mn Fossil Nodules Courtesy of Nick Shearer, WV DEP

Stromatolites built by cyanobacteria/algae, a

process over 1 billion yrs. old

www.terradaily.com

Ferricrete Deposits

Animas Basin, Colo.

Courtesy of USGS

Deposit of iron-cemented stream gravel (ferricrete) with embedded wood fragments

Natural Iron-rich Acidic Spring Flowing into

Cement Creek

Courtesy of USGS


Jim Gusek, PE 6

4/14/2016

Manganocrete Deposits

Animas Basin, CO & Patagonia, AZ

Alluvial manganocrete near the former Lake

Emma in Eureka Gulch

MnO2-cemented alluvium in Alum Creek

Courtesy of USGS

“Volunteer” iron terrace at abandoned metal mine in Colorado near a drinking water reservoir

0.5 miles upstream of Georgetown, CO (just off Guanella Pass)


Jim Gusek, PE 7

4/14/2016

Typical Wetland Ecosystem

Sulfate Reducing Bacteria (SRB’s) live here (anoxic conditions)

(oxidizing conditions)

Sulfate Reducing Bacteria (SRB’s) live here (anoxic conditions)

Oxidation and Reduction Processes in Competition

Acidithiobacillus - F. O. live here (oxidizing conditions)


Jim Gusek, PE 8

4/14/2016

Maj

or

Min

or

Natural Metal Removal Mechanisms

• Sulfide and carbonate precipitation via sulfate reducing bacteria, et al.

• Hydroxide and oxide precipitation by acidithiobacillus ferro-oxidans bacteria, et al.

• Filtering of suspended materials and precips• Carbonate dissolution/replacement• Metal uptake into live roots, stems and

leaves• Adsorption and exchange with plant, soil and

other biological materials

?

Passive Treatment Chemistry 101

SO4-2 + 2 CH2O HS- + 2HCO3

- + H+

(Sulfate reduction and neutralization by bacteria)

Zn+2 + HS- ZnS (s) + H+

(Sulfide precipitation)

Fe+3 + 3 H2O Fe(OH)3 (s) + 3 H+

(Hydroxide precipitation)

H+ + CaCO3 Ca+2 + HCO3-

(Limestone dissolution)

REDUCING/ANAEROBIC CONDITIONS

OXIDIZING CONDITIONS

ALLCONDITIONS


Jim Gusek, PE 9

4/14/2016

Aluminum Precipitation

Al3+ + 3H2O => Al(OH)3 (Gibbsite) + 3H+

(problematic due to sludge buildup)

Conditions within BCRs are favorable for aluminum hydroxysulfateprecipitation:

3Al3+ + K+ + 6H2O + 2SO42- => KAl3(OH)6(SO4)2 (Alunite) + 6H+

6Ca2+ + 2Al3+ + 38H2O + 3SO42- => Ca6Al2(SO4)3(OH)12:26H2O

(Ettringite) + 12H+

Passive Treatment System Components

Biological Components

• Anaerobic Biochemical Reactors (BCRs)

• Aerobic Cells or Rock Filters

• Successive Alkalinity Producing Systems (SAPS)

Limestone Components

• Limestone Sand

• Anoxic Limestone Drains (ALD’s)

• Alkaline Ponds

• Open Limestone Channels

Settling Ponds & Flow Equalization Ponds


Jim Gusek, PE 10

4/14/2016

Passive Treatment Decision Tree 2016

Typical Metal Mine PTS Design

RELATIVELY BAD WATERRELATIVELY GOOD WATER

1 18

1 2

H 2 13 14 15 16 17 He

3 4 5 6 7 8 9 10

Li Be B C N O F Ne

11 12 13 14 15 16 17 18

Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

87 88 89 104 105 106 107 108 109 110 111 112 114 116 118

Fr Ra Ac~ Rf Db Sg Bh Hs Mt --- --- --- --- --- ---

The Periodic Table of Elements

92

U


Jim Gusek, PE 11

4/14/2016

Periodic Table of Passive Treatment

1 18

1 2

H 2 13 14 15 16 17 He

3 4 5 6 7 8 9 10

Li Be B C N O F Ne

11 12 13 14 15 16 17 18

Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36


37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54


55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86


87 88 89 104 105 106 107 108 109 110 111 112 114 116 118


LEGEND92 Red‐ passive untreatable Green ‐ beneficial

Actinide Series U Blue – anaerobic (BCR) Uncertain ‐ untreatable?

Orange – oxidizing (Aerobic Cell) }Anaerobic and oxidizing

Periodic Table of Passive Treatment Re‐Visited

1 18

1 2

H 2 13 14 15 16 17 He

3 4 5 6 7 8 9 10

Li Be B C N O F Ne

11 12 13 14 15 16 17 18

Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36


37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54


55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86


87 88 89 104 105 106 107 108 109 110 111 112 114 116 118


LEGEND92 Red‐ passive untreatable Green ‐ beneficial

Actinide Series U Blue – anaerobic (BCR) Uncertain ‐ untreatable?

Orange – oxidizing (Aerobic Cell) }Anaerobic and oxidizing

Adsorption to MnO2

SEE: 2013 IMWA Proceedings – paper to be presented 8/8/13 @10:05a


Jim Gusek, PE 12

4/14/2016

Passive Treatment Chemistry 101

SO4-2 + 2 CH2O HS- + 2HCO3

- + H+

(Sulfate reduction and neutralization by bacteria)

Zn+2 + HS- ZnS (s) + H+

(Sulfide precipitation)

Fe+3 + 3 H2O Fe(OH)3 (s) + 3 H+

(Hydroxide precipitation)

H+ + CaCO3 Ca+2 + HCO3-

(Limestone dissolution)

REDUCING/ANAEROBIC CONDITIONS

OXIDIZING CONDITIONS

ALLCONDITIONS

Settling/Surge Ponds

Collection of suspended

solids & clarifying,

flow equalization

Skimmer unit discharge


Jim Gusek, PE 13

4/14/2016

Anaerobic Biochemical Reactors (BCRs)

Aluminum and heavy metal removal,

selenium removal, de-nitrification, pH

adjustment, alkalinity & hardness addition

AKA

Vertical Flow Reactors

or

Sulfate Reducing Bioreactors (SRBRs)

WATER SURFACE

DISCHARGE

DRAINAGE SYSTEM

ORGANIC MATTER &LIMESTONE MIX

(SUBSTRATE)

INFLOW

Anaerobic Biochemical Reactors (BCRs)

SO IT CAN BE CONSTRUCTED UNDERGROUND OR BURIED

Septic Infiltration Chambers

PLANTS ARE NOT REQUIRED FOR A BCR


Jim Gusek, PE 14

4/14/2016

BCR Cell Construction – Substrate Placing

BCR Cell Construction – Burial

Infiltrator Systems Inc. Septic H-20 Chambers


Jim Gusek, PE 15

4/14/2016

Sulfate Reducing Bacteria Sources

Cellulolytic Bacteria Source

Seyler, et al., 2003

<1% of Total Bugs!!!


Jim Gusek, PE 16

4/14/2016

Aerobic Cells

Fe, As, Biochemical

Oxygen Demand (BOD), and Mn

removal

(plus adsorbed metals)

AKA Rock Filters

Iron Terraces – Aerobic Special Case

Some ferricrete deposits in the Animas Basin are 9,000 yrs. old!

Modern Aerobic Wetlands & Ferricrete/Iron Terraces

Forest litter


Jim Gusek, PE 17

4/14/2016

Natural Treatment Chemistry 102

IRON TERRACE REACTIONS

6H+ + (C6H10O5)n + 3/2 O2 6C + 16 H2O + heat(Cellulose Dehydration by Acidity)

Reaction consumes H+

(acid) & pH rises and iron or aluminum can drop out

Volunteer Aluminum Terrace Deposition Idaho

pH 2.5; Al 800 mg/LFe 500 mg/L


Jim Gusek, PE 18

4/14/2016

Compare to Red and Bonita Mine Portal


Volunteer MnMitigation

Manganese (70 mg/L) Oxidation Assisted by

Algae in Arizona

12 Biotic mechanisms identified for Mn removal

(Robbins, 1999)

Manganese Oxidation at Neutral pH

“Manganocrete”(MnO2)


Jim Gusek, PE 19

4/14/2016

Algae Holdfast of MnO2

River Rock

Algae Strand

leptothrix discophora

Manganese/algae in outfall from Leadville Colorado (El. 10,000ft/3,050m) WTP in March

Manganese Oxidation at Neutral pH

Manganocrete from paleo-channel near Prescott, AZ

Iron & Manganese Oxidation on Moss

Mn 2+ + 2H2O → MnO2 + 4H+ + 2e-

Moss had 39% Mn by Dry Wt!

Atlantic City Iron Mine in Wyoming Elev. 8,000 ft (2,500m)


Jim Gusek, PE 20

4/14/2016

Arsenic

Copper

Lead

Zinc

Cadmium

Mercury

Molybdenum

Cobalt

Nickel

Selenium

Uranium

Radium

Silver

ManganeseOxide

(black stain on stream

gravel)

Why is manganese removal so important?

(MoreManganese)

Manganese Removal Beds

MRBs can be operated as saturated beds or as trickling filters; Fe must be removed first

Ref: Swoboda-Colberg, 1994

Ref: Hedin & Gusek, 2013

Manganocrete


Jim Gusek, PE 21

4/14/2016

The Gold King PTS Design Conditions

Parameter Value Units Assumed Condition

Flow 300 gpm Spring freshet

Flow 200 gpm Steady state

pH 3.0 S.U. Steady state

Aluminum 25 mg/L Steady state

Arsenic 22 µg/L Steady state

Iron 126 mg/L Steady state

Cadmium 75 µg/L Steady state

Copper 6.0 mg/L Steady state

Cobalt 111 µg/L Steady state

Manganese 35 mg/L Steady state

Sulfate 1,760 mg/L Steady state

Zinc 26 mg/L Steady state

US EPA, 2016Chemistry from Aug-Sept 2015


Gold King Conceptual PTS Design 1


IronTerrace


Jim Gusek, PE 22

4/14/2016

Conceptual Gold King PTS #1


Gold King Conceptual PTS Design 2


IronTerrace


Jim Gusek, PE 23

4/14/2016

Conceptual Gold King PTS #2

Organic Complexation of Metals & MnO2 Deposition in Stream Bed

Gold King PTS Sites?

7 acres Iron

Terrace

0.7 acres BCR


Jim Gusek, PE 24

4/14/2016

PART 2 – Source ControlIntroduction to the Acid Rock

Drainage Tetrahedron

ARD is a global bacterial infection.

There are plenty of geo-antibiotics available but the current situation might be a lack of education. We’ve know about this for over 25 years.

What’s needed is a mining-analogue to an I-V drip of tetracycline and/or oral antibiotics.

And then there’s the question: Do we need to Vaccinate or Medicate and what do these concepts mean?

A Medical Analogue


Jim Gusek, PE 25

4/14/2016

Acid Rock Drainage Tetrahedron

Oxidizer(Air, Fe+3) Bacteria

Pyrite

WaterFuel

Air Heat

FIRE

ARD

Common Pyrite Forms

• Crystalline• Framboidal

~20 µm

Ref: GARD Guide

Framboidal pyrite offers much more opportunity for bacterial colonization


Jim Gusek, PE 26

4/14/2016


Bad Bacteria

Water

Pyrite

Oxidizer(Air, Fe+3)

DO NOTHING = PERPETUAL TREATMENT

DO SOMETHING (anything) = PATHWAY TO WALK-AWAY


GoodBacteria

Water

Pyrite

Oxidizer(Air, Fe+3)

“PROBIOTIC” PATHWAY TO WALK-AWAY


Jim Gusek, PE 27

4/14/2016

Pyrite Oxidation Review

Initiator Reaction:

Propagation Cycle:

FeS2 + 3.5 O2 + H2O Fe2+ + 2 SO42- + 2 H+

Pyrite Acid

14 Fe3+ + FeS2 + 8 H2O

15 Fe2+ + 2 SO42- + 16 H+

Acid

Fe2+ + 0.25 O2 + H+ 0.5 H2O + Fe3+

Pyrite

6Bacteria 10 X

ORGANIC MATTER

Known “bactericides” (low‐hanging “pHruit”?)

Sodium lauryl sulfate (shampoo)

Alkyl-benzene sulfonate (laundry soap)

Waste milk (bacteria out-complete acido-thiobacillus)

Sodium Thiocyanate (NaSCN)

Bi-Polar LipidsNote: We need to consider the physics of delivering and distributing a weak bactericide solution into a porous, unsaturated medium.

Bacteria enhance pyrite oxidation rates ten-fold or more


Jim Gusek, PE 28

4/14/2016

“Control of acid generation for prolonged periods greatly enhances reclamation

efforts and can reduce reclamation costs by reducing the amount of topsoil

needed to establish vegetation. Three natural processes resulting from strong

vegetative cover for three years or more can break the acid production cycle.

These processes are:

1. A healthy root system that competes for both oxygen and moisture with acid-

producing bacteria;

2. Populations of beneficial heterotrophic soil bacteria and fungi that are reestablished,

resulting in the formation of organic acids that are inhibitory to T. ferrooxidans (Tuttle

et al. 1977); and

3. The action of plant root respiration and heterotrophic bacteria increase CO2 levels in

the spoil, resulting in an unfavorable microenvironment for growth of T. ferrooxidans.”

ARD Prevention Concept is Not New

Sobek, A. A., D.A. Benedetti, & V. Rastogi. 1990.

IT’S ALL A MATTER OF TIMING


Jim Gusek, PE 29

4/14/2016

Vaccination or Medication Concepts

Vaccination (Prevention) Medication (Mitigation)

Waste rock dumps at active mines (“sterilize” ARD rock by the truckload (or lift) before it is placed in the dump)

Small-scale “dog hole” abandoned underground mines that produce ARD

Active coarse coal refuse piles (sterilize refuse by adding a bactericide and/or “probiotic” in the feed hopper of a conveyor belt)

Waste rock dumps or coarse coal refuse facilities at abandoned mines (even if they are capped)

Active tailings storage facilities (sterilize the cycloned coarse tails (or paste) in the embankment – the material most likely to form ARD before capping and revegetation)

Abandoned underground mine stopes (use geophysics for targeting and inject bactericide and/or “probiotic” through bore holes or land applied on the surface with drip irrigation technology)

Active underground mine stopes (amend backfill materials)

Backfilled pits that are poorly capped (and then revegetate!)

The “Heat‐Seeking Missile” Effect in ARD Suppression

Pyrite oxidation is exothermic

Some reactants respond (positively) to acid

If a reactant mixture encounters a “hot zone” with elevated pyrite: the delivery media should collapse and preferentially

deposit the “active ingredients”, and/or

the active ingredient itself would preferentially coat the pyrite.

These features could potentially give some technologies a “heat-seeking missile” advantage that could automatically deliver more ARD-suppressing active ingredients in the zones where they are needed the most.


Jim Gusek, PE 30

4/14/2016

A Bulkheading Special Case

• Closed historic Keystone underground hardrockmine, SW Colorado

• Effluent (450 gpm) treated for cadmium and zinc with a lime do$ing plant

• Owner (US Energy) planned to bulkhead five adits to minimize discharge & passively treat bulkhead leakage under the VCUP statute

• Mine would likely fill with acidic water – potential for off-site migration through fractures


Keystone Mine Drawing Courtesy of US Energy, Riverton, WY


Jim Gusek, PE 31

4/14/2016


• Install bulkheads

• Recirculate a powdered limestone slurry (you can’t overdose) as the mine pool fills with neutralized MIW

• Monitor pH, metals, and alkalinity

• Build passive treatment system (manganese removal bed) for estimated 30 gpm of bulkhead leakage (pH ~7-8)

• Monitor off-site seepage (if any) for geochemical fingerprint (Ca/Mg ratio)

VCUP Plan Summary

The Gold King Site



Jim Gusek, PE 32

4/14/2016

2 miles

The Gold King Site


Bad Bacteria

Water

Pyrite

Oxidizer(Air, Fe+3)

DO NOTHING = PERPETUAL TREATMENT

DO SOMETHING (anything) = PATHWAY TO WALK-AWAY


Jim Gusek, PE 33

4/14/2016


GoodBacteria

Water

Pyrite

Oxidizer(Air, Fe+3)

“PROBIOTIC” PATHWAY TO WALK-AWAY

REVIEW – Pathway to Walk‐Away

1. Primary Source Control to minimize flow, metals concentrations, and loading

2. Reclamation/Remediation to sustain primary source control measures for the long term

3. Passively Treat residual conditions– pH 2.5 to 8.5

– Metals (Fe, Cu, Pb, Zn, Cd, Cr, Mn, Hg, Mo, Al, Se, As, U, Co, Tl)

– Non-metals (CN, SO4, NO3, NH3, BOD5, P)– Temperatures (0 to 30 deg C)– Major processes are:

• Chemical precipitation (usually facilitated by bugs) in aerobic and anaerobic conditions

• Adsorption to MnO2, etc. (facilitated by algae)


Jim Gusek, PE 34

4/14/2016

[email protected]

“In the fields of observation, chance favors only the prepared mind.”

L. Pasteur

Thank You

Documents

How could the Gold King Mine be treated with passive treatment